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Chapter 1 - VLE Part 2
Chapter 1 - VLE Part 2
Chapter 1 - VLE Part 2
VAPOR LIQUID
EQUILIBRIUM PART 2
2
Example of situation
Troom = 303.15K
Tc H2O = 648.15K
Tc N2 = 126.2K
3
Example 1
If a system of air in contact with liquid water is presumed at
equilibrium, then the air is saturated with water.
5
Example 2
Assuming that carbonated water contains only CO2(1) and H2O(2),
determine the compositions of the vapor and liquid phases in a sealed can
of “soda” and the pressure exerted on the can at 10°C (283.15K). Henry’s
constant for CO2 in water at 10°C (283.15K) is about 990 bar.
6
With H1 = 990 bar and P2sat = 0.01227 bar (from steam table),
P = x1 Η1 + x2 P2sat
P = (0.01)(990) + (0.99)(0.01227) = 9.912 bar
x2 P2sat (0.99)(0.01227)
y2 = = = 0.0012
P 9.912
So,
y1 = 1 − y2 = 1 − 0.0012 = 0.9988
7
VLE by Modified Raoult’s Law
Apply for vapor phase is an ideal gas but the liquid
is not an ideal solution.
8
Bubblepoint calculations (xi given)
N N
∑ y P =∑xγ P
i =1
i
i =1
i i i
sat
(i = 1,2 ,...,N )
N N N
P ∑ yi = ∑ xiγ i Pi sat
∑y i =1
i =1 i =1 i =1
N
P = ∑ xiγ i Pi sat Eq. (10.6)
i =1
9
Dewpoint calculations (yi given)
yi P
= xi (i = 1,2 ,...,N )
γ i Pi sat
N N
yi P
∑
i =1 γ i Pi
sat
= ∑ xi = 1
i =1
N
yi
P∑ =1
i =1 γ i Pi
sat
1
P= N
yi
∑
Eq. (10.7)
i =1 γ i Pi
sat
10
Example 1
For the system methanol(1)/methyl acetate(2), the following equations
provide a reasonable correlation for the activity coefficients:
ln γ1 = Ax22 ln γ2 = Ax12 where A = 2.771 - 0.00523T
In addition, the following Antoine equations provide vapor pressures:
3643.31
ln P1sat = 16.59158 −
T − 33.424
2665.54
ln P2sat = 14.25326 −
T − 53.424
where T is in Kelvin and the vapor pressures are in kPa. Assuming the
validity of Eq. (10.5), calculate
a) P and {yi}, for t/T = 45oC/318.15K and x1 = 0.25
b) P and {xi}, for t/T = 45oC/318.15K and y1 = 0.60
c) T and {yi}, for P = 101.33 kPa and x1 = 0.85
d) T and {xi}, for P = 101.33 kPa and y1 = 0.40
e) The azeotropic pressure, and the azeotropic composition,
for t/T=45oC/318.15K
11
Solution (a) P and {yi}, for t/T = 45oC/318.15K and x1 = 0.25
BUBL P calculations
1) Calculate P1sat and P2sat using Antoine equations
At 318.15K, P1sat = 44.51kPa and P2sat = 65.64kPa
2) Calculate activity coefficients (γ) from the given equations:
A = 2.771 – 0.00523T = 2.771 – 0.00523(318.15) = 1.107
γ1 = exp(Ax22) = exp[(1.107)(0.75)2] = 1.864
γ2 = exp(Ax12) = exp[(1.107)(0.25)2] = 1.072
3) Calculate pressure, P:
N
P = ∑ xiγ i Pi sat
i =1
P = (0.25)(1.864)(44.51) + (0.750)(1.072)(65.64)
P = 73.50kPa
4) Calculate value of yi using Modified Raoult’s Law expression:
yi = ( xiγ i Pi sat ) / P
y1 = 0.282 y2 = 0.718
12
Solution (b) P and {xi}, for t/T = 45oC/318.15K and y1 = 0.60
DEW P calculations
1) Calculate P1sat and P2sat using Antoine equations
At 318.15K, P1sat = 44.51kPa and P2sat = 65.64kPa
13
6) Calculate x1 using modified Raoult’s Law equations
y1 P
x1 = x2 = 1 − x1
γ 1 P1sat
7) Evaluate activity coefficient; return to the first step.
14
Solution (c) T and {yi}, for P = 101.33 kPa and x1 = 0.85
BUBL T calculations
1) Calculate T1sat and T2sat using Antoine equations
Bi
Ti sat = − Ci
Ai − ln P
At P = 101.33kPa, T1sat = 337.71K and T2sat = 330.08K
iii. Find a new value for T from the Antoine equation for species 1
iv. Return to the initial step. 15
4) Iteration to convergence on a value for T yields final values:
16
Solution (d) T and {xi}, for P = 101.33 kPa and y1 = 0.40
DEW T calculations
1) Calculate T1sat and T2sat using Antoine equations
Bi
Ti sat = − Ci
Ai − ln P
At P = 101.33kPa, T1sat = 337.71K and T2sat = 330.08K
iv. Find a new values for P1sat from Eq. (10.7) written:
y1 y2
P sat
= P + α
γ1 γ 2
1
vi. Return to initial step and iterate with current value of γ1 and γ2 until
convergence value of T.
18
Solution (e) The azeotropic pressure, and the azeotropic composition,
for t/T = 45oC/318.15K
1) First determine whether or not an azeotrope exists at the given
temperature.
γ 1 P1sat
α12 = Eq. (10.9)
γ 2 P2sat
19
The correlating equations for activity coefficients show that
when x1 = 0, γ2 = 1 and γ1 = exp(A);
when x1 = 1, γ1 = 1 and γ2 = exp(A).
Therefore in these limits,
P1sat exp( A) P1sat
(α12 ) x1 =0 = sat
and (α12 ) x1 =1 = sat
P2 P2 exp( A)
For T = 318.15 K or 45oC, calculate
P1sat = 44.51 kPa P2sat = 65.64 kPa A = 1.107
20
Because the value at one limit is greater than 1, whereas the
value at the other limit is less than 1, an azeotrope does exist,
because α12 is a continuous function of x1 and must pass through
the value of 1.0 at some intermediate composition.