PH1102E

Thermodynamics
Engineering Physics Sem-I
Monsoon 2024-2025
Problem Sheet-1
Course Instructor: Sayani Chatterjee
email: sayani@nitc.ac.in
17.09.2023

1. A 0.01 Kg sample is composed of 50 molecular percent H2 , 30 molecular percent HD (Hydrogen Deuteride),

and 20 molecular percent D2 . What additional mass of D2 must be added if the mole fraction of D2 in
the final mixture is to be 0.3?
2. One tenth of a Kg of an aqueous solution of HCl is poured into 0.2 Kg of an aqueous solution of NaOH.
The mole fraction of the HCl solution was 0.1, whereas that of the NaOH solution was 0.25. What are
the mole fractions of each of the components in the solution after the chemical reaction has come to
completion?
3. The limiting value of the ratio of pressure of a gas at the steam point and at the triple point of water
when the gas is kept at constant volume is found to be 1.365954. What is the ideal-gas temperature of
the steam point?
4. The equilibrium states of superheated steam are represented by Callendar’s equation
rT a
v−b= − m,
P T
where b, r, a, and m are constants. Calculate the volume expansivity β = β(T, P ).
5. A block of copper at pressure 1 atm, a volume of 100 cm3 , and a temperature of 10◦ C experiences a rise
in temperature of 5◦ C and an increase in volume of 0.005 cm3 . Assuming that the volume expansivity
and isothermal compressibility remain constant at the vaues of 4.95 × 10−5 K−1 and 6.17 × 10−12 Pa−1 ,
calculate the final pressure.
6. For a particular gaseous system, the internal energy is given by

U = 2.5P V + constant (1)

Figure 1: Figure-1

1
 The system is initially in the state P = 0.2 MPa, V = 0.01 m3 ; designated as point A in the figure. The
system is taken through the cycle of three processes (A → B, B → C, C → A) as shown in the figure.
Calculate Q and W for each of the three processes. Calculate Q and W for a process from A to B along
the parabola P = 105 + 109 × (V − 0.02)2 .

7. Calculate the work done upon expansion of 1 mol of gas quasi-statically and isothermally from volume vi
to a volume vf , when the equation of state is
 a
P + 2 (V − b) = RT, (2)
b
where a and b are van der Waals constants.
If a = 1.4 × 109 N.m4 /mole and b = 3.2 × 10−5 m3 /mole, how much work is done when the gas expands
from a volume of 10 litres to a volume of 22.4 litres at 20◦ C?
8. A combustion experiment is performed by burning a mixture of fuel and oxygen in a constant-volume
container surrounded by a water bath. During the experiment, the temperature of the water rises. If the
system is the mixture of fuel and oxygen:

• Has heat been transferred?

• Has work been done?
• What is the sign of ∆U ?
9. A liquid is regularly stirred in a well-insulated container and thereby experiences a rise in temperature.
If the system is liquid:
• Has heat been transferred?
• Has work been done?
• What is the sign of ∆U ?

10. Calculate the work performed by 10 gm of oxygen expanding isothermally at 20◦ C from 1 to 0.3 atm of
pressure.
11. Evaluate F, G, and H as defined by
Z
F = (x2 dy + ydx) (3)
Z
G = [(x − y)dy + (y 2 − 2x)dx] (4)
Z
H = [2y(x − 2y)dx + x(x − 8y)dy] (5)

over each of the following paths from x = 0, y = 0 to x = 1, y = 2:

• y = 2x
• y = 2x2
• y = 2x1/2
Identify whether they are point or path functions.
12. Evaluate I, J, and K as defined by
Z
I = (xydy + xydx) (6)
Z
J = [(x + y − 20)dx − (x − 2y)dy] (7)
Z
H = 2ydx (8)

over each of the following paths from x = 20, y = 20 to x = 40, y = 60:

• y = 2x − 20
• y = 0.025x2 + 0.5x

2
 • y = 60 − 0.10(x − 40)2
Identify whether they are point or path functions.
13. The magnetic moment M of a paramagnetic material placed in a uniform magnetic field H can be repre-
sented with sufficient accuracy by the equation (Curie’s Law)

H
M = CC , (9)
T
where CC is the Curie constant. Check whether the magnetization can be a ‘property’ of the paramagnetic
system.
14. The Dieterici equation of state is
P (v − b) exp(a/vRT ) = RT. (10)
Find the expansivity β of a substance which obeys the above equation of state.
At high temperatires and large specific volumes all gases approximate idea gases. Verify that for large
values of T and v, the Dieterici equation and the expression of β both go over to the corresponding
equations for an ideal gas.
15. (a) Consider U ≡ U (T, P ) for Ideal Gas to show
 
∂U κT
= P V κT − (Cp − Cv ) .
∂P T β

κT is isothermal compressibility.
(b) Consider U ≡ U (P, V ) for Ideal Gas to show
 
∂U Cv κT
= .
∂P V β

(c) Derive the relation between the efficiency of a heat engine η and the coefficient of performance of a
refrigerator χ.
16. (a) For a gas obeys the van der Waals equation of state
 a
P + 2 (v − b) = RT,
v
the molar internal energy is given by
a
u = cT − ,
v
where a, b, c, and R are constants. Find the expressions of molar specific heats cv and cp .
(b) Refer to the following Figure-2.

Figure 2: Figure 2

3
 When a system is taken from state a to state b, along the path a-c-b, 80 J of heat flows into the
system, and the system does 30 J of work. (a) Find the heat flow into the system along path a-d-b,
if the work done is 10 J? (b) The system is returned from state b to state a along the curved path.
The work done on the system is 20 J. Find out the amount of heat liberated/absorbed by the system.
(c) If ua = 0 and ud = 40 J , find the heat absorbed in the processes a-d and d-b.
17. (a) Show that the coefficient of volume expansion of a van der Waals gas is

Rv 2 (v − b)
β= .
RT v 3 − 2a(v − b)2

Derive the β for ideal gas with proper justification.

(b) Systems 1 and 2 have the following equations of state:

1 3 N1
= R ,
T1 2 U1
1 5 N2
= R ,
T2 2 U2
where R is gas constant. The mole number of the gases are N1 = 2 and N2 = 3 respectively. When
the two systems are put in contact through a diathermal wall, the total energy of the composite
system is 2.5 × 103 J. The composite system is kept isolated. What is the internal energy of each
system at equilibrium?

(c) The equation of state of an ideal elastic substance is

L20
 
L
F = CT − 2 ,
L0 L

where C is a constant and L = L0 for F = 0. Show that the isothermal Young’s modulus is

F L2
Y = + 3CT 02 .
A AL

18. A volume V at temperature T contains nA moles of ideal gas A and nB moles of ideal gas B. The gases
do not react chemically.
(a) Show that the total pressure P of the system is given by

P = pA + pB ,

where pA and pB are the pressures that each gas would exert if it were in the volume alone. The
quantity pA is called the partial pressure of gas A. Identify the law mentioned in the above equation?
(b) Show that pA = xA P where xA is the mole fraction of A in the system.
19. A hypothetical substance has an isothermal compressibility κT = av and an expansivity β = 2bT v where
a and b are constants. Find out the equation of state. It is given that at a pressure P = P0 , and the
temperature T = T0 , the specific volume is v = v0 .
20. Two Carnot heat engines are operating in series such that the heat sink of the first engine serves as
the heat source of the second one. If the source temperature of the first engine is 1600K and the sink
temperature of the second engine is 300K and the thermal efficiencies of both engines are the same, find
out the temperature of the intermediate reservoir.
21. A thermoelectric device cools a small refrigerator and discards heat to surroundings at 25◦ C. The maximum
electric power consumption for which the device is designed is 100W . The heat load on the refrigerator
(that is, the rate of heat leaking through the walls which must be removed by the thermoelectric device)
is 350W. What is the minimum temperature that can be maintained in the refrigerator? Assume the
refrigerator works in a reversible cycle.

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