11/29/2011

Phase Diagrams
of
Binary Liquid Systems
A. Completely miscible binary liquids
When C = 2,
Intensive Variables: P, T, C1/C2
If T or P = k
F=3P
If T = k, P vs. C
If P = k, T vs. C

Raoults Law
For each volatile component of an ideal mixture of
liquids at constant T
T=k
Pi = i Pi

PA = A PA

PB

P = (1B) PA + B PB

and
P B = B P B
Since, Ptot = Pi

PB = B PB

P = PA + PB
=A PA + B PB

PA

PA = A PA

= (1B) PA + B PB

= (1 A)PA

B or YB

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For the vapor in equilibrium with the liquid

Pi = Yi Ptotal

T=k

PA = YA Ptotal
PB

and
PB = YB Ptotal
For the vapor above
the solution

V
L+V

B PB

YB =

(1B) PA + BPB

PA

B or YB

Ideal Solutions
1. IFA are completely balanced, A - - A = A - - B = B - - B
T=k
PB

L
P
L+V

PA

s
B or YB

v
B

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Nonideal Solutions
1. A - - A A - - B B - - B
closest to ideal behavior
intermediate values of Psoln
Intermediate values of Tsoln

T=k
PB
L
L+V
P
V
PA

B or YB

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Temperature Composition Diagram

P=k

TA
V
T
L+V
L
TB

B or YB

Fractional distillation
P=k

TA
V
T
L+V
L
TB

d1
B or YB

d2

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IFA are unbalanced

1. A - - A > A - - B < B - - B
Exhibits maximum vapor pressure
Exhibits minimum boiling point

Vapor Pressure Diagram

T=k
Pmax
L

L
L+V

L+V

PB

PA
E: Azeotrope

B or YB

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Poling Point Diagram

P=k
TA
V
L

L+V

TB
V

L+V L
Tmin

B or YB

2. A - - A < A - - B > B - - B
Exhibits minimum vapor pressure
Exhibits maximum boiling point

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Vapor Pressure Diagram

T=k
PA
L
V

L+V

PB
L

L+V V
Pmin

B or YB

Boiling PointDiagram
P=k
Tmax
V

V
L+V

L+V

TB

TA

B or YB

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Partially miscible liquid pairs

Unbalanced strength of IFA at certain concentration
range

A in B
A(l)

B(l)

B in A

Since only the liquid phase is involved, P = k

F=CP+1
=2P+1
=3P

1. Miscibility is enhanced by increase in T

A--A>A--B<B--B
p=k
P=1
F=31=2
(T, %A / %B)

cstmax
T2
P=2
F=1
(T / %A / %B)

Temp
T1

ccst

y y

composition, wt %

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Material Balance

Consider a mixture of
composition m kept at T1

p=k

x = comp. of Arich layer

y = comp. of Brich layer
Tf

wt of Arich layer

T2

wt of Brich layer

ym
mx

If mixture m is heated to T2
x = comp. of Arich layer

T1

y = comp. of Arich layer

wt of Arich layer

y y

wt of Brich layer

y m
m x

Tf = temp of complete
miscibility

composition, wt %

If while T1 is kept constant,

B is added to m until the
composition of the mixture
is m

p=k

x = comp. of Arich layer

y = comp. of Brich layer
wt of Arich layer

wt of Brich layer

y m
=

m x

T1

composition, wt %

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2. Miscibility is enhanced by decrease in T

A--A<A--B>B--B
p=k

T2
P=2

Temp
T1
cstmin

P=1
A

ccst

y y

composition, wt %

3. Miscibility is enhanced by increase or decrease in T

A- -AA- - B B - - B
p=k
cstmax

P=1

T2

P=2

Temp
T1
cstmin
A

Ccst

Ccst,

y y

composition, wt %

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Completely immiscible liquid pairs

For a pair of immiscible

liquids at constant T
Ptotal = PA + PB
At the boiling pt. of the mixt.

Patm

PA = vapor pressure of A
PB = vapor pressure of B
A+B

YA =

PA

nA

Ptot

nvap

PA

YA /YB

A
PB

nA / nB
wA / MA

wB / MB
T

Tb

PA / Ptot
PB / Ptot

nA/nvap
nB/nvap

= PA / PB
= PA / PB

wA / wB = MAPA / MBPB

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