Intensive Revision Program

of
Physical Chemistry

By : Brijesh Jindal Sir

KEY CONCEPTS
Thermochemistry is the branch of physical chemistry which deals with the thermal or heat changes
caused by chemical reactions. It is based on first law of thermodynamics.

ENTHALPY
Chemical reactions are generally carried out at constant pressure (atmospheric pressure) so it has
been found useful to define a new state function Enthalpy (H) as :
H = U + PV
and hence, H = U + (PV)
At constant pressure
H = U + P V
Combining with first law,
H = qp
Hence, transfer of heat at constant pressure brings about a change in the enthalpy of the system.
Enthalpy change, rH of a reaction-Reaction enthalpy-Heat of reaction
The enthalpy change accompanying a reaction is called the reaction enthalpy. It may also be defined as
the amount of heat lost or gained in the chemical reaction, when all the reactants and products are
maintained at the same temperature and pressure.

Hess's law of constant heat summation:

According to Hess’s law (a consequence of first law), if a set of reactants is converted into a set of
product by more than one sequence of reactions, the total enthalpy change will be the same for every
sequence.

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 As such, the chemical equations can be treated ordinary algebraic expressions and can be added or
subtracted to yield the required equation. The corresponding enthalpy changes are also manipulated in
the same way to obtain the enthalpy change for the desired equation.

Standard enthalpy of Reaction, rH° :

As enthalpy of a reaction depends on the conditions under which a reaction is carried out, it is necessary
to specify some standard conditions. The standard enthalpy of reaction is the enthalpy change for a
reaction, when all the participating substance (reactants and products) are in their standard condition.

The standard condition are :

* Solid / liquid / gas should be at 1 bar
* for substance dissolved in solution concentration should be 1M.

Some common Enthalpy changes in chemical reactions :

(1) Enthalpy of Formation, fH :

It is the enthalpy change when one mole of a substance is formed from its elements in their most
abundant naturally occuring form (also called reference states). For example, the reference state of
oxygen, carbon and sulphur are O2 gas, Cgraphite and Srhombic , respectively. Some reactions with
standard molar enthalpies of formation are :
1
H2(g) + O (g)  H2O(l) ; fH° = – 285.8 kJ mol–1
2 2
By convention, enthalpy of formation fH°, of an element in reference state is taken as zero.
The enthalpy of formation can be used to determine the enthalpy change of any reaction as

rH =  a i  f H(Products) –  bi  f H(reactants)

i i

where ai and bi represent the coefficients of the products and reactants in the balanced chemical
equation.

(2) Enthalpy of Combustion, CH :

It is the enthalpy change (always negative) when one mole of the substance undergo complete
combustion.
For example
CH4(g) + 2O2(g)  CO2(g) + 2H2O(l) ; cH = – 890.8 kJ mol–1 at 298 K.

(3) Enthalpy changes during phase transformations :

(i) Enthalpy of Fusion, fus.H : It is the enthalpy change that accompanies melting of one mole of a
solid substance at constant temperature (melting point of solid) and pressure.
for example,

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 H2O(s)  H2O(l) ; fusH = + 6.00 kJ mol–1

(ii) Enthalpy of Vaporisation, vapH :

It is the amount of heat required 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 heat required 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

(4) Bond Enthalpies (Bond energies), bondH :

The bond enthalpy of diatomic molecules like H2, Cl2, O2 etc. may be defined as the enthalpy change
(always positive) when one mole of covalent bonds of a gaseous covalent substance is broken to form
products in the gas phase, under conditions of constant pressure and temperature. For example
Cl2(g)  2Cl(g) ; Cl–ClH = +242 kJ mol–1
O2(g)  2O(g) ; O=OH = +428 kJ mol–1
In case of polyatomic molecules, bond dissociation enthalpy is different for different bonds within the
same molecule. In such cases, mean bond enthalpy is used. Mean bond enthalpy may be defined as the
average enthalpy change to dissociate a particular type of bond in the compounds.
In gas phase reactions, the standard enthalpy of reaction, rH°, is related with the bond enthalpies of
reactants and products as
rH° =  bond enthalpies (reactants) –  bond enthalpies (products)

(5) Ionisation Enthalpy (iH)

It is the enthalpy change (always positive) when an electron is remove from an isolated gaseous atom
in its ground state under conditions of constant temperature and pressure.
X(g)  X+(g) + e¯

(6) Electron Gain Enthalpy (egH)

It is the enthalpy change when an electron is added to a natural gaseous atom to convert it into a
negative ion under conditions of constant temperature and pressure.
X(g) + e¯  X¯(g)

(7) 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 under conditions of constant temperature and
pressure.
Na+Cl¯(s)  Na+(g) + Cl¯(g) ;

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 lattice H = + 788 kJ mol–1

(8) Enthalpy of Atomisation, aH :

It is the enthalpy change (always positive) when one mole of a substance is completely dissociated into
atoms in the gaseous state, under constant pressure and temperature condition.
For example
H2(g)  2H(g) ; aH = 435.0 kJ mol–1
CH4(g)  C(g) + 4H(g) ; aH = 1665 kJ mol–1

(9) Enthalpy of Transition

It is the enthalpy change when one mole of one allotropic form changes to another under conditions of
constant temperature and pressure. For example
C(graphite)  C(diamond) trsH = 1.90 kJ mol–1

(10) Enthalpy of Hydration, hydH :

It is the enthalpy change (always negative) when one mole of an anhydrous (or partly hydrated) compound
combines with the required number of moles of water to form a specific hydrate at the specified
temperature and pressure. For example :
CuSO4(s) + 5H2O(l)  CuSO4 · 5H2O(s) ; (hyd)H = – 78.20 kJ mol–1

(11) Enthalpy of Solution, solH :

It is the enthalpy change when one mole of a substance is dissolved in a specified amount of solvent
under conditions of constant temperature and pressure. When large volume of solvent is taken, the
enthalpy change is called enthalpy of solution at infinite dilution. For example
NaCl(s)  NaCl(aq) ; solH = + 4kJ mol–1
or, NaCl(s)  Na+ (aq) + Cl¯(aq) ; solH = + 4kJ mol–1
(12) Enthalpy of Neutralisation neutH :
It is the enthalpy change (always negative) when one g-equivalent of an acid and one g-equivalent of a
base undergo complete neutralisation in aqueous solution and all the reactants & products are at the
same specified temperature and pressure.
HCl(aq) + NaOH(aq)  NaCl(aq) + H2O(l) ; neutH = – 57.7 kJ eq–1
The enthalpy of neutralisation of strong acid and strong base is always constant (– 57.7 kJ eq–1),
independent from the acid and base taken. However, the magnitude of enthalpy change of neutralisation
decreases when any one of the acid or base taken is weak.

(13) Resonance energy :

It shows the difference in energy of most stable resonating structure and actual resonance hybrid.

Measurement of U and H : calorimetry

The process of measurement of energy changes in the physical or chemical processes is carried out in

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 a vessel called Calorimeter, which is immersed in a known volume of a liquid, knowing the heat
capacity of the Calorimeter and the liquid in which Calorimeter is immersed, it is possible to determine
the heat absorbed or evolved in the process by measuring temperature changes. Measurements are
made under two different conditions :
(i) At constant volume, qv or U or E
(ii) At constant pressure, qp or H

(i) U measurement : For chemical reactions, heat absorbed at constant volume, is measured in a
bomb Calorimeter. In this Calorimeter, a steel vessel (the bomb) is immersed in a water bath. A
combustible substance is burnt in pure oxygen supplied in the 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.

(ii) H measurement : Measurement of heat change at constant pressure (generally at atmospheric

pressure) can be done in a Calorimeter shown in the figure. In this case, the Calorimeter is left open to
atmosphere. As the reaction occurs in the Calorimeter, the temperature change is noticed and then heat
of reaction is measured with the knowledge of heat capacity of Calorimeter system.

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 OBJECTIVE
Q.1 For which of the following change H E?
(A) H2 (g) + I2 (g) 2HI (g) (B) HCl (aq)+ NaOH(aq)  NaCl(aq) + H2O(l)
(C) C(s) + O2(g)  CO2(g) (D) N2 (g)+ 3H2(g)  2NH3(g)

Q.2 The reaction CH4(g) + Cl2(g)  CH3Cl(g) + HCl(g) has H = –25 kCal.

Bond
Bond Energy
kCal
 C—Cl 84
 H—Cl 103
 C—H x
 Cl—Cl y
x:y= 9 :5

From the given data, what is the bond enthalpy of Cl—Cl bond
(A) 70 kCal (B) 80 kCal (C) 67.75 kCal (D) 57.75 kCal

Q.3 Reactions involving gold have been of particular interest to a chemist . Consider the following reactions,
Au(OH)3 + 4 HCl  HAuCl4 + 3 H2O , H =  28 kCal
Au(OH)3 + 4 HBr HAuBr4 + 3 H2O , H =  36.8 kCal
In an experiment there was an absorption of 0.44 kCal when one mole of HAuBr4 was mixed with
4 moles of HCl . What is the percentage conversion of HAuBr4 into HAuCl4 ?
(A) 0.5 % (B) 0.6 % (C) 5 % (D) 50 %

Q.4 If x1, x2 and x3 are enthalpies of H–H, O=O and O–H bonds respectively, and x4 is the enthalpy of
vaporisation of water, estimate the standard enthalpy of combustion of hydrogen
x2 x2 x2 x2
(A) x1+ –2x3+x4 (B) x1+ –2x3–x4 (C) x1+ –x3+x4 (D) 2x3–x1– –x4
2 2 2 2

Q.5 For the allotropic change represented by the equation C (graphite)  C (diamond), H = 1.9 kJ.
If 6 g of diamond and 6 g of graphite are separately burnt to yield CO2, the enthalpy liberated in first
case is
(A) less than in the second case by 1.9 kJ
(B) more than in the second case by 11.4 kJ
(C) more than in the second case by 0.95 kJ
(D) less than in the second case by 11.4 kJ

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 Q.6 NH3(g) + 3Cl2(g) l NCl3(g) + 3HCl (g); –H1
N2(g) + 3H2(g) l 2NH3(g); H2
H2(g) + Cl2(g) l 2HCl (g) ; H3
The enthalpy of formation of NCl3 (g) in the terms of H1, H2 and H3 is
H 2 3 H 2 3
(A) Hf = – H1 +  H3 (B) Hf = H1 +  H3
2 2 2 2

H 2 3
(C) Hf = H1 –  H3 (D) None
2 2
Q.7 Ethanol can undergoes decomposition to form two sets of products

C2H5OH (g) 

if the molar ratio of C2H4 to CH3CHO is 8 : 1 in a set of product gases, then the enthalpy involved in
the decomposition of 1 mole of ethanol is
(A) 65.98 kJ (B) 48.137 kJ (C) 48.46 kJ (D) 57.22 kJ

Q.8 Hydrazine, a component of rocket fuel, undergoes combustion to yield N2 and H2O.
N2H4 (l) + O2 (g)  N2 (g) + 2H2O (l)
What is the enthalpy combustion of N2H4 (kJ/mole)
Given Reaction H/kJ
2NH3 (g) + 3N2O (g)  4N2 (g) + 3H2O (l) – 1011 kJ
N2O (g) + 3H2 (g)  N2H4 (l) + H2O (l) – 317 kJ
4NH3 (g) + O2 (g)  2N2H4 (l) + 2H2O (l) – 286 kJ
1
H2 (g) + O (g)  H2O (l) – 285 kJ
2 2
(A) – 620.5 (B) – 622.75 (C) 1167.5 (D) + 622.75

Q.9 Find rU° for the reaction 4HCl (g) + O2 (g) l 2Cl2(g) + 2H2O (g) at 300 K. Assume all gases are
ideal.
o
Given: H2(g) + Cl2(g)  2HCl (g)  r H 300 = – 184.5 kJ/mole
o
2H2(g) + O2(g)  2H2O (g)  r H 300 = – 483 kJ/mole (Use R = 8.3 J/mole)
(A) 111.5 kJ/mole (B) –109.01 kJ/mole (C) –111.5 kJ/mole (D) None

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 Q.10 The enthalpy changes of the following reactions at 27°C are
1
Na(s) + Cl (g)  NaCl (s) rH = –411 kJ/mol
2 2
H2(g) + S (s) + 2O2 (g)  H2SO4 (l) rH = –811 kJ/mol
2Na(s) + S(s) + 2O2 (g)  Na2SO4 (s) rH = –1382 kJ/mol
1 1
H2(g) + Cl2(g)  HCl (g) rH = –92 kJ/mol; R = 8.3 J/K-mol
2 2
from these data, the heat change of reaction at constant volume ( in kJ/mol) at 27°C for the process
2NaCl (s) + H2SO4 (l)  Na2SO4 (s) + 2HCl (g) is
(A) 67 (B) 62.02 (C) 71.98 (D) None

Q.11 What is the ratio of the enthalpy yield on combustion of hydrogen atoms to steam to the yield on
combustion of an equal mass of hydrogen molecules to steam?
1
Given : H2(g) + O (g)  H2O(g) H = – 242 kJ
2 2
B.E. (H – H) = 436 kJ
(A) 0.80 : 1 (B) 1 : 0.80 (C) 1.80 : 1 (D) 2.80 : 1

Q.12 The molar heat capacities at constant pressure (assume constant with respect to temperature) of A, B
and C are in ratio of 1.5 : 3.0 : 2.0 . If enthalpy change for the exothermic reaction A + 2B  3C
a t
300 K is – 10 kJ/mol & Cp,m (B) is 300 J/mol then enthalpy change at 310 K is :
(A) – 8.5 kJ/mol (B) 8.5 kJ/mol (C) – 11.5 kJ/mol (D) none of these

Q.13 (i) Cis2  butene  trans  2  butene, H1

(ii) Cis  2 butene  1  butene, H2
(iii) Trans  2  butene is more stable than cis  2  butene.
(iv) Enthalpy of combustion of 1butene, H = 649.8 kCal/mol
(v) 9H1 + 5  H2 = 0
(vi) Enthalpy of combustion of trans 2  butene, H = 647.0 kCal/mol.
The value of H1 & H2 in KCal/mole are
(A) 1.0 , 1.8 (B) 1.8, -1.0 (C) –5, 9 (D) –2, 3.6

Q.14 The lattice enthalpy of solid NaCl is 772 kJmol–1 and enthalpy of solution is 2 kJmol–1. If the
hydration enthalpy of Na+ & Cl– ions are in the ratio of 3:2.5, what is the enthalpy of hydration of
chloride ion?
(A) –140 kJmol–1 (B) –350 kJmol–1 (C) –351.81 kJmol–1 (D) None

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 Q.15 H 0f of water is – 285.8 kJ mol–1. If enthalpy of neutralisation of monoacid strong base is

–57.3 kJ mol–1, H 0f of OH– ion will be

(A) – 228.5 kJ mol–1 (B) 228.5 kJ mol–1 (C) 114.25 kJ mol–1 (D) –114.25 kJ mol–1

Q.16 100 ml 0.5 N H2SO4 (strong acid) is neutralised with 200 ml 0.2M NH4OH in a constant pressure
Calorimeter which results in temperature rise of 1.4 °C. If heat capacity of Calorimeter content is
1.5 kJ/°C. Which statement is/are correct
Given : HCl + NaOH  NaCl + H2O + 57 kJ
CH3COOH + NH4OH  CH3COONH4 + H2O + 48.1 kJ
(A) Enthalpy of neutralisation of HCl v/s NH4OH is – 52.5 kJ/mol
(B) Enthalpy of dissociation (ionization) of NH4OH is 4.5 kJ/mol
(C) Enthalpy of dissociation of CH3COOH is 4.6 kJ/mol
(D) H for 2H2O(l)  2H+ (aq.) + 2OH¯(aq.) is 114 kJ

Q.17 From the following data at 25°C

Reaction rH° kJ/mol
1 1
H2(g) + O2(g)  OH (g) 42
2 2
1
H2(g) + O (g)  H2O(g) –242
2 2
H2(g)  2H(g) 436
O2(g)  2O(g) 495
Which of the following statement(s) is/are correct:
(A) rH° for the reaction H2O (g)  2H(g) + O(g) is 925.5 kJ/mol
(B) rH° for the reaction OH(g)  H(g) + O(g) is 502 kJ/mol
(C) Enthalpy of formation of H(g) is –218 kJ/mol
(D) Enthalpy of formation of OH(g) is 42 kJ/mol

Q.18 Which of the following is true?

(A) For the reaction CaCO3(calcite)  CaCO3 (aragonite)
given :  f G o298 (calcite) = –1128.8 kJ/mol,  f G o298 (aragonite) = – 1127.75 kJ/mol,
then calcite form is thermodynamically more stable at standard conditions.
(B) For the reaction,
(a) C(diamond) + 2H2 (g)  CH4(g) H1
(b) C(g) + 4H(g)  CH4(g) H2
then more heat is evolved in reaction (b).
(C) fH° (I2, g) = subH [I2, s] at 25°C.
(D) For the exothermic reaction 2Ag(s) + 1/2 O2(g)  2Ag2O(s) at 298 K. H < U

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 Q.19 Which of the following do(es) not represent H formation of the product.
1 2
(A) H (g) + (aq)  H+(aq) (B) O (g)  O2(g) + e¯
2 2 3 3

(C) NH 4 (g) + Cl–(g)  NH4Cl(s) (D) P4(black) + 5O2 (g)  P4O10(s)

(E) Reaction representing Hcombustion of C (graphite).

Q.20 Which of the following statement(s) is/are true?

(A) When (Gsystem)T,P < 0; the reaction must be exothermic
(B) f H° (S, monoclinic)  0
(C) If dissociation enthalpy of CH4(g) is 1656 kJ/mole and C2H6 (g) is 2812 kJ/mole, then value
of C–C bond enthalpy will be 328 kJ/mole
(D) If H+(aq) + OH–(aq)  H2O(l) rH° = –56 kJ/mol
f H°(H2O, g) = –242 kJ/mole;Enthalpy of vaporization of liquid water = 44 kJ/mol
then, f H°(OH–, aq) will be –142 kJ/mole

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 SUBJECTIVE

Q.21 Calculate the enthalpy of combustion of benzene (l) on the basis of the following data :
(i) Resonance energy of benzene(l) =  152 kJ/mol
(ii) Enthalpy of hydrogenation of cyclohexene(l) =  119 kJ/mol
(iii) Hºf of C6H12(l) =  156 kJ/mol
(iv) Hºf of H2O(l) =  285.8 kJ/mol
(v) Hºf of CO2(g) =  393.5 kJ/mol

Q.22 The enthalpy of formation of C2H5OH(l) is  66 k Cal/mol . The enthalpy of combustion of

CH3OCH3 is  348 k Cal/mol . Given that the enthalpies of formation of CO2(g) and H2O(l) are
 94 k Cal/mol &  68 k Cal/mol respectively, calculate H for the isomerisation of ethanol to
methoxymethane. All data are at 25º C.

Q.23 A person takes 15 breaths per minute . The volume of air inhaled in each breath is 448 ml and contains
21% of oxygen by volume . The exhaled air contains 16% of oxygen by volume . If all the oxygen
is used in the combustion of sucrose, how much of the latter is burnt in the body per day & how much
heat is evolved . Hcom of sucrose is =  6000 kJ mol1 . Take temperature to be 300 K throughout.

Q.24 The standard enthalpy of combustion of sucrose is  5645 kJ mol1 . What is the advantage
(in kJ mol1 of energy released as heat) of complete aerobic oxidation compared to anaerobic hydrolysis
of sucrose to lactic acid ? Hfº for lactic acid, CO2 and H2O is 694, 395.0 and 286.0 respectively.

Q.25 The standard enthalpy of formation of FeO & Fe2O3 is  65 kCal mol1 and 197 kCalmol1
respectively. A mixture of two oxides contains FeO & Fe2O3 in the mole ratio 2 : 1 . If by oxidation, it
is changed into a 1 : 2 mole ratio mixture, how much of thermal energy will be released per mole of the
initial mixture ?

Q.26 The enthalpies of neutralization of a weak acid HA & a weak acid HB by NaOH are
 6900 Cal/equivalent &  2900 Cal/equivalent respectively . When one equivalent of NaOH is
added to a solution containing one equivalent of HA & one equivalent of HB, the enthalpy change was
 3900 Calories . In what ratio is the base distributed between HA & HB ?

Q.27 For reduction of ferric oxide by hydrogen, Fe2O3(s) + 3 H2(g)  2 Fe(s) + 3 H2O(l) ;
Hº298 =  35.1 kJ . The reaction was found to be too exothermic to be convenient . It is desirable
that Hº should be at the most  26 kJ . At what temperature is it possible ?
CP[Fe2O3] = 104.5, CP[Fe(s)] = 25.5, CP[H2O(l)] = 75.3, CP[H2(g)] = 28.9 (all in J/mol)

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 Q.28 Calculate the enthalpy change for the reaction XeF4  Xe+ + F + F2 + F.
The average XeF bond enthalpy is 34 kCal/mol, first I.E. of Xe is 279 kCal/mol, electron affinity of
F is 85 kCal/mol & bond dissociation enthalpy of F2 is 38 kCal/mol.

Q.29 Calculate the proton gain enthalpy of NH3(g) from the following data (in kJ/mole)
H dissociation : H2(g) = 218 ; H dissociation : Cl2(g) = 124

H formation : NH3(g) = – 46 ; H f : NH4Cl(s) = –314

Lattice enthalpy of NH4Cl (s) = – 683
Ionization enthalpy of H = 1310
Electron affinity of Cl = 348

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 ANSWER KEY
OBJECTIVE

Q.1 D Q.2 D Q.3 C Q.4 B Q.5 C Q.6 A Q.7 B

Q.8 A Q.9 C Q.10 B Q.11 D Q.12 C Q.13 A Q.14 B

Q.15 A

Q.16 A,B,D Q.17 A,D Q.18 A,B,C,D Q.19 A,B,C,D

Q.20 B,C

SUBJECTIVE

Q.21 HCº(benzene) = – 3267.4 kJ mol–1 Q.22 kCal mol1

Q.23 9.822 MJ/day evolved Q.24 advantage = 5396 kJ.mol1

Q.25 Heat released= 13.4 kCal. per mol of initial mixture

Q.26 1 : 3 Q.27 404.18 K

Q.28 292 kCal/mol Q.29 – 718 kJ/mol

THERMOchem.pmd 13 12/17/2019, 7:38 PM