JP5214420B2 - Electrolyte analysis method and electrolyte analyzer - Google Patents

Description

  The present invention relates to an electrolyte analysis method and an electrolyte analyzer for measuring the electrolyte concentration of a sample by supplying a diluted sample to a measurement unit using an ion selective electrode, and particularly an electrolyte such as urine or serum (Na: sodium, (K: potassium, Cl: chlorine, Ca: calcium, etc.) The present invention relates to an electrolyte analysis method and an electrolyte analyzer.

  2. Description of the Related Art Conventionally, an electrolyte analyzer using an ion selective electrode is known as a device for measuring an electrolyte concentration such as urine and serum. As such an apparatus, an electromotive force of a diluted sample solution produced by diluting a sample with a diluent is measured using an ion selective electrode and a reference electrode, and an electromotive force of a reference liquid for comparison is measured. Measure. Then, based on the measurement data of each of the diluted sample solution and the reference solution, the electrolyte concentration that is the component to be measured contained in the diluted sample solution is measured.

  Specifically, first, a sample such as urine or serum is diluted in a dilution container, and the diluted diluted sample solution is guided to an electrode portion where an ion selective electrode is used, corresponding to the electrolyte concentration of the sample. Measure the electromotive force. Subsequently, the diluted internal standard solution is guided to the electrode section through the dilution container, and the electromotive force of the diluted internal standard solution is measured. And the electrolyte concentration of a sample is calculated | required from the difference of the electromotive force of the sample mentioned above and the electromotive force of an internal standard solution (for example, refer the following patent document 1). Since this method always performs measurements with reference to the diluted internal standard solution, it is less susceptible to temperature fluctuations than the conventional method of measuring a diluted internal standard solution filled in a bottle. have.

Japanese Patent Laid-Open No. 10-62375

  However, in such an electrolyte analyzer, when the output of the electrode suddenly decreases, the change follows the change, so that an abnormality cannot be detected and an inaccurate analysis result is output. The problem was happening. Further, in the conventional electrolyte analyzer, since a plurality of (for example, three) syringes (pumps) are used to discharge the sample and the diluted solution, three motors are required, and noise and heat generation from the motor, etc. As a result, there was also a problem of causing measurement abnormality.

  In order to eliminate the above-mentioned problems caused by the prior art, the present invention obtains the dilution ratio of the diluted internal standard solution in advance and refers to the value each time, so that the fluctuation is within the normal range. It is an object of the present invention to provide an electrolyte analysis method and an electrolyte analysis apparatus that can determine whether the battery is abnormal or abnormal.

In order to solve the above-described problems and achieve the object, an electrolyte analysis method according to the present invention includes a sample supply step for supplying a sample to a dilution container, and a predetermined amount of a component to be measured previously in the dilution container. A diluent supplying step for supplying a diluent added with a salt containing ions, a sample dilution step for mixing the sample supplied to the dilution container and the diluent to generate a diluted sample solution, and A diluted sample measurement step of measuring the electrolyte concentration as a component to be measured contained in the diluted sample solution while taking out the diluted sample solution from the dilution vessel; and an internal standard solution supplying step of supplying an internal standard solution to the dilution vessel; An internal standard solution diluting step for producing a diluted internal standard solution by mixing the internal standard solution supplied to the diluting vessel and the diluting solution supplied to the diluting vessel in the diluting solution supplying step; Said rare And diluting the internal standard solution measurement process which measures the electrolyte concentration to be measured component contained in the dilution internal standard solution the dilutions internal standard solution with extraction of the use container,
A calculation step of calculating a dilution rate of the diluted internal standard solution, a determination step of determining whether or not the dilution rate of the diluted internal standard solution calculated in the calculation step is within a predetermined range, at the determination step, when the dilution ratio of the dilution internal standard solution is determined not within the predetermined range set in advance, early days including a notification control step of outputting the information to the effect that reporting predetermined abnormality, the And features.

  According to the present invention, a dilution liquid measurement step for measuring an electrolyte concentration as a component to be measured contained in the dilution liquid while taking out only the dilution liquid is added using the dilution liquid supply process, and the dilution ratio of the internal standard liquid is added. Thus, the detection of abnormal values can be facilitated.

  According to the present invention, when the dilution rate is not within the predetermined range set in advance, it can be notified that it is abnormal.

The electrolyte analysis method according to the present invention includes a sample supply step for supplying a sample to a dilution container, and a dilution liquid in which a salt containing a certain amount of the same ion as the component to be measured is added to the dilution container in advance. A diluent supply step to be supplied; a sample dilution step in which the sample supplied to the dilution container and the diluent are mixed to produce a diluted sample solution; and taking out the diluted sample solution in the dilution container A diluted sample measuring step for measuring an electrolyte concentration as a component to be measured contained in the diluted sample solution, an internal standard solution supplying step for supplying an internal standard solution to the dilution vessel, and the internal supplied to the dilution vessel An internal standard solution diluting step of mixing the standard solution and the diluting solution supplied to the diluting vessel in the diluting solution supplying step to generate a diluting internal standard solution, and the diluting internal standard solution in the diluting vessel Take out While the dilution internal standard solution measurement process which measures the electrolyte concentration to be measured component contained in the dilution internal standard solution, a calculation step of calculating a dilution ratio of the dilution internal standard solution, the diluted sample measuring step or the diluting And a dilution container cleaning step for cleaning using a diluted internal standard solution as a cleaning solution after the internal standard solution measuring step .

  According to this invention, the measurement electromotive force change of the electrode for electrolyte concentration measurement can be suppressed, the responsiveness of the electrode can be improved, and a more stable measurement result can be obtained.

The electrolyte analysis method according to the present invention includes a sample supply step for supplying a sample to a dilution container, and a dilution liquid in which a salt containing a certain amount of the same ion as the component to be measured is added to the dilution container in advance. A diluent supply step to be supplied; a sample dilution step in which the sample supplied to the dilution container and the diluent are mixed to produce a diluted sample solution; and taking out the diluted sample solution in the dilution container A diluted sample measuring step for measuring an electrolyte concentration as a component to be measured contained in the diluted sample solution, an internal standard solution supplying step for supplying an internal standard solution to the dilution vessel, and the internal supplied to the dilution vessel An internal standard solution diluting step of mixing the standard solution and the diluting solution supplied to the diluting vessel in the diluting solution supplying step to generate a diluting internal standard solution, and the diluting internal standard solution in the diluting vessel Take out While containing a diluent internal standard solution measurement process which measures the electrolyte concentration to be measured component contained in the dilution internal standard solution, and a calculation step of calculating a dilution ratio of the dilution internal standard solution, the internal standard solution supplied the process according to the electrolyte concentration in advance is set for each component to be measured in the diluted sample solution, and the supply amount of the internal standard solution into a variable, to supply dilution internal standard solution close to the electrolyte concentration of the diluted sample solution Features.

  According to this invention, the difference in the measured electromotive force can be suppressed, the influence on the measurement result due to temperature fluctuation can be suppressed, and the responsiveness of the electrode can be enhanced, thereby obtaining a more stable measurement result.

Moreover, the electrolyte analyzer according to the present invention mixes a sample or internal standard solution with a diluted solution in which a certain amount of a salt containing the same ion as the component to be measured is added in advance, and uses the diluted sample solution or diluted internal standard solution. A dilution container for generating, a sample supply means for supplying the sample to the dilution container, an internal standard solution supply means for supplying the internal standard solution to the dilution container, and the dilution to the dilution container A diluent supply means for supplying the solution, and the diluted sample solution, the diluted internal standard solution or the diluted solution in the dilution container, while the diluted sample solution, the diluted internal standard solution or the solution contained in the diluted solution is removed. measuring means for measuring the electrolyte concentration is measured component, and calculating means for calculating a dilution ratio of the dilution internal standard solution, dilution ratio of the dilution internal standard solution calculated by said calculating means in advance A determination unit that determines whether or not the predetermined internal range is within a predetermined range, and a notification of a predetermined abnormality when the determination unit determines that the dilution factor of the diluted internal standard solution is not within a predetermined range. And a notification control means for outputting information to the effect .

  According to this invention, even when the analyzer outputs an abnormal value, the detection can be facilitated.

  According to the present invention, when the dilution rate is not within the predetermined range set in advance, it can be notified that it is abnormal.

Moreover, the electrolyte analyzer according to the present invention mixes a sample or internal standard solution with a diluted solution in which a certain amount of a salt containing the same ion as the component to be measured is added in advance, and uses the diluted sample solution or diluted internal standard solution. A dilution container for generating, a sample supply means for supplying the sample to the dilution container, an internal standard solution supply means for supplying the internal standard solution to the dilution container, and the dilution to the dilution container A diluent supply means for supplying the solution, and the diluted sample solution, the diluted internal standard solution or the diluted solution in the dilution container, while the diluted sample solution, the diluted internal standard solution or the solution contained in the diluted solution is removed. measuring means for measuring a measurement component electrolyte concentration, and calculating means for calculating a dilution ratio of the dilution internal standard solution, after measuring the diluted sample solution after measurement or dilution internal standard solution, diluted as cleaning fluid A diluent container washing means for cleaning Using parts standard solution, characterized in that it comprises a.

  According to this invention, the measurement electromotive force change of the electrode for electrolyte concentration measurement can be suppressed, the responsiveness of the electrode can be improved, and a more stable measurement result can be obtained.

Moreover, the electrolyte analyzer according to the present invention mixes a sample or internal standard solution with a diluted solution in which a certain amount of a salt containing the same ion as the component to be measured is added in advance, and uses the diluted sample solution or diluted internal standard solution. A dilution container for generating, a sample supply means for supplying the sample to the dilution container, an internal standard solution supply means for supplying the internal standard solution to the dilution container, and the dilution to the dilution container A diluent supply means for supplying the solution, and the diluted sample solution, the diluted internal standard solution or the diluted solution in the dilution container, while the diluted sample solution, the diluted internal standard solution or the solution contained in the diluted solution is removed. measuring means for measuring the electrolyte concentration is measured components, and a calculating means for calculating a dilution ratio of the dilution internal standard solution, the internal standard solution supplying means for each component to be measured in the diluted sample solution Depending on the electrolyte concentration to be fit set, and the supply amount of the internal standard solution into a variable, and supplying the diluting internal standard solution close to the electrolyte concentration that is assumed in the diluted sample solution.

  According to the present invention, the influence on the measurement result due to the temperature fluctuation can be suppressed and the responsiveness of the electrode can be enhanced to obtain a more stable measurement result.

Moreover, the electrolyte analyzer according to the present invention mixes a sample or internal standard solution with a diluted solution in which a certain amount of a salt containing the same ion as the component to be measured is added in advance, and uses the diluted sample solution or diluted internal standard solution. A dilution container for generating, a sample supply means for supplying the sample to the dilution container, an internal standard solution supply means for supplying the internal standard solution to the dilution container, and the dilution to the dilution container A diluent supply means for supplying the solution, and the diluted sample solution, the diluted internal standard solution or the diluted solution in the dilution container, while the diluted sample solution, the diluted internal standard solution or the solution contained in the diluted solution is removed. measuring means for measuring a measurement component electrolyte concentration, and calculating means for calculating a dilution ratio of the dilution internal standard solution, diluting liquid after measurement, diluting the internal standard solution after dilution sample solution or measurement after measurement Adjustment to adjust the operation timing of the waste liquid drive unit to be discharged, the dilution liquid supply drive unit to be used and the internal standard liquid supply drive unit, the waste liquid solenoid valve, the dilution liquid supply solenoid valve and the internal standard liquid supply solenoid valve e Bei means, wherein the waste drive unit, the diluent supply drive portion and the internal standard solution supply driving unit may be constituted by a single drive unit.

  According to the present invention, the number of parts can be reduced, the manufacturing cost can be reduced, and the heat generation of the motor which is compact and affects the measurement result can be suppressed.

  According to these inventions, even when the output of the electrode suddenly decreases, it can be determined whether the fluctuation is within the normal range or abnormal. Can be obtained. Further, by using a single motor, it is possible to provide an electrolyte analyzer that is inexpensive, simple, and suppresses heat generation of the motor.

  According to the present invention, when measuring sodium, potassium, chlorine, etc., by adding a predetermined amount of salt as a predetermined amount of salt in the diluent to be used so that a small amount of sodium ion, potassium ion, chlorine ion is present, It is possible to calculate the dilution factor of the internal standard solution at the time of calibration. Therefore, by referring to this calculated value as necessary, even when the output of the electrode suddenly drops, the operator can check whether the fluctuation is within the normal range or abnormal. Since it becomes possible to judge, a stable measurement result can always be obtained.

  In addition, the use of a single motor simplifies the structure, reduces equipment and manufacturing costs, reduces noise that tends to hinder electrolyte measurement, eliminates unnecessary waste heat, and reduces maintenance costs. It becomes possible. In particular, stable measurement results can be obtained by reducing noise and eliminating unnecessary waste heat.

  Also, depending on the specimen type, even if the difference in electromotive force between the diluted sample solution and the diluted internal standard solution is large, and it is easily affected by the responsiveness of electrodes and temperature fluctuations, if the specimen type is known in advance, Control the influence of temperature fluctuations on the measurement results by controlling the difference in measured electromotive force by supplying the diluted internal standard solution close to the expected concentration of the diluted sample solution by adjusting the amount of the internal standard solution. In addition, since the responsiveness of the electrode can be improved, a more stable measurement result can be provided.

  Further, by using the diluted internal standard solution for washing after measurement of the diluted sample solution, it is possible to improve the responsiveness of the electrode to the next measurement as compared with washing with a normal diluent.

  Exemplary embodiments of an electrolyte analysis method and an electrolyte analyzer according to the present invention will be explained below in detail with reference to the accompanying drawings.

  FIG. 1 is a configuration diagram of an electrolyte analyzer according to an embodiment of the present invention. The electrolyte analyzer 100 includes a sample supply unit 110, a diluent supply unit 120, a sample dilution unit 130, a measurement unit 140, a waste liquid unit 150, and an internal standard solution supply unit 160.

  The sample supply means 110 includes a movable crane 111 that can move in the vertical and horizontal directions in the drawing, and a sample dispensing nozzle 112 provided in the movable crane 111. The sample dispensing nozzle 112 is connected to the pipe 113. Although not shown, the sample supply unit 110 has a cleaning mechanism for cleaning the inner wall and the outer wall of the sample dispensing nozzle 112.

  A sample container 114 is provided in the middle of movement of the movable crane 111. In the sample container 114, a sample 115 such as urine or serum is accommodated. By moving the movable crane 111 and performing a suction operation, the sample dispensing nozzle 112 dispenses the sample 115 from the sample container 114 by a certain amount. The separated sample 115 is moved to the movable crane 111 and dispensed into the dilution container 131 of the sample dilution means 130. When the electrolyte analyzer of the present invention is provided as a unit of an automatic analyzer, the sample supply means 110 may be provided in the automatic analyzer body and is not always necessary.

  The diluent supply means 120 includes a diluent container 121, a diluent supply pump 122, a solenoid valve 123, a suction pipe 124, a pump connection pipe 125, a supply pipe 127, and a diluent supply nozzle 126. Has been. For the diluent, for example, tris (hydroxymethyl) aminomethane aqueous solution, monomethanolamine aqueous solution, diethanolamine aqueous solution, triethanolamine aqueous solution, sulfuric acid, phosphoric acid, boric acid buffer, etc., or good buffers such as MOPS, HEPES, etc. are used. It is done.

  In particular, in this embodiment, if these diluents are diluents used in analyzers that measure a certain amount of salt, such as sodium, potassium, and chlorine, sodium, potassium, and chlorine are 1% of the internal standard solution. Add to a concentration of about. For example, when the sodium concentration of the internal standard solution is 140 mmol / L, 1.4 mmol / L, when the potassium concentration of the internal standard solution is 4 mmol / L, 0.04 mmol / L, and the chlorine concentration of the internal standard solution is 100 mmol / L. If so, it is added to a concentration of 1 mmol / L. The internal standard solution is contained in the internal standard solution container 161, and is a liquid that serves as a reference for comparison when the sample 115 is measured.

  The dilution liquid delivery nozzle 126 delivers the dilution liquid toward the dilution container 131. By the operation of the dilution liquid supply pump 122, a predetermined amount of dilution liquid is collected from the dilution liquid container 121 through the suction pipe 124, and is sent to the dilution container 131. By diluting the sample 115 dispensed into the dilution container 131 with this diluted solution, a diluted sample solution diluted, for example, about 30 times is generated.

  A stirring mechanism 132 is provided inside the dilution container 131 of the sample dilution means 130. The stirring mechanism 132 mixes the sample 115 dispensed from the sample container 114 by a predetermined amount by the sample supply means 110 and the diluent sent from the diluent container 121 by the diluent supply means 120 by a predetermined amount, A homogeneous diluted sample solution is produced. A diluted sample solution or a diluted solution (also referred to as a diluted internal standard solution and these are called measurement solutions) is taken out from the dilution container 131 and sent out to the measuring means 140.

  The measuring unit 140 measures the measurement liquid supply pipe 141 connected to the dilution container 131, the plurality of electrode parts 142 (142a to 142d) provided on the path through which the measurement liquid passes, and the electromotive force of the electrode part 142. The electromotive force measurement unit 143 and the discharge pipe 144 through which the measurement liquid after passing through the electrode unit 142 passes are configured.

  The electrode unit 142 includes ion selective electrodes 142a to 142c and a comparison electrode 142d. The ion selective electrodes 142a to 142c are electrodes that output a potential difference sensitive to specific ions such as Na, K, and Cl, for example. The ion selective electrodes 142a to 142c and the comparison electrode 142d output the respective potentials of the measurement liquids taken out from the dilution container 131 and sent from the measurement liquid supply pipe 141. More specifically, the ion-selective electrodes 142a to 142c and the comparison electrode 142d are arranged such that when the measurement liquid sent from the measurement liquid supply pipe 141 passes through the electrode portion 142, each ion of the measurement liquid that passes therethrough. A predetermined potential difference between the selective electrodes 142a to 142c and the comparison electrode 142d is measured.

  The electromotive force measurement unit 143 measures the electromotive force of each of the diluted sample solution and the diluted internal standard solution that passes through the measurement solution supply pipe 141 through the electrode unit 142. That is, when the diluted sample solution is sent via the measurement solution supply pipe 141, the electromotive force measurement unit 143 has a potential difference between the potential indicated by the ion selective electrodes 142a to 142c and the potential indicated by the comparison electrode 142d. Measure. Further, when the diluted internal standard solution is sent via the measurement solution supply pipe 141, the potential difference between the potential indicated by the ion selective electrodes 142a to 142c and the potential indicated by the comparison electrode 142d is measured.

  Furthermore, when determining the dilution factor of the internal standard solution, only the diluted solution is sent to the electrode part 142, and the potential difference between the potential indicated by the ion selective electrodes 142a to 142c and the potential indicated by the comparison electrode 142d is measured.

Here, a method for calculating the dilution rate will be described. At the calibration curve creation stage, the concentration of the high-concentration standard solution is CH, the concentration of the low-concentration standard solution is CL, the concentration of the internal standard solution is CM, the concentration of the diluted solution is Cb, and S is the slope sensitivity of the measurement electrode and E0 is measured. The standard potential of the electrode, Sr is the slope sensitivity of the reference electrode, Er is the standard potential of the reference electrode, Cr is the concentration of the reference solution, r is the dilution ratio of the high concentration standard solution and the low concentration standard solution, and the internal standard solution is diluted When the magnification is rm,
The measurement potential difference EH between the measurement electrode of the diluted high concentration standard solution and the reference electrode is
EH = E0 + S · log (((r−1) · Cb + CH) / r) −Er−Sr · logCr (1) The measurement potential difference EL between the measurement electrode of the diluted low concentration standard solution and the reference electrode is
EL = E0 + S · log (((r-1) · Cb + CL) / r) −Er−Sr · logCr (2) The measurement potential difference EM between the measurement electrode of the diluted internal standard solution and the reference electrode is
EM = E0 + S * log (((rm-1) * Cb + CM) / rm) -Er-Sr * logCr (3) Formula (1) Formula-(3) Formula and (2) Formula-(3) From the above formula, the above formula is
EH-EM = S.log (((r-1) .Cb + CH) / r) -S.log (((rm-1) .Cb + CM) / rm) (4) Formula EL-EM = S. log (((r-1) .Cb + CL) / r) -S.log (((rm-1) .Cb + CM) / rm) (5) where the measurement of the diluted solution having the concentration Cb. Measurement of the potential difference Eb between the reference electrode and the reference electrode,
Eb = E0 + S · logCb−Er−Sr · logCr (6) From the formula (3) and the formula (6),
EM-Eb = S.log (((rm-1) .Cb + CM) / rm) -S.logCb (7) and S.log (((rm-1) .Cb + CM) / rm) = EM -Eb + S · logCb (8) By substituting Equation (8) into Equation (4) and Equation (5), S and r can be obtained. Further, the dilution factor rm of the internal standard solution is obtained from the equation (8) by using the obtained S and the actually measured value EM-Eb. Rm is calculated by measuring Eb during or between analyses, and if it deviates from a predetermined threshold value, it can be output as an abnormality.

Here, a specific example of calculating the dilution rate of the internal standard solution based on the measured potential difference is shown by sodium measurement. In the calibration curve creation stage, the concentration of the high concentration standard solution is 160 mmol / L, the concentration of the low concentration standard solution is 130 mmol / L, the concentration of the internal standard solution is 140 mmol / L, the concentration of the diluted solution is 1.4 mmol / L, S Is the slope sensitivity, the dilution ratio of the high-concentration standard solution and the low-concentration standard solution is r, and the dilution ratio of the internal standard solution is rm,
The measurement potential difference between the diluted high concentration standard solution and the diluted internal standard solution is EH-EM = 2.2 mV
The measurement potential difference between the diluted low concentration standard solution and the diluted internal standard solution is EL-EM = −2.0 mV.
The measurement potential difference between the diluted internal standard solution and the diluted solution is EM-Eb = 37 mV
If
EH-EM = S * log (((r-1) * 1.4 + 160) / r) -S * log (((rm-1) * 1.4 + 140) / rm) = 2.2 (11) ) Formula EL-EM = S.log (((r-1) .1.4 + 130) / r) -S.log (((rm-1) .1.4 + 140) / rm) =-2.0 .. (12) Formula EM-Eb = S * log (((rm-1) * 1.4 + 140) / rm) -S * log1.4 = 37 (13) From Formula (13), S * log (((Rm−1) · 1.4 + 140) / rm) = 37 + S · log1.4 (14) Approximate value by substituting equation (14) into equation (11) and equation (12) S≈61.5 and r≈33.9 are obtained.
Substituting S = 61.5 into the equation (14), rm≈33.0 is obtained as an approximate value.

  The waste liquid means 150 includes a solenoid valve 151, a pump connection pipe 152, a waste liquid pump 153, a waste liquid pipe 154, and a waste liquid container 155. The solenoid valve 151 is connected to one end of the discharge pipe 144. One end of the pump connection pipe 152 is connected to the electromagnetic valve 151, and the other end is connected to the waste liquid pump 153. One end of the waste liquid pipe 154 is connected to the electromagnetic valve 151 and the other end is opened. A waste liquid container 155 for receiving the dropped waste liquid is installed at the lower part of the open end of the waste liquid pipe 154. The measurement liquid stored in the dilution container 131 by the operation of the waste liquid pump 153 is taken out so as to pass through the measurement means 140, measured by the measurement means 140, and then discharged to the waste liquid container 155.

  That is, the measurement liquid that has passed through the electrode part 142 passes through the discharge pipe 144 and is temporarily stored in the waste liquid pump 153 via the electromagnetic valve 151. Thereafter, by switching the electromagnetic valve 151, the waste liquid sent from the waste liquid pump 153 passes through the waste liquid pipe 154 and is discharged to the waste liquid container 155 via the electromagnetic valve 151.

  The internal standard liquid supply means 160 includes an internal standard liquid container 161, an internal standard liquid supply pump 162, a solenoid valve 163, a suction pipe 164, a pump connection pipe 165, a supply pipe 167, and an internal standard liquid delivery nozzle. 166. By switching the solenoid valve 163 to the supply pipe 167 side, a predetermined amount of the internal standard solution in the internal standard solution container 161 can be supplied from the internal standard solution delivery nozzle 166.

  The supplied internal standard solution is diluted at a predetermined dilution rate in the dilution container 131 by the diluent supply means 120 and used as a diluted internal standard solution for measurement. The internal standard solution supply means 160 is also used for cleaning the sample dilution means 130 and the measurement means 140 after measurement of the diluted sample solution.

  FIG. 2 is a block diagram showing a control unit used in the present embodiment. The control unit 200 includes a microcomputer system, and includes a drive control unit 201, a measurement processing unit 202, and a timer 203.

  Based on the input information from the operation unit 210, the drive control unit 201 uses a previously stored program to move the movable crane 111, the electromagnetic valve 123, the diluent supply pump 122, the electromagnetic valve 163, and the internal standard. The liquid supply pump 162, the electromagnetic valve 151, and the waste liquid pump 153 are driven and controlled. Specifically, the drive control unit 201 determines the position of the movable crane 111 and sends a control signal to a moving mechanism (not shown), so that the moving mechanism moves in the X direction shown in FIG. The dispensing nozzle 112 is moved to a predetermined position. Further, the drive control unit 201 sends a valve switching signal to the electromagnetic valve 123, the electromagnetic valve 151, and the electromagnetic valve 163, and supplies the dilution liquid supply pump 122, the waste liquid pump 153, and the internal standard liquid supply pump 162. Sends an operation control signal.

  The measurement processing unit 202 receives the electromotive force measured by the electromotive force measurement unit 143, measures the electrolyte concentration of the diluted sample solution, and displays the measurement result on the display unit 220 such as a display. Specifically, the measurement processing unit 202, based on the electromotive force measured by the electromotive force measurement unit 143, the components to be measured (Na, K, Cl contained in the diluted sample solution sent from the measurement liquid supply pipe 141) ) Is measured, and the numerical value of each component is displayed on the display unit 220.

  In addition, the measurement processing unit 202 constantly monitors the measurement result by calculating the dilution factor of the internal standard solution via the electromotive force measurement unit 143, and if an abnormality is recognized, the display unit 220 is abnormal. Is displayed to prevent the use of incorrect measurement results. The measurement processing unit 202 corresponds to the calculation unit, determination unit, and notification control unit of the present invention.

  The timer 203 measures the time after the end of measurement. For example, measurement is started for each measurement of the measurement liquid. The timer 203 starts measuring time when information on the end of one measurement of the measurement liquid is sent from the measurement processing unit 202. When a predetermined time elapses, the timer 203 sends time-up measurement information to the drive control unit 201. To send. When time-up measurement information is input, the drive control unit 201 enters a standby state where no measurement is performed.

  FIGS. 3A and 3B are flowcharts illustrating a schematic example of the calibration process according to the present embodiment. 3A and 3B, the control unit 200 determines whether to perform calibration (step S101). The start of calibration is started by an operation input for starting measurement by the operation unit 210. When calibration is not performed (step S101: No), the process proceeds to a measurement process described later in FIG. When calibration is started (step S101: Yes), the diluent in the diluent container 121 is sent to the dilution container 131 according to an instruction from the drive control unit 201 (step S102). This diluted solution is guided to the electromotive force measuring unit 143, and the electromotive force is measured (step S103). After the measurement is completed, the diluted solution is discharged (Step S104).

  Next, the diluent in the diluent container 121 is delivered to the dilution container 131 (step S105). The internal standard solution supply means 160 that has received the internal standard solution discharge amount information from the control unit 200 sends the internal standard solution to the dilution container 131 based on the discharge amount information (step S106). Next, the diluted solution and internal standard solution in the dilution container 131 are stirred by the stirring mechanism 132 to generate a diluted internal standard solution (step S107). This diluted internal standard solution is guided to the electromotive force measuring unit 143, and the electromotive force is measured (step S108). After completion of the measurement, the diluted internal standard solution is discharged (step S109).

  Next, the diluent in the diluent container 121 is sent to the dilution container 131 (step S110), and the high-concentration standard solution in the sample container 114 is dispensed into the dilution container 131 (step S111). Then, the diluted solution and the high-concentration standard solution in the dilution container 131 are stirred by the stirring mechanism 132 to generate a diluted high-concentration standard solution (step S112). The diluted high concentration standard solution is guided to the electromotive force measuring unit 143, the electromotive force is measured (step S113), and the diluted high concentration standard solution is discharged after the measurement is completed (step S114).

  Next, the electromotive force measurement of the diluted low concentration standard solution is performed in the same manner as in steps S110 to S114, and the diluted low concentration standard solution is discharged after the measurement is completed (step S115 to step S119). The measured electromotive force information is processed by the measurement processing unit 202 of the control unit 200, and the slope of the electrode and the dilution rate of each standard solution are calculated (step S120). The validity of the calculated slope and dilution factor is determined based on information set in advance by the measurement processing unit 202 (step S121). If valid (step S121: Yes), the calibration process is terminated, The measurement process described later in FIG.

  In addition, when it is determined that it is not appropriate (step S121: No), the necessity of maintenance is determined again based on information set in advance by the measurement processing unit 202 (step S122). (S122: Yes), the measurement is stopped, maintenance is performed (step S123), and the process proceeds to step S101. If it is determined that maintenance is not necessary (step S122: No), the process proceeds to step S102 in order to perform calibration again.

  FIG. 3C and FIG. 3D are flowcharts illustrating a schematic example of the measurement process in the present embodiment. In FIGS. 3-3 and 3-4, the control unit 200 determines whether or not the sample measurement is started (step S124). The sample measurement is started by an operation input for starting measurement by the operation unit 210, and is on standby until that time (step S124: No loop). When the measurement is started (step S124: Yes), the diluent in the diluent container 121 is sent to the dilution container 131 in accordance with an instruction from the drive control unit 201 (step S125). The internal standard liquid supply means 160 that has received the internal standard liquid discharge amount information from the control unit 200 sends the internal standard liquid to the dilution container 131 based on the discharge amount information (step S126).

  Next, the diluted solution and the internal standard solution in the dilution container 131 are stirred by the stirring mechanism 132 to generate a diluted internal standard solution (step S127). This diluted internal standard solution is guided to the electromotive force measuring unit 143, and the electromotive force is measured (step S128). After completion of the measurement, the diluted internal standard solution is discharged (step S129). Next, the diluent in the diluent container 121 is delivered to the dilution container 131 (step S130). Then, the sample in the sample container 114 is dispensed into the dilution container 131 (step S131). Then, the diluted solution and the sample in the dilution container 131 are stirred by the stirring mechanism 132 to generate a diluted sample solution (step S132). This diluted sample solution is guided to the electromotive force measurement unit 143, and the electromotive force is measured (step S133). After completion of the measurement, the diluted sample solution is discharged (step S134).

  Thereafter, the diluent in the diluent container 121 is sent to the dilution container 131 (step S135). The internal standard solution supply means 160 that has received the internal standard solution discharge amount information from the control unit 200 sends the internal standard solution to the dilution container 131 based on the discharge amount information (step S136). Next, the diluted solution and the internal standard solution in the dilution container 131 are stirred by the stirring mechanism 132 to generate a diluted internal standard solution (step S137). Since this diluted internal standard solution is used for cleaning the dilution container 131 and the electrode part 142, it is discharged without measuring the electromotive force (step S138). This contributes to stable measurement value calculation by improving the responsiveness of the electrodes by suppressing changes in the measured electromotive force of the ion selective electrodes 142a to 142c and the comparison electrode 142d rather than cleaning using only the diluent. Is possible.

  Based on these measurement results, the measurement processing unit 202 of the control unit 200 calculates the electrolyte concentration that is the component to be measured contained in the diluted sample solution (step S139), and the result is valid based on the preset information. Is determined (step S140). If the result is valid (step S140: Yes), if there is no schedule for the next sample measurement (step S141: No), the process is terminated. If there is a schedule for the next sample measurement (step S141: Yes), the process returns to the standby state in preparation for the measurement (step S124: No loop). If the result is not valid (step S140: No), if it is necessary to determine whether there is an abnormality in the apparatus, that is, if it is necessary to measure the dilution factor (step S142: Yes), the dilution factor measurement step (Steps S144 to S151) are performed, and the dilution factor is calculated by the measurement processing unit 202 of the control unit 200 (Step S152).

  Then, the validity is determined based on a preset threshold value, and if it is within the threshold value (step S153: Yes), the sample supply unit 110 may be abnormal. Therefore, the measurement is interrupted and the sample supply unit 110 is maintained. Is performed (step S154). When it deviates from a threshold value (step S153: No), a measurement is interrupted and the electrolyte analyzer 100 is maintained (step S155).

  If it is not necessary to measure the dilution rate in step S142 (step S142: No), it is determined whether or not the next sample measurement is scheduled (step S143). If there is no schedule for the next sample measurement (step S143: No), the process is terminated. If there is a schedule for the next sample measurement (step S143: Yes), it returns to the standby state in preparation for the measurement (step S124: No loop).

  In step S140, when the measurement result is not valid (step S140: No), the determination of the dilution factor (step S142) can be performed by the operator of the electrolyte analyzer 100, or the electrolyte analyzer 100 can be determined. It is also possible to judge.

  Details of the measurement of the diluted sample solution shown in FIGS. 3-3 and 3-4 will be described with reference to FIG. For convenience of explanation, it is assumed that the electromagnetic valve 123 connected to the suction pipe 124 is in a closed state. Further, as an initial state, it is assumed that the diluent is sent to the suction pipe 124 and exists in the suction pipe 124.

  From this state, the electromagnetic valve 123 is opened, and the diluent staying in the open supply pipe 127 is sent to the dilution container 131 through the diluent sending nozzle 126 by the operation of the diluent supply pump 122. To do.

  Next, an operation of sending the internal standard solution to the dilution container 131 is performed. As an initial state, it is assumed that the electromagnetic valve 163 connected to the suction pipe 164 is closed. From this state, the electromagnetic valve 163 is opened, and the internal standard solution staying in the supply pipe 167 that has been opened by the operation of the internal standard solution supply pump 162 is passed through the internal standard solution delivery nozzle 166 to the dilution container. Dispense into 131. Thereafter, the mixture is stirred by the stirring mechanism 132 to generate a diluted internal standard solution in which the internal standard solution and the diluted solution are uniformly mixed.

  Next, the diluted internal standard solution generated in the dilution container 131 is guided to the measurement solution supply pipe 141 by the suction operation of the waste solution pump 153. Then, the diluted internal standard solution passes through the electrode part 142 as a measurement solution. At this time, the electromotive force measurement unit 143 measures the potential difference of the diluted internal standard solution through the ion selective electrodes 142a to 142c and the comparison electrode 142d. Thereafter, the diluted internal standard solution is guided to the waste liquid container 155 and discarded.

  Thereafter, the electromotive force of the diluted sample solution is measured by the same process as the series of processes described above. Specifically, the sample dispensing nozzle 112 dispenses a predetermined amount of the sample 115 accommodated in the sample container 114, and dispenses the dispensed sample into the dilution container 131 to which the diluent is sent. . Thereafter, the sample is stirred by the stirring mechanism 132 to generate a diluted sample solution in which the sample and the diluent are uniformly mixed.

  Next, the diluted sample solution generated in the dilution container 131 is guided from the dilution container 131 to the measurement liquid supply pipe 141 by the suction operation of the waste liquid pump 153. At this time, the diluted sample solution passes through the electrode portion 142. At this time, the electromotive force measurement unit 143 measures the electromotive force of the diluted sample solution through the ion selective electrodes 142a to 142c and the comparison electrode 142d. Thereafter, the diluted sample solution is guided to the waste liquid container 155 and discarded.

  Then, the measurement processing unit 202 of the control unit 200 performs the measurement of the target contained in the diluted sample solution based on the electromotive force of the diluted sample solution and the electromotive force of the diluted internal standard solution measured by the electrode unit 142 and the electromotive force measuring unit 143. The concentration of electrolyte as a measurement component is calculated.

  Thereafter, the movable crane 111 moves, and the sample dispensing nozzle 112 is not shown, but is placed at the cleaning position. Then, the sample dispensing nozzle 112 is washed. On the other hand, the dilution container 131 is used as a cleaning liquid for washing the dilution container 131 by mixing and stirring the dilution liquid and the internal standard solution in the dilution container 131 in the same manner as the electromotive force measurement process for the internal standard solution described above. At the same time, the measuring means 140 is cleaned.

  If the control unit 200 determines that the dilution ratio of the internal standard solution needs to be measured after washing the dilution container, the dilution liquid supply pump is used in the same manner as the diluted sample solution generation process or the diluted internal standard solution generation process described above. 122, the dilution liquid is supplied to the dilution container 131, the electromotive force measurement unit 143 measures the electromotive force of only the dilution liquid, and calculates the difference between the electromotive force of the diluted internal standard solution and the dilution liquid, Used by the measurement processing unit 202 to calculate the dilution factor of the internal standard solution.

  If the measurement is performed after this, the above-described measurement process is repeated. In this way, one measurement by the electrolyte analyzer 100 is performed.

(Another example of electrolyte analyzer)
Next, another example of the electrolyte analyzer used in this embodiment will be described with reference to FIGS. FIG. 4 is a configuration diagram of the electrolyte analyzer when the three pumps in the electrolyte analyzer 100 of FIG. 1 are operated by a single motor. In addition, in the electrolyte analyzer 400 shown in FIG. 4, the same code | symbol is attached | subjected to the component similar to the electrolyte analyzer 100 shown in FIG. 1, and detailed description is abbreviate | omitted suitably. FIG. 5 is a timing chart of the electrolyte analyzer 100 shown in FIG. 1 and the electrolyte analyzer 400 shown in FIG.

  In FIG. 4, the electrolyte analyzer 400 includes a diluent supply pump 122 for supplying a diluent, an internal standard solution supply pump 162 for supplying an internal standard solution, and a measurement solution in the dilution container 131. Is connected to a waste liquid pump 153 that leads to the electromotive force measuring unit 143 and to the waste liquid container 155 by a single drive plate 171, and this drive plate 171 is configured to be driven by a single motor. Yes.

  When the diluted sample solution is generated, the drive valve 171 descends from the initial position to the lowest point with the solenoid valves 123, 151 and 163 closed (see reference numeral 501 in FIG. 5), and then the solenoid valve 123 is opened. Then, the drive plate 171 moves up (see reference numeral 502 in FIG. 5) until the diluent supply pump 122 discharges the required amount of diluent, and only the diluent is guided to the dilution container 131. When a necessary amount of the diluent is discharged, the solenoid valve 123 is closed, the drive plate 171 is raised to the initial position, and the excess diluent is returned to the diluent container 121.

  On the other hand, the sample dispensing nozzle 112 dispenses a predetermined amount of the sample 115 accommodated in the sample container 114, and dispenses the dispensed sample 115 into the dilution container 131 to which the diluent is sent. Thereafter, the sample is stirred by the stirring mechanism 132 to generate a diluted sample solution in which the sample 115 and the diluent are uniformly mixed.

  Next, when the diluted internal standard solution is generated, the drive plate 171 descends from the initial position to the lowest point with the solenoid valves 123, 151, and 163 closed (see reference numeral 511 in FIG. 5). 163 is opened, and the drive plate 171 rises until a required amount of internal standard solution with a small discharge amount is discharged (see reference numeral 512 in FIG. 5). Then, after closing only the solenoid valve 163, the drive plate 171 is further raised, and after the required amount of diluent is discharged, the solenoid valve 123 is closed, and the excess diluent and the internal standard solution are stored in their respective containers (diluents). It is returned to the container 121 and the internal standard solution container 161). Thereafter, the mixture is stirred by the stirring mechanism 132 to generate a diluted internal standard solution in which the internal standard solution and the diluted solution are uniformly mixed.

  When the measurement liquid (diluted sample solution or diluted internal standard solution) supplied to the dilution container 131 is guided to the electromotive force measurement unit 143, the measurement liquid is measured for electromotive force with the solenoid valves 123, 151, and 163 closed. The drive plate 171 descends until the ion selective electrodes 142a to 142c and the comparison electrode interior 142d of the part 143 are filled (see reference numerals 503 and 513 in FIG. 5), and after measuring the electromotive force of the measurement liquid, the drive plate 171 is at the bottom. The measurement liquid is lowered to the point (see reference numerals 504 and 514 in FIG. 5), and all the measurement liquid is introduced into the waste liquid pump 153. Thereafter, the electromagnetic valve 151 is opened, and the measurement liquid is guided to the waste liquid container 155.

  When performing the operation of guiding the measurement liquid to the electromotive force measurement unit 143, the suction operation for discharging the diluted sample or the diluted liquid for measuring the diluted internal standard solution and the internal standard solution is also performed in parallel (FIG. 5). No. 501, 511). Further, when the measurement liquid is guided to the waste liquid container 155, the operation of leading the dilution liquid or the dilution liquid and the internal standard liquid to the dilution container 131 is also performed in parallel (see symbols 502 and 512 in FIG. 5).

  As described above, the electrolyte analyzer 400 shown in FIG. 4 adjusts the operation timing of each electromagnetic valve and drives the three pumps by one motor. Similar to the electrolyte analyzer 100, not only can the sample be analyzed, but also heat generation and noise from the motor can be minimized, and stable analysis can be performed. Moreover, according to such an electrolyte analyzer 400, the cost of the apparatus can be reduced.

  Next, the relationship between the electrode potential and time of the electrolyte analyzer 100 (400) according to the present embodiment will be described with reference to FIGS. FIG. 6 is a graph showing the relationship between the electrode potential and time when a diluent is used as the cleaning liquid used for cleaning the dilution container 131 and the measuring means 140 after the sample solution measurement. The electrode potential M indicates the potential when measuring the diluted internal standard solution. The electrode potential S indicates the potential when measuring the diluted sample solution. The electrode potential W indicates the potential at the time of cleaning. In FIG. 6, since the electrode potential W at the time of washing is extremely low compared to the sample solution or the diluted internal standard solution, the potential difference of the diluted internal standard solution to be measured next is large and the response becomes dull. There is a tendency. This is the same even when the diluted sample solution is measured before the diluted internal standard solution regardless of the order of measurement.

  FIG. 7 is a graph showing the relationship between the electrode potential and time when a diluted internal standard solution is used as the cleaning solution used for cleaning the dilution container 131 and measuring unit 140 after the sample solution measurement. In FIG. 7, since the diluted internal standard solution is used as the cleaning solution, the electrode response is very good with almost no potential difference between the electrode potential W at the time of cleaning and the electrode potential M of the diluted internal standard solution in the next measurement. It shows that it is fast.

  These phenomena in FIG. 6 and FIG. 7 are also related to the response speed of the electrode when the specimen type changes like urine measurement after serum measurement. For example, when a urine measurement request is received after serum measurement, By increasing the supply amount of the internal standard solution from the internal standard solution supply pump 162 to the dilution container 131 and increasing the concentration of the diluted internal standard solution, the electrode potential M during the diluted internal standard solution measurement and the diluted sample solution measurement It is possible to suppress the difference from the electrode potential S of the electrode, increase the responsiveness of the electrode, and calculate a stable measurement result. Furthermore, due to the characteristics of the ion selective electrodes 142a to 142c, the smaller the difference between the electrode potential M and the electrode potential S, the less affected by temperature fluctuations, and the more stable measurement results can be calculated.

  As described above, according to the present embodiment, after the measurement of the diluted sample or the diluted internal standard solution, the cleaning is performed using the diluted internal standard solution as the cleaning solution. Therefore, the measurement of the electrolyte concentration measuring electrode is performed. It is possible to suppress changes in electromotive force, increase the responsiveness of the electrodes, and obtain more stable measurement results.

  FIG. 8 is a table showing the relationship between the concentration of the internal standard solution and the dilution factor and the threshold values according to this embodiment. In the table 800, an assumed sample concentration 801 is an assumed electrolyte concentration of the diluted sample solution. The internal standard solution volume 802 is a volume when a diluted internal standard solution is generated for each electrolyte concentration of the assumed sample concentration 801. The normal dilution factor 803 is a factor for diluting the diluted internal standard solution. The internal standard solution concentration 804 is an electrolyte concentration when the internal standard solution amount 802 is diluted at a normal dilution ratio 803. A threshold lower limit 805 indicates a lower limit value of the dilution rate. A threshold upper limit 806 indicates the upper limit of the dilution factor.

  By using such a table 800, it is possible to supply a diluted internal standard solution close to the electrolyte concentration of the diluted sample solution by changing the supply amount of the internal standard solution according to each electrolyte concentration of the assumed sample concentration 801. It is. Further, such a table 800 is used, for example, when determining whether or not it is within a threshold in step S153 of FIG. 3-4. Specifically, in step S153 of FIG. 3-4, the values of the threshold lower limit 805 and the threshold upper limit 806 of the table 800 are used.

  Thus, according to the present embodiment, in the supply of the internal standard solution, the supply amount of the internal standard solution is made variable according to the electrolyte concentration of the component to be measured, and the diluted internal standard close to the electrolyte concentration of the diluted sample solution Since the liquid is supplied, the difference in measurement electromotive force is suppressed, the influence on the measurement result due to temperature fluctuation is suppressed, and the responsiveness of the electrode is enhanced, so that a more stable measurement result can be obtained.

  As described above, according to the present embodiment, for example, when measuring sodium, potassium, chlorine, etc., such a salt is diluted by a certain amount so that a trace amount of sodium ion, potassium ion, chlorine ion is present. Since it is added to the solution, the dilution rate of the internal standard solution can be calculated at the time of calibration. Therefore, by referring to this value as necessary, even when the output of the electrode suddenly drops, the operator can determine whether the fluctuation is within the normal range or abnormal. Therefore, stable measurement results can always be obtained.

  As described above, the electrolyte analysis method and the electrolyte analyzer according to the present invention are useful for stable measurement of the electrolyte concentration of a sample such as urine and serum.

It is a block diagram of the electrolyte analyzer concerning embodiment of this invention. It is a block diagram which shows the control part used for this Embodiment. It is a flowchart which shows the schematic example of the calibration process in this Embodiment. It is a flowchart which shows the schematic example of the calibration process in this Embodiment. It is a flowchart which shows the schematic example of the measurement process in this Embodiment. It is a flowchart which shows the schematic example of the measurement process in this Embodiment. It is a block diagram of the electrolyte analyzer at the time of operating three pumps in the electrolyte analyzer of FIG. 1 with a single motor. 5 is a timing chart of the electrolyte analyzer shown in FIG. 1 and the electrolyte analyzer shown in FIG. 4. It is the graph which showed the relationship between an electrode potential and time at the time of using a diluent for the washing | cleaning liquid used for the washing | cleaning of the container for dilution after a sample solution measurement, and the washing | cleaning of a measurement means. It is the graph which showed the relationship between an electrode potential and time at the time of using a dilution internal standard solution for the washing | cleaning liquid used for the washing | cleaning of the container for dilution after a sample solution measurement, and the washing | cleaning of a measurement means. It is a graph which shows the relationship between the density | concentration of the internal standard solution concerning this Embodiment, a dilution rate, and a threshold value.

Explanation of symbols

DESCRIPTION OF SYMBOLS 100 Electrolyte analyzer 110 Sample supply means 112 Sample dispensing nozzle 120 Dilution liquid supply means 122 Dilution liquid supply pump 123 Solenoid valve 126 Dilution liquid delivery nozzle 130 Sample dilution means 131 Dilution container 140 Measurement means 142 Electrode part 143 Electromotive force measurement Unit 150 Waste liquid means 151 Electromagnetic valve 153 Waste liquid pump 160 Internal standard liquid supply means 162 Internal standard liquid supply pump 163 Electromagnetic valve 171 Drive plate 200 Control section 201 Drive control section 202 Measurement processing section 203 Timer 400 Electrolyte analyzer

Claims (7)

A sample supply step for supplying the sample to the dilution container;
A diluent supply step of supplying a dilution solution in which a salt containing the same ions as the component to be measured is previously added to the dilution container ;
A sample dilution step of mixing the sample supplied to the dilution container and the diluent to generate a diluted sample solution;
A diluted sample measurement step of measuring an electrolyte concentration as a component to be measured contained in the diluted sample solution while taking out the diluted sample solution from the dilution container;
An internal standard solution supplying step for supplying the internal standard solution to the dilution container;
An internal standard solution diluting step for producing a diluted internal standard solution by mixing the internal standard solution supplied to the diluting vessel and the diluting solution supplied to the diluting vessel in the diluting solution supplying step;
A diluted internal standard solution measuring step for measuring an electrolyte concentration which is a component to be measured contained in the diluted internal standard solution while taking out the diluted internal standard solution from the dilution container;
A calculation step of calculating a dilution ratio of the diluted internal standard solution;
A determination step of determining whether or not the dilution ratio of the diluted internal standard solution calculated in the calculation step is within a preset predetermined range;
A notification control step of outputting information to notify a predetermined abnormality when it is determined in the determination step that the dilution factor of the diluted internal standard solution is not within a predetermined range set in advance;
The electrolyte analysis wherein the early days including the. A sample supply step for supplying the sample to the dilution container;
A diluent supply step of supplying a dilution solution in which a salt containing the same ions as the component to be measured is previously added to the dilution container;
A sample dilution step of mixing the sample supplied to the dilution container and the diluent to generate a diluted sample solution;
A diluted sample measurement step of measuring an electrolyte concentration as a component to be measured contained in the diluted sample solution while taking out the diluted sample solution from the dilution container;
An internal standard solution supplying step for supplying the internal standard solution to the dilution container;
An internal standard solution diluting step for producing a diluted internal standard solution by mixing the internal standard solution supplied to the diluting vessel and the diluting solution supplied to the diluting vessel in the diluting solution supplying step;
A diluted internal standard solution measuring step for measuring an electrolyte concentration which is a component to be measured contained in the diluted internal standard solution while taking out the diluted internal standard solution from the dilution container;
A calculation step of calculating a dilution ratio of the diluted internal standard solution;
After the diluted sample measurement step or the diluted internal standard solution measurement step, a dilution container washing step for washing using a diluted internal standard solution as a washing solution ,
It characterized electrolytic electrolyte analyzing method comprises a. A sample supply step for supplying the sample to the dilution container;
A diluent supply step of supplying a dilution solution in which a salt containing the same ions as the component to be measured is previously added to the dilution container;
A sample dilution step of mixing the sample supplied to the dilution container and the diluent to generate a diluted sample solution;
A diluted sample measurement step of measuring an electrolyte concentration as a component to be measured contained in the diluted sample solution while taking out the diluted sample solution from the dilution container;
An internal standard solution supplying step for supplying the internal standard solution to the dilution container;
An internal standard solution diluting step for producing a diluted internal standard solution by mixing the internal standard solution supplied to the diluting vessel and the diluting solution supplied to the diluting vessel in the diluting solution supplying step;
A diluted internal standard solution measuring step for measuring an electrolyte concentration which is a component to be measured contained in the diluted internal standard solution while taking out the diluted internal standard solution from the dilution container;
A calculation step of calculating a dilution ratio of the diluted internal standard solution;
Including
In the internal standard solution supplying step, the supply amount of the internal standard solution is made variable according to the electrolyte concentration set in advance for each measured component of the diluted sample solution, and the diluted internal standard solution close to the electrolyte concentration of the diluted sample solution to that electrolytic electrolyte analysis method characterized by supplying. A dilution container for generating a diluted sample solution or diluted internal standard solution by mixing a sample or internal standard solution with a predetermined amount of a diluted solution containing a salt containing the same ion as the component to be measured in advance,
Sample supply means for supplying the sample to the dilution container;
An internal standard solution supply means for supplying the internal standard solution to the dilution container;
A diluent supply means for supplying the diluent to the dilution container;
Measurement for measuring the concentration of an electrolyte that is a component to be measured contained in the diluted sample solution, the diluted internal standard solution or the diluted solution while taking out the diluted sample solution, the diluted internal standard solution or the diluted solution in the dilution container Means,
A calculating means for calculating a dilution ratio of the diluted internal standard solution;
Determining means for determining whether or not the dilution ratio of the diluted internal standard solution calculated by the calculating means is within a predetermined range set in advance;
A notification control means for outputting information for notifying a predetermined abnormality when the determination means determines that the dilution factor of the diluted internal standard solution is not within a predetermined range set in advance;
An electrolyte analyzer characterized by comprising: A dilution container for generating a diluted sample solution or diluted internal standard solution by mixing a sample or internal standard solution with a predetermined amount of a diluted solution containing a salt containing the same ion as the component to be measured in advance,
Sample supply means for supplying the sample to the dilution container;
An internal standard solution supply means for supplying the internal standard solution to the dilution container;
A diluent supply means for supplying the diluent to the dilution container;
Measurement for measuring the concentration of an electrolyte that is a component to be measured contained in the diluted sample solution, the diluted internal standard solution or the diluted solution while taking out the diluted sample solution, the diluted internal standard solution or the diluted solution in the dilution container Means,
A calculating means for calculating a dilution ratio of the diluted internal standard solution;
A dilution container cleaning means for cleaning using a diluted internal standard solution as a cleaning solution after measuring a diluted sample solution or after measuring a diluted internal standard solution ,
The electrolyte analyzing apparatus, characterized in that it comprises a. A dilution container for generating a diluted sample solution or diluted internal standard solution by mixing a sample or internal standard solution with a predetermined amount of a diluted solution containing a salt containing the same ion as the component to be measured in advance,
Sample supply means for supplying the sample to the dilution container;
An internal standard solution supply means for supplying the internal standard solution to the dilution container;
A diluent supply means for supplying the diluent to the dilution container;
Measurement for measuring the concentration of an electrolyte that is a component to be measured contained in the diluted sample solution, the diluted internal standard solution or the diluted solution while taking out the diluted sample solution, the diluted internal standard solution or the diluted solution in the dilution container Means,
A calculating means for calculating a dilution ratio of the diluted internal standard solution;
With
The internal standard solution supply means varies the supply amount of the internal standard solution according to the electrolyte concentration set in advance for each component to be measured of the diluted sample solution, thereby diluting the diluted sample solution close to the assumed electrolyte concentration. you and supplying the internal standard solution electrolytic electrolyte analyzer. A dilution container for generating a diluted sample solution or diluted internal standard solution by mixing a sample or internal standard solution with a predetermined amount of a diluted solution containing a salt containing the same ion as the component to be measured in advance,
Sample supply means for supplying the sample to the dilution container;
An internal standard solution supply means for supplying the internal standard solution to the dilution container;
A diluent supply means for supplying the diluent to the dilution container;
Measurement for measuring the concentration of an electrolyte that is a component to be measured contained in the diluted sample solution, the diluted internal standard solution or the diluted solution while taking out the diluted sample solution, the diluted internal standard solution or the diluted solution in the dilution container Means,
A calculating means for calculating a dilution ratio of the diluted internal standard solution;
A waste liquid drive unit for discharging a diluted solution after measurement, a diluted sample solution after measurement or a diluted internal standard solution after measurement, a diluent supply drive unit to be used, and an internal standard solution supply drive unit;
Adjusting means for adjusting the operation timing of the solenoid valve for waste liquid, the solenoid valve for dilution liquid supply, and the solenoid valve for internal standard liquid supply;
Bei to give a,
The waste drive unit, the diluent supply drive portion and the internal standard solution supply drive unit, electrolytic electrolyte analyzer characterized in that it is constituted by a single drive unit.

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