CN106908492B - A kind of discrimination method of aromatic isomer 3- hydroxybenzoic acid and 4-HBA - Google Patents
A kind of discrimination method of aromatic isomer 3- hydroxybenzoic acid and 4-HBA Download PDFInfo
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Abstract
A kind of discrimination method of aromatic isomer 3- hydroxybenzoic acid and 4-HBA, it is characterised in that: apply " H2SO4‑NaBrO3‑[CuL](ClO4)2Malic acid " nonlinear chemical oscillation system, which is used as, identifies solution, different to oscillatory response caused by the system with 4-HBA according to aromatic isomer 3- hydroxybenzoic acid, and then realizes that aromatic series identifies the differentiation of isomer；[CuL](ClO4)2Middle L is 5,7,7,12,14,14- vegolysen, tetra- azepine of 4,8,11-, 14-4,11- diene.Oscillation map provided by this identification method has more intuitive, it not only can be convenient and quickly identify aromatic isomer 3- hydroxybenzoic acid and 4-HBA, it can also be widely used in other isomers, and equipment is simple, accuracy is high, easily operated and observation.
Description
Technical field
The present invention relates to a kind of differentiation discrimination methods, specifically a kind of 14 cyclic diolefine copper complex of four azepine
[CuL](ClO4)2 The nonlinear chemical system of catalysis is to aromatic isomer 3- hydroxybenzoic acid and 4-HBA
Discrimination method.Belong to qualitative analysis chemical field.
Background technique
3- hydroxybenzoic acid and 4-HBA molecular formula having the same, belong to aromatic isomer,
Structure is as shown in the formula (I).3- hydroxybenzoic acid is used as fungicide, coating, preservative, ion-exchanger, plasticizer and medicine
Intermediate, it is also possible to synthesize azo dyes etc..4-HBA is mainly as the basic material of fine chemical product, it is also
It is widely used in and prepares each middle dyestuff, fungicide, colour cinefilm and various solvent-soluble color couplers etc., and 4- hydroxy benzenes first
Esters of gallic acid can be used as the preservative of food, medicine and cosmetics.
Since 3- hydroxybenzoic acid is identical with 4-HBA molecular formula, structure is close, so that some physics and chemistry
Property is also similar, and the appearance of the two is also very much like, and the two is caused to be difficult to differentiate between.Although many reports existing at present are about fixed
The method of amount analysis hydroxybenzoic acid concentration, such as HPLC, electrochemical methods, capillary electrophoresis.But about to 3- hydroxyl
The differentiation identification of two kinds of isomers of yl benzoic acid and 4-HBA there is no report.Therefore, there is an urgent need to a kind of identifications
Effect it is good and it is easy to operate quickly, the result method that easily determines identify both substances.
(I)
Summary of the invention
The present invention is directed to for aromatic isomer 3- hydroxybenzoic acid and 4-HBA provide it is a kind of novel and
Discrimination method is conveniently distinguished, i.e., with four azepine 14 cyclic diolefine copper complex [CuL] (ClO4)2The non-linearization of catalysis
For system to the discrimination method of 3- hydroxybenzoic acid and 4-HBA, this discrimination method is complex-catalyzed non-based on this
Linear chemical system (i.e. oscillation system) is responded to the acumen of aromatic isomer and a kind of electrochemical oscillation body of exploitation
It is method.Wherein, [CuL] (ClO4)2In L be 5,7,7,12,14,14- vegolysen, tetra- azepine ten of 4,8,11-
Four -4,11- diene.Specifically, being that same concentrations sample to be identified is added separately in oscillation system, according to be identified
Sample is different to oscillatory response caused by oscillation system (variation for vibrating map), realizes qualitative point to sample to be identified
Analysis.
The present invention solves technical problem, adopts the following technical scheme that
The discrimination method of aromatic isomer 3- hydroxybenzoic acid and 4-HBA of the present invention, feature exist
In:
Using secondary distilled water as solvent, the solution of sample to be identified is prepared；
Using " H2SO4 - NaBrO3 - [CuL](ClO4)2 Malic acid " nonlinear chemical oscillation system is molten as identifying
Liquid records the oscillation map of oscillation system.At any one stable current potential minimum point that oscillation generates, to two groups of oscillating bodies
The solution of sample to be identified is separately added into system, it is real according to sample to be identified to the difference of oscillatory response caused by oscillation system
Now to the qualitative analysis of sample to be identified；
The sample to be identified is 3- hydroxybenzoic acid and 4-HBA；
Into two groups of oscillation systems, after being separately added into the solution of sample to be identified, it is suppressed if vibrating, by one section
Inhibit the time, then revert to the damped oscillation that amplitude is gradually reduced, then the sample to be identified is 3- hydroxybenzoic acid；If vibration
The system of swinging directly becomes the damped oscillation that amplitude is gradually reduced, and does not occur the inhibition time, then the sample to be identified is 4- hydroxyl
Benzoic acid.
The 3rd ~ 21 current potential that any one the stable current potential minimum point for wherein vibrating generation refers to that oscillation generates is minimum
Point in any one.
So-called four azepines, the 14 cyclic diolefine copper complex of the present invention is 5,7,7,12,14,14- vegolysen,
4,8,11- tetra- azepines 14-4,11- diene are four major esters copper (II) complex of ligand, are denoted as [CuL] (ClO4)2,
Its structure is as shown in the formula (II), and L is 5,7,7,12,14,14- vegolysens, 4,8,11- tetra- azepines 14-4,11- diene.
(II)
Four major esters catalyst plays a crucial role in the present invention, and configuration is broadly divided into two steps: 1)
Prepare L2HClO4；2) by L2HClO4Prepare [CuL] (ClO4)2
1) L·2HClO4Synthesis:
The reaction carries out under condition of ice bath always.98.5mL ethylenediamine is added in the three-necked bottle of 500 mL, uses dropping liquid
126 mL70% perchloric acid are slowly added dropwise in funnel, and the mixing speed for adjusting magnetic stirring apparatus is 500r/min.Initial reaction is violent
And generated with white cigarette, so rate of addition control is dripped in every five seconds clock 1, ice is formed in funnel bottom if too fast solution is added dropwise
Column and cause funnel blockade.It is gradually decreased as reaction carries out white cigarette, the severe degree of reaction, which also gradually mitigates, suitably to be added
Fast rate of addition obtains transparent solution until dripping.224 mL anhydrous propanones and violent are added to the clear solution
Stirring, solution becomes cloudy quickly is formed simultaneously very viscous mixture.Mixing speed should be properly increased at this time, adjust stirring speed
Degree is 1000r/min, keeps 2-3 hours under conditions of ice-water bath still sufficiently to react.It is sticky to finally obtain milk yellow
Gained viscous fluid is transferred to Buchner funnel and carries out suction filtration separation, and sufficiently washed with acetone by liquid, can obtain pure white solid.It will
This pure white solid recrystallizes in the methanol-water solution of heat, is dried in vacuo with silica-gel desiccant, obtains 80 g white crystals, this
White crystal is L2HClO4。
Bibliography:
1.Curtis, N. F. and Hay, R. W. , J. Chem. Soc. , Chem. Commun. ,
1966, p. 534.
2.Gang Hu, Panpan Chen, Wei Wang, Lin Hu, Jimei Song, Lingguang Qiu,
Juan Song, E1ectrochimica Acta, 2007, Vol. 52, pp. 7996-8002.
3. Lin Hu, Gang Hu, Han-Hong Xu, J. Ana1. Chem. , 2006, Vol. 61, NO.
10, pp. 1021-1025.
4. Hu Gang, China Science & Technology University's doctoral thesis, p25-27, Hefei, 2005.
2) by L2HClO4Prepare [CuL] (ClO4)2:
It is separately added into 19.5g Cu (AC)24H2The L2HClO of O and 21g4It is placed in 1000mL three-necked bottle, adds
The methanol of 500mL.After hot bath is heated to reflux 3-4 hours, there is red precipitate.Red precipitate is filtered, filtrate is in hot bath
On be concentrated into original volume 1/2-1/3, stand overnight.After sufficient crystallising, available red crystals.Red crystals are transferred to cloth
Family name's funnel ethanol washing recrystallizes in the ethanol-water solution of heat, is dried in vacuo, can obtain about 9g [CuL] (ClO4)2It is red brilliant
Body.
Bibliography:
1. Hu Gang, China Science & Technology University's doctoral thesis, Hefei, 2005
2.D. A. House and N. F. Curtis, Transition meal complexes with
alipatic Schiff bases.V.copper (II) and nickel(II) complexes of 1,3-
Propanediamine and their reations with acetone[J] J. Amer. Chem. Soc., 1964,
86;223-225.
Detection method difference with the prior art of the present invention is that the present invention applies " H2SO4 - NaBrO3 -
[CuL](ClO4)2 The oscillation system of malic acid " is as solution is identified, according to aromatic isomer 3- hydroxybenzoic acid
With 4-HBA to the difference of acumen oscillatory response caused by the reaction system, and then realize to aromatic series isomerism
The differentiation of body identifies.Aromatic isomer 3- hydroxybenzoic acid and 4-HBA identify in solution identify it is dense
Spending range is 7.0 × 10-5 - 2.5 × 10-4Mol/L, it is tests determined optimal concentration that this, which can identify concentration range,
Range, the difference that 3- hydroxybenzoic acid and 4-HBA generate response to oscillation in the concentration range are very clear bright
It is aobvious, it is easy to identification can be realized；It is as shown in table 1 to identify each component concentration in solution, the optium concentration determined through test of many times
It is as shown in table 2:
Table 1: the concentration range of each component in oscillation system
| Sodium bromate (mol/L | Sulfuric acid (mol/L) | Malic acid (mol/L) | [CuL](ClO4)2(mol/L) |
| 1.625×10-2-2.437×10-2 | 0.95-1.0 | 0.2-0.225 | 2.61×10-3-2.83×10-3 |
Table 2: the optium concentration of each component in oscillation system
| Sodium bromate (mol/L) | Sulfuric acid (mol/L) | Malic acid (mol/L) | [CuL](ClO4)2(mol/L) |
| 0.01625 | 1 | 0.2 | 2.61×10-3 |
Concrete operations are as follows:
1, it is prepared by solubility best in table and identifies solution, and recorded the E-t curve that the solution potential changes over time and change
Learn electrical oscillation map.
Firstly, taking in a 50 mL small beakers and being put into sizeable magneton, it is placed on constant temperature magnetic heating stirrer
On, speed is kept stirring in 500 r/min.Oscillation system each component solution is added into beaker.Ready working electrode
(platinum electrode) and reference electrode (double salt bridge calomel electrodes) are inserted into beaker, and working electrode and reference electrode pass through amplifier
(Instrument Amplifier) is connected to data collector (GO!LINK it) is then connected on computer by USB again.It opens
Computer equipped with logger lite software, using logger lite software to solution potential change with time situation carry out
(sample to be tested is not yet added) in acquisition in real time at this time, to make blank control.It is dense with each component in blank control experiment to two groups
It spends in identical oscillation system, at any one stable current potential minimum point that oscillation generates, is rapidly added respectively to be identified
The solution of sample, according to sample to be identified to the difference of oscillatory response caused by oscillation system, sample to be identified is determined in realization
Property analysis.That is: after being separately added into the solution of sample to be identified into two groups of oscillation systems, if oscillation is suppressed, by one
Section inhibits the time, then reverts to the damped oscillation that amplitude is gradually reduced, then the sample to be identified is 3- hydroxybenzoic acid；If
Oscillation system directly becomes the damped oscillation that amplitude is gradually reduced, and does not occur the inhibition time, then the sample to be identified is 4- hydroxyl
Yl benzoic acid.
Chemical potential oscillation map basic parameter include:
Amplitude of oscillation: in oscillatory process from a potential minimum to the potential difference next maximum potential.
Cycle of oscillation: in oscillatory process the time required to from minimum (height) current potential to next minimum (height) current potential.
Maximum potential: the current potential highest point that system occurs when stable oscillation stationary vibration.
Potential minimum: the current potential minimum point that system occurs when stable oscillation stationary vibration.
Inhibit the time: after addition prepare liquid, vibrating suppressed to recovery oscillation required time again.
Detailed description of the invention
Fig. 1 is when sample to be identified not being added, to identify the oscillation map of solution (oscillation system) in embodiment 1.
Fig. 2, Fig. 3 are to be separately added into 1.6 × 10 in embodiment 1-4Mol/L 3- hydroxybenzoic acid and 4-HBA
Afterwards, oscillation system oscillatory response map obtained.
Fig. 4 is when sample to be identified not being added, to identify the oscillation map of solution (oscillation system) in embodiment 2.
Fig. 5, Fig. 6 are to be separately added into 1.7 × 10 in embodiment 2-4Mol/L 3- hydroxybenzoic acid and 4-HBA
Afterwards, oscillation system oscillatory response map obtained.
Fig. 7 is when sample to be identified not being added, to identify the oscillation map of solution (oscillation system) in embodiment 3.
Fig. 8, Fig. 9 are to be separately added into 1.8 × 10 in embodiment 3-4Mol/L 3- hydroxybenzoic acid and 4-HBA
Afterwards, oscillation system oscillatory response map obtained.
Figure 10 is when sample to be identified not being added, to identify the oscillation map of solution (oscillation system) in embodiment 4.
Figure 11, Figure 12 are to be separately added into 2.0 × 10 in embodiment 4-4Mol/L 3- hydroxybenzoic acid and 4-HBA
Afterwards, oscillation system oscillatory response map obtained.
Figure 13 is when sample to be identified not being added, to identify the oscillation map of solution (oscillation system) in embodiment 5.
Figure 14, Figure 15 are to be separately added into 2.3 × 10 in embodiment 5-4Mol/L 3- hydroxybenzoic acid and 4-HBA
Afterwards, oscillation system oscillatory response map obtained.
Figure 16 is when sample to be identified not being added, to identify the oscillation map of solution (oscillation system) in embodiment 6.
Figure 17, Figure 18 are to be separately added into 2.5 × 10 in embodiment 6-4Mol/L 3- hydroxybenzoic acid and 4-HBA
Afterwards, oscillation system oscillatory response map obtained.
Specific embodiment
Embodiment 1:
The present embodiment verifies aromatic isomer 3- hydroxybenzoic acid and 4- hydroxy benzenes first of the present invention as follows
The feasibility of the discrimination method of acid:
(1) solution is prepared
Use first 98% the concentrated sulfuric acid and distilled water prepare 1.0mol/L sulfuric acid as stock solution, then use 1.0mol/L
Sulfuric acid solution prepared respectively as solvent the bromic acid sodium solution of 0.65mol/L, the malic acid solution of 2mol/L, 1.74 ×
10-2[CuL] (ClO of mol/L4)2Solution.
Simultaneously with second distillation water as solvent, 0.16mol/L 3- hydroxybenzoic acid and 4-HBA are prepared respectively
Solution.
(2) map is vibrated
Magneton is added into 50mL small beaker, sequentially adds 29mL 1.0mol/L sulfuric acid solution, 1mL 0.65mol/L
Bromic acid sodium solution, 4mL 2mol/L malic acid solution, be eventually adding 6mL 1.74 × 10-2[CuL] (ClO of mol/L4)2
Solution, maintenance system total volume are 40mL, guarantee " H2SO4 - NaBrO3 - [CuL](ClO4)2 Malic acid " oscillation system
In (identifying solution), the molar concentration of each component is respectively sulfuric acid 1.0mol/L, sodium bromate 0.01625mol/L, malic acid
0.2mol/L、[CuL](ClO4)2 2.61×10-3mol/L.It is molten that identification is recorded with the computer equipped with logger lite program
The oscillation map that liquid current potential changes over time.
Fig. 1 be under typical concentration (sulfuric acid 1.0mol/L, sodium bromate 0.01625mol/L, malic acid 0.2mol/L,
[CuL](ClO4)2 2.61×10-3Mol/L), the oscillation map of sample to be tested is not added for above-mentioned identification solution, to make blank pair
According to.The color of observation oscillation solution can be found that the continuous generating period variation of the color of solution: purple-brown color-purple,
And periodic variation is also presented in potential.
Take one group of each component concentration identification solution (sulfuric acid 1.0mol/L, sodium bromate identical with above-mentioned concentration
0.01625mol/L, malic acid 0.2mol/L, [CuL] (ClO4)2 2.61×10-3Mol/L), the 4th electricity is reached in oscillation map
When the minimum point of position, 40uL 0.16mol/L 3- hydroxybenzoic acid is added with liquid-transfering gun, so that it is in the concentration identified in solution
1.6×10-4Mol/L, resulting oscillatory response map are as shown in Figure 2.
Another group of each component concentration identification solution identical with above-mentioned concentration is taken, reaches the 4th current potential most in oscillation map
When low spot, 40uL 0.16mol/L 4-HBA is added with liquid-transfering gun, so that it is 1.6 identifying the concentration in solution
×10-4Mol/L, resulting oscillatory response map are as shown in Figure 3.
(3) it distinguishes and identifies
As aromatic isomer 3- hydroxybenzoic acid and 4-HBA to anti-due to molecular structure difference
System is answered to generate the difference of oscillatory response.As shown in Figure 2, compared to Figure 1, the addition of 3- hydroxybenzoic acid presses down oscillation
System, by one inhibition time, then reverts to the damped oscillation that amplitude is gradually reduced；And from the figure 3, it may be seen that compared to Figure 1, phase
With the addition of the 4-HBA of concentration, so that oscillation system is directly become the damped oscillation that amplitude is gradually reduced, do not press down
Time processed.By above-mentioned identification experiment it is found that can be realized according to the difference (having the unrestraint time) of oscillatory response map to 3- hydroxyl
The differentiation of benzoic acid and 4-HBA identifies.
Take the sample to be identified of two 0.16mol/L prepared in advance solution (one of them for 3- hydroxybenzoic acid it is molten
Liquid, another is 4-HBA solution, but the two is not yet distinguished), it is 1 by one of label, another label
For sample 2；
Two groups of each component concentration identification solution identical with above-mentioned concentration is prepared, respectively the corresponding oscillation map of acquisition, and
The sample 1 and sample 2 of 40uL 0.16mol/L are separately added at the 4th current potential minimum point, so that they are in identifying solution
Concentration be 1.6 × 10-4mol/L。
Known to analysis relatively: the oscillation map of sample 1 compared to Figure 1 compared with the addition of, sample 1 so that oscillation is suppressed,
By one inhibition time, the damped oscillation oscillation that amplitude is gradually reduced then is reverted to, it is corresponding with Fig. 2, not right with Fig. 3
It answers, therefore sample 1 is 3- hydroxybenzoic acid.The oscillation map of sample 2 compared to Figure 1 compared with, the addition of the sample 2 of same concentrations,
So that oscillation directly becomes the damped oscillation that amplitude is gradually reduced, do not occur the inhibition time, it is corresponding with Fig. 3, not right with Fig. 2
It answers, therefore sample 2 is 4-HBA.Therefore, it according to the difference of oscillatory response map (having the unrestraint time), realizes pair
The differentiation of isomer 3- hydroxybenzoic acid and 4-HBA.
Embodiment 2:
The present embodiment verifies aromatic isomer 3- hydroxybenzoic acid and 4- hydroxy benzenes first of the present invention as follows
The feasibility of the discrimination method of acid:
(1) solution is prepared
Use first 98% the concentrated sulfuric acid and distilled water prepare 1.0mol/L sulfuric acid as stock solution, then use 1.0mol/L
Sulfuric acid solution prepared respectively as solvent the bromic acid sodium solution of 0.65mol/L, the malic acid solution of 2mol/L, 1.74 ×
10-2[CuL] (ClO of mol/L4)2Solution.
Simultaneously with second distillation water as solvent, 0.17mol/L 3- hydroxybenzoic acid and 4-HBA are prepared respectively
Solution.
(2) map is vibrated
Magneton is added into 50mL small beaker, sequentially adds 28.5mL 1.0mol/L sulfuric acid solution, 1.5mL
The malic acid solution of the bromic acid sodium solution of 0.65mol/L, 4mL 2mol/L, is eventually adding 6mL 1.74 × 10-2Mol/L's
[CuL](ClO4)2Solution, maintenance system total volume are 40mL, guarantee " H2SO4 - NaBrO3 - [CuL](ClO4)2 Apple
In acid " oscillation system (identifying solution), the molar concentration of each component is respectively sulfuric acid 1.0mol/L, sodium bromate 0.02437mol/
L, malic acid 0.2mol/L, [CuL] (ClO4)2 2.61×10-3mol/L.Remembered with the computer equipped with logger lite program
Record identifies the oscillation map that solution potential changes over time.
Fig. 4 be above-mentioned identification solution (sulfuric acid 1.0mol/L, sodium bromate 0.02437mol/L, malic acid 0.2mol/L,
[CuL](ClO4)2 2.61×10-3Mol/L the oscillation map of sample to be tested is not added) to make blank control.Observation oscillation solution
Color can be found that the color of solution continuous generating period variation: purple-brown color-purple, and week is also presented in potential
The variation of phase property.
Take one group of each component concentration identification solution (sulfuric acid 1.0mol/L, sodium bromate identical with above-mentioned concentration
0.02437mol/L, malic acid 0.2mol/L, [CuL] (ClO4)2 2.61×10-3Mol/L), the 4th electricity is reached in oscillation map
When the minimum point of position, 40uL 0.17mol/L 3- hydroxybenzoic acid is added with liquid-transfering gun, so that it is in the concentration identified in solution
1.7×10-4Mol/L, resulting oscillatory response map are as shown in Figure 5.
Another group of each component concentration identification solution identical with above-mentioned concentration is taken, reaches the 4th current potential most in oscillation map
When low spot, 40uL 0.17mol/L 4-HBA is added with liquid-transfering gun, so that it is 1.7 identifying the concentration in solution
×10-4Mol/L, resulting oscillatory response map are as shown in Figure 6.
(3) it distinguishes and identifies
As aromatic isomer 3- hydroxybenzoic acid and 4-HBA to anti-due to molecular structure difference
System is answered to generate the difference of oscillatory response.As shown in Figure 5, compared with Fig. 4, the addition of 3- hydroxybenzoic acid presses down oscillation
System, by one inhibition time, then reverts to the damped oscillation that amplitude is gradually reduced；And it will be appreciated from fig. 6 that compared with Fig. 4, phase
With the addition of the 4-HBA of concentration, so that oscillation system is directly become the damped oscillation that amplitude is gradually reduced, do not press down
Time processed.By above-mentioned identification experiment it is found that can be realized according to the difference (having the unrestraint time) of oscillatory response map to 3- hydroxyl
The differentiation of benzoic acid and 4-HBA identifies.
Take the sample to be identified of two 0.17mol/L prepared in advance solution (one of them for 3- hydroxybenzoic acid it is molten
Liquid, another is 4-HBA solution, but the two is not yet distinguished), it is 1 by one of label, another label
For sample 2；
Two groups of each component concentration identification solution identical with above-mentioned concentration is prepared, respectively the corresponding oscillation map of acquisition, and
The sample 1 and sample 2 of 40uL 0.17mol/L are separately added at the 4th current potential minimum point, so that they are in identifying solution
Concentration be 1.7 × 10-4mol/L。
Known to analysis relatively: compared with Fig. 4, the addition of sample 1 is suppressed the oscillation map of sample 1 so that vibrating,
By one inhibition time, the damped oscillation that amplitude is gradually reduced then is reverted to, it is corresponding with Fig. 5, do not corresponded to Fig. 6,
Therefore sample 1 is 3- hydroxybenzoic acid.The oscillation map of sample 2 is compared with Fig. 4, the addition of the sample 2 of same concentrations, so that
Oscillation directly becomes the damped oscillation that amplitude is gradually reduced, and does not occur the inhibition time, corresponding with Fig. 6, do not correspond to Fig. 5,
Therefore sample 2 is 4-HBA.Therefore, it according to the difference of oscillatory response map (having the unrestraint time), realizes to same
The differentiation of enantiomers 3- hydroxybenzoic acid and 4-HBA.
Embodiment 3:
The present embodiment verifies aromatic isomer 3- hydroxybenzoic acid and 4- hydroxy benzenes first of the present invention as follows
The feasibility of the discrimination method of acid:
(1) solution is prepared
Use first 98% the concentrated sulfuric acid and distilled water prepare 1.0mol/L sulfuric acid as stock solution, then use 1.0mol/L
Sulfuric acid solution prepared respectively as solvent the bromic acid sodium solution of 0.65mol/L, the malic acid solution of 2mol/L, 1.74 ×
10-2[CuL] (ClO of mol/L4)2Solution.
Simultaneously with second distillation water as solvent, 0.18mol/L 3- hydroxybenzoic acid and 4-HBA are prepared respectively
Solution.
(2) map is vibrated
Magneton is added into 50mL small beaker, sequentially adds 28.5mL 1.0mol/L sulfuric acid solution, 1mL
The malic acid solution of the bromic acid sodium solution of 0.65mol/L, 4.5mL 2mol/L, is eventually adding 6mL 1.74 × 10-2Mol/L's
[CuL](ClO4)2Solution, maintenance system total volume are 40mL, guarantee " H2SO4 - NaBrO3 - [CuL](ClO4)2 Apple
In acid " oscillation system (identifying solution), the molar concentration of each component is respectively sulfuric acid 1.0mol/L, sodium bromate 0.01625mol/
L, malic acid 0.225mol/L, [CuL] (ClO4)2 2.61×10-3mol/L.With equipped with logger lite program computer come
Record identifies the oscillation map that solution potential changes over time.
Fig. 7 be above-mentioned identification solution (sulfuric acid 1.0mol/L, sodium bromate 0.01625mol/L, malic acid 0.225mol/L,
[CuL](ClO4)2 2.61×10-3Mol/L the oscillation map of sample to be tested is not added) to make blank control.Observation oscillation solution
Color can be found that the color of solution continuous generating period variation: purple-brown color-purple, and week is also presented in potential
The variation of phase property.
Take one group of each component concentration identification solution (sulfuric acid 1.0mol/L, sodium bromate identical with above-mentioned concentration
0.01625mol/L, malic acid 0.225mol/L, [CuL] (ClO4)2 2.61×10-3Mol/L), the 4th is reached in oscillation map
When current potential minimum point, 40uL 0.18mol/L 3- hydroxybenzoic acid is added with liquid-transfering gun, so that it is identifying the concentration in solution
It is 1.8 × 10-4Mol/L, resulting oscillatory response map are as shown in Figure 8.
Another group of each component concentration identification solution identical with above-mentioned concentration is taken, reaches the 4th current potential most in oscillation map
When low spot, 40uL 0.18mol/L 4-HBA is added with liquid-transfering gun, so that it is 1.8 identifying the concentration in solution
×10-4Mol/L, resulting oscillatory response map are as shown in Figure 9.
(3) it distinguishes and identifies
As aromatic isomer 3- hydroxybenzoic acid and 4-HBA to anti-due to molecular structure difference
System is answered to generate the difference of oscillatory response.As shown in Figure 8, compared with Fig. 7, the addition of 3- hydroxybenzoic acid presses down oscillation
System, by one inhibition time, then reverts to the damped oscillation that amplitude is gradually reduced；And as shown in Figure 9, compared with Fig. 7, phase
With the addition of the 4-HBA of concentration, so that oscillation system is directly become the damped oscillation that amplitude is gradually reduced, do not press down
Time processed.By above-mentioned identification experiment it is found that can be realized according to the difference (having the unrestraint time) of oscillatory response map to 3- hydroxyl
The differentiation of benzoic acid and 4-HBA identifies.
Take the sample to be identified of two 0.18mol/L prepared in advance solution (one of them for 3- hydroxybenzoic acid it is molten
Liquid, another is 4-HBA solution, but the two is not yet distinguished), it is 1 by one of label, another label
For sample 2；
Two groups of each component concentration identification solution identical with above-mentioned concentration is prepared, respectively the corresponding oscillation map of acquisition, and
The sample 1 and sample 2 of 40uL 0.18mol/L are separately added at the 4th current potential minimum point, so that they are in identifying solution
Concentration be 1.8 × 10-4mol/L。
Known to analysis relatively: compared with Fig. 7, the addition of sample 1 is suppressed the oscillation map of sample 1 so that vibrating,
By one inhibition time, the damped oscillation that amplitude is gradually reduced then is reverted to, it is corresponding with Fig. 8, do not corresponded to Fig. 9,
Therefore sample 1 is 3- hydroxybenzoic acid.The oscillation map of sample 2 is compared with Fig. 7, the addition of the sample 2 of same concentrations, so that
Oscillation directly becomes the damped oscillation that amplitude is gradually reduced, and does not occur the inhibition time, corresponding with Fig. 9, do not correspond to Fig. 8,
Therefore sample 2 is 4-HBA.Therefore, it according to the difference of oscillatory response map (having the unrestraint time), realizes to same
The differentiation of enantiomers 3- hydroxybenzoic acid and 4-HBA.
Embodiment 4:
The present embodiment verifies aromatic isomer 3- hydroxybenzoic acid and 4- hydroxy benzenes first of the present invention as follows
The feasibility of the discrimination method of acid:
(1) solution is prepared
Use first 98% the concentrated sulfuric acid and distilled water prepare 1.0mol/L sulfuric acid as stock solution, then use 1.0mol/L
Sulfuric acid solution prepared respectively as solvent the bromic acid sodium solution of 0.65mol/L, the malic acid solution of 2mol/L, 1.74 ×
10-2[CuL] (ClO of mol/L4)2Solution.
Simultaneously with second distillation water as solvent, 0.2mol/L 3- hydroxybenzoic acid and 4-HBA are prepared respectively
Solution.
(2) map is vibrated
Magneton is added into 50mL small beaker, sequentially adds 28.5mL 1.0mol/L sulfuric acid solution, 1mL
The malic acid solution of the bromic acid sodium solution of 0.65mol/L, 4mL 2mol/L, is eventually adding 6.5mL 1.74 × 10-2Mol/L's
[CuL](ClO4)2Solution, maintenance system total volume are 40mL, guarantee " H2SO4 - NaBrO3 - [CuL](ClO4)2 Apple
In acid " oscillation system (identifying solution), the molar concentration of each component is respectively sulfuric acid 1.0mol/L, sodium bromate 0.01625mol/
L, malic acid 0.2mol/L, [CuL] (ClO4)2 2.83×10-3mol/L.Remembered with the computer equipped with logger lite program
Record identifies the oscillation map that solution potential changes over time.
Figure 10 be above-mentioned identification solution (sulfuric acid 1.0mol/L, sodium bromate 0.01625mol/L, malic acid 0.2mol/L,
[CuL](ClO4)2 2.8×10-3Mol/L the oscillation map of sample to be tested is not added) to make blank control.Observation oscillation solution
Color can be found that the color of solution continuous generating period variation: purple-brown color-purple, and week is also presented in potential
The variation of phase property.
Take one group of each component concentration identification solution (sulfuric acid 1.0mol/L, sodium bromate identical with above-mentioned concentration
0.01625mol/L, malic acid 0.2mol/L, [CuL] (ClO4)2 2.8×10-3Mol/L), the 4th electricity is reached in oscillation map
When the minimum point of position, 40uL 0.2mol/L 3- hydroxybenzoic acid is added with liquid-transfering gun, so that it is in the concentration identified in solution
2.0×10-4Mol/L, resulting oscillatory response map are as shown in figure 11.
Another group of each component concentration identification solution identical with above-mentioned concentration is taken, reaches the 4th current potential most in oscillation map
When low spot, with liquid-transfering gun be added 40uL 0.2mol/L 4-HBA so that its identify solution in concentration be 2.0 ×
10-4Mol/L, resulting oscillatory response map are as shown in figure 12.
(3) it distinguishes and identifies
As aromatic isomer 3- hydroxybenzoic acid and 4-HBA to anti-due to molecular structure difference
System is answered to generate the difference of oscillatory response.As shown in Figure 11, compared with Figure 10, the addition of 3- hydroxybenzoic acid, make oscillation by
Inhibit, by one inhibition time, then reverts to the damped oscillation that amplitude is gradually reduced；And as shown in Figure 12, with Figure 10 phase
Than the addition of the 4-HBA of same concentrations makes oscillation system directly become the damped oscillation that amplitude is gradually reduced, do not go out
Now inhibit the time.By above-mentioned identification experiment it is found that can be realized according to the difference (having the unrestraint time) of oscillatory response map to 3-
The differentiation of hydroxybenzoic acid and 4-HBA identifies.
Take the sample to be identified of two 0.2mol/L prepared in advance solution (one of them for 3- hydroxybenzoic acid it is molten
Liquid, another is 4-HBA solution, but the two is not yet distinguished), it is 1 by one of label, another label
For sample 2；
Two groups of each component concentration identification solution identical with above-mentioned concentration is prepared, respectively the corresponding oscillation map of acquisition, and
The sample 1 and sample 2 of 40uL 0.2mol/L are separately added at the 4th current potential minimum point, so that they are in identifying solution
Concentration is 2.0 × 10-4mol/L。
Known to analysis relatively: compared with Figure 10, the addition of sample 1 is suppressed the oscillation map of sample 1 so that vibrating,
By one inhibition time, the damped oscillation that amplitude is gradually reduced then is reverted to, it is corresponding with Figure 11, not right with Figure 12
It answers, therefore sample 1 is 3- hydroxybenzoic acid.The oscillation map of sample 2 is compared with Figure 10, the addition of the sample 2 of same concentrations,
So that oscillation directly becomes the damped oscillation that amplitude is gradually reduced, do not occur the inhibition time, and Figure 11 corresponding with Figure 12 is not
It is corresponding, therefore sample 2 is 4-HBA.Therefore, it according to the difference of oscillatory response map (having the unrestraint time), realizes
Differentiation to isomer 3- hydroxybenzoic acid and 4-HBA.
Embodiment 5:
The present embodiment verifies aromatic isomer 3- hydroxybenzoic acid and 4- hydroxy benzenes first of the present invention as follows
The feasibility of the discrimination method of acid:
(1) solution is prepared
Use first 98% the concentrated sulfuric acid and distilled water prepare 1.0mol/L sulfuric acid as stock solution, then use 1.0mol/L
Sulfuric acid solution prepared respectively as solvent the bromic acid sodium solution of 0.65mol/L, the malic acid solution of 2mol/L, 1.74 ×
10-2[CuL] (ClO of mol/L4)2Solution.
Simultaneously with second distillation water as solvent, 0.23mol/L 3- hydroxybenzoic acid and 4-HBA are prepared respectively
Solution.
(2) map is vibrated
Magneton is added into 50mL small beaker, sequentially add 27mL 1.0mol/L sulfuric acid solution, 2mL distilled water,
The malic acid solution of the bromic acid sodium solution of 1mL 0.65mol/L, 4mL 2mol/L, is eventually adding 6mL 1.74 × 10-2Mol/L's
[CuL](ClO4)2Solution, maintenance system total volume are 40mL, guarantee " H2SO4 - NaBrO3 - [CuL](ClO4)2 Apple
In acid " oscillation system (identifying solution), the molar concentration of each component is respectively sulfuric acid 0.95mol/L, sodium bromate
0.01625mol/L, malic acid 0.2mol/L, [CuL] (ClO4)2 2.61×10-3mol/L.With equipped with logger lite program
Computer identify the oscillation map that changes over time of solution potential to record.
Figure 13 be above-mentioned identification solution (sulfuric acid 0.95mol/L, sodium bromate 0.01625mol/L, malic acid 0.2mol/L,
[CuL](ClO4)2 2.61×10-3Mol/L the oscillation map of sample to be tested is not added) to make blank control.Observation oscillation solution
Color can be found that the color of solution continuous generating period variation: purple-brown color-purple, and week is also presented in potential
The variation of phase property.
Take one group of each component concentration identification solution (sulfuric acid 0.95mol/L, sodium bromate identical with above-mentioned concentration
0.01625mol/L, malic acid 0.2mol/L, [CuL] (ClO4)2 2.61×10-3Mol/L), the 4th electricity is reached in oscillation map
When the minimum point of position, 40uL 0.23mol/L 3- hydroxybenzoic acid is added with liquid-transfering gun, so that it is in the concentration identified in solution
2.3×10-4Mol/L, resulting oscillatory response map are as shown in figure 14.
Another group of each component concentration identification solution identical with above-mentioned concentration is taken, reaches the 4th current potential most in oscillation map
When low spot, 40uL 0.23mol/L 4-HBA is added with liquid-transfering gun, so that it is 2.3 identifying the concentration in solution
×10-4Mol/L, resulting oscillatory response map are as shown in figure 15.
(3) it distinguishes and identifies
As aromatic isomer 3- hydroxybenzoic acid and 4-HBA to anti-due to molecular structure difference
System is answered to generate the difference of oscillatory response.As shown in Figure 14, compared with figure 13, the addition of 3- hydroxybenzoic acid, make oscillation by
Inhibit, by one inhibition time, then reverts to the damped oscillation that amplitude is gradually reduced；And as shown in Figure 15, with Figure 13 phase
Than the addition of the 4-HBA of same concentrations makes oscillation system directly become the damped oscillation that amplitude is gradually reduced, do not go out
Now inhibit the time.By above-mentioned identification experiment it is found that can be realized according to the difference (having the unrestraint time) of oscillatory response map to 3-
The differentiation of hydroxybenzoic acid and 4-HBA identifies.
Take the sample to be identified of two 0.23mol/L prepared in advance solution (one of them for 3- hydroxybenzoic acid it is molten
Liquid, another is 4-HBA solution, but the two is not yet distinguished), it is 1 by one of label, another label
For sample 2；
Two groups of each component concentration identification solution identical with above-mentioned concentration is prepared, respectively the corresponding oscillation map of acquisition, and
The sample 1 and sample 2 of 40uL 0.23mol/L are separately added at the 4th current potential minimum point, so that they are in identifying solution
Concentration be 2.3 × 10-4mol/L。
Known to analysis relatively: the oscillation map of sample 1 compared with figure 13 compared with the addition of, sample 1 so that oscillation is suppressed,
By one inhibition time, the damped oscillation that amplitude is gradually reduced then is reverted to, it is corresponding with Figure 14, not right with Figure 15
It answers, therefore sample 1 is 3- hydroxybenzoic acid.The oscillation map of sample 2 compared with figure 13 compared with, the addition of the sample 2 of same concentrations,
So that oscillation directly becomes the damped oscillation that amplitude is gradually reduced, do not occur the inhibition time, and Figure 14 corresponding with Figure 15 is not
It is corresponding, therefore sample 2 is 4-HBA.Therefore, it according to the difference of oscillatory response map (having the unrestraint time), realizes
Differentiation to isomer 3- hydroxybenzoic acid and 4-HBA.
Embodiment 6:
The present embodiment verifies aromatic isomer 3- hydroxybenzoic acid and 4- hydroxy benzenes first of the present invention as follows
The feasibility of the discrimination method of acid:
(1) solution is prepared
Use first 98% the concentrated sulfuric acid and distilled water prepare 1.0mol/L sulfuric acid as stock solution, then use 1.0mol/L
Sulfuric acid solution prepared respectively as solvent the bromic acid sodium solution of 0.65mol/L, the malic acid solution of 2mol/L, 1.74 ×
10-2[CuL] (ClO of mol/L4)2Solution.
Simultaneously with second distillation water as solvent, 0.25mol/L 3- hydroxybenzoic acid and 4-HBA are prepared respectively
Solution.
(2) map is vibrated
Magneton is added into 50mL small beaker, sequentially adds 29mL 1.0mol/L sulfuric acid solution, 1mL 0.65mol/L
Bromic acid sodium solution, 4mL 2mol/L malic acid solution, be eventually adding 6mL 1.74 × 10-2[CuL] (ClO of mol/L4)2
Solution, maintenance system total volume are 40mL, guarantee " H2SO4 - NaBrO3 - [CuL](ClO4)2 Malic acid " oscillation system
In (identifying solution), the molar concentration of each component is respectively sulfuric acid 1.0mol/L, sodium bromate 0.01625mol/L, malic acid
0.2mol/L、[CuL](ClO4)2 2.61×10-3mol/L.It is molten that identification is recorded with the computer equipped with logger lite program
The oscillation map that liquid current potential changes over time.
Figure 16 be under typical concentration (sulfuric acid 1.0mol/L, sodium bromate 0.01625mol/L, malic acid 0.2mol/L,
[CuL](ClO4)2 2.61×10-3Mol/L), the oscillation map of sample to be tested is not added for above-mentioned identification solution, to make blank pair
According to.The color of observation oscillation solution can be found that the continuous generating period variation of the color of solution: purple-brown color-purple,
And periodic variation is also presented in potential.
Take one group of each component concentration identification solution (sulfuric acid 1.0mol/L, sodium bromate identical with above-mentioned concentration
0.01625mol/L, malic acid 0.2mol/L, [CuL] (ClO4)2 2.61×10-3Mol/L), the 5th electricity is reached in oscillation map
When the minimum point of position, 40uL 0.25mol/L 3- hydroxybenzoic acid is added with liquid-transfering gun, so that it is in the concentration identified in solution
2.5×10-4Mol/L, resulting oscillatory response map are as shown in figure 17.
Another group of each component concentration identification solution identical with above-mentioned concentration is taken, reaches the 5th current potential most in oscillation map
When low spot, 40uL 0.25mol/L 4-HBA is added with liquid-transfering gun, so that it is 2.5 identifying the concentration in solution
×10-4Mol/L, resulting oscillatory response map are as shown in figure 18.
(3) it distinguishes and identifies
As aromatic isomer 3- hydroxybenzoic acid and 4-HBA to anti-due to molecular structure difference
System is answered to generate the difference of oscillatory response.As shown in Figure 17, compared with Figure 16, the addition of 3- hydroxybenzoic acid, make oscillation by
Inhibit, by one inhibition time, then reverts to the damped oscillation that amplitude is gradually reduced；And as shown in Figure 18, with Figure 16 phase
Than the addition of the 4-HBA of same concentrations makes oscillation system directly become the damped oscillation that amplitude is gradually reduced, do not go out
Now inhibit the time.By above-mentioned identification experiment it is found that can be realized according to the difference (having the unrestraint time) of oscillatory response map to 3-
The differentiation of hydroxybenzoic acid and 4-HBA identifies.
Take the sample to be identified of two 0.25mol/L prepared in advance solution (one of them for 3- hydroxybenzoic acid it is molten
Liquid, another is 4-HBA solution, but the two is not yet distinguished), it is 1 by one of label, another label
For sample 2；
Two groups of each component concentration identification solution identical with above-mentioned concentration is prepared, respectively the corresponding oscillation map of acquisition, and
The sample 1 and sample 2 of 40uL 0.25mol/L are separately added at the 5th current potential minimum point, so that they are in identifying solution
Concentration be 2.5 × 10-4mol/L。
Known to analysis relatively: compared with Figure 16, the addition of sample 1 is suppressed the oscillation map of sample 1 so that vibrating,
By one inhibition time, the damped oscillation that amplitude is gradually reduced then is reverted to, it is corresponding with Figure 17, not right with Figure 18
It answers, therefore sample 1 is 3- hydroxybenzoic acid.The oscillation map of sample 2 is compared with Figure 16, the addition of the sample 2 of same concentrations,
So that oscillation directly becomes the damped oscillation that amplitude is gradually reduced, do not occur the inhibition time, and Figure 17 corresponding with Figure 18 is not
It is corresponding, therefore sample 2 is 4-HBA.Therefore, it according to the difference of oscillatory response map (having the unrestraint time), realizes
Differentiation to isomer 3- hydroxybenzoic acid and 4-HBA.
As can be seen from the above embodiments, the 3- hydroxybenzoic acid and 4-HBA of smaller or larger concentration can also be with
Identified by the method for the invention.
Claims (4)
1. a kind of discrimination method of aromatic isomer 3- hydroxybenzoic acid and 4-HBA, it is characterised in that:
Using secondary distilled water as solvent, the solution of sample to be identified is prepared；
Using " H2SO4-NaBrO3--[CuL](ClO4)2Malic acid " nonlinear chemical oscillation system is recorded as solution is identified
The potential of oscillation system changes with time map, at any one stable current potential minimum point that oscillation generates, to two groups
Identify the solution that sample to be identified is separately added into solution (Non-Linear Ocsillation system), according to sample to be identified to oscillation system
Oscillatory response is different, realizes the identification to sample to be identified；
[CuL](ClO4)2Middle L is 5,7,7,12,14,14- vegolysen, tetra- azepine of 4,8,11-, 14-4,11- diene；
Identify the molar concentration of each component in solution are as follows: sulfuric acid 1.0mol/L, sodium bromate 0.01625mol/L, [CuL] (ClO4)2
2.61×10-3Mol/L, 0.20 mol/L of malic acid；
The sample to be identified is 3- hydroxybenzoic acid and 4-HBA.
2. discrimination method according to claim 1, it is characterised in that:
After being separately added into the solution of sample to be identified into two groups of oscillation systems, if oscillation is suppressed, inhibit by one section
Then time reverts to the damped oscillation that amplitude is gradually reduced, then the sample to be identified is 3- hydroxybenzoic acid；If oscillating body
System directly becomes the damped oscillation that amplitude is gradually reduced, and does not occur the inhibition time, then the sample to be identified is 4- hydroxy benzenes first
Acid.
3. discrimination method according to claim 1 or 2, it is characterised in that: any one of the oscillation generation is stable
Current potential minimum point refers to any one in the 3-21 current potential minimum point that oscillation generates.
4. discrimination method according to claim 1 or 2, it is characterised in that: sample to be identified is identifying reflecting in solution
Other concentration range is 7.0 × 10-5 -2.5×10-4 mol/L。
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