CN115656269B - Method for detecting acid value of edible oil based on platinum electrode - Google Patents
Method for detecting acid value of edible oil based on platinum electrode Download PDFInfo
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Abstract
The application discloses a method for detecting the acid value of edible oil based on a platinum electrode, which comprises the following steps: the edible oil to be detected is injected into a rectangular sample tank, two pairs of orthogonally placed platinum electrodes are arranged in the sample tank, wherein one pair of platinum electrodes is two platinum plate electrodes oppositely arranged along the length direction of the sample tank, and the other pair of platinum electrodes is two platinum needle electrodes oppositely arranged along the width of the sample tank; then, at room temperature, an excitation voltage signal is applied between two platinum plate electrodes, meanwhile, a detection voltage signal between two platinum needle electrodes is collected, and then the edible oil acid value is calculated and obtained according to a relation between the absolute value delta theta of the difference value between the pre-established excitation voltage signal phase and the detection voltage signal phase and the edible oil Y. The application has the advantages of no need of using a large number of platinum electrodes and complex equipment, no need of using chemical reagents, simple and convenient operation in the detection process, high detection result precision, good accuracy, low cost, environmental protection and wide application prospect.
Description
Technical Field
The application relates to a method for detecting the quality of edible oil, in particular to a method for detecting the acid value of edible oil based on a platinum electrode, belonging to the field of sample detection.
Background
Edible oil is an indispensable food in life of people and has an important effect on human health. With prolonged preservation time, the edible oil is decomposed to generate free fatty acids due to the action of microorganisms, light and heat radiation. The acid value is an important index for evaluating the quality of the edible oil, reflects the degree of oxidative cleavage of the oil, and the content of free fatty acids in the oil is generally characterized in terms of acid value. The nutritive value of the edible oil is reduced along with the increase of the acid value, and long-term use of the edible oil with too high acid value can influence the health of human bodies and cause chronic diseases such as cardiovascular diseases, tumors and the like.
Currently, methods for detecting the acid value of edible oil mainly include chromatography, near infrared spectroscopy, potentiometric titration, voltammetry, chemical titration, and the like, for example, methods specified in GB 5009.229-2016. However, based on the convenience of operation and cost factors, the methods have the defects that a large amount of chemical reagents and medicines are needed by a chemical titration method, the pretreatment process is complex, and the on-site rapid detection is difficult to realize; the chromatographic method and the near infrared spectrum rule need standard substances as comparison, and are more suitable for the measurement of single fatty acid and components; the electrochemical detection methods such as potentiometric titration method and voltammetry method also need complicated pretreatment or auxiliary detection by adding a stabilizer, and the process is also complicated. For example, CN213302079U provides a method for electrochemically detecting the acid value of grease, which is implemented by using special screen printing electrodes, wherein the screen printing electrodes comprise 2 carbon working electrodes, 2 auxiliary electrodes and 2 Ag/AgCl reference electrodes which are printed on a substrate, that is, the whole process needs a large number of electrodes with different functions, the cost is high, and the quick, simple, accurate and low-cost detection requirement of edible oleic acid in the modern society is difficult to meet.
Disclosure of Invention
The application mainly aims to provide a method for detecting the acid value of edible oil based on a platinum electrode, so as to overcome the defects in the prior art.
In order to achieve the purpose of the application, the technical scheme adopted by the application comprises the following steps:
one aspect of the present application provides a method for detecting the acid value of edible oil based on a platinum electrode, comprising:
(1) Injecting edible oil to be detected into the rectangular sample groove;
(2) Two pairs of orthogonally placed platinum electrodes are arranged around the rectangular sample groove, wherein one pair of platinum electrodes is two platinum plate electrodes oppositely arranged along a first direction, the other pair of platinum electrodes is two platinum needle electrodes oppositely arranged along a second direction, and the first direction is perpendicular to the second direction;
(3) Applying an excitation voltage signal with the frequency of 10kHz between two platinum plate electrodes at the temperature of 15-25 ℃, collecting detection voltage signals between two platinum needle electrodes, calculating the absolute value delta theta of the difference value between the phase of the excitation voltage signal and the phase of the detection voltage signals, and calculating the acid value of edible oil to be detected according to the following formula (1);
y=0.05Δθ+c— (1)
Wherein C is 0.02-0.45. In some cases, 0.ltoreq.Δθ.ltoreq.180.
In one embodiment, the edible oil includes peanut oil, olive oil, sesame oil, corn oil, soybean oil, or the like, and is not limited thereto.
In one embodiment, the first direction is a length direction of the rectangular sample cell and the second direction is a width direction of the rectangular sample cell.
In one embodiment, the rectangular sample tank cavity has a length of 20-30mm, a width of 20-30mm, and a depth of 30-50mm.
In one embodiment, the rectangular sample groove is made of quartz glass, polytetrafluoroethylene (teflon), or the like, and is not limited thereto.
In one embodiment, the platinum plate electrode has a length of 5-10mm, a width of 5-10mm, and a thickness of 0.2-0.5mm.
In one embodiment, the platinum needle electrode has a length of 10-20mm and a diameter of 0.5-1mm.
Furthermore, the platinum plate electrode and the platinum needle electrode are at least partially immersed in the edible oil. The two platinum plate electrodes are respectively arranged near two ends of the rectangular sample groove in the length direction, and the two platinum needle electrodes are respectively arranged near two ends of the rectangular sample groove in the width direction.
In one embodiment, the excitation voltage signal is a sine wave.
In one embodiment, the level of the excitation voltage signal is 10-100mV peak-to-peak.
In one embodiment, the method specifically comprises the following steps: and (3) taking a series of edible oil standard samples with different acid values, and performing treatment through the operations of the steps (1) - (3), so as to construct a formula (1), wherein the detection range corresponding to the formula (1) is 0.02-9.45mg/g.
Another aspect of the present application provides an edible oil acid value detection apparatus, comprising:
the rectangular sample groove is used for accommodating edible oil to be detected;
two pairs of orthogonally placed platinum electrodes are arranged around the rectangular sample groove, wherein one pair of platinum electrodes is two platinum plate electrodes oppositely arranged along a first direction, the other pair of platinum electrodes is two platinum needle electrodes oppositely arranged along a second direction, and the first direction is perpendicular to the second direction;
the signal generator is connected with the two platinum plate electrodes and is used for applying an excitation voltage signal between the two platinum plate electrodes;
and the signal collector is connected with the two platinum needle electrodes and is used for collecting detection voltage signals between the two platinum needle electrodes.
In one embodiment, the first direction is the length direction of the rectangular sample groove, the second direction is the width direction of the rectangular sample groove, and the length of the inner cavity of the rectangular sample groove is 20-30mm, the width is 20-30mm, and the depth is 30-50mm.
Further, the distance between the two platinum plate electrodes is preferably 20-30mm, and the distance between the two platinum needles is preferably 20-30mm.
In one embodiment, the rectangular sample groove is formed of an insulating material such as quartz glass, polytetrafluoroethylene, or teflon, and is not limited thereto.
In one embodiment, the platinum plate electrode has a length of 5-10mm, a width of 5-10mm, and a thickness of 0.2-0.5mm.
In one embodiment, the platinum needle electrode has a length of 10-20mm and a diameter of 0.5-1mm.
In one embodiment, the excitation voltage signal is a sine wave and its level is 10-100mV peak-to-peak.
Compared with the prior art, the edible oil acid value detection method provided by the application has the advantages that only two pairs of platinum electrodes are needed to be matched with the conventional signal collector and the signal generator in implementation, complex equipment is not needed, any chemical reagent is not needed, the detection process is simple and convenient to operate, the detection result can be obtained within a few minutes, the detection precision is high, the accuracy is good, the cost is low, the environment is protected, and the application prospect is wide.
Drawings
FIG. 1 is a schematic diagram of a method for detecting the price of edible oleic acid according to the application;
FIG. 2 is a schematic diagram of a device for detecting the price of edible oleic acid used in the embodiments of the present application;
reference numerals illustrate: 101. a rectangular sample cell; 102. a platinum plate electrode; 103. a platinum needle electrode; 104. a signal collector; 105. a signal generator.
Detailed Description
As described above, in view of the shortcomings of the prior art, the present application provides a method for detecting the acid value of edible oil, and the principle thereof can be mainly shown in fig. 1. Specifically, peroxide and lower fatty acids (see a in FIG. 1) released by the fat system during rancidity, which are respectively negatively and positively charged, are subjected to the influence of an alternating electric field between the plates, and undergo oscillatory migration (see b in FIG. 1), and after a pair of platinum probes positioned at the right middle position of the electric field region are turned on, positively charged small fatty acid molecules near the platinum probes are rapidly accumulated around the probes and partiallyAdsorption takes place (see c in fig. 1), the solid (PI) -liquid layer (CH 3 [CH 2 ] n COOH, n values of about 2 to 24) has capacitive properties and a specific potential difference, resulting in a specific phase difference of the measurement signal and the generated signal. When the physical environment parameters of the excitation signal voltage, frequency, probe material, platinum plate electrode spacing, platinum needle electrode spacing and the like are fixed, the phase difference value proportion has a fixed numerical relation with the fatty acid content of the sample, namely the acid value.
The technical scheme, implementation process and principle thereof, etc. will be further explained below with reference to the accompanying drawings and specific embodiments, and unless otherwise specified, the raw materials, reagents, reaction equipment, etc. used in the embodiments of the present application are all commercially available, and the detection methods, etc. used are also known in the art.
The structure of the edible oil acid value detection device used in the following embodiment can be shown in fig. 2, and includes a rectangular sample tank 101, a platinum electrode, a signal collector 104 and a signal generator 105. Wherein the platinum electrodes are two pairs of orthogonally placed platinum electrodes and are distributed around the rectangular sample cell 101. Wherein, two platinum plate electrodes 102 are oppositely arranged along the length direction of the rectangular sample tank 101 and are electrically connected with a signal generator 105; two platinum needle electrodes 103 are arranged opposite to each other in the width direction of the rectangular sample cell 101, and are electrically connected to a signal collector 104. The signal collector 104 and the signal generator 105 may be voltage signal generating devices and voltage signal collecting devices commonly used in the art. When the detection device is used for detection, the platinum plate electrode and the platinum needle electrode are both partially immersed into edible oil contained in the rectangular sample groove 101, and the two platinum plate electrodes are respectively clung to the inner walls of the rectangular sample groove on two sides in the length direction, and the two platinum needle electrodes are respectively clung to the inner walls of the rectangular sample groove on two sides in the width direction.
Example 1
The method for detecting the acid value of the olive oil based on the platinum electrode comprises the following steps of:
(1) The olive oil to be detected is placed in a rectangular sample tank, the sample tank is made of Teflon, and the length, width and depth of an inner cavity of the sample tank are 25mm, 20mm and 35mm respectively.
(2) Two pairs of orthogonally placed platinum electrodes are arranged around the sample groove, wherein the length, width and thickness of one pair of platinum plate electrodes are respectively 6mm, 5mm and 0.3mm, and the length and diameter of one pair of platinum needle electrodes are respectively 15mm and 0.8mm.
(3) At 20 ℃, an excitation voltage sine wave signal with the frequency of 10kHz is applied between two platinum plate electrodes, the peak-peak voltage level is 10mV, meanwhile, a detection voltage signal between two platinum needle electrodes is collected, the absolute value delta theta of the difference value between the phase of the excitation voltage signal and the phase of the detection voltage signal is calculated, and then the acid value in the olive oil to be detected is obtained according to a predetermined relation Y=0.05delta theta+0.38 between the signal phase difference delta theta and the acid value Y of the olive oil.
Wherein the relation is established after a series of olive oil standard samples with different acid values are treated by the operations of the steps (1) - (3), and the corresponding detection range is 0.38-9.38mg/g.
The accuracy of the method of this example is fully demonstrated by the following Table 1, which shows the results of the detection of 10 olive oils sold by different manufacturers, using the method of this example and the method of GB 5009.229-2016 (referred to as the control method).
Table 1 results of the test of the acid value of commercially available olive oil by the method of example 1 and the method of the control group
Note that: the data in the above table are all the average values of the detection results obtained after the detection of a plurality of groups of samples.
In addition, the average detection time of the detection method of the embodiment is 5min, compared with 30min of the detection method of GB 5009.229-2016, which is far longer than the detection method of the embodiment.
Example 2
A method for detecting peanut oil acid value based on a platinum electrode comprises the following steps:
(1) Peanut oil to be detected is placed in a rectangular sample groove, the sample groove is made of quartz glass, and the length, width and depth of an inner cavity of the sample groove are 28mm, 22mm and 36mm respectively.
(2) Two pairs of orthogonally placed platinum electrodes are arranged around the sample groove, wherein the length, the width and the thickness of one pair of platinum plate electrodes are respectively 8mm, 6mm and 0.2mm, and the length and the diameter of one pair of platinum needle electrodes are respectively 18mm and 0.6mm.
(3) At 25 ℃, an excitation voltage sine wave signal with the frequency of 10kHz is applied between two platinum plate electrodes, the peak-peak voltage level is 100mV, meanwhile, a detection voltage signal between two platinum needle electrodes is collected, the absolute value delta theta of the difference value between the phase of the excitation voltage signal and the phase of the detection voltage signal is calculated, and then the acid value in peanut oil to be detected is obtained according to the relation Y=0.05delta theta+0.07 of the signal phase difference delta theta and the predetermined acid value Y of the peanut oil.
Wherein the relation is established after a series of peanut oil standard samples with different acid values are treated by the operations of the steps (1) - (3), and the corresponding detection range is 0.07-9.07mg/g.
The accuracy of the method of this example is fully demonstrated by the following Table 2, which shows the results of the detection of 10 peanut oils sold by different manufacturers using the methods of this example and GB 5009.229-2016 (abbreviated as control group method).
Table 2 results of the example 2 method and the control method for detecting acid value of commercial peanut oil
Note that: the data in the above table are all the average values of the detection results obtained after the detection of a plurality of groups of samples.
In addition, the average detection time of the detection method of the embodiment is 5min, compared with 30min of the detection method of GB 5009.229-2016, which is far longer than the detection method of the embodiment.
Example 3
The method for detecting the acid value of sesame oil based on the platinum electrode comprises the following steps of:
(1) Substantially the same as in step (1) of example 1, but the length, width and depth of the sample well cavity were 30mm, 25mm and 50mm, respectively.
(2) The procedure was substantially the same as in step (2) of example 1, but the length, width and thickness of the pair of platinum plate electrodes were 10mm, 5mm and 0.5mm, respectively, and the length and diameter of the pair of platinum needle electrodes were 10mm and 0.5mm, respectively.
(3) Substantially the same as in step (3) of example 1, but with an excitation voltage level peak-peak of about 60mV, the relation y=0.05Δθ+0.02 is employed, which corresponds to a detection range of 0.02-9.02mg/g.
After the detection method of the embodiment is adopted to detect various sesame oils on the market, the detection result is basically consistent with the detection result obtained by the GB 5009.229-2016 method.
Example 4
The method for detecting the acid value of the corn oil based on the platinum electrode comprises the following steps of:
(1) Substantially the same as in step (1) of example 1, but the length, width and depth of the sample cell cavity were 30mm, 20mm and 35mm, respectively.
(2) The procedure was substantially the same as in step (2) of example 1, but the length, width and thickness of the pair of platinum plate electrodes were 10mm, 10mm and 0.3mm, respectively, and the length and diameter of the pair of platinum needle electrodes were 20mm and 1mm, respectively.
(3) Substantially the same as in step (3) of example 1, but with an excitation voltage level peak-to-peak of about 60mV, the relationship y=0.05Δθ+0.45 is employed, which corresponds to a detection range of 0.45-9.45mg/g.
After the detection method of the embodiment is adopted to detect various corn oils on the market, the detection result is basically consistent with the detection result obtained by the method of GB 5009.229-2016.
In addition, the present inventors have also conducted detection of the acid value of various commercially available soybean oil, rapeseed oil, linseed oil, sunflower seed oil, etc. by referring to the methods of examples 1 and 2, and have obtained accurate detection results at a high speed and at a low cost.
It should be understood that the above embodiments are merely for illustrating the technical concept and features of the present application, and are intended to enable those skilled in the art to understand the present application and implement the same according to the present application without limiting the scope of the present application. All equivalent changes or modifications made in accordance with the spirit of the present application should be construed to be included in the scope of the present application.
Claims (7)
1. The method for detecting the acid value of the edible oil based on the platinum electrode is characterized by comprising the following steps of:
(1) Injecting edible oil to be detected into the rectangular sample groove, wherein the edible oil is selected from peanut oil, olive oil, sesame oil, corn oil or soybean oil;
(2) Two pairs of orthogonally placed platinum electrodes are arranged in a rectangular sample groove, wherein one pair of platinum electrodes is two platinum plate electrodes oppositely arranged along a first direction, the other pair of platinum electrodes is two platinum needle electrodes oppositely arranged along a second direction, the first direction is perpendicular to the second direction, and the rectangular sample groove is formed by insulating materials;
(3) Applying an excitation voltage signal between two platinum plate electrodes at 15-25deg.C, wherein the excitation voltage signal is sine wave, frequency is 10kHz, and level is peak-peak 10-100mV, simultaneously collecting detection voltage signal between two platinum needle electrodes, and calculating absolute value delta of difference between phase of the excitation voltage signal and phase of the detection voltage signalθThen calculating the acid value of the edible oil to be detected according to the following formula (1);
Y=0.05Δθ+C- - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - (1)
Wherein C is 0.02-0.45.
2. The method according to claim 1, characterized in that: the first direction is the length direction of the rectangular sample groove, and the second direction is the width direction of the rectangular sample groove.
3. The method according to claim 2, characterized in that: the length of the inner cavity of the rectangular sample groove is 20-30mm, the width is 20-30mm, and the depth is 30-50mm.
4. The method according to claim 1, characterized in that: the rectangular sample groove is made of quartz glass or Teflon.
5. The method according to claim 1, characterized in that: the length of the platinum plate electrode is 5-10mm, the width of the platinum plate electrode is 5-10mm, and the thickness of the platinum plate electrode is 0.2-0.5mm.
6. The method according to claim 1, characterized in that: the length of the platinum needle electrode is 10-20mm, and the diameter is 0.5-1mm.
7. The method according to claim 1, characterized in that it comprises in particular: and (3) taking a series of edible oil standard samples with different acid values, and performing treatment through the operations of the steps (1) - (3), so as to construct a formula (1), wherein the detection range corresponding to the formula (1) is 0.02-9.45mg/g.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101893595A (en) * | 2010-06-25 | 2010-11-24 | 中国农业大学 | Chemically modified electrode, preparation thereof and method for rapid determination of acid value of plant oil |
| CN109521077A (en) * | 2018-11-13 | 2019-03-26 | 国电南瑞科技股份有限公司 | A kind of two-wave interpretation formula online Analysis Apparatus of Permanganate Index titration end-point instruction device |
| WO2021237974A1 (en) * | 2020-05-26 | 2021-12-02 | 江苏大学 | Volt-ampere electronic tongue-based device and method for rapid testing of physical and chemical indicators of soybean sauce |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101893595A (en) * | 2010-06-25 | 2010-11-24 | 中国农业大学 | Chemically modified electrode, preparation thereof and method for rapid determination of acid value of plant oil |
| CN109521077A (en) * | 2018-11-13 | 2019-03-26 | 国电南瑞科技股份有限公司 | A kind of two-wave interpretation formula online Analysis Apparatus of Permanganate Index titration end-point instruction device |
| WO2021237974A1 (en) * | 2020-05-26 | 2021-12-02 | 江苏大学 | Volt-ampere electronic tongue-based device and method for rapid testing of physical and chemical indicators of soybean sauce |
Non-Patent Citations (1)
| Title |
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| 采用聚吡咯膜修饰电极检测植物油中亚油酸;张春娥 等;食品科技;第36卷(第02期);第273-279页 * |
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