CN111751433A - Method for measuring chloride ion content by adopting B-Z chemical oscillation reaction - Google Patents

Method for measuring chloride ion content by adopting B-Z chemical oscillation reaction Download PDF

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CN111751433A
CN111751433A CN202010643985.5A CN202010643985A CN111751433A CN 111751433 A CN111751433 A CN 111751433A CN 202010643985 A CN202010643985 A CN 202010643985A CN 111751433 A CN111751433 A CN 111751433A
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concentration
solution
mol
jacket
induction time
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杨文静
韦雪云
徐娜
李安琪
冉燕青
付春燕
简燕
郭铸
牛丽丹
湛铠源
张春宇
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Chongqing University
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    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N27/00—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means
    • G01N27/26—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating electrochemical variables; by using electrolysis or electrophoresis
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Abstract

The method for measuring the content of chloride ions by adopting the B-Z chemical oscillation reaction comprises the following steps: providing a catalyst containing CH2(COOH)2、KBrO3、H2SO4And KCl, and heating the mixed solution to a predetermined temperature; providing (NH)4)2Ce(SO4)3(NH) in an aqueous solution and likewise heated to said predetermined temperature4)2Ce(SO4)3The aqueous solution is added to the above mixed solution to form an electrolytic solution. Firstly, KCl with standard variable concentration is adopted to obtain a concentration reference curve corresponding to the induction time of an electrolyte system. And replacing KCl with the solution containing chloride ions to be measured, and obtaining the corresponding actually measured induction time under the unchanged other conditions. And according to the actual measurement induction time, obtaining the concentration of the solution containing the chloride ions to be measured through the concentration reference curve. The invention can accurately and conveniently measure the concentration of chloride ions, and the upper limit of the detection can reach 1.76 x 10‑2mol/L, thereby providing a brand new chloride ion detectionA measuring method and a sensor.

Description

Method for measuring chloride ion content by adopting B-Z chemical oscillation reaction
Technical Field
The invention relates to an electrochemical determination method for chloride ion content.
Background
Common methods for detecting chloride ions in solution include titration methods such as nitrate or mercuric nitrate titration and the like, and ion chromatography. Titration is generally performed by gradually dropping a reagent prepared in a solution to be measured, and identifying the end point of the reaction by a color change or the like caused by an indicator. Ion chromatography typically involves injecting a sample into a carbonate and bicarbonate solution and flowing through a series of ion exchange resins to separate the chloride ions to be detected based on the difference in the relative affinity of the anions in the sample for a low capacity, strongly basic anion resin (separation column). The separated chloride ions are converted to the acid form of high conductivity and the carbonate-bicarbonate to carbonic acid of weak conductivity (background-clearing conductivity) when passing through a strong acid cation resin (suppression column). The chloride ions converted into the corresponding acid form are measured with a conductivity detector, compared with a standard chloride ion solution, and quantified according to the peak height or peak area.
These existing chloride ion measurement methods are not only cumbersome to operate, high in cost, but also limited in accuracy.
Disclosure of Invention
The invention aims to provide a method for determining the content of chloride ions by adopting a B-Z chemical oscillation reaction with reliable performance.
The inventor finds that when the interfering substance chloride ion is added into the B-Z oscillation system, certain elementary reaction in the system is influenced, so that the interference is generated on the oscillation system, the induced time parameter of the system is changed, and the shape of the oscillation curve is changed.
Therefore, according to a first aspect of the present invention, there is provided a chloride ion content measuring method comprising:
providing a positive electrode in an electrolysis reaction chamber (electrolysis cell) of an electrolysis device;
providing a negative electrode in an electrolysis reaction chamber of an electrolysis device;
providing a solution containing CH in an electrolysis chamber of an electrolysis device2(COOH)2、KBrO3、H2SO4And KCl, and heating the mixed solution to a predetermined temperature, for example, 25 ℃;
providing (NH)4)2Ce(SO4)3An aqueous solution, and likewise heated to said predetermined temperature,
will be (NH)4)2Ce(SO4)3Adding an aqueous solution to the above mixed solution to form an electrolyte solution in the electrolytic cell, wherein CH2(COOH)2The concentration is 0.05-0.20 mol/L, KBrO3The concentration is 0.05-0.10 mol/L, H2SO4The concentration is 0.25-1.25 mol/L (NH)4)2Ce(SO4)3The concentration was 1.25 x 10-3～2.25*10-3mol/L, wherein the concentration of KCl is a standard variable concentration;
monitoring the oscillation of the electromotive force of the electrode from the time of adding the formed electrolyte until the electromotive force reaches the first trough, and counting the period of time as induction time;
changing the standard variable concentration of KCl, measuring corresponding induction time, and drawing a corresponding concentration reference curve according to the induction time;
replacing KCl with the same volume of chloride ion-containing solution to be measured for the standard variable concentration, and obtaining corresponding actual measurement induction time under the same conditions;
and according to the actual measurement induction time, obtaining the concentration of the solution containing the chloride ions to be measured through the concentration reference curve.
According to the invention, the upper limit of the content of chloride ions in the solution containing chloride ions to be tested is 1.76 x 10-2mol/L. According to the invention, the monitoring of the electromotive force of the electrodes is preferably carried out by means of an electrochemical workstation connected to a computer. In this case, a corresponding concentration reference curve can be drawn by the computer, and the concentration of the solution containing chloride ions to be detected can be calculated and output according to the actually measured induction time.
According to a preferred embodiment of the present invention, the electrolysis apparatus may comprise:
the jacket reactor is provided with an electrolytic reaction chamber and a constant-temperature water jacket at the periphery of the electrolytic reaction chamber;
jacketed preheater for preheating (NH)4)2Ce(SO4)3An aqueous solution, the jacket preheater having an inner cavity and a peripheral jacket; and
and the constant-temperature water supply device is sequentially connected in series with a constant-temperature water jacket of the jacket reactor and a peripheral jacket of the jacket preheater to form a constant-temperature water loop.
According to another aspect of the present invention, there is also provided a chloride ion sensor including:
an electrolytic reaction chamber;
a positive electrode and a negative electrode disposed in the electrolytic reaction chamber; and
CH for forming electrolyte2(COOH)2、KBrO3、H2SO4And (NH)4)2Ce(SO4)3。
The invention can accurately and conveniently measure the concentration of chloride ions, and the upper limit of the detection is 1.76 x 10-2mol/L, thereby providing a brand-new chloride ion detection method and sensor.
Drawings
FIG. 1 is a schematic view of the construction of an electrolysis apparatus according to the present invention;
FIG. 2 is an electrolyte system (Cl-free)-) Graph of induction time versus electrode electromotive force;
FIG. 3 is Cl-Concentration of 1.2 x 10-3-1.7*10-3E-t diagram of mol/L B-Z oscillating system;
FIG. 4 is Cl-The concentration is 1.8 x 10-3-2.3*10-3E-t diagram of mol/L B-Z oscillating system;
FIG. 5 is Cl-Concentration versus system induction time standard curve.
Detailed Description
The present invention will be described in further detail with reference to the accompanying drawings.
FIG. 1 shows a schematic view of the structure of an electrolysis apparatus of the present invention. As shown in the figure, the electrolysis apparatus generally comprises a constant temperature water supplier 1, a jacket preheater 2 and a jacket reactor 5. The jacket preheater 2 has an inner cavity 20 and a peripheral jacket 21. The jacketed reactor 5 has an electrolytic reaction chamber 50 and a constant-temperature water jacket 51 at the periphery of the electrolytic reaction chamber 50. The constant-temperature water supplier 1 is connected in series with the constant-temperature water jacket 51 of the jacket reactor 5 and the peripheral jacket 21 of the jacket preheater 2 in this order to form a constant-temperature water circuit. The bottoms of the jacketed preheater 2 and the jacketed reactor 5 are also shown to be provided with discharge valves, respectively.
The top of the jacketed reactor 5 is provided with a sealing plug 11, and a positive electrode (platinum electrode) 7, a negative electrode (calomel reference electrode) 8, a liquid adding funnel 9 and a stirrer 10 respectively penetrate through the sealing plug 11 and extend into an electrolytic reaction chamber 50 of the jacketed reactor 5. The volume of the electrolytic cell or electrolytic reaction chamber 50 is about 100 ml.
The prepared reagent concentrations were: h2SO4Is 3.00 mol/L; KBrO3Is 0.35 mol/L; CH (CH)2(COOH)21.00 mol/L; (NH)4)2Ce(SO4)3Is 7.0 x 10-3mol/L; the KCl standard sample is 9.6 x 10-3～1.76*10-211 standard samples within the range (see table 1 for each sample concentration after 8-fold dilution).
The above prepared reagents are added to the electrolytic reaction chamber 50 through the addition funnel 9: 20mlH2SO4，20mlKBrO3，10ml CH2(COOH)2And one of 10ml KCl standard samples. 20mL of the prepared reagent (NH) was added to the inner chamber 20 of the jacket preheater 24)2Ce(SO4)3。
The temperature of the constant temperature water supply is set to 25 ℃, the constant temperature water circuit is started, and the stirrer 10 is started to stir. Preheating the reagent (NH) in the jacket preheater 2 for a period of time after the above reagents have been kept constant at 25 deg.C4)2Ce(SO4)3Discharged and added into the electrolytic reaction chamber 50 through the charging funnel 9 to form an electrolyte to start the B-Z chemical oscillation reaction.
The positive electrode 7 and the negative electrode 8 are respectively connected to the electrochemical workstation 4. The electrochemical workstation 4 is used for monitoring the electrode electromotive force (voltage difference between the positive electrode and the negative electrode) and transmitting the monitored electrode electromotive force to the computer 3 connected with the electrochemical workstation. The computer 3 starts monitoring the oscillation of the electromotive force of the electrode through the electrochemical workstation 4 from the time when the B-Z chemical oscillation is initiated by adding the forming electrolyte until the electromotive force oscillates to the first trough, and this time is counted as the induction time, as shown in fig. 2 (in which the concentration of KCl of the standard sample is zero, i.e. it is replaced with pure water).
The concentrations of KCl in table 1 were used as standard variable concentrations in the electrolyte to obtain the corresponding induction times, respectively. FIG. 3 shows the KCl concentration in the electrolyte system at 1.2 x 10-3-1.7*10-3E-t diagram of mol/L B-Z oscillating system; FIG. 4 shows KCl concentration of 1.8 x 10-3-2.3*10-3B-Z shaking system E-t diagram of mol/L.
Table 1: cl-Concentration versus system induction time table
Figure BDA0002572439170000041
Figure BDA0002572439170000051
Table 1 examination of Cl by the Linear analysis method-Induce systemThe effect of time.
As Cl in the electrolyte system listed in Table 1-Concentration (1.20 x 10)-3mol/L、1.30*10-3mol/L、1.40*10- 3mol/L、1.50*10-3mol/L、1.60*10-3mol/L、1.70*10-3mol/L、1.80*10-3mol/L、1.90*10-3mol/L、2.00*10-3mol/L、2.10*10-3mol/L、2.20*10-3mol/L) is an abscissa, and a linear relation is considered with a logarithm corresponding to the induction time as an ordinate, the linear regression equation is △ T-1983.06 (1gC) +3.44, the fitting degree is 0.996, and a standard curve containing a concentration reference curve is drawn by using the computer 3, as shown in fig. 5.
During detection, 10ml of solution to be detected containing chloride ions is used for replacing the standard sample KCl, other conditions are unchanged, corresponding B-Z chemical oscillation reaction is carried out, and the solution is converted into corresponding Ln (t) according to actually measured induction timeLure) And comparing the value with a concentration reference curve through the computer 3 to output the concentration of the solution containing the chloride ions to be detected.

Claims (6)

1. A method for determining chloride ion content, comprising:
providing a platinum electrode as a positive electrode in an electrolysis reaction chamber of an electrolysis device;
providing a negative electrode in an electrolysis reaction chamber of an electrolysis device;
providing a solution containing CH in an electrolysis chamber of an electrolysis device2(COOH)2、KBrO3、H2SO4And KCl, and heating the mixed solution to a predetermined temperature;
providing (NH)4)2Ce(SO4)3An aqueous solution, and likewise heated to said predetermined temperature,
will be (NH)4)2Ce(SO4)3Adding an aqueous solution to the above mixed solution to form an electrolyte solution in the electrolytic cell, wherein CH2(COOH)2The concentration is 0.05-0.20 mol/L, KBrO3The concentration is 0.05-0.10 mol/L, H2SO4The concentration is 0.25-1.25 mol/L，(NH4)2Ce(SO4)3The concentration was 1.25 x 10-3～2.25*10-3mol/L, wherein the concentration of KCl is a standard variable concentration;
monitoring the oscillation of the electromotive force of the electrode from the time of adding the formed electrolyte until the electromotive force reaches the first trough, and counting the period of time as induction time;
changing the standard variable concentration of KCl, measuring corresponding induction time, and drawing a corresponding concentration reference curve according to the induction time;
replacing KCl with the same volume of chloride ion-containing solution to be measured for the standard variable concentration, and obtaining corresponding actual measurement induction time under the same conditions;
and according to the actual measurement induction time, obtaining the concentration of the solution containing the chloride ions to be measured through the concentration reference curve.
2. The method according to claim 1, wherein the upper limit of detection of chloride ions in the solution containing chloride ions to be tested is 1.76 x 10- 2mol/L。
3. The method of claim 1, wherein the monitoring of the electromotive force of the electrode is performed by an electrochemical workstation connected to a computer.
4. The method of claim 3, wherein a corresponding concentration reference curve is drawn by the computer and the concentration of the chloride ion-containing solution to be tested is calculated and output based on the measured induction time.
5. The method of claim 1, wherein the electrolysis device comprises:
the jacket reactor is provided with an electrolytic reaction chamber and a constant-temperature water jacket at the periphery of the electrolytic reaction chamber;
jacketed preheater for preheating (NH)4)2Ce(SO4)3An aqueous solution, the jacket preheater having an inner cavity and a peripheral jacket; and
and the constant-temperature water supply device is sequentially connected in series with a constant-temperature water jacket of the jacket reactor and a peripheral jacket of the jacket preheater to form a constant-temperature water loop.
6. A chloride ion sensor comprising:
an electrolytic reaction chamber;
a positive electrode and a negative electrode disposed in the electrolytic reaction chamber; and
CH for forming electrolyte2(COOH)2、KBrO3、H2SO4And (NH)4)2Ce(SO4)3。
CN202010643985.5A 2020-07-07 2020-07-07 Method for measuring chloride ion content by adopting B-Z chemical oscillation reaction Pending CN111751433A (en)

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