Page 40 - Pharmaceutical Analytical Chemistry II - Pharm D Clinical- 07-PA202
P. 40

WHY starch is added just before the eq point

- Iodine-starch complex is ONLY slowly dissociated, and
- a diffuse e.p. would result if a large amount of iodine is adsorbed
on starch
- Most iodometric titns are performed in strongly acidic solutions
and the starch has a tendency to hydrolyze in acid solution

CHCl3 or CCl4
-suitable for highly acidic solutions
-Iodine dissolves in such solvents giving intense purple color. Ep is
marked by the disappearance of purple color in the organic solvent
layer (vigorous shaken during titn is required)

5- Applications

1- Determination of Cu2+

Cu2+ + e−           Cu+

E0 Cu2+/ Cu+ = + 0.15 V                 E0 I2/I−  = + 0.536 V

To force the reaction---oxidation of I– by Cu2+--- you have to ↑E of

Cu2+/ Cu+ system to be > 0.53 V

BY:

adding SCN− OR I− reagent to ppt Cu+ --- [Cu+] ↓ → ↑E of Cu2+/Cu+

       E = Eo –     0.059             [Cu+ ]
NOTE
                               log  [Cu2+ ]
                                            E↑
                       1
                       [Cu+] ↓

I– has 2 functions

(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.

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