Thermodynamics(Chemistry)

Numerical Problems Questions with Answers, Solution

53. Calculate the work done when 2 moles of an ideal gas expands reversibly
and isothermally from a volume of 500 ml to a volume of 2 L at 25°C and
normal pressure.

n = 2 moles

Vi = 500ml = 0.5lit

Vf = 2lit

T = 25°C = 298K

w = −2.303 nRT log (Vf / Vi)

w = −2.303 × 2 × 8.314 × 298 × log(2/0.5)

w = −2.303 × 2 × 8.314 × 298 × log(4)

w = − 2.303 × 2 × 8.314 × 298 × 0.6021

w = − 6871J

w = − 6.871kJ

54. In a constant volume calorimeter, 3.5 g of a gas with molecular weight 28

was burnt in excess oxygen at 298 K. The temperature of the calorimeter was
found to increase from 298 K to 298.45 K due to the combustion process. Given
that the calorimeter constant is 2.5 kJ K−1. Calculate the enthalpy of
combustion of the gas in kJ mol−1.
Given

Ti = 298K

Tf = 298.45K

k = 2.5 kJK−1

m = 3.5g

Mm = 28

Heat evolved = kΔT

= k(Tf − Ti)

= 2.45 kJK−1 × (298.45 − 298)K

= 1.12 kJ

Heat evolved for 3.5 g of a gas = 1.12 kJ

∴ Heat evolved for 28g of gas ( 1 mole)

= (1.125×28) / 3.5

The enthalpy of combustion of the gas

ΔHC = 9JK mol−1

55. Calculate the entropy change in the system, and surroundings, and the total
entropy change in the universe during a process in which 245 J of heat flow out
of the system at 77°C to the surrounding at 33°C.

Given:
Tsys = 77oC = (77 + 273 ) = 350K

Tsurr = 33oC = (33 + 273) = 306K

q = 245J

Solution:

ΔSsys = q/Tsys = −245 / 350 = − 0.7 JK−1

ΔSsurr = q/Tsys = +245 / 350 = +0.8 JK−1

ΔS = ΔSsys + ΔSsurr

ΔS univ = −0.7 JK−1 + 0.8 JK−1

ΔS univ = −0.1 JK−1

56. 1 mole of an ideal gas, maintained at 4.1 atm and at a certain temperature,
absorbs heat 3710J and expands to 2 litres. Calculate the entropy change in
expansion process.

Given:

p = 4.1 atm,

v = 2 lit,

q = +3710 J,

n = 1 mol

Solution:

The ideal gas equation is

= ( 4.1 atm × 2 lit ) / ( 0.0821 lit atm mol−1 K−1 × 1 mol )

T = 100 K

ΔSexpansion = qexpansion / T = 3710J / 100k = 37.1 JK−1

ΔSexpansion = 37.1 JK−1

57. 30.4 kJ is required to melt one mole of sodium chloride. The entropy
change during melting is 28.4 JK−1 mol−1 . Calculate the melting point of
sodium chloride.

Given :

ΔHfusion = 30.4 kJ mol −1

ΔSfusion = 284.4 JK−1 mol−1

Solution:

ΔSfusion = ΔHfusion / Tf

Melting point of NaCl, Tf = ΔHfusion / ΔSfusion

= 30.4 kJ mol−1 / 28.4 JK−1 mol−1 = ( 30.4 × 1000 J mol−1 ) / ( 28.4 JK−1 mol−1)

Melting point of NaCl, Tf = 1070.4 K

58. Calculate the standard heat of formation of propane, if its heat of
combustion is −2220.2 KJmol−1 the heats of formation of CO2 (g) and H2O(1)
are −393.5 and −285.8 kJ mol−1 respectively.

Given :

ΔH0f CO2 = −393.5 kJ mol−1

ΔH0f H2O = −285.8 kJ mol−1

ΔH0f C3H8 = −2220.2 kJ mol−1

Solution:

Combustion of propane

C3H8 + 5O2 → 3CO2 + 4H2O

ΔH0c = ∑ ΔH0f p − ∑ ΔH0f r

−2220.2 = −1180.5 − 1143.2 − ΔH0f C3H8

ΔH0f C3H8 = −103.5 kJ mol−1

ΔH0f C3H8 = −103.5 KJ

59. You are given normal boiling points and standard enthalpies of
vapourisation Calculate the entropy of vapourisation of liquids listed below.
Solution

For Ethanol:

Given

Tb = 78.4oC = (78.4 + 273) = 351.4K

ΔHV (Ethanol) = + 42.4kJ mol−1

ΔSV = ΔHV/Tb

ΔSV = + 42.4kJ mol−1 / 351.4K

ΔSV = +42400 J mol−1 / 351.4K

ΔSV = +120.66 JK−1mol−1

For Toluene:

Given

Tb =110.6°C = (110.6 +273) = 383.6K

ΔHV (Toluene) = + 35.2 kJ mol−1

ΔSV = ΔHV / Tb

ΔSV = 35.2 kJ mol−1 / 383.6 K

ΔSV = +91.76 JK−1 mol−1

60. For the reaction Ag2O(s) —> 2Ag(s) + ½ O2(g) : ΔH = 30.56 kJ mol−1 and
ΔS=6.66JK−1 mol−1 (at 1 atm). Calculate the temperature at which ΔG is equal
to zero. Also predict the direction of the reaction (i) at this temperature and (ii)
below this temperature.

Given:

ΔH = 30.56 kJmol−1

= 30560Jmol−1

ΔS = 6.66 ×10−3kJK−1mo1−1

T = ? at which ΔG = 0

ΔG = ΔH − TΔS

0 = ΔH − TΔS

T = ΔH / ΔS

T = (30.56 kJmol−1) / (6.66×10−3 kJK−1mol−1)

T = 4589K

(i) At 4589K ; ΔG = 0 the reaction is in equilibrium.

(ii) At temperature below 4589k, ΔH > T ΔS ΔG = ΔH −T ΔS > 0, the reaction in

the forward direction, is non spontaneous. In other words the reaction occurs in the
backward direction.

61. What is the equilibrium constant Keq for the following reaction at 400K.
2NOCl ⇌ 2NO(g) + Cl2(g)

given that ΔHo = 77.2 kJ mol−1 ; and ΔS° = 122 JK−1 mol−1

Given:

T = 400 K

ΔH°c = 77.2 KJmol−1

= 77200 Jmol−1

ΔG° = − 2.303RT log Keq

log Keq = − ΔG° / 2.303 RT

log Keq = − (ΔH° − T ΔS°) / 2.303 RT

log Keq = − ( [77200 – 400 × 122] / [2.303 × 8.314 × 400] )

log Keq = − (28400 / 7659)

log Keq = − 3.7080

Keq = antilog (−3.7080)

Keq = 1.95 ×10-4

62. Cyanamide (NH2CN) is completely burnt in excess oxygen in a bomb

calorimeter, ΔU was found to be -742.4 kJ mol−1, calculate the enthalpy change
of the reaction at 298K. NH2CN(s) + 3/2 O2(g) → N2 (g) + CO2 (g) + H2O(l)
ΔH= ?

Given
T = 298K; Δ U= −742.4kJmol−1

ΔH = ?

Solution:

ΔH = ΔU + ΔngRT

ΔH = ΔU+ (np − nr) RT

ΔH = -742.4 + (2- 3/2) × 8.314 × l0−3 × 298

= −742.4 + (0.5 × 8.314 × 10−3 × 298)

= −742.4 + 1.24

= −741.16 kJmol−1

63. Calculate the enthalpy of hydrogenation of ethylene from the following

data. Bond energies of C-H, C-C, C = C and H - H are 414, 347, 618 and 435 kJ
mol−1

Given:

EC-H = 414kJ mol−1

Ec-c = 347 kJ mol−1

Ec-c = 618kJ mol−1

EH-H = 435 kJ mol−1

Solution:
ΔHr = ∑(Bond energy)r − ∑p (Bond energy)p

ΔHr = (Ec-c + 4EC-H + EH-H) − (Ec-c + 6EC-H)

ΔHr = (618 + (4 × 414) = 435) − (347 + (6 × 414))

ΔHr = 2709 − 2831

ΔHr = −122 kJ mol−1

64. Calculate the lattice energy of CaCl2 from the given data

Ca (s)+Cl2(g) → CaCl2(s) ∆H0f = − 795 kJ mol−1

Ca(s) + Cl2(g) → CaCl2(s) ΔH°f = −795 kJ mol−1

Atomisation : Ca(s) → Ca(g) ΔH°1 = +121 kJ mol−1

Ionisation: Ca(g) → Ca2+(g) + 2e− ΔH°2 = +2422 kJ mol−1

Dissociation : Cl2(g) → 2Cl(g) ΔH°3 = +242.8 kJ mol−1

Electron affinity : Cl(g) + e− → Cl−(g) ΔH°4 = −355 kJ mol−1

Solution:
ΔHf = ΔH1 + ΔH2 + ΔH3 + 2 ΔH4 + u

−795 = 121 + 2422 + 242.8 + (2 × −355) + u

−795 = 2785.8 − 710 + u

−795 = 2075.8 + u

u = − 795 − 2075.8

u = −2870.8 kJ mol−1

65. Calculate the enthalpy change for the reaction Fe2O3 + 3CO → 2Fe + 3CO2
from the following data.

2Fe + 3/2 O2 → Fe2O3; ΔH = -741kJ

C + 1/2 O2 → CO; ΔH = −137kJ

C+ O2 → CO2; ΔH = − 394.5kJ

­Given :

ΔHf (Fe2O3) = − 741kJmol−l

ΔHf (CO) = − 137kJmol−1

ΔHr = ?

Solution:

Fe2O3 +3CO → 2Fe + 3CO2

ΔHr = ∑( ΔHf) products − ∑ (ΔHf )reactants

ΔHr = [0+ 3(− 394.5)] − [−741 + 3(− 137)]

ΔHr = [−1183.5] − [−1152]

ΔHr = −1183.5 + −1152

ΔHr = −31.5 kJ mol−1

66. When 1-pentyne (A) is treated with 4N alcoholic KOH at 175°C, it is

converted slowly into an equilibrium mixture of 1.3% 1-pentyne (A), 95.2%
2-pentyne (B) and 3.5% of 1,2 pentadiene (C) the equilibrium was maintained
at 175°C, calculate ΔG0 for the following equilibria.

B⇌A ΔG01 = ?

B⇌C ΔG02 = ?

Given :

T= 175° C = 175 + 273 = 448K

Concentration of 1-pentyne [A] = 1.3%

Concentration of 2-pentyne [B] = 95.2%

Concentration of 1, 2-pentadiene [C] = 3.5%

B [95.2%] ⇌ A [3.5%]

K1 = 1.3 / 95.2 = 0.0136

B [95.2%] ⇌ C [3.5%]

K2 = 3.5 / 95.2 = 0.0367

⇒ ΔG01 = −2.303 RT logK1

ΔG01 = −2.303 × 8.314 × 448 × log0.0136

ΔG01 = −2.303 × 8.314 × 448 × −1.8664

ΔG01 = +16010J

ΔG01 = +16 kJ

ΔG02 = −2.303 RT logK2

ΔG02 = −2.303 × 8.314 × 448 × log 0.0367

ΔG02 = −2.303 × 8.314 × 448 × −1.4353

ΔG02 = +12312 J

ΔG02 = +12.312 kJ

67. At 33K, N2O4 is fifty percent dissociated, calculate the standard free energy
change at this temperature and at one atmosphere

Given:

N2O4 ⇌ 2NO2

Initial mole 1
At Equilibrium remaining mole

Total moles at equilibrium 0.5 + 1 = 1.5

Total pressure = 1atm

Partial pressure = mole fraction × total pressure

PN2O4 = (0.5/1.5) × 1 = 0.5 / 1.5

PNO2 = (1/1.5) × 1 = 1/ 1.5

KP = PNO2 / PN2O4 = (1/1.5)2 / (0.5/1.5) = 1.33

We know that,

ΔG° = −2.303RT log Keq

= −2.303 × 8.314 × 331og 1.33

= −2.303 × 8.314 × 33 × 0.1239

ΔG° = −78.29Jmol−1

[Alternative Answer]
68. The standard enthalpies of formation of SO2and SO3are −297 kJ mol−1 and
−396 kJ mol−1 respectively. Calculate the standard enthalpy of reaction for the
reaction: SO2 + ½ O2 → SO3

Given:

ΔHof (SO2) = −297 kJ mol−1

ΔHof (SO2) = −396 kJ mol−1

SO2 + ½ O2 → SO3

ΔHo1 = ?

Solution:
ΔHor = (ΔHof)compound

− ∑ (ΔHf)elements

ΔHor = ΔHof (SO3) − ( ΔHof (SO2) + 1/2 ΔHof (O2) )

ΔHor = −396 kJ mol−1

= − (−297kJ mol−1 + 0)

ΔHor = −396 kJ mol−1 + 297

ΔHor = − 99kJ mol−1

69. For the reaction at 298 K: 2A +B —> C

ΔH = 400 J mol−1; ΔS = 0.2 JK−1mol−1

Determine the temperature at which the reaction would be spontaneous.

Given :

ΔH = 400 J mol−1

ΔS = 0.2 J K−1 mol−1

T = 298 K

Solution:

We know that ΔG = ΔH − TΔS

At equilibrium, ΔG = 0

∴ TΔS = ΔH
T = ΔH / ΔS = ( 400 J mol−1 ) / ( 0.2 Jk−1 mol−1)

T = 2000K

ΔG = 400 − (2000 × 0.2)

=0

if T > 2000K ΔG will be negative

The reaction would be spontaneous only beyond 2000K

70. Find out the value of equilibrium constant for the following reaction at
298K, 2NH3(g) + CO2(g) ⇌ NH2CONH2(aq) + H2O (1) Standard Gibbs energy
change, ΔGr0 at the given temperature is −13.6 kJ mol−1.

Solution :

Given:

T = 298K

ΔGr0 = −13.6 kJ mol−1

ΔG0 = −2.303 RT log Keq

log Keq = −ΔG0 / 2.303RT

log Keq = [−(−13.6)] / [2.303 × 8.314×10–3 × 298]

log Keq = 2.38

Keq = antilog (2.38)

Keq = 239.88
71. A gas mixture of 3.67 lit of ethylene and methane on complete combustion
at 25°C and at 1 atm pressure produce 6.11 lit of carbondioxide. Find out the
amount of heat evolved in kJ, during this combustion. (ΔHc(CH4) = - 890 kJ
mol−1 and (ΔHc(C2H4) = −1423 kJ mol−1

Solution:

ΔHC (CH4) = − 890 kJ mol−1

ΔHC (C2H4) = − 1423 kJ mol−1

Let the mixture contain x lit of CH4 and (3.67 − x) lit of ethylene.

CH4 + 2O2 → CO2 + 2H2O

x lit x lit

C2H4 + 3O2 → 2CO2 + 2H2O

(3.67-x) lit 2 (3.67 - x) lit

Volume of Carbondioxide formed

= x + 2 (3.67− x) = 6.11 lit

x + 7.34 − 2x = 6.11

7.34 - x = 6.11

x = 1.23 lit

Given mixture contains 1.23 lit of methane and 2.44 lit of ethylene, hence
ΔHc = [(ΔHc (CH4) / 22.4) × (x)] + [ (ΔHc (C2H4) / 22.4) × (3.67 - x) ]

ΔHc = [ (−890kJmol−1 / 22.4) × 1.23] + [ (−1423/22.4) × (3.67 − 1.23) ]

ΔH = [ −48.87kJmol−1] + [−155kJmol−1]

ΔHc = −203.87 kJmol−1

Problem

The standard enthalpies of formation of C2H5OH(l), CO2(g) and H2O(l) are -

277, -393.5 and -285.5 kJ mol-1 respectively.

Calculate the standard enthalpy change for the reaction

C2H5OH(l)+3O2(g) →2CO2(g)+ 3 H2O(l)

The enthalpy of formation of O2(g) in the standard state is Zero, by definition

Solution:

For example, the standard enthalpy change for the combustion of ethanol can be
calculated from the standard enthalpies of formation of C2H5OH(l), CO2(g) and
H2O(l). The enthalpies of formation are –277, – 393.5 and –285.5 kJ mol–1
respectively.

C3H5OH(l) + 3O2(g) → 2CO2(g) + 3H2O(l)

=[ −787 − 856 . 5] − [ −277]

= - 1643 .5 + 277

∆H0r = −1366 . 5 KJ

Problem
Calculate the value of ∆U and ∆H on heating 128.0 g of oxygen from 0o C to
1000 C. CV and CP on an average are 21 and 29 J mol-1 K-1. (The difference is
8Jmol-1 K-1 which is approximately equal to R)

Solution.
We know
∆U = n Cv (T2-T1)

∆H = n CP (T2- T1)

Here

n= 128/32 4 moles ;

T2 = 1000

C =373K;

T1 = 00

C = 273K

∆U = n Cv (T2-T1)

∆U = 4 x 21 x (373 - 273)

∆U = 8400 J

∆U = 8.4 kJ

∆H = n Cp (T2- T1)

∆H = 4 × 29 × (373- 273)

∆H = 11600 J

∆H = 11.6 kJ

Problem:

If an automobile engine burns petrol at a temperature of 816o C and if the

surrounding temperature is 21o C, calculate its maximum possible efficiency.
Solution:

Here

Th = 816+273= 1089 K;

Tc= 21+273= 294K

%Efficiency=( 1089-294 / 1089) x100

%Efficiency=73%

Problem:

Calculate the standard entropy change for the following reaction( ∆S0f ), given
the standard entropies of CO2(g), C(s),O2(g) as 213.6 , 5.740 and 205 JK−1
respectively.

C(g) + O2(g) →CO2(g)

S0r = ∑ S0products − ∑ Sreac0 tan ts

S0r = {S0CO 2 } − {SC0 + S0O2 }

S0r = 213.6 − [5.74 + 205]

S0r = 213.6 −[210.74]

S0r = 2.86 JK−1

Problem:
Calculate the entropy change during the melting of one mole of ice into water
at 00 C and 1 atm pressure. Enthalpy of fusion of ice is 6008 J mol-1

Given:

∆Hfusion = 6008 Jmol−1

Tf = 0 0

C = 273 K

H 2O(S) --273 K→ H 2O ( l)

S fusion = 22 .007 J K −1 mole−1

Problem:
Problem:

Calculate ΔG0 for conversion of oxygen to ozone 3/2 O2 ↔ O3(g) at 298 K, if Kp

for this conversion is 2.47 u 10−29 in standard pressure units.

Solution:

ΔG0 = − 2.303 RT log Kp

Where

R = 8.314 JK−1mol−1

Kp = 2.47 x10−29

T = 298K

ΔG0=−2.303(8.314)(298)log(2.47u10−29)
ΔG0 = 16300 Jmol−1

ΔG0 = 16.3 KJ mol−1

1. Calculate ∆Hf° for the reaction

CO2(g)+ H2(g) → CO(g)+ H2O(g)

given that ∆Hf° for CO2 (g), CO (g) and H2O(g) are – 393.5, – 111.31 and – 242
kJ mol–1 respectively.

Solution :

Given

∆Hf0 CO2 = -393.5 kJ mol-1

∆Hf0 CO = -111.31 kJ mol-1

∆Hf0 (H2O) = -242 kJ mol-1

CO2(g) + H2(g) → CO(g) + H2O(g)

∆Hr0 = ?

∆Hr0 = Σ (∆Hf0 )products– Σ (∆Hf0)reactants

∆Hr0 = [∆Hf0 (CO) + ∆Hf0 (H2O)] – [∆Hf0 (CO2 )+∆Hf0

(H2)] ∆Hr0 = [– 111.31 + (– 242)] – [– 393.5 + (0)]

∆Hr0 = [– 353.31] + 393.5

∆Hr0 = 40.19

∆Hr0 = + 40.19 kJ mol–1

2. Calculate the amount of heat necessary to raise 180 g of water from 25° C to
100° C. Molar heat capacity of water is 75.3 J mol-1 K-1

Solution :

Given :

number of moles of water n

=180g / (18g mol-1 )= 10 mol

molar heat capacity of water

CP = 75.3 J K–1 mol–1

T2 = 1000 C = 373 K

T1 = 250 C= 298 K

ΔH = nCP (T2 – T1)

ΔH = 10 mol × 75.3 J mol–1 K–1 × (373 – 298) K

ΔH = 56475 J

ΔH = 56.475 kJ

3. From the following data at constant volume for combustion of benzene,

calculate the heat of this reaction at constant pressure condition.

C6H6(l) + 7½ O2(g) → 6CO2 (g) + 3 H2O(l)

ΔU at 25° C = -3268.12 kJ

Solution :
T = 250 C = 298 K ;

∆U = –3268.12 kJ mol–1

∆H = ?

∆H = ∆U + ∆ngRT

∆H = ∆U + (np – nr) RT

H = -3268.12+ (6 - 7/2) x 8 314 × 10 -3 x 298.

∆U = –3268.12 + (2.5 × 8.314 ×10-3 × 298)

∆U = – 3268.12 + 6.19

∆U = – 3261.93 kJ mol–1

4. When a mole of magnesium bromide is prepared from 1 mole of magnesium

and 1 mole of liquid bromine, 524 kJ of energy is released.

The heat of sublimation of Mg metal is 148 kJ mol–1. The heat of dissociation of

bromine gas into atoms is 193 kJ mol–1. The heat of vapourisation of liquid
bromine is 31 kJ mol–1. The ionisation energy of magnesium is 2187 kJ mol–1
and the electron affinity of bromine is – 662 kJ mol–1. Calculate the lattice
energy of magnesium bromide.

Solution :

Given :

Mg(S) + Br2(1) →

MgBr2(S) ∆Hf0 = –524 KJ mol–1

Sublimation :

Mg(S) → Mg(g)

∆H10 = +148 KJ mol–1

Ionisation:

Mg(g) → Mg2+(g) + 2e–

∆H20 = 2187 KJ mol–1

Br2(1) → Br2(g)

∆H30 = +31 KJ mol–1

Dissociation :

Br2(g) → 2Br(g)

∆H40 = +193 KJ mol–1

Electron affinity:

Br(g) + e – → Br – (g)

∆H50 = – 331 KJ mol–1

Solution :
ΔHf =ΔH1 + ΔH2 + ΔH3 + ΔH4 +2ΔH5 + u

– 524 = 148 + 2187 + 31 + 193+(2 × – 331) + u

– 524 = 1897 + u

u =–524 – 1897

u =– 2421 kJ mol–1

5. An engine operating between 1270 C and 470 C takes some specified amount
of heat from a high temperature reservoir. Assuming that there are no
frictional losses, calculate the percentage efficiency of an engine.

Solution:

Given

Th = 1270 C = 127 + 273 = 400

K TC = 470 C = 47 + 273 = 320

K % efficiency η = ?
6. Urea on hydrolysis produces ammonia and carbon dioxide. The standard
entropies of urea, H2O, CO2, NH3 are 173.8, 70, 213.5 and 192.5J mole-1K-1
respectively. Calculate the entropy change for this reaction.

Solution: