CN109668941A - A kind of method of sulfuric acid and manganese sulfate concentration in measurement electrolyte aqueous solution - Google Patents
A kind of method of sulfuric acid and manganese sulfate concentration in measurement electrolyte aqueous solution Download PDFInfo
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- CN109668941A CN109668941A CN201811487655.0A CN201811487655A CN109668941A CN 109668941 A CN109668941 A CN 109668941A CN 201811487655 A CN201811487655 A CN 201811487655A CN 109668941 A CN109668941 A CN 109668941A
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- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N27/00—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means
- G01N27/02—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating impedance
- G01N27/04—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating impedance by investigating resistance
- G01N27/06—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating impedance by investigating resistance of a liquid
Abstract
The present invention discloses a kind of method for measuring sulfuric acid and manganese sulfate concentration in electrolyte aqueous solution, comprising: (1) provides an electrolyte aqueous solution sample；(2) it is gradually added aqueous slkali, and measures the conductivity that corresponding aqueous sample when volume is added in different aqueous slkalis；(3) function of the analysis conductivity value as alkali additional amount, by the feature of the function with: (i) acid-base reaction terminal and (ii) manganese sulfate and alkali reaction end are associated, obtain the corresponding alkali addition volume of the two terminals；(4) concentration that volume is scaled sulfuric acid and manganese sulfate in original solution is added in the corresponding alkali of the two terminals；The addition of alkali corresponding to the two terminals volume is scaled sulfuric acid mass M in raw sample1With the mass M of manganese sulfate2；The concentration of sulfuric acid and manganese sulfate in original solution is determined according to the volume of sample.Operation of the present invention is simple, can greatly improve detection efficiency, reduces the usage amount of chemical reagent, improves the reliability of detection data.
Description
Technical field
The present invention relates to chemical analysis fields and electrolytic manganese dioxide production technical field, and in particular to a kind of measurement includes
The method of sulfuric acid concentration and manganese sulfate concentration in the electrolyte aqueous solution of sulfuric acid and manganese sulfate.
Background technique
MnSO is generally used in current electrolysis manganese dioxide (calling EMD in the following text) production process4Solution as electrolyte, electrolysis
Anode is the pole plate of titanium or titanium alloy material, and cathode is the pole plate of copper, graphite or similar materials.In direct current in electrolytic process
The lower Mn dissociated of effect2+Generate MnO2And it is deposited on anode surface, while generating H in a cell2SO4And H2.Therefore in reality
Production process in, the practical electrolyte being contained in electrolytic cell is a kind of MnSO4With H2SO4Mixed aqueous solution.It had been electrolysed
Cheng Zhong, the H in electrolyte2SO4And MnSO4Concentration large effect can be generated to the performance of the electrolytic manganese dioxide of generation, sternly
Lattice control the H of electrolyte in electrolytic process2SO4And MnSO4Concentration is particularly significant.Generally it is electrolysed using traditional titration measuring
MnSO in liquid4With H2SO4, i.e., H is detected as the acid base neutralization titration method of titrant using NaOH or KOH2SO4Concentration, and adopt
To KMnO4It is the oxidimetry detection MnSO of titrant4Concentration.In process of production, using conventional method to big
Electrolyte in the electrolytic cell of amount carry out independent analysis be not easy to observe there are cumbersome, chemical reaction terminal, analyze speed slowly,
Chemical reagent consumption amount is big, is not easy the disadvantages of realizing operation automation.
Summary of the invention
The object of the present invention is to provide a kind of sulfuric acid concentration of electrolyte aqueous solution of the measurement comprising sulfuric acid and manganese sulfate and
The method of manganese sulfate concentration, this method is easy to operate, can greatly improve detection efficiency, reduces the usage amount of chemical reagent, improves
The reliability of detection data.
The technical solution adopted in the present invention includes:
(1) providing a volume is V0The electrolyte aqueous solution sample comprising sulfuric acid and manganese sulfate；
(2) it is gradually added a kind of equivalent concentration and is the aqueous slkali of N, and measure different aqueous slkalis and corresponding water when volume is added
It is molten
The conductivity of liquid sample；
(3) function of the analysis conductivity value as alkali additional amount, by the feature of the function and: (i) acid-base reaction terminal and
(ii) manganese sulfate and alkali reaction end are associated, obtain the corresponding alkali of the two terminals and volume is added；
(4) concentration that volume is scaled sulfuric acid and manganese sulfate in original solution is added in the corresponding alkali of the two terminals；By this
Alkali corresponding to two terminals is added volume and is scaled sulfuric acid mass M in raw sample1With the mass M of manganese sulfate2；According to sample
Volume determines the concentration of sulfuric acid and manganese sulfate in original solution.
The alkali is sodium hydroxide or potassium hydroxide.
Linked character includes the maximum value for determining second dervative.
The maximum value of the second dervative is determined by finding the solution of three order derivatives.
Linked character further includes:
Two maximum local maximums for finding second dervative respectively correspond two equivalent points of reaction；Alkali additional amount compared with
That low relevant equivalent point is the equivalent point of acid-base reaction, and it is V that volume, which is added, in corresponding alkali1；Another equivalent point is
The equivalent point of manganese sulfate and alkali reaction, it is V that volume, which is added, in corresponding alkali2。
Alkali addition volume is converted to the quality of sulfuric acid and manganese sulfate according to following calculation method:
M1=V1×N×98.079÷2
Wherein V1Unit be to rise, the unit of N is mole every liter；
M2=[(V2-V1)×N×151.002÷2]×a+b
Wherein V1And V2Unit be to rise, the unit of N is mole every liter；
A is M2The Gradient correction coefficient of calculated value, dimensionless；
B is M2The intercept correction value of calculated value, unit g；
Calculate M1Divided by V0To obtain sulfuric acid concentration, M is calculated2Divided by V0To obtain manganese sulfate concentration.
The conductivity of corresponding aqueous sample, obtains the electricity of aqueous solution when the present invention is by measuring different alkali addition volumes
Conductance data series corresponding with alkali addition volume.Second dervative is carried out to data series obtained to calculate and three order derivative meters
It calculates, is solved by three order derivatives to find two local maximums of second dervative, the i.e. corresponding drop of the two local maximums
Two equivalent points during fixed.That lower equivalent point of alkali additional amount is the terminal of acid-base reaction, and corresponding alkali adds
Entering volume is V1；Another equivalent point is the terminal of manganese sulfate and alkali reaction after acid-base reaction, and corresponding alkali is added volume and is
V2.The addition volume of alkali is finally scaled by sulfuric acid and manganese sulfate in tested electrolyte aqueous solution according to corresponding calculation method
Concentration.
By the present invention in that being titrated with single titrant agent by one-time continuous while to obtain sulfuric acid in solution to be measured dense
Degree and manganese sulfate concentration, and the accurate equivalent point for finding reaction, analysis result obtained are calculated by second order and three order derivatives
Accurately and reliably, detection efficiency is high.It is corresponding to determine that it is applied to the electrolyte detection in electrolytic manganese dioxide production process
Sulfuric acid concentration and manganese sulfate concentration, can quickly handle a large amount of samples and obtain accurate detection as a result, for production during and
When adjust each electrolytic cell electrolytic condition provide foundation, be conducive to stablize and improve electrolytic manganese dioxide quality.This method
Learn stability high NaOH or the KOH redox titrant low instead of chemical stability, such as KMnO4, improve measurement number
According to reliability.This method can reduce chemical reagent usage amount simultaneously, artificial required for detection required for reducing, can be effective
Reduce testing cost.
Detailed description of the invention
Fig. 1 is aqueous solution conductivity variations schematic diagram in titration.
Fig. 2 is the relevant titration curve of embodiment 1, Second derivative curves and three order derivative curves.
Specific embodiment
The present invention is described in detail below in conjunction with specific embodiment.
Conductivity (Conductivity) is the inverse of resistance, is usually indicated with S/m or μ S/cm.It is electrolyte system
Special parameter-its conductive capability measurement.The factor for determining conductive capability power includes the electrically charged number of ion, electricity
The mobile speed of lotus, ion concentration and the temperature of electrolyte solution etc..Kohlrausch makes as drawn a conclusion: in infinite dilution
Solution in, ion moves independently of one another, is independent of each other.Because the conductive capability of each ion is not in the solution of infinite dilution
It is influenced by other ions, therefore is believed that the molar conductivity of electrolyte is the sum of the molar conductivity of anions and canons.The present invention
The limiting molar conductivity of ion involved in the electrolyte aqueous solution of concern is found in table 1.
The limiting molar conductivity of 1. relevant ions of table
| Ionic type | Limiting molar conductivity (* 104s.m2/mol) |
| H+ | 349.8 |
| Na+ | 50.1 |
| K+ | 73.5 |
| 1/2Mn2+ | 53.1 |
| OH- | 198.0 |
| 1/2SO4 2- | 79.8 |
It is right although the total conductivity of the solution can be obtained by theoretical calculation for the conductivity of infinite dilute solution
The method of various electrolyte solutions in actual production, theoretical calculation can not be applicable in.Compare limiting molar conductivity number
According to can be determined that even if under nonideality, H+Na can be also several times as much as to the contribution of the conductivity of studied system+、K+Or1/2Mn2+.Similarly, Na+(or K+) and OH-Synergistic effect will be much larger than Na+(or K+).And so on, we are it can be concluded that as follows
Inference: the ion concentration of Multicomponent electrolyte solution system is changed, the variation of conductivity is also regular seeks.More than
Become theoretical basis of the invention.Since detected solution is nonideal solution, electrical conductivity of solution is by ion concentration, environment
Temperature, electrolyte to non-electrolyte the factors such as change influence, the response of conductivity also will be nonlinear curve.
The present invention aqueous solution main electrolyte comprising sulfuric acid and manganese sulfate of interest is H2SO4And MnSO4.With NaOH
For titration, acid-base neutralization reaction can first occur in titration process:
H2SO4+ NaOH=NaSO4+H2O
After acid-base neutralization reaction is complete, as reacting for manganese sulfate and alkali can occur for the increase that volume is added in NaOH.Sulphur
Generation between sour manganese and alkali react and the pH value of solution has biggish association.When the pH value of solution reaches 4.5 to 5, by
In the molar ratio of manganese sulfate and NaOH height, it is easier to that the precipitation reaction of following alkali formula manganese sulfate: 2MnSO occurs4+ 2NaOH=Na2SO4
+Mn2(OH)2SO4
When pH value of solution reaches 7 or so, following react can occur between manganese sulfate and NaOH:
2MnSO4+ 2NaOH=Na2SO4+Mn2(OH)2
As shown in Figure 1, after the reaction occurs, as continuing growing for volume, manganese sulfate and NaOH molar ratio is added in NaOH
The generation of alkali formula manganese sulfate becomes difficult after being lower, Mn (OH)2Generation gradually occupy leading position.It is titrated from using NaOH solution
MnSO4Process for, Mn (OH)2Generation reaction be whole process main reaction.
Hydrogen ion conductivity with higher in solution, using in aqueous slkali titration process due to H+And OH-In conjunction with generation
H2O, the lower Na of conductivity in solution+Or K+The constantly substitution higher H of conductivity+, the total conductivity of solution constantly reduces.When
H in solution2SO4It is reacted completely with aqueous slkali, reaches first reaction equivalent point, the conductivity in solution is minimum.Continue to be added dropwise
Aqueous slkali, alkali and MnSO4Reaction generates Mn (OH)2Precipitating, Mn2+Constantly by Na+Or K+Substitution, due to1/2Mn2+And Na+Conductivity
It is not much different, the conductivity variations of solution are little, when more than NaOH and MnSO4The equivalent point of reaction, it is continuous with aqueous slkali
It is added, the OH in solution-It is continuously increased, the conductivity of solution will be stepped up.The titration of KOH is then different.Due to K+Pole
Limit molar conductivity is significantly greater than1/2Mn2+, at Mn (OH)2During precipitating, electrical conductivity of solution will take ascendant trend.Therefore,
Work as Mn2+The further up trend of conductivity caused by after depleted is obvious not to the utmost.This spirit for also determining the second equivalent point
Sensitivity is declined.
Therefore, the conductivity of the titration system is as the increase that volume is added in aqueous slkali can be in now in the acid-base reaction stage
Drop trend；Acid-base reaction enters manganese sulfate and alkali reaction interval afterwards completely can then show conductivity ascendant trend；Work as manganese sulfate
The trend of accelerating is showed with after alkali reaction angstrom completely.The turning point in the curve each stage is the equivalent point reacted.
But the non-linear property of the conductivity due to the system and aqueous slkali additional amount is added from electrical conductivity of solution to be measured and alkali
The turning point that each different phase directly can not be accurately determined in the corresponding data series of volume, i.e., can not accurately determine in soda acid
The equivalent point reacted with the equivalent point and manganese sulfate of reaction with alkali.But it carries out single order by the data series to such broken line type to lead
After number calculates, the inflection point of first derivative is the turning point (corresponding to equivalent point) of corresponding former data series.Further, one
The inflection point of order derivative can be by determining to its local maximum is found after data series progress second dervative calculating.And two
After the maximum value of order derivative data series again can be by carrying out three order derivative calculating to the data series, then to three order derivative systems
Column, which are solved and (find the corresponding points that three order derivatives are 0), to be determined.
In addition, the reaction for manganese sulfate and alkali, since the reaction occurred between them is hybrid reaction, although manganese sulfate
The reaction that generation manganous hydroxide is reacted with alkali is main reaction, but is reacted due to generating the reaction of alkali formula manganese sulfate with manganous hydroxide is generated
Reaction molar equivalent it is inconsistent, volume is added according to the corresponding alkali of stoichiometric point and individually using the reaction molar equivalent of main reaction
The concentration for directly to calculate manganese sulfate can generate minus deviation.But it is dense using the manganese sulfate that traditional manganese sulfate titration method detects
Degree result alkali additional amount corresponding with the equivalent point determined using the method for the present invention directly calculates institute by the reaction equivalent of main reaction
As a result, the Gradient correction coefficient and intercept correction value to direct calculated result can be returned out.It is revised by comparing
Calculated result is consistent with conventional method.
Embodiment and comparative example
It is V that sample to be measured, which is volume, in the embodiment of the present invention0The electrolysis comprising certain density sulfuric acid and manganese sulfate
Matter aqueous sample.The titration apparatus used is Mei Teletuo benefit T70 autotitrator, and it is specified as instrument to set mixing speed
The 50% of revolving speed, pre- mixing time 10S, the titrant used are the aqueous slkali that concentration is N.It needs to set aqueous slkali according to different
Titrant adds mode, records the conductivity value of aqueous solution, and it is corresponding to obtain conductivity and the alkali addition volume of aqueous solution to be measured
Data series.The first derivative data series of the data series, second dervative data series and three are calculated according to this data series
Order derivative data series obtain the coincidence point that second dervative peak value and three order derivatives are 0 by calculated result, are identified as in soda acid
The equivalent point reacted with the equivalent point and manganese sulfate of reaction with alkali.That lower relevant equivalent point of alkali additional amount is in soda acid
With the equivalent point of reaction, it is V that volume, which is added, in corresponding alkali1；Another equivalent point is the equivalent point that manganese sulfate and alkali react,
It is V that volume, which is added, in corresponding alkali2.Alkali addition volume is converted to the quality of sulfuric acid and manganese sulfate according to following calculation method:
M1=V1×N×98.079÷2
Wherein V1Unit be to rise, the unit of N is mole every liter；
M2=[(V2-V1)×N×151.002÷2]×a+b
Wherein V1And V2Unit be to rise, the unit of N is mole every liter；
A is M2The Gradient correction coefficient of calculated value, dimensionless；
B is M2The intercept correction value of calculated value, unit g；
Calculate M1Divided by V0To obtain sulfuric acid concentration, M is calculated2Divided by V0To obtain manganese sulfate concentration.
Embodiment 1: as shown in Fig. 2, the electrolyte aqueous solution sample 1 containing certain density sulfuric acid and manganese sulfate is accurate
1ml is drawn, is placed in 100mL beaker, 80ml distilled water is added, using the NaOH of 0.5mol/L as titrant, with 0.02ml/
The titrant of 5S is added mode and is titrated, and records the conductivity value of each titration point, records the conductivity value of aqueous solution, obtain
The conductivity of aqueous solution to be measured data series corresponding with alkali addition volume are looked by carrying out all-order derivative calculating to data series
The coincidence point that second dervative peak value and three order derivatives are 0 out, is respectively identified as the equivalent point that NaOH is reacted with sulfuric acid and manganese sulfate,
The sulfuric acid and sulfuric acid manganese content of sample are calculated further according to above-mentioned calculation method.
Embodiment 2: accurately drawing 1ml for above-mentioned sample 1 respectively, be placed in 100mL beaker, 80ml distilled water is added,
Using the NaOH of 0.5mol/L as titrant, mode is added with the titrant of 0.10ml/3S and is titrated, the electricity of aqueous solution is recorded
The corresponding data series of volume are added in conductivity value, the conductivity and alkali for obtaining aqueous solution to be measured, each by carrying out to data series
Order derivative calculates the coincidence point for finding that second dervative peak value and three order derivatives are 0, is respectively identified as NaOH and sulfuric acid and manganese sulfate
The sulfuric acid and sulfuric acid manganese content of sample are calculated further according to above-mentioned calculation method for the equivalent point of reaction.
Embodiment 3: accurately drawing 1ml for above-mentioned sample 1 respectively, be placed in 100mL beaker, 80ml distilled water is added,
Using the KOH of 0.5mol/L as titrant, mode is added with the titrant of 0.02ml/5S and is titrated, the electricity of aqueous solution is recorded
The corresponding data series of volume are added in conductivity value, the conductivity and alkali for obtaining aqueous solution to be measured, each by carrying out to data series
Order derivative calculates the coincidence point for finding that second dervative peak value and three order derivatives are 0, is respectively identified as NaOH and sulfuric acid and manganese sulfate
The sulfuric acid and sulfuric acid manganese content of sample are calculated further according to above-mentioned calculation method for the equivalent point of reaction.
Embodiment 4: accurately drawing 1ml for above-mentioned sample 1 respectively, be placed in 100mL beaker, 80ml distilled water is added,
Using the KOH of 0.5mol/L as titrant, mode is added with the titrant of 0.10ml/3S and is titrated, the electricity of aqueous solution is recorded
The corresponding data series of volume are added in conductivity value, the conductivity and alkali for obtaining aqueous solution to be measured, each by carrying out to data series
Order derivative calculates the coincidence point for finding that second dervative peak value and three order derivatives are 0, is respectively identified as NaOH and sulfuric acid and manganese sulfate
The sulfuric acid and sulfuric acid manganese content of sample are calculated further according to above-mentioned calculation method for the equivalent point of reaction.
Comparative example 1: conventional titration method is used, NaOH is used to make the acid base neutralization titration method of titrant and with KMnO4It does and drips
The oxidation-reduction method for determining agent titrates above-mentioned sample 1 and sample 2, acquires the sulfuric acid and sulfuric acid manganese content of sample.
Embodiment 1, embodiment 2, embodiment 3, embodiment 4, the result of comparative example 1 are listed in table 1
Table 1
Embodiment 5: using Mei Teletuo benefit T70 autotitrator, by the identification condition of Titration Conditions and equivalent point, meter
Calculation method solidifies setting into the titration procedure of titrator, realizes that titrator automatic Titration, automatic identification terminal are automatic to calculate simultaneously
Titration results are exported, for improving detection efficiency and convenient for automatically processing a large amount of samples, reduce testing staff's workload.It will contain
The electrolyte aqueous solution sample 2 of certain density sulfuric acid and manganese sulfate, sample 3, sample 4, sample 5, sample 6 are accurate respectively to be drawn
1ml is placed in 100mL beaker, 80ml distilled water is added, using the NaOH of 0.5mol/L as titrant, with 0.10ml/3S's
Titrant is added mode progress automatic Titration and is calculated automatically by the automatic automatic identification terminal of titrator and exported titration results.
Comparative example 2: conventional titration method is used, NaOH is used to make the acid base neutralization titration method of titrant and with KMnO4It does and drips
The oxidation-reduction method for determining agent is titrated, and measures sulfuric acid content and sulfuric acid manganese content in above-mentioned sample respectively.
Table 2 is listed in embodiment 5 and to the result of comparative example 2.
Table 2
It is important to note that the embodiment of the present invention application process only need using a kind of aqueous slkali (NaOH or
KOH it) is used as titrant, and the conventional titration method of comparative example is needed using NaOH and KMnO4Two kinds of titrant.Due to KMnO4Tool
There are strong oxidizing property, KMnO4Titrant in reservoir internal stability not as good as NaOH or KOH titrant, if longer using the holding time
KMnO4The accuracy of comparative example testing result certainly will be influenced when being detected, therefore uses KMnO4Frequency is needed when as titrant
The preparation and calibration for carrying out titrant numerously, increase the workload of detection.In addition, traditional analysis method is not easy to realize certainly
Dynamicization detection.
In addition, detecting the sulfuric acid concentration and sulfuric acid in 60 samples using detection method of the invention in terms of detection time
The time that manganese concentration needs is about 3 hours, and the work that analyst is operated is mainly that sample is drawn and diluted；And it adopts
Completing the time that same detection workload needs with conventional method is about 8 hours, and analyst's whole process needs be sampled,
Sample preparation, titration and calculating, working strength greatly increase.
The embodiments of the present invention have been described in detail above, but content is only the preferred embodiment of the present invention,
It should not be considered as limiting the scope of the invention.All changes and improvements made in accordance with the scope of the present invention, should all
It still belongs within this patent covering scope.
Claims (6)
1. a kind of method of sulfuric acid and manganese sulfate concentration in measurement electrolyte aqueous solution, characterized by comprising:
(1) providing a volume is V0The electrolyte aqueous solution sample comprising sulfuric acid and manganese sulfate；
(2) it is gradually added a kind of equivalent concentration and is the aqueous slkali of N, and measure different aqueous slkalis and corresponding aqueous solution when volume is added
The conductivity of sample；
(3) function of the analysis conductivity value as alkali additional amount, by the feature of the function and: (i) acid-base reaction terminal and (ii)
Manganese sulfate and alkali reaction end are associated, obtain the corresponding alkali of the two terminals and volume is added；
(4) concentration that volume is scaled sulfuric acid and manganese sulfate in original solution is added in the corresponding alkali of the two terminals；By the two
Alkali corresponding to terminal is added volume and is scaled sulfuric acid mass M in raw sample1With the mass M of manganese sulfate2；According to the volume of sample
Determine the concentration of sulfuric acid and manganese sulfate in original solution.
2. according to the method described in claim 1, it is characterized by: the alkali is sodium hydroxide or potassium hydroxide.
3. according to the method described in claim 1, it is characterized by: linked character includes the maximum value for determining second dervative.
4. according to the method described in claim 3, it is characterized by: the maximum value of the second dervative is led by finding three ranks
Several solution determines.
5. according to the method described in claim 3, it is characterized by: linked character further includes:
Two maximum local maximums for finding second dervative respectively correspond two equivalent points of reaction；The lower phase of alkali additional amount
That equivalent point closed is the equivalent point of acid-base reaction, and it is V that volume, which is added, in corresponding alkali1；Another equivalent point is sulfuric acid
The equivalent point of manganese and alkali reaction, it is V that volume, which is added, in corresponding alkali2。
6. according to the method described in claim 1, it is characterized by:, according to following calculation method by alkali addition volume be converted to
The quality of sulfuric acid and manganese sulfate:
M1=V1×N×98.079÷2
Wherein V1Unit be to rise, the unit of N is mole every liter；
M2=[(V2-V1)×N×151.002÷2]×a+b
Wherein V1And V2Unit be to rise, the unit of N is mole every liter；
A is M2The Gradient correction coefficient of calculated value, dimensionless；
B is M2The intercept correction value of calculated value, unit g；
Calculate M1Divided by V0To obtain sulfuric acid concentration, M is calculated2Divided by V0To obtain manganese sulfate concentration.
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