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二氧化钛(钛白粉)
二氧化钛(钛白粉)
" ?4 G, I! U5 |5 a. C
" Q/ y% k7 H( X+ d) @$ T6 X, E' rJECFA关于二氧化钛(钛白粉)的结论
' j5 b0 S7 H* X) }8 A, a9 P+ e1 {2 D/ r
摘要: 2006年JECFA关于二氧化钛的结论- V/ ^( h' b; w+ k' g6 _7 Q) h
ADI值:不作限制。' T( l/ B- M: y( N5 D+ p! |
功能:着色剂( }& K/ E* C# V8 r: V9 ^% m$ u3 U4 b
1 }0 A- P8 q) F& C5 l) uTITANIUM DIOXIDE$ I- B, N/ {- O, m1 z
Prepared at the 67th JECFA (2006) and published in FAO JECFA) J- N8 H; ], G
Monographs 3 (2006), superseding specifications prepared at the 63rd
: F, P! K3 \% O% [JECFA (2004) and published in FNP 52 Add 12 (2004) and in the
2 {0 F; F: G1 yCombined Compendium of Food Additive Specifications, FAO JECFA
: u: f F1 }$ a9 E/ T2 n& qMonographs 1 (2005). An ADI “not limited” was established at the 13th1 Z$ i k4 D. q. e$ {
JECFA (1969).( C0 a6 d7 C' y7 W
SYNONYMS
" n& F' \( C! W( c- T7 ]3 k' _( qTitania, CI Pigment white 6, CI (1975) No. 77891, INS No. 171
$ Y" \+ p) X F5 [4 c7 mDEFINITION& m$ M2 F9 v# Q
Titanium dioxide is produced by either the sulfate or the chloride' ]1 t m5 |. Z
process. Processing conditions determine the form (anatase or rutile
- K& m" C8 Q2 U0 xstructure) of the final product.+ O! Q+ v: Q" | V3 u6 r3 e7 p
In the sulfate process, sulfuric acid is used to digest ilmenite (FeTiO3)
; P: ?+ N( K! s' B1 [; M( u0 oor ilmenite and titanium slag. After a series of purification steps, the
: E* w: v; v, ?" e+ zisolated titanium dioxide is finally washed with water, calcined, and1 K' N. n& V$ l+ m9 b# Q& e
micronized.
2 r( K+ M3 Q3 U2 v( _2 x. {8 qIn the chloride process, chlorine gas is reacted with a titaniumcontaining0 q' K; Q b/ C: W& O4 f8 `
mineral under reducing conditions to form anhydrous: i0 w) ^3 j: X+ X& D
titanium tetrachloride, which is subsequently purified and converted to
2 F, E* b1 M4 T* k; Vtitanium dioxide either by direct thermal oxidation or by reaction with: B. F' v5 j9 P: \( ~
steam in the vapour phase. Alternatively, concentrated hydrochloric5 a [) s4 T7 g8 f! d# h5 U
acid can be reacted with the titanium-containing mineral to form a
7 c8 J8 E! ?: y3 r- psolution of titanium tetrachloride, which is then further purified and
0 m _* `; r8 yconverted to titanium dioxide by hydrolysis. The titanium dioxide is% U9 e" K8 r. U( ?1 L
filtered, washed, and calcined.0 V4 p, q/ @( @: p5 |4 |
Commercial titanium dioxide may be coated with small amounts of
# q+ J& r! @7 zalumina and/or silica to improve the technological properties of the' M: u. [: i: z3 Z3 B/ _' p! m
product.
Q2 y2 ]$ i& i, { }4 U& U$ g# LC.A.S. number 13463-67-7$ c0 y! y& X6 @9 n
Chemical formula TiO2, u' p2 {. B+ M& W0 j
Formula weight0 ], }$ ~5 q7 F; h4 ?& }, T
79.88
# t" \- G! [6 D# A R J* {Assay
9 w! P* r" Q. o% Q7 z9 n0 ONot less than 99.0% on the dried basis (on an aluminium oxide and5 N% |/ n5 D# z' S7 O
silicon dioxide-free basis)' L- V; c9 i6 |" x' I1 f: ^6 A
DESCRIPTION
5 d1 i& e1 N5 }' {! s t. o1 P) }White to slightly coloured powder
/ n# d* X* C) q' p& f8 mFUNCTIONAL USES
' m; w! f3 ^ i3 O: q. [Colour
+ Q: i3 D1 i2 F/ p- K. H. H% W! HCHARACTERISTICS
8 ^7 k: F, W0 y4 r+ n1 fIDENTIFICATION
6 h v2 n; X$ q) ESolubility (Vol. 4)' d0 P; A( T- L& m0 O4 K3 M
Insoluble in water, hydrochloric acid, dilute sulfuric acid, and organic3 J, W* o; G- I4 C# e5 r# @
solvents. Dissolves slowly in hydrofluoric acid and hot concentrated
4 S! D. B: o4 r% ?$ ]+ S @- esulfuric acid.4 W# F9 F8 a; u8 w( y. I( O' C
Colour reaction
, r- F2 R6 T. uAdd 5 ml sulfuric acid to 0.5 g of the sample, heat gently until fumes of
, Q3 C. W" h/ I2 ?: r( f2 Rsulfuric acid appear, then cool. Cautiously dilute to about 100 ml with
& k& M z8 }, V0 \0 Twater and filter. To 5 ml of this clear filtrate, add a few drops of
5 h0 ~+ D- F* W, ?! `. I7 Lhydrogen peroxide; an orange-red colour appears immediately.) S3 r% I( I- U5 u8 D( u R
PURITY# t4 ~1 n0 q @/ @7 C
Loss on drying (Vol. 4) Not more than 0.5% (105°, 3 h)
& P! V% d& F+ V" H8 R& V- d2 w* y$ B- qLoss on ignition (Vol. 4)* h; e$ y- x, @& {1 P
Not more than 1.0% (800o) on the dried basis! b# T$ L8 c9 ~: A
Aluminium oxide and/or7 A5 l; u) D5 @% K5 D+ `
silicon dioxide4 D1 l0 A; S B% v! ` M2 N" p6 k& {
Not more than 2%, either singly or combined9 j3 ^' c6 \% B* `3 c9 f9 j% H
See descriptions under TESTS4 Q$ G8 N! l2 B- t1 @( V8 a: f1 P5 v
Acid-soluble substances Not more than 0.5%; Not more than 1.5% for products containing0 S3 x2 t$ F/ D( s5 y
alumina or silica.; n; _3 K" _! d9 I! ]# p9 v/ c
Suspend 5 g of the sample in 100 ml 0.5 N hydrochloric acid and2 z! ^( r8 _* c& V- ^: Z1 c z
place on a steam bath for 30 min with occasional stirring. Filter
7 g c; E8 y1 g. }9 l/ t5 i' T2 L% f% hthrough a Gooch crucible fitted with a glass fibre filter paper. Wash6 V- U! }2 v, l0 x
with three 10-ml portions of 0.5 N hydrochloric acid, evaporate the& |1 H1 `7 T4 _4 j8 B4 C5 l0 L
combined filtrate and washings to dryness, and ignite at a dull red
5 j; f$ F. u: t& v) iheat to constant weight.# p6 L9 O' p* X& a9 N' X! q, `6 l
Water-soluble matter' I E& G l6 L( N4 k
(Vol. 4)
# h( r F1 Q% }8 v( sNot more than 0.5%
3 \/ l5 L2 q Q; W* z" N/ wProceed as directed under acid-soluble substances (above), using$ I4 j8 ?% B2 }. j5 T
water in place of 0.5 N hydrochloric acid.3 w# u! @7 u9 V; {) L+ Q! E# t+ s
Impurities soluble in 0.5 N7 ?7 q$ @! z2 k: J8 e1 c7 Q
hydrochloric acid: y% ]2 x2 a7 S1 ]1 a: }' g9 T4 c
Antimony Not more than 2 mg/kg
) N/ [; s9 J# [1 BSee description under TESTS
( v2 B0 H) |* E: ^5 WArsenic Not more than 1 mg/kg
, q+ i1 k9 m8 _See description under TESTS
- T& e# f' n$ e0 Q; BCadmium Not more than 1 mg/kg
6 w2 {# m5 ?4 L1 T, fSee description under TESTS
! y1 T" [6 d4 r$ C3 H7 S' q# v( t: gLead4 g9 q& i/ F$ @# A
Not more than 10 mg/kg6 {1 H0 i B! O+ x4 f7 W
See description under TESTS5 [0 S9 S8 O! o7 I5 m1 q9 @: k
Mercury (Vol. 4) Not more than 1 mg/kg
. u- P* l% C5 f0 YDetermine using the cold vapour atomic absorption technique. Select a
$ W2 |, _: n! `5 k) ]sample size appropriate to the specified level
" K4 {% S7 x$ l. D, L1 fTESTS8 X. W2 g8 V6 ~
PURITY TESTS. W) K: C8 }- P/ V% U' q6 ?
Impurities soluble in 0.5 N
$ y4 @) z [1 {! x. r8 n1 O" uhydrochloric acid
( {# D W0 \- [: F1 u9 L" PAntimony, arsenic,
; K) X* F0 z! e' h4 p1 icadmium and lead) W- g, l; t8 M, R# k
(Vol.4)# x5 S9 J: L _. a$ T* w9 `. x
Transfer 10.0 g of sample into a 250-ml beaker, add 50 ml of 0.5 N7 D' }- i) J8 w7 y& Z2 Z( B: C
hydrochloric acid, cover with a watch glass, and heat to boiling on a
" o' q2 y0 n& N& bhot plate. Boil gently for 15 min, pour the slurry into a 100- to 150-ml& d* l# t, v) L b2 v0 K
centrifuge bottle, and centrifuge for 10 to 15 min, or until undissolved
! |6 B7 T+ L8 j6 cmaterial settles. Decant the supernatant extract through a Whatman
3 ~+ q, \+ a' {6 aNo. 4 filter paper, or equivalent, collecting the filtrate in a 100-ml5 H4 B* r) {" k. f0 ?1 C, I
volumetric flask and retaining as much as possible of the undissolved2 b' e9 {. ^. C; U3 a; x
material in the centrifuge bottle. Add 10 ml of hot water to the original
' R6 N4 ]9 N$ s( Z( @ [- abeaker, washing off the watch glass with the water, and pour the! Y8 ~7 f% F: ~1 Q- i( z1 w7 V
contents into the centrifuge bottle. Form a slurry, using a glass stirring
( j5 i3 M4 N8 W; grod, and centrifuge. Decant through the same filter paper, and collect' J$ ~ |8 r+ s1 N& {
the washings in the volumetric flask containing the initial extract.* Q7 k+ G: l k9 F
Repeat the entire washing process two more times. Finally, wash the
, k1 |0 m% a5 Z/ F7 ]( Afilter paper with 10 to 15 ml of hot water. Cool the contents of the flask
$ o$ a* G+ f# b% vto room temperature, dilute to volume with water, and mix.
( x; @& Q5 j' O$ B1 @Determine antimony, cadmium, and lead using an AAS/ICP-AES
' s" q$ {! c3 f2 etechnique appropriate to the specified level. Determine arsenic using the' ] [% z( S; g7 ]& Q3 |
ICP-AES/AAS-hydride technique. Alternatively, determine arsenic using
- g) ~# X" g% `/ P) cMethod II of the Arsenic Limit Test, taking 3 g of the sample rather than1 A( f( k0 j* ?! ^& V/ P9 J9 I
1 g. The selection of sample size and method of sample preparation/ @& F- W/ E( w1 K4 t4 M: Y
may be based on the principles of the methods described in Volume 4.
6 Z" ?$ I4 ^5 gAluminium oxide Reagents and sample solutions
4 j2 M+ o. W& } {/ {0.01 N Zinc Sulfate
. [7 }6 G z) L+ {% u% lDissolve 2.9 g of zinc sulfate (ZnSO4 ? 7H2O) in sufficient water to, n( }8 ]& w* R) e% j- ^' E
make 1000 ml. Standardize the solution as follows: Dissolve 500 mg) ?% O. k( H7 i. X$ Q9 U0 d
of high-purity (99.9%) aluminium wire, accurately weighed, in 20 ml of
. ~5 T: ~, q/ K( Mconcentrated hydrochloric acid, heating gently to effect solution, then/ Z) |2 |9 j$ t/ u+ J+ J0 g/ q
transfer the solution into a 1000-ml volumetric flask, dilute to volume
- Y1 L# L, S! V# ^& A, P8 T2 Kwith water, and mix. Transfer a 10 ml aliquot of this solution into a 500
6 x( ]4 B; X6 vml Erlenmeyer flask containing 90 ml of water and 3 ml of
: E. c% a9 g6 L' o5 u% g4 t' Oconcentrated hydrochloric acid, add 1 drop of methyl orange TS and
% r, o. g, ?7 G4 U% Z25 ml of 0.02 M disodium ethylenediaminetetraacetate (EDTA) Add,
3 ?& R: X2 g$ l# C8 Pdropwise, ammonia solution (1 in 5) until the colour is just completely
, t* c+ h* w# Q6 `9 {2 G; bchanged from red to orange-yellow. Then, add:
( ]4 W/ T+ o; F$ c5 V(a): 10 ml of ammonium acetate buffer solution (77 g of
5 g2 K$ B+ ]5 } W0 V3 fammonium acetate plus 10 ml of glacial acetic acid, dilute to( W3 P k. U p! g! a" ]9 u4 _/ D& f
1000 ml with water) and$ J, Q! a* _* n3 g7 i$ V. d
(b): 10 ml of diammonium hydrogen phosphate solution (150 g
, g) A8 H& p3 m/ u5 x8 @of diammonium hydrogen phosphate in 700 ml of water,
/ `* b w) q( A5 |. N2 ~adjusted to pH 5.5 with a 1 in 2 solution of hydrochloric acid,
5 @; M. ~2 U/ K, ]then dilute to 1000 ml with water).
8 V* t4 c( X1 O+ D, N( hBoil the solution for 5 min, cool it quickly to room temperature in a0 g" H% ?7 K/ j7 V4 \& M6 x
stream of running water, add 3 drops of xylenol orange TS, and mix.0 q# {: ]& y4 v' i+ |
Using the zinc sulfate solution as titrant, titrate the solution to the first
: j; l" w+ G4 S: P8 wyellow-brown or pink end-point colour that persists for 5-10 sec. (Note:
* C' E6 J$ T" |$ h3 V6 A8 y' v+ ?This titration should be performed quickly near the end-point by
8 ~# Z) ]& }( N! Q1 t; q. \adding rapidly 0.2 ml increments of the titrant until the first colour
5 ~ Y: k) r3 B% echange occurs; although the colour will fade in 5-10 sec, it is the true
( f1 G: `+ M) q4 l. G* l& yend-point. Failure to observe the first colour change will result in an/ n& u2 S" C8 d0 t
incorrect titration. The fading end-point does not occur at the second
* m1 |* \; C( L4 B, x: Iend-point.)
/ {2 p/ z* s0 S3 RAdd 2 g of sodium fluoride, boil the mixture for 2-5 min, and cool in a: ~: y8 O6 H7 Q* c5 Q4 ?
stream of running water. Titrate this solution, using the zinc sulfate
. \: D8 @& t' Usolution as titrant, to the same fugitive yellow-brown or pink end-point
8 \: p3 H! }7 U q/ B. Mas described above.) c( Y; F' Q/ S5 ^4 L/ P8 y
Calculate the titre T of zinc sulfate solution by the formula:+ ~. |* O' S* q# A; {$ ]0 v
T = 18.896 W / V: [: r9 m0 V n
where* m; a+ A- C m1 p$ k! G# m# k% D
T is the mass (mg) of Al2O3 per ml of zinc sulfate solution
1 ~# ^ n! u4 x p- d4 R6 z8 uW is the mass (g) of aluminium wire. ?& D. `! Y' F2 J# m) J; Q/ f. A
V is the ml of the zinc sulfate solution consumed in the8 c6 g4 c% }! ]: n9 j
second titration
9 e* H$ O; C- ~$ }4 Y' {2 _18.896 = (R × 1000 mg/g × 10 ml/2)/1000 ml and
* y: B8 Y0 R3 s) j4 f& TR is the ratio of the formula weight of aluminium oxide to
" i$ _- p% x, B" l: Sthat of elemental aluminium." g* E6 h" m# Q1 |( b
Sample Solution A( @( }9 H% o0 e% p! g
Accurately weigh 1 g of the sample and transfer to a 250-ml high-silica
* `, [' I) v, Mglass Erlenmeyer flask. Add 10 g of sodium bisulfate (NaHSO4 ? H2O).
3 k: `1 ]& U) Y) Q6 B2 X% W(Note: Do not use more sodium bisulfate than specified, as an excess
3 {( Y9 V0 l7 H9 y" y& |" f& Aconcentration of salt will interfere with the EDTA titration later on in the( h" ?; @. @5 |' q/ e! X
procedure.) Begin heating the flask at low heat on a hot plate, and; E1 d9 B" P/ f9 J
then gradually raise the temperature until full heat is reached.! G) R- `' O2 n* w1 K/ j' q
(Caution: perform this procedure in a well ventilated area. ) When
8 i' f# W, @ x" f) Pspattering has stopped and light fumes of SO3 appear, heat in the full/ q9 p7 a/ R% ]
flame of a Meeker burner, with the flask tilted so that the fusion of the
5 w+ Q6 q6 F; ]$ Z7 Lsample and sodium bisulfate is concentrated at one end of the flask.
) ^8 v" {' m0 z; G3 rSwirl constantly until the melt is clear (except for silica content), but
! Q1 O Q t, O) i! B& R9 Gguard against prolonged heating to avoid precipitation of titanium' }0 ]' [' H7 A7 {3 ?
dioxide. Cool, add 25 ml sulfuric acid solution (1 in 2), and heat until
/ B0 @- Z7 N( f4 Sthe mass has dissolved and a clear solution results. Cool, and dilute to
( D8 N- }1 [/ T( [# U3 ~' C; H120 ml with water. Introduce a magnetic stir bar into the flask.: q. m l1 E& r4 ?$ A
Sample Solution B2 q, Z/ ~- ~. R
Prepare 200 ml of an approximately 6.25 M solution of sodium1 R) l5 Z% l6 x3 z" U+ A
hydroxide. Add 65 ml of this solution to Sample Solution A, while+ k( u7 H, [) ^" M" L) E
stirring with the magnetic stirrer; pour the remaining 135 ml of the% W' P5 U& V, Z- @
alkali solution into a 500-ml volumetric flask.
2 L0 C- \9 W4 H9 o f$ {, tSlowly, with constant stirring, add the sample mixture to the alkali
% F" S! }9 @" u4 J+ Tsolution in the 500-ml volumetric flask; dilute to volume with water,
0 Y0 T0 [4 o) p! ?and mix. (Note: If the procedure is delayed at this point for more than! e# G& n8 a3 B$ T: Q6 ?2 j
2 hours, store the contents of the volumetric flask in a polyethylene7 I# S( [3 h( f' k/ M
bottle.) Allow most of the precipitate to settle (or centrifuge for 5 min),
4 a6 b+ z1 w, o& ^5 T- E: D" Bthen filter the supernatant liquid through a very fine filter paper. Label
+ H6 T3 \" m" |9 Ythe filtrate Sample Solution B.% i$ ?/ b. V) a7 s& l) z* p
Sample Solution C
h! P9 [7 O Z& d+ E* P) _7 BTransfer 100 ml of the Sample Solution B into a 500-ml Erlenmeyer
( l+ \& ]$ r) q, @$ R( l5 Hflask, add 1 drop of methyl orange TS, acidify with hydrochloric acid! p9 f( V4 {* }8 G' Q% e3 K
solution (1 in 2), and then add about 3 ml in excess. Add 25 ml of 0.02
7 ~* E/ h5 r) eM disodium EDTA, and mix. [Note: If the approximate Al2O3 content is
; a( k. Y' d( U; u5 a5 \known, calculate the optimum volume of EDTA solution to be added+ F5 ^* j7 H4 Z2 [8 [9 m) d( x
by the formula: (4 x % Al2O3) + 5.]
3 l( ]( L* d8 B- nAdd, dropwise, ammonia solution (1 in 5) until the colour is just: d6 f/ Q0 N) E2 n$ p
completely changed from red to orange-yellow. Then add10 ml each/ q, `$ N- N- Y1 u! a
of Solutions 1 and 2 (see above) and boil for 5 min. Cool quickly to
0 @2 t9 b. t6 troom temperature in a stream of running water, add 3 drops of xylenol
% h- o$ `; t9 I+ e& xorange TS, and mix. If the solution is purple, yellow-brown, or pink,
4 }6 u' P- K) M ^# H6 M) Z/ _bring the pH to 5.3 - 5.7 by the addition of acetic acid. At the desired: H/ _) N) {1 v' U1 O& K# w/ e3 n r
pH, a pink colour indicates that not enough of the EDTA solution has
2 g m1 Q1 B$ l0 V7 Gbeen added, in which case, discard the solution and repeat this
7 A. I( j: ] ^ Y: Uprocedure with another 100 ml of Sample Solution B, using 50 ml,
" B% G- z, Z% P jrather than 25 ml, of 0.02 M disodium EDTA.
. S1 x+ I! o$ c+ r) ?* U& Z( @6 _* oProcedure
8 j, Q1 k8 Z; H, r9 b* mUsing the standardized zinc sulfate solution as titrant, titrate Sample
4 {0 a5 I& F: [7 S1 Y5 A3 oSolution C to the first yellow-brown or pink end-point that persists for, @! C/ F/ c- g& u* `* ^
5-10 sec. (Important: See Note under “0.01 Zinc sulfate”.) This first9 B. ~0 y4 X0 U% [7 e. k8 w1 d
titration should require more than 8 ml of titrant, but for more accurate) |5 V- O8 t6 a1 V
work a titration of 10-15 ml is desirable.
9 C! v) {0 _) xAdd 2 g of sodium fluoride to the titration flask, boil the mixture for 2-5) u; Y/ }$ R) \. D1 a* B
min, and cool in a stream of running water. Titrate this solution, using
6 w; @1 T3 c& w* B athe standardized zinc sulfate solution as titrant, to the same fugitive" D/ T, w1 K" f
yellow-brown or pink end-point as described above.
" Z" H7 J8 G8 r6 J- |5 z- KCalculation:" x3 d6 x7 q! N0 Q
Calculate the percentage of aluminium oxide (Al2O3) in the sample o& |/ `& L; v$ S7 w! F0 Q
taken by the formula:3 v9 K- Q6 H) H) Y' r& n+ W
% Al2O3 = 100 × (0.005VT)/S
1 m( q" t& U& o; s9 bwhere n! U) ]( K( T& f. G6 H. m/ W
V is the number of ml of 0.01 N zinc sulfate consumed in
7 R6 x1 T- v+ O% z1 c+ tthe second titration,
* ?. B/ L% h) i0 X9 z m1 r( x: rT is the titre of the zinc sulfate solution,
& {" h. ~2 A% ~# qS is the mass (g) of the sample taken, and# c+ V( `0 l. N/ S# w3 K+ Z4 b
0.005 = 500 ml / (1000mg/g × 100 ml).5 y" _5 |2 g8 {- I0 A3 o
Silicon dioxide Accurately weigh 1 g of the sample and transfer to a 250-ml high-silica
% N( b. u9 K* w: ?: n! l. Lglass Erlenmeyer flask. Add 10 g of sodium bisulfate (NaHSO4 ? H2O).
, t9 [- `) o) @$ f$ U& ~% Q3 qHeat gently over a Meeker burner, while swirling the flask, until
- B5 y5 @! r: x5 {decomposition and fusion are complete and the melt is clear, except
0 d s5 v3 B& `- a: F- p7 \for the silica content, and then cool. (Caution: Do not overheat the: D+ F/ d) s* \
contents of the flask at the beginning, and heat cautiously during
, Y. q) t1 w; P+ Q+ mfusion to avoid spattering.)" _* I! C2 Y) s; x0 ?
To the cooled melt add 25 ml of sulfuric acid solution (1 in 2) and heat) `2 L! R$ S% D6 k5 z' _
carefully and slowly until the melt is dissolved. Cool, and carefully add8 l; u$ `1 l( l" O$ p" G
150 ml of water by pouring very small portions down the sides of the
0 A- S; s# W; ]; ]flask, with frequent swirling to avoid over-heating and spattering. Allow# h0 f$ R8 W, s. x, r
the contents of the flask to cool, and filter through fine ashless filter
7 ?: B: J) @* C4 N+ @4 W/ U; spaper, using a 60 degree gravity funnel. Rinse out all the silica from
' g" R3 y6 {( l5 Z/ h- hthe flask onto the filter paper with sulfuric acid solution (1 in 10).
& A) [( p- O- e, O2 k! j; PTransfer the filter paper and its contents into a platinum crucible, dry in
+ R' Q$ O0 _% O2 S$ v3 F% fan oven at 1200, and heat the partly covered crucible over a Bunsen* f; }* x' x/ y5 { U
burner. To prevent flaming of the filter paper, first heat the cover from' ?- T6 E! O& v
above, and then the crucible from below., z- s5 z6 C8 m1 E
When the filter paper is consumed, transfer the crucible to a muffle. o" I7 x; p5 w) q; i9 J
furnace and ignite at 1000o for 30 min. Cool in a desiccator, and2 q* ~$ C# E: O( N4 b, {7 u
weigh. Add 2 drops of sulfuric acid (1 in 2) and 5 ml of concentrated6 v3 S. d" k4 J! Q3 S# ]
hydrofluoric acid (sp.gr. 1.15), and carefully evaporate to dryness, first1 c0 R/ \5 x, i9 N) ]& G
on a low-heat hot plate (to remove the HF) and then over a Bunsen& X7 g6 J" Q" G& q
burner (to remove the H2SO4). Take precautions to avoid spattering,3 k! P! Y) Y/ t5 [
especially after removal of the HF. Ignite at 1000o for 10 min, cool in a
, h' [1 T* Q; y% `( sdesiccator, and weigh again. Record the difference between the two# e5 b: l$ ^: v( u' m) l6 Q
weights as the content of SiO2 in the sample.
& c, s2 W' ?9 u' ~# ? U- mMETHOD OF ASSAY
, L q0 Z$ a5 B0 R: cAccurately weigh about 150 mg of the sample, previously dried at 105o( Z; _9 M" L9 k$ E8 q/ X- z! g
for 3 hours, and transfer into a 500-ml conical flask. Add 5 ml of water
1 L+ {1 c/ p6 f2 ~/ L: @; Gand shake until a homogeneous, milky suspension is obtained. Add 30
4 D% T+ B, U1 K9 _9 V" Iml of sulfuric acid and 12 g of ammonium sulfate, and mix. Initially& D) N1 M4 }5 c4 W! e* r) X9 A
heat gently, then heat strongly until a clear solution is obtained. Cool,- F$ _% T; G( T4 F! V M
then cautiously dilute with 120 ml of water and 40 ml of hydrochloric
. `# O" K. t: \% |* u d8 x4 ]acid, and stir. Add 3 g of aluminium metal, and immediately insert a
. s) j. |2 i$ z0 Nrubber stopper fitted with a U-shaped glass tube while immersing the
$ }/ i6 h* F- U# i) C6 cother end of the U-tube into a saturated solution of sodium% d' k% B8 }$ ]
bicarbonate contained in a 500-ml wide-mouth bottle, and generate, U G1 e: @% R3 e$ t3 s' W
hydrogen. Allow to stand for a few minutes after the aluminium metal8 V0 @! Y8 A9 k; L4 I
has dissolved completely to produce a transparent purple solution.- h$ f! a3 C+ `
Cool to below 50o in running water, and remove the rubber stopper
S0 ?6 w0 {- j6 f! q# B' F& y% L2 Zcarrying the U-tube. Add 3 ml of a saturated potassium thiocyanate
1 W5 {, b7 K- K& i- \2 p2 X* Asolution as an indicator, and immediately titrate with 0.2 N ferric
8 [) ]* i( M5 J- X+ g& |ammonium sulfate until a faint brown colour that persists for 30 b5 q$ z, f( [5 |$ P0 k
seconds is obtained. Perform a blank determination and make any
' w5 W; N" s# e0 ?' Znecessary correction. Each ml of 0.2 N ferric ammonium sulfate is
; |: @6 d0 \" s* t7 y7 ^equivalent to 7.990 mg of TiO2." W' T3 r% K& ~( `" K
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