Redox Titrations

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 Introduction

 The volumetric analysis which are based on neutralization,

complexometric, precipitation titration or ion combination reactions .

 Redox are based on the transfer of electrons between the titrant and the
analyte.
 Titrations that involve the processes of oxidation and reduction

 On the other hand, oxidation – reduction method of analysis involve a

change in valence by transferring electrons from one substance to other,

termed electron transfer rxn.

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 Cont.…
 Oxidation: - loss of electron (↑ in oxidation number)
- Addition of oxygen, such as SO2 + O → SO3
- Removal of hydrogen, e.g. H2S + O → H2O + S

 Reduction: - gain of electron (↓ in oxidation number)

- Addition of hydrogen e.g. CHCH + 2H →CH2 = CH2
- Removal of oxygen, e.g. . CuO + 2H → Cu + H2O

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 What are oxidation-reduction reactions?
 Oxidation reduction reactions are chemical reactions that
involve the transfer of electrons between the reacting species.

 These electron transfers are accompanied by a change in the

oxidation state of the reactants.

 In a chemical reaction, oxidation and reduction occur

simultaneously. If one atom is oxidized, other is reduced.

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 Reducing agent
 is one which loses the electrons, i.e reduces the other substance by donating

electrons to it.

An oxidizing agent
 Is one which accepts electrons, i.e oxidizes the other substance by stripping

off electrons from it

 its oxidation state decreases.

 Oxidation and reduction reactions always occur simultaneously; i.e.

when one substance is oxidized the other substance is reduced and vice versa.
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 cont...
During a redox reaction the oxidizing agent itself undergoes
reduction while the reducing agent undergoes its oxidation.

Thus reduction reaction is represented as

 Oxidant + ne = Reductant

 Oxidation reaction is represented as

 Reductant = Oxidant + ne
The relative tendency to accept or lose electrons by any reagent is
measured in terms of their standard reduction potential values.

 The standard electrode potential enable us to predict which ions

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will oxidize or reduce other ions.
 The chief oxidizing & reducing agents used in volumetric work

oxidizing agents reducing agents

 potassium permanganate  oxalic acid,

 potassium dichromate  potassium arsenite,

 iodine  ferrous ammonium sulphate

 potassium iodate  Titanium chloride and sulphate

 ceric  sodium thiosulphate

The half reactions:-{

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 Redox titration
 KMnO4+ FeSO4+ H2SO4→ MnSO4+ Fe2 (SO4)3 + K2SO4+H2O
(Here, electrons are transferred from FeSO4to KMnO4)

 Mn (+7) in KMnO4 has been reduced to Mn(+2) in MnSO4.

 Fe(+2) in FeSO4 has been oxidized to Fe(+3) in Fe2 (SO4)3.

 Thus, KMnO4 acts as oxidizing agent and FeSO4 acts as reducing

agent in acidic medium.

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 Redox titration…….
 Redox titration is based on an oxidation reduction reaction
between the titrant and the analyte

 These types of titrations sometimes require the use of a

potentiometer or a redox indicator

 In order to evaluate redox titrations, the shape of the

corresponding titration curve must be obtained

 In these types of titration, it proves convenient to monitor the

reaction potential instead of monitoring the concentration of a
reacting species
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 Redox titration…….

 In redox titrations, two reactions take place simultaneously,

oxidation and reduction.

 Oxidation and reduction reactions, each are known as half

reactions.

 Consider the following reaction: Ce+4+ Fe+2 → Ce+3+ Fe+3

 Oxidation half reaction may be written as: Fe+2 → Fe+3+ e−

 Reduction half reaction may be written as:Ce+4+ e− → Ce+3

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 Redox titration…….

 Hence, ferrous sulphate can be estimated quantitatively by its

reaction with ceric sulphate.

 Detection of endpoint in redox titrations can be performed

either by color indicators or by Potentiometry.

 Color indicators are compounds which change color from their

oxidized to reduced form.

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 Redox titration…

REDOX TITRATION CURVES

 By plotting the redox potential corresponding to different points in the

titration, a titration curve similar to the curve obtained in an acid-base
method is obtained.

Example: titration of 100 cm3 of 0.1M iron (II) with 0.1 M cerium (IV) in the
presence of dilute sulphuric acid.

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 Redox titration…….
Redox indicators
1. Self indicator :- The titrant itself acts as a self indicator.

 It shows the intense colour at the end point.

 For example:- potassium permanganate, ceric ammonium

sulphate , iodine

 A titrants like MnO−4, have oxidized and reduced forms whose

colors in solution are significantly different.

 In acidic solutions, however, permanganate’s reduced form,

Mn2+, is nearly colorless.
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 Redox titration…….

 When MnO−4 is used as an oxidizing titrant, the solution

remains colorless until the first drop of excess MnO−4 is added.

 The first permanent shade of purple signals the end point.

 KMnO 4 gets reduced in redox titration as follows

 MnO4−(purple)+ 4H + Mn 2 +(colorless) + 4H2O

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 Redox titration…….

2. Redox indicators
 These are added to the reaction mixture during the titration.

 A redox indicator is a compound that under go a redox

reaction and changes color depending on the potential of the
solution. i.e. OxIn and RedIn have two different colors.

 Since the indicator changes color in response to the

electrochemical potential, and not to the presence or absence
of a specific species, these compounds are called general redox
indicators. 15
 Redox titration…….
 The oxidized and reduced form of the indicator should have a contrast
difference in the colours. Inoxd + ne = Inred

 At potential E, the ratio of the concentration of two forms is given by the Nernst
equation - For the generalized half - cell reaction,
Ox  ne -  Red
- The potential is given by the generalized form of the Nernst equation
RT aRed RT aRed
EE  0
ln  E  2.303
o
log
nF aOx nF aOx
0.05916 [Red]
EE  0
log
n [Ox]
Where, E o  Standard electrode potential aRed  activity of reduced form
R  Molar gas constant ( 8.314 joule/k - mole) aOx  activity of oxidized form
T  temper ature in kelvin, 25o C F  Faraday’ s constant (96 485 C)
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n  number of electrons transfer red
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 Redox titration…….

3. Specific indicator:- a substance which reacts in a specific manner

with one of the reagents in a titration to produce colour.
 Some indicators form a colored compound with a specific oxidized or
reduced form of the titrant or the titrand

 Starch, for example, forms a dark blue complex with I3- and can be used

 to signal the presence of excess I3- (color change: colorless to blue), or

 the completion of a reaction in which I3- is consumed (color change: blue to

colorless).
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 Redox titration…….

 Starch is not a redox indicator;

 it responds specifically to the presence of I2, not to a change in

redox potential.

 Another example of a specific indicator is thiocyanate, which

forms a soluble red-colored complex, Fe(SCN)2+, with Fe3+.

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 Redox titration…….

4. Potentiometric Method:-
 It is a physicochemical method where the equivalence point is
detected by large changes in potential.

 This method can be used when suitable indicators are not

available, visual method is of limited accuracy coloured
solutions or very dilute solutions).

 Potential is measured by a potentiometer.

 At end point, there is sudden rise in potential

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 Applications of redox titrations

 In oxidimetric titrations the oxidising agents are used to

determine the reducing and while is reductimetric agents
are employed for the determination of oxidising agents.
I. Oxidimetric Reagents

 Used for the analysis of reducing agents.

 The choice of which of several common oxidizing titrants is best for a

particular analysis depends on the ease with which the analyte can be

oxidized.
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 Applications ……..

 Types of redox titrations depends on Oxidimetric Reagents

Redox titration Titrant

1. Dichrometry Potassium dichromate

2. Titration involving iodine (Iodometry & Iodimetry) Iodine(I2)

3. Bromatometry Bromine(Br2)

4. Cerimetry Cerium(IV)salts

5. Permanganometry Potassium permanganate

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 Applications ……..

 The quantitative estimations of a number of pharmaceutical

substances may be carried out by using these variety of potential
oxidizing agents and reducing agent.
1. Potassium permanganate titration methods
 The vital application of potassium permanganate as a potential
oxidizing agent in all medium but it is strong in acidic medium

 The medium is maintained by the use of dilute sulfuric acid

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 Applications ……..

 It is readily available and inexpensive It requires no indicators

except in very dilute solutions

 Permanganate undergoes a variety of chemical reactions, since

manganese can exist in oxidation states of +2, +3, +4, +6 & +7

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 Applications ……..

 Ionically we have :
 MnO4−(purple/Violet) + 8H + + 5e Mn 2 +(colorless) + 4H2O …Eored = +1.51V

 Purple mangnate ion ↔ Colorless manganese ion

 MnO4 is a self-indicator
 Can be used for the analysis of many reducing agents, weak or strong.

 Examples

• Determination of peroxide: eg. Hydrogen peroxide, ZnO2

• Determination of ferrous salt

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 Applications ……..

 Limitation:

 KMnO2 not being a primary standard.

 its solution needs to be filtered off MnO2 after prolonged

period of storage.

 More so its solution needs to be stored in dark so as to check

formation of MnO2 catalysed by light. (unstable to light, heat ...)

 Reading assignment : preparation of KMnO2

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 Applications……

2. Potassium dichromate
 It is a strong oxidant in acidic medium; the reduction equation
being the following.

 Potassium dichromate is also a very strong oxidizing agent but

less than permanganate

 Still it is widely used in redox titrations because of several

advantages over permanganate.
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 Applications……

 Unlike potassium permanganate, potassium dichromate is

available in high purity (primary standard) and is highly
stable

 It can’t be used as a self indicator like KMnO4.

 The end point in titrations with dichromate ion is generally

detected by using suitable redox indicators such as
diphenylamine, sodium diphenylamine sulphonate etc.
 Thus it can be used to determine iron(II) in hydrochloric acid medium.

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 Redox titration involving iodine:
Reading assignment

Hint : Iodimetric titrations:

 Used to detrmie a reducing analyte

 One step reaction

 Standard solution: Iodine (I2)

Iodometric titrations:

 Used to determine an oxidizing analyte

 Two step reactions

 Standard solution: Sodium thisulfate 29

Drugs direct titrated with standard iodine solution:

Benzylpencillin potassium

Ascorbic acid Captopril

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 Practical Problem

 The amount of ascorbic acid, C6H8O6, in orange juice was determined by

oxidizing the ascorbic acid to dehydroascorbic acid, C6H6O6, with a known

excess of I3– and back titrating the excess I3– with Na2S2O3.

 A 5.00-mL sample of filtered orange juice was treated with 50.00 mL of

excess 0.01023 M I3–. After the oxidation was complete, 13.82 mL of 0.07203

M Na2S2O3 was needed to reach the starch indicator end point. Report the

concentration of ascorbic acid in milligrams per 100 mL.

a. C6H8O6 + I3- (excess )→ CçH6O6 + 3I- + 2H+

b. 31
 Thus, there is 2.43 mg of ascorbic acid in the 5.00-mL sample, or
48.6 mg/100 mL of orange juice.
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 Applications……
B. REDUCTIMETRIC REAGENTS

 Standard solutions of reducing agents are not used as widely as

oxidising agents, because most of them are oxidized by dissolved
and atmospheric oxygen.

 They are, therefore, less convenient to prepare and use.

 Thiosulphate is the only common reducing agent that is stable to

air oxidation and can be kept for long periods of time.

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 Applications……

Common reductimetric reagents

 Iron

 Chromium (II) and Titanium(III)

 Sodium Thiosulfate, Na2S2O3

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 Applications...

Butylhydroxybenzoate
Amylmetacresol Benzylhydroxybenzoate

Chloroxylenol

Chlorocresol

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Diazotization Titration

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 Diazotization Titration or Nitrite Titration

 Diazotization is used in the analysis of aromatic compounds

containing an amino group in the molecules.

 Aromatic primary amine reacts with sodium nitrite in acid

solution (i.e, nitrous acid) to form diazonium salts.

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 Diazotization

 Is used in the quantitative analysis of aromatic cpds containing an

amino group in the molecules.

 This analysis is based on the reaction between aromatic primary amine

(Ar–NH2) & HNO2 in presence of excess mineral acids.
– By measuring the volume of NaNO2 solution required to convert them into
diazonium salts.

 NaNO2 is generally used in direct method of diazotization.

– It gives nirtous acid (HNO2) insitu in acidic solution.

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 Principle
 The typical reaction of diazotization reaction in presence of HCl is:

 When all the aromatic amine has reacted with NaNO2 then the excess of
NaNO2 added to the solution converted to HNO2 that remain in the solution &

 It can be detected by the starch paper or paste as an external

indicator.

 This appearance of free HNO2 in solution indicates that

diazotization reaction is complete and equivalence point is attained.

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 Condition for diazotization

• Rate of titration
• Temperature of the solution

Rate of titration:
– Depending on the rate of conversion into azo cpds, amines are
classified as:
• Rapidly diazotisable &
• slowly diazotisable amines

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 Diazo....

– Slow diazotisable cpds that contain:

• sulpha groups, nitrous oxide group, or carboxylic group in
aromatic ring.
– Fast diazotisable cpds do not contain any substituent group
other than amino group;
• but some times they may contain –CH3 or –OH group along
with NH2 group.
– Example: - aniline and aminophenol.
– In case of slowly diazotisable cpd:
• Sufficient Time (5-10 min) should be given to the solution
under test.
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 Diazo....
– It is also suggested that the burette tip is placed below the
surface of reaction mixture to prevent the loss of HNO2.

• Temperature:

– The diazonium cpds so formed are instable and readily

decompose at elevated temperature.
• To eliminate this problem, the titration is carried out at reduced
temperature (0-5 C).

– Optimum temperature for most amine is 10-15 C, where they

form relatively stable diazo cpds.

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 End point determination

• Visual method
• Electrometric method

Visual end point determination method:

– Principle: - aromatic primary amine reacts with sodium nitrite in acid
solution to form diazonium salts. amino benzene or phenylamine
C6H5NH2 + NaNO2 + HCl →→ C6H5N2Cl + NaCl + 2H2O
– Observation of end point depends upon the detection of small excess
of nitrous acid, which is then present.
– This can be demonstrated visually by using starch iodide paste as
external indicator.
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 Diazo....

• Starch iodide paper or paste is the starch solution plus equal volume of 5%
KI solution in H2O.
– Starch iodide paste with reaction mixture is as follows-

– The liberated I2 reacts with starch to give blue colour.

– The diazotization proceeds quantitatively only in presence of inorganic
acid.
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 application …….

• An important pharmaceutical application of sodium

nitrite titration is the analysis of sulphonamides.
• More list of cpds assayed by sodium nitrite titration:
– Dapsone - Benzocaine
– Procaine hydrochloride - Calcium amino salicylate
– Sodium amino salicylate - Sulphacetamide tablet
– Sulphadoxine - All sulpha drugs

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 Assay of Benzocaine
• Assay Weight accurately about 0.25 g of Ethyl Amino-benzoate, previously dried,
dissolved in 10 mL of hydrochloric acid and 70 mL of water, add 10 mL of a solution
of potassium iodide and cool to a temperature below 15 ºC. Then titrate with 0.1
mol/L sodium nitrite VS using starch paste as Endpoint Detection Methods. The
total volume of 0.1 mol/L sodium nitrite consumed by benzocaine is 15 ml.
Calculate the percent purity of benzocaine in the sample.

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47
– Solution
– - Each mL of 0.1 mol/L sodium nitrite = 16.519 mg of C9H11NO2
– 1ml = 16.519 mg
– 15ml = x , x = 247.785mg
– % purity = 247.785/250 * 100 = 99.114%

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