Chemical Energetics

Learning Objectives
To predict the energy changes associated
with chemical processes

Energy

Defined as capacity of matter to do

work.
Can exist in many forms, such as
chemical, electrical, heat, nuclear or
light energy
Matter has potential and kinetic
energy

What is potential energy?

Known as stored energy and is called the
heat content or enthalpy of a substance
Given as symbol H
It is the energy in the object due to its
position
Example:
Gasoline is a source of chemical potential
energy.
It burns when combined with oxygen and
the heat released decreases potential
energy

What is kinetic energy?

Energy that matter possesses due to

its motion
Moving bodies possess kinetic energy

How molecules take up thermal energy?

Temperature is a measure of the average

kinetic energy due to translational motions
of molecules
Vibrational and rotational motions of
molecules can also accept thermal energy
and raise the heat capacity of a substance
Monoatomic species (noble gas elements)
have the lowest heat capacities
Such species do not have vibrational and
rotational motions

Polyatomic molecules have the other

motions which contribute to an
increase heat capacity

Enthalpy (heat capacity)

In chemical reactions the enthalpy

depends on temperature
Every substance has a characteristic
heat capacity and is also known as
specific heat (H)
Specific heat is defined as the
quantity of heat (lost or gained)
required to change the temperature
of 1g of that substance by 1C

The greater the heat capacity of a

substance, the smaller will be the
effect of a given absorption or loss of
heat on its temperature
The relation between mass, specific
heat, temperature change (t) and
quantity of heat lost or gained by a
system is expressed by the equation

(mass of ) (specific heat) t = heat

substance
substance

Example

What is the amount of heat needed to

raise the temperature of 200g of
water by 10C? (specific heat of water
is 4.18 J/gC)

= 200 x 4.18 x 10C = 8.36 x 103 J

Common assumptions for reaction mixtures made up of

aqueous solutions:
density of aqueous solution assumed to be the same as for
water, 1g/mL
eg, 100mL of solution is said to have a mass of 100g
additivity of volumes of reactants is assumed
eg, 100mL of reactant a + 200mL of reactant b = 300mL of
reaction mixture
specific heat capacity of the reaction mixture assumed to be
the same as water,
ie, specific heat capacity = 4.184 JK-1g-1

Energetics of chemical reactions

A zero in enthalpy is when the elements

exist in a stable form at 298K and 1atm
pressure
If enthalpy decreases during a chemical
reaction, a corresponding amount of
energy must be released to the
surroundings.
This can be observed in combustion
reactions
CH4 (g) + 2O2 (g)
CO2(g) + 2H2O(g) +
energy

The release of energy for reactions

like this is represented by the figure
below

The enthalpy difference between the

reactants and products is equal to the
amount of energy released to the
surroundings
Such reactions where energy is
released to the surroundings is known
as an exothermic reaction
The stored potential energy has
become lower for the products than
the reactants

Reactions which absorb energy result

products to have greater enthalpy
than reactants
This can be seen in the reaction
below
4C (s) + 8S(g) + energy
4CS 2 (g)

The enthalpy difference between the

reactants and products is equal to the
amount of energy absorbed from the
surroundings
Such reactions are known as endothermic
reactions
The enthalpy of products is greater then
the reactants
Exothermic reactions release energy
causing the surroundings to heat up
Endothermic reactions absorb energy from
the surroundings, causing the
surroundings to cool down

Describing energy changes in chemical

reactions

H values are negative for exothermic

reactions and positive for endothermic
reactions
In exothermic reactions, final enthalpy is
less than initial enthalpy
In endothermic reactions the final enthalpy
is greater than the initial enthalpy

The sign H reflects the change in

enthalpy of the system
For example
H2O (g)
H2(g) + 1/2O2 (g)
H is +242kJ indicating that 242kJ of
heat are absorbed in the
decomposition of one mole of steam

Sometimes the equation is written as

below:
H2O (g)

H2(g) + 1/2O2 (g) + 242kJ

Note that the quantity of heat is written as

part of the equation.

In the combustion of sulfur,

S (s) + O2 (g)
SO2 (g)

H is -297kJ which indicates that

297kJ of heat are released when one
mole of sulfur reacts with oxygen to
form sulfur dioxide

Enthalpy of formation (Hf o )

The standard enthalpy of formation, Hf o

of a substance is defined as the heat
change required to produce one mol of the
substance from its elements in their
standard states.
e.g. Ag (s) + Cl2 (g) AgCl (s);
Hf o = -127 kJ mol-1
In general, the standard enthalpy change
for any reaction is given by the following
expression

Hfo is the sum of the standard

enthalpies of formation of all
products and reactants.
By definition, the standard enthalpy
(heat) of formation of an element in
its standard state is zero, Hfo = 0.

Calculation:

The heat of formation of CH4(g), CO2(g) and H2O

(l) are -74.8 kJmol-1, -393.5 kJmol-1 and 285.8
kJmol-1 respectively. Calculate the heat change
for the reaction.

Solution:
H for the reaction,

is: H = Hfo(products) -Hfo(reactants)

{Hfo[CO2(g)] + 2 Hfo[H2O(l)]} - {Hfo[CH4(g)] + 2 Hfo[O2(g)]}
Hfo[CO2(g)] = -393.5kJmol-1, Hfo[H2O(l)] = - 285.8kJmol-1
Hfo[CH4(g)] = - 74.8kJmol-1, Hfo[O2(g)] = 0
H = {-393.5 + 2(-285.8)} - {-74.8 + 2 x 0)}
= - 965.1 + 74.8 = - 890.3kJmol-1

Hesss Law
The standard enthalpy of reaction depends only
on the difference between the total standard
enthalpy of the products and the total standard
enthalpy of the reactants. It does not depend on
the route by which the reaction occurs.
In other word, if a reaction can take place by more
than one route, the overall change in the enthalpy
is the same, whichever route is followed.

Question 1:
Given the following information, calculate the enthalpy of
formation of C2H4Cl2(g) in kJ/mol:
2 C(s) + 2 H2(g) + Cl2(g)

C2H4Cl2 (g)

Given:
2 C(s) + 2 H2(g)
C2H4Cl2(g)

C2H4(g); Ho = +52.3 kJ/mol

Cl2(g) + C2H4(g); Ho = +116 kJ/mol

Question 2.
Given the following equations and
Ho values, determine the heat of reaction
(kJ/mol) at 298 K for the reaction:
N2(g) + 1/2 O2(g)

N2O(g)

Given:
2 NH3(g) + 3 N2O(g)

4 N2(g) + 3 H2O(l)
Ho = -1010 kJ/mol

4 NH3(g) + 3 O2 (g)

2 N2(g) + 6 H2O(l)
Ho = -1531 kJ/mol

Question 3.
Calculate Ho/kJmol-1 for the following reaction
using the listed standard enthalpy of reaction data:
3 C2H2 (g)

C6H6 (g)

Given:
C2H2(g)

2 C(s) + H2(g)

Ho = +226.7 kJ/mol
6 C(s) + 3 H2(g)

C6H6(g)

Ho = +82.93 kJ/mol

Question 4.
Given the following equations and Ho values,
determine the heat of reaction at 298 K for the
reaction which occurs in a welder's acetylene
torch:
2 C2H2 (g) + 5 O2 (g)

4 CO2 (g) + 2 H2O (l)

Given:
H2(g) + 1/2 O2(g)

H2O(l)

Ho = -285.8 kJ/mol

2 C(s) + H2(g)

C2H2(g)

Ho = +226.7 kJ/mol

C(s) + O2(g)

CO2(g)

Ho = -393.5 kJ/mol

Enthalpy of combustion (Hc o)

The standard enthalpy of combustion, Hco of

a substance is defined as the heat released
when one mole of a substance is completely
burnt in oxygen in their standard states.

e.g. C2H4 (g) + 3O2 (g) 2CO2 (g) + 2H2O (l);

Hco = -1411 kJ mol-1

Note that the Hco applies to the complete

combustion of the carbon to CO2, not CO.

Hco are always ve as heat is always

released in a combustion process.

The heats of reaction for the formation of some compounds at 25C at 1 atm

Say a chemist is interested to determine

the heat of combustion of propane.
C3H8 (g) + 5O2 (g)

a)

3CO2(g) + 4H2O(g)

From the table, locate equations involving

C3H8, CO2, H2O (g)
3C (s) + 4H2(g)
C3H8 (g) H = -104kJ/mol
C(s) + O2(g)
CO2 (g) H = -394kJ/mol
H2(g) + 1/2O2 (g)
H2O(g) H = -242kJ/mol

b) The equations are rearranged so that C 3H8

appear on left hand side and CO 2, H2O (g)
on right hand side.
The equations are multiplied so that the
coefficients are the same as those in the
overall equation
C3H8 (g)

3C (s) + 4H2(g) H = +104 kJ/mol

3C(s) + 3O2(g)
4H2(g) + 2O2 (g)

3CO2 (g) H = -1182 kJ/mol

4H2O(g) H = -968 kJ/mol

c) Add the equations and the H values

C3H8 (g) + 5O2 (g)
3CO2 (g) + 4H2O (g)
H = -2046 kJ/mol
When you add the equations, the C (s)
and H2 (g) terms cancel out.
Thus the sum of the H values give the
heat of reaction as -2046kJ/mol for the
combustion of one mole of C3H8

a)
b)
c)

This principal of additivity of heats of

reaction is known as Hess Law
Questions:
Calculate the heats of reaction for the
following reactions.
NO (g) + 1/2O2(g)
NO2 (g)
CH4 (g) + 2O2(g)
CO2(g) + 2H2O(g)
SO2(g) + 1/2O2(g) + H2O(l)
H2SO4 (l)

Born-Haber Cycle

An approach in analyzing reaction

energies
The cycle involves the formation of an
ionic compound from the reaction of a
metal (often a Group I or Group II
element) with a non-metal.
Used in calculating lattice enthalpies

What do we mean by lattice enthalpy?

For an ionic compound the lattice
enthalpy (U) is the enthalpy
change when one mole of solid in
its standard state is formed from its
ions in the gaseous state.

The lattice enthalpy cannot be measured

directly and so we make use of other
known enthalpies and link them together
with an enthalpy cycle.
This enthalpy cycle is the Born-Haber cycle.

Born Haber Cycle

Born Haber cycle calculates this lattice

enthalpy through a comparison of the
standard enthalpy of formation of the
ionic compound to the enthalpy
required to make gaseous ions from
the elements.

It is slightly complex as it is required to

atomise elements before it is possible to
make gaseous ions

If the element is a molecule, we have to

consider the bond dissociation enthalpy,
sublimation enthalpy, ionization energy,
lattice energy and electron affinity must
also be considered.

Example

Look at the Born-Haber cycle provided

below. Calculate the enthalpy of formation
for sodium chloride, NaCl
The net energy changes during the formation of sodium
chloride from metallic sodium and chlorine gas can be
represented by Hf

The overall process is thought to take place in following

intermediate steps:

Intermediate steps:
(i) Metallic sodium into gaseous sodium atom
The energy required per mole of sodium is 'enthalpy of sublimation'
which is represented by Hs . This step is energy consuming process.

(ii) Dissociation of chlorine molecule into chlorine atoms

The energy required per mole of chlorine is 'enthalpy of dissociation'
represented by Hd.

(iii) Gaseous sodium atom into gaseous cation

The energy required in this process is called Ionization energy (IE).

(iv) Gaseous chlorine atom into gaseous anion

This step involves the release of energy referred as Electron Affinity
(EA).

(v) Combination of oppositely charged gaseous ions to form solid

crystal
This involves the release of energy referred as lattice energy (U).

The various energy changes in different

steps are as shown below:

Practice

i)

Given below are the reaction energies in the

formation of Zinc sulfide (ZnS).
Calculate the lattice enthalpy for ZnS &
Construct the Born Haber cycle by placing and
labeling the reactions in the cycle.
Zn(g)

Zn2+(g) + 2e-

Zn(s)
S(s)

Zn(g)
S(g)

S(g) + 2eZn2+(g)+S2-(g)
Zn(s)+ S(s)

S2-(g)
ZnS(s)
ZnS(s)

+2680 kJ

+116 kJ

+264 kJ

+246 kJ

= ? kJ

-182 kJ

Practice

i)

Given below are the reaction energies in the

formation of Magnesium Fluoride.
Calculate the lattice enthalpy for the compound
& construct the Born Haber cycle by placing and
labeling the reactions in the cycle.
Hs of Mg

= 146.4 kJ

IE1 and IE2 values of Mg

= 737 and 1449 kJ

Hd of F2

= 158.8 kJ

EA of F

= - 328 kJ

Hf of Magnesium Fluoride = - 1096.5 kJ

Practice

i)

Given below are the reaction energies in the

formation of hypothetical compound ArCl.
Calculate the Hf for the compound &
construct the Born Haber cycle by placing
and labeling the reactions in the cycle.
IE1 of Ar
Hd of Cl2
EA of Cl
Lattice energy (U) of ArCl (s)

= 526.3 kJ
= 243 kJ
= - 349 kJ
= - 703 kJ

Practice
Given below are the reaction energies in the formation of
Lithium Fluoride (LiF).
Construct the Born Haber cycle by placing and labeling
the reactions in the cycle.
Li (g) Li+ (g) + 1e-

Ho = +520 kJ

Li (s) Li (g)

Ho = +161 kJ

F2 (g) 2F (g)

Ho = +159 kJ

F (g) + 1e- F- (g)

Ho = -328 kJ

Li+ (g) + F- (g) LiF (s)

Ho = ? kJ

Li (s) + F2 (g) LiF (s)

H = -617 kJ