2.6.14
Reduction
AOAC Official Method 967.01
Iron in Fertilizers
Titrimetric Method
First Action 1967
Final Action 1969
A. Reagents
(a) Diphenylamine solution.—Dissolve 1 g in 100 mL H2SO4.
(b) Diphenylamine sulfonate solution.—Dissolve 0.5 g in H2O in
100 mL volumetric flask and dilute to volume.
(c) Potassium dichromate standard solutions.—0.01667M and
0.001667M. Prepare 0.01667M K2Cr2O7 as in 949.13C (see
A.1.0.9). Prepare 0.001667M solution by diluting 100 mL
0.01667M solution to 1 L.
(d) Mercuric chloride saturated solution.—Shake HgCl2 with
H2O and let settle.
(e) Stannous chloride solution.—Dissolve 20 g SnCl2⋅2H2O in
20 mL HCl, warming gently. Add 20 mL H2O and dilute to 100 mL
with HCl (1 + 1). Keep warm until clear; then add few granules Sn.
Dispense from dropping bottle.
B. Preparation of Test Solution
(a) Suitable for all fertilizers.—Treat 1 g test portion as in
957.02B(e) (see 2.3.01), using 15 mL HClO4. Hold ≥1 h at ca 170°C
to remove HNO3 completely. Dilute to 200 mL.
(b) Suitable for soluble salts and oxides.—Dissolve 1 g test por-
tion in 10 mL HCl, warming gently. Dilute to 200 mL.
C.
Heat aliquot of test solution (100 mL and 50 mL, respectively, for
solutions containing <0.5 and 0.5–4.0% Fe) to bp. Add few drops
diphenylamine sulfonate solution; then SnCl2 solution dropwise un-
til violet color is discharged and 2 drops excess. (Usually 1–6 drops
are required. Larger amount may be used with test solutions contain-
ing large amount of Fe.) If reduction does not occur, discard and pro-
ceed as follows with second aliquot:
Add few granules Zn, boil few min, and either filter off excess Zn,
washing with hot H2O, or let Zn dissolve. Heat to bp and finish re-
duction with SnCl2 and diphenylamine sulfonate indicator as before.
Add 10 mL HCl (1 + 1). Adjust volume to 75–110 mL with H2O.
Cool rapidly in cold H2O. Add 10 mL saturated HgCl2 solution, swirl
gently, add 5 mL H3PO4, and titrate immediately. (Small amount of
HgCl must precipitate to ensure complete reduction.)
D. Titration
Add 1 drop diphenylamine indicator by pipet (no more; excess
will interfere with end point if amount of Fe is small). Titrate with
0.005M K2Cr2O7 solution. Since end point may be difficult to see
with very small amount Fe, approach end point slowly, allowing few
s for color to develop. Titrate to permanent blue (sometimes green
with very small amount Fe). For solutions containing >4% Fe, use
0.05M K2Cr2O7 for titration. 1 mL 0.01667M K2Cr2O7 = 0.00558 g
Fe; 1 mL 0.001667M = 0.000558 g Fe.
Reference: JAOAC 50, 397(1967).
CAS-7439-89-6 (iron)
© 2000 AOAC INTERNATIONAL