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二氧化钛(钛白粉)
二氧化钛(钛白粉)
9 t: T3 ~1 y' @- e* A7 H
/ p0 v, b b5 ?. rJECFA关于二氧化钛(钛白粉)的结论% A6 N3 }( @ Z! F0 `
" w$ P# ^) I2 q5 X% g6 o$ N
摘要: 2006年JECFA关于二氧化钛的结论
/ E! D! m/ k, B' D5 { `) f( gADI值:不作限制。8 _5 M, [. a, V
功能:着色剂2 J! d5 w) w6 I4 u4 O% y
' q2 F) {& X* V! f8 i5 VTITANIUM DIOXIDE
/ I6 {% z" \0 x" ZPrepared at the 67th JECFA (2006) and published in FAO JECFA
4 S# d' d. M- c0 g* j8 D" sMonographs 3 (2006), superseding specifications prepared at the 63rd
0 g' e/ g$ a4 v+ J$ OJECFA (2004) and published in FNP 52 Add 12 (2004) and in the' x& r: X8 K$ V3 s* s+ i
Combined Compendium of Food Additive Specifications, FAO JECFA
) Q; I- f8 J' ]Monographs 1 (2005). An ADI “not limited” was established at the 13th( d9 Q2 m( w- X) j6 f" x
JECFA (1969).
; E, n2 R" l" mSYNONYMS! \* ^ D' _" S9 R% C( j
Titania, CI Pigment white 6, CI (1975) No. 77891, INS No. 1710 c. O8 n3 P k5 n% }
DEFINITION
$ \4 Y/ K/ r0 Z4 g4 r' Z* VTitanium dioxide is produced by either the sulfate or the chloride
/ A( N/ X5 o5 n, Sprocess. Processing conditions determine the form (anatase or rutile
+ j% O( M* A0 X% ?+ Zstructure) of the final product.
& d& F3 }+ u5 P# }3 l2 zIn the sulfate process, sulfuric acid is used to digest ilmenite (FeTiO3)
& g3 F- C$ n: C: Gor ilmenite and titanium slag. After a series of purification steps, the
" G' Z- i, o" k3 Y. Kisolated titanium dioxide is finally washed with water, calcined, and
/ `+ x. h7 k* m. g7 e8 s/ wmicronized.. @: ?; F$ e! ^8 G: b' v+ i1 `8 e
In the chloride process, chlorine gas is reacted with a titaniumcontaining
6 \" Z- \/ b- A/ i8 ^mineral under reducing conditions to form anhydrous1 _( F, [! H7 R
titanium tetrachloride, which is subsequently purified and converted to K* m2 b0 B: G8 J' X1 M
titanium dioxide either by direct thermal oxidation or by reaction with% m9 [: @ H) b" z7 o
steam in the vapour phase. Alternatively, concentrated hydrochloric
5 K% o- ~. W0 R6 \; [% I8 Racid can be reacted with the titanium-containing mineral to form a! e+ J' A" y8 y6 ~
solution of titanium tetrachloride, which is then further purified and: ?; e" ]" ]! W, l& t3 j
converted to titanium dioxide by hydrolysis. The titanium dioxide is# m+ {* @6 ?6 K8 K- ]
filtered, washed, and calcined.8 {! A+ d6 U! z0 U
Commercial titanium dioxide may be coated with small amounts of
( _" p* z" u0 R- G' u. o' M! |& f4 Q, Ualumina and/or silica to improve the technological properties of the3 Q9 j1 V# x7 _1 T. }* u
product.
0 Q5 ^! w& a \/ BC.A.S. number 13463-67-7
# u9 [2 j' d' }5 e( O) ZChemical formula TiO22 [' O$ I4 l9 ]
Formula weight
# g9 r8 u1 G9 W, o4 d79.88% ~+ F& b- S2 L' j
Assay0 G% C/ a7 i5 ]! o8 M; g
Not less than 99.0% on the dried basis (on an aluminium oxide and, D9 ~& M4 p/ Z6 p' `8 ^7 C
silicon dioxide-free basis)
: f3 Q2 }' \. N9 x( x8 e5 QDESCRIPTION
2 I+ S' s. R; nWhite to slightly coloured powder
3 ]/ m5 V3 b0 Y; t9 FFUNCTIONAL USES2 \4 D. Y! z+ b, [4 W# A% y
Colour
' y. v2 V, I9 x1 ^CHARACTERISTICS @% b. Y9 H4 N* F
IDENTIFICATION
- h3 q G3 k6 ~% d! n" ZSolubility (Vol. 4) v4 o: |4 \' N
Insoluble in water, hydrochloric acid, dilute sulfuric acid, and organic8 V8 @' N* N9 f/ ]) Q' K7 U
solvents. Dissolves slowly in hydrofluoric acid and hot concentrated6 T' w# L" c6 Y% E' D2 y I
sulfuric acid.
1 t7 z# `% \% z! d! wColour reaction
- a( t/ K- @9 n1 L* jAdd 5 ml sulfuric acid to 0.5 g of the sample, heat gently until fumes of
5 g, V7 |2 E9 V3 msulfuric acid appear, then cool. Cautiously dilute to about 100 ml with8 Z5 b' ~, h$ O' d. ?1 w1 h: M+ L
water and filter. To 5 ml of this clear filtrate, add a few drops of G. z" {/ c) G5 l* L% ^3 [
hydrogen peroxide; an orange-red colour appears immediately.& a' D6 [5 Y! N. W" i& b* Z
PURITY
9 v+ f! n/ b$ U6 [& r6 ~Loss on drying (Vol. 4) Not more than 0.5% (105°, 3 h)
9 x; E( f! w2 K4 DLoss on ignition (Vol. 4)
. M! ]# W; E6 B t/ N* F2 FNot more than 1.0% (800o) on the dried basis
! W! l9 q% X6 p' @Aluminium oxide and/or6 D, }: Z v: m0 A
silicon dioxide
( |# J, Z! g2 M$ P$ [Not more than 2%, either singly or combined+ [# i* k3 @4 ~1 x
See descriptions under TESTS
' ?0 |( d. r* x& Y) `Acid-soluble substances Not more than 0.5%; Not more than 1.5% for products containing1 u5 B, F5 r o2 G$ G; e
alumina or silica.
7 {+ H* d: i! o# N7 S" [/ s0 HSuspend 5 g of the sample in 100 ml 0.5 N hydrochloric acid and
/ u! p* E: @# |; k& {* ?/ L8 Tplace on a steam bath for 30 min with occasional stirring. Filter
4 d8 u8 ^! r1 Y8 r t( h; v, Jthrough a Gooch crucible fitted with a glass fibre filter paper. Wash J- p9 i, T( j' a* V
with three 10-ml portions of 0.5 N hydrochloric acid, evaporate the& Y0 [" s" d8 }4 E
combined filtrate and washings to dryness, and ignite at a dull red
+ G3 ?4 `. i) f6 i- l' ^* E$ v. Zheat to constant weight.3 ~9 X" Z$ t6 C2 A6 R
Water-soluble matter7 s7 A% E! Y5 R' `7 |- d
(Vol. 4)! m! A+ Z4 N6 n( ^) Y3 i
Not more than 0.5%
" d: R b) L3 tProceed as directed under acid-soluble substances (above), using
, W# {" ]. J9 T% Twater in place of 0.5 N hydrochloric acid.8 M9 |4 w" `2 B! k1 H
Impurities soluble in 0.5 N
% i+ C$ T. _" W; c: g u' R8 t- ~8 hhydrochloric acid
- B! k9 B! u! [' Q4 UAntimony Not more than 2 mg/kg: `- w$ f7 z8 i4 S9 D
See description under TESTS
) Q9 l; q& v0 P7 YArsenic Not more than 1 mg/kg
2 r l& g* R, X5 l8 x% I' C$ d. xSee description under TESTS
- K& \( [! F9 `Cadmium Not more than 1 mg/kg$ j# v8 L- M9 t$ n
See description under TESTS
, T& ?* Y2 t/ w7 @- ]3 l% _Lead
# Z, Y2 N9 v% q* K2 TNot more than 10 mg/kg
, ]1 L7 W6 s# u6 c# j- w2 hSee description under TESTS+ t" n% `% J& q' g' O, S& \
Mercury (Vol. 4) Not more than 1 mg/kg K; M" f& n9 T/ r
Determine using the cold vapour atomic absorption technique. Select a# o& l4 y o! w8 x7 u
sample size appropriate to the specified level
6 Y; p8 U8 G# Z- |* q% }- t% G6 zTESTS6 G3 k4 ^1 S# K
PURITY TESTS, F7 n# p: r# {& I7 }* |- U' D0 Z
Impurities soluble in 0.5 N" x1 j% X0 H" O, v6 ?; Q* d1 I; W5 ]
hydrochloric acid; Z* R1 E) T o) J) Q
Antimony, arsenic,
7 Y7 p0 S) g* m: X- \cadmium and lead
( K- d* a: }. v* H(Vol.4)
" M% g. M9 ^- W3 E W- O* vTransfer 10.0 g of sample into a 250-ml beaker, add 50 ml of 0.5 N5 ~, N8 m! p( e% H. z; w; p
hydrochloric acid, cover with a watch glass, and heat to boiling on a1 N! z3 d0 D# B; g, H' Y- d
hot plate. Boil gently for 15 min, pour the slurry into a 100- to 150-ml# n" Q1 J Y- d4 R# M x
centrifuge bottle, and centrifuge for 10 to 15 min, or until undissolved5 _' l: _2 q, W3 ]' V
material settles. Decant the supernatant extract through a Whatman
/ I/ A. t& u- O8 N' F$ I) TNo. 4 filter paper, or equivalent, collecting the filtrate in a 100-ml
6 n( s* e, Z9 [( Y, ]/ svolumetric flask and retaining as much as possible of the undissolved& E2 t5 t+ D0 ]: g* Y
material in the centrifuge bottle. Add 10 ml of hot water to the original
# d( q' z: I M9 z8 e& B% D+ Q- |5 M+ tbeaker, washing off the watch glass with the water, and pour the
+ x; h% b; Q) }4 e( P% }6 rcontents into the centrifuge bottle. Form a slurry, using a glass stirring
) \: [/ m, k; i: p0 j( lrod, and centrifuge. Decant through the same filter paper, and collect' J7 P3 i5 ?. ]1 g, g
the washings in the volumetric flask containing the initial extract.
! {2 |. t7 b) V8 w+ {3 ]Repeat the entire washing process two more times. Finally, wash the: o F8 U( q2 k8 q0 g/ ~0 R+ }
filter paper with 10 to 15 ml of hot water. Cool the contents of the flask
5 ~6 |1 W5 r- N! [9 o0 kto room temperature, dilute to volume with water, and mix.' c. r' ?( {/ L7 [+ Q
Determine antimony, cadmium, and lead using an AAS/ICP-AES
5 V) Q8 L" J5 Z) s" ytechnique appropriate to the specified level. Determine arsenic using the( P8 B; r- W7 i4 e/ U7 N! _
ICP-AES/AAS-hydride technique. Alternatively, determine arsenic using, w6 A, r! L# K/ [( W# o: s
Method II of the Arsenic Limit Test, taking 3 g of the sample rather than% U( }+ T6 s- Z3 z7 x
1 g. The selection of sample size and method of sample preparation
9 ?0 U+ C( J) xmay be based on the principles of the methods described in Volume 4.8 y) P* B; W2 m9 c" F4 ?) g
Aluminium oxide Reagents and sample solutions
# I2 S: Z* p0 |0.01 N Zinc Sulfate
8 F6 U' J% ^5 l h. ^) d+ s5 z4 D6 LDissolve 2.9 g of zinc sulfate (ZnSO4 ? 7H2O) in sufficient water to; @6 C/ L0 f% [- l# o1 U7 t
make 1000 ml. Standardize the solution as follows: Dissolve 500 mg
: V& m! a8 a4 V, W* @; Oof high-purity (99.9%) aluminium wire, accurately weighed, in 20 ml of0 D) V9 T9 W9 e2 w9 s; [
concentrated hydrochloric acid, heating gently to effect solution, then3 l8 p x: J( Z! z6 c
transfer the solution into a 1000-ml volumetric flask, dilute to volume
6 Y) E% C9 l R6 H3 w, M2 Jwith water, and mix. Transfer a 10 ml aliquot of this solution into a 500% N2 P: H* o8 p; q! B
ml Erlenmeyer flask containing 90 ml of water and 3 ml of
6 Y6 w2 y) b% ~+ mconcentrated hydrochloric acid, add 1 drop of methyl orange TS and2 ]" v! a* k& |, ~, i* T. K
25 ml of 0.02 M disodium ethylenediaminetetraacetate (EDTA) Add,
5 H1 L# H9 s3 Z# M ?: q4 edropwise, ammonia solution (1 in 5) until the colour is just completely! [+ K$ R/ u2 s/ Y; {8 u/ H9 C
changed from red to orange-yellow. Then, add:
' u9 A L \! T4 c A0 t1 Y* ^(a): 10 ml of ammonium acetate buffer solution (77 g of5 j3 ^# O0 q& u8 Z: a( H3 B
ammonium acetate plus 10 ml of glacial acetic acid, dilute to1 K+ P- p( {; }2 Y3 F
1000 ml with water) and3 q$ f7 c& H* ~# g# i9 F
(b): 10 ml of diammonium hydrogen phosphate solution (150 g& a4 i! P3 C- J# _ x% [" }
of diammonium hydrogen phosphate in 700 ml of water,
" w' a9 S3 E, _adjusted to pH 5.5 with a 1 in 2 solution of hydrochloric acid,% Y7 l+ l4 Q8 }2 D$ x0 G
then dilute to 1000 ml with water).8 o( E+ m1 i' H6 D" X
Boil the solution for 5 min, cool it quickly to room temperature in a
: w. [$ ?4 b. g+ \0 Kstream of running water, add 3 drops of xylenol orange TS, and mix.8 D2 I: W8 k8 \3 j2 T
Using the zinc sulfate solution as titrant, titrate the solution to the first8 t. c3 j4 _7 s+ Y* U$ v
yellow-brown or pink end-point colour that persists for 5-10 sec. (Note:' u% s! c# u3 w+ e- l9 |% B
This titration should be performed quickly near the end-point by& {) x2 R a' L( R+ v
adding rapidly 0.2 ml increments of the titrant until the first colour+ \# q1 H9 P: Q3 S3 Q. O; ^, k/ S
change occurs; although the colour will fade in 5-10 sec, it is the true( t) J6 @# G* m# R5 r% a
end-point. Failure to observe the first colour change will result in an) O# j4 M* U1 A& Y; ]
incorrect titration. The fading end-point does not occur at the second
( J- i. M' F$ t X& o, eend-point.)
1 g# Q) C) ~, ?8 w+ {' i$ ^Add 2 g of sodium fluoride, boil the mixture for 2-5 min, and cool in a
. e' u0 \* Y1 O0 F+ I, v4 Fstream of running water. Titrate this solution, using the zinc sulfate r R" ~- E# T
solution as titrant, to the same fugitive yellow-brown or pink end-point
' _0 U8 e( f: e/ e0 J% y/ k: Q8 \as described above.
' M3 q5 L2 `) J( H: X6 WCalculate the titre T of zinc sulfate solution by the formula:# ^ \1 Q0 A# e' N1 ^
T = 18.896 W / V/ L. v, m8 \4 t$ I0 r
where
9 R2 Y6 N( V9 L2 ]+ kT is the mass (mg) of Al2O3 per ml of zinc sulfate solution* h2 Y. g/ l9 g
W is the mass (g) of aluminium wire
! q8 s' R5 Z) P# [V is the ml of the zinc sulfate solution consumed in the
/ U. W K4 m1 h$ Rsecond titration
2 y# K; O r! I" q# K18.896 = (R × 1000 mg/g × 10 ml/2)/1000 ml and [/ o, b) U' Z
R is the ratio of the formula weight of aluminium oxide to' Q6 N3 u# f+ @7 @ ^$ c& J C# C) J3 v
that of elemental aluminium.* v0 H; X. N. Z
Sample Solution A5 L4 L4 g; U W0 _( R
Accurately weigh 1 g of the sample and transfer to a 250-ml high-silica) L5 D' c6 b2 a1 J4 N
glass Erlenmeyer flask. Add 10 g of sodium bisulfate (NaHSO4 ? H2O).
( O" l2 o8 K3 u; |5 L" ~(Note: Do not use more sodium bisulfate than specified, as an excess, H- A9 J' Y' p$ A0 U. f* l
concentration of salt will interfere with the EDTA titration later on in the) J8 ?& ?0 ?9 l+ l; I1 C+ l7 I+ H4 y
procedure.) Begin heating the flask at low heat on a hot plate, and
. V- a4 ^4 R7 _then gradually raise the temperature until full heat is reached.1 c! _( k% \' _7 o+ T4 t
(Caution: perform this procedure in a well ventilated area. ) When: F$ `$ M* v. o2 `! B' l
spattering has stopped and light fumes of SO3 appear, heat in the full. a- t6 t0 u7 l w2 \. o
flame of a Meeker burner, with the flask tilted so that the fusion of the6 c6 e" |) n6 N7 f
sample and sodium bisulfate is concentrated at one end of the flask.6 } R4 R5 w. o0 g" j
Swirl constantly until the melt is clear (except for silica content), but
. i" C3 v6 S: X) A$ V$ j% gguard against prolonged heating to avoid precipitation of titanium1 r* U& J' i. ]5 }% R5 s. }# l c
dioxide. Cool, add 25 ml sulfuric acid solution (1 in 2), and heat until
6 }9 A$ i& y7 L: Hthe mass has dissolved and a clear solution results. Cool, and dilute to
4 I! B% ]: f5 k$ F2 z- A# Z120 ml with water. Introduce a magnetic stir bar into the flask.
* a m* E" K" i5 K) lSample Solution B
7 ~4 B% J6 q+ P8 F0 n1 K6 |$ UPrepare 200 ml of an approximately 6.25 M solution of sodium/ u9 ^- v, V# o- g" e5 ^5 _5 _
hydroxide. Add 65 ml of this solution to Sample Solution A, while
) J. s' |; b! {2 B" Astirring with the magnetic stirrer; pour the remaining 135 ml of the* i! D& ?( \5 D3 a
alkali solution into a 500-ml volumetric flask.
Z# R3 S! i+ o8 GSlowly, with constant stirring, add the sample mixture to the alkali+ C% h4 v0 y" @6 U7 w
solution in the 500-ml volumetric flask; dilute to volume with water,
% ?8 I0 p6 }" _ W$ land mix. (Note: If the procedure is delayed at this point for more than1 H% L" z) ~4 v. `
2 hours, store the contents of the volumetric flask in a polyethylene4 d3 M+ T2 R( R8 G! o
bottle.) Allow most of the precipitate to settle (or centrifuge for 5 min),
y# ^; |- V7 t9 Xthen filter the supernatant liquid through a very fine filter paper. Label
- l ]. P+ t( S, |. M9 A3 Qthe filtrate Sample Solution B.; Y/ c% z/ B* P
Sample Solution C
/ K3 c( ?- Z+ ^4 fTransfer 100 ml of the Sample Solution B into a 500-ml Erlenmeyer' U0 r" ?2 g- e
flask, add 1 drop of methyl orange TS, acidify with hydrochloric acid
9 m; p+ D5 @+ L( ^9 y7 ~3 {solution (1 in 2), and then add about 3 ml in excess. Add 25 ml of 0.02
/ P0 g- _0 d. h; b' C4 C8 xM disodium EDTA, and mix. [Note: If the approximate Al2O3 content is) \. w% a, E; @9 f# c; g
known, calculate the optimum volume of EDTA solution to be added& ?3 k) S) G2 F2 ?* q2 u& g. }( s" ~. K
by the formula: (4 x % Al2O3) + 5.]
R) j; r: ]! Q' n# W' HAdd, dropwise, ammonia solution (1 in 5) until the colour is just
$ O6 f" }0 {# k2 t6 e$ ? v) ^completely changed from red to orange-yellow. Then add10 ml each
3 N9 E% l. O$ u* W, c. K) ~' Bof Solutions 1 and 2 (see above) and boil for 5 min. Cool quickly to
; i4 v5 b+ X( o2 o# @% f0 q2 }0 i; Oroom temperature in a stream of running water, add 3 drops of xylenol" T, f* s+ l9 X! X2 P+ N
orange TS, and mix. If the solution is purple, yellow-brown, or pink,' N4 p0 X( o$ F( E% v# Q
bring the pH to 5.3 - 5.7 by the addition of acetic acid. At the desired
' U- Y; ^, ]) K! u6 epH, a pink colour indicates that not enough of the EDTA solution has* n7 P& u& q9 e, x4 `: |
been added, in which case, discard the solution and repeat this
& y5 |$ S4 v5 o* I. l$ u# hprocedure with another 100 ml of Sample Solution B, using 50 ml,
, c8 k3 a# P) R! o N- e: h7 grather than 25 ml, of 0.02 M disodium EDTA.
n4 Y3 x5 r, |% l: ^+ _Procedure
0 N5 ?$ L6 Y. Z4 e2 c% nUsing the standardized zinc sulfate solution as titrant, titrate Sample
$ O6 [8 G. f9 M O/ u7 a7 B1 PSolution C to the first yellow-brown or pink end-point that persists for; H2 a7 D# c3 l/ K8 o/ |) I
5-10 sec. (Important: See Note under “0.01 Zinc sulfate”.) This first. s& a0 Z6 H* t1 g1 X* a$ b% O
titration should require more than 8 ml of titrant, but for more accurate: c% Y& V ]$ A5 d" {: v) o5 S
work a titration of 10-15 ml is desirable.
7 g$ C8 Q: d0 ~/ b3 NAdd 2 g of sodium fluoride to the titration flask, boil the mixture for 2-58 { a9 }0 s8 B& ]* W7 L
min, and cool in a stream of running water. Titrate this solution, using
+ B' n4 \% W9 M( L ]; Wthe standardized zinc sulfate solution as titrant, to the same fugitive% Z! `3 l2 h5 x; h1 H
yellow-brown or pink end-point as described above.1 T& {0 H/ r* @$ R! M
Calculation:
4 x: d+ U0 M5 F0 M3 t6 E2 MCalculate the percentage of aluminium oxide (Al2O3) in the sample- l- [3 F( b' l' M" Y: a
taken by the formula:- H7 q8 @6 r% Q
% Al2O3 = 100 × (0.005VT)/S# y3 j% y( A8 t7 j
where; @3 W( n- \& _8 o8 _
V is the number of ml of 0.01 N zinc sulfate consumed in
Q( V+ B; t& R& l; ]) R/ L% {the second titration,
+ S; k0 r5 c( I1 f7 u. e$ gT is the titre of the zinc sulfate solution,
( p4 y( j9 U& K: wS is the mass (g) of the sample taken, and
w- f5 ]) E& s" x7 v0.005 = 500 ml / (1000mg/g × 100 ml).
- C3 G5 J2 G0 s% d; T$ ASilicon dioxide Accurately weigh 1 g of the sample and transfer to a 250-ml high-silica% b6 n) D) J ]/ u% y' H
glass Erlenmeyer flask. Add 10 g of sodium bisulfate (NaHSO4 ? H2O).7 `& x/ x# o: g1 k4 \
Heat gently over a Meeker burner, while swirling the flask, until ^: {3 m6 s! t; i0 D
decomposition and fusion are complete and the melt is clear, except
x! n; D) c R' h/ ]7 c- hfor the silica content, and then cool. (Caution: Do not overheat the1 f& \7 O. V. E" C- W
contents of the flask at the beginning, and heat cautiously during: c) q8 ?0 ]) g/ Y3 ]3 v
fusion to avoid spattering.)' P8 j# X: b& F% l5 p
To the cooled melt add 25 ml of sulfuric acid solution (1 in 2) and heat% D3 G8 n" c# [" e3 m4 U# I
carefully and slowly until the melt is dissolved. Cool, and carefully add
0 Y, z- }5 l! ?! `' x150 ml of water by pouring very small portions down the sides of the
5 T! j; r! T* L+ U, z" Fflask, with frequent swirling to avoid over-heating and spattering. Allow7 p% E4 r# {1 @
the contents of the flask to cool, and filter through fine ashless filter" T' i2 g! f9 o' E* k
paper, using a 60 degree gravity funnel. Rinse out all the silica from
# e E0 D& m" j# e/ H w# P. Ithe flask onto the filter paper with sulfuric acid solution (1 in 10).
& b: Y$ E) r4 x1 Y) e& q5 m, UTransfer the filter paper and its contents into a platinum crucible, dry in. {: A& l8 B N0 b
an oven at 1200, and heat the partly covered crucible over a Bunsen8 X. R4 ?) M* n, D' Y3 U5 I/ J
burner. To prevent flaming of the filter paper, first heat the cover from- K* d6 D3 ~- ~6 t5 i5 D; g
above, and then the crucible from below.# h( k" ]- J0 k& D
When the filter paper is consumed, transfer the crucible to a muffle
7 X- h# L a- U e. ?- ~furnace and ignite at 1000o for 30 min. Cool in a desiccator, and* O4 [7 @( F* o: t
weigh. Add 2 drops of sulfuric acid (1 in 2) and 5 ml of concentrated% a$ ]) I% Y0 i6 n1 o
hydrofluoric acid (sp.gr. 1.15), and carefully evaporate to dryness, first
: |: {9 d" c' P' w+ a1 Kon a low-heat hot plate (to remove the HF) and then over a Bunsen
" X% C! i/ x3 E# c2 Z! rburner (to remove the H2SO4). Take precautions to avoid spattering,$ k) \/ q5 }0 M$ x) a% ?0 G- R$ u
especially after removal of the HF. Ignite at 1000o for 10 min, cool in a+ f! p& a" y- ~" g# C7 F! v
desiccator, and weigh again. Record the difference between the two
: p# j* d) R2 M8 qweights as the content of SiO2 in the sample.
+ Q* S3 {3 D x! y7 lMETHOD OF ASSAY) @" t4 [: l( l
Accurately weigh about 150 mg of the sample, previously dried at 105o
; @) h3 F1 K' `: lfor 3 hours, and transfer into a 500-ml conical flask. Add 5 ml of water. x. P/ ~0 I+ E9 j8 B$ [
and shake until a homogeneous, milky suspension is obtained. Add 30
, [ H0 z4 N" r, f! Nml of sulfuric acid and 12 g of ammonium sulfate, and mix. Initially
3 I; u/ ?0 ]( o/ Nheat gently, then heat strongly until a clear solution is obtained. Cool,
' c5 B1 X& z+ T" j7 N( Hthen cautiously dilute with 120 ml of water and 40 ml of hydrochloric
" Y2 W1 _3 W# u! C1 y- m/ N* Dacid, and stir. Add 3 g of aluminium metal, and immediately insert a% B \4 f3 x; G( H" d
rubber stopper fitted with a U-shaped glass tube while immersing the" \# [: c7 c0 \8 y
other end of the U-tube into a saturated solution of sodium
* a+ @0 ?% q% w- I" j; }% fbicarbonate contained in a 500-ml wide-mouth bottle, and generate
0 ^6 `, q$ e M" R. [4 b& ^hydrogen. Allow to stand for a few minutes after the aluminium metal
( M/ }* y% A/ E3 j! ?has dissolved completely to produce a transparent purple solution. {! x* G7 B/ t9 ~2 ]4 ]0 F# {
Cool to below 50o in running water, and remove the rubber stopper* M$ X* `7 s0 P3 C( P, y6 b
carrying the U-tube. Add 3 ml of a saturated potassium thiocyanate
, z+ b8 E3 a& G, ~2 M8 asolution as an indicator, and immediately titrate with 0.2 N ferric: e3 h: e' h& x6 X1 V1 F5 ~3 L
ammonium sulfate until a faint brown colour that persists for 30
8 q9 u% w' z+ u2 F% i! S! [seconds is obtained. Perform a blank determination and make any) D( ?0 ]/ U- d+ O
necessary correction. Each ml of 0.2 N ferric ammonium sulfate is
/ ^$ }8 }1 I+ U5 R* vequivalent to 7.990 mg of TiO2.
f4 P) ~. f4 T |
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