Potentiometry

Dr. Kathlia A. De Castro-Cruz

Analytical Chemistry for ChE
 Potentiometry
 branch of electrochemistry concerned with the
relationship between the potential of an
electrochemical cell and the concentration of
the contents of the cell.
 Basis of the methods:
 difference between the E values of two halves of a cell
giving rise to Ecell
 if one half reaction is known and held constant, the
concentration of species on the other side can be
measure
 Potentiometry
 Potentiometric method
Cell Representation:
reference electrode|salt
bridge|analyte
solution|indicator
electrode

Ecell = Eind - Eref + Ej

 Potentiometry
 Electrode
 a conductor at the surface of which electron
transfer to or from the surrounding solution
takes place.

 Maybe:
 Reference
 Indicator
 Potentiometry
 Reference Electrode
 is a half cell having a known electrode
potential that remains constant at constant
temperature and is independent of the
composition of the analyte solution
 always treated as the left-hand electrode
(anode)
 Common reference electrodes:
 Hydrogen electrode (SHE)
 Calomel Electrode (SCE)
 Silver/Silver chloride electrode
 Potentiometry
 Hydrogen Electrode (SHE)
 The ultimate reference
electrode
 Difficult to work with
 H2 is constantly
bubbled into a 1M HCl
solution (Pt/H2(1atm),
1M H+//)
 E0= 0.000000V
Potentiometry

If the reduced form in a

particular half-reaction in
the table comes into
contact with the oxidized
form in a half-reaction
above it in the table, a
redox reaction between
these two forms will occur.

If a reduced form in a
given reaction comes in
contact with an oxidized
form in a half-reaction
below it in the table, will
not occur.
 Potentiometry
 Calomel Electrode (SCE)

Crystal structure of calomel

Calomel Electrode:
½ Hg2Cl2(s) + e- ⇌ Hg(l) + Cl- E0 = +0.268 V
E (saturated KCl) = +0.2444 V
 Potentiometry
 Calomel Electrode (SCE)
 More commonly used electrode
 Hg/Hg2Cl2(sat),KCl//
 Chloride is used to maintain constant ionic strength
 The electrode maybe separate or built into the sensing
electrode (combination electrode)
 Use different concentrations of KCl
 0.1M & 1.0M – least temperature sensitive
 Saturated (4.6M) –
 E0=0.2444V at 250C
 most widely used due to the ease of preparation
 Temperature dependent
 Advantageous because of the [Cl-] does not change if
some liquid evaporates.
 Potentiometry
 Silver/silver chloride electrode
 Potentiometry
 Silver/silver chloride electrode
 also a common reference electrode
 easier to produce a combination electrode
 Employs a silver electrode immerse in a solution
saturated with both KCl and AgCl
 (Ag/AgCl(sat’d), KCl(sat’d)//)
 Potential is 0.199 V at 250C
 Potentiometry
 Typical commercial reference electrodes: (a) An SCE
(b) Silver/silver chloride electrode
Potentiometry
 Potentiometry
 Problems with reference electrodes
 porous plugs become clogged, thus causing sluggish,
unstable electrical response.
 Some designs incorporate a free-flowing capillary in
place of the porous plug.
 Other designs allow you to force fresh solution from
the electrode through the electrode-analyte junction
prior to a measurement.
 Potentiometry
 Junction potential
 Liquid junction potential
 Source of the junction potential
 The distance from – to + charge
junction represent relative
mobilities of the ions
 Salt bridge
 Used to minimize the liquid-
junction potential
 The salt bridge is effective if it
can make the mobilities of the
ions equal at the junction and
their concentrations large
 Potentiometry
 Indicator (sensing) electrodes
 Has a potential that varies in a known way with
variations in the concentration of an analyte
 It should response rapidly and reproducibly to
changes in the concentration of an analyte
 Types:
 Metallic (simple metal)
 Membrane (Glass membrane, Liquid membrane,
Solid State, Enzyme, Gas sensing)
 Ion-sensitive field effect transistors (ISFET)
 Potentiometry
 Simple metal indicator
 A bare metal in contact with a solution of its cation:
Mn+ + ne-  M(s) (indicator electrode)

0 .0592 1
E ind E 
0
log
n [M n ]

 Classes:
 Electrodes of the first kind
 Electrodes of the second kind
 Electrodes of the third kind
 Metallic redox
 Potentiometry
 Electrode of the first kind
 Pure metal electrode that is in direct equilibrium
with its cation in the solution
 A single reaction is involved: Xn+(aq) + ne- ⇌ X(s)
 Not widely used for potentiometric determinations
 not very selective and respond not only to their own
cations but also to other more easily reduced cations
 some metal electrodes can only be used for neutral or
basic conditions (Zn, Cd)
 Some metals are easily oxidized
 Some hard metals do not provide reproducible
potentials (Fe, Cr, Co, Ni)
 Potentiometry
 Electrode of the first kind
 Electrode system of the first
kind:
 Ag/Ag+ and Hg/Hg2+ for neutral
solution
 Cu+/Cu2+, Zn/Zn+2 etc. for
deareated solution
 The following equation is
applicable:
 Potentiometry
 Electrode of the second kind
 Metals not only served as
indicator electrodes for their
own cations but also respond
to the activities of anions that
form sparingly soluble
precipitates or stable
complexes with such cations
 Electrode reaction:
AgCl(s) + e- ⇌ Ag(s)+ Cl-(aq)
 Potentiometry
 Electrode of the third kind
 A metal electrode can be made to respond to a
different cation
 Example: mercury electrode has been used for the
determination of the pCa of calcium-containing
solutions
 Metallic Redox Indicator
 Electrodes fashioned from platinum, gold, palladium,
or other inert metals often serve as indicator
electrodes for red0x systems
 The inert electrode acts as a source for electrons
transferred from redox system in the solution
 Potentiometry
 Sample Problem
 A silver wire is dipped into a silver nitrate solution. A
potential of 0.450V was measured vs. SCE. What is
the [Ag+] for the unknown solution?

Solution:
 Metal electrodes are also sensitive to anions that
form low solubility precipitates with metal cations
 Example: Cl- with a silver electrode
AgCl  Ag+ + Cl-
Ag+ + e-  Ag(s)
Overall: AgCl + e-  Ag(s) + Cl-
 Potentiometry
 The working equation:

1
E 0
AgCl E 0
Ag  0.0592 log
[ Ag  ]
 For [Ag+], consider the ionic equilibria:
KspAgCl = [Ag+][Cl-]

 The new working equation:


[Cl ]
E 0 AgCl  E Ag  0.0592 log
0

KspAgCl
 Potentiometry

E 0
AgCl E 0
Ag  0.0592log KspAgCl  0.0592log[Cl ]

E 0 AgCl  0.799V  0.0592log1.82x1010  0.0592pCl

Eind  E 0 AgCl  0.222  0.0592 pCl

 Analogous to acid-base titration

 As the Ag+/Cl- titration proceeds, [Ag+] increases and
pAg ( -log[Ag+]) decreases.
 The cell responds to a change in [Cl-], which
necessarily changes [Ag+] because [Ag+][Cl-] = Ksp.
 Potentiometry
 Membrane indicator electrode
 Commonly known as ion-selective electrodes
because of the high selectivity of most of these
devices
 Also referred as pIon electrodes because their output
is usually recorded as a p-function, such as pH, pCa
or pNO3
 Properties
 Minimal solubility
 Electrical conductivity
 Selective reactivity with the analyte
Potentiometry
 Potentiometry
 Typical electrode system for measuring pH: (a) A glass electrode (indicator)
and SCE (reference) immersed in a solution of unknown pH (b)
Combination probe consisting of an indicator glass electrode and a
Silver/silver chloride referencecc

Cell representation of
figure (a)
 Potentiometry
 Glass Membrane electrode
 A potential difference is created across a membrane
that can be measured
 There is no change in the solution of actual
contact
 Example: pH electrode
 A combination electrode wherein the reference
electrode is inside of the pH electrode
 First discovered
 Still the most significant
 Relies on glass membrane
 Potentiometry
 Composition and Structure of Glass Membrane
 A special glass is used with a
composition:22%Na2O, 6% CaO, 72% SiO2
 Specific in its response toward hydrogen ions up
to a pH of about 9
 Potentiometry
 pH electrode
 In order to work, the glass must be hydrated
(already have partial silicate production)
 H3O+ partially populates both the inner and
outer SiO2 surfaces
 The concentration difference results in a
potential across the glass membrane
 This explains why electrodes are always kept
moist or in solution
 Selective to H3O+ but other ions can cause a
response especially if present in excess
 Potentiometry
 pH electrode
 The hydration of a pH-sensitive glass membrane
involves an ion-exchange reaction between singly
charged cations in the interstices of the glass lattice
and protons from the solution
 Ion-exchange reaction:

 Membrane potentials
 Reference electrode 1 (SCE)
 Reference electrode 2 (EAg, AgCl)
 Junction potential, Ej
 Boundary potential, Eb (varies with the pH of the analyte
solution)
 Potentiometry
 Boundary Potential
 Difference in potential
between the two boundaries
 Potentiometry
 Asymmetry Potential
 Arises when the boundary potential is not zero when
identical solutions and reference electrodes are
placed on the two sides of the glass membrane
 Sources of asymmetry potential
 Differences in strain on the two surfaces of the
membrane imparted during manufacture,
mechanical abrasion on the outer surface during
use, and chemical etching of the outer surface
 Remedy: calibration against several standards
carried out at least daily and more often when the
electrode receives heavy use
 Potentiometry
 Glass Electrode Potential
 It is the indicator potential
 Three components:
 Boundary potential
 Potential of the internal Ag/AgCl reference
electrode
 Small asymmetry potential
 Equation:
 Potentiometry
 Alkaline error
 False response when the electrode responds not
only to H3O+ but also to alkali metals (Na+, K+)
 Worsen when [Na+] > [H3O+]
 Common source of Na+ is NaOH (the electrode
shows no response to –OH ions)
 Sodium Electrode
 An electrode more sensitive to Na+ compared to H3O+
 Done by modifying the glass membrane
 Acid error
 Values registered by the glass electrode tend to be
somewhat high when pH < 0.5
 Potentiometry
 Liquid Membrane
Electrode
 Similar to a pH electrode
except the membrane is an
organic polymer saturated
with a liquid ion exchanger
 Interaction with target ions
results in a potential across
the membrane that can be
measured
 Ca2+ electrode is one of the
best example
 Potentiometry
 Liquid Membrane Electrode
 Liquid membrane calcium ion
electrode
 The active ingredient in an ion
exchanger is calcium dialkyl
phospahte (nearly water-insoluble)
 The ion exchanger is dissolved in an
immiscible organic liquid that is
forced by gravity into the pores of a
hydrophobic porous disk
 The exchanger forms complexes
with the species of interest
 This results in a concentration
difference and the resulting V is
measured
 Potentiometry
 Liquid Membrane Electrode
 Potentiometry
 Solid state Electrode
 Solid membranes that are selective towards anions
 A very popular type of ion specific electrode
 As easy to maintain as a pH electrode
 F- electrode
 The original solid state electrode
 Works by creating defects in a LaF3 crystal
 Other solid state electrode work based on the
presence of a primary absorbed ion
 The primary absorbed ions result in a
concentration gradient and ΔV is produced
 Potentiometry
 Solid state Electrode
 Potentiometry
 Solid state Electrode
 Potentiometry
 Enzyme Electrode
 A normal pH electrode is coated with a
urease impregnated gel
 Urea will permeate the gel where the
enzyme will attack resulting in the
formation of ammonium
 The resulting change in pH can be
measured
 Advantages
 The potential exists for developing
electrodes for any permeable species
where a pH dependent reaction results
 Potentiometry
 Enzyme Electrode
 Disadvantages
 Gels must be replaced regularly
 Each measurement results in a
cumulative response
 The response is time dependent
 Potentiometry
 Enzyme Electrode
 Potentiometry
 Gas-sensing Probes
 Gas-sensing probe is a
galvanic cell whose
potential is related to
the concentration of a
gas in a solution
 Components:
 Tube containing
reference electrode
 Selective ion electrode
 Electrolyte solution
 Widespread used in
dissolved gases
determination on water
and in other solvents
 Potentiometry
 Gas-sensing probe
 An indicating electrode
is placed into a specific
solution
 There is a permeable
membrane on the
opposite side
 Permeation of the target
analyte results in an
equilibrium change that
can be measure
 Potentiometry
 Gas-sensing probe
 Examples:
 CO2 H2CO3 H+ + HCO3-
 pH electrode is used for indicating
 2HCN 2HCN 2CN- + Ag+ Ag(CN)2-
 Silver electrode is used for indicating
 Potentiometry
 Gas-sensing probe
 Potentiometry
 Ion-selective Field Effect Transistors (ISFET)
 Potentiometry
 Ion-selective Field Effect Transistors (ISFET)
 Improved MOSFETS (metal oxide field effect
transistor)
 Advantages over membrane electrodes
 Ruggedness
 Small size
 Inertness towards harsh environments
 Rapid response
 Low electrical impedance
 Potentiometry
 Ion-selective Field Effect
Transistors (ISFET)
 Commercial example: i-STAT
portable clinical analyzer
 Potentiometry
 Analytical techniques
 Direct Potentiometry
 Simply calculate concentration based on E cell
 Not very good: must have ideal behaviour and
know all properties of the electrode
 Seldom done
nEcell  K 
pX   log a X  
0.0592
nEcell  K 
pA   log a A 
0.0592
 Potentiometry
 Analytical techniques
 Electrode Calibration Method
 Advantages
 Simple
 Speed
 Applicability to the continuous monitoring of pX and
pA
 Disadvantage
 Limited accuracy because of uncertainties in junction
potential
 Assumption
 K is constant
 K is evaluated with a standard solution of the
analyte
 Potentiometry
 Analytical techniques
 Electrode Calibration Method
 Assumption
 K is determined by measuring Ecell for one or
more standard solutions of known pX and pA
 K is not changed when the standard is
replaced by the analyte solution
 Inherent error
 Results from the assumption that K is
constant after calibration
  1 mV or more
 K is evaluated with a standard solution of the
analyte
 Potentiometry
 Analytical techniques
 Null Point Potentiometry
 Use of two indicating electrodes for the same half
reaction
 One electrode is known and the other is unknown
 The known concentration is varied until Ecell = 0
 Cancel out the activity problems but very time
consuming
 Potentiometry
 Analytical techniques
 Standard Curve Method
 Measure a range of standards and produce a
calibration curve
 The response is log based; standards must vary
by a factor of 10 (example: 1, 10, 100, 1000 ppm)
 Potentiometry
 Analytical techniques
 Standard Addition Method
 Involves determining the potential of the
electrode system before and after a measured
volume of a standard has been added to a known
volume of the analyte
 Known varying amounts of the assayed substance
are added to several equal portions of the sample
solution
 Plot measured parameter vs. concentration of the
standard solutions
 Linear plot is extrapolated to the concentration
axis (x-intercept)
 Potentiometry
 Analytical techniques
 Standard Addition Method

 Use to aid the significant problems encountered

with using an ISE at low concentrations
 Long time to reach equilibrium
 Large relative error
If you want to achieve great things,
you must begin with a dedicated
heart and a faith in your heart and a
faith in your calling