Faculty of

Faculty of Chemical
FACULTY OF PETROLEUM & RENEWABLE ENERGY ENGINEERING
Petroleum &
Renewable Energy Course Learning Outcomes & Energy
Engineering
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At the end of this course students will be able to

CHAPTER 6 Apply Raoult’s Law for a single condensable species

Explain the meaning of Ideal solution and the
applicability of Henry’s Law and Raoult’s Law
MULTIPHASE Use Txy and Pxy diagram to determine the Bubble and
SYSTEMS Dew point temperatures and pressures, compositions
and relative amounts of each phase in a two phase
mixture
The effects of varying temperature and pressure on
Bubble point, Dew Points, and phase amounts and
compositions.
Chap. 6 - 1

Sem I (2013/14) Sem 2 (2015/16) 2

Faculty of Chemical Single Component Phase Faculty of Chemical

Multiphase Systems & Energy
Engineering Equilibrium - Phase Diagrams forwww.utm.my/petroleum
H2O
& Energy
Engineering
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Process 1 Process 2
Ethanol Important concepts:
vapor Benzene P
Ethanol
Benzene Solid
distillation Qut MP FP
Critical • Vapor Pressure
Benzene Liquid
crystallizer Point • Boiling Point (b.p.)
218.3 atm • b.p. temperature
liquid
liquid
760 mmHg
C D E • Normal b.p.
Ethanol
Solid • Sublimation Point (SP)
17.54 mmHg
water extractor B @ (T,P) • Melting Point (MP)
Triple
4.58 mmHg Vapor
Ethanol 3 mmHg Point
A
• Freezing Point (FP)
Benzene decanter SP • Triple Point
liquid 1 Process 3 -5 0.0098 20 100 373.4

liquid 2

Sem 2 (2015/16) 3 Sem 2 (2015/16) 4

 Faculty of Chemical
Vapor Pressure (p* ) & Energy
Engineering
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Vapor Pressure (p* ) – Applications in Faculty of Chemical
Chemical Engineering
& Energy
Engineering
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Volatility of a species is the degree to which the species tends to

transfer from the liquid or solid state to the vapor state
constant P
Highly volatile species tends to be more likely in vapor phase Dew point
p* is used in : T curve

Vapor pressure (p* ) - a measure of species volatility (2)

(1) Bubble P calculations - T-xy diagram.
The higher the vapor pressure for a given temperature the (given T, xi, calculate P, yi) Bubble point (1)
greater the volatility of species. curve
(2) Dew P calculations - T-xy diagram.
(given yi, T, calculate xi, P)
Vapor pressure is related to boiling - liquids with high vapor
pressures (volatile liquids) will boil at lower temperatures.
xi,yi
The vapor pressure and hence the boiling point of a liquid
In general, p* is crucial (among others) for VLE calculations…….
mixture depends on the relative amounts of the components
in the mixture.

Sem 2 (2015/16) 5 Sem 2 (2015/16) 6

Application of vapor pressure in Faculty of Chemical

& Energy
Vapor Pressure ( p*) Faculty of Chemical
& Energy
distillation process www.utm.my/petroleum
Engineering Estimation www.utm.my/petroleum
Engineering

Distillation occurs because of the differences in the vapor pressure

(volatility) of the components in the liquid mixture
i. Claussius-Clapeyron equation
ii. Cox Chart
iii. Antoine equation

Sem 2 (2015/16) 7 Sem 2 (2015/16) 8

 Faculty of Chemical Faculty of Chemical
Vapor Pressure ( p* ) Estimation & Energy
Engineering
Example I & Energy
Engineering
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Calculate the vapor pressure of benzene at 50°C using the Antoine

Equation. Also estimate the normal boiling point of benzene (the vapor
pressure at 1 atm)
Antoine Equation
B
log10 p* = A −
B T+C
log10 p* = A − Table B.4
T+C
Compound Range (°C) A B C
• Antoine constants (A, B and C) for many compounds are
Benzene 14.5 to 80.9 6.89272 1203.531 219.888
available in the literature Table B.3 for water only (pg.
638-639) and Table B.4 (pg. 640-641) in the textbook T = 50oC …. P* = 271.2 mm Hg
Also estimate the normal boiling point of benzene (the vapor pressure
at 1 atm)
Antoine Equation – Microsoft Excel P* = 760 mm Hg …… T = 80.1oC

Sem 2 (2015/16) 9 Sem 2 (2015/16) 10

Gas-Liquid Systems - Faculty of Chemical

& Energy
Single Condensable Component Engineering
Dry
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air + vapor air+ liquid water
liquid Air
+ @ equilibrium
water @ 75oC
760 mm Hg water T = 75 oC
A (e.g. water) P = 760 mmHg
T,P pH2O = yH2OP
C = water & air, P = liquid & vapor
A Evaporation
B Drying Transfer of liquid specify 2 of T, P, or yH2O
C Qin Humidification to gas phase
If a gas at temperature T and pressure P contains a saturated vapor
B,C whose mole fraction is yi and if this vapor is the only species that
A,B would condense if the temperature were slightly lowered, the partial
T,P
Qout pressure of the vapor in the gas equals the pure-component vapor
Condensation A
Transfer of gas to pressure p*i(T) at the system temperature.
Dehumidification B
liquid phase
C

C (e.g. water) Raoult’s Law,

single condensable species : pi = yiP = pi*(T)

Sem 2 (2015/16) 11 Sem 2 (2014/15) 12

 Faculty of Chemical
Example II & Energy
Engineering
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• A gas in equilibrium with a liquid must be saturated with the
volatile component of that liquid.
Air and liquid water are contained at equilibrium in closed
container at 75 oC and 760 mmHg. Calculate the molar air + vapor
• Partial pressure of a vapor at equilibrium in a gas mixture
composition of the gas phase containing a single condensable component cannot exceed the
water vapor pressure of the pure component in the system ;
pi (= yiP) ≤ p*
Raoult’s Law, single condensable species : yH2O = pH2O*(T)/P
= 289.2/760
For a given temperature, a vapor (vapor pressure) present
pH2O = yH2OP = pH2O*(T) = 0.381 mol H2O/mol
in a gas is less than its saturation amount, pi < p* , is called
yDA = 0.609 mol dry air/mol superheated vapor
B
log10 p* = A − If a superheated vapor is cooled down at constant
Table B.4 T+C pressure, the temperature at which pi = p* (saturated
vapor) is known as the dew point of the gas
Compound Range (°C) A B C T p*

Water 60 to 150 7.96681 1668.21 228 75 289.2 • Any attempt to increase pi by either adding more vapor or
increasing total pressure, would lead to condensation.

Sem 2 (2015/16) 13 Sem 2 (2014/15) 15

Faculty of Chemical
Example IV & Energy
Engineering
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b. Calculate the percentage of vapor that condenses

A stream of air at 100oC and 5260 mm Hg contains 10% and the final composition of the gas phase if the gas
water by volume. is cooled to 80oC at constant pressure.
a. Calculate the dew point of the air

Partial pressure ; pH2O = yH2OP = (0.1)(5620) mm Hg = 526

Basis : 100 mol feed gas
mmHg
100 mol Q2 mol vapor
Vapor pressure @ 100oC; pH2O*(100oC) = 760 mmHg 0.1 mol H2O/mol y ( mol H2O/mol)
Hence, p* H2O > pH2O ==> the vapor is superheated 0.9 mol BDA/mol (1-y) (mol BDA/mol)
T = 100oC, P =5260 mm Hg T = 80oC, P =5260 mm Hg
If pH2O = pH2O*(Tdp) = 526 mm Hg; from Table B.4, Saturated with H2O
Tdp = 90oC Q1 mol H2O (liquid)

Sem 2 (2015/16) 16 Sem 2 (2014/15) 17


Saturation condition at outlet:
Antoine’s equation
c. Calculate the percentage of vapor that condenses and the final
gas phase composition if instead of being cooled at constant
y P = pH2O*(T); pressure the gas is compressed isothermally (at constant
y = pH2O*(80)/P temperature) to 8500 mm Hg.
=355 mmHg/5260mmHg = 0.0675 mol H2O/mol

Balance on Dry Air 100 mol 0.9 mol BDA = (1 - y) Q2 mol Basis: 100 mol Feed Gas
mol

Q2 = 96.5 mol

Total Mole balance 100 mol = Q1 + Q2; (Q2 = 96. 5 mol) Q2 mol
100 mol y mol H2O/mol
Q1 = 3.5 mol H2O condensed (1-y) mol BDA/mol
0.1 mol H2O/mol T = 100oC, P = 8500 mmHg
% condensation 3.5 mol H2O condensed x 100% = 35% 0.9 mol BDA/mol
T=100oC, P=5260 mm Hg Q1 mol H2O (l)
(0.1 x 100) mol H2O fed

Sem 2 (2014/15) 18 Sem 2 (2014/15) 19

Multi-component Gas-Liquid Faculty of Chemical

& Energy
Initially, yH2O P < pH2O*(100oC). Saturation occurs when P is high enough. Systems Engineering
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When pi=p* … saturated vapor …. pi=p* = yiP

Psaturation = pH2O*(100oC) /yH2O = 760 mmHg/0.1 = 7600 mmHg

Any increase in P above saturation pressure, i.e. P > 7600 mm Hg, must lead
to condensation

Products from compression to 8500 mm Hg must include a liquid stream.

Saturation condition
y = pH2O*(100oC)/P = 760 mmHg/ 8500 mmHg = 0.0894 mol H2O/mol

Balance on BDA (100)(0.900) = Q2(1 - y); (y = 0.0894)

Q2 = 98.8 mol

Total mole balance 100 = Q1 + Q2; (Q2 = 98.8 mol)

Q1 = 1.2 mol H2O condensed

% condensation 1.2 mol H2O condensed x 100% = 12 %

(0.1 x 100) mol H2O fed

Sem 2 (2014/15) 20 Sem 2 (2015/16) 21

 Multicomponent Gas-Liquid Systems Faculty of Chemical Faculty of Chemical

- Raoult’s Law -
& Energy
Engineering
Example VI & Energy
Engineering
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yA, yB
A, B
(liquid) i. A benzene-toluene mixture containing
@T,P
pA = yAP; pB = yBP 30mole% benzene vapor is placed a closed
container at 1 atm and 115°C. Is the vapor
xA, xB
mixture is in equilibrium with liquid mixture ?
F=2+C-P=2 specify 2 of T,P, yH2O
ii. An equal-molar liquid mixture of benzene (B)
Raoult’s Law pA= yAP = xApA*(T) …. .. Ideal solution and toluene (T) is in equilibrium with its
pB= yBP = xBpB*(T)
Valid vapors at 50oC. What is the system pressure
• when xi ==> 1.0 (liquid is almost pure i); when xi = 1 (single condensable
species)
and composition of the vapor?
• for the entire range of compositions for mixtures of similar substances, e.g.
paraffinic hydrocarbon of similar molecular weight

Sem 2 (2015/16) 22 Sem 2 (2015/16) 23

An equal-molar liquid mixture of benzene (B) and toluene (T) is in

A benzene-toluene mixture containing 30 mole% benzene vapor equilibrium with its vapors at 50oC. What is the system pressure
is placed a closed container at 1 atm and 115°C. Is the vapor and composition of the vapor?
mixture is in equilibrium with liquid mixture
Basis : 100 mol of liquid mixture
assuming ideal solution, so
Raoult’s law : pT= yTP = xT pT*(T)
p i = y i P = x i p (T)
* pB= yBP = xB pB*(T)
i

(
y B P = x Bp*B (T) ..... 0.3(760) = x Bp*B 115o C ) xB = 0.5
y T P = x Tp *
T (T) ..... 0.7(760) = x p (115 C)
T
*
T
o xT= 0.5

pB*(50oC) = 271 mm Hg pB = (0.5) (271) = 135.5 mm Hg

pT*(50oC) = 92 mm Hg pT = (0.5) (92) = 46 mm Hg
pB*= 1990 mm Hg
P= pT + pB = 181.5 mm Hg
pT*= 859 mm Hg
yT=0.253
yB= 0.747
xB = 0.11 and xT = 0.62
xB + xT = 0.73 ≠ 1 ….. the mixture is not in equilibrium
Sem 2 (2014/15) 24 Sem 2 (2014/15) Chap. 6 - 25
 Vapor Liquid Equilibrium (VLE) for ideal Faculty of Chemical
& Energy
Application of Vapor Liquid Equilibrium Faculty of Chemical
& Energy
Solutions - Mixture of Components www.utm.my/petroleum
Engineering (VLE) in distillation process www.utm.my/petroleum
Engineering

• In a vaporization process of liquid mixture Distillation occurs because of the differences in the vapor pressure
containing several components at constant Constant P (volatility) of the components in the liquid mixture
pressure, the vapor composition will have a
composition different from that of the Vapor
liquid. T phase
Dew point
Liquid & curve
• As vaporization proceeds the composition vapor
of the remaining liquid continuously changes phase
and hence does so its vaporization
temperature. Liquid
phase
• A similar phenomenon occurs if a mixture
Bubble point
of vapors is subjected to condensation at curve
constant pressure – the composition of
vapor and the condensation temperature xi,yi
both change.

Sem 2 (2015/16) 26 Sem 2 (2015/16) 27

Vapor Liquid Equilibrium (VLE) for ideal Faculty of Chemical Bubble Point Calculations for Faculty of Chemical
& Energy & Energy
Solutions - Mixture of Components www.utm.my/petroleum
Engineering Ideal Liquids Solutions www.utm.my/petroleum
Engineering

constant P Bubble-point temperature (Tbp) of the liquid - the temperature at

which the first bubble vapor forms when the liquid is heated at given
Ideal solutions – Raoult’s and Henry’s law are
pressure
obeyed & the gas vapor can be Dew point
considered as ideal gas curve D
T
C
Raoult’s law :
∑ x p (T )
i
*
i bp
Constant P heating path on a T-x-y diagram C’ p i = y i P = x i p*i (Tbp ) hence, ∑ yi =1 = i
(trial & error)
P
A – subcooled liquid B
B’ and Bubble-point pressure (Pbp) of the liquid - the pressure at
B - saturated liquid (Bubble Point Temp.)
C - saturated vapor (Dew Point Temp.) A which the first bubble vapor forms when the liquid is heated at given
D - superheated vapor temperature
B’ - vapor composition in equilibrium with
Bubble point
curve
p i = y i Pbp = x i p*i (T )
liquid at bubble point. temp.
C’ - liquid composition in equilibrium with ∑ x p (T )
i
*
i
vapor at dew point. temp. xi,yi ∑y i =1 = i
hence, Pbp = ∑ x i p*i (T )
Pbp i

Sem 2 (2015/16) Chap. 6 - 28 Sem 2 (2015/16) 29

 Vapor Liquid Equilibrium (VLE) for ideal Faculty of Chemical Dew Point Calculations for Faculty of Chemical
& Energy & Energy
Solutions - Mixture of Components Engineering Ideal Vapor Solutions Engineering
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constant P Dew-point temperature (Tdp) of the vapor – temperature at which the

first drop of liquid forms when the vapor is cooled at given pressure
Constant P cooling path on a T-x-y Dew point A
diagram curve Raoult’s law :
T yi P
A – superheated vapor
B p i = y i P = x i p*i (Tdp ) hence, ∑x =1= (trial & error)
p (Tdp )
i *
B’
B - saturated vapor (Dew point Temp.) i

C - saturated liquid (Bubble Point Temp.)

D - subcooled liquid C C’
B’ – liquid composition in equilibrium with Dew-point pressure (Pdp) of the vapor – pressure at which the first
vapor at dew point. temp. drop of liquid forms when the vapor is cooled at given temperature
Bubble point
C’ - vapor composition in equilibrium with D curve
liquid at bubble point. temp. yi 1
∑x i = 1 = Pdp ∑
p*i (T ) hence, Pdp =
yi
xi,yi
i i
∑ p (T )
i
*
i

Sem 2 (2015/16) 30 Sem 2 (2015/16) 31

Faculty of Chemical
Example VII & Energy
Engineering
www.utm.my/petroleum a. At what temperature does the first drop of condensate form? What is
its composition?
A vapor mixture containing 30 mole% benzene and
Tdp = ? and P = 1 atm (760 mm Hg)
70% toluene at 1 atm is cooled isobarically a closed
container from an initial temperature of 115°C. assuming ideal solution, so

a. At what temperature does the first drop of p i = y i P = x i p*i (Tdp )

condensate form? What is its composition? yiP 0.3(760) 0.7(760)
∑x i =1= *
= * +
p (Tdp ) p B (Tdp ) p*T (Tdp )
i

b. At one point during the process the system

temperature is 100°C. Determine the mole Trial and error until ∑xi=1
fraction of benzene in the vapor and liquid phases.
Tdp ~ 104°C

c. Calculate the ratio of total moles in vapor to total xB = 0.15 and xT = 0.85
moles liquid at the system of 100°C

Sem 2 (2015/16) 32 Sem 2 (2014/15) 33

 b. At one point during the process the system temperature is 100°C.
Determine the mole fraction of benzene and toluene in the vapor and
c. The ratio (total moles in vapor/total moles liquid) at the system
liquid phases
temperature is 100°C

p i = y i P = x i p *i (T ) Basis : F = 1 mol feed

y BP = x B p *B (T ) ..... y B P = (100 C )
x B p *B o

..... y B (760) = x B p *B (100 o

C)
y TP = (T ) ..... (1 - y B )P = (1 - x B )p *T (100 o C )
x T p *T V mol Overall balance :- 1 = L + V .. (1)
..... (1 - y B ) (760) = (1 - x B ) p *T (100 o C )
yB ~ 0.46
yT ~ 0.54
Benzene Balance:- 0.3(1) = 0.46V + 0.26L .. (2)
pB*= 1350 mm Hg Solve eq. (1) & (2) simultaneously
F = 1mol T=100oC
pT*= 556 mm Hg fB ~ 0.3
fT ~ 0.7 L = 0.8 mol
xB = 0.26 and yB = 0.46 V = 0.2 mol
xT = 0.74 and yT = 0.54 L mol
xB ~ 0.26 Hence, V/L ~ 0.25 mol vapor/mol liquid
xT ~ 0.74

Sem 2 (2014/15) 34 Sem 2 (2014/15) 35