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Reduction- Oxidation

Reactions
lecture

5th

Ceric as titrant: Ce4+

Properties

Ceric as titrant: Ce4+

Ce4+ salts are strong oxidants in H2SO4


Ce4+ + e Ce3+
Yellow
Colorless
Although it could be used as self indicator it is
preferable to use ferroin as indicator especially in case of
det. of ferrous salts.
Ce4+ cannot be used in neutral or alkaline solution due to
hydrolysis to hydrated ceric oxide
They have wide range of oxidising power but
they dont oxidise HCl even in presence of Fe2+ salts
Ce4+ forms more stable complexes than Ce3+
Ceric salts are much more stable than MnO4-

Ceric as titrant: Ce4+

Preparation and standardization of Ce 4+ solu


Prepared from primary standard Ce(NO 3)6 (NH4)2
in conc H2SO4 or in 72% HClO4. If using other
salts it should be standardized
(1) Against arsenious trioxide:
2Ce4+ + H3 AsO3 + H2O 2Ce3+ + H3AsO4+ 2H+
(2) Against oxalate
2Ce4++ H2C2O4 2Ce3+ + 2CO2 + 2H+
In both cases , the reaction is slow it requires heat
to 50C, using ICl as catalyst and ferroin indicator

Applications

Ceric as titrant: Ce4+

(a)Direct titrations:
determination of reducing agents
Fe2+, AsO33- , C2O42-, H2O2, I-,
Fe(CN)64- using ferroin indicator
Color change from red to pale blue

[ Fe (CN)6]4-+ Ce4+ Ce3++ [ Fe (CN)6]3H2O2 + 2Ce4+ 2Ce3+ + 2H+ + O2


Advantages:
Better than MnO4- as it is less subject to
interference of organic matter
It is preferable to be used instead of MnO 4- in the
determination of Fe2+ since we can use HCl.

Ceric as titrant: Ce4+

Applications of Ce4+
(b) Back titrations:
Determination of polyhydroxy
alcohols, aldehydes, hydroxy acids.
example: glycerol, citric acid
C3H8O3+8Ce4++3H2O 3HCOOH+8Ce3++8H+
The excess Ce4+ is titrated against sodium oxalate
or AsO33- using ICl as catalyst and ferroin as
indicator at 50oC.

Potassium dichromate as titrant

Properties

Potassium dichromate as titrant

It is a primary standard due to the stability of its


solution and is obtainable in high purity
Its oxidation potential is lower than KMnO 4 and
Ce4+ so it is limited in use
It does not oxidise Cl- into Cl2, oxalic acid ,
ferrocyanide Its main application is the direct and
indirect determination of Fe2+ ion

Potassium dichromate as titrant

It can not serve as a self indicator reagent


Cr2O72- (Orange) + 14H+ + 6e 2Cr3+ (green) + 7H2O

Many redox indicators are unsuitable:


because of their high oxidation potential, and
because of the deep green colour of Cr 3+ which
causes the colour change of the indicator to be
less clear
The indicators usually used are:
diphenyl amine sulphonic acid.
4,7-dimethyl 1, 10 phenanthroline ferrous.

Potassium dichromate as titrant

Applications
1-Determination of Fe2+ Iron (internal indicator)
E Fe3+/Fe2+ 0.77
E ferroin 1.06
E diphenylamine 0.76
Is there need for
H3PO4
H3PO4??
diphenyl Titrate with
2Cr
O
2 7
amine
0
E
= 1.33 v
H2SO4
Fe3+
Fe2+
Role of H3PO4 or F-:
decreases the Fe3+/Fe2+ system potential so that Fe2+ ion will
be oxidized before the indicator
and to remove the dark colour of Fe3+ ion giving a more clear
colour change.

Applications

Potassium dichromate as titrant

1-Determination of Fe2+ Iron external indicator


Ferricyanide:Fe2+ is titrated with dichromate in
acidic medium.Occasionally remove a drop from
the solution and add it to ferricyanide solu. a blue
color of ferrous ferricyanide is formed. At the E.P.
No more Fe2+ is present so no blue color is
formed.
Diphenylcarbazide: After oxidation of Fe2+ to
Fe3+, the first exx of dichromate oxidizes the
indicator and gives a red color.

Applications

Potassium dichromate as titrant

2- Determination of some oxidising agents


Add a measured exx of Fe2+ ion and back titrate
the exx. using Cr2O72- and diphenylamine as
indicator.

Applications
3-reducing agents
Na2SO3

Potassium dichromate as titrant


4-Organic compd
glycerol

5-Pb2+
PbO

Add measured exx of Cr2O72- in presence of:

Sulphuric acid
Sulphuric acid
glacial HAC
ICl as catalyst
The excess dichromate is titrated iodometrically
Cr2O72- + 6I- + 14 H+ 2Cr3+ + 3I2 + 7
H2O
3 SO32- + Cr2O72- + 8H+ 3 SO42- + 2Cr3+ + 4H2O
3C3H8O3 + 7 Cr2O72- + 56 H+ 14Cr3+ + 9 CO2 +
H2O
2Pb2+ + Cr2O72- + H2O 2PbCrO4 (ppt)+ 2H+

Iodine as oxidant

Properties:

Iodine as oxidant

The iodine/iodide half reaction is


I2 + 2e 2I E
E
(Eo = +0.535V)
I- can be oxidized by systems I2 can oxidize systems of
of higher oxidation potential
lower oxidation potential
MnO4-/Mn2+
Sn4+/Sn2+
Cr2O72-/Cr3+
S4O62-/S2O32ClO3-/ClS/S2Iodometric method
Iodimetric method
Indirect titration
Direct titration with I2
Add KI to oxidizing agents,
To determine reducing
equivalent I2 is libarated and
agents
titr with Na2S2O3
To determine oxidizing agents

Properties:

Iodine as oxidant

Systems having oxidation potentials near to


that of iodine/iodide e.g AsO43-/AsO33-, Fe3+/Fe2+

Their reactions with Iodine is directed forward or


backword by control of experimental conditions.
i.e. Change in oxidation potential
1-the pH of the medium
2-addition of complexing agents
3-addition of precipitating agents

Factors affecting the potential of I2/I- system:


1-Effect of pH:

The potential of:

AsO43-/AsO33-= +0.57
I2/2I- = +0.54
To determine arsenite sample using Iodine
the pH of the solution should be adjusted to 8.3
by adding NaHCO3
I2 + AsO33- + H2O 2I- + AsO43- + 2H+
E AsO43-/ AsO33- =Eo 0.059 / 2 log [AsO33- ] / [AsO43-][H+]2
[H+] by addition of NaHCO3 the oxidation
potential of AsO43- / AsO33- system.
NaHCO3 reacts with H+ giving CO2 and H2O shifting the reaction
to the right and prevent reversibility.
At higher pH if using NaOH, I2 reacts with OH- producing OI- so
consuming more I2. Also OI- has oxidizing properties which
differ than I .

2-Effect of Complexing agents:


I2 + 2 e 2IE= = Eo -

Iodine as oxidant

0.059 Log [I-]2 / [ I ]


2
2

When HgCl2 is added to the I2/I- system it forms


[HgI4]2- Thus:
removing the I- ions from the share of the
reaction,
minimizing its concentration,
increasing the ratio of I2 / [I-]2
increasing the oxidation potential of I 2 /2I- system
So I2 could determine AsO33-.

Another example

Iodine as oxidant

E Fe3+/Fe2+= 0.77V
How to determine Ferrous
E I2/ 2I- = 0.54V
salts using Iodine?
Fe3+ + e Fe2+
E Fe2+ / Fe3+ = 0.559 -

0.059
[ Fe 2 ]
log
1
[ Fe 3 ]

When pyrophosphate, EDTA or F- is added to the


Fe3+/Fe2+ system it form [FeF6]3- or [Fe(PO4)6]3Thus:
removing the Fe3+ ions from the share of the reaction,
minimizing its concentration,
decreasing the ratio of Fe3+ / Fe2+
lowering the oxidation potential of Fe 3+/ Fe2+
below that of I /2I- system.

Iodine as oxidant

3- Effect of precipitating agents


Fe(CN)63- + e Fe (CN)64-

E Ferri/Ferro= 0.36V
E I2/ 2I- = 0.54V

To determine [Fe(CN)6]3- ion iodometrically; Zn2+


should be present:
it precipitate Zn2[ Fe(CN)6] ion
0.059
[Fe (CN) 6 ]4E = log
31
[Fe(CN)
]
o
6
E -

minimizing conc of ferrocyanide

increasing ferri/ferro potential


So Ferri/Ferro system can oxidize I- to I2

E Cu2+/Cu+ = 0.46
E I2/2I- = 0.54

Iodine as oxidant
How to determine Cu2+
salts using KI ?

It is expected that I2 oxidizes Cu+ (cuprous), however, Cu2+


(cupric) oxidizes IProcedure: Cu2+ is treated with KI and the liberated I2 is
titrated with S2O322Cu2+ + 4I- I2 + Cu2I2
The precipitation of Cu2I2 increases the oxidation potential
of
Cu2+ /Cu+
E = E0 - 0.059 log [Cu+]
1
[Cu2+] So Cu2+ oxidizes I- to I2

I2 tends to be absorbed on Cu2I2 so the reaction with S2O32is incompltete so add SCN- near the end point to form Cu2(SCN)2
which has no tendency to adsorb I .

To reverse the reaction i.e. To allow iodine to


oxidize cuprous.
Add tartarate or citrate which forms with cupric a
stable complex so decreasing the oxidation
potential of Cu2+/Cu+
E = E0 - 0.059 log Cu+
1
Cu+2

Iodine as oxidant
Titration methods:
Since iodine may be either reduced or produced by
oxidation
Direct
Indirect
Iodimetric method Iodometric method
Iodine
I- is added to oxidizing
Titrating agent for determination
agents,the librated I2
of reducing agents
is titr. with Na2S2O3
Added near the
Added at the
Indicator
end of titr (when the
beginning of titr.
(Starch)
brown color of I2
becomes pale)
E.P.

permanent blue
color

disappearance of
blue color

Iodine

Na2S2O3

Iodine as oxidant
Na2S2O3

oxidant
+
KII2

Reductant
+
starch
.
P
.
E

Add starch
Colorless E.P.

Iodine as oxidant
Detection of the end point in iodine titrations:
1- The use of starch:

Starch is used in the form of colloidal Solu giving


a deep blue adsorbtion complex with traces I 2

In exx I2 an irreversible blue adsorption complex


is formed which is not changed

Starch consists of amylase and amylopectin


I2 gives blue adsorption complex with amylase.
In strong acid medium: starch hydrolyses giving
products which give with iodine non reversible
reddish color masking the end point change.

Iodine as oxidant

Detection of the end point in iodine titrations:


1- The use of starch:
Starch can not be used in alcoholic solu.because
alcohol hinders the adsorption of I 2 on starch
The sensitivity of the blue color decreases with
temperature due to gelatinization of starch and
volatility of Iodine

Starch indicator solution must be freshly prepared


when it stands decomposition takes place and its
sensitivity is decreased. A preservative can be
added

Iodine as oxidant

Detection of the end point in iodine titrations:


2- Use of organic solvent (CHCl3 or CCl4)
In presence of alcohol or conc acids, organic solvents
are recommended as indicators.

These solvents dissolve iodine to give intensely


coloured purple solution, so that a trace of I2 gives an
intense colour, and the end point will be the appearance
Or disappearance of the colour in the organic solvent layer.
I2 is soluble in CHCl3 or CCl4 90 times more than in H2O
It is important that the mixture be shaken well near the
end point in order to equilibrate the iodine between the
aqueous and organic phases to enable aqueous S2O32to react with I2 in CHCl3

Sources of error in iodimetry


Iodine as oxidant
A- Error due to I2:
(1)I2 is volatile especially at high temp and at a low
Conc of I- ion so: Use stoppered glass containers
Avoid elevated temp & cool during titratn
Moisten the stopper with II-+I2 I3- (triiodide) less volatile and more stable
(2) I2 conc is changed if the solution gets in contact with
rubber, organic matter, dust, SO2, H2S
(3) I2 may undergo disproportionation into HOI and I I2 + H2O HOI + I- + H+
To overcome this difficulty the solution may be acidified
to shift the reaction to the left.

Sources of error in iodimetry


Iodine as oxidant
B- Error due to I- ion:
I- ion is liable to atmospheric oxidation.

4H+ + 4I- + O2 2I2 + 2H2O


This is catalysed by light, heat, Cu2+, NO gas
The medium must be completely free from O 2 so
introduce CO2 (add little NaHCO3).
In titration which needs standing for time, standing
should be away from light.
If we need acid medium, never use HNO3, it contains
nitrous oxide.

Sources of error in iodimetry

Iodine as oxidant

C- Error due to S2O32- ion:


Thiosulphate is affected by pH, the most
favourable pH is 7 till pH 9
Under these conditions: S2O32- is oxidized to
S4O62-, where every 2 S2O32- is oxidized by 1 I2 to
S4O62- (tetrathionate) 2S2O32-+I2 S4O62-+2I Under acidic conditions: thiosulphate is
changed to bisulphite (HSO3-) with the
precipitation of S. Every 2 HSO3- is oxidized by 2
I2 to 2HSO4 Therefore, The consumed I 2 in acid medium is
double that consumed in neutral medium.

Sources of error in iodimetry

Iodine as oxidant

C- Error due to S2O32- ion:


In pH>9: I- changes to IO- (hypoiodite) oxidizing
S2O32- to SO42- which is an incomplete reaction
Thiosulphate is decomposed during storage by
thiobacteria, so:
boiling water is used as a solvent,
preservatives e.g. sodium benzoate, CHCl 3, or
HgI2 may be added.
The pH is adjusted by adding borax, Na 2CO3
or NaHCO3 to about pH 9 which inhibits
bacterial action.

Sources of error in iodimetry

Iodine as oxidant

D- Error due to starch:


Starch may be decomposed by microorganisms
into products e.g.
glucose causes error due to its reducing action
other products gives nonreversible reddish color
with I2 which masks the true end point.
To avoid this, preservatives e.g. H3BO3 and
formamide are added.