Thermochemistry

BRIJESH JINDAL ( BJ SIR )

• No. 1 Physical Chemistry educator on Unacademy.
• BTech (Computer Science) MNIT Jaipur
• 15 year experience of IIT JEE in Physical Chemistry
• Mentor of many top rankers including AIR-1
• Ex. Senior Faculty of Vibrant Academy, Kota, Allen Career Institute, Kota and Bansal
Classes, Kota
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EXERCISE-1 (Subjective Questions)

ENTHALPY OF FORMATION AND COMBUSTION
Q.1
s ir
Calculate standard enthalpy of formation (fH°) in KJ/mol of SrCO3(s) by given data :

s ir 1
B J
B J
Sr(s) + O (g)  SrO(s)
2 2
H° = – 600 kJ/mol
b y
b y PC
SrO(s) + CO2(g)  SrCO3(s) H° = – 200 kJ/mol
C(graphite) + O2(g)  CO2(g) H° = – 400 kJ/mol

Q.2
PC
Calculate enthalpy of formation of H2SO4(aq) from following data :

1
SO2(g) + O  SO3(g) H° = – 100 kJ/mol
2 2

si r
SO3(g) + H2O(l)  H2SO4(aq) H° = – 230 kJ/mol
s ir
J
BJ
 f HSO2 (g ) = – 300 kJ/mol 0
f H (H2O(l ) ) = – 170 kJ/mol

y B
b y b
C PC
Q.3 Consider the reaction :
P 2SO2(g) + O2(g)  2SO3(g)
Carried out at 27°C and 1 atm. Calculate H°, S° & G° for reaction using the following data :
Substance fH° (kJ/mol) S°m (J K–1 mol–1)
SO2(g) – 300 250
SO3(g) – 400 260
O2(g) 0 200

s ir ir
Q.4
J
For the reaction at 27°C :
B J s
b y CH3OH (l) +
3
O (g)  2H2O(l) + CO2(g)
y B
PC
2 2
b
PC
Substance fH°(kJ/mol) Sm°(J/K-mol) fG°(kJ/mol)
CH3OH – 238.5 126 – 166
H2O(l) – 285.5 70 – 237
CO2(g) – 393.5 213 – 394
Calculate absolute entropy S°, per mol of O2(g).

Q.5 Use the thermodynamics parameter to estimate standard boiling point of methanol.

ir
CH3OH(l) CH3OH(g)
fG°(kJ/mol)
fH°(kJ/mol)
J s – 166
– 237
– 162.5
– 201

y B
–1 –1
S°m (JK -mol ) + 124 + 244
s ir
b J
PC
Q.6
B
(a) Write the chemical equation that defines the normal boiling of CCl4(l)
(b) What is the value of G for the equilibrium in part(a)
b y
PC
(c) Estimate normal boiling point of CCl4.
[Given : fH°(CCl4(g)) = – 100 kJ/mol, S°m(CCl4(g)) = 310 J/mol
fH°(CCl4(l)) = – 140 kJ/mol, S°m(CCl4(l)) = 210 J/mol ]

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Q.7 Given values of fG° at 27°C for liquid ethanol (– 175 kJ/mol) and gaseous ethanol (–170kJ/mol).
Calculate vapour pressure of ethanol at 27°C. [ln (0.13) = – 2] [R = 8.3 J/mol-K]

Q.8
s ir
One method of synthesizing methanol(CH3OH) involves reacting gaseous carbon monoxide and hydro-
gen.
s ir B J
B J CO(g) + 2H2(g)  CH3OH(l)

b y
Calculate G at 27°C for this reaction, in which carbon monoxide gas at 5 atm and hydrogen gas at 2

b y
atm are converted to liquid methanol.
PC
PC
[Given : f G°(CH3OH) = – 166 kJ, fG°(CO(g)) = – 136 kJ]
25
[ln10 = 2.3, ln2 = 0.7, R = J/mol-K]
3

Q.9 What is G° for following reaction at 1127°C ?

CaCO3(s) l CaO(s) + CO2(g)

si r
fH° (kJ/mol) fS° (J/mol)
s ir
CaCO3(s)
J
– 1222.94 93
B J
B
CaO(s) – 635 38

b
CO2(g)
y – 393.5 213
b y
PC
(a) Is this reaction spontaneous at 1127°C ?

P C (b) What is partial pressure of CO2(g) at 1127°C ?

(c) What is the value of equilibrium constant ?
(d) At what minimum temperature decomposition of CaCO3 will take place?
(e) Is it entropy driven process or enthalpy driven process?
(f) In which direction reaction system will shift on increasing temperature?

Q.10
s ir ir
When 2 moles of C2H6(g) are completely burnt 3120 kJ of heat is liberated . Calculate the enthalpy of

J s
formation, of C2H6(g) . Given fH for CO2(g) & H2O (l) are - 395 & - 286 kJ respectively.
B J
b y y B
Q.11

PC b
Calculate standard enthalpies of formation of carbondisulphide (l) . Given the standard enthalpy of

PC
combustion of carbon (s) , sulphur (s) & carbondisulphide (l) are :  393.4,  2346.4 and
 1108 kJ mol 1 respectively.

Q.12 From the following data at 25°C, Calculate the standard enthalpy of formation of FeO(s) and of Fe2O3(s).
Reaction  r H o (kJ/mol)
(i) Fe2O3(s) + 3C(graphite)  2Fe (s) + 3CO(g) 492.5
(ii)
s ir
FeO (s) + C(graphite)  Fe(s) + CO(g) 155.5
(iii)
B J
C(graphite) + O2(g)  CO2(g) –393.5
(iv)
b y
CO(g) +1/2 O2(g)  CO2(g) –283
s ir
J
PC
Q.13 Given the following data :
2ClF(g) + O2(g)  Cl2O(g) + F2O(g) b y B
H = 167.4 kJ/mol
2ClF3(g) + 2O2(g)  Cl2O(g) + 3F2O(g)
2F2(g) + O2(g)  2F2O(g) PC H = 341.4 kJ/mol
H = – 43.4 kJ/mol
Calculate H for the reaction
ClF(g) + F2(g)  ClF3(g) Page # 2
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Q.14 Given the following data :
2NH3(g)  N2(g) + 3H2(g) H = 92 kJ
2H2(g) + O2(g)  2H2O(g) H = – 48 kJ
Calculate H for the reaction :
s ir
ir
2N2(g) + 6H2O(g)  3O2(g) + 4NH3(g)
s B J
Q.15
B J b y
The enthalpy change for the reaction C3H8(g) + H2(g)  C2H6(g) + CH4(g) at 25º C is

b y PC
 55.8 kJ/mol. Calculate the enthalpy of combustion of C 2H6(g). The enthalpy of combustion of

PC
H2, & CH4 are 285.8 & 890.0 kJ/mol respectively. Enthalpy of combustion of propane is
2220 kJ mol1.

Q.16 At 300 K, the standard enthalpies of formation of C 6H5COOH(s), CO2 (g) & H2O (l) are 
– 408, – 393 & –286 kJ mol–1 respectively .
Calculate the heat of combustion of benzoic acid at:

si r s ir
(a) constant pressure
J
(b) constant volume.

B J
y B b y
b
Q.17 Calculate the mass of mercury which can be liberated from HgO at 27º C by the treatment of excess

C PC
HgO with 45.4 kJ of heat at :
P (a) constant pressure (b) constant volume
Given : Hfº (HgO, s) =  90.8 kJ mol1 & M (Hg) = 200.6 g mol1 .

Q.18 It is observed that on combustion of 5.6 gm of but - 1-ene(g), 70Kcal of heat is liberated in a closed
rigid vessel at 300K. What could be a theoretical value of H combustion of but-2-ene at same temperature.

s ir ir
Q.19
J
Calculate H for the reaction
J s
yB C4H4(g) + 2H2(g)  C4H8(g)
B
Cb y
Given : CH° (C4H4(g)) = 22340 kJ/mol CH° (H2(g)) = 22755 kJ/mol

P
CH° (C4H8(g)) = 2286 kJ/mol b
Q.20 PC
When hydrogen gas undergoes complete combustion, the following enthalpy values are obtained :
2H2(g) + O2(g)  2H2O(g) H = – 242 kJ/mol
2H2(g) + O2(g)  2H2O(l) H = – 286 kJ/mol
Calculate H for H2O(l)  H2O(g)

Q.21 Three isomers with formula C4H8 their enthalpy of combustion data is given as :
Compound
s ir CH(kJ/mol)

B J
cis-2-butene – 2687.5

b y
tras-2-butene – 2684.2
s ir
J
1-butene –2696.2

PC B
What is the enthalpy change for conversion of cis-2-butene to trans-2-butene?

b y
PC
OTHER TYPES OF ENTHALPY OF REACTION
Q.22 If the enthalpy of formation of HCl (g) and Cl – (aq) are –92.3 kJ/mol and – 167.3 kJ/mol, find the
enthalpy of solution of hydrogen chloride gas.
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Q.23 The lattice enthalpy of AgF is 958 kJ/mol and AgCl is 905 kJ/mol. The enthalpy of hydration of Ag+(g)
is – 446 kJ/mol, that of F– is – 506 kJ/mol and that of Cl–(g) is – 364 kJ/mol. Calculate the solH of
AgCl(s) and AgF(s).

s ir
Q.24
s ir J
The enthalpy of solution of anhydrous CuSO 4 is – 15.9 kCal and that of CuSO4.5H2O is 2.8 kCal.
B
J
Calculate the enthalpy of hydration of CuSO4.
B b y
Q.25 b y PC
The enthalpies of neutralization of NaOH & NH4OH by HCl are  13680 Cal and  12270 Cal

PC respectively . What would be the enthalpy change if one gram equivalent of NaOH is added to one gram
equivalent of NH4Cl in solution ? Assume that NH4OH and NaCl are quantitatively obtained.

Q.26 From the data of H of the following reactions

C(s) + 1/2O2(g) — CO(g) ; H = –110 kJ
and
si r
C(s) + H2O(g) — CO(g) + H2(g) ; H = 130 kJ
s ir
J J
Calculate the mole composition of the mixture of steam and oxygen on being passed over coke at
B
B y
1273 K, keeping the reaction temperature constant and their is no heat exchange with surrounding.
y b
b
P
Q.27
C PC
The polymerisation of ethylene to linear polyethylene is represented by the reaction
nCH2 = CH2  (–CH2 CH2–)n
where n has a large integral value . Given that the average enthalpies of bond dissociation for C=C &
CC at 298 K are  590 & + 331 kJ mol1 respectively. Calculate the enthalpy of polymerisation
per mole of ethylene at 298 K .

Q.28
s ir
The enthalpies of neutralization of a weak acid HA & a weak acid HB by NaOH are
ir
J s
 6900 Cal/equivalent &  2900 Cal/equivalent respectively . When one equivalent of NaOH is added
B J
y B
to a solution containing one equivalent of HA & one equivalent of HB, the enthalpy change was
b y
PC b
 3900 Calories . In what ratio is the base distributed between HA & HB ?

BOND ENTHALPY PC
Q.29 Using bond enthalpy data, calculate enthalpy of formation of isoprene. Neglect resonance in isoprene.

5 C(s) + 4 H2(g)  H2C = C — C = CH2(g)

| |
CH 3 H

Given :

J si r
C  H = 98.5 k Cal ;
C  C = 83 k Cal ;
H  H = 104 k Cal
C = C = 147 k Cal
;
&

y B C(s)  C(g) = 171 k Cal .

s ir
C b B J
P
Q.30
bond enthalpy of the P–P bond? b y
The enthalpy of atomization of PH3 is 954 kJ mol–1 and that of P2H4 is 1.485 M J mol–1. What is the

PC
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Q.31 Using the bond enthalpy data given below, calculate the enthalpy change for the reaction.
C2H4(g) + H2(g)  C2H6 (g)

ir
Data:
Bond
ir
C–C C=C C–H
J s H–H
Bond Enthalpy
J s 337 kJ/mol 606 kJ/mol
B
410.4 kJ/mol 431.8 kJ/mol

B b y
Q.32
y PC
Compute the enthalpy of formation of liquid methyl alcohol in kJ mol 1, using the following data.
b
PC
Enthalpy of vaporisation of liquid CH3OH = 38 kJ/ mol .
Enthalpy of formation of gaseous atoms from the elements in their standard states are
H  218 kJ / mol ; C 715 kJ / mol ; O  249 kJ / mol.
Average Bond energies
C  H  415 kJ / mol ; C  O  356 kJ / mol ; O  H  463 kJ / mol

Q.33
si r
From the following data :
s ir
Enthalpy of formation of CH3CN = 90 kJ/mol
J B J
B
Enthalpy of formation of C2H6 = – 85 kJ/mol
y b y
bEnthalpy of sublimation of graphite = 720 kJ/mol

P C Enthalpy of dissociation of nitrogen = 945 kJ/mol

Enthalpy of dissociation of H2 = 435 kJ/mol PC
C–H bond enthalpy = 415 kJ/mol
Calculate the bond enthalpy of (i) C – C ; (ii) C  N

Q.34 The enthalpy of combustion of acetylene is –312 kCal per mole. If enthalpy of formation of CO2 &

s ir
H2O are 94.5 & 68 kCal per mole respectively, calculate C  C bond enthalpy.
ir
J s
Given that enthalpy of atomisation of C is 150 kCal per mole and H – H bond enthalpy and C – H bond
B J
y
enthalpy are 103 kCal per mole and 93.50 kCal per mole respectively.
b y B
PC
Q.35
b
Using the given data calculate enthalpy of formation of acetone (g) . [All values in kJ mol1]
bond enthalpy of :
C  H = 415 ; C  C = 345 ; PC
(C = O) = 728.0 ;
(O = O) = 495.0 ; H  H = 436 ; subH of C = 720

Q.36 Find the enthalpy of S–S bond from the following data.
 f H  = – 147 kJ/mol
ir
(i) C2H5 – S – C2H5 (g)

(ii)
J s
C2H5 – S – S – C2H5 (g)  f H  = – 202 kJ/mol

y B s ir
(iii)
b S (g)  f H  = 225 kJ/mol
J
PC
Q.37
y B
Use the mean bond enthalpy data to calculate the enthalpy of combustion of ethanol.
CH3CH2OH(g) + 3O2(g)  2CO2(g) + 3H2O(g) b
PC
[Given : Bond energy (C – H) = 412 kJ/mol ; (C = O) = 743 kJ/mol
(C – C) = 348 kJ/mol ; (C – O) = 360 kJ/mol
(O = O) = 496 kJ/mol ; (O – H) = 463 kJ/mol
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RESONANCE ENERGY
Q.38 Calculate resonance energy of CO2(g) from the following data.

ir
Hcombustion of CO = –280 kJ / mol Hf CO = –120 kJ/mol

ir
Hatomisation of C(graphite)= 720 kJ / mol HBE O = O = 500 kJ mol–1
J s
J s HBE C = O = 710 kJ /mol
B
Q.39
B y
Calculate the enthalpy of combustion of methyl alcohol at 298 K from the following data
b
Bond
b y CH CO OH
PC
O=O C=O

PC
1
Bond Enthalpy(kJ mol ) 415 352 465 494 710
Resonance energy of CO2 =  143 kJ mol1
Latent heat of vaporisation of methyl alcohol = 35.5 kJ mol1.
Latent heat of vaporisation of water = 40.5 kJ mol1.

ir
Q.40 What will be the value of resonance energy of N2O if

J si r
HBDE N = N = 400 kJ/mol ; H of N2O = 100 kJ mol–1

B J s
y B
HBDE N  N = 950 kJ/mol ;
HBDE O = O = 500 kJ/mol
HBDE N = O = 600 kJ mol–1

b y
b
P C CALORIMETERY PC
Q.41 0.16 g of methane was subjected to combustion at 27º C in a bomb Calorimeter . The temperature of
Calorimeter system (including water) was found to rise by 0.5º C . Calculate the heat of combustion of
methane at
(a) constant volume

s ir
(b) constant pressure .
ir
B J
The thermal capacity of Calorimeter system is 17.7 kJ K1 . (R =
25
J
J mol1 K1)s
b y 3
y B
PC
Q.42
b
When 0.2 mol of ethane is burnt completely in a bomb calorimeter, the temperature of calorimeter

PC
system increased by 2 K. What should be the increase in temperature of the same calorimeter system,
when 0.4 mol of CH4 is burnt ?
[Given :  C U C 2 H 6 g  = – 400 Kcal/mol and  C U CH 4 g  = – 200 Kcal/mol]

Q.43 Two solutions initially at 25°C were mixed in an adiabatic constant pressure Calorimeter. One contains
400 ml of 0.2 M weak monoprotic acid solution. The other contain 100 ml of 0.80 M NaOH. After

ir
mixing temperature increased to 26.2 °C. How much heat is evolved in the neutralization of 1 mole of
s
J
acid? Assume density of solution 1.0 g/cm3, and specific heat of solution 4.0 J/g-K. Neglect heat capacity

B
of the Calorimeter.

b y s ir
J
PC B
Q.44 Benzoic acid is a common standard used in Bomb calorimeters, which maintain a constant volume. If

b y
1.22 gm of benzoic acid gives off 31.7 J of energy when burned in the presence of just sufficient oxygen

PC
at an initial temperature of 24.6°C, calculate molar heat capacity at constant volume of final product
mixture if all the heat produce is used for increasing temperature of the final product mixture and the final
temperature is 49.6°C. Also calculate, w and U for the given amount, assuming ideal gas behaviour.
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KIRCHOFF'S EQUATION

Q.45 For a reaction : 2A + 3B  C + D H 300 = 30 kJ/mol; S300 = 20 J/K mol

If molar heat capacites at constant pressure are given as :
s ir
s ir
CP,m A = 10 J/mol K; CP,m B = 15 J/mol K
B J
B J
CP,m C = 25 J/mol K; CP,m D = 20 J/mol K
b y
b y PC
4
Then calculate | Suniverse | (in J/k) if the above reaction is carried out at 400K. (ln   = 0.28)

PC
3
[Round off to nearest integer ]

Q.46 The standard enthalpy for the reaction H2(g) + 1/2 O2(g)  H2O(l) is – 285.76 kJ at 298 K.
Calculate the value of H at 373K. The molar heat capacities at constant pressure (C P) in the given
temperature range of H2 (g), O2(g) and H2O (l) are respectively 38.83, 29.16 and 75.312 JK–1mol–1.

Q.47
si r s ir
At 298 K, H°combustion (sucrose) = –5737 KJ/mol & G°combustion (sucrose) = –6333 KJ/mol.

J B J
Estimate additional non-PV work that is obtained by raising temperature to 310 K.
B
Assume rCP = 0 for this temperature change
y b y
b
P C PC

s ir ir
B J J s
b y y B
PC b
PC

s ir
B J
b y s ir
J
PC b y B
PC
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EXERCISE-2 (Objective Questions)

Single correct
Q.1 For which of the following change H not equal to E?
s ir
s ir
(A) H2 (g) + I2 (g)  2HI (g)
J
(B) HCl (aq)+ NaOH(aq)  NaCl(aq) + H2O(l)
B
B J
(C) C(s) + O2(g)  CO2(g) (D) N2 (g)+ 3H2(g)  2NH3(g)

b y
Q.2
b y
Find f H° for HCl(g) from the following data:
PC
PC
NH3(g) + HCl(g)  NH4Cl(s); rH° = –176 kJ/mol
N2(g) + 3H2(g)  2NH3(g); rH° = –92 kJ/mol
N2(g) + 4H2(g) + Cl2(g)  2NH4Cl(s); rH° = –629 kJ/mol
(A) 536.5 kJ/mol (B) –361 kJ/mol (C) –92.5 kJ/mol (D) None

Q.3 Calculate H combustion of acetone if H f of acetone = – 250 kJ

si r s
H combustion of Cgraphite = – 390 kJ/mol & H combustion of H2(g) = – 280 kJ/mol :ir
J B J
B
(A) – 1230 kJ/mol (B) – 1760 kJ/mol (C) – 1370 kJ/mol (D) – 1410 kJ/mol

b y b y
PC
Q.4 Reactions involving gold have been of particular interest to a chemist . Consider the following reactions,

P C Au(OH)3 + 4 HCl  HAuCl4 + 3 H2O ,

Au(OH)3 + 4 HBr HAuBr4 + 3 H2O ,
H =  28 kCal
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.5
s ir ir
The enthalpy of tetramerization of X in gas phase (4X(g)  X4(g)) is – 100 kJ/mol at 300 K.

B J J s
The enthalpy of vaporisation for liquid X and X4 are respectively 30 kJ/mol and 72 kJ/mol respectively.

y
S for tetramerization of X in liquid phase is – 125 J / K mol at 300 K.
b y B
PC
What is the G at 300 K for tetramerization of X in liquid phase ?
b
PC
(A) –52 kJ/mol (B) –89.5 kJ/mol
(C) –14.5 kJ/mol (D) None of these

Q.6 The reaction CH4(g) + Cl2(g)  CH3Cl(g) + HCl(g) has H = –25 kCal.
Bond
Bond Energy
kCal

s ir  C—Cl 84

B J  H—Cl 109

b y  C—H x
s ir
J
PC B
 Cl—Cl y
x:y=9:5
b y
PC
From the given data, what is the bond enthalpy of Cl—Cl bond
(A) 70 kCal (B) 80 kCal (C) 67.75 kCal (D) 60 kCal

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Q.7 Calculate C – H Bond energy from the following data :

fH(C,g) = 716.68 kJ/mol fH(H,g) = 217.97 kJ/mol fH(CH4,g) = – 74.81 kJ/mol
(A) 1663.37 kJ (B) 415.84 kJ (C) 179.17 kJ (D) 74.81 kJ

s ir
ir

Q.8 Which of the following reactions defines H f ?
s B J
B J
(A) C(diamond) + O2(g)  CO2(g)
(C) N2(g) + 3H2(g)  2NH3
(B) 1/2 H2(g) + 1/2 F2(g)  HF(g)

b y
(D) CO(g) + 1/2O2(g)  CO2(g)

b y PC
PC
Q.9 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

Q.10 Find rU° for the reaction 4HCl (g) + O2 (g)  2Cl2(g) + 2H2O (g) at 300 K. Assume all gases are
ideal.
si r s ir
J
BJ B
o
Given: H2(g) + Cl2(g)  2HCl (g)  r H 300 = – 184.5 kJ/mol

b y b y
PC
o
2H2(g) + O2(g)  2H2O (g)  r H 300 = – 483 kJ/mol (Use R = 8.3 J/mol)

P C
(A) 111.5 kJ/mol (B) –109.01 kJ/mol (C) –111.5 kJ/mol (D) None

Q.11 Which of the following represent standard formation reaction of given compound?
1
(A) Ag+(aq) + Cl–(aq)  AgCl(s) (B) CO(g) + O (g)  CO2(g)
2 2
1
s ir ir
(C)
2 2
B J
H (g) + (aq)  H+(aq) + 1e– (D) 2H2(g) + O2(g)  2H2O(l)
J s
b y y B
Q.12

PC b
The combustion 1.22g benzoic acid (M = 122) in a bomb calorimeter at 300K caused a temperature

PC
rise of 3K, while combustion of 0.88g ethyl ethanoate (M = 88) caused a temperature rise of 2K.
Calculate the enthalpy change of combustion of CH3COOC2H5(l) at 300K.
Given : Internal energy change of combustion for benzoic acid = – 3000kJmol–1 at 300K
(A) – 2000kJ (B) – 2002.49kJ (C) – 2006.5kJ (D) – 3002.5kJ

Q.13 In order to solve a complex physical chemistry problem, brain requires some "neural energies" which are
electrical in nature. Each problem on an average requires 21 Joules of neural energy. Calculate minimum

ir
amount of glucose required to solve 10 such problems if all electrical energy is obtained from oxidation
of glucose.
J s
yB ir
1000
[Given : H combustion of glucose = – 2800 kJ/mole, Scombustion of glucose = –
s
J/molK,

C b Temperature = 300K ]
B J
3

P (A) 14 gm (B) 14 mg (C) 20 gm

b y (D) 120 mg

Q.14
PC
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
Page # 9
 THERMOCHEMISTRY

Q.15 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

ir
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
ir
(B) 8.5 kJ/mol (C) – 11.5 kJ/mol
s
(D) none of these
J
J s B
Q.16
B b y
What is the ratio of the enthalpy yield on combustion of hydrogen atoms to steam to the yield on combustion

b y
of an equal mass of hydrogen molecules to steam?
PC
PC 1
Given : H2(g) + O2(g)  H2O(g) H = – 242 kJ
2
B.E. (H – H) = 436 kJ
(A) 0.80 : 1 (B) 1 : 0.80 (C) 1.80 : 1 (D) 2.80 : 1

Q.17
si r s ir
H 0f of water is – 285.8 kJ mol–1. If enthalpy of neutralisation of monoacid strong base is

J B J
B
–57.3 kJ mol–1, H 0f of OH– ion will be
y b y
P Cb
(A) – 228.5 kJ mol–1 (B) 228.5 kJ mol–1
PC
(C) 114.25 kJ mol–1 (D) –114.25 kJ mol–1

Q.18 Select the correct option.

(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)

s ir
(D) Hcombustion [H2(g)] is equal to Hf [H2(g)]
ir
Q.19
B J
From following Born Haber cycle, identify incorrect statement :
J s
b y y B
PC
C(g) + 4H(g)
b
PC
872 kJ
C(g) + 2H2(g)
715 kJ
Energy
C(graphite) + 2H2(g)
75 kJ
CH4(g)
(A) fH(CH4) = – 75 kJ (B) Bond energy of (C–H) = 145 kJ/mol

s ir
(C) sublimationH of C = 715 kJ/mol (D) formationH of H(g) = 218 kJ/mol

B J
Q.20
y
Study the following thermochemical equations:
b s ir
A  B ; H = + 100 Kcal
J
PC B  C ; H = – 80 Kcal
The correct order of enthalpies of formation of A, B and C is b y B
(A) A < B < C (B) A < C < B
PC
(C) C < A < B (D) B < C < A
s

Page # 10
 THERMOCHEMISTRY

Q.21 H of of atomic B is 134.5 Kcal/mol and H of of atomic F is 118 Kcal/mol. H of of BF3(g) is

– 271.5 Kcal /mol. Average B – F energy would be

ir
(A) 97.7 Kcal / mol (B) 116.6 Kcal / mol (C) 135.4 Kcal / mol (D) 253.3 Kcal / mol

ir J s
Q.22
s B
Calculate enthalpy of combustion of propane [C3H8 (g)] in kJ/mol at 298 K.
J
Given : B.E.(O = O) = 498 kJ/mol
B
; B.E. (C = O) = 804 kJ/mol
b y
b y
B.E. (C–H) = 410 kJ/mol
B.E. (C–C) = 345 kJ/mol
;
;
B.E.(O–H) = 464 kJ/mol

PC
Resosnace energy of CO2(g) = – 143 kJ/mol

PC Hvaporization (H2O, l ) = 41 kJ/mol

(A) –1996 (B) –2669 (C) –2324 (D) None of these

Q.23 For a reaction : 2A(g) + B(g)   C(g) , U° = 30 Kcal/mol, S° = 100 cal/K mol at 300K.
What will be the value of G°rxn at 400K? [R = 2 cal/K mol] [ C Prxn = 0]
(A) 0
si r
(B) – 1.2 Kcal (C) – 11.2 Kcal
s ir
(D) – 10 Kcal

J B J
B
Q.24 0.2 M, 100 ml NaOH is mixed with 0.4 M, 100 ml HCl solution. Determine energy released during the

b y
reaction.
b y
PC
Given : H+ (aq) + OH¯ (aq)  H2O (l)  H = – 57.5 kJ mol–1

P C (A) 1150 J (B) 1150 kJ (C) 2300 J (D) 2300 kJ

Q.25 Enthalpy of neutralization of H3PO3 acid is –106.68 kJ/mol using NaOH. If enthalpy of neutralization of
HCl by NaOH is –55.84 kJ/mol. Calculate Hionization of H3PO3 into its ions
(A) 50.84 kJ/mol (B) 5 kJ/mol (C) 2.5 kJ/mol (D) None

Q.26
s ir ir
When 100 ml 0.2 M KOH is mixed with 100 ml 0.2 M HCl, temperature of solution increases by t1oC

B J J s
while when 300 ml 0.1 M KOH is mixed with 300 ml 0.1 M HCl then increase in temperature is t o2C

b y y B
then which one is correct.(Assuming density as well as specific heat of final solutions are same)

PC
(A) t1 = t2 (B) t1 > t2 (C) t1 < t2 b (D) Can't be predicted

Q.27 The value of change in enthalpy for 1 mole of H2O in PC

H2O (l, 1 atm, 373K)  H2O (g, 1 atm, 393 K)
Given : CP(H2O, l) = 75.3 JK–1mol–1 , CP = (H2O, g) = 35 JK–1mol–1,
vapH at 373K = 40 kJ/mol
(A) 740 kJ (B) 39.3 kJ (C) 40.7 kJ (D) 740 J
More than one may correct

s ir
Q.28 Which of the following do(es) not represent H formation of the product.

B J
ir
1 1
(A)
b y
2
H2(g) +
2
Br2(g)  HBr (B) H2 (g) + Cl2 (g) 2HCl
J s
PC (C) NH 4 (g) + Cl–(g)  NH4Cl(s)
y B
(D) P4(black) + 5O2 (g)  P4O10(s)
b
Q.29
(A) G = 0 (B) G° = 0
PC
Which of the following is correct for boiling of CCl4(l) at its standard boiling point?
(C) S°>0 (D) H°vap > 0
Page # 11
 THERMOCHEMISTRY

Q.30 From the following data at 25°C

Reaction rH° kJ/mol
1 1
H (g) + O2(g)  OH (g)
2 2 2
42
s ir
1
s ir
H2(g) + O2(g)  H2O(g)
B J
J
–242
2
B b y
b y
H2(g)  2H(g)
O2(g)  2O(g)
436

PC
PC
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

si r s ir
Q.31
J J
100 ml 0.25 M H2SO4 (strong acid) is neutralised with 200 ml 0.2M NH4OH in a constant pressure
B
B y
Calorimeter which results in temperature rise of 1.4 °C. If heat capacity of Calorimeter content is
y b
b
PC
1.5 kJ/°C. Which statement is/are correct

P C 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

ir
(D) H for 2H2O(l)  2H+ (aq.) + 2OH¯(aq.) is 114 kJ

J s s ir
B
Assertion Reason

y B J
b
Q.32 Statement-1 : The enthalpy of neutralization of the reaction between HCl and NaOH is

b y
PC
– 13.7 kCal / mol. If the enthalpy of neutralization of oxalic acid (H2C2O4) by a

PC
strong base is – 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.

ir
(D) Statement-1 is false, statement-2 is true.
s
B J
Q.33
y ir
Statement-1: Standard enthalpy of isomerisation of an enantiomer into the other is zero.
b s
J
Statement-2: The two enantiomers of any chiral compound have the same enthalpy of formation.

PC y B
(A) Statement-1 is true, statement-2 is true and statement-2 is correct explanation for statement-1.
b
(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. PC
Page # 12
 ANSWER KEY THERMOCHEMISTRY

EXERCISE-1

Q.1 – 1200 kJ/mol Q.2 – 800 kJ/mol

s ir
s ir
H rxn  – 200 kJ/mol, Srxn = – 180 J/K, G° = – 146 kJ/mol
B J
Q.3

B J b y
Q.4
y
204.67 J/K-mol
b
Q.5 T = 300 K
PC
Q.6
PC
(a) CCl4(l) l CCl4(g) (Equilibrium at 1 atm pressure)
(b) G = 0
(c) 400 K

Q.7 Vapour pressure = 0.13 bar. Q.8 – 37.5 kJ/mol

Q.9
si r
(a) YES, As G°rxn = –ve ie reaction is spontaneous at 1127°C,
s ir
(b) 10 bar
J
(c) 10 bar (d) 1230.6 K
B J
y B
(e) It is entropy driven process
(f) In forward direction
b y
b
Q.10
P
Q.11
C – 88 kJ/mol

128 kJ Q.12
PC
–266 kJ/mol and –824 kJ/mol Q.13 –108.7 kJ / mol

Q.14 – 40 kJ/mol Q.15 –1560 kJ mol–1

Q.16 (a)  3201 kJ/mol; (b)  3199.75 kJ/mol

si r ir
Q.17 (a) 100.3 g; (b) 101.69 g Q.18 – 700 Kcal/mol

Q.19
BJ
65564 kJ /mol Q.20 22 kJ/mol
J s
Q.21
b y
Cis-2-butene  Trans-2-butene Hr = ?
y B
P C b
PC
rH = – 3.3 kJ/mol

Q.22 – 75 kJ/mol Q.23 solH of AgF(s) = 6 kJ/mol ; Hsoln AgCl = 95 kJ/mol

Q.24 – 18.7 kCal / mol Q.25  1410 Cal

Q.26 mole % O2(g) = 37.14, H2O(g) = 62.86 Q.27  72 kJ mol–1

Q.28 1:3 Q.29 + 23 k Cal Q.30 213 kJ / mol

Q.31 – 120 kJ/mol

s ir Q.32 - 266 kJ mol–1 Q.33 (i) 340 kJ/mol–1;(ii) 890 kJ/mol–1
J
Q.34
yB
EC º C = 161 kCal / mol Q.35  192.5 kJ mol1 Q.36
s ir
280 kJ/mol

Q.37
P Cb
– 1031 kJ/mol Q.38 200 kJ
y B J
Q.39 – 665.5 kJ mol-1

Q.40 100 kJ / mol Q.41 (a)  885 kJ/mol (b)  890 kJ/mol
b Q.42 2K

Q.43 –30 kJ/mol Q.44 PC

C = 12.68 J/mole-K, w = 0, U = –31.7 J

Q.45 56 Q.46 H 373 (H2O (l) )= – 284.11 kJ Q.47 24 kJ/mol

Page # 13
 THERMOCHEMISTRY

Exercise-2

ir
Q.1 D Q.2 C Q.3 B Q.4 C
Q.5 C
ir
Q.6 D Q.7 B Q.8
JBs
J s B
Q.9 C
B
Q.10 C Q.11 C
b y
Q.12 B
Q.13 B
b y Q.14 B Q.15 C

PC
Q.16 D

PC
Q.17 A Q.18 C Q.19 B Q.20 B
Q.21 D Q.22 B Q.23 C Q.24 A

Q.25 B Q.26 B Q.27 C

Q.28 ABCD Q.29 ABCD Q.30 AD Q.31 ABD
Q.32 D

si r
Q.33 A
s ir
J B J
y B b y
b
P C PC

s ir ir
B J J s
b y y B
PC b
PC

s ir
B J
b y s ir
J
PC b y B
PC
Page # 14