MODULE 3

ELECTROCHEMISTRY
ELECTROCHEMISTRY
- branch of chemistry that deals with the interconversion of electrical energy and
chemical energy.
ELECTROCHEMICAL PROCESS
- are redox (oxidation-reduction) reactions in which the energy released by a
spontaneous reaction is converted to electricity or in which electrical energy is used to
cause a nonspontaneous reaction to occur
REDOX REACTIONS
- Electron-transfer reactions
- Oxidation: lose electrons
- Reduction: gain electrons
OXIDATION NUMBER
- Or oxidation state
- signifies the number of charges the atom would have in a molecule (or an ionic
compound) if electrons were transferred completely.
RULES FOR ASSIGNING OXIDATION NUMBERS
1. Elements that are not combined will have an oxidation number of 0.
Example: H2 , Br2 , Na, Be, K, O2 , P4 = 0
2. Elements in monoatomic ion will have an oxidation number equal to its charge.
Li+ ion = +1; Ba2+ ion = +2; I- ion = -1; O2- ion, -2
3. The oxidation number of oxygen is usually -2, except in peroxide (O2-2 ), it is -1.
H2O, O = -2 ; H2O2, O = -1
4. The oxidation number of H is +1 except if bonded to metals in a binary compound it
will be -1.
LiH, NaH, CaH → H = +1
5. The GIA will have a charge of +1, GIIA will have +2, and fluorine will also have a
charge of -1.
6. In a neutral molecule, the sum of the oxidation numbers of all the atoms must be zero.
In a polyatomic ion, the sum of oxidation numbers of all the elements in the ion must be
equal to the net charge of the ion.
 Example: in NH4+, the oxidation number of N is -3 and that of H is +1.
Thus -3 + 4(+1) = +1, which is equal to the net charge of the ion.
7. Oxidation numbers do not have to be integers.
Example :the oxidation number of O in the superoxide ion, O2-, is -1/2.
TYPES OF ELECTROCHEMICAL CELLS
GALVANIC CELL
- Energy released by spontaneous redox reaction is converted to electrical energy
ELECTROLYTIC CELL
- Electrical energy is used to drive nonspontaneous redox reaction
GALVANIC CELL
- Experimental apparatus for generating electricity through the use of a spontaneous
reaction (ΔG<0)
- Named after the Italian scientists Luigi Galvani and Alessandro Volta
- found in all batteries which are used to light your flashlight, load your gadgets, and
other electrical devices
- ANODE (Zn electrode)
- CATHODE (Cu electrode)
- REDCAT = (RED)uction (CAT)hode
- ANOX=(AN)ode (OX)idation)
SALT BRIDGE
• An inverted U tube containing an inert electrolyte solution, such as KCl or NH4NO3
CELL DIAGRAM
Zn (s) | Zn2+ (aq) (1 M) || Cu2+ (aq) (1 M) | Cu (s)
| - phase boundary
|| - salt bridge
Left side – anode
Right side – cathode
STANDARD REDUCTION POTENTIALS
- the voltage associated with a reduction reaction at an electrode when all solutes are 1
M and all gases are at 1 atm.
- Daniell cell: 1.10 V at 25°C
- For Hydrogen electrode (reference):
- H2 → 2H+ + 2e-
 - Under standard conditions:
- 2H+(1 M) + 2e- → H2(1 atm) E°= 0 V
- Standard hydrogen electrode (SHE)
KEYPOINTS USING THE TABLE
1. The E° values apply to the half-cell reactions as read in the forward (left to right)
direction
2. The more positive E° is, the greater the tendency for the substance to be reduced.
F2(1 atm) + 2e- → 2F-(1 M) E° = 2.87 V
Li+(1 M) + e- → Li(s) E° = -3.05 V
3. The half-reactions are reversible depending on the conditions whether it is used as an
anode or cathode but its magnitude remains the same
4. Changing the stoichiometric coefficient doesn’t change the value of Eo half-cell since this is
an intensive property.
F2(g) + 2e- → 2F-(aq) Eo = 2.87 V
2F2(g) + 4e → 4F (aq) Eo = 2.87 V
- -

THE EFFECT OF CONCENTRATION ON CELL EMF

• Nernst Equation
𝑜 0.0257 𝑉
𝐸𝑐𝑒𝑙𝑙 = 𝐸𝑐𝑒𝑙𝑙 − ln 𝑄 or
𝑛

𝑜
0.0592 𝑉
𝐸𝑐𝑒𝑙𝑙 = 𝐸𝑐𝑒𝑙𝑙 − l𝑜𝑔 𝑄
𝑛
For any conditions.

LESSON 3.2
BATTERIES
BATTERY
- a galvanic cell, or a series of combined galvanic cells
- can be used as a source of direct electric current at a constant voltage.
- completely self-contained
- requiring no auxiliary components such as salt bridges.
PRIMARY BATTERY
- Dry Cell / Alkaline Battery
- Mercury and Silver Button
- Primary Lithium Battery
DRY CELL
- Leclanché cell
ALKALINE BATTERY
- More expensive
MERCURY AND SILVER BUTTON BATTERY
- More expensive than dry cell
- Mercury battery: HgO - oxidizing agent
- Silver battery: Ag2O – oxidizing agent
PRIMARY LITHIUM BATTERY
- extremely high energy/mass ratio producing 1 mol of the electron (1 F) from less than
7g of Li metal
- anode - Li metal foil which requires a nonaqueous electrolyte
- cathode - metal oxide where Li+ lie between oxide layers
SECONDARY BATTERY
- lead-acid battery
- nickel-metal hydride (Ni-MH) battery
- lithium-ion battery
LEAD-ACID BATTERY
- six identical cells joined together in series
- anode – lead
- cathode - PbO2 packed on a metal plate
NICKEL-METAL HYDRIDE (Ni-MH) BATTERY
- Replacement for Nickel-cadmium battery
- Lightweight but high power
LITHIUM-ION BATTERY
- anode - conducting carbonaceous material, usually graphite, with spaces that hold Li
atoms and Li+ ions
- cathode - transition metal oxide such as CoO2, which can also hold Li+ ions
FUEL CELLS
- Special type of battery
- requires a continuous supply of reactants to keep functioning
CONCENTRATION CELLS
- a cell based solely on the emf generated because of a difference in a concentration
LESSON 3.3
CORROSION
CORROSION
- redox reaction thus metals that is with the lowest standard reduction potential are
preferably oxidized (corroded).
- When two different metals contact the corrosion of the more reactive metal will speed
up. The most reactive metals are those in Group IA.
- Some metals such as Al produce an insoluble oxide that adheres to the surface and
prevents further corrosion. Aluminum oxide is a powdery white or dull gray coating
and as it hardens it creates a protective layer over the newly exposed corroded
surface. Unlike the iron, the oxides formed will crumble and deteriorate the iron
metal further
- Corrosion such as rusting of iron will not occur in the absence of water. Water
contains electrolytes that may facilitate electron transfer from the anodic region to the
cathodic region of the metal. An example of an environment with high electrolyte
content is the sea which contains a lot of dissolved salt.
- The H+ ions are a catalyst for corrosion. The lower the pH in the environment means
the more acidic thus the faster the metal to corrode. Gaseous by-products of burning
fossil fuels such as the oxides of sulfur and nitrogen combine in water which yields
acidic products.
- Heat also plays a vital role in corrosion. A higher temperature is also accompanied by
higher rates of corrosion. Weather also affects how fast the metal corrodes. In cold
weather, corrosion is less but it can change based on other factors. Weather with a low
temperature but high humidity can lead to an increased rate of corrosion.

FACTORS AFFECTING CORROSION

• Nature of the Metal
• Nature of Oxide Forms
• Presence of Moisture and Electrolyte
• Acidity and alkalinity:
• Temperature
TYPES OF CORROSION
• Uniform Corrosion
• Bimetallic Corrosion
• Crevice Corrosion
• Pitting Corrossion
• Inter-Granular Corrosion
• Exfoliation Corrosion
• Stress Cracking Corrosion
• Cavitation Corrosion
• Hydrogen Embrittlement

LESSON 3.4
ELECTROLYSIS AND ELECTROPLATING
ELECTROLYSIS
- electrical energy is used to cause a nonspontaneous chemical reaction to occur
ELECTROLYTIC CELL
- an apparatus for carrying out electrolysis
STOICHIOMETRY OF ELECTROLYSIS
1 mole e- = 96,500 C
1 C =1A⋅ 1 s
Current (A) = charge (C) / time (s)