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Ideal Gas: PV =RT

Use (2) to find Pcalculated until P


converges.
Use Daltons to find xi

o
o
o

Use Antoine, find Psat


Use Daltons to find P
Use Raouls to find yi

o
o
o

Use Antoine, find Psat


Use (2) to calculate P.
Use Raoults to calculate x1

Antoine : ln P sat =A

B
T+C

Raoul t ' s : y 1P=x 1P1sat


sat
Dalto n' s : P tot =x1 Psat
1 + x 2 P2

Linear with

Ideal
sat

P
K
Rel . Votality : 12 = 1sat = 1 ( weak fucntion of T )
K2
P2

3. Bubble P :Given x 1T . Calculate y !P

4. Dew P :Given y 1T . Calculate Px 1

5.Given T PFind x i y i

sat
sat
P ( x 1P 1 + x 2P2 )1
=
P2sat
Psat
2

o
o

Use Antoine, find Psat


Use Daltons to find x

PPsat
x 1= sat 2 sat
P1 P2

P
P
> P =
=
(1)
sat
x

x 1P1
1
12 + x 2
+ x2
Psat
2
sat
2

Use Raoults to find yi

Assume T, calculate P1sat and P2sat


from Antoine.
Use Daltons to find Pcalculated
Use Pcalculated to find y1 using
Raoults.
Repeat until ys converge. Or until
P converges.

6.Given x yFind T P

Component 1 is more volatile.

F=2 + N where = of phases , N= of species

o
o

1. Bubble T :Given x 1P . Calculate T y 1 .


o

At given P, find T1sat and T2sat


(boiling points) if available ->
sat
T initial =x 1T sat
1 + x 2T 2

Or just assume T, calculate P1sat and


P2sat from Antoine.
Put those into Daltons Law
to see if get the same P,
repeat until P converges. Use
Raoults to find ys
Or, find P2sat from (1). Plug it
back to Antoine to find T
until T converges.

2. Dew T :Given y 1P . Calculate T x1 .


y iP

y iP

Test see if there are two phasenot

Z 1(1 )=x 1L+ y 1V ( 3 ) with L+V =1


o
o
o

At Bubble Point: L = 1, V = 0 => Z1(1)


= x1
At Dew Point: L = 0, V = 1 => Z1(1) =
y1

Pbubble =Z 1P1sat + ( 1Z1 )Psat


2
Pdew=

1
Z 1 1Z1
+ sat
sat
P1
P2

P1

If Pdew < P<PBubble = 2 phases

1
1
> P=
=
(2)
y1
y2
yi
+
sat
P2
Psat
Pi
1

If P> Pbubble = All liquid

If P< Pdew = All vapor

x i=1x i=

( )

sat
1

= 1=

sat

sat

Assume T, find Psat

Z 1=x 1(1V ) + y 1V =V =

Z 1x 1
(4)
y 1x 1

Modified Raoults Law:


sat
y 1 P= 1x 1P1 ( 5 ) where =activity coef .

Case I:

is independent of xi ( H . C)

10.Given P , x1 Find T , y 1Same as 8. Assume T

y 1 1Psat
1
=
x1
P

11. Given T , PFind x 1 , y 1

K values for light H.C chart 10.13 and


10.14

y1
=K 1 . If K >1=alcohol ,<1=H 2 O
x1

Pdew=

y1

y2
+
sat
1P 1 2P2

sat

sat
Pbubble =x1 Psat
1 1 + ( 1x1 ) P 2 2

Pbubble =x1
Find Psat using Antoine
Find K1 using:
sat
1

y 1P= x1P K 1P=P

y 1=
o

y i=1
y i=1=x 1K 1+ ( 1x 1 )K 2
12.Given x 1 , y 1Z 1Find P , T
o

Assume T, find Psat

Choose

sat
Psat
2 < P I< P 1

that satisfies

these Psat
At this P,T read Ks or use Raoults to
find out either x or y. Compare the
calculated to the given.

y 1P= x1H

Since H P2sat , can ignore second term .

Find V using (4)

Find y 1 by Substitute x 1=

Henrys Constant depends on T only

P=x 1 H 1 + x 2P2sat

sat
1

y1
into ( 3 ) ,
K1

Z 1K 1
(6)
1+ V( K 1 1 )

* Azeotrope

y 1=x 1 K 1=1=x 1K 1 + ( 1x 1 )K 2(7)


o

Assume Pdew <P I < Pbubble

Read K 1K 2 chart , plug( 7 )


Repeat until find a P where (7) is
satisfied.

9. GivenT , y 1Find P , x1

x 1= y 1 /K 1= 1= y 1 / K 1 + ( 1 y 1 )K 2 (8)

Use for modified Raoults

Law*
o

If 1 only depends on T , P .Use K like normal

Use Raoults or (4) to find x

8. GivenT , x 1Find P , y 1

Read Ks or use Raoults to find K


Assume x1 to calculate y1 until

o
o

Henr y ' s ConstantP .357 at T =25 o C

7.Given T , P , Z Calculate x , y , V

Repeat until find a P where (8) is


satisfied

Let

o
o

Read K 1K 2 chart , plug( 8 )

depends on T , Px i

Case II:

Solve (5)

Assume Pdew <P I < Pbubble

If i depends on xi

=> Azeotrope may

exist
az

az

az

az

x 1 = y 1 x 2 = y 2

1 P1
y2
sat
y1
2 P2
P
=
=
x1
x2
P

sat

y1
sat
x1 1P1
> 12 = =
y 2 2P2sat
x2

x1 Psat
1
y 1=
P
x2 Psat
2
y 2=
P

Test for Azeotrope


Find lim 12 lim 12

x1 1

1
o

x 2 1

compare to

If same sign no azeotrope

If opposite sign azeotrope . No Raoul t ' s Law .


az

o
o

P = 1 P1

az

az

sat

az

sat

1 P1

P
= 1az = 2sat
sat
2P2
2 P1

az
12=1=

y 3=

( 1x 1x 2 ) P sat
3
P

4 equations, 4 unknowns.

Three components system

Non Raoults

Given T, P, Z Calculate x, y and V


Read Ks from graphs

sat

Three components system

Recall eqt ( 4 )( 6 ) . y i=1=

Z 1K 1
1+V ( K 11 )

Find V easily then plug back in and find


individual ys.
Raoults

sat
P=x 1 P1sat + x2 Psat
2 + ( 1x 1x 2 ) P 3

Calculate x using K.