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? H E N E R N S? D I ST R I B U ? I O N L A W

N e r n st D i st r ibu t io n l
aw
I n 18 7 2 B e r t h e l o t a d J
i
in
n
u n gf l e is h f o u n d t ha t w h e n s o l u t i o n s o f io d n e
b
c a r o n d i su l ph i d e
o f d i f fe r e n t
c o n c e n t r a t io n s
d
i
e
b
t
i
d
u
t
r
i
s
th e i o d n e
w e r e s h a k e n w i th d i s t i l le d w a t e r
it s e l f b e t w e e n th e tw o so l v
e n ts in s u c H a
ti
w a y th a t a t a
gi v e n t e m p e r a t u r e th e r a t i o o f i t s c o n c e n t r a o n s
i n th e t w o l a y e r s w a s c o n s t
a n t i r r e s e c t iv e
d
o f th e a m
r
s
p
h
o
f
i
i
d
I
u t
t er w
,

02

m
Th e

K o is te r m

c o n stan t

C S2
C

H 2o

J C2

ne

Ko

e d a s th e

p a r ti t io n c o e f fi c ie n t o r dis t r ib u t io n c o e f & c i e n t
N e m s t h o w e v e r s h o w e d th t h
a
t e r a t i o c l l c 2 i s c o n s t a n t o n l y w h e n th e s o l u t e h a s t h e s a m e
m o le c u la r c o n dit io n s
i e
t h e s a m e m o ta r m a s s i n t h e t w o s o l v e n t s I f a s o l u t e
p a r tly a s so c ia te s to
f o r m do u bl e m o l e c u l e s i n o n e s o l v e n t b u t
n o t in the o the r
t h e l a w i s v a l i d o n l y i f th e r a t io o f
c o n c e n t r a t i o n s o f s i n g l e m o l e c u l e s i n th e tw
h
i t k
i
id
o
ti
,

T h e d ist r ib u t io n

f ben z
ist s m

o ic

id be tw

a se s

n to

en

co ns

on

era

be ta k e n a s a typ ic a l e x a m p l e
In be n z e n e , ho w e v e r
a s s i n gl e m o l e c u l e s
,
i e
a s C H s C 0 0 H
be n z o ic a c id e x i s ts as a s so c i a te d m o le c u l e s , i e
a s (C H 4 C 0 0 H ) 2 a l o n g w i t h o n l y a s n 1a l l p r o p o r t i o n
T h e N e r n s t d i s t r i b u t io n l a w i s v a l i d o n l y fo r c o n c e n t r a t i o n s o f s i n g l e m o l e c u l e s
o f s in g l e m o l e c u l e s
in t h e t w o p h a s e s T h e r e f o r e i f t o t al c o n c e n t r a t i o n o f b e n z o ic a c id i n b e n z e n e i s t a k e n th e l a w w i l l

In

th e

w ate r

ac

id

ex

ac

w ate r

ee n

d be m

an

o stly

ene

m ay

not

ho ld go o d

Th e N e m

st

d i s t r i b u t io n l a w

m ay

th u

be

s tate

as

fo llo w

W h e n a s o l u t e d i s t r i b u t e s i t s e l f be t w e e n tw o im m i s c ib l e s o l v e n t s i n c o n t a c t w i t h e a c h o th e r
th e r e e x i s t s , f o r s i m i l a r m o l e c u l a r s p e c i e s a t a g i v e n t e m p e r a t u r e a c o n s t a n t r a t i o o f d i s t r i b u t i o n
b e t w e e n t h e t w o s o l v e n t s i r r e s p e c t i v e o f t h e t o t a l a m o u n t o f th e s o l u t e a n d i r r e s p e c t i v e o f a n y o t h e r
m o le c u l a r sp e c i e s w h ic h m ay be pr e se n t
,

i t i on s f or t he v a l i di t y o f t he
v a l i d i t y o f th e d i s t r i b u t i o n l a w a r e
1

C o n s t a n t t e m pe r a t u r e

E x i ste n

In

a dd i t io n

ce o
,

th e

s im

ilar

an

i st r i bu t i on

aw .

he

e s s e n t i al

wo

pr

si t es

er e w i

or

he

in th e tw

m o l e c u la r spe c ie s

f o ll o w in g

con

a r e also

d it io n s

n ec e ssa r

pha se s in

c o n tac

t w ith e a c h o th e r

T h e de p a r t u r e s u s u a l l y s e t i n a t h i gh e r c o n c e n t r a t io n s G e n e r a l l y
1 Th e s o l u t i o n s a r e d i l u t e
I n a n e x t r e m e c a s e b o th t h e
t he l a r ge r is th e d e v ia t io n
e n t r a t io n
t h e h i gh e r th e c o n c
sp e a k i n g
i
i
h
K D i s giv e n by
h
t
n
t
o
n
c o e f fi c ie n t
T
e
a
n
e
i
t
p
d w i th r e s p c t t o th e s o u e
so l v e n t s m a y b e s a tu r a t e
(2 )
KD - s Js2
,

he r e

be

sl

an

str ic t ly v a

52 a r e

l id

on

t he

ly if

s o lu

51 an

b i l i t ie s
d

82 a r e

f th e s o l u t e i n t h e t w
i f the
i e
n o t la r ge
,

6 9 7

so lv e n t

so lu t e

is

laye r s

sp a r in

gl y

T he
so lu

a bo v e

e qu a t io n

b l e in

eac

ill

so lv e n t

698
I
p R I N C I P L ES O F P H Y S C A L C H EM I ST RY

2
w ater

in

The tw o li
qu i d s
d the ir m
u tu a l

c o n tac

so lv e n t

a n o th e r

t w i th

2 i s 11
2
i e ,
,

e ac

W hen tw

H
th e r e fo r e
,

or

also

R T In

R T ]n q

fo

phase 1

1l z

02

R T ln 02

fo

Ph a s e 2

(6)

R T In

al

112

R T In

R T In

a c o n stan t

(a J a z )

Ft

(7 )

rt
po te n ti a l s P

( be i n g th e

g a s c o n s ta n t
=

t f o l l o w

(a t

c o n sta n t

a /a z

her e x l

an

c o n st an t s

x 2 a r e the m o le

f o r th e

s o lu

t e in

s in c e

if

c o n c en tr a

a su

c o n st an

t he s o l u t i o n s a r e d il u te
,
ti o n s

bstan

ce

ar e

i s pr

X2

esen t

CJ C

J Cz

r e

law

(8)
ac co r

c o n st a n t

(a t

c o n sta n t te m

c o n sta n

in tw

c o n stan t

ph a s e s ir i

c o n sta n t

din g to

h ic h

pha se s

pe r atu

(a t

re

a c t i v it y

an

d kl

an

at c o n sta n t te m

i th

e ac

p e r a tu

(9)
a r e th e

H enr y

'

( 10)
is

pe r a tu r

r e

d kz

c o n st an t te m

c o n tact w

t t e m p e r a tu r e )

t h e r a t i o o f th e m o l e f r a c t i o n s

s in c e R

c o n st a n

ph a se

so l u te i n the t w

(a t

d p

alm

Hence,
X

T hu

k t x 1/ k

pe r atu

d hen e H

an

each

f r a c t i o n s o f th e
the tw o ph ase s

x l l 1z

F u r th e r
a ti o o f the

in

ye

an

s tha t

c o n st a n t t em

ce

law

(4)

th e s o l u t i o n s a r e d i l u te t h
e y be ha v e id e a l l y
,
is p r o po r t io n a l t o m o l e fr a c tio n i
d
s o be

e n e and

rt l

al j
Si n

be

H en c e

is

1
s u p p o s e f u r t h e r t h a t i t s c h e m i c a l p o t e t i a l i n s o l v e n t 1 i s p r a n d in
q
p h a s e s a r e i n e qu i l i b r i u m , th e i r c h e m i c a l p o t e n t i a l s w : l l b e e qu a l to o n e

the r

Si n c e

an

(e g

i i ble
m u tu a l l
y im m i s c j b l e o r o n l y v e r y s p a r i n g l y m s c
i s c ib i l i ty i s n o t a l t
lu te
e r e d b y th e p r e s e n c e o f th e s o

are

an

the r

o st the

sam e

a s th e

(11)

s in

gle

th e n , a t e q u il i b r i u m

T hi s i s th e N e r n s t d i s tr i bu t i o n l a w

C2

th e to t a l c o n c e n t r a ti o n o

A pp lyin g the l a w
(X )n
o le c u le s v iz
,

f th e
f

c
n

so

l u t e i n t h i s ph a s e

be

F ig

h e m i c a l e qu i l i b r i u m t o t h e e qu i l i b r i u
i n t h e s e c o n d ph a s e , w e h a v e
,

P(] "

O C).

s s o c ia t io n

betw

een

th e

in

o ne

t he

a sso c iate

p h a se s

an

0 21

T H E N ERN ST D IST R I B U T I O N LA W

P(]

or

/K

699

[(X ) , ]

I f th e s o l u t e e x i s t s l a r e l
g y
d il u t io n s th e c o n c e n t r a t i o n o f t h

Fr o m E qs

13

an

d 14

pq

c o n s ta n t

F r o m Eq s
Eq

15

an

d 16

17 h a s b e e n

id

ac

v a lid o n l
y

fo r

0 51

c o n c e n tr a t iqn s o

m o le c u la r

i lar

sim

s pe c ie s

ci

07

Ko

g th e d i s t r ibu t i o n o f b e m o i c a c i d b e t w e e n w a t e r a n d b e
(C H 4 C 0 0 H ) 2 i n b e m e n e b u t i n n o r m a l s t a t e i n w a t e r

stu dyin

e x i st s a lm o s t e n t ir e l
y as

So l u t i o n
er

c a se

Phe n n l i n
t he r a t i o

c ho l o r o fo r m

c 1/ c 2 s h o u

l d be

th e n u m b e r o f m o l e c u l e s o f p h e n o l
v a lu e s

T he

Jc2

J c 2 in t he

E v id e n t l y , t h e
v a lu e s

A fa ir l y

r es u

ra t io

hic h

a s s o c ia t e t o

16 3

O 3 70 1 ;

b e p r e se n t e i th e r a s
hil e in the la tt e r

m ay

c/c2

is

c o n sta n t v a lu e o f

cl

s ho w s t h a t

an

or

c2

in

st a t e

m o l ec u l a r

the

So l u t i o n

Let

u s a ssu m e

so lu

f t he

' '

a n d t he

th e s a m e

"

se c o n d

he n c e

that

aM um e
s te ps

th e

f c r is

m o le c u l e s

ld b e

c o n st an t

t he

for

In

the

g iv i n g

0 0 80 3

be

n o t e x i st a s s in

fo llo w

as

e x i st s a s

t e b et w

m o le c u le s

in

c hl o ro

fo rm

do u ble

m o lec u les

(c l )

w a ter

een

gle

an

in

c hlo r o fo r m

chlo r o fo r m

0 02 3 7

0 33 8

0 753

(c z ) ,

t h e f o ll o w i n g

o fo r m

Ko

(N e m

F o r t h e Fi r s t s t e p c 2 l c l - 0 3 38 10 160 = 2 1 1
d if fe r e n t , he n c e o u r a s s u m pt io n i s w r o n g
Let

fi r s t

t e in

hlo r

mol che

0 0 1 60

c h lo r

v e

tha i
c 2/ c l

ar e

sa lu

ga n i c

Cl

ph e n o l

ga

5 4 30

H e n c e , p he n o l d o e s

v a r i o u s c as e s c o m e o u t t o

a s a s so c ia t e d
sho u

0 436

O 13 7 3

rm

en e

1 850

n o t c o n sta n t

in th e

fo l lo w

as

0 2 142 ;

m o l e c u le s o r

t h e r a t io

c as e

a s i n g l e a s s o c ia t e d

be

0 76 1

E x a m p l e 2 F o r t h e di s t r i b u t i o n
lt s w er e o bt a in e d

D et er

g iv e

no rm a

c o n sta n t w

v a r i o u s c a se s c o m e o u t t o

0 2 54

T he

0 61

MaM

c o n st an t

h e c k e d by

con

E x a m p l e 1 E x p e r i m e n t s i n t h e s t u d o f t he di t i b t i
s r
u
o n o f p h e n o l b et w e e n w a t e r a n d c h l o r o f o
y
f o l l o w i n g r e s 11l t s
C o n c e n t r a t i o n i n a q u e o u s s o l u t i o n s (c )
0 494
0 16 3
0 436
0 2 54
1
C o n c e n t r a t i o n i n c hl o r o f o r m s o l u t i o n (c )
0 - 2 54
0 76 1
1 850
5-4 3 0
2
W h a t c o n c l u s i o n c a n b e d r a w n f r o m t h es e r es u l t s c o n c e r n i n g t h e m o l e c u l a r c o n d i t i o n o f p h e n o l i n
so l u t i o n ?

fo r m

i n th e t w

CAX

T he

t l a r ge
hic h is ge n e r a l l y t r u e e x c e p t a
the to t a l
[ ( x ). ] m a y b e t a k e n a s e q u a l t o c 2

m o le c u le s ,

Si n c e t h e d i s t r i b u t i o n l a w i s

ph a s e s , h e n c e

0 31

e a sso c ia te d
m o lecu le s,

c o n c e n tr a t io n

as so c i ate d

as

c o n stan t

v alues

c o n s ta n t

f,

T he

'

/ cl
s o l u te

an d

f o r t he

se c o n d st e p ,

Th e s o 1u t e
are

36 3

and

e x is t s a .

36 6 ,

thu s e x ist s a s a

d im

c 2/ c l

d im

er

r e s pe c t i v e l y
er

in

0 7 53/ 0 0 2 37

in

c hlo r o fo rm

Si n c e t h e t w

hlo ro fo r m

318

W
o

st

d i s t r ib u t io n l a w )
T he tw o

v alu es

f in d tha t fo

v a lu e s a r e

the

p r a c t ic a l ly

H CA L C H EM IST RY
p R i N C i p LES O F P

700

2 D is s o c ia t io n o f t h e
f o r Dr u l a o f t h e s o l u t e S
u
in to A
co

d B i n th e
n c e n t r a t io n i n t h e
an

f the so lv e n ts L e t x
i t do e s n o t dis so c i a te i n the so l v e n
a r k e d 11 L e t c l b e i t s

so lu

ppo s e ,
l
so v e n t m
fi r s t so l v

te in

en

on e

an

c2

t m

l i d o n l y f o r t h e r a t io
l
o e c u la r s e c ie s in th e tw
p
v a

Su p p o s e

c o n c e n tr a tio n s o

Ph a s e r
n o

c2
,

(1

CC2 0

o ta

c2

l co

Cz a

C2

n c

D is s o c ia t i o n i n

F ig

c 2a

c 2a

din g to t he distr ibu tio n la w

ac c o r

p hase II
d i s s o c ia t io n

x
C2( 1

ar io u s

belo w
X

d i s so c i a t io

c l

o n c

sa l u te

a s sho w n

ilar

i s t h e d e g r e e o f d i s s o c i a t i o n o f th e
T h e n t h e c o n c e n t f a ti o n s o f th e v

X in pha se I I
spec ie s w o u ld b e

T h e r e fo r e

s im

so l v en ts

to t a l

th e

is

the n o r m al
be f o r e r e pr e se n t
d is so c ia tes
b
t
u
2
i
)
a r k e d I (F g

as

one

pha se s

the

0 81

CH

So l u t e e n t e r s i n t o c h e m i c a l c o m b i n a t i o n w i t h
f t h e s o l v e n t s W h e n t h e s o l u te e n t e r s i n to c h e m i c a l
c o m bi n a t i o n w i t h o n e o f t h e s o l v e n t s , t h e r e i s n o c h a n g e
i n th e g e n e r a l e qu a t i o n o f t h e N e r n s t d i s t r i bu t i o n l a w
a s sho w n be lo w

P ha s e I

on e o

Co

c l

n c

II1

qr

b e t h e c o n c e n t r a t i o n o f th e s o l u t e X i n o n e
o f th e s o l v e n t s i n w h ic h i t d o e s n o t u n de r g o a n y c h e m i c a l
3) a n d c 2 i t s t o t a l c o n c e n t r a t i o n i n t h e
c h a n g e (F i g
s e c o n d s o l v e n t w i t h w h i c h i t e n t e r s i n to c h e m i c a l
c o m bi n a ti o n f o r m in g c o m p l e x m o l e c u le s , a s r e p r e s e n te d
Let

C o n c en tr atio n

n c e n tr a t io n o

Co

A pp l y i n g th e l a w

u n co m

f the
che m

o le c u la r

Si n

ce

con c

Co

c2

b in a t io n

ith the s o lv

en t

ic al

c M

D i v i d in g E q

cz

ed

b in a t i o n

i t h th e

so lv en t

th e

th e n

c 2ce

qu i l ib r i u m

o c ) [ s o 1v e n t

(1

(1

r e p r e s ( n te

19 ,

d by E q

w e

hav e

(2 0 )

r e

ac

Eq

t io n

23

v a

J c 2

f th e

m ay
c

l id

on

so lv ( n ts

2 1, w

22 by Eq

th e f r

g iv e n t e m p e r a tu

czo

20

c o n MM

the

cl

fo r m

qu i l ib r iu m to th e

d i s tr i b u t io n l a w i s
o l e c u l e s o f X , in bo th th e

ce

in t o c h e m ic a l c o
o u l d b e a s fo l lo w

( 19 )

be take n a s c o n st an t
i
th e s o l v e n t i s i n l a r g e e x c e s s , it s c o n c e n t r a t o n m a y
c zce

No

sp e c ie s w

m o lec u le s

ple x

(2

gle

o ta

F ig

s o ]u t e m o l e c u l e s

bin e d

com

so l u te tha t e n te r s

concen

i s th e fr a c t i o n o f th e
t r a t io n o f th e v a r i o u s m

If

sin

e qu a ti o n

by the

Sin

X +

c 1

P h a s e J
b i n a tio n
i th so lv en t

co m

con M

e
-

ly f o r
hen c e ,

ti o n s

sim

ila r

m o

lec u lar

s p ec ie s

122 1

hav e

(23 )

c o n stan t

s o lu te tha t
h
t e r e f o r e , be

Jcz

c o n c en tr a

c o n sta n t

com

b in

es

i th t h e

sam e

so l v e n t

is

a lso

c o n s ta n t

at

w r itte n a s

(24 )

702

T he

[ 13 ]
T he

c o n c e n tr
a t io n s o

lts

r e su

m o

P RI N C I P LES O F PH YSIC A L C H EM IST RY

f th e
3

l dm

v a r io u s s e c i
es
p

[ 12 ]

o f de te r m in a i
t ons

in

the a qu e o u s
3

l dm

m o

c a r r ie d o u t
at

[i ]

3o c

laye r
A

il l b e

(B

as

fo llo w

l dm

m o

g i v e n in T a bl e 1

are

T AB L E 1

T he f a c t t ha t K i s
f the c o m l e x i o n i l
p
s

r e a so n abl
y c o n stan t

in

sp ite o

Ex a m ple 3 Ca lc l
u a t e t he d iss o c i t i
a o n c o n st a n t o f
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i n t h e l a b o r a to r y a s w e l l a s i n i n du s t r y I n th e l a bo r a t o r y f o r i n s qn c e i t i s f r e qu e n t l y
e x tr a c tio n
f a d i s s o l v e d o r ga n i c s u b s t a n c e f r o m a q u e o u s s o l u t i o n i t h s o l v e n t s s u c h a s
u s e d fo r t he r e m o v a l o
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etc
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h
l
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r
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par ti t io n c o e c e n o
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T H E N ER N ST D IST
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Th e

ON L W

s am e

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u n ex t r ac ted
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KDV
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e x tr ac t o n

th e a m o u n t w t h a t
2

am o u n t tha t r e
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e
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en

by

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id e n t th a t i n o r de r t o
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o
Po s s i b l e B u t n x v i s e qu a l t o t h e t o t l
a v o lu m e o f the e x t r a c t in
it
g l i qu i d a v a i l a b l e i e
i s c o n s t a n t T h e r e f o r e i t i s be t t
e r to k e e
p n l a r ge a n d v sm a l l r at h e r th a n th e r e v e r se I n o th e r
w o r ds
th e e f f ic ie n c
y o f e x t r a c t i o n i n c r e a s e s by in c r e a s i n th e n u m b
e r o f e x tr a c t i o n s u s in
g
g o nly a
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fr

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w ashin g o

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f p r e c ip i t a t e s i t i s m
be r o f t i m e s

o r e e f fe c t iv e

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e n c a r b o n t e tr a c h lo r i de a n d
w
b o n t e t r a c h l o r i de C a lc u l a t e t h e v o l u m e o f c a r b o n t e t r a c hl n r i d
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case

29

H tr

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K. V

W = 100 , V = 100

in E q

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8855
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100

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F PH Y SI C A L C H EM IST RY
p R IN C I p LES O

704

h
n d e t h e r , t e w a ter
E x a m ple 5
w h e n o 83 g o f s u c c i n i c a c i d w a s s h a k e n w i t h 1o o m l e a c h o f w a t e r a
'
c ted Ir om
a
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r
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e
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e
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W
705

s ta t e t he D i s t r i b u t io n l
aw

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How

1 Re
.

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on

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2

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