HERNY

Preparation for A LEVELS: H2 CHEMISTRY

PHYSICAL CHEMISTRY
CONTENTS:
1) Atoms, Molecules & Stoichiometry *
2) Atomic Structure
3) Chemical Bonding
4) Gases *
5A) Chemical Energetics 1: Enthalpy *
5B) Chemical Energetics 2: Entropy *
6) Reaction Kinetics *
7) Chemical Equilibrium *
13A) Ionic Equilibrium 1: Acid-Base Equilibrium *
13B) Ionic Equilibrium 2: Solubility Equilibrium*
18) Electrochemistry

ALL THE BEST BRO

(Chapters 1,3,4,5,6 and 7 can be found in a separate

document)
ATOMIC STRUCTURE (Lecture Notes 2)
2.1) Sub-Atomic Particles of Matter (pg 2-5)
ELECTRIC FIELD
Neutron – not deflected
Proton – deflected towards –ve plate
Electron – deflected towards +ve plate
 Protons and electrons are deflected in opposite directions
 Extent of deflection is different
 Angle of Deflection is inversely proportional to the Radius of deflection
 Particles with lower mass/higher charge will be deflected more (smaller radius of
deflection)
Angle of Deflection  DEPENDENT on relative masses of the particles & charge of particles

CHARGE Q
ANGLE OF DEFLECTION ∝ (denoted as )
MASS m
Q Q
For example: for proton = 1/1 = 1, for electron = 1/ (1/1840) = 1840
m m
Thus, the extent of deflection for electrons is more than protons.
If a proton 11H  and a deuteron 12 H  were to pass through an electric field, being
positively-charged, both will deflect towards the negatively charged plate (cathode).
However, the angle of deflection for the deuterons will be half that for the protons since
a deuteron has twice the mass of a proton.
Q Q
1
1 H  has a ratio of 1/1 = 1, while 2
1 H  has a ratio of 1/2 = 0.5
m m
2.2) Electronic Structure (pg 6-10)
ELECTRONIC STRUCTURE: Arrangement of electrons in atoms (or ions)
 Electrons in an atom are arranged in different principal quantum shells which
comprise of one or more subshells
 Each subshell contains one or more orbitals
o Provides us with information like: number of electrons in atom/ion
o Distribution of electrons in atom/ion
o Energies of the electrons
ORBITALS: Region in space where there is a high probability (>95%) of finding an electron
 Electrons in an atom do not occupy fixed positions. They also do not circulate the
nucleus in a fixed path (orbit)
 Electrons may be considered to move almost everywhere and occupy a certain
region around the nucleus.
 Characteristics of Orbitals:
o Each orbital denotes an allowed energy state of the electron.
o Has a distinctive geometrical shape
o Electron in orbital  described by four quantum numbers (where no two
electrons have the same 4 quantum numbers)
FOUR QUANTUM NUMBERS
(a) Principal Quantum Number: number of shells
PRINCIPAL  Specifies the energy of an electron, the size of the orbital and the
QUANTUM average distance of the electron from the nucleus of an atom.
NUMBER  As the value of n ↑,
(Shells) o the further the electron is from the nucleus
o the higher the energy level of the electron
o the less tightly the electron is bound to the nucleus
o the larger the orbital
 Each principal quantum shell can contain a max of 2n² electrons
(b) (a) For shells with quantum number, n:
ORBITAL = 0 1 2 3 4 … n-1
QUANTUM
s p d f g
NUMBER
(Subshells/
E.g. : When n = 2, there are only 2 possible values for :
Orbitals) = 0 (i.e. 2s), = 1 (i.e. 2p)
Relative energy: s<p<d<f<g
This divides an energy level into sub-levels and describes the shape of the
orbital
Principal Quantum Shell, n Type of Subshell
1 1s
2 2s, 2p
3 3s, 3p, 3d
4 4s, 4p, 4d, 4f
(c) (a) For sub-shells with orbital quantum number,
MAGNETIC M = - , -( -1), -( -2), …, -1, 0, 1, …., ( -2), ( -1),
QUANTUM
This describes the:
NUMBER
 Number of orbitals in each subshell
(No. of
 Orientation of orbital in space E.g., when:
orbitals)
= 0, M = 0: In the s subshell, there is only 1 orbital
= 1, M = -1, 0 ,1: In the p subshell, there are 3 orbitals
= 2, M = -2, -1, 0 ,1, 2: In the d subshell, there are 5 orbitals

Subshell Number of Orbitals Type of Subshell

s 1 s
p 3 px , p y , pz
d 5 (not in syllabus!!)
 Each orbital is designated by its principal quantum number and type.
(orbital in 3rd quantum shell and in s subshell  3s)
 Orbitals within given subshell (e.g: 2 px , 2p y , 2pz ) have the same energy
(degenerate)
(d) ms = +½, -½ , or ↑↓
SPIN
 ms describes the spin of an electron on its own axis
QUANTUM
 Spin can be clockwise or anti-clockwise
NUMBER
 Each orbital can hold a maximum of 2 electrons

No. of orbitals in ms =
subshell +½, -½

1 +½, -½
1 +½, -½
3 +½, -½
1 +½, -½
3 +½, -½
5 +½, -½
1 +½, -½
3 +½, -½
5 +½, -½
7 +½, -½

SHAPES OF ORBITALS
TYPE OF DESCRIPTION OF ORBITAL SHAPES OF ORBITAL
ORBITAL
s orbital -Each s subshell : only one orbital
-All s orbitals:
o SPHERICAL shape
o NON-DIRECTIONAL
(as charge cloud is not concentrated in any
particular direction)

-s orbitals of different shells have same shape,

but different size:
-size of 1s orbital < 2s orbital < 3s orbitals

-As n increases, the orbitals become more

diffused (further)
(Hence, distance of electrons from nucleus in
1s orbital < 2s orbitals < 3s orbitals)
p orbital  Each p subshell : has three orbitals
 All s orbitals:
o DUMBBELL shape
o DIRECTIONAL
(as electron density is concentrated in certain
directions along the x, y, z axes)
-3 types of p orbitals, px , p y , pz all have
same shape and size, but different
orientation. (along the x, y, z axes)

-The px , p y , pz orbitals from the same

shell have the same energy (degenerate)
-p orbitals of different shells have same shape
but different size:
size of 2p orbital < 3p orbital
(3p orbital is more diffuse than 2p orbital)
(d and f orbitals NOT IN SYLLABUS HOOOOOOORAY! :D)
 IMPORTANT: 4s subshell has a lower energy level than 3d subshell
(when it is not occupied by electrons)
2.3) Electronic Configurations (pg 10-14)
ELECTRONIC CONFIGURATION: Way in which electrons are distributed among the orbitals
 Two common notations to indicate electronic configuration:
o s p d f notation (1s²2s²2p⁶…. etc.)
o electron-in-box diagram (orbital box diagram)
 3 IMPORTANT RULES:
1.The Aufbau (Building Up) Principle, 2.Pauli Exclusion Principle, 3.Hund’s Rule

1. The Aufbau (Building Up) Principle

Electrons are placed into the orbital of lowest energy,
then the orbital of the next lowest energy, and so on.
Factors affecting Energy of Orbitals:
- Principal Quantum Number, n: As n ↑, energy ↑
- Orbital Quantum Number, :
Relative order of energy: s < p < d < f
*Note that 4s orbital is filled before the 3d orbitals as
the 4s orbital is lowered in energy by their ability to
penetrate close to the nucleus.

2. Pauli Exclusion Principle

 Each orbital may hold only a maximum of
TWO electrons.
 They must have OPPOSITE SPINS.
 3. Hund’s Rule
Orbitals of a subshell must be occupied singly and with parallel spins before pairing
occurs. This is to ensure electrons are as far apart as possible to minimize inter-
electronic repulsion.
* NOTE that when writing electronic configuration, 3d should be written before 4s, even
though 4s orbital is filled before 3d orbital.
ANOMALOUS ELECTRONIC CONFIGURATIONS
Electronic configurations for chromium (₂₄Cr) & copper (₂₉Cu) are anomalous.

Expected Configuration: ₂₄Cr [Ar] = 1s²2s²2p⁶3s²3p⁶ 3d⁴4s²

Actual Configuration: ₂₄Cr [Ar] = 1s²2s²2p⁶3s²3p⁶ 3d⁵4s 1

Reason: 3d and 4s orbitals are about equal in energy by the time Cr is reached. By having one
electron each in the 3d and 4s orbitals, electron-electron repulsion is minimized.

Expected Configuration: ₂₉Cu [Ar] = 1s²2s²2p⁶3s²3p⁶ 3d⁹4s²

Actual Configuration: ₂₉Cu [Ar] = 1s²2s²2p⁶3s²3p⁶ 3d 10 4s 1

Reason: The fully-filled 3d subshell is unusually stable due to symmetrical charge

distribution around the metal centre.

Ions are formed when atoms gain or lose electrons.

(a) Anions (Negative Ions)
General rule: Electrons are added to the next available orbital in the atom.
(b) Cations (Positive Ions)
General rule: Electrons are first removed from orbitals with the highest energy. For
atoms/ions with more than 20 electrons, 4s electrons are removed first before 3d electrons.

Once occupied by electrons, the 3d subshell is closer to the nucleus. The electrons in the 3d
subshell repel the 4s electrons from the nucleus and cause the 4s electrons to be at a higher
energy level.

Isoelectronic Configurations
When 2 different species have the same number of electrons, we say that they are
isoelectronic with one another (e.g: N³⁻, O²⁻)

2.4) Ionization Energies (pg 14-20)

When an electron in an atom occupies the lowest energy levels, atom is in its ground state.
When an electron is promoted to one of the higher energy level, the atom is unstable and is
said an excited state

M (g)  M⁺ (g) + e⁻ ∆H = 1st I.E.

First Ionization Energy (1st IE): Energy required to remove one mole of electrons from one
mole of gaseous atoms (at the ground state) to form one mole of gaseous singly charged
cations.
M⁺ (g)  M²⁺ (g) + e⁻ ∆H = 2nd I.E.
Second Ionization Energy (2nd IE): The energy required to remove one mole of electrons
from one mole of gaseous singly-charged cations to form one mole of gaseous doubly-
charged cations.

Ionization energies affect the type of bond formed by the atom with other atoms. Elements
with low ionization energies lose an electron easily to form a cation, resulting in ionic bonds
being formed.

Ionization energies are positive values (endothermic) since energy is absorbed during
ionization to overcome the attraction between electron and nucleus

The 2nd IE > 1st IE because more energy is required to remove an electron from a positive ion
due to greater electrostatic attraction between the positive ion and the valence electron.

FACTORS INFLUENCING IONISATION ENERGIES

(a) EFFECTIVE NUCLEAR CHARGE, Zeff

An electron in the atom faces two main electrostatic forces, namely the attractive forces by
the nucleus (nuclear charge), and the repulsive force by electrons closer than itself to the
nucleus. (shielding effect)

Zeff is combined effect of nuclear charge, Z and shielding effect, S, caused by inner
electrons: Zeff = Nuclear charge (Z) –Shielding Effect (S)

Higher Zeff 
o stronger forces of attraction between nucleus and valence electron
o higher ionization energy

(i) SIZE OF POSITIVE NUCLEAR CHARGE

o Indicates the electrostatic forces of attraction between the protons in the
nucleus and the valence electrons
Nuclear charge increases with an increase in proton number
 Stronger attraction between the positive nucleus and valence electrons
 More energy is required to remove the valence electron
(ii) SHIELDING/SCREENING EFFECT OF THE INNER ELECTRONS, S
Shielding of valence electrons from electrostatic attraction of the +vely charged nucleus by
inner electrons (electrons in same subshell offer poor shielding for one another)
* Number of inner electrons ↑, Shielding Effect ↑
o Weaker attraction between positive nucleus and valence electrons
o Less energy is required to remove the valence electrons

(b) DISTANCE OF OUTERMOST ELECTRON FROM NUCLEUS (Size/Radius)

Attraction of the positive nucleus for the valence electron decreases as
distance of electron from nucleus increase
o Ionization energy decreases as n (no of shells) increase
TRENDS IN FIRST IEs

Across WHY?
period:  As proton number ↑, nuclear charge ↑
IE ↑  Successive members of period have one electron added to the same
outermost shell.
 Increase in screening effect = negligible
 Effective Nuclear Charge ↑ (nuclear charge – shielding effect)
 More energy required to remove more tightly held electrons, thus IE ↑

IRREGULARITIES at Group II/III

 Across Period 3, 1st IE of Al is unexpectedly lower than that of Mg.
o Mg: 1s² 2s² 2p⁶ 3s², Al: 1s² 2s² 2p⁶ 3s² 3p 1
Less Energy is needed to remove the 3p electron of Al, which is at a higher
energy level than the 3s electron of Mg (Hence 1st IE of Al lower)
 Across Period 3, 1st IE of S is unexpectedly lower than that of P.

Less Energy is needed to

remove the paired 3p electron
of S, compared to the unpaired
3p electron from P, as inter-
electronic repulsion is
predominant between the 3p
electrons in the doubly filled
3p orbital of S. (Hence 1st IE of
S lower)

Down WHY?
 Down a group, the number of filled principal quantum shell increases,
group:
and each successive element has its valence electrons located in a shell
IE ↓ with a larger principal quantum number n.
 Hence, valence electrons are increasingly further away from nucleus
down a group (DISTANCE ↑), attracted less strongly by the nucleus
 Less energy required to remove the valence electrons, hence IE ↓

If asked to compare the IE of two elements, write out the electronic configuration of the two
elements, and firstly see which electron is removed, then compare:
Distance from nucleus, presence of inter-electronic repulsion etc.
IMPORTANT POINTS:
 Logarithm of IE are often plotted instead of actual IE for convenience, as IE values
vary over a wide range of values.
 The energy gap between subshells is not as steep as that between principal
quantum shells and is sometimes not discernible

 Increment in IE is due to removal of electrons from an ion of increasing +ve charge

o Due to the increase in electrostatic attraction, outer electrons are attracted
nearer to the nucleus, leading to a decrease in ionic size
o As the outer electrons are held more tightly, more energy is required to
remove them

 The large increments in IE from 1st  2nd, and 9th  10th, are due to the fact that an
electron is being removed from an inner principal quantum shell and is nearer to
the nucleus (at a lower energy level)

 The slight jump in IE from 7th  8th , is due to an electron being removed from a
different subshell. This is due to the 2s electrons being at a lower energy (closer to
the nucleus) than the 2p electrons. Slightly more energy is thus required to remove
the 2s electron. (hence IE increases)

2.5) TRENDS IN ATOMIC AND IONIC RADII (pg 21-24)

ATOMIC RADII
Increases down a group because:
-- Number of filled principal quantum shell increases and each
successive element has its valence electrons located in a shell
with a larger principal quantum number n.

-- Hence, valence electrons are increasingly further away from

the nucleus  weaker attractive forces  atomic radius increases

Decreases across a period because:

-- Nuclear charge↑, Shielding effect is constant, Effective nuclear charge ↑, valence
electrons increasingly pulled towards nucleus, hence atomic radii ↓
IONIC RADIUS
Ionic Radius: Half the distance between ‘centres’ of two
ions of the same element
Radius of cation is always smaller than that of the parent atom:
SIMILARITIES:
- Same number of protons, hence nuclear charge remains constant
DIFFERENCES:
 Cation  fewer number of electrons/electron shells
 Electrons in cation  experience smaller shielding effect
CONSEQUENCES:
- The nuclear charge exerts a greater attractive force on the remaining electrons, shrinking
its electron cloud
-------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------

Radius of anion is always larger than that of the parent atom:

SIMILARITIES:
- Same number of protons, hence nuclear charge remains constant
DIFFERENCES:
- Anion  greater number of electrons/electron shells
CONSEQUENCES:
- Inter-electronic repulsion increases (or effective nuclear charge decreases), resulting in an
expansion of the electric cloud of anionThe nuclear charge exerts a greater attractive force
on the remaining electrons, shrinking its electron cloud

IONIC RADIUS
 Ionic radii of isoelectronic ions (ions with same number of electrons) decreases as
the nuclear charge increases

N3- O2- F- Na+ Mg2+ Al3+

no of protons 7 8 9 11 12 13

electronic structure of ion 2, 8 2, 8 2, 8 2, 8 2, 8 2, 8

ionic radius (nm) (0.171) 0.140 0.133 0.102 0.072 0.054

 Across period 2, ionic radius decreases gradually from Li⁺ to B³⁺, increases sharply
from B³⁺ to N³⁻, decreases gradually from N³⁻ to F.
Across a period, the size of isoelectronic ions DECREASES.
o Na⁺, Mg²⁺, Al³⁺ have same no. of inner electrons, hence shielding effect is similar
o However, the nuclear charge increases from Na⁺ to Al³⁺, so the nucleus attracts the
valence electrons more strongly.

o P³⁻, S²⁻, Cl⁻ have same no. of inner electrons, hence shielding effect is similar
o However, the nuclear charge increases from P³⁻ to Cl⁻, so the nucleus attracts the
valence electrons more strongly.

Anions are larger than cations. E.g: from Al³⁺ to P³⁻

Al³⁺: 1s²2s²2p⁶ P³⁻: 1s²2s²2p⁶3s²3p⁶
 P³⁻ has an extra shell of electrons more than Al³⁺, but only has 2 more protons.
 There is significantly higher shielding effect in P³⁻. The outer electrons are in a larger
principal quantum shell, and further from the nucleus.
 Hence, P³⁻ is much larger than Al³⁺
From P³⁻ to Cl⁻ to Al³⁺
 Isoelectronic
However, they have different number of protons  electrons are pulled towards
nucleus more effectively as nuclear charge increases across the series- electron cloud of
ion contracts.
IONIC EQUILIBRIUM (Lecture Notes 13a)
13.1) Theories of Acids, Bases & Conjugate Acid-Base Pairs (pg 2-4)
(NOTE: Unlike Org. Chem, Ionic Eqm requires lots of practice)
Arrhenius Theory: - Acids: Contains H in its formula, dissociates in water to form H+ ions.
- Bases: Contains OH in its formula, dissociates in water to form OH- ions.
Limitations: Only applies to reactions which take place in the aq. medium, compounds like
ammonia cannot be classified as bases even though they form OH- ions in water.

***Bronsted-Lowry Theory of Acids & Bases:

- Acids: Can donate proton to another substance: acid is a proton donor.
- Bases: Can accept proton from another substance: base is a proton acceptor.
An acid is only an acid in the presence of base,
and a base is only a base in the presence of an
acid, as an acid-base reaction involves the
transfer of a proton from the acid to the base.

Lewis Acids & Bases: - Acids: Accept e pair from base  acid is an electron-pair acceptor.
- Bases: Donates e pair to acid  base is an electron-pair donor.
Limitations: Only applies to reactions which take place in the aq. medium, compounds like
ammonia cannot be classified as bases even though they form OH- ions in water.
CONJUGATE ACID-BASE PAIRS
The Bronsted-Lowry Theory of Acids and Bases are of most use to us.

HA (acid) + B (base) A- (conjugate base of HA) + HB+ (conjugate acid of B)

In the forward reaction:
HA = acid, as it donates a proton to B. B = base, as it accepts a proton from HA.
In the backward reaction:
HB+ = acid, as it donates a proton to A-. HB+ = conjugate acid of base B.
A- = base, as it accepts a proton from HB+. A- = conjugate base of acid HA.
Acid HA loses a proton to form its conjugate base A-. HA & A-  conjugate acid-base pair.
Base B gains a proton to form its conjugate acid HB+. B & BH+  conjugate acid-base pair.
Every acid has a conjugate base, every base has a conjugate acid. ***

13.2) pH Scale (pg 4-5)

pH: Measure of acidity/alkalinity of solution.
- pH scale is between 0 & 14, though it can be -1 or 15 etc.
- The higher the [H+], the lower the pH, the more acidic
- Aq. solution with pH = 7 at 25oC is considered to be neutral.
pOH: Measure of concentration of hydroxide ions in aq. solution
- pH scale is between 0 & 14, though it can be -1 or 15 etc.
- The higher the [H+], the lower the pH, the more acidic
- Aq. solution with pH = 7 at 25oC is considered to be neutral  pH + pOH = 14
pH can be measured with the determination of [H+] via
- universal indicator paper/solution (approximate value) OR –pH meter (accurate value)
 13.3) Ionic Product of Water, Kw (pg 6-8)
Self-Ionization of water: Ensures electrical conductivity never falls to exactly zero even with
the purest water. Represented by: H2O (l) + H2O (l) H3O+ (aq) + OH- (aq).
At equilibrium, Kc [H2O]2 = [H3O+] [ OH-]
Since water is a weak electrolyte, amount of water ionized is considered negligible (very
small amount). [H2O] is essentially constant  Kw = Kc [H2O]2 is another constant. Hence:
Ionic Product of Water, Kw = [H3O+] [OH-] (units: mol2 dm-6)
At 25oC, Kw = [H3O+] [ OH-] = 1.0 x 10-14 mol2 dm-6
Kw Kw
- Can also be expressed as Kw = [H+] [OH-]  [H  ]  or [OH  ] 
[OH  ] [H  ]
- When [H+] becomes larger, [OH-] becomes smaller and vice versa.
By definition, pKw = -lg Kw = -lg [H+] [OH-] = pH + pOH
At 25oC, pKw = pH + pOH = 14

As temp ↑, value of Kw ↓, pH ↓(more acidic) (as self-ionization of water is endothermic)

The increase in temperature leads to a rightward shift in equilibrium position to absorb the
heat energy supplied (Le Chatelier’s Principle). Hence more water molecules dissociate as
temperature ↑ [H+] and [OH-] ↑. Since Kw = [H3O+] [OH-], Kw ↑ when temp ↑
13.4) Strengths of Acid & Bases, Ka & Kb (pg 9-22)

STRONG ACIDS: Ionizes completely in solution. STRONG BASES: Ionizes completely in solution.
[H+] = n[acid] (n = no. of H+ formed per mol of acid) [OH-] = n[base] (n = no. of OH- formed per mol of base)
Monobasic: dissociates to form 1 mol of H+ Monoacidic: dissociates to form 1 mol of OH-
Dibasic: dissociates to form 2 mol of H+: [H+] =2[acid] Dacidic: dissociates to form 2 mol of OH-: [OH-] =2[base]

In questions, during calculation of pH, there are 2 sources of H3O+ in a solution of dil. HCl  from ionization of HCl &
self-ionization of H2O. If high conc. of strong acid is used, amt of H3O+ from self-ionization of water is negligible: [H3O+]
= [HCl]. However, if low conc. of strong acid is used, amt of H3O+ from self-ionization of water is NOT negligible.
*In the presence of H3O+ (or OH-), self-ionization of water is suppressed due to Common Ion Effect. H3O+ & OH- from
self-ionization of water are ignored when concentration of ANY of these two ions are greater than 10 -7 mol dm-3
WEAK ACIDS: Ionizes partially in solution. WEAK BASES: Ionizes partially in solution.
- +
CH3COOH (aq) + H2O (l) CH3COO (aq) + H3O (aq)
Due to incomplete ionization, the undissociated species of the weak acids still exist in relatively large amounts in the
dilute solution. Consider 0.10 moldm-3 HCN: HCN (aq) H+ (aq) + CN- (aq)
Initial amt: 0.10 0 0
Final amt: 0.10 – a a a
In this solution, [H+] = [CN-]. At eqm, [HCN] >> [H+] or [CN-]
ACID DISSOCIATION CONSTANT, Ka **Strength of Acid VS Concentration of Acid:
- Ka measures the strength of acid. The larger the value Strength of acid: Extent of dissociation of acid
the stronger the acid. Conc of acid: No. of moles of acid per dm3 of solution
- It provides a quantitative indication of the extent to *A strong acid can be of low concentration, a weak acid
which the acid is dissociated. can have a high concentration and vice versa.
- It has units of moldm-3, BASE DISSOCIATION CONSTANT, Kb
-The value is dependent on temperature.
- Kb measures the basic strength of weak base B. The
larger the value the stronger the base.
Dissociation of a weak monobasic acid: - It measures the ability of the Bronsted-Lowry base B to
CH3COOH (aq) + H2O (l) CH3COO- (aq) + H3O+ (aq) accept a proton.
+ -
- It has units of moldm-3,
At eqm, Kc = [H 3O ][CH 3COO ] . Rearranging,
[CH 3COOH][H 2O] -The value is dependent on temperature.
+ - + -
Kc [H2O] = Ka = [H3O ][CH 3COO ] = [H ][CH3COO ] Dissociation of a weak monoacidic base:
[CH 3COOH] [CH3COOH] NH3 (aq) + H2O (l) NH4+ (aq) + OH- (aq)
pKa = -lg Ka + -
At eqm, Kc = [NH 4 ][OH ] . Rearranging,
As Ka/moldm-3 ↓, pKa ↑, acid strength decreases [NH 3 ][H 2O]
(becomes weaker/pH becomes higher) + -
Kc [H2O] = Kb = [NH 4 ][OH ]
If Ka of HF > Ka of HCN (or pKa of HF < pKa of HCN) [NH 3 ]
- HF is a stronger acid than HCN
pKb = -lg Kb
- For HF (aq) & HCN (aq) of the same concentration: -3
As Kb/moldm ↓, pKb ↑, basic strength decreases
* HF dissociates to a greater extent than HCN, (becomes weaker/pH becomes lower)
HF contains a higher [H+] than HCN, If Kb of NH3 > Kb of CH3COO- (pKb of NH3<pKb of CH3COO-)
pH of HF is lower than that of HCN. - NH3 is a stronger base than CH3COO-
For dissociation of a dibasic acid (happens twice), there - For NH3 (aq) & CH3COO- (aq) of the same conc:
are two dissociation constants: Ka1 and Ka2. * NH3 contains a higher [OH-] than CH3COO-,
Hence, overall Ka = Ka1 X Ka2 pOH of NH3 is lower than that of CH3COO-,
Note that Ka1 >> Ka2>> Ka3… since +vely charged protons pH of NH3 is higher than that of CH3COO-
are more readily lost from neutral acid molecules than
from negatively charged conjugate bases of the acids.
CALCULATION OF pH OF WEAK ACIDS: CALCULATION OF pH OF WEAK BASES:
-3
Consider a weak acid HA (aq) of concentration Co moldm Consider a weak base B (aq) of concentration Co moldm-3
HA (aq) H+ (aq) + A- (aq) B (aq) + H2O (l) BH+ (aq) + OH- (aq)

Let [H+] be x moldm-3 at equilibrium. Ignoring self- Let [OH-] be x moldm-3 at equilibrium. Ignoring self-
ionization of water, [H+] = [A-] = x moldm-3 ionization of water, [OH-] = [BH-] = x moldm-3
Conc/moldm-3 HA (aq) H+ (aq) + A- (aq) Conc/moldm-3 B (aq) BH+ (aq) + OH- (aq)
Initial amt: Co 0 0 Initial amt: Co 0 0
Change: -x +x +x Change: -x +x +x
Eqm: (Co – x) x x Eqm: (Co – x) x x
+  
Ka = [H ][A ]  ( x)( x)  x2 +
Kb = [BH ][OH ]  ( x)( x)  x
2

[HA] (Co  x) (Co  x ) [B] (Co  x ) (Co  x )

Since HA is a weak acid, assume x << Co, so (Co – x) ≈ Co. As B is a weak base, assume x << Co, so (Co – x) ≈ Co.
2 
Therefore, Kb = x  x  [OH ] 
2
Therefore, Ka = x  x  [ H  ]  Ka Co Kb Co
Co Co

pH = -lg Ka Co pOH = -lg Kb Co , pH = pKw - pOH

Two key assumptions: [H+] from the self-ionization of Two key assumptions: [OH-] from the self-ionization of
water is negligible. Also, x << Co such that (Co – x) ≈ Co, water is negligible. Also, x << Co such that (Co – x) ≈ Co,
where Co = initial [HA] and x = [H+] = [HA]dissociated. where Co = initial [B] and x = [OH-] = [B]dissociated.

To see if the 2nd assumption is valid, we apply the 5% rule. To see if the 2nd assumption is valid, we use the 5% rule.
2 2
If x x 100% ≤ 5%, the assumption is valid, If x x 100% ≤ 5%, the assumption is valid,
Co Co
approximation can be used. If not, assumption is not approximation can be used. If not, assumption is not
valid, quadratic equation must be solved to find x. Simple valid, quadratic equation must be solved to find x. Simple
C
rule of thumb: if o > 1000, then (Co – x) ≈ Co.
C
rule of thumb: if o > 1000, then (Co – x) ≈ Co.
Ka Kb
Relationship between Kw, Ka and Kb/Relative Strengths of conjugate acid-base pairs:
(Ka of acid HA) x (Kb of conjugate base A-) = Kw (Kb of base B) x (Ka of conjugate acid BH+) = Kw
HA (aq) H+ (aq) + A- (aq) B (aq) + H2O (l) BH+ (aq) + OH- (aq)
14 14
Kb of conjugate base A- = Kw = 1.0  10 Ka of conjugate acid BH+ = Kw = 1.0  10
Ka of HA Ka of HA Kb of B Kb of B
thus Kb of a conjugate base can be calculated from the Ka thus Ka of a conjugate acid can be calculated from the Kb
of the acid. of the base.
The larger the Ka of an acid, the smaller the Kb of its conjugate base. If HA is a stronger acid than HB, A- is a weaker
base than B-. (exists in opposites  strong acid has weak conjugate base and vice versa)
For an acid HA to react appreciably with a base, B, HA must be a stronger acid than the conjugate acid of B (BH +).
Consider the reaction between HA and B to form A- and BH+: HA (aq) + B (aq) A- (aq) + BH+ (aq), Kc = Ka of HA
Ka of BH 
Kc is large if Ka of HA >>> Ka of BH  HA reacts with B to a great extent. But B does not react with HA.
+

Kc is small if Ka of HA <<< Ka of BH+  reaction between HA and B hardly occurs.

If Kc = big value, position of eqm lies far to the right  reaction occurs.

DEGREE OF DISSOCIATION, 𝜶
Degree of dissociation, α, of an electrolyte can be defined as the fraction of molecules with is ionized at equilibrium:
number of moles of molecules which are ionized at eqm
α=
number of moles of molecules present initially
-The degree of ionization may also be expressed in %.
For strong acids/bases which ionize completely, α = 1, For weak acids/bases which ionize partially, 0 < α < 1
Consider a weak monobasic acid HA of concentration Co moldm-3 and degree of ionization α. In aqueous solution, the
following eqm is established: Conc/moldm-3 HA (aq) H+ (aq) + A- (aq)
Initial amt: Co 0 0
Change: - α Co + α Co + α Co
Eqm: Co (1- α) α Co α Co

Ka = [H ][A ]  ( Co )( Co )   Co
+  2

[HA] Co (1   ) (1   )
Since Ka is constant at a given temp, dilution law states that any decrease in concentration must be accompanied by an
increase in the degree of ionization. For a weak acid in which α is very small such that (1- α) ≈ 1. Therefore,

Ka = α2 Co    Ka Kb = α2 Co    Kb
Co Co
For a weak acid, α increases with increasing dilution and is therefore NOT constant at a given temperature.
 13.5) Salts of Weak Acids and Bases- Salt Hydrolysis (pg 22-25)
- Salts are produced when acids react with bases, making up of a cation (from base) and an
anion (from acid). When salts dissolve in water to form solutions, the resultant cations/
anions can undergo hydrolysis to form acidic or alkaline solutions.
- Whether the salt dissolves to form a neutral, acidic or alkaline solution depends on the acid
and the base which react to give the salt:
Types giving Elaboration
rise to salt
Strong base- When added to water, complete dissociation of NaCl occurs. Both Na+ and Cl- ions do not
strong acid undergo hydrolysis, so [H+] = [OH-] in aq. NaCl and the solution is thus neutral. pH = 7 at 25oC
(aq Na+Cl-)
Strong base- When added to water, complete dissociation of CH3COO- Na+ occurs. Being the anion of a
weak acid weak acid, CH3COO- is a relatively strong conjugate base and hydrolyses in water (partially
(aq CH3COO- cuz it’s still a weak base as seen by its low Kb value) to give OH- ions.
Na+) CH3COO- (aq) + H2O (l) CH3COOH (aq) + OH- (aq)
Slight excess of OH- ions generated by hydrolysis of the anion of a weak acid causes the
solution to be alkaline. pH > 7 at 25oC
weak base- When added to water, complete dissociation of NH4Cl occurs. Being the cation of a weak
strong acid base NH3, NH4+ is a relatively strong conjugate acid and hydrolyses in water (partially cuz it’s
(aq NH4+Cl-) still a weak acid as seen by its low Ka value) to give H3O+ ions.
NH4+ (aq) + H2O (l) NH3 (aq) + H3O+ (aq)
Slight excess of H3O+ ions generated by hydrolysis of the cation of a weak base causes the
solution to be acidic. pH < 7 at 25oC
weak base- When added to water, complete dissociation of CH3COO- NH4+ occurs. CH3COO- is a strong
weak acid conjugate base and NH4+ is a strong conjugate acid. The aq solution may be slightly
(aq CH3COO- acidic/alkaline or neutral depending on the relative conc. of H3O+ & OH- ions formed.
NH4+) Acidic if Ka of cation > Kb of anion,
Neutral if Ka of cation = Kb of anion
Alkaline if Ka of cation < Kb of anion
Since Ka of NH4+ > Kb of CH3COO-, a solution of CH3COONH4 is weakly acidic.
Solutions of Salts of Weak Acid Solutions of Salts of Weak Base
Salts of weak acids contain anion of weak acids. Since the Salts of weak bases contain cations which are conjugate
anion of the weak acid hydrolyses partially in water to acids of weak bases. Since the cation of the weak base
give OH-, it has a Kb and is related to Ka of weak acid by: hydrolyses partially in water to give H3O+, it has a Ka and
14
Kb of conjugate base A- = Kw = 1.0  10 is related to Kb of weak base by:
Ka of HA Ka of HA Ka of conjugate acid BH+ = Kw = 1.0  10 14
The pH of a solution of the salt of a weak acid with initial Kb of B Kb of B
conc, Co, may be calculated given its Kb of the anion OR The pH of a solution of the salt of a weak base with initial
Ka of the weak acid, or vice versa. conc, Co, may be calculated given its Ka of the cation OR
If we assume [OH-] << Co, so (Co – [OH-]) ≈ Co. Kb of the weak base, or vice versa.
If we assume [H+] << Co, so (Co – [H+]) ≈ Co.
x  [OH  ]  Kb Co = Kw
Co
Ka x  [ H  ]  Ka Co = Kw Kw
Co , pH = -lg Co
pOH = -lg Kw , pH = pKw - pOH Kb Kb
Co
Ka
13.6) Buffer Solutions (pg 26-32)
Buffer Solution: Able to resist a change in pH upon addition of a small amount of acid/base.
Buffer solutions contain both an acidic species and a basic species (in large amounts) to react
respectively with any base/acid added:
 Acidic buffer: consists of a mixture of a weak acid and its salt.
 Alkaline buffer: consists of a mixture of a weak base and its salt.
Acidic Buffers
- Consists of a mixture of a large reservoir of unionized weak acid & a salt containing the
conjugate base of the weak acid.
CH3COOH (aq) CH3COO- + H+ (aq)  (reaction 1  partial dissociation)
CH3COO-Na+ (aq) CH3COO- + Na+ (aq)  (reaction 2  complete dissociation)
According to Le Chatelier’s Principle, the presence of CH3COO- ions from the complete
dissociation of sodium ethanoate further suppresses the dissociation of ethanoic acid
(reaction 1), in fact more ethanoic acid is produced! Hence the buffer solution contains a
relatively high concentration of the unionized ethanoic acid (weak acid) and ethanoate ion
(conjugate base of the weak acid). These relatively high concentrations of both the ethanoic
acid and the ethanoate ion enable the solution to function as a buffer. The acidic buffer:
1) Adds a small amount of acid (H+ ions) to the solution
- When a small amount of H+ ions is added, nearly all the H+ added will be removed by the
large reservoir of CH3COO- ions to form CH3COOH. [H+] does not increase significantly and
the pH is kept approximately constant.
2) Addition of base (OH- ions) to the solution
- When a small amount of OH- ions is added, nearly all the OH- added will be removed by the
large reservoir of CH3COOH ions to form CH3COO-. [OH-] does not increase significantly and
the pH is kept approximately constant.

Alkaline Buffers
- Consists of a mixture of a large reservoir of unionized weak base & a salt containing the
conjugate acid of the weak base.
NH3 (aq) + H2O (l) NH4+ + H+ (aq)  (reaction 1  partial ionization)
NH4Cl (aq) NH4+ + Cl- (aq)  (reaction 2  complete ionization)
According to Le Chatelier’s Principle, the presence of NH4+ ions from the complete ionization
of ammonium chloride further suppresses the ionization of aq ammonia (reaction 1), in fact
more ammonia is produced! Hence the buffer solution contains a relatively high
concentration of the unionized aq ammonia (weak base) and ethanoate ion (conjugate base
of the weak acid). These relatively high concentrations of both the ethanoic acid and NH4+
ions. The alkaline buffer:

1) Adds a small amount of acid (H+ ions) to the solution

- When a small amount of H+ ions is added, nearly all the H+ added will be removed by the
large reservoir of NH3 to form NH4+. [H+] does not increase significantly and the pH is kept
approximately constant.
 2) Addition of base (OH- ions) to the solution
- When a small amount of OH- ions is added, nearly all the OH- added will be removed by the
large reservoir of NH4+ ions to form NH3. [OH-] does not increase significantly and the pH is
kept approximately constant.

Calculating pH of buffer solutions:

Consider a buffer solution containing a weak acid HA and a salt of the acid Na+A-:
Na+A- (aq) Na+ (aq) + A- (aq)
HA (aq) H+ (aq) + A- (aq)
HA, being a weak acid, undergoes slight dissociation in aqueous solution. Its dissociation is
further suppressed by the presence of A- ions from the complete dissociation of Na+A-. This is
in accordance with Le Chatelier’s Principle. Hence at equilibrium,
[HA] ≈ Initial [HA], the initial concentration of acid after mixing.
[A-] ≈ Initial [A-], the initial concentration of salt after mixing.
 
At equilibrium, Ka = [ A ][ H ]  [H+] = K a [HA]

[ HA] [A ]
 
-lg [H+] = -lg Ka + lg [ A ]  pH = pKa + lg [ A ] OR pH = pKa + lg [ salt ]
[HA] [HA] [acid]
Similarly for an alkaline buffer solution containing weak base B and salt of base BH+Cl-

-lg [OH-] = -lg Kb + lg [BH ]  pOH = pKb + lg [BH ] OR pOH = pKb + lg [ salt ]


[B] [B] [base]

* When calculating pH/pOH of buffer solutions:
- Identify the type of solution (acidic/alkaline buffer)
- Apply above formulas accordingly.
- Determine [HA] and [A-] or [B] and [BH+] in the buffer mixture
- Substitute equilibrium concentrations into equation and solve for pH/pOH.

Buffering Capacity:
Amount of acid/base that may be added to a buffer solution before its pH changes
appreciably, it represents the ability of a buffer to resist changes in pH. Buffer solution is
most effective in resisting changes in pH when:
(a) the number of moles of both the weak acid/base and its salt are large relative
to that of the acid/base to be added to the buffer solution
(b) Weak acid/base to salt concentration ratio is close to 1:1.
ACIDIC BUFFER ALKALINE BUFFER
 
[ A ] ≈ 1, pH = pKa + lg [ A ] ≈ pKa [BH  ] ≈ 1, pOH = pKb + lg [BH ] ≈ pKb
[HA] [HA] [B] [B]
 
When [ A ] = 1, maximum buffer capacity is When [BH ] = 1, maximum buffer capacity is
[HA] [B]
 
attained. pH = pKa, since lg [ A ] = lg 1 = 0. attained. pOH = pKb, since lg [BH ] = lg 1 = 0.
[HA] [B]
 
Effect of Dilution on pH of buffer: pH = pKa + lg [ A ] , pOH = pKb + lg [BH ]
[HA] [B]
From that equation, it can be seen that diluting the buffer has no effect on the pH/pOH
because the concentrations of HA and A- (or B and BH+) are reduced by the same extent (i.e.
the value [ A ] / [BH  ] is unchanged.)
[HA] [B]
However, dilution has a marked effect on buffering capacity. It reduces the ability of the
buffer to cope with contaminating acid and base.

Preparation of buffer solution: pH = pKa + lg [ salt ]

[acid]
From that equation, it can be seen that two terms on the RHS determine the pH. The first
term is the pKa, responsible for the ‘course selection’ of pH. The second term involves the
ratio [ salt ] and provides the ‘fine tuning’ to the final desired pH. Hence, the strategy for
[acid]
preparing an acidic buffer solution of a desired pH is to select an acid whose pKa is within
about one pH unit of the desired pH. The ratio of salt of acid concentrations is then adjusted
to achieve the desired pH. There are two ways in which an acidic buffer may be produced:
(1) Mixing a solution of a weak acid and its salt
(2) Partially neutralizing a solution of a weak acid with a strong base

Uses of buffer solution:

Buffers are important in living systems: pH of human blood is controlled using different
buffers: H2CO3/HCO3- buffer notably. Blood acts as a biological buffer  must be kept at pH
7.4, if <6.8 or >7.8  death.
H2CO3 (aq) HCO3- (aq) + H+ (aq) Important buffers in human blood are made up of
carbonic acid (H2CO3) and hydrogencarbonate ion (HCO3-). H2CO3 in blood originates from
dissolved CO2. CO2 (g) + H2O (l) H2CO3 (aq) If the concentration of H+ ions in the blood
increases, the HCO3- present reacts with the additional H+ ions and thus the pH remains
virtually unchanged. HCO3- (aq) + H+ (aq) H2CO3 (aq) If the concentration of OH- ions in
the blood increases, H2CO3 present reacts with the additional OH- ions and thus a constant
pH is maintained. H2CO3 (aq) + OH- (aq) HCO3- (aq) + H2O (l)

13.7) Acid-Base Titration Curves (pg 32-40)

Equivalence Point: Point were reaction between equivalent/stoichiometric amounts of acid
& base is just complete.
End Point: Point at which an indicator changes colour distinctly in this titration.
Choices of Indicators
Acid-Base indicators such as phenolphthalein and methyl orange are weak acids or weak
bases which change colour according to the pH of the solution to which they are added 
used to test for acidity/alkalinity  by detecting end-point in acid-base titrations.
A suitable indicator is one where its working range coincides with the region of rapid pH
change in the titration curve. Upon one drop of titrant added, indicator should give a sharp
and distinct colour change.
Consider an indicator which is a weak acid with the general formula HIn:
  
HIn (aq) (COLOUR A) + H2O (l) H3O+ (aq) + In- (aq) (COLOUR B) KIn = [In ][ H 3O ]
[ HIn]
-
HIn and In have different colours, so that colour changes are observed when equilibrium
shifts to the left/right. The colour of an indicator depends on the relative proportions of HIn

and In-, which is in turn dependent on the pH of the solution: pH = pKIn + lg [In ]
[HIn]
In a strongly acidic solution In a strongly alkaline solution
+ +
[H3O ] is very high, so the equilibrium position lies far to [H3O ] is very low, so the equilibrium position lies far to
the left  colour of the indicator in the acidic solution is the right  colour of the indicator in the alkaline solution
the colour of HIn, Colour A. When the ratio of [HIn] : [In-] is the colour of In-, Colour B. When the ratio of: [In-]: [HIn]
is at least 10:1, the colour of HIn will dominate. is at least 10:1, the colour of In- will dominate.
Ratio of [HIn] : [In-] > 10  Colour A is observed
Ratio of [HIn] : [In-] = 10  Change of colour starts, Colour A still dominates (pH = pKIn -1)
Ratio of [HIn] : [In-] = 1  End-point of titration, midpoint of colour change. Colour
A& B will be observed (pH = pKIn)
Ratio of [HIn] : [In-] = 0.1  Change of colour ends, Colour B now dominates (pH = pK In +1)
Ratio of [HIn] : [In-] < 0.1  Colour B is observed
The working range of an indicator is generally given by pKIn ± 1. The end-point during an
acid-base titration is the stage where the indicator used gives a distinct colour change. This
happens when the indicator has a colour half-way between its extreme colours,
[HIn (aq)] (colour A) = [In- (aq)] (colour B)

Since lg [In ] = lg 1 = 0, pH = pKIn at the end point of the reaction. Colour at end point is A + B.
[HIn]

Indicator Working Colour in Acid Colour in Base Colour at end-point

Range (colour of HIn) (colour of In-)
1) Methyl Orange Red Yellow Orange
2) Screened Methyl Orange pH 3.2 -4.4 Violet Green Grey
3) Bromothymol Blue pH 6.0 -7.6 Yellow Blue Green
4) Thymol Blue
5) Phenolphthalein pH 8.3 -10.0 Colourless Pink Light Pink if titrant is alkali,
colourless if titrant is acid

TYPE OF TITRATION e.g. of acid e.g. of base Marked pH change Suitable indicator
Strong acid- strong base HCl NaOH 4 - 10 All can use (1,4 preferred)
Weak acid- Strong base CH3COOH NaOH 7.5 - 10.5 4,5
Strong acid- weak base HCl NH3 3.5 - 6.5 1,2
Weak acid- weak base CH3COOH NH3 No marked change NIL
 Titration Curve of Strong Acid-Strong Base Reaction
The graph below shows the change in pH of the reaction
mixture when aq NaOH of concentration 0.100moldm-3 was
added to 25.0cm of 0.100moldm-3 dil HCl:
START: Initial pH is low because EQUIVALENCE POINT: Region of rapid pH END: Excess NaOH is added
the acid used is a strong acid. pH change: Sudden increase in pH over the after equivalence point.
3
remains low from 0-25cm as the equivalence point (pH 410) when one Titration curve flattens out
solution still contains strong acid or two drops of base are added from the at a high pH as the base
that has not yet been neutralized. burette. At equivalence point, solution used is a strong acid.
contains NaCl, pH = 7 (neutral).

Titration Curve of Weak Acid-Strong Base Reaction

The graph below shows the change in pH of the reaction mixture
when aq NaOH of concentration 0.100moldm-3 was added to
25.0cm of 0.100moldm-3 dil CH3COOH:

START: Initial HALF- EQUIVALENCE POINT: EQUIVALENCE POINT: Region of rapid pH END: Excess
pH (1<pH <7) Change in PH is fairly constant change: Shorter and occurs at a higher pH base 
is not very low due to the formation of a range than that of a SA-SB titration. At titration curve
as a weak acid effective buffer when large equivalence point, CH3COOH is exactly flattens out at
is used. ([H+] = amounts of the weak acid and neutralized by aq NaOH and solution a high pH as
KaCo , its salt are present. (pH at contains CH3COO-Na+ (aq) pH of the the base used
calculate pH) half-eqv pt is where [HA ] = [A- resultant solution is >7, as CH3COO- is a strong
], pH = pKa) hydrolyses in water to give OH-. base.

Titration Curve of Strong Acid-Weak Base Reaction

The graph below shows the change in pH of the reaction
mixture when aq HCl of concentration 0.100moldm-3
was added to 25.0cm of 0.100moldm-3 aq NH3:

START: Initial HALF- EQUIVALENCE POINT: EQUIVALENCE POINT: Region of rapid pH END: Excess
pH (7<pH <13) Change in PH is fairly constant change: Shorter and occurs at a lower pH acid 
is not very due to the formation of a range than that of a SA-SB titration. At titration curve
high as a weak effective buffer when large equivalence point, NH3 is exactly flattens out at
base is used. amounts of the weak base and neutralized by dil HCl and solution a low acidic pH
[OH-] = KbCo , its salt are present. (pOH at contains NH4Cl. The pH of the resultant as the acid
calculate pH) half-eqv pt where [B] = [BH+], solution is <7, as NH4+ hydrolyses in water used is a
pOH = pKb) to give H+. strong acid.
 Titration Curve of Weak Acid-Weak Base Reaction
The graph below shows the change in pH of the reaction
mixture when aq NH3 of concentration 0.100moldm-3 was
added to 25.0cm of 0.100moldm-3 ethanoic acid:

START: Initial EQUIVALENCE POINT: There is no straight, vertical END: After eqv pt has passed,
pH is relatively section on the graph  change in pH at the equivalence titration curve flattens out at a
high because point is not as sharp as any of the previous titrations. fairly low alkaline pH value
the acid used is - pH at eqv pt < 7, if Ka of WA > Kb of WB since excess base present is a
a weak acid. - pH at eqv pt > 7, if Ka of WA < Kb of WB weak base.

* NO suitable indicator for this titration as rapid pH change is absent in WA-WB titration.

Double Indicator Method

This method is used to determine the composition of
mixtures of weak and strong bases:
- sodium carbonate & sodium hydroxide
- sodium carbonate & sodium hydrogen carbonate
OR mixtures of weak and strong acids:  ethanoic acid
(weak) and hydrochloric acid (strong)

It is named the double indicator method, as there are two equivalence points that can be
identified using 2 different indicators.

The reaction of Na2CO3 with HCl occurs in two stages:

(A) Na2CO3 (aq) + HCl (aq)  NaHCO3 (aq) + NaCl (aq)
(B) NaHCO3 (aq) + HCl (aq)  NaCl (aq) + CO2 (g) + H2O (l)
Overall, Na2CO3 (aq) + 2HCl (aq)  2NaCl (aq) + CO2 (g) + H2O (l)

From the titration curve, every equivalence point can be identified by using:
- Phenolphthalein indicator: solution changes from pink to colourless when reaction A is
complete (when sodium carbonate is only half-neutralized)
- Methyl Orange indicator: solution changes from yellow to orange when reaction B is
complete (when sodium carbonate is completely neutralized –CO2 formed)
 SOLUBILITY EQUILIBRIUM (Lecture Notes 13b)
13.8) Dissolution as an Equilibrium Process (pg 2)
Soluble Salts: Dissociate fully in solution into their constituent ions.
Sparingly Soluble Salt:
Dissociates partially in solution to their constituent ions, as salt added↑, concentration of
ions ↑till point of saturation (contains maximum amount of dissolved solute at a particular
temperature in the presence of undissolved solute) (Unsaturated solution: less solute than
solution is capable of dissolving under the same given conditions)

Ions in saturated solution are in dynamic equilibrium (dissolution and precipitation happen
at the same rate, rate of Frwd rxn = rate of bkwd rxn) with excess undissolved solid. There
is no net change in concentrations of the ions.
13.9) Solubility Product, Ksp (pg 2-3)
Equilibrium established in a saturated solution of a sparingly soluble salt with general
formula MaXb: MaXb (s) aMb+ (aq) + bXa- (aq)
The concentration of a pure solid, which is proportional to its density is constant at a
particular temperature. Since [MaXb (s)] is constant at a given temp, then:
Kc[MaXb (s)] = [Mb+ (aq)]a [Xa- (aq)]b = constant.
Hence we can define a new equilibrium constant called solubility product, Ksp:
Ksp of MaXb (s) = [Mb+ (aq)]a [Xa- (aq)]b units: (moldm-3) a+b
Solubility product, Ksp  equilibrium constant (Kc) for the equilibrium established
between the undissolved sparingly soluble salt & its constituent ions in a SATURATED
solution. Ksp varies with temperature. If a solution at a particular temperature is
unsaturated, the equilibrium between the excess undissolved solute and the dissolved ions
DOES NOT EXIST  Ksp is not defined.

13.10) Solubility (pg 4-6)

Solubility: Maximum amount of solute which can dissolve in a given amount of solvent at a
particular temperature  solubility of the solute in that solvent  usually expressed as
moldm-3 or gdm-3 (number of moles/mass of solute dissolved in 1dm3 of solution)
- soluble  solubility ≥ 0.1 moldm-3 at 298K
- sparingly soluble  solubility < 1.0 x10-3 moldm-3 at 298K
SOLUBLE COMPOUNDS SPARINGLY SOLUBLE COMPOUNDS
-
All nitrates (NO3 ) -
- - -
Most halides (Cl , Br , I ) Halides of Ag+, Pb2+, Cu+
2-
Most sulfates (SO4 ) Sulfates of Pb2+, Ca2+, Ba2+
+ + + 2+ 2+
Oxides of Na , K , NH4 & larger Group 2 cations (Ca , Ba ) Most oxides (O2-)

Hydroxides of Na+, K+ & larger Group 2 cations (Ca2+, Ba2+) Most hydroxides (OH-)
Sulfides of Na+, K+, NH4+ & Group 2 cations (Ca2+, Mg2+, Ba2+) Most sulfides (S2-)
Carbonates/ Phosphates of Na+, K+, NH4+ Most carbonates (CO32-) & phosphates
(PO43-)
Chromates of Na+, K+, NH4+ & small Group 2 cations (Mg2+) Most chromates (CrO42-)
Solubility and Solubility Product:
Solubility products give a direct comparison of the solubility of two salts only IF the total
number of ions produced in solution is the SAME in both cases (AgCl and BaCO3)  in that
case, the higher the Ksp value, the higher the solubility of the ionic compound. If total no.
of ions produced is different, then solubility products do not give a comparison of solubilities
and a calculation must be performed.

* You will need to calculate Ksp from solubility/solubility from Ksp. There might be
discrepancy between the calculated Ksp vs theory due to the incorrect assumption that the
salt dissociates completely in aq solution. There might be another equilibrium reaction to
consider for the dissolution of the salt. Also, use ‘s moldm-3’ and not ‘x moldm-3’ when
calculating solubility.

13.11) Ionic Product (pg 7-10)

When a solution containing M+ ions is mixed with another containing X-, it is possible to
predict whether precipitation would occur once the ionic product is calculated & compared
with the solubility product. Given: MaXb (s) aMb+ (aq) + bXa- (aq)
Ionic product: Product of the concentration of the constituent ions in the solution at that
instant raised to the appropriate powers:
Ionic Product = [Mb+ (aq)]a [Xa- (aq)]b units: (moldm-3) a+b
While both ionic & solubility products have the same equation, Ksp  equilibrium
concentrations of the ions in the presence of undissolved MaXb (in a saturated solution) For
ionic product, [Mb+ (aq)] & [Xa- (aq)]  instantaneous concentrations of the ions. In short:
Solubility product, Ksp  equilibrium constant (Kc)
Ionic product  reaction quotient  at equilibrium, ionic product = solubility product.
VERY IMPORTANT:
Consider Ionic product = [Ca2+ (aq)][OH- (aq)]2
2+ -
Ca(OH)2 (s) Ca (aq) + 2OH (aq), Ksp = [Ca2+ (aq)][OH- (aq)]2 = 6.5 x 10-6 mol3d
Initially, as solution containing OH- (aq) is added dropwise to the solution containing Ca2+
(aq), ionic product will ↑gradually  here, ionic product < Ksp, NO PRECIPITATION occurs.
In some point in time, [OH- (aq)] in the resulting mixture will be high enough that ionic
product = Ksp. (dissolving max amt of Ca(OH)2 (s) (SATURATION) in water, given that [OH-
(aq)] need not be twice of [Ca2+ (aq)], and there is no excess solid Ca(OH)2 in the solution.)
Upon adding a small vol. of OH- (aq) to the saturated solution of Ca(OH)2, ionic product >
Ksp. The solution cannot fit the excess OH ions and white ppt of Ca(OH)2 is formed.
When no more ppt is observed, equilibrium has been reached, ionic product = Ksp. Solution
is now saturated with Ca(OH)2 in the presence of excess, solid Ca(OH)2
You will need to calculate and compare ionic and solubility products to predict the formation
of a ppt given Ksp value. Also, you will have to calculate the minimum concentration of ions
required for ppt formation, and predict which ion will form a precipitate first given two ions
which can form a ppt on the addition of another ion. (if the minimum conc. required to ppt
out A is less than that of B, then A will ppt out first)
13.12) Common Ion Effect (pg 11)
.Given: AgI (s) Ag+ (aq) + I- (aq) , Ksp = [Ag+ (aq)][I- (aq)]
AgI: Ag+: I- = 1:1:1. Hence, eqm [Ag+ (aq)] = eqm [I- (aq)]
Upon adding AgNO3 to a saturated solution of AgI:
- AgNO3 contains the common ion Ag+.
- Hence, upon adding AgNO3 into AgI solution, [Ag+ (aq)] will increase  (ionic product > Ksp)
- According to Le Chatelier’s principle, eqm position will shift to the left to produce more AgI
(s) ppt, [I-] will also decrease. Hence in the presence of common ion Ag+, solubility of AgI is
reduced. (This is known as the common ion effect.) This works with addition of KI too, where
I- is the common ion.
Common Ion Effect: Reduced solubility of a salt in a solution that already contains an ion
common to that salt.
13.13) Applications of the Solubility Product Principle (pg 12-15)
Solubility product principle can be applied to the formation of metal hydroxide ppts, made
use in QA analysis. Consider the addition of NaOH (aq), NH3 (aq)or a mixture of NH3 and
NH4Cl into an aq solution of metal cations.

- Aq. NaOH (strong base) ionizes completely in aq solution to give OH- ions
- Aq. NH3 (weak base) ionizes partially in aq solution to give OH- ions
NH3 (aq) + H2O (l) NH4+ (aq) + OH- (aq)

In a mixture of NH3 (aq) & NH4Cl (aq), ionization of NH3 to form OH- ions is suppressed by the
common ion effect since NH4Cl undergoes complete dissociation to NH4+ & Cl- ions. Thus, the
increase in [NH4+] suppresses the partial ionization of NH3 (aq). The position of equilibrium
shifts to the left such that the [OH-] in solution which is low at any time is made even lower.

The formation of a ppt depends on the Ksp value of the metal hydroxide.
(1) Metal ions, whose hydroxides have a moderately low Ksp forms a ppt in aq NH3 but
not in a mixture of NH3 and NH4Cl. (For example, when aq NH3 is added to Mg2+ (aq)
solution, [OH-] increases. At that instant, ionic product > Ksp, Mg(OH)2 is ppted out.
When a mixture of NH3 and NH4Cl is added to the same Mg2+ solution, [OH-]
increases but is too low to make the ionic product > Ksp  no ppt results.
(2) Metal ions, whose hydroxides have a very low Ksp forms a ppt in both aq NH3 and a
mixture of NH3 and NH4Cl. Despite the low conc of OH- available in the mixture of
NH3 and NH4Cl, it is not high enough for ionic product > Ksp. Thus ppt occurs even
when a mixture of NH3 and NH4Cl was added to a solution containing Cr3+ ions.

The solubility of a sparingly soluble salt may be enhanced upon the addition of a reagent
that consumes the cation/anion of the salt (reagent forms a complex ion with the cation) .
When the conc of the anion is decreased, according to LCP, eqm position will shift to the
right (ionic product < Ksp) to counteract the decrease in the ion and cause more salt to
dissolve. MaXb (s) aMb+ (aq) + bXa- (aq)
ELECTROCHEMISTRY (Lecture Notes 18)
18.1) Preamble (pg 2-5)
RECALL FROM CHAPTER 1: OXIDATION NUMBERS AND STATES
* Recall negative/positive oxidation number  more/less electronegative respectively
*Recall oxidizing: increase in oxidation state, loss of electrons, occurs at anode.
*Recall reducing: decrease in oxidation state, gain of electrons, occurs at cathode.
*Recall oxidizing agent: oxidize another substance, is reduced itself.
*Recall reducing agent: reduce another substance, is oxidized itself.
*Recall disproportionation reactions. (Chpt 1)
Electrolyte: Conducts electric current (and is decomposed) when it is in aqueous solution or
molten state. An electrolyte conducts electricity due to the flow of charge carried by its ions.
Strong/Weak/Non Electrolyte:
Compound which ionizes fully/partially/not at all in aqueous/molten solution respectively

A) ELECTRODE POTENTIALS
18.2.1) Introduction (pg 5-6)
When a strip of metal M is placed in a solution of its ions, M can be oxidized, Mn+ can be
reduced. Over time, the separation of charge across the metal-solution interface creates a
potential difference between the metal and solution. Electrode potential, E of an element is
the potential difference between an aqeous solution of its ions and the element when it is in
equilibrium with that solution. Electrode potential depends on standard conditions (25oC, 1
moldm-3, 1 atm). Standard conditions are mentioned in Chapter 5, under enthalpy.
Mn+ (aq) + ne- M (s) E = positive OR negative, depending on position of equilibrium
2+ -
Zn + 2e Zn (s) E<0
- Position of equilibrium lies more to the left. Zn has a greater tendency to dissolve as
ions and a lower tendency to be deposited as metal.
Cu2+ + 2e- Cu (s) E>0
- Position of equilibrium lies more to the right. Cu has a greater tendency to dissolve
as ions and a lower tendency to be deposited as metal.

18.2.2) Standard Hydrogen Electrode [S.H.E] (pg 6-7)

The absolute electrode potential of a single electrode system cannot be measured directly.
To measure the potential difference/electromotive force/emf between two electrode
systems, a half-cell is connected to another half-cell. One electrode system is used as a
reference, and all other electrode systems can be
measured against this reference. Thus, the standard
hydrogen electrode is chosen as the reference
electrode and the potentials of all other electrode
systems can be compared with it. The S.H.E consists
of a platinum electrode coated with finely divided
Pt (called platinum black), immersed in an aq
solution of H+ where [H+] = 1 moldm-3, with
hydrogen gas bubbling at pressure of 1atm, at 25oC.
 18.2.3) Half Cells & Standard Electrode
o
Potential, E (pg 7-8)
A half-cell is a system that contains:
*A conductive electrode and a surrounding conductive electrolyte,
*An oxidized species and a reduced species.
Oxidized species +ne- reduced species.
3 types of half cells:
Metal/Metal ion Half cell: (shown above)
For example, the Cu2+(aq)/Cu half-cell 
Cu2+ (aq) + 2e- Cu (s)

Gas/Ion Half cell: (shown right)

For example, the H2 (g)/H (aq) half-cell 
+

H2 (g) + 2e- 2H+ (aq)

Ion/Ion Half cell: (shown right)

For example, the Fe (aq)/ Fe (aq) half-cell 
3+ 2+

Fe3+ (aq) + e- Fe2+ (s)

The ion/ion half-cell consists of an inert electrode dipped into a solution containing ions of
the same element in 2 different oxidation states.

Each system primarily contains the same element in different oxidation states. In the
absence of a metal in the half-cell, platinum is used as the inert electrode. When a half-cell
is connected to a S.H.E, the resultant system has a potential difference (I.e. electromotive
force or e.m.f), measured with a voltmeter. If this e.m.f is measured under standard
conditions, its value is known as the standard electrode potential, Eo of the Mn+/M half cell.

Standard Electrode Potential, Eo, of a half cell electromotive force btwn half-cell &
standard hydrogen electrode(S.H.E) measured at standard conditions (298K/1atm/1moldm-3)

18.2.4) Measuring the Standard Electrode Potential, Eo (pg 8-12)

Set up the given half-cell and the S.H.E next to each other and ensure standard conditions.
Connect the two solutions in the two half-cells with a “salt bridge”, commonly made up of
saturated KNO3 solution. Measure the potential difference between the given half-cell and
the S.H.E using a high-resistance voltmeter. Value shown on the voltmeter is the standard
electrode potential (emf) of the half cell!  Note that the first reading should be taken, as
subsequent readings will no longer be at standard conditions.

Salt Bridge: COMPLETES the circuit, does not allow mixing of the solutions in the two half-
cells. It is also used to maintain electrical neutrality. As oxidation and reduction occur, ions
in the salt bridge migrate so as to ‘neutralize’ the increasing charge in the two half-cells.
Migration of ions is necessary to ensure the continuous smooth operation of the
electrochemical cell until the reactants are used up. The cations migrate to the cathode,
while the anions migrate to the anode.
 a) MEASURING STANDARD ELECTRODE
POTENTIAL FOR METAL/METAL ION SYSTEM:
You must learn to draw this! 
Electrons flow from the metal/metal ion half-cell to
the S.H.E (since oxidation takes place) (flow of e is
opp. to direction of conventional current)
Anode: Mg  Mg2+ +2e- (Mg is oxidized to Mg2+)
Cathode: 2H+  2e- +H2 (H+ is reduced to H2)

At standard conditions, the reading first shown on the voltmeter gives the standard
electrode potential, Eo, of the Mg2+(aq)/Mg (s) half cell.
Mg2+(aq) + 2e- Mg (s) Eo = -0.76 V
The Eo is often written as a reduction potential. The voltmeter measures the potential
difference between the two half cells. Since the potential for the S.H.E is arbitrarily assigned
as zero volts, the voltmeter reading can be treated as the potential of the metal half-cell.
b) MEASURING STANDARD ELECTRODE
POTENTIAL FOR GAS/ION SYSTEM:
You must learn to draw this!  Electrons
flow from the S.H.E to the gas/ion half-cell
(unlike earlier example since reduction takes
place! (Positive Eo value))
Anode: H2  2H+ +2e- (oxidation)
Cathode: F2 + 2e-  2F- (reduction)
F2 (g) + 2e- 2F- (aq) Eo = +2.87 V
c) MEASURING STANDARD ELECTRODE POTENTIAL FOR ION/ION SYSTEM:
You must learn to draw this!  Electrons flow from the S.H.E to the ion/ion half-cell (unlike
earlier example since reduction takes place! (positive Eo value)
Anode: H2  2H+ +2e- (oxidation)
Cathode: Fe3+ + e-  Fe2+ (reduction)
Fe3+ (aq) + e- Fe2+ (aq) Eo = +0.77 V
18.2.5) Information obtained from Standard Electrode Potential, Eo
(pg 12-14)
By convention, redox potentials are written as reduction processes (like how you see them
on your data booklet) The electrode potentials of half cells, E, are known as redox potentials.
Standard electrode potentials (Eo) are relative values since all electrode potentials are
measured wrt the standard hydrogen electrode. The magnitude of Eo measures the
tendency of reduction. The more positive the Eo value, the more likely reduction occurs wrt
the standard hydrogen electrode. For example,
Cu2+ (aq) + 2e- Cu (s) Eo = +0.34V
Reduction of Cu2+  Cu occurs more favourably compared to the reduction of H+  H2.
Hence, reduction will occur in the Cu2+/Cu half cell (CATHODE )and oxidation will occur in
the H+/H2 half-cell (ANODE). Thus, a positive Eo value  position of eqm lies to the right,
while a more negative Eo value  position of eqm lies to the left.
*Note! Multiplying a half-equation by “2” or any other factor will not alter the value of Eo.

Redox Series: Compilation of standard electrode potentials Eo found in the data booklet.
- Species on LHS are reduced in forward reaction, act as oxidizing agents
- Species on RHS are oxidized in backward reaction, act as reducing agents
For series arranged in order of decreasing Eo values, species on LHS at the top are strong
oxidizing agents, those on the RHS at the bottom are strong reducing agents. Therefore,
standard reduction potentials Eo can be used to compare the relative oxidizing/reducing
powers for a given set of species.

Reactivity Series of Metals: Relative reactivity of metals  ease of which metals lose é.
Mn+ (aq) +ne- M (s) Eo
Given Ag+ (+0.80V) to Li+ (-3.04V), reactivity increases from Ag+ to Li+, Eo becomes more
negative and loses electrons more readily, thus forming positive ions more readily. Metal
oxidizes more readily and becomes stronger reducing agents. Thus from this given example,
Li is the strongest reducing agent while Ag is the weakest. Thus given two Eo values, we are
able to predict which redox reactions will occur if we were to connect any two half-cells.
Al3+ (aq) + 3e- Al (s) Eo = -1.66V
Cu2+ (aq) + 2e- Cu (s) Eo = +0.34V
Overall redox reaction: 3Cu2+ (aq) + 2Al (s)  3Cu (s) + 2Al3+ (aq)
Cu2+/Cu half-cell has a more positive Eo value as compared to the Al3+/Al half-cell. Thus, Cu2+
has a greater tendency to be reduced. Al is thus oxidized. Electricity is thus generated and
electrons flow from the Al3+/Al half-cell to the Cu2+/Cu half-cell.

18.2.6) Standard Cell Potential, Ecello (pg 14-18)

When converting chemical energy to electrical energy,
we are making use of the inherent potential difference
between two half-cells. This cell (note, not half-cell) is
known as a VOLTAIC CELL, which are batteries (also
called galvanic/electrochemical cells) since they
convert chemical energy to electrical energy.
 Calculating the Voltaic Cell Potential, Ecello

Standard cell potential (Ecello ): Maximum potential difference between two half-cells
under standard conditions. It gives a measure of the electromotive force (emf) which
“pumps” electrons around the circuit. By convention, oxidation half-cell is placed on the left,
while the reduction half-cell is placed on the right. éflow from anode (ox) to cathode (red)

Ecello = Eocathode - Eoanode

Eocathode = reduction potential of half-cell undergoing reduction.
Eoanode = reduction potential of half-cell undergoing oxidation.
DO NOT change the sign of Eo given in the data booklet.
*IMPORTANT. You’ll be asked questions on voltaic cells: cue half equations, overall reaction,
Ecello value, and finally drawing. Example of question:
Given Zn2+ (aq) + 2e- Zn (s) Eo = -0.76V
Cu2+ (aq) + 2e- Cu (s) Eo = +0.34V
(i) Write equations for reactions at cathode, anode, and the overall cell reaction.
(ii) Calculate the Ecello value
(iii) Draw a labelled diagram for the voltaic cell, showing the direction of electron
flow in the external circuit.
Voltaic Cell Checklist/Comments
 Copy eqns/correct values from data booklet/qn.
Half-cells 2+
Zn (aq) + 2e -
Zn (s) E = -0.76V Note: since Eo of Zn2+/Zn is less positive than Eo of
o

Cu2+ (aq) + 2e- Cu (s) Eo = +0.34V Cu2+/Cu, Cu2+ is more likely to be reduced, and acts as
an oxidizing agent. Hence Zn2+ is oxidized and loses é.
Cathode rxn (red) Cu2+ (aq) + 2e-  Cu (s)  USE FULL ARROWS, not
Anode rxn (ox) Zn (s)  Zn (aq) + 2e
2+

Overall rxn Cu (aq) + Zn (s)  Cu (s) + Zn2+ (aq)

2+
 NO electrons in a balanced redox reaction
o
E cell + 0.34V – (- 0.76V) = + 1.10V  Signs and units
 Voltmeter
 Salt Bridge
 é flow from anode (left) to cathode (right)
 Cathode, anode labelled
 Polarity (+/-) of electrodes labelled
 Temperature, pressure, concentration
(standard conditions) labelled
NOTE: The negative electrode (anode) is the one where
electrons are produced at (oxidation), while the
positive electrode (cathode) is the one where electrons
are absorbed and attracted to. (reduction)
18.2.7) Predicting Spontaneity of a Redox Rxn using Ecello (pg 19-20)
Under standard conditions,
Eocell > 0  reaction is thermodynamically feasible/spontaneous
Eocell = 0  system is in equilibrium, there are no net redox reactions occurring
Eocell < 0  reaction is NOT thermodynamically feasible/spontaneous (but the reverse rxn is)
Consider the following examples: Zn2+ (aq) + 2e- Zn (s) Eo = -0.76V
Cu2+ (aq) + 2e- Cu (s) Eo = +0.34V
Cu2+ & Zn2+  NOT spontaneous, since both are oxidizing agents
Cu & Zn  NOT spontaneous, since both are reducing agents
Cu2+ & Zn  Spontaneous!! :D +0.34V –(- 0.76V) = +1.10V, Eocell > 0
Cu & Zn2+  NOT spontaneous -0.76V – 0.34V = -1.10V, Eocell < 0
When presenting working (recall answering techniques in SPA):
- Write out both half-equations and Eo values
- Circle species given, identify species that will undergo oxidation/reduction
- Calculate Eocell value, check for spontaneity. If spontaneous (>0), give overall eqn.
Eo (Zn2+/Zn) is more positive than Eo (Cu2+/Cu). Also, Eocell = +0.34V –(- 0.76V) = +1.10V > 0.
Hence, reaction is thermodynamically feasible.

18.2.8) Effects of Concentration Changes on Ecello Values (pg 21-22)

Under non-standard conditions,
Eo  Eo where Eo is the electrode potential of a half-cell
where Eo is the standard electrode potential of a half cell.
Since electrode potentials are written as reduction processes, forward is reduction.
Conditions that favour reduction will result in E > Eo
Conditions that favour oxidation will result in E < Eo
Given Fe3+ (aq) +e- Fe2+ (aq), Eo = +0.77V
If the [Fe3+ (aq)] is increased/decreased such that it becomes greater/lesser than 1 moldm-3,
the position of equilibrium will shift to the right/left and E >/< +0.77V (i.e. E >/< Eo)
respectively. The conditions are no longer standard. Adding water to a system with a solid
and a solution will decrease the concentration of ions in the solution to decrease. However
adding water to a system of two solutions will not have any effect as both are diluted to the
same extent. Size of the solid electrode and source of ions (MgO or MgCl2) doesn’t affect.
Similiarly, a voltaic cell under non-standard conditions: Ecell = cell potential = Ecathode - Eanode
Conditions that increase Ecathode OR decrease Eanode will increase Ecell  Ecell > Eocell
Conditions that decrease Ecathode OR increase Eanode will decrease Ecell  Ecell < Eocell

18.2.9) Limitation of Spontaneity Predictions based on Ecello values (pg 22-24)

Non-Standard Conditions
Eocell > 0  might not mean that a reaction will occur
Eocell < 0  might not mean that a reaction will not occur
Given MnO2 + 4H+ + 2e- Mn2+ + 2H2O Eo = +1.23V
Cl2 + 2e- 2Cl- Eo = +1.36V
Hence, MnO2 + 4HCl  2MnCl2 + 2H2O + Cl2 Eocell = +1.23V – (+1.36V) = -0.13V < 0
Assuming under standard conditions, this reaction will NOT occur. However, such a reaction
actually occurs when concentrated HCl is used instead of 1.00 moldm-3 HCl (aq). The
reaction will still proceed despite a negative Eocell, because since conc. HCl is used, [H+] & [Cl-]
will be >> 1moldm-3, E(MnO2/Mn2+) will increase to be > +1.23V, while E(Cl2/Cl-) will decrease
to be < +1.36V. Overall Ecell may be positive, meaning the reaction may be
thermodynamically feasible under non-standard conditions.
Kinetic Factor: High Activation Energy
Eocell is a measure of the position of equilibrium, but gives NO INDICATION OF RATE. Many
reactions have high activation energy, although Eocell >0 and is thermodynamically feasible, it
is so slow (years) that no change is observed. An example is the reaction of H2 & Cu2+ 
since activation energy for reaction is so high, even though the reaction is energetically
feasible, it is kinetically NOT feasible.

Side Reactions Might Occur

Side reactions may make a non-spontaneous reaction become spontaneous!
Given I2 (aq) + 2e- 2I+(aq) Eo = +0.54V
Cu2+ + e- Cu+ Eo = +0.15V
Since Eocell = +0.15V – (+0.54V) = -0.39V < 0 (not thermodynamically feasible)
As Eocell < 0, no reaction is expected. However a reaction actually does occur!!! :O
2Cu2+ (aq) + 4I- (aq)  2CuI (s) + I2 (aq)

A cream ppt (CuI) in brown solution (I2) is observed when blue Cu2+ (aq) is mixed with
colourless I- (aq) as CuI is insoluble. Due to side reaction happening, [Cu2+ (aq)] becomes
VERY LOW, such that Ecathode becomes much larger than +0.15V. Thus, it is possible for Ecell to
be > 0  spontaneous

18.2.10) Batteries & Fuel Cells (pg 24-29)

Batteries consist of 1 or more electrochemical/voltaic cells in which chemical reactions occur
to produce electricity.
Primary Cell: Redox reactions occurring in the cells are irreversible, stored chemical
energy is simply used up. Cannot be recharged as electrodes/electrolyte cannot be restored
to their original states by applying an external current. It provides a low voltage and a very
low current. E.g. common batteries for electrical appliances.

Secondary Cell: Can be recharged by passing a current of electricity from an external

source through the cell. Redox reaction can be reversed, electrical energy from external
source is converted into stored chemical energy, which can be released again when redox
reaction occurs during discharging process.
Fuel Cells : Voltaic cells which converts chemical energy of a continuous supply of rxts
into electrical energy. A fuel is supplied to one electrode, and an oxidant to the other.
ANODE: Fuel (usually hydrogen gas) is oxidized & é are released to the external circuit
CATHODE: Oxidant (usually oxygen gas) is reduced by é received from the external circuit
The most common type of fuel cell is the hydrogen-oxygen fuel cell.

In this cell, there are 3 compartments separated

from one another by porous carbon electrodes. H2
(g) is fed into one component, O2 (g) is fed into
another. These gases diffuse slowly through the
electrodes and react with an alkaline KOH
electrolyte sandwiched between the anode and
cathode. (There is NO NEED to memorize the fuel
cell diagram)
 HYDROGEN-OXYGEN FUEL CELL:
Electrolyte: KOH (aq)
Anode (-): H2 (g) + 2OH- (aq)  2H2O (l) + 2e- (oxidation)
Cathode (+): O2 (g) + 2H2O (l) +4e  4OH (aq)
- -
(reduction)
Overall: 2H2 (g) + O2 (g)  2H2O (l)
Eocell = + 0.40V – (-0.83V) = +1.23V > 0, reaction is thermodynamically feasible.
Advantages Disadvantages
High efficiency of conversion of chemical energy  Expensive (large amts of platinum are required as
electrical energy. catalysts for electrode reactions)
Product of reaction is non-polluting (oxygen and Easily poisoned by CO2 (g) in the air through
water) [water produced is actually safe to drink!] conversion of KOH to K2CO3 which block the pores of
the electrodes  purification of H2 & O2 before
feeding into fuel cell is very costly.
High energy:mass ratio compared to batteries. Able Most fuels require high temperatures to react in a
to attain max power with min weight/volume, impt. fuel cell.
Fuel cells ‘do not go dead’ as reactants are supplied Hydrogen is potentially explosive and difficult to
continuously, products are continually removed. transport.
Improvement of cells in general is sought in terms of smaller size/lower mass/higher voltage/longer
life/greater reliability/quicker recharging/environmentally friendly etc. (electric car and solar cells etc)

B) ELECTROLYSIS
18.3.1) Introduction (pg 30-31)
Electrolysis: Process of passing electricity from an
external source to force a non-spontaneous redox rxn to
occur, by converting electrical energy  chemical energy.
It takes place in a cell called the electrolytic cell.

The electrolytic cell consists of an external source of voltage

(battery), electrodes (anode and cathode), and an
electrolyte (molten or aqueous). During electrolysis, there
are two possibilities for “chemical change”.

(a) Electrolyte: Components/contents are oxidized/reduced

(b) Electrode - Reactive anode is oxidized

Due to the redox processes occurring, some possible physical observations:

- Electrolyte changes colour
- Bubbling at cathode/anode (gas produced)
- Solid metal deposits on the cathode
- Anode decreasing in size and mass (dissolves)

Substances are described as being liberated/discharged during electrolysis

 VOLTAIC CELL ELECTROLYTIC CELL
Spontaneous redox reaction in cell produces Electricity from external sources forces non-spontaneous
electricity. (chemical energy  electrical energy) redox reaction to occur (electrical energy  chemical energy)

No external source External source present as batteries

Salt bridge No salt bridge
Anode (-) : Oxidation Anode (+): Oxidation
Cathode (+) : Reduction Cathode (-): Reduction
Electrons flow from the anode to the cathode (oxidation  reduction)

18.3.2) Factors affecting Selective Discharge of Ions (pg 31-37)

When an electrical potential is applied across the 2 electrodes in an electrolyte cell, not all
species present undergo simultaneous discharge. In fact, the cation or anion that is
discharged is the one that requires the least energy. This is called selective discharge. The
order in which ions are discharged at the electrodes are influenced by 4 main factors:
(a) Molten vs Aqueous Electrolytes
Consider the electrolysis of molten NaCl. Since molten
electrolytes contain only their constituent ions (Na+, Cl-), only
the ions present in the salt will be discharged.

Na+ (cation) migrates to the cathode (-) and is discharged as

Na (l) (reduction takes place)
Cl- (anion) migrates to the anode (+) and is discharged as Cl2 (g)
(oxidation takes place)
Overall redox reaction: 2NaCl (l)  2Na (l) + Cl2 (g)
However, for electrolysis of aqueous electrolytes, in addition to their constituent ions, water
is also present! (Using previous e.g., ions present will be Na+(aq), Cl-(aq), H2O (l)) Thus water
can also be discharged at either the anode or cathode (reduced/oxidized)
Reduction of water at cathode (-): 2H2O + 2e-  H2 + 2OH-
Oxidation of water at anode (+): 2H2O  O2 + 4H+ + 4e-

More than one species can be reduced/oxidized. Which species will be preferentially
discharged at the electrodes will depend on the electrode potentials of the competing
species (which require referring to the Data Booklet)
 (b) Position of Ions in the Redox Series
At the cathode, both Na+ (aq) & H2O (l) molecules are competing to undergo reduction.
Based on Eo values, 2H2O (l) + 2e- (aq) H2 (g) + 2OH- (aq) Eo = -0.83V
Na+ (aq) + e- Na (s) Eo = +1.36V
Since the Eo (H2O/H2) is less negative (more positive) than Eo (Na+/Na), H2O has a greater
tendency to be reduced than Na+ and is thus preferentially discharged. Hence,
Cathode reaction: 2H2O + 2e-  H2 + 2OH-
At the anode, both Cl- (aq) & H2O (l) molecules are competing to undergo oxidation.
Based on Eo values, O2 (g) + 4H+ (aq) + 4e- 2H2O (l) Eo = +1.23V
Cl2 (g) + 2e- 2Cl- (aq) Eo = +1.36V

Since the Eo (O2/H2O) is less positive than Eo (Cl2/Cl-), H2O has a greater tendency to be
oxidized than Na+ and is thus preferentially discharged. Hence,
Anode reaction: 2H2O (l)  O2 (g) + 4H+ (aq) + 4e-
OVERALL REACTION: 2H2O (l)  2H2 (g) + O2 (g)
Hence, electrolysis of NaCl (aq) actually results in the electrolysis of water!!!
(c) Relative Concentrations of the Species
The higher the concentration of any aqueous ion in the electrolyte, the more likely it will be
discharged. This factor often overrides the factor of the “position of the ions” (ion in high
concentration may be discharged even though its Eo value makes it unfavourable) Consider
the electrolysis of brine (conc NaCl):
O2 (g) + 4H+ (aq) + 4e- 2H2O (l) Eo = +1.23V EQUATION 1
Cl2 (g) + 2e- 2Cl- (aq) Eo = +1.36V EQUATION 2
o
Under non-standard conditions, prediction using E values fail. Here, [Cl] is much greater
than [H2O]  position of equilibrium of Cl2 reduction equation shifts to
the left, such that E becomes much less than +1.36V. Thus, Cl- (aq) is
preferentially discharged to form Cl2 (g), as the first equation has a
more positive Eo value than the second equation now.

(d) Active vs Inert Electrodes

Active electrodes are those that participate in the electrolysis reaction.
Consider the electrolysis of CuSO4 using ACTIVE copper electrodes:
At the cathode, both Cu2+ (aq) & H2O (l) molecules are competing to undergo reduction.
Based on Eo values, 2H2O (l) + 2e- (aq) H2 (g) + 2OH- (aq) Eo = -0.83V
Cu2+ (aq) + 2e- Cu (s) Eo = +0.34V
Since the Eo (Cu2+/Cu) is more positive than Eo (H2O/H2), Cu2+ has a greater tendency to be
reduced than H2O and is thus preferentially discharged. Hence,
Cathode reaction: Cu2+ (aq) + 2e-  Cu (s)
At anode: both SO42- (aq), H2O (l) & Cu (from electrode) are competing to undergo oxidation.
Based on Eo values, O2 (g) + 4H+ (aq) + 4e- 2H2O (l) Eo = +1.23V
S2O82- (aq) + 2e- 2SO42- (aq) Eo = +2.01V
Cu2+ (aq) + 2e- Cu (s) Eo = +0.34V
Since the Eo (Cu2+/Cu) is the least positive, Cu has the greatest tendency to be oxidized and
is thus preferentially discharged. Hence, Anode reaction: Cu (s)  Cu2+ (aq) + 2e-
IF INERT electrodes such as graphite are used, then:
- At the cathode, Cu2+ is still preferentially discharged.
- At anode, only SO42- & H2O molecules are competing (no more Cu from Cu electrode)
O2 (g) + 4H+ (aq) + 4e- 2H2O (l) Eo = +1.23V
S2O82- (aq) + 2e- 2SO42- (aq) Eo = +2.01V
Here, since Eo (O2/H2O) is less positive, H2O has a greater tendency to be oxidized and is
thus preferentially discharged. Hence, anode reaction: 2H2O (l)  O2 (g) + 4H+ (aq) + 4e-

18.3.3) Industrial Applications of Electrolysis (pg 38-40)

a) Anodizing of Aluminium
Al (aq) + 3e-
3+
Al (s) Eo = -1.66V
Based on the very negative Eo value, Al
should be highly reactive. However, it is
actually highly corrosion resistant.

This is because upon exposure to air, aluminium acquires a protective layer of aluminium
oxide (Al2O3) which protects the underlying metal from water and any further chemical
attack. However, the layer is not thick enough and can be enhanced through anodizing,
which is the process of coating aluminium objects with aluminium electrolytically.

Electrolyte: dil H2SO4 (aq)

Anode: Aluminium object to be anodized. 2H2O (l) + 2e- (aq) H2 (g) + 2OH- (aq)
Oxygen gas evolved at the anode reacts with the aluminium and the surface oxide layer of
Al2O3 is thickened. 4Al (s) + 3O2  2Al2O3 (s)

Advantages: -Substantial commercial value as aluminium is widely used

- Anodic film is hard, resistant to wear and a good electrical insulator
- Freshly formed film can be dyed to give colour-anodized aluminium
b) Electrolytic Purification of Copper
Copper contains impurities like other metals, which reduce the
electrical conductivity of copper so impure copper must be
purified before being used (electrical wires). The purification of
metals is known as refining.
Electrolyte: CuSO4 (aq)
Cathode: Pure copper, Cu2+ (aq) + 2e-  Cu (s)
Anode: Impure copper to be refined. Cu (s)  Cu2+ (aq) + 2e-
The cell potential is adjusted such that Cu at the anode
dissolves. Over a period of time, the anode dissolves & reddish-
brown copper is deposited on the cathode.

Impurities with Eo value MORE positive than Cu (e.g. Ag)

Ag+ (aq) + e- Ag (s) Eo = +0.80V
Cu2+ (aq) + 2e- Cu (s) Eo = +0.34V
Since the Eo (Cu2+/Cu) is less positive, Cu is preferentially oxidized at the anode. Thus Ag
impurities will not be oxidized and they fall to the bottom as sludge.
 Impurities with Eo value LESS positive than Cu (e.g. Zn)
Zn2+ (aq) + 2e- Zn (s) Eo = -0.76V
Cu2+ (aq) + 2e- Cu (s) Eo = +0.34V
Since Eo (Zn2+/Zn) is less positive, Zn is preferentially oxidized at the anode and goes into the
solution (as Zn2+ ions) first, followed by Cu. However, at the cathode, since Eo (Cu2+/Cu) is
more positive than that of Eo (Zn2+/Zn), Cu2+ is preferentially reduced and deposited on the
pure Cu rod. Zn2+ ions remain at the electrolyte and are not plated onto the cathode.

18.3.4) Faraday’s Law of Electrolysis (pg 40-43)

a) FARADAY’S FIRST LAW
Mass of substance and/or volume of gas liberated during electrolysis is directly proportional
to the amount of charge that passed through the cell. Amount of substance formed is not
dependent on temperature or concentration.

M ∝ Q, where Q = It = amount of charge in coulumbs, C

I = current in amperes, A (Current of 1A passed for 1s = 1C of
t = time in seconds, s electricity passed)
m = mass deposited in grams, g
Cu2+ (aq) + 2e-  Cu (s): Greater quantity of electricity (Q) passed through the cell 
greater amount of é passing through  a greater mass of Cu (s) is deposited. This is
achieved by using a stronger current/ passing current through for a longer duration. ↑ conc
of Cu2+ will not result in a greater mass of Cu (s) deposited within the same duration.
b) FARADAY’S CONSTANT **
1 Faraday F (C mol-1) is the charge carried by 1 mol of electrons.
Where L = Avogadro’s Constant (6.02 x 1023 mol-1)
e = charge on 1 electron (-1.60 x 10-19 C)

F = Le = 6.02 x 1023 x 1.60 x 10-19 = 96500 Cmol-1

Since 1 mol of é carried 96500 C, we can relate the amount of é passed through the circuit
with the total quantity of charge, Q, passed through:

Amount of electrons, ne = Q
96500
mol or Q = neF
c) FARADAY’S SECOND LAW ***** (v impt)
Amt of charge required to discharge 1 mole of an element depends on charge, z, of an ion. In
other words, number of Faradays required to discharge 1 mole of ion at electrode EQUALS
the number of charges on the ion.
To discharge 1 mole of Implications
Na+ requires 1F (96500C) of electricity Na+ + e-  Na (96500C to produce 23.0g of Na)
Mg2+ requires 2F (2 X 96500C) of electricity Mg2+ + 2e-  2Mg (193000C to produce 24.3g of Mg)
Al3+ requires 3F (3 X 96500C) of electricity Al3+ + 3e-  Al (289500C to produce 27.0g of Al)