THERMOCHEMISTRY

THERMOCHEMISTRY
Thermochemistry deals with the transfer of heat between a chemical system and its
surroundings when a change of phase or a chemical reaction takes place within the
system.
In general, a chemical reaction can be either exothermic or endothermic. In the former case,
heat is released to the surroundings when the reactants at a given temperature and pressure
are converted to the products at the same temperature and pressure, and in the latter heat
is absorbed by the system, from the surroundings .

Sign conventions: If the heat is absorbed by the system (q > 0) then the reaction is said to
be endothermic and ∆E or ∆H value is given a positive sign. If the heat is evolved (q < 0) the
reaction is said exothermic, and ∆E or AH values is given negative sign.

Standard states: In the computation of heat of reactions it is a convention to assume that

the heat of formation of elements in their standard states is zero. The standard state is taken
as 1 atm pressure and a constant temperature. Standard states for various forms of matter
are summarized below:

STATE STANDARD STATE

Gas Ideal gas at 1 atm and the given temperature

Liquid Pure liquid at 1 atm and the given temperature

Solid Stable crystalline form at 1 atm and given T

(e.g. graphite form of carbon, rhombic form of sulphur)

At the heat of reactions are denoted by ∆E° or ∆H° at given temperature.

For example, the standard state of liquid ethanol at 298 K is pure liquid ethanol at 1 bar;
standard state of solid iron at 500 K is pure iron at 1 bar.

Note: Usually, data are taken at 298 K. Standard conditions are denoted by adding the
superscript ° to the symbol ΔH, e.g., ΔH°

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MEASUREMENT OF ∆U AND ∆H: CALORIMETRY
CALORIMETRY :
Experimental technique used to measure energy change with chemical or physical
process is defined as calorimetry.

CALORIMETER :
The process carried out in a vessel during calorimetry is called calorimeter , which is
immersed in a known volume of a liquid.

MEASUREMENT OF ∆U AND ∆H:

Knowing the heat capacity of the liquid in which calorimeter is immersed and the heat
capacity of calorimeter, it is possible to determine the heat evolved in the process by
measuring temperature changes. Measurements are made under two different
conditions:
i) at constant volume, qV
ii) at constant pressure, qp

∆U MEASUREMENTS(qV)
For chemical reactions, heat absorbed at constant volume, is measured in a bomb
Calorimeter.

Here, a steel vessel (the bomb) is immersed in a water bath. The whole device is called
calorimeter. The steel vessel is immersed in water bath to ensure that no heat is lost to
the surroundings.

Bomb calorimeter

A combustible substance is burnt in pure dioxygen supplied in the steel bomb. Heat
evolved during the reaction is transferred to the water around the bomb and its
temperature is monitored. Since the bomb calorimeter is sealed, its volume does not
change i.e., the energy changes associated with reactions are measured at constant
volume.

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Under these conditions, no work is done as the reaction is carried out at constant
volume in the bomb calorimeter. Even for reactions involving gases, there is no work
done as
∆V = 0.
Temperature change of the calorimeter produced by the completed reaction is then
converted to qv , by using the known heat capacity of the calorimeter as,
∆U = n (Cm)V ∆T = qv

∆H MEASUREMENTS(qp)
Measurement of heat change at constant pressure (generally under atmospheric
pressure) can be done in a calorimeter shown in Fig

Calorimeter for measuring heat changes at constant pressure

(atmospheric pressure).

We know that ∆qp (at constant p) and, therefore, heat absorbed or evolved, qp at
constant pressure is also called the heat of reaction or enthalpy of reaction, ∆rH.

In an exothermic reaction, heat is evolved, and system loses heat to the surroundings.
Therefore, qp will be negative and ∆rH will also be negative. Similarly in an endothermic
reaction, heat is absorbed, qp is positive and ∆rH will be positive.

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Problem
1g of graphite is burnt in a bomb calorimeter in excess of oxygen at 298 K and 1
atmospheric pressure according to the equation

C (graphite) + O2 (g)  CO2 (g)

During the reaction, temperature rises from 298 K to 299 K. If the heat capacity
of the bomb calorimeter is 20.7kJ/K, what is the enthalpy change for the above
reaction at 298 K and 1 atm?
Sol.
Given:

C (graphite) + O2 (g)   CO2 (g)

Δng = 1 − 1 = 0
weight of C =1g
T1=298 and T2=299
Cv=20.7 KJ/k
ΔH = ?
1
Mol =
12
We know
ΔH = ΔU + ΔngRT
Or ΔH = ΔU
Heat evolved at constant volume
Qv = - Cv ΔT = -20.7 x ( 299-298)
Qv = -20.7 kJ
Q -20.7
ΔU= V = = - 20.7 x 12 kJ /mol
n 1
12
So , ΔH = ΔU= -20.7 x 12 kJ/mol = -248.4 kJ/mol

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LAWS OF THERMOCHEMISTRY

(i) Lavoisier and Laplace law :

Heat absorbed or evolved in a process is equal to the heat evolved or absorbed when the
process is reversed.
H2(g)   2H(g) ; ∆H = +104 kcal,
2H(g)   H2(g) ; ∆H = –104 kcal
It follows from this law that thermochemical equation may be reversed.

(ii) Hess's law of constant heat summation :

If a reaction takes place in several steps then its standard reaction enthalpy is the
sum of the standard enthalpies of the intermediate reactions into which the
overall reaction may be divided at the same temperature.
Or
Heat change of a process is the same whether the process takes place in one step or several
steps. It follows from this law that the thermochemical equation may be treated like alzebric
equations.

Hess's law is helpful in calculating those heat changes which cannot be determined
experimentally. It has been experimentally verified and is also a consequence of the law of
conservation of energy.

For example : Carbon can be converted into CO2 is 1

step
C(s) + O2(g)   CO2(g), ∆H = –94 kcal
Or in two steps
1
C(s) + O2(g)   CO(g), ∆H1 = –26.4 kcal
2
1
CO(g) + O2(g)   CO2(g), ∆H2 = –67.6 kcal
2
According to Hess's law :
∆H = ∆H1 + ∆H2 = –26.4 – 67.6 = –94 kcal.

Problem :
Calculate the heat of reaction for the hydrogenation of acetylene to ethylene at constant
volume at 25°C from the following data.
(i) Enthalpy of formation of water = –285.8 kJ mol–1
(ii) Enthalpy of combustion of acetylene = –1299.6 kJ mol–1
(iii) Enthalpy of combustion of ethylene = –1410.8 kJ mol–1

Sol. :
1
(i) H2(g) +  H2O(l) , ∆H = –285.8 kJ mol–1
O2(g) 
2
5
(ii) C2H2(g) + O2(g)   2CO2(g) + H2O(l) , ∆H = –1299.6 kJ mol–1
2
5

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(iii) C2H4(g) + 3O2(g)   2CO2(g) + 2H2O(l) , ∆H = –1410.8 kJ mol–1
Equation (ii) + equation (i) – equation (iii), we get
C2H2(g) + H2(g)   C2H4(g)
∆H = –1299.6 – 285.8 + 1410.8 = –174.6 kJ mol–1
∆H = ∆U + ∆ngRT

∆U = –174.6 –(–1)(8.314 × 10–3)(298) = – 172.12 kJ mol–1

Problem :
Calculate ∆H° for the reaction
FeO(s) + 2H+(aq)   H2O(l) + Fe2+ (aq.)
Given that
3
2Fe(s) + O2(g)   Fe2O3(s) ; ∆H° = –822.2 kJ mol–1
2
1
2FeO(s) + O2(g)   Fe2O3(s) ; ∆H° = –284.2 kJ mol–1
2
1
H2(g) + O2(g)   H2O(l) ; ∆H° = –286.0 kJ mol–1
2
Fe(s) + 2H+(aq.)   Fe2+(aq.) + H2(g) ; ∆H° = –284.1 kJ mol–1

Sol.
1 1
Eq.(iii) + Eq.(iv) – × Eq. (i) + × Eq.(ii).
2 2
∆H°required = (–286.0) + (–284.1) – (–822.2) + (–284.2) = –301.1 kJ/mol.

(iii) Kirchoff's Law:

Dependence of ∆H and ∆E on Temperature
For a given reaction, ∆H and ∆U vary with temperature. If ∆H1 and ∆H2 are the enthalpies of
the reaction at temperatures T1 and T2 respectively, and ∆CP is the difference in the heat
capacities of the products and the reactants at constant pressure, we have
ΔH 2 - ΔH1
ΔCP =
T2 - T1
If the reaction takes place at constant volume then
ΔU 2 - ΔU1
ΔCV =
T2 - T1
where ∆Cv and ∆CP is the difference in the heat capacities of the products and reactants at
constant volume and constant pressure respectively.
ΔCV =  CV(Products) - CV(Reactants)
And ΔCP =  CP(Products) - CP(Reactants)
[Note: The heat capacities of all the substances taking part in the reaction must be included.
The elements cannot be omitted as they remain in calculating enthalpy differences.]

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ENTHALPY CHANGE, ∆rH OF A REACTION
Or REACTION ENTHALPY
In a chemical reaction, reactants are converted into products and is represented by,
Reactants   Products
The enthalpy change accompanying a reaction is called the reaction enthalpy.

The enthalpy change of a chemical reaction, is given by the symbol ∆rH

∆rH = (sum of enthalpies of products) – (sum of enthalpies of reactants)

Or Δr H = a Hi
i Product - b Hi
i Reactant

At standard condition

Δ r H =  a i HProduct -  b H i Reactant
i i

Here  is used for summation and ai and bi are the stoichiometric coefficients of the
products and reactants respectively in the balanced chemical equation.

For example, for the reaction

CH4 (g) + 2O2 (g)   CO2 (g) + 2H2O (l)
Δr H = a H
i
i Product - b H
i
i Reactant

Or Δ r H =  H m  CO2 , g  + 2H m  H 2O, l   -  H m  CH 4 , g  +2H m  O 2 , g  

where Hm is the molar enthalpy.

VARIOUS TYPES OF ENTHALPIES OF REACTIONS

Enthalpy of formation:
Enthalpy change when one mole of a given compound is formed from its elements.

(a) Formation of H2O

H2(g) + 1/2O2(g) → H2O(l).
(b) Formation of Ammonia
N2(g) + 3 H2(g)  2NH3(g)

Standard enthalpy of reaction from standard enthalpy of formation :

The knowledge of standard enthalpy of formation of various substances can be used to
calculate the standard enthalpy of reactions under standard conditions. The standard enthalpy
of any reaction (∆H°) is equal to the difference between the ∆fH° of all the products and the
reactants.
 Sum of the standard enthalpy of   Sum of the standard enthalpy of 
ΔH° =  - 
 formation of products   formation of reactants. 

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i.e Δ r H° =  a i Δ f H Product - b Δ H i f Reactant
i i

For a reaction, aA + bB 
 cC + dD
Δ r H°= cΔ f H°  C  + dΔ f H°  D   - aΔ f H°  A  + bΔ f H°  B  

Problem
Standard enthalpies of formation of CO(g), CO2(g), N2O(g) and N2O4(g) are
–110, –393, –81 and 10 kJ/moe, respectively. Find the ∆rH° for the reaction
N2O4(g) + 3CO   N2O(g) + 3CO2(g)

Sol.

Δ r H° =  a i Δ f H Product - b Δ H
i f Reactant
i i

For a reaction, N2O4(g) + 3CO 

 N2O(g) + 3CO2(g)

Δ r H°= Δ f H°  N 2 O  + 3Δ f H°  CO 2   - Δ f H°  N 2 O 4  + 3Δ f H°  CO  

= [81 + 3 × (–3393)] – [10 + 3 × (–110)] = –778 kJ/mol.

Enthalpy of combustion (∆cH):

Enthalpy of combustion is defined as the enthalpy change per mole (or per unit amount)
of a substance, when it undergoes combustion.

Combustion reactions are exothermic in nature.

Standard enthalpy of combustion (∆cH°) is defined as the enthalpy change per mole
(or per unit amount) of a substance, when it undergoes combustion and all the
reactants and products being in their standard states at the specified temperature.

Enthalpy change when one mole of a substance is burnt in oxygen,

(a) Combustion of CH4
CH4 + 2O2(g) 
 CO2(g) + 2H2O(l)
(b) Combustion of C2H2
C2H2 + 5/2 O2(g) 
 2CO2(g) + H2O(l)

CALORIFIC VALUE:
The energy released by the combustion of foods or fuels is usually compared in terms of their
combustion energies per gram. It is known as calorific value.

Mathematically, calorific value can be expressed as the amount of heat produced in calorie or joule
when one gram of a substance (food or fuel) is completely burnt or oxidised.

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Heat of combustion of fuel
calorific value =
Atomic weight or molecular weight of the fuel

When methane burns, 890.3 kJ mol-1 of energy is released.

Enthalpy of neutralization (∆neutH) :

Enthalpy change when one equivalent of an acid is neutralized by a base in dilute solution. This is
constant and its values is -13.7 kcal for neutralization of any strong acid and strong base since in
dilute solutions they completely dissociate into ions.

Overall reaction for strong acid and strong base

H+ (aq) + OH- (aq) 

 H2O(l) ; ∆H°= -13.7 kcal

For weak acids and bases, heat of neutralization is different because they are not dissociated
completely and during dissociation some heat is absorbed. So total heat evolved during
neutralization will be less.

e.g. HCN + NaOH 

 NaCN + H2O ; ∆H° = -2.9 kcal

Heat of ionization in this reaction is equal to (-2.9 + 13.7) kcal = 10.8 kcal

The enthalpy of neutralization of weak acid and weak base :

Consider the neutralisation of weak acid HA with weak base BOH.
Where, ∆Hionisation (HA) = Enthalpy of ionization of acid HA
= Enthalpy to ionize 1 mole of weak acid in aq. soln.

∆Hionisation (BOH) = Enthalpy of ionization of base BOH

∆Hneutralisation (H+/OH) = Enthalpy change for the reaction of H+ and OH– to form water.

Thus for weak acid :

∆Hneut (BOH/HA) = ∆Hion. (HA) + ∆Hion (BOH) + ∆Hneut (H+/ OH–)

Enthalpy of hydration:
Enthalpy of hydration of a given anhydrous or partially hydrated salt is the enthalpy change when it
combines with the requisite no. of mole of water to form a specific hydrate.

For example, the hydration of anhydrous copper sulphate is represented by

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CuSO4(s) + 5H2O (l) 
 CuSO4 5H2O(s) ; ∆hydH°= -18.69 kcal

Enthalpy of transition:
Enthalpy change when one mole of a substance is transformed from one allotropic form to another
allotropic form.

C (graphite) 
 C (diamond) ; ∆tranH= 1.9 kJ/mol

Enthalpy of sublimation:
It is the enthalpy change involved in the conversion of one mole of a solid directly into its vapour at a
given temperature below its melting point.

For example,

I2(s) 
 I2(g) ; ∆subH = 14.9 kcal/mol

Note : ∆Hsublimation = ∆Hfusion + ∆Hvapourization

Enthalpy of Atomization( ∆aH)

It is the enthalpy change on breaking one mole of bonds completely to obtain atoms in
the gas phase.

Standard enthalpy of atomisation ( ∆aH°) : It is the enthalpy change on breaking

one mole of bonds completely to obtain atoms in the gas phase at standard condition.

Consider the following example of atomization of dihydrogen

H2(g)   2H(g) ; ∆aH° = 435.0 kJ mol–1

Note : for solid metal like Na ,Li ,Fe etc enthalpy of atomisation will be same
as the enthalpy of sublimation.
Ex : Na(s)   Na(g) ; ∆aH°= 108.4 kJ mol–1

Bond Enthalpy ( ∆aH°)

Chemical reactions involve the breaking and making of chemical bonds. Energy is
required to break a bond and energy is released when a bond is formed.

It is possible to relate heat of reaction to changes in energy associated with breaking

and making of chemical bonds.

With reference to the enthalpy changes associated with chemical bonds, two different
terms are used in thermodynamics.
(i) Bond dissociation enthalpy
(ii) Mean bond enthalpy
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Let us discuss these terms with reference to diatomic and polyatomic molecules.
Diatomic Molecules: Consider the following process in which the bonds in one mole of
dihydrogen gas (H2) are broken:
H2(g)   2H(g) ; ∆aH°= 435.0 kJ mol–1

The enthalpy change involved in this process is the bond dissociation enthalpy of H–H
bond. The bond dissociation enthalpy is the change in enthalpy when one mole of
covalent bonds of a gaseous covalent compound is broken to form products in the
gas phase.

Note that it is the same as the enthalpy of atomization of dihydrogen. This is true for all
diatomic molecules. For example:
Cl2(g)   2Cl(g) ; ∆Cl–ClH° = 242 kJ mol–1
O2(g)   2O(g) ; ∆O=OH° = 428 kJ mol–1
Note: In the case of polyatomic molecules, bond dissociation enthalpy is different for
different bonds within the same molecule

Note: For polyatomic Molecules like methane, CH4. The overall thermochemical
equation for its atomization reaction is given below:
CH4 (g)   C(g) + 4H(g) ; ∆aH° = 1665 kJ mol–1

In methane, all the four C – H bonds are identical in bond length and energy. However,
the energies required to break the individual C – H bonds in each successive step differ :
CH4(g)   CH3(g)+H(g) ; ∆bond H° = +427 kJ mol–1
 CH2(g)+H(g)
CH3(g)  ; ∆bond H° = +439 kJ mol–1
 CH(g)+H(g)
CH2(g)  ; ∆bond H° = +452 kJ mol–1
 C(g)+H(g)
CH(g)  ; ∆bond H° = +347 kJ mol–1
Therefore,
CH4(g)   C(g)+4H(g) ; ∆aH° = 1665 kJ mol–1
In such cases we use mean bond enthalpy of C – H bond.

For example in CH4, ∆C–HH° is calculated as:

∆C–HH° = ¼ (∆a H°) = ¼ (1665 kJ mol–1) = 416 kJ mol–1

The reaction enthalpies are very important quantities as these arise from the changes
that accompany the breaking of old bonds and formation of the new bonds.

We can predict enthalpy of a reaction in gas phase, if we know different bond

enthalpies.

The standard enthalpy of reaction, ∆rH° is related to bond enthalpies of the reactants
and products in gas phase reactions as:
Δ r H° =  Bond enthalpy Reactant -  Bond enthalpy Product

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This relationship is particularly more useful when the required values of ∆f H° are not
available. The net enthalpy change of a reaction is the amount of energy required
to break all the bonds in the reactant molecules minus the amount of energy
required to break all the bonds in the product molecules.

Remember that this relationship is approximate and is valid when all substances
(reactants and products) in the reaction are in gaseous state.

Some Mean Single Bond Enthalpies

in kJ mol–1 at 298 K

Some Mean Multiple Bond Enthalpies

in kJ mol–1 at 298 K

Lattice Enthalpy(∆latticeH°)
The lattice enthalpy of an ionic compound is the enthalpy change which occurs
when one mole of an ionic compound dissociates into its ions in gaseous state.

 Na+(g) + Cl- g;

Na+Cl–(s)   ∆latticeH° = +788 kJ mol–1

Since it is impossible to determine lattice enthalpies directly by experiment, we

use an indirect method where we construct an enthalpy diagram called a Born-Haber
Cycle.

Let us now calculate the lattice enthalpy of Na+Cl–(s) by following steps given below :
1. sublimation of sodium metal
Na(s)   Na(g) , ∆subH° = 108.4 kJ mol–1
2. ionization of sodium atoms, ionization enthalpy
Na(g)   Na(g) e(g) , ∆iH° = 496 kJ mol–1
3. the dissociation of chlorine, the reaction enthalpy is half the bond dissociation
enthalpy

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Cl2(g)   2Cl(g), ∆bondH° = 121 kJ mol–1
4. e l e c t r on gained by chlorine atoms. The electron gain enthalpy,
 Cl- (g) ; ∆egH° = – 348.6 kJ mol–1.
Cl(g) e- (g) 
5. lattice enthalpy of Na+Cl–(s)
Na+ (g) + Cl− (g)   Na+Cl− (s)

The sequence of steps is shown in Fig. is known as a Born-Haber cycle. The importance
of the cycle is that, the sum of the enthalpy changes round a cycle is zero. Applying
Hess’s law, we get,
∆fH° = ∆latticeH° + ∆subH° + ∆bondH° + ∆iH° + ∆egH°
∆latticeH° =∆fH° - (∆subH° + ∆bondH° + ∆iH° + ∆egH° )
∆latticeH° =411.2 + 108.4 + 121 + 496 – 348.6
∆latticeH° = + 788kJ
Where ∆fH° is enthalpy of formation of NaCl

Enthalpy of Solution (symbol : ∆solH° )

Enthalpy of solution of a substance is the enthalpy change when one mole of it
dissolves in a specified amount of solvent.

The enthalpy of solution at infinite dilution is the enthalpy change observed on

dissolving the substance in an infinite amount of solvent when the interactions between
the ions (or solute molecules) are negligible.

When an ionic compound dissolves in a solvent, the ions leave their ordered positions
on the crystal lattice. These are now more free in solution. But solvation of these ions
(hydration in case solvent is water) also occurs at the same time. This is shown
diagrammatically, for an ionic compound, AB (s)
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 
The enthalpy of solution of AB(s), ∆solH°, in water is, therefore, determined by the
selective values of the lattice enthalpy, ∆latticeH°
and enthalpy of hydration of ions, ∆hydH° as
∆solH° = ∆latticeH° + ∆hydH°

For most of the ionic compounds, ∆solH° is positive and the dissociation process
is endothermic. Therefore the solubility of most salts in water increases with rise of
temperature.
If the lattice enthalpy is very high, the dissolution of the compound may not take place
at all.

Enthalpy of Dilution(∆dilH°)
It is known that enthalpy of solution is the enthalpy change associated with the addition
of a specified amount of solute to the specified amount of solvent at a constant
temperature and pressure.

This argument can be applied to any solvent with slight modification.

Enthalpy change for dissolving one mole of gaseous hydrogen chloride in 10 mol of
water can be represented by the following equation.
For convenience we will use the symbol aq. for water

HCl(g) + 10 aq.   HCl.10 aq. ∆H = –69.01 kJ / mol

Let us consider the following set of enthalpy changes:
HCl(g) + 25 aq.   HCl.25 aq. ∆H = –72.03 kJ / mol
HCl(g) + 40 aq. 
 HCl.40 aq. ∆H = –72.79 kJ / mol
 HCl.  aq.
HCl(g) +  aq.  ∆H = –74.85 kJ / mol

The values of ∆H show general dependence of the enthalpy of solution on amount of solvent. As
more and more solvent is used, the enthalpy of solution approaches a limiting value, i.e, the value in
infinitely dilute solution. For hydrochloric acid this value of ∆H is given above in equation If we
subtract the first equation (equation S-1) from the second equation (equation S-2)
in the above set of equations, we obtain–
HCl.25 aq. + 15 aq.   HCl.40 aq.
∆H = [ –72.79 – (–72.03)] kJ / mol = – 0.76 kJ / mol
This value (–0.76kJ/mol) of ∆H is enthalpy of dilution. It is the heat withdrawn from
the surroundings when additional solvent is added to the solution.

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Note: The enthalpy of dilution of a solution is dependent on the original
concentration of the solution and the amount of solvent added.

ENTHALPY CHANGES DURING PHASE TRANSFORMATIONS :

(i) Enthalpy of Fusion, ∆fus.H :
It is the enthalpy change that accompanies melting of one mole ofa solid substance at
constant temperature (melting point of solid) and pressure.
For example,
H2O(s)   H2O(l) ; ∆fusH = + 6.00 kJ mol–1

(ii) Enthalpy of Vaporisation, ∆vapH :

It is the enthalpy change to vapourise one mole of a liquid substance at constant temperature
(boiling point of liquid) and pressure for example :
H2O(l)   H2O(g) ; ∆vapH = + 40.79 kJ mol–1

(iii) Enthalpy of Sublimation, ∆subH :

It is the amount of enthalpy change to sublime one mole of a solid substance at constant
temperature (sublimation temperature of solid) and pressure. For example
CO2(s)   CO2(g) ; ∆subH = +25.2 kJ mol–1

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Problem
If EC – C is 344 kJ mol–1 and EC – H is 415 kJ mol–1, calculate the enthalpy of
formation of propane. The enthalpies of atomization of carbon(s) and hydrogen (g) are
716 kJ mole–1 and 433 kJ mole–1 respectively.

Sol. :
The enthalpy of formation is the sum of the atomization and bond energies. For propane, the
enthalpies of atomization are
3C(s)   3C(g) ; ∆H = 3 × 716 = 2148 kJ

4H2(g)   8H(g) ; ∆H = 4 × 433 = 1732 kJ

The bond enthalpies are
2∆H C – C = 2 × –344 = –688 kJ
8∆H C – H = 8 × –415 = –3320 kJ
Adding
3C + 4H2   C3H8 ; ∆Hf = 2148 + 1732 – 688 – 3320 = –128 kJ mole–1

Problem
The acids HA, HB & HC are neutralised seperately by NaOH. If ∆neutH are –12.1, –3.9 &
–7.2 kcal/eq. Arrange the acids in the increasing order of their acidic strength.
Sol. :
A>C>B

Problem
DneutH of H2C2O4 by NaOH is –8.7 kcal/mol, ∆ionH of oxalic acid is
Sol. :
–27.4 + ∆ionH = –8.7
∆ionH = +18.7 kcal/mol

Problem
Calculate the proton affinity of NH3(g) from the following data (in kJ/mole)
∆H°dissociation:H2 (g) = 218
∆H°formation : NH3 (g) = –46
Lattice energy of NH4Cl = –683
Ionisation energy of H = 1310
Electron affinity of Cl = 348
Bond dissociation energy Cl2(g) = 124
∆H°formation : NH Cl(s) = –314
Sol:
We have to calculate ∆H for the following equation
NH3(g) + H+(g)   NH4+ (g)
Given :
H2(g)   2H(g) : ∆H1 = 218 kJ/mole
1 3
N (g)+ H (g)   NH3(g) : ∆H2 = –46 kJ/mole
2 2
NH4Cl(s)   NH4+ (g) + Cl–(g) : ∆H3 = +683 kJ/mole
H(g)   H (g)
+
: ∆H4 = 1310 kJ/mole
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Cl2(g)  Cl–(g) : ∆H5 = –348 kJ/mole
Cl2(g)  2Cl(g) : ∆H6 = 124 kJ/mole
1 1
N2 (g) + 2H2 (g) + Cl2 (g) 
 NH4 Cl(s) : ∆H7 = –314 kJ/mole
2 2
1 1
∆H = - ∆H1 + ∆H2 + ∆H3 - ∆H4-+ ∆H5 - ∆H6 + ∆H7
2 2
1 1
= - x 218 + 46 + 683 - 1310 + 348 - x 124 - 314
2 2
= – 768 kJ/mole

Problem:
Calculate the heat of reaction for the hydrogenation of acetylene to ethylene at constant
volume at 25°C from the following data.
(i) Enthalpy of formation of water = –285.8 kJ mol–1
(ii) Enthalpy of combustion of acetylene = –1299.6 kJ mol–1
(iii) Enthalpy of combustion of ethylene = –1410.8 kJ mol–1
Sol. :
(i) H2(g) + O2(g)   H2O(l), ∆H = –285.8 kJ mol–1
(ii) C2H2(g) + O2(g)   2CO2(g) + H2O(l), ∆H = –1299.6 kJ mol–1
(iii) C2H4(g) + 3O2(g)   2CO2(g) + 2H2O(l), ∆H = –1410.8 kJ mol–1

Equation (ii) + equation (i) – equation (iii), we get

C2H2(g) + H2(g)   C2H4(g)

∆H = –1299.6 – 285.8 + 1410.8 = –174.6 kJ mol–1
∆U = –174.6 – (–1) (8.314 × 10–3) (298) = – 172.12 kJ mol–1

Problem:
From the following data, determine ∆Hf (B2H6 ) at 298 K;
(a) B2H6(g) + 3O2(g)   B2O3(s) + 3H2O(g), ∆H = –1941 kJ mol–1
3
(b) 2B(s) + O2(g)   B2O3(s) , ∆H = –2368 kJ mol–1
2
1
(c) H2(g) + O2(g)   H2O(g), ∆H = –241.8 kJ mol–1
2

Sol.
B2H6(g)  2B(s) + 3H2(g) ; ∆H = – 36
3
2B(s) + O2   B2O3(s) ; ∆H = – 1273
2
3H2O(l)  3H2O(g) ; ∆H = 3 × 44
3
3H2 + O2 (g)   3H2O(l) ; ∆H = –286 × 3
2
__________________________________________________________________
B2H6(g) + 3O2(g) 
 B2O3(s) + 3H2O(g) ; ∆H = – 2035 kJ/mol.
For eq.(a),

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(–1941) = [(–2368) + 3 (–241.8)] – Δf H°B2H6  g  + 3 x 0
 
Δf H°B2H6 g = - 1152.4 kJ/mol

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