CN101639437A - Method for quantitatively analyzing cobalt content in cobaltic sample - Google Patents

Method for quantitatively analyzing cobalt content in cobaltic sample Download PDF

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CN101639437A
CN101639437A CN200810126269A CN200810126269A CN101639437A CN 101639437 A CN101639437 A CN 101639437A CN 200810126269 A CN200810126269 A CN 200810126269A CN 200810126269 A CN200810126269 A CN 200810126269A CN 101639437 A CN101639437 A CN 101639437A
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cobalt
substance solution
absorbance
standard
sample
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CN101639437B (en
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盛允
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BYD Co Ltd
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BYD Co Ltd
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Abstract

The invention provides a method for quantitatively analyzing the cobalt content in a cobaltic sample. The method comprises the following steps: obtaining the absorbance value of a cobaltic substance solution and the absorbance value of a standard cobaltic substance solution respectively; and calculating the cobalt content in a cobalt sample according to directly relation that the concentration andthe absorbance of the cobalt is in direct proportion, wherein the cobaltic substance solution is the solution obtained by dissolving the cobaltic sample in an acid aqueous solution; the standard cobaltic substance solution is the solution obtained by dissolving a standard cobaltic substance in the acid aqueous solution, the standard cobalt substance is the cobalt substance with known cobalt masspercentage content; and the absorbance values are the absorbance values after eliminating the pH value influence. According to the method, relative errors of the measured cobalt content in the cobaltic substance are within 1 percent, and the accuracy is very high.

Description

A kind of quantitative analysis method that contains cobalt content in the cobalt sample
Technical field
The present invention relates to a kind of quantitative analysis method that contains cobalt content in the cobalt sample.
Background technology
Cobalt (Co) is the hard metal with steel grey and metallic luster, and its Main physical, chemical parameters and iron, nickel are approaching.The content of cobalt in the earth's crust is 0.0023%, and essential mineral has cabalt glance (CoAsS), skutterudite (CoAs 3), smaltite (CoAs 2), earthy cobalt (CoO2MnO 24H 2O), sphaerocobaltite (CoCO 3), cobalt bloom (3CoOAs 2O 58H 2O), carrollite (CuCo 2S 4), cobalt pyrite (Co 3S 4), the reserves of cobalt are very big in the manganese nodule in seabed, are the important distant view resources of cobalt.The compound of common cobalt has: CoO, Co 2O 3, Co 3O 4, Co (OH) 2, CoSO 4, CoCO 3, LiCoO 2, CoOOH etc.
Secondary rechargeable battery can use a large amount of cobalt compounds usually.The content of cobalt element in the employed cobalt compound in the secondary rechargeable battery can directly have influence on parameters such as the capacity of secondary rechargeable battery and charge efficiency.The lithium ion secondary rechargeable battery of scrapping at present is more and more, the positive electrode of overwhelming majority lithium ion battery all is a lithium cobalt oxygen, the recycling of cobalt element also is a very important problem in the waste battery, and the mass content of cobalt element is to carry out the basis of reclaiming cobalt element work in the waste battery and quantitative test goes out.Therefore, to contain the content of cobalt element in the cobalt material be very important in quantitative test.
The quantitative analysis method of cobalt element has a lot, and common have atomic emission spectrometry, atomic absorption spectrography (AAS), chemical titration and a spectrophotometer method etc.Wherein spectrophotometric method is a kind of optical instrument analytical approach that builds on the absorption spectrum basis that is produced in the molecule of material and the photon interaction process, this assay method is simple and highly sensitive, is to use one of quantitative analysis method comparatively widely at present.Adopt this method to measure that cobalt content is the principle that is directly proportional with the absorbance and the concentration of cobalt-carrying solution to be measured according to the standard cobalt-carrying solution in the cobalt compound, thereby can calculate the cobalt content in the cobalt compound.
But cobalt element content still has bigger error in the cobalt sample to adopt containing that spectrophotometric method measures at present.
Summary of the invention
The objective of the invention is to overcome the content that contains cobalt element in the cobalt sample that the available technology adopting spectrophotometric method measured has the defective of bigger error, provides a kind of accuracy the higher quantitative analysis method that contains cobalt content in the cobalt sample.
The invention provides a kind of quantitative analysis method that contains cobalt content in the cobalt sample, this method comprises obtains the absorbance that the absorbance that contains the cobalt substance solution and standard contain the cobalt substance solution respectively, calculate the cobalt content that contains in the cobalt sample according to the relation that the concentration and the absorbance of cobalt is directly proportional, the described cobalt substance solution that contains is to contain the solution that the cobalt sample is dissolved in gained behind the aqueous acid, it is that standard contains the solution that the cobalt material is dissolved in gained behind the aqueous acid that described standard contains the cobalt substance solution, described standard contain the cobalt material for the quality percentage composition of cobalt wherein known contain the cobalt material, wherein, described absorbance is for eliminating the absorbance after the pH value influences.
According to method provided by the invention, after absorbance having been eliminated the influence of pH value, can improve to a great extent and measure the accuracy that contains cobalt content in the cobalt sample, for example, the relative error that contains cobalt content in the cobalt sample that the method according to this invention is measured in 1%, and do not eliminate in the prior art pH value to the relative error of the cobalt content of the influence of absorbance up to 10%.
Embodiment
The quantitative analysis method that contains cobalt content in the cobalt sample provided by the invention comprises, comprise and obtain the absorbance that the absorbance that contains the cobalt substance solution and standard contain the cobalt substance solution respectively, calculate the cobalt content that contains in the cobalt sample according to the relation that cobalt concentration and absorbance are directly proportional, the described cobalt substance solution that contains is to contain the solution that the cobalt sample is dissolved in gained behind the aqueous acid, it is that standard contains the solution that the cobalt material is dissolved in gained behind the aqueous acid that described standard contains the cobalt substance solution, described standard contain the cobalt material for the quality percentage composition of cobalt wherein known contain the cobalt material, wherein, described absorbance is for eliminating the absorbance after the pH value influences.
According to method provided by the invention, under the preferable case, the described cobalt content β that contains in the cobalt sample calculates according to following formula (1),
β = A d * A b * × M b M d × V d V b × α - - - ( 1 )
In the formula (1), A d *Be the absorbance after the elimination pH value that contains the cobalt substance solution and the chlorine ion concentration influence, M dFor containing the quality that contains the cobalt sample in the cobalt substance solution, V dFor containing the volume of cobalt substance solution; A b *For standard contains the elimination pH value of cobalt substance solution and the absorbance after the chlorine ion concentration influence, M bFor standard contains the quality that contains the cobalt material in the cobalt substance solution, V bFor standard contains the volume of cobalt substance solution, α is the quality percentage composition that standard contains cobalt in the cobalt material.
According to method provided by the invention, under the preferable case, describedly contain cobalt substance solution and described standard to contain the pH value of cobalt substance solution identical or different, for greater than 0 and smaller or equal to 1, absorbance after described elimination pH value and the chlorine ion concentration influence is meant the absorbance after the absorbance of actual measurement multiply by correction coefficient K, and described correction coefficient K is shown in following formula (2):
K = 1 - 1 n × 10 - P - - - ( 2 )
Wherein said P is that the standard of obtaining this absorbance contains the cobalt substance solution or contains the pH value of cobalt substance solution, 11＜n＜13, preferred n=11.5-12.5, more preferably n=12.In correction coefficient K, being used for that standard contains the n and the P of cobalt substance solution and contain the n and the P of cobalt substance solution separately can be identical or different, as long as can obtain higher measuring accuracy in above-mentioned numerical range.
A preferred embodiment of the invention, the quantitative analysis method that contains cobalt content in the cobalt sample provided by the invention comprises following concrete steps,
1, preparation contains the cobalt substance solution: taking by weighing quality is M dContain the cobalt sample, dissolve this with aqueous acid and contain the cobalt sample, and to be settled to volume be V d, obtain to contain the cobalt substance solution;
2, preparation standard contains the cobalt substance solution: weighing in the balance and getting quality is M bStandard contain the cobalt material, dissolve this standard with aqueous acid and contain the cobalt material, and to be settled to volume be V b, the acquisition standard contains the cobalt substance solution, and the quality percentage composition that known standard contains cobalt in the cobalt material is α;
3, measure absorbance: the absorbance that measurement standard contains the cobalt substance solution is A b, and to measure the absorbance contain the cobalt substance solution be A d
4, measure pH value: adopt measure the pH value instrument for example the pH meter bioassay standard pH value that contains the cobalt substance solution be P b, measure the pH value that contains the cobalt substance solution and be P d
5, the absorbance A that contains the cobalt substance solution according to the standard after the following formula calculating elimination pH value concentration affects b *:
A b * = A b × K = A b ( 1 - 1 n × 10 - P b ) , In the formula, 11＜n＜13;
6, according to correction coefficient K, the absorbance A that contains the cobalt substance solution after pH value, the chlorine ion concentration influence is eliminated in calculating d *:
A d * = A d × K = A d ( 1 - 1 n × 10 - P d ) , In the formula, 11＜n＜13;
7, calculate the content that contains cobalt element in the cobalt sample:
β = A d * A b * × M b M d × V d V b × α .
According to method provided by the invention, under the preferable case, described aqueous acid is hydrochloric acid or the mixing aqueous acid that contains hydrochloric acid.The described mixing aqueous acid that contains hydrochloric acid be hydrochloric acid with nitric acid, perchloric acid and sulfuric acid solution in one or more mix aqueous acid.To make the chlorine ion concentration that contains the cobalt substance solution to be measured be 0.3-1.2 mol, 0.5-0.9 mol more preferably to the proportioning of hydrochloric acid and nitric acid, perchloric acid and sulfuric acid in the described mixing aqueous acid that contains hydrochloric acid, and the chlorine ion concentration that described standard contains the cobalt substance solution is 0.6-1.2 mol, 0.6-0.9 mol more preferably.
Be used to prepare contain the cobalt substance solution be used for aqueous acid that preparation standard contains the cobalt substance solution can be identical, also can be different.In the preferred case, more accurate in order to measure, be used to prepare that to contain the cobalt substance solution be identical with being used for the aqueous acid that preparation standard contains the cobalt substance solution, comprise that composition is all identical with content.
According to method provided by the invention, under the preferable case, in order further to improve the measuring accuracy of this method, with pH meter, the concentration of described acid solution is the 6-12 mol.
According to method provided by the invention, under the preferable case, in order further to improve the measuring accuracy of this method, described absorbance adopts spectrophotometry, and the employed measurement wavelength of described spectrophotometric method is the 500-520 nanometer.
In order to eliminate the error of being brought by instrument as far as possible, under the preferable case, described to contain the volumetric molar concentration that cobalt substance solution and standard contain cobalt in the cobalt substance solution be the 0.04-0.13 mol.
According to method provided by the invention, described standard contains the cobalt material can be various forms of cobalts, as in oxide, cobalt salt and the cobaltatess of metallic cobalt, cobalt one or more.Described metallic cobalt can also can be the alloy cobalt for simple substance cobalt, the oxide of described cobalt can be one or more in cobaltosic oxide, cobalt protoxide, the cobalt sesquioxide, described cobalt salt can be one or more in the inferior cobalt of cobalt nitrate, colbaltous nitrate and sulfuric acid, and described cobaltatess can be lithium cobalt oxygen.
The described cobalt sample that contains can be various forms of cobalts, as in oxide, cobalt salt and the cobaltatess of metallic cobalt, cobalt one or more.Described metallic cobalt can also can be the alloy cobalt for simple substance cobalt, the oxide of described cobalt can be one or more in cobaltosic oxide, cobalt protoxide, the cobalt sesquioxide, described cobalt salt can be one or more in the inferior cobalt of cobalt nitrate, colbaltous nitrate and sulfuric acid, and described cobaltatess can be lithium cobalt oxygen.For example can be lithium ion battery lithium oxygen plus plate material, comprise the lithium ion battery lithium oxygen plus plate material of scrapping.Standard contain the cobalt material can with contain the cobalt sample in the existence form of cobalt identical, also can be different, for example can be the oxide of cobalt, also can be cobalt salt or cobaltatess.
When the relation that is directly proportional according to the concentration and the absorbance of cobalt is calculated the cobalt content that contains in the cobalt sample; because the described cobalt substance solution that contains is generally and contains the solution that the cobalt sample is dissolved in gained behind the aqueous acid; described standard contains the cobalt substance solution and is generally standard and contains the solution that the cobalt material is dissolved in gained behind the aqueous acid; the absorbance that standard contains the cobalt substance solution and contains the cobalt substance solution can be subjected to the influence of this pH value of solution value usually; thereby influence the accuracy of absorbance; therefore need calibration standard to contain cobalt substance solution and the absorbance that contains the cobalt substance solution; just can make the influence of absorbance and contain the accurately reflection content of cobalt in the cobalt material and the content that standard contains cobalt in the cobalt material of containing to be measured of absorbance that cobalt substance solution and standard contain the cobalt substance solution to eliminate this pH value of solution value, this also is that the employing spectrophotometry of prior art contains the one of the main reasons that cobalt element content in the cobalt sample still has bigger error.According to method provided by the invention, multiply by the absorbance that obtains behind the correction coefficient K described in the present invention by the absorbance that makes actual measurement, can reflect the content that contains cobalt in the cobalt sample exactly, thereby improve measuring accuracy greatly.On the other hand, when described aqueous acid is hydrochloric acid or the mixing aqueous acid that contains hydrochloric acid, not only pH value of aqueous solution can impact absorbance, and the chlorion in the solution also can influence absorbance, make absorbance can not accurately reflect the cobalt content that contains in the cobalt sample, and after multiply by the correction coefficient K described in the present invention by the absorbance that makes actual measurement, then can eliminate the influence of chlorion greatly, the absorbance that obtains can reflect the content that contains cobalt in the cobalt sample exactly, thereby improves measuring accuracy greatly.
Adopt the mode of embodiment that the present invention is described in further detail below.
Embodiment 1
The instrument that uses: 752N type ultraviolet-visible pectrophotometer;
Shanghai great achievement pHS-25 type acidometer;
Sai Duolisi BS124S type electronic balance;
YXJT type cast iron temperature adjustment heating plate.
Standard model: metallic cobalt, purity 99.98%, General Research Inst. of Iron and Steel, Ministry of Metallurgical Industry production.
Contain the cobalt sample: lithium cobalt oxygen, cobalt content are 59.75%;
Reagent: hydrochloric acid, top grade is pure, and concentration is 12 mol, Guangzhou east reddening plant produced.
1, preparation contains the cobalt substance solution:
Take by weighing 5 parts with electronic balance and contain the cobalt sample, quality is respectively 0.7000g, 0.8000g, 0.9000g, 1.0000g and 1.1000g, contain the beaker that the cobalt sample places 5 100ml respectively with load weighted, be numbered L1, L2, L3, L4 and L5, in each beaker, add 8ml hydrochloric acid respectively, surface plate is added a cover in the beaker top, places heating for dissolving on the heating plate then.Above-mentioned consoluet 5 duplicate samples are transferred to constant volume in the 100ml volumetric flask.
2, preparation standard contains the cobalt substance solution
Take by weighing 3 parts of 0.5g standard models with electronic balance, load weighted standard model is placed the beaker of 3 100ml respectively, be numbered B1, B2, B3 adds 8ml hydrochloric acid respectively in each beaker, and surface plate is added a cover in the beaker top, places heating for dissolving on the heating plate then.Above-mentioned consoluet 3 duplicate samples are transferred to constant volume in the 100ml volumetric flask separately.
3, adopt ultraviolet-visible pectrophotometer under the wavelength of 510nm, measure the absorbance that contains the cobalt substance solution, the results are shown in Table 1 for gained, and measurement standard to contain the absorbance of cobalt substance solution as follows: B1 is 0.425, B2 is 0.424, B3 is 0.425.
4, the results are shown in Table 1 to adopt the acidometer measurement to contain cobalt substance solution gained, and measurement standard to contain the pH value of cobalt substance solution as follows: B1 is 0.72, B2 is 0.70, B3 is 0.73.
5, basis A b * = A b ( 1 - 1 n × 10 - P b ) The pH value is eliminated in calculating, chlorine ion concentration influences the absorbance that the back standard contains the cobalt substance solution, and the n value is 12.The gained result is: B1 is 0.418, B2 is 0.417, B3 is 0.418, and their mean value is 0.418.
6, basis A d * = A d ( 1 - 1 n × 10 - P d ) Contain the absorbance of cobalt substance solution after calculating elimination pH value, the chlorine ion concentration influence, the n value is 12, and the results are shown in Table 1 for gained.
7, basis β = A d * A b * × M b M d × V d V b × α Calculating contains cobalt element content in the cobalt sample, and the results are shown in Table 1 for gained.
Comparative Examples 1
The content that contains cobalt in the cobalt sample according to the method measurement of describing among the embodiment 1, different is, contain the cobalt sample and be numbered DL1, DL2, DL3, DL4 and DL5 respectively, and do not proofread and correct containing the absorbance that cobalt substance solution and standard contain the cobalt substance solution, the results are shown in Table 1 for gained.
Embodiment 2
The instrument that uses: 752N type ultraviolet-visible pectrophotometer;
Shanghai great achievement pHS-25 type acidometer;
Sai Duolisi BS124S type electronic balance;
YXJT type cast iron temperature adjustment heating plate.
Standard model: metallic cobalt, purity 99.98%, General Research Inst. of Iron and Steel, Ministry of Metallurgical Industry production.
Contain the cobalt sample: cobaltosic oxide, cobalt content are 72.82%;
Reagent: aqueous acid adopts the mixing aqueous acid that contains hydrochloric acid and sulfuric acid, and wherein, the volume ratio of the concentrated hydrochloric acid and the concentrated sulphuric acid is 4: 1 during preparation, and with pH meter, the concentration of mixing aqueous acid is 7 mol.
1, preparation contains the cobalt substance solution:
Take by weighing 5 parts with electronic balance and contain the cobalt sample, quality is respectively 0.5000g, 0.6000g, 0.7000g, 0.8000g and 0.9000g, contain the beaker that the cobalt sample places 5 100ml respectively with load weighted, be numbered C1, C2, C3, C4 and C5, in each beaker, add the 15ml aqueous acid respectively, surface plate is added a cover in the beaker top, places heating for dissolving on the heating plate then.Above-mentioned consoluet 5 duplicate samples are transferred to constant volume in the 100ml volumetric flask.
2, preparation standard contains the cobalt substance solution
Take by weighing 3 parts of 0.5g standard models with electronic balance, load weighted standard model is placed the beaker of 3 100ml respectively, be numbered B1, B2, B3 adds the 15ml aqueous acid respectively in each beaker, surface plate is added a cover in the beaker top, places heating for dissolving on the heating plate then.Above-mentioned consoluet 3 duplicate samples are transferred to constant volume in the 100ml volumetric flask.
3, adopt ultraviolet-visible pectrophotometer under the wavelength of 510nm, measure the absorbance that contains the cobalt substance solution, the results are shown in Table 1 for gained.And measurement standard to contain the absorbance of cobalt substance solution as follows: B1 is 0.430, B2 is 0.432, B3 is 0.432.
4, the results are shown in Table 1 to adopt the acidometer measurement to contain cobalt substance solution gained, and measurement standard to contain the pH value of cobalt substance solution as follows: B1 is 0.45, B2 is 0.44, B3 is 0.42.
5, basis A b * = A b ( 1 - 1 n × 10 - P b ) The pH value is eliminated in calculating, chlorine ion concentration influences the absorbance that the back standard contains the cobalt substance solution, and the n value is 11.5.The gained result is: B1 is 0.417, B2 is 0.418, B3 is 0.418, and their mean value is 0.418.
6, basis A d * = A d ( 1 - 1 n × 10 - P d ) Contain the absorbance of cobalt substance solution after calculating elimination pH value, the chlorine ion concentration influence, the n value is 11.5, and the results are shown in Table 1 for gained.
7, basis β = A d * A b * × M b M d × V d V b × α Calculating contains cobalt element content in the cobalt sample, and the results are shown in Table 1 for gained.
Embodiment 3
The instrument that uses: 752N type ultraviolet-visible pectrophotometer;
Shanghai great achievement pHS-25 type acidometer;
Sai Duolisi BS124S type electronic balance;
YXJT type cast iron temperature adjustment heating plate.
Standard model: metallic cobalt, purity 99.98%, General Research Inst. of Iron and Steel, Ministry of Metallurgical Industry production.
Contain the cobalt sample: cobalt nitrate, cobalt content are 18.48%; 1Guanghua Chemical Plant Co., Ltd., Guangdong produces.
Reagent: aqueous acid adopts the mixing aqueous acid that contains hydrochloric acid and nitric acid, and wherein, the volume ratio of concentrated hydrochloric acid and red fuming nitric acid (RFNA) is 3: 1 during preparation, and with pH meter, the concentration of mixing aqueous acid is concentration 9 mol.
1, preparation contains the cobalt substance solution:
Take by weighing 5 parts with electronic balance and contain the cobalt sample, quality is respectively 2.4000g, 2.6000g, 2.8000g, 3.0000g and 3.2000g, contain the beaker that the cobalt sample places 5 100ml respectively with load weighted, be numbered N1, N2, N3, N4 and N5, in each beaker, add the 10ml acid solution respectively, surface plate is added a cover in the beaker top, places heating for dissolving on the heating plate then.Above-mentioned consoluet 5 duplicate samples are transferred to constant volume in the 100ml volumetric flask.
2, preparation standard contains the cobalt substance solution
Take by weighing 3 parts of 0.5g standard models with electronic balance, load weighted standard model is placed the beaker of 3 100ml respectively, be numbered B1, B2, B3, in each beaker, add the 10ml acid solution respectively, surface plate is added a cover in the beaker top, places heating for dissolving on the heating plate then.Above-mentioned consoluet 3 duplicate samples are transferred to constant volume in the 100ml volumetric flask.
3, adopt ultraviolet-visible pectrophotometer under the wavelength of 510nm, measure the absorbance that contains the cobalt substance solution, the results are shown in Table 1 for gained.And measurement standard to contain the absorbance of cobalt substance solution as follows: B1 is 0.427, B2 is 0.428, B3 is 0.429.
4, the results are shown in Table 1 to adopt the acidometer measurement to contain cobalt substance solution gained, and measurement standard to contain the pH value of cobalt substance solution as follows: B1 is 0.56, B2 is 0.59, B3 is 0.52.
5, basis A b * = A b ( 1 - 1 n × 10 - P b ) The pH value is eliminated in calculating, chlorine ion concentration influences the absorbance that the back standard contains the cobalt substance solution, and the n value is 12.5.The gained result is: B1 is 0.418, B2 is 0.419, B3 is 0.419, and their mean value is 0.419.
6, basis A d * = A d ( 1 - 1 n × 10 - P d ) Contain the absorbance of cobalt substance solution after calculating elimination pH value, the chlorine ion concentration influence, the n value is 12.5, and the results are shown in Table 1 for gained.
7, basis β = A d * A b * × M b M d × V d V b × α Calculating contains cobalt element content in the cobalt sample, and the results are shown in Table 1 for gained.
Embodiment 4
The instrument that uses: 752N type ultraviolet-visible pectrophotometer;
Shanghai great achievement pHS-25 type acidometer;
Sai Duolisi BS124S type electronic balance;
YXJT type cast iron temperature adjustment heating plate.
Standard model: metallic cobalt, purity 99.98%, General Research Inst. of Iron and Steel, Ministry of Metallurgical Industry production.
Contain the cobalt sample: cobaltous sulphate, cobalt content are 15.27%; 1Guanghua Chemical Plant Co., Ltd., Guangdong produces.
Reagent: aqueous acid adopts the mixing aqueous acid that contains hydrochloric acid and perchloric acid, and wherein, the volume ratio of concentrated hydrochloric acid and dense perchloric acid is 8: 1 during preparation, and with pH meter, the concentration of mixing aqueous acid is 8 mol.
1, preparation contains the cobalt substance solution:
Take by weighing 5 parts with electronic balance and contain the cobalt sample, quality is respectively 3.0000g, 3.2000g, 3.4000g, 3.6000g and 3.8000g, contain the beaker that the cobalt sample places 5 100ml respectively with load weighted, be numbered S1, S2, S3, S4 and S5, in each beaker, add the 12ml aqueous acid respectively, surface plate is added a cover in the beaker top, places heating for dissolving on the heating plate then.Above-mentioned consoluet 5 duplicate samples are transferred to constant volume in the 100ml volumetric flask.
2, preparation standard contains the cobalt substance solution
Take by weighing 3 parts of 0.5g standard models with electronic balance, load weighted standard model is placed the beaker of 3 100ml respectively, be numbered B1, B2, B3 adds the 12ml acid solution respectively in each beaker, surface plate is added a cover in the beaker top, places heating for dissolving on the heating plate then.Above-mentioned consoluet 3 duplicate samples are transferred to constant volume in the 100ml volumetric flask.
3, adopt ultraviolet-visible pectrophotometer under the wavelength of 510nm, measure the absorbance that contains the cobalt substance solution, the results are shown in Table 1 for gained.And measurement standard to contain the absorbance of cobalt substance solution as follows: B1 is 0.432, B2 is 0.431, B3 is 0.430.
4, the results are shown in Table 1 to adopt the acidometer measurement to contain cobalt substance solution gained, and measurement standard to contain the pH value of cobalt substance solution as follows: B1 is 0.43, B2 is 0.48, B3 is 0.44.
5, basis A b * = A b ( 1 - 1 n × 10 - P b ) The pH value is eliminated in calculating, chlorine ion concentration influences the absorbance that the back standard contains the cobalt substance solution, and the n value is 12.The gained result is: B1 is 0.419, B2 is 0.419, B3 is 0.417, and their mean value is 0.418.
6, basis A d * = A d ( 1 - 1 n × 10 - P d ) Calculate and eliminate pH value, the chlorine ion concentration influence back absorbance that contains the cobalt substance solution to be measured, the n value is 12, and the results are shown in Table 1 for gained.
7, basis β = A d * A b * × M b M d × V d V b × α Calculate cobalt element content in the testing sample, the results are shown in Table 1 for gained.
Error analysis
Calculate the relative error that contains cobalt content in the cobalt sample that the foregoing description 1-2 and Comparative Examples 1 are measured according to following formula:
Relative error=(measured value-actual value) ÷ actual value * 100%,
(wherein, actual value is the known cobalt content value of testing sample.)
Result of calculation is listed in the table 1.
Data from table 1 as can be seen, the cobalt content that contains in the cobalt sample that the method according to this invention is measured is very accurate, the relative error of measured value and actual value is in 1%.
Table 1
Quality (g) The absorbance measuring value The pH value The absorbance correction value Test result (%) Relative error (%)
??L1 ??0.7000 ??0.362 ??0.37 ??0.349 ??59.63 ??-0.20
??L2 ??0.8000 ??0.413 ??0.42 ??0.400 ??59.80 ??0.08
??L3 ??0.9000 ??0.461 ??0.49 ??0.449 ??59.66 ??-0.15
??L4 ??1.0000 ??0.511 ??0.54 ??0.499 ??59.68 ??-0.12
??L5 ??1.1000 ??0.561 ??0.60 ??0.549 ??59.69 ??-0.10
??DL1 ??0.7000 ??0.318 ??- ??- ??53.43 ??-10.58
??DL2 ??0.8000 ??0.380 ??- ??- ??55.87 ??-6.49
??DL3 ??0.9000 ??0.441 ??- ??- ??57.64 ??-3.53
??DL4 ??1.0000 ??0.501 ??- ??- ??58.93 ??-1.37
??DL5 ??1.1000 ??0.562 ??- ??- ??60.09 ??1.57
??C1 ??0.5000 ??0.313 ??0.48 ??0.304 ??72.73 ??-0.12
??C2 ??0.6000 ??0.376 ??0.42 ??0.364 ??72.57 ??-0.34
??C3 ??0.7000 ??0.437 ??0.53 ??0.426 ??72.80 ??-0.03
??C4 ??0.8000 ??0.501 ??0.47 ??0.486 ??72.67 ??-0.21
??C5 ??0.9000 ??0.566 ??0.45 ??0.549 ??72.97 ??0.21
??N1 ??2.4000 ??0.380 ??0.49 ??0.370 ??18.40 ??-0.43
??N2 ??2.6000 ??0.412 ??0.48 ??0.401 ??18.41 ??-0.38
??N3 ??2.8000 ??0.444 ??0.45 ??0.431 ??18.39 ??-0.49
??N4 ??3.0000 ??0.477 ??0.51 ??0.465 ??18.50 ??0.11
??N5 ??3.2000 ??0.508 ??0.54 ??0.496 ??18.50 ??0.11
??S1 ??3.0000 ??0.399 ??0.45 ??0.387 ??15.40 ??0.85
??S2 ??3.2000 ??0.423 ??0.48 ??0.411 ??15.33 ??0.39
??S3 ??3.4000 ??0.442 ??0.53 ??0.431 ??15.13 ??-0.92
??S4 ??3.6000 ??0.467 ??0.58 ??0.457 ??15.15 ??-0.79
??S5 ??3.8000 ??0.498 ??0.56 ??0.487 ??15.29 ??0.13

Claims (9)

1, a kind of quantitative analysis method that contains cobalt content in the cobalt sample, this method comprises obtains the absorbance that the absorbance that contains the cobalt substance solution and standard contain the cobalt substance solution respectively, calculate the cobalt content that contains in the cobalt sample according to the relation that the concentration and the absorbance of cobalt is directly proportional, the described cobalt substance solution that contains is to contain the solution that the cobalt sample is dissolved in gained behind the aqueous acid, it is that standard contains the solution that the cobalt material is dissolved in gained behind the aqueous acid that described standard contains the cobalt substance solution, described standard contain the cobalt material for the quality percentage composition of cobalt wherein known contain the cobalt material, it is characterized in that described absorbance is for eliminating the absorbance after the pH value influences.
2, method according to claim 1 wherein, is calculated the cobalt content that contains in the cobalt sample according to following formula (1),
β = A d * A b * × M b M d × V d V b × α - - - ( 1 )
In the formula (1), β is the quality percentage composition that contains the cobalt in the cobalt sample, A d *Be the absorbance after the elimination pH value influence that contains the cobalt substance solution, M dFor being used to prepare the quality that contains the cobalt sample that contains the cobalt substance solution, V dFor containing the volume of cobalt substance solution; A b *Contain the absorbance after the elimination pH value influence of cobalt substance solution for standard, M bFor being used for the quality that standard that preparation standard contains the cobalt substance solution contains the cobalt material, V bFor standard contains the volume of cobalt substance solution, α is the quality percentage composition that standard contains cobalt in the cobalt material.
3, method according to claim 1 and 2, wherein, describedly contain cobalt substance solution and described standard to contain the pH value of cobalt substance solution identical or different, for greater than 0 and smaller or equal to 1, absorbance after described elimination pH value influences is meant the absorbance after the absorbance of actual measurement multiply by separately correction coefficient K, and described correction coefficient K is shown in following formula (2):
K = 1 - 1 n × 10 - P - - - ( 2 )
Wherein said P is that the standard of obtaining this absorbance contains the cobalt substance solution or contains the pH value of cobalt substance solution, 11＜n＜13.
4, method according to claim 3, wherein, n=11.5-12.5.
5, method according to claim 1, wherein, described aqueous acid is hydrochloric acid or the mixing aqueous acid that contains hydrochloric acid.
6, method according to claim 5, wherein, the described mixing aqueous acid that contains hydrochloric acid be hydrochloric acid with nitric acid, perchloric acid, sulfuric acid in one or more mix aqueous acid.
7, according to claim 5 or 6 described methods, wherein, with pH meter, the concentration of described aqueous acid is the 6-12 mol.
8, method according to claim 1 and 2, wherein, described absorbance adopts spectrophotometry, and the employed measurement wavelength of described spectrophotometric method is the 500-520 nanometer.
9, method according to claim 1 and 2, wherein, it is in the inferior cobalt of metallic cobalt, colbaltous nitrate, lithium cobalt oxygen, cobaltosic oxide, cobalt protoxide, cobalt sesquioxide and sulfuric acid one or more that described standard contains the cobalt material, and the described cobalt sample that contains is one or more compound or the composition that contains in lithium cobalt oxygen, cobaltosic oxide, cobalt protoxide, cobalt sesquioxide, colbaltous nitrate, cobalt nitrate, the inferior cobalt of carbonic acid, metallic cobalt and the inferior cobalt of sulfuric acid.
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CN102353642A (en) * 2011-07-14 2012-02-15 东北大学 Determination method for cobalt content in high-copper high-iron cobalt ores
CN102507492A (en) * 2011-10-21 2012-06-20 白银有色集团股份有限公司 Measurement method for gold content of anode copper
CN103604767A (en) * 2013-11-26 2014-02-26 中国南方航空工业(集团)有限公司 Method for measuring cobalt content of cutting oil
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CN102353642A (en) * 2011-07-14 2012-02-15 东北大学 Determination method for cobalt content in high-copper high-iron cobalt ores
CN102353642B (en) * 2011-07-14 2013-05-08 东北大学 Determination method for cobalt content in high-copper high-iron cobalt ores
CN102507492A (en) * 2011-10-21 2012-06-20 白银有色集团股份有限公司 Measurement method for gold content of anode copper
CN103604767A (en) * 2013-11-26 2014-02-26 中国南方航空工业(集团)有限公司 Method for measuring cobalt content of cutting oil
CN103604767B (en) * 2013-11-26 2016-05-04 中国南方航空工业(集团)有限公司 The assay method of cobalt content in cutting oil
CN108844910A (en) * 2018-06-13 2018-11-20 南昌大学 As (V) double mode detection method based on CoOOH nanometer sheet peroxidase characteristic
CN108844910B (en) * 2018-06-13 2020-12-04 南昌大学 As (V) dual-mode detection method based on CoOOH nanosheet peroxidase characteristics

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