366

trends in analytical chemistry, vol. 21, no. 5, 2002

Multicommutation as a powerful new analytical tool

Icardo M. Catala Department of Analytical Chemistry, University of Valencia, Valencia, Spain a Mateo J. V. Garc Department of Chemistry Sciences, University Cardenal Herrera, Valencia, Spain nez Calatayud* J. Mart Department of Analytical Chemistry, University of Valencia, Valencia, Spain
This review presents the state of the art of the emerging continuous-ow methodology based on solenoid valves. This uses ow networks to deliver sample and reagent solutions by controlling the time of ow through the ON/OFF modes of solenoid valves and takes advantage of existing ow injection analysis (FIA) or sequential injection analysis (SIA) device or manifold congurations. It allows one to insert a single plug of sample (or reagent) into the carrier or carrier-reagent stream, mimicking the approaches of FIA or SIA. In addition to the modes used in FIA and SIA, the methodology provides a different mode, based on delivery of a series of alternating sequential insertions of very small volumes of sample and reagent. This gives rise to different hydrodynamic and chemical processes and new analytical potential. The fundamentals of the methodology are discussed together with a broad view and critical survey of the advantages and the possible trends. # 2002 Published by Elsevier Science B.V. All rights reserved.
Keywords: Continuous ow; Multicommutation; Tandem ow

1. Introduction
Flow assemblies comprise a variable number of lines through which the solutions, sample and reagents are propelled on their way to the
*Corresponding author. Tel./Fax: +34 96 386 40 62. E-mail: jose.martinez@uv.es

detector. Especially prominent among ow techniques is ow injection analysis (FIA). Its inception over 20 years ago brought about dramatic changes in the way a solution could be handled and dispersion controlled. Its progress has rested on the development of ingenious assemblies and devices that allow the reproducible insertion of the sample solution into a owing system. Over time, such devices have evolved from the hypodermic syringe used by Ruzicka and Hansen in the early days of FIA, to the proportional injector, to the six-port rotary valve, which is currently the most widely used injection system in FIA. With the six-port rotary valve, the sample is loaded and inserted by pushing a mobile element between two xed positions, the volume of sample being determined by the length of the sample loop and the inner volume of the rotary valve. In the emerging multicommutation mode, the volumes of sample and other solutions are controlled by the time during which the stream, owing at a known rate, is allowed to circulate, so that uncertainty in the sample volume depends mainly on the precision with which the time can be controlled. With electronic timing devices, the associated error is minimal. The insertion of pre-set volumes of sample by controlling time was achieved by early FIA researchers. However, multicommutation methodology uses solenoid valves as differential elements and replaces insertion volumes with
# 2002 Published by Elsevier Science B.V. All rights reserved.

0165-9936/02/$ - see front matter PII: S0165-9936(02)00505-8

trends in analytical chemistry, vol. 21, no. 5, 2002

367

insertion times, thereby expanding the scope of time-based sampling methods. One other immediate result of using solenoid valves is that the ensuing assemblies are highly exible and easy to alter. In multicommutation assemblies using three-way solenoid valves, a ow network, comprising a variable number of valves, each acting as an independent commutator, is established and is controlled by computer. Such a network can be assimilated to an electronic circuit with a variable number of active nodes capable of individually adopting two different states: ON and OFF. This permits sample and reagent dispersion to be effectively controlled and opens up new avenues for development in ow analysis. The main foundation of this new methodology is the use of the solenoid valve (Fig. 1). Solenoid valves have been used previously in analytical chemistry as ancillary components for various purposes involving the handling of solutions and gases. Such valves have been used frequently in chromatography, for example, for the insertion of sample and solvents and for developing empirical approaches to mixtureresolution in countercurrent chromatography. Solenoid valves have also been used in gas chromatography, as components of sample micro-dispensers in synthetic processes, or to

control the inow and outow of gas. The many other applications include the introduction of solutions for determination by mass spectrometry, or controlling the ow in refractive-index determinations. In this review, we describe the development, modes, and uses of a new ow methodology that uses a manifold including several solenoid valves, which allow the operator to handle the solutions involved in the analytical process (i.e., a ow network). The Brazilian group at Piracicaba, led by B.F. Reis B. F. and E.A.G. Zagatto, who pioneered the development, has so far been the most active in its application. The emerging ow methodology has been used by FIA workers as a matter of preference. Its earliest precursor was probably the use of a solenoid valve integrated into an FIA assembly as an ancillary component for specic purposes (usually, controlling the sampleinsertion system). In some cases, a solenoid rather than a valve was used to actuate a piston valve (a syringe) [1]. There have been several attempts at integrating one or more valves in FIA assemblies; however, all are much more recent than those described above. Examples include: the use of a solenoid valve to avoid oscillations in the ow during sample insertion [2]; the use of a twoway valve as an alternative to other time-based injection systems [3]; in the determination of magnesium and of copper traces in water samples [4], a series of valves was employed to insert solid samples into an FIA assembly. Recently, an FIA-related technique called sequential injection analysis (SIA) was used with a set of three solenoid valves as an interface between a microwave oven for sample digestion and a conventional assembly for the determination of iron [5].

2. The insertion prole in multicommutation

Fig. 1. Working cycle of a three-way solenoid valve.

Three-way solenoid valves allow the design of active networks for precise control of sample

368

trends in analytical chemistry, vol. 21, no. 5, 2002

and reagent dispersion, and hence the development of gradient-based methods that are difcult to implement in FIA. A three-way solenoid valve behaves as a switch between two states: ON and OFF (Fig. 2). Two of the three valve ports are permanently connected. While the valve is OFF, the carrier solution is aspirated into the detector; when ON, an electronic pulse of programmable length allows the sample to be inserted into the carrier. The volume of sample inserted is proportional to the pulse length and can be altered by changing the prole of the insertion sequence; a single sample segment, or several segments of the same or different length, can be intercalated with the carrier solution. The result is a exible system that allows the insertion of volumes of sample that are variable via software. In addition, electronic control of the pulse length ensures reproducible insertion of sample volumes as low as a few microlitres. The amount of sample used is that aspirated during the time the valve is ON; no ushing, and hence no additional consumption of sample, is required. The use of small sample segments sandwiched between carrier microsegments facilitates thorough mixing of the sample and carrier solutions, even with large injected volumeswhich simply require more microinjections of sample. Finally, solenoid valves are easily automated.

3. Advantages and disadvantages of multicommutation versus classical FIA

Multicommutation is not simply a more convenient, effective alternative to classical methods for the insertion of sample and reagent solutions into a carrier stream. The use of small networks, with nodes consisting of solenoid valves acting as switchers and controlled via straightforward software, has dramatically expanded the analytical potential of continuousow analysis, which has been enormously boosted by FIA methodology in recent years. Multicommutation provides some valuable advantages, including the following: (a) Miniaturization of ow assemblies. The small size of solenoid valves and electronic interfaces permits the development of compact, integrated systems and of portable equipment for on-site analyses. (b) Reduced sample and reagent consumption. Simple multicommutation congurations (see Section 4.2.) allow the sample and reagents to be micro-dispensed very precisely; volumes of a few microlitres, which correspond to insertion times of fractions of a second, can thus be inserted very precisely. (c) Increased reproducibility. Solenoid valves require minimal operator intervention.

Fig. 2. Time-controlled insertion proles using solenoid valves.

trends in analytical chemistry, vol. 21, no. 5, 2002

369

The insertion process (namely, the ON OFF cycles in each valve of the ow assembly) can be controlled via computer software. In this way, multicommutation facilitates the development of fully automatic analytical methods. (d ) Economy and simplicity. Because solenoid valves can be switched on and off by a simple electrical pulse (usually 12 V and 100 mA), no additional power supply is needed; a card inserted into the computers motherboard governs the whole system. Finally, their operation can be controlled via user-friendly, exible software developed in common programming languages, such as QuickBasic or TurboPascal. (e) Flexibility. Multicommutation allows reactor lengths, inserted sample volumes, and ultimately any variable inuencing dispersion proles, to be changed readily without the need physically to alter assemblies. Changes can be made simply by resetting the duration of the electrical pulses that switch the valves on and off, or by altering their commutation sequence. ( f ) Expanded possibilities for ow analysis. The electronic control of dispersion, which results in more efcient spatial and temporal control of dispersion than in FIA, and the increased exibility of multicommutation have enabled the reliable implementation of gradient modes (stopped ow, merging zones, zone penetration, zone sampling), automated methods for multi-parameter determinations, and complex multichannel systems that can be operated in a simple, effective manner. However, multicommutation is subject to the following shortcomings: (a) Restrictions in inserted volumes. With very small sample segments and reagent segments, the operation of the propulsion system must be synchronized with the micro-insertions; otherwise, pump pulses

introduce irreproducible distortions in the dispersion proles. (b) The need to aspirate the sample and reagents. Because three-way valves act as switches, one of their two inow or outow positions must invariably be OFF, and circulation through the corresponding channel halted. This requires placing the propulsion unit behind the valves (although not always) and aspirating, rather than pumping, the sample and reagents (see Section 5). (c) Limited commercial availability. The scarcity of commercially available equipment (mainly electronic interfaces and software) for controlling solenoid valves is reected in the fact that virtually all the reported applications of multicommutation use laboratory-made hardware and software.

4. FIA modes and multicommutation

The exibility of multicommutation has resulted in increased simplicity and efciency in controlling sample and reagent dispersion relative to other ow methods. In this respect, it is of interest to consider some basic multicommutation congurations.

4.1. Insertion of discrete solution volumes and mimicking insertion in FIA

The exibility of multicommutation arises in part from the fact that it enables the faithful reproduction of the injection mechanism of the six-port rotary valve typically used in FIA (Fig. 3). In the loading position, the carrier solution and the sample are circulated through different channels; the sample volume to be injected is that contained in the length, L, of the sample loop connecting valves, V2 and V3. The loop can be lled by using a second propulsion unit (for example, a solenoid pump actuated automatically during the loading process to provide an intermittent, pulsating ow). During sample insertion, simultaneous switching of the

370

trends in analytical chemistry, vol. 21, no. 5, 2002

Fig. 3. Multicommutation reproducing the insertion of ow injection analysis (FIA): W=waste; Vn=solenoid valve; P=peristaltic or solenoid pump; S=sample; D=detector; C=carrier; T=connector; L=reactor.

three solenoid valves allows the carrier solution to sweep the sample to the detector.

4.2. Multiparameter determinations based on efcient discrimination of the sample in the carrier or carrier-reagent stream
If, as with basic circuits in electronics, a basic or standard conguration were to exist for multicommutation, it would be a serial or parallel array of solenoid valves acting as sample and reagent micro-dispensers. The procedure by which aliquots of sample and reagents are

sequentially inserted into the sole channel where chemical reactions are effected in the system the channel being connected to the propulsion (aspiration) unit is referred to as binary sampling. Fig. 4 shows the assemblies involved and a typical insertion prole. In both systems, valve V1 is intended to aspirate samples and standards, ush the system, and remove any bubbles formed in switching between different solutions. In the serial arrangement, once the system has been lled with sample solution, each reagent is inserted consecutively. Reactors L1L3 provide spatial

Fig. 4. Basic manifolds in multicommutation: C=carrier; S=sample; Rn=reagent; L=Reactor; W=waste; P=pump.

trends in analytical chemistry, vol. 21, no. 5, 2002

371

discrimination of the different samplereagent sandwiches. In the parallel arrangement, one of the inlets of valves V2V5 is shut, so the reagents must be inserted at intervals, using segments of the carrier solution in between. The insertion sequence must be programmed in such a way as to ensure that each solution in the system will circulate under constant conditions, unaffected by the other valves in the circuit. The congurations described above immediately provide apparent advantages, as follows. Sample and reagent consumption are minimal, and the ability to control dispersion individually in each dispensed solution permits the determination of different parameters in the same sample, with no overlap between peaks (in theory, one peak per inserted reagent). In an FIA assembly, one would have to use a very long reactor to avoid overlap of dispersion proles in order to discriminate between peaks.

sample and titrant volumes at any time during the process. This is so, provided the volume is proportional to the Fig. 5 insertion time, which can be controlled very precisely and altered at will over a wide range via software for programming the insertion sequence and time. The simplest way of achieving these goals is by using binary sampling (see Section 4.2.), where the sample and titrant solutions are dispensed in variable proportions. Fig. 5 illustrates a typical insertion sequence for a multicommutated titration. In an FIA assembly, this entails using very long or wide coils or mixing chambers capable of providing a high dispersion. Thus, reaching the end-point and completing the titration takes a long time, as a result of the high dispersion on which the method relies. Also, determining the analyte concentration occasionally entails the processing of non-linear curves.

4.3. Optimization of concentration proles: ow titrations

One of the most important features of multicommutation is the high efciency with which solution proles or concentration gradients can be established. This facilitates on-line dilution by up to several orders of magnitude, without the need to use mixing chambers or long coils. The effect can be accomplished by changing the insertion proles and sequence via software to simulate an alteration in the inserted volumes and reactor lengths. One excellent example of dispersion control and the generation of a la carte gradients over a wide concentration range is provided by pseudo ow titrations. Multicommutation allows accurate knowledge of the

4.4. Mimicking SIA

One other example of the high potential of multicommutation with solenoid valves is the ability to mimic other, more recent, ow techniques intended to improve the performance of unsegmented ow analysis. Such is the case with SIA, which uses a switching valve instead of the typical injection valve. In this method, accurately measured volumes of carrier, sample, and reagents are aspirated by means of a pump that allows periodic alteration of the ow direction. As a result, inserted solutions lie next to one another in the coil. A similar insertion prole, and the ability to reverse the ow direction when the sample and reagent reach the detector ow-cell, can be Fig. 6 accomplished by using

Fig. 5. Insertion sequence for a multicommutation titration.

372

trends in analytical chemistry, vol. 21, no. 5, 2002

Fig. 6. Multicommutation reproducing the sequential injection analysis (SIA) approach: C=carrier; S=sample; Rn=reagent; L=Reactor; W=waste; P=pump; D=detector; Vn=solenoid valve.

several solenoid valves, arranged as shown in Fig. 6. The insertion of adjacent segments can be achieved by using the binary sampling approach at some point in the assembly; once the mixture reaches the detector, the ow can be reversed by repeating the sequence depicted in Fig. 6 as many times as required, without the need to manipulate the propulsion unit.

5. Analytical applications
The analytical uses of multicommutation are summarized in two tables below. Table 1 gives the results obtained in quantitative determinations of analytes. Table 1 is divided into sectors showing groups of analytes of a similar nature, and the analytical features of the determination procedure used with each. Not all applications involved the determination of a single analyte; thus, Rocks [6] developed an assembly for quantifying several species in clinical samples using a multi-analyser to subject samples to a series of tests. The exibility of multicommutation allows the use of ow networks provided with a relatively high number of solenoid valves. This has simplied the multi-parameter determination with a single sample insertion; nitrite, nitrate and ammonium can be determined spectrophotometrically using an eight-solenoid valve manifold [7]. More than half the work dealing with multicommutation employs ow networks, such as that depicted in Fig. 4, although sometimes with slight changes.

Plant materials and water have received most attention, with between 20% and 30%, respectively, of the published papers. Most of the work dealing with plant materials is by the research group active at Piracicaba, Brazil. Multicommutation allows the use of all kinds of optical and electrochemical detectors. More than half the work involves the use of UV-visible spectroscopy. Also remarkable is the large proportion (about 20%) of work that employs atomic absorption detection. Although aspiration is more popular than propulsion, the problem caused by placing the pump prior to the network of valves can be circumvented by connecting several solenoid valves, acting in some cases as a by-pass, and even by pumping the solution to a reservoir from which it is aspirated. These strategies have been employed in cases where the type of detector makes impossible the use of the aspirating mode (for example, AAS, ICP-MS, ICP-AES) [810]. From the data in Table 1, it follows that reproducibility, sensitivity, limit of detection, and selectivity are (obviously) similar to those of FIA. These features depend more markedly on the type of detector and chemistry used than on the type of assembly employed to handle samples and reagents. However, the reproducibility is more sensitive to differences in handling procedures. In any case, multicommutation methods are as reliable as their FIA counterparts. Table 2 shows the gures of merit of spectrophotometric and potentiometric multicommutated titrations. The assemblies for the implementation of titrations in this technique are not always ow networks of the same type as those used in determination of analytes; in

trends in analytical chemistry, vol. 21, no. 5, 2002

Table 1 Analytical determinations in the multicommutation methodology Analyte Sample matrix Detector Linear range (LOD) RSD,% Sample throughput, Number of Ref. three-way h1 /Sample solenoid volume, ml valves 5 [16]

1. Metallic ions Ag/Cd/Hg/Pb/Tl

As

Dogsh muscle; bovine liver; corn bran; rice our Beer; tomato; mussel; liver paste

ET ICP MS

From 0.15 to 41 ng/g, for different samples and preparation procedures 10 x detection limit to 100 ppm (beer, 0.5 ng/g; tomato, 2 ng/g; mussel, 50 ng/g; liver, 5 ng/g) t=20s up to 60ppb; t=5s up to 350ppb; t=1s > 300ppb (t=80s 0.50.2 ppb) 15 ppb (Bi, 0.25 ppb/Pb, 0.21 ppb) 0.251000 ppm (7 ppb) Beer 8; Tomato 11; mussel 9; liver 4 2.2 (n=8)

ICP AES

[17]

As(III)/As(V)

Potable water

PSVI

[18]

Bi(III)/Pb(II) Ca

Ca/K Ca/Mn/Zn Cd/Pb/Ni

Steel; Al foil Water; plant materials; milk; pharmaceutical formulations; fertilizer; rocks Plant materials Plant materials Water (bottled, mineral, tap, sea)

ET AAS S (575 nm)

419 0.83 (n=10)

/20 4268/10500

Bi 6; Pb 7 56

[8] [19]

AAS/AES ICP AES ET AAS

Ca, 0100 ppm; K, 010 ppm (Cd, 2.2 ng/l; Pb, 23 ng/l; Pb, 75 ng/l)

1 (100 ppm) Cd < 5; Pb < 4; Ni < 6 (n=10) 2.63.1 (n=10)

Ca 50; K 70 30/3000

Ca 5; K 4 4

[9] [20] [10]

Co Cr(VI)/NH+ 4 Cu Cu

Blood Water Plant materials; Foods Water

ET AAS S (Cr: 545 nm) AAS AAS ET ICP MS

Up to 50ppb (0.3 ppb) Cr(VI) 0.53 ppm (10 ppb); NH+ 4 0.315 ppm (7 ppb) (1 ppb) 265 ppb (1.5 ppb)
63

[21] [22]

Cu/Cd/Pb/Bi/Se(IV) Water

Cu-65Cu 0.0750.6 ppb (54 ng/l) Cd 0.0250.15 ppb (0.2 ng/l) 208 Pb 0.01250.1 ppb (0.3 ng/l) 209 Bi 0.00250.02 ppb (0.06 ng/l) 77 Se(IV) 0.01250.4 ppb (5 ng/l)
111

3 (n=10, 21.75 ppb) 0.62.5 (n=14, 4.218.8 ppb) >10 (n=6)

48 8000 5

[23] [4] [24]

373

374

Table 1 (continued) Analyte Sample matrix Detector Linear range (LOD) RSD,% Sample throughput, Number of Ref. three-way h1 /Sample solenoid volume, ml valves 45/300 220 60 50 Ni 60; FeCr 130 5 4 6 4 Ni 4; FeCr 5 3 [25] [26] [27] [28] [29]

Cu/Zn Fe Fe/Al Mn2+ Ni/Fe/Cr 2. Inorganic anions Chlorine

Plant materials Plant materials Plant materials Plant materials Steel alloys

S(620 nm) S (480 nm) S (540 nm) S (548 nm)

Cu 01 ppm (0.05 ppm); Zn 02 ppm (0.04 ppm) 010 ppm Fe up to 12ppm (0.2 ppm); Al up to 15 ppm (0.5 ppm) 2.540 ppm (1.2 ppm)

S (Ni: 460 nm, Ni 550 ppm; Fe 25200 ppm; FeCr: 526 nm) Cr 2060 ppm S (445 nm) 30s preconcentration: 0.051.30 ppm (0.05 ppm); 120 s preconcentration: 0.020.43 ppm (0.43 ppm) Up to 10 000 ppm 102104 M Up to 10 ppm, b**= 10cm; Up to 25 ppm, b= 5cm; Up to 300 ppm, b= 1 cm Methylamines, up to 100 nM; NH3, up to 1000 nM N, 25125 ppm; P, 2.512.5 ppm

Cu 0.7; Zn 1.7 0.8 (n=10, 6.8 ppm) Fe 1.2; Al 1.8 (n=8) 0.27 (n=9, 17.1 ppm) 1

Bleach; tablets; water

Chloride Chloride I2

Parenteral solutions S (480 nm) Water; soft drink ISE Water; urine S (464 nm)

30s,1.5 (n=42, 0.72 ppm); 120s, 1.8 (n=33, 0.23 ppm) 1.8 (n=5) 2 (n=10)

30s,38; 120s, 20

[30]

5 2 (+15*) 3

[31] [32] [33]

NH3/methylamines
3 NH+ 4/PO4

Water; air Plant materials

C S (660 nm)

<8 80 NH+ 4, 2 (n=8, 73.1 ppm N); PO3 4 , 1.5 (n=8, 8.3 ppm P) 0.4 (n=15, 15/1400 6.4105 M NO 3) NO 2 , 0.32; NO 3 , 0.42; NH+ 4, 0.72 (n=20) 2 (n=11) 60 6

[34] [35]

trends in analytical chemistry, vol. 21, no. 5, 2002

NO 2 /NO3

+ NO 2 /NO3 /NH4

Lake and fountain water; fertilizers; sausage; soils River water

S (328 nm)

Phosphorus SO2 4

Water Plant materials

S (635 nm) T (410 nm)

4 NO or 0.85104 M 2 : 01.4510 (3.3107 or 1.9107 M); 4 NO M (3.3107 M) 3 : 01.4510 0.0251.0 ppm NO2 (5 ppb); 0.105.0 ppm NO 3 (15 ppb); 0.12.0 ppm NH+ 4 (25 ppb) Up to 2 ppm (0.05 ppm) Up to 500 ppm

[36]

[7]

100 / 54 (100500 ppm) 94 (0150 ppm)

2 5

[37] [38]

(continued)

trends in analytical chemistry, vol. 21, no. 5, 2002

Table 1 (continued) Analyte Sample matrix Detector Linear range (LOD) RSD,% Sample throughput, Number of Ref. three-way h1 /Sample solenoid volume, ml valves 13/460 5+3* [39]

Chemical Oxygen Demand 3. Organic compounds Amiloride.HCl Carbaryl Cephalexin Creatinine Ethanol Glucose Hypoxanthine Phenol

Water

Automated micro batch analyzer S (545 nm) S (596 nm) S(262 nm) S S (600 nm) S (510 nm) CH CH

(10ppm)

Pharmaceutical formulations Pharmaceutical formulations Urine Alcoholic beverages Sugar-cane juice; Soft drinks Sardine; Grunt Water

Up to 120 ppm (1 ppm) (26 ppb) Up to 1250 ppm (1.57 ppm)

2.2 (n=10) 0.5 (n=8, 5.8 ppm) 0.662.1 2.9 (n=10, 1.26 g/l) 1.6 (n=11, 42.1%) 0.3 (n=6, 0.1%)

30 70/50 180 24 40/18296 30

2+3** 5 2 3

[40] [41] [42] [43] [44]

1050 0.050.2% (w/v) 1 M-3mM (5 ppb)

4 3

[45] [46] [47]

Pindolol p-nitrophenol (1) / salicylic acid (2) / Ibuprofen (3)

Pharmaceutical formulations

S (635 nm) S (1), 399nm; (2), 237nm; (3), 296 nm

5120ppm (1), 0.11 mM; (2), 0.13 mM; (3), 0.13 mM

1.1 (n=10) 214

1260 (without preconcentration) 30

5 11*

[48] [49]

* Two-way solenoid valve ** Path-lengths of the ow cell. S: Spectrophotometer; PSVI: Portable Stripping Voltammetric Instrument; ET ICP MS: Electrothermal-vaporization inductively coupled plasma mass spectrometry; ET AAS: Electrothermal atomic absorption spectrometry; ICP AES: inductively coupled plasma atomic emission spectroscopy; C: Conductimetry; CH: Chemiluminescence; T: Turbidimetry; ISE: Ion-selective electrode

375

376

trends in analytical chemistry, vol. 21, no. 5, 2002

Table 2 Spectrophotometric and potentiometric titrations in a multicommutated ow network Analyte Sample matrix Detector/reactive RSD,% Sample throughput, h1/ volume, ml Number of three-way solenoid valves 5 25/600 P, 180/100 5 4* Ref.

HCl/HAc H+/OH Ca/ PO3 4

Vinegar; Coca Cola; lemon soda; Isotonic drink; orange juice Wines Natural water

ISE/NaOH S/NaOH-m-cresol indicator Ca, ISE/ ethylenebis (oxyethylenenitrilo) tetra-acetic acid P, S (650nm)/molybdenum blue method S (540 nm)/NaOHphenolphthalein S/NaOH S (548 nm)/NaOHphenolphthalein

1 (n=9) 0.7 (n=6) Ca, 0.5 (n=10, 1mM)

[50] [12] [11]

HCl HCl H+ Red and white vinegar

60/667 110 mM 1.22.1 (n=12)

[51] [10] [9]

fact, these insert the sample and reagent in proportions variable according to the time the valves remain ON. The procedure for determining calcium is illustrates this point: in the rst cycle, 70% of the ON interval is used to insert the reagent and 30% the sample: in the second cycle, both are inserted for identical periods: in the third cycle, the proportions of the rst cycle are inverted. By using a largeenough number of intervals, a ow gradient ranging from 100% reagent to 100% sample can be obtained [11]. The titration efciency is a function of the efciency of sample-reagent mixing in the resulting ow. In this respect, it should be noted that only one of the ve titrations reported in four specic papers [12] used a mixing-reaction chamber; the others used a piece of coil as reactor and several pumping points to examine the effect of altering the ow rate and its stability. A similar assembly was used to determine the acidity of vinegar [13]. In any case, a single pump sufces in practice, even when several channels are used. De Andrade, Poppy and Cascione [14] used a three-valve module to titrate HCl with NaOH in the monosegmented ow mode (that is, with a bubble behind the sample), using spectrophotometric detection.

6. Trends and conclusions

First of all, users should agree on a common designation for a methodology that has so far been referred to as a multicommutation ow system, multicommutation approach, binary sampling, ow networks, binary search, automated mono-segmented ow system, multi-insertion of small solution volumes, time-division multiplexed technique or even, simply, FIA. The abovementioned group at Piracicaba, Brazil, recently put forward the name Tandem Flow Analysis. Although this methodology should naturally expand by addressing new problems or improving on existing solutions with the use of novel, imaginative ow systems, there will also be an inevitable trend to transferring processes that have previously been tackled successfully with other continuous-ow methodologies. This will entail the replication (mechanization) and new validation of established FIA applications such as those involving: (a) the use of solid-phase reactors for preconcentration, separation, analyte derivatization, in situ preparation of unstable reagents, reagent purication and enzyme-catalysed reactions; (b) the pretreatment of solid samples (suspensions);

trends in analytical chemistry, vol. 21, no. 5, 2002

377

(c) heterogeneous (liquidgas) systems, the use of which is bound to expand in the future; and, (d) liquid-liquid extractions. Multicommutation introduces a new hydrodynamic concept and thus requires new theoretical studies concerning the phenomena of dispersion caused by the use of solenoid valves for inserting solutions, and the development of ow networks through which variable sequences of micro-insertions of sample and reagents are interacting. Multicommutation should lend itself readily to use in combination with any type of detector, with performance similar to FIA. Also, it may provide increased operational reproducibility with microsensors. Three-way solenoid valves have so far been virtually the sole types used, and peristaltic pumps have been the main propulsion units (piston and gas pressure pumps have also been used, but only occasionally). More sophisticated assemblies are bound to include alternative types of propulsion device. It should be noted that the new methodology is easier to automate. This is bound to promote the development of portable eld equipment for on-site analyses (for example, in hospitals), water supply monitoring, environmental analysis, industrial process control, and similar purposes. In summary, it is not too adventurous to state that the new methodology constitutes a rm step towards the development of more exible, readily automated systems for operation under ow conditions. As indicated by the group at Piracicaba, Brazil: Evolution of the commutation concept has lead to the proposal and development of different generations of ow analyzers. [15].

References
[1] J.R. Chippereld, P.J. Worsfold, Anal. Chim. Acta 181 (1986) 283. [2] A.F. Kapauan, M.C. Magno, Anal. Chem. 58 (1986) 509. [3] J.L. Burguera, M. Burguera, C. Rivas, M. de la Guardia, A. Salvador, Anal. Chim. Acta 234 (1990) 253. [4] J.L. Burguera, M. Burguera, P. Carrero, J. Marcano, C. Rivas, M.R. Brunetto, J. Autom. Chem. 17 (1995) 25.

[5] J.Y. Neira, N. Reyes, J.A. Nobrega, Lab. Rob. Autom. 12 (2000) 246. [6] B.F. Rocks, Anal. Proc. 26 (1989) 321. [7] F.R.P. Rocha, B.F. Reis, Anal. Chim. Acta 409 (2000) 227. [8] M.B.O. Giacomelli, E.M. Ganzarolli, A.J. Curtius, Spectrochim. Acta, Part B 55 (2000) 525. [9] M.F. Gine, A.P. Packer, T. Blanco, B.F. dos Reis, Anal. Chim. Acta 323 (1996) 47. [10] M.M. Silva, M.A.Z. Arruda, F.J. Krug, P.V. Oliveira, Z.F. Queiroz, M. Gallego, M. Valcarcel, Anal. Chim. Acta 368 (1998) 255. [11] Z.D. Wang, T.J. Cardwell, R.W. Cattrall, R.P. Dyson, G.E. Jenkins, Anal. Chim. Acta 368 (1998) 105. [12] R.S. Honorato, M.C.U. Araujo, R.A.C. Lima, E.A.G. Zagatto, R.A.S. Lapa, J.L.F. Costa-Lima, Anal. Chim. Acta 396 (1999) 91. [13] R.S. Honorato, M.C.U. Araujo, G. Veras, E.A.G. Zagatto, R.A.S. Lapa, J.L.F. Costa-Lima, Anal. Sci. 15 (1999) 665. [14] J.C. de Andrade, R.J. Poppi, A.R. Coscione, J. Autom. Chem. 18 (1996) 199. [15] E.A.G. Zagatto, B.F. Reis, C.C. Oliveira, R.P. Sartini, M.A.Z. Arruda, Anal. Chim. Acta 400 (1999) 249. [16] D. Pozebon, V.L. Dressler, A.J. Curtius, Talanta 51 (2000) 903. [17] M.L. Cervera, R. Montoro, J.E.S. Uria, A.M. Garc a, A.S. Medel, Atom. Spectrosc. 16 (1995) 139. [18] H. Huang, P.K. Dasgupta, Anal. Chim. Acta 380 (1999) 27. [19] F.R.P. Rocha, P.B. Martelli, R.M. Frizzarin, B.F. Reis, Anal. Chim. Acta 366 (1998) 45. [20] B. Freire dos Reis, M. Fernanda Gine, F. Jose Krug, H. Bergamin-Filho, J. Anal. At. Spectrom. 7 (1992) 865. [21] M. Burguera, J.L. Burguera, C. Rondon, C. Rivas, P. Carrero, M. Gallignani, M.R. Brunetto, J. Anal. Atom. Spectrom. 10 (1995) 343. [22] D.J.M. Lawes, C. Pasquini, J. Autom. Chem. 10 (1) (1988) 25. [23] C.E.S. Miranda, S. Olivares, B.F. Reis, F.M. Luzardo, J. Brazilian Chem. Soc. 11 (2000) 44. [24] D. Pozebon, V.L. Dressler, A.J. Curtius, J. Anal. Atom. Spectrom. 13 (1998) 363. [25] C.C. Oliveira, R.P. Sartini, B.F. Reis, E.A.G. Zagatto, Anal. Chim. Acta 332 (1996) 173. [26] B.F. Reis, M.F. Gine, E.A.G. Zagatto, J.L.F. Costa-Lima, R.A. Lapa, Anal. Chim. Acta 293 (1994) 129. [27] E.A.M. Kronka, B.F. Reis, Quim. Anal. 17 (1998) 15. [28] M. Smiderle, B.F. Reis, F.R.P. Rocha, Anal. Chim. Acta 386 (1999) 129. [29] P.B. Martelli, B.F. Reis, E.A.M. Kronka, F.H. Bergamin, M. Korn, E.A.G. Zagatto, J.L.F. Costa-Lima, A.N. Araujo, Anal. Chim. Acta 308 (1995) 397. [30] M. Catala Icardo, J.V. Grac a Mateo, J. Mart nez Calatayud, Analyst 126 (2001) 2089. [31] R.A.S. Lapa, J.L.F. Costa-Lima, B.F. Reis, J.L.M. Santos, Anal. Chim. Acta 377 (1998) 103. [32] H. Hara, N. Ishio, K. Takahashi, Anal. Chim. Acta 281 (1993) 45. [33] J.E. Atwater, R.R. Wheeler Jr., R.L. Sauer, J.R. Schultz, Instrum. Sci. Technol. 22 (1994) 217. [34] S.W. Gibb, J.W. Wood, R. Fauzi, C. Mantoura, J. Autom. Chem. 17 (1995) 205. [35] E.A.M. Kronka, B.F. Reis, M. Korn, H. Bergamin-Filho, Anal. Chim. Acta 334 (1996) 287.

378

trends in analytical chemistry, vol. 21, no. 5, 2002

[36] J. Mart nez Calatayud, J.V. Garc a Mateo, V. David, Analyst (Cambridge) 123 (1998) 429. [37] R.L. Benson, Y.B. Truong, I.D. McKelvie, B.T. Hart, G.W. Bryant, W.P. Hilkmann, Water Res. 30 (1996) 1965. [38] J.A. Vieira, B.F. Reis, E.A.M. Kronka, A.P.S. Paim, M.F. Gine, Anal. Chim. Acta 366 (1998) 251. [39] P.K. Dasgupta, K. Petersen, Anal. Chem. 62 (1990) 395. [40] R.A.S. Lapa, J.L.F. Costa-Lima, J.L.M. Santos, Anal. Chim. Acta 407 (2000) 225. [41] B.F. Reis, A.M. Rubio, M. de la Guardia, Anal. Chim. Acta 392 (1999) 265. [42] L.F. Gouveia, J.L.F. Costa-Lima, J.A.G. Morais, Anal. Chim. Acta 366 (1998) 271. [43] A.N. Araujo, J.L.F. Costa-Lima, B.F. Reis, E.A.G. Zagatto, Anal. Chim. Acta 310 (1995) 447. [44] A.L.D. Comitre, B.F. Reis, Lab. Rob. Autom. 12 (2000) 31. [45] E.A.M. Kronka, A.P.S. Paim, B.F. Reis, J.L.F. Costa-Lima, R.A. Lapa, Fresenius J. Anal. Chem. 364 (1999) 358. [46] K. Hayashi, T. Okugawa, Y. Kozuka, S. Sasaki, K. Ikebukuro, I. Karube, J. Food Sci. 61 (1996) 736. [47] J. Michalowski, P. Halaburda, A. Kojlo, Anal. Lett. 33 (2000) 1373. [48] R.A.S. Lapa, J.L.F. Costa-Lima, B.F. Reis, J.L.M. Santos, E.A.G. Zagatto, Anal. Chim. Acta 366 (1998) 209.

[49] E.E. Sideris, C.A. Georgiou, M.A. Koupparis, P.E. Macheras, Anal. Chim. Acta 289 (1994) 87. [50] P.B. Martelli, B.F. Reis, M. Korn, J.L.F. Costa-Lima, Anal. Chim. Acta 387 (1999) 165. [51] M. Korn, L.F.B.P. Gouveia, E. De Oliveira, B.F. Reis, Anal. Chim. Acta 313 (1995) 177.

J. Mart nez Calatayud is Professor of Analytical Chemistry at the University of Valencia (Spain). He is currently working on continuous-ow methodologies, basically in FIA and tandem-ow. His topics of interest are pharmaceutical and environmental samples, mainly surface waters and marine waters. J. V. Garc a Mateo is lecturer in analytical chemistry at the University Cardenal Herrera in Valencia, Spain. His research work also deals with ow methodologies and pharmaceutical and environmental samples. M. Catala Icardo is in the Department of Analytical Chemistry of the University of Valencia, where she has a postdoctoral position working on a European Proposal on the analytical control of drinking waters.