Solutions

 Definition of a solution: A homogeneous mixture of two or more

substances, which have the same chemical composition and the same
physical properties throughout.

 Ideal solution: In an ideal solution there are no special forces of

attraction between the constituent molecules (enthalphy=0).
 Vapor pressure of an ideal solution

 Raoult’s Law states that for an ideal solution, the partial pressure of a component in
the vapor is equal to the product of the mole fraction of that component in the liquid
and the vapor pressure of the pure component.
where Pi = partial pressure of the ith component in the vapor
Pi  x i Pvi Xi = mole fraction of the ith component in liquid solution
Pvi = vapor pressure of the pure ith component
PT   x i Pvi where PT = total pressure of exerted by the vapor
= vapor pressure of the solution
= bubble point pressure

 Dalton’s Law states that for an ideal gas the partial pressure of a component in the
vapor is equal to the product of the mole fraction of that component in the vapor and
the vapor pressure of the solution.
Pi
Pi  yi PT or yi 
PT
 Example

At 0oF calculate the bubble-point pressure and the composition of the vapor at the
bubble point for a two-component solution having a mole fraction of propane equal to
0.5 and a mole fraction of butane equal to 0.5. Repeat these calculations for a solution
whose mole fraction of propane is 0.25 and whose mole fraction of butane is 0.75. The
vapor pressures of pure propane and butane at 0 oF are 38.20 psia and 7.30 psia,
respectively.
For the solution of propane and butane of each 0.5 mole fraction:
Component Pi xi Pi = xiPvi yi = Pi/PT
C3 H 5 38.20 0.50 19.10 0.840
C4H10 7.30 0.50 3.65 0.160

PT = 22.75 psia
Thus, bubble-point pressure for this solution is 22.75 psia at 0 oF, and
the mole fractions of propane and butane are 0.840 and 0.160, respectively
For the solution of propane = 0.25, and butane = 0.75 mole fractions:

Component Pi xi Pi = xiPvi yi = Pi/PT

C3H5 38.20 0.25 9.55 0.635
C4H10 7.30 0.75 5.48 0.365

PT = 15.03 psia

Thus, bubble-point pressure for this solution is 15.03 psia at 0 oF, and
the mole fractions of propane and butane are 0.635 and 0.365, respectively
 Liquid and Vapor Composition of Two-Component
System in the Two-Phase Region

(1) x1 Pv1  x 2 Pv2  PT But, x1  x 2 1  x 2 1  x1

(2) x1 Pv1   1  x1  Pv2  PT

PT  Pv2 PT  Pv1
(3) x1  , and x 2   1  x1
Pv1  Pv2 Pv2  Pv1

Dalton’s Law for the vapor:

P1 x1 Pv1 P x P
(4) y1   , and y 2  2  2 v2 1  y 2
PT PT PT PT
Note: Equations (1) to (4) are applicable anywhere in the two-phase region, include at the
bubble point and dew point.
 Example

Assuming ideal solution behavior for a system of one mole n-butane and one mole n-
pentane.
a) Calculate the composition of the liquid and vapor at 180 oF and 95 psia.
b) Calculate the bubble point and the composition of the vapor at 180 oF.
c) Calculate the dew point pressure and the composition of the liquid at the dew point
at 180oF.
a) We know that, PvC4 = 160 psia, and PvC5 = 54 psia (Amyx pg. 313-314)
Mole faction in the liquid:
PT  PvC5 95  54
x C4    0.394, and x C5  1  x C4 1  0.394  0.606
PvC4  PvC5 160  54

Mole faction in the vapor: x c4 PvC4 0.394 x160

yC4    0.665
PT 95
yC5 1  y C4  1  0.665  0.335
b) The bubble point and the composition of the vapor at 180 oF?

Since the overall composition and the composition of liquid are equal at
bubble point, xC4 = xC5 = 0.5.

PT  54
0.5   PT 107 psia  bubble po int pressure 
160  54

Mole faction of the vapor at bubble point pressure:

x c4 Pv4 0.5 x160

yC4    0.747
PT 107
yC5 1  yC4 1  0.0.747  0.253
c) The dew point pressure and the composition of the liquid at the dew point at 180 oF?

Since the overall composition and the composition of vapor are equal at dew point,
yC4 = yC5 = 0.5.
x c4 Pv4
yC4  where PT = dew point pressure
PT

x C4 
PT  PvC5
, thus y C4 
  PT  PvC5   PvC4  PvC5   PvC4
PvC4  PvC5 PT

thus yC4 
P T  54   160  54   160
 PT  80.8 psia  dew po int pressure 
PT
Mole faction of the liquid at dew point pressure:
80.8  54 x C5 1  0.243  0.757
x C4   0.243
160  54
 Calculation Summary

For a system composed of 1 mole of n-butane and 1 mole of n-pentane at 180 oF.

 Bubble point pressure (Pb) = 107 psia

 Composition of vapor at Pb: yC4 = 0.747, yC5 = 0.253

 Compositions of liquid and vapor at 95 psia: xC4 = 0.394, xC5 = 0.606;

yC4 = 0.665, yC5 = 0.335

 Dew point pressure (Pd) = 80.8 psia

 Composition of liquid at Pd: xC4 = 0.243, xC5 = 0.757

 Multi-Component Systems
z i n  x i n l  yi n v
BPP   x i Pvi  Raoult’s Law
Application of Raoult’s Law and
Dalton’s Law
Pi x i Pvi Pvi
yi    Dalton’s Law zi n  x i n l  xi n v
PT BPP PT
Let, zi n
 xi 
 P
n = total number of mole in the system n l  vi n v
 nl = total number of mole in the liquid PT
 zi n
nv = total number of mole in the vapor
 Since  x i 1:  xi   1
 zi = mole fraction of ith component in the Pvi
nl  nv
overall system PT
 xi = mole fraction of ith component in the liquid
zi n
 yi = mole fraction of ith component in the vapor For vapor
 yi   PT
1
 n = 1, and nl + nv = 1 nv  nl
Pvi
 Example

A system consists of 20 mole percent propane, 30 mole percent pentane, and

50 mole percent heptane at 150oF. Assuming ideal solution behavior calculate
the composition of the liquid and the vapor at 20 psia. Given that vapor
pressures at 150oF are PvC3 = 345 psia, PvC5 = 36.6 psia, and PvC7 = 5 psia.

Step 1: assume initial value of nl, thus nv = 1 - nl

Step 2: use the following equation, and check whether  x i  1 , if not make new
assumption of nl, and repeat the calculations. It is considered converge if
(1 - total xi) < 0.002.
zi n
 i  Pvi 1
x 
nl  nv
PT
A system consists of 20 mole percent propane, 30 mole percent pentane, and
50 mole percent heptane at 150oF. Assuming ideal solution behavior calculate
the composition of the liquid and the vapor at 20 psia. Given that vapor
pressures at 150oF are PvC3 = 345 psia, PvC5 = 36.6 psia, and PvC7 = 5 psia.

assume nl = 0.45, thus nv = 0.55

Component zi PVi Pvi/PT = Pvi/20 xi

C3 0.20 345 0.020
C5 0.30 36.6 0.206
C7 0.50 5 0.851
1.077
x i Pvi
Step 3: Calculate yi, use yi 
PT
A system consists of 20 mole percent propane, 30 mole percent pentane, and 50 mole
percent heptane at 150oF. Assuming ideal solution behavior calculate the composition
of the liquid and the vapor at 20 psia. Given that vapor pressures at 150oF are PvC3 =
345 psia, PvC5 = 36.6 psia, and PvC7 = 5 psia.

P 20 psia
nl assumption
T 150 0.50 0.55 0.55 ng 0.45
Comp zi Pvi xi corrected xi yi yi corrected
c3 0.2 345 0.0219 0.0241 0.0239 0.02 0.412052 0.41
c5 0.3 36.6 0.2120 0.2184 0.2179 0.22 0.398873 0.40
c7 0.5 5 0.8000 0.7547 0.7580 0.76 0.189537 0.19
1 1.0339 0.9972 0.9998 1.000 1.000462 1

nl 0.5462

zi n
zi * n
 i  Pv i  1.0
x   yi   PT
1
nl  nvi nv  nl
Pt Pvi
A system consists of 20 mole percent propane, 30 mole percent pentane, and 50 mole
percent heptane at 150oF. Assuming ideal solution behavior calculate the bubble point and dew point pressure
of the liquid. Given that vapor pressures at 150oF are PvC3 =
345 psia, PvC5 = 36.6 psia, and PvC7 = 5 psia.

Bubble pt Dew pt
calc. xi=zi calc
T 150 zi*Pvi yi =? zi/Pvi xi = ?
Comp zi Pvi zi*Pvi/Pb zi*Pd/Pvi
c3 0.2 345.0 69.00 0.84 0.00 0.01
c5 0.3 36.6 10.98 0.13 0.01 0.08
c7 0.5 5.0 2.50 0.03 0.10 0.92
1 82.48 1.00 9.19 1.00
Pb Pd
 Homework due:

A system consists of 25 mole percent propane, 35 mole percent pentane, and 40 mole
percent heptane at 150oF. Assuming ideal solution behavior calculate the composition
of the liquid and the vapor at 20 psia. Given that vapor pressures at 150 oF are PvC3 =
345 psia, PvC5 = 36.6 psia, and PvC7 = 5 psia.
A system consists of 25 mole percent propane, 35 mole percent pentane, and 40 mole
percent heptane at 150oF. Assuming ideal solution behavior calculate the composition
Of the liquid and the vapor at 20 psia. Given that vapor pressures at 150oF are PvC3 =
345 psia, PvC5 = 36.6 psia, and PvC7 = 5 psia.

Pt (psia) 20
nl
T (F) 150 0.38 0.45 0.382 bubble pt Dew pt
comp zi Pvi (psia) xi yi ziPvi yi=? zi/Pvi) xi = ?
C3 0.25 345 0.023 0.025 0.023 0.390 86.25 0.85 0.0007 0.008026
C5 0.35 36.6 0.231 0.240 0.231 0.423 12.81 0.13 0.0096 0.105915
c7 0.4 5 0.749 0.681 0.746 0.186 2 0.02 0.0800 0.886059
1 1.002 0.946 1.000 1.000 101.06 1 11.0757 1.0000
nl 0.382 Pbp Pdp

zi n
z *n
 xi   i Pv i  1.0  yi   PT
1
nl  nvi nv  nl
Pt Pvi
 NON-IDEAL SOLUTIONS

Facts:
 For non-ideal solutions, Raoult’s Law and Dalton’s Law are not applicable

 For ideal solution, yi  Pvi x i , but for non-ideal solution become, yi  K i x i

PT
 Ki or equilibrium constant is an experimentally determined constant.

 Ki is a function of both temperature and pressure.

 Equilibrium constants increase with

increasing temperature and decrease
with increasing pressure

 Ki is experimentally determined using

yi
Ki 
xi
 USE of Ki for NON-IDEAL SOLUTIONS
Multi-component systems:
Two-component systems:
zi n
1)  x i   1
1 K2 n l  Ki n v
1) x1 
K1  K 2
1  K1 zi n
2)  yi   1
2) x 2  1  x1  nl
K 2  K1 nv 
Ki
3) y1  K1 x1
Note 1: use similar technique when the liquid
4) y 2 1  y1  K 2 x 2 and the vapor composition are calculated in
ideal solutions.
Note 2: if  x  1 , the next assume value of
i

nl should be increased, and if  x  1

i , nl
should be decreased.
 Bonus Homework: due

A hydrocarbon system has the following composition. Calculate the

composition of the liquid and the vapor if a separation is conducted at
200 psia and 100oF. Assume non-ideal solution behavior.

Component Mole Fraction

CH4 0.15
C2H6 0.05
C3H8 0.25
i-C4H10 0.05
n-C4H10 0.15
n-C5H12 0.25
n-C6H14 0.10
 Bubble Point and Dew Point Pressure

 At the bubble point the system is entirely in the liquid state except for an
infinitesimal amount of vapor
 Thus at BPP, nv = 0, and n = nl
 Consequently, zi n zi n
 nl  1   n   K i zi 1
nv  0
Ki Ki

 The system at bubble point is all liquid, so  K i x i 1

 At the dew point the system is entirely in the vapor state except for an infinitesimal
amount of liquid
 Thus at DPP, nl = 0, and n = nv
 Consequently, zi n zi n zi
 n K n  1   0  K n  K 1

l i v i v i

 The system at dew point is all vapor, so yi

 K 1
i
 Example

A system has the following overall composition. At 160oF calculate the bubble-
point pressure, the composition of the vapor at the bubble point, the dew-point
pressure, and the composition of the liquid at the dew point.
Component Mole Fraction Pvi at 160oF, psia
n-C4H10 0.403 123
n-C5H12 0.325 43.0
n-C6H14 0.272 15.8

Step 1: assume initial value of Pb using Raoult’s Law at 160oF

Pb = 0.403 x 123 + 0.325 x 43.0 + 0.272 x 15.8 = 67.85 psia ~ 70 psia

Step 2: first trial-and-error solution using  K i x i 1 at 70 psia
Component xi Ki (70 psia and 160oF) Ki xi

n-C4H10 0.403 1.63 0.657

n-C5H12 0.325 0.61 0.198
n-C6H14 0.272 0.25 0.068
0.923
Step 3: Next, since the summation is less than one a lower pressure of 60 psia is chosen.
Component xi Ki (60 psia and 160oF) K i xi
n-C4H10 0.403 1.86 0.750
n-C5H12 0.325 0.70 0.228
n-C6H14 0.272 0.285 0.077
1.055
Step 4: The summation is greater than one so Pb is between 60 and 70 psia.
By interpolation the bubble point is found to be, Pb = 64.2 psia
70  60 0.923  1.055
  Pb  64.2 psia
70  Pb 0.923  1.000

Step 5: Calculate the composition of the vapor at K values at 160°F and Pb = 64.2 psia
are obtained by interpolation from the appropriate charts and K i xi computed.
Component xi Ki (64.2 psia and 160oF) yi = Ki xi
n-C4H10 0.403 1.76 0.709
n-C5H12 0.325 0.66 0.214
n-C6H14 0.272 0.27 0.073
0.996
Step 6: For the dew-point pressure, choose a pressure of 35 psia as a point of
departure and calculate as required by yi
 K 1
i

Component yi Ki (35 psia and 160oF) yi/Ki

n-C4H10 0.403 3.17 0.127
n-C5H12 0.325 1.17 0.278
n-C6H14 0.272 0.47 0.579
0.984
Step 7: Since the required summation is too low the calculation is repeated at 40
psia
Component yi Ki (40 psia and 160oF) yi/Ki
n-C4H10 0.403 2.75 0.147
n-C5H12 0.325 1.01 0.322
n-C6H14 0.272 0.41 0.663
1.132
Step 8: Since the summation is greater than one the dew-point pressure is between 35
psia and 40 psia. Interpolation leads to a value of 35.5 psia

Step 9: The composition of the dew-point liquid is computed an shown below

Component yi Ki (35.5 psia and 160oF) xi = yi/Ki

n-C4H10 0.403 2.75 0.147
n-C5H12 0.325 1.01 0.322
n-C6H14 0.272 0.41 0.663
1.132
 Homework: due

A non-ideal system has the following overall composition. At 120 oF calculate the
bubble-point pressure, the composition of the vapor at the bubble point, the
dew-point pressure, and the composition of the liquid at the dew point.
Component Wt
C3H8 5 lb
C4H10 30 lb
C5H12 10 lb
C6H14 30 lb
C7H16 25 lb