Curso de Quimica I

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On-Line Learning Center for "Organic

Chemistry" (Francis A. Carey)
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Chapter 1: Chemical Bonding
Chapter 2: Alkanes
Chapter 3: Conformational Analysis of Alkanes and Cycloalkanes
Chapter 4: Alcohols and Alkyl Halides
Chapter 5: Structure and Preparation of Alkenes. Elimination Reactions
Chapter 6: Reactions of Alkenes. Addition Reactions
Chapter 7: Stereochemistry
Chapter 8: Nucleophilic Substitution
Chapter 9: Alkynes
Chapter 10: Conjugation in Alkadienes and Allylic Systems
Chapter 11: Arenes and Aromaticity
Chapter 12: Reactions of Arenes: Electrophilic Aromatic Substitution
Chapter 13: Spectroscopy
Chapter 14: Organometallic Compounds

Chapter 15: Alcohols, Diols and Thiols
Chapter 16: Ethers, Epoxides and Sulfides
Chapter 17: Aldehydes and Ketones. Nucleophilic Addition to C=O
Chapter 18: Enols and Enolates
Chapter 19: Carboxylic Acids
Chapter 20: Carboxylic Acid Derivatives. Nucleophilic Acyl Substitution
Chapter 21: Ester Enolates
Chapter 22: Amines
Chapter 23: Aryl Halides
Chapter 24: Phenols
Useful Concepts
Chapter 1: Chemical Bonding <>

Summary:
Understanding the structure and bonding of organic molecules is fundamental to being able to
understand their properties and reactions. This is because the properties and reactions are controlled
by the interactions between molecules which are in turn dictated by the types of bonds within those
molecules.
Although you may feel that most of this chapter is review from your General Chemistry course(s),
many students are not as strong as they need to be to survive the adventure that lies ahead, so make
sure you start your organic course in good shape.
As you will see later, understanding the location of electrons is especially important as it is the
arrangement of the electrons that creates the bonds between the atoms, and chemical reactions are
just a reorganisation of those electrons to form new bonds.
Review: What should I already know about ?
Atoms, Electrons and Orbitals
Bond types: Ionic, Covalent, Polar Covalent
Lewis Structures and Formal Charge
The Shapes of Molecules
Hybridisation
More practice problems ?
Atoms:
All matter is composed of atoms. Atoms are a collection of various subatomic particles.
You should be familiar with the subatomic particles how to determine how many of each a
specific atom has and what the atomic mass of an atom represents. Try some questions. If you
are not comfortable perhaps you need to look a bit more in depth.
In organic chemistry, as far as the compounds are concerned, the atoms of greatest interest are
located the first three rows of the periodic table. Later when one probes deeper into synthetic
methods, one needs to be familiar with some of the heavier metals as well.
Electrons and Orbtials:

The subatomic particle of greatest interest with respect to chemical bonding, is the electron.
Electrons are 'said' to occupy orbitals in an atom. The term orbital is somewhat 'erroneous' as
electrons do not 'orbit' around a nucleus. These orbitals, also, do not really exist. They are
mathematical constructs which make use of a wavefunction, , that describes the motion of an
electron.
An orbital is, more correctly, a mathematical function, 4r22, which describes a region of high
probability in 3D space, about a nucleus, where an electron may be found. In organic chemistry
one needs to be most familiar with the s- and p-type orbitals. These orbitals can be described by
using quantum numbers. The orbitals for the electrons in carbon, and the associated quantum
numbers are given below. The nucleus of the carbon atom would reside at the centre of the x,y,z
coordinate.
You should be familiar with the meaning of quantum numbers, how to name an orbital using
quantum numbers or what orbital a set of quantum numbers defines. Try some questions. If your
struggling you'll need to review the meaning of quantum numbers.
The electron configuration of an atom describes the number of electrons that atom possesses and
the orbitals in which those electrons are to be found.
e.g. electron configurations of carbon
simple 1s2 2s2 2p2

short form [He]2s2 2p2
orbital energy diagram
You should be familiar with how to determine an electron configuration for an atom and identify
the valence electrons. You should be able to identify both ground and excited state electron
configurations. Try some questions. If you are having trouble you should review how to
determine electron configurations.
Bond types:
Why is it important to understand the structural arrangement of electrons in an atom?
In everyday life, chemistry arises out of the interaction of molecules with molecules... but what is a
molecule? It is a collection of atoms. When the atoms come together their electron clouds interact
with one another and if this interaction is 'favourable' then bonding occurs.
One of the driving forces behind bonding is an atoms desire to obtain a stable valence electron
configuration. For the atoms that are most important in organic chemistry, (N, C, O, Cl, Br, and I),
this is an octet of electrons, which is similiar to the valence electron configuration of the nearest
noble gas (ns2np6).
Ionic bonds result when electrons are tranfered between atoms.

Covalent bonds result when valence electrons are shared between atoms.
You should be able to identify whether an ionic or covalent bond is being formed between atoms.
Try some questions. If you are having difficulty then you need to review bonding.
Most bonds within organic molecules will be covalent. The execeptions will be compounds which
possess metal atoms (where the metal atoms should be treated as ions). It is important to note that
the electron distribution within a covalent bond is not always symmetrical. If it is not then the bond
is said to be polar as opposed to non-polar.
If a bond is covalent you should be able to identify whether it is polar or non-polar. Try some
questions. If you are having difficulty then you need to review bond polarity.
Lewis Diagrams:
Lewis Diagrams give the connectivity between atoms in a molecule; they tell you nothing about
the arrangement of the atoms of a molecule within 3D space (that is left to VSEPR or
Hybridisation).
You should be able to draw a Lewis diagram for both organic and inorganic molecules as the
latter are often used as reagents in organic syntheses. Examples. If you are not yet comfortable
with detemining a Lewis diagram, take a look at an outline of how to determine a Lewis diagram.
In reality, electrons in a molecule are being delocalized within that molecule. Consequently, more
than one Lewis diagram can be used to describe molecules which possess multiple bonds.
Collectively these Lewis diagrams are then known as resonance structures and their sum is often
represented as the resonance hybrid (note a resonance hybrid is not a Lewis diagram!).
You should be able to draw all reasonable resonance structures for a given organic molecule.
Examples. If you are not yet comfortable with examining the resonance in a molecule you should
review the concept of resonance.
Shapes of Molecules:
In order to view some of the structures for this section, you will need the web "plug-in", "CHIME".
If you do not have it already installed, you should be able to download it for free from the linked
Website. CHIME is a browser that allows you to visualise and manipulate molecules as 3D
structures. Check here if you don't know how to use Chime.
When determining the shape of a molecule the premise is that groups of electrons surrounding an
atom are repelled as far as possible from each other to minimize the overall energy of the molecule.
Groups of electrons can refer to electrons that participate in bonding (single, double, or triple) or to
those that are non-bonding (e.g. lone pair electrons). The number and types of groups are
determined from a Lewis diagram.
Not only is it important for a chemist to be able to visualize a structure, they must also be able to
effectively (clearly!) transfer this knowledge onto a piece of paper!!!!!!
A molecule is visualized as if it were centered in the plane of the paper and, generally, so that the
most number of atoms possible are in that plane. Unbroken lines are used to represent bonds in the
plane of the paper, hashed wedges represent bonds going back out of the plane of paper and solid
wedges represent bonds coming out of the plane of the paper.
There may be several different ways that you can represent a molecule on a piece of paper. You
should be able to discriminate which of those drawings most clearly represent the structure of a
molecule.
You should be able to determine the shape of a molecule by looking at the electronic and
molecular geometry about all non-terminal atoms. In doing so you must be able to present clear
drawings of your conclusions. Try some questions. If you are having problems doing this you will
need to review VSEPR.
Once the shape of a molecule is known, by referring to the sum of the bond polarities, the
molecular polarity can be determined. This is important when examining the reactivity of a
molecule.
You should be able to indicate a molecule's polarity.
Hybridisation:
Covalent bonds are formed when atomic orbitals overlap. There are two types of orbital overlap
that an organic chemist needs to be familiar with. Sigma, , overlap occurs when there is one
bonding interaction that results from the overlap of two orbitals. Pi, , overlap occurs when two
bonding interactions result from the overlap of orbitals.
The organic chemist also needs to realise how these orbital overlaps relate to the type of bonding
that is occuring between atoms:
single bond overlap
double bond and overlaps
triple bond and two overlaps
If one tries to correlate the overlap of atomic orbitals to the shape of a molecule, however, the
expected geometry does not correspond to a maximum orbital overlap. Take a look at methane,
CH4. VSEPR predicts a tetrahedral geometry about the carbon atom but this is not achieved when
one considers a maximum orbital overlap between four 1s orbitals of H and the 2s, 2p x, 2py and 2pz
orbitals of carbon.
Hybridisation is a solution to this problem. It is the imaginary mixing of the 2s, 2px, 2py and 2pz
atomic orbitals of carbon to form a new set of 'hybrid' orbitals that orient themselves in the
desired VSEPR geometry. The hybrid orbitals are equivalent to one another making all orbital
overlaps equivalent, therefore, all C-H bonding interactions equivalent.
Hybrid orbitals are named by considering the type and number of atomic orbitals from which they
arose. For CH4 then the hybridisation for the carbon is sp3. One sees that the hybridisation of an
atom can be determined very quickly by considering the number of electron groups about an
atom. Hybrid orbitals are responsible for all the bonding overlaps in a molecule.Unhybridised
orbitals are responsible for all the bonding overlaps in a molecule
.
You should be able to predict the hybridisation of all non-hydrogen and non-terminal atoms in a
molecule and draw the bonding interactions in that molecule based on the hybridisation model.
Try some questions.
If you are still having difficulty with hybridisation, then you will need to review your concept of
hybridisation.
Chapter 2 : Alkanes <>
Summary:
With the basis of structure and bonding behind us, we are ready to begin examining the structure,
reaction and applications of organic compounds, and this start with the simplest organic systems,
the alkanes.
As you head into all the material ahead, it is important the remember that in almost all of the
reactions that you will encounter, the reactions occur directly at or adjacent to the functional
groups within the molecule.
The physical properties of molecules such as melting points, boiling points and solubility are
dictated by intermolecular forces.
Functional Groups
What is a functional group ?
List of functional groups
Sample questions
Hydrocarbons
Types of hydrocarbons ?
Alkanes
Nomenclature
Physical Properties
Structure
Isomers
Stability
Reactivity
Sample questions
Cycloalkanes
Nomenclature
Physical Properties
Structure
Reactivity
Thermodynamics and Stability
Heat of Combustion
Oxidation and Reduction

Identifying Oxidation and Reduction reactions
Oxidation states for organic molecules
Drill Problems
Chapter 2 : Alkanes
Functional Groups
A functional group is an atom or a group of atoms within a molecule, that prescribes a
particular type of reactivity when subjected to a particular set of reaction conditions.
As organic chemistry unfolds, take notice that the reactions occur directly at or immediately
adjacent to the functional groups, and that recognising the functional groups is the key to
recognising the type of reaction.
What is a reaction ?
A reaction is the process by which one compound is transformed into a new compound.
Chapter 2 : Alkanes
List of Functional Groups
The more important functional groups are shown below, with the key structural element and a 3D
CHIME image of a simple example. It is important that you are able to recognise these functional
groups because they are the key to being able to recognise the patterns within organic chemistry.
Alkane
Alkene
Alkyne
Arene
Alcohol
Alkyl halide
Amine
Epoxide
Ether
Nitrile
Nitroalkane
Thiol
Aldehyde
Ketone
Carboxylic Acid
Acyl halide
Acid anhydride
Ester
Amide
Chapter 2 : Alkanes
Functional Group Questions

Qu : The structure of EPOTHILONE A, a compound with
anticancer activity similar to Taxol is shown to the right.
(a) Identify the functional groups in Epothilone A.
(b) What is the hybridisation at each of the following atoms

in Epothilone A ?
C1 C8 C12 C14 C17 C19
(c) Arrange the following bonds in Epothilone A in order of

decreasing length: C14-C15 C15-C17 C17-C18
(d) What type of bonding MOLECULAR orbitals are

involved in the bonds between C3-C4 and C17-C18 ?
Answers ?
Chapter 2 : Alkanes
Hydrocarbons
Hydrocarbons are compounds that only contain H and C atoms, but they can be subdivided
according to the following tree diagram depending on the bond types that are present.
Hydrocarbons
CcHh
Alkanes Alkenes Alkynes Arenes

Only CC bonds CC and bonds CC and 2bonds 6 C cyclic array
all C sp3 hybridised C=C CC all C sp2 hybridised
Chapter 2 : Alkanes
Alkanes:
Simplest organic molecules with only C and H atoms. Commercially important as fuels and oils.
Nomenclature:
Functional group suffix = -ane (review)
Functional group prefix = alkyl-
Physical Properties:
The low polarity of all the bonds n alkanes means that the only intermolecular forces between
molecules of alkanes are the very weak induced dipole - induced dipole forces, which are easily
overcome. As a result, compared to other functional groups, alkanes tend to have low melting and
boiling points and very low solubility in polar solvents such as water (remember "oil and water
don't mix" and the adage "like dissolves like").
Structure:
Alkanes are the simplest organic compounds, comprised of only sp 3 hybridised C and H atoms
connected by bonds.
They have a generic formula of CnH2n+2 (a relationship that also defines the maximum number of
hydrogen atoms that can be present for a given number of C atoms).
Structures of the simple C1 to C4 alkanes are shown below in a variety of representations. As the
number of C atoms increases then other isomeric structures are possible
Methane
CH4
(b.pt. = -160oC)
Ethane
C2H6
(b.pt. = -89oC)
Propane
C3H8
(b.pt. = -42oC)
Butane
C4H10
(b.pt. = -0.4oC)
Stability:
More branched alkanes are more stable that linear alkanes, e.g. 2-methylpropane is more
stable than n-butane.
Reactivity:
Since C and H atoms have very similar electronegativities, so all the bonds in alkanes (C-C
and C-H) are non-polar.
As a result, alkanes are not particularly reactive as functional groups go.
Infact, it is often convenient to regard the hydrocarbon framework of a molecule as an
unreactive support for the more reactive functional groups.
Chapter 2 : Alkanes
Isomeric Alkanes
The molecular formulae for the C1 to C3 alkanes lead to single, unique structures.
However for C4H10, there are two possible constitutional isomers. It is important to be able to
recognise isomers because there can have different chemical, physical properties and biological
properties. The constitutional isomers of C4H10 are shown below along with some properties:
m.pt.= -139oC
b.pt. = -0.4oC
Hf = -125.6 kJ/mol
n-butane (-30.0 kcal/mol)
Hc = -2877 kJ/mol
(-687 kcal/mol)
m.pt.= -161oC
b.pt. = -10.2oC
Hf = -135.6 kJ/mol
isobutane (-32.4 kcal/mol)
Hc =-2868 kJ/mol
(-685 kcal/mol)
For C5H12 has three possible constitutional isomers:
b.pt. = 36.1 oC
Hf = -147 kJ/mol
n-pentane
(-35.1 kcal/mol)
Hc = - 3509 kJ/mol
(- 839 kcal/mol)
b.pt. = 30 oC
Hf = -154.1 kJ/mol
isopentane (-36.8 kcal/mol)
Hc = -3502 kJ/mol
(-837 kcal/mol)
b.pt. = 9.5 oC
Hf = -168.0 kJ/mol
neopentane (-40.1 kcal/mol)
Hc = -3493 kJ/mol
(- 835 kcal/mol)
Chapter 2 : Alkanes
Cycloalkanes
Another type of molecule containing only sp3 hybridised C and H atoms connected by bonds is
possible with a ring of 3 or more C atoms. These are the cycloalkanes which are fairly common in
the world of organic chemistry, both man-made and natural.
Nomenclature:
Functional group prefix = cyclo- (review)
Physical Properties:
Like alkanes, the low polarity of all the bonds in cycloalkanes means that the only intermolecular
forces between molecules of cycloalkanes are the very weak induced dipole - induced dipole forces,
also known as van der Waals forces which are easily overcome. As a result, compared to other
functional groups, but like alkanes, cycloakanes tend to have low melting and boiling points.
Structure:
They have a generic formula of CnH2n, (note: there 2 less H atoms compared to the analogous
alkane).
The C3 to C6 cycloalkanes are shown below in a variety of representations.
Cyclopropane
C3H6
Cyclobutane
C4H8
Cyclopentane
C5H10
Cyclohexane
C6H12
Reactivity:
Very similar reactivity to the closely related alkanes which have the same types of bonds.
Since C and H atoms have very similar electronegativities, both the C-H and C-C bonds are
non-polar.
As a result, cycloalkanes, like alkanes, are not a very reactive functional group
Basic Organic Nomenclature
Mono-Cyclic Alkanes
The bonding of carbon atoms is not limited to simple chains. Carbon atoms can form cyclic
structures as well. The general formula for a linear or branched chain is C nH2n+2 where n is the
number of carbon atoms. In a mono cyclic ring the general formula is C nH2n . The loss of the two
hydrogen atoms represents the additional carbon-carbon bond in the ring.
Naming cyclic rings follows the same rules as for linear chains, with the addition of the
prefix cyclo to the name of the compound.
Names of the simple cyclic hydrocarbons
Formula Name Line Diagram Molecular Model

C3H6 cyclopropane
C4H8 cyclobutane
C5H10 cyclopentane
C6H12 cyclohexane
Substitution on the ring is also possible. When the ring is larger than the longest continuous chain of
carbon atoms in a substituent, the ring will be the parent compound.
Example 1.)
The ring is larger than the ethyl group so the name is: ethylcyclopentane
NOTE: no number is needed as there is only a single substituent.
Multiple substituents are located on the ring by numbering clockwise or counter-clockwise

from one substituent to the other(s), thus there will always be a substituent at carbon number
1. The substituent, and direction of numbering, are chosen to give the lowest total for all
substituents, i.e. starting at one substituent what is the shortest distance arround the ring, in
either direction, to the next substituent.. If the numbers for the substituents will be the same
in either direction, then the substituent that comes first alphabetically should have the lower
number.
Example 2.)
The ring is larger than both groups so the name is: 1-ethyl-2-methylcyclobutane
NOTE: the ethyl group is first alphabetically so it gets the lower number..
Example 3.)
The name is: 4-isopropyl-1,2-dimethylcyclohexane

NOTE:
o this gives to lowest total number for the three substituents, i.e. the shortest distance
from the two methyl groups to the isopropyl group.
o the isopropyl comes before the dimethyl
When the chain is longer than the ring, the ring becomes a substituent on the chain. As a substituent,
the ring is named following the rules for alkanes, drop the -ane and replace it with -yl. For example
a cyclopropane ring as a substituent becomes a cyclopropyl group.
Example 4.)
The chain is larger so the name is: 4-cyclobutyl-5-cyclopropyl-2-methylheptane

Next Page: Cycloalkanes - Stereochemistry
Return to Index
Useful Concepts
Oxidation and Reduction

An important part of the task of electron book-keeping.
Oxidation, [O], and reduction, [R], are opposites and both must occur simultaneously, hence
redox reactions.
Organic chemists will normally describe a reaction as either oxidation or reduction
depending on the fate of the major organic component.
Oxidation:
more C-O bonds (or other atoms more electronegative than C)
less C-H bonds
loss of electrons
increased oxidation state, e.g. +1 to +3 (see below)
Reduction:
more C-H bonds
less C-O bonds (or other atoms more electronegative than C)
gain of electrons
decreased oxidation state, e.g. +1 to -1 (see below)
Calculating Oxidation Number or State (there are several methods for doing this, pick the one
that works for you !)
This allows for a more formal, quantitative decription of the oxidation state for the C atoms and is
based on looking at what atoms are attached to the C atom in question. The algebraic sum of the
oxidation states must equal the charge of the molecule.
for attached C atoms, i.e. C-C bonds electrons shared, count 0
for attached X atoms, i.e. C-X bonds (X more electronegative), count -1 (per bond)
for attached H atoms, i.e. C-H bonds (H is less electronegative than C), count +1
Add the total for atoms attached to the C in question, then switch the sign.
Here are a few examples, and a couple of schemes that show important relationships:
Tips: In General Chemistry or High School you may have learnt that O is always -2, however it is
better to count each bond to an O as -1 since there is a difference between C=O and C-O as seen by
comparing the aldehyde and the alcohol in the diagram above. After all , the -2 statement is
wrong.... for example in oxygen gas, the oxidation state is zero
Chapter 3:
Conformations of Alkanes and Cycloalkanes <>
Summary:
The different spatial arrangments that a molecule can adopt due to rotation about sigma bonds are
called conformations and hence conformational isomers or conformers.
The study of the energy changes that occur during these rotations is called conformational
analysis.
This is important because the structure of a molecule can have a significant influence on the
molecular properties, including dictating the outcome of a reaction. Although the ideas are
developed for the simplest functional groups, the alkanes, the same principles can be expanded and
applied to other functional groups.
Conformational analysis has its own language. A list of the key terms is provided with direct links
to explanations.
The ability to draw and interpret the different diagrams (wedge-dash, sawhorse, Newman) used to
represent the different conformations is also important.
Conformational Analysis of:

Simple alkanes: Methane, Ethane and Propane
Higher alkanes: Butane and beyond
Cycloalkanes
Substituted cyclohexanes
Polycyclics
Heterocycles
Interesting Molecules
Sample questions
Drill Problems
Ch3 On-Line Assessment
Chapter 3:
Conformations of Alkanes and Cycloalkanes
Conformational Language
An alphabetical list of key terms in the language of conformational analysis is provided below,
linked to the more detailed descriptions within the chapter pages
Description given to two substitutents

Anti attached to adjacent atoms when their bonds
are at 180o with respect to each other.
A high energy conformation where the bonds

Eclipsed
on adjacent atoms are aligned with each other.
A low energy conformation where the bonds

Staggered on adjacent atoms bisect each other,
maximising the separation.

Gauche attached to adjacent atoms when their bonds

Syn attached to adjacent atoms when their bonds
Different spatial arrangments that a molecule

Conformations
can adopt due to rotation about sigma bonds.
Conformers Contracted version of conformational isomers.
Alternative expression for conformational
Rotamers
isomers.
Conformational Structures that can be interconverted by
isomers rotation about sigma bonds.
Cycloalkane An ring containing only C-C bonds.
Heteroatom A non-carbon atom such as O,N,S etc.
A cyclic molecule that includes a heteratom
Heterocycle
such as O,N,S etc. as part of the ring.
Puckered A non-planar geometry of a cyclic structure.
The process by which a ring changes it's
Ring flipping
conformation.
A position on a chair cyclohexane in which
the bond to the ring is perpendicular to the
Axial
average plane of the ring (i.e. pointing
towards the poles).
A position on a chair cyclohexane in which
the bond to the ring is approximately in the
Equatorial
average plane of the ring (i.e. around the
equator).
The most stable conformation for
Chair
cyclohexane.
A high energy conformation of cyclohexane
Boat
that occurs during ring flipping.
Energy associated with a system due to it's
Strain
geometry.
Destabilisation due to distortion of a bond
angle from it's optimum value caused by the
Angle strain
electrostatic repulsion of the electrons in the
bonds.
Destabilisation due to the repulsion between
the electron clouds of atoms or groups. Also
known as Van der Waals strain or repulsion.
Steric strain
This occurs when atoms or groups are too
close to each other due to the electrostatic
repulsion of the electrons.
Destabilisation due to the repulsion between
Torsional strain pairs of bonds caused by the electrostatic
repulsion of the electrons in the bonds.
Angle between C-X and C-Y bonds in a X-C-

Torsional angle
C-Y system. Also known as a dihedral angle.
The destabilisation of a cyclic structure

compared to a related non-cyclic structure,
Ring strain mainly due to angle and torsional strain. This
extra energy is released when the ring is
broken.
Chapter 3:
Drawing and Understanding Diagrams

The ability to draw and interpret the different diagrams that are used to represent the different
conformations is an important skill to acquire. Maximise your artistic talents ! The only person that
will be decieved by your poor diagrams is you ! Your instructor will be able to tell instantly that you
are struggling....
These diagrams allow 3D representations of molecules to be drawn on the 2D world of a piece of

paper (or computer screen), in a similar way to which one can look at the plans for a house.
wedge-dash sawhorse Newman cyclohexane
Wedge-dash diagrams:
Usually drawn with two bonds in the plane of the page, one infront, and one behind to give the
molecule perspective. When drawing wedge-dash it is a good idea to visualise the tetrahedral
arrangement of the groups and try to make the diagram "fit" this. As a suggestion, they seem to be
most effective when the "similar" pairs of bonds (2-in-plane, 2-out-of-plane) are next to each other,
see below:
Sawhorse:
Sawhorse diagrams are similar to wedge-dash diagrams, but without trying to use "shading" to
denote the perspective. The representation to the right of propane has been drawn so that we are
looking at the molecule which is below us and to our left.
Newman:
These projections are drawn by looking directly along a particular bond in the system (here a C-C
bond) and arranging the substituents symmetrically around the atoms at each end of that bond. The
protocol requires that the atoms within the central bond are defined as shown below:
In order to draw a Newman projection from a wedge-dash diagram, it is useful to imagine putting
your "eye" in line with the central bond in order to look along it. Let's work through an example,
consider drawing a Newman projection by looking at the following wedge-dash diagram from the
left hand side.
First draw the dot and circle to represent the front and back C respectively
Since the front carbon atom has an H atom in the plane of the page pointing up we can add
that first
The back carbon atom has an H atom in the plane of the page pointing down
Now add the other bonds to each C so that it is symmetrical
The groups / bonds (blue) that were forward of the plane of the page in the original wedge-
dash diagram are now to our right
Those behind (green) the plane are now to our left
Try the same thing, but looking from the right to generate the other Newman projection
Cyclohexane
Drawing cyclohexane so that it looks like a chair can be the key to appreciating the axial and
equatorial positions....
First step is drawing the chair itself. Although the chair "looks better" when slightly angled, it
maybe easier to "learn" to draw it with the middle protion horizontal.
Chapter 3:
Alkanes
By starting with simple alkanes we can prepare ourselves for the more complex world that lies
beyond.....
Methane: CH4
Although sigma bonds are able to

rotate about the internuclear axis, the
spherical symmetry of H atoms
means that methane has only a single
unique conformation.
Ethane: CH3-CH3
Rotation about the C-C bond in

ethane (see animation) produces
different conformations. Although
an infinite number of conformations
are possible, the staggered
conformation and the eclipsed
conformation which represent the
most and least stable respectively are
the most important.
These can be seen by rotating the
ethane molecule to view it directly
down the C-C bond, as in a Newman
projection.
STAGGERED
Look at how the each H-C-H bond angle is bisected by a C-H bond on the
adjacent C atom. This is the most stable conformation for ethane since the
torsional strain is minimised.
ECLIPSED
Think like an astronomer....each of the C-H bonds is aligned with a C-H
bond on the adjacent C atom so that the H attached to the front C obscures
(eclipses) those on the rear C
Propane: CH3-CH2-CH3
Although there are 2 C-C bonds in

propane, they are equivalent and
rotation produces conformations that
are similar to those of ethane except
that the "extra" methyl group is
interacting with the H atoms.
These can be seen by rotating the
propane molecule to view directly
down the C-C bond, similar to a
Newman projection.
Chapter 3:
Higher Alkanes
The same basic ideas of conformational analysis developed for simple alkanes also apply, but some
new situations are encountered.
Butane: CH3-CH2-CH2-CH3
In butane it is the rotation about the C2-C3 bond that is of most

interest since the relative position of the two methyl groups is
important.
This can be seen most easily by rotating the molecule to view it

down the C2-C3 bond.
The more important conformations are shown below:
ANTI
a staggered conformation with the Me
groups at 180o with respect to each other
GAUCHE
SYN
an eclipsed conformation with the Me
GAUCHE
(note: the two gauche conformations are not quite the same, try to convince yourself of this. How
are they related ?)
Chapter 3:
Cycloalkanes
Commonly encountered in natural products, such as steroids. Cyclopentanes and cyclohexanes are
the most common. Other than cyclopropane these are non-planar or "puckered" systems. This
puckering relieves some of the ring strain by lowering angle and torsional strains.
Cyclohexane: C6H12
The most stable conformation of cyclohexane is the chair form shown to the right. The C-C-C
bonds are very close to 109.5o, so it is almost free of angle strain. It is also a staggered
conformation and so is free of torsional strain. You can rotate the molecule in the image to show
this just like a Newman projection.
The chair is the most stable conformation of cyclohexane.
A second, much less stable conformer is the boat conformation. This too is almost free of angle
strain, but in contrast has torsional strain associated with eclipsed bonds at four of the C atoms. You
can rotate the molecule in the image to show this just like a Newman projection.
In addition, a steric interaction of the H atoms inside the bow and the stern, known as the flagpole
interaction also destabilises the boat.
Click here to highlight flagpole hydrogen atoms
Click here to reset colors

A third conformation is produced by twisting the boat to give the twist or skew-boat conformation.
The twist relieves some of the torsional strain of the boat and moves the flagpole H further apart
reducing the steric strain. Consequently the twist boat is slightly more stable than the boat.
Click here to highlight flagpole hydrogen atoms

Conformational rotation (also known as ring-flipping) of cyclohexane interconverts two chair
forms. This proceeds from chair to twist boat to boat to twist boat to chair. Watch the animation
carefully.
Chair Cyclohexane
In chair cyclohexane there are two types of positions, axial and equatorial. The axial positions
point perpendicular to the plane of the ring, whereas the equatorial positions are around the plane
of the ring. These can be highlighted in the diagram below.
Click here to highlight an equatorial hydrogen atom;
Click here to highlight all equatorial hydrogen atoms;
Click here to highlight an axial hydrogen atoms
Click here to highlight all axial hydrogen atoms
Click here to highlight the carbon skeleton

OTHER CYCLOALKANES
Other than cyclopropane (which must be planar), cycloalkanes are also "puckered" to relieve some
of the ring strain. The structures of some of the smaller cycloalkanes are shown below with the
planar structures for contrast. In each case, manipulate the images to look for the deviation from
planarity and the effect this has on the eclipsing interactions of adjacent H atoms and C-C bonds. In
order to be able to compare the strain in each member of the cycloalkane series, the heat of
combustion per methylene (i.e. -CH2-) is also given.
C3H6
CYCLOPROPANE
Hc / CH2 = 166.6 kcal/mol
C4H8
CYCLOBUTANE
planar most stable structure
C5H10
CYCLOPENTANE
C6H12
CYCLOHEXANE
Chapter 3:
Substituted Cyclohexanes
Substituents on cyclohexane can, in principle, occupy either axial or equatorial positions. However,
in general, equatorial substituents are more preferred since they are more stable because of reduced
steric interactions.
This is shown in the following example for methycyclohexane.

In the equatorial system, the methyl group is anti to the C-C bonds in the rest of the ring system.
However, in the axial conformation, a steric interaction of the methyl group with the two axial
hydrogen atoms on the same face of the ring destabilises the axial conformation. In the images
below, this 1,3-diaxial interaction can be highlighted and contrasted with the equatorial conformer.
The effect is most obvious when viewed in the spacefilling model.
EQUATORIAL AXIAL</B< CENTER>

Click here to highlight methyl hydrogen atoms
Click here to highlight methyl hydrogen atoms
Click here to highlight 1,3-diaxial hydrogen atoms

The larger the alkyl substituent is, the greater the preference for the equatorial position since the
larger the group the greater the steric interaction with the axial hydrogens.
Chapter 3:
Polycyclic Systems
Both nature and mankind has created many examples of compounds that contain more than one
ring system. These can be classified depending on how many rings are present and how the rings
are joined together.
If there is a single carbon atom common to two rings, then the

system is said to be "spirocyclic" and the carbon can be described
as the "spirocenter". The simplest example is spiropentane.
If two or more atoms are shared between more than one ring then
the system is said to be "polycyclic" in general terms or as
bicyclic, tricyclic, tetracyclic etc. depending on how many rings
systems are present. The simplest polycyclic system is
bicyclobutane.
When there are two common atoms in the rings, then it is a
"fused" system, as in bicyclobutane.
If there are more than two common atoms then the a "bridged"
system is obtained, the simplest example being
bicyclo[1.1.1]pentane.
Some interesting examples are provided below. See if you can recognise which class they would
belong to.
Cubane
Adamantane
Chapter 3:
Heterocycles
Of course atoms other than C can occur as part of the cyclic structure. Such atoms, which are
known as heteroatoms, e.g. N, O, S give rise to heterocycles. These heterocycles are, in general,
very similar to the analogous hydrocarbons, check out the Chime images of a few common simple
heterocylces and a few more complex natural heterocycles shown below.
Tetrahydrofuran
(THF)
Pyrrolidine
Piperidine
Morpholine
Chapter 3:
This page contains some examples of interesting polycyclic and / or heterocyclic molecules. When
looking at the Chime images, look at the types of ring systems that are present.
RANITIDINE: C13H22N4O3S, mol. wt. = 314.41 g/mol

o
Physical properties: Solid, mp = 69-70 C. US patent is held by Allen and Hanburys.
The hydrochloride of Ranitidine is called Zantac, one of the most prescribed drugs in the western
world. Zantac is an off white solid, mp = 133-134 oC. It is soluble in acetic acid, water and
methanol, sparingly soluble in ethanol, insoluble in chloroform.
Ranitidine is a histamine H2-receptor antagonist which inhibits gastric acid secretion.
Therapeutically it is used as an antiulcerative.
PRONTOSIL : C12H13N5O2S, mol. wt. = 291.33 g/mol
o
The hydrochloride salt is an orange-red cyrstaline material, mp : 248-250 C, solubility: 1g in 400
ml water, much more soluble in hot water, soluble in alcohol, acetone, fats and oils.
Prontosil was original prepared as an "azo-dye" and used for dyeing wool fibres. However, it was
part of an in vivo study for antibacterial activity (found to be active against Gram-positive
infections) and became a prototype compound that led to the development of the important
sulphonamide antibacterials. Prontosil was first drug introduced to treat bacterial infections.
Therapeutically it is used as an antibacterial, but it is also used as a specific stain for carbonic
anhydrase in polyacrylamide gels.
PROMAZINE: C17H20N2S, mol. wt. = 284.43 g/mol
Physical properties: an oily liquid, having an "amine" odour. bp(0.3) : 203-210 oC.
Prepared by heating a xylene solution of phenothiazine and 3-dimethylamino-1-chloro-propane in
the presence of sodamide. US patent for Promazine is held by Rhone-Poulenc.
The hydrochloride salt, Prazine (also known as Talofen or Sparine) is a white/yellow crystalline
material that oxidises in air. One gram is soluble in 3 ml of water. it is also soluble in alcohols and
chloroform, insoluble in diethyl ether and benzene. Aqueous solutions are slightly acidic to litmus.
Therapeutically it is used as an antipsychotic and an antihistamine in man and as a tranquilizer for
animals.
NOVOCAIN: C13H20N2O2.HCl, mol. wt. = 273.07 g/mol
Novocain is the hydrochloride salt of another pharmaceutical, Procaine. Novocain is a crystaline
material:mp = 153-156 oC. Numbing taste. Air stable. Solubility: 1g dissolvesin 1ml water and 30ml
of alcohol, slightly soluble in chloroform, virtuallyinsoluble in diethyl ether. pH of 0.1M solution is
6.0. Aqueous solutionscan be sterilised by boiling. LD50 (mice mg/kg) = 660.
Novocain was synthesised to replace cocaine due to the abuse of cocaine.It was designed to have the
same pain-killing properties but not the psychologicalside effects.
Therapeutically used as a local anesthetic for humans and animals.
LIDOCAINE: C14H22N2O, mol. wt. = 234.34 g/mol
o
Physical properties: crystaline needles (from benzene or alcohol) mp = 68-69 C, bpt (4mm) = 180-
182oC.
Soluble in chloroform, benzene, ether and alcohol. Insoluble in water.
Lidocaine was developed from Procaine (ie Novocain), the structure of which is shown above.
Compare the two structures. Due to the presence of a labile ester bond, Procaine has only a short
lifetime/duration of action. Changing this to a more stable amide linkage as in Lidocaine provides a
material with a longer lifetime and therefore duration. The US patent is held by Astra.
Also known as Lignocaine and Xylocaine amongst many other names.
Therapeutically it is used as a local anesthetic and a class IB antiarrhythmic.
DIAZEPAM: C16H13ClN2O, mol. wt. = 284.74 g/mol
Physical properties: crystaline plates (from acetone and petroleum ether) mp = 125-126 oC.
pKa = 3.4. Soluble in chloroform, dimethyl formamide, benzene, acetone and alcohol. Slightly
soluble in water. LD50 (orally for rats) = 710mg/kg
This is a controlled substance in US code of Federal Regulations. US patent is held by Hoffmann-La
Roche.
Also known as Valium, Novazam amongst many other names.
Therapeutically it is a anxiolytic, a skeletal muscle relaxant.
NORETHINDRONE: C20H26O2, mol. wt. = 298.43 g/mol
Physical properties: crystaline (from ethyl acetate) mp = 203-204 oC. Specific rotation = -31.7 in
chloroform.
Prepared from 19-nor-4-androstene-3,17-dione. US patent is held by Syntex.
Also known as Coniudag, Menzol, Micronor, Micronovum, Mini-Pe, Norcuolut, Noriday, Norluten,
Norlutin, Nor-Qd, Primolut N, and, Utovlan.
Norethindrone is a synthetic steroid and was developed since it was known that natural steroids have
potent physiological effects.
Therapeutically it is a progestogen. Norethindorne and its acetate with estrogen is used as an oral
contraceptive. The enanthate is an injectable contraceptive.
MIFEPRISTONE: C29H35NO2, mol. wt. = 429.60 g/mol
o o
Physical properties: mp = 150 C. Specific rotation = +138.5 (c = 0.5 in chloroform). Mifepristone is
a progesterone receptor antagonist with partial agonist activity. When used with prostaglandins,
Mifepristone terminates pregnancy within the first 9 weeks of gestation. Structurally it is very
similar to Norethindrone. The US patent is held by Rousell-UCLAF. Also known as RU-486 and
Mifegyne.
Therapeutically it is used as an abortifacient.
Information source: The Merck Index. 12th edition
Chapter 7 : Stereochemistry <>

Summary:
Despite what one may perceive from a printed page or even the computer screen you are now
looking at, most molecules are not 2D objects, they are 3D as a result of the spatial arrangement of
the atoms, groups and bonds. The interaction of molecules (reactions) which occur as the result of
collisions between these 3D objects in 3D space, can therefore also have 3D requirements and
characteristics. Stereochemistry is all about the 3D properties of molecules and reactions.
Isomer types
What are the different types of isomers ?
Types of Stereoisomers
What are stereoisomers ?
Enantiomers
What do I need to know about Enantiomers ?
Diastereomers
What do I need to know about Diastereomers ?
The Stereogenic Centre

What is a stereogenic centre ?
Carbon-based stereogenic centres
Stereogenic centres other than carbon
Optical Activity
What is optical activity ?
Measuring optical activity
Determining optical purity
I'd like to try some problems
Absolute Relative Configuration

What is the difference between Absolute and Relative Configurations ?
I'd like to try some problems
Cahn-Ingold-Prelog R/S notation

How to name enantiomers
Fischer projections
What are Fischer projections ?
Chapter 7 : Stereochemistry
Isomer types:
Compounds that have the same molecular formula but different chemical structures are isomers or
isomeric.
Depending on the type of difference between the structures, it is possible to classify isomers into
various sub-types.
The following tree diagram contains questions that helps you to decide which isomeric relationship
applies.
If you "click" on the yellow named boxes, there is a link to a definition and an example.
Isomers are compounds with the same molecular formulae but that are structurally different in
some way.
It is important to be able to recognise isomers because there can have different chemical, physical
properties and biological properties.
Constitutional (or structural) isomers differ in the order in which the atoms are connected so they
contain different functional groups and / or bonding patterns:
example: 1-propanol, 2-propanol and ethyl methyl ether (C 3H8O)
Stereoisomers contain the same functional groups and bond connectivities, they differ only in the
arrangement of atoms (or groups) in space.
Conformational isomers (or conformers or rotamers) are stereoisomers produced by rotation about
bonds, typically rapidly interconverting at room temperature:
example 1: butane : staggered (left) and eclipsed (center).The C2-C3 bond rotation is
animated (right). Try rotating the model to look along the C-C to see the two forms.
example 2: cyclohexane : chair (left) and boat (right).These two forms can be interconverted
by twisting the ring structure.
Configurational isomers are stereoisomers that do not readily interconvert at room temperature and
can (in principle at least) be separated. In practice it may not be a simple task.
Geometric isomers are configurational isomers that differ in the spatial position around a bond with
restricted rotation (e.g. a double bond):
E-2-butene and Z-2-butene
Optical isomers are configurational isomers that differ in the 3D relationship of the substituents
about one or more atoms
Enantiomers are optical isomers that are non-superimposable mirror images.

(R)- or (S)-2-chlorobutane. Try moving the images to show that they are mirror images, and
make sure you can assign their configurations correctly.
R- S-
Diastereomers are optical isomers that are not enantiomers.

(S,R)- or (R,R)-2-bromo-3-chlorobutane. Try moving the images to convince yourself that
they are not mirror images or superimposable.
Deriving Possible Isomers
There is no simple way to know how many isomers exist for a given molecular formula, and
therefore, it is important to have a systematic method to derive them. Important preliminary steps in
the process are to determine the IHD to see what types of structures you should be considering, then
list the functional groups that are possible based on the molecular formula and IHD. Once you have
done that, here are a few suggestions to aid the drawing process.....
start with the longest continuous chain (or ring) first

move substituents systematically along the chain
if you have C=C consider E- and Z- possibilities or cis- and trans- for ring systems
decrease the the chain length one step at a time and introduce new alkyl groups
watch out that you don't repeat structures
if chiral centers are present then need to consider R and S stereoisomers, do this by
identifying the chiral centers.
Enantiomers
Molecules that are non-superimposable mirror images are enantiomers, look at the two molecules
shown below and set them up to show this. Note that your left and right hands are a pair of
enantiomers.
(R)-2-chlorobutane (S)-2-chlorobutane
You should be able to draw these molecules, as given below the Chime images, and indicate how
they are mirror images!
Enantiomers are known as chiral molecules (derived from the Greek meaning hand), therefore, a
molecule that is superimposable on its mirror image is said to be achiral.
You should be able to draw the two mirror images of an achiral molecule and then see how if you
rotate one of the images the two molecules are actually the same.
A mixture containing equal quantities of enantiomers is called a racemate or a racemic mixture.
Enantiomers are characterised by the presence of a stereogenic centre.

The Stereogenic Centre:

A stereogenic centre is also known as a chiral centre. It is characterised by an atom which has
different groups bound to it in such a manner that its mirror image is non-superimposable. Below
are the enantiomers of 2-chlorobutane.
(R)-2-chlorobutane (S)-2-chlorobutane
Note you should be learning to relate the chime images to the drawn images. More importantly
you should be able to reproduce the drawn images as that is what you will be expected to do on
exams or assignments!
The presence of a single stereogenic centre in a molecule results in a chiral molecule.
Molecules can, however, possess more than one stereogenic centre. Such molecules may or may
not be chiral.
Isomers of chiral molecules that possess two or more stereogenic centres, may be either
enantiomers or diastereomers (stereoisomers that are not mirror images).
(S,R)-2-bromo-3-chlorobutane (R,R)-2-bromo-3-chlorobutane
Diastereomers can have quite different physical and chemical properties from one another.
Isomers of achiral molecules, that possess two or more stereogenic centres, are known as meso
isomers (stereoisomers that are superimposable). You should be able to draw a pair of meso
isomers and see how one relates to the other by simple rotation.
Image A above is the mirror image of B, but can be seen to be the same as B once it has been
rotated. A quick way of recognising whether a molecule is achiral is to look for a plane of
symmetry.
Carbon-based Stereogenic Centres:

The most prevalent stereogenic centres in organic chemistry are carbon atoms, which have four
different groups bound to them.
Stereogenic Centres other than Carbon:

Any atom which has four different groups bound to it is a stereogenic centre. The more common of
these atoms, with which an organic chemist should be familiar, are Si, N and P. They may be
tetrahedral molecules (where the four different groups are atoms) or trigonal pyramidal molecules
(where a lone pair is included as one of the four different groups).
CAUTION: many trigonal pyramidal molecules (especially those of nitrogen) exhibit rapid
pyramidal inversion:
In this case, even though a stereogenic centre is present in each molecule, a sample is optically
inactive as the optical activity of the two extremes of inversion averages out.
The larger the atom, though, the slower the pyramidal inversion and as a result many optically
active compounds for P and S have been prepared.
Optical Activity:
Optical activity is the ability of a chiral molecule to rotate the plane of plane-polairsed light. It is
measured using a polarimeter, which consists of a light source, polarising lens, sample tube and
analysing lens.
When light passes through a sample that can rotate plane polarised light, the light appears to dim to
the eye because it no longer passes straight through the polarising filters. The amount of rotation is
quantified as the number of degrees that the analysing lens must be rotated by so that it appears as if
no dimming, of the light has occurred.
Measuring Optical Activity:

When rotation is quantified using a polarimeter it is known as an observed rotation, because
rotation is affected by path length (l, the time the light travels through a sample) and concentration
(c, how much of the sample is present that will rotate the light). When these effects are eliminated a
standard for comparison of all molecules is obtained, the specific rotation, [].
[] = 100 / cl when concentration is expressed as g sample /100ml solution

Specific rotation is a physical property like the boiling point of a sample and can be looked up in
reference texts. Take a look at a problem.
Enantiomers will rotate the plane of polarisation in exactly equal amounts (same magnitude) but in
opposite directions.
Dextrorotary designated as (+), clockwise rotation (to the right)

Levorotary designated as (-), anti-clockwise rotation (to the left)
If only one enantiomer is present a sample is considered to be optically pure. When a sample
consists of a mixture of enantiomers, the effect of each enantiomer cancels out, molecule for
molecule.
For example, a 50:50 mixture of two enantiomers or a racemic mixture will not rotate plane
polarised light and is optically inactive. A mixture that contains one enantiomer excess, however,
will display a net plane of polarisation in the direction characteristic of the enantiomer that is in
excess.
Determining Optical Purity:

The optical purity or the enantiomeric excess (ee%) of a sample can be determined as follows:
Optical purity = % enantiomeric excess = % enantiomer 1 - % enantiomer2

= 100 []mixture / []pure sample
ee% = 100 ([R]-[S]) / ([R]+[S])
where [R] = concentration of the R-isomer

[S] = concentration of the S-isomer
Look at some problems like these more in depth.
Diasteromeric substances can have different rotations both in sign and in magnitude.
Absolute and Relative Configurations:

When the precise arrangement of substituents at a stereogenic centre is known the absolute
configuration of the molecule is known. This is usually accomplished by solving the x-ray crystal
structure of a molecule, a method that is not always readily available.
The arrangement of atoms in an optically active molecule, based on chemical interconversion from
or to a known compound, is a relative configuration. Relative, because there is no way of
knowing just by looking at a structure whether the assignment of (+) or (-) is correlated to a
particular isomer, R or S.
If the name of a compound includes both the sign of rotation and the designation R or S then the
absolute configuration of that compound is known.
Let's see how chemists can determine the relative configurations of optically active compounds by
chemically interconverting them.
The reaction of an alcohol with TsCl is known to occur with retention of configuration, that is the
group priority of the stereogenic centre has not been altered. The reaction of the tosylate with
nitrile occurs with inversion, as a result the group priority at the stereogenic centre has been altered.
The absolute configuration of the parent is known while only the relative configurations of the
tosylate and the nitrile are known. The mechanistic aspects behind this will be discussed in more
detail in the next chapter.
Cahn-Ingold-Prelog R/S Notation:

The Cahn-Ingold-Prelog R/S rules are used for naming enantiomers.
NB: The term stereogenic has superceded the term chiral.
1. Identify the stereogenic centers (most commonly an sp3 C with 4 different groups attached)
2. Assign the priority to each group (high = 1, low = 4) based on atomic number of the atom
attached to the stereogenic center
3. Position the lowest priority group away as if you were looking along the C-(4) sigma bond. If
you are using a model, grasp the group in your fist
4. For the other 3 groups, determine the direction of high to low priority (1 to 3)
5. If this is clockwise, then the center is R (Latin: rectus = right)
6. If this is counter clockwise, then it is S (Latin: sinister = left)
Example: chlorofluoroiodomethane
The stereogenic center is easy to spot, and the four attached groups are I (purple), Cl (green),
F(brown) and H (white), listed in priority order, highest to to lowest. Rotate the CHIME image
below so the you are looking along the C-H bond and the H is away from you, then determine the
direction of high to low priority. It decreases clockwise, so this is the R enantiomer.
Subrules:
Isotopes: H vs D ? Still use atomic number so D > H

Same atom attached ? By moving out one unit at a time, locate the first point of difference
and apply rules there.
Can you convey this on a piece of paper?
Fischer Projections:
Fischer Projections are abbreviated structural forms that allow one to convey valuable
stereochemical information to a chemist without them having to draw a 3D structural representation
of a molecule. These representations are only used for molecules that contain stereogenic centers,
which are then represented as simple crosses.
They can be derived by considering the more accurate 3D representation using wedges and
assuming the convention that horizontal lines represent bonds coming out of the plane of the paper
and vertical lines represent bonds going behind the plane of the paper.
Memory Aid ?
A student once told me that she remembered the relative arrangement of the bonds by the fact that
the horizontal bonds were coming out to hug her !
When relating one Fischer projection to another it may only be manipulated within the 2D plane in
which it is drawn (that is it may not be rotated within 3D space), and only rotated a total a 180o
Why can't you rotate it 90o? A 90o rotation is equivalent to breaking bonds and exchanging two
groups, which would result in the formation of the other enantiomer.
CAUTION Fischer projections are often confused with simpler Lewis diagrams. Lewis
diagrams, however, are not intended to give any stereochemical information!
Fischer projections a can be used to describe molecules with more than one stereogenic centre.
If a Fischer projection of this type can be divided into two-halves that are mirror images than the
molecule may be identified as a meso isomer.
Assignment of the configuration at a stereogenic centre, in a Fischer projection, is based on the

Cahn-Ingold-Prelog rules.
1. Priorities are assigned to the substituents of a stereogenic centre.
2. That of lowest priority is placed on a vertical line, this is equivalent to making sure the lowest
priority group is positioned away from you as if you were looking along the C-(4) bond (see
figure far right below).
3. The configuration is assigned by moving from the substituent of highest priority to those of
second and third priority.
4. If this is clockwise, then the center is R (Latin: rectus = right)
5. If this is counter clockwise, then it is S (Latin: sinister= left)
Consider the molecules A and B above. What are their configurations ?
Tema: Enlace Qumico.
Resumen.
Entender la estructura y enlazar las molculas orgnicas es fundamental para poder entender sus caractersticas,
propiedades y reacciones. Esto debido a que las caractersticas y las reacciones son controladas por interacciones entre
las molculas y cuyo comportamiento es dictaminado por los tipos de enlaces que se encuentran dentro de esas
molculas.
Aunque usted puede pensar que la mayora de los conceptos que encierra este tema es una revisin de sus cursos
anteriores de qumica general, muchos estudiantes no estn tan solidamente empapados de los conceptos bsicos de la
qumica y requieren de estos conocimientos bsicos para poder sobrevivir la aventura que a partir de este momento
experimentara, as que deber estar conciente de que usted comienza su curso de qumica orgnica con buenos
fundamentos. As pues usted ms adelante, entender la localizacin de los electrones, ya que este estos arreglos de
electrones son los que crean los enlaces entre tomos y las reacciones qumicas que se crean justamente por una
reorganizacin de estos electrones para formar nuevos enlaces.
Qu conceptos debo conocer para dar respuesta a esto?
tomos, Molculas, Electrones y Orbtales

Tipos de enlace: Inico, Covalente, Polar Covalente
Estructura de Lewis, carga neta y formal
Forma de las molculas
Hibridacin
Tipos de enlace, ngulos y longitud. Enlaces y .
Concepto cido-base
Tema: Reactividad Qumica e Hidrocarburos
Resumen.
Con el adecuado conocimiento del enlace qumico y otros conceptos bsicos conocidos.
Empecemos a analizar las estructuras qumicas de los principales grupos funcionales y familias, los
principales tipos de reacciones y aplicaciones que se realizan en la qumica orgnica.
Comenzaremos a caminar con la primera familia de la qumica orgnica que son los hidrocarburos y
dentro de ellos estn como los ms simples los alcanos.
Qu conceptos debo conocer para dar respuesta a esto?
Grupos Funcionales
Que es un grupo funcional?

Cuales son los principales grupos funcionales.
Ejemplos
Reactividad Qumica.
Tipos de reacciones qumicas

Tipos de reactivos
Hidrocarburos
Tipos de hidrocarburos
El petrleo, como fuente de suministro
Alcanos
Nomenclatura
Propiedades Fsicas
Estructure
Ismeros
Estabilidad
Reactividad
Anlisis conformacional
Ejemplos
Cicloalcanos
Nomenclatura
Propiedades Fsicas
Estructura
Reactividad
Termodinmica y estabilidad
Calor de reaccin, estados de transicin, energa de activacin, perfil de reaccin.
Mecanismos de reaccin
Reacciones endotrmicas y exotrmicas
Reacciones
Halogenacin, mecanismo de reaccin y reactividad.
Combustin
Pirolisis, Cracking o desintegracin
Mtodos de obtencin
Sntesis sin modificacin del nmero de tomos de carbono

Reaccin de acoplamiento Corey-House.
Tema: Estereoqumica
Resumen
Las estructuras moleculares que observamos en nuestros cuadernos de apuntes o en una

representacin en la computadora solo nos muestran a las estructuras en dos dimensiones, sin
embargo las molculas existen en tres dimensiones debido a la disposicin espacial de los tomos
que forman una molcula, estos arreglos espaciales de los tomos dan al mismo tiempo propiedades
especiales a las molculas orgnicas por lo que su adecuado conocimiento y anlisis es bsico para
la descripcin de las estructuras, as como en su impacto en las diferentes reacciones orgnicas. Su
anlisis implica el conocimiento de conceptos bsicos que se describen con detalle en este tema.
Tipos de Ismeros
Cuales son los diferentes tipos de ismeros?
Tipos de estereoismeros
Que es un estereoismero?
Enantimeros
Que debo conocer acerca de un Enantimero?
Diasteroismeros
Que debo conocer acerca de un Diasteroismero?
Centro Estreogenico o Quiral

Que es un centro quiral?
Centros quirales basados en carbonos
Centros quirales basados en otros tomos
Actividad ptica
Que es la actividad ptica?
Medida de la actividad ptica
Determinacin de la pureza ptica
Anlisis de problemas
Configuracin Absoluta y Relativa

Cual es la diferencia entre configuracin absoluta y relativa?
Anlisis de problemas
Cahn-Ingold-Prelog (nomenclatura R y S)
Como describir y nombrar a los enantimeros

Reglas de proyeccin
Proyecciones de Fischer
Que es una proyeccin de Fischer?

Tarea.
La estructura del compuesto que a continuacin se describe corresponde a la Epotilona A un

compuesto con actividad anticancergena, similar al Taxol
(a) Identifique los grupos funcionales presentes en la Epotilona A.
(b)Que tipo de hibridacin muestran cada uno de los siguientes tomos?
C1 C7 C12 C14 C17 O16 O24 N23
(c) Arregle usted en sentido decreciente a sus longitudes de enlace las siguientes uniones: C14-
C15 C15-C17 C17-C18 C1-O24
(d) Que tipo de enlace esta involucrado en las siguientes uniones C3-C4, C17-C18, C15-O16 y S21-
C22?
(e) Marque con un pequeo circulo los carbones primarios existentes en la estructura, con una X a
los secundarios y con un pequeo triangulo a los terciarios.
(f) Cinco son los elementos que integran esta estructura; mencinelos y ordnelos en funcin de su
electronegatividad.
(g) En la proyeccin; que indican las lneas obscuras y las rayadas y que tipo de proyeccin se esta
utilizando para representar esta estructura.
(h) Dentro de que familia de la qumica orgnica colocara usted a este compuesto.
Dr. Eloy Vzquez Labastida

Tarea.
Alcanos CnH2n+2
Escriba usted el nombre correcto de los compuestos hidrocarburos arriba citados.
Identifique usted los carbonos primarios, secundarios terciarios y cuaternarios en cada caso.
En las dos ultimas estructuras, realice usted el anlisis conformacional a travs del eje de los
carbones 2 y 3 para el primer caso y de los carbones 4 y 5 para el segundo y muestre un
diagrama de energa en el que se indique la posicin de cada conformero.
The chemistry of animal life

Animals, like all lifeforms, are composed of and dependent upon the chemicals of life. To
understand the chemistry of life, we need to first understand the basics of general chemistry. So to
begin, here are some definitions:
matter - anything that occupies space and has mass (matter includes things that are solids,
liquids, gases)
mass - the amount of matter in an object
element - the most basic unit of matter; a substance that cannot be decomposed into
simpler substances by chemical or physical means
atom - the smallest component of an element having the chemical properties of the
element
protons - postively charged particles located in the nucleus of an atom (p+)
neutrons - uncharged particles in the nucleus of an atom
electrons - negatively charged particles that move around the nucleus (e-)
atomic mass - each element has an atomic mas which is the number of neutrons and
protons in the atom's nucleus
atomic number - each element has an atomic number which is the number of protons in
the nucleus of one of the element's atoms
molecule - a bonded collection of two or more atoms of the same or different elements
compound - a substance with constant composition that can be broken down into
elements by chemical processes
The elements that naturally occur in animals include (in order of descending percent body weight,
approx):
oxygen (65%)
carbon (19%)
hydrogen (10%)
nitrogen (3%)
calcium (1%)
phosporus (1%)
potassium (0.2%)
sulfur (0.1%)
sodium (0.1%)
chlorine (0.1%)
magnesium (0.1%)
manganese (0.1%)
iron (0.1%)
copper (0.1%)
iodine (0.1%)
Molecules can be subdivided into two main groups, those that contain carbon, organic molecules
and those that lack carbon, inorganic molecules. The chemistry of the organic molecules is
influenced primarily by the characteristics of carbon. Carbon atoms bond together with other
carbon atoms to form chains and rings of a wide range of lengths and configurations. Some
examples of organic molecules include:
carbohydrates (animals' main source of energy)
lipids (building blocks of fats, make up cell parts and supply energy)
proteins (structural material, hormones, enzymes, metabolic functions, endocrine functions)
nucleotides (building blocks of nucleic acids, DNA and RNA)
Tarea
Alkanes
Organic Chemistry Nomenclature & Numbering
The simplest organic compounds are hydrocarbons. Hydrocarbons contain only two elements, hydrogen and
carbon. A saturated hydrocarbon or alkane is a hydrocarbon in which all of the carbon-carbon bonds are
single bonds. Each carbon atom forms four bonds and each hydrogen forms a single bond to a carbon. The
bonding around each carbon atom is tetrahedral, so all bond angles are 109.5. As a result, the carbon
atoms in higher alkanes are arranged in zig-zag rather than linear patterns.
Straight Chain Alkanes
Here is a table that gives the names of the straight chain alkanes. It's a good idea to commit this table to
memory. The general formula for an alkane is CnH2n+2 where n is the number of carbon atoms in the
molecule. There are two ways of writing a condensed structural formula. For example, butane may be written
as CH3CH2CH2CH3 or CH3(CH2)2CH3.
Molecular Structural
# Carbon Name
Formula Formula
1 Methane CH4 CH4
2 Ethane C2H6 CH3CH3
3 Propane C3H8 CH3CH2CH3
4 Butane C4H10 CH3CH2CH2CH3
5 Pentane C5H12 CH3CH2CH2CH2CH3
6 Hexane C6H14 CH3(CH2)4CH3
7 Heptane C7H16 CH3(CH2)5CH3
8 Octane C8H18 CH3(CH2)6CH3
9 Nonane C9H20 CH3(CH2)7CH3
10 Decane C10H22 CH3(CH2)8CH3
Rules for Naming Alkanes
The parent name of the molecule is determined by the number of carbons in the longest chain.
In the case where two chains have the same number of carbons, the parent is the chain with the
most substituents.
The carbons in the chain are numbered starting from the end nearest the first substituent.
In the case where there are substituents having the same number of carbons from both ends,
numbering starts from the end nearest the next substituent.
When more than one of a given substituent is present, a prefix is applied to indicate the number of
substituents. Use di- for two, tri- for three, tetra- for four, etc. and use the number assigned to the
carbon to indicate the position of each substituent.
Branched Alkanes
Branched substituents are numbered starting from the carbon of the substituent attached to the
parent chain. From this carbon, count the number of carbons in the longest chain of the substituent.
The substituent is named as an alkyl group based on the number of carbons in this chain.
Numbering of the substituent chain starts from the carbon attached to the parent chain.
The entire name of the branched substituent is placed in parentheses, preceded by a number
indicating which parent-chain carbon it joins.
Substituents are listed in alphabetical order. To alphabetize, ignore numerical (di-, tri-, tetra-) prefixes
(e.g., ethyl would come before dimethyl), but don't ignore don't ignore positional prefixes such as iso
and tert (e.g.,. triethyl comes before tertbutyl).
Cyclic Alkanes
The parent name is determined by the number of carbons in the largest ring (e.g., cycloalkane such
as cyclohexane).
In the case where the ring is attached to a chain containing additional carbons, the ring is considered
to be a substituent on the chain. A substituted ring that is a substituent on something else is named
using the rules for branched alkanes.
When two rings are attached to each other, the larger ring is the parent and the smaller is a
cycloalkyl substituent.
The carbons of the ring are numbered such that the substituents are given the lowest possible
numbers.
Tarea.
De los compuestos arriba citados escriba usted.
Su nombre qumico correcto.

Obtenga usted cada uno de ellos mediante una sntesis de Gignard y escriba usted el nombre
del compuesto de Grignard, que generara el hidrocarburo.
Sintetice cada uno de ellos mediante una sntesis de Corey-House y describa la ruta de
trabajo con los halogenuros por usted seleccionados, as como los nombres de cada especie
empleada.
Someta a halogenacin con bromo, cada uno de ellos e indique los porcentajes de los mas
abundantes as como su nombre y estructura, y muestre usted si existe para alguno de ellos
algn centro quiral.
Si encuentra centros quirales muestre las estructuras R y S para cada uno de ellos.
Lo que a continuacin se describe viene de:

ffsite.htm?zi=1/XJ&sdn=chemistry&zu=http%3A%2F
%2Fwww.faqs.org%2Ffaqs%2Fsci%2Fchem-faq
%2Fpart5%2F
Al abrir esta paguina aparecen mas apartados refiriendose a

otros conceptos interesantes en pequeas notas.
Sci.chem FAQ - Part 1 of 7
There are reader questions on this
topic!
Help others by sharing your
knowledge
From: Bruce Hamilton <B.Hamilton@irl.cri.nz>

Newsgroups: sci.chem
Subject: Sci.chem FAQ - Part 1 of 7
Date: Thu, 15 Jan 2004 22:06:54 +1300
Message-ID: <pslc00l3l7nii4m1686oarr4q2dtgq1l6c@4ax.com>
Reply-To: B.Hamilton@irl.cri.nz
Archive-name: sci/chem-faq/part1
Posting-Frequency: monthly
Last-modified: 22 October 1999
Version: 1.17
FAQ: Sci.chem
Editor: Bruce Hamilton
B.Hamilton@irl.cri.nz
This FAQ is posted monthly to the Usenet groups sci.chem, sci.answers and
news.answers, and the latest version should be obtained from any of those
groups, or from the Dejanews or Altavista WWW sites that also offer Usenet.
It can be obtained by FTP from the FAQ archive site at rtfm.mit.edu in the
pub/usenet-by-hierarchy/sci/chem directory, where other chemistry-related
FAQs are also archived as ascii files in their sub-directories.
The FAQ is also available, along with many other Usenet FAQs, on the WWW at
www.faqs.org, in both ascii and simple hypertext formats. Due to propagation
delays, some WWW and archive sites may not contain all parts of the latest
version, but a WWW search engine should locate those parts at other sites.
Changes:
- revised WWW sections.

- updated various email addresses,
- updated references
Subject: 1. Dedication
This FAQ is dedicated to the memory of the late Larry Lippman, who departed
from this group ( and life ) in 1991. His superb posts on a wide range of
chemical topics were both informative and entertaining. He established the
sci.chem tradition of friendly, authoritative, and accurate answers to
many chemistry-related questions.
Subject: 2. Introduction and Intent.
This FAQ is intended to provide answers to chemistry-related questions that

have appeared several times in sci.chem. It is also intended to guide the
curious to written and electronic information sources for the major areas
of chemistry that are discussed in sci.chem. The curious reader is
encouraged to explore those treasure-troves, and this FAQ, prior to posting
their question to sci.chem. I have assumed that most posters will have
access to institutional or public libraries, and most of the references
should be available from them, either on the shelves, via private loans
from staff in chemistry departments, or via library Interloan services.
I have also assumed readers have a basic knowledge of how to use a technical
library, and how to locate chemistry information sources. If you are lost
in your library, ask the nearest librarian :-). As sci.chem is a chemistry
discussion group, posters should have at least used any available basic
reference texts to ensure their question is coherently presented. The first
steps are yours, we will then endeavour to help you walk, and perhaps even
run, safely through the minefields of chemistry :-).
Subject: 3. Table of Contents
Part 1.
1. Dedication
2. Introduction and Intent
3. Contributors
Jason Bruce Chin
Jim Corton
Neil Flatter
Bruce Hamilton
Vince Hamner
Theodore Heise
Knut Irgum
Jim Oliver
Yogi Shan
Mark Perks
Dave Young
4. Table of Contents
5. Sci.chem
5.1 What topics does sci.chem cover?.
5.2 What guidelines are available about posting to sci.chem?.
5.3 Should I post my homework question?.
5.4 Should I answer an obvious homework question?.
5.5 I'm offering or seeking employment. Can I post here?.
5.6 Can I post here if my news feed doesn't include the correct group?.
5.7 Can I post here if my library doesn't have the specified reference?.
5.8 Can I post articles I found in Usenet or on the Internet?.
5.9 Should I post the email address of an expert I found?.
5.10 Should I post corporate advertising material?.
5.11 Should I state why I require the requested information?.
5.12 What other chemistry-focused newsgroups exist?.
5.13 What questions are best answered elsewhere in Usenet?.
5.14 Why is the sci.chem.* hierarchy not rational?.
5.15 How do I create a sub-group for my pet topic?.
5.16 Where are the sci.chem archives?.
5.17 Who was Larry Lippman?.
6. Common terms and abbreviations frequently used in sci.chem.

6.1 Abbreviations used in this FAQ.
6.2 Common Terms used in this FAQ.
Part 2.
7. General Chemistry-related Information on the Internet

7.1 How can I access databases such as Chemical Abstracts?.
* 7.2 What chemistry-related material is on the WWW?.
7.3 What information is available commercially on-line?.
7.4 What information is available free on-line?.
7.5 What chemical patent information is available on-line?.
7.6 Which FTP sites contain chemistry-related material?.
7.7 What chemistry-focused mailing lists exist?.
7.8 How can I contact Chemical Societies electronically?.
7.9 How can I contact large chemical companies?.
7.10 How can I contact chemical suppliers?.
7.11 How can I contact equipment suppliers?.
7.12 How can I contact US government agencies?.
7.13 Where can I find compilations of science humour?.
7.14 Where can I purchase scientific software?.
8. Laboratory and Chemical Safety Information on the Internet

8.1 Where can I find Material Safety Data Sheets?.
8.2 Where can I find detailed safety & toxicity data?.
8.3 Where can I find occupational exposure limits?.
8.4 Where can I find hazard information for a chemical?.
8.5 Where can I find laboratory safety guides?.
8.6 Where can I find other safety information?.
9. Traditional ( Non-Internet ) General Chemistry Information Sources

9.1 When can I find Chemical Abstracts?.
9.2 Where can I obtain chemical patent information?.
9.3 Where can I purchase chemicals?.
9.4 Where can I purchase laboratory equipment?.
9.5 What reference texts should I search first?.
9.6 Where can I find physical and spectral properties of chemicals?.
9.7 Where can I find production data for commercial chemicals?.
9.8 Where can I find the composition of a proprietary chemical?.
9.9 Where can I find out about the history of Chemistry?.
9.10 Where can I find out about the discovery of an element?.
9.11 What inspirational books about chemistry should I read?.
10. Traditional Laboratory and Chemical Safety Information Sources

10.1 Where can I find Material Safety Data Sheets?.
10.2 Where can I find detailed safety & toxicity data?.
10.3 Where can I find occupational exposure limits?.
10.4 Where can I find hazard information for a chemical?.
10.5 What is the most poisonous compound?.
10.6 Where can I find laboratory safety guides?.
10.7 Are contact lenses a hazard in laboratories?.
Part 3.
11. Traditional Specialist Chemical Information Sources

11.1 Where can I find spectral libraries/databases?.
11.2 Where can I find polymer chemistry information?.
11.3 Where can I find analytical chemistry information?.
11.4 Where can I find environmental chemistry information?.
11.5 Where can I find physical chemistry information?.
11.6 Where can I find inorganic chemistry information?.
11.7 Where can I find organic chemistry information?.
11.8 Where can I find industrial chemistry information?.
11.9 Where can I find pharmaceutical chemistry information?.
12. Nomenclature
12.1 What are CAS Registry Numbers?.
12.2 What are the correct names of recently-discovered elements?.
12.3 What is the nomenclature system for CFCs/HCFCs/HFCs?.
12.4 How can I get the IUPAC chemical name from traditional names?.
12.5 What does "omega-3 fatty acids" mean?.
12.6 What is Conjugated Linoleic Acid?.
12.7 What are "heavy" metals?.
12.8 What is the difference between Molarity and Normality?.
12.9 Where can I find the composition of common named reagents?.
13. Illicit and Government-Controlled Substances

13.1 What news groups/mailing lists discuss illegal drugs?.
13.2 Where can I obtain a list of illegal drugs?.
13.3 What is the chemical structure of common illegal drugs?.
13.4 How do I obtain chemical information on illegal drugs?.
13.5 Where are the synthesis instructions for illegal drugs?.
13.6 Should I post detailed recipes for illegal chemicals?.
13.7 What news groups/mailing lists discuss explosives?.
13.8 What is the chemical structure of common explosives?.
13.9 How do I obtain chemical information on common explosives?.
13.10 What news groups/mailing lists discuss pyrotechnics?.
14. Academic Course Information

** 14.1 Where do I find information on US courses?.
** 14.2 Where do I find information on other nations' courses?.
Part 4.
15. Chemical Demonstrations

15.1 Are there any good compilations of demonstrations?.
* 15.2 What are good outdoor demonstrations for under 12s?.
* 15.3 What are good outdoor demonstrations for over 12s?.
* 15.4 What are good indoor demonstrations for under 12s?.
* 15.5 What are good indoor demonstrations for over 12s?.
15.6 How do I safely perform the Glowing Pickle experiment?.
15.7 How do I make Slime?.
16. Laboratory Procedures

16.1 What are the best drying agents for liquids and gases?.
16.2 What is the effect of oven drying on volumetric glassware?.
16.3 What does the Karl Fischer titration measure?.
16.4 What does the Dean and Stark distillation measure?.
16.5 What does Kjeldahl nitrogen measure?.
16.6 What does a Soxhlet extractor do?.
16.7 What is the best method for cleaning glassware?.
17. Preparation of chemicals

17.1 Where do I find laboratory-scale procedures for organics?.
17.2 Where do I find laboratory-scale procedures for inorganics?.
17.3 Where do I find industrial chemical process details?.
18. Sensory properties of chemicals

18.1 How do light sticks work?, and how can I make one?.
18.2 How do hand warmers work?, and how can I make one?.
18.3 What are the chemicals that give fruity aromas?.
18.4 What is the most obnoxious smelling compound?.
18.5 What is the nicest smelling compound?.
Part 5.
18.6 What is the most bitter compound?.

18.7 What is the sweetest compound?.
18.8 What salts change the colour of flames?.
18.9 What chemicals change colour with heat, light, or pressure?.
19. Physical properties of chemicals

19.1 Rheological properties and terminology
19.2 Flammability properties and terminology
19.3 Supercritical properties and terminology
19.4 Formation of gaseous bubbles in liquids
19.5 Why is Mercury a liquid at room temperature?.
20. Optical properties of chemicals

20.1 Refractive Index properties and terminology
20.2 Polarimetry properties and terminology
21. Molecular and Structural Modelling

21.1 What hardware do I need to run modelling programmes?.
21.2 Where can I find a free modelling programme?.
21.3 Where can I find structural databanks?.
21.4 Where can I find ChemDraw or ChemWindows?.
22. Spectroscopic Techniques

22.1 Ultra-Violet/Visible properties and terminology
22.2 Infra-Red properties and terminology
22.3 Nuclear Magnetic Resonance properties and terminology
22.4 Mass Spectrometry properties and terminology
22.5 X-Ray Fluorescence properties and terminology
22.6 X-Ray Diffraction properties and terminology
22.7 Fluorescence/Phosphorescence properties and terminology
23. Chromatographic Techniques

23.1 What is Paper Chromatography?.
23.2 What is Thin Layer Chromatography?.
23.3 What is Gas Chromatography?.
23.4 What is Column Chromatography?.
23.5 What is High Pressure Liquid Chromatography?.
23.6 What is Ion Chromatography?.
23.7 What is Gel Permeation Chromatography?.
23.8 What is Capillary Electrophoresis?.
23.9 How do I degas chromatographic solvents?.
23.10 What is chromatographic solvent "polarity"?.
24. Extraction Techniques
24.1 What is Solvent Extraction?.
24.2 What is Solid Phase Extraction?.
24.3 What is Supercritical Fluid Extraction?.
24.4 What traditional process extracted perfume from flower petals?.
25. Radiochemical Techniques

** 25.1 What is radiochemistry?.
Part 6.
26. Electrochemical Techniques

26.1 What is pH?.
26.2 How do pH electrodes work?.
26.3 What are ion-selective electrodes?.
26.4 Who supplies pH and ion-selective electrodes?.
27. Fuel Chemistry

27.1 Where does crude oil come from?.
27.2 What are CNG/LPG/gasoline/kerosine/diesel?.
27.3 What are oxygenates?.
27.4 What is petroleum ether?.
27.5 What is naphtha?.
27.6 What is white spirits?.
27.7 What are biofuels?.
27.8 How can I convert cooking oil into diesel fuel?.
28. Pharmaceutical Chemistry

** 28.1 Does Thalidomide racemise in humans?.
29. Adhesive Chemistry

**
30. Polymer Chemistry

30.1 How can I simply identify common plastics?.
30.2 What do the plastics recycling codes mean? .
31. Others
31.1 How does remote sensing of chemical pollutants work?.
31.2 How does a Lava Lamp work?.
31.3 How do I make a Lava Lamp?.
31.4 What is Goretex?.
31.5 What causes an automobile airbag to inflate?.
31.6 How hazardous is spilt mercury?.
31.7 Did molasses really kill 21 people in Boston?.
31.8 What is the active ingredient in mothballs?.
31.9 Is vinegar just acetic acid?.
31.10 What are the different grades of laboratory water?.
Part 7.
31.11 What is Sarin nerve gas?.

31.12 What are Dioxins?.
31.13 What is Red Mercury?.
31.14 How do I remove stains and deposits?.
31.15 How do I remove rust?.
31.16 How do I remove silver tarnish?.
31.17 How do I electroplate or anodise materials?.
31.18 How fast do solvents pass through human skin?.
31.19 What is the pH of Coca-Cola?.
32. References
Subject: 5. Sci.chem
5.1 What topics does sci.chem cover?.
Sci.chem is an unmoderated discussion group, and it covers the discussion

of all scientific aspects of chemistry. It is not intended to be an
educational resource that replaces your local library - which should still
be your first port of call when seeking information. Because sci.chem was
created in the 1980s, there is no Charter that would define topics for
discussion in the group, however common sense suggests that posts should be
focused on aspects of chemistry not discussed elsewhere on Usenet. Newer
groups in the hierarchy do have Charters.
There are no eligibility requirements, anybody can post to sci.chem, but

remember that far more people read the groups than actually post. There are
very many knowledgeable lurkers who prefer to email their assistance, rather
than publicly post to the group. When posting, it is a good idea to always
assume that there will be readers who know more about the topic than you,
but that should not inhibit you from presenting your perception.
There is no talk.chemistry group, consequently discussion often drifts away

from the narrow focus of the science of chemistry. There are several groups
that also cover specialist areas ( refer Section 5.12 ), and prospective
sci.chem posters should check to ensure their post would not be more
appropriate in one of those groups. Please do not crosspost to all chemistry
groups, and please do not post to groups that you are not currently reading,
asking for email replies. When responding to posts in widely-crossposted
threads, examine the "Newsgroups" line, delete irrelevant groups, and set
the "Followup-To" header. Posts to cross-posted threads that have no ongoing
" chemistry " requirement should have the "Followup-To" header diverted back
to the original group.
Because sci.chem is an unmoderated discussion group inhabited by a diverse

range of humanity, posted "facts" are not always correct, and may not always
be corrected, so don't blame us if your teacher marks your answer wrong :-).
5.2 What guidelines are available about posting to sci.chem?.
Sci.chem is a discussion group, not an alternative to your nearest library.

We expect posters to have explored some of the chemical resources usually
available in libraries ( refer Section 9.5 ) and on the Internet ( refer
Sections 7.2 and 7.4 ) prior to posting questions to the group. Posting basic
questions, without performing any preliminary work, is likely to invoke posts
suggesting ( with varying degrees of politeness ) that you visit a library or
perform a WWW search.
Sci.chem is also not part of a global facility for teachers to point their
students towards as an alternative to a library. Teachers should not ask
students to post unsupervised questions to the group as part of assignments.
Teachers should recognise the positioning of the group as a resource to be
utilised only if more appropriate resources, such as libraries and Internet
WWW searches, have failed to identify suitable sources of information. The
teacher should also use DejaNews to ensure questions have not been answered
previously on Usenet. Teachers should ensure that students asking a question
in sci.chem also post, along with the question, a summary of what they have
discovered so far, and where they have already searched.
Teachers should also realise that sci.chem also reflects the diverse range of
humanity that can post to it, consequently some posts may not match the image
of chemistry that they wish to present to their students.
Most of the general guidelines about posting to Usenet that appear in

news.announce.newusers are also appropriate for sci.chem. It is important
that the grammar and spelling of posts to sci.chem are of sufficient quality
to ensure that readers can easily, and unambiguously, understand your
request or contribution. If a poorly-written post appears, some readers are
more likely to flame, ridicule, or ignore you, rather than carefully consider
your request or contribution. Minor typos and spelling errors only require
cancelling, or a follow-up post correcting the error, if the error is
likely to create confusion.
If you are posting, or viewing, drawings of chemical structures in ascii,

please use a fixed-pitch font, otherwise the structure will appear different
than intended, resulting in confusion. If you are posting via WWW access, or
posting WWW information, please ensure all HTML markers are removed from your
posts to the group. Do not post binaries to the group, even if they are
relevant to a thread. Post them to a binaries group, or make them available
on the WWW, and post a message to the group pointing to the location.
Please do not use sci.chem for test posts, or to discuss problems with your
Internet Services Provider, or any other totally irrelevant topics, as there
are bound to be more appropriate Usenet groups. There are plenty of *.test
groups which are monitored by programmes providing automated responses to
confirm that your test post has successfully propagated throughout the
Internet.
If you believe the "noise" content of sci.chem is too high, learn to use
the filtering features of your newsreading software. Most software has the
ability to create killfiles or only display posts that match certain criteria
- such as the number of groups in the Newsgroups line. Such features can make
posts from individuals, and much of the widely cross-posted junk, disappear.
If your software does not support those features, there may be alternative
software available from your provider.
Please do not post messages complaining about what you perceive as noise in
the group, as such posts usually just generate additional noise. If you wish,
you can email posters asking them to desist from posting the material that
offends you, but don't be surprised if you are also offended by their
responses.
Some news-reading software can not display, or post, long articles ( like
this FAQ ), and you may have to ask your system administrator or ISP for
alternative software. A consistent inability to display large posts is
usually a problem with your reading software, not a mistake by the posters.
5.3 Should I post my homework question?.
In general, definitely not. Your homework question is designed to challenge

you to understand an aspect of chemistry, and your teacher will have
ensured that there are appropriate resources available to you at your
institution. The library is always an excellent place to start, and the
librarians are skilled at finding information - if you ask for assistance.
Before posting to the group, consider if a similar question could have

arisen in the past, and check DejaNews using relevant keywords. However,
if you find that the library and other available resources can not fully
satisfy your curiosity, then carefully outline your problem, list the
information resources you have investigated, and post only to the most
appropriate group. If it is the wrong group, somebody will point you to the
correct one. Do not expect to receive the actual answer, most readers will
carefully consider your request, and usually frame a response to ensure that
you need to perform some work before you can answer your own question. The
most obvious technique is to respond with a similar worked example which is
sufficiently different to ensure that you can not simply plug in numbers and
arrive at your correct answer. Often posters will point to specific library
resources for you to locate and read.
Also, remember that posters are not obliged to provide only correct answers,
they can deliberately introduce errors to ensure direct copying without
comprehension results in the wrong answer - it is not their homework :-).
Teachers can identify dramatic changes in students' writing styles, and a
quick search using Alta Vista or DejaNews can readily confirm their
suspicions. Do not expect sensible or accurate responses if you post from
anonymous servers.
5.4 Should I answer an obvious homework question?.
In general, definitely not. Teachers will set homework assignments that

do not require sci.chem responses. The poster was too lazy to consult the
resources that their teacher would have ensured were available locally, and
also too lazy to disguise their homework question. Continual answering of
obvious homework problems will merely attract more homework questions to the
group from other lazy students.
If the question does have some interesting aspects that you wish to comment
on, then the best course of action is to respond by answering a similar
question. If you change the question sufficiently, the poster will have to
understand the concepts you are offering, and then apply them to the
original question. This approach does require a little more effort and
imagination on your part, but it also encourages any interested students,
whilst also discouraging any lazy students.
In some homework questions, a small hint may be useful to point the student
towards a reference, or the correct answer, especially if their post
indicates that they are completely off-course. Hints are also a very useful
technique when you can not decide if posts are slightly modified homework
questions.
Some questions about chemicals in the home and workplace may arise from
curious adults who don't have a formal chemical education, and such questions
are certainly appropriate for sci.chem - so please ensure that the question
is actually a homework question before igniting your flamethrower.
5.5 I'm offering or seeking employment. Can I post here?.
Sci.chem is the most popular chemistry-related group, and thus would provide
the largest target audience. However, the appropriate group for advertising
vacancies and seeking employment is misc.jobs.fields.chemistry. Please post
CVs, Resumes, and Job Descriptions there, and frequently review the group.
Misc.jobs.fields.chemistry will have a very small readership, so it may be
worthwhile for those offering employment to also select a few relevant groups
and post a brief pointer to the post listing essential information. If you
have posted your resume or CV to m.j.f.c, then you just have to wait and hope
those with vacancies are reviewing the group. Do not post pointers to your CV
or Resume to other groups. Posting your CV/Resume to sci.chem may annoy some
readers who could be prospective employers in the future, so you have to
assume that those currently offering employment will review m.j.f.c. Also,
remember that all posts ( including CVs and Resumes posted to m.j.f.c ) may
be archived at sites such as DejaNews, and thus available for scrutiny by
future employers, unless you use the X-No-Archive header.
5.6 Can I post here if my newsfeed doesn't include the correct group?.
No. The onus is on you to obtain access to the correct group. As hard disk
storage prices are plummeting, you should be able to encourage your access
provider to carry more groups :-). If your employer restricts you to sci.*
comp.* and other boring groups, you may have to seek out a commercial
access provider. Be assured that you are not the first to encounter this
problem, and there are various ways you can access newsgroups using other
Internet facilities besides direct Usenet access. Check out the news.*
groups for information on alternative methods of Usenet access.
5.7 Can I post here if my library doesn't have the specified reference?.
No. Once again the onus is on you to obtain the texts. We have tried to
ensure that there are several choices to help minimise the problem. The
advantage of expending effort to obtain the reference is that it is likely
to provide a more comprehensive answer, and will enhance your understanding
of the subject. If the reference is obscure, then a carefully-constructed
post requesting the specific information you require is acceptable, but
you should also state that you have tried to obtain the information, and
perhaps suggest email replies if you believe other readers will not be
interested. Chemistry teachers and other chemistry professionals may also
have their personal copies of some of the reference texts, and may permit
you to use their copy, if asked politely.
5.8 Can I post articles I found in Usenet or on the Internet?.
No. Most countries have signed the Berne Convention, and adjusted their
national laws to reflect the concept that copyright ownership is the
property of the author of any piece of work. Thus any redistribution or
reproduction of that work has to have the author's express permission.
The act of posting to Usenet does carry an implicit acknowledgment that

followup articles will requote parts of the original for clarity, and
perhaps will be subsequently crossposted to additional groups and archived
at DejaNews or other archive sites. If an author of a post or article does
not want their post archived, your software may permit you to select the
"X-No-Archive" header and, if the software does not support that header,
you can also add it manually as the first line of a post, but some archive
sites may still ignore that header and archive the post.
The copyright of the article is still owned by the original author, and
consent is required before distribution extends outside of Usenet - including
placing it on the WWW. Most posters will readily give permission if asked.
Commercial WWW sites also have specific copyright notices just to remind
readers that the material can not be redistributed. "Fair Use" is a very
specific and limited concept, and does not permit significant copying of
copyrighted material - it expects the user to selectively edit and repost
only the minimum necessary material. Two FAQs ("Copyright Myths" and the
more detailed "Copyright" ) are posted to news.newusers.questions,
news.admin.misc, and some other groups that discuss intellectual property.
5.9 Should I post the email address of an expert I found?.
Not without their consent. Email the expert and ask if you can identify them
in sci.chem. In general, people who email information to you will want
complete control over their exposure on Usenet. Often they do not want a
lot of email requesting assistance, and in some countries ( such as New
Zealand ) people have to pay for both incoming and outgoing email. If the
email address is posted publicly - as in this FAQ, email the person and ask
if you can repost their address in a different forum.
When sending unsolicited email, remember that you are accosting a stranger,
and he/she is not required to respond, although most will respond to polite
requests.
5.10 Should I post corporate advertising material?.
No. Sci.chem is a discussion group. However, if your corporate material will

help resolve an issue being discussed, post a brief note pointing to where
the information can be obtained. If you believe that knowledge of your
corporation would help Internet users, you should arrange a World Wide Web
home page or email address, and then ensure the address is included in
compilations of chemistry-related material available on the Internet.
Continual repeat posting of inappropriate commercial material is likely to
annoy sci.chem readers. One method of raising the profile of your site is to
add a pointer to your signature file, and make useful contributions to
relevant discussions. Some readers may then visit the site out of curiosity.
5.11 Should I state why I require the requested information?.
Generally, yes. Knowing why somebody is requesting information often helps

those considering responding to the request. It also helps to ensure that
responses will help solve the problem, rather than lead off on a tangent,
interesting though it may become. You should also indicate your level of
expertise, and where you have looked, as that prevents well-intentioned
people wasting time suggesting sources you have already tried.
If you require the information for a commercial or historical enterprise,

you should alway state that. The ability to download and edit information
is even more convenient than photocopying, and original copyright can easily
be inadvertently omitted. If you note that there may be a possible commercial
outcome, responders will try to ensure that the original source is fully
credited. A polite request to the copyright owner will usually result in
approval for your enterprise.
5.12 What other chemistry-focused newsgroups exist?.
Sci.chem is the most popular group covering diverse chemistry topics.

Other chemistry-focused groups include;-
alt.drugs.chemistry - discusses the chemistry of all drugs.
misc.jobs.fields.chemistry - chemistry employment opportunities.
rec.drugs.chemistry - discusses the chemistry of recreational drugs.
sci.chem.analytical - discusses analytical chemistry.
sci.chem.coatings - discusses all aspects of surface coatings.
sci.chem.electrochem - discusses electrochemistry topics
sci.chem.electrochem.battery - discusses electrochemical cells.
sci.chem.labware - discusses laboratory equipment.
sci.chem.organomet - discusses organometallic chemistry.
sci.chem.organic.synthesis - discusses organic synthesis - moderated.
sci.engr.chem - discusses chemical engineering and industrial chemistry.
sci.techniques.mag-resonance - discusses magnetic resonance.
sci.techniques.mass-spec - discusses mass spectrometry.
sci.techniques.xtallography - discusses crystallography
Other groups cover specific topics that also have significant chemistry
components, including:-
alt.drugs.* - discusses all drugs.
rec.drugs.* - discusses recreational drugs.
rec.pyrotechnics - discusses pyrotechnics.
alt.cesium - cesium is discussed, along with much else.
soc.history.science - the history of science, including chemistry.
There are also chemistry groups in many national hierarchies. Some of these
groups are distributed fairly widely, and may be available from your ISP,
even though they may be in a language other than English.
There are also several other chemistry-related FAQs available, including

the sci.chem.electrochem FAQ maintained by Zoltan Nagy, and the Mass
Spectrometry Internet Resources FAQ maintained by Kermit Murray.
5.13 What questions are best answered elsewhere in Usenet?.
a. Anything concerning Usenet and Internet abuse, guidelines or behaviour.

- Start in the news.* hierarchy, such as news.admin.net-abuse.misc.
b. Anything concerning the provision of Internet services by your provider.

- Start in the specific, in-house, discussion groups - this includes
any apparent, sudden lack of posts in sci.chem.
c. Anything concerning illicit drugs.

- Start in the alt.drugs.* hierarchy and the rec.drugs.chemistry group,
as the various FAQs point to diverse chemical information sources.
- Refer to sections 13.1 - 13.6 of this FAQ for some available choices.
d. Anything concerning Ludwig/Archimedes Plutonium.

- Start at sci.physics, as they directed him to sci.chem :-). If you don't
like his posts, killfile him. Please don't start a campaign to remove
him, as all that happens is the group usually get flooded with junk.
For those interested in his theories, try the following WWW site.
http://www.newphys.se/elektromagnum/physics/LudwigPlutonium/
e. Anything concerning bubbles in newly-opened drinks.

- Start with sci.physics, the solubility behaviour of dissolved gases when
the pressure is reduced is predominantly a physical effect, although
section 19.4 briefly touches on the subject.
f. Anything scientific concerning the Ozone Hole and Climate Change.

- Start with sci.environment, in particular with Robert Parson's superb
FAQ on ozone, and Jan Scloerer's Climate Change - The Basics, both
available at the rtfm.mit.edu FTP site for Usenet FAQs. Non-scientific
discussions should always be moved to talk.environment.
g. Anything concerning explosives.

- Refer to sections 13.7 - 13.10 of this FAQ for the available choices.
5.14 Why is the sci.chem.* hierarchy not rational?.
As the sci.chem group has up to 80 posts/day, some specialists believe they

would be better served having their own group. They draft a charter, submit
it to the news.advice group, who ensure it is consistent with the overall
structure of Usenet and, after discussion, the group is voted on. If the
group passes it is created. Groups appear only if some motivated people
arrange to form them. That is why the structure is not rational.
There is currently no formal structural plan for the hierarchy and, given
the diverse nature of current contributions, it is proving difficult to
develop such a plan - as no one wishes to compromise the diversity of
sci.chem. If you learn to use the features of your newsreader correctly,
the current size of sci.chem is easily handled, and most threads of interest
can be captured as they pass.
5.15 How do I create a sub-group for my pet topic?.
First of all, discuss your idea extensively in sci.chem and other relevant
groups and mailing lists, ensure you have sufficient support for your
proposal, and take note of all comments, whether positive or negative.
The next stages are well documented in a FAQ available in news.groups.
Basically, you email group-advice@uunet.uu.net, who will help you prepare
the charter and Request For Discussion, and may even provide a mentor to
guide you through the process.
If the proposal has an additional vote that could affect another group by
renaming or changing the hierarchy, return to that group and consult the
participants to ensure there is support for any proposed changes prior
to issuing the RFD. Group advice is not mandatory, so if the added vote
is contentious, drop it. Post the RFD twice, and remind people to ensure
they cross post to news.groups, even if they do not read that group, as
that is where all post-RFD discussion is supposed to occur. Take note of
the discussion in news.groups and other groups where you posted the RFD,
and modify the RFD, if appropriate, and post it again. Then follow the
guidelines for the actual vote, others will administer the vote and create
the groups, if they pass.
5.16 Where are the sci.chem archives?.
Given the nature, number, and diversity of sci.chem posts, no formal

archives exist, however the Usenet archives at DejaNews on the WWW will
contain most of the articles for the last couple of years,
http://www.dejanews.com/
There are also several other WWW sites that offer access to, and
keyword searching of, recent Usenet posts. One site is Alta Vista.
http://altavista.digital.com/
The total number of articles that you will see in sci.chem will depend
on how your system administrators have set the News system. If they set
a short Expire time, and set the software to ignore the Expiry date line,
you may actually miss some articles that have long propagation times.
The best solution is to politely ask the administrators to increase the

Expire time - usually they are more sympathetic to requests to increase
Sci.* expire times than they are to requests for longer Alt.* expire times.
Sometimes they just can't oblige, so you may have to read the group more
frequently, but please check DejaNews before posting requests for old
articles.
It should also be remembered that Usenet archive sites like DejaNews

will retain all of your posts - unless you set the "X-No-Archive" header
appropriately. Some posting software does not have the facility to set
such headers, but it can be added manually to the first line of a post.
It has been reported that some employers now review such archive sites for
posts when evaluating job applications. Although DejaNews honours the
"X-No-Archive" header, that does not mean that all archiving sites will,
so your posts may still be hiding somewhere on the Internet.
5.17 Who was Larry Lippman?.
When sci.chem was formed (1988?), there were only a few posts per week, and
a considerable number were requests for information. Larry Lippman soon
established his superb practical and theoretical chemical credentials, and
set about responding to those plaintive pleas for information. His posts
were excellent examples of informative, educational responses delivered in
a friendly, helpful style. His posts demonstrated how knowledgeable sci.chem
posters could respond to requests in such a way that all readers would
understand, regardless of formal chemical training. He died in late 1991
in his early 40s. Unfortunately, only a few of his posts to sci.chem have
survived. If you have any of his posts I would appreciate a copy, as I am
collecting them to be made available as a single "Lippman posts" file.
Subject: 6. Common terms and abbreviations frequently used in sci.chem.
6.1 Abbreviations used in this FAQ and sci.chem
ACGIH = American Conference of Governmental Industrial Hygienists

ACS = American Chemical Society
AOAC = Association of Official Analytical Chemists
AOCS = American Oil Chemists Society
APHA = American Public Health Association
API = American Petroleum Institute
ASTM = American Society for Testing Materials
BP = British Pharmacopoeia
CA = Chemical Abstracts
CAS RN = Chemical Abstracts Service Registry Number ( usually as [x.y.z] ).
C&EN = Chemical & Engineering News ( journal )
CMR = Chemical Marketing Reporter ( journal )
DIN = Deutsches Institut fur Normung
EP = European Pharmacopoeia
GMP = Good Manufacturing Practice
IP = Institute of Petroleum
IPCC = Intergovernmental Panel on Climate Change
ISO = International Standards Organisation
ISO 9000 = The 9000 series (esp.9001) Quality System Standards
MSDS = Material Safety Data Sheet
RTECS = Registry of Toxic Effects of Chemical Substances
TLV = Threshold Limit Value ( defined by the ACGIH )
USP = United States Pharmacopoeia
6.2 Common Terms used in this FAQ.
These terms apply to well-known reference texts. Note that those with a "*"
are also available from commercial database suppliers and/or as CD-ROMs.
The electronic versions may be accessible via an institution library, if the
library does not have the hardcopy version available.
* Beilstein = Handbuch der Organischen Chemie [1].
* Bretherick = Handbook of Reactive Chemical Hazards [2].
* Chem.Abs. = Chemical Abstracts [3].
Cotton and Wilkinson = Advanced Inorganic Chemistry [4].
Fieser & Fieser - Reagents for Organic Synthesis [5].
* Gardner = Chemical Synonyms and Trade Names [6].
Gmelin = Handbuch der Anorganischen Chemie [7].
Goodman & Gilman = The Pharmacological Basis of Therapeutics [8].
* Hawley = Condensed Chemical Dictionary [9].
* Heilbron = Dictionary of Organic Compounds [10].
* Kirk Othmer = Kirk Othmer Encyclopedia of Chemical Technology [11].
Lange = Handbook of Chemistry [12].
* Martindale = The Extra Pharmacopoeia [13].
McKetta = Encyclopedia of Chemical Processing and Design [14].
Mellor = Comprehensive Treatise on Inorganic and Theoretical Chemistry [15].
* Merck = The Merck Index [16].
Perry = The Chemical Engineers' Handbook [17].
* RTECS = Registry of Toxic Effects of Chemical Substances [18].
Rubber Handbook = CRC Handbook of Chemistry & Physics [19].
* Sax = Dangerous Properties of Industrial Chemicals [20].
Shreve = The Chemical Process Industries [21].
Ullmann = Encyclopedia of Industrial Chemistry [22].
Vogel = "Inorganic" = Quantitative Inorganic Analysis [23].
= "Qualitative Inorganic" = Qualitative Inorganic Analysis [24].
= "Organic" = Practical Organic Chemistry [25].
= "EPOC" = Elementary Practical Organic Chemistry [26].

topic!
knowledge

Date: Thu, 15 Jan 2004 22:07:52 +1300
Message-ID: <m1mc00tc9oucbfi07dbk9bcce7v83kh6vi@4ax.com>
Version: 1.17
Subject: 7. General Chemistry-related Information on the Internet
Compiled by: Neil Flatter

Lev A. Gorenstein
Theodore Heise
Mark Perks
Mutilated by: Bruce Hamilton
There are so many references that relate to chemistry on the Internet

that this section could become overwhelming in size. Instead of trying to
provide a comprehensive listing of all such sites, what follows is more a
collection of pointers to other sources that carry a diverse range of
material related to chemistry. By knowing where to look for an answer,
these references should provide a springboard for an information search
on the Internet. Specialist software and search engines are available to
search for keywords using Gopher and the WWW, and they will also point to
additional sources not accessed by the sites below.
7.1 How can I access databases such as Chemical Abstracts?
These databases are almost all inevitably commercial, it costs serious

money to build and update them, thus it will cost money to access them.
Either you or your institution will be paying the supplier. Do not
expect to find copyrighted databases ( such as the Merck Index, Chemical
Abstracts, Kirk Othmer, or Sax ) freely available on the Internet.
There are several commercial suppliers of databases that contain chemical
information. These can usually be accessed either via the Internet or
telephone Packet Switching Networks. The most well known specialist database
is the American Chemical Society's Chemical Abstracts [1], which is provided
by the Chemical Abstracts Service. CAS offers a commercial database service
called STN International, which contains over 190 scientific and technical
databases.
These databases cover all aspects of Chemistry, including CAS

Registry Numbers, and are accessible via the WWW.
http://www.cas.org/ Chemical Abstracts Service.
http://info.cas.org/stn.html STN Introduction
http://www.dialog.com/ Dialog
The most universal and comprehensive database supplier is Knight Ridder,

whose Dialog service offers over 40 databases that solely concentrate
on aspects of chemistry, including Chemical Abstracts since 1967 ( but it
does not offer the actual abstract, just the bibliographic information )
and the CAS RN database [2]. Dialog also offers several hundred other
commercial and technical databases, and Knight Ridder also offers selected
general and technical databases on a low-cost, home user ( off-peak :-) )
system known as " Knowledge Index " at approx 25% of the normal Dialog cost.
Knowledge Index is also available from some on-line suppliers such as
Compuserve - but remember that KI does not include CA.
The ability to perform on-line searches is becoming an essential attribute

for modern chemists. Major database suppliers offer a wide range of training
courses and there are several excellent articles on searching the chemical
literature ( database and/or journals) in journals such as J.Chem.Ed.[3-5].
If you have access to a CD-ROM database, you should practise your search
logic on that first, before going on-line. Because of the cost structure of
database suppliers such as Dialog, and the inappropriate selection of
keywords by authors :-), it is often more cost-effective to focus on grabbing
around 100-200 titles and scanning them offline ( using the 30 minutes
"hold search" function ), and then going back online to grab the desired
abstracts and citation information.
7.2 What chemistry-related material is on the WWW?
Searching
There are several well-known search engines available on the WWW that will
provide updated searches for keywords. Because of the huge expansion of the
WWW, I've decided to select some sites and allow users to use search
engines and/or web crawlers to locate resources. If you find a real
treasure house of chemical goodies, email me the address and I'll check it
out. It is important to realise that many of the WWW search engines are
complementary, and so it is useful to utilise several when trying to locate
information on the web - good places to start are directories of various
WWW search engines.
http://home.netscape.com/home/internet-search.html
http://cuiwww.unige.ch/meta-index.html
Free search engines include:-
http://altavista.digital.com/ Alta Vista

http://www.google.com/ Google
http://www.lycos.com/ Lycos
http://www.yahoo.com/ Yahoo
http://infoseek.go.com/ Infoseek
http://www.excite.com/ Excite
http://www.webcrawler.com/ Webcrawler
Chemistry Overview sites
http://chemfinder.camsoft.com/
The fastest and best way to discover information about chemicals on
the WWW is CambridgeSoft Corporation's Chemfinder free searching
server. This has to be one of the most convenient ways to obtain
chemical information on the Internet. Highly recommended.
http://www.chemsoc.org/crl/links.htm
The Royal Society of Chemistry maintains an excellent list of sites
containing chemistry-related material, and is a good starting point.
http://www.chemcenter.org/
This is the new WWW site from the American Chemical Society, and
is intended to be their prime location of chemical information.
Other very useful sites include;-

http://www.chemdex.org/
The University of Sheffield comprehensive listing of WWW Chemical info.
Over 2200 sites indexed as of September 1996.
http://www.chemie.uni-regensburg.de/external.html
List of Chemical Services and Resources
http://webbook.nist.gov/
Comprehensive compilation of the NIST Chemistry WebBook, which
includes thermochemical, IR, and mass spectral data.
http://www.chem.ucla.edu/chempointers.html
The World-Wide Web Virtual Library: Chemistry.
http://rustico.chem.indiana.edu/
Gary Hieftje's site, covering many aspects of spectrochemistry.
http://www.indiana.edu/~cheminfo/
Gary Wiggins' extensive compilation of WWW chemical sites.
http://www.netsci-journal.com/
Internet Journal of Science - Biological Chemistry
http://www.cas.org/
Chemical Abstracts Service offers a diverse range of information
with a search facility.
http://www.camsoft.com/
CambridgeSoft site, ChemDraw, glassware, clip-art
http://www.chem.vt.edu/chem-ed/vt-chem-ed.html
The Chemistry Hypermedia project, especially chemical education.
http://www.rpi.edu/dept/chem/cheminfo/chemres.html
Another listing of Chemistry Internet Resources
http://dir.yahoo.com/science/chemistry/
The searchable Yahoo Collection of Chemistry Resources
http://www.mdli.com/
Home of the ISIS/DRAW chemical structure drawing programme
( free for academic and personal home use ).
Chemistry Education
Many of the WWW chemistry directories above also have extensive links to
educational resources, services, and institutions:-
http://www.chemdex.org/
http://www.chemie.uni-regensburg.de/external.html
http://www.chem.ucla.edu/chempointers.html
http://www.indiana.edu/~cheminfo/
http://www.chem.vt.edu/chem-ed/vt-chem-ed.html
Additional useful sites include:-
http://jchemed.chem.wisc.edu/
Journal of Chemical Education Online.
http://www-hpcc.astro.washington.edu/scied/chemistry.html
A comprehensive listing of education resources.
http://www.inform.umd.edu:8080/UMS+State/UMD-
Projects/MCTP/Technology/Chemistry.html
Internet Resources for Science and Mathematics Education compiled
by Tom O'Haver.
http://www-sci.lib.uci.edu/SEP/SEP.html
UC Irvine Science Education Program, not only chemistry.
http://ice.chem.umbc.edu/Chem351l/index.html
Typical University Organic Chemistry Laboratory information.
http://http://scifun.chem.wisc.edu/scifun.html
Bassam Shakhashiri's home page - full of entertaining information.
Other Chemistry-related Resources
http://www.che.ufl.edu/WWW-CHE/index.html
The Virtual Chemical Engineering Library
http://electrochem.cwru.edu/estir/
The Electrochemical Science and Technology Information Resource.
http://www.improb.com/
For the best science satire around, check out the Annals of Improbable
Research, successor to the Journal of Irreproducible Results. Whilst
the full version is only available via subscription services, such as
ClariNet, smaller items are published free in the Mini AIR.
http://www.chemheritage.org
Chemical Heritage Foundation site about history of chemical industry
http://www.acdlabs.com/
Diverse range of chemistry drawing, interpretation, and modelling software.
General Education Resources
Many of the Chemistry Overview sites also point to general science sites,
and use of the large search engines is recommended, but some additional
sites include:-
http://www.ccc.uni-erlangen.de/jmolmod/index.html
Journal of Molecular Modeling
http://www.inform.umd.edu:8080/UMS+State/UMD-Projects/MCTP/Technology
/MCTP_WWW_Bookmarks.html
Internet Resources for Science and Mathematics Education compiled
by Tom O'Haver.
Chemical Reference Spectra
http://webbook.nist.gov/
Comprehensive compilation of the NIST Chemistry WebBook, which
includes thermochemical, IR, and mass spectral data.
7.3 What information is available commercially on-line?
As well as the database suppliers such as Knight-Ridder's Dialog ( and

low-cost home-user Knowledge Index ) and CAS's STN International, there are
several other technical database suppliers that include chemistry-related
material, eg Orbit. These organisations usually approach institutional
librarians and provide comprehensive descriptions of their available
services. The best place to start is at your local library, talking to the
librarian in charge of on-line services to ascertain what is available, and
what levels of support are provided.
The obvious first places to start are Dialog and STN. The range of chemistry-
related databases are extensive. There are several full-text databases of
patents, full-text newspapers and journals, and many specialised databases.
- industry-specific Aluminium Industry Abstracts, Paperchem
- subject-specific Fine Chemicals Database, Chemical Engineering and
Biotech Abstracts
- chemical properties Beilstein, Heilbron, Merck Index, Agrochemicals
Handbook
- location-specific IMS World R&D focus.
- chemical market Chemical Business Newsbase, Chemical Industry Notes,
Freedonia Market Research.
If you plan on using Knight Ridder's lower cost Knowledge Index, ensure that
the databases you are interested in are available on KI, as not all Dialog
databases are.
With nearly 200 databases on STN and approximately 500 on Dialog, they both
offer access to a wide range of information. For more specialist information,
accessing individual businesses is required, and they can provide specialist
sales, marketing and technical support for their products - many such
businesses are now accessible via the WWW. There are also the various
registry companies like Thomas that list chemical and equipment suppliers,
and who also offer a free evaluation period:-
http://www.thomasregister.com/
7.4 What information is available free on-line?
The best technique is to use a WWW search engine to locate information

you desire, but some interesting locations are listed below.
CambridgeSoft Corporation's Chemfinder free searching server will
locate much of the diverse information about chemicals ( physical
properties, CAS RN, MSDS, etc. ) available on the Internet.
http://chemistry.mond.org/
Chemistry Today is a daily news service that can also be obtained
by email.
Several science journals are now making some of their commentary items and
abstracts available on the WWW, however subscriptions are still required
for access to the full journal. These include:-
http://www.nature.com/ Nature
http://www.newscientist.com/ New Scientist
Many of the Journals published by the American Chemical Society and Royal
Society of Chemistry also have homepages or articles available. The ACS
index also includes some of the UK and Japanese journals as well.
American Chemical Society

http://pubs.acs.org/about.html ACS Journal Index
http://pubs.acs.org/journals/cenear/about.html Chemical & Engineering News
http://dchas.cehs.siu.edu/Magazine/default.htm Chemical Health & Safety
http://pubs.acs.org/journals/ancham/index.html Analytical Chemistry
http://pubs.acs.org/journals/esthag/index.html Environmental Science
and Technology
http://pubs.acs.org/journals/jacsat/index.html Journal of the American
Chemical Society
http://pubs.acs.org/journals/joceah/index.html Journal of Organic
Chemistry
Royal Society of Chemistry
http://www.rsc.org/is/journals/j1.htm RSC Journal Index
http://www.rsc.org/is/journals/current/jcr/jcrpub.htm Journal of Chemical
Research
http://www.rsc.org/is/journals/current/oprd/oprpub.htm Organic Process R&D.
Society of Chemical Industry

http://ci.mond.org/ Chemistry & Industry
The Bulletin of the Chemical Society of Japan homepage is also available

via the ACS publications page.
http://pubs.acs.org/journals/bljapan/about.html
7.5 What chemical patent information is available on-line?
Both Dialog and STN offer commercial access to US and International patents
online, many with full text - however the international ones, especially
those devoted to capturing the current status of patents can be expensive,
so ensure your searching skills are honed if you wish to avoid a large
bill.
http://patent.womplex.ibm.com/
http://www.patents.ibm.com/
A new site that offers free searching of the last 20+ years of US
patents, and also provide the abstracts, some images, and the claim
summary free. Complete copies of the patents can also be ordered.
It has a good search engine, and probably should be the first site to
visit, but note that it requires a browser that supports frames
(eg version 3 of Netscape or Internet Explorer).
http://metalab.unc.edu/patents/intropat.html STO Patent retrieval service
Gregory Aharonian has struggled for several years to provide a free,
comprehensive patent title service. This excellent free service offers
the titles of chemical, mechanical, or electrical patents via email
to subscribers. Recently he also offered one years worth of patent
abstracts, but requires some financial donations to expand the
service. The abstracts are freely retrievable by patent number (sorry
no searching yet, that needs the big donations). For subscription info,
send 'help' to patents@world.std.com.
http://www.uspto.gov/patft/index.html USPTO/CNIDR Patent Project
This page provides access to both the U.S. Patent Bibliographic
Database, which includes bibliographic data from 1976 to 1997, and
the AIDS Patent Database, which includes the full text and images
of AIDS related patent issued by the U.S., European and Japanese
Patent offices.
7.6 Which FTP sites contain chemistry-related material?
ftp://kekule.osc.edu/pub/chemistry/
Jan Labanowsky's server, also contains an archive of the computational
chemistry mailing list.
ftp://qcpe6.chem.indiana.edu/
QCPE archive
ftp://oak.oakland.edu/pub/simtelnet/
Dos and Windows public domain and shareware
7.7 What chemistry-focused mailing lists exist?
LISTSERV@Beaver.Bemidji.MSUS.edu
Chemistry laboratories (both academic and research), students'
experiments (high school, college and university), classroom
demonstrations and shows for the public of chemical processes,
chemistry stockroom management, lab safety, and small-scale chemical
waste handling procedures.
7.8 How can I contact Chemical Societies electronically?
In general, most WWW sites will also contain email addresses that they
can be contacted through.
http://www.acs.org/
The American Chemical Society homepage provides access information,
and additional email support is available via the following:-
division@acs.org ACS Division information
expo@acs.org ACS expositions
meminfo@acs.org ACS membership information
natlmtgs@acs.org ACS national meeting information
rxnt@acs.org Reaction Times (college newspaper)
reglmtgs@acs.org ACS regional meeting information
slga@acs.org ACS state and local government affairs
http://www.rsc.org/
marketing@rsc.org
The UK Royal Society of Chemistry, WWW and email address.
http://sci.mond.org/
The UK Society of Chemical Industry.
http://www.gdch.de/
pr@gdch.de
The German Chemical Society (Gesellschaft Deutscher Chemiker, GDCh)
http://wwwsoc.nacsis.ac.jp/csj/index-e.html
The Chemical Society of Japan ( English index )
7.9 How can I contact large chemical companies?
Check their WWW pages for information.

http://www.argus.it/ Argus Chemicals
http://www.dow.com/ Dow Chemicals
http://www.eastman.com/ Eastman Chemicals
http://www.ge.com/plastics/ GE Plastics
http://www.hoechst.com/ Hoechst
http://www.lilly.com/ Eli Lilly
http://www.monsanto.com/ Monsanto
http://www.chemfirst.com/qci/ Quality Chemicals
http://www.rohmhaas.com/ Rohm and Haas
http://www.sigma-aldrich.com/ Sigma, Aldrich and Fluka
http://www.sumitomo-chem.co.jp/ Sumitomo Chemicals
You can observe the naming conventions, so try www.company-name.com for

other companies not listed, and you can also try using the on-line version
of the Thomas Register.
7.10 How can I contact chemical suppliers?
Several major chemical suppliers now have on-line catalogues on the WWW.
http://www.sigma-aldrich.com/
Sigma, Aldrich, Fluka, and Riedel de Haen chemical catalogues
http://www.fisherscientific.com/
Acros Chemicals catalogue
Fisher Chemical catalogue
http://www.romil.com/
Romil Chemicals catalogue ( high purity chemicals )
Check out the FAQs in rec.pyrotechnics and alt.drugs, they may also list
some legal suppliers. With the rapid growth of the WWW, it is usually
a good idea to conduct a search to locate suppliers, and you could try
the Chemsources or Thomas Register sites to locate addresses.
http://www.chemsources.com/
Use of WWW search engines and specific terms like "biochemicals"

will locate the WWW and email addresses of speciality suppliers
7.11 How can I contact equipment suppliers
Check out the FAQs in rec.pyrotechnics and alt.drugs, they may also list
some legal suppliers. With the rapid growth of the WWW, it is usually
a good idea to conduct a search to locate suppliers on the Internet,
and using the Thomas Register site to locate suppliers not on the Internet.
Thomas Register ( manufacturers and suppliers )
Sigma, Aldrich, Fluka and Supelco ( techware and books )
Fisher Catalogue ( general lab equipment )
7.12 How can I contact US government agencies?
http://www.fedworld.gov/
telnet://fedworld.gov/
FedWorld Information Network at the National Technical Information
Service NTIS) was created "to provide a one-stop location for the public
to locate, order, and have delivered to them, U.S. Government
information."
gopher://marvel.loc.gov/11/federal/fedinfo/byagency/executive
Executive Branch Gophers (Library of Congress)
http://www.nist.gov/
National Institute of Standards and Technology
http://www.atsdr.cdc.gov/atsdrhome.html
Agency for Toxic Substances and Disease Registry (Searchable)
http://www.dot.gov/
Department of Transportation
http://www.epa.gov/
Environmental Protection Agency
http://www.fcc.gov/
Federal Communications Commission
http://www.access.gpo.gov/
Government Printing Office
7.13 Where can I find compilations of science humour?
http://www.improb.com/
For the best science satire around, check out the Annals of Improbable
Research, successor to the Journal of Irreproducible Results. Whilst
the full version is available via subscription services, such as
ClariNet, smaller items are published free in the Mini AIR.
ftp://ftp.in.umist.ac.uk/pub/Text/
http://www.xs4all.nl/~jcdverha/scijokes/
A huge 500kB compilation of science jokes regularly posted to Usenet.
http://dir.yahoo.com/Entertainment/Humor/By_Topic/Science/
Annals_of_Improbable_Research/
Search selections from the Annals of Improbable Research
7.14 Where can I purchase scientific software?
Aldrich and Fisher sell software, as do some of the Chemical Societies

Sigma, Aldrich, Fluka and Supelco
Fisher Catalogue
http://www.acdlabs.com/
Diverse range of chemistry drawing, interpretation and modelling software.
Refer also to "Chemistry Overview Sites " and "Other Chemistry-related

Resources" in section 7.2.
Subject: 8. Laboratory and Chemical Safety Information on the Internet
Compiled by: Neil Flatter

Lev A. Gorenstein
Theodore Heise
Mark Perks
Mutilated by: Bruce Hamilton
8.1 Where can I find Material Safety Data Sheets?
Manufacturers are required by OSHA to provide MSDSs for the chemicals they
produce, but most include liability disclaimers. For MSDSs obtained from
online sources, the user must be sure the MSDS meets his/her needs. As with
most information obtained from the Internet, use at your own risk!. If you
don't know how to interpret the data, find an expert to explain the
significance of the information presented. Because the number of WWW sites
with MSDS are changing all the time, it is often preferable to use a WWW
search engine to find the latest sources of data sheets.
http://hazard.com/msds/
http://haz1.siri.org/
The comprehensive Vermont SIRI location is an excellent first port of
call when searching for chemical safety information. ~180,000 MSDS
http://msds.pdc.cornell.edu/issearch/msdssrch.htm
The Cornell site mirrors the Vermont SIRI site and also contains the
US Department of Defence CD-ROM MSDS. ~325,000 MSDS
http://www.ilpi.com/msds/
The Dept. of Chemistry, University of Kentucky, maintains an up-to-date
" Where to find MSDS on the Internet " site pointing towards over
thirty useful locations.
CambridgeSoft Corporation's Chemfinder free searching server will also
locate safety information for chemicals, including ~60,000 MSDS.
The Fisher Scientific Chemical Catalog is available online. In addition
to MSDSs, you can order chemicals.
http://ulisse.etoit.eudra.org/Ecdin/Ecdin.html
Environmental Chemicals Data and Information Network in Italy provides
a searchable database with 120,000 MSDS.
8.2 Where can I find detailed safety & toxicity data?
http://hazard.com/msds/
http://haz1.siri.org/
The comprehensive Vermont SIRI location is an excellent first port of
call when searching for chemical safety information.
CambridgeSoft Corporation's Chemfinder free searching server will
also locate safety information on chemicals, including MSDS.
http://www.atsdr.cdc.gov/atsdrhome.html
The Agency for Toxic Substances and Disease Registry (ATSDR) at the
Centers for Disease Control maintains a searchable database which
contains toxicological profiles of about 200 chemicals.
Note that many government departments now have made their databases
available to both commercial database suppliers ( such as Knight Ridder )
and private citizens. Some are free, and some charge, it is worth contacting
government agencies like OSHA, NIOSH, EPA, NIH and asking about what is
available. Some databases ( like NIH library ) can be accessed via telnet,
as also can Dialog ( once you have an account number ). eg
http://www.ncbi.nlm.nih.gov/PubMed/medline.html
Medline, a medical database maintained by the NIH
telnet://Dialog.com
8.3 Where can I find occupational exposure limits?
http://www.acgih.org/
The most well-known list of occupational exposure limits is the annual
list of TLVs and BEIs compiled by the ACGIH, who also offer a diverse
range of reports and pointers to other sources of information.
http://law.house.gov/cfr.htm
Recent (but perhaps not most current, but it is being updated) site
for the Code of Federal Regulations. Title 29 of the CFR (Labor)
section 1910.1000 lists OSHA's permissible exposure limits (PELs)
for air contaminants.
8.4 Where can I find hazard information for a chemical?
In general, the first contact should be the safety professional at your

institution, local poison centre or local fire department - as they will
be trained to review and comprehend the information they have access to.
A WWW visit to the sites in sections 8.1 and 8.2 will also provide some
information, and point to other sources. The following site has pointers
to several useful sources.
http://www.christie.ab.ca/safelist/
Carolla Christie of Christie Communications maintains an excellent
list of environmental and occupational health and safety information
resources available on the Internet. Many of the useful organisation
and institutional resources currently are only contactable via email.
8.5 Where can I find laboratory safety guides?
list of environmental and occupational health and safety information
resources available on the Internet.
http://www.sra.org/riskanal.htm RISKANAL mailing list.
discusses environmental and occupational health and safety issues,
particularly those associated with college and university campuses,
although a wide range of subjects is encouraged.
8.6 Where can I find other safety information?
Many of the Chemistry Overview WWW sites in Section 7.2 also have safety
sections with extensive numbers of pointers to WWW sites. Some US
Government departments ( OSHA, EPA, NIH ) have WWW sites with information,
which can be accessed directly, or via some of the sites in Section 7.12.
http://dchas.cehs.siu.edu/
The ACS division of Chemical Health and Safety homepage.
http://www.setac.org/
The Society for Environmental Toxicology and Chemistry
http://www.aiha.org
The American Industrial Hygiene Association
The WWW site below has large numbers of pointers to other sites with
extensive ranges of information on chemical, laboratory, and general
safety issues.
list of safety information resources available on the Internet.
The list is also posted to the SAFETY mailing list above.
Subject: 9. Traditional General Chemistry Information Sources
9.1 When can I find Chemical Abstracts?
Chemical Abstracts is produced by the ACS and is available either in

hardcopy or CD-ROM form in most institution libraries that have a chemistry
department. It is expensive, and is also available commercially from several
online database suppliers ( refer to Section 7.1 ). It is not legally
available free over the Internet. Some libraries have accidentally enabled
limited search access for anonymous users, but this is usually soon
curtailed, so enjoy them while you can :-).
If your school does not have access, the librarian should be able to
ascertain the nearest library that holds the hardcopy CA and also permits
public access. CA volumes are not available for interloan. All chemicals are
given an arbitrary Registry Number as they are encountered by the Chemical
Abstracts Service ( Section 12.1 ). Many information sources now also use
the CAS RN to overcome potential nomenclature confusion.
9.2 Where can I obtain chemical patent information?
Most governments have a patent office, and there are usually branches in main
centres. If you are able to obtain access to the patents at the patent office,
and are familiar with patent codes, or know the patent number, the cost will
be lower than using a patent attorney. If you do not know how to search for
patents, and your time is valuable, you will find that using a patent
attorney will be very cost effective. An excellent guide to the general
concepts of patents and what you can expect to find, along with the
advantages and disadvantages, is " What Every Engineer Should Know About
Patents" [1].
9.3 Where can I purchase chemicals?
The chemicals usually found in home chemistry sets can usually be purchased
at the shop where the set was obtained, or the local hardware shop or
pharmacist, provided the chemical is not subject to government or state
restrictions. Many chemicals are only available to approved purchasers.
If the chemical is used for a hobby, then it is very likely the FAQ for that
Usenet group ( eg rec.pyrotechnics ), will contain information on suppliers.
Most national chemical societies publish an annual listing of suppliers with
their journals. Standard trade directories ( eg Chem Sources [2,3] and OPD
Chemical Buyers Directory [4] ) list companies who specialise in chemicals,
however few will be interested in small purchases.
Smaller specialist and boutique suppliers are usually more likely to sell
small quantities of chemicals to individuals. Most larger suppliers of high
purity laboratory and industrial chemicals ( eg Aldrich-Sigma [5], J.T.Baker
[6] ) will only sell a limited range of chemicals to individuals , and
usually do not provide any discounts for individuals - unless they have an
account with the company. I'm not sure about the US, but here in NZ discounts
can halve the price of most chemicals.
If you are intending to acquire a wide range of chemicals over time, an

account may be a good idea, however remember that you may then be subject to
inspection visits by regulators if you purchase certain chemicals. Most
government and corporate organisations and laboratories also have policies
of not supplying unknown individuals with *any* chemical. Some chemical
suppliers are also accessible via the Internet ( refer Section 7.10 )
9.4 Where can I purchase laboratory equipment?
As with chemicals, simple laboratory equipment can be purchased from the

suppliers of home chemistry sets. Some government and state authorities
require certain equipment ( eg stills ) to be registered, especially if it
can be used to produce illegal substances. Most larger suppliers may
require an account, but often specialist supplies can be purchased from
hobby shops such as home brew kit suppliers. Once again the FAQ of
relevant newsgroups ( such as alt.drugs and rec.pyrotechnics ) may provide
the names of suppliers, as can trade directories and the Yellow Pages.
Cole Palmer and Fisher offer free comprehensive catalogues that identify
what is available. Some equipment suppliers are accessible via the Internet
( refer Section 7.11 ).
9.5 What reference texts should I search first?
If you require basic physical information about a chemical then many

chemical suppliers catalogues also include common properties - such as
boiling point, melting point, density, and flash point. Aldrich, Merck,
and Lancaster provide information on organic chemicals, and Sigma covers
biochemicals. Chemical catalogues also often provide cross references to the
Chemical Abstracts Registry Numbers, the Merck Index, spectral libraries,
safety, and preparation information. The actual product purity may limit the
accuracy of the data, and more accurate information could be available
in the Rubber Handbook or Merck Index. As catalogues are usually free on
request ( Aldrich catalogue is also available on disk as a searchable
database for $25 ), they are an excellent initial information source that
will often direct you to appropriate reference texts. You may be able to
acquire an older edition by asking your chemistry teacher or chemical
storeroom supervisor.
Depending on the type of chemical information required, some specialist

reference texts may be required, but there are several texts that are common
to most fields of chemistry. These are usually found in the reference
section of most public and technical libraries and, because they are often
heavily discounted for students, many chemists have copies of several of
them. If your library does not have them, ask some of your teachers for
access to their personal copy.
Many of these texts are now also available on CD-ROM, usually at a slightly
lower cost than the hardcopy, however the Merck Index is an exception where
the CD-ROM version costs significantly more than the hardcopy. The Merck
Index is an excellent starting point for information on organic chemicals
used in the agricultural, biochemical, chemical, and pharmaceutical
industries. It is usually available, along with the Rubber Handbook, in the
reference section of libraries. Don't expect a $7,000 encyclopedia set like
Kirk Othmer to be freely available over the Internet, or available on
CD-ROM for $100 :-). I have also marked those that are commercially
available through online services with an asterisk.
For more detailed aspects of individual compounds, common texts include:-
CRC Handbook of Chemistry & Physics ( aka Rubber Handbook ) [7]

- tabulations of diverse chemical and physical properties.
- start here for physical data with minimal description.
The Merck Index * [8]
- brief monographs on most common organic chemicals, especially those
used in the chemical, biochemical, and pharmaceutical industries.
- excellent source for physical and physiological properties, common
names, and CAS RN.
- monographs point to more descriptive sources.
- available on CD-ROM, but the hardcopy version is much cheaper.
Lange's Handbook of Chemistry [9]
- tabulations of chemical properties.
Hawley's Condensed Chemical Dictionary [10]
- very brief monographs on a wide range of common industrial chemicals.
- very good starting point to ascertain physical properties of both
inorganic and organic chemicals used in commerce.
- Available on CD-ROM
Tables of Physical and Chemical Constants ( aka Kaye and Laby ) [11]
- tabulations of constants, often not in the Rubber Handbook
The Chemical Technicians' Ready Reference Handbook [12]
- tabulations of various common chemicals and materials.
The Matheson Gas Data Book [13]
- tabulations of properties of a diverse range of gases
There are several good general "science" texts that provide basic coverage
of aspects of chemistry, eg the concise version of the McGraw Hill
Encyclopedia of Science and Technology [14] or Van Nostrand's Scientific
Encyclopedia [15]. There are also several single volume chemistry books
that provide brief monographs covering diverse aspects of chemistry, such as
the McGraw Hill Encyclopedia of Chemistry [16]. These texts are often found
in the reference sections of general libraries.
The next source is usually the encyclopedia sets that are also found in the
reference section of general libraries. There are some general ones that
cover all fields of science, and often have annual updates. An example is
the 20 volume McGraw Hill Encyclopedia of Science and Technology, available
in hardcopy or CD-ROM versions [17].
For more detailed, but still with general coverage, there are at least two
popular large multi-volume chemistry encyclopedias. One, or both, of these
is usually found in the reference sections of technical and large public
libraries. These have become the standard first point of reference for
information on properties, production, and applications of industrial
chemicals.
Kirk Othmer Encyclopedia of Chemical Technology - 4th edition * [18]

- excellent 27 volume set
- extensive monographs on chemical families and processes.
- start here if you wish to obtain up-to-date, easy-to-read, comprehensive
technical information on an amazingly diverse range of chemistry.
( available in hardcopy ($324/volume, around $7,000/set), online, on
CD-ROM, and as a greatly-abridged concise volume (3rd Edition = $110)
Ullmann's Encyclopedia of Industrial Chemistry - 5th edition [19]
- excellent translation from the original German edition.
- extensive monographs on common industrial processes
- the style is different to Kirk Othmer in that information is not so well
integrated into the monograph, but often contains more hard information
and good reviews of specific topics.
( In 1997 the fifth edition was made available on CD-ROM, with the sixth
edition was started in 1998, with each CD holding the equivalent of
three printed volumes. The full book/CD-ROM sixth edition will cost
around $14,000 )
There are also the very large multi-volume sets of specialised chemical
information that are mainly only found in institutions that have a strong
chemistry or chemical engineering component, such as:
Beilstein * [20]
- provides detailed monographs of most organic chemicals, covering
preparation, properties and structure.
Gmelin [21]
- provides detailed information on most elements and inorganic chemicals
Heilbron * [22]
- provides short monographs of many organic compounds, mainly listing
properties and references to preparations. An excellent way to
quickly find information on chemicals.
McKetta - Encyclopedia of Chemical Processing and Design [23]
- extensive monographs containing technical data on chemical processes.
Encyclopedia of Polymer Science and Engineering - 2nd edition * [24]
( available in hardcopy, online, and in a greatly-abridged concise volume )
- detailed monographs on common polymers and processes
Thorpe's Dictionary of Applied Chemistry [25]
- getting old, but *still* contains lots of excellent information on the
properties and industrial applications of chemicals
- is very useful for historical information on how a product developed.
For more specialised references, refer to the appropriate section of this

FAQ, however I will list a few texts covering general laboratory techniques
not mentioned elsewhere. If your local bookshop does not carry specialist
technical books, many are also available from appropriate chemical and
equipment suppliers, such as Aldrich-Sigma and Supelco.
Vacuum = High Vacuum Techniques for Chemical Syntheses and Measurements [26].
= High Vacuum Techniques [27]
Pipework = Swagelok Tube Fitting and Installation Manual [28]
Thermocouples = Thermocouples: Theory and Practice [29]
( The Omega catalogues are also a good source of practical information
on a wide range of temperature, flow and pressure sensors )
Many of the laboratory safety texts also include sections on design and
management of laboratories.
9.6 Where can I find physical and spectral properties of chemicals?
Some chemical suppliers catalogues ( eg Aldrich [5] ), also include common

properties such as boiling point, melting point, density, flash point.
Most will provide a catalogue free on request, but it is often easier to
obtain an obsolete edition from your institution, as they usually just throw
them out. The most information is often in catalogues from international
laboratory chemical suppliers ( eg J.T.Baker [6], Merck [30], Rhone-Poulenc
[31] ), and specialist organic chemical suppliers ( eg Aldrich [5],
Sigma [32], Janssen [33], Lancaster [34] ), however it should be remembered
that the product purity will affect the value reported, and that more
accurate values may be available in references such as the Merck Index or
Rubber Handbook.
Once you have checked the catalogues, and checked the standard texts above,
then more specialised compilations should be checked. For spectral
properties, there are several large compilations of detailed spectral
properties, including infra-red [35-37], NMR [38-40], and mass-spec [41,42].
These are usually located near the instruments, rather than in the library,
however the NIST IR and mass spectral libraries are accessible via the WWW
( refer Section 7.2 ).
Most transportation safety compilations and MSDS also list common physical
properties, as do the most of the encyclopedia sets ( refer Section 9.5 ).
More specialised information is usually found in specialist books or
journals, such as the Journal of Chemical and Engineering Data.
9.7 Where can I find production data for commercial chemicals
Both Kirk Othmer and Ullmann tabulate production data, and identify
major manufacturers, and more recent information is found in monographs
in CMR. C&EN also tabulates production data for the major industrial
chemicals and publishes an annual listing of the top 50 chemicals. Lists of
manufacturers of chemicals are found in compilations such as Chemical
Sources [2,3] and trade directories. There are also industry organisations
such as the Chemical Manufacturers Association that maintain records of
production. Specialist industry journals usually provide annual surveys
of production and capacity. Government departments ( often the Dept. of
"Trade & Industry" or "Commerce" ) also compile national production
statistics.
9.8 Where can I find the composition of a proprietary chemical?
If it has been patented, the composition will be detailed in the patent,

and any local patent agent should be able to locate and obtain a copy.
Transportation regulations usually require manufacturers to list components,
consequently examination of the MSDS often provides an indication of major
components, some of which are likely to just be the solvent. There are also
compilations of chemical tradenames that may also indicate what the major
components in a proprietary chemical. Hawley, Gardner, Industrial
Chemical Thesaurus [43], Encyclopedia of Industrial Chemical Additives [44],
and the Chemical Tradenames Dictionary [45] are good starting points.
In some countries only the "active" or "toxic" ingredients have to be

disclosed, consequently chemical analysis would have to be undertaken.
Another technique is to look for equivalent formulations - to ascertain what
ingredients are typically used, and the multi-volume Chemical Formulary [46]
is one of the best sources if you can not justify a patent search.
9.9 Where can I find out about the history of Chemistry?
There is a soc.history.science Usenet group that is very knowledgeable and

active, and includes individual events in the history of chemistry. There
are usually several overview books on the history of chemistry in most school
and public libraries, and example is "The History of Chemistry" by J.Hudson
[47]. There are also several outstanding biographies of famous chemists, and
many chemical societies and chemical firms have commissioned books on
specific aspects of chemistry history. The Journal of Chemical Education
often has articles on specific historical aspects of chemistry.
9.10 Where can I find out about the discovery of an element?
The Rubber Handbook has a monograph on each element, including a brief

discussion of the discovery. "Chemistry of the Elements" by Greenwood and
Earnshaw [48], and "The Elements" by Emsley [49], also provide good
discussions, and Gmelin provides a fairly comprehensive discussion of
discovery of each element. In each of the above, the discovery of each
element is taken in isolation. The best general overview that provides a
cohesive framework explaining the overall progression of discoveries, is
"Discovery of the Elements" by Weeks [50], and it should be available in most
libraries. For the more recent elements, there usually are brief reports and
discussions in C&EN and the Journal of Chemical Education.
9.11 What inspirational books about chemistry should I read?
Do they exist :-)?. You could try "The Chemical Bond: Structure and Dynamics"
edited by A.Zewail [51]. It contains articles by several Nobel Laureates.
If you want to be entertained, and only have time for a short read, try the
"Chemistry in the Next Century" [52] article in Industrial and Engineering
Chemistry written in May 1935 by Thomas Midgley, Jr.. He was responsible for
the discovery and development of CFCs and alkyl lead octane enhancers for
gasoline - two chemical developments that became so pervasive and useful
that their use resulted in unintentional environmental pollution.
For a brief story about their discovery, try "Midgley - Saint or Serpent"
[53] in Chemtech. It confirms that old saying " Luck is when preparation
meets opportunity ".
Subject: 10. Traditional Laboratory and Chemical Safety Information Sources
10.1 Where can I find Material Safety Data Sheets?
Most suppliers of chemicals will provide a MSDS on request if you are a

customer. Several major chemical suppliers have combined their own MSDS
sheets and issued major compilations, eg Sigma-Aldrich [1] ( available on
CD-ROM or Magnetic Tape for $1,650), which may be available in the
library. If a librarian can not locate the MSDS database, then try the
Health and Safety Officer, who should know where to find MSDS. Larger
organisations often purchase a compilation and make it available on a
computer network for in-house use. The US Department of Defence CD-ROM
of approximately 200,000 MSDS is available for approximately $100.
10.2 Where can I find hazard information for a chemical?
Chemical suppliers usually include common hazard information in their

catalogues. Merck and Hawley also list some information. Large compilations
include Sax, Fire Protection Guide to Hazardous Materials [2],
Sigma-Aldrich Library of Chemical Safety Data [3], CRC Handbook of
Laboratory Safety [4], and Hazards in the Chemical Laboratory [5]. It is very
important to realise that hazard information is frequently updated, and so
information should be complemented with an online search of safety databases.
If the chemical is already being used at your site, it is probable that the
Safety Officer or Laboratory Manager already have the required information.
The Handbook of Reactive Chemical Hazards [6], can be used to check for
possible hazardous reactions. Highly toxic, radioactive, and carcinogenic
compounds require special precautions, and the Safety Officer or Laboratory
Manager should be able to provide the appropriate resources to ascertain if
the compound can be handled safely.
10.3 Where can I find detailed safety & toxicity data?

The very first question you should ask is, "Am I qualified to assess
the data?". If the answer is no, then your best option is to locate somebody
who is. This can be a Health and Safety Officer, staff of an appropriate
government organisation (eg OSHA, NIOSH ), or a specialist consultant.
Most institutions have a policy of ensuring workers are given sufficient
information about hazards to ensure they can make an informed decision.
There are several major compilations that are usually found in libraries,
including RTECS, Sax, and the three-volume Sigma-Aldrich Library of
Regulatory and Safety Data [7]. In general, because safety information can
become obsolete rapidly, these should only be used as an introductory guide,
and they should be complemented with either an on-line search or consultation
with
an expert. Detailed information for unusual chemicals is often difficult to
locate in the published literature, and may only be available to qualified
professionals in the health and safety fields. Sometimes the toxicity has to
be inferred from published information on related compounds, and such
assessments should always be performed by experts.
10.3 Where can I find occupational exposure limits?
There are several organisations responsible for establishing the

occupational exposure limits. The values used most extensively in industry,
but also the most controversial, are those of the ACGIH. Their TLVs and
Biological Exposure Indices [8] have been used in many countries as initial
guidelines until relevant local expertise can assess their suitability.
They are also misused, despite the clear warnings in the front of the
booklet.
The US Government also has Permissible Exposures Limits set by the Dept. of
Labor Occupational Safety and Health Administration, and Recommended
Exposure Limits set by the US National Institute for Occupational Safety and
Health. The Deutsche Forschungsgemeinschaff Maximum Concentrations in the
Workplace are often also used. The ACGIH publishes an excellent compilation
of all these limits [9], thus facilitating a review of how experts perceive
the occupational hazards. The International Labour Office in Geneva
publishes a comprehensive " Encyclopedia of Occupational Health and Safety "
which also covers chemicals [10].
10.5 What is the most poisonous compound?
" All substances are poisons. There is not one that is not a poison. The
correct dose differentiates a poison and a remedy". (Paracelsus 1493-1541)
The McGraw Hill Encyclopedia of Science and Technology [11] lists the
following table:
"Approximate Median Lethal Doses of Some Toxins per kg of Bodyweight"

Toxin Dose Test Animal
tetanus 1 nanogram mouse, probably human
botulinal neurotoxin 1 nanogram mouse, human
shigella 1 nanogram monkey, human
shigella 1 microgram mouse
ricin 1 microgram human
diphtheria 100 nanograms human
diphtheria 1.6 milligrams mouse
Ricin is a toxin lectin and hemagglutinin isolated from the castor bean.
Merck reports the lethal dose in mice as 1 microgram of ricin D nitrogen
(ip) per kg, and that ricin molecular weight is about 65,000. Ricin has
been shown to contain four lectins, of which the RCL III (aka Ricin D )
and RCL IV are the toxins. Merck also reports the following LD50 per kg
of bodyweight:-
Toxin Dose Test Animal

palytoxin 60 nanograms dog (iv)
( from coral ) 450 " mouse (iv)
( C129H223N3054 ) 50-100 " " (ip)
saxitoxin 3-5 micrograms mouse (iv)
( from shellfish ) 10 " " (ip)
( [C10H17N7O4]2+ ) 263 " " (oral).
tetrodotoxin 10 " mouse (ip)
( from globefish )
aflatoxin M1 332 micrograms duckling (oral)
aflatoxin M2 1.2 milligrams " "
aflatoxin B1 364 micrograms duckling (oral)
aflatoxin B2 1.6 milligrams " "
aflatoxin G1 784 micrograms " "
aflatoxin G2 3.4 milligrams " "
The complex structure of palytoxin is shown in Merck, and it is listed as

the most toxic non-proteinaceous substance known.
10.6 Where can I find laboratory safety guides?
The journals "Chemical Health and Safety", and "Journal of Chemical

Education" have articles on many aspects of laboratory safety. Safety
Officers and Laboratory Managers at educational institutions and companies
are likely to have several guides, and a polite request should obtain a loan
or copy of one, even if you aren't at that institution.
There are several useful books. The most popular are:-

CRC Handbook of Laboratory Safety [4]
- good general discussion of laboratory safety issues.
Hazards in the Chemical Laboratory [5]
- good general discussion of laboratory safety concepts with data.
Guidelines for Laboratory Design: Health and Safety Considerations [12].
- modern design concepts for new and refurbished laboratories.
Laboratory Health and Safety Handbook: A Guide for the Preparation of a
Chemical Hygiene Plan [13]
- such a plan is required by OSHA, and additional examples may also be
available from chemistry departments of local educational institutes.
10.7 Are contact lenses a hazard in laboratories?
There are a lot of myths about the occupational use of contact lenses, many
of which relate back to a Bethlehem Steel welder in Baltimore who, on the
26 July 1967, accidentally caused an arc flash that hit his hard contact
lens. He waited until the next day to report eyesight problems, and an
ophthalmologist found severe ulcerations on his cornea, but attributed
the damage to the wearing of the hard lenses for 17-18 hours after the
incident. The cornea healed completely in a few days, with no permanent
vision loss, and investigators found no link between the damage and the
arc flash, but the myth of the welder removing parts of the cornea with
the lens, and consequently being permanently blinded, continues [14].
The banning of contact lenses from modern chemical laboratories is being

reconsidered in the light of increasing evidence that case-by-case
evaluations are more appropriate. Routine wearers of contact lenses may
suffer " spectacle blur " when they switch to spectacles, and this temporary
reduction in visual efficiency could result in the misreading of labels.
Contact lenses are not eye protection devices, and OSHA believes that
if eye hazards are present, appropriate eye protection must be worn
instead of, or in conjunction with, contact lenses. There may still be some
laboratory environments where the provided personal protection equipment
does not protect wearers of contact lenses, and they will remain banned.
There are three major areas of concern about the hazards of wearing
contact lenses in chemical laboratories.
1. They can hold particulate or liquid material against the cornea.

The modern soft contact lenses are considered suitable for most
environments, except where heavily contaminated with metal particles.
Hard contact lenses are not considered suitable for use in
particle-contaminated areas.
2. Contact lenses can be difficult to remove after a chemical splash.

This is a concern, and is one reason why wearers of contact lenses in
laboratories should be obviously identifiable to first-aid and
professional secondary care providers. The copious irrigation procedures
with water ( whilst holding the eye open ) that should immediately follow
chemical splashes may wash the lenses out, and trained staff can remove
any remaining lenses later. Experiments with concentrated sodium
hydroxide solution, sulfuric acid, acetic acid, acetone and n-butylamine
have shown that contact lenses may actually provide some protection [14].
3. Contact lenses may absorb and retain chemical vapours.

This effect was not observed in the splash experiments above, and soft
lenses have been shown to reduce the effect of acids, perhaps because
tears can dilute the acid by the time it passes through the lens.
Some chemical vapours may be absorbed and retained, but often exposure
should be eliminated by personal protection equipment anyway.
The January/February 1995 issue of Chemical Health and Safety had three
articles on contact lenses, including an excellent article on how to prepare
for, and act during, contact lenses emergencies [15]. All three articles
note that changing technologies have resulted in improved lenses that may
now be acceptable in many modern laboratories, however the merits of each
case should be carefully examined before approval. The issue of contact
lenses in laboratories is still being carefully reviewed, as there are also
legal implications for both employers and employees, and laboratory safety
literature should be monitored to obtain the latest perceptions [16,17].

topic!
knowledge

Date: Thu, 15 Jan 2004 22:10:05 +1300
Message-ID: <l5mc00tkmrnmar0lmu6tdo2asoggot7rcm@4ax.com>
Version: 1.17
Subject: 11. Traditional Specialist Chemical Information Sources
11.1 Where can I find spectral libraries/databases?
The most likely place is near to an instrument. These are not usually
in general technical libraries, but are kept near the instruments.
A polite request to the person in charge of the instrument should identify
who to contact for permission to use the library or database. There is
some spectral information in reference texts, such as the Rubber Handbook
and the Merck Index, but most compilations are now so large that they cover
several volumes. There are several compilations that are available
commercially, either in hard copy (HC) or CD-ROM (CD) - which is usually
more expensive because of the included searching software. Chemical
manufacturers, such as Aldrich, may also sell spectral libraries, eg
IR $495(HC) [1], FT-IR $875(HC) or $1578(CD) [2], 60MHz H1 NMR $495(HC) [3],
and 300MHz H1 + 75MHz C13 NMR $1072(HC) [4], as well as offering
compilations from government agencies, eg the NIST/EPA/NIH Mass Spectral
database $1320(CD)[5]. The databases are also sold by several instrument
manufacturers. One commercial supplier of spectral information ( Fiveash
Data Management, Inc. ) may be accessible via the Internet [6].
11.2 Where can I find polymer chemistry information?
The first stop should be the multi-volume Encyclopedia of Polymer Science

and Engineering [7], which should be in most technical libraries. Specific
polymers are covered in much less detail in Kirk Othmer. There are
several journals devoted to polymer science and chemistry, including the
Journal of Polymer Science.
11.3 Where can I find analytical chemistry information?
There is a sci.chem.analytical group where specific questions can be

posted after you have attempted to find the information in the following
sources. For qualitative information, the spot test books by Fiegl [8,9]
and "Semi-micro Vogel"[10], are good starting points. For introductory
quantitative analysis, "Quantitative Inorganic" [11],"Practical Organic
Chemistry"[12] by Vogel are good introductions to non-instrumental
techniques. The multi-volume "Treatise on Analytical Chemistry" by
Kolthoff and Elving [13] comprehensively discusses most techniques, and
several volumes of the ACS Series "Techniques in Chemistry" [14] also cover
analytical procedures. " Instrumental Methods of Analysis" by Willard,
Merritt, Dean and Settle [15], and "Analytical Instrumentation Handbook" by
Ewing [16] provide a good introduction to chemical instrumentation. Most
educational institutions will have equivalent texts if they are not using the
above.
For specific analyses it is often desirable to use standard procedures,

especially if your laboratory is seeking ISO 9001 accreditation, or if the
results are likely to be disputed. Some well known compilations of standard
methods include:-
Laboratory Reagents
- usually specified by manufacturers or chemical societies
BDH 'Analar' Standards for Laboratory Chemicals [17]
ACS Reagent Chemicals [18]
Materials, Industrial Chemicals, and Finished Products.

- usually the monographs in the following volumes also specify assay and
impurity limits, as well as detailing the analytical procedure.
ASTM - Issued annually, cover physical and chemical testing of a wide range
of industrial products. Often require specialised test equipment.
ISO - International standards, usually derived from US(ASTM), UK(BSI) or
FRG(DIN) standards. Similar to above.
Pharmaceuticals
- usually the pharmacopoeia have monographs and methods, but some methods
are also specified in National Formulary or Pharmaceutical Codex volumes,
which may be separate from the pharmacopoeia.
- common pharmacopoeia are USP, BP, and EP - with Martindale [19] often used
to ascertain where and when a specific monograph appeared.
Food
- often the procedures specified in Government legislation.
- The Official Methods of the AOAC [20] covers many routine US methods.
Environmental Pollution
- the procedures are usually specified in the relevant legislation, and
frequently US EPA procedures are used. Several common EPA procedures are
now available on computer disk [21,22].
Petroleum
- usually covered by ASTM, ISO or DIN, but there are some unique IP
( Institute of Petroleum - UK ) procedures that are also used.
- "Chromatography in Petroleum Analysis"[23], summarises popular techniques.
Gases
- instrument manufacturers have fairly detailed procedures for process gases.
- "The Analysis of Gases by Chromatography"[24], provides useful examples.
Water and Wastewater

- the APHA/WWA/WPCF standard methods are most often used [25]
- many tests are also covered by ASTM, ISO, and DIN procedures
- alternative techniques are described in "Water Analysis" [26]
- organics in water are covered by Crompton [27]
- most aspects of water chemistry are detailed in Franks [28]
Sample Preparation
- consumable and instrument manufacturers often provide detailed manuals
and guides free.
- "Methods of Decomposition in Inorganic Analysis" [29] covers a wide range
of preparations for spectroscopy.
- The "Handbook of Analytical Derivatization Reactions" [30] and the
" Handbook of Derivatives for Chromatography" [31] cover many of the
techniques for gas and liquid chromatography.
Obviously there are several journals devoted to various aspects of

analytical chemistry. The April issue of Analytical Chemistry publishes
a review of papers published during the previous two years. The review
alternates between Fundamental and Application Reviews and is a quick means
of catching current trends if you are unable to locate an expert.
11.4 Where can I find environmental chemistry information?
There are several standard texts used by environmental chemistry classes

that provide good general introductions, eg "Environmental Chemistry" [32]
"Fundamentals of Environmental Chemistry [33], and "Environmental Organic
Chemistry" [34]. They should be available in most technical libraries. The
monthly journal "Environmental Science and Technology" covers most aspects
of environment chemistry. "Chemosphere" concentrates on toxins such as PCBs
and Dioxin, and " Science of the Total Environment also covers many aspects.
Government agencies such as the EPA also publish large amounts of
information, and many environmental groups also provide significant amounts
of technical information. There are a range of specialist texts that cover
specific pollutants, eg "Metals and their Compounds in the Environment:
Occurrence, Analysis and Biological Relevance" [35].
The sci.environment Usenet group may well be a better place to request

environmental chemistry information than sci.chem, but please remember
to move discussions to talk.environment.
11.5 Where can I find physical chemistry information?
General introductory information will be available in any technical library

where chemistry is taught, and one of the more popular modern texts is
"Physical Chemistry" by P.W.Atkins [36], and a classical text is
"Textbook of Physical Chemistry" by S.Glasstone [37]. The multi-volume ACS
series "Physical Methods of Chemistry"[38] also covers many physical
chemistry techniques. There are also the Journal of Chemical Physics and the
Journal of Physical Chemistry. Frankly, I would not have a clue where else
to go.
11.6 Where can I find inorganic chemistry information?

where chemistry is taught. One popular text is "Inorganic Chemistry" by
D.F.Shriver, P.W.Atkins, and C.H.Langford [39], which also has the answers
available as a separate book. "Inorganic Vogel"[40], also discusses the theory
of the analyses. There are three major multi-volume inorganic encyclopedias.
Mellor is frequently found in public libraries, and provides a broad cover
of the field, however the more comprehensive is Gmelin [41], which will be
available in most institution libraries. The more recent developments and
mechanisms are covered in the multi-volume "Encyclopedia of Inorganic
Chemistry" [42], which may be difficult to find due to its $2500 price.
"Advanced Inorganic Chemistry" [43] by F.A.Cotton and G.Wilkinson provides a
good base to start. There are several journals that cover aspects of
inorganic chemistry.
11.7 Where can I find organic chemistry information?

where chemistry is taught. One popular modern text is " Organic Chemistry "
by T.W.G.Solomons [44], but my favourite is "Organic Chemistry"[45] by Fieser
and Fieser - a much more practical discussion of organic molecules.
Once you are familiar with organic chemistry mechanisms then "Advanced
Organic Chemistry" by Carey and Sandberg [46] is a good overview.
There are several compilations of organic synthesis techniques to assist

researchers. The multi-volume sets "Organic Reactions" [47], and "Reagents
for Organic Synthesis" [48], are examples of sets that will be available from
institution libraries. There are some good theoretical texts available, eg
"The Logic of Chemical Synthesis" [49]. For specific preparation and
properties of individual compounds, then Heilbron [50] and Beilstein [51],
are the initial resources of choice. There are several journals devoted to
organic chemistry in general, including Journal of Organic Chemistry,
Tetrahedron, etc.. Specific branches of organic chemistry, such as
Carbohydrates, Lipids, or Proteins have their own journals, as do
applications such as pharmaceuticals and pesticides.
11.8 Where can I find industrial chemistry information?

The best single volume remains Shreve's "Chemical Process Industries" [52].
There are three major multi-volume encyclopedias, Kirk Othmer, Ullmann,
and McKetta, that cover many aspects of industrial chemistry and at
least one is usually available in a public library. There are also several
journals that provide good overviews of industrial chemistry, the easiest
to read being C&EN, and Chemtech. Research is usually published
in Industrial and Engineering Chemistry ( which is an excellent source
for historical research ), and specialist chemical engineering journals.
11.9 Where can I find pharmaceutical chemistry information?
Pharmaceutical research often is initially reported in patent literature,

consequently patent searching is a good place to start. The Merck Index is
focused on pharmaceuticals, and also provides excellent leads to the
research literature. There are several pharmaceutical chemistry books, such
as Goodman and Gilman [53], and "Essentials of Medicinal Chemistry" [54],
that provide overviews of the field. The Journal of Pharmaceutical Chemistry
is a good source for research articles. Details of chemicals appearing in
formulated products can be found in the "Handbook of Pharmaceutical
Excipients" [55].
Subject: 12. Nomenclature
12.1 What are CAS Registry Numbers?
When chemicals are first encountered by the Chemical Abstracts Service, they
are assigned a unique number when they are registered. These numbers are not
related to any structure or property of the molecule, they are arbitrarily
assigned. It should be remembered that occasionally a compound may be
accidentally assigned two or more numbers - especially industrial products
that have not been completely characterised. When this is discovered, one of
the numbers is no longer used. The numbers usually take the form of
[xx-yy-z to xxxxxx-yy-z] and square brackets are often used in monographs to
identify the CAS Registry Number [RN]. The easiest way to locate the CAS RN
for commercially-available chemicals is to look in suppliers catalogues
( eg Aldrich) or compilations ( eg Merck or Hawley ), almost all chemical
texts now list the RN, and several ( eg Merck Index and Aldrich ) have a
cross-reference Index. The RN is extremely useful for on-line searching of
Chemical Abstracts and several other popular chemistry-related databases,
but is not particularly useful for the hardcopy version, except to confirm
compound identity.
12.2 What are the correct names of recently-discovered elements?
The Transfermium Working Group was established in 1986 by the International

Union of Pure and Applied Chemistry (IUPAC) and the International Union of
Pure and Applied Physics (IUPAP). The working group published several
reports, and then recommended that elements should not be named after living
persons [1]. This greatly upset the USA - who wanted to name an element after
G. Seaborg. After protracted negotiations, a compromise selection of names
was finally approved by the IUPAC Commission on Nomenclature in Inorganic
Chemistry, the IUPAC Inorganic Division, the IUPAC Bureau, and the selection
was eventually ratified by the IUPAC Council meeting in Geneva during August
1997 [2].
101 Mendelevium Md D. Mendeleev (Russia)

102 Nobelium No Nobel Institute (Sweden)
103 Lawrencium Lr E. Lawrence (USA)
104 Rutherfordium Rf E. Rutherford (NZ)
105 Dubnium Db Dubna = Russian Research Centre
106 Seaborgium Sg G. Seaborg (USA)
107 Bohrium Bh N. Bohr (Denmark)
108 Hassium Hs Latin name for German state of Hesse
109 Meitnerium Mt L. Meitner (Austria)
Note that Hesse is where the German heavy-element laboratory is based.

The Gesellschaft fur Schwerionenforschung (GSI) was responsible for the
first man-made creation of elements 107-110. The compromise will now move
attention to the naming the recently-discovered elements 110-112.
12.3 What is the nomenclature system for CFCs/HCFCs/HFCs?
The CFC naming system was developed by T.Midgley,Jr. and A.L.Henne in 1929,
and further refined by J.D.Park. Originally, organic molecules that contained
Chlorine and Fluorine were all referred to as CFCs. Today, the group is
subdivided into CFCs, HCFCs, and HFCs. The naming system consists of:-
CFC-01234a where 0 = number of double bonds ( omitted if zero )

1 = Carbon atoms - 1 ( omitted if 0 )
2 = Hydrogen atoms + 1
3 = Fluorine atoms
4 = Chlorine atoms replaced by Bromine ("B" prefix added )
a = letter added to identify isomers, the "normal" isomer
in any number has the smallest mass difference on each
carbon, and a, b, or c are added as the masses diverge
from normal.
If the compound is cyclic, then the number is prefixed with "C". There are
several other refrigerants, some of which are hydrocarbons, hydrocarbon
blends, or CFC blends. Full details of the nomenclature system are specified
in ANSI/ASHRAE Standard 34-1992 with additional annual supplements. Chemical
names are frequently used in place of the numbers for common materials
- such as trichloroethylene and chloroform. The specified ANSI/ASHRAE
prefixes were FC ( FluoroCarbon ), or R ( Refrigerant ), but today most are
prefixed by more specific classifications - such as CFC, HCFC, and HFC.
CFC-11 CCl3F trichlorofluoromethane [75-69-4]

CFC-12 CCl2F2 dichlorodifluoromethane [75-71-8]
CFC-113 CCl2F-CClF2 1,1,2-trichlorotrifluoroethane [76-13-1]
HCFC-22 CHClF2 chlorodifluoromethane [75-45-6]
HCFC-123 CHCl2-CF3 2,2-dichloro-1,1,1-trifluoroethane [306-83-2]
HCFC-123a CHClF-CClF2 1,2-dichloro-1,1,2-trifluoroethane [354-23-4]
HFC-23 CHF3 trifluoromethane [75-46-7]
HFC-134 CHF2-CHF2 1,1,2,2-tetrafluoroethane [359-35-3]
HFC-134a CH2F-CF3 1,2,2,2-tetrafluoroethane [811-97-2]
R-20 CHCl3 chloroform [67-66-3]
R-22B1 CHBrF2 bromodifluoromethane [1511-62-2]
R-1120 CHCl=CCl2 trichloroethylene [79-01-6]
R-1150 CH2=CH2 ethylene [74-85-1]
R-C316 C4Cl2F6 1,2-dichlorohexafluorocyclobutane
Another technique for naming CFCs uses the addition of 90 to the CFC number
to produce a "def" number which corresponds to the CHF composition. If
(e + f) < (2d + 2), then additional atoms are required for saturation. This
technique has been described in detail in the Journal of Chemical Education
[3].
ASHRAE +90 Empirical Composition Formula

C H F (+Cl)
CFC-11 101 1 - 1 3 CCl3F
CFC-12 102 1 - 2 2 CCl2F2
HCFC-22 112 1 1 2 1 CHClF2
HCFC-123 213 2 1 3 2 CHCl2-CF3
HFC-134a 224 2 2 4 - CH2F-CF3
Halons are numbered according to a totally different system developed by

the US Army Corps of Engineers, and the prefix term is always "Halon".
Hydrogen is not numbered, and terminal zeros are not expressed.
Halon-0123 where 0 = number of carbon atoms

1 = number of fluorine atoms
2 = number of chlorine atoms
3 = number of bromine atoms
Halon-1211 CBrClF2 bromochlorodifluoromethane [353-59-3]

Halon-1301 CBrF3 bromotrifluoromethane [75-63-8]
Halon-2402 CBrF2-CBrF2 1,2-dibromo-1,1,2,2-tetrafluoroethane [124-73-2]
12.4 How can I get the IUPAC chemical name from traditional names?
It depends. Usually the quickest way is to look the name up in a chemical

supplier's catalog, MSDS, or a standard text like Merck or Hawley. You can
also often find the correct name if you refer to an old chemistry text that
lists both the traditional and IUPAC naming conventions. Some traditional
or common names also refer to mixtures of chemicals, eg aqua regia, piranha
solution.
One reason why traditional names have been replaced is because the same name
could be used for different compounds. An example is the use of caprylic to
describe 1-Octanol and 2-Octanol, and attempts to qualify the name with
"primary" and "secondary" were less than successful. Octyl alcohol has been
used to describe both 1-octanol and 2-ethylhexanol, thus explaining why the
well known dioctyl phthalate (DOP) is actually bis(2-ethylhexyl) phthalate.
The following examples highlight the diversity of names often encountered.
Carbon Alkane Alcohol Aldehyde Acid
1 methane methanol form- formic

carbinol
2 ethane ethyl acet- acetic
methyl carbinol
3 n-propane n-propyl propion- propionic
ethyl carbinol
4 n-butane n-butyl n-butyr- n-butyric
propyl carbinol
5 n-pentane n-amyl n-valer- n-valeric
butyl carbinol
6 n-hexane hexyl capro- caproic
amyl carbinol caproic
7 n-heptane enanthyl enanth- enanthic
enanthic
hexyl carbinol
8a n-octane capryl capryl- caprylic
primary caprylic caprylic
heptyl carbinol
1-octanol
8b capryl
secondary caprylic
methyl hexyl carbinol
2-octanol
9 n-nonane pelargonic pelargonic pelargonic
octyl carbinol
10 n-decane capric capr- capric
nonyl carbinol capric
12 n-dodecane lauryl laur- lauric
lauric lauryl
14 n-tetradecane myristyl myrist- myristic
16 n-hexadecane cetyl palmit- palmitic
cetane
18 n-octadecane stearyl stearic
20 n-eicosane arachidyl arachidic
Primary
- alcohol R1CH2OH
- amine R1NH2
eg normal straight chain normal octane n-octane
normal butanol 1-butanol
iso branched chain iso-butane 2-methylpropane
iso-butanol 2-methyl-1-propanol
iso-octane 2,2,4-trimethylpentane
Secondary
- alcohol R1R2CHOH
- amine R1R2NH
eg sec-butanol 2-butanol
iso-propanol 2-propanol
Tertiary
- alcohol R1R2R3COH
- amine R1R2R3N
eg tert-butanol 2-methyl-2-propanol
- substitution onto the benzene ring

1,2 = ortho ortho-xylene
1,3 = meta meta-xylene
1,4 = para para-xylene
However other names get more tricky, especially historical names, where
several names may be used for the same chemical and, even worse, different
chemicals can be described by the same name. Examples include:-
- calcium carbonate = limestone, chalk, calcite.
- calcium hydroxide = slaked lime, hydrated lime, caustic lime.
- calcium oxide = calx, lime, quicklime, unslaked lime, burnt lime.
- hydrochloric acid = muriatic acid, spirits of salts.
- nitric acid = aqua fortis.
- potassium carbonate = potash, artificial alkali, vegetable alkali.
- potassium hydroxide = caustic potash, lye.
- sodium carbonate - any form = soda, natural alkali, mineral alkali.
- anhydrous = soda ash.
- dodecahydrate = sal soda, washing soda.
- monohydrate = soda crystals.
- sodium chloride = rock salt.
- sodium hydroxide = caustic soda, lye, soda lye.
- sulfuric acid = oil of vitriol
Some old chemical terms are seldom encountered these days, but have very
specific meanings, eg
" flowers " described any product of sublimation, hence "flowers of sulfur".
" specific " in front of any quantity means " divided by mass ", hence
"specific gravity".
" ether " described a volatile liquid, not only compounds with the Cx-O--Cy
structure, and also often known today as "spirit".
" aromatic " described a liquid that had an aroma, not only those derived
from benzene, or which benzene ring structure.
" oil " described a liquid that was not miscible with water, thus it
described different products in different chemical industries :-
- Essential oils = volatile and odoriferous liquid plant extracts.
Essential oils can be obtained by extraction or distillation ( steam ),
often contain terpenes ( based on the isoprene structure ), are usually
smelly ( aromatic ), and are used for perfumes, flavours and aromas, eg
lemon oil and pine oil.
- Triglyceride oils = fats and oils based on the glycerol molecule that
can be obtained from plant and animal material, frequently by melting or
cold pressing. They are a significant, and important, component in our
diet, eg soya oil, lard, fish oils, and anhydrous milk fat.
- Petroleum oil = a mixture of a large number of hydrocarbons that are
usually derived from 0.1 to 3 billion-year-old organic matter. Crude oil
can contain hundreds of hydrocarbons with one to sixty carbon atoms, and
the hydrocarbons are usually grouped and reported by type, eg alkane
( paraffin ), alkene ( olefin ), or arene ( aromatic ).
Almost all old industries had easy-to-remember names for chemicals they
commonly encountered, but today many of those names can cause confusion
if used outside the industry. Some common examples, just from the petroleum
industry alone are:-
- " ether " is a volatile hydrocarbon fraction that does not contain the
Cx-O-Cy structure, eg petroleum ether ( aka petroleum spirit ).
- " naphthene " is a cyclic paraffin, does not contain naphthalene, and is
not a major component of naphtha ( refer Section 27.5 ).
- Benzene, toluene and xylene are often called benzol, toluol, and xylol,
even though they do not contain an -OH group.
- Benzine ( ligroin ) was a saturated hydrocarbon fraction that boiled
between 20C and 135C. Gasoline/petrol fractions are still called benzine
by some older people.
- Diesel fuel is often called "gas oil", which is a historical term for
hydrocarbon distillate fractions. Atmospheric gas oil has a boiling
range between 220C - 450C, and vacuum gas oil boils from 350C to 550C.
12.5 What does "omega-3 fatty acids" mean?
Chemists recognise that they should always number carbon chains from the
end with the functional group, so the location of double bonds in
unsaturated fatty acids are numbered from the carboxylic acid end, and
are usually designated by "delta" in their abbreviated names.
Biochemists are more interested in the actual role that chemicals play,
consequently they will consider the position from the end that is important.
In the case of natural fatty acids the double bonds are usually cis
configured, and it is the distance of the first double bond from the
terminal end of the carbon chain that is important. They use "omega" to
signify that the double bond is cis, and they are counting from the other
end. The great advantage is that chain length can be ignored, and compounds
that are subjected to the same biochemical processes are grouped together.
In 1967, the IUPAC/IUB commission responsible for lipid nomenclature

recommended that for unsaturated fatty acids with cis double bonds, that
the "omega" symbol be replaced with "n-x", where n = the length of the
carbon chain, and x is the distance from the terminal end.
Some examples:-
Common Chemical Chemical Biochemical

Name Name d = delta o = omega
Oleic cis-9-octadecenoic c-C18:1d9 C18:1o9

Elaidic trans-9-octadecenoic t-C18:1d9 -
Ricinoleic D-(+)-12-hydroxy-octadec-cis-9-enoic c-C18:1d9-12OH -
Linoleic cis-9,12-octadecadienoic c-C18:2d9 C18:2o6
alpha Linolenic cis-9,12,15-octadecatrienoic c-C18:3d9 C18:3o3
gamma Linolenic cis-6,9,12-octadecatrienoic c-C18:3d6 C18:3o6
Arachidonic cis-5,8,11,14-eicosatetraenoic c-C20:4d5 C20:4o6
EPA cis-5,8,11,14,17-eicosapentaenoic c-C20:5d5 C20:5o3
Erucic cis-13-docosenoic c-C22:1d13 C22:1o9
DHA cis-4,7,10,13,16,19-docosahexaenoic c-C22:6d4 C22:6o3
EPA and DHA are widely known as the omega-3 fatty acids present in high
concentrations in marine lipids, and are considered beneficial in diet,
although research is not complete [4,5].
12.6 What is Conjugated Linoleic Acid?
Conjugated linoleic acid describes the group of positional and geometric

isomers of linoleic acid ( cis-9,12-octadecadienoic acid ) that have a
conjugated double bond system starting at carbon 9, 10, or 11. They can be
either cis or trans, or various combinations of them. The more abundant
isomers in food are believed to be the cis-9, trans-11, and the trans-10,
cis-12 isomers. It's very difficult to separate the cis-9, trans-11 and
trans-9, cis-11 isomers, however the cis-9, trans-11 form is usually
considered the important and usually dominant isomer.
They are typically produced by bacteria in the rumen of ruminants because

the hydrolysis of fats in the rumen produces more unesterified linoleic
acid than is available to bacteria in other digestive systems. Plants
also contain conjugated linoleic acid, but there is much less of the
cis-9, trans-11 isomer, which is believed to be the biologically active
isomer. Foods that contain CLA are lamb, beef, turkey and dairy fat products,
ranging from 2.5 - 11 mg/g of fat - of which 75% or more is the cis-9,
trans-11 ( or trans-9, cis-11 ) isomer. CLA is of interest because it has
displayed antimutagenic activity in animals and human cell tests [6,7].
12.7 What are "heavy" metals?
There appears to be no standard definition, however the general consensus

appears to be all metals with a density greater than 4 or 5 [8,9,10]. If
you also consider the conventional analytical chemistry definition of "heavy
metals" ( precipitation of sulfides from acidic solutions ), you obtain
quite a diverse mixture of possible candidates. Moving the density limit
from 4 to 5 really only just impacts on Ti, Y and Se. Some other texts use
more complex definitions that may also include accepted "light" metals with
densities less than 4, eg Hawley uses "A metal of atomic weight greater
than sodium (22.9) that forms soaps on reaction with fatty acids. e.g.,
aluminum, lead, cobalt". The term " heavy-element " is commonly used to
describe the transfermium elements, - elements with an atomic number
greater than 100.
12.8 What is the difference between Molarity and Normality?.
A Molar solution contains one gram molecular weight ( aka mole ) of the
reagent in one litre of solution, and is represented by " M ". In modern
usage, "molar" is intended to only mean " divided by amount of substance",
and is not supposed to be used to describe 1M solutions. There are already
exceptions to the rule ( molar conductivity, molar extinction coefficient ),
so I would only worry about correct usage in exams, as in the real world
most chemists use Molar to describe 1M solutions.
A Molal solution is one gram molecular weight of the reagent in 1 kilogram

of solvent, and is usually represented by "m". This concentration unit is
relatively uncommon in the real world, so it's worth checking that the "m"
is not a "M" typo.
A Normal solution contains one gram equivalent weight ( aka equivalent )

of the reagent in one litre of solution, and is represented by " N ".
The equivalent weight of a reagent may vary according to the reaction, but
if considering just acid and base moles and equivalents, then:-
1M H2SO4 + 2M NaOH -> 2H2O + Na2SO4

1N H2SO4 + 1N NaOH -> H20 + 0.5Na2SO4
1N HCl + 1N NaOH -> H2O + NaCl
So you can see that the equivalent weight of an acid is that which contains
1.0078 grams of replaceable hydrogen which, in the case of sulfuric acid,
would be half the mole weight, but, in the case of hydrochloric acid, would
be the mole weight.
The equivalent weight of a base is that which contains one replaceable

hydroxyl group ( ie 17.008g of ionisable hydroxyl ). Thus the equivalent
weight of sodium hydroxide ( NaOH ) and potassium hydroxide ( KOH ) would
be the mole weight, but for calcium hydroxide ( Ca(OH)2 ) it would be half
the mole weight.
The equivalent weight of an oxidising or reducing agent is that weight of

the reagent that reacts with or contains 1.008 grams of available hydrogen
or 8.000 grams of available oxygen. "Available" means being able to be
utilised in oxidation or reduction reactions. The equivalent weight of an
oxidising agent is determined by the change in oxidation number which the
reduced element experiences, eg the reduction of potassium permanganate in
dilute H2SO4 gives;-
K Mn O4 --> Mn S O4
(Oxidation Number) +1 +7 -8 +2 +6 -8
This results in a change of the manganese from +7 to +2, so the equivalent
weight is 1/5 of a mole. However, in neutral solution the change would only
be 3 because the product is MnO2, giving an equivalent weight of 1/3 of a
mole. If reacted in strongly alkaline solution the product is MnO4--, giving
an equivalent weight of one mole.
The equivalent weight of a reducing agent is determined by the change in

oxidation number that the oxidised element undergoes. For the conversion of
ferrous sulfate into ferric sulfate;-
2 (Fe SO4) --> Fe2 (SO4)3
(Oxidation Number) 2x(+2 -2 ) (+3)x2 (-2)x3
The change in oxidation number per atom of iron is 1, so the equivalent
weight of ferrous sulfate is 1 mole.
There are wide range of rules about the determination of the oxidation
number, but if you have been taught to use molarity, I would not bother too
much about normality, as it is mainly used these days by analytical
chemists - because it is convenient for many common titrations. Analysts
assume that 1 ml of 1N reagent will react with 1 ml of 1N reagent. However,
there has been a recent Journal of Chemical Education article that claims
using normality and equivalent weight does help students understand
chemistry, but those concepts are unlikely to become widespread again [11].
12.9 Where can I find the composition of common named reagents?.

Often the best place to start are MSDS sheets or catalogues from commercial
suppliers. Some textbooks include a list of named reagents and their
composition that are mentioned in the text. The very common reagents are
usually also detailed in Hawley or the Merck Index. One chemistry field that
has a lot of named reagents is analytical chemistry, especially in Thin Layer
Chromatography, where many of the spray detection reagents have common names.
Merck produces a handy guide describing the composition and production of
common TLC spray reagents [12].
Some common reagents include:-

- aqua regia = 1 part nitric acid and 3 or 4 parts hydrochloric acid.
- piranha solution = highly dangerous ( explodes on contact with traces of
organics ), warm (65C), 70:30 mixture of 100% sulfuric acid and 30%
hydrogen peroxide. It is used, with comprehensive safety precautions,
in the semiconductor industry, and also in some laboratories to clean
glassware [13,14,15]. Many chemical laboratories prohibit it, and there
are much safer, equally effective, alternatives available - refer
Section 16.7.
Subject: 13. Illicit and Government Controlled Substances
Contributed by : Yogi Shan

## <yshan@nortel.ca>
[ mutilated by Bruce Hamilton, who agrees with what Yogi has written, but
has tried to make the FAQ format consistent, and added his opinion. ]
13.1 What newsgroups/mailing lists discuss illegal drugs?
Current Usenet Newsgroups:

alt.drugs.* ( 18 different groups including a.d.c )
alt.drugs.chemistry
alt.psychoactives
alt.hemp
talk.politics.drugs
alt.rave
alt.consciousness
# rec.drugs.announce
# rec.drugs.cannabis
rec.drugs.chemistry
# rec.drugs.misc
# rec.drugs.psychedelic
# rec.drugs.smart
Mailing lists:
mdma/ecstasy/"E":
To subscribe, send mail to listpimp@underground.net with the message:
SUBSCRIBE mdma <your name>
psychedelics:
Leri-L (Leri-L Metaprogramming Mail Service)
Contact: leri-request@pyramid.com
TTIL is a moderated mailing list whose purpose is the respectful
discussion of Psychedelic Religion.
To subscribe send email to: listproc@phantom.com and put in the body
of the message: subscribe ttil <your email address>
There are several useful FAQs available in alt.drugs - start there with
Yogi's Clandestine Chemistry FAQ. Comprehensive overviews of illicit drug
information available on the Internet are maintained at several sites, eg
http://hyperreal.com/drugs/
13.2 Where can I obtain a list of illegal drugs?
From the "Law" Section of the "alt.drugs Clandestine Chemistry Primer/FAQ"

by Yogi Shan (yshan@nortel.ca), reproduced by permission:
The drug statutes (possession, conspiracy, and sale), including Schedules
I to V of the Controlled Substances Act (listing all banned and federally
regulated drugs and precursors) are in Title 21 [of the United States
Code] Sections 800-900 (21 USC 800-900).
The US Code is available on the Internet:

http://www.pls.com:8001/his/usc.html
http://thorplus.lib.purdue.edu/gpo/
or as gzip compressed files (by Title):

ftp://etext.archive.umich.edu/pub/Politics/Conspiracy/AJTeel/USC/
A current list of proscribed drugs may be obtained by writing to:

Drug Enforcement Administration
Attn: Drug Control Section
1405 "I" Street, N.W.
Washington, D.C. 20537
13.3 What is the chemical structure of common illegal drugs?
See the Merck Index for the chemical structure of your favourite poison.
Heilbron ( aka "Dictionary of Organic Compounds ), a multi-volume set,
is also excellent, and more up to date, though less commonly available.
Serious structure chasers should also check Beilstein, which often provides
far more detail of properties and structure than Merck or Heilbron.
13.4 How do I obtain chemical information on illegal drugs?
Merck, Heilbron and Beilstein all provide information on drugs that have
a significant presence in the market. Lesser-known homebake and analogues
are usually not covered, and a search of Chemical Abstracts may not even
provide information. Because of the various techniques used to "refine"
and "cut" the active ingredients, most illegal drugs are seldom
sufficiently pure to match published data. The drugs are marketed on their
pharmacological and psychological activity, rather than chemical purity
- similar to vitamin units of activity :-). I suggest you start by reading
the various alt.drugs FAQs - they all list hardcopy references, and if they
do not identify an information source, try posting to alt.drugs or rec.drugs.
13.5 Where are the synthesis instructions for illegal drugs?
By asking the question in sci.chem, you already have signalled your level
of knowledge of illicit chemistry discussions on Usenet. You should be in
alt.drugs.* hierarchy and perhaps other groups in section 13.1 :-).
For the short answer, refer to Merck, Heilbron or Beilstein, they will
provide references to the original synthesis papers. Note that large scale
production techniques often use procedures that were developed later, and
street procedures often are significantly different, usually due to
financial, equipment, or chemical feedstock constraints.
For the long answers, see the "alt.drugs Clandestine Chemistry Primer/FAQ"
by Yogi Shan (yshan@nortel.ca), and visit some sites listed in the Network
Resources FAQ available in alt.drugs. For a fairly comprehensive overview,
( but no warranty implied for info available there ), you could start at:
http://hyperreal.com/drugs/
An interesting article on the link between methylenedioxymethamphetamine

( MDMA, ecstasy, XTC, Adam ) illegal synthesis and the sassafras tree is
available [1].
13.6 Should I post detailed recipes for illegal chemicals?
Well, if you do a lot of people will hate you. On the other hand many people
will love you. Of course, most people won't care one way or another.
Or maybe they'll just roll their eyes back, mumble something about
"dissipated/mis-spent youth", and hit the "next" button.
Posting them to sci.chem means you will be attempting to teach grandmother

how to suck eggs, most regulars of sci.chem *know* where to find the
complete instructions, how to perform the synthesis, and have authorised
access to all the equipment and chemicals. The readers of sci.chem are
probably not your target audience, and may be a little annoyed that you had
such a low opinion of their chemistry abilities. If you do not want a
lot of flames, try posting to the groups in section 13.1, they will probably
appreciate your contribution more, but will still flame you if it is wrong.
This is Usenet, do what you want as long as you think you can get away with
it. And don't ever let anyone tell you that you can't. It's a truism on
Usenet that whatever you do, someone's going to be mad at you. For every
anarchistic Free Spirit (TM), there's going to be at least one anal-retentive
busy-body who has nothing better to do that feign outrage at something or
other. Some idiot in Australia even had the nerve to flame me for posting my
Clandestine Chemistry FAQ to sci.chem, and I think drugs are terrible, and
said so. So go figure.
The only caveat to this is that posting mis-information, or information

that you personally do not understand, is likely to result in a lot of
flames. If you attempt to post anonymously to sci.chem, it is likely that
you will encounter far more opposition than if you use your email address.
As with all of Usenet, posters who sign their names to posts will be held
accountable for the content, so posting obviously incorrect or incomplete
syntheses to a group where knowledgeable chemists hang out is more likely to
harm your credibility. Your posts are unlikely to gain you further knowledge
of the synthesis, because if you post incorrect details, readers will be
pointed to the more accurate Clandestine Chemistry FAQ, and also directed to
the groups in section 13.1 to find the latest details.
In the late 1980s, and early 1990s a poster began to post all the detailed
synthesis methods from Pihkal to sci.chem. "Pihkal" is Alexander and Ann
Shulgin's standard text " Phenethylamines I Have Known and Loved [2a]", which
has recently been supplemented with "Tihkal" ( Tryptamines I have Known and
Loved ) [2b].
From vague memory, the poster was just listing the recipes, and not entering
into discussions or responding to questions or comments. There was the usual
outrage, but I believe he had to stop because of copyright violation of the
book he was posting - he could not demonstrate to his access provider that
he had approval from the copyright holder :-). Shulgin has now made Part Two
of PiKAL freely available, and copies are littered around the Internet, so
check out the various alt.drugs FAQs for their location.
13.7 What newsgroups/mailing lists discuss explosives?
Rec.pyrotechnics and alt.engr.explosives are two newsgroups that discuss

explosives, much to the consternation of some subscribers to the former.
The rec.pyrotechnics FAQ is excellent, and is posted regularly to
rec.pyrotechnics, news.answers, and rec.answers.
There's an "Anarchist Cookbook FAQ" posted semi-regularly to rec.pyrotechnics

and alt.engr.explosives that tells you why the AC is lousy. See also:
http://www.cwi.nl/cwi/people/Jack.Jansen/spunk/cookbook.html
This review goes a little overboard: the mercury fulminate and picric
acid recipes the he refers to are fine by my estimation.
See also [but no warranty implied for info available on]:

http://paradox1.denver.colorado.edu
http://www.wiretap.spies.com
13.8 What is the chemical structure of common explosives?
Exothermic oxidation-reduction reactions are the source of energy, and they

can be produced from mixtures of discrete fuels and oxidisers, or from
molecular decomposition - such as from nitroglycerine. Propellants and
explosives produce large volumes of gases, whereas pyrotechnics do not.
Gas Reaction Ignition
Volume Heat Temperature
(cm3/g) (MJ/KG) (C)
Photoflash (30:40:30 Ba(NO3)2:Al:KClO4) 15 8.989 700
TNT 710 4.560 310
Most explosives are organic compounds or mixtures that contain carbon,

hydrogen, oxygen and nitrogen. Metallic fuels ( eg aluminium ) may be
added to increase the heat of reaction. Industrial dynamites traditionally
used nitroglycerine, nitrocellulose, and inorganic salts as sources of
oxygen, but these have been replaced by formulations that use ammonium
nitrate as the primary oxygen source. Note that the specific energy is
usually lower than the combustion of common fuels in air because the fuels
obtain their oxygen from air.
Many explosive can either burn or detonate, usually depending on the

type of initiation, confinement, and physical properties of the fuel.
When initiated, burning first occurs at an increasing rate during the first
few microseconds as it creates a high velocity, high pressure shock wave
that exothermically decomposes the explosive as it passes. The wave is
sustained by the transfer of energy from the reacted explosive to the
unreacted explosive via shock compression. The reaction rate depends on
the rate of propagation of the shock wave, rather than the rate of heat
transfer - as occurs during burning.
Explosives are usually classified into:

Low Explosives or Propellants
eg colloidal cellulose nitrate ( smokeless powder ), black powders,
gun and rocket propellants.
- they are usually mixtures of chemical compounds that produce large
volumes of high temperatures gases at controllable rates, and do not
require atmospheric oxygen. Ammonium perchlorate and ammonium nitrate
are commonly used as oxidisers.
Initiating or Primary Explosives ( detonators )

eg lead azide, mercury fulminate, diazodinitrophenol (DDNP).
- they are used to initiate the next component of an explosive chain, and
are usually dense, organometallic compounds.
- these are sensitive materials and fairly dangerous to handle as they
can be ignited by heat, shock and electrostatic energy.
Lead Mercury DDNP
Azide Fulminate
Density (g/cm3) 4.0 4.2 1.60
Heat of Combustion (MJ/KG) 2.64 3.93 13.58
Heat of Detonation (MJ/KG) 1.54 1.79 3.43
Gas Volume (cm3/g at STP) 308 316 876
Detonation Velocity (m/s) 5100 5400 6900
High or Secondary Explosives

There is a distinction between secondary and high, however many of the
common explosives are considered "secondary high explosives".
eg cyclotrimethylenetrinitramine (RDX), 2,4,6-trinitrotoluene (TNT),
cyclotetramethylenetetranitramine (HMX), ammonium picrate (AP).
"Secondary explosives" include trinitrophenylmethylnitramine (Tetryl),
nitrocellulose (NC) nitroglycerine (NG), pentaerythritol tetranitrate
(PETN), and nitromethane. High and secondary explosives require explosive
shock to initiate their detonation, otherwise they would only burn if
unconfined or unshocked.
NG TNT AP RDX HMX Tetryl
Density (g/cm3) 1.59 1.65 1.72 1.85 1.90 1.70
Heat of Combustion (MJ/KG) 6.80 15.02 12.09 9.46 9.88 12.24
Heat of Detonation (MJ/KG) 6.29 4.23 4.31 4.54 5.67 4.63
Gas Volume (cm3/g) 715 710 680 780 755 760
Detonation Velocity (m/s) 7600 6940 7050 8570 9160 7920
Detonation Pressure (GPa) - 18.9 - 33.8 39.3 26.2
RDX and HMX are substantially desensitized when mixed with TNT or coating
with polymer/elastomer binders. Most RDX in the USA is converted into
"Composition B" (59.5:39.5:1 RDX:TNT:Wax)
"A5" (98.5:1.5 RDX:Stearic Acid)
"C4" (91:5.3:2.1:1.6 RDX:dioctyl sebacate:polyisobutylene:oil).
Amatol AN
B 80/20 C4 AN ANFO Slurry
Density (g/cm3) 1.72 - 1.64 1.72 0.93 1.40
Heat of Combustion (MJ/KG) 11.67 4.19 - 2.62 - -
Heat of Detonation (MJ/KG) 5.28 4.10 6.61 2.63 3.76 3.05
Gas Volume (cm3/g) - 860 - 980 - -
Detonation Velocity (m/s) 7900 5200 8340 2700 4560 6050
Detonation Pressure (GPa) 29.5 - 25.7 1.1 6.0 10.4
Note that explosives usually have less potential energy than gasoline, but
it is the high rate of energy release that produces the blast pressure.
TNT has a detonation velocity of 6,940 m/s compared to 1,680 m/s for the
detonation of pentane in air, and the 0.34 m/s stoichiometric flame speed
of gasoline combustion in air.
Other than ammonium nitrate/fuel oil (ANFO), most common explosives are
trinitrated organic compounds. Nitroglycerine (glyceryl nitrate),
trinitrotoluene (TNT), picric acid, C4 (plasticized RDX/Cyclonite),
and tetryl (2,4,6-trinitrophenylmethylnitramine), fall into this category.
Refer to Merck or Kirk Othmer for chemical structures of common explosives.
A range of Semtex plastic explosives were produced by the Semtin Glassworks

in Czechoslovakia ( now known as VCHZ Synthesia ). Semtex-H is commonly used
by terrorists and, although examples are of variable composition, it
typically contains approximately 8% oil, 9% rubber, and approximately equal
quantities of RDX and PETN, but with known composition ranges of >21.5% RDX
and <64.5% of PETN. [3,4].
ANFO was proposed in 1867, but it was the development of anti-caking agents
in the 1950s that made ANFO suitable for rock blasting. Typical commercial
ANFO blasting agents consist of 94% ammonium nitrate prills (coated with an
anti-caking agent) and 6% fuel oil. They are reclassified as blasting
explosives if the formulation is sensitised by the addition of high
explosive. ANFO explosives are usually initiated by a high-explosive booster
such as formulation B. Maximum sensitivity to initiation occurs around 2-4%
fuel oil, with the presence of water decreasing sensitivity. The recent bomb
in Oklahoma City (estimated 1800kg ANFO)[5], demonstrated the destructive
capacity of ANFO explosives.
There were solubility problems using ANFO in wet drill holes, so aqueous-
based slurries were developed. These are usually thickened suspensions
dispersed in a saturated salt solution that has been made water resistant
by the addition of hydrophilic colloids that inhibit water migration.
Ammonium nitrate-based explosives account for 97% of the US industrial
explosives.
The infamous nitrogen tri-iodide ( touch powder ) produced by the reaction

of ammonia with iodine, is not actually NI3, but a nitrogen iodide/ammonia
complex with the structure NI3(NH3)n where n = 1, 3, or 5 - depending on
conditions. NI3 has only recently been isolated, and is stable at -196C,
decomposes slowly at -78C, and decomposes spontaneously at 0C [6]. Refer to
an older inorganic chemistry text, such as "The Chemical Elements and their
Compounds"[7], for further details and references.
Recently, there has been great interest in the development of more energetic
materials, and several new compounds are expected to replace existing
materials - once manufacturing costs are reduced. Examples include;- ADN
(Ammonium Dinitramide - NH4N(NO2)2, used as a propellant by the Soviet Union),
CL-20 (2,4,6,8,10,12-hexanitro-2,4,6,8,10,12-hexazaisowurtzitane, aka HNIW,
the most powerful single-component explosive known - which, when combined
with a polymer binder is also known as LX19), and TNAZ
(1,3,3-trinitroazetidine) [8,9,10].
13.9 How do I obtain chemical information on common explosives?
There is an excellent, well-referenced "Explosives and Propellants" monograph

in Kirk Othmer [11] and there are also the popular books "Explosives" by Meyer
[12], and "Chemistry of Powder and Explosives" by Davis [13]. Many of the
relevant properties of fuels and explosives are found in an easily-accessible
Bureau of Mines report "Investigations of Fire and Explosion Accidents in the
Chemical, Mining, and Fuel-Related Industries - A Manual" by J.M.Kuchta [14].
There is also the "Propellants, Explosives and Pyrotechnics" journal. Merck
lists most common, and many uncommon explosives, giving their structure,
selected properties, and pointers to synthesis and more detailed information.
Shreve and Kirk Othmer also discuss explosives manufacture.
Tadeusz Urbanski wrote a massive four-volume reference set on explosives

"The Chemistry and Technology of Explosives" [15] that should be available
in any university science library (it's something like US$700 otherwise).
The "Encyclopedia of Explosives and Related Items", aka "PATR 2700"

(Picatinny Arsenal Technical Report) [16], is a U.S. Army (Picatinny
Arsenal, Dover, NJ), all-encompassing compilation (10 volumes) of
explosives properties and chemistry. Like Urbanski, it's also quite
expensive.
13.10 What newsgroups/mailing lists discuss pyrotechnics?
rec.pyrotechnics is the "official" newsgroup for fireworks/pyrotechnics

discussions, though many have fled to the mailing lists due to the large
numbers of juvenile "mad bomber" type posts that abound.
Mark A. Buda < buda@star.enet.dec.com >
The original rec.pyro exile fireworks list.
"Mad Bomber" posts forbidden.
The Pyro Mailing List is a "Real" pyrotechnic discussion group moderated by
a pyrotechnician. No mad bombers.
To subscribe apply to pml@vnet.net and follow the instructions.
One must supply the info and there are reasonable guidelines to follow.
Murr Rhame <murr@jazzmin.vnet.net>
Show-Fire entertainment pyrotechnics mailing list.
"Mad Bomber" posts forbidden.
To subscribe send the following one line message to listserv@vnet.net:
subscribe show-fire name@your.address
Ken Harthun <omckenh@pipeline.com>
PyroTechniques, The Newsletter for Pyrotechnic Enthusiasts. It is FREE
for the asking. Just email me with a request to be added to the list.
See also:
http://mercury.aichem.arizona.edu/~tip/pyro.html
http://nickel.ucs.indiana.edu/~flinn/pyro/pyro.html
http://fireworks.com/
Subject: 14. Academic Course Information
14.1 Where do I find information on US courses?
The advent of the WWW has meant that many educational institutions now have
their courses listed. A WWW search should reveal the address of most
institutions, and several of the more popular chemical courses are linked to
some of the general chemistry education sites listed in section 7.2.
Note that most US educational institutions will have a *.edu (education)
Internet address. Also check out the various Chemical Society homepages.
14.2 Where do I find information on other nations' courses?
Once again, try using the WWW, as many educational institutions worldwide
are placing course information on their home pages. It is worth remembering
that not all countries use *.edu (education), as the educational institution
address, some countries use *.ac (academic) eg vuw.ac.nz is Victoria
University in Wellington, New Zealand.

topic!
knowledge

Date: Thu, 15 Jan 2004 22:10:47 +1300
Message-ID: <j7mc00hfvco369p5dgq2h7rbsrktu6c5sk@4ax.com>
Version: 1.17
Subject: 15. Chemical Demonstrations
15.1 Are there any good compilations of demonstrations?
Yes. Good places to start are the four volume "Chemical Demonstrations"
by B.Z.Shakhashiri [1], the two volume "Chemical Demonstrations - A
Sourcebook for teachers" by Summerlin and Ealy [2], or "Chemical Magic"
by Ford and Grundmeier [2a]. The Journal of Chemical Education is also an
excellent on-going source of novel demonstrations and developments of
traditional demonstrations.
15.2 What are good outdoor demonstrations for under 12s?

15.3 What are good outdoor demonstrations for over 12s?
15.4 What are good indoor demonstrations for under 12s?
15.5 What are good indoor demonstrations for over 12s?
While waiting for a promised contribution, here is my only contribution,

and some from my sci.chem archives. Unfortunately, enthusiastic editing
by others allows some of the culprits to go uncredited :-).
The ability of water-miscible solvents to mask the hydrophobic nature of

Goretex can be demonstrated. Goretex is just a porous PTFE, the same
material as PTFE filters - such as Millipore HF. You can easily filter
liquid water through porous PTFE, provided the filter is previously wetted
with a water-miscible solvent ( usually ethanol ). If a filter is set up on
a vacuum flask, ensure the filter is completely wetted with ethanol, turn on
the vacuum, and immediately add water - it rapidly filters through. Once it
has stopped, it only takes about 15 seconds for the air to dry the filter,
then ask a student to filter more water from the same flask. No chance.
Pour off the water, surreptitiously add a few mls of ethanol, immediately
followed by the same water - and watch it filter through again :-).
This is the nearest equivalent our laboratory has to the workshop practice
of sending an apprentice out to purchase a spark plug for a diesel engine.
It does relate slightly to the real world - indicating why "breathing"
fabrics like Goretex should not be used with solvents.
From: brom@yoyo.cc.monash.edu.au (David Bromage) Date: Tue, 14 Sep 1993

Subj: Re: Need: A safe chemical display
The so-called "Blue Bottle Reaction" might be useful.
Half fill a 1 litre flask with water and add 10g of NaOH, then add 10g
of glucose and up to 1ml of 1% methylene blue. Stopper the flask and
swirl gently to dissolve the contents. On standing for a few minutes the
solution should turn colourless. When the flask is shaken the solution
will turn blue then decolorise on standing.
Methylene blue exists in solution as a reduced colourless form and an
oxidised blur form. The initially blue dye is reduced by the alkaline
form of glucose and re-oxidised by dissolved oxygen. When the solution
is shaken, atmospheric oxygen enters into solution at a more rapid rate
than when left standing. The dye acts here as a catalyst whose colour
indicates the redox state.
[ This demonstration, and different coloured versions of it, have recently

been discussed in the J.Chem.Ed.[3]. ]
How about a chemical garden?
Make up (or dilute a commercial preparation) of sodium silicate to

1.1g/ml. Place this solution in a large glass container then add 'lumps'
or large crystals of salts to be grown. Lumps should not be more than
0.5cm in diameter. As a salt dissolves it forms an insoluble silicate
which forms a membrane around the lump of salt. The membrane is
permeable to water which enters and dissolves more salt. The resulting
pressure bursts the membrane releasing more salt solution to form more
membrane. As the salt solution is less dense than the silicate solution,
the membrane grows as a convoluted vertical tube.
Salt Colour Growth time

Ferric chloride brown 1 hour
Ferrous sulphate grey-green 3 hours
Cobalt chloride purple 5 hours
Chromium chloride grey-green 6 hours
Nickel sulphate yellow-green ~24 hours
Cupric sulphate blue ~24 hours
Potassium aluminium sulphate white ~1 day
To produce a "garden" which is not completely overgrown with the faster

species it is necessary to take growth rates into account. Distilled
water should be used as Ca and Fe in tap water can cause cloudiness.
If you really want oscillating reactions, I know of two.
A. Iodate reaction.
Make up 3 solutions
1) Dilute 200ml of 100 vol hydrogen peroxide to 500ml
2) dissolve 21g of potassium iodate (KIO3) and 1.5ml of conc sulphuric
acid in 500ml of water.
3) Dissolve 7.8g of malonic acid and 1.4g of manganese sulphate in 400ml
of water and add 1.5g of starch in 100ml of water.
Add equal volumes (50-100ml) of each solution to a flask in any order.

Colourless-blue oscillations should start within 2 minutes. If not, try
10-20% variations in relative volumes. (try increasing 2 first).
Oscillations should last up to 10 minutes but I my experience have lasted
up to 3 hours.
B. The Belusov reaction

Prepare 5 solutions.
1) 58g of malonic acid on 500ml of water
2) 6M sulphuric acid
3) 21g of potassium bromate (KBrO3) in 500ml of water
4) Dilute 5ml of solution 2 to 500ml then add 1.75g of cerous sulphate.
5) 1.6g of 1,10-phenanthroline and 0.7g of ferrous sulphate in 100ml of
water (or commercial ferroin solution to 0.025M)
Mix together 50ml of 1 to 4 and 5ml of solution 5. Blue-pink oscillations

should start within a few minutes.
For either oscillating reaction the choice exists of complete mixing with
uniform oscillations or waves of colour (eg in a measuring cylinder).
Some interchange of reagents is possible. The Bray reaction omits
malonic acid from the Iodate reaction. Malonic acid can be replaced by
citric or succinic acids.
[ There have been several good discussions [4,5], and recipe compilations
[6], for many popular oscillating chemical reactions.]
A particularly dramatic 'trick' is not to burn paper. Make up a solution

containing 57% v/v ethanol and 43% v/v water with 5% w/w sodium
chloride. Soak a filter circle in the solution and hold it near a flame
(with tongs) just long enough to ignite. After the flames die down the
filter circle will still be intact. The ethanol burns but just enough
water remains in the paper to prevent ignition. NaCl is added to provide
a more convincing flame. To add drama, 'burn' a banknote - but ensure
that all of the note, especially the corners, is soaked.
From: lmartin@uclink.berkeley.edu (Lonnie C Martin) Date: 17 Feb 1993

Subj: Re: Growing a Silver Tree in Beaker?
In article <...> xslkkk@oryx.com (kenneth k konvicka) writes:

>Am trying to do a demo for elementary school kids. How do you grow a tree
>of silver using copper wire(?) submerged in a solution of AgNO3? Saw one
>in high school physics class about a thousand years ago at good ol' Reagan
>HS, Austin, Tx. Was really beautiful. The silver formed nice large
>plates. Any demonstration books you could steer me toward?
What you have described is about all there is to it. I do this

demonstration for the chemistry classes here at Berkeley about twice a
year, or so. Just make a "tree" out of copper wire (you might clean it
with sandpaper or steel wool) so that it will fit into a beaker of your
choice (we use 4 litre here), and pour in the silver nitrate solution.
I think we use 0.1 molar, but as long as the concentration is fairly close
to that, it will work just fine.
It is not necessary to make the tree very "bushy". The silver will fill it
out nicely with fuzzy thick hanging globs of crystals. The solution will
change from colourless to blue, as copper nitrate is formed. A very nice
experiment. You can expect this to take on the order of an hour to get
fully developed.
From: flatter@rose-hulman.edu (Neil Flatter) Date: Tue, 14 Sep 1993

Subj: Re: Need: A safe chemical display
We use cobalt (II) chloride in a saturated sodium chloride solution to

demonstrate cooling coils. It changes from red/pink to a blue/purple when
heated and reverses as it is cooled. We cycle it through a condenser from
a distillation to illustrate that portion of a simple set-up.
Subject: Stupid lab tricks -Compiled- VERY LONG Date: 7 Jul 92
From: Nazman <nasadk@rpi.edu>
Ever try taking an empty ditto fluid can, put some water in it, heat it
until steam is coming out, cap it back up and let it cool off?. You would
be surprised what a little air pressure can do. That one amazed me when I
was young.
I was amazed again when I saw a brief description on TV of how science

teachers are trying to make science fun again. Four teachers on stage, set
up a few ring stands and a few bunsen burners, and placed a 55 gallon oil
drum on top. Boiled the water, capped it. Put a hell of a dent in the drum
when it collapsed.
A favourite of mine requires a little preparation, but is great fun. Try

tearing an aluminum can in half. Kinda difficult. Now, if you take an empty
can, gently score around the circumference on the inside, (the inside is
coated to prevent a reaction between the soda and the can) and fill the can
with a solution of warm water and Copper(II)Chloride (CuCl2) so that the
solution is just above the score mark. Let this sit for a few minutes.
You are done with the solution when the outside of the can appears brownish
(blackish) where the score mark is. Gently pour out the solution (keep it)
and let the can sit. When ready, hold the top of the can in one hand and
the bottom in the other, and break like you are breaking a stick in half.
Two bits of advice :

BE CAREFUL!. You will end up with the sharp edge of the can, which can cut
severely!
Try this ahead of time just to make sure you get it right. Wait too long,
and when you pick up the can, it will split due to the weight of the
solution. Don't wait long enough and it won't work. My guess is about
5 minutes
P.S. This is more of a demonstration of structure of an aluminum can, but

if you want to demonstrate the "strength" before you rip it in half, place
the can on the floor, so it is sitting like it normally would, and balance
on one foot off the top of the can. It helps to have something nearby to
hold on to, and the can cannot have any dents. You would be surprised how
strong an empty can is. I weigh about 190 lbs, and have stood on an empty
soda can for 30 seconds, get off the can, and not have it collapse. This
takes some practice, so give it a try.
From: A_ROSATI@GUVAX.GEORGETOWN.EDU <Anthony V. Rosati>
You can followup the bromophenol blue trick by brewing a cup of tea
and, while they watch, add some lemon juice. The color will lighten.
There is an indicator in tea that changes with the acidity of
ascorbic acid.
Another neat trick is to demonstrate the dehydration capacity of

concentrated sulfuric acid. Take a 500 mL beaker about one third full
of white table-sugar. Then add about a half-inch to one inches worth
of concentrated sulfuric acid. (This demonstration _MUST_ be conducted
in a hood) Let it sit for about five minutes. Within that time, the
sulfuric acid will seep in, start turning the color of the sugar
brown, and then black, followed by an intense, hot dehydration. The
sugar will start to form a jet black, smelly, sticky column that rises
out of the beaker. It is really impressive.....
You might want to also look up "oscillating reactions" in your

chemistry library. Many of these are simple to set up and generate
neat color cycles that would impress the kids!
From: mfrancis@ucsd.edu < Lyn Francisco >
1. Take a balloon, blow it up, tie it, then stick it in a vat of

liquid nitrogen. Wait until it shrinks (around 3 s or so), take it
out, and then watch it inflate in your hands. This will very nicely
illustrate the relation between temperature and pressure.
2. We did this during a demonstration to let the world know about

ACS on campus. Take a large container (like one of those 10-gallon
water containers, cut in half or something), fill it up with water,
then put in one can of the original Coke and one can of diet Coke.
Make sure that both cans are unopened. Now, drop a few pieces of
dry ice in the container. The original Coke should drop to the
bottom, and the diet Coke stay up toward the top. It was cool, and
attracted all the frat-types and non-science people to our table.
From: dfield@nike.calpoly.edu < Dan Field >
If you really want to fire them up, my favorite has always been the
hydrogen balloons. Just fill up several balloons, one color with air or
He, another with H2, and another with 2H2 + O2. You can fill them ahead of
time, or better yet if demonstration time allows, use the products of one
of your demonstration reactions to fill the balloons. Light a candle on
a L O N G stick, dim the lights, and pop!, boom!, B O O O M !!.
You'll have instantly created little monsters, young pyromaniacs virtually
guaranteed to associate some excitement with chemistry.
[ Warning - the sound level of such explosions has recently been found to
exceed health and safety guidelines, and people should read the article
before demonstrating this experiment to students or children [7]. ]
From: edremy@d31ha0.Stanford.edu < Eric R.>
There are lots of things you can do with liquid N2. Try freezing a
banana and using it as a hammer. (Follow by using an unfrozen banana:
kids love it!) Simply adding some to a test tube and (lightly!) corking
it is fun, provided you're careful with the cork. Shattering a
superball is also good.
However, my personal favorite for spectacular demos is the HCl fountain.

Ascii graphics follow
---------
\ / Top flask is filled with HCl gas
\ S S=rubber stopper w/ hole for needle
\ /
-|-
/ | \ Run tube from top into bottom
/--|--\ Bottom flask filled with water and
/ | \ acid/base indicator.
-----------
MAKE SURE THAT THESE FLASKS ARE VACUUM SAFE!!!
To start this whole extravaganza, inject 20-30 cc of water into the top
flask. The HCl gas goes into solution, creating a partial vacuum, sucking
the water up from the bottom. As the water spurts out of the tube, it
collects more HCl (And changes color as it becomes acid) and accelerates
the reaction... Quite impressive.
We used to do this for our chemistry magic show every year. The only
problem is that the failure mode is somewhat dangerous: One year the
top flask had a flaw and imploded, sending glass and HCl everywhere.
Best to do behind a shield
From: Bill
I believe that the same thing can be done with ammonia.

The same precautions apply.
From: ?
Bubble H2 through a soap solution and you get bubbles that float up.
Have them float through a bunsen burner flame suspended over the table and
they explode. VERY NEAT effect.
From: joec@morgan.com <Joe>
USUAL WARNINGS: many chemicals are poisonous and some reactions

may be difficult to control. Use your head.
Best done indoors

-----------------
Dissolve silver nitrate in warm water. Get some copper wire
and clean it with steel wool. Insert copper wire (preferably coiled
at one end) in the solution and it will immediately dull. Some time later,
silver crystals will be CLEARLY visibly growing on the copper.
The best effect is to let it sit overnight. The resulting
effect is downright beautiful
Dissolve Cobalt Chloride in warm water. Put some Aluminum foil

in it and watch it tarnish. Clean, polished Aluminum works
best but household aluminum foil also works (just slower).
The Aluminum slowly disappears and Cobalt metal shows up at the bottom.
This is a slow one but it does work.
Light an alcohol lamp, i.e. denatured alcohol and bring a magnet near
the flame but not above it- to the side. Watch the flame get pulled in
the direction of the magnet.
Sprinkle iron filings over the same alcohol lamp and watch sparks fly!
Ignite some Magnesium ribbon and drop into an atmosphere of CO2. It

will continue to burn with lots of noise and sparks. Carbon dust will
rain down as a byproduct.
Mix water and household (3 in 1) oil. Note the phase boundary.

Add soap and shake. Watch the phase boundary disappear.
Heat up a piece of blackboard chalk with a propane torch. Chalk

is CaCO3 - heating it up will drive off CO2, leaving CaO (also known
as lime). Heating up lime will cause the it to emit a whitish light,
which is where the phrase 'limelight' comes from.
[ Note - not all blackboard chalk is CaCO3 - test carefully first ]
Do these outdoors:
------------------
Get some KMnO4 and pour into a small pile. Depress the center of
the pile slightly and add a drop or two of Glycerine and stand back.
Something between 1-5 minutes later, it will burst into flame.
When it dies down, drop some more glycerine on it to have it flare up
again. Be careful disposing of the KMnO4 left over - its a powerful
oxidizer.
We also do THERMITE periodically (Aluminum powder and rust). Details for

those who ask - it burns *BRIGHT* and *HOT*.
Drop some dry ice chunks into a 2 liter PLASTIC soda bottle 1/2 full with
warm water which is then quickly sealed. Get at least 50' ft back rather
quickly. The pressure will build up and detonate with a LOUD *BOOM* after
a brief and unpredictable time. The bottle will break into many hundreds
of parts (don't use GLASS!) and you will get a mist cloud some 20-30'
across. Note: It is quite LOUD and may scare a younger audience.
Make Hydrogen soap bubbles and set them off. Get an erlenmeyer flask and
fit a cork into the top and route a glass tube through the tube and
have it bend down and into a jay of soapy water. Remove the cork and
drop in Zinc metal and pour in somewhat dilute HCl. Put the
cork back in and let the H2 bubble into the soapy water. This will
make H2 soap bubbles. Let them break free and ignite them with a light
match on long pole.
Thermite reaction
First of all....this is a fairly vigorous reaction so take the usual

precautions:
1-Do it outside, preferably on sand or dirt. Since it burns at 4000 degrees
fahrenheit, it will melt most anything. By the way, a nuclear explosion
burns at 8000 and the surface of our Sun burns at 10000. It will readily
melt rock salt, beach sand, etc. You get the idea.
2-It can spray sparks around. Keep it away from combustible materials. The
burning sparks are either molten Aluminum or molten Iron.
3-It is VERY bright so you shouldn't stare at it.
4-It puts out lots of smoke.
Here is how I do it.
Ingredients:
1-Aluminum powder
2-Iron Rust (Red-Fe2O3).
Grind carefully and separately into a powder-like consistency.

Mix in roughly equal proportions, by volume with an excess of rust.
Mix thoroughly to get an even color.
Pour the powder mixture on the ground in a pile.
Get magnesium ribbon and lay it on top of the pile, and press partially
into the pile. Do not smother the Mg ribbon. Ignite the ribbon with a
propane torch and get back quickly.
When done, be careful...it will leave molten, glowing red iron as a

byproduct.
You can make rust by mixing household clorox with steel wool pads and let
sit overnight and then filtering out the rust.
Have fun and be careful.
Usual disclaimers apply
From: gallivan@after.math.uiuc.edu < Justin Gallivan >
This works nicely with soap bubbles in a dish. If you have the H2 and O2
tanks available, Try a few with the H2 only which makes a nice quiet
flame and add the O2 later for a little shock value. You may want to
try this first for safety's sake but it always went off without a hitch in
my general chemistry days.
From: Rob
I hope I'm not too late. An extremely simple trick is done with a chunk
of styrofoam (larger the better) and some acetone, which is an excellent
theta-solvent for styrofoam.
Simply spray the acetone out of a bottle onto the styrofoam, and the
styrofoam rapidly decomposes, losing its structure, and appears to
actually be melting. It is quite a "dramatic" demonstration, and can be
offset against how nicely styrofoam coffee cups hold water/coffee, but not
acetone.
From: ?
I thought this one was neat...
Take a bottle (should be reasonable size, like a ketchup bottle)

fill it to within 2" of the top, color light blue (not opaque!)
with methylene blue. Drop in a NaOH pellet and a few drops of
Karo clear syrup. Other reducing sugars might work; I just know
it works with this syrup. (Or did; the last time I tried it was
almost 20 years ago, and they may have changed the formula since
then.)
Over a period of a few minutes, the blue color will fade. Shake
the bottle, and suddenly it's blue again. Leave it, and it will
slowly fade. It'll last for a couple of days, until random
microbes do in the sugar I suppose.
From: ?
A "Bottle of fire" for lighting bunsen burners and such:
Get a dark, heat-resistant glass bottle, and put just enough pentane
in it to wet the sides. (i.e., rinse it with pentane and dump out
the excess.) Light the top of the bottle. The flame will burn down
into the neck of the bottle a little, but be almost invisible to the
audience. Pick up the bottle, turn it over, and flames will pour
out. Set it down, and the flames seem to go out.
When Dr. Toffel did this, someone said "There's something in the
bottle!" He said "Nope," poured some water from the faucet into the
bottle, dumped fire and water into the sink, then showed that the
bottle would still "pour fire". (This probably takes some practice.)
From: mvp@hsv3.lsil.com < Mike Van Pelt >
Portable bunsen burner:

Bubble air through a test tube of pentane, and run this to
your bunsen burner. You can use a large balloon as your air source,
or have a vict... I mean, volunteer, blow through the tube.
From: Howard Clase.
One experiment that I like was you make a solution of lead nitrate,
which is clear, and a solution of some iodide salt (potassium iodide),
which is also clear. When you mix the two of them together you form
a yellow solid - lead iodide.
This is only half of it! If you don't use too much of the chemicals
to produce your "instant orange juice" - but DON'T let anyone drink it.
You will find that the lead iodide will dissolve if you heat the solution.
On
Cooling it re-precipitates as beautiful golden spangles.
From: mgray1@metz.une.oz.au < Matthew Gray >
Another exciting and easy impress all trick is to get two solutions, one
of Ag(I) and another of Cu(I), usually both hexamine complexes. When
these two are mixed, a redox reaction takes place, producing a silver
mirror effect. Other reducing metals can be used, such as iron, but I
haven't tried these myself.
From: ?
Grind some potassium permanganate to a fine powder (to speed up the

reaction). Put it in a small heap (1 teaspoon) on a tile, make a dent in
the top and pour one drop of glycerine in the hole. After about 10-15
seconds the heap will catch fire.
From: torin.walker@rose.com
Here are some that are rather interesting. All of these tests have been
performed in my workshop and are all safe (with the exception of the
handling of HCl and the irritating effect of experiment #2). Experiment #3
is by far the most fascinating.
1 Copper Sulfate couple grams in a test tube.

Sodium Bicarbonate - same as above.
These two liquids are transparent but when mixed, turn into a soft blue
opaque suspension.
2 Glycerin and HCl
Takes a long time (couple of hours) to complete but when these two clear
liquids are mixed together, it turns from clear to a deep transparent red
and slowly goes brown. Warning - this is extremely irritating to the eyes
if you are exposed to it for a while - usually, an hour is enough to
really get you annoyed.
3 (My favorite) Acetone (you can buy large tins of this stuff (1L) at a
hardware store in the automotive section (usually with the bondo and
other body repair supplies) and styrofoam (a large bag of popcorn type
packaging filler will be needed.)
When styrofoam is placed in acetone, the styrofoam ( large volume of

styrofoam for a small volume of acetone ) dissolves and becomes a wet,
play-dough like substance that feels cold to the touch.
This experiment is harmless unless swallowed :-) and should prove to be

quite interesting to the students.
The coldness is due to the evaporation of the acetone from your skin
(ever use nail polish remover? That's acetone.) The acetone will
eventually all evaporate (a 2 inch sphere of this will take a day or two)
and the result will be a porous (trapped acetone bubbles) material that
can be molded to any shape you wish.
From; David O'Driscoll. University of Central Queensland...
Hope someone hasn't already done this one, I have been studying for
exams so have not been reading all of them.
The one we use at our high school demos are pH clocks....

quite good as they are not static displays.
First, take three or four large (1L) beakers and 3/4 fill them then
take your favourite pH indicators (ones with good colours), and add a
few drops to them, then add some dilute sodium hydroxide or something
to make them slightly basic. Next add a handful of dry ice to each beaker.
This creates a nice bubbling mixture with good visual effects, what happens
is obvious (I hope!!!). Some of the CO2 is dissolved in the water, turning
the mixture acidic and when the end-point of the indicator is reached the
colour changes - sometimes quite dramatically. The kids seem to like it and
the chemistry is not too involved.
From:webbb@mbf.UUCP ( Bryan Webb )
I didn't see the originating message of this thread, but from the
responses that have made it here, I think this is the kind of stuff
you might be looking for. In earlier times, I've done these:
1) Place a small pile (several grams) of powdered magnesium on a surface

you don't care about in an environment provided with plenty of
ventilation. On top of this, place a couple of grams of powdered
iodine (well, as close as you can get to it, though that might not
be crucial). Now, put a couple drops of water on the iodine ...
enough to also contact the magnesium ... and stand back. The heat
of the reaction vaporizes some of the remaining iodine into a purple
vapor.
2) This is pretty dangerous, so be very careful. Take a couple of grams

of red phosphorous and place on top of a couple of grams of potassium
iodate. Rapidly stand back... spontaneous combustion. My experience
was a time delay of a couple of seconds, but I wouldn't want to count
on it... I discovered this accidentally... boy was I surprised. The
speed of the reaction may be related to the humidity.
3) Potassium dichromate is normally bright orange at room temperatures. If

it is cooled to liquid nitrogen temperatures, it becomes yellow. If
heated, it becomes a deeper red color. I'm not aware of any other
inorganics that have this range of color change when the temperature
is varied.
4) Ahhh, my favorite... When I was in high school, I took the 2nd year
chemistry class that was offered. We had the resources of the
school at our disposal, so long as the experiment we wanted to do
was "in a book". The book I had was "Chemistry Magic", and described
an "experiment" where some cotton balls were placed on a fireproof
surface, a few grams of Sodium Peroxide was placed on top, and then
you put a drop or two of water that will wet at least a little bit
of both the peroxide and the cotton.
It's a long story, but I this experiment worked, at least on other

cellulose objects like paper towels. In fact, the fire in the
metal trash basket was hot enough to melt/burn away the bottom,
the linoleum underneath, and some of the concrete in the floor.
The flames formed a "solid" yellow flame and lots of thick white
smoke (containing NaOH dust). You really don't want to breathe
this stuff. We didn't, anyway :-)
5) Oh, another thing we did in that class was take the gas outlet used
for the bunsen burners and direct it into a test tube that was
partially submerged in liquid nitrogen. (The whole system was
sealed.) The gas condenses into a liquid... the only problem
was safe disposal. It helps to plan ahead! :-)
[ Note that nuke@reed.edu subsequently supplied the following warning ]

" If you decide to try this be aware that liquid nitrogen will condense
liquid oxygen in a vessel open to the air immersed in it. Liquid O2
forms explosive mixtures with many organics. IF you still want to try
it, immerse the tube in the nitrogen and then immediately run the gas
in. only do a little bit. How much you get depends on what proportion
of weights of low hydrocarbons the gas contains ( I think methane
condenses at this temp, but not quantitatively like some stuff, unless
there is a large surface area)."
6) One of my classmates made luciferin [sic]. It's a liquid that

glows in the dark for about 12 hours. That was fun too!
Happy researching!
Standard disclaimers apply; I'm not sure my company would have hired
me if they had the foregoing admissions before them.
Non-standard disclaimers too: I don't recommend you do any of these things
either.
From: fred@theory.chem.pitt.edu < fred >
If you would like to condense out methane gas in a relatively safe way,
fill a balloon with the gas and THEN condense the gas with liquid N2.
You can use scissors to cut the balloon, and pour the liquid CH4 into
a beaker with water in it (notice that it floats, forms ice, etc.) and
light it. Only the fumes burn as they mix with atmospheric oxygen.
This makes a fair "olympic torch." Wear goggles etc.
From: Larry (Call me "Lefty") C
One that can be safely performed with a long enough spatula.

Mix Calcium Carbide with any strong oxidizer (KMnO4, NaNO3, even MnO2
works). Proportions aren't real important here.
Using face shield, gloves, lab coat and long spatula, drop a SMALL
amount (say, 1 gram or so) of this into common household bleach.
Acetylene and chlorine are evolved, which immediately, uh... exploded
Delightful chlorinated hydrocarbons result, unfortunately :(
15.6 How do I safely perform the Glowing Pickle experiment?
This experiment consists of electrically heating a vegetable that has been

soaked in a brine solution to conduct electricity. Because this experiment
involves electricity at dangerous voltages, the experiment should be
performed on special apparatus under qualified supervision. I'm not going
to detail the equipment and procedures, as they have been described in
an Journal of Chemical Education article [8]. The experiment has not just
been limited to table salt and pickles, many other vegetables and salts
that produce different colours have been investigated and described in the
same issue of the Journal of Chemical Education [9]. People intending to
perform the experiment should obtain both articles.
15.7 How do I make Slime?.
" Slime " is a trademarked commodity obtained by cross-linking guar gum and
borax, and is marketed by the Mattel Toy Corporation. The slime produced for
demonstrations is usually made by cross-linking a poly vinyl alcohol (PVA)
product using borate. The normal method is to carefully prepare a 4%
mass/volume aqueous solution of a hydrolysed high molecular weight PVA
( >100,000 ) - available from Eastman Kodak. Commercial PVA-based adhesives
( such as Elmer's Glue ) will also produce a reasonable quality slime, as
will polymeric materials that have multiple hydroxyl groups and can form
highly-hydrated gels, such as guar gum - but some experimentation may be
required to ascertain optimum ratios.
High MW polymers are difficult to dissolve in solvents ( including water ),
and the best method is to carefully sprinkle the powder over a beaker of
water that is being gently stirred, and continue gentle stirring until a
uniform solution with no gelatinous lumps is obtained.
Any grade of borax ( Na2B4O7.10H2O ) can be used to prepare a 4% mass/mass

aqueous solution. The slime is made by vigorously mixing the two solutions
in the ratio of 1-2 parts of the borax solution to 10 parts of the PVA
solution using a paddle stirrer. Details of a suitable procedure for use in
classrooms have been published [10]. A firmer, less messy, slime can be
prepared from an 8% PVA solution - using equal ratios of the 4% borax
solution [11].
The properties of slime indicate that the cross-linking mechanism does not
consist of strong covalent bonds. Borax hydrolyses in water to form a boric
acid-borate buffer with an approximate pH of 9.
B(OH)3 + 2H2O <==> (B(OH)4)- + H3O+ pK = 9.2
The borate ion is tetrafunctional when interacting with the alcohol groups
of polyols, and thus builds the cross-linking structure. PVA has about 1-2%
of 1,2 diols amongst the remaining 98-99% of 1,3 diols. To obtain the desired
properties, the bonds between the borate and the PVA must be weak, and it is
believed they are hydrogen bonds ( shown as ... below ).
PVA Borate PVA
H H
| |
O-H...O O-H...O
\ / \ / \ /
H-C \ / C-H
/ B- \
CH2 / \ CH2
\ / \ /
H-C-O...H-O O...H-O-C-H
/ | | \
H H
Although individual hydrogen bonds are weak, the large number of available
OH groups in highly-hydrolysed PVA will result in a hydrated, 3-dimensional,
gel, rather than a borate precipitate. The continual breaking and reforming
of the bonds under low mechanical stress, and the large amount of water
incorporated into the gel, are responsible for the rheological properties of
the hydrated gel. Slime can be broken down by reducing the concentration of
borate by titration with a strong acid, and details of such a procedure have
been recently published [12].
Subject: 16. Laboratory Procedures
16.1 What are the best drying agents for liquids and gases?
The Rubber Handbook lists the traditional information on drying agents

that involve on chemical action. This lists phosphorus pentoxide and
magnesium perchlorate as the most effective desiccants. However, later
work by Burfield [1-9] has demonstrated that much of the traditional
information is misleading. He found that the efficiency of the desiccant
is strongly dependent upon the solvent. He also found that Drierite
( anhydrous calcium sulphate ) is only a moderately efficient desiccant for
organic solvents [9], and that correctly prepared molecular sieves are
often the preferred desiccant [2]. His publications are highly recommended.
16.2 What is the effect of oven drying on volumetric glassware?
Many older laboratory texts insist that volumetric glassware should not
be oven dried because of the danger of irreversible and unpredictable
volume changes. However most modern laboratory glassware is now made of
Pyrex, and work by D.R.Burfield has demonstrated that low temperature
drying does not significantly affect the calibration of volumetric
glassware [10]. He demonstrated that exposing volumetric flasks and
pipettes to 320C, either continuously or thermally cycled, resulted in no
significant detectable change to the calibration. He concluded that
"oven temperatures in the range of 110-150C should provide efficient drying
of glassware with no risk of discernible volume changes, even after
prolonged use, providing that Pyrex glass is the material of construction".
16.3 What does the Karl Fischer titration measure?
In 1935 Karl Fischer used the reaction between iodine, sulfur dioxide, and
water to produce a technique for quantifying water [11]. In aqueous solution,
the reaction can be presented as I2 + SO2 + 2H2O <=> 2HI + H2SO4.
He used anhydrous methanol to dissolve the I2 and SO2, and added pyridine
to move the equilibrium to the right by reacting the acidic products.
Fischer assumed his modifications did not change the reaction and one mole of
iodine was equivalent to two moles of water. Smith et al.[12], demonstrated
that both the methanol and pyridine participate in the reaction and one mole
of iodine is equivalent to one mole of water. They suggested two steps:-
(1) SO2 + I2 + H2O + 3RN -> 2RN.HI + RN(SO2)O
(2) RN(SO2)0 + CH3OH -> RN(SO4CH3)H (where R = base = C5H5 for pyridine)
This was further investigated by E.Scholz [13], who proposed:

(1) CH3OH + SO2 + RN -> (RNH)SO3CH3
(2) H20 + I2 + (RNH)SO3CH3 + 2RN -> (RNH)SO4CH3 + 2(RNH)I (where R = Base)
The advantage of the Karl Fischer titration is that it has few interferences
and can quantify water from < 1ppm to 100% in diverse samples, ranging from
gases to polymers. It will measure all water that is made available to the
reagent. the endpoint is usually ascertained using a dead-stop endpoint,
and for low water levels coulometric techniques are used to quantitatively
produce the iodine by anodic oxidation of iodide. The procedures are
described in detail in ASTM, AOAC etc.
16.4 What does the Dean and Stark distillation measure?
The Dean and Stark procedure can be used to measure the water content of
a diverse range of samples, and has been extensively used in industrial
laboratories to measure water in petroleum oils. The technique can measure
% levels of water, but is not as accurate as the Karl Fischer titration,
and is not applicable to samples where the water is not liberated by the
solvent. The sample is mixed with a solvent ( usually a toluene/xylene mix )
and refluxed under a condenser using a special receiver. There are two common
designs of receivers, one for solvents that are heavier than water, and the
more common one for solvents that are lighter than water - illustrations will
be shown in most laboratory glassware supplier catalogues.
The water and solvent are refluxed, and as they condense the two phases
separate as they run into the receiver. The water remains in the receiver
while the solvent returns to the flask. The Dean and Stark technique is also
useful for removing unwanted water from reactions, eg the synthesis of
dibutyl ether by the elimination of water from two molecules of n-butanol
using acidic conditions. An example of this is provided in the preparation
of dibutyl ether described in Vogel, and detailed procedures for the
determination of water using Dean and Stark are provided in ASTM and AOAC.
16.5 What does Kjeldahl nitrogen measure?
The Kjeldahl procedure is routinely used to measure the protein nitrogen

content of organic compounds, especially natural foodstuffs. Contrary to
popular belief, the procedure does not determine total nitrogen on all
organic compounds, as it is not applicable to materials containing N-O or
N-N linkages without modifications to the method. This discrepancy is
becoming of more significance as automated nitrogen analysers using other
techniques are producing different results because they measure the total
nitrogen present.
The method usually involves high temperature ( 390C ) digestion of the

sample using concentrated sulfuric acid, a catalyst ( Cu, Hg, or Se ),
and a salt to elevate the acid boiling point. In some cases 30% hydrogen
peroxide is also used, making the digestion effectively a high-temperature
piranha solution attack on the organic matter. After digestion, the sample
is made strongly alkaline and the ammonia is steam distilled into a boric
acid solution, and aliquots are titrated against a standard acid using an
indicator solution endpoint.
Some organics compounds require aggressive digestion conditions to make

all the organic nitrogen available, consequently Kjeldahl procedures should
not normally be used on samples that may have N-O or N-N bonds. Details of
procedures for foods are in the AOAC handbooks, and general Kjeldahl
procedures are detailed in the ASTM volumes.
16.6 What does a Soxhlet extractor do?
The soxhlet extractor enables solids to be extracted with fresh warm solvent
that does not contain the extract. This can dramatically increase the
extraction rate, as the sample is contacting fresh warm solvent. The sample
is placed inside a cellulose or ceramic thimble and placed in the extractor.
The extractor is connected to a flask containing the extraction solvent, and
a condenser is connected above the extractor. The solvent is boiled, and the
standard extractor has a bypass arm that the vapour passes through to reach
the condenser, where it condenses and drips onto the sample in the thimble.
Once the solvent reaches the top of the siphon arm, the solvent and extract
are siphoned back into the lower flask. The solvent reboils, and the cycle
is repeated until the sample is completely extracted, and the extract is
in the lower flask.
There is an alternative design where the hot solvent vapour passes around
the thimble, thus boiling the solvent in the thimble - this can be a problem
if low-boiling azeotropes form. Procedures for using soxhlet extractors are
described ( along with illustrations which might make the above description
comprehensible :-) ), in Vogel and many other introductory organic laboratory
texts.
16.7 What is the best method for cleaning glassware?.
As scientific glassware can be used for a variety of purposes, from the

ultra-trace determination of sub-ppq levels of dioxin, to measuring %
concentrations of inorganic elements, there is no single cleaning method that
is "best" for all circumstances. Difficult and intractable deposits often
involve the use of hazardous and corrosive chemicals, and details of the
necessary safety precautions for each cleaning solution should obtained
before attempting to clean glassware. The use of heat and/or ultrasonic
agitation can greatly improve the removal rate of many deposits, especially
inorganic and crystalline deposits.
Whilst the semiconductor industry use piranha solution ( refer Section

12.9 ), and several other reactive and toxic chemicals for cleaning, those
reagents can react dangerously with the residues found in laboratories, and
their use is prohibited in some institutions. Such chemicals should only be
used after extensive prior consultation with laboratory management and safety
staff - to either identify safer alternatives, or to ensure that appropriate
protective and safety systems are in place.
If the probable composition of material deposited on the glassware is known,

then the most appropriate cleaning agent can be readily selected. There are
several safe aqueous cleaning solutions that are routinely used. If possible,
glassware should be washed or soaked immediately with an appropriate solvent
for the residue. This will make subsequent cleaning easier, but all traces
organic solvents must be removed before using any cleaning solution.
The most common aqueous-based soaking solutions are commercial formulations

that usually contain alkalis, chelating agents, and/or surfactants, and can
be used either at ambient temperature, or temperatures up to boiling ( with
ventilation - caustic fumes are noxious ). These are very effective for
general grime, most labels, pyrogens, and many common chemical residues, and
well known examples include RBS-35, Decon, Alconox, and Pyroneg. Their main
advantages are low toxicity and ease of disposal.
The next common strategy involves physical abrasion to remove deposits

inside flasks, usually with a bottle brush and an aqueous cleaning solvent
( like those above ) or a suitable organic solvent. A refinement is to add
sand, pumice, glass spheres, or walnut shell chips, along with some water
or solvent, and shake vigorously. It's important that the sand should not
have sharp edges - as it can scratch the glass. It has been suggested that
table salt in solvent ( eg petroleum spirit, methylene chloride, acetone )
is superior, as it doesn't scratch the glass, can be easily removed by
washing with water, and has minimal disposal problems [14].
The traditional glassware cleaning solution is "chromic acid", and many

analytical chemistry texts detail the preparation [15,16]. Chromium (VI) is
highly toxic ( mutagenic, carcinogenic ), and disposal is expensive, as all
solutions containing more than 5 mg/l of chromium are considered hazardous
waste in the USA. Disposal of chromic acid requires a two-stage process,
involving bisulfite addition to reduce Cr(VI) to Cr(III), followed by
neutralisation of the acid. There have also been several reports of
spontaneous explosions of chromic acid cleaning solutions [17,18,19],
consequently the use of chromic acid for cleaning glassware is declining,
and several alternative glassware cleaners have recently been evaluated [20].
Sodium dichromate dihydrate is usually used to prepare chromic acid, as

potassium dichromate is less soluble in sulfuric acid. One technique is to
dissolve 140g of technical grade sodium dichromate dihydrate in approximately
100 ml of water. Add two litres of technical grade 98% sulfuric acid to a 4-5
litre glass beaker that is sitting in a cold water bath in a fume cupboard.
Carefully stir the acid gently and pour a few mls of the dichromate solution
slowly into the acid. Keep repeating the addition every few seconds - after
the previous dose has been dispersed. As long as the stirring is gentle and
continuous, little or no splattering should occur, but the solution will
become quite warm. Allow to cool before storing in a glass-stoppered reagent
bottle. Always ensure that the stopper is sufficiently loose to release any
gas pressure. Never use a screw-capped or similar types of sealed containers.
If made correctly, the chromic acid solution should have no precipitate, will
be a deep red colour, and will last for years in a glass-stoppered bottle.
Ensure the glassware to be cleaned does not have any residual organic
solvents. Chromic acid is very effective at around 80C, but an overnight soak
at ambient temperature is commonly used. If the solution develops a green
hue, it is exhausted and should be disposed of, or regenerated, using
appropriate procedures. Slowly pouring used acid down a drain with the cold
water tap fully open is no longer considered appropriate. There is a recent
report of a technique to regenerate chromic acid cleaning solution ( by
distillation of water and oleum ) that reduces disposal quantities [21].
The major problems with chromic acid are the multiple rinses, and perhaps
even alkaline EDTA treatment [16], that are necessary to remove all the
chromium from glassware - especially if it is required for cell culture or
trace analysis, and the increasing problems of safe and legal disposal of
spent solutions.
An alternative to chromic acid is "Nochromix", which is commercial solid

formulation that contains 90-95% of ammonium persulfate ( ((NH4)2)S208 )
along with surfactants and other additives. The powder is dissolved in
water and mixed with 98% sulfuric acid. The solution is clear, but turns
orange as the oxidizer is consumed, and further additions of solid are
routinely required. It is available from Godax Laboratories, New York.
A similar bath that is reported to be very effective can be made by the

addition of 19 grams of reagent grade ammonium persulfate to two litres of
reagent grade 98% sulfuric acid [22]. Add more ammonium persulfate and acid
every few weeks, as necessary.
One popular replacement for chromic acid in organic laboratories has been
alcoholic sodium hydroxide or potassium hydroxide solutions. These remove
most deposits, with metals and hydrocarbons greases ( Apiezon ), as notable
exceptions. One advantage they have is that they will remove silicone grease
deposits from joints and stopcocks, especially if warmed to 65C, and the
glassware immersed for up to 10 minutes [23]. Prolonged immersion, even at
ambient temperature, will damage ground-glass joints, dissolve glass sinters,
and will leave glass surfaces translucent or opaque. The solution can be
prepared by either adding two litres of 95% ethanol to 120 mls of water
containing 120 grams of sodium hydroxide [16], or by dissolving 100 grams of
potassium hydroxide in 50 ml of water and, after cooling, make up to one
litre [15].
Solutions based on hydrofluoric acid, usually containing 1-5% of HF, also

rapidly attack glass, and destroy sinters, but are very effective for removal
of carbonaceous and fine silica deposits. They also remove silicone greases,
but alcoholic caustic solutions are preferred [23,24,25]. Hydrofluoric acid
is corrosive and extremely nasty if it comes in contact with humans. It
requires extensive safety precautions before use. For most deposits, only a
few minutes are required, and ultrasonic agitation often assists the removal
of deposits. Cleaned glassware usually remains transparent. Cleaners
containing HF should not be used on volumetric glassware.
Another acidic solution, comprising of a 3:1 mixture of concentrated sulfuric

acid and fuming nitric acid, is also extremely effective for removing grease
and dirt, but also requires extensive safety precautions. The grease and dirt
can often be removed more safely using hot aqueous-based cleaners.
If you have intractable organic-based deposits in flasks without standard

ground glass ( or clear glass ) joints, then some deposits can be carefully
burned off in a glass annealing furnace. The glass needs to carefully
follow a slow heating and cooling schedule to minimise thermal stresses and
distortion. My experience has been that standard joints do tend to freeze
more often after such treatment. Also note that glassblowers may not want
to coat their annealing furnace with your rubbish, so they may prohibit
the use of their furnace for such activity.
Subject: 17. Preparation of chemicals
17.1 Where do I find laboratory-scale procedures for organics?
The best introductory handbooks are practical textbooks, eg "Organic" Vogel

and "EPOC" Vogel. They provide a diverse range of experiments that soon help
develop synthetic skills. If you master the preparations in Vogel you are
at the stage where you can start to obtain papers from organic chemistry
journals and reproduce their syntheses. There are also several texts that
discuss techniques for purifying laboratory chemicals, eg [1] The parameters
of common specialist synthetic procedures usually are fully described in
specialist texts that will only normally be available in chemistry department
libraries ( eg Palladium Reagents in Organic Syntheses [2]). Most educational
institutions will have a structured laboratory programme to develop skills.
17.2 Where do I find laboratory-scale procedures for inorganics?
Most synthetic chemistry of inorganics appears to be devoted more to complex

organometallics, superacids and superconductors than common inorganics, but
it is worth considering that, of the top fifteen industrial chemicals
produced, the only organic compounds are ethylene, propylene, ethylene
dichloride and urea. There are specialist texts available that describe how
to purify inorganic laboratory reagents, eg [1]. I expect some inorganic
chemists to berate me for not knowing the standard inorganic synthesis
textbooks. ;-)
17.3 Where do I find industrial chemical process details?
The standard text for common processes remains Shreve, and I must admit that
I enjoy reading the 1945 first edition to obtain a good overview of an
industry. McKetta provides excellent process design details, along with
comparisons of various processes. Kirk Othmer provides an excellent update
on the various processes and chemicals used extensively today. Kirk Othmer
remains the first port of call, but Ullmann is a close second. Both of these
provide extensive references to more specific texts.
Industry journals, eg Hydrocarbon Processing, offer annual reviews of the

processes used in their industry. Patent literature has to be treated
cautiously, as it is not always immediately obvious which patents detail
actual viable processes. Chemical engineering texts, eg Perry, provide
comprehensive detail of the equipment and operational parameters.
Subject: 18. Sensory properties of chemicals
18.1 How do light sticks work?, and how can I make one?
From: perks@umbc.edu (Mark Perks) Date: 15 Sep 1994

Subject: Re: Chemiluminescence Sticks
Chemical Demonstrations [[1] v.1 p.146- ], by Bassam Shakhashiri, offers a
thorough discussion of Cyalume lightsticks. Professor Shakhashiri is at
the University of Wisconsin, Madison, I believe.
"The Cyalume lightstick contains dilute hydrogen peroxide in a

phthalic ester solvent contained in a thin glass ampoule, which is
surrounded by a solution containing a phenyl oxalate ester and the
fluorescent dye 9,10-bis(phenylethynyl)anthracene...When the ampoule is
broken, the H2O2 and oxalate ester react.."
From: chideste@pt.Cyanamid.COM (Dale Chidester) Date: Mon, 13 Mar 1995

Subject: Re: How to make chemical light ?
The following produce rather spectacular results. Chemicals are

available through Fluka and Aldrich. The dyes are expensive.
Dyes:-
9,10-bis(phenylethynyl)anthracene (BPEA) (yellow) [10075-85-1] Fluka 15146
9,10-diphenylanthracene (DPA) (blue) [1499-10-1] Fluka 42785
5,6,11,12-tetraphenylnaphthacene (rubrene) (red) [517-51-1] Fluka 84027
Other reagents required:-

bis(2-carbopentyloxy-3,5,6-trichlorophenyl)oxalate (CPPO)
[75203-51-9] Aldrich 39,325-8
bis(2-ethylhexyl)phthalate (DOP) (solvent) [117-81-7] Fluka 80032
sodium salicylate (catalyst) [54-21-7] Fluka 71945
35% hydrogen peroxide [7722-84-1] Fluka 95299
Saturate solvent with dye and CPPO. Sonicate to help solvation. Start with
about 50 mg dye (BPEA, DPA or rubrene) in 10 g solvent with 50 mg CPPO and
5 mg sodium salicylate. CPPO is limiting reagent.
Put small quantity (20 drops) in a small vial and add equal volume of
hydrogen peroxide. Mix vigorously. There will be two phases. Avoid skin
contact! Don't cap tightly!
The following explanation of the chemistry was provided:-

From: sbonds@jarthur.claremont.edu (007)
All of the material below is taken from a chemical demonstrations book

[[1], v.1, p.146 ].
The oxidant is hydrogen peroxide contained in a phthalate ester solvent.

The concentration is very low, less than 0.5%. The fluorescing solution
consists of a phenyl oxalate ester and a fluorescent dye. The dye used is
9,10-bis-(phenylethynyl)anthracene (for green) or 9,10-diphenylanthracene
(for blue).
Here is the reaction sequence:
1) (Ph)-O-CO-CO-O-(Ph) + H2O2 --> (Ph)-O-CO-CO-O-OH + (Ph)-OH
2) (Ph)-O-CO-CO-O-OH --> O-O

| | + (Ph)-OH
OC-CO
3) C2O4 + Dye --> Dye* + 2CO2
4) Dye* --> Dye + hv
In 1) The hydrogen peroxide oxidizes the phenyl oxalate ester to a

peroxyacid ester and phenol. The unstable peroxyacid ester decomposes to
the cyclic peroxy compound and more phenol in step 2). The cyclic peroxy
compound is again unstable and gives off energy to the dye as it decomposes
to the very stable carbon dioxide. The dye then radiates this energy as
light.
An alternative chemiluminescence demonstration involves the H2O2 oxidation

of lucigenin ( bis-N-methylacridinium nitrate [2315-97-1] Aldrich B4,920-3 ),
[ [1] v.1 p.180-185 ] which has recently been modified to provide a slow
colour change across the visible spectrum [2]. One of the reagents in that
lucigenin oxidation ( Rhodamine B ) is a mutagen and suspected carcinogen.
18.2 How do hand warmers work?, and how can I make one?
They consist of an aqueous solution of sodium acetate with a small "clicker"

disk to provide a small clean surface that initates crystallisation. The solute
is dissolved into solution by prior warming. When heat is required, the disk
is "clicked" to scrape a small surface, and this clean surface will initiate
the sodium acetate crystallisation from the now supersaturated solution. The
heat of crystallisation is slowly released.
18.3 What are the chemicals that give fruity aromas?
Most of the desirable food aromas come from low to medium molecular weight
organic compounds - usually alcohols, aldehydes, esters, ketones, and
lactones. These may be " natural " ( extracted from natural sources ),
" nature-identical " ( synthetic, but identical to known natural compounds ),
and " artificial " ( synthetic, not found in nature ). The perceived aroma of
molecules can change dramatically with minor isomeric or structural changes,
and common fruity aromas are usually complex mixtures of several compounds.
Because man-made chemicals are frequently made from chemicals derived from
fossil fuels, the isotopic ratios of the carbon atoms has been used to
discriminate between natural and nature-identical chemicals. Natural
processes usually involve the use of enzymes that selectively produce a
specific isomer, and some man-made aromas are now produced enzymatically.
Chiral chemistry, often utilising chiral chromatography that was initially
developed for pharmaceuticals, is now also being used for the production
and testing of man-made aromas, as enantiomerically-pure aroma chemicals
command premium prices.
Some chemicals are listed below, along with their use in either fragrances
and/or flavours, and boiling point ( 760 mmHg, unless otherwise stated ).
Some of them are also considered toxic, and thus their use may be controlled.
Volume A11 of Ullmann has an excellent monograph on flavours and fragrances,
and more detail can be obtained from the journal Perfumer and Flavorist.
The catalogues of well-known suppliers such as Dragoco GmbH ( Germany ),
L.Givaudin and Cie ( Switzerland ), and Takasago Perfumery Company ( Japan ),
also contain information on chemical composition and health and safety.
Chemical BP CAS RN Application

C (mmHg)
acetoin 148 [513-86-0] butter
acetophenone 202 [98-86-2] orange blossom
benzyl acetate 206 [140-11-4] jasmine
butyl acetate 125 [123-86-4] apple
2,3-butanedione 88 [431-03-8] butter
(+)-carvone 230 [2244-16-8] caraway, dill
(-)-carvone 230 [6485-40-1] spearmint
citral 229 [5392-40-5] lemon
citronellal 207 [2385-77-5] balm mint
decanal 208 [112-31-2] citrus
dihydromyrcenol 78 (1) [18479-58-8] lavender
2,6-dimethyl-2-heptanol 171 [13254-34-7] freesia
ethyl butyrate 120 [105-54-4] pineapple
ethyl 2t-4c-decadienoate 71 (45) [3025-30-7] pear
ethyl hexanoate 168 [123-66-0] pineapple
ethyl isovalerate 132 [108-64-4] blueberry
ethyl 2-methylbutyrate 133 [7452-79-1] apple
geraniol 229 [1066-24-1] roselike
hexyl acetate 169 [142-92-7] pear
hexyl salicylate 168 (12) [6259-76-3] azalea
1-(4-hydroxyphenyl)-3-butanone [5471-51-2] raspberry
isoamyl acetate 143 [123-92-2] banana
(+)-limonene 176 [5989-27-5] lemon
linalool 198 [78-70-6] lily of the valley
linalyl acetate 220 [115-95-7] bergamot
8-mercapto-p-menthan-3-one 57 (8) [38462-22-5] blackcurrant
1-p-methene-8-thiol 40 (1) [71159-90-5] grapefruit
3-methyl-2-cyclopenten-2-ol-1-one [80-71-7] caramel
4-methyl-2(2-methyl-1-propenyl)tetrahydropyran
70 (12) [16490-43-1] rose
myrcenol 78 (50) [543-39-5] lime
2t-6c-nonadien-1-ol 98 (11) [28069-72-9] violet
3-octanol 175 [20296-29-1] mushroom
1-octen-3-ol 84 (25) [3391-86-4] mushroom
phenethyl acetate 238 [103-45-7] rose
phenethyl alcohol 220 [60-12-8] rose
phenethyl isoamyl ether [56011-02-0] chamomile
2-propenyl hexanoate pineapple
alpha-pinene 156 [80-56-8] pine
alpha-terpineol 217 [98-55-5] lilac
alpha-trichloromethylbenzyl acetate [90-17-5] rose
18.4 What is the most obnoxious smelling compound?
Many low molecular weight sulfur-containing compounds tend to induce adverse

reactions in people, even if they have not encountered them before, eg the
glandular emissions of skunk (n-butyl mercaptan, dicrotyl sulfide).
Butyric acid reminds people of vomit, and cadaverine ( 1,5 Pentadiamine )
reminds people of rotten tissue, but without an earlier association, they
may not regard them as unusually obnoxious.
18.5 What is the nicest smelling compound?
Aside from thinking about your stomach, when the smell of cooking foods
is attractive, then most people like the smell of flowers and citrus fruits.
These are volatile, aromatic, oils, whose major components are complex
mixtures of medium volatility compounds, often derived from terpenes, eg
Oil of Rose ( 70 - 75% geraniol = (E)-3,7-dimethyl-2,6-octadiene-1-ol ),
Oil of Bergamot ( 36 - 45% linalyl acetate = 3,7-dimethyl-1,6-octadien-3-yl
acetate ). Many aromatic oils are mixtures of terpene esters ( oil of
geranium = 20 - 35% geraniol esters ) or aldehydes ( oil of lemon grass =
75 - 85% citral = 3,7-dimethyl-2,6-octadienal ). Merck briefly describes
nearly 100 volatile oils, from Oil of Amber to Oil of Yarrow, along with
typical applications. Flower perfumes are complex blends of compounds, and
detailed compositions of your favourite smell are often available in the
journal " Perfumer and Flavorist ".
Expensive flower petal perfumes, such as rose and jasmine, are produced
using extracts obtained by the traditional "enfleurage" process ( refer to
Section 24.4 ).
topic!
knowledge

Date: Thu, 15 Jan 2004 22:11:36 +1300
Message-ID: <39mc001ubmoa3otpev8i4d9gmttnffgqvg@4ax.com>
Version: 1.17
18.6 What is the most bitter compound?
Denatonium Benzoate = Bitrex, or even in some strange chemistry circles,

N-[(2-[2,6-Dimethylphenyl)amino]-2-oxoethyl]-N,N-diethylbenzenemethan-
aminium benzoate [3734-33-6]. It is added to toxic chemicals ( such as
methylated spirits ) as a deterrent to accidental ingestion.
18.7 What is the sweetest compound?
Most scales use sucrose as a sweetness of 1, and compare the relative

sweetness of other sweeteners to sucrose.
Name Relative Sweetness Category

D-Glucose 0.46 Natural Food Product
Lactose 0.68 " " "
D-Fructose 0.84 " " "
Sucrose 1 " " "
Cyclamate 30 EC Permitted, USA Prohibited
Aspartame 200 EC, USA Permitted.
Saccharin 300 EC Permitted, USA Prohibited
Sucralose 650 Au, Ca Permitted, trials elsewhere
Alitame 2,000 Undergoing trials
Thaumatin 3,000 EC permitted, US chewing gum only.
Carrelame 160,000 Guanidine sweetener
Bernardame 200,000 " "
Sucrononate 200,000 " "
Lugduname 220,000 " "
The guanidine sweeteners are not expected to be approved for food use.
There are several other important attributes of sweeteners, such as
low toxicity, no after-taste, whether metabolised or excreted, etc.,
that must also be considered.
The potency scale is fairly flexible, and differing publications can

assign different values. The August 1995 copy of the Journal of Chemical
Education contained several papers from a symposium on sweeteners [3,4],
and an article in Chemistry and Industry also discusses sweeteners from
both natural and artificial sources [5], and Kirk Othmer has a monograph
on sweeteners.
The sweetener used in "diet" beverages is usually Aspartame, and they

are usually required to display a warning for phenylketurics that the
product contains a source of phenylalanine. As Aspartame slowly degrades
in acid solutions, such products also have a "use-by" date.
Although banned by the FDA in 1970 ( because a mixture of saccharin and

cyclamate caused tumours in test animals ), saccharin has been still
marketed under extensions of approval, Ironically, subsequent work
implicated the saccharin, and the cyclamate was found not to be the
tumour-causing agent, but it is still banned.
18.8 What salts change the colour of flames?.
Both Vogel ( qualitative inorganic ) and the Rubber Handbook list details of
flame tests for elements. The spectra of the alkaline earth compounds are
relatively complex, so using filters to view the flame can change the colour
observed as dominant lines are filtered out. In general, except for copper,
any compound of an element can be used, however toxic salts ( such as
cyanides ) should not be used. Halogen salts are usually readily available,
and are reasonably volatile. In all cases, perform experiments in a
well-ventilated area - preferably a fume hood. The emission spectra in the
visible region is the sum of several emission lines, with dominant lines
masking others. The visible spectrum is approximately :-
Red 800 - 620 nm
Orange 620 - 600 nm
Yellow 600 - 585 nm
Green 585 - 505 nm
Blue 505 - 445 nm
Violet 445 - 400 nm
There are also the various bead tests employing borax ( sodium tetraborate
Na2B4O7.10H2O ), Microcosmic salt ( NaNH4HPO4 ), or sodium carbonate
(Na2CO3), using both oxidising and reducing flames. The bead test procedures
are detailed in Vogel ( qualitative inorganic ), and similar texts.
Element Colour Some of the contributing lines, and comments.
Arsenic Light Blue 449.4 nm, 450.7 nm.

( Arsenic is highly toxic - only perform in fume hood under supervision )
Barium Green-Yellow 553.6 nm, 539.1 nm, 536.1nm, 614.2 nm.
Blue (faint) 455.4 nm, 493.4 nm.
Cesium Red-Violet 852.1 nm.
Calcium Orange 618.2 nm, 620.3 nm.
Yellow-Green 530.7 nm, 559.5 nm.
Violet (faint) 422.7 nm.
Greenish with blue glass.
Copper Emerald Green 521.8 nm, 529.2 nm, 515.3 nm.
Not chloride, or in presence of HCl
Azure Blue 465.1 nm.
Copper chloride, or HCl present
Lead Light Blue 500.5 nm.
( Lead is highly toxic - only perform in fume hood under supervision )
Lithium Carmine Red 670.78 nm, 670.79 nm.
Orange (faint) 610.1 nm.
Violet with blue glass
Potassium Red 766.5 nm, 769.9 nm.
Violet 404.4 nm, 404.7 nm.
Purple-red with blue glass
Rubidium Violet 780.0 nm, 794.8 nm.
Sodium Yellow 589.0 nm, 589.6 nm.
Invisible when viewed with blue glass
Strontium Scarlet Red 640.8 nm, 650.4 nm, 687.8 nm, 707.0 nm.
Violet 460.7 nm, 421.5 nm, 407.8 nm.
Violet with blue glass
Tellurium Green 557.6 nm, 564.9 nm, 566.6 nm, 570.8 nm.
( Tellurium is highly toxic - only perform in fume hood under supervision )
Thallium Green 535.0 nm.
( Thallium is highly toxic - only perform in fume hood under supervision )
Zinc Whitish Green Large number of peaks between 468.0-775.8 nm.
( Zinc fumes are toxic - only perform in a fume hood under supervision )
Impressive coloured flames have been obtained using chlorides and a methanol
flame in a petri dish [6]. Even more spectacular results have been obtained
by nitrating cellulose filter paper, and impregnating it with salts prior
to ignition [7].
18.9 What chemicals change colour with heat, light, or pressure?.
Compounds that visibly and reversibly change colour when subjected to a

change in their environment are known as chromogenic materials. There are
four major categories - electrochromic, photochromic, piezochromic, and
thermochromic, all of which are extensively discussed in a recent, well
referenced, monograph in Kirk Othmer [8].
Electrochromic materials exhibit a change in light transmittance or

reflectance induced by direct current at potentials of approximately one
volt. The change usually is an oxidation-reduction reaction, using either
inorganic or organic compounds, and the colour change can occur at either
the anode or the cathode - which are usually thin films. There are two major
classes, the ion-insertion/extraction type - such as tungsten trioxide, and
the noninsertion group - such as the viologens, a family of halides of
quaternary bases derived from 4,4'-bipyridinium. One viologen example is
1,1'-diheptyl-4,4'-bipyridinium bromide [6159-05-3], which changes from
clear to bluish purple. The most common application of viologens has been
the electrochromic interior rearview mirrors available for cars since 1988.
These utilise a substituted viologen as the cathode colouring material, with
a compound like phenylene diamine as the anode colouring electrochromic
material. The mechanism details, along with a description of the ingenious
control system, are described in a recent comprehensive review of
electrochromic materials [9].
Photochromic materials undergo a reversible change in light absorption that

is induced by electromagnetic radiation, however most common applications
involve reversible changes in colour or transparency on exposure to visible
or ultraviolet light. This is often seen as a change in the visible spectrum
( 400 - 700 nm ), and can be rapid or very slow. There are two major classes
of photochromic materials, inorganic and organic.
Examples of the inorganic type are the silver halides, which are suspensions
of fine ( 10-20 nm ) silver halide crystals dispersed throughout a glass that
has been slowly cooled. An alternative technique involves diffusion of the
silver halide into the surface of the glass. The cuprous ion can catalyse
both the photochromic darking and thermal fading reactions, and the colour
can be shifted from grey to brown by the addition of gold or palladium -
which may be added to the glass in trace amounts. The most popular current
application for glass containing silver halide is for prescription eyewear.
The organic photochromic systems can be subdivided according to the type of

reaction. Geometric isomerism can result in different optical properties,
eg azobenzene ( C12H10N2 [103-33-3] ) undergoes photoisomerization, and the
cis form [1080-16-6] has higher absorbance than the trans form [17082-12-1].
Cycloaddition can produce photochromism, such as the reversible formation of
the colourless 4b,12b,endoperoxide ( C28H14O4 [74292-77-6] ) from the red
parent compound dibenzo(a,j)perylene-8,16-dione ( C28H14O2 [5737-94-0] ).
Dissociation, either heterolytic ( photolysis of triphenylmethyl chloride
[76-83-5] ), or homolytic ( photolysis of bis(2,4,5-triphenylimidazole
[63245-02-3] to form a red-purple free radical ), may also produce
photochromism.
UV can excite polycyclic aromatics, such as 1,2,5,6-dibenzacridene ( C21H13N

[226-36-8] ), to their triplet state, which has a different absorption
spectrum. Viologens may undergo redox reactions and exhibit photochromic
behaviour when crystalline and subjected to UV. The most popular photochromic
materials utilise reversible electrocyclic reactions, and are often indolino
spiropyrans and indolino spiroxazines, however the mechanism also covers
fulgide, stilbene, and dihydroindolizine examples. Details and structures
are provided in the Kirk Othmer monograph [8], and the Journal of Chemical
Education has published descriptions and preparation techniques for both
inorganic [10] and organic photochromic compounds and sunglasses [11].
Piezochromic materials change colour as they are compressed. There are three
common types:- organic molecules ( such as N-salicylidene-2-chloroaniline
[3172-42-7] ), metal cluster compounds ( such as the octahalodirhenates,
(Re2X8)2-, where X=Cl,Br,I ), and copper (II) organic complexes with
compounds like ethylene diamine. They are still being researched, and
interested readers should investigate the references in the Kirk Othmer
monograph [8].
Thermochromic materials reversibly change colour as their temperature is

changed. There are a very large number of systems, but one common example
of thermochromic transitions in metal complexes is the transition between
the blue tetrahedral and pink octahedral coordinations of cobalt (II) when
cobalt chloride is added to anhydrous ethanol and the temperature changed.
Examples of thermochromic transitions in inorganic compounds include
Ag2HgI4 [12344-40-0] and VO2, and several inorganic sulfides also have large
changes occurring in the infra-red range, and are being considered for IR
imaging applications.
There are thousands of organic thermochromic compounds, with well known

examples including di-beta-naphthospiropyran [178-10-9] ( thermally-induced
heterolytic bond cleavage resulting in ring opening), poly(xylylviologen
dibromide [38815-69-9] ( charge transfer interactions resulting in hydration-
dehydration changes ), and ETCD polydiacetylene [63809-82-5] ( thermally-
induced transitions in the unsaturated backbone resulting in rearranged side
groups ). Information on photochromism in organic and polymeric compounds is
available in published reviews [12,13].
Subject: 19. Physical properties of chemicals
19.1 Rheological properties and terminology
Contributed by Jim Oliver
RHEOLOGY
What is RHEOLOGY ?
RHEOLOGY describes the deformation of a material under the influence of
stresses. Materials in this context can be solids, liquids or gases. In this
FAQ we will be concerned only with the rheological properties of liquids.[1]
Perry discusses the some aspects of the behaviour of gases, and Ullmann
discusses elastic solids.
When liquids are subjected to stress they will deform irreversibly and flow.
The measurement of this flow is the measurement of VISCOSITY. IDEAL liquids
are very few, whereas non-ideal examples abound. Ideal liquids are : water
and pure paraffin oil. Non-ideal examples would be toothpaste or cornflour
mixed with a little water. [2]
What is VISCOSITY ?
VISCOSITY is expressed in Pascal seconds (Pa.s) and to be correct the
conditions used to measure the VISCOSITY must be given. This is due to the
fact that non-ideal liquids have different values of VISCOSITY for different
test conditions of SHEAR RATE, SHEAR STRESS and temperature. [3,4]
A graph describing a liquid subjected to a SHEAR STRESS (y axis) at a

particular SHEAR RATE (x axis) is called a FLOW CURVE. The shape of this
curve reveals the particular type of VISCOSITY for the liquid being studied.
[3]
What is a NEWTONIAN LIQUID ?

NEWTONIAN LIQUIDS are those liquids which show a straight line drawn from the
origin at 45 degrees, when graphed in this way. Examples of NEWTONIAN liquids
are mineral oil, water and molasses. (Isaac NEWTON first described the laws
of viscosity) [1] All the other types are NON NEWTONIAN.
What does NON NEWTONIAN mean ?

a. PSEUDOPLASTIC liquids are very common. These display a curve starting at
the origin again and curving up and along but falling under the straight
line of the NEWTONIAN liquid. In other words increasing SHEAR RATE results
in a gradual decreasing SHEAR STRESS, or a thinning of viscosity with
increasing shear. Examples are toothpaste and whipped cream.
b. DILATANT liquids give a curve which curves under then upward and higher
than the straight line NEWTONIAN curve. (Like a square law curve) Such
liquids display increasing viscosity with increasing shear. Examples are
wet sand, and mixtures of starch powder with small amounts of water. A car
may be driven at speed over wet sand, but don't park on it, as the car may
sink out of sight due to the lower shear forces (compared to driving over)
the wet sand.
There are other terms used which include :
THIXOTROPY - this describes special types of PSEUDOPLASTIC liquids. In this

case the liquid shows a YIELD or PLASTIC POINT before starting to thin out.
What this means is the curve runs straight up the y axis for a short way then
curves over following ( but higher and parallel to ) the PSEUDOPLASTIC curve.
This YIELD POINT is time dependant. Some water based paints left overnight
develop a FALSE BODY which only breaks down to become useable after rapid
stirring. Also: the curve describing a THIXOTROPIC liquid will be different
on the way up (increasing shear rate) to the way down (decreasing shear rate).
The area inside these two lines is a measure of it's degree of THIXOTROPY.
This property is extremely important in industrial products, e.g to prevent
settling of dispersed solids on storage. [3]
A RHEOPECTIC liquid is a special case of a DILATANT liquid showing increasing

viscosity with a constant shear rate over time. Again, time dependant but in
this case _increasing_ viscosity.
Why do some liquids become solid ?
A few special liquids (dispersions usually) display extraordinary DILATANT
properties. A stiff paste slurry of maize or cornflour in water can appear to
be quite liquid when swirled around in a cup. However on pouring some out
onto a hard surface and applying extreme shear forces (hitting with a hammer)
can cause a sudden increase in VISCOSITY due to it's DILATANCY. The
VISCOSITY can become so high as to make it appear solid. The "liquid" then
becomes very stiff for an instant and can shatter just like a solid material.
It should be noted that the study of viscosity and flow behaviour is

extremely complex. Some liquids can display more than one of the above
properties dependant on temperature, time and heat history.
What are Electrorheological Fluids? ( added by Bruce Hamilton )
Electrorheological (ER) fluids change their flow properties when an electric

field is applied, and are usually dispersions of polarizable particles in an
insulating base fluid [5]. Their apparent viscosity can change by orders of
magnitude in milliseconds when a fews watts of electrical power are applied.
The shear stress versus shear rate properties of ER fluids vary as a function
of the applied electric field, When an electric field is applied, the fluid
switches from a liquid to semisolid. The particles are usually irregularly-
shaped 0.5-100um and present at concentrations of 10-40% by mass. ER fluids
are dielectric particles in an insulating medium ( such as silicone oil ),
along with additives ( such as surfactants, dispersants, and possibly a
polar activator ). ER fluid effectively function as leaky capacitors. The
electric field can be either AC, pulsed DC, or DC, with AC producing less
electrophoresis of particles to electrodes.
There are two categories of ER particulate materials, extrinsically

polarizable materials ( which require a polar activator ), and intrinsically
polarizable materials. Extrinsically polarizable materials can be polar
nonionic compounds ( such as silica, alumina, or polysaccharides ), or polar
ionic materials ( such as the lithium salt of polymethacrylic acid ),
Intrinsically polarizable materials provide simpler systems - because a polar
activator is not required, and they have a lower thermal coefficient of
conductance. The most common examples are the ferroelectrics like barium
titanate (BaTiO3 ) and polyvinylidene difluoride, however their performance
has been poor, as has been that of metal powders ( such as iron and
aluminium - even when coated with an insulating layer ), and research is
concentrating on conducting polymers ( such as polyanilines and pyrolysed
hydrocarbons ) [5,6].
The ability to utilise computer-based electrical switching to control ER

fluid properties has resulted in vehicle suspension and industrial vibration
control as major target applications for ER fluids. Demonstration systems
have been built, and they match performance predictions, however cost and
durability issues still have to be solved [7].
19.2 Flammability properties and terminology
There are several properties of flammable materials that are frequently

reported. It should be remembered that most discussions concerning
flammable liquids usually consider air as the oxidant, but oxygen and
fluorine can also be used as oxidants for combustion, and they will result
in very different values.
The flammability limits in air are usually reported as the upper and lower
limits ( in volume percent at a certain temperature, usually 25C ), and
represent the concentration region that the vapour ( liquid HCs can not burn )
must be within to support combustion. Hydrocarbons have a fairly narrow range,
( n-hexane = 1.2 to 7.4 ), whereas hydrogen has a wide range ( 4.0 to 75 ).
The minimum ignition energy is the amount of energy ( usually electrical )

required to ignite the flammable mixture. Some mixtures only require a very
small amount of energy (eg hydrogen = 0.017mJ, acetylene = 0.017mJ ),
whereas others require more (eg methanol = 0.14mJ, n-hexane = 0.29mJ,
diethyl ether = 0.20mJ, acetone = 1.15mJ, dichloromethane = 133mJ @ 88C ),
and some require significant amounts, (eg ammonia = >1000mJ ).
The flash point is the most common measure of flammability today, especially
in transportation of chemicals, mainly because most regulations use the flash
point to define different classes of flammable liquids. The flash point of a
liquid is the temperature at which the liquid will emit sufficient vapours
to ignite when a flame is applied. The test consists of placing the liquid
in a cup and warming it at a prescribed rate, and every few degrees applying
a small flame to the air above the liquid until a "flash" is seen as the
vapours burn. Note that the flame is not applied continuously, but is
provided at prescribed intervals - thus allowing the vapour to accumulate.
There are a range of procedures outlined in the standard methods for

measuring flash point ( ASTM, ISO, IP ) and they have differing cup
dimensions, liquid quantity, headspace volume, rate of heating, stirring
speed, etc., but the most significant distinction is whether the space above
the liquid is enclosed or open. If the space is enclosed, the vapours will be
contained, and so the flash point is several degrees lower than if it is
open. Most regulations specify closed-cup methods, either Pensky-Martens
Closed Cup or Abel Closed Cup. It is important to remember that these methods
are only intended for pure chemicals, if there is water or any other volatile
non-flammable compounds present, their vapours can extinguish or mask the
flash. For used lubricants, this may be partially overcome by using the TAG
open cup procedure - which is slightly more tolerant of non-flammable
vapours. A material can be flammable, but may not have a flash point if other
non-flammable volatile compounds are present. For alkane hydrocarbons, flash
point increases with molecular weight.
There is an older measure, called the fire point, which is the temperature
at which the liquid emits sufficient vapours to sustain combustion. The fire
point is usually several degrees above the flash point for hydrocarbons.
The minimum autoignition temperature is the temperature at which a material

will autoignite when it contacts a surface at that temperature. The procedure
consists of heating a glass flask and squirting small quantities of sample
into it at various temperatures until the vapours autoignite. The only
source of ignition is the heat of the surface. For the smaller hydrocarbons
the autoignition temperature is inversely related to molecular weight, but it
also increases with carbon chain branching. Autoignition temperature also
correlates with gasoline octane ratings ( refer to Gasoline FAQ available in
rec.autos.tech, which lists octane ratings and autoignition temperatures for
a range of hydrocarbons.)
Flash Point Autoignition Flammable Limits
Temperature Lower Upper
( C ) ( C ) ( vol % at 25C)
methane -188 630 5.0 15.0
ethane -135 515 3.0 12.4
propane -104 450 2.1 9.5
n-butane -74 370 1.8 8.4
n-pentane -49 260 1.4 7.8
n-hexane -23 225 1.2 7.4
n-heptane -3 225 1.1 6.7
n-octane 14 220 0.95 6.5
n-nonane 31 205 0.85 -
n-decane 46 210 0.75 5.6
n-dodecane 74 204 0.60 -
n-tetradecane 99 200 0.50 -
19.3 Supercritical properties and terminology?
Supercritical fluids have some very unusual properties. When a compound is

subjected to conditions around the critical point ( which is defined as
the temperature at which the gas will not revert to a liquid regardless how
much pressure is applied ), the properties of the supercritical fluid become
very different to the liquid or the gas phases. In particular, the solubility
behaviour changes. The behaviour is neither that of the liquid or that of the
gas. The transition between liquid and gas can be completely smooth.
The pressure-dependant densities and corresponding Hildebrand solubility

parameters show no break on continuity as the supercritical boundary is
crossed. Physical properties fall between those of a liquid and a gas.
Diffusivities are approximately an order of magnitude higher than the
corresponding liquid, while viscosities are an order of magnitude lower.
These properties ( along with low surface tension ) allow SCFs to have
liquid-like solvating power with the mass transport characteristics of
a gas.
Potential Supercritical Fluids

Compound Critical Critical Density
Temperature Pressure
( C ) ( bar ) (g cm^-3)
Ammonia 132.4 112.8 0.235
Carbon dioxide 30.99 73.75 0.468
CFC-12 111.8 41.25 0.558
Dimethyl ether 126.9 52.7 0.271
Ethane 32.4 49.1 0.212
HCFC-22 96.15 49.90 0.524
HCFC-123 183.68 36.62 0.550
HFC-116 19.7 29.8 0.608
HFC-134a 101.03 40.57 0.508
Methanol 240.1 83.1
Nitrous oxide 36.4 72.54 0.453
Propane 96.8 42.66 0.225
Water 374.4 227.1
Xenon 16.6 58.38 1.105
Nitrous oxide is seldom used because early researchers reported explosions.

Note that using liquid CO2 at pressure ( as for the commercial extraction
of hops ) is still just liquid CO2 extraction, not supercritical CO2
extraction. There are several good general introductions to supercritical
fluids [8,9,10]
19.4 Formation of gaseous bubbles in liquids
Discussions about the behaviour of dissolved gases in liquids, especially

when discussing carbonated beverages, are usually more appropriate in
sci.physics and/or sci.mech.fluids, and there is a good text available [11].
Section 23.9 of this FAQ lists the change in solubility with temperature
for common atmospheric gases in water at near-ambient pressure. As the
temperature increases, the solubility decreases, creating a supersaturated
solution that can result in bubble formation. A similar effect occurs if the
pressure is reduced. The formation of bubbles can be understood in
thermodynamic terms using the Gibbs free energy of the bubble.
Gibbs free energy = -n * R * T ln(C/Cs) + gamma * A
A = Surface area of the bubble.

C = Concentration of gas in the liquid,
Cs = Concentration of gas in the liquid at saturation,
gamma = Interfacial tension between the gas and the liquid
n = Number of moles of gas in the bubble
= (P*V)/(R*T), where P = pressure, and V = volume of a sphere.
R = Gas Constant
T = Temperature
After inserting the expressions for the surface area of a sphere (r = radius)
and number of moles, and differentiating, then we obtain:-
r(mininum) = 2 * gamma / ( P * ln(C/Cs))
This describes the size of a bubble that would continue to grow under the
existing conditions, rather than redissolve. Of course, the expression
assumes homogeneous precipitation of the bubble, and in real life most
bubbles are created heterogeneously. Statistics and kinetics are also
required to determine the rate of formation of bubbles, and predict the
effect of changing parameters such as temperature. As the liquid is warmed,
bubbles may be created faster, as the higher temperatures overcome the
activation barrier - which is the difference between the Gibbs free energy
when r is less than r(minimum), and the Gibbs free energy at r(minimum).
The formation of a bubble also dramatically perturbs the system, even

causing secondary bubbles to form. Secondary bubble formation may be
implicated in the production of copious quantities of froth from shaken,
quickly-opened, carbonated drink containers. The sites for gaseous bubble
formation in supersaturated drinks are typically small particles, or minor
flaws on the smooth surface of the container.
19.5 Why is Mercury a liquid at room temperature?.
First, let's look at the melting points of some of the elements surrounding
mercury in the periodic table ( in degrees C ) :-
Period IB IIB IIIA
4s3d4p Cu 1083 Zn 419.5 Ga 29.8
5s4d5p Ag 960.8 Cd 320.9 In 157
6s(4f)5d6p Au 1063 Hg -38.4 Tl 304
The interesting comparison is between Hg and Au, as their properties differ

dramatically, although their electron structures are similar:-
14 10 1
Au(g) : Xe | 4f , 5d , 6s
79 54
14 10 2
Hg(g) : Xe | 4f , 5d , 6s
80 54
Very few chemistry textbooks discuss relativistic effects on chemical

properties, despite the availability of a comprehensive review by P.Pyykko
[12]. There several good introductory articles on the derivation and
calculation of various relativistic effects in molecules and atoms, so I'm
not going to include details [13,14,15]. Suffice to say, that whilst
smaller elements can treated simply, larger elements need treatment based
on the Dirac equation, which shows that the s electrons are approaching
the speed of light, consequently relativistic effects are important.
If we take the relativistic mass of mercury (m);-
Mo where
m = -------------------- c (speed of light) = ~137 atomic units
_____________ v = Z = 80
/ ( v ) 2 Mo = rest mass
/ 1 - ( - )
\/ ( c )
The masses of the 1s electrons are increased by approximately 20% over

their rest masses, which means that the radius is decreased by 20% - since
mass appears in the denominator of Bohr radius calculations. All the other
s shells also contract, with the 6s contracting ~14%, because their electron
speeds near the nucleus are comparable, and the contraction of the inner part
of the wave function also pulls in the outer tails. The p orbitals also
contract a similar amount, and these contractions also results in increases
the screening for d and f orbitals, which may then expand - about 3% for the
5d orbital of mercury.
In mercury, the relativistically-contracted 6s2 orbital is full, thus the

the two electrons do not contribute much to the metal-metal bond, which is
not the situation for gold. The bonding in mercury is believed to be mainly
van der Waals forces with a contribution from 6p orbital interaction. The
relativistic contraction of the filled 6s2 orbital, when added to the
contraction across the sixth row of the periodic table, results in relatively
weak Hg-Hg bonds that are responsible for mercury being a liquid at room
temperature. For those curious to know more, a recent article in J.Chem.Ed.
provides much more detail and several good references [16]. Relativistic
effects are also responsible for the colour of gold ( partially explained
by the 5d -> 6s transition in gold requiring less energy than the 4d -> 5s
transition in silver, resulting in a smaller d-s gap ) [12,14,16].
Subject: 20. Optical properties of chemicals
20.1 Refractive Index properties and terminology
When light passes between media of different density, the direction of the
beam is changed as it passes through the surface, and this is called
refraction. In the first medium, the angle between the light ray and the
perpendicular is called the angle of incidence (i), and the corresponding
angle in the second medium is called the angle of refraction (r). The
ratio sine i / sine r is called the index of refraction, and usually the
assumption is that the light is travelling from the less dense (air) to more
dense, giving an index of refraction that is greater than 1. Although the
theoretical reference is a vacuum, air ( 0.03% different ) is usually used.
The refractive index of a compound decreases with increasing wavelength
( dispersion ), except where absorption occurs, thus the wavelength should
be reported. The D lines of sodium are commonly used.
The refractive index of a liquid varies with temperature and pressure, but
the specific refraction ( Lorentz and Lorentz equation ) does not. The molar
refraction is the specific refraction multiplied by the molecular weight,
and is approximately an additive property of the groups or elements
comprising the compound. Tables of atomic refractions are available in the
literature, as are descriptions of the common types of refractometers [1].
20.2 Polarimetry properties and terminology
Supplied by: Vince Hamner <vinny@vt.edu>

Polarimetry is a method of chemical analysis that is concerned
with the extent to which a beam of linearly polarised light is rotated
during its transmission through a medium containing an optically active
species.[2] Helpful discussions regarding polarised light may be found
elsewhere.[3,4] In general, a compound is optically active if it has
no plane of symmetry and is not superimposable on its mirror image.
Such compounds are referred to as being "chiral". Sucrose, nicotine,
and the amino acids are only a few of these substances that exhibit
an optical rotary power.
A simple polarimeter instrument would consist of:
1). a light source -- typically set to 589 nm (the sodium "D" line)
2). a primary fixed linear polarising lens (customarily called the
"polariser")
3). a glass sample cell (in the form of a long tube)
4). a secondary linear polarising lens (customarily called the
"analyser") and
5). a photodetector.[5]
Biot is credited with the determination of the basic equation

of polarimetry.[6,7] The specific rotation of a substance (at a given
wavelength and temperature) is equivalent to the observed rotation (in
degrees) divided by the path length of the sample cell (in decimeters)
multiplied by the concentration of the sample (for a pure liquid,
-density- replaces concentration). Influences of temperature,
concentration, and wavelength must always be taken into consideration.
If necessary, it is possible to apply corrections for each of these
variables.[8] A few early contributors to our understanding of optical
activity and polarimetry include: Malus, Arago, Biot, Drude, Herschel,
Fresnel, and Pasteur.
Subject: 21. Molecular and Structural Modelling
Supplied by: Dave Young (young@slater.cem.msu.edu)
21.1 What hardware do I need to run modelling programs?
There are two types of programs that are referred to as molecular

modeling programs. This first is a program which graphically displays
molecular structures as Lewis structures, ball & stick, etc. The second
is a program which does a calculation to tell you something about the
molecule, such as it's energy, dipole moment, spectra, etc.
For an introductory description of various types of computations,

see http://www.cem.msu.edu/~young/topics/contents.html
There are many programs of both sorts available for a large range
of machines. The speed, memory, graphics and disk space on the machine
will determine the size of molecules that can be modelled, how accurate
the model is, and how good the images will look. There are a few programs
that will run on a 286 PC with Windows. There are some fairly nice things
that can be done on a 386 with about 8 MB of RAM and Windows. The
professional computational chemists are generally using work stations and
larger machines.
Currently many computational chemists are using machines made by

Silicon Graphics (SGI) ranging from the $5,000 Indy to the $1,000,000
power challenge machines. These are all running Irix, which is SGI's
adaptation of Unix. SGI is popular for two reasons; first that the power
is very good for the price, second that SGIs run the largest range
of chemical software. However, you will find some computational chemistry
software that can run on almost any machine.
As far as graphics quality, the SGI Onyx (about $250,000) is about

the top of the line. Even if you find a machine that claims to have better
graphics than this, chances are you won't find and chemistry software that
can utilise it.
For chemical calculations there is no limit to the computing

power necessary. There are some calculations that can only be done
on the biggest Crays or massively-parallel machines in the world. There
are also many calculations which are too difficult for any existing
machine and will just have to wait a few years or a few centuries.
21.2 Where can I find a free modelling program?
The single best place for public domain modelling software

is probably the anonymous FTP server at ccl.osc.edu in the directory
pub/chemistry/software. "ccl" stands for "computational chemistry
list server" and is a list frequented mostly by professional
computational chemistry researchers. This machine contains their
archives with quite a bit of information as well as software.
For work stations and larger, the program GAMESS (General Atomic
and Molecular Electronic Structure System) can be obtained as source
code from Mike Schmidt at mike@si.fi.ameslab.gov GAMESS is a quantum
mechanics, ab initio and semi-empirical program. It is powerful. but
not trivial to learn how to use.
The COLUMBUS program for work stations and larger can be obtained
by anonymous FTP from ftp.itc.univie.ac.at It is a HF, MCSCF and
multi-reference CI program. This is probably the most difficult program
to use that is in use today since it requires the user to input EVERY
detail manually. However, because you control everything there are some
calculations that can only be done with COLUMBUS.
CACAO is an extended Huckel program available by anonymous FTP

at cacao.issecc.fi.cnr.it
21.3 Where can I find structural databanks?
21.4 Where can I find ChemDraw or ChemWindows
For ChemDraw (Macintosh, Windows, UNIX)

CambridgeSoft Corporation
875 Massachusetts Avenue
Cambridge, MA 02139
Phone: (800) 315-7300 or (617) 491-2200
Fax: (617) 491-7203
Internet: info@camsci.com
http://www.camsci.com
For ChemIntosh or ChemWindows

SoftShell
1600 Ute Avenue
Grand Junction, CO 81501
Phone: (970) 242-7502
Fax: (970) 242-6469
Internet: info@softshell.com
http://www.softshell.com
Subject: 22. Spectroscopic Techniques
All of these are covered in texts on instrumental Analysis [1-4], and I

will eventually include a paragraph about each.
22.1 Ultra-Violet/Visible properties and terminology

22.3 Nuclear Magnetic Resonance properties and terminology
22.4 Mass Spectrometry properties and terminology
22.5 X-Ray Fluorescence properties and terminology
22.6 X-Ray Diffraction properties and terminology
22.7 Fluorescence/Phosphorescence properties and terminology
Subject: 23. Chromatographic Techniques
There are chromatography mailing lists and WWW sites available that provide
comprehensive introductions and access to chromatography experts. The
following are simple introductions to popular techniques.
23.1 What is Paper Chromatography?
Paper chromatography was the first analytical chromatographic technique

developed, allegedly using papyrus (Pliny). It was first published by Runge
in 1855, and consists of a solvent moving along filter or blotting paper.
The interaction between the components of the sample, the solvent, and the
paper, results in separation of the components. Most modern paper
chromatography is partition chromatography, where the cellulose of the
paper is the inert support, and the water adsorbed ( hydrogen bonded ) from
air onto the hydroxyl groups of the cellulose becomes the stationary phase.
If the mobile phase is not saturated with water, then some of the stationary
phase water may be removed from the cellulose - resulting in a separation
that is a mixture of partition and adsorption. Paper chromatography remains
the method of choice for a wide range of coloured compounds, and is used
extensively in both natural and artificial pigment research. The technique
is suitable for any molecules that are significantly less volatile than the
solvent, and many examples and references are provided in Heftmann [1].
23.2 What is Thin Layer Chromatography?
Thin layer chromatography involves the use of a particulate sorbant on an

inert sheet of glass, plastic, or metal. The solvent is allowed to travel
up the plate with the sample spotted on the sorbant just above the solvent.
Depending on the sorbant, the separation can be either partition or
adsorption chromatography ( cellulose, silica gel and alumina are commonly
used ). The technique came to prominence during the late 1930s, however it
did not become popular until Merck and Desaga developed commercial plates
that provided reproducible separations. The major advantage of TLC is the
disposable nature of the plates. Samples do not have to undergo the
extensive clean-up steps required for HPLC. The other major advantage is the
ability to detect a wide range of compounds cheaply, using very reactive
reagents ( iodine vapours, sulfuric acid ) or indicators. Non-destructive
detection ( fluorescent indicators in the plates, examination under a UV
lamp ) also means that purified samples can be scraped off the plate and
be analysed by other techniques. There are special plates for such
preparative separations, and there are also high-performance plates that can
approach HPLC resolution. The technique is described in detail in Stahl [2]
and Kirchner [3].
23.3 What is Gas Chromatography?
Gas chromatography is the use of a carrier gas to convey the sample ( as a

vapour ) through a column consisting of an inert support and a stationary
phase that interacts with sample components, thus it is usually partition
chromatography. There are also a range of materials, especially for permanent
gas and light hydrocarbon analysis that utilise adsorption. The simplest
partition systems consisted of a steel tube filled with crushed brick that
had been coated with a hydrocarbon that had a high boiling point, eg
squalane. Today, the technique uses very narrow fused silica tubes ( 0.1 to
0.3mm ID ) that have sophisticated stationary phase films ( 0.1 to 5um )
bonded to the surface and also cross-linked to increase thermal stability.
The ability of the film to retard specific compounds is used to ascertain

the "polarity" of the column. If benzene elutes between normal alkanes
where it is expected by boiling point ( midway between n-hexane and
n-heptane ), then the column is "non-polar" eg squalane and methyl silicones.
If the benzene is retarded until it elutes after n-dodecane, then the column
is "polar" eg OV-275 ( dicyanoallyl silicone ) and 1,2,3-tris (2-cyanoethoxy)
propane. In general, polar columns are less tolerant of oxygen and reactive
sample components, but the ability to select different polarity columns to
obtain satisfactory peak resolution is what has made GC so popular.
The column is placed in an oven that has exceptional temperature control,

and the column can be slowly heated up to 350-450C ( sometimes starting at
-50C to enhance resolution of volatile compounds ) to provide separation of
wide-boiling range compounds. The carrier gas is usually hydrogen or helium,
and the eluting compounds can be detected several ways, including flames
( flame ionisation detector ), by changes in properties of the carrier
( thermal conductivity detector ), or by mass spectrometry. The availability
of "universal" detectors such as the FID and MS, makes GC a popular tool in
laboratories handling organic compounds. There are also columns that have a
layer of 5-10 um porous particulate material (such as molecular sieve or
alumina ) bonded to the inner walls ( PLOT = Porous layer open tubular ),
and these are used for the separation of permanent gases and light
hydrocarbons. GC is restricted to molecules ( or derivatives ) that
are sufficiently stable and volatile to pass through the GC intact at the
temperatures required for the separation. Specialist books on the production
of derivatives for GC are available [4,5].
There are several manufacturers of GC instruments whose catalogues and

brochures provide good introduction to the technique. (eg Hewlett Packard,
Perkin Elmer, Carlo Erba ). The catalogues of suppliers of chromatography
consumables also contain explanations of the criteria for selection of the
correct columns and conditions for analyses, and they provide an excellent
indication of the range of applications available. Well-known suppliers
include Alltech Associates, Supelco, Chrompack, J&W, and Restek. They also
sell most of the standard GC texts, as do the instrument manufacturers.
Popular GC texts include "Basic Gas Chromatography" [6], "High-Resolution
Gas Chromatography" [7], and "Open Tubular Column Gas Chromatography" [8].
There are Standard Retention Index Libraries available [9], however they
really only complement unambiguous identification by mass spec. or
dual-column analysis.
23.4 What is Column Chromatography?

Column chromatography consists of a column of particulate material such as
silica or alumina that has a solvent passed through it at atmospheric or low
pressure. The separation can be liquid/solid (adsorption) or liquid/liquid
(partition). The columns are usually glass or plastic with sinter frits to
hold the packing. Most systems rely on gravity to push the solvent through.
The sample is dissolved in solvent and applied to the front of the
column. The solvent elutes the sample though the column, allowing the
components to separate based on adsorption ( alumina, hydroxyapatite) or
partition ( cellulose, diatomaceous earth ). The mechanism for silica
depends on the hydration. Traditionally, the solvent was non-polar and the
surface polar, although today there are a wide range of packings including
bonded phase systems. Bonded phase systems usually utilise partition
mechanisms rather than adsorption. The solvent is usually changed stepwise,
and fractions are collected according to the separation required, with the
eluted solvent usually monitored by TLC.
The technique is not efficient, with relatively large volumes of solvent

being used, and particle size is constrained by the need to have a flow of
several mls/min. The major advantage is that no pumps or expensive equipment
are required, and the technique can be scaled up to handle sample sizes
approaching a gram in the laboratory. The technique is discussed in detail
in Heftmann [1].
23.5 What is High Pressure Liquid Chromatography?
HPLC is a development of column chromatography. it was long realised that

using particles with a small particle size ( 3, 5, 10um ) with a very narrow
size distribution would greatly improve resolution, especially if the flow
rate and column dimensions could be adjusted to minimise band-broadening.
Pumps were developed that could handle both the chemicals and pressures
required. Traditional column chromatography ( nonpolar solvent and
polar surface ) is described as "normal" and, as well as silica, there are
columns with amino, diol, and cyano groups. If the system uses a polar
solvent ( water, methanol, acetonitrile etc. ) and a non-polar surface it
is described as "reverse-phase". Common surface treatments of silica include
octadecylsilane ( aka ODS or C18), and it has been the development of
reverse-phase HPLC that has experienced explosive growth. Reverse-phase HPLC
is the method of choice for larger non-volatile biomolecules, however it is
only recently that a replacement "universal" detector ( evaporative
light-scattering ) has emerged. The most popular detector (UV), places
constraints on the solvents that can be used, and the refractive index
detector can not easily be used with solvent gradients. There are several
excellent books introducing HPLC, including the classic "Introduction to
Modern Liquid Chromatography" [10]. HPLCs can be a pain to operate, and
novices should borrow "Troubleshooting LC Systems" by Dolan and Snyder [11].
There is also a handy basic primer on developing HPLC methods by Snyder and
Kirkland [12], however, unlike GC, you also need to search the journals
( Journal of Chromatography, Journal of Liquid Chromatography ) to find
relevant examples to assist with method development.
23.6 What is Ion Chromatography?
Ion chromatography has become the method of choice for measuring anions
( eg Cl-, SO4=, NO3- ) in aqueous solutions. It is effectively a development
from ion-exchange systems ( which were extensively developed to deionise
water and soften aqueous process streams ), and brings them down to HPLC
size. IC uses pellicular polymeric resins that are compatible with a wide pH
range. The sample is eluted through an ion-exchange column using a dilute
sodium hydroxide solution. The eluant is passed through self-regenerating
suppressors that neutralise eluant conductance, ensuring electrochemical
detectors ( conductivity or pulsed amperometric ) can detect the ions down
to sub-ppm concentrations. The major manufacturer of such systems is Dionex,
who hold several patents on column, suppression, and detection technology.
There are several books covering various aspects of the technique [13,14].
23.7 What is Gel Permeation Chromatography?
Gel Permeation chromatography ( aka Size Exclusion chromatography ) is based

on the ability of molecules to move through a column of gel that has pores of
clearly-defined sizes. The larger molecules can not enter the pores, thus
they pass quickly through the column and elute first. Slightly smaller
molecules can enter some pores, and so take longer to elute, and small
molecules can be delayed further. The great advantage of the technique is
simplicity, it is isocratic ( single solvent - no gradient programming ),
and large molecules rapidly elute. The technique can be used to determine
the molecular weight of large biomolecules and polymers, as well as
separating them from salts and small molecules. The columns are very
expensive and sensitive to contamination, consequently they are mainly used
in applications where alternative separation techniques are not available,
and sample are fairly clean. The best known columns are the Shodex
cross-linked polystyrene-divinylbenzene columns for use with organic solvents,
and polyhydroxymethacrylate gel filtration columns for use with aqueous
solvents. "Modern Size Exclusion Chromatography" [15], and Heftmann [1],
provide good overviews, and there are some good introductory booklets from
Pharmacia.
23.8 What is Capillary Electrophoresis?
Capillary electrophoresis uses a small fused silica capillary that has been
coated with a hydrophilic or hydrophobic phase to separate biomolecules,
pharmaceuticals and small inorganic ions. A voltage is applied and the
analytes migrate and separate according to their charge under the specific
pH conditions, as also happens for electrophoresis. The capillary can also
be used for isoelectric focusing of proteins. The use of salt or vacuum
mobilisation is no longer required.
23.9 How do I degas chromatographic solvents?
One major problem with pressurising chromatography systems using liquid

solvents is that pressure reductions can cause dissolved gases to come out
of solution. The two locations where this occurs are the suction side of the
pump ( which is not self-priming, consequently a gas bubble can sit in the
pump and flow is reduced ), and at the column outlet ( where the bubbles
then pass through the detector causing spurious signals). Note that the
problem is usually restricted to solvents that have relatively high gas
solubilities - usually involving an aqueous component, especially if a
gradient is involved where the water/organic solvent ratio is changing.
As water usually has a higher dissolved gas content, then a gradient
programme may cause the gases to come out of solution as the mobile phase
components mix.
There are three traditional strategies used to remove problem dissolved

gases from chromatographic eluants. Often they are used in combination to
lower the dissolved gases.
a. Subject the solvent to vacuum for 5-10 mins. to remove the gases.
b. Subject the solvent to ultrasonics for 10-15 mins. to remove the gases.
c. Sparge the solvent with a gas that has a very low solubility compared
to the oxygen and nitrogen from the atmosphere. Helium is the preferred
choice - 5 minutes of gentle bubbling from a 7um sinter is usually
sufficient, although maintaining a positive He pressure is even better.
Note that most aqueous-based solvents usually have to be degassed every
24 hours. Also remember that solubility of gases increases as temperature
decreases, so ensure eluants are at instrument temperature prior to
degassing. Helium is preferred as the degassing solvent because it has
relatively low solubility in water, and the solubility is less affected by
temperature.
The following data is from Kaye and Laby, 13th edition, and the units are
the number of cm3 of gas at 0C and 760 mmHg which dissolve in 1 cm3 of water
at the temperature stated ( when the gas is at 760 mmHg pressure and in
equilibrium with the water ).
Temp.(C) 0 10 20 30 40 50 60
Helium 0.0098 0.0091 0.0086 0.0084 0.0084 0.0086 0.0090
Hydrogen 0.0214 0.0195 0.0182 0.0170 0.0164 0.0161 0.0160
Nitrogen 0.0230 0.0185 0.0152 0.0133 0.0119 0.0108 0.0100
Oxygen 0.047 0.037 0.030 0.026 0.022 0.020 0.019
Argon 0.054 0.041 0.032 0.028 0.025 0.024 0.023
CO2 1.676 1.163 0.848 0.652 0.518 0.424 0.360
I've no explanation for the aberrant trend for helium at higher temperatures,
but I assume it's real - but it's irrelevant for HPLC solvents that are
usually stored at ambient temperature. Points to note - the lower solubility
of helium over the range of concern, *and* the lower rate of change of
decreasing solubility with increasing temperature. There is heat generated
in the compression of the solvent, along with friction in HPLC pump heads
and, more importantly, HPLC columns are often heated - thus the solvent
could outgas and form bubbles in UV detector cells that are at ambient.
By using helium, there is less chance of that happening. For example, if the
temperature increased from 10C to 40C, the undissolved gas volume would be
0.0007 cm3 for helium, and 0.0066 cm3 for nitrogen.
Modern HPLCs are sold with a "solvent degassing module" that removes
undissolved gases in the solvent automatically. These usually consist of
a tube made from gas-permeable membrane that passes through a vacuum
chamber.
23.10 What is chromatographic solvent "polarity"?
There are four major intermolecular interactions between sample and solvent
molecules in liquid chromatography, dispersion, dipole, hydrogen-bonding,
and dielectric. Dispersion interactions are the attraction between each pair
of adjacent molecules, and are stronger for sample and solvent molecules
with large refractive indices. Strong dipole interactions occur when both
sample and solvent have permanent dipole moments that are aligned. Strong
hydrogen-bonding interactions occur between proton donors and proton
acceptors. Dielectric interactions favour the dissolution of ionic
molecules in polar solvents. The total interaction of the solvent and
sample is the sum of the four interactions. The total interaction for a
sample or solvent molecule in all four ways is known as the "polarity" of
the molecule. Polar solvents dissolve polar molecules and, for normal
phase partition chromatography, solvent strength increases with solvent
polarity, whereas solvent strength decreases with increasing polarity
in reverse-phase systems. The subject is discussed in detail in Snyder
and Kirkland [10].
------------------------------
Subject: 24. Extraction Techniques
24.1 What is Solvent Extraction?

Solvent extraction is usually used to recover a component from either a solid
or liquid. The sample is contacted with a solvent that will dissolve the
solutes of interest. Solvent extraction is of major commercial importance
to the chemical and biochemical industries, as it is often the most efficient
method of separation of valuable products from complex feedstocks or
reaction products. Some extraction techniques in involve partition between two
immiscible liquids, others involve either continuous extractions or batch
extractions. Because of environmental concerns, many common liquid/liquid
processes have been modified to either utilise benign solvents, or move to
more frugal processes such as solid phase extraction. The solvent can be a
vapour, supercritical fluid, or liquid, and the sample can be a gas, liquid
or solid. There are a wide range of techniques used, and details can be found
in Organic Vogel, Perry, and most textbooks on unit operations.
24.2 What is Solid Phase Extraction?
Solid Phase Extraction (SPE) is an alternative to liquid/liquid extraction,

and has become the method of choice for the separation and purification of
a wide range of samples in the laboratory. The sample is usually dissolved
in an appropriate solvent and passed through a small bed of adsorbent of
very consistent particle size and shape to maximise separation efficiency.
The compounds are eluted with step changes of small volumes of solvents.
The major advantage is that solvent volumes are greatly reduced. There is
a newer, modified technique that is used in analytical laboratories, called
Solid Phase Micro Extraction. This immerses a fused silica fibre coated with
a stationary phase into the sample solution for several minutes, The analytes
adsorb onto the stationary phase, which is subsequently pushed into a hot GC
injector to rapidly desorb the sample for analysis.
24.3 What is Supercritical Fluid Extraction?
Refer to Section 19.3 for some critical data on common supercritical fluids.
Supercritical fluids have been investigated since last century, with the
strongest commercial interest initially focusing on the use of supercritical
toluene in petroleum and shale oil refining during the 1970s. Supercritical
water is also being investigated as a means of destroying toxic wastes, and
as an unusual synthesis medium [1]. The biggest interest for the last decade
has been the applications of supercritical carbon dioxide, because it has
a near-ambient critical temperature (31C), thus biological materials can
be processed at temperatures around 35C. The density of the supercritical
CO2 at around 200bar pressure is close to that of hexane, and the solvation
characteristics are also similar to hexane, thus it acts as a non-polar
solvent. Around the supercritical region CO2 can dissolve triglycerides at
concentrations up to 1% mass. The major advantage is that a small reduction
in temperature, or a slightly larger reduction in pressure, will result in
almost all of the solute precipitating out as the supercritical conditions
are changed or made subcritical. Supercritical fluids can produce a
product with no solvent residues. Examples of pilot and production scale
products include decaffeinated coffee, cholesterol-free butter, low-fat meat,
evening primrose oil, squalene from shark liver oil. The solvation
characteristics of supercritical CO2 can be modified by the addition of an
entrainer, such as ethanol, however some entrainer remains as a solvent
residue in the product, negating some of the advantages of the "residue-free"
extraction.
There are other near-ambient temperature supercritical fluids, including

nitrous oxide and propane, however there are safety issues with some of them.
There are several introductory texts on supercritical fluid extraction,
including some the ACS Symposium series [2-4]. There are also a large
number of articles on applications of the technique, including processing [5],
extraction of natural products [6], and chemical synthesis [7]. The major
concentration of information occurs in the various proceedings of the
International Symposium on Supercritical Fluids [8]. There is also a Journal
of Supercritical Fluids.
24.4 What traditional process extracted perfume from flower petals?
The traditional cold-fat extraction process is known as " enfleurage".

It is a very interesting, historical process used to obtain the essential
oils and perfume components from rose, jasmine, and other flowers. The
rose and jasmine flowers continue to produce perfume during the long
process. Thus the technique can obtain more perfume from those flowers than
if they were just macerated and extracted by hot fat, solvent or steam
when they were picked - as happens to many other plant perfume sources.
The process uses a fat comprised of 40 parts of beef tallow and 60 parts
of lard. The two fats are melted together, and repeatedly beaten under
cold water and alum solutions to purify them. Benzoin is added to the
fat mixture to prevent biological degradation.
The fat is spread about 4mm thick on both sides of 0.5 x 0.5 metre glass
plates in wooden frames. Flowers are pressed into the fat on one side of
the frame only, and the frames stacked vertically so that the flowers are
very close to the layer of fat on the frame above. After 1-3 days, the
flowers are stripped off and fresh flowers added to the other layer of fat
that had not been used, and the frame are again stacked. The cycle is
repeated about 30 - 35 times, or until the fat is saturated with perfume.
The saturated fat is known as "pomade". The fat is removed from the frames
and extracted with alcohol to collect the perfume. the alcohol is cooled
and filtered to remove most of the dissolved fat. The alcohol solution
is called the "extract", and the residue after evaporation of the solvent
is known as the "enfleurage absolute".

topic!
knowledge

Date: Thu, 15 Jan 2004 22:12:19 +1300
Message-ID: <jamc00dq37vc96orlc4s5qfmk7bbmenjf5@4ax.com>
Version: 1.17
Subject: 26. Electrochemical Techniques
26.1 What is pH?
The pH scale determines the degree of acidity or alkalinity of a solution,

but as it involves a single ion activity it can not be measured directly.
pH = - log10 ( gamma H x m H )
where gamma H = hydrogen ion single ion activity coefficient

m H = molality of the hydrogen ion.
As pH can not be directly measured, it is defined operationally according to

the method used to determine it. IUPAC recommend several standardised methods
for the determination of pH in solution in aqueous solutions. There are
seven primary reference standards that can be used, including 0.05 mol/kg
potassium hydrogen phthalate as the Reference Value Standard. There is an
ongoing debate concerning the relative merits of having a multiple primary
standard scale ( that defines pH using several primary standards, and their
values are determined using a cell without a liquid junction ) or a single
primary standard ( that requires a cell with a liquid junction ). Interested
readers can obtain further information on the debate in [1]. Bates [2], is a
popular text covering both theory and practise of pH measurement.
26.2 How do pH electrodes work?
Contributed by Paul Willems <Paul.Willems@rug.ac.be>, and slightly modified

by Bruce Hamilton.
The most common type of pH electrodes are the "glass" electrodes. They
consist of a special glass membrane that is sensitive to variations in pH,
as pH variation also changes the electrical potential across the glass. In
order to be able to measure this potential, a second electrode, the
"reference" electrode, is required. Both electrodes can be present in a
"combined" pH electrode, or two physically-separate electrodes can be used.
The glass electrode consists of a glass shaft on which a bulb of a special

glass is mounted. The inner is usually filled with 3 Mol/Litre aqueous KCl
and sealed. Electrical contact is provided by a silver wire immersed in the
KCl.
For "combined" electrodes, the glass electrode is surrounded by a concentric

reference electrode. The reference electrode consists of a silver wire in
contact with the almost-insoluble AgCl. The electrical contact with the meter
is through the silver wire. Contact with the solution being measured is via
a KCl filling solution. To minimise mixing of the solution to be measured and
the filling solution, a porous seal, the diaphragm, is used. This is usually
a small glass sinter, however other methods which allow a slow mixing contact
can also be used, especially for samples with low ionic strength. Besides the
"normal" KCl solutions, often solutions with an increased viscosity, and
hence lower mixing rate are used. A gel filling can also be used, which
eliminates the necessity for slow mixing devices.
In contact with different pH solutions a typical glass electrode gives, when

compared to the reference electrode, a voltage of about 0 mV at pH 7,
increasing by 59 mV per pH unit above 7, or decreasing by 59 mV per pH unit
below 7. Both the slope, and the intercept of the curve between pH and
generated potential, are temperature dependent. The potential of the
electrode is approximated by the Nernst equation :
E = E0 - RT log [H+] = E0 + RT pH
Where E is the generated potential, E0 is a constant, R is universal
gas constant and T is the temperature in degrees Kelvin.
All pH-sensitive glasses are also susceptible to other ions, such as Na or K.

This requires a correction in the above equation, so the relationship between
pH and generated voltage becomes nonlinear at high pH values. The slope tends
to diminish both as the electrode ages, and at high pH. As the electrode has
a very high impedance, typically 250 Megohms to 1 Gigohm, it is necessary to
use a very high impedance measuring instrument.
The reference electrode has a fairly constant potential, but it is

temperature dependent, and also varies with activity of the silver ions in
the reference electrode. This occurs if a contaminant enters the reference
electrode.
Calibration
From the preceding, it is obvious that frequent calibration and adjustment of

pH meters are necessary. To check the pH meter, at least two standard buffer
solutions are used to cover the range of interest. The pH meter should be
on for at least 30 minutes prior to calibration to ensure that all components
are at thermal equilibrium, and calibration solutions should be immersed for
at least a minute to ensure equilibrium.
First use the buffer at pH 7, and adjust the zero (or the intercept).
Then, after thorough rinsing with water, use the other buffer to adjust the
slope. This cycle in repeated at least once, or until no further adjustments
are necessary. Many modern pH meters have an automatic calibration feature,
which requires each buffer only once.
Errors
People assume pH measurements are accurate, however many potential errors

exist. There can be errors caused by the pH-sensitive glass, reference
electrode, electrical components, as well as externally generated errors.
Glass Electrode Errors
The pH-sensitive glass can be damaged. Major cracks are obvious, but minor
damage can be difficult to detect. If the internal liquid of the pH-measuring
electrode and the external environment are connected, a pH value close to 7
will be obtained. It will not change when the electrode is immersed in a
known solution of different pH. The electrical resistance of the glass
membrane will also be low, often below 1 megohm, and it must be replaced.
Similar results occur if the glass wall between the inner and outer part of
a combined electrode breaks. This may occur if the outer part is plastic.
The inner part can crack without any external signs. The electrical
resistivity over the glass electrode is intact, but actual measuring between
both electrodes reveals a low resistivity. The electrode must be replaced.
The glass can wear out. This gives slow response times, as well as a lower
slope for the mV versus pH curve. To rejuvenate, immerse the electrode in a
3 Molar KCl solution at 55 degrees Celsius for 5 hours. If this does not
solve the problem, try removing a thin layer of the glass by immersion for
two minutes in a mixture of HCl and KF (be careful, do not breathe the fumes,
and wear gloves). The electrode is then immersed for two more minutes in HCl,
and rinsed thoroughly. As an outer layer of glass has been removed, the new
surface will be like a new electrode, however the thinner glass will result
in a shorter electrode life. Frequent recalibration will be required for
several days.
The glass can be dirty. A deposit on the glass will slow the response time,
make the response sensitive to agitation and ionic strength, and also give
the pH of the film, not the sample solution. If the deposit is known, use a
appropriate solvent to remove it, and rehydrate the electrode in 3M KCl.
If the deposit is not known, first immerse the electrode for a few minutes
in a strongly alkaline solution, rinse thoroughly, and immerse it in a
strong acid (HCl) solution for several minutes. If this does not help, try
using pepsin in HCl. If still unsuccessful, use the above HCl/KF method.
Reference Electrode Errors
The diaphragm of the reference can become blocked. This is seen as unstable
or wrong pH measurements. If the electrical resistivity of the diaphragm is
measured, high values are reported (Most multimeters will give an over-range
error). The most common reason is that AgS formed a precipitate in the
diaphragm. The diaphragm will be black in this case. The electrode should be
immersed in a solution of acidic thiourea until the diaphragm is white, and
then replace the internal filling liquid of the reference electrode
There is no contact across the diaphragm, due to air bubbles. This appears
as if the diaphragm were blocked, except that the diaphragm is white. Ensure
that the filling solution level in the reference electrode is always well
above the sample, so that liquid is always slowly flowing from the reference
electrode towards the sample.
The electrode filling solution is contaminated. This appears as unstable or

wrong pH measurements. Often the 0mV pH differs considerably from pH 7. The
diaphragm has its normal colour and the electrical resistivity is normal.
However, the solution often becomes contaminated due to low filling solution
levels, and air bubbles may also appear in the diaphragm, which obviously
affects electrical resistivity. Replacing the reference filling solution
several times should solve the problem, but the electrode may have been
permanently damaged. The problem can be avoided by choosing gel-filled
reference electrodes, double-junction electrodes, or ensuring there is an
outflow of reference filling solution towards the sample.
The electrode was filled with the wrong reference solution. This appears as
as displaced pH measurements. Flush and replace the reference liquid.
Electrical errors
Condensation or sample contamination of the electrode connecting cable. This

appears as an almost-constant measurement of about pH 7, even when the pH
electrode is disconnected from the cable, or as a pH which changes less than
it should, when tested with two standard solutions. If the cable is
disconnected from the meter, the pH will start to drift.
There is a short circuit in the cable. The symptoms are similar to the above
case, except that bending the cable may create sharp, spurious readings. In
most pH cables, between the two copper conductors there are two layers which
appear to be insulators. The inner layer is an insulator, whereas the outer
layer is a conductor to avoid trace electrical effects. If this outer layer
does contact the inner conductor, there will be a short circuit. Replace
suspect cables.
The input stage of the meter is contaminated with conducting liquid. The
symptoms are the same as above, except that removing the cable has no
effect. Closely examine the input stage of the meter for liquid or deposits.
If present, rinse with distilled water, then ethanol, and dry thoroughly.
The input stage of the meter is faulty. This gives random measurements.
Shorting both input wires does not make any difference. Repair the meter.
The input stage appears faulty. Shorting both input wires gives a stable
pH measurement of about 7. The meter may be faulty, but probably the problem
is elsewhere in the electrical circuit.
Externally-generated Errors
If a significant flow of liquid passes the electrode, then there can

be a minor electrical effect. This generates a potential on the glass
membrane, which is superimposed on the actual pH measurement. This effect
becomes negligible for highly-conducting liquids. It is seldom observed.
If the trace electric effect does influence pH measurements, the addition
of a little salt to increase the conductivity, or changing the flux of
liquid around the electrode, should solve the problem.
Ground loops and spurious electrical currents may generate unexpected

electrical signals. Such signals can strongly influence pH measurements.
A pH reading in the range of -15 to +20 is possible, even if the pH is 7.
Ground loops can be eliminated by grounding the system according to the
manufacturer's instructions, and ensuring insulation is in good condition.
Often these problems can be extremely difficult to detect and remedy.
Low ionic strength samples can be affected by electrolyte from the electrode,
and special electrodes are available.
26.3 What are ion-selective electrodes?
Ion selective electrodes are electrochemical sensors whose potential varies

with the logarithm of the activity of an ion in solution. Available types:
1. The membrane is a single compound, or a homogeneous mixture of compounds.
2. The membrane is a thin glass whose chemical composition determines the
response to specific ions.
3. The support, containing an ionic species, or uncharged species, forms the
membrane. The support can be solid or porous.
Popular texts on applications of ion-selective electrodes include
"Ion-Selective Electrodes in Analytical Chemistry" [3], and "Ion-selective
Electrode Methodology" [4].
26.4 Who supplies pH and ion-selective electrodes?
The best known manufacturer of ion-selective electrodes is Orion Research.

There are several pH electrode manufacturers, including Radiometer and
Metrohm.
Subject: 27. Fuel Chemistry
27.1 Where does crude oil come from?.
The generally-accepted origin of crude oil is from plant life up to 3

billion years ago, but predominantly from 100 to 600 million years ago [1].
"Dead vegetarian dino dinner" is more correct than "dead dinos".
The molecular structure of the hydrocarbons and other compounds present
in fossil fuels can be linked to the leaf waxes and other plant molecules of
marine and terrestrial plants believed to exist during that era. There are
various biogenic marker chemicals such as isoprenoids from terpenes,
porphyrins and aromatics from natural pigments, pristane and phytane from
the hydrolysis of chlorophyll, and normal alkanes from waxes, whose size
and shape can not be explained by known geological processes [2]. The
presence of optical activity and the carbon isotopic ratios also indicate a
biological origin [3]. There is another hypothesis that suggests crude oil
is derived from methane from the earth's interior. The current main
proponent of this abiotic theory is Thomas Gold, however abiotic and
extraterrestrial origins for fossil fuels were also considered at the turn
of the century, and were discarded then. A large amount of additional
evidence for the biological origin of crude oil has accumulated, however
Professor Gold still actively promotes his theory worldwide, even though
it does not account for the location and composition of all crude oils.
27.2 What are CNG/LPG/gasoline/kerosine/diesel?.
Crude oil consists mainly of hydrocarbons with carbon numbers between one and
forty. The petroleum refinery takes this product and refines it into several
fuel fractions that are optimised for their intended application. For spark
ignition engines, the very volatile and branched chain alkane hydrocarbons
have desirable combustion properties, and several fractions are produced.
CNG ( Compressed Natural Gas ) is usually around 70-90% methane with 10-20%
ethane, 2-8% propanes, and decreasing quantities of the higher HCs up to
pentane. The major disadvantage of compressed gaseous fuels is the reduced
range. Vehicles may have between one to three cylinders ( 25 MPa, 90-120
litre capacity), and they usually provide about 50% of the gasoline range.
LPG ( Liquefied Petroleum Gas ) is predominantly propane with iso-butane

and n-butane. It has one major advantage over CNG, the tanks do not have
to be high pressure, and the fuel is stored as a liquid. The fuel offers
most of the environmental benefits of CNG, including high octane - which
means higher compression, more efficient, engines can be used. Approximately
20-25% more fuel than gasoline is required, unless the engine is optimised
( CR 12:1 ) for LPG, in which case there is no decrease in power or any
significant increase in fuel consumption [4,5].
Gasoline contains over 500 hydrocarbons that may have between 3 to 12

carbons, and gasoline used to have a boiling range from 30C to 220C at
atmospheric pressure. The boiling range is narrowing as the initial boiling
point is increasing, and the final boiling point is decreasing, both
changes are for environmental reasons. A detailed description of the
composition of gasoline, along with the properties and compositions of CNG,
LPG, and oxygenates can be found in the Gasoline FAQ, which is posted monthly
to rec.autos.tech.
Kerosine is a hydrocarbon fraction that typically distils between 170-270C

(narrow cut kerosine, or Jet A1) or 100-250C ( wide cut kerosine, or JP-4 ).
It contains around 20% of aromatics, however the aromatic content will be
reduced for high quality lighting kerosines, as the aromatics reduce the
smoke point. The major use for kerosines today is as aviation turbine (jet)
fuels. Special properties are required for that application, including high
flash point for safe refuelling ( 38C for Jet A1 ), low freezing point for
high altitude flying ( -47C for Jet A1 ), and good water separation
characteristics. Details can be found in any petroleum refining text and
Kirk Othmer.
Diesel is used in compression ignition engines, and is a hydrocarbon fraction

that typically distils between 250-380C. Diesel engines use the Cetane
(n-hexadecane) rating to assess ignition delay. Normal alkanes have a high
cetane rating, ( nC16=100 ) whereas aromatics ( alpha methylnaphthalene = 0 )
and iso-alkanes ( 2,2,4,4,6,8,8-hexamethylnonane = 15 ) have low ratings,
which represent long ignition delays. Because of the size of the hydrocarbons,
the low temperature flow properties control the composition of diesel, and
additives are used to prevent filter blocking in cooler temperatures. There
are usually summer and winter grades. Environmental legislation is reducing
the amount of aromatics and sulfur permitted in diesel, and the emission of
small particulates ( diameters of <10um ) that are considered possibly
carcinogenic, and are known to cause other adverse health effects. Details
can be found in any petroleum refining text and Kirk Othmer.
27.3 What are oxygenates?.
Oxygenates are just pre-used hydrocarbons :-). They contain oxygen, which can
not provide energy, but their structure provides a reasonable anti-knock
value, thus they are good substitutes for aromatics, and they may also reduce
the smog-forming tendencies of the exhaust gases [6]. Most oxygenates used
in gasolines are either alcohols ( Cx-O-H ) or ethers (Cx-O-Cy), and contain
1 to 6 carbons. Alcohols have been used in gasolines since the 1930s, and
MTBE was first used in commercial gasolines in Italy in 1973, and was first
used in the US by ARCO in 1979. The relative advantages of aromatics and
oxygenates as environmentally-friendly and low toxicity octane-enhancers are
still being researched.
Ethanol C-C-O-H C2H5OH
C
|
Methyl tertiary butyl ether C-C-O-C C4H9OCH3
(aka tertiary butyl methyl ether ) |
C
They can be produced from fossil fuels eg methanol (MeOH), methyl tertiary
butyl ether (MTBE), tertiary amyl methyl ether (TAME), or from biomass, eg
ethanol(EtOH), ethyl tertiary butyl ether (ETBE)). MTBE is produced by
reacting methanol ( from natural gas ) with isobutylene in the liquid phase
over an acidic ion-exchange resin catalyst at 100C. The isobutylene was
initially from refinery catalytic crackers or petrochemical olefin plants,
but these days larger plants produce it from butanes.
Oxygenates have significantly different physical properties to hydrocarbons,

and the levels that can be added to gasolines are controlled by the EPA in
the US, with waivers being granted for some combinations. Initially the
oxygenates were added to hydrocarbon fractions that were slightly-modified
unleaded gasoline fractions, and these were commonly known as "oxygenated"
gasolines. In 1995, the hydrocarbon fraction was significantly modified, and
these gasolines are called "reformulated gasolines" ( RFGs ). The change to
reformulated gasoline requires oxygenates to provide octane, but also that
the hydrocarbon composition of RFG must be significantly more modified than
the existing oxygenated gasolines to reduce unsaturates, volatility, benzene,
and the reactivity of emissions.
Oxygenates that are added to gasoline function in two ways. Firstly they
have high blending octane, and so can replace high octane aromatics
in the fuel. These aromatics are responsible for disproportionate amounts
of CO and HC exhaust emissions. This is called the "aromatic substitution
effect". Oxygenates also cause engines without sophisticated engine
management systems to move to the lean side of stoichiometry, thus reducing
emissions of CO ( 2% oxygen can reduce CO by 16% ) and HC ( 2% oxygen can
reduce HC by 10%)[7]. However, on vehicles with engine management systems,
the fuel volume will be increased to bring the stoichiometry back to
the preferred optimum setting. Oxygen in the fuel can not contribute
energy, consequently the fuel has less energy content. For the same
efficiency and power output, more fuel has to be burnt, and the slight
improvements in combustion efficiency that oxygenates provide on some
engines usually do not completely compensate for the oxygen.
There are huge number of chemical mechanisms involved in the pre-flame

reactions of gasoline combustion. Although both alkyl leads and oxygenates
are effective at suppressing knock, the chemical modes through which they
act are entirely different. MTBE works by retarding the progress of the low
temperature or cool-flame reactions, consuming radical species, particularly
OH radicals and producing isobutene. The isobutene in turn consumes
additional OH radicals and produces unreactive, resonantly stabilised
radicals such as allyl and methyl allyl, as well as stable species such as
allene, which resist further oxidation [8,9].
The major concern with oxygenates is no longer that they may not be
effective at reducing atmospheric pollution, but that their greater water
solubility, and very slow biodegradability, can result in groundwater
pollution that may be difficult to remove. Their toxicological and
environmental effects are also still being researched.
27.4 What is petroleum ether?.
Petroleum ether ( aka petroleum spirits ) is a narrow alkane hydrocarbon

distillate fraction from crude oil. The names "ether" and "spirit" refer
to the very volatile nature of the solvent, and petroleum ether does not
have the ether ( Cx-O-Cy ) linkage, but solely consists of hydrocarbons.
Petroleum ethers are defined by their boiling range, and that is typically
20C. Typical fractions are 20-40C, 40-60C, 60-80C, 80-100C, 100-120C etc.
up to 200C. There are specially refined grades that have any aromatic
hydrocarbons removed, and there are specially named grades, eg pentane
fraction (30-40C), hexane fraction (60-80C, 67-70C). It is important to
note that most "hexane" fractions are mixtures of hydrocarbons, and pure
normal hexane is usually described as "n-hexane".
27.5 What is naphtha?.
Naphtha is a refined light distillate fraction, usually boiling below 250C,

but often with a fairly wide boiling range. Gasoline and kerosine are the
most well-known, but there are a whole range of special-purpose hydrocarbon
fractions that can be described as naphtha. The petroleum refining industry
calls the 0-100C fraction from the distillation of crude oil "light virgin
naphtha" and the 100-200C fraction " heavy virgin naphtha". The product
stream from the fluid catalytic cracker is often split into three fractions,
<105C = "light FCC naphtha", 105-160C = "intermediate FCC naphtha" and
160-200C "heavy FCC naphtha".
27.6 What are white spirits?.
White spirits are petroleum fractions that boil between 150-220C. They can
have aromatics contents between 0-100%, and Shell lists eight grades with
aromatics contents below 50%, and six grades with aromatics contents above
50%. The two common "white spirits" are defined by British Standard 245,
which states Type A should have aromatics content of less that 25% v/v and
Type B should have an aromatics content of 25-50% v/v. The most common
" white spirit" is type A, and it typically has an aromatics content of
20%, boils between 150-200C, and has an aniline point of 58C, and is
sometimes known as Low Aromatic White Spirits. The next most common is
Mineral Turpentine (aka High Aromatic White Spirits ), which typically has
an aromatics content of 50%, boils between 150-200C and has an aniline
point of 25C. For safety reasons, most White Spirits have Flash Points
above ambient, and usually above 35C. Note that "white gas" is not white
spirits, but is a volatile gasoline fraction that has a flash point below
0C, which is also known by several other names. Do not confuse the two
when purchasing fuel for camping stoves and lamps, ensure you purchase the
correct fuel.
27.7 What are biofuels?.

Biofuels are produced from biomass ( land and aquatic vegetation, animal
wastes, and photosynthetic organisms ), and are thus considered renewable
within relatively short time-frames. Examples of biofuels include wood,
dried animal dung, methyl esters from triglyceride oils, and methane from
land-fills. The renewable aspect of most biofuels is essentially the use
of solar energy to grow crops that can be converted to energy. There is
a large monograph "Fuels from Biomass" in Kirk Othmer, and the subject
is frequently discussed in alt.energy.renewable, sci.energy, and
sci.energy.hydrogen.
27.8 How can I convert cooking oil into diesel fuel?.
Diesel engines can run on plant and animal triglycerides such as tallow
and seed oils, however most trials have resulted in reduced engine life, or
increased service costs. The solution is to transesterify the triglycerides
into esters, taking care to avoid the formation of monoacylglycerides
that will precipitate out at low temperatures or when diesel is encountered.
There are several plants in Austria that produce Rapeseed Oil Methyl Esters
as fuels for diesel engines. The economics of the process are very
dependant on the price of diesel and the market for the glycerol byproduct.
The common catalysts used to transesterify triglycerides are sodium

hydroxide, sodium methoxide and potassium carbonate. If the esters are to
be blended with diesel fuel, then a two stage reaction is usually required
to ensure that monoacylglycerides are kept below 0.05%. Usually this
involves using 22g of methanol ( containing 0.6g of sodium hydroxide ) and
100g of tallow refluxed for 30 minutes. The mixture is cooled, the glycerol
layer removed, and a further 0.2g of sodium hydroxide is reacted for 5
minutes at 35C in a stirred reactor. The glycerol phase is allowed to
separate, and the ester phase is washed with water to remove residual
catalyst, glycerol and methanol. Note that sodium hydroxide is the most
cost-effective catalyst, but also has the worst tendency to form soaps.
The catalyst and methanol can be of industrial grade without further
purification required, however care should be taken to prevent additional
water entering the reaction [10].
The fuel can be converted into other esters, such as ethyl and butyl, but
it really depends on the availability of cheap alcohol along with the
desired properties of the fuels. The effect of catalysts, reagent ratio,
temperature, and moisture on the production of methyl, ethyl, and butyl
esters from some common oils has been investigated [11]. The New Zealand
government investigated a wide range of techniques for turning various
vegetable and animal triglycerides into esters for diesel, and the reports
cover many aspects of the kinetics and efficiencies [12]. There is a general
overview of the current processes and technology available in Inform [13].
A specific technique for analysing the monoglycerides has been published
[14], however I have found that acetylation followed by narrow bore
( 0.1mm ID ) capillary chromatography is faster and cheaper.
Subject: 28. Pharmaceutical Chemistry
28.1 Does Thalidomide racemise in humans?.
Thalidomide ( N-phthaloyl-alpha-aminoglutarimide ) is well known as an

enantiomeric sedative-hypnotic drug that caused tragic birth defects in
the early 1960s. It has often been claimed that the defects were caused by
the presence of the other isomer in the production batches, and if the pure
enantiomer had been sold, then the tragic defects would have been avoided.
Unfortunately, thalidomide is optically unstable in solution; the pure

isomers of thalidomide racemise by the opening of the phthalimide ring, with
half-lives of 4-5 hours in buffer at pH 7.4, and less than 10 minutes in the
blood. Thus shortly after administration of either enantiomer, the other
enantiomer will be present in significant quantities [1].
Some recent work has revealed that thalidomide inhibits the production of
tumour necrosis factor alpha. Elevated levels of TNF-alpha are associated
with several inflammatory conditions. This has led to the development of
analogues that are chirally stable in reconstituted human plasma, and which
are undergoing development as anti-inflammatory drugs [2].
Subject: 29. Adhesive Chemistry
Subject: 30. Polymer Chemistry
30.1 How can I simply identify common plastics?.
Read the recycle code :-). Alternatively, give it to the nearest IR

spectroscopist who has a polymer library. But if you want some fun, try the
following.
There are several simple tests that can be performed in the home that can
assist in separating common plastics, however it is important to realise that
formulated products contain large quantities of pigments, plasticisers, and
fillers that can dramatically alter the following properties. If possible
repeat the tests on a reference sample of the plastic.
a. Visually examine the sample, looking for recycle codes :-)

While you are at it, you can check for indications of how the plastic
was made - moulded, injected, rolled, machined etc.
b. Try assessing the flexibility by bending, and look at the bending zone
- does the material stretch or is it brittle?
c. Test the hardness, try scratching it with pencils of differing hardness
( B,HB,1-6H ) to ascertain which causes a scratch in the plastic.
Alternatively, attempt to scuff the sample with a fingernail.
d. Cut a small slither with a sharp knife. Does the sample cut cleanly
( thermoplastic )?, or does it crumble ( thermosetting )?.
e. Hold sample in small flame, note whether it burns, self-extinguishes on
removal from the flame, colour of the flame, and smell/acrid nature of
fumes when flame is blown out ( Caution - the fumes are likely to be
toxic ). Also attempt to press melted sample against a cold surface, and
pull away - does sample easily form long threads.
f. Drop onto a hard surface, does the sample "ring" or "thud"?
g. Place it in water. Does it float, sink slowly, or sink rapidly?
If it sinks rapidly, it is likely to be halogenated ( PVC, Viton, PTFE )
If it sinks slowly, possibly nylon
If it floats possibly polyethylene or polypropylene.
- you can ascertain the actual density by adding measured volumes of a
low density solvent like methanol until the sample neither rises nor
sinks.
Cutting thin slivers results in powdery chips ( thermosetting )

- carbolic smell in flame, self extinguishing = phenol formaldehyde
- self extinguishing, black smoke, acrid = epoxide
- fishy smell = urea formaldehyde, or melamine formaldehyde
cutting thin slivers results in smooth sliver ( thermoplastic )

- metallic "ring", burns (styrene smell) = polystyrene
(note that high impact polystyrene may not give "ring" )
- "thud", floats, hard, glossy surface, burns (paraffin wax smell) =
polypropylene
- "thud", floats, medium-hard surface, burns (sealing wax smell) =
high density polyethylene
- "thud", floats, soft surface, burns (paraffin wax smell) =
low density polyethylene
- "thud", sinks, burns ( fruity smell ) = acrylic
- "thud", sinks, burns ( burning paper smell ) = cellulose acetate or
propionate.
- "thud", sinks, burns ( rancid butter smell ) = cellulose acetate butyrate
- "thud", sinks, difficult to ignite ( greenish tinge ) = PVC
- "thud", sinks, difficult to ignite ( yellow colour, formaldehyde smell )
= polyacetal
- "thud", sinks, difficult to ignite ( yellow colour, weak smell ), draws
into long threads = Nylon
- "thud", sinks, difficult to ignite ( minimal flame, decomposition but no
charring, cellular structure forms = polycarbonate.
30.2 What do the plastics recycling codes mean?.
The recycle codes for plastics are currently being reviewed, and new codes
( probably inside a totally different symbol ) will soon be introduced.
1 = PET
2 = High density polyethylene
3 = Vinyl
4 = Low density polyethylene
5 = Polypropylene
6 = Polystyrene
7 = Others, including multi-layer
Subject: 31. Others
31.1 How does remote sensing of chemical pollutants work?.
The are several techniques, but the one of most interest to the public is
the system being used to identify grossly polluting vehicles. The system
consists of an infra-red source on one side of the road, and a detector
system on the other. The collimated beam of IR is directed at a gas filter
radiometer equipped with two liquid-nitrogen-cooled indium antimide
photovoltaic detectors. The beam is split, and passes through a 4.3um
bandpass filter to isolate the CO2 spectral region, a 4.6um filter to
isolates the CO region, and a third filter to isolate the HC region.
A non-absorbing region is also used to compensate for signal strength.
There are various specific enhancements, such as the spinning gas-filter
correlation cell in the University of Denver FEAT ( Fuel Efficiency
Automobile Test ) system used to cost-effectively identify grossly-polluting
vehicles [1]. "Optical remote sensing for air pollutants - review " by
M.Simonds et al [2], provides a good introduction to the diverse range of
instruments used for remote sensing of pollutants.
31.2 How does a Lava Lamp work?.
Contributed by: Jim Webb <jnw4347@email.unc.edu>
A container filled with clear or dyed liquid contains a non-water-soluble

substance (the "lava") that's just a little bit denser (heavier), and has
a greater thermal coefficient of expansion, than the liquid around it.
Thus, it settles to the bottom of the container. A heat source at the
bottom of the container warms the substance, making it expand and become
less dense than the liquid around it. Thus, it rises. As it moves away
from the heat source, it cools, contracts a bit, and becomes (once again)
heavier than the medium. Thus, it falls. Heavy, light, heavy, light.
Sounds like a Milan Kundera novel.
(Actually, to be more precise: dense, less dense, dense, less dense.)
31.3 How do I make a Lava Lamp?.
Contributed by: Jim Webb <jnw4347@email.unc.edu>
Method 1. A new, easy, simple, cheap lava lamp recipe
Use mineral oil as the lava. Use 90% isopropyl alcohol (which most
drugstores can easily order) and 70% isopropyl alcohol (grocery-store
rubbing alcohol) for the other ingredient. In 90% alcohol the mineral oil
will sink to the bottom; slowly add the 70% alcohol (gently mixing all
the while; take your time) until the oil seems lighter and is about to
"jump" off the bottom. Use the two alcohols to adjust the responsiveness
of the "lava."
This mixture is placed in a closed container (the "lava lamp shape" is

not required, although something fairly tall is good) and situated over a
40-watt bulb. If the "lava" tends to collect at the top, try putting a
dimmer on the bulb, or a fan at the top of the container.
To dye the lava, use an oil-based dye like artists' oil paints or a
chopped-up sharpie marker. To dye the liquid around it, use food
coloring.
Two suggestions for better performance: 1) Agitation will tend to make

the mineral oil form small bubbles unlike the large blobs we're all used
to. The addition of a hydrophobic solvent to the mixture will help the
lava coalesce. Turpentine and other paint solvents work well. To make
sure what you use is hydrophobic, put some on your hand (if it's so toxic
you can't put it on your hand, do you want to put it in a container that
could break all over your room/desk/office?) and run a little water on
it. If the water beads, it should work fine. 2) For faster warm-up time,
add some antifreeze or (I've not tried it) liquid soap. Too much will
cloud the alcohol. Keep in mind that the addition of these chemicals may
necessitate your readjusting the 90% to 70% alcohol mixture.
Method 2. The "official" way - from a patent [3].
The patent itself is not very specific as to proportions of ingredients.

The solid component (i.e., the waxy-looking stuff that bubbles) is said
to consist of "a mineral oil such as Ondina 17 (R.T.M.) with a light
paraffin, carbon tetrachloride, a dye and paraffin wax."
The medium this waxy stuff moves in is roughly 70/30% (by volume) water
and a liquid which will raise the coefficient of cubic thermal expansion,
and generally make the whole thing work better. The patent recommends
propylene glycol for this; however, glycerol, ethylene glycol, and
polyethylene glycol (aka PEG) are also mentioned as being sufficient.
This mixture is placed in a closed container (the "lava lamp shape" is

not required, although something fairly tall is good) and situated over a
40-watt bulb. If the "lava" tends to collect at the top, try putting a
dimmer on the bulb, or a fan at the top of the container.
Method 3. The "less official" way - from Popular Electronics [4].
Several non-water-soluble chemicals fall under the category of being

"just a little bit heavier" than water, and are still viscous enough to
form bubbles, not be terribly poisonous, and have a great enough
coefficient of expansion. Among them: Benzyl alcohol (Specific Gravity
1.043 g/cm3), Cinnamyl Alcohol (SG 1.04), Diethyl phthalate (SG 1.121)
and Ethyl Salicylate (SG 1.13). [The specific gravity of distilled water
is 1.000.]
Hubscher recommends using Benzyl Alcohol, which is used in the

manufacture of perfume and (in one of its forms) as a food additive. It can
be obtained from chemical or laboratory supply houses (check your yellow
pages); the cheapest I could find it for was $25 for 500 ml (probably 2,
maybe 3 regular-sized lava lamps' worth). An oil-soluble dye is nice to
color the "lava"; Hubscher soaked the benzyl in a chopped up red felt-tip
pen and said it worked great. [Benzyl alcohol is "relatively harmless",
but don't drink it, and avoid touching & breathing it.]
Hubscher found that the benzyl and the water alone didn't do much, so he
raised the specific gravity of the water a little bit by adding table
salt. A 4.8% salt solution (put 48 grams of salt in a container and fill
it up to one liter with water) has a specific gravity of about 1.032,
closer to benzyl's 1.043. I find that the salt tends to cloud the water a
bit.. you might want to experiment with other additives. (Antifreeze?
Vinegar?)
This is put into a closed container and placed above a 40-watt bulb, as
above. Either way, I would suggest using distilled water and consider
sterilising the container by immersing it in boiling water for a few
minutes.. algae growing in lava lamps is not very hip.
Caveat: Some of these chemicals are not good for you. Caveat 2: Some of
these companies are not good for you if they find you've been infringing
on their patent rights and trying to sell your new line of "magma
lights." Be careful.
31.4 What is Goretex?.
Goretex is a dispersion-polymerised PTFE that is patented by W.L.Gore and

Associates [5]. It is classed as a stretched semi-crystalline film, and is
produced by extrusion under stress ( faster take-up rate than extrusion
rate ). The extrudate is stretched below the melting temperature, often
in the presence of an aromatic hydrocarbon that swells the amorphous region,
creating porosity. The hydrophobic nature of the PTFE means that liquid
water is repelled from the pores, whereas water vapour can pass through.
It is important to realise that once the PTFE pores are filled with liquid
water, the fabric can allow liquid water to pass though until it is dry
again. Thus Goretex-containing fabrics ( such as Nomex/Goretex - which
consists of an outer aramid fabric, a central Goretex layer, and a cotton
backing ) should never be used as protection from chemicals as many will
pass straight through. Any water-miscible solvent ( eg alcohol ) can fill
the pores, and then liquid water can displace it and continue to rapidly
pass through until the fabric is fully dried out.
31.5 What causes an automobile airbag to inflate?.
The final cause is the production of nitrogen from 10s of grams of sodium
azide, but there are some extra chemicals involved along the way.
Sodium azide is toxic, The airbag inflators are aluminium-encased units
that contain an igniter (squib), gas generating pellets ( or wafers of
sodium azide propellant ), and filters to screen out combustion products.
The electrical signal ignites a few milligrams of initiator pyrotechnic
material. The pyrotechnic material then ignites several grams of booster
material, which ignites the tens of grams of sodium azide, and the azide
burns very rapidly to produce nitrogen gas and sodium.
The sodium azide is pelletised to control the rate of gas generation by

controlling its surface area. The free sodium would form sodium
hydroxide when it contacts the water in people's noses, mouths, and
eyes so, to prevent this, the manufacturers mix in chemicals that will
produce sodium salts ( silicates, aluminates, borates ) on combustion.
Inflator units also often have a layer of matted material of alumina and
silica called Fiberfrax in the particulate filter. The Fiberfrax mat reacts
with most of the remaining free sodium in the generated gas. A typical
reaction pathway is as follows [6];-
300C
2 NaN3 ------> 2 Na + 3 N2
10 Na + 2 KNO3 ------> K2O + 5 Na20 + N2
K2O + Na2O + SiO2 ------> alkaline silicate glass.
There are apparently also corn starch and talcum powder used as lubricants
in the bag, and if the bag explodes these are the powders that contaminate
people - not the toxic chemicals in the inflator.
One article quotes 160 grams of propellant for a drivers-side bag

( 60 litres of gas) and 450 grams for a passengers-side bags
( which are 3-5 times larger) . I suspect that may include all of the
above ingredients in the igniter, but not the bag lubricants.
The bag fills until it reaches slightly above atmospheric pressure, and
the manufacturers now control the bag inflation speed to 90-200mph, which
is less than the early models - because they were too violent and could
harm occupants. The actual sequence goes something like:-
0 - Impact
15 - 20 milliseconds -
sensors signal severe frontal collision.
pyrotechnic squib fired
nylon bag inflates
the driver ( who has moved forward 5 inches)
slams into the fully inflated bag
85 -100 milliseconds - the driver "rides the bag down" as the air
cushion deflates.
Recently, there have been calls to change the crash testing procedures to
allow the test dummy to be belted in, as seat belt usage is now about 67%.
Having a belted dummy would permit the use of slower inflating airbags, as
the deaths of 30 children ( up to Dec. 1996 ) have been attributed to the
speed of inflation of the larger passenger-side bag. Early in 1997, the
US NHTSA finally permitted depowering and/or disabling of passenger-side
airbags. A major airbag supplier is Breed Automotive, Boonton Township, N.J.
More details can be found in specialist articles [7-9], and research is

continuing into alternative inflation mechanisms, such as compressed gases.
There has been extensive work over the last decade on "hybrid" airbag
systems. These two-stage systems often use cylinders of compressed gas,
which can be released at ambient temperatures for situations where low-speed
deployment is appropriate, or the gas can be rapidly heated for high-speed
deployment.
31.6 How hazardous is spilt mercury?.
First step - ensure any broken thermometer actually contained mercury, as

many only contain alcohol. Mercury has an appreciable vapour pressure at
ambient temperatures, thus if the mercury has split somewhere warm and with
limited air circulation, then vapour concentrations can accumulate. When
mercury drops any distance onto a surface, it splatters into hundreds of
minute globules, resulting in a large surface area. The major hazard is
the mercury vapour produced from the spill. Mercury usually ends up in carpet
or cracks in the surface, and so really is only a significant hazard to
children crawling around the floor. Do not over-react. If the location is
relatively cool and well-ventilated, there is little danger to adults. Remove
as much mercury as conveniently possible, and just remember when toddlers
come visiting that there is a slight potential hazard if the area is not
well-ventilated and is warm. Obviously, if you increase the ventilation, the
concentrations will decrease faster. The USA ACGIH TLV for mercury vapour is
0.05mg/m3, whilst the DFG ( Germany ) limit is 0.01mg/m3, and the vapour
pressure of mercury at 25C is 0.0018mm. At 25C, the equilibrium concentration
would be about 20mg/m3, which is 400 times the permitted TLV. It is unlikely
that this equilibrium would be reached in areas where there are significant
airflows, unless the mercury had been finely dispersed ( as in a blown
manometer, or dropped onto a very rough surface ).
Mercury vapour is rapidly oxidised to divalent ionic mercury by the tissues

of the body. Human volunteers exposed to tracer doses of elemental Hg
demonstrated first order kinetics for excretion with a half life of 60 days.
The lethal concentration for humans is apparently not known, but acute
mercurialism has resulted from exposures to concentrations within the range
1.2 - 8.5mg/m3. The human organism is able to absorb and excrete substantial
amounts of mercury, in some cases as high as 2 mg/day without exhibiting
any abnormal symptoms or physical signs [10].
The Dietary uptake for mercury was estimated to be :-

3 micrograms/day Adults
1 " " young children
1 " " infants.
and the adult uptake was estimated to comprise of
0.3 air via Hg(0),
0.1 water via Hg(2+),
3 food via Hg(CH3Hg+).
( EPA Mercury Criteria Document 1979 )
The CRC Handbook of Laboratory Safety [11] has a chapter on mercury hazards.
A good discussion of mercury ( and other metals ) is found in "Metals and
their Compounds in the Environment: Occurrence, Analysis and Biological
Relevance" [12].
The best method of removing spilt mercury is to use a vacuum with a flask
and pasteur pipette and chase the little globules around the floor while not
breathing :-). Seriously, a simple vacuum system, or even a pasteur pipette,
can remove most of the large globules. There are special commercial vacuum
cleaners, but never use a household one - as the expelled air will contain
mercury vapour, and the fine metal globules will contaminate the cleaner.
For nooks, crannies, and cracks - where the mercury is likely to remain
undisturbed, you can either apply flowers of sulfur ( fine elemental sulfur )
or zinc dust, with vigorous brushing to facilitate contact, and sweep up the
excess. If the mercury is going to be re-exposed ( by cleaning, foot traffic
etc., ), then the zinc dust may be preferred because of an apparently faster
reaction rate. However, if you have a light-coloured carpet, pouring yellow
or grey powder is not usually an option, and if the location is warm and not
well-ventilated near ground level, ensure that toddlers do not spend hours
every day playing there.
There have been several studies on the best methods to clean up spills,
including "Vaporisation of Mercury spillage" [13]. The abstract reports " A
report on an investigation of the problem in laboratories and industries of
mercury (Hg) vaporisation from small droplets in cracks and floors. The
efficacy of other fixing agents besides flowers of sulfur was metered.
The results show that the use of a sulfur, calcium oxide and water mixture
was the most successful mixture for fixing mercury droplets. A second
convenient technique is the use of an aerosol hair spray. A chelating soap
is available in some countries, and this would presumably be the method of
choice in dealing with spillages."
Another article includes methods based on amalgamating with zinc impregnated

in a metal sponge or scrubbing pad for picking up mercury [14], and another
investigates substances that can be used to remove spilled mercury - such as
iodised activated carbon, copper or zinc powders, molecular sieves of copper
or silver ions, and silica gel [15].
Dental amalgam is apparently a finely divided powder of a silver, tin,

and copper alloy that is mixed with the mercury. The setting time probably
is a function of the slow dissolution of the alloy in the mercury due to
the particle size of the powder used. The mass % of each individual metal
amalgam when mercury is saturated at 20C is Ag = 0.04, Cu = 0.0032, and
Sn = 0.62, but I've no idea if that is the ratio actually used. I presume
the ratio may be varied to obtain the desired physical properties, and that
there would be a theoretical excess of the alloy to ensure minimal free
mercury. The actual amount of mercury vapour from dental amalgam is low, but
directly measurable by sensitive mercury vapour analysers. The significance
of mercury vapour from dental amalgam to health has been very controversial,
however there are now practical alternatives in widespread use.
31.7 Did molasses really kill 21 people in Boston?.
From: mica@world.std.com (mitchell swartz) Date: Sun, 4 Jul 1993

Subject: Molasses Accident
[excerpt from the Book of Lists #3 (Wallace et alia)]
THE GREAT BOSTON MOLASSES FLOOD

"On Jan. 15, 1919, the workers and residents of Boston's North End, mostly
Irish and Italian, were out enjoying the noontime sun of an unseasonably
warm day. Suddenly, with only a low rumble of warning, the huge cast-iron
tank of the Purity Distilling Company burst open and a great wave of raw
black molasses, two stories high, poured down Commercial Street and oozed
into the adjacent waterfront area. Neither pedestrians nor horse-drawn
wagons could outrun it. Two million gallons of molasses, originally
destined for rum, engulfed scores of persons - 21 men, women, and children
died of drowning or suffocation, while another 150 were injured. Buildings
crumbled, and an elevated train track collapsed. Those horses not
completely swallowed up were so trapped in the goo they had to be shot by
the police. Sightseers who came to see the chaos couldn't help but walk in
the molasses. On their way home they spread the sticky substance throughout
the city. Boston smelled of molasses for a week, and the harbor ran brown
until summer."
From this we see 21 people were killed, the half life was fairly short for
the contaminants. Long term effects were probably negligible.
31.8 What is the active ingredient in mothballs?.
Mothballs were originally made from camphor ( C10H16O, [76-22-2], MP 176C,

BP 204C ), or naphthalene ( C10H8, [91-20-3], MP 82C, BP 218C ),
but para-dichlorobenzene ( C6H4Cl2, [106-46-7], MP 55C, BP 173C ), became
cheaply available as an unwanted by-product of ortho-dichlorobenzene
production, and thus became the most common active ingredient. However
para-dichlorobenzene is also a suspected carcinogen, and naphthalene
has again become a common active ingredient. Consequently, the best
method of finding the active ingredient is to read the label on the packet,
Note that adding mothballs to modern gasolines will not increase the octane
rating of the fuel - refer to the Gasoline FAQ posted in rec.autos.tech for
more details.
31.9 Is vinegar just acetic acid?.
Most countries have food regulations that permit the use of acetic acid as
clearly-labelled "synthetic white vinegar". Most vinegars are actually malt
vinegars ( fermented ), and synthetic acetic acid is not allowed to be sold
as Malt Vinegar. Most natural, unfortified, malt vinegars are appropriately
labelled. The classification can get rather messy when bulk suppliers dilute
malt vinegar concentrates with acetic acid, which itself could either be
synthetic, or from another fermentation process. Regulations usually require
any addition of acetic acid to be clearly marked on the label, and the
product is not normally legally sold as pure "malt vinegar". The amount of
acetic acid in "natural" malt, cider, or wine vinegars usually ranges from
4% - 6%, but some examples can have up to approximately 20%. Vinegar is
produced by the exothermic aerobic bacterial oxidation of ethanol to acetic
acid via acetaldehyde.
31.10 What are the different grades of laboratory water?.
There are several techniques used in chemical laboratories to obtain the

required purity of water. There are several grading systems for water, but
the most well-known is the ASTM system, although certain applications (HPLC)
often require purer water than ASTM Type I, consequently additional
treatments such as ultrafiltration and UV oxidation may also be used to
reduce concentrations of uncontrolled impurities, such as organics.
ASTM Type I II III

Specific Conductance (max. uMhos/cm.) <0.06 <1.0 <1.0
Specific Resistance (min. Mohms/cm.) >16.67 >1.0 >1.0
Total Matter ( max. mg/l ) <0.1 <0.1 <1.0
Silicate ( max. mg/l ) N/D N/D 0.01
KMnO4 Reduction ( min. mins ) >60.0 >60.0 >10.0
Type A B C
Colony Count (Colony forming units/ml) 0 Bacteria <10 <100
pH NA NA 6.2-7.5
The techniques to purify natural waters - which may be almost saturated

with some contaminants - are frequently used in combination to obtain high
purity laboratory water. Some purification techniques use less energy than
distilling the water, and may be used in combination where large volumes of
"pure" water are required. The design of purified water systems, and the
materials used for construction, are selected according to the important
contaminants of the water. For some applications, 316L stainless steel may
be required, whereas other applications may require polyvinylidene difluoride
and polytetrafluoroethylene materials. Systems are carefully designed to
minimise the volume of water remaining static and in "dead ends" - where
microbes could grow.
The first treatment is usually a coarse physical filtration using a depth

filter that can remove undissolved large particles and other insoluble
material in the feed water.
For smaller volumes, distillation is the pretreatment method of choice.

Distilled water is water that has been boiled in a still and the vapour
condensed to obtained distilled water. While many impurities are removed
( especially dissolved and undissolved inorganics that make water "hard",
most organisms, etc. ), some impurities do remain ( volatile and some
non-volatile organics, dissolved gases, and trace quantities of fine
particulates ). Distilled water has lost many of the ionic species that
provided a pH buffer effect so, as it dissolves some CO2 from the air
during condensation and storage, the pH moves to around 5.5 ( usually from
close to the neutral pH of 7.0 ). Distilled water has the vast majority of
impurities removed, but often those residual compounds still make it
unsuitable for demanding applications, so there are alternative methods of
purifying water to remove specific undesirable species.
The next common treatment is ion-exchange, which involves using a bed of

resin that exchanges with unwanted dissolved species, such as those that
cause "hardness" ( calcium, magnesium ) in water. Two resins are used, one
that exchanges anions ( usually a strong anion exchanger such as Amberlite
IRA-400 - a quaternary ammonium compound on polystyrene ), and one that
exchanges cations ( usually a strong cation exchanger such as Amberlite
IR-120 - a sulfonic acid compound on polystyrene ). These resins can also
be combined in "mixed bed" resins, such as Amberlite MB-1A, which is a
mixture of IRA-400 [OH- form] and IR-120 [H+ form]. The porosity of the
polystyrene-based resin is dependant on the amount of cross-linking, which
is, in turn, dependant on the proportion of divinyl benzene used in the
process. Unfortunately, selectivity of a highly porous resin is inferior
to that of a less porous, more cross-linked, resin, so a balance between
the rate of exchange and the selectivity is sought. Agarose, cellulose,
or dextran can be used in place of the polystyrene base. Sophisticated
systems can have many beds in sequence, using both stronger and weaker
ion exchange resins.
The exchange potential for ions depends on a number of factors, including

molecular size, valency and concentration. In dilute solutions, exchange
potentials increase with increasing valency, but in concentrated solutions
the effect of valency is reversed, favouring the absorption of univalent
ions rather than polyvalent ions. This explains why calcium and magnesium
can be strongly absorbed from feedwater in softening processes, but then are
easily removed from the ion exchange resin when concentrated sodium chloride
is used as regenerant. In dilute solutions, the order of common anion
exchange potentials on strong anion exchangers is sulfate > chromate >
citrate > nitrate > phosphate > iodide > chloride. In dilute solutions, the
order of common cation exchange potentials on strong cation exchangers is
Fe3+ > Al2+ > Ba2+ > Pb2+ > Ca2+ > Cu2+ > Zn2+ = Mg2+ > NH4+ = K+ > Na+ >
H+ > Hg2+.
There are two forms of ion exchange for water purification. To "deionise"
feed water, the resins are in the OH- ( anion exchanger ) and H+ ( cation
exchanger ) forms. If sodium chloride was present in the feed water, the
sodium ion would displace the hydrogen ion from the cation resin, while
the chloride would displace the hydroxyl ion from the anion resin. The
displaced ions can combine to form water. Separate beds of resins can be
regenerated using 1 Normal acid ( HCl or H2SO4 ) for strongly-acid cation
resins, or 1 Normal sodium hydroxide for strongly-basic anion resins.
The amount of regenerant is approximately 150 - 500% of the theoretical
exchange capacity of the bed.
If the intention is to merely "soften" the feed water to reduce deposits,

the beds can be in the Cl- ( anion exchanger ) and Na+ ( cation exchanger )
forms. These are replaced by the dilute polyvalent species in the water that
rapidly form undesirable insoluble deposits as process water evaporates,
like calcium, magnesium and sulfate. The beds can be regenerated by passing
highly concentrated salt ( sodium chloride ) solutions through them until
all the polyvalent ions on the resins have been replaced. This technique
produces "soft" process water that used in industry.
When a dilute feedwater solution containing salt passes through a cation

exchange resin bed in the hydrogen form, the reaction that occurs is:-
Na+ + Cl + R.SO3H <=> H+ + Cl- + R.SO3Na
Obviously, the acidity of the water strongly increases as it moves down the
bed, which inhibits the exchange process. If a mixed bed is used, the
products soon encounter the anion exchange resin and are also removed:-
H+ + Cl- + R.NH2 <=> R.NH3 + Cl-
H+ + Cl- + R.NH3OH <=> R.NH3 + Cl- + H2O
Mixed bed resins are usually more efficient than equivalent single beds.
If the water feeding the resin beds has already been distilled ( very common
in laboratories - the resin beds then last much, much longer, and the
distillation has also removed other impurities ), then the water is called
"distilled and deionised". Laboratory water that has had most of the ionic
impurities removed will have a high electrical resistance, and is often known
as "18.3 megohm" water because the electrical resistance is >18,300,000
ohm/cm, but note that non-ionic impurities may still be present.
An alternative process that has increasingly replaced ion-exchange is

reverse-osmosis, which uses osmotic pressure across special membranes to
remove most of the impurities. It is called reverse-osmosis because the feed
side is pressurised to drive the purified water through the membrane in the
opposite direction than would occur if both sides were the same pressure.
The two common membrane materials are cellulose acetate or polysulfone
coated with polyamine, and typical rejection characteristics are:-
Monovalent Divalent Pyrogens, Bacteria
Ions Ions Organics > 200 MW
Cellulose Acetate >88% >94% >99%
Polyamine >90% >95% >99%
The huge advantage of RO is that membranes can easily be maintained

( occasional chemical sterilisations ), are largely self-cleaning, and can
produce large amounts of water with no chemical regeneration and minimal
energy requirements - just the pressure ( 200 psi ) required to push the
water along the membrane surfaces and improve the osmotic yield. RO is
commonly used as a pretreatment stage when very pure water is required, and
for situations where large volumes of reasonably pure water are required.
Organic species and free chlorine are usually removed from water by passing
the water through a bed of activated carbon where they form a low energy
chemical link with the carbon. These filters are often installed upstream
of the ion-exchange and reverse osmosis stages to protect them from chlorine
and organics in the feed water. Polyamine RO membranes require feedwater
containing <0.1ppm free chlorine, however cellulose acetate membranes can
tolerate up to 1.5ppm free chlorine.
The final stage of producing "pure" laboratory water usually involves

passing the deionised water through a 0.22um filter, which is sufficiently
small to remove the vast majority of organisms ( the smallest known
bacterium is around 0.3um ), thus sterilising the water.
Recently, ultrafiltration has become popular as a means of reducing pyrogens

( they are usually lipopolysaccharides from the degradation of gram negative
bacteria ). They are measured by either injecting a sample into test rabbits
and measuring body temperature increase or by the more sensitive Limulus
Amebocyte Lysate (LAL) test. The internal membrane of an ultrafiltration
system has a pore size of <0.005um. This will remove most particles,
colloidal silica, and high MW organics such as pyrogens, down to about
10,000MW. These are usually for cell-culture and DNA research, and are
located at the point of use, however the ultrafiltration unit has to be
regularly sanitized to prevent microbial growth.
Ultraviolet irradiation can be used as a bactericide (254nm) or to destroy

organics by photo-oxidation (185nm). The water is exposed to UV for periods
up to 30 minutes, and the UV interacts with dissolved oxygen to produce
ozone. The ozone promotes hydroxyl radical formation, which result in the
destruction of organic material. Usually a high intensity, quartz mercury
vapour lamp is used, and is followed by an ion exchange and organic scavenger
cartridge to collect decomposition products. The product water is very low in
total organic carbon.
Dissolved gases can be removed by passing the water through a vacuum

degassing module that utilises an inert, gas-permeable membrane surrounded
by a vacuum to remove dissolved gases from the water.
The purest laboratory water is usually obtained after passing through a

system that can include reverse osmosis or distillation of the feed water,
followed by activated carbon to remove chlorine and organics. The water is
passed through ion exchange resins to remove inorganic ions, through a
UV oxidation stage, followed by a combined ion exchange and organic scavenger
cartridge, and finally through a 0.22um filter. An additional stage of vacuum
degassing to remove dissolved gases may be added for some applications - such
as for semiconductor production.
These pure water systems are regarded as " point-of-use ", because it is
extremely difficult to prevent the reintroduction of contamination during
storage and distribution. The water is commonly known as " 18.3 Megohm "
water, because it has a specific resistance greater than 18.3 Megohm-cm
at 25C. It also contains < 5 ppb of total organic carbon, < 10 ppb of total
dissolved solids, and < 1 colony forming unit / mL of micro-organisms.
Details of laboratory and industrial water-purification processes are

available in the catalogues of equipment suppliers such as Barnstead [16]
and Millipore [17].

topic!
knowledge

Date: Thu, 15 Jan 2004 22:13:09 +1300
Message-ID: <0cmc005it9tiu2vnt3umkmkvvkb4bqift4@4ax.com>
Version: 1.17
Sarin is a nerve gas that was used in 1988 by Iraq against its Kurdish
population, and in 1995 by Japanese terrorists against Tokyo subway users.
Sarin and its companion nerve gases ( Tabun and Soman ) were discovered
in the late 1930s by Gerhard Schrader at I.G.Farben during research into
pesticides. The lethal dose for humans may be as low as 0.01mg/kg [18],
unless treated immediately. Sarin inhibits acetylcholinesterase, an enzyme
that breaks down acetylcholine. Acetylcholine carries signals between nerves
and muscles, and build-up causes over-stimulation of muscles ( including
the involuntary ones controlling eye, lungs, bowel ), which then go into
spasms. Treatment involves atropine ( shuts down the overstimulated nerves ),
or oxime drugs ( can prise Sarin off the enzyme ), and must be immediate.
More details and references can be found in the Merck Index.
There are many different methods of manufacture, but the Tokyo product
appears to have been prepared using a procedure involving phosphorus
trichloride and methyl iodide. The product was impure and diluted with
acetonitrile to improve volatility. To stockpile Sarin, the product has to
be pure ( 90-99% of the Iraqi Sarin degraded in < 2 years, whereas US Sarin
only degraded a few % over 30 years ). The standard US government procedure
( aka "di-di" ) starts with dimethyl methylphosphonate (DMMP), and ends
with a distillation to remove impurities [19].
O O O O CH3
|| thionyl || HF || isopropyl || /
CH3-P-OCH3 ------> CH3-P-Cl --> CH3-P-F ---------> CH3-P-O-CH
| chloride | | alcohol | \
OCH3 Cl F F CH3
DMPP Dichlor Difluor Sarin (GB)
"Dioxins" are a group of closely-related compounds which are known as

polychlorinated dibenzo-p-dioxins (PCDDs). "dioxins" also commonly includes
polychlorinated dibenzofurans (PCDFs). All organic molecules that contain
chlorine are also members of the "organochlorine" family.
1 9 1 9
2/ \ _o_ / \8 2/ \ ___ / \8
| O |_o_| O | | O |_o_| O |
3\ / \ /7 3\ / \ /7
4 6 4 6
Dibenzo-p-dioxin Dibenzofuran
As dioxins are fat soluble, they will accumulate in fatty tissue. In general,
it is only the biologically active ( molecules containing the 2,3,7,8
substitution ) congeners that accumulate, with levels of the higher
homologues predominating [20]. It is important to remember that of all the
dioxins and furans, only those containing 4 to 8 chlorine atoms, _and_ with
chlorine atoms in the 2,3,7,8 positions are currently considered toxic.
The compounds only containing 0 to 3 chlorine atoms are currently not
considered toxic, however once all four of the 2,3,7,8 positions are filled,
the most toxic congener is created ( 2,3,7,8 TCDD = "dioxin" ). As additional
chlorines are added, the toxicity decreases, except that 2,3,4,7,8
pentachlorodibenzofuran is more toxic than 2,3,7,8 tetrachlorodibenzofuran.
There is evidence that suggests concentrations of dioxins and furans in

human adipose tissue are falling [21]. The analysis for dioxin can reliably
detect ppq ( parts per quadrillion = picograms/kilogram ) levels, but some
evidence suggests dioxins may still have toxic effects at such low levels.
The toxicity of dioxins is currently being carefully assessed by the US EPA
- who are due to present a comprehensive report in the next few months. The
draft of the report, and various reviews, have been available for public
comment and external peer review. A good discussion of current perceptions
is available in a special report published in the January 1995 Environmental
Science and Technology [22], where both sides of the debate are presented.
Dioxins can arise naturally from forest fires, but the major sources are
from incineration and the manufacture and use of organic chemicals. The most
well-known source is perhaps as an impurity in the defoliant Agent Orange
which was widely used in Vietnam. Agent Orange was a 50:50 mixture of the
n-butyl esters of the herbicides 2,4-D ( 2,4-dichlorophenoxyacetic acid ) and
2,4,5-T ( 2,4,5-trichlorophenoxyacetic acid ), and dioxin was present as
an impurity in the 2,4,5-T. Another well known incident was an industrial
accident at a 2,4,5-trichlorophenol manufacturing plant in Seveso, Italy
on 10 July 1976 which resulted in the release of 1-5 kg of dioxin.
Other dioxin sources involve combustion ( leaded gasoline, coal combustion,
metallurgical processes )[20].
As the various congeners have differing toxicity, dioxins are usually

reported using Toxic Equivalents systems. These assign to each congener a
toxicity factor relative to 2,3,7,8-TCDD, and these factors are used to
calculate the 2,3,7,8-TCDD Toxic Equivalent. The International Toxic
Equivalent Factor (I-TEF) system, proposed by the Challenges to Modern
Society Committee of the North Atlantic Treaty Organisation is widely used.
Food is the major source of dioxins for humans, and typical dietary intakes
in the US for a 65kg adult were estimated to be between 18-192 pgTEQ/day [23],
and UK intakes were estimated to be 125 pgTEQ/day [20]. The Regional Office
for Europe of the World Health Organisation suggests 10 pg/kg body weight/day
for 2,3,7,8-TCDD ( 600 pgTEQ/day for 60kg person ), as a Tolerable Daily
Intake, whereas the US-EPA suggests an intake of 0.006 pg/kg/day over a 70
year life will lead to one excess cancer in one million people.
Sources of Dioxins in the UK diet pgTEQ/day
Meat, meat products, poultry, and offals 38
Cow's milk 23
Fats and oils 19
Milk products 12
Fish 7.7
Eggs, cereal products, fruit, and vegetables 25.3
Red mercury is supposed to be a very powerful explosive that is being made

in Russian nuclear reactors. According to one report, it is a cherry red and
semi-liquid compound of pure mercury and mercury antimony oxide that is
irradiated for up to 20 days in a nuclear reactor [24]. It is claimed that
when incorporated in a fusion bomb, it can yield sufficient chemical energy
to fuse tritium atoms. Experts are sceptical that such an energetic compound
could be sufficiently stable to be used as an explosive, and no compelling
evidence for the existence of red mercury has yet been produced.
31.14 How do I remove stains and deposits?
- Test any planned treatment on an unimportant part of the material first,

(spots and holes aren't currently fashionable ).
- Chemicals for removing stains are often toxic and corrosive, handle with
care, and follow any provided safety instructions.
- Often stains are a diverse mix of chemicals, and the best solution is
to solubilise as much as possible, remove insoluble material through
washing, and then carefully bleach. Chemists should not assume they can
perform this process better than housewives.
- Some stains are more easily removed by physical means - such as using
abrasives ( household cleaning pastes, steel wool, metal polishes, etc ),
or freezing solid and scraping ( chewing gum ).
- The fresher the stain, the easier to remove. Avoid using hot water or soap
on unknown stains, and use solvents (eg glycerine) to help keep the stain
fresh. In cases when the stain is known to be water-soluble (eg bird
droppings ), it is often preferable to allow the stain to dry and carefully
scrape most away, before additional treatment.
- When using solvents, apply around the outer edge of the stain and work
towards the centre to prevent a stain ring forming.
- Many stains result from pigments, and they are seldom soluble, so once the
other components are removed, use physical agitation to remove the
insoluble material.
- Sometimes a dried stain can be "freshened" by using more of the stain
before treating - but use this approach very cautiously.
There are books on stain removal [25,26,27], and many of the common recipes
are also often found in some home-care and cookery books. Home-care magazines
also have question and answer sections that frequently include advice on
how to remove specific stains. Very few chemical books cover chemical
cleaning and stain removal, and smart chemists avoid offering to remove
stains :-). Common stains are usually attacked with the household chemical
arsenal that may include:-
* Absorbents - Cornflour, French chalk, fuller's earth, starch, talcum powder.
* Acids - Inorganic = hydrochloric ( galvanising remover, concrete cleaner ).
- Organic = acetic ( white vinegar ), citric ( lemon juice ),
tartaric ( cream of tartar )
* Alkalis - Sodium hydroxide ( drain cleaner ), ammonia solution,
* Bleaches - Sodium hypochlorite solution ( household bleach ), calcium
hypochlorite ( bleaching powder ), hydrogen peroxide
* Drycleaning Fluids - 1,1,1-trichloroethane, perchloroethylene.
* Enzymes - Pepsin
* Petroleum Fractions - mineral turpentine, kerosine, gasoline, white spirits.
* Sodium carbonate ( washing soda ), sodium bicarbonate ( baking soda ),
sodium tetraborate ( borax ).
* Solvents - Acetone ( nail polish remover ), amyl acetate, methanol, ethanol
( methylated spirits ), glycerine, toluene, xylenes, iso propyl
alcohol.
* Terpenes - Eucalyptus oil, citrus oil, camphor
Specific Stain Strategies.
Ballpoint - methylated spirits, fullers earth, glycerine.

Blood - cold salty water, cornflour paste, or dilute bleach.
Copper deposits on sink or bathtub - ammonia (1 hr) then detergent.
Chewing Gum - freeze, or sponge with eucalyptus oil.
Chocolate - methylated spirits, or soak in 5% borax solution
Lipstick - glycerine, eucalyptus oil, dry-cleaning fluids.
Rust - oxalic acid, citric acid, tartaric acid
Tar - toluene, xylenes, eucalyptus oil.
Tea or Coffee - glycerine, warm borax solution
Wine - glycerine, borax solution, lemon juice
It depends on the sample and amount of rust. If the material is heavily

rusted, then physical techniques ( sand blasting ) may be appropriate.
Chemical techniques on steel usually involve phosphoric acid, and the
concentration depends whether the treatment can be washed off. An
excellent discussion is available in Product Finishing [28], along with
simple formulations. For removing light rust without subsequent removal
of the solution, 15% phosphoric acid + 4% n-butanol + <0.1% sulfuric acid
is used, but if the solution can be washed away, then a faster acting
33% phosphoric acid + 2% n-butanol mixture is preferred.
Several commercial silver polishes use a fine abrasive ( such as calcium

carbonate ) to physically remove the tarnish, and also include in their
formulation components ( such as benzotriazole ), that form complexes or
films that slow the reappearance of tarnish. There are also a variety of
chemical tarnish removers that contain sulfuric acid, sodium thiosulfate,
or hot sodium phosphate, a chemical formulary should contain recipes.
A very popular technique for removing tarnish ( silver sulfide ), involves

an electrochemical cell that utilises the electrochemical series. In an
electrochemical cell, oxidation occurs at one electrode, whilst reduction
occurs at the other. Electrical contact between the two metals provides the
pathway for electron migration to occur from the anode to the cathode, and
when immersed in an electrolyte, charge will be balanced by transfer of
the sulfide ions.
The standard electrode potential at 25C of Ag+ + e- -> Ag is +0.799V, and if

the other metal is anodic relative to silver, the silver in the sulfide at
the cathode will gain electrons and revert to metallic silver. The metal
at the anode will be oxidized by the removal of electrons. The sulfide ions
can travel to the anode via the electrolyte. The electrochemical series
indicates metals that will work, and some readily-available and cheap metals
are iron, zinc, aluminium and magnesium. The standard electrode potential at
25C of Al3+ + 3e- -> Al is -1.66V, and aluminium foil is cheap.
When aluminium is the anode, and water is the electrolyte, the aluminium
surface will eventually be coated with an insulating film of aluminium
sulfide - which will gradually decrease the cleaning speed. Adding sodium
bicarbonate ( baking soda ) or sodium carbonate ( washing soda ) to the
electrolyte will assist in the evolution of hydrogen as the silver is
converted, and the hydrogen will combine with the sulfide ions to produce
some hydrogen sulfide gas ( rotten eggs smell ). The aluminium at the anode
will be converted to aluminium oxide.
Aluminium oxidises on contact with air, forming an insulating layer of oxide

that is present on the surface of foil, disposable alumimium dishes, or
pots that are commonly used as the anode when cleaning silver at home.
Such a layer is brittle, and can micro-crack in hot water, and the higher
temperatures can also increase the redox reaction rate. Cleaning formulations
may include sodium chloride ( table salt ), boric acid, or borax. It should
be noted that the process is not converting the silver back to the original
hard, lustrous surface, but into a soft, white powder that can be removed by
rubbing. The sulfide has actually dislocated some silver atoms from the metal
surface, and the cleaning treatment will not relocate them, but it will
eliminate the unsightly, dark, tarnish.
A typical procedure is to line a pyrex glass dish with alumimium foil so the
bright side of the foil will contact the solution. Add one litre of water,
and heat until near boiling. Add one tablespoon of sodium chloride and one
tablespoon of sodium bicarbonate, and gently stir to dissolve. Ensure that
the silverware has been washed in warm dishwashing detergents, and well
rinsed in warm water, to remove dirt and grease. Carefully add the silverware
to the dish, ensuring that each item is in contact with the aluminium foil,
and leave until the tarnish has disapppeared. Because no protective film
has been provided, the tarnish may reappear rapidly.
There are several excellent books and journals on metal treatments in the
hobbies and metalworking sections of public libraries. For the serious
plater, the journals Surface Finishing and Product Finishing discuss all the
the chemical and electrical aspects - including disposal and destruction of
wastes. Their Annual Handbooks, along with the Canning Handbook of
Electroplating, have many recipes and details for the serious electroplater.
In any metal finishing process, the preparation of the substrate is of
great importance, and the recommended sequence of cleaning, pickling,
plating, and especially passivating should be carefully followed.
Failure to correctly passivate newly-deposited protective surfaces is the
main cause of the rapid formation of unsightly corrosion products.
31.18 How fast do solvents pass through human skin?
It obviously depends on the solvents, and traditional measurements have

been made using dead skin, but some recent work has provided a simple
comparison of individual solvents. It must be emphasised that mixtures of
solvents may have significantly different rates [29].
Permeability Constants in g/m2h

Solvent Average Standard Deviation
Dimethylsulfoxide 176 42
N-Methyl-2-pyrrolidone 171 59
Dimethylacetimide 107 19
Dimethylformamide 98 1.1
Methyl ethyl ketone 53 29
Methylene chloride 24 8.4
Water [^3H radiolabeled] 14.8 0.1
Ethanol 11.3 0.5
Butyl acetate 1.6 0.1
gamma butyrolactone 1.1 0.1
Toluene 0.8 0.7
Propylene carbonate 0.7 0.4
Sulfolane 0.2
31.19 What is the pH of Coca-cola?.
Phosphoric acid is an approved food-grade acid that is added to Coca-cola

to provide some of the taste. When CO2 is added to "carbonate" aqueous
solutions, carbonic acid is formed. A tin of coca-cola was cooled in a
refrigerator to 7C and the pH of the sample measured over time. The pH
electrode was not temperature-compensated, so a correction was applied.
Time pH pH
(when opened) (corrected)
Initial 2.75 @ 7C 2.6
30 seconds 2.78 @ 7C 2.6
60 seconds 2.80 @ 7C 2.6
2 minutes 2.82 @ 7C 2.7
4 minutes 2.80 @ 7C 2.6
A sample was degassed in an ultrasonic bath for several minutes and the
pH measured, and compared to a control sample maintained at the same
temperature and time profile.
pH
Degassed pH 2.52 @ 21c
RT sample 2.50 @ 20C
So the conclusion is that the pH of Coca-Cola is approximately 2.5 - 2.7.

Not surprisingly, the relatively weak carbonic acid from the dissolved CO2
did not significantly affect the pH of the beverage. The aluminium beverage
containers are lined with a thin polymer or lacquer coating to prevent the
aluminium metal dissolving into the beverage.
Note that the differing flotation characteristics of cans of the normal

versions of carbonated beverages like Coca-Cola ( they may sink ), and
the diet versions ( they may float ), has nothing to do with the amount
of CO2 present. It is due to the increase in solution density from the
few percent of sugar added to the normal version, while the diet version
has only a few hundred ppm of an artificial sweetener that is much sweeter
than sugar.
Subject: 32. References
Note: "Refer 6.1" = Section 6, Reference 1.
Section 6:
[1] Beilstein's Handbuch der Organischen Chemie - 4th edition

F.K.Beilstein
(edited by P.Jacobson, B.Prager, F.Richter, H.G.Boit et al)
Springer (1918-)
[2] Bretherick's Handbook of Reactive Chemical Hazards - 6th edition

L.Bretherick, ( edited by P.G.Urben )
Butterworth-Heinemann ( December 1999 ) ISBN 075063605X
[3] Chemical Abstracts Service

CAS Internet E-mail: help@cas.org
2540 Olentangy River Rd Customer Service Telephone: 800-753-4227
PO Box 3012 or 614-447-3600 or (614) 447-3731
Columbus, OH 43210 Telefax: 614-447-3751
Fax: (614) 447-3751
http://www.cas.org
[4] Advanced Inorganic Chemistry - 6th edition

F.A.Cotton, G.Wilkinson, C.A.Murillo, M.Bochmann
John Wiley & Sons (April 1999) ISBN 0471199575
[5] Reagents for Organic Synthesis.

L.F.Fieser, M.Fieser.
Wiley (1980-) ISSN 0271-6747(v1-7) ISSN 0271-616X(v8-)
[6] Gardner's Chemical Synonyms and Trade Names - 11th edition
George W. A. Milne (Editor)
Ashgate Publishing Company (July 1999) ISBN 0566081903
[7] Gmelin's Handbuch der Anorganischen Chemie

E.Pietsch et al (editors)
Verlag Chemie (1926-)
[8] The Pharmacological Basis of Therapeutics - 9th edition

L.S.Goodman, A.G.Gilman, L.E.Limbird, P.B.Milinoff. (editors)
McGraw Hill (1996) ISBN 00702-62667
[9] Hawley's Condensed Chemical Dictionary - 13th edition

R.J.Lewis (editor)
John Wiley & Sons (December 1997) ISBN 0471292052 ;
CD-ROM Van Nostrand Reinhold (March 1998) ISBN 0471291919
[10] Dictionary of Organic Compounds ( formerly Heilbron ) - 6th edition

J.Buckingham, F.MacDonald (editors)
Chapman & Hall (December 1995) ISBN 0412540908
[11] Kirk-Othmer Encyclopedia of Chemical Technology - 4th edition.

Editor. M.Howe-Grant.
Wiley. ISBN 0-471-52681-9 (1993-) 25 volumes, approx. US$320/vol.
- available on CD-ROM.
[12] Lange's Handbook of Chemistry - 15th edition

J.A.Dean (editor)
McGraw-Hill (October 1998) ISBN 0070163847
[13] Martindale : The complete drug reference - 32nd edition

K.Parfitt (editor)
Pharmaceutical Press (April 1999) ISBN 085369429X
[14] Encyclopedia of Chemical Processing and Design

J.J.McKetta
Marcel Dekker (1990-) ISBN 0-8247-2497-6
[15] A Comprehensive Treatise on Inorganic and Theoretical Chemistry

J.W.Mellor
Longman (1922-1967)
[16] Merck Index - 12th edition

S.Budavari et al. (editors)
Chapman and Hall (1996) ISBN 0-911910-12-3
- available on CD-ROM for approximately three times the hardcopy price,
check out the Merck WWW site for details.
[17] Chemical Engineers' Handbook - 7th edition

R.H.Perry and D.W.Green (editors)
McGraw-Hill (1997) ISBN 0-07-049841-5
CD-ROM Version McGraw-Hill (January 1999) ISBN 0071344128
[18] Registry of Toxic Effects of Chemical Substances

National Institute for Occupational Safety and Health
Cincinnati, Ohio 45226.
[19] CRC Handbook of Chemistry and Physics 1999-2000 - 80th edition

D.R.Lide (editor)
CRC Press (June 1999) ISBN 0849304806
[20] Sax's Dangerous Properties of Industrial Materials - 10th edition
N.I.Sax ( edited by R.J.Lewis Sr. )
John Wiley & Sons (November 1999) ISBN 0471354066
CD-Rom edition John Wiley & Sons (November 1999) ISBN 0471378607
Book & CD-Rom edition John Wiley & Sons (November 1999) ISBN 0471378585
[21] Shreve's Chemical Process Industries - 5th edition

R.N.Shreve and G.T.Austin
McGraw Hill (1984) ISBN 0-07-057147-3
[22] Ullmann's Encyclopedia of Industrial Chemistry - 6th edition.

Editors, J.E.Bailey, J.Brinder, M.Bohnet
VCH. Book & CD-Rom edition (July 1999) ISBN 3527201637
[23] Vogel's Textbook of Quantitative Chemical Analysis - 5th edition

A.I.Vogel
(previously Vogel's Textbook of Quantitative Inorganic Analysis )
5th Ed. (revised by G.H.Jeffery et al) Longman (1989) ISBN 0-470-21517-8
4th Ed. (revised by J.Bassett et al.) Longman (1978) ISBN 0-582-46321-1
3rd Ed. Longman (1962) ISBN 0-582-44247-8
(Note - I personally prefer the 3rd edition which was the last written
by A.I.Vogel, he provided more alternatives for each analysis,
especially for titrations )
[24] Vogel's Qualitative Inorganic Analysis - 7th edition

A.I.Vogel
( previously Macro and Semi-micro Qualitative Inorganic Analysis )
7th Ed. ( revised by G.Svehla ) Longmans (1996) ISBN 058-221866-7
4th Ed. Longmans (1954) SBN 582 44246 X
( Note - I've never seen the 7th edition - I'm very happy with the 4th
edition, which was the last by A.I.Vogel )
[25] Vogel's Textbook of Practical Organic Chemistry - 5th edition

A.I.Vogel
5th Ed. (revised by A.R.Tatchell et al) Wiley (1989) ISBN 0582-46236-3
4th Ed. (revised by B.S.Furniss et al) Longman (1978) ISBN 0582-44250-8
3rd Ed. Longmans (1956)
( Note - the 3rd edition was the last by A.I.Vogel, but the 4th has the
advantage of discussing of modern techniques. I have not seen the 5th.)
[26] Vogel's Elementary Practical Organic Chemistry - 3rd edition

A.I.Vogel. ( revised by B.V.Smith and N.M.Waldron )
Longman (1980) ISBN 0-582-47009-99v10
Section 7:
[1] Refer 6.3
[2] Dialog
Knight-Ridder Information, Inc.
www http://www.dialog.com
email info@dialog.com
phone 800-334-2564, or 415-254-7000
fax 415-254-7070
[3] Information Sources for Organic Chemistry, 1-3.

A.S.Somerville
J.Chem.Ed v.68 p.553-561 (1991)
J.Chem.Ed v.68 p.842-853 (1991)
J.Chem.Ed v.69 p.379-386 (1992)
[4] Searching the Beilstein Database Online: A comparison of systems.
R.E.Buntrock, M.A.Palma
Database, December 1990. p.19-34
[5] A Wealth of Information Online

M.J.Mazzella
Chemical Engineering. June 1989 p.112-127
Section 9:
[1] What Every Engineer Should Know About Patents - 2nd edition
W.G.Konold, B.Tittel, D.F.Frei, D.S.Stallard
Marcel Dekker (1989) ISBN 0-8247-8010-8
[2] Chem Sources : International ( biennial edition )

Chemical Sources International, Inc.
P.O. Box 1824 Clemson, SC 29633
Phone: 864-646-7840 Fax: 864-646-9938
E-mail: csinfo@chemsources.com http://www.chemsources.com
[3] Chem Sources : USA ( annual edition )

Phone: 864-646-7840 Fax: 864-646-9938
[4] OPD Chemical Buyers Directory - 82nd edition

( issued as part of subscription to Chemical Marketing Reporter)
Scnell Publishing (1995) ISBN 1-878800-04-3
[5] The Aldrich Catalog/Handbook ( annual edition )

Aldrich Chemical Company
P.O.Box 355
Milwaukee. Wl 53201
Orders: Mail PO Box 2060, Milwaukee Wl 53201 USA.
Phone. 414-273-3850
Fax. 414-273-4979
Customer Service: Phone 414-273-3850
[6] J.T.Baker Inc.

222 Red School Lane
Phillipsburg. NJ 08865
Phone 800-582-2537
Fax. 908-859-9318
[7] Refer 6.19
[8] Refer 6.16
[9] Refer 6.12
[10] Refer 6.9
[11] Tables of Physical and Chemical Constants - 16th edition

G.W.C Kaye and T.H.Laby ( now by a panel of editors )
Longman (1995) ISBN 0-582-226295
[12] Chemical Technicians' Ready Reference Handbook - 4th edition

G.J.Shugar, J.T.Ballinger, and L.M.Dawkins
McGraw Hill (1996) ISBN 0-07-057186-4
[13] Matheson Gas Data Book - 6th edition
W.Braker and A.L.Mossman
Matheson Gas Products (1980) ISBN 999-267037-1
[14] McGraw-Hill Concise Encyclopedia of Science and Technology - 4th edition

S.P.Parker, J.Weil, S.R.Felsenfeld (editors)
McGraw-Hill (January 1998) ISBN: 0070526591
[15] Van Nostrand's Scientific Encyclopedia - 8th edition

D.Considine ( editor )
Van Nostrand Reinhold (1994) ISBN 0-442-01864-9
CD-Rom John Wiley & Sons (January 1999) ISBN 0471293237
[16] McGraw Hill Encyclopedia of Chemistry

S.P.Parker
McGraw-Hill (1993) ISBN 0-07-045455-8
[17] McGraw-Hill Encyclopedia of Science and Technology - 8th edition

S.P.Parker
McGraw-Hill (January 1997) ISBN 0079115047
McGraw-Hill Concise Encyclopedia of Science and Technology - 3rd edition
S.P.Parker
McGraw-Hill (June 1994) ISBN 0070455600
[18] Refer 6.11
[19] Refer 6.22
[20] Refer 6.1
[21] Refer 6.7
[22] Refer 6.10
[23] Refer 6.14
[24] Encyclopedia of Polymer Science and Engineering - 2nd edition

H.F.Mark et al (editors)
John Wiley (1985-1990) ISBN 0-471-89540-7(v1)
Concise Polymeric Materials Encyclopedia
J.C.Salamone
CRC Press (September 1998) ISBN 084932226X
[25] Thorpe's Dictionary of Applied Chemistry - 4th edition

I.Heilbron et al (editors)
Longmans (1954)
[26] High Vacuum Techniques for Chemical Synthesis and Measurements.

P.H.Plesch
Cambridge University Press (1989) ISBN 0-521-25756-5
[27] High Vacuum Technique: Theory, Practice and Properties of Materials

- 4th Edition
J.Yarwood
[28] Swagelok Tube Fitting and Installation Manual

F.J.Callahan
Markad Service Co. (1985)
[29] Thermocouples: Theory and Properties
D.D.Pollock
CRC Press (1991) ISBN 0-8493-4243-0
[30] Merck KGaA

D-64271 Darmstadt
Germany
Phone ++496151/72-0
Fax ++496151/72-2000
[31] Rhone-Poulenc Prolabo Division

12 Rue Pelee
75011 Paris
France
[32] Sigma Chemical Company

P.O.Box 14508
St.Louis, MO.
USA 63178-9916
[33] Janssen Chimica Division

Janssen Pharmaceuticalaan 3
2440 Geel
Belgium
[34] Lancaster Synthesis Ltd

Eastgate, White Lund
Morecombe, Lancashire LA3 3DY
United Kingdom.
[35] Standard Infrared Spectra

Sadtler Research Laboratories
[36] The Aldrich Library of Infrared Spectra - 3rd edition

C.J.Pouchert
Aldrich Chemical (1981) ISBN 0-941633-07-1
[37] The Aldrich Library of FT-IR Spectra -2nd edition

C.J.Pouchert
Aldrich Chemical (1985-) ISBN 0-941633-20-9(v1&2), 0-941633-19-5(v3)
[38] Standard NMR Spectra

[39] The Aldrich Library of C13 and H1 FT-NMR Spectra

C.J.Pouchert and J.Behnke
[40] The Aldrich Library of NMR Spectra - 2nd edition

C.J.Pouchert
Aldrich Chemical (1983) ISBN 0-941633-08-X
[41] NIST/EPA/NIH Mass Spectral Data Base

S.R.Heller and G.W.A.Milne
US Govt. Printing Office (1978) NSRDS-NBS 63
CD-ROM ( MS-Windows - Aldrich Z25,737-0 US$1320 )
## http://www.nist.gov/srd/nist1.htm
[42] Wiley/NBS Registry of Mass Spectral Data

F.W.Lafferty and D.B.Stanffer ( editors )
John Wiley (1988)
[43] Industrial Chemical Thesaurus - 2nd edition
M.B. Ash, I.A. Ash
John Wiley & Sons (January 1997) ISBN 047118893X
[44] Encyclopedia of Industrial Chemical Additives

M.Ash and I.Ash
Chemical Publishing Co. (1987) ISBN 0-8206-0320-1
[45] Chemical Tradename Dictionary

M.Ash and I.Ash
VCH (1993) ISBN 1-569081-625-2
[46] The Chemical Formulary

( 35 volume series that is still growing )
Chemical Publishing Company (1933-) ISBN 0820603635 (1999 vol)
Cumulative Index - Volumes 1-34
Chemical Publishing Company (March 1999) ISBN: 0820603554
[47] The History of Chemistry

J.Hudson
Routledge Chapman and Hall (1992) ISBN 0-412-03641-X
[48] Chemistry of the Elements - 2nd edition

N.N.Greenwood and A.Earnshaw
Butterworth Heineman (1997) ISBN 0-08-0379419
[49] The Elements - 3rd edition

J.Emsley
Oxford University Press (1997) ISBN 0-19-855959-3
[50] Discovery of the Elements - 7th edition

M.E.Weeks ( revised by H.M.Leicester )
Journal of Chemical Education (1968) ISBN 0-317-09341-X
[51] The Chemical Bond: Structure and Dynamics

A.Zewail (Ed)
Academic Press (1992) ISBN 0-12-779620-7
[52] Chemistry in the Next Century

Thomas Midgley, Jr.
Ind.Eng.Chem. v.27 n.5 p.494-498 (1935)
[53] Midgley: Saint or Serpent?.

G.B.Kauffman.
Chemtech, December 1989. p.717-725.
Section 10:
[1] Sigma-Aldrich CD-ROM of 70,000+ MSDS

Aldrich Catalogue Z17,500-5
Annual Subscription US$1650
[2] Fire Protection Guide to Hazardous Materials - 12th edition

National Fire Protection Assiciation (November 1997) ISBN 0877654271
[3] The Sigma-Aldrich Library of Chemical Safety Data - 2nd edition

R.E.Lenga (editor)
Sigma-Aldrich (1988) ISBN 0-941633-16-0
[4] CRC Handbook of Laboratory Safety - 4th edition.

A.K.Furr (editor)
CRC Press (1995) ISBN 08493-2518-8
[5] Hazards in the Chemical Laboratory - 5th edition

S.G.Luxon (editor)
Royal Society of Chemistry (1992) ISBN 0-85186-229-2
[6] Refer 6.2
[7] The Sigma-Aldrich Library of Regulatory and Safety Data

R.E.Lenga and K.L.Votoupal (editors)
[8] Threshold Limit Values and Biological Exposure Indices - 1990/91 edition
- issued annually, and latest edition should be obtained and used.
TLV-BEI (1990) ISBN 0-936712-86-4
ACGIH ( 6500 Glenway Ave., Bldg.D-7., Cincinnati, OH 45211-4438 )
[9] Guide to Occupational Exposure Values - 1990-1991

Guide to Occupational Exposure Values (1990) ISBN 0-936712-87-2
[10] Encyclopedia of Occupational Health and Safety - 3rd edition

L.Parmeggiani
International Labour Office - Geneva (1989) ISBN 92-2-103289-2
[11] Refer 9.17
[12] Guidelines for Laboratory Design: Health and Safety Considerations

- 2nd edition
L.J.Diberardinis et al.
John Wiley & Sons (1993) ISBN 0-471-55463-4
[13] Laboratory Health and Safety Handbook - 2nd edition

R.S.Stricoff and D.B.Walters
John Wiley & Sons (1995) ISBN 0-471-02628-X
[14] Contact Lenses and Chemicals: An Update

E.B.Segal
Chemical Health and Safety. January/February 1995 p.16-21.
[15] Contact Lens Emergencies

A.P.Cullen
[16] Contact Lenses and Chemicals: Update 1997

E.B.Segal
Chemical Health and Safety. May/June 1997 p.33-37
[17] Contact lenses in industry: The ongoing discussion.

B.R.Blais
Chemical Health and Safety. July/August 1997 p.22-26
Section 11:
[1] Refer 9.36
[2] Refer 9.37
[3] Refer 9.40

[4] Refer 9.39
[5] Refer 9.41
[6] Fiveash Data Management, Inc. Reference Spectra Databases,

P. O. Box 400 Books, and Chemical Information
Fort Atkinson, WI 53538 USA
[7] Refer 9.24
[8] Spot Tests in Organic Analysis - 7th edition

F. Fiegl
Elsevier (June 1966) ISBN 0444402098
[9] Spot Tests in Inorganic Analysis - 6th edition

F.Feigl and V.Anger ( translated by R.E.Oesper )
Elsevier (1972) ISBN 0-444-409297
[10] Refer 6.24
[11] Refer 6.23
[12] Refer 6.25
[13] Treatise on Analytical Chemistry - 2nd edition

I.M.Kolthoff and P.J.Elving
Wiley Interscience (1978) ISBN 0-471-80648-X (p1.v14.)
[14] Techniques of Chemistry series

A.Weissberger
( Previously known as Techniques of Organic Chemistry and Techniques of
Inorganic Chemistry )
Wiley Interscience (1970-)
[15] Instrumental Methods of Analysis - 7th edition

H.H.Willard, L.L.Merritt, J.A.Dean, F.A.Settle, (editors).
Wadsworth Publishing (February 1988) ISBN 0534081428
[16] Analytical Instrumentation Handbook

G.W.Ewing (editor)
[17] 'Analar' Standards for Laboratory Chemicals - 8th edition

D.J.Bucknell
BDH Chemicals/Whitefriars Press (1984) ISBN 0-9500439-4-X
[18] Reagent Chemicals - 9th edition

American Chemical Society (September 1999) ISBN 0841236712
[19] Refer 6.13
[20] Official Methods of Analysis - 16th edition

P.A.Cunniff (editor)
Association of Official Analytical Chemists (1995) ISBN 0-935584-54-4
[21] Compilation of EPA Sampling and Analysis Methods

L.H.Keith (editor)
Lewis Publishers Boca Raton (1991)
[22] EPA Sampling and Analysis Methods Database

- available on computer disk ( Aldrich Cat. Z23,084-7 US$257.95 )
[23] Chromatography in Petroleum Analysis

K.H.Altgelt and T.H.Gouw (editors)
Marcel Dekker (1979) ISBN 0-8247-6790-X
[24] The Analysis of Gases by Chromatography

C.J.Cowper and A.J.DeRose
Pergamon Press (1983) ISBN 0-08-024027-5
[25] Standard Methods for the Examination of Water and Wastewater

- 20th Edition ( APHA,AWWA, and AWPF joint methods )
A.E.Greenberg, A.D.Eaton, L.S.Cleseri
American Public Health Assn. (January 1999) ISBN 0875532357
Book & CD-Rom edition (March 1999) ISBN 0875532403
CD-Rom edition (March 1999) ISBN 087553239X
[26] Water Analysis

W.Fresenius, K.E.Quentin, and W.Schneider (editors)
Spring-Verlag (1988) ISBN 0-387-17723-X
[27] Determination of Organic Substances in Water

T.R.Crompton
Wiley-Interscience (1985) ISBN 0-471-90468-6 (v1), 0-471-90469-4 (v2).
[28] Water - A Comprehensive Treatise ( six volumes )

F.Franks (editor)
Plenum Press (1972-1979) ISBN 0-306-37181-2 (v1)
[29] Methods of Decomposition in Inorganic Analysis

Z.Sulcek and P.Povondra
CRC Press (1989) ISBN 0-8493-4963-X
[30] Handbook of Analytical Derivatization Reactions

D.R.Knapp
John Wiley (1979) ISBN 0-471-03469-X
[31] Handbook of Derivatives for Chromatography - 2nd edition

K.Blau and J.M.Halket (editors)
John Wiley (1993) ISBN 0-471-92699-X
[32] Environmental Chemistry - 6th Ed.

S.E.Manahan
Lewis Publishers (1994) ISBN 1-56670-088-4
[33] Fundamentals of Environment Chemistry

S.E.Manahan
Lewis Publishers (1993) ISBN 0-873-71587-X
[34] Environmental Organic Chemistry

R.P.Schwarzenbach, P.M.Gschwend, and D.M.Imboden
John Wiley (1993) ISBN 0-471-83941-8
[35] Metals and their Compounds in the Environment: Occurrence, Analysis

and Biological Relevance.
E. Merian (editor)
VCH (1991) ISBN 0-89573-562-8
[36] Physical Chemistry - 6th edition

P.W.Atkins
Book & CD-Rom edition W H Freeman (December 1997) ISBN 0716728710
Physical Chemistry (Solutions Manual)
P.W. Atkins, C. A. Trapp, M. P. Cady, C. Giunta
W H Freeman (December 1997) ISBN 0716731673
[37] Textbook of Physical Chemistry - 2nd edition

S.Glasstone
Van Nostrand/MacMillan (1946)
[38] Physical Methods of Chemistry Series - 2nd edition

B.W.Rossiter, J.F.Hamilton
( Previously known as Volume 1 of the Techniques of Chemistry series )
[39] Inorganic Chemistry - 3rd edition

D. F. Shriver, P. W. Atkins
W H Freeman (February 1999) ISBN 0716736241
[40] Refer 6.23
[41] Refer 6.7
[42] Encyclopedia of Inorganic Chemistry

B.R.King (editor)
John Wiley (1994) ISBN 0-471-936200
CD-ROM edition John Wiley & Sons (August 1997) ISBN 047196798X
[43] Refer 6.4
[44] Organic Chemistry - 7th edition

T.W.G.Solomons, C.B.Fryhle, T.G.Solomons
John Wiley & Sons (July 1999) ISBN 0471190950
[45] Organic Chemistry - 3rd edition

L.F.Fieser and M.Fieser
Reinhold (1956)
[46] Advanced Organic Chemistry - 3rd edition

F.A.Carey and R.J.Sundberg
Plenum Press (1990) ISBN 0-306-43447-4(A), 0-306-43457(B)
[47] Organic Reactions

L.A.Paquette, R.Bittmen
( A 54 volume series that is still growing )
John Wiley & Sons (1942+) Vol 54 (June 1999) ISBN 0471348880
[48] Refer 6.5
[49] The Logic of Chemical Synthesis

X.Cheng, E.J.Corey
John Wiley & Sons (June 1995) ISBN: 0471115940
[50] Refer 6.10
[51] Refer 6.1
[52] Refer 6.21
[53] Refer 6.8
[54] Essentials of Medicinal Chemistry - 2nd edition

A.Korolkovas (editor)
John Wiley (1988) ISBN 047-188356-5
[55] Handbook of Pharmaceutical Excipients - 3rd edition

A.Wade, P.J.Weller
American Pharmaceutical Assoc. (November, 1999) ISBN 091733096X
Section 12:
[1] Names and Symbols of Transfermium Elements

Pure and Appl.Chem. v.66 p.2419-2421 (1994)
[2] Heavy Element name saga ends

M.Freemantle
C&EN 8 September 1997 p.9-10
[3] Interconversion of ASHRAE Refrigerant Numbers and Chemical Compositions

A.A.Woolf
J.Chem.Ed. v.70 p.35-36 (1993)
[4] Polyunsaturated fatty acids in diet and health

I.S.Newton
Chemisty and Industry 21 April 1997 p.302-305.
[5] Nutritional aspects of n-3 fatty acids

Inform v.8 n.5 p.428,429,433,434,437,439,440,443,444,447 (May 1997)
[6] Conjugated Linoleic Acid - The Good News about Animal Fat.
C.Steinhart
J.Chem.Ed. v.73 p.A302-A303 (December 1996)
[7] Conjugated Linoleic Acid, a newly recognised nutrient

M.W.Pariza
Chemistry and Industry. 16 June 1997 p.464-466.
[8] Concise Encyclopedia Biochemistry and Molecular Biology - 3rd edition

T.Scott, E.I.Mercer
Walter De Gruyter (December 1996) ISBN 3110145359
[9] International Encyclopedia of Chemical Science

D.Van Nostrand. (1964)
[10] Webster's Third New International Dictionary

P.B.Gove (editor)
Merriam Webster (1993) ISBN 0877792011
[11] Bring Back Equivalent Weight - If You Want the Kids To "Think"!
M.Laing
J.Chem.Ed. v.72 p.1007-1012 ( November 1996 )
[12] Dyeing Reagents for Thin Layer and Paper Chromatography

22/II 13/2699/10/1170L
E.Merck, Darmstadt.
[13] Piranha solution explosion

D.A.Dobbs, R.G.Bergman, K.H.Theopold
C&EN 23 April 1990 p.2
[14] Cleaning glass funnels

T.Wnuk
C&EN 25 June 1990 p.2
[15] Piranha solution explosions
C.V.Erickson
C&EN 13 August 1990 p.2
Section 13:
[1] The Sassafras Tree and Designer Drugs - From Herbal Tea to Ecstasy.
L.G.French
J.Chem.Ed. v.72 n.6 p.484-491. (June 1995).
[2a] Pihkal : A Chemical Love Story

A.Shulgin, A.Shulgin
Transform Press (September 1991) ISBN 0963009605
[2b] Tihkal : The Continuation
A.Shulgin
[3] Analysis of Semtex Explosives

J.R.Hobbs
p.409-427
Advances in Analysis and Detection of Explosives
J.Yinon (editor)
Kluwer Academic Publishers ISBN 0-7923-2138-3 (1993).
[4] The Semtex-H Story

A.W.Feraday
p.67-72.
J.Yinon (editor)
[5] Oklahoma bomb shows common items' power

M.Rouhi
C&EN. 1 May 1995. p.8
[6] Nitrogen Triiodide

I.C.Tornieporth-Oetting, T.M.Klapotke
Angew.Chem.Int.Ed.Engl. v.29 p.677-679 (1990)
[7] The Chemical Elements and their Compounds

N.V.Sidgwick
Oxford University Press (1950)
[8] Advanced Energetic Materials Emerge for Military and Space Applications
S.Borman
C&EN 17 January 1994 p.18-22.
[9] Recent Advances in Explosives and Solid Propellants

J.C.Bottaro
Chemistry & Industry (UK) 1 April 1996 p.249-252.
[10] Transforming Explosive Art in Science

A.Heller
Science & Technology Review June 1997 p.4-13.
[11] Refer 6.11

v.10. p.1-125. "Explosives and Propellants"
[12] Explosives - 4th edition, English

J.Kohler
John Wiley and Sons (November 1992) ISBN 3527285067
[13] Chemistry of Powder and Explosives

T.L.Davis
Angriff Press (June 1972) ISBN 0913022004
- available from Delta Press (deltagrp@eldonet.com),
or Loompanics (loompanx@olympus.net)
P.O. Box 1197, Port Townsend. WA 98368.
[14] Investigations of Fire and Explosion Accidents in the Chemical, Mining,

and Fuel-Related Industries - A Manual
J.M.Kuchta
US Dept. of the Interior. Bureau of Mines Bulletin 680 (1985).
[15] The Chemistry and Technology of Explosives

T.Urbanski
Pergamon. v.1-3 (1967) v.4 (1984) ISBN 0-08-030252-1
[16] The Encyclopedia of Explosives and Related Items

B.T.Federoff, O.E.Sheffield, and S.Kaye
PATR 2700, v.1-10. ARDEC, Dover, NJ.
Section 15:
[1] Chemical Demonstrations - A Handbook for Teachers of Chemistry

B.Z.Shakhashiri
University of Wisconsin Press (4 vols.) ISBN 0-318-56863-2 (1992)
http://scifun.chem.wisc.edu/demoser.html
Vol 001 (December 1983) ISBN 0299088901
Vol 002 (January 1986) ISBN 0299101304
Vol 003 (April 1989) ISBN 0299119505
Vol 004 (March 1992) ISBN 0299128601
[2] Chemical Demonstrations - A Sourcebook for Teachers - 2nd edition

L.R.Summerlin, J.L.Ealy Jr.
Amer.Chem.Soc. (1988) ISBN 0-8412-1481-6 (v1), 0-8412-1535-9 (v2)
[2a] Chemical Magic - 2nd edition

L.A.Ford, E.W.Grundmeier (Designer)
Dover Pubications (August 1993) ISBN 0486676285
[3] The Blue Bottle Experiment Revisited

A.G.Cook, R.M.Tolliver, and J.E.Williams.
J.Chem.Ed. v.71 n.2 p.160-161 (February 1994)
[4] Oscillating Chemical Reactions

I.R.Epstein, K.Kustin, P.De Kepper, and M.Orban
Scientific American p.96-108 (1983)
[5] Oscillating Chemical Reactions and Nonlinear Dynamics

R.J.Field and F.W.Schneider
J.Chem.Ed v.66 p.195-204 (March 1989)
[6] Recipes for Belousov-Zhabotinsky Reagents

W.Jahnke and A.T.Winfree
J.Chem.Ed v.68 p.320-324 (April 1991)
[7] Hydrogen Balloon Explosions

R.Battino, B.S.Battino
J.Chem.Ed. v.69 n.11 p.921-923 (November 1992)
[8] The Incredible "Glowing" Pickle and Onion and Potato and...
P.M.Weimer, R.Battino
J.Chem.Ed. v.73 n.5 p.456-457 (May 1996)
[9] Glowing Veggies

P.Scharlin, A.A.Cleveland, R.Battino, and M.E.Thomas.
J.Chem.Ed. v.73 n.5 p.457-459 (May 1996)
[10] The Gelation of Polyvinyl Alcohol with Borax

E.Z.Casassa, A.M.Sarquis, and C.H.Van Dyke
J.Chem.Ed. v.63 n.1 p.57-60 (January 1986)
[11] Slime and Poly(Vinyl Alcohol) Fibers

G.S.Stroebel, J.A.Whitesell, and R.M.Kriegel
J.Chem.Ed. v.70 n.11 p.893 (November 1993)
[12] The Gelation of Poly(Vinyl Alcohol) with Na2B4O7.10H2O: Killing Slime

K.W.McLaughlin, N.K.Wyffels, A.B.Jentz, and M.V.Keegan
J.Chem.Ed v.74 n.1 p.97-99 (January 1997)
Section 16:
[1] Desiccant Efficiency in Solvent Drying. A Reappraisal by

Application of a Novel Method for Solvent Water Assay.
D.R.Burfield, K.H.Lee, R.H.Smithers.
J.Org.Chem. v.42, p.3060-3065. (1977).
[2] Molecular Sieves - Dessicants of Choice.

D.R.Burfield, G.H.Gan, R.H.Smithers.
J.Appl.Chem.Biotech. v.28, p.23-30. (1978).
[3] Desiccant Efficiency in Solvent Drying. 3. Dipolar Aprotic Solvents

D.R.Burfield and R.H.Smithers
J.Org.Chem. v.43, p.3966-3968 (1978).
[4] Desiccant Efficiency in Solvent Drying. Applications of Cationic Exchange

Resins.
J.Chem.Tech.Biotechnol. v.30, p.491-496 (1980)
[5] Desiccant Efficiency in Solvent and Reagent Drying. 5. Amines

D.R.Burfield, R.H.Smithers, and A.S.C.Tan
J.Org.Chem. v.46, p.629-631 (1981).
[6] Drying of Grossly Wet Ether Extracts

D.R.Burfield, R.H.Smithers
J.Chem.Ed. v.59, p.703-704 (1982)
[7] Desiccant Efficiency in Solvent and Reagent Drying. 7. Alcohols.

J.Org.Chem. v.48, p.2420-2422 (1983)
[8] Desiccant Efficiency in Solvent and Reagent Drying. 8. Molecular Sieve

Column Drying of 95% Ethanol: An Application of Hygrometry to the Assay
of Solvent Water Content.
D.R.Burfield, G.T.Hefter, and D.S.P.Koh
J.Chem.Tech.Biotechnol. v.34A, p.187-194 (1984)
[9] Desiccant Efficiency in Solvent and Reagent Drying. 9. A Reassessment of

of Calcium Sulfate as a Drying Agent.
D.R.Burfield.
J.Org.Chem. v.49, p.3852-3854 (1984)
[10] Oven Drying of Volumetric Glassware

D.R.Burfield and G.Hefter
J.Chem.Ed. v.64 p.1054 (1987)
[11] Neues Verfahren zur maBanalytischen Bestimmung des Wassergehaltes

von Flussigkeiten und festen Korpern
K.Fischer
Angew. Chem., v.48 p.394-396 (1935)
[12] Titrimetric Determination of Water in Organic Liquids using Acetyl

Chloride and Pyridine
D.M.Smith and W.M.D.Bryant
J.Amer.Chem.Soc., v.57 p.841-845 (1935)
[13] Karl Fischer Titration

E.Scholz
Springer-Verlag (1984) ISBN 3-540-13734-3
[14] An Effective Technique for Cleaning Glassware

D.P.Higley
J.Chem.Ed. v.52 p.306 (1975)
[15] Refer 6.23
[16] Standard Glassware Cleaning Solutions

The Chemist's Companion
J.Wiley & Sons ISBN 0-471-31590-7 (1972)
[17] Laboratory Hazards - an explosion involving "chromic acid".

W.R.Bryson
Chem.Brit. v.11 p.377 (1975)
[18] Chromic Acid explosions

M.J.Pitt
Chem. Brit. v.11 p.456 (1975)

S.Downing
Chem. Brit. v.11 p.456 (1975)
[20] A Less Hazardous Chromic Acid Substitute for Cleaning Glassware

P.L.Manske, T.M.Stimpel, and E.L.Gershey
J.Chem.Ed. v.67 p.A280-A282 (1990)
[21] Regeneration of Chromic Acid Cleaning Solution

D.Schwab and P.Martinez
J.Chem.Ed. v.66 p.528 (1989)
[22] Oxidising Acid Baths - without Chromate Hazards

H.M.Stahr, W.Hyde, and L.Siegler
Anal.Chem. v.54 p.1452A (1982)
[23] How to Remove Silicone Compounds or Greases.

Dow Corning Silicone Bulletin 06-005 (1962)
[24] Removing Silicone Grease from Glassware

T.H.Lowry
J.Chem.Ed. v.74 p.841 (1997)
[25] Removing Silicone Greases from Round Bottom Flasks
T.J.Reilly
J.Chem.Ed. v.73 p.381 (1996)
Section 17:
[1] Purification of Laboratory Chemicals - 4th edition

W.L.F.Armarego, D.D.Perrin
Butterworth-Heinemann (December 1997) ISBN 0750637617
[2] Palladium Reagents in Organic Syntheses

R.F.Heck
Academic Press (1985)
Section 18:
[1] Refer 15.1
[2] A Multicolored Luminescence Demonstration

P.E.Smith, K.Johnston, D.M.Reason, and G.M.Bodner
J.Chem.Ed. v.69 n.10 p.827-828 (October 1992)
[3] Overview of Sweeteners

J.W.Ellis
J.Chem.Ed. v.72 n.8 p.671-675 (August 1995)
[4] Discovery of Highly Sweet Compounds from Natural Products

A.D.Kinghorn, E.J.Kennelly
[5] Sweeteners: A question of taste

G.G.Birch
Chemistry and Industry 3 February 1997 p.90-94.
[6] Rediscovering the Wheel - The Flame Test Revisited

R.O.Ragsdale and J.A.Driscoll
[7] Flame Colors Demonstration

J.R.Peyser and J.R.Luoma.
J.Chem.Ed. v.65 n.5 p.452-453 (May 1988)
[8] Refer 6.11

Chromogenic Materials v.6 p.312-343.
[9] Electrochromic Materials

R.J.Mortimer
Chem.Soc.Revs. v.26 p.147-156 (1997)
[10] Sunglasses that Respond to Brightness

S.D.Stookey
J.Chem.Ed. v.47 p.176 (1970)
[11] Photochromic Sunglasses

B.Osterby, R.D.McKelvey, and L.Hill
J.Chem.Ed. v.68 p.424-425 (1991)
[12] Thermochromism
J.H.Day
Chem.Rev. v.63 p.65-80 (1963)
[13] The Physics and Chemistry of Color
K.Nassau
John Wiley & Sons. (1983) ISBN 047-186776-4
Section 19:
[1] Solutions to Sticky Problems. Booklet

More Solutions to Sticky Problems. Booklet
BROOKFIELD Engineering Laboratories Inc, MA, USA.
[2] Introduction to Practical Viscometry. Booklet

HAAKE, Mess-Technik GmbH.
[3] Principles and Applications of Rheology.

A.G.Frederikson
Prentice-Hall Inc. NJ.
[4] Viscosity and Flow Measurement.

Van Wazer, Lyons, Kim, Colwell.
Interscience Publishers. NY
[5] Electrorheological technology: The future is now.

K.O.Havelka and J.W.Pialet.
Chemtech p.36-45 ( June 1996 )
[6] Electrorheological Fluids: Mechanisms, Properties, Technology and

Applications.
Edited by R.Tao and G.Roy
World Scientific, Singapore (1994) ISBN 98102-16394
[7] Active Damping using ERM fluids.

Automotive Engineering p.19-23 (June 1993).
[8] Extraction with Supercritical Fluids

G.M.Schneider, E.Stahl, G.Wilke
Verlag Chemie (1980) ISBN 352725854X
[9] Solvents get the big squeeze

D.Bradley
New Scientist, 6 August 1994. p.32-35.
[10] Past, Present, and Possible Future Applications of Supercritical

Fluid Extraction Technology
C.L.Phelps, N.S.Smart, and C.M.Wai
J.Chem.Ed. v.73 n.12 p.1163 (December 1996)
[11] Cavitation and Bubble Dynamics

C.E. Brennen.
[12] Relativistic Effects in Structural Chemistry

P.Pyykko
Chem. Rev. v.88 p.563-594 (1988)
[13] Relativistic Effects on Chemical Properties

D.R.McKelvey
J.Chem.Ed. v.60 p.112-116 (February 1983)
[14] Relativistic Effects at the Freshman Level

M.S.Banna
J.Chem.Ed. v.62 p.197-198 (March 1985)
[15] Periodic Contractions among the Elements
J.Mason
J.Chem.Ed. v.65 p.17-20 (January 1988)
[16] Why is Mercury Liquid?

L.J.Norby
Section 20:
[1] Refer 11.15
[2] Chemical Instrumentation: A Systematic Approach. - 3rd edition

H.A. Strobel
John Wiley (1989) ISBN 0-471-61223-5
[3] Polarized Light.

W.A. Shurcliff and S.S. Ballard
Princeton: D. Van Nostrand, (1964)
[4] Optics - 3rd edition

E.Hecht, A.Zajac, K.Guardino (editors)
Addison-Wesley Publishing (August 1997) ISBN 0201838877
[5] The Chemist's Ready Reference Handbook

G.J. Shugar and J.A. Dean
New York: McGraw-Hill (1990) ISBN 0-07-057178-3
[6] Molecular Optical Activity and the Chiral Discriminations.

S.F. Mason
[7] Molecular Light Scattering and Optical Activity

L.D. Barron
[8] Problems and Experiments in Instrumental Analysis.

C.E. Meloan and R.W. Kiser
Charles E. Merrill Books, Inc. 1300 Alum Creek Drive,
Columbus 16, OH, (1963).
Section 22:
[1] Refer 11.13
[2] Refer 11.14
[3] Refer 11.15
[4] Refer 11.16
Section 23:
[1] Laboratory Handbook of Chromatographic and Electrophoretic Methods

- 3rd edition
E.Heftmann
[2] Thin Layer Chromatography - 2nd edition

E.Stahl
[3] Techniques of Chemistry - Vol. XIV

Thin-Layer Chromatography - 2nd edition
J.G.Kirchner
Wiley-Interscience (1978) ISBN 0-471-93264-7
Sigma Chemical (1990) ISBN 0-941633-25-X (reprint)
[4] Refer 11.30
[5] Refer 11.31
[6] Basic Gas Chromatography

H.M. McNair, J.M.Miller
John Wiley & Sons (October 1997) ISBN 047117260X
[7] High-Resolution Gas Chromatography

K.J.Hyver and P.Sandra
Hewlett Packard (1989) P/N=5950-3562 ISBN 999-184716-2
[8] Open Tubular Column Gas Chromatography

M.L.Lee, F.J.Yang, K.D.Bartle
[9] Sadtler Gas Chromatography Standard Retention Index Library

Sadtler Research Laboratories (1986).
[10] Introduction to Modern Liquid Chromatography - 2nd edition

L.R.Snyder and J.J.Kirkland
[11] Troubleshooting LC Systems

J.W.Dolan and L.R.Snyder
Humana Press (1989) ISBN 0-89603-151-9
[12] Practical HPLC Method Development - 2nd edition

L.R.Snyder, J.J.Kirkland, and J.L.Glajch.
[13] The Practice of Ion Chromatography

F.C.Smith Jr. and R.C.Chang
Krieger Publishing (1991) ISBN 089464-502-1
[14] Ion Chromatography

H.Small
Plenum Press (1989) ISBN 0-306-43290-0
[14a] Ion Chromatography - 2nd edition

J.Weiss
John Wiley & Sons (December 1994) ISBN 3527286985
[15] Modern Size Exclusion Chromatography

W.W.Yau, J.J.Kirkland, D.Bly
Section 24:
[1] Reactions in Supercritical Fluids

L.Boock, B.Wu, C.LaMarca, M.Klein, and S.Paspek
Chemtech. December 1992. p.719-723.
[2] Supercritical Fluid Extraction and Chromatography
B.A.Charpentier and M.R.Sevenants
Amer.Chem.Soc. Symposium Series v.366 (1988) ISBN 0841214697
[3] Supercritical Fluid Science and Technology

K.P.Johnston and M.L.Penninger
[4] Supercritical Fluid Engineering Science: Fundamentals and Applications

E.Kiran, J.F.Brennecke
Amer.Chem.Soc. Symposium Series v.514 (1993) ISBN 0-8412-2513-3
[5] Solving Process Problems with Supercritical Extraction

J.Via, L.T.Taylor
Chemtech. November 1993. p.38-44.
[6] The Use of Supercritical Fluids in the Isolation of Natural Products

C.D.Bevan and P.S.Marshall
Natural Products Reports, 1994. p.451-466.
[7] Supercritical Chemistry: Synthesis with a Spanner.

M.Poliakoff and S.Howdle
Chemistry in Britain. February 1995. p.118-121
[8] Proceedings of the International Symposium on Supercritical Fluids

- 2nd (1991) Baltimore. USA. ( proceedings edited by M.A.McHugh,
published by John Hopkins University. Baltimore. MD21218 )
- 3rd (1994) Strasbourg. France. ( proceedings published by Institut
National Polytechnique de Lorraine. ISBN 2-905267-23-8 ).
Section 26:
[1] International pH Scales and Certification of pH.

H.B.Kristenson, A.Salomon, and G.Kokholm
Anal.Chem. v.63, p.885A-891A (1991).
[2] Determination of pH, Theory and Practise - 2nd edition

R.G.Bates
John Wiley & Sons. (1973) ISBN 0-317-09107-7
[3] Ion-Selective Electrodes in Analytical Chemistry

H.Freiser (editor)
Plenum Publishing Volume 1 (October 1978) ISBN 0306339072
[4] Ion-Selective Electrode Methodology

A.K.Covington (editor)
CRC Press. (1979) ISBN 0-8493-5247-9 (2 vols)
Section 27:
[1] Modern Petroleum Technology - 5th edition.

Editor, G.D.Hobson.
Wiley. ISBN 0 471 262498 (1984).
- Chapter 1. G.D.Hobson.
[2] Hydrocarbons from Fossil Fuels and their Relationship with Living
Organisms.
I.R.Hills, G.W.Smith, and E.V.Whitehead.
J.Inst.Petrol., v.56 p.127-137 (May 1970).
[3] Refer 27.1
- Chapter 9. R.E.Banks and P.J.King.
[4] Refer 27.1

- Chapter 20. K.Owen.
[5] Comparative Studies of Methane and Propane as Fuels for Spark Ignition
and Compression Ignition Engines.
G.A.Karim and I.Wierzba.
SAE Paper 831196. (198?).
[6] Experiments with MTBE-100 as an Automobile Fuel.

K.Springer, L.Smith.
Tenth International Symposium on Alcohol Fuels.
- Proceedings, v.1 p.53 (1993).
[7] Oxygenates for Reformulated Gasolines.

W.J.Piel, R.X.Thomas.
Hydrocarbon Processing, July 1990. p.68-73.
[8] The Chemical Kinetics of Engine Knock.

C.K.Westbrook, W.J. Pitz.
Energy and Technology Review, Feb/Mar 1991. p.1-13.
[9] The Chemistry Behind Engine Knock.

C.K.Westbrook.
Chemistry & Industry (UK), 3 August 1992. p.562-566.
[10] The Methanolysis of Tallow

P.J.S.Bain
Report of Investigation 2590 (1988)
DSIR. PO Box 31-310, Lower Hutt, New Zealand.
[11] Variables Affecting the Yields of Fatty Esters from Transesterified

Vegetable Oils
B.Freedman, E.H.Pryde, T.L.Mounts
JAOCS v.61 p.1638-1643 (1984)
[12] NZ Liquid Fuels Trust Board Reports LF1199 - LF1210

Available ( for a fee ) from Liquid Fuels Management Group Limited
P.O.Box 17, Wellington, New Zealand.
[13] Evaluating Vegetable Oils as a Diesel Fuel

T.Murayama
Inform v.5 p.1138-1145 (1994)
[14] Quality Control of Vegetable Oil Methyl Esters used as Diesel Fuel
Substitutes: Quantititative determination of mono-, di-, and
triglycerides by Capillary GC.
C.Plank and E.Lorbeer
J. High Resolut. Chromatog. v.15 p.609-612. (1992)
Section 28:
[1] Chiral Pharmacology and the Regulation of New Drugs

John Caldwell
Chemistry and Industry 6 March 1995 p.176-179
[2] Thalidomide: From tragedy to new drug discovery.

G.W.Muller
Chemtech January 1997 p.21-25.
Section 31:
[1] IR Long-Path Photometry: A Remote Sensing Tool for Automobile Emissions

G.A.Bishop, J.R.Stanley, A.Ihlenfeldt, W.J.Williams, and D.H.Stedman
Anal.Chem. v.61, p.671A-677A. (1989)
[2] Optical Remote Sensing for Air Pollutants - Review.

M.Simonds, H.Xiao, and S.P.Levine
Am.Ind.Hyg.Assoc.J. v.55, p.953-965 (1994)
[3] US Patent 3,570,156. March 16, 1971.
[4] How to make a Lava Lamp

R.Hubscher
Popular Electronics. March 1991, p. 31 (4). Gernsback Publications.
- also in Popular Electronics' "1992 Electronics Hobbyists Handbook".
[5] Goretex patent

U.S. Pat. 3,962,153 (8 June 1976) R.W.Gore (to W.L.Gore and Associates)
[6] The Chemistry behind the Air Bag

A.Madlung
J.Chem.Ed v.73 n.4 p.347-348 (April 1996)
[7] Automotive safety is in the bag

Steven Ashley
Mechanical Engineering. January 1994. p.58-64
( best technical descriptions)
[8] Airbags : Education and Experience

Automotive Engineering. September 1993. p.29-32
[9] Everything you need to know about airbags

Autocar & Motor (UK). 3 March 1993. p.55-57
[10] The Toxicology of Inorganic Mercury

L.J.Goldwater
Ann. N.Y. Acad. Sci., v.65 p.498-503 (1957)
[11] Refer 10.4
[12] Refer 11.35
[13] Vaporisation of Mercury spillage.

J.F.Copplestone and D.A.McArthur.
Archives of Environmental Health v.13. p.675 (1966)
[14] The clean up of spilled mercury by a new technique.

J.Shurgan and L.Harris
J.Amer.Ind.Hyg.Assn. v.38 p.146 (March 1977).
[15] Elimination of liquid mercury.

K.Wacks
Fette-seifen-Anstrichmittel. v.76 p.425-426. (1974, in German)
[16] The Water Book - Barnstead 1990 Catalogue.

Barnstead Thermolyne Corporation
2555 Kerper Blvd. Dubuque. IA 52001. USA
Phone 319-556-2241 800-553-0039
Fax 319-556-0695
[17] Millipore Catalogue.
Millipore Corporation
Bedford, MA 01730. USA.
Phone 617-275-9200 800-225-1380
Fax 617-275-8200
[18] Nerve Gases Unveiled

C&EN v.31 p.4676,4678 (1953)
[19] Tokyo Subway Attack - Chemical Weapon Possible Terrorist Tool.

L.Ember
C&EN. 27 March 1995. p.6-7.
[20] Dioxins in Food

UK Ministry of Agriculture, Fisheries and Food
Food Surveillance Paper No. 31
HMSO (1992) ISBN 0-11-242926-2
[21] Polychlorinated dibenzo-p-dioxin and dibenzofuran concentration levels

in human adipose tissue samples from the continental US collected from
1971 through 1987
J.S.Stanley et al.
Chemosphere v.20 p.895-901 (1990).
[22] Dioxin Risk - Are We Sure Yet?. ( p.24A-25A )

EPA's Dioxin Reassessment. ( p.26A-28A )
EPA on the Right Track ( p.29A-30A )
EPA Assessment Not Justified ( p.31A-32A )
ES&T v.29 p.24A-32A. ( January 1995 )
[23] Dioxins in U.S.Food and Estimated Daily Intake

A.Schecter et al.
Chemosphere v.29 p.2261-2265 (1994)
[24] Cherry red and very dangerous

R.Edwards
New Scientist. 29 April 1995. p.4-5
[25] The Super Stain Remover Book

J.Cassimatis
Sterling Publications (November 1996) ISBN 0806994835
[26] Removing Stains from Fabrics

Home and Garden Bulletin No. 62
Science and Education Administration
United States Department of Agriculture (1978)
[27] Stain Removal from Fabrics by Home Methods

Dept. of University Extension. Otago University (NZ).
Whitcoulls (1977)
[28] Surface pretreatment for phosphoric acid-based rust removers

M.Svoboda and B.Knapek
Product Finishing v.22 p.41-46 (1969)
[29] Permeability of Commercial Solvents Through Living Human Skin

C.Ursin, C.M.Hansen, J.W.Van Dyk, P.Jensen, I.J.Christensen, J.Ebbehoej.
Am.Ind.Hyg.Assoc.J. v.56 p.651-660 (1995)
Version: 1.17
Sarin is a nerve gas that was used in 1988 by Iraq against its Kurdish
population, and in 1995 by Japanese terrorists against Tokyo subway users.
Sarin and its companion nerve gases ( Tabun and Soman ) were discovered
in the late 1930s by Gerhard Schrader at I.G.Farben during research into
pesticides. The lethal dose for humans may be as low as 0.01mg/kg [18],
unless treated immediately. Sarin inhibits acetylcholinesterase, an enzyme
that breaks down acetylcholine. Acetylcholine carries signals between nerves
and muscles, and build-up causes over-stimulation of muscles ( including
the involuntary ones controlling eye, lungs, bowel ), which then go into
spasms. Treatment involves atropine ( shuts down the overstimulated nerves ),
or oxime drugs ( can prise Sarin off the enzyme ), and must be immediate.
More details and references can be found in the Merck Index.
There are many different methods of manufacture, but the Tokyo product
appears to have been prepared using a procedure involving phosphorus
trichloride and methyl iodide. The product was impure and diluted with
acetonitrile to improve volatility. To stockpile Sarin, the product has to
be pure ( 90-99% of the Iraqi Sarin degraded in < 2 years, whereas US Sarin
only degraded a few % over 30 years ). The standard US government procedure
( aka "di-di" ) starts with dimethyl methylphosphonate (DMMP), and ends
with a distillation to remove impurities [19].
O O O O CH3
|| thionyl || HF || isopropyl || /
CH3-P-OCH3 ------> CH3-P-Cl --> CH3-P-F ---------> CH3-P-O-CH
| chloride | | alcohol | \
OCH3 Cl F F CH3
DMPP Dichlor Difluor Sarin (GB)
"Dioxins" are a group of closely-related compounds which are known as

polychlorinated dibenzo-p-dioxins (PCDDs). "dioxins" also commonly includes
polychlorinated dibenzofurans (PCDFs). All organic molecules that contain
chlorine are also members of the "organochlorine" family.
1 9 1 9
2/ \ _o_ / \8 2/ \ ___ / \8
| O |_o_| O | | O |_o_| O |
3\ / \ /7 3\ / \ /7
4 6 4 6
Dibenzo-p-dioxin Dibenzofuran
As dioxins are fat soluble, they will accumulate in fatty tissue. In general,
it is only the biologically active ( molecules containing the 2,3,7,8
substitution ) congeners that accumulate, with levels of the higher
homologues predominating [20]. It is important to remember that of all the
dioxins and furans, only those containing 4 to 8 chlorine atoms, _and_ with
chlorine atoms in the 2,3,7,8 positions are currently considered toxic.
The compounds only containing 0 to 3 chlorine atoms are currently not
considered toxic, however once all four of the 2,3,7,8 positions are filled,
the most toxic congener is created ( 2,3,7,8 TCDD = "dioxin" ). As additional
chlorines are added, the toxicity decreases, except that 2,3,4,7,8
pentachlorodibenzofuran is more toxic than 2,3,7,8 tetrachlorodibenzofuran.
There is evidence that suggests concentrations of dioxins and furans in

human adipose tissue are falling [21]. The analysis for dioxin can reliably
detect ppq ( parts per quadrillion = picograms/kilogram ) levels, but some
evidence suggests dioxins may still have toxic effects at such low levels.
The toxicity of dioxins is currently being carefully assessed by the US EPA
- who are due to present a comprehensive report in the next few months. The
draft of the report, and various reviews, have been available for public
comment and external peer review. A good discussion of current perceptions
is available in a special report published in the January 1995 Environmental
Science and Technology [22], where both sides of the debate are presented.
Dioxins can arise naturally from forest fires, but the major sources are
from incineration and the manufacture and use of organic chemicals. The most
well-known source is perhaps as an impurity in the defoliant Agent Orange
which was widely used in Vietnam. Agent Orange was a 50:50 mixture of the
n-butyl esters of the herbicides 2,4-D ( 2,4-dichlorophenoxyacetic acid ) and
2,4,5-T ( 2,4,5-trichlorophenoxyacetic acid ), and dioxin was present as
an impurity in the 2,4,5-T. Another well known incident was an industrial
accident at a 2,4,5-trichlorophenol manufacturing plant in Seveso, Italy
on 10 July 1976 which resulted in the release of 1-5 kg of dioxin.
Other dioxin sources involve combustion ( leaded gasoline, coal combustion,
metallurgical processes )[20].
As the various congeners have differing toxicity, dioxins are usually

reported using Toxic Equivalents systems. These assign to each congener a
toxicity factor relative to 2,3,7,8-TCDD, and these factors are used to
calculate the 2,3,7,8-TCDD Toxic Equivalent. The International Toxic
Equivalent Factor (I-TEF) system, proposed by the Challenges to Modern
Society Committee of the North Atlantic Treaty Organisation is widely used.
Food is the major source of dioxins for humans, and typical dietary intakes
in the US for a 65kg adult were estimated to be between 18-192 pgTEQ/day [23],
and UK intakes were estimated to be 125 pgTEQ/day [20]. The Regional Office
for Europe of the World Health Organisation suggests 10 pg/kg body weight/day
for 2,3,7,8-TCDD ( 600 pgTEQ/day for 60kg person ), as a Tolerable Daily
Intake, whereas the US-EPA suggests an intake of 0.006 pg/kg/day over a 70
year life will lead to one excess cancer in one million people.
Sources of Dioxins in the UK diet pgTEQ/day
Meat, meat products, poultry, and offals 38
Cow's milk 23
Fats and oils 19
Milk products 12
Fish 7.7
Eggs, cereal products, fruit, and vegetables 25.3
Red mercury is supposed to be a very powerful explosive that is being made

in Russian nuclear reactors. According to one report, it is a cherry red and
semi-liquid compound of pure mercury and mercury antimony oxide that is
irradiated for up to 20 days in a nuclear reactor [24]. It is claimed that
when incorporated in a fusion bomb, it can yield sufficient chemical energy
to fuse tritium atoms. Experts are sceptical that such an energetic compound
could be sufficiently stable to be used as an explosive, and no compelling
evidence for the existence of red mercury has yet been produced.
31.14 How do I remove stains and deposits?
- Test any planned treatment on an unimportant part of the material first,

(spots and holes aren't currently fashionable ).
- Chemicals for removing stains are often toxic and corrosive, handle with
care, and follow any provided safety instructions.
- Often stains are a diverse mix of chemicals, and the best solution is
to solubilise as much as possible, remove insoluble material through
washing, and then carefully bleach. Chemists should not assume they can
perform this process better than housewives.
- Some stains are more easily removed by physical means - such as using
abrasives ( household cleaning pastes, steel wool, metal polishes, etc ),
or freezing solid and scraping ( chewing gum ).
- The fresher the stain, the easier to remove. Avoid using hot water or soap
on unknown stains, and use solvents (eg glycerine) to help keep the stain
fresh. In cases when the stain is known to be water-soluble (eg bird
droppings ), it is often preferable to allow the stain to dry and carefully
scrape most away, before additional treatment.
- When using solvents, apply around the outer edge of the stain and work
towards the centre to prevent a stain ring forming.
- Many stains result from pigments, and they are seldom soluble, so once the
other components are removed, use physical agitation to remove the
insoluble material.
- Sometimes a dried stain can be "freshened" by using more of the stain
before treating - but use this approach very cautiously.
There are books on stain removal [25,26,27], and many of the common recipes
are also often found in some home-care and cookery books. Home-care magazines
also have question and answer sections that frequently include advice on
how to remove specific stains. Very few chemical books cover chemical
cleaning and stain removal, and smart chemists avoid offering to remove
stains :-). Common stains are usually attacked with the household chemical
arsenal that may include:-
* Absorbents - Cornflour, French chalk, fuller's earth, starch, talcum powder.
* Acids - Inorganic = hydrochloric ( galvanising remover, concrete cleaner ).
- Organic = acetic ( white vinegar ), citric ( lemon juice ),
tartaric ( cream of tartar )
* Alkalis - Sodium hydroxide ( drain cleaner ), ammonia solution,
* Bleaches - Sodium hypochlorite solution ( household bleach ), calcium
hypochlorite ( bleaching powder ), hydrogen peroxide
* Drycleaning Fluids - 1,1,1-trichloroethane, perchloroethylene.
* Enzymes - Pepsin
* Petroleum Fractions - mineral turpentine, kerosine, gasoline, white spirits.
* Sodium carbonate ( washing soda ), sodium bicarbonate ( baking soda ),
sodium tetraborate ( borax ).
* Solvents - Acetone ( nail polish remover ), amyl acetate, methanol, ethanol
( methylated spirits ), glycerine, toluene, xylenes, iso propyl
alcohol.
* Terpenes - Eucalyptus oil, citrus oil, camphor
Specific Stain Strategies.
Ballpoint - methylated spirits, fullers earth, glycerine.

Blood - cold salty water, cornflour paste, or dilute bleach.
Copper deposits on sink or bathtub - ammonia (1 hr) then detergent.
Chewing Gum - freeze, or sponge with eucalyptus oil.
Chocolate - methylated spirits, or soak in 5% borax solution
Lipstick - glycerine, eucalyptus oil, dry-cleaning fluids.
Rust - oxalic acid, citric acid, tartaric acid
Tar - toluene, xylenes, eucalyptus oil.
Tea or Coffee - glycerine, warm borax solution
Wine - glycerine, borax solution, lemon juice
It depends on the sample and amount of rust. If the material is heavily

rusted, then physical techniques ( sand blasting ) may be appropriate.
Chemical techniques on steel usually involve phosphoric acid, and the
concentration depends whether the treatment can be washed off. An
excellent discussion is available in Product Finishing [28], along with
simple formulations. For removing light rust without subsequent removal
of the solution, 15% phosphoric acid + 4% n-butanol + <0.1% sulfuric acid
is used, but if the solution can be washed away, then a faster acting
33% phosphoric acid + 2% n-butanol mixture is preferred.
Several commercial silver polishes use a fine abrasive ( such as calcium

carbonate ) to physically remove the tarnish, and also include in their
formulation components ( such as benzotriazole ), that form complexes or
films that slow the reappearance of tarnish. There are also a variety of
chemical tarnish removers that contain sulfuric acid, sodium thiosulfate,
or hot sodium phosphate, a chemical formulary should contain recipes.
A very popular technique for removing tarnish ( silver sulfide ), involves

an electrochemical cell that utilises the electrochemical series. In an
electrochemical cell, oxidation occurs at one electrode, whilst reduction
occurs at the other. Electrical contact between the two metals provides the
pathway for electron migration to occur from the anode to the cathode, and
when immersed in an electrolyte, charge will be balanced by transfer of
the sulfide ions.
The standard electrode potential at 25C of Ag+ + e- -> Ag is +0.799V, and if

the other metal is anodic relative to silver, the silver in the sulfide at
the cathode will gain electrons and revert to metallic silver. The metal
at the anode will be oxidized by the removal of electrons. The sulfide ions
can travel to the anode via the electrolyte. The electrochemical series
indicates metals that will work, and some readily-available and cheap metals
are iron, zinc, aluminium and magnesium. The standard electrode potential at
25C of Al3+ + 3e- -> Al is -1.66V, and aluminium foil is cheap.
When aluminium is the anode, and water is the electrolyte, the aluminium
surface will eventually be coated with an insulating film of aluminium
sulfide - which will gradually decrease the cleaning speed. Adding sodium
bicarbonate ( baking soda ) or sodium carbonate ( washing soda ) to the
electrolyte will assist in the evolution of hydrogen as the silver is
converted, and the hydrogen will combine with the sulfide ions to produce
some hydrogen sulfide gas ( rotten eggs smell ). The aluminium at the anode
will be converted to aluminium oxide.
Aluminium oxidises on contact with air, forming an insulating layer of oxide

that is present on the surface of foil, disposable alumimium dishes, or
pots that are commonly used as the anode when cleaning silver at home.
Such a layer is brittle, and can micro-crack in hot water, and the higher
temperatures can also increase the redox reaction rate. Cleaning formulations
may include sodium chloride ( table salt ), boric acid, or borax. It should
be noted that the process is not converting the silver back to the original
hard, lustrous surface, but into a soft, white powder that can be removed by
rubbing. The sulfide has actually dislocated some silver atoms from the metal
surface, and the cleaning treatment will not relocate them, but it will
eliminate the unsightly, dark, tarnish.
A typical procedure is to line a pyrex glass dish with alumimium foil so the
bright side of the foil will contact the solution. Add one litre of water,
and heat until near boiling. Add one tablespoon of sodium chloride and one
tablespoon of sodium bicarbonate, and gently stir to dissolve. Ensure that
the silverware has been washed in warm dishwashing detergents, and well
rinsed in warm water, to remove dirt and grease. Carefully add the silverware
to the dish, ensuring that each item is in contact with the aluminium foil,
and leave until the tarnish has disapppeared. Because no protective film
has been provided, the tarnish may reappear rapidly.
There are several excellent books and journals on metal treatments in the
hobbies and metalworking sections of public libraries. For the serious
plater, the journals Surface Finishing and Product Finishing discuss all the
the chemical and electrical aspects - including disposal and destruction of
wastes. Their Annual Handbooks, along with the Canning Handbook of
Electroplating, have many recipes and details for the serious electroplater.
In any metal finishing process, the preparation of the substrate is of
great importance, and the recommended sequence of cleaning, pickling,
plating, and especially passivating should be carefully followed.
Failure to correctly passivate newly-deposited protective surfaces is the
main cause of the rapid formation of unsightly corrosion products.
31.18 How fast do solvents pass through human skin?
It obviously depends on the solvents, and traditional measurements have

been made using dead skin, but some recent work has provided a simple
comparison of individual solvents. It must be emphasised that mixtures of
solvents may have significantly different rates [29].
Permeability Constants in g/m2h

Solvent Average Standard Deviation
Dimethylsulfoxide 176 42
N-Methyl-2-pyrrolidone 171 59
Dimethylacetimide 107 19
Dimethylformamide 98 1.1
Methyl ethyl ketone 53 29
Methylene chloride 24 8.4
Water [^3H radiolabeled] 14.8 0.1
Ethanol 11.3 0.5
Butyl acetate 1.6 0.1
gamma butyrolactone 1.1 0.1
Toluene 0.8 0.7
Propylene carbonate 0.7 0.4
Sulfolane 0.2
31.19 What is the pH of Coca-cola?.
Phosphoric acid is an approved food-grade acid that is added to Coca-cola

to provide some of the taste. When CO2 is added to "carbonate" aqueous
solutions, carbonic acid is formed. A tin of coca-cola was cooled in a
refrigerator to 7C and the pH of the sample measured over time. The pH
electrode was not temperature-compensated, so a correction was applied.
Time pH pH
(when opened) (corrected)
Initial 2.75 @ 7C 2.6
30 seconds 2.78 @ 7C 2.6
60 seconds 2.80 @ 7C 2.6
2 minutes 2.82 @ 7C 2.7
4 minutes 2.80 @ 7C 2.6
A sample was degassed in an ultrasonic bath for several minutes and the
pH measured, and compared to a control sample maintained at the same
temperature and time profile.
pH
Degassed pH 2.52 @ 21c
RT sample 2.50 @ 20C
So the conclusion is that the pH of Coca-Cola is approximately 2.5 - 2.7.

Not surprisingly, the relatively weak carbonic acid from the dissolved CO2
did not significantly affect the pH of the beverage. The aluminium beverage
containers are lined with a thin polymer or lacquer coating to prevent the
aluminium metal dissolving into the beverage.
Note that the differing flotation characteristics of cans of the normal

versions of carbonated beverages like Coca-Cola ( they may sink ), and
the diet versions ( they may float ), has nothing to do with the amount
of CO2 present. It is due to the increase in solution density from the
few percent of sugar added to the normal version, while the diet version
has only a few hundred ppm of an artificial sweetener that is much sweeter
than sugar.
32. References
Note: "Refer 6.1" = Section 6, Reference 1.
Section 6:
[1] Beilstein's Handbuch der Organischen Chemie - 4th edition

F.K.Beilstein
(edited by P.Jacobson, B.Prager, F.Richter, H.G.Boit et al)
Springer (1918-)
[2] Bretherick's Handbook of Reactive Chemical Hazards - 6th edition

L.Bretherick, ( edited by P.G.Urben )
Butterworth-Heinemann ( December 1999 ) ISBN 075063605X
[3] Chemical Abstracts Service

CAS Internet E-mail: help@cas.org
2540 Olentangy River Rd Customer Service Telephone: 800-753-4227
PO Box 3012 or 614-447-3600 or (614) 447-3731
Columbus, OH 43210 Telefax: 614-447-3751
Fax: (614) 447-3751
http://www.cas.org
[4] Advanced Inorganic Chemistry - 6th edition

F.A.Cotton, G.Wilkinson, C.A.Murillo, M.Bochmann
John Wiley & Sons (April 1999) ISBN 0471199575
[5] Reagents for Organic Synthesis.

L.F.Fieser, M.Fieser.
Wiley (1980-) ISSN 0271-6747(v1-7) ISSN 0271-616X(v8-)
[6] Gardner's Chemical Synonyms and Trade Names - 11th edition

George W. A. Milne (Editor)
Ashgate Publishing Company (July 1999) ISBN 0566081903
[7] Gmelin's Handbuch der Anorganischen Chemie
E.Pietsch et al (editors)
Verlag Chemie (1926-)
[8] The Pharmacological Basis of Therapeutics - 9th edition

L.S.Goodman, A.G.Gilman, L.E.Limbird, P.B.Milinoff. (editors)
McGraw Hill (1996) ISBN 00702-62667
[9] Hawley's Condensed Chemical Dictionary - 13th edition

R.J.Lewis (editor)
John Wiley & Sons (December 1997) ISBN 0471292052 ;
CD-ROM Van Nostrand Reinhold (March 1998) ISBN 0471291919
[10] Dictionary of Organic Compounds ( formerly Heilbron ) - 6th edition

J.Buckingham, F.MacDonald (editors)
Chapman & Hall (December 1995) ISBN 0412540908
[11] Kirk-Othmer Encyclopedia of Chemical Technology - 4th edition.

Editor. M.Howe-Grant.
Wiley. ISBN 0-471-52681-9 (1993-) 25 volumes, approx. US$320/vol.
- available on CD-ROM.
[12] Lange's Handbook of Chemistry - 15th edition

J.A.Dean (editor)
McGraw-Hill (October 1998) ISBN 0070163847
[13] Martindale : The complete drug reference - 32nd edition

K.Parfitt (editor)
Pharmaceutical Press (April 1999) ISBN 085369429X
[14] Encyclopedia of Chemical Processing and Design

J.J.McKetta
Marcel Dekker (1990-) ISBN 0-8247-2497-6
[15] A Comprehensive Treatise on Inorganic and Theoretical Chemistry

J.W.Mellor
Longman (1922-1967)
[16] Merck Index - 12th edition

S.Budavari et al. (editors)
- available on CD-ROM for approximately three times the hardcopy price,
check out the Merck WWW site for details.
[17] Chemical Engineers' Handbook - 7th edition

R.H.Perry and D.W.Green (editors)
McGraw-Hill (1997) ISBN 0-07-049841-5
CD-ROM Version McGraw-Hill (January 1999) ISBN 0071344128
[18] Registry of Toxic Effects of Chemical Substances

National Institute for Occupational Safety and Health
Cincinnati, Ohio 45226.
[19] CRC Handbook of Chemistry and Physics 1999-2000 - 80th edition

D.R.Lide (editor)
CRC Press (June 1999) ISBN 0849304806
[20] Sax's Dangerous Properties of Industrial Materials - 10th edition

N.I.Sax ( edited by R.J.Lewis Sr. )
John Wiley & Sons (November 1999) ISBN 0471354066
CD-Rom edition John Wiley & Sons (November 1999) ISBN 0471378607
Book & CD-Rom edition John Wiley & Sons (November 1999) ISBN 0471378585
[21] Shreve's Chemical Process Industries - 5th edition

R.N.Shreve and G.T.Austin
McGraw Hill (1984) ISBN 0-07-057147-3
[22] Ullmann's Encyclopedia of Industrial Chemistry - 6th edition.

Editors, J.E.Bailey, J.Brinder, M.Bohnet
VCH. Book & CD-Rom edition (July 1999) ISBN 3527201637
[23] Vogel's Textbook of Quantitative Chemical Analysis - 5th edition

A.I.Vogel
(previously Vogel's Textbook of Quantitative Inorganic Analysis )
5th Ed. (revised by G.H.Jeffery et al) Longman (1989) ISBN 0-470-21517-8
4th Ed. (revised by J.Bassett et al.) Longman (1978) ISBN 0-582-46321-1
3rd Ed. Longman (1962) ISBN 0-582-44247-8
(Note - I personally prefer the 3rd edition which was the last written
by A.I.Vogel, he provided more alternatives for each analysis,
especially for titrations )
[24] Vogel's Qualitative Inorganic Analysis - 7th edition

A.I.Vogel
( previously Macro and Semi-micro Qualitative Inorganic Analysis )
7th Ed. ( revised by G.Svehla ) Longmans (1996) ISBN 058-221866-7
4th Ed. Longmans (1954) SBN 582 44246 X
( Note - I've never seen the 7th edition - I'm very happy with the 4th
edition, which was the last by A.I.Vogel )
[25] Vogel's Textbook of Practical Organic Chemistry - 5th edition

A.I.Vogel
5th Ed. (revised by A.R.Tatchell et al) Wiley (1989) ISBN 0582-46236-3
4th Ed. (revised by B.S.Furniss et al) Longman (1978) ISBN 0582-44250-8
3rd Ed. Longmans (1956)
( Note - the 3rd edition was the last by A.I.Vogel, but the 4th has the
advantage of discussing of modern techniques. I have not seen the 5th.)
[26] Vogel's Elementary Practical Organic Chemistry - 3rd edition

A.I.Vogel. ( revised by B.V.Smith and N.M.Waldron )
Longman (1980) ISBN 0-582-47009-99v10
Section 7:
[1] Refer 6.3
[2] Dialog
Knight-Ridder Information, Inc.
www http://www.dialog.com
email info@dialog.com
phone 800-334-2564, or 415-254-7000
fax 415-254-7070
[3] Information Sources for Organic Chemistry, 1-3.

A.S.Somerville
J.Chem.Ed v.68 p.553-561 (1991)
J.Chem.Ed v.68 p.842-853 (1991)
J.Chem.Ed v.69 p.379-386 (1992)
[4] Searching the Beilstein Database Online: A comparison of systems.

R.E.Buntrock, M.A.Palma
Database, December 1990. p.19-34
[5] A Wealth of Information Online
M.J.Mazzella
Chemical Engineering. June 1989 p.112-127
Section 9:
[1] What Every Engineer Should Know About Patents - 2nd edition
W.G.Konold, B.Tittel, D.F.Frei, D.S.Stallard
[2] Chem Sources : International ( biennial edition )

Phone: 864-646-7840 Fax: 864-646-9938
[3] Chem Sources : USA ( annual edition )

Phone: 864-646-7840 Fax: 864-646-9938
[4] OPD Chemical Buyers Directory - 82nd edition

( issued as part of subscription to Chemical Marketing Reporter)
Scnell Publishing (1995) ISBN 1-878800-04-3
[5] The Aldrich Catalog/Handbook ( annual edition )

Aldrich Chemical Company
P.O.Box 355
Milwaukee. Wl 53201
Orders: Mail PO Box 2060, Milwaukee Wl 53201 USA.
Phone. 414-273-3850
Fax. 414-273-4979
Customer Service: Phone 414-273-3850
[6] J.T.Baker Inc.

222 Red School Lane
Phillipsburg. NJ 08865
Phone 800-582-2537
Fax. 908-859-9318
[7] Refer 6.19
[8] Refer 6.16
[9] Refer 6.12
[10] Refer 6.9
[11] Tables of Physical and Chemical Constants - 16th edition

G.W.C Kaye and T.H.Laby ( now by a panel of editors )
Longman (1995) ISBN 0-582-226295
[12] Chemical Technicians' Ready Reference Handbook - 4th edition

G.J.Shugar, J.T.Ballinger, and L.M.Dawkins
McGraw Hill (1996) ISBN 0-07-057186-4
[13] Matheson Gas Data Book - 6th edition

W.Braker and A.L.Mossman
Matheson Gas Products (1980) ISBN 999-267037-1
[14] McGraw-Hill Concise Encyclopedia of Science and Technology - 4th edition
S.P.Parker, J.Weil, S.R.Felsenfeld (editors)
McGraw-Hill (January 1998) ISBN: 0070526591
[15] Van Nostrand's Scientific Encyclopedia - 8th edition

D.Considine ( editor )
CD-Rom John Wiley & Sons (January 1999) ISBN 0471293237
[16] McGraw Hill Encyclopedia of Chemistry

S.P.Parker
McGraw-Hill (1993) ISBN 0-07-045455-8
[17] McGraw-Hill Encyclopedia of Science and Technology - 8th edition

S.P.Parker
McGraw-Hill (January 1997) ISBN 0079115047
McGraw-Hill Concise Encyclopedia of Science and Technology - 3rd edition
S.P.Parker
McGraw-Hill (June 1994) ISBN 0070455600
[18] Refer 6.11
[19] Refer 6.22
[20] Refer 6.1
[21] Refer 6.7
[22] Refer 6.10
[23] Refer 6.14
[24] Encyclopedia of Polymer Science and Engineering - 2nd edition

H.F.Mark et al (editors)
John Wiley (1985-1990) ISBN 0-471-89540-7(v1)
Concise Polymeric Materials Encyclopedia
J.C.Salamone
CRC Press (September 1998) ISBN 084932226X
[25] Thorpe's Dictionary of Applied Chemistry - 4th edition

I.Heilbron et al (editors)
Longmans (1954)
[26] High Vacuum Techniques for Chemical Synthesis and Measurements.

P.H.Plesch
[27] High Vacuum Technique: Theory, Practice and Properties of Materials

- 4th Edition
J.Yarwood
[28] Swagelok Tube Fitting and Installation Manual

F.J.Callahan
Markad Service Co. (1985)
[29] Thermocouples: Theory and Properties

D.D.Pollock
CRC Press (1991) ISBN 0-8493-4243-0
[30] Merck KGaA
D-64271 Darmstadt
Germany
Phone ++496151/72-0
Fax ++496151/72-2000
[31] Rhone-Poulenc Prolabo Division

12 Rue Pelee
75011 Paris
France
[32] Sigma Chemical Company

P.O.Box 14508
St.Louis, MO.
USA 63178-9916
[33] Janssen Chimica Division

Janssen Pharmaceuticalaan 3
2440 Geel
Belgium
[34] Lancaster Synthesis Ltd

Eastgate, White Lund
Morecombe, Lancashire LA3 3DY
United Kingdom.
[35] Standard Infrared Spectra

[36] The Aldrich Library of Infrared Spectra - 3rd edition

C.J.Pouchert
[37] The Aldrich Library of FT-IR Spectra -2nd edition

C.J.Pouchert
Aldrich Chemical (1985-) ISBN 0-941633-20-9(v1&2), 0-941633-19-5(v3)
[38] Standard NMR Spectra

[39] The Aldrich Library of C13 and H1 FT-NMR Spectra

C.J.Pouchert and J.Behnke
[40] The Aldrich Library of NMR Spectra - 2nd edition

C.J.Pouchert
Aldrich Chemical (1983) ISBN 0-941633-08-X
[41] NIST/EPA/NIH Mass Spectral Data Base

S.R.Heller and G.W.A.Milne
US Govt. Printing Office (1978) NSRDS-NBS 63
CD-ROM ( MS-Windows - Aldrich Z25,737-0 US$1320 )
## http://www.nist.gov/srd/nist1.htm
[42] Wiley/NBS Registry of Mass Spectral Data

F.W.Lafferty and D.B.Stanffer ( editors )
John Wiley (1988)
[43] Industrial Chemical Thesaurus - 2nd edition

M.B. Ash, I.A. Ash
John Wiley & Sons (January 1997) ISBN 047118893X
[44] Encyclopedia of Industrial Chemical Additives
M.Ash and I.Ash
Chemical Publishing Co. (1987) ISBN 0-8206-0320-1
[45] Chemical Tradename Dictionary

M.Ash and I.Ash
VCH (1993) ISBN 1-569081-625-2
[46] The Chemical Formulary

( 35 volume series that is still growing )
Chemical Publishing Company (1933-) ISBN 0820603635 (1999 vol)
Cumulative Index - Volumes 1-34
Chemical Publishing Company (March 1999) ISBN: 0820603554
[47] The History of Chemistry

J.Hudson
Routledge Chapman and Hall (1992) ISBN 0-412-03641-X
[48] Chemistry of the Elements - 2nd edition

N.N.Greenwood and A.Earnshaw
Butterworth Heineman (1997) ISBN 0-08-0379419
[49] The Elements - 3rd edition

J.Emsley
[50] Discovery of the Elements - 7th edition

M.E.Weeks ( revised by H.M.Leicester )
Journal of Chemical Education (1968) ISBN 0-317-09341-X
[51] The Chemical Bond: Structure and Dynamics

A.Zewail (Ed)
Academic Press (1992) ISBN 0-12-779620-7
[52] Chemistry in the Next Century

Thomas Midgley, Jr.
Ind.Eng.Chem. v.27 n.5 p.494-498 (1935)
[53] Midgley: Saint or Serpent?.

G.B.Kauffman.
Chemtech, December 1989. p.717-725.
Section 10:
[1] Sigma-Aldrich CD-ROM of 70,000+ MSDS

Aldrich Catalogue Z17,500-5
Annual Subscription US$1650
[2] Fire Protection Guide to Hazardous Materials - 12th edition

National Fire Protection Assiciation (November 1997) ISBN 0877654271
[3] The Sigma-Aldrich Library of Chemical Safety Data - 2nd edition

R.E.Lenga (editor)
[4] CRC Handbook of Laboratory Safety - 4th edition.

A.K.Furr (editor)
CRC Press (1995) ISBN 08493-2518-8
[5] Hazards in the Chemical Laboratory - 5th edition

S.G.Luxon (editor)
Royal Society of Chemistry (1992) ISBN 0-85186-229-2
[6] Refer 6.2
[7] The Sigma-Aldrich Library of Regulatory and Safety Data

R.E.Lenga and K.L.Votoupal (editors)
[8] Threshold Limit Values and Biological Exposure Indices - 1990/91 edition
TLV-BEI (1990) ISBN 0-936712-86-4
[9] Guide to Occupational Exposure Values - 1990-1991

Guide to Occupational Exposure Values (1990) ISBN 0-936712-87-2
[10] Encyclopedia of Occupational Health and Safety - 3rd edition

L.Parmeggiani
International Labour Office - Geneva (1989) ISBN 92-2-103289-2
[11] Refer 9.17
[12] Guidelines for Laboratory Design: Health and Safety Considerations

- 2nd edition
L.J.Diberardinis et al.
[13] Laboratory Health and Safety Handbook - 2nd edition

R.S.Stricoff and D.B.Walters
[14] Contact Lenses and Chemicals: An Update

E.B.Segal
[15] Contact Lens Emergencies

A.P.Cullen
[16] Contact Lenses and Chemicals: Update 1997

E.B.Segal
Chemical Health and Safety. May/June 1997 p.33-37
[17] Contact lenses in industry: The ongoing discussion.

B.R.Blais
Chemical Health and Safety. July/August 1997 p.22-26
Section 11:
[1] Refer 9.36
[2] Refer 9.37
[3] Refer 9.40
[4] Refer 9.39
[5] Refer 9.41

[6] Fiveash Data Management, Inc. Reference Spectra Databases,
P. O. Box 400 Books, and Chemical Information
Fort Atkinson, WI 53538 USA
[7] Refer 9.24
[8] Spot Tests in Organic Analysis - 7th edition

F. Fiegl
Elsevier (June 1966) ISBN 0444402098
[9] Spot Tests in Inorganic Analysis - 6th edition

F.Feigl and V.Anger ( translated by R.E.Oesper )
Elsevier (1972) ISBN 0-444-409297
[10] Refer 6.24
[11] Refer 6.23
[12] Refer 6.25
[13] Treatise on Analytical Chemistry - 2nd edition

I.M.Kolthoff and P.J.Elving
Wiley Interscience (1978) ISBN 0-471-80648-X (p1.v14.)
[14] Techniques of Chemistry series

A.Weissberger
( Previously known as Techniques of Organic Chemistry and Techniques of
Inorganic Chemistry )
[15] Instrumental Methods of Analysis - 7th edition

H.H.Willard, L.L.Merritt, J.A.Dean, F.A.Settle, (editors).
Wadsworth Publishing (February 1988) ISBN 0534081428
[16] Analytical Instrumentation Handbook

G.W.Ewing (editor)
[17] 'Analar' Standards for Laboratory Chemicals - 8th edition

D.J.Bucknell
BDH Chemicals/Whitefriars Press (1984) ISBN 0-9500439-4-X
[18] Reagent Chemicals - 9th edition

American Chemical Society (September 1999) ISBN 0841236712
[19] Refer 6.13
[20] Official Methods of Analysis - 16th edition

P.A.Cunniff (editor)
Association of Official Analytical Chemists (1995) ISBN 0-935584-54-4
[21] Compilation of EPA Sampling and Analysis Methods

L.H.Keith (editor)
Lewis Publishers Boca Raton (1991)
[22] EPA Sampling and Analysis Methods Database

- available on computer disk ( Aldrich Cat. Z23,084-7 US$257.95 )
[23] Chromatography in Petroleum Analysis

K.H.Altgelt and T.H.Gouw (editors)
Marcel Dekker (1979) ISBN 0-8247-6790-X
[24] The Analysis of Gases by Chromatography

C.J.Cowper and A.J.DeRose
Pergamon Press (1983) ISBN 0-08-024027-5
[25] Standard Methods for the Examination of Water and Wastewater

- 20th Edition ( APHA,AWWA, and AWPF joint methods )
A.E.Greenberg, A.D.Eaton, L.S.Cleseri
American Public Health Assn. (January 1999) ISBN 0875532357
Book & CD-Rom edition (March 1999) ISBN 0875532403
CD-Rom edition (March 1999) ISBN 087553239X
[26] Water Analysis

W.Fresenius, K.E.Quentin, and W.Schneider (editors)
Spring-Verlag (1988) ISBN 0-387-17723-X
[27] Determination of Organic Substances in Water

T.R.Crompton
Wiley-Interscience (1985) ISBN 0-471-90468-6 (v1), 0-471-90469-4 (v2).
[28] Water - A Comprehensive Treatise ( six volumes )

F.Franks (editor)
Plenum Press (1972-1979) ISBN 0-306-37181-2 (v1)
[29] Methods of Decomposition in Inorganic Analysis

Z.Sulcek and P.Povondra
CRC Press (1989) ISBN 0-8493-4963-X
[30] Handbook of Analytical Derivatization Reactions

D.R.Knapp
John Wiley (1979) ISBN 0-471-03469-X
[31] Handbook of Derivatives for Chromatography - 2nd edition

K.Blau and J.M.Halket (editors)
John Wiley (1993) ISBN 0-471-92699-X
[32] Environmental Chemistry - 6th Ed.

S.E.Manahan
Lewis Publishers (1994) ISBN 1-56670-088-4
[33] Fundamentals of Environment Chemistry

S.E.Manahan
Lewis Publishers (1993) ISBN 0-873-71587-X
[34] Environmental Organic Chemistry

R.P.Schwarzenbach, P.M.Gschwend, and D.M.Imboden
John Wiley (1993) ISBN 0-471-83941-8
[35] Metals and their Compounds in the Environment: Occurrence, Analysis

and Biological Relevance.
E. Merian (editor)
VCH (1991) ISBN 0-89573-562-8
[36] Physical Chemistry - 6th edition

P.W.Atkins
Book & CD-Rom edition W H Freeman (December 1997) ISBN 0716728710
Physical Chemistry (Solutions Manual)
P.W. Atkins, C. A. Trapp, M. P. Cady, C. Giunta
W H Freeman (December 1997) ISBN 0716731673
[37] Textbook of Physical Chemistry - 2nd edition
S.Glasstone
Van Nostrand/MacMillan (1946)
[38] Physical Methods of Chemistry Series - 2nd edition

B.W.Rossiter, J.F.Hamilton
( Previously known as Volume 1 of the Techniques of Chemistry series )
[39] Inorganic Chemistry - 3rd edition

D. F. Shriver, P. W. Atkins
W H Freeman (February 1999) ISBN 0716736241
[40] Refer 6.23
[41] Refer 6.7
[42] Encyclopedia of Inorganic Chemistry

B.R.King (editor)
John Wiley (1994) ISBN 0-471-936200
CD-ROM edition John Wiley & Sons (August 1997) ISBN 047196798X
[43] Refer 6.4
[44] Organic Chemistry - 7th edition

T.W.G.Solomons, C.B.Fryhle, T.G.Solomons
John Wiley & Sons (July 1999) ISBN 0471190950
[45] Organic Chemistry - 3rd edition

L.F.Fieser and M.Fieser
Reinhold (1956)
[46] Advanced Organic Chemistry - 3rd edition

F.A.Carey and R.J.Sundberg
Plenum Press (1990) ISBN 0-306-43447-4(A), 0-306-43457(B)
[47] Organic Reactions

L.A.Paquette, R.Bittmen
( A 54 volume series that is still growing )
John Wiley & Sons (1942+) Vol 54 (June 1999) ISBN 0471348880
[48] Refer 6.5
[49] The Logic of Chemical Synthesis

X.Cheng, E.J.Corey
John Wiley & Sons (June 1995) ISBN: 0471115940
[50] Refer 6.10
[51] Refer 6.1
[52] Refer 6.21
[53] Refer 6.8
[54] Essentials of Medicinal Chemistry - 2nd edition

A.Korolkovas (editor)
John Wiley (1988) ISBN 047-188356-5
[55] Handbook of Pharmaceutical Excipients - 3rd edition

A.Wade, P.J.Weller
American Pharmaceutical Assoc. (November, 1999) ISBN 091733096X
Section 12:
[1] Names and Symbols of Transfermium Elements

Pure and Appl.Chem. v.66 p.2419-2421 (1994)
[2] Heavy Element name saga ends

M.Freemantle
C&EN 8 September 1997 p.9-10
[3] Interconversion of ASHRAE Refrigerant Numbers and Chemical Compositions

A.A.Woolf
J.Chem.Ed. v.70 p.35-36 (1993)
[4] Polyunsaturated fatty acids in diet and health

I.S.Newton
Chemisty and Industry 21 April 1997 p.302-305.
[5] Nutritional aspects of n-3 fatty acids

Inform v.8 n.5 p.428,429,433,434,437,439,440,443,444,447 (May 1997)
[6] Conjugated Linoleic Acid - The Good News about Animal Fat.
C.Steinhart
J.Chem.Ed. v.73 p.A302-A303 (December 1996)
[7] Conjugated Linoleic Acid, a newly recognised nutrient

M.W.Pariza
Chemistry and Industry. 16 June 1997 p.464-466.
[8] Concise Encyclopedia Biochemistry and Molecular Biology - 3rd edition

T.Scott, E.I.Mercer
Walter De Gruyter (December 1996) ISBN 3110145359
[9] International Encyclopedia of Chemical Science

D.Van Nostrand. (1964)
[10] Webster's Third New International Dictionary

P.B.Gove (editor)
Merriam Webster (1993) ISBN 0877792011
[11] Bring Back Equivalent Weight - If You Want the Kids To "Think"!
M.Laing
J.Chem.Ed. v.72 p.1007-1012 ( November 1996 )
[12] Dyeing Reagents for Thin Layer and Paper Chromatography

22/II 13/2699/10/1170L
E.Merck, Darmstadt.
[13] Piranha solution explosion

D.A.Dobbs, R.G.Bergman, K.H.Theopold
C&EN 23 April 1990 p.2
[14] Cleaning glass funnels

T.Wnuk
C&EN 25 June 1990 p.2
[15] Piranha solution explosions

C.V.Erickson
C&EN 13 August 1990 p.2
Section 13:
[1] The Sassafras Tree and Designer Drugs - From Herbal Tea to Ecstasy.
L.G.French
J.Chem.Ed. v.72 n.6 p.484-491. (June 1995).
[2a] Pihkal : A Chemical Love Story

A.Shulgin, A.Shulgin
[2b] Tihkal : The Continuation
A.Shulgin
[3] Analysis of Semtex Explosives

J.R.Hobbs
p.409-427
J.Yinon (editor)
[4] The Semtex-H Story

A.W.Feraday
p.67-72.
J.Yinon (editor)
[5] Oklahoma bomb shows common items' power

M.Rouhi
C&EN. 1 May 1995. p.8
[6] Nitrogen Triiodide

I.C.Tornieporth-Oetting, T.M.Klapotke
Angew.Chem.Int.Ed.Engl. v.29 p.677-679 (1990)
[7] The Chemical Elements and their Compounds

N.V.Sidgwick
Oxford University Press (1950)
[8] Advanced Energetic Materials Emerge for Military and Space Applications
S.Borman
C&EN 17 January 1994 p.18-22.
[9] Recent Advances in Explosives and Solid Propellants

J.C.Bottaro
Chemistry & Industry (UK) 1 April 1996 p.249-252.
[10] Transforming Explosive Art in Science

A.Heller
Science & Technology Review June 1997 p.4-13.
[11] Refer 6.11

v.10. p.1-125. "Explosives and Propellants"
[12] Explosives - 4th edition, English

J.Kohler
John Wiley and Sons (November 1992) ISBN 3527285067
[13] Chemistry of Powder and Explosives

T.L.Davis
Angriff Press (June 1972) ISBN 0913022004
- available from Delta Press (deltagrp@eldonet.com),
or Loompanics (loompanx@olympus.net)
P.O. Box 1197, Port Townsend. WA 98368.
[14] Investigations of Fire and Explosion Accidents in the Chemical, Mining,

and Fuel-Related Industries - A Manual
J.M.Kuchta
US Dept. of the Interior. Bureau of Mines Bulletin 680 (1985).
[15] The Chemistry and Technology of Explosives

T.Urbanski
Pergamon. v.1-3 (1967) v.4 (1984) ISBN 0-08-030252-1
[16] The Encyclopedia of Explosives and Related Items

B.T.Federoff, O.E.Sheffield, and S.Kaye
PATR 2700, v.1-10. ARDEC, Dover, NJ.
Section 15:
[1] Chemical Demonstrations - A Handbook for Teachers of Chemistry

B.Z.Shakhashiri
University of Wisconsin Press (4 vols.) ISBN 0-318-56863-2 (1992)
http://scifun.chem.wisc.edu/demoser.html
Vol 001 (December 1983) ISBN 0299088901
Vol 002 (January 1986) ISBN 0299101304
Vol 003 (April 1989) ISBN 0299119505
Vol 004 (March 1992) ISBN 0299128601
[2] Chemical Demonstrations - A Sourcebook for Teachers - 2nd edition

L.R.Summerlin, J.L.Ealy Jr.
Amer.Chem.Soc. (1988) ISBN 0-8412-1481-6 (v1), 0-8412-1535-9 (v2)
[2a] Chemical Magic - 2nd edition

L.A.Ford, E.W.Grundmeier (Designer)
Dover Pubications (August 1993) ISBN 0486676285
[3] The Blue Bottle Experiment Revisited

A.G.Cook, R.M.Tolliver, and J.E.Williams.
J.Chem.Ed. v.71 n.2 p.160-161 (February 1994)
[4] Oscillating Chemical Reactions

I.R.Epstein, K.Kustin, P.De Kepper, and M.Orban
Scientific American p.96-108 (1983)
[5] Oscillating Chemical Reactions and Nonlinear Dynamics

R.J.Field and F.W.Schneider
J.Chem.Ed v.66 p.195-204 (March 1989)
[6] Recipes for Belousov-Zhabotinsky Reagents

W.Jahnke and A.T.Winfree
J.Chem.Ed v.68 p.320-324 (April 1991)
[7] Hydrogen Balloon Explosions

R.Battino, B.S.Battino
J.Chem.Ed. v.69 n.11 p.921-923 (November 1992)
[8] The Incredible "Glowing" Pickle and Onion and Potato and...
P.M.Weimer, R.Battino
J.Chem.Ed. v.73 n.5 p.456-457 (May 1996)
[9] Glowing Veggies
P.Scharlin, A.A.Cleveland, R.Battino, and M.E.Thomas.
J.Chem.Ed. v.73 n.5 p.457-459 (May 1996)
[10] The Gelation of Polyvinyl Alcohol with Borax

E.Z.Casassa, A.M.Sarquis, and C.H.Van Dyke
J.Chem.Ed. v.63 n.1 p.57-60 (January 1986)
[11] Slime and Poly(Vinyl Alcohol) Fibers

G.S.Stroebel, J.A.Whitesell, and R.M.Kriegel
J.Chem.Ed. v.70 n.11 p.893 (November 1993)
[12] The Gelation of Poly(Vinyl Alcohol) with Na2B4O7.10H2O: Killing Slime

K.W.McLaughlin, N.K.Wyffels, A.B.Jentz, and M.V.Keegan
J.Chem.Ed v.74 n.1 p.97-99 (January 1997)
Section 16:
[1] Desiccant Efficiency in Solvent Drying. A Reappraisal by

Application of a Novel Method for Solvent Water Assay.
D.R.Burfield, K.H.Lee, R.H.Smithers.
J.Org.Chem. v.42, p.3060-3065. (1977).
[2] Molecular Sieves - Dessicants of Choice.

D.R.Burfield, G.H.Gan, R.H.Smithers.
J.Appl.Chem.Biotech. v.28, p.23-30. (1978).
[3] Desiccant Efficiency in Solvent Drying. 3. Dipolar Aprotic Solvents

J.Org.Chem. v.43, p.3966-3968 (1978).
[4] Desiccant Efficiency in Solvent Drying. Applications of Cationic Exchange

Resins.
J.Chem.Tech.Biotechnol. v.30, p.491-496 (1980)
[5] Desiccant Efficiency in Solvent and Reagent Drying. 5. Amines

D.R.Burfield, R.H.Smithers, and A.S.C.Tan
J.Org.Chem. v.46, p.629-631 (1981).
[6] Drying of Grossly Wet Ether Extracts

J.Chem.Ed. v.59, p.703-704 (1982)
[7] Desiccant Efficiency in Solvent and Reagent Drying. 7. Alcohols.

J.Org.Chem. v.48, p.2420-2422 (1983)
[8] Desiccant Efficiency in Solvent and Reagent Drying. 8. Molecular Sieve

Column Drying of 95% Ethanol: An Application of Hygrometry to the Assay
of Solvent Water Content.
D.R.Burfield, G.T.Hefter, and D.S.P.Koh
J.Chem.Tech.Biotechnol. v.34A, p.187-194 (1984)
[9] Desiccant Efficiency in Solvent and Reagent Drying. 9. A Reassessment of

of Calcium Sulfate as a Drying Agent.
D.R.Burfield.
J.Org.Chem. v.49, p.3852-3854 (1984)
[10] Oven Drying of Volumetric Glassware

D.R.Burfield and G.Hefter
J.Chem.Ed. v.64 p.1054 (1987)
[11] Neues Verfahren zur maBanalytischen Bestimmung des Wassergehaltes

von Flussigkeiten und festen Korpern
K.Fischer
Angew. Chem., v.48 p.394-396 (1935)
[12] Titrimetric Determination of Water in Organic Liquids using Acetyl

Chloride and Pyridine
D.M.Smith and W.M.D.Bryant
J.Amer.Chem.Soc., v.57 p.841-845 (1935)
[13] Karl Fischer Titration

E.Scholz
[14] An Effective Technique for Cleaning Glassware

D.P.Higley
J.Chem.Ed. v.52 p.306 (1975)
[15] Refer 6.23
[16] Standard Glassware Cleaning Solutions

The Chemist's Companion
J.Wiley & Sons ISBN 0-471-31590-7 (1972)
[17] Laboratory Hazards - an explosion involving "chromic acid".

W.R.Bryson
Chem.Brit. v.11 p.377 (1975)

M.J.Pitt
Chem. Brit. v.11 p.456 (1975)

S.Downing
Chem. Brit. v.11 p.456 (1975)
[20] A Less Hazardous Chromic Acid Substitute for Cleaning Glassware

P.L.Manske, T.M.Stimpel, and E.L.Gershey
J.Chem.Ed. v.67 p.A280-A282 (1990)
[21] Regeneration of Chromic Acid Cleaning Solution

D.Schwab and P.Martinez
J.Chem.Ed. v.66 p.528 (1989)
[22] Oxidising Acid Baths - without Chromate Hazards

H.M.Stahr, W.Hyde, and L.Siegler
Anal.Chem. v.54 p.1452A (1982)
[23] How to Remove Silicone Compounds or Greases.

Dow Corning Silicone Bulletin 06-005 (1962)
[24] Removing Silicone Grease from Glassware

T.H.Lowry
J.Chem.Ed. v.74 p.841 (1997)
[25] Removing Silicone Greases from Round Bottom Flasks

T.J.Reilly
J.Chem.Ed. v.73 p.381 (1996)
Section 17:
[1] Purification of Laboratory Chemicals - 4th edition

W.L.F.Armarego, D.D.Perrin
Butterworth-Heinemann (December 1997) ISBN 0750637617
[2] Palladium Reagents in Organic Syntheses

R.F.Heck
Academic Press (1985)
Section 18:
[1] Refer 15.1
[2] A Multicolored Luminescence Demonstration

P.E.Smith, K.Johnston, D.M.Reason, and G.M.Bodner
[3] Overview of Sweeteners

J.W.Ellis
[4] Discovery of Highly Sweet Compounds from Natural Products

A.D.Kinghorn, E.J.Kennelly
[5] Sweeteners: A question of taste

G.G.Birch
Chemistry and Industry 3 February 1997 p.90-94.
[6] Rediscovering the Wheel - The Flame Test Revisited

R.O.Ragsdale and J.A.Driscoll
[7] Flame Colors Demonstration

J.R.Peyser and J.R.Luoma.
J.Chem.Ed. v.65 n.5 p.452-453 (May 1988)
[8] Refer 6.11

Chromogenic Materials v.6 p.312-343.
[9] Electrochromic Materials

R.J.Mortimer
Chem.Soc.Revs. v.26 p.147-156 (1997)
[10] Sunglasses that Respond to Brightness

S.D.Stookey
J.Chem.Ed. v.47 p.176 (1970)
[11] Photochromic Sunglasses

B.Osterby, R.D.McKelvey, and L.Hill
J.Chem.Ed. v.68 p.424-425 (1991)
[12] Thermochromism
J.H.Day
Chem.Rev. v.63 p.65-80 (1963)
[13] The Physics and Chemistry of Color

K.Nassau
John Wiley & Sons. (1983) ISBN 047-186776-4
Section 19:
[1] Solutions to Sticky Problems. Booklet

More Solutions to Sticky Problems. Booklet
BROOKFIELD Engineering Laboratories Inc, MA, USA.
[2] Introduction to Practical Viscometry. Booklet

HAAKE, Mess-Technik GmbH.
[3] Principles and Applications of Rheology.

A.G.Frederikson
Prentice-Hall Inc. NJ.
[4] Viscosity and Flow Measurement.

Van Wazer, Lyons, Kim, Colwell.
Interscience Publishers. NY
[5] Electrorheological technology: The future is now.

K.O.Havelka and J.W.Pialet.
Chemtech p.36-45 ( June 1996 )
[6] Electrorheological Fluids: Mechanisms, Properties, Technology and

Applications.
Edited by R.Tao and G.Roy
World Scientific, Singapore (1994) ISBN 98102-16394
[7] Active Damping using ERM fluids.

Automotive Engineering p.19-23 (June 1993).
[8] Extraction with Supercritical Fluids

G.M.Schneider, E.Stahl, G.Wilke
Verlag Chemie (1980) ISBN 352725854X
[9] Solvents get the big squeeze

D.Bradley
New Scientist, 6 August 1994. p.32-35.
[10] Past, Present, and Possible Future Applications of Supercritical

Fluid Extraction Technology
C.L.Phelps, N.S.Smart, and C.M.Wai
J.Chem.Ed. v.73 n.12 p.1163 (December 1996)
[11] Cavitation and Bubble Dynamics

C.E. Brennen.
[12] Relativistic Effects in Structural Chemistry

P.Pyykko
Chem. Rev. v.88 p.563-594 (1988)
[13] Relativistic Effects on Chemical Properties

D.R.McKelvey
[14] Relativistic Effects at the Freshman Level

M.S.Banna
J.Chem.Ed. v.62 p.197-198 (March 1985)
[15] Periodic Contractions among the Elements

J.Mason
J.Chem.Ed. v.65 p.17-20 (January 1988)
[16] Why is Mercury Liquid?
L.J.Norby
Section 20:
[1] Refer 11.15
[2] Chemical Instrumentation: A Systematic Approach. - 3rd edition

H.A. Strobel
John Wiley (1989) ISBN 0-471-61223-5
[3] Polarized Light.

W.A. Shurcliff and S.S. Ballard
Princeton: D. Van Nostrand, (1964)
[4] Optics - 3rd edition

E.Hecht, A.Zajac, K.Guardino (editors)
Addison-Wesley Publishing (August 1997) ISBN 0201838877
[5] The Chemist's Ready Reference Handbook

G.J. Shugar and J.A. Dean
New York: McGraw-Hill (1990) ISBN 0-07-057178-3
[6] Molecular Optical Activity and the Chiral Discriminations.

S.F. Mason
[7] Molecular Light Scattering and Optical Activity

L.D. Barron
[8] Problems and Experiments in Instrumental Analysis.

C.E. Meloan and R.W. Kiser
Charles E. Merrill Books, Inc. 1300 Alum Creek Drive,
Columbus 16, OH, (1963).
Section 22:
[1] Refer 11.13
[2] Refer 11.14
[3] Refer 11.15
[4] Refer 11.16
Section 23:
[1] Laboratory Handbook of Chromatographic and Electrophoretic Methods

- 3rd edition
E.Heftmann
[2] Thin Layer Chromatography - 2nd edition

E.Stahl
[3] Techniques of Chemistry - Vol. XIV

Thin-Layer Chromatography - 2nd edition
J.G.Kirchner
Sigma Chemical (1990) ISBN 0-941633-25-X (reprint)
[4] Refer 11.30
[5] Refer 11.31
[6] Basic Gas Chromatography

H.M. McNair, J.M.Miller
John Wiley & Sons (October 1997) ISBN 047117260X
[7] High-Resolution Gas Chromatography

K.J.Hyver and P.Sandra
Hewlett Packard (1989) P/N=5950-3562 ISBN 999-184716-2
[8] Open Tubular Column Gas Chromatography

M.L.Lee, F.J.Yang, K.D.Bartle
[9] Sadtler Gas Chromatography Standard Retention Index Library

Sadtler Research Laboratories (1986).
[10] Introduction to Modern Liquid Chromatography - 2nd edition

L.R.Snyder and J.J.Kirkland
[11] Troubleshooting LC Systems

J.W.Dolan and L.R.Snyder
Humana Press (1989) ISBN 0-89603-151-9
[12] Practical HPLC Method Development - 2nd edition

L.R.Snyder, J.J.Kirkland, and J.L.Glajch.
[13] The Practice of Ion Chromatography

F.C.Smith Jr. and R.C.Chang
Krieger Publishing (1991) ISBN 089464-502-1
[14] Ion Chromatography

H.Small
Plenum Press (1989) ISBN 0-306-43290-0
[14a] Ion Chromatography - 2nd edition

J.Weiss
John Wiley & Sons (December 1994) ISBN 3527286985
[15] Modern Size Exclusion Chromatography

W.W.Yau, J.J.Kirkland, D.Bly
Section 24:
[1] Reactions in Supercritical Fluids

L.Boock, B.Wu, C.LaMarca, M.Klein, and S.Paspek
Chemtech. December 1992. p.719-723.
[2] Supercritical Fluid Extraction and Chromatography

B.A.Charpentier and M.R.Sevenants
[3] Supercritical Fluid Science and Technology
K.P.Johnston and M.L.Penninger
[4] Supercritical Fluid Engineering Science: Fundamentals and Applications

E.Kiran, J.F.Brennecke
Amer.Chem.Soc. Symposium Series v.514 (1993) ISBN 0-8412-2513-3
[5] Solving Process Problems with Supercritical Extraction

J.Via, L.T.Taylor
Chemtech. November 1993. p.38-44.
[6] The Use of Supercritical Fluids in the Isolation of Natural Products

C.D.Bevan and P.S.Marshall
Natural Products Reports, 1994. p.451-466.
[7] Supercritical Chemistry: Synthesis with a Spanner.

M.Poliakoff and S.Howdle
Chemistry in Britain. February 1995. p.118-121
[8] Proceedings of the International Symposium on Supercritical Fluids

- 2nd (1991) Baltimore. USA. ( proceedings edited by M.A.McHugh,
published by John Hopkins University. Baltimore. MD21218 )
- 3rd (1994) Strasbourg. France. ( proceedings published by Institut
National Polytechnique de Lorraine. ISBN 2-905267-23-8 ).
Section 26:
[1] International pH Scales and Certification of pH.

H.B.Kristenson, A.Salomon, and G.Kokholm
Anal.Chem. v.63, p.885A-891A (1991).
[2] Determination of pH, Theory and Practise - 2nd edition

R.G.Bates
John Wiley & Sons. (1973) ISBN 0-317-09107-7
[3] Ion-Selective Electrodes in Analytical Chemistry

H.Freiser (editor)
[4] Ion-Selective Electrode Methodology

A.K.Covington (editor)
CRC Press. (1979) ISBN 0-8493-5247-9 (2 vols)
Section 27:
[1] Modern Petroleum Technology - 5th edition.

Editor, G.D.Hobson.
Wiley. ISBN 0 471 262498 (1984).
- Chapter 1. G.D.Hobson.
[2] Hydrocarbons from Fossil Fuels and their Relationship with Living
Organisms.
I.R.Hills, G.W.Smith, and E.V.Whitehead.
J.Inst.Petrol., v.56 p.127-137 (May 1970).
[3] Refer 27.1

- Chapter 9. R.E.Banks and P.J.King.
[4] Refer 27.1

- Chapter 20. K.Owen.
[5] Comparative Studies of Methane and Propane as Fuels for Spark Ignition
and Compression Ignition Engines.
G.A.Karim and I.Wierzba.
SAE Paper 831196. (198?).
[6] Experiments with MTBE-100 as an Automobile Fuel.

K.Springer, L.Smith.
Tenth International Symposium on Alcohol Fuels.
- Proceedings, v.1 p.53 (1993).
[7] Oxygenates for Reformulated Gasolines.

W.J.Piel, R.X.Thomas.
Hydrocarbon Processing, July 1990. p.68-73.
[8] The Chemical Kinetics of Engine Knock.

C.K.Westbrook, W.J. Pitz.
Energy and Technology Review, Feb/Mar 1991. p.1-13.
[9] The Chemistry Behind Engine Knock.

C.K.Westbrook.
Chemistry & Industry (UK), 3 August 1992. p.562-566.
[10] The Methanolysis of Tallow

P.J.S.Bain
Report of Investigation 2590 (1988)
DSIR. PO Box 31-310, Lower Hutt, New Zealand.
[11] Variables Affecting the Yields of Fatty Esters from Transesterified

Vegetable Oils
B.Freedman, E.H.Pryde, T.L.Mounts
JAOCS v.61 p.1638-1643 (1984)
[12] NZ Liquid Fuels Trust Board Reports LF1199 - LF1210

Available ( for a fee ) from Liquid Fuels Management Group Limited
P.O.Box 17, Wellington, New Zealand.
[13] Evaluating Vegetable Oils as a Diesel Fuel

T.Murayama
Inform v.5 p.1138-1145 (1994)
[14] Quality Control of Vegetable Oil Methyl Esters used as Diesel Fuel
Substitutes: Quantititative determination of mono-, di-, and
triglycerides by Capillary GC.
C.Plank and E.Lorbeer
J. High Resolut. Chromatog. v.15 p.609-612. (1992)
Section 28:
[1] Chiral Pharmacology and the Regulation of New Drugs

John Caldwell
Chemistry and Industry 6 March 1995 p.176-179
[2] Thalidomide: From tragedy to new drug discovery.

G.W.Muller
Chemtech January 1997 p.21-25.
Section 31:
[1] IR Long-Path Photometry: A Remote Sensing Tool for Automobile Emissions

G.A.Bishop, J.R.Stanley, A.Ihlenfeldt, W.J.Williams, and D.H.Stedman
Anal.Chem. v.61, p.671A-677A. (1989)
[2] Optical Remote Sensing for Air Pollutants - Review.

M.Simonds, H.Xiao, and S.P.Levine
Am.Ind.Hyg.Assoc.J. v.55, p.953-965 (1994)
[3] US Patent 3,570,156. March 16, 1971.
[4] How to make a Lava Lamp

R.Hubscher
Popular Electronics. March 1991, p. 31 (4). Gernsback Publications.
- also in Popular Electronics' "1992 Electronics Hobbyists Handbook".
[5] Goretex patent

U.S. Pat. 3,962,153 (8 June 1976) R.W.Gore (to W.L.Gore and Associates)
[6] The Chemistry behind the Air Bag

A.Madlung
J.Chem.Ed v.73 n.4 p.347-348 (April 1996)
[7] Automotive safety is in the bag

Steven Ashley
Mechanical Engineering. January 1994. p.58-64
( best technical descriptions)
[8] Airbags : Education and Experience

Automotive Engineering. September 1993. p.29-32
[9] Everything you need to know about airbags

Autocar & Motor (UK). 3 March 1993. p.55-57
[10] The Toxicology of Inorganic Mercury

L.J.Goldwater
Ann. N.Y. Acad. Sci., v.65 p.498-503 (1957)
[11] Refer 10.4
[12] Refer 11.35
[13] Vaporisation of Mercury spillage.

J.F.Copplestone and D.A.McArthur.
Archives of Environmental Health v.13. p.675 (1966)
[14] The clean up of spilled mercury by a new technique.

J.Shurgan and L.Harris
J.Amer.Ind.Hyg.Assn. v.38 p.146 (March 1977).
[15] Elimination of liquid mercury.

K.Wacks
Fette-seifen-Anstrichmittel. v.76 p.425-426. (1974, in German)
[16] The Water Book - Barnstead 1990 Catalogue.

Barnstead Thermolyne Corporation
2555 Kerper Blvd. Dubuque. IA 52001. USA
Phone 319-556-2241 800-553-0039
Fax 319-556-0695
[17] Millipore Catalogue.

Millipore Corporation
Bedford, MA 01730. USA.
Phone 617-275-9200 800-225-1380
Fax 617-275-8200
[18] Nerve Gases Unveiled

C&EN v.31 p.4676,4678 (1953)
[19] Tokyo Subway Attack - Chemical Weapon Possible Terrorist Tool.

L.Ember
C&EN. 27 March 1995. p.6-7.
[20] Dioxins in Food

UK Ministry of Agriculture, Fisheries and Food
Food Surveillance Paper No. 31
HMSO (1992) ISBN 0-11-242926-2
[21] Polychlorinated dibenzo-p-dioxin and dibenzofuran concentration levels

in human adipose tissue samples from the continental US collected from
1971 through 1987
J.S.Stanley et al.
Chemosphere v.20 p.895-901 (1990).
[22] Dioxin Risk - Are We Sure Yet?. ( p.24A-25A )

EPA's Dioxin Reassessment. ( p.26A-28A )
EPA on the Right Track ( p.29A-30A )
EPA Assessment Not Justified ( p.31A-32A )
ES&T v.29 p.24A-32A. ( January 1995 )
[23] Dioxins in U.S.Food and Estimated Daily Intake

A.Schecter et al.
Chemosphere v.29 p.2261-2265 (1994)
[24] Cherry red and very dangerous

R.Edwards
New Scientist. 29 April 1995. p.4-5
[25] The Super Stain Remover Book

J.Cassimatis
Sterling Publications (November 1996) ISBN 0806994835
[26] Removing Stains from Fabrics

Home and Garden Bulletin No. 62
Science and Education Administration
United States Department of Agriculture (1978)
[27] Stain Removal from Fabrics by Home Methods

Dept. of University Extension. Otago University (NZ).
Whitcoulls (1977)
[28] Surface pretreatment for phosphoric acid-based rust removers

M.Svoboda and B.Knapek
Product Finishing v.22 p.41-46 (1969)
[29] Permeability of Commercial Solvents Through Living Human Skin

C.Ursin, C.M.Hansen, J.W.Van Dyk, P.Jensen, I.J.Christensen, J.Ebbehoej.
Am.Ind.Hyg.Assoc.J. v.56 p.651-660 (1995)

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www.chem.ucalgary.ca/courses/351/Carey/Carey.

On-Line Learning Center for "Organic

Project Overview How to use this resource General Information Feedback ?

Chapter 1: Chemical Bonding

Chapter 3: Conformational Analysis of Alkanes and Cycloalkanes

Chapter 4: Alcohols and Alkyl Halides

Chapter 5: Structure and Preparation of Alkenes. Elimination Reactions

Chapter 6: Reactions of Alkenes. Addition Reactions

Chapter 8: Nucleophilic Substitution

Chapter 10: Conjugation in Alkadienes and Allylic Systems

Chapter 11: Arenes and Aromaticity

Chapter 12: Reactions of Arenes: Electrophilic Aromatic Substitution

Chapter 13: Spectroscopy

Chapter 14: Organometallic Compounds

Chapter 16: Ethers, Epoxides and Sulfides

Chapter 17: Aldehydes and Ketones. Nucleophilic Addition to C=O

Chapter 18: Enols and Enolates

Chapter 19: Carboxylic Acids

Chapter 20: Carboxylic Acid Derivatives. Nucleophilic Acyl Substitution

Chapter 21: Ester Enolates

Chapter 22: Amines

Chapter 23: Aryl Halides

Chapter 24: Phenols

Chapter 1: Chemical Bonding <>

Bond types: Ionic, Covalent, Polar Covalent

Lewis Structures and Formal Charge

The Shapes of Molecules

More practice problems ?

Chapter 1: Chemical Bonding

Electrons and Orbtials:

e.g. electron configurations of carbon

simple 1s2 2s2 2p2

orbital energy diagram

Ionic bonds result when electrons are tranfered between atoms.

Chapter 1: Chemical Bonding

You should be able to indicate a molecule's polarity.

Chapter 1: Chemical Bonding

Oxidation and Reduction

Functional Group Questions

(a) Identify the functional groups in Epothilone A.

(b) What is the hybridisation at each of the following atoms

C1 C8 C12 C14 C17 C19

(c) Arrange the following bonds in Epothilone A in order of

(d) What type of bonding MOLECULAR orbitals are

Alkanes Alkenes Alkynes Arenes

For C5H12 has three possible constitutional isomers:

The C3 to C6 cycloalkanes are shown below in a variety of representations.

Basic Organic Nomenclature

Names of the simple cyclic hydrocarbons

Formula Name Line Diagram Molecular Model

Multiple substituents are located on the ring by numbering clockwise or counter-clockwise

The name is: 4-isopropyl-1,2-dimethylcyclohexane

The chain is larger so the name is: 4-cyclobutyl-5-cyclopropyl-2-methylheptane

Oxidation and Reduction

Conformational Analysis of:

Description given to two substitutents

A high energy conformation where the bonds

A low energy conformation where the bonds

Description given to two substitutents

Description given to two substitutents

Different spatial arrangments that a molecule

Angle between C-X and C-Y bonds in a X-C-

The destabilisation of a cyclic structure