Lecture4

Potentiometry
IonSelectiveElectrodes

LearningOutcomes
y Attheendofthislecturestudentsshouldbeable:
y Todiscussthetheoryandapplicationofpotentiometry
y Toexplainthetheory,characteristicsandthe
p
y

performanceofionselectiveelectrodes

Potentiometry
y Analysis

that are
based on
measuring
the
potential
of
electrochemical
cells
without
drawing appreciable current.
y This technique is used to locate
endpoints in titrations AND to
measure ion concentration directly
from the potential of ionselective
membrane electrodes.
y These
Th
electrodes,
l
d
f
free
f
from
interferences and provide a rapid,
convenient and nondestructive
means
of
Q
QUANTITATIVELY
determining anions and cations.
e.g. pH or [Cu2+]
referenceelectrode|saltbridge|analyte
|
g |
y solution|indicatorelectrode
|

Eref

Ej

Eind

Potentiometry
y...aquickintroduction
Many types of membranes have been developed (glass, solid state, and even
liquid) to detect a wide variety of analytes; but the electrical potential across
that
is
h membrane
b
i the
h signal
i
l that
h must be
b measured.
d In
I order
d to measure this
hi
potential, a reference electrode and a meter are required. Most reasonable
pH meters are capable of acquiring signals from different types of ion selective
electrodes (ISEs).
(
)
Ionselectiveelectrode(ISE) isatransducer
(sensor)whichconvertstheactivityofa
specificiondissolvedinasolutionintoan
electricalpotentialwhichcanbemeasuredbya
voltmeterorpHmeter

Basic Principles
BasicPrinciples

Potentiometer
y A device for measuring the potential of an electrochemical
cell without drawing a current or altering the cell
cellss
composition.
y The potential of an electrochemical cell is measured under
static conditions.
y Because no current, or only a negligible current flows while
measuring a solution
solutionss potential,
potential its composition remains
unchanged.
y For this reason, p
potentiometryy is a useful q
quantitative
method.

Principles of potentiometric analysis

Principlesofpotentiometricanalysis
y Referenceelectrode/saltbridge/analytesolution/indicator

electrode

Ecell = Eind Eref + E j

y SinceEref andEj areconstant,thenEcelldependsonEind whichin

turnrelatedtotheactivityorconcentrationoftheanalyte.

Electrodes
y Referenceelectrode:halfcellwithaccurately

knownelectrodepotential,Eref.e.g.H2
electrode,saturatedcalomelelectrode
l t d t
t d l
l l t d
(SCL)andsilversilverchlorideelectrode
( g g )
(Ag/AgCl).
y Indicatorelectrode:whichisimmersedina
solutionoftheanalyte,developsapotential,
Eind.,thatdependsontheactivityoftheanalyte.
h d
d h i i f h
l
y Mostindicatorelectrodesusedin
potentiometryareselectiveintheirresponses.
potentiometryareselectiveintheirresponses
7

Referenceelectrode
y Ithasastandardpotentialonitsownanditspotentialdoes

notchangetowhicheversolutionitisdipped.
y Alwaystreatedasthelefthandelectrode
Alwaystreatedastheleft handelectrode
y Exampleofreferenceelectrode:
y Standardhydrogenelectrode(SHE)
y Saturatedcalomelelectrode(SCE)
y Silversilverchlorideelectrode(Ag/AgCl)
g g

Standard hydrogen electrode (SHE)

Standardhydrogenelectrode(SHE)

y DefinedasthepotentialthatisdevelopedbetweenH2

gasadsorbedonthePt metalandH+ ofthesolution.

y Itisusedfor
y determinationofelectrodepotentialofmetal
electrodesystem
y determinationofpHofthesolution
Pt,H2 (g,1atm)|H+ (aq,a=1.00)||2 H+(aq)+2e H2 (g)

Saturatedcalomel(Hg2Cl2)Electrode(SCE)
y Containsofaninnerjacketandoutersleeve.
y InnerjackethaswirecontactwithHgand

pluggedwithamixtureofcalomelHg2Cl2 &KCl.
y OutersleevehascrystalsofKCl &porousplugof
asbestos
y Advantages:easeofconstructionandstabilityof

p
potential.
Hg(l)|Hg2Cl2 (satd),KCl (aq,satd)|| Hg2Cl2(s)+2e
2Hg(l)+2Cl(aq)

10

Silversilverchlorideelectrode
y Widelyusedbecausesimple,

inexpensive,verystableandnontoxic.
y Mainlyusedwithsaturatedpotassium
chloride(KCl)electrolyte.
y Advantages:easytouse
Ad
t

t
Ag(s)|AgCl (sat
(satd),KCl
d),KCl (xM)||AgCl(s)+e
(xM)||AgCl(s)+e
Ag(s)+Cl (aq)

11

12

13

Sensing Electrodes
SensingElectrodes
y Thepotentialofthesensingelectrodeinapotentiometric

electrochemicalcellisproportionaltotheconcentrationof
analyte.
y Theindicatorelectrodesthatarealwaysusedin
potentiometry:
y membraneelectrodes(ionselectiveelectrodes)
y glasspHelectrode
l H l t d

14

Membraneelectrodes
GlasspHelectrode
y AdvantagesoverotherelectrodesforpHmeasurements:
y Itspotentialisessentiallynotaffectedbythepresenceof
I
i li
i ll ff
db h
f
oxidizingorreducingagents.
y ItoperatesoverawidepHrange
ItoperatesoverawidepHrange.
y Itrespondsfastandfunctionswellinphysiological
systems.

15

Eglass = constant 2.303RT/F log (aH+ int/ aH+ ext)

The hydrated glass responds to aH+.
The asymmetry potential off the glass membrane is unknown,
so the electrode must be calibrated with a standard buffer.

Makeselectrical
contactwithglass,
andsetspotentialof
ref.electrode.

Glass pH electrode.
16

This is two electrodes in one.

The porous plug salt bridge must be immersed in the solution.

Combination pH-reference electrode.

17

The potential determining membrane is a layer of water-immiscible

liquid
ion exchanger
membrane face.
q
g at the porous
p

Liquid-membrane electrode.
18

Principle:
y Thepotentialdifferencebetweeninnerandoutersilversilverchloride
p

electrodesdependsonthechlorideconcentrationineachelectrode
compartmentandonthepotentialdifferenceacrosstheglass
membrane.

y Because[Cl]isfixedineachcompartmentandbecause[H+]isfixed

ontheinsideoftheglassmembrane,theonlyvariableisthepHof
analyte solutionoutsidetheglassmembrane.

y ThevoltageoftheidealpHelectrodechangesby59.16mVforeverypH

unitchangeofanalyte activityat25C.

19

Theoryoftheglassmembranepotential
y Boththeinsideandoutsidesurfacesoftheglass
y

y
y

membraneintheGEbulbhaveSiOH groups.
Theinteriorsurfaceoftheglassmembraneisin
Th i
i f f h l
b
i i
contactwithaconstantconcentrationofHCl,andso
thenumberofSiO groupsontheinteriorsurface
remainsconstant.
i

Bycontrast,thenumberofSiO groupsontheexterior
g
g
p
oftheglassmembranewillchangewhenthepHofthe
solutiontheglassmembraneisimmersedinchanges.
Thedifferenceinchargeontheinsideandoutsideof
theglassmembraneresultsinamembranepotential.
Ifwecansetupanexperimenttomeasurethe
membranepotential,thenthiscorrespondsto
measuringthepHofthesolutioninwhichtheglass
electrodeisimmersed.
20

Alk li E
AlkalineError
y SystematicerroroccurswhenusingglasspHelectrodeto

measurepHofextremelyalkalinesolution
y GlasspHelectroderespondsveryselectivelytoH+ions,

but,sensitivetoalkalimetalionstoo
,
y Causedbyinterferenceofhighconcentrationofalkaline
+,Na+,K+
metalions,e.g:Li
l

21

Alkaline Error
AlkalineError
y In basic solution,
solution glass electrodes respond to the concentration of

both hydrogen ion and alkali metal ions.

y The actual pH measurements depend on the magnitude of both
cations present and composition of the glass membrane.
membrane
y Contribution from other cations or anions other than hydrogen
ion can be described as selectivity of the electrode (membrane).

22

Alk li E
AlkalineError
y

AthighpHwhere[H+]<<<[Na+],electrodebeginsto
respondto[Na+].
y Ionexchangereactionoccursatmembranesurface

AlkalineionswillreplaceH+ionscompletely/partiallyin
outergellayerofglassmembrane.
g
y
g
y Result:pHvaluemeasured<actualpH
y Usuallynoticeable: pH>12
[Li+ /Na+]0.1mol/litre
23

DeviationfromlinearpH
dependenceduetoalkalineerror

Alkalineerror pHvalue alkaline concentration

24

Ion Selective Electrodes (ISE)

IonSelectiveElectrodes(ISE)

Constantion
concentration
Constant
potential

Variableion
concentration
25

Membranepotentialreflectsthegradientofactivityoftheanalyte
ionintheinnerandoiter (sample)solution.

26

27

PolymericMembranescanbemadeselectiveforionsbyusingligands
IONOPHORESwhichselectivelybindions
AtypicalcompositionforanISE:
p y
ApolymersuchasPVC
Aplasticiser
Ananionicsalttoreducethemembraneresistance
Abindingligandsuchascrownether(18crown6,15crown5,12crown4,
etc)
t )

O
O

O
O

O
O

28

H
i
l ti
l t d
k
Howionselectiveelectrodeswork
y Respondselectivelytooneion.
y Donotinvolveredoxprocesses.
y Featuresathinmembranecapableofbindingonlythe

intendedion.
y Theelectricpotentialdifferenceacrosstheion
Th l
i
i ldiff

h i
selectivemembraneismeasuredwithtworeference
electrodes.

29

30

31

PARAMETERSFORANISE
y Sensitivity
y Selectivity
y LimitofDetection
y Responsetime

32

I
l i i
Ionselectivity
p
y p
p
y Aspecificionelectrodewillonlyrespondtothepresenceof
onespecies.
y Inreality,ionselectiveelectrodescanexperience
i t f
interferencesbyrespondingtothepresenceofotherions.
b
di t th
f th i
y Wecanaccountforthelackof100%specificityby
incorporatingtheactivityofjandaselectivitycoefficient
p
g
y j
y
ff
(Kij)intothisequation:

33

Selectivity
Nicolsky EisenmannEquation
zi
2.303RT
pot
E=E
logai + Kij (a j ) z j

nF

Whereai=activityoftargetion,aj=activityofinterferrentions,
ziandzjaretherespectivecharges

pot
ij

ai
zi

aj

zj

Iscalledtheselectivitycefficient

34

h
l
ff
l
f
y Theselectivitycoefficientisanumericalmeasureof
y
y

y
y

howwellthemembranecandiscriminateagainstthe
interferingion.
Toputthisinperspective,ifanelectrodehas
equivalentresponsestothetwoions,thenkij =1.0.
From the equation,
equation the smaller the kij values,
values the less
impact the interfering ion will have on the measured
potential.
When kij values are less than 1,
1 the ISE is more
responsive to the analyte ion
When kijj values are greater than 1, the ISE is more
responsive
i to the
h interfering
i
f i
i
ion.
For example,
l a kij
value of 0.01 means that the electrode is 100 times
more responsive to ion i over j.
35

i)separate solution method

Th larger
The
l
the
th potential
t ti l difference,
diff
the
th more selective
l ti the
th electrode.
l t d

The separate solution method of determining

selectivity coefficient for ion A with respect to ion B
B.
36

ii) Fixed interference method

The calibration curve for A is prepared in the presence of fixed activity of interfering ion.
zA and zB are the charges of the ions.
The intersection is where the electrode responds equally to both ions.
ions

Fixed interference calibration curve.

37

y Theselectivity oftheISEisdeterminedbythe

i i f h
b
compositionofthemembrane.
y Ideallythemembraneallowstheuptakeofonly
onespecificionintoit.
onespecificionintoit
y Thethreemaincomponentsofmakinga
measurementatanISEare
y aninnerreference,orstandardsolution
y anouteranalyte,orsample,
y solutionseparatedbyathinmembrane.
l ti
t db thi
b

y Thepotentialdevelopedatthemembraneisthe
resultofeitheranionexchangeprocessoranion
g p
transportprocessoccurringateachinterface
betweenthemembraneandsolution.

38

Ion Exchange Process

IonExchangeProcess

Lithiumcation displacesapotassiumcation fromthe

organicanion,R:
KR+Li+ LiR +K+
WecanimbedthelipophilicR inamembraneandplace
itinasolutionofLi+
KR(mem)+Li+(aq) LiR(mem)+K+(aq)
39

y Toconstructanionselectiveelectrodeaninner

f
l ti dd dt th th id fth
referencesolutionaddedtotheothersideofthe
membrane.
y Thissolutionwouldcontainafixedconcentrationof
theionofinterest,Li+inthisexample.
y Thisistypicallyaccomplishedbyplacingathin
membraneattheendoftheplastictubeandfillingthe
b
h d f h l i b dfilli h
tubewithastandard(knownconcentration)solution
y
oftheanalyte.
y Areferenceelectrodeisplacedintheinnersolution
andasecondreferenceelectrodeisincontactwiththe
analyte (outer)solution.
(outer)solution

40

Iontransport

Amembrane,containinganionophore,betweenan
unknownanalyte
unknown analyte solutionanda
solutionandaknownreference
known reference
solution.
Theionophore isaneutralcarriermolecule
representedbytheblueoval.
db h bl l
41

y Theionophore cannotdiffuseoutofthemembrane

andbutcantraptheanalyte ion(A+)attheinterface
betweenthesolutionandmembrane.
y Withouttheionophore,theanalyte wouldbeunableto
partitionintotheorganicmembrane.
y Aswiththeion
Aswiththeionexchangeprocess
exchangeprocess,equilibriumis
equilibriumis
establishedatbothsolutionmembraneinterfaces.The
resultingchargeseparationateachinterfaceleadstoa
g
g
p
phaseboundarypotential.
y Nowpotentialdevelopacrossthemembrane.

42

S iti it
Sensitivity
y Ability to detect primary ion at the lower concentration.
y Theoretical value of S=59mV
S=59mV,represents
represents 100%

sensitivity.
y The value of S varies with Kij

43

DetectionLimit
etect o
t
y Defined by the intersection of the two extrapolated linear

parts of the ion-selective calibration curve.

y LOD ~ 10-5-10-6 M is measured for most ISE.
y Observed LOD is often governed by the presence of other
interfering ions or impurities.
y Metal buffers can be used to eliminate the effects which
lead to the contamination of very dilute solutions. May
reduce LOD to 10-10 M.

44

Sensitivity & Limit of Detection

Sensitivity&LimitofDetection

Nernstequation

E = E 0 k log a
Wherekistheslope=RT/nF
Monovalent:59.16mV/dec
Di l
Divalent:29.58mV/dec

8 V/d
45

Responsetime
p
IUPACdefinition:
Timetakentoreachavalueofwithin1mVoftheequilibrium
value.

From the time the ISE and a reference electrode are dipped in the
sample solution (or the time at which the ion concentration in a
solution in contact with ISE and a reference electrode is changed )
to when the potential of the cell becomes equal to its steady-state
steady state
value within 1 [mV] or has reached 90% of the final value (in certain
cases also 63% or 95%).
The response time usually increases with decreasing determinand
concentration

Acceptable<60secs fordiptypesensors;<30secforFIA.
46

ApplicationofISE
pp
AGRICULTURE

COSMETICS
INDUSTRIAL
PRODUCTION

WATERMONITORING

ISE
WASTEWATER
TREATMENT

FISHERIES

POLLUTION
CONTROL

BLOODTESTING

47