32.1.

32
AOAC Official Method 956.03
Bromates and Iodates in
White and Whole Wheat Flour
Final Action

(Caution: See Appendix B, safety notes on handling acids.)

A. Qualitative Test for Bromates and Iodates

Cover bottom of white pan (ca 150 square inches) with reagent
prepared by mixing equal volumes HCl (1 + 7) and 1% KI solution.
Distribute ca 4 g flour evenly over liquid by sifting through No. 60
sieve. Alternatively, sift flour over surface of dry pan and spray
mixed reagent onto flour from glass atomizer until all particles are
wetted. Black specks or purple spots not observed before the reagent
was added indicate presence of bromate or iodate.
B. Qualitative Test for Iodates

(Caution: See Appendix B, safety notes on handling acids.)

(a) Applicable to 10 ppm or more.Distribute ca 1 g flour evenly
over bottom of Petri dish and completely cover with freshly
prepared mixture of 1 volume 1% KSCN to 4 volumes HCl (1 + 32).
Break up any lumps with stirring rod and observe with dish on white
surface. Interpret results as in 956.03A.
(b) Applicable to 1 ppm or more.Proceed as in 956.03A but
use acid-KSCN reagent, (a).
Quantitative Method for Bromates

(Applicable in absence of iodates.)

C. Reagents

(Caution: See Appendix B, safety notes on pipets, centrifuge, handling acids and alkalies.)
(a) Zinc sulfate solution.Dissolve 20 g ZnSO47H2O in 800 mL
H2O and dilute to 1 L.
(b) Sodium hydroxide standard solution.0.4N. Dissolve 17 g
NaOH in 1 L H2O. Titrate against standard acid and adjust to 0.4
0.01N.
(c) Sodium hydroxide standard solution.0.5N. Dissolve 21 g
NaOH in 1 L H2O. Titrate against standard acid and adjust to 0.5
0.01N.
(d) Dilute sulfuric acid.Approximately 4N. Add 112 mL
H2SO4 to 800 mL H2O. Cool, and dilute to 1 L.
(e) Potassium iodide solution.Dissolve 25 g KI in 30 mL H2O
and dilute to 50 mL. Store in amber bottle in cool place. Discard
solution showing yellow (free I).
(f) Ammo niu m molybd ate solution. D i s s o l v e 3 g
(NH4)6Mo7O244H2O in 80 mL H2O and dilute to 100 mL.
(g) Potassium bromate standard solutions.(1) Stock solution.5 mg/mL. Dissolve 5.000 g KBrO3 (dried 1 h at 110) in ca
800 mL H2O and dilute to 1 L. (2) Working solution.0.25 mg/mL.
Dilute 25 mL stock solution to 500 mL.
(h) Potassium iodate standard solutions.(1) Stock solution.
0.0898N. Dissolve 3.204 g KIO3 (dried 1 h at 110) in ca 800 mL
H2O and dilute to 1 L. (2) Working solution.0.00359N. Dilute 10
mL stock solution to 250 mL. Prepare fresh daily.

(i) Sodium thiosulfate standard solutions.(1) Stock solution.

Dissolve 22.5 g Na2S2O35H2O and 0.06 g anhydrous Na2CO3 in 800
mL H2O, and dilute to 1 L. Dilute 10 mL to 250 mL. Transfer 5 mL
diluted solution to 200 mL Erlenmeyer. Add 100 mL H2O, 10 mL
dilute H2SO4, and 1 mL KI solution. Add 5 mL freshly prepared
starch solution (mix 1 g soluble starch with enough cold H2O to make
thin paste, add 100 mL boiling H2O, and boil ca 1 min), and titrate
with 0.00359N KIO3 from 10 mL buret graduated in 0.05 mL. Adjust
stock Na2S2O3 solution so that 10 to 250 dilution is 0.00359N. Store
stock solution in amber bottle in cool place.
(2) Sodium thiosulfate working solution.0.00359N. Dilute 10
mL stock solution to 250 mL. Prepare fresh daily and check titer at
least monthly. 1 mL = 0.1 mg KBrO3.
D. Determination

Quantitatively transfer 200 mL ZnSO4 solution to 600 or 800 mL

beaker and stir with speed-controlled, motor-driven glass stirrer.
(Enough agitation to disperse flour is provided by vortex ca 40 mm
deep which does not extend to bottom of beaker.) Transfer 50 0.1
g sample to stirred solution in 25 g portions. Continue stirring ca 5
min, or until all dry flour on surface is uniformly dispersed in liquid.
While stirring, add 50 mL 0.4N NaOH from pipet. Decrease speed
of stirrer and stir ca 5 min. Filter or centrifuge, clarifying supernate
by filtration, if necessary (24 cm Whatman No. 12 folded paper, or
equivalent, is satisfactory).
Transfer 50 mL of this sample solution to 200 mL Erlenmeyer.
If smaller aliquot is taken, dilute to ca 50 mL with H2O. Add 10 mL
4N H2SO4, 1 mL KI solution, 1 drop ammonium molybdate solution, and 50 mL H2O. While stirring, add 510 mL 0.00359N
Na2S2O3 (an excess). Add 5 mL freshly prepared starch solution
and titrate excess Na2S2O3 with 0.00359N KIO3. (Use 10 mL buret
graduated in 0.05 mL for standard solutions. End point is best
observed straight down.) As end point approaches, add KIO3 solution slowly, 1 or 2 drops at time, swirling and viewing flask after
placing it on white surface after each addition. Take first reddish or
purple tinge as end point; then add several more drops to confirm.
Add additional 1 mL Na2S2O3 solution, and again titrate to additional end point. Average the 2 differences between amounts of
Na2S2O3 solution added and KIO3 used in titrations; ppm KBrO3 =
10 (mL 0.00359N Na2S2O3 mL 0.00359N KIO3). Correct results
by recovery factor determined as below.
E. Recovery Factor

Dilute known volume (x mL), >3 mL but <10 mL, of standard

KBrO3 solution to 250 mL. Using 50 mL aliquot, proceed as in
second paragraph of determination.
Added bromate in ppm =
10 (mL 0.00359N Na2S2O3 mL 0.00359N KIO3)
Suspend 50 g portions nonbromated flour in 2 separate 200
mL portions ZnSO4 solution by stirring as above. To 1 (blank)
suspension, add 10 mL H2O; to other (recovery) suspension, add
x mL standard KBrO3 solution and (10 x) mL H2O. Continue
as above, except add 40 mL 0.5N NaOH from pipet with
continuous stirring. Use 5 mL standard Na2 S2 O3 for blank
and 10 mL for recovery. Deduct blank value, if any, from
value of KBrO3 found in recovery determination and multiply result by 10 to obtain ppm recovered bromate.

Copyright 1998 AOAC INTERNATIONAL

Recovery factor = added bromate/recovered bromate

Reference: JAOAC 39, 664(1956).

Copyright 1998 AOAC INTERNATIONAL