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\% 2%) J. Flow Injection Anal., Vol. 16, No. 2 (1999)

Intelligent Devices for Advanced Chemical Analyses Using Flow Injection Method

Keiro HIGUCBIx and Shoj M O T O M .

Department of Chemistry; FacuttyofSakn~e, Okayama Universs'ty, 3-1-1 Tbushimanaka,

Okayama 700-8530, Japan

h a t address: FIADivision, Tb&yo Kasei Kbgyo Co. Ltd, 6-15-9 Tbshima, Kita-ku,

7bkyo 114-0003, Japan

In flow injection analysis o, it is very important to devdope novel chemical and 1 or pretreatment devices as well as new sensing systems and new chemical reaction systems, for advancing chemical analyses. In this paper, several intelligent devices, in which specific chemical reactions can be carried out on-line with high efficiency and high precision, are reviewed with respect of the enhancement of SPARS and ZEC; SPARS means "Sensitivity and Selectivity, Precision, Accuracy, Rapidity and Simplicity" , ZEC "Zero Emission Concept" . Devices for oxidation 1 reduction reactions, photo reactions,

gas difiusion, solvent extraction, chromatomembrane and acceleration of a precipitation reaction are referred in this paper.

Rg.1 Schematic FIA diagram far the determination of nitrate OS, &r solution (EOTA + LM&O); RS, reagent solution (sulfanilamide + N-1-naphthylethyienediamine); P, double-plunger micro pump (each flow rate : 0.5ml nun") S, sample injector (lOOul); M C , Cd 1 Cu reduction column (2mrni.d X 10cm); RC, reaction coil (0.5mmi.d X 2m); TC, temperature-controlled bath; D, detector (540nin); Ft, recorder; W waste.

v Time.

Rg.2 Row signals for the calibration graphs of nitrate and nitrite IN-NO,-] IppmA, 0; B, 03.; C, 0.4;D, 0.6; E, 0.8; F, 1.0 [N-NOg] /ppm a, 0; b, 02; c, 0.4; d, 0.6; e, 0.8; f, 1.0 ~NO~]IppbG,O;H,20;1,40; J,60;K,80;L, 100 [N-NO;] lppb g, 0; h, 20; i, 40; j, 60; k, 80; I, 100.

Fig.3 Qarolation between the results obtained by FIA method and JIS method for the deteranmation of nitrate ion in aver water samples.

R

Fig.4 Schematic FIA diagram for the determination of nitrate and nitrite by photo-reduction method CS, carrier solution (EDTA+phosphate buffer); RS, reagent solution (sulfamlanride + N-1-naphthylethylenediamine); P, doubleplunger micro pump; S, sample injector ; PR, photo- reactor; Be by-pass tubmg; RC, reaction coil; D, detector (54Gnm); R, recorder; R! waste.

Motomizu ^My %M=T34)!/2LT W L + T < ~ ~ A ~ S % & S % ~ ~ - 7 W to BMl ^ m 93-76? HL\ ~ t 3 S 7 ^ & @ P 3 ] l & H l ^ LT, ^ T L L ^ K ^ ^ ~ ^ ^ ~ ^ J A L ^ 21'.

mtomizu ' 3 c D r n B ^ ^ m W ^ ^ ~ ~ & > Z S R ~ R - ^ ~ ~ Y ~ A @ Re.4 tar. ,%%W%EtA 4W CN-XE 7 -7 >Â¥ (W 14mm. i%$ 134mm) 2 ^W\^, Z ^W 0.8mm, 9i-@ 1.58mm, f?$ 3m @ PTFE 93--7'8-7 >TTlW^-^T, M^-?rn^^"^ ; Â ¥ W ) ~ ^ % T T S ^ S ^ J K P J ~ ~ ~ T ~ Â j^tZi-feLfe. ^^wm^^->^ wr ->ai5iB ij /;awfw^ WT^/ntz) T4 I f7. &BtW^. s^f3 4

LT-W^^C%TML^gJ, F'5@ 0.8mm cD PTFE ?-3--7fl3?3;Â¤7 W t l ^ \ Z W t > i ^ k . m^^ <Wl ttS^^--^^^ I? ^ t tmtpSLhtfe . ^fey ?l7tW^kVÂ¥ fea^^W^~,Wt^~1^^ ! )^~ t~-^vC^l-Lfe%5E, EDTA WT<D^. ^^^^^T ll fe-g, ^ mi

Time Fig.6 Effect of UV-irradiation for the photo-decomposition of phosphorus compounds' (4, .lamp on; (b), lamp off A, orthophosphate; B, glucose-1-phcephciric add; C, glucose- 6-phosphoric a+& D, ribose-5-phosphoric add; E, riboflavine phosphate(Na salt); F, a -glycerophcsphate @Na salt); G, 1-aminoethylphosphoric add; H, methyltriphenylphosphonium bromide; I, AMP; J, ADP; K, ATP; L, sodium diphosphate; M, sodium tripolyphosphate.

. .

EN?=-Â¥^' 7 9 Ã‘@@^SL(120 16O0C)Kh@% L T M L k @ , â 1) 7F> 7:i /-~7m-r W) ->awws.i~_ cfc^ fiT- a- . L^L, lwc &Mshu As miy ^@@5fc

aW^^&;5. S K Y IJ^ff iTW^Â # Y aim7m%afflW^hffi3~^ F^^LY m, B@TBammbR w<m^-^.

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^W^î^^M^T-srn^Â¥ 'l>^<^W&^fe. -77, Higuchi 5 icb^@ro^BS^^ Lab $%,!z.7k Â¥>^^W^L PTFE 93-7% 1) 7^-^LT^^ÊÊî

@itÃ‘#R&&kJ?+I >a FIA Z2Li3&@H% Lfe !@. 4W Df&E7J<^Â >YtZF^ 0.5mm, W 1.58mmY S 5m QI PTFE F-L-7'" @iS^Ô, m ~ m a - 3 f e % % ! g^b^W^(0.5%4)b

0 2 4 6 8

Heat-deoomposition Method / pun

Fig.7 Correlation between the results obtained by the p q m d plioto-deco&tion method and the heat- decomposition method y=0.9797x-0.0325 (~0.9986, n=16).

Fig8 Gas diffusion unita 1, carrier solution inlet; 2, reagent solution inlet; 3, ferrule; 4, porous PTFE tubing; 5, glass tube; 6, reagent solution; 7, carrier solution; 8, O-ring; 9, carrier solution to the waste; 10, reagent solution to the spectrophotometer.

Fig9 S d ~ e h diagram of a flow system for the determination of ammonium ion CS, earner solution (0.02M NaOH); RS, reagent solution (2.5 X KTM Cresol Red, 4 X 10%4 HEPES, pH7.0); P, double-plunger micro pump (each flow rate : 0,5uilnmi'1); S, sample injector (ZOO&; RC, reaction coil (O.6mmi.d Xlm); GD, gas diffusion unit; TC, temperature-controlled bath (40Â°C) D, detector (550nm); R, recorder; Wrs, carrier solution waste, Wm reagent solufion waste.

Aqueous phase

Organic phase

Aqueous phasn

Fig.10 Segmentor(a) and phase sepambqb) used for solvent extraction 1 FIA.

Segment wa

(to detectart

Fig. 11 Douhls-membrane phase & p a r a 9 Wi, Wg, aqueous phase waste; Wg, organic phase; MF,, MFÃ micropomus PTFE membrane.

4.12 1) *A, P h 11 '>AO^a 7) '1 iMF^l /* '1 32R42g4 3- >

a~^a#$ffi"?Â¥iÂ ^ 7 'b* (DBTRBÂ£S^L-S~- .Dl' 2 > M 3 y ^ ^ f i q 4 3 l J R m

Tb-5. *U"7A^>05Â£ ^fcL 9 %Xb^f^L-C 1 8 - f i W - 6 , p ^WM 4-(4^s^7^ 7xr: )b7V)-2,5-^ D ~^>e>X)i^>@% -Â£^^-?^HI'I ^>-Y^â‚ ^ D U W - >(l:l)Sl Xfc: TS; ^% hk. (Q^&I:: A i3.&XRBfftiA 10% T-, 5~ 10'M ~ ~ Y b 1) WI'%X?)$$ ^-^WL/5^. ^fey t% lmm, ^ 20cm 0 PTFE TÂ¥L-74291 W^W R L T < W L k h 7 A - Â £ & > 7 >C#B.&A o , ? h 'J $A, A 1) 9A??^>V' 18- 7 7 9 > - 6 i@@k LTB#Lk@, W(Q > > ^ ^

+>:=â‚ 5' D ~ ^ > - t f > ( l : l ) ^ - & ~ I t ~ % ) ffib, WmynbWtQD 450am T-a@ WSaIJZLTi- b 1) $A, A '1 A IB) iT*W%mn)6 B?.

non-polar liquid or gas

I

Fig. 12 Chromatomembrane cellq m& porous PTFE membrane

Bpomus PTFE block..

Fig.13 Schematic FIA diagram for the determination of sulfato ion CS, carrier solution 0); RS, reagent solution (banurn- DMSffl); P, double-plunger micro pump (each flow rate : 0.751111 d'); S, sample injector (200y3); OBC, cation exchange resin column (Smim.cLX Ih); RC, Barn.,- i m n ~ o w dais beads ~~?acirx wlumn-d X 1b) ; D, detector (662nm); R, recorder W, waste.

. . - I 8min

Time

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(Received November 30, 1999)

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