28 PROPERTIES OF PURE SUBSTANCES [CHAP.

EXAMPLE 2.4 Two lb of water is contained in a constant-pressure container held at 540 psia. Heat is added
until the temperature reaches 700  F. Determine the final volume of the container.
Solution: Use Table C-3E. Since 540 psia lies between the table entry values, the specific volume is simply

v ¼ 1:3040 + ð0:4Þð1:0727  1:3040Þ ¼ 1:2115 ft3=lbm

The final volume is then V ¼ mv ¼ ð2Þð1:2115Þ ¼ 2:423 ft3 .

2.5 THE IDEAL-GAS EQUATION OF STATE

When the vapor of a substance has relatively low density, the pressure, specific volume, and tem-
perature are related by the specific equation

Pv ¼ RT ð2:6Þ

where R is a constant for a particular gas and is called the gas constant. This ideal-gas equation is an
equation of state in that it relates the state properties P, v, and T ; any gas for which this equation is valid
is called an ideal gas or a perfect gas. Note that when using the ideal-gas equation the pressure and
temperature must be expressed as absolute quantities.
The gas constant R is related to a universal gas constant Ru , which has the same value for all gases, by
the relationship
Ru
R¼ ð2:7Þ
M
where M is the molar mass, values of which are tabulated in Tables B-2 and B-3. The mole is that
quantity of a substance (i.e., that number of atoms or molecules) having a mass which, measured in
grams, is numerically equal to the atomic or molecular weight of the substance. In the SI it is convenient
to use instead the kilomole (kmol), which amounts to x kilograms of a substance of molecular weight x.
For instance, 1 kmol of carbon is a mass of 12 kg (exactly); 1 kmol of molecular oxygen is 32 kg (very
nearly). Stated otherwise, M ¼ 12 kg/kmol for C, and M ¼ 32 kg/kmol for O2 . In the English system one
uses the pound-mole (lbmol); for O2 , M ¼ 32 lbm/lbmol.
The value of Ru is

Ru ¼ 8:314 kJ=ðkmolKÞ ¼ 1545 ft-lbf=ðlbmol-  RÞ ¼ 1:986 Btu=ðlbmol-  RÞ ð2:8Þ

For air M is 28.97 kg/kmol (28.97 lbm/lbmol), so that for air R is 0.287 kJ/kgK (53.3 ft-lbf/lbm-  R),
a value used extensively in calculations involving air.
Other forms of the ideal-gas equation are

PV ¼ mRT P ¼ RT PV ¼ NRu T ð2:9Þ

where N is the number of moles.

Care must be taken in using this simple convenient equation of state. A low-density  can be
experienced by either having a low pressure or a high temperature. For air the ideal-gas equation is
surprisingly accurate for a wide range of temperatures and pressures; less than 1 percent error is
encountered for pressures as high as 3000 kPa at room temperature, or for temperatures as low as
–130  C at atmospheric pressure.
The compressibility factor Z helps us in determining whether or not the ideal-gas equation should be
used. It is defined as
Pv
Z¼ ð2:10Þ
RT
and is displayed in Fig. 2-6 for nitrogen. Since air is composed mainly of nitrogen, this figure is
acceptable for air also. If Z ¼ 1, or very nearly 1, the ideal-gas equation can be used. If Z is not
CHAP. 2] PROPERTIES OF PURE SUBSTANCES 29

Fig. 2-6 The compressibility factor.

approximately 1, then (2.10) may be used. Additional real-gas effects (deviations from ideal-gas beha-
vior) are considered in a subsequent chapter.
The compressibility factor can be determined for any gas by using a generalized compressibility
chart presented in Fig. G-1 in the appendix. In the generalized chart the reduced pressure PR and reduced
temperature TR must be used. They are calculated from
P T v
PR ¼ TR ¼ vR ¼ ð2:11Þ
Pcr Tcr RTcr =Pcr

where Pcr and Tcr are critical-point pressure and temperature, respectively, of Table B-3, and vR is the
pseudo-reduced volume.

EXAMPLE 2.5 An automobile tire with a volume of 0.6 m3 is inflated to a gage pressure of 200 kPa. Calculate
the mass of air in the tire if the temperature is 20  C.
Solution: Air is assumed to be an ideal gas at the conditions of this example. In the ideal-gas equation,
PV ¼ mRT , we use absolute pressure and absolute temperature. Thus, using Patm ¼ 100 kPa,

P ¼ 200 + 100 ¼ 300 kPa and T ¼ 20 + 273 ¼ 293 K

The mass is then calculated to be

PV ð300 000 N=m2 Þð0:6 m3 Þ

m¼ ¼ ¼ 2:14 kg
RT ð287 Nm=kgKÞð293 KÞ

The units in the above equation should be checked.

EXAMPLE 2.6 The temperature in the atmosphere near the surface of the earth (up to an elevation of 10 000 m)
can be approximated by T ðzÞ ¼ 15  0:00651z  C. Determine the pressure at an elevation of 3000 m if at z ¼ 0,
P ¼ 101 kPa.
30 PROPERTIES OF PURE SUBSTANCES [CHAP. 2

Solution: Equation (1.8) relates the pressure change to the elevation change. We can put the ideal-gas
equation for air in the form
 
287
P ¼ 287T ¼ ðwT Þ ¼ 29:3 wT
9:81

Hence, (1.8) can be written as

P
dP ¼  dz
29:3T

Using the given equation for T ðzÞ we have

P
dP ¼  dz
ð29:3Þð288  0:00651zÞ

where we have added 273 to express the temperature in kelvins. To integrate the above equation we must
separate variables as

dP dz
¼
P ð29:3Þð288  0:00651zÞ

Now integrate between the appropriate limits:

Z Z    Z 3000
P
dP 3000
dz 1 1 0:00651dz
¼ − =
101 P 0 ð29:3Þð288  0:00651zÞ 29:3 0:00651 0 288  0:00651z

P
ln ¼ ½5:24 lnð288  0:00651zÞ3000
0 ¼ 0:368
101

There results P=(101)(e0:368 )=69.9 kPa.

2.6 EQUATIONS OF STATE FOR A NONIDEAL GAS

There are many equations of state that have been recommended for use to account for nonideal-gas
behavior. Such behavior occurs where the pressure is relatively high (> 4 MPa for many gases) or when
the temperature is near the saturation temperature. There are no acceptable criteria that can be used to
determine if the ideal-gas equation can be used or if the nonideal-gas equations of this section must be
used. Usually a problem is stated in such a way that it is obvious that nonideal-gas effects must be
included; otherwise a problem is solved assuming an ideal gas.
The van der Waals equation of state is intended to account for the volume occupied by the gas-
molecules and for the attractive forces between molecules. It is
RT a
P¼  ð2:12Þ
v  b v2

where the constants a and b are related to the critical-point data of Table B-3 by

27R2 Tcr2 RTcr

a¼ b¼ ð2:13Þ
64Pcr 8Pcr

These constants are also presented in Table B-8 to simplify calculations.

CHAP. 2] PROPERTIES OF PURE SUBSTANCES 31

An improved equation is the Redlich–Kwong equation of state:

RT a
P¼  pffiffiffiffi ð2:14Þ
v  b vðv + bÞ T

where the constants are given by

R2 Tcr2:5 RTcr
a ¼ 0:4275 b ¼ 0:0867 ð2:15Þ
Pcr Pcr

and are included in Table B-8.

A virial equation of state presents the product Pv as a series expansion. The most common expan-
sion is

RT BðT Þ CðT Þ
P¼ + 2 + 3 +  ð2:16Þ
v v v

where interest is focused on B(T) since it represents the first-order correction to the ideal-gas law. The
functions BðT Þ, CðT Þ, etc., must be specified for the particular gas.

EXAMPLE 2.7 Calculate the pressure of steam at a temperature of 500  C and a density of 24 kg/m3 using
(aÞ the ideal-gas equation, (b) the van der Waals equation, (c) the Redlich–Kwong equation, (d) the compres-
sibility factor, and (e) the steam table.
Solution:
(a) Using the ideal-gas equation, P ¼ RT ¼ ð24Þð0:462Þð773Þ ¼ 8570 kPa, where the gas constant for
steam is found in Table B-2.
(b) Using values for a and b from Table B-8, the van der Waals equation provides

RT a ð0:462Þð773Þ 1:703
P¼  ¼ 1   2 ¼ 7950 kPa
v  b v2 24  0:00169 1
24

(c) Using values for a and b from Table B-8, the Redlich–Kwong equation gives

RT a ð0:462Þð773Þ 43:9
P¼  pffiffiffiffi ¼ 1   1  1 pffiffiffiffiffiffiffiffi ¼ 7930 kPa
v  b vðv + bÞ T 24  0:00117 24 24 + 0:00117 773

(d) The compressibility factor is found from the generalized compressibility chart of Fig. G-1 in the
appendix. To use the chart we must know the reduced temperature and pressure:

T 773 P 8000
TR ¼ ¼ ¼ 1:19 PR ¼ ¼ ¼ 0:362
Tcr 647:4 Pcr 22 100

where we have used the anticipated pressure from parts (a), (b), and (c). Using the compressibility
chart (it is fairly insensitive to the precise values of TR and PR , so estimates of these values are quite
acceptable) and (2.10), we find

ZRT ð0:93Þð0:462Þð773Þ
P¼ ¼ ¼ 7970 kPa
v 1=24

(e) The steam table provides the most precise value for the pressure. Using T ¼ 500  C and
v ¼ 1=24 ¼ 0:0417 m3 /kg, we find P ¼ 8000 kPa. Note that the ideal-gas law has an error of 7.1 percent,
and the error of each of the other three equations is less than 1 percent.
32 PROPERTIES OF PURE SUBSTANCES [CHAP. 2

Solved Problems
3
2.1 For a specific volume of 0.2 m /kg, find the quality of steam if the absolute pressure is (a) 40 kPa
and (b) 630 kPa. What is the temperature of each case?
ðaÞ Using information from Table C-2 in (2.3), we calculate the quality as follows:

v ¼ vf + xðvg  vf Þ 0:2 ¼ 0:001 + xð3:993  0:001Þ ∴ x ¼ 0:04985

The temperature is found in Table C-2 next to the pressure entry: T ¼ 75:9  C.
ðbÞ We must interpolate to find the correct values in Table C-2. Using the values at 0.6 and 0.8 MPa we have
 
0:03
vg ¼ ð0:2404  0:3157Þ + 0:3157 ¼ 0:3044 vf ¼ 0:0011
0:2

Using (2.3), we have

0:2 ¼ 0:0011 + xð0:3044  0:0011Þ ∴ x ¼ 0:6558

The temperature is interpolated to be

 
0:03
T ¼ ð170:4  158:9Þ + 158:9 ¼ 160:6  C
0:2

2.2 Calculate the specific volume of water at (a) 160  C and (b) 221  C if the quality is 85 percent.
ðaÞ Using the entries from Table C-1 and (2.3) we find

v ¼ vf + xðvg  vf Þ ¼ 0:0011 + ð0:85Þð0:3071  0:0011Þ ¼ 0:2612

ðbÞ We must interpolate to find the values for vg and vf . Using entries at 220  C and 230  C, we determine
 
1
vg ¼ ð0:07159  0:08620Þ + 0:08620 ¼ 0:08474 f ¼ 0:00120
10

Using (2.3) v ¼ 0:00120 + ð0:85Þð0:08474  0:00120Þ ¼ 0:07221 m3 /kg.

2.3 Ten pounds of steam is contained in a volume of 50 ft3 . Find the quality and the pressure if the
temperature is 263  F.
The temperature is not a direct entry in Table C-1E. We interpolate between temperatures of 260  F and
270  F to find
 
3
vg ¼ ð10:066  11:768Þ + 11:768 ¼ 11:257 vf ¼ 0:017
10

From the given information we calculate

V 50
v¼ ¼ ¼ 5:0 ft3 =lbm
m 10

The quality is found from (2.3) as follows:

5 ¼ 0:017 + xð11:257  0:017Þ ∴ x ¼ 0:4433

The pressure is interpolated to be

 
3
P¼ ð41:85  35:42Þ + 35:42 ¼ 37:35 psia
10