WO1989007266A1 - Assaying aluminium in drinking water - Google Patents
Assaying aluminium in drinking water Download PDFInfo
- Publication number
- WO1989007266A1 WO1989007266A1 PCT/GB1989/000077 GB8900077W WO8907266A1 WO 1989007266 A1 WO1989007266 A1 WO 1989007266A1 GB 8900077 W GB8900077 W GB 8900077W WO 8907266 A1 WO8907266 A1 WO 8907266A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- aluminium
- fluoride
- mixed liquid
- sample stream
- solution
- Prior art date
Links
- 239000004411 aluminium Substances 0.000 title claims abstract description 43
- 229910052782 aluminium Inorganic materials 0.000 title claims abstract description 43
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 title claims abstract description 41
- 239000003651 drinking water Substances 0.000 title description 3
- 235000020188 drinking water Nutrition 0.000 title description 3
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 claims abstract description 34
- 238000000034 method Methods 0.000 claims abstract description 24
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 23
- 239000007788 liquid Substances 0.000 claims description 33
- 239000000243 solution Substances 0.000 claims description 20
- 150000002500 ions Chemical class 0.000 claims description 18
- -1 fluoride ions Chemical class 0.000 claims description 16
- 239000012086 standard solution Substances 0.000 claims description 11
- 239000002253 acid Substances 0.000 claims description 5
- 239000008139 complexing agent Substances 0.000 claims description 5
- 159000000013 aluminium salts Chemical class 0.000 claims description 4
- 229910000329 aluminium sulfate Inorganic materials 0.000 claims description 4
- 230000015572 biosynthetic process Effects 0.000 claims description 3
- 230000000536 complexating effect Effects 0.000 claims description 3
- 238000005259 measurement Methods 0.000 claims description 3
- 238000011437 continuous method Methods 0.000 claims description 2
- 229910021645 metal ion Inorganic materials 0.000 claims description 2
- 239000012266 salt solution Substances 0.000 claims description 2
- 150000003839 salts Chemical class 0.000 claims description 2
- PUZPDOWCWNUUKD-UHFFFAOYSA-M sodium fluoride Chemical compound [F-].[Na+] PUZPDOWCWNUUKD-UHFFFAOYSA-M 0.000 abstract description 4
- 235000013024 sodium fluoride Nutrition 0.000 abstract description 2
- 239000011775 sodium fluoride Substances 0.000 abstract description 2
- VTLYFUHAOXGGBS-UHFFFAOYSA-N Fe3+ Chemical compound [Fe+3] VTLYFUHAOXGGBS-UHFFFAOYSA-N 0.000 description 4
- 229910001447 ferric ion Inorganic materials 0.000 description 4
- 239000003643 water by type Substances 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- 150000001450 anions Chemical class 0.000 description 3
- 230000002452 interceptive effect Effects 0.000 description 3
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 description 2
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 2
- 229940037003 alum Drugs 0.000 description 2
- JLDSOYXADOWAKB-UHFFFAOYSA-N aluminium nitrate Chemical compound [Al+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O JLDSOYXADOWAKB-UHFFFAOYSA-N 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 230000002572 peristaltic effect Effects 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 239000003929 acidic solution Substances 0.000 description 1
- 230000002547 anomalous effect Effects 0.000 description 1
- 229960005070 ascorbic acid Drugs 0.000 description 1
- 235000010323 ascorbic acid Nutrition 0.000 description 1
- 239000011668 ascorbic acid Substances 0.000 description 1
- 238000003556 assay Methods 0.000 description 1
- 239000000872 buffer Substances 0.000 description 1
- 230000009918 complex formation Effects 0.000 description 1
- 238000010668 complexation reaction Methods 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 230000035622 drinking Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000013536 elastomeric material Substances 0.000 description 1
- 238000011067 equilibration Methods 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 230000000737 periodic effect Effects 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 238000012163 sequencing technique Methods 0.000 description 1
- 239000007974 sodium acetate buffer Substances 0.000 description 1
- 238000011144 upstream manufacturing Methods 0.000 description 1
- 238000010792 warming Methods 0.000 description 1
Classifications
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N31/00—Investigating or analysing non-biological materials by the use of the chemical methods specified in the subgroup; Apparatus specially adapted for such methods
- G01N31/16—Investigating or analysing non-biological materials by the use of the chemical methods specified in the subgroup; Apparatus specially adapted for such methods using titration
- G01N31/166—Continuous titration of flowing liquids
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N33/00—Investigating or analysing materials by specific methods not covered by groups G01N1/00 - G01N31/00
- G01N33/18—Water
- G01N33/1813—Specific cations in water, e.g. heavy metals
Definitions
- This invention is concerned with the determination of trace quantities of aluminium in a water supply.
- This invention seeks to provide an improved method of and e ⁇ uipment for assaying the aluminium content in drink ⁇ ing water which w ' i11 reduce and at best solve the aforesaid problem.
- an automated continuous method of assaying the aluminium content of water comprises abstracting a sample stream from a stream of water, flowing an acid buffered standard active fluoride ion solution at a rate which is in constant proportion to the rate of flow of the sample stream, mixing the sample stream of water and the flowing solution to form a mixed liquid, imposing a standard temperature on the mixed liquid, allowing active fluoride ions to form a complex with aluminium in the mixed liquid, flowing the mixed liquid into contact with a calibrated fluoride ion selec ⁇ tive electrode and a reference electrode, sensing the potential difference between the said electrodes, and electron cally computing the aluminium content of the sample from the sensed potential difference.
- acid is a ded to an abstracted stream to bring the aluminium content into solution at a pH of around 2.0 following which the required sample stream is taken and mixed with the buffered fluoride ion solution.
- the preferred range of pHs employed in the process is 4.0 to 5.5 and the buffered standard solution is desirably chosen to maintain a narrow band of pH within 'that range.
- the band width is 4.5 to 5.0.
- the value of the numeral x in the generic formula given above is determined experimentally, and should be about 2.1 in line with the expected predominance of the species [A1(H_0).F ? ] at the preferred pH band, but in some waters containing an anion which competes with fluoride in complexing aluminium, the value of x will be less than 2. This result is, first of all, an indication of the presence or incursion of such an ion, which in itself may be useful. Should the concentration of the interfering anion be a constant feature of the water, the experimentally determined value of x wi 11 be a constant and may be used in the assay of aluminium. Otherwise the interfering anion can be complexed into an inactive form.
- the method of the invention requires a measurable residual active fluoride ion content in the mixed liquid following the formation of the aluminium complex and the linear response of the potential difference between the electrodes to the logarithm of the concentration of active fluoride ions is preserved when the residual concentration is greater than 0.2 milligrams per litre of such fluoride ions; below that concentration the linearity of the rela ⁇ tionship is lost and the potential difference sensed no longer gives accurate determinations of aluminium content.
- An active ion meter is the preferred instrument for sensing the potential difference appearing between the electrodes and translating the sensed value into a measure of the aluminium content of the sample.
- a microprocessor is desirably incorporated to facilitate calibration and calculation of measurement parameters. Where such a microprocessor is present it can be used to control the automatic sequencing of valves in automated equipment provided to operate the method, as will be more fully described hereafter.
- the standard ' temperature imposed on the mixed liquid is preferably above ambient temperature and is thus normal ⁇ ly achieved by warming the mixed liquid.
- the complex forms more rapidly a ⁇ the temperature rises and, at about 45°C, the period needed to achieve equilibration of the complex is of the order of one minute at the preferred pH band.
- the method of the invention preferably utilises periodic recal ibration of the ion selective electrode and it is convenient for this recal ibration to be carried out automatically.
- a stream of a standard solution of aluminium ions can be substituted for the sample stream in the method of the invention and the mixed liquid flow maintained across the electrodes until a steady potential difference is attained.
- the datum can then be logged in a suitable memory.
- Repeating the method with a second standard solution of different aluminium content identifies a second level of potential difference which can also be logged.
- Using logged data from two such measurements with known aluminium contents enables the slope of the linear relationship of the sensed potential difference to the logarithm of the concentration of active fluoride ions to be determined and the selective electrode is thereby recalibrated.
- [Al] is the concentration of aluminium in the sample stream
- V. is the volume of the sample stream
- V Target is the volume of the buffered fluoride ion solution
- x is the number of fluoride ions in the complex molecule
- ferric ion should be rendered inactive before the aluminium determination is carried out.
- Complexing agents are available which will combine with ferric ion whilst not interfering with aluminium, and one example would be ascorbic acid. Therefore buffered fluoride solutions which also contain a ferric complexing agent are useful in carrying out the method of this invention.
- the invention also extends to automated assaying equipment for carrying out the method, and in this aspect comprises an active ion meter, a reference electrode and a calibrated fluoride ion selective electrode electrically connected via the ion meter, a first conduit adapted to contain the sample stream, a second conduit adapted to conduct the buffered standard active fluoride solution, means to induce a constant rate of flow in each of the first and second conduits, a confluence of the first and second conduits adapted to allow the combination of the sample stream and fluoride ion solution to form a mixed liquid, means to impose a standard temperature on the mixed liquid, means to conduct the mixed liquid into contact with the said electrodes, and means to record the EMF generated between said electrodes as determined by the ion meter.
- the equipment preferably also com ⁇ prises two reservoirs adapted to contain, respectively, first and second standard solutions of an aluminium salt differing in salt concentration, valve means to control the flow of standard solution from each reservoir, a third conduit adapted to receive liquid from the valve means, a confluence of the third conduit with the second conduit, valve means to control the entry of the sample stream into the first conduit and an automatic sequencer adapted to open the valve means in sequence for predetermined periods in such a way that only one of the sample stream, the first and the second standard aluminium salt solutions may flow into the confluence with the second conduit at a time.
- the conduits used in the equipment are preferably of small bore tubing to encourage linear flow therein and to minimise back-mixing.
- the preferred means to induce a constant rate of flow in each of the first and second conduits is a peristaltic pump operating on both similarly sized conduits simultaneously. This requires that each conduit, at least over the length in contact with the pump, is made of an elastomeric material.
- the means to impose a standard temperature on the mixed liquid includes a digester coil and one or more reactor coils all maintained at the desired temperature.
- the said means warms the mixed liquid to 45°C for at least five minutes to ensure the equi ibration of complex formation and, to this end, it is convenient that the conduit for the mixed liquid should be a helix or other labyrinthine structure within a heated member (e.g. a heated fluid bath).
- Figure 1 is a schematic block diagram of one embodi ⁇ ment of equipment for carrying out the method
- FIG. 2 is a more detailed block diagram of a second embodiment of equipment according to the invention.
- a conduit 1 is a side branch on a pipe 2 through which water to be sampled is flowing in the direction of the arrow A.
- Reservoirs 3 and 4 respec ⁇ tively contain different standard solutions of aluminium nitrate S.. and S 2 (one may be devoid of aluminium and is then a zero standard solution) and are connected via valves 5 and 6 with the conduit 1.
- Valve 7 in conduit 1 controls the flow of the stream of sampled water.
- Reservoir 8 contains a standard sodium fluoride solution, say 5 mil ⁇ ligrams of fluoride ions per litre, buffered to a pH of between 4.5 and 5.0 with an acetic acid/sodium acetate buffer.
- Reservoir 8 is connected via conduit 9 with a confluence 10 where conduits 1 and 9 join.
- Conduits 1 and 9 pass collaterally through a peristaltic pump 11 upstream of the confluence 10 and as the conduits where they pass through the pump 11 are flexible tubes of identically sized bores, the effect of the pump 11 is to deliver equal volumes of liquids through the conduits 1 and 9 to the confluence 10.
- Downstream of the confluence 10 the mixed liquid is contained in the conduit 1, passing through a heated block 12, which imposes a temperature of 45°C on the mixed liquid, and into operative contact with a reference electrode 13 and a fluoride ion selective electrode 14, the electrodes 13 and 14 being electrically connected via an active ion meter 15.
- the active ion meter comprises a millivolt meter, and a microprocessor/random access memory circuit to cope, by known methods, with retaining the datum calibration voltages established experimentally and to carry out the calculation.
- the active ion meter 15 is electrically connected to a digital display 16 and a pen recorder 17 on both of which a direct reading of the concentration of aluminium in the sampled water is displayed.
- the active ion meter 15 can also house a sequencer 18 arranged to control, via connections 19, the scheduled sequential opening and closing of valves 5, 6 and 7 so that only one valve is open at any time.
- the equipment With the valve 7 open, the equipment is in its analy ⁇ tic mode and the sample stream is metered by the pump 11 into contact with a metered flow of the buffered standard fluoride solution.
- the mixed liquid thus formed passes through the heated block 12, attaining a temperature of 45°C and shortly thereafter (e.g. five minutes later) comes into operative contact with the electrodes 13 and 14.
- Changes in the logarithm of concentration of aluminium in the sampled water are directly related to electropositive changes in the EMF appearing between the electrodes 13 and 14 and such changes are translated electronicall into a direct read out on the recorder 17 of the aluminium con ⁇ centration in the sampled water.
- valve 7 In its calibration mode, valve 7 is closed and valve 5 is opened to allow the first standard aluminium solution S from reservoir 3 to enter the conduit 1 where within a short interval it displaces the residue of the sample stream. The remainder of the process remains unchanged with the exception that by the time a steady signal charac- teri ⁇ tic of the mixed calibrating liquid has been estab ⁇ lished, the correlation of a known aluminium content and the experimentally determined EMF are transferred as a datum to the electronic memory. Closing valve 5 and opening valve 6 allows the process to be repeated with the second standard aluminium solution S ? providing a second datum for transfer to the memory. These data determine the slope, k of the linear relationship set forth in equation 2 above. At the completion of the calibration procedure, valve 6 is closed and valve 7 opened so that the analytic mode is reintroduced.
- Figure 2 shows a modified form of equipment and, where appropriate the same reference numerals as have been used in Figure 1 are employed. The main features of difference between the Figure 1 and Figure 2 arrangements are:
- Reservoir 8 is divided into a tank 8A for acid and a tank 8B for buffer.
- the pump 11 is shown as two linked pumps 11A and 11B.
- a digester coil 20, a reactor coil 21 and a cell 22 are immersed in a common heated water bath 23.
- An interface output 24 (e.g. to RS 232) is provided on the meter 15.
Landscapes
- Life Sciences & Earth Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical & Material Sciences (AREA)
- Biochemistry (AREA)
- Physics & Mathematics (AREA)
- Analytical Chemistry (AREA)
- General Health & Medical Sciences (AREA)
- General Physics & Mathematics (AREA)
- Immunology (AREA)
- Pathology (AREA)
- Molecular Biology (AREA)
- Engineering & Computer Science (AREA)
- Food Science & Technology (AREA)
- Medicinal Chemistry (AREA)
- Investigating Or Analyzing Non-Biological Materials By The Use Of Chemical Means (AREA)
Abstract
Description
Claims
Priority Applications (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DK463389A DK463389A (en) | 1988-01-29 | 1989-09-20 | METHOD AND APPARATUS FOR ANALYSIS OF WATER ALUMINUM CONTENTS |
NO89893869A NO893869L (en) | 1988-01-29 | 1989-09-28 | ANALYSIS OF ALUMINUM IN DRINKING WATER. |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
GB888802069A GB8802069D0 (en) | 1988-01-29 | 1988-01-29 | Assaying aluminium in drinking water |
GB8802069 | 1988-01-29 |
Publications (1)
Publication Number | Publication Date |
---|---|
WO1989007266A1 true WO1989007266A1 (en) | 1989-08-10 |
Family
ID=10630775
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/GB1989/000077 WO1989007266A1 (en) | 1988-01-29 | 1989-01-27 | Assaying aluminium in drinking water |
Country Status (5)
Country | Link |
---|---|
EP (1) | EP0352319A1 (en) |
AU (1) | AU600194B2 (en) |
DK (1) | DK463389A (en) |
GB (1) | GB8802069D0 (en) |
WO (1) | WO1989007266A1 (en) |
Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE2505255A1 (en) * | 1975-01-23 | 1976-07-29 | Aligena Ag | Separation of complex-forming metal ions - by treating aqs. soln. with complex -forming agent |
GB1574225A (en) * | 1976-05-29 | 1980-09-03 | Hoechst Ag | Quantitative analysis of aluminium/carbon and aluminium/hydrogen bonds |
FR2524641A1 (en) * | 1982-04-01 | 1983-10-07 | Lyonnaise Eaux Eclairage | Appts. to prepare samples of water e.g. from treatment plant - by adsorption on column packing for subsequent elution and analysis |
-
1988
- 1988-01-29 GB GB888802069A patent/GB8802069D0/en active Pending
-
1989
- 1989-01-27 AU AU30418/89A patent/AU600194B2/en not_active Ceased
- 1989-01-27 WO PCT/GB1989/000077 patent/WO1989007266A1/en not_active Application Discontinuation
- 1989-01-27 EP EP19890902062 patent/EP0352319A1/en not_active Ceased
- 1989-09-20 DK DK463389A patent/DK463389A/en not_active Application Discontinuation
Patent Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE2505255A1 (en) * | 1975-01-23 | 1976-07-29 | Aligena Ag | Separation of complex-forming metal ions - by treating aqs. soln. with complex -forming agent |
GB1574225A (en) * | 1976-05-29 | 1980-09-03 | Hoechst Ag | Quantitative analysis of aluminium/carbon and aluminium/hydrogen bonds |
FR2524641A1 (en) * | 1982-04-01 | 1983-10-07 | Lyonnaise Eaux Eclairage | Appts. to prepare samples of water e.g. from treatment plant - by adsorption on column packing for subsequent elution and analysis |
Also Published As
Publication number | Publication date |
---|---|
GB8802069D0 (en) | 1988-02-24 |
DK463389D0 (en) | 1989-09-20 |
AU3041889A (en) | 1989-08-25 |
EP0352319A1 (en) | 1990-01-31 |
AU600194B2 (en) | 1990-08-02 |
DK463389A (en) | 1989-09-20 |
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