KR100485988B1 - Glassy carbon electrode system and electronic system and controling method thereof - Google Patents

Abstract

The trace element measuring system of the present invention has a configuration in which a plurality of unit devices are installed in the housing 900 in order to measure the versatile trace element, and the stirring and combined glass carbon electrode 130, the mercury electrode 128, and the reference electrode ( An electrode cassette 100 having a 141 and an auxiliary electrode 142; Nitrogen purging cell 220 is disposed on the side of the electrode cassette 100, a third switch valve 230 is disposed at the lower portion thereof, and a standard-nitrogen cassette at which the standard sample cell 210 is mounted at the lower portion thereof. 200); The fourth switch valve 340 and the fifth switch valve 350 are disposed on the side of the standard-nitrogen cassette 200, and are connected to the valves 340 and 350 by a connection pipe to pump the high head in the lower position. A standard sample cassette 300 having a pump 310 and a standard sample pump 320 for pumping the standard sample of the standard sample cell 210 into the main cell 150 through the third switch valve 230. Wow; The microcomputer 850, the computer 870, the power supply unit 810, the solenoid control unit 820, to collectively control the operation of the components mounted on the cassettes 100, 200, and 300, and the computer operation and external communication. Measurement electronic system 800 and control method comprising a motor drive control unit 830, a cell control and measurement unit 840.

Description

Trace element measuring system using glass carbon electrode and accumulated mercury electrode and its electronic system and control method {GLASSY CARBON ELECTRODE SYSTEM AND ELECTRONIC SYSTEM AND CONTROLING METHOD THEREOF}

The present invention relates to a trace element measuring system using a glass carbon electrode and a red mercury electrode, an electronic system and a control method thereof, and more particularly, to measure a component of a sample containing a relatively simple mercury component and to stir the measuring object. The present invention relates to a measurement system, an electronic system, and a control method provided to simultaneously use a glass carbon electrode having a microelement and a trace element measurement function.

Conventionally, when performing quantitative qualitative analysis using polarography using the principle that voltage-current characteristics are determined in proportion to the type and concentration of analyte, a dropping mercury electrode system has been used.

As a technique for overcoming the disadvantages of the existing dropping mercury electrode system, there is a trace element measuring system using a dropping mercury electrode, such as registered Patent No. 265024.

Here, a schematic description of the trace element measuring system using the mercury electrode, as shown in Figure 1, the pedestal 10 holding the cell 12 and the cell 12 containing the sample solution, and Capillary tube 30 installed on the pedestal 10 by screwing, agitator 22 for removing mercury droplets 52 fixed on the upper seating groove 30a of the capillary tube 30, and stores mercury Accurate injector 60 to accurately measure the mercury introduced through the supply pipe 54 from the mercury storage container 50 to the capillary 30 and the supply pipe 54 and the precision according to the set position of the pipeline 46 A drip mercury electrode is provided having a switch valve 40 for selectively communicating the injector 60 and the capillary tube 30 to control the supply of mercury. Here, a plurality of ports 41 to 44 through which mercury is introduced and discharged are radially formed at an outer circumferential portion of the switch valve 40, and a platinum which maintains a contact state with mercury is formed at the center of the first pipe line 46. 48) is inserted. The working electrode 70 is connected to the platinum 48, and the opening and closing valve 56 is installed in the supply pipe 54 for supplying mercury to the first switch valve 40.

The red mercury electrode system with this configuration supplies liquid contained in the pure water tank, the electrolyte container, and the sample through the cell through a number of precision injectors, complicated connection lines, and switch valves, or cleans the remaining liquid in the pipe using pure or nitrogen. While removing, precise trace element measurements are performed.

However, the conventional trace element measuring system has a disadvantage in that it is used for the purpose of excessively washing pure water or nitrogen in order to supply the remaining liquid in the line inside the cell or to remove the air that can be injected with the sample. The operation method was complicated according to the transfer line, and the use of expensive precision injectors increased the cost of the product, which is uneconomical. The container containing the pure water, the electrolyte and the sample was simply connected by a hose, and there was inconvenience in using the sample. In this case, the potential difference could not be detected, resulting in a limitation in use.

Therefore, an object of the present invention is to solve the above-mentioned problems, it is possible to detect the mercury by the glass carbon electrode having a measuring function and a stirring function at the same time, instead of expensive precision injector (DBS pump) The present invention provides a trace element measuring system using a glass carbon electrode and a mercury electrode in which the sample, the electrolyte and the pure water supply passage are united by a nitrogen purging cell.

In addition, another object of the present invention is to provide an electronic system of a trace element measuring system using a glass carbon electrode and a suitable mercury electrode that is easy to use and can perform a unified process by integrally mounting a microcomputer and a computer in a housing. have.

In addition, another object of the present invention is to provide a trace element measurement system using a glass carbon electrode and an accumulated mercury electrode that can remove the residual solution to the outside air and optimally control the use of nitrogen.

The above-described objects of the present invention include: an electrode cassette mounted as a unit in a housing and having an agitated glass carbon electrode, an accumulated mercury electrode, a reference electrode, and an auxiliary electrode; A nitrogen purging cell is disposed on the side of the electrode cassette, a third switch valve is disposed at the lower part thereof, and a standard-nitrogen cassette at which the standard sample cell is mounted; A fourth switch valve and a fifth switch valve are arranged on the side of the standard-nitrogen cassette, and the high-pump pump and the standard sample of the standard sample cell are connected to the valves and connected to the connection pipe by the third switch. A standard sample cassette having a standard sample pump for pumping the valve through the valve; It includes a measurement electronic system consisting of a microcomputer, a computer, a power supply, a solenoid control unit, a motor drive control unit, a cell control unit, and a measurement unit so as to collectively control the operation of the components mounted on the cassette and the computer operation and external communication. This is achieved by a trace element measurement system using a glass carbon electrode and a mercury electrode.

Hereinafter, a trace element measuring system using a glass carbon electrode and an accumulated mercury electrode according to a preferred embodiment of the present invention will be described in detail with reference to FIGS. 2 to 6.

2 is an external view of a trace element measuring system using a glass carbon electrode and an accumulated mercury electrode according to an embodiment of the present invention, and FIG. 3 is a circuit configuration of an electronic system used in the measuring system shown in FIG. 4 is a configuration diagram for explaining the coupling relationship and the operation relationship of the measurement system shown in FIG.

As shown in FIG. 2, the trace element measuring system according to the present invention includes an electrode cassette 100 including a glass carbon electrode 130 and a dropping mercury electrode 128, a reference electrode 141, and an auxiliary electrode 142. ), A standard-nitrogen cassette 200, a standard sample cassette 300, and an electronic system 800 for measurement.

The electrode cassette 100 is mounted on the panel installation position 101 as a unit on the front right side of the housing 900. The disc assembly 156 and the main cell 150 are disposed on the pedestal 103, The upper surface of the main cell 150 is coupled to the electrode cover 137 on which the glass carbon electrode 130, the reference electrode 141, and the auxiliary electrode 142 are mounted. In addition, only one precision injector 129 is disposed below the pedestal 103 to inject a predetermined amount of mercury into the capillary to form the mercury electrode 128. The precision injector 129 is connected to a second switch valve (not shown) for mercury injection inside the pedestal 104. The first switch valve 110 is disposed on the right side of the main cell 150.

The standard-nitrogen cassette 200 is mounted on the left side of the electrode cassette 100 at the front right side of the housing 900, and a nitrogen purging cell 220 is disposed on an upper portion thereof, and a lower portion thereof is formed on a lower portion thereof. The three switch valve 230 is disposed, the lower portion of the standard sample cell 210 is mounted.

The standard sample cassette 300 is mounted on the left side of the standard-nitrogen cassette 200 at the front right side of the housing 900, and replaces the existing precision injectors to inject the quantitative liquid into the fourth switch. The valve 340 and the fifth switch valve 350 are disposed, and the high-lift pump pump 310 is mounted at the lower position by being connected to the connection pipe. Of course, the standard sample cassette 300 is interposed between the third switch valve 230 and the standard sample cell 210 to pass through the standard sample of the standard sample cell 210 through the third switch valve 230. A standard sample pump 320 which is pumped into the main cell 150 is further provided.

On the other hand, the floppy diskette drive slot 877 and the PCMCIA card slot 878 are disposed on the left side of the housing 900 based on the liquid crystal monitor 877 which is a kind of output device of the measurement electronic system 800. A keypad 851 used for operation control and a mouse to keyboard 871 required for computer operation are connected to an IBM compatible computer 870 mounted inside the left housing 901.

As shown in FIG. 3, the measurement electronic system 800 provided in the present invention is an electronic circuit which collectively controls the operation of the present invention and computer operation and external communication, which will be described in detail below. It can be converted to IP communication and controlled through a network at a remote location.The data value measured by the microcomputer 850 can be calculated by the IBM compatible computer 870 for component analysis or as a data result value suitable for other computer applications. It has a role to output.

The electronic system 800 includes a solenoid control unit 820, a motor drive control unit 830, a cell control and measurement unit 840 that operates as a power supply unit 810 capable of supplying voltages + 5V, + 12V, and ± 15V. ) Is connected in parallel.

Here, the solenoid control unit 820 controls the opening and closing operations of the plurality of nitrogen flow control first to fourth solenoids SSR1 to SSR4 electrically connected.

The motor drive control unit 830 includes a first switch valve 110 having a DC motor for controlling a main cell connection valve, a second switch valve 120 having a DC motor for controlling a mercury valve, and a DC motor for controlling a standard sample valve. A fourth switch valve 340 having a three switch valve 230, a DC motor for controlling a nitrogen purging cell connection valve, a fifth switch valve 350 having a DC motor for controlling a sample, pure water, and electrolyte solution injection valve, and It is electrically connected to a switch valve 360 having a DC motor for cost valve control.

In addition, the motor drive control unit 830 may include a step motor of the high lift pump pump 310, a step motor of the standard sample pump 320, a step motor of the recovery pump 610, and spare first and second step motors. 133 and 323, which are responsible for controlling their operation. In addition, the motor drive control unit 830 is electrically connected to the mercury injection step motor 123 for operating the feed shaft of the precision mercury injector and the pump reserve relay 611, and supplies power to each of the motors and the relays. It manages the supply of time, the interruption of power for a certain time, and the control signals to shut down or reset the power.

In addition, the cell control and measurement unit 840 is connected to the auxiliary electrode 142 and the reference electrode 141 through the digital-to-analog converter 841, and the glass carbon electrode serving as the working electrode through the analog-to-digital converter 842. It is connected to the electric wire 131 of 130 and the electric wire 125 of the mercury electrode 128, and the potential difference of a sample and a standard sample is measured, converting a measurement current into data according to a use place.

In addition, the microcomputer 850 receives power from the power supply unit 810 and according to a predetermined control algorithm stored in the system ROM, the solenoid control unit 820, the motor drive control unit 830, and the cell control and measurement unit 840. A built-in printer 853 which transmits an operation command or receives measurement values, an external device 852 connected through various serial communications with a keypad 851 for receiving a user's operation signal, and outputs the result to the ground. ) Is connected. The microcomputer 850 is interoperable with the IBM compatible computer 870 through serial communication (RS232).

The computer 870 is responsible for measuring and outputting the components of the sample by comparing and calculating the measurement result received from the microcomputer 850, and for this purpose, the liquid crystal monitor 877, the keyboard 871, the mouse 872, and the hard drive. And a data storage device 873 such as a disk and a floppy disk, an external printer 874, a serial communication module 875, and a TCP / IP module 876 for LAN connection.

In the following, a coupling relationship and an operation relationship between the trace element measuring system using the glass carbon electrode and the accumulated mercury electrode of the present invention operated by the electronic system 800 will be described.

As shown in FIG. 4, the mercury electrode 128 in the electrode cassette 100 has the same configuration as described in the related art. That is, the precision injector 129 is lowered by the piston shaft to the mercury injection step motor 123 so that a certain amount of mercury is injected when the cylinder 127 and the mercury container 122 are connected by the operation of the second switch valve 120. Mercury in the mercury canister 122 is introduced into the cylinder 127, and then, the second switch valve 120 cuts off the connection with the mercury canister 122, and at the same time, the cylinder 127 and the mercury The capillary of the electrode 128 is connected. In this case, the mercury injection step motor 123 raises and lowers the piston shaft, and mercury introduced into the cylinder is injected into the capillary of the mercury electrode 128. The mercury injected in this way is settled in the seating groove 126 formed at the end of the capillary tube to be in a state capable of measuring the potential difference.

In addition, the glass carbon electrode 130 mounted on the electrode cover 137 to be used for the measurement of the sample containing mercury is equipped with a stirrer motor 132 inside the disassembly and assembly housing, the rotary shaft of the stirrer motor 132 An inert polymer (PEEK) shaft connecting member, a stainless shaft, and a hollow teflon bar are coupled to each other, and a glass carbon electrode bar electrically connected to the driving shaft is assembled to the lower shaft center of the teflon bar. An electrode connector having a contactor capable of receiving a current from the driving shaft is inserted into the circumference of the shaft assembly thus fastened, and the contactor of the electrode connector is connected to the wire 131 of the glass carbon electrode 130. The measurement current can be transmitted to the cell control and measurement unit 840. The stirring blade 139 is mounted at the end of the shaft assembly of the glass carbon electrode 130, and when power is applied to the stirrer motor 132 according to a control signal, the stirring blade together with the rotating shaft and the shaft assembly of the motor ( 139 rotates at high speed. Therefore, in the glass carbon electrode 130, the stirrer motor 132 may leave the mercury deposited in the seating groove 126 of the silver cumulative mercury electrode 128, depending on its operation. Introduced into the inside of the cell 150 may perform a role of stirring to mix well.

The first switch valve 110 connects the output port 159 of the disk assembly 156 and the input port of the recovery pump 610 to recover the mercury or the solution after use, or 2). The nitrogen purging cell 220 and the main cell 150 are connected to each other, or 3) the nitrogen purging cell 220 and the recovery pump 610 are connected to each other by connecting hoses.

Switch valves (110, 120, 230, 340, 350) described in the present invention has a selection pipe (A, date, T-shape) to selectively control or open or close the flow direction of liquid to gas, these selection When the duct is rotated, it is arranged as “도면” in the drawing when the downward operating angle (hereinafter referred to as “angle”) is 0 °, the leftward angle is 90 °, the upward angle is 180 °, and the rightward angle is 270 °. do.

For example, when the selection passage 111 of the first switch valve 110 has an angle of 0 ° (downward), the main port is connected by connecting the output port 159 of the disk assembly 156 and the input port of the recovery pump 610. The mercury in the cell 150 is recovered in the mercury recovery container 600 through the recovery pump 610, and the liquid in the main cell 150 is the recovery pump 610, mercury recovery container 600, a plurality of Through the recovery port 440 of the port cassette 400 having the connection port is recovered to the use liquid recovery container 620. In addition, when the selection line 111 is 180 degrees (upward), by connecting the nitrogen purging cell 220 and the main cell 150, nitrogen or liquid filled in the nitrogen purging cell 220 is the main cell ( 150 is introduced into the interior. In addition, when the selection line 111 is at an angle of 270 ° (right), the input port of the nitrogen purging cell 220 and the recovery pump 610 is connected, so that nitrogen, air, liquid, etc. of the nitrogen purging cell 220 It flows into the recovery pump 610 and is recovered as a result.

Hereinafter, the coupling relationship between the second and fourth switch valves 120, 230, 340, and 350 is not only similar to the coupling relationship of the first switch valve 110 described above, but also through an operation method to be described in detail below. Since those skilled in the art can fully understand the description, it is omitted here.

However, the fifth switch valve 350 is disposed radially on the circumferential surface, and the first port 352 connected to the electrolyte port 410 of the port cassette 400 and the external air at a 90 ° interval to such a port. The second port 353 into which is introduced, and the third port 354 connected to the sample port 430 while still forming a 90 ° interval, and the fourth port connected to the pure water port 420 while still forming a 90 ° interval. 355, and a fifth port 356, which is arranged to protrude in the center and connected to the input 312 of the high lift pump pump 310 by a connecting pipe.

In the present invention, a nitrogen port 450 connected to the pressure regulator 710 of the nitrogen cylinder 700 to supply nitrogen gas to the first to fourth solenoids SSR1 to SSR4 and the recovered liquid are used. The recovery port 440 for sending to the liquid recovery container 620, the sample port 430 for fastening the sample to the fifth switch valve 350 is fastened with the sample container, and the fifth switch valve ( A pot cassette consisting of a pure water port 420 for supplying pure water to the 350, and also an electrolyte port 410 for supplying electrolyte to the fifth switch valve 350 and also connected with the electrolyte solution container 400 is further provided.

As shown in FIG. 5, the operation control method of the measurement system of the present invention will be described in detail step by step as follows.

-Discard preservation solution (S10)

The first switch valve 110 is connected to the main cell 150 and the recovery container (600, 620) by positioning the selection pipe 111 at an angle of 0 °, the second switch valve 120 is selected pipe angle of 90 ° The capillary of the cylinder 127 of the precision injector 129 and the mercury electrode 128 is positioned in the state of being connected to. The recovery pump 610 is operated to lower the internal pressure of the main cell 150, and the stirrer motor 132 of the glass carbon electrode 130 rotates the stirring blade 139 by a predetermined time while the solution is recovered. Stir the solution, after which the operation of the recovery pump 610 is stopped, the stirrer motor 132 of the glass carbon electrode 130 is stopped.

-Injecting pure water into nitrogen purging cell (S20)

The fourth switch valve 340 is connected to the output 311 and the nitrogen purging cell 220 of the high-lift pump pump 310 by positioning the selection pipe 341 at an angle of 0 °, the fifth switch valve 350 is The selection duct 351 is positioned at an angle of 0 °, and connects the input 312 of the high lift pump pump 310 and the pure water port 420. Thereafter, the high lift pumping pump 310 is operated for a fixed amount, and then rests for a predetermined delay time. The fifth switch valve 350 places the selection line 351 at an angle of 270 ° to input the high lift pumping pump 310 ( 312) and the external air. Thereafter, when the high lift pumping pump 310 is operated, air is injected to inject the remaining solution in the tube into the nitrogen purging cell 220.

-Mercury replacement (S30)

The third switch valve 230 checks the origin, the second switch valve 120 is positioned by the selection line 121 at an angle of 0 °, the cylinder 127 of the mercury container 122 and the precision injector 129 Connect it. The mercury injection step motor 123 lowers the piston shaft, and a small amount of mercury to be measured once in the mercury can 122 is introduced into the cylinder 127. In addition, the second switch valve 120 cuts off the connection with the mercury container 122 by placing the selection channel 121 at an angle of 90 ° and connects the capillary of the cylinder 127 and the mercury electrode 128 at the same time. do. Thereafter, the mercury injection step motor 123 raises and lowers the piston shaft, and mercury introduced into the cylinder is injected into the capillary of the mercury electrode 128.

Recovering mercury (S31)

Power is applied to the stirrer motor 132 of the glass carbon electrode 130, and the stirrer motor 132 moves the stirring blade 139 at a high speed for a predetermined time so that mercury deposited in the seating groove 126 of the capillary tube falls. Rotate and stop after time.

Injecting the electrolyte solution into the nitrogen purging cell (S40)

The fourth switch valve 340 is connected to the output 311 and the nitrogen purging cell 220 of the high-lift pump pump 310 by positioning the selection pipe 341 at an angle of 0 °, the fifth switch valve 350 is The selection duct 351 is positioned at an angle of 90 °, and is connected to the input 312 of the high lift pumping pump 310 and the electrolyte port 410 connected to the electrolyte container containing the electrolyte solution. Thereafter, the high lift pumping pump 310 is operated for a fixed amount, and then rests for a predetermined delay time. The fifth switch valve 350 places the selection line 351 at an angle of 270 ° to input the high lift pumping pump 310 ( 312) and the external air. Thereafter, when the high lift pumping pump 310 is operated, air is injected to inject the remaining solution in the tube into the nitrogen purging cell 220.

Injecting into the main cell after purging nitrogen (S50)

The fourth switch valve 340 connects the first solenoid SSR1 and the nitrogen purging cell 220 by positioning the selection channel 341 at an angle of 270 °. At this time, according to the opening operation of the first solenoid (SSR1), the nitrogen of the nitrogen cylinder 700 to the fourth switch valve 340 through the pressure regulator 710, nitrogen port 450, the first solenoid (SSR1). While being introduced, it is supplied to the nitrogen purging cell 220 while pushing out the remaining solution in the tube. In addition, according to the opening operation of the third solenoid SSR3, nitrogen is directly supplied to the nitrogen purging cell 220. After time has passed for nitrogen to flow into the nitrogen purging cell 220, the first switch valve 110 connects the nitrogen purging cell 220 to the main cell 150 by placing the selection line 111 at an angle of 180 °. Let's do it. Then, according to the closing operation of the third solenoid (SSR3), the nitrogen supply to the nitrogen purging cell 220 is cut off, and after a predetermined delay time, the first solenoid (SSR1) performs the closing operation, the nitrogen by free fall The solution of the purging cell 220 moves into the main cell 150. Thereafter, the first switch valve 110 cuts the connection of the nitrogen purging cell 220 and the main cell 150 by placing the selection line 111 at an angle of 270 °.

-Purging pure water and then injecting it into the main cell (S51)

This step is the same as the above step (S50), detailed description thereof will be omitted.

Injecting the sample solution into the nitrogen purging cell (S60)

The first switch valve 110 connects the main cell 150 and the recovery vessels 600 and 620 by positioning the selection line 111 at an angle of 0 °. The fourth switch valve 340 is connected to the output 311 and the nitrogen purging cell 220 of the high-lift pump pump 310 by positioning the selection pipe 341 at an angle of 0 °, the fifth switch valve 350 is The selection channel 351 is positioned at an angle of 180 ° and is connected to the input port 312 of the high lift pump pump 310 and the sample port 430 connected to the sample container containing the sample solution. Thereafter, the high lift pumping pump 310 is operated for a fixed amount, and then rests for a predetermined delay time. The fifth switch valve 350 places the selection line 351 at an angle of 270 ° to input the high lift pumping pump 310 ( 312) and the external air. Thereafter, when the high lift pumping pump 310 is operated, air is injected to inject the remaining solution in the tube into the nitrogen purging cell 220.

Injecting the standard sample solution into the main cell (S70)

The third switch valve 230 is located at an angle of 180 ° to the selection duct 231 to connect the output 321 of the standard sample pump 320 and the main cell 150, in this case, the standard sample pump 320 The input 322 and the standard sample cell 210 is connected. Thereafter, the standard sample pump 320 is operated for a fixed amount, and then rests for a predetermined delay time. The third switch valve 230 positions the selection duct 231 at an angle of 270 ° so that the second solenoid SSR2 and the main cell are positioned. Connect 150. At this time, according to the opening operation of the second solenoid (SSR2), the nitrogen of the nitrogen tank 700 to the third switch valve 230 through the pressure regulator 710, nitrogen port 450, the second solenoid (SSR2) As it is introduced, it is supplied to the main cell 150 while removing the remaining solution in the tube. Then, after the delay time for nitrogen to flow into the main cell 150 is maintained, the third switch valve 230 positions the selection duct 231 at an angle of 0 ° so that the second solenoid SSR2 and the main cell 150 are maintained. )). In addition, the second solenoid SSR2 performs a closing operation to block nitrogen from being supplied to the main cell 150.

-Initialization of switch valve, solenoid, pump (S80)

The first switch valve 110 is a state in which the selection line 111 is located at 0 ° to connect the main cell 150 and the recovery containers 600 and 620.

The second switch valve 120 is in a state in which the mercury can 122 and the cylinder 127 of the precision injector 129 are connected by positioning the select passage 121 at an angle of 0 °.

The third switch valve 230 is a state in which the connection of the second solenoid (SSR2) and the main cell 150 by placing the selection line 231 at an angle of 0 °.

The fourth switch valve 340 is a state in which the selection pipe 341 is positioned at an angle of 0 ° to connect the output 311 of the high head pressure pump 310 and the nitrogen purging cell 220.

The fifth switch valve 350 is located at an angle of 0 ° to the selection duct 351, and is connected to the input 312 of the high lift pump pump 310 and the pure water port 420.

The solenoids SSR1, SSR2, SSR3 and the pumps 610, 310, 320 are in a stopped state.

As shown in FIG. 6, the measuring method of the measuring system of the present invention will be described step by step.

-Measurement waiting state (AQ0)

-Measurement without sample (AQ1)

First, after injecting the above-described electrolyte solution into the nitrogen purging cell (S40), purging the nitrogen and then injecting into the main cell (S50), replacing the mercury (S30) continuously, through the glass carbon electrode 130 The component is measured, or the component is measured through mercury droplets deposited on the mercury electrode 128, and the mercury recovery (S31) ends.

Sample measurement (AQ2)

Here, the sample solution is injected into the nitrogen purging cell (S60), after purging the nitrogen, and then injected into the main cell (S50) and mercury replacement (S30) step, the glass carbon electrode 130 and red mercury The component is measured by the electrode 128, and the mercury recovery (S31) is completed.

-Measurement of standard samples (AQ3)

Here, after injecting the standard sample solution into the main cell (S70), replacing the mercury (S30) step in order, the component is measured by the glass carbon electrode 130 and the mercury electrode 128, and mercury recovery Finishing step (S31).

Automatic measurement (AQ4)

Here, after discarding the preservation solution (S10), injecting pure water into the nitrogen purging cell (S20), injecting the pure water into the main cell after purging (S51), and then discarding the preserving solution (S10) in sequence, a 1 second delay time After the excitation, the measurement (AQ1) is performed without a sample, and again, a 3 second delay time is performed, and the measurement of the sample is again performed (AQ2), followed by a 3 second delay time, and then the measurement of the standard sample (AQ3). Injecting pure water into the nitrogen purging cell (S20) and initializing the switch valve, solenoid and pump (S80).

As described in detail above, the trace element measurement system using the glass carbon electrode and the mercury electrode of the present invention supplies external liquid together with nitrogen to supply the remaining liquid in the line into the cell or to remove the air that can be injected with the sample. It is configured to use, so that the nitrogen consumption rate can be minimized, which is very economical.

In addition, the present invention can provide a simple solution transfer pipe by employing a high-pump pump and nitrogen purging cell and a standard sample cell, it is mounted on the housing with a cassette structure has the effect of maximizing user convenience.

In addition, the present invention provides a port cassette in which a plurality of ports are arranged in one cassette so that a plurality of solutions can be concisely connected, so that the replacement of the solutions is very easy.

In addition, the present invention can measure trace elements in parallel with the glass carbon electrode, and therefore has excellent performance of detecting a potential difference even when mercury is contained in the sample.

Although the technical idea of the trace element measuring system using the glass carbon electrode and the mercury electrode of the present invention, the electronic system and the control method of the present invention described above are described together with the accompanying drawings, this will be described as an exemplary embodiment of the present invention. It does not limit the invention. In addition, it is obvious that any person skilled in the art can make various modifications and imitations without departing from the scope of the technical idea of the present invention.

1 is a block diagram for explaining a mercury electrode system according to the prior art;

2 is an external view of a trace element measuring system using a glass carbon electrode and a mercury electrode according to an embodiment of the present invention;

3 is a circuit diagram of an electronic system used in the measurement system shown in FIG.

4 is a configuration diagram for explaining the coupling relationship and the operation relationship of the measurement system shown in FIG.

5 is a flowchart for explaining an operation control method of the measurement system shown in FIG. 2;

6 is a flowchart for explaining a measuring method of the measuring system shown in FIG.

♣ Explanation of symbols for main part of drawing ♣

100: electrode cassette 110, 120, 230, 340, 350: switch valve

128: red mercury electrode 130: glass carbon electrode

141: reference electrode 142: auxiliary electrode

150: main cell 200: standard-nitrogen cassette

220: nitrogen purging cell 210: standard sample cell

300: standard sample cassette 310: pressure pump

320: standard sample pump 800: electronic system

810: power supply unit 820: solenoid control unit

830: motor drive control unit 840: measurement unit

850: Micom 870: Computer

900: housing SSR1 to SSR4: solenoid

Claims (5)

In the housing 900 is equipped with a plurality of unit devices in the trace element measuring system using a glass carbon electrode and a red mercury electrode for measuring the components and trace elements of the sample containing the mercury component, respectively, The precision injector 129 connected to the second switch valve 120 is installed at the lower portion of the pedestal 103 to form the mercury electrode 128, and the disk assembly 156 and the main cell 150 are installed at the upper portion thereof. An electrode cover 137 having a first switch valve 110 installed on the right side thereof is located, and the glass carbon electrode 130 having the electric motor 132, the reference electrode 14, and the auxiliary electrode 142 are disposed on the electrode cover. An electrode cassette 100 provided at 137; A standard sample cell 210 storing a standard sample, a nitrogen purging cell 220 filled with any one of nitrogen and a predetermined liquid connected to the main cell 150 therein, and a standard of the standard sample cell 210 according to its operation. A standard-nitrogen cassette 200 configured to consist of third switch valves 230 for supplying a sample solution to the main cell 150 and purging the sample after supplying nitrogen to the main cell 150; The nitrogen gas is supplied to the nitrogen purging cell 220 according to the operation of the fourth switch valve 340, and the sample solution of the electrolyte is supplied to the nitrogen purging cell 220 according to the operation of the fifth switch valve 350. A high lift pumping pump 310 for purging by supplying external air to the nitrogen purging cell 220 after a predetermined time after the measurement of the sample is finished; A standard sample cassette 300 having a standard sample pump 320 for pumping the standard sample of the standard sample cell 210 to the main cell 150 through the third switch valve 230; First to fourth switches connected to the first to fifth switch valves 110, 120, 230, 340 and 350 connected to the main cell 150 and sixth switch valves 360 for preliminary valve control. A solenoid control unit 820 which opens and closes the snoroids SSR1 to SSR4; Operation of the high head pressure pump 310, the standard sample pump 320, the recovery pump 610 and the first and second step motors 133 and 323, the mercury injection step motor 123, and the pump spare relay 611. A motor drive control unit 830 for controlling the driving force; Digital-to-analog converter 841 connected to the auxiliary electrode 142 and the reference electrode 141, and an analog-to-digital converter 842 connected to the glass carbon electrode 130 and the mercury electrode 128, the measurement sample and the standard A cell control and measurement unit 840 for measuring the potential difference of the sample; The solenoid controller 820 and the motor drive controller 830 according to a predetermined system program; A microcomputer 850 for operating control commands or receiving measurement signals to the cell control and measurement unit 840; Trace element using a glass carbon electrode and a red mercury electrode, characterized in that the electronic system 800 composed of computers 870 to compare and calculate the measurement results from the microcomputer 850 to measure and output the components of the sample Measuring system. The method of claim 1, A nitrogen port 450 connected to the pressure regulator 710 of the nitrogen container 700 to supply nitrogen gas to the first to fourth solenoids SSR1 to SSR4, and the recovered liquid is used as a liquid recovery container 620. And a recovery port 440 for sending to the sample, a sample port 430 for fastening the sample to the fifth switch valve 350, and a pure water pipe for fastening the sample to the fifth switch valve 350. Further, a port cassette 400 consisting of an electrolyte port 410 for supplying electrolyte to the fifth switch valve 350 and also connected to the electrolyte solution container for supplying the electrolyte is further connected. Trace element measurement system using a glass carbon electrode and a mercury electrode, characterized in that it comprises. The method of claim 1, The fifth switch valve 350 is disposed radially on the circumferential surface, and the first port 352 connected to the electrolyte port 410 of the port cassette 400 and the external air at a 90 ° interval to the port. Is connected to the second port 353 and the third port 354 connected to the sample port 430 while forming a 90 ° interval, and also connected to the pure port 420 while forming a 90 ° interval. A glass carbon electrode and a red mercury electrode, characterized by having a fourth port 355 and a fifth port 356 arranged to protrude in the center and connected to an input 312 of the high lift pump pump 310 as a connecting pipe. Trace element measurement system using. delete In the control method of the trace element measuring system using the glass carbon electrode and the red mercury electrode, In the step (S10) of discarding the storage solution in the main cell 150, the first switch valve 110 is operated to connect the main cells 150 and the recovery containers 600 and 620, and the recovery pump 610 and the glass carbon. Operating the stirrer motor 132 of the electrode 130 to stir and recover the storage solution; Injecting pure water into the nitrogen purging cell (S20) operates the fourth switch valve 340 to be connected to the high-pump pressure pump 310 and the nitrogen purging cell 220, the fifth switch valve 350 is operated The high lift pump pump 310 is connected to the pure water port 420 so that pure water and external air are sequentially supplied to the nitrogen purging cell 220. In the step of replacing mercury (S30), by operating the second switch valve 120 and the mercury injection step motor 123 while the third switch valve 230 is at the origin of the appropriate amount of mercury electrode 128 Positioning the mercury in the chamfer groove 126 of the capillary, in the step of recovering the mercury (S31) by operating the stirrer motor 132 of the glass carbon electrode 130 to rotate the stirring blade 139 at high speed; In operation S40 of injecting the measurement electrolyte solution into the nitrogen purging cell 220, the fourth switch valve 340 and the fifth switch valve 350 are sequentially operated to allow the high lift pump pump 310 to purge the electrolyte solution. Supplying to the jingsel 220 and injecting external air into the nitrogen purging cell 220 after a predetermined relay time to remove the remaining solution in the tube; Injecting the remaining solution on the pipeline into the main cell 150 after nitrogen purging (S51) by operating the fourth switch valve 340 to open the first solenoid (SSR1) to the residual solution on the pipeline by nitrogen By opening the third solenoid (SSR3) to supply nitrogen to the nitrogen purging cell 220; Injecting the sample solution into the nitrogen purging cell (S60), the first switch valve 110, the fourth switch valve 340 and the fifth switch valve 350 is operated to a predetermined position and the high lift pump pump 310 In the step S70 of supplying the sample solution and the external air from the sample port 430 to the nitrogen purging cell 220 and removing the remaining solution and supplying the standard sample solution to the main cell 150 (S70), In operation 230, the standard pump pump 320 is operated and the standard sample is supplied to the standard sample cell 210, and at the same time, the second solenoid SSR2 is opened to supply nitrogen to the main cell 150. To become; In the step S80 of initializing the switch valve, the solenoid, and the pulp, the initial position of the first switch valve 110 is in a state of connecting the main cell 150 and the recovery containers 600 and 620, and the second switch valve ( The initial position of the 120 is a state in which the mercury container 122 and the cylinder 127 are connected, and the initial position of the third switch valve 230 blocks the second solenoid SSR2 and the main cell 150. The initial position of the fourth switch valve 340 is a state in which the high lift pumping pump 310 and the nitrogen purging cell 220 are connected, and the initial position of the fifth switch valve 350 is the high lift pumping pump 310 and the pure water. The port 420 is connected, and the solenoids SSR1, SSR2 and SSR3 and the pumps 610, 301 and 320 are in a stopped state; By selectively selecting the steps (S10) to (S80) by applying any one of the glass carbon electrode 130 and the mercury electrode (AQ1) to measure the state without the sample (AQ1), the sample solution is a glass carbon electrode ( 130) and the mercury electrode 128 is applied to measure the component (AQ2) so that the component is measured. The standard sample is a glass carbon electrode 130 and the mercury electrode 128 to measure the component and recover mercury. Glass measuring characterized in that the measurement (AQ3), and perform the measurement (AQ1), (AQ2) and (AQ3) to perform the automatic measurement (AQ4) to perform the system initialization step (S80) in sequence Control method of trace element measurement system using carbon electrode and accumulated mercury electrode.