CN108896629B - Three-point flow type calibration device and method for sodium ion concentration meter - Google Patents
Three-point flow type calibration device and method for sodium ion concentration meter Download PDFInfo
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Abstract
The invention relates to a sodium ion concentrationThe method and the device realize the consistency of the sodium ion concentration meter in the calibration and measurement process conditions; the method and the device calculate sodium ions C inevitably brought in by various reasons in the whole processsTo the prepared calibration solution C1、C2Performing calculation calibration, and then using a standard solution (C)1+Cs)、(C2+Cs) Calibrating a sodium ion concentration meter; the method and the device scientifically solve the problems of a two-point calibration method and a standard addition calibration method, and are easy to operate.
Description
Technical Field
The invention relates to a sodium ion concentration meter, in particular to a three-point flow type calibration method of the sodium ion concentration meter.
Background
The sodium ion concentration meter is an on-line chemical analysis meter, is applied to the fields of electric power, petrifaction and the like, and is mainly used for monitoring the sodium ion concentration of boiler feed water, condensed water, saturated steam, superheated steam and the like of a power plant. The sodium ion content of the water sample in the production process can be continuously monitored, the method is suitable for the use environment of an industrial field, and the actual requirements of maintenance personnel are met. The sodium ion concentration meter must be calibrated before measuring the sodium ion concentration, and the sodium ion concentration meter is accurately calibrated and the sodium ion concentration is accurately measured.
The sodium ion concentration meter consists of a sensor, an intelligent high-resistance millivoltmeter, a control panel, a chemical flow path system and the like. The sensor of the sodium ion concentration meter consists of a sodium ion selective electrode, a reference electrode, a temperature electrode and a water sample in a measuring cell, also called as a measuring cell, and the relationship between the electromotive force of the measuring cell and the sodium ion concentration in the water sample conforms to the Nernst equation:
E＝E0+S(T/298.15)lgC/Ciso
where E-measuring the cell electromotive force;
E0the potential of the equipotential point, which does not vary with temperature, is calibrated E0Is a determined value;
c is the sodium ion concentration of the water sample;
Ciso-the sodium ion concentration of the isoelectric point is a determined value for the determined electrode;
s-conversion slope, the value has corresponding relation with the performance of the sodium ion selective electrode and the reference electrode, and S is a determined value after calibration;
t is the temperature of the water sample.
1. Sodium ion concentration measurement: according to the Nernst equation, at known E0、S、CisoUnder the condition of (1), a sodium ion concentration meter measures the potential value E and the water sample temperature T of the measured water sample, and the Nernst equation is used, wherein E is E0+S(T/298.15)lgC/CisoAnd C is solved.
2. And (3) calibrating a sodium ion concentration meter: according to the Nernst equation, under the condition of known C, a sodium ion concentration meter measures the potential value E of a standard water sample, and the Nernst equation is used for: e ═ E0+S(T/298.15)lgC/CisoSolving for E0And S.
When calibrated, two (or more) standard solutions (e.g. C) of known sodium ion concentration are prepared1、C2，CiAnd, respectively, measuring their potential values (e.g., E)1、E2、Ei) And the standard solution temperature T, establishing an equation:
E1＝E0+S(T/298.15)log(C1/Ciso)
E2＝E0+S(T/298.15)log(C2/Ciso)
solving the above equation set to obtain E0S, i.e. after calibration E0S and CisoThereby constructing the Nernst equation
E＝E0+S(T/298.15)lgC/CisoUsing this nernst equation, a sodium ion concentration meter measures the sodium ion concentration.
The prior calibration device and method for the sodium ion concentration meter mainly comprise a dynamic two-point calibration device and a dynamic two-point calibration method for the sodium ion concentration meter, and a calibration device and a calibration method for a secondary standard addition method for the sodium ion concentration meter.
The dynamic two-point calibration device of the sodium ion concentration meter is shown in fig. 1, and the technical problems of the dynamic two-point calibration device of the sodium ion concentration meter and the calibration method thereof are mainly reflected in the following problems:
requiring diluting sodium chloride standard solution with higher concentration with fresh primary reagent water to prepare sodium ion concentration C1And C2Two standard solutions of (a), department of electrical power specifications: the conductivity of fresh primary reagent water is less than 0.1 mu s/cm, and the content of sodium ions is less than 0.2 mu g/L. In actual operation, the fresh primary reagent water is not easy to reach the standard that the conductivity is less than 0.1 mu s/cm and the content of sodium ions is less than 0.2 mu g/L after being produced and stored on site; on the other hand, due to the extensive existence of sodium ions, air, containers, experimental equipment, manipulations and the like can pollute the reagent water and the standard solution in the processes of moving the reagent water and preparing the standard solution, and the two aspects are combined to ensure that the sodium ion true concentration value of the standard solution is (C)1+Cs) And (C)2+Cs)，CsIt is reagent water, the process of preparing standard solution introduces positive error, it is uncertain in each calibration.
The calibration device of the sodium ion concentration meter by the secondary standard addition method is shown in fig. 2, and the technical problems of the calibration device of the sodium ion concentration meter by the secondary standard addition method and the calibration method thereof are mainly reflected in the following aspects:
1. the operating regulation must be carried out within 2 to 3 hours after the activation treatment of the sodium ion selective electrode, which is an operation of removing an old sensitive film of the sodium ion selective electrode using a corrosive substance to expose a new sensitive film, and this brings about the following problems:
A. the performance of the sodium ion selective electrode is inconsistent in the calibration and measurement processes, and the principle deviates from the consistency principle of the calibration and measurement conditions of the instrument;
B. the electrode activation treatment reduces the service life of the sodium ion selective electrode and increases the maintenance cost;
C. in the electrode activation treatment, substances with extremely strong corrosiveness are used, and protective glasses and gloves are needed to be worn during operation, so that the danger of operators is increased;
2. standard solution (190 ml volume) was circulated in the measuring cup under air agitation during calibration; during measurement, a measured water sample (with the volume of 23ml) flows through the measuring cup, the states and flow rates of the two process liquids are inconsistent, and the principle deviates from the consistency principle of the calibration and measurement conditions of an instrument;
3. the solution is stirred in the measuring cup during calibration, potassium ions (or lithium ions) seeped from the reference electrode also circulate in the measuring cup, the sodium ion selective electrode responds to univalent ions such as potassium ions (or lithium ions), and the increased response is not sodium ions from the standard solution and interferes with calibration;
4. the secondary standard addition method is calibrated to operate on the instrument using field and is limited by the field environment, conditions and the level of operators, and the volume V of the water sample injected into the measuring cup is measured during calibration0Standard solution C No. 11Volume V of1Standard solution C No. 21Volume V of2Difficult accomplish accurately, according to:
dc1＝C1×V1/(V1+Vc)
dc2＝C2×V2/(V1+V2+Vc)
ensuring dc1、dc2The accuracy of (2) has certain difficulty;
5. the sodium ion concentration of the water sample during calibration is not more than a certain range (micro sodium meter 1 mug/L, low sodium meter 19 mug/L), so that the application of calibration is limited, if the sodium ion concentration of the water sample to be tested is more than the range within a certain period, the sodium ion concentration meter can not be calibrated within the period;
6. the calibration operation has more limiting conditions and more calibration operation steps. Activating the ion selective electrode before calibration; the sodium ion concentration of the water sample is checked to be not more than a certain range (micro sodium table 1 mug/L, low sodium table 19 mug/L); switching the operation of the measuring cup; checking whether various components in the measuring cup are installed in placeDetermining the volume of liquid in the measuring cup if the switching valve of the measuring cup has micro leakage, and inputting a new volume if the volume changes; accurate addition of C1、C2And confirming operation for a plurality of times according to the prompt of the instrument.
Disclosure of Invention
The invention aims to overcome and solve the defects of the calibration technology of the existing sodium ion concentration meter, designs a three-point flow type calibration device of the sodium ion concentration meter, which has reasonable structure, convenient use and accurate calibration according to the calibration principle of the sodium ion concentration meter, and creatively provides a three-point flow type calibration method of the sodium ion concentration meter, which is scientific, reasonable, strong in applicability and good in effect.
One of the technical schemes adopted for realizing the purpose of the invention is as follows: a three-point flowing type calibration device of a sodium ion concentration meter comprises a tested water sample inlet valve 1, a constant pressure overflow cup 2, a water sample pipeline 3, an alkalization device 5, a temperature electrode 6, an ion selection electrode 7, a reference electrode 8, an electrode lead 9, an intelligent high-resistance millivoltmeter 10, a flowing type measuring pool 11, a waste water collector 12 and an overflow pipe 13, wherein the tested water sample inlet valve 1 is arranged on the water sample pipeline 3, the inlet end of the constant pressure overflow cup 2 is connected with the outlet end of the tested water sample inlet valve 1 through the water sample pipeline 3, the outlet end of the constant pressure overflow cup 2 is connected with the inlet end of the alkalization device 5 through the water sample pipeline 3, the outlet end of the alkalization device 5 is connected with the temperature electrode 6 through the water sample pipeline 3, the temperature electrode 6 is connected with the ion selection electrode 7 through the water sample pipeline 3, the ion selection electrode 7 is connected with the reference electrode 8 through the water sample, the temperature electrode 6, the ion selection electrode 7 and the reference electrode 8 are arranged in a flow-through measuring cell 11, the temperature electrode 6, the ion selection electrode 7 and the reference electrode 8 are respectively and electrically connected with an intelligent high-resistance millivoltmeter 10 through electrode leads 9, an overflow port of the constant-pressure overflow cup 2 is connected with a wastewater collector 12 through an overflow pipe 13, the constant-pressure overflow cup is characterized by further comprising a distributor 4, a base sample electromagnetic valve 14, a first standard sample electromagnetic valve 15, a measured water sample electromagnetic valve 16, a second standard sample electromagnetic valve 17, a base sample reagent barrel 18, a first standard sample reagent barrel 19 and a second standard sample reagent barrel 20, the distributor 4 is arranged on a water sample pipeline 3 connected between the constant-pressure overflow cup 2 and an alkalization device 5, the measured water sample electromagnetic valve 16 is arranged on the water sample pipeline 3 connected between the constant-pressure overflow cup 2 and the distributor 4, the base sample electromagnetic valve 14 is arranged on the water sample pipeline 3 connected between the base sample reagent barrel 18 and the distributor 4, the sample one electromagnetic valve 15 is arranged on the water sample pipeline 3 between the sample one reagent barrel 19 and the distributor 4, the sample two electromagnetic valve 17 is arranged on the water sample pipeline 3 between the sample two reagent barrel 20 and the distributor 4, the reference electrode 8 is connected with the waste water collector 12 through the water sample pipeline 3, and the water sample pipeline 3 is arranged at the bottom of the flow-through measuring tank 11.
The second technical scheme adopted for realizing the purpose of the invention is as follows: a three-point flow type calibration method for a sodium ion concentration meter comprises the following steps:
1) preparing a three-point flowing type calibration standard water sample:
preparing a reference water sample with the sodium ion concentration of 10-20 mug/L by using reagent water in a laboratory, taking out the sodium ion concentration of the reagent water, namely a base sample for short, taking a stock solution with the sodium ion concentration of 1000 mug/L, diluting the stock solution by 5 times by using the base sample, taking out the sodium ion concentration of the base sample, preparing a standard solution I, namely a standard sample I for short, taking a stock solution with the sodium ion concentration of 10mg/L, diluting the stock solution by 5 times by using the base sample, preparing a standard solution II, taking out the sodium ion concentration of the base sample, namely a standard sample II for short;
2) adding a base sample into a base sample reagent barrel 18 of the instrument, adding a first standard sample into a first standard sample reagent barrel 19, and adding a second standard sample into a second standard sample reagent barrel 20;
3) the instrument enters a calibration state, the electromagnetic valve 16 of the water sample to be tested is automatically turned off, and the first standard sample is input to 200 mug/L; inputting a second standard sample into 2000 mug/L;
4) opening a base sample electromagnetic valve 14, closing a first standard sample electromagnetic valve 15, a tested water sample electromagnetic valve 16, a second standard sample electromagnetic valve 17 and a tested water sample inlet valve 1, introducing the base sample into and flushing a distributor 4, a water sample pipeline 3 and an alkalization device 5, alkalizing the base sample, introducing the base sample into a flow-through measuring pool 11, and starting to detect and display the temperature T of the base sample by using an intelligent high-resistance millivoltmeter 101And electromotive force Es, Es is stable when the time reaches 25 minutes, and the intelligent high-resistance millivoltmeter 10 stores the stable Es;
5) the standard-one solenoid valve 15 is opened,closing the base sample electromagnetic valve 14, the tested water sample electromagnetic valve 16, the standard sample two electromagnetic valve 17 and the tested water sample inlet valve 1, enabling the standard sample I to enter and flush the distributor 4, the water sample pipeline 3 and the alkalization device 5, alkalizing the standard sample I at the same time, entering the flow-through measuring pool 11, detecting and displaying an electromotive force E of the standard sample by the intelligent high-resistance millivoltmeter 101Time to 20 minutes E1Stable, intelligent high-impedance millivoltmeter 10 storage-stable E1；
6) Opening a second standard sample electromagnetic valve 17, closing the base sample electromagnetic valve 14, the first standard sample electromagnetic valve 15, the detected water sample electromagnetic valve 16 and the detected water sample inlet valve 1, enabling a second standard sample to enter and flush the distributor 4, the water sample pipeline 3 and the alkalization device 5, alkalizing the second standard sample, enabling the second standard sample to enter the flow-through measuring pool 11, detecting and displaying a second standard sample electromotive force E by using the intelligent high-resistance millivoltmeter 102Time to 15 minutes E2Stable, intelligent high-impedance millivoltmeter 10 storage-stable E2；
7) According to the nernst equation, a system of equations is established:
Es＝E0+S(T/298.15)log[Cs/Ciso]
E1＝E0+S(T/298.15)log[(Cs+200)/Ciso]
E2＝E0+S(T/298.15)log[(Cs+2000)/Ciso]
in the formula, Es is used as a basic sample to measure the electromotive force of the battery
E1-measuring the battery electromotive force of a standard sample
E2-measuring the battery electromotive force of the standard sample two
E0The potential of the equipotential point
CsActual sodium ion concentration of the base sample, requirement Cs≯40μg/L
CisoConcentration of sodium ions at the isoelectric point
S-conversion slope, the value has corresponding relation with the performance of sodium ion selective electrode and reference electrode and the temperature of water sample, and after calibration, S is a determined value
T-water sample temperature
The three equations are solved by an intelligent high-resistance millivoltmeter to obtain CsS and E0，
Bringing the calibration result into the Stokes
E＝E0+S(T/298.15)lgC/Ciso
And the water sample is stored in an intelligent high-resistance millivoltmeter and used for on-line measurement of the water sample, and a corresponding concentration value C is calculated.
The three-point flowing type calibration method for the sodium ion concentration meter has the beneficial effects that:
1. as long as the standard solution (base sample, first standard sample and second standard sample) is prepared according to the three-point flow type calibration method, the actual sodium ion concentration of the reagent water is in a certain range, and the standard solution is not required to be prepared strictly like the standard solution prepared by the two-point calibration technology. Such as the actual sodium ion concentration of the base sample, requirement Cs≯40μg/L；
2. A three-point flowing type calibration method for a sodium ion concentration meter has the following formula:
Es＝E0+S(T/298.15)log[Cs/Ciso]
E1＝E0+S(T/298.15)log[(Cs+200)/Ciso]
E2＝E0+S(T/298.15)log[(Cs+2000)/Ciso]
the calibration calculation comprises sodium ions brought in by various reasons in the whole process of reagent water production and use, standard solution preparation and storage, and the problem of inaccurate two-point flow calibration is solved;
3. the three standard solutions are prepared in a laboratory, and the preparation conditions are superior to those of standard solutions prepared by a field secondary standard addition method, so that the preparation of the standard solutions is easy to operate, and the concentration of the prepared standard solutions is relatively accurate;
4. the device has simple structure and simple field operation, and only needs to add each standard solution into the reagent barrel of the sodium ion concentration meter, after the sodium ion concentration meter enters a calibration interface, the first standard input is 200 mug/L, the second standard input is 2000 mug/L, and the instrument automatically finishes the calibration operation after the determination;
5. the sodium ion concentration meter can be calibrated without activating the sodium ion selective electrode, and the performance of the sodium ion selective electrode is consistent during measurement and calibration;
6. introducing a reference water sample technology, artificially adding a certain amount of sodium ion concentration into the reagent water, and measuring the cell EsThe establishment of (2) is fast and stable;
7. the measuring cell of the sodium ion concentration meter also adopts a special flow-through design, the solution (standard solution or measured water sample) firstly flows through the temperature electrode and the sodium ion selective electrode and then flows through the reference electrode, potassium ions exuded by the reference electrode are taken out of the measuring cell by the solution and cannot be diffused to the upstream sodium ion selective electrode, and the interference of the potassium ions on calibration and measurement is prevented;
8. the consistency of the flow state and the flow speed of the standard solution during calibration and the measured water sample during measurement is realized, and the accuracy of calibration data is ensured.
Drawings
FIG. 1 is a schematic diagram of a dynamic two-point calibration device of a sodium ion concentration meter;
FIG. 2 is a schematic diagram of a calibration device of a sodium ion concentration meter by a secondary standard addition method;
FIG. 3 is a schematic diagram of a three-point flow type calibration apparatus for a sodium ion concentration meter;
FIG. 4 is a calibration flow chart of a three-point flow type calibration method for a sodium ion concentration meter.
In the figure: 1. the device comprises a tested water sample inlet valve, 2, a constant pressure overflow cup, 3, a water sample pipeline, 4 distributors, 5, an alkalization device, 6, a temperature electrode, 7, an ion selection electrode, 8, a reference electrode, 9, an electrode lead, 10, an intelligent high-resistance millivoltmeter, 11, a flow-through measuring pool, 12, a wastewater collector, 13, an overflow pipe, 14, a base sample electromagnetic valve, 15, a first standard sample electromagnetic valve, 16, a tested water sample electromagnetic valve, 17, a second standard sample electromagnetic valve, 18, a base sample reagent barrel, 19, a first standard sample reagent barrel, 20, a second standard sample reagent barrel, 21, an air pump, 22, a high overflow valve of the measuring cup, a low overflow valve of the measuring cup, 24 and a clean valve of the measuring cup.
Detailed Description
The present invention will be described in further detail with reference to fig. 3 and 4, and the embodiments described herein are only for explaining the present invention and are not intended to limit the present invention.
As shown in fig. 3: a water sample pipeline 3 is connected with an inlet of a constant pressure overflow cup 2, a tested water sample inlet valve 1 is arranged on the water sample pipeline 3, an outlet of the constant pressure overflow cup 2 is connected with an inlet of a distributor 4 through a water sample pipeline 3, a tested water sample electromagnetic valve 16 is arranged on the water sample pipeline 3, an outlet of the distributor 4 is connected with an inlet of an alkalization device 5 through a water sample pipeline 3, an outlet of the alkalization device 5 is connected with the bottom of a temperature electrode 6 through the water sample pipeline 3, the middle part of the temperature electrode 6 is connected with the bottom of an ion selection electrode 7 through the water sample pipeline 3, the middle part of the ion selection electrode 7 is connected with the bottom of a reference electrode 8 through the water sample pipeline 3, the temperature electrode 6, the ion selection electrode 7 and the reference electrode 8 are arranged in a flow-type measuring pool 11, the temperature electrode 6, the ion selection electrode 7 and the reference electrode 8 are respectively connected with an intelligent high, be connected with waste water collector 12, 2 overflow openings of constant pressure overflow cup pass through water sample pipeline 3 with waste water collector 12 and are connected, basic sample reagent bucket 18 passes through water sample pipeline 3 with 4 entries of distributor and is connected, be equipped with basic sample solenoid valve 14 on the water sample pipeline 3, a standard sample reagent bucket 19 passes through water sample pipeline 3 with 4 entries of distributor and is connected, be equipped with a standard sample solenoid valve 15 on the water sample pipeline 3, two reagent buckets of standard sample 20 distributor 4 entries pass through water sample pipeline 3 and connect, be equipped with two solenoid valves of standard sample 17 on the water sample pipeline 3.
As shown in fig. 4:
1) preparing a three-point flowing type calibration standard water sample:
preparing a reference water sample with the sodium ion concentration of 10-20 mug/L by using reagent water in a laboratory, taking out the sodium ion concentration of the reagent water, namely a base sample for short, taking a stock solution with the sodium ion concentration of 1000 mug/L, diluting the stock solution by 5 times by using the base sample, taking out the sodium ion concentration of the base sample, preparing a standard solution I, namely a standard sample I for short, taking a stock solution with the sodium ion concentration of 10mg/L, diluting the stock solution by 5 times by using the base sample, preparing a standard solution II, taking out the sodium ion concentration of the base sample, namely a standard sample II for short;
2) respectively adding the base sample, the first standard sample and the second standard sample into a base sample reagent barrel 18, a first standard sample reagent barrel 19 and a second standard sample reagent barrel 20 of the instrument;
3) the instrument enters a calibration state, the electromagnetic valve 16 of the water sample to be tested is automatically turned off, and the first standard sample is input to 200 mug/L; inputting a second standard sample into 2000 mug/L;
4) opening the base sample electromagnetic valve 14, and closing the first standard sample electromagnetic valve 15, the tested water sample electromagnetic valve 16, the second standard sample electromagnetic valve 17 and the tested water sample inlet valve 1;
5) the base sample enters and washes the distributor 4, the water sample pipeline 3 and the alkalization device 5, the base sample is alkalized and enters the flow-type measuring cell 11, the intelligent high-resistance millivoltmeter 10 starts to detect and display the temperature T of the base sample1And electromotive force Es, Es is stable when the time reaches 25 minutes, and the intelligent high-resistance millivoltmeter 10 stores the stable Es;
6) the base sample solenoid valve 14 is turned off;
7) opening the first standard sample electromagnetic valve 15, and closing the base sample electromagnetic valve 14, the tested water sample electromagnetic valve 16, the second standard sample electromagnetic valve 17 and the tested water sample inlet valve 1;
8) the first standard sample enters and washes the distributor 4, the water sample pipeline 3 and the alkalization device 5, the first standard sample is alkalized at the same time and enters the flow-through measuring cell 11, and the intelligent high-resistance millivoltmeter 10 detects and displays an electromotive force E of the first standard sample1Time to 20 minutes E1Stable, intelligent high-impedance millivoltmeter 10 storage-stable E1；
9) Closing the electromagnetic valve 15 of the standard sample;
10) opening the second standard sample electromagnetic valve 17, and closing the base sample electromagnetic valve 14, the first standard sample electromagnetic valve 15, the tested water sample electromagnetic valve 16 and the tested water sample inlet valve 1;
11) the second standard sample enters and washes the distributor 4, the water sample pipeline 3 and the alkalization device 5, the second standard sample is alkalized at the same time and enters the flow-through measuring cell 11, and the intelligent high-resistance millivoltmeter 10 detects and displays the second electromotive force E of the standard sample2Time to 15 minutes E2Stable, intelligent high-impedance millivoltmeter 10 storage-stable E2；
12) Closing the second electromagnetic valve 17 of the standard sample;
13) according to the nernst equation, a system of equations is established:
Es＝E0+S(T/298.15)log[Cs/Ciso]
E1＝E0+S(T/298.15)log[(Cs+200)/Ciso]
E2＝E0+S(T/298.15)log[(Cs+2000)/Ciso]
in the formula, Es is used as a basic sample to measure the electromotive force of the battery
E1-measuring the battery electromotive force of a standard sample
E2-measuring the battery electromotive force of the standard sample two
E0The potential of the equipotential point
CsActual sodium ion concentration of the base sample, requirement Cs≯40μg/L
CisoSodium ion concentration at the isoelectric point (determined value for a determined electrode)
S-conversion slope, the value has corresponding relation with the performance of sodium ion selective electrode and reference electrode and the temperature of water sample, and after calibration, S is a determined value
The three equations are solved by T-water sample temperature intelligent high-resistance millivoltmeter to obtain CsS and E0，
Bringing the calibration result into the Stokes
E＝E0+S(T/298.15)lgC/Ciso
Storing in an intelligent high-resistance millivoltmeter, and judging whether S meets the requirement;
14) if the S does not meet the requirement, recalibrating;
15) if the S meets the requirement, the calibration is successful, the calibration is stored in the intelligent high-resistance millivoltmeter, the calibration program is exited, the calibration result is brought into the Stott equation to be used for water sample on-line measurement, and the corresponding concentration value C is calculated.
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and improvements can be made without departing from the principle of the present invention, and these should be considered as the protection scope of the present invention.
Claims (1)
1. A three-point flowing type calibration method for a sodium ion concentration meter is characterized in that the method adopts a three-point flowing type calibration device for the sodium ion concentration meter, and comprises the following steps: the device comprises a tested water sample inlet valve (1), a constant pressure overflow cup (2), a water sample pipeline (3), a distributor (4), an alkalization device (5), a temperature electrode (6), an ion selection electrode (7), a reference electrode (8), an electrode lead (9), an intelligent high-resistance millivoltmeter (10), a flow-type measuring pool (11), a wastewater collector (12), an overflow pipe (13), a base sample electromagnetic valve (14), a standard sample electromagnetic valve (15), a tested water sample electromagnetic valve (16), a standard sample electromagnetic valve (17), a base sample reagent barrel (18), a standard sample reagent barrel (19) and a standard sample reagent barrel (20), wherein the tested water sample inlet valve (1) is arranged on the water sample pipeline (3), the inlet end of the constant pressure overflow cup (2) is connected with the outlet end of the tested water sample inlet valve (1) through the water sample pipeline (3), the outlet end of the constant pressure overflow cup (2) is connected with the inlet end of the alkalization device (5) through the water sample pipeline (3), the outlet end of the alkalization device (5) is connected with a temperature electrode (6) through a water sample pipeline (3), the temperature electrode (6) is connected with an ion selection electrode (7) through the water sample pipeline (3), the ion selection electrode (7) is connected with a reference electrode (8) through the water sample pipeline (3), the temperature electrode (6), the ion selection electrode (7) and the reference electrode (8) are arranged in a flow-through measuring pool (11), the temperature electrode (6), the ion selection electrode (7) and the reference electrode (8) are respectively and electrically connected with an intelligent high-resistance millivoltmeter (10) through an electrode lead (9), an overflow port of a constant-pressure overflow cup (2) is connected with a wastewater collector (12) through an overflow pipe (13), a distributor (4) is arranged on the water sample pipeline (3) which is connected between the constant-pressure overflow cup (2) and the alkalization device (5), the device comprises a sample water overflow cup (2), a distributor (4), a sample water electromagnetic valve (16), a sample base electromagnetic valve (14), a sample first electromagnetic valve (15), a sample second electromagnetic valve (17), a reference electrode (8), a sample water collector (12), a sample water pipeline (3) and a flow-through measuring pool (11), wherein the sample water electromagnetic valve (16) is arranged on the sample water pipeline (3) between the sample base electromagnetic valve (14) and the distributor (4), the sample water pipeline (3) between the sample base electromagnetic valve (18) and the distributor (4), the sample first electromagnetic valve (15) is arranged on the sample water pipeline (3) between the sample first reagent barrel (19) and the distributor (4), the sample second electromagnetic valve (17) is arranged on the sample water pipeline (3) between the sample second reagent barrel (20) and the distributor (4), and the reference electrode (8) is connected with the sample water collector (12) through the;
the method comprises the following steps:
1) preparing a three-point flowing type calibration standard water sample:
preparing a reference water sample with the sodium ion concentration of 10-20 mug/L by using reagent water in a laboratory, taking out the sodium ion concentration of the reagent water, namely a base sample for short, taking a stock solution with the sodium ion concentration of 1000 mug/L, diluting the stock solution by 5 times by using the base sample, taking out the sodium ion concentration of the base sample, preparing a standard solution I, namely a standard sample I for short, taking a stock solution with the sodium ion concentration of 10mg/L, diluting the stock solution by 5 times by using the base sample, preparing a standard solution II, taking out the sodium ion concentration of the base sample, namely a standard sample II for short;
2) adding a base sample into a base sample reagent barrel (18) of the instrument, adding a first standard sample into a first standard sample reagent barrel (19), and adding a second standard sample into a second standard sample reagent barrel (20);
3) when the instrument enters a calibration state, the electromagnetic valve (16) of the water sample to be measured is automatically turned off, and the first standard sample is input to 200 mug/L; inputting a second standard sample into 2000 mug/L;
4) the method comprises the following steps that a base sample electromagnetic valve (14) is opened, a first standard sample electromagnetic valve (15), a tested water sample electromagnetic valve (16), a second standard sample electromagnetic valve (17) and a tested water sample inlet valve (1) are closed, a base sample enters and washes a distributor (4), a water sample pipeline (3) and an alkalization device (5), the base sample is alkalized and enters a flow-through measuring pool (11), an intelligent high-resistance millivoltmeter (10) starts to detect and display the temperature T of the base sample1And electromotive force Es, Es is stable when the time reaches 25 minutes, and the intelligent high-resistance millivoltmeter (10) stores the stable Es;
5) open first electromagnetic valve of trade sample (15), base sample electromagnetic valve (14), by survey water sample electromagnetic valve (16), two electromagnetic valves of trade sample (17) and by survey water sample inlet valve (1) close, the first entering of trade sample washes distributor (4), water sample pipeline (3), alkalization device (5), alkalizes first trade sample simultaneously, gets into circulation measuring cell (11), and intelligence high resistant millivoltmeter (10) detect and show an electromotive force E of trade sample1Time to 20 minutes E1Stable, intelligent high-impedance millivoltmeter (10) storage stable E1；
6) The second electromagnetic valve (17) of the standard sample is opened, the electromagnetic valve (14) of the base sample, the first electromagnetic valve (15) of the standard sample and the electromagnetic valve (17) of the water sample to be measured16) And the inlet valve (1) of the detected water sample is closed, the second standard sample enters and washes the distributor (4), the water sample pipeline (3) and the alkalization device (5), the second standard sample is alkalized at the same time and enters the flow-type measuring pool (11), and the intelligent high-resistance millivoltmeter (10) detects and displays the second electromotive force E of the standard sample2Time to 15 minutes E2Stable, intelligent high-impedance millivoltmeter (10) storage stable E2；
7) According to the nernst equation, a system of equations is established:
Es＝E0+S(T/298.15)log[Cs/Ciso]
E1＝E0+S(T/298.15)log[(Cs+200)/Ciso]
E2＝E0+S(T/298.15)log[(Cs+2000)/Ciso]
in the formula, Es is used as a basic sample to measure the electromotive force of the battery
E1-measuring the battery electromotive force of a standard sample
E2-measuring the battery electromotive force of the standard sample two
E0The potential of the equipotential point
CsActual sodium ion concentration of the base sample, requirement Cs≯40μg/L
CisoConcentration of sodium ions at the isoelectric point
S-conversion slope, the value has corresponding relation with the performance of sodium ion selective electrode and reference electrode and the temperature of water sample, and after calibration, S is a determined value
T-water sample temperature
The three equations are solved by an intelligent high-resistance millivoltmeter to obtain CsS and E0，
And (3) substituting the calibration result into an Nernst equation:
E＝E0+S(T/298.15)lgC/Ciso
and the water sample is stored in an intelligent high-resistance millivoltmeter and used for on-line measurement of the water sample, and a corresponding concentration value C is calculated.
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| CN1523347A (en) * | 2003-09-12 | 2004-08-25 | 李永生 | Trace quantity sodium ion automatic rapid determination method and apparatus |
| CN1793887A (en) * | 2005-12-17 | 2006-06-28 | 承慰才 | On-line full automatic sodium ion concentration analyzer |
| CN101750445A (en) * | 2008-11-27 | 2010-06-23 | 河南农业大学 | Determination method for chloride ions of foods |
| CN102435648A (en) * | 2011-11-25 | 2012-05-02 | 江南大学 | Automatic three-spot calibration and temperature compensation method for pH measurer |
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| EP3271712B1 (en) * | 2015-03-16 | 2020-05-06 | CRC Care Pty Ltd | A method of recalibrating a device for assessing concentration of at least one analyte ion in a liquid |
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| CN1523347A (en) * | 2003-09-12 | 2004-08-25 | 李永生 | Trace quantity sodium ion automatic rapid determination method and apparatus |
| CN1793887A (en) * | 2005-12-17 | 2006-06-28 | 承慰才 | On-line full automatic sodium ion concentration analyzer |
| CN101750445A (en) * | 2008-11-27 | 2010-06-23 | 河南农业大学 | Determination method for chloride ions of foods |
| CN102435648A (en) * | 2011-11-25 | 2012-05-02 | 江南大学 | Automatic three-spot calibration and temperature compensation method for pH measurer |
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