Lecture 4

Analytical Chemistry-II
(Clinical)
Redox Titration
BY
Shimaa S. Soliman
Lecturer of Analytical Chemistry
Faculty of pharmacy – October 6 University
Applications of Redox Titration:

1- Ferrous iron
(Fe2+) 3- Ferrocyanides
& ferricyanides
5- Oxalates

7- Hydrogen
peroxide
2- Ferric iron (H2O2)
(Fe3+) 4- Metallic iron
in presence of
6- Oxidizing
iron oxide substances
capable of
oxidizing oxalates
 Applications of Redox Titration

1- Determination of ferrous iron

A- Using standard permenganate solution (MnO4-).

B- Using standard dichromate solution (Cr2O72-).

C- Using standard ceric sulphate solution (Ce4+).

 1- Determination of ferrous iron
A- Using standard permenganate solution (MnO4-).
 Titration of Fe2+ using KMnO4
• MnO4-/Mn2+ E = 1.52 v
• Cl2/Cl- E = 1.36 v
• Fe3+/Fe2+ E = 0.77 v

 If Fe2+ is titrated with potassium permanganate in presence of

chloride ions  unless the oxidation potential of MnO4-/Mn2+
system is reduced, Cl- will also be attacked by potassium
permanganate leading to higher results.
 In such case, Zimmermanns' reagent is added to the solution to be
titrated  permanganate is thus unable to oxidize chloride ions.
 Role of Ziemermann Reagent

 Ziemmermann solution: used if the titrated solution contains chloride ions.

• Prepared by adding manganous sulphate solution to a cooled mixture of

H2SO4 :H2O (1: 3) respectively, followed by syrupy phosphoric acid.
• MnSO4: Mn2+ salt lowers the oxidation potential of MnO4-/Mn2+ system
(common ion effect)
• H3PO4: phosphate ions lower the oxidation potential of Fe3+/Fe2+ system by
forming a complex with ferric iron (Fe(PO4)2)3- .
• The end point becomes more visible in the presence of phosphate as the iron
complex is colorless while Fe3+ is colored yellow.
 1- Determination of ferrous iron
B- Using standard dichromate solution (Cr2O72-).
 Diphenylamine indicator as internal redox indicator.
 Phosphoric acid must be added in order to lower the oxidation potential
of Fe3+ / Fe2+ system (see internal redox indicators).
 OR use potassium ferricyanide as external indicator.
C- Using standard ceric sulphate solution (Ce4+).
 Carry out titration with Ce4+ till the solution acquires a pale yellow color
(that of excess titrant, self indicator).
 M.R. can be used as irreversible redox indicator; in this case titration with
ceric sulphate is continued till the red color of the indicator in acid solution
is bleached.
 Applications of Redox Titration

2- Determination of ferric iron

A- Using standard titanous chloride solution (Ti3+).

B- Reduction with stannous chloride (SnCl2).

Several methods are used
for the reduction of Fe3+ to
Fe2+  The produced
C- Reduction with zinc metal and sulphuric acid. ferrous salt can be
determined as
under ferrous iron

D- Reduction with amalgamated zinc.

7
 2- Determination of ferric iron
A- Using standard titanous solution

Titrant:
Ferric ions can be directly titrated with titanous chloride solution.

Indicators:
The end point is detected by the use of methylene blue  which is reduced to the
leuco-compound (colorless) by the first excess of the titrant .

SCN- can be also used as indicator  the solution remains red as long as Fe3+ ions
are present. 8
 B- Reduction with stannous chloride
Reagent (reducing agent):
• SnCl2 solution is added dropwise with stirring to hot solution of ferric salts (in 5-6N HCl)
until the disappearance of the yellow color of Fe3+ ions.
SnCl2 + 2FeCl3  SnCl4 + 2FeCl2
Yellow color Colorless
• Excess reducing agent (SnCl2) is removed by adding saturated mercuric chloride
solution  where mercurous chloride is precipitated as a silky white precipitate.

Titrant:
• KMnO4 can be used as titrant.

• The standard oxidizing agent has

no appreciable effect upon small
amounts of mercurous chloride
suspended in the solution.
 C- Reduction with zinc metal and sulphuric acid
Reagent (reducing agent):

• Using granulated zinc/H2SO4 as reducing agent and copper sulphate as a catalyst.

• The reaction is allowed to proceed  until the disappearance of

the yellow color of FeCl3.

• Test for complete reduction: using thiocyanate spot test (till no red
color).

• The excess unreacted zinc is removed by filtration through glass

wool.

• Hydrogen saturating the solution should be driven off by a gentle

boiling  During boiling the flask should be fitted with a Bunsen
valve  to prevent the entrance of air  thus prevent oxidation
with atmospheric oxygen.
 C- Reduction with amalgamated zinc
Reagent (reducing agent):

• The amalgamated zinc (obtained by treating zinc with

mercuric chloride solution)  is an excellent reducing
agent.
2 Fe3+ + Zno  2 Fe2+ + Zn2+

• Reduction is done by passing the cold acidified

solution of ferric salts through a column of
amalgamated zinc (Jone’s reductor)  the column is
then washed with 2.5 % H2SO4 followed by water 
the washings are collected with the reduced iron
solution. Jone’s reductor
 Notes:
1- Reducing substances capable of reducing Fe3+ to Fe2+  are determined
by treating with an excess of ferric salt solution  the produced Fe2+ is
titrated with standard KMnO4 as before.
Examples

• Zinc powder
Zno + 2 Fe 3+  Zn 2+ + 2 Fe 2+

• Metallic iron
Feo + 2 Fe3+  3 Fe2+

N.B. Zinc oxide and iron oxides do not interfere.

 Notes:
2- Oxidizing substances capable of oxidizing Fe2+ to Fe3+  are allowed to
react with a known excess of standard ferrous sulphate solution  The
residual Fe2+ is then titrated with standard permanganate.
Examples
• Potassium persulphate
S2O82- + 2 Fe2+  2 SO42- + 2 Fe3+
• Potassium chlorate
ClO3- + 6 Fe2+ + 6 H+  Cl- + 6 Fe3+ + 3 H2O
• Manganese dioxide
MnO2 + 2 Fe2+ + 4 H+  Mn2+ + 2 Fe3+ + 2 H2O
N.B. Manganese dioxide (in pyrolusite)  is dissolved by boiling with known excess of
ferrous sulphate acidified with sulphuric acid until no black particles remain undissolved. A
Bunsen valve should be fitted on the flask during boiling to prevent aerial oxidation of Fe2+
 3- Determination of ferrocyanides & ferricyanides

• Ferrocyanide: is determined by oxidation with either potassium

permanganate or with standard ceric solution  In the last case phenyl-
anthranilic acid or ferroin is used as indicator.
[Fe(CN)6]4- + O + 2H+  [Fe(CN)6]3- + H2O

[Fe(CN)6]4- + Ce4+  [Fe(CN)6]3- + Ce3+

• Ferricyanide: may be first reduced to ferrocyanide (with sulphite, sulphide,

iodide, sodium peroxide)  Excess reductant is then removed and the
liquid is titrated with standard potassium permanganate.

2Na3[Fe(CN)6] + Na2O2  2Na4[Fe(CN)6] + O2

 4- Determination of Metallic iron in presence of iron oxide
• Reduced iron is prepared by reducing ferric oxide by hydrogen.
• Determination is based on the fact that “Fe/Fe2+ system has more negative
electrode potential than Cu/Cu2+ or Hg/Hg2+ systems”  It can be assayed
by shaking a known weight of reduced iron with either mercuric chloride or
copper sulphate solution on hot  thus metallic iron will displace copper or
mercury from their salt solutions.
Feo + HgCl2  Hgo + FeCl2
Feo + CuSO4  Cuo + FeSO4
• The produced ferrous is titrated with permanganate.
• If mercuric chloride solution is used, Zimmermann's reagent should be
added.
• Iron oxide do not interfere.
 5- Determination of Oxalates
A- Soluble oxalates
• Oxalic acid and oxalates are strong reducing agents  So can be directly titrated with
permanganate or ceric solutions.
H2C2O4 + H2O + O  2CO2 + 3 H2O
Potassium permanganate (MnO4-) Ceric sulphate (Ce4+)
• Titration is done at 600C in presence • Titration is done on hot in
of dilute sulphuric acid. presence of H2SO4 till the
solution is colored pale yellow
(self indicator).
• The reaction is slow at the beginning
but once small amount of Mn2+ is • Alternatively an excess of
formed the reactions becomes very standard ceric solution is added
rapid (autocatalytic reaction).  The mixture is warmed at
500C for 5 minutes  The excess
is then back titrated with FeSO4
5C2O42- + 2MnO4- + 16H+  10 CO2 + 2 Mn2+ + 8 H2O using N-phenylanthanilic acid or
ferroin as indicator.
 5- Determination of Oxalates
B- Cations forming insoluble oxalates (Pb2+ & Ca2+)
The oxalate is precipitated quantitatively and washed free of soluble/exx
oxalate (used as precipitant) and either:

• The washed precipitate is • The residual oxalic acid

transferred quantitatively to a (precipitant) in the filtrate and
beaker  then dilute H2SO4 is washings is back titrated with
added and titration is done with KMnO at 600C .
4
standard KMnO4 at 60 C.
0

• The method is used for the determination of calcium salts, lead in litharge
(PbO)  which should be dissolved in glacial acetic acid, diluted with water
and then precipitated as oxalate .
6- Determination of Oxidizing substances capable of oxidizing
oxalates
Examples
e .g. chlorate, nitrate, persulphate and MnO 2
• They are treated with a known excess of standard oxalate solution  the
residual oxalate is then back titrated with pot. permanganate.

• Manganese dioxide: should be heated with standard oxalate in 6N H2SO4

until no black particles remain undissolved .
• Care should be taken to avoid strong heating as oxalic acid is decomposed
by heat.
 7- Determination of hydrogen peroxide (H2O2)

The determination is based on the reaction of H2O2 with potassium

permanganate.

5 H2O2 + 2 MnO4- + 6 H+  5 O2 + 2Mn2+ + 8 H2O

The equation shows that in this reaction H2O2 acts as a reducing agent and
is oxidized to oxygen.

H 2O 2  O 2 + 2 H + + 2 e
 Properties of some oxidizing agents

• Potassium permanganate: KMnO4

• Potassium dichromate: K2Cr2O7
• Ceric ammonium sulphate
• I2
• Potassium iodate: KIO3
• Potassium bromate: KBrO3
 Potassium permanganate: KMnO4
• It is a very strong oxidizing agent and it serves as its own indicator  It is
a secondary standard??

• Permanganate solutions deteriorate rapidly on standing.

4 MnO4- + 2 H2O  4 MnO2 + 4 OH- + 3 O2

• The reaction is auto catalyzed by MnO2, and also by weak acids and light.

• Standard solution is prepared by dissolving KMnO4 crystals (which always

contain MnO2 on their surface) in water  the solution is boiled gently for
15-30 minutes to destroy any oxidizable impurities in the water and then
filtered through a non reducing medium e.g. glass wool, sintered glass.
 Potassium permanganate: KMnO4
The solution must then be standardized against standard reducing
agents. For example:

• Iron wire : The analytical annular (A.R) quality is used. It is dissolved in H2SO4
giving FeSO4 titrated with permanganate.

• Sodium oxalate : This is dissolved in H2SO4  the solution is then titrated with
KMnO4 at 60oC The reaction is catalyzed by the produced Mn2+ (autocatalytic).

• Arsenious trioxide
 Potassium permanganate: KMnO4
Acid medium:
MnO4- is reduced to Mn2+
 Permanganate could also be reduced to
Mn3+  however this needs the presence
of fluoride or phosphate ions that form
highly stable complexes with Mn3+.

Alkaline medium:

 MnO4- is reduced to either:

• MnO2
• Manganate MnO42- (in presence of barium due to precipitation of barium
manganate).
 Potassium Dichromate: K2Cr2O7
• It is a primary standard and its solution is stable.

• It is an oxidizing agent but of limited use.

• It dose not oxidize HCl.

• It can not oxidize oxalic acid or ferrocyanide.

• Its main application is the determination of ferrous iron .

• It cannot serve as a self indicator because the orange Cr2O72- is reduced

to the green Cr3+ ion.
 Ceric : Ce4+
• It has the following half reaction:
Ce4+ + e  Ce3+
Yellow (orange) Colorless

• Although it can be used as self indicator  it is better to use a redox indicator e.g.
ferroin.

• Acid medium is needed to prevent the precipitation of CeO2.XH2O (cerium oxide

hydrate).
• Formal potential of the system depends on the type of the acid added  It is greatest
in nitric and perchloric acids which are poor complex former for Ce4+.

• Ammonium hexanitrato cerate (NH4)2Ce(NO3)6 is a primary standard.

• Ceric solutions can also be standardized using sodium oxalate or arsenious trioxide.
26