PHÂN TÍCH ĐIỆN HÓA

TS. Đỗ Minh Huy

Email: domhuy@hcmus.edu.vn

02/2023
 Content

▪ PHƯƠNG PHÁP ĐO ĐIỆN THẾ KHÔNG DÒNG - POTENTIOMETRY

▪ PHƯƠNG PHÁP VON – AMPE

2
 References
➢ Electroanalytical Methods: Guide to Experiments and
Applications
Fritz Scholz
➢ Electrochemical Methods: Fundamentals and Applications
Allen J. Bard, Larry R. Faulkner

3
 Categories
Electroanalytical methods

Interfacial methods Bulk methods

Static methods Dynamic methods

(i = 0) (i ≠ 0)

Potentiometry Controlled potential Controlled current

Variable potential Fix potential Controlled-current

coulometry
Amperometry Controlled-potential
coulometry
Stirred solution Quiescent solution

Hydrodynamic
voltammetry

Linear potential Pulsed potential Cyclical potential 4

 Applications

Study Redox Chemistry

• Electron transfer reactions, oxidation, reduction, organics & inorganics, proteins
• Adsorption of species at interfaces

Electrochemical Synthesis
Organics, inorganics, materials, polymers

Electrochemical analysis
• Measure the Potential of reaction or process
E = const + k log C (potentiometry)
• Measure the Rate of a redox reaction; Current (I) = k C (voltammetry)

5
 Applications

914 pH/Conductometer Polarographic Dissolved Oxygen Sensors ElectrochemicalSensors

6
Applications
 Definition

The majority of chemical reactions:

➢ Acid/Base Reactions: proton transfer
➢ Oxidation/Reduction (Redox) Reactions : electron transfer

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Definition

9
Definition

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Definition

Electrochemistry is the study of electricity and

how it relates to chemical reactions. In
electrochemistry, electricity can be generated
by movements of electrons from one element
to another in a reaction known as redox or
oxidation-reduction reaction.

Electrochemistry is the study of electron

movement in an oxidation or reduction
reaction at a polarized electrode surface.
Each analyte is oxidized or reduced at a
specific potential and the current measured is
proportional to concentration.
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 Definition
Electroanalytical methods are a class of
techniques in analytical chemistry, which study an
analyte by measuring the potential (volts) and/or
current (amperes) in an electrochemical cell
containing the analyte.
The three main categories are potentiometry (the
difference in electrode potentials is measured),
coulometry (the cell's current is measured over
time), and voltammetry (the cell's current is
measured while actively altering the cell's potential).
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Definition

13
 Electrochemical Cells
Galvanic Cells

14
 Electrochemical Cells
Galvanic Cells
A galvanic cell (also called a voltaic cell) uses a
spontaneous chemical reaction to generate
electricity. To accomplish this, one reagent must be
oxidized and another must be reduced. The two
cannot be in contact, or electrons would flow directly
from the reducing agent to the oxidizing agent.
Instead, oxidizing and reducing agents are
physically separated, and electrons are forced to
flow through a wire to go from one reactant to the
other. 15
 Electrochemical Cells
Galvanic Cells

A DC electrochemical cell consists of two electrical

conductors called electrodes, each immersed in a
suitable electrolyte solution. For a current to develop in
a cell, it is necessary (1) that the electrodes be
connected externally with a metal conductor, (2) that
the two electrolyte solutions be in contact to permit
movement of ions from one to the other, and (3) that
an electron transfer reaction can occur at each of the
two electrodes. 16
 Electrochemical Cells
Galvanic Cells
Conduction in a Cell

1. Metals
2. Solution (ion migration)
3. Electrode reactions (at interfaces)

17
 Electrochemical Cells
Galvanic Cells
Conduction in a Cell
In the silver and copper electrodes, as well as in the external
conductor, electrons are the charge carriers, moving from the copper
electrode through the external conductor to the silver electrode.

Within the solutions the flow of charge is the result of migration of

both cations and anions. In the halfcell on the left, copper ions
migrate away from the electrode into the solution, and sulfate and
hydrogen sulfate ions move toward it; in the half-cell on the right,
silver ions move toward the electrode and anions move away from it.
Inside the salt bridge, charge is carried by migration of potassium
ions to the right and chloride ions to the left. Thus, all of the ions in
the three solutions participate in the flow of charge.

A third process occurs at the two electrode surfaces. At these

interfaces, an oxidation or a reduction reaction couples the ionic
conduction of the solution with the electron conduction of the
electrode to provide a complete circuit for the flow of charge
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 Electrochemical Cells
Galvanic Cells
Conduction in a Cell

19
 Electrochemical Cells
Galvanic Cells
Conduction in a Cell

Cathode Anode
Denoted by a positive Denoted by a negative
sign since electrons are sign since electrons are
consumed here liberated here
A reduction reaction An oxidation reaction
occurs in the cathode of occurs here
an electrochemical cell
Electrons move into the Electrons move out of
cathode the anode

20
 Potentiometry
Galvanic Cells
Electrochemical reaction

➢ The chemical reaction is called a homogeneous

reaction, because it occurs everywhere within
the medium at a uniform rate

➢ In contrast, an electrode process is a

heterogeneous reaction occurring only at the
electrode-electrolyte interface

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 Electrochemical Cells
Galvanic Cells

22
 Potentiometry

Reduction Oxidation
2+ – 2+ –
Cu ( aq ) + 2 e → Cu( s) Zn ( s ) → Zn ( aq ) + 2e

Cu 2+(aq ) + Zn ( s ) ↔
→ Zn 2+(aq ) + Cu (s )

➢ Zn (the reducing agent) is being oxidized (its oxidation number is going from 0 to +2)
➢ Cu2+ (the oxidizing agent) is being reduced (its oxidation number is going from +2 to 0)

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 Electrochemical Cells
➢ Electrochemistry
➢ Electroanalytical chemistry
➢ Galvanic Cells (Components of Electrochemical Cells, Conduction)

24
 Electrochemical Cells
Electrolytic Cells

25
 Electrochemical Cells
Galvanic Cells

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 Electrochemical Cells
Galvanic Cells
Salt bridge
- Acts to isolate two halves of
electrochemical cell while allowing
migration of ions and current flow
- Usually consists of a tube filled with KNO3
or others
- Separate species to prevent direct
chemical reactions

27
 Potentiometry
Galvanic Cells
Salt bridge
Daniell Cell without salt bridge

Carefully merge
Liquid-liquid interface

two solutions.
Make CuSO4 more
dense than ZnSO4.
Sheath Cu
electrode in glass.

28
 Electrochemical Cells
Line Notation

Anode (oxidation) Cathode (reduction)

–ive salt bridge +ive
Zn metal Cu metal

ZnSO4 (aq) CuSO4 (aq)

Zn(s) → Zn2+(aq) + 2e– Cu2+(aq) + 2e– → Cu(s)

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 Electrochemical Cells
Line Notation

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 Electrochemical Cells
Line Notation

➢ Begin with the anode and continue to

the cathode
➢ (|) to identify a boundary between two
phases where a potential develops,
➢ (,) to separate species in the same
phase or to identify a boundary between
two phases where no potential
develops.
➢ (||) indicates the salt bridge

Zn(s) | ZnCl2 (aq, aZn2+ =0.0167) || AgNO3 (aq, aAg+ = 0.100) | Ag

31
 Electrochemical Cells
Line Notation

32
 Electrochemical Cells
Standard Potentials

33
 Electrochemical Cells
Standard Potentials

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 Electrochemical Cells
Standard Potentials

A reaction is spontaneous if ΔG
is negative and E is positive.
ΔG and ΔE refer to the free
energy change and potential
when the activities of reactants
and products are unity.
ΔG = -nFE

35
 Electrochemical Cells
Nernst Equation

2
36
 Electrochemical Cells
Nernst Equation for a Complete Reaction

The measured voltage is the difference between the potentials of the two electrodes:
E = ECathode - EAnode

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 Electrochemical Cells
Nernst Equation for a Complete Reaction
Step 1 Write reduction half-reactions for both half-cells and find E° for each.
Multiply the half-reactions as necessary so that they both contain the same number of
electrons. When you multiply a reaction, you do not multiply E°.
Step 2 Write a Nernst equation for the right half-cell, which is attached to the positive
terminal of the potentiometer. This is ECathode
Step 3 Write a Nernst equation for the left half-cell, which is attached to the negative terminal
of the potentiometer. This is EAnode
Step 4 Find the net cell voltage by subtraction: E = ECathode - EAnode
Step 5 Write the net cell reaction by subtracting the left half-reaction from the right
halfreaction. (Subtraction is equivalent to reversing the left half-reaction and adding.)
38
 Electrochemical Cells
Nernst Equation for a Complete Reaction
Find the voltage of the cell if the right half-cell contains 0.50 M AgNO3(aq) and the left half-cell
contains 0.010 M Cd(NO3)2(aq). Write the net cell reaction and state in which direction electrons
flow.

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 Electrochemical Cells
Nernst Equation for a Complete Reaction

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 Electrochemical Cells
Nernst Equation for a Complete Reaction

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 Electrochemical Cells
Nernst Equation for a Complete Reaction

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 Electrochemical Cells
Nernst Equation for a Complete Reaction

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 Electrochemical Cells
LIQUID JUNCTION POTENTIALS
The interface between electrochemical solution and
the salt bridge (liquid-liquid interface)
→ could develop as junction potential

Ecell = Ecathode – Eanode + Eliquid junction

Origin of the junction potential between a solution

of 0.1 M HCl and a solution of 0.01 M HCl
44
 Electrochemical Cells
Summary

➢ Electrochemistry
➢ Electroanalytical chemistry
➢ Galvanic Cells
➢ Line Notation
➢ Nernst Equation
➢ Liquid junction potentials

45
 Potentiometry
The Standard Electrode Potential

46
 Potentiometry
Standard Hydrogen Electrode - SHE
The SHE consists of platinum wire that is connected to a Pt
surface in contact with an aqueous solution containing 1 M
H+ in equilibrium with H2 gas at a pressure of 1 atm. In the
molecular view, the Pt surface catalyzes the oxidation of
hydrogen molecules to protons or the reduction of protons
to hydrogen gas.
The convention is to select a particular electrode and
assign its standard reduction potential the value of 0.0000V.
This electrode is the Standard Hydrogen Electrode.

2H+(aq) + 2e– ↔ H2(g)

𝑬𝒐𝑷𝒕𝑰𝑯𝟐,𝑯+ = 0.000 V (at all temperatures)

Pt(s), H2 (k, 1 atm) | H+ (a = 1.00) || 47

 Potentiometry
The Standard Electrode Potential

48
 Potentiometry
Standard Hydrogen Electrode - SHE

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 Potentiometry
Standard Hydrogen Electrode - SHE

➢ Platinum is used in the Standard Hydrogen Electrode due to

the following reasons:
➢ Platinum is a relatively inert metal which does not corrode
easily.
➢ Platinum has catalytic qualities which promotes the proton
reduction reaction.
➢ The surface of platinum can be covered with platinum black,
a fine powder of platinum. This type of platinum electrode is
called a platinized platinum electrode.
➢ Platinum also improves the reaction kinetics by adsorbing
hydrogen at the interface

Trassati’s volcano plot for the hydrogen 50

evolution reaction in acid solutions
Potentiometry

51
 Potentiometry
Đo hiệu thế giữa hai điện cực nhúng vào một dung dịch nhất
định
➢ Điện cực so sánh có thế không đổi (Reference electrode: maintains a fixed
potential)
➢ Điện cực chỉ thị có thế thay đổi theo bản chất và nồng độ của ion cần xác
định (Indicator electrode: responds to analyte activity)
Từ thế E thay đổi có thể suy ra hoạt độ hoặc nồng độ của ion
cần xác định dựa trên phương tr.nh Nernst.
Hệ hoạt động với cường độ d.ng gần như bằng 0 (i~0), không có phản ứng điện hóa
xảy ra, thành phần dung dịch không đổi. 52
 Potentiometry

➢ l Điện cực so sánh (RE)

➢ l Điện cực chỉ thị (IE)

➢ l Cầu muối (SB)

➢ l Dung dịch phân tích (A)

➢ l Một máy đo thế

53
 Potentiometry
The Standard Electrode Potential

Disadvantage ???

54
 Potentiometry
The Standard Electrode Potential

55
 Potentiometry
SILVER/SILVER CHLORIDE ELECTRODES

➢ The silver - silver chloride electrode can be constructed

as a thin tube that is dipped into solution
➢ The standard reduction potential for the Ag | AgCl half-
cell is +0.222 V at 25°C
➢ The potential of the electrode in a saturated solution of
KCl at 25°C is +0.197 V with respect to S.H.E. at 25°C

56
 Potentiometry
SILVER/SILVER CHLORIDE ELECTRODES

Tinh thế điện cực so sánh vs SHE khi nồng độ KCl 3M? 57
 Potentiometry
SILVER/SILVER CHLORIDE ELECTRODES

58
 Potentiometry
SILVER/SILVER CHLORIDE ELECTRODES

59
 Potentiometry
SILVER/SILVER CHLORIDE ELECTRODES
First, we prepared the autopipettor tip with gel by mixing 1.4g agarose, 100 ml water and 5.0g KNO3, and heat the
solution to boiling with constant stirring

After preparing the solution, we placed the

autopipettor tip upright in the solution and
allow it to cool and gel for 24 hours.

60
 Potentiometry
SILVER/SILVER CHLORIDE ELECTRODES

Next, we prepared the silver wire with silver chloride coating by

dipping a fine silver wire in the bleach solution for 10 minutes until the
presence of a dark deposit on the silver wire. OCl- ion and Cl- ion in
the bleach solution react with silver to form silver chloride, which is
shown in the equation below.

61
 Potentiometry
SILVER/SILVER CHLORIDE ELECTRODES

Finally, we filled the autopipettor tip with 3.0 M KCl solution, and inserted the wire into the tip.
We used the parafilm to both prevent the evaporation of the KCl solution and stablised the silver
wire.

62
 Potentiometry
SATURATED CALOMEL ELECTRODES - SCE

The standard potential for this reaction is +0.268 V. If

the cell is saturated with KCl at 25°C, the potential is
+0.241 V. A calomel electrode saturated with KCl is
called a saturated calomel electrode, abbreviated
S.C.E. (and pictured to the right). The advantage in
using saturated KCl is that [Cl−] does not change if
some liquid evaporates

63
 Potentiometry
CALOMEL ELECTRODES

Hg2Cl2(s) + 2e− ↔ 2Hg(l) +2Cl−

Temperature dependent!
64
 Potentiometry
Example
The potential for an Fe3+/Fe2+ half-cell is +0.750 V relative to the standard hydrogen electrode.
What is its potential when using a saturated calomel electrode or a saturated silver/silver
chloride electrode?

We can use the same equation to calculate the potential when using a saturated calomel electrode

or a saturated silver/silver chloride electrode

65
 Potentiometry
Example
The potential for an Fe3+/Fe2+ half-cell is +0.750 V relative to the standard hydrogen electrode.
What is its potential when using a saturated calomel electrode or a saturated silver/silver
chloride electrode?

66
 Potentiometry
The Reference Electrode
Yêu cầu của điện cực so sánh

➢ Điện cực có thế hằng định và biết trước.

➢ Thế tuân theo phương trình Nernst và trở lại thế ban đầu khi chịu một

dòng điện rất nhỏ. Phản ứng điện cực hoàn toàn thuận nghịch

➢ Thế ít thay đổi theo nhiệt độ

➢ Độ lặp lại cao, dễ chế tạo, dễ bảo quản

➢ Không nhạy với chất phân tích

67
 Potentiometry
INDICATOR ELECTRODES

Ideal indicator electrode: responds rapidly and

reproducibly to changes in the concentration of an
analyte ion (or group of analyte ions)

➢ Metallic indicator electrodes (electrodes of the first

kind, electrodes of the second kind, redox electrodes)
➢ Membrane electrodes

68
 Potentiometry
INDICATOR ELECTRODES

Yêu cầu của điện cực chỉ thị

➢ Thế chỉ phụ thuộc vào hoạt độ chất cần xác định và tuân theo phương trình Nernst
➢ Ổn định, độ lặp lại cao
➢ Thời gian đáp ứng nhanh
➢ Cấu tạo thiết bị đơn giản, dễ sử dụng và bảo quản

69
 Potentiometry
INDICATOR ELECTRODES - Electrodes of the first kind
A pure metal electrode : in direct equilibrium with its cation in the solution

𝑴+𝒏 𝒂𝒒 + 𝒏𝒆− ↔ 𝑴(𝒔ሻ

𝟎. 𝟎𝟓𝟗𝟐 𝟏
𝑬𝒊𝒏𝒅 = 𝑬𝟎 − 𝒍𝒐𝒈 𝒏+
𝒏 𝑴

70
 Potentiometry
INDICATOR ELECTRODES - Electrodes of the first kind

If a metal, M, is in a solution of Mn+, the cell potential is

K is a constant that includes the standard-state potential for the Mn+/M redox couple, the
potential of the reference electrode, and the junction potential

71
 Potentiometry
INDICATOR ELECTRODES - Electrodes of the first kind
If we place a copper electrode in a solution containing Cu2+, the electrode’s potential due to the
reaction: 𝟐+ −
𝑪𝒖 𝒂𝒒 + 𝟐𝒆 ↔ 𝐂𝐮 (𝒔൯
is determined by the activity of Cu2+

If copper is the indicator electrode in a potentiometric electrochemical cell that also includes a
saturated calomel reference electrode

then we can use the cell potential to determine an unknown activity of Cu2+ in the indicator
electrode’s half-cell
𝟎. 𝟎𝟓𝟗𝟏𝟔 𝟏
𝑬𝒄𝒆𝒍𝒍 = 𝑬𝒊𝒏𝒅 − 𝑬𝑺𝑪𝑬 + 𝑬𝒋 = +𝟎. 𝟑𝟒𝟏𝟗 𝑽 − 𝒍𝒐𝒈 − 𝟎. 𝟐𝟒𝟒𝟒 𝑽 + 𝑬𝒋 72
𝟐 𝒂𝑪𝒖𝟐+
 Potentiometry
Indicator electrodes

Problems
• Electrode of the first kind is not very popular because...
➢ Metallic indicator electrodes are not very selective and respond not only to their own cations
but also to other more easily reduced cations.
➢ Many metal electrodes can be used only in neutral or basic solutions because they dissolve
in the presence of acids
➢ Easily oxidized, can be used only when analyte solutions are deaerated to remove oxygen
➢ Certain hard metals (Fe, Cr, Co, Ni) do not provide reproducible potentials
• Limited electrodes are: Ag/Ag+ and Hg/Hg2+ in neutral solutions and Cu/Cu2+, Zn/Zn2+, Cd/Cd2+,
Bi/Bi3+, Tl/Tl+, and Pb/Pb2+ in deaerated solutions.

73
 Potentiometry
INDICATOR ELECTRODES - Electrodes of the second kind
➢ Dùng để xác định các anion Xn-.
➢ Dùng một kim loại M làm điện cực. Kim loại này tạo hợp chất ít tan hoặc tạo phức bền với anion X.

74
 Potentiometry
INDICATOR ELECTRODES - Electrodes of the second kind

The potential of a silver electrode in a solution of Ag+ is given by

If we saturate the indicator electrode’s half-cell with AgI, the solubility reaction

determines the concentration of Ag+; thus

75
 Potentiometry
INDICATOR ELECTRODES - Electrodes of the second kind
where Ksp, AgI is the solubility product for AgI

we find that the potential of the silver electrode is a function of the activity of I-. If we
incorporate this electrode into a potentiometric electrochemical cell with a saturated calomel
electrode

The cell potential is

where K is a constant that includes the standard-state potential for the Ag+/ Ag redox couple, the
solubility product for AgI, the reference electrode’s potential, and the junction potential
76
 Potentiometry
INDICATOR ELECTRODES - Electrodes of the second kind
Mercury : indicator electrode of second kind for the EDTA anion Y4-. When a small amount of
HgY 2- is added to a solution containing Y4-, the half-reaction of a Hg electrode

77
 Potentiometry
INDICATOR ELECTRODES - redox electrodes
A Redox electrode will measure the ratio of oxidized species to reduced species in a solution
where both are present. The indicator electrode will measure the electron movement and to do
this, it must be chemically inert and an excellent electron conductor.

78
 Potentiometry
Membrane electrodes

79
 Potentiometry
pH Electrode
What is pH? Potential Hydrogen or Power of Hydrogen
H3O+ + OH- ↔ 2H2O
[HCl] 0.1 M and [CH3COOH] 0.1 M ???? CH3COOH + H2O ↔ CH3COO- + H3O+
pH = -log[aH+]

80
 Potentiometry
pH Electrode

81
 Potentiometry
pH Electrode

82
 Potentiometry
pH Electrode

83
 Potentiometry
pH Electrode

84
 Potentiometry
pH Electrode

1. Internal Reference Potential

2. Inner Glass/Solution Potential
3. External Reference Potential
4. LIQUID JUNCTION POTENTIAL

85
 Potentiometry
pH Electrode

86
 Potentiometry
pH Electrode

87
 Potentiometry
pH Electrode

88
 Potentiometry
pH Electrode

89
 Potentiometry
pH Electrode
Temperature effects
➢ Electrode
➢ Calibration
➢ Buffers
➢ Samples

90
 Potentiometry
pH Electrode
Temperature effects

91
 Potentiometry
pH Electrode

92
 Potentiometry
pH Electrode
pH Calibration

93
 Potentiometry
pH Electrode
pH Calibration
Bracket your process pH
➢ Cardinal Rules for pH Calibration
Always have your calibration buffers “bracket” your process
pH measurement of interest.
-Example; Process pH of 8.2 should utilize 7 and 10
buffers
➢ Never calibrate with two buffers more than 3 pH units apart

94
 Potentiometry
pH Electrode
pH Calibration

Always ensure the electrode is clean before calibration.

➢ Zero point: pH 7 buffer. The E0 point is a critical point in the calibration curve and an
indication of sensor status. Should be close to 0 mV
➢ Use fresh buffers.
➢ Bracket your process measurement when calibrating
➢ Rinse the electrode and dab dry between calibration measurements. Do not rub the
electrode. Rubbing could cause static charges and disrupt sensor function.
➢ Make sure you have an acceptable slope and fast response time.
Good transmitters will tell you how your sensor is doing.
Good slopes range from 90% to 101% (possibly even lower)
A pH sensor should reach a stable value in buffer in 30s or less 95
 Potentiometry
pH Electrode
Stable Readings
➢ Electrode performance and efficiency
➢ Junction and bulb function (non-clogged and non-coated)
➢ Electrode Type (gel effects, open junction, etc.)
➢ Meter stabilization settings (if available)
➢ Resolution settings (0.1 or 0.01 or 0.001)
➢ Inner fill solution freshness
➢ Low ionic strength samples
Use open junction electrode and stir samples when measuring
➢ Air bubbles near junction

96
 Potentiometry
pH Electrode
Electrode Care and Maintenance
When do you need to clean your electrode?
➢ Check slope range
Ideal range: 95 % - 102 %
Cleaning range: 92% - 95%
Replacement range: below 92%
➢ Check response times in buffers
Electrode stability within 30 seconds
➢ Check precision of electrode by reading buffers as samples
➢ Check for any drift of electrode in pH buffer
97
 Potentiometry
pH Electrode
Electrode Care and Maintenance
➢ General electrode bulb cleaning
Soak in Cleaning Solution for 30 minutes
Replace electrode fill solution
Soak in storage solution for at least 2 hours
➢ Electrode junction cleaning
Soak in 0.1M KCl for 15 minutes at 70 oC
Replace electrode fill solution
Soak in electrode storage solution for 2 hours
➢ Check junction by suspending in air for ten minutes
98
Observe KCl crystal formation
 Potentiometry
pH Electrode
Keys to Accuracy
➢ Always use fresh buffers
Check bottle expiration and date opened
➢ Fresh buffer for each calibration
➢ Replace the fill solution in the electrode every week
Fill solution concentration is maintained
KCl crystallization is prevented
➢ Make sure to use the correct fill solution

99
 Potentiometry
pH Electrode
Keys to Accuracy

➢ Make sure level of fill solution is high

➢ Gently stir buffers and samples

➢ Shake any air bubbles out of the electrode

➢ Use insulation between stir plate and sample container to minimize heat transfer

➢ Blot electrodes between samples

➢ Uncover fill hole during measurement

100
 Potentiometry
pH Electrode
Troubleshooting pH Problems
➢ Common measurement problems
▪Readings not reproducible
▪Slow response
▪Noisy response
▪Drifty response
▪Inaccurate
➢ Troubleshooting Sequence Meter
▪ Buffers
▪ Reference electrode
▪ pH electrode
▪ Sample
101
▪ Technique
 Potentiometry
pH Electrode
Electrode Check
➢ Check Slope Range (102% -95%)
➢ Check response time in buffers (stable reading in 30 seconds)
➢ Verify mV readings are in the correct range for each buffer
pH 4.01 is +178 mV +/-30 mV
pH 7.00 is 0 mV +/-30 mV
pH 10.01 is -178 mV +/-30 mV
IF the Electrode Check FAILS:
➢ Check for air bubbles near bulb
➢ Verify correct filling solution is being used
➢ Check for salt crystal formation inside electrode
➢ Check junction is open by suspending in air for 10 minutes and KCl crystal formation should
occur
➢ Use Junction cleaning procedures
➢ Re-check instruction manual for electrode conditioning procedures 102
 Potentiometry
pH Electrode
Alkaline error

• Exhibited at pH > 9
• Electrodes respond to H+ and alkali
cations
• C,D,E and F: measured value is < true
value
• Electrode also responds to other
cations
• Higher pH at lower [Na+]

103
 Potentiometry
pH Electrode
Acid error

• Exhibited at pH < 0.5

• pH readings are higher (curves A and

B)
• Saturation effect with respect to H+

104
 Potentiometry
pH Electrode

105
 Potentiometry
pH Electrode

106
 Potentiometry
pH Electrode
Cleaning Electrodes
General Cleaning: Soak the electrode in 1:10 dilution of reagent in a 0.1 to 0.5% liquid
detergent solution in hot water with vigorous stirring for 15 minutes. Place junction
under warm, running tap water for 15 seconds. Drain/refill the reference chamber. Soak
the electrode in storage solution for at least 10 minutes

Salt Deposits: Dissolve the deposit by immersing the electrode in 0.1 M HCl for five
minutes, followed by immersion in 0.1 M NaOH for five minutes, and thorough rinsing
with distilled water

Oil/Grease Films: Wash electrode pH bulb in mild detergent or methanol. Rinse

electrode tip with distilled water
107
 Potentiometry
pH Electrode
Cleaning Electrodes
Clogged Reference Junction: Heat a diluted KCl solution to 60 to 80°C. Place the
reference portion of the pH electrode into the heated KCl solution for approximately
10 minutes. Allow the electrode to cool while immersed in unheated KCl solution

Protein Deposits: Dissolve the deposit by immersing the electrode in a 1% pepsin

solution with a background of 0.1 M HCl for five minutes, followed by thorough
rinsing with distilled water

Air Bubbles: If air bubbles appear in the electrode (especially with microelectrode
and narrow test tube electrodes), open up the fill hole, grab the cable of the probe
about 18" from the connection to the electrode, and spin in a circular motion over
your head (like a helicopter) for about a minute. The centrifugal force should force
108
the air bubble to the fill hole/top of the electrode
 Potentiometry
pH Electrode
Cleaning Electrodes
General
Soak in 0.1M HCl or 0.1M HNO3 for half an hour. For refillable electrodes. Drain and refill the
Electrode Filling Solution. Soak the electrode in Filling or Storage Solution for 1 hour.
Inorganic
Soak in 0.1M tetrasodium EDTA solution 15 minutes. Drain and refill the Electrode Filling
Solution. Soak the electrode in Filling or Storage Solution for 1 hour.
Protein
Soak in 1% pepsin in 0.1M HCl for 15 minutes. Drain and refill the Electrode Filling Solution.
Soak the electrode in Filling or Storage Solution for 1 hour.
Grease and Oil
Rinse with mild detergent or methanol solution. Drain and refill the Electrode Filling Solution.
Soak the electrode in Filling or Storage Solution for 1 hour.
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 Potentiometry
pH Electrode

First commercial glass electrodes (Corning 015):

22 % Na2O, 6 % CaO and 72 % SiO2

pH range of approximately 0.5 to 9

Replacing Na2O and CaO with Li2O and BaO

110
 Potentiometry
pH Electrode

111
 Potentiometry
pH Electrode

112
 Potentiometry
Membrane electrodes

➢ Glass electrode
➢ Crystalline-Membrance electrode
➢ Liquid membrance electrode

113
 Potentiometry
Membrane electrodes
Crystalline-Membrane electrode

➢ Polycrystalline or monocrystalline materials

➢ Crystalline membranes provide a basis for potentiometric measurements of a number of
analytes, including anions and also cations
➢ Mixed crystals of low-soluble silver salts and heavy metal sulfides (silver sulfide and another
low-soluble silver salt)
➢ Significantly lower resistance than those made of glass or of plasticized polymers

114
 Potentiometry
Membrane electrodes
Crystalline-Membrane electrode

115
 Potentiometry
Membrane electrodes
Crystalline-Membrane electrode

Ag2S 116
 Potentiometry
Membrane electrodes
Crystalline-Membrane electrode

Ag2S + AgCl 117

 Potentiometry
Membrane electrodes
Crystalline-Membrane electrode

where aM is the activity of the metal ion

2+

Ag2S + CdS, CuS, or PbS

118
 Potentiometry
Membrane electrodes
Crystalline-Membrane electrode

119
 Potentiometry
Membrane electrodes
Crystalline-Membrane electrode

120
 Potentiometry
Membrane electrodes
Crystalline-Membrane electrode

Migration of F– through LaF3 doped with EuF2

Potential caused by charge imbalance from migrating ion across membrane
121
 Potentiometry
Membrane electrodes
Liquid membrance electrode

di-(n-decyl) phosphate is immobilized in a

polyvinyl chloride (PVC) membrane

122
 Potentiometry
Membrane electrodes
Gas sensing electrode

➢ Measurement of PCO2 in routine blood gases

➢ A modified pH electrode with a CO2 permeable membrane
covering the glass membrane surface
➢ A bicarbonate buffer separates the membranes
➢ Change in pH is proportional to the concentration of
dissolved CO2 in the blood

123
 Potentiometry
DIRECT POTENTIOMETRY

➢ A rapid and convinient method of detecting the activity of cations and anions
➢ The technique used in this method is a comparison of the potential developed by the
indicator electrode when it is immersed in the solution with that when it is immersed in
standard solution of the analyte

124
Potentiometry

125
 Potentiometry
POTENTIOMETRIC MEASUREMENT
➢ Calibration Method
➢ Standard Addition Method

➢ It is applied for determination of substance

by direct potentiometry
➢ In which we plot potential of the cell Vs a
series of standard solution of extragrade of
the substance to be determined
➢ Then measure the potential prodused when
using the unknown solution and from the
calibration curve we can obtain its
concentrations

126
 Potentiometry
POTENTIOMETRIC MEASUREMENT
➢ Calibration Method
➢ Standard Addition Method

127
 Potentiometry

Hạn chế của phương pháp điện thế trực tiếp:

➢ Cần phải biết hệ số hoạt độ

➢ Phải biết thế nối Ej do

128
 Potentiometry
POTENTIOMETRIC TITRATION
➢ Involves measurement of the potential of a suitable indicator electrode as a function of
titrant volume
➢ Provides MORE RELIABLE data than the usual titration method
➢ Useful with colored/turbid solutions
➢ May be automated
➢ More time consuming

129
 Potentiometry
POTENTIOMETRIC TITRATION

➢ Is a technique similar to direct titration of a redox reaction.

➢ No indicator is used, (instead the potential across the analyte) typically an
electrolyte solution is measured.
➢ To do this, two electrodes are used, an indicator electrode and a reference
electrode.
➢ The indicator electrode forms an electrochemical half cell with the interested ions
in the test solution.
➢ The reference electrode forms the other half cell, holding a consistent electrical
potential. 130
 Potentiometry
POTENTIOMETRIC TITRATION

➢ Điện cực so sánh

➢ Điện cực chỉ thị
➢ Buret
➢ Máy khuấy từ
➢ Vôn kế
➢ Cốc thủy tinh chứa dung dịch đo

131
 Potentiometry
POTENTIOMETRIC TITRATION

132
 Potentiometry
POTENTIOMETRIC TITRATION

➢ Thế của điện cực chỉ thị tỉ lệ với logarit hoạt độ của
chất phân tich (lga).
➢ Trong qua trinh chuẩn độ, hoạt độ giảm dần, lga thay
đổi chậm theo thế E đo được.
➢ Gần đến điểm tương đương, hoạt độ tiến đến 0, lga
và thế E biến thiên mạnh
➢ Nếu ΔE la độ biến thiên của thế ứng với thể tích thêm
vào thì ΔE/ ΔV biến thiên chậm khi còn xa điểm tương
đương, tăng rất nhanh khi đến gần điểm tương đương,
qua một cực đại ở điểm tương đương, sau đo giảm dần.

133
 Potentiometry
POTENTIOMETRIC TITRATION

It is used when the endpoints are very difficult to determine either when:
➢ Very diluted solution.
➢ Coloured and turbid solution.
➢ Absence of a suitable indicator.

134
 Potentiometry
POTENTIOMETRIC TITRATION

Application of potentiometric titration

➢ Neutralization reactions: glass / calomel electrode for determination of Ph
➢ Precipitation reactions: Membrane electrodes for the determination of the
halogens using silver nitrate reagent
➢ Complex formation titration: metal and membrane electrodes for determination
of many cations (mixture of Bi3+, Cd2+ and Ca2+ using EDTA)
➢ Redox titration: platinum electrode. Reaction of Fe3+/ Fe2+ with Ce4+/Ce3+

135