Redox Titration

Redox Titration
Pharmaceutical Analysis
-:Prepared By:-
Dr. Nilesh K. Patel
Assistant Professor
B. K. Mody Government Pharmacy College,
Rajkot (212)
Introduction to Redox Titration
• In 1787, Claude Berthollet introduced a method for the quantitative analysis of chlorine water (a mixture of Cl, HCl, and
HOCl) based on its ability to oxidize solutions of the dye indigo (indigo is colorless in its oxidized state).
• In 1814, Joseph Louis GayLussac (1778–1850), developed a similar method for chlorine in bleaching powder.
• The number of redox titrimetric methods increased in the mid-1800s with the introduction of MnO4– , Cr2O72– and I2 as
oxidizing titrants, and Fe as reducing titrants.
• Oxidation-reduction reactions involve a transfer of electrons. The oxidising agent accepts electrons and the reducing agent
gives electrons. In working out the equation for a redox reaction we can use the half-equation method.
• In this method we use the half-equation for the oxidising agent and the half-equation for the reducing agent then add them
together.
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Mr. Nilesh Patel, Assistant Professor, BKMGPC, Rajkot , Email Id:-nkpatel_99@yahoo.com
Examples of half-reaction equations
Iron(III) salts are reduced to iron(II) salts.

The half equation is
Fe3+  Fe2+
For the equation to balance the charge on the RHS must equal the charge on the LHS. This can be accomplished by
inserting an electron on the LHS
Fe3+ + e-  Fe2+
When chlorine acts as an oxidizing agent it is reduced to Cl- ions
Cl2  2Cl-
To obtain a balanced equation 2 electrons must be inserted on the LHS
Cl2 + 2e-  2Cl-
Potassium magnate (VII) is an oxidizing agent. In acid solutions it is reduced to a manganese(II) salt
MnO4- + 8H+ + 5e-  Mn2+ + 4H2O
Potassium dichromate(VI) is also an oxidizing agent. It is reduced to a chromium(III) salt
Cr2O7- + 14H+ + 6e-  2Cr3+ + 7H2O

Using half equations to obtain the equation for the reaction
Find the equation for the reaction of iron(III) with chloride ions
The 2 half reactions needed are

1 Fe3+ + e-  Fe2+
2 Cl2 + 2e-  2Cl-
We need iron(III) and chloride as reactants so equation 2 must be reversed
3 2Cl-  Cl2 + 2e-
Now we must balance the electrons, then add the half equations together to obtain the full equation. To balance the
electrons we multiply equation 1 by 2
1 Fe3+ + e-  Fe2+ x2
2 2Fe3+ + 2e-  2Fe2+

3 2Cl-  Cl2 + 2e-
2Fe3+ + 2Cl-  2Fe2+ + Cl2
There must be the same no of electrons on each side which then cancel.
Construct an equation for the reaction of potassium manganate(VII) with ethanedioate ion
Ethanedioate ion is C2O42- and the half equation is
C2O42-  2CO2 + 2e-
2MnO4- + 16H+ + 5C2O42-  2Mn2+ + 8H2O + 10CO2

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Reagents used in redox titration
Reducing agents
Ferrous salts :
• ammonium iron(II) sulfate hexahydrate (Mohr’s salt) FeSO4(NH4)2SO4· 6H2O
• iron(II) ethylene diamine sulfate (Oesper’s salt) FeC2H4(NH3)2(SO4)2· 4H2O
• Sodium thiosulfate pentahydrate Na2S2O3·5H2O
• Arsenic trioxide: arsenious oxide As2O3
• Sodium oxalate and oxalic acid dihydarte Na2(COO)2 , (COOH)2·2H2O
• Titanium trichloride TiCl3
• Potassium ferrocyanide K4Fe(CN)6 · 3H2O
Arsenious oxide, As4O6

As4O6 + 6H2O = 4H3AsO3
H3AsO3 + I3– + H2O = H3AsO4 + 3I– + 2H+
The As4O6 molecule consists of an As4 tetrahedron with a bridging

oxygen atom on each edge

Sodium thiosulfate, Na2S2O3
Thiosulfate ion is a moderately strong reducing agent that has been widely used to determine oxidizing agents by an
indirect procedure that involves iodine as an intermediate. With iodine, thiosulfate ion is oxidized quantitatively to
tetrathionate ion according to the half-reaction:
2S2O3 2–  S4O6 2– + 2e Eo = 0.08
Ex. Determination of hypochlorite in bleaches [CaCl(OCl)H2O]:

OCl– + 2I– + 2H+  Cl– + I2 + H2O (unmeasured excess KI)
I2 + 2 S2O3 2–  2I– + S4O6 2–
Indicator: soluble starch (-amylose)
Standardization of thiosulfate solution:
Primary standard : potassium iodate (KIO3), K2Cr2O7, KBrO3
Titration reactions:
KIO3 + 5KI + 6HCl  3I2 + 6KCl + 3 H2O
I2 + 2Na2S2O3  2NaI + Na2S4O6
KIO3  3I2  6Na2S2O3·5H2O  6 Equivalent
Stabilizer for sodium thiosulfate solution : Na2CO3
Na2S2O3 + H2O + CO2  Na2CO3 + H2S2O3
H2S2O3  H2SO3 + S

Schematic structure of the starch-iodine complex. The
amylose chain forms a helix around I6 unit.
Structure of the repeating unit of the sugar amylose.
• Starch is the indicator of choice for those procedures involving iodine because it
forms an intense blue complex with iodine. Starch is not a redox indicator; it
responds specifically to the presence of I2, not to a change in redox potential.
• The active fraction of starch is amylose, a polymer of the sugar α-d-glucose.
• In the presence of starch, iodine forms I6 chains inside the amylose helix and the View down the starch helix, showing iodine, inside
color turns dark blue
the helix

Oxidizing agents
• Potassium permanganate KMnO4 : Permanganometry
• Ceric sulfate / Ceric ammonium sulfate Ce(SO4)2·2(NH4)2SO4· 4H2O : Cerimetry
• Potassium dichromate K2Cr2O7 : Dichrometry
• Iodine I2 : Iodimetry, Iodometry
• Potassium iodate KIO3 : Iodatimetry
• Potassium bromate KBrO3 : Bromatimetry
• Sodium nitrite NaNO2 :
• Calcium hypochlorite Ca(ClO)2 :

Permanganate titration
Oxidation with permanganate : Reduction of permanaganate
KMnO4 Powerful oxidant that the most widely used.

In strongly acidic solutions (1M H2SO4 or HCl, pH  1)
MnO4– + 8H+ + 5e = Mn2 + + 4H2 O Eo = 1.51 V
violet color colorless manganous
KMnO4 is a self-indicator.
In feebly acidic, neutral, or alkaline solutions
MnO4– + 4H+ + 3e = MnO2 (s) + 2H2 O Eo = 1.695 V
brown manganese dioxide solid
In very strongly alkaline solution (2M NaOH)
MnO4– + e = MnO42 – Eo = 0.558 V
green manganate
Standardization of KMnO4 solution
Potassium permanganate is not primary standard, because traces of MnO 2 are invariably present.
Standardization by titration of sodium oxalate (primary standard) :
2KMnO4 + 5 Na2(COO)2 + 8H2SO4 = 2MnSO4 + K2SO4 + 5Na2SO4 + 10 CO2 + 8H2O
2KMnO4  5 Na2(COO)2  10 Equivalent

mw 158.03 mw 134.01
158.03 g / 5  134.01 g / 2  1 Eq.
31.606 g  67.005 g
1N × 1000 ml  67.005 g
x N × V ml ag
x N = ( a g × 1N × 1000 ml) / (67.005 g × V ml)
Preparation of 0.1 N potassium permanganate solution
KMnO4 is not pure. Distilled water contains traces of organic reducing substances which react slowly with
permanganate to form hydrous managnese dioxide. Manganesse dioxide promotes the autodecomposition of
permanganate.
1) Dissolve about 3.2 g of KMnO4 (mw=158.04) in 1000ml of water, Heat the solution to boiling, and keep slightly below
the boiling point for 1 hr. Alternatively , allow the solution to stand at room temperature for 2 or 3 days. Filter the liquid
through a sintered-glass filter crucible to remove solid MnO2. Transfer the filtrate to a clean stoppered bottle freed
from grease with cleaning mixture. Protect the solution from evaporation, dust, and reducing vapors, and keep it in
the dark or in diffuse light. If in time managanese dioxide settles out, refilter the solution and restandardize it.
Applications of permanganometry
(1) H2O2
2KMnO4 + 5 H2O2 + 3H2SO4 = 2MnSO4 + K2SO4 + 5O2 + 8H2O
(2) NaNO2
2NaNO2 + H2SO4 = Na2SO4 + HNO2
2KMnO4 + 5 HNO2 + 3H2SO4 = 2MnSO4 + K2SO4 + 5HNO3 + 3H2O
(3) FeSO4
2KMnO4 + 510 FeSO4 + 8H2SO4 = 2MnSO4 + K2SO4 + 5Fe2(SO4)3 + 8H2O
(4) CaO
CaO + 2HCl = CaCl2 + H2O CaCl2 + H2C2O4 = CaC2O4 + 2HCl (excess oxalic acid)
2KMnO4 + 5 H2C2O4 + 3H2SO4 = 2MnSO4 + K2SO4 + 10CO2 + 8H2O (back tit)
(5) Calcium gluconate
[CH2OH(CHOH)4COO]2Ca + 2HCl = CaCl + 2CH2OH9CHOH)4COOH
(NH4)2C2O4 + CaCl2 = CaC2O4 + 2 NH4Cl CaCl2 + H2SO4 = H2C2O4 + CaSO4
2KMnO4 + 5 H2C2O4 + 3H2SO4 = 2MnSO4 + K2SO4 + 10CO2 + 8H2O

redox indicators
• Titrants whose oxidized and reduced forms differ significantly in color could be used as their own indicator.
• A redox indicator (also called an oxidation-reduction indicator) is an indicator that undergoes a definite color change at a
specific electrode potential.
• The requirement for fast and reversible color change means that the oxidation-reduction equilibrium for an indicator redox
system needs to be established very fast. Therefore only a few classes of organic redox systems can be used for indicator
purposes.
• There are two common type of redox indicators:
– metal-organic complexes (Ex. phenanthroline)
– true organic redox systems (Ex. Methylene blue)
• Sometimes colored inorganic oxidants or reductants (Ex. Potassium manganate, Potassium dichromate) are also
incorrectly called redox indicators. They can’t be classified as true redox indicators because of their irreversibility.
• Almost all redox indicators with true organic redox systems involve a proton as a participant in their electrochemical
reaction. Therefore sometimes redox indicators are also divided into two general groups: independent or dependent on
pH.
Type of Redox Indicators

• Self Indicators Many a times the titrant itself may be so strongly colored that after the equivalence point, a single drop of
the titrant produces an intense color in the reaction mixture. e.g. potassium permanganate. Such Indicators are called
self indicators. Self indicators generally are strongly colored as a result of charge transfer transitions in them.
• Internal indicator Such indicators are added into the reaction mixtures Such indicators always have reduction potential
values lower than the analyte system so that they react with the titrant only when whole of the analyte has been
consumed, producing a readily detectable color change.
• External indicator In case a suitable redox indicator is not available for a given system, an indicator may be employed
which will indicate the completion of reaction by physically or chemically reacting with the analyte (not through redox
reaction). This reaction between indicator and the analyte may sometimes be an irreversible one and in some cases may
even lead to precipitation. In those case indicators are not added to the reaction mixture on the whole, rather used
externally on a grooved tile. Such indicators are called external indicators.
• Potentiometric Methods The most accurate method to judge the completion of redox titration is however potentiometric
method which deals with the measurement of e.m.f. between a reference electrode and the indicator (redox) electrode
during the stages of redox titration. This method in fact tells us the equivalence point of the reaction and not the end point
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pH independent Redox indicators
Indicator E0, V Color of Oxidized form Color of Reduced form
2,2'-Bipyridine (Ru complex) +1.33 V colorless yellow

N-Phenylanthranilic acid +1.08 V violet-red colorless
2,2`-Bipyridine (Fe complex) +0.97 V cyan red
5,6-Dimethylphenanthroline (Fe complex) +0.97 V yellow-green red
Sodium diphenylamine sulfonate +0.84 V red-violet colorless
Diphenylbenzidine +0.76 V violet colorless
Diphenylamine +0.76 V violet colorless
pH dependent redox indicators
E0, V E0, V Color of Color of

Indicator
at pH=0 at pH=7 Oxidized form Reduced form
Sodium 2,6-Dibromophenol-indophenol
+0.64 V +0.22 V blue colorless
or Sodium 2,6-Dichlorophenol-indophenol
Sodium o-Cresol indophenol +0.62 V +0.19 V blue colorless
Thionine (syn. Lauth's violet) +0.56 V +0.06 V violet colorless
Methylene blue +0.53 V +0.01 V blue colorless
Indigotetrasulfonic acid +0.37 V -0.05 V blue colorless
Indigotrisulfonic acid +0.33 V -0.08 V blue colorless
Indigomono sulfonic acid +0.26 V -0.16 V blue colorless
Phenosafranin +0.28 V -0.25 V red colorless
Safranin T +0.24 V -0.29 V red-violet colorless
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Types of Redox Titrations
Methods Involving Iodine
• Iodimetry: a reducing analyte is titrated directly with iodine (to produce I−).
• iodometry, an oxidizing analyte is added to excess I− to produce iodine, which is then titrated with standard
thiosulfate solution.
• Iodine only dissolves slightly in water. Its solubility is enhanced by interacting with I-
Quantitative Classical
Chemical Analysis
Gravimetr
y Titrations
Acid-base Precipitation Complexometric Redox
Titrations involving
Dichromatometric
iodine (I2)
Iodimetry
Permanganimetric
Iodometry
Iodometric titration of
copper 15
When a reducing analyte is titrated with iodine (the titrant), the method is called iodimetry.
Iodimetry: A direct titration with only 1 reaction:
analyte + titrant (iodine I2) → product (iodide I-)

unknown known
When a reducing analyte is titrated with iodine (the titrant), the method is called iodimetry.
Example: Quantification of Ascorbic Acid (Vitamin C)
C6H8O6 + I2 → CçH6O6 + 2I- + 2H+
Iodine rapidly oxidizes ascorbic acid, C6H8O6 , to produce

dehydroascorbic acid, C6H6O6 .
Ascorbic acid Dehydroascorbic acid
Iodimetric titrations:
a) A reducing analyte
b) One reaction
c) Standard solution: Iodine (I2)

Iodometry is the titration of iodine (I2) produced when an oxidizing analyte is added to excess I -(iodide).
Then the iodine (I2) is usually titrated with standard thiosulfate solution.
Iodometry: Not a direct titration because there are 2 reactions:
analyte + I- → I2
unknown
I2 + titrant (standard thiosulfate) → product

Known
Iodometric titrations:
a) An oxidizing analyte
b) Two reactions
Example: Quantification of Copper
c) Standard solution: Sodium thisoufate
2 Cu 2+ + 4I- → 2CuI + I2
Analyte of unknown concentration
I2 + 2S2O32- → 2I- + S4O62-
Titrant
-standrard solutions: sodium thiosulfate
-known concentration
Preparation and Standardization of Solutions
• Acidic solutions of I3- are unstable because the excess I− is slowly oxidized by air:
• In neutral solutions, oxidation is insignificant in the absence of heat, light, and metal ions. At pH ≳ 11, triiodide
disproportionates to hypoiodous acid (HOI), iodate, and iodide.
• An excellent way to prepare standard I3- is to add a weighed quantity of potassium iodate to a small excess of KI.
Then add excess strong acid (giving pH ≈ 1) to produce I2 by quantitative reverse disproportionation:

Determining water with the Karl Fisher Reagent
The Karl Fisher reaction :

I2 + SO2 + 2H2O  2HI + H2SO4
For the determination of small amount of water, Karl Fischer(1935) proposed a reagent prepared as an anhydrous
methanolic solution containing iodine, sulfur dioxide and anhydrous pyridine in the mole ratio 1:3:10. The reaction with
water involves the following reactions :
C5H5N•I2 + C5H5N•SO2 + C5H5N + H2O  2 C5H5N•HI + C5H5N•SO3
C5H5N+•SO3– + CH3OH  C5H5N(H)SO4CH3
Pyridinium sulfite can also consume water.
C5H5N+•SO3– + H2O  C5H5NH+SO4H–
It is always advisable to use fresh reagent because of the presence of various side reactions involving iodine. The
reagent is stored in a desiccant-protected container.
The end point can be detected either by visual( at the end point, the color changes from dark brown to yellow) or
electrometric, or photometric (absorbance at 700nm) titration methods. The detection of water by the coulometric
technique with Karl Fischer reagent is popular.
Pyridine free Karl Fisher reagent

In recent years, pyridine, and its objectionable odor, have been replaced in the Karl Fisher reagent by other amines, particularly
imidazole.
(1) Solvolysis 2ROH + SO2  RSO3– + ROH2+
(2) Buffering B + RSO3– + ROH2+  BH+SO3R– + ROH
(3) Redox B•I2 + BH+SO3R– + B + H2O  BH+SO4R– + 2 BH+I–

cerrimetry
• Cerimetry or cerimetric titration, also known as cerate oximetry, is a method of volumetric chemical analysis, a redox
titration in which a Fe2+-1,10-phenanthroline complex (ferroin) color change indicates the end point. Ferroin can be
reversibly discolored in its oxidized form upon titration with a Ce4+ solution. The use of cerium(IV) salts as reagents
for volumetric analysis was first proposed in the middle of 19th century, but systematic studies did not start until about
70 years later. Standard solutions can be prepared from different Ce4+ salts, but often cerium sulfate is chosen.
• Since Cerimetry is linked to the Fe3+/Fe2+ redox pair, it can be used for analyses of nonstoichiometric levels that
either oxidize Fe2+ or reduce Fe3+. For the case of oxidation, a precise excess of high-purity crystalline Mohr’s salt is
added upon the oxide digestion in aqueous hydrogen chloride (HCl), while for the case of reduction, an excess of 1 M
iron trichloride (FeCl3) is added. In the both cases, this is Fe2+ ions which will be titrated subsequently. Because the
Ce4+ solution is prone to hydrolysis, the titration is done in a strongly HCl-acidic solution into which some phosphoric
acid (H3PO4) is added to obtain a less colored phosphate complex of Fe3+.
• According to tabulated values of standard potentials at pH = 0 for the first-row transition metals, any nonstoichiometry
below the following oxidation states will reduce 1 M FeCl3 solution whereas any nonstoichiometry above them will
oxidize the Mohr’s salt: Ti4+, V4+, Cr3+, Mn2+, Co2+, and Ni2+. In addition, any nonstoichiometry in the Fe(III)–Fe(II)
range is titrated directly with no additives, any nonstoichiometry below Fe2+ will reduce 1 M FeCl3 whereas any
nonstoichiometry above Fe3+ will oxidize Mohr’s salt. In the second- and third-row transition metals, only the early
elements would be suitable for the titration, and the limiting oxidation states are Zr4+, Nb5+, Mo4+, Hf4+, Ta5+, and
W6+. Standard potentials involving rhenium ions are too close to E° for Fe3+/Fe2+ as well as to each other.
Nonstoichiometry of oxides containing several elements in oxidation states suitable for cerimetry is determined in one
titration.
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Oxidation with Ce4+
Ce4+ + e = Ce3+ 1.7V in 1 N HClO4
yellow colorless 1.61V in 1N HNO 3
1.47V in 1N HCl
1.44V in 1M HSO4
Indicator : ferroin, diphenylamine
Preparation and standardization:
Ammonium hexanitratocerate, (NH4)2Ce(NO3)6, (primary standard grade)
Ce(HSO4)4, (NH4)4Ce(SO4)4·2H2O
Standardized with Sodium oxalate.
Applications of cerimetry
(1) Menadione (2-methylnaphthoquinon: vitamin K3)
(2) Iron
2FeSO4 + 2 (NH4)4Ce(SO4)4 = Fe2(SO4)3 + Ce2(SO4)3 + 4 (NH4)2SO4

Mercurymetry
• The mercuric nitrate test is a quantitative method used to determine Cl- or NaCl in parts per million in an aqueous solution.
It is a quick and simple test to perform and gives accurate and consistent results.
• Chemicals:
1. Diphenylcarbazone-bromophenol blue indicator
2. 0.02N mercuric nitrate solution.
3. Sulfuric acid
• formulas:
T x N x 0.03545 x 1,000,000
20
= T x N x 1772.5 = ppm Cl-
T x N x 0.05846 x 1,000,000
20
= T x N x 2923 = ppm NaCl
where
T = amount of mercuric nitrate titrated
N = normality of mercuric nitrate
• Throughout this entire process, the glassware must be kept clean and uncontaminated. To prevent cross contamination, a
clean beaker and stirring rod should be used for each electrolyte sample, or these items should be washed thoroughly and
rinsed with de-ionized water between each sample. Purple mercuric nitrate stains can be removed from the stirring rods by
immersing them in dilute solution of nitric acid.
• The diphenylcarbazone-bromophenol end point is to some degree subjective, but most individuals are consistent about their
end point. Therefore, the most reliable and consistent results are obtained when only one individual is responsible for
monitoring the electrolyte.
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Diazotization nitrite titrations
• Diazotization is used in the analysis of aromatic compounds containing an amino group in the molecules. This analysis is
based on the reaction between aromatic primary amine (–NH2), HONO, in presence of excess mineral or inorganic acids.
• NaNO2 is generally used in direct method of diazotization. It gives HNO2 in acidic solution. Many aromatic primary amine
with free –NH2 group can be analyzed quantitatively by measuring the volume of NaNO2 solution required to convert them
into diazonium salts. The typical reaction of diazotization reaction in presence of HCl is given as
• When all the aromatic amine has reacted with NaNO2 then next portion (excess) of NaNO2 added to the solution under test,
converted to HONO that remain in the solution and 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.
• Starch iodide paper or paste is the starch solution plus equal volume of 5% KI solution in H 2O. 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. It is important to check the acidity at the end of the titration. If there is no excess of acid present, starch –iodide paper
will not detect excess HNO2 and so will not indicate the end point.
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• Condition for diazotization
(1) Rate of titration
(2) Temperature of the solution
• Application of diazotization titration: An important pharmaceutical application of sodium nitrite titration is the analysis of
sulphonamides by diazotization of primary aromatic amino group usually present in this class of drugs. Several
sulphonamides require the formation of primary amine prior to diazotization step.
• Example – phthalylsulphathiazole and succinyl sulphathiazole are first hydrolyzed to give primary aromatic amine and
determined by NaNO2 titration method.
• List of compounds assayed by sodium nitrite titration:
(1) Dapsone
(2) Benzocaine
(3) Procaine hydrochloride
(4) Calcium amino salicylate
(5) Sodium amino salicylate
(6) Sulphacetamide tablet
(7) Sulphadoxine
(8) All sulpha drugs
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2,6-dichlorophenol indophenol titrations
• 2,6-dichlorophenolindophenol, ( DCPIP ) is a blue chemical compound used as a redox dye. Oxidized DCPIP is blue, reduced
DCPIP is colorless.
• The rate of photosynthesis can be measured by the rate at which this dye changes color (is reduced) when exposed to light in a
photosynthetic system. This reaction is reversible, as colorless DCPIP can be reoxidized to blue. It is often used in measurements
of the electron transport chain in plants because of its higher affinity for electrons than ferredoxin. For example, it is possible to
compare rates of photosynthesis with DCPIP. Due to the reductions that occur during the light reactions, DCPIP can be
substituted for NADPH, the final electron carrier in the light reactions. The light reactions will reduce the DCPIP and turn it
colorless. As DCPIP is reduced and becomes colorless, the following increase in light transmittance can be measured by a
spectrophotometer.
• DCPIP is a redox dye commonly used as a monitor of the light reactions in photosynthesis because it is an electron acceptor that
is blue when oxidized and colorless when reduced. It is part of the Hill reagents family. DCPIP is commonly used as a substitute
for NADP+. The dye changes color when it is reduced, due to its chemical structure. The rate of photosynthesis light-dependent
reaction can be measured with this property of DCPIP, because one of the stages of the light reaction is an electron transport
chain that normally ends with the reduction of NADP+. When DCPIP is present, it also gets reduced by the light reaction. The
amount of DCPIP reduced can be found by measuring the solution's light transmittance with a spectrophotometer.
• DCPIP can also be used as an indicator for Vitamin C. If vitamin C, which is a good reducing agent, is present, the blue dye,
which turns pink in acid conditions, is reduced to a colorless compound by ascorbic acid.
• DCPIP (blue) + H+ ——→ DCPIPH (pink) DCPIPH (pink) + VitC ——→ DCPIPH2 (colorless) C6H8O6 + C12H7NCl2O2 ——→
C6H6O6 + C12H9NCl2O2 In a titration, when all the ascorbic acid in the solution has been used up, there will not be any
electrons available to reduce the DCPIPH and the solution will remain pink due to the DCPIPH. The end point is a pink color that
persists for 10 seconds or more. Pharmacological experiments suggest that DCPIP may serve as a pro-oxidant chemotherapeutic
targeting human cancer cells in an animal model of human melanoma; DCPIP-induced cancer cell death occurs by depletion of
intracellular glutathione and upregulation of oxidative stress
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Titration curve
The shape of a redox titration curve
• A redox titration is based on an oxidation-reduction reaction between analyte and titrant.

• Consider the titration of iron(II) with standard cerium(IV), monitored potentiometrically with Pt and calomel
electrodes.
The potentials show above is in 1 M HClO4 solution.
• There are three distinct regions in the

titration of iron(II) with standard
cerium(IV), monitored potentiometrically
with Pt and calomel electrodes.
1. Before the equivalence point, where the

potential at Pt is dominated by the
analyte redox pair.
2. At the equivalence point, where the
potential at the indicator electrode is the
average of their conditional potential.
3. After the equivalence point, where the
potential was determined by the titratant
redox pair.

Before the equivalence point: using analyte’s concentration to calculate E+
At the equivalence point: needs both redox pairs to calculate (why?)

After the equivalence point:
There are two special points during the above titration process: (1) when V = ½ Ve, [Fe3+] = [Fe2+] and E+ = E°(Fe3+ | Fe2+) ; (2)
when V = 2 Ve, [Ce4+] = [Ce3+] and E+ = E°(Ce4+ | Ce3+) = 1.70 V.
Summary
• The greater the difference in reduction potential between analyze and titrant, the sharper will be the end point.
• The voltage at any point in this titration depends only on the ratio of reactants; it will be independent of dilution.
• Prior to the equivalence point, the half-reaction involving analyze is used to find the voltage because the
concentrations of both the oxidized and the reduced forms of analyte are known.
• After the equivalence point, the half-reaction involving titrant is employed. At the equivalence point, both half-
reactions are used simultaneously to find the voltage.
Finding the end point
• A redox indicator is a compound that

changes color when it goes from its oxidized
to its reduced state.
For ferroin, with E° = 1.147 V

we expect the color change to
occur in the approximate range
1.088 V to 1.206 V with respect SHE

A redox titration is feasible if the difference between analyte and titrant is > 0.2 V. If the difference in the
formal potential is > 0.4 V, then a redox indicator usually gives a satisfactory end point.

Adjustment of analyte oxidation state
• Sometimes one needs to adjust the oxidation state of analyte before it can be titrated.
• Pre-adjustment must be quantitative and one must eliminate excess pre-adjustment reagent so that it won’t
interference the subsequent titration.
• Pre-oxidation: powerful oxidants that can be easily removed after preoxidation include peroxydisulfate, silver(II)
oxide, sodium bismuthate.
Definition:
• Disproportionation: a reactant oxidizes and reduces itself, such as H2O2 in boiling water.
• Pre-reduction: Process of reducing an analyte to a lower oxidation state prior to performing a titration with an
oxidizing agent.
• Amalgam: a solution of anything in mercury.
Oxidation with potassium permanganate
• KMnO4 is a strong oxidant with an intense violet color. In strongly acidic solutions (pH < 1), it is reduced to Mn 2+.
• In neutral or alkaline solution, it is reduced to brown solid MnO2.
• In strongly alkaline solution ( 2 M NaOH), green manganate ion (MnO42-) is produced.

Now we can do a titration calculation using this equation!
A 25.0ml portion of sodium ethanedioate solution of concentration 0.200 mol/L is warmed and titrated against a solution
of potassium manganate(VII). If 17.2ml of potassium manganate(VII) is required what is its concentration?
No of moles ethanedioate in 25.0ml of solution of conc 0.200 mol/L =

0.200 x 25 = 0.005000 mols
1000
Ratio of ethanedioate to manganate(VII) = 2:5
 no of mols of manganate(VII) in 17.2ml =
0.005000 x 2 = 0.002000 mols

5
 conc of manganate(VII) = 0.002000 x 1000
17.2
= 0.116 mol/L

calculations of potentials
38
• References :
1. Modern analytical chemistry by D.Harvey
2. Practical Pharm. Chemistry, Vol. B – Backett, The athlone Press of University of London.
3..Fundamentals of Analytical Chemistry – Skoog, Harcourt College Publishers.
4. Quantitative chemical analysis – Vogel A.I, Pearson Education.
5. Text Book of Pharmaceutical Analysis – K. A. Connor, John Willey & Sons
39

Redox Titration

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Redox Titration

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Redox Titration

Iron(III) salts are reduced to iron(II) salts.

When chlorine acts as an oxidizing agent it is reduced to Cl- ions

To obtain a balanced equation 2 electrons must be inserted on the LHS

Cl2 + 2e-  2Cl-

MnO4- + 8H+ + 5e-  Mn2+ + 4H2O

Potassium dichromate(VI) is also an oxidizing agent. It is reduced to a chromium(III) salt

Cr2O7- + 14H+ + 6e-  2Cr3+ + 7H2O

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The 2 half reactions needed are

2 Cl2 + 2e-  2Cl-

We need iron(III) and chloride as reactants so equation 2 must be reversed

3 2Cl-  Cl2 + 2e-

2 2Fe3+ + 2e-  2Fe2+

Ethanedioate ion is C2O42- and the half equation is

C2O42-  2CO2 + 2e-

2MnO4- + 16H+ + 5C2O42-  2Mn2+ + 8H2O + 10CO2

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Arsenious oxide, As4O6

The As4O6 molecule consists of an As4 tetrahedron with a bridging

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Ex. Determination of hypochlorite in bleaches [CaCl(OCl)H2O]:

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Structure of the repeating unit of the sugar amylose.

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KMnO4 Powerful oxidant that the most widely used.

2KMnO4  5 Na2(COO)2  10 Equivalent

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Type of Redox Indicators

Indicator E0, V Color of Oxidized form Color of Reduced form

2,2'-Bipyridine (Ru complex) +1.33 V colorless yellow

pH dependent redox indicators

E0, V E0, V Color of Color of

Acid-base Precipitation Complexometric Redox

Iodimetry: A direct titration with only 1 reaction:

analyte + titrant (iodine I2) → product (iodide I-)

Example: Quantification of Ascorbic Acid (Vitamin C)

C6H8O6 + I2 → CçH6O6 + 2I- + 2H+

Iodine rapidly oxidizes ascorbic acid, C6H8O6 , to produce

Ascorbic acid Dehydroascorbic acid

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Iodometry: Not a direct titration because there are 2 reactions:

I2 + titrant (standard thiosulfate) → product

Analyte of unknown concentration

I2 + 2S2O32- → 2I- + S4O62-

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The Karl Fisher reaction :

Pyridine free Karl Fisher reagent

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• A redox titration is based on an oxidation-reduction reaction between analyte and titrant.

The potentials show above is in 1 M HClO4 solution.

• There are three distinct regions in the

1. Before the equivalence point, where the

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At the equivalence point: needs both redox pairs to calculate (why?)

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• A redox indicator is a compound that

For ferroin, with E° = 1.147 V

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Oxidation with potassium permanganate