Oxidation and Reduction

Transfer of electrons between species

Thermodynamic
Kinetics
Conditions
Procedures for evaluating redox
Trends in oxidation
Reduction
Electron gain
Oxidation
Electron loss
Reducing agent supplies electrons
Oxidizing agent removes electrons
For an element, redox results in change of
oxidation state

6-1

Periodic Variations of Oxidation State

1

18
13-17

2
3

constant

6-12

Steps of 1

Steps of 2
Mainly 3+
6-2

Oxidizing and Reducing Agents

Oxidizing Agents
F2
Cl2
Br2
Ag+
Strong
I2
Cu2+
H+
Fe2+
weak
Zn2+
Al3+
Na+

Reducing Agents
FClBrAg
ICu
H2
Fe
Zn
Al
Na

6-3

Extraction of the elements

Origin of the term Oxidation
From the reaction of an element with O2
Reduction from oxide to metal
Separation by reduction
Metal oxides reduced at higher temperature
in the presence of a reducing agent
Carbon used in early smelting
Electrolysis
Electric current used for reduction
6-4

Thermodynamics
Gibbs free energy
G=-RTlnK= H-T S
Negative value
spontaneous
Phase changes effect
free energy due to
entropy
* Exploited in
metal reduction
Temperature dependence
on free energy
Metal reduced by C or
CO
Eappl G/nF

6-5

Pyrometallurgy

6-6

Extraction by oxidation

Separations of halogens
2 Cl- +2 H2O2 OH-+H2+Cl2 G=422 kJ/mol
Apply overpotential
Overpotential always reduces theoretical cell potential when
current is flowing
= Ecurrent - Eequilibrium
Overpotential due to electrode polarization:
concentration polarization - mass transport limited
adsorption/desorption polarization - rate of surface
attach/detachment
charge-transfer polarization - rate of redox reaction
reaction polarization - rate of redox reaction of
intermediate in redox reaction
Overpotential means one must apply greater potential before
redox chemistry occurs
6-7

Redox Reactions
Zn + Cu2+ <--> Zn2+ + Cu
Zn is oxidized, Cu is reduced
Transfer of electrons from one metal to another
May not involved charge species
C + O2 <--> CO2
Oxidation agent oxidizes another species and is reduced
Reduction agent reduces another species and is
oxidized

6-8

Balancing Redox Equations

Balancing can be accomplished through examining ionelectron half reactions
H+ + NO3- + Cu2O <--> Cu2+ + NO + H2O
Identify reduced and oxidized species
Cu2O to Cu2+ (1+ to 2+): oxidized
NO3- to NO (5+ to 2+): reduced
Balance oxidized/reduced atoms
Cu2O <--> 2Cu2+
Add electrons to balance redox of element
Cu2O <--> 2Cu2+ + 2e NO3- + 3e- <--> NO
6-9

Balancing Redox Equations

Add H+ (or OH-) to balance charge of reaction
2H+ + Cu2O <--> 2Cu2+ + 2e4 H+ + NO3- + 3e- <--> NO
Add water to balance O and H, then balance other
atoms if needed
2H+ + Cu2O <--> 2Cu2+ + 2e- + H2O
4 H+ + NO3- + 3e- <--> NO + 2 H2O
Multiple equations to normalize electrons
3(2H+ + Cu2O <--> 2Cu2+ + 2e- + H2O)
2(4 H+ + NO3- + 3e- <--> NO + 2 H2O)
6-10

Balancing Equations
Add the reactions together
14H+ + 2NO3- + 3Cu2O <--> 6Cu2++2NO +7 H2O
Important for reactions involving metal with multiple
oxidation states
Disproportionation
Some elements with intermediate states can react to
form species with different oxidation states
Species acts as both oxidation and reduction agent
2 Pu4+ <--> Pu3+ + Pu5+

6-11

Electrochemistry
Chemical transformations produced by
electricity
Corrosion
Refining
Electrical Units
Coulomb (C)
Charge on 6.25 x 1018 electrons
Amperes (A)
Electric current
A=1C/sec
6-12

Electrochemistry
Volt (V)
Potential driving current flow
V= 1 J/C
Ohms law
= IR
= potential, I =current, and R=resistance
symbol
Charge
q
Current I
Potential
Power
P
Energy
E
Resistance R

unit
Coulomb (C)
Ampere (A)
Volt (V)
Watt (W)
Joule (J)
Ohm ()

relationships
I=q/t (t in s)
=IR
P= I
Pt= It= q
R= /I

6-13

Electrolysis
Production of a chemical reaction by means of an
electric current
2 H2O <--> 2H2 + O2
Cathode
Electrode at which reduction occurs
Cations migrate to cathode
Cu2+ + 2e- <--> Cu
Anode
Electrode at which oxidation occurs
Anions migrate to anode
2Cl- <-->Cl2 + 2e6-14

Electrolysis
Redox depends upon tendencies of elements or
compounds to gain or lose electrons
electrochemical series
Lists of elements or compounds
Half cell potentials
Related to periodic tendencies

6-15

Electrolysis of CuCl2
Anode: 2Cl-->Cl2+2eCathode: Cu2++2e-->Cu
C electrode
Cu Plating on C
electrode

C electrode

Cl2

6-16

NaCl
Solutions
Dilute NaCl solution

anode: 2 H2O <--> O2 + 4H+ + 4e cathode: 2 H2O + 2e- <--> H2 + 2OH Concentrated NaCl (Brines)
anode: 2Cl- <--> Cl2 + 2e cathode: 2 H2O + 2e- <--> H2 + 2OH Molten Salt
anode: 2Cl- <--> Cl2 + 2e cathode: Na+ + e- <-->Na
Na metal produced by electrolysis of NaCl and
Na2CO3
Lower melting point than NaCl

6-17

Faraday Laws
In 1834 Faraday demonstrated that the quantities of
chemicals which react at electrodes are directly
proportional to the quantity of charge passed through
the cell
96487 C is the charge on 1 mole of electrons = 1F
(faraday)

6-18

Faraday Laws
Cu(II) is electrolyzed by a current of 10A for 1
hr between Cu electrode
anode: Cu <--> Cu2+ + 2ecathode: Cu2+ + 2e- <--> Cu
Number of electrons
(10A)(3600 sec)/(96487 C/mol) = 0.373 F
0.373 mole e- (1 mole Cu/2 mole e-) =
0.186 mole Cu

6-19

Electrochemical cell

6-20

Conduction in a cell
Charge is conducted
Electrodes
Ions in solution
Electrode surfaces
Oxidation and reduction
Oxidation at anode
Reduction at cathode
Reaction can be written as half-cell potentials
6-21

Half-cell potentials
Standard potential
Defined as =0.00V
H2(atm) <--> 2 H+ (1.000M) + 2e Cell reaction for
Zn and Fe3+/2+ at 1.0 M
Write as reduction potentials
Fe3+ + e- <--> Fe2+
=0.77 V
Zn2+ + 2e- <-->Zn
=-0.76 V
Fe3+ is reduced, Zn is oxidized
6-22

Half-Cell Potentials
Overall
2Fe3+ +Zn <--> 2Fe2+ + Zn2+ =0.77+0.76=1.53 V
Half cell potential values are not multiplied
Application of Gibbs
If work is done by a system
G = -nF (n= e-)
Find G for Zn/Cu cell at 1.0 M
Cu2+ + Zn <--> Cu + Zn2+ =1.10 V
2 moles of electrons (n=2)
G =-2(96487C/mole e-)(1.10V)
G = -212 kJ/mol

6-23

Reduction Potentials
Electrode Couple
Na+ + e- --> Na
Mg2+ + 2e- --> Mg
Al3+ + 3e- --> Al
Zn2+ + 2e- --> Zn
Fe2+ + 2e- --> Fe
Cd2+ + 2e- --> Cd
Tl+ + e- --> Tl
Sn2+ + 2e- --> Sn
Pb2+ + 2e- --> Pb
2H+ + 2e- --> H2(SHE)
S4O62- + 2e- --> 2S2O32Sn4+ + 2e- --> Sn2+
SO42- + 4H+ + 2e- --> H2O + H2SO3(aq)
Cu2+ + e- --> Cu+
S + 2H+ + 2e- --> H2S
AgCl + e- --> Ag + ClSaturated Calomel (SCE)
UO22+ + 4H+ + 2e- --> U4+ + 4H2O

"E0, V"
-2.7144
-2.3568
-1.676
-0.7621
-0.4089
-0.4022
-0.3358
-0.141
-0.1266
0
0.0238
0.1539
0.1576
0.1607
0.1739
0.2221
0.2412
0.2682
6-24

Reduction Potentials
Hg2Cl2 + 2e- --> 2Cl- + 2Hg
Bi3+ + 3e- --> Bi
Cu2+ + 2e- --> Cu
Fe(CN)63- + e- --> Fe(CN)64Cu+ + e- --> Cu
I2 + 2e- --> 2II3- + 2e- --> 3IH3AsO4(aq) + 2H+ + 2e- -->H3AsO3(aq) + H2O
2HgCl2 + 4H+ + 2e- -->Hg2Cl2 + 2ClHg2SO4 + 2e- --> 2Hg + SO42I2(aq) + 2e- --> 2IO2 + 2H+ + 2e- --> H2O2(l)
O2 + 2H+ + 2e- --> H2O2(aq)
Fe3+ + e- --> Fe2+
Hg22+ + 2e- --> Hg
Ag+ + e- --> Ag
Hg2+ + 2e- --> Hg
2Hg2+ + 2e- --> Hg22+
NO3- + 3H+ + 2e- -->HNO2(aq) + H2O

0.268
0.286
0.3394
0.3557
0.518
0.5345
0.5354
0.5748
0.6011
0.6152
0.6195
0.6237
0.6945
0.769
0.7955
0.7991
0.8519
0.9083
0.9275
6-25

Reduction Potentials
VO2+ + 2H+ + e- --> VO2+ + H2O
HNO2(aq) + H+ + e- --> NO + H2O
Br2(l) + 2e- --> 2BrBr2(aq) + 2e- --> 2Br2IO3- + 12H+ + 10e- -->6H2O + I2
O2 + 4H+ + 4e- --> 2H2O
MnO2 + 4H+ + 2e- -->Mn2+ + 2H2O
Cl2 + 2e- --> 2ClMnO4- + 8H+ + 5e- -->4H2O + Mn2+

1.0004
1.0362
1.0775
1.0978
1.2093
1.2288
1.1406
1.3601
1.5119

2BrO3- + 12H+ + 10e- -->6H2O + Br2

1.5131

6-26

Nernst Equation
Compensated for non unit activity (not 1 M)
Relationship between cell potential and activities
aA + bB +ne- <--> cC + dD
[C]c [D]d
2.30RT
log
=
nF
[A]a [B]b
At 298K 2.3RT/F = 0.0592
What is potential of an electrode of Zn(s) and 0.01 M
Zn2+
Zn2+ +2e- <--> Zn = -0.763 V
activity of metal is 1
0.0592
1
= 0.763
log
= 0.822V
2
0.01
6-27

Kinetic Factors

Overpotential of 0.6 V for

metal reactions
Oxidation of water
Reduction of hydrogen
ions
Added potential
beyond equilibrium
conditions
Electron transfer
Outer sphere transfer
Minimal change in
complex
* No change in
coordination
sphere
* Minimal bond
distance
Rapid kinetics
dN/dtexp(E)

6-28

Kinetic Factors

Inner-sphere electron transfer

Change in coordination
sphere
Ligand change after
redox
Non-complementary redox
reaction
Changes in oxidation
numbers of agents are
unequal
Slow reactions since
multiple steps
Oxidation of pblock oxoanions by
d-block ions
* Steps of 2 by
steps of 1
High oxidation state, smaller
radius, slower reduction

6-29

Cyclic Voltammetry

Oxidation and reduction

Variation of rates
Peak potentials
Anode (bottom peak)
Cathode (top peak)
Difference 0.0592/n
Peak currents
Cathode (line to peak)
Anode (slope to bottom)
Peak currents equal
and opposite sign
Mechanisms and rates of
redox
6-30

Redox stability in water

Water redox
Reduced to H2
2 H2O + 2e-H2 +
2OH- E=-0.059V*pH
Oxidized to O2
O2+4H++4e- 2
H2O E=1.23V0.059V*pH
Oxidation by water
M + H+M++0.5 H2
s block except Be,
Group 4 to Group 7
May need to occur in
acid rather than water
Reduction by water
Ion reduced by water with
O2 evolution
6-31

Oxidation by O2
Oxidation of metals by O2 in air
Fe3+/Fe2+ = 0.77 V
Consider O2 half reaction
* O2+4H++4e- 2 H2O E=1.23V0.059V*pH
At pH=0, E=0.46 V
At pH 7, E=0.047 V
Consider Cu metal oxidation
Cu2+/Cu=0.34 V
6-32

Potential Diagrams
Latimer Diagrams
Quantitative data for each element
Frost Diagrams
Qualitative description of relative oxidation
state stabilities
Latimer Diagrams
Shows changes in oxidation state and
species for a given element
6-33

6-34

Potential Diagrams
ClO4- and ClO3- represents the half-reaction
ClO4- +2H+ +2e- ClO3- + H2O, E=1.20 V
Reaction is acidic, so proton is added
For basic conditions the diagram is

Cl2+ 2 e- 2 Cl- has no protons

Need to include OH- for basic reaction for
balance
Non-adjacent species redox
Find based on G = -nF (n= e-) and
G = G+ G
-nF= -nF + -nF , n=n+n
= (n + n)/(n)

6-35

Disproportionation

2 M+M + M2+
Positive E, spontaneous
Evaluate half reactions to determine thermodynamics
Tends to disproportionate if right potential is higher than
left potential
2H2O2 2H2O + O2
H2O2+2H++2e-2H2O E= 1.76 V
O2+2H++2e-2H2O2 E= 0.69 V
E=1.07 V
6-36

Frost Diagrams

Plot of nE versus oxidation number

nE= -G/F
Most stable oxidation state is
lowest nE value
Slope related to potential

Can construct Frost diagrams

from Latimer diagram
Need to consider electrons
transferred in reactions
Consider Tl

Tl to Tl+ nE=-0.336

Tl to Tl3+ nE=2.16
Construct Frost diagram
2.5

nE (V)

1.5

0.5

6-37
-0.5
-0.5

0.5

1.5

Oxidation number

2.5

3.5

Utilization of Frost Diagrams

Thermodynamic stability at the bottom of the diagram

Mn (II) is the most stable species.

species located on a convex curve can undergo
disproportionation

MnO42- and Mn (III) tends to disproportionate.

species on a concave curve do not typically
disproportionate

MnO2 does not disproportionate

species on the upper left side is a oxidizing agent

MnO4- is a strong oxidizer.

species located on the upper rignt side of the diagram is
reducing agent

manganese metal is a moderate reducing agent

information obtained from a Frost diagram is for species
under standard conditions

(pH=0 for acidic solution and pH=14 for basic

solution)
Changes in pH may change the relative stabilities of the
species
potential of any process involving the hydrogen ion will
change with pH because the concentration of this species is
changing

Need to consider in speciation

Under basic conditions aqueous Mn2+ does not

exist, insoluble Mn(OH)2 forms

6-38

Pourbaix Diagram
Eh-pH diagrams
shows thermodynamically foavored form of
an element as a function of potential and
pH
provide a visual representation of the
oxidizing and reducing abilities of the
major stable compounds of an element
used frequently in geochemical,
environmental and corrosion applications

6-39

Pourbaix Diagram

Strong oxidizing agents and

oxidizing conditions are found
at the top
Reducing agents and reducing
conditions are found at the
bottom
When the predominance area
for a given oxidation state
disappears completely above or
below a given pH and the
element is in an intermediate
oxidation state, the element will
undergo disproportionation
species that ranges from the top
to the bottom of the diagram at
a given pH will have no
oxidizing or reducing properties
at that pH
Horizontal lines indicate no
proton involved in reaction

Mn2++2e- Mn
6-40

Complexation and potentials

Metal complexes have different potentials than aquo
coordinated ions
Can stabilize oxidation state
Against both oxidation and reduction
Fe(CN)6 3+/2+ = 0.36 V
* Related to stability
More stable complexes are more
resistant to reduction
Consider Fe3+ to Fe
Which complex is more stable, hydroxide or S?

6-41