REDOX TITTRATIONS

Analytical Chemistry Laboratory 2012

FUNDAMENTAL TERMS

Reactive species in this reaction type is the electron, which is transferred from the reductant to the oxidant Most elements are capable of exhibiting more than one oxidation state It is customary to describe redox reaction in electrochemical terms because transfer electron may also be carried out in an electrochemical cell

Redox Reactions
Oxidation process : loss of electron Reduction process : gain of electron Reducing agent is oxidized Oxidizing agent is reduced

NERSNT EQUATION

To relate electrochemical potentials to activities (concentration) of species in the system, we can draw on the thermodynamics relationship involving free energy change and activities, namely : G = G0 + RT ln Q G = -nFE - nFE = -nFE0 + RT ln Q E = E0 - RT/nF ln Q E = E0 - 0,05916/n log Q

 E0 = electrochemical potential for the reaction when all species are in their standard state Its describe the tendency of the ion to reductizes

REDOX TITRATION CURVEs

To evaluate a redox titration we must know the shape of its titration curve For redox titration, it is convenient to monitor electrochemical potential coz we are dealing with electron Nernst equation relates the electrochemical potential to the concentrations of reactants and products participating in a redox reaction

 Consider, for example a titration in which the analyte in a reduced state, Ared is titrated with a titrant in an oxidized state Tox. The titration reaction is : A red + T ox T red + Aox the electrochemical potential for the reaction is the difference between the reduction potentials for the reduction and oxidation half reaction; thus Erxn = ETox/Tred EAox/Ared

 Before the equivalence point the titration mixture consists of appreciable quantities of both the oxidized and reduced forms of the analyte, but very little unreacted titrant. The potential, therefore, is best calculated using the nernst equation for the analytes half reaction EAox/Ared = E0Aox/Ared RT/nF ln [Ared]/[Aox]

 After each addition of titrant, the reaction between the analyte and titrant reaches a state of equilibrium. The reactions electrochemical potential, Erxn, therefore is zero, and E Tox/Tred = E Aox/Ared

 After the equivalence point, the potential is easiest quast to calculate using the Nernst equation for the titrants half reaction, since significant quantities of its oxidized and reduced forms are present
ETox/Tred = E0Tox/Tred RT/nF ln [Tred]/[Tox]

Example
Calculate the titration curve for the titration of 50 mL of 0,1 M Fe2+ with 0,1 M Ce4+ in a matrix of 1M HClO4. (after 5 mL, 50 mL and 60 mL titrant added) the reaction is
Fe 2+ + Ce 4+ Fe 3+ + Ce 3+

assume analyte and titrant react completely

Answer
We calculate volume we need to reach the equivalent point. From the stoichiometry we know that :

So volume Ce4+ needed were :

Before equivalent point : Easier for us to measure the potential from analyte half potential reaction

Substituting these concentration into potential halfs reaction, gives us :

Equivalent Point :

Mol of [Fe2+] and [Ce4+] equal but so small, so we cant calculate the potential from reactant or titrant halfs reaction only. We have to combine the two Nernst Equation.

Adding together this two Nernst equation, give us :

At the equivalent point , the titration reaction stoichiometry requires that

So the ratio of concentration become one and the log become zero, the potential then:

After adding 60 mL titrant : (the condition are after equivalent point), we can calculate the potential from potential of titrant halfs reaction

Substituting these concentration gives us :

Evaluating the end point

Finding the end point with visual indicator

Redox indicator : substances that do not participate in the redox titration, but whose oxidized and reduced forms differ in color When added to a solution containing analyte, the indicator imparts a color that depends on the solutions electrochemical potential Since the indicator changes color in response to the elctrochemical potential, and not to the presence or absence of a specific species, these compounds are called general redox indicator Specific redox indicator : react with the presence of a specific species

Types of indicators used to signal end point : MnO4when MnO4- is used as an oxidizing titrant, the solution remains colorless until the first drop of excess MnO4- is added. The first tinge purple signals the end point Starch (Specific Indicator) forms a dark blue complex with I2 and can be used to signals the presence of excess I2 (color change : colorless to blue), or the completion of a reaction in which I2 is consumed (color change : blue to colorless) Thiocyanate (specific indicator) forms a soluble red-colored complex Fe(SCN)2+, with Fe3+

REDOX TITRATION METHODS

Titration Involving Iodine : Iodometry and Iodimetry

Titration With Oxidizing Agent : Permanganometry,

Cerimetry, potassium dichromate

Iodimetry
Titration with I2 solution

Titration performed in neutral or mildy alkaline (pH 8) to

a weakly acid solution Reason avoiding the pH too acid : starch as indicator

tends to hydrolyze in strong acid, reducing power of

some reducing agent decreases in acid solution, iodide

produced in the reaction tends to be oxidized by dissolved

oxygen in acid solution Indicator : Starch

Iodometry
Add excess of Iodide (I-) to a solution of an oxidizing agent, I2 produced in an equivalent amount to the oxidizing agent I2 present can be titrated with reducing agent such as sodium thiosulfate I2 + 2S2O32- 2I- + S4O62End point titration detected with starch (by disappearance of the blue

starch-I2 color)
Most titration performed in acid solution

Example : assay of potassium dichromate

Structure of the repeating unit of the sugar amylose. Schematic structure of the starchiodine complex. The amylose chain forms a helix around I6 unit.

View down the starch helix, showing iodine, inside the helix

Permanganometry
Use potassium permanganate as oxidizing titrant Acts as self indicator for end point detection

Oxidation with Ce4+

Ce4+ + e = Ce3+
yellow colorless 1.7V in 1 N HClO4 1.61V in 1N HNO3 1.47V in 1N HCl 1.44V in 1M H2SO4 Indicator : ferroin, diphenylamine

Preparation and standardization:

Ammonium hexanitratocerate, (NH4)2Ce(NO3)6, (primary standard grade)
Ce(HSO4)4, (NH4)4Ce(SO4)42H2O

Standardized with Sodium oxalate.

Applications of cerimetry

(1) Menadione (2-methylnaphthoquinon: vitamin K3)

O
CH3

HCl, Zn
Reduction

OH
CH3

2 Ce(SO4)2

OH

(2) Iron
2FeSO4 + 2 (NH4)4Ce(SO4)4 = Fe2(SO4)3 + Ce2(SO4)3 + 4 (NH4)2SO4

Oxidation with potassium dichromate

Cr2O72 + 14H+ + 6e = 2Cr3+ + 7H2O Eo = 1.36 V

K2Cr2O7 is a primary standard.

Indicator : diphenylamine sulphonic acid

End point colour : violet

Ex. Redox titration ( hydroquinone vs dichromate standard

solution ) Cr2O72 + 14H+ + 6e Eo= 1.33 3 2 Cr3+ + 7 H2O

HO

OH

+ 2H+ + 2e

Eo= 0.700

3 HO

OH + Cr2O72 + 8H+ O

O + 2 Cr3+ + 7 H2O

Eo= Eocathode Eoanode = 1.33 0.700 0.63 V

K = 10 nEo/0.05916 = 10 6(0.63) / 0.05916 = 10 64 redox indicator : diphenylamine

Very large : quantitative : complete reaction

colorless to violet

Example
A solution of sodium thiosulfate was standardized by dissolving 0,1210 g of

KIO3 (mw 214 g/mol) in water, adding a large excess of KI, and acidifying with
HCl. The liberated iodine required 41,64 mL of the thiosulfate solution to

decolorize the blue starch/iodine complex. Calculate the molarity of the

Na2S2O3.

Reaction : IO3- + 5I- + 6H+ I2 + 2S2O3 2-

3 I2 + 3H2O
2I- + S4O6 2-

Solution :
1 mol IO3 equivalent to 3 mol I2 equivalent to 6 mol S2O3 2-

Amount of S2O3 2- = [(0,1210 x 1000) / 214 ] x 6 = 3,392 mmol Molarity of S2O3 2- = 3,392 : 41,64 mL = 0,0842 M

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 1:1:3 The reaction with water involves the following reactions :

C5H5NI2 + C5H5NSO2 + C5H5N + H2O 2 C5H5NHI + C5H5NSO3

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 desiccantprotected 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
(2) Buffering

2ROH + SO2 RSO3 BI2

+ ROH2+ BH+SO4R + 2 BH+I

B + RSO3 + ROH2+ BH+SO3R + ROH

(3) Redox

+ BH+SO3R + B + H2O

HOME WORK
Derive a curve for the titration of 50 mL of 0,025 M U 4+ with 0,1 M Ce 4+ after adding 5 mL , 25mL, and 30 mL of Ce 4+ . Assume that the solution Is 1.0 < in H2SO4 throughout the titration ([H+] for such a solution will be about 1.0 M) The analytical reaction is : U 4+ + 2H2O + 2 Ce 4+

UO22+ + 2 Ce 3+ + 4H+

From the handbook : Ce 4+ + e UO 2 2+ + 4H+ + 2e

Ce 3+ U 4+ + 2H2O

Eo = +1.44 V Eo = +0,334 V