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二氧化钛(钛白粉)
二氧化钛(钛白粉)
& ~$ U: I$ ?* P) F: c
3 v L4 f( T& r$ FJECFA关于二氧化钛(钛白粉)的结论2 R u! s9 y& Q) A2 m
& R, w; }' p' g" ~/ [
摘要: 2006年JECFA关于二氧化钛的结论$ }( _* i% E2 t: Q; Y
ADI值:不作限制。
n- T2 B2 J2 C" _; G- x功能:着色剂
% l' p! L! S" u* Q: ^8 F V8 u. A y0 O8 z9 R1 j& m
TITANIUM DIOXIDE( ?- g/ }6 }) [% E
Prepared at the 67th JECFA (2006) and published in FAO JECFA
5 W: w3 Q- ?" G3 d& WMonographs 3 (2006), superseding specifications prepared at the 63rd( X Y3 u: y, |! f; m" N3 [
JECFA (2004) and published in FNP 52 Add 12 (2004) and in the
3 G0 {$ o! Q2 B) @Combined Compendium of Food Additive Specifications, FAO JECFA
& J& N: m1 G1 S1 J2 L* E) G. KMonographs 1 (2005). An ADI “not limited” was established at the 13th) u1 w! m* e% d3 f* r+ c
JECFA (1969).0 F) f. I! @! e$ E
SYNONYMS
& D4 P! N' S( L' z: LTitania, CI Pigment white 6, CI (1975) No. 77891, INS No. 171: n1 \! J# v+ V3 [+ {3 l
DEFINITION2 a4 K! J+ c3 L0 n; t
Titanium dioxide is produced by either the sulfate or the chloride
q# f/ Y) Z3 |process. Processing conditions determine the form (anatase or rutile$ v/ ?2 Y9 r( E4 P% q$ P" w* i
structure) of the final product.
4 m: ?# [' [* \$ v$ F1 B+ V6 ~In the sulfate process, sulfuric acid is used to digest ilmenite (FeTiO3)1 ]: Z$ U3 N# d6 ?
or ilmenite and titanium slag. After a series of purification steps, the
1 }0 h3 H2 o5 \' [+ }isolated titanium dioxide is finally washed with water, calcined, and
" |. g& n) G" F' B x2 Gmicronized.$ S# M2 C0 h: p0 `
In the chloride process, chlorine gas is reacted with a titaniumcontaining
- ]( q$ P- E: T0 E* ?$ D7 Jmineral under reducing conditions to form anhydrous
3 y+ v3 [) i( w1 u" k( a9 Ztitanium tetrachloride, which is subsequently purified and converted to3 W4 M1 r- E- x4 Q* t3 k
titanium dioxide either by direct thermal oxidation or by reaction with, [9 w1 B r4 F% M k. t8 s
steam in the vapour phase. Alternatively, concentrated hydrochloric
5 M& B3 w5 _0 l7 Bacid can be reacted with the titanium-containing mineral to form a
0 f' j6 T& y& S1 F! N4 N7 x) Nsolution of titanium tetrachloride, which is then further purified and9 i+ L0 x/ L7 q0 \: r
converted to titanium dioxide by hydrolysis. The titanium dioxide is1 M( C. G! q& ~8 S8 E- w
filtered, washed, and calcined.: P4 S) x5 V; b
Commercial titanium dioxide may be coated with small amounts of, e8 C+ i) u) l S& T
alumina and/or silica to improve the technological properties of the6 ]6 ~/ A& P, C: h& ]: l, k
product.
' V8 [- W1 R; mC.A.S. number 13463-67-7/ s! d8 M$ Q# f1 H- g9 F. t! Z1 A
Chemical formula TiO28 @" {8 @# @* V8 [7 L& [- T B# u
Formula weight
' F; G a' k- c+ P7 _3 l1 e79.88
: |6 p4 @- a' } A. l8 ^- V+ O% |* D8 ?Assay
/ F! u% O5 r! m2 g$ M. YNot less than 99.0% on the dried basis (on an aluminium oxide and
: ^( b5 v, i- }% V% r0 v# esilicon dioxide-free basis)
# g; F' B& s, A" bDESCRIPTION
. E& D- |" ^" v# h8 C3 DWhite to slightly coloured powder8 x7 \% v3 {; u
FUNCTIONAL USES
2 l2 O8 o) O9 {3 |+ ZColour) D9 Y( \) {9 c+ b9 _, g- S
CHARACTERISTICS6 D& a, S1 h# ~5 l
IDENTIFICATION- ~" D1 d6 D/ `. R6 F3 u, Z
Solubility (Vol. 4)
: I7 x- w3 _; ZInsoluble in water, hydrochloric acid, dilute sulfuric acid, and organic5 \; v3 ]( C' N! Q6 n% L# y. W( H
solvents. Dissolves slowly in hydrofluoric acid and hot concentrated* g9 U9 s; e% Y0 H5 x" y, ~
sulfuric acid.
! R6 V4 @( U, ~, ^Colour reaction0 p0 X; Z- i+ Q9 c; F& Q! L- u
Add 5 ml sulfuric acid to 0.5 g of the sample, heat gently until fumes of1 V0 j/ J: @$ ~+ ?: y
sulfuric acid appear, then cool. Cautiously dilute to about 100 ml with
* ~% D; H7 ?! C6 }8 b- lwater and filter. To 5 ml of this clear filtrate, add a few drops of" Z3 E6 Q" @3 j( [
hydrogen peroxide; an orange-red colour appears immediately.
2 c2 R' m) [9 T5 d F+ A$ wPURITY9 L9 y' E9 Z1 o* }. R9 P
Loss on drying (Vol. 4) Not more than 0.5% (105°, 3 h)
# C# L+ S' N7 S! \- c7 n" T9 Y& K% DLoss on ignition (Vol. 4)
" ]9 @! g1 Q+ Y, J9 sNot more than 1.0% (800o) on the dried basis
, m6 R+ g0 X6 l, mAluminium oxide and/or
+ v w+ c/ E1 i( V; L- b. }: s' G! Qsilicon dioxide
4 r8 Y/ q2 _' l# yNot more than 2%, either singly or combined
7 v* X2 D6 ~. T* JSee descriptions under TESTS
; y1 V' }7 W' mAcid-soluble substances Not more than 0.5%; Not more than 1.5% for products containing
2 K% O3 S6 m/ n/ g5 Lalumina or silica.
( |; S; s) q3 n8 W* P/ PSuspend 5 g of the sample in 100 ml 0.5 N hydrochloric acid and
5 F& U) j, x4 c" xplace on a steam bath for 30 min with occasional stirring. Filter
: S: m3 \2 M) ~& c) H+ zthrough a Gooch crucible fitted with a glass fibre filter paper. Wash! I( Q- h9 G5 J( r
with three 10-ml portions of 0.5 N hydrochloric acid, evaporate the2 o. D3 N: ^8 M; `
combined filtrate and washings to dryness, and ignite at a dull red
4 D7 S* a2 O' L0 D' P8 fheat to constant weight.
- g; T$ b5 ~, e5 r- YWater-soluble matter
: ?# B f+ t& p, G6 ^* ^, [(Vol. 4)
6 N% L9 R$ l G" S6 V9 R- q. dNot more than 0.5%1 V6 W) {& W0 h( ~# i: f
Proceed as directed under acid-soluble substances (above), using' i- H( A" i* d3 Y8 x7 u
water in place of 0.5 N hydrochloric acid.9 {7 u: e" B8 p7 q6 q
Impurities soluble in 0.5 N
" `8 F f0 H' y! j: Thydrochloric acid, Z1 o& F9 l8 P: v1 M! C% A/ s
Antimony Not more than 2 mg/kg7 }. @ s- p: j+ r0 m- O' t
See description under TESTS4 B: T9 Y4 P; T7 d. P/ K
Arsenic Not more than 1 mg/kg. [6 X: J h2 W8 P) W
See description under TESTS
* M' M' ^6 D, ^2 x; {3 [* cCadmium Not more than 1 mg/kg
8 W# S# } G0 T: ^% zSee description under TESTS* t& }6 {4 @/ `: V- E# F0 ?, ~
Lead
- ]7 x9 `$ b* _" ZNot more than 10 mg/kg
8 x! ]3 z, K' H3 k" k7 x# oSee description under TESTS6 ^8 P" ^# t/ E
Mercury (Vol. 4) Not more than 1 mg/kg
: s- E1 c# g/ u) `0 TDetermine using the cold vapour atomic absorption technique. Select a
5 T1 z. y* D6 i/ ssample size appropriate to the specified level
: o' J4 ?* O" G* ^' NTESTS
' Z, i4 Q0 N0 x- M$ wPURITY TESTS. Q& n- h- V, O8 s" H0 c ^
Impurities soluble in 0.5 N: Q P( ?5 \$ N5 M5 W6 f2 _
hydrochloric acid
$ T6 u" o5 B8 Z- qAntimony, arsenic,
) J5 Z4 a2 k7 h1 M" Z5 f/ ?+ }9 O5 Y3 c- k1 Fcadmium and lead% L; a& L( R8 A0 T; }1 G
(Vol.4)% \$ {$ o5 f- x$ H% @4 y
Transfer 10.0 g of sample into a 250-ml beaker, add 50 ml of 0.5 N0 O4 k* t Y, D+ m: M
hydrochloric acid, cover with a watch glass, and heat to boiling on a
- Z9 _$ X, x; K `) bhot plate. Boil gently for 15 min, pour the slurry into a 100- to 150-ml, G+ X6 B" w, n/ Y( ^/ m! t0 F0 u; I" `
centrifuge bottle, and centrifuge for 10 to 15 min, or until undissolved
- a* e, C" r5 k6 Cmaterial settles. Decant the supernatant extract through a Whatman8 `" C; @4 \ I+ X$ R3 V$ [6 V
No. 4 filter paper, or equivalent, collecting the filtrate in a 100-ml
, s8 r0 _5 r9 b, T8 O2 e. Bvolumetric flask and retaining as much as possible of the undissolved
7 L! O9 Q; A: I$ W/ l* omaterial in the centrifuge bottle. Add 10 ml of hot water to the original& n4 q c+ Y- _2 X, {
beaker, washing off the watch glass with the water, and pour the
) `& t' B4 D- Ncontents into the centrifuge bottle. Form a slurry, using a glass stirring0 E7 p: D g* v0 a" B
rod, and centrifuge. Decant through the same filter paper, and collect+ V7 r1 _7 L4 B3 Q( U- i
the washings in the volumetric flask containing the initial extract.
* O7 B, v# h' Z5 aRepeat the entire washing process two more times. Finally, wash the
8 y3 Z2 c% i5 S$ b! A3 U8 Hfilter paper with 10 to 15 ml of hot water. Cool the contents of the flask* _+ H* z7 @- L0 n) S5 @
to room temperature, dilute to volume with water, and mix.
4 u1 J3 p9 e' ], f2 T* HDetermine antimony, cadmium, and lead using an AAS/ICP-AES( `7 h: r8 K- K" I, a, g s0 L
technique appropriate to the specified level. Determine arsenic using the# U9 K3 O# F3 `2 g* G1 E; e
ICP-AES/AAS-hydride technique. Alternatively, determine arsenic using
8 `6 \4 a( R& ]5 h) S* FMethod II of the Arsenic Limit Test, taking 3 g of the sample rather than
* J/ G8 F$ o/ p& H1 g. The selection of sample size and method of sample preparation( I3 y0 m7 B- N# Y' M
may be based on the principles of the methods described in Volume 4.9 w9 e1 n% V. c; d7 @6 X; m. N
Aluminium oxide Reagents and sample solutions$ y3 J$ _* [( P6 ^' F0 ?0 w) k6 I
0.01 N Zinc Sulfate
. R2 @3 F8 G h1 o8 p1 TDissolve 2.9 g of zinc sulfate (ZnSO4 ? 7H2O) in sufficient water to* m5 y/ O2 @4 a7 Q+ t2 A
make 1000 ml. Standardize the solution as follows: Dissolve 500 mg
& W$ @) s5 ` d$ @* r2 Q' F. Dof high-purity (99.9%) aluminium wire, accurately weighed, in 20 ml of9 m8 i% |/ ?% M' i* r* K) I; V6 Q
concentrated hydrochloric acid, heating gently to effect solution, then! g* i/ c+ y N1 K" L0 ~1 `
transfer the solution into a 1000-ml volumetric flask, dilute to volume
! G& S) K# R) z1 uwith water, and mix. Transfer a 10 ml aliquot of this solution into a 5004 G8 Y- ^" _6 K3 j$ `- N: M' A0 _9 F& F) e3 p
ml Erlenmeyer flask containing 90 ml of water and 3 ml of P2 S9 H* k( p" V2 N
concentrated hydrochloric acid, add 1 drop of methyl orange TS and
9 [2 O+ `# l# r# M6 c9 T2 a25 ml of 0.02 M disodium ethylenediaminetetraacetate (EDTA) Add,
' i$ T3 w% a( B( b6 Edropwise, ammonia solution (1 in 5) until the colour is just completely' c* I3 A: r. W' F9 z B7 J2 z
changed from red to orange-yellow. Then, add:' ]; c( C t3 A9 p$ L( T
(a): 10 ml of ammonium acetate buffer solution (77 g of
) ]6 A8 O5 e/ Y% o2 V v3 qammonium acetate plus 10 ml of glacial acetic acid, dilute to
- I, I2 p" a( c, i( R( \2 w' T; Z1000 ml with water) and
% V6 Q/ h; h$ Z. F(b): 10 ml of diammonium hydrogen phosphate solution (150 g* m0 P" @7 k5 l" Q9 r! q; t
of diammonium hydrogen phosphate in 700 ml of water,/ r' f9 N" J( T o8 u$ }1 m
adjusted to pH 5.5 with a 1 in 2 solution of hydrochloric acid,; |' K) s, r y7 A: x! `
then dilute to 1000 ml with water).6 @4 Q+ M0 Y) R, X$ `
Boil the solution for 5 min, cool it quickly to room temperature in a
; o" o1 F% U$ z+ B3 }& Ustream of running water, add 3 drops of xylenol orange TS, and mix.
! n+ V1 L8 f# p# E* o( }Using the zinc sulfate solution as titrant, titrate the solution to the first
( w1 O5 B4 e% C! Hyellow-brown or pink end-point colour that persists for 5-10 sec. (Note:
9 e4 o6 @! T" O6 {This titration should be performed quickly near the end-point by
9 f3 g. J/ d9 e) I) t* p1 ~6 Jadding rapidly 0.2 ml increments of the titrant until the first colour
! q1 k% d( ]3 J' B. N! K6 `change occurs; although the colour will fade in 5-10 sec, it is the true6 w$ T O6 M' d5 d0 c, A! d$ j
end-point. Failure to observe the first colour change will result in an
/ p7 I* \/ J% f- Tincorrect titration. The fading end-point does not occur at the second0 z7 B& g; q' u3 u6 W. X
end-point.) I) w' D/ L! G4 Y. Y8 W
Add 2 g of sodium fluoride, boil the mixture for 2-5 min, and cool in a
% _' e% ?3 E, @ v; q1 ~stream of running water. Titrate this solution, using the zinc sulfate$ I" d ^. Q0 {' J& I
solution as titrant, to the same fugitive yellow-brown or pink end-point. f% g0 v6 _0 r# {" }6 f0 [+ B
as described above.7 t& ^% I' u1 W* Y4 f
Calculate the titre T of zinc sulfate solution by the formula:# {/ t% ~7 o6 t. C) Z8 T
T = 18.896 W / V
3 o% a- b% g3 x7 M4 jwhere
. z5 |4 {% O2 b6 ~6 Y \T is the mass (mg) of Al2O3 per ml of zinc sulfate solution
l$ c7 t! L/ T& z# pW is the mass (g) of aluminium wire
7 C" c! G @. ^% X+ lV is the ml of the zinc sulfate solution consumed in the: |% X7 [6 b) y+ O2 ^' ?
second titration
2 |- J' \& m- Y18.896 = (R × 1000 mg/g × 10 ml/2)/1000 ml and
6 }* w8 O: |( fR is the ratio of the formula weight of aluminium oxide to2 t( t. F# _7 @ U- t3 m0 x
that of elemental aluminium.% g; J X1 c$ T( _" H+ j W
Sample Solution A5 I2 N6 B, N( I h' s
Accurately weigh 1 g of the sample and transfer to a 250-ml high-silica
5 ^; W/ J, S. q. v+ m v7 s+ Xglass Erlenmeyer flask. Add 10 g of sodium bisulfate (NaHSO4 ? H2O).
+ d1 L. n( Q ~; N: `(Note: Do not use more sodium bisulfate than specified, as an excess
0 L" ?2 c1 x4 s; t- J6 b- |; lconcentration of salt will interfere with the EDTA titration later on in the
3 B9 p$ j% v0 Q, R. a( Gprocedure.) Begin heating the flask at low heat on a hot plate, and- M5 t2 V9 ~# C9 e# I1 G9 s
then gradually raise the temperature until full heat is reached.. ^2 O% p/ r6 a# s
(Caution: perform this procedure in a well ventilated area. ) When; j6 h O$ A( A3 p# J& w7 D
spattering has stopped and light fumes of SO3 appear, heat in the full
; D2 A7 G: s4 O( d" ^) ^flame of a Meeker burner, with the flask tilted so that the fusion of the! f" f9 R4 A p& Q, _
sample and sodium bisulfate is concentrated at one end of the flask.
" O% D" R1 \: ]5 i0 u/ `Swirl constantly until the melt is clear (except for silica content), but2 l% i) r0 Y: d) ]: C9 K$ S) C
guard against prolonged heating to avoid precipitation of titanium
; M( s' ~- X! K- R- M+ ?dioxide. Cool, add 25 ml sulfuric acid solution (1 in 2), and heat until
7 {; H3 k. p7 k. L/ p. U* rthe mass has dissolved and a clear solution results. Cool, and dilute to
; [% P1 F( ? z V" ]! i& N$ k120 ml with water. Introduce a magnetic stir bar into the flask.
3 t. }+ Y# W/ Q& W/ tSample Solution B
# L6 T3 y) u1 R: W7 K7 wPrepare 200 ml of an approximately 6.25 M solution of sodium+ f3 W( U$ X. T' r
hydroxide. Add 65 ml of this solution to Sample Solution A, while
) l: p- X- i- I( ^9 @5 q ystirring with the magnetic stirrer; pour the remaining 135 ml of the
* Y2 u# Z, ~: Q/ A1 G" Palkali solution into a 500-ml volumetric flask.. Z5 w; P( V# s9 h; A4 M& U }6 B
Slowly, with constant stirring, add the sample mixture to the alkali
! }2 d6 C0 w1 r% P+ f' osolution in the 500-ml volumetric flask; dilute to volume with water,& m" P, m' T5 [& u4 L
and mix. (Note: If the procedure is delayed at this point for more than5 G$ K3 p7 ]) j A, ^
2 hours, store the contents of the volumetric flask in a polyethylene6 @1 u; w5 |6 F. M& V) x
bottle.) Allow most of the precipitate to settle (or centrifuge for 5 min),5 X3 I$ C8 U3 k4 @' p
then filter the supernatant liquid through a very fine filter paper. Label- b% U; L! w' U! h
the filtrate Sample Solution B.
$ v e/ u: k, `8 M/ {3 {9 e7 JSample Solution C
* t* t y& Y: w% T" _Transfer 100 ml of the Sample Solution B into a 500-ml Erlenmeyer( w1 ~& e" ~( @7 w' W
flask, add 1 drop of methyl orange TS, acidify with hydrochloric acid) K0 n2 O0 ^) X1 u
solution (1 in 2), and then add about 3 ml in excess. Add 25 ml of 0.02
; ^ D* K& w, r# ?+ k2 M j6 y- NM disodium EDTA, and mix. [Note: If the approximate Al2O3 content is
9 D+ a: u3 t. E/ ?: xknown, calculate the optimum volume of EDTA solution to be added- k# a8 w0 L- D! X! G# q
by the formula: (4 x % Al2O3) + 5.]
$ `9 ^8 x$ H7 S5 Q- P+ ?% ]Add, dropwise, ammonia solution (1 in 5) until the colour is just5 P& b% Q% n# ?8 o9 Z+ F
completely changed from red to orange-yellow. Then add10 ml each
# h3 [& _9 k/ ]9 L6 ^" \, p8 E4 sof Solutions 1 and 2 (see above) and boil for 5 min. Cool quickly to R+ l+ l h6 `, f( r' U
room temperature in a stream of running water, add 3 drops of xylenol% c e6 A! ]2 ?! L0 E3 x5 Z
orange TS, and mix. If the solution is purple, yellow-brown, or pink,/ A0 E2 D7 b1 P0 J$ |
bring the pH to 5.3 - 5.7 by the addition of acetic acid. At the desired2 k% d1 e2 c4 |" U, ]: ?# E
pH, a pink colour indicates that not enough of the EDTA solution has4 v0 w% P' j3 ` @+ t& b
been added, in which case, discard the solution and repeat this
3 \: ?% Y5 I3 V7 u. R7 m, iprocedure with another 100 ml of Sample Solution B, using 50 ml,
9 N- {6 {6 A" {, Arather than 25 ml, of 0.02 M disodium EDTA.5 w: p) F e* F
Procedure
6 h1 R3 ^. F9 L, V& Q5 d. iUsing the standardized zinc sulfate solution as titrant, titrate Sample
9 |! H, y9 o! p+ @# |* J9 kSolution C to the first yellow-brown or pink end-point that persists for
1 i2 a2 y' g' j" a; E8 r" W& C5-10 sec. (Important: See Note under “0.01 Zinc sulfate”.) This first; V: b2 o% c. h
titration should require more than 8 ml of titrant, but for more accurate
! p& z; H0 C, C, D; _4 swork a titration of 10-15 ml is desirable.& \1 J w% o3 a- r9 Y
Add 2 g of sodium fluoride to the titration flask, boil the mixture for 2-56 H& n) g7 K" k0 r# d# @
min, and cool in a stream of running water. Titrate this solution, using U1 e! @7 w4 ]# |4 L. e4 e# N1 c
the standardized zinc sulfate solution as titrant, to the same fugitive0 W* k, h) [2 O5 l5 Y
yellow-brown or pink end-point as described above.
3 X5 v; @& F/ t# E) |. ^9 @Calculation:- W9 A8 _8 M( |6 B9 c
Calculate the percentage of aluminium oxide (Al2O3) in the sample& F# Z' P) |$ Z4 d
taken by the formula:
( V5 y0 z# w# G% Al2O3 = 100 × (0.005VT)/S8 Y& C9 q$ n! y h
where
: h6 k# I7 D* t' h- r; P$ VV is the number of ml of 0.01 N zinc sulfate consumed in% @! R& w: X3 v2 U" f
the second titration,' m2 }4 x7 v9 b; @2 T7 ^
T is the titre of the zinc sulfate solution,* R: I- _0 O! V( L8 i
S is the mass (g) of the sample taken, and
1 m3 @/ z) {, J$ z* [: h0.005 = 500 ml / (1000mg/g × 100 ml).; A7 `" {+ v, G9 N
Silicon dioxide Accurately weigh 1 g of the sample and transfer to a 250-ml high-silica
/ J, Q3 y6 C4 i: J8 _8 iglass Erlenmeyer flask. Add 10 g of sodium bisulfate (NaHSO4 ? H2O).
8 g( b+ ]* r/ l; R7 a. DHeat gently over a Meeker burner, while swirling the flask, until8 e% G, u- u9 G
decomposition and fusion are complete and the melt is clear, except% P9 l. l/ h8 o* `$ g4 ~8 m0 ?# E
for the silica content, and then cool. (Caution: Do not overheat the0 G9 A8 p+ s$ s8 v: T- i; h% b- `; c
contents of the flask at the beginning, and heat cautiously during) ]" v8 H K2 E5 M7 S
fusion to avoid spattering.)
4 o% r' D. D. g" y. c% Y8 W ?4 TTo the cooled melt add 25 ml of sulfuric acid solution (1 in 2) and heat
- c/ A2 u# R- B6 I+ ecarefully and slowly until the melt is dissolved. Cool, and carefully add
6 H' E) X# R+ _1 ], g150 ml of water by pouring very small portions down the sides of the
X% P' |- W1 t& T) Yflask, with frequent swirling to avoid over-heating and spattering. Allow, n, [! j/ B2 v6 w1 k
the contents of the flask to cool, and filter through fine ashless filter
( s2 g% F3 U+ t, m5 i1 gpaper, using a 60 degree gravity funnel. Rinse out all the silica from
2 k, u8 p4 M# h- ?: w2 othe flask onto the filter paper with sulfuric acid solution (1 in 10).# r3 e/ G) q9 u/ J
Transfer the filter paper and its contents into a platinum crucible, dry in! N) F7 w: q5 I4 r! `. x) A. U# k
an oven at 1200, and heat the partly covered crucible over a Bunsen
; Y( R1 b2 O* x4 I! Bburner. To prevent flaming of the filter paper, first heat the cover from: s# d; k: m% {
above, and then the crucible from below.( V8 `) ^5 B4 c
When the filter paper is consumed, transfer the crucible to a muffle4 a3 s5 p6 l. m3 ], k/ Z
furnace and ignite at 1000o for 30 min. Cool in a desiccator, and, O! W& l8 ~, a( P3 `( H* u
weigh. Add 2 drops of sulfuric acid (1 in 2) and 5 ml of concentrated
/ ]& {9 z8 }% E+ `. ?hydrofluoric acid (sp.gr. 1.15), and carefully evaporate to dryness, first
0 t+ T' N7 E9 W( aon a low-heat hot plate (to remove the HF) and then over a Bunsen* E. k: p& v- ~$ w9 i
burner (to remove the H2SO4). Take precautions to avoid spattering,
6 p) g8 z( N% z n; aespecially after removal of the HF. Ignite at 1000o for 10 min, cool in a
& C, X' z; g4 k c! _5 }desiccator, and weigh again. Record the difference between the two- [) T; L9 ^2 `) e) r7 S
weights as the content of SiO2 in the sample.# i/ l' Q6 {$ X7 O3 x" _" @- [
METHOD OF ASSAY8 w* l2 r2 \% r, A7 O5 n p! `
Accurately weigh about 150 mg of the sample, previously dried at 105o
# |7 U2 s3 Q6 r) W/ Efor 3 hours, and transfer into a 500-ml conical flask. Add 5 ml of water
; d8 A5 m! b/ T% L4 a2 _1 G# `" dand shake until a homogeneous, milky suspension is obtained. Add 30
, n1 ]4 h+ A- D6 k% d- L, H1 ^ml of sulfuric acid and 12 g of ammonium sulfate, and mix. Initially* W: b" J. {; @9 Z- I- d7 j* G. Q
heat gently, then heat strongly until a clear solution is obtained. Cool,
! L+ q% K2 A0 h- i# m! y0 Vthen cautiously dilute with 120 ml of water and 40 ml of hydrochloric! F- h- G1 f p. c* e: C' l; y% q4 c! e
acid, and stir. Add 3 g of aluminium metal, and immediately insert a: q7 L- X0 H& J: F
rubber stopper fitted with a U-shaped glass tube while immersing the
( ]/ P; @8 x! \* w; X* V8 H3 kother end of the U-tube into a saturated solution of sodium
8 } b- G( ~' `! F3 D- |bicarbonate contained in a 500-ml wide-mouth bottle, and generate7 X" y. c8 @# d; w. o2 r; C
hydrogen. Allow to stand for a few minutes after the aluminium metal0 A9 }8 C. f: t0 w8 ]0 S
has dissolved completely to produce a transparent purple solution.* r9 c+ M/ @- e, [/ q+ d
Cool to below 50o in running water, and remove the rubber stopper
3 w( P% ]+ \# [- _carrying the U-tube. Add 3 ml of a saturated potassium thiocyanate$ u8 Y; P3 `0 y1 F: @
solution as an indicator, and immediately titrate with 0.2 N ferric- L1 y& ?2 W+ C4 @6 ~, O# R
ammonium sulfate until a faint brown colour that persists for 308 i- p5 _6 J8 l1 `
seconds is obtained. Perform a blank determination and make any
! p4 M7 b2 a" Nnecessary correction. Each ml of 0.2 N ferric ammonium sulfate is
1 \( w+ B5 S! U) V3 v% n' _* eequivalent to 7.990 mg of TiO2.2 r \$ u$ v+ n p+ @7 l
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