Question 1

The balloon portion of a dirigible contains 5000 moles of helium. Initially, the
helium is at T1 = 288 K and P1 = 96.26 kPa, and is 500 m off the ground
(where the atmospheric pressure is also 96.26 kPa). The dirigible flies south
at a constant height and a slow velocity, and gradually warms to T2 = 298 K
(though the pressure remains constant). How much heat was added to the
balloon during the process? Helium can be treated as an ideal gas with Cp =
5/2R.

Initial Dirigible Final Dirigible

500 m
5000 moles He; P = 5000 moles He; P =
96.26 kPa; T1 = 288 K 96.26 kPa; T2 = 298 K
 Question 1
Analysis: It is a slow process with constant pressure. We can treat it as a
reversible isobaric process. Thus dW = -PdV. Then we use first law for
closed system to find Q.

Solution:
𝑑𝑊 = −𝑃𝑑𝑉

Integrate (P is a constant),
𝑇2 𝑇1
𝑊 = −𝑃∆𝑉 = −𝑃 𝑉2𝑡 − 𝑉1𝑡 = −𝑛𝑅𝑃 − = −𝑛𝑅(𝑇2 − 𝑇1 )
𝑃2 𝑃1
𝑊 = −5000 × 8.314 × 298 − 288 = −415.7 𝑘𝐽
 Question 1
𝑇2
5
∆𝐻 = න 𝐶𝑃 𝑑𝑇 = 𝐶𝑃 ∆𝑇 = 𝑅 × 10 = 0.20785 𝑘𝐽/𝑚𝑜𝑙
𝑇1 2

∆𝑈 = ∆𝐻 − ∆ 𝑃𝑉 = ∆𝐻 − 𝑅∆𝑇 = 0.20785 − 0.08314 = 0.12471𝑘𝐽/𝑚𝑜𝑙

∆𝑈 𝑡 = 𝑛∆𝑈 = 5000 × 0.12471 = 623.55 𝑘𝐽

Apply 1st law for closed system:

𝑄 = ∆𝑈 𝑡 − 𝑊 = 623.55 + 415.7 = 1039.25 𝑘𝐽

Alternatively, since this is a reversible, isobaric process, Q = ∆H = Cp ∆T

Also can!
 Question 2
1 mol of an ideal gas undergoes state changes from 1 to 3 via two pathways: a)
goes from state 1 to state 2 through an isobaric step first, and then reaches
state 3 via an isochoric process; b) goes directly from state 1 to state 3. In this
system, P1 = 0.1 MPa, T1 = 300 K, V2 = 3V1, P3 = 2P2. Treat all steps to be
reversible; Cv = 3/2R.
Find Q1-2, Q2-3, and Q1-3. Prove: Q1-2 + Q2-3 ≠ Q1-3;
Question 2
Analysis: Find out Q1-2, Q2-3, and Q1-3 respectively. No direct way to find
Q, find ∆U and W instead. Note that for reversible process, dW = -PdV
Solution:
Step 1-2 is isobaric
𝑑𝑊 = −𝑃𝑑𝑉

𝑊1−2 = −𝑃1 ∆𝑉 = −𝑃1 𝑉2 − 𝑉1 = −2𝑃1 𝑉1 = −2𝑅𝑇1

𝑊1−2 = −2 × 8.314 × 300 = −4988.4 𝐽/𝑚𝑜𝑙

𝑉2
∆𝑈1−2 = 𝐶𝑉 ∆𝑇 = 𝐶𝑉 𝑇2 − 𝑇1 = 𝐶𝑉 𝑇1 −1
𝑉1
3𝑅
∆𝑈1−2 = × 300 × 2 = 7482.6 𝐽/𝑚𝑜𝑙
2

𝑄1−2 = ∆𝑈1−2 − 𝑊1−2 = 12471 𝐽/𝑚𝑜𝑙

 Question 2
Step 2-3 is isochoric
𝑑𝑊 = 0
𝑃3 𝑉2 𝑃3
∆𝑈2−3 = 𝐶𝑉 ∆𝑇 = 𝐶𝑉 𝑇3 − 𝑇2 = 𝐶𝑉 𝑇2 − 1 = 𝐶𝑉 𝑇1 −1
𝑃2 𝑉1 𝑃2
3𝑅
∆𝑈2−3 = × 300 × 3 = 11223.9 𝐽/𝑚𝑜𝑙
2
𝑄2−3 = ∆𝑈2−3 = 11223.9 𝐽/𝑚𝑜𝑙

Step 1-3 is not a typical process that we discussed in the lecture, but P
and V has a liner relationship along the process
Numerically, we have P = VP1/2V1 + 0.5P1 for step 1-3

𝑉 𝑃1
𝑑𝑊 = −𝑃𝑑𝑉 𝑑𝑊1−3 =− + 0.5𝑃1 𝑑𝑉
2 𝑉1
 Question 2
𝑉3
𝑉 𝑃1 𝑉12 − 𝑉32 𝑃1
𝑊1−3 =න − + 0.5𝑃1 𝑑𝑉 = − 0.5𝑃1 𝑉3 − 𝑉1 = −3𝑃1 𝑉1
𝑉1 2 𝑉1 4 𝑉1

𝑊1−3 = −3𝑅𝑇1 = −3 × 8.314 × 300 = −7482.6 𝐽/𝑚𝑜𝑙

𝑃3 𝑉3 3𝑅
∆𝑈1−3 = 𝐶𝑉 𝑇3 − 𝑇1 = 𝐶𝑉 𝑇1 −1 = × 300 × 5 = 18706.5
𝑃1 𝑉1 2

𝑄1−3 = ∆𝑈1−3 − 𝑊1−3 = 26189.1 𝐽/𝑚𝑜𝑙

𝑄1−2 + 𝑄2−3 = 23694.9 𝐽/𝑚𝑜𝑙 ≠ 𝑄1−3

We can also check ∆U

𝐽
∆𝑈1−2 + ∆𝑈2−3 = 18706.5 = ∆𝑈1−3
𝑚𝑜𝑙
Tips for Solving Problems for Open Systems
• Draw a diagram schematically;
• Define the system clearly;
• Write down the MB & EB equations;
• In many cases, simplify your MB and EB
equations;
• Evaluate your MB and EB equations

Align your way of thinking towards this procedure!!!

Question 3
Nitrogen flows at steady state through a horizontal, insulated pipe with
inside diameter of 38.1 mm. A pressure drop results from flow through a
partially opened valve. Just upstream from the valve the pressure is 690
kPa, the temperature is 322.15 K, and the average velocity is 6.09 m/s. If
the pressure just downstream from the valve is 138 kPa, what is the
temperature? Assume for nitrogen that PV/T is constant, CV = (5/2)R, and CP
= (7/2)R.

flow
690 kPa 138 kPa
38.1 mm
322.15 K X 38.1 mm
 Question 3
Analysis: open, system, steady state. Ep can be ignored. On the other
hand, velocity must be changed after passing through the valve.
Without calculation, we may not ignore Ek.

Solution: Apply steady state energy balance equation for open system,
simplify it, we get:
1 2 1
0 = 𝑄ሶ + 𝑊ሶ + 𝑚[(𝐻
ሶ 𝑖𝑛 + 𝑢 𝑖𝑛 + 𝑔𝑧𝑖𝑛) − (𝐻𝑜𝑢𝑡 + 𝑢 𝑜𝑢𝑡
2 + 𝑔𝑧
𝑜𝑢𝑡 )]
2 2
1 2
∆𝐻 = (𝑢𝑖𝑛2 − 𝑢𝑜𝑢𝑡 ) (Equation 1)
2
Apply mass balance equation for steady state
𝑚ሶ 𝑖𝑛 = 𝜌𝑖𝑛 𝑢𝑖𝑛 𝐴𝑖𝑛 = 𝑚ሶ 𝑜𝑢𝑡 = 𝜌𝑜𝑢𝑡 𝑢𝑜𝑢𝑡 𝐴𝑜𝑢𝑡
𝜌𝑖𝑛 𝑢𝑖𝑛 𝑉𝑜𝑢𝑡 𝑢𝑖𝑛 𝑇𝑜𝑢𝑡 𝑃𝑖𝑛 𝑢𝑖𝑛
𝜌𝑖𝑛 𝑢𝑖𝑛 = 𝜌𝑜𝑢𝑡 𝑢𝑜𝑢𝑡 𝑢𝑜𝑢𝑡 = = = (Equation 2)
𝜌𝑜𝑢𝑡 𝑉𝑖𝑛 𝑃𝑜𝑢𝑡 𝑇𝑖𝑛
 Question 3
Combining eqs 1-2, and consider ∆H = Cp∆T It is very easy to make a mistake
here. In energy balance equation, the
1 2 𝑇𝑜𝑢𝑡 𝑃𝑖𝑛 2] unit for H is kJ/kg. However, using
𝐶𝑃 (𝑇𝑜𝑢𝑡 − 𝑇𝑖𝑛 )/𝑀𝑊 = 𝑢𝑖𝑛 [1 −
2 𝑃𝑜𝑢𝑡 𝑇𝑖𝑛 ∆H=CP∆T the unit for H is kJ/mol

From the question statement, Cp = (7/2)R, Tin = 322.15, uin = 6.09 m/s, Pin
= 690 kPa, Pout = 138 kPa, MW = 0.028 kg/mol, Tout is the only unknown
value in the equation.

Solve the equation, we get:

Tout = 321.7 K

Note: such a device is called a throttling device (or expansion valve). The
major function is to reduce the pressure of a working fluid. From this
example, we realize the kinetic energy induced enthalpy change is not
significant (as reflected by the small change of temperature). In reality,
we can often ignore Ek for a throttling device .
Question 1
Derive an equation for the work of mechanically reversible, isothermal
compression of 1 mol of a gas from an initial pressure P1 to a final
pressure P2 when the equation of state is the virial expansion truncated
to Z = 1+B’P.

How does the result compare with the corresponding equation for an
ideal gas?
Question 1
Analysis: reversible process, dW = -PdV. Either, we have to replace P as a
function of V, or, we have to replace dV with dP. In this particular case, it
is better to replace dV with dP, since the integration limit for P is known
(P1 to P2), but the limit for V has to be determined with extra steps.
Proof:
𝑃𝑉
𝑍 =1+ 𝐵′ 𝑃 Since 𝑍 ≡
𝑅𝑇
𝑃𝑉 𝑅𝑇
= 1 + 𝐵′ 𝑃 𝑉= + 𝐵′ 𝑅𝑇
𝑅𝑇 𝑃
Isothermal process, T is constant; B’ is a function of T, so it is also a constant.
𝑅𝑇
Differentiate: 𝑑𝑉 = − 2 𝑑𝑃
𝑃
𝑃2
𝑅𝑇 1 𝑃2
𝑑𝑊 = −𝑃𝑑𝑉 = 𝑑𝑃 𝑊 = 𝑅𝑇 න 𝑑𝑃 = 𝑅𝑇𝑙𝑛
𝑃 𝑃1 𝑃 𝑃1
Interestingly, this expression is the same as the one derived for ideal gas in
lecture notes.
Question 2
49.9 kg of liquefied natural gas (LNG) is stored in a rigid, sealed vessel
with Vt = 0.142 m3. Due to a failure in the cooling/insulation system, the
temperature increases to 199.82 K. What is the resulting pressure of the
LNG? If the vessel is rated as safe for pressures of up to 500
atmospheres (50.66 MPa), will the vessel rupture? In this problem, treat
LNG as 100% methane.

Determine using
1) the ideal gas law.
2) the van der Waals EOS.
3) use NIST website to identify the pressure of methane in the final
state. Compare the data with 1) and 2). Which way is more accurate?

http://webbook.nist.gov/chemistry/fluid/
Question 2
Analysis: First of all, we need to know after temperature raises, whether
methane stays in the form of liquid/gas mixture or in a single phase. If it
is a mixture, we need to find the relative ratio; if it is in a single phase, we
can calculate its molar volume, V, based on total volume and molar
amount. Then use T and V to find P via EOS.
Solution:
From table B.1:
M = 16.043 g/mol; Tc = 190.6 K, Pc = 45.99 bar, ω = 0.012

The final temperature is higher than the Tc, methane can not stay in
liquid form. Final state is a single phase.
n = m/M = 49.9 x 103/16.043 = 3110.4 mol

V = Vt/n = 0.142/3110.4 = 4.565 x 10-5 m3/mol

ρ = 1/V = 2.19 x 104 mol/m3

 Question 2
Treat LNG as ideal gas:
𝑅𝑇 8.314 × 199.82
𝑃= = −5 = 36.39 𝑀𝑃𝑎 < 50.66 𝑀𝑃𝑎
𝑉 4.565 × 10

The vessel will not rupture

Treat LNG as van der Waals gas:

27𝑅 2 𝑇𝑐 2 27(8.314)2 (190.6)2 6𝑃𝑎𝑚𝑜𝑙 −2
𝑎= = = 0.2303 𝑚
64𝑃𝑐 64 × 45.99 × 105

𝑅𝑇𝑐 8.314 × 190.6 −5 𝑚3𝑚𝑜𝑙 −1

𝑏= = = 4.307 × 10
8𝑃𝑐 8 × 45.99 × 105
Question 2
𝑅𝑇 𝑎 8.314 × 199.82 0.2303
𝑃= − 2= −5 −5
−
𝑉−𝑏 𝑉 4.565 × 10 − 4.307 × 10 (4.565 × 10−5 )2

𝑃 = 643.9 − 110.5 𝑀𝑃𝑎 = 533.4 𝑀𝑃𝑎 ≫ 50.66 𝑀𝑃𝑎

The vessel will rupture

Which one should we trust?

Go to authoritative source for answers!

http://webbook.nist.gov/chemistry/fluid/
On NIST website,
choose the correct
parameters,
Click “Press to
Continue”
Input these values,
Select “Press for Data”
Question 2

Search through this Density-Pressure curve;

Find the point which is closest to 2.19 x 104 mol/m3

The pressure is 38 MPa. Ideal gas law

is much more accurate!
Question 3
35000 kg of propane, estimate the volume of tank required.
(a) as a gas at 10 ºC and 1 atm.
(b) as a liquid in equilibrium with its vapour at 10 ºC and 6.294 atm. For
this mode of storage, 90% of the tank volume is occupied by liquid.
use the generalized virial equation for both a) and b)
 Correlations for Second Virial Coefficient
𝐵𝑃 𝐵𝑃𝑐𝑃𝑟 𝑃𝑟 𝐵𝑃𝑐
𝑍 =1+ =1+ = 1 + 𝐵෠ (𝐵෠ = )
𝑅𝑇 𝑅𝑇𝑐𝑇𝑟 𝑇𝑟 𝑅𝑇𝑐

Pitzer and coworkers proposed: 𝐵෠ = 𝐵0 + 𝜔𝐵1

0
0.422 1
0.172
𝐵 = 0.083 − 1.6 𝐵 = 0.139 −
𝑇𝑟 𝑇𝑟 4.2

What are the two advantages of this correlation

compared with correlation with Z ?

Self-study: Correlations for Third Virial Coefficient (Page 103, not required)

12
Appendix in your textbook
Question 3
Solution for (a):
From Table B.1 Mw = 44.097 g/mol, Tc = 369.8 K, Pc =42.48 bar, ω = 0.152.
Total mass m = 35000 kg, thus the total mole is
𝑚 35000 5 𝑚𝑜𝑙
𝑛= = = 7.937 × 10
𝑀𝑊 44.097 × 10−3

𝑇 283.15 𝑃 1.01 × 105

𝑇𝑟 = = = 0.766 𝑃𝑟 = = = 0.0238
𝑇𝑐 369.8 𝑃𝑐 42.48 × 105

0.422 0.422
𝐵0 = 0.083 − = 0.083 − = −0.563
𝑇𝑟 1.6 0.7661.6

0.172 0.172
𝐵1 = 0.139 − = 0.139 − = −0.388
𝑇𝑟 4.2 0.766 4.2

𝐵෠ = 𝐵0 + 𝜔𝐵1 = −0.563 + 0.152 × −0.388 = −0.622

Question 3
𝑃𝑟 0.0238
𝑍 = 1 + 𝐵෠ = 1 − 0.622 = 0.981
𝑇𝑟 0.766

𝑍𝑅𝑇 0.981 × 8.314 × 283.15 3 −1

𝑃𝑉 = 𝑍𝑅𝑇 𝑉= = = 0.02286 𝑚 𝑚𝑜𝑙
𝑃 1.01 × 105

𝑉𝑡𝑜𝑡𝑎𝑙 = 𝑛𝑉 = 7.937 × 105 × 0.02286 = 1.8 × 104 𝑚3

Analysis for (b):

We need to find out the liquid and gas molar volume of propane under
the new conditions, both can be done by generalized correlations.

(1−𝑇𝑟 )2/7
𝑉 𝑠𝑎𝑡 = 𝑉𝑐 𝑍𝑐 Two more constants are needed.

What should we do afterwards ?

 Question 3
Solution for (b): For the vapor phase
𝑃 6.294 × 1.01 × 105
𝑇𝑟 = 0.766 𝑃𝑟 = = 5
= 0.150
𝑃𝑐 42.48 × 10
𝐵0 = −0.563 𝐵1 = −0.388 𝐵෠ = 𝐵0 + 𝜔𝐵1 = −0.622
𝑃𝑟 0.150
𝑍 = 1 + 𝐵෠ = 1 − 0.622 = 0.878
𝑇𝑟 0.766
𝑍𝑅𝑇 0.878 × 8.314 × 283.15 3 𝑚𝑜𝑙 −1
𝑉𝑣𝑎𝑝𝑜𝑟 = = = 0.003251 𝑚
𝑃 6.294 × 1.01 × 105

For the liquid phase use Rackett equation

𝑠𝑎𝑡 (1−𝑇𝑟 )2/7 −6 (1−0.766)0.2857
𝑉𝑙𝑖𝑞𝑢𝑖𝑑 = 𝑉𝑐 𝑍𝑐 = 200.0 × 10 × 0.276 = 85.47 × 10−6 𝑚3 𝑚𝑜𝑙−1
90% × 𝑉𝑡𝑜𝑡𝑎𝑙 10% × 𝑉𝑡𝑜𝑡𝑎𝑙
𝑛 = 𝑛𝑙𝑖𝑞𝑢𝑖𝑑 + 𝑛𝑔𝑎𝑠 = 𝑠𝑎𝑡 + = 𝑉𝑡𝑜𝑡𝑎𝑙 (10530 + 31)
𝑉𝑙𝑖𝑞𝑢𝑖𝑑 𝑉𝑣𝑎𝑝𝑜𝑟
7.937 × 105
𝑉𝑡𝑜𝑡𝑎𝑙 = ≈ 75 𝑚3
10561
Question 4
A closed cylinder has two chambers, separated by a piston. The left chamber
contains N2 and the right chamber contains O2. Both the cylinder and the piston
are made of insulating materials. The piston can move freely without frictions. At
the initial stage (1), we have TA1 = TB1 = 300 K, PA1 = PB1 = 0.1 MPa, and VA1 = VB1 =
0.5 m3. Electrical heating has been slowly delivered to the left chamber. The final
state (2) of N2 in the left chamber has PA2 = 0.22 MPa. Treat N2 and O2 as ideal
gases with constant CP (7/2 R)

Determine:
1) TB2 and VB2
2) TA2 and VA2
3) The work done by chamber A to B (WA→B), and electrical heat Q (Take N2 as
the system)
4) ∆SN2 and ∆SO2 (solve this problem after the next chapter)
5) Is N2 undergoing a polytropic process or not?

Hint: the amount of gas is not 1 mol

 Question 4
Solution
1) In this problem, it can be regarded as a reversible process
we always have PA = PB
Final state: PA2 = PB2 = 0.22 MPa
For ideal gas, CV = CP – R = 5/2 R
γ = CP/CV = 1.4
O2 undergoes adiabatic, reversible process
γ γ γ
𝑃𝐵1 𝑉𝐵1 = 𝑃𝐵2 𝑉𝐵2 𝑉𝐵2 = 0.4545 × 0.3789 = 0.1722

𝑉𝐵2 = 0.2847 𝑚3

Apply ideal gas law to O2

𝑃𝐵2 𝑉𝐵2 𝑃𝐵1 𝑉𝐵1 𝑃𝐵2 𝑉𝐵2 0.22 × 0.2847

= 𝑇𝐵2 = 𝑇𝐵1 = 300 = 375.8 𝐾
𝑇𝐵2 𝑇𝐵1 𝑃𝐵1 𝑉𝐵1 0.1 × 0.5
Question 4
2) 𝑉𝐴2 = 𝑉𝑡𝑜𝑡𝑎𝑙 − 𝑉𝐵2 = 1 − 0.2847 = 0.7153 𝑚3

Apply ideal gas law to N2

𝑃𝐴2 𝑉𝐴2 0.22 × 0.7153

𝑇𝐴2 = 𝑇𝐴1 = 300 = 944.2 𝐾 944 K is fine
𝑃𝐴1 𝑉𝐴1 0.1 × 0.5
3) O2 undergoes adiabatic process, Q = 0.
Apply energy balance equation for O2
𝑊 = ∆𝑈 = 𝐶𝑉 ∆𝑇 = 2.5 × 8.314 × 375.8 − 300 = 1575.5 𝐽/𝑚𝑜𝑙
𝑃𝐵1 𝑉𝐵1 0.1 × 106 × 0.5
𝑛= = = 20.05 𝑚𝑜𝑙
𝑅𝑇𝐵1 8.314 × 300
Take N2 as system, the work is negative

𝑊𝐴→𝐵 = −𝑛𝑊 = −31583 𝐽 ≈ −31.58 𝑘𝐽

Question 4
3) (continued)
Apply energy balance equation for N2
𝑄 = ∆𝑈 𝑡𝑜𝑡𝑎𝑙 − 𝑊𝐴→𝐵 = 𝑛𝐶𝑉 ∆𝑇 − 𝑊𝐴→𝐵
= 20.05 × 2.5 × 8.314 × 944.2 − 300 + 31583
𝑄 = 300046 𝐽 ≈ 300 𝑘𝐽
𝑉𝐴2 𝑉𝐵2
𝑊𝐴→𝐵 = −𝑛 න 𝑃𝐴 𝑑𝑉𝐴 = 𝑛 න 𝑃𝐵 𝑑𝑉𝐵 Use this equation to find W is also correct
𝑉𝐴1 𝑉𝐵1

𝑇𝐴2 𝑉𝐴2
4) ∆𝑆𝑁2 = 𝑛𝐶𝑉 𝑙𝑛 + 𝑛𝑅𝑙𝑛
𝑇𝐴1 𝑉𝐴1
5 944.2 0.7153
= 20.05 × ( × 8.314 × 𝑙𝑛 + 8.314𝑙𝑛 )
2 300 0.5
= 20.05 × (23.83 + 2.977) = 537.5 𝐽/𝐾

If ∆S is provided in the unit of J/K/mol, without

∆𝑆𝑂2 = 0 considering moles, it is also correct.
Question 4
5) If N2 follows a polytropic process

𝑃𝐴 𝑉𝐴 𝛿 = 𝑐𝑜𝑛𝑠𝑡𝑎𝑛𝑡 = 𝑀

Consider PA = PB, VA = 1 - VB
𝑃𝐵 (1 − 𝑉𝐵 )𝛿 = 𝑀

𝑃𝐵 𝑉𝐵 γ = 𝑐𝑜𝑛𝑠𝑡𝑎𝑛𝑡 = 𝑁

(1 − 𝑉𝐵 )𝛿 𝑀
γ = = 𝑐𝑜𝑛𝑠𝑡𝑎𝑛𝑡 VB is a constant!
𝑉𝐵 𝑁

But VB is changing!

Therefore N2 does not follow a polytropic process

 Question 1
Question 1 1

An ideal gas, CP = (7/2)R and CV = (5/2)R, undergoes a cycle consisting of the

following mechanically reversible steps:
• An adiabatic compression from 1 (P1, V1, T1) to 2(P2, V2, T2)
• An isobaric expansion from 2 (P2, V2, T2) to 3 (P3, V3, T3)
• An adiabatic expansion from 3 (P3, V3, T3) to 4 (P4, V4, T4)
• A constant-volume process from 4 (P4, V4, T4) to 1 (P1, V1, T1)

Sketch this cycle on a PV diagram and determine its thermal efficiency if T1 =

473.15 K, T2 = 1273.15 K, and T3 = 1973.15 K.
 Q1 Solution
Question 1 2

Analysis: need to calculate W and Q for each

2 3 step. Find W and Qh for the entire cycle. A
better way is, analyse the entire cycle, simply
the expression for ƞ.
4
Solution:
1 First, sketch this cycle on a PV diagram
Two adiabatic steps; one isochoric; one isobaric
𝑊 = 𝑊2→3 + 𝑊3→4 − 𝑊1→2 𝑄𝐶 = 𝑄4→1 𝑄ℎ = 𝑄2→3

From energy balance, we have 𝑊 = 𝑄ℎ − 𝑄𝐶 In this case, finding Q is

simpler than finding W

𝑊 𝑄ℎ − 𝑄𝐶 𝑄4→1 𝐶𝑉 (𝑇4 − 𝑇1 )
𝜂= = =1− =1−
𝑄ℎ 𝑄ℎ 𝑄2→3 𝐶𝑃 (𝑇3 − 𝑇2 )
 Q1 Solution
Question 1 3

All numbers are known except T4 Need to use linkages between

1, 2, 3 and 4 to find T4
For steps 1-2 and 3-4,
𝛾−1 𝛾−1 𝛾−1 𝛾−1
𝑇1 𝑉1 = 𝑇2 𝑉2 𝑇3 𝑉3 = 𝑇4 𝑉4
For steps 4-1, 𝑉1 = 𝑉4
𝑉2 𝑉3
For steps 2-3, 𝑃2 = 𝑃3 =
𝑇2 𝑇3
𝑇2 −𝛾 1273.15 −1.4
Solve these equations: 𝑇4 = 𝑇1 ( ) = 473.15 × ( ) = 873.76 𝐾
𝑇3 1973.15
𝐶𝑉 𝑇4 − 𝑇1 873.76 − 473.15
𝜂 =1− = 1 − 0.7143 × = 59.1%
𝐶𝑃 𝑇3 − 𝑇2 1973.15 − 1273.15

Note: this is a typical thermodynamic cycle for the Diesel Engine. Read
more in chapter 8.2 (page 302-310) if you have further interests in
internal combustion engines.
 Question 2
Question 2 4

1) 2 kg air kept in a cylinder undergoes a reversible, adiabatic compression

from initial state P1 = 0.1034 MPa, T1 = 299.7 K to final pressure P2 = 0.517
MPa. Determine the work involved in the process.

2) 2 kg air is converted from the same initial state to the same final state, by
passing through a compressor operated under a reversible, adiabatic
condition. Assume the compressor was operated under steady state when
air passed. Determine the work involved in the process.

3) What is the change of entropy to air in these two cases?

Air can be regarded as an ideal gas. Cv = 0.716 kJ·kg-1·K-1, Cp = 1.005 kJ·kg-

1·K-1.
 Q2 Solution
Question 2 5

Analysis: the first part is a reversible adiabatic process for closed system.
We should use the path equation for adiabatic process. For the second
part, we should apply steady state energy balance equation.
Solution:
Note, for 1) you can also use
𝐶 1.005 this equation to solve.
1) γ ≡ 𝑃 = = 1.4036
𝐶𝑉 0.716 𝑇2
𝑑𝑇 𝑃2
∆𝑆 = න 𝐶𝑃 − 𝑅𝑙𝑛
1 − γ 1 − 1.4036 𝑇1 𝑇 𝑃1
= = −0.2875
γ 1.4036
For reversible, adiabatic process in a closed system
(1−𝛾)/𝛾 (1−𝛾)/𝛾
𝑇1 𝑃1 = 𝑇2 𝑃2 𝑇2 = 476.04 𝐾

Apply 1st Law for closed system ∆𝑈 𝑡 = 𝑄 + 𝑊 = 𝑊

𝑊 = ∆𝑈 𝑡 = 𝐶𝑉 ∆𝑇 = 2 × 0.716 × 476.04 − 299.7 = 252.52 𝑘𝐽

 Q2 Solution
Question 2 6

2) For open systems under steady state

1 2 1
0 = 𝑄ሶ + 𝑊ሶ + 𝑚[(𝐻
ሶ 𝑖𝑛 + 𝑢𝑖𝑛 + 𝑔𝑧 𝑖𝑛) − (𝐻𝑜𝑢𝑡 + 𝑢𝑜𝑢𝑡2 + 𝑔𝑧𝑜𝑢𝑡 )]
2 2
𝑊ሶ = 𝑚∆𝐻
ሶ

𝑊 = 𝑚∆𝐻 = 𝑚𝐶𝑃 ∆𝑇 = 2 × 1.005 × 476.04 − 299.7 = 354.44 𝑘𝐽

3) In both cases, reversible, adiabatic. These are isentropic processes.

∆𝑆 = 0
 Question 3
Question 3 7

A gas at T = 450 oC and P = 0.5 MPa flows at steady state through an

adiabatic and reversible nozzle. The exiting pressure is 0.1 MPa. The
entering velocity is very low and can be ignored during calculation. Find the
velocity and temperature of the exiting stream if

1) The gas is steam.

2) The gas is an ideal gas with CV = 3 R and molecular weight = 75 kg/kmol.

Tin = 450oC Tout = ?

Pin = 0.5 MPa Pout = 0.1 MPa
vin ≈ 0 vout = ?
 Q3 Solution
Question 3 8

Analysis: this is a steady state, open system. Only one property (P) is
given for the final state. We have to analyse entropy and energy balance
equations, find out the hidden constrains for the process.
Solution:
The entropy balance equation

𝑑(𝑚𝑆)𝐶𝑉 Qሶ j
𝑆𝐺ሶ = −෍ − 𝑆𝑖𝑛 𝑚ሶ 𝑖𝑛 + 𝑆𝑜𝑢𝑡 𝑚ሶ 𝑜𝑢𝑡
𝑑𝑡 Tσ,j
j

ሶ 𝑑(𝑚𝑆)𝐶𝑉
Adiabatic, Q j = 0; Steady state, 𝑚ሶ 𝑖𝑛 = 𝑚ሶ 𝑜𝑢𝑡 ; =0
𝑑𝑡
Reversible, 𝑆𝐺ሶ = 0

The entropy balance equation is reduced to:

𝑆𝑖𝑛 = 𝑆𝑜𝑢𝑡 We identified the hidden constrains of the

process (i.e., S does not change)
 Q3 Solution
Question 3 9

The energy balance equation for steady state, open system:

1 2 1
0 = 𝑄ሶ + 𝑊ሶ + 𝑚[(𝐻
ሶ 𝑖𝑛 + 𝑢𝑖𝑛 + 𝑔𝑧 𝑖𝑛) − (𝐻𝑜𝑢𝑡 + 𝑢𝑜𝑢𝑡2 + 𝑔𝑧𝑜𝑢𝑡 )]
2 2
The energy balance equation is reduced to:
1
𝑢𝑜𝑢𝑡2=𝐻𝑖𝑛 − 𝐻𝑜𝑢𝑡
2
1) From steam table, at Tin = 450oC, Pin = 0.5 MPa

Hin = 3377.2 kJ/kg, Sin = 7.9454 kJ/kgK

Sout = Sin = 7.9454 kJ/kgK

From steam table, at Pout = 0.1 MPa, Sout = 7.9454 kJ/kgK

Tout = 227.2 oC, Hout = 2929.2 kJ/kg
1
𝑢𝑜𝑢𝑡2=𝐻𝑖𝑛 − 𝐻𝑜𝑢𝑡 = 4.48 × 105 𝐽/𝑘𝑔 𝑢𝑜𝑢𝑡=947 m/s
2
 Q3 Solution
Question 3 10

2) For ideal gas

𝑇𝑜𝑢𝑡
𝑑𝑇 𝑃𝑜𝑢𝑡
∆𝑆 = න 𝐶𝑃 − 𝑅𝑙𝑛 =0
𝑇𝑖𝑛 𝑇 𝑃𝑖𝑛
𝑇𝑜𝑢𝑡
𝑑𝑇 𝑃𝑜𝑢𝑡
න 𝐶𝑃 = 𝑅𝑙𝑛
𝑇𝑖𝑛 𝑇 𝑃𝑖𝑛

𝑇𝑜𝑢𝑡 1
4𝑙𝑛 = 𝑙𝑛 𝑇𝑜𝑢𝑡 = 483.6 𝐾
723.15 5
1
𝑢𝑜𝑢𝑡2=𝐻𝑖𝑛 − 𝐻𝑜𝑢𝑡 = −𝐶𝑃 ∆𝑇/𝑀𝑤 = 4 × 8.314 × (723.15 − 483.6) ÷ 0.075
2
𝑢𝑜𝑢𝑡=460.9 m/s

Note: nozzle is a simple device that can significantly increase the velocity of
the working fluid (normally gas), at the expense of decreased enthalpy.
 Question 4
Question 4 11

Consider an adiabatic tank with volume 0.5 m3. It was full of liquid initially
at T = 300 K. At t = 0s, valves opened, allowing 0.33 kg/s of liquid at T = 400
K to enter the tank while 0.33 kg/s of liquid removed from the tank. How
much entropy is generated within the tank during the 300 s? Liquid within
the tank can be instantly well-mixed. (For liquid, 𝐶𝑉 = 𝐶𝑝 = 𝐶 = 3 kJ/kg
K, independent of T and P, treat density of the liquid to be a constant, 0.8
g/ml, use MATLAB to solve the final integration).

Flow rate = 0.33 kg /s

Tin = 400 K

X V = 0.5 m3
T0 = 300 K
V Flow rate = 0.33 kg /s
T=?K
Tout = T
ρ = 800 kg/m3
C = 3 kJ/kg K
X
 Q4 Solution
Question 4 12

Analysis: this is a non-steady state open system. We have to combine

entropy and energy balance equations to solve the problem.
Solution:
𝑑(𝑚𝑈)𝐶𝑉
The energy balance equation: = 𝑚ሶ 𝑖𝑛𝐻𝑖𝑛 − 𝑚ሶ 𝑜𝑢𝑡𝐻𝑜𝑢𝑡
𝑑𝑡
m in the tank is a constant; 𝑚ሶ 𝑖𝑛 = 𝑚ሶ 𝑜𝑢𝑡 ;
𝑑𝑈𝐶𝑉
𝑚 = 𝑚(𝐻
ሶ 𝑖𝑛 − 𝐻𝑜𝑢𝑡)
𝑑𝑡
𝑑𝑈𝐶𝑉 𝐶𝑉 𝑑𝑇
Consider: = 𝐻𝑖𝑛 − 𝐻𝑜𝑢𝑡 = CP(Tin −Tout) = C(Tin −T)
𝑑𝑡 𝑑𝑡
𝑑𝑇 𝑚 𝑑𝑇
𝑚 ሶ Tin − 𝑇)
= 𝑚( 𝑑𝑡 = −
𝑑𝑡 𝑚ሶ 𝑇 − Tin
Integrate from t = 0s to t = 300s
𝑚 𝑇 − 𝑇𝑖𝑛 400 𝑇 − 400
𝑡 = − 𝑙𝑛( ) 300 = − 𝑙𝑛( ) 𝑇 = 322𝐾
𝑚ሶ 𝑇0 − 𝑇𝑖𝑛 0.33 −100
 Q4 Solution
Question 4 13

The entropy balance equation

𝑑(𝑚𝑆)𝐶𝑉 Qሶ j
𝑆𝐺ሶ = −෍ − 𝑆𝑖𝑛 𝑚ሶ 𝑖𝑛 + 𝑆𝑜𝑢𝑡 𝑚ሶ 𝑜𝑢𝑡
𝑑𝑡 Tσ,j
j

m in the tank is a constant; 𝑚ሶ 𝑖𝑛 = 𝑚ሶ 𝑜𝑢𝑡 ; Qሶ j = 0; 𝑆𝑜𝑢𝑡 = 𝑆

𝑑𝑆𝐺 𝑑(𝑆)𝐶𝑉
The equation simplifies as: ሶ
= 𝑆𝐺 = 𝑚 + 𝑚(𝑆
ሶ − 𝑆𝑖𝑛 )
𝑑𝑡 𝑑𝑡

𝑑𝑆𝐺 = 𝑚𝑑 𝑆)𝐶𝑉 + 𝑚(𝑆

ሶ − 𝑆𝑖𝑛 𝑑𝑡

Integrating: 𝑆𝐺 = 𝑚∆(𝑆)𝐶𝑉 +𝑚ሶ න 𝑆 − 𝑆𝑖𝑛 𝑑𝑡

Now we need to find a relationship between S and T.

Then find
∆(𝑆)𝐶𝑉 and න 𝑆 − 𝑆𝑖𝑛 𝑑𝑡 respectively
 Q4 Solution
Question 4 14

Imagine a reversible process to cool down water in a closed system

𝑑𝑈 = 𝑑𝑄𝑟𝑒𝑣 + 𝑑𝑊 = 𝑑𝑄𝑟𝑒𝑣 − 𝑃𝑑𝑉

Note that the density is a constant, dV = 0 𝑑𝑈 = 𝑑𝑄𝑟𝑒𝑣

Note: it is easier to understand this after
𝑑𝑄𝑟𝑒𝑣 𝑑𝑈 𝐶𝑉 𝑑𝑇 learning the next chapter, where you
𝑑𝑆 = = =
𝑇 𝑇 𝑇 can directly use fundamental relations
dU = TdS – PdV, or dH = TdS + VdP
322 𝐾
𝐶𝑑𝑇 322
∆(𝑆)𝐶𝑉 = න 𝑑𝑆 = න = 3 × ln = 0.212 𝑘𝐽/𝑘𝑔𝐾
300 𝐾 𝑇 300

Now we move on to find න 𝑆 − 𝑆𝑖𝑛 𝑑𝑡

 Q4 Solution
Question 4 15

𝑇
𝐶𝑑𝑇 𝑇
𝑆 − 𝑆𝑖𝑛 𝑑𝑡 = ∆𝑆 𝑑𝑡 = 𝑑𝑡 න 𝑑𝑆 = 𝑑𝑡 න = 𝐶𝑙𝑛 𝑑𝑡
400 𝐾 𝑇 400
𝑚 𝑑𝑇
𝑑𝑡 = −
𝑚ሶ 𝑇 − Tin

𝐶𝑚 𝑇 𝑑𝑇 𝐶𝑚 𝑇 𝑑𝑇
𝑆 − 𝑆𝑖𝑛 𝑑𝑡 = − 𝑙𝑛 =− 𝑙𝑛
𝑚ሶ 400 𝑇 − 𝑇𝑖𝑛 𝑚ሶ 400 𝑇 − 400

322 𝐾
𝑇 𝑑𝑇
𝑚ሶ න 𝑆 − 𝑆𝑖𝑛 𝑑𝑡 = −𝐶𝑚 න 𝑙𝑛 = −74.4 𝑘𝐽/𝐾
300 𝐾 400 𝑇 − 400

Note: it is a difficult integration. We have to use Taylor expansion.

Alternatively, use MATLAB, or POLY-MATH to evaluate the integral
numerically. Not required in CN2121 quiz and exam though.

𝑆𝐺 = 𝑚∆(𝑆)𝐶𝑉 +𝑚ሶ න 𝑆 − 𝑆𝑖𝑛 𝑑𝑡 = 84.8 − 74.4 = 10.4 𝑘𝐽/𝐾

Question 1 1
Question 1 - Solution 2
 Question 2 Question 1 - Solution 3

a): for the residual part, from Table B.1:

ω = 0.224; Tc = 304.2 K; Pc = 73.83 bar
For state 1: Tr1 = 1.05; Pr1 = 0.217

For state 2: Tr2 = 0.995; Pr2 = 0.0137

From Table E: (𝐻1𝑅 )0 (𝐻1𝑅 )1

= −0.21 = −0.167
𝑅𝑇𝑐 𝑅𝑇𝑐
(𝐻2𝑅 )0 (𝐻2𝑅 )1
= −0.0138 = −0.0125
𝑅𝑇𝑐 𝑅𝑇𝑐

𝐻𝑅 (𝐻𝑅 )0 (𝐻𝑅 )1 𝐻1𝑅 𝐻2𝑅

= +𝜔 = −0.247 = −0.0166
𝑅𝑇𝑐 𝑅𝑇𝑐 𝑅𝑇𝑐 𝑅𝑇𝑐 𝑅𝑇𝑐
𝐻2𝑅 𝐻1𝑅
∆𝐻𝑅 = 𝑅𝑇𝐶 − = 0.583 𝑘𝐽/𝑚𝑜𝑙
𝑅𝑇𝑐 𝑅𝑇𝑐
 Question 2 Question 1 - Solution 4

a): for the residual part, from Table B.1:

∆𝐻 = ∆𝐻𝑅 + ∆𝐻𝑖𝑔 = 0.583 − 0.588 = −0.005𝑘𝐽/𝑚𝑜𝑙 ≈ 0

Similarly, from Table E:

(𝑆1𝑅 )0 (𝑆1𝑅 )1 (𝑆2𝑅 )0 (𝑆2𝑅 )1

= −0.136 = −0.153 = −0.0095 = −0.0117
𝑅𝑇𝑐 𝑅𝑇𝑐 𝑅𝑇𝑐 𝑅𝑇𝑐

𝑆 𝑅 (𝑆 𝑅 )0 (𝑆 𝑅 )1 𝑆1𝑅 𝑆2𝑅
= +𝜔 = −0.170 = −0.0121
𝑅 𝑅 𝑅 𝑅 𝑅
𝑅 𝑅
𝑆2 𝑆1
∆𝑆 𝑅 = 𝑅 − = 1.313 𝐽/𝑚𝑜𝑙𝐾
𝑅 𝑅

𝑅 𝑖𝑔
22.36𝐽
∆𝑆 = ∆𝑆 + ∆𝑆 = 1.313 + 21.047 = >0
𝑚𝑜𝑙𝐾

Since ∆S > 0, ∆H ≈ 0, it is likely that CO2 passes through a throttling device.

Question 2 5
Question 3 Question 2 - Solution 6
Solution
𝜕𝑃
(a) 𝑑𝑈 = 𝐶𝑉 𝑑𝑇 + [𝑇( )𝑉 − 𝑃]𝑑𝑉
𝜕𝑇
𝜕𝑃 𝑅 𝑅𝑇
Since: 𝑃 𝑉 − 𝑏 = 𝑅𝑇 𝑇( )𝑉 − 𝑃 = 𝑇 − =0
𝜕𝑇 𝑉−𝑏 𝑉−𝑏
So 𝑑𝑈 = 𝐶𝑉 𝑑𝑇

As 𝐶𝑉 is constant, U is ONLY a function of T.

𝑅𝑇 𝑅𝑇
(b) 𝑃= 𝑉= +𝑏
𝑉−𝑏 𝑃
𝜕𝑃 𝜕𝑉 𝑅 𝑅
𝐶𝑃 = 𝐶𝑉 + 𝑇( )𝑉 ( )𝑃 = 𝐶𝑉 + 𝑇 = 𝐶𝑉 + 𝑅
𝜕𝑇 𝜕𝑇 𝑉−𝑏𝑃
𝐶𝑃 𝑅 Refer example in lecture notes, on page 16
𝛾≡ =1+ = 𝑐𝑜𝑛𝑠𝑡.
𝐶𝑉 𝐶𝑉
13
Question 3 Question 2 - Solution 7
𝑅𝑇
(c) 𝑑𝑄 = 𝐶𝑉 𝑑𝑇 + 𝑃𝑑𝑉 𝑃=
(𝑉 − 𝑏)
𝑅𝑇
𝐶𝑉𝑑𝑇 = −𝑃𝑑𝑉 = − 𝑑𝑉
(𝑉 − 𝑏)
𝑇2
𝑑𝑇 𝑅 𝑑𝑉 𝑑𝑇 𝑅 𝑉2 𝑑(𝑉 − 𝑏)
=− න =− න
𝑇 𝐶𝑉 (𝑉 − 𝑏) 𝑇1 𝑇 𝐶𝑉 𝑉1 (𝑉 − 𝑏)

𝑇2 𝑅 𝑉2 − 𝑏 𝑇2 𝑉1 − 𝑏 𝑅/𝐶
𝑙𝑛 = − 𝑙𝑛 =( ) 𝑉
𝑇1 𝐶𝑉 𝑉1 − 𝑏 𝑇1 𝑉2 − 𝑏

𝑃(𝑉 − 𝑏) 𝑃2 (𝑉2 − 𝑏) 𝑉1 − 𝑏 𝑅/𝐶

Since: T = =( ) 𝑉
R 𝑃1 (𝑉1 − 𝑏) 𝑉2 − 𝑏

𝑃(𝑉 − 𝑏)1+𝑅/𝐶𝑉 = 𝑃(𝑉 − 𝑏)𝛾 = 𝑐𝑜𝑛𝑠𝑡.

14
Question 3 8
Question 4 Question 3 - Solution 9

Solution
a) The gas follows: 𝑃(𝑉 − 𝑏) = 𝑅𝑇
For isothermal step 1→2:
∆𝑈 = 0 (refer to Question 4 (a))
𝑉2 𝑉2
𝑅𝑇ℎ 𝑉2 − 𝑏
𝑄ℎ = 𝑊1→2 = න 𝑃𝑑𝑉 = න 𝑑𝑉 = 𝑅𝑇ℎ 𝑙𝑛
𝑉1 𝑉1 𝑉 − 𝑏 𝑉1 − 𝑏

Similarly, for isothermal step 3:

∆𝑈 = 0
𝑉2 − 𝑏
𝑄ℎ 𝑇ℎ 𝑙𝑛
𝑉3 − 𝑏 𝑉1 − 𝑏
𝑄𝑐 = |𝑊3→4 | = 𝑅𝑇𝑐 𝑙𝑛 =
𝑉4 − 𝑏 𝑄𝑐 𝑇𝑐 𝑉 −𝑏
𝑙𝑛 3
𝑉4 − 𝑏
Question 4 Question 3 - Solution 10

Based on question 3 (c), we have:

For a mechanically reversible, adiabatic process, 𝑃(𝑉 − 𝑏)𝛾 = 𝑐𝑜𝑛𝑠𝑡.

𝑇(𝑉 − 𝑏)𝛾−1 = 𝑐𝑜𝑛𝑠𝑡𝑎𝑛𝑡

For adiabatic steps 2→3 and 4→1:

𝑇2 (𝑉2 − 𝑏)𝛾−1 = 𝑇3 (𝑉3 − 𝑏)𝛾−1 𝑇4 (𝑉4 − 𝑏)𝛾−1 = 𝑇1 (𝑉1 − 𝑏)𝛾−1

Consider: 𝑇1 = 𝑇2 = 𝑇ℎ 𝑇3 = 𝑇4 = 𝑇𝑐

𝑇ℎ (𝑉2 − 𝑏)𝛾−1 = 𝑇𝑐 (𝑉3 − 𝑏)𝛾−1 𝑉3 − 𝑏 𝑉2 − 𝑏

=
𝑇𝑐 (𝑉4 − 𝑏)𝛾−1 = 𝑇ℎ (𝑉1 − 𝑏)𝛾−1 𝑉4 − 𝑏 𝑉1 − 𝑏
Question 4 Question 3 - Solution 11

𝑉2 − 𝑏
So 𝑄ℎ 𝑇ℎ 𝑙𝑛 𝑇ℎ
𝑉1 − 𝑏
= =
𝑄𝑐 𝑇𝑐 𝑉 −𝑏 𝑇𝑐
𝑙𝑛 3
𝑉4 − 𝑏

|W| 𝑄ℎ − 𝑄𝑐 𝑄𝑐 𝑇𝑐
𝜂≡ = =1− =1−
𝑄ℎ 𝑄ℎ 𝑄ℎ 𝑇ℎ

b) For any working fluid, consider the entire cycle:

| W| 𝑄ℎ − 𝑄𝑐 𝑄𝑐
𝜂≡ = =1−
𝑄ℎ 𝑄ℎ 𝑄ℎ
𝑑𝑄
Since all steps are reversible, Q = Qrev in all 4 steps 𝑑𝑆 =
𝑇
 Question 4 Question 3 - Solution 12

Since steps 1→2, and 3→4 are isothermal:

𝑇ℎ (𝑆2 − 𝑆1 ) = 𝑄ℎ 𝑇𝑐 (𝑆4 − 𝑆3 ) = 𝑄𝑐

Since steps 2→3, and 4→1 are adiabatic and reversible: ∆S = 0

𝑆4 = 𝑆1 𝑆2 = 𝑆3

Therefore: |𝑆2 − 𝑆1 | = |𝑆4 − 𝑆3 |

𝑄𝑐 𝑇𝑐 𝑆2 − 𝑆1 𝑇𝑐
𝜂 =1− =1− =1−
𝑄ℎ 𝑇ℎ 𝑆4 − 𝑆3 𝑇ℎ

Note: the thermal efficiency of a Carnot engine depends only on the

temperature levels and not upon the working substance of the engine.
Question 4 13