POTENTIOMETRIC

Methods of Analysis
1Potentiometry:
Reference and
Working Electrodes
Potentiometric methods of analysis

§ are based upon measurements of the

potential of electrochemical cells in the
absence of appreciable currents (I=0)

cathode
(indicator
electrode)
electrochemical
cells anode
(reference
electrode)
Potentiometry
• measurement of the potential between
ü an electrode which responds to the analyte
(called an ion selective or indicator electrode) and
ü a reference electrode
in an electrically conductive solution.

• the reference electrode has a constant potential,

the measured potential depends on the activity of
analyte.

• the measurement is taken when there is no current

flow.
 Electroanalytical Methods
Potentiometry General Concept

§ Electrodes are at
equilibrium with
solution.

§ Current doesn't flow.

§ Cell potential can be

explained in terms of
thermodynamics
(Nernst Equation).
Potentiometric method

potential measuring

device

Indicator Reference
Electrode
(cathode)
Electrode Ecell = Ecathode - Eanode + Ejunction
(anode)

Ecell = Eind - Eref + Ejunction

Ecathode Eanode

Salt bridge

Analyte

solution
Junction potential

• a junction potential is due to the build up of

charge at an interface.
• Any time two dissimilar electrolytes are in
contact, a small potential difference (called the
junction potential) develops at their interface.

• When two ionic solutions are separated across an

interface that prevents bulk mixing of the ions,
• but has ionic permeability, a potential (drop)
develops called the liquid junction potential.
Junction potential

• in electrolytes containing many different ions

the magnitude of the junction potential
cannot be easily estimated.

• Junction potentials are highest when

(a) there is a large concentration
difference between the phases
(b) where cation and anion mobilities are
notably different
Junction potential

• The junction potential is determined by

differences in mobilities of ions:
Ion Mobility (cm2/Vs)
Na+ 5.19 x 10-4
Cl- 7.91 x 10-4
ü build up of charge at an interface.
Junction potential
• Junction potential can be minimized by filling up the
salt bridges or/and reference electrodes with high
concentration of electrolytes with similar
mobilities for positive and negative ions
• e.g. KCl or NH4NO3.

Ion Mobility (cm2/Vs)

H+ 3.62 x 10-3
Na+ 5.19 x 10-4
K+ 7.62 x 10-4
NH4+ 7.61 x 10-4
Cl- 7.91 x 10-4
I- 7.96 x 10-4
NO3- 7.40 x 10-4
Junction potential

• the junction potential can be in the

range of ± 1 mV

• this puts a fundamental limitation on

the accuracy of direct potentiometric
measurements.
Membrane potential

• Membrane potential develops across a

membrane which is permeable to ions.

• Ion-selective membranes are here of

particular interest; these membrane are
permeable only to one kind of ions.
REFERENCE ELECTRODES

Properties of ideal reference electrodes

§ has known potential
§ exhibits a potential that is constant with time
§ has potential that is insensitive to the
composition of the solution under study
§ reversible and obeys the Nernst equation
§ returns to its original potential after being
subjected to small currents
§ exhibits little hysteresis with temperature cycling.
A. Standard Hydrogen Electrode (SHE)
§ universally adopted
primary standard reference H2 gas
electrode p=1 atm

§ consists of Pt wire or foil,

coated with Pt black, platinized

immersed in a hypothetical Platinum

solution of unit H+ ion

activity and in equilibrium
§ with H2 gas at unit partial
pressure. H+(a=1)
Standard Hydrogen Electrode (SHE)
Ø representation:
Pt/H2(p=1atm), H+(a=1)
H2 gas

Ø reaction: p=1 atm

2H+ + 2e Û H2
platinized

Platinum

Ø Nernst eqn:
Eref = E0 – 0.05916 log (pH2)
2 [H+]2
E0 = 0.000V (at all temp) H+(a=1)

• by convention
• however, not convenient to use
Standard Hydrogen Electrode (SHE)

A) Platinum electrode
Hydrogen electrode: 2H+ + 2e = H2(g)

E = Eo H+/H2 - 0.05916 log (pH2)

2 [H+]2

Standard Hydrogen Electrode (SHE)

aH+ = 1 E = Eo H+/H2 = 0
A scale of EM values can be established against the SHE
Standard Hydrogen Electrode (SHE)

Platinum electrode V

Mn+ + n e = M H2 (1 atm)
1
E = EoMn+/M - 0.05916 log Pt
aMn+ M

If n =1, DE = 1 mV ® 4/100 ai H+ 1M Mn+

Liquid junction

Pt (H2) | H+ (1M) || Mn+ | M

B. Calomel Electrode
§ consists of Hg in contact with a
solution that is saturated with
Hg2Cl2 (calomel) and also contains
a known concentration of KCl
Calomel Electrode

Ø representation:
Hg/Hg2Cl2(satd), KCl (xM)

Ø reaction:
Hg2Cl2 (s) + 2e Û 2Hg(s) + 2Cl-

Ø Nernst eqn:
Eref = E0 – 0.05916 log [Cl-]2
2
Eref = E0 – 0.05916 log [Cl-]
Calomel Electrode
Type of Calomel Ecell vs SHE, V
Electrode
at 20ºC at 25ºC
0.1M calomel 0.3359 0.3356
3.5M calomel 0.252 0.250
Satd. (4.17M) calomel 0.2479 0.2444

• Saturated Calomel electrode (SCE) - widely used

because ease of preparation
• however, temperature coefficient is significantly larger
• when temperature is changed, the potential comes to a
new value only slowly because of the time required for
solubility equilibrium for the KCl to be reestablished.
 Saturated Calomel Electrode (SCE)

Hg2+2 + 2e = 2 Hg(s) EoHg+/Hg

Pt Hg2Cl2(s) = Hg2+2 + 2 Cl- KHg2Cl2

_____________________________
Hg
Overall response
Hg/Hg2Cl2 Hg2Cl2 (s) + 2 e = 2 Hg + 2 Cl-
KCl (satd)
E = EoHg2Cl2/Hg - 0.05916 log a Cl-

Hg | Hg2Cl2 | KCl (satd) || sample | indicator electrode

C. Ag/AgCl Electrode
ü most widely marketed reference
electrode
ü consists of Ag electrode
immersed in a solution of KCl
that has been saturated with
AgCl
Ag/AgCl Electrode

Ø representation:
Ag/AgCl(satd), KCl (xM)

Ø Half-cell reaction:
AgCl(s) + e Û Ag(s) + Cl-

Ø Nernst eqn:
Eref = E0 – 0.05916 log [Cl-]
Ag/AgCl Electrode
Type of AgCl Ecell vs SHE, V
Electrode (at 25ºC)

3.5M Ag/AgCl 0.205

Satd. Ag/AgCl 0.199

• can be used at temperature greater than 60 ºC

• reacts with more sample components than Hg(I) ions

(e.g. protein), leads to plugging of junction between
electrode and analyte

• less toxicity and environmental problem with

consequent cleanup disposal difficulties in the event of
broken electrode.
 Ag/AgCl Electrode
Primary response
Ag+ + e = Ag (s) EoAg+/Ag

Secondary response
AgCl (s) = Ag+ + Cl- K AgCl
Ag
Overall response
AgCl AgCl (s) = Ag (s) + Cl-

KCl E = Eo AgCl/Ag - 0.05916 log aCl-

Ag | AgCl | KCl (c) || sample | indicator electrode

Precautions in the Use of Reference
Electrodes

1) level of internal liquid

should always be kept above AgCl
that of sample solution KCl

• to prevent contamination of
electrode solution by plugging analyte solution

of the junction due to reaction

of analyte solution with Ag+ or
Hg+ ions from internal solution
con’t. Precautions in the Use of Reference Electrodes

2) with liquid level above the analyte

solution, some contamination of
sample is inevitable (although in most
instances, contamination is slight)
• special precaution for analysis of AgCl
K+, Cl-, Ag+, and Hg+ is necessary KCl
• also for samples containing halides,
KNO3
cyanides, proteins, tris buffers and
heavy metals 2
nd junction
or salt bridge analyte solution

Solution: use double junction

electrode containing a second salt
bridge which has a non-interfering
electrolyte such as KNO3 or Na2SO4
con’t. Precautions in the Use of Reference Electrodes

3) electrodes should be filled with the

right electrolyte solution
 D E (potential difference
between electrodes) depends

i) The nature of electrodes

ii) The nature and
concentration of the solutions
DE (potential difference between electrodes) depends
i) The nature of electrodes
ii) The nature and concentration of the solutions

Quantitative relationship: Nernst equation

Ox + ne = Red (in solution)
• At 298 K (25 oC)
RT ared 0.05916 ared
E= Eo - ln E = Eo - log
nF aox n arox
y b m x
y = mx + b
nature of the nature and
electrodes concentration
of the solutions
INDICATOR ELECTRODES

Ideally, indicator electrode responds

ü rapidly and reproducibly to changes in

activity of the analyte ion.
Potentiometry

• The potential depends on the activity of the analyte,

however concentration of analyte is normally the
question of interest.

• In solutions with low (near zero) ionic strength, the

activity coefficient approaches unity and
concentration is equivalent to activity.

• But, it is not possible to make accurate

electrochemical measurements in solutions of low
ionic strength because these solutions are
nonconductive.
Activity versus Concentration

Ø electrode response is related to

activity rather than to analyte
concentration

Ecell = K - 2.303 log a

nF
Activity versus Concentration

a=fC
,a = activity
,f = activity coefficient
,c = molar concentration
-log fA = 0.509 ZA2 Öµ
1 + 0.328 aA Öµ

fA = activity coefficient of species A

ZA = charge on species A
µ = ionic strength of solution
aA = effective diameter of hydrated ion (in Å)
0.509 & 0.328 – constants at 25C
Activity versus Concentration

µ = 1 (m1Z12 + m2Z22 + m3Z32 + m4Z42 + . . . )

2

,m = molar conc of various ions in soln

,Z = charge of respective ions
,µ = ionic strength of solution
Activity versus Concentration

a=fC

§ f = activity coefficient varies with ionic strength of

solution, which in turn varies with concentration of solution

§ as ionic strength (concentration) increases, f decreases

§ as the solution approaches infinite dilution (µ à 0), f à 1

thus am » [C]

§ E vs log C plot is only linear at low concentration or at

dilute solutions
Potentiometry
§ Potentiometric measurements (including pH
measurements) are based on a calibration curve
where the signal (E) is graphed against either the
log of analyte concentration or p-function of
the analyte concentration.

§ The only difference in these graphs is the

direction of the slope.

§ In pH measurements, the calibration curve is

stored in the meter when the
standardization/calibration buffers are measured
Potentiometry

§ An indicator electrode or, more commonly, ion

selective electrode (ISE) is an electrode whose
potential responds to a specific substance.

§ These electrodes are selective rather than

specific, which means that they might also
respond (although with a smaller signal) to other
ions, particularly those with similar chemistry.
Potentiometry

§ these electrodes are selective enough that

they only respond to one form of the ion.
(i.e., different oxidation states, complexation,
or acid/base forms will not be detected)

§ to get accurate results, the analyst must take

into account the chemistry of the analyte and
the matrix of the analyte solution.
IA. Metallic Indicator Electrodes

a) Metallic electrodes of the first kind

üconsists of metal electrode immersed in its

cationic solution

üresponds to the activity (or conc.) of the

cation solution
I. Metallic Indicator Electrodes

a) Metallic electrodes of the first kind

e.g. Cu/Cu2+

half cell rxn: Cu2+ + 2e Û Cu(s)

Nernst eqn: Eind = E0 – 0.05916 log 1
2 [Cu2+]
I. Metallic Indicator Electrodes

a) Metallic electrodes of the first kind

e.g. Zn/Zn2+ Cd/Cd2+ Ag/Ag+

Pb/Pb2+ Hg/Hg2+

-reversible behavior
II. Metallic electrodes of the second kind

üconsists of metal electrode in contact with an

anion with which it forms a precipitate or stable
complex ion.
üresponds to the activity (or conc) of the anion

e.g. Ag electrode with AgCl immersed in Cl-

representation: Ag/AgCl(satd), Cl- (xM)

reaction: AgCl + e- Û Ag(s) + Cl-

Nernst eqn: Eind = E0 – 0.05916 log [Cl-]

Con’t. II. Metallic electrodes of the second kind

e.g. Hg electrode, in the presence of small

concentration of stable Hg(II)-EDTA (HgY2-)
complex, immersed in EDTA anion, Y4-

representation: Hg/HgY2-, Y4- (xM)

reaction: HgY2- + 2e- Û Hg(l) + Y4-

Nernst eqn: Eind = E0 – 0.05916 log [Y4-]

2 [HgY2-]
Con’t. II. Metallic electrodes of the second kind

Eind = E0 – 0.05916 log [Y4-]

2 [HgY2-]

•a small concentration of HgY2- introduced to

analyte solution remains essentially constant over
a wide range of Y4- concentrations.

Hence,
Eind = E0 - 0.05916 log [Y4-] - K
2
üuseful for establishing endpoints for EDTA
titrations
III. Metallic electrodes of the third kind

üconsists of metal electrode in contact with a

complexing anion, the stable metal-anion
complex formed, and another cation which
complexes with the anion.

ücan be made to respond with the different cation

e.g. Hg electrode for determination of Ca2+ ions

con‘t. III. Metallic electrodes of the third kind

e.g. Hg electrode for determination of Ca2+ ions

• a small conc of EDTA complex of Hg(II) is

introduced into the solution containing EDTA

• as before, Nernst eqn:

Eind = E0 - 0.05916 log [Y4-] - K

2
con‘t. III. Metallic electrodes of the third kind

§ in addition, a small volume of solution containing

EDTA complex of Ca2+ (CaY2-) is also introduced

CaY2- Û Ca2+ + Y4- 1 = [Ca2+][Y4-]

Kf [CaY2-]

,Y4- = [CaY2-]
Kf [Ca2+]
Eind = E0 - 0.05916 log [Y4-] - K
2
Substituting into the Nernst eqn:
Eind = E0 - K - 0.05916 log [CaY2-]
2 Kr [Ca2+]
con‘t. III. Metallic electrodes of the third kind

Eind = E0 - K - 0.05916 log [CaY2-]

2 Kr [Ca2+]

• If a constant amount of CaY2- is used in analyte

solution and in solutions for standardization,

Eind = E0 - K - K’ - 0.05916 log 1 _

2 [Ca2+]
IV. Metallic redox electrodes

§ The electrode is normally made of platinum,

which is electrically conductive without
participating in the reaction.

§ Redox electrodes are used to give an overall

indication of the reactivity of the solution and
are often used to construct titration curves of
redox titrations.
IV. Metallic redox electrodes

üconsists of inert metal electrodes (e.g., Pt, Au,

Pd, or C) immersed in an oxidation/reduction
system

e.g. Pt electrode immersed in a solution containing

Ce(III) and Ce(IV)

representation: Pt/Ce3+(xM), Ce4+ (yM)

reaction: Ce4+ + e- Û Ce3+

Nernst eqn: Eind = E0 – 0.05916 log[Ce3+]

[Ce4+]
 con’t. IV. Metallic redox electrodes

• Pt electrode can serve

as the indicator
electrode in a titration in
which Ce4+ serves as
the standard oxidizing
agent.

• for example,
determination of Fe2+
with Ce4+
2 Ion Selective
Electrodes (ISEs)
Potentiometry: ISEs

§ An indicator electrode or, more commonly, ion

selective electrode (ISE) is an electrode whose
potential responds to a specific substance.

§ These electrodes are selective rather than

specific, which means that they might also
respond (although with a smaller signal) to other
ions, particularly those with similar chemistry.
Potentiometry: ISEs

§ these electrodes are selective enough that

they only respond to one form of the ion.
(i.e., different oxidation states, complexation,
or acid/base forms will not be detected)

§ to get accurate results, the analyst must take

into account the chemistry of the analyte and
the matrix of the analyte solution.
Potentiometry: ISEs

Commercial ISEs tend to be

categorized as

§ glass
§ gas sensing
§ membrane solid state
§ redox (or ORP) electrodes.
Membrane Indicator Electrodes

• also referred as ion-selective electrodes (ISEs)

because of high selectivity of most of these devices

(but erroneously called as ion-specific electrode)

• develops a kind of junction potential across the

membrane that separates the analyte solution
from a reference solution
 Ion Selective membrane electrodes

• Membrane potential
develops across a
membrane which is
permeable to ions.

• Ion-selective
membranes are
here of particular
interest; these
membrane are
permeable only to
one kind of ions.
Properties of ion-selective membranes

1) selective reactivity with analyte

• membrane or some species contained within
the membrane matrix must be capable of
selectively binding the analyte ion.
con’t. Properties of ion-selective membranes

2) minimal solubility

• solubility of membrane in analyte solution

(usually aqueous) must approach zero

• membranes are formed from large

molecules or molecular aggregates such as
silica glasses or polymeric resins

• Ionic inorganic compounds of low solubility

can also be converted to membranes
con’t. Properties of ion-selective membranes

3) electrical conductivity

• membrane must exhibit some electrical

conductivity, albeit small

• this conduction takes the form of

migration of singly charged ions within the
membranes.
Classification of Ion-selective
Membrane Electrodes
Non-crystalline membrane Crystalline membrane
1) Glass 1) single crystal
e.g. silicate glass for H+ and e.g., LaF3 for F- electrode
Na+

2) Liquid 2) polycrystalline or mixed

e.g. liquid ion exchanger for crystal
Ca2+ e.g., Ag2S/AgX forS2- and
Ag+
3) immobilized liquid in a rigid
polymer
e.g., PVC matrix for Ca2+ and
NO3-
Relationship Between Concentration and
Potential
• potential of an ion-selective electrode for an
ion with a charge of z is

Ecell = K + 0.05916 log (aA)samp

z

, K is a constant that includes

• the potentials of the ion-selective electrode's internal and
external reference electrode

• any asymmetry potential associated with the ion-selective

electrode's membrane, and,
• the analyte's activity in the ion-selective electrode's internal
solution
Relationship Between Concentration and
Potential

0.05916
Ecell = K + log (aA)samp
z
• is a general equation and applies to all types of ion-selective
electrodes
Note:

ü when the analyte is a cation, an increase in the analyte's

activity results in results in an increase in the potential

ü when the analyte is an anion, which makes z a negative

number, an increase in the analyte's activity results in a
decrease in the potential.
Relationship Between Concentration and
Potential

0.05916
Ecell = K + log (aA)samp
z

ü concentrations of ions in solution often are reported as

pX values: pX = -log ax

0.05916
Ecell = K - pA
z
Relationship Between Concentration and
Potential

0.05916
Ecell = K - pA
z

Note:

ü For a cation, an increase in pA results in a decrease in

the potential

ü When the analyte is an anion, an increase in pA results in

an increase in the potential.
Sign conventions
Ecell = Eind – Eref + Ejunc

ü Indicator electrode = cathode

ü Reference electrode = anode

for CATIONS: Ecell = K + 0.05916 log aM

z
Ecell = K - 0.05916 pM
z
Ecell ü For a cation, an increase in
pA results in a decrease in
the potential
pM
Sign conventions
Ecell = Eind – Eref + Ejunc

ü Indicator electrode = cathode

ü Reference electrode = anode

for ANIONS: Ecell = K - 0.05916 log aA

z
Ecell = K + 0.05916 pA
z

Ecell
ü For an anion, an increase
in pA results in an increase
in the potential.
pA
2A Non-Crystalline Membrane Electrode

Glass Membrane
Electrode
Non-crystalline membrane
Glass-electrode for pH
•consists of a thin pH-sensitive
glass membrane sealed onto one
end of a heavy-walled glass or
plastic tube
•a small volume of dilute HCl
saturated with AgCl (or a buffer
containing Cl- ion) is contained in
the tube and a silver wire in this
solution forms an internal Ag/AgCl
reference electrode, which is
connected to one of the terminals of
a potential measuring device.
Combination electrode

§ Combination electrodes combine the

reference and indicator electrodes in one
electrode body.

§ Most pH electrodes are designed as

combination electrodes.
Combination Glass pH electrode

Reference Reference
electrode 1 Analyte electrode 2
Glass electrode
(external) solution (internal)
Hg / Hg2Cl2(satd), Cl-=4.17M // [H+]ext = a1 / glass membrane / [H+]int = a2, [Cl-]= 4.17 M, AgCl(satd) / Ag
E1 E2
Eboundary = Eb = = E1 – E2
Composition and structure of glass
membrane

• reactivity of membrane is
dependent on its
composition

• glass membrane,
consisting of ~ 22% Na2O,
6% CaO, and 72% SiO2, is
specific in its response
toward H+ ions up to
about pH 9.
pH Glass membrane

üAt higher pH, the glass becomes somewhat

responsive to Na+
üGlass consists of an infinite three dimensional
network of SiO44- groups in which each Si is bonded to
4 oxygens and each oxygen shared by 2 silicons.

üWithin the interstices of this structure are sufficient

cations to balance the negative charge of the silicate
groups

üSingly charged cations (eg Na+ or Li+) are mobile in

the lattice and are responsible for the electrical
conduction within the membrane
Hygroscopicity of glass membrane

•surface of glass membrane must be hydrated

before it will function as a pH electrode

•the hydration of a pH sensitive glass membrane

involves an ion-exchange reaction between
singly charged cations in the glass lattice and
protons from the solution,

H+ + Na+Gl- Na+ + H+Gl-

soln glass soln glass
Membrane potential
H+int
H+int H+int
H+int H+ + Gl- Û H+Gl-
Gl-
Gl -
Gl-
Gl- solnint glassin
Gl-
+
glassint Eint
Na Na+
Gl- Gl-
Gl- Gl-
H+ext Gl- Gl- H+ext

H+ext
H+ext H+ + Gl- Û H+Gl-
H+ext
solnext glassext
glassext Eext

• positions of these two equilibria are determined by the

hydrogen ion activities of H+ in the solutions on the external
and internal sides of the membrane, respectively.

• the surface at which greater dissociation occur becomes

negative with respect to the other surface where less dissociation
has taken place.
Boundary Potential

Reference Reference
electrode 1 Analyte Glass electrode 2
(external) solution electrode (internal)
Hg / Hg2Cl2(satd), Cl-=4.17M // [H+]ext = a1 / glass membrane / [H+]int = a2, [Cl-]= 4.17 M, AgCl(satd) / Ag

E1 E2
Eb = E1 – E2
con’t. Membrane potential
üBoundary potential, Eb, develops across the membrane, the
magnitude of the potential depends upon the ratio of the two
solutions.
Eb = Eext – Eint = 0.05916 log [H+ext]
[H+int]
,since [H+int] is constant

Eb = L’ + 0.05916 log[H+ext]

Eb = L’ - 0.5916 pHext

Eind = Eb + Eref2

= L’ - 0.05916 pHext + Eref2

Eind = L - 0.05916 pHext Eind = L + 0.05916 log [H+]

pH Glass membrane

§ In addition to H+ ions, the glass will also interact with sodium

ions.

§ in solutions of high pH, Na+ concentrations tend to be high

while H+ concentration are low, so the measured potential
may be due to Na+ rather than H+ and pH measurements are
not accurate.

§ by varying the composition of the glass slightly, glass

electrodes can be made give a larger signal for sodium ion,
thus creating a sodium ion selective electrode
The alkaline error of pH glass
electrodes

v at high pH (> pH 9), glass electrodes respond to the

conc. of both H+ and alkali metal ions (Na+, K+)

v pH electrodes give lower readings than actual pH

H+Gl- + B+ Û B+Gl- + H+
glass soln glass soln

v the activity of Na+ ions relative to that of H+ ions

becomes so large that electrode responds to both
species
Acid error of pH glass electrode

§ occurs at pH < 0.5

§ pH readings tend to be higher than

actual pH
Summary of errors affecting pH measurements
with the glass electrode

1. alkaline error
- become sensitive to alkali metal ions at pH > 9;
values tend to be lower than actual pH

2. acid error
- at pH < 0.5 , values tend to be higher than actual
pH
3. dehydration
- dehydration causes unstable performance and error

4. errors in low ionic strength solutions

- errors may occur for samples of very low ionic strength
or low buffering capacity
con’t.Summary of errors affecting pH
measurements with the glass electrode

5. error in the pH of standard buffer

- any inaccuracies in the preparation of the buffer used for
calibration, or changes in its composition during storage,
will be propagated as errors in pH measurements
- common cause of deterioration is action of bacteria on
organic components of buffers.

6. variation in junction potential

- variation in junction potential between standard and
sample leads to uncertainty in the measurement of pH
Selectivity coefficient

ü The smaller the selectivity coefficient,

the more selective the electrode to ion H,
thus, the less interference from foreign ion B

kH,B = 0 - no interference

kH,B > 1 - high interference

Selectivity coefficient

• For a K+ ion-selective electrode it has

following selectivity coefficients:

• kK+,Na+ = 1 x 10-5 • Na+ hardly interferes with the

measurement

• kK+,Cs+ = 0.44 • Cs+ interferes to greater extent

• kK+,Rb+ = 2.8 • The electrode responds

more to Rb+ than K+
Selectivity coefficient

ü For interfering ion with charge, zB, the response of

the ion selective electrode can be described by the
equation:

0.05916 ZH / ZB
E = L’ ± log [ aH + kH,B (aB) ]
n

aH = concentration of analyte ion

aB = concentration of interfering ion
ZH = charge analyte ion
ZB = charge interfering ion
kH,B = selectivity coefficient
Example: Selectivity coefficient

One commercial sodium ion-selective electrode has a

selectivity coefficient of kNa+,H+ = 36. When this electrode
was immersed in 1.00 mM NaCl at pH = 8.00, a potential
of -38 mV (vs. SCE) was recorded.

(a) Neglecting activity coefficient, calculate the potential if

the electrode was immersed in a 5.00 mM NaCl
solution at pH 8.00

(a) What would be the potential for 2.00 mM NaCl at pH

3.78?
 Example: Selectivity coefficient
One commercial sodium ion-selective electrode has a selectivity
coefficient of kNa+,H+ = 36. When this electrode was immersed in 1.00
mM NaCl at pH = 8.00, a potential of -38 mV (vs. SCE) was recorded.

(a) Neglecting activity coefficient, calculate the potential if the

electrode was immersed in a 5.00 mM NaCl solution at pH 8.00
Solution
MNaCl = 0.001 M [H+] = 10-8 M (pH = - log [H+])
0.05916 ZNa+/ZH+
E = constant + log [ aNa+ + kNa+,H+ (aH+) ]
n
-0.038 V = constant + 0.05916 log [ 0.001 + (36) (1 x 10-8)]
constant = 0.1393 V 1

E = 0.1393 V + 0.05916 log [ 0.005 + (36) (1 x 10-8)]

1
E = 0.0033 V or 3.3 mV
Example: Selectivity coefficient
One commercial sodium ion-selective electrode has a selectivity coefficient
of kNa+,H+ = 36. When this electrode was immersed in 1.00 mM NaCl at pH
= 8.00, a potential of -38 mV (vs. SCE) was recorded.

(b) What would be the potential for 2.00 mM NaCl at pH 3.78?

Solution MNaCl = 0.001 M [H+] = 10-8 M

0.05916 ZNa+/ZH+
E = constant + log [ aNa+ + kNa+,H+ (aH+) ]
n
-0.038 V = constant + 0.05916 log [ 0.001 + (36) (1 x 10-8)]
constant = 0.1393 V 1
(b) MNaCl = 0.002 M [H+] = 1.660 x 10-4 M

E = 0.1393 V + 0.05916 log [ 0.002 + (36) (1.660 x 10-4)]

1
E = 0.0152 V or 15.2 mV
 Sources of Error with a pH Meter
• Calibration standards (±0.01 pH)
• Junction potential (~0.01 pH)
• Junction potential drift (recalibrate ~2 h)
• Sodium error (when H+ is low and Na+ is high)
• Acid error
• w/ strong acid, the glass surface can saturate
• Equilibration time (Electrode requires ~30s)
• Hydration of glass (If the electrode is dry)
• Temperature
• Must be calibrated at same T as measurements
Glass-electrode for other cations

Ø by changing the composition of the glass

membrane, the selectivity/reactivity to other
cations can also change leading to the
development of glass electrodes for other
cations

Ø e.g., Na+, K+, Li+, NH4+, Rb+, Cs+, and Ag+

2B Non-Crystalline Membrane Electrode

Liquid membrane
electrodes
Liquid membrane electrodes

§ liquid membranes are formed from

immiscible liquids that selectively bind
certain cations
 Ways of preparation 3) Liquid membrane electrodes

a. immiscible liquid ion-

exchanger is retained in a
porous hydrophobic, inert,
solid plastic disk
support

§wick action caused the

pores of the disk to stay
filled with the organic
liquid from the reservoir in
the outer of the two
concentric tubes.
 con’t. Ways of preparation
3) Liquid membrane electrodes

§ the inner tube

contained an aqueous
satd soln of MCl2,
where M2+ is the
cation whose activity
is to be determined

§this solution is also

saturated with AgCl to
form a Ag/AgCl
reference electrode
with the silver lead
wire.
con’t. Ways of preparation
3) Liquid membrane electrodes

b. liquid exchanger is immobilized in tough

polyvinyl chloride membranes

• liquid ion exchanger and polyvinyl chloride are

dissolved in a solvent such as tetrahydrofuran;
evaporation of the solvent leaves a flexible
membrane, which can be cut and cemented to the
end of a glass or plastic tube.

• basis for newer type of liquid membrane

electrodes
 Kinds of active substances in
liquid membranes 3) Liquid membrane electrodes

1) cation exchanger

2) anion exchanger

3) neutral macrocyclic compound

which selectively complex certain
cations
 Ca2+ - selective electrode
3) Liquid membrane electrodes

ü active ingredient is a
cation exchanger
consisting of an
aliphatic diester of
R-O O O O-R
phosphoric acid P P
dissolved in a polar R-O O--Ca--O O-R
solvent; reacts with
Ca2+ to form the
structure

ü R = 8-16 C atoms
 con’t. Ca2+ selective electrode
3) Liquid membrane electrodes

• the internal aqueous solution in contact with the

exchanger contains a fixed concentration of CaCl2
and a Ag/AgCl reference electrode

• the equilibrium established at each interface of the

membrane can be represented as:
[(RO)2POO]2Ca Û 2(RO)2POO- + Ca2+

• potential develops across the membrane when

the extent of dissociation (or concentration) at
one surface differs from that of the other surface
 con’t. Ca2+ selective electrode
3) Liquid membrane electrodes

• potential develops across the membrane when

the extent of dissociation (or conc) at one surface
differs from that of the other surface
Eb = Eext - Eint = 0.05916 log [Ca]ext
2 [Ca]int

Eb = L + 0.05916 log [Ca]ext

2
Eb = L - 0.05916 pCaext
2
con’t. Ca2+ selective electrode
3) Liquid membrane electrodes

ü valuable tool for physiological studies

because Ca2+ plays important roles in

• nerve conduction
• bone formation
• muscle contraction
• cardiac conduction and contraction
and
• renal tubular function.
con’t. Ca2+ selective electrode
3) Liquid membrane electrodes

Electrode characteristics:
• Nernstian response down to 5 x 10-5 M
• Selectivity is about
3000 for Ca2+ over Na+, K+
200 over Mg2+
70 over Sr2+
• used between pH 5.5 – 11; above pH 11
Ca(OH)2 precipitates
• PO43- buffer should not be used because Ca2+
activity is lowered by complexation or
precipitation.
 K+ selective electrode
3) Liquid membrane electrodes

• based upon the antibiotic

valinomycin, an uncharged
macrocyclic ether that has a
strong affinity for K+

• a liquid membrane consisting

of valinomycin in diphenyl
ether is 10000 times as
responsive to K+ as Na+

• conc. range: 100 to 1 x 10-6 M

Other available liquid membrane electrodes

Electrode Concentration range

BF4- 100 to 7 x 10-6 M

NO3- 10-3 to 6 x 10-6 M

ClO4- 10-3 to 6 x 10-6 M

Water hardness 10-3 to 6 x 10-6 M

(Ca2+ & Mg2+)
Example No. 1: Electrode Potential

A cyanide ion-selective electrode obeys the equation

E = K - 0.05916 log [CN-]. The potential was - 0.230 V
when the electrode is immersed in 1.00 mM NaCN.

(a) Evaluate the constant in the preceding equation

(b) Using the result in (a), find [CN-], if E = - 0.300 V

(c) Find the [CN-] if E = - 0.450 V

Example No. 1: Electrode Potential
A cyanide ion-selective electrode obeys the equation
E = K - 0.05916 log [CN-]. The potential was -0.230 V when
the electrode is immersed in 1.00 mM NaCN.

(a) Evaluate the constant in the preceding equation

E = constant - 0.05916 log [CN-]
- 0.230 V = K - 0.05916 log (1 x 10-3 M)
Constant, K = - 0.407 V

(b) Using the result in (a), find [CN-], if E = - 0.300 V

E = constant - 0.05916 log [CN-]
- 0.300 V = - 0.407 V - 0.05916 log [CN-]
[CN-] = 1.55 x 10-2 M
 Example No. 1: Electrode Potential
A cyanide ion-selective electrode obeys the equation
E = K - 0.05916 log [CN-]. The potential was -0.230 V when the
electrode is immersed in 1.00 mM NaCN.
• Without getting and evaluating the constant, K, in the
preceding equation
(b) Using the result in (a), find [CN-], if E = - 0.300 V
- 0.230 V = K - 0.05916 log (1 x 10-3 M)
_
- 0.300 V = K - 0.05916 log [CN-]
- 0.230 V + (0.300 V) = (0.05916 ) {-log (1 x 10-3) + log [CN-]}
0.07 V = (0.05916 ) {(3) + log [CN-]}
1.1832 = 3 + log [CN-]
-1.8168 = log [CN-]
[CN-] = 1.52 x 10-2 M
Example No. 1: Electrode Potential
A cyanide ion-selective electrode obeys the equation
E = K - 0.05916 log [CN-]. The potential was -0.230 V when
the electrode is immersed in 1.00 mM NaCN.

(a) Evaluate the constant in the preceding equation

E = constant - 0.05916 log [CN-]
- 0.230 V = K - 0.05916 log (1 x 10-3 M)
Constant, K = - 0.407 V

(c) Find the [CN-] if E = - 0.450 V

E = constant - 0.05916 log [CN-]
- 0.450 V = - 0.407 V - 0.05916 log [CN-]
[CN-] = 1.88 x 10-1 M
Example No. 1: Electrode Potential
A cyanide ion-selective electrode obeys the equation
E = K - 0.05916 log [CN-]. The potential was -0.230 V when the electrode is
immersed in 1.00 mM NaCN.
• Without getting and evaluating the constant, K, in the
preceding equation
(c) Find the [CN-] if E = - 0.450 V
- 0.230 V = K - 0.05916 log (1 x 10-3 M)
_
- 0.450 V = K - 0.05916 log [CN-]
- 0.230 V – (-0.450 V) = 0.05916 ) {-log (1 x 10-3) + log [CN-]}
0.220 V = (0.05916) {(3) + log [CN-]}
3.7187 = 3 + log [CN-]
0.7187 = log [CN-]
[CN-] = 1.91 x 10-1 M
Thank you.