OxidationReduction Reactions

Oxidation Loss of electrons

Reduction Gain of electrons

Zn( s ) + 2 H + ( aq ) Zn +2 ( aq ) + H 2 ( g )

Zn is oxidized
H+ is reduced

Zn is the reducing agent reductant

H+ is the oxidizing agent oxidant
 Oxidation Numbers
1. For an atom in its elemental form the
oxidation number is zero.
2. For any monoatomic ion the oxidation
number equals the charge on the ion.
K+, O-2, Al+3, etc
3. Nonmetals usually have negative
oxidation numbers.
a. the oxidation number of O is usually -2
b. the oxidation number of H is +1 when it is
bonded to a non metal (H2O, NH3, H3PO4,
etc. ) and -1 when it is bonded to a metal
(CaH2, NaH, etc.)
c. the oxidation number of F is always -1.
The other halogens are usually -1 but when
combined with oxygen in oxycations it is +1
( OCl-1, O2Cl-2, etc. )
If this were an ionic compound, what
would the charges be?
Identify the oxidation numbers

H 2O
NiO2

MnO 4

Ni( OH )2
Al( OH )4
2
C2 O 4

NH 3
2
Cr2O 7

ClO3
 Balancing Oxidation Reduction Reactions
Half-Reaction Method

Sn +2 ( aq ) + Fe +3 ( aq ) Sn +4 ( aq ) + Fe +2 ( aq )

Sn +2 ( aq ) Sn +4 ( aq ) + 2e

Fe +3 ( aq ) + e Fe +2 ( aq )

2 Fe +3 ( aq ) + 2e 2 Fe+2 ( aq )
Sn +2 ( aq ) Sn +4 ( aq ) + 2e
Sn +2 ( aq ) + 2 Fe+3 ( aq ) Sn +4 ( aq ) + 2 Fe+2 ( aq )
MnO4 ( aq ) + C2O42 ( aq ) Mn +2 ( aq ) + CO2 ( g ) Acidic solution

2 MnO4 ( aq ) + 5C2O42 ( aq ) + 16 H + ( aq ) 2 Mn +2 ( aq ) + 10CO2 ( g ) + 8 H 2O( l )

2 MnO4 ( aq ) + 5C2O42 ( aq ) + 16 H + ( aq )

2 Mn +2 ( aq ) + 10CO2 ( g ) + 8H 2O( l )
 MnO4 ( aq ) Mn +2 ( aq ) + 4 H 2O( l )

8 H + ( aq ) + MnO4 ( aq ) Mn +2 ( aq ) + 4 H 2O( l )

5e + 8 H + ( aq ) + MnO4 ( aq ) Mn +2 ( aq ) + 4 H 2O( l )

C2O42 ( aq ) 2CO2 ( g )

C2O42 ( aq ) 2CO2 ( g ) + 2e

10e + 16 H + ( aq ) + 2 MnO4 ( aq ) 2 Mn +2 ( aq ) + 8 H 2O( l )

5C2O42 ( aq ) 10CO2 ( g ) +10e

2MnO4 ( aq ) + 5C2O42 ( aq ) + 16 H + ( aq )

2Mn +2 ( aq ) + 10CO2 ( g ) + 8H 2O( l )
 Rules (Acidic Solution)

1. Divide the reaction into half-reactions

2. Balance each half-reaction

a. First balance elements other than O & H
b. Balance O atoms using H2O
c. Balance H atoms with H+
d. Balance charge with e-

3. Multiply each half reaction by an integer

so each has the same number of electrons

4. Add half reactions and simplify

5. Check!
 Balancing in a basic solution

Use OH- & H2O

Given

CN ( aq ) + MnO4 ( aq ) CNO ( aq ) + MnO2 ( s )

Balanced Equation

3CN ( aq ) + 2MnO4 ( aq ) + H 2O( l )

3CNO ( aq ) + 2MnO2 ( s ) + 2OH ( aq )
 A Fundamental Observation

When a strip of Zn is placed in a solution

containing Cu+2(aq) ions the Cu+2(aq) ions
react with the Zn and form Cu metal while
the Zn dissolves, forming Zn+2(aq) ions.

Cu +2 ( aq ) + Zn( s ) Cu( s ) + Zn +2 ( aq )
 Voltaic Cell

A device in which a spontaneous oxidation-

reduction reaction occurs with the passage
of electrons through an external circuit.

Electrodes Two solid metals connected

by the external circuit

Anode Electrode at which oxidation

occurs

Cathode Electrode at which reduction

occurs

Salt Bridge Electrical contact between

the two solutions that
prevents them from mixing
but permits ion flow
 Electrodes need not enter into reaction

Beaker A H2O, K2Cr2O7, & H2SO4

Beaker B HI & H2O

Put Pt electrode in both beakers

Connect electrodes with wire

Connect beakers with salt bridge

Spontaneous reaction

Cr2O72 ( aq ) + 14 H + ( aq ) + 6 I ( aq )

2Cr +3 ( aq ) + 3I 2 ( s ) + 7 H 2O( l )
Cell EMF

The potential energy of the electrons is

higher at the anode
so they flow spontaneously through the
external circuit to the cathode.

The difference in potential energy is

measured in volts

A volt is one joule per coulomb of charge

J
1V = 1
C
Charge on one electron is 1.602 x 10-19 C
1Coulomb corresponds to the charge
on 6.24 x 1018 electrons.

Potential difference is called the

electromotive force (EMF) or cell voltage

Zn( s ) + Cu +2 ( aq,1M ) Zn +2 ( aq,1M ) + Cu( s ) Ecell

0
= +1.10V
Standard Reduction (Half-Cell) Potentials
A B
AB
Ecell = E( B ) E( A )

XA
XA
Ecell = E( A ) E( X )
X B
XB
Ecell = E( B ) E( X )

AB
Ecell = Ecell
XB
( B ) Ecell
XA
( A)

X is the reference electrode

XB XA
Ecell ( B )& Ecell ( A)
are called the standard reduction potentials
XB
Ecell ( B ) = Ered
0
(B)
XA
Ecell ( A ) = Ered
0
( A)
 Reference Electrode is the Standard
Hydrogen Electrode

2 H + ( aq,1M ) + 2e H 2 ( g ,1atm ) Ered

0
= 0V
 EMF Example

Determine the half-reactions that occur at

the anode and cathode and the cell EMF for
the half cells

+3
Al( s ) / Al ( aq )
I 2 ( s ) / I 1( aq )

Cr2O72 ( aq ) / Cr +3 ( aq )
1
I 2 ( s ) / I ( aq )

+2
Co ( aq ) / Co( s )
AgCl( s ) / Ag( s )
EMF, Free Energy & the Nernst Equation

G = nFEcell
F = the Faraday
the charge on one mole of electrons
(6.02214 x 10 23 e/mol)(1.60218 x 10 -19 C/e)=96500C/mol

n = the number of electrons transferred in the reaction

G = G + RT ln Q 0

nFEcell = nFE 0
cell + RT ln Q
RT
Ecell = E 0
cell ln Q
nF

0.0592
Ecell = E 0
cell log Q
n
 Example of Nernst Equation

Zn( s ) + Cu +2 ( aq ) Zn +2 ( aq ) + Cu( s )

0.0592V [ Zn +2 ( aq )]
Ecell = 1.10V log
2 [ Cu +2 ( aq )]

[ Cu +2 ] = 5.0 M , [ Zn +2 ] = 0.05M

0.0592V 0.05
Ecell = 1.10V log
2 5 .0
0.0592V
Ecell = 1.10V log 102
2

Ecell = 1.10V + 0.0592V = 1.16V

 G Examples

Given the reaction

3Ni +2 ( aq ) + 2Cr( OH )3 ( s ) + 10OH ( aq )

3Ni( s ) + 2CrO42 ( aq ) + 8H 2O( l )

What is the value of n?

What is G 0 ?

Same question for

1
2 Ag( s ) + O2 ( g ) + 2 H + ( aq ) 2 Ag + ( aq ) + H 2O( l )
2
 Nernst Equation Example

Zn( s ) + 2 H + ( aq ) Zn +2 ( aq ) + H 2 ( g )

If the voltage in this cell is 0.45V at 250C

when [Zn+2] =1.0M and PH2=1.0 atm, what
is the concentration of H+?
 Concentration Cell Examples
Two Hydrogen electrodes
Electrode 1
PH 2 = 1.00atm, [H + (aq)]=?
Electrode 2
PH 2 = 1.00atm, [H + (aq)]=1.00M

T=298K Ecell = 0.211 V

Current flow: electrode 1 to electrode 2
pH = ?

Consider two Zn(s)-Zn+2(aq) half cells

[ Zn +2 ( aq )]( cell 1 ) = 1.35M

[ Zn +2 ( aq )]( cell 2 ) = 3.75 x104 M

Which is anode?

What is emf of cell?

Strengths of Oxidizing/Reducing Agents

Standard reduction potentials can be used to

understand aqueous reaction chemistry

0
The more positive Ered the greater
the tendency for the reactant of the
half reactant to be reduced and,
therefore, to oxidize another species.

F2 ( g ) + 2e 2 F ( aq ) 0
Ered = +2.87 V

The half-reaction with the smallest

0
(algebraically) Ered
is most easily reversed as an oxidation

Li + ( aq ) + e Li( s ) 0
Ered = 3.05 V
 Rank the following ions in order of
increasing strength as oxidizing agents

NO3 ( aq )

Ag + ( aq )

Cr2O7-2 ( aq )

Rank the following ions in order of

increasing strength as reducing agents

I ( aq )

Fe(s)

Al(s)
 Batteries
Portable, self-contained electrochemical
power source that consists of one or more
voltaic cells
Primary Cell Cannot be recharged
Secondary Cell Can be recharged
Lead-Acid Battery
Cathode:
PbO2 (s)+HSO4 ( aq ) + 3H + ( aq ) + 2e

PbSO4 ( s ) + 2 H 2O( l ) Ered
0
= +1.685 V

Anode:
Pb( s ) + HSO4- ( aq )

PbSO4 ( s ) + H + ( aq ) + 2e 0
Ered = 0.356 V
Cell Reaction:
PbO2 (s)+Pb(s)+2HSO4- ( aq ) + 2 H + ( aq )

2 PbSO4 ( s ) + 2 H 2O( l )

0
Ecell = E 0 ( cathode ) E 0 ( anode )

0
Ecell = ( +1.685 V ) - (-0.356 V ) = + 2.041 V

12 V lead-acid battery
consists of 6 voltaic cells and is
rechargeable
 Alkaline Battery
Cathode:
2MnO2 (s)+2H 2O(l)+2e-

2 MnO( OH )( s ) + 2OH ( aq )

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

0
Ecell = 1.55V
 Fuel Cells

Cathode :
O2 ( g ) + 2 H 2O( l ) + 4e 4OH ( aq ) Ered
0
= +0.40V

Anode :
2 H 2 ( g ) + 4OH ( aq ) 4 H 2O( l ) + 4e 0
Ered = 0.83V

Re action :
2 H 2 ( g ) + 2O2 ( g ) 2 H 2O( aq ) Ecell
0
= +1.23V
Batteries in series
 Corrosion

Corrosion occurs when a metal undergoes a

spontaneous redox reaction and is converted
to an unwanted substance.

Oxidation is usually the thermodynamically

favored process for a metal

Corrosion of Iron

Preventing Iron from Corroding

Cathodic Protection
 Electroplating
Electrolysis with an active electrode

Ni( s ) Ni +2 ( aq ) + 2e 0
Ered = 0.28V

2 H 2O( l ) O2 ( g ) + 4 H + ( aq ) + 4e 0
Ered = +1.23V

Ni +2 ( aq ) + 2e Ni( s ) 0
Ered = 0.28V

2 H 2O( l ) + 2e H 2 ( g ) + 2OH ( aq ) Ered

0
= 0.83V
 Quantitative Aspects of Electrolysis

Stoichiometry of a half-reaction shows how

many electrons are needed for the
electrolysis

+
Na + e Na
Cu +2 + 2e Cu
+3
Al + 3e Al

Current measured in amperes (A)

Coulomb C
1A = 1 =1
sec ond s

Coulombs of charge=magnitude of current x duration of current

 Calculate the number of grams of Al
produced in 1.00 hour by the electrolysis of
molten AlCl3 if the current is 10.0A.

The half-reaction for the formation of

magnesium metal upon electrolysis of
molten MgCl2 is
Mg +2 + 2e Mg
Calculate the mass of magnesium formed
upon the passage of a current of 60.0A for
4.00x103 s
 Electrical Work

Free energy change in a process is equal to

the maximum useful work that can be
extracted from the process.

G = wmax = nFE
wmax = nFEexternal > 0

The unit of electrical power is the Watt(W)

Joule J
1Watt = 1 =1
sec ond s

Unit of energy employed by utility

companies is kilo-Watt-hour (kWh)

1kWh = 3.6 x10 J 6

Calculate the number of kilowatt-hours required
to produce 1.0 x 103 kg of Al by electrolysis of
Al+3 if the applied voltage is 5.50V

w = nFE
Cell EMF and Chemical Equilibrium

G = G 0 + RT ln Q
At equilibrium

G = 0 & Q = K eq

G 0 = RT ln K eq = nFEcell
0

0
nFEcell
ln K eq =
RT
0
nEcell
log K eq = ; T=298K
0.0592
 Calculate the equilibrium constant for the
oxidation of Fe+2 by O2 in an acidic solution

Fe +2 ( aq ) + O2 ( g ) Fe +3 ( aq ) + H 2O( l )

Fe +2 Fe +3 + e 0
Ered = +0.77V

O2 ( g ) 2 H 2O( l )
4 H + ( aq ) + O2 ( g ) 2 H 2O( l )
4 H + ( aq ) + O2 ( g ) + 4e 2 H 2O( l ) Ered
0
=+1.23V

n = 4 ; Ecell
0
= +1.23V 0.77V = 0.46V

4 x 0.46V
log K eq = = 31
0.0592V

K eq = 1.0 x1031