CN112611749A - Method for detecting content of ammonium citrate in liquid - Google Patents
Method for detecting content of ammonium citrate in liquid Download PDFInfo
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- CN112611749A CN112611749A CN202011188214.8A CN202011188214A CN112611749A CN 112611749 A CN112611749 A CN 112611749A CN 202011188214 A CN202011188214 A CN 202011188214A CN 112611749 A CN112611749 A CN 112611749A
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- 239000007788 liquid Substances 0.000 title claims abstract description 88
- 238000000034 method Methods 0.000 title claims abstract description 55
- YWYZEGXAUVWDED-UHFFFAOYSA-N triammonium citrate Chemical compound [NH4+].[NH4+].[NH4+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O YWYZEGXAUVWDED-UHFFFAOYSA-N 0.000 title claims abstract description 39
- 238000004448 titration Methods 0.000 claims abstract description 51
- 239000000126 substance Substances 0.000 claims abstract description 21
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 claims abstract description 20
- 229910001431 copper ion Inorganic materials 0.000 claims abstract description 19
- 239000007800 oxidant agent Substances 0.000 claims abstract description 11
- 230000001590 oxidative effect Effects 0.000 claims abstract description 11
- 239000012535 impurity Substances 0.000 claims abstract description 9
- 238000000605 extraction Methods 0.000 claims abstract description 6
- 239000000243 solution Substances 0.000 claims description 104
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 60
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 36
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 36
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 33
- NLKNQRATVPKPDG-UHFFFAOYSA-M potassium iodide Chemical compound [K+].[I-] NLKNQRATVPKPDG-UHFFFAOYSA-M 0.000 claims description 27
- 229910052782 aluminium Inorganic materials 0.000 claims description 25
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 25
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical class [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 18
- 229910001868 water Inorganic materials 0.000 claims description 17
- 239000012153 distilled water Substances 0.000 claims description 16
- AKHNMLFCWUSKQB-UHFFFAOYSA-L sodium thiosulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=S AKHNMLFCWUSKQB-UHFFFAOYSA-L 0.000 claims description 16
- 235000019345 sodium thiosulphate Nutrition 0.000 claims description 16
- 239000002904 solvent Substances 0.000 claims description 16
- 239000012286 potassium permanganate Substances 0.000 claims description 15
- 239000011259 mixed solution Substances 0.000 claims description 12
- 229920002472 Starch Polymers 0.000 claims description 11
- 239000008107 starch Substances 0.000 claims description 11
- 235000019698 starch Nutrition 0.000 claims description 11
- SQQMAOCOWKFBNP-UHFFFAOYSA-L manganese(II) sulfate Chemical compound [Mn+2].[O-]S([O-])(=O)=O SQQMAOCOWKFBNP-UHFFFAOYSA-L 0.000 claims description 9
- 239000004215 Carbon black (E152) Substances 0.000 claims description 8
- JBTWLSYIZRCDFO-UHFFFAOYSA-N ethyl methyl carbonate Chemical compound CCOC(=O)OC JBTWLSYIZRCDFO-UHFFFAOYSA-N 0.000 claims description 8
- 238000001914 filtration Methods 0.000 claims description 8
- 229930195733 hydrocarbon Natural products 0.000 claims description 8
- 150000002430 hydrocarbons Chemical class 0.000 claims description 8
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 8
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 claims description 4
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 claims description 4
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 claims description 4
- KXKVLQRXCPHEJC-UHFFFAOYSA-N acetic acid trimethyl ester Natural products COC(C)=O KXKVLQRXCPHEJC-UHFFFAOYSA-N 0.000 claims description 4
- 239000008346 aqueous phase Substances 0.000 claims description 4
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 claims description 4
- 239000012071 phase Substances 0.000 claims description 3
- 239000012086 standard solution Substances 0.000 claims description 3
- GJRQTCIYDGXPES-UHFFFAOYSA-N iso-butyl acetate Natural products CC(C)COC(C)=O GJRQTCIYDGXPES-UHFFFAOYSA-N 0.000 claims description 2
- FGKJLKRYENPLQH-UHFFFAOYSA-M isocaproate Chemical compound CC(C)CCC([O-])=O FGKJLKRYENPLQH-UHFFFAOYSA-M 0.000 claims description 2
- OQAGVSWESNCJJT-UHFFFAOYSA-N isovaleric acid methyl ester Natural products COC(=O)CC(C)C OQAGVSWESNCJJT-UHFFFAOYSA-N 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- 238000001514 detection method Methods 0.000 abstract description 70
- 230000007547 defect Effects 0.000 abstract description 3
- 238000006243 chemical reaction Methods 0.000 description 13
- 230000000052 comparative effect Effects 0.000 description 13
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 12
- 238000010438 heat treatment Methods 0.000 description 12
- 238000007747 plating Methods 0.000 description 9
- 239000010410 layer Substances 0.000 description 8
- 239000010949 copper Substances 0.000 description 7
- 239000000203 mixture Substances 0.000 description 7
- 239000003960 organic solvent Substances 0.000 description 7
- 239000007787 solid Substances 0.000 description 5
- 238000001816 cooling Methods 0.000 description 4
- 239000012488 sample solution Substances 0.000 description 4
- 239000011780 sodium chloride Substances 0.000 description 4
- 235000002639 sodium chloride Nutrition 0.000 description 4
- 239000002699 waste material Substances 0.000 description 4
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 3
- 238000004458 analytical method Methods 0.000 description 3
- 238000009713 electroplating Methods 0.000 description 3
- 238000005265 energy consumption Methods 0.000 description 3
- 239000011521 glass Substances 0.000 description 3
- 150000002500 ions Chemical class 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 229910019142 PO4 Inorganic materials 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 238000004364 calculation method Methods 0.000 description 2
- 238000005119 centrifugation Methods 0.000 description 2
- 238000004140 cleaning Methods 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 238000010790 dilution Methods 0.000 description 2
- 239000012895 dilution Substances 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 239000003337 fertilizer Substances 0.000 description 2
- 239000008235 industrial water Substances 0.000 description 2
- 230000002452 interceptive effect Effects 0.000 description 2
- 239000012046 mixed solvent Substances 0.000 description 2
- -1 permeation aid Substances 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 2
- 239000010452 phosphate Substances 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 239000000523 sample Substances 0.000 description 2
- 238000010998 test method Methods 0.000 description 2
- 239000012085 test solution Substances 0.000 description 2
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 1
- IOVCWXUNBOPUCH-UHFFFAOYSA-M Nitrite anion Chemical compound [O-]N=O IOVCWXUNBOPUCH-UHFFFAOYSA-M 0.000 description 1
- 208000012322 Raynaud phenomenon Diseases 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-N Sulfurous acid Chemical compound OS(O)=O LSNNMFCWUKXFEE-UHFFFAOYSA-N 0.000 description 1
- 239000003929 acidic solution Substances 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 239000000872 buffer Substances 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 239000008139 complexing agent Substances 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 239000003599 detergent Substances 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 239000003995 emulsifying agent Substances 0.000 description 1
- 239000003759 ester based solvent Substances 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 235000013305 food Nutrition 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 239000010842 industrial wastewater Substances 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 239000000543 intermediate Substances 0.000 description 1
- PNDPGZBMCMUPRI-UHFFFAOYSA-N iodine Chemical compound II PNDPGZBMCMUPRI-UHFFFAOYSA-N 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- 238000004811 liquid chromatography Methods 0.000 description 1
- 238000003760 magnetic stirring Methods 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 239000011572 manganese Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000002906 medical waste Substances 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000006996 mental state Effects 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 210000000056 organ Anatomy 0.000 description 1
- 239000012044 organic layer Substances 0.000 description 1
- CMFNMSMUKZHDEY-UHFFFAOYSA-M peroxynitrite Chemical compound [O-]ON=O CMFNMSMUKZHDEY-UHFFFAOYSA-M 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 210000000697 sensory organ Anatomy 0.000 description 1
- 239000002689 soil Substances 0.000 description 1
- 239000006228 supernatant Substances 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 239000001393 triammonium citrate Substances 0.000 description 1
- 235000011046 triammonium citrate Nutrition 0.000 description 1
- 229910021642 ultra pure water Inorganic materials 0.000 description 1
- 239000012498 ultrapure water Substances 0.000 description 1
Classifications
-
- 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
-
- 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
- G01N1/34—Purifying; Cleaning
-
- 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
Abstract
The invention discloses a method for detecting the content of ammonium citrate in liquid, which comprises the following steps: (1) removing impurities from an original liquid to be detected: (a) removing organic substances in the original liquid to be detected by extraction; (b) after the treatment of the step (a), removing copper ions in the liquid to be detected to obtain the liquid to be detected after removing the copper ions; (c) after the treatment of the step (b), removing the oxidant in the liquid to be detected; (2) and (3) determination: and (3) adding the liquid to be detected after the treatment in the step (1) into a potentiometric titrator, and determining the content of ammonium citrate in the liquid to be detected through titration. Compared with the traditional manual detection, the method has the advantages that the mode of combining manual detection and machine detection is adopted, so that errors caused by human operation are avoided, and the accuracy is improved; on the other hand, the defect that machine detection cannot be realized, and all detection methods can be carried out according to the same program is overcome.
Description
Technical Field
The invention relates to the technical field of chemical analysis, in particular to a method for detecting the content of ammonium citrate in liquid.
Background
Ammonium citrate, also called triammonium citrate, with molecular formula C6H5O7(NH4)3It is easily soluble in water and insoluble in ethanol, diethyl ether and acetone. Ammonium citrate is mainly used in industrial water treatment, metal cleaning (petroleum pipeline cleaning), ceramic dispersant, permeation aid, detergent material and soil improver, and may be also used in medicine, electronic industry, etc. Can also be used as a cyanide-free plating complexing agent in the electroplating industry; in analytical chemistryThe method is used as a chemical reagent, such as the determination of phosphate in the fertilizer, the determination of phosphate and effective phosphoric acid in the fertilizer; in the mechanical industry for the formulation of rust inhibitors; as buffers, emulsifiers and the like in the food industry. When ammonium citrate is used in these industrial applications, the content of ammonium citrate may need to be detected and analyzed due to the requirements of the process itself, for example, when ammonium citrate is used in the electroplating industry, the content of ammonium citrate needs to be determined due to the large influence of the content of ammonium citrate on the properties of the coating film, and the content of ammonium citrate needs to be detected.
Generally, the detection method is divided into manual detection and machine detection, and the manual detection is the dominant role in the detection process, but the method is easy to generate operation errors due to different reactions or habits of individual sense organs and motor organs of a detector or an observer, and the errors are different from person to person and have close relation with the mental state of the detector or the observer at the time. Therefore, the final titration process brings inevitable errors to people, and heating is needed to help the reaction in the process of preparing the detection solution, which also increases energy consumption and causes energy waste.
The whole process of detection by a machine has limitations because not all detection methods can be performed according to the same procedure, some solutions to be detected must react with some substances first, some substances in the solutions may precipitate after certain conditions are met (for example, after a sample is taken, the pH value may need to be adjusted, some substances in the solutions may precipitate, or the detection process often has many steps, which cannot be achieved by one step, and the process often has multiple steps, which cannot be achieved in one device), and the solutions to be detected can be added into a detection instrument for reaction with a titration solution, while the reaction process of the solutions to be detected and other substances usually needs filtration or other steps which are not suitable for being performed in the detection instrument (for example, when the detection steps are multiple steps, solids need to be added into a container, and the solids can act after being dissolved, and the reaction can be difficult to achieve in a narrow detection device, or, when the detection steps are multi-step, one solution must be added into the other solution, and the solution in the device is inconvenient to move in and out, which causes inaccurate detection), which is difficult or impossible to realize by a machine.
In addition, from the viewpoint of environmental protection, the reaction can be promoted only by heating or obviously heating (for example, heating to more than 70-80 ℃) and other processes in the existing detection method of ammonium citrate, so that the energy consumption is greatly increased from the viewpoint of large-scale detection, and the method does not conform to the concept of green development.
Disclosure of Invention
In view of the problems in the prior art, an object of the present invention is to provide a method for detecting the content of ammonium citrate in a liquid.
Further, another object of the present invention is to provide a method for preparing a detection solution for detecting the content of ammonium citrate.
According to the invention, a mode of combining manual detection and machine detection is adopted, so that compared with the traditional manual detection, errors caused by human operation are avoided, and the accuracy is improved. On the other hand, the defect that machine detection cannot be realized, and all detection methods can be carried out according to the same program is overcome.
The invention adopts the following technical scheme:
in various embodiments, a method for detecting the level of ammonium citrate in a liquid (or a solution, or an aqueous solution, or a mixture, or a liquid containing ammonium citrate, or a solution containing ammonium citrate, or a mixture containing ammonium citrate, as these terms are to be broadly understood) includes the steps of:
(1) removing impurities from an original liquid to be detected:
(a) removing organic substances or organic solvents in the original liquid to be detected by extraction, and collecting an aqueous phase layer; wherein the organic substance may be any organic substance that may be present in the original liquid to be detected;
(b) removing copper ions in the solution to be detected after the treatment of the step (a) to obtain the solution to be detected after the copper ions are removed;
(c) after the treatment of step (b), removing the oxidant in the liquid to be detected, wherein the oxidant can be any substance with an oxidizing property less than that of potassium permanganate, such as peroxynitrite ion, sulfite, nitrite, etc. (in the liquid to be detected), and the term "oxidant" is to be broadly understood herein;
(2) and (3) determination: and (3) adding the liquid to be detected after the treatment in the step (1) into a potentiometric titrator, and determining the content of ammonium citrate in the liquid to be detected through titration.
Further, the method for detecting the content of ammonium citrate in the liquid needs to firstly carry out the impurity removal process in the step (1) and then carry out the measurement process in the step (2). The impurity removing process of the step (1) comprises the steps (a), (b) and (c) described above.
Further, in the impurity removing process in the step (1), the process in the step (a) is generally performed first, followed by the process in the step (b), and then followed by the process in the step (c).
The original liquid to be detected can be industrial wastewater, industrial water, intermediate water in industrial production process, or other liquids requiring detection and analysis of ammonium citrate content, such as plating solution, electroplating solution, medical waste liquid, electronic factory waste liquid, chemical factory waste liquid, mechanical factory waste liquid, etc. Optionally, the original solution to be detected is not subjected to impurity removal treatment, or is only subjected to treatment of filtering to remove solid substances.
Specifically, in the process of removing impurities in the step (1), (a) organic substances or organic solvents in the original liquid to be detected are removed by extraction to obtain the liquid to be detected (namely, the collected water phase layer) after the organic substances or the organic solvents are removed; removing copper ions in the solution to be detected to obtain the solution to be detected after removing the copper ions; and (c) removing the oxidant in the liquid to be detected after the treatment of the step (b) to obtain the liquid to be detected after the oxidant is removed. Then, the measuring process of the step (2) is carried out: and (3) adding the liquid to be detected after the treatment in the step (1) into a potentiometric titrator, and determining the content of ammonium citrate in the liquid to be detected through titration.
Further, in the step (a), extracting the original liquid to be detected by using a mixed extraction liquid of saturated saline solution, hydrocarbon solvent and ester solvent, removing organic substances or organic solvent in the original liquid to be detected according to the correlation properties among the solvents, and collecting an aqueous phase layer for subsequent detection; wherein the hydrocarbon solvent comprises at least one of dichloromethane, cyclohexane and n-hexane, preferably dichloromethane; the ester solvent comprises at least one of methyl acetate, ethyl acetate, butyl acetate and isobutyl acetate, and ethyl acetate is preferred. As an example, the volume ratio of the original liquid to be detected to the mixed extraction liquid (i.e. the mixed solution of the saturated saline solution, the hydrocarbon solvent and the ester solvent) is 1: 0.5-10, preferably 1: 1 to 10, more preferably 1: 1 to 8, more preferably 1: 1 to 7, more preferably 1: 1 to 6, more preferably 1: 1 to 5, more preferably 1: 1 to 4, more preferably 1: 1 to 3, more preferably 1:2 to 3, for example 1: 2.2.
in a preferred embodiment, the volume ratio of the saturated saline solution, the hydrocarbon solvent and the ester solvent is 1: 1-5: 2-10, preferably 1: 2-4: 3 to 9, more preferably 1: 2-4: 5 to 8, for example 1: 3.33: 6.67. the saturated saline solution was added to prevent the organic and aqueous layers in the solution from separating significantly.
The term "saturated saline solution" as used herein may also be referred to as a "saturated sodium chloride solution" having a meaning generally understood in the art, and may be generally formulated by the solubility of common salt or sodium chloride at various temperatures, where the temperature generally refers to room temperature, unless otherwise specified herein. Alternatively, as a non-limiting example, common salt or sodium chloride may be dissolved in water, and the solution may be left to stand until it is not dissolved and then slightly excess, and the supernatant may be taken out.
Among them, hydrocarbon solvents, ester solvents such as methylene chloride, ethyl acetate are commercially available and can be used as they are.
The purity grade of the substance purchased or used herein is chemically pure, analytically pure or guaranteed, preferably analytically pure, more preferably guaranteed, unless otherwise specified herein.
Specifically, in certain embodiments, for example, 5ml (raw) of the liquid to be detected (which can be taken using a pipette) is taken, and the amount of the liquid to be detected is measured using 1ml of saturated saline and 10ml of a volume ratio of 1:2 (for example, dichloromethane) and an ester solvent (for example, ethyl acetate), extracting the liquid to be detected, collecting the aqueous phase layer for later use, and discarding the organic layer.
In a preferred embodiment, in the step (b), the solution to be detected (i.e., the solution to be detected after removal of organic substances or organic solvents, or the aqueous layer solution after the treatment in the step (a)) is mixed with dilute sulfuric acid in a volume ratio of 1: 1 to 20 (e.g., 1: 1 to 20, 1: 1 to 18, 1: 1 to 16, 1: 1 to 14, 1: 1 to 12, 1: 1 to 10, 1: 1 to 8, 1:2 to 8, or 1: 3 to 7, specifically, e.g., 1: 5.4), followed by adding aluminum, reacting, and filtering to remove copper ions in the liquid to be detected. Further, the dilute sulfuric acid in the step (b) has a relative density of 1.84g/cm3The volume ratio of concentrated sulfuric acid to distilled water is 1: 5 to 30 (e.g., 1: 5 to 30, 1: 5 to 25, 1: 5 to 20, 1: 5 to 15, or 1: 10 to 15, specifically, e.g., 1: 12.5). It is noted that the dilute sulfuric acid used in the description herein may be a dilute sulfuric acid formed by adding concentrated sulfuric acid and an appropriate amount of water. For example, the dilute sulfuric acid used in step (b) may be simultaneously added in a volume ratio of 1: 5-30 parts of concentrated sulfuric acid and distilled water.
The term "concentrated sulfuric acid" as used herein is an aqueous sulfuric acid solution having a mass fraction of 70% or more, unless otherwise specified. Concentrated sulfuric acid is commercially available. In addition, a commonly used concentrated sulfuric acid H2SO4Has a mass fraction of 98.3% and a density of 1.84g cm-3The mass concentration of the substance is 18.4 mol.L-1Melting point: 10 ℃; boiling point: 338 ℃. As an example, another concentrated sulfuric acid has a density of 1.64g cm-3。
As used herein, and unless otherwise specified, the term "dilute sulfuric acid" refers to an aqueous solution of sulfuric acid having a solute mass fraction of less than 70%. The dilute sulfuric acid can be obtained by mixing concentrated sulfuric acid with water for dilution.
In a preferred embodiment, the ratio of the added mass of aluminum to the volume of the liquid to be detected after the treatment in step (a) is 0.02 to 1g/mL, preferably 0.05 to 0.5g/mL, more preferably 0.1 to 0.3g/mL, more preferably 0.1 to 0.2 g/mL. Further, aluminum used in the present application is pure aluminum, such as pure aluminum sheet, pure aluminum block, pure aluminum strip, pure aluminum rod, pure aluminum wire, and the like. The term "pure aluminum" as used herein has a general definition in the usual sense and should be understood broadly, for example, commercially pure aluminum is generally defined as aluminum having a purity of 99.0% to 99.9%; or, the Chinese standard is aluminum with the purity of 98.8-99.7%; but also includes pure aluminum standards established in other areas or industries.
In view of the specificity in the field of analytical detection, the water used herein is preferably distilled water, optionally deionized water, and more preferably ultrapure water.
Specifically, as a non-limiting example, the process of step (b) may be: taking 5ml of the liquid to be detected after the treatment of the step (a) (which can be measured by a pipette), 25ml of distilled water and 2ml of concentrated sulfuric acid into a container, adding 0.5-1g of pure aluminum sheet into the container, and reacting until the solution is colorless (mainly Cu is used in the process)2+The ions are oxidized to Cu by aluminum, and the color is changed from Cu2+The blue color disappears, and the solution is understood to be colorless and transparent) (in the process, heating can be selected, but the heating temperature is lower, and is generally controlled to be 30-40 ℃, cooling (for example, cooling to room temperature), placing the cooled solution in a centrifuge for centrifugation, and filtering to obtain the solution to be detected after copper ions are removed.
Optionally, the solution after the treatment of step (b) (i.e. the solution to be detected after removing copper ions obtained after filtration) is transferred into a volumetric flask (for example, 100ml specification), diluted to a scale by adding distilled water, and shaken to obtain a mixed solution a, in other words, the mixed solution a is the solution to be detected after removing copper ions after dilution, for example, the solution to be detected after removing copper ions is diluted by about 1 to 5 times, for example, 3.33 times to obtain the mixed solution a.
Considering the handling and reaction itself and the factors of water addition, the volume of the original liquid to be detected is approximately equivalent to the volume of the liquid to be detected after removal of the organic substance or organic solvent, i.e., about 1: 1.
the volume of the solution to be detected after removal of copper ions is about 3 to 10 times, for example, 6 times, the volume of the solution to be detected after removal of organic substances or organic solvents, in consideration of the operation and reaction itself and the factors of water addition.
The volume of the mixed solution a is about 1 to 5 times, for example, 3.33 times, the volume of the solution to be detected after removal of copper ions.
Further, in the step (c), the solution to be detected after being processed in the step (b) is mixed with dilute sulfuric acid, then manganous sulfate and potassium permanganate are added, and then potassium iodide and starch are added to remove the oxidant in the solution to be detected.
Further, the ratio of the added mass of the manganous sulfate to the volume of the original liquid to be detected is 0.5-10 g/mL, such as 0.5-8 g/mL, 0.5-6 g/mL, 1-6 g/mL or 2-5 g/mL, specifically, such as 3 g/mL.
Further, the ratio of the added mass of potassium permanganate (molecular weight is 158.034) to the volume of the original solution to be detected is 0.001-0.5 g/mL, such as 0.005-0.5 g/mL, 0.01-0.3 g/mL, 0.05-0.3 g/mL or 0.05-0.2 g/mL, specifically, such as 0.08 g/mL.
Further, the ratio of the added mass of potassium iodide to the volume of the original liquid to be detected is 0.01-10 g/mL, such as 0.05-8 g/mL, 0.1-6 g/mL, 0.5-6 g/mL or 1-5 g/mL, specifically, such as 2 g/mL.
Further, the ratio of the added mass of starch to the volume of the original liquid to be detected is 0.001-0.1 g/mL, such as 0.005-0.1 g/mL, 0.005-0.05 g/mL, 0.01-0.05 g/mL or 0.01-0.03 g/mL, specifically, such as 0.02 g/mL.
Alternatively, the starch is a starch solution, such as a l% (mass fraction) starch solution.
Alternatively, 20ml of the mixed solution A (which may be measured by a pipette), 100ml of distilled water, and 5ml of sulfuric acid are taken in a 500ml conical flask, and 25ml of a solution of 3g of manganous sulfate and 0.02mol/L of potassium permanganate are added thereto, and left to stand for 15 to 20 minutes, and then 2g of potassium iodide (solid), 2ml of a starch solution (e.g., a L% (mass fraction) starch solution) are added thereto to obtain a solution to be assayed after removing the oxidizing agent. The sulfuric acid here is 1: 4 sulfuric acid, i.e. to 4ml1.64g/cm3Concentrated sulfuric acid (the density of the concentrated sulfuric acid is 1.64 g/cm)3) To which 1ml of water was added. The sulfuric acid was mixed with 100ml of distilled water to obtain dilute sulfuric acid.
In various embodiments, in step (2), the titration solution used in the potentiometric titrator is a sodium thiosulfate standard solution.
In a preferred embodiment, in step (2), the titration solution used in the potentiometric titrator is a 0.1mol/L sodium thiosulfate standard solution.
Optionally, adding the solution to be detected after impurity removal into a titration cell of a potentiometric titrator, adding 0.1mol/L standard sodium thiosulfate titration solution into a burette of the potentiometric titrator, and carrying out titration detection analysis.
Wherein, the operating principle of the automatic potentiometric titrator is as follows: the proper indicating electrode and reference electrode are selected to form a working battery with the measured solution, and with the addition of titrant, the concentration of the measured ion changes continuously due to chemical reaction, so that the potential of the indicating electrode changes accordingly. In the vicinity of the titration end point, the measured ion concentration abruptly changes to cause a sudden electrode potential jump, and therefore the titration end point can be determined from the sudden electrode potential jump. Automatic potentiometric titrators are prior art and their construction is not described herein.
The principle of the invention is as follows: firstly, Cu is coated by an aluminum sheet+2Reducing the solution into metallic copper, filtering and removing the metallic copper, wherein the solution becomes acidic, ammonium citrate becomes citric acid in the acidic solution, and an aluminum sheet is adopted to mainly remove interfering copper ions in the solution. Then, quantitatively oxidizing the citric acid by using potassium permanganate, adding potassium iodide after the reaction is finished, enabling the residual high-valence manganese and potassium iodide to generate free iodine, titrating by using sodium thiosulfate, and when the color disappears from blue, the reaction reaches the end point, and automatically calculating the content of the ammonium citrate by using a potentiometric titrator.
The reaction mechanism of citric acid and potassium permanganate is as follows: h3C6H5O7+6KMnO4----H2O+3CO2↑+6KCOOH+6MnO2Then the detection liquid is put into a titration cell of the titration liquid, and 0.1 is addedThe mol sodium thiosulfate solution is added into a burette in a potentiometric titrator. And (3) starting a potentiometric titrator, and recording the obtained data when the titration of the sodium thiosulfate solution is finished until the blue color disappears.
The calculation equation is:
in the formula: c1 is the molar concentration of a standard potassium permanganate solution; v1 is the volume (mL) consumed standard potassium permanganate solution; c2 is the molar concentration of a standard sodium thiosulfate solution; v2 is the volume (mL) consumed standard sodium thiosulfate solution;
as used herein, "and/or" includes any and all combinations of one or more of the associated listed items. The terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention. As used herein, the singular forms "a", "an" and "the" are intended to include the plural forms as well, unless the context clearly indicates otherwise. It will be further understood that the terms "comprises" and/or "comprising," when used in this specification, specify the presence of stated features, integers, steps, operations, elements, and/or components, but do not preclude the presence or addition of one or more other features, integers, steps, operations, elements, components, and/or groups thereof.
Unless defined otherwise, all terms (including technical and scientific terms) used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. It will be further understood that terms, such as those defined in commonly used dictionaries, should be interpreted as having a meaning that is consistent with their meaning in the context of the relevant art and will not be interpreted in an idealized or overly formal sense unless expressly so defined herein.
The exemplary invention described herein may suitably lack any one or more of the element limitations, which are not specifically disclosed herein. Thus, the terms "comprising," "including," "containing," and the like are to be construed broadly and in a non-limiting sense. Furthermore, the terms used herein are used as terms of description and not of limitation, and there is no intention in the use of such terms to describe only some of their characteristics but, in the light of the claims, various modifications are possible within the scope of the invention. Thus, while the present invention has been particularly disclosed in terms of preferred embodiments and optional features, modification of the invention herein disclosed to embody it may be noted by those skilled in the art, and such modifications and variations are considered to be within the scope of the invention.
Compared with the prior art, the invention has the beneficial effects that:
the invention provides a method for detecting the content of ammonium citrate in liquid, which adopts a mode of combining manual detection and machine detection, on one hand, compared with the traditional manual detection, the method avoids errors caused by human operation, improves the accuracy, and does not need the steps of increasing energy consumption, such as heating and the like, in the existing detection method; on the other hand, the defect that machine detection cannot be realized, and all detection methods can be carried out according to the same program is overcome.
Detailed Description
For better explanation of the present invention, the following specific examples are further illustrated, but the present invention is not limited to the specific examples.
Example 1
Preparation before experiment:
1, 6 and 5ml pipettes, 2 and 25ml pipettes, 10ml pipettes, 100ml volumetric flasks, 20ml pipettes, 100ml graduated cylinders and 500ml erlenmeyer flasks were prepared in a separatory funnel, washed with distilled water, and then dried in an oven for use.
Preparation of a solvent:
saturated saline solution, 1:2, a mixed solution of dichloromethane and ethyl acetate, having a relative density of 1.84g/cm3Concentrated sulfuric acid, manganous sulfate, pure aluminum sheet, 1: 4 sulfuric acid solution. 0.02mol/L potassium permanganate solution, potassium iodide (solids), L% starch solution, 0.1mol/L standard sodium thiosulfate solution, wherein 1: 4The sulfuric acid solution was added to 4ml of 1.64g/cm3To the concentrated sulfuric acid of (1) was added 1ml of water.
The method for detecting the content of ammonium citrate in the liquid comprises the following steps:
first, 5ml of the original liquid to be detected, a 1:2 mixed solvent of dichloromethane and ethyl acetate, and 1ml of saturated saline were taken, extracted in a separatory funnel, and the aqueous layer was taken. Transferring 5mL of the solution to be detected by using a 5mL pipette, placing the solution in a 100mL beaker, transferring 2mL of concentrated sulfuric acid by using the 5mL pipette along the wall of the beaker, and slowly placing the solution in the beaker while stirring, so that the sulfuric acid can be prevented from splashing on human skin to cause danger due to heat release when meeting water, then transferring 25mL of distilled water by using a 25mL pipette in the 100mL beaker, uniformly stirring the mixed solution by using glass, adding 0.5g of pure aluminum sheet into the stirred mixed solution, and slightly heating (30 ℃) until no Cu exists2+The aluminum sheet is added to replace the copper ions in the solution so as to prevent the color of the copper ions from interfering the detection, and the reaction equation is as follows: al + Cu+2----Al+3+ Cu, centrifuge the above solution in centrifuge, filter, transfer the solution into l00mL volumetric flask, wash the excess aluminum sheet with distilled water for next use, add distilled water to volumetric flask to dilute to the scale, shake well. The solution in the volumetric flask was pipetted 20mL with a 20mL pipette into a 250mL conical flask, 100mL of water was added to the volumetric flask with a distilled water bottle, and l: 4, adding 3g of manganous sulfate into 5mL of sulfuric acid in a conical flask, adding a magnetic stirrer, placing the conical flask on a magnetic stirring device, starting a stirring switch, reducing the oxidizing agent possibly existing in the solution to be detected by using the manganous sulfate as a reducing agent, and completely reacting without heating, so that the energy is saved, adding 25mL of 0.02mol/L potassium permanganate solution into a 25mL pipette, shaking the conical flask, then placing for 15min, and cooling to prepare a detection liquid for detecting the ammonium citrate.
Then the detection solution was put into a titration cell of a titration solution, and 0.1mol of a sodium thiosulfate solution was added to a burette in a potentiometric titrator (instrument model: ZDJ-4B Autopotentiometric titrator, manufacturer: Raynaud's magnet). And (3) starting a potentiometric titrator, and recording the obtained data when the titration of the sodium thiosulfate solution is finished until the blue color disappears. The use of potentiometric titrators and detection methods and procedures are known to those skilled in the art.
The calculation equation is:
in the formula: c1 is the molar concentration of a standard potassium permanganate solution; v1 is the volume (mL) consumed standard potassium permanganate solution; c2 is the molar concentration of a standard sodium thiosulfate solution; v2 is the volume (mL) consumed standard sodium thiosulfate solution;
comparative example 1
The same liquid to be tested (plating solution) as in example 1 was tested. The whole course of the detection process of the comparative example 1 only uses the mode of manual titration detection (the mode of the whole course manual titration detection is a common mode in the field), and does not use the combined mode of manual titration detection and machine titration of the invention.
The manual titration test procedure of comparative example 1 was substantially: the sample was taken from the field using a 500ml glass beaker and then the following steps were followed: taking 5ml of a liquid to be detected from a 500ml glass beaker, extracting the liquid with 1ml of saturated common salt water and 10ml of a mixed solvent of dichloromethane and ethyl acetate in a ratio of 1:2, taking a water phase layer for standby, transferring 5ml of the liquid to be detected, 25ml of distilled water and 2ml of concentrated sulfuric acid into a container, adding 0.5-1g of pure aluminum sheets into the container, heating the mixture until the mixture is colorless, cooling the mixture, placing the cooled solution into a centrifuge for centrifugation, filtering the mixture, transferring the filtered solution into a corresponding 100ml volumetric flask, adding distilled water to dilute the solution to a scale, and shaking the solution uniformly to obtain a mixed solution. 20ml of the mixed solution obtained in step 2, 100ml of distilled water, 1: 4, adding 25ml of 3g of manganous sulfate and 0.02mol/L potassium permanganate solution into a 500ml conical flask, standing for 15-20 minutes, and then adding 2g of potassium iodide and 2ml of starch solution to obtain a detection solution of ammonium citrate. Then, 0.1mol of sodium thiosulfate solution is added into a 50ml dropping tube to the scale mark, and the detection solution is placed under the mouth of the titration tube, and titration is started until the blue color of the detection solution disappears as the end point.
Example 2
Another batch of the solution to be detected (plating solution) is taken again. The procedure of example 1 was repeated by completely reconstituting each solvent or sample solution, but replacing methylene chloride with cyclohexane and ethyl acetate with methyl acetate, and further, the amount or ratio of each solvent or sample solution was appropriately adjusted within the range.
Comparative example 2
The same liquid to be tested (plating solution) as in example 2 was tested. The procedure of comparative example 1 was repeated by completely reconstituting the various solvents or test solutions, but replacing dichloromethane with cyclohexane and ethyl acetate with methyl acetate. The whole detection process of the comparative example 2 only uses the mode of manual titration detection, and does not use the combined mode of manual titration detection and machine titration.
Example 3
The solution to be detected (plating solution) was sampled again. The procedure of example 1 was repeated by completely reconstituting each solvent or sample solution, but replacing n-hexane with dichloromethane and butyl acetate with ethyl acetate, and the amount or ratio of each solvent or sample solution was appropriately adjusted within the range.
Comparative example 3
The same liquid to be detected (plating liquid) as in example 3 was detected. The test procedure of comparative example 1 was repeated with complete reconstitution of the various solvents or test solutions, but with dichloromethane replaced by n-hexane and ethyl acetate by butyl acetate. The whole detection process of the comparative example 3 only uses the mode of manual titration detection, and does not use the combined mode of manual titration detection and machine titration.
The results of the detection accuracy of each example and comparative example are shown in table 1. The accuracy is calculated in the following manner: taking a liquid to be detected (such as a plating solution) to perform liquid chromatography to obtain the content of citric acid, calculating the amount V of sodium thiosulfate to be consumed according to the equation, then respectively using an artificial titration result V1 and an artificial and machine titration result V2 for the liquid to be detected (such as the plating solution), obtaining the artificial titration accuracy by using V1/V, and obtaining the accuracy of the artificial titration and machine titration detection results by using V2/V.
Table 1:
| detection mode | Accuracy of |
| Comparative example 1 (Manual titration data 1) | 89％ |
| Example 1 (Manual titration + machine titration data 1) | 95％ |
| Comparative example 2 (Manual titration data 2) | 91％ |
| Example 2 (Manual titration + machine titration data 2) | 97％ |
| Comparative example 3 (Manual titration data 3) | 88％ |
| Example 3 (Manual titration + machine titration data 3) | 94％ |
As can be seen from table 1, the combined detection mode of manual titration detection and machine titration according to the present invention has significantly improved detection accuracy compared to the mode using only manual detection. And, need not the external world and give the heating almost, compare in the traditional heat that needs the heating in the in-process of preparing the detection liquid, can ignore, saved a large amount of energy, accord with the environmental protection theory of green development. Furthermore, the detection cannot be completed by using only machine detection during the detection process, and the detection cannot be satisfied by using only machine titration detection, because the pretreatment is required by using only machine titration detection, and these steps cannot be performed and completed in a narrow space within the machine.
The above description is only exemplary of the present invention and is not intended to limit the scope of the present invention, which is defined by the claims appended hereto, as well as the appended claims.
Claims (10)
1. The method for detecting the content of ammonium citrate in the liquid is characterized by comprising the following steps of:
(1) removing impurities from an original liquid to be detected:
(a) removing organic substances in the original liquid to be detected by extraction, and collecting an aqueous phase layer;
(b) after the treatment of the step (a), removing copper ions in the liquid to be detected to obtain the liquid to be detected after removing the copper ions;
(c) after the treatment of the step (b), removing the oxidant in the liquid to be detected;
(2) and (3) determination: and (3) adding the liquid to be detected after the treatment in the step (1) into a potentiometric titrator, and determining the content of ammonium citrate in the liquid to be detected through titration.
2. The method according to claim 1, wherein in step (a), the liquid to be detected is extracted by a mixed solution of saturated saline solution, hydrocarbon solvent and ester solvent, and the water phase layer is collected; wherein the hydrocarbon solvent comprises at least one of dichloromethane, cyclohexane and n-hexane; the ester solvent comprises at least one of methyl acetate, ethyl acetate, butyl acetate and isobutyl acetate.
3. The method for detecting the content of ammonium citrate in the liquid according to claim 2, wherein the volume ratio of the saturated saline solution to the hydrocarbon solvent to the ester solvent is 1: 1-5: 2 to 10.
4. The method for detecting the content of ammonium citrate in the liquid according to claim 1, wherein in the step (b), the liquid to be detected after the treatment in the step (a) is mixed with dilute sulfuric acid according to a volume ratio of 1: 1-20, adding aluminum, reacting, filtering, and removing copper ions in the liquid to be detected.
5. The method as claimed in claim 4, wherein the dilute sulfuric acid has a relative density of 1.84g/cm3The volume ratio of concentrated sulfuric acid to distilled water is 1: 5-30, and mixing.
6. The method for detecting the content of ammonium citrate in liquid according to claim 4, wherein the ratio of the added mass of aluminum to the volume of the liquid to be detected after the treatment in the step (a) is 0.02-1 g/mL.
7. The method according to claim 1, wherein in step (c), the solution to be detected after the treatment in step (b) is mixed with dilute sulfuric acid, and then manganous sulfate and potassium permanganate are added, and then potassium iodide and starch are added to remove the oxidant in the solution to be detected.
8. The method for detecting the content of ammonium citrate in the liquid according to claim 7, wherein the ratio of the added mass of manganous sulfate to the volume of the original liquid to be detected is 0.5-10 g/mL; the ratio of the adding mass of the potassium permanganate to the volume of the original liquid to be detected is 0.001-0.5 g/mL.
9. The method for detecting the content of ammonium citrate in liquid according to claim 7, wherein the ratio of the added mass of potassium iodide to the volume of the original liquid to be detected is 0.01-10 g/mL; the ratio of the added mass of the starch to the volume of the original liquid to be detected is 0.001-0.1 g/mL.
10. The method for detecting the content of ammonium citrate in liquid according to any one of claims 1-9, wherein in the step (2), the titration solution used in the potentiometric titrator is a standard solution of sodium thiosulfate.
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