c O n c e n t r a o n c e l s

CONCENTRATION CELLS
cae of galvanic cells discussed earlier, the electrical energy arises from the chemical
place in the cells. There is,
ions
reactions which take
which take however, another category of cells in which the
MF arises not due to any chemical reaction but due to transfer of matter from half-cell to the
hecause of a difference in the concentrations of the species involved. These are called concentration
one

other
els.

Cocentration cells are of two types, viz.,

. Electrode-Concentration Cells and 2. Electrolyte-Concentration Cells.

1. Electrode-Concentration Cells. In these cells, two like electrodes at different concentrations

are dipping in the same solution. Two hydrogen electrodes at unequal gas pressures immersed in the
same solution of hydrogen ions constitute an electrode-concentration cell. This may be represented as
follows

Pt:H2p)| Solution of H* ions, say, HCI solution | H2P2); Pt

 A

1 1 11 11 1, 1
1 11 11

JO
 CHEMISTRY-Il. EMF OF GALVANIC CELLS
ELECTROCH 855
19.
Example 19. Calculate the EMP of the electrode-concentration cell: Pt; HzPi), HCI, H2p:) re***
and p2=400 torr.
torr
600
Solution: The cell reactions in this case are

2H+2e
R.H.E.
HP2) Reduction)

L.H.E. HP) 2H +2e Oxidation)

Overall reaction: H2P) H2P)
E 0 0591 log 400 torr
2
= -

0-02955 log= 519x10 v

600 torr

2. Electrolyte-Concentration Cells. In these cells, the two electrodes of the

ning in solutions of metal 1ons of different concentrations and hence of different same meta One
activities. a
1S represented below
Such cell
Zn, Zn(a+)) | Zn2* (a,)2, Zn
In this case, both the electrodes are of the same metal (Zn) and these are in contact with
calutions of the same 1ons (Zn-"). The concentrations and hence activities of the ions are, however,
diferent. Let (a) and (a.h be the activities of zinc ions in the two electrolytes surrounding the
electrodes. 1The two electrolytes, which are generally ZnSO solutions, are separated from each other
by a salt bridge. This is represented by the double line put in between the two half-cells.

Thereactions occurring are

R.H.E. Znt(a-h + 2e Zn(s) (Reduction)

L.H.E. Zn(s) Zn(a) + 2e (Oxidation)
Overall reaction: Zn2t(a+ Zn (a)
The net process thus involves the transfer of 1 mole of Zn?+ ions from the solution in which the
activity is (a+» to the solution in which the activity is (a+)1
According to Nernst equation, the reduction potentials of R.H.E. and L.H.E. are given by

ER = E RT
- n =E + In (a,+)2
nF a)» el T ..45)
nF

and EL =E - In E n (a,) .(46)

Ecell E= ER - EL = In2 ..(47)

For the process to be feasible, EMF should be positive. Hence, (a,)> >
(a-)
Substituting activities (a+)\ and (a+» by molalities m and nm> (vide Eq. 38), in Eq. 47, we have

RT
EcellE = 2F In Ym, .(48)
Y1
Where y1 and 72 are activity coefficients of the electrolytes in the two solutions.

Consider another similar concentration cell represented by

Pt, Hzlg), H*(a) l| H*(a,)>, Ha(g). P
atm I atm
 E

11 11 1
1 11 1

(C
 EMISTRY-Il. EMF OF GALVANIC CELLS 857
LECTROC
we see that when a2 d1, E is positive so that the process is spontaneous from ng
Hereonsists in the dilution of HCI from activity a2 to activity a even though the two
leftre not in contact with each other.
solution

late the EMF of the concentration cell

20. Calculat in a
nple consisting of zinc electrodes, one immersed
ExaQ molality (number of moles dissolved per kg of the solvent) and the other in a solution of 0-1 molality
soluti

a t2 5 °
The two solutions
C
are separated by a salt bridge. "The mean activity coefficient of the electrolyte may be
be unity.
to
aumed

Solton.
The cell may be represented as

Zn, Zn (m1 =
0-01) Znt (m=0:1), Zn
ot the cell, E, is given by
The EMF

E =In a,)2 2:303 RT 72m2 (Eq. 48)

2F log

-0-0591
2
log 00-01 at 25°C (71 72 = 1)

= 0-0295V

Fxample 21. Find the pontential difference between the hydrogen electrodes in the cell
Pt, Ha(g), HC1, AgCIs), Ag | Ag, AgCls), HCI1, H(g), Pt
atm m= 0-01 m=0-10 1 atm

at The activity coefficients of 0-01 m and 0-10 m solutions are 0-95 and 0-85, respectively.
Solution: The potential difference (E) between the two hydrogen electrodes is given by Eq. 49, viz,

RT" a+)2 2303 RTr

E F (a,))
nF
log Y2/m2
Y1m

0-0591
1
log 0-10 x 85
0-01 x 95
at 25°C = 0-056 V

Types of Electrolyte-Concentration Cells

Electrolyte-concentration cells in which solutions of the same electrolyte of different concentrations
are used are of two types. In one of the types. the two electrolytic solutions are not in direct contact
with each other and the transference of ions from one solution to the other does not take place
directly. These are called concentration cells without transference. The two solutions are separated
from each other by means of a salt bridge or by some other means to be considered shortly. In the
second type, the two solutions are in direct contact with each other. The transference of ions from
one solution to the other takes place directhly. Such cells are called concentration cells with transference
We shall consider here both the types of concentration cells.
Concentration Cells Without Transference. The two concentration cells discussed above in
which the two solutions are separated from each other through a salt bridge fall in this category. But.
more often some other means are employed to keep the solutions apart and bring about the transference
of ions indirectly.
In order to understand the setting up of such a cell, consider a simple electrochemical cell
Such as

H2(8). HCI (a,)| AgCls). Ag

I atm
Let the activity of H ions in the solution be (a+)1 and that of Cl ions be (a_)1. Since reduction
lakes place at the right hand electrode and oxidation at the left hand electrode, the two half-cell
858 PRINCIPLES OF PHYSICAL CHEMISTPV
reactions will be as follows
Reduction half-cell reaction
AgCIs) +e Cl (a)+ Ag(s) ..)
Oxidation half-cell reaction
H ( a ) +e
1/2 H8) ...i)
in the cell for one faraday of electricity is obtained by
The net reaction taking place adding
equations (i) and (ii). Thus.

1/2H8) + AgCI)= H(a) + Cl(a.)+ Ag(s)

Now consider the same cell with the difference that the activity of HCI solution is now a
d2.
Pt, H2(g). HCIla2) | AgCls), Ag
atm

The net cell reaction for one faraday of electricity will now be as follows

1/2 Hg) + AgCI) H*a)2 + C (a.)> + Ag(s)

Finally, consider the situation when the two cells are connected to each other in such a way that
they send current in opposite direction. Thus,
Pt. Hg), HCla). AgCIs), Ag | Ag. AgCI), HCIa2), Hag). Pt
atm I atm

The overall reaction of the combined cell for the passage of one faraday of electricity will,
evidently, be obtained by subtracting equation (iv) from equation (iü), i.e.,
Ha)2 + Clr(a)2 == Ha+) + Cl(a. .51)
Thus, for the flow of one faraday of electricity, the overall reaction is the transfer of one mole
of each of H* and Cl ions or one mole of HCI, from a solution of activity a2 to that of activity a.

Hence, EMF of such a cell would be given by

Ew.o. In n (a ..(52)

= a)3 ...(53)
(vide Eq. 37)
F
(a
where (a)1 and (a,)2 are the mean ionic activities of the electrolyte in the two solutions and the
subscript w.o.t. stands for "without transference'. Applying Eq. 43, we have
Ew.ot = (RTIF) In (a2/aj) ..54)
where a and a2 are the activities of hydrochloric acid in the two solutions.

It will be observed that the cell reaction does not involve transfer of electrolyte from one
solution to the other directly. It takes place indirectly. The cell is, therefore, a concentration cell
without transference.
If the middle electrode, viz., Ag, AgCl(s), is withdrawn, the two solutions of HCI will be in
direct contact with each other. The cell will then become a concentration cell with transference. A
little reflection shows that a concentration cell with transference in which the two electrodes are
 HEMISTRY-II. EME F GALVANIC CELLS 859
UECTROC
with respect ect to cations
(H 1ons in the present case) can be converted into a tion
eversible u t

ference by interposing in between another electrode

t r a n s f e r e n c e
concen ra pect
e l lw i ü h o u
ions ( C I ions in the present case).
which is reversible w
example of a
concentration cell without transference. in which the electrodes are reversible
A o t

to a
cation.
cati is given below
respect

ith Zn. ZnSO,(a1). PbSO4(s). Phb, PbSO4(s). ZnSOg(a,). Zn

tration cells without transterence in which the end
C o n c e n t r a
electrodes
hich an electrode reversible with respect to
and in whi a cation are reversible
is inserted
with
resPare
in between.
nion
Ioan .
known. One such cell is as represented below :

Ag. AgCI(s), HCl(a). H2(g). HC\a2).

AgCl(s). Ag
The end electro
lectrodes are reversible With respect to Cl ions while the intermediate electrode is reversipic
ions.
with
respect
to H
centration Cells with 'Transference. Now consider a concentration cell formed by combining
rogen gas electrodes in contact with HCI solutions of different concentrations. The two
rwo
HO hy hydro
a r e in rect contact with each other, as shown
olutions
Pt. H2(g), HCI(a1) HCI(a2), H28). Pt
atm 1 atm
Ht
CI
The reaction on the left involves oxXidation and that on the right involves reduction, as usual.

The following changes are involved for the flow of one faraday of electricity
Left Hand Electrode

Halg) H* (a+)1 + e ..(i)

Right Hand Electrode

H(a+)2 +e }H:(8) .. (ii)

Thus. Ht ions are generated at the left hand electrode and consumed at the right hand electrode
as the current follows. Since the solutions are in direct contact with each other, the ions are free to
move from one solution to the other when current flows through the cell. In the
present evidently,
case,
H ions move from the solution on the left hand side to that on the right hand side. Since anions
move in direction
opposite to that in which cations move, CI ions migrate from right to left. as
shown in the cell above.
Let r be the transport number of CI ion and
t+ (= 1 t) that of Ht ion in HC1. Then, for -

one faraday of electricity passing through, t faraday will be carried by Cl ions and I+
Hions. According to faraday by
Faraday's second law, t equivalent of Cl ions will be transferred from the
solution of activity az to the solution of
activity aj. This may be represented as
tCI(a)2 Cla ) .(iii)
At the same time, t+ equivalent of Ht ions will be transferred from the solution of
TO that of
activity a2 which may be
activity a
represented as

tH*(a+)1 tH*(a+2 . . (iv)

ne net
result for the flow of one faraday of electricity is summed up below
Let Hand Electrode. The following operations occur at this electrode
Gain of 1 gram equivalent of H* ions by process (i)
Loss of gram equivalent of H+ ions by process (iv)
 PRINCIPLES OF PHYSICCA
860
equivalent
=
1 gram equivalent
CHEMISs
Net gain of H ions = (1 - 1.) gram

At the same time,

equivalent by process (iüi)
ions L gram
of Cl
=
Net gain
occur at this electrode
Right Hand Electrode. The following operations
Loss of I gram equivalent of H ions by process fi)

Gain of 1 gram equivalent of H* ions by process (iv)

ions (1 t ) gram equivalent =
gram equivalent
Net loss of H* = -

At the same time.

Net loss of Cl ions equivalent by process (ii)
=
1 gram
Thus. for every one faraday of electricity, there is net transfer of t gram equivalent of H
and gram equivalent of Cl ions from right to left, i.e., from the solution in which activity of
CI
is a to that in which activity of HCI is d1.

These changes are represented as

H(a)2 t . H(a-)
L Cl(a)2 1 . Cl(a.)
The EMF of concentration cell with transport, on analogy with Eq. 52, therefore, is given by

Ewt =
In t Rna ...(55)
F (an (a_)
If (a-)) and (a-)z are the mean ionic activities of the two hydrochloric acid solutions. it follows
by the definition given in Eq. 33 that

( a f = (a-)y(a)) and (a5 = (a.pla.)2

Eq. 55. therefore, may be put as

Ewt In 5 .(56)
F
(a.
Knowing that the activity of a uni-univalent electrolyte is given by a=(a-?, Eq. 56 may also be
written as

.57)

where a2 and a, as already stated, are activities of HCI solutions of the right and the left hand
electrode, respectively.
Eq. 57 is used for calculating activity of an electrolyte at a given concentration from the experimenta
value of Ew.. One of the solutions used should be of known
activity.
Liquid Junction Potential (LJ.P.)
Eq. 57 derived above for the EMF of a concentration cell with transference includes the potenna
at the junction of the two solutions of HCl as well.
Eq. 53 for EMF derived earlier when the
wo
 CHEMISTRY-I, EMF OF GALVANIC CELLS
EIFCTROCH! 861
not in
in direct contact with each other
are
does not include the ential.
tond53
solutions

a n d
33 may be reproduced
m a

as liquid junctton P
57

Eys.

Ew RTn , )
=21 I
(58)
F
(a,h
RT (a,)
Ew.o.t. F
In ..(59)
(a
Hence, liquid ction potential E is given by

E= E. Ew.ot =(21. -1)In (a,)

(a
( ( + (1 -

t,) - 1] In 4,)2
(a
(1. -t,) In ,J ...60)
F (a
tis evident from Eq. 60 that the sign as well as the magnitude of L.J.P. depends on the
ference numbers of tne anion and cation. If the transference numbers of the anion and cation of
lectrolyte are the same or nearly the same, i.e., t = t4, then L.J.P. = 0 or negligibly small. If
tTAnsference number of cation iS greater than that of anion, i.e., t+ > t, then L.J.P. will be
the
eafive and if reverse is the case, i.e., t > t4, then L.J.P. will be positive and will add to the
2ega
EMF of the cell.
Potassium chloride and ammonium nitrate are amongst the electrolytes in which transference
numbers of cations and anions are nearly the same. The solutions of these electrolytes are, therefore,
freauendly used as salt bridge because the liquid junction potential is then reduced to a minimum.

Example 22. Calculate the liquid junction potential at 25°C between two solutions of HCI having mean
ionic activities of 0-01 and 0-001, respectively. The transference number of Ht ion (t+) in HCI may be taken
as 0-83.

Solution In this case,t 0-83 that t. 1- t+ 0 17

=
so = =

(a+ = 0-01; ( 2 0-001

E=(t -t) In 2
(Eq. 60)
(a-h
0-001
=
(0:17 0-83) 0-0591 log.1 =0-0039 V (at 25°C)

Example 23. Calculate the liquid junction potential associated with the following cell
Ag), AgCMS), HCI (m=1:0, Y1 = 0-809): HCI (m^=0-05, Y2=0-830), AgCl\s), Ag(s).
if the transference number of H* is 0-83.
Solution: =0-83 so that = l -0-83 = 0:17. Hence, from Eq. 60,

E = (t. t4) I n 2 = (t. - t) n Ym2

(a
0 83 x005
=
(0-17 083)x0-0591 log 0 809 x1-0
at 25°C

= 0-050 volt 50 mV
 PRINCIPLES OF PHYS
862 CHEMISTRY
the concentration cell with transference, viz.,
Example 24. The EMF of
0-009) HCI (a4 =
0-017), H2(1 atm) ; Pt,
Pt: H2 (1 atm), HCI (a = :

of the corresponding cell without

transference is O-017 V. Calculate th.
is 0-028 V at 25°C. The EMF liquid
transference number of the H* ion.
junction potential, E, and the
includes in it the liquid junction potential while
le
Solution Since the concentration cell with transference
:
would be given by
without transference does not. the liquid junction potential
0-028 0-017 0-011 V =

E Ew.t. -

Ew.ot. = -

the operation of the cell, there is transfer of HCI from a sohutice

ution of
Using Eq. 60 and remembering that during
higher activity to one of lower activity, we have
E = (. - t4) n = (( - t4)x0-0591 log
0-009
0017
F (a1
0-011 1 - t+)x(- 0-0167)

0-011 = 0-65
or
- I 0-017
+ I. = 1, hence 4 = 0:825
Since
Thus. the transference number of Ht ion = 0-8255