CN102928427A - Method for determining pentavalent vanadium in vanadyl sulfate - Google Patents
Method for determining pentavalent vanadium in vanadyl sulfate Download PDFInfo
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- CN102928427A CN102928427A CN2012104140577A CN201210414057A CN102928427A CN 102928427 A CN102928427 A CN 102928427A CN 2012104140577 A CN2012104140577 A CN 2012104140577A CN 201210414057 A CN201210414057 A CN 201210414057A CN 102928427 A CN102928427 A CN 102928427A
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Abstract
The invention provides a method for determining pentavalent vanadium in vanadyl sulfate. The method comprises the following sequential steps of: putting a vanadyl sulfate sample into a vessel which can be plugged; adding sample decomposition acid and potassium iodide to the vessel to form a solution system and controlling the pH value of the solution system to 2-3, wherein the sample decomposition acid can completely decompose the sample and does not change the valence state of pentavalent vanadium ions in the sample; adding a fluoride masking agent to the vessel so as to complex impurity metal ions; adding glacial acetic acid to the vessel so as to adjust pH of a reagent in the vessel to 3.5-4; mounting a plug to the vessel and placing in a dark place for scheduled time; with a starch solution as an indicator, carrying out titration on a sodium thiosulfate standard titration solution and finishing titration when purple of the reagent disappears to obtain the content of pentavalent vanadium in the sample. The determining method disclosed by the invention has the advantages of high speed, simpleness and convenience, accuracy, strong operability and the like.
Description
Technical field
The invention belongs to the chemical analysis technology field, more particularly, relate to a kind of method of measuring the pentavalent vanadium in the vanadic sulfate.
Background technology
Usually, vanadic sulfate is called again vanadium sulfate acyl, vanadic sulfate, and its molecular formula is: VOSO
4.nH
2O, molecular weight is: 163.0 (in anhydrides), its physical and chemical performance is: blue look crystallization, contain water of crystallization, can reach 50%, soluble in water.At present, vanadic sulfate is the most important raw material of commercial production vanadium cell (VRB).In addition, vanadic sulfate is at chemical industry and widely purposes is medically also arranged, wherein, and at industrial main mordant as the dyeing and weaving industry, such as the colorant as glass and pottery; Mainly as catalyzer, mainly be used as the electrolytic solution of all-vanadium flow battery in chemical industry in the energy and material industry; Can promote the synthetic of protein and help to carry nutrition at vanadic sulfate pharmaceutically, enter the myocyte as carrying amino acid and glucose, increase myocyte's volume, the function that is similar to insulin is arranged simultaneously, there is medicinal effects in diabetes.
Along with the development of China's chemical industry, energy industry and pharmacy industry, the demand of vanadic sulfate increases year by year.In the index of product supply, the pentavalent content of vanadium in the vanadic sulfate product has been done requirement, require≤0.5%.In the prior art, mainly be assay method to pentavalent content of vanadium in the high-load barium oxide about the mensuration of pentavalent vanadium, mensuration such as different valence state vanadium in the samples such as the vanadium oxide after reductibility barium oxide, the carbon reduction, V electrolyte, assay method adopts ferrous ammonium sulfate titration and potentiometric titration, can not be applicable to analysis and the mensuration of pentavalent vanadium in the vanadic sulfate.
In addition, document " separation determination of pentavalent vanadium in the vanadium sulfate acyl " (yellow valuable, the super .[J of Korea Spro's book]. Hunan metallurgy .1997, (6): 54～56.) introduced BPHA-CHCl
3Pentavalent vanadium in the extract and separate spectrophotometry vanadic sulfate, but the method operation is loaded down with trivial details, has used organic extractant, and not only cost is high, and analysis efficiency is low.
In addition, owing to the difference of vanadic sulfate according to its preparation technology, the phase of vanadium also may exist trivalent vanadium and pentavalent vanadium except existing with a large amount of tetravalence vanadium, so the pentavalent vanadium in the Accurate Determining vanadic sulfate is material phase analysis, and difficulty is larger.
Summary of the invention
For the above-mentioned deficiency of prior art, the object of the invention is to solve at least one in the problems referred to above at least.
For example, one of purpose of the present invention is to provide a kind of pentavalent content of vanadium that can measure in the vanadic sulfate sample that contains definite trivalent vanadium of measuring and pentavalent vanadium.
The invention provides the assay method of pentavalent vanadium in a kind of vanadic sulfate, described method comprises the following steps of carrying out successively: the sample of vanadic sulfate is put into can be had a container of plug; Add sample in the described container and decompose acid and potassium iodide forming solution system, and the pH value of controlling described solution system is 2～3, wherein, the sour valence state that can decompose sample fully and not change pentavalent vanadium ion in the sample of described sample decomposition; In described container, add the fluoride screening agent with complexing foreign metal ion; Add glacial acetic acid in the described container and be adjusted to 3.5～4 with the pH with test solution in the described container; Give described container tool plug, and place the dark place schedule time; As indicator, and adopt the sodium thiosulfate standard titration solution to carry out titration with starch solution, disappear as titration end-point with described test solution purple, obtain the content of pentavalent vanadium in the sample.
In exemplary embodiment of the present invention, described fluoride screening agent is ammonium bifluoride or potassium fluoride.
In exemplary embodiment of the present invention, the described schedule time is 10min～30min.
In exemplary embodiment of the present invention, the amount of putting into of described sample is not less than 1.0g.
In exemplary embodiment of the present invention, it is the aqueous solution of sulfuric acid that described sample decomposes acid.
In exemplary embodiment of the present invention, described foreign metal ion comprises Fe
3+, As
5+, Sb
5+
In exemplary embodiment of the present invention, contain pentavalent vanadium ion and the trivalent vanadium ion of the amount of determining in the sample of described vanadic sulfate.
Compared with prior art, assay method of the present invention has the advantages such as quick, easy, accurate, strong operability.
Embodiment
Hereinafter, describe the assay method of pentavalent vanadium in the vanadic sulfate of the present invention in detail in connection with exemplary embodiment.
In one exemplary embodiment of the present invention, the assay method of pentavalent vanadium comprises the following steps of carrying out successively in the vanadic sulfate:
The sample of vanadic sulfate put into to have a container of plug; In described container, add the sample decomposition acid (for example, the aqueous solution of sulfuric acid) that to decompose sample fully and not change the valence state of pentavalent vanadium ion in the sample, be controlled to be 2～3 with the pH value with solution in the described container; In described container, add potassium iodide, make pentavalent vanadium and the potassium iodide generation elemental iodine that reacts; In described container, add the fluoride screening agent with complexing foreign metal ion; Add glacial acetic acid in the described container and be adjusted to 3.5～4 with the pH with solution in the described container, and can play buffer action; Give described container tool plug, and place the dark place schedule time; As indicator, and adopt the sodium thiosulfate standard titration solution to carry out titration with starch solution, disappear as titration end-point with described test solution purple, obtain the content of pentavalent vanadium in the sample.Here, described sample decomposes can adding in the described container regardless of order of acid and potassium iodide.
The key reaction principle of this example is:
That is, pentavalent vanadium and iodide ion react, and generate elemental iodine, are scaled the amount of pentavalent vanadium by sodium thiosulfate titration elemental iodine.In this example, contain a small amount of trivalent vanadium element in the sample, trivalent vanadium in the sample in adding the process that acid decomposes preferentially by the oxygen in the reaction system (for example, sample decomposes the oxygen of carrying secretly in the acid) oxidation, the redox normal potential of oxygen is 1.23, the standard oxidationreduction potential of pentavalent vanadium is 0.999, adds to have a large amount of potassium iodides in the reaction system, so trivalent vanadium can not react with the pentavalent vanadium.In addition, add glacial acetic acid with the pH of test solution to being adjusted to 3.5～4, the sodium thiosulfate in the test solution is reacted fully and up hill and dale with iodine.
In another exemplary embodiment of the present invention, described fluoride screening agent can be ammonium bifluoride or potassium fluoride.But the invention is not restricted to this, if in can the complexing sample such as Fe
3+, As
5+, Sb
5+All can Deng foreign metal ion fluoride screening agent.
In another exemplary embodiment of the present invention, the described schedule time is preferably 10min～30min.But the invention is not restricted to this, as long as pentavalent vanadium and potassium iodide are fully reacted.
In another exemplary embodiment of the present invention, the addition of sample can be according to the wherein height selection of pentavalent content of vanadium, if the pentavalent content of vanadium in the sample is lower, then its addition can suitably increase.For example, generally, the amount of putting into of sample preferably is not less than 1.0g.
In another exemplary embodiment of the present invention, it is aqueous sulfuric acid that described sample decomposes acid.For example, in the described aqueous sulfuric acid, the volume ratio of sulfuric acid and water can be 1: 100.Yet, the invention is not restricted to this, as long as all can be used as sample, the aqueous sulfuric acid that can decompose sample and not change the valence state of pentavalent vanadium ion in the sample decomposes acid, and can be 2～3 with the pH value of solution in the described container by regulating its addition, thereby provide suitable Acidity Range for the reaction of pentavalent vanadium and iodide ion.
In another exemplary embodiment of the present invention, the assay method of pentavalent vanadium also can adopt following mode to realize in the described vanadic sulfate:
A, take by weighing an amount of testing sample, sample size can be selected according to the height of pentavalent content of vanadium, usually be not less than 1.0g, in can the analytical implement of tool plug, such as iodine flask;
B, add 30～50mL sample in the testing sample and decompose acid, 0.5～3.0g potassium iodide adds 0.3～1.0g ammonium bifluoride or potassium fluoride, adds 5.0～10.0mL glacial acetic acid again, makes test solution pH be stabilized in 3.5～4, shakes up.Give analytical implement tool plug, place the dark place so that pentavalent vanadium and potassium iodide fully react, for example, the reaction time can be 10min～30min.For example, sample decomposes acid can be low-concentration sulfuric acid solution, and for example, wherein the volume ratio of sulfuric acid and water can be 1: 100.
C, take out from the dark place, add 3～5mL starch indicator (10g/L) appropriate amount of starch solution as indicator, the purple disappearance that is titrated to solution with the sodium thiosulfate standard titration solution is terminal point.
Here, comprise potassium iodide, sulfuric acid, ammonium bifluoride or potassium fluoride, glacial acetic acid all reagent purity grade for analyze pure more than.
In this exemplary embodiment, the fluoride screening agent of adding can with such as Fe
3+, As
5+, Sb
5+Deng foreign metal ion generation complex reaction, thereby avoid these foreign metal ions of high price and potassium iodide to react; But the pH of the adding regulator solution of glacial acetic acid is between 3.5～4, and glacial acetic acid also has buffer action, can stablize test solution pH.
Below, prove absolutely exemplary embodiment of the present invention by the description to concrete example, and the present invention is not limited to these examples.
Example 1
Take by weighing the 1# vanadic sulfate sample of 2.000g and put into the 300mL iodine flask, add the 0.8g potassium iodide, the sulfuric acid solution (wherein the volume ratio of sulfuric acid and water is 1: 100) that adds scheduled volume is take the solution of formation pH in iodine flask as 2, shake sample is decomposed fully, add the 0.5g ammonium bifluoride, the 6.0mL glacial acetic acid shakes up, cover the stopper of iodine flask, 20min is placed in the dark place.Take out, add 3mL starch indicator (10g/L) and be titrated to the purple disappearance with the sodium thiosulfate standard titration solution.
Table 1 shows the result who adopts after 1 pair of 1# vanadic sulfate of example sample carries out measuring for 8 times.
Pentavalent vanadium measurement result in the table 1 1# vanadic sulfate sample
Example 2
Take by weighing the 2# vanadic sulfate sample of 3.000g and put into the 300mL iodine flask, add the 1.5g potassium iodide, the sulfuric acid solution (wherein the volume ratio of sulfuric acid and water is 2: 100) that adds scheduled volume is take the solution of formation pH in iodine flask as 2.5, add the 1.0g potassium fluoride, 8.0mL glacial acetic acid, shake up, cover the stopper of iodine flask, 10min is placed in the dark place.Take out, add 5mL starch indicator (10g/L) and be titrated to the purple disappearance with the sodium thiosulfate standard titration solution.
Table 2 shows the result who adopts after 2 pairs of 2# vanadic sulfates of example sample carries out measuring for 8 times.
Pentavalent vanadium measurement result in the table 2 1# vanadic sulfate sample
Example 3
Take by weighing the 5.000g sample in the 300mL iodine flask, add the 2.0g potassium iodide, the sulfuric acid solution (wherein the volume ratio of sulfuric acid and water is 1: 5) that adds scheduled volume is take the solution of formation pH in iodine flask as 3, shake sample is decomposed fully, add the 1.0g ammonium bifluoride, the 10.0mL glacial acetic acid shakes up, cover the stopper of iodine flask, 10min is placed in the dark place.Take out, add 3mL starch indicator (10g/L) and be titrated to the purple disappearance with the sodium thiosulfate standard titration solution.
Table 3 shows the result who adopts after 3 pairs of 3# vanadic sulfates of example sample carries out measuring for 8 times.
Pentavalent vanadium measurement result in the table 3 3# vanadic sulfate sample
In above-mentioned example 1-3, sodium thiosulfate standard titration solution concentration is 0.02mol/L.
Can find out from table 1～3, adopt assay method of the present invention to measure the pentavalent content of vanadium in the vanadic sulfate, and the measurement result favorable reproducibility, method stability is high.
In addition, adopt above example 1～3 to carry out the mark-on recovery test of pentavalent vanadium standard solution, the recovery that obtains the pentavalent vanadium all between 98.9～102%, proves that method of the present invention has higher accuracy, can satisfy the facies analysis requirement.
In sum, method of the present invention can be used in the mensuration of pentavalent vanadium in the vanadic sulfate, and measure lower limit and can reach 0.01%, relative standard deviation (n=8, RSD%＜2%), the recovery of standard addition of pentavalent vanadium is between 98.9%～102%.Therefore, assay method of the present invention has the advantages such as quick, easy, accurate, strong operability.
Although the above has described the present invention in conjunction with exemplary embodiment, those of ordinary skills should be clear, in the situation of the spirit and scope that do not break away from claim, can carry out various modifications to above-described embodiment.
Claims (6)
1. the assay method of pentavalent vanadium in the vanadic sulfate is characterized in that described method comprises the following steps of carrying out successively:
The sample of vanadic sulfate put into to have a container of plug;
Add sample in the described container and decompose acid and potassium iodide forming solution system, and the pH value of controlling described solution system is 2～3, wherein, the sour valence state that can decompose sample fully and not change pentavalent vanadium ion in the sample of described sample decomposition;
In described container, add the fluoride screening agent with complexing foreign metal ion;
Add glacial acetic acid in the described container and be adjusted to 3.5～4 with the pH with test solution in the described container;
Give described container tool plug, and place the dark place schedule time;
As indicator, and adopt the sodium thiosulfate standard titration solution to carry out titration with starch solution, disappear as titration end-point with described test solution purple, obtain the content of pentavalent vanadium in the sample.
2. the assay method of pentavalent vanadium in the vanadic sulfate according to claim 1 is characterized in that, described fluoride screening agent is ammonium bifluoride or potassium fluoride.
3. the assay method of pentavalent vanadium in the vanadic sulfate according to claim 1 is characterized in that, the described schedule time is 10min～30min.
4. the assay method of pentavalent vanadium in the vanadic sulfate according to claim 1 is characterized in that the amount of putting into of described sample is not less than 1.0g.
5. the assay method of pentavalent vanadium in the vanadic sulfate according to claim 1 is characterized in that, it is the aqueous solution of sulfuric acid that described sample decomposes acid.
6. the assay method of pentavalent vanadium in the vanadic sulfate according to claim 1 is characterized in that, described foreign metal ion comprises Fe
3+, As
5+, Sb
5+
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Cited By (5)
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| CN104034726A (en) * | 2013-03-06 | 2014-09-10 | 广东先导稀材股份有限公司 | Method for determining bismuth content and vanadium content of bismuth vanadate |
| CN105259302A (en) * | 2015-11-13 | 2016-01-20 | 攀钢集团攀枝花钢铁研究院有限公司 | Method for directly measuring content of trivalent vanadium in vanadium slag |
| CN107449772A (en) * | 2017-08-22 | 2017-12-08 | 淄博火炬能源有限责任公司 | Pregnant solution type lead acid accumulator electrolyte method for detecting impurities |
| CN107655882A (en) * | 2017-09-18 | 2018-02-02 | 攀钢集团攀枝花钢铁研究院有限公司 | The assay method of pentavalent vanadium and application in a kind of vanadium slag |
| CN108037114A (en) * | 2018-02-07 | 2018-05-15 | 四川星明能源环保科技有限公司 | A kind of detection method of the component of the method for detecting impurities of vanadic sulfate and the hydrate of vanadium containing tetravalence |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104034726A (en) * | 2013-03-06 | 2014-09-10 | 广东先导稀材股份有限公司 | Method for determining bismuth content and vanadium content of bismuth vanadate |
| CN105259302A (en) * | 2015-11-13 | 2016-01-20 | 攀钢集团攀枝花钢铁研究院有限公司 | Method for directly measuring content of trivalent vanadium in vanadium slag |
| CN105259302B (en) * | 2015-11-13 | 2016-11-02 | 攀钢集团攀枝花钢铁研究院有限公司 | Directly measure the method for trivalent vanadium content in vanadium slag |
| CN107449772A (en) * | 2017-08-22 | 2017-12-08 | 淄博火炬能源有限责任公司 | Pregnant solution type lead acid accumulator electrolyte method for detecting impurities |
| CN107655882A (en) * | 2017-09-18 | 2018-02-02 | 攀钢集团攀枝花钢铁研究院有限公司 | The assay method of pentavalent vanadium and application in a kind of vanadium slag |
| CN108037114A (en) * | 2018-02-07 | 2018-05-15 | 四川星明能源环保科技有限公司 | A kind of detection method of the component of the method for detecting impurities of vanadic sulfate and the hydrate of vanadium containing tetravalence |
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