preadjustment of analyte oxidation state it is necessary to adjust the oxidation state of the...

Preadjustment of analyte oxidation state

It is necessary to adjust the oxidation state of the analyte to one that can be titratedwith an auxiliary oxidizing or reducing agent.

Ex. Preadjustment by auxiliary reagent

Fe(II), Fe(III) Fe(II)4–

Titration

Ce4+

Preoxidation : Peroxydisulfate ( (NH4)2S2O8 )2– )

Sodium bismuthate ( NaBiO3)

Hydrogen peroxide (H2O2)

920310 1http:\\asadipour.kmu.ac.ir 33 slides

Prereduction : Stannous chloride ( SnCl2) Chromous chloride Jones reductor (zinc coated with zinc amalgam) Walden reductor ( solid Ag and 1M HCl)

Reagents used in redox titration

Reducing agents

1) ammonium iron(II) sulfate hexahydrate (Mohr’s salt) FeSO4(NH4)2SO4· 6H2O

2) iron(II) ethylene diamine sulfate (Oesper’s salt) FeC2H4(NH3)2(SO4)2· 4H2O

3) Sodium thiosulfate pentahydrate Na2S2O3·5H2O

4) Arsenic trioxide: arsenious oxide As2O3

5) Sodium oxalate and oxalic acid dihydarte Na2(COO)2 , (COOH)2·2H2O


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)920310 5http:\\asadipour.kmu.ac.ir 33

slides

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

S2O32- +H+ ⇋ HSO3- +S(s)pH, Microorganisms, Concentration, Cu2+, Sunlight

Stabilizer for sodium thiosulfate solution : Na2CO3

Na2S2O3 + H2O + CO2 Na2CO3 + H2S2O3

H2S2O3 H2SO3 + S920310 6http:\\asadipour.kmu.ac.ir 33

slides

16-2 Finding the end point

A redox indicator is a compound

that changes color

when it goes from its oxidized

to its reduced state.

or

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


Starch is the indicator of choice for those procedures involving iodine because it forms an intense blue colourwith iodine. Starch is not a redox indicator; it responds specifically to the presence of I2,

not to a change in redox potential.

Starch-Iodine Complex

Structure of the repeating unit of the sugar amylose.


Arsenious oxide, As4O6

As4O6 + 6H2O = 4H3AsO3

H3AsO3 + I3– + H2O = H3AsO4 + 3I– + 2H+


Reagents used in redox titration

Oxidizing agents

1) Potassium permanganate KMnO4 : Permanganometry

2) Ceric sulfate / Ceric ammonium sulfate Ce(SO4)2·2(NH4)2SO4· 4H2O : Cerimetry

3) Potassium dichromate K2Cr2O7 : Dichrometry

4) Iodine I2 : Iodimetry, Iodometry

5) Potassium iodate KIO3 : Iodatimetry

6) Potassium bromate KBrO3 : Bromatimetry


Permanganate titration

Oxidation with permanganate : Reduction of permanaganate

KMnO4 Powerful oxidant that the most widely used.

1) In strongly acidic solutions (1M H2SO4 or HCl, pH 1)

MnO4– + 8H+ + 5e = Mn2 + + 4H2 O Eo = 1.51 V

KMnO4 is a self-indicator.

2) In feebly acidic, neutral, or alkaline solutions

MnO4– + 4H+ + 3e = MnO2 (s) + 2H2 O Eo = 1.695 V

3) In very strongly alkaline solution (2M NaOH)

MnO4– + e = MnO4

2 – Eo = 0.558 V


Permanganate titration

Duration of colour in end point (30 seconds)

MnO4– + 3Mn2+ + 2H2O 5MnO2 + 4H+ K=1*1047

Stability of aqoues solution of MnO4-

MnO4– + 2H2O 4MnO2 (s) + 3O2 (g) +4OH-


Standardization of KMnO4 solution

Potassium permanganate is not primary standard, because traces of MnO2

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


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.

2) Filter the liquid through a sintered-glass filter crucible to remove solid MnO2.

3) Transfer the filtrate to a clean stoppered bottle freed from grease with cleaning mixture.

4) Protect the solution from evaporation, dust, and reducing vapors, and keep it in the dark or in diffuse light.

5) If in time managanese dioxide settles out, refilter the solution and restandardize it.

920310 17http:\\asadipour.kmu.ac.ir 33

slides

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 = CaCl2 + 2CH2OH9CHOH)4COOH

(NH4)2C2O4 + CaCl2 = CaC2O4 + 2 NH4Cl

CaCl2 + H2SO4 = H2C2O4 + CaSO4

2KMnO4 + 5 H2C2O4 + 3H2SO4 = 2MnSO4 + K2SO4 + 10CO2 + 8H2O


Oxidation with Ce4+

Ce4+ + e = Ce3+ 1.7 V in 1 N HClO4

yellow colorless 1.61 V in 1N HNO3

1.47 V in 1N HCl

1.44 V in 1M H2SO4

Indicator : ferroin, diphenylamine

Preparation and standardization:

Ammonium hexanitratocerate, (NH4)2Ce(NO3)6, (primary standard grade)

Sodium oxalate.


Applications of cerimetry

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

O

O

CH3

OH

OH

CH3

2 Ce(SO4)2

HCl, Zn

Reduction

(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


Ex. Redox titration ( hydroquinone vs dichromate standard solution )

HO OH O O + 2H+ + 2e Eo= 0.700

Cr2O72– + 14H+ + 6e 2 Cr3+ + 7 H2O Eo= 1.33

3

3 HO OH + Cr2O72– + 8H+ 3 O O + 2 Cr3+ + 7 H2O

Eo= Eocathode – Eo

anode = 1.33 – 0.700 = 0.63 V

K = 10 nEo/0.05916 = 10 6(0.63) / 0.05916 = 10 64

redox indicator : diphenylamine

colorless to violet

Very large : quantitative : complete reaction


Iodimetry and iodometry

• 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.


I2 + V.C→ 2I- + ……

I- + Cu2+→ I2 + Cu+

I2 + S2O32- → 2I- + S4O6

2-

1) Iodine only dissolves slightly in water. Its solubility is enhanced by interacting with I-

2) 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 I3- by quantitative reverse disproportionation:

3) Cu2++4I- 2CUI + I2

standard I3-


Stability of I2 Solutions

• In 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.


I2 + OH- ⇌ IO- + I- + H+ 3IO- ⇌ IO3- + 2I-


Iodimetry


iodometry

Bromatimetry

BrO3– + 5Br– + 6H+ 3Br2 + H2O

2I– + Br2 I2 + 2Br–


I2 + 2 S2O32– 2I– + S4O6

2–

Addition reactions


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.


preadjustment of analyte oxidation state it is necessary to adjust the oxidation state of the...

Documents

s s ph

slides slide

h hso

znhg s

equivalent s

o unmeasured excess

zn s hg

hcl slide