CN104024842A - Electrochemical measurement method and measurement device for measuring chemical oxygen demand or total organic carbon - Google Patents
Electrochemical measurement method and measurement device for measuring chemical oxygen demand or total organic carbon Download PDFInfo
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- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 title claims abstract description 9
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Classifications
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N33/00—Investigating or analysing materials by specific methods not covered by groups G01N1/00 - G01N31/00
- G01N33/18—Water
- G01N33/1806—Biological oxygen demand [BOD] or chemical oxygen demand [COD]
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N33/00—Investigating or analysing materials by specific methods not covered by groups G01N1/00 - G01N31/00
- G01N33/18—Water
- G01N33/1826—Organic contamination in water
- G01N33/1846—Total carbon analysis
-
- 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
- G01N27/28—Electrolytic cell components
- G01N27/30—Electrodes, e.g. test electrodes; Half-cells
- G01N27/308—Electrodes, e.g. test electrodes; Half-cells at least partially made of carbon
-
- 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
- G01N27/416—Systems
- G01N27/49—Systems involving the determination of the current at a single specific value, or small range of values, of applied voltage for producing selective measurement of one or more particular ionic species
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- Health & Medical Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Food Science & Technology (AREA)
- Medicinal Chemistry (AREA)
- Physics & Mathematics (AREA)
- Analytical Chemistry (AREA)
- Biochemistry (AREA)
- General Health & Medical Sciences (AREA)
- General Physics & Mathematics (AREA)
- Immunology (AREA)
- Pathology (AREA)
- Biodiversity & Conservation Biology (AREA)
- Biomedical Technology (AREA)
- Emergency Medicine (AREA)
- Molecular Biology (AREA)
- Measuring Or Testing Involving Enzymes Or Micro-Organisms (AREA)
Abstract
A novel measurement method and a measurement device for measuring chemical oxygen demand (COD) or total organic carbon (TOC) are provided. A counter electrode and a working electrode comprising an electrically-conductive diamond electrode are brought into contact with a test solution containing organic matter; changes in a current that flows between the electrodes when a voltage is applied between the working electrode and the counter electrode are detected; and the quantity of a charge is measured until a detected current value matches a background current value, and the COD or TOC of the test solution is determined from the quantity of the charge that was measured. Furthermore, the measurement device is provided with: a cell in which the counter electrode and the working electrode comprising the electrically-conductive diamond electrode are integrated; a means for applying a voltage between the working electrode and the counter electrode; a means for detecting changes in a current that flows due to said applied voltage; and an information processing means for measuring the quantity of the charge until the detected current value matches the background current value, and for determining the COD or TOC of the test solution from the quantity of the charge that was measured.
Description
Technical field
The present invention relates to electrochemical assay method and the analyzer of a kind of chemical oxygen demand (COD) (COD) or total organic carbon (TOC).
Background technology
COD and TOC are for judging the important indicator of the water quality of industrial waste water, lower draining, lakes and marhshes water, rivers and creeks water etc.The computing method of COD are: utilize oxygenant, to contained in sample, mainly take the oxidized material that organism is object and be oxidized, according to the amount of the oxygenant that used at that time, try to achieve the required oxygen amount of oxidation and converted and obtain.In JIS method, by utilizing the method regulation of potassium permanganate, be standard determination method, a lot of commercially available COD analyzers are based on the method.In addition, the computing method of TOC are: organism contained in sample is carried out to oxygenolysis, measure the amount of the carbon dioxide occurring, calculate accordingly the total amount of carbon contained in organism.The paced work of carbon dioxide, adopts non-dispersive type infrared gas detector to carry out conventionally.
Prior art document
Patent documentation
Patent documentation 1: Japanese Patent Laid-Open 2001-281220 communique
Patent documentation 2: Japanese Patent Laid-Open 2007-263815 communique
Patent documentation 3: Chinese patent application discloses instructions No. 101105472
Summary of the invention
The problem that invention will solve
The object of the invention is to, assay method and the analyzer of a kind of new COD or TOC is provided.
For the scheme of dealing with problems
For achieving the above object, every inventor of the present invention conducts in-depth research, and has found a kind of assay method and analyzer thereof, has completed the present invention.In the present invention, on conductive diamond electrode, organism contained in solution to be measured is carried out to complete oxidation decomposition, according to its quantity of electric charge, try to achieve COD or TOC.
Assay method of the present invention, to utilize electrode and the working electrode that formed by conductive diamond electrode, the COD that contains organic solution to be measured or TOC are carried out to the assay method of electrochemical mensuration, it is characterized in that: above-mentioned working electrode is contacted with above-mentioned solution to be measured electrode with above-mentioned, detection is in above-mentioned working electrode and the above-mentioned variation that flows in the electric current of two interpolars while applying voltage between to electrode, measure the current value detecting and reach the consistent front quantity of electric charge with background current value, according to the measured quantity of electric charge, try to achieve COD or the TOC of above-mentioned solution to be measured.
In addition, analyzer of the present invention, is a kind of analyzer that the COD that contains organic solution to be measured or TOC are measured, and it is characterized in that, it possesses: groove, and it is built-in with electrode and the working electrode that consists of conductive diamond electrode; Voltage bringing device, it is at above-mentioned working electrode and above-mentionedly apply voltage between to electrode; Curent change pick-up unit, its detection applies the variation of the electric current of voltage current downflow at this; Signal conditioning package, it is measured the current value detecting and reaches the consistent front quantity of electric charge with background current value, tries to achieve COD or the TOC of above-mentioned solution to be measured according to the measured quantity of electric charge.
The effect of invention
According to the present invention, can provide assay method and the analyzer of a kind of new COD or TOC.
Accompanying drawing explanation
Fig. 1 is the concept map that the analyzer of an embodiment of the invention is shown.
Fig. 2 is the figure that lasts variation that the electric current while applying voltage to lactic acid solution is shown.
Fig. 3 is the figure that the concentration of lactic acid solution and the relation of the quantity of electric charge before complete oxidation decomposition and COD are shown.
Fig. 4 be theory T OC that the solution that the molal quantity with 1:1 contains glucose and Potassium Hydrogen Phthalate is shown with according to complete oxidation, decompose before the figure of relation of the TOC that calculates of the quantity of electric charge.
Fig. 5 is the figure that the relation of the theory T OC of solution that the molal quantity with 1:1 contains glucose and Potassium Hydrogen Phthalate and the value of commercially available TOC instrument is shown.
Fig. 6 is the figure of relation that the TOC of theory T OC and mensuration is shown.
Symbol description
10 working electrodes
20 pairs of electrodes
30 contrast electrodes
40 stirring rod
50 measure groove
60 potentiostats
70 signal conditioning packages
S solution to be measured
Embodiment
Below, with reference to accompanying drawing, embodiments of the present invention are described.Fig. 1 is the concept map that the analyzer of an embodiment of the invention is shown.
The internal measuring instrument of present embodiment is standby: working electrode 10, to electrode 20 and contrast electrode 30; And measure groove 50, it is built-in with this 3 electrodes.Working electrode 10, electrode 20 and contrast electrode 30 are connected to potentiostat 60, and are connected with signal conditioning package 70 on potentiostat 60.In addition, measure in groove 50 and be provided with stirring rod 40, it stirs solution S to be measured.Below, various piece is described.
The working electrode 10 that the present invention is used, can adopt conductive diamond electrode.
Adamas is good insulator originally.But by adding the Huo of 13 family 15 family's impurity, it can show the electric conductivity of semiconductor～metal species.In the present invention, the adamas that shows the electric conductivity of semiconductor～metal species is used as to electrode.
In order to make these adamass there is electric conductivity, can mix the element of the above-mentioned 13 Ji of family 15 families, preferably mix boron, nitrogen, phosphorus, especially preferably mix boron.The potential window wider (oxidizing potential and reduction potential are wider) of the boric diamond electrode of doped with high concentration boron, compares with other electrode materials, has the advantageous feature that background current is lower.In addition, boric diamond electrode also has excellent performance at aspects such as chemical resistance, permanance, electric conductivity, corrosion resistances.
The addition of the material mixing in order to make these adamas tool electric conductivity is suitably determined in the scope that makes adamas tool electric conductivity, and for example, preferably addition is for giving 1 * 10
-2～10
-6the amount of Ω cm left and right electric conductivity.To this addition, conventionally in manufacturing process, controlled.
Although conductive diamond itself needn't rely on the support of base material to can be used as electrode, preferably forms the film of conductive diamond on base material, connects a wire to this film, becomes electrode.Base material can adopt Si (for example, monocrystalline silicon), Mo, W, Nb, Ti, Fe, Au, Ni, Co, Al
2o
3, SiC, Si
3n
4, ZrO
2, MgO, graphite, single-crystal diamond, cBN, quartz glass etc., preferably adopt monocrystalline silicon, Mo, W, Nb, Ti, SiC, single-crystal diamond.
Thickness for conductive diamond film is not particularly limited, and is preferably 1～100 μ m left and right, is especially preferably 5～50 μ m left and right.
In the present invention, conductive diamond electrode also can adopt the form of microelectrode.So-called " diamond electrode of microelectrode form " herein, refers to such as the end of the fine rule of Pt etc. is cut off and fined away, and makes it more sharp-pointed with electrolysis lapping mode, then the film in its end surface formation conductive diamond forms.
Conductive diamond film can utilize chemical vapour deposition technique manufacture.So-called " chemical vapour deposition technique ", refers to the method that makes gas raw material generation chemical reaction synthetic in gas phase, is commonly referred to as CVD (Chemical Vapor Deposition) method.The method is widely used in semiconductor fabrication process, is applied to the manufacture of conductive diamond film of the present invention after also can being improved according to object.
The synthetic mode of carrying out of adamantine chemical gaseous phase is: the potpourri of the carbonaceous gas such as methane and hydrogen of take is unstrpped gas, by excitaton source, is excited, and is supplied to and on substrate, makes its deposition.
Excitaton source can adopt heated filament, microwave, high frequency, direct current glow discharge, direct-current arc electric discharge, combustion flame etc.In addition, also can, by several being used in combination wherein, regulate nucleus to generate density, to realize large area or equalization.
Raw material can adopt and contain carbon and the decomposition by excitaton source and excite and can generate C, C
2isoreactivity charcoal and CH, CH
2, CH
3, C
2h
2deng the various compounds of hydrocarbon free radical, in preferred embodiment, gas has CH
4, C
2h
2, C
2h
4, C
10h
16, CO, CF
4, liquid has CH
3oH, C
2h
5oH, (CH
3)
2cO, solid has graphite, fullerene etc.
In chemical gas phase synthetic method, give the interpolation of the material of adamas electric conductivity, can carry out by the following method.For example the disk that adds material is positioned in system, is similarly excited with carbon source raw material, interpolation material is imported to carbon gas phase; Or in advance interpolation material is made an addition to carbon source, and import together with carbon source in system, by excitaton source, excited, thereby interpolation material is imported to carbon gas phase etc.Wherein, preferred the latter's method.Especially, when carbon source adopts the liquid such as acetone, methyl alcohol, preferably by boron oxide (B
2o
3) be dissolved in wherein as the method in boron source, so not only easily control the concentration of boron, and comparatively easy.In chemical gas phase synthetic method, when boron is made an addition to carbon source, concentration is 10～12,000ppm left and right conventionally, and preferred concentration is 1,000～10,000ppm left and right.
Chemical gas phase synthetic method, preferably using plasma chemical gas phase synthetic method.The advantage of this plasma chemical gas phase synthetic method is, causes that the active-energy of chemical reaction is larger, and reaction is very fast.And, according to the method, can generate the chemical species that non-thermodynamics high temperature can not exist, make to react and become possibility at low temperature.The manufacture of the conductive diamond film based on plasma chemistry gas phase synthesis method, can be according to for example Yano et al., J.Electrochem.Soc., and 145 (1998) 1870 contained methods are carried out.
The boric diamond electrode that the present invention is used, for example can be by having adopted the manufacture method of the wave plasma auxiliary chemical vapor deposition method of following explanation to manufacture.Concrete manufacture method is as follows.First, in the chamber that has been full of hydrogen, generate hydrogen plasma, by being dissolved with the acetone of boron class and the mixed gas of methyl alcohol, import wherein, and import carbon source, make it on such as the electric conductivity such as silicon substrate (or semiconduction) substrate, vapour deposition occur.Substrate adopts silicon substrate { Si (100) }, and substrate surface is carried out for example,, after quality processing (, being ground with the bortz powder of 0.5 μ m), substrate being installed on the support of film formation device.Film deposition source adopts the potpourri (liquid, mixing ratio is volume ratio 9:1) of acetone and methyl alcohol, by boron oxide (B
2o
3) be dissolved into this potpourri, make boron/carbon (B/C) than reaching 10
4ppm.Then, in this film deposition source, as carrier gas, pass into pure H
2after gas, its introduction chamber is indoor, by another pipeline hydrogen injecting, (for example, 532ml/min) be adjusted to the pressure (for example, 115Torr=115 * 133.322Pa) of regulation in advance.Then, input 2.45GHz microwave power, make its electric discharge after, by power adjustments to 5kW.Then, after it is stable, as carrier gas, to film deposition source, inject pure H
2gas (for example, 15ml/min), carries out film forming.
By having adopted the manufacture method of above-mentioned wave plasma auxiliary chemical vapor deposition method, in the situation that film forming speed is 1～4 μ m/ hour, carried out the film forming of diamond thin until thickness reaches approximately 30 μ m, now, though heated substrates, does not observe temperature under steady state (SS) and reaches approximately 850～950 ℃.In addition, measured the Raman spectrum of resulting diamond thin, at 1333cm
-1only observe single crest.In addition, electric conductivity is about 10
-3cyclic voltammetric has been measured in about Ω cm in the sulfuric acid of 0.5M, confirm to have-1.25～+ 2.3V (with respect to SHE) compared with broad potential window.
In above-mentioned conductive diamond electrode, also can inject at least one element that is selected from the group that gold, white gold, silver, palladium, ruthenium, rhodium and iridium forms at its surface ion.The electrode of manufacturing by ion implantation, stability is higher, is using metal in the situations such as Ultrasonic Cleaning also can not peel off, and is having excellent metal dispersion.
In addition, while carrying out Implantation, along with sneaking into of ionization element, the irradiation damage that meeting produce power causes.For this reason, heat-treat (annealing), to repair irradiation damage, and the injection element that makes to sneak into position between lattice moves.By this annealing in process, the skin section sustaining damage is recovered original crystalline texture along the atomic arrangement of bottom crystallization.The element injecting in this process exposes to surface, the catalysis that this element performance is expected.
Above-mentioned element, by using known ion implantation apparatus and known ion implantation technique, carries out Implantation.Ion needn't be injected into the deep inside of diamond thin, only need be near surface load.Therefore the energy that, ion is accelerated needn't be too high.Number 10keV～1MeV left and right is enough.
In addition, preferably injection rate IR is 1～10 * 10
14ions/cm
2left and right.Above-mentioned element is only brought into play the catalysis of the electrochemical oxidation reaction of determination object etc., self does not consume, as long as it is just enough therefore to have the adhesion amount of described degree.If injection rate IR is too much, can there is decrystallized phenomenon.
In above-mentioned conductive diamond electrode, also can be on its surface as catalyst load oxide catalyst.The oxide catalyst can adopt brown lead oxide, Han bi brown lead oxide, fluorine-containing brown lead oxide, containing cobalt brown lead oxide, tin oxide, containing antimony oxidation tin, nickeliferous aluminium oxide etc.The load of these oxide catalyst, only need be according to known method, for example, by brown lead oxide particulate load when the conductive diamond electrode, in the perchloric acid of the 1M of the plumbi nitras that contains 10mM, take the method for electric potential scanning (sweep velocity 5mV/s, potential range+1.4～+ 1.8Vvs.Ag/AgCl, 3 circulations).In addition, after also can using constant potentiometric electrolysis and applying the lead acetate of presoma, heated oxide obtains the method for brown lead oxide etc., as long as can be from Pb through certain oxidation processes
2+ion is manufactured brown lead oxide particle.
Above-mentionedly to electrode 20, can adopt for example platinum, carbon, stainless steel, gold, adamas, SnO
2deng.
Above-mentioned contrast electrode 30 can utilize known technology, can adopt standard hydrogen electrode, silver silver chloride electrode, full mercurous chloride electrode, the hydrogen palladium electrode etc. of closing.By contrast electrode is contacted, can control and put on working electrode and the absolute value to the voltage between electrode.
The structure of said determination groove 50 is: its inside stockpiles above-mentioned solution S to be measured, and this solution S to be measured can contact above-mentioned working electrode 10, above-mentioned to electrode 20 and above-mentioned contrast electrode 30.Material for said determination groove 50 is not particularly limited, as long as its inside can stockpile above-mentioned solution S to be measured, preferably it is by such as the resin manufacture such as teflon of inhibition of impurities stripping to greatest extent.
40 pairs of above-mentioned stirring rod stockpile in the solution S above-mentioned to be measured of said determination groove 50 and stir.By above-mentioned stirring rod 40, stir above-mentioned solution S to be measured, the efficiency of the organic oxidative decomposition that the generation of the OH free radical on above-mentioned working electrode and OH free radical cause is improved.Method of operating for the flabellum shape of above-mentioned stirring rod 40 and material, flabellum is not particularly limited, preferably it can stir fully to above-mentioned solution S to be measured, and the generation of inhibition of impurities and micro powder etc. and produce bubble from electrode surface to greatest extent, for example, preferably adopt cross stirring rod.Be stirred in volume of sample effective when larger, while measuring a small amount of sample, needn't stir.
Above-mentioned potentiostat 60 under the current potential that makes above-mentioned working electrode 10 state constant with respect to above-mentioned contrast electrode 30, detect above-mentioned working electrode 10 with above-mentioned to electrode 20 between the electric current of generation, its detection signal is sent to above-mentioned signal conditioning package 70.Above-mentioned potentiostat 60 remains current potential constant function except having, and also has with constant speed scanning current potential, skips to the function of selection of appointed at interval of certain hour.These functions needn't be arranged at 1, for example, also current potential can be kept function and electric potential scanning function setting on different potentiostats.
Above-mentioned signal conditioning package 70 is universal or special equipment, and it possesses the output units such as input media, display, A/D converter, the D/A converters etc. such as CPU, storer, input and output channel, keyboard.Above-mentioned CPU and peripherals thereof are according to the program concerted action of storing in the regulation field of above-mentioned storer, the signal above-mentioned potentiostat 60 being detected with this is analyzed, measure the quantity of electric charge before the organism complete oxidation decomposition in above-mentioned solution S to be measured, according to the measured quantity of electric charge, try to achieve COD or the TOC of above-mentioned solution S to be measured.In addition, above-mentioned signal conditioning package 70 is integrated setting physically, also can be divided into a plurality of machines by wired or wireless.
Next, the assay method of COD of the present invention or TOC is illustrated.Electrode aspect, for example, working electrode adopts boric diamond electrode, and electrode is adopted to platinum, and contrast electrode adopts silver silver chloride electrode.
First, only will be not containing the electrolyte solution of solution S to be measured, do not inject and measure groove 50, on one side with stirring rod 40, stirred, apply a certain constant voltage on one side, mensuration background current last variation.Electrolyte solution adopts conventionally used, for example, can adopt metabisulfite solution, phosphate buffer solution etc.
Then, with the solution S to be measured of equivalent, replace the electrolyte solution of measuring in groove 50, Yi Bian stirred, Yi Bian apply the voltage being equal to while measuring electrolyte solution, measure the variation that lasts of electric current.When the current value of solution S to be measured reaches the value identical with background current, treat as the complete oxidation decomposition such as organism contained in solution S to be measured, according to from measuring the difference of lasting variation changing with background current of lasting start to the electric current of solution S to be measured complete oxidation decomposable process, try to achieve the quantity of electric charge.
In general, electric decomposing organic matter need to apply higher current potential, this can cause the decomposition of electrode self aging, or produces this spinoff of electric decomposition of water.And in the mensuration of the quantity of electric charge of trying to achieve by said method, can get rid of the impact of aging or spinoff.
At this, the relation of complete oxidation being decomposed to the required quantity of electric charge and COD describes.
In solution S to be measured, contained oxidized material is mainly organism.Use C
ah
bn
co
drepresent this organism.COD is the required oxygen amount of oxygenolysis, first according to formula 1, tries to achieve required oxygen molal quantity x, by formula 2, represents.
C
ah
bn
co
d+ xO
2→ aCO
2+ b/2H
2o+cNO
2(formula 1)
X=a+b/4+c-d/2 (formula 2)
In addition,, in COD assay method of the present invention, organism is by betiding the high oxidative capacity of the OH free radical of electrode surface, the oxygenolysis shown in generating polynomial 3.Now, oxygenolysis needs the electronics of the y shown in formula 4 mole.
C
ah
bn
co
d+ yOH-→ aCO
2+ (b+y)/2H
2o+cNO
2+ ye
-(formula 3)
Y=4a+b+4c-2d (formula 4)
Therefore, the oxygen x of formula 2 mole with the pass of electronics y mole of formula 4 is
Y=4x (formula 5)
Proportionate relationship, needn't rely on and limit organic value a～d, can decompose the required quantity of electric charge according to complete oxidation and try to achieve COD accurately.This means, according to the method, even contained composition is failed to understand in solution S to be measured, still can try to achieve COD accurately.
Next, illustrate that the actual measurement quantity of electric charge Y coulomb that rises solution to be measured according to Z tries to achieve the method for COD value X (mg/L).
According to Faraday constant, the electric charge that carry the electron institute of 1 mole is 96485 coulombs, therefore, and can be in the hope of
X＝Y/96485﹡1/Z﹡1/4﹡32﹡10
3
=0.083 ﹡ Y/Z (formula 6)
And, as similar technology, patent documentation 3 discloses the method for COD of trying to achieve a kind of, draws the calibration curve that utilizes the current value of boric diamond determination of electrode and the COD of standard sample that is:, from the current value recording, according to typical curve, try to achieve COD under same test conditions.
But in fact, current value can be different and different because of composition contained in tested sample from the relation of COD, cannot try to achieve COD according to the current value of the not clear tested sample of composition.
For example, in No. 2001/098766 International Publication patent, record utilize that diamond electrode is measured, about the concentration of caffeine and theophylline and the calibration curve of crest current value, based on this, the checking computations COD of calculated value and the related coefficient of crest current value, owing to being two compounds and difference cannot define COD according to crest current value.That is, why the method that patent documentation 3 is recorded can measure COD, is because contained organic principle is known in the waste water of its determination object.If composition is unknown, cannot measure COD according to current value.
On the other hand, assay method of the present invention is to try to achieve COD according to the quantity of electric charge, therefore, even if composition is unknown, still can measure COD.
The relation of next, complete oxidation being decomposed to the required quantity of electric charge and TOC describes.
Because TOC is full organic carbon, it is equivalent to a in above-mentioned formula 1.In addition, in the oxygenolysis of electrode surface as shown in above-mentioned formula 3.Contained organism C in solution S to be measured
ah
bn
co
dwhen middle c=0 and b=2d, for example, when it is glucose or lactic acid, can obtain the relation of x=a, y=4a, therefore, same during with COD, measure complete oxidation and decompose the required quantity of electric charge, can try to achieve TOC accurately.
Even contained organism C in solution to be measured
ah
bn
co
din not c=0 and b=2d, as long as draw composition and the known theory T OC of solution S to be measured and the calibration curve of the quantity of electric charge of concentration, can decompose the required quantity of electric charge according to the identical solution complete oxidation to be measured of composition and try to achieve its TOC.If the composition of solution S to be measured is not clear, about above-mentioned solution S to be measured, if make in advance the calibration curve that the complete oxidation of having measured decomposes the value of the required quantity of electric charge and the value of commercially available TOC instrument, afterwards, can use above-mentioned calibration curve to try to achieve the TOC as the scaled value of TOC instrument according to the quantity of electric charge.
Embodiment
Below enumerate embodiment, the present invention will be described in more detail.But the present invention is not limited in these embodiment.
(embodiment 1)
Working electrode adopts the boric diamond electrode that the concentration by microwave plasma CVD device manufacture, institute's boracic is 10000ppm, adopts platinum electrode as to electrode, adopts silver silver chloride electrode as contrast electrode, is placed on mensuration groove.The HZ-5000 that potentiostat has adopted Big Dipper electrician to manufacture.
The metabisulfite solution that is 0.1M by the concentration of 3mL adds mensuration groove, stir on one side, apply the voltage of 2.5V on one side, observed response current, after 600 seconds, become steady state (SS), by its electric current as a setting.
Then, the metabisulfite solution in said determination groove adds lactic acid, becomes the lactic acid solution that concentration is 15 μ M, keeps applying the voltage of 2.5V, stir on one side, measured the response current of 14000 seconds on one side.Result is referring to Fig. 2.Tried to achieve before the time that shows the current value that is equal to background current, be equivalent in Fig. 2 the quantity of electric charge of the gable area of 600～10000 seconds, result is 52mC.Therefore, having tried to achieve concentration that complete oxidation decomposes 3mL is that the required quantity of electric charge of lactic acid solution of 15 μ M is 52mC.This is consistent with the theoretical value height of 52.1mC.In addition, except adopting to the said method of measuring metabisulfite solution in groove and add lactic acid, also having adopted, take the lactic acid solution that the concentration of modulating is in advance 15 μ M and all replace the method for measuring the solution in groove, still tried to achieve the identical quantity of electric charge.
(embodiment 2)
The concentration that makes to measure the lactic acid solution in groove except adding lactic acid becomes 5 μ M and 10 μ M, and other operations are all identical with embodiment 1, measures the variation that lasts of response current, has tried to achieve complete oxidation and has decomposed the required quantity of electric charge.The quantity of electric charge and theoretical value that experiment value in various situations is obtained are shown in Fig. 3.Experiment value is consistent with theoretical value height.
The COD trying to achieve according to above-mentioned formula 6 has been shown in Fig. 3.Like this, can try to achieve COD according to the quantity of electric charge.
(embodiment 3)
The boric diamond electrode identical with embodiment 1 of take is working electrode, take platinum line as to electrode, take silver silver chloride electrode as contrast electrode, is arranged at mensuration groove.The HZ-5000 that potentiostat has adopted Big Dipper electrician to manufacture.
The metabisulfite solution that is 0.1M by the concentration of 4mL adds mensuration groove, stir on one side, apply the voltage of 2.5V on one side, observed response current, after 1000 seconds, become steady state (SS), by its electric current as a setting.
Then, in the metabisulfite solution in said determination groove, add glucose and each 50nmol of Potassium Hydrogen Phthalate, the sample that to have modulated theory T OC be 2.1mg/l.The voltage that keeps applying 2.5V to this sample, stir on one side, the response current that shows first 10000 seconds of the time of the current value that is equal to background current measured on one side.Tried to achieve the quantity of electric charge of the integrated value of the difference that is equivalent to response current and background current, result is 0.262C.
The reaction of glucose and Potassium Hydrogen Phthalate can represent by formula 7 and formula 8, therefore, by the complete electrolysis of the glucose of 1mol and the Potassium Hydrogen Phthalate of 1mol, adds up to the electronics that obtains 54mol, and its quantity of electric charge is 5210190C as calculated.
C
6h
12o
6+ 24OH → 6CO
2+ 18H
2o+24e
-(formula 7)
C
8h
5o
4 -+ 29OH → 8CO
2+ 17H
2o+30e
-(formula 8)
In said sample, contain each 50nmol of glucose and Potassium Hydrogen Phthalate, therefore, the theoretical quantity of electric charge is 0.261C as calculated.Therefore, the measured value of the quantity of electric charge is consistent with theoretical quantity of electric charge height.
The carbon atom amount of the glucose of 1mol and the Potassium Hydrogen Phthalate of 1mol adds up to 14mol, and therefore, the carbon atom amount of calculating according to the quantity of electric charge is 0.704 μ mol, and known TOC is 2.11mg/L as calculated.
In the above-mentioned solution that contains glucose and each 50nmol of Potassium Hydrogen Phthalate, continue to add glucose and each 50nmol of Potassium Hydrogen Phthalate, obtain containing glucose and each 100nmol of Potassium Hydrogen Phthalate solution (theory T OC is 4.2mg/l) time, and the glucose and the Potassium Hydrogen Phthalate that again continue to add each 50nmol, obtain containing glucose and each 150nmol of Potassium Hydrogen Phthalate solution (theory T OC is 6.3mg/l) time, the same variation that lasts of measuring response current, has tried to achieve complete oxidation and has decomposed the required quantity of electric charge.
By the theory T OC in each situation with the relationship marking of the TOC calculating according to the quantity of electric charge in Fig. 4, find that rectilinearity is higher, the coefficient of determination is 0.9979.And theory T OC is basically identical with the TOC calculating according to the quantity of electric charge.Like this, in the solution that can contain glucose and Potassium Hydrogen Phthalate at the molal quantity with 1:1, according to complete oxidation, decompose the required quantity of electric charge and try to achieve the basic TOC consistent with theoretical value.
Then, add glucose and Potassium Hydrogen Phthalate to concentration in the metabisulfite solution that is 0.1M, having modulated concentration is the solution (theory T OC is separately 2.1mg/l, 4.2mg/l, 6.3mg/l) of 12.5 μ M, 25.0 μ M, 37.5 μ M.Utilize commercially available TOC instrument (Shimadzu TOC-L CPH), measured the TOC of these solution.By theory T OC with by the value that TOC instrument is measured, mark in Fig. 5, find that rectilinearity is higher, the coefficient of determination is 0.9996.Fig. 6 shows the situation after overlapping by Fig. 4 and Fig. 5.Known theory T OC and the TOC trying to achieve with electrochemical method are basically identical, compare with utilizing commercially available TOC instrument, and the order of accuarcy of the TOC that the method according to this invention is tried to achieve is higher.
Claims (4)
1. an assay method, it utilizes electrode and the working electrode that consists of conductive diamond electrode, and the chemical oxygen demand (COD) that contains organic solution to be measured (COD) or total organic carbon (TOC) are carried out to electrochemical mensuration, wherein,
Described working electrode is contacted with described solution to be measured electrode with described,
Detection is in described working electrode and the described variation that flows in the electric current of two interpolars while applying voltage between to electrode,
Measure the current value detecting and reach the consistent front quantity of electric charge with background current value,
According to the measured quantity of electric charge, try to achieve COD or the TOC of described solution to be measured.
2. assay method according to claim 1, wherein, is stirring under the state of described solution to be measured, at described working electrode with describedly apply voltage between to electrode.
3. an analyzer, this analyzer is measured the chemical oxygen demand (COD) that contains organic solution to be measured (COD) or total organic carbon (TOC), wherein,
Described internal measuring instrument is standby:
Groove, it is built-in with electrode and the working electrode that consists of conductive diamond electrode;
Voltage bringing device, it is at described working electrode and describedly apply voltage between to electrode;
Curent change pick-up unit, its detection applies the variation of the electric current of voltage current downflow at this;
Signal conditioning package, it is measured the current value detecting and reaches the consistent front quantity of electric charge with background current value, draws COD or the TOC of described solution to be measured according to the measured quantity of electric charge.
4. analyzer according to claim 3, wherein, described analyzer also possesses stirring apparatus, and described stirring apparatus stirs the solution described to be measured being injected in described groove.
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| PCT/JP2012/083984 WO2013100101A1 (en) | 2011-12-27 | 2012-12-27 | Electrochemical measurement method and measurement device for measuring chemical oxygen demand or total organic carbon |
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| CN104459169A (en) * | 2014-09-26 | 2015-03-25 | 浙江工商大学 | Concentration detection device and method for D-fructose solution |
| CN105203608A (en) * | 2015-11-03 | 2015-12-30 | 中国航天员科研训练中心 | Electrochemical oxygen sensor for hydrogen palladium electrode |
| CN112903772A (en) * | 2021-01-16 | 2021-06-04 | 中国科学院南京土壤研究所 | In-situ initial measurement and prejudgment method for TOC concentration of solution |
| CN113740406A (en) * | 2021-09-09 | 2021-12-03 | 南开大学 | Portable miniaturized COD electrochemical measuring device and measuring method thereof |
| CN114341636A (en) * | 2019-08-30 | 2022-04-12 | Bl科技公司 | Total organic carbon and conductivity validation and calibration using a single sample |
| CN117949516A (en) * | 2024-03-22 | 2024-04-30 | 山西天和盛环境检测股份有限公司 | Water body detection device |
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| CN103743693A (en) * | 2013-10-30 | 2014-04-23 | 浙江大学 | Total organic carbon analysis instrument and method based on electrochemical catalytic oxidation |
| JP6492381B2 (en) * | 2015-03-02 | 2019-04-03 | 学校法人慶應義塾 | Detection unit and measuring device |
| US11092585B2 (en) * | 2018-02-27 | 2021-08-17 | Giner, Inc. | Electrochemical method for detection and quantification of organic compounds in water |
| CN112147711A (en) * | 2019-06-28 | 2020-12-29 | 中国石油化工股份有限公司 | Method and system for rapidly acquiring marine shale total organic carbon in field |
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| CN105203608A (en) * | 2015-11-03 | 2015-12-30 | 中国航天员科研训练中心 | Electrochemical oxygen sensor for hydrogen palladium electrode |
| CN105203608B (en) * | 2015-11-03 | 2017-12-15 | 中国航天员科研训练中心 | Hydrogen palladium electrode oxygen sensor |
| CN114341636A (en) * | 2019-08-30 | 2022-04-12 | Bl科技公司 | Total organic carbon and conductivity validation and calibration using a single sample |
| CN112903772A (en) * | 2021-01-16 | 2021-06-04 | 中国科学院南京土壤研究所 | In-situ initial measurement and prejudgment method for TOC concentration of solution |
| CN112903772B (en) * | 2021-01-16 | 2022-01-04 | 中国科学院南京土壤研究所 | In-situ initial measurement and prejudgment method for TOC concentration of solution |
| CN113740406A (en) * | 2021-09-09 | 2021-12-03 | 南开大学 | Portable miniaturized COD electrochemical measuring device and measuring method thereof |
| CN117949516A (en) * | 2024-03-22 | 2024-04-30 | 山西天和盛环境检测股份有限公司 | Water body detection device |
Also Published As
| Publication number | Publication date |
|---|---|
| JPWO2013100101A1 (en) | 2015-05-11 |
| WO2013100101A1 (en) | 2013-07-04 |
| KR20140116373A (en) | 2014-10-02 |
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