Electrochemistry

Chemical reactions and Electricity

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 Introduction

Electron transfer
The basis of electrochemical processes is
the transfer of electrons between
substances.
A e - + B

Oxidation; the reaction with oxygen.

4 Fe(s) + 3O 2 (g) Fe2O3 (s)

Why is rust Fe2O3 , 2Fe to 3O?

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 Oxidation of Iron
Electron transfer of iron- Electron
transfer to oxygen
Fe Fe3+ + 3e- 1/2 O2 + 2e- O2-

Net reaction:
4 Fe(s) + 3O2(g) Fe2O3(s)
Fe(+3) O(-2)

Fe2O3 : Electrical neutrality

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 Oxidation States
Definition -
Oxidation Process- (charge increase)
Lose electron (oxidation)
i.e., Fe Fe+3 + 3e- (reducing agent)
Reduction Process-(charge decrease)
Gain electrons (reduction)
i.e., 1/2 O2 + 2e- O2- (oxidizing agent)
Redox Process is the combination of an
oxidation and reduction process.

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 Symbiotic Process
Redox process always occurs together. In
redox process, one cant occur without the
other.
Example: 2 Ca (s) + O2 2CaO
Which is undergoing oxidation ? Reduction?
Oxidation: Ca Ca+2
Reduction: O2 O-2

Oxidizing agent; That which is responsible to oxidize

another.
O2 ; Oxidizing agent; The agent itself undergoes reduction

Reducing agent; That which is responsible to reduce

another.
Ca; Reducing agent; The agent itself undergoes oxidation
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 Rules of Oxidation State Assignment
1. Ox # = 0: Element in its free
state (not combine with different
element)

2. Ox # = Charge of ion:
Grp1 = +1, Grp2 = +2, Grp7
= -1, ...
3. F = -1: For other halogens (-1)
except when bonded to F or O.
4. O = -2: Except with fluorine or
other oxygen.
5. H = +1: Except with electropositive
element (i.e., Na, K) H = -1.
Ox. # = charge of molecule or
ion.

Highest and lowest oxidation

numbers of reactive main-group
elements. The A group number
shows the highest possible
oxidation number (Ox.#) for a
main-group element. (Two
important exception are O, which
never has an Ox# of +6 and F,
which never has an Ox# of +7.)
For nonmetals, (brown) and
metalloids (green) the A group
number minus 8 gives the lowest
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 Detailed: Assigning Oxidation
Number
Rules for Assigning an Oxidation Number (Ox#)
General
General rules
rules
1. For an atom in its elemental form (Na, O2, Cl2 ) Ox# = 0
2. For a monatomic ion: Ox# = ion charge
3. The sum of Ox# values for the atoms in a compound equals zero.
The sum of Ox# values for the atoms in a polyatomic ion equals the
ion charge.

Rules for specific atoms or

or periodic
periodic table
table groups.
groups.
1. For fluorine: Ox# = -1 in all compounds
2. For oxygen: Ox# = -1 in peroxides
Ox# = -2 in all other compounds (except with
F)
3. For Group 7A(17): Ox# = -1 in combination with metals,
nonmetals (except O), and other halogens lower in the
group.
4. For Group 1A(1): Ox# = +1 in all compounds
5. For Group 2A(2): Ox# = +2 in all compounds
6. For hydrogen: Ox# = +1 in combination with nonmetals
Ox# = -1 in combinations with metals and
7 boron
 Redox Reactions - Ion electron
method.
Under Acidic conditions
1. Identify oxidized and reduced species
Write the half reaction for each.

2. Balance the half rxn separately except H & Os.

Balance: Oxygen by H2O
Balance: Hydrogen by H+
Balance: Charge by e -

3. Multiply each half reaction by a coefficient.

There should be the same # of e- in both half-rxn.

4. Add the half-rxn together, the e - should cancel.

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 Example: Acidic Conditions
I- + S2O8-2 I2 + S2O42-
Half Rxn (oxid): I- I2
Half Rxn (red): S2O8-2 I2 + S2O42-
Bal. chemical and e- : 2 I- I 2 + 2 e-
Bal. chemical O and H : 8e- + 8H+ + S2O8-2 S 2 O4 2 - +
4H2O

Mult 1st rxn by 4: 8I- 4 I2 + 8e-

Add rxn 1 & 2: 8I- 4 I2 + 8e-
8e- + 8H+ + S2O8-2 S2O42- + 4H2O

8I- + 8H+ + S2O8-2 4 I2 + S2O42- + 4H2O

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 Redox Reactions - Ion electron
method.
Under Basic conditions
1, 2. Procedure identical to that under acidic
conditions
Balance the half reaction separately except H & Os.
Balance Oxygen by H2O
Balance Hydrogen by H+
Balance charge by e-

3. Mult each half rxn such that both half- rxn

have same number of electrons

4. Add the half-rxn together, the e- should

cancel.

5. Eliminate H+ by adding:
10 H+ + OH- H O
 Example: Basic Conditions

H2O2 (aq) + Cr2O7-2(aq ) Cr 2+

(aq) + O2 (g)
Half Rxn (oxid): 6e- + 14H+ + Cr2O7-2 (aq) 2Cr3+ + 7
H 2O
Half Rxn (red): ( H 2O 2 (aq) O2 + 2H+ + 2e- ) x 3

8 H+ + 3H2O2 + Cr2O72- 2Cr+3 + 3O2 + 7H2O

add: 8H2O 8 H+ + 8 OH-

8 H+ + 3H2O2 + Cr2O72- 2Cr+3 + 3O2 + 7H2O

8H2O 8 H+ + 8 OH-

Net Rxn: 3H2O2 + Cr2O72 - + H2O 2Cr+3 + 3O2 + 8 OH-

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 Exercise

Try these examples:

1. BrO4- (aq) + CrO2- (aq) BrO3- (aq) + CrO42- (aq) (basic)

2. MnO4- (aq) + CrO42- (aq) Mn2+ (aq) + CO2 (aq) (acidic)

3. Fe2+ (aq) + MnO4- (aq) Fe3+(aq) + Mn2+ (aq) (acidic)

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 Redox Titration
Balance redox chem eqn: Solve problem using stoichiometric
strategy.
Q: 1.225 g Fe ore requires 45.30 ml of 0.0180 M KMnO 4. How pure is the ore
sample?

When iron ore is titrated with KMnO4 . The equivalent point results
when:
KMnO4 (purple) Mn2+ (pink)
Mn (+7) Mn(+2)

Rxn: Fe+2 + MnO4- Fe+3 + Mn2+

Bal. rxn: 5 Fe2+ + MnO4- + 8 H+ 5 Fe3+ + Mn2+ + 4 H 2O

Note Fe2+ 5 Fe3+ : Oxidized Lose e- : Reducing Agent

Mol of MnO4- = 45.30 ml 0.180(mol/L) = 0.8154 mmol MnO 4-

Amt of Fe:= 0.8154 mmol 5 mol Fe+2 55.8 g =

0.2275 g
1 mol MnO4- 1 mol Fe2+
% Fe = (0.2275 g / 1.225 g) 100 = 18.6 %

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 Redox Titration: Example

1. A piece of iron wire weighting 0.1568 g is converted

to Fe2+ (aq) and requires 26.24 mL of a KMnO 4 (aq)
solution for its titration. What is the molarity of the
KMNO4 (aq) ?

2. Another substance that may be used to standardized

KMNO4 (aq) is sodium oxalate, Na2C2O4. If 0.2482 g of
Na2C2O4 is dissolved in water and titrated with 23.68 mL
KMnO4, what is the molarity of the KMnO 4 (aq) ?

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