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Electroanalytical

Methods -I

UNIT 3 POTENTIOMETRY-II (pH METRY)


Structure
3.1

Introduction
Objectives

3.2
3.3
3.4
3.5
3.6
3.7
3.8
3.9
3.10

3.1

Concept of pH
Glass Membrane Electrodes
pH Meter
Measurement of pH
pH Titration
Modified Glass and Solid State Membrane Electrodes
Summary
Terminal Questions
Answers

INTRODUCTION

In the previous unit, you have seen that potentiometric methods mainly include two
major types of analysis. First being direct measurement of an electrode potential from
which the activity (or concentration) of an active ion may be derived. The other type
involves, measuring the changes in the electromotive force (emf) brought about by the
addition of a titrant to the sample.
The principle of potentiometry can be applied to measure the emf, in terms of pH unit
on pH scale by suitable modifying the common voltmeter to high input impedance mV
meter. The acid-base titrations, involving measurement of change in pH to detect the
end point, can be termed as pH metry instead of potentiometry.
Objectives of developing pH metry lies in recognising the importance of pH, the very
important test performed in studying chemical, biochemical, microbiological
processes involved in various unit operations and processes in small to large scale
industrial productions. In every phase of water and wastewater treatment processes,
i.e. in acid-base neutralization, water softening, precipitation, coagulation in the field
of both production and environmental protection technologies, all these processes are
carried out at specific range.

Objectives
After studying this unit, you should be able to:

draw and level a glass electrode,

write the Nernst equation for a glass electrode,

describe how the pH meter can be used to measure the pH, and

describe how the pH data can be used to determine the equivalence point in acid
base titrations, and

list the applications of ion-selective electrodes

3.2

CONCEPT OF pH

At a given temperature the intensity of the acidic or basic character of a solution is


indicated by pH or hydrogen ion activity. By definition it is the negative logarithm of
the hydrogen ion activity a + .
H

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pH = log a

Potentiometry-II
(pH Metry)

In dilute solution the hydrogen ion activity is approximately equal to the concentration
of hydrogen ion. Pure water is very slightly ionized and at equilibrium the ionic
product is
[H+][(OH] = Kw = 1.0 10-14 at 25C
or [H+] = [OH ] = 1.005 10-7
A logarithmic form is
log [H+] log [OH ] = log Kw
or pH + pOH = pKw
From the above equilibrium it is clear that the pH scale for an aqueous solution lies
between 0 and 14. The pH of most raw water sources lies within the range of 6.5-8.5,
slightly basic due to the presence of bicarbonates and carbonates of the alkali and
alkaline earth metals.
The pH is generally measured with glass electrode and a pH meter. The glass
membrane electrode or glass electrode is one of the most common examples of an ionselective indicator electrode. The overall cell, when the glass electrode is used with an
external reference electrode such as standard calomel electrode (SCE), can be
represented by:
Glass membrane H +

SCE

To compute the cell potential, it could be assumed that the SCE is more positive than
the glass electrode. Thus,

Ecell = ESCE + Ej (E oG 0.059 log[H+])


where Ej is liquid-junction potential and E oG is the standard electrode potential of the
glass electrode.
or Ecell = E* + 0.059 log [H+]

(3.1)

Ecell = E* 0.059 pH

(3.2)

In terms of pH,
Thus, cell potential is directly proportional to pH i.e. :

Ecell pH
*

where E includes the standard electrode potential of glass electrode, potential of


reference electrode and liquid-junction potentials between the reference electrode and
solution. Beside these three potentials there is another potential called the asymmetry
potential which is also contributing to this. Asymmetry potential is a small potential
which exists across the membrane, even when the inner reference solution and the test
solution are identical. The sources of asymmetric are not much clear. It may be due to
the degree of hydration of the inner and outer surface of the glass membrane or due to
its structural design or due to mechanical and chemical attack whilst in use. The
degree of hydration of outer surface will also change if the electrode is allowed to dry
out for some time. Because of this it is advised that the electrode should be stored
either in water or in damp cotton wool. It is not possible to determine the value of
asymmetry potential, therefore, it is necessary to calibrate glass membrane electrode
with suitable buffer solutions. As the value of the asymmetry potential can change
with electrode use, it is necessary to carry out calibration at least daily.

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Electroanalytical
Methods -I

SAQ 1
Why is it necessary to calibrate the glass electrode before use?
...
...
...

3.3

GLASS MEMBRANE ELECTRODES

The pH glass electrode although somewhat mechanically fragile, resists a variety of


sample media and with the exception of hydroxide is largely free from interferences.
Moreover, pH-sensitive glass electrodes form the basis of many successful sensors for
environmentally sensitive gases. Thus, glass membranes represent an important class
of solid-membrane ion selective electrodes (ISEs).
As illustrated in Fig. 3.1(a), these electrodes have thin glass membrane fused to the
end of a glass or plastic body. The main body of the electrode contains an internal
reference electrode typically Ag/AgCl and is filled with a solution that is usually the
The majority of pH
electrodes available
commercially are
combination electrodes
that have both glass H+
ion sensitive electrode
and additional reference
electrode conveniently
placed in one housing
(see figure below). For
some specific
applications separate pH
electrodes and reference
electrodes are still used they allow higher
precision needed
sometimes for research
purposes. In most cases
combination electrodes
are precise enough and
much more convenient to
use.

aqueous HCl of concentration around 1.0 mol dm 3 . The selectivity coefficient of


glass-membrane is such that excellent dissemination against common cationic species
is achieved.

(a)

(b)

Fig. 3.1: Glass electrode: (a) Typical glass electrode consisting of both an indicator glass
electrode and a silver/silver chloride reference; (b) illustration showing an ion exchange

Combination electrodes

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The pH electrode responds to hydrogen ions as a result of the thin ion-exchange sites
on the surface of a hydrated glass membrane. The electrode consists of a thin layer of
glass, typically about 50 m thick. Charge is transported across the membrane by
sodium or lithium ions within the glass. The membranes are primarily made from
Lithia (Lithium oxide) or sodium oxide, and SiO2, and some amount of Al2O3 and
B2 O3 or multi-component glasses whose sensitivity pattern depends on the
composition of the glass. The surface layer of the glass consist of silicate group
associated with sodium ion (- Si O Na + ) as shown in Fig. 3.1 (b). When this electrode
is dipped in water, the sodium ions exchanged with the protons in water.

- Si O Na + + H +

SiO H + +

Surface of
solution
Glass electrode
before hydration

Potentiometry-II
(pH Metry)

Na+

Glass surface
after hydration

If glass electrode is placed in a test solution its glass membrane will have an inner and
outer hydrated layers and potential difference is developed due to the difference in
hydrogen ion activities between test solution and outer hydrated surface of glass
electrode as well as inner solution and inner hydrated surface. This potential is called
boundary potential and it varies with the activity or pH of the solution. Overall
boundary potential is the potential difference between both the boundary potentials.
We can write chemical equation for both the boundary potentials
H + Gl (s )  H + (aq) + Gl

Outer surface
of glass

Outer solution

H + Gl (s )  H + (aq) + Gl

Inner surface
of glass

(3.3)

(3.4)

Inner solution

For the Eq. (3.3), the boundary potential is


E1 (a1 ah)

where a1 and ah are the activity of the hydrogen ions in the test solution and the outer
hydrated layer, respectively. Similar for Eq. (3.4), the boundary potential is
E2 (a2 ah)

where the activity of inner solution is a2.


Thus, overall boundary potential,
Eb = E1 E2 (a1 ah) (a2 ah)

If we assume that the activities of the hydrogen ions in the inner and outer hydrated
layer are the same, the above equation can be written as:
Eb

(a1 a2)

But the activity of the hydrogen ions in the inner solution is a constant and this
equation reduces to:
Eb a1
Eb can be expressed for can in Nernst form:
Eb = E1 E2 = 0.0591 log

a1
a2

Eb = K1 + 0.0591 log a1 = K1 0.0591 pH

(3.5)

where K1 is constant, it includes the constant factor related to hydrogen ion activity of
inside solution, a2, that is, 0.0591 log a2.
Thus, the boundary potential is a measurement of the hydrogen ion activity or the pH
of the external solution. For measuring pH with glass electrode the arrangement shown
in Fig. 3.2 are commonly employed. This arrangement has glass electrode with
Ag/AgCl internal reference electrode and external reference electrode such as

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Electroanalytical
Methods -I

saturated calomel electrode (SCE). For such arrangement complete cell may be
represented as:
Reference electrode H+
Glass membrane H+ Reference electrode
(internal)
(internal)
(extenal)
(SCE)

Glass electrode

Fig. 3.2: A typical electrode system for measuring pH

The cell potential is expressed as


Ecell = (E ind ) ESCE + Ej

(3.6)

where ESCE is the potential due to external reference electrode, Ej is liquid-junction


potential, and E ind is electrode potential of the glass electrode, which is actually a
combination of three components: (i) the boundary potential, Eb, (ii) the potential of
the internal Ag/AgCl reference electrode, and (iii) the asymmetry potential, Easy.
From Eq. (3.5), substitute the value of Eb.
Thus, Ecell = (Eb + EAg/AgCl + Easy) ESCE + Ej

(3.7)

Substitute the value of Eb in this equation


Ecell = (K1 + 0.0591 log a1 + EAg/AgCl + Easy) ESCE + Ej

or Ecell = E* + 0.0592 log a1 = E* 0.0591 pH

(3.8)

where E is a constant, it includes all the constants and near constant source of
potentials, i.e. potential of both reference electrodes, liquid-junction potential between
the external reference electrode and the solution, asymmetry potential and internal
boundary potential.
It is very difficult to determine the value of E* both experimentally as well as
theoretically. Therefore, calibration method is used to eliminate this factor. In this
method, first test solution is comprised of a standard buffer solution with the pH
precisely known. Thus, for the standard, we can write following expression:
(Ecell )s = E* 0.0592 (pH)s

(3.9)

This step is followed by measurement of cell potential for unknown solution. The
expression will be
(Ecell )u = E* 0.0592 (pH)u

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(3.10)

Potentiometry-II
(pH Metry)

To eliminate E* subtract Eq. (3.9) from Eq. (3.10), we find


(pH)u = (pH)s

( E cell ) u ( E cell ) s
0.0591

(3.11)

Eq. (3.11) has been adopted throughout the world as the operational definition of pH.
pH determination using glass electrode is most accurate and widely used method
despite a few disadvantages viz. the glass membrane being very fragile, it requires
great care while using. The ordinary potentiometer cannot be used for measuring the
potential of the glass electrode. Thus, the electronic potentiometers are required to be
used, needs frequent standardization and, cannot be employed in pure ethyl alcohol,
acetic acid and gelatin. The following features of glass electrode have made it more
versatile to be used be as indicator electrode for pH measurement.

It may be used in the presence of strong oxidizing and reducing solutions in


viscous media and in presence of proteins which interfere with operation of
other electrodes.

It can be used for solutions having pH values 2 to 10 with some special glass,
measurements can be extended to pH values greater than 10.

It is simple to operate and immune to poisoning.

The equilibrium is reached quickly

While measuring pH you should be little care full as there are few factors which limit
the accuracy of pH measurements. We are listing few of them below:
1.

The alkaline error: It is noticed that the ordinary glass electrode becomes
sensitive to alkali ions and gives low reading in high pH range above 9 or 10
pH units. The reason for the error is that whilst the glass membrane is selective
to hydrogen ion, it also responds to other ions. This becomes more significant
when the activity of the other ions is higher to activity of the hydrogen ion.
Fig. 3.3 shows the error produced by different cations at different
concentrations. You may have noticed that alkaline error is relatively more in
case of sodium ion. This is because of higher selective coefficient of sodium ion.
This due to sodium ion can be reduced by the use of Li2 O glass in place of Na2O
glass.

Fig. 3.3: Deviation in pH measurement using a glass electrode under alkaline


conditions

2.

The acid error: At low pH range less than 0.5, the values determined by the
glass electrode tend to be somewhat higher. This error is due to the activity of
water which we have ignored while writing Nernst equation for the indicator
electrode. We have assumed that activity of water may be taken to be unity as it
is in large excess in the solution and it behaves as a pure substance. However, in
highly acidic solution, the activity of the water becomes less than unity because
a good amount is used in hydrating the protons. Similar effects are also observed

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Electroanalytical
Methods -I

on addition of large amount of any dissolved salt and on addition of a miscible


non-aqueous solvent such as ethanol. The net result in each case is the measured
pH will be too high.
3.

Variation in junction-potential: In most of the cases the composition of the


standard buffer solution and test solution are different. In such situation, the
liquid junction potential will be different.

4.

Error in the pH of the standard buffer: There may be possibility that buffer
solution is not prepared with full care or its composition may change during
storage. All these factors will cause an error in subsequent pH measurements.

5.

Temperature: A change in temperature may affect on pH measurements,


because change in temperature affects the activities of the ions as well as the
liquid-junction potentials. Therefore, it is advised to calibrate the electrode at the
temperature of the test solution.

6.

Calibration procedures: Buffer solution cannot be prepared more accurately


than 0.01 pH units. Therefore, we cannot calibrate the electrode better than
this.

7.

Equipment related: These errors may due to the power fluctuations, parallax
errors in reading analogue scales, etc.

With this theoretical background now we will see how the pH is measured using pH
meter, but before that try following SAQs.

SAQ 2
How will you define boundary potential?
...
...
...
...........................................................................................................................................

SAQ 3
List some factors which may cause errors in pH measurements.
...
...
...
..........................................................................................................................................

3.4

pH METER

The instrumentation required to perform potentiometric measurements includes a


reference electrode, an indicator electrode and a high input-impedance mV (pH/pion)
meter as depicted in Fig 3.2.
Ordinary laboratory volt meters cannot be used for the measurement of the emf of a
glass electrode cells because of the high electrical resistance of glass electrode
(typically 10-200 megaohms), special high-impedance voltmeter circuits are required,
which draw 10-12 amperes or less from the circuit. The pH meter is a voltmeter but
with several critical addition functions. Not only does it measure the potential across
the pH-sensing and reference electrode system, but it also converts the potential

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difference measurement at a given temperature into pH terms, and it provides


mechanisms to correct for the non-ideal behaviour of the electrode system. The
operational amplifier not only serves as high-impedance voltmeter, but also provides
stability and automatic operation through the use of the feed-back loop. The
operational controls on a pH meter are best understood by reference to the operational
manual provided by manufacture of individual instrument. Modern electronic
techniques permit the production of simplified pH meter that measures pH with an
accuracy of + 0.1 pH unit. The microprocessor equipped pH meters include a
temperature probe to display temperature compensation, a memory for the pH values
of standard buffers, a waiting period to allow draft before taking pH readings and built
in diagnostics to alert for electronic malfunctions or defective electrodes. Along with
pH meter we also require a reference electrode and a glass membrane electrode which
acts as indicator electrode in pH measurement. Details of reference electrode were
discussed in earlier unit of this block and details of glass membrane electrode were
discussed in previous section.

Potentiometry-II
(pH Metry)

The two most popular types of reference electrode are


Reference Electrode:
the saturated calomel and silver/silver chloride systems. Both types of reference
electrodes exhibit many of ideal characteristics, those include maintaining fixed
potential over time and temperature, having long-term stability and returning to
the initial potential after being subject to small currents.
i)

The saturated calomel electrode (SCE) is composed of metallic Hg, solid


mercurous chloride (Hg2Cl2 ) and a saturated solution KCl a equilibrium.
Consequently, the potential of the SCE (+0.241/2 V versus the standard
hydrogen electrode) remains constant even if some of the liquid
evaporates over time. The SCE is more popular and with a constant
temperature bath, the error caused by fluctuating temperature can be
eliminated. The SCE can be used as a reference electrode in a sample that
does not exceed 80 C.

ii)

The Ag/AgCl electrode includes a silver wire, coated on one end with the
insoluble AgCl salt. When the electrode is immersed in a saturated KCl
solution, its potential at 25 C depends only on the Cl concentration
and is +0.192V versus the standard hydrogen electrode. The Ag/AgCl
electrode should not be used in the solutions that contains species that can
precipitate or complex with silver.
Reference electrode should be prepared and maintained so that the level of
the internal liquid is kept above sample solution to avoid infusion of
sample into reference electrode. This is a commonly used precautionary
measure to avoid any contamination of the sample by Cl , Ag + or Hg 2+
ions.

3.5

Indicating Electrode (glass electrode): As described in Section 3.3.

MEASUREMENT OF pH

pH measurements are part of routine tests done to check and comtroll many our day to
day activities like potable water quality, soil usability for different plants, water
quality in aquaristics, they are done to control industrial processes, in wine-making
and beer-making, to check milk quality, to check cosmetics - not to mention all labs
throughout the world where pH measurements are performed many times a day to
control reactions and analysis conditions.
pH can be measured in several ways, of which two are widely used. One - simple and
often enough precise - is a use of colorimetric indicator methods, i.e. use of pH strips

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Electroanalytical
Methods -I

(pH papers). Second, more costly and more demanding in terms of procedure that have
to be used, but giving much more precise results - is a potentiometric method with
usage of glass electrodes and pH meters. Colorimetric (spectroscopic) methods have
never gained much popularity, although they are occasionally used in places where
glass electrodes. The mail disadvatage of this procedure is that it can't be immersed in
the test solution.
Thus, the pH determination is usually done by potentiometric methods, which is the
most accurate methods and free of interferences.
Potentiometric Method of pH Measurement

The pH is determined by measurement of the emf of a cell comprising an indicator


electrode (an electrode responsive to hydrogen ions such as glass electrode) immersed
in the test solution and a reference electrode (usually a saturated calomel electrode,
SCE) contact between the test solution and the reference electrode is achieved by
means of liquid-junction, which form the part of a reference electrode. The emf of this
cell is measured with pH. The description of pH-meter has already been made in
Section 3.4, however procedure for stepwise calibration of pH meter and measurement
of pH of a test sample is given below:
Apparatus

a)

pH meter: consisting of potentiometer, a glass electrode, a reference electrode


and a temperature compensating device. A balanced circuit is completed
through potentiometer when the electrodes are immersed in the test solution.

b)

Reference electrode: consisting of a half-cell that provides a standard electrode


potential. General colomel (SCE) or silver/ silver-chloride electrodes are used as
a reference electrode.

c)

Glass membrane electrode: Several types of glass electrodes are available. Even
combination (glass and reference) electrodes are available for pH measurement
of different test solutions and at varying test conditions.

d)

Beakers: Preferably use polyethylene or TFE beakers.

e)

Stirrer: Use a magnetic TFE coated stirring bar.

Reagents
Calibrate the electrode system against standard buffer solutions of known pH:
Buffer tablets having pH 4.0, 7.0 and 9.2 are commercially available. Because buffer
solutions may deteriorate as a result of mold growth or contamination, prepare fresh as
needed. Alternatively buffer solutions can also be prepared as following:
pH 4 buffer solution : Dissolve 10.2 gm anhydrous potassium biphthalate (KHC8H4)
using boiled and cooled distilled water. Dilute to 1 dm3 .
pH 7 buffer solution: Dissolve 1.361 gm anhydrous potassium dihydrogen phosphate
(KH2 PO4), and 1.42 gm anhydrous disodium hydrogen phosphate, Na2HPO4 both of
which have been dried at 110C to 130C. Use distilled water which have been boiled
and cooled. Dilute to 1 dm3.
pH 9.2 buffer solution : Dissolve: 3.81 gm borax (Na2B4 O7 10H2O) in distilled water.
Dilute to 1 dm3.
Procedure

Numerous pH meters of various designs are marketed by several instrument


manufactures. General purpose pH meters are either line operated instruments that are

64

readable to 0.05 pH unit or battery operated instruments suitable for field job. These
days digital pH meters readable to 0.01 pH unit are more popular as compared to
scale-needle instruments.

Potentiometry-II
(pH Metry)

Measurement of pH of a solution with the instrument (analog meter) shown in Fig. 3.4
can be made following the procedure given below in a step-wise manner.
1.

Keep the selector switch on zero position and adjust the zero position by a
screwdriver if the pointer does not indicate zero.

2.

Before using pH meter, remove electrodes from storage solutions


(recommended by manufacturer) and rinse with distilled water. Dry electrodes
by gently blotting with a soft tissue paper.

3.

Mount the electrodes in the clip on the stand.

4.

Connect the power cable to a 220V AC supply. Switch on the instrument and
wait for a few minutes till the instrument warms up.

5.

Adjust the temperature/solution temperature value.

6.

Take the standard buffer solution of desired range (e.g. buffer of pH 4 for acidic
solutions) in a beaker. The electrode assembly is immersed in the pH reference
buffer and the solution is agitated gently by swirling the solution in the region of
the glass electrode surface so as to bring it into pH equilibrium. It should be
ascertained that the glass electrode membrane is completely immersed in the
solution. The electrodes should not touch each other or the side or the bottom of
the beaker.
II

III

VII

IV

VI

Fig. 3.4: A direct reading pH meter (front view) legend:


I. On/off switch
II. Set zero III. Selector
IV. Electrode support
V. Temperature compensation VI. Set buffer VII. Meter

7.

Put the selector switch to suitable pH range (0-7 for acidic or 7-14 for basic
solutions) and adjust set buffer knob in manner that the pointer reads the pH of
the standard buffer solution (placed in the beaker).

8.

Put the selector switch back to zero position. Remove the electrodes from the
buffer solution, wash the electrodes with distilled water and wipe them gently
with tissue paper.

9.

Immerse the electrodes in a second buffer below pH 10, approximately 3 pH


units different from the first one; the reading should be within 0.1 units for the
pH of the second buffer. (If the meter response shows a difference greater than
0.1 pH unit from expected value looks for trouble with the electrodes or pH
meter.

10.

Transfer the standard buffers back to the storage bottle and wash the beaker well
with distilled water.

11.

Take the sample solution in the beaker. Introduce the electrodes in the solution
and swirl it gently.

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Electroanalytical
Methods -I

12.

Set the selector switch in the suitable range position and read the pH on the
scale.

13.

Put the selector switch back to zero position. Remove the electrodes from the
solution, wash them with distilled water and keep the electrodes in distilled
water, when not in use.

Precautions

i)

Never touch the membrane of the glass electrode with anything else except soft
tissue paper since it is fragile and is easily ruined if scratched or bumped.

ii)

The electrode(s) must not be removed from the solution unless the selector
switch is at zero.

iii)

Never dip the glass electrode in a solution with a dehydrating action.

iv)

For sample analysis establish equilibrium between electrodes and sample by


stirring sample to ensure homogeneity and measure pH.

v)

If used for measuring pH of albuminous substances, the glass electrode must be


cleaned with suitable solvents and then the electrode is placed in distilled water
for a few hours before it is used to measure the pH of the other solution.

vi)

For basic solutions with pH more than 11, glass electrodes of special
composition are required to avoid interference due to sodium ion.

vii)

The glass electrode may be covered with a sleeve to save it from jerks.

viii) The standard buffer of pH value as close as possible to the sample pH value
must be taken for the calibration of the system. Commercially available standard
buffers of pH values 4, 7 and 9.2 are commonly used.

3.6

pH TITRATION

Similar to potentiometric titrations, in contrast to direct pH measurements, pH


titrations generally offer increased accuracy and precision. Accuracy is increased
because, measured pH are used to detect rapid changes in activity that occur at
equivalence point of the titration. Furthermore, it is the change in pH versus titre
volume rather than absolute value of pH that is of interest. Thus, the errors due to
liquid-junction potentials and activity coefficients are minimized. pH titrations may be
applied to a variety of systems including those involving weak acids and weak bases.
In such titration, it is difficult to get end point using indicator method. A typical acidbase titration using pH metry is briefed as follows.
It is known that the neutralization of acids and bases is always accompanied by the
changes in the concentration of H+ and OH ions. It is evident that hydrogen electrode
may be employed in these titrations. The reference electrode used in these titrations is
1 M-calomel electrode. The apparatus used for acid-base titrations is as shown in
Fig. 3.5.
The critical problem in titration is the recognition of point at which the quantities of
reacting species are presented in equivalent amounts, i.e. the equivalence point. The
titration curve can be followed point by point plotting as the ordinate successive
values of the pH versus the corresponding volume of titrant added as the abscissa.
Addition of the titrant should be the smallest accurately measurable increments that
provide an adequate density of points, particularly in the vicinity of equivalence point.

66

Over most of the titration range the pH varies gradually, but near the end point
the pH changes very abruptly. The resulting titration curve resembles
Fig. 3.6 (a).

Potentiometry-II
(pH Metry)

Fig. 3.5: Typical Instrumental set up for pH titration

By inspection, the end point can be located from the inflection point of the
titration curve.

This is the end point that corresponds to maximum rate of change of pH per unit
volume of titrant added (0.05 cm3 or 0.1 cm3).

The distinction of the end point increases as the reaction involved becomes more
nearly quantitative.

Once the pH has been established for a given titration, it can be used to indicate
subsequent end points for the same chemical reaction.

The equivalence point can be more precisely located from the 1st and 2nd
derivative curves as illustrated in Fig. 3.6 (b) and 3.6 (c). Solutions more dilute
than 10-3 M generally do not give satisfactory end points. This is limitation of
pH metry and potentiometric titrations.

(a)

(b)

(c)

Fig. 3.6: pH titration curves; (a) Normal curve; (b) First derivative curve; and (c)
second derivative curve
`

Titration of a Weak Acid with a Strong Base

So far titration curve shown in Fig. 3.6 (a) describe the progress of the titration of
strong acid and strong base. We now consider the titration of 25 cm3 of 0.05 M
CH3COOH solution with 0.05 M NaOH solution to explain how the pH of the titration
is changed at different stages of the titration. For this purpose we will be using many
expressions used in theory of neutralization titrations which you may have studied in
first course on Basics of Analytical Chemistry or in your undergraduate physical
chemistry courses.

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Electroanalytical
Methods -I

Starting point of the titration curve: The starting point of the titration curve of
0.05 M CH3COOH solution is considerably lower than that of 0.05 M HCl solution.
This is because acetic acid is dissociated almost by 100 times less than hydrochloric
acid. (the degree of electrolytic dissociation of 0.05 M CH3COOH solution 1 per
cent; for 0.05 M HCl solution, 90 per cent). Hence [H+] in 0.05 M CH3 COOH
solution is also 100 times less than in 0.05 M HCI solution. And pH will be 3, and not
unity.

A more precise pH value of the starting point of the titration curve is found by the
following way. Write the expression for acid dissociation constant for acetic acid:
Hydrolysis of salt of a
weak acid and a strong
base may be represented
as
A + H2OHA + OH
Hydrolysis constant is
given by
[HA ] [OH ]
Kh =
[A ]
[ HA ] [OH ] [H + ]
=
[ A ] [H + ]
=

Kw

But at equilibrium, [HA]


= [OH ], therefore,

[OH ] 2 [OH ]
=

c salt
[A ]
2
Kw
=
.(ii)
[ H + ] 2 c salt
Combining Eqs. (i) and
(ii) gives
Kh =

2
Kw
[H + ]2 c

=
salt

Kw

At equilibrium, [H + ] = [ A ] . As the degree of ionization of acetic acid is small,

therefore at equilibrium, the concentration of unionized acid is approximately


equal to total concentration of acid(cacid), i.e. cacid = [HA] + [A ] [ HA] .
Therefore,
6

Ka =

[H + ]2 [H + ]2
=
[ HA]
cacid

[H+] =

K a c acid

For acetic acid K a = 1.75 10 5


[H + ] = 1.75 10 5 0.05 M

= 9.35 10 4 M

[ ]

pH = log H + = log (9.35 10 4 ) = 3.03

Equivalence Point: We can also determine the pH at the equivalence point. At the
moment when titration is completed, equivalent quantities of the CH3COOH and
NaOH solution will be present. Hence, the titrating flask will have a salt solution
formed by a weak acid and a strong base. For the solution of such salt (see marginal
remark):
[H+] =

Ka

i.e.
[H + ] =

[ H + ] [A ]
[ HA]

where cacid is the concentration of acidic acid.

...(i)

Ka

Ka =

Kw Ka
csalt

The salt concentration in comparison with 0.05 M will halved;


Ka K

/c

salt

csalt = 0.025 M

[H ] =
+

1.0 10 14 1.75 10 5
0.025

= 2.65 10 9

pH = log [H+] = log 2.65 10-9


= 8.58

Intermediate Points: After determining the starting and end points of the titration, we
will now consider pH calculations for the intermediate points. These points of the
curve correspond to the simultaneous presence in the solution of an un-titrated weak
acid and a salt which is formed as a result of its partial neutralization. Hence, for
calculation, we may use the formulas for finding the values of [H+] and pH in

68

Potentiometry-II
(pH Metry)

solutions of a weak acid in the presence of its salt of strong base (see marginal
remark):
[H+] =

K a c acid
c salt

Let us calculate the first intermediate point which corresponds to 5 cm3 of 0.05 M
NaOH solution poured in. We first determine the quantity (in cm3 of 0.05 M solution)
of the residual acid. It will be 25 5 = 20 cm3, since 5 cm3 of 0.05 M NaOH solution
have titrated CH3COOH. Consequently, cacid in the titration flask is not 0.05M, but
cacid =

0.05 20
= 0.033 M
30

Let us now determine the concentration of the salt formed at this moment of titration.
As we have seen earlier, 5 cm3 of 0.05 M CH3COONa solution were formed, but this
quantity of the salt is also in the total volume of 30 cm3 . Therefore,
csalt =

0.05 5
= 0.008 M
30

A weak acid in the


presence of its salt of
strong base be be
represented as
H+ + A

HA + H2O

OH +HA
A + H2O
Since for weak acid,

Ka =

[H + ] [A ]
[ HA ]
[ H + ] [c

salt ]
[c acid ]

For acetic acid Ka is 1.75 10-5


Substituting all these data in the formula for finding the pH of the solution, we obtain
the following for the first intermediate point:
[H + ] =

1.75 10 -5 0.033
M
0.008

pH = - log [H + ] = - log 7.22 10-5


= 4.14
Let us calculate the next point of the titration curve for the moment at which 12.5 cm3
of NaOH solution will be poured in:
cacid =

0.05 (25 12.5)


= 0.017 M
25 + 12.5

csalt =

0.05 12.5
1.75 10 -5 0.017
M
= 0.017 M; [H + ] =
37.5
0.017

pH = log [H+] = log 1.75 10-5


= 4.76
That is pH = pKa
We now calculate the pH of the third intermediate point for V = 15 cm3
cacid =

0.05 ( 25 15)
= 0.014 M
( 25 + 15)

csalt =

0.05 15
0.021 M
35

[H + ] =

1.75 10 -5 0.014
0.021

pH = log [H+] = log 11.67 106 = 5.9

After equivalence point (on addition of 25.01 NaOH): In this situation both the
excess NaOH and acetate are source of hydroxide ion. We may consider that the
contribution from the acetate ion will be small, because the excess of strong base
repress the reaction of acetate with water. We have then

69

Electroanalytical
Methods -I

[OH ] cNaOH =

0.05 (25.01 25 )
= 9.99 10 6
25.01 + 25

pH = 14.00 [ log ( 9.99 10 6 ) = 8.99


On further titration, the pH of the solution will be determined only by excess 0.05 M
NaOH solution.
Thus, the curve of titration of a weak acid with a strong alkali has the following signs:
1.

The starting point of titration is in a medium which is less acidic than when a
strong acid is being titrated,

2.

the equivalence point is in a weakly alkaline medium,

3.

the middle part of the titration curve is more slanting than that of the titration
curve of a strong acid;

4.

the titration jump is not great, ranging from pH 8 to pH 10, and accordingly, the
vertical part of the curve is considerably smaller than that when a strong acid is
being titrated.

Buffering action of the CH3COO ion: One will see without any difficulty that this
curve is much smoother than the curve of titration of a strong acid with a strong alkali,
and it does not have a sharp inflection.
When HCl solution was titrated with alkali, 22 cm3 of the titrant had to be added in
order to change pH by unit, while in this case, approximately 5 cm3 were enough
(Fig. 3.7).
This difference is due to the fact that when titrating a strong acid with a strong alkali,
the concentration of H+ ions decrease only as a result of their combination with OH
ions.

(a)

(b)

Fig. 3.7: pH titration curves: (a) For 0.50 HCl with 0.50 NaOH; (b) 0.50 Acetic acid with
0.50 NaOH.

When titrating a weak acid with a strong alkali, H+ ions combine not only with OH
ions, but also with anions (in this case, with CH3COO ions), as a result of which [H+]
decreases much more rapidly at the beginning of titration, and the titration curve bends
downwards much more sharply.
Such an effect of the CH3COO ion, which smoothens out the titration curve, is
known as the buffering action. The value of [H+] in the solution of a weak acid in the
presence of its salt is determined by the following formula.

70

[H ] =

K a c acid

Potentiometry-II
(pH Metry)

c salt

It follows that if the acid concentration in the solution is equal to the salt concentration
then

K a c acid
c salt

= [H + ] = K acid and pH = pK acid

This means that if cacid and csalt have close values in such a mixture, the pH of the
solution will remain constant even when considerable quantities of acid and alkali are
added. Precisely such a relationship between cacid and csalt is observed in the case of
titration of a weak acid with a strong base at the second intermediate point.

SAQ 4
Calculate the pH during the titration of 50.00 cm3 of 0.05 M HCl with 0.10 M NaOH
at different stages of titration (i) initial point, (ii) after addition of 10 cm3 of NaOH,
(iii) after addition 25 cm3 of NaOH and (iv) after addition of 25.50 cm3 of NaOH.
...
...
.........................................................................................................................................

3.7

MODIFIED GLASS AND SOLID STATE MEMBRANE


ELECTRODES

Glass electrode can be made selective for ions other than hydrogen ion by some
modifications. This modification is possible by changing the composition of the glass
and the internal solution of glass electrode. By adding aluminum oxide to sodium
oxide and silicon oxide glass and changing internal filling solution from hydrochloric
acid to sodium chloride, such electrode becomes selective to Na+ ions. There is another
types of glass electrode with composition of Li2O, Al2O3 and SiO2 is also used as
sodium electrode. Sodium electrode has many applications in measurement of sodium
in water analysis and in biological fluid analysis. For measuring potassium and
ammonium ions, modified glass containing 27 % of Na2O, 4 % Al2O3 and 69 % SiO2.
Potassium/ammonium electrode is now replaced by other ion selective electrodes
using more selective membrane.
Solid State Membrane Electrodes

In solid state membrane electrode we use a doped single crystal membrane in place of
glass membrane. These changes enable us to design electrodes which have a response
to a number of different anions and cations such as F , Cl , and Ag + . A typical
design is shown in Fig. 3.8.
In this electrode system similar to glass electrode internal solution and electrode form
the internal reference. For example, fluoride ion selective electrode consists of LaF3
membrane and an internal Ag, AgCl reference electrode immersed in an internal
solution of KF, KCl. LaF3 membrane is highly selective and responds to fluoride ion
only. If this electrode used with reference saturated calomel electrode, the complete
cell may be written as:
Hg,Hg2Cl2 (s)KCl F (unknown)LaF3(s) NaF(0.1 M) NaCl (0.1M)AgCl (s),
Ag

71

Electroanalytical
Methods -I

Fig. 3.8: A typical solid state electrode

The potential of cell is given by

Ecell = ESCE ( 0.0591log a


Ecell = E * 0.0591log a

+ E AgCl + E asy + E j )

where E * includes EAgCl ,ESCE, Easy and Ej constant potential representing internal
reference electrode, external reference electrode, asymmetry potential, and liquid
junction, respectively. Calibration with the known fluoride activity eliminates the need
of knowing these constants. Fluoride electrode has many applications such as fluoride
determination in bone, air and stack gas samples, chromium plating baths, minerals,
water, and toothpastes.
Similar to fluoride ion selective electrode many other solid state membrane electrodes
can be developed. In Table 3.1, we are listing few such ion selective electrodes.
Table 3.1: Some example of solid state membrane ion selective electrodes
Selective ion

Membrane

LaF 3

Lower
limit
of
measurement/mol
dm-3
10 7

Cl

AgCl

10 5

AgBr

10

AgI

10

S2

Ag2S

10 7

SCN

AgSCN

10 6

Ag+

Ag2S

10 8

Hg2+

HgS/Ag2S

10 8

Cu2+

CuS/Ag2S

10 9

Cd2+

CdS/Ag2S

10 7

Pb2+

PbS/Ag2S

10

Bi3+

Bi2S3/Ag2S

10 11

Br
I

72

Based on the principle of ion selective electrodes many gas sensing electrodes have
been developed in past few years. They are available primarily for the measurement of
ammonia, carbon dioxide, and nitrogen oxide. This type of electrode has a gas
permeable membrane and an internal buffer solution. The pH of the buffer solution
changes as the gas reacts with it. The change is detected by a combination pH sensor
within the housing. This type of electrode does not require an external reference
electrode. In Table 3.2, we have summarized some commercial gas sensing electrodes.

Potentiometry-II
(pH Metry)

Table 3.2: Several typical gas sensing electrodes


Test ion

Internal
electrolyte
NH4Cl

Internal ion
selective
electrode (ISE)
pH

NH3

Membrane

ptfe (polytetrafluoroethylene)

CO2

NaHCO3

pH

ptfe

NOx

NaNO2

pH

ptfe

SO2

K2S2O5

pH

silicone rubber

H2S

Citrate buffer

S2-

silicone rubber

Applications Ion Selective Electrodes

Ion selective electrodes along with pH-sensitive glass electrode are widely used in
clinical, biological, water, air, oceanographic, and pharmaceutical research and routine
analytical determinations. So far there are reliable commercially available electrodes
for detecting H+, F, Cl, Br, I, Cd2+, Cu2+, CN, BF 4 , Pb2+, NO 3 , ClO 4 , Ag+, S2,
Na+, K+, and SCN, for NH3, H2S, SO2, CO2, nitrogen oxides gases, and for several
different enzymes. Glass membrane electrode is the most commonly used ion selective
electrode. pH measurements have many applications some of which are summarized
below:

pH metric or electrometric methods help in detecting the end point of acid-base


titration more accurately and precisely as compared to indicator methods.

pH metry is an important analytical tool in studying the acid-base equilibria


which is controlled by the carbon dioxide-bicarbonate-carbonate equilibrium
system in most natural waters.

The estimation of alkalinity and acidity based on pH metry serves a useful


information of buffering capacity of water.

In water and wastewater treatment, it gives an estimate of available of alkalinity


to react with the coagulant viz alum, Ferrous sulphate etc. or otherwise to be
supplemented with lime.

Industrial process control especially in batch or flow-through configurations;


through online pH monitoring and chemical dosing system.

In neutralization of wastewaters, to evaluate the doses of acid or alkali to be


added.

Development of biosensors based pH sensitive immobilized enzymes and other


academic studies.

Further the flexibility in available configurations allows the ions mentioned above to
be monitored in a single sample solution (batch mode) or continuously in a flow
through apparatus (flow-injection analysis).

73

Electroanalytical
Methods -I

3.8

SUMMARY

One of the most common and earliest applications of potentiometry is pH


determination, and titration for the determination of electro active species. Through
development of electrodes that selectively determine target ions, potentiometry in
general is replacing many older, more expensive and time consuming techniques for
analytically monitoring and measuring ion activity. Recent developments in the ion
selective electrodes (ISE) branch of potentiometry have made the monitoring of
inorganic, organic, gaseous and biologically important ions possible. The flexibility in
available configurations allows these ions to be monitored in a single sample solution
(batch mode) or continuously in a flow through apparatus (flow-injection analysis).

3.9

TERMINAL QUESTIONS

1.

Discuss the source of pH dependence in a glass membrane electrode.

2.

What is the source of the asymmetry potential in a glass membrane electrode?

3.

What are the advantages of a pH metric titration over a direct pH metry?

4.

Drive an expression for the operational definition of pH.

5.

What is the source of the potential of an ion selective electrode used to


determine the concentration of fluoride ion?

6.

Calculate the pH during the titration of 50.00 cm3 M NaOH with 0.10 M HCl
after the addition of the following volume of acid : (i) 24.50 cm3, (ii) 25.00 cm3
and (iii) 25.50 cm3.

7.

Calculate the pH during titration of 50.00 cm3 M NaCN with 0.10 M HCl after
the addition of the following volume of acid : (i) 0.00 cm3, (ii) 10 cm3, (iii)
25.00 cm3 and (iv) 26 cm3. (Hint: Kw = KaKb and acid dissociation constant for
HCN = 6.2 10 10 )

3.10 ANSWERS
Self Assessment Questions

74

1.

It is not possible to determine the values of asymmetry potential as well as


liquid- junction potential in glass/calomel electrode, therefore, it is necessary to
calibrate glass membrane electrode with suitable buffer solutions before use.

2.

When glass electrode is placed in a test solution its glass membrane will have an
inner and outer hydrated layer and potential difference is developed due to the
difference in hydrogen ion activities between test solution and outer hydrated
surface of glass electrode as well as inner solution as inner hydrated surface.
This potential is called boundary potential and it varies with the activity or pH of
the solution. Overall boundary potential is the potential difference between both
the boundary potentials.

3.

i)

Alkaline error

ii)

Acid error

iii)

Variation in junction potential

iv)

Error in the pH of the standard buffer

v)

Temperature

4.

vi)

Calibration procedures

vii)

Equipment related

Potentiometry-II
(pH Metry)

Initial Point
Before any base is added, the solution is 0.05 M in H+, and
pH= log[H+] = log 0.0500 = 1.30

After Addition of 10.00 M of acid: The hydrogen ion concentration is decreased


as a result of the reaction with the base and dilution. So the analytical
concentration of HCl is
cacid =

No. mmol HCl remaining after addition of NaOH


Total volume solution

Original no. mmol HCl No. mmol NaOH added


Total volume solution
(50.00 cm 3 0.05 M ) (10.00 cm 3 0.10 M )
50.00 cm 3 + 10.00 cm 3
.

= 2.500 10 2 M
[H + ] = 2.500 10 2 M
and pH = log [ H + ] = log (2.500 10 2 ) = 1.60

After addition of 25.00 M of acid: The Equivalence Point


At the equivalence point, neither HCl nor NaOH is in excess and so the
concentrations of hydrogen and hydroxide ions must be equal. Substance
equality into the ion-product constant for water yields

[H + ] =

K w = 1.00 10 14 = 1.00 10 7 M

pH = log (1.00 10 7 ) = 7.00

After Addition of 25.10 M of acid: The solution now contains an excess of


NaOH, and we can write
c base =
=

No.mmol NaOH added Original no mmol HCl


Total volume solution

25.10 0.10 50.00 0.05


= 1.33 10 4 M
75.10

and the equilibrium concentration of hydroxide ion is

[OH ] = c base = 1.33 10 4 M


pOH = log (1.33 10 4 ) = 3.88
and pH = 14.00 3.88 = 10.12

Terminal Questions
1.

When glass electrode is placed in a test solution its glass membrane will have an
inner and outer hydrated layers and potential difference is developed due to the
difference in hydrogen ion activities between test solution and outer hydrated
surface of glass electrode as well as inner solution and inner hydrated surface.

75

Electroanalytical
Methods -I

This potential is called boundary potential and it varies with the activity or pH
of the solution. Overall boundary potential is the potential difference between
both the boundary potentials. Concentration of inner solution is kept constant,
thus the boundary potential is a measurement of the hydrogen ion activity or the
pH of the external solution.
2.

The asymmetry potential in a membrane arises from difference in the structure


of the inner and outer surfaces. These difference may be due to the manufacture
reason or due to its use.

3.

pH titrations generally offer increased accuracy and precision. Accuracy is


increased because measured pH are used to detect rapid changes in activity that
occur at equivalence point of the titration. Furthermore, it is the change in pH
versus titre volume rather than absolute value of pH that is of interest. Thus, the
errors due to liquid-junction potentials and activity coefficients are minimized.

4.

Cell potential for the standard buffer can be expressed as


(Ecell )s = E* 0.0592 (pH)s

(i)

Cell potential for unknown solution will be expressed as


(Ecell )u = E* 0.0592 (pH)u

(ii)

To eliminate E* subtract Eq. (i) from Eq. (ii), we find


(pH)u = (pH)s

( E cell ) u ( E cell ) s
0.0591

(iii)

Eq. (iii) is the operational definition of pH.


5.

When ion selective electrode is dipped in the solution containing fluoride ions,
the equilibrium will be established between both the fluoride ions in test
solution and LaF3 crystal and fluoride ions in inner solution and LaF3. The
activity of the F at the inner surface is likely to be different to that at the outer
surface. This results in a development of the diffusion potential between two
surfaces similar to liquid junction potential. As the activity of internal solution is
constant value, the diffusion potential is, thus, dependent on the activity of F in
the test solution.

6.

i)

At 24.50 cm3 added, [H+] is very small and cannot be computed from
stoichiometric considerations but can be obtained from [OH ]
[OH ] = c base =

Original no. mmol NaoH No. mmol HCl added


Total volume of solution

50.00 0.05 24.50 0.10


= 6.71 10 4 M
50.00 + 24.50

[H + ] = K w / (6.71 10 4 ) = 1.00 10 14 /(6.71 10 4 )


= 1.49 10 11 M
pH = log(1.49 10 11 ) = 10.83

ii)

76

This is the equivalence point where [H+]= [OH-]

[H ] =

Kw =

1.00 10

14

= 1.00 10

Potentiometry-II
(pH Metry)

pH = log (1.00 10 7 ) = 7.00

iii)

At 25.50 cm3 added,


[H + ] = c HCl =

( 25.50 0.10 50.00 0.05)


75.50

= 6.62 10 4 M

= log (6.62 10 4 ) = 3.18

pH

7.

i)

The pH of a solution of NaCN can be calculated as


CN + H 2O  HCN + OH

Kb =

[OH ][HCN ]
[CN ]

K w 1.00 10 14
=
= 1.61 10 5
10
Ka
6.2 10

Sinceanequ ivalentamo untof [OH ] and [ HCN] areformed


[OH ] = [ HCN]
[CN ] = c NaCN [OH ] c NaCN = 0.05M

Substitution into the above dissociation-constant expression gives, after


rearrangement,
[OH ] = K b cNaCN =

1.61 105 0.05 = 8.97 10 4

pH = 14.00 ( log 8.97 10 4 ) = 10.95

ii)

10.00 cm3 of Reagent


Addition of acid produces a buffer with a composition given by

50.00 0.05 10.00 0.100 1.50


=
M
60.00
60.00
10.00 0.10 1.000
=
=
M
60.00
60.00

c NaCN =
c HCN

These values are then substituted into the expression for the acid
dissociation constant of HCN to give [H+] directly:
[H + ] =

[H + ] =

K a c acid
csalt

6.2 1010 (1.000 / 60.00)


= 4.13 1010
1.50 / 60.00
pH = log (4.13 1010 ) = 9.38

iii)

25.00 cm3 of Reagent


This volume corresponds to the equivalence point, where the principal
solution species is the weak acid HCN. Thus,

77

Electroanalytical
Methods -I

c HCN =

25.00 0.10
= 0.033M
75.00

Applying following Equation gives


[H + ] = K a c HCN = 6.2 10 10 0.033 = 4.45 10 6 M
pH = log (4.45 10 6 ) = 5.34

iv)

26.00 cm3 of Reagent


The excess of strong acid now present represses the dissociation of the
HCN to the point where its contribution to the pH is negligible. Thus,
[H + ] = c HCl =

26.00 0.10 50.00 0.05


= 1.32 10 3 M
76.00
pH = log(1.32 10 3 ) = 2.88

78

Potentiometry-II
(pH Metry)

Appendix I
Standard Electrode Potentials*
Reaction

E0 at 25 C,V

MnO 4 + 8 H+ + 2e  Mn2+ + 4H2O

+ 1.51

Cl2(g)+ 2e 2Cl

+ 1.359

Cr2 O2 + 14 H+ + 6e  2Cr3+

+ 1.33

O2 (g)+4H+ + 4e  2H2O

+ 1.229

Br2(aq) + 2e  2Br

+ 1.087

Br2(l) +2e  2Br

+ 1.065

Ag+ + e  Ag (s)

+ 0.799

Fe3+ + e  Fe2+

+ 0.771

I-3 + 2e  3I

+ 0.536

Cu2+ + 2e  Cu (s)

+ 0.337

UO22+ + 4H++2e U4+ + 2H2O

+ 0.334

Hg2Cl2 (s) + 2e  2Hg (l) + 2Cl

+ 0.268

AgCl(s) + e  Ag(s) + Cl

+ 0.222

Ag(S2O3)3-2 + e  Ag (s) + 2S2O 32

+ 0.017

2H+ + 2e  H2(g)

0.000

AgI(s) + e  Ag(s) + I

0.151

PbSO4 + 2e  Pb(s) + SO 24

0.350

Cd2+ + 2e  Cd (s)

0.403

Zn2+ + 2e  Zn(s)

0.763

Ce4+ + e  Ce3+

1.70 V

Mg 2 + + 2e  Mg (s)

2.363

79