Chapter 21

Potentiometry

1
 Potentiometric methods
• Potentiometric methods of analysis are based on measuring the potential
of electrochemical cells without drawing appreciable currents.

• Applications:
 Determine end points in titration
 Determine ion concentrations with ion-selective membrane
electrodes
 Measure pH
 Determine thermodynamic equilibrium constants , such as Ka, Kb,
Ksp…

2
 Potentiometric methods
General principles
• A typical cell for potentiometric analysis can be represented as:

reference electrode | salt bridge | analyte solution | indicator electrode

Eref Ej Eind

Ecell = Eind – Eref + Ej

• For most electroanalytical

methods, the junction potential
is small enough to be neglected.

3
 Potentiometric methods
General principles
reference electrode | salt bridge | analyte solution | indicator electrode
Eref Ej Eind
• Reference electrode:
 A half-cell having a known electrode potential (Eref) that remains constant at
constant temperature and is independent of the composition of the analyte
solution.
 SHE can be reference electrode but seldom is used.
 Always treated as the left-hand electrode.
• Indicator electrode:
 Immersed in a solution of the analyte
 has a potential (Eind) that depends on the activity of the analyte.
 Usually are selective in response
• Salt Bridge:
 Prevents components of the analyte solution from mixing with those of the
reference electrode
 KCl is a nearly ideal electrolyte for the salt bridge because the mobilities of
the K+ and Cl- are nearly equal.

4
 Reference Electrodes
• The ideal reference electrode has a potential that is accurately known,
constant, and completely insensitive to the composition of the analyte
solution.
• The electrode should be rugged, easy to assemble, and should maintain a
constant potential while passing minimal currents.

Calomel Reference Electrodes

• It consists of mercury in contact with a solution that is saturated with
mercury(I) chloride (calomel) and that also contains a known
concentration of potassium chloride.
Hg | Hg2Cl2(sat’d), KCl(x M) ||
 x represents the molar concentration of potassium chloride in the solution.
 Conc. of KCl are commonly 0.1M, 1M, and saturated (4.6M)
 The saturated calomel electrode (SCE) is the most widely used ref. electrode,
easy to prepare for use, potential is 0.2444 V at 25oC

Hg2Cl2(s) + 2e-  2Hg(l) + 2Cl-(aq)

5
 Reference Electrodes
• Table lists the compositions and formal electrode potentials for
common reference electrodes.

• Three calomel electrodes contain saturated Hg2Cl2 and

the cells differ only with respect to KCl concentration.

• The commercial calomel electrode ().

 Saturated KCl acts as a salt bridge through a piece
of porous Vycor seal.
 This type of junction has relatively high resistance
(2~3kW) and a limited current-carrying capacity
but with minimal leakage of KCl.
 SCE is less common in use because of concerns
with mercury contamination.
6
 Reference Electrodes
Silver/Silver Chloride Reference Electrodes
• The most widely marketed reference electrode system consists of a silver
electrode immersed in a solution of potassium chloride that has been saturated
with silver chloride:
Ag | AgCl(sat’d), KCl(sat’d) ||

• The electrode potential is determined by the Reference electrode

half-reaction: potential (Eref)

AgCl(s) + e-  Ag(s) + Cl-

• The electrode is prepared with a saturated or a

3.5M KCl solution
• Advantage:
 can be used at > 60oC (SCE cannot)
• Disadvantage:
 Ag+ may react with sample components
which may lead to plugging of the junction
between electrode and the analyte solution junction
potential (Ej)
7
 Liquid-Junction Potentials
• When two electrolyte solutions of different composition are in contact
with one another, there is a potential difference across the interface as a
result of an unequal distribution of cations and anions across the
boundary.
• The liquid junction for the 1M/0.01M HCl solution can be represented as:
HCl(1 M) | HCl(0.01 M)
• Both H+ and Cl- ions tend to diffuse across the
inert porous barrier.
• The driving force for each ion is proportional to
the activity difference between two solutions.
• H+ ions diffuse more rapidly than Cl- ions results a
separation of charge.
• The potential difference resulting from this charge
separation is the junction potential.
• The magnitude of the liquid junction potential can
be minimized by placing a salt bridge between two
solutions.
8
 Indicator electrodes
• An ideal indicator electrode responds rapidly and reproducibly to changes
in the concentration of an analyte ion (or group of analyte ions).
• Three types of indicator electrodes: (1) Metallic, (2) Membrane, and (3)
Ion-Selective Field Effect Transistor

Metallic indicator electrodes

• classified as (1) electrodes of the first kind, (2) electrodes of the second
kind, and (3) inert redox electrodes.
• An electrode of the first kind is a pure metal electrode that is in direct
equilibrium with its cation in the solution.
Example: Cu+2 (aq) + 2e-  Cu(s)
0.0592 1 0.0592 0.0592
Eind  ECu
0
 log  ECu
0
 log aCu 2  ECu
0
 pCu
2 aCu 2 2 2

• A general expression for any metal and its cation is:

0.0592 0.0592
Eind  EX0 n / X  log a X n  EX0 n / X  pX
n n
9
 Indicator electrodes
0.0592 0.0592
Eind  EX0 n / X  log a X n  EX0 n / X  pX
n n
• Electrodes of the first kind are not widely used for
potentiometric determinations…
1. Metallic indicator electrodes are not very selective and
respond not only to their own cations but also to other
more easily reduced cations.
=> Ex: Copper electrodes cannot be used for Cu2+ in the
presence of Ag+.
2. Many metal electrodes can only be used in neutral or
basic solutions because they dissolve in acidic condition.
3. Easily oxidized. So they can be used only when analyte solutions are deaerated
to remove oxygen.
4. Certain metals do not provide reproducible potentials. Plots of Eind vs. pX yield
slopes that differ significantly and irregularly from (-0.0592/n).
• The only electrodes for the first kind are Ag/Ag+, Hg/Hg2+ in neutral solution,
Cu/Cu2+, Zn/Zn2+, Cd/Cd2+, Bi/Bi3+, Tl/Tl+, Pb/Pb2+ in deaerated solutions.
10
 Indicator electrodes
• Electrodes of the second kind: Metals not only serve 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.
• The potential of a silver electrode correlates reproducibly with the activity
of chloride ion in a solution saturated with silver chloride.
AgCl(s) + e-  Ag(s) + Cl-(aq) E0AgCl/Ag = 0.222 V

• The Nernst expression for this process is:

Eind  E AgCl
0
/ Ag  0.0592 log aCl   E AgCl / Ag  0.0592 pCl
0

• In a solution saturated with AgCl, a Ag electrode can

serve as an indicator electrode of the second kind for Cl-
ion.

11
 Indicator electrodes

• Inert Metallic Electrodes for Redox Systems: several relatively inert

conductors respond to redox systems.
• Materials as platinum, gold, palladium, and carbon can be used to monitor
redox systems.
• Example:
 The potential of a Pt electrode immersed in a solution containing
Ce3+ and Ce4+:
Eind = EoCe4+/Ce3+ - 0.0592 log(aCe3+/aCe4+)

 A platinum electrode is a convenient indicator electrode for titrations

involving standard cerium(IV) solutions.

12
 Membrane Indicator Electrodes
• Membrane indicator electrodes are sometimes called p-ion electrodes because
the data obtained from them are usually presented as p-functions, such as pH,
pCa, or pNO3.
• Membrane electrodes are fundamentally different from metal electrodes both in
design and in principle.
• Example: The Glass Electrode for Measuring pH
1. A thin glass membrane separating two solutions with different [H+]
2. The sensitivity and selectivity of glass membrane toward H+ are well
understood.

• Typical electrode system for

measuring pH.
a) Glass electrode (indicator)
and SCE (reference) immersed
in a solution of unknown pH.
b) Combination probe consisting
of both an indicator glass
electrode and a silver/silver
chloride reference.

13
 pH Electrodes
• The internal reference electrode is not the pH-sensing element.
• The thin glass membrane bulb at the tip of the electrode that responds to pH.
• There is a charge imbalance across any material, there is an electrical potential
difference across the material.
• The concentration of protons inside the membrane is constant.

Diagram of glass/calomel cell for the measurement of pH

• ESCE is the potential of the reference electrode,
• Ej is the junction potential,
• E1 and E2 are the potentials on either side of the glass membrane,
• Eb is the boundary potential which varies with the pH of the analyte solution
• a1 is the activity of hydronium ions in the analyte solution, a2 is the activity of
hydronium ion in the internal reference solution.
14
The Composition and Structure of Glass Membranes
• Glass composition affects the sensitivity of membranes to protons and
other cations.
• Corning 015 glass has been widely used for membranes and it exhibits
excellent specificity to H+ up to pH 9. However, it responses to Na+ as well
as to other singly charged cations.

• (a) Cross-sectional view of a silicate glass structure. In addition to the

three SiO bond shown, each silicon is bonded to an additional oxygen
atom, either above or below the plane of the paper.
15
The Composition and Structure of Glass Membranes
• The two surfaces of a 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 interstices of the glass
lattice and hydrogen ions from the solution.
H+ + Na+Gl-  Na+ + H+Gl-

• This process involves +1 cations exclusively because +2 and +3 cations are

too strongly held within the silicate structure to exchange with ions in the
solution.
• The equilibrium constant for this process is so large that the surfaces of a
hydrated glass membrane normally consist entirely of silicic acid (H+Gl-).
• In highly alkaline solution, H+ is small, so a significant fraction of the sites
are occupied by Na+.

16
 Membrane Potentials
• Four potentials develop in a cell when pH is being determined with a
glass electrode.
1. EAg,AgCl and ESCE, are reference electrode potentials that are constant.
2. Ej, the junction potential is across the salt bridge that separates the
calomel electrode from the analyte solution.
3. The fourth potential is called the boundary potential Eb that varies with
the pH of the analyte solution.

17
 Boundary Potentials
• The boundary potential is determined by potentials, E1 and E2, which appear at
the two surfaces of the glass membrane.
• The source of these two potentials is the charge that accumulates as a
consequence of the reactions: Glass1/Solution1: the interface
between the exterior of the
H+Gl- (s)  H+ (aq) + Gl- (s)
glass and the analyte solution
H+Gl- (s)  H+ (aq) + Gl- (s) Glass2/Solution2:the interface
between the internal solution and
the interior of the glass
• These two reactions cause the two glass surfaces to be negatively charged with
respect to the solutions with which are in contact.
• The boundary potential is related to the activities of hydrogen ions in the solutions
expressed by the Nernst-like equation:
Eb = E1 – E2 = 0.0592 log a1/a2
a1 is the activity of the analyte solution; a2 is that of the internal solution.

18
 Boundary Potentials

Eb = E1 – E2 = 0.0592 log a1/a2

• For a glass pH electrode, the hydrogen ion activity of the internal

solution, a2, is held constant so the equation simplifies to:

Eb = L’ + 0.0592 log a1 = L’ – 0.0592 pH

Where L’ = -0.0592 log a2

• The boundary potential is then a measure of the H+ activity of the

external solution.

19
Boundary Potentials
• Potential profile across a glass membrane from the
analyte solution to the internal reference solution
is showing in figure.
• The potential profile is regardless of the absolute
potential inside the hygroscopic layers or the glass.
• The boundary potential is determined by the
difference in the potential on either side of the
glass membrane.

• The asymmetry potential: identical solutions are

placed on the two sides of the glass membrane but
showing non-zero boundary potential.
• To eliminate the bias caused by the asymmetry
potential, membrane electrodes must be calibrated
against standard analyte solutions.
20
 The Glass Electrode Potentials

• The potential of a glass indicator electrode, Eind, has three components:

(1) the boundary potential;
(2) the potential of the internal Ag/AgCl reference electrode; and
(3) the small asymmetry potential, Easy, which changes slowly with time.

Eind  Eb  E Ag / AgCl  Easy

Eind  L'  0.0592 log a1  E Ag / AgCl  Easy

Eind  L  0.0592 log a1  L  0.0592 pH
L is a combination of the three constant terms

• The mechanisms of charge separation that result in these expressions

are considerably different.

21
 The Alkaline Error
• In basic solutions, glass electrodes respond to the concentration of both
hydrogen ion and alkali metal ions.
• The magnitude of the resulting alkaline error for four different glass
membranes is shown in the graph.

• The error (pHread – pHtrue) is negative

suggesting that the electrode is
responding to Na+ as well as to H+.

22
The Alkaline Error

In solution

In glass

23
 Selectivity
• The effect of an alkali metal ion on the potential across a membrane can
be accounted for by inserting an additional term called the selectivity
coefficient (kH,B), which is a measure of the response of an ion-selective
electrode to other ions.
Eb = L’ + 0.0592 log (a1 + kH,Bb1)

• Selectivity coefficients range from zero (no interference) to values greater

than unity.
• If an electrode for ion A responds 20 times more strongly to ion B, than to
ion A, kH,B = 20
• kH,Bb1 is usually small relative to a1 provided that the pH < 9 in glass pH
electrode.
• At high pH and at high conc. of a singly charged ion, (a1 + kH,Bb1) becomes
important in determining Eb.

24
 The Acid Error
• In solution of pH less than 0.5, the negative error (pHread – pHtrue)
indicates that pH readings tend to be too high.
• One source causes the acid error is a saturation effect that occurs when
all the surface sites of the glass are occupied with H+ ions.
• Under these conditions, the electrode no longer responds to further
increases in the H+ concentration and the pH readings are too high.

25
 Glass Electrodes for Other Cations
• Glass compositions permit the determination of cations other than
H+.
• Incorporation of Al2O3 or B2O3 in the glass helps to eliminate the
alkaline error in glass electrodes.
• Glass electrodes that permit the direct potentiometric
measurement of such singly charged species as Na+, K+, NH4+, Rb+,
Cs+, Li+, and Ag+ have been developed.
• Glass electrodes for Na+, Li+, NH4+, and total conc. of univalent
cations are commercially available now.

26
 Liquid-Membrane Electrodes
• The potential of liquid-membrane electrodes develops across the
interface between the solution containing the analyte and a liquid-ion
exchanger that selectively bonds with the analyte ion.
• Liquid-membrane electrodes have been developed for the direct
potentiometric measurement of numerous polyvalent cations as well as
certain anions.

• Diagram of a liquid-membrane electrode

for Ca+2. It consists:
1. A conducting membrane that selectively
binds Ca2+.
2. An internal solution containing a fixed
conc. of CaCl2.
3. A silver electrode that is coated with AgCl
to form an internal reference electrode.

27
 Comparison of a liquid-membrane calcium ion
electrode with a glass pH electrode
• The active membrane
ingredient is an ion exchanger
that consists of a calcium
dialkyl phosphate that is
nearly insoluble in water.
• The ion exchanger is dissolved
in an immiscible organic liquid
that is forced by gravity into
the pores of a hydrophobic
porous disk.
• This disk serves as the
membrane that separates the
internal solution from the
analyte solution.

28
 Calcium Ion Electrode
• A dissociation equilibrium develops at each membrane interface:
[(RO)2POO]2Ca  2(RO)2POO- + Ca2+
R is a high-molecular mass aliphatic group.

• As with the glass electrode, a potential develops across the membrane when the
extent of dissociation of the ion exchanger dissociation at one surface differs from
that at the other surface.
• The relationship between the membrane potential and the calcium ion activities
of the internal and external solutions is given by
• a1 and a2 are activities of
0.0592 a
Eb  E1  E 2  log 1 Ca2+ in the external analyte
2 a2 and internal standard
solutions
0.0592 0.0592
Eb  N  log a1  N  pCa
2 2
N is a constant
• The sensitivity for Ca2+ is 50X to Mg2+ and 1000X than Na+ or K+.
• It has good performance between pH 5.5 and 11.
• At lower pH, H+ replaces some of the Ca2+ on the exchanger and cause bias. 29
Liquid-Membrane Electrodes

• A liquid membrane consists of valinomycin

in diphenyl ether is about 1000 times as
responsive to K+ as to Na+.
• A tiny electrode can be used for
determining the K+ in a single cell.

30
Liquid-Membrane Electrodes

31
 Crystalline-Membrane Electrodes
• Some solid membranes are selective toward anions in the same way that
glasses respond to cations.
 Membranes prepared from cast pellets of silver halides have been used
for selective determination of Cl-, Br-, and I-.
 An electrode based on a polycrystalline Ag2S membrane is for the
determination of sulfide ion.
 In both types of membranes, Ag+ ions are mobile to conduct electricity
through the solid medium.

32
 Ion-Sensitive Field Effect Transistors (ISFETs)
• The field effect transistor, or the metal oxide field effect transistor
(MOSFET), is a tiny solid-state semiconductor device that is widely used in
computers and other electronic circuits as a switch to control current flow
in circuits.
• Its drawback is its pronounced sensitivity to ionic surface impurities.

• A metal oxide field effect

transistor (MOSFET)
1. Cross-sectional diagram
2. Circuit symbol

33
Ion-Sensitive Field Effect Transistors (ISFETs)
• ISFETs offer significant advantages over membrane electrodes
including ruggedness, small size, inertness toward harsh
environments, rapid response, and low electrical impedance.
• ISFETs do not need hydration before use and can be stored
indefinitely in the dry state.

• The ion-sensitive surface of

ISFET is sensitive to pH changes.
• The device can be modified to
become sensitive to other
species by coating the silicon
nitride gate insulator with a
polymer containing molecules
that tend to form complexes
with species other than H+.
• Sensing for multiple
measurements at the same
time is possible.
34
 Gas-Sensing Probes
• A gas-sensing probe is a galvanic cell whose potential is related to the
concentration of a gas in a solution.
• A thin, replaceable, gas-permeable membrane attached to one end of the
tube serves as a barrier between the internal and analyte solutions.
• This device is a complete electrochemical cell and is more properly
referred to as a probe.
• A microporous membrane is fabricated
from a hydrophobic polymer.
• The average pore size of membrane is less
than 1 mm and allows the free passage of
gases.
• The water-repellent polymer prevents
water and solute ions from entering the
pores.
• The thickness of the membrane is about
0.1 mm.
35
 Gas-Sensing Probes
• The mechanism of response:
 Using carbon dioxide as an example, we can represent the transfer of gas to the
internal solution in the electrode as:

 The last equilibrium causes the pH of the internal surface film to change.
 This change is then detected by the internal glass/calomel electrode system. So
the overall process is:

 The thermodynamic equilibrium constant for this reaction is

 [CO2(aq)]ext is the molar concentration of the gas in the analyte solution.

36
 Gas-Sensing Probes
• aHCO3- is constant, so

• For a neutral species CO2, if we allow a1 to be the hydrogen ion activity of the internal
solution,

• Substitute to Eind  L  0.0592 log a1  L  0.0592 pH

• We can obtain:

• Combining the two constant terms leads to a new constant L’

Eind = L’ + 0.0592 log[CO2(aq)]ext

• Also, Ecell = Eind – Eref

• Then, • Thus, the potential between the glass
electrode and the reference electrode
is determined by CO2 concentration in
the external solution.

37
Portable Instrumentation

• Most of the analytes are determined by

potentiometric measurements using
membrane-based ion-selective electrode
technology, such as pCO2, Na+, K+, Ca2+, pH.
• The hematocrit (Hct, the ratio of the volume
of red blood cells to the total volume of a
blood sample) is measured by electrolytic
conductivity detection.
• pO2 is determined with a Clark voltammetric
sensor.

38
 Instruments for measuring cell potential
• Most cells containing a membrane electrode have very high electrical
resistance (108 ohms or higher).
• In order to measure potentials of such high-resistance circuits
accurately, it is necessary that the voltmeter have an electrical
resistance that is several orders of magnitude greater than the
resistance of the cell being measured.
• If the meter resistance is too low, current is drawn from the cell, which
has the effect of lowering its output potential, thus creating a negative
loading error.
• Numerous high-resistance, direct-
reading digital voltmeters with internal
resistance of > 1011 ohms.
• These meters are commonly called pH
meters but could more properly be
referred to as pIon meters or ion
meters.

39
 Direct Potentiometry
• Direct potentiometric measurements provide a rapid and convenient
method for determining the activity of a variety of cations and anions.
• The technique requires only a comparison of the potential developed in a
cell containing the indicator electrode in the analyte solution with its
potential when immersed in one or more standard solutions of known
analyte concentration.
• If the response of the electrode is specific for the analyte, no preliminary
separation steps are required.
• Direct potentiometric measurements are also readily for continuous and
automatic recording of analytical data.

40
 Direct Potentiometry
Equations Governing Direct Potentiometry
• For direct potentiometric measurements, the potential of a cell can then be
expressed in terms of the potentials developed by the indicator electrode,
the reference electrode, and a junction potential,
Ecell = Eind – Eref + Ej

• For the cation Xn+ at 25°C, the electrode response takes the general Nernstian
form: 0.0592 0.0592
E  L
ind pX  L  log a X
n n
L: a constant for either metallic indicator electrodes and membrane
electrodes, ax is the activity of the cation
 Ecell  ( E j  Eref  L) 
• Rearrange: pX   log a X    
 0.0592 / 2 
• Combined to give a new constant K:
( Ecell  K ) n( Ecell  K )
pX   log a X   
0.0592 / n 0.0592

41
 Direct Potentiometry
• For an anion An-:
( E cell K ) n( Ecell  K )
pA  
0.0592 / n 0.0592

• When the two equations are solved for Ecell, we find that for cations:
0.0592
Ecell  K  pX
n
• Thus, for a cation-selective electrode, an increase in pX results in a
decrease in Ecell.
• When a high-resistance voltmeter is connected to the cell (indicator
electrode attached to the positive terminal), the meter reading
decreases as pX increases.

0.0592
• For anions: Ecell  K  pA
n

42
 Direct Potentiometry
The Electrode-Calibration Method
( Ecell  K ) n( Ecell  K ) ( E cell K ) n( Ecell  K )
pX   log a X    pA  
0.0592 / n 0.0592 0.0592 / n 0.0592
• The constant K is made up of several constants, such as the junction
potential.  K has to be determined with a standard solution of analyte.
• The electrode-calibration method is also referred to as the method of
external standards.
• The electrode-calibration method offers the advantages of simplicity,
speed, and applicability to the continuous monitoring of pX or pA.

• However, there is an inherent error (of the order of 1 mV) in the

electrode calibration method that results from the assumption that K
remains constant after calibration.
• The electrolyte composition of the unknown may differ from that of the
solution for calibration.  K varies slightly.

43
 Direct Potentiometry
Inherent Error in the electrode-calibration procedure
• The magnitude of the error in analyte concentration can be estimated by
differentiating one equation while assuming Ecell constant.
( Ecell  K ) n( Ecell  K )
pX   log a X   
0.0592 / n 0.0592
dax da dK
differentiate  log 10 e  0.434 x  
ax ax 0.0592 / n
dax ndK
  38.9ndK
ax 0.0257
• When dax and dK are replaced with finite increments and multiple by 100%,
the percent relative error = Da x
100 %  38.9nDK 100 %
ax

• Ex: DK is +/- 0.001V, a relative error in activity of about +/- 4n%

• This error is characteristic of all measurements involving cells containing a
salt bridge.
• This error cannot be eliminated by even the most careful measurements or
the most sensitive and precise measuring devices.
44
 Direct Potentiometry
Activity vs. Concentration
• Electrode responses is related to analyte activity rather than concentration.
• Activity coefficients are seldom available because the ionic strength of the
solution either is unknown or too large that the Debye-Huckel equation is not
applicable.
• Figure: Response of a liquid-membrane
electrode to variations in the concentration
and activity of calcium ion.
• The nonlinearity is due to the increase in
ionic strength—and the consequent
decrease in the activity of calcium ion—
with increasing electrolyte concentration.
• Activity coefficients for singly charged
species are less affected by changes in ionic
strength.  H+, Na+ less affected.
• A total ionic strength adjustment buffer Solid line: activity with a
(TISAB) is used to control the ionic strength theoretical slope of
and the pH of samples and standards in ion- 0.0592/2 = 0.0296 V
selective electrode measurements.
45
 Direct Potentiometry
The Standard Addition Method
• The standard addition method
involves determining the
potential of the electrode
system before and after a
measure volume of a standard
has been added to a known
volume of the analyte solution.

46
Potentiometric pH Measurement with the Glass
Electrode
• The glass/calomel electrode system is a remarkably versatile tool for the
measurement of pH under many conditions.
• It can be used without interference in solutions containing strong
oxidants, strong reductants, proteins, and gases.

• However, there are distinct limitations to the electrode:

1. The alkaline error: pH > 9
2. The acid error: pH < 0.5
3. Dehydration: cause erratic electrode performance
4. Errors in low ionic strength solutions
5. Variation in junction potential
6. Error in the pH of the standard buffer

47
Potentiometric pH Measurement with the Glass
Electrode
The Operational Definition of pH
•The operational definition of pH, endorsed by the National Institute of Standards and
Technology (NIST) and IUPAC, is based on the direct calibration of the meter with
carefully prescribed standard buffers followed by potentiometric determination of the
pH of unknown solutions.
•When electrodes are immersed in a standard buffer: ES  K
pH S 
0.0592

EU  K
•When electrodes are immersed in an unknown solution: pHU  
0.0592
( EU  ES )
•Therefore, the operational definition of pH is pHU  pH S 
0.0592

•The strength of the operational definition of pH provides a coherent scale for the
determination of acidity or alkalinity.
•The operational definition of pH does not yield the exact pH as defined by the
equation: pH   log  [ H  ]
U H

48
 Potentiometric titrations
• In a potentiometric titration, we measure the potential of a suitable
indicator electrode as a function of titrant volume.
• Potentiometric titrations are not dependent on measuring absolute
values of Ecell.
• Potentiometric titration results depend most heavily on having a titrant of
accurately known concentration.
• This characteristic makes the titration relatively
free from junction potential uncertainties.

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 Detecting The End Point
• A direct plot of potential as a function of reagent volume
• The inflection point in the steeply rising portion of the curve and
take it as the end point.

Titration Curve

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 Detecting The End Point

• Calculate the change in potential per unit

volume of titrant (DE/DV)
• If the titration curve is symmetrical, the point
of maximum slope coincides with the
equivalence point.

First-derivative curve

• Calculate the second derivative for the

data changes sign at the point of
inflection.
• This change is used as the analytical
signal in some automatic titrator.

Second-derivative curve

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 Neutralization Titrations
• Usually, the experimental curves are somewhat displaced from the theoretical
curves along the pH axis because concentrations rather than activities are used in
their derivation.
• Potentiometric neutralization titrations are quite useful for analyzing mixtures of
acids or polyprotic acids.

Determining Dissociation Constants

• An approximate numerical value for the dissociation constant of a weak acid or
base can be estimated from potentiometric titration curves.
• At half-titration point:

• It is important to note the use of concentrations instead of activities may cause

the value for Ka to differ from its published value by a factor of 2 or more.
• The more correct form of dissociation constant for a weak acid HA is:
• The activity coefficient HA doesn’t change
significantly as ionic strength increases
because HA is a neutral species.
• A- decreases as the electrolyte concentration
increases.
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Potentiometric determination of equilibrium constants
• Numerical values for solubility-product constants (Ksp), dissociation constant (Kd),
formation constant (Kf) are evaluated through the measurement of cell potentials.

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• Any electrode system in which H+ are participants can be used to evaluate
dissociation constants for acids and bases.

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