MASTERING CHEMISTRY 1

NBS GURUKUL
TARGET X+1-2019
CHEMICAL THERMODYNAMICS
WORK SHEET -1
TOPIC : WORK DONE

Prof. Adarsh Bhatti

M.Sc. (Gold Medalist )
1. Assign the sign of work done (based on SI convention) in the following chemical change taking place against
external atmospheric pressure :
(a) 3H2(g) + N2(g)  2NH3(g)
(b) CH4(g) + 2O2(g)  CO2(g) + 2H2O(g)
(c) CaCO3(s)  CaO(s) + CO2(g)
(d) NH4HS(s))  NH3(g) + H2S(g)
(e) PCl5(g)  PCl3(g) + Cl2(g)
(f) C(s) + CO2(g)  2CO(g)
(g) C2H6(g) + 3.5O2 (g)  2CO2(g) + 3H2O (l)
2. In the following cyclic process, A to F specify the type of changes taking place given that
Temperature at A, B and F = T1
Temperature at C, D and E = T2 < T1

3. Calculate the maximum work obtained when 0.75 mol of an ideal gas expands isothermally and reversible at
27o C from a volume of 15 L to 25 L. Ans.  955.5 J
4. Calculate the amount of work done in each of the following case:-
(i)One mole of an ideal gas contained in a bulb of 10 litre capacity at 1 atm is allowed to enter into an
evacuated bulb of 100 litre capacity.
(ii) One mole of a gas is allowed to expand from a volume of 1 litre to a volume of 5 litres against the
constant external pressure of 1 atm (1 litre atm = 101.3J) Ans.  405.2 J
6. A 5-litre cylinder contained 10 moles of oxygen gas at 27 C. Due to sudden leakage through the hole, all the
o

gas escaped into the atmosphere and the cylinder got empty. If the atmospheric pressure is 1.0 atmosphere,
calculate the work done by the gas. Ans.  2444J
7. Calculate the work done when 56 g of iron reacts with hydrochloric acid in (a) a closed vessel of fixed
volume, (b) an open beaker at 27oC. Ans. - 600 cal
8. A certain amount of an ideal gas passes from state A to B first by means of process 1, then by means of
process 2. In which of the process is the amount of heat absorbed by the gas greater ?

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 MASTERING CHEMISTRY 2

9. The diagram shows a P-V graph of a thermodynamic behavior of an ideal gas. Find out form this graph :

(i) work done in the process A B , B  C, C  D and D  A

(ii) work done in the complete cycle A  B  C  D  A. Ans. - 5000 J
10. The work done in changing the state from (P0, V0) to (P1 ,V1) in the following system is :

a) - 7.5  10-5 J (b) - 7.5  105 J (c) - 7.5  105 erg (d) - 7.5  10-5 erg
11. The net work done through a series of changes reported in figure at the end of cycle for an ideal
gas is equal to :

a) Zero (b) - 2PV (c) -3PV (d) - 5PV

12. The net work done through a series of changes reported in figure for ideal gas is :

a) -6  105 J (b) -7  105 J (c) -12  105 J d) + 12  105 J

13. A given mass of gas expands from the state A to the state B by three paths 1, 2 and 3 as shown in
the figure. If w1, w2 and w3 respectively be the work done by the gas along three paths then :

a) w1 > w2> w3 (b) w1 < w2 < w3 (c) w1 = w2 = w3 (d) w2 < w3 < w1

14. An ideal gas is taken around the cycle ABCA as shown in P-V diagram. The net work done during
the cycle is equal to :

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 MASTERING CHEMISTRY 3

a) 12P1V1 (b) 6P1V1 (c) 5P1V1 (d) P1V1

15. What will be the nature of change in internal energy in case of processes shown below ?

a) +ve in all cases (b) –ve in all cases (c) -ve in I and III & +ve in II and IV (d) zero in all cases
16. One mole of an ideal gas is taken from a to b along two paths denoted by the solid and the dashed
lines as shown in the graph below. If the work done along the solid line path is ws and that along
the dotted line path is wd, then the integer closest to the ratio wd/ws is

V (lit.)
Ans. 2
17. The reversible expansion of an ideal gas under adiabatic and isothermal conditions is shown in the figure.
Which of the following statement(s) is (are) correct ?

a) T1 = T2 (b) Ta > T1 (c) wisothermal > wadiabatic (d) ∆Uisothermal > ∆Uadiabatic Ans.(A, C, D)
18. An ideal gas is expanded from (p1, V1, T1) to (p2, V2, T2) under different conditions. The correct statement(s)
among the following is(are) JEE-ADVANCED-2017
(A) The work done on the gas is maximum when it is compressed irreversibly from (p 2, V2) to (p1, V1)
against constant pressure p1
(B) The work done on the gas is less when it is expanded reversibly from V1 to V2 under adiabatic conditions
as compared to that when expanded reversibly from V1 to V2 under isothermal conditions.
(C) The change in internal energy of the gas (i) zero, if it is expanded reversibly with T1 = T2, and (ii)
positive, if it is expanded reversibly under adiabatic conditions with T1  T2
(D) If the expansion is carried out freely, it is simultaneously both isothermal as well as adiabatic

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 MASTERING CHEMISTRY 4
Sol. (A,B,D)

(A) (i) U = nCv T = 0 (isothermal hence T = 0

(ii) U = q + w = -ve (q = 0, w < 0)
U = nCV T  T < 0
(D)q = 0 (adiabtic), w = 0 (free expansion)
U = 0  T = 0 (isothermal )
WORK SHEET -2
TOPIC : FIRST LAW OF THERMODYNAMICS
19. Express the change in internal energy of a system when
(i) No heat is absorbed by the system from the surroundings, but work (w) is done on the system. What
type of wall does the system have ?
(ii) No work is done on the system, but q amount of heat is taken out from the system and given to the
surroundings. What type of wall does the system a have ?
(iii) w amount of work is done by the system and q amount of heat is supplied to the system. What type
of system would it be ?
20. In a process, 701J of heat is absorbed by a system and 394 J of work is done by the system. What is the
change in internal energy of the process ? Ans. + 307 J
21. A “0.25 hp” electric motor uses 187 w of electrical energy while delivering 35 J of work each second. How
much energy must be dissipated in the form of function (heat) ? Ans. 152 J
22. When 150 joule of heat energy is supplied to a system having internal energy E 1, 75 joules of work is
done on the system to change its state. Calculate (i) the energy of the system in the new state and (ii) change
in internal energy of the system. Ans. 225 J ,(225+E1) J
23. A cylinder containing a gas is fitted with a frictionless and weightless piston. The gas is allowed to expand
from 1 litre to 5 litre against a constant pressure of one atmosphere. During this process 200 joules of heat
is absorbed from the surrounding. Calculate the change in the internal energy change of the system.
Ans.  205.2J
24. Calculate the internal energy change in each a of the following cases : -
(i) A system absorbs 15 kJ of heat and does 5 kJ of work. Ans. 10 kJ
(ii) 5 kJ of work is done on the system and 15 kJ of heat is given out by the system. Ans. - 10 kJ
25. Carbon monoxide is allowed to expand isothermally and reversibly from 10 m 3 to 20 m3 at 300 K and work
obtained is 4.754 kJ. Calculate the number of moles of carbon monoxide. Ans. 2.75 moles
26. A certain electric motor produced 15 kJ of energy each second as mechanical work and lost 2 kJ as heat to
the surroundings. What is the change in the internal energy of the motor and its power supply each second
? Ans. = - 17 kJ
27. Two litres of an ideal gas at a pressure of 10 atm expands isothermally into vacuum until its total volume is
10 L
How much heat is absorbed and how much work is done in the expansion ?
What would be the heat absorbed and work done
(i) If the same expansion takes place against a constant external pressure of 1 atm ? Ans. 8 litre atm
(ii) If the same expansion takes place to a final volume of 10 litres conducted reversibly ? Ans.32.2 L atm

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 MASTERING CHEMISTRY 5
28. When 1 mol of a gas is heated at constant volume, temperature is raised from 298 to 308 K. Heat supplied
to the gas is 500 J. Then which statement is correct ?
a) q = W = 500 J, ∆U = 0 (b) q = ∆U = 500 J, W = 0
c) q = W = 500 J, ∆U = 0 (d) ∆U = 0, q = W = - 500 J
29. A piston filled with 0.04 mol of an ideal gas expands reversily from 50.0 mL of 375 mL at a constant
temperature of 37.0oC. As it does so, it absorbs 208 J of heat. The values of q and w for the process will be:
(R = 8.314J/mol K)(ln 7.5 = 2.0) JEE MAINS-2013
a) q = - 208J, w = +208J (b) q = + 208J, w = + 208 J (c) q = + 208J, w = - 208J (d) q =- 208J, w = - 208J
30. U equal to : JEE MAINS-2017
(1) Isobaric work (2) Adiabatic work (3) Isothermal work (4) Isochoric work
Sol. (2) For Adiabatic process Q = 0
Now, U = Q + W
 U = W
31. A gas is allowed to expand in a well insulated container against a constant external pressure of
2.5atm from an initial volume of 2.50 L to a final volume of 4.50L. The change in internal energy U
of the gas in joules will be: NEET-2017
(1) —500J (2) —505J (3) +505J (4) 113625J
Sol. (2) Work done in irreversible process
W = - Pext V
= - 2.5 [4.5 - 2.5] = - 5L atm
= - 5  101.3J = - 505 J
Since system is well insulated q = 0
By FLOT E = q + W
E = W = - 505 J
WORK SHEET -3
TOPIC :  H =  E +  ng RT
32. Under what conditions.
(1) H =  E (2)  H >  E (3)  H <  E.
33. Show that H = q p.
34. Derive q p = qv +  ng RT
35. The reaction of cyanamide, NH2CN(s), with dioxygen was carried out in a bomb calorimeter, and U was
found to be – 742.7 kJ mol-1 at 298 K. Calculate the enthalpy change of the reaction at 298 K.
3
NH2CN(s) + O2(g)  N2(g) + CO2(g) + H2O (l) Ans. - 741.5 kJ mol-1.
2
36. The enthalpy change (H) for the reaction:
N2(g) + 3H2(g) 2NH3(g) is 92.38 kJ at 298 K. What is E at 298K ? Ans.  87.425 kJ
37. Calculate the difference between heats of reaction at constant pressure and constant volume for the reaction
at 25oC in kJ.
2C6H6 (l) +15O2(g) 12CO2(g) + 6H2 O(l) Ans. 7.43Kj
38. (∆H - ∆U) for the formation of carbon monoxide (CO) from its elements at 298 K is
a) – 2477.57 J mol-1 (b) 2477.57 J mol-1 (c) – 1238.78 J mol-1 (d) 1238.78 J mol-1 AIEEE-2006
39. The combustion of benzene (l) gives CO2(g) and H2O(l). Given that heat of combustion of benzene at
constant volume is —3263.9 kJ moE1 at 25°C; heat of combustion (in kJ mol-1 ) of benzene at constant
pressure will be (R = 8.314 JK-1 mol-1 ) JEE MAINS-2018
(1) 3260 (2) - 3267.6 (3) 4152.6 (4) - 452.46

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 MASTERING CHEMISTRY 6
Sol. (2)

40. Enthalpy of combustion of carbon to CO2 (g) is -393.5kJ mol-1. Calculate the heat released upon the
formation of 35.2 g of CO2 from carbon and dioxygen gas. Ans. 314.8 kJ
41. If water vapour is assumed to be perfect gas, molar enthalpy change at 1 bar and 100 oC is 41 kJ mol-1.
Calculate the internal energy change when
(i) 1 mole of water is vaporized at 1 bar pressure and 100oC. Ans. 37.90 kJ mol-1
(ii) 1 mol of water is converted into ice. Ans. 41.00 kJ mol-1
42. When 0.532 g of benzene (C6H6), boiling point 353 K is burnt with excess of oxygen in a constant volume
system, 22.3 kJ of heat is given out. Calculate H for the combustion process. Ans. - 3273.26 kJ/mol
43. A swimmer coming out from a pool is covered with a film of water weighing about 18g. How much heat
must be supplied to evaporate this water at 298K? Calculate the internal energy of vaporization at 100oC.
vapHo for water at 373 K = 40.66 kJ mol-1. Ans.37.56 kJ mol-1
44. Assuming that water vapour is an ideal gas, the internal energy change (∆U) when 1 mole of water is
vapourised at 1 bar pressure and 100oC (Given : Molar enthalpy of vapourisation of water at 1 bar and 373 K
= 41 kJ mol-1 and R = 8.3 J mol-1 K-1) will be AIEEE 2007
a) 41.00 kJ mol (b) 4.100 kJ mol (c) 3.7904 kJ mol (d) 37.904 kJ mol
-1 -1 -1 -1

45. One mol of a non-ideal gas undergoes a change of state (2.0 atm, 3.0 L, 95 K) → (4.0 atm, 5.0L, 245 K) with
a change in internal energy, ∆U = 30.0L atm. The change in enthalpy (∆H) of the process in L atm is
a) 40.0 (b) 42.3 (c) 44.0 (d) not defined, because process is not constant IIT-2002
46. The heat of combustion of naphthalene (C10H8(s) at constant volume was found to be -5133 kJ mol-1.
Calculate the value of enthalpy change. Ans. - 5138 kJ mol-1
WORK SHEET -4
TOPIC : HEAT CAPACITY
47. Two moles of an ideal gas expand isothermally and reversibly from 1 litre to 10 litre at 300 K. The enthalpy
change (in kJ) for the process is
a) 11.4 kJ (b) - 11.4 kJ (c) 0 kJ (d) 4.8 kJ IIT-2004
48. Calculate the number of kJ necessary to raise the temperature of 60.0 g of aluminium from 35o to 55oC.
Molar heat capacity of Al is 24J mol-1 K-1. Ans. 1066.6 J
49. A swimming pool contains 1  10 L of water. How much energy in joules is required to raise the
5

temperature of water from 20oc to 25oc ? The specific heat capacity of water is 4.184 J/oC /g.
Ans. 2.092  106 kJ
50. (a) Calculate the heat that must be supplied to raise the temperature of 2 kg of water from 25 oC to its boiling
point at atmospheric pressure. The average specific heat of water in the range 25 – 100oC is 4.184 J K-1 g-1.
(b) How long will a 2 kW heater take to supply this energy ? Ans. 627.6 kJ, 5.23 min.
51. (a) Calculate the energy needed to raise the temperature of 10.0 g of iron from 25 oC to 250oC if specific heat
capacity of iron is 0.45 J oC-1 g-1. Ans. 1012.5 J
(b) What mass of copper (specific heat capacity = 0.385 J oC-1 g-1 can be heated through the same
temperature difference when supplied with the same amount of energy as above. Ans. 11.68 g
52. A chemist while studying the properties of gaseous C 2Cl2F2, a chorofurorocarbon refeigerant cooled a 1.25 g
sample at constant atmospheric pressure of 1.0 atm from 320 to 293 K. During cooling, the sample volume

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 MASTERING CHEMISTRY 7
decreased from 274 to 248 mL. Calculate H and U for the chloroflurocarbon for this process. For
C2Cl2F2, Cp = 80.7 J/mol K. Ans. H = - 20.48 kJ/mol , U = - 17.85 J.
53. Calculate the enthalpy change on freezing of 1.0 mol of water at 10 o C to ice at -10oC
fusHo = 6.03 kJ mol-1 at 0oC
Cp [H2O(l)] = 75.3 J mol-1 K-1
Cp [H2O(s) = 36.8 J mol-1 K-1 Ans. - 7.151 kJ mol-1
54. Specific heat of Li(s), Na(s) K(s), Rb(s) and Cs(s) at 398 K are 3.57, 1.23, 0.756, 0.363 and 0.242 Jg -1 K-1
respectively. Compute the molar heat capacity of these elements and identify any periodic trend. If there is
trend, use it to predict the molar heat capacity of Fr.
Ans. 25.01 J mol-1 K-128.3 J mol-1 K-129.5 J mol-1 K-130.86 J mol-1 K-132.2 J mol-1 K-1
55. 5.6 dm3 of an unknown gas at S.T.P. requires 52.25 J of heat to raise its temperature by 10oc at constant
volume. Calculate CvCp and atomicity of the gas. Ans. 1.4
56. Specific heat of an elementary gas is found to be 0.313 J at constant volume. If the molar mass of the gas is
40 g mol-1, what is the atomicity of the gas ? Ans.1.66
57. Consider a class room that is roughly 5m × 10m × 3m. Initially, t = 20 C and P = 1 atm. There are 50
o

people in the class, each losing energy to the room at the average rate of 150 watt. Assume that the walls,
ceiling, floor, and furniture are perfectly insulated and do not absorb any heat. How long will the physical
chemistry examination last if the professor has foolishly agreed to dismiss the class when the air temperature
in the room reaches body temperature, 37oC ? For air, Cp = 7/2R. Loss of air to the outside as the
temperature rises may be neglected. Ans. 411.3 second.
58. 50 students sitting in the room of 5  10  3 m dimensions. The air inside the room is at 27oC and 1 atm
3

pressure. If each student loses 100 watt heat per second assuming the walls, ceiling, floor and all the
material present inside the room is perfectly insulated as well as neglecting loss of air to the outside as the
7
temperature is raised, how much rise in temperature will be noticed in 10 minutes ? Given Cp = R for air.
2
Ans. 16.90oC
59. A gas expands from a volume of 3.0 dm to 5.0 dm against a constant external pressure of 3.0 atm. The
3 3

work done during the expansion is used to heat 10.0 mol of water of temperature 290.0 K. Calculate the
final temperature of water. Ans. 290.81 K
60. If the sum of Cp values of the products is equal to the sum of Cp values of the reactants, then H at t +
300K is ………… than H at 200K.
a) Less than (b) 2 times less c) 4 times greater than (d) Equal to
61. 1 g of graphite is burnt in a bomb calorimeter in excess of oxygen at 298 K and 1 atmospheric pressure
according to the equation
C (graphite ) + O2(g)  CO2(g)
During the reaction, temperature rises from 298 K to 299 K. If the heat capacity of the bomb
calorimeter is 20.7 kJ/K, what is the enthalpy change for the above reaction at 298 K and 1 atm ?
Ans. - 248.4 kJ mol-1
62. 0.562 g of graphite kept in a bomb calorimeter in excess of oxygen at 298 K and 1 atmospheric pressure was
burnt according to the reaction :
C (graphite) + O2 (g)  CO2 9g)
During the reaction the temperature rises from 298 K to 298.80 K. If the heat capacity of the magnitude
calorimeter and its contents is 20.7 kJ/K, what is the enthalpy change for the above reaction at 298 K and 1 atm
? Ans. - 393.4 kJ mol-1
63. 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

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 MASTERING CHEMISTRY 8
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 IIT 2009 Ans. 9 kJ mol-1
64. One kg of graphite is burnt in a closed vessel. The same amount of the same sample is burnt in an open
vessel. Will the heat evolved in the two cases be same ? If not, in which case it would be greater ?
65. A 1.250g sample of octane (C8H18) is burned in excess of oxygen in a bomb calorimeter. The temperature of
calorimeter rises from 294.05 K to 300.78 K. If heat capacity of calorimeter and its contents is 8.93 kJ/K,
calculate the heat transferred to calorimeter. Ans. 60.1 kJ
66. 20 g of ammonium nitrate (NH4NO3) is dissolved in 125 g of water in a coeffee- cup calorimeter, the
temperature of which falls from 296.5 K to 286.4 K. Find the value of q for the calorimeter (Treat heat
capacity of water as the heat capacity of the calorimeter and its contents). Ans. -5.285 kJ
WORK SHEET -5
TOPIC : ENTHALPIES & HESS’S LAW
ENTHALPIES
67. Calculate standard enthalpy change (Ho) and standard internal energy change (Eo) for the reaction:
OF2(g) + H2O(g)  O2(g) + 2HF(g)
Given that standard enthalpies of formation, Hfo of OF2(g), H2O(g) and HF(g) are +23.0, 241.8 and 
268.8 kJ mol-1 respectively. Ans. 318.4 kJ, 320.9 kJ.
68. Which of the following gas has the highest heat of combustion ?
a) Methane (b) Ethane (c) Ethylene (d) Acetylene
69. Equal volume of C2H2 and H2 are combusted under identical condition. The ratio of their heat of
combustion is :
H2(g) + ½ O2(g) = H2O(g); H = - 241.8 kJ
C2H2(g) + 2 ½ O2(g) = 2CO2(g) + H2O(g) ; H = - 1300kJ
a) 5.37/1 (b) 1/5.37 (c) 1/1 (d) None of these
70. Heat of combustion of CH4, C2H4, C2H 6 are – 890, - 1411 and – 1560 kJ/mol respectively. Which has the
lowest calorific fuel value in kJ/g ?
a) CH4 (b) C2H4 (c) C2H6 (d) All same
71. Calculate the amount of heat evolved when

(i) 500cm3 of 0.1 M hydrochloric acid is mixed with 200 cm3 of 0.2 M sodium hydroxide solution.
(ii) 200 cm3 of 0.2M sulphuric acid is mixed with 400 cm3 of 0.5 M potassium hydroxide solution.
Assuming that the specific heat of water is 4.18 JK-1 g-1 and ignoring the heat absorbed by the container,
thermometer, stirrer etc., what would be the rise is temperature in each of the above cases ?
Ans. (i) 2.284 kJ, 0.78o C, (ii) 4.568 kJ , 1.82o
72. Equal volume of 1 M HCl and 1 M H2SO4 are neutralized by dilute NaOH solution and x and y kcal of heat
are liberated respectively. Which of the following is true ?
a) x = y (b) x = 0.5 y (c) x = 0.4 y (d) None of these
73. A solution 200 mL of 1 M KOH is added to 200 mL of 1 M HCl and the mixture is well shaken. The rise in
temperature T1 is noted. The experiment is repeated by using 100 ml of each solution and increase in
temperature T2 is again noted. Which of the following is correct ?
a) T1 = T2 (b) T2 is twice as large as T1
c) T1 is twice as large as T2 (d) T1 is four times as large as T2
74. The standard enthalpy change for the neutralization of hydrocyanic acid and NaOH is Δ H o298 = - 2460
calories. Given that the standard enthalpy change for the neutralization of HCl and NaOH is Δ H o298 = -
13,360 calories. What is the heat of ionization of HCN ?

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 MASTERING CHEMISTRY 9
a) - 15,820 calories (b) + 10, 900 calories (c) - 10, 900 calories (d) + 15,820 calories
HESS’S LAW
75. In the energy cycle given below, what is the value of ∆Hof (C2H2)g ?
∆Hof
2C (s) + H2 (g) + 2 ½ O2 (g) C2H2 (g) + 2 ½ O2 (g)

- 1072 kJ - 1300 kJ

2 CO2 (g) + H2O (g)

a) - 228 kJ mol -1
(b) + 228 kJ mol-1 (c) 2372 kJ mol-1 (d) - 2372 kJ mol-1
Applications of Hess's law.
I. It helps in calculation of H from Hf.
76. Calculate the standard enthalpy change for the reaction::
CH4(g) + 2O2(g) CO2(g) + 2H2O (l)
The standard enthalpies of formation of CH4(g), CO2(g) and H2O(l); are 74.8kJ mol-1, -393.5 kJ mol-1 and -
285.8 kJ mol-1 respectively. Ans. 890.3 kJ mol-1
II. It helps in calculation of Hf
77. Calculate the enthalpy of formation of anhydrous aluminium chloride, Al 2 Cl6 from the following data :-
(i) 2Al(s) + 6HCl(aq)  Al2Cl6(aq) + 3H2(g); H =  1004.0 kJ
(ii) H2(g) + Cl2(g)  2HCl(g); H =  183.9 kJ
(iii) HCl(g) + (aq)  HCl(aq); H=  73.2 kJ
(iv) Al2Cl6(s) +(aq)  Al2Cl6(aq); H =  643 kJ
Ans.  1351.9 kJ
78. The heats of combustion of carbon and carbon monoxide are -393.5 and -283.5 kJ mol-1,
respectively. The heat of formation (in kJ) of carbon monoxide per mole is:
(1) 110.5 (2) 676.5 (3) - 676.5 (4) -110.5 JEE MAINS -2016

Sol. (1)

III. It helps in calculation of H from Hcomb.

79. Calculate enthalpy of Reaction
C2 H4 (g) + H2 (g)  C2 H6 (g)
at 298 K given that enthalpies of combustion of ethylene, H2 and C2 H6 are -1415.4 kJ,  287.3 kJ and 
1566.1 kJ/mol respectively. Ans.  136.6 KJ
80. The standard enthalpies of formation of CO2(g), H2O(l) and glucose(s) at 25oC are - 400 kJ/mol, - 300
kJ/mol and - 1300 kJ/mol, respectively. The standard enthalpy of combustion per gram of glucose at 25 oC
is JEE ADVANCE-2013
a) + 2900 kJ (b) - 2900 kJ (c) - 16.11 kJ (d) + 16.11 kJ
IV. It helps in determination of enthalpy of transition.
81. The enthalpies of combustion of diamond and graphite are -395.4 kJ and -393.5 kJ respectively. Calculated
the enthalpy of transformation from diamond to graphite. Ans. -1.9 kJ

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 MASTERING CHEMISTRY 10
V. It helps in calculation of the Heat of Hydration.
82. Calculate the heat of hydration of anhydrous copper sulphate (CuSO 4) into hydrated copper sulphate
(CuSO4. 5H2O). Given that the heats of solutions of anhydrous copper sulphate and hydrated copper
sulphate are - 66.5 and + 11.7 kJ mol-1 respectively. Ans. - 78.2 kJ
83. At 298 K, the heat of solution of MgSO4(s) is -91.21 kJ mol and that of MgSO4.7H2O(s) is 13.81 kJ mol-1.
-1

Calculate heat of hydration of MgSO4(s) Ans. - 105.02 kJ mol-1

VI. It helps in calculation of ∆H from Bond Energy
84. Calculate H for the reaction:
H

H C  Cl(g)  C(g) + 2H(g) + 2Cl(g)

Cl
The average bond energies of C  H bond and C  Cl bond are 413.0 kJ mol-1 and 326.0 kJ mol-1 respectively.
Ans. 1478 kJ.
85. Calculate the bond energy of C-H bond, given that the heat of formation of CH4, heat of sublimation of
carbon and heat of dissociation of H2 are - 74.8 , +719.6 and 435.4 kJ mol-1 respectively. Ans. 416.3 kJ mol-1
86. Calculate the CC bond energy from the following data:
(i) 2C(graphite) +3H2 (g)  C2H6(g); H =  84.67 kJ mol-1
(ii) C(graphite)  C(g); H= 716.7 kJ mol-1
(iii) H2(g)  2H(g); H = 435.9 kJ mol-1
(iv) Bond energy of CH bond is 416 kJ mol-1 Ans. 329.77 kJ mol-1
87. Calculate the resonance energy of N2O from the following data :
Hof of N2O = 82 kJ mol-1, Bond energies of N  N, N = N, O = O and N = O bonds are 946,
418, 498 and 607 kJ mol-1 respectively. Ans. 88 kJ mol-1.
87. Given : C(graphite) + O2(g)  CO2(g) rHo = - 393.5 kJ mol-1+
H2(g) + 1/2 O2(g)  H2O(l); rHo = - 285.8 kJ mol-1
CO2(g) + 2H2O(l)  CH4(g) + 2O2(g) ; Ho = + 890.3 kJ mol-1
Based on the above thermochemical equations, the value of rHo at 298 K for the reaction
C(graphite) + 2H2(g)  CH4(g) will be: JEE MAINS-2017
(1) +144.0 kJ mol -1
(2) -74.8 kJ mol (3) - 144.0 kJ mol (4 +74.8 kJ mol
-1 -1 -1

Ans. (2) C(graphite) + O2(g)  CO2(g)

Hr = -393.5 kJ/mol = HrCO2(g)
H2(g) + 1/2 O2(g)  H2O(  )
Hr = - 285.8 kJ/ mol = Hf H2O(l)
CO2(g) + 2H2O(  )  CH4(g) + 2O2(g)
Hr = Hf(CH4) - HfCO2(g) - 2HfH2O(  ) = 890.3
 HfCH4 + 393.5 + 2  285.8 = 890.3
 HfCH4(g) = - 74.8 kJ/mol.
NCERT PROBLEMS
88. The enthalpy of combustion of methane, graphite and dihydrogen at 298 K are – 890.3 kJ mol-1, -393.5 kJ
mol-1 and -285.8 kJ mol-1 respectively. Enthalpy of formation of CH4(g) will be

(i) – 74.8 kJ mol-1 (ii) – 52.27 kJ mol-1 (iii) + 74.8 kJ mol-1 (iv) + 52.26 kJ mol-1

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 MASTERING CHEMISTRY 11
89. Enthalpies of formation of CO(g), CO2(g), N2O(g) and N2O4(g) are – 110, - 393, 81 and 9.7 kJ mol-1
respectively. Find the value of r H for the reaction
N2O4(g) + 3 CO(g)  N2O(g) + 3CO2(g) Ans. - 777.7 kJ
90. Given : N2(g) + 3H2(g)  2 NH3(g) ; rH + - 92.4 kJ mol . What is the standard enthalpy of formation
o -1

of NH3 gas ? Ans. - 46.2 kJ mol-1.

91. Calculate the standard enthalpy of formation of CH3OH (l) from the following data :
(i) CH3OH (l) + 3/2O2(g)  CO2(g) + 2H2O(l); rHo = - 726 kJ mol-1.
(ii) C(s) + O2(g)  CO2(g) ; cHo = - 393 kJ mol-1
(iii) H2(g) + ½ O2(g)  H2O(l) ; f Ho = - 286 kJ mol-1. Ans. - 239 kJ mol-1.
92. Calculate the enthalpy change for the process
CCl4(g)  C(g) + 4Cl(g)
And calculate bond enthalpy of C  Cl in CCl4(g)
Given : vap Ho (CCl4) = 30.5 kJ mol-1
fHo (CCl4) = - 135.5 kJ mol-1
 Ho (C) = 715.0 kJ mol-1 where Ho is enthalpy of atomization
Ho (Cl2) = 242 kJ mol-1 Ans. 326 kJ mol-1.
ADDITIONAL NUMERICALS.
93. Propane has the structure H3C – CH2 – CH3 . Calculate the change in enthalpy for the following reaction :
C3H8(g) + 5 O2(g)  3 CO2(g) + 4H2O(g)
Given that average bond enthalpies are :
C–C C–H C=O O=O O–H
34 414 741 498 464 kJ mol-1 Ans. - 1662 kJ mol-1
94. Calculate the enthalpy of formation of carbon monoxide (CO) from the following data :
(i) C(s) + O2(g)  CO2(g) ; rHo = - 393.5 kJ mol-1
(ii) CO(g) + ½ O2(g)  CO2(g) rHo = - 283.0 kJ mol-1 Ans.- 110.5 kJ mol-1
95. The enthalpy of combustion of ethyl alcohol (C2H5OH) is 1380.7 kJ mol . If the enthalpies of formation of
-1

CO2 and H2O are 394.5 and 286.6 kJ mol-1 respectively calculate the enthalpy of formation of ethyl alcohol.
Ans. - 268.1 kJ mol-1
96. Calculate the heat of formation of KCl from the following data :
(i) KOH (aq) + Cl (aq)  KCl (aq) + H2O(l), H = - 57.3 kJ mol-1
(ii) H2 (g) + ½ O2 (g)  H2O(l), H = - 286.2 kJ mol-1
(iii) ½ H29g) + ½ Cl2 (g) + aq  HCl (aq), H = - 164.4 kJ mol-1
(iv) K(s) + ½ O2(g) + ½ H2(g) + aq  KOH (aq), H = - 487.4 kJ mol-1
(v) KCl (s) + aq  KCl (aq), H = + 18.4 kJ mol-1 Ans. - 441.3 kJ mol-1
97. Which of the following reaction defines ∆Hfo ?
a) C(diamond) + O2(g) → CO2(g) (b) ½ H2(g) + ½ F2(g) → HF (g)
c) N2(g) + 3H2(g) → 2 NH3(g) (d) CO(g) + ½ O2(g) → CO2(g) IIT-2003
98. If the bond dissociation energies of XY, X2 and Y2 (all diatomic molecules) are in the ratio 1 : 1 : 0.5 and
∆Hf for the formation of XY is – 200 kJ mol-1, the bond dissociation energy of X2 will be
a) 100 kJ mol-1 (b) 200 kJ mol-1 (c) 400 kJ mol-1 (d) 800 kJ mol-1 AIEEE-2005
99. The bond dissociation energies of X2, V2 and XY are in the ratio of 1 : 0.5 : 1. ΔH for the formation of XV
is —200 kJ mol-1 , The bond dissociation energy of X2 will be NEET-2018
(1) 200 kJ mol (2) 100 kJ mol (3) 400 kJ mol (4) 800 kJ mol
-1 -1 -1 -1

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 MASTERING CHEMISTRY 12
1
Sol (4) The reaction of ΔfHo(XY) X 2 , Y2 ( g )  XY(g)
2
X
Bond energies of X2, Y2 and XV are x, , x respectively.
2

 X X
On solving, we get     = - 200
 2 4
 x = 800 kJ/mole
100. The standard enthalpy of formation (∆fHo) at 298 K for methane, CH4(g), is – 74.8 kJ mol-1. The
additional information required to determine the average energy for C – H bond formation would be
a) the first four ionization energies of carbon and electron gain enthalpy of hydrogen
b) the dissociation energy of hydrogen molecule, H2
c) the dissociation energy of H2 and enthalpy of sublimation of carbon
d) latent heat of vaporization of methane. AIEEE-2006
101. Oxidising power of chlorine in aqueous solution can be determined by the parameters indicated below:

1
Cl 2 ( g ) 
The energy involved in the conversion of 2 to Cl ( aq ) (using the data,
 diss H Cl 2 = 240 kJ mol1,  eg H Cl   349 kJ mol1,  hyd H Cl    381 kJ mol1)
will be
(1)  610 kJ mol-1 (2) 850 kJ mol-1 (3)+120 kJ mol-1 (4)+ 152 kJ mol-1 AIEEE-2008
102. The enthalpy of hydrogenation of cyclohexene is -119.5 kJ mol . If resonance energy of benzene is –
-1

150.4 kJ mol-1, its enthalpy of hydrogenation would be

a) -269.9 kJ mol-1 (b) -358.5 kJ mol-1 (c) – 508.9 kJ mol-1 (d) – 208.1 kJ mol-1 AIPMT-2006
103. Consider the following reactions :
(i) H+ (aq) + OH- (aq) = H2O(l), ∆H = - X1 kJ mol-1
(ii) H2(g) + ½ O2(g) = H2O(l), ∆H = - X2kJ mol-1
(iii) CO2(g) + H2O (g) = CO(g) + H2O(l) = X3kJ mol-1
(iv) C2H2(g) + 5/2 O2(g) = 2CO2(g) + H2O(l) + X4kJ mol-1
Enthalpy of formation of H2O(l) is
a) +X1kJ mol-1 (b) – X2kJ mol-1 (c) + X3 kJ mol-1 (d) – X4kJ mol-1 AIPMT-2007
104. Given that bond energies of H – H and Cl – Cl are 430 kJ mol and 240 kJ mol respectively and ∆fH
-1 -1

for HCl is – 90 kJ mol-1. Bond enthalpy of HCl is.

a) 245 kJ mol-1 (b) 290 kJ mol-1 (c) 380 kJ mol-1 (d) 425 kJ mol-1 AIPMT-2007
105. Bond dissociation enthalpy of H2, Cl2 and HCl are 434, 242 and 431 kJ mol respectively. Enthalpy of
-1

formation of HCl is :
1) – 93 kJ mol-1 (2) 245 kJ mol-1 (3) 93 kJ mol-1 (4) - 245 kJ mol-1 AIPMT-2008
106. The standard enthalpy of combustion at 25 C of H2, C6H10 and cyclohexane (C6H12) are -241, - 3800 and
o

– 3920 kJ mol-1 respectively. Calculate heat of hydrogenation of cyclohexene (C 6H10). Ans. - 121 kJ
107. Calculate standard heat of formation of CS2. Given that standard heat of combustion of C,S and CS2 are
– 393.3, - 293.72 and – 1108.76 kJ mol-1. Ans. + 128.02 kJ

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 MASTERING CHEMISTRY 13
108. Standard heat of formation of CH4, CO2 and H2O(g) are -76.2, -394.8 and – 241.6 kJ mol-1 respectively.
Calculate the amount of heat evolved by burning 1 m3 of CH4 measured under normal conditions.
Ans. 35.795 × 103 kJ
109. 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) + O2(g) → B2O3(s) ; ∆H = - 1273 kJ … (1)
2
1
H2(g) + O2(g) → H2O(l); ∆H = - 286 kJ …(2)
2
H2O(l) → H2O(g); ∆H = 44 kJ … (3)
2B(s) + 3H2(g) → B2H6(g); ∆H = 36 kJ …(4)
Ans. - 2035 kJ
110. Calculate ∆H f for chloride ion from the following data :
o

½ H2(g) + ½ Cl2(g) → HCl(g) ; ∆Hof = - 92.4 kJ

HCl(g) + nH2O → H+ (aq.) + Cl- (aq.) ; ∆Ho = - 74.8 kJ
∆Hof H+ (aq.) = 0.0 kJ Ans. - 167.2 kJ
111. A cooking gas cylinder is assumed to contain 11.2 kg isobutene having heat of combustion – 2658 kJ
mol-1. If a family needs 15 × 103 kJ energy per day for cooking, how long a cylinder can last. Also if 30%
heat is lost due to incomplete combustion, then how long would it take to last. Ans. 24
112. An athlete is given 100 g glucose of energy equivalent to 1560 kJ. He utilizes 50% of this gained energy
in an event. In order to avoid storage of energy in body, calculate the weight of water he would need to
perspire. Enthalpy of H2O for evaporation is 44 kJ mol-1 Ans. 319.09 g
113. An athlete takes 20 breaths per minute at room temperature. The air inhaled in each breath is 200 mL
which contains 20% oxygen by volume, while exhaled air contains 10% oxygen by volume. Assuming that
all the oxygen consumed if used for converting glucose into CO2 and H2O(l), how much glucose will be
burnt in the body in one hour and what is the heat produced ? (Room temperature = 27oC and enthalpy of
combustion of glucose is – 2822.5 kJ mol-1 at 0oC) Ans. 29.25 g, 458.66 kJ
114. 3.67 litre of ethylene and methane gaseous mixture on complete combustion at 25 oC produces 6.11 litre
of CO2. Find out the amount of heat evolved on burning one litre of gaseous mixture. The heats of
combustion of C2H4 and CH4 are – 1423 and -891 kJ mol-1 at 25oC. Ans. 50.91 kJ
115. An intimate mixture of Fe2O3 and Al is used in solid fuel rocket. Calculate the fuel value per g and per
mL of mixture.
∆ H Al 2 O 3 = 399.0 kcal, ∆ H Fe 2 O 3 = 199.0 kcal
Density of Fe2O3 and Al are 5.2 g /mL and 2.7 g/mL respectively. Ans. 0.9346 kcal/g, 3.94 kcal/mL
116. Heat of atomization of NH3 and N2H4 are x kcal mol and y kcal mol respectively. Calculate average
-1 -1

3y - 4x
bond energy of N ― N bond. Ans. kcal mol-1
3
117. Using the data (all values in kcal mol-1 at 25oC) given below, calculate bond energy of C ― C and C ― H
bonds.
C(s) → C(g) ; ∆H = 172
H2 → 2H ; ∆H = 104
1
H2 + O2 → H2O(l) ; ∆H = - 68.00
2
C(s) + O2 → CO2 ; ∆H = - 94.0
Heat of combustion of C2H6 = - 372.0 Ans. 82 kcal, 99 kcal

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 MASTERING CHEMISTRY 14
118. The standard molar enthalpies of formation of cyclohexane (l) and benzene (l) at 25 oC are – 156 and +
49 kJ mol-1 respectively. The standard enthalpy of hydrogenation of cyclohexene (l) at 25oC is – 119 kJ mol-
1
. Use these data to estimate the magnitude of the resonance energy of benzene. Ans. - 152 kJ
WORK SHEET -6
TOPIC : ENTROPY
119. A Heated copper Block at 130 C loses 340 J of heat to the surroundings which are at room temperature
o

of 32o. Calculate

(i) The entropy change of the System (copper block) Ans. - 0.84 JK-1
(ii) The entropy change in the surroundings Ans. + 1.11 J K-1
(iii) The total entropy change in the universe due to this process. Ans. 0.27 JK-1
Assume that the temperature of the block and the surroundings remains constant.
120. One mole of an ideal gas at 300 K in thermal contact with surroundings expands isothermally
from 1.0 L to 2.0 L against a constant pressure of 3.0 atm. In this process, the change in entropy of
surroundings (Ssurr) in JK-1 is (1 L atm = 101.3 J)
(a) 5.763 (b) 1.013 (c) -1.013 (d) - 5.763 JEE ADVANCED-2016
Sol. (c) E = q + w
0 = q - Pext V
q = Pex V = 3 atm (2 - 1) L = 3 atm L
= (3  101.3) Joule
q 3 × 101.3
Ssurr = = = - 1.013 Joule/K
T 300
121. The rusting of Iron takes place according to the equation
4 Fe(s) + 3O2(g)  2Fe2O3 (s)
The standard enthalpy of formation of Fe2 O3(s) is – 824.2 kJ/mol and the standard entropy change for
the reaction is – 549 J K-1 mol. Calculate the entropy change of the Surrounding and predict whether rusting of
iron is spontaneous or not at 298K. Ans. 5531.54 JK-1 , 4982.5 JK-1
122. 10 kg of cold water at 2oC absorbs 50 J heat from the surroundings which are at temperature of 37 oC.
What is the entropy change of (i) the system (ii) the surrounding (iii) the universe assuming the change in
temperature of water and surroundings to be negligible. Ans. 0.02 JK-1
123. Calculate the entropy change involved in the conversion of one mole (18 g) of solid ice at 273 K to
liquid water at the same temperature. ( latent heat of fusion = 6025 J/mol.) Ans. 22.1 JK-mol-
124. Calculate the entropy change involved in the conversion of one mole (18 g) of liquid water 373 K to
vapour at the same temperature. ( latent heat of vapourisation of water = 2.257 kJ/g.) Ans. 108.9 JK-mol-
125. Two ideal liquids which are not associated in water have the same Svap = 21 cal/mole. If their boiling
points are in the ratio 1.2 : 1, their Hvap values will be in the ratio
a) 1 : 1.2 (b) 1 : 1 (c) 1.2 :1 (d) 2 : 2
126. What is the value of So0,m for CO and CO2 ?
a) 0,0 Jk - mol-1 (b) 0, 5.7 Jk - mol-1 (c) 5.7, 0 Jk - mol-1 (d) ) 5.7, 5.7 Jk - mol-1
127. The direct conversion of A to B is difficult. Hence, it is carried out by the following shown path :
∆S(A → C) = 50 e.u., ∆S(C → D)= 30 e.u., ∆S(B → D) = 20 e.u. , Where e.u. is entropy unit, then ∆S(A → B) is
a) + 100 e.u. (b) + 60 e.u. (c) - 100 e.u. (d) - 60 e.u. IIT-2006
128. The enthalpy change for the transition of liquid water to steam is 40.8 kJ mol at 373K. Calculate the
-1

entropy of vaporization of water. Ans. 109.4 JK-1 mol-1

129. Calculate the enthalpy of vaporization per mole for ethanol. Given ∆S − = 109.8 JK-1 mol-1 and boiling
point of ethanol = 78.5oC. Ans. 38.595 kJ mol-1

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 MASTERING CHEMISTRY 15
130. For a reaction taking place in a container in equilibrium with its surroundings, the effect of temperature
on its equilibrium constant K in terms of change in entropy is described by JEE-ADVANCED-2017
(A) With increase in temperature, the value of K for exothermic reaction decreases because the entropy
change of the system is positive
(B) With increase in temperature, the value of K for endothermic reaction increases because unfavourable
change in entropy of the surroundings decreases
(C) With increase in temperature, the value of K for exothermic reaction decreases because favourable
change in entropy of the surroundings decreases
(D) With increase in temperature, the value of K for endothermic reaction increases because the entropy
change of the system negative
Sol. (B,C)

WORK SHEET -7
TOPIC : GIBB’S FREE ENERGY
131. Titanium metal is used extensively in the aerospace industry because the metal imparts strength to
structures but does not unduly add to their masses. The metal is produced by the reduction of TiCl 4(l),
which in turn is produced from the mineral rutile (TiO 2). Can the following reaction for the production of
TiCl4(l) be carried out at 25oC ?

TiO2(s) + 2Cl2(g)  TiCl4(l) + O2(g)

Given Substance Hof, kJ mol-1 So, J mol-1 K-1
TiO2(s) -944.7 50.3
TiCl4(l) -804.2 252.3
Cl2(g) 0.0 233.0
O2(g) 0.0 205.1
a) spontaneous (b) Non spontaneous (c) Equilibrium (d) unpredictable
132. The free energy change when a mole of water is converted to steam at a pressure of 1 atmosphere and
100 oC is
a) 200 kJ mol-1 (b) 100 kJ mol-1 (c) 50 kJ mol-1 (d) 0 kJ mol-1
133. Enthalpy and entropy changes of a reaction are 40.63 kJ mol-1 and 108.8 JK-1 mol-1 respectively. Predict
the feasibility of the reaction at 27o C. Ans. Non-spontaneous
134. Calculate the free energy change on dissolving one mole of sodium chloride at 298K.
Lattice energy = + 777.8 kJ mol-1
Hydration energy for NaCl = - 774.1 kJ mol-1
S at 298 K = 0.043 kJ K-1 mol-1 Ans.  9.14 kJ mol-1
135. The following reaction is performed at 298 K.
2NO(g) + O2(g) 2NO2(g)
Te standard free energy of formation of NO(g) is 86.6 kJ/mol at 298 K. What is the standard free energy of
formation of NO2(g) at 298 K ? (Kp = 1.6  1012) JEE MAINS-2015
ln( 1.6 × 10 12 )
(1) 86600 (2) 0.5[2  86,600 - R(298) ln (1.6  1212)]
R( 298 )
(3) R(298) ln(1.6  1012) - 86600 (4) 86600 + R (298) ln (1.6  1012)

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 MASTERING CHEMISTRY 16
Sol. (2)Gorxn = 2 Go f(NO2) - 2Gf
o(NO)

Gf (NO2) = 1/2[G rxn + 2Gfo(NO)]

o o

Gfo(NO2) = 0.5 [2  86600 - R(298)ℓn(1.6  1012)]

136. H and S for the reaction
Ag2O(s)  2Ag(s) + 1/2 O2(g)
are 30.56 kJ mol-1 and 66.0 JK-1 mol-1 respectively. Calculate the temperature at which the free energy change for
the reaction will be zero. Predict whether the forward reaction will be favoured above or below this
temperature. Ans. The reaction will be spontaneous above 463 K
136. For a given reaction, H = 35.5 kJ mol-1 and S = 83.6 JK-1 mol-1. The reaction is spontaneous
at (Assume that H and S do not vary with temperature) NEET-2017
(1) T > 425 K (2) All temperatures (3) T> 298 K (4) T < 425 K
Sol. (1) G + H - TS for equilibrium G = 0
H = TS

Since the reaction is endothermic it will be spontaneous at T > 425 K.

137. In a fuel cell methanol is used as fuel and oxygen gas is used as an oxidizer. The reaction is
CH3OH(l) + 3/2 O2(g)  CO2 (g) + 2H2O (l)
At 298 K standard Gibb’s energies of formation for CH3OH(l), H2O(l) and CO2 (g) are  166.2, - 237.2 –
394.4 kJ mol-1 respectively. If standard enthalpy of combustion of methanol is – 726 kJ mol-1, efficiency of
the fuel cell will be : AIEEE-2009
a) 80 % (b) 87% (c) 90% (d) 97%
138. Kp for the reaction. A(g) + B(g) 2C(g) is equal to 0.5 at T = 298K, if initially P A = 1 atm, PB =
10 atm and PC = 5 atm, then initially.
a) G = 0 (b) G < 0 (c) G > 0 (d) H = TS
139. Calculate the standard free energy change for the reaction
4NH3(g) + 5O2(g)  4NO(g) + 6H2O (l)
Given tat the standard free energies of formation (rGo) for NH3 (g) , NO(g) and H2O(l) are – 16.8 , +
86.7 and – 237.2 kJ mol-1 respectively. Predict the feasibility of the above reaction at the standard state.
Ans. The process is feasible.
140. Which of the following statements is correct for a reversible process in a state of equilibrium? AIPMT-2015
(1) G = -2.30 RT log K (2) G = 2.30RTlogK
(3) G°=-2.30 RT log K (4)G° = 2.30 RT log K
Sol.(3) Go = -2.303 RT log K
141. The equilibrium constant for the reaction:
PCl5(g) PCl3(g) + Cl2(g)
at 298 K has been found to be 1.8 x 10 . Calculate Go for the reaction.
-7
Ans. 38.5 kJ mol-1
142. At 60oC, dinitrogen tetroxide is fifty percent dissociated. Calculate the standard free energy change at
this temperature and one atmosphere. Ans. - 790 J mol-1
143. Calculate equilibrium constant for the reaction at 400 K.
2NOCl(g) 2NO(g) + Cl2(g)
Ho = 77.2 kJ mol-1 and So = 122 JK-1 mol-1 at 400K Ans. 1.96  10-4
144. For the melting of ice at 25oC : H2O(s)  H2O(l)

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 MASTERING CHEMISTRY 17
The enthalpy of fusion is 6.97 kJ mol-1 and entropy of fusion is 25.4 J mol-1 K-1. Calculate the free energy
change and predict whether melting of ice is spontaneous or not at this temperature.
Ans. - 0.6 kJ mol-1 , spontaneous
145. Calculate ∆G and ∆Go for the reaction :
A + B C + D
At 27 C. Equilibrium constant (K) for this reaction = 102.
o
Ans. ∆G = 0 , ∆Go = - 11.488 kJ mol-1
146. The standard state Gibbs free energies of formation of C(graphite) at T = 298 K are
fGo [C(graphite)] = 0 kJ mol-1
fGo [C(diaond)] = 2.9 kJ mol-1
The standard state means that the pressure should be 1 bar, and substance should be pure at a given
temperature. The conversion of graphite [C(graphite)] to diamond [C(diamond)] reduces its volume by 2 
10-6 m3 mol-1. If C(graphite) is converted to C(diamond) isothermally at T = 298K, the pressure at which
C(graphite) is in equilibrium with C(diamond), is JEE-ADVANCED-2017
(Useful information : 1 J = 1 kg m s ; 1 Pa = 1 kg m s ; 1 bar = 10 Pa]
2 -2 -1 -2 5

(a) 14501 (b) 29001 bar (c) 58001 bar (d) 1405 bar
Sol. (a) C(graphite)  C(diamond) ; Go = GfGodiamond - fG0graphite = 2.9 kJ/mole at 1 bat As dGT = V.dP.

147. One mole of CH3COOH undergoes dimerization in vapour phase at 127oC as :

2CH3COOH(g) (CH3COOH)2(g)
Calculate the change in standard entropy during dimerization if dimmer formation is due to two H-bonds
involved in dimer, each of 33 kJ strength and the degree of dimerisation of acetic acid 98.2%
Ans. - 104.102 J/mol.
148. For an isomerisation reaction A B, the temperature dependence of equilibrium constant is given by
2000
loge K = 4.0 -
T
The value of ∆S at 300 K is therefore :
o

a) 4R (b) 5R (c) 400 R (d) 2000R

149. For the reaction A(s) B(l) + 2C(g), ∆Go (in joules)
= 90800 – 100T
The partial pressure of C(g) at 600 K in Torr is :
a) 15 (b) 22 (c) 35 (d) 46
150. The densities of graphite and diamond at 298 K are 2.25 and 3.51 g cm -3, respectively. If the standard
free energy difference (∆Go) is equal to 1895 J mol-1, the pressure at which graphite will be transformed into
diamond at 298 K is :
a) 9.9 × 106 Pa (b) 9.9 × 105Pa (c) 9.9 × 109 Pa (d) 9.9 × 107 Pa
151. Predict whether it is possible or not to reduce magnesium oxide using carbon at 298 K according to the
reaction
MgO(s) + C(s)  Mg(s) + CO(g)
rHo = + 491.18 kJ mol-1 and rSo = 197.67 JK-1` mol-1
If not at what temperature, the reaction becomes spontaneous.

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 MASTERING CHEMISTRY 18
Ans. The reaction will be spontaneous above 2484.8 K (or 2211.8 oC)
152. Calculate the standard Gibbs free energy change from the free energies of formation data for the
following reaction :
15
C6H6(l) + O 2 ( g )  6 CO2(g) + 3H2O(g)
2
Given that fGo [C6H6(l)] = 172.8 kJ mol-1
fGo [CO2(g)] = - 394.4 kJ mol-1
fGo [H2O(g)] = - 228.6 kJ mol-1 Ans. - 3225 kJ mol-1.
153. Calculate rGo for the following reactions using fGo values and predict which reactions are
spontaneous.
(a) Ca(s) + Cl2(g)  CaCl2 (s)
(b) HgO(s)  Hg(l) + ½ O2(g)
(c) NH3(g) + 2O2(g)  HNO3(l) + H2O(l), fGo value (kJ mol-1) are :
CaCl2(s) = - 748.1, HgO(s) = - 58.84
NH3(g) = - 16.45, HNO3(l) = - 80.71
H2O(l) = - 237.13 Ans. - 748.1 kJ ,58.84 kJ , - 301.39 kJ
154. For the water gas reaction
C(s) + H2O(g) CO(g) + H2(g)
The standard Gibbs energy for the reaction at 1000 K is -8.1 kJ mol-1. Calculate its equilibrium constant.
Ans. 2.64
155. Calculate rG for conversion of oxygen to ozone :
o

3/2O2(g)  O3(g) at 298 K.

Kp for this conversion is 2.47  10-29 Ans. 163.2 kJ mol-1
156. For the reaction at 298 K
2A(g) + B(g)  2D(g)
Uo = - 10.5 kJ and So = - 44.1 JK-1
Calculate Go for the reaction and predict whether the reaction may occur spontaneous or not.
Ans. 0.16 kJ mol-1 the reaction is not spontaneous.
157. An athelete in a gymnasium room lifts a 50kg mass through a vertical distance of 2.0 m; g = 9.8 ms -2.
The mass is allowed to fall through 2.0m distance while coupled to an electrical generator. The electrical
generator produces an equal amount of electrical work. This electrical work is used to produce aluminium
by Hall’s process involving the change
Al2O3 (molten) + 3C(s)  2Al(l) + 3CO(g)
The reaction require standard free energy change equal to 593 kJ. How many times must the athelete
lift the 50kg mass and to drop and couple with generator to produce sufficient Gibbs free energy to
produce 27g Al?
a) 100 (b) 200 (c) 300 (d) 400
158. Air contain 99% N2 and O2 gases. Then why don’t they combine to form NO under the standard
conditions ? Given that the standard free energy of formation of NO(g) is 86.7 kJ mol-1.
159. For an irreversible process taking place at constant T and pressure and in which only pressure-volume
work is being done, the change in Gibb’s free energy (dG) and change in entropy (dS) satisfy the criteria
a) (dS)V.E < 0 (dG)T.P < 0 (b) (dS)V.E > 0, (dG)T.P < 0
c) (dS)V.E = 0, (dG)T.P.= 0 (d) (dS)V.E = 0, (dG)T.P > 0
160. Which of the following relationships is correct ?

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 MASTERING CHEMISTRY 19
o o
o
TS - H o
H - TS o
TS - H o o
H - TS o
a) K = (b) K = (c) ln K = (d) ln K =
RT RT RT RT
161. The value of log10 K for a reaction A  B is (Given : ∆r H 298K = - 54.07 kJ mol-1
o

∆r So298K = 10 J K-1 mol-1 and R = 8.314 J K-1 mol-1; 2.303 × 8.314 × 298 = 5705)
a) 5 (b) 10 (c) 95 (d) 100 IIT-2007
162. For the process H2O(l) (1 bar, 373 K) → H2O(g) (1 bar, 373K), the correct set of thermodynamic
parameters is
a) ∆G = 0, ∆S = +ve (b) ∆G = 0, ∆S = -ve (c) ∆G = + ve, ∆S = 0 (d) ∆G = -ve, ∆S = +ve
IIT-2007
163. In the conversion of limestone to lime
CaCO3(s) → CaO (s) + CO2(g)
The values of ∆Ho and ∆So are + 179.1 kJ mol-1 and 160.2 J/K at 298 K and 1 bar. Assuming that ∆Ho and
∆So do not change with temperature, minimum temperature above which conversion of limestone to lime
will be spontaneous is
a) 1118 K (b) 1008 K (c) 1200 K (d) 845 K AIEEE 2007
164. The values of H and S for the reaction, C(graphite) + CO2(g)  2CO(g) are 170 kJ and 170 JK-1,
respectively. This reaction will be spontaneous at :
a) 1110 K (b) 510 K (c) 710 K (d) 910 K AIPMT-2009
165. If the enthalpy change for the transition of liquid water to steam is 30 kJ mol at 27oC, the entropy
-1

change for the process would be AIPMT 2011

1) 100 J mol K
-1 -1
(2) 10 J mol K (3) 1.0 J mol K (4) 0.1 J mol K
-1 -1 -1 -1 -1 -1

166. In which of the following reactions, standard reaction entropy change (∆S°) is positive and standard
Gibb's energy change (ΔG°) decreases sharply with increasing temperature? AIPMT 2012

(1) Mg(s) + ½ O2(g) → MgO(s) (2) ½ C graphite + ½ O2(g) → ½ CO2(g)

(3) C graphite + ½ O2(g) → CO(g) (4) CO(g) + ½ O2(g) → CO2(g)
167. For an ideal gas, consider only P-V work in going from in initial state X to the final state Z. The final
state Z can be reached by either of the two paths shown in the figure. Which of the following choice(s) is
(are) correct ? [take ∆S as change in entropy and w as work done] IIT-2012

a) ∆Sx → z = ∆Sx →y + ∆Sy →z (b) wx → z = wx → y + wy → z (c) wx → y → z = Wx + y (d) ∆Sx → y →z  ∆Sx → y

168. An ideal gas in a thermally insulated vessel at internal pressure = P1, volume = V1 and absolute
temperature = T1 expands irreversibly against zero external pressure, as shown in the diagram. The
final internal pressure, volume and absolute temperature of the gas are P2, V2 and T2, respectively. For
this expansion,

JEE ADVANCED-2014

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 MASTERING CHEMISTRY 20
(A) q = 0 (B) T2 = T1
(C) P2V2 = P1V1 (D) P2V 2 = P1V 1
169. For the process H2O(ℓ)  H2O(g)
at T = 100 oC and 1 atmosphere pressure, the correct choice is JEE ADVANCED-2014
a) Ssystem > 0 and Ssurroundings > 0 (b) Ssystem > 0 and Ssurroundings < 0
c)Ssystem < 0 and Ssurroundings > 0 (d) Ssystem < 0 and Ssurroundings < 0
170. For the reaction : X2O4(l)  2 XO2(g) AIPMT-2014
U = 2.1 k cal, S = 20 cal K at 300 K
-1

Hence , G is :
a) 2.7 k cal (b) - 2.7 k cal (c) 9.3 k cal (d) - 9.3 k cal
171. For complete combustion of ethanol JEE MAINS-2014
C2H5OH(l) + 3O2(g)  2CO2(g) + 3H2O(l)
the amount of heat produced as measured in bomb calorimeter, is 1364.47 kJ mol-1 at 25oC. Assuming
ideality the Enthalpy of combustion, cH, for the re-action will be: (R = 8.314 kJ mol-1)
a) - 1460.50 kJ mol-1 (b) -1350.50 kJ mol-1 (c) -1366.95 kJ mol-1 (d) - 1361.95 kJ mol-1

172. Match the thermodynamic processes given under Column-I with the expressions given under
Column -II JEE ADVANCED -2015
Column - I Column - II
(A) Freezing of water at 273 K and 1 atm (P) q = 0
(B) Expansion of 1 mole of an ideal gas into a vacuum under
isolated conditions (Q) w = 0
(C) Mixing of equal volumes of two ideal gases at constant
temperature and pressure in an isolated container (R) Ssys < 0
(D) Reversible heating of H2(g) at 1 atm from 300 K to 600 K (S) U = 0
(T) G = 0

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