Vapor-Liquid Equilibria: Introduction To Chemical Engineering Calculations
Vapor-Liquid Equilibria: Introduction To Chemical Engineering Calculations
Vapor-Liquid Equilibria: Introduction To Chemical Engineering Calculations
Lecture 7.
Vapor-Liquid Equilibria
7 Vapor-Liquid Equilibria and Saturation
Vapor
A substance that is below its critical temperature.
Gas
A substance that is above its critical temperature
(but below the critical pressure).
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Prof. Manolito E Bambase Jr. Department of Chemical Engineering. University of the Philippines Los Baños
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7 Vapor-Liquid Equilibria and Saturation
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Prof. Manolito E Bambase Jr. Department of Chemical Engineering. University of the Philippines Los Baños
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7 Vapor-Liquid Equilibria and Saturation
Definition of Terms
Vapor Pressure
Pressure of the vapor when the vapor and liquid of a pure
component are in equilibrium. Also referred to as saturated
pressure.
Saturated Temperature
Temperature at which the vapor and liquid will co-exist at a
given pressure. C om m on ly referred to as the boiling or
condensation point.
Dew Point
The temperature when the vapor starts to condense.
Bubble Point
The temperature when the liquid starts to vaporize.
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7 Vapor-Liquid Equilibria and Saturation
Definition of Terms
Subcooled Liquid
A liquid that is below its saturated T at a given pressure.
Compressed Liquid
A liquid that is above its saturated P at a given temperature.
Superheated Vapor
A vapor that is above its saturated T at a given pressure.
Quality
For a saturated mixture, quality refers to the m a s s fraction of the
vapor in the mixture.
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Prof. Manolito E Bambase Jr. Department of Chemical Engineering. University of the Philippines Los Baños
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7 Vapor-Liquid Equilibria and Saturation
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7 Vapor-Liquid Equilibria and Saturation
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7 Vapor-Liquid Equilibria and Saturation
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Prof. Manolito E Bambase Jr. Department of Chemical Engineering. University of the Philippines Los Baños
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7 Vapor-Liquid Equilibria and Saturation
Hˆ l (1 x) Hˆ g (x) Hˆ
mixture
Uˆ l (1 x) Uˆ g (x) Uˆ
mixture SLIDE
Prof. Manolito E Bambase Jr. Department of Chemical Engineering. University of the Philippines Los Baños
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7 Vapor-Liquid Equilibria and Saturation
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Prof. Manolito E Bambase Jr. Department of Chemical Engineering. University of the Philippines Los Baños
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7 Vapor-Liquid Equilibria and Saturation
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Prof. Manolito E Bambase Jr. Department of Chemical Engineering. University of the Philippines Los Baños
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7 Vapor-Liquid Equilibria and Saturation
Vm
ˆl 3
/ kg and Vm
ˆg 3 / kg
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Prof. Manolito E Bambase Jr. Department of Chemical Engineering. University of the Philippines Los Baños
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7 Vapor-Liquid Equilibria and Saturation
m3
m3 m3
1 x x 0.505
kg kg kg
Solving for x,
x = 0.69
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Prof. Manolito E Bambase Jr. Department of Chemical Engineering. University of the Philippines Los Baños
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7 Vapor-Liquid Equilibria and Saturation
B
ln (p*) A
C
T
Where p* = vapor pressure of the substance, m m H g
T = temperature, K
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Prof. Manolito E Bambase Jr. Department of Chemical Engineering. University of the Philippines Los Baños
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7 Vapor-Liquid Equilibria and Saturation
dP* Hˆ V
dT T(Vˆg
Where p* = vaporVˆpressure
l) of the
substance T = temperature
H V = latent heat of vaporization
Vg , V l = specific molar volumes of vapor
and liquid, respectively
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Prof. Manolito E Bambase Jr. Department of Chemical Engineering. University of the Philippines Los Baños
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7 Vapor-Liquid Equilibria and Saturation
P
RT
Vg
ˆ *
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Prof. Manolito E Bambase Jr. Department of Chemical Engineering. University of the Philippines Los Baños
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7 Vapor-Liquid Equilibria and Saturation
dP* P* HˆV
dT
RT2
dP* HˆV dT2
R
P * and
Separating the variables integrating to yield
the Clausius-Clapeyron equation,
T
HˆV
ln(P*) RT B
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Prof. Manolito E Bambase Jr. Department of Chemical Engineering. University of the Philippines Los Baños
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7 Vapor-Liquid Equilibria and Saturation
Solution:
A = 15.9008
B = 2788.51
C = -52.36
SLIDE
Prof. Manolito E Bambase Jr. Department of Chemical Engineering. University of the Philippines Los Baños
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7 Vapor-Liquid Equilibria and Saturation
2788.51
ln (760 mmHg) 15.9008
52.36
T
Solving for temperature, T = 353.3
K
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Prof. Manolito E Bambase Jr. Department of Chemical Engineering. University of the Philippines Los Baños
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7 Vapor-Liquid Equilibria and Saturation
T1 = 7.6 0C P*1 = 40 mm Hg
T2 = 15.4 0C P*2 = 60 mm
Hg
Calculate the latent heat of vaporization and the
parameter B in the Clausius-Clapeyron equation and then
estimate P* at 42.2 0 C us ing this equation.
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Prof. Manolito E Bambase Jr. Department of Chemical Engineering. University of the Philippines Los Baños
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7 Vapor-Liquid Equilibria and Saturation
x1 y
ln(P*)
T
Hˆ V
m
bB
R
Solving for slope, m:
R x 1 1 T1 T2
T T
m
Hˆ V
y ln(P *2 )2 ln(P
1 *1)
T1T2
ln(P *2 /P *1 ) SLIDE
Prof. Manolito E Bambase Jr. Department of Chemical Engineering. University of the Philippines Los Baños
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7 Vapor-Liquid Equilibria and Saturation
60 mmHg
280.8 K288.6 K ln
m V
40 mmHg
HR
ˆ
280.8 K 288.6
HˆV
m R 4213 KK
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Prof. Manolito E Bambase Jr. Department of Chemical Engineering. University of the Philippines Los Baños
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7 Vapor-Liquid Equilibria and Saturation
Hˆ V
B ln(P *1 ) RT1 ln(P 2* ) RT2
Hˆ V
B ln(40 ) 4213
280.8
18.69
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Prof. Manolito E Bambase Jr. Department of Chemical Engineering. University of the Philippines Los Baños
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7 Vapor-Liquid Equilibria and Saturation
ln(P*) 4213
T 18.69
4213
ln(P*) 315.418.69 5.334
Vapor
YA (PA)
YB (PB)
Heating
Liquid
XA0
Liquid
XA
XB0 XB
Pi = f(xi)
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Prof. Manolito E Bambase Jr. Department of Chemical Engineering. University of the Philippines Los Baños
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7 Vapor-Liquid Equilibria and Saturation
Henry’s Law:
Pi = x i H i
where Pi = partial pressure of component i in the
vapor phase.
= y i P T (if the vapor behaves ideally)
H i = Henry’s law
constant
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Prof. Manolito E Bambase Jr. Department of Chemical Engineering. University of the Philippines Los Baños
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7 Vapor-Liquid Equilibria and Saturation
Raoult’s Law:
Pi = xiP*i
where Pi = partial pressure of component i in the
vapor phase.
= y i P T (if the vapor behaves ideally)
P T = total
pressure
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Prof. Manolito E Bambase Jr. Department of Chemical Engineering. University of the Philippines Los Baños
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7 Vapor-Liquid Equilibria and Saturation
yiPT = xiP*i
Rearranging the equation,
yi P *i
xi iK
PT
where K i is the V-L equilibrium constant.
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Prof. Manolito E Bambase Jr. Department of Chemical Engineering. University of the Philippines Los Baños
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7 Vapor-Liquid Equilibria and Saturation
A = 15.9798
B = 3127.60
C=–
63.63
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Prof. Manolito E Bambase Jr. Department of Chemical Engineering. University of the Philippines Los Baños
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7 Vapor-Liquid Equilibria and Saturation
Solution:
y A P *A x A
PT
y B P *B x B
PT
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Prof. Manolito E Bambase Jr. Department of Chemical Engineering. University of the Philippines Los Baños
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7 Vapor-Liquid Equilibria and Saturation
Hence,
B
ln (P*) A
C
T
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Prof. Manolito E Bambase Jr. Department of Chemical Engineering. University of the Philippines Los Baños
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7 Vapor-Liquid Equilibria and Saturation
For n-hexane:
2697.55
P* A exp15.8366 48.78 T
For n-octane:
3127.60
P* B exp15.9798 63.63 T
Since vaporization temperature is not given, the next
step in the calculation is to determine its value.
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Prof. Manolito E Bambase Jr. Department of Chemical Engineering. University of the Philippines Los Baños
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7 Vapor-Liquid Equilibria and Saturation
PT = PA + PB
f (Tk )
Tk1 Tk f '(T )
k
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Prof. Manolito E Bambase Jr. Department of Chemical Engineering. University of the Philippines Los Baños
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7 Vapor-Liquid Equilibria and Saturation
Differentiating f(T):
63.63
A n y value for the 2
temperature may be used as initial guess.
For this example, the following initial guess is used:
T0 = 1000 K
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Prof. Manolito E Bambase Jr. Department of Chemical Engineering. University of the Philippines Los Baños
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7 Vapor-Liquid Equilibria and Saturation
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Prof. Manolito E Bambase Jr. Department of Chemical Engineering. University of the Philippines Los Baños
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7 Vapor-Liquid Equilibria and Saturation
P*A = 3019.92 mm Hg
P*B = 665.86 mm Hg
y B 665.68
760 0.960 0.841
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Prof. Manolito E Bambase Jr. Department of Chemical Engineering. University of the Philippines Los Baños
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7 Vapor-Liquid Equilibria and Saturation
Vapor
YA (PA)
YB (PB)
Gas Mixture
YA (PA) Cooling
YB (PB)
Liquid
XA
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Prof. Manolito E Bambase Jr. Department of Chemical Engineering. University of the Philippines Los Baños
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7 Vapor-Liquid Equilibria and Saturation
PV
1 0 0
s r h r P * V
m a s s of vapor P V MW V
s a h a m a s s o f vapor-free gas
PT PV MW G
Molal Saturation (Molal Humidity)
moles of vapor PV
s m h m
molesof vapor-free gas PT PV
Prof. Manolito E Bambase Jr. Department of Chemical Engineering. University of the Philippines Los Baños
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7 Vapor-Liquid Equilibria and Saturation
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Prof. Manolito E Bambase Jr. Department of Chemical Engineering. University of the Philippines Los Baños
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7 Vapor-Liquid Equilibria and Saturation
y H2O PH 2O
PT
h r
PH 2O P* H 2O 100
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Prof. Manolito E Bambase Jr. Department of Chemical Engineering. University of the Philippines Los Baños
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7 Vapor-Liquid Equilibria and Saturation
At T = 75 0 C,
P*H2O = 289 mm Hg
nA P V 1.1bar1000 m3 / h 38.0 h
kmol
RT
m3 bar
0.0831kmol K 75 273 K
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Prof. Manolito E Bambase Jr. Department of Chemical Engineering. University of the Philippines Los Baños
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7 Vapor-Liquid Equilibria and Saturation
kmol O2
kmol DA 0.21kmol O2
n O2 34.0 h kmol
7.14 h
DA
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Prof. Manolito E Bambase Jr. Department of Chemical Engineering. University of the Philippines Los Baños
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7 Vapor-Liquid Equilibria and Saturation
ha PH 2O MWH 2O
86.718 0.0726
kg H2 O
kg
PT PH2O DA
825 86.729
DA
MW
The molal humidity (hm):
86.7
hm PH2O 0.117 mol
mol H 2 O
PT H 825
2O 86.7 DA
P
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Prof. Manolito E Bambase Jr. Department of Chemical Engineering. University of the Philippines Los Baños
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7 Vapor-Liquid Equilibria and Saturation
T = 48.70C
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Prof. Manolito E Bambase Jr. Department of Chemical Engineering. University of the Philippines Los Baños
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