CN1059966A - Measure the method and apparatus of dissociable population in the liquid - Google Patents

Measure the method and apparatus of dissociable population in the liquid Download PDF

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Publication number
CN1059966A
CN1059966A CN91108794A CN91108794A CN1059966A CN 1059966 A CN1059966 A CN 1059966A CN 91108794 A CN91108794 A CN 91108794A CN 91108794 A CN91108794 A CN 91108794A CN 1059966 A CN1059966 A CN 1059966A
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liquid
electrode
dissociable
electric field
electric current
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沃夫冈·迪特利西
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Huels AG
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Huels AG
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    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N27/00—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means
    • G01N27/02—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating impedance
    • G01N27/04—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating impedance by investigating resistance
    • G01N27/06—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating impedance by investigating resistance of a liquid
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N27/00—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means
    • G01N27/26—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating electrochemical variables; by using electrolysis or electrophoresis
    • G01N27/416—Systems
    • G01N27/42—Measuring deposition or liberation of materials from an electrolyte; Coulometry, i.e. measuring coulomb-equivalent of material in an electrolyte
    • G01N27/423—Coulometry

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  • Health & Medical Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Analytical Chemistry (AREA)
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  • Chemical Kinetics & Catalysis (AREA)
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  • Investigating Or Analyzing Materials By The Use Of Electric Means (AREA)
  • Electrostatic Separation (AREA)

Abstract

The present invention relates to the method for dissociable particle (ion pair) number in a kind of mensuration liquid, wherein an electric field is imposed on the electrode pair, this electrode pair is arranged in liquid, and demonstrate lower charge carrier injection capacity, wherein be integrated in regular turn because of the formed electric current of electric field, and the mensuration integrated value, as the measured value of the original contained dissociable population of this liquid.

Description

Measure the method and apparatus of dissociable population in the liquid
The present invention relates to the method for dissociable particle (ion pair) number in a kind of mensuration liquid.
Measure the electrochemical method of liquid intermediate ion, early known by everybody.All these methods are all based on the mensuration to liquid electric conductivity.In these methods, apply on the electrode pair in testing liquid-voltage ， And measures formed electric current by means of surveying instrument.
Dissociable particle constitutes the impurity in the liquid, exists with disassociation state or non-disassociation state usually.
Between this two states, set up a specific balance.Have only the particle (becoming charge carrier) of moment disassociation could constitute flowing of electric current.
Therefore, be not suitable for the accurate mensuration of dissociable population in the liquid based on these methods ， And of conductance measurement because partly particle perseverance between this test period is non-disassociation state, so to conductivity without any contribution.In addition, use traditional electrode right, charge carrier injects liquid quantitatively, therefore, also makes the measurement result distortion.
Therefore, one of the present invention purpose, propose a kind of simple but can very accurately measure the method for dissociable population in the liquid.
According to the present invention, this purpose can realize via following method: wherein an electric field is imposed on the electrode pair, this electrode pair is arranged in liquid ， And and demonstrates lower charge carrier injection capacity,
Wherein in a special time, the formed electric current of electric field is carried out integration successively,
And measures integrated value, as the measured value of original contained dissociable population in this liquid.
In the inventive method, during whole integration step, the particle that has not only dissociated when method begins can become the factor of measurement result, and at the particle that dissociates because of electric field action after a while, also becomes the factor of measurement result.
Moreover, can prevent that extra charge carrier from entering in the liquid, therefore can not become the part of current integration, because use the special electrode that charge carrier is had lower injection capacity.This can promote the accuracy of measurement.
The present invention preferably implements a period of time, just stops to measure when the electric current amount of flow in fact no longer reduces.Because the actual conditions that some remaining electric current is bound to exist, so can't wait until that electric current pauses fully.If the remaining electric current of this type is arranged, it must be excluded in outside the current integration.
After integration operation finishes, can suppose that all dissociable particles all are its disassociation state ， And and have become order to be moved on the electrode by ion.Therefore, Sheng Xia liquid is the high-purity state.
Following relevant disassociation particle (ion pair) N EAnd the relational expression between streaming current I exists forever, wherein N EFor during electric field action, in the unit volume by the disassociation particle of liquid extraction:
NE = 1 e · v · ∫ 0 t Idt
Wherein e is an elementary charge, and V is a volume.
After the fully long time, all dissociable particles all become to dissociate state ， And and shifted to electrode, so electric current stops.Therefore, the number N of the initial contained dissociable particle of per unit volume in the liquid DFor:
N D-N E
t→∞
Certainly hypothesis liquid dissociates or not even disassociation hardly in the following formula, so electric current is in fact, and impurity causes.
The electrode that reduces injection capacity can be following type:
For example available so-called purifying electrode.
Some electrode, its capacity that injects electronics reduces significantly by suitable pre-service.Use commercially available brass electrode, for example its purifying can be finished with following open-and-shut method: the electrode contraposition that will desire purifying imposes electric field or electric power, for example 10KV/cm to it in the electrolytic tank that contains propylene carbonate (PC).After a period of time, electrode is purified.In the example of brass electrode and PC, purifying can be understood by the brown phenomenon of fading on the electrode surface.Electrode so that this mode purifying is crossed can be used among the present invention.
Other of injection capacity that reduce commercially available untreated (naked) electrode may comprise: in the electrode sections direction, coated with ion exchange membrane.Film can prevent that ion from entering in the liquid.
At last, inventor etc. also have been found that: between the liquid that the commercially available electrode of be untreated (naked) and desire detect, insert one deck and have high dielectric constant materials, can reduce the injection capacity of electrode.Therefore, available significantly this coated materials is on electrode.But have been found that in test: though pottery is particularly suitable for preventing to annotate the people, can not be made into the shape of expection without a doubt, following array apparatus is considered to comparatively ideal in the test of carrying out:
Between liquid and each electrode, insert a ceramic wafer, liquid is confined between two plates, and electrode can be fixed on the side of plank back to liquid.
The present invention preferably uses the electric field of number KV/cm.Therefore, can in the fully short time, implement ， And of the present invention and estimate that all dissociable particles can dissociate.
Though do not witness, can suppose that dissociable particles all under a certain electric field intensity may dissociate fully.(PC) is liquid with propylene carbonate, when using the purifying electrode as electrode, under the electric field intensity of about 100V/cm, observed the disassociation of certain degree.Basically we can say that when having big electric field intensity, it is very fast that this method is carried out, because big electric field intensity can be promoted the rate of dissociation K of particle.
Based on this purpose, can use commercially available device, to measure and record gained electric current.
For example use the storage type recording camera or comprise the current measurement instrument of record cell.The integration of gained electric current can be tried to achieve through planimetric method via assessment decision or the current curve that is write down by these devices.Certainly, also can use the instrument and equipment that to measure integrated value automatically.The present invention preferably uses the liquid with high-k.
Because dissociable particle is an impurity of desiring tracer liquid, therefore,, can predict the time that passivation liquid is required via measuring dissociable population.
Suppose that electric current descends according to a specific function (for example exponential function), then the integration assessed value of electric current can be done to judge reliably according to reasonable time constant τ is made short time measurement.Therefore, in this case, this method needn't last till that electric current almost reduces to till the remaining electric current that can not exempt from.Traditional storage type recording camera is particularly suitable for observing electric current and descends, with the evaluation time constant.As everyone knows, the integration of exponential function is the product of time constant and initial value.Therefore, following formula can be used as the dissociable population in the unit volume:
N D = τ · I 0 e · V
Wherein τ represents the time constant of exponential function, and I 0Be the electric current initial value.
Below in conjunction with an instantiation of dissociable population in the description of drawings mensuration propylene carbonate (PC), wherein
Fig. 1 explanation: the device of implementing this method;
Fig. 2 explanation: the measurement electrolytic tank that this method is suitable for;
Fig. 3 explanation: this method measured current curve of conducting period.
Measure electrolytic tank 1 and be shown in Fig. 1, in order to the propylene carbonate 3 of splendid attire desire detection.A pair of passivated electrodes 2 is connected to voltage source 5.Rheometer recording device 4 is between electrode and voltage source.Register 6 is the rheometer recording device, and it prints the current curve as the function of time.This method can be by switch 7 closures are started.
The mutual spacing of electrode is for example 0.5cm.Institute's voltage of executing is between 100 to 1000V.Formed electric field intensity is 200 to 2000V/cM.
The analyzed mensuration of the content of following major impurity in propylene carbonate:
Sodium chloride, tetramethylammonium bromide, propylene glycol, water.
These impurity contents mainly exist with the ppm level.Before applying electric field, disassociation particle N and dissociable particle N DRatio, be called dissociation degree α (α=N/N D).If propylene carbonate is polluted by water, then dissociation degree is 10 -6, polluted by propylene glycol, then be 10 -4, be chlorinated sodium or tetramethylammonium bromide and pollute, then be between 0.1 to 1.
Fig. 2 illustrates an instantiation measuring electrolytic tank.Obviously, this is an airtight measurement electrolytic tank 2.On the electrode 1 wherein coated with amberplex 3.In addition, can certainly use passivated electrodes shown in Figure 1.
This method during carrying out measured current curve be plotted in Fig. 3.
Behind the switch closure, on passivated electrodes 2, will set up electric field among Fig. 1.With rheometer recording device 4, sensing mainly is to be depicted in Fig. 3 by the formed electric current ， of disassociation electric current And.Can clearly be seen that from Fig. 3 electric current has the trend of index decreased.After about 5 minutes, electric current is reduced to I R, after this value, in fact no longer descend.The remaining electric current that exists is this value forever.
When measuring the integration of the 0th minute area that current curve encloses between the 5th minute, the remaining electric current of integration system of Fig. 3 bend part constitutes, and should not count.
Moreover current curve has a deviation in the place of beginning as seen from Figure 3.This deviation is two formed results of overlapping process.At first, the particle of the state that become to dissociate becomes the main composition factor of electric current.This causes initial big electric current I O， And is at τ 1Time constant in descend rapidly.At current curve after a while, then determined by the particle that comes out that newly dissociates in a continuous manner.This main electric current is partly with τ 2For time constant descends.
The decline of electric current is by register shown in Figure 16 records.Electricity area that curve encloses is easy to be measured as area metering with the current curve that is write down.As above-mentioned, the oblique line among Fig. 3 partly is not counted in the current integration, because this oblique line is made of remaining electric current.
If current integration is known, following formula can be used the population N in the hope of unit volume D, it is a storage initial in the liquid:
N D = τ · I 0 e · V
Wherein Q is disassociation whole electric charges that electric current constituted.
The initial conductivity of propylene carbonate is 5 * 10 -10S/cm, the ND value that records is 6 * 10 13L/cm 3This two numerical value constitutes a concrete measurement result.Certainly, conductivity and dissociable population N DBetween, there is not fixing relation basically, because initial conductivity, in fact be that the corresponding dissociation degree by dopant species and these particles is determined.
Proved this method to about the operation of while in conjunction with the purifying and the generation passivated electrodes of propylene carbonate, very favourable.
The inventive method can simply and accurately be measured the pollution level of propylene carbonate.Especially can predict the purifying time of propylene carbonate.
Can predict that the dissociable population that this method has mensuration in the liquid of high-k is extremely useful, it is as the same to be used for electrostatic mechanical.

Claims (11)

1, the method for dissociable particle (ion pair) number in a kind of mensuration liquid,
Wherein an electric field is imposed on the electrode pair, this electrode pair is arranged in liquid, and demonstrates lower charge carrier injection capacity;
Wherein be integrated in regular turn because of the formed electric current of electric field; With
Measure integrated value, as the measured value of the original contained dissociable population of this liquid.
2,, it is characterized in that integration step stops when electric current in fact no longer descends according to the method for claim 1.
3,, it is characterized in that electrode used therein is right to being passivated electrodes according to the method for claim 1 or 2.
4, according to the method for claim 1 or 2, it is characterized in that electrode used therein to last coated with amberplex.
5, according to the method for claim 1 or 2, it is characterized in that electrode used therein to for bare electrode, and will be described and this liquid isolation with having high dielectric constant materials (is preferable with stupalith) layer.
6, according at least one described method in the aforesaid right requirement, it is characterized in that the electric field intensity that applies is higher than 100V/cm.
7, according at least one described method in the aforesaid right requirement, liquid has high-k.
8, requiring the wherein used liquid of 7 described methods according to aforesaid right is propylene carbonate.
9, require the 6th or 7 described method according to aforesaid right, be used to measure the purifying time of liquid.
10, a kind of in order to implement device as method as described in the claim 1 to 6 at least one, it is characterized in that:
-container, in order to this liquid of splendid attire,
At least two electrodes place this container, and its phase mutual edge distance has certain relation, and And presents the injection capacity of reduction,
-voltage source joins with electric connecting mode and described electrode,
-current sensing device is in order to measure and record current this device and this voltage source and described electrode polyphone.
11, device according to claim 10 is characterized in that this current sensing device is the storage type recording camera.
CN91108794A 1990-09-10 1991-09-09 Measure the method and apparatus of dissociable population in the liquid Pending CN1059966A (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE4028716A DE4028716A1 (en) 1990-09-10 1990-09-10 METHOD FOR DETERMINING THE NUMBER OF DISSOCIATIVE PARTICLES IN LIQUIDS
DEP4028716.5 1990-09-10

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JP (1) JPH06501097A (en)
KR (1) KR930702671A (en)
CN (1) CN1059966A (en)
CA (1) CA2091347A1 (en)
DE (1) DE4028716A1 (en)
FI (1) FI931035A (en)
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WO (1) WO1992004624A1 (en)

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KR101142409B1 (en) * 2008-10-21 2012-05-07 호쿠토 덴시 고교 가부시키가이샤 Method and device for the detection of particle size in liquid

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RO75812A (en) * 1974-06-05 1981-02-28 Aluminium Pechiney,Fr METHOD FOR THE CONTINUOUS DETERMINATION OF INTERNAL RESISTANCE OF AN ELECTROLYSIS UNIT AND INSTALLATION FOR APPLICATION OF THE PROCESS
US4009998A (en) * 1975-09-05 1977-03-01 Phillips Petroleum Company Acid concentration measurement
JPS6453146A (en) * 1987-01-09 1989-03-01 Hitachi Ltd Method and instrument for measuring electrical conductivity of solution and water quality control method

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TW240293B (en) 1995-02-11
KR930702671A (en) 1993-09-09
FI931035A0 (en) 1993-03-09
JPH06501097A (en) 1994-01-27
WO1992004624A1 (en) 1992-03-19
EP0548133A1 (en) 1993-06-30
DE4028716A1 (en) 1992-03-12
FI931035A (en) 1993-04-06

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