KMK20003

THERMODYNAMICS FOR CHEMICAL ENGINEERING

CHAPTER 2
PROPERTIES OF PURE SUBSTANCE (PART 1)
WEEK 2

1
2.1 Pure Substance

A pure substance has a homogeneous and invariable chemical composition and may
exist in more than one phase.

Examples:
1. Water (solid, liquid, and vapor phases)
2. Mixture of liquid water and water vapor
3. Carbon dioxide, CO2
4. Nitrogen, N2
5. Mixtures of gases, such as air, as long as there is no change of phase

2
2.1 Pure Substance
Let's consider the results of heating liquid water from 20C, 1 atm while keeping the
pressure constant. We will follow the constant pressure process shown in Figure 2-1.
First place liquid water in a piston-cylinder device where a fixed weight is placed on
the piston to keep the pressure of the water constant at all times. As liquid water is
heated while the pressure is held constant, the following events occur.

Process 1-2:

The temperature and specific volume will

increase from the compressed liquid, or
subcooled liquid, state 1, to the saturated
liquid state 2. In the compressed liquid
region, the properties of the liquid are
approximately equal to the properties of
the saturated liquid state at the
temperature.

3
2.1 Pure Substance
Process 2-3:

At state 2 the liquid has reached the temperature at which it begins to boil, called the saturation
temperature, and is said to exist as a saturated liquid. Properties at the saturated liquid state
are noted by the subscript f and v2 = vf. During the phase change both the temperature and
pressure remain constant.

At state 3 the liquid and vapor phase are in equilibrium and any point on the line between states
2 and 3 has the same temperature and pressure.

4
2.1 Pure Substance
Process 3-4:

At state 4 a saturated vapor exists and vaporization is complete.

The subscript g will always denote a saturated vapor state. Note
v 4 = vg .

Thermodynamic properties at the saturated liquid state and saturated vapor state are
given in Table A-4 as the saturated temperature table and Table A-5 as the saturated
pressure table. These tables contain the same information. In Table A-4 the
saturation temperature is the independent property, and in Table A-5 the saturation
pressure is the independent property. The saturation pressure is the pressure at
which phase change will occur for a given temperature. In the saturation region the
temperature and pressure are dependent properties; if one is known, then the other is
automatically known.

5
2.1 Pure Substance
Process 4-5:

If the constant pressure heating is continued, the temperature will begin to increase above the
saturation temperature, 100 C in this example, and the volume also increases. State 5 is called
a superheated state because T5 is greater than the saturation temperature for the pressure and
the vapor is not about to condense. Thermodynamic properties for water in the superheated
region are found in the superheated steam tables, Table A-6.

This constant pressure heating process is illustrated in the following figure.

6
 99.975 

Figure 2-6

Consider repeating this process for other constant pressure lines as shown below.

7
If all of the saturated liquid states are connected, the saturated liquid line is
established. If all of the saturated vapor states are connected, the saturated vapor
line is established. These two lines intersect at the critical point and form what is
often called the “steam dome.” The region between the saturated liquid line and the
saturated vapor line is called by these terms: saturated liquid-vapor mixture region,
wet region (i.e., a mixture of saturated liquid and saturated vapor), two-phase region,
and just the saturation region. Notice that the trend of the temperature following a
constant pressure line is to increase with increasing volume and the trend of the
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pressure following a constant temperature line is to decrease with increasing volume.
 P2 = 1000 kPa

P1 = 100 kPa

179.88oC

99.61oC

9
The region to the left of the saturated liquid line and below the critical temperature is
called the compressed liquid region. The region to the right of the saturated vapor
line and above the critical temperature is called the superheated region. See Table
A-1 for the critical point data for selected substances.

Review the P-v diagrams for substances that contract on freezing and those that
expand on freezing given in Figure 3-21 and Figure 3-22.

At temperatures and pressures above the critical point, the phase transition from
liquid to vapor is no longer discrete.

10
Figure 3-25 shows the P-T diagram, often called the phase diagram, for pure
substances that contract and expand upon freezing.

The triple point of water is 0.01oC, 0.6117 kPa (See Table 3-3).

The critical point of water is 373.95oC, 22.064 MPa (See Table A-1).

11
Plot the following processes on the P-T diagram for water (expands on freezing)
and give examples of these processes from your personal experiences.

1. process a-b: liquid to vapor transition

2. process c-d: solid to liquid transition
3. process e-f: solid to vapor transition

12
2.1 Properties Table
In addition to the temperature, pressure, and volume data, Tables A-4 through A-8
contain the data for the specific internal energy u the specific enthalpy h and the
specific entropy s. The enthalpy is a convenient grouping of the internal energy,
pressure, and volume and is given by

H  U  PV
The enthalpy per unit mass is
h  u  Pv

We will find that the enthalpy h is quite useful in calculating the energy of mass
streams flowing into and out of control volumes. The enthalpy is also useful in the
energy balance during a constant pressure process for a substance contained in a
closed piston-cylinder device. The enthalpy has units of energy per unit mass, kJ/kg.
The entropy s is a property defined by the second law of thermodynamics and is
related to the heat transfer to a system divided by the system temperature; thus, the
entropy has units of energy divided by temperature. The concept of entropy is
explained in Chapters 6 and 7.
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2.1 Properties Table
Saturated Water Tables

Since temperature and pressure are dependent properties using the phase change, two
tables are given for the saturation region. Table A-4 has temperature as the
independent property; Table A-5 has pressure as the independent property. These two
tables contain the same information and often only one table is given.
For the complete Table A-4, the last entry is the critical point at 373.95oC.

TABLE A-4

Saturated water-Temperature table

See next slide.

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Temp., Sat. Specific volume, Internal energy, Enthalpy, Entropy,
T C Press., m3/kg kJ/kg kJ/kg kJ/kgK
Psat kPa
Sat. liquid, Sat. Sat. Evap., Sat. Sat. Evap., Sat. Sat. Evap., Sat.
vf vapor, liquid, ufg vapor, liquid, hfg vapor, liquid, sfg vapor,
vg uf ug hf hg sf sg

0.01 0.6117 0.001000 206.00 0.00 2374.9 2374.9 0.00 2500.9 2500.9 0.0000 9.1556 9.1556

5 0.8725 0.001000 147.03 21.02 2360.8 2381.8 21.02 2489.1 2510.1 0.0763 8.9487 9.0249

10 1.228 0.001000 106.32 42.02 2346.6 2388.7 42.02 2477.2 2519.2 0.1511 8.7488 8.8999

15 1.706 0.001001 77.885 62.98 2332.5 2395.5 62.98 2465.4 2528.3 0.2245 8.5559 8.7803

20 2.339 0.001002 57.762 83.91 2318.4 2402.3 83.91 2453.5 2537.4 0.2965 8.3696 8.6661

25 3.170 0.001003 43.340 104.83 2304.3 2409.1 104.83 2441.7 2546.5 0.3672 8.1895 8.5567

30 4.247 0.001004 32.879 125.73 2290.2 2415.9 125.74 2429.8 2555.6 0.4368 8.0152 8.4520

35 5.629 0.001006 25.205 146.63 2276.0 2422.7 146.64 2417.9 2564.6 0.5051 7.8466 8.3517

40 7.385 0.001008 19.515 167.53 2261.9 2429.4 167.53 2406.0 2573.5 0.5724 7.6832 8.2556

45 9.595 0.001010 15.251 188.43 2247.7 2436.1 188.44 2394.0 2582.4 0.6386 7.5247 8.1633

50 12.35 0.001012 12.026 209.33 2233.4 2442.7 209.34 2382.0 2591.3 0.7038 7.3710 8.0748

55 15.76 0.001015 9.5639 230.24 2219.1 2449.3 230.26 2369.8 2600.1 0.7680 7.2218 7.9898

60 19.95 0.001017 7.6670 251.16 2204.7 2455.9 251.18 2357.7 2608.8 0.8313 7.0769 7.9082

65 25.04 0.001020 6.1935 272.09 2190.3 2462.4 272.12 2345.4 2617.5 0.8937 6.9360 7.8296

70 31.20 0.001023 5.0396 293.04 2175.8 2468.9 293.07 2333.0 2626.1 0.9551 6.7989 7.7540

75 38.60 0.001026 4.1291 313.99 2161.3 2475.3 314.03 2320.6 2634.6 1.0158 6.6655 7.6812

80 47.42 0.001029 3.4053 334.97 2146.6 2481.6 335.02 2308.0 2643.0 1.0756 6.5355 7.6111

85 57.87 0.001032 2.8261 355.96 2131.9 2487.8 356.02 2295.3 2651.4 1.1346 6.4089 7.5435

90 70.18 0.001036 2.3593 376.97 2117.0 2494.0 377.04 2282.5 2659.6 1.1929 6.2853 7.4782

95 84.61 0.001040 1.9808 398.00 2102.0 2500.1 398.09 2269.6 2667.6 1.2504 6.1647 7.4151

100 101.42 0.001043 1.6720 419.06 2087.0 2506.0 419.17 2256.4 2675.6 1.3072 6.0470 7.3542

۰ ۰ ۰ ۰ ۰ ۰ ۰ ۰ ۰ ۰ ۰ ۰ ۰

۰ ۰ ۰ ۰ ۰ ۰ ۰ ۰ ۰ ۰ ۰ ۰ ۰

360 18666 0.001895 0.006950 1726.16 625.7 2351.9 1761.53 720.1 2481.6 3.9165 1.1373 5.0537

365 19822 0.002015 0.006009 1777.22 526.4 2303.6 1817.16 605.5 2422.7 4.0004 0.9489 4.9493

370 21044 0.002217 0.004953 1844.53 385.6 2230.1 1891.19 443.1 2334.3 4.1119 0.6890 4.8009 15
373.95 22064 0.003106 0.003106 2015.8 0 2015.8 2084.3 0 2084.3 4.4070 0 4.4070
TABLE A-5
Saturated water-Pressure table
Press. Sat. Temp., Specific volume, Internal energy, Enthalpy, Entropy,
P kPa Tsat C m3/kg kJ/kg kJ/kg kJ/kgK

Sat. Sat. Sat. Evap., Sat. Sat. Evap., Sat. Sat. Evap., Sat.
liquid, vapor, liquid, ufg vapor, liquid, hfg vapor, liquid, sfg vapor,
vf vg uf ug hf hg sf sg

0.6117 0.01 0.001000 206.00 0.00 2374.9 2374.9 0.00 2500.9 2500.9 0.0000 9.1556 9.1556

1.0 6.97 0.001000 129.19 29.30 2355.2 2384.5 29.30 2484.4 2513.7 0.1059 8.8690 8.9749

1.5 13.02 0.001001 87.964 54.69 2338.1 2392.8 54.69 2470.1 2524.7 0.1956 8.6314 8.8270

2.0 17.50 0.001001 66.990 73.43 2325.5 2398.9 73.43 2459.5 2532.9 0.2606 8.4621 8.7227

2.5 21.08 0.001002 54.242 88.42 2315.4 2403.8 88.42 2451.0 2539.4 0.3118 8.3302 8.6421

3.0 24.08 0.001003 45.654 100.98 2306.9 2407.9 100.98 2443.9 2544.8 0.3543 8.2222 8.5765

4.0 28.96 0.001004 34.791 121.39 2293.1 2414.5 121.39 2432.3 2553.7 0.4224 8.0510 8.4734

5.0 32.87 0.001005 28.185 137.75 2282.1 2419.8 137.75 2423.0 2560.7 0.4762 7.9176 8.3938

7.5 40.29 0.001008 19.233 168.74 2261.1 2429.8 168.75 2405.3 2574.0 0.5763 7.6738 8.2501

10 45.81 0.001010 14.670 191.79 2245.4 2437.2 191.81 2392.1 2583.9 0.6492 7.4996 8.1488

15 53.97 0.001014 10.020 225.93 2222.1 2448.0 225.94 2372.3 2598.3 0.7549 7.2522 8.0071

20 60.06 0.001017 7.6481 251.40 2204.6 2456.0 251.42 2357.5 2608.9 0.8320 7.0752 7.9073

25 64.96 0.001020 6.2034 271.93 2190.4 2462.4 271.96 2345.5 2617.5 0.8932 6.9370 7.8302

30 69.09 0.001022 5.2287 289.24 2178.5 2467.7 289.27 2335.3 2624.6 0.9441 6.8234 7.7675

40 75.86 0.001026 3.9933 317.58 2158.8 2476.3 317.62 2318.4 2636.1 1.0261 6.6430 7.6691

50 81.32 0.001030 3.2403 340.49 2142.7 2483.2 340.54 2304.7 2645.2 1.0912 6.5019 7.5931

75 91.76 0.001037 2.2172 384.36 2111.8 2496.1 384.44 2278.0 2662.4 1.2132 6.2426 7.4558

100 99.61 0.001043 1.6941 417.40 2088.2 2505.6 417.51 2257.5 2675.0 1.3028 6.0562 7.3589

125 105.97 0.001048 1.3750 444.23 2068.8 2513.0 444.36 2240.6 2684.9 1.3741 5.9100 7.2841

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۰ ۰ ۰ ۰ ۰ ۰ ۰ ۰ ۰ ۰ ۰ ۰ ۰

20,000 365.75 0.002038 0.005862 1785.84 509.0 2294.8 1826.59 585.5 2412.1 4.0146 0.9164 4.9310

21,000 369.83 0.002207 0.004994 1841.62 391.9 2233.5 1887.97 450.4 2338.4 4.1071 0.7005 4.8076

22,000 373.71 0.002703 0.003644 1951.65 140.8 2092.4 2011.12 161.5 2172.6 4.2942 0.2496 4.5439
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22,064 373.95 0.003106 0.003106 2015.8 0 2015.8 2084.3 0 2084.3 4.4070 0 4.4070
For the complete Table A-5, the last entry is the critical point at 22.064 MPa.

Saturation pressure is the pressure at which the liquid and vapor phases are in
equilibrium at a given temperature.

Saturation temperature is the temperature at which the liquid and vapor phases are
in equilibrium at a given pressure.

In Figure 3-11, states 2, 3, and 4 are saturation states.

The subscript fg used in Tables A-4 and A-5 refers to the difference between the
saturated vapor value and the saturated liquid value region. That is,
u fg  ug  u f
h fg  hg  h f
s fg  sg  s f
The quantity hfg is called the enthalpy of vaporization (or latent heat of vaporization).
It represents the amount of energy needed to vaporize a unit of mass of saturated
liquid at a given temperature or pressure. It decreases as the temperature or
pressure increases, and becomes zero at the critical point.
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2.2.1 Quality and Saturated Liquid-Vapor Mixture
The quality is zero for the saturated liquid and one for the saturated vapor (0 ≤ x ≤ 1).
The average specific volume at any state 3 is given in terms of the quality as follows.
Consider a mixture of saturated liquid and saturated vapor. The liquid has a mass mf
and occupies a volume Vf. The vapor has a mass mg and occupies a volume Vg.

masssaturated vapor mg
x 
masstotal m f  mg

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We note
V  V f  Vg
m  m f  mg
V  mv , V f  m f v f , Vg  mg v g
mv  m f v f  mg v g
mf v f mg v g
v 
m m
Recall the definition of quality x
mg mg
x 
m m f  mg
Then
mf m  mg
  1 x
m m
Note, quantity 1- x is often given the name moisture. The specific volume of the
saturated mixture becomes
v  (1  x )v f  xv g

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The form that we use most often is
v  v f  x (v g  v f )

It is noted that the value of any extensive property per unit mass in the saturation
region is calculated from an equation having a form similar to that of the above
equation. Let Y be any extensive property and let y be the corresponding intensive
property, Y/m, then
Y
y   y f  x( yg  y f )
m
 y f  x y fg
where y fg  y g  y f

The term yfg is the difference between the saturated vapor and the saturated liquid
values of the property y; y may be replaced by any of the variables v, u, h, or s.

We often use the above equation to determine the quality x of a saturated liquid-
vapor state.

The following application is called the Lever Rule:

20
 y  yf
x
y fg

The Lever Rule is illustrated in the following figures.

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2.2.2 Superheated Water
A substance is said to be superheated if the given temperature is greater than the
saturation temperature for the given pressure.
State 5 in Figure 3-11 is a superheated state.

In the superheated water Table A-6, T and P are the independent properties. The
value of temperature to the right of the pressure is the saturation temperature for the
pressure.

The first entry in the table is the saturated vapor state at the pressure.

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2.2.3 Compressed Liquid
A substance is said to be a compressed liquid when the pressure is greater than the
saturation pressure for the temperature.

It is now noted that state 1 in Figure 3-11 is called a compressed liquid state because
the saturation pressure for the temperature T1 is less than P1.

Data for water compressed liquid states are found in the compressed liquid tables,
Table A-7. Table A-7 is arranged like Table A-6, except the saturation states are the
saturated liquid states. Note that the data in Table A-7 begins at 5 MPa or 50 times
atmospheric pressure.

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2.2.3 Compressed Liquid
At pressures below 5 MPa for water, the data are approximately equal to the
saturated liquid data at the given temperature. We approximate intensive parameter
y, that is v, u, h, and s data as

y  y f @T
The enthalpy is more sensitive to variations in pressure; therefore, at high pressures
the enthalpy can be approximated by

h  h f @T  v f ( P  Psat )
For our work, the compressed liquid enthalpy may be approximated by

h  h f @T

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2.2.4 Saturated Ice-Water Vapor
When the temperature of a substance is below the triple point temperature, the
saturated solid and liquid phases exist in equilibrium. Here we define the quality as
the ratio of the mass that is vapor to the total mass of solid and vapor in the saturated
solid-vapor mixture. The process of changing directly from the solid phase to the
vapor phase is called sublimation. Data for saturated ice and water vapor are given in
Table A-8. In Table A-8, the term Subl. refers to the difference between the
saturated vapor value and the saturated solid value.

25
The specific volume, internal energy, enthalpy, and entropy for a mixture of saturated
ice and saturated vapor are calculated similarly to that of saturated liquid-vapor
mixtures.
yig  y g  yi
y  yi  x yig
where the quality x of a saturated ice-vapor state is
mg
x
mi  mg

26
2.2.5 Choosing Right Table
The correct table to use to find the thermodynamic properties of a real substance can
always be determined by comparing the known state properties to the properties in
the saturation region. Given the temperature or pressure and one other property from
the group v, u, h, and s, the following procedure is used. For example if the pressure
and specific volume are specified, three questions are asked: For the given pressure,

Is v  v f ?
Is v f  v  v g ?
Is v g  v ?

The answer to one of these questions must be yes. If the answer to the first question
is yes, the state is in the compressed liquid region, and the compressed liquid tables
are used to find the properties of the state. If the answer to the second question is
yes, the state is in the saturation region, and either the saturation temperature table
or the saturation pressure table is used to find the properties. Then the quality is
calculated and is used to calculate the other properties, u, h, and s. If the answer to
the third question is yes, the state is in the superheated region and the superheated
tables are used to find the other properties.
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Example 2-1
A rigid tank contains 50 kg of saturated liquid water at 90 °C. Determine the
pressure in the tank and the volume of the tank.

28
Example 2-2
A piston–cylinder device contains 0.0566 m3 of saturated water vapor at 350 kPa.
Determine the temperature and the mass of the vapor inside the cylinder.

29
Example 2-3
A mass of 200 g of saturated liquid water is completely vaporized at a constant
pressure of 100 kPa. Determine
(a)the volume change
(b)(b) the
amount of energy transferred to the water.

30
Example 2-4
A rigid tank contains 10 kg of water at 90 C. If 8 kg of the water is in the liquid form
and the rest is in the vapor form, determine (a) the pressure in the tank and (b) the
volume of the tank.

31
Example 2-5
An 80-L vessel contains 4 kg of refrigerant-134a at a pressure of 160 kPa.
Determine (a) the temperature, (b) the quality, (c) the enthalpy of the refrigerant,
and (d) the volume occupied by the vapor phase.

32
Example 2-6
Determine the temperature of water at a state of P = 0.5 MPa and h = 2890 kJ/kg.

33
Example 2-7

34
Example 2-8
Determine the internal energy of refrigerant-134a at a temperature of 0C and a
quality of 60%.

Using Table A-11, for T = 0C,

then,

u  u f  x (u g  u f )
 51.63  (0.6)(230.16  51.63)
kJ
 158.75
kg

35
Example 2-9
Consider the closed, rigid container of water shown below. The pressure is 700 kPa,
the mass of the saturated liquid is 1.78 kg, and the mass of the saturated vapor is
0.22 kg. Heat is added to the water until the pressure increases to 8 MPa. Find the
final temperature, enthalpy, and internal energy of the water. Does the liquid level
rise or fall? Plot this process on a P-v diagram with respect to the saturation lines
and the critical point.

P
mg, Vg

Sat. Vapor

mf, Vf
Sat. Liquid
v
36
 mg1 0.22 kg
x1    011
.
m f 1  mg1 (178
.  0.22) kg
Then, at P = 700 kPa
v1  v f 1  x1 (vg1  v f 1 )
 0.001108  (0.11)(0.2728  0.001108)
m3
 0.031
kg
State 2 is specified by:
P2 = 8 MPa, v2 = 0.031 m3/kg

At 8 MPa = 8000 kPa,

vf = 0.001384 m3/kg vg = 0.02352 m3/kg

at 8 MPa, v2 = 0.031 m3/kg.
Is v2  v f ? No
Is v f  v2  v g ? No
Is v g  v2 ? Yes
37
Therefore, State 2 is superheated.

Interpolating in the superheated tables at 8 MPa, v = 0.031 m3/kg gives,

T2 = 361 C
h2 = 3024 kJ/kg
u2 = 2776 kJ/kg

Since state 2 is superheated, the liquid level falls.

38