Electrochemistry

Chapter 21
 Electrochemistry and Redox

Oxidation-reduction: “Redox”

Electrochemistry:
study of the interchange between chemical
change and electrical work

Electrochemical cells:
systems utilizing a redox reaction to produce
or use electrical energy
 Redox Review
Redox reactions: electron transfer processes

Oxidation: loss of 1 or more e-

Reduction: gain of 1 or more e-

Oxidation numbers:imaginary charges

(Balancing redox reactions)

 Oxidation Numbers (O.N.)
1.Pure element O.N. is zero

2.Monatomic ion O.N. is charge

3.Neutral compound:sum of O.N. is zero

Polyatomic ion: sum of O.N. is ion’s charge

*Negative O.N. generally assigned to more

electronegative element
 Oxidation Numbers (O.N.)
4.Hydrogen
assigned +1
(metal hydrides, -1)
5.Oxygen
assigned -2
(peroxides, -1; OF2, +2)
6.Fluorine
always -1
 Oxidation-reduction
Oxidation is loss of e-
O.N. increases (more positive)

Reduction is gain of e-
O.N. decreases (more negative)

Oxidation involves loss OIL

Reduction involves gain RIG
 Redox

Oxidation is loss of e-
causes reduction
“reducing agent”

Reduction is gain of e-
causes oxidation
“oxidizing agent”
 Balancing Redox Reactions
1. Write separate equations (half-reactions) for
oxidation and reduction

2. For each half-reaction

a. Balance elements involved in e- transfer

b. Balance number e- lost and gained

3.To balance e-
multiply each half-reaction by whole numbers
 Balancing Redox Reactions: Acidic
4.Add half-reactions/cancel like terms (e -)

5. Acidic conditions:
Balance oxygen using H2O
Balance hydrogen using H+
Basic conditions:
Balance oxygen using OH-
Balance hydrogen using H2O

6.Check that all atoms and charges balance

 Examples
Acidic conditions:
- 2 acid 2 3
MnO 4(aq)  Fe (aq) 
 Mn (aq)  Fe (aq)

Basic conditions:

 base 
Ag (s)  CN (aq)  O 2(g) 
 Ag(CN)2(aq)
 Types of cells

Voltaic (galvanic) cells:

a spontaneous reaction generates electrical energy

Electrolytic cells:
absorb free energy from an electrical source to
drive a nonspontaneous reaction
 Common Components
Electrodes:
conduct electricity between cell and
surroundings

Electrolyte:
mixture of ions involved in reaction or
carrying charge

Salt bridge:
completes circuit (provides charge balance)
 Electrodes
Anode:
Oxidation occurs at the anode

Cathode:
Reduction occurs at the cathode

Active electrodes: participate in redox

Inactive: sites of ox. and red.
 Voltaic (Galvanic) Cells

A device in which chemical energy

is changed to electrical energy.

Uses a spontaneous reaction.

17_360

e– e–

e– e–
Porous disk

Oxidation Reduction

e– Reducing Oxidizing e–
agent agent

(a) Anode (b) Cathode

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

Zn gives up electrons to Cu
— “pushes harder” on e-

— greater potential energy

— greater “electrical potential”

Spontaneous reaction due to

— relative difference in metals’ abilities to give e -

— ability of e- to flow
 Cell Potential

Cell Potential / Electromotive Force (EMF):

The “pull” or driving force on electrons

Measured voltage (potential difference)

work or electrical potential energy J

E cell   V
unit of charge moved C
 17_363

e– e–

e–
e– Ecell = +1.10 V

+ +
Zn 2 Cu 2
– –
SO 4 2 SO 4 2
Zn(s) Cu(s)
+ +
1.0 M Zn 2 1.0 M Cu 2
solution solution

Anode Cathode
 Cell Potential, E0cell

E0cell
cell potential under standard conditions

elements in standard states (298 K)

solutions: 1 M
gases: 1 atm
 Standard Reduction Potentials
E0 values for reduction half-reactions with
solutes at 1M and gases at 1 atm

Cu2+ + 2e  Cu
E0 = 0.34 V vs. SHE

SO42 + 4H+ + 2e  H2SO3 + H2O

E0 = 0.20 V vs. SHE
 E0cell and DG0

E0cell > 0 DG0 < 0 Spontaneous

E0cell < 0 DG0 > 0 Not

E0cell = 0 DG0 = 0 Equilibrium

 Calculating E0cell
E0cell = E0cathode - E0anode

Br2(aq)+2V3+ +2H2O(l)  2VO2+(aq)+ 4H+(aq)+ 2Br-(aq)

Given: E0cell = +1.39 V

E0Br2 = +1.07 V

What is E0V3+ and is the reaction spontaneous?

 E0 values
More positive:
Stronger oxidizing agent
More readily accepts e-

More negative:
Stronger reducing agent
More readily gives e-

Stronger R.A. + O.A.  Weaker R.A. + O.A.

Free Energy and Cell Potential

0 0
wmax  G   nFE

n: number of moles of e-
F: Faraday’s constant
96485 C
mol of e-
 DG0, E0, and K
0 0
G   RTlnK   nFE
0 RT
so E  lnK
nF
At equilibrium: DG0 = 0 and K = Q
At 298 K:
0 0.0592
E  logK
n
 Nernst Equation
Under nonstandard conditions
0
G  G  RTlnQ
0
 nFE   nFE  RTlnQ

0 RT
E cell E  lnQ
nF
298K 0 0.0592
E cell E  lnQ
n
 Concentration Cells

. . . a cell in which both compartments

have the same components but at
different concentrations
17_366

e– e–

e– Porous e–
disk
Ag Ag

0.1 M Ag+ 1 M Ag+

– –
0.1 M NO 3 1 M NO 3

Anode Cathode
17_369

Reference solution of
dilute hydrochloric acid

Silver wire coated with

silver chloride

Thin-walled membrane
 Batteries

A battery is a galvanic cell or, more

commonly, a group of galvanic
cells connected in series.
 Fuel Cells
Galvanic cells
Reactants are continuously supplied.
2H2(g) + O2(g)  2H2O(l)

anode: 2H2 + 4OH  4H2O + 4e

cathode: 4e + O2 + 2H2O  4OH
 Corrosion

Some metals, such as copper, gold, silver and

platinum, are relatively difficult to oxidize.

These are often called noble metals.

 Electrolysis

Forcing a current through a cell to

produce a chemical change for
which the cell potential is negative.
17_378

Electrodes of
graphite rods
To external
power source

Carbon
dioxide Molten Al 2O3/Na3AlF6
formed at mixture
the anodes
Molten
aluminum
Carbon-lined iron tank

Plug
 Stoichiometry

How much chemical change occurs with the flow

of a given current for a specified time?

current and time  quantity of charge 

moles of electrons  moles of analyte 
grams of analyte