CN1448712A - A potentiometric titration instrument - Google Patents
A potentiometric titration instrument Download PDFInfo
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- CN1448712A CN1448712A CN 02116523 CN02116523A CN1448712A CN 1448712 A CN1448712 A CN 1448712A CN 02116523 CN02116523 CN 02116523 CN 02116523 A CN02116523 A CN 02116523A CN 1448712 A CN1448712 A CN 1448712A
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Abstract
The potential titrator includes liquid sucking titration unit, data collecting and converting unit, driving unit, computer and application software. It has modular structure, in which the system unit and computer are connected serially for communication and the whole control process and data processing are performed via software automatically. The titrator can display real-time titration curve, terminate titration and display test data automatically, and is suitable for determining alkaline nitrogen content in petroleum and petroleum product and the potential titration of other specimens.
Description
The present invention relates to a kind of potentiometric titrimeter.
Chinese patent CN 2384221 (99236433.7) discloses a kind of multifunctional microcomputer control autotitrator, this autotitrator is made up of microcomputer, dripping control device, liquid-adding device, titration cell, pick-up unit and analog to digital converter, drive the stepper motor of liquid-adding device by dripping control device, to the titration cell liquid feeding, photometric titration and potentiometric titration dual mode are arranged.
CN 2258989 (96225056.2) discloses a kind of electrotitration apparatus, this titrator comprises titration, solution stirring, titration end-point and circuit are controlled four parts, titration partly comprises buret and places charging valve up and down, the titration valve, it is respectively by lead and charging valve switch, the rate of titration regulator, the titration on ﹠ off switch joins, solution stirring partly comprises the micromotor that is fixed with magnetic patch on the arbor, the stirring sinker is magnetic in the solution container, the titration end-point control section comprises the darkroom that is provided with the color identifying device, and the circuit control section is regulated by monostable triggering, titration, stir, the titration end-point control circuit is formed.
CN 1104334 (94104539.0) discloses a kind of automatic titration device, it is characterized in that described device comprises accurate charger, signal converter, signal amplifier, data recording portion and signal controlling part; Described accurate charger is a peristaltic pump; Described signal converter is made up of chemical reactor, sensitive element and stirrer, tested chemical substance is in chemical reactor, and sensitive element places measured matter, and sensitive element is the pH combination electrode, or for contrast electrode and signal electrode combine, stirrer places the chemical reactor bottom; Described signal amplifier is made up of filtering circuit and signal amplifier, and filtering circuit comprises four differential amplifiers; Described data recording section is divided into registering instrument or is A/D converter; Described signal control part branch comprises two triodes, and relay is in order to control accurate charger, and described accurate charger is high-order galvanostat.
CN 2141084 (92238548.3) discloses a kind of base number autotitrator, this titrator is a kind of automatic potentiometric titrimeter of controlled by single chip microprocessor, it comprises single-chip microprocessor system, adjustable high resistance measurement circuit, A/D converter, electronic peristaltic pump, magnetic stirring apparatus, switching power supply, the light-emitting nixie tube display, keyboard and casing, it is characterized in that: A/D converter adopts 41/2 double integration circuit of high precision, photoelectric coupler isolation is all adopted in its titration control of electronic peristaltic pump and the pulse measurement of consumption liquid measure, pulse signal is directly taken out by rp-drive, and directly by single-chip microcomputer timing ga(u)ge/number device metering, magnetic stirring apparatus passes through the control interface pilot relay by microcomputer after shaping in pulse, the mixing time of stirrer is accurately set by program, magnetic stirring apparatus, electronic peristaltic pump, display and keyboard combination are as a whole.
CN 86103336 (86103336) discloses a kind of automatical potentiometric titrimeter, be characterized in that liquid road control executive component is an air intercepting valve, the air valve port that dams directly or by a conduit and the suitable for reading of dropping liquid gauge line links, and electronic control system only connects another output amplifier with a simple differential amplifier as input circuit.
J.Chem.Educ., 77 (3), 389-390,2000, reported a kind of laboratory autotitrator, the feature of this titrator is that titrant is carried with constant speed with volume pump, electrode output is directly delivered to a register by an analog differentiation device, this analog differentiation device is made up of an operational amplifier, and operational amplifier is amplified to a scope that is suitable for register with electrode output, and the back is two differentiating circuit.This titrator has pump and register, inserts the power bar of a standard in the register, when power bar opens or closes, and beginning or termination titration.
Analytical instrument, (2), 24-27,1997 have reported a kind of digital automatical potentiometric titrimeter, and it is made up of a Mriotte steady flow titrator, a socle English timer, an accurate stabilized voltage supply, automatic stoichiometric point judgement controller, indicator electrode (inert electrode and ion-selective electrode) and a magnetic stirrer.This titrator carries out potentiometric titration, can when carrying out accurate colorimetric titration, need not show the terminal point current potential automatically with vs.
LaborPraxis, 20 (4), 50,53-4,57-8 (German) 1996 has reported computer-controlled conventional titration, has narrated the titration system series that is connected with computer.This titration system satisfies ISO 900X and the GLP requirement about data file, the robotization when having realized using the sample transducer, because system is controlled by elements such as sensors, titration system is safe and reliable.
Univ.Iagellon.Acta Chim., 36,85-8 (English) 1993 has reported the potentiometric titrimeter of a kind of general calculation machine control, is made of the module of cheap easy acquisition.Can measure two kinds or three kinds of ions in the solution simultaneously by the simple potential titration curve.Terminal point defines three kinds of methods: (a) by point of inflexion on a curve; (b) by the peak of curve, curve is titration required time-vs volume curve; (c) according to Gran ' s method.
Through the domestic and foreign literature retrieval, do not see the identical bibliographical information of a kind of potentiometric titrimeter major technique of major technique feature and the present invention feature.
The purpose of this invention is to provide a kind of potentiometric titrimeter.
A kind of potentiometric titrimeter of the present invention, comprise imbibition titration unit, data acquisition and converting unit, drive gear unit, computing machine and application software, it is characterized in that imbibition titration unit comprises imbibition/transmitter (2), reversal valve (3), woven hose (4), standard solution storage bottle (6), titration/interchanger base (7), non-proliferation titrating head (11), magnetic stirring apparatus (15) and chemical reactor (24), data acquisition and converting unit comprise data converter (9), auxiliary electrode (12), contrast electrode (13), indicator electrode (14), the electrode wires (16) of band shielding, drive gear unit and comprise driving/transmission and gear-shift mechanism (8) and circuit control panel (25), computing machine and application software elements comprise the computing machine (1) that has application software, and main frame comprises driving/transmission and gear-shift mechanism (8), data converter (9) and circuit control panel (25).
Potentiometric titrimeter of the present invention, it is characterized in that wherein driving/transmission and gear-shift mechanism (8) comprise stepper motor, the multi-stage speed-reducing gear, drive lead screw and driving stem, imbibition/transmitter (2) sends pipe for titration, by multi-stage speed-reducing gear and drive lead screw, become the rectilinear motion of the circular motion of stepper motor into imbibition/transmitter (2) plunger, piston rod and driving stem are linearly and main drive gear and drive lead screw concentric, on, lower limit has the optoelectronic switch of accurate positioning, imbibition finishes back automatic backlash compensation, and mould/number conversion signal value is accurately corresponding with buret transmission volume.
Potentiometric titrimeter of the present invention, it is characterized in that wherein data acquisition and converting unit be furnished with the input of two high resistant input amplifiers and three electrodes, indicator electrode in the three-electrode system (14) is the pH glass electrode, contrast electrode (13) is two liquid mercurous chloride electrodes that connect, auxiliary electrode (12) is a platinum electrode, adopts biproduct somatotype A/D converter.
Potentiometric titrimeter of the present invention is characterized in that the interior liquid of described indicator electrode (14) is lithium chloride-ethanolic solution, and the interior salt bridge solution of contrast electrode (13) is saturated lithium chloride-ethanolic solution, and outer salt bridge solution is lithium perchlorate-propionic acid-glacial acetic acid solution.
Potentiometric titrimeter of the present invention is characterized in that described non-proliferation titrating head (11) is equipped with impermeable one-way membrane.
Potentiometric titrimeter of the present invention is characterized in that described non-proliferation titrating head (11) is equipped with the plunger of bending-type micro channel.
Potentiometric titrimeter of the present invention, it is characterized in that described titration/interchanger base (7) and main frame are plug-in type combination isolating constructions, titration/interchanger base (7) is gone up collection imbibition/transmitter (2), reversal valve (3), woven hose (4), standard solution storage bottle (6), non-proliferation titrating head (11), and main frame is positioned at the below of titration/interchanger base (7).
Potentiometric titrimeter of the present invention is characterized in that described imbibition finishes back automatic backlash compensation and is meant that eliminate automatically in the gap to driving/gear unit under software control.
Potentiometric titrimeter of the present invention is characterized in that data direct accesses (DMA), the level exchanged form of conversion is automatically adopted in the signal transmission between main frame and the computing machine, and titration process and terminal point determining are controlled by computer program.
Potentiometric titrimeter of the present invention is characterized in that described terminal point determining is meant to adopt to set up endpoint signal mathematical model, the automatic differentiation of pseudo end point and rejecting and digital filtering technique, and titration end-point is differentiated.
Below be described in detail the present invention.
A kind of potentiometric titrimeter of the present invention comprises imbibition titration unit, and data acquisition and converting unit drive gear unit, and computing machine and application software, structure are as shown in Figure 1.
Imbibition titration unit comprises imbibition/transmitter (2); reversal valve (3); the teflon woven hose (4) of band protective sleeve; dry permeability cell (5); standard solution storage bottle (6), titration/interchanger base (7), electrode/titration folder (10); non-proliferation titrating head (11), magnetic stirring apparatus (15) and chemical reactor (24).Electrode/titration folder (10) can clamping non-proliferation titrating head (11), and clamping auxiliary electrode (12), contrast electrode (13) and indicator electrode (14).
Data acquisition and converting unit comprise the electrode wires (16) of data converter (9), auxiliary electrode (12), contrast electrode (13), indicator electrode (14), band shielding.
Drive gear unit and comprise driving/transmission and gear-shift mechanism (8) and circuit control panel (25).For guaranteeing drive part and imbibition titration unit interface coupling, screw mandrel and lifting frame adopt respective element, make piston rod and driving stem be arranged in a linear, and analog to digital conversion signal value and buret send volume and coincide.Upper and lower spacing for the optoelectronic switch of accurate positioning.Adopt gear to carry out secondary and three grades of decelerations.
The circuit control of potentiometric titrimeter of the present invention, by valve controling circuit, the titration control circuit, motor-drive circuit, subtraction circuit, high impedance input circuits etc. are integrated, control and finish serial communication with computing machine with single-chip microcomputer, all electrode connecting lines adopt shielded cables.
Computing machine and application software elements comprise the computing machine (1) that has application software.
The software control of potentiometric titrimeter of the present invention: adopt the establishment of assembly language and VB6 language, RS232C standard serial mouth, the WINDOWS operating platform, adopt man-machine conversation methods of operating such as menu, soft key, characteristic according to the titration sample, the parameter setting of a plurality of indexs is provided, guarantees that endpoint is correct.
Main frame comprises driving/transmission and gear-shift mechanism (8), data converter (9) and circuit control panel (25).
The theory diagram of potentiometric titrimeter of the present invention as shown in Figure 2.
The hardware components composition frame chart of potentiometric titrimeter of the present invention as shown in Figure 3.
The electrode system of potentiometric titrimeter of the present invention is a three-electrode system, is made up of the electrode wires (16) of auxiliary electrode (12), contrast electrode (13), indicator electrode (14) and band shielding.
Solution potential stability is relevant with solvent, relevant with contrast electrode on the other hand on the one hand.Because disturbing factor is many, single salt bridge contrast electrode does not have that two to connect liquid contrast electrode antijamming capability strong.The outer salt bridge solution of contrast electrode of the present invention is perchlorate solution, and interior salt bridge solution is lithium chloride solution, and potential value is more stable relatively.Be used for the indicator electrode of non-aqueous solution soda acid potentiometric titration commonly used be glass electrode, it is easy to use, responds comparatively rapidly, but the current potential reappearance is not fine in oil product solution, this potentiometric titrimeter is to decide terminal point according to the potential change rate, and the good and bad influence of reappearance is less.This titrator selects for use lithium glass electrode and aforesaid contrast electrode adapted effect better.
In the electrode of potentiometric titrimeter of the present invention, the interior liquid of indicator electrode (14) is lithium chloride-ethanolic solution, and the interior salt bridge solution of contrast electrode (13) is saturated lithium chloride-ethanolic solution, and outer salt bridge solution is lithium perchlorate-propionic acid-glacial acetic acid solution.
Titrator of the present invention has carried out architecture advances to titrating head.
Titrating head is bigger to the titration results influence, and the titrating head on the conventional potentiometric titrimeter is generally the glass head of volumetry buret.If titrating head directly inserts in the solution, sample will infiltrate lentamente, exchange from titrating head, show as and make the titrant variable color, and color change interval is along the upwards slowly diffusion always of titrating head inwall.Do not dripped solution if titrating head does not contact, when then each small size sent titrant, titrant can be suspended on the titrating head, made actual titer and terminal point potential break produce error.Like this, not only influence result's collimation but also influenced the accuracy of data.
The non-proliferation titrating head (11) of potentiometric titrimeter of the present invention is equipped with impermeable one-way membrane, the plunger of bending-type micro channel perhaps is housed, eliminates exchangeing problem of solution in the titrating head substantially, improved the potentiometric titration precision, even when analyzing the low content sample, still have better parallel.
The structure of non-proliferation titrating head of the present invention (11) is seen Fig. 4.
Potential electrode adopts three-electrode system, and system is made up of auxiliary electrode (12), contrast electrode (13), indicator electrode (14).Because the glass electrode internal resistance is near 10
9Ω, therefore, having matched, (impedance should be not less than 10 in two high resistant inputs
12Ohm), its DC potential becomes the single-ended A/D of exporting to circuit behind subtraction circuit, convert 12 position digital signals to.The biproduct somatotype A/D converter that adopts has higher sensitivity and precision and anti-strongly common mode interference ability.Between main frame and computing machine, set up serial interface circuit, realize host CPU and the data of computing machine and the transmission of status information.Data processing and end point judging, drawing and display result are finished by computing machine.Main frame is according to valve controling circuit, titration sending controling circuit and status information, and by able to programme and outside expansion parallel I/O interface circuit, control reversal valve and titration send, and the turning to and open, stop of two stepper motors.Wherein CPU has adopted the cmos device that includes flash memory of low-power consumption.Expansion external data memory adopts the static random-access memory.Commutation/imbibition/transmission drives, and needs big electric current to start, and other adds Drive and Control Circuit.For guaranteeing that gearing and valve, titration send the accurate reliable fit of piston, running part adopts the transmission of high-quality gears.Titration sends the promotion of pipe, and by multi-stage speed-reducing gear, transmission precision screw mandrel, the circular motion that becomes stepper motor sends the Precision Linear Moving of tubing string plug into titration by stepper motor.
In imbibition titration unit, all defeated spool lines all adopt the good plastic flexible pipe of chemical stability, are provided with outside titration/transmitter and cover the light overcoat, and all and solution contact portion and magnetic stirring apparatus table top are corrosion-resistant material.
The system software of potentiometric titrimeter of the present invention adopts assembly language and VB6.0 language to mix and works out, the wherein control of motor, transmission, and the A/D conversion, data acquisition, the serial communication supervisor is write by the fast assembly language of travelling speed.Master routine, menu, data and subroutines such as Flame Image Process, endpoint have comprised the automatic discrimination technology of pseudo end point by the VB6 language compilation, software balance acquisition technique, digital filtering technique etc.General design of software block diagram such as Fig. 5.
System software is a control module with full-localized drop-down menu and popup menu, and modification of program is convenient, and dirigibility is strong.The frequent menu function that uses is made quick strong button and has been improved operating efficiency, and the validity of each shortcut button, changes along with the variation of opening window, with anti-misoperation.The titration curve of quota of expenditure liquor capacity-electric potential relation is drawn on titration limit, native system limit, helps the analyst further to judge the reliability of titration results.After the online initialization, system just is ready.
The feature of potentiometric titrimeter of the present invention is to be provided with the endpoint program.Because the chemical reaction of sample and vs is weak phase chemistry kinetic reaction sometimes, hop is little, and a plurality of hop points are arranged again sometimes.For eliminating terminal point erroneous judgement problem, except that on analytical approach, doing suitably improvement, also worked out the titration end-point determining program, the endpoint program circuit is seen Fig. 6.
The key technical indexes of potentiometric titrimeter of the present invention is as follows:
(1) potential measurement scope: 0 ± 1999mv
(2) electronic unit fundamental error: reading ± 0.1% (FS)
(3) temperature range: 5～35 ℃
(4) input impedance: 〉=1 * 1012 Ω
(5) basic n content measurement range: NB 〉=1.0 μ g/g, the minimum amount of measuring 0.5 μ g/g.
(6) data sampling speed: 3～10 times/S
(7) stability of instrument: ± 1.0mv/3h
(8) titration sends pipe precision: ± 0.1% (FS)
(9) titration sends pipe rate of liquid aspiration: 43 ± 1S/FS
Potentiometric titrimeter of the present invention can be used for measuring the basic nitrogen in the oil product, also can be used for the potentiometric titration of other samples.
The domestic automatic potential titrator tests stand oil product neutral and alkali nitrogen content that attempt to adopt in recent years, still, these titrators all exist in the analytic process potential stability poor, problems such as terminal point erroneous judgement.
By measuring all kinds of petroleum products basic n contents mensuration in dimethylbenzene-glacial acetic acid or the benzene-glacial acetic acid medium, checked the performance of potentiometric titrimeter of the present invention.Take by weighing quantity of sample, the perchloric acid standard titration solution after perchloric acid titration agent or employing improve in the employing standard method carries out titration with potentiometric titrimeter of the present invention, measures the content of oil product neutral and alkali nitrogen, has obtained titration results preferably.
Potentiometric titrimeter of the present invention is used to measure oil product neutral and alkali nitrogen, has not only eliminated the error that the manual titration of SH/T0162 standard method varies with each individual, and has widened its measurement range, makes that dark, light oil product neutral and alkali nitrogen can both accurately be measured.Compare simultaneously, improved the potential stability of oil product in volumetric soiutions with traditional potentiometric titration, operate easier, more perfect antijamming capability is arranged, eliminated the terminal point erroneous judgement and improved measuring accuracy, titration shows in real time intuitively.
Fig. 1 is a potentiometric titrimeter structural representation of the present invention.
Fig. 2 is a potentiometric titrimeter theory diagram of the present invention.
Fig. 3 is a potentiometric titrimeter hardware components composition frame chart of the present invention.
Fig. 4 is a potentiometric titrimeter titrating head structural drawing of the present invention.
Fig. 5 is a potentiometric titrimeter workflow diagram of the present invention.
Fig. 6 is a potentiometric titrimeter general design of software block diagram of the present invention.
Fig. 7 is a potentiometric titrimeter endpoint process flow diagram of the present invention.
Among Fig. 1,1 computing machine for the band application software, 2 are imbibition/transmitter; 3 is reversal valve, 4 teflon woven hoses for the band protective sleeve, and 5 is dry permeability cell; 6 are standard solution storage bottle; 7 are titration/interchanger base, and 8 are driving/transmission and gear-shift mechanism, and 9 is data converter; 10 is electrode/titration folder; 11 is the non-proliferation titrating head, and 12 is auxiliary electrode, and 13 is contrast electrode; 14 is indicator electrode; 15 is magnetic stirring apparatus, 16 electrode wires for the band shielding, and 17 is power switch; 18 is the ground connection terminal; 19 is the AC power supplies socket, and 20 is the indicator electrode socket, and 21 is auxiliary electrode ground terminal; 22 is the contrast electrode socket; 23 is standard RS232C serial port, and 24 is chemical reactor, and 25 is circuit control panel.
Among Fig. 4,1 is the sample introduction pipe, and 2 are the titration headpin, and 3 are the titration headgear, and 4 is titrating head.
It is as follows that potentiometric titrimeter of the present invention is applied to the embodiment of petroleum oil product neutral and alkali nitrogen determination:
Computing machine enters application program, and with the online initialization of potentiometric titrimeter main frame of the present invention after, given on computers all titration conditions.Take by weighing the 1.512g refined diesel oil in low mouthful of beaker of 150ml cleaning drying, adding prepares 80mL dimethylbenzene-anhydrous acetic acid (1: 1) mixed solvent, turn on agitator in advance.After treating sample dissolution, the perchloric acid standard solution of computer control 0.02047M carries out titration at interval with the volume of 0.05～0.10mL, titrator is sought terminal point automatically, calculates and demonstrate basic n content 449 μ g/g, titration curve, potential change rate curve automatically by computing module.With with the quadrat method titration, get blank value 0.05mL.The volume of titrant that terminal point consumes is 2.40mL.
After electrode soaks pre-service, insert in the measuring cell online initialization.Take by weighing the 0.4489g miscella in low mouthful of beaker of 150ml cleaning drying, adding prepares 80mL dimethylbenzene-anhydrous acetic acid (1: 1) mixed solvent, turn on agitator in advance.After treating sample dissolution, the perchloric acid standard solution of computer control 0.02047M carries out titration at interval with the volume of 0.05～0.10mL, titrator is sought terminal point automatically, calculates and demonstrate basic n content 1044 μ g/g, titration curve, potential change rate curve automatically by computing module.With with the quadrat method titration, get blank value 0.12mL.The volume of titrant that terminal point consumes is 1.87mL.
Claims (10)
1. potentiometric titrimeter, comprise imbibition titration unit, data acquisition and converting unit, drive gear unit, computing machine and application software, it is characterized in that imbibition titration unit comprises imbibition/transmitter (2), reversal valve (3), woven hose (4), standard solution storage bottle (6), titration/interchanger base (7), non-proliferation titrating head (11), magnetic stirring apparatus (15) and chemical reactor (24), data acquisition and converting unit comprise data converter (9), auxiliary electrode (12), contrast electrode (13), indicator electrode (14), the electrode wires (16) of band shielding, drive gear unit and comprise driving/transmission and gear-shift mechanism (8) and circuit control panel (25), computing machine and application software elements comprise the computing machine (1) that has application software, and main frame comprises driving/transmission and gear-shift mechanism (8), data converter (9) and circuit control panel (25).
2. potentiometric titrimeter according to claim 1, it is characterized in that wherein driving/transmission and gear-shift mechanism (8) comprise stepper motor, the multi-stage speed-reducing gear, drive lead screw and driving stem, imbibition/transmitter (2) sends pipe for titration, by multi-stage speed-reducing gear and drive lead screw, become the rectilinear motion of the circular motion of stepper motor into imbibition/transmitter (2) plunger, piston rod and driving stem are linearly and main drive gear and drive lead screw concentric, on, lower limit has the optoelectronic switch of accurate positioning, imbibition finishes back automatic backlash compensation, and mould/number conversion signal value is accurately corresponding with buret transmission volume.
3. potentiometric titrimeter according to claim 1, it is characterized in that wherein data acquisition and converting unit be furnished with the input of two high resistant input amplifiers and three electrodes, indicator electrode in the three-electrode system (14) is the pH glass electrode, contrast electrode (13) is two liquid mercurous chloride electrodes that connect, auxiliary electrode (12) is a platinum electrode, adopts biproduct somatotype A/D converter.
4. according to the described potentiometric titrimeter of claim 1, it is characterized in that the interior liquid of described indicator electrode (14) is lithium chloride-ethanolic solution, the interior salt bridge solution of contrast electrode (13) is saturated lithium chloride-ethanolic solution, and outer salt bridge solution is lithium perchlorate-propionic acid-glacial acetic acid solution.
5. potentiometric titrimeter according to claim 1 is characterized in that described non-proliferation titrating head (11) is equipped with impermeable one-way membrane.
6. potentiometric titrimeter according to claim 1 is characterized in that described non-proliferation titrating head (11) is equipped with the plunger of bending-type micro channel.
7. potentiometric titrimeter according to claim 1, it is characterized in that described titration/interchanger base (7) and main frame are plug-in type combination isolating constructions, titration/interchanger base (7) is gone up collection imbibition/transmitter (2), reversal valve (3), woven hose (4), standard solution storage bottle (6), non-proliferation titrating head (11), and main frame is positioned at the below of titration/interchanger base (7).
8. according to the described potentiometric titrimeter of claim 2, it is characterized in that described imbibition finishes back automatic backlash compensation and is meant that eliminate automatically in the gap to driving/gear unit under software control.
9. potentiometric titrimeter according to claim 1 is characterized in that data direct accesses (DMA) are adopted in the signal transmission between main frame and the computing machine, and level is the exchanged form of conversion automatically, and titration process and terminal point determining are controlled by computer program.
10. potentiometric titrimeter according to claim 9 is characterized in that described terminal point determining is meant to adopt to set up endpoint signal mathematical model, the automatic differentiation of pseudo end point and rejecting and digital filtering technique, and titration end-point is differentiated.
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2002
- 2002-03-29 CN CNB021165238A patent/CN1176372C/en not_active Expired - Fee Related
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