CN113358586B - Novel determination method for trace chloride ion content in copper sulfate solution - Google Patents
Novel determination method for trace chloride ion content in copper sulfate solution Download PDFInfo
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- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 title claims abstract description 73
- 238000000034 method Methods 0.000 title claims abstract description 41
- 229910000365 copper sulfate Inorganic materials 0.000 title claims abstract description 37
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 title claims abstract description 37
- 238000012360 testing method Methods 0.000 claims abstract description 21
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 107
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 78
- 239000000243 solution Substances 0.000 claims description 70
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 52
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 claims description 46
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 24
- 229910017604 nitric acid Inorganic materials 0.000 claims description 24
- 229910001961 silver nitrate Inorganic materials 0.000 claims description 23
- 239000012488 sample solution Substances 0.000 claims description 22
- 239000000523 sample Substances 0.000 claims description 17
- 239000012086 standard solution Substances 0.000 claims description 15
- 238000002835 absorbance Methods 0.000 claims description 13
- 239000008367 deionised water Substances 0.000 claims description 13
- 229910021641 deionized water Inorganic materials 0.000 claims description 13
- 150000002500 ions Chemical class 0.000 claims description 11
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 10
- 238000007865 diluting Methods 0.000 claims description 9
- 238000002156 mixing Methods 0.000 claims description 9
- 238000001816 cooling Methods 0.000 claims description 8
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 7
- OJKANDGLELGDHV-UHFFFAOYSA-N disilver;dioxido(dioxo)chromium Chemical compound [Ag+].[Ag+].[O-][Cr]([O-])(=O)=O OJKANDGLELGDHV-UHFFFAOYSA-N 0.000 claims description 6
- ZXSQEZNORDWBGZ-UHFFFAOYSA-N 1,3-dihydropyrrolo[2,3-b]pyridin-2-one Chemical compound C1=CN=C2NC(=O)CC2=C1 ZXSQEZNORDWBGZ-UHFFFAOYSA-N 0.000 claims description 5
- JKFYKCYQEWQPTM-UHFFFAOYSA-N 2-azaniumyl-2-(4-fluorophenyl)acetate Chemical compound OC(=O)C(N)C1=CC=C(F)C=C1 JKFYKCYQEWQPTM-UHFFFAOYSA-N 0.000 claims description 5
- 229910021612 Silver iodide Inorganic materials 0.000 claims description 5
- 239000003153 chemical reaction reagent Substances 0.000 claims description 5
- ADZWSOLPGZMUMY-UHFFFAOYSA-M silver bromide Chemical compound [Ag]Br ADZWSOLPGZMUMY-UHFFFAOYSA-M 0.000 claims description 5
- 229910001958 silver carbonate Inorganic materials 0.000 claims description 5
- LKZMBDSASOBTPN-UHFFFAOYSA-L silver carbonate Substances [Ag].[O-]C([O-])=O LKZMBDSASOBTPN-UHFFFAOYSA-L 0.000 claims description 5
- 229940045105 silver iodide Drugs 0.000 claims description 5
- XNGYKPINNDWGGF-UHFFFAOYSA-L silver oxalate Chemical compound [Ag+].[Ag+].[O-]C(=O)C([O-])=O XNGYKPINNDWGGF-UHFFFAOYSA-L 0.000 claims description 5
- 229910000161 silver phosphate Inorganic materials 0.000 claims description 5
- FJOLTQXXWSRAIX-UHFFFAOYSA-K silver phosphate Chemical compound [Ag+].[Ag+].[Ag+].[O-]P([O-])([O-])=O FJOLTQXXWSRAIX-UHFFFAOYSA-K 0.000 claims description 5
- 229940019931 silver phosphate Drugs 0.000 claims description 5
- 239000011780 sodium chloride Substances 0.000 claims description 5
- AKHNMLFCWUSKQB-UHFFFAOYSA-L sodium thiosulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=S AKHNMLFCWUSKQB-UHFFFAOYSA-L 0.000 claims description 5
- 235000019345 sodium thiosulphate Nutrition 0.000 claims description 5
- 239000000706 filtrate Substances 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims description 4
- 238000005303 weighing Methods 0.000 claims description 4
- 238000003860 storage Methods 0.000 claims description 3
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 15
- 238000005259 measurement Methods 0.000 description 15
- 150000001450 anions Chemical class 0.000 description 11
- 239000011889 copper foil Substances 0.000 description 7
- 229910021607 Silver chloride Inorganic materials 0.000 description 6
- 230000001154 acute effect Effects 0.000 description 6
- 231100000570 acute poisoning Toxicity 0.000 description 6
- 231100000739 chronic poisoning Toxicity 0.000 description 6
- 238000001514 detection method Methods 0.000 description 6
- 230000008569 process Effects 0.000 description 6
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 description 6
- 238000004448 titration Methods 0.000 description 6
- 229910052802 copper Inorganic materials 0.000 description 5
- 239000010949 copper Substances 0.000 description 5
- 238000007747 plating Methods 0.000 description 5
- -1 silver ions Chemical class 0.000 description 5
- 238000004458 analytical method Methods 0.000 description 4
- 239000002244 precipitate Substances 0.000 description 4
- 239000000498 cooling water Substances 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- GBZANUMDJPCQHY-UHFFFAOYSA-L mercury(ii) thiocyanate Chemical compound [Hg+2].[S-]C#N.[S-]C#N GBZANUMDJPCQHY-UHFFFAOYSA-L 0.000 description 3
- 238000002798 spectrophotometry method Methods 0.000 description 3
- ZFWAHZCOKGWUIT-UHFFFAOYSA-N 1-anilino-3-phenyliminourea Chemical compound C=1C=CC=CC=1N=NC(=O)NNC1=CC=CC=C1 ZFWAHZCOKGWUIT-UHFFFAOYSA-N 0.000 description 2
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- 208000005374 Poisoning Diseases 0.000 description 2
- 230000002378 acidificating effect Effects 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 238000000975 co-precipitation Methods 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 238000011109 contamination Methods 0.000 description 2
- 239000000599 controlled substance Substances 0.000 description 2
- 229910001431 copper ion Inorganic materials 0.000 description 2
- ZMZDMBWJUHKJPS-UHFFFAOYSA-N hydrogen thiocyanate Natural products SC#N ZMZDMBWJUHKJPS-UHFFFAOYSA-N 0.000 description 2
- 238000002347 injection Methods 0.000 description 2
- 239000007924 injection Substances 0.000 description 2
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical compound [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 description 2
- 229910001987 mercury nitrate Inorganic materials 0.000 description 2
- DRXYRSRECMWYAV-UHFFFAOYSA-N nitrooxymercury Chemical compound [Hg+].[O-][N+]([O-])=O DRXYRSRECMWYAV-UHFFFAOYSA-N 0.000 description 2
- 239000002574 poison Substances 0.000 description 2
- 231100000614 poison Toxicity 0.000 description 2
- 231100000572 poisoning Toxicity 0.000 description 2
- 230000000607 poisoning effect Effects 0.000 description 2
- 230000010287 polarization Effects 0.000 description 2
- 238000011002 quantification Methods 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 229910052709 silver Inorganic materials 0.000 description 2
- 239000004332 silver Substances 0.000 description 2
- 239000004575 stone Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 230000009747 swallowing Effects 0.000 description 2
- 235000019605 sweet taste sensations Nutrition 0.000 description 2
- 231100000331 toxic Toxicity 0.000 description 2
- 230000002588 toxic effect Effects 0.000 description 2
- 238000004879 turbidimetry Methods 0.000 description 2
- 230000000007 visual effect Effects 0.000 description 2
- QLOKJRIVRGCVIM-UHFFFAOYSA-N 1-[(4-methylsulfanylphenyl)methyl]piperazine Chemical compound C1=CC(SC)=CC=C1CN1CCNCC1 QLOKJRIVRGCVIM-UHFFFAOYSA-N 0.000 description 1
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 description 1
- DXUPZCASGCUOJL-UHFFFAOYSA-N CO.N#CS Chemical compound CO.N#CS DXUPZCASGCUOJL-UHFFFAOYSA-N 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- 229910021591 Copper(I) chloride Inorganic materials 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 235000005811 Viola adunca Nutrition 0.000 description 1
- 240000009038 Viola odorata Species 0.000 description 1
- 235000013487 Viola odorata Nutrition 0.000 description 1
- 235000002254 Viola papilionacea Nutrition 0.000 description 1
- 230000002159 abnormal effect Effects 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000003213 activating effect Effects 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- HUTDDBSSHVOYJR-UHFFFAOYSA-H bis[(2-oxo-1,3,2$l^{5},4$l^{2}-dioxaphosphaplumbetan-2-yl)oxy]lead Chemical compound [Pb+2].[Pb+2].[Pb+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O HUTDDBSSHVOYJR-UHFFFAOYSA-H 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 239000011449 brick Substances 0.000 description 1
- 125000002091 cationic group Chemical group 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 150000001805 chlorine compounds Chemical class 0.000 description 1
- RCTYPNKXASFOBE-UHFFFAOYSA-M chloromercury Chemical compound [Hg]Cl RCTYPNKXASFOBE-UHFFFAOYSA-M 0.000 description 1
- ZCDOYSPFYFSLEW-UHFFFAOYSA-N chromate(2-) Chemical compound [O-][Cr]([O-])(=O)=O ZCDOYSPFYFSLEW-UHFFFAOYSA-N 0.000 description 1
- 238000004587 chromatography analysis Methods 0.000 description 1
- KRVSOGSZCMJSLX-UHFFFAOYSA-L chromic acid Substances O[Cr](O)(=O)=O KRVSOGSZCMJSLX-UHFFFAOYSA-L 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 235000009508 confectionery Nutrition 0.000 description 1
- OXBLHERUFWYNTN-UHFFFAOYSA-M copper(I) chloride Chemical compound [Cu]Cl OXBLHERUFWYNTN-UHFFFAOYSA-M 0.000 description 1
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 229940045803 cuprous chloride Drugs 0.000 description 1
- 238000004042 decolorization Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 239000003480 eluent Substances 0.000 description 1
- 230000032050 esterification Effects 0.000 description 1
- 238000005886 esterification reaction Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- AWJWCTOOIBYHON-UHFFFAOYSA-N furo[3,4-b]pyrazine-5,7-dione Chemical compound C1=CN=C2C(=O)OC(=O)C2=N1 AWJWCTOOIBYHON-UHFFFAOYSA-N 0.000 description 1
- 238000007429 general method Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 230000005764 inhibitory process Effects 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 238000004255 ion exchange chromatography Methods 0.000 description 1
- 239000003456 ion exchange resin Substances 0.000 description 1
- 229920003303 ion-exchange polymer Polymers 0.000 description 1
- SUBFIBLJQMMKBK-UHFFFAOYSA-K iron(3+);trithiocyanate Chemical compound [Fe+3].[S-]C#N.[S-]C#N.[S-]C#N SUBFIBLJQMMKBK-UHFFFAOYSA-K 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
- BQPIGGFYSBELGY-UHFFFAOYSA-N mercury(2+) Chemical compound [Hg+2] BQPIGGFYSBELGY-UHFFFAOYSA-N 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000008239 natural water Substances 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 230000009965 odorless effect Effects 0.000 description 1
- 239000006259 organic additive Substances 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 230000008092 positive effect Effects 0.000 description 1
- 238000003918 potentiometric titration Methods 0.000 description 1
- 238000004094 preconcentration Methods 0.000 description 1
- 238000004451 qualitative analysis Methods 0.000 description 1
- 238000004445 quantitative analysis Methods 0.000 description 1
- 230000027756 respiratory electron transport chain Effects 0.000 description 1
- 230000000717 retained effect Effects 0.000 description 1
- 238000005070 sampling Methods 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
Classifications
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- 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
- G01N21/17—Systems in which incident light is modified in accordance with the properties of the material investigated
- G01N21/25—Colour; Spectral properties, i.e. comparison of effect of material on the light at two or more different wavelengths or wavelength bands
- G01N21/31—Investigating relative effect of material at wavelengths characteristic of specific elements or molecules, e.g. atomic absorption spectrometry
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D21/00—Processes for servicing or operating cells for electrolytic coating
- C25D21/12—Process control or regulation
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N1/00—Sampling; Preparing specimens for investigation
- G01N1/28—Preparing specimens for investigation including physical details of (bio-)chemical methods covered elsewhere, e.g. G01N33/50, C12Q
- G01N1/38—Diluting, dispersing or mixing samples
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- Chemical & Material Sciences (AREA)
- Physics & Mathematics (AREA)
- Pathology (AREA)
- Engineering & Computer Science (AREA)
- Health & Medical Sciences (AREA)
- Analytical Chemistry (AREA)
- Biochemistry (AREA)
- General Health & Medical Sciences (AREA)
- General Physics & Mathematics (AREA)
- Immunology (AREA)
- Spectroscopy & Molecular Physics (AREA)
- Life Sciences & Earth Sciences (AREA)
- Automation & Control Theory (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Materials Engineering (AREA)
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- Investigating Or Analyzing Non-Biological Materials By The Use Of Chemical Means (AREA)
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Abstract
The invention belongs to the technical field of chloride ion determination, and in particular relates to a novel determination method for the content of trace chloride ions in a copper sulfate solution. The novel method for measuring the content of the trace chloride ions in the copper sulfate solution is simple to operate, has higher precision than the existing measuring method, performs anti-interference treatment before testing, and ensures the measuring accuracy of the content of the chloride ions.
Description
Technical Field
The invention relates to a novel method for measuring the content of trace chloride ions in a copper sulfate solution. Belonging to the technical field of chloridion determination.
Background
Chloride ions are an indispensable substance in acidic copper plating solutions, and are usually added to copper plating solutions in the form of sodium chloride or hydrochloric acid. The main functions of chloride ions are: (1) The copper sulfate can play an activating role in the copper sulfate solution and serve as an electron transfer bridge between copper ions and metallic copper; (2) The appropriate amount of chloride ions can reduce cathode polarization and eliminate plating stripes in a high current density region; interacting with organic additive to realize the brightness and leveling of the coating; (3) The anode activity is improved, a layer of uniform anode film is formed on the surface of the anode, the loss of noble metal is reduced, the anode is protected, and chloride ions can enlarge cathode polarization and inhibit abnormal growth of metal so as to improve the elastic strength, hardness and smooth feel of the copper foil; (4) Effectively eliminating or reducing internal stress of the cathode deposit in a proper range; (5) The peak value of the surface of the copper foil can be increased, and the crystal grains of the copper deposit can be fine and compact.
Meanwhile, chloride ions can influence the surface morphology, structure, microhardness, lattice orientation and internal stress of the plating layer.
When the chloride ion content is too low: the surface of the copper foil is easy to show branch-shaped lines, and the flatness is reduced, so that a plating layer with high leveling performance and good brightness is not obtained.
When the chloride ion content is too high: (1) The roughness phenomenon can occur on the coating, so that the copper foil is fogged in the low current density region and burnt in the high current density region, the cathode roll surface is seriously oxidized, the surface of the copper foil is blossomed, and the glossiness is reduced. (2) The effect of the organic matters is weakened, so that the effect of the organic matters is weakened. Copper chloride generated on the surface of the cathode can obstruct copper ion adsorption, influence the surface diffusion of adsorbed copper atoms, cause the formation of insoluble cuprous chloride, be mixed among grain boundaries, and enable the copper foil to be rough and long in copper thorns. (3) the equipment corrosion speed is increased.
Therefore, the method has the advantages that the concentration of the chloride ions is reasonably controlled in the production process, the method has positive effects on producing high-quality high-performance electrolytic copper foil, and the accuracy of analysis and detection of the chloride ions is improved.
Disclosure of Invention
The invention provides a novel method for determining the content of trace chloride ions in a copper sulfate solution, which is simple to operate, has higher precision than the prior measuring method, performs anti-interference treatment before testing, ensures the accuracy of determining the content of the chloride ions, and solves the problems in the prior art.
In order to solve the technical problems, the technical scheme of the invention is as follows:
a novel method for measuring the content of trace chloride ions in a copper sulfate solution comprises the following steps:
step one: nitric acid and dechlorinated ion water are mixed according to a volume ratio of 1:1, mixing to prepare a nitric acid solution;
Glycerol or glycol and dechlorinated ion water are mixed according to a volume ratio of 1:5, mixing to prepare glycerol solution or ethylene glycol solution;
Preferably, glycerol is selected to be more suitable, and ethylene glycol is toxic and harmful to swallowing and can cause death. The ethylene glycol acute and chronic poisoning is not a case which is fatal in China, so the ethylene glycol acute and chronic poisoning is harmful, but the ethylene glycol acute and chronic poisoning is not classified as a controlled drug by the country. Based on the data published by U.S. poison control centers, there have been cases of death due to glycol poisoning events. Ethylene glycol has a sweet taste, which is its greatest point of temptation, and also its greatest point of mortality. The price of the ethylene glycol is higher than that of the glycerol, and the glycerol has higher viscosity, so that the ethylene glycol can be diluted for use in the detection and use process, and the cost is further reduced.
Silver nitrate and dechlorinated ion water are mixed according to the mass ratio of 1:100 to prepare 1 percent silver nitrate solution, mixing and then placing the mixture into a brown bottle for storage;
step two: accurately weighing 0.1648g of sodium chloride which is burnt to constant quality at 500-600 ℃, and fixing the volume in a 1000mL volumetric flask by using deionized water to prepare 0.1mg/mL chloride ion standard solution;
Step three: taking a copper sulfate sample solution in a colorimetric tube, sequentially adding a nitric acid solution, a glycerol solution or an ethylene glycol solution and a silver nitrate solution, shaking uniformly, keeping the temperature in a water bath at 60 ℃ for 10min, taking out, cooling to room temperature, diluting to a scale with deionized water, shaking uniformly, testing the absorbance of the sample solution at the wavelength of 550nm by using a 1cm cuvette, and simultaneously performing a sample blank test and a reagent blank test;
Step four: respectively adding chloride ion standard solution 0, 0.1mL, 2.0mL, 3.0mL, 4.0mL and 5.0mL into 6 colorimetric tubes, respectively sequentially adding nitric acid solution, glycerol solution or ethylene glycol solution and silver nitrate solution, shaking uniformly, taking out after keeping constant temperature in a water bath at 60 ℃ for 10min, cooling to room temperature, diluting to a scale with deionized water, shaking uniformly, testing absorbance with a 1cm cuvette at a wavelength of 550nm, drawing a standard working curve by taking the chloride ion content in filtrate containing the chloride ion working standard solution as a horizontal coordinate and the absorbance as a vertical coordinate, and drawing the standard curve;
step five: and (5) checking the mass m of the chloride ions on a standard curve, and calculating the mass concentration of the chloride ions.
In the third step, the volume ratio of the copper sulfate sample solution, the nitric acid solution, the glycerol solution or the ethylene glycol solution to the silver nitrate solution is 10:2:10:1.
And thirdly, carrying out anti-interference treatment on the copper sulfate sample solution.
The anti-interference treatment comprises the steps of taking a copper sulfate sample solution in a colorimetric tube, and adding sodium thiosulfate to neutralize silver bromide and silver iodide.
The anti-interference treatment comprises the steps of taking a copper sulfate sample solution in a colorimetric tube, and adding a second part of nitric acid to neutralize silver carbonate, silver chromate, silver phosphate and silver oxalate.
At present, the following eight methods are generally adopted for detection in China:
1. molar titration: detection range: 3-150mg/L, principle of measurement: when potassium chromate is used as an indicator and silver nitrate is used for titrating chloride, as the solubility of silver chloride is smaller than that of silver chromate, silver ions in the added silver nitrate solution are completely precipitated by silver chloride firstly and then are combined with chromic acid root to generate brick red precipitate, so that the titration end point of chloride ions is indicated. The application range is as follows: the method is suitable for measuring the chloride ion content of natural stone, circulating cooling water and boiler water taking softened water as makeup water.
2. Mercury nitrate titration: measurement range: 5-150ppm, principle of measurement: the acidified sample (ph=3.0-3.5) was titrated with mercury nitrate to form poorly dissociable mercury chloride with chloride, and when titrated to endpoint, the excess mercury ion and the diphenyl carbazone formed a blue-violet mercury complex of diphenyl carbazone indicating endpoint. The application range is as follows: the method is suitable for measuring the chloride ion content in natural water, boiler water and cooling water. The cloudiness has a darker color and is measured by filtration or by sampling after decolorization.
3. Potentiometric titration: measurement range: 5-1000ppm, principle of measurement: the potential titration method is to use chlorine electrode as indication electrode, glass electrode as reference, silver nitrate standard solution for titration, voltmeter to measure the potential change between two electrodes, and the instrument reading is the titration end point when the potential change is maximum in the process of constantly adding small amount of silver nitrate. The application range is as follows: the method is suitable for measuring the chloride ion content of natural stone, circulating cooling water and boiler water taking softened water as makeup water.
4. Mercury thiocyanate spectrophotometry: measurement range: 1.0-100ppm. The measurement principle is as follows: adding mercury thiocyanate into the sample solution, completely replacing thiocyanate radical in the mercury thiocyanate by chloride ions in the sample, reacting the replaced thiocyanate radical with ferric nitrate to generate ferric thiocyanate, displaying red, and measuring absorbance of the colored solution at the wavelength of 450 nm. The application range is as follows: the method is suitable for measuring the chloride ion content in furnace water.
5. Coprecipitation enrichment spectrophotometry: measurement range: 10.0-100ug/L, principle of measurement: and (3) taking lead phosphate precipitate as a carrier, carrying out high-speed centrifugal separation on the coprecipitation enriched trace chloride, completely dissolving the precipitate by using an iron nitrate-perchloric acid solution, adding a mercuric thiocyanate-methanol solution to display orange red, and indirectly measuring the trace chloride in water by using a spectrophotometry. The application range is as follows: is suitable for measuring the chloride ion content in desalted water and boiler feed water.
6. Visual turbidimetry (chloride determination general method): measurement range: 1-4ppm. The measurement principle is as follows: the chloride ions and silver ions in the nitric acid medium generate indissolvable silver chloride. When the chloride ion content is low, silver chloride is in suspension in a certain period of time to cause turbidity of the solution, and the method can be used for measuring chloride by a visual turbidimetry method. The application range is as follows: the method is suitable for the determination and detection range of trace chlorides in chemical reagents.
7. Ion chromatography: lower limit of measurement 0.1ppm, principle of measurement: the principle of ion exchange is utilized to continuously carry out qualitative and quantitative analysis on various anions. The ion exchange resins through which the sample flows are separated from each other based on the relative affinities of the anions to be tested for the low capacity strongly basic anion resins (separation columns). The anions that are separated are converted into highly conductive acid-type ions when flowing through a strongly acidic cationic resin (inhibition column), and the anions that are converted into the corresponding acid-type are measured with a conductivity detector, compared with a standard, and are characterized according to retention time, peak height or peak area quantification. The application range is as follows: the method is suitable for measuring anions in water samples such as boiler feed water, condensed water, steam, boiler water and the like. Determining trace ug/L anions in water and steam by using a large-volume sample quantitative ring, such as 1mL direct injection or concentration column pre-concentration water sample; sample introduction methods using small volume sample quantification rings, such as 10uL direct or water dilution; can be used for measuring trace mg/L anions in water. Notice that: contamination is a serious problem when performing ppb or less analyses, and care must be taken to avoid contamination during all parts of the test. As with other chromatography, when the concentration of a component in a sample is very high, peaks corresponding to very large peaks can appear in the spectrum to mask other substances and cause interference. This interference can generally be reduced by properly diluting the sample according to the concentration of other anions. When the concentration column is used, certain high-concentration strong retained anions can play a role of eluent, weak anions can be eluted, and the quantitative loop of the large-volume sample is suitable for direct sample injection under the condition.
The invention relates to a novel determination method for the content of trace chloride ions in a copper sulfate solution, which comprises the following steps: 0.1-500ppm, silver chloride white precipitate is generated by chloridion and silver nitrate, ethylene glycol is added to ensure that the silver chloride cannot be rapidly precipitated, and the operation is simple and the precision is higher than that of the 7 methods.
If bromide ions, iodide ions, carbonate ions, chromate ions, phosphate ions, oxalate ions and the like exist in the sample, the test of the chloride ions can be influenced by interference, and the anti-interference treatment is carried out before the test, so that the accuracy of measuring the content of the chloride ions is ensured.
Drawings
In order to more clearly illustrate the embodiments of the invention or the technical solutions of the prior art, the drawings which are used in the description of the embodiments or the prior art will be briefly described, it being obvious that the drawings in the description below are only some embodiments of the invention, and that other drawings can be obtained according to these drawings without inventive faculty for a person skilled in the art.
FIG. 1 is a comparative diagram of a novel method for determining the trace chloride ion content of a copper sulfate solution according to the present invention.
Detailed Description
The following describes the embodiments of the present invention further with reference to the drawings. The description of these embodiments is provided to assist understanding of the present invention, but is not intended to limit the present invention. In addition, the technical features of the embodiments of the present invention described below may be combined with each other as long as they do not collide with each other.
A novel method for measuring the content of trace chloride ions in a copper sulfate solution comprises the following steps:
step one: nitric acid and dechlorinated ion water are mixed according to a volume ratio of 1:1, mixing to prepare a nitric acid solution;
Glycerol or glycol and dechlorinated ion water are mixed according to a volume ratio of 1:5, mixing to prepare glycerol solution or ethylene glycol solution;
Preferably, glycerol is selected to be more suitable, and ethylene glycol is toxic and harmful to swallowing and can cause death. The ethylene glycol acute and chronic poisoning is not a case which is fatal in China, so the ethylene glycol acute and chronic poisoning is harmful, but the ethylene glycol acute and chronic poisoning is not classified as a controlled drug by the country. Based on the data published by U.S. poison control centers, there have been cases of death due to glycol poisoning events. Ethylene glycol has a sweet taste, which is its greatest point of temptation, and also its greatest point of mortality. The price of the ethylene glycol is higher than that of the glycerol, and the glycerol has higher viscosity, so that the ethylene glycol can be diluted for use in the detection and use process, and the cost is further reduced.
Silver nitrate and dechlorinated ion water are mixed according to the mass ratio of 1:100 to prepare 1 percent silver nitrate solution, mixing and then placing the mixture into a brown bottle for storage;
step two: accurately weighing 0.1648g of sodium chloride which is burnt to constant quality at 500-600 ℃, and fixing the volume in a 1000mL volumetric flask by using deionized water to prepare 0.1mg/mL chloride ion standard solution;
step three: taking a copper sulfate sample solution in a colorimetric tube, sequentially adding a nitric acid solution, a glycerol solution or an ethylene glycol solution and a silver nitrate solution, shaking uniformly, keeping the temperature in a water bath at 60 ℃ for 10min, taking out, cooling to room temperature, diluting to a scale with deionized water, shaking uniformly, testing the absorbance of the sample solution at the wavelength of 550nm by using a 1cm cuvette, and simultaneously performing a sample blank test and a reagent blank test; in the third step, the volume ratio of the copper sulfate sample solution, the nitric acid solution, the glycerol solution or the ethylene glycol solution to the silver nitrate solution is 10:2:10:1.
Step four: respectively adding chloride ion standard solution 0, 0.1mL, 2.0mL, 3.0mL, 4.0mL and 5.0mL into 6 colorimetric tubes, respectively sequentially adding nitric acid solution, glycerol solution or ethylene glycol solution and silver nitrate solution, shaking uniformly, taking out after keeping constant temperature in a water bath at 60 ℃ for 10min, cooling to room temperature, diluting to a scale with deionized water, shaking uniformly, testing absorbance with a 1cm cuvette at a wavelength of 550nm, drawing a standard working curve by taking the chloride ion content in filtrate containing the chloride ion working standard solution as a horizontal coordinate and the absorbance as a vertical coordinate, and drawing the standard curve;
step five: and (5) checking the mass m of the chloride ions on a standard curve, and calculating the mass concentration of the chloride ions.
And thirdly, carrying out anti-interference treatment on the copper sulfate sample solution. The anti-interference treatment comprises the steps of taking a copper sulfate sample solution in a colorimetric tube, and adding sodium thiosulfate to neutralize silver bromide and silver iodide. The anti-interference treatment comprises the steps of taking a copper sulfate sample solution in a colorimetric tube, and adding a second part of nitric acid to neutralize silver carbonate, silver chromate, silver phosphate and silver oxalate.
Example 1:
a novel method for measuring the content of trace chloride ions in a copper sulfate solution comprises the following steps:
step one: 100mL of nitric acid is mixed with 100mL of dechlorinated water;
100mL of ethylene glycol was mixed with 500mL of deionized water
1G of silver nitrate is weighed and dissolved in 100mL of dechlorinated ion water, and the mixture is stored in a brown bottle;
step two: accurately weighing 0.1648g of sodium chloride which is burnt to constant quality at 500-600 ℃, and fixing the volume in a 1000mL volumetric flask by using deionized water to prepare 0.1mg/mL chloride ion standard solution;
Step three: taking 10mL of copper sulfate sample liquid in a 25mL colorimetric tube, sequentially adding 2mL of nitric acid, 10mL of ethylene glycol and 1mL of 1% silver nitrate, shaking uniformly, taking out after keeping constant temperature in a water bath at 60 ℃ for 10min, cooling to room temperature, diluting to a scale with deionized water, shaking uniformly, testing absorbance by using a 1cm cuvette at a wavelength of 550nm, and simultaneously performing a sample blank test and a reagent blank test;
Step four: respectively adding chloride ion standard solution 0, 0.1mL, 2.0mL, 3.0mL, 4.0mL and 5.0mL into 6 colorimetric tubes, respectively sequentially adding 2mL of nitric acid, 10mL of ethylene glycol and 1mL of 1% silver nitrate, shaking uniformly, taking out after keeping constant temperature in a water bath at 60 ℃ for 10min, cooling to room temperature, diluting to a scale with deionized water, shaking uniformly, testing absorbance with a 1cm cuvette at a wavelength of 550nm, drawing a standard working curve by taking the chloride ion content in filtrate containing chloride ion working standard solution as a horizontal coordinate and the absorbance as a vertical coordinate, and drawing the standard curve;
step five: and (5) checking the mass m of the chloride ions on a standard curve, and calculating the mass concentration of the chloride ions.
Example 2:
unlike example 1, ethylene glycol was changed to glycerol. Glycerol is a colorless odorless sweet viscous liquid with a boiling point of 290 ℃, strong water absorption, alcohol-like general property, and can react with metallic sodium to generate hydrogen. Esterification, ether formation, etc. may also occur.
Example 3:
unlike example 2, example 3 was subjected to an anti-interference treatment, i.e., a copper sulfate sample solution was taken in a cuvette, and sodium thiosulfate was added to neutralize silver bromide and silver iodide.
Example 4:
Unlike example 2, example 4 was subjected to an anti-interference treatment, i.e., a copper sulfate sample solution was taken in a cuvette, and a second portion of nitric acid was added to neutralize the silver carbonate, silver chromate, silver phosphate and silver oxalate.
Example 5:
unlike example 2, example 4 was subjected to an anti-interference treatment by taking a copper sulfate sample solution into a cuvette, and adding sodium thiosulfate and a second nitric acid to neutralize silver bromide, silver iodide, silver carbonate, silver chromate, silver phosphate and silver oxalate, respectively.
Experimental data 1:
A group of 3.0mL of a chloride ion standard solution having a concentration of 0.1mg/mL was used for 6 groups of measurement according to the two analytical methods of example 1 and example 2, respectively.
| Numbering device | 1# | 2# | 3# | 4# | 5# | 6# | Average value of | Standard deviation of | Relative deviation% |
| Glycol process | 3.02 | 3.03 | 3.02 | 3.04 | 2.97 | 2.97 | 3.0083 | 0.02223 | 0.74 |
| Glycerol process | 3.01 | 2.99 | 3.00 | 3.02 | 2.98 | 3.02 | 3.0033 | 0.01833 | 0.61 |
Compared with the glycerol method, the glycol method has basically similar accuracy, and can completely meet the analysis requirement. However, glycerol is nontoxic, is safer to human health in the use process, has better operability in medicine management, and effectively reduces the enterprise cost.
Experimental data 2:
A set of 3.0mL of chloride ion standard solutions with a concentration of 0.1mg/mL was measured according to examples 1 to 5, and 6 sets of measurements were performed in each of examples 1 to 5, and the 6 sets of data were added to obtain leveling values.
The concentration of the chloride ions obtained by the embodiment of the anti-interference treatment is closer to the concentration of the chloride ion reference liquid, closer to the standard value, higher in precision and higher in accuracy.
The embodiments of the present invention have been described in detail above with reference to the accompanying drawings, but the present invention is not limited to the described embodiments. It will be apparent to those skilled in the art that various changes, modifications, substitutions and alterations can be made to these embodiments without departing from the principles and spirit of the invention, and yet fall within the scope of the invention.
Claims (5)
1. A novel method for measuring the content of trace chloride ions in a copper sulfate solution is characterized by comprising the following steps: the method comprises the following steps:
step one: nitric acid and dechlorinated ion water are mixed according to a volume ratio of 1:1, mixing to prepare a nitric acid solution;
Glycerol or glycol and dechlorinated ion water are mixed according to a volume ratio of 1:5, mixing to prepare glycerol solution or ethylene glycol solution;
silver nitrate and dechlorinated ion water are mixed according to the mass ratio of 1:100 to prepare 1 percent silver nitrate solution, mixing and then placing the mixture into a brown bottle for storage;
step two: accurately weighing 0.1648g of sodium chloride which is burnt to constant quality at 500-600 ℃, and fixing the volume in a 1000mL volumetric flask by using deionized water to prepare 0.1mg/mL chloride ion standard solution;
Step three: taking a copper sulfate sample solution in a colorimetric tube, sequentially adding a nitric acid solution, a glycerol solution or an ethylene glycol solution and a silver nitrate solution, shaking uniformly, keeping the temperature in a water bath at 60 ℃ for 10min, taking out, cooling to room temperature, diluting to a scale with deionized water, shaking uniformly, testing the absorbance of the sample solution at the wavelength of 550nm by using a 1cm cuvette, and simultaneously performing a sample blank test and a reagent blank test;
Step four: respectively adding chloride ion standard solution 0, 0.1mL, 2.0mL, 3.0mL, 4.0mL and 5.0mL into 6 colorimetric tubes, respectively sequentially adding nitric acid solution, glycerol solution or ethylene glycol solution and silver nitrate solution, shaking uniformly, taking out after keeping constant temperature in a water bath at 60 ℃ for 10min, cooling to room temperature, diluting to a scale with deionized water, shaking uniformly, testing absorbance with a 1cm cuvette at a wavelength of 550nm, drawing a standard working curve by taking the chloride ion content in filtrate containing the chloride ion working standard solution as a horizontal coordinate and the absorbance as a vertical coordinate, and drawing the standard curve;
step five: and (5) checking the mass m of the chloride ions on a standard curve, and calculating the mass concentration of the chloride ions.
2. The novel method for determining the content of trace chloride ions in a copper sulfate solution according to claim 1, wherein the method comprises the following steps: in the third step, the volume ratio of the copper sulfate sample solution, the nitric acid solution, the glycerol solution or the ethylene glycol solution to the silver nitrate solution is 10:2:10:1.
3. The novel method for determining the content of trace chloride ions in a copper sulfate solution according to claim 1 or 2, which is characterized in that: and thirdly, carrying out anti-interference treatment on the copper sulfate sample solution.
4. A novel method for determining the trace chloride ion content in a copper sulfate solution according to claim 3, wherein: the anti-interference treatment comprises the steps of taking a copper sulfate sample solution in a colorimetric tube, and adding sodium thiosulfate to neutralize silver bromide and silver iodide.
5. A novel method for determining the trace chloride ion content in a copper sulfate solution according to claim 3, wherein: the anti-interference treatment comprises the steps of taking a copper sulfate sample solution in a colorimetric tube, and adding a second part of nitric acid to neutralize silver carbonate, silver chromate, silver phosphate and silver oxalate.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106706613A (en) * | 2015-11-17 | 2017-05-24 | 内蒙古鄂尔多斯电力冶金股份有限公司氯碱化工分公司 | Analytic method for content of phosphorus in dried calcium carbide dregs |
| CN109781634A (en) * | 2018-12-20 | 2019-05-21 | 九江德福科技股份有限公司 | A kind of measuring method of chloride ion content |
| WO2020233150A1 (en) * | 2019-05-22 | 2020-11-26 | 南京市产品质量监督检验院 | Method for calculating content of sodium chloride in edible salt |
| CN112345479A (en) * | 2020-11-20 | 2021-02-09 | 格林美（江苏）钴业股份有限公司 | Method for measuring chloride ion content in cobaltosic oxide by using double-beam turbidimetry |
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN109781634A (en) * | 2018-12-20 | 2019-05-21 | 九江德福科技股份有限公司 | A kind of measuring method of chloride ion content |
| WO2020233150A1 (en) * | 2019-05-22 | 2020-11-26 | 南京市产品质量监督检验院 | Method for calculating content of sodium chloride in edible salt |
| CN112345479A (en) * | 2020-11-20 | 2021-02-09 | 格林美（江苏）钴业股份有限公司 | Method for measuring chloride ion content in cobaltosic oxide by using double-beam turbidimetry |
Non-Patent Citations (1)
| Title |
|---|
| 酸性镀铜溶液中氯离子分析方法研究;索春艳;张彦峰;代凤双;;印制电路信息;20140910(第09期);全文 * |
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