CHEMICAL ENGINEERING THERMODYNAMICS

3. VLE of Pure Fluid

Professor Sheng Dai

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What Have We Learnt?

• Vapor-liquid equilibrium is an important topic for Chemical
Engineers
• In the two phase region of VLE, H, V, S, U can be calculated
using the lever rule from the steam table
• In the two phase region of VLE, T, P, G, GR, f and f keep
constant
• At the VLE, vapour pressure is Psat, which is a function of T but
not of V, three equations to correlate T and Psat
• Introduction of fugacity f and fugacity coefficients f, their
relations with GR and P
• Four methods to calculate fugacity and fugacity coefficient
R
V f
f = P eG / RT
= fP d ln f =
RT
dP (cons. T) G = G 0 + RT ln
f0
G R = RT ln f
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Two Steam Tables

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Two Steam Tables

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Question 1 Steam Tables and States

A 12 m3 pressurized vessel contains 200 kg of steam

at 40 bar. What is the temperature?

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Solution
12 m 3
V= = 0.06 m 3 /kg
200 kg
From stable tables with P = 40 bar and V = 0.06 m3/kg, we obtain
T1 = 300 oC V1 = 0.0589 m3/kg
T2 = 350 oC V2 = 0.0665 m3/kg

f2 - f1
f = f1 + ( x - x1 )
x2 - x1
350 - 300
T = 300 + ( 0.06 - 0.0589)
0.0589 - 0.0665
T = 307.2 0 C

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Question 2 Lever Rule and Quality

An additional 170 kg of steam is added to the tank of

the Question 1. If the final pressure is 50 bar,
determine the temperature and phase of the contents
of the tank.

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Solution
From steam table
P = 50 bar; T = 263.94 oC: VL = 0.0012864 m3/kg; VV = 0.039446
m3/kg
12 m 3
V= = 0.03243 m 3 /kg
( 200 +170 ) kg
0039446 - 0.03243
V - VL V -V xL = = 0.184 = 18.4%
xV = , xL = V 0.039446 - 0.0012864
VV - VL VV - VL
xV = (1- 0.184 ) = 0.816 = 81.6%

Therefore, the quality of the steam in the tank is 81.6%

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Question 3 Saturated Liquid

Calculate the fugacity and fugacity coefficient of

saturated liquid water at 25oC.

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Solution
The fugacity of the saturated liquid is equal to the saturated vapour

fV = f L = f sat P sat
The saturation pressure at 25oC is 0.03166 bar and at such low
pressure the vapour phase is ideal, that is ϕsat ≈ 1. Therefore, the
fugacity is equal to the saturation pressure.

fV = f L » 0.03166 bar
and the fugacity coefficient is 1.

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Question 4 Poynting Factor

Calculate the fugacity and fugacity coefficient of water

at 25 oC, 100 bar, using data from the steam tables.

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Solution
Under these conditions the water is a compressed liquid, the
Poynting equation can be used. The liquid volume at 25 oC is VL =
1.003 cm3/g = 18 × 10-6 m3/mol
At 25 oC, the
æ P - P sat ö low pressure
f = f sat P sat exp ç VL ÷
è RT ø gives the value
æ (100 - 0.03166)105 ö of 1 for fugacity
f = f sat P sat exp ç
çè (8.314) ( 298) (
18x10-6 )÷÷ø coefficients

f = f sat P sat (1.075) = (1) ( 0.03166) (1.075) = 0.034 bar

f 0.034 bar
The fugacity coefficient is f= = = 3.4 ´ 10-4
P 100 bar

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Question 5 Fugacity of Steam using Z

Estimate the fugacity of steam at 300 oC, 70 bar if the

density of steam at this state is 33.898 kg/m3.

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Solution
1 1
V = = = 0.0295 m 3 /kg = 5.314 x 10-4 m3 /mol
r 33.998

Z =
PV
=
( )(
70x105 5.314 x 10-4 )
= 0.780685
RT (8.314) (573.15)

ln f = 0.780685-1 = -0.219315 Þ f = 0.803

( )( )
f = f P = 0.803 70 bar = 56.2 bar

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 Pig = 70 bar

Pact = 56.2 bar

(Eq. 7.8)

V = 5.314 x 10-4 m3/mol

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Question 6 Generalized Graphs

Calculate the fugacity of benzene at T = 64 oC, P = 34

bar using the Lee-Kesler method.

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Solution

Tc = 562.1 K; Pc = 48.9 bar; w = 0.210

TR = 0.6; PR = 0.7bar;
By interpolation in Tables E.13 and E.14 at these conditions
f (0) = 0.04415; f (1) = 0.02145
f = (f (0) ) (f (1) ) = ( 0.04415) ( 0.02145)
w 0.210
= 0.0197
f = f P = ( 0.0197) ( 34 ) = 0.67 bar

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Figure 7-2: Generalized graph for (ln ϕ)(0) and (ln ϕ)(1) (extended
range of pressures)

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Question 7 Generalized Graph

Estimate a value for the fugacity of 1-butene vapour at

200 oC and 70 bar

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Solution
Tc = 420.0 K; Pc = 40.43 bar; w = 0.191
TR = 1.27; PR = 1.731 bar;
By interpolation in Tables E.15 and E.16 at these conditions
f (0) = 0.627; f (1) = 1.096
f = (f (0) ) (f (1) ) = ( 0.627) (1.096)
w 0.191
= 0.638
f = f P = ( 0.638) ( 70 ) = 44.7 bar

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Question 8 Fugacity from the SRK

Calculate the fugacity of CO2 at 4.5 oC, 15 bar, using
the SRK equation
R 2TC2 é
( )
2
a = 0.42748 1+ W 1- T r1/2 ù
PC ë û
RTC
b = 0.08664
PC
W = 0.480 + 1.574w - 0.176w 2
( )
Z 3 - Z 2 + A ¢ - B ¢ - B ¢ 2 Z - A ¢B ¢ = 0
aP bP
A¢ = ; B¢ =
( RT )
2
RT

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Solution
Tc = 304.2 K; Pc = 73.8 bar; w = 0.225
The parameters of the SRK equation are
a = 0.3893 J m 3 /mol2 ; A' = 0.112141
b = 2.971x10 -5 m 3 /mol2 ; B' = 0.0193049
The cubic equation for Z is
-0.00216488 + 0.00924639 Z - Z 2 + Z 3 = 0
Z1 = 0.0401352; Z 2 = 0.0599377; Z 3 = 0.899927
Since the phase is vapour, we select the largest root, Z = 0.899927.
f = 0.908246
f = f P = ( 0.908246 ) (15 ) = 13.62 bar

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Question 9 Saturation Pressure from EoS

and Phase Diagram Based on SRK

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 Solution
Equalities between properties of saturated phases of pure component:

G L = GV ; G LR = G LR
f V
= f L; fV = f L
Based on the SRK Equation
RT a
P= -
(V - b ) V (V + b )
R 2TC2 é
( )
2
a = 0.42748 1+ W 1- T r1/2 ù
PC ë û
RTC
b = 0.08664
PC
W = 0.480 + 1.574w - 0.176w 2

Problem: how to locate points L and V, which mark the saturated phase or Psat?

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Fugacity coefficient of ethylene based on the SRK. Branches AB and CD

correspond to the same ones in Figure 7.3, Why?
Procedure to determine the saturation
pressure:
1. Assume a pressure
2. Substitute the assumed P value into
Eq. (2.40 to 2.44) and Eq. (2.36) to
calculate for Z values
3. There are always 3 real roots.
4. Use the smallest root to calculate
the fugacity coefficient of the liquid
and the largest root to calculate the
fugacity of the vapour by using Eq.
(7.21).
5. If the two coefficients are not equal, (Eq. 7.21)
go back to step 1, until the fugacity
coefficients for both phases agree to ln f = (Z -1) - ln ( Z - B ¢ ) - A ¢ ln æç Z + B ¢ ö÷
within an acceptable tolerance. B¢ è Z ø

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