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lecture
5th
Properties
Applications
(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
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.
Properties
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
Applications
Applications
3-reducing agents
Na2SO3
5-Pb2+
PbO
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
Properties:
Iodine as oxidant
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 .
Iodine as oxidant
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 ]
Iodine as oxidant
E Ferri/Ferro= 0.36V
E I2/ 2I- = 0.54V
E Cu2+/Cu+ = 0.46
E I2/2I- = 0.54
Iodine as oxidant
How to determine Cu2+
salts using KI ?
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 .
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:
Iodine as oxidant
Iodine as oxidant
Iodine as oxidant
Iodine as oxidant
Iodine as oxidant