Chemistry :

Energetics

SECTION - I
SUBJECTIVE TYPE PROBLEMS

Problem 1: A certain volume of dry air at NTP is expanded reversibly to four times its volume (a)
isothermally (b) adiabatically. Calculate the final pressure and temperature in each
case, assuming ideal behaviour.

 
Cp for air = 1.4 

C
 v 

Solution : Let V1 be the initial volume of dry air at NTP.

(a) Isothermal expansion : During isothermal expansion, the temperature remains the
same throughout. Hence, final temperature will be 273 K.
Since P1V1 = P2V2
P1V1 1 V1
P   0.25 atm
2 V2 4V1
(b) Adiabatic expansion :
T V 1

1 2
 
T2  V1 

273   4V
1
1.4

1
 40.4

T2  V1 

273
T   156.79 K
2
40.4
Final pressure :

P V 
1
 2
P2  V1 

11.4  4V
  41.4
 1
P2  V1 

P2  1
 0.143 atm
41.
4

Problem 2: A constant pressure calorimeter consists of an insulated beaker of mass 92 g made

 Chemistry :

up of glass with heat capacity 0.75 J K –1

g . The beaker contains
–1

100 mL of 1 M HCl of 22.6°C to which 100 mL1 M NaOH at 23.4°C is added. The
final temperature after the reaction is complete is 29.3°C. What is ΔH per mole for
this neutralization reaction ? Assume that the heat capacities of all solutions are equal
 Chemistry :
Energetics

to that of same volumes of water.

Solution : Initial average temperature of the acid and base

22.6  23.4
= 2  23.0C
Rise in temperature = (29.3 – 23.0) = 63°C
Total heat produced = ( 92 × 0.75 + 200 × 4.184) × 6.3
= (905.8) × 6.3 = 5706.54 J
57065.54
Enthalpy of neutralisation = – 10001
100
= – 57065.4 J = – 57 kJ

Problem 3: Show that the reaction,

CO(g) + ( 1/2 ) O2(g)  CO2(g)
at 300 K is spontaneous and exothermic, when the standard entropy change is
– 0,094 kJ mol–1 K–1. The standard Gibb’s free energies of formation of CO and
2
CO are – 394.4 and –137.2 kJ mol–1 respectively.

Solution: The given reaction is,

CO(g) + (1/2) O2(g) 
CO2(g)

(for reaction) = G

G 1 
 G
G CO2 CO   O2
 2
= – 394.4 – ( – 137.2 ) – 0
= – 257.2 kJ mol–1
G = H – TS
– 257.2 = H – 298 × (0.094)
or H = –288.2 kJ
G is –ve, hence the process is spontaneous, and H is also –ve, hence the process is
also exothermic.
Problem 4: Using the data (all values are in kJ/mol at 25°C) given below
(i) Enthalpy of polymerisation of ethylene = – 72
(ii) Enthalpy of formation of benzene (l) = 49
(iii) Enthalpy of vaporization of benzene (l) = 144
(iv) Resonance energy of benzene (l) = – 152
(v) Heat of formation of gaseous atoms from the elements in their standard states
H = 218, C = 715
(vi) Average bond energy of C—H bond = 415.
Calculate the bond energy of C —C and C==C bonds.
Solution : nCH2 = CH2  [—CH2—CH2—]n,
For breakage of each double bond, there is formation of two single bonds.
H = n [C=C – 2C–C]
 Chemistry :

H
= C–C – 2C–C = – 72 kJ/mol ...(i)
n
Resonance energy of benzene = Hf(benzene) – H°f(benzene)
(observed) (theoretical)
H°f(benzene) = H°f(benzene) – resonance energy = 49 + 152 = 210 kJ/mol.
(theoretical) (observed)

6C(s) + 3H2(g)  (l), H°f = 210 kJ/mol

Hf = [6HC(s)C(g) + 3H–H ] – [3C=C + 6C–H +3C–C + Hvap]

Given, C(s)  C(g), H = 715 kJ/mol
½ H2(g)  H(g), H = 218 kJ/mole
201 = [(6 × 715) + (218 × 6)] – [(3C=C + 3C–C + (6 × 415) + 144]
3C=C + 3C–C = 2763 kJ/mol ...(ii)
Solving equation (i) and (ii), we get
C–C = 331 kJ/mol
C=C = 590 kJ/mol
Problem 5 : Two moles of a perfect gas undergo the following processes :
(a) a reversible isobaric expansion from (1.0 atm, 20.0 L) to (1.0 atm, 40.0 L);
(b) a reversible isochoric change of state from (1.0 atm, 40.0 L) to (0.5 atm, 40.0 L);
(c) a reversible isothermal compression from (0.5 atm, 40.0 L) to (1.0 atm, 20.0 L);
(i) Sketch with labels each of the processes on the same P–V diagram.
(ii) Calculate the total work (w) and the total heat change (q) involved in the
above processes.
(iii) What will be the values of ΔU, ΔH and ΔS for the overall process?
P
1 2
1 atm
Solution : (i)
0.5 atm 3

20.0L 40.0L

V1
(ii) W = W1 2 + W2  3 + W3  1 = P(V2 – V1) + 0 + nRT ln
V3
20
= [1.04 × 105 (40 × 10–3 – 20 × 10–3)] + [(0.5 × 1.01 × 105 × 40 × 10–3) ln ]
40
[since nRT = P3V3]
= 2020 + [2020 × (– 0.693)] = 620.14 J
q = 620.14 J (since for cyclic process w = q).
 Chemistry :
Energetics

(iii) U = 0;
H = 0 and
S = 0
(As it is a cyclic process).
Problem 6 : Magnetite Fe3O4 is reduced to iron by hydrogen or carbon monoxide as
(i) Fe3O4(s) + 4H2(g) ⎯ ⎯→ 3Fe(s) + 4H2O(g)
(ii) Fe3O4(s) + 4CO(g) ⎯ ⎯→ 3Fe(s) + 4CO2(g)
Calculate the enthalpy change involved during the reduction to get 1g of iron. Data
given are
Substance : Fe3O4(s) CO(g) CO2(g) H2O(g)
ΔHf(298 K) 1117.1 110.5 393.5 241.8
[kJ/mol]
Solution : (i) Fe3O4(s) + 4H2(g) 3Fe(s) + 4H2O(g)
⎯⎯→
H1 = 4Hf (H2O, g) – Hf Fe3O4 (s)
= 4 × 241.8 – 1117.1 = – 149.9
149.9
Enthalpy change during the reduction to get 1g of Iron = 0.89226 kJ/g
= 3× 56

= 892.26 J/g
(ii) Fe3O4(s) + 4CO(g) ⎯⎯→ 3Fe(s) +
4CO2(g)
H2 = 4Hf (CO2, g) – 4Hf (CO, g) – Hf (Fe3O4, s)
= 4 × 393.5 – 4 × 110.5 – 1117.1 = 14.9 kJ
Enthalpy change during the reduction to get 1g of iron
14.9
= = 0.08869 kJ/g = 88.69 J/g
3× 56

Problem 7 : Calculate the resonance energy of C6H6 using kekule formula for C6H6 from the
following data.
(i)
ΔH 0 for C6H6 = – 358.5 kJ mol –1
f
(ii) Heat of atomisation of C = 716.8 kJ mol–1
(iii) Bond energy of C–H, C–C, C=C and H–H are 490, 340, 620, 436.9 kJ mol–1
respectively.

Solution : (i) 6C(s) + 3H (g) ⎯⎯→ H = – 358.5 kJ mol–1

2 e

(ii) 6C(s) + 3H (g) ⎯⎯→

 Htheoretical = ?
2
 Chemistry :
Htheoretical = [6HC(s)  C(g) + 3HH–H] – [3HC=C + 3HC–C + 6HC–H]
Chemistry :
Energetics

= [6 × 716.8 + 3 × 436.9] – [3 × 620 + 3 × 340 + 6 × 490]

= – 208.5 kJ mol–1
 Resonance energy
= Hexp – Htheoretical
= – 358.5 – (–208.5) = – 150.0 kJ mol–1
Problem 8 : When maltose, C12H22O11(s) burns in a calorimetric bomb at 298 K yielding water and
carbon dioxide, the heat of combustion is –1350 k cal/mol. Calculate the heat of
combustion of maltose at constant pressure if the water vapour resulting from the
combustion is (a) condensed and (b) not condensed.
Solution : The combustion reaction of maltose can be shown for (a) and (b) as follows.
(a) C12H22O11(S) + 12O2(g) ⎯⎯→ 12CO2(g) + 11H2O( 𝑙 )
(b) C12H22O11(s) + 12O2(g) ⎯⎯→ 12CO2(g) + 11H2O(g)
Case A : When water is condensed
It is given that
Hv = – 1350 k cal/mol
n = 0, R = 1.987 × 10–3 k cal mol–1 K–1
T = 298 K
On inserting these value in the expression
HP = HV + nRT
HP = – 1350 + 0 × RT = – 1350 kcal/mol
Case B : When water is not condensed
It is given that,
HV = – 1350 k cal/mol
n = (12 + 11 – 12) = 11
R = 1.987 × 10–3 kcal/mol
T = 298 K
On inserting these values in the expression
HP = HV + nRT
H = [– 1350 + (11 × 1.987 × 10–3 × 298)] kcal
P
HP = – 1343 kcal/mol

Problem 9 : A Carnot’s engine works between 120°C and 30°C. Calculate the efficiency. If the
power produced by the engine is 400 watts, calculate the heat absorbed from the
source and rejected to the sink every second.
T1  T2
Solution : Efficiency,  =
T1
Here T1 = 273 + 120 = 393 K
T2 = 273 + 30 = 303 K

393  303
= = 0.229 = 22.9%
393
 Chemistry :

Q1  Q2 W
Again  Q1  Q1
=
Thus, heat absorbed from the source,

W 400
Q1 = = 1747 watts.
  0.229

Q2
Also T2
Q1  T1
 The heat rejected to the sink
T2
Q2 = Q1  303
T1 = 1747  = 1347 watts
393
Problem 10: When 12.0 g of carbon reacted with oxygen to form CO and CO 2 at 25°C and constant
pressure, 75.0 kcal of heat was liberated and no carbon remained. Calculate the
mass of oxygen needed for it and moles of CO and CO2 formed. Given ΔHf CO2 = –
94.05 and ΔHf CO = –26.41 kcal mole –1
Solution: Here C + O2  CO2 ; H = –94.05 kcal
C + ½ O2  CO ; H = –26.41 kcal
Let a mole of carbon reacts to form CO2 and b moles of carbon reacts to form CO.
Since 12g or 1 mole carbon is used up
12
a+b= =1 ...(1)
12
a  94.05 + b 26.41 = 75 ...(2)
a = 0.718 i.e. mole of CO2 formed
b = 0.282 i.e. mole of CO formed
0.282
Also moles of O2 used for this change = 0.718 = 0.859
+ 2
Thus weight of O2 used = 0.859  32 = 27.49 gm
 Chemistry :

SECTION - II
SINGLE CHOICE PROBLEMS
Problem 1 : AB, A and B are diatomic molecules, if the bond enthalpies of A , AB and B are in the
ratio of2 1 : 1 :20.5 and the enthalpy of formation of AB from A2 and2 B2 is – 1002 kJ mol –1,
combustion
500 of A2 gives AO and HC = – 1200 kJ mol . Bond energy of (O = O) bond is
–1

kJ mol . What is the bond enthalpy of (A – O) bond ?

–1

(a) 400 kJ mol–1 (b) 1650 kJ mol–1

(c) 1200 kJ mol–1 (d) 200 kJ mol–1
Solution : ½A2 + ½B2  AB; H = – 100
½A–A + ½B–B – A–B = – 100
Let A—A bond energy is x, then
x x
  x  100
2 4
x = + 400 kJ mol–1|
½A2 + ½O2   AO; H = – 1200 kJ mol–1
C
½(400) + ½ – = – 1200 kJ mol–1
O–O
 = 200 + 250 + 1200 = 1650 kJ mol–1
A
(b)
Problem 2 : The normal boiling point of an ether is 307 K. Ether is to be stored in aluminium drums that
can withstand a pressure of 10atm. If vapourisation of ether is 27kJ mol–1 at its boiiling
point, the maximum temperature to which the drums of ether could be safely exposed is
(a) 293 K (b) 315 K
(c) 392 K (d) 420 K
Solution : For the reaction,

Ether (l) □ □ □ Ether (g); Kp = pether (g) = 1 atm at 307 K

We have to find the temperature at which its K p value i.e. the pressure of vapourised ether
becomes equal to the limiting value of pressure (10 atm) and for this purpose, we have the
enthalpy of above reaction. Therefore

log P2 H 1 1  log 10 = 27000  1 1 

P = 2.303 R T  T 1 2.303 8.314 307 T
1  1 2  2

 T2 = 392.47 K
(c)
Problem 3 : Generally alkali metals form their oxides by an average increment of 6 kJ mol–1 K–1 in
their entropies. If at 25°C, G ° of Al O (s) = – 1582 kJ
f 2 3
mol –1
; H °
of f
Li2O(s) = 1244 kJ and Hf° of Na2O(s) = 1411 kJ. The aluminium oxide can be reduced to
Al metal by
(a) sodium (b) lithium
 Chemistry :

(c) both (d) none

 Chemistry :

Solution : For LI2O,

2Li(s) + ½O2(g)  Li2O(s)
Gf°(Li2O) = Hf° – T.S°
= 1244 – (298 × 6) = – 544 kJ mol–1
For Na2O,
2Na(s) + ½O2(g)  Na2O(s)
Gf°(Na2O) = Hf° – T.S°
= 1411 – (298 × 6) = – 377 kJ mol–1
Now for reaction
Al2O3(s) + 6Na(s) 3Na2O(s) + 2Al(s)
G° = 3 × Gf°(Na2O) – Gf°(Al2O3)
= 3 × (–377) – (–1582) = + 451 kJ mol–1
Similarly, when Li is used
G° = 3 × Gf°(Li2O) – Gf°(Al2O3)
= 3 × (– 544) – (– 1582)
= – 1632 + 1582 = – 50 kJ mol–1
G° is negative when Li is used for the reduction, so the reaction is feasible,
(b)
Problem 4 : 4.8 g of C (diamond) on complete combustion evolves 1584kJ of heat. The standard heat
of formation of gaseous carbon is 725 kJ/mol. The energy required for the process
(i) C(graphite)  C(gas)
(ii) C(diamond)  C(gas) are
(a) 725, 727 (b) 727, 725
(c) 725, 723 (d) none of these
Solution : The expression for standard heat of formation of gaseous carbon is is
C (graphite)  C(gas)
H = 725 kJ/mol
As graphite is thermodynamically more stable than diamond so the heat reqired to convert
graphite to gaseous carbon should be more.
(c)
Problem 5 : A reversible isothermal evaporation of 90 g of water is carried out at 100°C. Heat of
evaporation of water is 9.72 kcal mol–1. Assuming water vapour to behave like an ideal gas,
what is the change in internal energy of the system ?
(a) 48.6 kcal (b) 52.23 kcal
(c) 44.87 kcal (d) 56.06 kcal
Solution : Change in enthalpy (H) = Heat of evaporation × Number of moles = 9.72 × 5
H = E + nRT
E = 48.6 – (5 × 2 × 10–3 × 373) = 44.87 kcal
(c)
 Chemistry :

Problem 6 : When a polyatomic gas undergoes an adiabatic process, its temperature and volume are
related by the equation TV  – 1 = constant the value of n will be
(a) 1.33 (b) 0.33
(c) 2.33 (d) 1
Solution : For adiabatic process
TV – 1 = constant
For polyatomic
gas
4
=
3 = 1.33 n = 1.33 – 1 = 0.33
 (b)
Problem 7 : Heat of solution of BaCl .2H O = 200 kJ mol–1
Heat of hydration of BaCl22
= – 150 kJ mol– 1
Hence heat of solution of BaCl2 is
(a) 350 kJ (b) 50 kJ
(c) – 350 kJ (d) none
Solution : We have
BaCl2 . 2H2O + aq ⎯⎯→ Ba2+ (aq) + 2Cl– (aq) + 2H2O; H = 200 kJ mol–
1 BaCl2 + 2H2O ⎯⎯→ BaCl2 . 2H2O H = – 150 kJ mol–1
On adding both equation we get
BaCl2 + aq ⎯⎯→ Ba2+ (aq) + 2Cl– (aq) H = 50 kJ mol–1
This is the reaction for dis solution of BaCl2. Therefore heat of this reactions is in fact the
heat of solution of BaCl2.
 (b)
Problem 8 : For the combustion of n - octane
C8H18 + O2  CO2 + H2O at 25°C (ignoring resonance in CO 2)
(a) H = E – 5.5  8.31  0.298 in kJ/mol
(b) H = E + 4.5  8.31  0.298 in kJ/mol
(c) H = E – 4.5  8.31  0.298 in kJ/mol
(d) H = E – 4.5 + 8.31  0.298 in kJ/mol
Solution : C8H18(l) + 12.5 O2(g)  8CO2(g) + 9H2O(l)
H = E + (8 – 12.5)  8.31  0.298 in kJ/mol
(c)
Problem 9 : In which case of mixing of a strong acid and a base each of 1 N concentration,
temperature increase is highest.
(a) 20 ml acid – 30 ml alkali (b) 10 ml acid – 40 ml alkali
(c/) 25 ml acid – 25 ml alkali (d) 35 ml acid – 15 ml alkali
 Chemistry :

Solution: Highest amount of heat will be released when equivalents of acid and base are equal i.e.,
complete neutralisation takes place.
 (c)
Problem 10 : The difference between the heat of reaction of constant pressure and constant volume for
the reaction
2C6H6(l) + 15O2(g)  12CO2(g) + 6H2O(l) at 25°C in kJ
is (a) –7.43 (b) 3.72
(c) –3.72 (d) 7.43
Solution : For the reaction
2C6H6(l) + 15O2(g)  12CO2(g) + 6H2O(l)
Here n = 12–15 = –3
As we know, H = E + nRT
or, H – E = nRT = – 3  8.314 × 298 = – 7.43 kJ
 (a)
 Chemistry :

SECTION - III
MULTIPLE CHOICE PROBLEMS
Problem 1: Identify the intensive properties among the following :
(a) Enthalpy (b) Temperature
(c) Volume (d) Refractive index
Solution : (b, d)
Temperature and refractive index are intensive properties because they do not depend upon
amount of substance.
Problem 2 : Which of the following is/are endothermic process :
(a) combustion of glucose
(b) decomposition of water
(c) dehydrogenation of ethane to ethene
(d) Conversion of graphite to diamond.
Solution : (b, c, d)
Are endothermic whereas (a) is incorrect as combustion of glucose is exothermic
(d) Graphite to diamond is endothermic process because graphite is more stable than
diamond.
Problem 3: For an ideal gas undergoing isothermal irreversible expansion.
(a) U =0 (b) H = 0
(c) S = 0 (d) w = 0
Solution : (a, b)
(a) is correct U = CVT
T = 0  U = 0
(b) is correct H = Cp T
T = 0  H = 0
V2
(c) is incorrect. During expansion, S increases, S = 2.303 R log
V
1

(d) is incorrect as during expansion, gas is doing work.

Problem 4 : Which of the following are correct at 298 K
(a) G 0 element = 0 (b) H 0 element = 0
f f
(c) S 0 element = 0 (d) G 0 compound = 0
f f
Solution : (a, b)
For an element at 298 K
Gf°, Hf° = 0
 (a) and (b) are correct
(c) and (d) are incorrect as at 298 K, any substance has some entropy and also at 298 K
andy compound has some free energy.
Problem 5 : Under which of the conditions the process will be spontaneous?
(a) G = – ve (b) STotal = + ve
(c) STotal = – ve (d) STotal = 0
 Chemistry :

Solution : (a, b)
Any process will be spontaneous if the free energy of the system decreases, i.e., GP–GR <
0, i.e., product is more stable than reactant  G = – ve
also according to equation,
G = H – TS
G can be negative if TS > H
 S should be +ve and G = – TSTotal  G will be –ve if TSTotal + ve, i.e.,
STotal = + ve
Hence (a), (b) correct while (c), (d) are not correct.
Problem 6 : The expression for the temperature dependence of free energy is given by
 P 
(a) G° = V P – ST (b)  G  V S

   
T T
 V  V

(c) (G / T)  (d) G = H – TS

H 
 T 
 P T2
Solution : (a, b, c)
Free energy G = H – TS
 G = H – TS – ST
G = U + PV + VP – TS – ST
TS = U + PV
 G = VP – ST
Hence, choice (a) is correct.
G   V  P   S
Further    
 T V  T V
Hence, choice (b) is correct,
Choice (c) is correct because this expression is telling about how free energy changes with
temperature.
Choice (d) is incorrect because this expression valid is at constant temperature.
Problem 7 : During an adiabatic reversible expansion of an ideal gas
(a) Internal energy of the system decreases
(b) Temperature of the system decreases
(c) The value of  changes
(d) Pressure increases
Solution : (a, b)
For an adiabatic process,
E = w
E = nCv(T2 – T1) = w
 When gas expands, w is –ve. Hence, U decreases
 T2 – T1 = – ve
 Temperature decreases
Hence, choices (a) and (b) are correct while (c) and (d) are incorrect.
 Chemistry :

Problem 8 : Which is an irreversible process

(a) Mixing of two gases
(b) Evaporation of water at 373 K and 1 atm in a closed system.
(c) dissolution of NaCl in water
(d) H2O(s) at – 4°C
Solution : (a, c, d)
When two gases are mixed, no chemical reaction takes place but the two cannot be
separated under the same set of conditions without bringing further changes in the
surrounding which is a characteristic of irreversible process.
Hence, choice (a) is correct.
When NaCl is dissolved in water, the two cannot be separated without bringing changes
in The surrounding. Hence, an irreversible process.
Hence, choice (c) is also correct.
H2O at – 4°C is in ice state only when it is brought to 0°C that H 2O(s) and H2O(l) coexist
together.
Hence, the changes are brought about in the surroundings. So, it is an irreversible process.
Thus, choice (d) is also correct. Evaporation of water at 373 K or 100°C at 1 atm.
Here, H2O(l) and H2O(g) both coexist together,
So, it is a reversible process since at this stage both exist together. Both can be separated
without bringing further changes in the surrounding and secondly, it is closed system.
Problem 9 : During the Joule Thomson effect
(a) A gas is allowed to expand adiabatically from a high pressure region to a low
pressure region.
(b) A gas is allowed to expand adiabatically at constant pressure
(c) H = 0 for ideal gas
(d) U = 0 for ideal gas
Solution : (a, c, d)
During Joule Thomson effect, a gas is allowed to expand from high pressure to a low
pressure.
 Choice (a) is correct and hence choice (b) is incorrect.
During such a process, if the gas is ideal and it is allowed to expand freely, W = 0.
 dU and dH = 0
as no temperature changes take place.
 Choices (c) and (d) are correct for ideal gases.
Problem 10 : Which of the following relationships are correct
(a)  dH    dU  ve

   
 dT   dT 


P V

 dV 
 0 for ideal gas
(b)
 T
 dV  R
(c)  for one more of ideal gas
 
 d P P
(d)
 dH Chemistry :
 0 for an
ideal gas
 T 
 Chemistry :

Solution : (a, c, d)
CP – CV = + ve
 dH 
CP = 
dT
 dU 
and CV =  
dT
  dH    dV 
    = + ve
 dT P  dT V
Hence, choice (a) correct.
PdV = RdT for one mole of an ideal gas
 dV  R
   =
 d P P
Hence, choice (c) is correct.
For an ideal gas undergoing expansion or compression at constant temperature.
dH = 0
 dH 
   =0
 d T
Hence, choice (d) is correct.
dV for no gas can be zero.
 dV 
   0
 d P
 Choice (b) is incorrect.
 Chemistry :

MISCELLANEOUS PROBLEMS
SECTION
COMPREHENSION TYPE - PROBLEMS
Write up – I
For an ideal gas, an illustration of three different paths A, (B + C) and (D + E) from an initial state
P1, V1, T1 to a final state P2, V2, T1 is shown in the given figure.

P1, V1, T1 D
P1, V2, T3

P A E
P2, V2, T1
B
C
P3, V2, T2
V

Path A represents a reversible isothermal expansion from P1, V1 to P2, V2. Path (B + C) represents
a reversible adiabatic expansion (B) from P 1V1,T1 to P3, V2, T2 followed by reversible heating the
gas at constant volume (C) from P 3, V2, T2 to P2,V2, T1. Path (D + E) represents a reversible
expansion at constant pressure P1(D) from P1, V1, T1 to P1, V2, T3 followed by a reversible cooling
at constant volume V2(E) from p1, V2, T3 to P2,V2, T1.

Problem 1 : What is qrev, for path (A) ?

V2
(a) zero (b) nR ln
V1
V2 V2
(c) nRT ln (d) nRT ln
1
1
V
1 V
1

Solution : Ans. (d)

Path (A) for reversible isothermal expansion :
v2
dV V
w  nRT1  = nRT1 ln
2

V V
1v 1

V2
nRT ln
qrev = – w =
1 V1
 Chemistry :

Problem 2 : What is S for path A?

V2 V2
(a) nR ln (b) nR ln
V1 V1
(c) Zero (d) nR(V2 – V1)
Solution : Ans. (a)
qrev 1 V2 V2
S    nRT ln  nR ln
T T 1
V V
1 1 1 1

Problem 3 : What is qrev. for the path (D + E)?

(a) P1(V2 – V1) (b) Zero

(c)
T1
CV (T) T3
(d)  CV (T)dT
dT
T
3 T T1

Solution : Ans. (a)

For path D + E
qrev = P, (V2 – V1)

Write-up II

Heat of neutralisation is amount of heat evolved or absorbed when 1 g-equivalent of an acid reacts
with 1 g-equivalent of a base in dilute solution. If weak acid or weak base are neutralised, the heat
released during neutralisation is somewhat lesser than –13.7 kcal or –57.27 kJ. Heat of
neutralisation is also referred as heat of formation of water from H+ and OH– ions i.e.,
H+ + OH– — H O; H = –13.7 kcal
2

Problem 4 : When 20 ml of strong acid is added to 20 ml of an alkali, the temperature rises by 5°C. If
200 ml of each liquid are mixed, the temperature rise would be
(a) 5°C (b) 50°C
(c) 20°C (d) 0.5°C
Solution : Ans. (a)
Heat evolved in the 1st case = 40 × 5 = 200 cal
Heat evolved in the 2nd case = 10 times because amounts taken are 10 times = 10 × 200
= 2000 cal = 400 × t or t = 5°C.
Problem 5 : When 1 M H2SO4 is completely neutralised by sodium hydroxide, the heat liberated is
114.64 kJ. What is the enthalpy of neutralisation?
(a) + 114.64 kJ (b) – 114.64 kJ
(c) – 57.32 kJ (d) + 57.32 kJ
Solution : Ans. (c)
1 M H2SO4 = 2 NH2SO4. As heat of neutralisation is heat evolved for 1 mole of H+ ions,
therefore enthalpy of neutralisation = – 114.64/2 = – 57.32 kJ.
 Chemistry :

Problem 6 : The amount of energy released when 20 ml of 0.5 M NaOH are mixed with 100 ml of 0.1
M HCl is x kJ. The heat of neutralisation (in kJ mol–1) is
(a) – 100 x (b) – 50 x
(c) + 100 x (d) + 50 x
Solution : Ans. (a)
20 ml of 0.5 M NaOH = 20 × 0.5 = 10 millimoles = 10 milliequivalents.
100 ml of 0.1 M HCl = 100 × 0.1 = 10
milliequivalents 10 milliequivalents on neutralisation
give heat = x kJ.
 1 g eq. i.e. 1000 milli equivalent will give heat = 100x kJ

MATCHING TYPE PROBLEM

7. Match the following :

Column (I) Column (II)
(a) Enthalpy (p) Intrinsic property
(b) Temperature (q) Path function
(c) Free energy (r) Function of E, P, V
(d) Work (s) State function
Sol. (a)  (r), (s); enthalpy is a state function and is a function of internal energy and pressure and
volume.
(b)  (p); Temperature is independent of the bulk matter of the system and hence it is a intrinsic
property but it is a state variable.
(c)  (r), (s); Free energy is a state function as it depends on the state of the system as well as it
depends on H, T, and S. It is also a function of E, P, V.
(d)  (q); Work is a path function as the amount of work done depends upon path undertaken.

ASSERTION-REASON TYPE PROBLEMS

The question given below consist of an ASSERTION and the REASON. Use the following key for the
appropriate answers
(a) If both Assertion and Reason are correct and Reason is the correct explanation for Assertion
(b) If both Assertion and Reason are correct and Reason is not the correct explanation for
Assertion
(c) If Assertion is correct but Reason is not correct.
(d) If Assertion is incorrect but Reason is correct.

8. Assertion : H and U are the same for the reaction N2(g) + O2(g) □ □ □ 2NO (g)
Reason : All reactants are products are gases
Solution : H and U are the same because n = zero.
Ans. (b)
 Chemistry :

9. Assertion : Enthalpy of formation of HCl is equal to bond energy of HCl.

Reason : Enthalpy of formation and bond energy both involve the formation of one mole of HCl
from the elements.
Solution : Reason is correct explanation for assertion.
Ans. (a)

10. Assertion : For a particular reaction, heat of combustion at constant pressure (qp) is always greater
than that of constant volume (qv).
Reason : Combustion reactions are invariably accompanied by increase in the number of moles.
Solution : This is according to the relation : = qv + ng RT.
qp
Ans. (d)