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Binary Liquid Systems Handout

This document discusses phase diagrams of binary liquid systems, including: - Completely miscible systems follow Raoult's law and form ideal solutions. - Nonideal solutions exhibit intermediate vapor pressures and boiling points. - Partially miscible systems show limited solubility over a range of concentrations. - Immiscible systems maintain separate liquid phases with vapor pressures equal to the sum of individual components.

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alyssa_marie_ke
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171 views11 pages

Binary Liquid Systems Handout

This document discusses phase diagrams of binary liquid systems, including: - Completely miscible systems follow Raoult's law and form ideal solutions. - Nonideal solutions exhibit intermediate vapor pressures and boiling points. - Partially miscible systems show limited solubility over a range of concentrations. - Immiscible systems maintain separate liquid phases with vapor pressures equal to the sum of individual components.

Uploaded by

alyssa_marie_ke
Copyright
© © All Rights Reserved
We take content rights seriously. If you suspect this is your content, claim it here.
Available Formats
Download as PDF, TXT or read online on Scribd
You are on page 1/ 11

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

11/29/2011

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

11/29/2011

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

11/29/2011

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

11/29/2011

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

11/29/2011

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

11/29/2011

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

11/29/2011

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 %

11/29/2011

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 %

11/29/2011

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 %

10

11/29/2011

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

11

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