CN104458878B - Saccharin sodium concentration detection device and saccharin sodium concentration detection method - Google Patents
Saccharin sodium concentration detection device and saccharin sodium concentration detection method Download PDFInfo
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- CN104458878B CN104458878B CN201410502330.0A CN201410502330A CN104458878B CN 104458878 B CN104458878 B CN 104458878B CN 201410502330 A CN201410502330 A CN 201410502330A CN 104458878 B CN104458878 B CN 104458878B
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Abstract
The invention discloses a saccharin sodium concentration detection device and a saccharin sodium concentration detection method. The saccharin sodium concentration detection device comprises a controller, a storage device, a container which is provided with an opening in the upper end and is capable of containing liquid, a cover plate which is arranged on the container, a counter electrode which is arranged on the cover plate, extends downwards and is made of a platinum material, an evolvent-shaped guide rail which is embedded into an opening in the lower end of the lower part of the cover plate, a rotating device which is arranged on the guide rail and can move along the guide rail, a stirring device which is arranged on the bottom of the container and a dropping funnel which is arranged on the cover plate and used for dropwise adding saccharin sodium solution into the container, wherein the counter electrode is connected with the cover plate through a first motor, one end of the guide rail is close to the first motor, and the other end of the guide rail is close to the edge of the cover plate. The saccharin sodium concentration detection device has characteristics of high detection precision, high speed, good stability and good repeatability.
Description
Technical field
The present invention relates to technical field of food detection, especially relate to a kind of detection accuracy height, fireballing saccharin sodium
Concentration detection apparatus and detection method.
Background technology
Existing sugar detection technical method has Instrumental Analysis detection method and chemical measure, although Instrumental Analysis detection method behaviour
Make simple, but there is the low defect of accuracy of detection；There is complex operation, the deficiency of poor repeatability in chemical measure.
Chinese patent mandate publication number: cn103528877a, authorizes publication date on January 22nd, 2014, discloses a kind of little
The online system of detecting concentration of sugar of type biochemical reactor, including 1 touch screen, is responsible for accepting the setting of Field Force and operation；2
Constant flow pump, is responsible for reactant liquor is diluted；1 online sugar analyzer, is responsible for the on-line checking of sugar concentration；1 sugared dense offline
Degree analyser, is responsible for the offline inspection of sugar concentration；1 flush bonding module bl2100, as the control unit of system, controls constant current
The flow velocity of pump and the action of sugared concentration analyzer, gather the sugared concentration Testing value of online sugar analyzer, collection value are carried out
Line corrects, and obtains in biochemical reactor accurately sugared concentration Testing value, and according to the value of offline sugar concentration analyzer, model is joined
Number is modified.The weak point of this invention is, accuracy of detection is low and the deficiency of poor repeatability.
Content of the invention
The goal of the invention of the present invention is to overcome detection method accuracy of detection of the prior art low and poor repeatability
Not enough, there is provided a kind of detection accuracy height, fireballing saccharin sodium concentration detection apparatus and detection method.
To achieve these goals, the present invention employs the following technical solutions:
A kind of saccharin sodium concentration detection apparatus, described saccharin sodium concentration detection apparatus are electrically connected with electrochemical workstation；Bag
Include controller, memorizer, fill the container of the upper end open of liquid, the cover plate on container, on cover plate to downward
The alloy platinum material stretched make to electrode, the involute shape guide rail of the lower ending opening of embedded cover plate bottom, on guide rail can edge
The tumbler of guide rail movement, located at container bottom agitating device and located on cover plate for into container instill saccharin sodium
The Dropping funnel of solution；Electrode is connected with cover plate by the first motor, guide rail one end is near the first motor, the guide rail other end
Near side edge thereof；
Described tumbler bottom is provided with the working electrode that foam copper product is made, and agitating device passes through waterproof machine and appearance
Device bottom is connected；Working electrode and to electrode all in bar shaped tabular；Described controller respectively with waterproof machine, memorizer,
One motor, tumbler and electrochemical workstation electrical connection；Electrode and working electrode are electrically connected with electrochemical workstation respectively.
The setting of the guide rail in involute shape of the present invention, makes working electrode and to the spacing continuously adjustabe between electrode,
It is easy to electrochemical workstation and find the optimum position residing for two electrodes when making highest current density, thus improving accuracy of detection
Property.Agitating device is used for the liquid in container is stirred, and tumbler is used for driving working electrode to move.
The present invention passes through to detect concentration known saccharin sodium solution, obtains the saccharin sodium concentration prediction model of saccharin na concn,
And the saccharin na concn of unknown concentration is detected with saccharin sodium concentration prediction model.
Therefore, the present invention has simple to operate, high degree of automation；Accuracy of detection is high, and speed is fast；Device stability is good,
Reproducible feature.
Preferably, described guide rail includes top board and two baffle plates located at top board both sides, two baffle plates are provided with relatively
The guide openings answered；Described tumbler includes motor fixing seat, the second motor in motor fixing seat and the second motor
Two gears connecting respectively of two rotating shafts and two extension rods being respectively arranged on outside two gears, two extension rods divide
Do not stretch in two guide openings；
Described guide rail bottom is provided with, at the position corresponding with two gears, the track plates that two upper surfaces carry groove；Lead
Rail is provided with for the dual-cavity with two gear cooperations, and two track plates two ends are all connected with guide rail, described working electrode
It is connected with motor fixing seat；Described second motor is electrically connected with the controller.
The setting of guide rail, tumbler and closed plate, makes the working electrode can be along the stable movement of guide rail.
Preferably, described agitating device includes the horizontal stirring pipe being connected with the rotating shaft of waterproof machine, level stirs
Pipe be provided with some to the through hole being oppositely arranged；It is vertical with the axial line of horizontal stirring pipe that horizontal stirring pipe is provided with several
Straight-bar.
Preferably, described straight-bar includes longitudinal rod and horizon bar.
The structure setting of agitating device, make that the solution in container can be stirred is more uniform.
Preferably, cover plate and container are all rounded；Cover plate lower surface is provided with annular groove, container upper end insertion annular
It is connected with cover plate in groove.
A kind of detection method being applied to saccharin sodium concentration detection apparatus, comprises the steps:
(6-1) it is provided with sweep interval a, scanning times maximum n, scanning times sequence number i in controller, i's is initial
It is worth for 1；
The 0.1m naoh taking 20 to 50ml inserts in container, cover plate is installed to container finish, makes working electrode and to electricity
Pole is stretched in naoh；
Electrochemical workstation exports the constant voltage of 0.40v to 0.6v to working electrode, and the saccharin sodium that regulation fills 0.1m is molten
The piston of the Dropping funnel of liquid, makes Dropping funnel instill a saccharin sodium solution in time a is to container；
(6-2) after instilling first saccharin sodium in Dropping funnel is to container to instill second saccharin sodium solution it
Before, controller controls agitating device to the liquid agitation time b in container, b ＜ a by waterproof machine；Controller controls first
Motor drives and electrode is horizontally rotated, and controls tumbler to drive working electrode to reciprocate along guide rail, electrochemical operation simultaneously
Stand and detect electric current density, when the electric current density of detection reaches maximum, controller controls tumbler and the first motor to stop
Work, obtains the optimum position to electrode and working electrode；
During mobile to electrode horizontal rotation and working electrode, electrode and working electrode are remained with maximum
Relative area；
Controller calculates the saccharin na concn k in current container1, by k1And with k1Corresponding electric current density s (t) storage
To in memorizer；
(6-3) Dropping funnel instills i+1 into container and drips saccharin sodium solution, and controller controls stirring by waterproof machine
Device is to the liquid agitation time b in container, b ＜ a；Electrochemical workstation detects electric current density, and controller calculates current container
Interior saccharin na concn ki+1, by ki+1And with ki+1Corresponding electric current density s (t) stores in memorizer；
(6-4) as i≤n-1, make i value increase by 1, proceed to step (6-3)；Otherwise, proceed to step (6-5)；
(6-5) n obtained electric current density s (t) is inputted second-order linear system accidental resonance model by controller respectively In；And make second-order linear system accidental resonance
Model resonates；
Wherein, x (t) is the displacement of vibration particle, and ω is angular frequency, r and ω is the attenuation quotient setting and linear respectively
The frequency of vibration particle, c is the signal adjustment coefficient setting, and b is the quadratic noise ξ setting2T the coefficient of (), ξ (t) is three discriminations
Noise, ξ (t) ∈ {-a, 0, a }, a ＞ 0, the dismutation of noise follows Poisson distribution, and its probability distribution is ps(a)=ps(-a)
=q, ps(0)=1-2q, wherein 0 ＜ q ＜ 0.5；
Noise average and dependency follow<ξ (t)>=0,<ξ (t) ξ (t+ τ)>=2qa2e-λτ；
Wherein λ is correlation ratio, and the glacing flatness of three discriminations noise ξ (t) is
Controller utilizes formulaCalculate and obtain and n electric current density s (t) point
Not corresponding output signal-to-noise ratio snr1, snr2..., snrn；
Controller reads the saccharin na concn k in memorizer1, k2..., kn；Controller utilizes point (k1, snr1), (k2,
snr2) ..., (kn, snrn) matching is in line, and draws saccharin sodium concentration prediction model according to the straight line of matching:The liquid of container is poured out, and vessel cleaning is clean；
(6-6) detection of the saccharin sodium solution w of unknown concentration:
The saccharin sodium solution w taking 20 to 50ml inserts in container, cover plate is installed to container finish, makes working electrode and right
Electrode stretches in saccharin sodium solution, and makes working electrode and be located at optimum position determined by step (6-2) to electrode；Electrochemistry
Work station exports the constant voltage of 0.40v to 0.6v, electrochemical workstation detection electric current density s (t) to working electrode, and controller will
In s (t) input second-order linear system accidental resonance model,
And utilize formulaCalculate and obtain output signal-to-noise ratio snr, snr is substituted intoObtain concentration k of saccharin sodium solution w.
Preferably, also including alarm, alarm and controller electrically connect；Also include alarm, alarm and control
Device electrically connects；Also include following electrode calibration step before the step (6-1):
(7-1) the 0.1m naoh taking 30 to 48ml inserts in the first beaker, by working electrode and to electrode insertion first burning
In the naoh solution of cup, be circulated voltammetry scanning using electrochemical workstation, make the driving voltage of working electrode-
First it is gradually increased in the range of 0.2v-0.75v, then is gradually reduced, obtaining abscissa is driving voltage, and vertical coordinate is electric current density
Curve, difference g between the maximum of calculating current density and minima；
(7-2) 0.1m naoh and 0.1mm saccharin sodium is taken to insert in the second beaker and stir all successively according to 3: 2 ratio
Even, insert in the solution of the second beaker by working electrode and to electrode, be circulated voltammetry scanning using electrochemical workstation,
So that the driving voltage of working electrode is first gradually increased in the range of -0.2v-0.75v, then be gradually reduced, obtaining abscissa is excitation
Voltage, vertical coordinate is the curve of electric current density, the difference g ' between the maximum of calculating current density and minima；
(7-3) controller utilizesCalculation error, when e≤4.7%, proceeds to step (6-1)；
Otherwise, controller controls alarm equipment alarm, and operator are to being surface-treated to electrode or changed to electrode；Return
Return step (7-1).
Because the working electrode that foam copper product is made is disposable, all examined with new working electrode every time
Survey, but alloy platinum material make to electrode will multiple Reusability, access times are more, and corrosion oxidized to electrode is more serious,
So needing to detect to the state of electrode, after calibration, only qualified detection is just used in electrode it is ensured that inspection
Survey the accuracy of result.
Preferably, driving voltage speed with 0.05v/s in the range of -0.2v-0.75v is first gradually increased, then with
The speed of 0.05v/s is gradually reduced.
Preferably, the area that foam copper and platinum electrode stretch into solution is 0.085cm2To 0.135cm2.
Preferably, a is 42 to 58 seconds, n is 10 to 108, b is 9 to 30 seconds.
Therefore, the invention has the following beneficial effects: simple to operate, high degree of automation；Accuracy of detection is high, and speed is fast；
Device stability is good, reproducible.
Brief description
Fig. 1 is a kind of structural representation of the present invention；
Fig. 2 is a kind of structural representation of the guide rail of the present invention；
Fig. 3 is a kind of structural representation of the tumbler of the present invention；
Fig. 4 is a kind of theory diagram of the present invention；
Fig. 5 is a kind of flow chart of embodiments of the invention 1；
Fig. 6 is the cyclic voltammetry calibration result figure of the present invention.
In figure: electrochemical workstation 1, controller 2, memorizer 3, container 4, cover plate 5, guide rail 6, platinum are to electrode 7, rotation dress
Put 8, agitating device 9, Dropping funnel 10, working electrode 11, the first motor 12, waterproof machine 13, stirring pipe 14, track plates 15,
Baffle plate 16, motor fixing seat 17, the second motor 18, rotating shaft 19, gear 20, extension rod 21, dual-cavity 22, through hole 23, longitudinal rod
24th, horizon bar 25.
Specific embodiment
The present invention will be further described with reference to the accompanying drawings and detailed description.
Embodiment 1
Embodiment as Figure 1 and Figure 4 is a kind of saccharin sodium concentration detection apparatus, saccharin sodium concentration detection apparatus with electricity
Chem workstation 1 electrically connects；Including controller 2, memorizer 3, fill the container 4 of the upper end open of liquid, on container
Cover plate 5, the alloy platinum material extending downwardly on cover plate make to electrode 7, located at container bottom agitating device 9 and located at
The Dropping funnel 10 for instilling saccharin sodium solution into container on cover plate；Agitating device includes the rotating shaft phase with waterproof machine
Connect horizontal stirring pipe 14, horizontal stirring pipe be provided with some to the through hole 23 being oppositely arranged；If horizontal stirring pipe is provided with
The dry straight-bar vertical with the axial line of horizontal stirring pipe.Cover plate is made using polytetrafluoroethylmaterial material, and container adopts glass material
Material is made.
Straight-bar includes longitudinal rod 24 and horizon bar 25.Cover plate and container are all rounded；It is recessed that cover plate lower surface is provided with annular
Groove, is connected with cover plate in container upper end insertion annular groove.
The involute shape guide rail 6 of the lower ending opening of embedded cover plate bottom as shown in Figure 2, on guide rail can be along guide rail
The tumbler 8 of movement,
As shown in figure 3, tumbler bottom is provided with the working electrode 11 that foam copper product is made, guide rail includes top board and sets
In two baffle plates 16 of top board both sides, two baffle plates are provided with corresponding guide openings；Tumbler includes motor fixing seat
17th, the second motor 18 in motor fixing seat is connected respectively with two rotating shafts 19 of the second motor two gears 20 and
It is respectively arranged on two extension rods 21 on outside two gears, two extension rods are respectively protruding in two guide openings；
Guide rail bottom is provided with, at the position corresponding with two gears, the track plates 15 that two upper surfaces carry groove；Guide rail
It is provided with for the dual-cavity 22 with the cooperation of two gears, two track plates two ends are all connected with guide rail, working electrode and electric
Machine fixed seat is connected；
As shown in figure 4, agitating device is connected with container bottom by waterproof machine 13；Working electrode and be in all to electrode
Bar shaped tabular；Controller is electrically connected with waterproof machine, memorizer, the first motor, tumbler and electrochemical workstation respectively；Right
Electrode and working electrode are electrically connected with electrochemical workstation respectively, and the second motor is electrically connected with the controller.
As shown in figure 5, a kind of detection method of saccharin sodium concentration detection apparatus, comprise the steps:
Step 100, is provided with sweep interval 50 seconds in controller, scanning times maximum n=10, scanning times sequence number
The initial value of i, i is 1；
The 0.1m naoh taking 30ml inserts in container, cover plate is installed to container finish, makes working electrode and electrode is stretched
Enter in naoh；
Electrochemical workstation exports the constant voltage of 0.5v to working electrode, adjusts the dropping liquid of the saccharin sodium solution filling 0.1m
The piston of funnel, make Dropping funnel every 50 seconds to container in instill a saccharin sodium solution；
Step 200, finds optimum position and by k1And with k1Corresponding electric current density s (t) stores in memorizer:
After instilling first saccharin sodium in Dropping funnel is to container to before instill second saccharin sodium solution, control
Device controls agitating device to the liquid agitation in container 10 seconds by waterproof machine；Controller controls the first motor to drive to electrode
Horizontal rotation, controls tumbler to drive working electrode to reciprocate along guide rail, electrochemical workstation detects electric current density simultaneously,
When the electric current density of detection reaches maximum, controller controls tumbler and the first motor to quit work, and obtains to electrode
Optimum position with working electrode；
During mobile to electrode horizontal rotation and working electrode, electrode and working electrode are remained with maximum
Relative area；
Controller calculates the saccharin na concn k in current container1(for example, every saccharin sodium solution is 0.05ml, controller
The total measurement (volume) that saccharin sodium solution according to having instilled in container drips solution in number and container calculates saccharin na concn k1), by k1With
With k1Corresponding electric current density s (t) stores in memorizer；
Step 300,
Dropping funnel instills i+1 into container and drips saccharin sodium solution, and controller controls agitating device by waterproof machine
To the liquid agitation in container 10 seconds；Electrochemical workstation detects electric current density, and controller calculates the saccharin sodium in current container
Concentration ki+1, by ki+1And with ki+1Corresponding electric current density s (t) stores in memorizer；
Step 400, when i≤9, makes i value increase by 1, proceeds to step 300；Otherwise, proceed to step 500；
Step 500, data processing:
Obtain 10 electric current densities s (t) are inputted second-order linear system accidental resonance model by controller respectively In；And make second-order linear system accidental resonance
Model resonates；
Wherein, x (t) is the displacement of vibration particle, and ω is angular frequency, r and ω is the attenuation quotient setting and linear respectively
The frequency of vibration particle, c is the signal adjustment coefficient setting, and b is the quadratic noise ξ setting2T the coefficient of (), ξ (t) is three discriminations
Noise, ξ (t) ∈ {-a, 0, a }, a ＞ 0, the dismutation of noise follows Poisson distribution, and its probability distribution is ps(a)=ps(-a)
=q, ps(0)=1-2q, wherein 0 ＜ q ＜ 0.5；
Noise average and dependency follow<ξ (t)>=0,<ξ (t) ξ (t+ τ)>=2qa2e-λτ；
Wherein λ is correlation ratio, and the glacing flatness of three discriminations noise ξ (t) is
Using formulaCalculate and obtain corresponding respectively with 10 electric current densities s (t)
Output signal-to-noise ratio snr1, snr2..., snr10；
Controller reads the saccharin na concn k in memorizer1, k2..., k10；Controller utilizes point (k1, snr1), (k2,
snr2) ..., (k10, snr10) matching is in line, and draws saccharin sodium concentration prediction model according to the straight line of matching:The liquid of container is poured out, and vessel cleaning is clean；
Step 600, the detection of the saccharin sodium solution w of unknown concentration:
The saccharin sodium solution w taking 30ml inserts in container, cover plate is installed to container finish, makes working electrode and to electrode
Stretch in saccharin sodium solution, and make working electrode and optimum position determined by step 200 is located to electrode；Electrochemical workstation
Export the constant voltage of 0.5v, electrochemical workstation detection electric current density s (t) to working electrode, s (t) is inputted second order by controller
In linear system accidental resonance model,
And utilize formulaCalculate and obtain output signal-to-noise ratio snr, snr is substituted intoObtain concentration k of saccharin sodium solution w.
Embodiment 2
Comprise all structures and the step part of embodiment 1 in embodiment 2, also include alarm, alarm and controller
Electrical connection；Following electrode calibration step was also included before step 100:
Step 710, takes the 0.1m naoh of 40ml to insert in the first beaker, by working electrode and to electrode insertion first burning
In the naoh solution of cup, be circulated voltammetry scanning using electrochemical workstation, make the driving voltage of working electrode-
First it is gradually increased in the range of 0.2v-0.75v, then is gradually reduced, obtaining abscissa is driving voltage, and vertical coordinate is electric current density
Curve, difference g between the maximum of calculating current density and minima；
Step 720, the ratio according to 3: 2 takes 0.1m naoh and 0.1mm saccharin sodium to insert in the second beaker successively, and stirs
Mix uniformly, insert in the solution of the second beaker by working electrode and to electrode, be circulated voltammetry using electrochemical workstation
Scanning, makes the driving voltage of working electrode first be gradually increased in the range of -0.2v-0.75v, then is gradually reduced, obtain abscissa
For driving voltage, vertical coordinate is the curve of electric current density, the difference g ' between the maximum of calculating current density and minima；
Step 730, controller utilizesCalculation error, when e≤4.7%, proceeds to step 100；
Otherwise, controller controls alarm equipment alarm, and operator detect to electrode, and in the present embodiment, it is right to find
Electrode surface has defect, is changed to electrode；Return to step 710.
Fig. 6 is the cyclic voltammetry calibration testing result figure showing on electrochemical workstation, can be drawn by figure,
G '=6.8v, g '=6.6v,Therefore proceed to step 100.
In the present embodiment, driving voltage speed with 0.05v/s in the range of -0.2v-0.75v is first gradually increased, then with
The speed of 0.05v/s is gradually reduced.The area that foam copper and platinum electrode stretch into solution is 0.1cm2.
It should be understood that the present embodiment is only illustrative of the invention and is not intended to limit the scope of the invention.In addition, it is to be understood that
After having read the content of present invention instruction, those skilled in the art can make various changes or modifications to the present invention, these etc.
Valency form equally falls within the application appended claims limited range.
Claims (10)
1. a kind of saccharin sodium concentration detection apparatus, described saccharin sodium concentration detection apparatus are electrically connected with electrochemical workstation (1)；Its
Feature is, including controller (2), memorizer (3), to fill the container (4) of the upper end open of liquid, the cover plate on container
(5), the alloy platinum material extending downwardly on cover plate make to electrode (7), gradually the opening of the lower ending opening of embedded cover plate bottom
Linear guide (6), on guide rail can along the tumbler (8) of guide rail movement, located at container bottom agitating device (9) and
Located on cover plate for into container instill saccharin sodium solution Dropping funnel (10)；To electrode pass through the first motor (12) with
Cover plate is connected, and near the first motor, the guide rail other end is near side edge thereof for guide rail one end；
Described tumbler bottom is provided with the working electrode (11) that foam copper product is made, and agitating device passes through waterproof machine (13)
It is connected with container bottom；Working electrode and to electrode all in bar shaped tabular；Described controller respectively with waterproof machine, storage
Device, the first motor, tumbler and electrochemical workstation electrical connection；Electric with electrochemical workstation respectively to electrode and working electrode
Connect.
2. saccharin sodium concentration detection apparatus according to claim 1, is characterized in that, described guide rail includes top board and located at top
Two baffle plates (16) of plate both sides, two baffle plates are provided with corresponding guide openings；Described tumbler includes motor to be fixed
Be connected respectively with two rotating shafts (19) of the second motor two of seat (17), the second motor (18) in motor fixing seat
Gear (20) and two extension rods (21) being respectively arranged on outside two gears, two extension rods are respectively protruding into two guiding and open
In mouthful；
Described guide rail bottom is provided with, at the position corresponding with two gears, the track plates (15) that two upper surfaces carry groove；Lead
Rail is provided with for the dual-cavity (22) with two gear cooperations, and two track plates two ends are all connected with guide rail, described work
Electrode is connected with motor fixing seat；Described second motor is electrically connected with the controller.
3. saccharin sodium concentration detection apparatus according to claim 1, is characterized in that, described agitating device includes and anti-water power
The horizontal stirring pipe (14) that the rotating shaft of machine is connected, horizontal stirring pipe be provided with some to the through hole being oppositely arranged (23)；Level
Stirring pipe is provided with several straight-bars vertical with the axial line of horizontal stirring pipe.
4. saccharin sodium concentration detection apparatus according to claim 3, is characterized in that, described straight-bar include longitudinal rod (24) and
Horizon bar (25).
5. the saccharin sodium concentration detection apparatus according to claim 1 or 2 or 3 or 4, is characterized in that, cover plate and container are in all
Circular；Cover plate lower surface is provided with annular groove, is connected with cover plate in container upper end insertion annular groove.
6. a kind of detection method of the saccharin sodium concentration detection apparatus being applied to described in claim 1, is characterized in that, including as follows
Step:
(6-1) it is provided with sweep interval a in controller, scanning times maximum n, scanning times sequence number i, the initial value of i is
1；
The 0.1m naoh taking 20 to 50ml inserts in container, cover plate is installed to container finish, makes working electrode and electrode is stretched
Enter in naoh；
Electrochemical workstation exports the constant voltage of 0.40v to 0.6v to working electrode, adjusts the saccharin sodium solution filling 0.1m
The piston of Dropping funnel, makes Dropping funnel instill a saccharin sodium solution in time a is to container；
(6-2) after instilling first saccharin sodium in Dropping funnel is to container to before instill second saccharin sodium solution, control
Device processed controls agitating device to the liquid agitation time b in container, b ＜ a by waterproof machine；Controller controls the first motor belt motor
Move and electrode is horizontally rotated, control tumbler to drive working electrode to reciprocate along guide rail, electrochemical workstation detects simultaneously
Electric current density, when the electric current density of detection reaches maximum, controller controls tumbler and the first motor to quit work, and obtains
To the optimum position to electrode and working electrode；
During mobile to electrode horizontal rotation and working electrode, electrode and working electrode are remained with the relative of maximum
Area；
Controller calculates the saccharin na concn k in current container1, by k1And with k1Corresponding electric current density s (t) stores deposits
In reservoir；
(6-3) Dropping funnel instills i+1 into container and drips saccharin sodium solution, and controller controls agitating device by waterproof machine
To the liquid agitation time b in container, b ＜ a；Electrochemical workstation detects electric current density, and controller calculates in current container
Saccharin na concn ki+1, by ki+1And with ki+1Corresponding electric current density s (t) stores in memorizer；
(6-4) as i≤n-1, make i value increase by 1, proceed to step (6-3)；Otherwise, proceed to step (6-5)；
(6-5) n obtained electric current density s (t) is inputted second-order linear system accidental resonance model by controller respectivelyIn；And make second-order linear system accidental resonance
Model resonates；
Wherein, x (t) is the displacement of vibration particle, and ω is angular frequency, r and ω is the attenuation quotient setting and linear oscillator respectively
The frequency of particle, c is the signal adjustment coefficient setting, and b is the quadratic noise ξ setting2The coefficient of (t), ξ (t) is three discrimination noises,
ξ (t) ∈ {-a, 0, a }, a ＞ 0, the dismutation of noise follows Poisson distribution, and its probability distribution is ps(a)=ps(- a)=q, ps
(0)=1-2q, wherein 0 ＜ q ＜ 0.5；
Noise average and dependency follow<ξ (t)>=0,<ξ (t) ξ (t+ τ)>=2qa2e-λτ,<ξ (t)>is the integral mean of ξ (t)
Value,<ξ (t) ξ (t+ τ)>is the integral mean of ξ (t) ξ (t+ τ)；
Wherein λ is correlation ratio, and the glacing flatness of three discriminations noise ξ (t) is
Controller utilizes formulaCalculate and obtain corresponding respectively with n electric current density s (t)
Output signal-to-noise ratio snr1, snr2..., snrn；
Controller reads the saccharin na concn k in memorizer1, k2..., kn；Controller utilizes point (k1, snr1), (k2,
snr2) ..., (kn, snrn) matching is in line, and draws saccharin sodium concentration prediction model according to the straight line of matching:The liquid of container is poured out, and vessel cleaning is clean；
(6-6) detection of the saccharin sodium solution w of unknown concentration:
The saccharin sodium solution w taking 20 to 50ml inserts in container, cover plate is installed to container finish, makes working electrode and to electrode
Stretch in saccharin sodium solution, and make working electrode and optimum position determined by step (6-2) is located to electrode；Electrochemical operation
Stand and export the constant voltage of 0.40v to 0.6v, electrochemical workstation detection electric current density s (t) to working electrode, controller is by s (t)
In input second-order linear system accidental resonance model,
And utilize formulaCalculate and obtain output signal-to-noise ratio snr, snr is substituted intoObtain concentration k of saccharin sodium solution w.
7. the detection method of saccharin sodium concentration detection apparatus according to claim 6, is characterized in that, also include alarm,
Alarm and controller electrical connection；Also include following electrode calibration step before the step (6-1):
(7-1) the 0.1m naoh taking 30 to 48ml inserts in the first beaker, inserts the first beaker by working electrode and to electrode
In naoh solution, it is circulated voltammetry scanning using electrochemical workstation, the driving voltage making working electrode is in -0.2v-
First it is gradually increased in the range of 0.75v, then is gradually reduced, obtaining abscissa is driving voltage, and vertical coordinate is the curve of electric current density,
Difference g between the maximum of calculating current density and minima；
(7-2) 0.1m naoh and 0.1mm saccharin sodium is taken to insert in the second beaker and stir successively according to 3: 2 ratio, will
In working electrode and the solution to electrode insertion the second beaker, it is circulated voltammetry scanning using electrochemical workstation, makes work
The driving voltage making electrode is first gradually increased in the range of -0.2v-0.75v, then is gradually reduced, and obtaining abscissa is excitation electricity
Pressure, vertical coordinate is the curve of electric current density, the difference g ' between the maximum of calculating current density and minima；
(7-3) controller utilizesCalculation error, when e≤4.7%, proceeds to step (6-1)；
Otherwise, controller controls alarm equipment alarm, and operator are to being surface-treated to electrode or changed to electrode；Return step
Suddenly (7-1).
8. the detection method of saccharin sodium concentration detection apparatus according to claim 7, is characterized in that, driving voltage-
In the range of 0.2v-0.75v, the speed with 0.05v/s is first gradually increased, then is gradually reduced with the speed of 0.05v/s.
9. the detection method of saccharin sodium concentration detection apparatus according to claim 7, is characterized in that, foam copper and platinum electrode
The area stretching into solution is 0.085cm2To 0.135cm2.
10. the detection method of the saccharin sodium concentration detection apparatus according to claim 6 or 7 or 8 or 9, is characterized in that, a is
42 to 58 seconds, n is 10 to 108, b was 9 to 30 seconds.
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