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1

Advanced Experiments in Physical and


Analytical Chemistry
CM3292 (I I )


Table of contents
1. Constructing a Binary Phase Eutectic Diagram from Cooling
Curves
2. Surface Phenomena : (a) Adsorption at Solid/Liquid Interface
(b) Surface Tension
(c) Micelle Formation
3. Second-Order Reaction Kinetics Determined by Conductometry.
4. (a) Raman and Infrared spectroscopy
(b) Powder X-Ray Diffraction (XRD)
5. Computational Chemistry
2
Introduction

This updated and corrected edition has been prepared through the contributions of many
people at the Department of Chemistry: members of the teaching staff, technicians,
demonstrators and finally you, the undergraduates whose stimulating questions prompted
many improvements in the text. The manual contains descriptions of experiments which
will help you visualize and understand the theoretical concepts encountered during
lectures. It is also a reminder that chemistry is an experimental discipline where all the
knowledge is ultimately derived from practical work in the laboratory. Only the most
essential details of every experiment are given in the manual. Further reading is therefore
strongly recommended. Always use appropriate SI units when reporting your results.

Consult this electronic web page for additional
information!
(http://www.science.nus.edu.sg/~webchm/lab/phylab.htm)

For theoretical background one may consult:

1) P.W. Atkins, Physical Chemistry, 7th ed., Oxford University Press 2002
2) I. N. Levine, Physical Chemistry, 4th ed., McGraw-Hill 1995

For details of a particular experiment refer to:

3) D.P. Shoemaker, C.W. Garland, J.W. Nibler,
Experiments in Physical Chemistry, 6th ed., McGraw-Hill 1996
4) R.J. Sime, Physical Chemistry: Methods, Techniques and Experiments, Saunders
College Publishing, 1990
5) G.P. Matthews, Experimental Physical Chemistry, Oxford University Press 1985


Useful handbooks:
a) Lange's Handbook of Chemistry, 13th ed., McGraw-Hill 1985
b) Handbook of Chemistry and Physics, 77th ed., CRC Press, Boca Raton 1996
c) Quantities, Units and Symbols in Physical Chemistry, prepared by:
I.Mills, T.Cvitas, N.Kallay, K.Homann, K.Kuchitsu, Blackwell, Oxford 1993

Sources for numerical data analysis (e.g. linear regression):

e) K.Ebert, H.Ederer, T.L.Isenhour, Computer Applications in Chemistry, VCH 1989



3

1. Constructing a Binary Phase Eutectic Diagram
from Cooling Curves

Introduction
In this experiment the heterogeneous equilibrium between solid and liquid phases
in a two-component (binary) system consisting of components A (o-nitrophenol) and B
(p-toluidine) will be observed. The cooling curves for systems of different compositions
are obtained by plotting the temperature vs. time. From them a phase diagram for the
system can be deduced. When a homogeneous binary liquid mixture is cooled, a solid
separates but its composition will depend entirely on the nature of the components. If the
molecular (atomic) sizes of the pure compounds (components) are similar or have the
same type of crystal structures the components will form solid solutions. This case often
occurs in metal systems where the solids separating from the liquid phase can have a
wide range of compositions. The two components can also form a solid compound which
has a defined stoichiometry and a crystal structure different from the two components. In
that case, the phase diagram will show a maximum surrounded by two eutectic minima.
In the case of organic compounds there is a high degree of crystal lattice incompatibility
and no solid compound formation the system will show a simple phase diagram with only
one eutectic minimum. In that case each of the two components crystallizes out
separately lowering the freezing point of the other.
Cooling curves often show two types of features: thermal arrest and break. The
former (found in single component systems) is caused by constant temperature achieved
while pure substance crystallizes. All phase changes of pure substances take place at
constant temperatures. The latter represents a change in slope (kink) of the binary system
curve. When crystals are being formed in the liquid the heat thus released in the process
will slow down the cooling of the liquid causing the change in slope. A difficulty often
encountered in this experiment is "super cooling" when the temperature of solution drops
below its freezing point before crystals start to separate. It is caused by a lack of nuclei of
crystallization and manifests itself as a dip in the cooling curve.
4
Aim
In this experiment a eutectic diagram for a binary mixture will be constructed from the
cooling curves.

Experiment
The apparatus consists of two boiling tubes and a cork carrying a stirrer and
digital thermometer. Using a top-pan balance weigh the empty inner (smaller) tube first
(standing in a beaker) and then filled with approximately 4 g of component A. The added
sample should cover the probe of the thermometer. The probe is inserted only after the
compound or mixture has melted to liquid and the inner tube is removed from the
hot water bath. Heat the inner tube in hot water bath until A becomes entirely liquid.
Remove the inner tube from the bath and insert it in the outer (larger) tube provided.
Allow the apparatus to cool slowly in a bath with stirring and record the temperature at
1/2 min intervals until all liquid has solidified. The temperature of the cooling bath is to
be adjusted at 10 C lower than that of the systemat all times by the addition of water or
ice (What is the rationale of doing this?). From the plotted cooling curve determine the
freezing point of A.
Weigh approximately 1 g of the second component B, add it to A and obtain the
cooling curve as described above. The new cooling curve will show a distinct change in
slope at the new freezing point of the mixture. The new freezing point will be
considerably lower than the freezing point of pure A. Keep measuring the temperature
until all liquid has solidified.
Add another 1 g of B to the mixture and obtain the cooling curve. Repeat the
procedure (by adding 0.75g, 0.75 g and 0.5g) until a total amount of 4 g of B has been
added. At this stage transfer the mixture into the waste container (in the fumehood),
clean (with acetone and water) and dry the inner tube. Repeat the experiment starting
with 4 g of pure B to which successive 1 g,1 g, 0.75g, 0.75g and 0.5g portions of A are
added.

5
Safety precaution: The organic compounds used are toxic and must be handled with due
care, minimizing skin contact and vapour inhalation. Discard all residues into bottle
provided in the fume-cupboard and rinse the glassware with acetone followed by water.

Data analysis
Plot the cooling curves and from them deduce the phase diagram of the binary
system studied. Detect eutectic temperature and eutectic mixture composition. Label
different points and areas on the diagram which represents relationship between freezing
points and composition (mole fraction) of one of the components.

Exercises
1. Why does the temperature remain constant during phase change of pure substance and
what does the rate of cooling depend on?
2. Consider the freezing points of pure water, 0.1M NaCl solution and 0.1M CaCl
2

solution. Order the freezing points according to their magnitudes (e.g. 0C, <0C, >0C).
3. If sea water is frozen what is the composition of the resulting solid (refer to the phase
diagram for sea water)?












6
Surface Phenomena
(2a) Adsorption at a solid/liquid interface

Introduction
The surface of a solid is in a state of strain similar to that existing in liquids and
has a residual attractive force. All solids consequently tend to adsorb on their surfaces
any gas or liquid with which they come into contact. Many solids are also capable of
adsorbing ions and molecules from solution; this effect is used for separation of
substances by chromatography. The concentration of a solute in solution is often reduced
by addition of a finely divided solid such as charcoal. The solute becomes partially
adsorbed on the surface of the solid. Adsorption from dilute solutions may be represented
by the empirical Freundlich isotherm: x =kc
n
, where k and n are experimental constants,
c is the equilibrium molar concentration of solute in solution and x is the number of
moles of solute adsorbed per gram of adsorbent. Another important relation describing
adsorption is the Langmuir isotherm: x =ac/(1+bc), where a and b are experimental
constants. Both expressions indicate that x increases with c, but the Langmuir equation
also indicates that at high concentrations, bc 1, ie., the adsorption becomes constant
and independent of further increase in concentration. At that point the surface of the solid
becomes fully covered by a monolayer of adsorbed solute molecules.

Aim
To study the adsorption of a weak acid on charcoal.
Experiment
Prepare 6 solutions in stoppered bottles according to the table:
Flask Number 1 2 3 4 5 6
0.5M acid (cm
3
) 100 80 60 40 20 10
H
2
O (cm
3
) 0 20 40 60 80 90
g of charcoal 2 2 2 2 2 2
aliquot of filtrate
for titration(cm
3
) 5 5 10 10 25 25
7
The charcoal must be weighed accurately and volumes of water and acid added
measured with burettes. Shake the flasks intermittently for about 20 min by which time
equilibrium should be established between adsorbed and dissolved acid. To remove the
charcoal, filter the solution and then titrate the appropriate volume (see Table) of clear
supernatant solution with 0.1 M NaOH using phenolphthalein indicator.

Data analysis
1. Tabulate data and calculate c and x for each flask in mol of the acid per gram of
charcoal.
2. Plot x vs. c and explain its significance.
3. Test the applicability of the Freundlich isotherm by plotting log {x} against log {c}.
If the relationship is linear, evaluate n and k using regression analysis.
4. The Langmuir isotherm can be also be written as: c/x=1/a+bc/a. Test the applicability
of the Langmuir isotherm by plotting c/x vs. c. If you find that the Langmuir isotherm
describes the adsorption process well, calculate a and b using regression analysis (see
Introduction)
5. The a/b ratio gives the value of x
max
which in turn allows the calculation of active
surface area of charcoal in m
2
/g assuming the area of the acid molecule to be 0.21
nm
2
. Compare the calculated area with the floor area of the laboratory.

Exercises
1. What assumptions are made in deriving the Langmuir adsorption isotherm and discuss
their validity?
2. Which of the two isotherms (Freundlich or Langmuir) describes the adsorption of
a weak acid on charcoal? (use regression analysis to obtain the answer)
8
2(b) & 2 (c) Surface tension

Introduction
The surface tension of solutions differs from that of pure solvents. J.W. Gibbs has
shown that for lowering of surface tension the solute concentration is higher at the
surface than in the bulk of the solution (i.e. there is a surface excess of solute) and
conversely the surface tension is larger than that of the pure solvent indicates surface
depletion of solute. The relationship between surface tension and concentration is given
by Gibbs adsorption equation:
=(-c/RT)(d/dc) (1)
where is the surface excess of solute in moles per unit area of surface, c molar
concentration and surface tension. Hence if the surface tension of a liquid is measured
at constant temperature for various concentrations, d/dc may be obtained for any
concentration from the tangents to the curve of against c. Values of may then be
calculated from (1). Assuming that the surface excess is concentrated in a monomolecular
layer, the surface area occupied by 1 molecule (A) can be estimated:

A =1/( N
A
) (2)
where N
A
is Avogadro constant. Assuming further that the molecules in the surface move
freely within the two dimensions of the surface, that their molecular cross-section is small
compared to the area they inhabit (A), and that there is no intermolecular interaction, the
following relationship holds:

A=kT (3)
where is the surface pressure (
solvent
-
solution
) and k Boltzmann constant.
Equation (3) resembles the ideal gas equation PV =nkT and is likewise not applicable at
high pressures. At high surface pressures a modified relationship can be used: (A-A
0
) =
xkT where A
0
is the molecular cross section and x coefficient representing intermolecular
attraction.
9
Solutions of highly surface active materials exhibit unusual physical properties. In
dilute solution they act as normal electrolytes but at fairly well defined concentrations
abrupt changes in several physical properties such as osmotic pressure, electric
conductance, turbidity and surface tension take place. This behavior can be explained in
terms of organized aggregates or micelles of surfactant ions in which the lipophilic
hydrocarbon chains are oriented towards the interior of the micelle leaving the
hydrophilic groups in contact with aqueous medium. The concentration above which
micelle formation becomes significant is called the critical micelle concentration.

2(b)
Aim
To study the surface tension of an alcohol in water

Experiment
Prepare 100 ml of 0.1M t-butyl alcohol in water using volumetric flask and from
that stock solution prepare 0.08M, 0.04M, 0.02M and 0.01M solutions by diluting with
water. (Use 0.08M solution to prepare 0.04M etc.) Measure the surface tensions of water
and the solutions using a Du Nouy tensiometer. Take the mean of 3 readings for each
solution and record the temperature. When measuring the surface tension of different
solutions, start with the least concentrated one first so that the glassware will not be
contaminated in subsequent measurements.

Data analysis
Plot a graph of surface tension vs concentration c by drawing a smooth curve
through the data points. Draw tangents to the curve at concentrations 0.01, 0.02, 0.04,
0.06 and 0.08M and determine d/dc at these points. Calculate values from (1) and plot
them against appropriate concentrations. Estimate the limiting value
lt
from the graph
and calculate 1/
lt
. Next calculate 1/ for each experimental concentration and thus
obtain A from (2). Finally plot A vs. and from that graph determine A
0
and x.


10

2(c)
Aim
To determine the CMC of a surfactant

Experiment
The second part of the experiment consists of the measurement of critical micelle
concentration (CMC). Prepare 250 ml of 0.02M solution of sodium dodecyl sulfate. By
diluting that solution further, prepare solutions with concentrations: 0.015, 0.01, 0.0075,
0.005, 0.0025, 0.0015 and 0.001M. Determine the surface tension of each of the above
solutions by pouring them into a tensiometer dish and allowing a 5-10 min interval before
starting measurement. This time is necessary for the micelles to form and reach
equilibrium with the bulk of solution.

Data Analysis
Plot the surface tension against the concentration of sodium dodecyl sulfate solution and
determine the CMC from the diagram.

References:
1. E.F. Meyer, G.M. Wyshel, J.Chem. Educ. 63 (1986) 996.












11




3. The Rate Constant of a Second-Order Reaction
determined by Conductometry



Introduction:

Many hydrolytic reactions are catalyzed by bases as well as acids. The reaction

RCOOR' +OH
-
=RCOO
-
+R'OH

can be monitored by titrating the unreacted alkali or measuring the electrical
conductivity. The net result of reaction above is progressive replacement of mobile OH
-

by less mobile RCOO
-
(RCOO
-
has approx. 5 times lower mobility), which causes the fall
in conductivity.
The rate law for the reaction is

k =(1/at) [x/(a-x)] (1)

where a is the initial concentration of both reactants and x is the number of moles reacted
after time t. (1) can be written in terms of conductivity rather than concentrations to
give

k =(1/at) [(
0
-
t
)/(
t
-

)] (2)

where
0
is initial conductivity of solution,
t
conductivity after time t and


conductivity after reaction is completed. Rearranging (2) we obtain

12

t
=(1/ak)[(
0
-
t
)/t] +

(3)

The rate constant k can then be calculated from the known initial concentration of
reactants a and a plot of
t
vs. (
0
-
t
)/t.

Experiment:

The solutions required are: 500 ml of 0.02M NaOH, 500 ml of 0.02M EtOAc (freshly
prepared) and 100 ml of 0.01M NaOAc made by neutralizing 20 ml of 0.05M NaOH with
20 ml of 0.05M CH
3
COOH and making up to 100 ml.
All solutions should be prepared with CO
2
free water. For that purpose boil 2l of
deionized water, in separate 1l beakers, cover the beaker and let the water cool to room
temperature.
All solutions should be stoppered to avoid evaporation.
Fill a 500 ml volumetric flask 3/4 full with boiled water, pipet the necessary volume of
EtOAc into the flask and make to volume with boiled water (Overall EtOAc
concentration should be 0.02M).
Clean dip-type conductivity cell with deionized water and allow it to dry. Then measure
conductivities at 30 C for the 0.01M NaOH solution (
0
) and 0.01M CH
3
COONa
solution (

).
Suspend two large boiling tubes in the thermostat at 30

C, one containing 70 ml of
0.02M NaOH and the other 70 ml of 0.02M EtOAc.
Allow the flasks to reach equilibrium temperature (10 min) and in the meantime clean
and dry the conductivity cell. Then mix the two solutions quickly and start the stop-clock.
Dip the conductivity cell in the mixture and take conductivity readings at 2, 3, 4, 5, 6, 7,
9, 11, 13, 15, 18, 20, 25, 30, 35 and 40 min after commencement of the experiment.
Repeat the experiment at 45 C and 60 C remembering to set the temperature switch
on the conductometer accordingly.



13

Data analysis:

Obtain linear least-squares fit of
t
vs. (
0
-
t
)/t and from its coefficients determine
approximate rate constant for the hydrolysis (k) and

. Calculate activation energy for


the reaction using Arrhenius equation.

Exercises:

1. Why is it necessary to use freshly prepared EtOAc solution and CO
2
free water?

2. Electrodes of the conductivity probe are dipped in water, dried and then dipped in
mercury. In which liquid(s) will the indicator light on the probe light up and why?

3. What is the definition and what are the SI units for conductivity?
























14



4 (a) Laser Raman Spectroscopy

Features of Raman spectroscopy
In the study of spectroscopy (refer to CM2101), we learn that photons interact with
molecules or matter to induce transitions between energy states. The scattering of photon
by molecules is an example of the type of interaction which include absorption, reflection
and emission. In Rayleigh scattering, the photons are elastically scattered which means
the emitted photon has the same wavelength as the absorbing photon. On the other hand,
the Raman effect is related to the relatively small percentage (about 1 in 10
7
photons) of
inelastic scattering of photons by molecules, which gives rise to the difference of energies
between the incident and scattered photons.
The energy of the scattered radiation is less than the incident radiation for the Stokes line
but more than the incident radiation for the anti-Stokes line. The energy changes is
related to the vibrational energy spacing in the ground electronic state of the molecule
and therefore the wavenumbers of the Stokes and anti-Stokes lines are a direct measure of
the vibrational energies of the molecule.
In the spectrum, the Stokes and anti-Stokes lines are displaced to opposite sides from the
Rayleigh line. This occurs because in either case, one vibrational quantum of energy is
gained or lost. Anti-Stokes lines are much less intense than the Stokes line because only
molecules that are vibrationally excited prior to irradiation can give rise to the former
line. At room temperature, the percentage of molecules occupying excited vibrational
states is small. Hence, only the more intense Stokes lines are normally measured.
Infrared (IR) and Raman spectroscopy both measure the vibrational energies of
molecules but these method rely on different selection rules. Recall that for a vibrational
motion to be IR-active, the dipole moment of the molecule must change. For example,
15
the symmetric stretch in carbon dioxide is not IR-active because there is no change in the
dipole moment while the asymmetric stretch is IR-active due to a change in dipole
moment. For a vibration to be Raman active, there must be a change in the polarizability
of the molecule which means that the symmetric stretch in carbon dioxide is Raman
active because the polarizability of the molecule changes. In general, IR transitions
recorded for a molecule possessing a centre of symmetry will not appear in the Raman
spectrum and vice-versa.
Experimental
In this experiment you will collect infrared and Raman spectra of three samples : (1)
dichloromethane, (2) chloroform and (3) diphenylacetylene in chloroform solution. The
infrared spectra will be collected using a liquid cell and the FTIR spectrometer. Raman
spectra will be collected using the Raman spectrometer with a solid-state laser as the
excitation source. Please consult the demonstrator who will show you the setup of the
Raman spectrometer.
In your laboratory report, you will need to include ;
1. sketch the Raman spectrometer setup and explain how the experiment is carried out.
2. describe the functions of the instruments and apparatus such as the monochromator,
photomultiplier tube, fiber optic cable and other important parts of the Raman
spectrometer.
3. Assign as many as possible transitions recorded in the IR and Raman spectra of the
three samples. It will be necessary for you to use the literature to help assign the peaks to
the particular vibrations in the molecule.
4. discuss the similarities and differences between the IR and Raman spectra of each
sample.


1
4(b)

Qualitative and Quantitative Analysis of Alkali Halide Mixture by Powder X-Ray
Diffraction (XRD)

Aims
1. To learn about the use of the X-ray powder diffraction technique for identification
of crystal structures
2. To determine the structural parameters for alkali halides
3. To quantitatively analyze the composition of alkali halide mixtures

I ntroduction

This experiment will be conducted in a group of 4 students and they will be assigned
beforehand in performing either part A or part B of the experiment. Experiment
procedures are similar for both part A and B but in part A alkali halides with different
cations (NaCl : KCl) will be analyzed while in part B alkali halides with different anions
(KCl : KBr) will be analyzed. This X-ray powder diffraction experiment involves three
major procedures: sample preparation, data acquisition and X-ray diffraction patterns
interpretation. A complete description of the theory required for this experiment is not
provided in this manual. Students are strongly advised to read the relevant textbook on X-
ray diffraction before conducting this experiment. Following is a brief introduction and
theory about X-ray diffraction:


Qualitative X-ray Diffraction Analysis

The determination of the chemical structure of molecules is indispensable to chemists in
their effort to gain insight into chemical problems. Only a few physical methods are
capable of determining chemical structure, and amongst these methods, diffraction
methods have been the most successful. Diffraction methods are capable of defining bond
lengths, bond angles and other important structural parameters for a particular crystalline
solid. Diffraction experiments can be carried out by using electromagnetic wave such as
X-ray or tiny particles such as electrons and neutrons. Over the years numerous
diffraction methods have been developed in order to determine the structure of a
crystallite sample. Among these techniques, single crystal X-ray diffraction (XRD) is a
powerful method that is commonly used to determine the structures of new materials.
However, the technique is limited by the ability to grow crystals with nearly perfect
structures and ideal sizes that are suitable for diffraction analysis. Due to this limitation
and the time and cost-intensive nature of the technique, single crystal diffraction is not
used for routine structural characterization of known materials. For routine structural
characterization of materials, powder XRD is far more common. The samples for powder
XRD may be large crystals, or they may be in the form of a powder composed of tiny
crystals that are too small to be seen by the human eye. The underlying principles of the
experiment are the same in both powder diffraction and single crystal diffraction,
although the data analysis is simpler in powder diffraction.
2


Figure 1. Illustration of Braggs law for X-ray diffraction.

Powder diffraction patterns are typically plotted as the intensity of the diffracted X-rays
against the angle 2u. Peaks will appear in the diffraction pattern at 2u values when
constructive interference is at a maximum, that is, when Braggs Law (eq. 1) is satisfied.

(eq. 1)

n = order of the reflection
= wavelength
d
hkl
= interplanar spacing of planes with Miller indices h, k and l
u = Braggs angle

From the above equation, it is evident that the structure of the solid (such as the distance
between the atoms) can be obtained if a monochromatic X-ray source is used. The
constructive interferences, that results at specific values of 2u, map out the interplanar
spacing of the solid. In this experiment the X-ray has a wavelength of 1.5405 (Cu K
o
1
line). For a cubic system with simple geometry,

(eq. 2)

a = unit cell dimension


n = 2d
hkl
sinu
d
hkl
2
= a
2
/(h
2
+k
2
+l
2
)
3
Combining both equation 1 and 2, a relation between the Miller indices and the Braggs
angle can be established,

(eq. 3)

For the simple cubic (SC) unit cells, all possible combinations of integer Miller indices
are possible. However for face-centered cubic (FCC) unit cells, certain combinations of
Miller indices are eliminated by destructive interference caused by the planes formed by
the atoms in the faces of the unit cell. The result is that for FCC type lattices reflections
occur only if h, k, and l are all even or all odd. Some of the possible combinations of
Miller indices for cubic unit cells are shown in the following table:

Table 1: Reflection planes for cubic unit cell.
Simple Cubic
(hkl)
Body-centered Cubic
(hkl)
Face-centered Cubic
(hkl)
h
2
+k
2
+l
2

100 1
110 110 2
111 111 3
200 200 200 4
210 5
211 211 6
7
220 220 220 8
221, 300 9
310 310 10
311 311 11
222 222 222 12

The systematic extinction of certain planes can then be used to assign the diffraction
patterns for a particular crystallite solid with cubic system. Once the Bravais lattice for
the specimen has been identified, the cell unit dimension, a, can be obtained by solving
equation 3.

h
2
+k
2
+l
2
= (4a
2
/
2
)sin
2
u
4
Quantitative X-ray Diffraction Analysis

Besides qualitative structural analysis of a particular crystallite solid, quantitative
analysis is also possible by using powder XRD. Quantitative analysis of diffraction data
usually refers to the determination of amounts of different phases in multi-phases sample.
While qualitative analysis usually involves the identification of peaks at certain Braggs
angles, qualitative analysis usually involves the measurement of peak area and intensity.
The peak intensities reflect the total scattering from each plane for a particular crystal
structure and therefore they are dependent on the distribution of particulars atoms in the
structure. The calculation of peak intensities is complicated as a lot of experimental
constants are involved. In any circumstances the peak intensities can be approximated by
using the following equation:

( )
( )
s
hkl
I

o

o o
X K
e
K
= (eq. 4)

I
(hkl)o
= intensity of reflection of hkl in phase o
K
e
= experimental constant
K
(hkl)o
= structural factor for phase o
X
o
= weight fraction of phase o

o
= density for the phase o
(/)
s
= mass absorption coefficient of the specimen (
s
is the linear
absorption coefficient of the specimen while
s
is the density of the
specimen)

If the value of (/)
s
is known then the amount of the phase o in the specimen can be
calculated. Unfortunately (/)
s
is not a constant as its value is dependant on the amounts
of the entire constituent phases in the specimen. This problem can be solved by using
internal standard method, which is one of the most widely applied techniques for
quantitative XRD. Assuming the specimen contains phase o (phase which need to be
quantified) and phase | (standard phase with known amount), the (/)
s
problem can be
eliminated by simply dividing the intensity equation for both phases to yield:

|
o
|
o
X
X
k
hkl
I
hkl
I
=
|
.
|

\
|
|
.
|

\
|
(eq. 5)

k = calibration constant derived from the plot of I
(hkl)o
/ I
(hkl)|
against X
o
/ X
|


Internal standard method is usually applicable in the determination of the composition of
multi-phases specimen. This method can be extended to the quantification of physical
mixture consisted of different crystallite solids. In the latter part of the experiment, the
students need to determine the composition (in weight percent) of an alkali halide
mixture by using the internal standard calibration method.
5
Experiment Procedures

The major steps in the acquisition of X-ray powder diffraction patterns are:
1. Sample preparation and mounting
2. Selection of suitable instrument parameters
X-ray: kV, mA and
Divergence and receiving slits
3. Data collection
Scanning range, step size, count time
4. Pattern processing
Smoothing
Stripping of K
o2

Peak search
Peak correction
Store/print the diffractogram
5. Interpretation

(NOTE: X-ray radiations are VERY DANGEROUS and all students MUST OBEY the
safety regulations listed inside the X-ray instrument room. NEVER attempt to operate
the X-ray instrument unless you have been trained properly in handling the X-ray
instrument.)

Part A. Analysis of NaCl and KCl

Sample preparation

1. Prepare samples of NaCl : KCl mixtures with various composition as according to
Table 2. (NOTE: Sample A1 and A5 are pure alkali halide)
2. Mix the mixture in the beaker thoroughly by using a metal spatula.
3. Grind the mixtures by using mortar and pestle.
4. Acquire six XRD sample holders and Unknown A from the lab technicians. The
sample holder has a circular well for mounting the sample.
5. Transfer and mount the samples onto the XRD sample holders by using press
and pull sample loading method (NOTE: The sample is loaded into the circular
well and pressed down with a glass slide. After that the glass slide is carefully
pulled to the side. This method produces a mounted sample with an extremely flat
and smooth surface).
6. Label the sample holder properly.

Acquisition of X-ray powder diffraction patterns

1. Submit the samples to the lab technicians for powder XRD patterns acquisition
(NOTE: Please do not attempt to operate the powder XRD instrument).
2. Take note of the important components of the powder XRD instrument.
3. For pure KCl (Sample A1) and NaCl (Sample A5), use the following parameters:
2u range : 20 to 80
6
Step size : 0.05

For the rest of the sample (Sample A2, A3, and A4) and Unknown A, use the
following parameters:
2u range : 20 to 35
Step size : 0.05

4. After the acquisition of X-ray diffraction patterns, process the patterns by using
EVA software. Identify the 2u value and peak intensities for all the peaks.
5. Print out a copy of the XRD diffractograms. Students may duplicate the
diffractograms by using the photocopy machine.


Part B. Analysis of KCl and KBr

Sample preparation

1. Prepare samples of KCl : KBr mixtures with various composition as according to
Table 2. (NOTE: Sample B1 and B5 are pure alkali halide)
2. Mix the mixture in the beaker thoroughly by using a metal spatula.
3. Grind the mixtures by using mortar and pestle.
4. Acquire six XRD sample holders and Unknown B from the lab technicians. The
sample holder has a circular well for mounting the sample.
5. Transfer and mount the samples onto the XRD sample holders by using press
and pull sample loading method (NOTE: The sample is loaded into the circular
well and pressed down with a glass slide. After that the glass slide is carefully
pulled to the side. This method produces a mounted sample with an extremely flat
and smooth surface).
6. Label the sample holder properly.

Acquisition of X-ray powder diffraction patterns

1. Submit the samples to the lab technicians for powder XRD patterns acquisition
(NOTE: Please do not attempt to operate the powder XRD instrument).
2. Take note of the important components of the powder XRD instrument.
3. For pure KBr (Sample B1) and KCl (Sample B5), use the following parameters:
2u range : 20 to 80
Step size : 0.05

For the rest of the sample (Sample B2, B3, and B4) and Unknown B, use the
following parameters:
2u range : 20 to 35
Step size : 0.05

4. After the acquisition of X-ray diffraction patterns, process the patterns by using
EVA software. Identify the 2u value and peak intensities for all the peaks.
7
5. Print out a copy of the XRD diffractograms. Students may duplicate the
diffractograms by using the photocopy machine.


Table 2. Composition of alkali halides mixture
Part A. Mixtures of NaCl and KCl
Sample
Weight (gram)
Weight
%
(200) Peak
intensity
(200) Peak
intensity %
NaCl KCl NaCl NaCl KCl NaCl KCl
A1 0.0 2.0
A2 0.5 1.5
A3 1.0 1.0
A4 1.5 0.5
A5 2.0 0.0
Unknown A
Part B. Mixtures of KCl and KBr
Sample
Weight (gram)
Weight
%
(200) Peak
intensity
(200) Peak
intensity %
KCl KBr KBr KCl KBr KCl KBr
B1 0.0 2.0
B2 0.5 1.5
B3 1.0 1.0
B4 1.5 0.5
B5 2.0 0.0
Unknown B












8
Data Analysis

Qualitative analysis

The structural parameters for a particular crystallite sample can be obtained by
interpreting the X-ray diffraction patterns and such data interpretation can be performed
conveniently by using the EVA software. However, in this experiment the students
should not rely on EVA software in doing the interpretation. Interpretation of X-ray
diffraction pattern usually starts from indexing of the significant peaks. Manual indexing
of peaks can be performed by following these steps:

1. Identify all the significant peaks from the diffractogram of a pure alkali halide.
2. By using a spreadsheet program such as Excel, enter the positions of each peaks
and label the columns as 2-theta.
3. Construct a second column that equals sin
2
u.
4. Label the third column as h
2
+k
2
+l
2
. Construct this column by dividing the
values of sin
2
u with sin
2
u value of the first peak. If the Bravais lattice of the
crystal is simple cubic, the result of this operation should give an integer series
starting with one (Table 1). If the Bravais lattice is face-centered cubic, then this
column need to be multiply by 3 before the integer series can be obtained.
5. Once the Bravais lattice for the alkali halide has been identified, create a fourth
column that contains the expected integer values for that Bravais lattice (for
example 1,2,3,4,5... for simple cubic). Label this column as Integer.
6. Create a plot of sin
2
u against the integer and obtain the best-fitted line for the plot.
The slope of the plot is equals (
2
/4a
2
). Calculate the unit cell dimension, a.
7. Calculate the crystallographic density of the alkali halide. Example: The face-
centered cubic cell contains four molecules. Therefore the crystallographic
density =mass of four molecules / volume of one unit cell.
8. Complete Table 3 and compare the crystallographic density value obtained with
the macroscopic density.
9. Sketch out the structure of the alkali halides. It is known that K
+
has an ionic radii
of 1.34 . Find out the ionic radii of the rest of the ions (Na
+
, Cl
-
and/or Br
-
) from
the crystal structure, assuming that the cation-anion contacts determine the edge
length of the ions.

Table 3. Structural parameters for alkali halides
Salt
Molecular
weight
(gmol
-1
)
Density
(gcm
-3
)
Bravais
lattice type
Unit cell
dimension
()
Crystallographic
density
(gcm
-3
)
NaCl 58.443 2.165
KCl 74.551 1.984
KBr 119.002 2.75
9
Qualitative analysis

1. Identify all the significant peaks on the diffractograms for sample 2, 3 and 4 and
Unknown A (or Unknown B) by making comparison with the diffractogram for
pure alkali halides.
2. Complete Table 2 by recording the intensity of the (200) peak on the
diffractograms for all the samples.
3. Calculate the peak intensity ratio and plot a calibration curve of peak intensity
ratio against weight percent of NaCl (or KBr).
4. Determine the composition of the unknown sample by using the calibration curve.


Questions

1. Explain why the (111) peak appears as a weak peak on the diffractograms of NaCl
or KBr, but disappears on the diffractogram of KCl.

2. Tungsten, also known as Wolfram, is a chemical element with very high melting
point. It has an atomic weight of 183.84 gmol
-1
and a macroscopic density of
19.25 gcm
-1
. The following diffraction data of Tungsten is obtained with Cu K
o1

radiation. Determine the Bravais lattice and unit cell dimension of Tungsten by
interpreting the diffraction data. It is known that the unit cell of Tungsten is a
cubic system.

2u (degree) Relative intensity (%)
40.262 100
58.251 15
73.184 23
86.996 8
100.632 11
114.923 4


References
[1] V. K. Pecharsky and P. Y. Zavalij, Fundamentals of Powder Diffraction and
Structural Characterization of Materials, Kluwer Academic Publishers, 2003

[2] A. Clearfield, J . Reibenspies and N. Bhuvanesh (eds.), Principles and Applications
of Powder Diffraction, Wiley, 2008

[3] R. J enkins and R. L. Snyder, Introduction to X-ray Powder Diffractometry, J ohn
Wiley & Sons, Inc, 1996
1

5. Activated Dienophiles in DielsAlder Cycloadditions
The most common (and synthetically most useful) DielsAlder reactions involve electron-
rich dienes and electron-deficient dienophiles.
Y
X
Y
X
Y= R, OR
X= CN, CHO, CO
2
H

The rate of these reactions generally increases with the donor ability of the diene
substituent, Y, and with the p acceptor ability of the dienophile substituent, X. This behavior
can be rationalized using Frontier Molecular Orbital (FMO) theory by examining the
interaction of the dienes highest-occupied molecular orbital (HOMO) and the dienophiles
lowest-unoccupied molecular orbital (LUMO).
Orbital
Energy
HOMO
LUMO
diene dienophile

The HOMOLUMO interaction lowers the reaction barrier by stabilizing the electrons in the
diene HOMO, and FMO theory suggests that this effect will be largest when the
HOMO
diene
LUMO
dienophile
energy difference is smallest. In other words, diene reactivity
should be positively correlated with HOMO energy, and dienophile reactivity should be
negatively correlated with LUMO energy.
Electrostatic interactions between the diene and dienophile may also play a significant role in
determining the reaction rate.
1
According to this view, rapid reactions occur when

1
S. D. Kahn, C. F. Pau, L. E. Overman and W. J. Hehre, J . Am. Chem. Soc., 108, 7381 (1986).
2

electrostatic interactions between the diene and dienophile are most attractive (least
repulsive). Thus, diene reactivity should increase as the electrostatic potential over the face
of the diene becomes more negative, and dienophile reactivity should increase as the
electrostatic potential over the face of the dienophile is made more positive.
The FMO and electrostatic models can also be used to predict the regiochemistry of a
cycloaddition reaction. According to the FMO model, the best HOMOLUMO interaction
for a given diene-dienophile pair results when there is good overlap between the interacting
orbitals. Thus, the best orientation for two unsymmetrical reactants is usually the one that
aligns the HOMO and LUMO so that the atomic orbitals that contribute most to each
molecular orbital are able to overlap.
2


The electrostatic potential model suggests that the best orientation is the one that brings
together the region of most negative potential on the diene with the region of most positive
potential on the dienophile.
In this experiment, you will explore to what extent the behaviour of a series of dienophiles
(cyanoalkenes) can be correlated with either their frontier molecular orbitals and/or their
electrostatic potentials as provided by ab initio calculations at HF/3-21G level.
Procedure

2
I. Fleming, Frontier Orbitals and Organic Chemical Reactions, Wiley, New York, 1976.
Experimental relative rates for DielsAlder cycloadditions of cyclopentadiene and
various dienophiles
3

1) Rates of DielsAlder cycloadditions:
Build the dienophiles listed in the table below, and optimize their geometries using the HF/3-
21G level of theory.

To build the structure:
1) Double click on the GaussView shortcut.
2) Click on File and choose New and choose Create MolGroup and a purple
screen to build the molecule will appear (Figure A).
3) From the Element fragment , choose a sp2 carbon and build 2 together to form
an ethene (Figure B).
4) Substitute a hydrogen with a cyano group from R-Group Fragments to form
the acrylonitrile (Figure C)
5) Minimize the molecule using the Clean icon .
6) Undo any errors with Ctrl + Z. Save the molecule on desktop as .gjf file.

3
J. Sauer, H. Wiest and A. Mielert, Chem. Ber., 97, 3164 (1964).
dienophile
3
relative rate (k
rel
)
acrylnitrile 1
trans-1,2-dicyanoethylene 78
cis-1,2-dicyanoethylene 88
1,1-dicyanoethylene 4.4 10
4

tricyanoethylene 4.6 10
5

tetracyanoethylene 4.1 10
7

4

7) When acrylonitrile has been optimized, add cyano groups to the optimized structure to
build the other dienophiles. (Optimized structure can be found by opening the log file
in Guassview in the same location as the gjf file)
Mouse Control

Left click: Press and hold on to left click and drag to rotate
Centre click/wheel: Press and hold to translate/move the molecule
Right click: Press and hold; dragging up and down Zooms in and out of the molecule.
Dragging left and right rotates the molecule in the plane of the screen.


Figure A
5


Figure B



Figure C





6

To optimize a structure:
1) Go the Calculate drop down menu and choose the Gaussian option.
2) Under the J ob Type drop-down menu choose Optimization (Figure D).
3) Under method, choose Hartree-Fock and use the 3-21G basis set. (Figure E).
4) Under Link 0, set the RAM as 1000Mb.
** Remember to have a different .chk file name for each dienophile as you will need
the LUMO map for the later exercises.
5) Input the additional keywords pop=npa to calculate the charge.
6) Repeat steps 1 to 5 for all the 6 dienophiles


Figure D.
7


Figure E.

Record the HF/3-21G LUMO energy (in eV) of each dienophile, and plot these energies
against the log of the experimental k
rel
values.
You can assess the LUMO for HOMOLUMO band gap by looking at the log file for the
first virtual eigenvalue (Al pha vi r t . ei genval ues) .
Using MS word to open the log file, using the Find function (Ctrl + F), change the options
from More to up instead of down and search Alpha from the last page to search for
the last optimization eigenvalues (Figure F). Convert the values from hartrees to eV.
From log file in MS Word:
Al pha occ. ei genval ues - - - 15. 65673 - 15. 65503 - 15. 65385 - 11. 40083 - 11. 38117
Al pha occ. ei genval ues - - - 11. 34508 - 11. 34262 - 11. 34195 - 1. 31718 - 1. 30679
Al pha occ. ei genval ues - - - 1. 30193 - 1. 20515 - 1. 01572 - 0. 87084 - 0. 80044
Al pha occ. ei genval ues - - - 0. 71553 - 0. 62530 - 0. 60821 - 0. 60578 - 0. 59781
Al pha occ. ei genval ues - - - 0. 55117 - 0. 53845 - 0. 53102 - 0. 52840 - 0. 51820
Al pha occ. ei genval ues - - - 0. 42897 HOMO
Al pha vi r t . ei genval ues - - - 0. 01183 LUMO 0. 14692 0. 17737 0. 19951
Al pha vi r t . ei genval ues - - 0. 22303 0. 23290 0. 28462 0. 30118 0. 33623
Al pha vi r t . ei genval ues - - 0. 40943 0. 45500 0. 53610 0. 56665 0. 59386

Figure F

8

The FMO model actually depends on two factors: the HOMO LUMO energy difference
and the degree of the HOMOLUMO overlap. Is there a relationship between the value of
the LUMO and the dienophile reactivity? If there is, is this relationship consistent with the
FMO model?
Next, consider the electrostatic argument.
1) Open the log file (Figure G) in Gaussview by clicking on File and picking the
Open option in the drop down menu. Choose File of Type as Gaussian Output
Files and look for the log file in the same folder as the input file (.gjf file).
2) Go to Results and under the drop down window, choose Charges and Show
charge number (Figure H).
3) Record the most positive charge found on the sp
2
bond forming carbon. Plot this
quantity against log(k
rel
).
What does the charge describe about the electronic properties of each atom? Are the two
correlated? If so, is the direction of the correlation consistent with the electrostatic
character of the dienophiles?

Figure G
9


Figure H

2) Regioselectivity in Diels-Alder cycloadditions:
You will use the reaction of 1-methylcyclopentadiene (MCP) with various unsymmetrical
dienophiles (acrylonitrile, 1,1-dicyanoethylene, and tricyanoethylene) to examine FMO
and electrostatic potential-based analyses of regioselectivity.
** (Regioselectivity is not equivalent to endo/exo selectivity)


10

Build 1-methylcyclopentadiene, optimize its HF/3-21G geometry.
1) In the Ring Fragments , choose cyclopentadiene and build. (Figure I)
2) Add a sp3 carbon to the H you want to substitute as the methyl using the Element
Fragment
3) Repeat optimization step 1 to 5 from Exercise 1 to optimize the structure.

Figure I

Display the HOMO of the diene and LUMO of the dienophiles using the checkpoint file.
1) Under File, choose Open in the drop down menu and set File of Type as
Gaussian Checkpoint Files. The .chk files are located in the directory
C:\G03W\Scratch.
2) Go to the Results menus again and choose Surfaces.
3) Under the Cube Actions drop-down menus choose New Cube. Yet another
dialog appears called the Generate Cubes dialog.
4) Under the Orbitals: drop-down menu, choose the HOMO or LUMO
accordingly. (Figure J)
5) Go to the Cubes Available: drop down menu and choose the HOMO or
LUMO accordingly.
6) Go to the Surface Actions and in the drop down menu and choose New Surface.
11


Figure J
Which end of the diene is best suited for overlap with an unsymmetrical dienophile? Next,
examine LUMO maps of the three unsymmetrical dienophiles. Which alkene carbon is best
suited for overlap? What product regioisomers are predicted by the overlap? Do you arrive
at the same predictions using resonance arguments? (Your answer should include drawings
of the specific resonance structures that your predictions are based on.)
Next examine the NBO charges of the diene and the three dienophiles. Which sp2 carbon
involved in the bond formation of the diene has the most negative potential? Which end of
each dienophile has the most positive potential? What product regioisomers are predicted by
the electrostatic model? Are the Molecular Orbitals and electrostatic predictions the same?
3) Lewis Acidity effects on Rate
Lewis acids such as BF
3
generally increase both the rate and regioselectivity of DielsAlder
reactions. These effects might be due to enhanced and more selective frontier orbital
interactions, or they might be due to changes in the nature of key electrostatic interactions.
Examine the effect of a simple Lewis acid, H
+
, on the reaction of acrylonitrile and 1-
methylcyclopentadiene. Lewis acids preferentially bind to the strongest Lewis base present,
the nitrogen lone pair of acrylonitrile.
12


Therefore, build an N-protonated acrylonitrile cation, optimize its geometry using the HF/3-
21G level of theory, and use the results to evaluate the reactivity and regioselectivity of this
dienophile.
1) Use the Add Valence icon to add a hydrogen atom to the N of acrylonitrile.
2) Repeat optimization step 1 to 5 from Exercise 1 but CHANGE THE CHARGE TO 1.
Which factors appear to contribute to this dienophile's enhanced reactivity and selectivity?

4) Transition state and kinetics
The most direct way to evaluate DielsAlder selectivity is to calculate energy barriers for
reactions involving the dienophiles. Build 4 transition states for the 4 possible products of
the reaction between 1-methylcyclopentadiene and acrylonitrile, using the template
method. That is, add cyano groups to a simpler transition state template of cyclopentadiene
and ethene:
Create the geometry of the transition state for constrained optimization
a. Open the optimized 1-methylcyclopentadiene.log and build an ethene inside the same
screen as the MCP (Figure K)
b. Orientate the ethene towards the two bond forming carbons in the optimized MCP (Figure
L). Press and hold on Alt, use the centre click to shift the molecules individually to the
desired position of the pseudo C-C bond formation in the Diels Alder reaction.
c. Add single bonds to the bond forming carbons using the Modify Bond option
and minimize the molecule using the Clean function (Figure M).
d. Set both the bond lengths to 2.19 (Figure M) using the Modify Bond option .
13


Figure K

Figure L


Figure M
14

e) Add the constraints to the two forming C-C bonds.
I. Click on the Redundant Coordinate Editor icon ( Figure N)
II. Click on the Add new constraints icon (Figure O).
III. Set the parameter (Bond) that you want to constrain under Coordinates and choose
Freeze coordinate (Figure O). Choose the two atoms which constitute the bond you
want to constrain.
IV. Go to Set value and set it as 2.19 A.
V. Repeat step II to IV for the other bond.
f) Optimize the constrained geometry by repeating optimization step 1 to 4 from Ex 1,
EXCLUDING the step of inputting the additional keyword.





Constrained optimization

Figure N

Click on R icon to
input constraints
15




Figure O



Use the optimized constraint structure to search for the HF/3-21G transition state.
1. Under Job type choose Opt+Freq. (Figure P)
2. Under Optimize choose TS(Berny),
3. Under Calculate Force Constants, choose Once and under Compute Raman,
choose No
4. Under method, input the usual Hartree-Fock /3-21g, 0 charge, singlet. (Figure Q)
5. Insert keyword opt=noeigentest and run the calculation
Add the cyano substituent at different position of the ethene in the obtained transition state to
generate the inputs for the different stereoisomers. Repeat the above steps 1-5. . (DO NOT
RUN CONSTRAI NED OPTI MI ZATI ON STEPS a to f AGAI N )

Operation specified Parameters
chosen
Parameters to be altered
Value to be constrained Add new
constraint
16


Figure P


Figure Q
17


Verify that these are transition states by their vibrational frequencies (a transition state
has only one imaginary frequency).
Use the HF/3-21G energy of each transition state along with those of the reactants to
obtain the energy barriers for each cycloaddition. Compare the activation barriers and
use Boltzmann distribution to identify the composition of the products (assuming the
degeneracy is the same for all the stereoisomers at standard state, 298K/1 atm).
Is the composition correlated with the regioselectivity predicted? What are the reasons
for the different in stabilities of the transition states?

E
A
= E
TS
E
Reactants
= E
TS
E
MCP
E
dienophile


To extract the energy of the operation, open the .log file in MS words and go to the
end of the file and find the line \HF=. The energy is in expressed in hartrees.




Sometimes even though the TS search did not terminate properly, both the vibration
calculation and TS search are completed. Open the log file in Guassview and click on
Results and choose Vibration. If the vibration frequencies are present means the
job is completed. To extract the energy from the improperly terminated files, open the
log file in MS words, go to the bottom of the file and search # upwards. It will bring
you to the start of the frequency calculation. Above it is the termination of the TS
search and you can look for the /HF there.

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