Numericals on Internal Energy

1. A gas expands against a constant pressure of 1 atmosphere from a volume of 5L to 10L.

During the process, system absorbs 400J of heat from the surroundings. Calculate the change
in the internal energy of the system. [1L atm = 101.3J]

Ans:- Since the gas expands, work is done by the system on the surroundings and ‘w’ is negative.

Heat absorbed by the system, q = 400J

Work done by the system, w = - PΔV

= -1 x (10 - 5)

= -5L atm

Therefore w = - 5L atm = - 5 x 101.3

= - 506.5J

According to the First Law of Thermodynamics

ΔE = q + w

= 400 + (- 506.5)

= -106.5 J

Hence the change in internal energy of the system is -106.5J

OR

According to the First Law of Thermodynamics

ΔE = q ± w

Work done by the system,

w = - PΔV

w = -1 x (10 - 5)

w = -5L atm

Therefore w = - 5L atm = - 5 x 101.3J

= - 506.5J

1
 ΔE = q ± w

ΔE = 400J - 506.5J

ΔE = -106.5 J

2. A 5 litres cylinder contained 10 moles of hydrogen gas at 27˚ C. Due to leakage, entire gas
escaped into the atmosphere. The atmospheric pressure is 1 atmosphere. Calculate the work
done by the gas assuming hydrogen to be an ideal gas.

Ans:- Initial volume of gas = 5L

Since hydrogen is assumed to behave as an ideal gas, the final volume is given by
$%&
V = '

() * ).),-( * .))
= (
= 246.3 L

ΔV = 246.3 – 5 = 241.3 L

Hence, w = - PΔV

= -1 x (241.3) L atm

= - 241.3 x 101.3 (since 1Latm = 101.3J)

= -24443.7J

= -24.4437kJ

3. A gas present in a cylinder fitted with a frictionless piston expands against a constant pressure
of 1 atmosphere from a volume of 2 litres to a volume of 6 litres. In doing so it absorbs 800J
heat from surroundings. Determine increase in internal energy of process.

Ans :- since work is done against constant pressure and thus irreversible.

Given, ΔV = (6-2) = 4L

P = 1 atm

W = - PΔV

W=-1x4L

= - 4 litres atomosphere
/0 * (.1,2
).),-(
[Since 0.0821 litre atmosphere = 1.987 cal]

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 = -96.81 cal

= -96.81 x 4.184 J [since 1 cal = 4.184 J]

= - 405.05 J

Now from First Law of Thermodynamics

ΔE = q + w

ΔE = 800 J – 405.05J

ΔE = 394.95 J

OR

According to the First Law of Thermodynamics

ΔE = q ± w

Work done by the system (Expansion of the gas)

w = - PΔV

ΔV = (6-2) = 4L

P = 1 atm

w = - PΔV

w = - 1atm x 4 L

w = - 4 L atm = - 4 x 101.3J ……. ( 1L atm = 101.3J)

w = - 405.2 J

So, ΔE = q ± w

ΔE = 800 J – 405.05J

ΔE = 394.95 J

4. Calculate the standard internal energy change for the reaction.

OF2 + H2O O2 + 2HF

(gas) (gas) (gas) (gas)

at 298K. The standard enthalpies of formation in kJmol-1 are

3
 OF2 = +20; H2O = -250; O2 = 0; HF = -270 (R = 8.314JK-1mol-1)

Ans:- ΔH˚ for the reaction

ΔH˚ = ΣΔH˚product - ΣΔH˚reactanat

ΔH˚ = [0 + 2 x (-270)] – [1 x (+20) + 1 x (-250)]kJ mol-1

= [(-540) – (20 - 250)]kJ mol-1

ΔH˚ = -540 + 230kJ = - 310 kJmol-1

For the given reaction,

Δng= Σn˚product - Σn˚reactanat

= [(1 + 2) – (1 + 1)] = +1

We know that,

ΔH˚ = ΔE˚ + (Δn)gRT

ΔE˚ = ΔH˚ - (Δn)gRT

= - 310kJ mol-1 – (1 mol x 8.314 x 10-3 kJ K-1mol-1 x 298K)

ΔE˚ = - 312.5 kJ mol-1

Numericals on Enthalpy

1. Calculate the difference between the heats of reaction at constant pressure and constant
volume for the reaction

2C6H6 + 15O2 12CO2 + 6H2O, at 25˚ C in kJ

(l) (g) (g) (l)

Ans:- Heat of reaction at constant pressure (ΔH) and heat of reaction at constant volume (ΔE) are
related as

ΔH = ΔE + ΔnRT

ΔH - ΔE = ΔnRT

For the give reaction

2C6H6 + 15O2 12CO2 + 6H2O

4
We know, Δn = Σn gas product - Σn gas reactant

= 12 – 15

=-3

Therefore, for the given reaction

ΔH - ΔE = ΔnRT

= -3 mol x 8.314 x 10-3 KJ mol -1 K -1 x 298 K

= - 743kJ

2. The heat of combustion of methane is measured in a bomb calorimeter at 298.2k and is found
to be - 885.5 kJmol-1. Find the value of enthalpy change ΔH.

Ans:- The combustion of methane takes place as follows

CH4 + 2O2 CO2 + 2H2O

(gas) (gas) (gas) (liquid)

Since heat of combustion is measured in a bomb calorimeter (i,e at constant volume)

ΔE = - 885.5kJ

For the given reaction

Δn = Σngas product - Σngas reactant

= 1- (1+2) = - 2

ΔH = ΔE + ΔnRT

= -885.5 + (-2) x 8.314 x 10-3 x 298.2

= - 890.46kJ

3. 0.16g of methane was subjected to combustion at 27˚C in a bomb calorimeter. The

temperature of the calorimeter system (including water) was found to rise by 0.5˚C. Calculate
the heat of combustion of methane at (i) constant volume and at (ii) constant pressure. The
thermal capacity of the calorimeter system is -17.7kJK-1 (R = 8.314JK-1mol-1)

Ans:- In a bomb calorimeter, reaction takes place at constant volume.

M
ΔE = Z x rise in T x
W
Therefore, heat gained by the calorimeter system is given by
5
 qv = -17.7 x 0.5

= - 8.85kJ
).(?
No. of moles of CH4 undergone combustion = (?
= 0.01 (molecular mass of CH4 = 16)

Hence, heat of combustion of methane at constant volume

B
ΔE = $DEC
F

/,.,G
ΔE = ).)(
= − 𝟖𝟖𝟓 kJmol-1

Combustion of methane at 27˚C takes place as follows

CH4 + 2O2 CO2 + 2H2O

Δn = 1 – (1+2) = -2

The heat of combustion of methane at constant pressure (ΔH) is given by

ΔH = ΔE + ΔnRT

= - 885 kJ mol -1 + ((-2) mol x 8.314x 10-3 kJ K -1 mol-1 x 300 K)

= - 890kJ mol-1

OR

Combustion of methane takes place at 27˚C = 300 K

Rise in temperature = 0.5 ˚C ……. (27˚C + 0.5 ˚C =27.5˚C = 300.5 K)

ΔT = (300.5K – 300 K = 0.5 K)

In a bomb calorimeter, reaction takes place at constant volume.

ΔE = 𝑞L

M
ΔE = Z x ∆T x
W
(? TUVW XY
ΔE = −17.7 7kJ𝐾 /( x 0.5 K x ).(? Z

ΔE = − 𝟖𝟖𝟓 kJmol-1

Combustion of methane at 27˚C takes place as follows

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 CH4 + 2O2 CO2 + 2H2O

Δn = 1 – (1+2) = -2

The heat of combustion of methane at constant pressure (ΔH) is given by

ΔH = 𝑞L

ΔH = ΔE + ΔnRT

= - 885 kJ mol -1 + ((-2) mol x 8.314x 10-3 kJ K -1 mol-1 x 300 K)

= - 890kJ mol-1

4. The heat of combustion of ethylene at 18˚C and constant volume is – 335.8 k.cal when water
is obtained in liquid state. Calculate the heat of combustion at constant pressure at 18˚C. [R =
2 x 10-3 k.c]

Ans:- The required equation is

C2H4 + 3O2 2CO2 + 2H2O

(gas) (gas) (gas) (liquid)

Given,

ΔE = - 335.8k.cal

Δn = 2 – 4 = -2

R = 2 x 10-3 k.cal

T = 291K

Substituting in the equation

ΔH = ΔE + ΔnRT

= - 335.8 k.cal + [(-2) x 2 x 10-3 x 291]

= - 335.8 – 1.164

= - 336.984 k cal

Numericals on Entropy

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1. Calculate the entropy change (ΔS ̊) for the following reaction at 25 ̊C
SO2 + 1⁄2O2 ® SO3

The absolute entropies at 25 ̊C and 1 atmosphere pressure for SO2, O2, and SO3 are 248.5,
-1 -1
205.0, and 256.2 JK mol respectively.


The entropy change for a reaction is given by

ΔS ̊ = ΣS ̊product - ΣS ̊ reactant

For the given reaction

SO2 + 1⁄2O2 ® SO3

(g) (g) (g)

ΔS ̊={S ̊[SO3]}–{S ̊[SO2]}+1⁄2xS ̊[O2]

(g) (g) (g)

= {256.2} – {248.5 + 1⁄2 x 205.0}

= 256.2 – 351.0

-1 -1
= - 94.8JK mol
-1
2. The following data are given for melting point of KCl. ΔH = 7.25 kJmol and ΔS = 0.007
-1 -1
kJmol K . Calculate the melting point.
The entropy of fusion is given by
ΔS f̊ us = ΔH ̊/ Tm

-1
Given that ΔH ̊fus = 7.25 kJmol
-1
ΔS ̊fus 
= 0.007 kJmol
Tm= ?

Substituting the value, we have

-1 -1
Tm= 7.25 kJmol / 0.007 kJmol
Tm= 1035.7 K

-1
3. For the reaction NH4Cl ® NH3 + HCl at 25 ̊C, enthalpy change ΔH = + 177 kJmol and
-1 -1
entropy change ΔS = + 285 Jmol K . Calculate the free energy change ΔG at 25 ̊C and
predict whether the reaction is spontaneous or not.
For the given reaction


8
 -1
ΔH = + 177 kJmol
-1 -1 -1 -1
ΔS = + 285 Jmol K = 0.285 kJmol K
T=25 ̊C=298K

ΔG is given by
:
ΔG=ΔH–TΔS

Therefore, for the given reaction

-1 -1 -1
ΔG=+177 kJmol – (298 K x0.285 kJmol K )
-1
= + 92.07kJmol 

+
The ve sign of ∆G indicates that the reaction is not spontaneous in the given direction.

4. The enthalpy change (ΔH) for the reaction

Ag2O ® 2Ag + 1⁄2O2
(S) (S) (g)

-1 -1 -1
is 30.54kJmol and entropy change (ΔS) is 0.06 kJK mol at 1 atm. Calculate the
temperature at which ΔG is equal to zero. Also predict the direction of reaction at a
temperature below the calculated temperature.
For the given reaction

-1
ΔH = +30.54 kJmol
-1 -1
ΔS = 0.06 kJK mol 


The reaction is in equilibrium. Therefore ΔG = 0.

ΔG is given by
ΔG=ΔH–TΔS
-1 -1 -1
0= +30.54 kJmol –Tx 0.06 kJK mol 

-1 -1 -1
T = 30.54 kJmol / 0.05 kJK mol 

T = 509 K

Therefore at 509K, ΔG = 0. Below 509K, TΔS < ΔH and ΔG = 0. Hence at temperature below
509K, the reaction will not occur in the forward direction. However ΔG is negative in the
reverse direction. Therefore below 509K, the given reaction will proceed in the backward
direction.

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