ELECTROCHEMISTRY

(Refer to Chapter 19 Electrochemistry)

OXIDATION __________ of electrons by an atom, molecule, ion, etc. NOTES:

REDUCTION __________ of electrons by an atom, molecule, ion, etc.

e.g. 2Na(s) + Cl2(g) 2NaCl(s)
Here the Na metal is _______________ to Na+ (1 electron lost per sodium atom)
and Cl2 is _______________ to 2Cl (1 electron gained per chlorine atom).

Aside: You may have heard the phrase: "LEO the lion says GER "
where LEO stands for "Loss of Electrons is Oxidation" and
GER stands for "Gain of Electrons is Reduction".
OR
OIL RIG where "OIL" stands for "Oxidation Is Loss (of
electrons)" and "RIG" stands for "Reduction Is Gain (of electrons)"

Question: All the following are oxidation-reduction reactions EXCEPT

A. H2(g) + F2(g) 2HF(g).
B. Mg3N2(s) + 6H2O(l) 3Mg(OH)2(s) + 2NH3(g).
C. 2K(s) + 2H2O(l) 2KOH(aq) + H2(g).
D. 6Li(s) + N2(g) 2Li3N(s).
E. Ca(s) + H2(g) CaH2(s).

Oxidation Reduction or REDOX Reactions

Reactions which involve _________ GAIN (reduction) and LOSS (oxidation) of
electrons. It is convenient to think of the overall REDOX reaction as two individual
HALF-rxns, namely an oxidation half reaction and a reduction half reaction, i.e.,
2Na(s) 2Na+(aq) + 2e (oxidation reaction)
+ Cl2(g) + 2e 2Cl (aq) (reduction reaction)
2Na(s) + Cl2(g) 2NaCl(aq)

Question: In the following, which species is oxidized?

3Ag2S(s) + 8H+(aq) + 2NO3(aq) 6Ag+(aq) + 3S(s) + 2NO(g) + 4H2O(l)
A. NO3
B. Ag2S
C. NO
D. H+
E. Ag+
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Oxidising AGENT causes another species to be _______________ by NOTES:
accepting/taking electrons from it.

Reducing AGENT causes another species to be _______________

reduced by donating electrons to it.

LEORA GEROA

LEORA Loss of Electrons is Oxidation and that species is a Reducing Agent.

GEROA Gain of Electrons is Reduction and that species is an Oxidising Agent.

Oxidation results in ____________ in the Oxidation State (or Number) by loss of

electrons. Reduction results in _____________ in the Oxidation State (or Number)
by gain of es.

Question: In the following redox reaction,

8H+(aq) + 6Cl(aq) + Sn(s) + 4NO3(aq) SnCl62(aq) + 4NO2(g) + 4H2O(l),
the oxidizing agent is
A. Cl.
B. H+.
C. Sn.
D. NO3.
E. SnCl62.

Rules for assigning Oxidation Numbers

(Refer to Section 4.5 to review oxidation and reduction reactions.)
1. For pure elements, their oxidation number = 0 (e.g., Fe(s), Br2(l) and N2(g), etc.).
2. Monatomic ions have oxidation numbers equal to their charge (e.g., Fe3+ or S2).
3. Fluorine in its compounds is ALWAYS 1
4. Hydrogen in covalent compounds with non metals is +1 (e.g., H2O, CH4, etc.),
in metal hydrides it is 1 (e.g., NaH, CaH2, etc.)
5. Oxygen in its covalent compounds is 2, except in peroxides (e.g., H2O2) where
it is 1 (rule #4) or in metal oxides such as KO2 where O is .
6. The sum of the oxidation numbers equal zero for a neutral (no charge)
compound; for an ion the sum of the oxidation numbers equals the ions
charge.
7. Look to the column number in the periodic table to assign oxidation numbers.
Note: As shown in rule #5, non-integral oxidation numbers are possible.

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Examples: Assign Oxidation Numbers (or States) to all the atoms in the following: NOTES:

CO2 NH3

Cr2O72 C2H6O

LiH C2H4O2

S4O62 I3

Other Examples (answers at end of notes):

PbS NO3 AlO2

CH4 H3PO4 ClO

SF6 H2PO4 ClO2

MnO4 F2O ClO4

Absolutely FOOL PROOF method for balancing ANY redox equation

(This method is different from the textbooks method.)
1. Assign Oxidation Numbers and write separate equations for each half
reaction, then work on each half reaction separately.
2. Balance the atoms being oxidised or reduced.
3. Based on the change in oxidation numbers, determine the number of es
involved and add them to the high oxidation number side of the equation.
4. Balance the charge, adding either H+ (if in ACID solution) or OH (if in
BASE solution).
5. Balance the OXYGENs by adding H2O to the appropriate side of the eqn.
6. Check that everything balances it will!
7. Scale the two half rxns so the number of es are equal in each equation.
8. Add the two half reactions.

To remember this order, use "AEIOU":

A after assigning oxidation numbers, check that the Atoms are balanced.
E add the Electrons to the half reactions.
I balance the Ions (charge) using either H+ or OH .
O balance the Oxygens in the half reactions by adding H2O.
U Unite the two equations together after scaling the two half reactions.

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Example 1 : MnO4 (aq) + Fe2+(aq) Fe3+(aq) + Mn2+(aq) in acid solution. NOTES:
Oxidation numbers: Mn in MnO4 is ___, in Mn2+ it is ____; Fe2+ is +2, Fe3+ is +3

Oxidation (Loss of e-): Fe2+(aq) Fe3+(aq) + 1e (steps 1,2,3)

Reduction (Gain of e-): MnO4 (aq) Mn2+(aq) (steps 1 and 2)

(step 3)

(step 4)

(step 5)

Visual check all OK (step 6)

Scale (step 7): 5Fe2+(aq) 5Fe3+(aq) + 5e (step 7)
8H+ + 5e + MnO4 (aq) Mn2+(aq) + 4H2O(l) (step 7)
Add the two half reactions together and cancel out the electrons (step 8):
8H+(aq) + MnO4 (aq) + 5Fe2+(aq) Mn2+(aq) + 4H2O(l) + 5Fe3+(aq)

Example 2 : In base, NO2 (aq) + Al(s) NH3(g) + AlO2(aq)

Oxidation Numbers: N in NO2(aq) is ______, in NH3(g) is _______

Al in Al(s) is ______, in AlO2 (aq) is _____

Oxidation: Al(s) AlO2(aq) + 3e (steps 1,2,3)

(steps 4)

(steps 5,6)

Reduction: NO2(aq) NH3(g) (steps 1 and 2)

(step 3)

(step 4)

(steps 5,6)

Scale (step 7):

8OH(aq) + 2Al(s) 2AlO2(aq) + 4H2O(l) + 6e
NO2 (aq) + 6e + 5H2O(l) NH3(g) + 7OH(aq)

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Add:
5H2O(l) + NO2(aq) + 8OH (aq) + 2Al(s) NH3(g) + 7OH(aq) + 2AlO2(aq) + 4H2O(l)

Tidy up (cancel superfluous water and hydroxide ions):

H2O(l) + NO2(aq) + OH(aq) + 2Al(s) NH3(g) + 2AlO2(aq)

Practice: Balance the following reactions.

1. H+(aq) + Cr2O72(aq) + C2H6O(l) Cr3+(aq) + CO2(g) (H+ in equation signifies acidic)
2. As2O3(s) + NO3(aq) H3AsO4(aq) + NO(g) (in acid)
2
3. MnO4 (aq) + S (aq) MnS(s) + S(s) (in base)
4. Cl2(g) Cl(aq) + ClO(aq) (in base)
5. HO2 (aq) + Cr(OH)3(aq) CrO42 (aq) (in base)

6. Ag2S(s) + CN (aq) + O2(g) S(s) + [Ag(CN)2] (aq) (in acid)
3
7. V(s) HV6O17 (aq) + H2(g) (in base)

8. CNS (aq) + O2(g) CO2(g) + NO2(g) + SO2(g) (in acid)

Qu#4: All the following half-reactions are balanced EXCEPT

A. 2H2O + 2e H2 + 2OH.
B. 2Ta + 5H2O Ta2O5+ 10H+ + 10e.
C. NO3 + 4H++ + 3e NO + 2H2O.
D. H2O2 2OH + 2e.
E. H3PO3 + H2O H3PO4 + 2H+ + 2e.

Answers to assigning oxidation number examples on page 68:

PbS S (like O) is 2; Pb is +2 since compound is neutral.
CH4 H = +1; C = 4 since compound is neutral.
SF6 F = 1; S = +6 since compound is neutral.
MnO4 O = 2, to solve for Mn use: x + 4(2) = 1; x = +7

NO3 O = 2, to solve for N: x + 3(2) = 1; x = +5
H3PO4 O = 2, H = +1; to solve for P: 3 + x + 4(2) = 0; x = +5

H2PO4 O = 2, H = +1; to solve for P: 2 + x + 4(2) = 1; x = +5
F2O F = 1, O = +2 (Rule 3) since compound is neutral.
AlO2 O is 2, Al = +3 since ion must add up to 1.

ClO O is 2, Cl = +1 since ion must add up to 1.

ClO2 O is 2, Cl = +3 since ion must add up to 1.

ClO4 O is 2, Cl = +7 since ion must add up to 1.

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Answers for Balancing Practice (page 70):

1. 16H+(aq) + 2Cr2O72(aq) + C2H6O(l) 4Cr3+(aq) + 2CO2(g) + 11H2O(l)

2. 3As2O3(s) + 4NO3(aq) + 4H+(aq) + 7H2O(l) 6H3AsO4(aq) + 4NO(g)

3. 2MnO4 (aq) + 7S2(aq) + 8H2O(l) 2MnS(s) + 5S(s) + 16OH(aq)

4. Cl2(g + 2OH(aq) Cl(aq) + ClO(aq) + H2O(l)

Note: In this example, Cl2 is used as a reactant in BOTH the oxidisation and reduction rxns, i.e.,
Oxidation: Cl2(g) 2ClO(aq); Reduction: Cl2(g) 2Cl(aq)
Also, the equation is divided by 2 to create the simplest expression.

5. 2HO2 (aq) + Cr(OH)3(aq) CrO42 (aq) + OH(aq) + 2H2O(l)

(Since a basic solution, use either OH or H2O as the product to balance the reduction half reaction.)

6. 2Ag2S(s) + 8CN(aq) + O2(aq) + 4H+(aq) 2S(s) + 4[Ag(CN)2] (aq) + 2H2O(l)

(Since under acidic conditions, one uses H2O as the product to balance the reduction half reaction.
Also keep "weird" atoms together, i.e., the CN must be in the half reaction with [Ag(CN)2] .)

7. 6V(s) + 14H2O(l) + 3OH (aq) HV6O173 (aq) + 15H2(g)

8. CNS (aq) + O2(g) CO2(g) + NO2(g) + SO2(g) (in acid)

To determine oxidation numbers for CNS (aq) use your knowledge of electronegativity:
Assign S (same group as O) as 2 and therefore C+N = +1. To get a sum of +1, C = +4 & N = 3
works (These assignments are based on which element is more electronegative. But, one can also
assign C = 4 & N = +5 and end up with the correct balanced equation at the end.)

Also, in this example, more than one element is being oxidized (i.e., both N & S). Just put them all in
the same half reaction and sum up the total number of electrons lost, to get the complete half reaction,
i.e.,

Oxidation half reaction: CNS (aq) CO2(g) + NO2(g) + SO2(g)

Ox. numbers: +4, 3, 2 +4 +4 +4

CNS (aq) CO2(g) + NO2(g) + SO2(g) + (7+6)e

CNS (aq) + 6H2O(l) CO2(g) + NO2(g) + SO2(g) + 12H+(aq) + 13e

Reduction half reaction: O2(g) + 4H+(aq) + 4e 2H2O(l)

Balanced overall equation:

4CNS (aq) + 13O2(g) + 4H+(aq) 4CO2(g) + 4NO2(g) + 4SO2(g) + 2H2O(l)

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