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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

RT = function of

Z = 1 + B'P + C'P + D'T +

B

or = 1 + +

V

C

V

2

+

Z = F(Tr, Pr); one example=Z 0 + w Z 1 ; w for gas (tables

or

or [Virial] PV = a + bP + cP 2 +

or van der Waals

P =

RT

V - b -

a

V

2 ; a and b for gas (table

Van der Waals equation P + V - b = a 2 V R T
Van der Waals equation
P
+
V -
b
=
a 2
V
R T
a
P
=
-
V -
b
V 2

R T

Parameters for the Van der Waals Equation

Gas

a, Pa-m 6 /mol 2

b, m 3 /mol x 10 3

O

2

0.1381

3.184

N

2

0.1368

3.864

H 2 O

0.5542

3.051

CH 4

0.2303

4.306

CO

0.1473

3.951

CO

2

0.3658

4.286

NH

3

0.4253

3.737

H 2

0.0248

2.660

He

0.00346

2.376

Redlich-Kwong Equation

R T a P = - V - b T 1/2 V V + b
R T
a
P =
-
V -
b
T 1/2 V V
+
b
Peng-Robinson Equation
R T
a T
P =
-
V
-
b
V V
+
b
+
bV
-
b \
Generalized Cubic Equation
R T
V
-
h q
P =
-
V -
b
V
+
bV 2
-
dV
+
e

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

Z 3

+ a Z 2

+ b Z

+ g

=

0

Solution for Selected Equations of State

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

Z 3

+

a

Z 2

+

b

Z

+

g

=

0

For the van der Waals, Redlich-Kwong, and Peng-Robinson equations, the Table below gives the relationship between the paramers a, b, g and the parameters for the respective equations of state.

 

van der Waals

Redlich-Kwong

Peng-Robinson

a

- 1 - B

- 1

- 1 + B

b

A

A - B - B 2 -AB

A - 3B 2 -2B

g

-AB

-AB + B 2 + B 3

where

A

=

Z

aP

R T 2
R
T 2

A

=

= P V

R T

and

B

=

P b

R T

for van der Waals and Peng-Robinson

a P

R T 2 T
R T 2
T

for Redlich-Kwong

Peng-Robinson Equation of State

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

Z 3

+

a

Z 2

+

b

Z

+

g

=

0

noting that the definitions of Z , A, and B are

Z

= P V

R T

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

0.45724P r s T r 2 T r
0.45724P r
s T r
2
T r

P R

T R

A

=

B = 0.07780 - T r
B = 0.07780
-
T r

-

with other parameters appropriately defined

s

T r

=

+

- 1

1

+k 1

k = 0.37464

So that the parameters in the cubic form are given by

b

=

a = 0.45724P r s T r 2 T r
a
=
0.45724P r
s T r
2
T r

-

1.5422w

0.26992w 2

P r

T r

+ 0.07780

2

2 P P r r 0.07780 - 3 0.07780 T T r r
2
P
P
r
r
0.07780
- 3 0.07780
T
T
r
r

g

=

P r 0.45724P r 0.07780 s T r 2 T r T r
P r
0.45724P r
0.07780
s T r
2
T r
T r

+

+2 P P r r 0.07780 - 3 0.07780 T T r r g = P 2 P P r r 0.07780 - 3 0.07780 T T r r g = P

2 P r 0.07780 T r
2
P
r
0.07780
T
r

To relate the two types of Representation:

P =

+b v-b where b = BRT & a = A RT 2

a

P

- b where b = B R T & a = A R T 2 a

P

RT

v - b - v v+b
v - b -
v v+b

P =

RT

v - BRT

P

gathering P in denominator

P =

RTP

Pv - BRT -

A RT 2 - P v v+ BRT + BRT v- BRT P P P
A RT 2
-
P
v v+ BRT
+ BRT v- BRT
P
P
P
A RT 2
P
v
P Pv+BRT + BRT
Pv-BRT
2
P

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

Pv

RT =

Pv

-

Pv - BRT

A RT *Pv Pv Pv+BRT +BRT Pv-BRT
A RT *Pv
Pv Pv+BRT +BRT Pv-BRT

Sub. for Z; top & bottom by 1/RT; top & bottom by 1/RTPV

0

Z =

Z

Z - B -

 

A

Pv+BRT

+B Pv-BRT

=

Z =

RT

Z

AZ

Z - B -

Z 2 + 2BZ -B 2

Pv

\

1 =

Z

A

Z -

B -

Z +B

+B - B 2

 

Z

1

A

Z - B -

Z 2 + 2BZ -B 2

0 =

0 =

Z - B

Z 1 A Z - B - Z 2 + 2BZ -B 2 0 = 0

Z 2 + 2BZ -B 2

-Z 2 - 2BZ +B 2 + A Z - B

Z 3 + Z 2 -B+ 2B -1 + Z -B 2 -2B 2 +A-2B + B 3 + B 2 -AB

0

= Z 3 +

Z 2 B -1

+ Z A -3B 2 -2B + B 3 + B 2 -AB

= Z 3 + Z 2 a

+

Z b

+ g

:wherea

= B -1 ; b

= A -3B 2 -2B ; g = B 3 + B 2 -AB

One approach to the use of the Peng-Robinson:

define

using w , Tc and Pc

k = 0.37464 + 1.54226w - 0.26992w 2

P =

1/2 = 1 +k 1-T r 2 a = a 0.45724 R 2 T c
1/2
= 1 +k
1-T r
2
a = a
0.45724 R 2 T c
P
c
b = 0.0778 RT c
P c
RT
a
-

v - b

v(v+b) +b(v-b)

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

v-b
v-b

calculate v+b

a P P v v+b +b v-b a P v v+b +b v-b
a P
P v v+b
+b
v-b
a P
v v+b
+b
v-b

v = b + RT -

P P v v+b +b v-b a P v v+b +b v-b v = b +

then v v+b v-b

+bthen

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 :

Z 3

+

a

Z 2

+

b

Z

+

g

=

0

,

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

1

q = 3 b

-

1 9 a 2

;

r

1 a
1
a

= 6

b

-

3g

-

1

27

a 3

If q 3 + r 2

>

0 ,

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

If q 3 + r 2

=

0 ,

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

If q 3 + r 2

<

0 ,

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

The roots can be expressed using the following definitions :

s 1

=

r

+ 3*

and the roots are :

q 3 + r 2
q 3
+
r 2

1

3 ;

Z 2

Z 3

=

=

= r - 3 q 3 + r 2 s 2 a Z 1 =
=
r
-
3
q 3
+
r 2
s 2
a
Z 1
=
s 1
+
s 2
-
3
3
+ i
s 1
-
s 2
2
+
s 2
a
3
- s 1
-
- i
s 1
-
s 2
2 3
2

1

3

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

Z 1

+

Z 2 +

Z 3

=

-a

;

Z 1 Z 2 Z 3

Z 1 Z 2

=

-g

+ Z 1 Z 3

+ Z 2 Z 3

=

b