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二氧化钛(钛白粉)
二氧化钛(钛白粉). C" I1 R1 w9 d
* `7 h5 N& j8 b+ G" B& r. \ u
JECFA关于二氧化钛(钛白粉)的结论) M* a2 k7 B% i( A
, O2 z& C) l" u1 I1 l/ x摘要: 2006年JECFA关于二氧化钛的结论) x# k/ n. p* k: V( j! |$ ~6 P( ]
ADI值:不作限制。2 H2 T# R8 _* P# K
功能:着色剂
+ z6 T0 \! E" z, p" S! G. h+ e% }+ p. [ P* m
TITANIUM DIOXIDE/ a# H- _4 g0 p# J+ ]: g0 d
Prepared at the 67th JECFA (2006) and published in FAO JECFA) W5 V: j( Q! c8 A! e3 R1 ?
Monographs 3 (2006), superseding specifications prepared at the 63rd7 S- E: S3 ?" O" F/ O! ~
JECFA (2004) and published in FNP 52 Add 12 (2004) and in the
/ o X l0 b" V( [% V( O M" z1 @Combined Compendium of Food Additive Specifications, FAO JECFA' Q( I4 o* k* f$ j/ ~7 s9 M
Monographs 1 (2005). An ADI “not limited” was established at the 13th
3 D( {* t* [! RJECFA (1969).
7 s7 z) P/ [' I9 j/ b/ F+ s+ c/ kSYNONYMS
8 \! V: z5 `5 }' PTitania, CI Pigment white 6, CI (1975) No. 77891, INS No. 1717 B# A1 k6 L+ d- Y; X
DEFINITION
1 t9 s. ~- i [7 W- f( @Titanium dioxide is produced by either the sulfate or the chloride2 H2 N/ R; C# L, e
process. Processing conditions determine the form (anatase or rutile
, k1 N& D' p& w. Q" Fstructure) of the final product.; v4 c8 q* B' ~* Z2 }
In the sulfate process, sulfuric acid is used to digest ilmenite (FeTiO3)
, U7 D5 r! d9 x) t$ W2 {or ilmenite and titanium slag. After a series of purification steps, the
R R% l, D! `6 C- kisolated titanium dioxide is finally washed with water, calcined, and
6 Q- }) B# I8 B: E$ x6 Q+ d$ k4 ~micronized.! K' J Q) W* y6 p0 J8 B
In the chloride process, chlorine gas is reacted with a titaniumcontaining: ^) [5 M+ x% ~3 r
mineral under reducing conditions to form anhydrous
, N5 A% E8 g) E" Mtitanium tetrachloride, which is subsequently purified and converted to6 V* e& t- s! @" ^
titanium dioxide either by direct thermal oxidation or by reaction with+ G& r% n" g) N2 x9 S! C
steam in the vapour phase. Alternatively, concentrated hydrochloric$ q& ?9 J' ]. A, {0 U+ I
acid can be reacted with the titanium-containing mineral to form a" K7 H( L% ]) O, ~) H% j+ ~% Z5 i' y
solution of titanium tetrachloride, which is then further purified and4 P, g* V8 h- V8 |' H) O* W
converted to titanium dioxide by hydrolysis. The titanium dioxide is
$ n3 v, `$ r" l3 Kfiltered, washed, and calcined.3 V* t, r' z5 P a/ N
Commercial titanium dioxide may be coated with small amounts of
: ]$ f) q7 i0 a0 i- yalumina and/or silica to improve the technological properties of the
* Y+ f! I: s1 X0 F; I8 V! m2 ]product.
, m" i5 b. \2 i" j( z+ L$ T- UC.A.S. number 13463-67-76 M& n4 a( p* a$ j
Chemical formula TiO2
* G( T) V8 t+ _. x, ?0 A* gFormula weight
0 Y$ z9 ~: V! B6 ^8 Z1 M79.88
" ?: g7 K! l5 K7 z" I2 }Assay
6 n% e* B7 @9 \% [" mNot less than 99.0% on the dried basis (on an aluminium oxide and
: h1 |7 \) s$ z% Q Gsilicon dioxide-free basis)
. e3 C/ K. T) T. j+ G: `; R( {% ADESCRIPTION' Z1 B0 J( q3 ?; Q
White to slightly coloured powder
/ g/ O8 q8 e- t- H0 SFUNCTIONAL USES8 @1 r& V1 x% f9 K
Colour
f" }8 K9 D5 V4 Z; Z! DCHARACTERISTICS+ R+ Y) l% s. {
IDENTIFICATION) F, n- l* d" q5 E0 O
Solubility (Vol. 4)
$ H# Z# Z# S- h9 `, ~4 q2 jInsoluble in water, hydrochloric acid, dilute sulfuric acid, and organic1 J+ Z* L: W1 }2 A
solvents. Dissolves slowly in hydrofluoric acid and hot concentrated
7 w l' z; m9 S/ v5 r. ysulfuric acid.
+ D) ]; F) S! F! ^" ^7 p/ B; e2 YColour reaction( B9 O9 I) Z2 `7 t5 `9 C
Add 5 ml sulfuric acid to 0.5 g of the sample, heat gently until fumes of( o k8 z) ^4 r* Z
sulfuric acid appear, then cool. Cautiously dilute to about 100 ml with* v# g. z' z4 \, V' L
water and filter. To 5 ml of this clear filtrate, add a few drops of* ` b. v. N/ D
hydrogen peroxide; an orange-red colour appears immediately.
! G' k% ?+ H. M+ Z( IPURITY
/ z# k+ J6 ^0 F% |Loss on drying (Vol. 4) Not more than 0.5% (105°, 3 h)- |/ [5 C$ u* \4 Z
Loss on ignition (Vol. 4)0 K, i$ f' G! N
Not more than 1.0% (800o) on the dried basis# B3 L3 Q# i$ L" c* F9 w5 L8 w
Aluminium oxide and/or# \3 k F7 O9 @5 |& j) s& C
silicon dioxide
& }8 J3 y/ ~, H; d$ A/ _4 }, Y$ BNot more than 2%, either singly or combined- {; Y9 n0 g0 L0 y9 z0 z
See descriptions under TESTS
: i3 M* q/ L u# cAcid-soluble substances Not more than 0.5%; Not more than 1.5% for products containing+ C0 R1 @8 J4 U' {. U; k8 d
alumina or silica.+ x% Y; S% i4 S* H+ K! b
Suspend 5 g of the sample in 100 ml 0.5 N hydrochloric acid and
! \- N: }/ x, M8 Y2 Hplace on a steam bath for 30 min with occasional stirring. Filter; ?! C6 h/ G5 f+ c' K
through a Gooch crucible fitted with a glass fibre filter paper. Wash
3 Q6 `! i# T. ~) ^2 S7 h% wwith three 10-ml portions of 0.5 N hydrochloric acid, evaporate the
( T2 x7 k% z6 h0 G; ~; Tcombined filtrate and washings to dryness, and ignite at a dull red4 F& D" T$ N/ c+ s6 D0 B5 U
heat to constant weight.
, r: x. @: [% A1 S, N+ F" GWater-soluble matter: n: K) r+ {& W4 V0 O
(Vol. 4)
5 U, U r! U2 I. C5 s. WNot more than 0.5%, ]6 q& h9 L+ `6 u, l+ c+ D
Proceed as directed under acid-soluble substances (above), using$ k6 z2 o$ l. [2 m2 |% ~5 ]9 r g
water in place of 0.5 N hydrochloric acid.* D( E/ z4 l3 |) A
Impurities soluble in 0.5 N1 w {/ i; T. o) C5 W/ o4 R6 d- T) O5 D
hydrochloric acid! L7 N& f/ m0 _8 K
Antimony Not more than 2 mg/kg) p& T8 n8 c0 O
See description under TESTS
1 A1 X9 O& P3 c' @Arsenic Not more than 1 mg/kg! X) T' I* a5 ]* y7 D
See description under TESTS8 H6 d* f3 [9 ]
Cadmium Not more than 1 mg/kg
: s5 g* |' A, l9 FSee description under TESTS
) \0 l: r4 C) t4 ]Lead1 ?9 f1 K' X5 H
Not more than 10 mg/kg
q" z+ \* }* }9 T0 nSee description under TESTS$ p3 `' D7 U6 G2 U' H
Mercury (Vol. 4) Not more than 1 mg/kg
5 H" z& Y2 r7 }: O' VDetermine using the cold vapour atomic absorption technique. Select a4 r, _/ w6 l4 ~ @7 j1 R9 I3 `
sample size appropriate to the specified level
1 r- u, [+ _6 G% N- j* ITESTS4 C9 o3 g u: c4 M j& [* x
PURITY TESTS
3 s& `& ?- d3 B$ k* A2 V) V* fImpurities soluble in 0.5 N: M+ W2 F$ b/ R) X0 S! F( y) _ Y
hydrochloric acid
; e" C3 Q. P5 P% RAntimony, arsenic,; X) Q/ K3 o1 i2 Q% e
cadmium and lead
; M& z$ |$ ]; G$ z( ?(Vol.4)
1 ?# F8 g2 D! I$ X6 m4 a6 ITransfer 10.0 g of sample into a 250-ml beaker, add 50 ml of 0.5 N
' m( e% F) {% g& F! X" Khydrochloric acid, cover with a watch glass, and heat to boiling on a6 w3 x+ T! W# E. x
hot plate. Boil gently for 15 min, pour the slurry into a 100- to 150-ml% v8 m! d" k+ u% f' b( \/ `7 Z& q
centrifuge bottle, and centrifuge for 10 to 15 min, or until undissolved
! v6 f" C% E: S u& k' C# i1 _material settles. Decant the supernatant extract through a Whatman( _9 @1 v+ o: S d2 s' P9 }' ]
No. 4 filter paper, or equivalent, collecting the filtrate in a 100-ml- r* F5 X8 Y* f' {8 ^
volumetric flask and retaining as much as possible of the undissolved2 X6 P3 \6 U* |. R" S c- i0 G6 j6 Q6 K
material in the centrifuge bottle. Add 10 ml of hot water to the original
* X& w! P! F1 e( Zbeaker, washing off the watch glass with the water, and pour the
}/ \& @3 _1 x; }: mcontents into the centrifuge bottle. Form a slurry, using a glass stirring7 q6 u- @ b" {( N
rod, and centrifuge. Decant through the same filter paper, and collect1 T8 N+ j% R* G6 T5 I+ n& H
the washings in the volumetric flask containing the initial extract." F, q' z1 a4 r7 |* ?3 K6 G
Repeat the entire washing process two more times. Finally, wash the( i+ f1 C0 q8 ], `
filter paper with 10 to 15 ml of hot water. Cool the contents of the flask
7 ?; G* j3 T4 A. k, J$ z* |to room temperature, dilute to volume with water, and mix.
- [% V! @' {+ q/ p7 z( V% qDetermine antimony, cadmium, and lead using an AAS/ICP-AES
) V7 a% F5 Q8 C" H! S7 I v% Gtechnique appropriate to the specified level. Determine arsenic using the' S) W* H9 ]7 I* X a% L
ICP-AES/AAS-hydride technique. Alternatively, determine arsenic using
0 `( y o z- h8 vMethod II of the Arsenic Limit Test, taking 3 g of the sample rather than
; A' e" V5 Q! @1 [$ t9 B( Z1 g. The selection of sample size and method of sample preparation* Y* r7 j' A/ t5 W7 O
may be based on the principles of the methods described in Volume 4.3 ?) Z% F& n+ O. |5 Y
Aluminium oxide Reagents and sample solutions8 x e: s5 ]; a" Y+ Y4 {/ Q# c! i: p
0.01 N Zinc Sulfate
" z: `: h0 a: t1 f/ ]Dissolve 2.9 g of zinc sulfate (ZnSO4 ? 7H2O) in sufficient water to Y1 ~$ c+ A7 d6 Q* x
make 1000 ml. Standardize the solution as follows: Dissolve 500 mg
5 T& e4 a/ {( A$ r8 D$ e+ \of high-purity (99.9%) aluminium wire, accurately weighed, in 20 ml of* [' j0 k0 y' n4 h9 U/ n
concentrated hydrochloric acid, heating gently to effect solution, then# @( k0 Q k8 M9 d; L3 I
transfer the solution into a 1000-ml volumetric flask, dilute to volume/ W$ O! c) x" B% O
with water, and mix. Transfer a 10 ml aliquot of this solution into a 500
5 E6 U' F2 a& W4 O3 W4 Rml Erlenmeyer flask containing 90 ml of water and 3 ml of) N0 D6 q1 U9 p- e
concentrated hydrochloric acid, add 1 drop of methyl orange TS and
1 D: w* `% Z0 W# [; F8 F25 ml of 0.02 M disodium ethylenediaminetetraacetate (EDTA) Add,
& ?1 e3 ?3 B! m4 p- u3 r! w3 A) Ndropwise, ammonia solution (1 in 5) until the colour is just completely X# B2 ?. u; L2 F5 }
changed from red to orange-yellow. Then, add: s5 y: p# N7 v" F9 m1 j* M
(a): 10 ml of ammonium acetate buffer solution (77 g of) t, ~( w" |- s/ v* L( d
ammonium acetate plus 10 ml of glacial acetic acid, dilute to
# z# W5 m5 _( R4 d) u, x. i9 [: @" B1000 ml with water) and
- o( N: t9 N3 Y3 F(b): 10 ml of diammonium hydrogen phosphate solution (150 g
. t- ?5 E$ K* b, ]& |* |, Jof diammonium hydrogen phosphate in 700 ml of water,
' i- l5 d3 v; p( I# D6 [1 `adjusted to pH 5.5 with a 1 in 2 solution of hydrochloric acid,) L1 H1 z5 r- i [( y5 t
then dilute to 1000 ml with water).
$ z3 S/ U. J X- zBoil the solution for 5 min, cool it quickly to room temperature in a
" @. C4 P0 Z2 F: q) C. T+ [stream of running water, add 3 drops of xylenol orange TS, and mix.$ Q8 a: p" |: H* A
Using the zinc sulfate solution as titrant, titrate the solution to the first' J5 f6 K: p5 u6 u7 I
yellow-brown or pink end-point colour that persists for 5-10 sec. (Note:
2 _" E( i. v" K+ R0 bThis titration should be performed quickly near the end-point by9 c8 H# S3 h" Z7 [( h0 ]' J
adding rapidly 0.2 ml increments of the titrant until the first colour: {/ @2 `) s9 H$ M7 N; d
change occurs; although the colour will fade in 5-10 sec, it is the true
% y. _+ \2 [( T) Uend-point. Failure to observe the first colour change will result in an
! L# a, W4 c) b: T, c2 D! h0 X; |incorrect titration. The fading end-point does not occur at the second
8 f" }% F/ j3 k- p$ t% jend-point.)/ E3 q1 V0 [1 j+ z8 @
Add 2 g of sodium fluoride, boil the mixture for 2-5 min, and cool in a
4 n$ C" n& ~2 Wstream of running water. Titrate this solution, using the zinc sulfate
. J" T* z; {+ |* D8 H1 v% \$ o* nsolution as titrant, to the same fugitive yellow-brown or pink end-point! |4 Y% r( Z7 }2 Y
as described above.( J$ ]0 S% {- U" \: H$ Q' x' H
Calculate the titre T of zinc sulfate solution by the formula:
6 B' S! \& c6 [" G. MT = 18.896 W / V/ |0 `* \# K5 v* S0 {
where w* r% | y% B. P6 A: E
T is the mass (mg) of Al2O3 per ml of zinc sulfate solution
" _/ d0 d$ G4 }W is the mass (g) of aluminium wire1 G6 i+ e5 i: R# k/ R/ ?9 f
V is the ml of the zinc sulfate solution consumed in the" {! M- v8 b6 Z% Q* U
second titration% s( ?& w; p* ?1 G+ R3 x
18.896 = (R × 1000 mg/g × 10 ml/2)/1000 ml and. `) F- M9 l( z
R is the ratio of the formula weight of aluminium oxide to
2 \/ t" R- w$ y! Jthat of elemental aluminium.& w# T- t" N# H0 J! A
Sample Solution A
^2 ?9 [* v( }) SAccurately weigh 1 g of the sample and transfer to a 250-ml high-silica
& |% O* |% W) U9 cglass Erlenmeyer flask. Add 10 g of sodium bisulfate (NaHSO4 ? H2O).
- `8 z6 a0 j5 B$ j9 _- W* u5 ^(Note: Do not use more sodium bisulfate than specified, as an excess
/ ~" b+ N- r: ]# Xconcentration of salt will interfere with the EDTA titration later on in the
. ?" D' Q" W: I) t( qprocedure.) Begin heating the flask at low heat on a hot plate, and
3 ^; b- n, U- L5 \then gradually raise the temperature until full heat is reached.
$ z: ]& q. c r6 F! L(Caution: perform this procedure in a well ventilated area. ) When
$ {& `0 I9 [2 X2 Q& F, p2 Vspattering has stopped and light fumes of SO3 appear, heat in the full
: t8 u# ^3 G% N+ T/ q! cflame of a Meeker burner, with the flask tilted so that the fusion of the
6 {! F" R6 B' psample and sodium bisulfate is concentrated at one end of the flask." a' p" X' x3 A/ H& J9 o6 @
Swirl constantly until the melt is clear (except for silica content), but
; @3 K0 P; h: bguard against prolonged heating to avoid precipitation of titanium* f" n( A! z$ p* X% C- b; m% \
dioxide. Cool, add 25 ml sulfuric acid solution (1 in 2), and heat until* A3 N. U$ A, Q/ u' ~% y
the mass has dissolved and a clear solution results. Cool, and dilute to4 _! t$ Z! `" o: g" N6 h
120 ml with water. Introduce a magnetic stir bar into the flask.8 R- v* M ~9 j& t. j) L
Sample Solution B0 z8 z( @. p2 {7 [- F
Prepare 200 ml of an approximately 6.25 M solution of sodium
0 D2 O9 p( \0 d+ Shydroxide. Add 65 ml of this solution to Sample Solution A, while- t7 K3 U8 b/ [- n5 `0 w) Q
stirring with the magnetic stirrer; pour the remaining 135 ml of the
8 v& t4 L/ W$ b6 W2 calkali solution into a 500-ml volumetric flask.; q2 w7 T( s; ^* L4 O* y
Slowly, with constant stirring, add the sample mixture to the alkali, m) `2 T9 R8 y* E6 M/ l2 s
solution in the 500-ml volumetric flask; dilute to volume with water,/ \! K. _- i I& A5 f. `# S. A
and mix. (Note: If the procedure is delayed at this point for more than+ e O( l) w; \7 S
2 hours, store the contents of the volumetric flask in a polyethylene
' ]- f4 \1 I6 h. T3 t- X8 Tbottle.) Allow most of the precipitate to settle (or centrifuge for 5 min),! K( ^% a: B$ j, Y1 q% ~
then filter the supernatant liquid through a very fine filter paper. Label" i1 a5 a! v* ~8 V, ^8 z K# M
the filtrate Sample Solution B.
& D& M1 @5 Z( v% b# s% R# b. @Sample Solution C
# u7 M2 L5 Q1 O# W3 K4 JTransfer 100 ml of the Sample Solution B into a 500-ml Erlenmeyer% r6 G, p, s8 X' y( l8 _
flask, add 1 drop of methyl orange TS, acidify with hydrochloric acid
' E5 f5 \ t2 F: ?solution (1 in 2), and then add about 3 ml in excess. Add 25 ml of 0.02
3 l& ^ M" Y; z- Y& i. A/ oM disodium EDTA, and mix. [Note: If the approximate Al2O3 content is6 M5 `- X7 O& m4 B) [% p0 B
known, calculate the optimum volume of EDTA solution to be added. k! [8 ?& ~: B+ q/ A
by the formula: (4 x % Al2O3) + 5.]
4 o& E5 |$ v% [/ t6 S6 eAdd, dropwise, ammonia solution (1 in 5) until the colour is just
3 V2 R6 j2 Z0 C% C+ r7 o) G/ Zcompletely changed from red to orange-yellow. Then add10 ml each! m8 I( y; ]1 k6 D+ I: x
of Solutions 1 and 2 (see above) and boil for 5 min. Cool quickly to
I4 ? ~, N d0 G- Wroom temperature in a stream of running water, add 3 drops of xylenol
8 H# X2 R: b# L1 T: |0 @orange TS, and mix. If the solution is purple, yellow-brown, or pink,
$ C5 o R* q, z2 _' ibring the pH to 5.3 - 5.7 by the addition of acetic acid. At the desired
* l1 N/ R0 X6 ]" X) ~) ~pH, a pink colour indicates that not enough of the EDTA solution has, b2 T, |5 c7 I! O& ^
been added, in which case, discard the solution and repeat this
. x: \4 q$ r0 ^procedure with another 100 ml of Sample Solution B, using 50 ml,
! ^0 G% ]+ X6 j, urather than 25 ml, of 0.02 M disodium EDTA.( f6 H _7 c0 K9 [0 ?
Procedure5 ~" g2 J% @) V7 G1 D
Using the standardized zinc sulfate solution as titrant, titrate Sample, c0 Q3 l: C: \# R( Y$ }
Solution C to the first yellow-brown or pink end-point that persists for) E4 c# ]2 l% u" Z2 o/ f
5-10 sec. (Important: See Note under “0.01 Zinc sulfate”.) This first
) q4 Q, m$ @2 g; D$ ]titration should require more than 8 ml of titrant, but for more accurate
% a3 Q8 m4 ]6 wwork a titration of 10-15 ml is desirable.
; ~* e; U* Q1 T2 Z, r+ ]+ hAdd 2 g of sodium fluoride to the titration flask, boil the mixture for 2-5
9 A. O* U9 R( d9 ~min, and cool in a stream of running water. Titrate this solution, using
4 s( l$ `/ y# t9 V" Bthe standardized zinc sulfate solution as titrant, to the same fugitive
1 l' j8 V$ V. ^( `yellow-brown or pink end-point as described above.
+ w) P+ i7 Y) k8 A& K& @5 W% `Calculation:
5 O" C5 b% M) L% pCalculate the percentage of aluminium oxide (Al2O3) in the sample
- @* v# T6 h( S2 Y7 m5 @- Qtaken by the formula:
# A; h# s( Y, k( ~/ D% Al2O3 = 100 × (0.005VT)/S) E: p' d& W3 @- t. B0 V# g
where
- B" u* V* X6 G4 Z ^# WV is the number of ml of 0.01 N zinc sulfate consumed in
) _, b1 t6 `% Tthe second titration," F! q+ R5 T( H) v/ E- h2 F0 }3 r
T is the titre of the zinc sulfate solution,5 a) J0 S- ?4 T/ l0 l
S is the mass (g) of the sample taken, and
! H9 B8 y: N. R4 V. j( y; T0.005 = 500 ml / (1000mg/g × 100 ml).# @# L" M1 P9 E: t
Silicon dioxide Accurately weigh 1 g of the sample and transfer to a 250-ml high-silica3 G, h8 N" \# Y
glass Erlenmeyer flask. Add 10 g of sodium bisulfate (NaHSO4 ? H2O).
- J4 N# G Y6 xHeat gently over a Meeker burner, while swirling the flask, until
* R2 o% r% \/ z. M% Y$ @decomposition and fusion are complete and the melt is clear, except1 j& [6 U9 `, s* ]
for the silica content, and then cool. (Caution: Do not overheat the
, Q( O) C7 h' }# a4 B: K5 D. d' Tcontents of the flask at the beginning, and heat cautiously during$ w2 t( H8 b- w' y7 P% s
fusion to avoid spattering.)
) z; ?3 F j$ \7 yTo the cooled melt add 25 ml of sulfuric acid solution (1 in 2) and heat
3 b0 v. ^! C% ]+ j+ @+ Bcarefully and slowly until the melt is dissolved. Cool, and carefully add
% K/ L4 I+ f2 O$ ^ N0 s150 ml of water by pouring very small portions down the sides of the
+ T9 E! l+ r6 Jflask, with frequent swirling to avoid over-heating and spattering. Allow) O \1 Z* W" S- h+ G$ Q8 `
the contents of the flask to cool, and filter through fine ashless filter
+ j% D S5 e2 L3 P5 H3 C, ^paper, using a 60 degree gravity funnel. Rinse out all the silica from
* `9 c! b1 A: H) Nthe flask onto the filter paper with sulfuric acid solution (1 in 10).
. ^ Y) ]3 K! p8 [2 {6 j' y, lTransfer the filter paper and its contents into a platinum crucible, dry in
" M6 B* Y7 K! Y4 Q3 t! c9 W/ ban oven at 1200, and heat the partly covered crucible over a Bunsen+ e9 y3 _5 L! [" h
burner. To prevent flaming of the filter paper, first heat the cover from2 X: H& F2 T2 [& `3 o5 q. D
above, and then the crucible from below.; t; J# o; v3 w4 o# [
When the filter paper is consumed, transfer the crucible to a muffle* g' z5 |' T0 F& F! J
furnace and ignite at 1000o for 30 min. Cool in a desiccator, and
" S/ b' b# |' i. \, Iweigh. Add 2 drops of sulfuric acid (1 in 2) and 5 ml of concentrated
$ S2 } r* W& U8 Zhydrofluoric acid (sp.gr. 1.15), and carefully evaporate to dryness, first
. {' M" g" _4 h- ]% R ?2 ion a low-heat hot plate (to remove the HF) and then over a Bunsen" P. a V3 [1 G* G2 }/ f1 k
burner (to remove the H2SO4). Take precautions to avoid spattering,
+ y: @& o" A: W% o5 S. J) y! q4 q- v" o5 iespecially after removal of the HF. Ignite at 1000o for 10 min, cool in a
+ O: p* J2 |- H* N& Rdesiccator, and weigh again. Record the difference between the two4 F# j0 j& A' Z- @3 K. r# ] a
weights as the content of SiO2 in the sample.3 u1 @% `) p/ |, w3 I" q
METHOD OF ASSAY$ u7 ]9 ]/ H) C4 M& T( f
Accurately weigh about 150 mg of the sample, previously dried at 105o
5 Y- n3 [7 u8 \1 nfor 3 hours, and transfer into a 500-ml conical flask. Add 5 ml of water
. t$ N' D Q- O2 m! V/ ^and shake until a homogeneous, milky suspension is obtained. Add 30' Z: G; h. F, r& c6 w6 Y
ml of sulfuric acid and 12 g of ammonium sulfate, and mix. Initially
$ F( X0 g1 L, J+ P9 s, Rheat gently, then heat strongly until a clear solution is obtained. Cool,
, v0 a$ o5 t+ P' @& N6 d) nthen cautiously dilute with 120 ml of water and 40 ml of hydrochloric
% S* X, {# e; `( f( R* racid, and stir. Add 3 g of aluminium metal, and immediately insert a5 s( n9 W# o- R& e1 w
rubber stopper fitted with a U-shaped glass tube while immersing the9 |6 Z$ C9 g- g. t
other end of the U-tube into a saturated solution of sodium9 J) q0 w N4 J: q
bicarbonate contained in a 500-ml wide-mouth bottle, and generate" v5 E# O6 V% ?
hydrogen. Allow to stand for a few minutes after the aluminium metal
" O( K+ K1 q7 c6 s1 Ohas dissolved completely to produce a transparent purple solution.
9 h$ X, p: Y% gCool to below 50o in running water, and remove the rubber stopper0 ^8 s! Z& X, j2 _
carrying the U-tube. Add 3 ml of a saturated potassium thiocyanate1 R7 G% Y2 V9 m
solution as an indicator, and immediately titrate with 0.2 N ferric
9 J! h. H3 H# E$ f0 s4 D$ rammonium sulfate until a faint brown colour that persists for 30
5 y+ ?' ~( C) aseconds is obtained. Perform a blank determination and make any
! D4 j4 H% O) L" @9 Lnecessary correction. Each ml of 0.2 N ferric ammonium sulfate is
7 T. C' q& Y) a g6 requivalent to 7.990 mg of TiO2.$ S7 t- T5 n; v `1 N/ g' t
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