Oxidation-Reduction Reactions

• The term oxidation was originally used to describe reactions in which an element
combines with oxygen.
• Example: The reaction between magnesium metal and oxygen to form magnesium oxide
involves the oxidation of magnesium.
2 Mg(s) + O2(g)  2 MgO(s)

• The term reduction comes from the Latin stem meaning "to lead back." Anything that that
leads back to magnesium metal therefore involves reduction.
• The reaction between magnesium oxide and carbon to form magnesium metal and carbon
monoxide is an example of the reduction of magnesium oxide to magnesium metal.

MgO(s) + C(s) Mg(s) + CO(g)

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 Oxidation–Reduction Reactions

Involves 2 Steps
Oxidation = Loss of Electrons (LEO)
Na Na+ + e Oxidation Half-Reaction
Reduction = Gain of electrons (GER)
Remember this
Cl2 + 2e 2Cl Reduction Half-Reaction phrase: LEO the lion
Net reaction: says GER.
2Na + Cl2  2Na+ + 2Cl
• Oxidation & reduction always occur together
• Can't have one without the other
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• LEO = Loss of Electrons is Oxidation
• GER = Gain of Electrons is Reduction
• Another way is to simply remember that reduction is to reduce the
oxidation number.
• Therefore, oxidation must increase the value.
• Oxidizing Agent - that substance which oxidizes somebody else. It is
reduced in the process.
• Reducing Agent - that substance which reduces somebody else. It is
oxidized in the process.

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Predicting oxidation numbers
• Oxidation number of atoms in element is zero in all cases
• Oxidation number of element in monatomic ion is equal to the
charge
• sum of the oxidation numbers in a compound is zero
• sum of oxidation numbers in polyatomic ion is equal to the
charge
• F has oxidation number –1
• H has oxidn no. +1; except in metal hydrides where it is –1
• Oxygen is usually –2. Except:
• O is –1 in hydrogen peroxide, and other peroxides
• O is –1/2 in superoxides KO2
• In OF2 O is +2
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Ex. Assigning Oxidation Number
1. Li2O
Li (2 atoms) × (+1) = +2
O (1 atom) × (–2) = –2
sum = 0
+2 –2 = 0 so the charges are balanced to zero
2. CO2
C (1 atom) × (x) = x
O (2 atoms) × (–2) = –4
sum = 0
x  4 = 0 or x = +4
C is in +4 oxidation state

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Learning Check
Assign oxidation numbers to all atoms:
Ex. ClO4
O (4 atoms) × (–2) = –8
Cl (1 atom) × (–1) = –1
(molecular ion) sum ≠ –1
O (4 atoms) × (–2) = –8
Cl (1 atom) × (x) = x
sum = –1–8 + x = –1 or x = 8 –1
So x = +7; Cl is oxidation state +7

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 Learning Check
Assign Oxidation States To All Atoms:
• MgCr2O7
Mg =+2; O = –2; and Cr = x (unknown)
+2 + 2x + {7 × (–2)} = 0
2x – 12 = 0 x = +3
Cr is oxidation # of +3
• KMnO4
K =+1; O = – 2; so Mn = x
+1 + x + {4 × (–2)} = 0
x–7=0 x = +7
Mn is oxidation # of +7

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 Redefine Oxidation-Reduction in
Terms of Oxidation Number
• A redox reaction occurs when there is a change in oxidation
number.
Oxidation
• Increase in oxidation number
• e loss
Reduction
• Decrease in oxidation number
• e gain

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Using Oxidation Numbers to
Recognize Redox Reactions
• Sometimes literal electron transfer:
decrease reduction
increase oxidation

+2 0 +2 0
Cu2+ + Zn Zn2+ + Cu
Cu: oxidation number decreases by 2
 reduction
Zn: oxidation number increases by 2
 oxidation

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Using Oxidation Numbers to Recognize
Redox Reactions
• Sometimes electron transferred in "formal" sense.
O: decrease reduction

C: increase oxidation

-4 +1 0 +4 -2 +1 -2
CH4 + 2O2 CO2 + 2H2O
• O: oxidation number decreases by 2
 reduction
• C: oxidation number increases by 8
 oxidation
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What is the oxidation number of
1) N in NO3¯
2) C in CO32¯
3) Cr in CrO42¯
4) Cr in Cr2O72¯
5) Fe in Fe2O3
6) Pb in PbOH+
7) V in VO2+
8) V in VO2+
9) Mn in MnO4¯
10) Mn in MnO42¯ 11
 What is a Half-Reaction?
• A half-reaction is simply one which shows either reduction OR
oxidation, but not both. Here is an example redox reaction:
• Ag+ + Cu ---> Ag + Cu2+
• It has BOTH a reduction and an oxidation in it. That is why we call it a
redox reaction, from REDuction and OXidation.

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• What you must be able to do is look at a redox reaction and separate out
the two half-reactions in it. To do that, identify the atoms which get
reduced and get oxidized. Here are the two half-reactions from the
example:
Ag+ ---> Ag
Cu ---> Cu2+
• The silver is being reduced, its oxidation number going from +1 to zero.
The copper's oxidation number went from zero to +2, so it was oxidized in
the reaction. In order to figure out the half-reactions, you MUST be able to
calculate the oxidation number of an atom.

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• When you look at the two half-reactions, you will see they are already
balanced for atoms with one Ag on each side and one Cu on each side. So, all
we need to do is balance the charge.
• To do this you add electrons to the more positive side. You add enough to
make the total charge on each side become EQUAL.
• To the silver half-reaction, we add one electron:
Ag+ + e¯ ---> Ag
• To the copper half-reaction, we add two electrons:
Cu ---> Cu2+ + 2e¯
Half-reactions NEVER occur alone.

notice that each half-reaction wound up with a total charge of zero on each side.
This is not always the case. You need to strive to get the total charge on each
side EQUAL, not zero.
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Half-Reactions Practice Problems
Balance each half-reaction for atoms and charge:
1) Cl2 ---> Cl¯
2) Sn ---> Sn2+
3) Fe2+ ---> Fe3+
4) I3¯ ---> I¯
5) ICl2¯ ---> I¯

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 Answers
1) Cl2 + 2e¯ ---> 2Cl¯
2) Sn ---> Sn2+ + 2e¯
3) Fe2+ ---> Fe3+ + e¯
4) I3¯ + 2e¯ ---> 3I¯
5) ICl2¯ + 2e¯ ---> I¯ + 2Cl¯

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Balancing Redox Equations in
Aqueous Solutions
• Many redox reactions in aqueous solution involve H2O
and H+ or OH
• Balancing the equation cannot be done by inspection.
• Need method to balance equation correctly
• Start with acidic solution then work to basic conditions

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Ion-Electron Method – Acidic Solution

1. Divide equation into 2 half-reactions

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Ion-Electron in Basic Solution
• The simplest way to balance an equation in basic
solution
Use steps 1-7 above, then
8. Add the same number of OH– to both sides of the
equation as there are H+.
9. Combine H+ & OH– to form H2O
10. Cancel any H2O that you can from both sides

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