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二氧化钛(钛白粉)
二氧化钛(钛白粉)6 a$ s9 g: W7 \1 O0 n
I' z$ Q1 p% V% mJECFA关于二氧化钛(钛白粉)的结论( ~% q5 Z {2 I' w* \
4 m$ N" ?3 D& y# r摘要: 2006年JECFA关于二氧化钛的结论* z, J& `& |+ X3 s3 g( x
ADI值:不作限制。
; b4 G* ]9 M6 y1 d功能:着色剂
$ j/ [/ R" H; m. o) x
2 E# Y& c* k- H" sTITANIUM DIOXIDE
3 U. t( U6 H; a. n1 d3 yPrepared at the 67th JECFA (2006) and published in FAO JECFA
3 q8 f3 h9 u% Y' x& J7 ] f5 k8 d+ `Monographs 3 (2006), superseding specifications prepared at the 63rd
4 `2 l: X8 }7 D9 k, {: Q0 @* LJECFA (2004) and published in FNP 52 Add 12 (2004) and in the
1 U8 P: A6 j, C4 `Combined Compendium of Food Additive Specifications, FAO JECFA
$ \7 I0 Z) U7 v3 N8 hMonographs 1 (2005). An ADI “not limited” was established at the 13th
2 ^2 |0 Y8 K9 N; E1 GJECFA (1969).. S U& I8 Y' X" K" |8 ^5 e1 H
SYNONYMS& V# e+ Y/ x7 v, A0 w
Titania, CI Pigment white 6, CI (1975) No. 77891, INS No. 171$ X* |4 M1 [7 O* G" a+ X
DEFINITION4 O1 [& S& ~4 o) E% P- i
Titanium dioxide is produced by either the sulfate or the chloride
! M v: e8 k! i7 G# u) L; ?process. Processing conditions determine the form (anatase or rutile
# I9 `% i3 G, C6 M0 _6 C6 F3 lstructure) of the final product.$ L* X" m. w8 N; Q
In the sulfate process, sulfuric acid is used to digest ilmenite (FeTiO3)5 C. Z( Q6 ?8 j; V) F. n$ d
or ilmenite and titanium slag. After a series of purification steps, the) f! H+ O' H9 T1 U0 t
isolated titanium dioxide is finally washed with water, calcined, and
$ E* L& o6 F. `9 W6 A- p6 Zmicronized.
# W! |' G, k' K% n8 pIn the chloride process, chlorine gas is reacted with a titaniumcontaining
* F6 ]; {$ q8 }3 n& p+ \* p8 Bmineral under reducing conditions to form anhydrous9 H, n( i0 |' b M
titanium tetrachloride, which is subsequently purified and converted to( C, h: g. m- Y$ g1 g; c8 K; o
titanium dioxide either by direct thermal oxidation or by reaction with
: c' N9 n: k) S$ A7 H* rsteam in the vapour phase. Alternatively, concentrated hydrochloric- Z9 B$ {# a2 c) u, a6 Z# F
acid can be reacted with the titanium-containing mineral to form a3 _; D9 j- {, s0 N8 p: g. ~- q: t
solution of titanium tetrachloride, which is then further purified and
! F [! W9 Q# [ E. o- }converted to titanium dioxide by hydrolysis. The titanium dioxide is5 R# M( R# v6 }0 [) z2 A8 v
filtered, washed, and calcined./ }1 h# f8 l4 V% R$ d9 M. W) g
Commercial titanium dioxide may be coated with small amounts of
( \ k a! ]6 Q4 j6 l+ Nalumina and/or silica to improve the technological properties of the2 F+ c0 F5 K; |5 d7 S
product.. o U& Q8 p7 ]# k& y
C.A.S. number 13463-67-7
9 |: X! X7 ^9 v+ u5 I: o9 fChemical formula TiO2
& w# V4 [, y# I$ VFormula weight! S0 l# D; m- \+ T
79.88
. ]; _ T; n, H* k# bAssay0 I0 ^) r3 l" I+ z% t! s
Not less than 99.0% on the dried basis (on an aluminium oxide and
; X& ]5 [+ g" E# ]& S7 e( S5 qsilicon dioxide-free basis)
& v% G( p% z+ B4 DDESCRIPTION* K. e+ J% K: G k3 m& f4 `( P
White to slightly coloured powder
( @* r! O# t( r0 X0 WFUNCTIONAL USES, e) c+ u7 q9 Z; v1 ]
Colour
- Z9 m$ M# a6 \+ Z4 `4 V9 K0 _CHARACTERISTICS6 |9 v6 e* @9 E9 Z' \
IDENTIFICATION
3 T" C- S% D5 S6 N3 M0 a z$ f& |$ V, XSolubility (Vol. 4)
" y/ f& Y& l9 [6 }Insoluble in water, hydrochloric acid, dilute sulfuric acid, and organic2 t) k6 y2 m! f% S
solvents. Dissolves slowly in hydrofluoric acid and hot concentrated
% b A8 Q+ H6 tsulfuric acid.5 h& r: A7 G5 K, @
Colour reaction6 k' F8 g' ~3 G( A
Add 5 ml sulfuric acid to 0.5 g of the sample, heat gently until fumes of
& E- v9 M$ L0 K- n3 B/ xsulfuric acid appear, then cool. Cautiously dilute to about 100 ml with9 O6 P# ?' @5 T- N# v5 l+ A
water and filter. To 5 ml of this clear filtrate, add a few drops of4 M. p2 x7 i: E* q% X; e8 v9 \
hydrogen peroxide; an orange-red colour appears immediately.
* h' }3 z+ G7 b, J" P' d# h% v \2 HPURITY2 J* B$ E& {1 x% S+ F
Loss on drying (Vol. 4) Not more than 0.5% (105°, 3 h) O3 A+ J) r4 _; C
Loss on ignition (Vol. 4)
; t8 E/ Z7 E+ u! B! @4 {Not more than 1.0% (800o) on the dried basis( c& w7 o1 B4 a% ~
Aluminium oxide and/or% I k, d2 r- T& n. P9 ?; v
silicon dioxide, U+ }- E+ e+ |7 n- n4 j' Q& U3 _. C
Not more than 2%, either singly or combined' k( o( H+ G( ]* ]. k# h
See descriptions under TESTS
& P) d4 ]( P- ]Acid-soluble substances Not more than 0.5%; Not more than 1.5% for products containing( B5 K% Z1 K4 D# b2 v
alumina or silica.
9 t, ]- l# R `$ nSuspend 5 g of the sample in 100 ml 0.5 N hydrochloric acid and
$ F1 F j$ z0 kplace on a steam bath for 30 min with occasional stirring. Filter
0 |6 q* _: U6 k% C- zthrough a Gooch crucible fitted with a glass fibre filter paper. Wash4 [, A0 t; }+ f/ W5 O o
with three 10-ml portions of 0.5 N hydrochloric acid, evaporate the
' l6 t# m& p0 P) ^ j2 L& Ocombined filtrate and washings to dryness, and ignite at a dull red
" B+ }! S/ e) R5 r. Sheat to constant weight.3 x; I5 c a6 @
Water-soluble matter
# E. z9 E( M6 N$ G+ x/ ?' C(Vol. 4)7 ?9 `4 l4 P2 Y7 P5 I7 n, J! }
Not more than 0.5%
) H2 }/ ?5 X; WProceed as directed under acid-soluble substances (above), using. s% d9 v5 |4 x3 ]& m
water in place of 0.5 N hydrochloric acid.! m/ ?# |" r7 x5 r) T; Q! n U
Impurities soluble in 0.5 N/ d3 d" Q, L' @2 U: `
hydrochloric acid
/ @: \8 U5 a6 e9 X% y- y: FAntimony Not more than 2 mg/kg
* ] n: r) |9 B; b; R9 R5 ESee description under TESTS
9 o h0 h2 q( n" C% l' T( PArsenic Not more than 1 mg/kg( R) J+ C+ x" `) Q1 R
See description under TESTS7 ]6 W+ ~$ o3 |5 {
Cadmium Not more than 1 mg/kg! D& |! G6 ?- s5 r8 t5 e
See description under TESTS
; l: E! I( K( l1 ?Lead% i# m; K3 P2 f' `1 _
Not more than 10 mg/kg
2 N9 W8 R# y) Y$ z1 _- ySee description under TESTS C4 x+ ]/ a( B$ X6 c; V
Mercury (Vol. 4) Not more than 1 mg/kg
( n/ |& L) S% a" g. tDetermine using the cold vapour atomic absorption technique. Select a6 h; j- R" A' G4 ?# ^
sample size appropriate to the specified level6 | o6 M4 b b- h
TESTS: a* U; A& Q) J$ j8 E
PURITY TESTS2 h0 {9 Y: r: b2 x3 S8 N- v
Impurities soluble in 0.5 N7 a5 T1 Z- u/ @" G
hydrochloric acid
! i7 S7 ^8 M- z! y( |6 o* ^Antimony, arsenic,
+ I1 t& ~1 H* x1 r8 U; lcadmium and lead; S x) N' _6 J/ U8 G
(Vol.4)
: _; t9 R1 v) \) Y) ]Transfer 10.0 g of sample into a 250-ml beaker, add 50 ml of 0.5 N$ g9 s' e9 z, s4 ]$ U
hydrochloric acid, cover with a watch glass, and heat to boiling on a
: C% X; w0 h9 Rhot plate. Boil gently for 15 min, pour the slurry into a 100- to 150-ml
0 j4 K) f5 g" \# Bcentrifuge bottle, and centrifuge for 10 to 15 min, or until undissolved" Z4 f4 X8 j, k9 u& J$ J0 o. E
material settles. Decant the supernatant extract through a Whatman
! B+ a% h& K0 cNo. 4 filter paper, or equivalent, collecting the filtrate in a 100-ml
; h5 A! s9 A4 Z( i' H. Kvolumetric flask and retaining as much as possible of the undissolved
! S) l) d; {7 f$ k& y6 jmaterial in the centrifuge bottle. Add 10 ml of hot water to the original
. O3 J) e0 P( P V6 W1 x' y/ [) Q& m% |beaker, washing off the watch glass with the water, and pour the4 p% ~& [/ J" r' U+ C# k# D9 M* [0 L/ W
contents into the centrifuge bottle. Form a slurry, using a glass stirring
& B! @9 l( B R8 {, frod, and centrifuge. Decant through the same filter paper, and collect5 ]9 {0 |1 @9 U
the washings in the volumetric flask containing the initial extract.
# f. J4 o( z) l, f9 ~! x- ZRepeat the entire washing process two more times. Finally, wash the3 s5 a; w$ b+ k8 h0 y) {5 V
filter paper with 10 to 15 ml of hot water. Cool the contents of the flask( z" c' a# b- t: i* U
to room temperature, dilute to volume with water, and mix.
( @7 N# ~# M' cDetermine antimony, cadmium, and lead using an AAS/ICP-AES
1 a0 N! p% f9 F3 I8 ` ntechnique appropriate to the specified level. Determine arsenic using the6 X4 X1 W: B9 q& x1 r+ S% x# K
ICP-AES/AAS-hydride technique. Alternatively, determine arsenic using/ t: E% n V4 P4 C1 d/ s
Method II of the Arsenic Limit Test, taking 3 g of the sample rather than
! {0 t2 C% D# @( q; C1 g. The selection of sample size and method of sample preparation
, o9 R0 D: K; }9 q9 x0 Bmay be based on the principles of the methods described in Volume 4.
& W) D. f% b+ m, w; @& s# K, qAluminium oxide Reagents and sample solutions r8 k: Z' k# O% N
0.01 N Zinc Sulfate( {5 \+ m$ Y6 A) j0 N
Dissolve 2.9 g of zinc sulfate (ZnSO4 ? 7H2O) in sufficient water to
N; L1 p- @4 Lmake 1000 ml. Standardize the solution as follows: Dissolve 500 mg, W2 l1 ^5 D$ b: q/ Y
of high-purity (99.9%) aluminium wire, accurately weighed, in 20 ml of+ u0 v( y1 y: {$ W
concentrated hydrochloric acid, heating gently to effect solution, then! y2 P6 s; { F e) c. P
transfer the solution into a 1000-ml volumetric flask, dilute to volume# K1 F( T8 h5 h5 b8 \. h5 u
with water, and mix. Transfer a 10 ml aliquot of this solution into a 500! l1 V' w" z1 C1 N" M0 J
ml Erlenmeyer flask containing 90 ml of water and 3 ml of
" B) Z e2 w( d$ x. ]! x$ t5 `9 c3 Rconcentrated hydrochloric acid, add 1 drop of methyl orange TS and4 `4 r( N" b5 g( g
25 ml of 0.02 M disodium ethylenediaminetetraacetate (EDTA) Add,% a/ X3 l# @4 X+ P
dropwise, ammonia solution (1 in 5) until the colour is just completely
+ i- q- n- r0 @changed from red to orange-yellow. Then, add:
# U# G# q& O4 E" }$ S9 |! A) S(a): 10 ml of ammonium acetate buffer solution (77 g of% N9 H! e# ^8 J" r' O8 Y
ammonium acetate plus 10 ml of glacial acetic acid, dilute to3 h$ E4 p2 D$ b B
1000 ml with water) and1 `: I; l* U8 b4 b% {7 A
(b): 10 ml of diammonium hydrogen phosphate solution (150 g" T: o, [& c9 S: e1 `' _
of diammonium hydrogen phosphate in 700 ml of water,
3 h3 g* Q* i2 D: A* cadjusted to pH 5.5 with a 1 in 2 solution of hydrochloric acid,
$ s2 u. d$ w* h1 i1 l' {then dilute to 1000 ml with water).7 @+ Z' m. d% h3 @; x j
Boil the solution for 5 min, cool it quickly to room temperature in a
) ?: v0 [0 [; t: |; tstream of running water, add 3 drops of xylenol orange TS, and mix.
5 s4 ~- b7 b0 @: J* G/ i8 KUsing the zinc sulfate solution as titrant, titrate the solution to the first
. e: [* x5 ]. q9 @; L, lyellow-brown or pink end-point colour that persists for 5-10 sec. (Note:+ ]9 W& t+ u+ y7 N
This titration should be performed quickly near the end-point by# a% R4 X& Y1 O; w; b5 ^- B
adding rapidly 0.2 ml increments of the titrant until the first colour2 r; U) S- F7 i1 l
change occurs; although the colour will fade in 5-10 sec, it is the true6 ]) r0 x5 O1 q9 T9 c3 X% N
end-point. Failure to observe the first colour change will result in an
- z( [6 Z t$ o4 r g( A) K9 E3 sincorrect titration. The fading end-point does not occur at the second3 \2 s# \$ E q# y1 Y# k0 I
end-point.)
- D3 _' \5 d' V% l! _8 B6 WAdd 2 g of sodium fluoride, boil the mixture for 2-5 min, and cool in a( t( [+ T8 I$ @2 E( e
stream of running water. Titrate this solution, using the zinc sulfate
- s2 e A7 Z4 }solution as titrant, to the same fugitive yellow-brown or pink end-point
8 ]* Z4 E9 x; D- U# c% Das described above.% w# p4 n* l6 W" X- d7 n5 `
Calculate the titre T of zinc sulfate solution by the formula:
: }0 S& h& b- J3 z4 V7 O* ET = 18.896 W / V; w+ b( o- s6 q! E& l
where7 U6 j0 s; j! R9 k
T is the mass (mg) of Al2O3 per ml of zinc sulfate solution
5 }+ P x- E+ N- A' P5 hW is the mass (g) of aluminium wire
( }1 E! a" k$ o* q9 e hV is the ml of the zinc sulfate solution consumed in the! v& i* v& l3 D/ ~) T8 y4 P
second titration
, f; ?! z* u: [$ E18.896 = (R × 1000 mg/g × 10 ml/2)/1000 ml and
7 Y2 w5 y* k/ A% qR is the ratio of the formula weight of aluminium oxide to
. U7 M7 F" I* c _2 X/ `' wthat of elemental aluminium.
% b, p- g1 n7 t9 _' X7 L- `Sample Solution A7 f) R5 [. R! u8 W( R @
Accurately weigh 1 g of the sample and transfer to a 250-ml high-silica/ C' V6 a3 l a0 e7 h
glass Erlenmeyer flask. Add 10 g of sodium bisulfate (NaHSO4 ? H2O).* ?6 @6 W" n$ s! _" X4 n
(Note: Do not use more sodium bisulfate than specified, as an excess
% @: k; i. ?' d" E( _8 @/ {concentration of salt will interfere with the EDTA titration later on in the
1 `- ?1 ^2 u @$ sprocedure.) Begin heating the flask at low heat on a hot plate, and
* ^ {# N- p$ Sthen gradually raise the temperature until full heat is reached.
9 {+ x2 j+ G7 P/ |- H(Caution: perform this procedure in a well ventilated area. ) When6 P. N0 n) E! m J
spattering has stopped and light fumes of SO3 appear, heat in the full
+ x( V: d+ Y. I5 g; \flame of a Meeker burner, with the flask tilted so that the fusion of the
& k4 p7 @, L# a- C* V% B' i) I8 Q9 r9 ?sample and sodium bisulfate is concentrated at one end of the flask.
z2 v: }" Z6 m9 n/ g% E" T- g, nSwirl constantly until the melt is clear (except for silica content), but
& b1 T8 Z; W. mguard against prolonged heating to avoid precipitation of titanium
: T$ W/ c! p: _7 odioxide. Cool, add 25 ml sulfuric acid solution (1 in 2), and heat until
5 M, ?2 \; F2 K' }2 othe mass has dissolved and a clear solution results. Cool, and dilute to
# f/ g" }) z/ U" y+ m120 ml with water. Introduce a magnetic stir bar into the flask.
9 V( ~, X8 f; {' r, K) l& [Sample Solution B
, T3 Y% b3 v; f4 C2 sPrepare 200 ml of an approximately 6.25 M solution of sodium! B5 J2 y0 Y6 I& g* }+ \8 i: h. C
hydroxide. Add 65 ml of this solution to Sample Solution A, while
# k( T2 p" d* Fstirring with the magnetic stirrer; pour the remaining 135 ml of the
- K$ u; R2 w4 u" j& walkali solution into a 500-ml volumetric flask.
3 E1 p: \, }( _& X8 H$ V' b$ w0 L rSlowly, with constant stirring, add the sample mixture to the alkali
8 B8 r% o4 P; I) ^2 Jsolution in the 500-ml volumetric flask; dilute to volume with water,
7 w8 f3 e+ z! s: Q0 }/ E8 R. wand mix. (Note: If the procedure is delayed at this point for more than, }' G W& j4 N9 K! Z* T$ Y
2 hours, store the contents of the volumetric flask in a polyethylene' Z7 ~7 w, \$ ?5 c6 \
bottle.) Allow most of the precipitate to settle (or centrifuge for 5 min),) }# z% `$ U& r
then filter the supernatant liquid through a very fine filter paper. Label" Y h" w, Y, N9 `
the filtrate Sample Solution B.' c8 A8 d/ K4 C, y+ Q
Sample Solution C+ |$ W- i7 g& ~& D3 o6 Y
Transfer 100 ml of the Sample Solution B into a 500-ml Erlenmeyer
% k) m1 x. n8 G% \7 U* ~. V. @flask, add 1 drop of methyl orange TS, acidify with hydrochloric acid" Q j; t) }1 z
solution (1 in 2), and then add about 3 ml in excess. Add 25 ml of 0.02: D6 W/ ~& {$ `0 o, ], G
M disodium EDTA, and mix. [Note: If the approximate Al2O3 content is
! B" ^3 S2 V3 z) Q: G1 S; t' `0 Rknown, calculate the optimum volume of EDTA solution to be added
0 B8 B5 I8 F j9 X$ u u$ Jby the formula: (4 x % Al2O3) + 5.]
1 B4 P" k5 x: OAdd, dropwise, ammonia solution (1 in 5) until the colour is just& e: l2 }4 B. t. Y. V
completely changed from red to orange-yellow. Then add10 ml each9 a- ~" z* w6 @# ~' y0 ?$ {
of Solutions 1 and 2 (see above) and boil for 5 min. Cool quickly to1 W3 m# e8 m' K" A8 O! {
room temperature in a stream of running water, add 3 drops of xylenol/ z. B1 A- R. y& a
orange TS, and mix. If the solution is purple, yellow-brown, or pink,: F+ o' ?: c! a! o: N4 p
bring the pH to 5.3 - 5.7 by the addition of acetic acid. At the desired
& l5 [" w( d+ p, z' j2 ipH, a pink colour indicates that not enough of the EDTA solution has
& j4 ~$ ]5 \! v ~0 I+ {been added, in which case, discard the solution and repeat this1 Y M6 U& L S# @' U, V. r+ V
procedure with another 100 ml of Sample Solution B, using 50 ml,
/ W, W1 h! }8 H' vrather than 25 ml, of 0.02 M disodium EDTA." A8 B) `5 b& p, o) b9 k
Procedure
2 }# e- g5 s# M( q' nUsing the standardized zinc sulfate solution as titrant, titrate Sample3 f/ C/ R9 m1 `/ \* I/ u* L
Solution C to the first yellow-brown or pink end-point that persists for
2 i# C8 ~; A. A; @" `5-10 sec. (Important: See Note under “0.01 Zinc sulfate”.) This first
0 A+ S5 G$ N5 F% F6 q) e* @titration should require more than 8 ml of titrant, but for more accurate) m# k6 ^8 h6 G7 x
work a titration of 10-15 ml is desirable.
' Y6 k+ h3 H8 CAdd 2 g of sodium fluoride to the titration flask, boil the mixture for 2-5
9 }) t4 b# z/ Z* Imin, and cool in a stream of running water. Titrate this solution, using
; P( h6 y* h$ O1 @! Bthe standardized zinc sulfate solution as titrant, to the same fugitive
& l' n; v0 i) k) J" h5 Q1 k# Uyellow-brown or pink end-point as described above.' i4 M2 u" x3 u% u E' M
Calculation:
0 c7 K# h4 m, t3 o+ _# y; ]Calculate the percentage of aluminium oxide (Al2O3) in the sample
. B1 L5 O% S4 x6 ]taken by the formula:
5 |* {/ O$ M3 h$ ]! ?: p. X% Al2O3 = 100 × (0.005VT)/S
4 t0 v. j) @" x: \where
& g( z$ ?9 u6 i. h! eV is the number of ml of 0.01 N zinc sulfate consumed in
( I+ b7 ~% x, g: O* jthe second titration,4 R; g$ n6 m) h7 p! i
T is the titre of the zinc sulfate solution,
: `) M: S, o% B0 @$ NS is the mass (g) of the sample taken, and
$ k5 ]# P u( |3 j3 p3 b7 a3 z0.005 = 500 ml / (1000mg/g × 100 ml).4 }5 ~ I+ s% ]' o
Silicon dioxide Accurately weigh 1 g of the sample and transfer to a 250-ml high-silica
$ a; r) Z9 h+ P: Cglass Erlenmeyer flask. Add 10 g of sodium bisulfate (NaHSO4 ? H2O).) ^! Z1 Z; M& u- k7 A& y/ V* A
Heat gently over a Meeker burner, while swirling the flask, until
& b. f; ?# w) C Mdecomposition and fusion are complete and the melt is clear, except3 ?% ^8 ?6 N. i, ?0 \
for the silica content, and then cool. (Caution: Do not overheat the: E- W- N V6 v# x0 o
contents of the flask at the beginning, and heat cautiously during( O8 `9 t/ _, p
fusion to avoid spattering.)
& M3 ?9 I9 @- T; W( D6 p" c( L% H9 aTo the cooled melt add 25 ml of sulfuric acid solution (1 in 2) and heat
- X' q" I1 k! _# m9 n, t' V8 dcarefully and slowly until the melt is dissolved. Cool, and carefully add# t9 L, Q. V5 y6 A" O3 e! B
150 ml of water by pouring very small portions down the sides of the7 `7 s* p, O, D6 H+ U
flask, with frequent swirling to avoid over-heating and spattering. Allow
( T2 }( I) ^) pthe contents of the flask to cool, and filter through fine ashless filter
0 }1 O, D/ G/ V; u; x5 a3 Kpaper, using a 60 degree gravity funnel. Rinse out all the silica from
- `( {% p9 W& l( j1 M0 y4 Uthe flask onto the filter paper with sulfuric acid solution (1 in 10).
% E6 E/ P1 C5 Y' Z' {Transfer the filter paper and its contents into a platinum crucible, dry in
5 b9 _5 m3 t& L' \4 [; h5 qan oven at 1200, and heat the partly covered crucible over a Bunsen; \8 s* l2 f7 W
burner. To prevent flaming of the filter paper, first heat the cover from
' H. ~! T! E. [: labove, and then the crucible from below.
$ g: {" d7 G0 }; T( yWhen the filter paper is consumed, transfer the crucible to a muffle
5 t3 B9 N: R7 V% s! I4 U. j, B' B! Dfurnace and ignite at 1000o for 30 min. Cool in a desiccator, and
1 D* Y2 r& |1 S: t/ o2 pweigh. Add 2 drops of sulfuric acid (1 in 2) and 5 ml of concentrated. `9 A0 a3 Y1 J4 U# ~( k% |: Y* |
hydrofluoric acid (sp.gr. 1.15), and carefully evaporate to dryness, first$ Y. \ j2 Z" M' O9 B
on a low-heat hot plate (to remove the HF) and then over a Bunsen @5 a! [$ T8 K3 f3 I7 a0 X
burner (to remove the H2SO4). Take precautions to avoid spattering,1 u* w! R' E. [2 [, x) m
especially after removal of the HF. Ignite at 1000o for 10 min, cool in a5 N) D0 p0 Z2 d
desiccator, and weigh again. Record the difference between the two4 R p& `: X3 V2 V% s' ?( n
weights as the content of SiO2 in the sample.
6 s# K' B; b& c4 d& C/ y0 l- VMETHOD OF ASSAY g% S! _, h8 l
Accurately weigh about 150 mg of the sample, previously dried at 105o0 z' S7 L' t" i% G+ e
for 3 hours, and transfer into a 500-ml conical flask. Add 5 ml of water) y! k$ W, r. d( J8 ?
and shake until a homogeneous, milky suspension is obtained. Add 309 V6 x$ s# K- l* L: A4 e, T/ g$ A
ml of sulfuric acid and 12 g of ammonium sulfate, and mix. Initially
8 G: M! r2 y2 m: }! b& Zheat gently, then heat strongly until a clear solution is obtained. Cool,
4 ]) d* A9 F- K1 Wthen cautiously dilute with 120 ml of water and 40 ml of hydrochloric
! A2 w9 v |* h- Y7 k: Kacid, and stir. Add 3 g of aluminium metal, and immediately insert a2 p: E# O8 y. @3 j5 o4 l1 K5 ~
rubber stopper fitted with a U-shaped glass tube while immersing the
- V. a* Z, a3 y8 A: _7 k: Lother end of the U-tube into a saturated solution of sodium6 |$ c! N6 f( t/ e3 X4 D) v/ v
bicarbonate contained in a 500-ml wide-mouth bottle, and generate
3 x/ a) W& s. y1 F8 q3 J* Zhydrogen. Allow to stand for a few minutes after the aluminium metal$ {7 i" Y; x5 E- F. h. S# q0 u
has dissolved completely to produce a transparent purple solution.
7 A* n6 \" l( ?4 b0 r7 I0 t7 TCool to below 50o in running water, and remove the rubber stopper
# S( }; Z4 u% M3 k: ucarrying the U-tube. Add 3 ml of a saturated potassium thiocyanate' j1 L) n# m) f6 D
solution as an indicator, and immediately titrate with 0.2 N ferric
2 ^; j# `' ~. q3 I9 N( `+ tammonium sulfate until a faint brown colour that persists for 30
- E9 G! a' |* F; Mseconds is obtained. Perform a blank determination and make any: z ]4 q" P6 o" I: Z& Q
necessary correction. Each ml of 0.2 N ferric ammonium sulfate is
% {1 J! h+ u% {$ F! Qequivalent to 7.990 mg of TiO2.
+ ?4 t1 e; T" f$ p' ] |
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