11.1.15 distillate. Dilute to volume (200 mL) and mix well.

To determine
AOAC Official Method 939.11 acidity, use 40 mL distillate, add 1 mL indicator, mix thoroughly, and
Fluoride in Water note mL 0.05N NaOH required for neutralization.
Colorimetric Method Repeat preparation and distillation, using 100 mL H2O in place of
First Action 1939 test portion, to determine blank.
Final Action
D. Determination
A. Reagents
Prepare one standard, one color comparison tube, and one or more
(a) Fluoride standard solution.—0.01 mg F/mL. Dissolve 2.21 g specimen tubes as follows:
NaF (minimum purity 98%) in 1 L H2O. Dilute 10 mL of this
(a) Color comparison tube.—To 40 mL H2O add 2 mL 0.05M
solution to 1 L.
HCl, 1 mL alizarin red indicator, 1 mL NH2OH⋅HCl solution, and
(b) Thorium nitrate solution.—Dissolve 0.25 g
enough Th(NO3)4 solution to give faint but definite pink end point.
Th(NO3)4⋅12H2O or 0.2 g Th(NO3)4⋅4H2O in 1 L H2O.
Compare all end point colors with this color.
(c) Alizarin red indicator.—0.01% aqueous solution sodium
(b) Specimen tube.—To specimen tube containing 40 mL
alizarin sulfonate (alizarin red S).
distillate add 1 mL indicator, 1 mL NH2OH⋅HCl solution, and
(d) Hydrochloric acid.—Exactly 0.05M.
volume 0.05M HCl such that total volume acid in tube (acidity
(e) Sodium hydroxide solution.—Exactly 0.05M.
previously determined plus volume 0.05M HCl added) equals 2 mL
(f) Hydroxylamine hydrochloride solution.—1.0 g/100 mL.
0.05M HCl. Dilute to volume and mix. If in preliminary acidity
B. Apparatus determination it is found that the 40 mL distillate requires >2 mL
(a) Claisen flask.—250 mL. 0.05M NaOH solution for neutralization, do not add the HCl
(b) Nessler tubes.—6 long-form 50 mL tubes with double optically solution to specimen tube, but add to standard tube same amount of
plane disks fused to tubes. Match tubes for length and test for optical acid as was found present in specimen tube. If 40 mL distillate
similarity as follows: Add ca 40 mL H2O, 1 mL indicator, 2 mL 0.05M requires >5 mL 0.05M NaOH, repeat distillation under conditions
HCl, and H2O to mark on tube. To one tube add amount of Th(NO3)4 favorable to low acidity. From 10 mL buret, graduated to 0.05 mL,
solution such that, after diluting to mark and mixing, color is barely add Th(NO3)4 solution with frequent mixing until faint pink appears,
changed to faint pink. Note amount of Th(NO3)4 solution used. Add comparable to comparison tube, (a). Note volume Th(NO3)4
same amount of Th(NO3)4 solution to each of remaining 5 tubes. Reject solution used.
tubes showing detectable differences in shade or intensity. (c) Standard tube.—To standard tube containing 40 mL H2O add
See also 944.08C (see 9.2.11). 1 mL indicator, 1 mL NH2OH⋅HCl solution, and ≥2 mL 0.05M
C. Preparation of Specimen HCl, as was required in specimen tube in (b). If aliquot chosen for
If specimen has odor of H2S, oxidize with 0.1 mL 30% H2O2 determination already contains 2–5 mL 0.05M acid, add exactly
solution before evaporation. same amount to standard tube. Add exactly same amount of
Place 100 mL specimen in porcelain or Pt dish, make alkaline to Th(NO3)4 solution as was added to spec imen tube. To standard
phenolphthalein with 10% NaOH solution (w/v) (avoid excess), and tube (now more highly colored than spec imen tube), add standard
evaporate to 20 mL over burner at temperature just below bp. During F solution from 10 mL buret with mixing until color matches that
evaporation keep solution alkaline by adding small amounts of of specimen tube. Dilute contents of both standard and specimen
0.05M NaOH from time to time. Transfer the 20 mL evaporated tubes to same volume. Mix solution in each tube and let all air
solution to Claisen flask containing glass beads or boiling tube bubbles escape before making color comparisons. Check end
previously rinsed with boiling 10% NaOH solution to eliminate all point by adding 1–2 drops standard F solution to standard tube.
traces of gelatinous SiO2 accumulating in flask. Distinct color change should de velop.
Place flask containing evaporated solution on insulating board E. Calculations
(15 × 15 × 0.6 cm with 2.5 cm center hole) over burner adjusted for Subtract mL F solution required by blank from mL F solution
medium flame. Close straight neck of flask with 2-hole rubber required by specimen.
stopper through which pass ther mometer and stem of small
separator with outlet constricted to 2 mm diameter. (Adjust mL F solution × mL total distillate × 10
thermometer and outlet tube of separator to extend almost to bottom = F (µg/mL)
mL aliquot titrated × weight test portion taken
of flask.) Close other neck of flask with solid rubber stopper.
(Alternatively, all-glass distillation assembly may be used.)
Connect flask with water condenser; add 20 mL 60% HClO4 to Example: 100 mL test portion, evaporated and distilled to 200
flask, rinsing evaporating dish and separator; then add amount of mL, of which 40 mL aliquot corresponds to 5 mL F solution, gives:
sat u rated AgClO 4 so lu tion that will pre cip i tate chlo rides
5 × 200 × 10
(determined previously by titration with standard AgNO3 solution), = 2.5 F (µg/mL)
and distil at 132° ± 3°C, adding H2O dropwise through separator to 40 × 100
maintain temperature during distillation. Collect nearly 200 mL Reference: JAOAC 22, 482(1939).

 2005 AOAC INTERNATIONAL