Chapter 2: Properties of a

Pure Substance
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Problem 2.15
Modern extraction techniques can be based on dissolving materials in
supercritical fluids such as carbon dioxide. How high are the pressure
and density of Carbon dioxide when the temperature and pressure are
at their critical values? Repeat for Ethyl Alcohol.

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Solution
From the thermodynamic table A.2, for Carbon Dioxide,

𝑃𝑐 = 7.38 𝑀𝑃𝑎 𝑇𝑐 = 304 𝐾 𝑣𝑐 = 0.00212 𝑚3 /𝑘𝑔

1 1
𝜌𝑐 = = = 471.698 𝑘𝑔/𝑚3
𝑣𝑐 0.00212

From the thermodynamic table A.2, for Ethyl Alcohol,

𝑃𝑐 = 6.14 𝑀𝑃𝑎 𝑇𝑐 = 514 𝐾 𝑣𝑐 = 0.00363 𝑚3 /𝑘𝑔

1 1
𝜌𝑐 = = = 275.482 𝑘𝑔/𝑚3
𝑣𝑐 0.00363

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Problem 2.19
Give the phase for the following states (use Table A.2)

a) CO2 at T=50°C and P=0.4 Mpa

b) Nitrogen at T=25°C and P=220 kPa

c) NH3 at T=180°C and P=550 kPa

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Solution
a) For Carbon Dioxide, from table A.2.,

𝑇𝑐 = 304.1 𝐾 = 30.95°𝐶 and 𝑃𝑐 = 7.38 𝑀𝑃𝑎

As 𝑇 > 𝑇𝑐 𝑎𝑛𝑑 𝑃 ≪ 𝑃𝑐 , Carbon dioxide exists as a superheated vapor at these

conditions.

b) For Nitrogen, from table A.2.,

𝑇𝑐 = 126.2 𝐾 = 146.95°𝐶 and 𝑃𝑐 = 3.39 𝑀𝑃𝑎

As 𝑇 > 𝑇𝑐 𝑎𝑛𝑑 𝑃 ≪ 𝑃𝑐 , Nitrogen exists as a superheated vapor at these conditions.

c) For Ammonia, from table A.2.,

𝑇𝑐 = 405.5°𝐶 = 132.35°𝐶 and 𝑃𝑐 = 11.35 𝑀𝑃𝑎

As 𝑇 > 𝑇𝑐 𝑎𝑛𝑑 𝑃 ≪ 𝑃𝑐 , Ammonia exists as a superheated vapor at these conditions.

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Problem 2.25
For refrigerant R-134a, in each of the following cases, determine
whether it is a compressed liquid, a superheated vapor, or a mixture of
saturated liquid and saturated vapor.

a) 60°C, 0.06 m3/kg

b) 1.2 MPa, 50°C

c) 150 kPa, 0.09 m3/kg

d) -15°C, 100 kPa

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Solution
a) At the given conditions of 60°C, using table B.5.1., we have,

𝑣𝑔 = 0.01146 𝑚3 /𝑘𝑔 and 𝑣𝑓 = 0.000951 𝑚3 /𝑘𝑔

As 𝑣 > 𝑣𝑔 , R-134a exists as a superheated vapor at these conditions

b) At the given temperature of 50°C,

𝑃𝑠𝑎𝑡 = 1318.1 𝑘𝑃𝑎

As 𝑃 < 𝑃𝑠𝑎𝑡 , R-134a exists as a superheated vapor at these conditions

c) At the pressure of 150 kPa, the volume of saturated vapor is equal to

𝑣𝑠𝑎𝑡 = 0.13139 𝑚3 /𝑘𝑔

As 𝑣 < 𝑣𝑠𝑎𝑡 , R-134a exists as a mixture of vapor and liquid at these conditions

d) At 100 kPa, the saturation temperature is equal to

𝑇𝑠𝑎𝑡 = −26.54°𝐶

As 𝑇 > 𝑇𝑠𝑎𝑡 , R-134a exists as a superheated vapor at these conditions.

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Problem 2.32
A sealed rigid vessel has volume of 1 m3 and contains 2 kg of water at
100°C. The vessel is now heated. If a safety pressure valve is installed,
at what pressure should the valve be set to have a maximum
temperature of 200°C?

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Solution
As the vessel is sealed and rigid, the process is an isochoric process. Thus, the
specific volume remains constant.

At the initial state, we have,

1
𝑣1 = = 0.5 𝑚3 /𝑘𝑔
2

From B.1.1., 𝑣𝑓 = 0.001044 𝑚3 /𝑘𝑔, 𝑣𝑔 = 1.67290 𝑚3 /𝑘𝑔.

As 𝑣𝑓 < 𝑣 < 𝑣𝑔, water exists as a mixture of vapor and liquid.

At state 2, it is given that 𝑇 = 200°𝐶, and 𝑣 = 0.5 𝑚3 /𝑘𝑔.

From table B.1.3., we can see that the pressure is between 400 kPa and 500 kPa, so
by using interpolation, we have,

500 − 400
𝑃 = 400 + 0.5 − 0.53422 = 431.308 𝑘𝑃𝑎
0.42492 − 0.53422

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Problem 2.42
A 400 m3 storage tank is constructed to hold Liquefied Natural Gas
(LNG) (assumed to be pure methane). If the tank contains 90% liquid
and 10% vapor by volume at 100 kPa, what mass of the LNG will the
tank hold? Also, what is the quality of the LNG within the tank?

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Solution
Using the tables of Appendix B, for methane, the specific volume values are given as

𝑣𝑓 = 0.002366 𝑚3 /𝑘𝑔 and 𝑣𝑔 = 0.55665 𝑚3 /𝑘𝑔

The mass of liquid within the tank is given as

𝑉𝑙𝑖𝑞 0.9 × 400

𝑚𝑙𝑖𝑞 = = = 152155.537 𝑘𝑔
𝑣𝑓 0.002366
The mass of vapor within the tank is given as

𝑉𝑣𝑎𝑝 0.1 × 400

𝑚𝑣𝑎𝑝 = = = 71.858 𝑘𝑔
𝑣𝑔 0.55665
Thus, the total mass of methane in the tank is
𝑚𝑡𝑜𝑡 = 𝑚𝑣𝑎𝑝 + 𝑚𝑙𝑖𝑞 = 152227.395 𝑘𝑔

The quality of the methane in the tank is given as

𝑚𝑣𝑎𝑝 71.858
𝑥= = = 0.000472
𝑚𝑡𝑜𝑡 152227.395
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Problem 2.46
Is it reasonable to assume that at the given states the substance
behaves as an ideal gas?

a) Oxygen at 30◦C, 3 Mpa

b) Methane at 30◦C, 3 Mpa

c) Water at 30◦C, 3 Mpa

d) R-134a at 30◦C, 3 Mpa

e) R-134a at 30◦C, 100 kPa

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Solution
Solution:

a) Oxygen, O₂ at 30°C, 3 MPa Ideal Gas (T ≫ 𝑇𝑐 = 155 K from A.2)

b) Methane, CH4 at 30°C, 3 MPa Ideal Gas (T ≫ 𝑇𝑐 = 190 K from A.2)

c) Water, H₂O at 30°C, 3 MPa NO. It is a compressed liquid as P > 𝑃𝑠𝑎𝑡

(B.1.1)

d) R-134a at 30°C, 3 MPa NO. It is a compressed liquid as P > 𝑃𝑠𝑎𝑡

(B.5.1)

e) R-134a at 30°C, 100 kPa Ideal Gas (P is low, P < 𝑃𝑠𝑎𝑡 ) (B.5.1)

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Problem 2.49
Helium in a steel tank is at 250 kPa, 300 K with a volume of 0.1 𝑚3 . It is
used to fill a balloon. When the pressure drops to 150 kPa, the flow of
helium stops by itself. If all the helium is still at 300 K, how big a balloon
is produced?

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Solution
𝑘𝐽
From the appendix A.5., the value of 𝑅 for helium is 𝑅 = 2.0771 .
𝑘𝑔 𝐾

At the initial state, 𝑇1 = 300 𝐾, 𝑃1 = 250 𝑘𝑃𝑎, 𝑉1 = 0.1 𝑚3 .

Thus, the mass of the gas is,
𝑃1 𝑉1 250 × 0.1
𝑚= = = 0.0401 𝑘𝑔
𝑅𝑇1 2.0771 × 300
At the final state, the pressure has reduced to 𝑃2 = 150 𝑘𝑃𝑎, while 𝑇2 = 𝑇1 = 300 𝐾.
The overall mass of helium is the sum of the masses in the tank and the balloon, which
is constant. Thus,
𝑃1 𝑉1 𝑃2 𝑉2
𝑚1 = 𝑚2 ⇒ = ⇒ 𝑃1 𝑉1 = 𝑃2 𝑉2
𝑅𝑇 𝑅𝑇
Thus,
𝑃1 𝑉1 250 × 0.1
𝑉2 = = = 0.16667 𝑚3
𝑃2 150
The volume of air filling the balloon is the difference between the two volumes, i.e.,
𝑉𝑏𝑎𝑙𝑙𝑜𝑜𝑛 = 𝑉2 − 𝑉1 = 0.16667 − 0.1 = 0.06667𝑚3
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Problem 2.56
A 1m3 rigid tank has propane at 125 kPa, 300 K and connected by a
valve to another tank of 0.5 m3 with propane at 250 kPa, 400 K. The
valve is opened, and the two tanks come to a uniform state at 325 K.
What is the final pressure?

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Solution
Propane is an ideal gas (as 𝑃 ≪ 𝑃𝑐 ) with 𝑅 = 0.1886 𝑘𝐽Τ𝑘𝑔𝐾 from table A.5
The mass of propane in tank A is:

𝑃𝐴 𝑉𝐴 125𝑘𝑃𝑎 × 1𝑚3
𝑚𝐴 = = = 2.2093 𝑘𝑔
𝑅𝑇𝐴 0.1886 × 300
The mass of propane in tank B is:
𝑃𝐵 𝑉𝐵 250𝑘𝑃𝑎 × 0.5𝑚3
𝑚𝐵 = = = 1.6564 𝑘𝑔
𝑅𝑇𝐵 0.1886 × 400
The total volume of propane is:
𝑉2 = 𝑉𝐴 + 𝑉𝐵 = 1.5 𝑚3
The total mass is:
𝑚2 = 𝑚𝐴 + 𝑚𝐵 = 3.8657 𝑘𝑔
Thus, from ideal gas law:
𝑚2 𝑅𝑇2 3.8657 × 0.1886 × 325
𝑃2 = = = 158 𝑘𝑃𝑎
𝑉2 1.5

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Problem 2.60
How close to ideal gas behavior is ammonia at saturated vapor at 100
kPa? What about at 2000 kPa.

Hint: calculate Z values at both states.

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Solution
From the table B.2.2., at 𝑃 = 100 𝑘𝑃𝑎,

𝑣1 = 1.1381 𝑚3 Τ𝑘𝑔, 𝑇1 = −33.6°𝐶, 𝑃1 = 100 𝑘𝑃𝑎

From the table B.2.2., at 𝑃 = 2000 𝑘𝑃𝑎,

𝑣2 = 0.06444 𝑚3 Τ𝑘𝑔, 𝑇2 = 49.37°𝐶, 𝑃2 = 2000 𝑘𝑃𝑎

From the table A.5., 𝑅 = 0.4882 𝑘𝐽Τ𝑘𝑔 𝐾 for Ammonia

Using the extended gas law, we have,

𝑃1 𝑉1 100 × 1.1381
𝑍1 = = = 0.973
𝑅𝑇1 0.4882 × (273.15 − 33.6)

𝑃2 𝑉2 2000 × 0.06444
𝑍2 = = = 0.8185
𝑅𝑇2 0.4882 × (273.15 + 49.37)

Thus, state 1 is close to ideal gas, while state 2 is not.

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Problem 2.70
𝑚3
Determine the pressure of nitrogen at 160 K and 0.00291 using ideal
𝑘𝑔

gas, van der Waal Equation of State and the nitrogen table.

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Solution
From the table A.2., the critical constants for Nitrogen are, 𝑇𝑐 = 126.2 𝐾, 𝑃𝑐 = 3390 𝑘𝑃𝑎

From the ideal gas equation:

𝑅𝑇 0.2968 × 160
𝑃= = = 16 319 𝑘𝑃𝑎
𝑣 0.00291
For van der waals equation of state, we have,

1 𝑅𝑇𝑐 1 × 0.2968 × 126.2

𝑏= = = 0.001381 𝑚3 Τ𝑘𝑔
8 𝑃𝑐 8 × 3390
𝑎 = 27 𝑏 2 𝑃𝑐 = 27 × 0.001381 2 × 3390 = 0.17456 𝑚3 Τ𝑘𝑔 2

Van der Waals equation of state is given by:

𝑅𝑇 𝑎 0.2968 × 160 0.17456

𝑃= − = − = 10444.375 𝑘𝑃𝑎
𝑣 − 𝑏 𝑣 2 0.00291 − 0.001381 0.002912
From the table B.6.2,
𝑃 = 10 000 𝑘𝑃𝑎
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Problem 2.69
𝑚3
Determine the pressure of nitrogen at 160 K and 0.00291 using the
𝑘𝑔

Soave EOS and the nitrogen table.

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Solution
From the table A.2., the critical constants for Nitrogen are, 𝑇𝑐 = 126.2 𝐾, 𝑃𝑐 = 3390 𝑘𝑃𝑎
The ideal gas constant for Nitrogen is 𝑅 = 0.2968 𝑘𝐽Τ𝑘𝑔 𝐾.
The reduced temperature is 𝑇𝑟 = 𝑇Τ𝑇𝑐 = 160Τ126.2 = 1.26783
For the Soave equation of state,
𝑅𝑇𝑐 0.2968 × 126.2
𝑏 = 𝑏0 = 0.08664 × = 9.57287 × 10−4 𝑚3Τ𝑘𝑔
𝑃𝑐 3390
From the table D.4., the acentric factor is 𝜔 = 0.039
The other parameters are given by:
𝑓 = 0.48 + 1.574𝜔 − 0.176𝜔 2 = 0.54112
2
1Τ2
𝑎0 = 0.42748 1 + 𝑓 1 − 𝑇𝑟 = 0.37118

𝑎0 𝑅2 𝑇𝑐2
𝑎= = 0.15362 𝑘𝑃𝑎 𝑚3Τ𝑘𝑔 2
𝑃𝑐
From the Soave eqn of state,
𝑅𝑇 𝑎
𝑃= − 2 ⇒ 𝑃 = 10 669 𝑘𝑃𝑎
𝑣 − 𝑏 𝑣 + 𝑐𝑏𝑣 + 𝑑𝑏 2
From the tables, 𝑃 = 10 000 𝑘𝑃𝑎
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 Problem 2.79
Consider two tanks, A and B, connected by a valve, as shown in Fig. Each
has a volume of 200 L, and tank A has R-410a at 25◦C, 10% liquid and 90%
vapor by volume, while tank B is evacuated. The valve is now opened, and
saturated vapor flows from A to B until the pressure in B has reached that in
A, at which point the valve is closed. This process occurs slowly such that all
temperatures stay at 25◦C throughout the process. How much has the quality
changed in tank A during the process?

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Solution
In tank A, at the initial state, we have from table B.4.1.,

𝑣𝑓 = 0.000944 𝑚3 /𝑘𝑔 and 𝑣𝑔 = 0.01514 𝑚3 /𝑘𝑔

The mass of R-410a in tank A is given as

𝑉𝑙𝑖𝑞1 𝑉𝑣𝑎𝑝1 0.1 × 0.2 0.9 × 0.2

𝑚𝐴1 = + = +
𝑣𝑓 𝑣𝑔 0.000944 0.01514
⇒ 𝑚𝐴1 = 21.186 + 11.889 = 33.075 𝑘𝑔
Thus, the quality of R-410a in tank A is given as

𝑚𝑣𝑎𝑝1 11.889
𝑥𝐴1 = = = 0.3594
𝑚𝑡𝑜𝑡 33.075

After the valve is opened and the system is allowed to attain equilibrium, for tank B, we
have,

𝑉𝐵 0.2
𝑚𝐵2 = = = 13.210 𝑘𝑔
𝑣𝑔 0.01514
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For tank A at equilibrium, we have,
𝑚𝐴2 = 33.075 − 13.210 = 19.865 𝑘𝑔

The specific volume in tank A at the final state is given as

0.2
𝑣𝐴2 = = 0.010068 𝑚3 /𝑘𝑔
19.865
From the equation of quality, we have,

𝑚3
𝑣𝐴2 = 0.010068 = 0.000944 + 𝑥𝐴2 × 0.01420
𝑘𝑔

Solving for quality, we have,

𝑥𝐴2 = 0.6425

Thus, the change in quality is given as

Δ𝑥 = 𝑥𝐴1 − 𝑥𝐴2 = 0.3594 − 0.6425 = 0.2831

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