CN113759072A - Method for measuring arsenic content in copper-arsenic intermediate alloy - Google Patents
Method for measuring arsenic content in copper-arsenic intermediate alloy Download PDFInfo
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- 229910052785 arsenic Inorganic materials 0.000 title claims abstract description 72
- RQNWIZPPADIBDY-UHFFFAOYSA-N arsenic atom Chemical compound [As] RQNWIZPPADIBDY-UHFFFAOYSA-N 0.000 title claims abstract description 72
- 238000000034 method Methods 0.000 title claims abstract description 39
- 229910045601 alloy Inorganic materials 0.000 title claims abstract description 38
- 239000000956 alloy Substances 0.000 title claims abstract description 38
- JEMGLEPMXOIVNS-UHFFFAOYSA-N arsenic copper Chemical compound [Cu].[As] JEMGLEPMXOIVNS-UHFFFAOYSA-N 0.000 title claims abstract description 36
- 239000012086 standard solution Substances 0.000 claims abstract description 50
- 239000003153 chemical reaction reagent Substances 0.000 claims abstract description 28
- 238000005303 weighing Methods 0.000 claims abstract description 17
- 239000007853 buffer solution Substances 0.000 claims abstract description 12
- 230000001376 precipitating effect Effects 0.000 claims abstract description 6
- BDOYKFSQFYNPKF-UHFFFAOYSA-N 2-[2-[bis(carboxymethyl)amino]ethyl-(carboxymethyl)amino]acetic acid;sodium Chemical compound [Na].[Na].OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O BDOYKFSQFYNPKF-UHFFFAOYSA-N 0.000 claims abstract description 3
- 230000001590 oxidative effect Effects 0.000 claims abstract description 3
- 239000000243 solution Substances 0.000 claims description 47
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 34
- 239000011734 sodium Substances 0.000 claims description 27
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 claims description 23
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 20
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 19
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 19
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 claims description 18
- MWUXSHHQAYIFBG-UHFFFAOYSA-N nitrogen oxide Inorganic materials O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 claims description 18
- 239000002244 precipitate Substances 0.000 claims description 17
- ZGTMUACCHSMWAC-UHFFFAOYSA-L EDTA disodium salt (anhydrous) Chemical compound [Na+].[Na+].OC(=O)CN(CC([O-])=O)CCN(CC(O)=O)CC([O-])=O ZGTMUACCHSMWAC-UHFFFAOYSA-L 0.000 claims description 16
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 claims description 16
- 230000003472 neutralizing effect Effects 0.000 claims description 13
- 238000004448 titration Methods 0.000 claims description 13
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 12
- HJTAZXHBEBIQQX-UHFFFAOYSA-N 1,5-bis(chloromethyl)naphthalene Chemical compound C1=CC=C2C(CCl)=CC=CC2=C1CCl HJTAZXHBEBIQQX-UHFFFAOYSA-N 0.000 claims description 11
- GOLCXWYRSKYTSP-UHFFFAOYSA-N arsenic trioxide Inorganic materials O1[As]2O[As]1O2 GOLCXWYRSKYTSP-UHFFFAOYSA-N 0.000 claims description 11
- CWERGRDVMFNCDR-UHFFFAOYSA-N thioglycolic acid Chemical compound OC(=O)CS CWERGRDVMFNCDR-UHFFFAOYSA-N 0.000 claims description 11
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 10
- 229910052802 copper Inorganic materials 0.000 claims description 10
- 239000010949 copper Substances 0.000 claims description 10
- 238000007865 diluting Methods 0.000 claims description 10
- 150000002500 ions Chemical class 0.000 claims description 10
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 9
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 9
- 235000019270 ammonium chloride Nutrition 0.000 claims description 9
- 229910017604 nitric acid Inorganic materials 0.000 claims description 9
- 239000007787 solid Substances 0.000 claims description 9
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 8
- 229910001629 magnesium chloride Inorganic materials 0.000 claims description 8
- 239000000203 mixture Substances 0.000 claims description 8
- 238000005406 washing Methods 0.000 claims description 8
- 238000001816 cooling Methods 0.000 claims description 7
- 238000004090 dissolution Methods 0.000 claims description 7
- 239000003109 Disodium ethylene diamine tetraacetate Substances 0.000 claims description 6
- 235000019301 disodium ethylene diamine tetraacetate Nutrition 0.000 claims description 6
- 239000007788 liquid Substances 0.000 claims description 6
- 238000002156 mixing Methods 0.000 claims description 6
- KJFMBFZCATUALV-UHFFFAOYSA-N phenolphthalein Chemical compound C1=CC(O)=CC=C1C1(C=2C=CC(O)=CC=2)C2=CC=CC=C2C(=O)O1 KJFMBFZCATUALV-UHFFFAOYSA-N 0.000 claims description 6
- 238000002360 preparation method Methods 0.000 claims description 6
- ORFSSYGWXNGVFB-UHFFFAOYSA-N sodium 4-amino-6-[[4-[4-[(8-amino-1-hydroxy-5,7-disulfonaphthalen-2-yl)diazenyl]-3-methoxyphenyl]-2-methoxyphenyl]diazenyl]-5-hydroxynaphthalene-1,3-disulfonic acid Chemical compound COC1=C(C=CC(=C1)C2=CC(=C(C=C2)N=NC3=C(C4=C(C=C3)C(=CC(=C4N)S(=O)(=O)O)S(=O)(=O)O)O)OC)N=NC5=C(C6=C(C=C5)C(=CC(=C6N)S(=O)(=O)O)S(=O)(=O)O)O.[Na+] ORFSSYGWXNGVFB-UHFFFAOYSA-N 0.000 claims description 6
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 claims description 5
- 229910001431 copper ion Inorganic materials 0.000 claims description 5
- 238000010438 heat treatment Methods 0.000 claims description 5
- HEQBUZNAOJCRSL-UHFFFAOYSA-N iron(ii) chromite Chemical compound [O-2].[O-2].[O-2].[Cr+3].[Fe+3] HEQBUZNAOJCRSL-UHFFFAOYSA-N 0.000 claims description 5
- 241000530268 Lycaena heteronea Species 0.000 claims description 4
- 238000009835 boiling Methods 0.000 claims description 4
- QKSIFUGZHOUETI-UHFFFAOYSA-N copper;azane Chemical compound N.N.N.N.[Cu+2] QKSIFUGZHOUETI-UHFFFAOYSA-N 0.000 claims description 4
- 239000000706 filtrate Substances 0.000 claims description 4
- 238000001914 filtration Methods 0.000 claims description 4
- 238000003756 stirring Methods 0.000 claims description 4
- 238000001035 drying Methods 0.000 claims description 3
- 230000003647 oxidation Effects 0.000 claims description 3
- 238000007254 oxidation reaction Methods 0.000 claims description 3
- 238000001556 precipitation Methods 0.000 claims description 3
- JLVVSXFLKOJNIY-UHFFFAOYSA-N Magnesium ion Chemical compound [Mg+2] JLVVSXFLKOJNIY-UHFFFAOYSA-N 0.000 claims description 2
- 229910001425 magnesium ion Inorganic materials 0.000 claims description 2
- 230000002452 interceptive effect Effects 0.000 claims 1
- 238000004458 analytical method Methods 0.000 abstract description 9
- 238000001514 detection method Methods 0.000 abstract description 6
- 229910001369 Brass Inorganic materials 0.000 description 7
- 239000010951 brass Substances 0.000 description 7
- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Natural products N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 6
- 229910000881 Cu alloy Inorganic materials 0.000 description 5
- 230000007797 corrosion Effects 0.000 description 4
- 238000005260 corrosion Methods 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 3
- 239000011777 magnesium Substances 0.000 description 3
- 229910052749 magnesium Inorganic materials 0.000 description 3
- 238000011084 recovery Methods 0.000 description 3
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 2
- 229910021529 ammonia Inorganic materials 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 239000011701 zinc Substances 0.000 description 2
- 229910000554 Admiralty brass Inorganic materials 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- 238000003723 Smelting Methods 0.000 description 1
- 229910001297 Zn alloy Inorganic materials 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 238000001391 atomic fluorescence spectroscopy Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 238000003926 complexometric titration Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000004993 emission spectroscopy Methods 0.000 description 1
- 239000013505 freshwater Substances 0.000 description 1
- 238000009616 inductively coupled plasma Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000004445 quantitative analysis Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000013535 sea water Substances 0.000 description 1
- 238000002798 spectrophotometry method Methods 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N31/00—Investigating or analysing non-biological materials by the use of the chemical methods specified in the subgroup; Apparatus specially adapted for such methods
- G01N31/16—Investigating or analysing non-biological materials by the use of the chemical methods specified in the subgroup; Apparatus specially adapted for such methods using titration
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
- G01N21/75—Systems in which material is subjected to a chemical reaction, the progress or the result of the reaction being investigated
- G01N21/77—Systems in which material is subjected to a chemical reaction, the progress or the result of the reaction being investigated by observing the effect on a chemical indicator
- G01N21/78—Systems in which material is subjected to a chemical reaction, the progress or the result of the reaction being investigated by observing the effect on a chemical indicator producing a change of colour
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- Biochemistry (AREA)
- Analytical Chemistry (AREA)
- General Health & Medical Sciences (AREA)
- General Physics & Mathematics (AREA)
- Immunology (AREA)
- Pathology (AREA)
- Molecular Biology (AREA)
- Engineering & Computer Science (AREA)
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- Investigating Or Analyzing Non-Biological Materials By The Use Of Chemical Means (AREA)
Abstract
A method for measuring the arsenic content in a copper-arsenic intermediate alloy comprises the following specific steps: preparing a buffer solution, preparing an arsenic standard solution, preparing and calibrating an ethylene diamine tetraacetic acid disodium standard solution, weighing a sample, dissolving the sample, oxidizing and precipitating, separating interference elements, titrating and calculating a result; the method is simple and convenient to operate, high in accuracy and superior to the existing method in the aspect of measuring the high-content arsenic, the adopted reagents are common reagents, expensive instruments and equipment are not needed, the detection cost is low, the method is suitable for daily analysis of the arsenic in the copper-arsenic intermediate alloy, and the vacancy of the method for analyzing the arsenic element in the copper-arsenic intermediate alloy is filled.
Description
Technical Field
The invention relates to the field of chemical analysis, and mainly provides a method for measuring arsenic content in a copper-arsenic intermediate alloy.
Background
Brass is an alloy of copper and zinc, and is widely used in the fields of mechanical parts, valves, water pipes, cartridge cases and the like at present. However, brass with a zinc content of greater than 15% generally has poor corrosion resistance, and dezincification corrosion occurs particularly when it comes into contact with fresh water or seawater. Research shows that the addition of a proper amount of arsenic element into brass can effectively inhibit the dezincification phenomenon of brass, enhance the corrosion resistance of brass and prolong the service life of materials. Arsenic is added to brass materials of grades C26130, C35330, C44300, C46500, C46800 and the like to enhance corrosion resistance, and some of the grades are already mature and applied as admiralty brass.
The copper-arsenic intermediate alloy is a main additive of arsenic element in the arsenic-containing brass smelting process, the adding temperature is low, and the components are easy to control. The currently commonly used copper-arsenic master alloy is named CuAs23, and the arsenic content is 20.0-25.0% according to the specification of the chemical components of CuAs in the nonferrous industry standard YS/T283-one 2009 copper master alloy ingot. Meanwhile, the standard provides that the arbitration analysis method for the chemical composition of the copper intermediate alloy is executed according to the specification of GB/T5121. At present, GB/T5121 mainly comprises an atomic fluorescence spectrometry, a spectrophotometry and an inductively coupled plasma emission spectrometry for measuring the arsenic content in copper and copper alloy. The maximum upper limit of the detection range of the detection methods is only 0.8%, the detection methods are only suitable for measuring trace and trace arsenic, and the measurement of high-content arsenic can be lack of accuracy or cannot be measured at all. Therefore, the methods are obviously not suitable for measuring the arsenic in the copper-arsenic intermediate alloy.
The method for measuring the arsenic content in the copper-arsenic intermediate alloy has no relevant literature at present. Therefore, the method for quickly and accurately measuring the arsenic in the copper-arsenic intermediate alloy at low cost is found, and has important significance for checking and accepting raw materials and controlling product quality.
In view of the above, a method for determining the arsenic content in a copper-arsenic master alloy has been developed.
Disclosure of Invention
The invention aims to overcome the defects in the prior art, and provides the method for measuring the arsenic content in the copper-arsenic intermediate alloy, which is simple and convenient to operate, can quickly and accurately measure the arsenic content in the copper-arsenic intermediate alloy, has high accuracy, has advantages in the aspect of measuring high-content arsenic compared with the prior art, adopts common reagents, does not need expensive instruments and equipment, has low detection cost, is suitable for daily analysis of arsenic in the copper-arsenic intermediate alloy, and fills the gap of the method for analyzing the arsenic element in the copper-arsenic intermediate alloy.
In order to achieve the purpose, the invention adopts the following technical scheme: a method for measuring the arsenic content in a copper-arsenic intermediate alloy comprises the following specific steps: preparing a buffer solution, preparing an arsenic standard solution, preparing and calibrating an ethylene diamine tetraacetic acid disodium standard solution, weighing a sample, dissolving the sample, oxidizing and precipitating, separating interference elements, titrating and calculating a result.
Preparing a buffer solution: weighing 54g of ammonium chloride, dissolving in water, adding 280mL of ammonia water (rho 0.90g/mL), diluting with water to 1000mL, and uniformly mixing for later use;
preparing an arsenic standard solution: putting the arsenic trioxide working reference reagent in an oven for drying for 2 hours at 110 ℃, putting the reagent in a dryer for cooling to room temperature, weighing 1.320g of the arsenic trioxide working reference reagent by using an electronic balance, putting the arsenic trioxide working reference reagent in a beaker, dissolving the arsenic trioxide working reference reagent by using 10mL-20mL of sodium hydroxide solution (100g/L), adding 2 drops of phenolphthalein ethanol solution (10g/L) after complete dissolution, neutralizing the solution by using hydrochloric acid (1+1) until the red color of the solution fades, adding the solution in an excess of 5mL, transferring the solution into a 1000mL volumetric flask, diluting the volumetric flask with water to a specified scale, and uniformly mixing, wherein 1mL of the standard solution contains 0.001g of arsenic.
Disodium ethylene diamine tetraacetate (Na)2EDTA) preparation and calibration of standard solutions:
preparation: 7.120g of disodium ethylene diamine tetraacetate solid reagent is weighed by an electronic balance, dissolved in 190-200mL hot water, cooled, transferred into a 1000mL volumetric flask, diluted to a designated scale by water and uniformly mixed for later use to prepare a Na2EDTA standard solution with the concentration [ Na2EDTA is approximately equal to 0.019mol/L ];
calibration: weighing 0.200g of pure copper, placing the pure copper in a 250mL beaker, adding 10mL of nitric acid (1+1), heating to dissolve the pure copper, boiling until liquid on the wall of the beaker flows down in an oily state to remove nitrogen oxides, adding 25.00mL of arsenic standard solution, adding 4-6 drops of hydrogen peroxide (30%), 5g of ammonium chloride solid reagent and 15mL of magnesium chloride solution (50g/L), diluting the mixture to about 100mL by using water, neutralizing the mixture by using ammonia water (rho 0.90g/mL) to generate dark blue cuprammonium complex ions, adding 10-15 mL of excessive cuprammonium complex ions, stirring for 3-5 minutes, and standing for 30-30 minutes;
filtering with slow filter paper, washing beaker and precipitate with ammonia water (1+99) for more than 10 times, dissolving precipitate with 20mL hot hydrochloric acid (1+1) in original beaker, washing filter paper with hot water for 3-4 times, and cooling to room temperature;
neutralizing with ammonia water (rho 0.90g/mL) until the solution becomes ammoniacal, adding 80mL of water, 10mL of buffer solution, 5 drops of thioglycolic acid, 2-3 drops of chrome black T-ethanol solution (2g/L), and adding prepared Na2Titrating the EDTA standard solution until the solution is pure blue;
the titer of the Na2EDTA standard solution to arsenic was calculated as follows:
in the above formula: T-Na2The titre of EDTA standard solution to arsenic, g/mL; v-consumption of Na by calibration2Volume of EDTA standard solution, mL.
Sample weighing: weighing 0.15g-0.25g of a copper-arsenic intermediate alloy sample by using an electronic balance, accurately weighing the sample to 0.0001g, and placing the weighed sample into a 250mL beaker;
sample dissolution: adding 5-15 mL of nitric acid (1+1) into a beaker, placing the beaker on an electric hot plate for heating to dissolve the nitric acid, and boiling until liquid on the wall of the beaker flows down in an oily state to remove nitrogen oxides;
oxidation and precipitation: adding 4-6 drops of hydrogen peroxide (30%), 5g of ammonium chloride solid reagent and 15mL of magnesium chloride solution (50g/L) into a beaker, and diluting with water to 90-100mL of volume; neutralizing with ammonia water (rho 0.90g/mL) until deep blue copper ammonia complex ions are generated, adding 10-15 mL of the copper ammonia complex ions, stirring for 3 minutes, standing for 30 minutes, and converting arsenic elements in the copper-arsenic intermediate alloy into NH4MgAsO4·6H2And (4) precipitating O.
Separating interference elements: filtering with slow filter paper, washing beaker and precipitate with ammonia water (1+99) for more than 10 times, dissolving precipitate with 20mL hot hydrochloric acid (1+1) in original beaker, washing filter paper with hot water for 3-4 times,cooling the filtrate in the beaker to room temperature, separating a large amount of interference elements such as copper ions, magnesium ions and the like in the solution to be detected, and removing NH4MgAsO4·6H2Dissolving the O precipitate into a solution state;
titration: neutralizing with ammonia water (rho 0.90g/mL) until the solution is ammoniacal, adding 80mL of water and 10mL of buffer solution to make the pH value of the solution be 10-11, adding 5 drops of thioglycolic acid to mask trace copper ions, using 2-3 drops of chrome black T-ethanol solution (2g/L) as indicator, and using Na with well-calibrated known titer2Titration of EDTA standard solution to a pure blue end point and recording Na consumption2Volume of EDTA standard solution;
and (4) calculating a result: after titration, the percentage content of As is calculated according to the following formula:
in the above formula: T-Na2The titre of EDTA standard solution to arsenic, g/mL; v-consumption of Na in titration2Volume of EDTA standard solution, mL; m-sample weight, g.
The invention has the beneficial effects that: the invention adopts nitric acid to dissolve copper-arsenic intermediate alloy into solution, uses hydrogen peroxide to oxidize arsenite radical in the solution into arsenite radical, then adjusts the solution into ammoniacal solution, and adds magnesium chloride solution to generate NH4MgAsO4·6H2O precipitates and the precipitate is then isolated. Due to NH4MgAsO4·6H2Dissolving the precipitate with hydrochloric acid at a molar ratio of magnesium to arsenic of 1:1 in O, and adding disodium edetate (Na) at pH of 10-112EDTA) standard solution can indirectly measure the arsenic content by titrating magnesium element; the invention provides a method for measuring arsenic in a copper-arsenic intermediate alloy, which comprises the step of adding magnesium chloride to generate NH in an ammoniacal environment4MgAsO4·6H2And (3) precipitating O, titrating magnesium to indirectly measure the arsenic content, realizing accurate analysis of high-content arsenic in the copper alloy, and widening the chemical analysis range of arsenic in the copper alloy. By using Na2EDTA complexometric titration, clear end point, withGood accuracy and precision; the method is simple and convenient to operate, high in accuracy and superior to the existing method in the aspect of measuring the high-content arsenic, the adopted reagents are common reagents, expensive instruments and equipment are not needed, the detection cost is low, the method is suitable for daily analysis of the arsenic in the copper-arsenic intermediate alloy, and the vacancy of the method for analyzing the arsenic element in the copper-arsenic intermediate alloy is filled.
Detailed Description
The present invention will be described in further detail with reference to the following examples and embodiments:
example 1
The analysis process of the arsenic content in the CuAs23 copper-arsenic master alloy comprises the following steps:
preparing a buffer solution: 54.00g of ammonium chloride is weighed, dissolved in water, added with 280mL of ammonia water (. rho.0.90 g/mL), diluted with water to 1000mL and mixed for later use.
Preparing an arsenic standard solution: putting the arsenic trioxide working reference reagent in an oven for drying for 2 hours at 110 ℃, and putting the reagent in a dryer for cooling to room temperature. Weighing 1.320g of arsenic trioxide working standard reagent by using an electronic balance, placing the arsenic trioxide working standard reagent in a beaker, adding 15mL of sodium hydroxide solution (100g/L) for dissolution, adding 2 drops of phenolphthalein ethanol solution (10g/L) after complete dissolution, neutralizing by using hydrochloric acid (1+1) until the red color of the solution fades and the excessive amount is 5 mL. Transferring into a 1000mL volumetric flask, diluting to the mark with water, and mixing uniformly. 1mL of this standard solution contained 0.001g of arsenic.
Disodium ethylene diamine tetraacetate (Na)2EDTA) preparation and calibration of standard solutions:
preparation: 7.1200g of disodium ethylenediaminetetraacetate solid reagent was weighed by an electronic balance, dissolved in about 200mL of hot water, and cooled. Transferring into a 1000mL volumetric flask, diluting to the scale with water, and mixing uniformly for later use.
Calibration: 0.200g of pure copper (99.9% or more) was weighed into a 250mL beaker, 10mL of nitric acid (1+1) was added thereto, heated and dissolved, and boiled until the liquid flowed down as an oil on the wall of the beaker to remove nitrogen oxides. 25.00mL arsenic standard solution was added, 5 drops of hydrogen peroxide (30%), 5g ammonium chloride solid reagent, 15mL magnesium chloride solution (50g/L) were added, and the mixture was diluted with water to a volume of about 100 mL. The resulting mixture was neutralized with aqueous ammonia (. rho.0.90 g/mL) to give dark blue copper ammine complex ions, and stirred for 3 minutes in an excess of 15 mL. And standing for 30 minutes.
Filter through slow filter paper, wash the beaker with ammonia (1+99) and precipitate 12 times. The precipitate was dissolved in portions in the original beaker with 20mL of hot hydrochloric acid (1+1), and the filter paper was washed 3 times with hot water. The filtrate in the beaker was cooled to room temperature.
Neutralizing with ammonia water (rho 0.90g/mL) until the solution becomes ammoniacal, adding 80mL of water, 10mL of buffer solution, 5 drops of thioglycolic acid, 3 drops of chrome black T-ethanol solution (2g/L), and adding prepared Na2The EDTA standard solution was titrated to a pure blue end point.
Calibrating in parallel three times, respectively consuming Na2EDTA standard solution 17.48mL, 17.45mL, 17.43 mL. Na was calculated as follows2The titre of EDTA standard solution to arsenic was 0.001430g/mL, 0.001433g/mL, 0.001434g/mL, respectively, and the average value was taken as T0.001432 g/mL.
In the above formula: T-Na2The titre of EDTA standard solution to arsenic, g/mL; v-consumption of Na by calibration2Volume of EDTA standard solution, mL.
Sample weighing: two parallel copper arsenic master alloy samples 1#0.2008g and 2#0.2001g were weighed by an electronic balance, and the weighed copper arsenic master alloy samples were placed in a 250mL beaker.
Sample dissolution: 10mL of nitric acid (1+1) was added to the beaker, dissolved by heating on a hot plate, and boiled until the liquid flowed down as an oil on the wall of the beaker to remove the nitrogen oxides.
Oxidation and precipitation: 5 drops of hydrogen peroxide (30%), 5g of solid reagent ammonium chloride, 15mL of magnesium chloride solution (50g/L) were added to a beaker and diluted with water to a volume of about 100 mL. The resulting mixture was neutralized with aqueous ammonia (. rho.0.90 g/mL) to give dark blue copper ammine complex ions, and stirred for 3 minutes in an excess of 15 mL. And standing for 30 minutes.
Separating interference elements: filter through slow filter paper, wash the beaker with ammonia (1+99) and precipitate 12 times. The precipitate was dissolved in portions in the original beaker with 20mL of hot hydrochloric acid (1+1), and the filter paper was washed 3 times with hot water. The filtrate in the beaker was cooled to room temperature.
Titration: neutralizing with ammonia water (rho 0.90g/mL) until the solution is ammoniacal, adding 80mL of water and 10mL of buffer solution to enable the pH value of the solution to be 10-11, adding 5 drops of thioglycollic acid to mask trace copper ions, taking 3 drops of chromium black T-ethanol solution (2g/L) as an indicator, and calibrating Na with known titer2Titration of EDTA standard solution to a pure blue end point and recording Na consumption2Volume of EDTA standard solution. Parallel sample No. 1 consumes Na2EDTA standard solution volume of 31.80mL, parallel sample No. 2 Na consumption2The volume of the EDTA standard solution was 31.60 mL.
And (4) calculating a result: after titration, the percentage content of As is calculated according to the following formula:
in the above formula: T-Na2The titre of EDTA standard solution to arsenic is 0.001432 g/mL; v-consumption of Na in titration2Volume of EDTA standard solution, mL; m-sample weight, g.
Parallel sample 1 #:
parallel sample 2 #:
and taking the average value, the arsenic content in the CuAs23 sample is 22.64 percent and meets the product standard.
The method is characterized by comprising the following steps of (1) verifying the accuracy and precision: in addition, in the invention, an arsenic standard solution is respectively added into a CuAs23 known sample with the arsenic content of 21.03%, the arsenic standard solution is converted into the arsenic content of 2.00%, 5.00% and 10.00% in the sample, the arsenic content is measured in parallel for six times by using the method, and the accuracy and precision of the method are verified through the recovery rate and the standard deviation. The recovery and standard deviation are shown in Table 1.
As can be seen from Table 1, the recovery rate of the sample detected by the method is 99.48-100.54%, and the relative standard deviation is 0.30-0.40%, which shows that the method has high accuracy and good precision when applied to the determination of the As content in the copper-arsenic intermediate alloy.
The above embodiments show that the method of the present invention solves the problem of accurate quantitative analysis of arsenic content in the copper-arsenic intermediate alloy, expands the analysis range of arsenic element in the copper alloy, and fills the gap of the method for analyzing arsenic element in the copper-arsenic intermediate alloy.
TABLE 1
Claims (5)
1. A method for measuring the arsenic content in a copper-arsenic intermediate alloy is characterized by comprising the following steps: the method comprises the following specific steps: preparing a buffer solution, preparing an arsenic standard solution, preparing and calibrating an ethylene diamine tetraacetic acid disodium standard solution, weighing a sample, dissolving the sample, oxidizing and precipitating, separating interference elements, titrating and calculating a result.
2. The method for determining the arsenic content in the copper-arsenic master alloy according to claim 1, wherein the method comprises the following steps:
preparing a buffer solution: weighing 54g of ammonium chloride, dissolving in water, adding 280mL of ammonia water (rho 0.90g/mL), diluting with water to 1000mL, and uniformly mixing for later use;
preparing an arsenic standard solution: putting the arsenic trioxide working reference reagent in an oven for drying for 2 hours at 110 ℃, putting the reagent in a dryer for cooling to room temperature, weighing 1.320g of the arsenic trioxide working reference reagent by using an electronic balance, putting the arsenic trioxide working reference reagent in a beaker, dissolving the arsenic trioxide working reference reagent by using 10mL-20mL of sodium hydroxide solution (100g/L), adding 2 drops of phenolphthalein ethanol solution (10g/L) after complete dissolution, neutralizing the solution by using hydrochloric acid (1+1) until the red color of the solution fades, adding the solution in an excess of 5mL, transferring the solution into a 1000mL volumetric flask, diluting the volumetric flask with water to a specified scale, and uniformly mixing, wherein 1mL of the standard solution contains 0.001g of arsenic.
3. The method for determining the arsenic content in the copper-arsenic master alloy according to claim 1, wherein the method comprises the following steps:
disodium ethylene diamine tetraacetate (Na)2EDTA) preparation and calibration of standard solutions:
preparation: 7.120g of disodium ethylene diamine tetraacetate solid reagent is weighed by an electronic balance, dissolved in 190-200mL hot water, cooled, transferred into a 1000mL volumetric flask, diluted to a designated scale by water and uniformly mixed for later use to prepare a Na2EDTA standard solution with the concentration [ Na2EDTA is approximately equal to 0.019mol/L ];
calibration: weighing 0.200g of pure copper, placing the pure copper in a 250mL beaker, adding 10mL of nitric acid (1+1), heating to dissolve the pure copper, boiling until liquid on the wall of the beaker flows down in an oily state to remove nitrogen oxides, adding 25.00mL of arsenic standard solution, adding 4-6 drops of hydrogen peroxide (30%), 5g of ammonium chloride solid reagent and 15mL of magnesium chloride solution (50g/L), diluting the mixture to about 100mL by using water, neutralizing the mixture by using ammonia water (rho 0.90g/mL) to generate dark blue cuprammonium complex ions, adding 10-15 mL of excessive cuprammonium complex ions, stirring for 3-5 minutes, and standing for 30-30 minutes;
filtering with slow filter paper, washing beaker and precipitate with ammonia water (1+99) for more than 10 times, dissolving precipitate with 20mL hot hydrochloric acid (1+1) in original beaker, washing filter paper with hot water for 3-4 times, and cooling to room temperature;
neutralizing with ammonia water (rho 0.90g/mL) until the solution becomes ammoniacal, adding 80mL of water, 10mL of buffer solution, 5 drops of thioglycolic acid, 2-3 drops of chrome black T-ethanol solution (2g/L), and adding prepared Na2Titrating the EDTA standard solution until the solution is pure blue;
the titer of the Na2EDTA standard solution to arsenic was calculated as follows:
in the above formula: T-Na2The titre of EDTA standard solution to arsenic, g/mL; v-consumption of Na by calibration2Volume of EDTA standard solution, mL.
4. The method for determining the arsenic content in the copper-arsenic master alloy according to claim 1, wherein the method comprises the following steps:
sample weighing: weighing 0.15g-0.25g of a copper-arsenic intermediate alloy sample by using an electronic balance, accurately weighing the sample to 0.0001g, and placing the weighed sample into a 250mL beaker;
sample dissolution: adding 5-15 mL of nitric acid (1+1) into a beaker, placing the beaker on an electric hot plate for heating to dissolve the nitric acid, and boiling until liquid on the wall of the beaker flows down in an oily state to remove nitrogen oxides;
oxidation and precipitation: adding 4-6 drops of hydrogen peroxide (30%), 5g of ammonium chloride solid reagent and 15mL of magnesium chloride solution (50g/L) into a beaker, and diluting with water to 90-100mL of volume; neutralizing with ammonia water (rho 0.90g/mL) until deep blue copper ammonia complex ions are generated, adding 10-15 mL of the copper ammonia complex ions, stirring for 3 minutes, standing for 30 minutes, and converting arsenic elements in the copper-arsenic intermediate alloy into NH4MgAsO4·6H2And (4) precipitating O.
5. The method for determining the arsenic content in the copper-arsenic master alloy according to claim 1, wherein the method comprises the following steps:
separating interference elements: filtering with slow filter paper, washing beaker and precipitate with ammonia water (1+99) for more than 10 times, dissolving precipitate with 20mL of hot hydrochloric acid (1+1) in original beaker, washing filter paper with hot water for 3-4 times, cooling filtrate in beaker to room temperature, separating a large amount of interfering elements such as copper ions and magnesium ions in solution to be measured, and separating NH4MgAsO4·6H2Dissolving the O precipitate into a solution state;
titration: neutralizing with ammonia water (rho 0.90g/mL) until the solution is ammoniacal, adding 80mL water and 10mL buffer solution to make the pH value of the solution be 10-11, adding 5 drops of thioglycolic acid to mask trace copper ions, using 2-3 drops of chrome black T-ethanol solution (2g/L) as indicator, and using a well-calibrated known titration methodDegree of Na2Titration of EDTA standard solution to a pure blue end point and recording Na consumption2Volume of EDTA standard solution;
and (4) calculating a result: after titration, the percentage content of As is calculated according to the following formula:
in the above formula: T-Na2The titre of EDTA standard solution to arsenic, g/mL; v-consumption of Na in titration2Volume of EDTA standard solution, mL; m-sample weight, g.
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