University of Mines and Technology

Chemical Thermodynamics
( CH & RP 263)
CHAPTER 3
Dr Benjamin Edem Meteku
Department of Chemical & Petrochemical Engineering
[email protected]
March 2024
 Thermochemistry
❖ Energy in the form of heat (thermal energy) is generally
evolved or absorbed as a result of chemical change.

❖ Thermochemistry is the branch of physical chemistry

which deals with the thermal (heat) changes caused by
chemical reactions.

❖ In the previous chapter, we learnt that every substance has

a definite amount of energy known as intrinsic energy or
internal energy, E or U
 Thermochemistry

❖ The exact value of internal energy cannot be determined

but the change in internal energy, ΔE/ΔU, can be accurately
measured experimentally.

❖ When the internal energy of reactants (Er) is greater than

the internal energy of the products (Ep), the difference of
internal energy, ΔE, is released as heat energy
ΔE = Eproducts – Ereactants
or
ΔE = Ep – Er
(Such a reaction is called exothermic reaction)
 Thermochemistry

❖ If the internal energy of the products (Ep) is greater than

that of the reactants (Er), heat is absorbed from the
surroundings
ΔE = Eproducts – Ereactants
ΔE = +ve
(Such a reaction is called endothermic reaction)
❖ The amount of heat released or absorbed in a chemical
reaction is termed the heat of reaction
 Thermochemistry

❖ The energy changes in chemical reactions are largely due

to the breaking of existing bonds between the atoms and the
formation of new bonds.

❖Thus thermochemistry provides useful information

regarding the bond energies
Thermochemistry
 Thermochemistry
Enthalpy of Reactions
❖ Just like internal energy, it is difficult to measure the
absolute value of Enthalpy (H).

❖ However, the ΔH accompanying a process can be

measured accurately. Using the relation:
ΔH = ΔHreaction = Hproducts - Hreactants
 Thermochemistry
Enthalpy of Reactions
❖ Endothermic Reactions
When Hproducts is greater than Hreactants then ∆H is positive and
heat is absorbed in the reaction, and the reaction will be
endothermic.
For example,
H2 (g) + I2(g) →2HI (g); ∆Hr = 52.5 kJ
 Thermochemistry
Enthalpy of Reactions
❖ Exothermic Reactions
When Hproducts is less than Hreactants then ∆H is negative and heat
is evolved in the reaction, and the reaction will be
exothermic.
For example,
CH4 (g) + 2O2 (g) →CO2 (g) + 2H2O (l); ∆Hr = – 890.4 kJ
 Thermochemistry
Standard Enthalpy of Reactions
❖Enthalpy of a reaction changes with pressure and temperature. It
is convenient to report enthalpies of the reactions in terms of
standard state of substances.

❖When substances are in their standard states, we call the

enthalpy of reaction as standard enthalpy of reaction.

❖It is defined as the enthalpy change for a reaction, when the

reactants and the products are in their standard states. It is
denoted by:
ΔHro
 Thermochemistry
Enthalpy of Formation (ΔH f )
❖ The enthalpy change involved when one mole of a pure
compound is formed from its elements in their most stable
states is called the enthalpy of formation and is denoted by
(ΔH f ) or (Δf H)
❖ When the reacting elements and the products formed are
all in their standard states, the enthalpy change
accompanying the chemical reaction is called the standard
enthalpy of formation and is denoted by
(ΔHf ͦ) or ∆fH°.
 Thermochemistry
Standard Enthalpy of Formation (ΔH f ͦ)
❖ By convention, we take the standard enthalpy of
formation of an element in its most stable state as zero.
Example
C (Graphite) + O2(g) → CO2 (g) ; ∆Hf°. = – 393.5 kJ mol–1

This means that carbon dioxide is formed from its elements

in their most stable states. Carbon in the form of graphite and
at room temperature and gaseous O2 and CO2 being at 1 bar.
 Thermochemistry
Standard Enthalpy of Formation (ΔH f ͦ)
Question
Given a hypothetical chemical equation with the variables A, B and C
representing different compounds
And the standard enthalpy of formation values

What is the standard enthalpy change for the reaction?

 Thermochemistry
Standard Enthalpy of Formation (ΔH f ͦ)
Question
Solution
 Thermochemistry
Standard Enthalpy of Formation (ΔH f ͦ)
Question
Given that, the enthalpy of formation of NO2(g):33.18kJ/mol and
NO(g): 90.25 KJ/mol. Calculate the ΔHreactionͦ for the formation of
NO2(g) from the reaction of NO and O2
NB
[ Standard enthalpy of formation for elements in their most stable
state is zero]
 Thermochemistry
Standard Enthalpy of Formation (ΔH f ͦ)
Question
Solution
 Thermochemistry
Enthalpy of Combustion (ΔHc)
❖ Enthalpy of combustion is the enthalpy change (heat
evolved) accompanying the complete combustion of 1 mole
of a substance in oxygen or air at a given temperature and 1
bar pressure. It is denoted ΔHc
❖ The standard enthalpy of combustion is denoted ΔHc ͦ
For example
C2H5OH (l) + 3O2 (g) →2CO2 (g) + 3H2O (l); ∆Hc = – 1365.6 kJ
Enthalpy of combustion of C2H5OH (l) is – 1365.6 kJ mol–1
 Thermochemistry
Enthalpy of Neutralisation (ΔHn)
❖ Enthalpy of neutralization is the enthalpy change (heat
evolved) when one mole of hydrogen ions (H+) is
neutralized by one mole of hydroxyl ions (OH-) in dilute
aqueous medium to form water.
❖ For example
H+ (aq) + OH–(aq) →H2O (l); ∆Hn = –57 kJ/mol
❖ Enthalpy of neutralization of a strong acid with a strong
base is always constant having a value of –57 kJ.
 Thermochemistry
Enthalpy of Neutralisation (ΔHn)

However, enthalpy of neutralization of strong acid with a

weak base or weak acid with a strong base will be different,
because of varying degree of ionization of weak acids and
bases
 Thermochemistry
Laws of Thermochemistry
There are two Laws of Thermochemistry;
❖ The Lavoisier–Laplace law
It states that the heat change (or enthalpy change) of a chemical reaction
is accurately equivalent but reverses in the sign for the reverse reaction.
In order words when a chemical equation is reversed, the sign of ∆Hr is
changed.
For example
N2 (g) + O2 (g) → 2NO (g); ∆Hr = 180.5 kJ
2NO (g) → N2 (g) + O2 (g); ∆Hr = –180.5 kJ
 Thermochemistry
Laws of Thermochemistry
❖ The Hess’s Law of Constant Heat Summation
It states the enthalpy of reaction is independent of the
number and the nature of the intermediate steps.

If a chemical change can be made to take place in two or

more different ways whether in one step or two or more
steps, the amount of total heat change is same no matter by
which method the change is brought about
 Thermochemistry
Laws of Thermochemistry
❖ The Hess’s Law of Constant Heat Summation
The law also follows as a mere consequence of the first law of
thermodynamics. Let us suppose that a substance A can be changed
to Z directly,

where Q1 is the heat evolved in the direct change. When the same
change is brought about in stages:
 Thermochemistry
Laws of Thermochemistry
❖ The Hess’s Law of Constant Heat Summation

Then, according to Hess’s Law,

The heat evolved for the direct step (Q1) is the same as the heat
evolved for the intermediary steps (Q2)
Q1 = Q2
 Thermochemistry
Laws of Thermochemistry
❖ The Hess’s Law of Constant Heat Summation

Q1 = q1 + q2 + q3
 Thermochemistry
Hess Law of Constant Heat Summation
Example
Burning of carbon to CO2. Carbon can be burnt to carbon dioxide directly or it may first be changed
to carbon monoxide which may then be oxidised to carbon dioxide

1st way: C(s)+ O2(g) CO2(g) ; ΔH = - 94.05kcal.

1
2nd way: C(s)+ O2(g) CO (g) ; ΔH = - 26.42kcal
2

1
CO(g) + O2(g) CO2 (g) ; ΔH = - 67.71kcal
2
 Thermochemistry
Hess Law of Constant Heat Summation
Example
Formation of Sodium hydroxide from Na. The formation of sodium hydroxide
from metallic sodium presents another example of Hess’s law. The process
can be carried out in two ways;
 Thermochemistry
Hess Law of Constant Heat Summation
Example

The heat evolved in carrying out the reaction in 2 different ways are
almost the same.
 Thermochemistry
Hess Law of Constant Heat Summation
Question
Calculate the enthalpy of this reaction from the following data
 Thermochemistry
Hess Law of Constant Heat Summation
Solution
 Thermochemistry
Hess Law of Constant Heat Summation
Solution
 Thermochemistry
Hess Law of Constant Heat Summation
Solution
 Thermochemistry
Hess Law of Constant Heat Summation
Question
Calculate the heat of formation for potassium hydroxide from the
following data
 Thermochemistry
Hess Law of Constant Heat Summation
Solution
 Thermochemistry
Hess Law of Constant Heat Summation
Question
Calculate the enthalpy for the following reaction:
 Thermochemistry
Hess Law of Constant Heat Summation
Solution
 Thermochemistry
Hess Law of Constant Heat Summation
Solution
 Thermochemistry
Hess Law of Constant Heat Summation
Question
Determine the heat of reaction for the oxidation of iron
 Thermochemistry
Hess Law of Constant Heat Summation
Solution
 Thermochemistry
Hess Law of Constant Heat Summation
Question
The heat evolved in the combustion of glucose is shown in the following
equation:

C6H12O6(s) + 6O2 (g) → 6CO2 (g) + 6H2O (l); ∆combH = – 2840 kJ/mol

How much energy will be required for the production of 1.08 g of glucose?
 Thermochemistry
Hess Law of Constant Heat Summation
Solution

Glucose will be prepared by the reverse reaction

6CO2 (g) + 6H2O (l) → C6H12O6 (s) + 6CO2 (g); ∆H = 2840 kJ.

This equation refers to 1 mol of glucose (180 g of glucose).

Production of 180 g of glucose requires 2840 kJ of energy.

Therefore, production of 1.08

2840/180 × 1.08 g = 17.04 kJ

 Thermochemistry
Hess Law of Constant Heat Summation
Question
Calculate the enthalpy of formation of ethane from the following data
 Thermochemistry
Hess Law of Constant Heat Summation
Question
Solution
Given

Equation (4) is our target reaction

 Thermochemistry
Hess Law of Constant Heat Summation
Question
Solution
First, lets multiply equation (1) by 2
2C(graphite) + 2O2(g) 2CO2 (g) ; ΔHf = -788 kJ/mol (5)

Second, lets multiply equation (2) by 3

3
3H2(g) + O
2 2(g)
3H2O(l) ; ΔHf = -858 kJ/mol (6)
 Thermochemistry
Hess Law of Constant Heat Summation
Question
Solution
Now, lets add equation (5) and equation (6)
7
2C(graphite) + 3H2(g) + O2(g) 3H2O(l) + 2CO2 (g) ; ΔHf = -1646 kJ/mol (7)
2

Now, lets subtract equation(3) from equation (7)

2C(graphite) + 3H2(g) - C2H6(g) 0 ; ΔHf = -86 kJ/mol
ΔHf ͦ for ethane = -86 kJ/mol
 Thermochemistry
Hess Law of Constant Heat Summation
Question

Calculate the heat of formation of ethyl alcohol from the following data
 Thermochemistry
Hess Law of Constant Heat Summation
Question
Solution
From the data given in question

(1)

(2)

(3)
Target reaction equation
(4)
 Thermochemistry
Hess Law of Constant Heat Summation
Question
Solution
First, lets multiply equation (2) by 2
2C(s) + 2O2(g) 2CO2 (g) ; ΔH= -188.6 kcal (5)

Second, lets multiply equation (3) by 3

3
3H2(g) + O
2 2(g)
3H2O(l) ; ΔH = - 205.5 kcal (6)
 Thermochemistry
Hess Law of Constant Heat Summation
Question
Solution
Now, lets add equation (5) and equation (6)
7
2C(s) + 3H2(g) + O2(g) 3H2O(l) + 2CO2 (g) ; ΔH= - 394.1 kcal (7)
2

Now, lets subtract equation(1) from equation (7)

1
2C(s) + 3H2(g) + O2(g- C2H5OH(l) 0 ; ΔH= -394.1 – (-330.0) kcal
2
ΔH for ethyl alcohol = - 64.1 kcal
 Thermochemistry
Hess Law of Constant Heat Summation
Question

Determine the ΔH for the reaction

 Thermochemistry
Hess Law of Constant Heat Summation
Question
Solution
From the data given in question

(1)

(2)

(3)
Target reaction equation
(4)
 Thermochemistry
Hess Law of Constant Heat Summation
Question
Solution
First, lets multiply equation (2) by 2
2H2(s) + O2(g) 2H2O (l) ; ΔH= -571.4 kJ (5)

Second, lets add equation (5) and (1)

C(S) + 2H2(g) + 2O2(g) 2H2O(l) +CO2(g) ; ΔH = - 965.1kJ (6)
 Thermochemistry
Hess Law of Constant Heat Summation
Question
Solution
Now, lets subtract equation(3) from equation (6)
2C(s) + 2H2(g) – CH4(g) 0 ; ΔH= -965.1 – (-890.3) kcal
ΔH for methane = - 74.8 kJ
 Thermochemistry
Hess Law of Constant Heat Summation
Question
Calculate the enthalpy of dimerisation for NO2 from the give data

[ Dimerisation reaction for NO2 given by 2NO2(g) N2O4(g) ]

 Thermochemistry
Hess Law of Constant Heat Summation
Question
Solution
From the data given in question

(1)

(2)

Target reaction equation

(3)
 Thermochemistry
Hess Law of Constant Heat Summation
Question
Solution
Now, lets subtract equation(1) from equation (2)
0 N2O4(g) - 2NO2(g); ΔH= 9.3 – (67.9) kJ
2NO2(g) N2O4(g) ; ΔH = -58.6 kJ

ΔH of Dimerisation of NO2 = - 58.6 kJ

 Thermochemistry
Bond Enthalpies
❖ In Chemical reactions, energy is either absorbed or
evolved.
❖ For each chemical reaction, bonds are broken as the
reactant species react and new bonds are formed as the
products are formed.
❖ The energy changes associated with chemical reactions
are therefore as a result of bonds being broken and new
ones being formed.
 Thermochemistry
Bond Enthalpies
❖ For gaseous reaction systems, the energy changes
involved are explicitly due to bond breakage and formation.
❖ Hence, lets consider some gaseous reaction systems.
❖ Example
At high temperature, Hydrogen molecule dissociates into
atoms
H2 (g) H (g) + H (g) ; ∆Hr = 435 kJ/mol
 Thermochemistry
Bond Enthalpies
❖ The heat absorbed in the dissociation reaction is used to
break the chemical bonds holding the H2(g) molecules
together
❖ For diatomic molecules such as H2(g), we define the
Bond Dissociation Energy:
Is the enthalpy change of the reaction in which one mole of
gaseous molecules are dissociated into gaseous atoms.
 Thermochemistry
Bond Enthalpies
❖ NB
Energy is always required to break a bond hence, the
enthalpy change associated with bond dissociation is always
positive (+ve) - An indication of energy being absorbed

Cl2 (g) Cl(g) + Cl (g) ; ∆Hr = (+) 242 kJ/mol

 Thermochemistry
Bond Enthalpies
❖ Now, let us consider a polyatomic molecule like H2O(g).
The dissociation may involve fragmenting the molecules
into an atom and a group of atoms, called a radical, as in:
H2O (g) → H (g) + OH (g); ∆rH ͦ = 502 kJ/mol
OH (g) → O (g) + H (g); ∆rH ͦ = 427 kJ/mol
❖In the first reaction, one of the two OH bonds in H2O (g)
dissociates with an enthalpy change of 502 kJ/mol and in
the second reaction, OH bond dissociates with an enthalpy
change of 427 kJ/mol.
 Thermochemistry
Bond Enthalpies
❖ The Bond enthalpy involved for H2O(g) to completely
dissociate into the individual atoms will be the average
enthalpy involved in the process:
(502 kJ + 427 kJ)/2 = 464.5 kJ
❖ Bond enthalpy is defined as the average amount of
enthalpy change involved in the dissociation of one mole of
bonds present in different gaseous compounds.
 Thermochemistry
Bond Enthalpies
❖ Although bond dissociation enthalpy and bond enthalpy
are often used interchangeably, there is a difference

❖Bond dissociation enthalpy refers to breaking a particular

bond in a particular molecule whereas bond enthalpy is the
average value of bond dissociation energies for a given type
of bond.
Thermochemistry
 Thermochemistry
Bond Enthalpies
❖ By using bond enthalpies (B.E.) it is possible to estimate
the energy released when a gaseous molecule is formed
from its gaseous atoms. For example, the energy released at
constant pressure for the reaction (∆rH),
3H (g) + C (g) + Cl (g) → CH3Cl (g)
is the sum of the energies of three C – H bonds, and one
C – Cl bond, all taken with a negative sign because energy is
released. Using the values of bond enthalpies (B.E.)
 Thermochemistry
Bond Enthalpies
ΔrH = -3B.E (C-H)+ -1B.E.(C-Cl)
= -3(413) – 1(339) kJmol-1
= -1238 -339
= -1578 kJmol-1
In the above, we used enthalpy of formation to estimate the
enthalpy of the reaction
 Thermochemistry
Bond Enthalpies
In principle, bond enthalpy data can be used to calculate
∆rH for a chemical reaction occurring in gaseous state by
making use of difference in energy absorbed in breaking the
bonds in reactants and energy released in formation of bonds
in products.
∆rH = ∑ B.E. (reactants) – ∑ B.E. (products)
 Thermochemistry
Bond Enthalpies
Example
Use bond enthalpy data to calculate the enthalpy of the
reaction.
CH4 (g) + Cl2 (g) → CH3Cl (g) + HCl (g)
 Thermochemistry
Bond Enthalpies
Solution
1. Write the equation using structural formula

H H
| |
H –C – H + Cl –Cl → H – C – Cl + H –Cl
| |
H H
 Thermochemistry
Bond Enthalpies
Solution
2. List the bonds broken and bonds formed under the equation as
shown

Bonds Broken Bonds formed

C-H =4 C-H = 3 H-Cl = 1
Cl-Cl =1 C-Cl =1
 Thermochemistry
Bond Enthalpies
Solution
3.Look up the values of bond enthalpies for the bonds in the
reactants and products and list them as shown
Reactants Products

B.E. (C-H) = 413 B.E.( Cl-C) = 339

B.E. (Cl-Cl) =239 B.E. (H-Cl) = 427
B.E. (C-H) = 413
 Thermochemistry
Bond Enthalpies
Solution
4. Enthalpy of reaction
∆rH = B.E. (reactants) - B.E. (products)
[4B.E. (C – H) + B.E. (Cl – Cl)] – [B.E. (C – Cl) + B.E. (H – Cl) + 3
B.E. (C – H)]
ΔrH = [( 4 x 413) + (239)] – [ (339) + (427) + (3x413)
[ 1652 +239] – [339+427+ 1239]
1891 – 2005
-114 kJmol-1
 Thermochemistry
Bond Enthalpies
Estimating Enthalpy of reaction using either enthalpy of
formation data or bon enthalpy data.

Example
Calculate ∆rH° for the reaction

Cl2 (g) + 2HF (g) → 2HCl (g) +F2 (g)

 Thermochemistry
Bond Enthalpies

(a) Using enthalpy of formation data

∆f H° (HCl) = – 92.5 kJ
∆f H° (HF) = – 269 kJ
(b) Using bond enthalpy data
B.E. (H – Cl) = 431 kJ mol–1
B.E. (F – F) = 155 kJ mol–1
B.E. (H – F) = 563 kJ mol–1
B.E. (Cl – Cl) = 242 kJ mol–1
 Thermochemistry
Bond Enthalpies
Using enthalpy of formation of compounds
Cl2 (g) + 2HF (g) → 2HCl (g) +F2 (g)
∆rH°= Products – Reactants
∆rH°= [2 ∆f H°(HCl) +∆f H°(F2)]- [2 ∆f H°(HF)+ ∆f H°(Cl2 )]
∆rH°= [2(-92.5) + 0] – [2(-269) +0]
= -185 + 538
= 353 kJ
 Thermochemistry
Bond Enthalpies
Using Bond enthalpy of compounds
Cl2 (g) + 2HF (g) → 2HCl (g) +F2 (g)
 Thermochemistry
Bond Enthalpies

Example
Given that energies for H–H, O=O and O–H bonds are 104,
118 and 111 kcal mol–1 respectively, calculate the heat of the
reaction

1
H2(g) + 2
O2(g) → H2 O(g)
 Thermochemistry
Bond Enthalpies
Solution
1
H-H + 2
O=O→ H-O-H
Bonds broken Bonds formed
H-H = 1 O-H = 2
O=O = 1/2
ΔHrxn = [∑ (Bonds broken) - ∑(Bonds formed)]
= [ (104)+ ½( 118)] – [ 2(111)]
= -59 kcal
 Thermochemistry
Bond Enthalpies
Example
Calculate ΔH for the following reaction, using average bond
enthalpies, assuming all compounds are in their gaseous
state.
CH4(g) + 2O2(g) CO2(g) + 2H2O(g)
Average bond enthalpies:
C-H = 413 kJ/mol C=O = 799 kJ/mol
C-C = 348 kJ/mol O-H = 463 kJ/mol
C-O = 358 kJ/mol O=O = 495 kJ/mol
 Thermochemistry
Bond Enthalpies
Solution

Bonds broken Bonds formed

C-H = 4 O-H = 4
O=O = 2 C=O =2
ΔHrxn = [∑ (Bonds broken) - ∑(Bonds formed)]
= [ (1652)+ ( 990)] – [ (1598)+(1852)]
= -808 kJ/mol
 Thermochemistry
Bond Enthalpies
Question
Calculate ΔH for the following reaction, using average bond
enthalpies, assuming all compounds are in their gaseous state.
C2H2(g) + HCl(g) H2C=CHCl(g)
Average bond enthalpies:
C-H = 413 kJ/mol C=O = 799 kJ/mol
C-C = 348 kJ/mol H-Cl = 431 kJ/mol
C-O = 358 kJ/mol C-Cl = 328 kJ/mol
C=C = 614 kJ/mol C≡C = 839 kJ/mol
 Thermochemistry
Bond Enthalpies
Solution

Bonds broken Bonds formed

C-H = 2 C-H = 3
C≡C = 1 C-Cl = 1
H-Cl = 1 C=C =1
ΔHrxn = [∑ (Bonds broken) - ∑(Bonds formed)]
= [ (826)+ (839)+ (431)] – [ (1239)+(614)+(328)]
= -85 kJ/mol
 Thermochemistry
Bond Enthalpies
Question

Ans = -964 kJ
 Thermochemistry
Bond Enthalpies
Question
Calculate the heat of reaction between propene and chlorine to give
1, 2-dichloropropane from the values of bond energies:
 Thermochemistry
Bond Enthalpies
Question
Solution

= -150.4 kJ/mol
 Thermochemistry
Bond Enthalpies
Question
Calculate the bond energy of HCl, given that H–H bond energy is
433 kJ mol–1, Cl – Cl bond energy is 242 kJ mol–1 and ∆Hf for HCl
is – 91 kJ mol–1.

Ans.
the bond energy of H–Cl is 428.5 kJ
 Thermochemistry
Bond Enthalpies
Question
Calculate the enthalpy of transition from monoclinic Sulphur to
rhombic Sulphur from their heats of combustion:

Ans = 4 kJ