Standard Iodine solution, I3−

• Properties
I2(s) + I− ↔ I3−

• Stability of standard solution

4I− + O2(g) + 4H+ → 2I2+ 2H2O

• Standardization
H3AsO3 + I2 + H2O ↔ H3AsO4 + 2I− + 2H+ , (NaHCO3)
I2 + 2S2O32− ↔ S4O62− + 2I−

• Conditions
• End point detection
• Applications
Reduction half reaction
• I2 + 2e ↔ 2I− E0 = 0.536 V

• OR

• I3− + 2e ↔ 3I−
• Eq. wt = M wt/ 2 for 1 mole iodine.
Titrations involving Iodine

Iodimetric titration:
• Direct
• For analyzing strong reducing agents
• H3AsO3 + I2 + H2O ↔ H3AsO4 + 2I− + 2H+ (NaHCO3, starch)
• Ep detection
Starch is used as indicator It is added at the beginning of the titration.
The first drop excess of I3− after the equivalence point causes the
solution to turn blue.
• Conditions:
Titrations occur in neutral or weakly alkaline solutions
AsO43– + 2H+ + 2e ↔AsO33– + H2O
0.059 [AsO33–]
E = Eo – ________log ______________
2 [AsO43–][H+]2
1- [H+] ↓ E ↓
2- Equilibrium shift to the right of the overall reaction.
H3AsO3 + I2 + H2O ↔ H3AsO4 + 2I− + 2H+ (NaHCO3,
starch)
• How to force iodine-analyte reaction toward
completion
• pH effect
I2 + 2e ↔ 2I− E0 = 0.536 V
pH has no effect on electrode potential.
• Complexing agent
Fe3+/ Fe2+ system,
Fe3+ + e− ↔Fe2+ E0 = 0.77 V
I3− + 2e ↔ 3I− E0 = 0.536 V
• Addition of complexing agents as F– or EDTA that
form stable cpx with Fe3+ → shift to lower E (E < 0.53
V) that allows oxidation of Fe2+ with I2
Sources of error in iodimetry
• Due to I2
Lack of stability (volatility, air oxidation of iodide)
• Due to starch
Decomposition products, e.g. glucose may be oxidized with iodine,
other products give irreversible reddish color with I2.
To Avoid, add preservative like boric acid or formamide.
Applications in Iodimetry
• By Direct Titrations

Determination of Na2S2O3
2S2O32− + I2 ↔ S4O62− + 2I−
tetrathionate

Determination of As3+

H3AsO3 + I2 + H2O ↔ H3AsO4 + 2I− + 2H+

- Starch ind, added at the beginning of titration

- The solution is neutral, use NaHCO3
By Back Titrations Technique
Determination of Aldehydes and aldoses
- Formaldehyde,
- Glucose (aldehydic reducing sugar),
- Sucrose (Non reducing sugar, after acid hydrolysis → equivalent amount of glucose)

St. I2 + 2OH− ↔ IO− (stronger oxidizing agent) + I− + H2O

RCHO + IO− + OH− ↔ RCOO− + I− + H2O

aldose

IO− (Xss unreacted) + I− + 2H+ (acidify) ↔ I2 + H2O

I2 + 2S2O32− ↔ 2I− + S4O62−

Starch is used as ind. In the back titration reaction, added after acidification.
Iodometric titration:
• Indirect
• For analyzing oxidizing agents
• Add xss I− to a solution of analyte. I2 is produced in an amount equivalent to
the oxidizing agent. Liberated I2 is tit ≠ st Na2S2O3

Cr2O72− + 6I− (xss) + 14H+ ↔ 2Cr3+ + 3I2 + 7H2O

I2 + 2S2O32− ↔ 2I− + S4O62−

Cr2O72− ≡ 3I2 ≡ 6S2O32−

Na2S2O3 is a universal titrant for I2 in neutral or acidic solutions

• Ep detection
Starch
CHCl3 or CCl4
Titrations occur in acidic solutions
MnO4− + 8H+ + 5e ↔ Mn2+ + 4H2O

0.059 [Mn2+]
E = Eo – ___________ log _______________
5 [MnO4–][H+]8

[H+] ↑ E ↑
(titration should be performed rapidly to minimize air
oxidation of iodide)
• How to force oxidation of iodide by analyte toward
completion
1-pH
↑ [H+] promotes oxidizing agent-iodide reaction (↑E of
oxidizing agent couple)
2- Precipitating agent
Cu2+ + e− ↔ Cu+
E0 Cu2+/ Cu+ = + 0.34 V // E0 I2/I− = + 0.536 V
adding SCN− OR I− reagent to ppt Cu+ --- [Cu+] ↓ → ↑E
of Cu2+/ Cu+
0.059 [Cu+ ]
E = Eo – ___________ log _____________
1 [Cu2+ ]
[Cu+] ↓ E ↑
Function of iodide
(a) reduce Cu2+ to Cu+
(b) precipitate Cu+ ion
2Cu2+ + 4I-  Cu2I2 ↓ + I2
But the precipitated Cu2I2 would adsorb I2 on its surface, so we add
(NH4)SCN to precipitate the more insoluble Cu2(SCN)2 and set free the
adsorbed I2.
Cu2I2 + 2SCN–  Cu2 (SCN)2 + 2I–
Sources of error in iodometry
• Decomposition of thiosulfate solution.
• Premature addition of starch and its decomposition.
• Due to I2
Lack of stability (volatility, air oxidation of iodide)
Iodometric

Determination of oxidizing agents

2MnO4− + 10I− + 16H+ ↔2Mn2+ + 5I2 + 8H2O

Cr2O72− + 6I− + 14H+ ↔2Cr3+ + 3I2 + 7H2O

Cl2 + 2I− ↔I2 + 2Cl−

BrO3− + 6I− + 6H+ ↔Br– + 3I2 + 3H2O

IO3− + 5I− + 6H+ ↔3I2 + 3H2O

2Fe3+ + 2I− ↔2Fe2+ + I2

H3AsO4 + 2I− + 2H+ ↔ H3AsO3 + I2 + H2O

Titrate the liberated I2 ≠ st Na2S2O3 , CCl4 ind

2S2O32− + I2 ↔S4O62− + 2I−

Titrations involving Iodine
Iodimetry
• Weakly alkaline or neutral solution
• If pH is too alkaline
I2 will disproportionate to
hypoiodide and iodide
I2 + 2OH− ↔IO− + I− + H2O
OI– is a stronger oxidant than I2
Iodometry
• Acidic solution
• Why titration solution kept NOT strongly
acidic
Starch ind. tends to hydrolyze in strong
acid.
I− tends to be oxidized by dissolved
oxygen. In strongly acidic medium
4I− + O2(g) + 4H+ → 2I2+ 2H2O
karl Fischer reagent for determination of water
• Reagent
Iodine, sulfur dioxide dissolved in pyridine (I2, SO2
exist as complex to prevent their volatilization) and
xss. methanol
C5H5N C5H5N.I2 C5H5N.SO2 MeOH
• Application
Determination of water in organic liquids and solids
which are soluble in methanol and can be analyzed by
direct titn (acids, alcohols, esters, anhydrides…)
• C5H5N.I2 + C5H5N.SO2 + C5H5N + H2O ↔
2C5H5N.HI + C5H5N.SO3
• Method: Direct titration
• E.p.: potentiometry
Color change from yellow (reaction
products) to brown (xss reagent, pyridine
iodine cpx)
• Stoichiometry: 1 mole of I2, 1 mole of SO2, for each
mole of H2O.
I2 ≡ H2O
Role of methanol in Karl Fisher Reagent

• C5H5N.SO3 + H2O ↔ C5H5NH.SO4H

• C5H5N.SO3 + CH3OH↔ C5H5NH.SO4CH3