9.

0 THERMOCHEMISTRY
Concept
of
Enthalpy
Important Terms
 Heat is energy transferred between two
bodies of different temperatures

 System is any specific part of the universe

 Surroundings is everything that lies outside

the system
 Open system is a system that can exchange
mass and energy with its surroundings

 Closed system is a system that allows the

exchange of energy with its surroundings

 Isolated system is a system that does not

allow the exchange of either mass or energy
with its surroundings
 Energy is the ability to do work

 SI unit of energy is kg m2 s-2 or Joule

(J)
 Non SI unit of energy is calorie (Cal)
 1 Cal = 4.184 J
 Thermochemistry
A study of heat change in chemical
reactions.

 Two types of chemical reactions:

 Exothermic

 Endothermic
Exothermic reactions
 Enthalpy of products < Enthalpy of
reactants, ΔH is negative.

 Energy is released from the

system to the surroundings.
 Consider the following reaction:
A (g) + B (g) → C (g) ΔH = ve
(reactants) (product)

reactants
enthalpy
H = -ve

products
Energy profile diagram for exothermic reaction
reaction pathway
 Endothermic Reactions

 Enthalpy of products > enthalpy

of reactants, ΔH is positive

 Energy is absorbed by the

system from the surrounding
 Consider the following reaction
A (g) + B (g) → C(g) ΔH = + ve
(reactants) (product)

Energy profile of diagram endothermic reactions

 Theheat content of a system or total
Enthalpy,
energy in theHsystem

 Enthalpy,
H of a system cannot be measured
when there is a change in the system.

 Example: system undergoes combustion or

ionisation.
Enthalpy of Reaction, ∆H and
Standard Condition
 Enthalpy of reaction:
 The enthalpy change associated with
a chemical reaction.

 Standard enthalpy, ∆Hº

 The enthalpy change for a particular
reaction that occurs at 298K and 1
atm (standard state)
Thermochemical Equation
 The thermochemical equation shows the
enthalpy changes.

Example : H2O(s)→ H2O(l) ΔH=+6.01 kJ

 1 mole of H2O(l) is formed from 1 mole

of H2O(s) at 0°C, ΔH = +6.01 kJ
 However, when 1 mole of H2O(s) is
formed from 1 mole of H2O(l), the
magnitude of ΔH remains the same
with the opposite sign of it.

H2O(l) → H2O(s) ΔH = 6.01 kJ

 Types of Enthalpies
 There are many kind of enthalpies
such as:
 Enthalpy of formation

 Enthalpy of combustion

 Enthalpy of atomisation

 Enthalpy neutralisation

 Enthalpy hydration

 Enthalpy solution
Enthalpy of Formation, ∆Hf
 The change of heat when 1 mole of a
compound is formed from its elements at their
standard states.

H2 (g) + ½ O2(g) → H2O (l) ∆Hf = 286 kJmol1

 The standard enthalpy of formation of any

element in its most stable state form is ZERO.
∆H (O2 ) = 0 ∆H (Cl2) = 0
 Enthalpy of Combustion, ∆Hc
 The heat released when 1 mole of substance
is burned completely in excess oxygen.

C(s) + O2(g) → CO2(g) ∆Hc = 393kJmol1

Enthalpy of Atomisation, Ha
 The heat change when 1 mole of gaseous atoms is
formed from its element

 Ha is always positive because it involves only

breaking of bonds
 e.g:

Na(s)  Na(g) Ha = +109 kJ mol-1

½Cl2(g)  Cl(g) Ha = +123 kJ mol-1

 Enthalpy of Neutralization, ∆Hn
 The heat change when 1 mole of water,
H2O is formed from the neutralization of
acid and base .

 HCl(aq)+ NaOH(aq) → NaCl(aq) +H2O(aq)

ΔHn = 58 kJ mol1
Enthalpy of Hydration, Hhyd

 The heat change when 1 mole of gaseous ions is

hydrated in water.
 e.g:
Na+(g)  Na+(aq) Hhyd = 406 kJ mol-1
Cl-(g)  Cl-(aq) Hhyd = 363 kJ mol-1
Enthalpy of Solution, Hsoln
 The heat change when 1 mole of a
substance is dissolves in water.

e.g:
KCl(s)  K+(aq) + Cl(aq) Hsoln = +690 kJ mol-1
Enthalpy of Sublimation,
Hsubl
The heat change when one mole of a
substance sublimes (solid into gas).

I2 (s) → I2(g) Hsubl = +106 kJ mol1

Calorimetry
 A method used in the laboratory to
measure the heat change of a reaction.

 Apparatus used is known as the calorimeter

 Examples of calorimeter
 Simple calorimeter

 Bomb calorimeter
Simple calorimeter
 The outer Styrofoam cup
insulate the reaction
mixture from the
surroundings (it is
assumed that no heat is
lost to the surroundings)
 Heat release by the
reaction is absorbed by
solution and the
calorimeter
A bomb calorimeter
Specific heat capacity, c
Important Terms
 Specific heat in Calorimeter
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 (Jg 1C1).

 Heat capacity, C
 Heat capacity,C is the amount of heat required

to raise the temperature of a given quantity of

the substance by one degree Celsius (JC1)
Heat released by Heat absorbed
= by calorimeter
substance

q = mc∆T

q = heat released by substance

m= mass of substance
C= specific heat capacity
∆T = temperature change
Basic Principle in Calorimeter
Heat released Heat absorbed
by a reaction = by surroundings

• Surroundings may refer to

the:
i. Calorimeter itself or;
ii. The water and calorimeter
• qreaction= mcΔT or CΔT
Example 1

In an experiment, 0.100 g of H2 and excess of O2

were compressed into a 1.00 L bomb and placed into
a calorimeter with heat capacity of 9.08 x 104
J0C1. The initial temperature of the calorimeter
was 25.0000C and finally it increased to 25.155 0C.
Calculate the amount of heat released in the
reaction to form H2O, expressed in kJ per mole.
Solution
Heat released = Heat absorbed by the
calorimeter

q = C∆T
= (9.08 X 104 J0C-1) X (0.1550C)
= 1.41 X 104 J
= 14.1 kJ

H2(g) + ½O2(g) → H2O(c)

mole of H2 = 0.100
2.016
= 0.0496 mol
moles of H2O = mole of H2

0.0496 mol of H2O released 14.1 kJ energy

14.1
1 mol H2O released = 0.0496 kJ

= 284 kJ
∆Heat of reaction, ∆H = - 284 kJ mol1
Example 2

1. Calculate the amount of heat released in a

reaction in an aluminum calorimeter with a
mass of 3087.0 g and contains 1700.0 mL of
water. The initial temperature of the
calorimeter is 25.0°C and it increased to
27.8°C.
Given:

Specific heat capacity of aluminum = 0.553Jg-1 °C-1

Specific heat capacity of water = 4.18 Jg-1 °C-1

Water density = 1.0 g mL-1

ΔT = (27.8 -25.0 )°C = 2.8°C

Solution

Heat = Heat absorbed + Heat absorbed

released by aluminium by
calorimeter water

q = mwcwΔT + mcccΔT
= (1700.0 g)(4.18 Jg-1 °C-1)(2.8 °C) +

(3087.0 g)(0.553 Jg-1 °C-1)(2.8°C)

= 24676.71 J
= 24.7 kJ
Hess’s Law state that when reactants are
converted
Hess Law to products, the change in
enthalpy is the same whether the reaction
takes place in one step or in the series of
steps.

 The enthalpy change depends only on the

nature of the reactants and products and is
independent of the route taken.
For example:

A H1
B

 
H 2 H 3
C

  
H1  H2  H3
Algebraic Method
Step 1
i.C  O CO H  -393kJmol-1
i. List
(S ) all2the
(g ) thermochemical
2( g ) equations involved
ii.H 1 O H O H  -286kJmol-1
2(g ) 2 2(g ) 2 (g)
iii.C H 7 O  2CO  3H O H  -1560kJmol-1
2 6(g ) 2 2(g ) 2(g ) 2 (g)
Algebraic Method
Step 1
i. List all the thermochemical equations
involved
i.C O  CO H  - 393kJmol- 1
(S) 2( g ) 2( g )
ii.H 1 O H O H  -286kJmol- 1
2( g ) 2 2( g ) 2 ( g)
iii .C H 7 O  2CO  3H O H  -1560kJmol -1

2 6( g ) 2 2( g ) 2( g ) 2 ( g)
ii. Write the enthalpy of formation reaction
for C2H6

H  ?
f
C  3H    C H
( s) 2( g ) 2 6( g )
iii. Add the given reactions so that the
result is the desired reaction.

(i )  2 2C( S )  2O2( g )  2CO2( g ) H1  2  -393 kJ

(ii )  3 3 H 2( g )  3 O2( g )  3 H 2O( g ) H 2  3  -286kJ

2
reverse (iii) 2CO 2(g)  3H 2O( g )  C 2 H 6( g )  7 O2( g ) H3  1560kJ
2
_______________________________________________________________
H f  ?
2C( s )  3 H 2( g )    C 2 H 6( g ) - 84kJ

H f  H1  H 2  H3
 -84kJ
Energy Cycle Method
Draw the energy cycle and apply Hess’s Law to
calculate the unknown value.

HOf
2C (s ) + 3H2 (g) C2H6 (g)

H O2 = 3(-286)
HO1 2O2 (g) 3/2 O2 (g)
7/2 O2 (g)
= 2(-393)
HO3 = - (-1560)

2CO2 (g) + 3H2O (g)

 ° ° ° °
ΔH f = 2( H1 ) + 3(H 2 ) + ΔH3
 -786 - 858  1560
 -84 kJmol - 1
Example 1

The thermochemical equation of combustion of

carbon monoxide is shown as below.
C(s) + ½ O2(g)  CO(g) H  = ?

given :
C(s) + O2(g)  CO2(g) ∆H= -394 kJ mol-
1

CO(s) + ½ O2(g)  CO2(g) ∆H= -283 kJ mol-1

Calculate the enthalpy change of the combustion of
carbon to carbon monoxide.
Example 2

Calculate the standard enthalpy of formation of

methane if the enthalpy of combustion of carbon,
hydrogen and methane are as follows:

∆H [C(s)] = -393 kJ mol-1

∆H [H2(s)] = -293 kJ mol-1

∆H [CH4(s)] = -753 kJ mol-1

Example 3

 Standard enthalpy of formation of ammonia,

hydrogen chloride and ammonium chloride is -46.1 kJ
mol-1, -92.3 kJ mol-1, 314.4 kJ mol-1 respectively.
Write the thermochemical equation for the
formation of each substance and calculate the
enthalpy change for the following reaction.

NH3(g) + HCl (g)  NH4Cl(s)

Exercise
1.Calculate the enthalpy of formation of benzene
if :
H f ∆H (CO2(g) ) = -393.3 kJ mol-1
H f ∆H (H2O(l) ) = -285.5 kJ mol-1
H f ∆H (C6H6(l) ) = -3265.3 kJ mol-1
Born-Haber
Cycle
Lattice Energy, Hlattice
 is the energy required to completely separate one mole of
a solid (ionic compound) into gaseous ions

 e.g:
NaCl(s)  Na+(g) + Cl-(g) Hlattice = +771 kJ mol-1
(lattice dissociation)

Na+(g) + Cl-(g)  NaCl(s) Hlattice = -771 kJ mol-1

(lattice formation)

 The magnitude of lattice energy increases as

 the ionic charges increase

 the ionic radii decrease

 There is a strong attraction between small
ions and highly charged ions so the H is more
negative.

 H for MgO is more negative than H for

Na2O because Mg2+ is smaller in size and has
bigger charge than Na+, therefore
Hºlattice (MgO) > Hºlattice (Na2O)
Hydration Process of Ionic Solid
 Na+ and Cl- ions in the solid crystal are separated
from each other and converted to the gaseous
state (Hlattice)

 The electrostatic forces between gaseous ions and

polar water molecules cause the ions to be
surrounded by water molecules (Hhydr)

Hsoln = Hlattice + Hhdyr

 Na+ and Cl- ion in
the gaseous state

He
r gy a to
n e fH
ic eE yd
tt ra
La tio
n

Heat of Solution

Na+ and Cl- ion in Hydrated Na+ and Cl- ion

the solid state
Born-Haber Cycle

 The process of ionic bond formation occurs in a few

stages. At each stage the enthalpy changes are
considered.
 The Born Haber cycle is often used to calculate the
lattice energy of an ionic compound.
 In the Born-Haber cycle energy diagram, by
convention, positive values are denoted as going
upwards, negative values as going downwards.
 Consider the enthalpy changes in the formation of
sodium chloride.
Example :
Na (s)  1
2 Cl 2(g)  NaCl (s)
 Given;
i. Enthalpy of formation NaCl = -411 kJmol-1
ii. Enthalpy of sublimation of Na = +108 kJmol-1
iii. First ionization energy of Na = +500 kJmol-1
iv. Enthalpy of atomization of Cl = +122 kJmol-1
v. Electron affinity of Cl = -364 kJmol-1
vi. Lattice energy of NaCl = ?
 Example: A Born-Haber cycle for NaCl
energy
Na+(g) + e + Cl(g)

Ionisation Electron Affinity of Cl

Energy of Na
Na+(g) + Cl- (g)
Na(g) + Cl(g)

HaCl
Na(g) + ½ Cl2(g)
+ve Lattice energy
HaNa

Na(s) + ½ Cl2(g) From Hess’s Law:

E=0
Hf = HaNa + HaCl +IENa +
Hf NaCl NaCl

-ve
NaCl(s) EACl + Lattice Energy
Calculation:
H0f  HS  IE Ha ( Cl )  EA  Hlattice

Hlattice  H0f   HS  IE Ha ( Cl )  EA

Hlattice  411 kJ    108 kJ  500 kJ  122 kJ    364 kJ 
Hlattice  777 kJ
 Exercise:
 Construct a Born-Haber cycle to explain why ionic compound NaCl 2 cannot
form under standard conditions. Use the data below:

i. Enthalpy of sublimation of sodium = +108 kJmol-1

ii. First ionization energy of sodium = +500 kJmol-1

iii. Second ionization energy of sodium= +4562 kJmol-1

iv. Enthalpy of atomization of chlorine= +121kJmol -1

v. Electron affinity of chlorine = -364 kJmol-1

vi. Lattice energy of NaCl2 = -2489 kJmol-1