JPH0598483A - Nonlinear vibrator - Google Patents

Abstract

PURPOSE:To simplify the device and to reduce the cost by determining the two physical values among the current value, temp. of acidic soln. and concn. of org. matter and widening the range of the third physical value. CONSTITUTION:A semipermeable membrane 3 is provided almost in the middle of a vessel 2 filled in with an acidic soln. 1 to divide the vessel into two sections. Org. matter is mixed with the acidic soln. in the one section to obtain a mixed soln. 4 of the acid and org. matter. Electrodes 5 and 6 are inserted into both sections, and a constant current is applied between both electrodes from a constant-current power source 7. The two physical values among the current value, temp. of the acidic soln. and concn. of the org. matter to be mixed are determined, and the range of the third physical value is widened to stabilize the potential vibration for a long period. Formic acid or formaldehyde is used as the org. matter, and the electrodes are made of ruthenium, rhodium or palladium. An electrical control with the fuzziness having one-(f)-th fluctuation is conducted with one electrochemical element.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a nonlinear oscillator having fluctuations in the period or amplitude, which is useful for fuzzy control and the like.
The present invention relates to a non-linear oscillator which operates stably in a range of 800 seconds.

[0002]

2. Description of the Related Art Conventionally, a microcomputer and software such as ROM have been required to incorporate fuzzy characteristics and 1 / f fluctuation in electric control.

[0003]

The above-mentioned conventional technique has a problem that the control is performed by the microcomputer, which causes the complexity and cost of the device. In order to solve these problems, an object of the present invention is to provide an element that stably generates fluctuation vibration for a long period of time.

[0004]

In order to achieve the above object, an electrochemical vibration phenomenon in the oxidation of organic substances is used. It has been known for a long time that oscillations of electric potential and electric current are observed in the electrochemical oxidation reaction of organic substances, and as a reference, for example, Zeitschrift Fuhr Electrochemie 34 (1928) 256-264 (Z. El.
microchem. 34 , 256-264 (192
8)) However, in the literature, the conditions under which the vibration is stable for a long period of time have not been clarified, nor has there been any fluctuation in the vibration. The present invention clarifies the conditions such as the limitation of organic substances and the concentration of organic substances and the reaction temperature for long-term stable vibration, and provides an element that generates fluctuating vibration.

[0005]

The present invention utilizes the fact that the potential oscillates when a constant current is externally applied to the electrodes.

The mechanism of action is as follows. By passing a constant current, the oxidation reaction of the organic substance proceeds, and at the same time, a chemical substance that inhibits the oxidation reaction by a side reaction is adsorbed on the electrode surface. As a result, the potential increases under the condition that the current is constant. When the potential becomes higher, the adsorbed inhibitor is removed by oxidation, and the surface becomes active,
The potential returns to the original low potential. It is considered that the above is repeated and the potential oscillates.

Since the rate of generation and disappearance of the inhibitor depends on the electric potential, the vibration pattern is a non-linear vibration pattern, which is different from the sinusoidal curve. The cycle can be controlled in the range of 0.01 to 1800 seconds depending on operating conditions.
Further, it is considered that the reason why the period and the amplitude fluctuate is that the vibration has nonlinearity.

The present invention will be specifically described below with reference to examples.

First, the overall structure of the apparatus will be described with reference to FIGS. 1 and 2. As shown in FIG. 1, a practical apparatus has a semipermeable membrane 3 in the middle of a container 2 filled with an acidic solution 1 and a mixed solution 4 of an acid and an organic material is provided only in one chamber of the container 2. The electrodes 5 and 6 are inserted into both chambers of the container 2, and a vibration of a potential obtained by passing a constant current from the constant current power supply 7 between them is output to the output terminal 8 as an inter-electrode voltage. However, in the constitution of the device used in the following examples, the electrodes were divided into three as shown in FIG. 2 in order to strictly verify the operation of the device shown in FIG. One is a sample electrode 20 and corresponds to the electrode 5 in FIG. The second one is the opposite pole 2
It is 1. The third one is the hydrogen reference electrode 22 and corresponds to the electrode 6 in FIG. A constant current from the constant current power supply 7 is passed between the sample electrode 20 and the counter electrode 21, and the sample electrode 20 that appears at that time
The potential of is output to the hydrogen reference electrode 22. These three electrodes are immersed in the mixed liquid 4 of acid and organic substance, and the counter electrode 21 and the hydrogen electrode 22 are mixed with the mixed liquid 4 of acid and organic substance through the pipes 23 and 24 containing the acidic solution 1.
Be immersed in. In the pipe 23, electrons can flow through the frit glass 25 on the bottom surface, and in the pipe 24, electrical connection can be made through the microscopic holes 26 in the bottom surface. Hydrogen gas is supplied to the pipe 24 through a thin tube 27. With this configuration, the state of the electrode surface can be examined in detail.

Example 1 Formic acid was oxidized at a constant current by using an electrolytic solution containing 0.5 mol of sulfuric acid and 0.1 to 13 mol of formic acid per liter at 23 ° C. and a platinum electrode. As a result of examining the state of potential oscillation at this time, as shown in Table 1, when the concentration of formic acid was 1 to 13 moles per liter, stable potential oscillation was observed for 1 hour or more. It can be seen from Table 1 that the cycle can be controlled between 20 and 300 seconds by controlling the current value. Further, the period and the amplitude fluctuated in all cases by about 5% as shown in the example of the typical potential oscillation pattern in the present invention in FIG. The period and amplitude

[0011]

[Table 1]

[0012] was slowly increasing and decreasing over time.

Example 2 An experiment was conducted in the same manner as in Example 1 except that the temperature of the electrolytic solution was 0 ° C., 40 ° C., 60 ° C. or 80 ° C., and the results shown in Table 2 were obtained. .. From Table 1 and Table 2, by controlling the temperature, the formic acid concentration, and the current value, respectively, the cycle is 0.7 to 1
It can be seen that the control can be performed within the range of 800 seconds. Further, the vibration pattern had fluctuations of about 5% in the period and the amplitude as in FIG.

[0014]

[Table 2]

<Example 3> As a result of performing an experiment in Example 1 using formaldehyde instead of formic acid,
As shown in Table 3, stable potential oscillation was observed for 1 hour or longer at a formaldehyde concentration of 0.01 to 10 mol per liter. The cycle is set to 0.5 by controlling the current value.
It can be seen from Table 3 that control can be performed within ~ 13 seconds. The period and the amplitude fluctuated as shown in FIG. 3 in all cases, but the fluctuation was as small as about 2%.

[0016]

[Table 3]

Example 4 An experiment was conducted in the same manner as in Example 3 except that the temperature of the electrolytic solution was 0 ° C., 40 ° C. or 60 ° C., and the results shown in Table 4 were obtained. From Table 3 and Table 4,

[0018]

[Table 4]

It is understood that the cycle can be controlled in the range of 0.01 to 36 seconds by controlling the temperature, the formaldehyde concentration and the current value, respectively. Further, the vibration pattern was similar to that of FIG. 3, and the period and the amplitude had a fluctuation of about 2%.

<Example 5> In Example 1, the organic substance was
As a result of conducting the experiment under the same conditions except that a 1: 1 mixture of formic acid and formaldehyde (1 mol per 1 liter each) was used, the mixing effect as shown in Table 5 was observed. That is, compared to the case of using formic acid alone, stable oscillation is exhibited from a low current value, and the cycle becomes short. On the contrary, Holmarde

[0021]

[Table 5]

The period is longer than that of the case of only the ridge, and although it is not always clear in Table 5, the oscillation is shown from a high current value. The fluctuation width was almost halfway between formic acid only and formaldehyde only.

<Example 6> In Example 5, the concentration of formaldehyde was fixed at 0.01 mol per liter, and the concentration of formic acid was adjusted to 0.01 mol per liter.
When the amount was increased to 1 mol and 1 mol, a mixing effect similar to that in Example 5 was observed, and the property of formic acid was more strongly exhibited as the concentration of formic acid was increased.

Example 7 Contrary to Example 6, the concentration of formic acid was fixed at 0.1 mol per liter, and the concentration of formaldehyde was 0.001 mol per liter,
When increased to 0.01 mol, 0.1 mol, 1 mol,
A mixing effect similar to that of Example 5 was seen, with more pronounced formaldehyde properties with increasing formaldehyde concentration.

<Embodiment 8> In the first or third embodiment, ruthenium, rhodium, palladium, osmium, iridium, or an alloy of platinum and palladium may be used instead of the platinum electrode.
Results similar to those of Example 1 or Example 3 were obtained. Also,
From these results, it can be easily inferred that the intermetallic alloy described in this example also exhibits similar properties.

<Embodiment 9> In Embodiment 1 or Embodiment 3, the concentration of dilute sulfuric acid is 0.01 mol, or 0.1 mol, or 5 instead of 0.5 mol per liter.
Even when a molar solution was used, stable potential oscillation tended to occur in this order, but similar results were obtained. Also, almost the same results were obtained when perchloric acid was used at the same concentration instead of dilute sulfuric acid.

<Example 10> In Example 1, substantially the same result was obtained even if the size of the entire electrochemical device was 10 mm cubic and the thickness of each electrode was 1 mm.

[0028]

EFFECTS OF THE INVENTION According to the present invention, fuzzyness and 1 / f
Since electric control having fluctuations can be performed by one electrochemical element, there is an effect of simplification of the device and cost reduction.

[Brief description of drawings]

FIG. 1 is a practical overall configuration of the present invention.

FIG. 2 is an overall configuration of the measuring device used in the experiment.

FIG. 3 is a typical potential oscillation pattern according to the present invention.

Claims (5)

[Claims] 1. A container filled with an acidic solution, a semipermeable membrane provided in the middle of the container, and an organic solution mixed only in the acidic solution in one of the chambers partitioned by the semipermeable membrane, and electrodes in both chambers. Is a device for inserting a constant current between the two by inserting an electric current value, the temperature of the acidic solution, and the concentration of the organic matter to be mixed, and decides two of them to give a range to the third physical quantity. A non-linear oscillator characterized by causing potential oscillation stably over a long period of time. 2. A nonlinear oscillator according to claim 1, wherein formic acid, formaldehyde or a mixture thereof is used as an organic substance. 3. A nonlinear oscillator according to claim 1, wherein ruthenium, rhodium, palladium, osmium, iridium, platinum, or an alloy thereof is used as an electrode. 4. The method according to claim 1, wherein 0.
A non-linear oscillator characterized in that an aqueous solution of sulfuric acid or perchloric acid having a concentration of 01 to 5 mol is used as an electrolytic solution. 5. The non-linear oscillator according to claim 1, wherein the formic acid concentration is 0.1 to 13 mol per liter, or the formaldehyde concentration is 0.01 to 10 mol per liter.