CN109270132A - Electrochemical determining device and stirrer - Google Patents
Electrochemical determining device and stirrer Download PDFInfo
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- CN109270132A CN109270132A CN201811081576.XA CN201811081576A CN109270132A CN 109270132 A CN109270132 A CN 109270132A CN 201811081576 A CN201811081576 A CN 201811081576A CN 109270132 A CN109270132 A CN 109270132A
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Abstract
There is provided it is a kind of constituted in such a way that stirrer is not contacted with active electrode, and stablize stirrer rotation, to make the stability-enhanced device of electrochemical gaging.Electrochemical determining device of the invention has: determination unit (2), accommodates fluid sample；Stirrer (91), is arranged at the inside of determination unit (2)；Contact surface (2P), its opposed faces (911a) for being contacted with the stirrer (91) opposed with electrode surface (5a) of active electrode (5) separates opposed faces (911a) from electrode surface (5a)；The faces different from opposed faces (911a) of retaining surface (2Q), stirrer (91) are rotated along retaining surface (2Q), for being kept stirring the rotation gesture of sub (91).
Description
The application be the applying date be on December 6th, 2013, priority date be on December 28th, 2012, application No. is
201310655479.8 application for a patent for invention " electrochemical analysis method, electrochemical analysis device and reagent set " division Shen
Please.
Technical field
The present invention relates to the method, apparatus and examination of the cadmium that electrochemically detection contains in the sample of biology
Agent group.
Background technique
Known cadmium is toxic to human body, if cadmium is put aside in vivo, renal function etc. will receive damage.Therefore, for packet
The amount for including the cadmium contained in the food including rice sets standard, be defined as 1ppm in food hygiene law, in brown rice hereinafter,
It cannot peddle when containing more than standard value cadmium, all be incinerated.In addition, being examined in brown rice according to the notice in the grain Room
The rice for measuring the cadmium of 0.4ppm or more is completely used as industrial use.
In the past, the method as analysis cadmium, it is known to the atomic absorption analysis method of the analytic approach as statutory regulation, ICP
Luminescence analysis, ICP mass analysis etc..But the huge valuableness of device of these analyses is carried out, and its operation is also complicated.
On the other hand, although working as will analyze also in the trial (patent document 1) for carrying out electrochemically analyzing cadmium
When the cadmium contained in food, the organic matter contained in the food hinders the realization of high-precision analysis as disturbing factor.
Patent document 1: Japanese Unexamined Patent Publication 2005-49275 bulletin
Summary of the invention
Therefore, the purpose of the present invention is to provide one kind high sensitive and accurately to detect and quantitative from life
Electrochemical analysis method, device and the reagent set of the cadmium contained in the sample of object.
That is, electrochemical analysis method of the invention, is electrochemically to analyze using to electrode and active electrode
The method of the cadmium contained in biogenic sample, has abstraction process, has oxidation to the sample addition from biology
Property and with cadmium formed complex compound acid, from it is above-mentioned from biology sample in extract cadmium.
By using the such a acid for having oxidisability and do not form complex compound with cadmium, always biogenic sample is mentioned
Cadmium is taken, so as to decompose the organic matter for being contained in the sample from biology well, and since the acid is not formed with cadmium
Complex compound, therefore the measurement of the detection of cadmium, its concentration can be accurately proceed.
The acid of complex compound is formed, it is preferable to use perchloric acid with oxidisability and not with cadmium as above-mentioned.Here, being sent out in ICP
In optical analysis, ICP mass analysis, although hydrochloric acid is used for the pretreatment of the sample from biology, if using salt
Acid carries out the extraction of cadmium, then current peak when cadmium is dissolved out from active electrode becomes smaller, it is difficult to carry out high-precision analysis.This be because
Complex compound is formed for hydrochloric acid, sulfuric acid and cadmium.
Preferably, the pH value of obtained extracting solution is adjusted to 3~7.More preferably pH value is 3~6.If pH value is not
Reach 3, then current peak when cadmium is dissolved out from active electrode becomes smaller, it is difficult to carry out high-precision analysis.On the other hand, if pH value
More than 7, then cadmium precipitates.
Preferably, slow using what is be made of organic acid and/or its salt when the pH value of said extracted liquid being adjusted to 3~7
Electuary.The carboxyl of organic acid has chelating effect, as gold such as the lead of disturbing factor, selenium, chromium, boron when carboxyl package analyzes cadmium
Belong to, to be speculated as preventing the interference to cadmium.As above-mentioned organic acid, preferably carboxyl has 1 or 2 in a molecule
It is a, for example, phthalic acid, acetic acid etc. can be enumerated.In addition, preferably pH value is adjusted in the case where using phthalic acid
It is 4 or so, in the case where using acetic acid, pH value is preferably adjusted to 5 or so.
In the extracting solution from the sample of biology, it is usually formed the complex of cadmium and copper, in this case, in electrochemistry
In analysis, the current peak of the complex from cadmium and copper is detected.Therefore, in order to make measurement result not by from biology
Sample in copper amount influence, can in advance from biology sample in add copper.As copper at this time
Additive amount, for example, not up to pre-determined reference value can be added (for example, as desired in the sample for deriving from biology of target
The maximum amount of copper) component copper, can also be with concentration (the big serious offense of 3~10 times or so of Cadmium detrmination concentration range
It is surplus) add copper.When adding copper, the copper compound of electrolyte of copper etc. can be used.
Electrochemical analysis method of the invention, it is preferred that have electrode clean process, in above-mentioned active electrode and solution
In the state that (acid of the solution and the composition of buffer and pH value and pH value said extracted liquid phase adjusted are same) contacts,
Apply positive voltage in above-mentioned active electrode.By carrying out the electrode clean process, it can remove in advance and be adhered to active electrode
Organic matter, heavy metal, therefore be able to carry out high-precision analysis.
As above-mentioned active electrode, there is no particular limitation, it is preferable to use carbon electrode, wherein more preferably uses conductive gold
Hard rock electrode.As the conductive diamond electrode, such as the electrode etc. doped with boron, nitrogen, phosphorus etc. can be enumerated, wherein preferably
It is the boron-doped diamond electrode of high concentration boron-doping.Boron-doped diamond electrode has potential window big (oxidizing potential and reduction potential
Range is wide), it is lower than other electrode material background currents, to the high sensitivity of reductant-oxidant, compared with gold, platinum etc., due to
It is difficult to generate the absorption of physics in electrode surface, therefore there is the excellent property for being difficult to occur the peak value other than oxygen, hydrogen generation.
In addition, boron-doped diamond electrode has excellent chemical durability, mechanical robustness, electric conductivity, corrosion resistance etc..More into one
Step, boron-doped diamond electrode also have the cleaning for being easy to carry out chemistry, physics, are easy to maintain electrode surface due to its hardness
The clean state the advantages of.
In addition, being able to use for example for above-mentioned to electrode by platinum, carbon, stainless steel, gold, diamond, SnO2Etc. compositions
Further in the case where using reference electrode, known electrode can be suitably used in electrode, be able to use for example silver-colored chlorine
Change silver electrode, calomel electrode, standard hydrogen electrode, palladium hydrogen electrode etc..
In the present invention, in the case where the active electrode used is conductive diamond electrode, in above-mentioned electrode clean
After process, further, preferably carries out applying negative voltage in above-mentioned conductive diamond electrode, seal electrode surface hydrogen
The hydrogen of endization blocks chemical industry sequence.The processing of hydrogen sealing endization is carried out by the surface so to conductive diamond electrode, so that
The sensitivity of electrode surface improves, and is able to carry out high-precision analysis.
Electrochemical analysis method of the invention, can be according to for example with such as being implemented with the analytical equipment of flowering structure.That is,
For electrochemically analyzing the device of cadmium contained in the sample for deriving from biology, have: extraction element, to deriving from
The sample addition of biology has oxidisability and does not form the acid of complex compound with cadmium, extracts in the sample of biology from above-mentioned
Cadmium；PH value adjusts device, and the pH value of obtained extracting solution is adjusted to 3~7；For built-in to electrode and active electrode, hold
Receive the unit of said extracted liquid；Bringing device in above-mentioned active electrode and above-mentioned makes cadmium or it is multiple to applying between electrode
Fit electro-deposition is in the voltage of above-mentioned active electrode, and then, application makes electro-deposition in the cadmium of above-mentioned active electrode or its is compound
The voltage of body dissolution；Detection device, detection result from above-mentioned active electrode and the above-mentioned electric current between electrode.So electricity
The analytical equipment of chemistry is also an aspect of of the present present invention.
In addition, when implementing electrochemical analysis method of the invention, in order to extract cadmium in biological sample from this, and
And the extracting solution that adjustment obtains can be used for measurement comprising forming the acid of complex compound with oxidisability and not with cadmium, by having
The reagent set of buffer and copper compound that machine acid and/or its salt are constituted.Reagent set so is also an aspect of of the present present invention.
In reagent set of the invention, the acid (A ingredient) of complex compound is formed with oxidisability and not with cadmium, by organic acid
And/or the buffer (B component) and copper compound (C ingredient) of its salt composition can be prepared respectively as individual reagent, it can also
So that A ingredient and C ingredient are contained in a kind of reagent or B component and C ingredient are made to be contained in a kind of reagent.In addition, as in the examination
The dosage form for the reagent that agent group contains, there is no particular limitation, can be solid-state (powdered, tablet), is also possible to liquid.
The present invention formed according to this can decompose organic matter contained in the sample from biology well,
And the complex compound with cadmium is not formed, therefore can be accurately proceed the measurement of the detection of cadmium, its concentration.
Detailed description of the invention
Fig. 1 is the schematic diagram for indicating the composition of electrochemical determining device of present embodiment.
Fig. 2 is the perspective view for showing schematically the heavy metal ion measurement device of same embodiment.
Fig. 3 is the sectional view for showing schematically the structure of determination unit of same embodiment.
Fig. 4 is the perspective view of the stirrer of same embodiment.
Fig. 5 is the top view of the stirrer of same embodiment.
Fig. 6 is the front view of the stirrer of same embodiment.
Fig. 7 is the right view of the stirrer of same embodiment.
Fig. 8 is the figure for showing schematically the manufacturing method of stirrer of same embodiment.
Fig. 9 is the 1st schematic diagram for indicating the specific structure inside the determination unit of same embodiment.
Figure 10 is the 2nd schematic diagram for indicating the specific structure inside the determination unit of same embodiment.
Figure 11 is VA characteristic curve when extracting cadmium from rice using perchloric acid.
Figure 12 is VA characteristic curve when extracting cadmium from rice using hydrochloric acid.
Figure 13 is the schematic diagram for indicating the variation of retaining surface.
Figure 14 is the schematic diagram for indicating the variation of retaining surface.
Symbol description:
100 electrochemical determining devices
2 determination units
2P contact surface
2Q retaining surface
2X inside circumference
3 pairs of electrodes
4 reference electrodes
5 active electrodes
91 stirrers
911a opposed faces
91b outside circumference
Through-hole is used in 91H insertion
911 body parts
912 blade parts
Specific embodiment
Hereinafter, being described with reference to electrochemical determining device of the invention.
The electrochemical determining device 100 of present embodiment is using three electricity to electrode, reference electrode and active electrode
The stripping voltammetry of pole mode analyzes the cadmium contained in the sample of biology such as rice.
(apparatus structure)
Specifically, electrochemical determining device 100 is as shown in Figure 1, have the determination unit 2 for accommodating fluid sample, with liquid
Sample contact setting to electrode 3, reference electrode 4 and active electrode 5, the change of the current potential that changes the current potential of active electrode 5
Portion 6, at least part that the fluid sample of determination unit 2 will be contained in and the acidic buffer displacement as measurement solution
Liquid replaces mechanism 11, active electrode 5 and the current detecting part 7 to the electric current between electrode 3 is detected, according to by current detecting part
7 current values detected calculate the concentration calculation portion 8 of concentration of heavy metal ion.
In addition, above-mentioned each component as shown in Fig. 2, be contained in cover C, be provided in the front lower of cover C and accommodate
The waste liquid tank T2 of the waste liquid of the buffering flow container T1 and buffer after receiving fluid sample, use etc. of above-mentioned acidic buffer.
In addition, in the front upper of cover C, the behaviour of setting power source ON/OFF button, measurement start button, correcting button, cleaning button etc.
Acting button group B and the display unit 801 for showing measurement result (concentration etc.).Further, it on the top of cover C, is provided with and uses
In the Sample introduction portion 21 that fluid sample is injected into said determination unit 2.
Firstly, illustrating current potential change portion 6, current detecting part 7, liquid displacement mechanism 11 and concentration calculation portion 8.
Current potential change portion 6 and current detecting part 7 are made of potentiostat PS.Potentiostat PS makes active electrode 5
Current potential be fixed for reference electrode 4 in the state of, active electrode 5 is detected and to the electric current generated between electrode 3, by the inspection
It surveys signal and is output to the calculation control device 8 with aftermentioned concentration calculation portion.
Potentiostat PS keeps the current potential of active electrode 5 heavy in heavy metal electricity for the function about current potential change portion 6
Product changes between the current potential of the heavy metal of active electrode 5 in the current potential of active electrode 5, and dissolution electro-deposition.Specifically, permanent
Potentiometer PS changes the current potential of active electrode 5 to negative potential direction with the state of 5 contact liq sample of active electrode, supply
Make the heavy metal electro-deposition for measuring target in the current potential on the surface of active electrode 5, then, with above-mentioned heavy metal electro-deposition in surface
The state that is contacted with the phthalate buffer as acidic buffer of active electrode 5, by the electric potential scanning of active electrode 5
To positive potential direction, supply makes electro-deposition in the current potential of the heavy metal dissolution of active electrode 5.
In addition, potentiostat PS is with regard to for current detection function, detection changes function by above-mentioned current potential and will make
When with electric potential scanning to the positive potential direction of electrode 5, active electrode 5 and to the electric current generated between electrode 3.
In addition, potentiostat PS also has in addition to the function of being kept fixed current potential and scans current potential with fixed speed, press
The functions such as step are carried out with the current potential specified according to fixed time interval.These functions are not required to be equipped on same dress
It sets, for example, it is also possible to keep function and electric potential scanning function to be set to other devices current potential.
Liquid replaces mechanism 11, as shown in Figure 1, having the row for the liquid in determination unit 2 to be discharged to waste liquid tank T2
Pipeline 12 out, and phthalate buffer is supplied to from buffer tank T1 the feeding pipe 13 of determination unit 2.
Discharge line 12 has the discharge pipe 121 that connect with determination unit 2, and being set to that the discharge pipe 121 is used for will
The fluid removal of determination unit 2 is contained in the discharge pump 122 of outside.Discharge pipe 121 is set as with attached on 5 surface of active electrode
The bottom wall part 2c of determination unit 2 is penetrated through (not shown) by the mode being closely open.In addition, downstream side and the waste liquid tank of discharge pipe 121
T2 connection.In addition, discharge pump 122 controls its working time etc. by aftermentioned calculation control device 8.
Feeding pipe 13 have be connected to determination unit 2 supply pipe 131 and be set to the supply pipe 131 for will
The phthalate buffer for being contained in buffering flow container T1 is supplied to the supply pump 132 of determination unit 2.Supply pipe 131 with to electricity
Pole 3 and reference electrode 4 similarly, tilt insertion in the sidewall portion 2b of determination unit 2 in a manner of towards active electrode 5 and fix
(not shown).In addition, the upstream side of supply pipe 131 is connect with buffering flow container T1.In addition, supply pump 132 passes through aftermentioned calculating
Control device 8 controls its working time etc..
Liquid displacement mechanism 11 is controlled by calculation control device 8, and the fluid sample that will be contained in determination unit 2 exists
In the state of at least keeping the liquid measure contacted to electrode 3 and active electrode 5 with fluid sample, liquid displacement is carried out.Specifically,
The discharge pump 122 and supply pump 132 of liquid displacement mechanism 11 are controlled by calculation control device 8, and it is single will to be contained in measurement
The fluid sample of member 2, which is divided into, is repeatedly replaced with the phthalate buffer as measurement solution.For example, liquid replacing machine
Structure 11 for example sets fluid sample several times (such as 4 times or so) with phthalate buffer half and halfly every time
It changes.Pass through confession after half is discharged by discharge line 12 in the fluid sample for being contained in determination unit 2 as method of replacing
To pipeline 13 for giving the considerable amount of phthalate buffer of discharge rate.So for example it is repeated several times.Alternatively, it is also possible to simultaneously
Carry out the discharge of fluid sample and the supply of phthalate buffer.
Calculation control device 8 is to obtain the detection signal detected by potentiostat PS, carry out the detection of heavy metal ion with
And the device of concentration mensuration.Specifically, calculation control device 8 is that have CPU, memory, I/O channel, display etc. defeated
The general and dedicated device of device 801, A/D converter, D/A converter etc. out, above-mentioned CPU and its periphery machine pass through
In the measurement program cooperative work that the presumptive area of above-mentioned memory stores, thereby executing aftermentioned mensuration program.In addition, meter
Control device 8 is calculated, need not be integrated in structure, it can also be by wired or be wirelessly divided into multiple machines.
Then, illustrate determination unit 2, be set to the electrode group 3~5 of the determination unit 2 and be set to the determination unit 2
Rabbling mechanism 9.
Determination unit 2, as shown in figure 3, in the device of the internal accommodation space 2S for forming fluid sample, wall portion on it
2a forms the Sample introduction portion 21 for importing fluid sample.
In addition, in the sidewall portion 2b of determination unit 2, to electrode 3 and reference electrode 4 with towards downside (side bottom wall part 2c)
Mode tilt insertion fix.Further, in the bottom wall part 2c active electrode 5 of determination unit 2 to expose in accommodation space 2S
Mode be fixed.
It here, is such as platinum electrode to electrode 3 for the electrode group 3~5 in relation to present embodiment, reference electrode 4 is
Such as silver-silver chloride electrode, active electrode 5 are boron-doped diamond (conductive diamond) electrode of high concentration boron-doping.
To electrode 3 and reference electrode 4, as previously mentioned, the sidewall portion 2b in determination unit 2 is set to measurement list with direction
The mode of the active electrode 5 of the bottom wall part 2c of member 2 tilts insertion and fixes.In this way, single in measurement to electrode 3 and reference electrode 4
The sidewall portion 2b of member 2 tilts insertion in a manner of towards active electrode 5 and fixes, therefore these electrodes 3,4 can be configured as not
Interfere surrounding structure.In addition, the insertion of aftermentioned stirrer 91 is inserted into in through-hole 91H to electrode 3 and reference electrode 4,
Electrode surface 5a of the front end of these electrodes 3,4 close to active electrode 5.
In addition, active electrode 5 is the bottom wall part 2c in determination unit 2 so that electrode surface 5a exposes in accommodation space 2S
The planar electrode that mode is arranged.The active electrode 5 is arranged to be blocked in the opening portion of bottom wall part 2c formation, accordingly, is formed
The structure that electrode surface 5a exposes in accommodation space 2S.In addition, in bottom wall part 2c and active electrode 5 or keeping the active electrode
Between 5 holding member (not shown), the seal member such as o-ring, the liquid for making to be contained in determination unit 2 are set
Sample does not escape to outside from gap.
It is set to the rabbling mechanism 9 of said determination unit 2, as shown in Figure 1, having the receiving for being contained in determination unit 2 empty
Between the stirrer 91 in 2S, the magnetic force operating mechanism 92 for rotating the stirrer 91 by magnetic force.In addition, magnetic operating
Mechanism 92 is arranged on the downside of the bottom wall part 2c of determination unit 2, specifically, is arranged on the downside of active electrode 5.
Stirrer 91 is made as shown in Figure 4 to 7 of the fluorine resin of such as PTFE etc., has cylindrical ontology
The open end 911p of portion 911 and the side in the axis direction of the body part 911 are formed continuously, and are extended along axis direction multiple
Blade part 912.In addition, being resistant to pollution structure since stirrer 91 is made of fluorine resin.In addition, though it is not shown,
In stirrer 91, before the corner of the radial outside of the open end 911q of another party of body part 911 and blade part 912
The corner etc. of end has been carried out chamfer machining (R chamfer machining) as shape with rounded corners.Accordingly, stirrer 91 becomes easy
In the structure of rotation.
The open end 911q of another party of the axis direction of body part 911 has in the state for being housed inside determination unit 2
Under, the opposed faces 911a opposed with the electrode surface 5a of active electrode 5.Opposed faces 911a is by another party of body part 911
Open end 911q open end formed face annular in shape.
In this way, in the rotating center section of stirrer 91, being formed for being inserted into electrode 3 since body part 911 is cylindrical
And the insertion of reference electrode 4 is with through-hole 91H (referring to Fig. 5).The insertion is the rounded hole in section with through-hole 91H.In this way, by
Then the rounded hole in section can make to be inserted into inserting to electrode 3 and reference electrode 4 in the case where stirrer 91 is rotation status
It is as large as possible to enter space.
Circumferencial direction of multiple blade parts 912 in the open end 911p of a side of body part 911 is equally spaced formed.This
In embodiment, 2 blade parts 912 are formed, are arranged to right in the radial direction of the open end 911p of a side of body part 911
It sets.In addition, multiple blade parts 912 are the components of mutually the same shape each other.The end face towards circumferencial direction of each blade part 912
912x is functioned as the mixing surface for the fluid sample that stirring is contained in accommodation space 2S (referring to Fig. 4 and Fig. 5).More into one
Step, the lateral surface 912m of blade part 912 is the continuous the same face of outside circumference 911m with above-mentioned body part 911.
In addition, multiple magnet 913 are built in inside in the body part 911 of stirrer 91.In view of stirrer 91 is whole
Weight balancing, multiple magnet 913 are axisymmetrically set to not formed blade part 912 on the circumferencial direction of body part 911
Partially (referring to Fig. 5).Specifically, respectively it is arranged more in rodlike magnet in opposed walls 911s, 911t of body part 911
913 (in Fig. 5, being respectively arranged 3 in each opposed walls 911s, 911t).It is built in the rodlike magnet 913 of each opposed walls 911s, 911t
It is set along the axis direction of body part 911 (referring to Fig. 6 and Fig. 7).It is set to the more rodlike magnetic of the opposed walls 911s of a side
It is the pole N that iron 913, which is configured to one side side of axis direction (912 side of blade part), and the another side (side opposed faces 911a) of axis direction is S
Pole.In addition, more rodlike magnet 913 for being set to the opposed walls 911t of another party are configured to one side side (blade part 912 of axis direction
Side) it is the pole S, the another side (side opposed faces 911a) of axis direction is the pole N.
For thus configured stirrer 91, in the rotary body of magnetic force operating mechanism 92, opposed with one side
Wall 911s corresponding part setting 91 side of stirrer is the magnet of the pole N, in portion corresponding with the opposed walls 911t of above-mentioned another party
Set up the magnet for setting that 91 side of stirrer is the pole S separately.Magnetic force operating mechanism 92 formed according to this, in Stirring 91, with
The magnet 913 of stirrer 91 be attracted to the magnet of rotary body state (that is, the opposed faces 911a of stirrer 91 be forced into it is aftermentioned
Contact surface 2P state) rotation.In this way, stirrer 91 is attracted to rotary body, opposed faces 911a in contact surface 2P to slide
Mode rotate, therefore the spin stabilization of stirrer 91 can be made.
In addition, the opposed faces 911a of stirrer 91, that is, in the open end of another party of the axis direction of body part 911
911q forms 1 or multiple recess portions 914 for releasing bubble to top.The recess portion 914 is in the another of body part 911
The part of inside circumference and the outside circumference opening of the open end 911q of one side.In present embodiment, in body part 911
The circumferencial direction of the open end 911q of another party is equally spaced formed, it is contemplated that the weight balancing of stirrer 91 is formed in leaf
The lower section (referring to Fig. 6) in piece portion 912.
Briefly describe the manufacturing method of the stirrer 91.As shown in figure 8, by the axis of cylindrical processing forepiece 900
The mutually opposed sidewall portion 901,902 of direction one end respectively with from the direction vertical with axis direction when it is axisymmetrically big
Cause is cut in a manner of in L-shaped cutting off.Accordingly, body part 911 and blade part 912 are formed.In addition, by above-mentioned processing
The open end of the another side of the axis direction of forepiece 900 forms recess portion, to form release bubble recess portion 914.More into
One step cuts the embedded hole for magnet 913 to be embedded in body part 911 by end mill(ing) cutter etc..Magnet 913 is embedded into this to bury
Apertured.After implementing so processing, R chamfer machining above-mentioned is implemented by component after processing and forms stirrer 91.In addition,
It can also implement R chamfer machining before being embedded to magnet 913.
As shown in Fig. 9 and Figure 10, the determination unit 2 of present embodiment has stirrer contact surface 2P and (hereinafter referred to as connects
Contacting surface 2P) and retaining surface 2Q.Contact surface 2P is contacted with the opposed faces 911a to the stirrer 91 for being placed in electrode surface 5a, keeps this right
Face 911a is set to separate from electrode surface 5a.Retaining surface 2Q is formed in the different location with contact surface 2P, is in stirrer 91
The faces different from opposed faces 911a along its rotate face, for be kept stirring son 91 rotation gesture.
Contact surface 2P is the face supported to contact the opposed faces 911a of stirrer 91 with electrode surface 5a.This connects
Contacting surface 2P be from the electrode surface 5a of active electrode 5 towards electrode surface 5a towards direction (upper direction) separation formed in circle
Cricoid plane loads stirrer 91.Specifically, contact surface 2P is on the top of the electrode surface 5a of active electrode 5, be formed in from
The protruding portion 22 annular in shape that the inside circumference 2x of determination unit 2 is prominent to radially inner side and is formed.Specifically, by protruding portion
22 plane (upper surface) formation with 5 opposite side of active electrode.
As described above, stirrer 91 attracted magnetic force operating mechanism 92, stirrer 91 in such contact surface 2P
Opposed faces 911a is rotated with the state for being forced into contact surface 2P.Accordingly, opposed faces 911a revolves in a manner of in contact surface 2P sliding
Turn, therefore the spin stabilization of stirrer 91 can be made, the fluid sample generated according to stirrer 91 in electrode surface 5a can be made
Convection current fix.
Retaining surface 2Q be the rotary shaft of stirrer 91 is approximately fixed for electrode surface 5a, be kept stirring son 91 rotation
The face of posture.Retaining surface 2Q is the cylindrical of the upside formation of the contact surface 2P (protruding portion 22) inside determination unit 2
Face.The central axis of retaining surface 2Q and the Pivot axle of stirrer are roughly the same.Specifically, retaining surface 2Q is by determination unit
2 cylindrical inside circumference 2x is formed.Retaining surface 2Q is big with the outside circumference 911m's of the body part 911 of stirrer 91
Cause the integrated spaced opposed formation in several gaps.In addition, the gap between the outside circumference 911m and retaining surface 2Q of body part 911,
Preferably it can ensure the degree of the rotation of stirrer 91 and as small as possible, such as 0.5mm or so.According to retaining surface 2Q,
Stirrer 91 can be prevented when rotating beginning or rotation inverts upside down on the way, inhibit the vibration of the rotary shaft of stirrer 91,
Or reduce the amplitude of the vibration of rotary shaft, it can substantially fixedly be kept stirring the rotation gesture of son 91.Therefore, can make
The spin stabilization of stirrer 91 can make substantially solid in the convection current of the electrode surface 5a fluid sample generated according to stirrer 91
It is fixed.
In addition, in the present embodiment, the outside circumference 911m of body part 911 and the lateral surface 912m of blade part 912 are
The same face, retaining surface 2Q are configured to the lateral surface 912m (referring to Fig.1 0) for being placed in blade part 912.Accordingly, stirrer 91 rotates
When, since the lateral surface 912m of blade part 912 is rotated also along retaining surface 2Q (the inside circumference 2x of determination unit 2), energy
Enough rotation gestures for being substantially fixedly kept stirring son 91.
(analysis method of cadmium)
Then, the method for illustrating to analyze cadmium by leaching using electrochemical analysis device 100.
1. extracting solution modulating process
Hereinafter, the case where illustrating using rice as from biological sample.Firstly, rice is crushed to obtain rice
Powder.Then, obtained rice flour is dissolved in perchloric acid, extracts cadmium while decomposing organic matter.By to obtained extracting solution
Implement to attract filtering to remove residue.Further, attracting filtered extracting solution addition Potassium Hydrogen Phthalate and hydrogen
PH value is adjusted to 4.0 or so as the extracting solution for cadmium measurement by sodium oxide molybdena.
It should be noted that cadmium is usually formed the complex with copper in the extracting solution of rice.It is formed in cadmium and copper is answered
In the case where zoarium, the current peak as caused by the complex of cadmium and copper is observed sometimes when dissolving out process, and by cadmium list
Current peak caused by body preferably only detects a kind of current peak as caused by cadmium for the ease of analysis.In addition, for cadmium
The detection sensitivity of the complex of monomer and cadmium and copper, electrochemical analysis is different.Therefore, in order to keep detection sensitivity consistent, just
In the discussion of analysis result, for using cadmium as with the detection of the complex of copper, the copper concentration in the extracting solution of rice is not achieved
In the case where benchmark concentration (for example, for anticipation maximum concentration 4ppm), the copper of not full measure can be added in extracting solution to supplement
Copper, alternatively, it is also possible to add significantly superfluous copper (for example, for cadmium with the concentration of the 3~10 of the cadmium concentration of anticipation times or so
The case where concentration is 50ppb adds copper in a manner of making concentration become 200~400ppb), using cadmium as the compound physical examination with copper
It measures and.Here, being able to use CuCl when said extracted liquid adds copper2Deng copper compound.The copper compound, Ke Yidan
Solely it is added to extracting solution, can also be added together with perchloric acid, or added together with Potassium Hydrogen Phthalate.
2. Electrode treatment process
By user's operation power source ON/OFF button, calculation control device 8 make the main power source of electrochemical analysis device 100 at
For ON.Thereafter, Electrode treatment button is pressed by user, calculation control device 8 is measured in device, specifically, is surveyed
The Electrode treatment of order member 2 controls.The Electrode treatment process is, firstly, will be mentioned using the feeding pipe 13 of liquid displacement mechanism 11
Liquid used when taking cadmium, such as perchloric acid, the concentration of Potassium Hydrogen Phthalate and sodium hydroxide and pH value and extracting solution
Identical phthalate buffer is supplied in determination unit 2, and passes through the adjacent benzene of the stirring supply of magnetic rabbling mechanism 9 on one side
Diformazan acid buffer applies positive voltage (for example, applying 60 seconds+3.5V in conductive diamond electrode 5 on one side on schedule
Voltage), be removed conductive diamond electrode 5 adhere to organic matter and heavy metal electrode clean processing.Then, exist
Conductive diamond electrode 5 applies negative voltage (for example, -3.5V voltage for applying 5 seconds) by the scheduled time, carries out electric conductivity
The hydrogen sealing endization on the surface of diamond electrode 5 is handled.Then, the O-phthalic is discharged from the discharge line 12 of liquid displacement mechanism 11
Acid buffer, to complete Electrode treatment process.
3. extracting solution injection process
After the completion of above-mentioned Electrode treatment process, user keeps the open-close lid for being set to the Sample introduction portion 21 on the top cover C mobile
To release position, extracting solution is injected from Sample introduction portion 21.Then, user presses measurement start button, and calculation control device 8 connects
It receives measurement commencing signal and starts Cadmium detrmination.It should be noted that at this moment, by detecting to electrode 3, conductive diamond electrode
5 and the liquid sensor that whether is contacted with extracting solution of reference electrode 4 acquirement detection signal (not shown), calculation control device 8
Judge whether electrode group 3~5 contacts with extracting solution.If being judged as contact, measurement work below is entered, if not in contact with,
Then carry out the report of wrong display etc..
4. electro-deposition process
Calculation control device 8 exports electro-deposition commencing signal to potentiostat PS.Accordingly, potentiostat PS makes conductive gold
The potential change of hard rock electrode 5 makes the current potential of the conductive diamond electrode 5 become more electric than the reduction of cadmium to the direction of negative potential
Low current potential (for example, -1.0V) is also wanted in position, makes cadmium electro-deposition in the surface 5a of conductive diamond electrode 5.Here, cadmium with
In the case that copper forms complex, the complex electro-deposition of cadmium and copper can be made in the surface 5a of conductive diamond electrode 5.It should
In the case of, electro-deposition current potential -0.8V or so can be made.The current potential of conductive diamond electrode 5 is lower than above-mentioned reduction potential
State keep completing the electro-deposition process after predetermined time (for example, 10 minutes).
5. liquid replaces process
After above-mentioned electro-deposition process, potentiostat PS is by the current potential of conductive diamond electrode 5 than above-mentioned reduction potential
Low state is kept fixed.Calculation control device 8 replaces mechanism 11 for the extraction in determination unit 2 by control liquid under the state
Liquid and phthalate buffer are divided into multiple displacement.In present embodiment, the extracting solution for being contained in determination unit 2 passes through discharge
Pipeline 12 is discharged after half, and the phthalate buffer for giving discharge rate a considerable amount is supplied by feeding pipe 13.Pass through
It repeatedly carries out the work (such as 4 times or so) and extracting solution is replaced into phthalate buffer.In this way, leading in liquid displacement process
Cross and be kept fixed the current potential of conductive diamond electrode 5 with the state lower than above-mentioned reduction potential, can prevent electro-deposition in
The cadmium of electrode 5 dissolves out in liquid displacement process.Here, the discharge rate of extracting solution and the supply amount of phthalate buffer can
It is provided with being based respectively on efflux time and service time.
6. dissolving out process (current detecting process)
After phthalate buffer will be replaced into determination unit 2 by above-mentioned liquid displacement process, control dress is calculated
8 are set, exports dissolution commencing signal to potentiostat PS.Accordingly, potentiostat PS is by the electric potential scanning of conductive diamond electrode 5
To positive potential direction, specifically, scanning to the current potential (for example,+1.0V) higher than the reduction potential of cadmium, by the complex of cadmium and copper
It dissolves out to phthalate buffer.
Once the complex of cadmium and copper dissolves out, adjoint with this, produced in conductive diamond electrode 5 and between electrode 3
Raw electric current.The electric current as caused by the complex of cadmium and copper, generates near+0.35V in this reaction system, the electric current (telecommunications
Number) it is sent to potentiostat PS, carry out control, the detection of the signal of each electrode.Here, the signal detected by potentiostat PS
It is sent to calculation control device 8.Phthalate buffer is discharged from the discharge line 12 of liquid displacement mechanism 11, to complete
Dissolve out process.
Figure 11 indicates an example of the VA characteristic curve obtained by the dissolution process.VA characteristic curve shown in Figure 11
In, the current peak observed near -0.35v derives from the complex of cadmium and copper, the current peak observed near 0.25V
Value derives from copper monomer.In addition, as the concentration of cadmium is got higher known in the VA characteristic curve shown in Figure 11, the peak value of electric current
Also it gets higher.
On the other hand, Figure 12 indicates that the C-V characteristic obtained in the case that the acid used when modulating extracting solution is hydrochloric acid is bent
An example of line.In the case where using hydrochloric acid when modulating extracting solution, the residual organic matter not being decomposed becomes disturbing factor, separately
Outside, since cadmium and hydrochloric acid form complex compound, as shown in figure 12, the current peak (near -0.6V) from cadmium is unobvious, thus
It cannot be by highly sensitive detection.
7. relation line production process
In present embodiment, to use standard addition method to analyze cadmium concentration, above-mentioned electro-deposition process is arrived using in offer
It further adds cadmium standard sample known to concentration in the extracting solution of~dissolution process and becomes predetermined concentration (such as 50ppb)
Sample carries out electro-deposition process~dissolution process similar to the above, the relationship of production cadmium concentration and current value or the quantity of electric charge
Line.
8. cadmium concentration calculation process
Calculation control device 8 is by obtained current value or the quantity of electric charge and the cadmium concentration of production and current value or the quantity of electric charge
Relation line comparison, calculate the cadmium concentration of extracting solution.At this moment, according to from as measured value current value or the quantity of electric charge subtract it is pre-
Differential electrical flow valuve or difference obtained by the base current value first only determined with phthalate buffer or the basic quantity of electric charge
Divide the quantity of electric charge to calculate cadmium concentration, so as to degree of precision calculates cadmium concentration.The cadmium concentration so calculated is shown in setting
In the display unit 801 of the front surface of cover C.
Electrowinning process after 9.
A period of time after the surface sweeping of current potential, by the way that the current potential of conductive diamond electrode 5 is maintained at+1.0V,
To make the cadmium of electro-deposition, copper all dissolve out, conductive diamond electrode 5 can be made to regenerate the state before being restored to measurement.
By so regenerating conductive diamond electrode 5, same electrode can be reused.Here, conductive diamond electrode 5 is again
It is raw, not just by the holding of fixed current potential, can also be realized by carrying out the multiple scanning of wide area current potential.
10. waste liquid process
After above-mentioned after electrowinning process, calculation control device 8 replaces the row of the discharge line 12 of mechanism 11 by control liquid
122 are pumped out, and solution after the measurement in determination unit 2 is discharged to waste liquid tank T2.After the waste liquid process, it is measured unit
Cleaning, power supply is set as OFF.
(effect of present embodiment)
There is the electrochemical determining device 100 of present embodiment formed according to this contact surface 2P, contact surface 2P to make
The electrode surface 5a of active electrode 5 is separated with the opposed faces 911a of stirrer 91, thus can be configured to stirrer 91 not with work
It is contacted with electrode 5, active electrode 5 will not be caused to damage by stirrer 91, be formed in the double of the electrode surface 5a of active electrode 5
Electric layer will not multilated.Hereby it is possible to improve the stability of electrochemical gaging.
In addition, having the retaining surface 2Q of the rotation gesture for being kept stirring son 91, therefore do not have to worry that stirrer 91 exists
Change posture in rotary course, generates the rotation failure that contacts or cannot rotate with active electrode 5 etc., stirrer 91 can be made
Rotation speed, rotation position stablize, the spin stabilization of stirrer 91 can be made.The spin stabilization for making stirrer 91 accordingly, from
And the convection current of fluid sample in the electrode surface 5a of active electrode 5 can be made approximately fixed, it can be improved electrochemical gaging
Stability.
Moreover, cadmium analysis method according to the present embodiment, using perchloric acid from rice etc. from the sample of biology
Product extract cadmium, decompose the organic matter for being contained in the sample from biology so as to not form the complex compound of cadmium, Neng Gougao
Carry out to precision the detection of cadmium and/or the measurement of its concentration.
In addition, use Potassium Hydrogen Phthalate as buffer in present embodiment, thus when measuring cadmium, as dry
The metal for disturbing lead, selenium, chromium, boron of factor etc. is wrapped up by carboxyl, as a result, being speculated as preventing the interference to cadmium.
Further, in the present embodiment, by carrying out including electrode clean processing and the electrode that hydrogen sealing endization is handled
Treatment process modifies the table of conductive diamond electrode to eliminate the organic matter for being adhered to active electrode, heavy metal in advance
Face, so as to further increase analysis precision.Particularly, it is believed that in the present embodiment, in phthalate buffer
It carries out electrode clean processing and generates CO free radical to be reacted by Ke Erbei, this can effectively carry out the decomposition of organic matter, removal.
In addition, the present invention is not limited to the above embodiments.
For example, it is also possible to form blade part in the cylindrical body part of stirrer.In this case, there is insertion
The hidden danger to be become smaller with the opening size of through-hole 91H, but the axis direction size of stirrer 91 can be made to become smaller.
In addition, the retaining surface 2Q of above embodiment is formed by the inside circumference 2x of determination unit 2, as shown in figure 13,
It can be set being arranged between the inside circumference 2x of determination unit 2 and the outside circumference 911m of stirrer 91, all on the inside of it
Face 10x is the distance member 10 of retaining surface 2Q.The distance member 10 is to have phase cross-section shape in the section vertical with axis direction
The cylindric component of shape.Here, can also be prominent from the inside circumference 10x of the distance member 10 to radially inner side by being formed
Cyclic lug, thus become with contact surface 2P device.
Further, in the above-described embodiment, stirrer 91 is the device with insertion through-hole 91H, but can also be with
It is the device without insertion through-hole 91H.In this case, cannot by electrode 3 and reference electrode 4 from the upper of stirrer 91
Portion is inserted into 5 side of active electrode, but is also possible to for example, making the distance ratio of contact surface 2P (protruding portion 22) and active electrode 5
Above embodiment is big, will be inserted into appearance to the side wall of electrode 3 and reference electrode 4 between protruding portion 22 and active electrode 5
It receives in the 2S of space, is configured to make to be located near the electrode surface 5a of active electrode 5 electrode 3 and reference electrode 4.
Moreover, the retaining surface 2Q of above embodiment be formed in a manner of surrounding the Pivot axle of stirrer 91 be in
Cylindric face is also possible to be configured to be formed in a manner of to above-mentioned contact surface 2P is placed in, contact with above-mentioned as shown in figure 14
Face 2P rotatably clamps stirrer 91.As retaining surface 2Q, it is also contemplated that being connect for the upper surface for example with stirrer 91
The plane annular in shape of touching.Retaining surface 2Q in the same manner as above-mentioned contact surface 2P, from the inside circumference 2x from determination unit 2 to
The lower surface of radially inner side cyclic lug 23 outstanding is formed.Here, Figure 14 illustrates the feelings using rodlike stirrer 91
Condition, can also be as embodiment described above, for the stirrer with insertion through-hole 91H.
Moreover, in the above-described embodiment, be have active electrode 5, to electrode 3 and reference electrode 4 by three electrodes
The device that method is measured is but it is also possible to be only having active electrode 5 and to the dress of electrode 3 being measured by two electrode methods
It sets.Although three-electrode method, which can control, is applied to active electrode 5 and the absolute value to the voltage between electrode 3, therefore can be into
The measurement of row precision and high sensitivity, but according to two electrode methods, the electrode used are only active electrode 5 and to electrode 3
Two electrodes, therefore can make determination unit 2 simple structure, miniaturization.
In the cadmium analysis method of above embodiment, as the production method of the relation line calculated for cadmium concentration, no
It is limited to standard addition method, in the case that the copper concentration in extracting solution is low, calibration curve method pre-production cadmium concentration also can be used
With the relation line of current value or the quantity of electric charge.
Further, the electrochemical determining device of above embodiment also can be applied to measure and contain in fluid sample
Any one of the heavy metal ion of Cu, As, Cd, Zn etc. or a variety of ingredients.
In the cadmium analysis method of above-described embodiment, although small so as to obtain noise by carrying out liquid displacement process
Signal, but process can also be replaced without liquid to measure the heavy metal ion of cadmium etc..
In addition, the present invention is not limited to above-mentioned embodiment, the range that as long as it does not depart from the spirit of the invention, so that it may into
The various changes of row.
Claims (5)
1. a kind of electrochemical determining device is the concentration for electrochemically measuring the predetermined ingredient for including in fluid sample
Electrochemical determining device has:
Determination unit accommodates aforesaid liquid sample；
Stirrer is arranged at the inside of said determination unit；
Contact surface is contacted with the opposed faces of the above-mentioned stirrer opposed with the electrode surface of active electrode, make above-mentioned opposed faces from
Above-mentioned electrode surface separation, above-mentioned active electrode are set as contacting with the fluid sample in said determination unit；
The faces different from above-mentioned opposed faces of retaining surface, above-mentioned stirrer are rotated along the retaining surface, and the retaining surface is for keeping
The rotation gesture of above-mentioned stirrer.
2. electrochemical determining device as described in claim 1, which is characterized in that
Above-mentioned retaining surface is formed in the inside circumference of said determination unit.
3. electrochemical determining device as claimed in claim 1 or 2, which is characterized in that
Above-mentioned stirrer has for the insertion through-hole in the insertion of its rotating center section to electrode or reference electrode.
4. electrochemical determining device as described in any one of claims 1-3, which is characterized in that
Above-mentioned stirrer have 1 that cylindrical body part and the open end of the side in above-mentioned body part formed or
Multiple blade parts,
The open end of another party of above-mentioned body part is the face with above-mentioned contact face contact,
The outside circumference of above-mentioned body part is the face rotated along above-mentioned retaining surface,
Above-mentioned multiple blade parts, by the open end in one side make stirrer center of gravity be overlapped with rotation center in a manner of shape
At.
5. a kind of stirrer, it is arranged at the inside for accommodating the determination unit of fluid sample, in the inside of said determination unit, with
From the electrode surface of the active electrode for being set as contacting with the fluid sample in said determination unit with above-mentioned electrode surface pair
The direction set separates the stirrer to be formed contact face contact rotation,
With prominent 1 or the multiple blades formed in end face from the end face opposite side with above-mentioned stirrer contact face contact
Portion.
Applications Claiming Priority (3)
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| JP2012286716A JP5759442B2 (en) | 2012-12-28 | 2012-12-28 | Electrochemical analysis method, electrochemical analyzer and reagent set |
| JP2012-286716 | 2012-12-28 | ||
| CN201310655479.8A CN103913490B (en) | 2012-12-28 | 2013-12-06 | Electrochemical analysis method, electrochemical analysis device and reagent set |
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| CN201811081576.XA Pending CN109270132A (en) | 2012-12-28 | 2013-12-06 | Electrochemical determining device and stirrer |
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| JP6871088B2 (en) * | 2017-07-05 | 2021-05-12 | アークレイ株式会社 | How to clean carbon electrodes |
| JP7277529B2 (en) * | 2021-09-14 | 2023-05-19 | 住友化学株式会社 | electrochemical sensor |
| US20240069002A1 (en) * | 2022-08-24 | 2024-02-29 | Hach Company | Electrochemical cell stirring |
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Also Published As
| Publication number | Publication date |
|---|---|
| CN103913490A (en) | 2014-07-09 |
| JP2014130031A (en) | 2014-07-10 |
| CN103913490B (en) | 2018-10-16 |
| JP5759442B2 (en) | 2015-08-05 |
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