CN107421948A - The method of detection solution colour change based on the CIELab colour spaces - Google Patents
The method of detection solution colour change based on the CIELab colour spaces Download PDFInfo
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Abstract
The present invention provides a kind of method of the detection solution colour change based on the CIE Lab colour spaces, and it comprises the following steps：(1) light source is provided, the light of light source is incided perpendicular to the transmittance section of reaction tank in reaction tank；(2) titrated using titration outfit into reaction tank, and record titration volumes；(3) emergent light through the solution in reaction tank is conducted into spectrometer；(4) spectrometer takes absorbance A bs signal values according to data sampling interval to being transmitted to spectral signal therein, and transmit signal value to data processing unit, space chromacity value L of the solution at corresponding titration volumes number is calculated in data processing unit absorbance A bs signal values according to corresponding to different wave length*、a*、b*Value.
Description
Technical field
The present invention relates to detection technique field, more particularly it relates to a kind of inspection based on the CIE Lab colour spaces
The method for surveying solution colour change.
Background technology
In technical field of analysis and detection, to be realized by the testing result measured and the chemical change of observing final
Purpose is typically to obtain the volume number of solution, so that it is determined that in volume number corresponding to each specified point place.
Generally, the method for measure liquid color both domestic and external includes artificial visual method, is exactly according to " visual impression → thinking
The program of judgement → language description " describes in words to the instant color change of configuration process, represents the color of terminal by operation
Person oneself understands.Its terminal is judged using phenolphthalein discoloration as mark.To reduce error, demarcated in national standard for standard titration solution
When control errors have be specified below：Provided in GB/T601-2002, must two people progress when demarcating the concentration of standard titration solution
Experiment, respectively does four parallel respectively, and the relative value of everyone four parallel determinations extreme differences cannot be greater than the phase of the critical extreme difference of repeatability
To value 0.15%；The relative value of two people totally eight parallel determinations extreme differences cannot be greater than the relative value of the critical extreme difference of repeatability
0.18%, the average value for taking the parallel determinations of two people eight is measurement result.
For " visual impression → thinking judgement → language description " method, it is very big by environment, people's sense organ and psychological impact,
There are larger discreteness and random error, the needs that food is quickly examined can not have been met." visual impression → thinking judgement → language
Speech description " method using human eye as sensor, is adopted to color change and described in words, its major defect is：
1) human eye influences the judgement of titration end-point color, causes result deviation occur to the sensitivity of different colours；
2) some color distinctions are difficult to grasp by the physiological threshold difference of age and ethnic group, even trained ripe
It is also difficult to practice personnel；
3) understanding between operator to language is different, causes the disunity of titration end-point color；
4) collimation error between operator is with regard to the entirely possible deviation for causing experimental result, and endpoint error is relatively
Greatly；
5) different titration environment are big to the visual impact of operator；
6) titration process and endpoint information can only be described with language, without digital information, can not transmission of quantity value, and trace
It is difficult；
7) when learning and teach, the aspectant mode of teaching of master and apprentice can only be taken to determine terminal colour；
8) labor intensity is big, is also easy to produce visual fatigue, influences the accurate of result；
9) it is affected by environment it is big, end reaction is blunt, it is difficult to improve accuracy of detection；
10) testing procedure is cumbersome, can not realize automation, the detection scale of mass.
During by eye-observation a certain kind color, different people has different descriptions to color, even same person,
Different visual effects can also be produced to same color under different illumination, therefore, certain can not be obtained by manual titration
Accurate volume number corresponding to one color.
In addition, the method for conventional measure liquid color also detects solution colour, electricity using the method for constant-current titration
Position titration is to determine the method for titration end-point by measuring potential change in titration process, before titration is reached home
Afterwards, often n order of magnitude of consecutive variations of the ion concentration to be measured in dropping liquid, causes the hop of current potential, is tested the content of composition still
So calculated by consuming the amount of titrant.However, tend not to enough accurately obtain terminal during constant-current titration or specify
The titration volumes number of point, this is due to cause potential break to be and the body as caused by some volume number in titration volumes
Product is typically what can not be determined.
Application No. CN201610090735.7 entitled chemical analysis liquid color CIE1976Lab colour spaces measure side
A kind of method that liquid color is determined using the CIE1976Lab colour spaces of the disclosure of the invention of method, for entering to measure liquid color
Row accurate description, however, not being described in detail in the invention to the corresponding relation between solution colour and titration volumes number.
Therefore, it is necessary to provide a kind of method for detecting solution colour change, it is not necessary to consider light and the subjective factor of people
Influence to colour measurement, makes the description of color become materialization, precision, digitlization, and obtains corresponding to any color
Accurate solution body product.
The content of the invention
It is an object of the invention to provide it is a kind of based on the CIE Lab colour spaces detection solution colour change method, its
Dynamic detection is carried out in titration process to the solution in reaction tank, and it is accurate corresponding to obtaining after testing result is handled
Titration volumes number.
Based on above-mentioned purpose, the present invention provides a kind of method of the detection solution colour change based on the CIE Lab colour spaces,
Comprise the following steps：
(1) light source is provided, the light of light source is incided perpendicular to the transmittance section of reaction tank in reaction tank；
(2) titrated using titration outfit into reaction tank, and record titration volumes；
(3) emergent light through the solution in reaction tank is conducted into spectrometer；
(4) spectrometer takes absorbance A bs signals according to data sampling interval to being transmitted to spectral signal therein
Value, and signal value is transmitted to data processing unit, data processing unit absorbance A bs signal values according to corresponding to different wave length
Space chromacity value L of the solution at corresponding titration volumes number is calculated*、a*、b*Value.
Further, according to a preferred embodiment of the invention, by L*、a*、b*Value is transmitted to the first computing unit,
According to the L received*、a*、b*Chroma value C and hue angle value H corresponding to value calculating at titration volumes number.
According to a preferred embodiment of the invention, the detection solution colour of the invention based on the CIE Lab colour spaces
The method of change also includes, there is provided a pH meter, the pH value in synchro measure reaction tank.
Further, according to a preferred embodiment of the invention, by L*、a*、b*Transmit to the second computing unit,
Second computing unit is according to the space chromacity value L received*、a*、b*Sampled point is calculated relative to other any one sampled points
Value of chromatism △ E.
According to a preferred embodiment of the invention, initialization of calibration is carried out to solution, by chromatic value L*Value is adjusted to
100, a*Value is adjusted to 0.00, b*Value is adjusted to 0.00, calculates the L of any one sampled point*Value, a*Value, b*Value and L0 *For 100,
a0 *It is worth for 0.00, b0 *It is worth for the aberration △ E between 0.00.
According to a preferred embodiment of the invention, the L of the titration desired value point of solution is specifiede *、ae *、be *Value, calculate
Any one sampled point relative to specified desired value point aberration.
According to a preferred embodiment of the invention, calculate between any one sampled point and the consecutive points of the sampled point
Value of chromatism.
Further, according to a preferred embodiment of the invention, it is any one relative to other to calculate a sampled point
The ratio between the value of chromatism △ E of sampled point and the pH value of the sample point, i.e. △ E/pH.
Alternatively, value of chromatism △ E and the sample point of the sampled point relative to other any one sampled points are calculated
L*Value, a*Value, b*Value, C*Value, H*The ratio between parameter in value, that is, calculate △ E/L*、△E/a*、△E/b*、△E/C*、△E/
H*One of.
Alternatively, according to a preferred embodiment of the invention, it is any one relative to other to calculate a sampled point
The ratio between titration volumes difference △ V of the value of chromatism △ E of sampled point and two sampled points, i.e. △ E/ △ V.
Further, the value of chromatism △ E burst data transmissions being calculated to the 3rd computing unit, the described 3rd are calculated
Unit calculates the poor △ △ E between any two value of chromatism.
According to a preferred embodiment of the invention, between the two neighboring value of chromatism of the 3rd computing unit calculating
Difference.
According to a preferred embodiment of the invention, the 3rd computing unit calculates phase in the way of difference is taken downwards
Difference between adjacent two values of chromatism.
According to a preferred embodiment of the invention, the 3rd computing unit calculates phase in the way of difference is taken upwards
Difference between adjacent two values of chromatism.
Further, the 3rd computing unit is also programmed to calculate the poor △ △ E between two values of chromatism and institute
The ratio between pH value of corresponding Standard Sampling Point, i.e.,
Alternately, the 3rd computing unit be also programmed to calculate two values of chromatism between poor △ △ E with it is corresponding
The ratio between the pH difference of two sampled points, i.e.,
Alternatively, the 3rd computing unit be also programmed to calculate two values of chromatism between poor △ △ E with it is corresponding
Standard Sampling Point L*Value, a*Value, b*Value, C*Value, H*The ratio between parameter in value, that is, calculate △ △ E/L*、△△E/a*、
△△E/b*、△△E/C*、△△E/H*One of.
Alternately, the 3rd computing unit be also programmed to calculate two values of chromatism between poor △ △ E with it is right
The ratio between benchmark value of chromatism △ E answered, i.e.,
Alternately, the 3rd computing unit be also programmed to calculate two values of chromatism between poor △ △ E with it is corresponding
The ratio between titration volumes difference △ V of two sampled points, i.e.,
Alternately, the 3rd computing unit be also programmed to calculate two values of chromatism between poor △ △ E with it is corresponding
Two sampled points L*The ratio between value difference, i.e.,
Alternately, the 3rd computing unit be also programmed to calculate two values of chromatism between poor △ △ E with it is corresponding
Two sampled points a*The ratio between value difference, i.e.,
Alternately, the 3rd computing unit be also programmed to calculate two values of chromatism between poor △ △ E with it is corresponding
Two sampled points b*The ratio between value difference, i.e.,
Alternately, the 3rd computing unit be also programmed to calculate two values of chromatism between poor △ △ E with it is corresponding
The ratio between chroma C value differences of two sampled points, i.e.,
According to a preferred embodiment of the invention, the sampling interval duration of the spectrometer is arranged on 0.1ms-
In the range of 1000ms, and the scope of the measurement wavelength of the spectrometer is arranged to 380nm-780nm.
It is provided by the invention based on the CIE Lab colour spaces detection solution colour change method can utilize optics and
CIE Lab colour spaces principles enter Mobile state measure, and the absorbance by measuring and the Lab of calculating to the solution in reaction tank
Value carries out accurate description to solution colour, can carry out the Lab values being calculated to store by data processor and further
Processing, obtains the poor value of aberration and aberration, and then can describe their relations relative to volume number so that once given one
Individual Lab values, i.e. a color, it becomes possible to accurately titration volumes number corresponding with the color.
Brief description of the drawings
Fig. 1 is a kind of titration system schematic diagram for implementing chemistry titration；
Fig. 2 is CIE Lab color space figures；
Fig. 3 is the relation between aberration and titration volumes between adjacent two sampled point according to a titration example；
Fig. 4 is the sampled point according to a titration example relative to the pass between the aberration and titration volumes of initial value point
System；
Fig. 5 is with titrating body according to the sampled point of a titration example relative to the ratio between the aberration of initial value point and volume differences
Long-pending relation；
Fig. 6 be aberration between adjacent two sampled point according to a titration example and the ratio between volume differences and titration volumes it
Between relation；
Fig. 7 is the ratio between difference and titration volumes difference of the aberration between the neighbouring sample point according to a titration example and titration
The relation of volume；
Fig. 8 is according to the ratio between the difference of the aberration relative to initial value point of a titration example and titration volumes difference and titration
The relation of volume；
In figure：1 is light source, and 2 be reaction tank, and 3 be agitating device, and 4 be titration outfit, 5 is spectrometer, 6 is data acquisition
And processing unit, 7 be collimating mirror, and 8 be focus lamp, and 9 be sensor, and 11 be incident light source, and 12 regulation light sources, 2a is reaction tank,
3a is magnetic stirring apparatus.
Embodiment
Embodiment of the present invention is described more fully below, the example of the embodiment is shown in the drawings, wherein certainly
Begin to same or similar label eventually to represent same or similar element or there is the element of same or like function.
It should be understood that embodiments below is only illustrative, the present invention is not construed as limiting.Protection scope of the present invention by
Claims limit.It should also be understood that in implementing the present invention, it may, all technologies in following embodiments need not be included
Feature, these technical characteristics can have multiple combinations.
It should be noted that herein, the sampled point exploitation before sampled point and the point is referred to as value forward, will be sampled
Point is referred to as value backward with the sampled point exploitation after the point.
Fig. 1 shows a kind of titration system schematic diagram for implementing chemistry titration.The titration outfit includes：Light source 1, reaction tank
2nd, agitating device 3, titration outfit 4, spectrometer 5, data acquisition and processing (DAP) unit 6, collimating mirror 7, focus lamp 8 and sensor 9.Drop
Determine device 4 and testing liquid is instilled into reaction tank 2, agitating device 3 is stirred to the solution body in reaction tank 2, is shone with light source 1
Penetrate reaction tank 2, the collimated mirror 7 of light is injected in reaction tank perpendicular to the transmittance section of reaction tank, through reaction tank and therein molten
Projected after liquid, project light line focus mirror 8 and sensor 9 is received by spectrometer 5, the spectrometer measures solution in reaction tank
Absorbance, and L is calculated according to absorbance*、a*、b*Value, then by above-mentioned L*、a*、b*Value passes to data acquisition and processing (DAP)
Unit 6, further data processing is carried out, this will be described below.
Light source 1 can send the spectrum for including 280nm~1100nm spectral regions, the spectrometer in continuous mode,
Interior, wavelength interval 0.1nm~100nm the specified any one group of wavelength of measurement 280nm~1100nm spectral regions of selectivity
Absorbance, the calculating for CIE Lab colour space parameters.In addition, absorbance measuring time interval is in 0.1ms~10min scopes
Interior setting so that spectrometer can dynamically measure absorbance, and a corresponding body titrated at each time of measuring point
Product, i.e., the volume number of the corresponding titration of each absorbance, further, every group of CIE Lab colour space parameter is all right
Answer the volume number of a titration.In the present embodiment, spectrometer is arranged to, light path selection 10nm, sampling time interval choosing
1000ms is selected, is all-wave length by measurement wave-length coverage selection, the scope of wherein all-wave length is arranged to 380~780nm, the ripple of measurement
Length is at intervals of 5nm.It should be understood that what above-mentioned arrange parameter was merely exemplary, specific arrange parameter is changeable.
In the present embodiment, light source uses LED light source, and its wave-length coverage is 280nm~1100nm, from syringe pump
SP1 is used to carry out titration operation, and SP1 is a compact-sized, for the product of accurate fluid transmission, passes through computer or micro- place
Reason device controls it, and is automatically performed liquid relief, dilution and distribution function, there is a higher precision, and relevant configured parameter is as follows：It is full
Stroke：60mm (6000 step)；Control resolution：0.01mm (1 step)；Stroke Control precision：≤5‰.
Spectrometer selects the hera01 model micro spectrometers of admesy companies, for measuring the spectrum of solution.It has
Following functions feature：Small volume, it is easy to neatly build spectroscopic system；With modularization and the characteristics of high speed acquisition；With reference to light
Source, optical fiber, measurement annex, can mix into various optical measuring systems；With internal structure it is compact, without moving parts, wavelength
The advantages that scope is wide, measuring speed is fast, price economy；It is widely used in portable, intelligent Detection exploitation and industry exists
The fields such as line monitoring.Micro spectrometer has high-resolution, pinpoint accuracy, high speed acquisition, high real-time in gatherer process
Advantage.
Fig. 2 is CIE Lab color space figures.As shown in Fig. 2 CIE Lab color spaces are the color of a space multistory
Description system, on Color Range, Lab patterns are most full color description patterns.In CIE Lab color spaces, L*For color
Lightness in space, a*For the red green chromaticity exponential quantity in the colour space, b*For the yellow blue chromaticity exponential quantity in the colour space, C* abFor
The chroma value of the colour space, habFor the hue angle value of the colour space.Any color all has corresponding L*、a*、b*Value, it is on the contrary
As the same, each point in CIE Lab color spaces corresponds to a color.
As previously described, spectrometer measures to the spectrum through reaction tank, the spectrum that spectrometer collection is arrived
Original value obtains space chromacity value by calculating.The transmitance of solution first is obtained with original spectrum, then obtains tristimulus values X10,
Y10, Z10, finally obtain the space chromacity value L of solution*、a*、b*、C*Deng its calculating process formula is specific as follows：
Wherein A is absorbance；
Wherein L is light path；
τ (λ)=10-A′, wherein τ (λ) is light transmittance；
Wherein S (λ) is the relative spectral power distribution of working flare；
Wherein κ10For normalization coefficient；
Wherein, L*For lightness, a*And b*For chromaticity index.
With L*、a*、b*Based on value, by L*、a*、b*Transmit to data processing unit, can calculate associated various
Index, for example, poor △ △ E of chroma C, hue angle H, aberration △ E, aberration etc..
The space chromacity value L of solution will be calculated in spectrometer*、a*、b*Transmit to the first computing unit, according to receiving
L*、a*、b*Chroma value C and hue angle value H values corresponding to value calculating at titration volumes number.
Preferably, above-mentioned titration system also includes pH meter, for measuring the pH value of the solution in reaction tank.By pH meter
PH value is measured to be passed in data processing unit 6, can be with for describing the relation between measurement color and acid-base value
The corresponding relation between each pH value and titration volumes number is described using the pH value measured.Further, it is also possible to measured using calculating
PH value and sample point L*、a*、b*、C*、H*The ratio between parameter in value.
For any one sampled point, the first computing unit utilizes L*、a*、b*Value can calculate the point relative to other
The value of chromatism △ E of one sampled point of meaning.So that using exemplified by 1976CIE Lab systems, the calculation formula of aberration is as follows：
WhereinL corresponding to respectively selected sampled point*、a*、b*Value, Li’ *、ai’ *、bi’ *It is worth and is
Space chromacity value corresponding to other any one sampled points.
It should be understood that other system computing aberration can also be used, such as 2000CIE Lab systems, its calculation formula is herein
No longer it is described in detail.
Other described any one sampled points can be initial value point, desired value point (titration end-point) or the sampling with the selection
An adjacent sampled point of point.
According to an aspect of the present invention, when calculating aberration constantly relative to solution initial value point, titration system preferably wraps
Calibration system has been included, the initial point of titration has been calibrated.
For example, the calibration system is made up of blank calibrated vessel and shift unit, in the blank calibrated vessel
Liquid containing specified absorbance, and the printing opacity light path for having blank calibrated vessel is identical with the printing opacity light path of reaction tank, preferably
Ground, blank calibrated vessel use the parallel transmitted light piece of spacing identical with reaction tank, irradiate the blank calibrated vessel, profit with light source
CIE Lab colour space parameters are calculated with spectrometer, and by the L in CIE Lab colour space parameters*Value correction is to 100, parameter a*Value
Correction is to 0, parameter b*Value correction is to 0, for comparing the CIE Lab colour spaces parameters of blank value and the CIE after titration before titration
Absolute difference between Lab colour space parameters.Blank calibrated vessel is removed using shift unit after calibration, and by reaction tank
Move into measurement position.
It should be understood that initial value can also be calibrated to a L specified*、a*、b*Value, and the L that this is specified*、a*、b*Value
As initial value.
Herein, by the L at initial value point*、a*、b*Value is referred to asNeeded when calculating aberration to initial
It is poor that point value is made, by taking 1976CIE Lab systems as an example, aberration
According to another aspect of the present invention, when need relative to desired value point (titration end-point) calculate aberration when, it is necessary to
L at desired value point*、a*、b*It is poor that value is made, and calculates value of chromatism △ E.In practice operates, for a titration operation, lead to
Often need to provide a titration end-point, then each parameter at titration end-point is known, and it is phase to carry out exploitation to desired value
To convenient.
Herein, by the L at desired value point*、a*、b*Value is referred to asUsing 1976CIE Lab systems as
Example, aberration
According to another aspect of the present invention, the aberration between one sampled point of calculating sampled point adjacent thereto is needed
When, it is necessary to the L at the neighbouring sample point*、a*、b*Value makees difference and calculates aberration.The consecutive points can be located at before sampled point,
It can be located at after sampled point, i.e., the neighbouring sample point can be a sampled point or choosing before the sampled point chosen
The sampled point latter one sampled point taken.
Fig. 4 is sampled point relative to the relation between the aberration and titration volumes of initial value point.Herein, by consecutive points
The L at place*、a*、b*Value is referred to asOr By taking 1976CIE Lab systems as an example, phase
For sampled point Si+1Aberration is calculated, then
It should be noted that in 1976CIE Lab systems, sampled point is latter to its to its previous sampled point value and sampled point
Individual sampled point value, do not influenceed on calculating value of chromatism, and for other counting systems, value direction difference may be made
It is different into value of chromatism, should be according to the specific program calculation of the counting system applied.
Further, according to a preferred embodiment of the invention, for any one sampled point, the sampled point is calculated
Relative to the value of chromatism △ E of other any one sampled points, and by the pH value of the value of chromatism being calculated and the sample point it
Than i.e. △ E/pH.The result for calculating gained can be as a critical parameter of detection solution colour change.
Furthermore it is possible to calculate value of chromatism △ E and the sample point of the sampled point relative to other any one sampled points
L*Value, a*Value, b*Value, C*Value, H*The ratio between parameter in value, that is, calculate △ E/L*、△E/a*、△E/b*、△E/C*、△
E/H*One of.The result for calculating gained can be as a critical parameter of detection solution colour change.
Adopted it is possible to further calculate a sampled point relative to the value of chromatism △ E of other any one sampled points with two
L between sampling point*The difference of value, a*The difference of value, b*The difference of value, C*The difference of value, H*The ratio between parameter in the difference of value, that is, calculate △
E/△L*、△E/△a*、△E/△b*、△E/△C*、△E/△H*One of.Detection solution face can be used as by calculating the result of gained
One critical parameter of color change.
Alternatively, according to a preferred embodiment of the invention, for any one sampled point, the sampled point is calculated
Relative to the value of chromatism △ E of other any one sampled points, and by the drop between the value of chromatism being calculated and two sampled points
Determine the ratio between volume differences △ V, i.e. △ E/ △ V.Similarly, the result for calculating gained can also be as the one of detection solution colour change
Individual critical parameter.
Preferably, exemplified by calculating value of chromatism relative to initial value point, the chromatic value at initial value point is referred to as E0, titration
Volume number is referred to as V0, the chromatic value of sample point is referred to as Ei, titration volumes number is referred to as Vi, thenFig. 5 is sampling
Point is relative to the relation of the ratio between the aberration of initial value point and volume differences with titration volumes.
Similarly, when the value of chromatism between calculating selected sampled point sampled point adjacent thereto, it is necessary to calculate corresponding
Aberration and the ratio between volume differences.
Relation of the ratio between the aberration and volume differences of Fig. 6 between adjacent two sampled point between titration volumes.
It should be noted that in the case, the value of volume differences is influenceed by value direction.
Further, by the value of chromatism △ E burst data transmissions being calculated to the 3rd computing unit.With relative to initial
Exemplified by value point calculates value of chromatism, for any one sampled point i
(i=1,2 ..., n, wherein n are total sampling number), calculates its aberration relative to initial value point, and be calculated
Chromatism data group transmit to the 3rd computing unit, value of chromatism △ E data groups are denoted as △ E1、△E2、…△En(n is total adopts
Number of samples), the 3rd computing unit can therefrom optional two values of chromatism, calculate the poor △ △ between any two value of chromatism
E。
Preferably, the 3rd computing unit calculates the difference between two neighboring value of chromatism.
According to a preferred embodiment of the invention, the 3rd computing unit calculates phase in the way of difference is taken downwards
Difference between adjacent two values of chromatism, i.e. calculated according to sampled point sequencing.A for example, sampled point S1Relative to
Its latter S2Sampled point calculates aberration △ E1, the latter sampled point S2Relative to its next sampled point S3Calculate color
Poor △ E2, then by △ E1-△E2Calculate the difference of aberration, and so on calculate △ E2-△E3..., △ En-1-△En。
According to a preferred embodiment of the invention, the 3rd computing unit calculates phase in the way of difference is taken upwards
Difference between adjacent two values of chromatism, this calculation takes downwards the mode of difference similar with above-mentioned, but value is in opposite direction.3rd
Unit performs following computing：△E2-△E1, △ E3-△E2..., △ En-△En-1。
In the following description, phase is calculated relative to initial value point calculating aberration, in a manner of taking difference downwards by sampled point
In case of difference between adjacent two values of chromatism, the specific embodiment of the present invention is described.
Further, the 3rd computing unit be also programmed to calculate two values of chromatism between it is poor with it is corresponding
The ratio between pH value of Standard Sampling Point, i.e.,Wherein, Δ Δ E=△ Ei-1-△Ei(wherein, 1<i<N, n are total sampling number),
△Ei-1For sampled point Si-1Relative to sampled point S0Aberration, △ EiFor sampled point SiRelative to sampled point S0Aberration, pH is adopts
Sampling point SiPH value.Can be as a critical parameter of detection solution colour change.
Alternately, the 3rd computing unit be also programmed to calculate two values of chromatism between it is poor with corresponding two
The ratio between pH difference of sampled point, i.e.,WithCritical parameter is similar, Δ Δ E=△ Ei-1-△Ei(wherein, 1<i<N, n are
Total sampling number), △ Ei-1For sampled point Si-1Relative to sampled point S0Aberration, △ EiFor sampled point SiRelative to sampled point S0
Aberration, Δ pH is sampled point SiWith sampled point Si-1PH value difference.
Alternately, the 3rd computing unit is also programmed to calculate the poor and corresponding base between two values of chromatism
The ratio between quasi- value of chromatism, i.e.,Wherein, Δ Δ E=△ Ei-1-△Ei(wherein, 1<i<N, n are total sampling number), △ Ei-1To adopt
Sampling point Si-1Relative to sampled point S0Aberration, △ EiFor sampled point SiRelative to sampled point S0Aberration, Δ E is sampled point SiPhase
For the value of chromatism of initial value point.
Alternately, the 3rd computing unit be also programmed to calculate two values of chromatism between it is poor with corresponding two
The ratio between titration volumes difference of sampled point, i.e.,Wherein, Δ Δ E=△ Ei-1-△Ei(wherein, 1<i<N, n are total sampled point
Number), △ Ei-1For sampled point Si-1Relative to sampled point S0Aberration, △ EiFor sampled point SiRelative to sampled point S0Aberration, Δ
V is sampled point SiWith sampled point Si-1The titration volumes at place are poor.The difference and titration volumes of aberration of the Fig. 7 between neighbouring sample point
The ratio between difference and the relation of titration volumes；Fig. 8 is with titrating body relative to the ratio between the difference of the aberration of initial value point and titration volumes difference
Long-pending relation.
Alternately, the 3rd computing unit be also programmed to calculate two values of chromatism between it is poor with corresponding two
The L of sampled point*The ratio between value difference, i.e.,Wherein, Δ Δ E=△ Ei-1-△Ei(wherein, 1<i<N, n are total sampling number), △
Ei-1For sampled point Si-1Relative to sampled point S0Aberration, △ EiFor sampled point SiRelative to sampled point S0Aberration, Δ L*To adopt
Sampling point SiWith sampled point Si-1The L at place*The difference of value.
Alternately, the 3rd computing unit be also programmed to calculate two values of chromatism between it is poor with corresponding two
The a of sampled point*The ratio between value difference, i.e.,Wherein, Δ Δ E=△ Ei-1-△Ei(wherein, 1<i<N, n are total sampling number), △
Ei-1For sampled point Si-1Relative to sampled point S0Aberration, △ EiFor sampled point SiRelative to sampled point S0Aberration, Δ a*To adopt
Sampling point SiWith sampled point Si-1The a at place*The difference of value.
Alternately, the 3rd computing unit be also programmed to calculate two values of chromatism between it is poor with corresponding two
The b of sampled point*The ratio between value difference, i.e.,Wherein, Δ Δ E=△ Ei-1-△Ei(wherein, 1<i<N, n are total sampling number), △
Ei-1For sampled point Si-1Relative to sampled point S0Aberration, △ EiFor sampled point SiRelative to sampled point S0Aberration, Δ b*To adopt
Sampling point SiWith sampled point Si-1The b at place*The difference of value.
Alternately, the 3rd computing unit be also programmed to calculate two values of chromatism between it is poor with corresponding two
The ratio between chroma C value differences of sampled point, i.e.,Wherein, Δ Δ E=△ Ei-1-△Ei(wherein, 1<i<N, n are total sampling number),
△Ei-1For sampled point Si-1Relative to sampled point S0Aberration, △ EiFor sampled point SiRelative to sampled point S0Aberration, Δ C is
Sampled point SiWith sampled point Si-1The difference of the chroma value C values at place.
It should be understood that shown in the embodiment above can as detection solution colour change some critical parameters, but
This is not limited to, critical parameter of any one or more characteristic values as detection solution colour change can be chosen, according to molten
PH value, aberration △ E values, the poor △ △ E values of aberration and the bulking value V of liquid can be generally divided into four classes, as shown in Table 1 and Table 2：
Table 1
Table 2
Exemplarily, the lines figure shown from Fig. 3 into Fig. 8, parameter △ E (△ V), △ E (△ V)/△ V, △ △ E
(V0)/△ V instructions are consistent, and △ △ E (△ V)/△ V are slightly advanced.
For peak height, △ E (△ V) and baseline separation are highly worst；△E(△V)/△V、△△E(△V)/△V、△
△ E (V0)/△ V and baseline separation are highly best, in 200--1000；
For peak shape：△ E (△ V), △ E (△ V)/△ V, △ △ E (V0)/△ V are unimodal；△△E(△V)/△V
There are multiple small peaks near top.
Consider parameter application priority：△ E (△ V)/△ V==△ △ E (V0)/△ V=△ E (△ V) ＞ △ △ E
(△V)/△V。
In described above by any one sampled point relative to initial value point calculate aberration, in a manner of taking difference downwards based on
In case of calculating the difference between two neighboring value of chromatism, the calculating to each critical parameter is illustrated, it should be appreciated that can be with
Each critical parameter is calculated according to other data decimation modes.
It should be noted that the above-mentioned curve map shown is only to be showed in a titration example, which specifically chosen ginseng
Number is it is also contemplated that its reaction condition, corresponding volume, condition determination etc..
Multiple critical parameters for being used to detect solution colour change are illustrated in the present invention, it should be appreciated that above-mentioned embodiment party
Case should not be understood as the limitation to protection scope of the present invention, and those skilled in the art can be carried out to parameter set forth above
Deformation is integrated, and for detection solution colour change, and all deformations to above-mentioned parameter all should belong to the protection of the present invention
Scope.
It is obvious to a person skilled in the art that the invention is not restricted to the details of above-mentioned one exemplary embodiment, Er Qie
In the case of without departing substantially from spirit or essential attributes of the invention, the present invention can be realized in other specific forms.Therefore, no matter
From the point of view of which point, embodiment all should be regarded as exemplary, and be nonrestrictive, the scope of the present invention is by appended power
Profit requires rather than described above limits, it is intended that all in the implication and scope of the equivalency of claim by falling
Change is included in the present invention.Any reference in claim should not be considered as to the involved claim of limitation.
Moreover, it will be appreciated that although the present specification is described in terms of embodiments, not each embodiment is only wrapped
Containing an independent technical scheme, this narrating mode of specification is only that those skilled in the art should for clarity
Using specification as an entirety, the technical solutions in the various embodiments may also be suitably combined, forms those skilled in the art
It is appreciated that other embodiment.
Claims (13)
- A kind of 1. method of the detection solution colour change based on the CIE Lab colour spaces, it is characterised in that comprise the following steps：(1) light source is provided, the light of light source is incided perpendicular to the transmittance section of reaction tank in reaction tank；(2) titrated using titration outfit into reaction tank, and record titration volumes；(3) emergent light through the solution in reaction tank is conducted into spectrometer；(4) spectrometer takes absorbance A bs signal values according to data sampling interval to being transmitted to spectral signal therein, and Signal value is transmitted to data processing unit, data processing unit absorbance A bs signal values according to corresponding to different wave length calculate Obtain space chromacity value L of the solution at corresponding titration volumes number*、a*、b*Value.
- 2. according to the method for claim 1, it is characterised in that methods described is also included L*、a*、b*Value is transmitted to first Computing unit, according to the L received*、a*、b*Chroma value C and hue angle value H corresponding to value calculating at titration volumes number.
- 3. method according to claim 1 or 2, it is characterised in that methods described also includes, there is provided a pH meter, it is synchronous Measure the pH value in reaction tank.
- 4. according to the method for claim 2, it is characterised in that methods described is also included L*、a*、b*Transmit to the second meter Unit is calculated, second computing unit is according to the space chromacity value L received*、a*、b*It is any relative to other to calculate sampled point The value of chromatism △ E of one sampled point.
- 5. according to the method for claim 4, it is characterised in that methods described also includes calculating a sampled point relative to it The ratio between the value of chromatism △ E of his any one sampled point and the pH value of the sample point, i.e. △ E/pH.
- 6. according to the method for claim 4, it is characterised in that methods described also includes calculating a sampled point relative to it The value of chromatism △ E of his any one sampled point and L of the sample point*Value, a*Value, b*Value, C*Value, H*A parameter in value it Than calculating △ E/L*、△E/a*、△E/b*、△E/C*、△E/H*One of.
- 7. according to the method for claim 4, it is characterised in that methods described also includes calculating a sampled point relative to it The ratio between titration volumes difference △ V of the value of chromatism △ E of his any one sampled point and two sampled points, i.e. △ E/ △ V.
- 8. according to the method described in any one of claim 4-7, it is characterised in that methods described also includes, and will calculate The value of chromatism △ E burst data transmissions arrived to the 3rd computing unit, the 3rd computing unit is calculated between any two value of chromatism Poor △ △ E.
- 9. according to the method for claim 8, it is characterised in that methods described also includes, the 3rd computing unit also by The ratio between poor △ △ E and corresponding pH value of Standard Sampling Point for being programmed for calculating between two values of chromatism, i.e.,
- 10. according to the method for claim 9, it is characterised in that methods described also includes, the 3rd computing unit also by The ratio between poor △ △ E and corresponding two sampled points pH difference for being programmed for calculating between two values of chromatism, i.e.,
- 11. according to the method for claim 8, it is characterised in that methods described also includes, the 3rd computing unit also by It is programmed for calculating the poor △ △ E between two values of chromatism and corresponding Standard Sampling Point L*Value, a*Value, b*Value, C*Value, H*Value In a ratio between parameter, that is, calculate △ △ E/L*、△△E/a*、△△E/b*、△△E/C*、△△E/H*One of.
- 12. according to the method for claim 8, it is characterised in that methods described also includes, the 3rd computing unit also by The ratio between poor △ △ E and corresponding benchmark value of chromatism △ E for being programmed for calculating between two values of chromatism, i.e.,
- 13. according to the method for claim 8, it is characterised in that methods described also includes, the 3rd computing unit also by The ratio between poor △ △ E and titration volumes difference △ V of corresponding two sampled points for being programmed for calculating between two values of chromatism, i.e.,
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| CN112540145A (en) * | 2020-11-04 | 2021-03-23 | 江苏大学 | Automatic chromatic aberration titrator and measuring method thereof |
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