CN115047028A - Method for identifying wine year - Google Patents

Abstract

The invention provides a method for identifying wine years, and specifically finds that the alcohol molecules and the water molecules are dispersed respectively, causing the confusion of the alcohol molecules and the water molecules, and the entropy value is introduced for the first time to measure the difference between the alcohol molecules and the water molecules. degree of dispersion. With the longer storage time of liquor, the more hydrogen bonds are formed, the greater the dispersion of alcohol molecular groups and water molecular groups, and the higher the entropy value of the wine system. Therefore, the entropy value follows the laws of nature and cannot be faked and is the only way to identify the vintage of wine.

Description

A method for identifying the vintage of wine

technical field

The invention relates to the technical field of wine identification, in particular, to a method for identifying wine years.

Background technique

The storage time of liquor is an important parameter affecting consumer choice and market price. The complex changes in the composition of liquor during storage make liquor taste mellow and rich. Generally, the longer liquor is stored, the more expensive it is. Due to the various objective differences in the production process of Chinese liquor, and the variety of styles and characteristics, the Chinese liquor industry is faced with scientific and technological problems in the identification of vintage liquors. In addition, some baijiu brewers label baijiu with false vintage labels in order to obtain higher profits. Due to the similar taste of baijiu of different years, it is difficult for consumers to identify the fraudulent year of baijiu, which requires a reliable method to identify the real production year of Chinese baijiu.

However, none of the existing liquor vintage detection methods in the industry can accurately identify the aged liquor, nor can it avoid the production of fake liquor. For example: CN104165825B patent discloses that the increase of surface tension of liquor is proportional to the age. However, if a surfactant is added to the liquor, the surface tension of the liquor will definitely change, and this method cannot avoid fake wine; CN109884146B patent discloses the use of high-frequency impedance measurement, time 2-3min, and then simulates the impedance spectrum of each year of wine The equivalent circuit is derived and principal component analysis is used. However, if a small amount of polyols is added to the liquor in order to hang the glass and improve the sweetness of the liquor, the electrochemical impedance spectrum of the liquor will also change, so the shoddy liquor will also be mixed into the vintage liquor. CN111521722A patent discloses a method for determining the content of flavor characteristic components in Fuyu-flavor finished liquor by using gas chromatography internal standard method, and establishes a partial least squares regression equation model of bottle storage year and flavor component content in Fuyu-flavor finished liquor, and then It is used for the identification of the storage year of the fragrant-flavored finished liquor bottles. However, this method is even more unreliable, because the current open secret of the liquor industry is that all volatile components can be added to the wine, and various acid esters can be purchased everywhere. In addition, various spectra and mass spectrometry are used to detect relevant characteristic components in wine, which can be achieved by exogenous addition or artificial addition. This method not only provides a method for illegal traders to cheat, but also provides a hotbed for deceiving consumers of vintage wine. .

SUMMARY OF THE INVENTION

Based on the above-mentioned background technology, in order to overcome the deficiencies of the method for identifying the age of the existing liquor, the invention provides a method for identifying the age of the wine, which is a physical method based on different storage times of wine and different degrees of dispersion of alcohol molecules. .

Specifically, the method provided by the present invention uses the concept of "entropy" in physics as a criterion for identifying vintage wines. Entropy is a thermodynamic concept. But in the development of history, it has created a very rich connotation and entered the field of vision of many disciplines. In many popular science articles, it is mentioned that entropy is used to measure chaos (dispersion). Entropy is important because it summarizes the basic law of development of the universe: everything in the universe has a tendency to spontaneously become more chaotic, which means that entropy will continue to increase. This is the principle of increasing entropy. Wine also follows the natural law of "entropy" in the process of appearance.

Alcohol molecules and water molecules are the two main components in liquor. In the new wine just distilled, alcohol molecules and water molecules exist independently in the system. As time goes by, hydroxyl (-OH) in alcohol molecules and hydrogen in water molecules (-H), forming hydrogen bonds (Figure 1). The reason is that the alcohol molecular groups and the water molecular groups are dispersed separately, which causes the confusion of the alcohol molecules and the water molecules. The entropy value of the wine system increases. The longer the storage time, the more hydrogen bonds are formed. The greater the degree of dispersion, the higher the entropy value of the wine system. Therefore, the entropy value follows the laws of nature and cannot be faked and is the only way to identify the wine year.

Further, the measurement principle of the detection method of the present invention: when the wine evaporates, the more hydrogen bonds, the more heat required to destroy the hydrogen bonds when evaporating into a gas, so the entropy change dS according to the system change process can be defined as

dS=δQr/T (1)

Among them, the thermodynamic temperature of the total heat in the entropy change process; the boiling point temperature of the sample wine t _wine +273. For example, the boiling point of alcohol at room temperature is t=78.3℃, and the absolute temperature is: T=78.3+273=351.3;

δQr is the reversible heat of the process, and the endothermic process is usually expressed as:

δQr=CMΔT=CM(TT ₀ ) (2)

Among them, T is the thermodynamic temperature of wine or alcohol when it boils, T ₀ is the initial thermodynamic temperature of wine or alcohol;

Preferably, the specific heat capacity of absolute ethanol C=0.58J/(kg·°C), and the relative density of absolute ethanol d=0.78934kg/m ³ ;

Preferably, the specific heat capacity of the 46° wine C=0.92J/(kg·°C), and the relative density of the 46° wine d=0.93776kg/m ³ .

Preferably, the 46° wine is Dili 46° liquor, which is provided by Henan Yangshao Wine Co., Ltd.

Preferably, a 2000W (2kJ/s) still is used in this experiment (Figure 2), the vacuum pump is turned on, and the vacuum degree during distillation is 0.1KPa.

Draw according to formula (1) and (2): the entropy value calculation formula of the present invention is:

dS=δQr/T=[CMΔT]/T (3)

Among them, ΔT is TT ₀ , T is the thermodynamic temperature of wine or alcohol when it boils, and T ₀ is the initial thermodynamic temperature of wine or alcohol;

Therefore, the change of dS (entropy value) in this experiment mainly depends on the change of absolute temperature and the quality of wine body during the distillation process. Calculate with formula (3).

Among them, the formula for calculating the quality of wine body is:

M=dV (4)

The standard molar entropy formula is:

dS _scale = dS/Mn (5)

Among them, V is the volume of the wine body during distillation; d is the relative density of the wine; Mn is the relative molecular mass of ethanol, which is 46.

The advantage of the present invention is that it is found that the dispersion of alcohol molecular groups and water molecular groups causes confusion of alcohol molecules and water molecules, and the entropy value is introduced for the first time to measure the dispersion degree of alcohol molecular groups and water molecular groups. With the longer storage time of liquor, the more hydrogen bonds are formed, the greater the dispersion of alcohol molecular groups and water molecular groups, and the higher the entropy value of the wine system. Therefore, the entropy value follows the laws of nature and is the only way to identify the vintage of wine that cannot be faked.

Description of drawings

Figure 1 shows the formation of hydrogen bonds between alcohol molecules and water molecules;

Fig. 2 is wine distillation apparatus;

Figure 3 shows the scatter plot fitting analysis.

Detailed ways

The present invention will be further described in detail below with reference to specific embodiments, so that those skilled in the art can understand the present invention more clearly.

The following examples are only used to illustrate the present invention, but not to limit the scope of the present invention. Based on the specific embodiments of the present invention, all other embodiments obtained by those of ordinary skill in the art without creative work fall within the protection scope of the present invention.

In the embodiments of the present invention, unless otherwise specified, all raw material components are commercially available products well known to those skilled in the art; in the embodiments of the present invention, unless otherwise specified, the technical means used are those of ordinary skill in the art well-known conventional means.

Pre-experiment (No. 3 in Table 1)

In a 500 ml distillation flask, add 190 ml of anhydrous ethanol, commercially available analytical grade; assemble the instrument as shown in Figure 2, check the air tightness of the device, pass cooling water (bottom in and top out), open the distillation pot, the power is at the highest level, Observe and record and convert absolute initial temperature (297K) and wine boiling temperature (303K).

Calculated according to formula (3):

dS=δQr/T=[CMΔT]/T=

(0.58J/(kg·K)*0.000190m ³ *0.78934kg/m ³ *6K)/303K=1.72E-06J/K;

Standard molar entropy dS _scale =1.72E-06/46=3.74E-08J/mol·K;

Embodiment 1 (No. 6 in Table 1)

In a 500ml distillation flask, add 185ml of wine (provided by Henan Yangshao Wine Industry Co., Ltd.) stored at 46° for 1 year; assemble the instrument as shown in Figure 2, check the air tightness of the device, and pass cooling water (bottom in and top out), Turn on the still pot with the highest power, observe and record and convert the absolute initial temperature (293K) and the boiling temperature of the wine (298.8K).

Calculated according to formula (3):

dS=δQr/T=[CMΔT]/T=

(0.92J/(kg·K)*0.000185m ³ *0.93776kg/m ³ *6K)/298.8K=3.10E-06J/K;

Standard molar entropy dS _scale =3.10E-06/46=6.74E-08J/mol·K;

The results show that: the wine stored for one year, the water molecules and the alcohol molecules interact to form a certain hydrogen bond, the entropy value is 6.74E-08J/mol·K, and the entropy value is increased by 80% compared with the pre-experiment No. 3 pure alcohol.

Embodiment 2 (No. 9 in Table 1)

In a 500ml distillation flask, add 225ml of wine stored at 46° for 3 years (provided by Henan Yangshao Wine Co., Ltd.); assemble the instrument as shown in Figure 2, check the air tightness of the device, and pass cooling water (bottom in and top out), Turn on the still pot with the highest power, observe and record and convert the absolute initial temperature (299K) and the boiling temperature of the wine (305.5K).

Calculated according to formula (3):

dS=δQr/T=[CMΔT]/T=

(0.92J/(kg·K)*0.000225m ³ *0.93776kg/m ³ *6K)/305K＝3.82E-06J/K

Standard molar entropy dS _scale = 8.30E-08J/mol·K

The results show that: on the basis of 1 year of storage, if the wine is stored for 2 years, that is, 3 years of wine, the interaction between water molecules and alcohol molecules forms more hydrogen bonds, and the entropy value is 8.30E-08J/mol·K, The entropy value of Example 1 (No. 6 in Table 1) increased by 23%.

Example 3 (No. 12 in Table 1)

In a 500 ml distillation flask, add 125 ml of wine (provided by Henan Yangshao Wine Co., Ltd.) that has been stored at 46° for 5 years; assemble the instrument as shown in Figure 2, check the air tightness of the device, and pass cooling water (bottom in and top out), Turn on the still pot with the maximum power, observe and record and convert the absolute initial temperature (293K) and the boiling temperature of the wine (305K).

Calculated according to formula (3):

dS=δQr/T=[CMΔT]/T=

0.92J/(kg·K)*0.000125m ³ *0.93776kg/m ³ *12K)/305K＝4.24E-06J/K

Standard molar entropy dS _scale = 9.22E-08J/mol·K

The results show that: the wine stored for 5 years, the action of water molecules and alcohol molecules to form more hydrogen bonds, the entropy value is 9.22E-08J/mol·K, and the entropy value of Example 2 (No. 9 in Table 1) 11% increase.

Example 4 (No. 15 in Table 1)

In a 1000ml distillation flask, add 260ml of wine stored at 46° for 7 years (provided by Henan Yangshao Wine Co., Ltd.); assemble the instrument as shown in Figure 2, check the air tightness of the device, and pass cooling water (bottom in and top out), Turn on the still pot with the maximum power, observe and record and convert the absolute initial temperature (293K) and wine boiling temperature (299K).;

Calculated according to formula (3):

dS=δQr/T=[CMΔT]/T=

(0.92J/(kg·K)*0.000260m ³ *0.93776kg/m ³ *6K)/299K＝4.50E-06J/K

Standard molar entropy dS _scale =9.79E-08J/mol·K

The results show that: the wine stored for 7 years, the action of water molecules and alcohol molecules to form more hydrogen bonds, the entropy value is 9.79E-08J/mol·K, and the entropy value of Example 3 (No. 9 in Table 1) 6% increase.

Example 5 (No. 18 in Table 1)

In a 500ml distillation flask, add 110ml of 9-year-old wine (provided by Henan Yangshao Wine Co., Ltd.) at 46°; assemble the instrument as shown in Figure 2, check the air tightness of the device, and pass cooling water (bottom in and top out), Turn on the still pot with the maximum power, observe and record and convert the absolute initial temperature (290K) and the boiling temperature of the wine (305K).

Calculated according to formula (3):

dS ₁₅ =δQr/T=[CMΔT]/T=

0.92J/(kg·K)*0.000110m ³ *0.93776kg/m ³ *15K)/305K＝4.67E-06J/K

Standard molar entropy dS _scale =1.01E-07J/mol·K

The results show that: the wine stored for 9 years, the action of water molecules and alcohol molecules, forms a lot of hydrogen bonds, the entropy value is 1.01E-07J/mol·K, and the entropy value of Example 4 (No. 9 in Table 1) increases. 4%.

Above-mentioned pre-experiment and embodiment carry out three parallel detections respectively under the same conditions, and the detection results are as shown in Table 1:

Table 1. Relationship between sample year and entropy value

It can be seen from the above table that with the prolongation of the storage year of liquor, the entropy value in the vintage wine system presents an upward trend, and the total entropy value presents a phenomenon of increasing year by year. Through the scatter plot fitting analysis (Figure 3), we can see that there is a good linear relationship between the entropy value in the vintage wine system and the age of the wine, and the relationship between the two can be reflected by the following formula: y=4E-09x+7E-08( R ² =0.9202), where x is the year of the wine, and y is the entropy value in the wine system. Through the linear fitting relationship, the year of the wine to be tested can be directly deduced according to the entropy value of the wine to be tested. The total entropy value can be used for the identification of the storage age of vintage wine, and the identification method can accurately identify the wine body of other different years, and the method is simple to operate.

It must be pointed out here that the above examples are only limited to further elaboration and explanation of the technical solutions of the present invention, and are not intended to further limit the technical solutions of the present invention. The method of the present invention is only a preferred embodiment, not a It is used to limit the protection scope of the present invention. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present invention shall be included within the protection scope of the present invention.

Claims (6)

1. a method for identifying the vintage of wine, it is characterized in that, the entropy value of wine is proportional to its year, and entropy change dS can be defined as dS=δQr/T, wherein, T is the thermodynamic temperature of the total heat of entropy change process, δQr is the reversible heat of the process. 2. method as claimed in claim 1 is characterized in that, δQr is according to the law of thermodynamics: δQr=CMΔT=CM(TT ₀ ); Wherein T is the thermodynamic temperature when wine boils, and T ₀ wine initial thermodynamic temperature; C is The specific heat capacity of the wine, M is the quality of the wine. 3. method as claimed in claim 2, is characterized in that, described wine is geographical advantage 46 ° liquor. The method according to claim 2 or 3, wherein the wine has a specific heat capacity C=0.92J/(kg·°C) and a relative density d=0.93776kg/m ³ . 5. method as claimed in claim 4 is characterized in that, what is used in described method is the still pot of 2000W (2kJ/s), and vacuum degree is 0.1KPa during distillation. 6. The method of claim 5, wherein the method is also applicable to the age identification of other liquor products.

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