CN112577948A - Copper ion rapid detection method and device - Google Patents
Copper ion rapid detection method and device Download PDFInfo
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- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 title claims abstract description 106
- 229910001431 copper ion Inorganic materials 0.000 title claims abstract description 105
- 238000001514 detection method Methods 0.000 title claims abstract description 30
- 238000000034 method Methods 0.000 claims abstract description 31
- 239000000463 material Substances 0.000 claims abstract description 19
- 239000000243 solution Substances 0.000 claims description 129
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 44
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 35
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 28
- 239000008367 deionised water Substances 0.000 claims description 23
- 229910021641 deionized water Inorganic materials 0.000 claims description 23
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonium chloride Substances [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 claims description 22
- 229910021529 ammonia Inorganic materials 0.000 claims description 22
- 239000007853 buffer solution Substances 0.000 claims description 22
- 239000003086 colorant Substances 0.000 claims description 21
- 229920000742 Cotton Polymers 0.000 claims description 19
- 238000001035 drying Methods 0.000 claims description 18
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 17
- 239000004744 fabric Substances 0.000 claims description 17
- 238000002360 preparation method Methods 0.000 claims description 14
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 14
- 229920002678 cellulose Polymers 0.000 claims description 13
- 239000001913 cellulose Substances 0.000 claims description 13
- 238000006243 chemical reaction Methods 0.000 claims description 12
- 238000003860 storage Methods 0.000 claims description 12
- 238000005520 cutting process Methods 0.000 claims description 11
- 239000012528 membrane Substances 0.000 claims description 10
- 229920002749 Bacterial cellulose Polymers 0.000 claims description 6
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 claims description 6
- 239000005016 bacterial cellulose Substances 0.000 claims description 6
- 239000007788 liquid Substances 0.000 claims description 3
- 229910000030 sodium bicarbonate Inorganic materials 0.000 claims description 3
- 235000017557 sodium bicarbonate Nutrition 0.000 claims description 3
- 235000019441 ethanol Nutrition 0.000 claims description 2
- 230000010355 oscillation Effects 0.000 claims description 2
- 238000012031 short term test Methods 0.000 claims 1
- 238000012360 testing method Methods 0.000 abstract description 11
- 230000035484 reaction time Effects 0.000 abstract description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 15
- 229910052802 copper Inorganic materials 0.000 description 15
- 239000010949 copper Substances 0.000 description 15
- 125000003431 oxalo group Chemical group 0.000 description 10
- 238000002791 soaking Methods 0.000 description 9
- 238000010586 diagram Methods 0.000 description 8
- 230000008901 benefit Effects 0.000 description 6
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- 102000004190 Enzymes Human genes 0.000 description 2
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- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 239000010842 industrial wastewater Substances 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 229910021645 metal ion Inorganic materials 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- 208000000044 Amnesia Diseases 0.000 description 1
- VTLYFUHAOXGGBS-UHFFFAOYSA-N Fe3+ Chemical compound [Fe+3] VTLYFUHAOXGGBS-UHFFFAOYSA-N 0.000 description 1
- 208000026139 Memory disease Diseases 0.000 description 1
- 208000025371 Taste disease Diseases 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- -1 ammonium ions Chemical class 0.000 description 1
- 238000003321 atomic absorption spectrophotometry Methods 0.000 description 1
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- 229910001447 ferric ion Inorganic materials 0.000 description 1
- 235000013373 food additive Nutrition 0.000 description 1
- 239000002778 food additive Substances 0.000 description 1
- 210000000232 gallbladder Anatomy 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 210000004185 liver Anatomy 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
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- 208000023060 memory loss Diseases 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 235000019656 metallic taste Nutrition 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
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- G01—MEASURING; TESTING
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- G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
- G01N21/75—Systems in which material is subjected to a chemical reaction, the progress or the result of the reaction being investigated
- G01N21/77—Systems in which material is subjected to a chemical reaction, the progress or the result of the reaction being investigated by observing the effect on a chemical indicator
- G01N21/78—Systems in which material is subjected to a chemical reaction, the progress or the result of the reaction being investigated by observing the effect on a chemical indicator producing a change of colour
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Abstract
The invention relates to a method for quickly detecting copper ions, which comprises the following steps: preparing a color developing solution; treating a base material; preparing a detector; preparing a sample to be detected; and (3) dropping a sample to be detected on the detector, and comparing the color of the detector with the color comparison card to obtain the concentration of copper ions in the sample to be detected. The invention also relates to a device for rapidly detecting the copper ions, a detector prepared by the method for rapidly detecting the copper ions and a standard colorimetric card. The method can obviously improve the detection timeliness, does not need to prepare a detection solution separately on site, does not pollute the environment, has a wide test range, does not need professionals for test operation, has short reaction time and better stability, does not need to carry other solutions or equipment, only needs to carry a detector and a standard colorimetric card, and is suitable for on-site and on-site detection.
Description
Technical Field
The invention relates to the technical field of copper ion detection, in particular to a method and a device for quickly detecting copper ions.
Background
Copper is one of metal elements that the human body cannot lack. In adults, 1 kg of body weight contains about 1.4mg to 2.1mg of copper; the copper content in blood is about 1.0mg to 1.5 mg. Copper is an important component of proteins and enzymes in the body, and many important enzymes require the participation and activation of trace amounts of copper. Meanwhile, copper is heavy metal ions, and the burden of liver and gallbladder in a human body can be increased by taking food containing excessive copper for a long time, so that memory loss, inattention, easy excitation and the like are caused, and therefore, the control of the copper intake of the human body is very important.
Copper is widely existed in industrial wastewater of electroplating plants, chemical plants and printing and dyeing plants, and also widely existed in food additives and drinking water, the copper content in the water is more than 1.5mg/L, the obvious metallic taste is provided, and the fabric can be dyed when the copper content is more than 1 mg/L. According to national regulations, the maximum allowable discharge concentration of copper and compounds thereof in industrial wastewater is 1mg/L, the maximum water for ground is not more than 0.1mg/L, the water for fishery is not more than 0.01mg/L, and the copper concentration of domestic water is not more than 1 mg/L. The detection of the copper content has important significance in the fields of industrial sewage discharge, environmental detection, agricultural application and food safety, and the currently common detection method of the copper content mainly comprises the following steps: atomic absorption spectrophotometry, atomic absorption spectrometry, iodometry, spectrophotometry, etc., which require operators to have certain analytical chemistry bases, and also require long detection time, high cost, and large-scale instruments, and cannot realize rapid detection.
Disclosure of Invention
The invention aims to provide a method for quickly detecting copper ions, which has the advantages of quick detection time, high sensitivity and wide test range.
The invention also aims to provide a copper ion rapid detection device which is simple to manufacture, convenient to carry, energy-saving, environment-friendly, low in cost and convenient to use.
The scheme adopted by the invention for realizing one of the purposes is as follows: a copper ion rapid detection method comprises the following steps:
(1) preparing a color developing solution: preparing a bicyclohexanoneoxalyl dihydrazone solution by using absolute ethyl alcohol and deionized water;
(2) treating a base material: placing the base material in a sodium carbonate or sodium bicarbonate solution at 80-100 ℃, taking out and drying;
(3) preparing a detector: immersing the treated base material obtained in the step (2) into the bicyclohexanoneoxalyl dihydrazone solution obtained in the step (1), oscillating at constant temperature, taking out, drying, and cutting to a proper size to obtain a detector;
(4) preparing a sample to be tested: adjusting the pH value of a sample to be detected to 7-9 by using an ammonia water-ammonium chloride buffer solution;
(5) and (4) dripping the sample to be detected obtained in the step (4) on the detector obtained in the step (3), and comparing the color of the detector with the color comparison card to obtain the concentration of copper ions in the sample to be detected.
In the above technical scheme, in the step (1), the mass ratio of ethanol in the bicyclohexanoneoxalyl dihydrazone solution is 30% -50%, the temperature during preparation is 20-45 ℃, and the concentration range of the prepared bicyclohexanoneoxalyl dihydrazone solution is 6-10 mmol/L.
In the above technical solution, in the step (2), the base material is a cotton cloth or a cellulose film or a bacterial cellulose film, and the sodium carbonate solution has a mass fraction range of: 8 to 10 percent. The cotton cloth has the advantages that: the cotton cloth is cellulose made of cotton, namely cotton cellulose, generally, the content of the cellulose in the cotton is higher and close to 100%, and the adsorption of the cellulose to the color-developing agent is better when the content of the cellulose is higher; the cellulose membrane has the advantages that: the cellulose content is higher, and loose porous surface does benefit to the absorption of developer, adopts the advantage of bacterial cellulose membrane to be: the cellulose content is 100%, the surface has abundant hydroxyl, the appearance presents a loose and porous structure and is beneficial to adsorbing a color developing agent, and the base material is placed in a sodium carbonate solution or a sodium bicarbonate solution to play the following roles: the hydroxyl on the surface of the substrate is fully exposed, and the hydrophilic property of the substrate is increased.
In the above technical scheme, in the step (3), the constant temperature shaking time is 1-2h, the temperature is 20-30 ℃, the drying treatment condition is drying in the shade in the dark, and the storage condition of the detector is storing in the shade in a sealed manner. The oscillation temperature is selected to be 20-30 ℃ and has the advantages that: protecting the decomposition of the color developing agent at high temperature. The principle that the drying treatment needs to be carried out in the dark is as follows: protecting the color developing agent from being decomposed under strong light. The principle that the detector needs to be stored in a sealed manner in a shade is as follows: the detector can be prevented from deteriorating and decomposing due to sealed preservation, and the service life of the detector is prolonged.
In the above technical solution, in the step (4), the sample to be measured is a liquid.
In the above technical solution, in the step (4), the concentration range of the copper ions in the sample to be detected is 4-16 mg/L. The concentration of copper ions is lower than 4mg/L, the color development is not obvious, the concentration of copper ions is higher than 16mg/L, the color development is not obvious,
in the above technical scheme, in the step (5), the preparation method of the standard color comparison card comprises: and (3) respectively preparing copper ion solutions with the concentrations of 4mg/L, 8mg/L, 12mg/L and 16mg/L and the pH value of 9, respectively dripping 0.1mL of the solutions into the copper ion solution prepared in the step (3) and adjusting the pH value of the ammonia water-ammonium chloride buffer solution to 9, respectively dripping 0.1mL of the solutions onto the detector prepared in the step (3) for reaction, respectively recording the corresponding colors by using a camera, collecting the colors by using photo processing software, and printing to obtain the standard colorimetric card.
In the above technical scheme, in the preparation method of the sample to be measured and the standard colorimetric card, after the pH value is adjusted by using the ammonia water-ammonium chloride buffer solution, the reaction process is accelerated due to the large amount of ammonium ions, so that the detection time is greatly shortened, and the purpose of rapidly determining the copper ion content is achieved.
The second scheme adopted by the invention for achieving the purpose is as follows: a copper ion rapid detection device, a detector and a standard colorimetric card prepared by the rapid detection method of copper ions. The detector and the standard colorimetric card are convenient to carry after being manufactured, other solutions or equipment do not need to be carried when the on-site detection is carried out, a plurality of detectors can be prepared in advance, and the detection of various samples is facilitated.
The invention has the beneficial effects that:
(1) the rapid detection method for copper ions provides convenient conditions for rapid detection of copper ion concentration, can detect milligram-level copper ion concentration in a sample to be detected in a semi-quantitative manner, preferably has the copper ion concentration range of 4-16mg/L, only needs 1-2 minutes for detection time, and can remarkably improve detection timeliness compared with the time spent by the traditional detection method, such as 20-1 hour, and the method does not need to prepare a detection solution separately on site, does not pollute the environment, has wide test range, and does not need professional personnel for test operation.
(2) The copper ion rapid detection device disclosed by the invention is short in reaction time, good in stability, free of carrying of other solutions or equipment, only needs to carry the detector and the standard colorimetric card, and suitable for on-site and on-site detection, and the preparation methods of the detector and the standard colorimetric card are simple, convenient to carry, energy-saving, environment-friendly, low in cost and convenient to use. The standard colorimetric card is used as the detection standard of the concentration of the copper ions, and compared with other detection standards, the method is simpler, more convenient and more intuitive, and is favorable for quickly obtaining a determination result.
Drawings
FIG. 1 is a schematic diagram of a standard color chart prepared in example 1 of the present invention;
FIG. 2 is a diagram showing a test object in example 1 of the present invention;
FIG. 3 is a diagram of a test object in example 2 of the present invention;
FIG. 4 is a diagram of a test object in example 3 of the present invention;
FIG. 5 is a graph showing the relationship between pH and absorbance in example 4 of the present invention;
FIG. 6 is a graph comparing the absorbance selectivity for various ions in example 5 of the present invention;
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1
The method for rapidly detecting the copper ions comprises the following steps:
(1) preparing a color developing solution: the mass ratio of 1: 1, preparing 10mmol/L dicyclohexyl oxalyl dihydrazone solution by using absolute ethyl alcohol and deionized water;
(2) treating a base material: placing cotton cloth in a sodium carbonate solution with the mass fraction of 10% at the temperature of 80 ℃, taking out and drying;
(3) preparing a detector: soaking the treated cotton cloth obtained in the step (2) into the bicyclohexanoneoxalyl dihydrazone solution obtained in the step (1), oscillating at constant temperature for 1h at 30 ℃, taking out, airing in shade, cutting to small blocks of 0.8cm x 0.6cm to obtain a detector, and placing the detector in a shade dry place for sealed storage;
(4) preparing a standard colorimetric card: respectively preparing copper ion solutions with the concentrations of 4mg/L, 8mg/L, 12mg/L and 16mg/L and the pH value of 9, respectively dripping 0.1mL of the solutions into the copper ion solution prepared in the step (3) and adjusting the pH value of the ammonia water-ammonium chloride buffer solution to 9, respectively dripping 0.1mL of the solutions onto the detector prepared in the step (3) for reaction, respectively recording the corresponding colors by using a camera, collecting the colors by using photo processing software, and printing to obtain a standard colorimetric card;
(5) preparing a sample to be tested: preparing 8mg/L copper ion solution by using deionized water, and adjusting the pH value of the copper ion solution to 9 by using ammonia water-ammonium chloride buffer solution;
(6) and (4) dripping 0.1mL of the sample to be detected obtained in the step (5) on the detector obtained in the step (3), and comparing the color of the detector with the color comparison card to obtain the concentration of copper ions in the sample to be detected.
Fig. 1 is a schematic diagram of a standard colorimetric card prepared in example 1 of the present invention, fig. 2 is a diagram of a test object in example 1 of the present invention, and when a color displayed by a detector is compared with the standard colorimetric card, a content of copper ions in a water sample in example 1 is as follows: 8 mg/L.
Example 2
The method for rapidly detecting the copper ions comprises the following steps:
(1) preparing a color developing solution: the mass ratio of 1: 1, preparing 9mmol/L dicyclohexyl oxalyl dihydrazone solution by using absolute ethanol and deionized water;
(2) treating a base material: placing cotton cloth in a sodium carbonate solution with the mass fraction of 10% at 85 ℃, taking out and drying;
(3) preparing a detector: soaking the treated cotton cloth obtained in the step (2) into the bicyclohexanoneoxalyl dihydrazone solution obtained in the step (1), oscillating at constant temperature for 1.5h at 25 ℃, taking out, airing in a shady and cool place in the dark, cutting to small blocks of 0.8cm x 0.6cm to obtain a detector, and placing the detector in a shady and dry place for sealed storage;
(4) preparing a standard colorimetric card: respectively preparing copper ion solutions with the concentrations of 4mg/L, 8mg/L, 12mg/L and 16mg/L and the pH value of 9, respectively dripping 0.1mL of the solutions into the copper ion solution prepared in the step (3) and adjusting the pH value of the ammonia water-ammonium chloride buffer solution to 9, respectively dripping 0.1mL of the solutions onto the detector prepared in the step (3) for reaction, respectively recording the corresponding colors by using a camera, collecting the colors by using photo processing software, and printing to obtain a standard colorimetric card;
(5) preparing a sample to be tested: preparing 4mg/L copper ion solution by using deionized water, and adjusting the pH value of the copper ion solution to 9 by using ammonia water-ammonium chloride buffer solution;
(6) and (4) dripping 0.2mL of the sample to be detected obtained in the step (5) on the detector obtained in the step (3), and comparing the color of the detector with the color comparison card to obtain the concentration of copper ions in the sample to be detected.
The preparation of the standard colorimetric card is consistent with that of example 1, fig. 3 is a test object diagram in example 2 of the present invention, and when the color displayed by the detector is compared with that of the standard colorimetric card, the content of copper ions in the water sample in example 1 is as follows: 4 mg/L.
Example 3
The method for rapidly detecting the copper ions comprises the following steps:
(1) preparing a color developing solution: the mass ratio of 1: 1, preparing 8mmol/L dicyclohexyl oxalyl dihydrazone solution by using absolute ethyl alcohol and deionized water;
(2) treating a base material: placing cotton cloth in a sodium carbonate solution with the mass fraction of 10% at 85 ℃, taking out and drying;
(3) preparing a detector: soaking the treated cotton cloth obtained in the step (2) into the bicyclohexanoneoxalyl dihydrazone solution obtained in the step (1), oscillating at constant temperature for 1.5h at 20 ℃, taking out, airing in shade, cutting to small blocks of 0.8cm x 0.6cm to obtain a detector, and placing the detector in a shade dry place for sealed storage;
(4) preparing a standard colorimetric card: respectively preparing copper ion solutions with the concentrations of 4mg/L, 8mg/L, 12mg/L and 16mg/L and the pH value of 9, respectively dripping 0.1mL of the solutions into the copper ion solution prepared in the step (3) and adjusting the pH value of the ammonia water-ammonium chloride buffer solution to 9, respectively dripping 0.1mL of the solutions onto the detector prepared in the step (3) for reaction, respectively recording the corresponding colors by using a camera, collecting the colors by using photo processing software, and printing to obtain a standard colorimetric card;
(5) preparing a sample to be tested: preparing 16mg/L copper ion solution by using deionized water, and adjusting the pH value of the copper ion solution to 9 by using ammonia water-ammonium chloride buffer solution;
(6) and (4) dripping 0.1mL of the sample to be detected obtained in the step (5) on the detector obtained in the step (3), and comparing the color of the detector with the color comparison card to obtain the concentration of copper ions in the sample to be detected.
The preparation of the standard colorimetric card is consistent with that of example 1, fig. 4 is a test object diagram in example 3 of the present invention, and when the color displayed by the detector is compared with that of the standard colorimetric card, the content of copper ions in the water sample in example 1 is as follows: 16 mg/L.
Example 4
The method for rapidly detecting the copper ions comprises the following steps:
(1) preparing a color developing solution: the mass ratio of 1: 1, preparing 10mmol/L dicyclohexyl oxalyl dihydrazone solution by using absolute ethyl alcohol and deionized water;
(2) treating a base material: placing the cellulose membrane in a sodium carbonate solution with the mass fraction of 10% at 80 ℃, taking out and drying;
(3) preparing a detector: soaking the treated cotton cloth obtained in the step (2) into the bicyclohexanoneoxalyl dihydrazone solution obtained in the step (1), oscillating at constant temperature for 1h at 30 ℃, taking out, airing in shade, cutting to small blocks of 0.8cm x 0.6cm to obtain a detector, and placing the detector in a shade dry place for sealed storage;
(4) preparing a standard colorimetric card: respectively preparing copper ion solutions with the concentrations of 4mg/L, 8mg/L, 12mg/L and 16mg/L and the pH value of 9, respectively dripping 0.1mL of the solutions into the copper ion solution prepared in the step (3) and adjusting the pH value of the ammonia water-ammonium chloride buffer solution to 9, respectively dripping 0.1mL of the solutions onto the detector prepared in the step (3) for reaction, respectively recording the corresponding colors by using a camera, collecting the colors by using photo processing software, and printing to obtain a standard colorimetric card;
(5) preparing a sample to be tested: preparing 8mg/L copper ion solution by using deionized water, and adjusting the pH value of the copper ion solution to 9 by using ammonia water-ammonium chloride buffer solution;
(6) and (4) dripping 0.1mL of the sample to be detected obtained in the step (5) on the detector obtained in the step (3), and comparing the color of the detector with the color comparison card to obtain the concentration of copper ions in the sample to be detected.
The preparation of the standard colorimetric card is the same as that in example 1, and when the color displayed by the detector is compared with the standard colorimetric card, the content of copper ions in the water sample in example 4 is as follows: 8 mg/L.
Example 5
The method for rapidly detecting the copper ions comprises the following steps:
(1) preparing a color developing solution: the mass ratio of 1: 1, preparing 9mmol/L dicyclohexyl oxalyl dihydrazone solution by using absolute ethanol and deionized water;
(2) treating a base material: placing the cellulose membrane in a sodium carbonate solution with the mass fraction of 10% at 85 ℃, taking out and drying;
(3) preparing a detector: soaking the treated cotton cloth obtained in the step (2) into the bicyclohexanoneoxalyl dihydrazone solution obtained in the step (1), oscillating at constant temperature for 1.5h at 25 ℃, taking out, airing in a shady and cool place in the dark, cutting to small blocks of 0.8cm x 0.6cm to obtain a detector, and placing the detector in a shady and dry place for sealed storage;
(4) preparing a standard colorimetric card: respectively preparing copper ion solutions with the concentrations of 4mg/L, 8mg/L, 12mg/L and 16mg/L and the pH value of 9, respectively dripping 0.1mL of the solutions into the copper ion solution prepared in the step (3) and adjusting the pH value of the ammonia water-ammonium chloride buffer solution to 9, respectively dripping 0.1mL of the solutions onto the detector prepared in the step (3) for reaction, respectively recording the corresponding colors by using a camera, collecting the colors by using photo processing software, and printing to obtain a standard colorimetric card;
(5) preparing a sample to be tested: preparing 4mg/L copper ion solution by using deionized water, and adjusting the pH value of the copper ion solution to 9 by using ammonia water-ammonium chloride buffer solution;
(6) and (4) dripping 0.2mL of the sample to be detected obtained in the step (5) on the detector obtained in the step (3), and comparing the color of the detector with the color comparison card to obtain the concentration of copper ions in the sample to be detected.
The preparation of the standard colorimetric card is the same as that in example 1, and when the color displayed by the detector is compared with the standard colorimetric card, the content of copper ions in the water sample in example 5 is as follows: 4 mg/L.
Example 6
The method for rapidly detecting the copper ions comprises the following steps:
(1) preparing a color developing solution: the mass ratio of 1: 1, preparing 8mmol/L dicyclohexyl oxalyl dihydrazone solution by using absolute ethyl alcohol and deionized water;
(2) treating a base material: placing the cellulose membrane in a sodium carbonate solution with the mass fraction of 10% at 85 ℃, taking out and drying;
(3) preparing a detector: soaking the treated cotton cloth obtained in the step (2) into the bicyclohexanoneoxalyl dihydrazone solution obtained in the step (1), oscillating at constant temperature for 1.5h at 20 ℃, taking out, airing in shade, cutting to small blocks of 0.8cm x 0.6cm to obtain a detector, and placing the detector in a shade dry place for sealed storage;
(4) preparing a standard colorimetric card: respectively preparing copper ion solutions with the concentrations of 4mg/L, 8mg/L, 12mg/L and 16mg/L and the pH value of 9, respectively dripping 0.1mL of the solutions into the copper ion solution prepared in the step (3) and adjusting the pH value of the ammonia water-ammonium chloride buffer solution to 9, respectively dripping 0.1mL of the solutions onto the detector prepared in the step (3) for reaction, respectively recording the corresponding colors by using a camera, collecting the colors by using photo processing software, and printing to obtain a standard colorimetric card;
(5) preparing a sample to be tested: preparing 16mg/L copper ion solution by using deionized water, and adjusting the pH value of the copper ion solution to 9 by using ammonia water-ammonium chloride buffer solution;
(6) and (4) dripping 0.1mL of the sample to be detected obtained in the step (5) on the detector obtained in the step (3), and comparing the color of the detector with the color comparison card to obtain the concentration of copper ions in the sample to be detected.
The preparation of the standard colorimetric card is the same as that in example 1, and when the color displayed by the detector is compared with the standard colorimetric card, the content of copper ions in the water sample in example 6 is as follows: 16 mg/L.
Example 7
The method for rapidly detecting the copper ions comprises the following steps:
(1) preparing a color developing solution: the mass ratio of 1: 1, preparing 10mmol/L dicyclohexyl oxalyl dihydrazone solution by using absolute ethyl alcohol and deionized water;
(2) treating a base material: placing the bacterial cellulose membrane in a sodium carbonate solution with the mass fraction of 10% at 80 ℃, taking out and drying;
(3) preparing a detector: soaking the treated cotton cloth obtained in the step (2) into the bicyclohexanoneoxalyl dihydrazone solution obtained in the step (1), oscillating at constant temperature for 1h at 30 ℃, taking out, airing in shade, cutting to small blocks of 0.8cm x 0.6cm to obtain a detector, and placing the detector in a shade dry place for sealed storage;
(4) preparing a standard colorimetric card: respectively preparing copper ion solutions with the concentrations of 4mg/L, 8mg/L, 12mg/L and 16mg/L and the pH value of 9, respectively dripping 0.1mL of the solutions into the copper ion solution prepared in the step (3) and adjusting the pH value of the ammonia water-ammonium chloride buffer solution to 9, respectively dripping 0.1mL of the solutions onto the detector prepared in the step (3) for reaction, respectively recording the corresponding colors by using a camera, collecting the colors by using photo processing software, and printing to obtain a standard colorimetric card;
(5) preparing a sample to be tested: preparing 8mg/L copper ion solution by using deionized water, and adjusting the pH value of the copper ion solution to 9 by using ammonia water-ammonium chloride buffer solution;
(6) and (4) dripping 0.1mL of the sample to be detected obtained in the step (5) on the detector obtained in the step (3), and comparing the color of the detector with the color comparison card to obtain the concentration of copper ions in the sample to be detected.
The preparation of the standard colorimetric card is the same as that in example 1, and when the color displayed by the detector is compared with the standard colorimetric card, the content of copper ions in the water sample in example 4 is as follows: 8 mg/L.
Example 8
The method for rapidly detecting the copper ions comprises the following steps:
(1) preparing a color developing solution: the mass ratio of 1: 1, preparing 9mmol/L dicyclohexyl oxalyl dihydrazone solution by using absolute ethanol and deionized water;
(2) treating a base material: placing the bacterial cellulose membrane in a sodium carbonate solution with the mass fraction of 10% at 85 ℃, taking out and drying;
(3) preparing a detector: soaking the treated cotton cloth obtained in the step (2) into the bicyclohexanoneoxalyl dihydrazone solution obtained in the step (1), oscillating at constant temperature for 1.5h at 25 ℃, taking out, airing in a shady and cool place in the dark, cutting to small blocks of 0.8cm x 0.6cm to obtain a detector, and placing the detector in a shady and dry place for sealed storage;
(4) preparing a standard colorimetric card: respectively preparing copper ion solutions with the concentrations of 4mg/L, 8mg/L, 12mg/L and 16mg/L and the pH value of 9, respectively dripping 0.1mL of the solutions into the copper ion solution prepared in the step (3) and adjusting the pH value of the ammonia water-ammonium chloride buffer solution to 9, respectively dripping 0.1mL of the solutions onto the detector prepared in the step (3) for reaction, respectively recording the corresponding colors by using a camera, collecting the colors by using photo processing software, and printing to obtain a standard colorimetric card;
(5) preparing a sample to be tested: preparing 4mg/L copper ion solution by using deionized water, and adjusting the pH value of the copper ion solution to 9 by using ammonia water-ammonium chloride buffer solution;
(6) and (4) dripping 0.2mL of the sample to be detected obtained in the step (5) on the detector obtained in the step (3), and comparing the color of the detector with the color comparison card to obtain the concentration of copper ions in the sample to be detected.
The preparation of the standard colorimetric card is the same as that in example 1, and when the color displayed by the detector is compared with the standard colorimetric card, the content of copper ions in the water sample in example 5 is as follows: 4 mg/L.
Example 9
The method for rapidly detecting the copper ions comprises the following steps:
(1) preparing a color developing solution: the mass ratio of 1: 1, preparing 8mmol/L dicyclohexyl oxalyl dihydrazone solution by using absolute ethyl alcohol and deionized water;
(2) treating a base material: placing the bacterial cellulose membrane in a sodium carbonate solution with the mass fraction of 10% at 85 ℃, taking out and drying;
(3) preparing a detector: soaking the treated cotton cloth obtained in the step (2) into the bicyclohexanoneoxalyl dihydrazone solution obtained in the step (1), oscillating at constant temperature for 1.5h at 20 ℃, taking out, airing in shade, cutting to small blocks of 0.8cm x 0.6cm to obtain a detector, and placing the detector in a shade dry place for sealed storage;
(4) preparing a standard colorimetric card: respectively preparing copper ion solutions with the concentrations of 4mg/L, 8mg/L, 12mg/L and 16mg/L and the pH value of 9, respectively dripping 0.1mL of the solutions into the copper ion solution prepared in the step (3) and adjusting the pH value of the ammonia water-ammonium chloride buffer solution to 9, respectively dripping 0.1mL of the solutions onto the detector prepared in the step (3) for reaction, respectively recording the corresponding colors by using a camera, collecting the colors by using photo processing software, and printing to obtain a standard colorimetric card;
(5) preparing a sample to be tested: preparing 16mg/L copper ion solution by using deionized water, and adjusting the pH value of the copper ion solution to 9 by using ammonia water-ammonium chloride buffer solution.
(6) And (4) dripping 0.1mL of the sample to be detected obtained in the step (5) on the detector obtained in the step (3), and comparing the color of the detector with the color comparison card to obtain the concentration of copper ions in the sample to be detected.
The preparation of the standard colorimetric card is the same as that in example 1, and when the color displayed by the detector is compared with the standard colorimetric card, the content of copper ions in the water sample in example 6 is as follows: 16 mg/L.
Example 10
In the present invention, the method for selecting the preferred pH value comprises the following steps:
(a1) adding 1mL of 10mmol/L dicyclohexyl oxalyl dihydrazone solution and 4mL of 6mg/L copper ion solution into 7 centrifuge tubes respectively, adjusting the pH values to 1, 3, 5, 7, 9, 11 and 13 respectively, and adding into a cuvette respectively;
(a2) 1mL of deionized water and 4mL of copper ion solution with the concentration of 6mg/L are mixed to be used as reference solution, and the reference solution is added into a cuvette;
(a3) the spectrophotometry of each solution at 600nm was measured with an ultraviolet spectrophotometer, and the data obtained are shown in fig. 5.
The above experimental results show that the preferred pH range of the present invention is 7-9.
Example 11
The steps of the test method of the interference of other metal ions are as follows:
(b1) preparing 10mg/L Pb from 11 centrifugal tubes by deionized water2+、Ba2+、Zn2+、Ni2+、Mg2+、Cd2+、Mn2+、Co2+、Cu2+、K+、Na+A solution;
(b2) adjusting the pH of each solution of step (a2) to 9, wherein ferric ions take the supernatant;
(b3) mixing each solution prepared in the step (b2) with a bicyclohexanoneoxalyl dihydrazone solution with the concentration of 10mmol/L, pH value of 9 according to the mass ratio of 2: 1, respectively adding the mixed solution into a cuvette after mixing;
(b4) mixing 1mL of bicyclohexanoneoxalyl dihydrazone solution with the concentration of 10mmol/L, pH and the value of 9 with 2mL of deionized water to serve as a reference solution, and adding the reference solution into a cuvette;
(b5) the spectrophotometry of each solution at 600nm was measured with an ultraviolet spectrophotometer, and the data obtained are shown in FIG. 6.
The experiment shows that the method has strong anti-interference capability, and if the liquid to be measured contains other metal ions besides copper ions, the determination of the concentration of the copper ions is not influenced.
While the present invention has been described with reference to the embodiments shown in the drawings, the present invention is not limited to the embodiments, which are illustrative and not restrictive, and it will be apparent to those skilled in the art that various changes and modifications can be made therein without departing from the spirit and scope of the invention as defined in the appended claims.
Claims (8)
1. A copper ion rapid detection method is characterized by comprising the following steps:
(1) preparing a color developing solution: preparing a bicyclohexanoneoxalyl dihydrazone solution by using bicyclohexanoneoxalyl dihydrazone, absolute ethyl alcohol and deionized water;
(2) treating a base material: placing the base material in a sodium carbonate or sodium bicarbonate solution at 80-100 ℃, taking out and drying;
(3) preparing a detector: immersing the treated base material obtained in the step (2) into the bicyclohexanoneoxalyl dihydrazone solution obtained in the step (1), oscillating at constant temperature, taking out, drying, and cutting to a proper size to obtain a detector;
(4) preparing a sample to be tested: adjusting the pH value of a sample to be detected to 7-9 by using an ammonia water-ammonium chloride buffer solution;
(5) and (4) dripping the sample to be detected obtained in the step (4) on the detector obtained in the step (3), and comparing the color of the detector with the color comparison card to obtain the concentration of copper ions in the sample to be detected.
2. The method for rapidly detecting copper ions according to claim 1, wherein the method comprises the following steps: in the step (1), the mass ratio of ethanol in the bicyclohexanoneoxalyl dihydrazone solution is 30-50%, the preparation temperature is 20-45 ℃, and the concentration range of the prepared bicyclohexanoneoxalyl dihydrazone solution is 6-10 mmol/L.
3. The method for rapidly detecting copper ions according to claim 1, wherein the method comprises the following steps: in the step (2), the base material is cotton cloth or a cellulose membrane or a bacterial cellulose membrane, and the mass fraction range of the sodium carbonate solution is as follows: 8 to 10 percent.
4. The method for rapidly detecting copper ions according to claim 1, wherein the method comprises the following steps: in the step (3), the constant-temperature oscillation time is 1-2h, the temperature is 20-30 ℃, the drying treatment condition is drying in the shade in the dark, and the storage condition of the detector is placing in the shade and dry place for sealed storage.
5. The method for rapidly detecting copper ions according to claim 1, wherein the method comprises the following steps: in the step (4), the sample to be detected is liquid.
6. The method for rapidly detecting copper ions according to claim 1, wherein the method comprises the following steps: in the step (4), the concentration range of the copper ions in the sample to be detected is 4-16 mg/L.
7. The method for rapidly detecting copper ions according to claim 1, wherein the method comprises the following steps: in the step (5), the preparation method of the standard colorimetric card comprises the following steps: and (3) respectively preparing copper ion solutions with the concentrations of 4mg/L, 8mg/L, 12mg/L and 16mg/L and the pH value of 9, dripping 0.1mL of the solutions onto the detectors prepared in the step (3) respectively for reaction and photographing, collecting colors on the detectors together, and printing to obtain the standard colorimetric card.
8. The utility model provides a copper ion short-term test device which characterized in that: the detector and the standard colorimetric card related to the method for rapidly detecting copper ions according to any one of claims 1 to 6.
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