9.2.

11
AOAC Official Method 944.08
Fluorine in Food
Distillation Method
First Action 1944
Final Action
A. Principle
Material is ashed with Ca(OH)
2
as F fixative; F is isolated by Wil-
lard-Winter distillation [Ind. Eng. Chem. Anal. Ed. 5, 7(1933)] from
HClO
4
, and estimated in distillate by Th(NO
3
)
4
back-titration
method [JAOAC 27, 246(1944)]. Technique and reagent concentra-
tions are designed to handle 10.0 mg F conveniently. Modifica-
tions applicable to specific products are described.
B. Precautions and Interferences
Control magnitude of determination blank by careful choice and
purification of reagents (see D). With care, blank will be low(13g
F), but with low-F foods it may represent considerable part of total F
determined; hence, it must be stable. Large part of it will be distilla-
tion blank apparently resulting from F leached from glassware of
still during distillation. This blank can be minimized by preliminary
treatment of stills, F, and average distillation blank determined if
stills of same material and design are routinely used; otherwise, each
still must bear its special blank. New, unused stills will usually be
found to exhibit high blank, which will diminish to constant low fig-
ure after several determinations. They should not be used until several
consecutive blank determinations yield constant, low amount of F.
Check ashing utensils by blank determinations with fixative solu-
tion to determine if they contribute appreciable F. Even Pt vessels
may become contaminated (owing presumably to slight Ca content)
if they have been used recently for HFvolatilization of SiO
2
. In addi-
tion, such blank determinations are useful for testing reagents and
apparatus used in method and also evaporators, hoods, furnaces, and
laboratory atmosphere for presence of F fumes and dust. If HF bot-
tles are permitted in same laboratory, seal immediately after use;
avoid contamination from roach powders.
Ordinary tap H
2
O may be source of F contamination, since 1 mL
H
2
O containing 2 ppm F will contribute 2g F if allowed to remain
or to dry in still. Therefore, routinely rinse all glassware (stills,
flasks, burets, etc.) with H
2
O, preferably redistilled from alkaline
KMnO
4
. Filter papers may contributeg amounts of F, and glass fil-
ters are preferred if filtration is required in micro determinations.
Interferences are gelatinous SiO
2
, Al, and B compounds, which
repress evolution of F as H
2
SiF
6
in distillation; materials such as ni-
trates, nitrites, peroxides, Cl, SO
2
, and H
2
S, which act upon indicator
in titration or otherwise interfere; halides (Cl), which distil to give
excessive acidity in distillate; and phosphates and sulfates, which re-
act with Th in titration to give high results. Method is so designed
that most of these interferences are automatically eliminated, but an-
alyst should be on guard against their possible occurrence under un-
usual circumstances.
C. Apparatus
(a) Fluorine still.Claisen 100125 mL distilling flask is most
practical for general work. It must be of Pyrex glass with auxiliary
neck sealed off immediately above side arm to prevent pocketing
and refluxing of distillate. Still should be as small and simply de-
signed as practicable; ordinary distilling flasks can be used for some
work and they are slightly more efficient than Claisen type, except
that danger of spraying over of distilling acid is greater.
Equip still with dropping funnel and 0150Cthermometer, latter
extending to within 6 mm of bottom of flask, so that bulb is im-
mersed in boiling acid mixture. Acid-alkali washed beads, prefera-
bly Pyrex, should be on hand. Clean rubber stoppers by boiling in
10% NaOH solution. All-glass apparatus with standard taper acces-
sories is convenient, especially in routine work, and eliminates need
for rubber stoppers.
While not entirely necessary for heating still, use of Wood metal
(50 Bi, 25 Pb, 12.5 Sn, 12.5 Cd) bath, adequately shielded, will pre-
vent undue decomposition of HClO
4
and aid materially in securing
low blank and low-acid distillate; hence, its use is strongly urged. If
metal bath is used, do not immerse flask so deeply that bath level is
above that of liquid in flask; if bath is not used, flask should be
heated on electric heating mantle with temperature controller. (Bath
and shielding boards prevent over-heating of upper still walls.)
At analysts option, distilling H
2
Omay be added as steaminstead
of through dropping funnel; electric boiler, Figure 938.09 (see
35.1.27), is convenient steam generator. If steam is used, inlet tube
should dip below surface of liquid in still. One advantage in adding
distilling H
2
O through funnel is that last portions of rinse H
2
O used
in transferring an ash can be used in distillation. If funnel plug is
thinly notched with sharp file on either side of bore, dropping rate
can be more easily controlled, and end of funnel stem need not ex-
tend into liquid in still. Still is used in conjunction with clean
straight-tube condenser no longer than necessary for adequate cool-
ing. (Vertical arrangement of condenser will conserve bench space.)
(b) Nessler tubes.Tall-form, 100 and 50 mL, glass-stoppered
type preferred. Matched in sets of 6. (100 mL size is used most fre-
quently in general method.)
(c) Additional apparatus.(See B.) Carefully cleaned and tested
Pt, or well-glazed porcelain, dishes of 100 mL size; 150 mL volu-
metric flasks, or if these are not available, 200 mL size; and 10 mL
burets (conveniently automatic) to deliver various solutions re-
quired in distillation and titration. Overhead radiant heater will be
found invaluable for drying and preliminary charring of test por-
tions, especially those of high-sugar type.
D. Reagents
(Caution: See Appendix B, safety notes on distillation, hydroflu-
oric acid, perchloric acid, and sulfuric acid.)
(a) Lime suspension.Carefully slake ca 56 g (1 mole) low-F
CaO (ca 2 ppm (g/g) F) with ca 250 mL H
2
O, and slowly add
250 mL 60% HClO
4
with stirring. Add few glass beads and boil
down to copious fumes of acid; cool, add 200 mL H
2
O, and boil
down again. Repeat dilution and boiling down once more; cool, di-
lute considerably, and filter through fritted glass filter, if precipi-
tated SiO
2
appears. Pour clear solution, with stirring, into 1 L NaOH
solution (100 g/L), let precipitate settle, and siphon off supernate.
Remove sodium salts from precipitate by washing 5 times in large
centrifuge bottles, shaking mass thoroughly each time. Finally,
shake precipitate into suspension and dilute to 2 L. Store in
paraffined bottles. [100 mLof this suspension should give no appre-
ciable F blank when evaporated, distilled, and carried through titra-
tion, (G).] Always shake suspension well before use.
(b) Perchloric acid solution.60%. Dilute HClO
4
with 34 vol-
umes H
2
O and boil down to original volume. Do not fume strongly.
Repeat, and store in Pyrex. (Prepared acid should be Cl-free by test.)
2000 AOAC INTERNATIONAL
(c) Sulfuric acid solution.Carefully mix equal volumes H
2
SO
4
and H
2
O, boil down to fumes, cool, dilute carefully, boil down once
more, and dilute to 1 + 1 volume.
(d) Silver perchlorate solution.50 g/100 mL.
(e) p-Nitrophenol indicator.0.5% alcoholic solution.
(f) Potassium hydroxide solution.Exactly 0.05M..
(g) Potassium chloride solution.0.05M (3.728 g/L).
(h) Hydroxylamine hydrochloride solution.1.0%.
(i) Hydrochloric acid solution.Exactly 0.05M..
(j) Alizarin indicator.0.01%aqueous solution of sodiumaliza-
rin sulfonate (Alizarin Red S).
(k) Potassium fluorosilicate standard solutions.(1) Stock so-
lution.0.5 mg F/mL. Dissolve and dilute 0.9661 g (corrected for
purity as indicated below) K
2
SiF
6
to 1 L (much more will not dis-
solve). Solution keeps indefinitely in paraffined bottle. (2) Working
solution.10g F/mL. Prepare solution used in titration, G, by di-
luting 20 mLstock solution to 1 L. Solution is stable several weeks in
ordinary volumetric ware.
If pure K
2
SiF
6
is not obtainable, prepare as follows: Add, through
dropping funnel, saturated solution of NaF, or suspension of crude
K
2
SiF
6
, into 500 mL Claisen distilling apparatus containing 60 mL
H
2
SO
4
(1 + 1), some glass beads, and 1020 g powdered SiO
2
(or
glass) kept at boiling temperature of 120125C. Distil into 25%so-
lution of KCl, held at simmering temperature on hot plate so that vol-
ume of distillate does not become excessive. If necessary, add more
H
2
O to mixture from dropping funnel in side-neck of still. Regulate
rate of addition of NaFto still and temperature of condensing H
2
Oso
that side arm and condenser do not become clogged with evolved
H
2
SiF
6
, which tends to lodge as gelatinous mass. K
2
SiF
6
is formed in
receiver, and although entirely crystalline it assumes appearance of
gelatinous mass.
When substantial amount collects, pour contents of receiver into
large centrifuge bottle and wash repeatedly by centrifuging (shaking
up precipitate thoroughly each time), until washings are Cl-free by
test. Collect on Bchner and either air dry or bring to constant weight
in vacuo at 5070C.
Determine purity by Travers titration, 921.04B (see 7.1.13), at boil-
ing temperature with 0.2MNaOH(1 mL = 0.01101 g K
2
SiF
6
); also by
conversion to K
2
SO
4
by treating 0.30.4 g in deep Pt dish with little
H
2
O, then H
2
SO
4
plus little HF, fuming off excess acid carefully (if
overheated, mixture has tendency to spatter), and heating to constant
weight of K
2
SO
4
at 650C. With glass apparatus, entirely pure prod-
uct is not usually obtained, as some contamination with SiO
2
results
fromleaching effect of vapors on condenser. Pure product can be ob-
tained by use of Pt still. Prepare stock solution, correcting weight of
0.9662 by purity factor of the K
2
SiF
6
(figure for purity obtained from
average of 2 above methods of assay).
(l) Thorium nitrate solution.0.25 g Th(NO
3
)
4
12H
2
O or 0.20 g
Th(NO
3
)
4
4H
2
O/L. Check titer against standard (10g/mL) F solu-
tion as follows: Measure 10, 20, 30, etc., up to 80 g F into 100 mL
Nessler tubes, andadd4.00mL0.05MHCl (2.00mLif 50mLNessler
tubes are used, and limiting range to only 50 g F) [JAOAC 24,
350(1941)]. Dilute mixture to ca 80 (or 40) mLmark and add 1.00 mL
1.0%NH
2
OHHCl solution. Mix; then add exactly 2.00 mL alizarin
indicator (or 1.00 mL for smaller tube) and add thorium solution
from buret, mixing frequently until, when sighting down tube to-
ward white reflecting surface, incipient pink or salmon pink color
is observed. Add little H
2
Ooccasionally so that solution is nearly to
mark as end point is approached. Finally, dilute exactly to mark and
mix thoroughly before checking final end point. Do not shake tube
vigorously (56 gentle inversions are enough).
Make effort to secure end point shade intermediate between yel-
lowish green of acid indicator and reddish purple of fully developed
thorium lake. Complete series and plot mL Th solution against mL
standard fluoride to obtain rough equivalence curve for 2 solutions.
Depending upon amount of Fknown to be present, add thoriumsolu-
tion in 12 mL portions at first, with final additions of 0.25 mL.
E. Preparation of Material
(Caution: See Appendix B, safety notes on distillation and
perchloric acid.)
Methods of material preparation are designed to furnish represen-
tative laboratory sample in workable amount of material and to ob-
tain test portion in condition for final distillation. Mineralization by
ashing is usually involved. Some mineral food products can be dis-
solved in and distilled from HClO
4
, F, provided no interferences ap-
pear in final distillate.
In general, 20 g dry material, 50100 mL liquid materials, and
50100 g undried food products or plant material can be taken for
analysis, depending upon expected Fcontent and interferences, such
as excessive Cl, which use of large test portions may introduce. For
reasonable precision in analysis of low-F foods, sample should be
sufficient to yield titer of 0.5 mL for aliquot taken in final titration.
However, it may not always be possible to handle this amount of ma-
terial. If adequate grinding and mixing equipment is available, it is
often feasible to prepare large amounts of material (vegetables,
mixed foods) and to take aliquot portions for analysis [Ind. Eng.
Chem. Anal. Ed. 13, 93(1941)].
Dry plant materials, feeds, bone meal, etc., can be ground to con-
venient size in Wiley mill and thoroughly mixed before test portion
is taken. Following special methods for certain products are indi-
cated:
(a) Direct ashing.Applicable to fibrous (not highly fatty)
foods, liquid samples and, in general, to all foods that can be thor-
oughly wet with aqueous fixative solution. This method will apply to
majority of food products.
Weigh suitable portion of prepared test portion into clean Pt dish
and add 25 mL Ca(OH)
2
suspension. (Porcelain casseroles or dishes
are second choice because they may contribute small amounts of F
and Al
2
O
3
to sample.) Mix in Ca(OH)
2
suspension with glass rod,
adding additional H
2
Oif necessary; rinse and remove rod. Dry thor-
oughly on steam bath or in hot air oven; then slowly char sample by
heating over low flame or electric plate with thermostat. Overhead
radiant heater is convenient for both drying and charring sample.
Control excessive swelling of high sugar foods by playing small
flame over surface of sample fromtime to time, and char these prod-
ucts slowly so that excessive acidity is not generated. When sample
is charred past danger of catching fire, ash in furnace at 600C. (For
very small test portions and minimumblanks, it may be advisable to
cover ashing vessel with inverted Pyrex Petri dish while ashing.)
For plants high in silica, fusion with NaOH may be necessary
[Anal. Chem. 25, 450, 1061(1953)].
When clean ash is obtained, cool dish and wet ash with ca 10 mL
H
2
O. (Small amount of unburned C does not interfere but if much
is apparent, dry down and repeat ashing.) Cover dish with watch
glass and cautiously introduce under cover just enough HClO
4
solu-
tion to dissolve ash. Rinse down cover with little H
2
O and transfer
solution to freshly prepared F still, F, through long-stem funnel.
Rinse dish with remainder of distilling acid, using ca 20 mL in all,
2000 AOAC INTERNATIONAL
and adding and transferring in several small portions. Do not pro-
long transferring operation. Finally rinse funnel and stirring rod into
dish, assemble still, and complete rinsing of dish with several small
portions H
2
O, pouring these into dropping funnel of still. If distilling
H
2
Ois added as steam, C(a), rinse dish with little additional H
2
Oand
add directly to acid mixture in still, but avoid excessive initial vol-
ume. Add ca 6 Pyrex beads and enough AgClO
4
solution, D(d), to
precipitate all Cl. (Reasonable excess of AgClO
4
does no harm;
enough solid Ag
2
SO
4
may also be used.) Proceed as in F.
(b) Preliminary distillation.[Necessary with certain products
high in phosphate, such as calcium phosphate and bone meal, in or-
der to eliminate distilled H
3
PO
4
that may be present in appreciable
amounts in first distillates. Also advisable with certain excessively
fatty materials that may not be thoroughly wet with Ca(OH)
2
fixa-
tive, thus causing F loss in direct ashing method.]
(1) For inorganic phosphatic materials, such as calcium phos-
phate.Weigh 10 g test portion into still; add few glass beads,
enough AgClO
4
to precipitate possible Cl, and ca 20 mL HClO
4
so-
lution. (If inorganic phosphatic material does not contain excessive
Ca [enough to cause heavy precipitate of CaSO
4
in still], use similar
amount of 1 + 1 H
2
SO
4
.) Distil at 135140C, collecting ca 200 mL
distillate. (For this preliminary distillation, extreme care in securing
low-acid distillate is not essential.) Evaporate distillate to dryness in
Pt dish after addition of excess Ca(OH)
2
suspension, assuring alka-
line conditions by testing with drop of phenolphthalein. (If H
2
SO
4
is
used in this preliminary distillation, add fewdrops F-free 30%H
2
O
2
to
distillate to oxidize possible sulfites.) Heat dried residue at 600C few
min to destroy indicator residues and possible Cl-containing com-
pounds. Transfer contents of dish to freshly prepared still, F, with
20 mLdistilling HClO
4
solution as in (a), and proceed with final distil-
lation as in F.
Take 20 mL samples of sirupy H
3
PO
4
and collect 300 mL first
distillate at 135C, letting H
3
PO
4
function as its own distilling acid.
(More distillate is necessary because H
3
PO
4
is less effective as Fdis-
tilling acid.) Neutralize with Ca(OH)
2
suspension, evaporate to dry-
ness, transfer to prepared still as above, and proceed as in F.
(2) For organic phosphatic materials, such as bone meal, feed
supplements, etc.As preliminary ashing treatment to destroy most
organic matter, moisten test portions with enough Ca(OH)
2
suspen-
sion, dry, char, and heat 23 h at 600C. Transfer ashed material to
still, which contains several beads and enough AgClO
4
to precipitate
Cl, with 20 mL distilling acid (HClO
4
or H
2
SO
4
, depending on Ca
content of material) as in (a), and continue as in (b)(1), beginning,
Distil at 135140C, . . ..
Certain organic phosphatic materials (small samples of bone,
25 g, such as entire bones of small test animals) in which amount of
organic matter is not excessive, may be distilled directly as in (b)(1)
without preliminary ashing. If sample contains appreciable Ca (bone
samples), use HClO
4
with reasonable precaution; if organic phos-
phatic material does not contain excessive Ca, use 1 +1 H
2
SO
4
. In ei-
ther case, add more Ca(OH)
2
to first distillates and ash for longer
periods to completely destroy distilled organic matter (fatty acids).
Transfer contents of dish to freshly prepared still, F, with 20 mL
HClO
4
solution as in (a) and proceed with final distillation, F.
Baking powders (calcium phosphate and combination types):
Place 10 g test portion in deep, covered Pt dish or casserole and slake
cautiously with ca 20 mL Ca(OH)
2
suspension. After action sub-
sides, rinse cover, dry contents of dish thoroughly, and ash 23 h at
600C. Cool dish and, because of excess of carbonate in ash, treat it
with several small portions of warm H
2
O, breaking up with flat-end
stirring rod, and transfer leachings to still. Transfer remaining con-
tents of dish with 20 mL HClO
4
solution, avoiding excessive effer-
vescence when acid is added to carbonate solution in still. Add
several glass beads and enough AgClO
4
solution, and proceed as in
(b)(1), beginning, Distil at 135140C, . . .. With combination or
sodiumaluminumsulfate baking powders, collect 400 mLprelimi-
nary distillate, (b)(4).
Use of special still trap makes possible analysis of highly
phosphatic inorganic or thoroughly ashed materials, and phosphoric
acids, with single distillation. Special trap, or scrubber, consists of
1215 g small, hollow glass beads supported in side-neck of the
125 mL Claisen flask by several indentations punched in side wall,
and capped by glass disk or inverted bottom of 15 mm test tube. Af-
ter construction of glass-bead scrubber, side-neck is sealed off im-
mediately above outlet tube. (Beads in scrubber must be wet with
little H
3
PO
4
[by tipping flask] before distillation to furnish liquid
acid phase.) Take 20 mL sirupy H
3
PO
4
, by itself, and 10 g test por-
tion calcium phosphate with 20 mL HClO
4
solution, for distillation,
and collect 400 mL distillate at 135C. With single distillation, ob-
serve precautions in C(a), and also in F, regarding neutralization of
final distillates. (Distillates should show practically no acidity.)
Presence of only traces of distilled H
3
PO
4
will vitiate titration; as lit-
tle as 20g P
2
O
5
will definitely interfere. Accordingly, if single dis-
tillation procedure is to be applied with confidence, it is necessary to
test distillates obtained from phosphatic materials, by means of the
special still, for presence of this interference.
For convenient test utilizing Schricker reagent [JAOAC 22,
167(1939)], add 5 mLof 1 +9 dilution of this reagent to 45 mLdistil-
late in 50 mL graduate or Nessler tube, mix, and immerse in steam
bath 510 min. Compare against blank by sighting down tube. Blue
or blue-green color indicates phosphate, and as little as 5 g (as
P
2
O
5
) is readily detected. If distillate shows traces, make sure that
such amounts are below interference level of 15 g in titration
aliquot before titrating additional portions of distillate. (Test with
Schricker reagent is also useful in usual double distillation where
phosphate interference is possible. Use of special trap will save time
where highly phosphatic materials are handled routinely, but it is not
justified in ordinary work because of poor efficiency owing to exces-
sive refluxing in distillation.)
(3) For excessively fatty and oily food materials (oil-packed
foods, certain meats, etc.; also entire undried and unground organs
of test animals).If there is danger of F loss through incomplete
wetting with Ca(OH)
2
fixation solution, handle as follows: Weigh
appropriate amount of test portion, usually 1025 g, into still, and
add Ag (preferably 0.10.2 g solid Ag
2
SO
4
), several glass beads, and
2025 mL H
2
SO
4
(1 + 1). Distil at 130135C and collect
200250 mL distillate in beaker or open vessel. If foaming is exces-
sive, increase volume of distilling acid, and where necessary, use
larger (250300 mL) still. If larger still or more acid is used, collect
proportionately more of first distillate. (Oil or fat of many of these
products will tend to prevent foaming, and, in some instances, use of
ca pea-size piece of pure paraffin is additional aid.)
Oxidize distillate in cold by cautious addition of 23 mL F-free
30% H
2
O
2
to remove sulfites, let stand few min, and evaporate
portionwise in Pt dish containing excess (1015 mL) Ca(OH)
2
sus-
pension. Ash residue at 600C until clean. Proceed as in (b)(1), be-
ginning Transfer contents of dish to freshly prepared still, . . ..
2000 AOAC INTERNATIONAL
Handle pure oils by similar procedure: Use 10 g test portion with
25 mL H
2
SO
4
(1 + 1) and carry temperature at first to ca 170C to
saponify; thencarefullybringtemperature downto140Cwithdistill-
ing H
2
Oand collect 250 mLdistillate. (It will probably be necessary
to use higher reading thermometer for this procedure.) Oxidize distil-
late with 30% H
2
O
2
and evaporate to dryness after adding excess
Ca(OH)
2
suspension. Ash at 600Cand after brief preliminary ash pe-
riod remove dish, add little H
2
Oplus additional 12 mLof the H
2
O
2
to
remove sulfides, dry, and complete ashing. Proceed as in (b)(1), be-
ginning Transfer contents of dish to freshly prepared still, . . ..
(4) For aluminumand boron compounds.Al and Brepress evo-
lution of F. Isolate F by preliminary distillation at elevated tempera-
ture. For this purpose, weigh test portion, usually 510 g, into still,
add 25 mLH
2
SO
4
(1 +1), and conduct first distillation at 160165C
(special thermometer), collecting 300 mL distillate. Oxidize distil-
late with 30% H
2
O
2
as above, evaporate in Pt dish with excess
Ca(OH)
2
suspension, ash briefly at 600C, and proceed as in (b)(1),
beginning, Transfer contents of dishtofreshlypreparedstill, . . ..
F. Final Distillation
(Caution: See Appendix B, safety notes on distillation and
perchloric acid.)
Always make final distillation from HClO
4
, and take precau-
tions to secure low-acid distillate, C(a). Since interferences, such
as organic matter, phosphate, sulfate, etc., must be absent from
distillate, make distillation with careful temperature control in
presence of enough Ag salt to repress HCl evolution, B. It is well
to check distillates for presence of possible phosphate as in
E(b)(2), and where advisable, as in E(b)(4), to test for sulfate
with little dilute BaCl
2
solution. HClO
4
used in final distillation is
usually used in transferring ash to still, E(a). Few acid-alkali
washed beads are used to control bumping. (Use of powdered
SiO
2
does not appear necessary for microdetermination.)
To promote better recoveries, and to minimize and render con-
stant distillation blank discussed in B and G, prepare still by special
cleaning process before this transfer by treating it with hot 10%
NaOHsolution after each determination, flushing out with tap H
2
O,
and then rinsing with distilled H
2
O. Occasionally (at least once
daily, and especially after it has stood idle for any length of time),
give still additional treatment by boiling down 1520 mLH
2
SO
4
(1 +
1) until still is filled with fumes. Cool, pour off acid, treat with the
10% NaOH solution, and thoroughly rinse out. (Cleaning should be
especially meticulous after high-F or high-SiO
2
test portions have
beendistilled, andinsuchcases condenser shouldalsobe cleaned.)
At this stage, prepared test portion has been transferred to spe-
cially treated still, as directed above, for final isolation of F. Begin
distillation, and when temperature reaches 137C, keep at this point
(2C) by adding H
2
Ofromdropping funnel, C(a). Heat still at such
rate that all distillations require ca same time. (Time promotes uni-
formity in blank correction.) Collect distillate in 150 or 200 mL vol-
umetric flask. After few mL distillate collects, add 12 drops
p-nitrophenol indicator, D(e), and keep distillate alkaline to this in-
dicator (faintest perceptible yellow) by occasionally adding
12 drops 0.05M KOH from 10 mL buret during distillation while
swirling receiver. So regulate this addition of alkali that distillate is
neutralized (within 1 drop of alkali) as it approaches mark. Carefully
note volume alkali used. Dilute distillate to volume and mix thor-
oughly. Do not let F distillate stand more than few min before neu-
tralizing.
If sample contains such large amounts of Cl that bumping in still
cannot be controlled, dissolve ash of another sample, and acidify
slightly with HClO
4
. Dilute considerably and precipitate Cl in dish
with AgClO
4
solution, avoiding large excess. Filter through glass
filter, wash precipitate thoroughly with hot H
2
O, and evaporate fil-
trate and washings to dryness after adding excess (to alkalinity) of
Ca(OH)
2
suspension. Transfer residue to still with HClO
4
solution
and repeat distillation as above.
G. Titration
Place aliquot of final distillate in Nessler tube and mark S (test
solution). (Optimum F content for titration is 6070g for 100 mL
Nessler tubes and 3040g for 50 mLsize, and it is well to make ex-
ploratory titration on small aliquot to check approximate F content
of distillate. Larger tubes are necessary for precise results on low-F
foods.)
Add 0.05M HCl, 4.00 mL for 100 mL tubes and 2.00 mL for
50 mL size, and 1.00 mL H
2
NOHHCl solution. (For routine work
with 100 mL tubes, dissolve 1.0 g H
2
NOHHCl in 500 mL 0.04M
HCl and dilute to 500 mL. Then proper amount of both reagents can
be added in single operation with 5 mLpipet.) Dilute to ca 90 (or 40)
mL, mix well, then add alizarin indicator (2.00 or 1.00 mL), and mix
again. Always add and mix in H
2
NOHHCl before adding indicator.
Prepare blank tube B by adding proper amount HCl and
H
2
NOHHCl, and amount 0.05M KCl solution representing same
proportion of total volume of 0.05M KOH used to neutralize distil-
late as aliquot volume taken for test solution tube represents of total
distillate volume. (Thus, if 1.50 mL 0.05M KOH was used to neu-
tralize distillate of 150 mLand aliquot taken for tube S was 75 mL,
add 0.75 mL 0.05M KCl to tube B.) Dilute and mix, allowing
slightly more headspace than in test solution tube. Then add proper
volume alizarin indicator and mix.
Measure Th solution into tube S, mixing between additions, un-
til end point of about proper shade is reached. Dilute to mark, mix,
and check this end point shade. Note from curve, D(l), approximate
volume standard F solution corresponding to this volume Th solu-
tion, and add ca 0.5 mL less than this amount of standard F solution
to B. Mix; then add exactly same volume Th solution as was added
to S, duplicating approximate increments in which it was added
and number of mixings. Dilute nearly to mark and compare colors of
S and B. (If volume standard F solution added to B was prop-
erly chosen, this tube should be only slightly pinker in shade than
sample tube.)
Bleach B tube to exact match with tube S by adding more
standard F solution to B in increments of 12 drops, mixing gently
between additions. Dilute to mark for final comparison and observe
usual precautions of letting bubbles subside and of transposing tubes
when final comparisons are made. (At match-point, Fcontent of tube
S equals amount added to tube B.) Check this end point by add-
ing 12 drops excess standard F solution to tube B. Distinct
overbleach should develop.
Repeat titration on aliquots of different size to obtain total amount
of F distilled. If time is available, repeat entire determination with
different weight test portion.
For precise work, evaluation of reagent and of distillation blank is
necessary, B. Determine distillation blank by making several distil-
lations with prescribed amounts HClO
4
and AgClO
4
solutions from
freshly cleaned still, titrating distillate as above with as large aliquot
as practicable. Average of values found should be 3 g F. If
amounts found by individual blank determinations are too small to
2000 AOAC INTERNATIONAL
be determined accurately, make 5 separate distillations and evapo-
rate distillates, 150 mLeach time, successively in same Pt dish for fi-
nal distillation and average blank figure. Distillation and total
determination blanks can usually be combined by carrying run (with
same amounts of reagents and similar evaporation and ashing treat-
ment) through entire determination. Reagents and manipulations
should increase distillation blank but little.
Calculate total amount Fdistilled fromamount found in aliquot ti-
trated, subtract proper blank, and refer net figure to weight test por-
tion taken. If double distillation procedure was used, make
appropriate blank correction.
References: JAOAC 27, 90, 246(1944); 28, 277(1945);
33, 587(1950).
CAS-7782-41-4 (fluorine)
Revised: March 1996
2000 AOAC INTERNATIONAL