Fundamentals of Electrochemistry

Subject: CHEM 725

Lecturer: Darwin F. Reyes, RCh, MSc

Outline:

 Redox reactions
 Electrochemical cells
 Cell potential
 Nernst equation

 Electrochemistry is the study of the interaction of

chemical reactions and electrical work.

 Electrochemical reactions are driven by the

movement of electron from one species to another.
 Movement of electron → redox reaction

 Redox reactions are reactions where species

undergo changes in the oxidation numbers.
 Oxidation number or oxidation state refers to
number of charges an atom would have in a molecule
if electrons were transferred completely based on the
differences on the electronegativity.
 Reduction reactions - gaining of e-s of oxidizing
agents
 Oxidation reactions - loss of e-s of reducing agents

 GEROA - Gain Electrons, Reduction, Oxiding

Agent
 LEORA - Loss Electrons, Oxidation, Reducing
Agent

Example:

 There are changes in the oxidation numbers,therefore

the reaction is a redox reaction.
Parts of a Voltaic Cell

 No changes in the oxidation numbers, therefore the
reaction is not a redox process.
1. Electrodes
 Anode - electrode where oxidation occurs; usually at
th left side; negative electrode
 Cathode - electrode where reduction occurs; usually
at the right side; positive electrode

Electrochemical Cells
→ Electrochemical system where the components
involved undergo redox processes.
 2 types of electrochemical cells based on the
spontaneity of process:
1. Voltaic/Galvanic cell - driven by a spontaneous redox
reaction (ΔG < 0) to generate electrical energy
2. Electrolytic cell - involves a redox reaction that is not
spontaneous (ΔG > 0) and requires an input of
electrical energy to accomplish a redox process.
→ AnOX, RedCat
2. Electrolyte solution - mixture of ions that are involved
in the reaction or ions that carry the charge
→ Zn electrode is dipped in Zn2+ solution
→ Cu electrode is dipped in Cu2+ solution
3. Salt bridge - serves as contact between the cathodic
and anodic compartments.
→ usually soluble salt in agar mixture
→ example: KNO3; K+ goes to the cathodic compartment
while NO3- goes to the anodic compartment

 Half-cell reactions - individual oxidation and  Inactive electrodes - electrodes used in the
reduction reactions electochemical cell set-up but that is not part of the
X → X+ + e- (oxidation) redox reaction; used if the reaction components does
Y+ + e- → Y (reduction) not have a physically available electrode. Examples
are carbon (graphite) and platinum.
Notation for a Voltaic Cell Solution:

Where: | refers to a phase boundary

|| is the salt bridge

Cell potential (E°cell)

- electrical energy proportional to the differences in

electrical potential between the two electrodes

Ecell > 0 - E for a spontaneous process

Ecell < 0 - E for a nonspontaneous process
Ecell = 0 - E for a reaction at equilibrium 2. What is the E for the Cu2+/Cu//Ag+/Ag cell if [Cu2+] =
0.10 M and [Ag+] = 10–2 M at 25°C?
 Standard cell potential (E°cell) - cell potential
measured at standard conditions Solution:
 Standard electrode potential (E°half-cell) - electrical
potential at a given half-cell reaction with all
components in a standard states

→ E°cell can be calculated from:

E°cell = E°cathode - E°anode

in some reference books: E°cell = E°right - E°left

E°cell = E°+ - E°-

→ Based on the standard cell potential tables, higher +E°

values > -E° values, that is, +2.87 V > 0.00 V > -0.76 V >
-3.05 V

Example: References:

(1) Ag+ + e- → Ag E° = 0.80 V Harris DC (2010). Quantitative Chemical Analysis (8th ed)
(2) Sn2+ + 2e- → Sn E° = -0.14 V New York, NY: W.H. Freeman and Company

1. Assign which reaction is a anodic or cathodic reaction. Skoog DA et al. (2014). Fundamental of Analytical
Since 0.80 V > -0.14 V, Ag is the cathode while Sn is the Chemistry (9th ed) Belmont, CA: Brooks/Cole
anode.
2. Reverse equation (2) to Sn → Sn2+ + 2e
3. Multiply equation (1) by 2 to balance the number of e-s
involved since for a redox reaction, number of e-s lost is
equal to the number of e-s gained. Take note that the
equation is multiplied by a factor but not the value of E°.
4. To calculate the E°, subtract 0.80 V to -0.14 V.
5. Therefore the final equation is 2Ag+ + Sn →2 Ag + Sn2+
and the E°cell = 0.94 V

Other example: Galvanic cell composed of Cl2 and Ni. E°cell

= 1.61 V

Nernst equation

- considers the effect of change in concentration in the

E°cell value obtaining a new E° value.

0.0592
E   E  cell  log K
n (at 25 °C)

Where n = number of electrons involved

Example:
1. What is the E for the Fe3+/Fe2+ half-cell if [Fe3+] = 10–4 M
and [Fe2+] is 10–1 M at 25°C?