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Lesson Objectives

At the end of this lesson, the❑ Recall the interconversion

(1) Introduction to
Electroanalytical Techniques
Jonyl L. Garcia, M.Sc., RCh.
Assistant Professor
Chemistry Department
student would be able to: between standard reduction
❑ Recall how to balance redox potentials, standard Gibbs
reactions; free energy, and equilibrium
❑ Recall the parts of an constants;
electrochemical cell; ❑ Recall the criteria for reaction
❑ Recall the cell notation; spontaneity;
❑ Recall the two types of❑ Recall the Nernst Equation
electrochemical cells; and associatied calculations;
❑ Recall the concept ❑
of Calculate for the cell potential
standard reduction potentials; associated with systems
involving precipitates or
complex ions.

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Electroanalytical Techniques

• Concerned with interplay between electricity and

chemistry
• Measurement of electrical quantities (e.g. current,
potential, charge) and their relationship to chemical
parameters (e.g. concentration)
• Applications
– Quality Control
–
REVIEW OF BASIC –
Research and Development
Environmental Monitoring
ELECTROCHEMISTRY – Medical Diagnostics
– Fundamental Research

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Family Tree of Electroanalytical Methods Electrochemical Processes

Electrochemical processes are oxidation-reduction reactions
in which:
• the energy released by a spontaneous reaction is
converted to electricity or
• electrical energy is used to cause a nonspontaneous
reaction to occur
0 0 2+ 2-
2Mg (s) + O2 (g) 2MgO (s)

2Mg 2Mg2+ + 4e- Oxidation half-reaction (lose e-)

O2 + 4e- 2O2- Reduction half-reaction (gain e-)

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Exercise 1 Redox Reactions & Electrochemical Cells

Acidic condition: ➢ In an electrochemical

cell, oxidizing agent
and the reducing
agent are physically
separated from each
other.
➢ Cell potential, is a
Basic condition: measure of the
NH3 + ClO¯ → N2H4 + Cl¯ tendency of the cell
Mn2+ Sn4+ → MnO2(s) + Sn2+ reaction to proceed
toward equilibrium.

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Parts of an Electrochemical Cell Types of Electrochemical Cells

➢ The cathode in an electrochemical cell is the electrode at ➢Galvanic, or voltaic, cells store electrical energy.
which a reduction reaction occurs.
➢Galvanic cells operate spontaneously,
➢ The anode is the electrode at which an oxidation takes
place.

➢An electrolytic cell requires an external source of

➢ A salt bridge isolates the reactants but maintains
electrical contact between the two halves of the cell.
electrical energy for operation.

➢ By convention, anode is drawn on the left-hand side,

while the cathode is drawn on the right-hand side.

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Cell Notation Standard Reduction Potentials

Zn (s) + Cu2+ (aq) Cu (s) + Zn2+ (aq)

[Cu2+] = 1 M and [Zn2+] = 1 M

Cell Diagram

phase boundary
Zn (s) | Zn2+ (1 M) || Cu2+ (1 M) | Cu (s)
anode salt bridge cathode

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SRP is determined experimentally SRP is determined experimentally

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SRP is determined experimentally

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Cell Potentials and Spontaneity

Type Reaction Anode Cathode Cell Potential ΔG0
Galvanic Spontaneous (-) (+) (+) (-)
Electrolytic Nonspontaneous (+) (-) (-) (+)

CELL POTENTIALS AND

SPONTANEITY

Analytical Chemistry 3: Module 1-2

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Exercise - 2 Exercise - 3

A galvanic cell consists of a Mg electrode in a 1.0 M

Mg(NO3)2 solution and Ag electrode in a 1.0 M AgNO3
solution. Write the cell notation for the electrochemical
cell and calculate the standard emf of this cell at 25°C.
E°Cu2+/Cu+ = 0.15 V
E°Sn2+/Sn = - 0.14 V

Analytical Chemistry 3: Module 1-2

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Exercise - 4 The Effect of Concentration on Cell Potential

DG = DG0 + RT ln Q DG = -nFE DG0 = -nFE 0

-nFE = -nFE0 + RT ln Q
Nernst equation

E°Ca2+/Ca = - 2.87 V
E = E0 - RT ln Q
nF
E°Au3+/Au= 1.50 V
At 298 K

0.0257 V 0.0592 V
E =E 0 - ln Q E =E 0 - log Q
n n

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Writing Nernst Expressions: Example - Writing Nernst Expressions: Example -

A B

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Writing Nernst Expressions: Example - Writing Nernst Expressions: Example -

C D

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Writing Nernst Expressions: Example -
E Writing Nernst Expressions
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Standard Reduction Potential:
Summary
• The standard electrode potential is a relative quantity.
• The standard electrode potential for a half-reaction
refers exclusively to a reduction reaction.
• The standard electrode potential measures the
relative force tending to drive the half-reaction from a
state in which the reactants and products are at unit
activity
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Standard Reduction Potential:
Summary
• The standard electrode potential is independent of
the number of moles of reactant and product shown.
• A positive electrode potential indicates that the half-
reaction in question is spontaneous with respect to
the standard hydrogen electrode half-reaction.
• The standard electrode potential for a half-reaction is
temperature dependent.
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Exercise - 5 Exercise - 6

Consider the galvanic cell shown below. In a certain

experiment, the emf (E) of the cell is found to be 0.54 V
at 25°C. Suppose that [Zn2+] = 1.0 M and PH2 = 1.0
atm. Calculate the molar concentration of H+.

E°Fe2+/Fe = - 0.44V
E°Co2+/Co = - 0.28 V

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Systems Involving Precipitates or Complex Systems Involving Precipitates or Complex

Ions Ions

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Systems Involving Precipitates or

Complex Ions
Exercise - 7

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Concentration Cells

QUESTIONS?

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