Pro. Dr.
Hala Zaazaa 1
A potential is produced when
A metal is dipped A metal covered inert electrode
in one of it’s own with one of it’s e.g pt. wire is
ions sparingly soluble put in a
salts is dipped in a solution
solution containing containing
the anion of the oxidant and
1 st Type sparingly soluble reductant in
electrode salt. the same
solution
2ndType
electrode Redox
electrode
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Classification of electrodes:
A- According to type B- According to function
1. First
Type
Reference electrode
Redox reactions
2. Second
Type Normal Hydrogen
electrode
Ag/AgCl reference
3. Redox electrode
electrode
Calomel reference
electrode
Ion selective Ion Indicator electrode
electrodes exchange
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I. Classification of electrodes According to the type:
1. Electrodes of the First Type
Consists of:
Metal dipped in its ions (TWO phase system) e.g. Cuo/Cu2+ , Zno/Zn2+
Potential: Cu-
metal
𝐶𝑢2+ + 2𝑒 − → 𝐶𝑢(𝑠)
0.0592
𝐸 = 𝐸0 + log [𝐶𝑢2+ ]
2
2+
Cu2+
𝐸∝ [𝐶𝑢2+ ], 𝐸∝ [𝑀𝑛+ ] Cu
Cu22+
+Cu
2+ 2
CuCu
+
Used for: determination of Metal ions (Cations)
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2- Electrode of second type
Silver
The electrode is a metal electrode which is covered with a metal
layer of its sparingly soluble salt dipped in solution if its
anion (THREE phases) 𝐴𝑔𝐶𝑙(𝑠)
Potential:
Potential 1/ [Anion]
Examples
Ag° electrode: Ag° / AgCl / Cl- EAg° 1/ [Cl-]
Calomel electrode: Hg° / Hg2Cl2 / Cl- EHg° 1/ [Cl-]
Mercury electrode: Hgo/ HgY2- /Y4- E 1/ [Y4-]
Used for:
Determination of ANIONS 5
3- Redox electrode:
The electrode is an inert wire, e.g. platinum wire put in a solution containing
oxidant and reductant in the same solution (ONE phase system electrode).
Potential: Platinum wire
E [Oxidized]/ [Reduced]
e.g Fe3+ / Fe2+ in presence of pt.
E25oC = Eo + 0.06 log [Fe3+]
n Fe2+ Fe3+
[Fe2+]
[ox] Fe3+
E25 C
o Fe2+
[Red]
Uses:
- To monitor the change in potential during redox titrations for concentration
determination
- To determine Eo for redox systems. 6
II. According to the Function
A) Reference Electrodes
Electrode with a known and constant potential,
Used as a reference to measure the potential of indicator
electrode through galvanic cell.
e.g.:1- Normal hydrogen electrode (N.H.E.),
2- Calomel electrode,
3- Silver electrode.
Indicator Reference
electrode electrode
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Normal hydrogen electrode (N.H.E)
H2/H+
Electrode reaction:
2H+ + 2e H2
Nernest equation:
E25oC = Eo + 0.06 log [H+]
i.e E [H+]
in N.H.E, [H+] = 1 , as log 1 = zero
Platinum black E25oC = Eo = zero
act as catalyst by
accumulation of H2
• As [H+]is fixed concentration , so the
potential is constant
Q. What if immersed in different conc. of HCl? 8
Advantage
It is a primary reference electrode ( electrode of first type), as its
potential is considered to be zero.
Disadvantages:
1- The presence of oxidant or reductant will interfere with the
equilibrium of the electrode.
2- We can't keep H2 gas at one atmosphere during all determinations
3- It needs replating of pt.black.
Thus, instead of this electrode, we use secondary reference
electrodes
e.g. Calomel or Silver electrode.
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Saturated Calomel Electrode
Hg/Hg2Cl2/Cl- ( sat) “ secondary type”
• As [Cl-]is fixed concentration , so the
potential is constant
Q. What if immersed in different conc. of KCl? 10
Saturated Silver Electrode
Ag/AgCl/Cl- ( sat) “ secondary type”
• As [Cl-]is fixed concentration , so the
potential is constant
Q. What if immersed in different conc. of KCl? 11
B) Indicator electrode
Indicator electrode is electrode dipped in unknown concentration of ions “ sample”
to determine its concentration
Its potential changes rapidly with the change of concentration of sample to be
determined.
It must give: 1- rapid response
2- Its response must be reproducible.
These electrodes are classified into two classes:
a)Metallic Electrodes b) Ion Selective Electrodes
where redox reaction (electron where charge (ions) exchange
transfer) takes place at electrode takes place at specific membrane
surface, It classified according to type of surface
reaction between standard and sample
Glass electrode
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Potentiometric Applications
1-Qualitative
2-Quantitative
(i)Direct potentiometry (Calibration Curve)
(ii)Indirect (Potentiometric titration curve)
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1) Quantitative
Determination of concentration of unknown sample
a) Direct potentiometry :-
By constructing a
calibration curve
1 2 3 4
Unknown sample log
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By constructing a calibration curve
- Prepare a series of standard solutions of
different concentrations of the same
substance of analyte to be measured.
- Measure the potential of the standard
solutions.
- Plot calibration curve of E versus log
concentration.
- Find the conc. of the unknown sample
from the calibration curve.
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b) Potentiometric titrations
• Measure potential of an indicator electrode
after successive addition of titrant
• Advantages over titrations with chemical
indicators:
o Provided more reliable data.
o Useful with colored or turbid samples
o Useful when no indicator is available
o Can be used in acid base ,
complexometric, preciptimetric and
redox titrations.
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1- Determination of pka of weak acid (e.g: CH3COOH)
1- Direct Potentiometry:
pH= ½ pKa + ½ pCa # NaOH
2- Indirect Potentiometry Na-acetate Acetic acid
Titration curve
Buffer is formed during titration
pH= pKa+ log [salt]/[ acid]
At half neutralization
[salt]=[ acid]
pH= pKa
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