RU171400U1 - MULTI-TOUCH COMPLEX FOR EVALUATING THE FRESHNESS OF UNPASTERIZED BEER IN NON-LABORATORY CONDITIONS - Google Patents

Abstract

Usage: to control changes in the quality of unpasteurized beer during its shelf life in non-laboratory conditions. The essence of the utility model is that a multisensor complex for assessing the freshness of unpasteurized beer under off-laboratory conditions, including a PD sensor connected to the control unit, consisting of two cases, the first of which is filled with KCl solution, and the second has a membrane made of perfluorinated sulfation cation exchange polymer in potassium form, silver chloride reference electrode, glass electrode for pH control, combined redox electrode, carbonate selective, sulfide selective, nitrite t-selective, nitrate-selective electrodes, a case for the sample, the control unit consisting of an electronic high-resistance multi-channel potentiometer with access to a personal computer, the electrodes are fixed in the holder-cap in such a way that when the holder-cap is connected to the sample case, the device is simultaneously immersed of all electrodes in the test sample, as well as the presence of an eight-section storage housing that is joined to the holder lid, and each section of the storage housing is filled with a corresponding the sport of each sensor with a storage solution. Effect: providing the ability to control changes in the quality of unpasteurized beer in off-laboratory conditions in a relatively short time. 1 ill.

Description

The utility model relates to the field of potentiometric analysis methods and membrane technologies. It can be used to monitor changes in the quality of unpasteurized beer during its shelf life in non-laboratory conditions.

Z. Haddi, A. Amari [et al.] // Sensors and Actuators B: Chemical. - 2013. - V. 177. - P. 989-996; Instrumental measurement of beer taste attibutes using electronic tongue / A. Rudnitskaya, E. Polshin, D. Kirsanov [et al.] // Analytica Chimica Acta. - 2009. - V. 646. - P. 111-118] и распознавания различных сортов пива [Discrimination and sensory description of beers through data fusion / L. Vera,

J. Guascha [et al.] // Talanta. - 2011. - V. 87. - P. 136-142; WO1999013325, МПК G01N 33/14, G01N 33/02, G01N 27/48, G01N 27/416, G01N 33/00, опубл. 18.03.1999]. Ни один из известных способов не решает задачу оценки изменения качества пива в течение его срока годности.Known electrochemical multisensor complexes for assessing bitterness [US 20040191918, IPC G01N 33/15, G01N 33/00, publ. 09/30/04] and other tastes [Hybrid electronic tongue based on multisensor data fusion for discrimination of beers /

Z. Haddi, A. Amari [et al.] // Sensors and Actuators B: Chemical. - 2013 .-- V. 177. - P. 989-996; Instrumental measurement of beer taste attibutes using electronic tongue / A. Rudnitskaya, E. Polshin, D. Kirsanov [et al.] // Analytica Chimica Acta. - 2009. - V. 646. - P. 111-118] and recognition of different types of beer [Discrimination and sensory description of beers through data fusion / L. Vera,

J. Guascha [et al.] // Talanta. - 2011. - V. 87. - P. 136-142; WO1999013325, IPC G01N 33/14, G01N 33/02, G01N 27/48, G01N 27/416, G01N 33/00, publ. 03/18/1999]. None of the known methods solves the problem of assessing changes in the quality of beer during its shelf life.

The closest type of analytical signal and device is a potentiometric multisensor measuring complex for the analysis of therapeutic and prophylactic food salt mixtures [RU 107590, IPC G01N 27/28, G01N 33/02, publ. 08/20/2011], including a control unit, a high-resistance multichannel voltmeter, a silver chloride reference electrode, a potassium selective electrode, a sodium selective electrode, calcium (magnesium) -selective electrode and a cross-selective PD sensor, all electrodes and a PD sensor are connected through a multichannel voltmeter to the control unit, the PD sensor consists of two housings interconnected via an airtight seal and closed by sealed plugs, one of which has an internal silver chloride reference electrode, in the other ovlena sulfokationitovaya perfluorinated polymer tube or membrane, or rod so that one of their end housed in said first body, and the other extends beyond the second body. Tubes, membranes and rods are made of perforated sulfocationionite polymer in potassium form. The case in which the internal silver chloride reference electrode of the cross-sensitive PD sensor is installed is filled with a 0.1 M KCl solution. The electrodes and the PD sensor are mounted, for example, on a tripod. However, this complex will not allow analysis in off-laboratory conditions.

The utility model is a device for assessing the freshness of unpasteurized beer, designed to monitor changes in the quality of beer during bottling and determine compliance with the manufacturer's stated production time.

The technical result consists in the development of a device that allows you to control the quality change of unpasteurized beer in off-laboratory conditions in a relatively short time.

The advantages of the utility model are also the low complexity of the analysis and the reduction of error accumulation due to the simultaneous measurement of the responses of the PD sensor and electrodes.

The technical result is achieved by the fact that the multisensor complex for assessing the freshness of unpasteurized beer in off-laboratory conditions, including a PD sensor connected to the control unit, consisting of two cases, the first of which is filled with KCl solution, and the second has a membrane made of perforated sulfocation exchange polymer in potassium form , silver chloride reference electrode and selective electrodes, according to a utility model, further comprises a glass electrode for monitoring pH, combined redox tric electrode, carbonate-selective, sulfide-selective, nitrite-selective, nitrate-selective electrodes, a case for a sample for rapid measurements were used as selective electrodes, and the control unit consists of an electronic high-resistance multi-channel potentiometer with access to a personal computer.

The functioning of the utility model is based on the simultaneous measurement of the responses of the PD sensor and electrodes, the multiplicative change of which is determined by the change in the ion-molecular composition of beer due to redox transformations, vital processes of microorganisms and enzymatic reactions involving sulfur-containing and nitrogen-containing substances.

Figure 1 (a) shows a general diagram of an electrochemical cell for assessing the freshness of unpasteurized beer. In FIG. 1 (b) shows the cap holder for electrodes, in FIG. 1 (c) is a photograph of the rear panel of the potentiometer; FIG. 1 (g) shows the PD sensor, and in FIG. 1 (e) housing for storing electrodes.

The work is implemented as follows. The PD sensor 1 is prepared for operation as follows: the storage solution (0.1 M KCl) in the housing 2 of the PD sensor 1 is replaced by a comparison solution (1 M KCl); from the housing 3 of the PD sensor 1, in which the membrane 4 is fixed, the storage solution is removed; the housing 2 is connected to the housing 3. A glass electrode 5 for monitoring pH, a carbonate-selective electrode 6, a sulfide-selective electrode 7, a nitrite-selective electrode 8, a nitrate-selective electrode 9, a combined redoxmetric electrode 10, a silver chloride comparison electrode 11 are being prepared according to their passports. The PD sensor 1 and electrodes 5-11 are fixed in the lid-holder 12. A sample of beer with a volume of 25 cm ^{3 is} poured into the housing 13. The holder cover 12 with the PD sensor 1 and electrodes 5-11 fixed therein is connected to the housing 12, i.e. immersion of the PD sensor 1 and electrodes 5-11 in the beer sample under study is carried out simultaneously. The PD sensor 1 and the electrodes 5-10 are connected to the measuring inputs 14-20 of the high-resistance electronic multi-channel potentiometer 21. The electrode 11 is connected to the input 22 for the reference electrode. The responses of the PD sensor 1 and the electrodes 5-10 relative to the electrode 11 are measured simultaneously using an electronic high-resistance multi-channel potentiometer 21 and are automatically output to a personal computer. Between measurements, the PD sensor 1 and the electrodes 5-11, mounted in the lid-holder 12, are immersed in the housing 23, each section of which contains solutions for storing the PD sensor 1 (0.1 M KCl) and electrodes 5-11 (according to their passports )

The multi-sensor complex includes the following components: case 13 (d = 8.5 cm, h = 8 cm) for the beer sample under study, an eight-section case 23 for standard solutions for storing electrodes (the volume of the central section is 25 cm ³ , the rest for each section 54 cm ³ ), a cover-holder 12 with holes (d = 1.2 cm) for electrodes, a cross-sensitive PD sensor 1, the design of which is described in RF patent 2376591 [IPC G01N 27/28, publ. December 20, 2009], electrodes 5-11 and an electronic high-resistance multi-channel potentiometer 21 with access to a personal computer. The cases for beer 13 and solutions 23 and the lid-holder 12 for the electrodes are made of non-conductive opaque material. The responses of the PD sensor 1 and the electrodes 5-10 immersed in the case with the beer sample under study are measured simultaneously with respect to the silver chloride electrode 11, also immersed in the case 12 with the beer sample under study, using an electronic high-resistance multi-channel potentiometer 21. Processing multidimensional cross-sensitive responses The PD sensor 1 and ion-selective electrodes 6-9 are carried out by the method of analysis of variance taking into account the multiplicative change in responses.

EXAMPLE

Preliminarily, “training” of the cross-sensitive PD sensor and electrodes in samples of unpasteurized beer of a certain grade is performed under various conditions. The initial data were the average values of the responses of the PD sensor and electrodes obtained by duplicating the experiment 6-8 times in samples of Hans Weller dark beer under conditions of bottling and storage in a keg. In the first case, samples at room temperature (t ° + 20 ... + 25 ° C) were studied for 1, 12, and 24 hours after bottling from kegs. In the second case, samples for analysis were taken from one keg every 24 hours for 8 days after opening (the keg was kept closed in the refrigerator at t ° + 5 ... + 12 ° C in accordance with the storage conditions of unpasteurized beer).

The mathematical processing of the response values of the cross-sensitive PD sensor and electrodes obtained in various beer samples was carried out according to the following algorithm. In addition to changing the individual responses of the PD sensor and the electrodes, we considered their multiplicative change depending on the composition of the test sample. The pairwise products of the average responses of the PD sensor and electrodes were calculated. Then the variances were determined for the average response values and according to the law of error multiplication for their products. Next, responses were selected that were significantly different for the beer samples being compared by comparing their variances and average values according to the Fisher and Student criteria, respectively (analysis was carried out with a confidence probability of 0.95). To give an equal statistical weight to the responses, each average value and their products were normalized to their standard deviations. On the basis of the data obtained, a “beer freshness scale” is constructed with intervals of normalized response values corresponding to the bottling time from “less than 1 hour” to “more than 24 hours” with a step of 3 hours (for beer analysis under bottling conditions) or from “less than 1 day of storage beer in kegs ”until“ more than 14 days of storing beer in kegs ”in 1 day increments (for analysis of beer in storage conditions).

To assess the freshness of unpasteurized beer, the responses of the PD sensor and electrodes in the studied sample of unknown composition are measured. The pairwise products of the average responses of the PD sensor and electrodes are calculated. The response is normalized. The conclusion about the freshness of the sample is made by assigning the response values to one of the intervals on the “beer freshness scale” obtained by “training” the PD sensor and electrodes.

Claims (1)

A multisensor complex for assessing the freshness of unpasteurized beer under off-laboratory conditions, including a PD sensor connected to the control unit, consisting of two cases, the first of which is filled with KCl solution, and the second has a membrane made of perfluorinated sulfocation-cation exchange polymer in potassium form, silver chloride reference electrode, glass pH control electrode, combined redox electrode, carbonate-selective, sulfide-selective, nitrite-selective, nitrate-selective electrodes, housing for the sample, and the control unit consists of an electronic high-resistance multi-channel potentiometer with access to a personal computer, characterized in that the electrodes are fixed in the holder lid in such a way that when the holder lid is connected to the sample case, all electrodes are simultaneously immersed in the test sample , as well as the presence of an eight-section storage housing that is interfaced with a cover-holder, and each section of the storage housing is filled with the corresponding passport of each sensor creates storage.

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