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POTENTIOMETRY

Kimia Analitik
Universitas Pertamina
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Electrochemistry Analysis
• Electrochemical analysis: an analysis using electrochemical
methods in determining the concentration of the analyte.
• There are various kinds of electrochemical analysis:

Method Definition

An analysis method based on measuring the potential of a cell in a

Potentiometry
condition in which the electric current does not flow.

Electrogravimetry Gravimetry analysis method which is done through electrolysis process.

An analysis method based on measuring the amount of electrical charge

Coulometry
used in the electrolysis process.

An analytical method based on the measurement of the current strength at

Voltametry
the cell potential being altered.

An analytical method based on measuring the current strength at a fixed

Amperometry
cell potential.
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The use of electrodes to measure

Potentiometry voltages that provide chemical
information
• Potentiometry: an analysis method based on measuring the cell
potential in a condition in which the electric current does not flow.
• The arrangement of the instrument is generally the same as
ordinary voltaic cells:
• The system consists of 2 pieces of
electrode: the indicator electrode
and the reference electrode that
functions as the cathode and
anode.
• Each of these electrodes is
immersed in a sample solution
and a comparative solution.
• Both solutions are connected with
salt bridges.
• Both electrodes are connected to
potentiometer.
• Application of Potentiometry
1.pH meter
2.Fluoride Electrode
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Electrode types
• Reference electrode
- self-contained
- has constant potential
• Indicator electrode
- immerse in analyte solution
- potential changes in order to measure things
• Both connected by salt bridge
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Reference Electrodes
• Comparative electrode: electrode that serves to produce reproducible
potential, known value, and fixed, so that the other electrode potential
(indicator electrode) can be measured.
• Standard Hydrogen Electrodes (SHE) are not practically used as comparative
electrodes in potentiometric analysis.

• There are two comparative electrodes typically used for potentiometry:

1. Silver Chloride Electrode

AgCl (s) + e- ⇌ Ag (s) + Cl- (aq) E0 = 0.222 V
2. Calomel Electrode (Mercury/Mercury Chloride):
Hg2Cl2 (s) + 2e- ⇌ 2 Hg (l) + 2 Cl- (aq) E0 = 0.268 V

• In both these electrodes, the insoluble chloride salt envelopes the free element
(Ag / Hg), and both are dipped in KCl (aq) which is known to be concentrated.

• Double junction electrode → analyte and electrode do not have direct contact
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Reference Electrodes
Silver-silver chloride electrode Saturated calomel electrode (S.C.E.)

Ag(s) | AgCl (sat’d), KCl (xM) | | Hg(l) | Hg2Cl2 (sat’d), KCl (sat’d) | |

AgCl(s) + e ⇌ Ag(s) + Cl– Eo = +0.222V electrode reaction in calomel half-cell

E = Eo – (0.05916/1) log [Cl–] Hg2Cl2 (s) + 2e ⇌ 2Hg(l) + 2Cl– Eo = +0.268V

E (saturated KCl) = + 0.199V (25oC) E = Eo – (0.05916/2) log[Cl–]2

= 0.244 V

c c
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Reference Electrodes
Reference Electrode Indicator Electrode

A galvanic cell to measure [Fe2+]/[Fe3+] in the

right half-cell.
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Indicator Electrodes
• Electrode Indicator: electrode that is in direct contact with the sample
solution and measures the potential associated with the analyte
concentration in the sample solution.
• There are three kinds of indicator electrodes: metallic, membrane, and
ion-sensitive field effect transistors.
Metallic Indicator Electrodes, classify as
1. Electrodes of the first kind
2. Electrodes of the second kind
3. Inert redox electrodes.
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SEE YOU NEXT

LECTURE
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Indicator Electrodes
• 1. Inert redox electrodes.made of inert metal such as: Pt, Pd, Au.
Example: Pt metal used as cathode to reduce Fe3+ → Fe2+
½ Reduction Reaction :: Fe3+ + e- ⇌ Fe2+
Nernst Equation:

The electrode is then connected to a comparative electrode. Measured cell

potential depends solely on [Fe3+] and [Fe2+] present in solution → can be used to
analyze Fe3+ concentration in sample solution.
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Indicator Electrodes
2. electrodes of the first kind, consisting of metals dipped in a
solution containing the metal cations.
Example : Ag wire which immersed in AgNO3 solution
½ reduction reaction: Ag+ + e- ⇌ Ag (s)
Nerst Equation:

The electrode is then connected to a comparative electrode.

The measured cell potential solely dependent on [Ag+] present in the sample
solution → can be used to analyze [Ag+] in the sample solution.
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Indicator Electrodes
3. electrodes of the second kind, consisting of metal covered by the
metal salt (which is difficult to dissolve) and immersed in a solution
containing anions of the salt.
Example : Ag wire which is covered in AgCl (s) and dipped in solution Cl-.
½ Reduction Reaction: Ag+ + e- ⇌ Ag (s)
Solubility Reaction: AgCl (s) ⇌ Ag+ + Cl-
Net Reaction: AgCl (s) + e-  Ag (s) + Cl-
Nernst Equation:

The electrode is then connected to a comparative electrode.

The measurable cell potential solely dependent on [Cl-] present in the sample
solution → can be used to analyze [Cl-] in the sample solution.
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Membrane indicator electrodes

- Not part of redox reaction
- Respond to one ion
- Analyte bound to membrane diffuses into the solution causing charge
separation, the potential difference
The electrodes are categorized according to the type of membrane they employ :
glass membrane,
polymer,
crystalline,
gas sensor.

The first practical glass

electrode. (Haber and
Klemensiewcz, Z. Phys.
Chem, 1909, 65, 385.
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pH Meter
pH meter is a volt meter that measures the electrical potential difference
between a pH glass electrode and a reference electrode and displays the result
in terms of pH value of the sample solution in which they are immersed
How does it work
- The pH sensitive glass surfaces from a hydrated gel in water in which metal
diffuses out and H+ diffuses in.
- An ion-exchange equilibrium occurs
- The porous plug serves as the salt bridge
- The ideal pH electrode potential changes by 59.16 mV for every unit pH
change of analyte at 25oC.
Instrumentation
A pH meter consists of a H+-selective membrane, an internal reference
electrode, an external reference electrode, and a meter with control electronics
and display. Commercial pH electrodes usually combine all electrodes into one
unit that are then attached to the pH meter.
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Typical electrode system for measuring pH. (a) Glass electrode (indicator) and saturated calomel electrode (reference)
immersed in a solution of unknown pH. (b) Combination probe consisting of both an indicator glass electrode and a
silver/silver chloride reference. A second silver/silver chloride electrode serves as the internal reference for the glass
electrode. The two electrodes are arranged concentrically with the internal reference in the center and the external
reference outside. The reference makes contact with the analyte solution through the glass frit or other suitable porous
medium. Combination probes are the most common configuration of glass electrode and reference for measuring pH.
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pH Meters
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Various of indicator electrode

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Salt Bridge
• The Salt Bridge serves to connect the solution in the cathode cell with the
solution in the anode cell to allow the electric current to flow.
• The salt bridge is made from a U-shaped glass tube filled with agar containing
potassium chloride (KCl) solution.
• Gelatin is a gel that serves to prevent the mixing of cathode cell solution with
anode cell solution, however salt solution in it will allow the ions to migrate
between the anode & cathode solution.
• When the solution in one cell begins to run out of negative ions (due to
reaction), then the Cl- ion will flow from the salt bridge to neutralize the
solution.
• In contrast, the K+ ions will flow in the opposite direction to neutralize the
excess of negative ions in the other cell.
• Although a salt bridge is absolutely necessary for an electrochemical cell, it
raises a problem in potentiometric analysis → Liquid-Junction Potentials
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Junction Potentials
• Caused by unequal mobility of different ions at liquid-liquid
interfaces.
• Ex : In a brine – water mixture, Cl- diffuses faster than Na+
• Unknown junction potentials can result in a limitation of
accuracy of potentiometric measurements
• Ecell is therefore uncertain, because
• Eobserved = Ecell +Ejunction
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Application of Potentiometry
Potentiometry is used for:
• Measurement of concentrations of analyte directly.
One of the most successful examples is: pH meter
This success is due to the tools: cheap, reliable, and selective (in the
sense of only detecting H+ ions, other unobtrusive ions).
• Potentiometric titration
Potential measurements are made to follow the course of a titration, to
determine the location of the titration equivalent point.
Combination with other instrument / analytical methods.
For example: combined with liquid chromatography to detect the
concentration of the analyte after they exit from the separation tube /
column.
Applications of ion selective electrodes 22

Ion-selective electrodes are used in a wide variety of applications for determining the
concentrations of various ions in aqueous solutions. The following is a list of some of the
main areas in which ISEs have been used.
- Pollution Monitoring: CN, F, S, Cl, NO3 etc., in effluents, and natural waters.
- Agriculture: NO3, Cl, NH4, K, Ca, I, CN in soils, fertilisers and feedstuffs.
- Food Processing: NO3, NO2 in meat preservatives.
- Salt content of meat, fish, dairy products, fruit juices, brewing solutions.
- F in drinking water and other drinks.
- Ca in dairy products and beer.
- K in fruit juices and wine making.
- Corrosive effect of NO3 in canned foods.
- Detergent Manufacture: Ca, Ba, F for studying effects on water quality.
- Paper Manufacture: S and Cl in pulping and recovery-cycle liquors.
- Explosives: F, Cl, NO3 in explosive materials and combustion products.
- Electroplating: F and Cl in etching baths; S in anodising baths.
- Biomedical Laboratories: Ca, K, Cl in body fluids (blood, plasma, serum, sweat).
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Potentiometry Titration
• In potentiometric titration, a potential measurement during
the course of a titration, then from the potential curve (E)
to the volume of titrant (V) we can determine the location
of the titration equivalent point. The instrument images
used in potentiometric titration are as follows:
• Potentiometric titration will provide a more
reliable equivalent point than the visual
indicator, especially when the color change
is difficult to observe or involves a cloudy
solution.
• However, this titration will take longer than
titration with visual indicators, when done
manually.
Apparatus for a • Currently the automatization of
potentiometric potentiometric titration has been
titration.
performed by a number of automatic
titrator manufacturers.
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Potentiometric Titration
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Potentiometric Titration
Titration of 2.433mmol of chloride ion with 0.1000M silver nitrate.

(a) Titration curve (b) First-derivative curve

(c) Second-derivative curve

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Equivalence Point
• Potentiometric Titration will get a sigmoid-shaped curve in
potentiometric titration:

• Equivalent point occurs when the most drastic

potential changes occur.

• The second way to determine the location of

the equivalence point is to use the first
derivative test.
• Equivalent point occurs when dE / dV reaches
its maximum value.
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Equivalence Point

The third way to determine the location of

the equivalence point is to use a second
derivative test.
According to this test, the equivalence point
occurs when d2E/dV2 is zero.

• The three methods of determining the location of the above equivalence point
are based on the assumption that: the titration curve is symmetrical around the
equivalence point. This assumption is valid if the titrant and the analyte react
in a 1: 1 ratio and when the reaction at the electrode is reversible.
• In many cases, the reaction does not take place equimolar, but because the
titration curve so sharp, the assumption was just a little error.
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(a) Experimental points in the

titration of 1.430 mg of xylenol
orange, a hexaprotic acid,
dissolved in 1.000 mL of aqueous
0.10 M NaNO3. The titrant was
0.06592 M NaOH.
(b) (b) The first derivative, dpH/dV, of
the titration curve.
(c) (c) The second derivative,
(dpH/dV)d/V, which is the
derivative of the curve in panel b.
Derivatives for the first end point
are calculated in Figure 10-6.
End points are taken as maxima
in the derivative curve and zero
crossings of the second
derivative.
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Spreadsheet Calculation Example

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Equivalent point determination

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Application of potentiometric titration

a) Neutralization reactions: glass / calomel electrode for
determination of Ph

b) Precipitation reactions: Membrane electrodes for the

determination of the halogens using silver nitrate reagent

c) Complex formation titration: metal and membrane

electrodes for determination of many cations (mixture of
Bi3+, Cd2+ and Ca2+ using EDTA)

d) Redox titration: platinum electrode For example for

reaction of Fe3+/ Fe2+ with Ce4+/Ce3+
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• Neutralization reactions:

glass / calomel electrode

for determination of pH
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• Precipitation reactions: Membrane

electrodes for the determination of the halogens
using silver nitrate reagent
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• Complex formation titration:

metal and membrane electrodes for
determination of many cations (mixture of Bi3+,
Cd2+ and Ca2+ using EDTA)
E, V vs Ag/AgCl, 1M KCl

0.12

E E/V
0.10

0.08

0.06

0.0 0.1 0.2 0.3 0.4 0.5 0.6

Volume, mL
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• Redox titration: platinum electrode

For example for reaction of Fe3+/ Fe2+ with
Ce4+/Ce3+
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Application of potentiometric Titration

Titration curve for 25 mL of red wine titrated with 0.1926 M

NaOH using autotitrator and its first derivative curve.
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Potentiometric determination of
Equilibrium constant
• Numerical value of Kf, Ksp, Ka can be determined by
measurement of cell potentials
• Ex:
• Calculate the formation constant Kf for Ag(CN)2-
Ag+ + 2CN- ⇌ Ag(CN)2-
If the cell
SCE || Ag(CN)2- (0.0075M), CN- (0.025M) |Ag
develops a potential of -0.625 V
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• solution
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Exercise
• Calculate the dissociation constant KHP for the weak acid
HP if the cell
SCE || HP (0.01 M), NaP (0.04 M) |Pt, H2 (1 atm)
• Develop a potential of -0.591 V
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