ELECTROCHEMISTRY-I.

ELECTROLYTIC CONDUCTANCE AND TRANSFERENCE 763

Example 19. Calculate the transport numbers of Li+ and Br ions when a current nows through an infinitcly dilute
aqueous solution of LiBr at 25oC, given the ionic mobilities of Li+ and Br- ions at inlinite dilution are .1.01 x l0-E ar d
8.09x10-t y-l r-1, respoctively,
^2
Solution : In this case, u: - 4'01 x l0-8 m2 V-l s-l and u"-:8'09x l0-8 rn2 V-l s-l
u+ 4.01 x l0-8 m2 V-l ,-l :
From Eq. 22, t+
o
=-=oo
tt+ + n- (4'01 + 8'09) x l0-8 m2 V-l s-l
0.331

o o
S;nce t, + t_
t
:I
-1

I - 0'331 :
o
t_ - 0'669

Examole 20. Molar ionic conductances at infinite dilution of Na+ and Cl- ions are 50.llxl0{ and
-O.}{ x lOJ S m2 moFl, respectively. Calculate the transport numbers of Na+ and CF ions.
Solution : According to Eq. 20,
50.11 x l0-4 S m2 mol-l
ti=
I'. + 1,"- (50.11 + 76.34) l0-4 s m2 mol-l
"
50.11 x lO-a S m2 mol-l : 0'396
126 -45 S nr2 mol-l

t-= o 76-34 x l0-a S m2 mol-l

= $'f[{
I:++l'-
+ I' (50.11 + 76.34) t l0-4S m2 nlol- I

As can be seen, ti + t: - 0'396aQ'SQd:l

Diffusion and Ionic Mobility. Electrical conductance is a consequence of the motion of ions in an
electric field. If the electric field is absent, the ions and the solvent molecules in solution move
=:lied
: ' random manner as a result of thermal energy. If there exists a concentration gradient for a given
: i::rolyte at constant temperature and pressure, then there is a tendency fbr the dift'usion of the
: .-:rolyte from a region of higher concentration to a region of lower concentration so as to reach an
:--:.ibrium condition wherein the concentration gradient is smoothed out. Diffusion is thus a process
- -.::r involves the migration of a component in solution down a gradient of its own concentration, i.e.,
-.:: a region of higher to a region of lower concentration.
.\n ion in a solution possesses a diffusion coefficient, D, which measures the mobility of thc ion
:-: :-. irs thermal energy, k7- lonic mobility, z, of the ion, on the other hand, measures the mobility of
-:: :-':r due to the kinetic energy imparted to it by the applied electric field. The parameters D and rt are
-: .::: b1' the Nernst-Einstein equation, vz.,
D ukT/ez : ...(23)
. -€:. e is the electronic charge and e is the charge number of the ion.

of N"J ion in 0'r M aqueous solution of NaCl at 25oC if the diffusion

---'';TJ,lil1'fi"f1'.3b.,11il'f #"3lTtv
i--,lurion z D - ukTlez IEq. 231

..*
*
D e z= (1 .30 x l0-e m2 s-l ;1t .602 x to-2e c;1t;
=
T to-23 I r -r Xzgg r)
= 5.06x10{m2V-lsl (J = volt-oulomb = VxC)
l-: :.:.,;ulared value compares very favourably wittr the experimental value of 5'19 x lg-8 rn2 y-l *-1.

\lolar Ionic Conductance and Viscosity. Consider

-1t.ra'
a single ion immersed in a liquid and subjected
i :: :.;r-*!ric field, E. As the ion moves through the liquid, its motion is retarded by the viscosity of the
. . - : l:: tiictional force, /, acting on a spherical ion of radius r, moving with a velocity v, is given by
 ELECTROCHEMISTRY-I. ELECTROLYTIC CONDUCTANCE AND TRANSFERENCE 767
Erample 25. At 25oC' the specilic conductance of a saturated solution of AgCl is 2.68 x 10-4 S m-l and that of *ater uith
rtjc"h the solution was made is 0'86 x 10{ S m-1. If motar conductances at infinite dilution of AgNO3, HNO3 and HCI are.
nspectively, 133'0xl0J,{21'0x10#and426.0xl0{Sm2mofl,calculatethesotubilityofAgCling;amsperdmJinrvater
x the given temperature.
SolutiOn! Kdui6n =KAgCt *K*ar",
... KAgct = Ksoludon-Kwater = (2.69-0.96)xlf4Sm-l = l.g2xl0-4S m-l
Since AgCl is formed according to the reaction
.-,
AgNO3 + HCI --+ AgCl + HNO3
:rrrce, using Kohlrauch's law,

ALnr., = A'*reruos +A'.ncr - A'nrHNor =(133.0 +426.0-421.0)xlO-4Sm2mol-l

= 138.0xlOa S m2 moFr

: r;: uEilI::;':::'::::11 "

A; 138.0 x l0-4smZmol-r
- -- " ^"
^*

= 1.32x l0-5 mol dm-3

.'. Solubility of AgCl = (1.32x1fr5 mol dm-3) (143.5 gmol-l; = 1.9;19-r g 6s1-l

Example 26. Calculate the solubility product of the sparingly solubte salt CaF2 from the following data : The molar
bnic conductances (at inflrnite dilutton) of Ca2+ and I- ions are l04x lOra and 48 x lOa S m2 mol-l, respectively. The
specific conductance of the saturated solution of CaF2 at roo4 temperature is 4.25x10-3 S m-l and the specific
conductance of water used for preparing the solution is 2xl(r4 S mJ.

Solution : [rt c mol dm-3 be ttre solubility of CaF2. Accordingly, the solubility equilibrium may be written as

caFz (s) ir ca2+(oq) + 2F(aq)

c?t
Then, at equilibrium, the solubility product of CaF2 is given by

K* = fCa2+l [F-]2 = (c) (2Qz = aS ...(i)

Specific conductance due to CaF2 alone

= r(soln)- K(water) : (4.25x1(r3 -2.OxlO4) S m-, = 4.05x103 S m-t

A'.tc"ql = li""r*, + 2?',.-, = (104 + 2xl8'yxto4Sm2mol-l:200xl0raSm2mol-l

For saturated solution of sparingly soluble salt, A, o l'r. Also, Am = rc/c

:. k_
c_ A,- =
4.05x10-3qm-r
= 2'025 x lo-rmol m-3 = 2'O25xl0a mol dm-3
tffi<;ffii:j-
Hence, from Eq. (i), K* = aC :4@'025x lOa mol dmJ;3 = 3'32x10-rl moP dm-e
4. Conductometric Titrations. Conductance measurements are frequently employed to find the end
points of acid-alkali and other titrations. The principle involved is that electrical conductance depends
upon the number and mobility of ions.
Consider, in the first instance, the titration of a strong acid, like hydrochloric acid, with a strong
base, like sodium hydroxide. The acid is taken in the conductivity vessel and the alkali in the burette. The
conductance ofhydrochloric acid is due to the presence ofhydrogen and chloride ions. As alkali is added
gradually, the hydrogen ions are replaced by slow moving sodium ions, as represented below :
H*(aq) + Cl-(aq) + [Na+(d4) + OH-(aq)l-----+ Na+(a4) + Cl-(aq) + H2O(r)
(unionised)

Hence, on continued addition of sodium hydroxide, the conductance will go on decreasing until the
acid has been completely neutralized. Any subsequent addition of alkali will result in introducing fast
moving hydroxyl ions. The conductance, therefore, after reaching a certain minimum value, will begin to
768 ELECTROCHEMISTRY-I. ELECTROLYTIC CONDUCTANCE AND TRANSFERENCE

increase. On plotting the conductance against the volume of alkali added, the points will lie on two
straight lines .dB and CD (Fig. 7). The point of intersection X of these two lines gives the volume of
alkali required for the neutralization.

D
trl EI
U
z zU
F F
U U
-) End point
o o
z z
o o
O U
\

VOLUME OF ALKALI ADDED VOLUME OF ALKALI ADDED

Fig. 7. Titration of a strong acid against Fig. 8. Titration of a weak acid against
a strong base. a strong base.

Suppose, it is required to titrate a weak acid like acetic acid, against a strong base, like sodium
hydroxide. The conductance of the acid will be low on account of its poor dissociation. On adding the
base, highly ionised sodium acetate is formed and herrce the conductance begins to increase.
CHTCOOH(aC) + [Na+(aq) + OH-(ag)]+ CH3COO-(aq) + Na+(44) + H2O(/)
(unionised)

When the acid is completely neutralized, further addition of the base introduces excess of fast moving
hydroxyl ions. The conductance of the solution, therefore, begins to increase even more sharply than
before. On plotting the conductance against the volume of the alkali added, the two lines obtained will be
as shown in Fig. 8. The point of intersection X gives the end point.
When a mixture of a strong and a weak acid is to be titrated
against a strong base, a combination of curves shown in Figs. 7 lIJ
U
and 8 is obtained. Suppose a mixture of HCI and CH3COOH is to z
F
be titrated against NaOH. Hydrochloric acid, being a much stronger U
D
acid, will get titrated first. The titration of acetic acid will o
z
commence only after hydrochloric acid has been completely o
U
neutralized. Hence, a combination of curves as mentioned above
is obtained. This is represented in Fig . 9. While the point B
VOLUME OF NaOH ADDIID
corresponds to the neutralisation of HCl, the point C corresponds
to the neutralisation of CH3COOH. Fig. 9. Titration of a rnixture of HCI
and CH3COOH against NaOH.
Finally, suppose it is required to titrate a strong acid like
hydrochloric acid, against a weak base, like ammonium hydroxide. The
conductance will fall at first due to the replacement of fast moving g+ gJ
ions by slow moving M{i ions. (J
z
H+(aq) + Cl-(aq'l + NH4OHI ----+ NHa*(aq) + Cl-(aq) + HzO(l) F
)o
U

After neutralisation of the acid, further addition of weakly ionised z

o
ammonium hydroxide will not cause any appreciable change in the U
conductance. The curves obtained will be as shown in Fig. 10.
voLtjME
5.Precipitation Titrations. The titration of silver nitrate against OF NH4OH ADDED

potassium chloride can also be carried out by this method. The reaction Fig. 10. Titration of a strong acid
involved may be represented as agairut a weak base.

Ag*(aq) + Not(aq) + [K+(aq)+ Cl-(aq)l-+ K+(ag) + NO;(<) + AgC(s)

Since the mobility of potassium ion is nearly the same as that of silver ion which it replaces, the
 ELECTROCHEMISTRY-I. ELECTROLYTIC CONDUCTANCE AND TRANSFERENCE 769

conductance will remain more or less constant and will begin to increase
onty after the end point. The curves obtained will be as shown in Fig. 1 1.
t!
U
In order to get accurate results, the change of volume during the z
titration should be as small as possible. For this purpose the titration F
U
solution in the burette is usually five to ten times stronger than the o
-a

solution taken in the conductivity vessel. z

o
O End point
Conductometric titrations have several advantages. Coloured solutions,
which cannot be titrated by ordinary volumetric methods with the help of
indicators, can be successfully titrated conductometrically. The method VOLUME OF KCI ADDED
can also be employed in the case of very dilute'solutions and also for Fig. I I . Titration of silver nitrate
weak acids and bases. Further, no special care is necessary near the end aqainst ootassiunt chloride.
point as it is determined graphically.

Ostwald's Dilution Law

As is well known, according to Arrhenius theory of electrolytic dissociation, the molecules of an
electrolyte in aqueous solution undergo spontaneous dissociation into positive and negati,ve ions and that
there is a dynamic equilibrium between ions and the unionised molecules. Ostwald, therefore, applied the
law of chemical equilibrium to such systems.
Consider an electrolyte AB, c motes of which are dissolved per dm3 of an aqueous solution. Let a be
its degree of dissociation, i.e., the fraction of total concentration of the electrolyte wltich exists in
dissociated state. Then,
AB=4++ B-
Initialconcs. c 0 0
Equilibrium concs. c (1 - a) ca ca
The equilibrium constant is given by the equation
,, ca cg. cdz
K=-=
x ...(29)
c(l -a) l-a
Eq. 29 is the mathematical representation of Ostwald's dilutlon law. The equilibrium constant K is
called the dissociation constant of the electrolyte.
The degree of dissociation a at different concentrations was determined by conductance measurements
:
using Eq. 4, viz., o A,ln"r. fn" hw was found to hold good in the case of weak electrolytes, such as
acetic acid and ammonium hydroxide.
However, the law failed completely when it was applied to strong electrolytes, such as hydrochloric
acid, sodium hydroxide or potassium chloride, The values of K obtained lor poqsliu_m chloride, fbr
example, varied from 2.350 io 0.015 as the concentration varied from l'00 M to 0'0001 M. The German
chemist,'W. Osgald (1847-1931) was awarded the 1909 Chemistry Nobel Prize for his work on catalysis,
chemical equilibria and rates of reactions.
We may mention here that Ostwald, van't Hoff and Arrhenius were the founding fathers of physical
chemistry which has become a magnificent edifice at the hands of theorists and experimenters.
Example 2?. At 25oC, the speciftc conductance of 0101 M.aqueous solution of acetic acid is l'63 x l0-2 S m-l and the
molar conduc{sne at infinite dihition is 390.7x 10.4 S m2 mol-I. Calculate the degree of dissociation and the dissociation
constant of the acid.
Solution: r = l'63x1(f2Sm-l ; c = 0'01 moldm-3 = 0'0lxldmolm-3

... A", =
* = offi$- = 16'3 x lo4s m2 mol-r

The degree of dissociation is given by

o 16.3 x l0-4 S m2 mol-l :
ct = Am/nm = O'Ml7
a9o .'l x lo-4 s m2 mol-l