CHAPTER

7
Oxidation reduction Titration

1
 Syllabus
Topics to be Covered
1. Oxidation- reduction reactions
2. Redox titration curves for Iron(II) with Cerium(IV) ,
Other redox couples
3. Redox indicators
The choice of redox indicators
Specific indicators
4. Feasibility of redox titration.

•.
2
 Oxidation–reduction (redox) reaction:
Oxidation is the process where a species loose electron and
converts to higher oxidation state (i.e. increase in oxidation
number) and vice versa for reduction. An oxidation-reduction is
that reaction where one species looses the electron and
• Sn2+ + 2Hg2+ 2Hg22+ + Sn4+
• 5Fe2+ + MnO4- +8H+ 5Fe3+ + Mn2+ + 4H2O
• Fe2+ + Ce4+ Fe3+ + Ce3+
• Sn2+ + 2Fe3+ Sn4+ + 2Fe2+
• U4+ + 2Ce4+ + 2H2O UO22+ + 2Ce3+ + 4H+
• 2MnO4- + 5H2C2O4 + 6H+ 2Mn2+ + 10CO2 + 8H2O
• HAsO2 + 2MnO4- + 6H+ H3AsO4 + 2Mn2+ + 2O2 + 8 H2O
another will gain that electron.

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

• HAsO2 + I2 +2H2O H3AsO4 + 2H+ + 2I-
• Cr2O72- + 6I- + 14H+ 2Cr3+ + 3I2 + 7H2O
• 2Cu2+ + 4I- Cu2I2 + I2
I2 + 2S2O32- 2I- + S4O62-
• Cr2O72- + 6I- + 14H+ 2Cr3+ + I2 + 7H2O
•

I2 + 2S2O32+ 2I- + S4O62-

Oxidation ： Loss of e−,
hence positive charge increases
Reduction ： Gain of e−,
hence positive charge lowers

• Reducing agent / Reductant:

– Electron donor
– Reducing agent will tend to give up
an electron/s
- Low reduction potential
– Get oxidized
(i.e. becomes more positive)
Fe2+ Fe3+ + e-
• Oxidizing agent / Oxidant:
– Electron acceptor
– Oxidizing agent will tend to receive
an electron/s
– High reduction potential
– Get reduced to a lower oxidation
state
(i.e. becomes more negative).
Ce4+ + e- Ce3+ 4
 Difference with acid base titration:
Acid Base: Redox:
Proton Transfer reaction Electron transfer reaction
Half reaction cannot be carried in can be written in the two half reaction
Separate position i.e. oxidation half and reduction half.
electron donor and acceptor can be kept
in separate solution.
acid base reactions are fast. Redox reactions are slow in some cases,
so temperature and catalyst are required
Only ionic bonds are broken not the Covalent bonds may be broken and
covalent bonds. formed, are completed in multi steps,
MnO4- + 8 H+ +5e- = Mn2+ + 2H2O. No
leveling effect for different solvents on
The strength of acid and base are the strength of oxidizing and reducing
labelled or differentiated by the solvents agents.

5
 Redox titration:
• Titration in which redox reaction occurs is redox titration.
Direct redox titration: Titrant and analyte undergo direct redox reaction.
Fe2+ + Ce4+ ⮀ Fe3+ + Ce3+
Indirect titration: Titrant and analyte donot react directly. Analyte reacts with next
reagent to generate a new species which is titrated with the titrant. The
stoichiometry is important in this case.
Cr2O72- + 6I- + 14H+ ⮀ 2Cr3+ + I2 + 7H2O
I2 + 2S2O32+ ⮀ 2I- + S4O62-
Permangnometric titration: Redox titration where KMnO4 is used.
MnO4- + 8 H+ +5e- = Mn2+ + 2H2O.
Iodimetric titration: Direct redox titration where iodine is involved.
HAsO2 + I2 +2H2O ⮀ H3AsO4 + 2H+ + 2I
Iodometric titration: Indirect redox titration where iodine is involved.

2Cu2+ + 4I- ⮀ Cu2I2 + I2

I2 + 2S2O32- ⮀ 2I- + S4O62-

• Auxiliary reagents: Reagents that are used for preliminary
redox reactions, which convert analytes into single oxidation
state and the excess amount can be removed .
• auxiliary reducing reagents:
– Metals (Zn, Al, Cd, Ni, Pb, Cu, Ag/Cl-)
– SO2 and H2S:
• auxiliary oxidizing agents:
– Sodium bismuthate (represented by NaBiO3)
– Potassium / Ammonium peroxy disulfate
((NH4)2S2O8)
– Sodium peroxide and hydrogen peroxide

7
Nernst equation: “relationship between cell potential and activity”
1889

R = 8.314J/K mole
F = 96500C
T = 298K

8
 Redox titration curve:
A plot of Cell potential VS V of titrant.
• Titration curve for Fe(II) with Ce (IV):
• Ce4+ solution is used as titrant
• Net Reaction:
Fe2+ +Ce4+ Fe3+ + Ce3+ (rapid and reversible)
• Half cell potential at any stage can be
calculated from any one of the half cell
reaction using Nernst equation:
• Half cell reactions:
– Fe3+ + e- Fe2+ E0 = 0.68V Before eq. point
– Ce4+ + e- Ce3+ E0 = 1.44V After e.q. point
– At equivalent point both equations are used.
– If indicator is used: In(OX) + ne- = In(RED), reaction also
generates the same potential. But it is difficult to
Before eq. Pt.: analyte redox pair
calculate the concentration of these species.
• The graph is generated.: Eq. Pt.: average of their
conditional potential
Electrode Potential vs Volume of titrant
After eq. Pt.: titratant redox pair
9
 Redox titration curve for Fe(II) with Ce (IV):
5.0mmole Fe2+ dissolved in 100mL H2SO4 is titrated with 0.10M Ce4+ sulphate
solution. Calculate the potential of inert electrode at various intervals of titration
and plot the titration curve. [E0|(Fe)=0.68V, E0|(Ce)=1.44 V
• The net redox reaction : Fe2+ +Ce4+ Fe3+ + Ce3+
• As the titration proceeds the concentration of redox species, Fe2+, Ce4+ , Fe3+, Ce3+ varies continuously
so the cell potential. The anode is SHE so the cell potential at an instant can be obtained from any
one of the half cell reaction by applying Nernst equation, which will be more appropriate for us.

• Before equivalent point Fe3+-Fe2+ couple is used and after the equivalent point Ce4+-Ce3+ couple is
used. At the equivalent point [Ce4+] and [Fe2+] are negligible so are difficult to calculate, the cell
potential is calculated from the standard cell potential of the two half. It is clearer from the example,

L
m
Condition Reaction
?

5 4
For determination of mmoles Fe2+ + Ce4+ ⇒ Fe3+ + Ce3+

er
Aft

L
concentration of ions Initial 5 0 0 0

m
L

L
construct the table

0
m

m
5
Change -1 -1 +1 +1

er
0

0
1

6
Aft
Equilibrium 4 ≈0 1 1
er

er
Aft

Aft
Final Volume 100 + 10 = 110 mL
Vol of [Fe2+ ] [Ce4+] ⇒ [Fe3+ ] [Ce3+] Vol of titrant [Fe2+ ] [Ce4+] ⇒ [Fe3+ ] [Ce3+]
titrant
50 mL (Eq. ??? ≈0 ??? 5/150 5/150
0 mL 99.99 0 0.01% 0 pt. ) ≈0
%
60 mL ???? ≈0 1/160 5/160 5/160
10 •mL At the beginning
4/110 ???? 1/110
of the titration: 1/110 • After addition of 60mL Ce(IV)
≈0
• [Fe2+] = [Fe3+] = ??? • Here, [Ce4+ ]= , [Ce3+ ]=
• Few of the Fe2+ may be oxidized to Fe3+ (by
• Ecell =
dissolved air and impurities).
= 1.40V
If we suppose 0.1% of Fe2+ is oxidized;
• The potential will be
E = 0.68-0.059log ( ) = 0.50V
• After addition of 10mL Ce(IV)

ECell = 0.68 – 0.0592 = 0.64V

• At equivalent point (After addition of 50mL Ce(IV)):

• At eq. pt. [Ce4+] = [Fe2+] = x ≈0
• And [Ce3+] = [Fe3+] = 5/150 mmole/mL

• = 1.06V 11
Calculate and construct the titration curve for the titration of 50.00mL of 0.02500M
Sn2+ with 0.1000M Ce4+ . E0Ce4+/Ce 3+=1.44, E0Sn 4+/Sn 2+= 0.15V
Try to get the solution:
Example :Obtain an expression for the equivalence-point potential in the titration of 0.0500
M U4+ with 0.1000 M Ce4+. Assume that both solutions are 1.0 M in H2SO4.

U4+ + 2Ce4+ + 2H2O ⮀ UO22+ + 2Ce3+ + 4H+

UO22+ + 4H+ + 2e- → U4+ + 2H2O E0 = 0.334 V
Ce4+ + e- ⮀ Ce3+ E0' = 1.44 V

×2

simply if [H+]=1 , Then…..

Eeq
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Titration of redox couples:-
• Compare the titration curves; for Fe+2 and U4+
with Ce4+
• If different redox couples like (Fe+2 -Fe+3 …), are
studied:
– generate different nature of potential versus
percent oxidized (i.e. amount of titrant/oxidant
added) curves. Which are shown in the figure
– couples with oxidation potential greater than 1
are on the right side (they are strong oxidizing
agents).
– The single titration curve is the combination of
two redox couples.
Facts –
about the titration
In other word we curves:
can say that combination of the
• Eeq and shape
two of curve
curves depends
in figure will upon the titration curve
give the
type of titrant /oxidant .
• Shape vs n: n =1 are steeper than n= 2 or higher (MnO4- , n=5 &
Cr2O7— , n = 6).
• asymptotic to the vertical axis at zero and 100% oxidation and
flatter near the middle point (≈50% oxidation), it corresponds to
the standard potential of the couples.
• The stabilization (poised) in this flat region is analogous to
buffering action of the acid base pair at the pH region
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 Feasibility of redox titration:
• Large equilibrium constant fast reaction, & indicator choice
Not feasible
• Arsenic (III) with Cerium (IV)[large K but slow].
H3AsO3 + 2Ce4+ + H2O 2Ce3+ + H3AsO4 + 2H+

• The completeness of reaction (is expressed in terms of

equilibrium constant) is high if change of potential around
equivalent point is high.
Q • For the redox reaction : Ox1 + Red2 Red1 + Ox2,
where Ox1 + e Red1 E 10 and Ox2 + e Red2 E20
• If, 50 mL of 0.1M Red2 is titrated with 0.1M Ox1, when 49.95 mL of titrant is
added, the reaction is complete and on addition of two more drops (1mL) of
titrant, the value of pRed2 changes by two units.

(i) Calculate the value of equilibrium constant for the these conditions?
(ii) What is the difference in standard potential of two redox couple for this value of
K?

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 Q
Solution where Ox1 + e Red1 E10
A) When 49.95mL titrant is added: and Ox2 + e Red2 E 20
V2 (Ox1) = 49.95 mL
V2(Ox1 ) = 49.95 + 0.1mL, ∆pRed2 = 2

B) When 50.05mL titrant is added:

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General indicators for redox titration:
• substances that show change in colour on being changed from reduced to
oxidized state or vice versa are termed as general redox indicators.
• An indicator which itself undergo redox reaction are called true redox indicators.
• If the change of colour sharply depends on potential it is called specific indicator.
• Specific indicator reacts in specific manner with one of the reagent to give
colour.
For example starch as indicator for iodine, SCN- with Fe(III).
• Self indicator: KMnO4.
• If no internal indicators are available: spot test indicators. Ferricyanide ion was
used to detect Fe(II). Fe (II)-ferricyanide ion gives turn bull’s blue colour.
• In some case end point can be determined by potentiometric titration (sigmoid,
differential & analytical/grans plot)

Indicator Range for the true indicators:

Next slide…………………
16
If we consider the true indicator, the half cell reaction be written as,

Thus for the detection of color change from reduced form to oxidized form, it requires
the change in concentration ratio by 100 folds (10 to 1/10).
If we apply this condition in Nernst equation,

change in potential for the colour transition

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 Selection of indicator:-
• should change colour at/near eq. pt.
• The potential fluctuation in titration curve at end point must be
Large, so that it will cross the indicator range.
For previous example, titration of Fe(II) with Ce(IV),
potential at eq point ≈1.06V,
So: ferroin is the suitable indicator. [Transtion pot: 1.11???]
Q. Fe(II) is treated with an oxidizing agent (in acidic medium)
What should be the transition potential of the indicator which
changes colour when all but 0.1% Fe2+ is oxidized to Fe3+. E0(Fe) = 0.61V
Here, E = 0.61 – 0.0592 log[Fe2+]/[ Fe3+]
= 0.61 – 0.0592 log 1/1000 = 0.79V
The transition potential should be around this value. Diphenyl
amine sulphonic acid is the selective indicator whose transition
potential is 0.85V.
[This is greater than required value so with this indicator colour change occur
for even low concentration of Fe2+]

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 Common indicators:

Phenosafranin Methylene Diphenyl amine 1-10 5-nitro (1,10

blue sulphonic acid[ Fe Phenonthroline phenonthroline)
(Phen)3 ]3+ + e =
[ Fe (Phen)3 ]2+ ;
1.06V

Ferroin

OX: Red OX: Red OX: Red-Violet OX: faint blue OX: faint blue
Red: ……. Red: ……. Red: ……. Red: Red Red: Red
TP: 0.28V TP: 0.53V TP: 0.85V TP: 1.11V TP: 1.25V
(1M acid) (1M acid) (dil. acid) (1M, H2SO4) (1M, H2SO4)

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• Short notes on
(a) Permangnometric titration
(b) Iodometric titration
II Asignment

nk Yo u
T ha
20
• Q, For the reaction A2+ + 2B3+ A4+ + 2B2+, a.
Calculate the equilibrium constant if, 50 mL of
0.1M A2+ is titrated with 0.2M B3+, when 49.95
mL of titrant is added , the reaction is
complete and on addition of two more drops
(1mL) of titrant, the value of pA changes by
two units.
• b. What is the difference in standard potential
of two redox couples?
• Application of redox titration:
• Auxiliary reagents: Reagents that are used for preliminary redox reactions, which convert analytes into single oxidation
state and also the excess amount used,can be removed are auxiliary reagents. For example in the determination of iron
in water iron must be converted into single oxidation state before titration.
• Some common auxiliary reducing reagents:
– Metals:- Zn, Al, Cd, Ni, Pb, Cu, Ag (in presence of Cl-) e.t.c. Stick/ coil of metal + analyte completion of reaction separated and
rinsed with water(manual/filtration). or the next way is the use of Jones Reductor, where filtration is carried by perforated or
fritted disk. Here analyte is passed through glass column containing granules of metal. Metal amalgam can also be used.
– SO2 and H2S:- (are mild reducing agents and are less used) in the solution they are oxidized as
H3SO3 + H2O = SO42- + 4H+ + 2e- 0.17V,
H2S = S + 2H+ + 2e- 0.14V, soluble and excess reagent can be removed.
Converts Fe3+ to Fe2+, V5+ to V4+ , Ce4+ to Ce3+
• Some common auxiliary oxidizing agents:
– Sodium bsmuthate (represented by NaBiO3)
• Strong oxidizing agent.
• Sparingly soluble.
• Uncertain composition.
• Salt is suspended and boiled in analyte solution
• Separated by filtration.
• The half reaction: NaBiO3 (s) + 4H+ + 2e- = BiO + Na+ + 2H2O
Oxidizes Mn2+ to MnO4-, Ce3+ to Ce4+, Cr3+ to Cr2O72-etc
– Potassium / Ammonium peroxy disulfate ((NH4)2S2O8):
• Strong oxidizing agent.
• Boiled for brief period.
• Catalyzed by Ag+ ion
• Excess reagent is decomposed by berief period of boiling (2S2O82- + 2H2O = 2SO42- + O2(g) + 4H+)
• The half reaction, S2O82- + 2e- = 2SO42-
Oxidizes Mn2+ to MnO4-, Ce3+ to Ce4+, Cr3+ to Cr2O72-etc
•
– Sodium peroxide and hydrogen peroxide: half reaction, H2O2 + 2H+ + 2e- = H2O E0 = 1.78V
• it is used in acid solution
• excess reagent removed by boiling 2H2O2 boil 2H2O+ O2
• Application of redox titration involving:
– Permanganate (MnO4-)
i. availability/toxicity and cost: Readily available, low cost colored
ii. Preparation and stability: Unstable can be oxidized by water and the reaction is catalyzed by light , heat, acid, and
bases, Mn2+, MnO2, 4MnO4- + H2O = 4MnO2 + 3O2 + 4OH-, reacts with organic matter and dust in solution,
acidic solution is not stable, 4(MnO4-H+) = 2MnO2 + 3O2 +2H2O,
Permanganic acid.
The reaction is slow in dilute solution and room temperature[using excess MnO4- and rising the temperature will
accelerate this reaction, cannot be filtered by filter paper. Weighed amount of permanganate salt is dissolved in
water , it is heated to destroy reducible substances and is filtered through asbestos/ sintered glass to remove MnO 2.
this solution is standardized and kept in dark without acidifying. it is stable for several months. filtration and re
standardization is required if solid is seen in the solution.
iii. Half cell reaction: Mn can exist in different oxidation states; +II, +III, +IV, +VI, +VII, thus reaction with variety of product
depending on the condition are obtained]
– Very acidic solution (0.1N), MnO4- +8H+ + 5e- = Mn2+ + 4H2O E0 = 1.51V
– low acidity (pH 2-12) MnO4- +4H+ + 3e- = MnO2 + H2O E0 = 1.70V
– Can be reduced to Mn 3+(which is unstable); if there is presence of pyrophosphate or fluoride as complexing agent MnO4- + 3H2P2O72- +
8H+ + 4e- = Mn(H2P2O7)3 + 4H2O E0 = 1.5V
– In very alkaline solution(1M): MnO4- + e- = MnO42- (manganate green) E = 0.54V , BaCl2 is added to precipitate BaMnO4 and can be
removed.
iv. Detecting end point:
– Purple/ pink color is self indicator
– For very few dilute solution; ferroin or diphenyl amine sulphonic acid is used.
– End point is considered if colour 30 seconds.
– error may occur due to slow reaction with water in presence of Mn2+,
MnO4- + 5Mn2+ + H2O = 5MnO2 + 4H+ slow
v. Standardization:
– By sodium oxalate/ oxalic acid:- 2MnO4- +5H2C2O4 + 6H+ = 2Mn2+ + 10 CO2 + 8H2O reaction is slow, heated at
60-900c and is catalyzed by Mn2+(auto catalytic) on heating air can oxidize oxalate ion and can give 0.1-0.4%
error. O2 + H2C2O4 = H2O2 + 2 CO2
– By As3+ oxide: catalysts KI, KClO3, ICl 2MnO4- +5HAsO2 + 6H+ + 2H2O = 2Mn2+ + 5H3AsO4
Vi. Determinations with MnO4-:-
– Fe in iron ores: Converted to acid solution converted to Fe2+ by John redactor
– Direct titration can be done for listed species in table: Sb (III), AS(III), Br 2, H2O2=, Fe2+, NO2-, C2O4-,Sn2+, U (IV), V(iV)
– Indirect determination of oxidizing agent – reduced by excess reagent which is then titrated
 Iodine:
Weak oxidizing agent, only used for strong reductants, so has limited applications.
i) Availability/toxicity/cost: Readily available, non toxic, low cost.
ii) Preparation of solution and stability: I2 is not soluble in water (1.34X10-3m/L) and is also not stable, it hydrolyzed to give hydroiodic and hypoiodous acids.
I2 + H2O = HIO + H+I-,
HIO will be decomposed by sunlight and basic solution, 2HIO (hn) = 2H+ + 2I- + O2(g), 3HIO (3OH-) = IO3- + 2I- + 3H2O
In presence of excess KI, the volatility decreases and solubility increases. 3-4% by weight of KI in 0.1N solution is used.
I2 is purified by sublimation; concentrated solution f KI is weighed before and after dissolving the iodine.
Iodine attacks organic matter (cork, stopper), organic dust, fumes etc so should be avoided.
Air may oxidize iodide io, is catalyzed by acid, heat and light.
I- + O2 + 4H+ = I2 + H2O; give error
I2 may be lost by volatilization; give error

iii) Half cell reaction: In KI solution it forms triiodide complex (I2 + I- = I3-), so the half cell reaction is written as ,
I3- + 2e- = 3I- E0 = 0.536V
iv) Detecting end point:
- 0.1N I2 is intense with its own colour. The colour is much intense in solutions like CCl 4, CHCl3 (1drop of 0.05M in 1L is observed discernible colour); disappearance of I2 colour can
serve as indicator.
- Starch can be used as indicator for iodine. Starch contains β-amylose and absorption of I2in helical chain of β-amylose give deep blue colour (Intense colour for slightly acidic
solution in presence of I-). The α-amylose (amylopectin) gives reddish adduct and the reaction is not reversible; so should be avoided. Commercial soluble starch has no α form (i.e.
α form is removed)
* Bacterial action will decompose aqueous starch solution. The decomposition product can consume I 2 and convert to reddish product. Decomposition can be controlled in sterile
condition or by using preservatives. HgI2 & CHCl3 are used. Simple method is to prepare fresh starch solution.
* Starch will get decomposed at higher concentration of I2, so use of indicator is delayed after the generation of pale yellow coloration from red brown.
* Sensitivity of indicator is decreased with increasing temperature and presence of organc species (like meOH, EtOH):
v) Standardization: Are standardized against anhydrous sdiumthiosulphate or barium thiosulphate monohydrate I 2 + S2O32- 2I- + S4O62-
vi) Determinations with Iodine:-
Direct Iodimetric Determinations: It is direct redox titration where I2 acts as oxidizing agent; Strong reducing agents like, S2O32-, As(III), Sb3+, S2+, Sn2+ and ferrocyanide are
determined. The reduction power of these species is pH-dependent, so pH should be maintained.
Indirect Iodometric processes: Strong oxidizing agents can be analyzed by adding KI in excess and the liberated iodine is titrated.
one example is; Determination of Cu2+.
2Cu2+ + 4I- = 2CuI2(unstable) = Cu2I2 + I2
I2 + 2S2O32- = 2I- + S4O62-
[2mole Cu2+ ≡ 1mole I2 ≡ 2moles S2O32- gives, moles Cu2+ = moles S2O32]
vii) Precautions: air oxidation of iodide ion (acid and sunlight)
NO2- shouldn’t be present, HNO2 + 2H+ + I- = NO(nitric oxide) + I2 + 2H2O; NO in turn is oxidized back to nitrite by aerial oxygen, 4NO + O2 + 2H2O= 4HNO2
KI should be free of iodates, IO3- + 5I- + 6H+ = 3I2(more I2) + 3H2O