Chemical and Phase Equilibria

H82CPE
Dr Ianatul Khoiroh
Room: DB02d, D building
Email: Ianatul.Khoiroh@nottingham.edu.my
Phone: +6(03) 8924 8361
Office Hours: Open door policy. When I am there, I am usually available.
To guarantee availability, make an appointment.

Equation of State (EoS)

for PVT Properties

Three Parameters CSP (Generalized EoS)

The law of corresponding state of Z is called two-parameters CSP,
because they require use of the two reducing parameters Tc and Pc.
Although these correlations are very nearly exact for simple fluids
(argon, krypton, and xenon), systematic deviations are observed
for more complex fluids
Appreciable improvement results from introducing a third
corresponding-state parameter (in addition to Tc and Pc),
characteristic of molecular structure: acentric factor,

1.0 log Prsat Tr 0.7

Lecture 1

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Three Parameters CSP (Generalized EoS)

The compressibility factor is given as:

Z Z ( 0 ) Z 1
Where Z(0) and Z(1) are generalized functions of reduced
temperature and pressure

( 0)

(1)

Lecture 1

Pr
1 B
Tr
o

Pr
B
Tr
1

( 0)

(1)

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0.422
0.083 1.6
Tr
0.172
0.139 4.2
Tr

Next: Virial EoS

Chapter 7

H81HMT

Virial EoS
Virial: derived from the latin word for force
The compressibility is expressed as an infinite series expansion in either
the density (V-1) or the pressure.

PV
B2V T B3V T B4V T
Z
1

...
2
3
RT
V
V
V
Z

PV
1 B2 P T P B3 P T P 2 B4 P T P 3 ...
RT

BnX are virial coefficients (B2V is a second virial coefficient)

Note that at very low pressures or densities (large molar volumes)
Z 1 which reflecting ideal behavior
Lecture 1

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Virial EoS
The 2nd Virial Coefficient
At low pressure:

Z 1 B2 P (T ) P
Z is linear in B2P

Slope(T) = B2P(T)

Through manipulation of the

two virial expansions, one can
also show that

B2V (T ) RTB2 P (T )

Lecture 1

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10

Virial EoS
Virial terms for Argon at 298 K

Unit of B2V is volume/mol

Lecture 1

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11

Virial EoS
What does B2V mean ?
At low pressure:

Z 1 B2 P (T ) P

RT
or V
RTB2 P T
P
Videal

So: V B2V T Videal

B2V(T)
or

B2V T V Videal

B2V is the difference between the observed molar volume and the
ideal gas molar volume

Lecture 1

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12

Virial EoS
B2V for various substances

B2V T V Videal

Again: attractive forces dominate at low T, repulsive at high T

Lecture 1

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13

Class Problem
1. What is the molar volume of N2(g) at 600 K and 600 bar
according to:
(a) Ideal gas law
(b) Generalized EoS
(c) The virial equation
2. Derive the relationships between two types of virial coefficients.

Lecture 1

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14

To use most of EoS, critical and and

other properties of fluids are needed.
What if such data are not available?

Estimation Method
Method of Joback
Method of Constaninou and Gani (CG)
Method of Wilson and Jasperson
Method of Marrero and Pardillo
etc

Chapter 7

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15

Joback Group Contribution

Critical Properties Estimation

Tc ( K ) Tb 0.584 0.965 N k (tck ) N k (tck )

k
k

Pc (bar ) 0.113 0.0032 N atoms N k pck

k

Vc (cm 3 mol 1 ) 17.5 N k vck

k

where the contributions are indicated as tck, pck, and vck. Nk is

the number of appearance.
Joback group contribution constants can be found from the
following link:
Lecture 1

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16

Joback Group Contribution

Group contributions:
Natoms= 9
Group 1: -CH3
Group 2: -CH2Group 3: -OH

Group k

Nk

Nk (tck)

-CH3

1 x (0.0141)

1 x (0.0012)

1 x (65)

-CH2-

1 x (0.0189)

1 x (0.0000)

1 x (56)

-OH

1 x (0.0741)

1 x (0.0112)

1 x (28)

0.0124

Nk (pck)

0.0124

Nk (vck)

149

Lecture 1

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17

Joback Group Contribution

Group k

Nk

Nk (tck)

-CH3

1 x (0.0141)

1 x (0.0012)

1 x (65)

-CH2-

1 x (0.0189)

1 x (0.0000)

1 x (56)

-OH

1 x (0.0741)

1 x (0.0112)

1 x (28)

0.0124

Nk (pck)

Nk (vck)

0.0124

149

Tb= 351.80 K (databank)

2 1

Tc ( K ) 351.80 0.584 0.9650.0124 0.0124

590.45 K

Pc (bar ) 0.113 0.0032(9) (0.0124) 59.72bar

2

Vc (cm 3mol 1 ) 17.5 (149) 166.5cm 3mol 1

Lecture 1

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18

Class Problem
3. Estimate critical properties Tc, Pc, and Vc of 2-propanol and
compare your results from NIST Webbook and Property Data
Bank*.

*The properties of gases and liquids

Lecture 1

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19