Tutorial-2: Entropy and Second Law
CH2010
Chemical Engineering Thermodynamics
Due: In Class, Wed, August 13, 2025
Problem 1. Consider an ideal gas undergoing the following processes. For each scenario,
determine whether the entropy change is positive, negative or zero:
(i) Isothermal compression (ii) Adiabatic compression (iii) Isobaric heating (iv) Isochoric
(constant volume) heating
Solution:
Let us take all of these processes to be reversible and let ∆s refer to the entropy change
of the system:
(i) Isothermal compression:
du = dq + dw
For an ideal gas undergoing an isothermal process: du = 0
RT
Therefore, dq = −dw = P dv = v
dv
dqrev
R
∆s = T
; substituting what we found for dq from above,
R v2
∆s = R v1
dv
v
=⇒ ∆s = Rln vv12
Since this is isothermal compression, the final volume is lower than the initial volume
Therefore: v2 < v1 ; ln vv21 < 0
Therefore, ∆s < 0
(ii) Adiabatic compression:
For an adiabatic process, dq = 0, therefore ∆s = 0
(iii) Isobaric heating:
1
Let’s start from the first law again:
du = dq + dw
For an ideal gas, we can use the expression for the internal energy as:
du = cRdT ; where c is a constant. Similarly, dw = −P dv
Substituting both, we obtain: dq = cRdT + P dv
dqrev
Now using the definition for entropy, ds = T
R T2 dT
R v2P
∆s = cR T1 T
+ v1 T
dv
Using the ideal gas law, we can rewrite this as:
R T2 dT
R v2 dv
∆s = cR T1 T
+R v1 v
∆s = cRln TT21 + Rlnv2 v1
Here, we can use the fact that the pressure is constant (isobaric) to obtain:
RT1 RT2
v1 = P1
and v2 = P1
Substituting this, we obtain:
∆s = cRln TT12 + Rln TT12
We also know that this is isobaric heating, therefore T2 > T1 , therefore, ∆s > 0
(iv) Isochoric heating:
Let’s start from the first law again:
du = dq + dw
Here, since its an isochoric process; dv = 0. Therefore dw = −P dv = 0
=⇒ dq = du = cRdT and
R T2
∆s = cR T1
dT
T
= cRln TT21
Since this is isochoric heating, T2 > T1 , therefore, ∆s > 0
2
Problem 2. An ideal gas is stored in a piston-cylinder assembly with an initial volume of
0.50 m3 at a pressure of 150 kPa and temperature of 30◦ C. This setup is compressed to
400 kPa in an isothermal process. Taking the surrounding temperature to also be 30◦ C, and
the heat capacity of the ideal gas cp = 25R, calculate the following:
(i) The heat exchanged during the process
(ii) The entropy change of the system, surroundings, and universe. Comment on if this
process is feasible according to the second law of thermodynamics.
Solution:
(i) From the first law,
dU = dQ + dW = 0; since it’s an isothermal process involving an ideal gas.
N RT
Therefore, dQ = −dW = P dV = V
dV ; where T is a constant (isothermal)
Integrating this gives, Q = N RT ln VV21 = N RT ln PP21 ; using the ideal gas law.
This gives, Q = (150 ∗ 0.5) ∗ ln 150
400
= −73.56 kJ; since N RT = P1 V1
(ii) One can use the general expression for the entropy of an ideal gas now:
∆ssys = cp ln TT12 − Rln PP21
Here, the first term will be zero since its an isothermal process.
Therefore, ∆ssys = −Rln PP21 ; and ∆Ssys = N ∆ssys = −N Rln PP21 = − P1TV1 ln PP12
Substituting and solving this gives, ∆Ssys = −0.24 kJ/K
∆Ssurr = Qsurr
T
= − (−73.56)
303
= 0.24 kJ/K
Therefore, ∆Suniv = 0.
This is a reversible process that is possible according to the second law.
Problem 3. Tempered steel is prepared by heating it to a high temperature followed by
quenching. Let us take a 40 kg steel casting with a heat capacity of cp = 0.5 kJ/kg K at
a temperature of 450◦ C. This is quenched in a 150 kg bath of oil with a heat capacity of
cp = 2.5 kJ/kg K at 25◦ C. Compute the change in entropy of the steel casting, and the bath
of oil. From your understanding of entropy, including the molecular definition learned in
class, explain what is happening in this process.
3
Solution:
We can perform an energy balance to first estimate the final temperature:
(mcp ∆T )steel + (mcp ∆T )oil = 0
40 ∗ 0.5 ∗ (T − 723) + 150 ∗ 2.5 ∗ (T − 298) = 0
Solving this gives the final temperature T = 319.52 K.
Now, the entropy change of the steel casting can be estimated as:
RT cp dT
∆Ssteel = m Ti T
= mcp ln TTi = 40 ∗ 0.5 ∗ ln 319.52
723
= −16.33 kJ/K
Similarly, the entropy change of the bath of oil can be estimated as:
RT cp dT
∆Soil = m Ti T
= mcp ln TTi = 150 ∗ 2.5 ∗ ln 319.52
298
= 26.15 kJ/K
As the steel quenches and cools down, the kinetic energy of the atoms also reduce, re-
sulting in more ordered states or fewer possible configurations, which results in a lowering
of its entropy. The opposite happens to the bath of oil.
Problem 4. Two input streams of air are mixed to produce a single output stream in a
steady-state flow process. The first input stream has 1 mol/s of air flowing at 600 K and
1 atm, while the second stream has 2 mol/s of air flowing at 450 K and 1 atm. The output
product stream is at 400 K and 1 atm. Determine the rate of heat exchanged in this process
and the rate of entropy generation, assuming that the input and output streams are ideal
gases with a constant heat capacity cp = 72 R, and the surroundings are at 300 K.
Solution:
We can assume that there is no shaft work in this case.
Using the first-law for open systems we can now write:
n˙1 h1 + n˙2 h2 − ṅh + Q̇ = 0
Therefore, Q̇ = ṅh − n˙1 h1 − n˙2 h2
where, ṅ = n˙1 + n˙2
Substituting this in the above equation, we get:
Q̇ = n˙1 (h − h1 ) + n˙2 (h − h2 ) = n˙1 cp (T − T1 ) + n˙2 cp (T − T2 )
4
Since both the inlet and outlet streams are ideal gases with cp = 72 R, we can substitute
all the values in the above expression and obtain:
Q̇ = −8729.7 J/s
Similarly, using the second law for open systems we can calculate the entropy generated:
Q̇ ds
n˙1 s1 + n˙2 s2 − ṅs + Tsurr
+ dt
=0
ds Q̇
Therefore, dt
= ṅs − n˙1 s1 − n˙2 s2 − Tsurr
Again, using ṅ = n˙1 + n˙2 , we can rewrite the above equation:
ds Q̇
dt
= n˙1 (s − s1 ) + n˙2 (s − s2 ) − Tsurr
Using the heat capacity and the definition for entropy,
ds Q̇
dt
= n˙1 cp ln TT1 + n˙2 cp ln TT2 − Tsurr
In the above expression all the values are provided and we have estimated Q̇ previously,
which can be used to obtain:
ds
dt
= 10.446 J/K s
