EXPERIMENT 11A: Preparation of Ferrous Sulfate, USP

FeSO4•7H2O Procedure:
Dissolve the iron nails in the measured volume of 50% w/v H2SO4 in an
Erlenmeyer flask equipped with a
INTRODUCTION: Bunsen valve. Concentrate by gentle heating. Filter off any unreacted iron nail,
dry, and weigh.
>> Ferrous Sulfate contains an amount of FeSO4 equivalent to not less than Crystallize the filtrate in an ice bath. Collect the crystals.
99.5% and not more than 104.5% of FeSO47H2O.
REVIEW QUESTIONS:
Official Preparations:
Dried Ferrous Sulfate, USP 1. What is the significance of diluting sulfuric acid with water prior to
Ferrous Sulfate Oral Solution, USP reaction with iron?
Ferrous Sulfate Tablets, USP Fe2+ has a high tendency to be oxidized into Fe3+. When Fe2+ salts are
Ferrous Sulfate Syrup, USP in solution, their transformation to the corresponding basic Fe3+ salt is
much more rapid.
Synonyms: Concentrated H2SO4 is a powerful oxidizing agent, and a dehydrating
Copperas, green vitriol or iron vitriol agent (due to its low water content). Dilution of H2SO4 to 50% prior to
dissolution of Fe nail can prevent or at least minimize the fast oxidation of
Physical Properties: Fe2+ to Fe3+. Also, the desired form of the product is heptahydrate.
• Molecular Weight: 278.02 (USPCI, 2007)
• Large, pale bluish-green monoclinic prisms 2. What is a hematinic?
• Odorless and has a saline, stypic taste Anti-anemic that increases blood hemoglobin through erythropoiesis.
• Efflorescent in dry air – becomes coated with anhydrous salt 3. Why is a Bunsen valve used in this preparation?
• Oxidizes in moist air forming a brown coating of basic ferric sulfate: Exposure to atmospheric oxygen causes rapid oxidation of Fe2+. The
4 FeSO4 + 2 H2O + O2 → 4 Fe(OH)SO4↓ Bunsen valve provides a close system for the reaction to take place. And
(Soine & Wilson, 1967, p. 604) since H2↑ is produced as a by-product of the preparation, providing a small
USP label: It is not to be used if it is coated with brownish-yellow basic ferric slit at the rubber tubing could provide an opening for the gas to escape. In
sulfate this case, build-up inside the set-up is avoided while maintaining O2↑ out of
Rate of oxidation increased by the addition of alkali or exposure to light the reaction.
• Forms tetrahydrate at 56.6°C; heating further to 65°C converts it to the
monohydrate ion 4. How should ferrous salts be stored in solution?
• @ 115˚C crystals disintegrate and lose most water of hydration Addition of Fe nail into the solution. The Fe nail will serve as the
“sacrificial lamb” that will undergo oxidation instead of Fe2+. Of course, this
• Soluble in water and insoluble in alcohol
is not pharmaceutically elegant especially in the case of commercial drugs.
In the case of FeSO4, mixing with glucose or fructose can be done to
prevent oxidation.
Starting Materials:
Molecular Weight (g/mol)
Iron (Iron nails) 55.845 (Merck & Co., 2000)
Sulfuric Acid 98.08 (Merck & Co., 2000)

Net Equation:
Fe↓ + H2SO4 + 7H2O → FeSO4•7H2O↓ + H2↑
(Soine & Wilson, 1967, p. 603)
OFFICIAL ID TESTS:

The product responds to tests for Ferrous Salts and Sulfate.

Ferrous Salts: Solutions of Ferrous salts yield a dark blue precipitate with potassium ferricyanide TS. This precipitate is insoluble in 3N Hydrochloric Acid, but is
decomposed by 1N sodium hydroxide. With 1N sodium hydroxide, solutions of ferrous salts yield a greenish-white precipitate, the color rapidly changing to
green then to brown when shaken.

Sulfate: With barium chloride TS, solutions of sulfates yield a white precipitate that is insoluble in hydrochloric acid and nitric acid. With lead acetate TS, neutral
solutions of sulfates yield a white precipitate that is soluble in ammonium acetate TS. Hydrochloric acid produces no precipitate when added to solutions of
sulfates (distinction from thiosulfates).

Guys, hindi pa nakabalance ung ibang equation.. sorry.

CHEMICAL EQUATIONS REAGENTS VISIBLE RESULTS PRINCIPLES INVOLVED
A. Ferrous Ion
1) FeSO4 + K3[Fe(CN)6] → Fe4[Fe(CN)6]3↓+ K33[Fe(CN)6] TS Dark blue precipitate Turnbull’s blue
K2SO4 (Svehla, 1996, p. 111) (USPCI, 2007) Fe4[Fe(CN)6]3 is known as Turnbull’s blue. This reaction is utilized as
a. Fe4[Fe(CN)6]3↓ + HCl → no 3 N HCl No dissolution of a sensitive test for ferrous ion, since ferric ion does not react with
reaction precipitate ferricyanide.
(USPCI, 2007) Addition of NaOH is a decomposition reaction
b. Fe4[Fe(CN)6]3↓ +NaOH → 1 N NaOH Precipitate turns greenish-
Na4[Fe(CN)6] + Fe(OH)2↓ + white
Fe(OH)3↓ (USPCI, 2007)

(Soine & Wilson, 1967, p. 606)

FeSO4 + 2 NaOH → Fe(OH)2↓ + 1 N NaOH
Na2SO4
(Svehla, 1996, p. 110)
4 Fe(OH)2↓ + 2 H2O + O2 → 4
Fe(OH)3↓
(Svehla, 1996, p. 110)
1) FeSO4 + BaCl2 → BaSO4↓ + FeCl2
a. BaSO4↓ + HCl → no reaction
Greenish-white precipitate
rapidly changes to green,
which Exposure to air and addition of H2O oxidize Fe(OH)2↓ to Fe(OH)3↓
turns brown upon shaking
(USPCI, 2007)
B. Sulfate Ion
BaCl2 TS Heavy, white precipitate
HCl No dissolution of CAUTION: Concentrated HCl and HNO3 must NOT be used in this
 precipitate case as it would precipitate out barium chloride or barium nitrate.
b. BaSO4↓ + HNO3 → no reaction HNO3 No dissolution of
precipitate
2) FeSO4 + Pb(CH3COO)2 → PbSO4↓+ Pb(CH3COO)2 White heavy precipitate The stability of the tetrahydroxoplumbate(II) complex is not very
Fe(CH3COO)2 TS great as the presence of let’s say chromate ion can precipitate lead
a. PbSO4↓ + 4 NH4CH3COO→ NH4CH3COO Precipitate dissolves chromate.
(NH4)2[Pb(CH3COO)4] + (NH4)2SO4 TS forming a clear colorless
solution
3) FeSO4 + 2 HCl → FeCl2 + H2SO4 HCl Clear, colorless solution Distinction from thiosulfates which slowly form white precipitates of
with no precipitate sulfur and an evolution of suffocating odor owing to SO2.