ㅤ 26 Problems in Chemistry

THERMODYNAMICS
PROBLEM 189 Suppose that a gas obeys the modified van der Waals’ equation P × (Vm – b) = RT and
b = 0.02 L mol –1 . If 0.5 mol of the gas is reversibly compressed from an initial volume of 2 dm 3 to a final
volume of 0.5 dm 3 , how much work is done on the system at 27°C.
PROBLEM 190 One mole of a monoatomic, ideal gas confined in a 5 L piston fitted cylinder at 300 K is
heated such that its temperature increased to 400 K but at the same time gas also expanded to a volume of
8 L. Calculate change in enthalpy of the system.
PROBLEM 191 One mole of a monoatomic ideal gas confined in a 5 L, piston fitted cylinder at 300 K is
heated to 800 K as well as allowed to expand to a volume of 8 L simultaneously. Calculate change in
enthalpy of the system.
PROBLEM 192 100 g of nitrogen gas at 300 K are held by a piston under 30 atmosphere. The pressure is
suddenly released to 10 atmosphere and gas is allowed to expand adiabatically. If CV = 20.8 JK –1 mol –1 ,
calculate ∆S System .
PROBLEM 193 Calculate entropy change when 0.5 L of an ideal gas (CV =12.6 JK –1 mol –1 ) at 300 K
and one atmosphere is allowed to expand to double its volume and simultaneously heated to 373 K.
PROBLEM 194 10 g of ice at 0°C are added to 20 g water at 90°C in a thermally insulated flask of
negligible heat capacity. The heat of fusion of ice is 6 kJ/mol. What is the final temperature, ∆S System ?
C p = 75.42 JK –1 mol –1 .

PROBLEM 195 One mole of a supercooled liquid water at – 10°C and one atmosphere turns into ice at
– 10°C. Calculate entropy change for the system. C p for liquid water and ice are 75.42 and
37.2 JK –1 mol –1 respectively.
PROBLEM 196 In an open beaker at 27°C and one atm pressure, 100 g of zinc are caused to react with
dilute sulphuric acid. Calculate the work done by the liberated hydrogen gas assuming it to behave
ideally. What would be the work done if the reaction took place in a sealed vessel?
PROBLEM 197 A balloon is 0.5 m in diameter and contains air at 25°C and 1 bar pressure. It is then
filled with air isothermally and reversibly until the pressure reaches to 5 bar. Assume that pressure is
proportional to the diameter of the balloon, calculate (a) final diameter and (b) work done in the process.
PROBLEM 198 One mole of an ideal gas initially at 10 bar and 300 K is allowed to expand against a
constant external pressure of 2.00 bar to a final pressure of 2 bar. During this process, the temperature of
this gas falls to 250 K. Construct a reversible path connecting this initial and final state as a combination
of reversible isothermal expansion followed by reversible adiabatic expansion so that the final state is
attained and calculate work done by the system in attaining the final state. C vm = 3/ 2 R .
PROBLEM 199 With the temperature maintained at 0°C, 2 mole of an ideal gas are allowed to expand
against a piston that supports 2.0 bar pressure. The initial pressure of the gas is 10 bar and the final
pressure 2 bar.
(a) How much energy is transferred to the surrounding during the expansion?
(b) What is the change in internal energy and enthalpy of the gas?
(c) How much heat the gas has absorbed?

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ㅤ Problems in Chemistry 27

PROBLEM 200 A gas behaving ideally was allowed to expand reversibly and adiabatically to twice its
volume. Its initial temperature was 25°C and C vm = (5 / 2) R , calculate ∆E m and ∆H m .
PROBLEM 201 One mole of a gas at 300 K is compressed isothermally and reversibly from an initial
volume of10 dm 3 to a final volume of 0.2 dm 3 mol –1 . Calculate work done on the system if the equation
of state of the gas is (Vm – b) P = RT with b = 0.03 dm 3 mol –3 .

PROBLEM 202 One mole of a gas at 100 K is compressed isothermally from an initial volume of
20 dm 3 to a final volume of 5 dm 3 . Calculate the work done on the system if the equation state is:
 a 
 P + 2  Vm = RT where a = 0.384 m 6 Pa mol –1
 Vm 

PROBLEM 203 Find q,W, ∆U and ∆H if 2.0 g of He undergoes a reversible isobaric expansion from 20
to 40 L at 0.8 atm pressure followed by reversible isochoric heating till pressure reaches to 1.0 atm.
Depict the change of state on a P-V diagram.
PROBLEM 204 One mole of liquid water at 30°C is adiabatically compressed, pressure increasing from
1.0 atm to 10.0 atm. Since, liquids and solids are rather incompressible, it is a fairly approximastion to
take V constant. Calculate q, ∆U and ∆H for the process. C p of H 2O( l) = 75.42 JK –1 mol –1 .

PROBLEM 205 For a perfect gas, C v = 2.5 R . 2.0 moles of this gas undergoes following change of state:
(a) A reversible isobaric expansion from 1.0 atm, 20 L to 1.0 atm, 40 L.
(b) A reversible isochoric change from 1.0 atm, 40 L to 0.5 atm, 40 L
(c) A reversible isothermal compression from 0.5 atm, 40 L to 1.0 atm, 20 L. Sketch each process on
the P-V diagram and calculate : q, W, ∆U and ∆H.
PROBLEM 206 A sample of an ideal gas underwent an adiabatic expansion from 298 K, 15 bar to 2.5
bar against a constant external pressure of 1.0 bar. What is the final temperature of the system and work
done by the system, assume C vm = 2.5 R?
PROBLEM 207 A gas behaves ideally and its C v is given by: C v = 21.52 + 8.2 × 10 –3 T (all parameters
in SI unit). A sample of this gas is initially at T1 = 300 K, P1 = 10 bar andV1 = 1 L. It is allowed to expand
until P2 = 1 atm and V2 = 10 L. What are ∆U and ∆H for this process? Could the process be carried out
adiabatically. Calculate C p at 300 K.
PROBLEM 208 The entropy change of argon is given to a good approximation by the expression:
Sm / JK –1 mol –1 = 36.36 + 20.79 ln T
Calculate change in Gibb’s free energy of one mole of argon gas if it is heated at constant pressure
from 25°C to 50°C.
PROBLEM 209 Initially at 300 K and 10 atm pressure, 1.0 mole of an ideal gas is allowed to expand
adiabatically against a constant pressure of 4.0 atm until equilibrium is established. Assume the gas to be
ideal with:
C p = 28.58 + 1.76 × 10 –2 T
Calculate ∆U , ∆H, and ∆S.

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ㅤ 28 Problems in Chemistry

PROBLEM 210 An ideal gas expand against a constant external pressure of 2.0 atmosphere from 20 L to
50 L and absorb 20 kJ of energy from surrounding. What is the change in internal energy of the system?
10
PROBLEM 211 A gas expands against a variable pressure given by P = atm, where V is volume of
V
gas at each stage of expansion. Further during expansion from volume 10 L to 100 L, the gas undergoes a
change in internal energy of 420 J. How much heat is absorbed by the gas during expansion?
PROBLEM 212 Three moles of an ideal gas is heated at constant pressure of one atmosphere from 27°C
to 127°C. If C v is expressed as: C v = 30 + 14 × 10 –3 T JK –1 mol –1 , determine W, ∆E and q.

PROBLEM 213 One mole of an ideal gas at state A (500 K, 5.0 atm) is cooled at constant volume to
B (300 K) and then expanded isothermally and reversibly to C and finally compressed adiabatically to A.
5
Sketch the change on a P-V diagram and determine the net work done in this cyclic process. γ = .
3
PROBLEM 214 One mole of an ideal gas is subjected the following change of state:
Reversible
A(5.0 atm, 500 K) → B
Isothermal expansion

Isochoric cooling Reversible

B → C (300 K) → A
Adiabatic compression
Depicting the above mentioned change on a P-V diagram, determine the net work done in the cyclic
process. C v =1.5 R .
PROBLEM 215 One mole of an ideal gas initially at A (300 K and 5.0 bar) is heated at constant pressure
to double its volume (B). The gas is then expanded isothermally and reversibly to a new state C. The gas
is then cooled at constant pressure to another new state D (200 K) and finally compressed adiabatically
and reversibly to A. Depicting on a P-V diagram, determine the net work done in the above cyclic
process. C v =1.5 R .
PROBLEM 216 One mole of an ideal gas at A (500 K, 5.0 bar) is expanded isothermally and reversibly
to a new state B and then cooled at constant pressure to C (250 K) and finally compressed adiabatically
and reversibly to A. Depicting on a P-V diagram, determine the net work done in the cyclic process.
C v =1.5 R .
PROBLEM 217 One mole of an ideal gas at 500 K and 10 bar, defined by state A is allowed to expand
isothermally and does a work equal to 4200 J. Construct a combination of initial irreversible expansion
upto 2.0 bar followed by reversible expansion so that final state is reached and determine final pressure
of the gas.
PROBLEM 218 One mole of an ideal gas at 500 K and 10 bar is allowed to expand till the final pressure
falls to 1.0 atmosphere and final temperature falls to 250 K. Construct a combination of reversible path
of:
(a) initial adiabatic expansion followed by isothermal expansion so that final state is reached and
determine the total work done. C v =1.5 R .
(b) Determine the work by reversing the order of combination in (a) and compare the two work
done.

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ㅤ Problems in Chemistry 29

PROBLEM 219 One mole of an ideal gas at 300 K and 1.0 atmosphere is heated to 500 K and expanded
simultaneously to 36 litre. Determine ∆H assuming heat capacity to be independent of temperature and
C v =1.5 R .
PROBLEM 220 One mole of a gas initially at 300 K is heated to 500 K. Determine the Gibb’s free
energy change, ∆G if S = 1.5 + 3 × 10 –3 T [JK –1 mol –1 ] and C v =1.5 R .

PROBLEM 221 One mole of an ideal gas at 300 K and 1.0 atmosphere is heated as well as expanded
simultaneously to 500 K and 2.0 atmosphere. Determine ∆S if C v = 2.5 R .
PROBLEM 222 One mole of an ideal gas is taken in a one litre sealed flask at 300 K and heated till the
pressure becomes equal to 40 atmosphere. If C v = 12 + 28 × 10 –3 T (in SI unit), determine ∆S.

PROBLEM 223 A gaseous reactant A forms two different product in a parallel reaction B and C as
follows:
A → B ; ∆H ° = – 3 kJ, ∆S ° = 20 JK –1

A → C ; ∆H ° = – 3.6 kJ, ∆S ° = 10 JK –1
Discuss the relative stability of B and C on the basis of Gibb’s free energy change at 27°C.
PROBLEM 224 One mole of an ideal gas contained in a sealed flask at 1.0 bar is heated from 27°C to
127°C. Determine ∆G if: S (JK –1 ) = 10 +12 × 10 –3 T .
PROBLEM 225 Two moles of NO 2 is heated at constant volume from 27°C to 127°C and
C p (JK –1 mol –1 ) = 28 + 31 × 10 –3 T

Determine ∆S.
PROBLEM 226 Two moles of an ideal gas is expanded isothermally and irreversibly at 27°C from
volumeV1 to 2.5 V1 and 4.17 kJ heat is absorbed from surroundines. Determine ∆S sys , ∆S surr and ∆S univ .
PROBLEM 227 One mole of He(g) is mixed isothermally and reversibly with 2.0 mole of Ne(g).
Determine ∆S.
PROBLEM 228 C vm for an ideal gas is 2.5 R and it is independent of temperature. If 2.0 moles of this gas
is subjected to the following change of state :
Reversible
A (1.0 bar , 20 L ) → B (1.0 bar, 40 L)
Isobaric heating

Isochoric cooling Reversible

B → C (0.5 bar, 40L) → A
Isothermal compression

Representing the above change of states on a P-V diagram, determine the net work done.

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ㅤ 30 Problems in Chemistry

PROBLEM 229 An ideal gas has

C vm = a + bT
where a = 25 JK mol and b = 0.03 JK mol –1 . If 3.0 moles of this gas is subjected to a
–1 –1 –2

thermodynamic change of state from A (300 K, 2.0 bar) to B (500 K, 3.0 bar), determine q, W, ∆E, ∆H
and ∆S.
PROBLEM 230 One mole of an ideal gas defined by state A (400 K, 5.0 bar) is heated at constant
pressure to B (500 K) and then cooled at constant volume to C. The gas is then expanded isothermally
and reversibly to a new state D (1.0 bar) and finally compressed adibatically to A. Depicting on a P-V
diagram, determine the net work done in this cyclic process. C v =1.5 R ..
PROBLEM 231 One mole of an ideal gas is subjected to the following change of state:
Reversible Isochoric cooling
A(500 K, 5.0 bar ) → B → C (250K, 1.0 bar)
Isothermal expansion

Reversible
C → D (3.0 bar); C v =1.5 R
Adiabatic compression
Depicting the above change on a P-V diagram, determine the net work done.
PROBLEM 232 The entropy of vaporization of benzene is 85 JK –1 mol –1 .
(a) Estimate the enthalpy of vaporization of benzene at its normal boiling point of 80°C.
(b) Determine the entropy change of surroundings when 100 g benzene vaporizes at its normal
boiling point.
PROBLEM 233 The entropy of vaporization of acetone is 85 JK –1 mol –1 .
(a) Estimate enthalpy of vaporization of acetone at its normal boiling point 56°C.
(b) Determine entropy change of surrounding if 100 g of acetone condenses at its boiling point.
PROBLEM 234 With the help of following reduction reactions:
TiO 2 ( s) + 2C( s) → Ti( s) + 2CO( g ) …(i)
TiO 2 ( s) + C( s) → Ti( s) + CO 2 ( g ) …(ii)
at 1000 K, given ∆Gf° (CO) = − 200 kJ mol –1 , ∆Gf° (CO 2 ) = − 396 kJ mol –1 and
∆G f° TiO 2 ( s) = − 762 kJ mol –1 , determine which will be the predominant mode of reduction of TiO 2 ( s)
at 1000 K.
PROBLEM 235 The reaction for the production of synthetic fuel ‘water gas’ from coal is:
C( gr ) + H 2O( g ) → CO( g ) + H 2 ( g )
Standard molar entropies of C( gr ), H 2O( g ), CO( g ) and H 2 ( g ) are 5.7, 70, 190 and 131 JK –1 mol –1
respectively. Also, standard enthalpy of formations of H 2O and CO are –242 and –111 kJ mol –1
respectively. Determine the standard reaction free energy of reaction at 27°C. Also, predict about the
spontaneity and effect of temperature on direction of reaction.

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ㅤ Problems in Chemistry 31

PROBLEM 236 The thermodynamic informations for isomerization of alkene (C 4 H 8 ) at 300 K are as
follows:
cis-2-butene trans-2-butene
H 3C CH 3 1 H 3C H
C==C C==C
H H H CH 3
∆G ° = 66 kJ mol –1 2 ∆G ° = 63 kJ mol –1
f 3 f
∆H ° = − 7 kJ mol –1 ∆H ° = −11.2 kJ mol –1
f f

H CH 3
C==C
H CH 3
2-methylpropene
∆G °f = + 58 kJ mol

If the temperature of the above system is increased to 400 K and equilibrium was allowed to
re-establish, mole percentage of trans-2-butene at new equilibrium was 18. Determine ∆H ° and ∆S ° for
the isomerization reactions below:
cis-2-butene 2-methylpropene
trans-2-butene 2-methylpropene
PROBLEM 237 At a temperature above 65 K, decarboxylation of acetic acid, (i.e., loss of CO 2 )
becomes spontaneous. If ∆H f° of CH 3COOH, CO 2 ( g ) and CH 4 are −484.5, − 394 and − 74.8 kJ/mol
respectively, determine standard state entropy change ( ∆S ° ) for the decarboxylation reaction. What is
the driving force for getting this reaction to proceed?
PROBLEM 238 For the reaction:
H 2 ( g ) + CO 2 ( g ) H 2O( g ) + CO( g )
∆G at 2000 K is 2540 J, where partial pressures of the species are PH = 0.25, PCO2 = 0.78,
2
PH O( g ) = 0.66 and PCO = 1.2 atm respectively. Determine equilibrium composition of the gaseous
2
mixture.
PROBLEM 239 Consider the thermal decomposition of solid CaCO 3 as:
CaCO 3 ( s) CaO( s) + CO 2 ( g ).
The equilibrium vapour pressure of CO 2 at 700°C and 950°C are 22.6 and 1830 mm of Hg. Calculate
∆H ° and ∆S ° for the reaction.
PROBLEM 240 A certain reaction is spontaneous at 72°C. If the enthalpy change for the reaction is
19 kJ, what is the minimum value of ∆S for the reaction?
PROBLEM 241 The internal engine of a 1200 kg car is designed to run on octane whose enthalpy of
combustion is 5510 kJ/mol. If the car is moving up a slope, calculate the maximum height to which the
car can be driven on 2.0 gallon of the fuel. Assume the cylinder temperature is 2200°C and the exit
temperature is 760°C and ignore all form of friction. The mass of 1.0 gallon of fuel is 3.1 kg.
PROBLEM 242 One gram sample of oxygen undergoes free expansion from 0.75 L to 3.0 L at 298 K.
Calculate ∆S , q, W , ∆H and ∆E.

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ㅤ 32 Problems in Chemistry

PROBLEM 243 A 550 ml sample of an ideal gas at 300 K exerts 3 atm. The thermodynamic state of the
system changes in a process. In the final state, P = 3.5 atm and V = 730 mL. Calculate ∆S and ∆E and
∆H, C vm = (5 / 2) R .
PROBLEM 244 A sample of 0.0133 mole of an ideal gas, initially at 5.00 atm, expands isothermally and
reversibly from 3.00 L to 10 L. Calculate ∆S , ∆G and ∆H.
PROBLEM 245 One mole of an ideal gas originally at a volume of 8.00 Lit. at 1000 K, is allowed to
expand adiabatically until final volume is 16.00 Lit. For the gas C v =1.5 R . Calculate values of ∆S for
the process when:
(a) The expansion takes place reversibly.
(b) The expansion takes place against a constant pressure of 3.00 atm.
(c) The change in volume involves a free expansion.
PROBLEM 246 One mole of an ideal gas at 0°C and 1.0 atm pressure is mixed adiabatically with one
mole of a different gas at 100°C and 1.0 atm to yield a mixture. If C P for each gas is (5 / 2) R, determine
∆S (mixing).
PROBLEM 247 For chloroform gas C PM is expressed as:
C PM = 24.9 + 14.8 × 10 −2 T − 9 × 10 −5 T 2 JK –1 mol –1 .
Assuming this gas to be ideal, determine entropy change involved in heating 2.0 mole of gas from
volume 100 L at 500 K to a volume of 70 Lit. at 700 K.
PROBLEM 248 For N 2 ( g ), entropy function as a function of temperature is expressed as:
S = 25.1 + 29.3 ln T
Determine Gibb’s free energy change ∆G of one mole of nitrogen if it is heated from 298 K to 348 K
at 2.0 atm pressure.
PROBLEM 249 One mole of an ideal gas initially at 400 K and 10 atm, is adiabatically expanded
against a constant pressure of 5.0 atm until equilibrium is attained. If CV = 18.8 + 0.021T JK –1 mol –1 ,
determine ∆E , ∆H and ∆S .
PROBLEM 250 Molar volume of C 6 H 6 (l) is 89 c.c. at 27°C and 1.0 atm pressure. Assuming the volume
to be constant, determine ∆G for compression of 5.00 moles of liquid benzene from 1.0 atm to 100 atm.
PROBLEM 251 One mole of an ideal gas at 25°C is subjected to a reversible isoentropic expansion until
final temperature reached to 75°C. If the initial pressure was 1.0 atm, determine final pressure
CV = (3 / 2) R .
PROBLEM 252 A flask containing 1.00 mol of N 2 at 4.00 atm and 298 K was connected to a flask
containing 1.00 mol of N 2 gas at 2.00 bar and 298 K. The gases were allowed to mix isothermally.
Determine the entropy change for the system.
PROBLEM 253 One mole of solid iron was vaporized in an oven at 3500 K. If iron boils at 3133 K and
enthalpy of vaporization is 349 JK –1 mol –1 , determine ∆S system , ∆S surroundings and ∆S universe .

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