9

9.10 i)

One-constant Margules equation

RT ln 1 = Ax22
Thus
RT ln 1* = RT ln

or

1* = exp

RT ln 1 x1 = 0 = A

a f

1 x1
= Ax22 A = A 1 x22
1 x1 = 0

LM Ac1 x h OP
MN RT PQ
2
2

LM c
MN

A 1 x22
x1 1000
exp
ms M1
RT

1 =

and

h
h OP
PQ

ii) Two-constant Margules equation

RT ln 1 x1 = 1x22 + 1x23

a f
RT ln a x = 0f = +
ax f
= RT ln
= c1 x h c1 x h
a x = 0f
L c1 x h c1 x h OP
= exp M
RT
MN
PQ
L c1 x h c1 x h OP
x 1000
expM
=
mM
RT
MN
PQ
1

RT ln 1*

2
2

3
2

2
2

*
1

and

Thus

2
2

3
2

3
2

iii) van Laar equation

a f

a
f ; ln ax = 0f =

ln a x f = ln a x f ln a x = 0f =

1 + a x x f
ln 1 x1 =

*
1

1 + x1 x2

or, upon rearrangement,

LM x a2 x + x f OP
N a x + x f Q
L x a2 x + x f OP
x 1000
expM
=
mM
N a x + x f Q
2

1* = exp

and

iv) Regular Solution Theory

a f

RT ln 1 x1 = V 1 22 1 2

(since 2 =

and RT ln 1 x1 = 0 = V 1 1 2

x2V 2
1 as x1 0 )
x1V 1 + x2V 2

Thus

a f

a f
a f c ha
LV c 1ha f OP and
= exp M
RT
PQ
MN
LV c 1ha f OP
x 1000
expM
=
mM
RT
PQ
MN

RT ln 1* x1 = RT ln 1 x1 RT ln 1 x1 = 0 = V 1 22 1 1 2
1

*
1

2
2

2
2

v) UNIQUAC Model

ln i = ln

i
xi

LM
c h
MM
N
ln a x 0f = lim aln f

z
qi ln i + li i
i
2
xi

x j l j qi 1 ln j ij
j

j ij
k kj
k

OP
PP
Q

xi 0

Now consider xi 0 , then j 1 and i 0

i
xi

a
f
a
f
O
FrI z Fq r I r L
ln = lnG J + q lnG J + l l q M1 lnc h
P
Q
Hr K 2 Hq r K r N

F r IJ + z q lnFG q r IJ x l + r l
= ln = lnG
ln
H x r K 2 H q r K x
r
a x 0f
LM
O

P
q M ln
+ ln +

P

MN
QP

xi ri
ri
1
, i = i;
=
x1r1 + x2r2 xi x1r1 + x2r2 xi rj
i

jj

j i

i j

j j

i i

j ij

j ij

x1 1000 *
1 where 1* is as given above.
ms M1

ij

ij

k kj

1 =

ij

i j

*
1

ij

q rj
i xi qi x1q1 + x2q2
=
= i
xi ri x1r1 + x2r2
ri q j
i

jj