Pre U Chemistry

Semester 2

CHAPTER 1:
THERMOCHEMISTRY

1.1
Introduction

Energy is one of the most fundamental parts of our universe. We use
energy to do work. Energy lights our cities. Energy powers our vehicles,
trains, planes and rockets. Energy warms our homes, cooks our food,
plays our music, gives us pictures on television. Energy powers
machinery in factories and tractors on a farm.

According to the conservation of energy law, energy can be neither
created nor destroyed; it can only be converted from one form into
another

From the angle of chemistry, when a chemical reaction occur, energy
changes occur generally in 2 ways, where it can be explained in terms
of kinetic energy and energetic energy. In this chapter, we focus more
on the study of energy changes, in the form of heat, which take place
during a chemical reaction occur, which is well known as
thermochemistry.

In order to understand thermochemistry, we must first understand what
is the difference between system and surrounding. System is the
specific part of substances that involved in chemical and physical
change, while surrounding is defined as the rest of the universe
outside the system.

There are generally 3 types of systems.

Open system

An open system can

exchange mass and
energy, usually in the
form of heat with its
surroundings

Closed system

closed system, which

allows the transfer of
energy (heat) but not
mass.

Isolated system

isolated system, which

does not allow the
transfer of either mass or
energy.

We shall focus more on a closed system throughout our lesson, with the
assumption that energy lost by system in a chemical reaction is the
same with the energy gained by surrounding. In thermochemistry
energy that were gained / lost by system were measured by heat energy.
In the laboratory, heat changes in physical and chemical processes are
measured with a calorimeter, a closed container designed specifically for
this purpose. Our discussion of calorimetry, the measurement of heat
changes, will depend on an understanding of specific heat and heat
capacity,
The specific heat capacity (c) of a substance is the amount of heat
required to raise the temperature of one gram of the substance by one
degree Celsius. It has the units J g-1C-1.
The heat capacity (C) of a substance is the amount of heat required to
raise the temperature of a given quantity of the substance by one degree
Celsius. Its units are J C-1.
Specific heat is an intensive property whereas heat capacity is an
extensive property.
The relationship between the heat capacity and specific heat capacity
of a substance is
C = c x m (mass)

1.2 Enthalpy and Enthalpy Change

Measurement of energy transferred during chemical reaction is made
under control conditions. However, in a closed system, we assume that
theres no changes in the volume of a system, hence no work is done
toward the heat change occur within the system. By that, we shall
deduce the energy transferred in a system is corresponding to the heat
transfer towards the surrounding. Heat transfer in this case is described
as enthalpy, H.
In a chemical reaction, where
reactants
products
The difference of energy changes occur on a chemical reaction is known
as enthalpy change, H, as the difference between the enthalpies of the
products and the enthalpies of the reactants
H = [
Hproduct Hreactant].
Such enthalpy is also known as enthalpy change of reaction
Since the enthalpy changes is a quantitative value use to measure the
difference by the heat given off before and after a reaction, so it may be
a positive value or negative value

Enthalpy heat content of the system

Enthalpy changes ; H ~ heat changes occur
during a chemical reaction.

H = [
Hproduct Hreactant]
Unit = kJ mol-1.

Hproduct > Hreactant

Hproduct < Hreactant

H = positive (+ve)

H = negative (ve)

Endothermic

exothermic

Process
Definition

Energy
profile

Endothermic

Process of heat
absorbed by system
Positive

Exothermic

Process of heat
released by system
Negative

Process

Endothermic

Exothermic

Temperature decrease

Temperature increase

3 STEPS ON CALCULATING
ENTHALPY CHANGE
1

q=mc

mass MV
mol =
or
MR
1000

H =

q
mol

Question 1 : Solution
Equation : Zn (s) + H2SO4 (aq) ZnSO4 (aq) + H2 (g)
Step 1 : q = m c @ q = (25.0) (4.18) (31.5 27.0)
q = 470.25 J

Step 2 : determine limitant

mol of Zn = mass / mol
mol of H2SO4 = MV /1000
= 6.00 / 65.3
= (0.100) (25.0) / 1000
= 0.0919 mol
= 0.00250 mol (lim)
Step 3 : H = q / mol @ H = 470.25 / 0.00250

H = 188 100 J / mol @ 188 kJ / mol

Question 2 : Solution
Equation : Na2SO4 + Ba(NO3)2  2 NaNO3 + BaSO4
Step 1 : q = m c
@ q = (20.0 + 30.0) (4.18) (34.0 30.0)
q = 836 J
Step 2 : determine limitant
mol Na2SO4 = MV /1000 mol Ba(NO3)2 = MV /1000
= (0.500) (20.0) / 1000
= (0.300) (30.0) / 1000
= 0.010 mol
= 0.0090 mol (lim)

Step 3 : H = q / mol @
H = 836 / 0.0090
H = 92889 J / mol  92.9 kJ / mol

Question 3 : Solution
Equation : 2 KI + Pb(NO3)2  2 KNO3 + PbI2
Step 1 : q = m c
@ q = (20 + 30) (4.18) (34 29)
q = 1045 J
Step 2 : determine limitant
mol KI = MV /1000
mol Pb(NO3)2 = MV /1000
= (0.18) (30) / 1000
= (0.15) (20) / 1000
= 0.0054 mol
= 0.0030 mol

*Since 2 mol of KI 1 mol of Pb(NO3)2 ;

KI is limitant
mol of reaction = 0.0027 mol

Step 3 : H = q / mol @
H = 1045 / 0.0027 mol
H = 387037 @ = 390 kJ / mol

Question 4 : Solution
NaCl + AgNO3  NaNO3 + AgCl
Step 3 : From H and mol ; find q
Step 2 :
mol of AgNO3 = MV / 1000 mol of NaCl = MV / 1000
= (1.00)(10.0) / 1000
= (0.800)(15.0) / 1000
= 0.010 mol (lim)
= 0.012 mol
so
q = H x mol @ q = ( 63400) (0.010)
q = 634 J

Step 1 : q = m c @

= q / mc
= 634 / [(4.18) (10.0 + 15.0)
= 6.07 oC

1.2.2 Standard condition for calculating enthalpy changes

The standard conditions of temperature and pressure for
thermochemical measurement are 298 K and 1 atm. Any
enthalpy changes measured under these conditions is
described as standard enthalpy of reaction, and the symbol
is written as H

In this Chapter, there are a total of 9 standard enthalpy
change of reaction that we shall learned through.

There are 3 basic rules applied when thermochemical
equations were used for calculations.

The total amount of energy released or absorbed is directly

proportional to the number of moles of the reactant used. For
example, in the combustion of methane :
CH4 (g) + 2 O2 (g)  CO2 (g) + 2 H2O (l) H = 890 kJ mol-1

If theres 2 mole of methane, CH4 are combusted
2 CH4 (g) + 4 O2 (g)  2 CO2 (g) + 4 H2O (l) H =

The enthalpy change for the reverse reaction is equal in
magnitude but opposite in sign to the enthalpy change for the
forward reaction.
Na+ (g) + Cl (g)  NaCl (s)
H = 770 kJ mol-1

If the reaction is reversed
NaCl (s)  Na+ (g) + Cl (g)
H =

The value of H for a reaction is the same whether it occurs in
one step or a series of steps. This shall be further discussed on the
coming sub-topic about Hess' Law

Enthalpy change of formation, Hf

Energy changes occur when 1 mol of substance is
formed from its individual elements under standard
condition.
E.g. : H2 (g) + O2 (g)  H2O (l)

Note the following important things
 The physical states of the substance involved is
stated accordingly under standard condition
 The Hf of water is not written as H2O (g) as it
is not in gas under standard condition.
 2 H2 (g) + O2 (g)  2 H2O (l) is not consider as
standard as substance formed is not 1 mole.

Hf of pure element is = 0 kJ / mol

Examples
CO2

: C (s) + O2 (g)  CO2 (g)

MgCO3 : Mg (s) + C (s) + 3/2 O2 (g)  MgCO3 (s)

NH3

: N2 (g) + 3/2 H2 (g)  NH3 (g)

NaCl

: Na (s) + Cl2 (g)  NaCl (s)

C6H12O6 : 6 C (s) + 6 H2 (g) + 3 O2 (g)C6H12O6 (s)

SO3

: 1/8 S8 (s) + 3/2 O2 (g)  SO3 (g)

CH3COOH :2C(s) + 2H2(g) + O2(g)CH3COOH (l)

Al2O3

: 2 Al (s) + 3/2 O2 (g)  Al2O3 (s)

Hf and Stability of Compound

Product formed via exothermic process are more
stable than product formed via endothermic process

Example : compare Hf of sodium halide
NaI < NaBr <
NaCl < NaF

Hf more exothermic
Reaction between Na and X2 more vigorous
Stability of compound formed increase
Hrxn of a reaction can be calculated using Hf
Hrxn = Hf (products) Hf (reactants)

Example 5

CO (g) + O2 (g)  CO2 (g)

Hrxn = Hf (products) Hf (reactants)
= (Hf CO2) Hf (CO + O2)
= ( 393 kJ / mol) ( 110 kJ / mol + 0)
= 283 kJ

Example 6

Hrxn

2 FeCl2 (s) + Cl2  2 FeCl3 (s)

= Hf (products) Hf (reactants)
= (2 x Hf FeCl3) Hf (2 FeCl2 + Cl2)
=(2 x 405 kJ / mol) ( 2 x 341 kJ / mol + 0)
= 128 kJ

*Extra Note Cyclohexene, C6H10 contain one carbon carbon

double bond, C=C. When cyclohexene undergoes hydrogenation, the
enthalpy change is 120 kJ / mol.

If a benzene ring (which has 3 C=C), react with hydrogen :

supposedly the enthalpy of hydrogenation must be 3 x -120 = -360 kJ

/ mol. However, when experiment involving hydrogenation is carried
out, the H of benzene is 208 kJ / mol, indicating that benzene
molecule does not contain three double bonds in its structure.
1 mol of benzene is 152 kJ / mol more stable than 1 mole of
cyclohexene.
The more stable the structure, the less heat given out during a
reaction. The real structure of benzene is a resonance hybrid
between the structure above

1.4 Enthalpy change of combustion, Hc

Energy liberated occur when 1 mol of substance is
burned with excess air (oxygen) under standard
condition.
E.g. : CH4 (g) + 2 O2 (g)  CO2 (g) + 2 H2O (l)

Note a few things in the thermochemical equation
above :
 The standard combustion of substance must be 1
mole of the reactant burned. The mole of
oxygen used must be balanced accordingly.
Oxygen is always combust in excess
 For Hc is always exothermic. MAKE SURE
THE MUST BE PLACED.

Examples
C : C (s) + O2 (g)  CO2 (g) [= Hfof CO2]
H2 : H2 (g) + O2 (g)  H2O (l) [= Hfof H2O]
C2H5COOH : C2H5COOH (l) + 7/2 O2 (g) 
3 CO2 (g) + 3 H2O (l)
C2H5OH : C2H5OH (l) + 3 O2 (g)  2 CO2 (g) + 3 H2O (l)
Mg : Mg (s) + O2 (g)  MgO (s)
P
: P4 (s) + 5 O2 (g)  P4O10 (s)
Al : Al (s) + 3/4 O2 (g)  Al2O3 (s)
C6H12O6 : C6H12O6 (s) + 6 O2 (g)  6 CO2 (g) + 6 H2O (l)



Calorimeter ~ instrument used to measure the heat

transferred during a chemical reaction.
Simple calorimeter :

Advantages :
 Simple

to be prepared and set-up

Disadvantages :
 The

experimental value is always lesser than the actual

Hc because of the following reason

Heat is easily lost to surrounding

Combustion of the sample is incomplete

Combustion is not done under standard condition

Example 7

Step 1 : q = m c
@ q = (150) (4.18) (71.0 27.8)
q = 27.1 kJ
Step 2 : calculate the mol of pentane burned
mol = mass / RMM = 4.30 / 72
= 0.0597 mol
Step 3 : H = q / mol @
H = 27.1 kJ / 0.0597 mol
H = 454 kJ / mol

Bomb Calorimeter

Bomb calorimeter consist of a

thick stainless steel pressure
vessel called bomb
Bomb is then sealed after
weighted sample is placed.
A volume of water is added
to ensure the surface is covered
Pure oxygen is pumped into the
valve until 25 atm. initial temperature
is recorded. Temperature of water is
taken from time until it reached maximum temperature. The difference of
temperature is taken as .
 Then, benzoic acid (C6H5COOH) is used to calibrate the instrument to
determine the heat capacity of the instrument.
 Heat capacity ~ heat required to raise the temperature of the whole
apparatus by 1 K
enthalpy change (q )

Heat capacity , C =

temperature change ( )

Steps of calculating Hc using bomb calorimeter

Calibration
Sample
(using benzoic acid)
(burned sample)
mol = mass
RMM

q = H x mol

C=q/

H =

q
mol

mol = mass
RMM

q=C

Example 10 :

H = 16.2 kJ
0.0123
=-1310 kJ/ mol

mol = 0.625
122
= 5.12 x 10-3mol

q = -3230 x 5.12 x
= 16.5 kJ

10-3

C =16.5 / 1.58
= 10.5 kJ / K

mol = 0.712
58
= 0.0123 mol

q = 10.5 x 1.54
= 16.2 kJ

1.5 Hess Law

~ stated that the heat absorbed or liberated during a
chemical reaction, is independent of route by which the
chemical changes occur.

Consider the following equation : A + B  C + D required 2
steps
A+BZ
ZC+D
A

B
HM
Z
HN

Example : In the reaction of formation of SO3, it is a 2 steps reaction.

Step 1 : 1/8 S8 (s) + O2 (g)  SO2 (g)
H1 = 297 kJ / mol
Step 2 : SO2 (g) + O2 (g)  SO3 (g)
H2 = 99 kJ
Overall : 1/8 S8 (s) + 3/2 O2 (g)  SO3 (g)
Hf = 396 kJ / mol

Energy / kJ
1/8 S8 (s) + 3/2 O2 (g)

SO2 (g) + O2 (g)

SO3 (g)

Using Hesss Law, the energy required to form intermediate can

also be determined.

Example : In the reaction of processing ammonia, the equation is
N2 (g) + 3 H2 (g)  2 NH3 (g)
H = 92.2 kJ

The 2 steps involve in the process of forming ammonia
Step 1 : N2 (g) + 2 H2 (g)  N2H4 (g)
H1 = x kJ/mol
Step 2 : N2H4 (g) + H2 (g)  2 NH3 (g)
H2 = 187 kJ / mol
Since Hrxn required is N2 + 2 H2  N2H4
While :
N2 (g) + 3 H2 (g)  2 NH3 (g) H = 92.2 kJ
Eq.2 is reversed 2 NH3 (g)  N2H4 (g) + H2 (g)
H2 = + 187 kJ
N2 (g) + 2 H2 (g)  N2H4 Hf = + 94.8 kJ / mol

Energy / kJ
N2H4 (g) + H2 (g)

N2 (g) + 3 H2 (g)
2 NH3 (g)

Example 9 :
Find H2 (g) + O2 (g)  H2O2 (l)
H2 (g) + O2 (g)  H2O (l)
Hf = - 286 kJ/mol
H2O2 (g)  H2O (l) + O2 (g)
H = - 188 kJ/mol
Reverse equation (2) => equation (3)
H2O (l) + O2 (g)  H2O2 (g) H = +188 kJ
(3)
H2 (g) + O2 (g)  H2O (l) Hf = - 286 kJ/mol
(1)
So, when equation (1) + (3)
H2 (g) + O2 (g)  H2O2 (l)
H = - 98 kJ/mol

(1)
(2)

Energy / kJ
H2 (s) + O2 (g)

H2O2 (l)

H2O (g) + O2 (g)

Example 10 :

From these data,
S(rhombic) + O2(g) SO2(g)
Hrxn = - 296.06 kJ/mol
S(monoclinic) + O2(g) SO2(g) Hrxn = - 296.36 kJ/mol

Calculate the enthalpy change for the transformation
S(rhombic) S(monoclinic)

(Monoclinic and rhombic are different allotropic forms of elemental sulfur.)

Since the equation required is

S(rhombic) S(monoclinic)
Make sure S(rhombic) is at the left while S(monoclinic) is at the right
By reversing eq (2) and compare to eq (1)
S(rhombic) + O2 (g) SO2(g)
Hrxn = - 296.06 kJ/mol
SO2(g) S(monoclinic) + O2 (g) Hrxn = + 296.36 kJ/mol
----------------------------------------------------------------------------------S(rhombic) S(monoclinic)
Hrxn = + 0.30 kJ / mol

Energy / kJ
sulphur (rhombic) + O2 (g)
sulphur (monoclinic) + O2 (g)

SO2 (g)

1.5.3 Relationship between Hc and Hf using Hess Law

For example, in determining the Hf of butane, C4H10. Given the
Hc for C4H10, C and H2 are 2 877 kJ / mol ; 393 kJ / mol
and -296 kJ / mol respectively.

Solution :
C (s) + O2 (g)  CO2 (g) Hc = - 393 kJ / mol .. (1)
H2 (g) + O2 (g)  H2O (l)
Hc = - 286 kJ / mol .. (2)
C4H10 (l) + 13/2 O2 (g)  4 CO2 (g) + 5 H2O (l)
Hc = - 2877 kJ /mol .. (3)
4 C (s) + 5 H2 (g)  C4H10 (l)
Hf = ? kJ / mol \. (4)

Since the equation of formation require 4 C (s) and 5 H2 (g), so
the overall equation for (1) and (2) are multiply by 4 and 5
respectively, where as in equation (3) are reversed.
4 C (s) + 4 O2 (g)  4 CO2 (g)
Hc = 1572 kJ
5 H2 (g) + 5/2 O2 (g)  5 H2O (l) Hc = 1430 kJ
4 CO2 (g) + 5 H2O (l)  C4H10 (l) + 13/2 O2 (g)
Hc = + 2877 kJ
4 C (s) + 5 H2 (g)  C4H10

(l)

Hf = 125 kJ / mol

Energy / kJ
4 C (s) + 5 H2 (g) + 13/2 O2 (g)
C4H10 (l) + 13/2 O2 (g)

4 CO2 (g)

+ 5 H2 (g) + 5/2 O2 (g)

4 CO2 (g) + 5 H2O (l)

Example 11 :
Given Hc of C2H2 and C6H6 are 1300 kJ / mol and 3270
kJ/mol respectively. Find 3 C2H2 (g)  C6H6 (l)
C2H2 (g) + 5/2 O2 (g)  2 CO2 (g) + H2O (l) Hc = 1300 (1)
C6H6 (l) + 15/2 O2(g)  6 CO2(g) + 3 H2O(l) Hc = 3270 (2)
Multiply equation (1) by 3
Reverse equation (2)
3C2H2 (g) + 15/2 O2 (g)  6 CO2 (g) + 3 H2O (l) Hc = 3900
6 CO2(g) + 3 H2O(l)  C6H6 (l) + 15/2 O2 (g) Hc = +3270
3 C2H2  C6H6 (l)

H = 630 kJ

Energy / kJ
3 C2H2 (g) + 15 / 2 O2 (g)
C6H6 (l) + 15/2 O2 (g)

3 H2O (g) + 6 CO2 (g)

Example 12 :
C3H6 (g) + H2 (g)  C3H8 (g)
H = 124 kJ/mol
C3H8(g) + 5 O2(g)  3 CO2(g) + 4 H2O(l) Hc = 2222 kJ/mol
H2 (g) + O2(g)  H2O (l)
Hc = 286 kJ / mol
Find for C3H6(g) + 9/2 O2(g)  3 CO2(g) + 3 H2O(l) Hc = ?
Reverse equation (3)
H2O (l)  H2 (g) + O2(g)
Hc = + 286 kJ / mol
C3H6 (g) + H2 (g)  C3H8 (g)
H = 124 kJ/mol
C3H8(g) + 5 O2(g)  3 CO2(g) + 4 H2O(l) Hc = 2222 kJ/mol
C3H6(g) + 9/2 O2(g)3 CO2(g) + 3 H2O(l) Hc= 2060 kJ/mol

Energy / kJ
C3H6 (g) + H2 (g) + 5 O2 (g)
C3H8 (g) + 5 O2 (g)
C3H6 (g)

+ 9/2 O2 (g) + H2O (l)

3 CO2 (g) + 4 H2O (l)

1.6
Enthalpy change of Neutralisation H neut
~ amount of energy liberated when 1 mol of hydrogen ion from
acid react with 1 mol of hydroxide ion from alkali to form 1
mole of water under standard condition.
Equation : H+ (aq) + OH (aq)  H2O (l)

Hneut for strong acid and strong base under standard
condition is 57.3 kJ / mol.

The value of Hneut will be different with weak acid / base is
used or if the acid used is a polyproctic acid

In laboratory, Hneut can be determine using simple cup
calorimeter (MPM Experiment 6)

The ways of calculating Hneut is still the same as we
learned previously.

Example

Equation : HCl (aq) + NH3 (aq)  NH4Cl (aq)
Step 1 : q = m c @ q = (25.0 + 30.0) (4.18) (31.3 27.6)
q = 850.63 J
Step 2 : determine limitant
mol of HCl = MV / 1000
= (1.00)(25.0)/1000
= 0.025 mol

mol of NH3 = MV /1000

= (0.800)(30.0) / 1000
= 0.024 mol (lim)

Step 3 : H = q / mol @ H = 850.63 / 0.0240

H = 35443 J / mol @ 35.4 kJ / mol

Hneut for weak acid or weak alkali reaction.

If Hneut is 57.3 kJ / mol depend on :

example above, it can be tell that, the Hneut for

weak acid and strong alkali is - 57.3 kJ / mol. This is
due to, some heat is absorbed by CH3COO-H to break the
O-H to form hydrogen ion. Therefore, it is less exothermic
than the expected value.

 the

Basicity of an acid : HCl  H+ + Cl

[monoproctic acid]
H2SO4  2 H+ + SO42- [diproctic acid]
H3PO4  3 H+ + PO43- [triproctic acid]
For example, when NaOH (aq) react with H2SO4 (aq)
Stage 1 :H2SO4 (aq) + NaOH (aq)  NaHSO4 (aq) + H2O (l)
Hneut = 61.95 kJ / mol
Stage 2 : NaHSO4 (aq) + NaOH (aq)  Na2SO4 (aq) + H2O (l)
Hneut = 70.90 kJ / mol
Overall : 2 NaOH (aq) + H2SO4 (aq)  Na2SO4 (aq) + 2 H2O (l)
Hneut = [-61.95 + (-70.90)]= - 132.85 kJ


Reaction involving HF :
HF (aq) + NaOH (aq)  NaF (aq) + H2O (l)
Hneut= 102.4 kJ / mol
The reaction become more exothermic than expected
despite that HF is consider as a weak acid. When HF is
dissolve in water, H-F dissociate in water to form H+ and F-.
The enthalpy of hydration, Hhyd of the fluoride ion is very
exothermic, making the overall process to be much
exothermic
F- (g) + water  F- (aq)
Hhyd = 63.4 kJ/mol

1.6
Standard Enthalpy Change of Atomisation, Hatom

~ energy absorbed when 1 mole of gaseous atoms are formed
from its element under standard condition.
Eq : A (s)  A (g)
Hatom = + ve kJ/mol
Example :
Mg (s)  Mg (g)
P4 (s)  P (g)
Cl2 (g)  Cl (g)

1/8 S (s)  S (g)

CH4 (g)  C (g) + 4 H (g)

PBr3 (s)  P (g) + 3 Br (g)

Since the reaction required the substance involve to become

gaseous atom, so the process involved an endothermic
process.
For a solid, the Hatom involves 2 processes. For example, in
sodium, Na, to become a gaseous sodium, the solid metal
undergoes melting process before vapourising to gas.
Energy required to change 1 mol of solid to liquid is named as
enthalpy change of fusion, while the energy required to change 1
mol of liquid to gas to called as enthalpy change of vapourisation,
according to the following equation



Na (s) Na (l)
Na (l) Na (g)

Na (s)  Na (g)

Hfusion
Hvapourisation

Hatom

Since noble gas exist naturally as monoatom gas the Enthalpy

Change of Atomisation for noble gas 0
As for the Bond enthalpy, it is the energy required to break the bond
between 2 covalently bond atoms.
For example, the bonding enthalpy of chlorine gas
Cl Cl (g)  2 Cl (g)
HBE = + 242 kJ / mol
Compare to the , Hatom of chlorine atom ;
Cl2 (g)  Cl (g)
Hatom = + 121 kJ / mol

1.7
Ionisation energy, HIE
~ energy absorbed when 1 mole of electron is removed from a
gaseous atom under standard condition.
Eq : A (g)  A+ (g) + eHIE = + ve kJ/mol

The process is always endothermic as heat is absorbed to
free one mole of electron from an atom (to overcome the
electrostatic forces of attraction between the nucleus and
outermost electron)

Generally, when goes down to Group, ionisation energy
decrease, while across the Period, ionisation energy
increase. These trend shall be further discussed in Chapter 3

It is believed that, when enormous amount of energies is
supplied, electrons in an atom can be removed completely
from an atom. The energies required to consecutively
remove the electrons from an atom is called as successive
ionisation energies

The total ionisation energy is the sum of all the successive

ionisation of the element involve. Example
1st IE of Al : Al (g)  Al+ (g) + e HIE = + 577 kJ / mol
2nd IE of Al : Al+ (g)  Al2+(g) + e HIE = + 1820 kJ / mol
3rd IE of Al : Al2+ (g)  Al3+(g) + e HIE = + 2740 kJ / mol
Overall : Al (g)  Al3+ (g) + 3e HIE = + 5137 kJ
The information of the 1st until the 4th ionisation energy of
elements can be obtained through Data Booklet supplied
during examination

1.8
Electron Affinity HEA
~ energy liberated when 1 mole of electron is received from gaseous
atom under standard condition.
Eq : O (g) + e-  O (g)
HEA = X kJ / mol

For 1st Electron Affinity, the process is always exothermic, since
upon receive an electron, the energy carries by the electron is
released upon combining with the gaseous atom.

The trend of of 1st electron affinity is the same as in Ionisation
energy, where 1st electron affinity decrease when going down
to group, whereas the 1st electron affinity increase when going
across Period.

However, unlike 2nd ionisation energy, after an atom received an
electron an form negative charged ion, upon receiving the second
electron, a repulsion forces is felt between the anion and electron
receive, due to the mutual charge between both substance.
Hence, for second electron affinity, heat is absorbed
(endothermic) by the anion to overcome the repulsion forces
between the anion and electron.

When forming O2 from O (2nd EA), electron is received by

negative ion.
erepulsion forces formed between anion
and electron received. Heat is absorbed
to overcome the forces of repulsion.
1st EA : O (g) + e  O (g) HEA= 142 kJ / mol
2nd EA : O (g) + e  O2 (g) HEA = + 844 kJ / mol
Overall : O (g) + 2e  O2 (g) HEA = + 702 kJ

1.9
Lattice Energy, HLE

~ energy liberated when 1 mole of solid crystal lattice is
formed from oppositely charged gaseous ions under
standard condition.
Eq : M+ (g) + X (g)  MX (s)
HLE = X kJ/mol

LE always negative (exothermic) : heat is released when
ionic bond is formed.

Examples of writing thermochemical equation :

NaF : Na+ (g) + F- (g)  NaF (s)

MgO : Mg2+ (g) + O2- (g)  MgO (s)
CaCl2 : Ca2+ (g) + 2 Cl- (g)  CaCl2 (s)
K2O : 2 K+ (g) + O2- (g)  K2O (s)
Al2O3 : 2 Al3+ (g) + 3 O2- (g)  Al2O3 (s)
AlN : Al3+ (g) + N3- (g)  AlN (s)

Factors influencing Lattice Energy

i) charge of ion
ii)
inter-ionic distance

Charge of ions (Zn+ . Zn)

Greater the charge ; greater

the forces of attraction ;
greater the value of Lattice
Energy (more exothermic)

Lattice energy

Inter-ionic distance (r+ + r)

Smaller the distance, greater

the attraction forces
between ions, greater the
lattice energy

Z n+ Z n
r+ + r

Compound

Total
charge

Ionic
radius

Compound

Total
charge

Ionic
radius

NaF

0.231

NaCl

0.276

KBr

0.328

KCl

0.314

CaO

0.239

MgO

0.205

Al2O3

0.190

K2O

0.273

The trend of lattice energy of these 8 compounds are

KBr < KCl < NaCl < NaF < K2O < CaO < MgO < Al2O3
Lattice energy increase

1.10 Born Haber Cycle

Lattice energy cannot be determined experimentally. They can
only be obtained by applying Hesss Law in an energy cycle called
Born-Haber Cycle, which is a cycle of reactions used for
calculating the lattice energies of ionic crystalline solids.

There are basically 5 types of Born Haber Cycle which is mostly
tested all times.
i) A+B- ii) A2+B2- iii)
A2+B2- iv) A2+B2- v) A23+B32
To build the Born Haber cycle, students must be able to write
Hf of the compound and HLE.

Here, we are going to build the Born Haber cycle using the 5
examples aboveSodium chloride, NaCl
 Calcium chloride, CaCl2
 Potassium oxide, K2O
 Magnesium oxide, MgO
 Chromium (III) oxide, Cr2O3

Na+ (g) + Cl (g) + eHEA of Cl

Hatom of Cl

Na+ (g) + Cl2 (g) + eNa+ (g) + Cl- (g)

HIE of Na

Na (g) + Cl2 (g)

Hatom of Na

HLEof NaCl

Na (s) + Cl2 (g)

Hf of NaCl

NaCl (s)
Hf = HLE + [Hatom Na + Hatom Cl + H1st IE Na + H1st EA Cl]
HLE = (-411) [(+108) + (+121) + (+494) + (-364)]
= 770 kJ/mol

Ca2+ (g) + 2 Cl (g) + 2 e2 x Hatom of Cl

2 x HEA of Cl

Ca2+ (g) + Cl2 (g) + 2 eH1st IE of Ca +

H2nd IE of Ca

Ca2+ (g) + 2 Cl- (g)

Ca (g) + Cl2 (g)

Hatom of Ca

HLEof CaCl2

Ca (s) + Cl2 (g)

Hf of CaCl2

CaCl2 (s)
Hf = HLE + [Hatom Ca + 2Hatom Cl + H1st IE Ca +
H2nd IE Ca + 2H1st EA Cl]
HLE = (-795) [(+132) + 2(+121) +(+590) +(1150) + 2(-364)]

= 2181 kJ/mol

2 K+ (g) + O2- (g)

H1st EA +
H2nd EA

2 K+ (g) + O (g) + 2 eHatom of O

2 K+ (g) + O2 (g) + 2 e2 X H1st IE of K

HLEof K2O

2 K (g) + O2 (g)
2 X Hatom of K

2 K (s) + O2 (g)
Hf of K2O

K2O (s)
Hf = HLE + [2Hatom K + HBE O + 2H1st IE K +
H1st EA O + H2nd EA O]

HLE = (-362) [2(+129) + (+498) + 2(418) + (-141)+(+844)]

= 2408 kJ/mol

Mg2+ (g) + O2- (g)

H1st EA +
H2nd EA of O

Mg2+ (g) + O (g) + 2 eHatom of O

Mg2+ (g) + O2 (g) + 2 eH1st IE of Mg +

H2nd IE of Mg

HLEof MgO

Mg (g) + O2 (g)
Hatom of Mg

Mg (s) + O2 (g)
Hf of MgO

MgO (s)
Hf = HLE + [Hatom Mg + HBE O +H1st IE Mg +
H2nd IEMg + H1st EA O + H2nd EA O]
HLE = (-612) [(+146) + (+498)+(736) + (1450) + (-141)+(+844)]
= 3896 kJ/mol

2 Cr3+ (g) + 3 O2- (g)

3 x (H1st EA O +
H2nd EA of O)

2 Cr3+ (g) + 3 O (g) + 6 e3 x Hatom of O

2 Cr3+ (g) + 3/2 O2 (g) + 6 e2 x (H1st IE of Cr +

H2nd IE of Cr +
H3rd IE of Cr)

HLEof Cr2O3

2 Cr (g) + 3/2 O2 (g)

2 x Hatom of Cr

2 Cr (s) + 3/2 O2 (g)

Hf of Cr2O3

Cr2O3 (s)
HLE = 16408 kJ/mol

1.12 Enthalpy Change of Hydration, hhyd

In terms of Thermochemistry, the solubility of ionic compound in
water depend on 2 factors
 The enthalpy change of hydration
 Lattice energy of the salt involved

Standard enthalpy change of hydration, Hhyd is

~ energy liberated when one mole of gaseous ion is hydrated by
\\\\\\\\\\\\\\\\\..\\\\\\\\\\\\

water.
\\\\\\\\\\\\\\\\\...under
standard condition.
n+ (g) + water  Mn+ (aq)
M
Hhyd = x kJ/mol
Equation :

Qn- (g) + water  Qn- (aq)

Hhyd = x kJ/mol
Intermolecular forces occur during hydration of ions are ion-dipole
forces, which were stronger than hydrogen bonding. Diagram
below shows the ion-dipole forces between a positively and
negatively charged ion with water respectively.

Since the intermolecular forces between ion and water is

strong, the Hhyd is always exothermic. Similar to lattice
energy, the magnitude of Hhyd depends on 2 factors :
 Charge of ion - Greater the charge of ion, stronger the
attraction between the water and ion, the more exothermic it
is enthalpy change of hydration of ions
 Size of ion - Smaller the size of ion, stronger the attraction
between the ions and water, the more exothermic it is the
enthalpy change of hydration of ions

Mn+

Hhyd for cation increase

Na+ < Mg2+ < Al3+

Qn-

Hhyd for anion increase

l < Br < Cl

1.12 Enthalpy change of solution, Hsoln

Energy change when 1 mole of solute is dissolved in a large
excess water to form an infinite dilute solution.
For ionic substance : MX (s) + water  M+ (aq) + X- (aq)
Some covalent subs : C6H12O6 (s) + water  C6H12O6 (aq)

Hsoln is determined by Hhyd and HLE
HLE :
M+ (g) + X- (g)  MX (s)
[reverse]
Hhyd :
M+ (g) + X- (g) + water  M+ (aq) + X- (aq)
HLE :
MX (s)  M+ (g) + X- (g)
MX (s) + water  M+ (aq) + X- (aq)
As a conclusion, Hsoln = Hhyd + ( HLE)
If Hsoln = - ve, then the salt is soluble in water
If Hsoln = + ve, then the salt is insoluble in water



In the solubility of Group 2 sulphate

both lattice energy and enthalpy change of hydration are
proportional to of the ions. Hence, when going down to Group 2
decrease As the size of
sulphate, both of these energies \\\\\\.
increase
metal ion \\\\\\\\..
Less significant
However, the rate decrease in lattice energy is \\\\\\\\
than the rate of decrease in Hhyd
This is because the size of sulphate ion is much larger than the
size of metal ions, so even though the size of cation increases,
the increase of (r+ + r-) is very small. This makes the lattice energy
changes become less significant when goes down to Group 2.
While in Hhyd it depend on both cation and anion. Since the
Hhyd for anion is constant, so the Hhyd is mainly depend on
the size of cation. When goes down to Group 2, the metal ion size
increase
less
\\\\\\\\\.
, making Hhyd become \\\\\
decrease of the heat become more
exothermic. So, the \\\\\.
significant thus causing the rate of Hhyd is greater than lattice
energy.

Group 2 sulphate

Be SO4

Mg SO4

Ca SO4

Sr SO4

Ba SO4

Hsolution (kJ / mol)

-95.3

-91.2

+ 17.8

+ 18.70

+19.4

Solubility
(g / 100mL)

41.0

36.4

0.21

0.010

0.00025

Hhydration

Hlattice energy

BeSO4

Mg SO4

CaSO4

Sr SO4

BaSO4

Example : Solubility of Group 2 sulphate :

Sr2+
Ba2+

Be2+
Ca2+

Mg2+

SO42-