OXIDATION - REDUCTION REACTIONS

[MH5; 4.4]

• Commonly called Redox reactions, these reactions involve a transfer

of electrons - one species gives them up, another receives them.
• They are easiest to deal with if we divide the overall reaction into
two half - reactions.
• In one half-reaction, electrons are LOST; this is called the
OXIDATION half - reaction.

EXAMPLES:
a) Na ! Na+ + e— b) Fe2+ ! Fe3+ + e—
• In each case, the reactant is losing electrons.

• In the other half!reaction, electrons are GAINED; this is called

the REDUCTION half!reaction.

EXAMPLES:
a) CR2 + 2 e— ! 2 CR— b) Cu2+ + 2 e— ! Cu
• In each case, the reactant is gaining electrons.

• It may help to remember that “ LEO says GER ” ......

Loss of Electrons is Oxidation and Gain of Electrons is Reduction

• The reactant taking part in the oxidation half - reaction is called

the REDUCING AGENT because it is reducing the other reactant.
• In doing so, it is OXIDIZED !
• The reactant taking part in the reduction half -reaction is called
the OXIDIZING AGENT because it is oxidizing the other
reactant.
• In doing so, it is REDUCED !

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EXAMPLE: 2 Fe2+ + CR2 ! 2 Fe3+ + 2 CR—

• Fe2+, the reducing agent, is reducing CR2; the Fe2+ is oxidized.

• CR2, the oxidizing agent, is oxidizing Fe2+; the CR2 is reduced
• Reduction and oxidation always go together; one cannot occur
without the other.
• Notice that there are no electrons in the “overall” equation......
• In any REDOX reaction, the electrons lost in the oxidation half -
reaction must exactly equal those gained in the reduction half -
reaction.

OXIDATION NUMBERS and BALANCING REDOX

EQUATIONS

• Balancing Redox Reactions is a bit of a tedious process, but

necessary.
• Any “method” giving the right answer may be used - use the one
that you prefer!
• We shall use a modification of that described in MH5, section 4.4,
the half-reaction method.
• Before beginning, it is often helpful (but not essential!!) to decide
what is being oxidized, and what is being reduced.

• To do that, we use Oxidation Numbers or States, an artificial way

of showing the “degree of oxidation” of an element.
• We assume that the more electronegative element in a compound
has acquired all the shared electrons in a covalent bond.

EXAMPLE: HBr H — Br Br is more electronegative

than H; Br gets the electron
+1 !1 (and the -1 charge)

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• Recall the order of electronegativity of the elements.....

F > O > CR > N > Br > C,S,I > H > ...metals

high low

Values are given in Table 6.5; MH5, p154

RULES FOR ASSIGNING OXIDATION NUMBERS [MH5; page 88]

1) Oxidation Number is always zero in the pure element:

(H2 (g) , CR2 (g) , Na (s) etc)

2) Oxidation Number is always equal to the charge on a monatomic ion:

Na+ is +1 Ba2+ is +2 CR— is !1 etc.

3) In a neutral molecule, the total charge on the molecule must be equal

to 0.

H - Br: (+1) + (!1) = 0 PBr5: (+5) + 5(!1) = 0

4) In a complex ion, the total charge must be equal to the charge on

the ion.

NH4+: (!3) + 4(+1) = +1 BF4—: (+3) + 4(!1) = !1

CRO4 — : (+7) + 4(!2) = !1

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5) Priority Rules (Memorize these!!!)

These rules, based on the electronegativity scale are useful in

assigning Oxidation Numbers in a compound:

a) Fluorine is always !1

b) Group I metals (Na, K, etc.) always +1

c) Group II metals (Ca, Mg, etc.) always +2

d) H is always +1 except when combined with a metal to

form a hydride .....
EXAMPLE: LiH is [Li+] [H—]; therefore H is -1

e) Oxygen is always !2 except when combined with fluorine

EXAMPLES: OF2 : O is +2 (because F is -1)

In Peroxides, which contain the O !O bond;

such as H - O - O - H (Hydrogen Peroxide), where O is !1

Na2O2: is 2 Na+ [O ! O]2! , therefore O is !1

f)Other Halogens (Group VII) are always !1, except when

combined with fluorine or oxygen.....

BrF5 : Br is + CR2O: CR is +

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 BALANCING REDOX EQUATIONS BY HALF
REACTIONS

EXAMPLE 1:
Permanganate ion oxidizes oxalate ions in ACIDIC solution.............

MnO4— + C2O4 2—
! Mn2+ + CO2

Separate the reaction into two half!reactions:

MnO4— ! Mn2+ & C2O42— ! CO2

Now, deal with each half reaction individually:

1) Balance non-O and non-H atoms as usual

MnO4— ! Mn2+

2) Add H2O to balance oxygen

MnO4— ! Mn2+

3) Add H+ to balance H atoms (regardless of acidic or basic)

MnO4— ! Mn2+ + 4 H2O

4) Add electrons to balance the charge

MnO4— + 8 H+ ! Mn2+ + 4 H2O

5) We are told the solution is acidic, so we may use H+ ions to balance

H.
6) Since e— appear on the left, this is REDUCTION (gain of electrons).

7) Mn goes from Oxidation Number +7 to Oxidation Number +2 ;

" it has gained 5 e —

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Now deal with the other half reaction:
C2O4 2— ! CO2

1) Balance non-O and non-H atoms as usual; in this case we must balance
the C:

C2O42— ! CO2

2) Add H2O to balance oxygen; oxygen is already balanced!!

3) Add H+ to balance H atoms (regardless of acidic or basic); there are

no H’s!!

4) Add electrons to balance the charge:

C2O42— ! 2 CO2

• Since e! appear on the right, this is OXIDATION (loss of electrons)

• Each Carbon has gone from Oxidation Number +3 to

Oxidation Number +4 ; " each C has lost one e—

• In a balanced redox equation, there are no electrons; we must make

the number of electrons in the two half reactions equal (then they
can be cancelled)
• So.......multiply each half !reaction by the number of e— in the other
half reaction!

Red: ×2

Ox: ×5

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• The 10 e — on each side may be cancelled; then add the two half
reactions together..........

• Always check that the equation is balanced for both atoms and
charge

EXAMPLE 2:
The following reaction occurs in BASIC solution.......

NH3(aq) + CRO — ! N 2 H4 + CR —

ammonia hypochlorite hydrazine

Separate the reaction into two half reactions:

NH3 ! N2H4 & CRO — ! CR —

1) Balance all non-O and non-H atoms; in this case balance N:

NH3 ! N2H4

2) Add H2O to balance oxygen; no need - as there is no oxygen present.

3) Add H+ to balance H atoms; although there is no appreciable H+

concentration in basic solution, we (temporarily) use H+ to balance
H.....
2 NH3 ! N2H4

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4) We are told the solution is basic, so use of H+ is NOT really
allowed......

5) We must neutralize the H+ by adding equal amounts of OH — to each

side; converting all H+ to H2O and retaining the balance:

2 NH3 ! N 2 H4 + 2 H +

6) Now combine the H+ and OH— on the right hand side to produce H2O:

2 NH3 + 2 OH— ! N 2 H4 +

7) Add electrons to balance the charge:

2 NH3 + 2 OH — ! N 2 H4 + 2 H2O

8) This is the OXIDATION half-reaction; electrons appear on the

right.

9) Each Nitrogen has gone from -3 to -2;

" each Nitrogen has lost one electron

Now for the other half reaction:

CRO — ! CR —

1) Balance all non-O and non-H atoms; the CR is already balanced.

2) Add H2O to balance oxygen:

CRO— ! CR—

3) Add H+ to balance hydrogen:

CRO— ! CR— + H2O

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4) Add OH! to remove H+:

CRO— + 2H+ ! CR— + H2O

5) Combine the H+ and OH - on the left hand side to produce H2O:

CRO— + ! CR— + H2O + 2 OH—

6) Add electrons to balance the charge:

CRO— + 2 H2O + ! CR— + H2O + 2 OH—

7) This is the REDUCTION half!reaction; electrons appear on the left.

8) CR has gone from +1 to -1;

" each CR has gained 2 electrons

9) As we have 2 electrons in each half reaction; add the two half

reactions together, cancelling the electrons.

10) Also cancel any H2O or OH— possible.......

CRO— + H2O + 2 e— ! CR— + 2 OH—

2 NH3 + 2 OH— ! N2H4 + 2 H2O + 2e—

• Check the final equation for balance in both atoms and charge.

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• A DISPROPORTIONATION reaction is a redox reaction in which a
substance in an intermediate oxidation state goes to both a higher
and a lower state by e! transfer.

EXAMPLE:
Copper, Cu, may exist in the +1 oxidation state, which is less stable
than either +2 or 0.

It may undergo disproportionation.......

1 e— oxidation
2 Cu+ ! Cu2+ + Cu(s)
1 e— reduction

• The opposite of disproportionation is CONPROPORTIONATION.

• There are two reactants; one is oxidized and one is reduced......but
there is only one product.
• The oxidation state of the product is an intermediate state to those
of the reactants.

EXAMPLE: CRO4— + CR —
! CRO3—

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EXAMPLE 1: Balance the following reaction which occurs in acidic
solution.

I3— ! IO3— + I—

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EXAMPLE 2:
Hydrazine, N2H4, is prepared by reaction of ammonia with chloramine in
basic solution, according to :

—
NH3 + NH2CR ! N2 H 4 + CR

Balance this equation.

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