The present invention relates to a method for determining at least one substance concentration or at least one substance in a liquid medium and also a device for this purpose according to the preamble of claim 10.
Spectroscopic analysis is a broad field, in which the composition and the properties of a substance in any phase—gas, liquid, solid—are determined by the electromagnetic spectra which result from the interaction (for example, absorption, luminescence, or emission) with energy.
One area of application, in particular known as absorption spectroscopy, comprises the measurement of optical absorption spectra of liquid substances. An absorption spectrum is the distribution of the light damping (by absorption) as a function of the light wavelength. The fundamental structure of a spectrophotometer is that the substance to be studied is provided in a transparent vessel—also referred to, for example, as a cuvette or sample cell. Electromagnetic beams (light) of a known wavelength A (for example, in the ultraviolet, infrared, visible, etc. range) and the intensity I are coupled into the vessel. A measuring unit or a detector, which measures the intensity of the exiting light, is arranged on the opposing side of the vessel. In this case, the length which the light covers in the sample is referred to as the path length or distance d.
In most spectrophotometers, standardized cuvettes are used, which have a path length of 1 cm and a capacity of 50 to 2000 μl.
For a sample which consists of a single homogeneous substance having a concentration c, the law of Lambert, Beer, and Bouguer applies to the light transmitted through the sample:
In this case, A is the extinction (or absorption), Φtr is the intensity after the transmission, Φ0 is the initial intensity, ε is the coefficient of extinction (which is generally constant at a predefined wavelength λ), c is the concentration, and d is the path length. For further specifications on the foundations of spectrophotometry and the terms and definitions used in this case, reference is made to the norm DIN 38404-3 (version of July 2005).
If multiple substances are contained in the sample, a total absorption Atot results as follows:
The laws briefly explained above also apply in particular in the monitoring of water quality, which is progressively performed repeatedly. As described in DIN 38404-3, the determination is performed at a wavelength λ=254 nm, possibly also additionally at λ=550 nm.
It has been shown in known devices that with so-called online monitoring, in which running and repeated determination of the water quality is performed using the same measuring instrument, as a result of soiling of the cuvette window, through which the electromagnetic waves are coupled in, a drift of the instrument zero point results, whereby measuring errors arise. The zero point can be redetermined at regular intervals by using a calibration liquid (for example, optically pure water according to DIN ISO 3696, 7.4) having known absorption for a measurement.
Another possibility for counteracting the problem of contamination is to use a so-called two-beam photometer, in which, in addition to the measuring channel, a reference channel, preferably having optically pure water, is used, wherein it is assumed that both channels are equally soiled and therefore the drift is equal. In this regard, reference is made to an article having the title “Drinking Water and Open Waters Application Sheet, V 2.0” (S::can Messtechnik GmbH, Vienna, page 5, chapter 4 under “Long-term stability”).
Finally, mechanical cleaning of the cuvette using a wiper or using compressed air has been proposed. In this regard, reference is also made to the above-mentioned article, specifically on page 5, chapter 3, under “Lower cross-sensitivity on turbidity, coloration, window deposit, etc.” and to the article having the title “UVAS plus sc—Die kontinuierliche Bestimmung der organischen Abwasserbelastung [the continuous determination of the organic wastewater load]” (page 2, chapter “Messprinzip [measuring principle]”, Hach Lange GmbH).
The known instruments have the disadvantage that the efficiency of the cleaning can be estimated only with difficulty or not at all, or a calibration results in interruptions in the monitoring. All known methods share the feature that they are relatively complex and thus costly to implement.
It is therefore the object of the present invention to specify a method which at least does not have one of the above-mentioned disadvantages.
The method claimed in claim 1 achieves the above-mentioned object. Further embodiment variants and a device are specified in further claims.
The present invention firstly relates to a method for determining at least one substance concentration or at least one substance in a liquid medium, wherein the method consists of the following steps,
By performing at least two intensity measurements at different fill levels of liquid medium in the vessel, a possible zero point drift, which can arise, for example, due to soiling of the vessel, has no influence on the accuracy of the obtained concentration. Cleaning of the vessel or calibration by means of a separate measuring channel or a measurement using optically pure water can be completely dispensed with. A much more robust and interference-resistant measuring instrument has thus been obtained.
One embodiment variant of the method according to the invention comprises the following further steps,
wherein ci is the i-th substance concentration, xi is the i-th fill level, Φi(xi) is a measured i-th intensity at a fill level xi, i is the index, which extends in integers from 1 to n, and ε is the coefficient of extinction, and wherein n has a value in the range of 1 to several hundred, preferably a value in the range of 10 to 100.
Further embodiment variants of the method according to the invention comprise the following further steps,
Further embodiment variants of the method according to the invention comprise the step that the substance concentration c is computed either by averaging from the n substance concentrations ci where i=0 . . . n or by means of linear regression, in particular by means of simple linear regression.
In further embodiment variants of the method according to the invention, the flow speed of the liquid medium is constant.
In further embodiment variants of the method according to the invention, the vessel is a cuvette, the longitudinal axis of which extend substantially vertically, and which has a constant cross-sectional area, wherein the electromagnetic waves are preferably coupled into the cuvette from below and the intensity is preferably measured above the cuvette.
Further embodiment variants of the method according to the invention comprise the following further steps,
Further embodiment variants of the method according to the invention comprise the step that the fill levels are ascertained via a time measurement.
Further embodiment variants of the method according to the invention comprise the step that the fill levels are ascertained via the absorption of a solvent, at a wavelength where only the solvent and not the dissolved substances absorb.
In further embodiment variants of the method according to the invention, the electromagnetic waves have a wavelength of 254 nm or 550 nm.
Furthermore, the invention relates to a device for determining a substance concentration and/or at least one substance in a liquid medium, wherein the device comprises:
One embodiment variant of the device according to the invention is distinguished in that,
wherein ci is the i-th substance concentration, xi is the i-th fill level, Φi(xi) is a measured i-th intensity at a fill level xi, i is the index, which extends in integers from 1 to n, and ε is the coefficient of extinction, and wherein n has a value in the range of 1 to several hundred, preferably a value in the range of 10 to 100.
Further embodiment variants of the device according to the invention are that,
Further embodiment variants of the device according to the invention are that the substance concentration c is computable in the computer unit either by averaging from the n substance concentrations ci where i=1 . . . n or by means of linear regression, in particular by means of simple linear regression.
Further embodiment variants of the device according to the invention are that a conveyor device is provided, which is operationally connected to the connecting channel, wherein the conveyor device preferably conveys liquid medium at constant flow speed into the vessel.
Further embodiment variants of the device according to the invention are that the conveyor device for filling and emptying the vessel comprises an automatically actuable switching valve.
Still further embodiment variants of the device according to the invention are that the vessel is a cuvette, the longitudinal axis of which extends essentially vertically, and which has a constant cross-sectional area, wherein the electromagnetic waves are preferably coupled from below into the cuvette and the intensity is preferably measured above the cuvette.
Further embodiment variants of the device according to the invention are that the vessel is arranged inverted in the sense of an immersion probe, wherein a fill level in the vessel is settable by means of air displacement.
Further embodiment variants of the device according to the invention are that electromagnetic waves having wavelengths of 254 nm and 550 nm can be generated using the source.
Further embodiment variants of the device according to the invention are that a viewing tube has a communicative connection to the vessel, via which at least the first fill level and the last fill level are determinable.
It is expressly noted that the above embodiment variants are combinable as desired. Only the combinations of embodiment variants which would result in a contradiction due to combination are excluded.
Exemplary embodiments of the present invention will be explained in greater detail hereafter on the basis of figures. In the figures:
A first embodiment variant of the device according to the invention is schematically illustrated in
The mentioned functions do not necessarily have to be implemented in one unit—the conveyor device 13 according to
The predetermined flow speed is generated, for example, using a metering pump (for example, in the form of a displacement pump, in particular a gearwheel pump) or using a vessel having constant sample level (constant head) and using a capillary as a sample drain into the cuvette.
A source 4 for generating electromagnetic waves 8 (light) is arranged below the vessel 1, for example, so that the electromagnetic waves 8 are coupled into the vessel 1 such that a path length covered by these electromagnetic waves is dependent on a fill level of liquid medium 3 in the vessel 1. Accordingly, the electromagnetic waves 8 run from below (as shown in
Lenses or lens systems 5 and 6 can be provided to bundle the electromagnetic waves 8 emitted by the source 4 and to concentrate the electromagnetic waves after the penetration of the liquid medium 3 contained in the vessel 1. The efficiency is thus increased by better light yield.
The source 4, the measuring unit 7, and the conveyor device 13 are operationally connected to a computer unit 16, whereby a control of the device according to the invention can be performed according to a sequence to be explained hereafter.
The vessel 1—as is apparent in
The electromagnetic waves 8 emitted by the source 4 have, for example, a wavelength λ of 254 nm or of 550 nm according to the above-mentioned norm DIN 38404-3 (July 2005). Depending on an absorption maximum, which is dependent on the ingredients to be detected, the wavelength can be selected arbitrarily. Accordingly, wavelengths other than the above-mentioned wavelengths are entirely conceivable.
In particular, it is also conceivable that—as indicated above—the electromagnetic waves 8 emitted by the source 4 cover a predefined spectrum, therefore a predefined wavelength range, and not only one or possibly two wavelengths, as is provided according to DIN 38404-3. At the same time, the measuring unit 7 has to be designed so that intensities can be ascertained and/or measured at multiple frequencies, therefore also in a predefined spectrum and/or wavelength range. The possibility is thus also provided of being able to determine the substances present and the proportions thereof in the liquid medium 3 in the meaning of the known method and/or device according to EP-0 600 334 B1. Corresponding to EP-0 600 334 B1, an array of measuring channels is provided, the results of which are processed accordingly in the computer unit 16.
In the embodiment variant shown in
Furthermore, a partially transmissive transmission unit 9 (for example, in the form of a partially transmissive mirror) is provided in the region of the source 4, which transmits the electromagnetic waves of the source 4 in the direction of the measuring unit 7, but also deflects the electromagnetic waves generated by a further source 11 in the direction of the measuring unit 7. Therefore, the sources 4 and 11 can generate electromagnetic waves having different wavelengths λ and can couple them simultaneously or offset in time into the liquid medium 3 in the vessel 1. Based on the requirement of norm DIN 38404-3 (version July 2015), for example, the source 4 can generate electromagnetic waves having a wavelength λ of 254 nm and the source 11 can generate electromagnetic waves having a wavelength λ of 550 nm. A compact instrument is therefore obtained, which enables a targeted measurement of the residual intensities at two different wavelengths λ.
As already in the case of the source 4, a lens or a lens system 10 is also connected downstream in the case of the further source 11, so that a maximum light yield can be achieved during a measuring procedure. Furthermore, the further source 11 is also operationally connected to the computer unit 16 for activation. This also applies to the light barriers LS1 and LS2, the detection signal of which is also supplied to the computer unit 16 for further processing.
Of course, it is also conceivable in this embodiment that the sources 4 and 11 can emit a predefined wavelength range as defined in EP-0 600 334 B1, to be able to ascertain the substances and/or substance concentrations provided in the liquid medium 3—again according to the teaching of EP-0 600334 B1.
The embodiment variant of the present invention shown in
Furthermore, the distance x between the two windows 21 and 22 can be ascertained using a read unit 23 via a scale applied to the lateral walls of the vessel 1 and the container 20, which are displaced in relation to one another depending on the distance x.
A further embodiment variant of the present invention is shown in
If the absorption measurements for a sample are completed, the vessel 1 is in turn emptied by pressing air—for example, from an existing compressed air system, which consists of a pressurized container—through the connecting channel 2 into the vessel 1, whereby the liquid medium 3 is displaced out of the vessel 1 via the opening 24. As soon as the vessel 1 has been completely or nearly completely emptied, a new measuring cycle can be started.
If the connecting channel 2 is arranged spaced apart from the measuring unit 7—as shown in
The method according to the invention will be explained hereafter on the basis of the flow chart illustrated in
In a step I, the conveyor device 13 (
In a step II, electromagnetic waves 8 having predefined wavelength λ are coupled into the liquid medium 3 contained in the vessel 1, wherein the electromagnetic waves 8 cover a path length in the liquid medium 3 which is dependent on a fill level xi of the liquid medium 3 in the vessel 1. The intensities of the received electromagnetic waves are measured using the measuring unit 7 (
The intensity measurement is repeated at at least one further point in time, i.e., with increased fill level in the vessel. In the flow chart according to
As soon as the measurements are completed (i.e., i=n), the substance concentration c is or substance concentrations ci are determined using the measured intensities ϕi and the at least two predefined fill levels xi in step III.
Therefore, in step IV, the vessel 1 can in turn be emptied and therefore made ready for a next concentration determination c. It is to be expressly noted that it is not necessary to wait after the last intensity measurement for step IV. In particular, it is not necessary to wait until the concentration determination according to step III is completed. Rather, the emptying of the vessel 1—and therefore step IV—can be begun immediately after the last intensity measurement under step II.
The measurement according to the invention of at least two intensities ϕi at at least two fill levels xi of the vessel 1 has the great advantage that a possible drift of the zero point as a result of soiling—for example, of the cuvette region, through which the electromagnetic waves are coupled into the liquid medium—has no influence on the measurement results and/or on the concentration c to be determined.
The substance concentration—with application of and by derivation of the known law of Lambert, Beer, and Bouguer—can be determined according to the following formula:
wherein ci is the i-th substance concentration, xi is the i-th fill level, Φi(xi) is a measured i-th intensity at a fill level xi, i is the index, which extends in integers from 1 to n, and ε is the coefficient of extinction, and wherein n has a value in the range of 1 to several hundred, preferably a value in the range of 10 to 100.
Accordingly, n intensities Φi are measured at n fill levels xi, wherein the n fill levels xi are preferably selected as equidistant.
The essential advantage in relation to known solutions manifests itself directly in the above formula: The intensity, which is responsible for the zero point, of the magnetic waves originating from the source 4 and coupled into the liquid medium 3 is eliminated by the differentiation according to the invention and/or by the derivation. For this reason, at least two measurements are necessary at different fill levels xi in the vessel.
The point in time ti and/or the fill level xi, at which an intensity Φi(xi) is measured can be produced in different ways: firstly, the option exists of initiating a first measurement by means of time measurement after completion of step IV and performing a further measurement or further measurements in each case after a further time span or after further time spans. Since if the flow speed is known during the filling of the vessel and the shape of the vessel is known, the fill level xi may also be readily determined. Fill level xi and point in time ti are directly related to one another under these conditions and if one variable is known, the other may be readily determined.
If n is selected as greater than 1, multiple values are obtained for the concentration c, namely n values for the concentration, so that an improved result is obtained for the concentration c, for example, by averaging or by means of linear regression, in particular by means of simple linear regression.
The above-explained method may also be determined in a similar manner for determining substances and/or substance proportions in the liquid medium 3. The embodiments in EP-0 600 334 B1 are applied accordingly.
Number | Date | Country | Kind |
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15182702.9 | Aug 2015 | EP | regional |
15191297.9 | Oct 2015 | EP | regional |
Filing Document | Filing Date | Country | Kind |
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PCT/EP2016/065900 | 7/6/2016 | WO | 00 |