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 Boyles 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
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 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.
M air 28.97
g kg lbm 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.
mNM
The ideal gas equation of state may be written several ways.
Pv RT V P RT m PV mRT
Here
P
v
T Ru
= absolute pressure in MPa, or kPa = molar specific volume in m3/kmol = absolute temperature in K = 8.314 kJ/(kmolK)
Some values of the universal gas constant are Universal Gas Constant, Ru 8.314 kJ/(kmolK) 8.314 kPam3/(kmolK) 1.986 Btu/(lbmolR) 1545 ftlbf/(lbmolR) 10.73 psiaft3/(lbmolR)
Compressibility Factor In order to determine how much the ideal gas equation of state deviates from the actual gas behavior, we can define Compressibility factor (Z). The deviation of a gas from ideal gas gas behavior can be accounted for by incorporation of compressibity factor Z, such that
Z = Pv / RT
It can also be expressed as
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.
Gases behave differently at a given temperature and pressure, but they behave very much the same at temperatures and pressures normalized with respect to their critical temperatures and pressures. T P TR and PR Tcr Pcr where Pcr and Tcr are the critical pressure and temperature, respectively.
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. This is known as the principle of corresponding states.
These charts show the conditions for which Z = 1 and the gas behaves as an ideal gas: 1. 2. PR << 1 or P << Pcr TR > 2 or T > 2Tcr
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
Tcr = 126.2 K, Pcr = 3.39 MPa R = 0.2968 kJ/kg-K T 300 K TR 2.38 Tcr 126.2 K
PR
P 8.0 MPa 2.36 Pcr 3.39 MPa
Since T > 2Tcr and P < 10Pcr, we use the ideal gas equation of state
Pv RT v RT P 0.2968 kJ (300 K ) 3 m MPa kg K 8.0 MPa 103 kJ
m3 0.01113 kg
Nitrogen is clearly an ideal gas at this state.
8
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.
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 25C 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 T3
T2
2
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,
T3 T1 T3 T1 T3
P3 V3 P 1 V1 2P 2 1 V1 / 3 T1 P V1 3 1
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2 (25 273) K 198.7 K 74.3C 3
