CN107796912A - The method for measurement of concentration of mixed acid solution - Google Patents
The method for measurement of concentration of mixed acid solution Download PDFInfo
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- CN107796912A CN107796912A CN201610804976.3A CN201610804976A CN107796912A CN 107796912 A CN107796912 A CN 107796912A CN 201610804976 A CN201610804976 A CN 201610804976A CN 107796912 A CN107796912 A CN 107796912A
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Abstract
A kind of method for measurement of concentration of mixed acid solution, including：Test nitration mixture is provided, the test nitration mixture is the mixed solution of hydrofluoric acid and nitric acid；The test nitration mixture is diluted using aprotic polar organic solvent, forms titration nitration mixture；The titration nitration mixture is titrated using titrant, obtains the titration end-point of hydrofluoric acid and the titration end-point of nitric acid；The concentration of hydrofluoric acid and the concentration of nitric acid in test nitration mixture are obtained according to the titration end-point of hydrofluoric acid and the titration end-point of nitric acid.Methods described improves the measuring accuracy of the concentration of hydrofluoric acid and the concentration of nitric acid in test nitration mixture.
Description
Technical field
The present invention relates to concentration determination field, more particularly to a kind of method for measurement of concentration of mixed acid solution.
Background technology
Wet etching is technique common in semiconductor fabrication.In wet etching, semi-conducting material or metal with
Etching liquid chemically reacts, so as to obtain certain figure in semiconductor material surface or metal surface.
Common semi-conducting material includes silicon.The etching liquid that wet etching use is carried out to silicon is usually hydrofluoric acid and nitric acid
Mixed solution.For the etching effect for accurately controlling etching process to reach optimal, to hydrofluoric acid and the concentration proportion of nitric acid
There are strict requirements.Therefore need accurately to measure hydrofluoric acid in the mixed solution and the respective concentration of nitric acid.
However, prior art is to the measuring accuracy of hydrofluoric acid concentration and concentration of nitric acid in the mixed solution of hydrofluoric acid and nitric acid
It is poor.
The content of the invention
The present invention is solved the problems, such as to be to provide a kind of method for measurement of concentration of mixed acid solution, tested with improving in nitration mixture
The measuring accuracy of hydrofluoric acid concentration and concentration of nitric acid.
To solve the above problems, the present invention provides a kind of method for measurement of concentration of mixed acid solution, including：Test is provided
Nitration mixture, the test nitration mixture are the mixed solution of hydrofluoric acid and nitric acid；The test is diluted using aprotic polar organic solvent
Nitration mixture, form titration nitration mixture；The titration nitration mixture is titrated using titrant, obtains the titration end-point and nitric acid of hydrofluoric acid
Titration end-point；The concentration and nitre of hydrofluoric acid in test nitration mixture are obtained according to the titration end-point of hydrofluoric acid and the titration end-point of nitric acid
The concentration of acid.
Optionally, the aprotic polar organic solvent is alcohol, isopropanol, acetone, tetrahydrofuran, MEK or diformazan
Base pyrrolidones.
Optionally, the titrant is alkaline solution.
Optionally, the alkaline solution is sodium hydroxide solution or potassium hydroxide solution.
Optionally, the concentration of solute is 0.1mol/L~2.0mol/L in the titrant.
Optionally, the volume of the aprotic polar organic solvent and the ratio of the volume of the test nitration mixture for 20~
200。
Optionally, constant-current titration is carried out to the titration nitration mixture using titrant, obtains the titration end-point and nitre of hydrofluoric acid
The titration end-point of acid.
Optionally, obtaining the method for the titration end-point of hydrofluoric acid and the titration end-point of nitric acid includes：Obtain titration nitration mixture
Potential value is with the potential function relation of the change of the titration volumes of titrant；Make to titrate body described in the potential function relation pair
Product first derivation, obtains single order conductive bit functional relation；Determine the first minimum point in the single order conductive bit functional relation
With the second minimum point, titration volumes corresponding to first minimum point are the first volume, and second minimum point is corresponding
Titration volumes be the second volume, the first volume is less than the second volume；First minimum point is defined as to the titration of nitric acid
Terminal, second minimum point is defined as to the titration end-point of hydrofluoric acid.
Optionally, the potential value of titration nitration mixture is obtained with the potential function relation of the change of the titration volumes of titrant
Method includes：Potential value using the titration volumes of titrant as abscissa, titration nitration mixture is ordinate, and it is bent to draw constant-current titration
Line；Obtaining the method for the single order conductive bit functional relation includes：Using the titration volumes of titrant as abscissa, titrate nitration mixture
Potential value is led to the single order of titration volumes as ordinate, drafting single order conductive bit titration curve.
Optionally, the concentration of hydrofluoric acid in test nitration mixture is obtained according to the titration end-point of hydrofluoric acid and the titration end-point of nitric acid
Method with the concentration of nitric acid is：The titrant of titration nitric acid consumption is obtained according to first volume and the concentration of titrant
Quality；The quality of the titrant consumed according to titration nitric acid obtains the quality of nitric acid in titration nitration mixture；According to nitre in titration nitration mixture
The quality of acid and the quality of test nitration mixture obtain the concentration of nitric acid in test nitration mixture；According to second volume and first body
Long-pending difference and the concentration of titrant obtain the quality of the titrant of titration hydrofluoric acid consumption；According to titration hydrofluoric acid consumption
Titrant quality obtain titration nitration mixture in hydrofluoric acid quality；According to the quality of hydrofluoric acid in titration nitration mixture and test nitration mixture
Quality obtain test nitration mixture in hydrofluoric acid concentration.
Optionally, the titration nitration mixture is titrated and obtains the concentration of hydrofluoric acid and the concentration of nitric acid in test nitration mixture
Afterwards, in addition to：Repeat n times titration nitration mixture be titrated to obtain the dense of the concentration of hydrofluoric acid and nitric acid in test nitration mixture
The step of spending, N are the integer more than or equal to 1；Obtain N+1 time to titrate nitration mixture titrated corresponding to hydrofluoric acid concentration put down
The average value of average and concentration of nitric acid.
Optionally, N is 2~4.
Compared with prior art, technical scheme has advantages below：
The method for measurement of concentration of mixed acid solution provided by the invention, titration nitration mixture use aprotic polar organic solvent
Dilution is tested nitration mixture and formed.Aprotic polar organic solvent has the stronger ability for tending to receive proton and stronger
Form the ability of hydrogen bond.On the one hand, aprotic polar organic solvent has the ability of stronger formation hydrogen bond so that non-proton pole
Property organic solvent fluorine ion and positively charged product are easily formed with the hydrofluoric acid molecule in titration nitration mixture, so as to reduce drop
Determine the content of hydrofluoric acid molecule in solution, and then reduce the quantity that hydrofluoric acid molecule and nitric acid combine in titration nitration mixture, reduce
The influence degree that hydrofluoric acid molecule ionizes to nitric acid in titration nitration mixture.The titration end-point of nitric acid can be accurately obtained,
So that the measuring accuracy of the concentration of nitric acid improves.On the other hand, aprotic polar organic solvent receive proton ability it is stronger, make
It is positive mobile that the ionization equilibrium of hydrofluoric acid in nitration mixture must be titrated, add the degree of ionization of hydrofluoric acid.There is hydrogen so as to avoid
The false titration end-point of fluoric acid.So that the measuring accuracy of the concentration of hydrofluoric acid improves.
Brief description of the drawings
Fig. 1 is the flow chart of the method for measurement of concentration of mixed acid solution in one embodiment of the invention；
Fig. 2 is the potentiometric titration curve obtained in one embodiment of the invention during the concentration mensuration of mixed acid solution
Figure.
Embodiment
As described in background, in the prior art for hydrofluoric acid concentration in the mixed solution of hydrofluoric acid and nitric acid and nitre
The measuring accuracy of acid concentration is poor.
A kind of method for measurement of concentration of mixed acid solution, including：Nitration mixture to be tested is provided, the nitration mixture to be tested is hydrogen
The mixed solution of fluoric acid and nitric acid；Using water-soluble dilution agent nitration mixture to be tested, obtain titrating nitration mixture；Using sodium hydroxide solution pair
The titration nitration mixture carries out constant-current titration, obtains the titration end-point of hydrofluoric acid and the titration end-point of nitric acid；According to the drop of hydrofluoric acid
The titration end-point for determining terminal and nitric acid obtains the concentration of hydrofluoric acid and the concentration of nitric acid in nitration mixture to be tested.
Constant-current titration titrates nitration mixture by measuring potential break in titration process changes to determine titration end-point.
The potential value of titration nitration mixture is obtained with the potential function relation of the change of the titration volumes of titrant, then by institute
Titration volumes first derivation described in potential function relation pair is stated, obtains single order conductive bit functional relation.It is conductive using the single order
Minimum point reaction titration end-point in bit function relation.
However, the hydrofluoric acid that the above method obtains concentration and nitric acid concentration measuring accuracy it is poor, it has been investigated that,
Reason is：
The highly polar compound that hydrofluoric acid is formed by hydrogen bond, is mainly gone out in aqueous solvent in the form of hydrofluoric acid molecule
It is existing.Due to titration nitration mixture by test nitration mixture by water-soluble dilution agent and formed, therefore titrate nitration mixture in hydrofluoric acid mainly with hydrogen fluorine
The form of acid molecule occurs.Hydrofluoric acid molecule in titration nitration mixture is easily combined generation HFH with the hydrogen ion in nitric acid+, it is larger
The hydrogen ion for reducing nitric acid and ionizing out of degree.Cause single order of the potential value corresponding to the titration end-point of nitric acid to titration volumes
The numerical value of derivative is smaller, and specially 20~26.Because potential value is more than 100 to the absolute value numerical value of the first derivative of titration volumes
When, it can accurately just tell titration end-point.Therefore, it is difficult to accurately tell the titration end-point of nitric acid.Thus cause nitric acid
Deviation be present in the test result of concentration.
Because hydrofluoric acid mainly occurs in nitration mixture is titrated in the form of hydrofluoric acid molecule, therefore hydrofluoric acid is in titration nitration mixture
In degree of ionization it is smaller, easily there is false titration end-point during titration.The false titration end-point is the single order conductive bit
A minimum point in functional relation, but titration end-point can not be reflected.So as to cause the test result of the concentration of hydrofluoric acid
Deviation be present.
On this basis, the present invention provides a kind of method for measurement of concentration of mixed acid solution, including：It is mixed to provide test
Acid, the test nitration mixture are the mixed solution of hydrofluoric acid and nitric acid；It is mixed using the aprotic polar organic solvent dilution test
Acid, form titration nitration mixture；The titration nitration mixture is titrated using titrant, obtains the titration end-point and nitric acid of hydrofluoric acid
Titration end-point；The concentration and nitric acid of hydrofluoric acid in test nitration mixture are obtained according to the titration end-point of hydrofluoric acid and the titration end-point of nitric acid
Concentration.
Aprotic polar organic solvent has the stronger ability for tending to receive proton and stronger formation hydrogen bond
Ability.On the one hand, aprotic polar organic solvent has the ability of stronger formation hydrogen bond so that aprotic polar organic solvent
Fluorine ion and positively charged product easily are formed with the hydrofluoric acid molecule in titration nitration mixture, so as to reduce hydrogen in volumetric soiutions
The content of fluoric acid molecule, and then the quantity that hydrofluoric acid molecule and nitric acid combine in titration nitration mixture is reduced, reduce titration nitration mixture
The influence degree that middle hydrofluoric acid molecule ionizes to nitric acid.The titration end-point of nitric acid can accurately be obtained so that nitric acid
The measuring accuracy of concentration improves.On the other hand, aprotic polar organic solvent receive proton ability it is stronger so that titration nitration mixture
The ionization equilibrium of middle hydrofluoric acid is positive mobile, adds the degree of ionization of hydrofluoric acid.There is the false of hydrofluoric acid so as to avoid
Titration end-point.So that the measuring accuracy of the concentration of hydrofluoric acid improves.
It is understandable to enable the above objects, features and advantages of the present invention to become apparent, below in conjunction with the accompanying drawings to the present invention
Specific embodiment be described in detail.
Fig. 1 is the flow chart of the method for measurement of concentration of mixed acid solution in one embodiment of the invention, mixed acid solution
Method for measurement of concentration comprise the following steps：
S01：Test nitration mixture is provided, the test nitration mixture is the mixed solution of hydrofluoric acid and nitric acid；
S02：The test nitration mixture is diluted using aprotic polar organic solvent, forms titration nitration mixture；
S03：The titration nitration mixture is titrated using titrant；
S04：Obtain single order conductive bit functional relation of the potential value to titration volumes of titration nitration mixture；
S05：Determine that the titration of the titration end-point of corresponding hydrofluoric acid and nitric acid in the single order conductive bit functional relation is whole
Point；
S06：According to the titration end-point of hydrofluoric acid and the titration end-point of nitric acid obtain in test nitration mixture the concentration of hydrofluoric acid and
The concentration of nitric acid.
Above-mentioned steps are described in detail below.
Perform step S01：Test nitration mixture is provided, the test nitration mixture is the mixed solution of hydrofluoric acid and nitric acid.
Specifically, initial hydrofluoric acid solution and initial salpeter solution are provided, the concentration of hydrofluoric acid in initial hydrofluoric acid solution
For C1, the concentration of nitric acid is C2 in initial salpeter solution；Prepared and surveyed using initial hydrofluoric acid solution and initial salpeter solution and water
Try nitration mixture.
C1 and C2 tests to obtain using titration.In the present embodiment, C1 and C2 test to obtain using potentiometric titration.
Because initial hydrofluoric acid solution and initial salpeter solution are unitary acid solution, constant-current titration process is relatively simple,
Respective titration end-point can be accurately obtained.Therefore the actual concentrations deviation of hydrofluoric acid is smaller in C1 and initial hydrofluoric acid solution,
The actual concentrations deviation of nitric acid is smaller in C2 and initial salpeter solution.
In other embodiments, C1 and C2 can be previously known numerical value.
It should be noted that C1 and C2 refer to mass percent concentration.
The step of preparing test nitration mixture using initial hydrofluoric acid solution and initial salpeter solution and water includes：Weighing quality is
The aqueous solvent that the initial salpeter solution and quality that W1 initial hydrofluoric acid solution, quality are W2 are W3；It is the initial of W1 by quality
The aqueous solvent that the initial salpeter solution and quality that hydrofluoric acid solution, quality are W2 are W3 mixes, and obtains testing nitration mixture.
The normal concentration C of hydrofluoric acid in test nitration mixture is calculated according to C1, W1, W2 and W3b1；According to C2, W1, W2 and W3
The normal concentration C of nitric acid in test nitration mixture is calculatedb2。
Specifically, Cb1=C1*W1/ (W1+W2+W3), Cb2=C2*W2/ (W1+W2+W3).
The concentration that the normal concentration of hydrofluoric acid is used to subsequently titrate the hydrofluoric acid obtained after test nitration mixture is contrasted, with weighing apparatus
Amount tests after nitration mixture the precision of the concentration of obtained hydrofluoric acid using titration.The normal concentration of nitric acid is used to subsequently titrate to test to mix
The concentration of the nitric acid obtained after acid is contrasted, to weigh the precision of the concentration using the nitric acid obtained after titration test nitration mixture.
Perform step S02：The test nitration mixture is diluted using aprotic polar organic solvent, forms titration nitration mixture.
The aprotic polar organic solvent has the stronger ability for tending to receive proton and stronger formation hydrogen
The ability of key.
The aprotic polar organic solvent is alcohol, isopropanol, acetone, tetrahydrofuran, MEK or dimethyl pyrrole
Alkanone.In the present embodiment, using aprotic polar organic solvent as acetone (CH3)CO(CH3) exemplified by illustrate.
On the one hand, aprotic polar organic solvent has the ability of stronger formation hydrogen bond so that aprotonic polar is organic
Solvent easily forms fluorine ion and positively charged product with the hydrofluoric acid molecule in titration nitration mixture, so as to reduce volumetric soiutions
The content of middle hydrofluoric acid molecule, and then the quantity that hydrofluoric acid molecule and nitric acid combine in volumetric soiutions is reduced, reduce titration
The influence degree that hydrofluoric acid molecule ionizes to nitric acid in solution.
Specifically, in the present embodiment, aprotic polar organic solvent is acetone, aprotic polar organic solvent easily with drop
Determine that hydrofluoric acid molecule in nitration mixture forms fluorine ion and the reaction equation of positively charged product is：
On the other hand, aprotic polar organic solvent receive proton ability it is stronger so that the ionization equilibrium of hydrofluoric acid is just
To movement, the degree of ionization of hydrofluoric acid is added.
Specifically, weighing a certain amount of test nitration mixture prepared, institute is then diluted using aprotic polar organic solvent
Test nitration mixture is stated, forms titration nitration mixture.
The ratio of the volume of the aprotic polar organic solvent and the volume of test nitration mixture is 20~200, this ratio model
Enclose with following meaning：If the ratio of the volume of aprotic polar organic solvent and the volume of test nitration mixture is less than 20, then drop
Determine that the content of aprotic polar organic solvent in nitration mixture is very few, to the promotion degree of hydrofluoric acid degree of ionization in titration nitration mixture compared with
Small, the increased degree of hydrogen ion content ionized out to nitric acid in titration nitration mixture is smaller；If the body of aprotic polar organic solvent
The ratio of product and the volume of test nitration mixture is more than 200, then the content of aprotic polar organic solvent is excessive in titration nitration mixture, makes
Wasted into technique.
Perform step S03：The titration nitration mixture is titrated using titrant.
The titration nitration mixture is titrated using titrant, acid-base neutralization occurs for the titrant and the titration nitration mixture
Reaction.
The titrant is alkaline solution.The alkaline solution can be sodium hydroxide solution or potassium hydroxide solution.This
It is that example illustrates by sodium hydroxide solution of the titrant in embodiment.
When the alkaline solution is sodium hydroxide solution or potassium hydroxide solution, the concentration of solute is in the titrant
0.1mol/L~2.0mol/L.
In the present embodiment, constant-current titration is carried out to the titration nitration mixture using titrant, obtains the titration end-point of hydrofluoric acid
With the titration end-point of nitric acid.
Specifically, the method for obtaining the titration end-point of hydrofluoric acid and the titration end-point of nitric acid refers to step S04 and step
S05。
Perform step S04：Obtain single order conductive bit functional relation of the potential value to titration volumes of titration nitration mixture.
Specifically, the potential value of titration nitration mixture is obtained with the potential function relation of the change of the titration volumes of titrant；
Titration volumes first derivation described in making the potential function relation pair, obtain single order conductive bit functional relation.
The potential value of titration nitration mixture is obtained with the method bag of the potential function relation of the change of the titration volumes of titrant
Include：Potential value using the titration volumes of titrant as abscissa, titration nitration mixture is ordinate, draws potentiometric titration curve.
Obtaining the method for single order conductive bit functional relation includes：Using the titration volumes of titrant as abscissa, titration nitration mixture
Potential value the single order of titration volumes is led for ordinate, draw single order conductive bit titration curve.
Specifically, Fig. 2 is the potentiometric titration curve obtained in the present embodiment during the concentration mensuration of mixed acid solution
Figure.Transverse axis is titration volumes (V) in Fig. 2, and unit is milliliter (ml).The longitudinal axis in left side is the potential value of titration nitration mixture in Fig. 2
(E), unit is millivolt (mV).The longitudinal axis on right side leads (dE/ for the potential value of titration nitration mixture to the single order of titration volumes in Fig. 2
DV), unit is (mV/ml).Curve A is that the current potential drop that the potential value of nitration mixture changes with titration volumes is titrated in titration process
Determine curve, curve B is the potentiometric titration curve to the single order conductive bit titration curve obtained after titration volumes first derivation.
Perform step S05：Determine the titration end-point and nitric acid of corresponding hydrofluoric acid in the single order conductive bit functional relation
Titration end-point.
The first minimum point and the second minimum point in the single order conductive bit functional relation are determined, that is, determines curve
The first minimum point and the second minimum point in B.Titration volumes corresponding to first minimum point are the first volume V1, institute
State titration volumes corresponding to the second minimum point and be less than the second volume V2 for the second volume V2, the first volume V1.
First minimum point is defined as to the titration end-point of nitric acid, second minimum point is defined as hydrofluoric acid
Titration end-point.
First minimum point is the titration end-point of nitric acid, and the second minimum point is the titration end-point of hydrofluoric acid, rather than phase
Instead, reason is：The dissociation constant of nitric acid is significantly larger than the dissociation constant of hydrofluoric acid, therefore is nitric acid and hydrogen fluorine to titration nitration mixture
When the mixed solution of acid is titrated, first titration end-point is the titration end-point of nitric acid, and second titration end-point is hydrofluoric acid
Titration end-point.Corresponding first minimum point of first titration end-point, corresponding second minimum point of second titration end-point.
Fig. 2 shows that potential value corresponding to the titration end-point of nitric acid is 350 to the value of the first derivative of titration volumes, hydrofluoric acid
Titration end-point corresponding to potential value be -8060 to the numerical value of the first derivative of titration volumes.Corresponding to the titration end-point of nitric acid
Potential value is to potential value corresponding to the absolute value of the numerical value of the first derivative of titration volumes and the titration end-point of hydrofluoric acid to drop
The absolute value for determining the numerical value of the first derivative of volume is all higher than 100, beneficial to accurately telling respective titration end-point.
It should be noted that under different test conditions, potential value corresponding to the titration end-point of hydrofluoric acid is to titrating body
Potential value corresponding to the numerical value of long-pending first derivative and the titration end-point of nitric acid can be with to the numerical value of the first derivative of titration volumes
For other numerical value.By repeatedly test, single order of the potential value corresponding to the titration end-point of nitric acid to titration volumes can be obtained
Numerical value of the potential value to the first derivative of titration volumes corresponding to the absolute value of the numerical value of derivative and the titration end-point of hydrofluoric acid
Absolute value be all higher than 100 result.
Perform step S06：Hydrofluoric acid in test nitration mixture is obtained according to the titration end-point of hydrofluoric acid and the titration end-point of nitric acid
Concentration and nitric acid concentration.
Specifically, the concentration of hydrofluoric acid in test nitration mixture is obtained according to the titration end-point of hydrofluoric acid and the titration end-point of nitric acid
Method with the concentration of nitric acid is：
Titration hydrofluoric acid is obtained according to second volume with the difference of first volume and the concentration of titrant to disappear
The quality of the titrant of consumption；The quality of the titrant consumed according to titration hydrofluoric acid obtains the quality of hydrofluoric acid in titration nitration mixture；
The concentration C of hydrofluoric acid in test nitration mixture is obtained according to the quality of hydrofluoric acid in titration nitration mixture and the quality of test nitration mixturej1；
The quality for the titrant that titration nitric acid consumes is obtained according to first volume and the concentration of titrant；According to titration
The quality of the titrant of nitric acid consumption obtains the quality of nitric acid in titration nitration mixture；According to the quality of nitric acid and test in titration nitration mixture
The quality of nitration mixture obtains the concentration C of nitric acid in test nitration mixturej2。
Because aprotic polar organic solvent reduces the influence degree that hydrofluoric acid molecule ionizes to nitric acid in titration nitration mixture,
Therefore the titration end-point of nitric acid can accurately be obtained.So that the measuring accuracy of the concentration of nitric acid improves.
Because aprotic polar organic solvent adds the degree of ionization of hydrofluoric acid in titration nitration mixture, therefore can avoid out
The false titration end-point of existing hydrofluoric acid.So that the measuring accuracy of the concentration of hydrofluoric acid improves.
In order to increase the reliability of test, the hydrogen fluorine in once being titrated to the titration nitration mixture and obtaining test nitration mixture
After the concentration of acid and the concentration of nitric acid, repeat n times and be titrated to hydrofluoric acid in acquisition test nitration mixture to titration nitration mixture
The step of concentration and the concentration of nitric acid, N are the integer more than or equal to 1；N+1 time is obtained to titrating corresponding to nitration mixture titrated
The average value of hydrofluoric acid concentration and the average value of concentration of nitric acid.
Wherein, when N is 2~4 so that the reliability of test is higher, while testing efficiency is higher.
In order to intuitively weigh the concentration C of hydrofluoric acid in the test nitration mixture obtained in the present embodimentj1With the concentration C of nitric acidj2
Accuracy, by the normal concentration C of hydrofluoric acidb1And Cj1Contrasted, by the normal concentration C of nitric acidb2And Cj2Contrasted.Together
When, the concentration C of the hydrofluoric acid obtained after the corresponding test nitration mixture of aqueous phase dilution will be used in conventional methodc1It is dense with the standard of hydrofluoric acid
Spend Cb1Contrasted, the concentration C of nitric acid is obtained after the corresponding test nitration mixture of aqueous phase dilution will be used in conventional methodc2With nitric acid
Normal concentration Cb2It is compared.
Data in form 1 reflect above-mentioned comparing result.
Form 1
Contrasted by the data of form 1, the test nitration mixture by aprotic polar organic solvent dilution is formed
Titration nitration mixture is titrated, and the concentration of obtained hydrofluoric acid and the concentration of nitric acid are closer to actual value.Thus, in the present embodiment,
The measuring accuracy of the concentration of hydrofluoric acid and the measuring accuracy of the concentration of nitric acid are higher.
Although present disclosure is as above, the present invention is not limited to this.Any those skilled in the art, this is not being departed from
In the spirit and scope of invention, it can make various changes or modifications, therefore protection scope of the present invention should be with claim institute
The scope of restriction is defined.
Claims (12)
- A kind of 1. method for measurement of concentration of mixed acid solution, it is characterised in that including：Test nitration mixture is provided, the test nitration mixture is the mixed solution of hydrofluoric acid and nitric acid；The test nitration mixture is diluted using aprotic polar organic solvent, forms titration nitration mixture；The titration nitration mixture is titrated using titrant, obtains the titration end-point of hydrofluoric acid and the titration end-point of nitric acid；The dense of the concentration of hydrofluoric acid and nitric acid in test nitration mixture is obtained according to the titration end-point of hydrofluoric acid and the titration end-point of nitric acid Degree.
- 2. the method for measurement of concentration of mixed acid solution according to claim 1, it is characterised in that the aprotonic polar Organic solvent is alcohol, isopropanol, acetone, tetrahydrofuran, MEK or dimethyl pyrrolidone.
- 3. the method for measurement of concentration of mixed acid solution according to claim 1, it is characterised in that the titrant is alkali Property solution.
- 4. the method for measurement of concentration of mixed acid solution according to claim 3, it is characterised in that the alkaline solution is Sodium hydroxide solution or potassium hydroxide solution.
- 5. the method for measurement of concentration of mixed acid solution according to claim 4, it is characterised in that molten in the titrant The concentration of matter is 0.1mol/L~2.0mol/L.
- 6. the method for measurement of concentration of mixed acid solution according to claim 1, it is characterised in that the aprotonic polar The ratio of the volume of organic solvent and the volume of the test nitration mixture is 20~200.
- 7. the method for measurement of concentration of mixed acid solution according to claim 1, it is characterised in that using titrant to institute State titration nitration mixture and carry out constant-current titration, obtain the titration end-point of hydrofluoric acid and the titration end-point of nitric acid.
- 8. the method for measurement of concentration of mixed acid solution according to claim 7, it is characterised in that obtain the drop of hydrofluoric acid Determining the method for the titration end-point of terminal and nitric acid includes：The potential value of titration nitration mixture is obtained with the potential function relation of the change of the titration volumes of titrant；Titration volumes first derivation described in making the potential function relation pair, obtain single order conductive bit functional relation；Determine the first minimum point and the second minimum point in the single order conductive bit functional relation, first minimum point Corresponding titration volumes are the first volume, and titration volumes corresponding to second minimum point are the second volume, the first small volume In the second volume；First minimum point is defined as to the titration end-point of nitric acid, second minimum point is defined as to the drop of hydrofluoric acid Determine terminal.
- 9. the method for measurement of concentration of mixed acid solution according to claim 8, it is characterised in that obtain titration nitration mixture Potential value includes with the method for the potential function relation of the change of the titration volumes of titrant：Using the titration volumes of titrant as Abscissa, the potential value of titration nitration mixture are ordinate, draw potentiometric titration curve；Obtaining the method for the single order conductive bit functional relation includes：Using the titration volumes of titrant as abscissa, titration nitration mixture Potential value the single order of titration volumes is led for ordinate, draw single order conductive bit titration curve.
- 10. the method for measurement of concentration of mixed acid solution according to claim 8, it is characterised in that according to hydrofluoric acid Titration end-point and the titration end-point of nitric acid obtain the method for the concentration of hydrofluoric acid and the concentration of nitric acid in test nitration mixture：The quality for the titrant that titration nitric acid consumes is obtained according to first volume and the concentration of titrant；According to titration nitric acid The quality of the titrant of consumption obtains the quality of nitric acid in titration nitration mixture；According to the quality of nitric acid in titration nitration mixture and test nitration mixture Quality obtain test nitration mixture in nitric acid concentration；Obtain what titration hydrofluoric acid consumed according to the concentration of the difference and titrant of second volume and first volume The quality of titrant；The quality of the titrant consumed according to titration hydrofluoric acid obtains the quality of hydrofluoric acid in titration nitration mixture；According to Titrate the concentration that the quality of hydrofluoric acid and the quality of test nitration mixture in nitration mixture obtain hydrofluoric acid in test nitration mixture.
- 11. the method for measurement of concentration of mixed acid solution according to claim 1, it is characterised in that mixed to the titration Acid is titrated and obtained in test nitration mixture after the concentration of hydrofluoric acid and the concentration of nitric acid, in addition to：Repeat n times to titration Nitration mixture be titrated to the step of obtaining the concentration of hydrofluoric acid and the concentration of nitric acid in test nitration mixture, and N is whole more than or equal to 1 Number；Obtain N+1 time to titrate nitration mixture titrated corresponding to the average value of hydrofluoric acid concentration and the average value of concentration of nitric acid.
- 12. the method for measurement of concentration of mixed acid solution according to claim 11, it is characterised in that N is 2~4.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109668941A (en) * | 2018-12-06 | 2019-04-23 | 普瑞斯伊诺康有限公司 | A kind of method of sulfuric acid and manganese sulfate concentration in measurement electrolyte aqueous solution |
| CN109738577A (en) * | 2019-01-10 | 2019-05-10 | 惠科股份有限公司 | Method for detecting content of mixed acid in aluminum etching solution |
| CN110286193A (en) * | 2019-06-04 | 2019-09-27 | 青海盐湖工业股份有限公司 | The method that a kind of pair of sodium hydroxide solution carries out assay |
| CN111855650A (en) * | 2020-07-30 | 2020-10-30 | 青岛科技大学 | Method for determining content of fluosilicic acid, hydrofluoric acid and nitric acid in etching acid |
| US11610783B2 (en) | 2014-07-30 | 2023-03-21 | Corning Incorporated | Ultrasonic tank and methods for uniform glass substrate etching |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102621273A (en) * | 2012-04-17 | 2012-08-01 | 昊诚光电（太仓）有限公司 | Method for detecting mixed acid solution in manufacturing process of polycrystalline silicon solar cell |
| CN104237332A (en) * | 2013-06-15 | 2014-12-24 | 无锡尚德太阳能电力有限公司 | Method for detecting concentration of mixed acid solution |
-
2016
- 2016-09-06 CN CN201610804976.3A patent/CN107796912A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102621273A (en) * | 2012-04-17 | 2012-08-01 | 昊诚光电（太仓）有限公司 | Method for detecting mixed acid solution in manufacturing process of polycrystalline silicon solar cell |
| CN104237332A (en) * | 2013-06-15 | 2014-12-24 | 无锡尚德太阳能电力有限公司 | Method for detecting concentration of mixed acid solution |
Non-Patent Citations (1)
| Title |
|---|
| 范保安等: "用非水溶液电位滴定法同时测定氢氟酸和三氟乙酸", 《化学世界》 * |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US11610783B2 (en) | 2014-07-30 | 2023-03-21 | Corning Incorporated | Ultrasonic tank and methods for uniform glass substrate etching |
| CN109668941A (en) * | 2018-12-06 | 2019-04-23 | 普瑞斯伊诺康有限公司 | A kind of method of sulfuric acid and manganese sulfate concentration in measurement electrolyte aqueous solution |
| CN109668941B (en) * | 2018-12-06 | 2021-08-03 | 普瑞斯矿业(中国)有限公司 | Method for measuring concentrations of sulfuric acid and manganese sulfate in electrolyte aqueous solution |
| CN109738577A (en) * | 2019-01-10 | 2019-05-10 | 惠科股份有限公司 | Method for detecting content of mixed acid in aluminum etching solution |
| CN110286193A (en) * | 2019-06-04 | 2019-09-27 | 青海盐湖工业股份有限公司 | The method that a kind of pair of sodium hydroxide solution carries out assay |
| CN111855650A (en) * | 2020-07-30 | 2020-10-30 | 青岛科技大学 | Method for determining content of fluosilicic acid, hydrofluoric acid and nitric acid in etching acid |
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