Professional Documents
Culture Documents
2005-9-23 66
1.5 Real Gases and the Virial Equation
The Virial Equation: (Virial: derived from the Latin word for force):
PVm B C
Z= = 1+ + 2 +L
RT Vm Vm
For over wider range of P, add more terms in power series (1/Vm).
B and C: the second and third virial coefficients, and both are
temperature dependent, but not on the pressure.
2005-9-23 67
Table 1.1 Second virial Coefficients, B
H2 14.1 350
He 11.8 121
N2 -4.5 1100
O2 -16.1 1200
Ar -15.8 1160
CO -8.6 1550
2005-9-23 68
1.5 Real Gases and the Virial Equation
2005-9-23 69
1.5 Real Gases and the Virial Equation
273 K 600 K
Ar -21.7 11.9
H2 13.7
He 12.0 10.4
N2 -10.5 21.7
O2 -22.0 12.9
Ne 10.4 13.8
Xe -153.7 -19.6
2005-9-23 70
1.5 Real Gases and the Virial Equation
Example Comparison of the ideal gas law with the virial equation
What is the molar volume of N2(g) at 600 K and 600 bar according to
(a) the ideal gas law and (b) the virial equation?
Answer: (a) The virial coefficient B of N2(g) at 600 K is 0.0217 L mol-1
RT
=Vm [ideal] =
(8.3145x10-2L bar K -1 mol-1) (600K)
= 8.3145x10-2 L mol-1
P 600bar
(b) Z = 1+
BP
= 1+
(0.0217 L mol-1)
= 1.261
RT (8.3145x10-2 L mol-1)
ZRT
Vm = = (1.261) (8.3145x10 2L mol-1) = 0.1048 L mol1
P
2005-9-23 71
1.5 Real Gases and the Virial Equation
2005-9-23 72
1.5 Real Gases and the Virial Equation
RT B BRT + C (RT
' '
)
2
Z = 1 + B P + C P + K = 1 + B
' ' 2 '
+ +K
Vm Vm2
B = B RT
' B ' = B / RT
C = BB RT + C (RT )
' ' 2 C B 2
C' =
(RT ) 2
2005-9-23 73
1.5 Real Gases and the Virial Equation
Compression Factor Z
The variation of the compression
factor, Z = PVm RT with pressure
for several gases at 0 C. A
perfect gas has Z = 1 at all
pressures. Notice that, although
the curves approach 1 as p 0,
they do so with different slopes.
2005-9-23 74
Boyle Temperature
Boyle Temperature TB
A plot of Z vs. P with a slope of dZ /dP :
dZ/dP = B + 2CP + ... (The slope is B at P = 0).
Although for a real gas Z ~ 1 at P ~ 0, the slope of Z against P does
not approach zero.
The properties of real gas may not always coincide with the perfect
gas values at low P.
There may be a temperature at which Z ~ 1 with zero slope B = 0
at P ~ 0, this temperature is called the Boyle temperature, TB .
At the Boyle temperature TB , the properties of real gas do coincide
with the perfect gas values as P ~ 0.
Since the second virial coeff. B vanished and the third virial coeff. C
and higher terms are negligibly small, then PVm ~ RTB over a more
extended range of P than at other temperature.
2005-9-23 75
1.5 Real Gases and the Virial Equation
Boyle Temperature TB
The compression factor Z
approaches 1 at low
pressures, but does so with
different slopes. For a perfect
gas, the slope is zero, but
real gases may have either
positive or negative slopes,
and the slope may vary with
temperature. At the Boyle
temperature, the slope is zero
and the gas behaves perfectly
over a wider range of
conditions than at other
temperatures.
2005-9-23 76
1.5 Real Gases and the Virial Equation
Fig. 1.10
At the Boyle temperature
(B=0), a gas behaves nearly
ideally over a range of
pressures.
2005-9-23 77
Table 1.2 Critical Constants and Boyle Temperatures
2005-9-23 78
1.6 P- V -T Surface for a one-component system
P, V ,T Surface Plot
A region of the P, V ,T
surface of a fixed amount
of perfect gas. The points
forming the surface
represent the only states
of the gas that can exist.
2005-9-23 79
1.6 P- V -T Surface for a one-component system
Paths on Surface
Sections through the surface
at constant temperature give
the isotherms, and the
isobars shown in here too.
2005-9-23 80
1.6 P- V -T Surface for a one-component system
Fig 1.11
P-V-T surface
for a one-
component
system that
contracts on
freezing.
2005-9-23 81
1.7 Critical Phenomena
2005-9-23 82
1.7 Critical Phenomena
2005-9-23 83
1.7 Critical Phenomena
2005-9-23 84
1.8 The van der Waals Equation
2005-9-23 85
1.8 The van der Waals Equation
RT a
P = 2
Vm b Vm
2005-9-23 86
Table 1.3 van der Waals Constants
Ar 1.337 3.20
He 0.0341 2.38
Xe 4.137 5.16
a and b : van der Waals coefficients
The VDW coefficients a and b are found by fitting the
calculate curves to experimental curves. They are
characteristic of each gas but independent of the
temperature.
2005-9-23 87
1.8 The van der Waals Equation
Van der Waals modified the ideal gas law by taking account two
effects: a). intermolecular forces, and b). molecular size.
Only free volume follows ideal gas law; p above ideal value by
size effect, P = RT / (Vm b),
2005-9-23 89
1.8 The van der Waals Equation
2005-9-23 90
1.8 The van der Waals Equation
2005-9-23 91
1.8 The van der Waals Equation
RT 2 a ab
VM b +
3 V +
M M
V =0
P P P
2005-9-23 92
1.8 The van der Waals Equation
3 b + RT 2 a ab
VM
V +
M M
V =0
P P P
2005-9-23 93
1.8 The van der Waals Equation
2005-9-23 94
1.8 The van der Waals Equation
dx dx x=0
2005-9-23 95
1.8 The van der Waals Equation
2
a 1 b
Z = 1+ b - + + L
RT Vm Vm
the second virial coefficient B = b a/RT, C = b 2
2005-9-23 96
1.8 The van der Waals Equation
2005-9-23 97
1.8 The van der Waals Equation
let (1 / RT) =
Z = 1 + (b a/RT) P + a 3 (2b a ) P 2 + ...
(dZ / dP ) = (b a ) + 2 a 3 (2b a ) P + ...
At P = 0, the initial slope
( Z/ P )p=0 = (b a )
= (1 / RT) (b a/RT)
= b (1/RT) a (1/RT)2
if bRT < a, attractive force dominated, (negative slope)
if bRT > a, repulsive force dominated, (positive slope)
at Boyle temperature, the second term vanished, B = 0;
bRT = a, then TB = a/bR
the Boyle temperature is relate to the VDW coefficients.
2005-9-23 98
1.8 The van der Waals Equation
Exercise
Given the van der Waals constants for ethane gas as a = 5.562 L2 bar/mol2, b = 0.06380
L/mol, for 10.0 mol of ethane at 300 K and under 30 bar,
(a) find the second virial coefficient B at this temperature.
(b) calculate the compressibility factor Z from the first two terms.
(c) estimate the approximate molar volume from Z.
(d) what is its Boyle temperature TB?
Ans:
(a) B = b - a/RT
= 0.06380 L/mol - [5.562 L2 bar/mol2 /(0.0831451 L-bar/K-mol * 300 K)]
= -0.159 L/mol
(b) Z = 1 + B (p/RT) + ...
= 1 + (-0.159 L/mol) [30 bar / (300 K*0.0831451 L-bar/K-mol)]= 0.81
(c) V/n = ZRT/p
= (0.81) (0.0831451 L-bar/K-mol) (300 K) / 30 bar = 0.67 L/ mol
(d) TB = a/bR
= 5.562 L2 bar/mol2 / (0.06380 L/mol * 0.0831451 L-bar/K-mol)
= 1049 K
2005-9-23 99
1.8 The van der Waals Equation
vdw Isotherms
Van der Waals isotherms at
several values of T/Tc . The
van der Waals loops are
normally replaced by
horizontal straight lines.
The critical isotherm is the
isotherm for T/Tc = 1.
For T < TC, the calculate
isotherms oscillates from
min max and converges
as T TC then coincide at
T = TC with flat inflection.
2005-9-23 100
1.8 The van der Waals Equation
p RTc 2a
= + 3 =0
V T =Tc (V c b )
2
Vc
2P 2 RTc 6a
= 4 =0
2
(
V T = Tc V c b )
3
Vc
2005-9-23 101
1.8 The van der Waals Equation
2005-9-23 102
1.8 The van der Waals Equation
p RTC 2a 27 R 2Tc2 9
= + 3 =0 a = = RT 2V
c
V T V C b
c
( )
2
VC
64 Pc 8 c
2 p 2RTC 6a RT V c
= 4 =0 b= c
=
V 2
(
Tc VC b
3
VC ) 8 Pc 3
2005-9-23 103
1.8 The van der Waals Equation
Derive the expression for the molar volume (Vc) temperature (Tc)
and pressure (Pc) at the critical point in terms of the van der Waals
constants.
Answer:
8a 8a
27R Tc
2 2
9 T = =
a= = RTc V c
2
c
9R V 27Rb
64Pc 8 c
V c = 3b
RTc V c RTc a
b= = Pc = =
8Pc 3 8 Pc 27b 2
2005-9-23 104
1.8 The van der Waals Equation
Critical Constants:
Vc =3b
a PcVc 3
Pc = Z c = =
27b 2
RTc 8
8a
Tc =
27Rb
2005-9-23 105
1.8 The van der Waals Equation
Example 1.9 Calculation of the molar volume using the VDW equation.
What is the molar volume of ethane at 350 K and 70 bar according
to (a) the ideal gas law and (b) the van der Waals equation?
(a = 5.562 L2 bar / mol2 and b = 0.0638 L / mol for C2H6)
Ans:
a) Vm=RT/P=(0.083145 L bar/K mol)(350 K)(70 bar)=0.416 L/mol
b) VDW equation: P = RT a2
V b V
m m
This yields Vm = 0.23 L/mol (Comparing with the real root: 0.2297
L/ mol)
2005-9-23 106
Thermodynamics: State of a Gas
Pr = P Vm Tr = T
Vr =
Pc Vc Tc
2005-9-23 107