Section 11

Potentiometry
 Potentiometric Electrodes
• Potentiometric electrodes measure:
• Activity not concentration
• Concepts to review:
• Activity and affect factors
 Potentiometric Electrodes
• Electrode of the First Kind:
• Metal in contact with Cation: M/Mn+
• Example: Ag/Ag+
• Ag+ + 1 e-  Ag(s)
• Nernst Equation:
• E = EoAg+/Ag – 2.303RT/nF(log1/aAg+)
• Where aAg+ = activity of silver ion
• Emeasured = Ecell = Eind vs NHE = Eind – ENHE
• Why does Ecell = Eind ?
• Eref  solution  Eind
 Potentiometric Electrodes
• Electrode of the Second Kind:
• General Form: MMXXn-
• Example: AgAgCl(S)Cl-
• AgCl + 1 e-  Ag(s) + Cl-
• Nernst Equation:
• E = EoAgCl/Ag – 2.303RT/nF(log aCl-)
• What observation can you make about
potential for this electrode?
 Potentiometric Electrodes
• Can the previous electrode be utilized to
measure aAg+ ?
 Potentiometric Electrodes
• Electrode of the Second Kind:
• General Form: MMXXn-
• Example: Calomel Electrode
• Hg Hg2Cl2(S)Cl-
• Hg22+ + 2 e-  Hg(s)
• E = EoHg22+/Hg – 2.303RT/nF(log 1/aHg22+
• Hg2Cl2(s) + 2e-  2 Hg + 2 Cl-
• E = EoHg2Cl2/Hg – 2.303RT/nF(log aCl-)2
• Kosp = aHg ‘ (aCl-)2
 Potentiometric Electrodes
• REDOX ELECTRODES:
• Inert Metal Electrode: Platinum, Pt
• Ma+ + n e-  M(a-n)+
• E = EoMa+/M(a-n)+ - 2.303RT/nF (log aM(a-n)+/ aMa+
• Example:
• MnO-4 + 8 H+ + 5e-  Mn2+ + 4 H2O
• Can you write the potential for this half cell?
 Potentiometric Electrodes
• Normal Hydrogen Electrode:
• H+ + e-  ½ H2(g)
• Can you write the Nernst Equation for this
half cell?
HH+ +++ee- -==½H
½H2 2
EE==EEoo––2.303RT/F
2.303RT/Flog
log(P
(PH2H2) )1/2/a/aH+H+
1/2

EEoo==0.000
0.000V.
V. IfIfPPH2H2==11atm.,
atm.,EE==-2.303RT/F
-2.303RT/FpH
pH

©Gary Christian,
Analytical Chemistry,
Fig. 13.1. Hydrogen electrode. 6th Ed. (Wiley)
 Potentiometric Electrodes
• Cells Without Liquid Junction:
• Two Half Cells Required
• Indicator Electrode
• Reference Electrode
• Example: Ptg), HCl (solution)gCl(s)g
• Can you write the cell potential Ecell for this
electrode system?
 Potentiometric Electrodes
• Cells With Liquid Junction:
• Two Half Cells Required
• Indicator Electrode
• Reference Electrode
• Example:
• HgHg2Cl2(sCl(saturated)Cl(solution), H2(g)Pt
• Can you write the cell potential Ecell for this
electrode system?
• Ecell = (Eright – Eleft) + Ej
EEj isisdue
duetotounequal
unequalmigration
migrationofofcations
cationsand
andanions
anionsat
atthe
theboundary
boundaryof
ofaaliquid
liquidjunction,
junction,
j
e.g.,
e.g.,at ataasalt
saltbridge
bridgeinterface.
interface.
This
Thischarge
chargeseparation
separationresults
resultsin
inaapotential
potentialat
atsteady
steadystate.
state.
EEj isisminimized
minimizedby byaahigh
highconcentration
concentrationofofaasalt
saltwith
withnearly
nearlyequal
equalmobilities
mobilitiesof
of cation
cation
j
and
andanion
anionin
inthe
thesalt
saltbridge,
bridge,e.g.,
e.g.,saturated
saturatedKCl.
KCl.
The
Theflux
fluxof
ofthe
themigration
migrationof
ofthis
thiselectrolyte
electrolyteisismuch
muchgreater
greaterthan
thanmore
moredilute
diluteones,
ones, and
and
largely
largelydetermines
determinesEEj. . j

Fig. 13.2. Representation of liquid-junction potential.

©Gary Christian, Analytical Chemistry, 6th Ed. (Wiley)
HH+ +and
andOH
OH-have
-
havehigh
highmobilities
mobilitiesand
andso
sopH
pHmarkedly
markedlyaffects
affectsEEj.j.
Therefore,
Therefore,pH
pHelectrode
electrodecalibration
calibrationshould
shouldbe
bedone
donenear
nearthe
thesample
samplepH.
pH.

©Gary Christian, Analytical Chemistry, 6th Ed. (Wiley)

 The
TheS.C.E.
S.C.E.isisaacommon
commonreference
referenceelectrode.
electrode.
The
Thecell
cellhalf-reaction
half-reactionis:
is: ½Hg
½Hg2Cl
Cl2 ++ee-==Hg
-
Hg++Cl
Cl.-.
-
2 2

EE==EEoo––0.0592
0.0592log
log1/a
1/aClCl- -==0.242
0.242VVfor
forsaturated
saturatedKCl.
KCl.

©Gary Christian,
Analytical Chemistry,
6th Ed. (Wiley)

Fig. 13.3. Commercial saturated calomel electrode.

 Reference
Referenceelectrode
electrodepotentials
potentialsare
areall
allrelative.
relative.
The
Themeasured
measuredcell
cellpotential
potentialdepends
dependsononthe
theone
oneused.
used.

Fig. 13.4. Schematic representation of electrode potential

relative to different reference electrodes.

©Gary Christian, Analytical Chemistry, 6th Ed. (Wiley)

AAcomplete
completecell
cellconsists
consistsof
ofan
anindicating
indicatingelectrode
electrodethat
thatresponds
respondsto
tothe
theanalyte
analyte
and
andaareference
referenceelectrode
electrodeof
offixed
fixedpotential.
potential.
The
Thepotential
potentialdifference
differencebetween
betweenthe
thetwo
twoisismeasured.
measured.

Fig. 13.5. Cell for potentiometric measurements.

©Gary Christian, Analytical Chemistry, 6th Ed. (Wiley)
EEglass ==constant
constant––2.303RT/F
2.303RT/Flog
log(a
(aH+H+intint/ /aaH+H+extext) )
glass

The
Thehydrated
hydratedglass
glassresponds
respondsto
toaaH+H+. .
The
Theasymmetry
asymmetrypotential
potentialof
ofthe
theglass
glassmembrane
membraneisisunknown,
unknown,
so
so the electrode must be calibratedwith
the electrode must be calibrated withaa
standard
standardbuffer.
buffer.

Makes electrical
contact with glass,
and sets potential of
ref. electrode.

 Fig. 13.6. Glass pH electrode.

©Gary Christian, Analytical Chemistry, 6th Ed. (Wiley)
 This
Thisisistwo
twoelectrodes
electrodesininone.
one.
The
Theporous
porousplugplugsalt
saltbridge
bridgemust
mustbe
beimmersed
immersedin
inthe
thesolution.
solution.

Fig. 13.7. Combination pH-reference electrode.

©Gary Christian, Analytical Chemistry, 6th Ed. (Wiley)
 When
 WhenaaH+H+isisvery
verysmall,
small,the
theglass
glasselectrode
electrodesenses
sensesother
othercations.
cations.
The
Thesolution
solutionappears
appearsmore
moreacidic
acidicthan
thanititreally
reallyis.
is.

Fig. 13.8. Error of Corning 015 glass electrode in

©Gary Christian,

strongly alkaline solutions containing various cations. Analytical Chemistry,

6th Ed. (Wiley)
In
Invery
veryacid
acidsolutions,
solutions,the
theactivity
activityof
ofwater
waterisisless
lessthan
thanunity
unity(it
(itsolvates
solvatesthe
theproton).
proton).
The
TheaaH+ isisdecreased,
decreased,and
andthe
thepH
pHreading
readingisisincreased.
increased.
H+

High
Highconcentrations
concentrationsof
ofdissolved
dissolvedsalts
saltsor
oradding
addingaanonaqueous
nonaqueoussolvent
solventdoes
doesthe
thesame.
same.

Fig. 13.9. Error of glass electrode in hydrochloric acid solutions.

©Gary Christian, Analytical Chemistry, 6th Ed. (Wiley)
These
Theseare
arereally
reallyaccurate
accurateto
to0.01
0.01pH,
pH,due
duetotoDebye-Huckel
Debye-Huckellimitations
limitationsinincalculating
calculatingactivity
activityof
ofthe
the
chloride ion in the Ag/AgCl reference electrode used in measurements.
chloride ion in the Ag/AgCl reference electrode used in measurements.
But
Butthey
theyare
arereproducible
reproducibleto
to0.001
0.001pH
pHunit.
unit.
Only
Onlythe
thephosphate
phosphatemixtures
mixturesare
arereally
reallybuffers.
buffers.
KKa values
valueschange
changewith
withtemperature,
temperature,and
andso
sothe
thepH
pHchanges.
changes.
a

©Gary Christian, Analytical Chemistry, 6th Ed. (Wiley)

The
Thepotential
potentialscale
scaleisiscalibrated
calibratedin
inpH
pHunits
units(59.16
(59.16mV/pH
mV/pHatat25
25 oC).
o
C).
AAtemperature
temperatureadjustment
adjustmentfeature
featurechanges
changesthe
theslope
slopeby
by2.303RT/F.
2.303RT/F.

Fig. 13.10. Typical pH meter.

©Gary Christian, Analytical Chemistry, 6th Ed. (Wiley)
The
Theisopotential
isopotentialpoint
point(usually
(usuallyat
atpHpH7) 7)of
ofaaglass
glasselectrode
electrodeisistemperature
temperatureinsensitive.
insensitive.
The
Thepotential
potentialisisset
setat
atzero
zerohere
here(if
(ifdifferent
differentthan
thanzero,
zero,this
thisisisthe
theoffset).
offset).

Fig. 13.11. Isopotential point.

©Gary Christian, Analytical Chemistry, 6th Ed. (Wiley)
The
Themost
mostcommon
commonion-selective
ion-selectiveelectrode
electrodeof
ofthis
thistype
typeisisthe
thefluoride
fluorideelectrode:
electrode:
LaF crystal doped with Eu(II) to increase conductivity.
LaF3 crystal doped with Eu(II) to increase conductivity.
3

Plastic
Plasticmembrane-ionophore
membrane-ionophoreelectrodes
electrodeshave
haveaasimilar
similardesign,
design,with
withaasoft
softplastic
plasticPVC
PVC
membrane
membrane containing a neutral lipophilic ionophore that selectively complexes withthe
containing a neutral lipophilic ionophore that selectively complexes with the
test ion.
test ion.

Fig. 13.12. Crystal membrane electrode.

©Gary Christian, Analytical Chemistry, 6th Ed. (Wiley)
The
Thepotential
potentialdetermining
determining“membrane”
“membrane”isisaalayer
layerof
ofwater-immiscible
water-immiscible
liquid
liquid ion exchanger at the porous membraneface.
ion exchanger at the porous membrane face.

Fig. 13.13. Liquid-membrane electrode.

©Gary Christian, Analytical Chemistry, 6th Ed. (Wiley)
 There
Thereare
arenumerous
numerousplastic
plasticmembrane-ionophore
membrane-ionophoreelectrodes electrodesalso,
also,
e.g., for Na +
, K +
, Li +
, and Ca 2+
e.g., for Na +, K+, Li+, and Ca2+. .

©Gary Christian, Analytical Chemistry, 6th Ed. (Wiley)

 The
Thecrown
crownether
ethercavity
cavitysize
sizeisisjust
justright
rightfor
forcomplexing
complexinglithium
lithiumion.
ion.
ItItisisplaced
placedin
inaaPVC
PVCplastic
plasticmembrane.
membrane.

Fig. 13.14. 14-Crown-4 ether that selectively binds lithium ion.

©Gary Christian, Analytical Chemistry, 6th Ed. (Wiley)
 Amide-based
 Amide-basedionophores
ionophoresin
inPVC
PVCmembranes
membranesare
aregood
goodcomplexers
complexersof
ofthese
theseions.
ions.

 
Fig. 13.15. Ionophores for H+, Na+, and Ca2+.
©Gary Christian, Analytical Chemistry, 6th Ed. (Wiley)
The
Thelarger
largerthe
thepotential
potentialdifference,
difference,the
themore
moreselective
selectivethe
theelectrode.
electrode.

The separate solution method of determining

selectivity coefficient for ion A with respect to ion B.
©Gary Christian, Analytical Chemistry, 6th Ed. (Wiley)
The
Thecalibration
calibrationcurve
curvefor
forAAisisprepared
preparedin
inthe
thepresence
presenceof
offixed
fixedactivity
activityof
ofinterfering
interferingion.
ion.
zzA and
andzzB are
arethe
thecharges
chargesofofthe
theions.
ions.
A B

The
Theintersection
intersectionisiswhere
wherethe
theelectrode
electroderesponds
respondsequally
equallyto
toboth
bothions.
ions.

Fig. 13.16. Fixed interference calibration curve.

©Gary Christian, Analytical Chemistry, 6th Ed. (Wiley)
These
Theseare
areion-selective
ion-selectivefield-effect
field-effecttransistor
transistorelectrodes.
electrodes.
AAsemiconductor
semiconductortransistor
transistorserves
servesas asthe
thebase
basefor
forelectrical
electricalcontact.
contact.
ItItisiscoated
coatedwith
withinsulating
insulatinglayers
layersof
ofSiO
SiO2 2and
andSi
Si3NN4, ,and
andthen
thenan
anion-sensitive
ion-sensitivemembrane.
membrane.
3 4

This
Thisone
oneisisaanon-glass
non-glassISFET
ISFETpH
pHelectrode.
electrode.

Fig. 13.17. Solid-state ISFET electrode.

©Gary Christian, Analytical Chemistry, 6th Ed. (Wiley)