Redox Reactions and

Electrochemistry
I. Redox Reactions
a) Oxidation Number
b) Oxidizing and Reducing Reagents
II. Galavanic or Voltaic Cells
a) Anode/Cathode/Salt Bridge
b) Cell Notations
c) Determining Cell Potential/Cell Voltage/Electromotive
force (emf)
III. Relating Cell Potential to K and G0
IV. Effect of Concentration on Cell Potential
 Redox Reactions and
Electrochemistry
V. Corrosion
VI. Batteries
VII. Fuel Cells
VIII.Electrolytic Cells
a) Calculating amounts of substances reduced or
oxidized
Electrochemistry: Interconversion of electrical and
chemical energy using redox reactions

Redox (Oxidation-Reduction) Reaction: Type of electron

transfer reaction. One substance gives up electrons;
the other accepts electrons.
OIL RIG

•Oxidation Half-Reaction; Oxidation Involves Loss of electrons

gge
•Reduction Half-Reaction; Reduction Involves Gain of electrons
e
Net Redox Rxn; 2Mg + O2 -> 2 Mg+2 + 2 O-2
 Oxidation number
The charge the atom would have in a molecule (or an
ionic compound) if electrons were completely transferred
to the more electronegative atom.

1. Oxidation number equals ionic charge for monoatomic ions

in ionic compound

CaBr2; Ca = +2, Br = -1
2. Metal ions in Family A have one, positive oxidation
number; Group IA metals are +1, IIA metals are +2

Li+, Li = +1; Mg+2, Mg = +2

4.4
 Oxidation number,continued
The charge the atom would have in a molecule (or an
ionic compound) if electrons were completely transferred
to the more electronegative atom.
3. The oxidation number of a transition metal ion is positive,
but can vary in magnitude.

4. Nonmetals can have a variety of oxidation numbers,both

positive and negative numbers which can vary in
magnitude.

5. Free elements (uncombined state) have an oxidation number

of zero. Each atom in O2, F2, H2, Cl2, K, Be has the same
oxidation number; zero.

4.4
 6. The oxidation number of fluorine is always –1.
(unless fluorine is in elemental form, F2)

7. The sum of the oxidation numbers of all the atoms in a

molecule or ion is equal to the charge on the molecule or
ion.
IF; F= -1; I = +1

8. The oxidation number of hydrogen is +1 except when it is

bonded to metals in binary compounds. In these cases, its
oxidation number is –1 or when it’s in elemental form (H2;
oxidation # =0).
HF; F= -1, H= +1
NaH; Na= +1, H = -1
9. The oxidation number of oxygen is usually –2. In H2O2 and
O22- it is –1, in elemental form (O2 or O3) it is 0.

H2O ; H=+1, O= -2
SO3; O = -2; S = +6

HCO3-
Oxidation numbers of all O = -2 H = +1
the atoms in HCO3- ?
3x(-2) + 1 + ? = -1
C = +4
4.4
 IF7
Oxidation numbers of all
the elements in the F = -1
following ?
7x(-1) + ? = 0
I = +7

K2Cr2O7
NaIO3
Na = +1 O = -2 O = -2 K = +1
3x(-2) + 1 + ? = 0 7x(-2) + 2x(+1) + 2x(?) = 0
I = +5 Cr = +6
4.4
 Determination of Oxidizing and
Reducing Agents
I. Determine oxidation # for all atoms in
both the reactants and products.
II. Look at same atom in reactants and
products and see if oxidation # increased
or decreased.
• If oxidation # decreased; substance reduced
• If oxidation # increased; substance oxidized
 Determination of Oxidizing and
Reducing Agents, continued

• Oxidizing Agent: Substance that oxidizes

the other substance by accepting electrons.
It is reduced in reaction.

• Reducing Agent: Substance that reduces the

other substance by donating electrons. It is
oxidized in reaction.
 Spontaneous Redox Reaction
Zn(s) + Cu+2 (aq) -> Cu(s) + Zn+2(aq)

Zn

Cu
Cu+2 time Zn +2
Gets Smaller -> <- Gets Larger
 Voltaic Cell Animation

Anode; Site of Oxidation AnOx or both vowels

Cathode; Site of Reduction Red Cat or both consonants

Direction of electron flow; anode to cathode (alphabetical)

Salt Bridge; Maintains electrical neutrality

+ ion migrates to cathode
- ion migrates to anode
 Cell Notation
1. Anode
2. Salt Bridge
3. Cathode

Anode | Salt Bridge | Cathode

| : symbol is used whenever there is a different phase

 Cell Notation
Zn (s) + Cu2+ (aq) Cu (s) + Zn2+ (aq)
[Cu2+] = 1 M & [Zn2+] = 1 M

Zn (s) | Zn2+ (1 M) || Cu2+ (1 M) | Cu (s)

anode cathode
More detail..
Zn (s)| Zn+2 (aq, 1M)| K(NO3) (saturated)|Cu+2(aq, 1M)|Cu(s)
anode Salt bridge cathode
19.2
Zn (s) + 2 H+(aq) -> H2 (g) + Zn+2 (aq)

K(NO3)

Zn(s)| Zn+2|KNO3|H+(aq)|H2(g)|Pt
 Electrochemical Cells
The difference in electrical
potential between the anode and
cathode is called:
• cell voltage
• electromotive force (emf)
• cell potential

E 0
Cell E 0
oxidation E 0
reduction

UNITS: Volts Volt (V) = Joule (J)

Coulomb, C

 Standard Electrode Potentials

Standard reduction potential (E0) is the voltage associated with a

reduction reaction at an electrode when all solutes are 1 M and
all gases are at 1 atm.

Reduction Reaction

eatm

V

Standard hydrogen electrode (SHE) 

Determining if Redox Reaction is Spontaneous

• + E°CELL ; spontaneous
reaction
• E°CELL = 0; equilibrium
• - E°CELL; nonspontaneous
reaction

More positive E°CELL ;

stronger oxidizing agent or
more likely to be reduced
• E0 is for the reaction as written
• The half-cell reactions are
reversible
• The sign of E0 changes when
the reaction is reversed
• Changing the stoichiometric
coefficients of a half-cell
reaction does not change the
value of E0
• The more positive E0 the
greater the tendency for the
substance to be reduced


 Relating E0Cell to G0
Units
work
ECell  work, Joule
ch arg e charge, Coulomb
Ecell; Volts

Faraday, F; charge on 1 mole e-

charge = nF F = 96485 C/mole

work = (charge)Ecell = -nFEcell

G = work (maximum)

G = -nFEcell
 Relating  CELL to the


Equilibrium Constant, K
G0 = -RT ln K
-RT ln K = -nFE0cell
G0 = -nFE0cell

 J 
RT  8. 31  298K 
E 0
Cell  ln K RT 

molK 
 0.0257
nF F 96485
C
mole

0.0257 0.0592
E0
Cell  ln K  log K
n n
Effect of Concentration on Cell Potential

G =G0 + RTlnQ
-nFEcell= -nFE0cell + RTln Q
G0 = -nFE0cell
Ecell= E0cell - RTln Q
nF
Ecell= E0cell - 0.0257ln Q Ecell= E0cell – 0.0592log Q
n n
Corrosion – Deterioration of Metals
by Electrochemical Process
Corrosion – Deterioration of Metals
by Electrochemical Process
Corrosion – Deterioration of Metals
by Electrochemical Process
Cathodic Protection
Abbreviated Standard Reduction
Potential Table
 Batteries

Dry cell

Leclanché cell

Anode: Zn (s) Zn2+ (aq) + 2e-

Cathode: 2NH4+ (aq) + 2MnO2 (s) + 2e- Mn2O3 (s) + 2NH3 (aq) + H2O (l)

Zn (s) + 2NH4 (aq) + 2MnO2 (s) Zn2+ (aq) + 2NH3 (aq) + H2O (l) + Mn2O3 (s)

19.6
 Batteries

Mercury Battery

Anode: Zn(Hg) + 2OH- (aq) ZnO (s) + H2O (l) + 2e-

Cathode: HgO (s) + H2O (l) + 2e- Hg (l) + 2OH- (aq)

Zn(Hg) + HgO (s) ZnO (s) + Hg (l)

19.6
 Batteries

Lead storage
battery

Anode: Pb (s) + SO42- (aq) PbSO4 (s) + 2e-

Cathode: PbO2 (s) + 4H+ (aq) + SO42- (aq) + 2e- PbSO4 (s) + 2H2O (l)

Pb (s) + PbO2 (s) + 4H+ (aq) + 2SO42- (aq) 2PbSO4 (s) + 2H2O (l)

19.6
 Fuel Cell vs. Battery
• Battery; Energy storage device
– Reactant chemicals already in device
– Once Chemicals used up; discard (unless rechargeable)

• Fuel Cell; Energy conversion device

– Won’t work unless reactants supplied
– Reactants continuously supplied; products continuously
removed
 Fuel Cell

A fuel cell is an
electrochemical cell
that requires a
continuous supply of
reactants to keep
functioning

Anode: 2H2 (g) + 4OH- (aq) 4H2O (l) + 4e-

Cathode: O2 (g) + 2H2O (l) + 4e- 4OH- (aq)

2H2 (g) + O2 (g) 2H2O (l)

 Types of Electrochemical Cells

• Voltaic/Galvanic Cell; Energy released

from spontaneous redox reaction can be
transformed into electrical energy.

• Electrolytic Cell; Electrical energy is used

to drive a nonspontaneous redox reaction.
 Charge =(Current)(Time)

Molar Mass

Faraday’s Constant Redox Eqn