CN109187854A - The measuring method of reaction solution extension rate when studying ionic crystal reaction nucleation rate - Google Patents
The measuring method of reaction solution extension rate when studying ionic crystal reaction nucleation rate Download PDFInfo
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- CN109187854A CN109187854A CN201810908095.5A CN201810908095A CN109187854A CN 109187854 A CN109187854 A CN 109187854A CN 201810908095 A CN201810908095 A CN 201810908095A CN 109187854 A CN109187854 A CN 109187854A
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Abstract
The invention belongs to Chemical Kinetics technical field, the measuring method of reaction solution extension rate when being related to studying ionic crystal reaction nucleation rate.The extension rate is under certain stationary temperature, ought wherein Aa+The concentration of ion is CAa+The first reaction solution and wherein Bb‑The concentration of ion is CBb‑The second reaction solution when being diluted after being mixed to form nucleus with isometric moment with dilution, both not new nucleus was formed, extension rate of the dilution to reaction mixture of the dissolution of nucleus has not been formed yet, the measuring method includes the following steps: (1) under certain stationary temperature, to when reaching dissolution sedimentation equilibrium after first reaction solution is mixed in equal volume with second reaction solution, A in reaction mixture is measureda+Ion and Bb‑The concentration C of ionAa+equAnd CBb‑equ；(2) the extension rate N is calculated using formula.Using measuring method of the invention, can calculate to obtain the extension rate of suitable reaction mixture.
Description
Technical field
The invention belongs to Chemical Kinetics technical field, reaction solution when being related to studying ionic crystal reaction nucleation rate
The measuring method of extension rate.
Background technique
For ionic precipitation reaction mAa++nBb-->AmBn, contain two kinds of precipitating ion A respectivelya+And Bb-Two kinds of reaction solutions
After mixing, moment generates precipitating particle A in reaction mixture under degree of supersaturation effectmBn.Unit volume in reaction mixture,
The precipitating particle A generated in unit timemBnTotal number be ionic crystal reaction nucleation rate, unit be /m3·s。
The size and A of the nucleation rate of ionic crystal reactiona+And Bb-Respective concentration is related when mixing.Work as use
When Nielsen type is nucleated the nucleation rate of measuring device measurement ionic crystal reaction, the identical two strands of reaction solutions of volume are divided
Jia Ru not be into two feeders with temperature incubation function, under the action of certain thrust, two strands in two feeders are reacted
Solution is pressed into nucleation pipe quickly, simultaneously.In nucleation pipe, two bursts of reaction solution mixing, and lured under high degree of supersaturation
Send out into karyogenesis nucleus.In the outlet of nucleation pipe, the diluted through proper volume makes reaction mixture in a vessel
Obtain Aa+And Bb-Concentration substantially reduce so that stopping at nuclear reaction, the nucleus formed later is by micro in dilution
Aa+And Bb-Ion concentration continued growth.And in ionic crystal reaction nucleation rate measurement, nucleus can be waited in reaction mixture and
After dilution mixes and grows to measurable size, by with particle collector measure in nucleation process the crystal grain number that generates into
The calculating of row ionic crystal reaction nucleation rate.
But when the reaction nucleation rate measurement of above-mentioned ionic crystal, dilution is necessary to the extension rate of reaction mixture
Suitably.Because extension rate is less than normal, then reaction mixture after the being nucleated degree of supersaturation after diluted is still larger, can be after
It is continuous to grow new nucleus；Extension rate is bigger than normal, then the degree of supersaturation after diluted of the reaction mixture after being nucleated is less than normal,
Nucleus through being formed can be partly dissolved.Regardless of which kind of situation occurs, it can all influence ionic crystal reaction nucleation rate and survey
Fixed accuracy.
Although the prior art gives reaction mixture and the mixed satiety of dilution when ionic crystal reaction occurs
And degree, but do not provide the calculation method or access approaches of extension rate.
Summary of the invention
The measuring method of reaction solution extension rate when reacting nucleation rate the object of the present invention is to provide research ionic crystal,
That, for the concentration of differential responses object, can calculate to obtain in the nucleation rate measurement for carrying out ionic crystal reaction
The extension rate of suitable reaction mixture, so that the nucleation rate measurement result for reacting ionic crystal is more accurate.
In order to achieve this, in the embodiment on basis, when the present invention provides research ionic crystal reaction nucleation rate
The measuring method of reaction solution extension rate is directed to Aa+The not excessive ionic precipitation reaction mA of iona++nBb-->AmBn；It is described
Extension rate be under certain stationary temperature, ought wherein Aa+The concentration of ion is CAa+The first reaction solution with wherein
Bb-The concentration of ion is CBb-The second reaction solution when being diluted after being mixed to form nucleus with isometric moment with dilution,
Both not new nucleus was formed, and had not also formed extension rate of the dilution to reaction mixture of the dissolution of nucleus；It is described
The composition of dilution, after concentration and first reaction solution, the sufficiently isometric hybrid reaction of the second reaction solution go precipitating, remove
Remove Aa+The composition of the mother liquor of ion, concentration are consistent；
Wherein the measuring method includes the following steps:
(1) under certain stationary temperature, first reaction solution and second reaction solution are mixed in equal volume
To when reaching dissolution sedimentation equilibrium after conjunction, A in reaction mixture is measureda+Ion and Bb-The concentration C of ionAa+equAnd CBb-equ；
(2) the extension rate N. as described in calculating the formula of following formula 1 is utilized
Wherein S is number of the setting value between 1.3-2.1.
In a preferred embodiment, reaction solution dilutes when the present invention provides research ionic crystal reaction nucleation rate
The measuring method of multiple, wherein certain stationary temperature is 5-90 DEG C.
In a preferred embodiment, reaction solution dilutes when the present invention provides research ionic crystal reaction nucleation rate
The measuring method of multiple, wherein the CAa+For 0.01-2mol/L, the CBb-For 0.01-4mol/L.
In a preferred embodiment, reaction solution dilutes when the present invention provides research ionic crystal reaction nucleation rate
The measuring method of multiple, wherein first reaction solution is that isothermal mixes with second reaction solution.
In a preferred embodiment, reaction solution dilutes when the present invention provides research ionic crystal reaction nucleation rate
The measuring method of multiple, wherein the time of the moment mixing is 1-100 milliseconds.
The beneficial effects of the present invention are reaction solution dilutes when reacting nucleation rate using research ionic crystal of the invention
The measuring method of multiple, can be in the nucleation rate measurement for carrying out ionic crystal reaction, for the concentration of differential responses object, all
It can calculate to obtain the extension rate of suitable reaction mixture, so that the nucleation rate measurement result for reacting ionic crystal is more
It is accurate to add.
Beneficial effects of the present invention are embodied in:
(1) the initial reaction concentration phase of the extension rate and reactive ion in two kinds of reaction solutions of the invention by reaction mixture
Association, so as to which extension rate suitable corresponding to different initial reactant concentration is calculated；
(2) present invention can reduce experiment number, reduce workload, obtain in time saving situation it is more accurate at
The measurement result of core rate；
(3) present invention is particularly suitable for the reactions of the ion precipitation of radioactive element, it is possible to reduce the suffered radiation of experimenter
The exposure dose of property substance；
(4) calculation formula of extension rate of the invention is simple, practical.
Detailed description of the invention
Fig. 1 is the measuring principle figure that Nielsen type used in embodiment 1 is nucleated measuring device.
Specific embodiment
A specific embodiment of the invention is further illustrated with attached drawing with reference to embodiments.
Embodiment 1:
1) 0.1mol/L hydrazine nitrate+0.05,0.07,0.09,0.15,0.20,0.30mol/L of certain volume are prepared
H2SO4+ 0.1mol/L oxalic acid is as dilution.
2) at 25 DEG C, respectively by the first reaction solution of 15.0mL (0.05,0.07,0.09,0.15,0.20,0.30mol/
L ferrous sulfate+0.1mol/L nitric acid hydrazine solution) and 15.0mL the second reaction solution (corresponding 0.25,0.27,0.29,0.35,
0.40,0.50mol/L oxalic acid+0.1mol/L nitric acid hydrazine solution) it is added in two feeders 2 shown in FIG. 1.
3) (C on the basis of calculating related concentrations valueAa+For the concentration of ferrous sulfate in the first reaction solution, CBb-It is second
The concentration of reaction solution mesoxalic acid；Under 25 DEG C of constant temperature, after the first reaction solution is mixed in equal volume with the second reaction solution in beaker
To when reaching dissolution sedimentation equilibrium, reaction mixture ferrous ions, i.e. A are measureda+Ion and oxalate denominationby, Bb-Ion
Concentration CAa+equAnd CBb-equ), dilution is calculated to the suitable extension rate N of reaction mixture, so that reaction by such as following formula 1
After mixed liquor and dilution mixing, both not new nucleus was formed, and had not also formed the dissolution of nucleus, and wherein S is 1.3,
4) as shown in Figure 1, the dilution of certain volume is added in rectangular pond 4, and constant temperature is preheated to 25 DEG C.Rectangular pond 4
It is stirred with magneton, sets stirring rate as 4000r/min.It is anti-by first by injecting systems 1 under the thrust of 0.52MPa
Answering liquid and the second reaction solution to be pressed into nucleation pipe 3 mixing and moment reaction generation nucleus, (experiment, which measures, to be formed the nucleus time and is
17 milliseconds).Then reaction mixture is pressed into rapidly into the rectangular pond 4 of high-speed stirred under the pressure of 0.5-0.8MPa, with
Make dilution to the extension rate N above-mentioned steps 3 of reaction mixture) measuring and calculating value, and after 5 seconds immediately by magneton stirring turn
Prompt drop keeps the temperature 10min under 25 DEG C of water-baths to allow nucleus continued growth down to 200r/min.With particle collector measurement precipitating
Grain total number n, the reaction nucleation rate G of the crystallization of ferrous oxalate under the conditions of this reactant concentration is measured in conjunction with nucleation time
(a/m3·s)。
5) concentration value for changing the first reaction solution and the second reaction solution repeats step 1) to step 4), measures differential responses
The reaction nucleation rate G of suitable extension rate N and ferrous oxalate crystallization under object concentration conditions, thus can measure careless at 25 DEG C
Sour ferrous reactive crystallization nucleation kinetics equation is G=3.3 × 1013m-3s-1exp[-3.6/(ln D)2], wherein D is the
One, solution degree of supersaturation when the second reaction solution moment mixed.
In the method for above-mentioned example, equation that oxalic acid is reacted with ferrous ion are as follows: Fe2++C2O4 2-+7H2O->
FeC2O4·7H2O (s), i.e. m=n=1.By ferrous iron concentration 0.05-0.30mol/L, concentration of oxalic acid 0.25-0.50mol/L, oxalic acid
Ferrous solubility 1.61 × 10-3Mol/L, oxalic acid excessive concentrations 0.1mol/L, S value 1.3, m=n=1 bring dilution times obtained by formula 1 into
Number N value is as shown in table 1.
The extension rate N of various concentration reactant when 1 ferrous oxalate crystallization reaction nucleation rate of table measures
Obviously, various changes and modifications can be made to the invention without departing from essence of the invention by those skilled in the art
Mind and range.If in this way, belonging to the model of the claims in the present invention and its equivalent technology to these modifications and changes of the present invention
Within enclosing, then the present invention is also intended to include these modifications and variations.Above-described embodiment or embodiment are only to the present invention
For example, the present invention can also be implemented with other ad hoc fashions or other particular form, without departing from of the invention
Main idea or substantive characteristics.Therefore, the embodiment of description is regarded as illustrative and non-limiting in any way.This
The range of invention should be illustrated that any variation equivalent with the intention and range of claim also should include by appended claims
Within the scope of the invention.
Claims (5)
1. the measuring method of reaction solution extension rate, is directed to A when studying ionic crystal reaction nucleation ratea+Ion is not excessive
Ionic precipitation reaction mAa++nBb-- > AmBn；The extension rate is under certain stationary temperature, ought wherein Aa+
The concentration of ion is CAa+The first reaction solution and wherein Bb-The concentration of ion is CBb-The second reaction solution with isometric moment
It is mixed to form after nucleus when being diluted with dilution, both not new nucleus was formed, and had not also formed the dissolution of nucleus
Extension rate of the dilution to reaction mixture；Composition, concentration and first reaction solution of the dilution, second are instead
After answering the sufficiently isometric hybrid reaction of liquid to go precipitating, A is removeda+The composition of the mother liquor of ion, concentration are consistent；
It is characterized in that, the measuring method includes the following steps:
(1) under certain stationary temperature, after first reaction solution is mixed in equal volume with second reaction solution
To when reaching dissolution sedimentation equilibrium, A in reaction mixture is measureda+Ion and Bb-The concentration C of ionAa+equAnd CBb-equ；
(2) the extension rate N as described in calculating the formula of following formula 1 is utilized,
Wherein S is number of the setting value between 1.3-2.1.
2. measuring method according to claim 1, it is characterised in that: certain stationary temperature is 5-90 DEG C.
3. measuring method according to claim 1, it is characterised in that: the CAa+For 0.01-2mol/L, the CBb-
For 0.01-4mol/L.
4. measuring method according to claim 1, it is characterised in that: first reaction solution is reacted with described second
Liquid is isothermal mixing.
5. measuring method according to claim 1, it is characterised in that: the time of the moment mixing is 1-100 milliseconds.
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Cited By (1)
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| CN111879809A (en) * | 2020-06-10 | 2020-11-03 | 中国原子能科学研究院 | Method for measuring and calculating dilution times of reaction liquid in research of crystal nucleation rate |
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| CN107855088A (en) * | 2017-12-20 | 2018-03-30 | 中国科学院青岛生物能源与过程研究所 | A kind of efficient, intelligence reactive crystallization equipment |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111879809A (en) * | 2020-06-10 | 2020-11-03 | 中国原子能科学研究院 | Method for measuring and calculating dilution times of reaction liquid in research of crystal nucleation rate |
| CN111879809B (en) * | 2020-06-10 | 2021-08-20 | 中国原子能科学研究院 | Method for measuring and calculating dilution times of reaction liquid in research of crystal nucleation rate |
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