CN105548104A - Method for determining impurity elements arsenic and antimony in industrial anode copper through closed microwave digestion atomic fluorescence spectrometry - Google Patents
Method for determining impurity elements arsenic and antimony in industrial anode copper through closed microwave digestion atomic fluorescence spectrometry Download PDFInfo
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Abstract
The invention discloses a method for determining impurity elements arsenic and antimony in industrial anode copper through closed microwave digestion atomic fluorescence spectrometry, and relates to the technical field of detection of impurities of anode copper. Compared with a conventional acid dissolution method, the method provided by the invention adopts closed microwave digestion, potassium iodide and thiourea-ascorbic acid for treating samples, thereby saving the use amount of a digestion reagent, reducing a blank value, and shortening the time of digestion; the method can effectively mask influence of interfering ions and combinations thereof; the method also can eliminate influence of a copper matrix on arsenic and antimony measurement, and makes arsenic and antimony measurement results more accurate; the method is suitable for analysis of large quantities of samples, has good economic benefits and industrial application value, and has important promotion value on guiding actual production.
Description
Technical field
The present invention relates to technical field, specifically the method for impurity elements arsenic, antimony in a kind of airtight microwave digestion AFS DETERMINATION industry anode copper.
Background technology
Anode copper quality as electrolytic anode is tough cathode electrolysis production process key one ring, makes its quality to a great extent by the restriction of anode copper quality.Because its impurity element there will be strong chemistry and thing phase change in process of production, antianode passivation, Cathode Copper Quality, electrolyte purification and from anode copper, reclaim valuable element all have a significant impact.Therefore the accurate grasp of antianode copper impurity content, is easy to Instructing manufacture process.
At present in the trace detection of impurity element, atomic fluorescence spectrometry is sent out application by wide, and scientific research personnel a large amount of has both at home and abroad done deep research to this.By consulting a large amount of documents and materials, " hydride occurs--arsenic antimony bismuth in AFS DETERMINATION lead pig " that retrieval has " physical and chemical inspection chemistry fascicle " 2000 (1) the high illuminate Yang Guang of Lu Yu fine jade delivers if to select for a post, 200238 (3) Chen Xin shine in articles such as the yellow will of Yuan Zhineng wears by force " hydride generation--micro amount of arsenic in AFS DETERMINATION tinned food ", 20087 (3) Zhang Jing of grey hair table, borderland, Guo Shuying deliver " in Urine by Atomic Fluorescence Spectrometry arsenic and antimony " has good Detection results to the mensuration of impurity; Further retrieval finds that there is Northeastern University Lee in 2009 and closes in the Master's thesis research of arsenic, tin element " in the hydride generation-AFS DETERMINATION zinc concentrate " of celebrating and have good testing result to Impurity Elements in Zinc Concentrates; Good Detection results is had to Determination of Trace Tin in hull steel in the patent of invention of some applications of No.China Shipbuilding Industry Group Co.ltd. 725 Institute, there is good testing result to the content of selenium, tellurium, arsenic, bismuth in pure chromium in the patent of invention of Beijing Institute of Aeronautical Materials, China Aviation Industry Group Corporation, in the patent of Baiyin Nonferrous Metal Group Co., Ltd.'s invention, have good result to the assay of bismuth, selenium in industrial anode copper.
But the context of detection of trace element arsenic, antimony in anode copper, the still rare report of application of airtight microwave digestion--atomic fluorescence spectrometry.With the impurity elements arsenic in AFS DETERMINATION anode copper, antimony, the ICP--AES delivered with 1999 " Jiangxi Copper engineering " measures impurity element in anode copper; Impurity element in the x-ray fluorescence spectrometry anode copper that 2012 " China Chemical Industry trade " is delivered; " spark source direct reading spectrometry measures 19 kinds of impurity elements in anode copper " that 2012 " organic analytical chemistry " is delivered is compared: airtight microwave digestion--AFS DETERMINATION trace element result is more accurate, sensitivity is higher, detection limit is low, the consumption that processing sample process is simple, quick, reagent is cleared up in saving, reduce blank value, shorten digestion time.It is low that ICP--measures trace element sensitivity; X ray--sample requirement is cast into cylindric solid, and processing sample process is loaded down with trivial details; Spark source direct reading spectrometry--sample is smelted into copper water and is cast into bulk, and force cooling with water, processing sample process is loaded down with trivial details.
Summary of the invention
Technical matters to be solved by this invention is to provide the method for impurity elements arsenic, antimony in a kind of airtight microwave digestion AFS DETERMINATION industry anode copper, need to add lanthanum salt enrichment impurity to be measured to solve prior art, detection speed is slow, and accuracy, precision can not meet the problem of production control requirement.
The technical scheme of technical solution problem of the present invention is: a kind of method of impurity elements arsenic, antimony in airtight microwave digestion AFS DETERMINATION industry anode copper, described assay method comprises the steps.
Prepared by solution.
Hydrochloric acid (1.1): ρ 1.19g/ml, top grade is pure.
Nitric acid (1.2): ρ 1.42g/ml, top grade is pure.
Hydrochloric acid (1.3): pipette 5ml hydrochloric acid (1.1) in 100ml beaker, be diluted with water to scale, mixing.
Thiocarbamide--ascorbic acid (1.4): take 5g top grade bright sulfur urea and the pure ascorbic acid of 5g top grade respectively, be dissolved in 100ml beaker, dissolves completely, mixing, matching while using.
Solution of potassium borohydride (1.5): first take 0.5g potassium hydroxide and be dissolved in 100ml beaker, then take 2g potassium borohydride, dissolves completely, is diluted to scale, mixing, matching while using.
Liquor kalii iodide (1.6): preparation method takes the pure potassium iodide of 5g top grade in 10ml measuring cup, dissolves completely, is diluted to scale, mixing.
Hydrochloric acid (1.7): pipette 50ml hydrochloric acid (1.1) in the 100ml beaker having 50ml water, mixing.
Current-carrying solution (1.8): pipette 25ml hydrochloric acid (1.1) in the 500ml beaker being added with 300ml water in advance, be diluted to scale, mixing, is cooled to room temperature.
Arsenic standard solution A: accurately take 0.1320gAs
2o
3in 300ml beaker, add 20ml potassium hydroxide solution (100g/L), heating for dissolving is complete, and hydrochloric acid is neutralized to subacidity, and cooling moves in 1000ml volumetric flask, is diluted with water to scale, mixing.
Arsenic standard solution B: pipette 10ml arsenic standard solution A in 100ml volumetric flask, be diluted to scale with hydrochloric acid (1.3), mixing.
Arsenic standard solution C: pipette 10ml arsenic standard solution B in 100ml volumetric flask, be diluted to scale with hydrochloric acid (1.3), mixing.
Arsenic standard solution D: pipette 10ml arsenic standard solution C in 100ml volumetric flask, be diluted to scale with hydrochloric acid (1.3), mixing.
Arsenic standard solution E: pipette 10ml arsenic standard solution D in 100ml volumetric flask, be diluted to scale with hydrochloric acid (1.3), mixing.
Antimony standard solution A: take 0.2740g potassium antimony tartrate (top grade is pure), be placed in 150ml beaker, add 100ml water, low-temperature heat is dissolved, and moves in 1000ml volumetric flask, adds nitric acid 10ml in above-mentioned steps 1.2, be diluted to scale, mixing.
Antimony standard solution B: pipette 10ml antimony standard solution A in 100ml volumetric flask, be diluted to scale with hydrochloric acid (1.3), mixing.
Antimony standard solution C: pipette 10ml antimony standard solution B in 100ml volumetric flask, be diluted to scale with hydrochloric acid (1.3), mixing.
Antimony standard solution D: pipette 10ml antimony standard solution C in 100ml volumetric flask, be diluted to scale with hydrochloric acid (1.3), mixing.
Antimony standard solution E: pipette 10ml antimony standard solution D in 100ml volumetric flask, be diluted to scale with hydrochloric acid (1.3), mixing.
Sampling and sample preparation.
Industry anode copper should sample according to the standard method YS/T521-2009 promulgated, sample is processed into chip, takes 5.0g sample, be accurate to 0.0001g.
Prepare sample solution.
A takes anode copper sample bits 5.0000g in teflon counteracting tank, adds 15ml nitric acid (1.2), tightens cover, insert in microwave dissolver, from one grade to third gear (0.5Mpa, 2min; 1.0MPa, 1min; 2.0MPa, 1min) timing gradient pressurization clear up, clear up complete, take out sample-dissolving pot, cooling after can opening.
Solution in counteracting tank moves in 200ml volumetric flask by b, rinses counteracting tank with water, and the liquid that counteracting tank is residual together moves in volumetric flask, and add 10ml hydrochloric acid (1.1), constant volume, shakes up.
C divides and gets the obtained solution 25ml of step b in 100ml volumetric flask, adds 5ml liquor kalii iodide (1.6), constant volume, mixing, clarification.
D divides and gets the obtained supernatant 10ml of step c in 100ml volumetric flask, adds 35ml hydrochloric acid (1.7), 10ml thiocarbamide--ascorbic acid (1.4), constant volume, mixing.
Repeat above-mentioned experimental procedure and prepare a series of sample solution.
Preparation is with reference to solution.
A, in teflon counteracting tank, adds 15ml nitric acid (1.2), tightens cover, insert in microwave dissolver, from one grade to third gear (0.5Mpa, 2min; 1.0MPa, 1min; 2.0MPa, 1min) timing gradient pressurization clear up, clear up complete, take out sample-dissolving pot, cooling after can opening.
Solution in counteracting tank moves in 100ml volumetric flask by b, counteracting tank is rinsed with water, the liquid that counteracting tank is residual together moves in volumetric flask, add 35ml hydrochloric acid (1.7), 10ml thiocarbamide--ascorbic acid (1.4), the arsenic of different volumes number, antimony standard solution is added in volumetric flask, constant volume, mixing, be diluted with water to scale.Room temperature can use after placing 30min.Arsenic, antimony standard solution choose according to learning arsenic in sample in advance, antimony content scope chooses, alternative arsenic, antimony standard solution are respectively: arsenic, antimony standard solution A.Arsenic, antimony standard solution B.Arsenic, antimony standard solution C.Arsenic, antimony standard solution D.Arsenic, antimony standard solution E.
Drawing curve.
Utilize with reference to solution, adopt atomic fluorescence spectrometer, select the hollow cathode lamp of arsenic, antimony respectively, arsenic in sequentially determining working curve solution, the fluorescence intensity of antimony, with the mass concentration of arsenic, antimony for horizontal ordinate, with the fluorescence intensity of arsenic, antimony for ordinate, drawing curve.Instrument uses argon gas (w (Ar) >=99.99%).Instrument passes into potassium borohydride (1.5) and current-carrying solution (1.8) when detecting.
Measure the mass concentration of element arsenic, antimony in sample solution.
Utilize sample solution, adopt atomic fluorescence spectrometer, select the hollow cathode lamp of arsenic, antimony respectively, measure the fluorescence intensity of arsenic, antimony in sample solution, on corresponding working curve, find the mass concentration of respective element arsenic, antimony by the fluorescence intensity of element arsenic, antimony in sample solution.Instrument uses argon gas (w (Ar) >=99.99%).Instrument passes into potassium borohydride (1.5) and current-carrying solution (1.8) when detecting.
Computation and measurement result, obtains the content of element arsenic in sample, antimony.
Be calculated as follows the mass percent w of element arsenic in sample, antimony, numerical value represents with %:
In formula: ρ: the mass concentration measuring element arsenic, antimony in sample solution, unit is every milliliter of microgram; ν: measure sample solution volume, unit milliliter; M: sample mass, unit of gram.
The condition of work measuring the atomic fluorescence spectrometer of element arsenic is as follows.
Photomultiplier negative high voltage 300V.
Atomizer temperature 200 DEG C.
Atomizer height 8.0mm.
Carrier gas flux 400mL/min.
Shield gas flow amount 800mL/min.
Lamp current 60mA.
Reading duration 15s.
Time delay 1s.
Metering system calibration curve method.
Reading manner peak area.
Repeat 2 times.
The condition of work measuring the atomic fluorescence spectrometer of element antimony is as follows.
Photomultiplier negative high voltage 300V.
Atomizer temperature 200 DEG C.
Atomizer height 8.0mm.
Carrier gas flux 400mL/min.
Shield gas flow amount 800mL/min.
Lamp current 60mA.
Reading duration 15s.
Time delay 1s.
Metering system calibration curve method.
Reading manner peak area.
Repeat 2 times.
Tool of the present invention has the following advantages.
1 hydrochloric acid (1.8) chooses 35ml can improve sensitivity and degree of accuracy.
Acid medium and acidity directly affect the degree that element to be measured is reduced.When element to be measured is in certain valence state, be just easy to the generation of hydrogenation.When element to be measured is in high-valence state, not easily form hydride gas.Therefore element to be measured is reduced sensitivity and the accuracy that degree affects method.
Pipette arsenic, each 0.1 μ g of antimony standard solution in 100mL volumetric flask, add 0 respectively, 15,20,25,30,35,40,45ml hydrochloric acid (1.8), constant volume, mixing, measure fluorescence intensity according to method of the present invention.Table 1 data can be obtained.Be optimum acidity condition by list data known selection 35mL hydrochloric acid (1.8).
Table 1
| Add hydrochloric acid total amount (ml) | 0 | 15 | 20 | 25 | 30 | 35 | 40 | 45 |
| The fluorescence intensity of arsenic | 120.3 | 128.0 | 110.5 | 109.5 | 112.1 | 119.2 | 120.0 | 126.4 |
| The fluorescence intensity of antimony | 103.5 | 106.0 | 101.6 | 104.9 | 106.3 | 110.8 | 116.2 | 148.3 |
2. the best recovery time selects 30min that fluorescence intensity not only can be allowed to stablize, and can also raise the efficiency simultaneously and save time.
Pipette arsenic, each 0.1 μ g of antimony standard solution in 100mL volumetric flask, add 35ml hydrochloric acid (1.8), constant volume, mixing, according to method of the present invention, respectively placement 5,15,25,30,40,60,120min time, measure fluorescence intensity.Recovery time is too short, and element to be measured can not be reduced completely, makes fluorescence intensity lower, even unstable.As shown in Table 2, the fluorescence intensity of placement more than 30min arsenic, antimony is basicly stable, and the present invention at ambient temperature, selects 30min to be top condition pre-reduction time (when room temperature is lower, proper extension pre-reduction time).
Table 2
| Standing time (min) | 5 | 15 | 25 | 30 | 40 | 60 | 120 |
| The fluorescence intensity of arsenic | 88.0 | 91.5 | 99.5 | 112.1 | 119.2 | 120.0 | 126.4 |
| The fluorescence intensity of antimony | 104.3 | 110.3 | 115.0 | 136.9 | 135.2 | 132.0 | 136.0 |
3 potassium borohydride concentration are that 20g/L can reach optimum determining effect.
When potassium borohydride concentration is too low, element reduction to be measured is incomplete, and fluorescence intensity is reduced.During potassium borohydride excessive concentration, diluted in hydrogen that excessive potassium borohydride and hydrochloric acid reaction the produce concentration of hydride, causes fluorescent quenching, flame instability, and reappearance is deteriorated.Potassium borohydride is originated as the hydrogen of reductive agent and hydrogen flame, pipettes arsenic, each 0.1 μ g of antimony standard solution in 100mL volumetric flask, adds 35ml hydrochloric acid (1.8), constant volume, mixing, measures fluorescence intensity according to method of the present invention.Result shows, potassium borohydride concentration is 20g/L is top condition.
Table 3
| Potassium borohydride concentration (g/L) | 5 | 10 | 15 | 20 | 25 | 30 | 40 |
| The fluorescence intensity of arsenic | 98.0 | 110.5 | 109.5 | 112.1 | 119.2 | 120.0 | 126.4 |
| The fluorescence intensity of antimony | 113.7 | 120.0 | 122.4 | 129.0 | 122.0 | 121.7 | 123.0 |
4 choose 10mL thiocarbamide--and ascorbic acid (1.5) can be sheltered copper base, reduce blank.
Too much through the known reagent that adds of many experiments, reagent blank can be caused too high.In order to ensure to reduce completely and shelter the needs of metallic ion, the present invention is according to the data selection 10mL thiocarbamide of many experiments--ascorbic acid (1.5) is for sheltering Copper substrate top condition.Concrete data are in table 4.
Table 4
| Thiocarbamide-ascorbic acid consumption (ml) | 0 | 5 | 10 | 15 | 20 | 25 |
| The fluorescence intensity of arsenic | 108.0 | 110.5 | 109.5 | 112.1 | 119.2 | 120.0 |
| The fluorescence intensity of antimony | 100.3 | 127.9 | 130.0 | 132.5 | 150.7 | 139.5 |
Embodiment
Below in conjunction with specific experiment step and the sample #1 to #4 that chooses, the present invention will be further described.
Choose sample #1 to #4 one by one through the following experiment of row, record experimental data simultaneously.
Prepared by solution.
Hydrochloric acid (1.1): ρ 1.19g/ml, top grade is pure.
Nitric acid (1.2): ρ 1.42g/ml, top grade is pure.
Hydrochloric acid (1.3): pipette 5ml hydrochloric acid (1.1) in 100ml beaker, be diluted with water to scale, mixing.
Thiocarbamide--ascorbic acid (1.4): take 5g top grade bright sulfur urea and the pure ascorbic acid of 5g top grade respectively, be dissolved in 100ml beaker, dissolves completely, mixing, matching while using.
Solution of potassium borohydride (1.5): first take 0.5g potassium hydroxide and be dissolved in 100ml beaker, then take 2g potassium borohydride, dissolves completely, is diluted to scale, mixing, matching while using.
Liquor kalii iodide (1.6): preparation method takes the pure potassium iodide of 5g top grade in 10ml measuring cup, dissolves completely, is diluted to scale, mixing.
Hydrochloric acid (1.7): pipette 50ml hydrochloric acid (1.1) in the 100ml beaker having 50ml water, mixing.
Current-carrying solution (1.8): pipette 25ml hydrochloric acid (1.1) in the 500ml beaker being added with 300ml water in advance, be diluted to scale, mixing, is cooled to room temperature.
Arsenic standard solution A: accurately take 0.1320gAs
2o
3in 300ml beaker, add 20ml potassium hydroxide solution (100g/L), heating for dissolving is complete, and hydrochloric acid is neutralized to subacidity, and cooling moves in 1000ml volumetric flask, is diluted with water to scale, mixing.
Arsenic standard solution B: pipette 10ml arsenic standard solution A in 100ml volumetric flask, be diluted to scale with hydrochloric acid (1.3), mixing.
Arsenic standard solution C: pipette 10ml arsenic standard solution B in 100ml volumetric flask, be diluted to scale with hydrochloric acid (1.3), mixing.
Arsenic standard solution D: pipette 10ml arsenic standard solution C in 100ml volumetric flask, be diluted to scale with hydrochloric acid (1.3), mixing.
Arsenic standard solution E: pipette 10ml arsenic standard solution D in 100ml volumetric flask, be diluted to scale with hydrochloric acid (1.3), mixing.
Antimony standard solution A: take 0.2740g potassium antimony tartrate (top grade is pure), be placed in 150ml beaker, add 100ml water, low-temperature heat is dissolved, and moves in 1000ml volumetric flask, adds nitric acid 10ml in above-mentioned steps 1.2, be diluted to scale, mixing.
Antimony standard solution B: pipette 10ml antimony standard solution A in 100ml volumetric flask, be diluted to scale with hydrochloric acid (1.3), mixing.
Antimony standard solution C: pipette 10ml antimony standard solution B in 100ml volumetric flask, be diluted to scale with hydrochloric acid (1.3), mixing.
Antimony standard solution D: pipette 10ml antimony standard solution C in 100ml volumetric flask, be diluted to scale with hydrochloric acid (1.3), mixing.
Antimony standard solution E: pipette 10ml antimony standard solution D in 100ml volumetric flask, be diluted to scale with hydrochloric acid (1.3), mixing.
Sampling and sample preparation.
Industry anode copper should sample according to the standard method YS/T521-2009 promulgated, sample is processed into chip, takes 5.0g sample, be accurate to 0.0001g.
Prepare sample solution.
A takes anode copper sample bits 5.0000g in teflon counteracting tank, adds 15ml nitric acid (1.2), tightens cover, insert in microwave dissolver, from one grade to third gear (0.5Mpa, 2min; 1.0MPa, 1min; 2.0MPa, 1min) timing gradient pressurization clear up, clear up complete, take out sample-dissolving pot, cooling after can opening.
Solution in counteracting tank moves in 200ml volumetric flask by b, rinses counteracting tank with water, and the liquid that counteracting tank is residual together moves in volumetric flask, and add 10ml hydrochloric acid (1.1), constant volume, shakes up.
C divides and gets the obtained solution 25ml of step b in 100ml volumetric flask, adds 5ml liquor kalii iodide (1.6), constant volume, mixing, clarification.
D divides and gets the obtained supernatant 10ml of step c in 100ml volumetric flask, adds 35ml hydrochloric acid (1.7), 10ml thiocarbamide--ascorbic acid (1.4), constant volume, mixing.
Repeat above-mentioned experimental procedure and prepare a series of sample solution.
Preparation is with reference to solution.
A, in teflon counteracting tank, adds 15ml nitric acid (1.2), tightens cover, insert in microwave dissolver, from one grade to third gear (0.5Mpa, 2min; 1.0MPa, 1min; 2.0MPa, 1min) timing gradient pressurization clear up, clear up complete, take out sample-dissolving pot, cooling after can opening.
Solution in counteracting tank moves in 100ml volumetric flask by b, counteracting tank is rinsed with water, the liquid that counteracting tank is residual together moves in volumetric flask, add 35ml hydrochloric acid (1.7), 10ml thiocarbamide--ascorbic acid (1.4), the arsenic of different volumes number, antimony standard solution is added in volumetric flask, constant volume, mixing, be diluted with water to scale.Room temperature can use after placing 30min.Arsenic, antimony standard solution choose according to learning arsenic in sample in advance, antimony content scope chooses, alternative arsenic, antimony standard solution are respectively: arsenic, antimony standard solution A.Arsenic, antimony standard solution B.Arsenic, antimony standard solution C.Arsenic, antimony standard solution D.Arsenic, antimony standard solution E.
Drawing curve.
Utilize with reference to solution, adopt atomic fluorescence spectrometer, select the hollow cathode lamp of arsenic, antimony respectively, arsenic in sequentially determining working curve solution, the fluorescence intensity of antimony, with the mass concentration of arsenic, antimony for horizontal ordinate, with the fluorescence intensity of arsenic, antimony for ordinate, drawing curve.Instrument uses argon gas (w (Ar) >=99.99%).Instrument passes into potassium borohydride (1.5) and current-carrying solution (1.8) when detecting.
Measure the mass concentration of element arsenic, antimony in sample solution.
Utilize sample solution, adopt atomic fluorescence spectrometer, select the hollow cathode lamp of arsenic, antimony respectively, measure the fluorescence intensity of arsenic, antimony in sample solution, on corresponding working curve, find the mass concentration of respective element arsenic, antimony by the fluorescence intensity of element arsenic, antimony in sample solution.Instrument uses argon gas (w (Ar) >=99.99%).Instrument passes into potassium borohydride (1.5) and current-carrying solution (1.8) when detecting.
Computation and measurement result, obtains the content of element arsenic in sample, antimony.
Be calculated as follows the mass percent w of element arsenic in sample, antimony, numerical value represents with %:
In formula: ρ: the mass concentration measuring element arsenic, antimony in sample solution, unit is every milliliter of microgram; ν: measure sample solution volume, unit milliliter; M: sample mass, unit of gram.
The condition of work measuring the atomic fluorescence spectrometer of element arsenic is as follows.
Photomultiplier negative high voltage 300V; Atomizer temperature 200 DEG C; Atomizer height 8.0mm; Carrier gas flux 400mL/min; Shield gas flow amount 800mL/min; Lamp current 60mA; Reading duration 15s; Time delay 1s; Metering system calibration curve method; Reading manner peak area; Repeat 2 times.
The condition of work measuring the atomic fluorescence spectrometer of element antimony is as follows.
Photomultiplier negative high voltage 300V.Atomizer temperature 200 DEG C.Atomizer height 8.0mm.Carrier gas flux 400mL/min.Shield gas flow amount 800mL/min.Lamp current 60mA.Reading duration 15s.Time delay 1s.Metering system calibration curve method.Reading manner peak area.Repeat 2 times.
Compared with the acid-soluble method of routine, the present invention uses airtight microwave digestion, potassium iodide and thiocarbamide--and ascorbic acid processing sample not only saves the consumption clearing up reagent, reduces blank value, shortens digestion time.Can the impact of effectively sheltering the interference ions and combination thereof.And the impact of Copper substrate on arsenic, antimony measurement itself can also be eliminated, make the measurement result of arsenic, antimony more accurate.Be applicable to the analysis of batch samples, there is good economic benefit and industrial application value, to instructing actual production, there is important promotional value.
Claims (1)
1. airtight microwave digestion AFS DETERMINATION industry anode copper in impurity elements arsenic, antimony a method, it is characterized in that: described assay method comprises the steps:
Prepared by solution:
Hydrochloric acid (1.1): ρ 1.19g/ml, top grade is pure;
Nitric acid (1.2): ρ 1.42g/ml, top grade is pure;
Hydrochloric acid (1.3): pipette 5ml hydrochloric acid (1.1) in 100ml beaker, be diluted with water to scale, mixing;
Thiocarbamide--ascorbic acid (1.4): take 5g top grade bright sulfur urea and the pure ascorbic acid of 5g top grade respectively, be dissolved in 100ml beaker, dissolves completely, mixing, matching while using;
Solution of potassium borohydride (1.5): first take 0.5g potassium hydroxide and be dissolved in 100ml beaker, then take 2g potassium borohydride, dissolves completely, is diluted to scale, mixing, matching while using;
Liquor kalii iodide (1.6): preparation method takes the pure potassium iodide of 5g top grade in 10ml measuring cup, dissolves completely, is diluted to scale, mixing;
Hydrochloric acid (1.7): pipette 50ml hydrochloric acid (1.1) in the 100ml beaker having 50ml water, mixing;
Current-carrying solution (1.8): pipette 25ml hydrochloric acid (1.1) in the 500ml beaker being added with 300ml water in advance, be diluted to scale, mixing, is cooled to room temperature;
Arsenic standard solution A:
Accurately take 0.1320gAs
2o
3in 300ml beaker, add 20ml potassium hydroxide solution (100g/L), heating for dissolving is complete, and hydrochloric acid is neutralized to subacidity, and cooling moves in 1000ml volumetric flask, is diluted with water to scale, mixing;
Arsenic standard solution B: pipette 10ml arsenic standard solution A in 100ml volumetric flask, be diluted to scale with hydrochloric acid (1.3), mixing;
Arsenic standard solution C: pipette 10ml arsenic standard solution B in 100ml volumetric flask, be diluted to scale with hydrochloric acid (1.3), mixing;
Arsenic standard solution D: pipette 10ml arsenic standard solution C in 100ml volumetric flask, be diluted to scale with hydrochloric acid (1.3), mixing;
Arsenic standard solution E: pipette 10ml arsenic standard solution D in 100ml volumetric flask, be diluted to scale with hydrochloric acid (1.3), mixing;
Antimony standard solution A:
Take 0.2740g potassium antimony tartrate (top grade is pure), be placed in 150ml beaker, add 100ml water, low-temperature heat is dissolved, and moves in 1000ml volumetric flask, adds nitric acid 10ml in above-mentioned steps 1.2, be diluted to scale, mixing;
Antimony standard solution B: pipette 10ml antimony standard solution A in 100ml volumetric flask, be diluted to scale with hydrochloric acid (1.3), mixing;
Antimony standard solution C: pipette 10ml antimony standard solution B in 100ml volumetric flask, be diluted to scale with hydrochloric acid (1.3), mixing;
Antimony standard solution D: pipette 10ml antimony standard solution C in 100ml volumetric flask, be diluted to scale with hydrochloric acid (1.3), mixing;
Antimony standard solution E: pipette 10ml antimony standard solution D in 100ml volumetric flask, be diluted to scale with hydrochloric acid (1.3), mixing;
Sampling and sample preparation:
Industry anode copper should sample according to the standard method YS/T521-2009 promulgated, sample is processed into chip, takes 5.0g sample, be accurate to 0.0001g;
Prepare sample solution:
A takes anode copper sample bits 5.0000g in teflon counteracting tank, adds 15ml nitric acid (1.2), tightens cover, insert in microwave dissolver, from one grade to third gear (0.5Mpa, 2min; 1.0MPa, 1min; 2.0MPa, 1min) timing gradient pressurization clear up, clear up complete, take out sample-dissolving pot, cooling after can opening;
Solution in counteracting tank moves in 200ml volumetric flask by b, rinses counteracting tank with water, and the liquid that counteracting tank is residual together moves in volumetric flask, and add 10ml hydrochloric acid (1.1), constant volume, shakes up;
C divides and gets the obtained solution 25ml of step b in 100ml volumetric flask, adds 5ml liquor kalii iodide (1.6), constant volume, mixing, clarification;
D divides and gets the obtained supernatant 10ml of step c in 100ml volumetric flask, adds 35ml hydrochloric acid (1.7), 10ml thiocarbamide--ascorbic acid (1.4), constant volume, mixing;
Repeat above-mentioned experimental procedure and prepare a series of sample solution;
Preparation is with reference to solution:
A, in teflon counteracting tank, adds 15ml nitric acid (1.2), tightens cover, insert in microwave dissolver, from one grade to third gear (0.5Mpa, 2min; 1.0MPa, 1min; 2.0MPa, 1min) timing gradient pressurization clear up, clear up complete, take out sample-dissolving pot, cooling after can opening;
Solution in counteracting tank moves in 100ml volumetric flask by b, counteracting tank is rinsed with water, the liquid that counteracting tank is residual together moves in volumetric flask, add 35ml hydrochloric acid (1.7), 10ml thiocarbamide--ascorbic acid (1.4), the arsenic of different volumes number, antimony standard solution is added in volumetric flask, constant volume, mixing, be diluted with water to scale; Room temperature can use after placing 30min; Arsenic, antimony standard solution choose according to learning arsenic in sample in advance, antimony content scope chooses, alternative arsenic, antimony standard solution are respectively: arsenic, antimony standard solution A; Arsenic, antimony standard solution B; Arsenic, antimony standard solution C; Arsenic, antimony standard solution D; Arsenic, antimony standard solution E;
Drawing curve:
Utilize with reference to solution, adopt atomic fluorescence spectrometer, select the hollow cathode lamp of arsenic, antimony respectively, arsenic in sequentially determining working curve solution, the fluorescence intensity of antimony, with the mass concentration of arsenic, antimony for horizontal ordinate, with the fluorescence intensity of arsenic, antimony for ordinate, drawing curve; Instrument uses argon gas (w(Ar) >=99.99%); Instrument passes into potassium borohydride (1.5) and current-carrying solution (1.8) when detecting;
Measure the mass concentration of element arsenic, antimony in sample solution:
Utilize sample solution, adopt atomic fluorescence spectrometer, select the hollow cathode lamp of arsenic, antimony respectively, measure the fluorescence intensity of arsenic, antimony in sample solution, on corresponding working curve, find the mass concentration of respective element arsenic, antimony by the fluorescence intensity of element arsenic, antimony in sample solution; Instrument uses argon gas (w(Ar) >=99.99%); Instrument passes into potassium borohydride (1.5) and current-carrying solution (1.8) when detecting;
Computation and measurement result, obtains the content of element arsenic in sample, antimony:
Be calculated as follows the mass percent w of element arsenic in sample, antimony, numerical value represents with %:
In formula:
ρ: the mass concentration measuring element arsenic, antimony in sample solution, unit is every milliliter of microgram;
ν: measure sample solution volume, unit milliliter;
M: sample mass, unit of gram;
The condition of work measuring the atomic fluorescence spectrometer of element arsenic is as follows:
Photomultiplier negative high voltage 300V;
Atomizer temperature 200 DEG C;
Atomizer height 8.0mm;
Carrier gas flux 400mL/min;
Shield gas flow amount 800mL/min;
Lamp current 60mA;
Reading duration 15s;
Time delay 1s;
Metering system calibration curve method;
Reading manner peak area;
Repeat 2 times;
The condition of work measuring the atomic fluorescence spectrometer of element antimony is as follows:
Photomultiplier negative high voltage 300V;
Atomizer temperature 200 DEG C;
Atomizer height 8.0mm;
Carrier gas flux 400mL/min;
Shield gas flow amount 800mL/min;
Lamp current 60mA;
Reading duration 15s;
Time delay 1s;
Metering system calibration curve method;
Reading manner peak area;
Repeat 2 times.
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| CN114459867A (en) * | 2021-11-19 | 2022-05-10 | 湖北省兴发磷化工研究院有限公司 | Method for measuring content of arsenic impurity in wet-process purified phosphoric acid |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN106124473A (en) * | 2016-08-22 | 2016-11-16 | 中国铝业股份有限公司 | The assay method of Soluble Arsenic in a kind of red mud |
| CN110057791A (en) * | 2019-02-25 | 2019-07-26 | 滕亚君 | The measuring method of arsenic, mercury, bismuth, lead, cadmium content in a kind of eucalyptus oil |
| CN112595710A (en) * | 2020-11-23 | 2021-04-02 | 长沙塞克陆德医疗科技有限公司 | Rapid detection kit and detection method for iodide ions in serum sample |
| CN112595710B (en) * | 2020-11-23 | 2023-05-12 | 长沙塞克陆德医疗科技有限公司 | Rapid detection kit and detection method for iodide ions in serum sample |
| CN114459867A (en) * | 2021-11-19 | 2022-05-10 | 湖北省兴发磷化工研究院有限公司 | Method for measuring content of arsenic impurity in wet-process purified phosphoric acid |
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