CHAPTER 8

Real gases

REAL GASES
Ideal gas:

P Vm = RT

P Vm Z= RT

Z=1

Z = compressibility factor (not isothermal compressibility!)

What is Z for a real gas? Z can be either > 1 or < 1 Z 1 as P 0 Z 1 as T

REAL GASES
Z can be either > 1 or < 1 Z 1 as P 0 Z 1 as T

What determines this behavior? molecular interactions

repulsive if the molecules come close available volume is less than V

attractive at larger distances pressure is lower than P

REAL GASES
Van der Waals equation:

a P+ 2 Vm P = RT Vm

(Vm

b) = RT a 2 Vm

RT b

Redlich-Kwong:

P =

Vm

a Vm (Vm + b)T 1/2

Virial equation of state: P Vm

B (T ) C (T ) D(T ) = RT 1 + + + + . . . 2 3 Vm Vm Vm
second virial coefficient third virial coefficient fourth virial coefficient

REAL GASES
Van der Waals equation:

a P+ 2 Vm P = RT Vm

(Vm

b) = RT a 2 Vm

RT b

Redlich-Kwong:

P =

Vm

a Vm (Vm + b)T 1/2

Virial equation of state: P Vm

B (T ) C (T ) D(T ) = RT 1 + + + + . . . 2 3 Vm Vm Vm
2 3

or

P Vm = RT 1 + B (T )P + C (T )P D (T )P + . . .

REAL GASES
Virial equation of state: P Vm

B (T ) C (T ) D(T ) = RT 1 + + + + ... 2 3 Vm Vm Vm

Calculating B(T) from the van der Waals equation

P =

RT Vm b

a 2 Vm

P Vm Vm Z= = RT Vm b = 2 1 3 1 b/Vm

a RT Vm a RT Vm

1 =1+ b/Vm

b Vm

b Vm

b Vm

+ ...

REAL GASES
Virial equation of state: P Vm

B (T ) C (T ) D(T ) = RT 1 + + + + ... 2 3 Vm Vm Vm

Calculating B(T) from the van der Waals equation

P =

RT Vm b

a 2 Vm

P Vm Vm Z= = RT Vm b = 1 1 b/Vm

a RT Vm a RT Vm

P Vm =1+ b RT

2 3 1 a b b + + + ... RT Vm Vm Vm B (T ) C (T ) = b
2

D(T ) = b

REAL GASES
P Vm =1+ b RT 2 3 1 a b b + + + ... RT Vm Vm Vm
when Vm >> b

when B = 0, the gas looks ideal

Gas mixtures The situation is much more complicated because the virial coefficients of a & b also depend on the mole fractions

REAL GASES

liquid and gas coexist in any proportion from pure liquid to pure gas liquid or gas = fluid

compress a lot Vm decreases a little

compress a little Vm decreases a lot

gas & liquid coexist

REAL GASES
Tc

liquid and gas coexist in any proportion from pure liquid to pure gas liquid or gas = fluid

all liquid mixture

all gas

At Tc liquid and gas coexistence goes away The remnant point of inflection: Pc, Tc, Vc

REAL GASES
Tc

all liquid mixture What makes a gas vs. a liquid? gas: kinetic energy wins liquid: potential energy wins

all gas

above Tc: no clear winner no sudden change in density

REAL GASES
Tc How to calculate the parameters of the equation of state using the critical data

Pc , T c , V c

a, b

van der Waals equation

Pc =

RTc Vm,c
RTc

a b
2 Vm,c

P Vm
at the critical point

=0
T

(Vm,c 2RTc (Vm,c

2a + 2 =0 2 b) Vm,c 6a + 4 =0 3 b) Vm,c

P 2 Vm

=0
T

REAL GASES
Tc How to calculate the parameters of the equation of state using the critical data

Pc , T c , V c

a, b

van der Waals equation

Pc =

RTc Vm,c b

a
2 Vm,c

Vm,c = 3b

8a Tc = 27Rb RTc b= 8 Pc

a Pc = 27b2
2 R 2 Tc a = 27 64Pc

REAL GASES
Tc Compressibility factor at the critical point

Pc Vm,c Zc = RTc Zc = 1 Zc = 0.25 0.30 3 Zc = = 0.375 8 1 Zc = = 0.333 3

ideal gases

real gases

vdw gases

R-K gases

REAL GASES
Tc vdW equation

The vdW and R-K equations as well as the virial expansion are all continuous and have continuous derivatives, and were really designed for real gases assuming the existence of small deviations from ideality. Real gas isotherms in the liquid-gas coexistence region dont behave this way!

P Vm

= discontinuous
T

REAL GASES
Tc vdW equation

metastable superheated liquid

P Vm

physically impossible

>0
T

metastable supercooled vapor

REAL GASES
The vdW and R-K equations as well as the virial expansion cannot describe the liquid-gas transition region correctly.

The vdW equation is not good for liquids while the R-K equation works in some cases

The equations of state can be used to predict the molar volumes of both liquid and gas in equilibrium and the vapor pressure

REAL GASES
The equations of state can be used to predict the molar volumes of both liquid and gas in equilibrium and the vapor pressure as well as Hvap

=
l
equation of state must hold

equation of state must hold

P =

RT Vm b

a 2 Vm

REAL GASES
The equations of state can be used to predict the molar volumes of both liquid and gas in equilibrium and the vapor pressure as well as Hvap

=
l
but

= G m = Am + P V m
g P (Vm
but

l Vm )

g (Am

l Am )

dAm =
g Am l Am

Sm dT
g P (Vm

P dVm
l Vm )

g Vm l Vm

Peos dVm =

REAL GASES
The equations of state can be used to predict the molar volumes of both liquid and gas in equilibrium and the vapor pressure as well as Hvap

Ag m

Al m =

g Vm l Vm

Peos dVm = RT
l Vm

g P (Vm

l Vm )

P =

a 2 l Vm a

P =
Maxwells equal areas

RT
g Vm

g2 Vm

REAL GASES
The critical state: Pc, Tc, Vc

At Tc

P Vm

=0
T

Vm P Vm P

=
T

1 Vm

From experiments

P T

>0
Vm 2

CP.m = CV,m + T Vm

REAL GASES
Law of corresponding states If the equations of state of real gases depend on at most 3 parameters that may differ from gas to gas (for the vdW and R-K equations there are only two parameters), then knowing Pc, Tc, and Vm,c would fix everything about the behavior.

Reduced variables

P Pr = Pc

T Tr = Tc

Vm,r

Vm = Vm,c

The equations of state for all gases look exactly the same when written in terms of these reduced variables

Vm,r = f (Pr , Tr )
vdW equation:

Pr +

3
2 Vm,r

Vm,r

1 3

8 = Tr 3

REAL GASES
Differences between ideal and real gases affect not only the equation of state but all thermodynamic properties (e.g, H, G, A, S...)

Real gas at T and Po

H = Hideal
T = constant

Hreal

Ideal gas at T and Po

Ha
Real gas at T and P = 0 bar

Hb

Hc
Ideal gas at T and P = 0 bar

ideal Hm

real Hm (T, P )

Vm T

Vm dP
P