Oxidation and Reduction F321 1

OXIDATION NUMBERS
Used to • tell if oxidation or reduction has taken place
• work out what has been oxidised and/or reduced
• construct half equations and balance redox equations

Atoms and ‘The number of electrons which must be

simple ions added or removed to become neutral’

atoms Na in Na = 0 neutral already ... no need to add any electrons

cations Na in Na+ = +1 need to add 1 electron to make Na+ neutral

anions Cl in Cl¯ = −1 need to take 1 electron away to make Cl¯ neutral

Q.1 What is the oxidation state of the elements in ?

a) N b) Fe3+ c) S2-

d) Cu e) Cu2+ f) Cu+

Molecules ‘The sum of the oxidation numbers adds up to zero’

Elements H in H2 = 0

Compounds C in CO2 = +4 and O = -2 +4 and 2(-2) = 0

• CO2 is neutral, so the sum of the oxidation numbers must be zero

• one element must have a positive ON, the other must be negative
• the more electronegative species will have the negative value
• electronegativity increases across a period and decreases down a group
• O is further to the right in the periodic table so it has the negative value (-2)
• C is to the left so it has the positive value (+4)
• one needs two O’s at -2 each to balance one C at +4

Q.2 If the oxidation number of O is -2, state the oxidation number of the other element in...

a) SO2 b) SO3 (c) NO d) NO2

e) N2O f) MnO2 g) P4O10 h) Cl2O7

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2 F321 Oxidation and Reduction

Complex ‘The sum of the oxidation numbers adds up to the charge on the ion’
ions
in SO42- S = +6 , O = -2 [ i.e. +6 + 4(-2) = -2 ] the ion has a 2- charge

Example What is the oxidation number (O.N.) of Mn in MnO4¯ ?

• the O.N. of oxygen in most compounds is -2

• there are 4 O’s so the sum of the O.N.‘s = -8
• the overall charge on the ion is -1, ∴ sum of all the O.N.‘s must add up to -1
• the O.S. of Mn plus the sum of the O.N.‘s of the four O’s must equal -1
• therefore the O.N. of Manganese in MnO4¯ = +7

WHICH OXIDATION NUMBER ?

• elements can exist in more than one oxidation state

• certain elements can be used as benchmarks

HYDROGEN (+1) except 0 atom (H) and molecule (H2)

-1 hydride ion, H¯ [in sodium hydride, NaH]

OXYGEN (-2) except 0 atom (O) and molecule (O2)

-1 in hydrogen peroxide, H2O2
+2 in F2O

FLUORINE (-1) except 0 atom (F) and molecule (F2)

Metals • have positive values in compounds

• value is usually that of the Group Number Al is +3
• values can go no higher than the Group No. Mn can be +2,+4,+6,+7

Non metals • mostly negative based on their usual ion Cl is usually -1

• can have values up to their Group No. Cl can be +1, +3, +5, +7
• to avoid ambiguity, the oxidation number is often included in the name
e.g. manganese(IV) oxide shows Mn is in the +4 oxidation state in MnO2
sulphur(VI) oxide for SO3
dichromate(VI) for Cr2O72-
phosphorus(V) chloride for PCl5.

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Oxidation and Reduction F321 3

Q.3 What is the theoretical maximum oxidation state of the following elements ?

Na P Ba Pb S Mn Cr

State the most common and the maximum oxidation number in compounds of...
Li Br Sr O B N
COMMON

MAXIMUM

Q.4 Give the oxidation number of the element other than O, H or F in

SO2 NH3 NO2 NH4+
IF7 Cl2O7 MnO42- NO3¯
NO2¯ SO32- S2O32- S4O62-

What is odd about the value of the oxidation state of S in S4O62- ?

Can it have such a value ? Can you provide a suitable explanation ?

Q.5 What is the oxidation number of each element in the following compounds ?
CH4 C= PCl3 P= NCl3 N=
H= Cl = Cl =

CS2 C= ICl5 I= BrF3 Br =

S= Cl = F=

MgCl2 Mg = H3PO4 H= NH4Cl N=

Cl = P= H=
O= Cl =

H2SO4 H= MgCO3 Mg = SOCl2 S=

S= C= O=
O= O= Cl =

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4 F321 Oxidation and Reduction

REDOX REACTIONS
O.S.
Redox When reduction and oxidation take place +7
+6
Oxidation Removal of electrons; species get less negative / more positive
+5
Reduction Gain of electrons; species becomes more negative / less positive +4
+3 O R
X E
REDUCTION in O.N. Species has been REDUCED +2
I D
+1 D U
e.g. Cl is reduced to Cl¯ (0 to -1)
0 A C
-1 T T
I I
-2 O O
INCREASE in O.N. Species has been OXIDISED
-3 N N
e.g. Na is oxidised to Na+ (0 to +1) -4
-5
-6
-7

OIL RIG Oxidation Is the Loss

Reduction Is the Gain of electrons

Q.6 Classify the following (unbalanced) changes as oxidation, reduction or neither.

a) Mg ——> Mg2+ b) O2- ——> O

c) Al3+ ——> Al d) Fe3+ ——> Fe2+

e) Ti3+ ——> Ti4+ f) 2Q ——> Q2

Q.7 What change takes place in the oxidation state of the underlined element ?
Classify the change as oxidation (O), reduction (R) or neither (N).
a) NO3¯ ——> NO b) HNO3 ——> N2O

c) CH4 ——> CO d) Cr2O72- ——> Cr3+

e) SO32- ——> SO42- f) Cr2O72- ——> CrO42-

g) H2O2 ——> H2O h) H2O2 ——> O2

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Oxidation and Reduction F321 5

How to balance redox half equations

Step 1 Work out the formula of the species before and after the change;
2 If different numbers of the relevant species are on both sides, balance them
3 Work out the oxidation number of the element before and after the change
4 Add electrons to one side of the equation so the oxidation numbers balance
5 If the charges on all the species (ions and electrons) on either side of the
equation do not balance, add H+ ions to one side to balance the charges
6 If the equation still doesn’t balance, add sufficient water molecules to one side

Example 1 Iron(II) being oxidised to iron(III).

Steps1/2 Fe2+ ———> Fe3+

Step 3 +2 +3
Step 4 Fe2+ ———> Fe3+ + e¯ now balanced

Example 2 MnO4¯ being reduced to Mn2+ in acidic solution

Steps 1/2 MnO4¯ ——> Mn2+

Step 3 +7 +2
Step 4 MnO4¯ + 5e¯ ——> Mn2+
Step 5 MnO4¯ + 5e¯ + 8H+ ———> Mn2+
Step 6 MnO4¯ + 5e¯ + 8H+ ——> Mn2+ + 4H2O now balanced

Q.8 Balance the following half equations

I2 —> I¯

C2O42- —> 2CO2

H2O2 —> O2

H2O2 —> H2O

Cr2O72- —> Cr3+

SO42- —> SO2

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6 F321 Oxidation and Reduction

Combining half equations

A combination of two ionic half equations, one involving oxidation and the other reduction,
produces a balanced REDOX equation. The equations can be balanced as follows...

Step 1 Write out the two half equations

2 Multiply the equations so that the number of electrons in each is the same
3 Add the equations and cancel out the electrons on either side of the equation
4 If necessary, cancel out any other species which appear on both sides

Example The reaction between manganate(VII) and iron(II).

Step 1 Fe2+ ——> Fe3+ + e¯ Oxidation

MnO4¯ + 5e¯ + 8H+ ——> Mn2+ + 4H2O Reduction

Step 2 5Fe2+ ——> 5Fe3+ + 5e¯ multiplied by 5

+ 2+
MnO4¯ + 5e¯ + 8H ——> Mn + 4H2O multiplied by 1

Step 3 MnO4¯ + 5e¯ + 8H+ + 5Fe2+ ——> Mn2+ + 4H2O + 5Fe3+ + 5e¯

MnO4¯ + 5e¯ + 8H+ + 5Fe2+ ——> Mn2+ + 4H2O + 5Fe3+ + 5e¯

gives MnO4¯ + 8H+ + 5Fe2+ ——> Mn2+ + 4H2O + 5Fe3+

Q.9 Construct balanced redox equations for the reactions between

a) Mg and H+
b) Cr2O72- and Fe2+
c) H2O2 and MnO4¯
d) C2O42- and MnO4¯
e) S2O32- and I2
f) Cr2O72- and I¯

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