2017 CHEM1011 DrBall Notes 1pp

CHEM1011 Essentials of Chemistry
Lecturer: Dr Graham E. Ball

Room 129 Dalton
email: g.ball@unsw.edu.au
About me
Dr Graham E. Ball, Dalton 129
http://www.chem.unsw.edu.au/staffprofiles/ball.html
Studies Sheffield, UK (BSc, PhD)
Post doctoral appointments University of British Columbia,
University of California, Berkeley
Research Interests
NMR spectroscopy
Organometallic chemistry Drug-DNA
Reactive intermediates interactions
Metal hydrides
Computational chemistry
Fullerenes
Lecture content - Week 1
Atoms and their structure.
Nomenclature of simple organic and inorganic ions.

Stoichiometry and balancing equations
Mole Concept. Solution stoichiometry

Empirical vs molecular formula
Percentage composition by mass
Learning objectives - Week 1
After this week you should be able to:
Name the constituent parts of an atom, together with their relative masses
and charges.
Calculate numbers of protons, neutrons, electrons in atoms of a particular
element.
Name simple inorganic compounds and write the formulae for simple
compounds from their name.
Write and balance simple chemical equations. Calculate molecular weight
from chemical formula.
Calculate % by mass of each element in a compound and determine empirical
formula from % by mass.
Calculate concentration of solutions in various units. Calculate yield in a
chemical reaction, determine the limiting reagent.
Chemistry: - The Central Science
ENGINEERING
MEDICINE BIOLOGY
CHEMISTRY
MATHEMATICS MATERIALS SCIENCE
PHYSICS
Chemistry (from Egyptian kme (chem), meaning "earth") is the science

concerned with the composition, structure, and properties of matter, as well as
the changes it undergoes during chemical reactions (Wikipedia)
Chemistry: - Study of Matter
anything that takes up
MATTER space and has mass
MIXTURES PURE SUBSTANCES
ELEMENTS COMPOUNDS
THE ATOM Blackman 1.2-1.4
Democritus: There be atoms and there be void.
Aristotle: Earth, Air, Fire & Water.
Alchemists: Base metals to gold.
Dalton: First atomic theory
supported with observation
and measurement.
John Dalton
1766-1844
First page of Dalton's "A New System of

Chemical Philosophy", published in 1808
THE ATOM
DALTON'S ATOMIC THEORY: (1803) mostly correct.
All matter consists of tiny particles :- ATOMS
Atoms of one element can neither be subdivided nor
changed into atoms of another element.
Atoms can neither be created, nor destroyed.
All atoms of the same element are identical in size, mass
and other properties.
Atoms of one element differ in mass and other properties
from the atoms of other elements.
Chemical combination is the union of atoms of different
elements, the elements combine in simple, whole number
ratios with each other.
The atomic theory
Law of conservation of mass (Lavoisier)
No detectable gain or loss of mass occurs in chemical
reactions. Mass is conserved.
Law of definite proportions (J.L.Proust)

In a given chemical compound, the elements are always
combined in the same proportions by mass.
Law of multiple proportions (post Daltons theory)

Whenever two elements form more than one compound, the
different masses of one element that combine with the same
mass of the other element are in the ratio of small whole
numbers
Law of multiple proportions example
The atomic theory fact!
Chemists no longer talk of

atomic theory, we
talk of atomic fact
Scanning tunnel microscopy and
atomic force microscopy allow us to
view and manipulate individual
atoms
Above image: Don Eigler

What are atoms made of?
Can they be broken down further?

CRITICAL
EXPERIMENTS POST-
DALTON.
The Cathode Ray:- A

stream of electrons.
(Faraday, Crookes,
Stoney, Thomson, Millikan)
see opposite
Canal Rays:- Protons.

(Goldstein and Wien)
J.J. Thomsons experiment to measure the mass of

cathode rays (1897)
Showed they were made of particles, but were around
1800 times lighter than the lightest atom, hydrogen. The
negatively charged particles were named electrons.
The Plum Pudding Model of the atom
the atoms of the elements consist of a number of negatively electrified

corpuscles enclosed in a sphere of uniform positive electrification
- J.J. Thomson, 1904.
- Accounts for the presence of electrons but overall neutral charge
- Disproved by Rutherfords experiment

GeigerMarsden Experiment CRITICAL
AKA EXPERIMENTS
Rutherford Gold foil POST-DALTON.
experiment
alpha - Particle
scattering:-
(Rutherford)
Showed that the mass of an atom is

concentrated in a very small volume
the nucleus
Atoms and their composition
ATOM: Smallest unit of an element,
Composed of three elementary particles
protons, neutrons and electrons
protons and neutrons are in the nucleus,
electrons are in surrounding shells.
Neutrons have mass about the same as a proton

but no charge.
Charges: Proton +1; electron -1.
Masses:
Proton mass = 1.673 x 10-27 kg (1)

Neutron mass = 1.675 x 10-27 kg (1)
Electron mass = 6.63 x 10-31 kg (1/ 1833)
Dimensions of the Atom
The H atoms electron cloud is
10,000 times larger than its
nucleus.
The nucleus of H is 1833 times

heavier than its electron.
THEREFORE:
The size of the atoms electron

cloud defines the atoms size.
The composition of the atoms

nucleus defines the atoms
weight.
Atoms vs Ions
NEUTRAL ATOM: number of protons = number of electrons
(Individual atoms are electrically neutral)
ION: Charged particle (single atom or group of atoms )
ANION: Negatively charged species, protons < electrons
CATION: Positively charged species, protons > electrons
Fundamental Property of elements:
- same number of protons in each atom.

Elements
A chemical element is a substance consisting of one
type of atom distinguished by its atomic number,
which is the number of protons in its nucleus.
So, it is the number of protons in the nucleus that

determine the element
1 proton => hydrogen
6 protons => carbon
79 protons => gold
Chemistry is just a counting exercise!

Dimitri Mendeleev, 1834-1907
Isotopes
Not all atoms of an element need be identical.
ISOTOPES: have same number of protons

different numbers of neutrons
different atomic mass numbers.
similar chemical properties

- slightly different physical properties.
Nuclear (Atomic) Arithmetic
M n Be sure to do the
Formalism:
Z A tute exercises!
A = symbol of element
M = mass number (protons plus neutrons)
Z = number of protons (atomic number)
12 6 protons, 6 neutrons, 6 electrons

Examples: C
6
13 2+
C 6 protons, 7 neutrons, 4 electrons
6
Isotopes of the Hydrogen atom
Names:
Symbols: H D T
(Dont have alternative names for other elements just name
the isotope number, e.g. carbon-14)
Picture: Dirk Hnniger, http://en.wikipedia.org/wiki/File:Protium_deuterium_tritium.jpg
Isotopes: Properties of Hydrogen
Boiling points: H2 (-253C); D2 (-250C)
Melting points: H2 (-259C); D2 (-255C)
Densities: H2 (0.1 g/ml); D2 (0.2 g/ml)
Molar mass: H2 (2 g/mol); D2 (4 g/mol)
Isotopes: Properties of Water

Boiling points: H2O (100C); D2O (101C)
Melting points: H2O (0C); D2O (4C)
Densities: H2O (1 g/ml); D2O (1.1 g/ml)
Molar mass: H2O (18 g/mol); D2O (20 g/mol)
Dimitri Mendeleev, 1834-1907
Atomic Mass:
To find mass of an atom? - Experimentally
ATOMIC MASS: average mass in amu of the atoms of the

naturally occurring mixture of isotopes.
ATOMIC MASS UNIT: 1/12 th of the mass of a carbon-12 atom
Example: Calculate the (average) atomic mass of naturally occurring

magnesium.
Isotope Mass Number Abundance Isotopic Weight

24 78.99% 23.98504
25 10.00% 24.98584
26 11.01% 25.98259
Atomic Mass =
Calculating average atomic mass
Average Atomic Mass =
(fraction each isotope) x (mass each isotope)

sum of
So for the magnesium data:
Isotope Mass Number Abundance Isotopic Weight
24 78.99% 23.98504
25 10.00% 24.98584
26 11.01% 25.98259
= (78.99/100)*23.98504 + (10.00/100)*24.98584 + (11.01/100)*25.98259

= 0.7899*23.98504 + 0.1000*24.98584 + 0.1101*25.98259
= 24.31 g mol-1 (4 sig fig)

EXAMPLE (with a different approach)
Copper occurs naturally as a mixture of two isotopes: 63Cu (abundance 69.09%)
and 65Cu (30.91%). Their atomic masses are 62.930 amu and 64.928 amu,
respectively. Calculate the average atomic mass of copper.
Whenever dealing with percentages, a useful trick is to consider 100 of whatever

the items are.
In this case, consider you have 10000 atoms of natural copper (2 decimal places)
Of these, 6909 atoms will be 63Cu, of weight = 6909 x 62.930 amu.

Similarly the weight of the 65Cu atoms will be = 3091 x 64.928 amu.
Thus, the total weight of all 10000 atoms
= [6909 x 62.930 + 3091 x 64.928] amu.
= 635480 amu.
Thus, the average atomic mass of one atom = 635480 /10000

= 63.55 amu.
More formally: sum of (fractions of each isotope x atomic mass each isotope)
CHEM1011 2017
Lecture set 2
Dr Ball
Where do elements come from?
Mostly they come from stars!
Hydrogen formation and some light elements - the big

bang
Elements carbon to iron formed in stars
Many elements heavier than iron formed by exploding

stars (supernovae)
Elements heavier than uranium are man made

Names of elements
Some from antiquity: Carbon Copper Gold Antimony
Iron Lead Silver Mercury
Sulfur
Some named from mythology:

Thorium Promethium Niobium Tantalum
Some named after people:

Meitnerium Curium Fermium Einsteinium
Nobelium Gadolinium
Greek: Hydrogen - water former Nitrogen - soda former

Oxygen - acid former Chlorine - greenish yellow
Iodine - violet Bromine - stench
Osmium smell
Some named after places:

Terbium
Ytterbium
Yttrium Polonium
Erbium
Lawrencium
Berkelium
Californium
Americium Francium Germanium
Gallium Rhenium
Beyond Elements some definitions
Compound: atoms of 2 or more elements combined chemically
Molecule: independent structural unit of 2 or more atoms

combined chemically. Held together by covalent bonds
- may be of the same element
Binary Compound: contains 2 element types - AxBy.
Formula: Empirical - simplest whole number ratio

in which elements combine.
Molecular - number of atoms of each element
type per molecule
CH = empirical formula for C2H2 and C6H6

A look at some compounds
Most materials are made of combinations of atoms and
elements compounds
Compounds may be composed of individual molecules or a
covalently bonded network of atoms
Do not have individual molecules of an ionic compound
Sodium chloride, NaCl, simply represents the
smallest repeating unit in an enormous 3D
array of Na+ and Cl ions
Ionic compounds have a cation (+ve) and an
anion (-ve). Overall charge for a solid is
neutral charges balance.
Chemists use various representations for the same

compounds
The Language of Chemistry
Representing Molecules
A Brief Introduction
Representations of molecules
(Blackman 2.2)
Three-dimensional structures represented in two
The language of Chemistry
six representations of Cisplatin
Ball and stick model Space filling model
H3N NH3 Names:

Cisplatin - common name
Pt
Cl Cl cis-diamminedichloroplatinum(II)
-formal name
Structure drawing
Cisplatin is a molecular compound Formula: Pt(NH3)2Cl2
Whats in a name?
Often systematic names are of little use
E.g., IUPAC name:

(2R,3R,4S,5S,6R)-2-[(2S,3S,4S,5R)-3,4-dihydroxy-2,5-
bis(hydroxymethyl)oxolan-2-yl]oxy-6-
(hydroxymethyl)oxane-3,4,5-triol
More useful names:

Sucrose or table sugar
and
A picture tells a thousand words!
Chemical formulae
(Blackman 2.2)
Chemical formulae
There is a standardised way of writing chemical formulae
Element symbols represent that atoms that are present in that
substance
Subscript shows the relative number of each type of atom present in a
substance
H2O
C30H34AuBClF3N6O2P2PtW
subscript refers only to the atom immediately preceding it, EXCEPT
when it follows a group of atoms enclosed in parentheses,
e.g. B(OH)3 contains one boron atom, three oxygen atoms and three
hydrogen atoms
A molecular formula is a chemical formula that refers to a discrete
molecule
Chemical formulae - Binary compounds
Binary compounds
Binary compounds contain exactly two different elements

Element further to the left of the periodic table appears first
KCl, Al2S3
Hydrogen is the exception to this rule

LiH, NH3, H2O2, HCl
Hydrogen written last except when combined with a
group 16 or 17 element
If both elements are from the same group the lowest element
appears first
SiC, BrF3
Chemical formulae - Ionic compounds
Binary compounds
In ionic compounds the cation is written first followed by

the anion
NaBr, MgCl2
Reminder: a subscripted number refers ONLY to the atom

immediately preceding it UNLESS the number comes
after a species enclosed in brackets
Chemical formulae beyond binary
compounds
Writing chemical formulae for compounds containing
more than two elements requires some knowledge of
the bonding within the compound.
Categorise as:
Ionic compounds
Covalent compounds
Chemical formulae - Ionic compounds
Write the cation followed by the anion, e.g., Ca(NO3)2
Note the positioning of the brackets around the NO3-
Total charge zero, so two NO3- ions per Ca2+ in this case:
Hydrate formation in the solid state common among ionic
compounds:
Ca(NO3)2.4H2O
water of crystallization or other solvents that are present in the

solid are written after the ionic formula separated by a full stop.
Dissolving in water, ionic compounds dissociate:
Ca(NO3)2 (s) Ca2+ (aq) + 2 NO3- (aq)
The superscripts indicate the charge of the species

Chemical formulae - Covalent compounds
Covalent compounds
Majority are carbon-based organic compounds

Chemical formulae are often written carbon first, followed by
hydrogen and then the remaining elements in alphabetical
order, e.g. C2H6O, C4H9BrO
Limited structural information in the chemical formula
Dealt with later in the course
Nomenclature (Blackman 2.3)
Nomenclature the system for naming of compounds
International Union of Pure and Applied Chemistry (IUPAC)
Some compounds are better known by their common

unsystematic name rather than their systematic IUPAC name
The systematic name of water is oxidane
Make sure you work through the DIY tutorial in the

course pack!!
Nomenclature
Naming Inorganic Compounds
Nonmetallic binary compounds

What happens if there is more than one possible
combination of two elements?
Guidelines for naming:
NO NO2 N2O5
Nitrogen monoxide Nitrogen dioxide Dinitrogen pentoxide
Nonmetallic binary compounds - naming guidelines
NO NO2 N2O5
Nitrogen monoxide Nitrogen dioxide Dinitrogen pentoxide
1. The element closer to the left of the periodic table appears first.
If both elements are from the same group of the periodic table, the lower
one appears first.
2. The element that appears first retains its elemental name.
3. The second element begins with a root derived from its elemental name
and ends with the suffix ide in place of the usual ending.
4. When there is more than one atom of a given element in the formula,
the name of the element usually contains a prefix that specifies the
number of atoms present. prefixes - mono, di, tri, tetra, penta, hexa, etc.
5. Omit prefix if name is unambiguous without prefix i.e., only one option
for the ratio of those two elements
Nomenclature Ionic Compounds
Cation, (usually the element closer to the left of the periodic table )
written first;
Anion, (usually the element closer to the right of the periodic table)
written second, with last syllable changed to -IDE
NaBr sodium bromide
K2S potassium sulfide
MgO magnesium oxide
BaCl2 barium chloride
Li3N lithium nitride
Note the space in the name between cation and anion
Note no numbers in the name for simple compounds where there is

no option for the ratio of ions/atoms involved
Nomenclature Ionic Compounds
Cation, (usually the element closer to the left of the periodic table )
written first;
Anion, (usually the element closer to the right of the periodic table)
written second, with last syllable changed to -IDE
NaBr sodium bromide
K2S potassium sulfide
MgO magnesium oxide
BaCl2 barium chloride
Li3N lithium nitride
Note the space in the name between cation and anion
Note no numbers in the name for simple compounds where there is

no option for the ratio of ions/atoms involved
Polyatomic ions
Ionic compounds may contain polyatomic ions:
Ammonium NH4+
Nitrate NO3-
Acetate CH3COO-
Oxalate C2O42-
note: these wont exist on their own in the solid state

need an electrically neutral species, e.g.:
Ammonium nitrate NH4NO3
Anions containing a central atom surrounded by oxygen

atoms are known as oxoanions, e.g., CO32- carbonate
Nomenclature oxoanions I
1. The name has a root taken from the name of the
central atom
Carbonate CO32-
Nitrite NO2-
2. When an element forms 2 different oxoanions, the

one with fewer oxygen atoms ends in ite, and the
other ends in ate
Sulfite SO32-
Sulfate SO42-
Nomenclature oxoanions II
3. Chlorine, bromine and iodine each form four
different oxoanions that are distinguished by
prefixes and suffixes
Hypochlorite ClO-
Chlorite ClO2-
Chlorate ClO3-
Perchlorate ClO4-
Examples with other central atoms:
BrO3- bromate
IO4- periodate
Nomenclature oxoanions II
3. Chlorine, bromine and iodine each form four
different oxoanions that are distinguished by
prefixes and suffixes
Hypochlorite ClO-
Chlorite ClO2-
Chlorate ClO3-
Perchlorate ClO4-
4. A polyatomic anion with a charge more

negative than 1- may add H+ to give another
anion. These anions are named from the parent
anion by adding the word hydrogen
Hydrogen carbonate HCO3-
Dihydrogen phosphate H2PO4-
Protonated polyatomic oxyanions Protonation implies
Uncharged species are named as acids adding H+
-ate ions = -ic acid, e.g. H2SO4 = sulfuric acid
-ite ions = -ous acid, e.g. H2SO3 = sulfurous acid
When needed, specify number of protons attached.

e.g. PO43 = phosphate ion
e.g. HPO42 = monohydrogenphosphate ion
e.g. H2PO4 = dihydrogenphosphate ion
e.g. H3PO4 = phosphoric acid
e.g. HCO3
e.g. HSO4
=
=
hydrogencarbonate ion
hydrogensulfate ion } No need to specify
number of protons
with a prefix
Patterns in Formulae of Oxyacids
Smaller central atom can fit around it a max. of three O atoms.
He
B C N O F Ne
Al Si P S Cl Ar
Ga Ge As Se Br Kr
Bigger central atom can fit In Sn Sb Te I Xn

around it a maximum of four O Po Rn
Tl Pb Bi At
atoms.
remember the H counts as 3, 2, 1 and 4, 3, 2, 1.

To get the formula of the lower oxyacids
just take off O atoms.
-ic acid
-ous acid
Knowing when to stop removing

oxygens requires chemical knowledge!
the alternative systematic approach
There are two ways of naming metal containing compounds when there
is more than one possibility for the oxidation number of the metal
The systematic nomenclature is useful for naming metal compounds,

with metal oxidation number in Roman numerals (in brackets).
MnCl2 manganese(II) chloride (manganous chloride)

FeCl2 iron(II) chloride (ferrous chloride) contains Fe2+
FeCl3 iron(III) chloride (ferric chloride) contains Fe3+
Hg2Cl2 mercury(I) chloride (mercurous chloride)
HgCl2 mercury(II) chloride (mercuric chloride)
ic and ous nomenclature still appears (more or less!)
Usually only one space in the name: separating cation from anion.
Oxidation Number (State)
(Blackman 12.1)
Definition: The number of charges an atom would have in a molecule
(or ion) if the shared electrons were transferred completely to the
more electronegative atom (see Blackman 12.1)
(Much more on what electronegativity means
and how to calculate oxidation numbers later!)
Rules: Oxidation states are
Elements in their uncombined state = 0 sometimes written as a
In neutral molecules, sum of ONs = 0 Roman numeral,
In an ion, sum of ONs = charge on ion e.g.; Fe(II), Cr(VI)
Usually:
Hydrogen: ON = +1 when combined with non-metals and = 1 with
metals
Oxygen: ON = 2 (except peroxides ON= 1)
Fluorine: ON = 1 (except in F2)
the alternative systematic approach
Can use for non-metals too
SYSTEMATIC naming needs no numerical prefixes.
Other naming uses numerical prefixes for ambiguous species.
leftmost element first for non metals
lower element first in same column
-ide ending
SYSTEMATIC COMMON
NO nitrogen(II) oxide nitrogen monoxide
N2O nitrogen(I) oxide dinitrogen oxide
N2O5 nitrogen(V) oxide dinitrogen pentoxide
NO2 nitrogen(IV) oxide nitrogen dioxide
N2O4 nitrogen(IV) oxide dinitrogen tetroxide
IF5 iodine(V) fluoride iodine pentafluoride
Nomenclature hydrogen compounds
Binary compounds of hydrogen
Hydrogen requires special consideration
It may appear first or second in the chemical formula of a
compound, therefore first or second in the name
Usually appears second when combined with a metallic element
Examples: H first groups 16 and 17;
H second groups 1 and 2
Lithium hydride LiH

Hydrogen fluoride HF
Hydrogen sulfide H2S
Calcium hydride CaH2
Groups 13, 14 and 15

Unsystematic names e.g. B2H6 diborane
Dr Ball Lecture set 3
CHEM1011 2017
Chemical reactions and stoichiometry
3
Chemical equations - Blackman 3.1
A chemical reaction is the mixing of two or more species to

produce new substances
A chemical equation describes what happens when a
chemical reaction occurs
Consider the following reaction:
2H2 + O2 2H2O
reactants: react to products:

hydrogen and oxygen produce water
Chemical equations
Stoichiometry is concerned with the relative amounts of
reactants and products in a chemical reaction
Stoichiometric coefficients indicate

the number of molecules,
ions or atoms among
the reactants
and products
Chemical equations
The law of conservation of mass says that atoms cannot be

created or destroyed during a chemical reaction
Stoichiometric coefficients are used to balance an equation

to meet this condition
Equations and Stoichiometry:
Physical Change: No change in chemical composition.

Changes of state (solid, liquid, gas).
H2O (s) H2O (l)
Chemical Change: Change in chemical composition occurs.

Product(s) have new different properties.
2 H2 (g) + O2 (g) 2 H2O (g)

Parts of a chemical equation. Chemical species.
1 P4 (s) + 5 O2 (g) 1 P4O10 (s)
Coefficients State symbols
In balancing an equation the numbers within each chemical

species CAN NOT be changed. This would be changing the
identities of the chemicals involved.
Coefficients can be changed to balance the equation.
State symbols tell the physical state of the species, which can
affect the reaction rate, and its energy change.
Chemical equations - states of matter
Specifying states of matter

It is useful to specify the physical states of the reactants
and products
This is done by writing:

(s) for solid,
(l) for liquid or
(g) for gas after the chemical formula
(aq), meaning aqueous solution, can also be used to

indicate that a particular substance is dissolved in water
Guide for writing equations
Write reactants on left, products on right (by convention).

Include states of matter.
Change coefficients to give the same count for each element on both
sides. (do not change subscript numbers):
1. Balance elements that appear in one species on both sides,
2. Balance elements that appear in several species on both sides.
For reactions in water, add H2O if needed to balance oxygen atoms.
For reactions in water, add H+ if needed to balance hydrogen atoms.
Give nett ionic equations if possible convey essential change.
You need to know formulae from name translations, and the nature of
solutions, to change a description into a chemical equation.
hydrochloric acid reacts with solid sodium hydroxide to produce a

sodium chloride solution and water.
aluminium sulfate solution and calcium nitrate solution are reacted to

give a precipitate of calcium sulfate and a solution of aluminium
nitrate.
Solid sodium oxide reacts with water to give a sodium hydroxide

solution.
Manganese dioxide reacts with lead dioxide when heated in

suspension in acidic water, to give permanganate ions and lead ions.
" solid sodium hydroxide is reacted with hydrochloric acid to produce a

sodium chloride solution and water".
Re-expressing names as chemical species:
Hydrochloric acid is HCl (aq), which contains H+ (aq) + Cl (aq)

Solid sodium hydroxide is NaOH (s), which contains Na+ ions and OH
ions packed close together in the crystals.
Sodium chloride solution contains Na+ (aq) ions and Cl (aq) ions.
H+ (aq) + Cl (aq) + NaOH (s) Na+ (aq) + Cl (aq) + H2O (l)
Nett equation: H+ (aq) + NaOH (s) Na+ (aq) + H2O (l)

In a nett equation, substances that are unchanged, i.e. the same on both
sides of the equation, are omitted. Cl- in this example.
What are Ions in Water ?
In an ionic solid, the ions bond

together strongly, owing to their
opposite charges (e.g. Na+ and Cl).
Ionic solids dissolve in water because

the breaking of ion-ion attractions of
the solid is compensated for by H2O
molecules forming strong bonds to
each individual ion (solvation).
Also favouring dissolving: ions in

solution can move randomly in the
bigger volume of liquid (increased
randomness).
"aluminium sulfate solution and calcium nitrate solution are

reacted to give a precipitate of calcium sulfate and a solution
of aluminium nitrate."
Al3+ (aq) + SO42 (aq) + Ca2+ (aq) + NO3 (aq)
CaSO4 (s) + Al3+ (aq) + NO3 (aq)
Nett: Ca2+ (aq) + SO42 (aq) CaSO4 (s)

"Solid sodium oxide reacts with water to give a sodium

hydroxide solution."
Na2O (s) + H2O (l) 2 Na+ (aq) + 2 OH (aq)
Equations and Stoichiometry: Blackman 3.3
Stoichiometry - ratio in which chemical species react - the coefficients of

species in a balanced chemical equation.
need to convert amu to weighable amounts - grams.
Use the MOLE - the chemists dozen.
The mole (abbreviated mol) is the SI unit of amount of substance
Definition: a mole of a substance is the mass of it, in grams, that contains the
same number of entities as there are in exactly 12.000 g of carbon-12.
Avogadros constant (6.0221 1023 mol-1) gives the number of entities in 1
mole (6.022140857 0.0000000741023 mol-1 to more significant figures)
the weight of a mole of a substance is its atomic or molecular mass expressed in
grams.
e.g. 1 mole of Fe (55.84 amu) weighs 55.84 g mol1.
The mole
The number of specified entities in a mole is constant
The mass of 1 mole depends on the mass of the individual

entities
The mole
The molar mass, M, is the mass of 1 mole of a substance
What is the molar mass of water (H2O)?

The chemical formula tells us it is made up of 2 hydrogen
atoms and 1 oxygen atom
Hence the molar mass is the sum of twice the atomic mass
of hydrogen (1.008 g) plus the atomic mass of oxygen
(15.999 g)
MH2O = (2 1.008 g) + 15.999 g = 18.015 g
The relationship between amount of substance (moles, n),

molar mass (M) and mass (m) is given by M = m/n
Molar masses can be used to measure out numbers of atoms

and molecules, in exact ratios, on a big scale.
Fe (s) + S (s) > FeS (s)

Atom/species ratio: 1 1 1
Weight atoms : 55.85 amu 32.06 amu 87.91 amu
Molar masses : 55.85 g 32.06 g 87.91 g
Equations and Stoichiometry: Limiting Reagent
What if we react chemicals in a non-stoichiometric ratio?

One of the reagents will be present in excess.
The moles of the other reagent will determine the maximum moles of
product that can be formed, if it all reacts. This reagent is called the
limiting reagent.
Fe (s) + S (s) FeS (s)
Atom/species ratio: 1 1 1
Weight atoms : 55.85 amu 32.06 amu 87.91 amu
Ideal molar masses: 55.85 g 32.06 g 87.91 g
Reaction mixture: 55.85 g 38.0 g 0.0 g
After reaction: 0.0 g 5.94 g 87.91 g
Limiting Excess
Reagent. Reagent.
Molecular and Formula masses are found by summing atomic masses of

the component atoms.
Amount of = actual mass of A

A (in moles) molar (atomic) mass
1000 g
e.g. Amount of H2O in 1000 g of water =
18 g mol1
= 55.6 mole
Note: Formula mass of ionic compounds

use its empirical formula.
e.g. 1 mole of NaCl = 22.99 + 35.45 = 58.44 g mol1
2 decimal places recommended!
Calculating empirical and molecular formulae
Empirical formulae (Blackman 3.4)
The empirical formula is the simplest whole-number ratio of

atoms within that compound.
For example, butane has the formula:
C4H10 molecular formula

However this isnt the simplest ratio as both 4 and 10
are divisible by 2. Hence butane has the empirical
formula:
C2H5 empirical formula

Empirical formulae and percent by mass
The relative masses of elements in a compound is
usually given as a percentage
This is called the percentage composition OR percentage

composition by mass
The percentage by mass of an element in a compound is

calculated using the following:
% element = mass of element x 100%

mass of whole sample
Empirical formulae
A molecular formula gives the chemical composition of one

molecule, e.g. P4O10
The empirical formula for this compound is P2O5
This gives the simplest whole number ratio between atoms
The empirical formula of a compound can be obtained

experimentally by determining the mass of each element in
a compound
Calculating empirical formulae
There are three steps necessary to determine the empirical formula:
1. Assume we are studying 100 g of the compound and

therefore individual mass percentages become the actual
masses
2. Convert the ratio of elements by mass to a ratio by amount,
by dividing the mass of each element by its molar mass
3. Divide the resulting numbers by the smallest of these
numbers, which may give the smallest whole-number ratios
of each element. If not, multiply all the ratios by a small
integer (e.g. 2, 3, 4) to get the lowest whole number ratio.
Empirical vs molecular formulae
The formula for ionic compounds is the same as the

empirical formula
For molecules, the molecular formula and empirical are

different much or most of the time.
The molecular formula will be a common multiplier times all

the coefficients in the empirical formula
If the experimental molecular mass is available, the

empirical formula can be converted into the molecular
formula
Example
A hydrocarbon was found to have the composition C = 92.3% and H = 7.7%.
(a) Find the empirical formula.
(b) Find the molecular formula, if the molar mass were:
(i) 26 g mol-1 or (ii) 78 g mol-1
(a) Consider 100 g of the hydrocarbon. (do this as a matter of routine)
Weight of C in the 100g = 92.3 g = 92.3/12.00 moles C = 7.69 moles.
Weight of H in the 100g = 7.7 g = 7.7/1.008 moles H = 7.64 moles.
Mole ratio of C:H = 7.69 : 7.64 = 1 : 1.007 1:1.
Atom ratio of C:H = 1:1
Empirical formula of hydrocarbon is CH (i.e. C1H1).
Empirical formula mass = 12.00 + 1.008 = 13.008 g mol1.
(b) (i) Ratio of (real molar mass)/(empirical formula mass) = 26/13.008 2/1.
Real molecular formula is (CH) x 2 = C2H2.
(ii) Ratio of (real molar mass)/(empirical formula mass) = 78/13.008 6/1.

Real molecular formula is is (CH) x 6 = C6H6.
A compound was found to have the composition:

Na = 20.7%, H = 0.91%, P = 27.9% and O = 50.5%.
The molar mass is 222 g mol1.
Find the empirical and molecular formula.
Consider 1 mole of compound.* 1 mole of compound = 222 g.
20.7% of its mass is Na, Multiply the fraction of each element by the
0.91 % of its mass is H, molar mass to get the mass
27.9 % of its mass is P, Divide the mass of each element by the atomic
50.5 % of its mass is O. mass to get the number of that element
Mass Na = (0.207 x 222) g = 45.95 g ; Moles Na = (45.95) / 23 = 2

Mass H = (0.0091 x 222) g = 2.02 g ; Moles H = (2.02) / 1.008 = 2
Mass P = (0.279 x 222) g = 61.93 g ; Moles P = (61.93) / 31.45 = 2
Mass O = (0.505 x 222) g = 112 g ; Moles O = (112) / 16.01 = 7
Empirical and 'Molecular' Formula = Na2H2P2O7

* If the molar mass is known already, considering 1 mole of compound is easier than
considering 100 g.
How to measure amount of a substance?
solids - weigh out material.
liquids - measure volume - use density = g cm-3

solutions and gases ?
solution - homogeneous mixture of solute and solvent
Solute - is dissolved. Solvent - does dissolving.
Use solution concentration to measure amount of substance in moles.

Solution stoichiometry (Blackman 3.6)
Chemical reactions are nearly always carried out in solution

to allow mixing mixing at the molecular level
A solution is a homogeneous mixture
When a solution forms, at least two substances are involved,

a solvent and one or more solutes
The solvent is the component present in largest amount
The solute is any substance dissolved in the solvent

Solution stoichiometry (Blackman 3.6)
Solution stoichiometry - molarity
The concentration of solutions
The concentration is most often defined as the amount of

solute dissolved in a particular volume of solution
The concentration of a substance X is represented as [X]

i.e. in square brackets [ ]
When the amount is given in moles and the volume in litres, it

is called the molarity or molar concentration
Solution stoichiometry
Molarity (or molar concentration) has the units mol L1 (often

abbreviated M)
Concentration is based on the ratio of the amount of solute to

the volume of solution
The equation defining concentration is:
n is the number
of moles
The units of c n
C=
are mol L-1 V V is the volume
(in Litres)
Measuring tools of the
trade for chemists
n
C=
V
Other methods of defining solution stoichiometry
(Blackman 10.5)
Molarity
Amount of substance in a particular volume of solution
Solutions (usually) increase in volume with increasing
temperature
The molarity of a solution changes as the temperature changes
Can create problems
Three other methods of defining stoichiometry that do not depend

on volume and so are temperature independent are molality (note
spelling), mole fraction and percentage composition by mass.
Molality
Amount of solute per kilogram of solvent
amount of solute (mol)

molality (b )
mass of solvent (kg)
Temperature independent
Mole fraction
The number of moles of a particular component divided
by the total number of moles of material in the solution
The mole fraction of A, XA, in a solution containing

substances A, B and C:
nA
XA
nA nB nC
Temperature independent
Sum of mole fractions for all components = 1

Percentage composition by Mass
(Blackman 3.4)
The relative masses of components of a solution (or

elements in a compound) may be given as a percentage
This is called the percentage composition OR percentage

composition by mass
The percentage by mass of a components is calculated

using the following:
% component = mass of component x 100%

mass of whole mixture
Measures of Concentration Summary:
Mass % mass of solute 100

= %
mass % x
mass of solution 1
moles of A
Mole Fraction A =
moles of (A + B + ...)
Note that A + B = 1 for a 2 component system.
moles of solute
Molarity = (Molar)
Molarity litres of solution
Units: M or mol L1
moles of solute
Molality Molality = (Molal)
kg of solvent
Units: mol kg1
Solution stoichiometry
Ionic compounds dissociate into their constituent ions when dissolved in
water
This can have important consequences in stoichiometric calculations
e.g. CaBr2 undergoes complete dissociation into Ca2+ and Br ions,

according to the equation CaBr2(s) Ca2+(aq) + 2Br (aq)
0.10 moles of CaBr2 yields 0.10 moles of Ca2+ and 0.20 moles of Br
In 0.10M CaBr2, the concentration of Ca2+ is 0.10 M and the

concentration of Br is 0.20 M
EXAMPLE
A concentrated solution of NH3 in water contains 256 g of NH3 per
litre of solution; the solution has a density of 0.880 g ml1.
Calculate the molarity, molality, mole fraction and % by mass of
NH3 in the solution.
256 g NH3
1L
(880 g)
% by mass:
Consider 1 litre of the solution:
Its density is 0.880 g ml1 , so 1000 ml of solution must weigh 880 g.
In this 1 litre of solution are 256 g of NH3.

% of NH3 in solution = (256g/880g) x 100 = 29.0 %.
(Continued )
EXAMPLE Continued
Molarity of NH3 :
In the 1 litre of the solution are 256 g of NH3
Moles NH3 = 256/(14.01 + 3(1.008)) = 15.06 moles.
molarity of NH3 = 15.1 mole L1.
256 g NH3 = 15.1 moles.
1L
(880 g)
Round up your answer to 3
significant figures (3 sig fig) as
you are given a minimum of 3 sig
fig for values in the question.
- See yellow section of course

pack for more details
EXAMPLE Continued
Note:
If 256 g of the 1000 ml of solution (weighing 880g) is NH3, then the
remaining weight is water*, = 880g 256g = 624 g.
We can use this knowledge in further calculations
256 g NH3
1L
(880 g) 624 g water
* - Key point: the only components of the solution are NH3 and water.
So whatever mass is not NH3 must be water and vice versa.
EXAMPLE Continued
Molality of NH3 :
The 1 litre of solution contains 256 g (= 15.06 moles) of NH3 and 624 g of
water. How many moles NH3 in 1000 g of water?
moles of NH3 in 1 kg of water
= 15.05(1000/624) = 24.1 mol kg1.
256 g NH3 =15.06 moles
1L
(880 g) 624 g water
EXAMPLE Continued
Mole fraction of NH3 :

The 1 litre of solution contains 256 g (15.06 moles) of NH3 and 624 g of
water. This = (624 g/18 g mol1 ) = 34.67 mole of water.
Total moles of all species in 1 litre = 15.06 + 34.67 = 49.73 moles.
NH3 =(moles NH3/moles of all components) = 15.06/49.73 = 0.303.
256 g NH3 = 15.06 moles
1L
(880 g) 624 g H2O = 34.67 moles
TOTAL = 49.73 moles

Other question types:

1. An aqueous solution containing 571.6 g of H2SO4 per litre of solution
at 20C has a density of 1.329 g cm-3.
Find the mass %, mole fraction, molarity and molality of H2SO4 in the
solution.
2. A sample of hydrochloric acid contains 40% HCl by mass.

The density of the solution is 1.20 g cm-3.
What is the molarity of HCl in this solution?

Stoichiometry, limiting reagents and
percentage yield (Blackman 3.5)
Percentage yield
In most experiments, the amount of a product isolated falls
short of the maximum amount
The actual yield of the desired product is simply how much

is isolated
The theoretical yield of the product is what would be

obtained if no losses occurred
The percentage yield is the actual yield calculated as a

percentage of the theoretical yield
Stoichiometry, limiting reagents and
percentage yield
Percentage yield is calculated using the following formula:
% yield = actual yield x 100%

theoretical yield
The calculation may be done in either grams or moles,

but both actual and theoretical yields must be in the same
units
The actual yield can never be more than the theoretical

yield
Lecture content - Week 2-3
Lecture content
Common reagents and their reactions

(acids, bases (Brnsted), oxides, carbonates).
Gases: properties, diffusion. Ideal gas law;

determination of molar mass; density.
Gas mixtures: partial pressures, Dalton's law.
Learning objectives - Week 2-3
After this week you should be able to:

Define what is meant by an acid and a base.
Know the names and formulae of common acids and bases.
Predict the products of reactions of acids and bases with oxides,
carbonates etc.
Describe the properties which distinguish gases from other states of
matter.
Calculate properties of gases and gas mixtures using the ideal gas
equation.
Common reagents:
Acids and bases
Acids and Bases
Definition 1 - Arrhenius
An acid is a substance containing a
hydrogen that dissociates in solution to
give H+ ions.
e.g. HCl, H2SO4, CH3CO2H
A base is a substance that contains

hydroxide groups and dissociates to
produce OH ions when dissolved in
water.
e.g. NaOH, Ba(OH)2, KOH Svante Arrhenius
1859-1927
Swedish physicist/chemist
Nett acid base reaction:
(Nobel prize, chemistry 1903)
H+(aq) + OH- (aq) H2O (l)
Acids and Bases
Definition 2 - Brnsted-Lowry
An acid is a substance that donates a proton.
E.g. HCl,
A base is a substance that accepts a proton.
Unlike Arrhenius definition:

The base does not have to contain OH, so NH3 and CH3CO2 are bases.
The acid-base reaction does not have to take place in water.
HCl (aq) + CH3CO2 (aq) Cl (aq) + CH3CO2H (aq)

acid base base acid
The BrnstedLowry definition of acids and
bases (Blackman 11.1)
For a proton to be measurably acidic, it must be bound
to another atom via an appreciably acidic bond
Acids tend to contain protons bound to group 16 or

17 elements
Basic species require the presence of one or more lone

pairs
Not all species containing lone pairs act as bases
Bases usually contain group 15 or 16 elements, the

atoms of which are often deprotonated (e.g. OH- )
Acids and Bases
STRONG ACID
A strong acid is one that dissociates essentially completely to release H+ ions in
solution.
E.g. HCl, HBr, HI (but not HF), HNO3, H2SO4, HClO3, HClO4
HCl (aq) H+ (aq) + Cl (aq)
A weak acid dissociates incompletely

Acids and Bases
STRONG BASE
A strong base is one that dissociates essentially completely (or reacts with
water completely ) to release OH ions in solution.
E.g. NaOH, KOH, Ba(OH)2
NaOH (s) + H2O (l) Na+ (aq) + OH (aq)
A weak base reacts incompletely with water
Strong acids and bases are strong electrolytes, as their dissolved species exist
as ions.
Common acids
Sulphuric acid, H2SO4 many industrial applications,
e.g. making rubber
Nitric acid, HNO3 many industrial applications,
e.g. making fertilizer
Acetic acid, CH3CO2H
present in vinegar
Carbonic acid, H2CO3
results from CO2 dissolved in water fizzy drinks
Q. What do these four acids have in common?

Phosphoric acid usage example
Formula: H3PO4
Several uses including rust remover and a food additive in

cola drinks!
Concentrations:
0.2-0.3% by mass in cola
~25% in a typical rust remover
Common bases
Caustic soda
sodium hydroxide
Garden lime Ammonia solution
mostly calcium carbonate
Strong acids and bases (Blackman 11.3)
Which acids are strong and which are weak?
Remember just the strong acids, as they are few.
Anything other acid (in first year chemistry!!) will be weak.
Not HF
HCl HNO3 H2SO4 HClO3 HClO4

HBr HBrO3 HBrO4
HI HIO3 HIO4
Multiprotic Acids
Some Brnsted acids can release more than one proton.

Monoprotic acids release one proton per molecule,
diprotic acids release two, and triprotic, three.
e.g.
Monoprotic hydrochloric acid: HCl (aq) H+ (aq) + Cl (aq)
Diprotic sulfuric acid: H2SO4 (aq) 2 H+ (aq) + SO42 (aq)
Triprotic phosphoric acid: H3PO4 (aq) 3 H+ (aq) + PO43 (aq)

Reactions of acids (1)
acid + base salt + water
BaO (s) + 2 HCl (aq) BaCl2 (aq) + H2O (l)
2 NaOH (aq) + H2SO4 (aq) Na2SO4 (aq) + H2O (l)
note that Na+ and SO42- are just spectator ions and the nett ionic
equation is H+ (aq) + OH- (aq) H2O (l)
Al2O3 (s) + 6 HClO4 (aq) 2 Al(ClO4)3 (aq) + 3 H2O (l)
Cu(OH)2 (s) + 2 HNO3 (aq) Cu(NO3)2 (aq) + 2 H2O (l)
In examples 1, 3 and 4 the base is a solid oxide or hydroxide compound

acid + carbonate salt + water + carbon dioxide
CaCO3 (s) + 2HCl (aq) CaCl2 (aq) + CO2(g) + H2O (l)
3 ZnCO3 (s) + 2 H3PO4 (aq) Zn3(PO4)2 (aq) + 3 CO2 (g) + 3 H2O (l)
Also for hydrogencarbonates:
2 NaHCO3 (aq) + H2SO4 (aq) Na2SO4 (aq) +2 CO2 (g) + 2 H2O (l)
the nett equation for this reaction is
HCO3- (aq) + H+ (aq) CO2 (g) + H2O (l)

acid + metal salt + hydrogen
note this reaction requires a metal that is more electropositive than

hydrogen (see later, week 11??)
Zn, Sn, Fe, Mg, Al

NOT Cu, Ag, Au, Pt
Zn (s) + 2 HCl (aq) ZnCl2 (aq) + H2 (g)

note the nett reaction for metals is:
M (s) + n H+ (aq) Mn+ + n/2 H2 (g)
Acids and Bases
STRONG ACID
A strong acid is one that dissociates extensively to release H+ ions in solution.
E.g. HCl, HBr, HI (but not HF), HNO3, H2SO4, HClO3, HClO4
HCl (aq) H+ (aq) + Cl (aq)

The strength of an acid can be expressed as its acidity constant, Ka.
[H+] means the concentration of H+(aq) ions in moles per litre.
For HCl, Ka is very large, as virtually no

molecular HCl exists in solutions.
A strong acid is a strong electrolyte, as
its dissolved species exist as ions.
(More on this in ~week 10!)
Acids and Bases
WEAK ACID
A weak acid is one that dissociates only slightly to release H+ ions in solution.
E.g. HF, HNO2, H2SO3, H3PO4, HClO, HClO2, CH3CO2H (and similar molecules)
CH3CO2H (aq) CH3CO2 (aq) + H+ (aq)

99.6% 0.4% 0.4%
For CH3CO2H, Ka = 1.74 x 105, so it exists 99.6% in the molecular form, when in
dilute aqueous solution.
A weak acid is a weak electrolyte, as its dissolved species exist mostly as neutral
molecules.
Acids and Bases
WEAK BASE
A weak base is one that dissociates or reacts only slightly with water, to accept a
proton and release some OH ions in solution.
E.g. NH3
A weak base like NH3 is a weak electrolyte, as its dissolved species exist mainly
as neutral molecules.
NH3 (aq) + H2O (l) NH4+ (aq) + OH (aq)

99.6% 0.4% 0.4%
Strong vs Weak
Eletrolytes
End Of Lecture
Set 4
Topic 3
Gases
Reference: Blackman Chapter 6
Sections 6.1-6.6
Branches of Chemistry
Chemistry often split into 4 branches:
Physical Analytical Inorganic Organic

chemistry chemistry chemistry chemistry
Boundaries blurred, much overlap

Categorization not essential
Gases topics usually put in the physical chemistry
basket
So what is physical chemistry about?
What is physical chemistry?
A simple definition for this diverse topic is not available
Physical chemistry is the explanation of the properties and

reactions of matter in terms of the fundamental forces of
nature (Colleague)
Physical chemistry is the study of the underlying physical

principles that govern the properties and behavior of chemical
systems. (Levine)
More than the other branches of chemistry, physical chemistry

is about WHY things happen at the molecular level
Gases what would we like to
know?
Why do gases behave the way they do?
How can the properties of gases be predicted?

(e.g., pressure, volume, density, diffusion rates)
Relate bulk properties such as pressure and temperature

to the behaviour of gases at the molecular level the
kinetic theory of gases
later in first year
Properties of Gases
Gas volume changes greatly with pressure and temperature;
Gases have relatively low viscosity; (viscosity is defined as a

measure of a fluids resistance to flow)
Most gases have relatively low densities under normal

conditions;
Gases are miscible, i.e., they mix with one another in any
proportions.
Describing gases (Blackman 6.2)
Gases expand to occupy all of the
space of their container
This implies that the individual gas

atoms or molecules are free to move
anywhere within their container
Therefore the forces between them

must be very weak
Describing gases
The defining characteristic of gases is the pressure they exert.
The pressure (p) exerted by a gas is dependent on:

The amount of gas present (n number of moles)
The volume in which it is contained (V)
Temperature (T)
Gas Pressure and Measurement
Pressure is defined as force exerted per unit area:
force
Pressure =
area
SI unit of force is newton (N)

1 N = 1 kg m s2,
and of pressure is pascal (Pa),
1 Pa = 1 N m2
1 bar = 1 105 Pa
Pressure differences
The Manometer
A manometer measures the

difference in pressures
exerted by two gases
Explains why mm Hg is a
popular alternative unit of
pressure
16
Gas Laws
Four variables define the physical behaviour of a sample of gas:

pressure (P), volume (V), temperature (T), amount / no. of
moles of gas (n);
Variables are interdependent: any one of them can be

determined by measuring the other three;
Three key relationships exist among the 4 gas variables:

Boyles, Charless and Avogadros laws
laws are special cases of the Ideal Gas Law.

Boyles Law
Relationship Between V and P
At constant temperature, the volume of a
fixed amount of gas is inversely
proportional to the applied (external)
pressure;
or PV = constant (note T and n are fixed)
The constant is the same for the great

majority of gases. Robert Boyle (1627-1691)
Irish natural philosopher
Boyles Experiments
Boyle investigated gases in a J-shaped tube
Determined that volume was inversely proportional to pressure

Charless Law
Relationship Between V and T
J. Charles & J.L. GayLussac: 18th/19th century
French scientists.
At constant pressure, the volume of a fixed

amount of gas is directly proportional to its
absolute temperature:
V
V T [ P and n fixed) or constant
T
If T increases, V increases, and vice versa.
Kelvin scale needs to be used in gas

calculations. 20
Avogadros Law
Relationship Between Volume and Amount
At fixed temperature and pressure, the volume of a gas is
directly proportional to the amount (mol) of gas:
V
V n (P and T fixed) = constant
n
At fixed T and P, equal volumes of any ideal gas contain

equal numbers of particles (or amounts in mol);
The constant is the same for all gases at fixed T and P.

Charles Law experiments
Charles Law
Determined the volume of a
gas is directly proportional
to its temperature
Avogadros Law
Gas volume is directly
proportional to the amount
of gas
The Ideal Gas Law
Boyles Law: V1/P (fixed n, T)
Charless Law: VT (fixed n, P)
Avogadros Law: Vn (fixed P, T)
Ideal Gas Law:
nT PV
V or PV nT or R
P nT
or PV = nRT
R is a proportionality constant known as the
universal gas constant = 8.314 J K1 mol1
The Ideal Gas Law
The gas equation becomes one of the individual gas laws
when two of the four variables are kept constant,
e.g., when initial conditions (subscript 1) change to final
conditions (subscript 2)
Dont forget always

use temperatures in
Kelvin
When P and T are constant, equation is:
Other units of pressure
The SI unit for pressure is pascal (Pa)
1 Pa = 1 N m-2
A number of non-SI units are used:
1 atm is the pressure that will support a column of
mercury 760 mm in height
1 atm = 1.01325 x 105 Pa
1 torr is the pressure exerted by a column of mercury
1 mm in height
1 atm = 760 torr
1 bar = 105 Pa
A word about units and the value of R
SI units: PV=nRT
P is in Pascals, Pa
V is in cubic metres, m3
IF V in m3 and P in Pa, R = 8.314 J mol-1 K-1
Commonly used units
P is in atmospheres, atm
V is in litres, L or dm3
IF V in L and P in atm, R = 0.08206 atm L mol-1 K-1
CONVERT TO ONE PAIR OF UNITS OR THE
28 OTHER
Gas Behaviour at Standard Conditions
Chosen set of standard conditions called

standard temperature and pressure (STP):
STP: O oC (273.15 K) & 1 atm (760 Torr)
Volume of 1 mol of an ideal gas at STP is called

standard molar volume (22.414 L)
At room temperature, ~25 oC or ~298K,

1 mole of gas occupies about 25 L.
The Density of a Gas
mass
Recall: density
volume
mass of compound
and number of moles, n
molar mass of compound
Using ideal gas law:
Note: Density of a gas is: directly proportional to its molar mass

and inversely proportional to its temperature (in K).
Molar mass from the density of a gas
Can use a simple rearrangement of the gas law to determine
the molar mass of an unknown gas or volatile liquid:
Example
Calculate the molar mass of a gas if 0.455 g occupies a

volume of 250.0 mL at 27 oC and 772 mmHg.
Answer
Calculate the molar mass of a gas if 0.455 g occupies a volume of
250.0 mL at 27 oC and 772 mmHg.
dRT
Use Mr
P
Remember to change to an appropriate set of units!
Using volume in litres, pressure in atm, temperature in K:
Volume = 250.0/1000 litres, 0.2500 L; then density = mass/ volume
Pressure converted to atmospheres = 772/760 atm
Temperature = 27 + 273.15 = 300.15 K
(0.455 / 0.2500)* 0.08206*300.15

=> Mr
(772 / 760)
Units for the answer is grams since we used a mass in33grams
Daltons Law of Partial Pressures
Partial Pressure of a Gas in a Mixture
John Dalton 1766-1844
English Chemist/Physicist
Father of atomic theory

Partial Pressure of a Gas in a Mixture
In a mixture of unreacting gases, the total pressure is the
sum of the partial pressures of the individual gases:
Ptotal = P1 + P2 + P3 +
Each gas in the mixture exerts a partial pressure, a

portion of the total pressure of the mixture, that is the
same as the pressure it exerts by itself.
The partial pressure for a given gas is the pressure it
would exert if it were the only gas in the same container
under the same conditions
(Blackman 6.5)
combine
Example
e.g., adding hydrogen gas to a fixed volume tank
containing nitrogen gas at a certain pressure.
Each gas behaves independently, hence:
nN2RT nH2RT
PN 2 and PH2
V V
At same volume V and T, the partial pressure
of each gas depends on its amount:
nN2 RT nH2RT ntotal RT
Ptotal PN2 PH2
V V V
Note: ntotal = nN2 + nH2
Mole Fractions and partial pressures
Each component in a mixture contributes a fraction of the total
number of moles in the mixture, the mole fraction (X) of that
component. e.g., in a N2/H2 mixture:
n N2 n N2
X N2
ntotal nN2 nH2
sum of mole fractions of all components in mixture = 1:
Ptotal PN 2 PH 2
(X N 2 Ptotal ) (X H 2 Ptotal )
1 Ptotal
The partial pressure of a component in a gas mixture is its mole
fraction multiplied by the total pressure
Gas stoichiometry Blackman 6.6
The principles of stoichiometry apply equally to solids,
liquids and gases
No matter what phase substances are in, their chemical

behaviour can be described in molecular terms
Stoichiometric calculations always require amounts in

moles
For gases, amounts in moles are usually calculated

from the ideal gas equation
Ideal Gas Law and Reaction Stoichiometry
The ideal gas law can be used to convert between gas

variables (P, T, V) and amount (mol) of gaseous reactants
and products;
do not need to measure mass.
Example (harder):
Hydrogen at 1200 torr pressure is in a constant volume,

constant temperature container, and nitrogen is introduced
until the total pressure is 2100 torr.
The formation of ammonia is started by adding a catalyst,

the whole place taking place at constant temperature.
Calculate the partial pressure of (i) hydrogen, and (ii)

ammonia, in the container when the partial pressure of
nitrogen is 650 torr.
Example (harder):
Hydrogen at 1200 torr pressure is in a constant volume,

constant temperature container, and nitrogen is introduced
until the total pressure is 2100 torr.
The formation of ammonia is started by adding a catalyst,

the whole place taking place at constant temperature.
Calculate the partial pressure of (i) hydrogen, and (ii)

ammonia, in the container when the partial pressure of
nitrogen is 650 torr.
Answer:
At the start, before reaction, PH2 = 1200 torr; Ptotal = 2100 torr
Daltons Law => Ptotal = PN2 + PH2 => PN2 = 2100 1200 = 900 torr
Reaction starts both N2 and H2 are consumed
Write out a balanced equation:
N2 + 3 H2 -> 2 NH3
so 1 mol of N2 reacts with 3 moles H2
and 1 mol of N2 produces 2 moles NH3
Remember that partial pressure of gas is directly proportional to number of

moles (from Daltons Law)
So for every one unit of pressure of N2 consumed, 3 units of pressure of
H2 are used and 2 units of pressure of NH3 are made.
N2 at start = 900 torr; N2 at end = 650 torr => N2 used = 900 650 = 250 torr
So, H2 used = 3 * 250 = 750 torr; so (i) PH2 remaining = 1200 750 = 450 torr
and (ii), PNH3 produced = 2 * 250 = 500 torr
Effusion and diffusion
Concern movement of gases
Allow us to answer questions such as:
Theres a pinhole in my spaceship which gas will
escape quickest?
There is a gas leak across the other side of the room -
how long before I can smell it?
Effusion and Diffusion
Effusion: process by which a
gas escapes from its container
through a tiny hole into an
evacuated space;
Grahams law of effusion: the rate of effusion of a gas is

inversely proportional to the square root of its molar mass:
1
Rate of effusion
Mr
Rates of Effusion
Rate A M r (B)
In general, for two gases A and B
Rate B M r (A)
The gas with a lower molar mass will effuse faster;
Grahams law can be used to determine the molar mass

of an unknown gas, X, by comparing its effusion rate with
that of a known gas, say He:
2
rate He
M r (X) M r (He)
rate X
Rates of Diffusion
Diffusion is the movement of
one gas through another;
Grahams law is used to
describe diffusion rates:
1
Rate of diffusion
Mr
eg., for equal pressures of NH3 and HCl through another gas
or air:
Rate NH3 Mr (HCl)

Rate HCl Mr (NH3 )
Example:
If it takes 1.25 minutes for 0.010 mol He to effuse,
how long will it take the same amount of ethane
(C2H6) to effuse?
0.010 mol
rate of effusion of He = 8.0 10 3 mol min 1
1.25 min
Now: Rate C 2H 6 M r (He )

Rate He M r ( C 2H 6 )
4.00 g mol 1
Rate C H = RateHe
2 6 30.04 g mol 1
= 8.0 10 3 mol min 1 0.363

= 2.9 10 3 mol min 1
Purifying uranium by effusion
Uranium hexafluoride, UF6 a gas just above room temperature
Can separate 235UF6 and 238UF6 based on the rate it effuses
Essentially repeat the effusion process hundreds of times, the
lighter 235UF6 will escape more quickly on average
K25,Oak Ridge,
Tennessee, USA
Built during WW II
Real Gases
Deviations from Ideal Behaviour
Ideal gases: no molecular volumes (points) and no
interactions between molecules;
Real gases: have non-zero volumes and have
interactions between molecules;
At relatively high T and low P conditions simple gases
exhibit nearly ideal behaviour;
At STP (0 oC, 1 atm) gases deviate slightly from ideal
behaviour.
The ratio PV/nRT = 1 for ideal gas at any pressure, but
not so for real gases.
More on real gases later (~week 7) 50
Examples (easier)
How many moles of gaseous arsine (AsH3)

occupy 0.0400 L at STP?
If 2.56 L of hydrogen gas at 27.1 oC and a

pressures of 0.682 atm has its temperature
lowered to 23.2 oC at its pressure increased to
0.824 atm, to what value will the volume of the
gas change?
51
ELECTRONICSTRUCTUREOFATOMS
Blackman4.14.9
Learningobjectives
Calculatewavelengthfromfrequencyandviceversaforelectromagnetic
radiation.
UsetheRydbergequationtocalculatethewavelengthsemittedor
absorbedbyaHatom.
Calculatephotonenergyfore.m.radiationfromitsfrequency.
Listtheallowedvaluesofthequantumnumbersfororbitalsinhydrogen
likeatoms.
Sketchtheshapesofs,p,anddorbitals.
Writegroundstateelectronconfigurationsforallmaingroupelements
andfirstrowtransitionmetalsandionsoftheseelementsusing'arrowsin
boxesand'1s1'notation.
Identifyisoelectronicspeciesandpredictrelativesizesofthesespecies.
Predictthemagneticpropertiesofisolatedatomsandions.
Predictrelativesizes,ionizationenergies,electronaffinitiesand
electronegativities ofatomsbasedonpositionintheperiodictable
Introduction
Wewilldiscussthepropertiesofatoms,lightandtheinteractions
betweenthem.
Lightinteractswithelectronsonatoms andhasbeenan
importanttooltoprobeatomicproperties.
Fromsuchstudyhascomethetheoryofquantummechanics,which
explainstheelectronicstructureofatoms,orbitalenergylevelsand
patternsofchemicalbehaviourintheperiodictable.
Electronsonthesurfaceofanatomdetermineitschemical
properties(isotopesofanelementhavenearlyidenticalchemical
properties).
Revision:Atomicstructure
Anatomconsistsofapositivenucleus(protons+neutrons),
wherethemassisconcentrated,surroundedbyanegative
electroncloud
Anatomiselectricallyneutral:itcontainsanequalnumber
ofprotonsandelectrons
Atomshavevariouspropertiesconsideringtheirnumbersof
neutrons,protonsandelectronsandcancombinetoform
molecules
CharacteristicsofLight
(Blackman4.2)
Waveparticledualityoflight
Wavelikepropertiesoflight
Lightorelectromagnetic
electromagnetic radiationisaselfsustaining,
wave direction
regularoscillationofelectric
andmagneticfieldsmoving
throughspace awave
Oscillatingelectric(E)and
From: magnetic(B)componentsare
http://en.wikipedia.org/wiki/El
ectromagnetic_radiation
perpendiculartoeachother
Wavelength():thedistancebetweentwo
successivecrests(inmornm)
Frequency():thenumberofwavespassinga
certainpointin1s(ins1 =Hz)
Amplitude:themaximumdisplacementofthe
wavefromitscentre(intensity)
Velocity dependsonthedensityofthe
substancepassingthelight.
Forvacuum,c=2.998x108 ms1.
c =
Example
Calculatethewavelengthofe.m.radiationof
frequency =104MHz?
Solution:
Theelectromagneticspectrum
Whatweperceiveaswhitelightactuallyconsistsofa
rangeofwavelengths(400800nm).
VisibleLight
Onlyasmallpartoftheelectromagneticspectrum
Visiblespectrummnemonic="ROYGBIV" Red,Orange,Yellow,Green,
Blue,Indigo,Violet
Monochromatic e.m.radiation/light:aselectionofonefrequencyof
e.m.radiation canbeusedforvariousscientificmeasurementsetc
Polychromatice.m.radiation/light:consistsofmanyfrequencies
suchasthelightwereceivefromthesun.
E.M.radiationshowstypicalwaveproperties:
REFRACTION: Itspathbendswhenpassedatanangle
throughaninterfacebetweendifferentphasesofmatter.
DIFFRACTION:Uponpassagethroughaslit,itexpandsinto
radiatingcircularwavefronts.
INTERFERENCE:Twolightwavescancombineconstructively
ordestructively,dependinguponhowtheirpeaksandtroughs
coincide.
BUT e.m.radiationalsoshowspropertiesthatcannotbe
explainedbywavetheory
Thephotoelectriceffect
Hertz(1887)foundthat
lightcouldejectelectrons
fromthesurfaceofa
metal.
Byconductingthe
experimentinavacuum,a
currentcouldflowto
anotherelectrode.
One of several unexplained effects in physics that could not be explained

prior to quantum mechanics
Experimentsshowed:
currentwouldflowifthelighthadafrequencyaboveacertain
thresholdvaluethatwascharacteristicofthemetalused.
nocurrentwouldflowusinglightbelowthethresholdfrequency,
nomatterhowintenseitwas.
abovethethresholdfrequency,thecurrent'ssizedependedupon
theintensityofthelight.
theenergyoftheelectronsejectedfromthemetaldependedupon
thefrequencyofthelight
Wavetheoryimpliedshouldbepossibletoprovideenough
energytoejectelectrons(atanylightfrequency)bymaking
thelightintenseenough(withabigenoughwaveamplitude).
NOTOBSERVED
Instead,Einstein(1905)proposedlightconsistedofpacketsof
energy(photons),
EXPLAINSOBSERVATIONS(Nobelprize1921).
Aphotonwithenoughenergystrikinganatomonthemetal
couldbeabsorbed,ejectinganelectron,whichgaveacurrent.
Eachphotonhasanenergythatisdirectlyproportionalto
itsfrequency
Ephoton =hphoton
histhePlancksconstant=6.626x1034Js
Energyofaphotonwiththethresholdfrequency(0)
correspondstothebindingenergyofanelectron(explains
thresholdenergy)
Electronkine cenergy=photonenergybindingenergy
Ekinetic(electron) =h h0 (explainsexcessenergy)
Diagramoftheenergybalanceforthe
photoelectriceffect:
Ekinetic(electron) =h h0
Acompletedescriptionoflightincludes
bothwavelikeandparticlelikeproperties
Plancksequationexample
QuantisationofEnergy
Agasheatedbypassageofelectriccurrentemits lightata
fewspecificwavelengths(calledlinespectra)
Whyweretheenergisedatomsnotemittingatall
wavelengths?
Explainresultsbyassumingthatatomsandphotonscan
haveonlycertainvaluesfortheirenergies quantisation
Bohr(1913)
atomscanadoptonlycertain,discrete,energylevels
atomchangingtoalowerenergylevelwouldloseadiscrete
amountofenergy,emittedasacertainfrequencyoflight
(alineemission)
Manyatomsinahotsamplewouldsimultaneouslyundergo
varioustransitionsbetweenallallowableenergylevels,to
emitasetoflinesoflightwhoseenergiescorrespondtothe
energydifferencesbetweentheenergylevels.
Whenanatomgoesfromoneenergyleveltoanother,a
photonisemittedwithenergy,E=h,equaltothedifference
betweenthetwolevels
Sampleofmanyatoms,theintensity oflightemitteddepends
uponthenumber ofatomsundergoingthecorresponding
energychangeatonetime
Groundstate:
lowestenergystateforan
atom
Excitedstate:
atomwithanenergy
abovethegroundstate
Atomicspectra
Absorption:atomsabsorbspecificandcharacteristic
frequenciesoflight
Emission:photonsareemittedbyatomsinexcitedstate
Eachelementhasuniqueabsorptionandemissionspectra,
providinginformationaboutatomicstructure
Absorptionspectra
Polychromaticwhitelightsourcepassedthroughsampleof
gas
Gaseousatomsabsorbatspecificdiscretefrequenciesas
wellleadingtodarkbandsinthespectra
Emissionatomicspectra:examples
Emissionspectrumofhydrogen
electronicstructureofhydrogenatomisrelativelysimple.
usefulmodelforunderstandinghowotheratomsbehave.
hothydrogengasgivesoffalineemissionspectrum,composed
ofgroupsoflines
visiblelines:
analysedby
Balmer(1885)
TheRydbergformula
Rydberg(1888),buildingonBalmerswork,discovereda
formulathatfittedthelinepatternsofthehydrogenemission
spectrum:
=wavelengthofline(m);RH =theRydbergconstant
(1.097x107 m1);n1 andn2 arepositiveintegers,withn2 >n1
TheBohrmodeloftheatom
Bohr(1913)partiallyexplainedRydberg'sformula
eachtermoftheequationderivedfromanallowedenergy
levelfortheHatom
Eachenergylevelhadenergy:
withnapositiveinteger
Eachintegervalueofndescribesanenergyleveloftheatom.
"n"foreachlevelisthequantumnumber
n=1,lowestenergylevel=>groundstate.
Heatingcanplacethehydrogenatomsinanexcitedstate
(n=2orhigher)whichisunstableandmayemitphotons
Transitionsinthehydrogenatom
Paschen
Balmer
Lyman
series:
Energyleveldiagrams
Energylevelsforthe
hydrogenatomand
someofthetransitions
betweenlevels
Notetheuneven
spacing!!
EnergyLevels,absorptionandemission
Energyleveldiagrams
Ananalogy:
aballon
staircaseshows
someproperties
ofquantised
energystates
Energylevelsinthehydrogenatom
Theenergyofanelectronictransitionisgivenby:
Theenergychangeofthetransitiontakestheformofa
photonofenergyE=h (=hc/).
SubstitutingforEgivesameformastheRydberg
equation:
CanuseRydbergequationtocalculateenergychangefora
transitionbetweenanytwolevelsofahydrogenatom.
Rydberg example ionizationenergy
Ionizationenergy energyrequiredtocompletelyremovean
electronfromaspeciesinitsgroundstate
"Completeremoval"ofanelectronmeansthattheelectron
hasbeenmovedtothen= energylevel
QuickQuizRydbergexample
Calculatethelongestwavelengthoflightcausingalineinthe
Balmerseriesoflines(n1 =2)forthehydrogenemissionspectrum
RH =theRydbergconstant=1.097x107 m1
Quantummechanics
Newtonianmechanics
inappropriateforatoms
Bohrmodel(right)asignificant
advancebutnotthefullstory
Quantummechanics,developedmostlyinthe1920s,
providesabettermodel.
Providesamathematicaldescriptionofmuchofthedual
particlelikeandwavelikebehaviourandinteractionsof
energyandmatter
Quantummechanics
locationin3DspaceoftheelectronofaHatomisdescribed
byawavefunction .
energyoftheelectroncalculatedusingthewavefunctionin
theSchrdingerequation:
probabilityelectrondensityabouttheatomcanbecalculated
fromthesquareofthewavefunction,2.
Schrdingerequationisawaveequation
deBroglie(1923)suggestedthewaveparticledualityfor
electrons(andotherparticles)
Thedoubleslitexperiment
Whathappensifwesendelectronsthroughtwo
closelyspacedslits? evidenceforwave properties
https://www.youtube.com/watch?v=YoQYnhHQ95U
Heisenberguncertaintyprinciple
HUPplaceslimitsonourabilitytofindtheexactpositionof
theelectronatanytime
Mathematically,theposition(x)andmomentum(p)ofa
particlewavearelinked
Themorepreciselythepositionisdetermined,theless
preciselythemomentumisknowninthisinstant,andvice
versa
Canonlyfindtheprobabilityoftheelectronbeinginacertain
volumeofspaceabouttheatom
Electronprobabilitydistributions
ForanelectroninHatominitsgroundstate,probability
densitymaximisesashortdistancefromnucleus
probabilitydensitydecreasesfartherawayfromnucleus.
Atomicorbitals
Forpracticalpurposes,thesizeoftheregionofspace
containing90%oftheelectronprobabilitydensityisdefined
asitsboundarysurface.
Theenclosedvolumeofspaceoccupiedbythatelectronis
calledtheatomicorbital.
Atomicorbitals
manyotherwavefunctionsfitSchrdinger'sequation
describeasetofatomicorbitalsthatarevalidforthe
hydrogenatom.
eachatomicorbitalischaracterisedbythreequantum
numbers
quantumnumbersdeterminetheenergy(quantised)and
shapeoftheorbital.
afourthquantumnumberdescribesthespin ofthe
electron
Quantisationandquantumnumbers
(Blackman4.4)
Principalquantumnumbern
Indexesenergyforanyatomcontainingonlyasingleelectron
Theprincipalquantumnumbermustbeapositiveinteger
(n =1,2,3)
n iscorrelatedwithorbitalsize
Asn increases,theenergyoftheelectronincreases,itsorbital
getsbiggeranditislesstightlyboundtotheatom
Azimuthalquantumnumber
Indexestheangularmomentumoftheorbital
Thevaluecorrelateswiththenumberofpreferredaxesina
particularorbital
Ittherebyidentifiestheshapeoftheelectrondistribution
withintheorbital
canbezerooranypositiveintegersmallerthann
Valueof 01234
Orbitaldesignationspdfg
MagneticquantumnumbermThemagneticquantumnumber
indexestherestrictednumbersofpossibleorientations
Themagneticquantumnumber(m)canbeanypositiveor
negativeintegerbetween0andl :m =0, 1, 2
thereare2+1possiblevaluesform
Spinquantumnumberms
Allelectronshaveapropertycalledspin
Thismeansthattheycanbehaveinoneoftwowaysina
magneticfield
Thespinquantumnumberindexesthisbehaviour
ThePauliexclusionprinciple
statesthateachelectroninanatomhasauniquesetofquantum
numbers,whichmustmeetalltherestrictionssummarised
below
directconsequenceisthatanyorbitalcancontainamaximumof
twoelectrons
Quantumnumbersummary
1. NAME:principlequantumnumber(n)
VALUES:1,2,3,...
PROPERTY:determinesthesizeoftheorbital,and
largelyitsenergy(especiallyfortheHatom).
2. NAME:angularmomentum(azimuthal)quantumnumber()
VALUES:0,1,2,3,....(n1)
PROPERTY:determinestheshapeoftheorbital.
3. NAME:magneticquantumnumber(m)
VALUES: ...0...
PROPERTY:determinestheorientationoftheorbital
4.NAME:spinquantumnumber(ms)
VALUES:+,(givesrisetotwoelectronsperorbital)
PROPERTY:twoorientationsinmagneticfield
Example QuickQuiz
Example
Shellsandsubshells
shell setoforbitalswiththesamevalueofn
Forthehydrogenatom,withitssingleelectron,allorbitals
inthesameshellhavethesameenergy.
subshell setoforbitalswiththesamen and .
Subshellslabeledwithassociatedletters,p,d,fetc
e.g.a"2s"orbitalhasn=2and=0
Atomicorbitalelectrondistributions
andenergies
Orbitalelectrondistributions
Distributionofelectronscanbedescribedusingelectron
density
Orbitalsdescribethedelocalisationofelectrons
Anatomthatcontainsmanyelectronscanbedescribedby
superimposingtheorbitalsforallofitselectronstoobtain
theoverallsizeandshapeoftheatom
Orbitaldepictions
Orbitalpicturesprovidemapsofhow
example:
anelectronwaveisdistributedin 2sorbital
space
Anelectrondensityplot(a):electron
distributionvsdistancefromthe
nucleusasa2Dgraph(radial
distribution)
Electrondensitypictures(b):
3Dnatureoforbital(aslice)
Aboundarysurfacediagram(c):
simplifiedorbitalpicture
sorbitals
=0correspondstoansorbital onlyonesorbitalforeachshell
sphericallysymmetrical,boundarysurfaceisasphere
ls orbitalhaspeakofelectrondensityclosetothenucleus,
decreaseswithdistancefromthenucleus(~12slidesback)
2s orbitalisalsospherical(previousslide),but
smallpeakofelectrondensityclosetothenucleus,thenanodeof
zerodensity,followedbymainpeakofdensityatgreaterdistance.
Peakofelectrondensityofthe2sorbitalisfurtherfromthe
nucleusthanlspeak,=>2selectronhigherinenergythanals.
ForHatom,n isagoodindicatorofelectronenergy.
porbitals
Thequantumnumber =1correspondstoaporbital
Foreachvalueofnthereare3porbitals(m =+l,0and1)
porbitalsconsistoftwolobesofelectrondensityonopposite
sidesofthenucleus,withanodalplane(zeroelectrondensity)
betweenthelobes
3porbitals,px,py,pz liealongx,y,zcartesianaxes
dorbitals
Thequantumnumber =2correspondstoadorbital
Foreachvalueofn thereare5dorbitalsm=+2,+1,0,1and2
Fourconsistof4lobesofelectrondensityarrangedinaquadrant
aboutnucleus,withtwonodalplanesbetweenlobes.
Ofthese,onehasits4lobesalongCartesianxandyaxes.other
threehavelobesbetweentheaxes,inplanesdefinedbyaxes
Fifthdorbitalhasjusttwomainopposedlobesofdensityalong
thezaxis,withasmalltorusofdensityatthewaist
Orbitalsize
Aspecificorbitalbecomes
Anorbitalgetslargeras
thevalueofn increases smallerasthenuclear
chargeincreases
Correspondingdecreasein
orbitalenergy
Theeffectofnuclearcharge
HandHe+ havebothoneelectronbuttheiremission
spectradiffer
Theeffectofnuclearcharge
energyofanorbitalcanbedeterminedby
measuringtheamountofenergyrequired
toremoveanelectroncompletely
thisistheionisationenergy(Ei)inspecific
cases
H H+ +e EiH =2.18x1018J
He+ He2+(g)+e EiHe+ =8.72x1018J

Manyelectronatoms
Inamultielectronatom,electronsrepeloneanotherina
complicatedway
EnergiesoforbitalsdonotquitefollowthesimpleHatom's
pattern
Agivenorbitalisofhigherenergyinamultielectronatomthan
inasingleelectronionwiththesamenuclearcharge
Electronsinorbitalswithlowern valuesareconcentratedcloser
tothenucleusthanthosewithhighern values
Resultsinshielding ofouterelectronsbytheinner("core")
electrons
Shielding
Electronelectronrepulsioncancels
aportionoftheattraction
betweenthenucleusandthe
incomingelectron
Avalenceelectroninamulti
electronatomexperiencesa
chargelessthanthefullnuclear
charge,thisiscalledtheeffective
nuclearchargeZeff
Effectofshieldingonorbitaltype
shieldingaffectselectronsofanoutershellunequally
selectronsofanoutershellhaveoneormoresmalllobes
ofdensityinsidetheregionofshieldingelectrons,andthus
arelessaffectedbyshielding:
effectprogressivelylessimportantforp,d,forbitals
degreeof"penetration"tothenucleusiss>p>d>f
differenceinshieldingresultsinenergiesoforbitalsineach
shellfollowingtheorders<p<d<f.
Energylevelsinmultielectronatoms
Energylevelsoforbitals ina Mnemonicforthecorrectorder

multielectronatom. offilling oforbitals.
Groundstateconfigurations
Aparticulararrangementofelectronsiscalledanelectron
configuration
Groundstateofanatomisthemoststablearrangement
Constructedbyplacingelectronsinorbitalsstartingwiththe
lowestinenergyandmovingprogressivelyupward
aufbau('buildingup')principle ahypotheticalsynthesisof
atoms,byassemblingprotonsonebyoneinthenucleuswhilst
addingthecorrespondingelectronsintotheorbitalsoflowest
energy
Rulesforfillingorbitals
Thelowestenergyruleprovidesthatorbitalswithlowest
principlequantumnumber,n,areusually occupiedfirst
Onlytwoelectronsmaximumperorbital(PauliPrinciple)
Hund'srule:Forasubshelloforbitals(whichhavethesame
energy),theaddedelectronsdistributeoneineachorbital(with
thesamespinquantumnumber),beforeasecondelectronis
addedtoeachorbital
Rationale:fortwoormoredegenerateorbitals,thelowest
energysituationresultswhenelectronsoccupytheorbitalsthat
keepthemfurthestapartduetorepulsion
Aufbauprincipleandorderof
orbitalfilling
1. Eachelectroninanatom
occupiesthemoststable
availableorbital.
2. Notwoelectronscanhave
identicalquantumnumbers.
3. Orbitalcapacitiesareas
follows:
sset:2electrons
p set:6electrons
d set:10electrons
f set:14electrons
Twousualwaysofwriting:
1.Listsubshellswithsuperscriptednumberstoshowthe
numberofelectrons,e.g.Beisls22s2
2.Arrowdiagram boxrepresentsorbital,arrowshows
electronandms value(upordown)
givesmoreinformationaboutelectronarrangement.
Sometimesboxesreplacedbyhorizontallines (e.g.in
Blackman)
Arrowdiagramsindicateallfourquantumnumbersofan
electron
Groundstateconfiguration
examples
Groundstateconfiguration
examples
Notes:Pauliexclusionprinciplefirstcomesintoeffectatlithium.
Hund's rulefirstcomesintoeffectatcarbon.
Shorthandelectronconfiguration
canwriteelectronconfigurationmoreconvenientlyby
substitutinganoblegassymbolasshorthandforthe
appropriatesetofcoreelectrons
e.g.chlorine(ls22s22p63s23p5)canbewrittenas[Ne]3s23p5
[Ne]representsthels22s22p6 partofconfiguration
shorthandemphasisesvalenceelectrons,e.g.3s23p5 forCl,
above
valenceelectronsareimportantinbondingandreactivity.
Coreelectronsgenerallyarenot.
Structureoftheperiodictable
(Blackman4.6)
Periodictableliststheelementsinorderofincreasing
atomicnumber
Alsoinorderofincreasingnumberofatomicelectrons
Elementsareplacedinrowscalledperiods suchthatthe
columnsareformedwithgroupsofelementsthathave
similarchemicalproperties
Propertiesinagroup (columns)aresimilarbecause
valenceelectronconfigurationsaresimilar
Firstthreerows
Orderoforbitalsforn> 3
3dorbitalshavepoorpenetrationtothenucleusrelativeto
the4sorbitals,
Hence3dand4sorbitalshavenearlyequalenergies
Foraneutral atom,the4sorbitalhaslower energythan

the3dorbitals,anditfillsfirst
Both4sand3delectronareregardedasvalenceelectrons
ofthetransitionmetals
Periodictableisdrawntoreflecttheorderofelectron
filling
Twootheranomaliesoccurinorbitalfilling atCrandCu.
Extrastabilityassociatedwithanexactlyhalffilled(3d5)orfilled
(3d10)subshellchangestheorderoffilling.
Similaranomaliesoffillingoccurlaterintheperiodictable.
periodictableaidsdescriptionofelectronconfiguration
coreconfigurationgivenbytheconfigurationoftheinertgas
intherowabovetheelement'srow
valenceconfiguration countacrossfromtheleftoftableto
theelement,takingaccountoffillinganomalies
Configurationsofions
Anions:addrequirednumberofelectronsaccordingtotheaufbau
principle.
e.g.WhereasOis[He]2s22p4,O is[He]2s22p5,and
O2 is[He]2s22p6,or[Ne].
Earliermaingroupcations (i.e.s andp blockelements):remove
requirednumberofelectronsfromthepositionsthatwerelast
addedaccordingtotheaufbauprinciple.
e.g.WhereasCais[Ar]4s2,Ca+ is[Ar]4sl,and
Ca2+ is[Ar],or[Ne]3s23p6.
Maingroupelementsformtheirmoststableanionorcationby
gain/lossofelectronstoattainthenearestnoblegasconfiguration
e.g.,Li+,Mg2+,Al3+,O2,Cl isoelectronic withnoblegas
Transitionmetalcations
Inneutral firstrowtransitionmetalatoms,the4sorbitalis
morestablethanthe3dorbitals.
Intransitionmetalcations,thereverseistrue,soalltheir
valenceelectronsresideinthedorbitals.
e.g.Feis[Ar]4s23d6 butFe+ is[Ar]3d7,andFe2+ is[Ar]3d6
Relativelyeasylossof4s2 pairofelectronsfromtransition
metalsaccountsforgeneraloccurrenceofstableM2+ ions.
furtherremovalof3delectronsgivesionsofhighervalency
Ingeneraltheorderofelectronremovaltoformcationsisnp,
thenns,then(n1)d.
e.g.Pbis[Xe]5d104f146s26p2,butPb2+ is[Xe]5dl04f146s2 andPb4+
is[Xe]5d104f14
Magneticpropertiesofatoms
Inafilled orbitaleachelectronwithspinorientation+1/2hasa
partnerwithspinorientation1/2
Oppositespinscanceleachother,givinganetspinofzero
Anatomorionwithallelectronspairedistermeddiamagnetic
repelledveryweaklyfromamagneticfield
Anatomorionwithoneormoreunpairedelectronsiscalled
paramagnetic attractedintoamagneticfield
EXAMPLE: IstheNi2+ ionparamagnetic?

Ni2+ is[Ar]3d8.valenceconfiguration(3d8)is
Sincethereisatleastoneunpairedelectron(twointhiscase),
Ni2+ isaparamagneticion.
Sizesofions
Anatomiccationisalwayssmallerthanthe
correspondingneutralatom
Anatomicanionisalwayslargerthanthe
correspondingneutralatom
Periodicityofatomicproperties
(Blackman4.8)
Atomicradii
Aconvenientmeasureofatomicsizeistheradiusoftheatom
Decreases withincreasingnuclearchargeandelectronsgoing
intothesameshellacrossaperiod
Increases downagroup outerelectronsinhighershells
furtherfromthenucleus
Firstionisationenergy
Itistheminimumofenergyneededtoremoveanelectronfrom
aneutralatom
Increases withincreasingnuclearchargeandelectronsgoing
intothesameshellacrossaperiod
Decreases downagroup outerelectronsinhighershellswith
higherenergyfurtherfromthenucleus
Secondandhigherionization
energies(IE)
Amultielectronatomcanlosemorethanoneelectron,
butionisationbecomesmoredifficultascationiccharge
increases
IE
1st
2nd
3rd
NOTE:ThereisaBIGjumpinionizationenergywhen
electronsareextractedfromashellwithalowerquantum
number.Inthatcase,electronsarebeingremovedfroma
specieswithanoblegasconfiguration(i.e.nowremovinga
coreelectron)
Electronaffinity
Itistheenergychangewhenanelectronisaddedto
anatomingasphasetoformananion
Electronaffinitytendstobecomemorenegativefrom
lefttorightacrossaperiodintheperiodictable
http://en.wikipedia.org/wiki/File:Electron_affinity_of_the_elements.svg
Predictingbondingproperties
Electronegativity
Nextmaintopicisbondinginchemicalsystems
Weusetheconceptofelectronegativity,specifically
thedifferenceintheelectronegativityvaluesofthe
twoatomsinvolvedinbondingtopredictthetypeof
bonding.
Electronegativitycanberegardedasameasureofthe
relativepowerofattractionofelectronsinabondfor
agivenelement
Variesperiodically
Electronegativity
Electronegativityvaluesarenumbersestimatedforeach
element,whichaimtoquantifytheattractionbetweenthe
elementandtheelectronsinbondsthatitforms.
Electronegativityvaluesforelementsrangefrom0.7(lower
leftoftheperiodictable)to4.0(upperright).
Thehigherthevalue,themorestronglyanelement
attractselectrons
Elementswithalowelectronegativityareknownas
electropositive elements
Weusethedifferenceinelectronegativitytopredictthe
typeofbondingincompounds.
Electronegativity values
PolarCovalentBonding
Whendissimilaratomsforma
covalentbond,theshared
electronsareusuallyfoundcloser
tooneatomthantheother.This
iscalledapolarcovalentbond.
Anionicbondcanberegardedas
theextremelimitofapolar
+ - indicates small positive covalentbond.
charge Anonpolarcovalentbondis
Arrow indicates a dipole, bond
generallyonlyfoundbetween
polarity atomsofthesametype
e.g.ClCl.
TheEnd!
Goodluckwiththerestofthecourse!!!

2017 CHEM1011 DrBall Notes 1pp

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2017 CHEM1011 DrBall Notes 1pp

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CHEM1011 Essentials of Chemistry

Lecturer: Dr Graham E. Ball

Nomenclature of simple organic and inorganic ions.

Mole Concept. Solution stoichiometry

MATHEMATICS MATERIALS SCIENCE

Chemistry (from Egyptian kme (chem), meaning "earth") is the science

MIXTURES PURE SUBSTANCES

First page of Dalton's "A New System of

Law of definite proportions (J.L.Proust)

Law of multiple proportions (post Daltons theory)

Chemists no longer talk of

Above image: Don Eigler

Can they be broken down further?

The Cathode Ray:- A

Canal Rays:- Protons.

J.J. Thomsons experiment to measure the mass of

the atoms of the elements consist of a number of negatively electrified

- Accounts for the presence of electrons but overall neutral charge

- Disproved by Rutherfords experiment

Showed that the mass of an atom is

Neutrons have mass about the same as a proton

Charges: Proton +1; electron -1.

Proton mass = 1.673 x 10-27 kg (1)

The nucleus of H is 1833 times

The size of the atoms electron

The composition of the atoms

(Individual atoms are electrically neutral)

ION: Charged particle (single atom or group of atoms )

ANION: Negatively charged species, protons < electrons

CATION: Positively charged species, protons > electrons

Fundamental Property of elements:

- same number of protons in each atom.

So, it is the number of protons in the nucleus that

Chemistry is just a counting exercise!

Not all atoms of an element need be identical.

ISOTOPES: have same number of protons

similar chemical properties

12 6 protons, 6 neutrons, 6 electrons

Isotopes: Properties of Water

ATOMIC MASS: average mass in amu of the atoms of the

ATOMIC MASS UNIT: 1/12 th of the mass of a carbon-12 atom

Example: Calculate the (average) atomic mass of naturally occurring

Isotope Mass Number Abundance Isotopic Weight

(fraction each isotope) x (mass each isotope)

= (78.99/100)*23.98504 + (10.00/100)*24.98584 + (11.01/100)*25.98259

= 24.31 g mol-1 (4 sig fig)

Whenever dealing with percentages, a useful trick is to consider 100 of whatever

Of these, 6909 atoms will be 63Cu, of weight = 6909 x 62.930 amu.

Thus, the average atomic mass of one atom = 635480 /10000

Hydrogen formation and some light elements - the big

Elements carbon to iron formed in stars

Many elements heavier than iron formed by exploding

Elements heavier than uranium are man made

Some named from mythology:

Some named after people:

Greek: Hydrogen - water former Nitrogen - soda former

Some named after places:

Molecule: independent structural unit of 2 or more atoms

Binary Compound: contains 2 element types - AxBy.

Formula: Empirical - simplest whole number ratio

CH = empirical formula for C2H2 and C6H6

Chemists use various representations for the same

H3N NH3 Names:

E.g., IUPAC name:

= (78.99/100)23.98504 + (10.00/100)24.98584 + (11.01/100)*25.98259