Equations of State

For non ideal gases we will need a relationship for work and this requires a
relationship for PVT (an equation of state):
What are the assumptions for an Ideal Gas and their interactions ?
How will real gases differ ?
Q and T (above)
V for T and P
Many first approximations start with a compressibility factor, Z:
PV = nZRT where for one mole: Z =PV = function of ?
RT
Z = 1 + B'P + C'P + D'T +... or = 1B++ C2 + . . .
V V
0
1
or Z = F(Tr, Pr); one example=Z + Z ; for gas (tables)
or [Virial] PV = a + bP + cP2 +...
or van der Waals
P = RT - a2 ; a and b for gas (tables)
V-b V
Van der Waals equation
P + a V- b = R T
2
V
P =

RT
a
V - b V2
Parameters for the Van der Waals Equation

O2

a, Pa-m6/mol2
0.1381

b, m3/mol x 103
3.184

N2
H2O

0.1368
0.5542

3.864
3.051

CH4

0.2303

4.306

CO
CO2

0.1473
0.3658

3.951
4.286

NH3
H2

0.4253
0.0248

3.737
2.660

He

0.00346

2.376

Gas

Redlich-Kwong Equation
P =

RT a
1/2
V - b T VV + b

Peng-Robinson Equation
P =

aT
RT V - b V V + b + bV - b\

Generalized Cubic Equation

P =

RT
V- b

V -
2

V + bV

- V +

Note that if Z = PV/NRT, the equation can be written as a cubic eqation in Z

Z3 + Z 2 + Z + = 0

Solution for Selected Equations of State

The usual cubic equations of state can all be expressed in the same form:

Z3 + Z 2 + Z + = 0
For the van der Waals, Redlich-Kwong, and Peng-Robinson equations, the Table below gives the relationship between
the paramers , , and the parameters for the respective equations of state.

van der Waals

-1-B
A

Redlich-Kwong
-1
A - B - B2

-AB

-AB

Peng-Robinson
-1+B
A - 3B2 -2B
-AB + B2 + B3

where

Z = P V and B = P b
RT
RT
A =

aP
for van der Waals and Peng-Robinson
RT2
A =

aP
for Redlich-Kwong
RT2 T

Peng-Robinson Equation of State

The cubic form of the Peng-Robinson equation is the following

Z3 + Z 2 + Z + = 0
noting that the definitions of Z , A, and B are

Z =PV
RT
Using the generalized form for the parameters in the Peng-Robinson Equation, we obtain a simplified set of parameters
to use in the equation

A =

0.45724Pr
Tr2

Tr

B = 0.07780

PR
TR

with other parameters appropriately defined

Tr = 1 + 1 -

Tr

= 0.37464 + 1.5422
- 0.26992 2

So that the parameters in the cubic form are given by

= - 1 + 0.07780

0.45724Pr

= 0.07780

Tr

Tr - 2 0.07780

Pr
Tr

Pr
Tr
- 3 0.07780

Pr 0.45724Pr
Pr
Tr + 0.07780
2
Tr
Tr
Tr

Pr
Tr

+ 0.07780

Pr
Tr

To relate the two types of Representation:

A RT
a
P = RT where b = BRT & a =
v - b v v+b +b v-b
P
P
A RT

P=

RT P
BRT
BRT
BRT
vv v+
+
v-BRT
P

gathering P in denominator
A RT

P=

RTP P
Pv - BRT v Pv+BRT +BRT Pv-BRT
2
P
P

Multiply byV/RT and elim. /P in second term:

A RT *Pv
Pv =
Pv
RT Pv - BRT Pv Pv+BRT +BRT Pv-BRT
Sub. for Z; top & bottom by 1/RT; top & bottom by 1/RTPV
A
A
Z= Z = Z 2
Pv+
BRT
PvBRT
B
Z-B
Z
+B
Z +B +B - B
RT
Pv
Z
Z
AZ
A
1 = 1 Z=
- 2
Z - B Z + 2BZ -B2
Z - B Z2 + 2BZ -B2
2

0 = Z - B Z + 2BZ -B -Z - 2BZ +B + A Z - B
0 = Z 3 + Z 2 -B+ 2B -1 + Z -B2-2B2 +A-2B + B3 + B2 -AB
0 = Z3 + Z2 B -1 + Z A -3B2-2B + B3 + B2-AB
0 = Z3 + Z2 +

Z + :where = B -1 ; = A -3B -2B ; = B + B -AB

One approach to the use of the Peng-Robinson:

using , Tc and Pc
define

= 0.37464 + 1.54226
- 0.269922
1/2
= 1 + 1-Tr
2

R Tc
a = 0.45724
Pc

RTc
Pc
a
P = RT v - b v(v+b) +b(v-b)
b = 0.0778

to iterate multiply by (v-b)/P and rearrange:

a
RT
P
v=b+
P v v+b + b
v-b
a
P
calculate v+b then v v+b + b then
v-b
v-b
v v+b + b
v-b
This then gives v, the next guess
Proceed until v does not vary

The solution of a Cubic Equation

If a cubic equation is stated as below :

Z3 + Z 2 + Z + = 0,

its roots can be obtained if we examine the following forms :

q=

1
1
- 2
3
9

r =
;

1
1 3
- 3

6
27

If q3 + r2 > 0 ,

there will be one real root and a pair of complex conjugate roots.

If q3 + r2 = 0 ,

all roots are real and at least two will be equal.

If q3 + r2 < 0 ,

all roots are real ( irreducible case, i.e., no analytical solution)

The roots can be expressed using the following definitions :

s1 = r + 3* q3 + r2

1
3

s2 = r - 3 q3 + r2

1
3

and the roots are :

Z1 = s1 + s2 -
3
Z2 = -

s1 + s2
2

- + i 3 s1 - s2
3
2

Z3 = -

s1 + s2
2

- i 3 s1 - s2
3
2

You should note some interesting and useful properties of the roots.

Z1 + Z2 + Z3

= -

Z1Z2 + Z1Z3 + Z2Z3 =

Z1Z2Z3 = -