CHAPTER THREE

3.0 Thermochemistry
The branch of chemistry dealing with the measurement and computation of energy changes (∆U) and
enthalpy changes (∆H) of various types of physical transformations and chemical reactions is called
thermochemistry. Now ∆U and ∆H are related to the heat exchanged between the system and the
surroundings, therefore, these properties are also called as heat of reactions.

3.1 : Types of heat of a reaction

Depending on the experimental conditions the heat of a reaction is classified as follows.

When the reaction is performed at constant volume the accompanying energy change
(∆U) is called heat af reaction at constant volume (qv)

∆U = qv = Heat of reaction at constant volume

When the reaction takes place at constant pressure the accompanying enthalpy change
(∆.H) is called the heat af reaction at constant pressure

∆H = qp = Heat of reaction at constant pressure

Since most of the experiments are performed at constant pressure, the enthalpy change (∆H) is used
to describe the thermal changes in various types of chemical reactions and physical transformations.
3.2: Type of enthalpy changes. The enthalpy changes are classified as follows

(1) Enthalpy changes in (2) Enthalpy changes in chemical

reactions (∆rH) physical transformation (∆trssH)

(a) Enthalpy of formation (∆fH) (i) Enthalpy of vaporization (∆vapH)

(b) Enthalpy of combustion (∆cH) (ii) Enthalpy of fusion (∆fusH)

(c) Bond enthalpy ∆H( A –B) (iii) Enthalpy of sublimation (∆subH)

d) Enthalpy of neutralization (∆nH) (iv) Enthalpy of solution (∆solH) Enthalpy of

reaction (∆rH)

The enthalpy of a reaction is defined as the heat absorbed or liberated when the reactants
are completely converted into products as represented by the balanced chemical equation at a given
temperature and pressure.. It is also called as the heat of reaction at constant pressure. Enthalpy of
reaction is denoted by ∆rH and expressed in the units of kJ mol–1.

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 3.3 : Standard state

The enthalpy change depends on temperature, pressure and the physical states of the reactants
and products. Therefore, it is the recommendation of the IUPAC to mention the standard
experimental condition while reporting the values of the enthalpy changes.
3.1: Standard states of different forms of matter

Physical state Notation Conditions of standard states

(1) Gas (g) Ideal gas at 1 bar at the specified temperature*

(2) Liquid (l) Pure liquid at 1 bar at the specified temperature*

(3) Solid (s) Pure crystalline and reactive form# at 1 bar and
temperature T
(4) (aq)
Solution in Unit molarity (1 mol /dm3) at 1 bar and temperature T
water

*The conventional temperature for thermodynamic tables is specified as 298.15 K

#graphite is taken as the standard state of carbon

#rhombic form is taken as the standard state of sulphur

Standard enthalpy of formation (∆fHυ)

Standard enthalpy of formation is defined as the heat absorbed or liberated when one mole of
a substance is formed from its constituent elements in their respective standard states. Standard
enthalpy of formation is denoted by ∆fHυ .and it is called standard heat of formation also. It
is expressed in the units of kJ mol–1.

For example, the standard enthalpy of formation of water is – 285.8 kJ mol–1. It is written as
∆fHυ (H2O) = – 285.8 kJ mol–1. This enthalpy change is described as follows:

H2(g) + ½ O2 (g) ⎯
⎯→ H2O (l) ∆fHυ (H2O) = – 285.8 kJ mol–1

Ideal gas Ideal gas pure liquid

1 bar, 298 K 1 bar, 298 K 1 bar, 298 K

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 Note:

(i) It is not always necessary to mention the standard conditions with the
reactants and products in the balanced chemical equation, because ∆ fHυ itself
tells that the value refers to standard state

(A) Standard enthalpy of formation of an element

The standard enthalpy of formation of an element is taken as zero. That is, ∆ f Hυ

(Element) = 0

Reason: An element cannot be synthesized or decomposed by chemical or physical methods.

(B) Standard enthalpy of formation of a gaseous atom

The heat absorbed when 1 mole of a gaseous atom is formed from its element in its standard
state is called the standard enthalpy of formation of that atom.

Enthalpy of combustion (∆cH)

The enthalpy of combustion is the heat liberated at a constant pressure when one mole of a fuel
is completely burnt in oxygen. It is denoted by notation ∆cH and expressed in the units of kJ mol-
1
. Enthalpy of combustion is called heat of combustion also.
A combustion reaction is always exothermic. For example, when one mole of methane burns
completely in the presence of oxygen, one mole of CO2 and two moles of H2O are formed and 890
kJ heat is liberated

3.4 : Relation between standard enthalpy of reaction and standard enthalpy of formation

Standard enthalpy of reaction (∆rHθ) and standard enthalpy of formation (∆fHθ) are related by

(∆rHθ) = ΣVp ∆fHθ (products) – Σ V r ∆rHθ (reactant)

where,

Vp = Stoichiometric coefficient of product

Vr = Stoichiometric coefficient of reactant

For a general chemical reaction

aA + bB⎯
⎯→ c C + d D

υ
Σ p ∆fH (products) =c ∆fHυ (C) + d ∆fHυ (D)

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 Σ vr ∆fHθ (reactants) =a ∆fHθ (A) + b ∆fHθ (B)

Thus

(∆rHθ ) = [c ∆fHθ (C) + d ∆fHθ (D)] – [a ∆fHθ (A) + b ∆fHθ (B)]

3.5 : Difference between the enthalpy of formation and enthalpy of reaction

™ The enthalpy change accompanying the formation of one mole of a compound from its
constituent elements in their respective standard stable states is called standard enthalpy of
formation . It is denoted by ∆fH Θ .
™ The enthalpy change in any type of chemical reaction namely combination, combustion,
hydrogenation, bond dissociation or neutralization is called the enthalpy of reaction. It is
denoted by ∆ rH Θ.
Important statements: Enthalpy of formation is always equal to the enthalpy of reaction
representing the formation of that compound. But the enthalpy of every reaction need not
be the enthalpy of formation

3.6 : Enthalpy of neutralization

The heat liberated when one mole of hydrogen ions (H+) is completely neutralized by a base
in dilute aqueous solution at constant temperature and constant pressure is called enthalpy of
neutralization. It is called the heat of neutralization also.

H+ (aq) + Base ⎯
⎯→ Salt + Water + Heat

Hess's law of constant heats summation

This law was formulated in 1840 by the Swiss-Russian chemist Germain Henri Hess and is
stated as follows

The heat of a reaction (reaction enthalpy) is the same whether the reaction takes place in

one step or in several steps under the same conditions.

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 Applications of Hess’s law of constant heat summation

(i) This law provides a practical method for computing the enthalpy change of a
reaction from the enthalpy changes of other reactions.

(ii) Hess’s law is used to calculate the reaction enthalpies even for those reactions
which are otherwise difficult to carry out in the laboratory

(iii) According to Hess's law the thermochemical equations may be treated as algebraic
equations.

Working rule of applications of Hess’s law

When a chemical equations is reversed, the sign of the enthalpy change is also reversed but
magnitude remains the same.

Bond enthalpies

In a chemical reaction, you have seen that energy is either absorbed or evolved. Do you know the
origin of this change in energy? You know that bonds are broken and new bonds are formed in
chemical reactions. Energy changes take place in breaking some bonds of the reactants and in
forming new bonds of the products. So the energy changes in a chemical reaction are a result of
energy changes in breaking and forming of bonds. Let us consider the gaseous reactions, because
in these, we encounter the energy changes due to breaking and forming of bonds only.

At high temperature, hydrogen molecules dissociate into atoms as

H2 (g) = H (g) + H (g); ΔHr = 435 kJ/mol

The heat absorbed in this reaction is used to break the chemical bonds holding the hydrogen atoms
together in the H2 molecules. For a diatomic molecule like H2 (g), we define bond dissociation
energy as the enthalpy change of the reaction in which one mole of the gaseous molecules
are dissociated into gaseous atoms.

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); ΔHr0 = 502 kJ/mol

OH (g) = O (g) + H (g); ΔHr0 = 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, second OH bond dissociates with an enthalpy change of
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427 kJ/mol. It is clear that the dissociation energy of the O – H bond is sensitive to its
environment. However, the difference is not very large. We take the average value (464.5 kJ/mol
in this case) in case of polyatomic molecules and call it bond enthalpy.

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.

Now you know the distinction between bond dissociation enthalpy and bond enthalpy. 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. The bond
enthalpies of some bonds are listed in table 11.1.

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 (ΔrH),

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.) from table 11.1 we
get,

ΔrH = – 3 × B.E. (C – H) – B.E. (C – Cl)

= (–3 415 – 335) kJ mol–1

= (–1245 – 335) kJ mol–1

= – 1574 kJ mol–1

We will now show you how to use bond enthalpy data to estimate the enthalpy of a reaction, when
direct calorimetric data are not available. Note that we used enthalpy of formation data to estimate
enthalpy of a reaction. In principle, bond enthalpy data can be used to calculate ΔrH 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.

ΔrH = ΔB.E. (Reactants) – ΔB.E. (Products)

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 Table 11.1 : Average Bond enthalpies

BOND BOND ENTHALPY /(kJ mol -1

)
H–H 435
C–H 415
C – Br 284
C–C 356
C=C 598
Br – Br 193
Cl – Cl 242
C – Cl 339
F–F 155
H – Cl 431
H–O 462
H–N 390

BON BOND ENTHALPY /(kJ )

H –F 56
H –Br 36
H –I 29
C–O 35
C=O 72
C–N
39
C=N 61
C =N 87
C =C 83

Example 1 Use bond enthalpy data given in table 11.1 to calculate the enthalpy of the reaction.

CH4 (g) + Cl2 (g) = CH3Cl (g) + HCl (g)

Solution:

1. Write the equation using structural formula

H –C – H + Cl –Cl = H – C – Cl + H –Cl

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 2. List the bonds broken and bonds formed under the equation as shown

H –C – H + Cl – Cl =H – C – Cl + H – Cl

Number of bonds broken number of bonds formed

C–H=4 C – Cl = 1
Cl – Cl = 1 H – Cl = 1
C–H=3
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) = 435 kJ mol–1 B.E. (Cl – C) = 339 kJ mol–1
B.E. (Cl – Cl) = 242 kJ mol–1 B.E. (H – Cl) = 431 kJ mol–1

B.E. (C – H) = 435 kJ/mol

Enthalpy of the reaction Δr H = ΔB.E. (Reactants) - ΔB.E. (Products)
= 4[B.E. (C – H) + B.E. (C – Cl)] – [B.E. (C – Cl) + B.E. (H – Cl) + 3 B.E. (C – H)]
= [4 X 435 + 242] – [339 + 431 + 3 X 435] = – 93 kJ
Now let us take one example in which we calculate the enthalpy of a reaction using

( i) Enthalpy of formation data ( ii) Bond enthalpy data.

Example 2 Calculate Δr H° for the reaction

Cl2 (g) + 2HF (g) = 2HCl (g) +F2 (g)

(a) Using enthalpy of formation data

Δf H° (HCl) = – 92.5 kJ

Δf H° (HF) = – 269 kJ

(b) Using bond enthalpy data

B.E. (H – Cl) = 431 kJ mol–1

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B.E. (F – F) = 155 kJ mol–1

B.E. (H – F) = 563 kJ mol–1

B.E. (Cl – Cl) = 242 kJ mol–1

Solution: (a) Using enthalpy of formation of compounds,

ΔrH = [2ΔfH0 (HCl) + ΔfH(F2)] – [2ΔfH0 (HF) +Δ fH0(Cl2)]

= [2x (– 92.5) + 0] – [2x – (269) + 0] kJ

= – 185 kJ + 538 kJ

= + 353 kJ

(b) Using bond enthalpies

ΔrH0 = Δ B.E. (reactants bonds) – Δ B.E. (products bonds)

= [B.E. (Cl – Cl) + 2B.E. (H – F)] – [2 B.E. (H – Cl) + B.E. (F – F)]
= [242 + 2 (563)] kJ – [2 × 431 + 155] kJ
= 1368 kJ – 1017 kJ

Δr H0 = 351 kJ

Δr H0 calculated by these two different methods are nearly the same.

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