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二氧化钛(钛白粉)
二氧化钛(钛白粉): f- G K/ a; J( U5 h
$ t- V+ g" c: m/ F- [: W, T( J! vJECFA关于二氧化钛(钛白粉)的结论0 u/ f2 e) F+ T
3 m* X) X5 B. Q' l v( t u
摘要: 2006年JECFA关于二氧化钛的结论
& h- I i T: _0 O: D$ U5 FADI值:不作限制。8 D. q3 `1 V6 {7 |$ | s( f2 |
功能:着色剂5 ~! w3 j4 [+ i; h; {% c+ S
/ a/ j o' ]: Y) l+ Q/ q
TITANIUM DIOXIDE
' a5 ~ v$ \) J7 [Prepared at the 67th JECFA (2006) and published in FAO JECFA- N( K5 o' v, I, x) d
Monographs 3 (2006), superseding specifications prepared at the 63rd$ Q7 x. M# h0 |0 o; a- b/ d+ @ \) L
JECFA (2004) and published in FNP 52 Add 12 (2004) and in the
$ t3 i9 G: O3 NCombined Compendium of Food Additive Specifications, FAO JECFA
, g$ l5 a4 U/ j. JMonographs 1 (2005). An ADI “not limited” was established at the 13th2 z: \; d5 i7 d8 e
JECFA (1969).$ H! h* O% v' P c
SYNONYMS
6 B" D$ J1 t0 c( WTitania, CI Pigment white 6, CI (1975) No. 77891, INS No. 171/ z# K C+ v' J; A2 m5 f; |
DEFINITION8 o7 n0 W- ^% q- a1 B: _
Titanium dioxide is produced by either the sulfate or the chloride2 ^% e+ O3 {* Z( T0 V# v
process. Processing conditions determine the form (anatase or rutile
! p, f( z4 d& Z/ Z& rstructure) of the final product.: [$ K3 c8 |* Z) K3 F
In the sulfate process, sulfuric acid is used to digest ilmenite (FeTiO3)
4 r& ~: N# d5 Nor ilmenite and titanium slag. After a series of purification steps, the
# j; O, I2 e6 U; x5 @0 A/ tisolated titanium dioxide is finally washed with water, calcined, and; H. D+ ?* I8 u" G7 r1 P
micronized.$ u) S0 H9 j2 c5 n* c9 ~% f
In the chloride process, chlorine gas is reacted with a titaniumcontaining
$ T" `1 S8 m8 c3 Smineral under reducing conditions to form anhydrous1 L/ [/ T, |& r- k% ~
titanium tetrachloride, which is subsequently purified and converted to$ E- `9 I2 W& O
titanium dioxide either by direct thermal oxidation or by reaction with4 |" b/ f6 Y3 B6 \
steam in the vapour phase. Alternatively, concentrated hydrochloric+ p$ t1 l2 G% g' t) b% ]- r9 g+ t
acid can be reacted with the titanium-containing mineral to form a2 o( e; {4 w- O, L
solution of titanium tetrachloride, which is then further purified and
3 v4 D7 J. K2 y2 T9 D. X9 g6 kconverted to titanium dioxide by hydrolysis. The titanium dioxide is
, W! I$ c' G8 `filtered, washed, and calcined.% x' u. ]5 I6 x. Q/ |. Y( C
Commercial titanium dioxide may be coated with small amounts of, F2 N6 j2 R+ q! Y
alumina and/or silica to improve the technological properties of the
6 V O* q @0 w( b# Cproduct.
$ ]3 y% N1 ?0 |6 b5 `C.A.S. number 13463-67-7
) `( j% e4 B" }7 vChemical formula TiO2
( X7 C2 \0 F3 k$ l! yFormula weight
3 H, P9 X. X9 h! F4 v+ K/ K79.88: `; l* J0 L+ {. B( U0 L j; R
Assay
) }0 A1 G. R: y2 L6 ^Not less than 99.0% on the dried basis (on an aluminium oxide and F$ b2 n. o0 i: l( L
silicon dioxide-free basis)
+ l, f0 B. T1 L' I- B! F7 ZDESCRIPTION$ m9 M! _- J. O- ^5 x) C
White to slightly coloured powder
# ~9 p1 M7 a8 j" p& j% k# |FUNCTIONAL USES
R0 O# a A7 u$ e% V. j5 RColour
5 i/ Q& C, P% ^' @$ c' kCHARACTERISTICS
/ w6 P9 w$ c& u% r% h# W C' oIDENTIFICATION" z$ S' G' ?! ]/ |' s" }7 E, k
Solubility (Vol. 4)) M6 U) A2 i9 R. R8 f
Insoluble in water, hydrochloric acid, dilute sulfuric acid, and organic
2 d" s, {- h' Y/ R7 d2 b- Zsolvents. Dissolves slowly in hydrofluoric acid and hot concentrated, {$ _- B8 i5 y- ^# { M
sulfuric acid.
" p# x$ s. x: H6 a, u& ~Colour reaction
% m2 l7 |# A6 \: ^% S% FAdd 5 ml sulfuric acid to 0.5 g of the sample, heat gently until fumes of
; m0 `% V, o! X% Z/ ]3 vsulfuric acid appear, then cool. Cautiously dilute to about 100 ml with4 }" n4 U8 J2 T: G
water and filter. To 5 ml of this clear filtrate, add a few drops of9 H( G Q2 {# D6 s: N5 l
hydrogen peroxide; an orange-red colour appears immediately.
( w: K: z( I. m: _/ r# KPURITY
- e$ I4 f* G1 xLoss on drying (Vol. 4) Not more than 0.5% (105°, 3 h) h) S& U1 m1 I9 B
Loss on ignition (Vol. 4)" X; X4 s9 p7 Z
Not more than 1.0% (800o) on the dried basis' R5 s$ e2 j( o8 q1 W! V2 ^2 T
Aluminium oxide and/or
0 o3 Q8 X2 G' q# x2 jsilicon dioxide# n+ D2 E8 ?5 m
Not more than 2%, either singly or combined
: `1 ?3 `: O) r! I, H; D7 _: B/ vSee descriptions under TESTS+ X1 u( g. E. J. B; ?
Acid-soluble substances Not more than 0.5%; Not more than 1.5% for products containing, A' I6 j6 k! K2 }
alumina or silica.9 T9 @$ e! E. ^9 p5 Q. a+ Z7 M6 E9 u
Suspend 5 g of the sample in 100 ml 0.5 N hydrochloric acid and5 w5 `6 f6 H, E4 D" C
place on a steam bath for 30 min with occasional stirring. Filter: h5 F# r! b- y: P# G9 O! h$ i. i
through a Gooch crucible fitted with a glass fibre filter paper. Wash7 D" F. W% {$ ?9 F
with three 10-ml portions of 0.5 N hydrochloric acid, evaporate the
( a7 ^- ^9 E7 H- n8 E0 W" X; v9 G0 zcombined filtrate and washings to dryness, and ignite at a dull red
2 |- f M) H# ~heat to constant weight.1 C7 d* i; i: t4 L. C) M
Water-soluble matter
9 }4 t5 g: c0 V$ H8 \9 W2 ~(Vol. 4)
0 O% F ~% {: gNot more than 0.5%
/ B' ^& c6 ~- BProceed as directed under acid-soluble substances (above), using2 D) ^2 {9 C- _
water in place of 0.5 N hydrochloric acid.
- t0 _' y0 s! A/ |5 c' X) N% X9 iImpurities soluble in 0.5 N8 z2 g% W {1 P7 l
hydrochloric acid& }+ K+ y5 |2 ?; Q
Antimony Not more than 2 mg/kg
2 o. ` u. S! mSee description under TESTS
* n) P8 _( B$ AArsenic Not more than 1 mg/kg
3 A; }, A) m M2 r+ G% wSee description under TESTS
2 z3 C7 N) Q9 o9 \+ K( @Cadmium Not more than 1 mg/kg( T% o/ W) p/ T/ H7 J% _' ^# o/ j
See description under TESTS
- C- A4 Y7 O8 A7 L3 x8 A4 `Lead+ E8 T: Y" \" u g; W3 D/ E$ f
Not more than 10 mg/kg
& i) u- B& h Q; B% p8 p( VSee description under TESTS
0 z. P2 J' `: ^$ S5 x+ @/ {Mercury (Vol. 4) Not more than 1 mg/kg
. ?( w) q6 a( d: a; WDetermine using the cold vapour atomic absorption technique. Select a
1 u. m9 N* o+ w6 K8 e, Fsample size appropriate to the specified level
* M. e6 [& g% C9 i, M3 a2 QTESTS. f1 Q, u1 F7 ?
PURITY TESTS
0 j) N4 m2 _ b& B% n7 [7 l2 V }) nImpurities soluble in 0.5 N
6 M6 l u3 o! f0 @/ ~8 l+ {hydrochloric acid
1 V ^8 S8 N8 S$ B' `6 lAntimony, arsenic,
4 @6 A/ c2 Y+ E/ V5 zcadmium and lead6 H3 x) U" b! A5 `( k
(Vol.4)' A' z$ i! T! A. ?) |: |
Transfer 10.0 g of sample into a 250-ml beaker, add 50 ml of 0.5 N2 n" D& ~9 }- Q( p' G
hydrochloric acid, cover with a watch glass, and heat to boiling on a
7 ?: ~, B) o W/ Q- A! q# w zhot plate. Boil gently for 15 min, pour the slurry into a 100- to 150-ml7 @& y8 Z6 J# X$ m8 e5 y! N7 I( i
centrifuge bottle, and centrifuge for 10 to 15 min, or until undissolved& s# T7 c: @- @8 R" U1 {
material settles. Decant the supernatant extract through a Whatman: |7 u: e2 r9 Y+ {0 b% j+ \6 G
No. 4 filter paper, or equivalent, collecting the filtrate in a 100-ml; o* E W- Z. @1 Y, C9 [
volumetric flask and retaining as much as possible of the undissolved ~" ?9 f" M$ B% j
material in the centrifuge bottle. Add 10 ml of hot water to the original
% E3 p4 {$ b! Y& Kbeaker, washing off the watch glass with the water, and pour the
' A: ~7 G% q% y, L4 qcontents into the centrifuge bottle. Form a slurry, using a glass stirring0 w5 T/ a1 R6 r# I1 D4 C
rod, and centrifuge. Decant through the same filter paper, and collect$ z; e* T, E# ^9 H
the washings in the volumetric flask containing the initial extract., Q+ l9 x( X. y, x& }9 e
Repeat the entire washing process two more times. Finally, wash the
j7 ?5 Y" U0 ?0 g8 h$ R- l$ mfilter paper with 10 to 15 ml of hot water. Cool the contents of the flask
5 P' I y3 w3 b8 ^- f: {to room temperature, dilute to volume with water, and mix.
5 r( P$ S' W0 T6 ? Z$ c, wDetermine antimony, cadmium, and lead using an AAS/ICP-AES
. i' ]9 O. N) ]/ f" utechnique appropriate to the specified level. Determine arsenic using the
/ P0 r$ D; q+ Y/ z& X4 [7 F. EICP-AES/AAS-hydride technique. Alternatively, determine arsenic using
0 O+ P5 K1 o/ @) J2 ]Method II of the Arsenic Limit Test, taking 3 g of the sample rather than! t9 z, _) Q0 r# |0 `, T5 S8 z$ r
1 g. The selection of sample size and method of sample preparation
5 B O! \1 y8 ?3 \' o Mmay be based on the principles of the methods described in Volume 4.6 M( a% @; B, i
Aluminium oxide Reagents and sample solutions
( k# b) O/ q. s0.01 N Zinc Sulfate5 O! {, j% f! ]; c
Dissolve 2.9 g of zinc sulfate (ZnSO4 ? 7H2O) in sufficient water to' m# y$ k8 u; U- G3 ~3 p, l
make 1000 ml. Standardize the solution as follows: Dissolve 500 mg
! Q, E; J3 E! l" U% t% h' Mof high-purity (99.9%) aluminium wire, accurately weighed, in 20 ml of' }. l' D& u3 u' E% G
concentrated hydrochloric acid, heating gently to effect solution, then/ u) c, C8 ]0 Y. Y- Q
transfer the solution into a 1000-ml volumetric flask, dilute to volume3 C1 Y, K1 a. u
with water, and mix. Transfer a 10 ml aliquot of this solution into a 5000 ~0 d9 v1 l* h3 ^$ C; n8 |
ml Erlenmeyer flask containing 90 ml of water and 3 ml of/ M0 l$ e( x3 ?
concentrated hydrochloric acid, add 1 drop of methyl orange TS and
8 H" A' T0 d8 G. N1 }; h/ M25 ml of 0.02 M disodium ethylenediaminetetraacetate (EDTA) Add,
% H8 t& ?2 t$ w) @( @dropwise, ammonia solution (1 in 5) until the colour is just completely. j$ i' e0 o6 Y( W, \* H
changed from red to orange-yellow. Then, add:
7 `3 z( D2 T H(a): 10 ml of ammonium acetate buffer solution (77 g of
; A! V- e" b9 R- Tammonium acetate plus 10 ml of glacial acetic acid, dilute to+ V" `, q3 W4 Q- H5 F; A& ]
1000 ml with water) and& B p8 n% ^) Y7 L( D3 O
(b): 10 ml of diammonium hydrogen phosphate solution (150 g
4 v, d D# [% G3 j( cof diammonium hydrogen phosphate in 700 ml of water,
' D% ~: l; ^0 g4 C: c% g% }( badjusted to pH 5.5 with a 1 in 2 solution of hydrochloric acid,
# ]3 O+ H2 T$ Uthen dilute to 1000 ml with water).* S3 k( ]4 O3 ]( U) W
Boil the solution for 5 min, cool it quickly to room temperature in a r" S. \: ^( D& T/ C2 P
stream of running water, add 3 drops of xylenol orange TS, and mix.
2 K3 c2 g) b& TUsing the zinc sulfate solution as titrant, titrate the solution to the first; x/ P n3 L5 E
yellow-brown or pink end-point colour that persists for 5-10 sec. (Note:
& O) V) Z- C; H, j* }This titration should be performed quickly near the end-point by9 \0 `# Y8 f/ j( m, w. h/ @
adding rapidly 0.2 ml increments of the titrant until the first colour% A/ {3 z# J$ ^! j3 N
change occurs; although the colour will fade in 5-10 sec, it is the true
4 r) p% E" U- ?0 J: kend-point. Failure to observe the first colour change will result in an
\1 r& P2 B8 N4 Aincorrect titration. The fading end-point does not occur at the second
/ _& e3 H7 @) G, j6 [% cend-point.)4 X) F$ d: \6 W; T, W$ l
Add 2 g of sodium fluoride, boil the mixture for 2-5 min, and cool in a3 g' V. n: t3 E5 l7 f3 t I5 {
stream of running water. Titrate this solution, using the zinc sulfate( N$ ]( ~8 \; x/ ^
solution as titrant, to the same fugitive yellow-brown or pink end-point
' B$ q# }! ]+ }' o6 N6 e6 ~as described above.
" W% ]! `. {$ o3 v+ F- f; z* bCalculate the titre T of zinc sulfate solution by the formula:% t9 k: ^& W+ N
T = 18.896 W / V9 P1 k. w+ Q$ C! r3 g+ F ]) X/ T
where9 v6 _+ h8 p& C0 l7 }6 R( M
T is the mass (mg) of Al2O3 per ml of zinc sulfate solution$ ?9 Q `( z2 e u i0 |2 P' n. D
W is the mass (g) of aluminium wire
- k6 n0 @9 v' p- d& v4 g& JV is the ml of the zinc sulfate solution consumed in the
. P _: N4 h4 E& `8 ssecond titration R2 H2 G3 a4 E; `% L5 u
18.896 = (R × 1000 mg/g × 10 ml/2)/1000 ml and
/ `/ r7 Z% p8 G( A' CR is the ratio of the formula weight of aluminium oxide to
* ^8 H' j0 m) s8 G. m ?that of elemental aluminium.
( {0 H0 y2 ?8 _! j8 d( sSample Solution A
2 R J8 Y7 k- ?4 Y+ f2 T, vAccurately weigh 1 g of the sample and transfer to a 250-ml high-silica
- }2 A) y; `: H3 x( p/ zglass Erlenmeyer flask. Add 10 g of sodium bisulfate (NaHSO4 ? H2O).4 o9 a- ~# w6 c2 Y" M
(Note: Do not use more sodium bisulfate than specified, as an excess& Y& O# q8 z, [3 c
concentration of salt will interfere with the EDTA titration later on in the. i# O( O: r7 E0 {0 f1 Y
procedure.) Begin heating the flask at low heat on a hot plate, and# e; ?8 m: N0 j0 w: X
then gradually raise the temperature until full heat is reached.7 _7 k; l/ `* m, [* y9 v% O" S
(Caution: perform this procedure in a well ventilated area. ) When! j& Q6 z$ W3 Y
spattering has stopped and light fumes of SO3 appear, heat in the full6 C, M* y0 Z+ H( P9 O% S" K* M6 p
flame of a Meeker burner, with the flask tilted so that the fusion of the: n3 \& v6 R) F3 [1 m& b6 a( ?' a
sample and sodium bisulfate is concentrated at one end of the flask.
! y! e3 H T& `) p( @: P0 [) NSwirl constantly until the melt is clear (except for silica content), but
; n4 q/ a! v9 G9 {' B Q+ z" o) ?guard against prolonged heating to avoid precipitation of titanium" w' D. Y( N* X W
dioxide. Cool, add 25 ml sulfuric acid solution (1 in 2), and heat until0 g- @6 z" \2 T
the mass has dissolved and a clear solution results. Cool, and dilute to: j, |/ M4 P$ Y( e( F
120 ml with water. Introduce a magnetic stir bar into the flask.
9 S+ G, y) N5 XSample Solution B
4 q0 T, b, L/ S" ~9 a: V' ~Prepare 200 ml of an approximately 6.25 M solution of sodium
" h; c- _; z; q* I! Chydroxide. Add 65 ml of this solution to Sample Solution A, while5 z0 s% M; r) b) e
stirring with the magnetic stirrer; pour the remaining 135 ml of the7 j6 n9 U5 B7 e
alkali solution into a 500-ml volumetric flask.( p4 ]7 E) t+ r! D$ `
Slowly, with constant stirring, add the sample mixture to the alkali
) n, P9 R8 l2 rsolution in the 500-ml volumetric flask; dilute to volume with water,
0 ~/ f6 _3 e% i) b+ D H- L* r6 gand mix. (Note: If the procedure is delayed at this point for more than
1 a- n' [9 e' Y2 hours, store the contents of the volumetric flask in a polyethylene* B4 b3 C/ [" `8 k4 [/ B; T
bottle.) Allow most of the precipitate to settle (or centrifuge for 5 min),
% K7 j, [$ t8 b2 i7 B$ {" J) s, y6 d! Vthen filter the supernatant liquid through a very fine filter paper. Label7 L6 k, b7 \, p' s
the filtrate Sample Solution B.8 I$ x4 Y: |- q3 k5 S# E; i
Sample Solution C' m1 O$ Q* u7 w
Transfer 100 ml of the Sample Solution B into a 500-ml Erlenmeyer
5 v1 s3 X1 L( i* B2 I, k- r$ l Rflask, add 1 drop of methyl orange TS, acidify with hydrochloric acid f$ T0 Y9 ?5 |/ H* E; M6 R3 q/ `
solution (1 in 2), and then add about 3 ml in excess. Add 25 ml of 0.02
+ Q8 j: \2 I6 T6 w5 o; jM disodium EDTA, and mix. [Note: If the approximate Al2O3 content is- }, T$ s5 `: N8 ~4 u3 ]
known, calculate the optimum volume of EDTA solution to be added F% E7 \% s1 m+ C# h: ?
by the formula: (4 x % Al2O3) + 5.]& x3 Z4 I0 M3 ^, ]2 C
Add, dropwise, ammonia solution (1 in 5) until the colour is just
, T% L, u% j" U3 ocompletely changed from red to orange-yellow. Then add10 ml each
( ^% X, y) X6 j" p7 t" b9 T3 g% qof Solutions 1 and 2 (see above) and boil for 5 min. Cool quickly to
: J0 w o. C1 m, T7 W( a( c6 Froom temperature in a stream of running water, add 3 drops of xylenol5 |# K" v9 L; p, j1 f1 m4 _
orange TS, and mix. If the solution is purple, yellow-brown, or pink,
& _3 z0 [/ z& k% s4 |bring the pH to 5.3 - 5.7 by the addition of acetic acid. At the desired
6 m7 y5 i* w. c; ?' y8 x: r- SpH, a pink colour indicates that not enough of the EDTA solution has; U% v8 T* O0 W8 k. |
been added, in which case, discard the solution and repeat this& G, Z! ]0 p* ]" a7 A, ? [) u; P
procedure with another 100 ml of Sample Solution B, using 50 ml,9 {. E3 F4 E& i5 d
rather than 25 ml, of 0.02 M disodium EDTA.
; ?1 g3 R$ }# xProcedure
" i, ?+ p, ~/ Y3 Z% |- i& T) X2 ^Using the standardized zinc sulfate solution as titrant, titrate Sample
$ a$ ]1 p5 h3 kSolution C to the first yellow-brown or pink end-point that persists for
- `/ Q e7 \: n3 w$ _1 f5-10 sec. (Important: See Note under “0.01 Zinc sulfate”.) This first6 e4 J3 e& b$ K! e% d
titration should require more than 8 ml of titrant, but for more accurate5 r4 @/ Q$ J3 S
work a titration of 10-15 ml is desirable." T# \* b+ P: {5 P, o p! n y
Add 2 g of sodium fluoride to the titration flask, boil the mixture for 2-50 M% v# z& |* ?
min, and cool in a stream of running water. Titrate this solution, using
0 M4 _7 N& C8 n6 k% x# Fthe standardized zinc sulfate solution as titrant, to the same fugitive% P* l& [2 K0 \- S8 H
yellow-brown or pink end-point as described above.
2 o# R2 B7 {/ }& f' `5 r) k1 xCalculation:8 F# h X* z. k) Q. F% ?: @, y
Calculate the percentage of aluminium oxide (Al2O3) in the sample
5 X1 c( U n5 q; _3 Btaken by the formula:8 a: U) n5 _& c9 d; L' y( ^- a
% Al2O3 = 100 × (0.005VT)/S. W7 N; X1 p5 g2 d7 h
where
- g. ]7 C& o( u9 JV is the number of ml of 0.01 N zinc sulfate consumed in
# Z6 g) t! Z/ x5 Pthe second titration,1 d) q; l6 B; ~: b! d7 A4 n# {& N
T is the titre of the zinc sulfate solution,
) l: q+ k' l2 f; Z0 V5 O* MS is the mass (g) of the sample taken, and
' a0 n7 o. e5 ]- f6 x0.005 = 500 ml / (1000mg/g × 100 ml).+ S8 [" r# I& J- E2 a/ e# u3 a( j
Silicon dioxide Accurately weigh 1 g of the sample and transfer to a 250-ml high-silica5 O- t4 z G3 G$ N
glass Erlenmeyer flask. Add 10 g of sodium bisulfate (NaHSO4 ? H2O).
4 s; l& N7 g4 v; G7 }$ I2 r( j6 AHeat gently over a Meeker burner, while swirling the flask, until
2 K$ q( O0 S3 n6 `" X1 k- Cdecomposition and fusion are complete and the melt is clear, except2 W/ k( _- X; Y5 A4 L% ?% X+ _
for the silica content, and then cool. (Caution: Do not overheat the; v' {- l' U5 o" d
contents of the flask at the beginning, and heat cautiously during: O8 ^. o& m4 {% m, |5 g) Z$ d
fusion to avoid spattering.)- J$ U5 |6 ~2 L% C& h h
To the cooled melt add 25 ml of sulfuric acid solution (1 in 2) and heat
9 x) n, W- B, dcarefully and slowly until the melt is dissolved. Cool, and carefully add' F; A2 A2 w' R2 M( \* N. P
150 ml of water by pouring very small portions down the sides of the
* k" }1 n9 s+ ]6 p' V9 n0 Dflask, with frequent swirling to avoid over-heating and spattering. Allow
3 r, ^# \, ^$ L# K" k+ p2 rthe contents of the flask to cool, and filter through fine ashless filter5 a2 x. j# \: {! z5 V- n, m
paper, using a 60 degree gravity funnel. Rinse out all the silica from
; m; B( [$ j. s; S7 Z0 _the flask onto the filter paper with sulfuric acid solution (1 in 10).$ n9 ]3 _. Y6 |& y; r
Transfer the filter paper and its contents into a platinum crucible, dry in/ ~: _) [0 w* b: C2 v6 ~6 U+ f
an oven at 1200, and heat the partly covered crucible over a Bunsen
1 k8 y( L5 J1 f" u2 p& tburner. To prevent flaming of the filter paper, first heat the cover from
/ T/ J- q5 X0 babove, and then the crucible from below.
* i- D! X2 U- S; T" J8 B" z) fWhen the filter paper is consumed, transfer the crucible to a muffle# Q2 r s% Q* i! C
furnace and ignite at 1000o for 30 min. Cool in a desiccator, and
, g. s7 ?- S3 Jweigh. Add 2 drops of sulfuric acid (1 in 2) and 5 ml of concentrated
9 ]2 m7 p3 C8 M( h( o. m1 { {hydrofluoric acid (sp.gr. 1.15), and carefully evaporate to dryness, first1 ?$ X% y/ L0 u% U: Z& W1 h! k
on a low-heat hot plate (to remove the HF) and then over a Bunsen: N5 S. \, @* w- s/ J8 J& ?
burner (to remove the H2SO4). Take precautions to avoid spattering,
M% E5 r9 V3 g7 e# }# Q, |4 R# Lespecially after removal of the HF. Ignite at 1000o for 10 min, cool in a
3 u# h1 t h# T# k* l. I, edesiccator, and weigh again. Record the difference between the two# u& [- W3 y P
weights as the content of SiO2 in the sample.
z/ i! b! u1 v5 W- iMETHOD OF ASSAY
4 _+ P* d" @7 T6 X2 ~9 n# QAccurately weigh about 150 mg of the sample, previously dried at 105o
9 a2 H+ [! W% I4 Z, ~( V- Z/ Ufor 3 hours, and transfer into a 500-ml conical flask. Add 5 ml of water o0 z& \( `2 c6 M1 F9 w. V5 o
and shake until a homogeneous, milky suspension is obtained. Add 30
4 t5 }+ j! w. Uml of sulfuric acid and 12 g of ammonium sulfate, and mix. Initially! w* @! y2 E' T9 |9 W
heat gently, then heat strongly until a clear solution is obtained. Cool,
! Q' \% S3 B7 j8 X9 Kthen cautiously dilute with 120 ml of water and 40 ml of hydrochloric; y) E% ]# y! E+ \3 M
acid, and stir. Add 3 g of aluminium metal, and immediately insert a( l1 o* L0 L8 E6 Z" T
rubber stopper fitted with a U-shaped glass tube while immersing the% o! Y$ j& Y3 J2 l( E+ S6 ^( _ C0 W" | |
other end of the U-tube into a saturated solution of sodium/ s$ U I0 g, w( Q6 B
bicarbonate contained in a 500-ml wide-mouth bottle, and generate# |7 u* n/ Q, u
hydrogen. Allow to stand for a few minutes after the aluminium metal" d- X. Z1 }& B7 K: X4 m/ l
has dissolved completely to produce a transparent purple solution.% }+ \7 @) a7 n6 D$ y: P
Cool to below 50o in running water, and remove the rubber stopper+ @6 o% s& A3 w& s7 l) P
carrying the U-tube. Add 3 ml of a saturated potassium thiocyanate
! c( p6 p- ]* O1 n, a' W2 Msolution as an indicator, and immediately titrate with 0.2 N ferric# H1 j; y9 |% C: [
ammonium sulfate until a faint brown colour that persists for 30
* ]* ]$ z+ `, Y/ |3 tseconds is obtained. Perform a blank determination and make any
" v. c, g# O! j2 G/ B# n1 G6 Tnecessary correction. Each ml of 0.2 N ferric ammonium sulfate is0 y2 e# i( ^5 P* O
equivalent to 7.990 mg of TiO2./ p* M* C$ C4 M2 G
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