_____________________________________________________________________CHEM 100 LECTURE

Unit 12. Electrochemistry

study of inter-conversion of electrical and chemical energy

the conversion takes place in an electrochemical cell
a redox reaction either produce or require electrical energy

I. Galvanic Cell (or Voltaic Cell)

any spontaneous redox reaction can serve as a source
of electrical energy
oxidation occurs at the anode; reduction at
the cathode
2+
2+
in this example, Zn is oxidized to Zn ; Cu is
reduced to Cu
electrons move from the anode to the
cathode
salt bridge close the circuit and maintain
electrical neutrality: Cl moves to the anode to
+
balance the accumulation of (+) charge; K to
the cathode to balance increase of (-) charge
2+
2+
cell notation: ZnlZn llCu lCu

Standard Hydrogen Electrode (SHE)

2H (aq) + 2e (aq) H2 (g)
Ered = 0.000
for cells involving gases, an inert
electrode like Pt or graphite is used
x+
2+
cell notation: MlM llH lH2, Pt
+

Standard Cell Voltage, Cell Potential (Ecell), or Electromotive Force (emf)

o
from the standard reduction potentials measured at standard conditions: 1M, 1atm, 25 C
a measure of spontaneity: (+) spontaneous; (-) non-spontaneous
an intensive property

the potential or voltage difference between the anode and the cathode: E cell = Eox + Ered
the oxidation potential (Eox) is taken by changing the sign of the reduction potential (Ered) since oxidation is
the reverse of reduction
Note: Values of Ered can be found in the Standard Reduction Potential Table (appendix J of lab manual).
Examples:
3+

2Fe

+ 2I (aq) 2Fe
-

(aq)

Ni(s) + Zn

2+

Ni(s) + Cu

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2Ni

(aq)

2+

(aq)

(aq)

(aq)

2Ni

(aq)

Cu

2+

Cu(s) + 2H

2+

2+

(aq)

2+
(aq)

+ I2 (s)

+ Zn (s)
+ Cu (s)
+ H2 (g)

_____________________________________________________________________CHEM 100 LECTURE

Corrosion
deterioration of metals by an electrochemical process
example: rusting of iron
remedy 1: attach a sacrificial anode, a more active metal like Mg
remedy 2: coat it with a less active metal like Zn (galvanization, hence galvanized iron)
Batteries
A. Non-rechargeable batteries
Dry Cell (1.5 V)
Anode:
Cathode:

Zn Zn + 2e
+
2NH4 + 2MnO2 + 2e Mn2O3 + 2NH3 + H2O
2+

Alkaline Cell uses KOH instead of NH4Cl in dry cell; prevent accumulation of NH3.
Mercury Cell (1.35 V)
Anode:
Cathode:

Zn(Hg) + 2OH ZnO + H2O + 2e

HgO + H2O + 2e Hg + 2OH
-

B. Rechargeable
Lead Storage Battery (2 V)
Anode:
Zn(Hg) + 2OH ZnO + H2O + 2e
Cathode:
HgO + H2O + 2e Hg + 2OH
Note: actual battery is 12 V, uses 6 panels of 2 V in series
Ni-Cd (1.2 V)
Anode:
Cathode:

Cd + 2OH Cd(OH)2 + 2e
2NiO(OH) + 2H2O + 2e 2Ni(OH)2 + 2OH
-

Li-ion (3.2 V)

II. Electrolytic Cell: Electrolysis

electrical energy is used to cause a non-spontaneous chemical reaction to occur

example: electrolysis of KI solution
a power source (like a battery) removes
electrons from the anode and pushes it to the
cathode
ox occurs at the anode, red at the cathode
I is oxidized to I2, producing yellow color (blue
with starch)
H2O produces H2 (bubbles) and OH (pink with
phenolphthalein indicator)

E cell is negative; this reaction will not occur

without the battery

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_____________________________________________________________________CHEM 100 LECTURE

Quantitative Aspect of Electrolysis (Electroplating or Electrodeposition)
current
charge
potential
energy
power

ampere (A)
coulomb (C)
volt (V)
joule (J)
watt (W)

1 C = 1 A.s
1 J = 1 V.C
1 W = 1 J/s

1 kWh = 3.6 x 10 J
1 mole e = 96480 C (Faradays constant)
Ag + e Ag
+

Cu

2+

1 mole of e = 1 mole Ag (107.9 g)

+ 2e Cu
-

2 moles of e = 1 mole Cu (63.55 g)

How to convert from charge to mass of metal:

-

1 mol e =
96480 C

C = A.s

A.s

MM metal

mole e

mole metal

mass metal

Example:
Chromium can be electroplated from an acid solution of CrO3 (Cr=52.00 g/mol)
CrO3 + 6H + 6e Cr + 3H2O
+

a. how many grams of Cr will be plated by a charge of 1.0 x 10 C? answer: 0.90 g

b. how long will it take (in min) to plate 1.0 g of Cr using 6.0 A of current? answer: 1855 sec or 31 min
c. how many grams of Cr can be plated by 150 mA of current if applied for 2.5 hours? answer: 0.12 g
d. If the applied voltage is 4.5 V, what is the amount of electrical energy absorbed in plating 1.0 g of Cr? answer: 50 kJ

An aqueous solution of platinum salt (PtCl4) is electrolyzed at a current of 2.5 A for 2.0 hrs. How many grams of Pt
(195.1 g/mol) will be deposited in the reaction? answer: 9.1 g

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