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Oxidation--Reduction

Oxidation

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Redox reactions - transfer of electrons between species.

All the redox reactions have two parts:

Oxidation Reduction
The Loss of Electrons is Oxidation.
An element that loses electrons is said to be oxidized.
The species in which that element is present in a
reaction is called the reducing agent.

The Gain of Electrons is Reduction.


An element that gains electrons is said to be reduced.
The species in which that element is present in a
reaction is called the oxidizing agent.

Mg Mg2+

Cu2+ Cu
Balancing Redox Equations
Fe2+ + MnO4- + H+ Mn2+ + Fe3+ + H2O

1. Assign oxidation numbers to each atom.


2. Determine the elements that get oxidized and reduced.
3. Split the equation into half-reactions.
4. Balance all atoms in each half-reaction, except H and O.
5. Balance O atoms using H2O.
6. Balance H atoms using H+.
7. Balance charge using electrons.
8. Sum together the two half-reactions, so that: e- lost = e-
gained
9. If the solution is basic, add a number of OH- ions to each
side of the equation equal to the number of H+ ions shown
in the overall equation. Note that H+ + OH- H2O
Example

Fe2+ + MnO4- + H+ Mn2+ + Fe3+ + H2O

MnO4- Mn2+ Reduction half reaction


(+7) (+2)

Fe2+ Fe3+ Oxidation half reaction

MnO4- + 8H+ + 5e Mn2+ + 4H2O

5Fe2+ 5Fe3+ +5e

5Fe2+ + MnO4- + 8H+ Mn2+ + 5Fe3+ + 4H2O


Disproportionation
the potential on the left of a species is less positive than that on the
right- the species can oxidize and reduce itself, a process known
as disproportionation.
Is it spontaneous?

H2O2(aq) + 2H+ (aq) +2e- 2H2O(aq) +1.76 V

O2(g) + 2H+(aq) +2 e- H2O2(aq) +0.7 V

H2O2(aq) O2 (g) + H2O(l) +0.7 V

Yes the reaction is spontaneous


Another example

2 Cu+(aq) Cu2+(aq) + Cu(s)

Cu+(aq) + e- Cu(s) E0 = + 0.52 V

Cu2+(aq) + e- Cu+(aq) E0 = =0.16 V

Cu(I) undergo disproportionation in aqueous solution


Comproportionation reaction

Reverse of disproportionation

Ag2+(aq) + Ag(s) 2Ag+(aq) E0 = + 1.18 V

we will study this in detail under Frost diagram


Nernst Equation

aOx1 +bRed2 aRed1 + bOx2

[Red1]a [Ox2]b RT
Q= E = E0 - nF ln Q
[Ox1]a [Red2]b

E0 = Standard Potential
R = Gas constant 8.314 J/K.mol
F- Faraday constant = 94485 J/V.mol
n- number of electrons
G0 = - n F E0

Note: if G0 < 0, then E0 must be >0

A reaction is favorable if E0 > 0

(a) 2H+ (aq) + 2e H2(g) E0 (H+, H2) = 0

(b) Zn2+ (aq) + 2e Zn(s) E0 (Zn2+, Zn) = -0.76 V

(a-b) 2H+ (aq) + Zn(s) Zn2+(aq) + H2(g) E0 = +0.76 V

Reaction is favorable
Hydrogen Electrode

consists of a platinum
electrode covered with
a fine powder of
platinum around
which H2(g) is bubbled.
Its potential is defined
as zero volts.
Hydrogen Half-Cell
H2(g) = 2 H+(aq) + 2 e-
reversible reaction
Galvanic Cell
-
Diagrammatic presentation of potential data

Latimer Diagram

Frost Diagram
Latimer Diagram
* Written with the most oxidized species on the left, and the most
reduced species on the right.

* Oxidation number decrease from left to right and the E0 values


are written above the line joining the species involved in the
couple.

w x y z
A+5 B+3 C+1 D0 E-2
What happens when Fe(s) react with H+?
Iron +2 and +3 G = -nFE
2+ -2 x F x -0.44 = 0.88 V
Fe + 2e Fe -0.440

Fe3+ + e Fe2+ -0.771 -1 x F x +0.771 = -0.771 V

Fe3+ + 3e Fe + 0.109 F
= -3 x F x 0.036
+0.036 Fe3+
Fe

+0.44 Fe2+

-0.036

Fe3+ +0.77 Fe2+ -0.44 Fe


-0.036

Fe3+ +0.77 Fe2+ -0.44 Fe

0.36
[Fe(CN)6]3- -1.16
[Fe(CN)6 ]4-

Oxidation of Fe(0) to Fe(II) is considerably more favorable in the


cyanide/acid mixture than in aqueous acid.

(1) Concentration
(2) Temperature
(3) Other reagents which are not inert
Oxidation of elemental copper
Latimer diagram for chlorine in acidic solution

- +1.2 - +1.18 +1.65 +1.63 +1.36


ClO4 ClO3 HClO2 HClO Cl2 Cl-
+7 +5 +3 +1 0 -1

- +1.2
ClO4 ClO3-

Can you balance the equation?

+1.63
HClO Cl2
balance the equation

2 HClO(aq) + 2 H+(aq) + 2 e- Cl2(g) + 2 H2O(l) E0 = +1.63 V


How to extract E0 for nonadjacent oxidation state?
E0 =?
- +1.2 - +1.18 +1.65 +1.63 +1.36
ClO4 ClO3 HClO2 HClO Cl2 Cl-
+7 +5 +3 +1
+1 00 -1
-1

Identify the two reodx couples 1 2

Find out the oxidation state of chlorine


Write the balanced equation for the first couple
HClO(aq) + H+(aq) + e Cl2(g) + H2O(l) +1.63 V
Write the balanced equation for the second couple
G = G + G
-FE = - FE - FE
Cl2(g) + e -
Cl (l) +1.36 V
E = E+ E
+
E = 1.5 V
Latimer diagram for chlorine in basic solution

- +1.2 - +1.18 +1.65 +1.63 +1.36


ClO4 ClO3 HClO2 HClO Cl2 Cl-
+7 +5 +3 +1 0 -1

+0.37 +0.3 +0.68 +0.42 +1.36


ClO4 - ClO3 - ClO2 - ClO- Cl2 Cl-

+0.89
+0.89
+0.42
ClO- Cl2
Balance the equation

2ClO- (aq) + 2H2O(l) + 2e- Cl2(g) + 4OH-(aq) E0 = 0.42 V


Find out the E0

+0.89
Disproportionation
Element is simultaneously oxidized and reduced.
2 M+(aq) M(s) + M2+(aq)
E0 E0
M(s) 2M+(aq) M2+(aq)

+0.37 +0.3 +0.68 +0.42 +1.36


ClO4 - ClO3 - ClO2 - ClO- Cl2 Cl-

the potential on the left of a species is less positive than that on


the right- the species can oxidize and reduce itself, a process known
as disproportionation.
+0.42 +1.36
ClO- Cl2 Cl-
+0.37 +0.3 +0.68 +0.42 +1.36
ClO4 - ClO3 - ClO2 - ClO- Cl2 Cl-

+0.42 +1.36
ClO- Cl2 Cl-

Cl2(g) + 2 e- 2Cl-(aq) +1.36


2ClO- (aq) 2H2O(l) +2e- Cl2(g) + 4OH-(aq) +0.42

Cl2 + 2OH- ClO- + Cl- + H2O

E = E0 (Cl2/Cl-) E0 (ClO-/Cl2) = 1.36 - +0.42 = 0.94

Reaction is spontaneous
Latimer diagram for Oxygen

1.23 V
Disproportionation
the potential on the left of a species is less positive than that on the
right- the species can oxidize and reduce itself, a process known
as disproportionation.
Is it spontaneous?

H2O2(aq) + 2H+ (aq) +2e- 2H2O(aq) +1.76 V

O2(g) + 2H+(aq) +2 e- H2O2(aq) +0.7 V

H2O2(aq) O2 (g) + H2O(l) +0.7 V

Yes the reaction is spontaneous


Another example

2 Cu+(aq) Cu2+(aq) + Cu(s)

Cu+(aq) + e- Cu(s) E0 = + 0.52 V


Cu2+(aq) + e- Cu+(aq) E0 = =0.16 V

Cu(I) undergo disproportionation in aqueous solution


Comproportionation reaction

Reverse of disproportionation

Ag2+(aq) + Ag(s) 2Ag+(aq) E0 = + 1.18 V

we will study this in detail under Frost diagram


Frost Diagram
Arthur A. Frost
Graphically illustration of the stability of different oxidation
states relative to its elemental form (ie, relative to oxidation
state= 0)

XN + Ne- X0

NE0 = -G0/F
Look at the Latimer diagram of nitrogen in acidic solution

a b c d e

f g h
c
a

b
d
g
G = G + G
-nFE = -nFE - nFE
N2 E = nE+ nE
f n+n

h
a NO3- + 6H+ + 5e- N2 + 3H2O E0 = 1.25V

b N2O4 + 4H+ + 4e- N2 + 2H2O E0 = 1.36V

c HNO2 + 3H+ + 3e- N2 + 2H2O E0 = 1.45V

d NO + 2H+ + 2e- N2 + H2O E0 = 1.68V

e N2O + H+ + e- N2 + H2O E0 = 1.77V

f N2 + 2H+ + H2O + e- NH3OH+ E0 = -1.87V

g N2 + 5/2 H+ + 2e- N2H5+ E0 = -0.23V

h N2 + 4H+ + 3e- NH4+ E0 = 0.27V


Oxidation state: species NE0, N
N(V): NO3- (5 x 1.25, 5)

N(IV): N2O4 (4 x 1.36, 4)

N(III): HNO2 (3 x 1.35, 3)

N(II): NO (2 x 1.68, 2)

N(I): N2O (1 x 1.77, 1)

N(-I): NH3OH+ [-1 x (-1.87), -1]

N(-II): N2H5+ [-2 x (-0.23), -2]

N(-III): NH4+ (-3 x 0.27, -3)


Frost Diagram N2
What do we really get from the Frost diagram?

the lowest lying species corresponds to


the most stable oxidation state of the
element
Slope of the line joining any two points is equal to the std
potential of the couple
couple..

NE0

NE0
NE0-NE0
N Slope = E0=
N-N
E0 of a redox couple
HNO2/NO

3, 4.4

2, 3.4

NE0-NE0
Slope = E0=
N-N
1V
Oxidizing agent? Reducing agent?

The oxidizing agent - couple with more positive slope - more


positive E

The reducing agent - couple with less positive slope

If the line has ive slope- higher lying species reducing agent

If the line has +ive slope higher lying species oxidizing agent
Identifying strong or weak agent?
NO Strong oxidant than HNO3
Comproportionation

In acidic solution
Mn and MnO2

Mn2+
Rate of the reaction hindered
insolubility?

In basic solution
MnO2 and Mn(OH)2

Mn2O3
From the Frost diagram for Mn.
* Thermodynamic stability is found at the bottom of the diagram.
Mn (II) is the most stable species.

* A species located on a convex curve can undergo disproportionation


example: MnO43- MnO2 and MnO42- (in basic solution)

Any species located on the upper right side of the diagram will be
a strong oxidizing agent. MnO4- - strong oxidizing agent.

Any species located on the upper left side of the diagram will be
a reducing agent. Mn - moderate reducing agent.
Disproportionation
Element is simultaneously oxidized and reduced.
2 M+(aq) M(s) + M2+(aq)
E0 E0
M(s) 2M+(aq) M2+(aq)

the potential on the left of a species is less positive than that on


the right- the species can oxidize and reduce itself, a process known
as disproportionation.
Disproportionation
What Frost diagram tells about this reaction?
A species in a Frost diagram is unstable with respect to disproportionation
if its point lies above the line connecting two adjacent species.
species.
Disproportionation. another example
Comproportionation reaction
Comproportionation is spontaneous if the intermediate species
lies below the straight line joining the two reactant species.
Favorable?
NE0
Disproportionation
Thank You

Best wishes

OC - 105 (Ph 83338)


Organic Chemistry Bldg.
Dept. of Chemistry
(Behind RTC)
Comproportionation

In acidic solution
Mn and MnO2

Mn2+
Rate of the reaction hindered
insolubility?

In basic solution
MnO2 and Mn(OH)2

Mn2O3
From the Frost diagram for Mn.
* Thermodynamic stability is found at the bottom of the diagram.
Mn (II) is the most stable species.

* A species located on a convex curve can undergo disproportionation


example: MnO43- MnO2 and MnO42- (in basic solution)

Any species located on the upper right side of the diagram will be
a strong oxidizing agent. MnO4- - strong oxidizing agent.

Any species located on the upper left side of the diagram will be
a reducing agent. Mn - moderate reducing agent.
* Although it is thermodynamically favorable for permanganate
ion to be reduced to Mn(II) ion, the reaction is slow except in the
presence of a catalyst. Thus, solutions of permanganate can be
stored and used in the laboratory.

* Changes in pH may change the relative stabilities of the species.


The potential of any process involving the hydrogen ion will
change with pH because the concentration of this species is
changing.

* Under basic conditions aqueous Mn2+ does not exist. Instead


Insoluble Mn(OH)2 forms.
*All metals are good reducing agents

*Exception: Cu
*Reducing strength: goes down
smoothly from Ca to Ni
*Ni- mild reducing agent

*Early transition elements: +3 state


Latter +2 state

*Fe and Mn many oxidation states


*High oxidation state:
Strong oxidizing agents