Redox Titrations
A redox titration is a type of titration based on a redox reaction between
the analyte and titrant.
Redox titration may involve the use of a redox indicator and/or a
potentiometer.
Oxidation-reduction reactions are commonly called redox reaction.
Example:
Oxidation: Reduction:
Similarly,
In the above reaction, an electron is transferred from Fe2+ to Ce4+ to form
Ce3+ and Fe3+ ions.
A substance that has a strong affinity for electrons, such as Ce4+, is called an
oxidizing agent, or an oxidant.
A reducing agent, or reductant, is a species, such as Fe2+, that donates
electrons to another species. 2
The reducing and oxidizing tendency of a substance will depend on its
reduction potential (E0).
Reduction potential (also known as redox potential, oxidation / reduction
potential) is a measure of the tendency of a chemical species to acquire
electrons and thereby be reduced.
(Reduction potentials tell you how likely an element or ion is to be
reduced by gaining electrons. The redox potential is used to describe a
system's overall reducing or oxidizing capacity.)
The more positive the value of E0, the stronger the tendency for the half
reaction to proceed in the direction of taking up electrons.
Reduction potential is measured in volts (V), or millivolts (mV).
E0
Mg2+ + 2e- = Mg -2.37 V
Cl2 + 2e- = 2Cl- 1.36 V
The oxidizing power of a species depends on its standard reduction
potential (Eo). The more positive Eo is, the stronger the oxidizing capability
3
of the substance.
By international agreement, a standard electrode potential, E° measures
the tendency for a reduction process to occur at an electrode.
Figure: Measuring standard electrode potentials (a) A standard hydrogen
electrode is the anode, and copper is the cathode. (b) This cell has the
same connections as that in part (a), but with zinc substituting for copper.
4
Ecell = +1.103 V
E0 = +0.34 V
E0 = -0.76 V
Zn(s) Zn2+(aq) + 2e-
Cu2+(aq) + 2e- Cu(s)
Figure: The reaction: Zn (s) + Cu2+ (aq) Zn2+ (aq) + Cu (s) in an
electrochemical cell. 5
6
Example of some important redox reactions
Zn (s) + Cu2+ (aq) Zn2+ (aq) + Cu (s)
Since titrants in a reduced state are susceptible to air oxidation, most
redox titrations are carried out using an oxidizing agent as the titrant.
7
The following table summarizes the properties of five of the most widely used
volumetric oxidizing reagents.
(1) -Napthoflavone; (2) 1,10-phenanthroline iron(II) complex (ferroin); and (3)
diphenylamine sulfonic acid.
† (a) indefinitely stable; (b) moderately stable, requires periodic standardization; and
(c) somewhat unstable, requires frequent standardization.
‡ E in 1 M H2SO4.
8
Ce(IV)−Fe(II) titration
Eo = + 1.70 V (1 M HClO4)
Eo = + 0.77 V (1 M HClO4)
Ecell = + 0.93 V
The end point can be determined by two methods:
1. Redox indicators – the indicator has different color at reduction and
oxidation state.
2. Indicator electrode (Potentiometric method).
Ce4+ is yellow and Ce3+ is colorless, but the color change is not distinct
enough for cerium to be its own indicator.
Ferroin and other substituted phenanthroline redox indicators are well
suited to titrations with Ce4+.
9
(1) Redox indicators
A redox indicator is a compound that changes color when it goes from its
oxidized to its reduced state.
As with acid-base indicators, the color of In(reduced) will be observed
when
and the color of In(oxidized) will be observed when
10
Table : Redox indicators
The indicator ferroin changes from pale blue (almost colorless) to red.
E0 = 1.06 V
11
The indicator action of diphenylamine can be understood as:
The diphenylamine (I) undergoes oxidation first into a colorless
diphenylbenzidine (II) which is the real indicator and is reversibly further
oxidized to diphenylbenzidine (III) blue-violet.
+ 2e + 2H+
+ 2e + 2H+
E0 = 0.76 V
12
➢ The redox indicator reaction must be both rapid, and it must be
reversible.
➢ If the reaction is slow or is irreversible (slow rate of electron transfer),
the color change will be gradual, and the end point will not be sharp.
(2) Potentiometric end point
Figure: Theoretical curve for titration of
Figure : Apparatus for potentiometric 50.0 mL of 0.100 M Fe2+ with 0.100 M Ce4+
titration of Fe2+ with Ce4+. in 1 M HClO4. 13
MnO4− − Fe(II) titration
The principal use of permanganate is for the volumetric titration of iron(II)
based on the following reaction:
E°red = + 1.51 V
E°red = + 0.77 V
This titration is performed in the presence of 0.1 M or greater
concentrations of sulfuric acid.
In less acidic media, the product may be Mn(III), Mn(IV), or Mn(VI),
depending on conditions.
For example, aqueous solutions of permanganate are thermodynamically
unstable due to its ability to oxidize water.
E°red = + 1.23 V
In strongly alkaline solution (2M NaOH), green manganate ion is produced.
E°red = +0.56 V
14
Permanganate solution decompose in presence of manganous ions.
The reaction is quite slow in acidic medium but attains a fast rate in
neutral solutions.
Thus, permanganate solution can not be considered as a primary
standard solution by simply making the calculations based on the
amount of permanganate weighed.
Hydrochloric acid is usually avoided because it reacts with KMnO4
according to the equation given below:
E°= Cl2/Cl− = + 1.36 V
Oxidation of chloride to chlorine by permanganate can be a source of
positive errors as permanganate is consumed in this reaction.
If HNO3 is used, then it oxidizes the Fe2+ instead of the MnO4− as it is a
strong oxidizing agent. If no acid is used, then an MnO2 precipitate is
produced. 15
Standardization of Potassium permanganate with sodium oxalate :
KMnO4
Na2C2O4 + H2SO4
Pale pink color
5 mmol C2O42- 2 mmol MnO4- 16
This titration is carried out in warm conditions ( 60oC).
❖ The reaction at room temperature is slow because of the equilibrium
nature of this reaction.
❖ CO2 is highly soluble in water and thus heating removes all dissolved
carbon dioxide out of the solution driving the reaction in forward
direction.
❖ Also at low temperature, the reduction of permanganate may not be
complete producing Mn(III) (in the form [Mn(C2O4)3]3−). The formation
of this species introduce errors in titrations as no. of electrons utilized
here are different as compared to production of Mn2+. This complex
however breaks on heating and hence reaction proceeds smoothly.
17
Estimation of Fe(II) with Potassium permanganate:
Fe2+ + Fe3+ (yellow)
1 600C HCl + SnCl2
Fe2+ (colorless)
HgCl2
Fe2+ + Hg2Cl2(Silky ppt)
Z-R reagent
Fe2+
Fe2+ + Hg2Cl2(Silky ppt)
KMnO4
[Fe(HPO4)]+ + Mn2+
18
As Fe2+ readily oxidizes to Fe3+, it is necessary to ensure that all of the iron
in the unknown is in the Fe2+ state prior to titration. The unknown is
treated with tin(II) chloride, which reduces any small amount of Fe3+ that
might be present:
The excess Sn2+ is then removed by reaction with mercury(II) chloride,
which produces insoluble mercury(I) chloride:
Due to the introduction of Cl− ion in the system, some permanganate may
be consumed in the formation of chlorine by the following reaction.
To overcome or suppress this reaction, Zimmermann and Reinhardt's
solution (this is sometimes termed preventive solution) is used.
Z-R reagent: 50 g of crystallized manganese(II) sulphate (MnSO4.4H2O) + 250
mL water + cooled mixture of 100 mL concentrated sulphuric acid and 300
mL water + 100 mL syrupy orthophosphoric acid.
19
Function of Zimmermann and Reinhardt's (Z-R) solution
➢ The manganese(II) sulphate lowers the reduction potential of the
MnO4− − Mn(II) couple and thereby makes it a weaker oxidizing agent;
the tendency of the permanganate ion to oxidize chloride ion is thus
reduced.
➢ The phosphoric (V) acid combines with the yellow Fe3+ ion to form the
complex ion [Fe(HPO4)]+, thus rendering the end point more clearly
visible.
➢ The phosphoric (V) acid lowers the reduction potential of the Fe(III)-
Fe(II) system by complexation, and thus tends to increase the reducing
power of the Fe2+ ion.
Under these conditions permanganate ion oxidizes iron (II) rapidly and
reacts only slowly with chloride ion. 20
Problem: Patients suffering from iron deficiency are often prescribed tablets
containing FeSO4.7H2O. Several tablets, 6.00 g, were dissolved in water and
made up to 200 mL in a volumetric flask. 25.00 mL portions of this solution
were then titrated against 20 mM KMnO4 solution. The mean titer volume
was 20.10 mL. Calculate the percentage of FeSO4.7H2O in the tablets.
Solution:
Amount KMnO4 = 20.10 mL × 0.02 M = 0.402 mmol KMnO4 [1 mM = 110−3 M]
𝟓 𝐦𝐦𝐨𝐥 𝐅𝐞𝟐+ 𝟏 𝐦𝐦𝐨𝐥 𝐅𝐞𝐒𝐎𝟒.𝟕𝐇𝟐𝐎 𝟐𝟕𝟖 𝐦𝐠
0.402 mmol KMnO4 ×
𝟏𝐦𝐦𝐨𝐥 𝐊𝐌𝐧𝐎𝟒 𝟏 𝐦𝐦𝐨𝐥 𝐅𝐞𝟐+ 𝟏 𝐦𝐦𝐨𝐥 𝐅𝐞𝐒𝐎𝟒.𝟕𝐇𝟐𝐎
𝐅𝐞𝐒𝐎𝟒𝟕𝐇𝟐𝐎
= 558.78 mg
𝟐𝟓.𝟎𝟎 𝐦𝐋
Mass of FeSO4.7H2O in 200 mL sample = 0.55878 8 g = 4.47 g
𝟒.𝟒𝟕 𝐠
% FeSO4.7H2O = × 100 = 74.5%
𝟔.𝟎𝟎 𝐠
21
Problem: Titration of 0.2121 g of pure Na2C2O4 (134.00 g/mol) required 43.31 mL
of KMnO4. What is the molar concentration of the KMnO4 solution (0.01462 M)?
The chemical reaction is
Problem: Calculate the percentage of iron in a sample of steel wire if 1.51 g of
the wire was dissolved in excess of dilute sulphuric acid and the solution made
up to 250 mL in a standard flask. 25.0 mL of this solution was pipetted into a
conical flask and needed 25.45 mL of 0.02 mol L-1 KMnO4 for complete oxidation.
Solution: Amount KMnO4 = 25.45 × 0.02 mmol
= 0.509 mmol KMnO4
𝟓 𝐦𝐦𝐨𝐥 𝐅𝐞𝟐+
0.509 mmol KMnO4 ×
𝟏𝐦𝐦𝐨𝐥 𝐊𝐌𝐧𝐎𝟒
∴ mmol Fe2+ in 25.0 mL solution = 2.545
mmol Fe2+ in 250 mL solution = 2.545 × 10
Mass Fe = 2.545 × 10 × 55.8 = 1420.1 mg = 1.42 g
𝟏.𝟒𝟐 𝐠
% Fe = × 100 = 94.0%
𝟏.𝟓𝟏 𝐠 22
Problem: The calcium in a 10.00 mL serum sample is precipitated as
CaC2O4 with ammonium oxalate. The filtered precipitate is dissolved in
acid, the solution is heated, and the oxalate is titrated with 1 mM KMnO4,
requiring 9.94 mL. Calculate the concentration of calcium in the serum
sample.
5H2C2O4 + 2MnO4− + 6H+ = 10 CO2 + 2Mn2+ + 8H2O
mmol Ca2+ mmol C2O42− 5/2 mmol MnO4−
Problem: Aqueous solutions of hydrogen peroxide sold in pharmacies are
usually approximately 3% H2O2 by mass. However, in solution, hydrogen
peroxide decomposes into water and oxygen. What is the percent by mass
of a solution of hydrogen peroxide, H2O2, prepared from 1.423 g of H2O2
which is titrated with 40.22 mL of 0.01143 M KMnO4.
The reaction occurs in an acidified solution.
23
Comparison of Ce(IV) with KMnO4
➢ For all practical purposes, the oxidizing strengths of permanganate and
cerium(IV) solutions are comparable.
Eo = + 1.51 V (1 M H2SO4)
Eo = + 1.44 V (1 M H2SO4)
Eo = + 1.70 V (1 M HClO4)
➢ Solutions of cerium(IV) in sulfuric acid, however, are stable indefinitely,
but permanganate solutions decompose slowly and thus require
occasional re-standardization.
➢ Furthermore, cerium(IV) solutions in sulfuric acid do not oxidize
chloride ion and can be used to titrate hydrochloric acid solutions of
analytes. In contrast, permanganate ion cannot be used with
hydrochloric acid solutions unless special precautions are taken to
prevent the slow oxidation of chloride ion that leads to
overconsumption of the standard reagent.
24
➢ A further advantage of cerium(IV) is that a primary-standard-grade
salt of the reagent is available (cerium ammonium nitrate,
Ce(NO3)4.2NH4NO3, in 1M H2SO4), thus making possible the direct
preparation of standard solutions.
➢ Despite these advantages of cerium solutions over permanganate
solutions, the latter are more widely used. One reason is the color of
permanganate solutions, which is intense enough to serve as an
indicator in titrations. A second reason for the popularity of
permanganate solutions is their modest cost.
➢ Another disadvantage of cerium(IV) solutions is their tendency to
form precipitates of basic salts in solutions that are less than 0.1 M in
strong acid.
25
Titration of Fe(II) with K2Cr2O7
Titrate with
SnCl2 K2Cr2O7
[(Fe2+ + Fe3+ + HCl) End point color
HgCl2 + H3PO4 + Indicator
solution]
26
Cr2O72- −Fe(II) titration
Potassium dichromate is a relatively strong oxidizing agent whose
principal advantages are its availability as a primary standard and the
long-term stability of its solutions.
It is not, however, as strong an oxidizing agent as MnO4– or Ce4+, which
prevents its application to the analysis of analytes that are weak reducing
agents. Its reduction half-reaction is
E = 1.33 V
Although solutions of Cr2O72– are orange and those of Cr3+ are green,
neither color is intense enough to serve as a useful indicator.
Diphenylamine, whose oxidized form is blue-violet and reduced form is
colorless, gives a very distinct end point signal with Cr2O72–.
The principal use of dichromate is for the volumetric titration of iron(II)
based on the following reaction
27
Often, this titration is performed in the presence of moderate
concentrations of sulfuric or hydrochloric acid.
As Fe2+ readily oxidizes to Fe3+, it is necessary to ensure that all of the iron
in the unknown is in the Fe2+ state prior to titration.
The unknown is treated with tin(II) chloride, which reduces any small
amount of Fe3+ that might be present:
The excess Sn2+ is then removed by reaction with mercury(II) chloride,
which produces insoluble mercury(I) chloride:
➢ Due to weak oxidizing nature of dichromate when compared to
permanganate, the reaction becomes slow at the end point. So syrupy
phosphoric acid should be added in order to increase the rate of
reaction at the end pint, by removing the yellow ferric ions as colorless
ferric phosphate [Fe(HPO4)]+ from the sphere of the reaction. Thus, the
end point is sharper. 28
➢ The reduction potential value of diphenylamine is E°red = +0.76V which is
very near to that of ferrous-ferric system (E°red = + 0.77V).
➢ The added phosphoric acid reduces the reduction potential of Fe(II)–
Fe(III) system by 0.15 – 0.3 volts, thereby reducing capacity is increased,
when compared to diphenylamine indicator. When once all the ferrous
iron ions completely oxidized with dichromate an excess drop of
dichromate will oxidize the indicator from bluish green to bluish violet.
Problem:
In a redox titration 12.50 mL of 80 mM K2Cr2O7 (aq) was used in acidic
solution to oxidize Sn2+ (aq) ions to Sn4+ (aq) ions. The volume of K2Cr2O7
(aq) used was just sufficient to oxidize all the Sn2+ (aq) in 10.0 mL of the
solution. Calculate the concentration of the Sn2+(aq) ions in the solution
according to the following unbalanced equation (Ans: 0.300 mol/L).
Cr2O72− (aq) + Sn2+(aq) → Sn4+(aq) + Cr3+(aq)
29
Titrations Involving Iodine
Iodimetry:
(Acidic solution)
Iodometry:
30
Iodimetry:
Iodine is a moderately strong oxidizing agent and can be used to titrate
reducing agents. Titrations with I2 are called iodimetric methods.
In iodimetry, the titrant is I2 and the analyte is a reducing agent.
The end point is detected by the appearance of the blue starch–iodine
color.
These titrations are usually performed in neutral or mildly alkaline (pH 8)
to weakly acidic solutions.
If the pH is too alkaline, I2 will disproportionate to hypoiodate and iodide:
There are three reasons for keeping the solution from becoming strongly
acidic.
31
First, the starch used for the end-point detection tends to hydrolyze or
decompose in strong acid, and so the end point may be affected.
Second, the reducing power of several reducing agents is increased in
neutral solution.
This equilibrium is affected by the hydrogen ion concentration. At low
hydrogen ion concentration, the equilibrium is shifted to the right.
In neutral solution the potential of the As(V)/As(III) couple is decreased
sufficiently that arsenic(III) will reduce I2.
The pH for the titration of arsenic(III) with I2 can be maintained neutral by
adding NaHCO3.
The bubbling action of the CO2 formed also helps remove the dissolved
oxygen and maintains a blanket of CO2 over the solution to prevent air
oxidation of the I−.
32
The third reason for avoiding acid solutions is that the I− produced in the
reaction tends to be oxidized by dissolved oxygen in acidic solution:
Because I2 is not a strong oxidizing agent, the number of reducing agents
that can be titrated is limited.
In most direct titrations with iodine (iodimetry) a solution of iodine in
potassium iodide is employed, and the reactive species is therefore the tri-
iodide ion I3−.
33
Iodine reacts with iodide to produce the triiodide ion:
K = 7.1 × 102
Due to this reaction, solid iodine is soluble in solutions of iodide salts.
However, most of the dissolved iodine is actually present as triiodide, not
as iodine. Thus, the reduction of iodine may be written as
E = 0.545 V
Iodine/triiodide solutions are unstable for a variety of reasons.
➢ First of all, aqueous iodine exerts a significant vapor pressure, i.e.
volatile nature of iodine.
➢ Under acidic conditions iodide is slowly air-oxidized to produce iodine
and this reaction is promoted by heat and temperature.
34
Strictly speaking, all equations involving reactions of iodine should be
written with I3− ; rather than with I2, e.g.
is more accurate than
For the sake of simplicity, however, the equations will usually be written in
terms of molecular iodine rather than the tri-iodide ion.
Iodometric titrations:
When an excess of iodide (I− ) is added to a solution of an oxidizing agent,
I2 is produced in an amount equivalent to the oxidizing agent present. The
liberated I2 is titrated with standard sodium thiosulfate solution, using
disappearance of the starch–iodine color for the endpoint.
Analysis of an oxidizing agent in this way is called an iodometric method.
Example:
35
Sodium thiosulfate solution is not a primary standard substance due to
the following reasons:
➢ Dissolved carbon dioxide (CO2 makes the solution acidic) promotes
disproportionation of S2O32−:
➢ Light exposure tends to hasten the decomposition.
➢ Moreover, decomposition may also be caused by bacterial action
particularly if the solution has been standing for some time.
The following precaution should be taken to prevent from
disproportionation of thiosulfate:
➢ Thiosulfate solutions should be stored in the dark.
➢ Addition of 0.1 g of sodium carbonate per liter maintains the pH in an
optimum range for stability.
➢ Three drops of chloroform should also be added to each bottle of
thiosulfate solution to help prevent bacterial growth.
36
❖ Sodium thiosulfate solution must be standardized before any analysis.
Standardization of Sodium Thiosulfate with Potassium Dichromate:
Potassium dichromate is reduced by an acid solution of potassium iodide,
and iodine is set free:
-----------(1)
-----------(2)
➢ The liberated iodine is titrated with thiosulfate solution and the end is
detected with starch.
➢ The disappearance of the blue starch−I2 color indicates the end point
of titration.
➢ Concentration of thiosulfate is calculated from the reaction
stoichiometry.
37
(d)
(a) H2O + HCl (b) Brown coloration of I2 becomes pale
yellow after titration with S2O32-.
NaHCO3 (c) After addition of starch
(d) End point color
KI K2Cr2O7 Keep in dark for five minutes
38
The above reaction encounters the following problems:
➢ Hydriodic acid (from excess of iodide and acid) is readily oxidized by
air, especially in the presence of chromium(III) salts;
➢ It is not instantaneous.
The best way to overcome above problems:
❖ A current of carbon dioxide is passed through the reaction flask
before and during the titration.
❖ A more convenient but less efficient method is to add some solid
sodium hydrogen carbonate to the acid solution, and to keep the flask
covered as much as possible, and to allow 5 minutes for its
completion.
Starch is not a redox indicator; it responds specifically to the presence of
I2, not to a change in redox potential.
In iodometry, I2 is present throughout the reaction up to the end point.
39
Starch is added near the end point due to the following reasons:
➢ Iodine-starch complex is not only slowly dissociated and a diffuse end
point would result if a large amount of iodine were adsorbed on the
starch.
➢ Most of the iodometric titrations are performed in strong acid medium
and starch has a tendency to hydrolyze in acid solution.
(a) Structure of the repeating unit of amylose (a polymer of the sugar α-D-glucose). (b) Schematic
structure of the starch iodine complex. The amylose chain forms a helix around I6 units, which have a
deep blue colour. (c) View down the starch helix, showing iodine inside the helix.
40
Problem:
2.05 g of potassium dichromate, K2Cr2O7 (FW = 294.3 g/mol), was
dissolved in water and made up to 250 mL. A 25.00 mL aliquot of this
solution was mixed with an excess of acidified potassium iodide
solution and then iodine was formed by the reaction,
Cr2O72− + 6I− + 14H+ → 2Cr3+ + 3I2 + 7H2O
The iodine produced was titrated with sodium thiosulphate solution
and 21.50 mL was needed to reach the end point.
2S2O32− + I2 → S4O62− + 2I−
What was the concentration of the sodium thiosulphate solution?
41
Iodometric determination of copper
(a) (b) (c)
KI 1. Na2S2O3
2. Starch
Na2S2O3
(f) (e) (d)
Na2S2O3
KSCN
(f) End point color (e) Mixture (d) + KSCN (d) Mixture (c) + Na2S2O3
(a) Cu2+ solution + NH3 solution + Acetic acid
(b) Solution (a) + KI → Keep in dark for five minutes
(c) Titration with Na2S2O3 + starch 42
Upon addition of excess iodide to a solution of Cu(II), a precipitate of
Cu2I2 is formed along with I2. The liberated iodine is then titrated with
standard sodium thiosulfate.
The pH of the solution must be maintained between pH 3 to 4 by the
addition of a buffer. It has been found that iodine is adsorbed onto the
surface of the copper(I) iodide precipitate and must be displaced to obtain
correct results.
Potassium thiocyanate is usually added just before the end point is
reached to displace the adsorbed iodine.
Cu2I2 (s) + 2 SCN− Cu2(SCN)2 (s) + 2I−
Accompanying this reaction is the release of the adsorbed iodine, which
thus becomes available for titration. 43
Precautions must be taken to avoid side reactions.
➢ For instance, iodine will slowly oxidize tetrathionate to sulfate,
especially at high pH values.
➢ At low pH sulfurous acid may be formed by thiosulfate.
➢ Another source of error in strong acid solution is air oxidation of
iodide:
4I− + O2 + 4H+ 2I2 + 2H2O
This is called oxygen error. These side reactions may be avoided by carrying
out the thiosulfate - iodine reaction in the pH range 2 - 5.
Problem: A 0.200 g sample containing copper is analyzed iodometrically.
Copper(II) is reduced to copper(I) by iodide:
What is the percent copper in the sample if 20.00 mL of 0.100 M Na2S2O3
is required for the titration of liberated I2 (FW of Cu = 63.54). Answer =
63.5%
44
Analysis of Hydrogen Peroxide by Iodometry
Solutions of hydrogen peroxide are widely sold as disinfectants. Since
hydrogen peroxide is an oxidizing agent, it will react with iodide in a redox
reaction:
The reaction is not instantaneous, but it is fast enough to form the basis
of a practical analysis by iodometric titration. The sample is added to an
acidic solution containing an unmeasured excess of iodide. After the
reaction is complete, the iodine produced by the above reaction is
titrated with sodium thiosulfate.
45
Determination of hexacyanoferrate(III)
When iodide is added to a solution of hexacyanoferrate(III), the
following equilibrium exists:
2[Fe(CN)6]3− + 2I− ⇌ 2[Fe(CN)6]4− + I2
Under a strongly acidic solution, the above equilibrium lies far to the
right-hand side but is reversed in an almost neutral solution. This makes
analysis of hexacyanoferrate (III) troublesome as the iodide and
thiosulfate decompose in a strongly acidic medium. To drive the
reaction to completion, an excess amount of zinc salt can be added to
the reaction mixture containing potassium ions, which precipitates the
hexacyanoferrate(II) ion quantitatively:
2[Fe(CN)6]3− + 2I− + 2K+ + 2Zn2+ → 2 KZn[Fe(CN)6] + I2
The precipitation occurs in a slightly acidic medium, thus avoiding the
problem of decomposition of iodide and thiosulfate in a strongly acidic
medium, and the hexacyanoferrate(III) can be determined by iodometry
as usual. 46
Iodometry Iodimetry
In Iodometric titrations, the Iodine In Iodimetry titrations, an Iodine
produced as a result of a previous solution is directly titrated with a
redox reaction is titrated with a reducing solution.
reducing agent such as thiosulfate
ions.
An Iodometric titration is an indirect Iodimetry is a direct analysis
method of analysis. method.
In Iodometry, two redox reactions In Iodimetry, only one redox
occur. reaction process takes place.
In Iodometry, Iodine is produced first In Iodimetry, Iodine only gets
by an oxidation reaction and then reduced.
reduced by a reducing agent.
Iodometry is more commonly seen Iodimetry is less common when
in experiments. compared to Iodometry.
47