ELECTROCHEMISTRY
REDUCTION-OXIDATION REACTIONS
REDUCTION-OXIDATION
REACTIONS (REDOX)
• Redox: Chemical reactions which involved electron
transfer
• Oxidation originally meant “combining with oxygen.”
• Reduction originally meant “combining with
hydrogen.”
• Modern definitions are broader:
– Oxidation: Losing electrons.
– Reduction: Gaining electrons.
REDOX
• An easy way to remember what happens in redox
reactions is to use this little acronym.
• LEO goes GER.
• Losing Electrons is Oxidation.
• Gaining Electrons is Reduction.
AN EXAMPLE
• Magnesium reacts with sulfur to form a
compound.
• Mg(s) + S(s) 🡪 MgS
• What are the charges of each of the
reactants and products?
• 0 0 2+ 2-
• Mg + S 🡪 MgS
• What happened electronically during the
reaction?
AN EXAMPLE
• How many valence electrons does Mg have?
• 2 is correct.
• What will Mg probably do with those 2 electrons?
• Give them away.
• What about S?
• It has 6 valence electrons and needs to gain 2 to
make an octet.
AN EXAMPLE
A Lewis dot diagram is a simple
way to show what happens.
2+ 2-
Mg S
REDOX
Lose 2 e- = oxidation
•0 0 2+ 2-
•Mg + S 🡪 MgS
Gain 2 e- = reduction
HALF-REACTIONS
• It is often useful to separate the oxidation part of
the reaction from the reduction part.
• But please remember, it is impossible to have
one without the other.
• Electrons can’t disappear, so if one substance is
being oxidized, something nearby must be getting
reduced.
HALF-REACTIONS
• Oxidation half-reaction:
• Mg 🡪 Mg2+ + 2 e-
• Reduction half-reaction:
• S + 2 e- 🡪 S2-
• When redox reactions occur, the total number of
electrons lost by one substance must equal those
gained by the other.
OXIDATION NUMBERS
• Keeping track of electrons involves knowing a
few basic rules.
• Any element, whether it is a free atom or
part of a molecule or ion can be assigned an
oxidation number.
• Sometimes the number represents an actual
charge, but often it does not.
• It is simply an electronic bookkeeping system.
OXIDATION NUMBER RULES
1. Free elements (including the HOFBrINCl’s) have ox.
# = 0.
Ex. K(s) = 0 Cl2(g) = 0
2. Single atom ions: ox. # = ionic charge.
Na+ = +1 Cl- = -1
3. The oxidation number for oxygen is -2 (except in
peroxides = -1)
4. The oxidation number for hydrogen is +1 (except in
metal hydrides = -1
OXIDATION NUMBER RULES
5. In a covalent compounds not containing H or O, the
more electronegative element is assigned an oxidation
number equal to its negative charge in an ionic
compound
6. All other oxidation numbers are assigned so that the
sum of the oxidation numbers equals the net charge
on the molecule or ion
7. All ox. #s in a polyatomic ion must add up to the
charge of the ion.
EXAMPLES
• +5 -2
• P O43-
• 0 • +5 + (4 x -2) = -3
• Ag(s)
• +1 -2
• +1 -1 • H2O
• K Cl
• 2 +4 -2
• Ca C O3
• +3 -1
• +2 +4 -6 = 0
• Al Br3
EXAMPLES
• +2 -2
• Fe O
• +1 -1
• K 2 O2 • +3 -2
• Fe2 O3
• -3 +1 -1
• N H4 Cl
• +2 +5 -2
• Mg (N O3)2
• +1 +5 -2 • +2 + 10 – 12 = 0
• Na N O3
MULTIPLE OXIDATION STATES
• Find the ox. # of N in • Answers:
these substances.
1. N2 1. 0
2. NH3 2. -3
3. NO 3. +2
4. N2O 4. +1
5. NO2 5. +4
6. N2O3 6. +3
7. N2O5 7. +5
CARBON IS ALSO VERY
VERSATILE.
1. C(s) 1. 0
2. CO 2. +2
3. CO2 3. +4
4. CH4 4. -4
5. CH2O 5. 0
6. H2CO3 6. +4
This versatility helps explain why C and N are the
important central atoms in many biological molecules.
A TOUGH ONE
• Find the oxidation numbers for the elements in this compound.
• +3 +6 -2
• Fe2(Cr2O7)3
• Solution: Dichromate ions are 2- ions.
• Therefore, Fe must be 3+. (2 x 3+) = +6
• O is -2. (7 x 3 x -2) = -42
• +6 + (2 x 3 x Cr) – 42 = 0
• (2 x 3 x Cr) must = 36. Cr must be +6.
ACTIVE OR PASSIVE?
• When a redox reaction occurs, something loses electrons
(gets oxidized) and something gains them (gets reduced).
(Passive view)
• But there is another side to that same coin.
• The element gaining electrons could be looked at as an
electron taker. (Active view.)
OXIDIZING AND REDUCING
AGENTS
• An electron taker causes the oxidation of another
element and so may be thought of as an oxidizing
agent.
• Oxidizing agents are reduced.
• Likewise, an electron giver causes the reduction
of another element and so can be thought of as a
reducing agent.
• Reducing agents get oxidized.
HALF-REACTIONS
• Often a redox reaction is separated into two half
reactions, one that shows reduction and one that
shows oxidation
• In half reactions, atoms must be balanced and the
net charge of each half reaction should be zero
• Half reactions do not include spectator ions
HALF REACTIONS EXAMPLE
Mg(s) + 2 AgNO3(aq) 🡪 2 Ag(s) + Mg(NO3)2
