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二氧化钛(钛白粉)
二氧化钛(钛白粉); I% i* D5 c- x- q5 a+ c
; j H+ V. i& O0 {; oJECFA关于二氧化钛(钛白粉)的结论5 \0 n3 y |% \% I% N2 i
$ Y& K- x3 ~. i# I3 b摘要: 2006年JECFA关于二氧化钛的结论
9 _" S1 b4 R# N) Y7 T* W% e, ?4 {ADI值:不作限制。' B5 v. q* G! v. F
功能:着色剂
/ ]1 V0 t; W* l2 R3 E3 P: D7 K# E8 A3 {# D3 U7 V
TITANIUM DIOXIDE
, n- }/ Q, i, K4 E% v' W( z- ?4 OPrepared at the 67th JECFA (2006) and published in FAO JECFA
0 Y& P0 G4 b R. N) J8 ?Monographs 3 (2006), superseding specifications prepared at the 63rd6 c5 `$ d/ t# t7 Y4 c
JECFA (2004) and published in FNP 52 Add 12 (2004) and in the
* m N/ H+ X9 z3 ^) t9 x; gCombined Compendium of Food Additive Specifications, FAO JECFA5 c# I# s% f3 Q; y
Monographs 1 (2005). An ADI “not limited” was established at the 13th$ t; a% V+ e/ u c: ?: X; D
JECFA (1969).4 e$ U Z* Q6 g! d
SYNONYMS
, l/ H) p/ g# D z* l' x& K# QTitania, CI Pigment white 6, CI (1975) No. 77891, INS No. 171. j- u! ]5 @" k/ a$ ^9 D6 `2 w
DEFINITION
5 G |9 G* |) z( y ATitanium dioxide is produced by either the sulfate or the chloride8 R$ \) s' y, t: D- {3 E
process. Processing conditions determine the form (anatase or rutile
. i3 H; m2 R, i& W( ?9 i7 Zstructure) of the final product.
" P' b& {0 |4 }3 FIn the sulfate process, sulfuric acid is used to digest ilmenite (FeTiO3)4 |2 ?+ D) T( Y! P+ n
or ilmenite and titanium slag. After a series of purification steps, the
& b4 q' R; O) `! Hisolated titanium dioxide is finally washed with water, calcined, and! Q" o8 w0 y8 U7 z3 y4 c: `
micronized.
% { n3 ]+ A. M( tIn the chloride process, chlorine gas is reacted with a titaniumcontaining6 ~5 H$ `: @7 i7 n
mineral under reducing conditions to form anhydrous1 N& P6 |# G2 M8 }
titanium tetrachloride, which is subsequently purified and converted to# E1 @2 P" [9 s( X: d
titanium dioxide either by direct thermal oxidation or by reaction with. h& o4 M2 H8 a8 r) ]6 [
steam in the vapour phase. Alternatively, concentrated hydrochloric
' z: G4 F! [8 ^( [. kacid can be reacted with the titanium-containing mineral to form a
/ d1 G9 F0 G) U1 E3 O7 ]' o3 ksolution of titanium tetrachloride, which is then further purified and- [" F! Y3 N+ }: b; H
converted to titanium dioxide by hydrolysis. The titanium dioxide is
* g! z: z# z) g2 f% z+ jfiltered, washed, and calcined.
h5 ?+ w1 t* W6 j; V! y* _6 NCommercial titanium dioxide may be coated with small amounts of( @$ J6 p9 a: [8 R8 H. m
alumina and/or silica to improve the technological properties of the( m+ t+ x2 x0 {- e, q' d
product.( @% S& ?* I: A! E
C.A.S. number 13463-67-7
% p( f* }0 |7 A9 JChemical formula TiO2
) S% h$ d6 R, \3 NFormula weight& _9 x) T% Y/ Q/ N7 o
79.88
1 O) d8 t$ u$ UAssay3 Y/ m- M3 b5 z; [5 _" z' t
Not less than 99.0% on the dried basis (on an aluminium oxide and
& V# N ~$ i+ F2 D nsilicon dioxide-free basis)
: U, |9 y6 \+ j |- g1 k1 y: HDESCRIPTION
/ {7 u) y2 o+ e u( O2 RWhite to slightly coloured powder$ V s( `/ G0 l3 H9 e
FUNCTIONAL USES
& S6 Q4 f* X Q j! NColour
2 G1 S6 l: y; u, w' ], @8 W9 ECHARACTERISTICS* P4 s' l! ?* J4 X" c) x o
IDENTIFICATION
' @- O% Y9 X4 E/ |Solubility (Vol. 4)
9 O% Z8 }# _5 P# m' O+ x, @6 RInsoluble in water, hydrochloric acid, dilute sulfuric acid, and organic6 s3 _: O" m2 w' D! [5 l
solvents. Dissolves slowly in hydrofluoric acid and hot concentrated
5 K+ {5 U5 v$ i8 }2 isulfuric acid.4 u" V4 ~ Q* g0 \ K) S
Colour reaction, m3 T6 U B4 V. T6 f# ]
Add 5 ml sulfuric acid to 0.5 g of the sample, heat gently until fumes of/ W6 ]6 @0 c: f$ i) T
sulfuric acid appear, then cool. Cautiously dilute to about 100 ml with
7 }% c3 y& P9 I T qwater and filter. To 5 ml of this clear filtrate, add a few drops of
( m6 G5 j* V G6 B% P' v% yhydrogen peroxide; an orange-red colour appears immediately.* l7 D9 O2 Y6 x: J; g* Y! u
PURITY
7 Y- N' H4 @+ ]9 LLoss on drying (Vol. 4) Not more than 0.5% (105°, 3 h)7 j9 E6 R$ x$ H, ~% ~; f* p# f" u
Loss on ignition (Vol. 4)
. ~4 u& S+ y+ QNot more than 1.0% (800o) on the dried basis
2 b* c/ `7 e; p5 ]* t) A, G" wAluminium oxide and/or
9 h5 j3 z& P3 Y; _3 F. L' ]silicon dioxide
0 Y; m& { Z2 a. WNot more than 2%, either singly or combined7 O: Q( z7 v8 n. \ l
See descriptions under TESTS. c3 A6 |* ]2 J0 b% f6 J7 R
Acid-soluble substances Not more than 0.5%; Not more than 1.5% for products containing
3 R3 C- y& W B6 |alumina or silica.+ y9 j; q8 C" H1 j# T! r: T/ s
Suspend 5 g of the sample in 100 ml 0.5 N hydrochloric acid and
; |! Z7 J" K* M) `& Q% Cplace on a steam bath for 30 min with occasional stirring. Filter7 J( }) n& ~5 T) J: f$ L, y
through a Gooch crucible fitted with a glass fibre filter paper. Wash
) }3 K' n7 a, i8 Mwith three 10-ml portions of 0.5 N hydrochloric acid, evaporate the( a, J; v* ~3 `, u* O2 z& \0 X
combined filtrate and washings to dryness, and ignite at a dull red( [% h( R/ x5 t# B7 {# @
heat to constant weight.
+ _! ?6 s# i7 J9 a# P1 j7 C9 n z' \* `" oWater-soluble matter( x1 K2 Q( c6 l
(Vol. 4)7 x) Q6 s0 _' s4 V2 V
Not more than 0.5%
' _0 [ V- V, {* k1 dProceed as directed under acid-soluble substances (above), using
! r5 x/ y) c9 \5 q; I$ z2 Mwater in place of 0.5 N hydrochloric acid.
% h G" |* A- h0 A2 M( W& XImpurities soluble in 0.5 N
% `/ w- O5 u# M' Khydrochloric acid, Z# w' G$ E! L4 p5 j2 T: ]
Antimony Not more than 2 mg/kg) u4 g% J7 A, c* d( ]/ z- W' Y: \
See description under TESTS, F; Z8 G$ u- e- m
Arsenic Not more than 1 mg/kg
X6 C" `) ~0 o: F0 s0 ]7 ~, P+ KSee description under TESTS
& S* D$ y0 p: w; ^4 Z7 g( FCadmium Not more than 1 mg/kg& l* J& m; p/ v/ `2 S7 S6 B. w" D
See description under TESTS
- a8 F: r3 V& ]$ D. bLead h8 V+ {( Y7 G; K2 z
Not more than 10 mg/kg+ z2 N7 u4 }. \3 a S4 z$ f1 r
See description under TESTS
, s4 M' C; ^7 X) V. g! |Mercury (Vol. 4) Not more than 1 mg/kg
& g( V2 d U6 i3 q7 {, [ U" ?Determine using the cold vapour atomic absorption technique. Select a
/ n# V. `8 g! q& R' Fsample size appropriate to the specified level3 k. @6 }$ p& M9 W n
TESTS% X6 ~6 S$ G1 M2 u) r8 {& _ N
PURITY TESTS: f% X3 f8 n" ~% U5 c4 h. O
Impurities soluble in 0.5 N! j) b( t5 [1 B( _: N, Z
hydrochloric acid
2 C1 _7 i h- W# C, o2 w' }Antimony, arsenic,
# U1 y: J/ T9 w4 I) n9 Q: a8 t# K! k# Kcadmium and lead' S' w1 t4 s f" d9 t
(Vol.4)2 C0 B" q0 i8 \% O* L
Transfer 10.0 g of sample into a 250-ml beaker, add 50 ml of 0.5 N4 q! G; n+ n/ N" [1 K$ Z9 ]
hydrochloric acid, cover with a watch glass, and heat to boiling on a" f S* ?, Z4 h- n/ `
hot plate. Boil gently for 15 min, pour the slurry into a 100- to 150-ml
Y$ _1 p6 C x% U' Jcentrifuge bottle, and centrifuge for 10 to 15 min, or until undissolved2 b) ^. i1 ?8 d; T1 ~
material settles. Decant the supernatant extract through a Whatman
# S' m/ C: Y9 N: xNo. 4 filter paper, or equivalent, collecting the filtrate in a 100-ml" L" B C: L/ Z! z4 Z
volumetric flask and retaining as much as possible of the undissolved6 E) t, l% ]/ `0 T3 ~+ F4 A
material in the centrifuge bottle. Add 10 ml of hot water to the original
7 e. y7 l) |1 h; E6 d# m3 y! Qbeaker, washing off the watch glass with the water, and pour the& ^# y& `( S+ T# ~9 h
contents into the centrifuge bottle. Form a slurry, using a glass stirring$ j) x4 w# P. i( V& o. S8 [. P; E
rod, and centrifuge. Decant through the same filter paper, and collect/ ?# ` O+ q$ d
the washings in the volumetric flask containing the initial extract.
& \& ~: Q4 a" u4 s% XRepeat the entire washing process two more times. Finally, wash the0 ^3 c8 U) Q- |+ |) v: l
filter paper with 10 to 15 ml of hot water. Cool the contents of the flask
6 e& T9 Z. S0 w2 x/ I6 {9 qto room temperature, dilute to volume with water, and mix.0 D( d4 B( h5 L5 c
Determine antimony, cadmium, and lead using an AAS/ICP-AES
9 d6 h2 o y! X: w+ R% Y" y# Atechnique appropriate to the specified level. Determine arsenic using the5 o$ o( g3 B* k# b9 |
ICP-AES/AAS-hydride technique. Alternatively, determine arsenic using1 V; d& t* k I& h
Method II of the Arsenic Limit Test, taking 3 g of the sample rather than: C' D& ~/ t1 a# A. K# @ u
1 g. The selection of sample size and method of sample preparation% Y8 K+ G8 G- V7 u
may be based on the principles of the methods described in Volume 4.
: k" W! F, k4 ?6 I2 y2 o3 c2 L UAluminium oxide Reagents and sample solutions7 a( r9 R' l! S8 N
0.01 N Zinc Sulfate
4 Q* x8 O3 I6 Z# u3 iDissolve 2.9 g of zinc sulfate (ZnSO4 ? 7H2O) in sufficient water to3 M& s% K$ t b2 X
make 1000 ml. Standardize the solution as follows: Dissolve 500 mg4 x8 Q' N# \3 J3 Z J
of high-purity (99.9%) aluminium wire, accurately weighed, in 20 ml of
& Q$ ` t! C( T- Jconcentrated hydrochloric acid, heating gently to effect solution, then# H' m1 ?$ s( E/ R, c
transfer the solution into a 1000-ml volumetric flask, dilute to volume: P- U% `0 `' R! z
with water, and mix. Transfer a 10 ml aliquot of this solution into a 500
% u& ^" M& M( x) ~ml Erlenmeyer flask containing 90 ml of water and 3 ml of
. ^! w: q" Z6 ?0 R+ ^concentrated hydrochloric acid, add 1 drop of methyl orange TS and$ I f: K6 E+ W2 S3 X2 `
25 ml of 0.02 M disodium ethylenediaminetetraacetate (EDTA) Add,
4 }1 ]' R0 t5 L5 sdropwise, ammonia solution (1 in 5) until the colour is just completely( G% e5 X5 m; m# k; c
changed from red to orange-yellow. Then, add:. [" ^% F/ L5 U0 k L |* H+ U' \
(a): 10 ml of ammonium acetate buffer solution (77 g of4 B; i! c p# Y9 {# _
ammonium acetate plus 10 ml of glacial acetic acid, dilute to
, x3 f! o, Z# @4 r1000 ml with water) and
. N/ k9 M7 Y* u: S0 |(b): 10 ml of diammonium hydrogen phosphate solution (150 g2 x3 s z% @1 X9 d/ c- U
of diammonium hydrogen phosphate in 700 ml of water,/ J/ e+ K5 E7 w! e
adjusted to pH 5.5 with a 1 in 2 solution of hydrochloric acid,
+ g2 i0 C, T1 n+ Y& L+ j% a) vthen dilute to 1000 ml with water).
; S$ y ~2 u; ^0 eBoil the solution for 5 min, cool it quickly to room temperature in a
- s3 V$ C+ b3 S& Ystream of running water, add 3 drops of xylenol orange TS, and mix., k/ V& U5 _1 B+ [1 C R
Using the zinc sulfate solution as titrant, titrate the solution to the first5 y' b& |/ X0 V2 S
yellow-brown or pink end-point colour that persists for 5-10 sec. (Note:
, g( b2 M0 N7 eThis titration should be performed quickly near the end-point by0 k6 F H0 g5 {2 f3 T0 d+ _
adding rapidly 0.2 ml increments of the titrant until the first colour
+ B# C( c9 p3 h, h, `. \1 ^change occurs; although the colour will fade in 5-10 sec, it is the true
j6 X- p8 M9 J: ~end-point. Failure to observe the first colour change will result in an
- x# h/ F. b" e8 D, aincorrect titration. The fading end-point does not occur at the second& g# W7 P( R) F2 Q% D/ E! d
end-point.)4 x) g" ]/ O' p! i+ q: |/ ?! ]! {
Add 2 g of sodium fluoride, boil the mixture for 2-5 min, and cool in a/ s3 T2 F0 e& D5 J+ g
stream of running water. Titrate this solution, using the zinc sulfate) k# U I) C. \
solution as titrant, to the same fugitive yellow-brown or pink end-point* m: E5 K1 T q) ], ?! O
as described above.
1 S' l1 }: S2 ]Calculate the titre T of zinc sulfate solution by the formula:
- N1 }8 V% }! X2 G! a8 xT = 18.896 W / V/ G: y* d A4 @# Z N# [4 H' t
where; N8 G, M2 L7 V: @& v* W. h
T is the mass (mg) of Al2O3 per ml of zinc sulfate solution) V/ W* W3 O4 B- m
W is the mass (g) of aluminium wire% ]/ N% r1 p" C* W- Z! y3 _! ?
V is the ml of the zinc sulfate solution consumed in the
1 O# q8 j! q# E. `9 b, Isecond titration
! c* t# Q+ x+ `18.896 = (R × 1000 mg/g × 10 ml/2)/1000 ml and
* P# Z9 A `7 L- x# l mR is the ratio of the formula weight of aluminium oxide to
. T$ n O7 m7 N5 `that of elemental aluminium.8 ?- Z8 l( v) q9 e1 s2 Y5 N
Sample Solution A& _% A/ C) L) k& y( @7 }% n
Accurately weigh 1 g of the sample and transfer to a 250-ml high-silica
9 s/ p- }9 o: t5 @glass Erlenmeyer flask. Add 10 g of sodium bisulfate (NaHSO4 ? H2O).
) q, o1 ?( S- X(Note: Do not use more sodium bisulfate than specified, as an excess
+ M5 N8 w1 ^5 m, v8 hconcentration of salt will interfere with the EDTA titration later on in the" |# u; O8 L2 i/ `+ q
procedure.) Begin heating the flask at low heat on a hot plate, and. z* }1 S; k2 b$ E2 \7 e
then gradually raise the temperature until full heat is reached.
1 |# k& X. Z( i" H* `, b, F(Caution: perform this procedure in a well ventilated area. ) When; L2 K* o5 y6 y2 T8 G5 m0 x5 o
spattering has stopped and light fumes of SO3 appear, heat in the full% O" K9 I0 i! q4 K4 N# T; [
flame of a Meeker burner, with the flask tilted so that the fusion of the
8 o6 a0 ~- x7 hsample and sodium bisulfate is concentrated at one end of the flask. I% T! B0 p0 V x& _1 m) j8 l
Swirl constantly until the melt is clear (except for silica content), but
# Q: Y" S% j3 L8 U5 gguard against prolonged heating to avoid precipitation of titanium
* Q" I% c4 P$ idioxide. Cool, add 25 ml sulfuric acid solution (1 in 2), and heat until
1 O, l, k& \: x# bthe mass has dissolved and a clear solution results. Cool, and dilute to
- `" Y) t( {! d; o9 U120 ml with water. Introduce a magnetic stir bar into the flask.. G* B5 y, a+ O5 @. y
Sample Solution B
; U7 a4 {3 g3 \/ |$ C: V' D1 X& Q. yPrepare 200 ml of an approximately 6.25 M solution of sodium5 Y- j0 |, j; R9 ~2 f( U
hydroxide. Add 65 ml of this solution to Sample Solution A, while
6 @) w' u) |6 ^) X& K" Rstirring with the magnetic stirrer; pour the remaining 135 ml of the
1 L; G% Y! N0 G$ e. Nalkali solution into a 500-ml volumetric flask.3 i- r j ^- A1 x1 @* D7 i
Slowly, with constant stirring, add the sample mixture to the alkali
; {" m* F2 I! ]- t+ w; J" ?3 |, rsolution in the 500-ml volumetric flask; dilute to volume with water,4 \' ^' W( R' s, [! [; H
and mix. (Note: If the procedure is delayed at this point for more than
* I0 k/ X+ H$ o+ M! ]$ G: _" T. |7 K4 d2 hours, store the contents of the volumetric flask in a polyethylene$ V; j2 E6 L. b6 ], f2 Q& F3 G" n
bottle.) Allow most of the precipitate to settle (or centrifuge for 5 min),& Y& b7 f5 Z* u
then filter the supernatant liquid through a very fine filter paper. Label0 }1 e6 V% X1 B6 f+ p; o
the filtrate Sample Solution B.
L, p/ l8 M% l0 m$ X6 F- bSample Solution C
W. p; k9 q+ S: f/ I; lTransfer 100 ml of the Sample Solution B into a 500-ml Erlenmeyer
8 u& P! ?6 Z5 p+ [flask, add 1 drop of methyl orange TS, acidify with hydrochloric acid" F* {6 t1 I w8 y% i2 q
solution (1 in 2), and then add about 3 ml in excess. Add 25 ml of 0.02
! C- I' G1 W- J7 Y, x" DM disodium EDTA, and mix. [Note: If the approximate Al2O3 content is
3 q* x6 u( j, `: F- yknown, calculate the optimum volume of EDTA solution to be added
/ W7 V% J& p" B. X+ |" Y( n4 Jby the formula: (4 x % Al2O3) + 5.]
( B* i" \/ ~* w! V; VAdd, dropwise, ammonia solution (1 in 5) until the colour is just
1 B$ ^. g3 E! `' X& j/ bcompletely changed from red to orange-yellow. Then add10 ml each
5 N- |" e$ @* F- |+ H( Xof Solutions 1 and 2 (see above) and boil for 5 min. Cool quickly to" _6 Y/ M" s" W
room temperature in a stream of running water, add 3 drops of xylenol' [1 x+ X$ t: b; Y% l* ]. H
orange TS, and mix. If the solution is purple, yellow-brown, or pink,
9 T6 u4 `- L1 ~. Sbring the pH to 5.3 - 5.7 by the addition of acetic acid. At the desired7 h: d6 B1 f, L% N9 U
pH, a pink colour indicates that not enough of the EDTA solution has
) V p4 g7 n- H0 Zbeen added, in which case, discard the solution and repeat this
. b$ h$ i7 P, R/ h$ c& xprocedure with another 100 ml of Sample Solution B, using 50 ml,
9 c$ R6 J7 _( R0 b) i( Erather than 25 ml, of 0.02 M disodium EDTA.
7 R2 M0 p+ g; K# U4 \* tProcedure
# e) Z& T8 p' p: O' {$ t6 sUsing the standardized zinc sulfate solution as titrant, titrate Sample
1 K$ @" ]* Y' W3 k: l! T% \) [* @Solution C to the first yellow-brown or pink end-point that persists for
1 \, |6 Q+ ~$ B- ?1 o/ V5-10 sec. (Important: See Note under “0.01 Zinc sulfate”.) This first
/ |/ M0 E" v: p# v* ftitration should require more than 8 ml of titrant, but for more accurate9 T s' Z$ y2 M% l( x0 V
work a titration of 10-15 ml is desirable.
8 f- E* q; M4 u) {8 a; A) aAdd 2 g of sodium fluoride to the titration flask, boil the mixture for 2-5- W0 s9 ?4 L6 v2 ~. p- r/ p4 R9 C: r
min, and cool in a stream of running water. Titrate this solution, using: [' {" K; y. |
the standardized zinc sulfate solution as titrant, to the same fugitive; d. O( \% p& L: e/ {3 z1 u
yellow-brown or pink end-point as described above.$ ]; t" w& Y4 N* @. i# _
Calculation:
3 H) F4 n+ m6 hCalculate the percentage of aluminium oxide (Al2O3) in the sample
$ G, ]$ C! ^& }8 X5 U W" p' htaken by the formula:
8 f" k& p+ {3 _% Al2O3 = 100 × (0.005VT)/S
/ a2 O+ V3 E6 ?5 Pwhere
. ?9 O' L& f* U. {) yV is the number of ml of 0.01 N zinc sulfate consumed in
/ X) ^9 y, @% t9 @the second titration," Y3 }$ \; z$ ~0 L
T is the titre of the zinc sulfate solution,
0 S/ l$ g3 }* `4 ~# r T, QS is the mass (g) of the sample taken, and
3 Z |( H5 Z6 I2 L: e2 `+ ?0.005 = 500 ml / (1000mg/g × 100 ml).$ V6 g( \' W8 R* Y' ?
Silicon dioxide Accurately weigh 1 g of the sample and transfer to a 250-ml high-silica2 N1 P! @% D, i) G% ~+ o
glass Erlenmeyer flask. Add 10 g of sodium bisulfate (NaHSO4 ? H2O).
' g, w9 ^+ j: {8 WHeat gently over a Meeker burner, while swirling the flask, until
& a9 _8 n9 c8 Ldecomposition and fusion are complete and the melt is clear, except8 r. o' S' G1 {* Y; h/ T/ V
for the silica content, and then cool. (Caution: Do not overheat the
+ T5 ~8 d `1 J. Acontents of the flask at the beginning, and heat cautiously during- K! V( H7 F* o9 l$ w: L
fusion to avoid spattering.)% N2 Q8 c: K) k
To the cooled melt add 25 ml of sulfuric acid solution (1 in 2) and heat5 ^7 r+ ]4 n6 z) R/ c8 Y: Y
carefully and slowly until the melt is dissolved. Cool, and carefully add
& V8 A, ~+ |7 V+ d A+ C8 {0 Z150 ml of water by pouring very small portions down the sides of the
0 ?' Y0 `' Y. `3 x9 o* N% U& b- \flask, with frequent swirling to avoid over-heating and spattering. Allow
" Z [- H+ v+ x: p4 uthe contents of the flask to cool, and filter through fine ashless filter7 Z" o' u2 I6 V
paper, using a 60 degree gravity funnel. Rinse out all the silica from% U' J, J( S6 C! Z% r. \9 E) k9 ^
the flask onto the filter paper with sulfuric acid solution (1 in 10).
; S' g8 V, d( ]2 X+ X BTransfer the filter paper and its contents into a platinum crucible, dry in
' C& |5 g9 L# E/ R5 R! xan oven at 1200, and heat the partly covered crucible over a Bunsen
( A4 ?6 S8 @/ }% I* f1 b- Bburner. To prevent flaming of the filter paper, first heat the cover from
* G h, z4 H4 Z9 Zabove, and then the crucible from below.9 @, O* I" R* l# V8 p: P
When the filter paper is consumed, transfer the crucible to a muffle- E( y+ d+ |+ z8 G8 d# f+ R; [
furnace and ignite at 1000o for 30 min. Cool in a desiccator, and8 C$ i0 W& L Q8 ?4 n9 ^4 Q" ?
weigh. Add 2 drops of sulfuric acid (1 in 2) and 5 ml of concentrated7 d! X% X h4 K: Z2 T
hydrofluoric acid (sp.gr. 1.15), and carefully evaporate to dryness, first
# V7 l( U" v! \7 Bon a low-heat hot plate (to remove the HF) and then over a Bunsen
4 X: f: a8 X- Dburner (to remove the H2SO4). Take precautions to avoid spattering,. ]0 _: g, l3 L0 n5 C) r
especially after removal of the HF. Ignite at 1000o for 10 min, cool in a9 k( i" }9 E Q
desiccator, and weigh again. Record the difference between the two+ b0 {" |7 x* h
weights as the content of SiO2 in the sample.. d4 I$ {$ T/ I5 _4 N( I7 h5 j
METHOD OF ASSAY
$ }7 N% U9 b2 AAccurately weigh about 150 mg of the sample, previously dried at 105o
) F N0 e8 a- b+ n A' E/ v7 wfor 3 hours, and transfer into a 500-ml conical flask. Add 5 ml of water6 h7 `) M2 Y2 C+ T# R5 r: l4 y1 p
and shake until a homogeneous, milky suspension is obtained. Add 30* c3 Y+ S7 F! M' I
ml of sulfuric acid and 12 g of ammonium sulfate, and mix. Initially2 G" r. Z) o3 d- q1 N5 w' q
heat gently, then heat strongly until a clear solution is obtained. Cool,7 X9 v: i+ c1 n$ ]& r
then cautiously dilute with 120 ml of water and 40 ml of hydrochloric
6 U/ I% m2 U% n# |5 Macid, and stir. Add 3 g of aluminium metal, and immediately insert a) S) Y, x3 G5 @( h& w# M- H- |
rubber stopper fitted with a U-shaped glass tube while immersing the
% L: ~; Q/ D0 G3 q6 ]0 @other end of the U-tube into a saturated solution of sodium
) S0 Y0 U$ V- ?# H4 h- Ibicarbonate contained in a 500-ml wide-mouth bottle, and generate7 p) V ^& g: ?! s z7 }
hydrogen. Allow to stand for a few minutes after the aluminium metal0 f% U1 X/ o' g9 ]8 ~4 @
has dissolved completely to produce a transparent purple solution.
7 i8 e9 {; p% pCool to below 50o in running water, and remove the rubber stopper8 G' M# _9 T8 A
carrying the U-tube. Add 3 ml of a saturated potassium thiocyanate
6 r, E3 T" u2 t$ g& csolution as an indicator, and immediately titrate with 0.2 N ferric7 e9 z* d8 u) f3 A' ?3 T/ q
ammonium sulfate until a faint brown colour that persists for 30
3 F& x! B; s$ a7 C% U8 X% Y4 i5 {* lseconds is obtained. Perform a blank determination and make any
3 l; X; M, ?( m; Q% _2 b5 V7 Tnecessary correction. Each ml of 0.2 N ferric ammonium sulfate is
: F+ Y9 x- l8 n& kequivalent to 7.990 mg of TiO2.8 x6 f. c. R: r7 @+ q
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