ACTIVITY COEFFICIENTS

F-M growth law:

ddp
dt
=
1
2
v
m

8RT
M
[CC
s
exp

4M
RTdp

] (1)
C
s
= C
sat
X
X=mole fraction in droplet
=activity coecient
What is the composition dependence of the activity coecient ?
Thermodynamics does not provide any detailed answer!
Only guidance comes from Gibbs-Duhem -equation: (binary system)
SdT V dp +n
a
d
a
+n
b
d
b
= 0
Of the 4 variables (T, p,
a
,
b
) only 3 can be varied independently.
Choose mole fractions x
a
, x
b
instead of
a
and
b
as independent variables:
(One mole fraction is enough!)
SdT V dp +n
a

a
T
dT +

a
p
dp +

a
x
dx

(2)
+n
b

b
T
dT +

b
p
dp +

b
x
dx

= 0 [x = x
a
]
Note: T- and p-dependence of

i
T
= S
i

i
p
= V
i
SdT V dp (n
a
S
a
+n
b
S
b
)dT (3)
+ (n
a
v
a
+n
b
v
b
)dp +

n
a

a
x
+n
b

b
x

dx
= 0
n
a

a
x
+n
b

b
x
= 0 | : (n
a
+n
b
)
x

a
x

T,p
+ (1 x)

b
x

T,p
= 0 (4)
G-D at constant T

n
i
d
i
= V dp
This is valid for any phase; apply it for the solution

sol
i
=
vap
i
=

i
+RTlnp
i
d
sol
i
= RTdlnp
i
RT

n
i
dlnp
i
= V dp | :

n
i
1
(A relationship between changes in the total pressure and changes in partial
pressures)

x
i
dlnp
i
=
V dp
RT

n
i
=
v
l
dp
RT
v
l
= mean molar volume in liquid phase
=
v
l
pd(lnp)
RT
=
v
l
v
g
d(lnp) 0
v
g
= mean molar volume in vapour phase

x
i
dlnp
i

= 0 [exact if p = constant]
BINARY: x
a
dlnp
a
+x
b
dlnp
b
= 0
At constant T, the changes in lnp
i
are due to changes in x
i
x
a

lnp
a
x
a

T
+x
b

lnp
b
x
a

T
= 0
x
a
+x
b
= 1 dx
a
+dx
b
= 0
x
a

lnp
a
x
a

T
= x
b

lnp
b
x
b

T
or
x
a
p
a

p
a
x
a

T
=
x
b
p
b

p
b
x
b

T
DUHEM-MARGULES EQUATIONS!
(Relationships between the gradients of the vapor pressure curves)
MAY BE USED TO CHECK THE CONSISTENCY OF THERMODYNAMIC
DATA!
Raoults law:
Henrys law:
Electrolytes:
(DENBIGH p.223-227, gs. 25-29)
Raoults law & Gibbs-Duhem
assume all components obey p
i
= K
i
x
i
(if K
i
= p

i
, this is Raoults law)
dlnp
i
= dlnK
i
+dlnx
i
= dlnx
i
=
1
x
i
dx
i

x
i
dlnp
i
=

x
i
1
x
i
dx
i
=

dx
i
= 0
GIBBS-DUHEM IS SATISFIED!
2
Assume that all solutes obey p
i
K
i
x
i
(i = 2, ..., n)(as x
i
0)
How about the solvent (i = 1)?

x
i
dlnp
i
= x
1
dlnp
1
+dx
2
+... +dx
n
= 0
x
1
dlnp
1
= dx
1
dlnp
1
= dlnx
1
p
1
= x
1
p

1
In other words.
If all solutes obey Henrys law, the solvent obeys Raoults law.
Margules and van Laar equations
Raoults & Henrys law are not the only permissible solutions to
x
a
lnp
a
x
a
+ (1 x
a
)
lnp
b
x
= 0
Margules solution: a power series
ln
p
a
p

a
x
a
=
a
(1 x
a
) +
1
2

a
(1 x
a
)
2
+
1
3

a
(1 x
a
)
3
+...
ln
p
b
p

b
x
b
=
b
(1 x
a
) +
1
2

b
(1 x
a
)
2
+
1
3

b
(1 x
a
)
3
+...
Insert into equation (3rd degree)

a
=
b
= 0

b
=
a
+
a

b
=
a
log
p
a
p

a
x
a
= (2B A)(1 x)
2
+ 2(AB)(1 x)
3
log
p
b
p

b
(1 x
a
)
= (2AB)x
2
+ 2(B A)x
3
1
3

b
= 2(B A)
1
3

a
= 2(AB)
1
2

b
= 2AB
1
3

a
= 2B A
3

b
= 4A2B
= 4B 2A+ 6(AB)
= 4A2B

/

A,B are coecients to be t into experimental data!

Van Laar equation:
log
p
a
p

a
=
A
[1 +
Ax
B(1x)
]
2
log
p
b
p

b
(1 x)
=
B
[1 +
B(1x)
Ax
]
2
EXERCISE: Look for vapor pressure and activity coecient for some binary
system and nd values for van Laar equation A and B.
4