EQUILIBRIUM
THE NATURE OF EQUILIBRIUM
THE PHASE RULE: DUHEM’S THEOREM
VLE: QUALITATIVE BEHAVIOR
SIMPLE MODELS FOR VAPOR LIQUID EQUILIBRUM: RAOULT’S LAW
THE NATURE OF EQUILIBRIUM
Equilibrium is a static condition in which no changes occur in the
macroscopic properties of a system with time.
The temperature, pressure and phase compositions reach final
values which thereafter remain fixed.
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Measures of composition
Mass or mole fraction is defined as the ratio of mass or number
of moles of a particular chemical species in a mixture or solution
to the total mass or number of moles of mixture or solution.
m m ni ni
xi i i xi
m m n n
Molar concentration is defined as the ratio of mole fraction of a
particular chemical species in a mixture or solution to molar
volume of the mixture or solution.
xi
Ci
V
or multiplying and dividing by molar flow rate, n
ni
Ci
q 3
The molar mass of a mixture or solution is the mole fraction-
weighted sum of the molar masses of all species.
M xi M i
i
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THE PHASE RULE; DUHEM’S
THEOREM
Phase rule:
F 2 N
F = no. of variables that may be independently fixed in a system at
equilibrium (degree of freedom).
= no. of phases
N = no. of chemical species
Duhem’s theorem:
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The Phase Rule & Duhem’s Theorem
On the basis of this result, Duhem’s theorem is
stated as follows:
For any closed system formed initially from
given masses of prescribed chemical species,
the equilibrium state is completely determined
when any two independent variables are fixed.
Phase Rule in VLE: Single Component Systems
For a two phase (=2) system of a single component (N=1):
F = 2- + N
F = 2- 2 + 1 = 1
Therefore, for the single component system, specifying either T or P fixes
all intensive variables.
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VLE for Pure Components
Pressure: kPa
600
400
200
0
270 320 370 420
Temperature: K
Acetonitrile Nitromethane
CHEE 311
Correlation of Vapour Pressure Data
Pisat, or
the vapour pressure of component i, is commonly represented
by Antoine Equation (Appendix B, Table B.2, SVNA 7th ed.):
B
ln Pisat A
TC
2945.47
ln P1sat / kPa 14.2724
T / C 224
For nitromethane (Component 2):
2972.64
ln P2sat / kPa 14.2043
T / C 209
80
Pressure, kPa
70
60
50
40
0.0 0.2 0.4 x1,y1 0.6 0.8 1.0
y1 x1
Phase Rule in VLE: Binary Systems (Txy
diagrams)
Alternatively, we can specify a system pressure and examine the VLE behaviour
as a function of temperature and composition.
85.0
Temp, deg C
80.0
75.0
70.0
65.0
0.00 0.20 0.40 0.60 0.80 1.00
x1,y1
y1 x1
Simple Models For VLE
The preceding section describes what is
observed through experiment. When
thermodynamics is applied to vapor/liquid
equilibrium, the goal is to find by calculation
the temperatures, pressures, and compositions
of phases in equilibrium.
Simple Models For VLE
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SIMPLE MODELS FOR
VAPOR/LIQUID EQUILIBRIUM
VLE calculation provides information on temperatures, pressures,
and compositions of phases in equilibrium.
Two simplest models, Raoult’s law and Henry’s law are used to
predict the behavior of systems in vapor liquid equilibrium.
Raoult’s Law
Assumption
◦ Vapour phase is an ideal gas
◦ Liquid phase is an ideal solution
Mathematical expression reflecting the two assumptions above is
expressed quantitatively in Raoult’s law as:
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Application of Raoult’s law:
Because iyi = 1, eq. (10.1) may be summed over all species to yield
P xi Pi sat (10.2)
i
This equation applied in bubblepoint calculations, where the vapor phase
compositions are unknown.
For a binary system with x2 = 1-x1,
P P2 sat P1sat P2sat x1
A plot of P vs. x1 at constant temperature is a straight line connecting
P2sat at x1 = 0 with P1sat at x1 = 1.
Equation (10.1) may also be solved for xi and summed over all species.
With ixi = 1, this yields
1
P
y
i
i Pi sat (10.3)
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Antoine’s equation is used to calculate P1sat and P2sat :
Bi
ln Pi sat kPa Ai
T K Ci
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Example 10.1
Binary system acetonitrile(1)/nitromethane(2) conforms closely to
Raoult’s law.Vapor pressures for the pure species are given by the
following Antoine equations:
2945.47
ln P1 sat 14.2724
T 49.15
2972.64
ln P2 sat 14.2043
T 64.15
(a) Prepare a graph showing P vs x1 and P vs y1 for a temperature of
75oC (348.15K)
(b) Prepare a graph showing T vs x1 and T vs y1 for a pressure of
70kPa
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Solution:
(a) Prepare P-x1-y1 diagram ( T is given (348.15K), x1 and y1 in the range
01)
BUBL P calculation
Calculate P1sat and P2sat from Antoine equations
At 348.15K,
P1sat = 83.21 kPa andP2sat = 41.98 kPa
0 0 41.98
100
0.1 0.1805 46.10 P1sat=83.21
0.2 0.3313 50.23 90
Subcooled liquid
0.3 0.4593 54.35 80
Bubble point
0.4 0.5692 58.47 70
0.5 0.6647 62.60
P/kPa
60
0.6 0.7483 66.72
50 Dew point
0.7 0.8222 70.84
40
0.8 0.8880 74.96
Superheated vapor
0.9 0.9469 79.09 30 P2sat=41.98
1 1 83.21 20
0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1
x1, y1
At 75oC and x1 = 0.45,
P = ?, y1 = ? BUBL P x1 y1
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(b) Prepare T-x1-y1 diagram ( P is given (70 kPa), x1 and y1 in the range 01)
Calculate T1sat and T2sat at the given pressure by using Antoine equation
Bi
Ti sat Ci
Ai ln P
For P = 70kPa,
T1sat = 342.99 K (69.84oC) and T2sat = 362.73 K (89.58oC)
Select T1sat < T < T2sat to calculate P1sat and P2sat for these temperature by
using Antoine equation, and evaluate x1 by equation:
P P2 sat
x1 sat
P1 P2 sat
For example take T = 78oC (351.15K), From eqn. (10.2)
sat
P1 = 91.76 kPa sat
P2 = 46.84 kPa x1 = 0.5156
Calculate y1 by equation (10.1),
T/K
0.2280 0.3614 357.15
0.1424 0.2401 359.15 350
Subcooled liquid
T1sat=342.99K
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0.0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1.0
x1, y1
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DEW T calculation
For y1 = 0.6 and P = 70kPa,T is determine by iteration .
Iterate as follow:
1. Calculate initial T using mole fraction-weighted average of T1sat and T2sat:
T = y1T1sat + y2T2sat
or select T1sat < T < T2sat as initial T. Use Antoine eqn.
2. Calculate P1sat and P2sat at initial T.
3. Calculate .
P1 sat P2sat
4. With the current value of , calculate P1sat .
P1sat = P y 1 +y 2 From eqn. (10.3)
5. Calculate T from Antoine equation for species 1:
2945.47
T 49.15
14.2724 ln P1 sat
*The result is T = 352.73K (79.58oC) and P1sat = 96.53 kPa. From eq (10.1), x1 =
0.4351
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REFERENCE
Smith, J.M.,Van Ness, H.C., and Abbott, M.M. 2005.
Introduction to Chemical Engineering Thermodynamics.
Seventh Edition. Mc Graw-Hill.
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