Electrochemistry

Electrochemistry Terminology #1
Oxidation A process in which an element attains a more positive oxidation state Na(s) Na+ + eReduction A process in which an element attains a more negative oxidation state Cl2 + 2e- 2Cl-

Electrochemistry Terminology #2
An old memory device for oxidation and reduction goes like this

LEO says GER Lose Electrons = Oxidation Gain Electrons = Reduction

Electrochemistry Terminology #3
Oxidizing agent The substance that is reduced is the oxidizing agent Reducing agent The substance that is oxidized is the reducing agent

Electrochemistry Terminology #4
Anode The electrode where oxidation occurs Cathode The electrode where reduction occurs
Memory device:

Reduction at the Cathode

Table of Reduction Potentials

Measured against the Standard Hydrogen Electrode

Measuring Standard Electrode Potential

Potentials are measured against a hydrogen ion reduction reaction, which is arbitrarily assigned a potential of zero volts.

Galvanic (Electrochemical) Cells

Spontaneous redox processes have:
A positive cell potential, E0 A negative free energy change, (-G)

Zn - Cu Galvanic Cell
From a table of reduction potentials: Zn2+ + 2e- Zn Cu2+ + 2e- Cu E = -0.76V E = +0.34V

Zn - Cu Galvanic Cell
The less positive, or more negative reduction potential becomes the oxidation

Zn Zn2+ + 2eCu2+ + 2e- Cu Zn + Cu2+ Zn2+ + Cu

E = +0.76V E = +0.34V E0 = + 1.10 V

Line Notation
An abbreviated representation of an electrochemical cell

Zn(s) | Zn2+(aq) || Cu2+(aq) | Cu(s)

Anode Anode | material solution

||

Cathode solution

Cathode material

Calculating G0 for a Cell

G0 = -nFE0
n = moles of electrons in balanced redox equation
F = Faraday constant = 96,485 coulombs/mol e-

Zn + Cu2+ Zn2+ + Cu
0

E0 = + 1.10 V

coulombs Joules G (2 mol e )(96 485 )(1.10 ) mol e Coulomb

G 212267 Joules 212 kJ

0

The Nernst Equation

Standard potentials assume a concentration of 1 M. The Nernst equation allows us to calculate potential when the two cells are not 1.0 M.

R = 8.31 J/(molK)

RT EE ln(Q) nF
0

T = Temperature in K n = moles of electrons in balanced redox equation F = Faraday constant = 96,485 coulombs/mol e-

Nernst Equation Simplified

At 25 C (298 K) the Nernst Equation is simplified this way:

0.0591 EE log(Q) n
0

Equilibrium Constants and Cell Potential

At equilibrium, forward and reverse reactions occur at equal rates, therefore: 1. The battery is dead 2. The cell potential, E, is zero volts Modifying the Nernst Equation (at 25 C):

0.0591 0 volts E log( K ) n

0

Calculating an Equilibrium Constant from a Cell Potential

Zn + Cu2+ Zn2+ + Cu E0 = + 1.10 V

0.0591 0 volts 1.10 log( K ) 2 (1.10)(2) log( K ) 0.0591

37.2 log( K )

10

37.2

K 1.58 x 10

37

???

Concentration Cell
Both sides have the same components but at different concentrations.

Step 1: Determine which side undergoes oxidation, and which side undergoes reduction.

???

Concentration Cell
Cathode Both sides have the same components but at different concentrations.

Anode

The 1.0 M Zn2+ must decrease in concentration, and the 0.10 M Zn2+ must increase in concentration

Zn2+ (1.0M) + 2e- Zn

(reduction)
(oxidation)

Zn Zn2+ (0.10M) + 2eZn2+ (1.0M) Zn2+ (0.10M)

???

Concentration Cell
Anode Cathode

Concentration Cell
Both sides have the same components but at different concentrations.

Step 2: Calculate cell potential using the Nernst Equation (assuming 25 C). Zn2+ (1.0M) Zn2+ (0.10M)

0.0591 EE log(Q) n
0

Nernst Calculations
Zn2+ (1.0M) Zn2+ (0.10M)

0.0591 EE log(Q) n
0

E 0.0 Volts
0

n2

(0.10) Q (1.0)

0.0591 0.10 E 0.0 log( ) 0.030 Volts 2 1.0

Electrolytic Processes
Electrolytic processes are NOT spontaneous. They have: A negative cell potential, (-E0) A positive free energy change, (+G)

Electrolysis of Water
In acidic solution

Anode rxn:

4 H O 4 e 2 H 4 OH Cathode rxn: 2 2

2 H 2O O2 4 H 4e

-1.23 V -0.83 V -2.06 V

2 H 2O 2 H 2 O2

Electroplating of Silver
Anode reaction:
Ag Ag+ + eCathode reaction:

Ag+ + e- Ag
Electroplating requirements: 1. Solution of the plating metal 2. Anode made of the plating metal 3. Cathode with the object to be plated 4. Source of current

Solving an Electroplating Problem

Q: How many seconds will it take to plate out 5.0 grams of silver from a solution of AgNO3 using a 20.0 Ampere current?
Ag+ + e- Ag 5.0 g 1 mol Ag 1 mol e96 485 C 1 s 20.0 C 1 mol e 107.87 g 1 mol Ag = 2.2 x 102 s