Redox Reactions

GCE Study Buddy Chemistry Notes

Oxidation and Reduction

Oxidation-reduction (redox) reactions involve transfer of
electrons Oxidation loss of electrons Reduction gain of electrons

Both half-reactions must happen at the same time

Any combustion process is classified as oxidation, as it

involves a gain in oxygen Eg, when methane burns, the carbon atoms in the methane
gain oxygen to form carbon dioxide and therefore have been oxidised. Can also think of the methane as losing hydrogen, which is also oxidation.

Oxidation and Reduction

Substances which help oxidation to occur are called
oxidising agents (oxidants) eg oxygen, acidifed potassium manganate(VIII), acidified
potassium dichromate

Substances which help reduction to occur are called

reducing agents (reductants) Eg carbon monoxide, carbon, hydrogen

Oxidation and Reduction

Oxidation Gain in oxygen Lose of electrons Lose of hydrogen Increase in oxidation state number Reduction Lose of oxygen Gain of electrons Gain in hydrogen Decrease in oxidation state number

Oxidising Agents are substances that Oxidise another substance & Reducing Agents are substances that Reduces another substance.

Question
(a) Define oxidation in terms of electron transfer.

(b) Name a substance which is an oxidizing agent in aqueous solution. Explain how aqueous potassium iodide can be used to confirm that this named substance is an oxidizing agent.
Answers
(a) Oxidation is the transfer of electron from one particle to another. The particle that looses the electron is said to be oxidized. (b) Chlorine is an oxidizing agent. Aqueous chlorine is added to aqueous potassium iodide with starch added. A dark blue solution is seen, indicating the presence of I2. So I- ion must have been oxidized to I2

Tests for oxidising and reducing agents

Test for oxidising agents
Add potassium iodide solution
If it changes from colorless to brown, than an oxidising agent
is present

Test for reducing agents

Add acidified potassium dichromate(VI).
If it changes from orange to green, then a reducing agent is
present

Oxidation States
Oxidation number assigned to element in molecule
based on distribution of electrons in molecule

There are set rules for assigning oxidation numbers

Substance All elements, noble gases, metals Group 1 ions, H+ Group 2 ions Al3+ Group 7 ions, Oxygen in H2O2, hydrogen in Metal hydrides e.g NaH O2-, S2-. Nitrides N3Oxidation number 0 +1 +2 +3 -1 -2 -3

Rules of oxidation number

Oxidation states and their colours

Chromium gives great example of different oxidation
numbers

Different oxidation states of chromium have different

colors Chromium (II) chloride = blue Chromium (III) chloride = green Potassium chromate = yellow Potassium dichromate = orange

Eg. Oxidation of Sodium chloride

Formation of sodium ions shows oxidation because each sodium atom loses an electron to become sodium ion Oxidation state represented by putting oxidation number above symbol of atom and ion Oxidation state of sodium changed from 0 (elemental state) to +1 (state of the ion) A species whose oxidation number increases is oxidized Sodium atom oxidized to sodium ion

Reduction
reactions in which the oxidation state of an element
decreases Eg. Chlorine in reaction with sodium Each chlorine atom accepts e- and becomes chloride ion

Oxidation state decreases from 0 to -1

A species that undergoes a decrease in oxidation state

is reduced

The chlorine atom is reduced to the chloride ion

Oxidation and Reduction as a Process

Electrons are made in oxidation and acquired in reduction

For oxidation to happen during chemical reaction, reduction

must happen as well

Number of electrons made in oxidation must equal number

of electrons acquired in reduction

Transfer of e- causes changes in oxidation states of one or

more elements

Oxidation-reduction reaction any chemical process in

which elements undergo changes in oxidation number

Eg. When copper oxidized and NO3- from nitric acid is

reduced

Half Reactions
Part of the reaction involving oxidation or reduction alone
can be written as a half-reaction

Overall equation is sum of two half-reactions Number of e- same of oxidation and reduction, they
cancel and dont appear in overall equation

Half Reactions
Electrons lost in oxidation appear on product side of
oxidation half-reaction

Electrons gained in reduction appear as reactants in

reduction half-reaction

When copper reacts in nitric acid 3 copper atoms are

oxidized to Cu+2 ions as two nitrogen atoms are reduced from a +5 oxidation state to a +2 oxidation state

Non-redox Reactions
If no atoms in reaction change oxidation state, it is NOT
a redox reaction

Eg. Sulfur dioxide gas dissolves in water to form acidic

solution of sulfurous acid

When solution of NaCl is added to solution of AgNO3, an

ion-exchange reaction occurs and white AgCl precipitates

Redox Reactions and Covalent Bonds

Substances with covalent bonds also undergo redox reactions

Unlike ionic charge, oxidation number has no physical meaning

Oxidation number based on electronegativity relative to other
atoms to which it is bonded in given molecule NOT based on charge

Eg. Ionic charge of -1 results from complete gain of one

electron by atom

An oxidation state of -1 means increase in attraction for a

bonding electron

Change in oxidation number does not require change in actual

charge

Redox Reactions and Covalent Bonds

When hydrogen burns in chlorine a covalent bond forms from sharing of
two e Two bonding e- in hydrogen chloride not shared equally

The pair of e- is more strongly attracted to chlorine atom because of

higher electronegativity

chlorine in HCl is assigned oxidation number of -1 Oxidation number for chlorine atoms changes from 0 So chlorine atoms are reduced oxidation number of each hydrogen atom in hydrogen molecule is 0 oxidation state of hydrogen atom in HCl is +1 Hydrogen atom oxidized

Redox Reactions and Covalent Bonds

No electrons totally lost or gained Hydrogen has donated a share of its bonding electron to chlorine It has NOT completely transferred that electron Assignment of oxidation numbers allows determination of partial
transfer of e- in compounds that are not ionic

Increases/decreases in oxidation number can be seen in terms of

completely OR partial loss or gain of e-

Reactants and products in redox reactions are not limited to

monatomic ions and uncombined elements

Elements in molecular compounds or polyatomic ions can also be

redoxed if they have more than one non-zero oxidation state Eg. copper and nitric acid

Redox Reactions and Covalent Bonds

Nitrate ion, NO3-, is converted to nitrogen monoxide,
NO

Nitrogen is reduced in this reaction Instead of saying nitrogen atom is reduced, we say
nitrate ion is reduced to nitrogen monoxide

Balancing Redox Equations

Equations for simple redox reactions can be balanced by
looking at them

Most redox equations require more systematic methods

Equation-balancing process needs use of oxidation

numbers

Both charge and mass are conserved

Half-reactions balanced separately then combined

Half-Reaction Method
1. Oxidation numbers assigned to all atoms and
polyatomic ions to determine which species are part of redox process

2. Half-reactions balanced separately for mass and

charge

3. Then added together

Half-Reaction Method
1. Write the equation. Then write the ionic equation

2. Assign oxidation numbers. Delete substances containing only elements that do not change oxidation states

Sulfur changes oxidation state from -2 to +6 Nitrogen changes from +5 to +4 Other substances deleted

3. Write the half-reaction for oxidation

In this eg, sulfur is being oxidized

a. Balance the atoms

To balance oxygen, H2O must be added to left side This gives 10 extra hydrogen atoms on that side So, 10 H atoms added to right side In basic solution, OH- ions and water can be used to balance atoms

b. Balance the charge

Electrons added to side having greater positive net charge Left side has no net charge Right side has +8 Add 8 electrons to product side oxidation of sulfur changes from -2 to +6 involves loss of 8 e-

4. Write the half-reaction for reduction

Nitrogen reduced from +5 to +4
a. Balance the atoms

H2O added to product side to balance oxygen atoms 2 hydrogen ions added to reactant side to balance H
atoms b. Balance the charge Electrons added to side having greater positive net charge

Left side has net charge of +1 1 e- added to this side balancing the charge

5. Conserve charge by adjusting the coefficients in front of the electrons so that the number lost in oxidation equals the number gained in reduction. Write the ratio of the number of electrons lost to the number of electrons gained

This ratio is already in lowest terms

If not, need to reduce Multiply oxidation half-reaction by 1

Multiple reduction half-reaction by 8

Electrons lost = electrons gained

6. Combine the half-reactions, and cancel out anything common to both sides of the equation.

Each side has 10H+, 8e-, and 4H2O They cancel out

7. Combine ions to form the compounds shown in the original equation. Check to ensure that all other ions balance.
The NO3- ion appeared as nitric acid in original equation Only 6 H ions to pair with 8 nitrate ions
So, 2 H ions must be added to complete this formula If 2 H ions added to left side, then 2 H ions must be added to the
right side

Sulfate ion appeared as sulfuric acid in original equation H ions added to right side used to complete formula for sulfuric
acid

Oxidizing and Reducing Agents

Reducing agent substance that has the potential to
cause another substance to be reduced They love electrons Attain a positive oxidation state during redox reaction Reducing agent is oxidized substance

Oxidizing agent substance that has the potential to

cause another substance to be oxidized Gain electrons Attain a more negative oxidation state during redox reactions Oxidizing agent is reduced substance

Strength of Oxidizing and Reducing Agents

Different substances compared and rated on
relative potential as reducing/oxidizing agents Eg. Activity series related to each elements
tendency to lose electrons

Elements lose electrons to positively charged ions

of any element below them in series

The more active the element the greater its

tendency to lose electrons

Better a reducing agent it is

Greater distance between two elements in list

means more likely that a redox reaction will happen between them

 Fluorine atom most most active oxidizing

agent because of strong attraction for its own e-,
fluoride ion is weakest reducing agent

Negative ion of strong oxidizing agent is weak

reducing agent

Positive ion of strong reducing agent is weak

oxidizing agent Eg. Li Strong reducing agents because Li is very
active metal When Li atoms oxidize they produce Li+ ions Li+ ions unlikely to reacquire e-, so its weak oxidizing agent

 Left column of each pair also shows relative

abilities of metals listed to displace other metals

Zinc is above copper so is more active reducing

agent Displaces copper ions from solutions of copper
compounds Copper ion is more active oxidizing agent than Zn

Any reducing agent is oxidized by oxidizing

agents below it

Eg. F2 displaces Cl-, Br-, and I- from their solutions

Auto-oxidation
Some substances can be both reduced and oxidized
Eg. Peroxide ions O2-2 has relatively unstable covalent bond

Each O atom has oxidation number of -1 Structure represents intermediate oxidation state between O2
and O2-2

So, peroxide ion is highly reactive

Hydrogen peroxide, H2O2, contains peroxide ion

Decomposes into water and oxygen as follows

Auto-oxidation
Hydrogen peroxide is both oxidized AND reduced
Oxygen atoms that become part of gaseous oxygen
molecules are oxidized (-1 0)

Oxygen atoms that become part of water are reduced (1 -2)

Autooxidation a process in which a substance acts

as both an oxidizing agent and a reducing agent

The substance is self-oxidizing and self-reducing

Auto-oxidation
Hydrogen peroxide is both oxidized AND reduced
Oxygen atoms that become part of gaseous oxygen
molecules are oxidized (-1 0)

Oxygen atoms that become part of water are reduced (1 -2)

Autooxidation a process in which a substance acts

as both an oxidizing agent and a reducing agent

The substance is self-oxidizing and self-reducing