ELECTROCHEMISTRY Oxidized substance and Reduced substance

 Branch of Chemistry that deals with the

interconversion of chemical energy and electrical
energy

Electrochemical processes

 Redox reaction in which energy released by Oxidation number (or state)

spontaneous reaction is converted to electricity
 Number assigned to the atoms in the molecule that
 Redox reaction in which electrical energy is used shows the general distribution of electrons among
to cause a non-spontaneous reaction to occur bonded atoms
Redox reaction  Oxidation number is the number of electrons
gained or lost by the element in making a
 derived from two reactions which involve compound
electron transfer: Reduction and Oxidation  Way of accounting for where the various electrons
which always occur simultaneously are in a compound
 Signifies the number of charges the atom would
Applications of Redox
have in a molecule if electrons were transferred
 Energy production completely
 Energy storage devices (batteries)
 Photographic processing
 Photosynthesis
 Cellular respiration
 Combustion of fuel
 Corrosion
 Bleaching

Redox Reaction

 Oxidation - reaction involving gain of oxygen

 Reduction - reaction involving removal of Oxygen

Oxidation

A chemical change in which a substance loses

electrons and thus increase in oxidation state.

Example: Mg → Mg2+ + 2e-

Reduction

A chemical change in which a substance gains

electrons and thus decreases in oxidation state
Redox reaction
Example: Cu2+ + 2e- → Cu
 Involves electron transfer

 Involves a change in the oxidation state of at

least two substances:
Redox – sum of two half-reactions Redox reaction

Mg → Mg2+ + 2e- Basis Oxidation Reduction

Cu2+ + 2e- → Cu Oxygen Gain O2 Loss2

Electrons Loss e- Gain e-

Oxidization increase decrease

state

Substances in redox

 Oxidizing agent

 Reducing agent
When a zinc strip is dipped into a copper(II) sulfate
Reducing agent
solution, electrons are transferred from zinc atoms to
copper ions.  Causes reduction of another substance by
providing electrons to another substance
Zn metal  Contains atom that shows increase in oxidation
With time, Cu plates out onto number
Zn metal strip, and Zn strip  Substance that is oxidized
Cu2+ ions  contains active metals that have low
“disappears.”
electronegativity and tend to give up electrons
Zn is oxidized and is the reducing agent readily
Zn(s) ---> Zn2+(aq) + 2e-  Also include substances that burn easily
forming strong bonds with O2 like H2, Carbon
Cu2+ is reduced and is the oxidizing agent and CH4
Cu2+(aq) + 2e- ---> Cu(s)
Oxidizing agent
Electrons are transferred from zinc atoms to copper
atoms.  causes the oxidation of another substance by
accepting electron from that substance
Zn(s) + Cu2+(aq) → Zn2+(aq) + Cu(s)  shows decrease in oxidation number
Redox  substance reduced
 strong oxidizing agents contain an atom with
Mnemonic commonly used to differentiate oxidation- high electronegativity such as F, O and Cl
reduction  If changes in oxidation number occur, the
reaction is a redox reaction.
“oil rig”  The element whose oxidation number increases
is oxidized and is the reducing agent.
Oxidation Is Loss of electron,
 The element whose oxidation number decreases
Reduction Is Gain of electron is reduced and is the oxidizing agent.

“leo ger”

Loss of Electron is Oxidation,

Gain of Electron is Reduction

Common oxidizing and reducing agents

Oxidizing Agent Reducing agent

O2 H2

metals
F2, Cl2, Br2, I2

HNO3 C

MnO4- Hydrocarbons

Cr2O72-

Where there is oxidation there is always reduction

Balancing redox reaction
Oxidizing agent Reducing agent
Principle in balancing redox reaction
Is itself reduced Is itself oxidized The number of electrons lost in oxidation must be equal
to the electrons gained in the reduction
Gains electrons Loses electrons
Increase in oxidation number = decrease in oxidation
Causes oxidation Causes reduction number

Method is balancing redox

For any two metals in an activity series, the more active 1. Half reaction method / ion electron method
metal is the more readily oxidized.
2. Valence electron method / oxidation number
method

Balancing redox equations: systematic methods

Oxidation number method – tracking changes in the

oxidation numbers

Half-reaction method – tracking changes in the flow of

electrons

Number of electrons gained must equal the number of

electrons lost.

Use oxidation numbers to determine what is oxidized

and what is reduced.
HALF REACTION METHOD 2Cr(s) + 3Ni+2(aq) → 2Cr+3(aq) + 3Ni(s)

 Also known as Ion-electron approach Oxidizing and reducing agents:

 The overall reaction is divided into 2 half
reactions, one for oxidation, one for reduction Oxidizing Agent - Ni+2(aq)
 the equations for the 2 reactions are balanced Reducing Agent - Cr(s)
separately and then added together to give the
overall balanced equation Balancing Redox in Aqueous Solution

Balancing Redox Equations in acidic solutions

1) Determine the oxidation numbers of atoms in both

reactants and products.

2) Identify and select out those which change oxidation

number (“redox” atoms) into separate “half reactions”.

3) Balance the “redox” atoms and charges (electron gain

and loss must equal!).

4) In acidic reactions balance oxygen with water, then

hydrogen from water with acid proton(s).

Example 1:

Fe+2(aq)+ Cr2O72-(aq) +H+(aq)  Fe3+(aq) + Cr3+(aq) + H2O(l)

Example 1: Fe 2+(aq)+ Cr2O72-(aq) +H+(aq)  Fe 3+(aq) + Cr 3+(aq) +H2O(l)

Ag+ + 1e- → Ag ? Cr oxidation number?

Al → Al3+ + 3e- x = ? Cr ; 2x+7(-2) = -2; x = +6

Fe 2+(aq)  Fe 3+(aq) + e -

Cr2O72-(aq) +  2Cr 3+(aq)

In the following redox reaction, which species is being
oxidized? Which one is being reduced?
Al(s) is being oxidized.
Ag+ (aq) is being reduced.
Cr = (6+)
6 (Fe 2+(aq) Fe3+(aq) + e - )
6 Fe 2+(aq)  6 Fe3+(aq) + 6 e -

Example 2: Cr(s) → Cr+3(aq) + 3e- Cr2O72-(aq) + 6 e -  2 Cr3+(aq)

Ni+2(aq) + 2e- → Ni(s) 6 Fe2+(aq)+ Cr2O72-(aq) + H+(aq)  6 Fe3+(aq) + 2 Cr3+(aq)+

H2O(l)
2Cr(s) → 2Cr+3(aq) + 6e-
Oxygen = 7 Hydrogen =1 Oxygen = 1 Hydrogen = 2
3Ni+2(aq) + 6e- → 3Ni(s)
Completely Balanced Equation:
2Cr(s) + 3Ni+2(aq) → 2Cr+3(aq) + 3Ni(s)
6 Fe2+(aq)+ Cr2O72-(aq) + 14 H+(aq)  6 Fe3+(aq) +
How many electrons are being transferred? 6 e-
2 Cr3+(aq)+ 7 H2O(l)
Balancing Redox Equations in basic solutions

1) Determine oxidation numbers of atoms in Reactants

and Products

2) Identify and select out those which change oxidation

number into separate “half reactions”

3) Balance redox atoms and charges (electron gain and

loss must equal!)

4) In basic reactions balance the Oxygen with hydroxide

then Hydrogen from hydroxide with water

Example:

MnO2 (aq)+ ClO31-(aq) + OH 1-aq)  MnO41- (aq)+ Cl 1-(aq) +

H2O(l)

MnO2  MnO4 1- + 3e-

Mn4+ Mn7+

ClO3 1- + 6 e-  Cl 1-

Cl+5

( MnO2  MnO4 1- + 3e- ) x 2

Mn4+ Mn7+

2 MnO2  2MnO4 1- + 6e-

ClO3 1- + 6 e-  Cl 1-

2 MnO2 (aq)+ ClO31-(aq)  2 MnO4 (aq)1- +Cl 1- (aq)

2MnO2 (aq)+ ClO31-(aq) + OH 1-aq)  2MnO41- (aq)+ Cl 1-(aq) +

H2O(l)

8 Oxygen 9 Oxygen

1 Hydrogen 2 Hydrogen

Completely Balanced Equation:

2 MnO2(aq)+ ClO31-(aq) + 2 OH 1-(aq)  2 MnO4(aq)1- + Cl1-(aq)

+ 1 H2O(l)