3.

CHEMICAL THERMODYNAMICS
AND ENERGETICS
1) Three moles of an ideal gas are ∴ 0.36 = –1.2 × (V2 – 0.5)
expanded isothermally from a volume 0.36
of 300 cm3 to 2.5 L at 300 K against a ∴ = –(V2 – 0.5)
1.2
pressure of 1.9 atm. Calculate the work
done in L atm and joules. ∴ 0.3 = –V2 + 0.5
Given : ∴ V2 = 0.2 L
V1 = 300 cm3
= 300 × 10–3 L ∴ V2 = 200 cm3
= 0.3 L
V2 = 2.5 L 3) Calculate the maximum work when 24
T = 300 K g of oxygen are expanded isothermally
P = 1.9 atm and reversibly from a pressure of
1.6 × 105 Pa to 100 kPa at 298 K.
To Find : Given :
Work done (W) Mass = 24 g
Formula : P1 = 1.6 × 105 Pa
W = –P∆
∆V P2 = 100 K Pa
Solution : = 100 × 103 Pa
∴ W = –P∆
∆V = 105 Pa
W = –1.9(2.5 – 0.3) 24
= –1.9 × 2.2 n =
32
= –4.18 L atm
= 0.75 moles
Now, 1 L atm = 101.33 J
R = 8.314 J K–1 mol–1
So –4.18 L atm = –423.56 J
T = 298 K
∴ W = –423.56 J
To Find :
2) One mole of an ideal gas is compressed Maximum mark (Wmax)
3
from 500 cm against a constant pressure Formula :
5
of 1.216 × 10 Pa. The work involved in P
the process is 36.50 J. Calculate the final Wmax = –2.303nRT log10 1
P2
volume.
Solution :
Given :
V1 = 500 cm3 P
= 0.5 L Wmax = –2.303nRT log10 1
P2
P = 1.216 × 105 Pa
= –2.303 × 0.75 × 8.314 × 298
= 1.2 atm
W = 36.50 J 1.6 × 10 5
= 0.36 L atm × log10
10 5
To Find :
= –2.303 × 0.75 × 8.314 × 298
Find Volume (V2)
× log10 1.6
Formula :
= –4273.39 × log 1.6
W = –P∆ ∆V
= –4279.39 × 0.204
Solution :
Wmax = –873 J
W = –P∆ ∆V
Chemical Thermodynamcs and Energetics
 .. 2

4) Three moles of an ideal gas are 5) 2.8 × 10–2 kg of nitrogen is expanded

compressed isothermally and reversibly isothermally and reversibly at 300 K
to a volume of 2L. The work done is from 15.15 × 105 Nm–2 when the work
0
2.983 kJ at 22 C. Calculate the initial done is found to be –17.33kJ. Find the
volume of the gas. final pressure.
Given : Given :
n = 3 moles
V2 = 2L 2.8 × 10 –2 × 10 3
n =
Wmax = 2.983 kJ 28
= 2.983 × 103 J = 1 mole
T = 220C T = 300 k
= 295 K P1 = 15.15 × 105 Nm–2
R = 8.314 JK–1 mol–1 Wmax = –17.33 kJ
To Find : = –17.33 × 103 J
Initial volume To Find :
Formula : Final pressure
Formula :
V
Wmax = –2.303nRT log10 2
V1 P
Wmax = –2.303nRT log10 1
Solution : P2
Solution :
V
Wmax = –2.303nRT log10 2
V1 P
Wmax = –2.303nRT log 1
∴ 2.983 × 10 3
= –2.303 × 3 × 8.314 P2
∴ –17.33 × 103 = –2.303 × 8.314
V2
× 295 log10
V1 15.15 × 105
× 300 log
3
P2
2.983 × 10 2
∴ – = log10 ∴ 17.33 × 10 3
16,945.22 V1
15.15 × 105
2 = 5.744 × 10 log 3
∴ –0.176 = log10 P2
V1
Take antilog on both sides. 17.33 15.15 × 105
∴ = log
2 5.744 P2
Antilog [–0.176] =
V1
15.15 × 105
2 ∴ 3.017 = log
P2
∴ 0.6668 =
V1 Taking antilog on both sides
2 15.15 × 105
∴ V1 = Antilog [3.017] =
0.6668 P2
∴ V1 = 2.999 L
∴ V1 = 3L 15.15 × 105
∴ 1039.92 =
P2

Chemical Thermodynamcs and Energetics

 .. 3

To Find :
15.15 × 10 5 W
∴ P2 =
1039.92 Formula :
P2 = 1456.8 Nm–2 W = –∆ ∆ nRT
Solution :
6) A sample of gas absorbs 4000 kJ of heat. i) 2SO2(g) + O2(g) 2SO3(g)
i) If volume remains constant, what is 1 mole of SO2 will 0.5 mole of O2 to give
∆U ? 1 mole of SO3.
ii) Suppose that in addition to W = –∆∆ n.RT
absorption of heat by the sample, the = –RT(n2 – n1)
surroundings does 2000 kJ of work W = –8.314 × 323(1 – 1.5)
on the sample, what is ∆U ? = –8.314 × 323 × (–0.5)
iii) Suppose that as the original sample W = 1342.7 J
absorbs heat, it expands against As W is positive, work is done on
atmospheric pressure and does 600 kJ system.
of work on its surroundings. What ii) NH 4NO 3(s) N2O(g) + 2H2O(g)
is ∆U ? 2 moles of NH 4NO 3(s) gives 2 moles of
Given : N2O(g) and 4 moles of H2O(g)
i) q = 4000 KJ So, ∆n = (6 – 0)
ii) W = 2000 KJ = 6
iii) w = 600 KJ W = –∆∆ n.RT
To Find : = –6 × 8.314 × 373
i) ∆U ii) ∆U iii) ∆U = –18606.75 J
Solution : W = –18.61 kJ
i) At constant volume, ∆H = ∆U As W is negative, work is done by the
So, ∆ U = 4000 kJ system.

ii) Surroundings does 2000 kJ of work on 8) The enthalpy change for the reaction
sample C 2
H4(g) + H2(g) C 2 H 6(g) is –620 J
So, ∆ U = 4000 + 2000 when 100 mL of enthylene and 100 mL
= 6000 kJ of H 2
react at 1 atm pressure. Calculate
iii) Original sample absorbs heat and expands the pressrure volume work and ∆U.
aginst atmospheric pressure. Work done Given :
on surroundings. ∆H = –620 J,
∆ U = 4000 – 600 V 1
= 200ml = 0.2 L
= 3400 kJ P = 1 atm
V2 = 100 ml = 0.1 L
7) Calculate the work done in each of the
following reactions. State whether work To Find :
is done on the system or by the system.. Pressure – Volume work (W)
i) The oxidation of one mole of SO2 at 500C ∆U
2SO2(g) + O2(g) 2SO3(g) Formula :
ii) Decomposition of 2 moles of NH4NO 3 W = –P∆
∆V
0
at 100 C Solution :
NH 4 NO 3(s) N2O(g) + 2H2O(g) W = –P∆
∆V
= –1 × (0.1 – 0.2)
= –1 × –0.1
Chemical Thermodynamcs and Energetics
 .. 4

W = 0.1L. atm 10) Calculate the standard enthalpy of

= 0.1 × 101.33 J formation of C2H6 from the following
= +10.13 J data :
∆H = ∆U + P∆V 2C2H6(g) + 7O2(g) 4CO2(g) + 6H2O(l),
W = –P∆V ∆H0 = –3119 kJ mol–1
10.13 = –P∆V ∆fH 0(CO2 ) = –285.8 kJ mol–1.
∴ P∆V = –10.13 J Given :
∆H = –620 J Standard enthalpy of reaction (∆ ∆ H0)
∴ ∆U = ∆H – P∆V = –3119 kJ
= –620 – (–10.13) ∆fH 0(CO2 ) = –393.5 kJ/mol
= –620 + 10.13 ∆fH 0(H 2O) = –285.8 kJ/mol
∴ ∆U = –609.9 J To Find :
Standard enthalpy of formation of
9) Calculate standard enthalpy of the C2H 6(∆∆ f H0 )
reaction Formula :
Fe2O3(s) + 3CO(g) 2Fe(s) + 3CO2(g) ∆H0 = ∑∆ fH0 (products)
From the following data : – ∑∆ fH0(reactants)
∆fH 0(Fe2 O3 )= –824.2 kJ mol–1, Solution :
0
∆fH (CO) = –110.5 kJ mol , –1 Standard enthalpy is given by,
∆fH 0(CO2 ) = –393.5 kJ mol–1 ∆H0 = ∑∆ fH0 (products)
Given : – ∑∆ fH0(reactants)
∆fH 0(Fe2 O3 ) = –824.2 kJ/mol = [4 moles of CO2 × ∆fH0 of
∆fH0 (CO) = –110.5 kJ/mol CO2 + 6 moles of H2O
0
∆fH (CO2 ) = –393.5 kJ/mol × ∆fH0 of H2O] –
[2 moles of C2H6 × ∆fH0 of
To Find : C2H6 + 0]
Standard enthalpy of reaction (∆ ∆ H0) = [4 × (–393.5) + 6 × –285.8]
Formula : – [2 × ∆fH0 of C2H6]
∆H0 = ∑∆ fH0 (products) ∴ –3119 = –1574 – 1714.8 – 2
– ∑∆fH (reactants)
0 × ∆fH0 of C2H6
Solution : ∴ –3119 = –3288.8 – 2
Standard enthalpy of reaction (∆ 0
∆H ) × ∆fH0 of C2H6
= 0
∆fH (products) ∴ 169.8 = –2 × ∆fH0 of C2H6
0
– ∆fH (reactants) ∴ –84.9 = ∆fH0 of C2H6
0
= [2 moles of Fe × 0 ∴ ∆fH of C2H6 = –84.9 kJ/mol
+ 3 moles of CO2
× ∆fH0 of CO2] – 11) How much heat is evolved when 12 g
[1 mole of Fe2O3 × ∆fH0 of of CO reacts with NO2 according to the
Fe2O3 + 3 moles of CO following reaction,
× ∆fH0 of CO] 4CO(g) + 2NO2(g) 4CO2(g) + N2 ,
= [0 + (–1180.5)] ∆ H 0 = –1198 kJ
– [–824.2 + (3 × –110.5)] Given :
= –1180.5 + 824.2 + 331.5 ∆H0 = –1198 kJ
= –24.8 kJ To Find :
Heat evolved

Chemical Thermodynamcs and Energetics

 .. 5

Solution : 13) Calculate ∆H0 of the reaction

According to the reaction, +1198 kJ of CH4(g) + O2(g) CH2O(g) + H2O(g)
heat is evolved. When 4 moles of CO From the following data :
reacts with NO 2. So heat evolved per Bond C–H O=O C=O O–H
0 –1
mole is +299.5 kJ. ∆H /kJ mol 414 499 745 464
Number of moles of CO Given :
Bond C–H O=O C=O O–H
mass of CO 0 –1
= ∆H /kJ mol 414 499 745 464
Molar mass of CO
To Find :
12
= ∆H0
28 Solution :
= 0.43 moles ∆H0 = ∑∆H 0(reactant bonds)
So, heat evolved when 0.43 moles of CO – ∑∆H0(product bonds)
reacts = 0.43 × 299.5 ∆H0(C–H) + ∆H0(O–O)]
= [4∆
= +128.8 kJ ∆H0(C–H) +∆
–[2∆ ∆H0 (C=O)]
+ 2(O–H)
12) 38.55 kJ of heat is absorbed when 6.0 g = [2 ∆H0 (C–H) + ∆H0 (O–O)]
of O 2 react with ClF according to the – ∆H0 (C=O) – 2 (O–H)
reation, = 2 × 414 + 499 – 745 – 2 × 464
2ClF(g) + O2(g) Cl2O(g) + OF2(g) = –346 kJ
What is the standard enthalpy of the
reaction ? 14) Calculate C–CI bond enthalpy from the
Given : following data :
Heat absorbed = 38.55 kJ CH3Cl(g) + Cl2(g) CH2Cl2(g) + HCl(g)
Mass of O2 = 6.0 g ∆H0 = –104 kJ
To Find : Bond C–H Cl=Cl H=Cl
Standard enthalpy of reaction
∆H0/kJ mol–1 414 243 431
Solution :
Number of moles of O2 Given :
C–H Cl=Cl H=Cl
mass of O 2
= 414 243 431
Molar mass of O2
To Find :
6 ∆H 0C–Cl
= Solution :
32
= 0.1875 ∆H0 = ∑∆H 0(reactant bonds)
38.55 kJ heat is absorbed when 0.1875 – ∑∆H0(product bonds)
moles react with ClF. = [3∆∆H0(C–H) + ∆H0
∆ 0(Cl–Cl)]
(C–Cl) + ∆H
38.55 –[2∆ 0
∆H (C–H) + 2∆ ∆ H0
∴ Heat absorbed for 1 mole =
0.1875 (C–Cl) +∆ 0
∆H (H–Cl)]
= 205.6 kJ = [∆∆H0(C–H) – ∆H 0(C–Cl)]
From reaction 2 moles of ClF reacts with + ∆H0(Cl–Cl)– ∆H0(H–Cl)
1 mole of O 2 so standard enthalpy of ∴ –104 = 414 – ∆H0(C–Cl) + 243
reaction is 205.6 kJ. – 431
∆H0(C–Cl) = 414 + 104 + 243 – 431
= 300 kJ/mol
Chemical Thermodynamcs and Energetics
 .. 6

15) Calculate the standard enthalpy of the 2C + 2O2 2CO2

reaction, ∆H0 = –787 kJ
2C(graphite) + 3H2(g) C2H 6(g) from the
following ∆H0 values : 2C(g) + 3H2(g) C2H6(g)

7 ∆ H 0 = 1560 + (–857.4) + (–787)

i) C2H6(g) + O
2 2(g) = –84.4 kJ
2CO2(g) + 3H2O(l), ∆H0 = –1560 kJ
16) Given the following equation Calculate
1
ii) H2(g) + O2(g) H 2 O (l), standard enthalpy of the reaction,
2
3
∆H0 = –285.8 kJ 2Fe(g) + O Fe2O3(s) ∆H0 = ?
iii) C(graphite) + O2(g) CO 2(g), 2 2(g)
i) 2Al(s) + Fe2O3(s)
∆H0 = –393.5 kJ
2 Fe(s) + Al2O(3)(s) ∆H0 = –847.6 kJ
Given : 3
ii) 2Al(s) + O Al 2 O (3)(s)
Equation are, 2 2(g)
7 ∆H0 = –1670 kJ
C2H6(g) + O Given :
2 2(g)
Equation are,
2CO2(g) ∆ 0 = –1560 kJ ...(i)
+ 3H2O(l), ∆H
2Al(s) + Fe2O3(s) 2Fe(s) + Al2O(3)(s)
1 ∆H0 = –847.6 kJ
H2(g) + O2(g) H 2O (l),
2 ...(i)
∆H0 = –285.8 kJ 3
...(ii) 2Al(s) + O Al2 O(3)(s)
2 2(g)
C(graphite) + O2(g) CO2(g),
∆H0 = –393.5 kJ ∆H0 = –1670 kJ
...(iii) ...(ii)
To Find : To Find :
∆H0 ∆H0
Solution : Solution :
Reverse equation (i) Reverse equation (i), so that it becomes
2Fe(s) + Al2O3(s) 2Al(s) + Fe2O3(s)
7 ∆ H0 = 847.6 kJ ...(iii)
2CO2(g) + 3H2O(l) C2H6(g) + O2(g)
2 Now add equation (ii) to equation (iii)
∆H0 = 1560 kJ ...(iv) 2Fe(s) + Al2O3(s) 2Al(s) + Fe2O3(s)
Multiply equation (ii) by 3 and (iii) by 2 ∆H0 = 847.6 kJ
then add (iv), (ii) and (iii)
3
7 2Al(s) + O2(g) Al2 O(3)(s)
2CO2(g) + 3H2O(l) C2H6(g) + O2(g) 2
2 ∆H0 = –1670 kJ
∆H0 = +1560 kJ
3 3
3H2(g) + O2(g) 3H 2 O (l), 2Fe(s) + O2(g) Fe2 O 3(s)
2 2
∆H0 = –857.4 kJ ∆ H 0 = 847.6 + (–1670)
= 847.6 – 1670
= –822.4 kJ

Chemical Thermodynamcs and Energetics

 .. 7

17) Given the following equation and ∆H0 18) Given the following equation and ∆H0
values at 250C, values at 250C,
i) Si(s) + O2(g) SiO 2(s) i) 2H3BO 3(aq)
∆H0 = –911 kJ B2O3(s)+ 3H2O(l), ∆H0 = +14.4 kJ
ii) 2C(graphite) + O2(g) 2CO(g) ii) H3BO 3(aq)
∆H0 = –221 kJ HBO2(aq) + H2O(l) ∆H0 = –0.02 kJ
iii) Si(s) + C(graphite) SiC(s)
iii) H2B4O 7(s)
2B2O3(s) + H2O(l)
∆H0 = –65.3 kJ
0 ∆H0 = 17.3 kJ
Calculate ∆ H for the following 0
Calculate ∆ H for the following
reaction,
reaction,
SiO2(s) + 3C(graphite) SiC(s) + 2CO(g),
H2B4O7(s) + H2O(l) 4HBO2(aq)
Given :
Given :
Equation are,
Equation are,
Si(s) + O2(g) SiO2(s)
2H3 BO 3(aq) B2O3(s)+ 3H2O(l),
∆H0 = –911 kJ ...(i) ∆H0 = +14.4 kJ ...(i)
2C(graphite) + O2(g) 2CO(g) H3BO 3(aq) HBO2(aq) + H2O(l)
∆H0 = –221 kJ ...(ii) ∆H0 = –0.02 kJ ...(ii)
Si(s) + C(graphite) SiC(s) H2 B4 O7(s) 2B2O3(s) + H2O(l)
∆H0 = –65.3 kJ...(iii) ∆H0 = 17.3 kJ...(iii)
To Find : To Find :
∆H0 ∆H0
Solution : Solution :
Reverse equation (i), so that it becomes Reverse equation (i) and multiply by (2)
SiO2(s) Si(s) + O2(g) 2B2O3(s)+ 6H2O(l) 4H3 BO 3(aq)
∆H0 = 28.8 kJ ...(iv)
∆H0 = 911 kJ ...(iv)
Multiply equations (ii) by 4
Add equations (iv), (ii), (iii),
4H3 BO 3(aq)
SiO2(s) Si(s) + O2(g)
4HBO2(aq)+ 4H2O(l)
∆H0 = 911 kJ ∆ 0 = (–0.08) kJ ...(v)
∆H
2C(graphite) + O2(g) 2CO(g) Now add equation (iv), (v) and (iii)
∆H0 = –221 kJ 2B2O3(s)+ 6H2O(l) 4H3BO3
∆H0 = 28.8 kJ
Si(s) + C(graphite) SiC(s) 4H3 BO 3(aq)
∆ 0 = –65.3 kJ
∆H 4HBO2(aq) + 4H2O(l)
∆H0 = (–0.08) kJ
SiO2(s) + 3C(graphite) SiC(s) + 2CO(g) H2 B4 O7(s) 2B2O3(s) + H2O(l)
∆H0 = 17.3 kJ
∆ H 0 = 911 + (–211) + (–65.3)
= 624.7 kJ H2B4O7(s)+ H2O(l) 4HBO2(aq)
∆ H 0 = –28.8 + (–0.08) + 17.3
= –11.58 kJ

Chemical Thermodynamcs and Energetics

 .. 8

19) Calculate Kp for the reaction, 21) Calculate ∆G0 for the reaction at 250C
C2H4(g) + H2(g) C2H 6(g), CO(g) + 2H2(g) CH3OH (g)
∆G = –100 kJmol at 250C
0 –1 0
∆G = –24.8 kJmol –1

Given : If PCO = 4 atm, PH = 2 atm, PCH OH = 2 atm

2 3
∆ G 0 = –100 kJ/mol Given :
0
= –100000J/mol ∆ G = –24.8kJ/mol
T = 250C = 298 K T = 250C = 298 K
To Find : PCO = 4 atm
Kp PH = 2 atm
2
Formula : PCH OH= 2 atm
3
∆ G 0 = –2.303RT log10 Kp To Find :
Solution : ∆G
∆G0 = –2.303RT log10 Kp Formula :
∴ –100000 = –2.303 × 3.314 × 298 ∆ G = ∆G0 + 2.303RT log10 Kp
× log10 Kp Solution :
∆ G = ∆G0 + 2.303RT log10 Kp
∴ 100000 = 5705.85 log10 Kp
PCH3OH
100000
∴ = log10 Kp ∴ QP =
5705.85 PCO × PH2 2
Take Antilog on both sides
∴ Anti [17.5258] = Kp 2 2
∴ QP = 2 = = 0.125
∴ 3.35 × 1017 = Kp 4 × (2) 16
∴ Kp = 3.35 × 1017
∴ ∆G = –24.8 + [2.303 × 8.314 × 10–3
× 298 × log(0.125)]
20) Kp for the reaction,
= –24.8 + [–5.153]
MgCO3(s) MgO(s) + CO2(s) is
= –24.8 – 5.153
9 × 10–10. Calculate ∆G0 for the reaction = 29.95 kJ
at 250C.
Given : 22) Calculate ∆ S (tota l) and hence show
Kp = 9 × 10–10 whether the following reaction is
T = 250C = 298 K spontaneous at 250C.
To Find : HgS(s) + O2(g) Hg(l) + SO2(g)
∆G0 ∆H = –238.6 kJ and ∆S0 = +36.7 JK–1
0

Formula : Given :
∆ G 0 = –2.303RT log10 Kp T = 250C = 298 k
Solution : 0
∆ H = –238.6 kJ
∆ G 0 = –2.303RT log10 Kp ∆ S0 = +36.7 JK–1
∴ ∆ G 0 = –2.303 × 8.314 × 298 × log9 To Find :
× 10–10 ∆ S(total)
= 51,613.96 J/mol Formula :
= 51.61 kJ
– ∆H0
∆Ssurr =
T

Chemical Thermodynamcs and Energetics

 .. 9

Solution : = 50 + 32.5
= 82.5 kJ
– ∆H 0  –238.6kJ  As ∆G is positive, the reactions is
∆Ssurr = =  
T  298k  nonspontaneous and the positive
= 0.8006 kJ/K value ∆ H indicates that the
= 800.6 J/K reaction is endothermic.
∆ Ssys = ∆ S0 = +36.7 J/K
∴ ∆S(total)= ∆Ssys + ∆Ssurr For the certain reaction, ∆H0 = –224 kJ
24)
= 36.7 + 800.6 and ∆S0 = –153 JK–1. At what temperature
= 837.3 J/K will it change from spontaneous to
As ∆S(total) is positive, the reaction is nonspontaneous ?
spontaneous at 298 K Given :
∆ H 0 = –224 kJ
23) Determine whether the reaction ∆H and ∆ S0 = –153 JK–1
∆ S values are spontaneous or = –0.153 kJ/K
nonspontaneous. State whether they are To Find :
exothermic or endothermic. Temperature (T) = ?
i) ∆H = –110 kJ and ∆S = + 40JK–1 Formula :
at 400 K
ii) ∆H = –50 kJ and ∆S = – 130 JK–1 at 400 K ∆H0
T =
∆S 0
Given : Solution :
∆H = –110 kJ and ∆S = + 40JK–1 at 400 K
∆H = –50 kJ and ∆S = – 130 JK–1 at 400 K ∆H0
T =
To Find : ∆S 0
To state whether the reactions are
–224
exothermic or endothermic and =
spontaneous or nonspontaneous. 0.153
Formula : = 1464.05 K
0
∆ G = ∆H – T∆ ∆S As ∆ H and ∆ S 0 both are negative,
Solution : reaction is spontaneous at lower
i) ∆ G = ∆H – T∆ ∆S temperature. So the reaction will be
∆ S = +40 J/K = 0.04 kJ/K spontaneous below 1464.05 K and
∆ H = –110 kJ nonspontaneous above 1464.05 K. The
∴ ∆ G = –110 – (400 × 0.04) change over between spontaneous and
= –110 –16 nonspontaneous occurs at 1464.05 K
= –126 kJ
Because ∆ G is negative, the 25) Determine whether the following
reactions is spontaneous and the reaction is spontaneous or
negative value ∆ H indicates that nonspontaneous under standard
the reaction is exothermic. condition ?
Zn(s) + Cu2+(aq) Zn2+ + Cu(s)
ii) ∆G = ∆H – T∆ ∆S ∆H0 = – 219 kJ, ∆S0 = – 21 JK–1
∆H = +50 kJ Given :
∆S = –130 J/K = –0.130kJ/k ∆ H 0 = – 219 kJ
∴ ∆G = 50 – (250 × –0.130) ∆ S0 = – 21 JK–1
T = 298 K
Chemical Thermodynamcs and Energetics
.. 10

To Find : Formula :
∆G0 W = – P∆∆V
Formula : Solution :
∆ G 0 = ∆H0 – T∆∆ S0 W = – P∆∆V
Solution : = –1 × (22.4)
∴ ∆ G 0 = ∆H0 – T∆∆ S0 = – 22.4 L atm
= –219 – (298 × –0.021) = – 22.4 × 101.33 J
= –219 – (–6.258) = –2269.8 J
= –219 + 6.258 Ans : W = –2.27 kJ
= –212.74 kJ ∆ H = ∆U + P∆ ∆V
As ∆ G 0 is negative the reaction ∴ –P∆∆V = –2.27
spontaneous. P∆∆ V = 2.27
∴ ∆ U = ∆H – P∆ ∆V
26) Determine whether the following = –2043 – 2.27
reaction is spontaneous under standard = –2045.27 kJ
conditions. ∴ ∆U = –20445.27 kJ
2H2O(l) + O2(g) 2H 2O 2(l)
∆H0 = + 196 kJ, ∆S0 = – 126 JK–1 28) What is the value of ∆ S surr for the
Does it have a cross-over temperatuer ? following reaction at 298 K ?
Given : 6CO2(g) + 6H2O(l) C6H 12O 6(s)
∆ H 0 = 196 KJ, ∆ S0 = –126 J/K + 6O2(g),
Solution : 0 –1
∆G = 2879 kJ mol
∆ G 0 = ∆H0 – T∆ ∆ S0
∆S0 = – 210 JK–1mol–1.
= 196 – (298 × –0.126)
Does it have a cross-over temperatuer ?
= 196 + (37.55)
Given :
= 233.55 kJ
∆ G 0 = 2879 kJ mol–1
As ∆ G0 is positive the reaction will be
∆ S0 = – 210 JK–1mol–1
nonspontaneous. As ∆H0 is positive and
= –0.210 kJ/K/mol.
As ∆S0 is negative. ∆G 0 will be always
T = 298 K
positive regardless of temperature. The
To Find :
reaction is therefore nonspontaneous at
∆ Ssurr
all the temperature. So it will not have
Formula :
cross-over temperature.
∆ G 0 = ∆H0 – T∆ ∆ S0
27) Oxidation of propane is represented as Solution 0:
C3H8(g) + 5O2(g) 3CO2(g) + 4H2O(g), ∆ G = ∆H0 – T∆ ∆ S0
0
2879 = ∆H – (298 × –0.210)
∆H0 = – 2043 kJ. 2879 = ∆H0 – (–62.58)
How much pressure volume work is ∆ H 0 = 2816.42 kJ
done and what is the value of ∆ U at
constant pressure of 1 atm when volume 2816.42
∆ Ssurr =
change i s+22.4 L. 298
Given : = 9.45 kJ/K
P = 1 atm
V = +22.4 L
To Find :
Work done (W)
Value of ∆U
Chemical Thermodynamcs and Energetics
 .. 11

29) Calculate the enthalpy change for the 498

reaction. ∆H = kJ mol .
2
H2O (g) 2H(g) + O(g)
H2O(g) 2H(g) + (O)(g)
And hence, calculate the bond enthalpy
of O – H bond H2O from the following
∆H = –44 + 285.8 + 436 + 249
data :
= 926.8 kJ ...(i)
∆vapH(H 2O) = 44.0 kJ mol–1 Bond enthalpy of O–H bond in H2O can
∆fH(H 2 O) = –285.8 kJ mol–1 be calculated as follows :
∆ aH(H 2 ) = 436.0 kJ mol–1 ∆ H = Σ (∆ ∆H of reactants)
– Σ (∆
∆H of products)
∆ H(O 2 ) = 498.0 kJ mol–1
= [2∆∆H (O–H)] – [O]
where ∆ a H is the enthalpy of ∆ H = 926.8 kJ ... from(i)
atomization ∴ 926.8 = 2 ∆H (O–H)
Given :
∆vapH(H2O) = 44.0 kJ mol–1 926.8
∴ ∆H (O–H) =
∆fH(H 2O) = –285.8 kJ mol–1 2
= 463.4 kJ/mol
∆ aH(H 2 ) = 436.0 kJ mol–1
∆H(O 2 ) = 498.0 kJ mol–1 30) Calculate ∆ S surr when one mole of
To Find : methanol (CH3OH) is formed from its
∆H(O–H) elements under standard conditions if
∆H ∆fH0(CH3OH) = –238.9 kJ mol–1.
Solution : Given :
Reaction can be given as follows
∆H 0( CH = –238.9 KJ/mol
H 2O (l) H2O(g) 3OH )

∆H = 44.0 kJ mol ...(i) To Find :

∆ Ssum
1 Solution :
H2(g) + O H2O
2 2(g)
∆H = –285.8 kJ mol ...(ii) ∆H0
∆Ssurr =
H2(g) 2H (g) T
∆H = 436 kJ mol ...(iii) ∆ fH 0 = –238.9 kJ mol
O2(g) 2(O)(g) = –238900 J/mol
∆H = 498 kJ mol ...(iv)
 238900 
Reverse equation (i) and (ii) and add ∴ ∆ Ssurr = –  – 
them to equation (iii) and (iv)  298 
H2O(g) H 2O (l) = 801.7 J/K
∆H = –44.0 kJ/mol
31) Calculate the total heat to melt 180g of
1 ice at 0 0 C, heat it to 100 0 C and then
H 2O (l) H2(g) + O2(g)
2 vaporize it at that temperature. ∆fusH(ice)
∆H = 285.8 kJ mol = 6.01 kJ mol–1 at 00C, ∆vapH(H2O) = 40.7
H2(g) 2H (g) kJ mol–1 at 1000C. Specific heat of water
∆H = 436 kJ mol = 4.28 J g–1 K–1.
1 2
O 2(O)(g)
2 2(g) 2
Chemical Thermodynamcs and Energetics
 .. 12

Given : 32) 6.24 g of ethanol are vaporized by

Wice = 180 g supplying 5.89 kJ of heat energy. What
∆fusH(ice) = 6.01 KJ/ mol is enthalpy of vaporization of ethanol ?
∆ vap H( H O ) = 40.7 KJ/mol Given :
2
Wethanol = 6.249
sp. heat of H2O = 4.28 Jg–1k–1 q = 5.89 KJ
To Find :
To Find :
Heat required to melt ice. ∆vapH
Solution :
Solution :
–H2O(g) Latent heat H2O(l) Heating Number of moles of ethanol
of fusion
00 C 00 C Mass of ethanol
= Molar mass of ethanol
H2O(l) Latent H2O(g)
heat of vaporization
0
100 C 1000C 6.24
=
Part I : 46
H2O(g) H 2O (l) = 0.1356 moles
Heat required = Latent heat for 180 g. 5.89 kJ heat is requiered to heat 0.1356
1 mol of H2O = 6.01 kJ moles.
1 mol of H2O = 18 g Then heat required to vaporize 1 mole
∴ 180 g = ? moles will be,
∴ 180 g of H2O = 10 moles of H2O
5.89
∴ 10 mol of H2O = 60.1 kJ =
∴ Heat required = 60.1 kJ ...(i) 0.1356
Part II : = 43.44 kJ
H 2O (l) H 2O (l)
00 C 00 C ∴ Enthalpy of vaporization of ethanol
Heat required = mass × Specific heat = 43.44 kJ
× ∆T
33) Enthalpy of fusion of ice is 6.01 kJ mol–1.
= 180 × 4.18 × 100
The enthalpy of vaporization of water
= 75240 J
is 45.07 kJ –1 . What is enthalpy of
= 75.240 kJ ...(ii)
sublimation of ice ?
Part III :
H 2O (l) H2O(g) Given :
1000C 1000C ∆ fusH = 6.01 kJ/mol
Heat required = Latent heat of ∆vapH = 45.07 kJ/mol
vaporization
1 mol of H2O = 40.7 kJ To Find :
∴ 1 mol of H2O = 18 g ∆ sub H
∴ 180 g of H2O = 10 moles of H2O Formula :
∴ Heat required = 407 kJ ...(iii) ∆ sub H = ∆fusH + ∆vapH
From (i), (ii) and (iii) Solution :
Heat required to melt ice ∆ sub H = ∆ fusH + ∆vapH
= 60.1 + 75.240 + 407 ∴ ∆ sub H = 6.01 + 45.07
= 542.34 kJ = 51.08 kJ/mol
Heat required to melt ice = 542.34 kJ 51.08 kJ

Chemical Thermodynamcs and Energetics