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二氧化钛(钛白粉)
二氧化钛(钛白粉)/ x# @9 M7 v2 g7 y! t9 K
* i9 e- }' J5 T, P' Y! l8 pJECFA关于二氧化钛(钛白粉)的结论3 A7 o0 d$ f7 W! K5 {
) d1 X1 K# w+ e- h" H& g$ m- I8 N摘要: 2006年JECFA关于二氧化钛的结论
: a# @ c. c1 ~/ z! e$ }ADI值:不作限制。
; e9 P* a. y2 U5 G Z* Q功能:着色剂
) V% l" y: V: A4 N9 T4 [9 S# \
# p# w$ V' }5 X( KTITANIUM DIOXIDE- i' [' E. D. R$ b: j! b$ t
Prepared at the 67th JECFA (2006) and published in FAO JECFA
, _' T: d. x( Z& o3 XMonographs 3 (2006), superseding specifications prepared at the 63rd- ~5 c; x6 J& C, J# ^1 W- T* _
JECFA (2004) and published in FNP 52 Add 12 (2004) and in the
5 A, C; O! L/ s3 x8 g( J3 pCombined Compendium of Food Additive Specifications, FAO JECFA3 |1 `" l7 A: H% w: P4 F# `; K
Monographs 1 (2005). An ADI “not limited” was established at the 13th0 ^/ A+ I, I. A
JECFA (1969).
( V$ A. e9 B3 L e) C" Q; `SYNONYMS1 C( u5 |2 \4 ]) ]7 _* l: q2 g3 f
Titania, CI Pigment white 6, CI (1975) No. 77891, INS No. 171+ }3 z. e* u' z% f, t
DEFINITION
! N ]" s6 J, {( y% P$ `4 OTitanium dioxide is produced by either the sulfate or the chloride
( a! S- K4 o& ~( {0 j4 Mprocess. Processing conditions determine the form (anatase or rutile# i+ t9 B- ^- S6 h3 f$ z3 f5 r
structure) of the final product.
; C$ b& S# |7 j' q. EIn the sulfate process, sulfuric acid is used to digest ilmenite (FeTiO3)
' Q' N0 ^8 r4 e/ M) G, r- Cor ilmenite and titanium slag. After a series of purification steps, the" s' P+ ?& y. X
isolated titanium dioxide is finally washed with water, calcined, and
7 }0 H) Q# u. M. n" [. n7 B8 lmicronized.9 j( E$ E% ]/ {7 g- T! I7 T
In the chloride process, chlorine gas is reacted with a titaniumcontaining
% W" a/ h! I! Z+ fmineral under reducing conditions to form anhydrous6 ]; ^& c8 z" e1 v
titanium tetrachloride, which is subsequently purified and converted to5 N6 \8 K- M0 e5 }# J
titanium dioxide either by direct thermal oxidation or by reaction with. {2 P! w9 A; Z% F V, p
steam in the vapour phase. Alternatively, concentrated hydrochloric* Y% ?- E) F9 `) t
acid can be reacted with the titanium-containing mineral to form a* y C" ^- {0 w9 | `9 x9 i
solution of titanium tetrachloride, which is then further purified and
: u4 N/ M2 K* h Xconverted to titanium dioxide by hydrolysis. The titanium dioxide is2 M4 n* P- @% x* ?; H
filtered, washed, and calcined./ o) m- K5 X6 P B0 e) [
Commercial titanium dioxide may be coated with small amounts of
% ^6 o4 _$ d- {3 [5 q3 A) walumina and/or silica to improve the technological properties of the
2 C* `; q9 a+ }( p' lproduct.
0 D3 S2 [! C* J/ p( p" B3 bC.A.S. number 13463-67-7
" I Q5 P* f8 w- I" e* Q0 j8 _* c8 NChemical formula TiO20 v; w# L( N9 j+ p' ^+ ^
Formula weight; A( o3 x' |7 V! ~# A
79.88+ J* r9 q0 C! r N) p4 R
Assay% K6 C8 W2 k7 F; y5 [$ m2 T2 K
Not less than 99.0% on the dried basis (on an aluminium oxide and$ T- Q( o% j7 r
silicon dioxide-free basis)% J& ]: @ @1 [" A( |7 D/ o
DESCRIPTION- D! f" v. Q5 ]/ t3 ~! O w( h. X
White to slightly coloured powder
$ l2 r3 E$ j F1 V" yFUNCTIONAL USES
8 r5 ~ a( q. \, s2 kColour
6 T5 i6 m3 G3 [( ^/ l' X1 `& H1 Y/ PCHARACTERISTICS7 P. A0 D/ ~2 j# F( I' }# |
IDENTIFICATION5 t6 e, z. @( w5 I2 m
Solubility (Vol. 4)
) \0 o! v2 \. m6 cInsoluble in water, hydrochloric acid, dilute sulfuric acid, and organic
5 y7 ^* e ]& l2 O. y& T A3 `5 ysolvents. Dissolves slowly in hydrofluoric acid and hot concentrated; A' ?! A* d$ o' A6 I. w, a+ D/ X
sulfuric acid.0 H, P$ C1 C* `: Z! N2 T
Colour reaction
# Y0 l; [' q& }: X/ b) d# n' j5 xAdd 5 ml sulfuric acid to 0.5 g of the sample, heat gently until fumes of! l% |4 \1 ]5 E& {$ {$ z k
sulfuric acid appear, then cool. Cautiously dilute to about 100 ml with! p9 h9 s( z2 S5 H" x) P
water and filter. To 5 ml of this clear filtrate, add a few drops of. [: t0 u# q) G
hydrogen peroxide; an orange-red colour appears immediately.
" H7 _7 U8 {2 kPURITY" m9 w5 O5 l8 U9 ?: j% c
Loss on drying (Vol. 4) Not more than 0.5% (105°, 3 h)9 ?7 G" c6 R$ l2 P& S
Loss on ignition (Vol. 4)1 ~1 ]- S f& K+ l9 {; Y. S. H
Not more than 1.0% (800o) on the dried basis
8 F# E8 g( }! i8 g' j6 J0 V9 hAluminium oxide and/or
8 I" _. B; l% u vsilicon dioxide
8 q' l% k; L) I0 E/ f1 I9 GNot more than 2%, either singly or combined
: \% a% S6 y+ J7 i# l4 PSee descriptions under TESTS. j% Z1 l' ^& ?5 c7 F, C6 w& X/ h2 |2 n
Acid-soluble substances Not more than 0.5%; Not more than 1.5% for products containing
' D! c" W0 l3 B( O6 Palumina or silica.8 A' j2 V, x E5 z$ h5 d f: F" M3 l
Suspend 5 g of the sample in 100 ml 0.5 N hydrochloric acid and
5 |* X; n6 {/ G, A0 N. o4 G6 @place on a steam bath for 30 min with occasional stirring. Filter' o! F& }# L6 ]/ Q
through a Gooch crucible fitted with a glass fibre filter paper. Wash
1 ~; o c9 t6 kwith three 10-ml portions of 0.5 N hydrochloric acid, evaporate the
2 e) `5 h' F3 t4 E! Lcombined filtrate and washings to dryness, and ignite at a dull red
( [4 M# I( |1 V9 j* Vheat to constant weight.3 w: _4 d' C. X4 W7 V5 h1 k8 N
Water-soluble matter
0 T A0 s2 t* \# m) I, E9 z(Vol. 4)+ l& I0 q' m7 C% b' a% ]
Not more than 0.5%; f7 u, S6 b4 ]# k0 G5 f5 m
Proceed as directed under acid-soluble substances (above), using
7 P0 m! i+ k1 @: G& \water in place of 0.5 N hydrochloric acid.; V9 n* a2 `8 ^9 m
Impurities soluble in 0.5 N' r/ D( l0 B# K, k5 s( }
hydrochloric acid! c/ j0 ?4 N+ V. T' r' I+ ~
Antimony Not more than 2 mg/kg( C/ H h, l% v' O5 G" @& i
See description under TESTS F' m) \4 t# m- V- |1 K/ f) v- V7 g
Arsenic Not more than 1 mg/kg- Y+ Q' ~! X5 z- ~, e. H i8 q
See description under TESTS- \7 x8 S% L9 Z0 Y
Cadmium Not more than 1 mg/kg1 Z ~4 V! x3 Q! @2 E
See description under TESTS$ V v5 o3 [, ?9 `- h. D
Lead
, O3 n$ u4 S% |5 U- oNot more than 10 mg/kg
/ L( t& I; B" P8 B- A9 gSee description under TESTS' q( Y" C$ g7 L9 G6 d( S5 ?
Mercury (Vol. 4) Not more than 1 mg/kg
* i( L2 t- ]5 x' r/ G* IDetermine using the cold vapour atomic absorption technique. Select a
( E3 V$ N; |2 rsample size appropriate to the specified level7 s' f0 S) V5 D" s0 w
TESTS
& m0 ?3 H5 Y/ `PURITY TESTS
2 V2 X) Y3 W5 K( s9 ]: ~Impurities soluble in 0.5 N+ C: a$ J; m8 e* x7 Z+ {
hydrochloric acid- r' {; I* u, i! D! ~' H
Antimony, arsenic,
6 B0 u$ _! j% h! [5 ~! ?1 ?4 D- Hcadmium and lead
+ `8 a. ^! o1 E0 {' Q, }(Vol.4)
. o) s: k$ R5 t0 J* sTransfer 10.0 g of sample into a 250-ml beaker, add 50 ml of 0.5 N* @/ c: e5 D; K3 k1 i) \
hydrochloric acid, cover with a watch glass, and heat to boiling on a0 Q: L! y( v. m8 D9 e7 ?* Y
hot plate. Boil gently for 15 min, pour the slurry into a 100- to 150-ml) \5 o3 ?: T' L& T& o9 ~% q
centrifuge bottle, and centrifuge for 10 to 15 min, or until undissolved
. {7 @. v+ q0 O/ K+ N) Zmaterial settles. Decant the supernatant extract through a Whatman
1 l) M8 Q: W; X! n3 o+ _/ J) o: bNo. 4 filter paper, or equivalent, collecting the filtrate in a 100-ml
6 {. z: Q6 n2 h; ^9 ^% \: L0 vvolumetric flask and retaining as much as possible of the undissolved
& f! e D" G9 J. imaterial in the centrifuge bottle. Add 10 ml of hot water to the original2 i; s5 U2 S/ y- x/ s
beaker, washing off the watch glass with the water, and pour the
* f. ~2 N# C& f' q, |contents into the centrifuge bottle. Form a slurry, using a glass stirring
/ g0 I" Y; z2 c2 S# {% Jrod, and centrifuge. Decant through the same filter paper, and collect
' _& m; B8 ]2 O; Sthe washings in the volumetric flask containing the initial extract.
. ]" C6 B; h: [Repeat the entire washing process two more times. Finally, wash the2 S0 p l$ f- B5 l: Z/ \
filter paper with 10 to 15 ml of hot water. Cool the contents of the flask
9 D5 ?; z. q0 L8 B' _* yto room temperature, dilute to volume with water, and mix.
% ]5 F' [7 E& p, fDetermine antimony, cadmium, and lead using an AAS/ICP-AES) w% C6 W" x' _. B. {
technique appropriate to the specified level. Determine arsenic using the* \% U, d$ q5 p7 G' f
ICP-AES/AAS-hydride technique. Alternatively, determine arsenic using
- t0 ~$ K/ w2 M' Z$ sMethod II of the Arsenic Limit Test, taking 3 g of the sample rather than
4 H2 M- Y) ]. U5 I$ X1 g. The selection of sample size and method of sample preparation
1 f7 V2 `: ?7 O4 o3 mmay be based on the principles of the methods described in Volume 4.
/ k5 |. y/ r% p0 QAluminium oxide Reagents and sample solutions' ]. E; `1 N- @0 a# o6 t4 a8 _
0.01 N Zinc Sulfate; {$ R" b3 b1 L7 J5 s
Dissolve 2.9 g of zinc sulfate (ZnSO4 ? 7H2O) in sufficient water to$ @8 V$ \8 T6 b" N8 B1 F4 i
make 1000 ml. Standardize the solution as follows: Dissolve 500 mg
) ?! d! @. m9 J/ J/ F7 n: ?of high-purity (99.9%) aluminium wire, accurately weighed, in 20 ml of
4 a1 a7 z- N l4 P {5 nconcentrated hydrochloric acid, heating gently to effect solution, then' U9 e- J% E0 r+ F" F! `
transfer the solution into a 1000-ml volumetric flask, dilute to volume
$ t! Q! B7 }7 C7 U$ r4 Pwith water, and mix. Transfer a 10 ml aliquot of this solution into a 500
$ C1 N. ] ]5 l8 w' S/ P4 yml Erlenmeyer flask containing 90 ml of water and 3 ml of+ J/ G% p: M8 j- z K# L
concentrated hydrochloric acid, add 1 drop of methyl orange TS and( m5 q B/ F# L' q2 g9 e
25 ml of 0.02 M disodium ethylenediaminetetraacetate (EDTA) Add,
( `8 Y8 X2 C6 f% Sdropwise, ammonia solution (1 in 5) until the colour is just completely6 D, i; n' P. @$ C9 o i: d- ]4 R
changed from red to orange-yellow. Then, add: D/ o7 u0 {# a
(a): 10 ml of ammonium acetate buffer solution (77 g of
! ? W l0 S7 u) B4 C$ m; Gammonium acetate plus 10 ml of glacial acetic acid, dilute to' ^; C! M6 [; |/ J5 P& e
1000 ml with water) and' n5 p* d$ r0 R
(b): 10 ml of diammonium hydrogen phosphate solution (150 g
3 }+ o& X1 p; E; O, }4 U. Vof diammonium hydrogen phosphate in 700 ml of water,
! B* g3 H! J/ H; badjusted to pH 5.5 with a 1 in 2 solution of hydrochloric acid,, Q2 g& Z7 c7 _9 N6 V7 O) j
then dilute to 1000 ml with water).
9 b b8 A& F, m) k" p! tBoil the solution for 5 min, cool it quickly to room temperature in a
& e# R: ~0 Q! Y( }stream of running water, add 3 drops of xylenol orange TS, and mix.; u1 N. Y3 B H# x) }
Using the zinc sulfate solution as titrant, titrate the solution to the first- R9 p5 Z6 q3 B. _; a! U1 \$ [
yellow-brown or pink end-point colour that persists for 5-10 sec. (Note:% f" {" o5 z' m0 f
This titration should be performed quickly near the end-point by
! ^* f1 ^. }) B( p& n9 d3 Ladding rapidly 0.2 ml increments of the titrant until the first colour
7 h$ E/ S" g! n8 ~7 f) g, dchange occurs; although the colour will fade in 5-10 sec, it is the true0 [+ Z5 u! L0 {
end-point. Failure to observe the first colour change will result in an
. i! D0 w, U0 S' C% Kincorrect titration. The fading end-point does not occur at the second$ s+ n) i) D# x" v
end-point.)% Q7 p0 U! D! ?3 i& t! R, X1 Z
Add 2 g of sodium fluoride, boil the mixture for 2-5 min, and cool in a7 h/ R3 i6 s+ `# G3 G% u& g! s
stream of running water. Titrate this solution, using the zinc sulfate
5 R+ I9 ]; Z5 _* ~7 X. x" Zsolution as titrant, to the same fugitive yellow-brown or pink end-point7 y8 B! v( _4 `; P
as described above.
2 Z9 r* T/ H+ {5 sCalculate the titre T of zinc sulfate solution by the formula:# z4 u! J9 Z; _) o }1 F
T = 18.896 W / V
! ^, f% I% B1 ?- j. |3 hwhere
& l, _* H- d( u) z' l$ f0 }* Y% W. }1 iT is the mass (mg) of Al2O3 per ml of zinc sulfate solution
/ K7 N! |$ b k D8 U+ HW is the mass (g) of aluminium wire* L, w8 R/ T9 \' @! Y8 A1 V
V is the ml of the zinc sulfate solution consumed in the2 Z, n, n+ E' \" G! @+ N
second titration" X1 ?4 J; _: U5 U" n
18.896 = (R × 1000 mg/g × 10 ml/2)/1000 ml and+ b) N9 y9 q& N. @8 m
R is the ratio of the formula weight of aluminium oxide to8 `- f( D. j2 ~8 g
that of elemental aluminium.
j' E) G, y* }0 N( e7 YSample Solution A
8 N v3 E! ?- Y0 F1 X8 F, PAccurately weigh 1 g of the sample and transfer to a 250-ml high-silica' H7 \- m: v* t& O
glass Erlenmeyer flask. Add 10 g of sodium bisulfate (NaHSO4 ? H2O).
5 z5 N- H' A+ O) ^6 I(Note: Do not use more sodium bisulfate than specified, as an excess
: ^ C: Q8 \8 x% Z$ u% l, o0 dconcentration of salt will interfere with the EDTA titration later on in the, W$ P8 a. ^& B: o8 r
procedure.) Begin heating the flask at low heat on a hot plate, and& F6 x8 B k. t7 a& B5 Y2 A
then gradually raise the temperature until full heat is reached.) C) K1 I7 x% E1 j ?
(Caution: perform this procedure in a well ventilated area. ) When/ D9 }& @' ~4 W) s& B% t6 |7 e
spattering has stopped and light fumes of SO3 appear, heat in the full
/ l) X6 j$ g4 |8 b. Kflame of a Meeker burner, with the flask tilted so that the fusion of the @' R' @9 U+ G2 Z/ ~
sample and sodium bisulfate is concentrated at one end of the flask.
# r3 T! ^* B/ o0 R0 u* ?, \Swirl constantly until the melt is clear (except for silica content), but
. }+ [9 z W/ dguard against prolonged heating to avoid precipitation of titanium! h' A& u3 T$ C, Y, H% R
dioxide. Cool, add 25 ml sulfuric acid solution (1 in 2), and heat until
) A0 m$ j8 x3 p6 G" ythe mass has dissolved and a clear solution results. Cool, and dilute to
1 T- a0 g( b8 v# A* i2 ?! I120 ml with water. Introduce a magnetic stir bar into the flask.5 K; _3 e3 `1 D
Sample Solution B# N: @2 r5 I( c8 l; _
Prepare 200 ml of an approximately 6.25 M solution of sodium+ g; t/ o% @" F' g
hydroxide. Add 65 ml of this solution to Sample Solution A, while4 _$ c$ N; K. m. I& r6 q( _' V
stirring with the magnetic stirrer; pour the remaining 135 ml of the- O2 }* m. |* t) [
alkali solution into a 500-ml volumetric flask., m1 m0 i$ |& U5 Z$ T1 M j1 {5 w
Slowly, with constant stirring, add the sample mixture to the alkali
) V$ B8 n2 \( }4 ~- Q" K4 zsolution in the 500-ml volumetric flask; dilute to volume with water,; {) y* Q8 c9 t( D) j d0 R$ O
and mix. (Note: If the procedure is delayed at this point for more than
; L) V1 Z. r+ | j. Q3 M8 b% H2 hours, store the contents of the volumetric flask in a polyethylene% m3 `( n$ C: ^
bottle.) Allow most of the precipitate to settle (or centrifuge for 5 min),
/ x/ x1 }$ h! q3 ~- A7 k2 bthen filter the supernatant liquid through a very fine filter paper. Label4 S% ]9 _$ u% n7 E% N1 @. M/ T! z
the filtrate Sample Solution B.' {# @( ]% Y- a* U
Sample Solution C: c- ]. I, B. M" c4 R
Transfer 100 ml of the Sample Solution B into a 500-ml Erlenmeyer
# h" _) C0 W6 E. s, jflask, add 1 drop of methyl orange TS, acidify with hydrochloric acid: U9 a% E2 L7 F
solution (1 in 2), and then add about 3 ml in excess. Add 25 ml of 0.02
/ E: c+ g- D4 D' A. I+ ZM disodium EDTA, and mix. [Note: If the approximate Al2O3 content is
6 K' p3 G/ I: g: ~known, calculate the optimum volume of EDTA solution to be added
' _( j4 k) J7 \( r; j9 a0 ]by the formula: (4 x % Al2O3) + 5.] W; f' e" E2 h( I9 y3 V
Add, dropwise, ammonia solution (1 in 5) until the colour is just
" L$ ?: w& x0 X$ Gcompletely changed from red to orange-yellow. Then add10 ml each: n% ]% o3 e" {7 v8 {$ C: J
of Solutions 1 and 2 (see above) and boil for 5 min. Cool quickly to4 j: r) r/ F+ Z s& x9 }
room temperature in a stream of running water, add 3 drops of xylenol
! `" M* D* C" d/ e. x8 w. Sorange TS, and mix. If the solution is purple, yellow-brown, or pink,- g- c+ v c5 o# k, m5 v/ R
bring the pH to 5.3 - 5.7 by the addition of acetic acid. At the desired( Q, s" b3 Q6 R, s
pH, a pink colour indicates that not enough of the EDTA solution has
4 o4 w9 Z# F Y3 f* K6 Bbeen added, in which case, discard the solution and repeat this6 ]% M6 S9 _* f+ ]+ k
procedure with another 100 ml of Sample Solution B, using 50 ml,$ s7 \/ s. r y) v+ @; H! Z
rather than 25 ml, of 0.02 M disodium EDTA.
8 q p7 X# u% ]. T! h( M1 v% CProcedure. f4 g, t2 U& L9 a) Y9 \8 x3 w
Using the standardized zinc sulfate solution as titrant, titrate Sample1 ^6 p% K& w7 w- q$ ~2 @5 J
Solution C to the first yellow-brown or pink end-point that persists for
* r0 Q8 z+ }/ |& s# O' a5 }# [# n5-10 sec. (Important: See Note under “0.01 Zinc sulfate”.) This first* q, l. z# U4 {+ f( P! N
titration should require more than 8 ml of titrant, but for more accurate
1 E. w$ Z! z7 l% U" @work a titration of 10-15 ml is desirable.
2 w0 i; m# b" E2 _. AAdd 2 g of sodium fluoride to the titration flask, boil the mixture for 2-5
+ u/ {7 u: {; A& r `min, and cool in a stream of running water. Titrate this solution, using
8 z+ z4 M1 l& ~: k$ b5 l( jthe standardized zinc sulfate solution as titrant, to the same fugitive0 W4 Y5 d Y2 ^% U+ }2 n1 E. T
yellow-brown or pink end-point as described above.$ w* _7 A# j' s6 M+ t/ r
Calculation:1 ~% M l2 i4 y" g L k6 |. z# E
Calculate the percentage of aluminium oxide (Al2O3) in the sample' w S& z6 |8 J" _ q9 N
taken by the formula:' q/ a1 _( \2 w9 q2 g: q( k) y/ D: v
% Al2O3 = 100 × (0.005VT)/S
+ s6 M, i+ \% v2 U) }$ mwhere
) j! |0 a# D9 _; _2 W2 R' DV is the number of ml of 0.01 N zinc sulfate consumed in8 d% l0 t2 z- Z% }! D4 d+ @* g
the second titration,
8 b7 E3 I1 Y4 b3 j3 M4 ET is the titre of the zinc sulfate solution,& i" `2 P. Q5 a" y) ?
S is the mass (g) of the sample taken, and
: q3 c2 q6 z0 H0.005 = 500 ml / (1000mg/g × 100 ml).3 d- x( E+ ?# N! U2 Q; d) [6 \
Silicon dioxide Accurately weigh 1 g of the sample and transfer to a 250-ml high-silica
. l: \! Y! k# E8 D: |6 N( A" d; a6 wglass Erlenmeyer flask. Add 10 g of sodium bisulfate (NaHSO4 ? H2O).
7 a) l% M$ B" Z! f* f; t+ \Heat gently over a Meeker burner, while swirling the flask, until
# x+ T7 I9 O4 j, sdecomposition and fusion are complete and the melt is clear, except( J! c$ E0 p3 M/ B4 Z. w: Y
for the silica content, and then cool. (Caution: Do not overheat the
5 O2 F* F; Q3 E- S, Ocontents of the flask at the beginning, and heat cautiously during- T" }8 [2 l( b
fusion to avoid spattering.)
: o0 A' }9 A6 rTo the cooled melt add 25 ml of sulfuric acid solution (1 in 2) and heat
3 K L, _: m& ycarefully and slowly until the melt is dissolved. Cool, and carefully add; |9 q) s: @% Y7 M* J6 {- r- g
150 ml of water by pouring very small portions down the sides of the' s1 X( x% q" |, p& H
flask, with frequent swirling to avoid over-heating and spattering. Allow
& o# k5 l4 K1 O a, Z1 `0 B/ ithe contents of the flask to cool, and filter through fine ashless filter8 M9 Z/ B) @* I; {
paper, using a 60 degree gravity funnel. Rinse out all the silica from
, G) n. D' n$ x } r7 _& x) _the flask onto the filter paper with sulfuric acid solution (1 in 10).
9 M# Z* o3 ]- YTransfer the filter paper and its contents into a platinum crucible, dry in2 m8 }! ^5 S( H& X2 o2 O& f' Y
an oven at 1200, and heat the partly covered crucible over a Bunsen
/ i' Y% f$ A9 ^5 Oburner. To prevent flaming of the filter paper, first heat the cover from
& @( ^9 V) L% m$ K* u. U4 y, Labove, and then the crucible from below.% }# C% c; y7 y, x: u
When the filter paper is consumed, transfer the crucible to a muffle3 { Y$ o- F9 p2 O" b* G
furnace and ignite at 1000o for 30 min. Cool in a desiccator, and B# c; x3 _) C
weigh. Add 2 drops of sulfuric acid (1 in 2) and 5 ml of concentrated1 ~; |& K* ^4 D" d7 R! U& z" V7 U
hydrofluoric acid (sp.gr. 1.15), and carefully evaporate to dryness, first
7 ^7 @: y! _9 J- K" _' U+ Qon a low-heat hot plate (to remove the HF) and then over a Bunsen
& z9 p, T9 ?4 B/ v0 ?burner (to remove the H2SO4). Take precautions to avoid spattering,* D$ u+ I' x0 T% J; k& w
especially after removal of the HF. Ignite at 1000o for 10 min, cool in a
) [! ]1 z' o' a( C* C* hdesiccator, and weigh again. Record the difference between the two& o3 {7 B* W, F- W6 C
weights as the content of SiO2 in the sample./ Z+ C; ]( a" I
METHOD OF ASSAY2 @- c$ y( p$ Z: s8 L
Accurately weigh about 150 mg of the sample, previously dried at 105o0 i3 H; k$ i2 p; T- B1 m* Q
for 3 hours, and transfer into a 500-ml conical flask. Add 5 ml of water
" h0 C8 D- y2 V/ K8 R8 Uand shake until a homogeneous, milky suspension is obtained. Add 30
) o, v5 U0 T( n. N6 Hml of sulfuric acid and 12 g of ammonium sulfate, and mix. Initially
% A- a/ I' |" f; ]( iheat gently, then heat strongly until a clear solution is obtained. Cool,$ g' ~8 c, Q* k* _" A( U
then cautiously dilute with 120 ml of water and 40 ml of hydrochloric" c" F+ q/ u+ j q
acid, and stir. Add 3 g of aluminium metal, and immediately insert a" C5 u' ]; n2 v, S/ X5 {
rubber stopper fitted with a U-shaped glass tube while immersing the
" q3 U( K! U# eother end of the U-tube into a saturated solution of sodium
0 F) u6 i) Q' ?* s/ D( V0 S& \bicarbonate contained in a 500-ml wide-mouth bottle, and generate4 p6 J9 [0 M' R8 x
hydrogen. Allow to stand for a few minutes after the aluminium metal0 b* r2 F# P2 Y6 d2 l9 k
has dissolved completely to produce a transparent purple solution.2 |# u8 v% @; N2 b/ H d! w2 ~
Cool to below 50o in running water, and remove the rubber stopper6 s4 t2 m- n" o: ]
carrying the U-tube. Add 3 ml of a saturated potassium thiocyanate
7 T& x- [) t* U) V. L( Asolution as an indicator, and immediately titrate with 0.2 N ferric( r: E7 K9 P9 l# w* r: L$ e
ammonium sulfate until a faint brown colour that persists for 30
9 j" M' @, q. t$ x% ^" oseconds is obtained. Perform a blank determination and make any
. Q6 w* j7 |( d! q4 F E* rnecessary correction. Each ml of 0.2 N ferric ammonium sulfate is
2 P( `! ~+ |2 h% P' B6 F6 Kequivalent to 7.990 mg of TiO2.3 u/ t( q4 w0 G5 p# c
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