OXIDATION – REDUCTION

REACTION
 DEFINITION
Oxidation – reduction reaction (abbreviated
“redox” reaction ) is a chemical reaction, in
which electrons are transferred between
reactants and the oxidation states of atoms are
changed.
 Redox reaction involves:
o Oxidation: loss of electrons
Ox1 + e → Red1 ( S +2e → S2-)
Reducing agents: Substance that cause oxidation
by being oxidized
o Reduction: Gain of electrons
Red2 – e → Ox2 ( Fe –2e → Fe2+)
Oxidizing agents: Substance that cause oxidation
by being oxidized
 Reduction and oxidation
• Oxidation and reduction always
occur simultaneously
• Redox couple is the pair of oxidizing
and reducing agents that are involved
in a particular reaction.
 AFFECTING FACTOR INTO SUBSTANCES’S
REDUCTION AND OXIDATION PROPERTIES
Reduction and oxidation potential of
substances depend on:
1. Electron configuration and oxidation state of
elements and ions. (Periodic table)
2 – Periodic trend of non- metal and metal
elements (Periodic trend of electronegativity)
3- Steady properties of substances.
4- Environment properties (acidic, basic or
neutral)
Balancing Oxidation Reduction Equation
Rule 1:
• The total electrons gained in reduction equals
the total lost in oxidation.
− Step 1: assign oxidation numbers to all atoms
and identify which are oxidized/reduced.
− Step 2: write unbalanced equation in ionic form
and use coefficients to equalize.
− Step 3: add the balanced half reactions to show
an ionic overall equation.
− Step 4: balance the equation.
Exampleï:
Al + CuSO4 → Al2(SO4)3 + Cu
Al -3e → Al+3 X2

Cu+2 + 2e → Cu X3

_______________________
→2Al + 3Cu+2 = 2Al+3 + 3Cu

2Al + 3CuSO4 → 2Al2(SO4)3 + 3Cu

Rule 2: Balancing Oxidation–
Reduction Reactions occurring in
acidic solution.
Balance the O by adding as much H2O as
needed to the side deficient in O and
adding H+ to another side.
 Example
KMnO4 + KNO2 + H 2 SO4 → MnSO4 + KNO3 + K 2 SO4 + H 2O
MnO −4 + 5e → Mn +2
NO −2 − 2e → NO 3−

MnO4− + 5e + 8 H + → Mn +2 + 4 H 2O X2

NO2− − 2e + H 2O → NO3− + 2 H + X5

2MnO −4 + 5NO 2 + 6H + = 2Mn + + 5NO 3− + 3H 2 O

⇒ 2KMnO 4 + 5KNO 2 + 3H 2 SO 4 = 2MnSO 4 + 5KNO 3 + K 2 SO 4 + 3H 2 O
 Rule 3:Balancing Oxidation–Reduction
Reactions occurring in acidic solution.
Balance the O by adding as much OH- as
needed to the side deficient in O and adding
H2O to another side.
 Example:

KClO 3 + CrCl 3 + KOH → K 2 CrO 4 + KCl − + H 2 O

ClO 3− + 6e + 3H 2 O = Cl − + 6OH − X1

Cr +3 − 3e + 8OH − = CrO 4−2 + 4H 2 O X2

+3 −2
ClO + 2Cr + 10OH = Cl + 2CrO + 5 H 2O
−
3
− −
4

KClO 3 + 2CrCl 3 + 10KOH = 7KCl + 2K 2 CrO 4 + 5H 2 O

Rule 4: Balancing Oxidation–
Reduction Reactions occurring in
neutral solution.
Adding water to left side, adding OH-
to the right side of reduction half
reaction, or H+ to the right side of
oxidation half reaction.
 Example:
KMnO 4 + KNO 2 + H 2 O → MnO 2 + KNO 3 + KOH

MnO −4 + 3e + 2H 2 O = MnO 2 + 4OH − X2

NO −2 − 2e + H 2 O = NO 3− + 2H + X3

2 MnO4− + 3 NO2− + 7 H 2O = 2 MnO2 + 3 NO3− + 8OH − + 6 H +

2MnO + 3NO + H 2 O = 2MnO 2 + 3NO + 2OH

−
4
−
2
−
3
−

⇒ 2KMnO 4 + 3KNO 2 + H 2 O = 2MnO 2 + 3KNO 3 + 2KOH

Voltaic Cells
 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
 Standard Reduction
Potentials
• the potential under standard conditions
(25oC with all ions at 1 M concentrations
and all gases at 1 atm pressure) of a half-
reaction in which reduction is occurring
 Some Standard Reduction
Potentials
Li+ + e- ---> Li -3.045 v
Zn+2 + 2 e- ---> Zn -0.763v
Fe+2 + 2 e- ---> Fe -0.44v
2 H+(aq) + 2 e- ---> H2(g) 0.00v
Cu+2 + 2 e- ---> Cu
+0.337v
O2(g) + 4 H+(aq) + 4 e- ---> 2 H2O(l)
+1.229v
F2 + 2e- ---> 2 F- +2.87v
 Semireaction Zn2+(aq) + 2e− → Zn(s) −0.76
ϕ0 (V)
1bar, 298K, Ci = 1M Cr3+(aq) + 3e− → Cr(s) −0.74
Li+(aq) + e− → Li(s) −3.05 Fe2+(aq) + 2e− → Fe(s) −0.44

K+(aq) + e− → K(s) −2.93 Cr3+(aq) + e− → Cr2+(aq) −0.42

Ba2+(aq) + 2e− → Ba(s) −2.91 Sn2+(aq) + 2e− → Sn(s) −0.13

2H+(aq) + 2e− → H2(g) 0.00
Ca2+(aq) + 2e− → Ca(s) −2.76
Sn4+(aq) + 2e− → Sn2+(aq) +0.15
Na+(aq) + e− → Na(s) −2.71
Cu2+(aq) + e− → Cu+(aq) +0.16
Mg2+(aq) + 2e− → Mg(s) −2.38
SO42−(aq) + 4H+ + 2e− →
+0.17
Be2+(aq) + 2e− → Be(s) −1.85 2H2O(l) + SO2(aq)

Al3+(aq) + 3e− → Al(s) −1.68 Cu2+(aq) + 2e− → Cu(s) +0.34

Ti3+(aq) + 3e− → Ti(s) −1.21 O2(g)+2H2O(l)+4e– → 4OH–(aq) +0.40

Mn2+(aq) + 2e− → Mn(s) −1.18
SO2(aq)+4H++4e−→S(s)+ 2H2O +0.50
Sn(s) + 4H+ + 4e− → SnH4(g) −1.07
Cu+(aq) + e− → Cu(s) +0.52
2 H2O(l)+2e–→H2(g)+2OH–(aq) −0.83
I2(s) + 2e− → 2I−(aq) +0.54
MnO4–(aq) + 2H2O(l) + 3e– → Br2(aq) + 2e− → 2Br−(aq) +1.09
+0.59
MnO2(s) + 4 OH–(aq)
2IO3−(aq) + 12H+ + 10e− → I2(s)
+1.20
S2O3 +
2− 6H+ + 4e− → 2S(s) + + 6H2O
+0.60
3H2O ClO4−(aq) + 2H+ + 2e− →
+1.20
ClO3−(aq) + H2O
O2(g) + 2H+ + 2e− → H2O2(aq) +0.70
O2(g) + 4H+ + 4e− → 2H2O +1.23
Fe3+(aq) + e− → Fe2+(aq) +0.77
MnO2(s) + 4H+ + 2e− →
Hg22+(aq) + 2e− → 2Hg(l) +0.80 +1.23
Mn2+(aq) + 2H2O
Ag+(aq) + e− → Ag(s) +0.80 Cl2(g) + 2e− → 2Cl−(aq) +1.36
NO3–(aq) + 2H+(aq) +e– → Cr2O72−(aq) + 14H+ + 6e− →
+0.80 +1.36
NO2(g) + H2O(l) 2Cr3+(aq) + 7H2O

Hg2+(aq) + 2e− → Hg(l) +0.85 MnO4−(aq) + 8H+ + 5e− →

+1.51
Mn2+(aq) + 4H2O
MnO4−(aq) + H+ + e− →
+0.90 2HClO(aq) + 2H+ + 2e− →
HMnO4−(aq) +1.63
Cl2(g) + 2H2O
2Hg2+(aq) + 2e− → Hg22+(aq) +0.91 MnO4−(aq) + 4H+ + 3e− →
+1.70
MnO2(s) + 2H2O
MnO2(s) + 4H+ + e− → Mn3+(aq)
+0.95
+ 2H2O H2O2(aq) + 2H+ + 2e− → 2H2O +1.76
 OXIDATION STATE RULES OF
ELEMENTS
• Two main groups of elements:
• Transition elements (d-block elements, f-block
elements).
• Non – transition elements (s-block elements,
p-block elements)
• Each group has some specific rules to
determine stable oxidation states of elements.
• Some characteristics of elements' oxidation
numbers are mentioned in following rules
1. Zero oxidation state of strong metal and strong
non-metal is unstable. The less active the elements
are, the more stable the zero oxidation state is. The
stable oxidation state of metalloids is zero.
2. The electron configuration for elements which
have stable oxidation state in compound is no
unpaired electrons in outermost s and p subshells.
Ex: The stable oxidation state of elements in group
IIA is +2, +1 oxidation state of these elements in
compounds which are prepared in normal
conditions, is non-existent.
p-block elements: Mendeleev’s odd even rule.
Even oxidation states of elements in even groups
are more stable than odd oxidation states.
Odd oxidation states of elements in odd groups are
more stable than even oxidation states.
− Example: Odd oxidation states of Cl (VIIA): -1, +1,
+3, +5, +7 are more stable than even oxidation
states.
Even oxidation states of S (VIA): 2, +2, +4, +6 are
more stable than odd oxidation state.
The oxidation state of Xe (VIIIA), known currently
are: +2, +4, +6 and +8.
Among the oxidation states following even-odd rule, the
oxidation states which are significantly more stable than
other must satisfy two requirements:
− Electron configuration correspond to that oxidation
state is electron configuration’s noble gas.
− The element in compound correspond to the oxidation
state must use whole electron distributed on p-
outermost subshell.
− Example:
The more stable oxidation states of Cl are -1(Ar); +7 (Ne)
(noble gas); and +5 because of using whole electron of 3p
sub shell
The more stable oxidation states of S are -2 (electron
configuration of Ar), +6 (electron configuration Ne) and
+4 because of using whole electron of 3p sub shell.
3/ s-block elements:
The unique positive oxidation state of s-block
elements is the equal to the order of group in
periodic table.

− Example: Stable oxidation state of Na(IA) and

Ca(IIA) are +1 and +2, respectively.
Except, stable oxidation state of H are +1 and -1,
however, +1oxidation state is more stable than -1
oxidation state.
4/ (Nguyeân toá p):Trong moät chu kyø töø traùi qua
phaûi soá oxy hoùa döông cao nhaát cuûa nguyeân toá
keùm beàn daàn (vì raát deã laáy laïi e ñaõ maát do maät ñoä ñieän
tích döông taêng daàn vaø r giaûm daàn).
Ví duï: Xeùt daõy chu kyø III (Al, Si, P, S vaø Cl)
− Al: Möùc oxy hoùa + 3 raát beàn vöõng, nhoâm trong caùc
hôïp chaát ôû ñieàu kieän thöôøng ñeàu coù soá oxy hoùa +3.
− Si: Möùc oxy hoùa +4 raát beàn vöõng (nhö Al).
− P: ion PO43- khaù beàn, nhöng khoâng coù tính oxy hoaù
duø trong moâi tröôøng acid ñaäm ñaëc.
H3PO4 + 2H++2e=H3PO3+H2O, ϕo=-0.276V,pH=0
PO43- + 2H2O+2e=HPO32-+3OH-, ϕo=-1.12V,pH=14
− S: ion SO42- khoâng coù tính oxy hoùa trong moâi tröôøng
kieàm, coù tính oxy hoaù raát yeáu ôû moâi tröôøng acid
(pH=0) vaø laø chaát oxy hoùa khaù maïnh khi laø acid
sulfuric nguyeân chaát (oxy hoùa ñöôïc baïc).
SO42- + 4H+ + 2e = H2SO3 + H2O, ϕo=0.17V,pH=0
SO42- + H2O + 2e = SO32- + 2OH-, ϕo=-0.93V,pH=14
− Cl: Hôïp chaát +7 cuûa Cl laø chaát oxy hoùa maïnh. ClO4-
laø chaát oxy hoùa maïnh ôû pH=0, HClO4 noå khi tieáp
xuùc caùc chaát höõu cô hoaëc khi bò chieáu saùng. Tính
oxy hoùa yeáu trong moâi tröôøng kieàm.
ClO4- + 2H+ + 2e = ClO3- + H2O, ϕo=1.19V,pH=0
ClO4- + H2O + 2e = ClO3- + 2OH-, ϕo=0.36V,pH=14
5/ p-block elements: Secondary periodicity law
From the top to bottom of representative block elements,
the highest oxidation state are unstable gradually.
However, the highest oxidation state of elements in
periodic 4 is significantly unstable than that of
elements in periodic 3, similarly, the highest
oxidation state of elements in periodic 6 is
significantly unstable than that of elements in
periodic 5.
− Example 1: Investigate groupVIIA.
In the same conditions, oxidation’s property of BrO4-
is stronger than ClO4-:
ClO4- + 2H+ + 2e = ClO3- + H2O, ϕo=1.19V,pH=0
BrO4- + 2H+ + 2e = BrO3- + H2O, ϕo=1.763V,pH=0
− +7 oxidation state of At cannot exist in water
because of it strong oxidation property.
Compounds of At7+ can oxidized water and release
oxygen, while I+7’s can exist in solution.
H5IO6 + H++2e= IO3- +3H2O, ϕo=1.64V,pH=0
Example 2: Investigate group IVA.
− Compounds of Si4+ is state and cannot be oxidized
in strong acid environment and nearly be reduced I
aqueous solution.
− Ge+4 has no oxidation and acid (pH=0) but it is
easily be oxidized to +2 oxidation sate
GeO2 (r) +2H++2e= GeO(r) +H2O, ϕo=-0.12V,pH=0
− SnO2 doesn’t show oxidation property at pH=0
while, PbO2 is strong oxidation compound in same
conditions.
SnO2 (r) +2H++2e= GeO(r) +H2O, ϕo=-0.088V,pH=0
PbO2 (r) +4H++2e= Pb2+ +2H2O, ϕo= 1.445V,pH=0.

Ex. 3: Investigate redox potential of +5 oxidation

state of elements in group VA.
H3PO4 + 2H+ + 2e = H3PO3 + H2O - 0,276
H3AsO4 + 2H+ + 2e = HAsO2 + 2H2O +0,56
Sb2O5 (r) + 6H+ + 2e = 2SbO+ + 3H2O +0,58
NaBiO3 (r) + 4H+ + 2e = BiO+ + Na+ + 2H2O > +1,8
 Bang so sanh the khu

200
150
100
Series1
50
0
-50 P As Sb Bi

Secondary periodicity law can be explained:

The first time presence of 3d subshell (elements in
periodic 4) and 4f subshell (elements in periodic 6) lead
to the inactive of electron of outermost s-subshell,
therefore the highest oxidation state of elements in
periodic 4 and 6 are more unstable than that of element
in previous periodic.
6/ The highest oxidation states of transition metals
in the same group are gradually stable.

Example: The highest oxidation state of elements

in group VIB:
Half reaction φ0 (V)

Cr2O72- + 14H+ + 4e → 2Cr4+ + 7H2O +0,95

MoO42- + 4H+ + 2e → MO2↓ + 2H2O +0,606

 First five transition metal (having un-paired electron (n-1)
subshell), whole of electrons can contribute to bond-making.
While, last five transition metal have paired electron on (n-
1)d subshell and some of them can contribute to bond-
making.
In some compounds, d-transition metals can have single
electron in (n-1)d subshell.
Example 1: The current highest oxidation state of d-
transition metal of periodic 4 :
IIIB IVB VB VIB VIIB VIIIB IB IIB

Sc Ti V Cr Mn Fe Co Ni Cu Zn

+3 +4 +5 +6 +7 +6 +5 +5 +5 +2

Example 2:
Electron configuration of Cr3+ in Cr2O3 compound is (n-1)d3

↑ ↑ ↑
7/ d-block elements:
In a periodic, from left to right, the highest
oxidation state of elements become unstable
gradually.
− Example 1: Investigate periodic 4: Ti(4), V(5),
Cr(6), Mn(7), Fe(8), Co(9), Ni(10), Cu(11) (the
number of electrons distributed on 3d and 4s
subshells are shown in ()).
TiO2++ 2H++e = Ti3+ +H2O, ϕo=0.1V,pH=0
VO43-+ 6H++2e = VO+ +3H2O, ϕo=1.26V,pH=0
Cr2O72-+ 14H++6e = 2Cr3++7H2O, ϕo=1.33V,pH=0
MnO4-+ 8H++5e = Mn2++4H2O, ϕo=1.51V,pH=0
− Compound of Fe+8 does not exist currently.
FeO4-+ 8H++3e = Fe3++4H2O, ϕo>1.9V,pH=0
− Compound of Co+8 does not exist, the highest
oxidation state of Co currently is +6. Compound of
Co3+ is the unique compounds of Co exist in
aqueous solution and can oxidize water.
Co3+ +e = Co2+, ϕo=1.84V,pH=0.
Similarly with Ni and Cu, Ni3+ ion cannot exist in
aqueous solution and stable oxidation state of Ni is
always +2.
Likewise, in normal conditions, the stable
oxidation states of Cu are +1, +2.
− Example 2: Investigate group IVB, based on redox
potential, Hf(+4) and Zr(+4) are more stable than
Ti(+4).
TiO2++ 2H++e = Ti3+ +H2O, ϕo=0.1V,pH=0
ZrO2++ 2H++4e = Zr↓ +H2O, ϕo=-1.5V,pH=0
HfO2++ 2H++4e = Hf↓ +H2O, ϕo=-1.7V,pH=0
− Example 3: Investigate group VIB, based on redox
potential, Mo(+6) and W(+6) are more stable than
Cr(+6).
Cr2O72-+ 14H++6e = 2Cr3+ +7H2O, ϕo=1.33V,pH=0
MoO22++e = MoO2+ ϕo=+0.48V
WO3(r)+ 2H++2e = W2O5(r) +H2O, ϕo=-0.03V,pH=0
8/ General rule:
− Elements, having intermediate oxidation states can play
roles as oxidizing agents to react with reducing agents
or reducing agents to react with oxidizing agents.
However, the specific properties of elements depend on
the stability of contiguous oxidation states.
− Example: The specific properties of Cl(+5)’s
compounds are oxidization because specific properties
of Cl(+7)’s compounds and Cl(0)’s compounds are
oxidization.
Investigate properties of S(+4): The specific properties
of S(+4) is reduction because of specific properties of
S(+6) (play role as reducing agent). Moreover, S(+4) is
a weak oxidizing agent because S(0) is a weak reducing
agent.
 Specific oxidization’s properties comparing rule
Elements, having unstable oxidization state tend to stable
oxidization state. If higher oxidation state is stable than this
compound, it has reduction property. If lower oxidation state
is stable than this compound, it has oxidization property. If
both of higher and lower oxidation states are stable than this
compound, it has both reduction and oxidization property.
Example : Specific properties of H2S is reduction because
zero oxidation of Sulfur is more stable than –2 oxidization
state.
Specific properties of HClO is oxidization because -1
oxidation state of Cl is stable.
Specific properties of Na2SO3 is oxidization and reduction
because stable oxidation states of S are +6 and +4.
Stability of compounds

+The higher bonding energy is, the more chemical

inactive the compounds is.

Example1: Electronegative of Oxygen and

Chlorine are 3.44 and 3.16 respectively. However,
at room temperature, Cl2 is strong oxidizing agent
while, O2 is soft oxidizing agent. The reason is
bonding energy of O2 (493 kJ/mol) is higher than
that of Cl2 (239 kJ/mol).
 +Ions exist in solid state compound cannot
participate in chemical reaction easily as existing
in freedom state:

Ex: Redox potential of Pb4+(aq) is significantly

higher than PbO2
PbO2(r) + 2H+(aq) + 2e- = Pb2+(aq) + 2H2O ϕo =+1,449V
Pb4+(aq) + 2e- = Pb2+(aq) ϕo = +1,694V

In conclusions, the more stable compounds is, the

more chemical inactive they are.
Oxidization property of compounds increase in acidic
enviroment and reduction property of compounds
increase in basic enviroment
In this case, using general definition for acid and base.
a) Effect of Acid – base Bronsted – Lawry to oxidization
and reduction properties:
Example 1: Redox potential of SO42- increase fast when pH
condition of solution transmit from basic to acid
environment:
pH = 0 : SO42- + 2H+ + 2e- = H2SO3 + H2O ϕo = +0,17V
pH = 14: SO42-+H2O + 2e- = SO32- + 2OH- ϕo = -0,93V
B) Effect of acid – base Lewis:
Example: Ag+.aq is a weak oxidizing agent in aqueous
solution:
Ag+ + e- = Ag ϕo = +0,799V
However, in the presence of CN-, it specific property is
weak reduction:
Ag(CN)2- + e- = Ag + 2CN- ϕo = -0,29V
c) Effect of acid – base Usanovich.
Recovering P from phosphorite at 15000C, in condition of
using and without using sand. Sand plays a role as Usanovic
acid to increase oxidization property of P(V):
2Ca3(PO4)2 + 10C + 6SiO2 = 6CaSiO3 + 10CO + P4
In this reaction, SiO2 reacts with photphorite to create
calcisilicat, and release P.
(Pls see phosphorite reduction process)
The presence of strange ions, creating with ions to
release insolubility, can lead to the change of oxidization
and reduction property of compound:

Example: Oxidization properties of Cu2+ increases

significantly because of the presence of Cl- (CuCl is
insolubility TCuCl = 1,2.10-6)
Cu2+ + e- = Cu+ ϕo = +0,153V
Cu2+ + Cl- + e- = CuCl(r) ϕo = +0,538V

(Increase the concentration of Cl-, CuCl can solute because

of the creation of [CuCl2]- coù Kkb = 10-5,35
Cu2+ + 2Cl- + e- = [CuCl2]- ϕo = +0,4633V)
 Applying Themochemistry function:

• The quantity ∆G° for a reaction can tell us whether a

mixture of substances will spontaneously react to
produce more reactants for oxidation reaction and
normal reaction.
• At room temperature, sign of ∆G° is the sign of
enthalpy of reaction. At high temperature, sign of ∆G°
depends on both value of ∆H° and ∆S°.
Note: most of heterogeneous inorganic reactions have
complicated mechanism, therefore, it is necessary to
investigate kinetic of reactions before applying
reactions in real conditions.
Redox potential and Nernst equation:

Value of redox potential shows the strength of

oxidizing agent and conjugate reducing agent. The
higher redox potential is, the stronger oxidizing
agent is and the weaker the conjugate reducing
agent is and reversed.

Ex: Redox potential of Au 3+/Au in acidic

environment is +1,68V, therefore, Au3+ ion is the
strong oxidizing agent, however, Au is the weak
reducing agent (Gold is the most stable metal).
 LATIMER DIAGRAM
• The redox potential can be
used to build a battery, or to
use an electrochemical
process in an analytical
technique. But it is not useful
to understand the complex
redox properties of elements.
To address this issue, Latimer
devised a very helpful way to
Lewis H. Latimer display redox potentials for
the elements by using Latimer
Diagram.
 Latimer Diagram’s construction
• Gibbs free energies of chemical reactions, ΔG,
obey algebra. ∆G = -nFE, and ∆GT = Σ∆Gi.
Ex: Redox potential of Fe3+ +3e → Fe.
Half reaction E0 = -nFE0
Fe2+ +2e → Fe -0.44V -2xFx0.44
Fe3+ +e → Fe2+ 0.771V -1xFx0.771

Fe3+ +3e → Fe E0T ≠ 0.331V -3xFxE0T

Thus, E0T = -0.036V

 Latimer Diagram’s construction for Iodine

- 1.589 - 1.154 1.430 .535 -

IO 
4 → IO 
→ HOI 
→ I 2 → I3
(+7) (+5) 1.299 (+1) (0) (-1)
o
-
2H + IO + 2e → IO + H 2 O
+ − - ∆G 1
4 3
-
5H + IO3 + 4e → HOI + 2H 2 O
+ −
∆G o2
-
7H + IO 4 + 6e → HOI + 3H 2 O
+ −
∆G 3o
2 ⋅1.589 + 4 ⋅1.154
o
∆G + ∆G = ∆G o o = 1.299
1 2 6
3

o o o 2E1o + 4E o2
n1FE1 + n 2 FE 2 = n 3 FE 3 o
= E3
6
 In Latimer Diagram
• The most highly oxidized form of the element is on the
left, with successively lower oxidation states to the right.
• The sign of the redox potential refers to the reaction as it
proceeds from left to right (clarified by arrows). The
numbers as written on the corresponding arrows are
standard redox potentials.
• In principle, the redox potentials decrease from left to
right.
• Disproportionation occurs when the E0 value on right
side is more positive than that on left. (An intermediate
oxidation state will DISPROPORTIONATE, convert
to the more oxidized species to its right and the more
reduced species to its left)
Ex 1: Iron’s Latimer Diagram.

Ex. 2: Latimer Diagram of Manganese in acidic and

basic environment. DISPROPORTIONATE
The factors affect the redox potential,
Latimer Series
− In general, the factors affect to the size of ∆G
(∆G = -nFE) are also effect to the value of reodx
potential (E0 or ϕ0).
RT aOx In aqueous 0.059 [Ox]
ϕ =ϕ + 0
ln solution at ⇒ϕ =ϕ +0
lg
nF aKh 0
n [ Kh]
250C:
− These factors are:
1. Concentration.
2. Temperature.
3. Other reagents which are not inert
4. pH (a special case of (3))
Ex: Investigating effect of pH. In case of ClO4-, the redox
potential in acidic and basic environment:
ClO4- + 2H+ + 2e = ClO3- + H2O, ϕo=1.19V,pH=0
ClO4- + H2O + 2e = ClO3- + 2OH-, ϕo=0.36V,pH=14
In acidic solution, H+ ions involved in redox reactions.
0.059 [ClO4− ][ H + ]2
⇒ ϕ = 1.19 + lg (V )
n [ClO3− ]
Therefore, increasing H+ ions concentration (increasing
pH) led to the increasing of redox potential, or increasing
oxidation property and reversed.
Likewise, in basic environment, increasing OH-
concentration (reducing pH) led to the reduce of ϕ or
increase redox property and reversed
0.059 [ClO4− ]
⇒ ϕ = 0.36 + lg − 2
(V )
n [ClO3 ][OH ]
−
Affect of pH condition to the compounds of Manganese
 FROST DIAGRAM
• In Frost diagram, values of standard redox
potential connecting various oxidation states of
an element are displayed.
• To construct Forst Diagram:
• Multiply the values of E0 with the number of
electrons (n) for all compounds.
• Graph of nE0 /V vs. oxidation number is plotted
(including unstable compounds)
• For example, the Frost Diagram for Manganese in
acidic and basic solution:
 How to use Frost Diagram?
• Determine oxidizing agent and reducing
agent:
− The higher compound is the oxidizing agent of its left
compound. Inversely, the higher compound is the
reducing agent of its right compound.
− The slope of the line joining two points in a Frost
diagram is equal to the standard potential value of the
couple formed by the two species. If the slope is
positive, the higher compound is the oxidizing agent
and reversed.
3. Determine strong and weak oxidizing –
reducing agent:
− The oxidizing agent in a couple (two states joined by a line)
undergoes easy (more spontaneous) reduction if the slope is
more positive. Similarly, the reducing agent in the couple
undergoes easier oxidation with less +ve slope.
4. Determine products of oxidation – reduction
reaction:
Compound, at the bottom of the diagram, having the small
Gibbs Free Energy, cannot reaction spontaneously.
Therefore, bottom compound is the final products of
oxidation – reduction process.
Ex: Mn2+ in acidic and Mn2O3 in basic solution are the
final products.
4. Determine disproportionation:
• An ion or molecule in a Frost diagram tends to
disproportionate if it lies above the line connecting
its two adjacent species.
Ex: In basic solution:
2MnO43- +2H2O → MnO42- + MnO2 + 4OH-
5. Determine comproportionation:
• Two species will tend to comproportionate (reverse
of disproportionation) if it lies below the line
connecting its two adjacent species.
• Ex: In acidic solution, MnO2 and Mn comproportionate
to +2 in Mn2+.
 THE STABILITY OF OXIDIZING AND
REDUCING AGENTS IN AQUEOUS SOLUTION

Water can involve oxidation – redox reaction as

oxidizing agent (H+) or reducing agent (O2-)
In specific conditions, compounds, having higher
redox potentian than that of water, can oxidize
water. Likewise, compounds, having lower redox
potentian than that of water, can redox water.
 Stability condition of reducing agent in aqueous solution

Reducing agent
• In non-standard condition, redox potential of 2H+/H2 at 25oC can be
calculated by using Nernst equation:
ϕ = ϕ° + 0,059/2.lg(pH2/[H+]2) = 0,0295lgpH2 – 0,059pH
Oxidizing property of water in different pH conditions are shown by
redox potential:
Acidic environment : (pH = 0)
2H+ + 2e  H2 ϕ° = ± 0,000V
Basic environment: (pH =14)
2H2O + 2e  H2 + 2OH- ϕ° = -0,83V
Neutral environment: (pH = 7)
2H2O + 2e  H2 + 2OH- ϕ° = - 0,41V
Thus, compounds, having higher redox potential than that of water at
defined pH conditions is stable in aqueous solution.
 Oxidizing agents
• In non-standard condition, redox potential of O2/H2O at 25oC
can be calculated by using Nernst equation:
ϕ = ϕ° + 0,059/4(lg[H+]4.po2/[H2O]2)
Reducing property of water in different pH conditions are
shown by redox potential:
Acidic environement: (pH = 0)
O2(k) + 4H+ + 4e  2H2O ϕ° = 1,23V
Basic environment: (pH = 14)
O2 (k) + 2H2O + 4e  4OH- ϕ° = 0,401V
Neutral environment (pH = 7):
O2(k) + 4H+ + 4e  2H2O ϕ° = 0,815V
So, compounds, having lower redox potential than that of
water at defined pH conditions is stable in aqueous solution.
(xem ví duï veà phaûn öùng vôùi nöôùc)
 Comparing reacting ability of recovery phosphorus from
phosphorite mineral using sand SiO2 and without using
sand.
List of enthalpy and entropy of substances at 25 0C

C P4
Ca3(PO4)2 SiO2 CaSiO3 CO CaO
(graphite)
∆Η0t,298
-4105 0 -912 -1635 -110 0 -635
(kJ/mol)
S0298
+241 +6 +41 +82 +198 +164 +43
(J/mol.K)
Reaction (without using sand) :
2Ca3(PO4)2 + 10C = 6CaO + 10CO + P4
∆Η0,298 (kJ/) = (-3810 – 1100 + 0) – (0 – 8210) = 3300 kJ
∆S0298 (J/K) = (258 + 1980 + 164 ) – ( 60 + 482) = 1860J/K
∆G0, 1773 = ∆Η0298 - 1773 x ∆S0298 = 2,22 kJ
Reaction (using sand):
2Ca3(PO4)2 + 10C + 6SiO2 = 6CaSiO3 + 10CO + P4
∆Η0298 (kJ/) = (-9810 – 1100 + 0) – ( -5472 + 0 – 8210) =
2772 kJ
∆S0298 (J/K) = (492 + 1980 + 164 ) – ( 246 + 60 + 482) =
1848 J/K
∆G01773 = ∆Η0298 - 1773 x ∆S0298 = -504,5 kJ
Note: Recovery reaction occurs more easily when using
sand because, sand plays a role as acid, which increases
oxidizing ability of phosphorite (back)
 Ex: Which substances are stable in aqueous solution
(without air) :
CoCl3, CrSO4, FeCl3 , KMnO4, Na2SO3.
These substances solute easily in water.
Standard redox potential of these substances in
acidic environment:

Co3+/Co2+ Cr3+/Cr2+ Fe3+/Fe2+ MnO4-/Mn2+ SO42-/H2SO3

ϕ°(V) 1,84 -0,41 0,771 1,51 0,17

Solution:
Comparing standard redox potentials of listed substances with
standard redox potential of water in acidic environment:
Reducing agents:
* Na2SO3 is stable because of ϕ° = 1,17V > 0,000V;
* CrSO4 is un stable because of ϕ° = -0,41V < 0,000V
2Cr2+ + 2H+ = 2Cr3+ + H2
Oxidizing agents:
* FeCl3 is stable because of ϕ° = 0,771 V< 1,23V.
* CoCl3 is unstable because of ϕ° = 1,84V > 1,23V
4 Co3+ + 2H2O = 4Co2+ + O2 + 4H+
* KMnO4 is unstable because of ϕ° = 1,51V > 1,23V
Tuy nhieân do vaán ñeà ñoäng hoïc phaûn öùng oxy hoùa –khöû giöõa kali
permanganat vaø nöôùc thöïc teá khoâng dieãn ra maø xaûy ra söï phaân huûy
chaäm cuûa ion permanganat trong nöôùc:
4MnO4- + 4H+= 3O2 + 4MnO2 + H2O
Standard redox potential in basic environment:
MnO4-/MnO2 (ϕ°=0,6V), SO42-/SO32- (ϕ°=-0,93V)
In basic environment:
Reducing agent:
* Na2SO3 is unstable because of ϕ° = -0,93 < -0,83V
However, redox reaction between sulfurous (SO32-) and water,
releasing H2 cannot occurs because of kinetic problems of
reaction.
Oxidizing agent:
* KMnO4 is unstable because of ϕ° = 0,6 > 0,401V
However, oxidation reaction between water and KMnO4
cannot occurs because of chemical kinetic problem.
Another substances react with OH- and produce
hydroxide, insoluble in water. (back)