KR102331950B1 - Apparatus and method for watar droplet-sensing in an organic solvent - Google Patents

Abstract

The present invention relates to an apparatus for detecting water droplets in an organic solvent, comprising: a reaction unit in which a solution containing water droplets, an electrolyte, and an organic solvent reacts; an electrode part located in the reaction part and including a reference electrode, a counter electrode, and a working electrode; and a measuring unit for measuring the intensity of current generated when the water droplet collides with or adsorbs on the surface of the working electrode of the electrode unit. By using the device for detecting water droplets in an organic solvent, the size, distribution of size, concentration, etc. of water droplets in an organic solvent, particularly, an organic solvent having hydrophobicity can be simultaneously detected. In particular, since water droplets in an organic solvent can be detected without redox species, a simpler detection device than the prior art can be proposed.

Description

Apparatus and method for detecting water droplets in organic solvents {APPARATUS AND METHOD FOR WATAR DROPLET-SENSING IN AN ORGANIC SOLVENT}

The present invention relates to an apparatus and method for detecting water in an organic solvent. Specifically, it relates to an apparatus and method for detecting the diameter, size distribution, or concentration of water droplets distributed or existing in an organic solvent by an electrochemical method.

Water is a typical contaminant in most organic solvents and is usually treated as a hindrance in chemical reactions and production processes where drying processes must be ensured. Especially in the case of the refining industry, water can induce metal corrosion, quench metal-based samples and cause catalyst deactivation. Therefore, it is very important to confirm the presence of water in the organic solvent and quantify its distribution. Water usually exhibits low solubility in organic solvents. Therefore, a very small amount of water (at ~ mM or less) is dissolved in the organic solvent and exists as a water molecule, but water above solubility is in the form of drops and is separated without mixing in the organic solvent and floats in the organic solvent. The size and number of these water droplets increases or decreases as the water content of the organic solvent increases.

In the case of the generally used Dynamic Light Scattering (DLS), the size distribution of water droplets in an organic solvent can be measured more accurately than the conventional laser scattering method. There is a disadvantage that the size of the droplet cannot be obtained. In addition, there is a problem in that the concentration of water in the organic solvent cannot be detected.

Recently, research on detecting water droplets distributed or existing in an organic solvent using an electrochemical method has been attempted. However, since a specific redox species is required, a detection method that does not use a redox species is required for a simpler detection method.

Patent Publication No. KR 10-2019-0074422

The present application is to solve the problems of the prior art described above, and relates to an apparatus for detecting water droplets in an organic solvent, comprising: a reaction unit in which a solution containing water droplets, an electrolyte and an organic solvent react; an electrode part located in the reaction part and including a reference electrode, a counter electrode, and a working electrode; and a measuring unit for measuring the intensity or collision frequency of a current generated when the water droplet collides or adsorbs on the surface of the working electrode of the electrode unit. By using the droplet detection device in the organic solvent, the droplet size, size distribution, or concentration of droplets distributed or present in an organic solvent, particularly, an organic solvent having hydrophobicity can be simultaneously detected. In particular, since water droplets in an organic solvent can be detected without redox species, a simpler detection device than the prior art can be presented.

Another object is to inject a solution containing water droplets, an electrolyte and an organic solvent into the reaction unit; providing an electrode unit including a reference electrode, a counter electrode, and a working electrode in the reaction unit; loading the working electrode with a voltage of 1.2 V to 1.6 V compared to the reference electrode; and measuring the intensity of the current or the collision frequency of the working electrode of the electrode part; to provide a method for detecting water in an organic solvent comprising a.

A water droplet detection apparatus in an organic solvent of the present invention for achieving the above technical problem includes a reaction unit in which a solution containing water droplets, an electrolyte, and an organic solvent reacts; an electrode part located in the reaction part and including a reference electrode, a counter electrode, and a working electrode; and a measuring unit for measuring the intensity or collision frequency of a current generated when the water droplet collides or adsorbs on the surface of the working electrode of the electrode unit.

It may further include a detection unit for detecting the diameter of the water drop in the reaction unit through a change in the intensity of the current measured by the measuring unit, but is not limited thereto.

The size distribution of the droplet may be obtained through the diameter of the droplet, but is not limited thereto.

It may be to obtain the concentration of the water droplet through the collision frequency, but is not limited thereto.

In order to measure the intensity of the current, the working electrode may be loaded with a voltage of 1.2 V to 1.6 V compared to the reference electrode, but is not limited thereto.

It may further include an output unit capable of displaying a change in the intensity of the current in the working electrode over time, but is not limited thereto.

The working electrode may include a material selected from the group consisting of carbon fiber, indium tin oxide, fluorine-doped tin oxide, boron-doped diamond, gold, silver, platinum, copper, nickel, and combinations thereof, but is limited thereto. it's not going to be

The electrolyte may _{include an electrolyte selected from the group consisting of MgSO 4} , CaSO ₄ , NaCl, KCl, HCl, KOH, NaOH, NaNO ₃ , KNO ₃ , H ₃ PO ₄ and combinations thereof, but is limited thereto. it's not going to be

The method for detecting water droplets in an organic solvent includes: injecting a solution containing water droplets, an electrolyte, and an organic solvent into a reaction unit; providing an electrode unit including a reference electrode, a counter electrode, and a working electrode in the reaction unit; loading the working electrode with a voltage of 1.2 V to 1.6 V compared to the reference electrode; and measuring the intensity of the current or the collision frequency of the working electrode of the electrode part.

It may be to detect the diameter of the water droplet through the change in the intensity of the current, but is not limited thereto.

The size distribution of the droplet may be obtained through the diameter of the droplet, but is not limited thereto.

The concentration of the water droplet may be obtained through the collision frequency, but is not limited thereto.

The above-described problem solving means are merely exemplary, and should not be construed as limiting the present application. In addition to the exemplary embodiments described above, additional embodiments may exist in the drawings and detailed description.

The disclosed technology may have the following effects. However, this does not mean that a specific embodiment should include all of the following effects or only the following effects, so the scope of the disclosed technology should not be construed as being limited thereby.

According to the problem solving means of the present application described above, by using the water droplet detection device in the organic solvent according to the present application, the size, distribution of size, concentration, etc. of water droplets distributed or existing in an organic solvent, particularly an organic solvent having hydrophobicity, can be simultaneously detected. can In particular, since water droplets in an organic solvent can be detected without redox species, a simpler detection device than the prior art can be proposed.

In addition, in the case of the dynamic light scattering method used in the prior art, since the distribution of the size of the water droplets is shown only on average, there is a disadvantage in that the diameter and exact size distribution of each water droplet distributed or present in the organic solvent cannot be detected. However, the diameter and accurate size distribution of each droplet (droplet) can be detected by using the droplet detection device in the organic solvent of the present application.

Furthermore, in the case of the dynamic light scattering method, the concentration cannot be measured, but the apparatus for detecting water droplets in an organic solvent according to the present application can measure the concentration of water droplets distributed or present in the organic solvent by using the collision frequency.

1 is a diagram of an apparatus for detecting water droplets in an organic solvent according to an embodiment of the present application.
2 is a view showing a change in current according to the oxidation of water droplets according to an embodiment of the present application.
3 is a graph of the collision frequency according to the concentration according to an embodiment of the present application.
4 is a flowchart of a method for detecting water droplets in an organic solvent according to an exemplary embodiment of the present application.
5A to 5E are graphs showing changes in current strength according to voltage in an electrochemical experiment according to an embodiment of the present application with time.
6A to 6D are graphs showing the current intensity according to the concentration of water droplets in an electrochemical experiment according to an embodiment of the present application.
7 is a graph showing the size distribution of water droplets in an electrochemical experiment according to an embodiment and a comparative example of the present application.
8 is a graph showing the size distribution of water droplets in an electrochemical experiment according to an embodiment and a comparative example of the present application.

Since the present invention can have various changes and can have various embodiments, specific embodiments are illustrated in the drawings and will be described in detail in the detailed description. However, this is not intended to limit the present invention to a specific embodiment, it should be understood to include all modifications, equivalents and substitutes included in the spirit and scope of the present invention.

In describing each figure, like reference numerals are used for like elements. The terms first, second, etc. may be used to describe various elements, but the elements should not be limited by the terms. The above terms are used only for the purpose of distinguishing one component from another.

For example, without departing from the scope of the present invention, a first component may be referred to as a second component, and similarly, a second component may also be referred to as a first component. The term “and/or” includes a combination of a plurality of related listed items or any of a plurality of related listed items.

Unless defined otherwise, all terms used herein, including technical or scientific terms, have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs.

Terms such as those defined in a commonly used dictionary should be interpreted as having a meaning consistent with the meaning in the context of the related art, and should not be interpreted in an ideal or excessively formal meaning unless explicitly defined in the present application. shouldn't

Throughout this specification, when it is said that a member is positioned "on", "on", "on", "under", "under", or "under" another member, this means that a member is positioned on the other member. It includes not only the case where they are in contact, but also the case where another member exists between two members.

Throughout this specification, when a part "includes" a certain component, it means that other components may be further included, rather than excluding other components, unless otherwise stated.

As used herein, the terms "about," "substantially," and the like are used in a sense at or close to the numerical value when the manufacturing and material tolerances inherent in the stated meaning are presented, and to aid in the understanding of the present application. It is used to prevent an unconscionable infringer from using the mentioned disclosure in an unreasonable manner. Also, throughout this specification, "step to" or "step to" does not mean "step for".

Throughout this specification, the term "combination of these" included in the expression of the Markush form means one or more mixtures or combinations selected from the group consisting of the components described in the expression of the Markush form, and the components It is meant to include one or more selected from the group consisting of.

Hereinafter, an apparatus and method for detecting water droplets in an organic solvent of the present application will be described in detail with reference to embodiments, examples, and drawings. However, the present application is not limited to these embodiments and examples and drawings.

Herein, a reaction unit in which a solution containing water droplets, an electrolyte and an organic solvent reacts; an electrode part located in the reaction part and including a reference electrode, a counter electrode, and a working electrode; And it relates to a water droplet detection device in an organic solvent comprising a; and a measuring unit for measuring the intensity or collision frequency of the current generated when the water droplet collides or adsorbs on the surface of the working electrode of the electrode unit.

By using the apparatus for detecting water droplets in an organic solvent according to the present application, the size, distribution, concentration, etc. of water droplets distributed or present in an organic solvent, particularly, an organic solvent having hydrophobicity can be simultaneously detected. In particular, since water droplets in an organic solvent can be detected without redox species, a simpler detection device than the prior art can be presented.

The water droplets in the organic solvent refer to water droplets separated in the form of water droplets without mixing with the organic solvent other than water dissolved in a molecular state in the organic solvent. That is, the present application relates to a detection device for measuring an aggregate of water present in the form of water droplets due to phase separation without mixing with the organic solvent.

Furthermore, the amount of water dissolved in a molecular state in the organic solvent may also be detected by measuring the background current using the detection device according to the present application.

1 is a diagram of an apparatus for detecting water droplets in an organic solvent according to an embodiment of the present application.

Specifically, the reaction unit 110 is a place where collision occurs between the working electrode 123 and the particles of water droplets distributed or existing in the organic solvent, and the water droplet, which is the detection target, is stored in the reaction unit 110 for a certain period of time. It may be to provide a space causing a collision with the working electrode 123, but is not limited thereto. The shape of the reaction unit 110 may be a cylinder, a plate, a cube, a cuboid, a regular polyhedron, a polygonal prism, or a sphere, but is not limited thereto.

The working electrode 123 refers to an electrode that directly participates in an electrode reaction to cause a reaction, and the working electrode 123 used in the present invention refers to an electrode that causes an oxidation reaction of the water droplet.

2 is a view showing a change in current according to the oxidation of water droplets according to an embodiment of the present application.

Specifically, the change in the intensity of the current appears due to electrons generated while the water droplets distributed or present in the organic solvent undergo an oxidation reaction on the working electrode 123 . That is, the size, size distribution, or concentration of water droplets can be detected by measuring the current strength and collision frequency that appear when water droplets distributed or present in the organic solvent directly oxidize on the surface of the working electrode. Therefore, since the direct oxidation reaction of water droplets is used, there is an advantage in that redox species are not required for the redox reaction.

The working electrode 123 may include a material selected from the group consisting of carbon fiber, indium tin oxide, fluorine-doped tin oxide, boron-doped diamond, gold, silver, platinum, copper, nickel, and combinations thereof. , but is not limited thereto.

The shape of the surface of the working electrode 123 may be polygonal, circular, elliptical, semi-circular, spherical, hemispherical, pyramidal, cylindrical, tetrahedral, hexahedral, recessed or irregular, such as triangle, square, pentagon, etc., but is limited thereto. it is not The shape of the surface of the working electrode 123 may be a circular shape. This is because the maximum distance from the center of the electrode to the edge of the circle is constant.

The working electrode 123 may be formed of an ultra-fine electrode, and the maximum diagonal length of the surface of the working electrode 123 may be 10 μm to 500 μm, but is not limited thereto.

The working electrode 123 may be one or two or more having different maximum diagonal lengths of the surface of the working electrode 123, and two or more working electrodes having different maximum diagonal lengths of the working electrode 123 ( 123), it is possible to simultaneously detect the size or concentration of water having different sizes.

The reference electrode 121 refers to an electrode capable of serving as a reference by having a constant unipolar potential when measuring an electric potential. The reference electrode may include a metal selected from the group consisting of Ag, Au, Pt, Cu, Al, and combinations thereof, but is not limited thereto.

The counter electrode 122 may refer to an electrode that causes an electrode reaction by being paired with the working electrode 123 or the reference electrode 121 . The counter electrode 122 may include a material selected from the group consisting of Pt, Au, IrO ₂ , Cu, Al, Ag, Ni, C, the reference electrode, and combinations thereof, but is limited thereto no.

The shape and size of the reference electrode 121 , the counter electrode 122 , and the working electrode 123 may be the same or different.

There is no limitation on positions at which the reference electrode 121 , the counter electrode 122 , and the working electrode 123 are mounted in the reaction unit 110 , but rather than being attached to the inner wall of the reaction unit 110 . It is preferable to be spaced apart. In addition, there is no limitation on the distance between the reference electrode 121 , the counter electrode 122 , and the working electrode 123 , but it is preferably arranged within 1 cm.

The electrolyte may _{include an electrolyte selected from the group consisting of MgSO 4} , CaSO ₄ , NaCl, KCl, HCl, KOH, NaOH, NaNO ₃ , KNO ₃ , H ₃ PO ₄ and combinations thereof, but is limited thereto. it's not going to be

The concentration of the electrolyte may be 10 mM to 100 mM, but is not limited thereto. When the concentration of the electrolyte is less than 10 mM, it cannot sufficiently serve to lower the overvoltage of the water droplet.

The electrolyte serves to lower the overvoltage of the water and stabilize the water droplet.

The measuring unit 130 measures the intensity or collision frequency of the current generated when the water droplet collides or adsorbs on the surface of the working electrode 123 .

It may further include a detection unit (not shown) for detecting the diameter of the water drop in the reaction unit 110 through the change in the intensity of the current measured by the measurement unit 130, but is not limited thereto.

In order to measure the intensity of the current, the working electrode 123 may be loaded with a voltage of 1.2 V to 1.6 V compared to the reference electrode, but is not limited thereto.

The reference electrode may be a silver/silver chloride reference electrode, but is not limited thereto.

When a voltage of less than 1.2 V is loaded on the working electrode, the oxidation of the water droplets does not occur sufficiently, so the strength of the current cannot be measured, and when a voltage exceeding 1.6 V is loaded on the working electrode, the background current and noise increases

The diameter of the water droplet may be obtained from Equation 1 below, but is not limited thereto.

In Equation 1, the d _drop is the diameter of the water droplet, Q is the integral value of the current strength, n is the number of electrons moving per molecule, F is the Faraday constant, and C _redox is The concentration of redox molecules in the water droplet.

Specifically, Q is an integral value obtained at a peak at which the intensity of the current appears.

Since two electrons are generated per water molecule as the water droplet is oxidized, n is 2.

The C _redox may be a concentration of redox species.

The redox species is water, and the C _redox means the concentration of water distributed or present in the organic solvent.

The diameter of the water droplet is a diameter when it is assumed that the water droplet is spherical.

The size distribution of the droplet may be obtained through the diameter of the droplet, but is not limited thereto.

The diameter of each of the water droplets (droplets) distributed or present in the organic solvent can be obtained through Equation 1, and the size distribution can be obtained based on this. In the case of the conventionally used dynamic light scattering method, since the distribution of the size of the water droplet was only averaged, the diameter and the exact size distribution of each droplet could not be detected. However, it is possible to detect the diameter and exact size distribution of each droplet (droplet) distributed or existing in the organic solvent by using the droplet detection device in the organic solvent of the present application.

It may be to obtain the concentration of the water droplet through the collision frequency, but is not limited thereto.

3 is a graph of the collision frequency according to the concentration according to an embodiment of the present application.

Specifically, the graph shown in FIG. 3 is a graph shown through repeated experiments (examples below).

Equation 2 is shown based on the graph shown in FIG. 3, and the concentration of the water droplet can be obtained through Equation 2 below.

In Equation 2, f _exp is an experimentally obtained collision frequency, and C _ems is the concentration of the water droplet in the organic solvent.

The theoretical value of the collision frequency can be obtained through Equation 3 below.

In Equation 3, the f _the is the theoretically obtained collision frequency, the D _ems is the diffusion coefficient of the water droplet, the C _ems is the concentration of the water droplet in the organic solvent, the r _e is the diameter of the electrode, the N _A is Avogadro's constant.

When the concentration of water droplets in the organic solvent is 14 pM, 32.7 pM, 49.1 pM and 65.5 pM, the collision frequencies obtained through Equation 3 are 0.35 Hz, 0.81 Hz, 1.21 Hz, and 1.62 Hz, respectively, whereas Equation 2 above The obtained collision frequencies were 0.03 Hz, 0.09 Hz, 0.14 Hz, and 0.21 Hz, which was found to be 8 to 10 times different from the theoretical value. Specifically, this occurs due to the aggregation and deposition of the water droplets that occur when the organic solvent and the water droplets are injected into the reaction unit 110 . If a strong emulsifier is added, the water droplets are evenly dispersed in the organic solvent, so that agglomeration and deposition do not occur, so that the experimentally obtained collision frequency and the theoretically obtained collision frequency coincide. However, in an actual situation, since the water droplets are stably dispersed in the organic solvent, the difference due to the aggregation and deposition can be neglected.

It may further include an output unit (not shown) capable of displaying a change in the intensity of the current in the working electrode over time, but is not limited thereto.

The present application includes the steps of injecting a solution containing water droplets, an electrolyte and an organic solvent into the reaction unit; providing an electrode unit including a reference electrode, a counter electrode, and a working electrode in the reaction unit; loading a voltage of 1.2 V to 1.6 V to the working electrode; and measuring the intensity of the current or the collision frequency of the working electrode of the electrode part.

4 is a flowchart of a method for detecting water droplets in an organic solvent according to an exemplary embodiment of the present application.

First, a solution containing water droplets, an electrolyte, and an organic solvent is injected into the reaction unit (S100).

Next, an electrode unit including a reference electrode, a counter electrode, and a working electrode is provided in the reaction unit (S200).

The electrode part may use a water droplet detection device in the organic solvent, but is not limited thereto.

Then, a voltage of 1.2 V to 1.6 V compared to the reference electrode is applied to the working electrode (S300).

The reference electrode may be a silver/silver chloride reference electrode, but is not limited thereto.

When a voltage of less than 1.2 V is loaded on the working electrode, the oxidation of the water droplets does not occur sufficiently, so the strength of the current cannot be measured, and when a voltage exceeding 1.6 V is loaded on the working electrode, the background current and noise increases

Then, the current strength or collision frequency of the working electrode of the electrode part is measured (S400).

It may be to detect the diameter of the water droplet through the change in the intensity of the current, but is not limited thereto.

The diameter of the water droplet may be obtained from Equation 1, but is not limited thereto.

The size distribution of the droplet may be obtained through the diameter of the droplet, but is not limited thereto.

The concentration of the water droplet may be obtained through the collision frequency, but is not limited thereto.

The concentration of the water droplets may be obtained from Equation 2, but is not limited thereto.

The method for detecting water droplets in an organic solvent according to the present application does not require redox species, so it is possible to detect water droplets in an organic solvent more simply than the prior art.

The present invention will be described in more detail through the following examples, but the following examples are for illustrative purposes only and are not intended to limit the scope of the present application.

First, in order to prepare a working electrode, Pt-UME was prepared according to a conventional procedure. More specifically, after washing the glass capillary with acetone, ethanol and distilled water, a Pt wire having a diameter of 25 μm was sealed in the capillary. Thereafter, the electrode was polished with a diamond film (0.1 μm, Allied High Tech Products, Inc.) and alumina powder (0.05 μm, Allied High Tech Products, Inc.) to obtain a mirror finish.

Then, after preparing Pt-UME (working electrode), the electrode was tested by standard redox electrochemistry in 1 mM ferrocene methanol solution, and then the experiment was performed.

Before performing each experiment, the Pt-UME (working electrode) was polished with diamond films of 3 μm and 0.1 μm until a mirror-like surface was observed.

Then, 1,2-dichloroethane (DCE) was used as an organic solvent, and the concentration of water in the solvent was 0.1 M. _{MgSO 4} was used as an electrolyte, _{and 40 μl of water containing MgSO 4} at a concentration of 55 mM was added to 5 ml of the DCE solution (including 0.1 M water) to prepare a mixed solution (98 pM). The mixed solution was dispersed by ultrasonic wave. 0.5 ml of the ultrasonically dispersed mixed solution (98 pM) was diluted with 3 ml of the DCE solution (including 0.1 M water) to prepare a mixed solution (14 pM). The concentration (C _ems ) of the diluted water droplet was estimated through Equation 4 below.

In Equation 4, the C _ems is the concentration of the diluted water droplet, the n _ems is the number of moles of the water droplet, the N _ems is the number of water droplets, the N _A is Avogadro's constant, V is the volume of the solution, and V _W is The volume of water, V _{ems ,} is the volume of one droplet. The V _ems can be obtained through Equation 5 below.

In Equation 5, r _ems is the diameter of the water droplet measured by DLS.

Then, CHI617 and 721 potentiotets (CH Instrument Inc., Austin, TX) consisting of a three-electrode cell comprising an Ag/AgCl electrode as a reference electrode, a Pt wire as a counter electrode, and the Pt-UME as a working electrode. ), the electrochemical experiment was measured using a potentiometer. All electrochemical experiments were performed in a Faraday cage (Wuhan Corrtest Instrument Co., Ltd, Wuhan, China).

A mixed solution (32.7 pM) was prepared in the same manner as in Example 1, except that 1 ml of the ultrasonically dispersed mixed solution (98 pM) was added to 2 ml of the DCE solution (including 0.1 M water).

A mixed solution (49.1 pM) was prepared in the same manner as in Example 1, except that 2 ml of the ultrasonically dispersed mixed solution (98 pM) was added to 2 ml of the DCE solution (including 0.1 M water).

A mixed solution (65.5 pM) was prepared in the same manner as in Example 1, except that 2 ml of the ultrasonically dispersed mixed solution (98 pM) was added to 1 ml of the DCE solution (including 0.1 M water).

[Comparative example]

The electrochemical experiment was performed in the same manner as in the Example, except that the electrochemical experiment was measured using a Dynamic Light Scattering (DLS) (Zetasizer Nano ZS90, Malvern Panalytical Ltd, Malvern, m UK).

[evaluation]

1. Current strength according to voltage

In the electrochemical experiments performed in Examples 1 to 4, the current intensity according to voltage was measured, and this is shown as FIG. 5 .

5A to 5E are graphs showing changes in current strength according to voltage in an electrochemical experiment according to an embodiment of the present application with time.

Specifically, an enlarged graph of a portion indicated by a circle in FIGS. 5A to 5E is shown on the right.

According to the results shown in FIGS. 5A and 5B , when 0.8 V and 1.0 V were applied to the working electrode, the strength of the current did not appear. This means that the current strength cannot be measured because the oxidation of water does not occur sufficiently. According to the results shown in FIGS. c to e, it can be seen that the background and noise increase as the voltage applied to the working electrode increases. Therefore, it is necessary not to load too high a voltage. That is, for accurate measurement, it is preferable to load a voltage of 1.2 V to 1.6 V to the working electrode.

2. Analysis of water droplets in organic solvent according to water concentration

In the electrochemical experiments performed in Examples 1 to 3 and Comparative Examples, the intensity of the current according to the concentration was measured and is shown in FIG. 6 .

6A to 6D are graphs showing the current intensity according to the concentration of water in an electrochemical experiment according to an embodiment of the present application.

Specifically, enlarged graphs of portions indicated by A, B, C, and D in FIGS. 6A to 6D are shown on the right. 6A to 6D are measured under a voltage of 1.4 V. 6B is a measurement of the mixed solution prepared according to Example 1, FIG. 6C is Example 2, and FIG. 6D is Example 3.

According to the results shown in FIG. 6a, when the solution (organic solvent) without water was measured, it was found that the current strength did not appear.

The diameter of water was obtained from Equation 1 using the intensity of the current shown in the results shown in FIGS. 6b to d. In the case of the diameter of the droplet according to the present embodiment, the diameter of each droplet distributed or existing in the organic solvent may be detected using Equation 1 above. A size distribution graph can be obtained by calculating the number according to the size of the water droplets, which is shown in FIG. 7 .

7 is a graph showing the size distribution of water droplets in an electrochemical experiment according to an embodiment and a comparative example of the present application.

According to the results shown in FIG. 7 , the average of the size (diameter) of the water droplets measured in the comparative example was 637 nm, while the average of the size (diameter) of the water droplets measured in the example was 128 nm. The reason for this result is that, in the apparatus for detecting water droplets in an organic solvent according to the present application, only partial oxidation of water occurs. Specifically, as water is oxidized, oxygen molecules, protons, and electrons are generated. Since the oxygen molecules, protons, and electrons are not diffused into the organic solvent around the water, the oxygen molecules, protons, and electrons become saturated around the working electrode, and additional oxidation does not occur. Only partial oxidation will occur. In the results according to the examples, only 0.81% of the oxidation of water was partially oxidized. Using this, the size and size distribution of water droplets when 100% oxidized can be estimated. Specifically, the average diameter of the DLS value, which can be referred to as the result when 100% oxidized, is 637 nm, and the average diameter of the water droplets in the organic solvent detected according to this embodiment is 128 nm, which is about a 5-fold difference occurs With reference to this, by multiplying the diameter of the water droplet in the organic solvent detected according to this embodiment by 5, a result value when 100% oxidized can be calculated.

8 is a graph showing the size distribution of water droplets in an electrochemical experiment according to an embodiment and a comparative example of the present application.

Specifically, FIG. 8 shows the result when 100% of water droplets in the organic solvent are oxidized according to the present embodiment. Referring to FIG. 8 , it can be confirmed that the result value when the water droplets in the organic solvent are 100% oxidized through the correction are accurately derived.

In the conventional DLS measurement method, the size of the particles can be measured only when the viscosity of the solvent containing the particles and the refractive index of the particles in the solvent are known. In addition, there is a disadvantage that the size of the particles dispersed in the solution and the concentration of the particles diluted in the solvent act as variables during measurement. In particular, the size of the average particle is expressed as an intensity distribution, which is naturally weighted according to the intensity of each particle or scattering, so the error as the presence of a small amount of agglomerates/agglomerates or large particle species dominates the distribution. may cause In addition, if the particles present in general samples to be measured do not have the same size, it is difficult to perform a similar multimodal distribution analysis.

However, in the case of the detection method using the apparatus for detecting water droplets in an organic solvent according to the present application, since light scattering is not used, it is not necessary to consider the viscosity of the solvent and the refractive index of the particles when analyzing water droplets in the organic solvent. In addition, there is an advantage in that the size of each water droplet having a multimodal distribution can be individually obtained with an electrochemical signal using the oxidation reaction of the water droplet. That is, since the apparatus for detecting water droplets in an organic solvent according to the present application can be applied to a multi-dispersion sample, it is more useful for detecting particles having various concentrations and various micro sizes.

Moreover, although the size distribution measured in the experiment performed in the comparative example shows only the average size of the droplet, the measurement result according to the present example can measure the size of each droplet, thereby indicating the size distribution. That is, there is an advantage in that not only the distribution or average size distribution of water droplets present in the organic solvent can be known, but the size of each water droplet can be known.

Furthermore, the number of collisions according to the diameter may be indicated, and the collision frequency may be calculated through the number of collisions, and the concentration of water droplets distributed or present in the organic solvent may be obtained using the collision frequency. This overcomes the disadvantage that the concentration of water droplets distributed or present in the organic solvent could not be obtained by the DLS measurement method used as a comparative example.

In the electrochemical experiment performed in the above example, the collision frequency according to the concentration was measured, and this is shown as FIG. 3 .

Equation 2 is shown based on the graph shown in FIG. 3, and the concentration of the water droplet can be obtained through Equation 2 below.

[Equation 2]

In Equation 2, f _exp is an experimentally obtained collision frequency, and C _ems is the concentration of the water droplet in the organic solvent.

Using Equation 2, it is possible to measure the concentration of water droplets distributed or present in the organic solvent through the value of the collision frequency. Specifically, in this embodiment, the relationship between the concentration and the collision frequency is expressed as an equation, and the concentration of an unknown sample (a solution in which the concentration of water droplets dispersed or present in an organic solvent is unknown) is later inferred through Equation 2 above. can do.

The theoretical value of the collision frequency can be obtained through Equation 3 below.

[Equation 3]

In Equation 3, the f _the is the theoretically obtained collision frequency, the D _ems is the diffusion coefficient of the water droplet, the C _ems is the concentration of the water droplet in the organic solvent, the r _e is the diameter of the electrode, the N _A is Avogadro's constant.

When the concentration of water droplets in the organic solvent is 14 pM, 32.7 pM, 49.1 pM and 65.5 pM, the collision frequencies obtained through Equation 3 are 0.35 Hz, 0.81 Hz, 1.21 Hz, and 1.62 Hz, respectively, whereas Equation 2 above The obtained collision frequencies were 0.03 Hz, 0.09 Hz, 0.14 Hz, and 0.21 Hz, which was found to be 8 to 10 times different from the theoretical value. This is specifically due to the aggregation and deposition of the water droplets that occur when the organic solvent and the water are injected into the reaction unit. If a strong emulsifier is added, the water droplets are evenly dispersed in the organic solvent, so that agglomeration and deposition do not occur, so that the experimentally obtained collision frequency and the theoretically obtained collision frequency coincide. However, in an actual situation, since the water droplets are stably dispersed in the organic solvent, the difference due to the aggregation and deposition can be neglected.

It was confirmed that the apparatus for detecting water droplets in an organic solvent according to the present application can simultaneously detect the size, size distribution, concentration, etc. of water droplets distributed or present in the organic solvent. In particular, by using a reaction in which water distributed or present in the organic solvent is oxidized directly on the surface of the working electrode, there is an advantage in that it is possible to analyze the characteristics of water droplets distributed or present in the organic solvent without redox species. That is, it is possible to present a simpler detection apparatus than the conventional one by not using redox species.

The above description of the present application is for illustration, and those of ordinary skill in the art to which the present application pertains will understand that it can be easily modified into other specific forms without changing the technical spirit or essential features of the present application. Therefore, it should be understood that the embodiments described above are illustrative in all respects and not restrictive. For example, each component described as a single type may be implemented in a dispersed form, and likewise components described as distributed may be implemented in a combined form.

The scope of the present application is indicated by the following claims rather than the above detailed description, and all changes or modifications derived from the meaning and scope of the claims and their equivalents should be construed as being included in the scope of the present application.

100: water droplet detection device in organic solvent
110: reaction unit
120: electrode part
121: reference electrode
122: counter electrode
123: working electrode
130: measurement unit

Claims (12)

a reaction unit in which a solution containing water droplets, an electrolyte, and an organic solvent reacts;
an electrode part located in the reaction part and including a reference electrode, a counter electrode, and a working electrode;
a measuring unit for measuring the intensity or collision frequency of a current generated when the water droplet collides or adsorbs on the surface of the working electrode of the electrode unit; and
a detection unit for detecting the diameter of the water droplet in the reaction unit through a change in the intensity of the current measured by the measuring unit;
The diameter of the water drop is obtained from Equation 1 below,
A device for detecting water droplets in an organic solvent, characterized in that the measurement is made in the absence of redox species:
[Equation 1]

In Equation 1, the d _drop is the diameter of the water droplet, Q is the integral value of the current strength, n is the number of electrons moving per molecule, F is the Faraday constant, and C _redox is The concentration of redox molecules in the water droplet.
delete The method of claim 1,
A water droplet detection device in an organic solvent, characterized in that the size distribution of the droplet is obtained through the diameter of the droplet.
The method of claim 1,
A water droplet detection device in an organic solvent, characterized in that the concentration of the water droplet is obtained through the collision frequency.
The method of claim 1,
A water droplet detection device in an organic solvent, characterized in that a voltage of 1.2 V to 1.6 V compared to the reference electrode is loaded to the working electrode for measuring the intensity of the current.
The method of claim 1,
The apparatus for detecting water droplets in an organic solvent, characterized in that it further comprises an output unit capable of displaying a change in the intensity of the current in the working electrode according to the passage of time.
The method of claim 1,
The working electrode is characterized in that it contains a material selected from the group consisting of carbon fiber, indium tin oxide, fluorine-doped tin oxide, boron-doped diamond, gold, silver, platinum, copper, nickel, and combinations thereof, organic solvent My water drop detection device.
The method of claim 1,
The electrolyte comprises an electrolyte _{selected from the group consisting of MgSO 4} , CaSO ₄ , NaCl, KCl, HCl, KOH, NaOH, NaNO ₃ , KNO ₃ , H ₃ PO ₄ and combinations thereof, organic solvent My water drop detection device.
injecting a solution containing water droplets, an electrolyte, and an organic solvent into the reaction unit;
providing an electrode unit including a reference electrode, a counter electrode, and a working electrode in the reaction unit;
loading the working electrode with a voltage of 1.2 V to 1.6 V compared to the reference electrode; and
Including; measuring the intensity of the current or the collision frequency of the working electrode of the electrode part;
Detecting the diameter of the water droplet through the change in the intensity of the current,
The diameter of the water drop is obtained from Equation 1 below,
A method for detecting water droplets in an organic solvent, characterized in that the measurement is made in the absence of a redox species:
[Equation 1]

In Equation 1, the d _drop is the diameter of the water droplet, Q is the integral value of the current strength, n is the number of electrons moving per molecule, F is the Faraday constant, and C _redox is The concentration of redox molecules in the water droplet.
delete 10. The method of claim 9,
A method for detecting water droplets in an organic solvent, characterized in that the size distribution of the water droplets is obtained through the diameter of the water droplets.
10. The method of claim 9,
A method for detecting water droplets in an organic solvent, characterized in that the concentration of the water droplets is obtained through the collision frequency.

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