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二氧化钛(钛白粉)
二氧化钛(钛白粉)# x# w6 I. _" q3 P0 B
, l. t% c$ }! L1 \/ `! d8 U0 OJECFA关于二氧化钛(钛白粉)的结论0 Y/ m* j& L5 X; J9 n* W
5 Q5 F8 {8 y$ r7 K, ~摘要: 2006年JECFA关于二氧化钛的结论: f7 U( y% i* L7 L J$ s
ADI值:不作限制。
2 f. y2 N2 }) U4 [ m, z功能:着色剂
0 s2 C6 |3 S) D3 [! } Z N8 Q; n
TITANIUM DIOXIDE8 t& J0 K( Q7 d! l
Prepared at the 67th JECFA (2006) and published in FAO JECFA( S& g# W; G8 c
Monographs 3 (2006), superseding specifications prepared at the 63rd; I# R% M- E* `/ k) N8 [
JECFA (2004) and published in FNP 52 Add 12 (2004) and in the
+ _9 v: Y. d3 L1 R9 ^: s" a2 a5 ?Combined Compendium of Food Additive Specifications, FAO JECFA* p4 k! U# `) N, Y. }
Monographs 1 (2005). An ADI “not limited” was established at the 13th P k1 A& O( D# \( }. [
JECFA (1969).
# ^) g" P* ^9 ~8 f% jSYNONYMS
; W0 k: V5 o& S/ {Titania, CI Pigment white 6, CI (1975) No. 77891, INS No. 171
" |' i( e, g5 O) I6 t0 x0 dDEFINITION
- B, R3 S$ s4 e# w8 d; cTitanium dioxide is produced by either the sulfate or the chloride
9 X8 J1 N$ H" X# j: Dprocess. Processing conditions determine the form (anatase or rutile3 \$ ~4 O* p% i& ]4 ^3 i
structure) of the final product.! `& d" L, V. @( C
In the sulfate process, sulfuric acid is used to digest ilmenite (FeTiO3)
( l1 E: }- W4 r5 X( `or ilmenite and titanium slag. After a series of purification steps, the. q# } s2 k. _2 L6 Y
isolated titanium dioxide is finally washed with water, calcined, and4 |0 y2 N9 ?6 C6 X D7 g
micronized.
7 J. | ?% j9 aIn the chloride process, chlorine gas is reacted with a titaniumcontaining. B( C6 W; q# C7 T% r+ N, R+ v1 |
mineral under reducing conditions to form anhydrous' u4 J) F! L4 \7 w9 w3 \/ p
titanium tetrachloride, which is subsequently purified and converted to* M) g$ z- d: h# u1 h8 l
titanium dioxide either by direct thermal oxidation or by reaction with. w4 z/ L3 d8 k! @, N" K+ L+ J8 E
steam in the vapour phase. Alternatively, concentrated hydrochloric% }' R! Q* |; _0 |) v
acid can be reacted with the titanium-containing mineral to form a: x: W! `( G. ^0 M$ p( U' ^: b
solution of titanium tetrachloride, which is then further purified and
7 ~. H, y; Z) |0 x( D/ Sconverted to titanium dioxide by hydrolysis. The titanium dioxide is6 s% Q. r$ U/ | E, k! }
filtered, washed, and calcined.! e7 R; X4 T# g% h! D3 I* i
Commercial titanium dioxide may be coated with small amounts of" w5 [0 d7 g5 s
alumina and/or silica to improve the technological properties of the* u& K& u( }( H
product.
: X- ~4 v; Z; VC.A.S. number 13463-67-7
+ K0 M( @! s" ~+ gChemical formula TiO2
" _, k, q0 s' c: k+ CFormula weight
$ \( z. E: f1 E# E# F- |9 T0 P79.88
0 i$ ?0 r) F x1 iAssay* l* b' X; f( S4 A2 g
Not less than 99.0% on the dried basis (on an aluminium oxide and) C: C: J9 H3 Y, p" [. K
silicon dioxide-free basis)
0 b3 y' M. v2 S' b! `: E# J cDESCRIPTION
8 H' s' N( M) E, G2 ~& z) g* |White to slightly coloured powder" R5 p$ `9 e t) l- v( d4 U8 p8 @
FUNCTIONAL USES
$ H# O+ G0 \/ y4 T0 i+ VColour( l- N( u) M+ o; O8 e
CHARACTERISTICS
. ~& z- [% S, h9 [4 S9 s2 | r0 XIDENTIFICATION! X. n/ M$ p# g/ M" e
Solubility (Vol. 4)4 F3 p$ B3 W& Q8 \6 ~. C/ |
Insoluble in water, hydrochloric acid, dilute sulfuric acid, and organic% y- A5 i7 l9 n7 ~ g, z5 E
solvents. Dissolves slowly in hydrofluoric acid and hot concentrated& l3 W- j% ^& t+ w
sulfuric acid.9 i( G% p6 L# |% u
Colour reaction
/ d- L8 y o) ^& f- O DAdd 5 ml sulfuric acid to 0.5 g of the sample, heat gently until fumes of
% Q4 D( X+ x! x0 Tsulfuric acid appear, then cool. Cautiously dilute to about 100 ml with
7 z' B; O# @3 V9 Q( C8 j2 \water and filter. To 5 ml of this clear filtrate, add a few drops of
! {" V- p9 [( ]) Z7 J& _hydrogen peroxide; an orange-red colour appears immediately.# v# ~$ I) M+ k$ }9 J
PURITY
4 }: p1 l- s4 K( T/ y, x+ B4 ~+ d, dLoss on drying (Vol. 4) Not more than 0.5% (105°, 3 h)# ]2 f( L/ _5 g8 e- b
Loss on ignition (Vol. 4)( X% J k0 d8 B) i
Not more than 1.0% (800o) on the dried basis
8 p* H8 r7 M- b CAluminium oxide and/or5 o- z8 `5 p% z; b- H7 G( f p6 L
silicon dioxide
# ?2 ?# I4 x- B& k* i+ M. I+ lNot more than 2%, either singly or combined
1 s7 z8 Q4 v# T2 l5 iSee descriptions under TESTS
D! E. a9 J, k. ]: fAcid-soluble substances Not more than 0.5%; Not more than 1.5% for products containing
7 E7 R: Y. b h, ~- nalumina or silica.
& i" w4 [8 `, WSuspend 5 g of the sample in 100 ml 0.5 N hydrochloric acid and6 K! q) U* M/ K" L
place on a steam bath for 30 min with occasional stirring. Filter% S" }* f2 k& B' y6 m- z
through a Gooch crucible fitted with a glass fibre filter paper. Wash1 d/ b1 j, O3 S0 |1 e# {
with three 10-ml portions of 0.5 N hydrochloric acid, evaporate the
. @$ M: o3 Y/ h8 vcombined filtrate and washings to dryness, and ignite at a dull red
- x) X. J( G z9 M& v) R4 ?' Xheat to constant weight.
) f/ p2 K6 W. S: n4 s3 j9 m, \. dWater-soluble matter# r5 @2 k: L$ b! S' I J
(Vol. 4)/ k7 k/ ?8 b: F. G4 g1 V2 \
Not more than 0.5%0 N5 M8 L) L" T% p5 _
Proceed as directed under acid-soluble substances (above), using6 V/ M) A1 N4 p: D
water in place of 0.5 N hydrochloric acid., [: ^* K# i% N* D
Impurities soluble in 0.5 N& N- ~4 p Z! R9 R* h0 o, H
hydrochloric acid' K5 p* w. _$ \, y
Antimony Not more than 2 mg/kg
: O6 K3 \1 d5 ~See description under TESTS
/ t; d# H4 R) z, ?# s# wArsenic Not more than 1 mg/kg9 M) Q. f% l. j; B" [% J+ H
See description under TESTS. ]9 ]! e0 B7 S) q
Cadmium Not more than 1 mg/kg
4 W6 ]' N4 v7 h% E' ZSee description under TESTS
/ r# y- }- `: f4 a# J$ ^) XLead
& {- n; G9 |9 g lNot more than 10 mg/kg0 e1 n( Q6 c. G% W3 w0 E2 H+ `
See description under TESTS
0 B2 L9 @; W) e4 xMercury (Vol. 4) Not more than 1 mg/kg4 U+ K! V2 A7 i* u" T# J
Determine using the cold vapour atomic absorption technique. Select a9 H" M; w5 x" r: c7 J
sample size appropriate to the specified level
+ P s6 ^2 w+ N$ B oTESTS
9 X2 u8 _ m3 OPURITY TESTS
& {- l" Y- Z* P: s9 EImpurities soluble in 0.5 N' J' G0 O) T3 v* L/ q
hydrochloric acid
# S8 E! i2 I) t! OAntimony, arsenic, c8 g/ m1 `" R% h$ ]) _
cadmium and lead
% Q7 B! K" d$ l(Vol.4)# f8 W) Y7 R1 H; U5 G9 G
Transfer 10.0 g of sample into a 250-ml beaker, add 50 ml of 0.5 N6 z3 p" W! p$ l3 Q
hydrochloric acid, cover with a watch glass, and heat to boiling on a+ h; q/ i2 W5 L* o1 a! ? x
hot plate. Boil gently for 15 min, pour the slurry into a 100- to 150-ml
" S) P W2 }" i" l4 e7 e; C5 Jcentrifuge bottle, and centrifuge for 10 to 15 min, or until undissolved6 G" P% n- R# ^
material settles. Decant the supernatant extract through a Whatman2 `1 b) z7 C2 c j# Q. ]2 o
No. 4 filter paper, or equivalent, collecting the filtrate in a 100-ml6 B" h" `5 X7 F9 S
volumetric flask and retaining as much as possible of the undissolved; v& d+ K! ]% e# O
material in the centrifuge bottle. Add 10 ml of hot water to the original3 l J3 `" ?1 w6 I: O" s" }
beaker, washing off the watch glass with the water, and pour the
6 Z. A% s3 C5 z# ?: Y$ ~% I/ Ncontents into the centrifuge bottle. Form a slurry, using a glass stirring
% U. |' G/ L2 j$ K4 a9 { }rod, and centrifuge. Decant through the same filter paper, and collect7 @, P- e0 w( O3 E: d
the washings in the volumetric flask containing the initial extract.+ m- {1 f! q5 ~4 ]5 {
Repeat the entire washing process two more times. Finally, wash the' e: a# I: @2 a; _( u1 p
filter paper with 10 to 15 ml of hot water. Cool the contents of the flask- h4 O2 D) {! t/ d; T; M
to room temperature, dilute to volume with water, and mix.
8 ]4 L, d, j t7 K7 X4 J- I3 pDetermine antimony, cadmium, and lead using an AAS/ICP-AES
J- r) y- x1 |5 r) Qtechnique appropriate to the specified level. Determine arsenic using the
/ h# z% x0 {: _ICP-AES/AAS-hydride technique. Alternatively, determine arsenic using9 y) Y7 q! I8 D0 q; I7 {) o
Method II of the Arsenic Limit Test, taking 3 g of the sample rather than. J; m9 d, A" e9 Q; ?4 e
1 g. The selection of sample size and method of sample preparation( O$ A! ?; L; K% Z
may be based on the principles of the methods described in Volume 4.6 r! ^2 _1 t6 y/ ]5 l
Aluminium oxide Reagents and sample solutions0 |* M( \4 }9 q8 w+ G- Q
0.01 N Zinc Sulfate. L1 g9 k9 `. I3 [
Dissolve 2.9 g of zinc sulfate (ZnSO4 ? 7H2O) in sufficient water to) }# q8 k' E% E9 h4 i
make 1000 ml. Standardize the solution as follows: Dissolve 500 mg' s" u6 w) T& Q( k- y: x0 B! {
of high-purity (99.9%) aluminium wire, accurately weighed, in 20 ml of) w1 C) W+ s) i& e
concentrated hydrochloric acid, heating gently to effect solution, then- V+ e+ }5 H$ ?! O, ?
transfer the solution into a 1000-ml volumetric flask, dilute to volume6 o' l2 u9 J4 [' G3 }0 x9 A
with water, and mix. Transfer a 10 ml aliquot of this solution into a 500' |; b. u& d( Q0 o
ml Erlenmeyer flask containing 90 ml of water and 3 ml of) @* q' R. l" y
concentrated hydrochloric acid, add 1 drop of methyl orange TS and
5 q$ E0 L2 K7 D; ?1 U25 ml of 0.02 M disodium ethylenediaminetetraacetate (EDTA) Add,
: ?8 z p3 V2 adropwise, ammonia solution (1 in 5) until the colour is just completely
+ R5 c# d: Y$ D2 ]: achanged from red to orange-yellow. Then, add:
5 w+ R) P1 e( H- n1 c(a): 10 ml of ammonium acetate buffer solution (77 g of
5 F- J* ] ^; _& I3 B' \& X6 Uammonium acetate plus 10 ml of glacial acetic acid, dilute to' L! w/ z6 Z! u# m
1000 ml with water) and
, S5 o+ z# i9 v( I$ n) N(b): 10 ml of diammonium hydrogen phosphate solution (150 g' J8 K: `1 d1 B( j% A8 J6 D+ w ^
of diammonium hydrogen phosphate in 700 ml of water,
. d) C) |+ g' `3 x O$ Jadjusted to pH 5.5 with a 1 in 2 solution of hydrochloric acid,
, m- y: P5 h! _+ L& |then dilute to 1000 ml with water).* d/ {( A6 w+ c. u. Q
Boil the solution for 5 min, cool it quickly to room temperature in a% A( o- t+ S7 J0 K
stream of running water, add 3 drops of xylenol orange TS, and mix.2 z9 R, [$ u7 Q0 y
Using the zinc sulfate solution as titrant, titrate the solution to the first
2 o( p, R6 }. zyellow-brown or pink end-point colour that persists for 5-10 sec. (Note:! U3 f9 ]* a0 q9 i( }
This titration should be performed quickly near the end-point by
1 j! T' ?! n8 [adding rapidly 0.2 ml increments of the titrant until the first colour
5 J! F7 `" ?% y: L4 Y3 ^, Ichange occurs; although the colour will fade in 5-10 sec, it is the true* c/ R; Z4 ]& b9 B
end-point. Failure to observe the first colour change will result in an8 F& I) y) D; G7 T& y
incorrect titration. The fading end-point does not occur at the second
: m: E" R* L; B$ R6 Rend-point.)
# R% }+ K4 K% T7 |! z! L# w1 f5 a3 _" FAdd 2 g of sodium fluoride, boil the mixture for 2-5 min, and cool in a
: ] K: h- ~/ @: f9 g4 e. ustream of running water. Titrate this solution, using the zinc sulfate
: r9 P+ B9 ]' a0 ^4 esolution as titrant, to the same fugitive yellow-brown or pink end-point
: p' s+ _4 N8 ?7 Pas described above.2 V! k9 C+ z" S
Calculate the titre T of zinc sulfate solution by the formula:
! K0 Q; p$ S' I- b$ U. E- h# eT = 18.896 W / V
" }& m m, w, L" O8 hwhere9 a/ H7 l9 ^* X) x( N" p9 W5 C
T is the mass (mg) of Al2O3 per ml of zinc sulfate solution! l9 a5 Q$ f A9 {+ r' U
W is the mass (g) of aluminium wire
$ j3 ^/ U8 m3 G/ PV is the ml of the zinc sulfate solution consumed in the' C& z, s$ G+ d0 `' r
second titration
2 s% ~) r) ]: l7 M- O18.896 = (R × 1000 mg/g × 10 ml/2)/1000 ml and
0 e% @" R) f4 f% D! XR is the ratio of the formula weight of aluminium oxide to8 z5 S/ }# s1 v- d
that of elemental aluminium.
, p4 O. u, W) `Sample Solution A2 O# b! \6 c: s3 S, N0 B8 H9 f$ j5 j
Accurately weigh 1 g of the sample and transfer to a 250-ml high-silica) w b) N }, l$ C8 a
glass Erlenmeyer flask. Add 10 g of sodium bisulfate (NaHSO4 ? H2O).
; x+ Z( v, j* n, [( D(Note: Do not use more sodium bisulfate than specified, as an excess
& T9 ?% ^/ u! D, B" t' Cconcentration of salt will interfere with the EDTA titration later on in the
/ W1 }9 F8 I' U. \; e. j& Tprocedure.) Begin heating the flask at low heat on a hot plate, and
6 }- y. _! }9 y+ B; s! ythen gradually raise the temperature until full heat is reached.
+ q3 u! J; ~7 }& S. n' e(Caution: perform this procedure in a well ventilated area. ) When
0 H2 W9 p/ Z1 ]4 yspattering has stopped and light fumes of SO3 appear, heat in the full
' W3 k1 b! B, u( I' U/ R0 Lflame of a Meeker burner, with the flask tilted so that the fusion of the1 W- r3 M4 @9 D( ^
sample and sodium bisulfate is concentrated at one end of the flask.
! W3 Z! h* l7 _" K* w& _" N9 Z3 {* ySwirl constantly until the melt is clear (except for silica content), but0 C/ n/ p+ }; j
guard against prolonged heating to avoid precipitation of titanium5 D# Q0 C6 c1 w) @ _
dioxide. Cool, add 25 ml sulfuric acid solution (1 in 2), and heat until
# O. T* W, q0 z( I/ kthe mass has dissolved and a clear solution results. Cool, and dilute to
* v* {6 P% n% S0 ~$ K120 ml with water. Introduce a magnetic stir bar into the flask.
" y# R4 O) }0 m6 b f' MSample Solution B
! O7 U9 G, s% I1 l" X ?Prepare 200 ml of an approximately 6.25 M solution of sodium
( r* a2 _* H+ chydroxide. Add 65 ml of this solution to Sample Solution A, while# c Y, b- S+ @) V( `
stirring with the magnetic stirrer; pour the remaining 135 ml of the
% a4 e% v, I3 P" x' L( s. C7 O, nalkali solution into a 500-ml volumetric flask.
# q' V3 l6 G) V) t1 {/ G. b/ kSlowly, with constant stirring, add the sample mixture to the alkali
J8 C; y: g% j7 G4 ?7 isolution in the 500-ml volumetric flask; dilute to volume with water,4 L) w: G+ N6 p- @2 G! a. t; N
and mix. (Note: If the procedure is delayed at this point for more than
" {* L( A. Z. s+ F2 hours, store the contents of the volumetric flask in a polyethylene
* C2 o/ E! s& kbottle.) Allow most of the precipitate to settle (or centrifuge for 5 min),
: M9 p h8 A. H( U: f: Fthen filter the supernatant liquid through a very fine filter paper. Label
: [. f) a9 M! i. _8 d, [the filtrate Sample Solution B.
1 Y$ Z7 b' l* X' OSample Solution C
$ ]4 `- b: R) B+ fTransfer 100 ml of the Sample Solution B into a 500-ml Erlenmeyer
1 B; q! K! Q! k4 M" yflask, add 1 drop of methyl orange TS, acidify with hydrochloric acid
7 Y* i$ Q% h3 E8 U6 csolution (1 in 2), and then add about 3 ml in excess. Add 25 ml of 0.02
* _$ X8 n1 \# x3 D, x k! O7 r. gM disodium EDTA, and mix. [Note: If the approximate Al2O3 content is
3 A" b( Z- _1 b, O$ Lknown, calculate the optimum volume of EDTA solution to be added9 j' b5 ^% I: i: r3 L0 v9 M
by the formula: (4 x % Al2O3) + 5.]7 E7 a* b% {; K B% m
Add, dropwise, ammonia solution (1 in 5) until the colour is just
+ P8 p5 R4 f' Mcompletely changed from red to orange-yellow. Then add10 ml each
& K+ }9 S, W6 u0 N3 k; ^9 ~0 j3 Gof Solutions 1 and 2 (see above) and boil for 5 min. Cool quickly to# z1 ^4 t; A0 R e, b" |5 y
room temperature in a stream of running water, add 3 drops of xylenol) \( j6 i; B9 j# _" J
orange TS, and mix. If the solution is purple, yellow-brown, or pink,
+ B9 U+ y' x9 V! x4 ^: D2 Kbring the pH to 5.3 - 5.7 by the addition of acetic acid. At the desired; g; Y* f! T# V1 A/ B B
pH, a pink colour indicates that not enough of the EDTA solution has5 G$ X# n, G, m- z
been added, in which case, discard the solution and repeat this
: `- ]$ R7 d: v v; r4 C# Bprocedure with another 100 ml of Sample Solution B, using 50 ml,, R: v% B5 ~1 e+ ?: _) v; d+ [
rather than 25 ml, of 0.02 M disodium EDTA.
+ Y# G* c7 s. o7 j) ZProcedure( N! i/ B2 H; k3 E+ X0 i4 t
Using the standardized zinc sulfate solution as titrant, titrate Sample
2 n7 D. D! P0 Z5 ]Solution C to the first yellow-brown or pink end-point that persists for
" W2 f7 q/ m d. ~5-10 sec. (Important: See Note under “0.01 Zinc sulfate”.) This first
) m/ `6 u' ~, I3 e# m/ S( K; dtitration should require more than 8 ml of titrant, but for more accurate
9 D6 Y5 q9 S2 e) c" V. Awork a titration of 10-15 ml is desirable.1 ~. H$ ?7 H t$ j2 {
Add 2 g of sodium fluoride to the titration flask, boil the mixture for 2-59 j' i: B7 J+ Q3 g, |
min, and cool in a stream of running water. Titrate this solution, using2 M u6 q7 h. z2 H
the standardized zinc sulfate solution as titrant, to the same fugitive
& [2 b* U. e; |yellow-brown or pink end-point as described above.
( E7 _7 m; G3 d0 Z T) V0 bCalculation:+ d+ s8 h- w+ T' L/ a( ~
Calculate the percentage of aluminium oxide (Al2O3) in the sample
7 F& ]2 N; w5 l" {$ y2 u4 ytaken by the formula:8 L0 [* r' n. N/ }. j/ x8 X# |
% Al2O3 = 100 × (0.005VT)/S
8 c7 n7 U& @8 X5 N1 m6 ~% R9 D4 Lwhere
8 ^' C: m7 U/ WV is the number of ml of 0.01 N zinc sulfate consumed in
5 u8 B. y/ M s+ J* r1 @the second titration,+ f* s6 a$ r: l6 `1 `
T is the titre of the zinc sulfate solution,
3 y7 B. _# d D+ oS is the mass (g) of the sample taken, and9 l9 ]8 q% q9 H% I! ?5 D
0.005 = 500 ml / (1000mg/g × 100 ml).
' Q( ]! N$ x4 }" X2 W4 m/ I+ ySilicon dioxide Accurately weigh 1 g of the sample and transfer to a 250-ml high-silica- J) q2 T0 w: w4 b* c4 |
glass Erlenmeyer flask. Add 10 g of sodium bisulfate (NaHSO4 ? H2O).. P; N; K7 |/ j- k
Heat gently over a Meeker burner, while swirling the flask, until
7 ]5 }5 L& w& t; P9 ^. A3 Gdecomposition and fusion are complete and the melt is clear, except
# g8 L2 E+ K9 c. O$ ~for the silica content, and then cool. (Caution: Do not overheat the M" [3 G/ q, [9 t6 B: M; _/ Z
contents of the flask at the beginning, and heat cautiously during
; |# H1 n7 w- P4 ]# z& u9 k5 p7 p6 Yfusion to avoid spattering.)* F2 T$ [$ _- _' U0 ~& b
To the cooled melt add 25 ml of sulfuric acid solution (1 in 2) and heat
: C3 ]& t' [( l$ G! @carefully and slowly until the melt is dissolved. Cool, and carefully add4 q2 c+ f* Z T8 J) @6 v6 o& T
150 ml of water by pouring very small portions down the sides of the
, Q3 p' Z) @8 K) E3 sflask, with frequent swirling to avoid over-heating and spattering. Allow
+ t8 C8 A& F G* H* j: b, Q$ ~5 Qthe contents of the flask to cool, and filter through fine ashless filter, E' ]& j) n! m( i% A5 i. L) r
paper, using a 60 degree gravity funnel. Rinse out all the silica from: P' Q7 Z# @; w) A' j! k6 ~1 z
the flask onto the filter paper with sulfuric acid solution (1 in 10).
/ z7 O/ B& b" ^+ y, qTransfer the filter paper and its contents into a platinum crucible, dry in
. z8 p; h7 Y+ k5 e: {+ G% xan oven at 1200, and heat the partly covered crucible over a Bunsen: ?: A6 V& X2 g* T7 e3 F( w# _
burner. To prevent flaming of the filter paper, first heat the cover from$ k% m# a4 S* X* ^2 ]; Z) Q$ O+ f
above, and then the crucible from below.
: n) y2 {2 T4 j: PWhen the filter paper is consumed, transfer the crucible to a muffle
4 F; e2 o- L* [, v, D* X, N# Rfurnace and ignite at 1000o for 30 min. Cool in a desiccator, and) |( n3 K) K+ \- F. ]6 Y' {6 A
weigh. Add 2 drops of sulfuric acid (1 in 2) and 5 ml of concentrated
! t4 g' Y+ m- w9 x/ ]hydrofluoric acid (sp.gr. 1.15), and carefully evaporate to dryness, first
+ `- U# W) h; F8 don a low-heat hot plate (to remove the HF) and then over a Bunsen0 P& H( p9 j0 W# j% I: B/ r4 B) E
burner (to remove the H2SO4). Take precautions to avoid spattering,
# Z2 p0 O8 x- C8 i: Lespecially after removal of the HF. Ignite at 1000o for 10 min, cool in a( g' J, f* O G6 q9 G# d
desiccator, and weigh again. Record the difference between the two
# W7 I# w* m5 T& W# B+ Vweights as the content of SiO2 in the sample.
# P t ]! N/ c: K3 UMETHOD OF ASSAY6 h# ^. J* M& H# c; E
Accurately weigh about 150 mg of the sample, previously dried at 105o, @9 x/ P0 h7 H, }: _6 G
for 3 hours, and transfer into a 500-ml conical flask. Add 5 ml of water$ G$ f3 A! @, }# Y0 F
and shake until a homogeneous, milky suspension is obtained. Add 30' n7 U! K8 y: ?. ? I
ml of sulfuric acid and 12 g of ammonium sulfate, and mix. Initially
$ O6 h- w. |4 Y2 h# z/ Rheat gently, then heat strongly until a clear solution is obtained. Cool,( {3 S/ C4 j/ t/ S2 d
then cautiously dilute with 120 ml of water and 40 ml of hydrochloric
" H0 H7 T1 K+ g, E i! ^acid, and stir. Add 3 g of aluminium metal, and immediately insert a
& X* X% e: A4 brubber stopper fitted with a U-shaped glass tube while immersing the0 ?6 w8 V* N$ ^ [. ` E" X
other end of the U-tube into a saturated solution of sodium5 } ]7 F# x4 G
bicarbonate contained in a 500-ml wide-mouth bottle, and generate
0 T) s1 {% p3 L+ x. ^hydrogen. Allow to stand for a few minutes after the aluminium metal
5 c0 h4 j3 s( `8 D" B/ q5 w. \has dissolved completely to produce a transparent purple solution.4 S! K9 ^8 M# M4 J# i8 |
Cool to below 50o in running water, and remove the rubber stopper
- {4 {7 [4 c$ X# ^$ U( I, z3 M6 |carrying the U-tube. Add 3 ml of a saturated potassium thiocyanate3 G$ ?& l$ o& V+ H9 J! y
solution as an indicator, and immediately titrate with 0.2 N ferric- E0 G9 a9 [ ~, O" U T
ammonium sulfate until a faint brown colour that persists for 30) d1 S W0 j- s7 S7 Z1 g
seconds is obtained. Perform a blank determination and make any) S' j6 V2 p# C" F5 }
necessary correction. Each ml of 0.2 N ferric ammonium sulfate is
% x- q' M5 C1 U, ?. vequivalent to 7.990 mg of TiO2.
6 i0 b% p9 ?+ h& B* b: y( ? |
|