CHM 111

LECTURE NOTE ON THERMOCHEMISTRY

LECTURER : Dr. G. O. ORODEPO

CHEMISTRY DEPARTMENT, UNIMED, ONDO

E-mail address: [email protected]; [email protected]

 OBJECTIVES
At the end of the lecture, the students should be able to:

(i) define terms such as thermochemistry, system, surroundings and universe

(ii) differentiate between change in internal energy and enthalpy of a system

(iii) define various enthalpies of physical changes and solve calculations on them

(iv) define different enthalpies of chemical changes and provide solutions to problems
on them

(v) write and apply Kirchhoff’s law to solve any given problem

(vi) state and apply Hess’s law and Born-Haber cycle to solve relevant questions

(vii) estimate bond energy of any given bond in a molecule

 THERMOCHEMISTRY
▪ Thermochemistry is the study of heat changes which accompany chemical reactions and
physical transitions

▪ During a chemical reaction, the reaction vessel and its contents constitute a system, and the
vicinity of the reaction forms the surroundings.

▪ The universe is the sum of the system and its surroundings

i.e universe = system + surroundings

▪ Heat is defined as the energy which flows into or out of a system due to the temperature
difference between the system and its surroundings.

▪ Calorimetry is the process of measuring the heat transfer between a system and its surroundings

▪ The amount of energy absorbed or released as heat by a reaction, represented as q, is the

change in internal energy (∆U) of the system if the reaction occurs at constant volume or a
change in enthalpy (∆H) if the reaction occurs at constant pressure
▪ The capacity of a system to do work i. e its total store of energy is referred to as its internal
energy, U

▪ It is impossible to measure the absolute value of the internal energy of a system, as this
include the energies of all the atoms, their electrons, and the components of their nuclei.
Hence, we can only measure the changes in the internal energy, ∆U

▪ When a system does work on the surroundings, its internal energy decreases by the
amount of work done; when work is done on the system, its internal energy increases
accordingly.

▪ When a system loses heat to the surroundings, the reaction is termed exothermic and the
∆H is negative since there is a decrease in the enthalpy of the system.

▪ A system which absorbs heat from the surroundings is referred to as endothermic and the
∆H is positive as this leads to increase in the enthalpy of the system

exothermic process: ∆H < 0 ; endothermic process: ∆H > 0

 Relationship between ∆H and ∆U
▪ Recall that q = ∆U (at constant volume) or ∆H (at constant pressure)

▪ For reactions that produce gases, ∆H = ∆U + ∆ngasRT (assuming ideal gas behavior)
where ∆ngas is the change in the amount of gas molecules in the reaction (ng(product) – ng(reactant))

▪ For reactions with no change in the amount of gas, ∆H = ∆U

Example 1:
A constant-volume calorimeter showed that the heat generated by the combustion of glucose
is as given below:
C6H12O6(s) + 6O2(g) ⇾ 6CO2(g) + 6H2O(g) is 2559 KJ at 298 K. (i.e ∆U = -2559 KJ)
What is the change in enthalpy for the same reaction?

Solution:
∆ngas = [(6 + 6) – 6] = 12 – 6 = 6 mol

∆H = ∆U + ∆ngasRT
∆H = -2559 x 103 J + [(6 mol) x (8.314 JK-1mol-1) x (298 K)]
∆H = -2559 x 103 J + 14.865 x 103 J
= -2544.135 KJ
⸫ ∆H = -2544 KJ
 STANDARD ENTHALPY CHANGES

▪ The standard enthalpy change, ∆Hᶱ, is the change in enthalpy for a process in which the
initial and the final substances are in their standard states

▪ The standard state of a substance at a specified temperature is its pure form at 1 bar or 1
atmosphere

▪ The standard enthalpy change for a reaction or a physical process is the difference between
the enthalpies of products in their standard states and the enthalpies of reactants in their
standard states, all at the same specified temperature
i.e ∆reaction H = Σ 𝑛 𝐻𝑝 − Σ 𝑚 𝐻𝑟 ……………………………………………..(1)
where Σ represents summation
n and m are the coefficients of the substances in the products and reactants,
respectively
Hp and Hr are the enthalpies of products and reactants, respectively

▪ The conventional temperature for reporting thermodynamic data is 25 ᵒC (298.15 K)

▪ A thermochemical equation is one in which the value of the enthalpy change of the reaction
is given along with the reaction. For example,
CH4(g) + 2O2(g) ⇾ CO2(g) + 2H2O(l) : ∆H = -890 KJmol-1
(a) Enthalpies of physical change
This is the enthalpy change that accompanies the transition of a substance or molecule from one
physical state to another. For example the standard enthalpy of vaporization and fusion of
water, are as shown below
H20(l) ⇾ H20(g) ∆vap Hᶱ(373 K) = +40.66 KJmol-1
Endothermic process
H20(s) ⇾ H20(l) ∆fus Hᶱ(273 K) = +6.01 KJmol-1

The enthalpy of freezing is the change in molar enthalpy when a liquid solidifies (Aliq. ⇾ Asol.)
Phase changes that increase molecular contact, such as freezing, are exothermic because
energy is given off when attractions form between molecules.

The enthalpy of freezing of a substance is the negative of its enthalpy of fusion. In general,
the enthalpy change for the reverse of any process is the negative of the enthalpy change for the
original process i.e ∆Hreverse process = - ∆Hforward process

The enthalpy change for a reverse process has the same value but the
opposite sign of the enthalpy change for the forward process at the same
temperature
 Sublimation is the direct conversion of a solid into its vapor, (Asolid ⇾ Avapor). The enthalpy
change associated with this process is called the enthalpy of sublimation, ∆subHᶱ.

Since enthalpy is a state function, the enthalpy of sublimation of a substance is equal to the sum
of the enthalpies of fusion and vaporization, provided they are measured at the same temperature
i. e ∆subHᶱ = ∆vapHᶱ + ∆fusHᶱ

Example 2: The enthalpy of fusion of sodium metal is 2.6 KJmol-1 at 25 oC, and the enthalpy of
sublimation of solid sodium at that temperature is 101 KJmol-1. What is the enthalpy of
vaporization of sodium at 25 oC?
Solution: Recall ∆subH = ∆vapH + ∆fusH
101 KJmol-1 = ∆vapH + 2.6 KJmol-1 ⇒ ∆vapH = (101 - 2.6) KJmol-1 = 98.4 KJmol-1
(b) Enthalpies of chemical change

(i) Standard Enthalpy of Formation, ∆f Hᶱ: This is the enthalpy change when one mole of a
compound is formed from its constituent elements in their standard states at 298 K and 1
atmospheric pressure. For example,
H2(g) + 1/2O2(g) ⇾ H20(l) ∆f Hᶱ, [H20(l)] = -285.9 KJmol-1

C(s) + 2H2(g) ⇾ CH4(g) ∆f Hᶱ, [CH4(g)] = -74.9 KJmol-1

NB: The standard enthalpy change of formation of an element in its standard states is zero, For
example,
∆f Hᶱ(O2(g)) = ∆f Hᶱ(H2(g)) = ∆f Hᶱ(C(s, graphite)) = 0

(ii) Standard Enthalpy of Combustion, ∆c Hᶱ: This is the enthalpy change when one mole of a
substance is completely burnt in oxygen under standard temperature (298 K) and pressure (1
atmosphere). For example,
C2H6(g) + 7/2O2(g) ⇾ 2CO2(g) + 3H2O(l) ∆c Hᶱ, [C2H6(g)] = -1559.5 KJmol-1

(iii) Standard Enthalpy of Atomization of an Element, ∆atomHᶱ: This occurs when one mole of
a gaseous atom is formed from the element in its physical state under standard conditions of
temperature (298 K) and pressure (1 atmosphere). For example,
1/2H2(g) ⇾ H(g) ∆atom.Hᶱ, [1/2H2(g)] = +218 KJmol-1
(iv) Standard Enthalpy of Atomization of a Compound, ∆atom Hᶱ: This is the enthalpy change
when one mole of the compound is converted into gaseous atoms under standard conditions of
temperature (298 K) and pressure (1 atmosphere). For example,
CH4(g) ⇾ C(g) + 4H(g) ∆atom.Hᶱ, [CH4(g)] = +1662 KJmol-1

(v) Standard Enthalpy of Neutralization, ∆neut.Hᶱ: This occurs when one mole of hydrogen ion
(from an acid) is just neutralized by a base in dilute aqueous solution under standard conditions
of temperature (298 K) and pressure (1 atmosphere). For example,
HCl(aq.) + NaOH(aq.) ⇾ NaOH(aq.) + H2O(l), ∆neut.Hᶱ = -57.3 KJmol-1

(vi) Standard Enthalpy of Reaction, ∆reactionHᶱ: This is the enthalpy change when the number of
moles of reactants as indicated in the balanced equation react together under standard conditions
of temperature (298 K) and 1 atmospheric pressure.

Generally, the enthalpy change for a reaction can be calculated using the equation below:
∆reactionHᶱ = Σ 𝑛 ∆𝑓𝐻ᶱ(𝑝𝑟𝑜𝑑𝑢𝑐𝑡𝑠) − Σ 𝑚 ∆𝑓𝐻ᶱ(𝑟𝑒𝑎𝑐𝑡𝑎𝑛𝑡𝑠)

where n and m are the coefficients of the substances in the products and reactants, respectively.
∆𝑓𝐻ᶱ is the standard enthalpy of formation of the substance
 Worked Examples
Example 3:
Calculate the amount of heat evolved when 300 kg of ammonia is produced according to the
following equation:

N2(g) + 3H2(g) ⇾ 2NH3(g) ; ∆reactionH = -91.8 KJ

[N = 14.00, H = 1.00 gmol-1]

Solution:

Number of moles of ammonia produced, nNH3 = mass of ammonia given/molar mass of NH3
Molar mass of NH3 = [(1x14) + (3x1)] = 17 gmol-1
Mass of ammonia given = 300 kg = 300 x 103 g
⸫ nNH3 = 300 x 103 g / 17 gmol-1 = 1.77 x 104 mol

From the balanced equation,

2 moles of NH3 liberated 91.8 KJ of heat
91.8 KJ
⸫ 1.77 x 104 mol of NH3 will liberate x 1.77 x 104 mol = 8.12 x 105 KJ
2 mol
(∆H = -8.12 x 105 KJ)
Example 4:
Nitroglycerine, C3H5(NO3)3, is a common explosive, which decomposes according to the
following chemical equation:

4C3H5(NO3)3(l) ⇾ 12CO2(g) + 10H2O(g) + O2(g) + 6N2(g) ∆reactionH = -5.72 x 103 KJ

Calculate the heat for the decomposition of 10.6 g of nitroglycerine

Solution:
No of moles of nitroglycerine produced, nC = mass given/molar mass of C3H5(NO3)3
3H5(NO3)3

Molar mass of C3H5(NO3)3 = [(3x12) + (1x5) + (3x14) + (9x16)] = 227 gmol-1

Mass of nitroglycerine given = 10.6 g

nC = 10.6 g / 227 gmol-1 = 4.67 x 10-2 mol

3H5(NO3)3

From the balanced equation,

4 moles of C3H5(NO3)3 liberated 5.72 x 103 KJ of heat

5.72 x 103 KJ
⸫ 4.67 x 10-2
mol of C3H5(NO3)3 will liberate x 4.67 x 10-2 mol = 66.78 KJ
4 mol
(∆H = -66.78 KJ)
Example 5:
Calculate the heat of formation of methane, given its heat of combustion as -891 KJmol-1 and the
heats of formation of carbon(IV)oxide and water are -394 KJmol-1 and -286 KJmol-1,
respectively.

Solution:
The chemical equation for the combustion of methane is given as follows:
CH4(g) + 2O2(g) ⇾ CO2(g) + 2H2O(g) ∆c H = -891 KJmol-1

∆reactionHᶱ = Σ 𝑛 ∆𝑓𝐻ᶱ(𝑝𝑟𝑜𝑑𝑢𝑐𝑡𝑠) − Σ 𝑚 ∆𝑓𝐻ᶱ(𝑟𝑒𝑎𝑐𝑡𝑎𝑛𝑡𝑠)

∆reactionHᶱ = ∆c Hᶱ = [∆f Hᶱ(CO2) + 2∆f Hᶱ(H2O)] – [∆f Hᶱ(CH4) + 2∆f Hᶱ(O2)]

-891 KJmol-1 = [-394 KJmol-1 + 2(-286) KJmol-1] – [∆f Hᶱ(CH4) + 0]

-891 = -394 - 572 - ∆f Hᶱ(CH4)

-891 = -966 - ∆f Hᶱ(CH4)

⸫ ∆f Hᶱ(CH4) = -966 KJmol-1 + 891 KJmol-1 = -75 KJmol-1

Example 6:
Given the following chemical reactions and their respective enthalpy changes:

C2H2(g) + 5/2O2(g) ⇾ 2CO2(g) + H2O(g) ∆c Hᶱ = -1299.6 KJmol-1

C(s) + O2(g) ⇾ CO2(g) ; ∆f Hᶱ = -393 KJmol-1
H2(g) + 1/2O2(g) ⇾ H2O(l) ; ∆f Hᶱ = -285.9 KJmol-1

Calculate ∆Hᶱ for the reaction; 2C(s) + H2(g) ⇾ C2H2(g)

Solution:
From the combustion reaction given above;
∆reactionHᶱ = Σ 𝑛 ∆𝑓𝐻ᶱ(𝑝𝑟𝑜𝑑𝑢𝑐𝑡𝑠) − Σ 𝑚 ∆𝑓𝐻ᶱ(𝑟𝑒𝑎𝑐𝑡𝑎𝑛𝑡𝑠)

∆reactionHᶱ = ∆c Hᶱ = [2∆f Hᶱ(CO2) + ∆f Hᶱ(H2O)] – [∆f Hᶱ(C2H2) + 5/2∆f Hᶱ(O2)]

-1299.6 KJmol-1 = [2(-393) KJmol-1 + (-285.9) KJmol-1] – [∆f Hᶱ(C2H2) + 5/2(0)]

-1299.6 = -786 - 285.9 - ∆f Hᶱ(C2H2) - 0

-1299.6 = -1071.9 - ∆f Hᶱ(C2H2)
⸫ ∆f Hᶱ(C2H2) = -1071.9 + 1299.6 = +227.7 KJmol-1

Hence the standard heat of formation of C2H2 from its constituent elements is 227.7 KJmol-1
 TEMPERATURE DEPENDENCE OF REACTION ENTHALPIES

▪ The temperature dependence of reaction enthalpy is expressed by Kirchhoff’s law

▪ When a substance is heated from T1 to T2, its enthalpy changes from H(T1) to
T
H(T2) = H(T1) + ‫׬‬T 2 𝐶𝑝𝑑𝑇……………………………………………(2)
1

▪ It is assumed that no phase transition takes place in the temperature range of interest. Since eq.
(2) applies to each substance in the reaction, the standard reaction enthalpy changes from
∆rHᶱ(T1) to
T
∆rHᶱ(T2) = ∆rHᶱ(T1) + ‫׬‬T 2 ∆r𝐶𝑝ᶱ𝑑𝑇…………………………………..(3) Kirchhoff’s law
1
where ∆r𝐶𝑝ᶱ is the difference of the molar heat capacities of products and reactants under
standard conditions weighted by the stoichiometric coefficients that appear in the chemical
equation:

∆r𝐶𝑝ᶱ = Σ v𝐶𝑝ᶱ (𝑝𝑟𝑜𝑑𝑢𝑐𝑡𝑠) - Σ v𝐶𝑝ᶱ(𝑟𝑒𝑎𝑐𝑡𝑎𝑛𝑡𝑠) … … … … . (4)

[∆r𝐶𝑝ᶱ is assumed to be independent of temperature]

 Example 7:
The standard enthalpy of formation of H2O(g) at 298 K (25 oC) is -241.82 KJ mol-1. Estimate its
value at 100 oC given the following values of the molar heat capacities at constant pressure:
Species Cpᶱ / J K-1mol-1
H2O(g) 33.58
H2(g) 28.82
O2(g) 29.36
Assume that the heat capacities are independent of temperature

Solution:
When ∆𝐶𝑝ᶱ is independent of temperature in the range T1 to T2 , the integral in eq. (3) becomes
(T2 – T1)∆r𝐶𝑝ᶱ
⸫ ∆rHᶱ(T2) = ∆rHᶱ(T1) + (T2 – T1)∆r𝐶𝑝ᶱ
We need to write the chemical equation, identify the stoichiometric coefficients and calculate
∆r𝐶𝑝ᶱ
The reaction is H2(g) + 1/2O2(g) ⇾ H2O(g)

∆r𝐶𝑝ᶱ = 𝐶𝑝ᶱ (H2O, g) – [𝐶𝑝ᶱ (H2, g) + ½ 𝐶𝑝ᶱ (O2, g) ]

= 33.58 – [28.82 + 1/2(29.36)] = 33.58 – 43.5 = -9.92 J K-1mol-1

⸫ ∆rHᶱ(373 K) = ∆rHᶱ(298 K) + (373 K – 298 K)∆r𝐶𝑝ᶱ

= -241.82 KJ mol-1 + (75 K)(-9.92 J K-1mol-1 )
= -241820 J mol-1 - 744 J mol-1
= -242,564 J mol-1 = -242.56 KJ mol-1
 Hess’s Law of Constant Heat Summation
▪ Hess’s law states that the standard enthalpy of an overall reaction is the sum of the standard
enthalpies of the individual reactions into which a reaction may be divided. This law is a
consequence of the fact that enthalpy is a state function, so that its change is path-independent.
(A state function is a property that depends only on the current state of the system and is independent of
how that state was prepared. Examples include pressure, volume, temperature and density of a system)

▪ Hess’s law is useful in the calculation of ∆H values of reactions which may be difficult to
determine directly

CO + 1/2O2

Q1 = q1 + q2 + q3

▪ To apply Hess’s law in solving problems, we need to be able to assemble the required equation
from the given equations, by addition or subtraction and do the same mathematical operation
with their ∆Hs.
Example 8:
Calculate the heat of formation of potassium hydroxide from the following data:
(i) K(s) + H2O(l) ⇾ KOH(aq.) + 1/2H2(g) ∆H = -48.0 KCal
(ii) H2(g) + 1/2O2(g) ⇾ H2O(l) ∆H = -68.5 KCal
(iii) KOH(s) ⇾ KOH(aq.) ∆H = -14.0 KCal

Solution:
The required equation is given by;
K(s) + 1/2O2(g) + 1/2H2(g) ⇾ KOH(s) ∆H = ?

Adding equations (i) and (ii) and subtracting (iii) gives;

K(s) + H2O(l) + H2(g) + 1/2O2(g) - KOH(s) ⇾ KOH(aq.) + 1/2H2(g) + H2O(l) - KOH(aq.)

K(s) + H2(g) - 1/2H2(g) + 1/2O2(g) ⇾ KOH(s) ; ∆H = -48.0 + (-68.5) – (-14.0) = -102.5 KCal

K(s) + 1/2H2(g) + 1/2O2(g) ⇾ KOH(s) ; ∆H = -102.5 KCal

⸫ The heat of formation of KOH from its constituent elements is -102.5 KCal
 Example 9:
Given the following thermochemical equations:
(i) CH2= CHCH3(g) + H2(g) ⇾ CH3CH2CH3(g) ∆H = -124 KJmol-1 (Hydrogenation of propene)
(ii) CH3CH2CH3(g) + 5O2(g) ⇾ 3CO2(g) + 4H2O(l) ∆H = -2220 KJmol-1 (Combustion of propane)
(iii) H2(g) + 1/2O2(g) ⇾ H2O(l) ∆H = -286 KJmol-1 (Formation of water)

Calculate the standard enthalpy of combustion of propene.

Solution:
The required combustion reaction is given by:
C3H6(g) + 9/2O2(g) ⇾ 3CO2(g) + 3H2O(l) ∆H = ?

This equation can be obtained by adding (i) and (ii) and subtracting (iii) from the resultant
equation:

C3H6(g) + H2(g) + C3H8(g) + 5O2(g) – H2(g) – 1/2O2(g) ⇾ C3H8(g) + 3CO2(g) + 4H2O(l) –H2O(l)

C3H6(g) + 9/2O2(g) ⇾ 3CO2(g) + 3H2O(l) ∆cH= [-124 + (-2220) – (-286)] = -2058 KJmol-1

⸫ The standard enthalpy of combustion of propene is -2058 KJmol-1

 Born-Haber Cycle
▪ The lattice energy , ∆HL , is the enthalpy change when one mole of an ionic compound is formed from its
constituent ions in the gaseous state. For example,
Na+(g) + Cl-(g) ⇾ NaCl(s) ∆HL = Lattice energy

▪ Lattice energies are difficult to determine experimentally, hence they are calculated by means of an
energy cycle called Born-Haber cycle. A closed path of transformations starting and ending at the same
point, one step of which is the formation of the solid compound from a gas of widely separated ions

▪ Lattice energies calculation embodies the principle of Hess’s law

▪ For example, consider NaCl,

where
∆HS = Sublimation energy Na+(g) + Cl-(g)
∆HD = Heat of dissociation of Cl2(g)
I. E = Ionization energy i.e energy required to
remove one mole of electron from a mole of an I. E E. A
atom in the gaseous state to form an ion of the atom ∆HL
Na(g) Cl(g)
E. A = Electron affinity i.e energy released when an
electron is added to a substance in a gaseous state
∆Hs ∆Hatom.
∆HL = Change in lattice energy i.e energy involved
when ions are completely separated in the gas state (or 1/2∆HD)
and are allowed to combine to form ionic solid Na(s) + 1/2Cl2(g) NaCl(s)
∆fHᶱ = Change in enthalpy of formation i.e ∆fHᶱ
energy involved when solid NaCl is formed from
its constituent elements in their standard states
 Using Hess’s law:
∆f Hᶱ = ∆HS + I. E + ∆HD + E. A + ∆HL ………………………………….(5)

For NaCl:
Na(s) ⇾ Na(g) ; ∆Hs = 109 KJmol-1
1/2Cl2(g) ⇾ Cl(g) ; 1/2∆HD = 121 KJmol-1
Na(g) ⇾ Na+ + e- ; I. E = 494 KJmol-1
Cl(g) + e- ⇾ Cl- ; E. A = -364 KJmol-1
Na(s) + 1/2Cl2(g) ⇾ NaCl(s) ; ∆f Hᶱ = -411 KJmol-1

From equation (5);

∆HL = ∆f Hᶱ - ∆HS - I. E - 1/2∆HD - E. A
= - 411-109- 494 - 121- (-364)
∆HL = - 771 KJmol-1

▪ Lattice energy is an important factor controlling whether a bond is ionic or covalent

▪ Lattice energy increases with increasing charges on the cation or anion and decreasing
distance between anion and cation
▪ A high lattice energy generally means that a salt will have a high melting point, and hence
ionic and vice-versa
 Bond Energy
▪ The bond energy is the average enthalpy change for the breaking of A-B bond in a molecule in
the gas phase
▪ For example, the value of the C-H bond energy (or B. E(C-H)) in methane can be obtained from
the experimentally determined enthalpy change for breaking of all its C-H bonds
CH4(g) ⇾ C(g) + 4H(g); ∆Hatom. = 1662 KJmol-1

Since 4 C-H bonds are broken; the average value for 1 C-H bond is obtained as:
∆H 1662
Average C-H bond energy = 4atom. = 4 = 415.5 KJmol-1

▪ The C-C bond energy can be determined in a similar manner; for example, in ethane, C2H6
C2H6(g) ⇾ 2C(g) + 6H(g); ∆Hatom. = +2822.7 KJmol-1

If B. E(C-H) = 415.5 KJmol-1 and ethane is made up of 1 C-C and 6 C-H bonds, then

the C-C bond energy is obtained as:

C-C bond energy = ∆Hatom. - 6 C-H bond energy
= 2822.7 – 6(415.5)
= 329.7 KJmol-1

NB: The average bond energies determined in this manner are approximately additive and can be
used to estimate heats of chemical reactions or enthalpy changes (i.e ∆H) accompanying gaseous
chemical reactions
▪ If the bonds being formed in a chemical reaction are stronger than those being broken,
then energy will be liberated and the reaction is exothermic

▪ In an endothermic reaction, the bonds formed are weaker than those being broken

▪ When bonds are broken, the standard enthalpy is positive, i.e ∆Hᶱ is +ve

▪ When bonds are formed, the standard enthalpy is negative, i.e ∆Hᶱ is –ve

▪ The enthalpy change of a chemical reaction is:

∆reactionHᶱ = Σ ∆bond formedHᶱ + Σ ∆bond brokenHᶱ …………………………….(6)

▪ Since bonds are formed in the products and bonds are broken in the reactants, then

∆reactionHᶱ = Σ n B. E(reactants) - Σ m B. E(products) ……………………………(7)

n and m are the number of bonds broken and formed in the reactants and products, respectively
Example 10:
Given below is a list of bond enthalpies at 298 K
Bond ∆Hᶱe / KJmol-1
C-C +348
C=C +612
H-H +436
C-H +412

Calculate the standard molar enthalpy change for the hydrogenation of ethene:
C2H4(g) + H2(g) ⇾ C2H6(g)

Solution:

Recall ∆reactionHᶱ = Σ n B. E(reactants) - Σ m B. E(products)

= [4(C-H) + 1(C=C) + 1(H-H)] – [6(C-H) + 1(C-C)]
= [4(412) + 612 + 436] – [6(412) + 348]
= 2696 – 2820 = -124 KJmol-1
⸫ ∆reactionHᶱ = -124 KJmol-1
 Example 11:
The standard enthalpy change for the reaction below is as given:
2NH3(g) + 3Cl2(g) ⇾ N2(g) + 6HCl(g) ; ∆reactionHᶱ = -464 KJ

Given the following bond enthalpies at 298 K

Bond ∆Hᶱe / KJmol-1
Cl-Cl +243
H-Cl +431
N≡N +941

Use the above information to determine the value of the enthalpy change for N-H bond
Solution:
The chemical reaction is:
(
2 ) (
3 ) (
6 )

∆reactionHᶱ = Σ n B. E(reactants) - Σ m B. E(products)

= [2x3(N-H) + 3(Cl-Cl)] – [1(N≡N) + 6(H-Cl)]
-464 = [6(N-H) + 3(243)] – [941 + 6(431)]
-464 = 6(N-H) + 729 - 3527
-464 -729 + 3527 = 6(N-H)
+2334 = 6(N-H)
⸫ N-H = +2334/6 = +389 KJmol-1
 Example 12:
Determine the bond energy of CO2, and hence average bond energy of C = O in CO2; given
the following information:

C(graphite) ⇾ C(g) ; ∆Hᶱ = 715 KJ …………………………….(i)

1/2O2(g) ⇾ O(g) ; ∆Hᶱ = 249 KJ ……………………………..(ii)
C(graphite) + O2(g) ⇾ CO2(g) ; ∆Hᶱ = -393 KJ …………………………….(iii)

Solution:
CO2 atomization C(g) + 2O(g)

∆Hatom. or B. E(CO2) = Σ n ∆H(products) - Σ m ∆H(reactants) ……………………*

= [∆Hatom.(C) + 2∆Hatom.(O) ] – [∆f Hᶱ(CO2) ]
= [715 + 2(249)] – [-393]

B. E(CO2) = 1606 KJ
The structure of CO2 is O = C = O ; therefore, there are 2 (C = O) bonds in CO2
B. E(CO2)
Average bond energy of C = O in CO2 = = 1606/2 = 803 KJ
2
Alternatively using Hess’s law
▪ Since we are interested in the bond energy of CO2, i.e ∆Hatom. of CO2; the CO2 in
equation (3) must appear on the L. H. S. So we reverse eqn (3), and the sign of the
∆H value will also change
▪ Eqn (2) should also be multiplied by 2 and then we add eqns (1), (2) and (3)
together:

C(graphite) ⇾ C(g) ; ∆Hᶱ = 715 KJ …………………………….(i)

2 x 1/2O2(g) ⇾ 2O(g) ; ∆Hᶱ = 2 x 249 KJ = 498 KJ ………………(iia)

CO2(g) ⇾ C(graphite) + O2(g) ; ∆Hᶱ = 393 KJ …………………………….(iiia)

CO2(g) ⇾ C(g) + 2O(g) ; ∆Hᶱ = 715 + 498 + 393 = 1606 KJ

B. E(CO2)
Average bond energy of C = O in CO2 = = 1606/2 = 803 KJ
2
 Example 13:
Calculate the enthalpy change for breaking the bonds in ethane, and
hence calculate the average bond energy (B. E) of C-H in ethane if
the B. E (C-C) is 348 KJ

C2H6(g) ⇾ 2C(g) + 6H(g)

Use the following information:

C(graphite) ⇾ C(g) ;………………………∆Hᶱ = 715 KJ

H2(g) ⇾ 2H(g) ; …………………………… ∆Hᶱ = 436 KJ

C(graphite) + O2(g) ⇾ CO2(g) ; ………………..∆Hᶱ = -393.5 KJ

2H2(g) + O2(g) ⇾ 2H2O(l) ; …………………∆Hᶱ = -571.7 KJ

C2H6(g) + 7/2O2(g) ⇾ 2CO2(g) + 3H2O(l) ;…..∆Hᶱ = -1560 KJ

Solution:
C2H6(g) ⇾ 2C(g) + 6H(g) (atomization)
B. E(C2H6) = Σ n ∆H(products) - Σ m ∆H(reactants)
= [2∆Hatom.(C) + 6∆Hatom.(H) ] – [∆f Hᶱ(C2H6)]
= [2(715) + 3(2∆Hatom.(H) )] – [∆f Hᶱ(C2H6)]
= [2(715) + 3(436 )] – [∆f Hᶱ(C2H6)]…………….(*)

∆f Hᶱ(C2H6) can be obtained from its combustion data:

C2H6(g) + 7/2O2(g) ⇾ 2CO2(g) + 3H2O(l) ;…..∆Hᶱ = -1560 KJ

∆HᶱC = Σ n ∆f Hᶱ(products) - Σ m ∆f Hᶱ(reactants)

= [2∆f Hᶱ(CO2) + 3∆f Hᶱ(H2O)] – [∆f Hᶱ(C2H6) + 7/2∆f Hᶱ(O2)]
-1560 = [2(-393.5) + 3/2(-571.7)] – [∆f Hᶱ(C2H6) + 7/2(0)]
-1560 = -787 - 857.55 - ∆f Hᶱ(C2H6)
⸫ ∆f Hᶱ(C2H6) = -1644.55 + 1560 = -84.55 KJmol-1
Hence B. E(C2H6) = [1430 + 1308] – [-84.55]…………from(*)
= 2738 + 84.55 = 2822.55 KJmol-1
 The structure of ethane is
There are 6 C-H and 1 C-C bonds and these constitute the bond energy of C2H6
⸫ 2822.55 = 1 B.E(C-C) + 6 B.E(C-H)
2822.55 = 348 + 6 B.E(C-H)
2822.55 – 348 = 6 B.E(C-H)
2474.55 = 6 B.E(C-H) ⇒ B.E(C-H) = 2474.55/6 = 412.43 KJ
⸫ B.E(C-H) = 412.43 KJ

ENTROPY AND FREE ENERGY

▪ Entropy, S, is defined as a measure of the degree of disorderliness or randomness of a system
▪ Any spontaneous change in an isolated system must be accompanied by an increase in entropy
▪ Systems having perfect order i.e pure crystalline compounds and elements at zero Kelvin have
zero entropy
▪ Entropy increases from solid to liquid and to gas (i.e on a scale of 1-3, solid has 1 and gas has
3)
▪ Like enthalpy (H), entropy (S) depends on the initial and final states of the system undergoing
change (i.e entropy is also a state function)
▪ Hence, ∆S = Σ nS(products) - Σ mS(reactants) ………………………………………..(8)
where n and m are the coefficients of the substances in the products and reactants,
respectively
 Example 14:
Consider the reactions given below, state whether the entropy will decrease or increase
during the reactions. Explain your answer.
(i) NH3(g) + HCl(g) ⇾ NH4Cl(s)
(ii) CO(g) + Br2(g) ⇾ COBr2(g)

Solution:
(i) NH3(g) + HCl(g) ⇾ NH4Cl(s)
In the above reaction, both reactants are in gaseous state, and hence more
disorderliness or entropy compare with the product which is in solid state with less
disorderliness. Using eqn (5), the entropy change for the reaction would be negative
(say 1- (3+3) = 1- 6 = -5). That is decrease in entropy as the product is formed

(ii) CO(g) + Br2(g) ⇾ COBr2(g)

Applying eqn (5) to the given reaction, the entropy change for the reaction would be
negative (i.e decrease), since there are more gaseous reactants than the product
 CALCULATION OF ENTROPY CHANGE
▪ Considering isothermal expansion of ‘n’ moles of an ideal gas from state 1 to state 2,
the change in internal energy, ∆E or ∆U = 0 (since ∆T = 0 for isothermal change)
▪ From the 1st law of thermodynamics, dq = dE + dW …………………………(9)
where q is the amount of heat put into the system and W is the work done on the
system

▪ For an isothermal process, dq = dW (since dE = 0 in eqn (9))…………………(10)

▪ For a reversible process, the entropy change, ∆S, is defined as the ratio of q to the
absolute temperature, T of the system;
i.e ∆S = dqrev./T…………………………………………………(11)

▪ For Pressure-Volume work, dW = PdV………………………..(12)

▪ From eqns (10) and (12), dq = PdV

⸫ ∆S = dqrev./ T = PdV/T ……………………………………….(13)

▪ But PV = nRT for ‘n’ moles of ideal gas;
⸫ P = nRT/V ………………………………………………………….(14)

Substituting eq (14) into eq (13) gives,

nRTdV nRdV
∆S = = ………………………………………………...(15)
TV V
Integration of eqn (15) between the limits V1 to V2 will give;
V2
𝑉 nRdV 𝑉 dV
∆S = ‫ 𝑉׬‬2 V = nR ‫ 𝑉׬‬2 V = nR ln V V1
= nR [lnV2 – ln V1]
1 1

V2
⸫ ∆S = nR ln ……………………(16) (since ln A- ln B = ln (A/B))
V1

▪ For ideal gas, P1V1 = P2V2 (Boyle’s law)

P V
⸫ 1 = 2 ……………………………………………………………(17)
P2 V 1
Eqn (16) can also be written as
P
∆S = nR ln 1 ………………………………………………………..(18)
P2
▪ Eqn (16) and (18) are used when volume and pressure changes are involved,
respectively
Example 15:
Calculate the entropy change accompany a four hundred fold expansion of 5 moles of
an ideal gas [R = 8.314 Jmol-1K-1]

Solution:
V2
Recall ∆S = nR ln
V1
If V1 = a dm3, V2 = 400 a dm3
400 a
⸫ ∆S = (5 mol)(8.314 Jmol-1K-1) ln
a
∆S = 249.07 JK-1
Example 16:
Calculate the entropy change when 15.25 g of sulphur(IV)oxide gas at 298 K is
compressed isothermally while the gas pressure is changed from 330 mmHg to 150
mmHg [Take S = 32.0 ; O = 16.0 gmol-1; R = 8.314 Jmol-1K-1]

Solution:
P1
Recall ∆S = nR ln
P2

Number of mole of SO2, nSO2 = mass given/molar mass of SO2

Molar mass of SO2 = 32.0 + 2(16.0) = 64.0 gmol-1

15.25 g
⸫ nSO2 = = 0.24 mol
64.00 gmol−1

Given P1 = 330 mmHg, P2 = 150 mmHg

330
⸫ ∆S = (0.24 mol)(8.314 Jmol-1K-1)ln
150
∆S = 1.57 JK -1
 ENTROPY CHANGE FOR PHASE TRANSITION

▪ All phase transitions (e.g CO2(s) ⇄ CO2(g)) are always in equilibrium with each other;
hence the change in free energy is zero, i.e ∆G = 0

▪ Enthalpy and entropy changes are related to free energy change by the following
expression;
∆G = ∆H -T∆S…………………………………………………………..(19)

▪ For phase transition, ∆G = 0 = ∆Ht -Tt∆St ………………………………(20)

∆Ht
Tt∆St = ∆Ht ⇒ ∆St =
Tt

∆Ht
⸫ ∆St = ……………………………………………………………….(21)
Tt
where ∆St = entropy change accompanying the transition
∆Ht = heat change accompanying the transition
Tt = temperature of transition
Example 17:

If the molar heat of transition that accompanied the transition, CO(g) ⇄ CO(s) at 60
oC is 95.8 KJmol-1 .Calculate the standard entropy change, ∆Sᶱ accompanying the

transition
Solution:
∆Ht
Recall ∆Stᶱ =
Tt

Given ∆Ht = 95.8 KJmol-1, Tt = 60 oC = 60 + 273 = 333 K

⸫ ∆Stᶱ = 95.8 x 103 Jmol-1 / 333 K = 287.7 Jmol-1K-1
 Gibbs Free Energy, G
▪ This is a measure of the useful work that a system is capable of doing (apart from
volume changes)
▪ Gibbs free energy, G, is defined by the equation:
G = H –TS…………………………………………………………….(22)
▪ Like enthalpy (H) and entropy (S), G depends on the initial and final states of the
system undergoing change (i.e G is also a state function)
▪ Recall ∆G = ∆H -T∆S…………………………………………………(19)
⇒ Gproducts – Greactants = Hproducts – Hreactancts – T(Sproducts - Sreactants)

▪ ∆G provides a direct measurement of the spontaneity or feasibility of a given

reaction
❖ If ∆G is negative (i.e ∆G = -ve); the reaction is spontaneous, i.e the reaction will
occur as written
❖ If ∆G is positive (i.e ∆G = +ve); the reaction is not spontaneous, i.e the reaction will
not occur as written
❖ If ∆G is zero (i.e ∆G = 0); the reaction is at equilibrium

▪ When ∆G is measured at 25 oC (298 K) and 1 atmospheric pressure (i.e standard

temperature and pressure, STP), it is referred to as standard Gibbs free energy
change, ∆Gᶱ
▪ Gibbs free energy change is also related to the equilibrium constant, K, by the
expression:
∆G = -RT ln K
∆G = -2.303 RT log10K…………………………………………………..(23)
where R is the gas constant = 8.314 Jmol-1K-1
T is the temperature in kelvin

ESTIMATION OF FREE ENERGY CHANGE

▪ Eqn (19), apart from being useful in estimating the values of ∆G, can also be used to
predict how systems will behave at low and high temperatures

(i) At low temperatures:

The factor T∆S becomes small and so ∆H controls the sign of ∆G. Therefore, only
exothermic reactions are feasible at low temperature because ∆G is negative when
∆H is negative

(ii) At high temperatures:

The factor T∆S becomes large and more important;
(a) Endothermic reactions:
For ∆G to be –ve, the endothermic reactions must be accompanied by an increase
in entropy, i.e entropy change must be large enough for the product T∆S to exceed
∆H
(b) Exothermic reactions:
Exothermic reactions become explosive and favorable at high temperatures
Example 18:
What is the standard Gibbs free energy change , ∆Gᶱ for the following reaction at
25 oC , given the following information:
N2(g) + 3H2(g) ⇾ 2NH3(g)
∆Hfᶱ (KJ mol-1): 0 0 -45.9
Sᶱ (JK-1) 191.5 130.6 193

Solution:
∆reactionHᶱ = Σ n ∆fH (products) - Σ m ∆fH(reactants)
= [2∆fH(NH3) ] – [∆fH(N2) + 3∆fH(H2) ]
= [2(-45.9)] – [0 + 0]
∆reactionHᶱ = -91.8 KJ

∆Sᶱ = Σ n Sᶱ(products) - Σ m Sᶱ(reactants)

= [2Sᶱ(NH3)] – [Sᶱ(N2) + 3Sᶱ(H2) ]
= [2(193)] – [191.5 + 3(130.6)]
= -197.3 JK-1 = -0.197.3 KJ K-1
Recall ∆Gᶱ = ∆Hᶱ -T∆Sᶱ
= -91.8 KJ –[298 K x (-0.1973 KJ K-1 )]
= -91.8 KJ + 58.80 KJ
⸫ ∆Gᶱ = -33.0 KJ
Tutorial Questions:
(1) Without doing any calculations, estimate the sign of the entropy change for each of the following
processes:(i) 2CaCO3(s) ⇾ 2CaO(s) + 2CO2(g) (ii) dissolution of table salt, NaCl(s) ⇾ NaCl(aq.)
(iii) the photosynthesis of glucose, 6CO2(g) + 6H2O(l) ⇾ C6H12O6(s) + 6O2(g) (iv) the evaporation of water
from damp clothes. Explain your answer

(2) Calculate the lattice enthalpy of MgBr2 from the following data:
Process ∆H (KJ mol-1)
Sublimation of Mg(s) +148
Ionization of Mg(g) to Mg2+(g) +2187
Vaporization of Br2(l) +31
Dissociation of Br2(g) +193
Electron attachment to Br(g) -331
Formation of MgBr2(s) from Mg(s) and Br2(l) -524

(3) Three moles of CO2 gas was compressed isothermally from a pressure of 15 atm to 3 atm. Calculate the
entropy change that accompanies this process if the gas behaves ideally [R = 8.314 J mol -1K-1]
(4) From the following data, determine ∆fHᶱ for diborane, B2H6(g) , at 298 K:
(i) B2H6(g) + 3O2(g) ⇾ B2O3(s) + 3H2O(g) ∆rHᶱ = -2036 KJ mol-1
(ii) 2B(s) + 3/2O2(g) ⇾ B2O3(s) ∆rHᶱ = -1274 KJ mol-1
(iii) H2(g) + 1/2O2(g) ⇾ H2O(g) ∆rHᶱ = -241.8 KJ mol-1
(5) Calculate the bond energy of C-C in C6H6 from the following information:
C(graphite) ⇾ C(g) ∆H atom. = 715 KJ
1/2H2(g) ⇾ H(g) ∆Hatom. = 218 KJ
6C(graphite) + 6H(g) ⇾ C6H6(l) ∆H = 49 KJ
(Given: B.E (C-H) = 411 KJ and B.E (C = C) of aromatic = 602 KJ)
1. The heats of formation of CO(g) and CO2(g) are -26.4 kCal and -94.0 kCal, respectively. The
heat of combustion of carbon(II)oxide according to Hess’s law will be
(a) +94.0 kCal (b) +26.4 kCal (c) -67.6 kCal (d) -120.4 kCal
2. ∆Hᶱ represents the enthalpy change at
(a) 0 oC and 1 atm pressure (b) 0 K and 1 atm pressure (c) 25 oC and 1 atm pressure (d) none of
the above
3. The heat change when one mole of a liquid is converted into vapor or gaseous state at its
boiling point is called
(a) heat of liquefaction (b) heat of fusion (c) heat of vaporization (d) heat of sublimation
4. The heat change in the equation H+(aq.) + OH-(aq.) ⇾ H2O(l) ∆H = -13.7 kCal represents
(a) heat of formation of water (b) heat of neutralization (c) heat of solution (d) heat of
dissociation of water
5. Which of the following always has a negative value?
(a) heat of reaction (b) heat of formation (c) heat of combustion (d) heat of solution
6. By convention, the standard heat of formation of all elements is assumed to be
(a) negative (b) zero (c) infinity (d) positive
7. The ∆fusH of water at 273 K is +6.0 KJmol-1. What is the change in enthalpy of freezing for
water at the same temperature? (a) -6.0 KJmol-1 (b) +6.0 KJmol-1 (c) 0 KJmol-1 (d) +12.0 KJmol-1
8. What mass of propane must be burned to supply 350 KJ of heat according to the equation:
C3H8(g) + 5O2(g) ⇾ 3CO2(g) + 4H2O(l) , ∆H∘ = -2220 KJ
(a) 13.88 g (b) 6.94 g (c) 3.47 g (d) 0.16 g

9. For the reaction, C6H12(l) + 9O2(g) ⇾ 6CO2(g) + 6H2O(l), ∆H = -3920 KJ at 298 K. What is
the change in internal energy for the reaction, ∆U?
(a) -3.91 x 103 KJ (b) -3.93 x 103 KJ (c) -3.91 KJ (d) -3.93 KJ

10. A sample of benzene, C6H6 , was heated to 80 oC, its normal boiling point. The heating was
continued until 15.4 KJ had been supplied; as a result, 39.1 g of boiling benzene was vaporized.
what is the enthalpy of vaporization of benzene at 80 oC?
(a) 30.7 KJ (b) 30.7 KJmol-1 (c) 7.7 KJmol-1 (d) 7.7 KJ