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1.

Calculate the heat of formation of anhydrous aluminium chloride from the following data:
H2(g) + Cl2(g) → 2HCl(g) + 184.1 kJ
HCl(g) + aq → HCl (aq) + 72.45 kJ
2Al(s) + 6HCl (aq) → Al2Cl6 (aq) + 3H2(g) + 1003.2 kJ
Al2Cl6 (s) + aq → Al2Cl6(aq) + 643.07 kJ
Ans: 1347.1 kJ

2. 2 litres of oxygen, initially at normal temperature and pressure, are expanded isothermally and
reversibly to a volume of 4 litres. Calculate the work done by the gas in joules.
Ans: 141.5 kJ
3. Two moles of an ideal monoatomic gas at 300 K are compressed to one quarter of the original
volume. calculate the final temperature of the gas.
Ans: 756 K

4. Two what pressure must a given volume of oxygen at 373 K and 1 bar pressure, be adiabatically
compressed in order to raise the temperature to 673 K?
Ans: 7.89 bar

5. Calculate the standard enthalpy of combustion of ethene from the following data
C2H4(g) + H2(g) → C2H6(g) + 87.86 kJ
7
C2H6(g) + O2(g) → 2CO2 (g) + 3H2O(g) + 1541.5 kJ
2
1
H2(g) + O2(g) → H2O(g) + 241.8 kJ
2
Ans: – 1387.5 kJ

6. The standard enthalpies of combustion of graphite and carbon monoxide are respectively – 394.6 and
– 282.06 kJ mol–1. Dissociation of O2 and CO into gaseous atoms takes place with the absorption of
491.23 and 964.87 kJ mol–1 respectively. Calculate the enthalpy of sublimation of carbon.
Ans: 606.71 kJ g atom–1

7. Calculate the enthalpy of formation of NaCl from the following data:


∆ H / kJ mol–1
Na(g) → Na+(g) + e– 500.01
1
Cl2(g) → Cl(g) 120.92
2
Na(s) → Na(g) 108.37
Na+(g) + Cl–(g) → NaCl(s) – 775.33
1
Cl(g) + e– → Cl2 – 365.28
2
Ans: – 411.31 kJ mol–1
8. 10 litres of an ideal gas at 273 K and 100 atm pressure are allowed to expand reversibly and
isothermally to a pressure of 10 atmospheres. Calculate the internal energy change and work done
during this process.
Ans: ∆ E = 0, W = – 233.22 kJ

9. 10 litres of hydrogen, initially at 2 atm are expanded reversibly and isothermally to 30 litres.
Calculate the work done during this process.
Ans: 1795.02 J

10. 12.25 g of N2 at 273 K and 10 atm pressure are allowed to expand reversibly and adiabatically to 1
atm pressure. Calculate the work done during this process.
Ans: – 1196.68 J

11. 0.5 mol of an ideal gas is allowed to expand reversibly at 300 K from a volume of 1 litre to a volume
of 10 litres against a constant pressure of 1 atmosphere. Calculate the entropy change and heat
absorbed during the process.
Ans: 1 = 912.2 J; ∆ S = 9.62 J deg–1

12. Calculate the entropy change when cadmium vapour at 1040 K and 1 atmosphere pressure is heated
to 1300 K and compressed to 6 atmosphere pressure.
Ans: – 2.47 cal deg–1 mol–1

13. If the standard entropies of C(graphite), H2(g) and C2H4(g) are respectively 1.36 and 31.21 and 52.48
eu. Then calculate the standard entropy change fro the reaction
2C(graphite) + 2H2(g) → C2H4(g)
Ans: – 12.66 eu

14. The standard free energies of formation of NO2 and N2O4 are respectively 51.34 and 98.08 kJ mol–1
respectively. Then calculate KC, KP and Kx at 298 K and 1 atmosphere pressure for the reaction
N2O4  2NO2
Ans: KP = 0.1579 atm;
KC = 6.463 × 10–3 M
Kx = 0.1579

15. A heat engine operates with mercury vapour between 623 K and 323 K. What is the amount of heat
that must be withdrawn from the hot reservoir to produce 500 J of work?
Ans: 1033.5 J

16. 11.21 litres of an ideal gas at 273 K and 1 atm pressure expands reversibly and isothermally to a final
pressure of 0.25 atm. Calculate the entropy change during this process.
Ans: 2.77 eu
17. A refrigerator operating in a room at 303 K converts 1000 g of water at 273 K into ice at 273 K. If the
latent heat of fusion of ice at 273 K is 333.9 J g–1. Calculate the minimum amount of work required
for the above said process.
Ans: 36.1 kJ kg–1

18. If the standard free energies of formation of AgCl(s), Ag+ (1 M) and Cl– (1 M) are –109.7, 77.19 and
–131.22 kJ respectively. Calculate the solubility product of AgCl at 298 K.
Ans: 2.014 × 10–10

19. The vapour pressures of acetone at different temperatures are given below
T/K 283 293 303 313 323
p/atm 0.152 0.2143 0.372 0.555 0.806

Using the above data, calculate the mean molar heat of evaporation of acetone.
Ans: 31.79 kJ mol–1

20. The molar heat capacity of anhydrous sodium sulphate at different temperatures are given below
T/K 14 20 25 35 50 100 219 282 298
CP 1.88 4.94 7.95 15.1 28.1 67.3 113.5 130.5 133.6
(J mol–1

Using the above data, calculate the absolute molar entropy of anhydrous sodium sulphate at 298 K.
Ans: 36.6 eu mol–1

21. For the hydrogenation of benzene to cyclohexene


C6H6 + 3H2 → C6H12
the enthalpy change of the reaction at 373 K is –192.47 kJ. The equilibrium partial pressures (at 373 K and
1 atmosphere) of H2, C6H6 and C6H12 are respectively 1.316 × 10–3, 9.079 × 10–2 and
9.079 × 10–1atm. Calculate the equilibrium constant, KP and the free energy change of the reaction at
373 K.
Ans: Kp (at 373 K) = 43.9 × 109 atm–3
∆ G (at 373 K) = – 69.46 kJ

22. For the reaction


2H2S(g)  2H2(g) + S2(g)
Calculate the enthalpy change from the following data
T/K p H2 / atm Ptotal/atm

1024 0.0553 1.0013


1216 0.1467 1.0013
Ans: 176.36 kJ

23. Calculate the standard free energy change for the reduction of CdS to Cd with H2 at 1373 K from the
following data
∆ G°/kJ
1
H2S(g) → H2(g) + S2(g) 48.96
2
1
CdS(g) → Cd(g) + S2(g) 127.20
2
Ans: 78.24 kJ

24. One mole of an ideal monoatomic gas at 1 atm pressure and 300 K is heated to 523 K and compressed
to a final pressure of 5 atm. Calculate the entropy change during this process.
Ans: – 0.441 eu mol–1

25. The standard enthalpies of formation of water and carbon dioxide are respectively 285.78 and 394.99
kJ mol–1. If the standard enthalpy of combustion of benzoic acid is 3226.86 kJ mol–1. Calculate the
standard enthalpy of formation of benzene.
Ans: – 395.41 kJ mol–1

26. The ∆ H for the reaction C + O2 → 2CO at 291 K is –175.53 kJ. Calculate the heat of the reaction at
333 K, given that the mean atomic and molecular heats (CP) of solid carbon and of gaseous CO and
CO2 are respectively 10.44, 29.17 and 37.93 J deg–1.
Ans: –175.12 kJ

27. Calculate the work done by 1 lit of hydrogen initially at 273 K and 1 atm pressure in expanding to a
volume of 2 litres also at 273 K.
Ans: 70.7 J

28. Calculate the work done when 5 lit of N2 at 2 atm pressure expands adiabatically to 20 litres.
ANs: 1.075 kJ

29. Calculate the work done when 28 g of O2 at 273 K and 5 atm pressure expands reversible and
adiabatically so that the final pressure is 1 atm.
Ans: 2.293 kJ

30. The enthalpies of neutralization of two monobasic acids HA and HB are respectively 57.11 and 46.86
kJ mol–1. When 1 g –equivalent of NaOH in dilute solution is added to a mixture of 1g–equivalent of
HA and 1g–equivalent of HB, 54.23 kJ are evolved. Compare the strengths of the two acids.

Solution
Let a fraction x g equivalent of NaOH be neutralized by HA then
x HA + x NaOH → x NaA + xH2O + (x × 57.11 kJ)
∴ formation of NaOH that reacts with HB = 1 – x
and therefore
(1 – x) HB + (1 – x) NaOH → (1 – x) NaB + (1 – x) H2O + (1 – x) (46.86 kJ)
∴ Total heat released = x × 57.11 kJ + (1 – x) (46.86 kJ)
= 54.23 kJ
Solving for x
i.e., (x × 57.11 kJ) + (1 – x) (46.86 kJ) = 54.23 kJ
on x = 0.72
(and) 1 – x = 0.28
strength of H A 0.72
∴ = = 2.57
strength of H B 0.28

31. Calculate the enthalpy of formation of C2H5 – O – C2H5 from the following data
C2H5OC2H5 + 6O2 → 4CO2 + 5H2O + 2761.57 kJ
C + O2 → CO2 + 405.87 kJ
1
H2 + O2 → H2O + 286.19 kJ
2
Ans: 292.89 kJ mol–1

32. The heats of formation of CO2 and N2O are respectively 393.3 kJ mol–1 and 74.06 kJ mol–1. Calculate
the heat of combustion of carbon in nitrous oxide.
Ans: 541.44 kJ

33. The heat of evaporation of mercury at its boiling point (630 K) is 59.27 kJ mol–1. The mean heat
capacities of the liquid and vapour in the range 573 – 630 K are 2716 and 20.84 J deg–1 mol–1
respectively. Calculate the heat of evaporation at 573 K.

Solution
According to Kirchoff’s equation
 ∂ (∆H) 
  = ∆C P
 ∂T P
Assuming ∆ CP to be independent of temperature, we can write
(∆ H2 – ∆ H1) = ∆ CP (T2 – T1)
∆ CP = CP( vap ) − C P( liq )
= 20.84 – 27.16
= – 6.32 J deg–1 mol–1
∆ H2 = 59270 J mol–1
T2 = 630 K
T1 = 573 K
Applying these data in the above equation, we get
(59270 –∆ H1) = – 6.32 (630 – 573)
(or) ∆ H1 = 59.63 kJ mol–1

34. The standard heat of formation of SO2 and SO3 are respectively –70.95and –94.40 K cal mol–1. The
heat capacities of SO2, SO3 and O2 in cal deg–1 mol–1 are given below:
SO2 : CP = 10.38 + 2.54 × 10–3 T – 1.42 × 105 T–2
SO3 : CP = 13.70 + 6.42 × 10–3 T – 3.12 × 105 T–2
O2 : CP = 7.16 + 1.00 × 10–3 T – 0.40 × 105 T–2
Ans: ∆ H = – 23,210 cal