Assay

Chromic Chloride,
USP 30

CrCl36H2O
98.0 %-101.0% of
CrCl36H2O

Indicator & Color

Chemical Equations, Factor & Derivation,
RFIS
Transition
Calculation for %P based on OR
Dissolve about 0.4 g of Chromic Chloride, accurately weighed, in 100 mL of water contained in a glass-stoppered, 500-mL conical flask, add 5 mL of 5 N sodium hydroxide, and mix. Pipet, slowly 4 mL of 30 percent hydrogen
peroxide into the flask, and boil the solution for 5 minutes. Cool the solution slightly, and add 5 mL of nickel sulfate solution (1 in 20). Boil the solution until no more oxygen is evolved, cool, and add 2 N sulfuric acid dropwise until
the color of the solution changes from yellow to orange. Add to the flask a freshly prepared solution of 4 g of potassium iodide and 2 g of sodium bicarbonate in 100 mL of water, then add 6 mL of hydrochloric acid. Immediately
insert the stopper in the flask, and allow to stand in the dark for 10 minutes. Rinse the stopper and the sides of the flask with a few mL of water, and titrate the liberated iodine with 0.1 N sodium thiosulfate VS to an orange color.
Add 3 mL of starch TS, and continue the titration to a blue-green endpoint. Each mL of 0.1 N sodium thiosulfate is equivalent to 8.882 mg of CrCl 36H2O.
1. addition of 5N NaOH
Iodometry using
Starch TS
Preliminary Treatment:
- to form tetraaquochromate (III) ions:
0.1 N Sodium
deep blue to blue-green
CrCl
+
3 NaOH Cr(OH)3 + 3 NaCl
3
CrCl3 + 3 NaOH Cr(OH)3 + 3 NaCl
Thiosulfate VS
Cr(OH)
3 + NaOH Na[Cr(OH)4]
Cr(OH)3 + NaOH Na[Cr(OH)4]
2 Na[Cr(OH)4] + 3 H2O2 + 2 NaOH 2 Na2CrO4 + 8 H2O
2. addition of 30% H2O2
Starch TS: Mix 1 g of
NiSO4 + 2 NaOH Ni(OH)2 + Na2SO4
- to oxidize tetraaquochromate (III) ions into chromate ions:
soluble starch with 10 mg
2 H 2 O2 (OH )2 2 H 2 O+O2
2 Na[Cr(OH)4] + 3 H2O2 + 2 NaOH 2 Na2CrO4 + 8 H2O
of red mercuric iodide and

3. boil for 5 minutes, cool, add nickel sulfate solution, boil until no more oxygen is evolved
sufficient cold water to
Ni(OH)2 + H2SO4 NiSO4+ 2 H2O
make a thin paste. Add
- excess H2O2 is decomposed by boiling
2 Na2CrO4 + H2SO4 Na2Cr2O7 + Na2SO4 + H2O
200 mL of boiling water,
NiSO4 + 2 NaOH Ni(OH)2 + Na2SO4
and boil for 1 minute with
nickel hydroxide is not oxidized by H2O2, instead, it catalyzes its decomposition:
reduction half-reaction: Cr2O72- + 14 H+ + 6e- 2 Cr3+ + 7 H2O
continuous stirring. Cool,
2 H 2 O2 (OH )2 2 H 2 O+O2
oxidation half-reaction: [2 I- I2 + 2 e-] x3
and use only the clear

net balanced equation: Cr2O72- + 14 H+ + 6 I- 2 Cr3+ + 7 H2O + 3 I2

solution. [Note
complete balanced equation:
Commercially available,
4. cool, add 2N H2SO4 dropwise until color of solution changes from yellow to orange
Na
Cr
O
+
14
HCl
+
6 KI 2 CrCl3 + 7 H2O + 3 I2 + 6 KCl + 2 NaCl
2
2
7
stabilized starch indicator
Ni(OH)2 + H2SO4 NiSO4+ 2 H2O
solutions may be used.]
- to convert chromate (yellow) to dichromate (orange-red) ions:
2 Na2CrO4 + H2SO4 Na2Cr2O7 + Na2SO4 + H2O
reduction half-reaction: I2 + 2e- 2 I5. add freshly prepared solution of KI & NaHCO3 in H2O, add HCl
oxidation half-reaction: 2 S2O32- S4O62- + 2 eNa2Cr2O7 + 6KI + 14HCl 3 I2 + 2 CrCl3 + 6 KCl + 2 NaCl + 7 H2O
net balanced equation: 2 S2O32- + I2 S4O62- + 2 I- KI may undergo atmospheric oxidation: 4 KI + O2 + 4 HCl 2 I2 + 4KCl + 2 H2O, which
complete balanced equation: 2 Na2S2O3 + I2 Na2S4O6 + 2 NaI
is catalyzed by acids, heat, light, certain metal ions and nitrite ions leading to oxygen error
f = 3 since 1 mole CrCl3 is equivalent to 0.5 mole Na2CrO4, while 1 mole
- thus NaHCO3 is added to minimize atmospheric oxidation of iodide by filling the
Na2CrO4 is equivalent to 3 moles I2, and 1 mole I2 is equivalent to 2 moles
atmosphere with inert CO2:
Na2S2O3; thus 1 mole CrCl3 is equivalent to 3 moles Na2S2O3.
KI + 2 HCl + NaHCO3 NaI + KCl + H2O + CO2
Type of Titration

6. excess KI is added to decrease volatility of iodine and increase its solubility through
formation of triiodide ion: KI + I2 KI3

7. rinse the stopper and the sides of the flask with few mL H2O solution is diluted before
titration to make endpoint more readily observed, since at the endpoint, the mixture does
not become colorless, but a light blue-green color due to Cr 3+
8. add starch TS only when the mixture is already orange-colored
- reversibility of the blue starch-iodo complex is decreased when iodine concentration is
high because some iodine tends to remain bound to starch particles
also, starch decomposes irreversibly in solutions containing large concentrations of iodine
which will interfere with the indicator properties of starch and may also be oxidized by iodine
9. reaction medium must be slightly acidic and temperature must not exceed 25C
- sensitivity of starch TS as indicator is greater in slightly acidic media and is decreased by
temperatures above 25C
- starch TS cant be used in strongly acidic medium because hydrolysis of starch occurs,
forming glucose, which is a reducing agent, and thus a possible source of error
10. efficient swirling is needed to prevent local excesses of thiosulfate because it is
decomposed in acid solution: Na2SO3 + 2 HCl H2SO3 + S + 2 NaCl

P=

266.45
3 1000
100
sample weight

0.1 NF V T