Junction Potential

Liquid Junction Potentials---occur at the boundary
between two solutions that have different ionic

compositions---
-Exist for all reference electrodes that are separated

from sample solution by frit, or some other type of
electrolytic contact interface---to prevent bulk
mixing of the reference electrode electrolyte with
the sample solution
-Occur at all liquid-liquid junctions--but magnitude of

Ej value is dependent on the exact method of forming
junction----
-restrained junction----e.g., microporous frit
-free flowing junction----simply bringing two
solutions in contact---but no mixing!
theory for junction potential calculations is always

based on “free flowing” type junction;
In cases of constrained junction---adsorption of sample

species onto the solid support can greatly alter the
Ej value by changing the mobilities of the ions across
the junction due to electrostatic effects
Origin of liquid junction potentials:
Ag/AgCl(s), HCl (1 M) / HCl (0.1M), AgCl(s)/Ag

α β
φβ − φα = Ej Ej
at t=0;
Conc α
distance
at steady-state-- − +
time--t: − +
[Cl-]
[Η+]
get breakdown of electroneutrality at the interface--
flux of H+ and Cl- at interface depend on two forms
of ionic movement------diffusion: dC/dx and mobility
and migration: movement of ions in electric field
as move from α to β phases---each element (plane)

of solution has more + than previous segment--
If cell were allowed to discharge spontaneously--

(short the two electrodes)
reaction at left elect: Ag + Cl- ----> AgCl(s) + 1 e-

reaction at right elect: AgCl(s) + 1 e- ----> Ag + Cl-
initial:
++++++ +++
------ -- -
α β
as cell discharges---chloride ion builds up in β phase-

and H+ build up in α phase-------but this can’t happen-
bulk of phases must be electroneutral----
Therefore---ions move between phases to compensate
build-up of excess charge!
for every 5 q (coulombs) of charge that passes in
external circuit---then 5 q of charge must transfer in
electrolyte soln to maintain electroneutrality---
H+ moves from α to β phase---and Cl- moves from β

to α.
++++++ +++
− −−−−−−−−
5 q of chloride 5 q of chloride
electrolyzed at gained--from
left elect. reduction of AgCl
after time t---you pass q total charge---
f(q)/F = moles of HCl added to β side---due to

generation of Cl- and movement of H+
f= fraction of current carried by movement of H+

ions
1-f=fraction of current carried by Cl- ions
f = t+ ; 1-f = t- ----cation and anion transference
numbers, respectively
for simple electrolyte---same electrolyte on each

side of junction----t+ + t- = 1
Different methods to measure transference # of

electrolyte solutions----
---Hittorf method---use electrolytic cell--starting

with same concentration of electrolyte in all
parts of a long tube---then pass current for
given time---and measure concentration of
electrolyte at different portions of tube!
---Moving boundary method---
current in cell is obviously dependent on movement

of ions---and migration of ions depends on
conductance of solution---
therefore--by measuring conductivity of electrolyte

you should be able to relate transference # with
conductivity of given electrolyte
Conductance = L = 1/Rsoln = K (A/l)
L = conductance ---Siemens, Ω−1

Κ = specific conductivity---siemens/cm
A = area of electrodes used for conductance
measurement---or cross-sectional area of solution
between the two electrodes
l= distance between electrodes
recall----Ru = x/KA same eqn as above--except

reciprical-and x=
K = F ∑ zi i Ci
i
µ I = mobility of ion in electric field--- cm2sec-1V-1
ions in solution will have continuous velocity v only

when electric force strength = frictional drag
electric force = zi e ε
V/cm = field strength
charge on
electron
frictional drag ---can estimate with Stokes eqn:
=6 πηr v
velocity of ion
hydrated radius of ion

viscosity (poise)
set frictional drag = electric force, and solve for

zi e
v/ε = µ i =
6 r
*movement of ions by migration usually much faster
than by diffusion!
Therefore---transference # is contribution by given

ion to total conductivity
zi Ci
ti =
i
∑z
j
j j Cj
for 1:1 electrolytes (e.g., HCl, NaCl, KCl, etc.)--
for HCl:
zH + H+
CH +
tH+ =
z Cl − Cl
− CCl − + z H + H
+ CH +
but since absolute value of charges is equal---and

CH+ = CCl- ; then:
+
H+
tH + = or t+ =
Cl −
+ H+ − + +
thus for Type 1 junctions:

intuitively---if t+ = t- then µ + = µ - ---and Ej = 0--
call equitransferent electrolyte----neither ion outraces
other across junction due to concentration gradient--
If t+ = 1 and t- = 0 ---then this would mean that

interface between two solutions was only permeable
to t+ ions in electrolyte------
Then we can treat potential difference in accordance
with phase boundary potential:
o( )
H+
− o( )
H+ RT aH +
− = + ln
zF zF aH +
this term is zero---since standard free

energy of ion in each of the two aqueous
solutions should be the same!
Then for β containing 0.1 M HCl, and α containing
1 M HCl, Ej = + 59 mV or 0.059 V (at 25o C)
Actual Ej must be between these two extreme values

since Cl- does have mobility across interface (unless
interface region had high concentration of negatively
charged sites---e.g. thin membrane---)
some fraction of Ej is due to gradient of H+

some fraction of Ej is due to gradient of Cl-
RT aH + RT aCl −
− = (t+ ) ln + (t − ) ln
zH + F aH + zCl − F aCl −
RT a1
− = (t+ − t − ) ln
F a2
where a1 = aM+α = aA-α = aMAα
a2 = aM+β = aA-β = aMAβ
since single ion activities cannot be measured---we
can only measure mean activities---and hence we
can make above assumptions to simplify previous
equation!
for HCl junction---if tH+ = 0.82, and tCl-= 0.18

then Ej = + 37.7 mV or 0.0377 V.
for Type II and Type III junctions---we cannot make

these simplistic assumptions----
ti values are changing considerably as your go across

junctions, since concentrations of the ions are
different----and the gradients for all the different ions
present on each side are different!-
See next handwritten pages for derivation of equation

based on first two terms of Nernst-Planck equation!

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Liquid Junction Potentials---occur at the boundary

between two solutions that have different ionic

-Exist for all reference electrodes that are separated

-Occur at all liquid-liquid junctions--but magnitude of

theory for junction potential calculations is always

In cases of constrained junction---adsorption of sample

Ag/AgCl(s), HCl (1 M) / HCl (0.1M), AgCl(s)/Ag

as move from α to β phases---each element (plane)

If cell were allowed to discharge spontaneously--

reaction at left elect: Ag + Cl- ----> AgCl(s) + 1 e-

as cell discharges---chloride ion builds up in β phase-

H+ moves from α to β phase---and Cl- moves from β

after time t---you pass q total charge---

f(q)/F = moles of HCl added to β side---due to

f= fraction of current carried by movement of H+

for simple electrolyte---same electrolyte on each

Different methods to measure transference # of

---Hittorf method---use electrolytic cell--starting

---Moving boundary method---

current in cell is obviously dependent on movement

therefore--by measuring conductivity of electrolyte

L = conductance ---Siemens, Ω−1

recall----Ru = x/KA same eqn as above--except

µ I = mobility of ion in electric field--- cm2sec-1V-1

ions in solution will have continuous velocity v only

hydrated radius of ion

set frictional drag = electric force, and solve for

Therefore---transference # is contribution by given

but since absolute value of charges is equal---and

thus for Type 1 junctions:

If t+ = 1 and t- = 0 ---then this would mean that

this term is zero---since standard free

Actual Ej must be between these two extreme values

some fraction of Ej is due to gradient of H+

for HCl junction---if tH+ = 0.82, and tCl-= 0.18

for Type II and Type III junctions---we cannot make

ti values are changing considerably as your go across

See next handwritten pages for derivation of equation

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