KMK20003

THERMODYNAMICS FOR CHEMICAL

ENGINEERING

CHAPTER 2
PROPERTIES OF PURE SUBSTANCE (PART 2)
WEEK 3

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Chapter 2 (Part 1) Week 2
2.1Pure Substances
2.2Phases of pure substances
2.3Phases change of pure substances
2.4Properties diagram of pure substances
T-v diagram
P-v diagram
P-T diagram
2.5Properties Table
Example 2-7

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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.

mg, Vg

Sat. Vapor

m f, V f
Sat. Liquid

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Chapter 2 (Part 3) Week 3
• 2.6Ideal gas equation
• 2.7Compressibility Factor
• 2.8Other equation of state
Equations of State

The relationship among the state variables, temperature, pressure, and specific volume is
called the equation of state. We now consider the equation of state for the vapor or gaseous
phase of simple compressible substances.

Ideal Gas

Based on our experience in chemistry and physics we recall that the combination of Boyle’s
and Charles’ laws for gases at low pressure result in the equation of state for the ideal gas as

where R is the constant of proportionality and is called the gas constant and takes on a
different value for each gas. If a gas obeys this relation, it is called an ideal gas. We often
write this equation as
Pv  RT

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The gas constant for ideal gases is related to the universal gas constant valid for all
substances through the molar mass (or molecular weight). Let Ru be the universal gas
constant. Then,
Ru
R
M
The mass, m, is related to the moles, N, of substance through the molecular weight or molar
mass, M, see Table A-1. The molar mass is the ratio of mass to moles and has the same value
regardless of the system of units.
g kg lbm
M air  28.97  28.97  28.97
gmol kmol lbmol
Since 1 kmol = 1000 gmol or 1000 gram-mole and 1 kg = 1000 g, 1 kmol of air has a mass of
28.97 kg or 28,970 grams.
mNM
The ideal gas equation of state may be written several ways.
Pv  RT
V
P  RT
m
PV  mRT 7
Here P = absolute pressure in MPa, or
kPa
v = molar specific volume in
m3/kmol
T = absolute temperature in K
Ru = 8.314 kJ/(kmolK)
Some values of the universal gas constant are
Universal Gas
Constant, Ru
8.314 kJ/(kmolK)
8.314 kPam3/(kmolK)
1.986 Btu/(lbmolR)
1545 ftlbf/(lbmolR)
10.73 psiaft3/(lbmolR) 8
 The ideal gas equation of state can be derived from basic principles if one
assumes

1. Intermolecular forces are small.

2. Volume occupied by the particles is small.
Example 2-5

Determine the particular gas constant for air and hydrogen.

Ru
R
M
kJ
8.314
Rair  kmol  K  0.287 kJ
kg kg  K
28.97
kmol

kJ
8.314
Rhydrogen  kmol  K  4.124 kJ
kg kg  K
2.016
kmol

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The ideal gas equation of state is used when (1) the pressure is small compared to the critical
pressure or (2) when the temperature is twice the critical temperature and the pressure is
less than 10 times the critical pressure. The critical point is that state where there is an
instantaneous change from the liquid phase to the vapor phase for a substance. Critical
point data are given in Table A-1.

Compressibility Factor

To understand the above criteria and to determine how much the ideal gas equation of state
deviates from the actual gas behavior, we introduce the compressibility factor Z as follows.

Pv  Z Ru T
or
Pv
Z
Ru T

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For an ideal gas Z = 1, and the deviation of Z from unity measures the deviation of the actual
P-V-T relation from the ideal gas equation of state. The compressibility factor is expressed as
a function of the reduced pressure and the reduced temperature. The Z factor is
approximately the same for all gases at the same reduced temperature and reduced pressure,
which are defined as
T P
TR  and PR 
Tcr Pcr
where Pcr and Tcr are the critical pressure and temperature, respectively. The critical
constant data for various substances are given in Table A-1. This is known as the
principle of corresponding states. Figure 3-51 gives a comparison of Z factors for
various gases and supports the principle of corresponding states.

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When either P or T is unknown, Z can be determined from the compressibility chart with the
help of the pseudo-reduced specific volume, defined as
vactual
vR 
R Tcr
Pcr
Figure A-15 presents the generalized compressibility chart based on data for a large number
of gases. 12
 These charts show the conditions for which Z = 1 and the gas behaves as an
ideal gas:

1.PR < 10 and TR > 2 or P < 10Pcr and T > 2Tcr

2.PR << 1 or P << Pcr

Note: When PR is small, we must make sure that the state is not in the
compressed liquid region for the given temperature. A compressed liquid state is
certainly not an ideal gas state.

For instance the critical pressure and temperature for oxygen are 5.08 MPa and 154.8 K,
respectively. For temperatures greater than 300 K and pressures less than 50 MPa (1
atmosphere pressure is 0.10135 MPa) oxygen is considered to be an ideal gas.

Example 2-6

Calculate the specific volume of nitrogen at 300 K and 8.0 MPa and compare the result with
the value given in a nitrogen table as v = 0.011133 m3/kg.

From Table A.1 for nitrogen

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 Tcr = 126.2 K, Pcr = 3.39 MPa R = 0.2968 kJ/kg-K
T 300 K
TR    2.38
Tcr 126.2 K
P 8.0 MPa
PR    2.36
Pcr 3.39 MPa
Since T > 2Tcr and P < 10Pcr, we use the ideal gas equation of state
Pv  RT
kJ
0.2968 (300 K ) 3
RT kg  K m MPa
v 
P 8.0 MPa 103 kJ
m3
 0.01113
kg
Nitrogen is clearly an ideal gas at this state.

If the system pressure is low enough and the temperature high enough (P and T are
compared to the critical values), gases will behave as ideal gases. Consider the T-v diagram
for water. The figure below shows the percentage of error for the volume ([|vtable –
videal|/vtable]x100) for assuming water (superheated steam) to be an ideal gas.
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We see that the region for which water behaves as an ideal gas is in the superheated region
and depends on both T and P. We must be cautioned that in this course, when water is the
working fluid, the ideal gas assumption may not be used to solve problems. We must use the
real gas relations, i.e., the property tables.

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Useful Ideal Gas Relation: The Combined Gas Law

By writing the ideal gas equation twice for a fixed mass and simplifying, the properties of an
ideal gas at two different states are related by
m1  m2

or
PV PV
1 1
 2 2
R T1 R T2
But, the gas constant is (fill in the blank), so
PV PV
1 1
 2 2
T1 T2
Example 2-7
An ideal gas having an initial temperature of 25C under goes the two processes described
below. Determine the final temperature of the gas.

Process 1-2: The volume is held constant while the pressure doubles.
Process 2-3: The pressure is held constant while the volume is reduced to
one-third of the original volume.
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 P T2
3
2
T3
Ideal
Gas T1
1

V
Process 1-3:
m1  m3
or
PV PV
1 1
 3 3
T1 T3
but V3 = V1/3 and P3 = P2 = 2P1

Therefore, P3 V3
T3  T1
P1 V1
2 P1 V1 / 3 2
T3  T1  T1
P1 V1 3
2
T3  (25  273) K  198.7 K  74.3C
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 Other Equations of State

Many attempts have been made to keep the simplicity of the ideal gas equation of
state but yet account for the intermolecular forces and volume occupied by the
particles. Three of these are

van der Waals:

a
(P  2
)(v  b)  R T
v
where

27 R 2 Tcr2 RTcr
a and b
64 Pcr 8 Pcr

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