EXERCISE I

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) 57.857 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 HAuBr 4 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 x 4 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 at
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) 1.0768 , 1.938 (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 Select the correct statement.

(A) Hf [H(g)] is equal to Hatomisation of H2(g)
(B) HBE (H–H) is equal to Hf of H(g)
(C) HBE (H–H) is equal to Hatomisation of H2(g)
(D) Hcombustion [H2(g)] is equal to Hf [H2(g)]

Q.17 The standard enthalpy of formation of ammonia gas is

Given: N2H4(g) + H2(g)  2NH3(g) ; H°r = – 40 kJ/mol
H°f [N2H4(g)] = – 120 kJ/mol.
(A) – 60 (B) – 180 (C) 40 (D) – 80

Q.18 Study the following thermochemical equations:

A  B ; H = + 100 Kcal
B  C ; H = – 80 Kcal
The correct order of enthalpies of formation of A, B and C is
(A) A < B < C (B) A < C < B (C) C < A < B (D) B < C < A

More than one may correct

Q.19 100 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.20 From the following data at 25°C

Reaction rH° kJ/mol
1 1
H (g) + O2(g)  OH (g) 42
2 2 2
1
H2(g) + O2(g)  H2O(g) –242
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

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Q.21 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.22 Select the option in which heat evolved is maximum.

Given : fH° (CO2,g) = – 75 kCal/mol ; fH° (CO,g) = – 25 kCal/mol
The product will be CO if excess amount of carbon is present and CO2 if excess O2 is present
(A) 10 moles of carbon and 4.5 moles of O2 (B) 24 gm of carbon and 64 gm of O2
(C) 4 moles of carbon and 3.5 moles of O2 (D) 30 gm of carbon and 80 gm of O2

Assertion Reason
Q.23 Statement-1 : The enthalpy of neutralization of the reaction between HCl and NaOH is
– 13.7 kCal / mol. If the enthalpy of neutralization of oxalic acid (H2C2O4) by a
strong base in – 25.4 kCal / mol, then the enthalpy change ( rH |) of the
process H2C2O4  2H+ + C2O42– is 11.7 kCal / mol.
Statement-2 : H2C2O4 is a weak acid.
(A) Statement-1 is true, statement-2 is true and statement-2 is correct explanation for statement-1.
(B) Statement-1 is true, statement-2 is true and statement-2 is NOT the correct explanation for statement-1.
(C) Statement-1 is true, statement-2 is false.
(D) Statement-1 is false, statement-2 is true.

Q.24 Statement-1: Standard enthalpy of isomerisation of an enantiomer into the other is zero.
Statement-2: The two enantiomers of any chiral compound have the same enthalpy of formation.
(A) Statement-1 is true, statement-2 is true and statement-2 is correct explanation for statement-1.
(B) Statement-1 is true, statement-2 is true and statement-2 is NOT the correct explanation for statement-1.
(C) Statement-1 is true, statement-2 is false.
(D) Statement-1 is false, statement-2 is true.

Match the column :

Q.25 From the following data, mark the option (s) where H is correctly written for the given reaction. Given:
H+(aq) + OH– (aq)  H2O (l) H = –57.3 kJ
Hsolution of HA (g) = – 70.7 kJ/mol
Hsolution of BOH(g) = 20 kJ/mol
Hionization of HA = 15 kJ/mol & BOH is a strong base
Reaction HR (kJ/mole)
(A) HA(aq) + BOH(aq)  BA(aq) + H2O (P) – 42.3
(B) HA(g) + BOH(g)  BA(aq) + H2O (Q) – 93
(C) HA(g)  H (aq) A (aq)
+ – (R) – 55.7
(D) B+(aq) + OH–(aq)  BOH(aq) (S) 0

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Q.26 Carefully observe the given diagrams which indicates standard enthalpy of formation of different states
of one mole Mg and 2 mole Cl atom and match the entries in column A and B provided.

Column I Column II
(A) Hf [Mg2+ (aq)] (P) – 1900 kJ/mole
(B) Hf [Cl– (aq)] (Q) + 460 kJ/mole
(C) Hhydration [Mg2+ (g)] (R) – 625 kJ/mole

(D) L.E.MgCl (S) + 2510 kJ/mole

2 (s )

L.E. = Lattice enthalpy

Comprehension (Q.No. 27 to Q.30 )

An intimate mixture of hydrogen gas and the theoretical amount of air at 25°C and a total pressure of
1 atm, is exploded in a closed rigid vessel. If the process occurs under adiabatic condition then using
the given data answer the questions that follow :
Given (i) CP = 8.3 Cal deg–1 mol–1; (ii) CP = 11.3 Cal deg–1 mol–1 ; H f [H2O(g)] = –57.8 kCal
[Take air as 80% N2, 20% O2 by volume]

Q.27 The value of CP of N2 & H2O will be (in Cal. deg.–1 mol–1)
(A) 8.3, 8.3 (B) 8.3, 11.3 (C) 11.3, 11.3 (D) 11.3, 8.3

Q.28 What will be the maximum temperature attained if the process occurs in adiabatic container ?
(A)  2937 K (B)  2665 K (C)  1900 K (D)  298 K

Q.29 What will be the final pressure in atm ?

(A)  8.5 (B)  7.6 (C)  5.46 (D)  0.85

Q.30 If at initial temperature T1 , E1 is initial internal energy & at higher final temperature T2 , E2 is the final
internal energy, then which option is true
(A) E1 > E2 (B) E2 > E1
(C) E1 = E2 (D) can't be compared from the given data

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 Comprehension(Q. No. 31 to Q.35 )
Using the data (all values are in kJ/mol at 25º C) given below :
Hºcombustion (ethane) =  1559.8 ; Hºcombustion (ethene) =  1410.9
Hºcombustion (acetylene) =  1299.7 ; Hºcombustion (acetaldehyde) =  1192.3
Hºf CO2(g) =  393.5 ; Hºf of H2O(l) =  285.8
Hº for C(s) (graphite)  C(g) = + 716.68 ; Bond enthalpy of H  H = 435.94
Bond enthalpy of O = O = 498.94
Calculate the following bond energies :
Q.31 CC
(A) 97.79 kJ (B) 195.62 kJ (C) 48.9 kJ (D) 434.3 kJ

Q.32 CH
(A) 227.32 kJ (B) 454.665 kJ (C) 151.54 kJ (D) 909.28 kJ

Q.33 C=O
(A) 402.13 kJ (B) 201.06 kJ (C) 804.56 kJ (D) 1608.52 kJ

Q.34 C=C
(A) 97.81 kJ (B) 195.62 kJ (C) 217.15 kJ (D) 434.28 kJ

Q.35 CC
(A) 733.07 kJ (B) 366.74 kJ (C) 1466.96 kJ (D) None of these

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 EXERCISE II
OBJECTIVE

Q.1 Which of the following reactions defines H f ?
(A) C(diamond) + C2(g)  CO2(g) (B) 1/2 H2(g) + 1/2 F2(g)  HF(g)
(C) N2(g) + 3H2(g)  2NH3 (D) CO(g) + 1/2O2(g)  CO2(g)

Q.2 H f for CO2(g), CO(g) and H2O(g) are – 393.5, –110.5 and –241.8 kJ mol–1 respectively. The

standard enthalpy change (in kJ) for the reaction

CO2(g) + H2(g)  CO(g) + H2O (g) is
(A) 524.1 (B) 41.2 (C) –262.5 (D) – 41.2

Q.3 Which of the following is not an endothermic reaction?

(A) Combustion of methane
(B) Decomposition of water
(C) Dehydrogenation of ethene to ethylene
(D) Conversion of graphite to diamond

SUBJECTIVE

Q.4 Diborane is a potential rocket fuel which undergoes combustion according to the reaction,
B2H6(g) + 3O2(g)  B2O3(s) + 3H2O(g)
From the following data, calculate the enthalpy change for the combustion of diborane :
3
2B(s) + O (g)  B2O3(s) ; H = –1273 kJ
2 2
1
H2(g) + O2(g)  H2O(l) ; H = –286 kJ
2
H2O(l)  H2O(g) ; H = 44 kJ
2B(s) + 3H2(g)  B2H6(g) ; H = 36 kJ

Q.5 Estimate the average S–F bond enthalpy in SF6. The Hf° values of SF6 (g), S(g), and F (g) are
– 1100 , 275 and 80 kJ/mol respectively.

Q.6 In a constant volume calorimeter, 3.5 g of a gas with molecular weight 28 was burnt in excess oxygen at
298.0 K. The temperature of the calorimeter was found to increase from 298.0 K to 298.45 K due to
the combustion process. Given that the heat capacity of the calorimeter is 2.5 kJ K –1, the numerical
value for the enthalpy of combustion of the gas in kJ mol–1 is

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 EXERCISE I
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 C Q.17 D Q.18 B Q.19 A,B,D Q.20 A,D
Q.21 A,B,C,D Q.22 C Q.23 D Q.24 A
Q.25 (A) P ; (B) Q ; (C) R ; (D) S Q.26 (A) Q, (B) R, (C) P, (D) S
Q.27 B Q.28 A Q.29 A Q.30 C Q.31 A Q.32 B Q.33 C
Q.34 D Q.35 A

EXERCISE II
Q.1 B Q.2 B Q.3 A Q.4 –2035kJ mol–1 Q.5 309.6 kJ/mol
Q.6 9

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