CN107817220B - Method for measuring mass concentration of easily released cyanide in thiocyanate-containing water - Google Patents
Method for measuring mass concentration of easily released cyanide in thiocyanate-containing water Download PDFInfo
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Abstract
The invention relates to a method for measuring the mass concentration of easily released cyanides in water containing thiocyanate, belonging to a method for measuring the mass concentration of easily released cyanides in the water containing thiocyanate. Performing primary distillation by using zinc nitrate and tartaric acid, transferring the distillate of the primary distillation into a distilled burned product, supplementing water, adding the zinc nitrate and the tartaric acid for performing secondary distillation treatment, collecting the distillate of the secondary distillation, and determining by using an isonicotinic acid-pyrazolone spectrophotometry. According to the invention, interference of thiocyanate is removed by a secondary distillation method, interference of thiocyanate is removed by selecting a reasonable mode, and the content of easily released cyanide is accurately determined.
Description
Technical Field
The invention relates to a method for quickly and accurately measuring easily released cyanides in water containing thiocyanate, in particular to a method for measuring the easily released cyanides in water in a colorimetric range and containing thiocyanate in water.
Background
People pay more and more attention to easily released cyanide nowadays because the easily released cyanide directly affects the personal safety and ecological environment of people, and countries pay more and more attention to the treatment of water quality containing the released cyanide nowadays, so that the accurate detection of the easily released cyanide is very important, and many enterprises can generate the easily released cyanide nowadays, for example, in the gold production process, a cyaniding gold leaching process is one of very important means, the water quality of the cyaniding gold leaching process contains the easily released cyanide and also contains higher thiocyanate, when the content of the easily released cyanide in the water quality is in the colorimetric range, the existing thiocyanate directly affects the accurate detection of the easily released cyanide by adopting the isonicotinic acid-pyrazolone spectrophotometry, because a part of the thiocyanate in the distillation process of the easily released cyanide detection can be evaporated and enters into an absorption liquid, and the thiocyanate and the cyanogen can directly react to generate the same final blue dye during the colorimetric process, the result is increased and very small amounts of thiocyanate have a great influence and must be removed in order to be able to determine accurately. The existing determination of easily released cyanide in water in the national standard and the ministry of environmental protection, such as HJ 484-2009 volumetric method and spectrophotometry for determining cyanide in water quality, does not consider the influence of thiocyanate.
Disclosure of Invention
The invention provides a method for measuring the mass concentration of an easily released cyanide in thiocyanate-containing water, aiming at finding an accurate method for measuring the content of the easily released cyanide in the existing thiocyanate-containing water to solve the problem of high measurement result of the easily released cyanide in the thiocyanate-containing water.
The technical scheme adopted by the invention is as follows: comprises the following steps:
(1) measuring 200mL of sample by using a measuring cylinder, recording the sample as a volume V, moving the sample into a distillation flask, adding a plurality of glass beads, adding 10-15 mL of zinc nitrate solution and 10-15 mL of tartaric acid solution, shaking uniformly, adding 10mL of sodium hydroxide solution into a receiving flask to serve as absorption liquid, connecting the upper end of a distillate conduit with the outlet of a condensation tube, inserting the lower end of the distillate conduit into the absorption liquid of the receiving flask, checking a connection part to ensure that the connection part is tight, and during distillation, inserting the lower end of the distillate conduit into the position below the liquid level of the absorption liquid to ensure that the absorption is complete;
(2) stopping distillation when the volume of the sample in the receiving bottle is 80-90 mL, flushing a distillate catheter with a small amount of water, taking out the receiving bottle, and fixing the volume to 100mL with water;
(3) transferring the distillate with the constant volume in the step (2) into a distillation flask, adding 100mL of distilled water, 10-15 mL of zinc nitrate solution and 10-15 mL of tartaric acid solution, and covering a bottle stopper; taking another receiving bottle, adding 10mL of sodium hydroxide solution as an absorption liquid, connecting the upper end of a distillate conduit with the outlet of a condensing tube, inserting the lower end of the distillate conduit into the absorption liquid of the receiving bottle, checking the connection part to ensure that the connection part is tight, and inserting the lower end of the distillate conduit into the position below the liquid level of the absorption liquid during distillation to ensure that the absorption is complete; opening the condensed water, opening an adjustable electric furnace, gradually increasing from a low level, and heating and distilling the distillate at the speed of 2-4 mL/min;
(4) stopping distillation when the volume of the sample in the receiving bottle in the step (3) is 80-90 mL, flushing the distillate conduit with a small amount of water, taking out the receiving bottle, and adding water to a constant volume of 100mL, which is recorded as a volume V1Marking the alkaline sample as 'A' to be detected;
(5) making a full procedure blank along with the sample to obtain an alkaline blank sample B to be detected;
(6) and (3) measuring the sample by the following steps:
1) the method for determining the mass concentration of the easily released cyanide by an isonicotinic acid-pyrazolone spectrophotometric method comprises the following steps:
drawing of standard curve
Taking 8 25mL colorimetric tubes with plugs, respectively adding 0.00mL, 0.20mL, 0.50 mL, 1.00 mL, 2.00 mL, 3.00 mL, 4.00 mL and 5.00mL of standard potassium cyanide solution, then adding 1g/L sodium hydroxide solution to 10mL, adding 5.0mL of phosphate buffer solution into each tube, uniformly mixing, rapidly adding 0.20mL of chloramine T solution, covering the plugs, uniformly mixing, standing for 3-5 min, adding 5.0mL of isonicotinic acid-pyrazolone solution into each tube, uniformly mixing, adding water to dilute to a marked line, and shaking uniformly; placing in a water bath device at 25-35 deg.C for 40min, performing color comparison, measuring absorbance with a spectrophotometer at 638nm wavelength by using a 10mm cuvette and reagent blank as reference, and drawing a calibration curve;
determination of basic sample "A
Draw 10.00mL of sample "A" into a 25mL stoppered cuvette and record as volume V2Adding 5.0mL of phosphate buffer solution into the tubes, uniformly mixing, rapidly adding 0.20mL of chloramine T solution, immediately covering a plug, uniformly mixing, standing for 3-5 min, adding 5.0mL of isonicotinic acid-pyrazolone solution into each tube, uniformly mixing, adding water for diluting, diluting to a constant volume of 25mL, shaking uniformly, standing in a water bath device at 25-35 ℃ for 40min, immediately carrying out color comparison, and using a spectrophotometer at a wavelength of 638nmMeasuring absorbance by taking a reagent blank as a reference in a 10mm cuvette, and calculating the corresponding mass A of the easily released cyanide from a calibration curve; simultaneously determining blank sample 'B', obtaining the mass A of the blank sample0。
In the step (1) and the step (3) of the invention,
the mass concentration of the zinc nitrate solution is 100 g/L: weighing 10.0g of zinc nitrate hexahydrate, dissolving in water, diluting to 100mL, and shaking up;
the tartaric acid solution has a mass concentration of 150 g/L: weighing 15.0g of zinc nitrate hexahydrate, dissolving in water, diluting to 100mL, and shaking up;
the mass concentration of the sodium hydroxide solution is 20 g/L: 20g of sodium hydroxide is weighed, dissolved in water, diluted to 1000mL, shaken up and stored in a polyethylene plastic container.
In the step (6) of the present invention,
the standard potassium cyanide solution used has the mass concentration: 1.00 mg/L;
weighing 1g of sodium hydroxide solution with the mass concentration of 1g/L, dissolving in water, diluting to 1000mL, shaking up, and storing in a polyethylene plastic container;
phosphate buffer solution, namely weighing 34.0g of anhydrous potassium dihydrogen phosphate and 35.5g of anhydrous disodium hydrogen phosphate, dissolving in water, diluting to a constant volume of 1000mL, and shaking up;
weighing 1.0g of chloramine T, dissolving in water, diluting to a constant volume of 100mL, shaking up, storing in a brown bottle, and preparing when in use;
isonicotinic acid-pyrazolone solution: weighing 1.5g of isonicotinic acid, dissolving in 25mL of sodium hydroxide solution with the mass concentration of 20g/L, adding water for dilution and fixing the volume to 100mL, weighing 0.25g of pyrazolone, dissolving in 20mL of N, N-dimethylformamide, and mixing the pyrazolone solution and the isonicotinic acid solution according to the ratio of 1:5, wherein the isonicotinic acid solution is prepared on site when in use.
In step (6) of the present invention, the result is calculated as follows:
the mass concentration rho of the easily released cyanide is calculated according to the following formula in terms of cyanide ions (CN-):
in the formula:
ρ: mass concentration of easily released cyanide, mg/L;
a: mass of sample, μ g;
A0: mass of blank sample, μ g;
v: volume of sample, mL;
V1: volume of sample (sample "a"), mL;
V2: volume of sample (sample "A" in colorimetry), mL.
The invention has the beneficial effects that: the content of cyanide which is easy to release in thiocyanate-containing water can be accurately determined, zinc nitrate and tartaric acid are used for primary distillation, distillate of the primary distillation is moved into a distillation burned product, water is supplemented, the zinc nitrate and the tartaric acid are added for secondary distillation treatment, distillate of the secondary distillation is collected, and the determination is performed by adopting an isonicotinic acid-pyrazolone spectrophotometry method. Thiocyanate in the secondary distillation distillate cannot be distilled out, so that thiocyanate interference is eliminated.
The invention successfully finds out that the interference of thiocyanate is removed by a secondary distillation method, a reasonable mode is selected, the interference of the thiocyanate is removed, and the content of the easily released cyanide is accurately determined.
Detailed Description
In the following examples, the reagents used were formulated as follows:
in the step (1) and the step (3) of the invention,
the mass concentration of the zinc nitrate solution is 100 g/L: weighing 10.0g of zinc nitrate hexahydrate, dissolving in water, diluting to 100mL, and shaking up;
the tartaric acid solution has a mass concentration of 150 g/L: weighing 15.0g of zinc nitrate hexahydrate, dissolving in water, diluting to 100mL, and shaking up;
the mass concentration of the sodium hydroxide solution is 20 g/L: 20g of sodium hydroxide is weighed, dissolved in water, diluted to 1000mL, shaken up and stored in a polyethylene plastic container.
In the step (6) of the present invention,
the standard potassium cyanide solution used has the mass concentration: 1.00 mg/L;
weighing 1g of sodium hydroxide solution with the mass concentration of 1g/L, dissolving in water, diluting to 1000mL, shaking up, and storing in a polyethylene plastic container;
phosphate buffer solution, namely weighing 34.0g of anhydrous potassium dihydrogen phosphate and 35.5g of anhydrous disodium hydrogen phosphate, dissolving in water, diluting to a constant volume of 1000mL, and shaking up;
weighing 1.0g of chloramine T, dissolving in water, diluting to a constant volume of 100mL, shaking up, storing in a brown bottle, and preparing when in use;
isonicotinic acid-pyrazolone solution: weighing 1.5g of isonicotinic acid, dissolving in 25mL of sodium hydroxide solution with the mass concentration of 20g/L, adding water for dilution and fixing the volume to 100mL, weighing 0.25g of pyrazolone, dissolving in 20mL of N, N-dimethylformamide, and mixing the pyrazolone solution and the isonicotinic acid solution according to the ratio of 1:5, wherein the isonicotinic acid solution is prepared on site when in use.
In step (6) of the present invention, the result is calculated as follows:
the mass concentration rho of the easily released cyanide is calculated according to the following formula in terms of cyanide ions (CN-):
in the formula:
ρ: mass concentration of easily released cyanide, mg/L;
a: mass of sample, μ g;
A0: mass of blank sample, μ g;
v: volume of sample, mL;
V1: volume of sample (sample "a"), mL;
V2: volume of sample (sample "A" in colorimetry), mL.
Example 1
Comprises the following steps:
(1) measuring 200mL of thiocyanate-containing sample by using a measuring cylinder, recording the volume as V, transferring the sample into a distillation flask, adding a plurality of glass beads, adding 10mL of zinc nitrate solution and 10mL of tartaric acid solution, shaking uniformly, adding 10mL of sodium hydroxide solution into a receiving flask to serve as absorption liquid, connecting the upper end of a distillate conduit with an outlet of a condensation tube, inserting the lower end of the distillate conduit into the absorption liquid of the receiving flask, checking a connection part to ensure that the connection part is tight, and during distillation, inserting the lower end of the distillate conduit into the lower part of the liquid level of the absorption liquid to ensure that the absorption is complete;
(2) when the volume of the sample in the receiving bottle is 80mL, stopping distillation, flushing a distillate catheter with a small amount of water, taking out the receiving bottle, and metering the volume to 100mL with water;
(3) transferring the distillate with the constant volume in the step (2) into a distillation flask, adding 100mL of distilled water, 10mL of zinc nitrate solution and 10mL of tartaric acid solution, and covering a bottle stopper; taking another receiving bottle, adding 10mL of sodium hydroxide solution as an absorption liquid, connecting the upper end of a distillate conduit with the outlet of a condensing tube, inserting the lower end of the distillate conduit into the absorption liquid of the receiving bottle, checking the connection part to ensure that the connection part is tight, and inserting the lower end of the distillate conduit into the position below the liquid level of the absorption liquid during distillation to ensure that the absorption is complete; opening the condensed water, opening an adjustable electric furnace, gradually increasing from a low level, and heating and distilling the distillate at the speed of 2 mL/min;
(4) when the volume of the sample in the receiving bottle in the step (3) is 80mL, stopping distillation, flushing a distillate catheter with a small amount of water, taking out the receiving bottle, and keeping the volume to be 100mL with water, wherein the volume is recorded as volume V1Marking the alkaline sample as 'A' to be detected;
(5) making a full procedure blank along with the sample to obtain an alkaline blank sample B to be detected;
(6) and (3) measuring the sample by the following steps:
1) the method for determining the mass concentration of the easily released cyanide by an isonicotinic acid-pyrazolone spectrophotometric method comprises the following steps:
drawing of standard curve
Taking 8 25mL colorimetric tubes with plugs, respectively adding 0.00mL, 0.20mL, 0.50 mL, 1.00 mL, 2.00 mL, 3.00 mL, 4.00 mL and 5.00mL of potassium cyanide standard use solution, then adding 1g/L sodium hydroxide solution to 10mL, adding 5.0mL of phosphate buffer solution into each tube, uniformly mixing, rapidly adding 0.20mL of chloramine T solution, covering the plugs, uniformly mixing, standing for 3min, adding 5.0mL of isonicotinic acid-pyrazolone solution into each tube, uniformly mixing, adding water to dilute to a marked line, and shaking uniformly; placing in a water bath device at 25 deg.C for 40min, performing color comparison, measuring absorbance with a spectrophotometer at 638nm wavelength by using 10mm cuvette and reagent blank as reference, and drawing calibration curve;
determination of basic sample "A
Draw 10.00mL of sample "A" into a 25mL stoppered cuvette and record as volume V2Adding 5.0mL of phosphate buffer solution into tubes, mixing uniformly, quickly adding 0.20mL of chloramine T solution, immediately covering a plug, mixing uniformly, standing for 3min, adding 5.0mL of isonicotinic acid-pyrazolone solution into each tube, mixing uniformly, adding water for dilution, fixing the volume to 25mL, shaking uniformly, standing in a water bath device at 25 ℃ for 40min, carrying out immediate colorimetry, measuring the absorbance by using a spectrophotometer at a wavelength of 638nm by using a 10mm cuvette and taking a reagent blank as a reference, calculating the corresponding amount A of the easily-released cyanide substance to be 2.00 mu g from a calibration curve, and simultaneously measuring a blank sample 'B' to obtain the mass A of the blank sample0；A0It was 0.008. mu.g.
Calculated to obtain the mass concentration of the easily released cyanide of 0.100 mg/L.
Example 2
Comprises the following steps:
(1) measuring 200mL of thiocyanate-containing sample by using a measuring cylinder, recording the volume as V, transferring the sample into a distillation flask, adding a plurality of glass beads, adding 12.5mL of zinc nitrate solution and 12.5mL of tartaric acid solution, shaking uniformly, adding 10mL of sodium hydroxide solution into a receiving flask to serve as absorption liquid, connecting the upper end of a distillate conduit with an outlet of a condensation tube, inserting the lower end of the distillate conduit into the absorption liquid of the receiving flask, checking a connection part to ensure that the connection part is tight, and inserting the lower end of the distillate conduit into the lower part of the liquid level of the absorption liquid during distillation to ensure that the absorption is complete;
(2) when the volume of the sample in the receiving bottle is 85mL, stopping distillation, flushing a distillate catheter with a small amount of water, taking out the receiving bottle, and metering the volume to 100mL with water;
(3) transferring the distillate with the constant volume in the step (2) into a distillation flask, adding 100mL of distilled water, 12.5mL of zinc nitrate solution and 12.5mL of tartaric acid solution, and covering a bottle stopper; taking another receiving bottle, adding 10mL of sodium hydroxide solution as an absorption liquid, connecting the upper end of a distillate conduit with the outlet of a condensing tube, inserting the lower end of the distillate conduit into the absorption liquid of the receiving bottle, checking the connection part to ensure that the connection part is tight, and inserting the lower end of the distillate conduit into the position below the liquid level of the absorption liquid during distillation to ensure that the absorption is complete; opening the condensed water, opening an adjustable electric furnace, gradually increasing from a low level, and heating and distilling the distillate at the speed of 3 mL/min;
(4) when the volume of the sample in the receiving bottle in the step (3) is 85mL, stopping distillation, flushing a distillate catheter with a small amount of water, taking out the receiving bottle, and keeping the volume to 100mL with water, wherein the volume is recorded as volume V1Marking the alkaline sample as 'A' to be detected;
(5) making a full procedure blank along with the sample to obtain an alkaline blank sample B to be detected;
(6) and (3) measuring the sample by the following steps:
1) the method for determining the mass concentration of the easily released cyanide by an isonicotinic acid-pyrazolone spectrophotometric method comprises the following steps:
drawing of standard curve
Taking 8 25mL colorimetric tubes with plugs, respectively adding 0.00mL, 0.20mL, 0.50 mL, 1.00 mL, 2.00 mL, 3.00 mL, 4.00 mL and 5.00mL of potassium cyanide standard use solution, then adding 1g/L sodium hydroxide solution to 10mL, adding 5.0mL of phosphate buffer solution into each tube, uniformly mixing, rapidly adding 0.20mL of chloramine T solution, covering the plugs, uniformly mixing, standing for 4min, adding 5.0mL of isonicotinic acid-pyrazolone solution into each tube, uniformly mixing, adding water to dilute to a marked line, and shaking uniformly; placing in a water bath device at 30 deg.C for 40min, performing color comparison, with a spectrophotometer at 638nm wavelength, measuring absorbance with 10mm cuvette and reagent blank as reference, and drawing calibration curve;
determination of basic sample "A
Draw 10.00mL of sample "A" into a 25mL stoppered cuvette and record as volume V2Adding 5.0mL of phosphate buffer solution into tubes, mixing uniformly, quickly adding 0.20mL of chloramine T solution, immediately covering a plug, mixing uniformly, standing for 4min, adding 5.0mL of isonicotinic acid-pyrazolone solution into each tube, mixing uniformly, adding water for dilution, fixing the volume to 25mL, shaking uniformly, standing in a 30 ℃ water bath device for 40min, carrying out immediate colorimetry, measuring the absorbance by using a spectrophotometer at a wavelength of 638nm by using a 10mm cuvette and taking a reagent blank as a reference, calculating the corresponding amount A of the easily-released cyanide substance to be 2.47 mu g from a calibration curve, and simultaneously measuring a blank sample 'B' to obtain the mass A of the blank sample0；A00.008 μ g;
calculated to obtain the mass concentration of the easily released cyanide of 0.123 mg/L.
Example 3
Comprises the following steps:
(1) measuring 200mL of thiocyanate-containing sample by using a measuring cylinder, recording the volume as V, transferring the sample into a distillation flask, adding a plurality of glass beads, adding 15mL of zinc nitrate solution and 15mL of tartaric acid solution, shaking uniformly, adding 10mL of sodium hydroxide solution into a receiving flask to serve as absorption liquid, connecting the upper end of a distillate conduit with an outlet of a condensation tube, inserting the lower end of the distillate conduit into the absorption liquid of the receiving flask, checking a connection part to ensure that the connection part is tight, and during distillation, inserting the lower end of the distillate conduit into the lower part of the liquid level of the absorption liquid to ensure that the absorption is complete;
(2) stopping distillation when the volume of the sample in the receiving bottle is 80-90 mL, flushing a distillate catheter with a small amount of water, taking out the receiving bottle, and fixing the volume to 100mL with water;
(3) transferring the distillate with the constant volume in the step (2) into a distillation flask, adding 100mL of distilled water, 15mL of zinc nitrate solution and 15mL of tartaric acid solution, and covering a bottle stopper; taking another receiving bottle, adding 10mL of sodium hydroxide solution as an absorption liquid, connecting the upper end of a distillate conduit with the outlet of a condensing tube, inserting the lower end of the distillate conduit into the absorption liquid of the receiving bottle, checking the connection part to ensure that the connection part is tight, and inserting the lower end of the distillate conduit into the position below the liquid level of the absorption liquid during distillation to ensure that the absorption is complete; opening the condensed water, opening an adjustable electric furnace, gradually increasing from a low level, and heating and distilling the distillate at the speed of 4 mL/min;
(4) when the volume of the sample in the receiving bottle in the step (3) is 90mL, stopping distillation, flushing a distillate catheter with a small amount of water, taking out the receiving bottle, and keeping the volume to be 100mL with water, wherein the volume is recorded as volume V1Marking the alkaline sample as 'A' to be detected;
(5) making a full procedure blank along with the sample to obtain an alkaline blank sample B to be detected;
(6) and (3) measuring the sample by the following steps:
1) the method for determining the mass concentration of the easily released cyanide by an isonicotinic acid-pyrazolone spectrophotometric method comprises the following steps:
drawing of standard curve
Taking 8 25mL colorimetric tubes with plugs, respectively adding 0.00mL, 0.20mL, 0.50 mL, 1.00 mL, 2.00 mL, 3.00 mL, 4.00 mL and 5.00mL of standard potassium cyanide solution, then adding 1g/L sodium hydroxide solution to 10mL, adding 5.0mL of phosphate buffer solution into each tube, uniformly mixing, rapidly adding 0.20mL of chloramine T solution, covering with the plugs, uniformly mixing, standing for 5min, adding 5.0mL of isonicotinic acid-pyrazolone solution into each tube, uniformly mixing, adding water to dilute to a marked line, and shaking uniformly; placing in a 35 deg.C water bath device for 40min, comparing color, measuring absorbance with a spectrophotometer at 638nm wavelength, using 10mm cuvette and reagent blank as reference, and drawing calibration curve;
determination of basic sample "A
Draw 10.00mL of sample "A" into a 25mL stoppered cuvette and record as volume V2Adding 5.0mL of phosphate buffer solution into the tubes, mixing uniformly, quickly adding 0.20mL of chloramine T solution, immediately covering a plug, mixing uniformly, standing for 5min, adding 5.0mL of isonicotinic acid-pyrazolone solution into each tube, mixing uniformly, adding water for dilution, diluting to a constant volume of 25mL, shaking uniformly, standing in a 35 ℃ water bath device for 40min, carrying out immediate colorimetry, measuring absorbance by using a spectrophotometer at a wavelength of 638nm by using a 10mm cuvette and taking a reagent blank as a reference, and calculating a corresponding easy calibration curveThe amount of released cyanide (A, 4.47. mu.g) was measured and the amount of blank sample (B) was measured to obtain the amount of blank sample (A)0；A00.008 μ g;
the mass concentration of the easily released cyanide is calculated to be 0.223 mg/L.
The effects of the present invention will be further described below by way of experimental examples.
Experimental example 1 measurement was carried out on a standard sample having a standard value of 0.136mg/L
(1) Measuring 200mL of standard sample by using a measuring cylinder, recording the standard sample as a volume V, transferring the standard sample into a distillation flask, adding a plurality of glass beads, then adding 200mg of sodium thiocyanate, adding 12.5mL of zinc nitrate solution and 12.5mL of tartaric acid solution, shaking uniformly, adding 10mL of sodium hydroxide solution into a receiving flask to be used as absorption liquid, connecting the upper end of a distillate conduit with an outlet of a condensation tube, inserting the lower end of the distillate conduit into the absorption liquid of the receiving flask, checking a connection part to ensure that the distillate conduit is tight, and inserting the lower end of the distillate conduit into the lower part of the liquid level of the absorption liquid during distillation to ensure that the absorption is;
(2) when the volume of the sample in the receiving bottle is 85mL, stopping distillation, flushing a distillate catheter with a small amount of water, taking out the receiving bottle, and metering the volume to 100mL with water;
(3) transferring the distillate with the constant volume in the step (2) into a distillation flask, adding 100mL of distilled water, 12.5mL of zinc nitrate solution and 12.5mL of tartaric acid solution, and covering a bottle stopper; taking another receiving bottle, adding 10mL of sodium hydroxide solution as an absorption liquid, connecting the upper end of a distillate conduit with the outlet of a condensing tube, inserting the lower end of the distillate conduit into the absorption liquid of the receiving bottle, checking the connection part to ensure that the connection part is tight, and inserting the lower end of the distillate conduit into the position below the liquid level of the absorption liquid during distillation to ensure that the absorption is complete; opening the condensed water, opening an adjustable electric furnace, gradually increasing from a low level, and heating and distilling the distillate at the speed of 3 mL/min;
(4) when the volume of the sample in the receiving bottle in the step (3) is 85mL, stopping distillation, flushing a distillate catheter with a small amount of water, taking out the receiving bottle, and keeping the volume to 100mL with water, wherein the volume is recorded as volume V1The basic sample is designated"A", to be measured;
(5) making a full procedure blank along with the sample to obtain an alkaline blank sample B to be detected;
(6) and (3) measuring the sample by the following steps:
1) the method for determining the mass concentration of the easily released cyanide by an isonicotinic acid-pyrazolone spectrophotometric method comprises the following steps:
drawing of standard curve
Taking 8 25mL colorimetric tubes with plugs, respectively adding 0.00mL, 0.20mL, 0.50 mL, 1.00 mL, 2.00 mL, 3.00 mL, 4.00 mL and 5.00mL of potassium cyanide standard use solution, then adding 1g/L sodium hydroxide solution to 10mL, adding 5.0mL of phosphate buffer solution into each tube, uniformly mixing, rapidly adding 0.20mL of chloramine T solution, covering the plugs, uniformly mixing, standing for 4min, adding 5.0mL of isonicotinic acid-pyrazolone solution into each tube, uniformly mixing, adding water to dilute to a marked line, and shaking uniformly; placing in a water bath device at 30 deg.C for 40min, performing color comparison, with a spectrophotometer at 638nm wavelength, measuring absorbance with 10mm cuvette and reagent blank as reference, and drawing calibration curve;
determination of basic sample "A
Draw 10.00mL of sample "A" into a 25mL stoppered cuvette and record as volume V2Adding 5.0mL of phosphate buffer solution into tubes, mixing uniformly, quickly adding 0.20mL of chloramine T solution, immediately covering a plug, mixing uniformly, standing for 4min, adding 5.0mL of isonicotinic acid-pyrazolone solution into each tube, mixing uniformly, adding water for dilution, fixing the volume to 25mL, shaking uniformly, standing in a 30 ℃ water bath device for 40min, carrying out immediate colorimetry, measuring the absorbance by using a spectrophotometer at a wavelength of 638nm by using a 10mm cuvette and taking a reagent blank as a reference, calculating the corresponding amount A of the easily-released cyanide substance to be 2.73 mu g from a calibration curve, and simultaneously measuring a blank sample 'B' to obtain the mass A of the blank sample0；A00.008 μ g;
the mass concentration of the substance which is easy to release and release cyanide is calculated to be 0.136 mg/L.
Claims (4)
1. A method for measuring the mass concentration of easily released cyanide in thiocyanate-containing water is characterized by comprising the following steps:
(1) measuring 200mL of sample by using a measuring cylinder, recording the sample as a volume V, moving the sample into a distillation flask, adding a plurality of glass beads, adding 10-15 mL of zinc nitrate solution and 10-15 mL of tartaric acid solution, shaking uniformly, adding 10mL of sodium hydroxide solution into a receiving flask to serve as absorption liquid, connecting the upper end of a distillate conduit with the outlet of a condensation tube, inserting the lower end of the distillate conduit into the absorption liquid of the receiving flask, checking a connection part to ensure that the connection part is tight, and during distillation, inserting the lower end of the distillate conduit into the position below the liquid level of the absorption liquid to ensure that the absorption is complete;
(2) stopping distillation when the volume of the sample in the receiving bottle is 80-90 mL, flushing a distillate catheter with a small amount of water, taking out the receiving bottle, and fixing the volume to 100mL with water;
(3) transferring the distillate with the constant volume in the step (2) into a distillation flask, adding 100mL of distilled water, 10-15 mL of zinc nitrate solution and 10-15 mL of tartaric acid solution, and covering a bottle stopper; taking another receiving bottle, adding 10mL of sodium hydroxide solution as an absorption liquid, connecting the upper end of a distillate conduit with the outlet of a condensing tube, inserting the lower end of the distillate conduit into the absorption liquid of the receiving bottle, checking the connection part to ensure that the connection part is tight, and inserting the lower end of the distillate conduit into the position below the liquid level of the absorption liquid during distillation to ensure that the absorption is complete; opening the condensed water, opening an adjustable electric furnace, gradually increasing from a low level, and heating and distilling the distillate at the speed of 2-4 mL/min;
(4) stopping distillation when the volume of the sample in the receiving bottle in the step (3) is 80-90 mL, flushing the distillate conduit with a small amount of water, taking out the receiving bottle, and adding water to a constant volume of 100mL, which is recorded as a volume V1Marking the alkaline sample as 'A' to be detected;
(5) making a full procedure blank along with the sample to obtain an alkaline blank sample B to be detected;
(6) and (3) measuring the sample by the following steps:
1) the method for determining the mass concentration of the easily released cyanide by an isonicotinic acid-pyrazolone spectrophotometric method comprises the following steps:
drawing of standard curve
Taking 8 25mL colorimetric tubes with plugs, respectively adding 0.00mL, 0.20mL, 0.50 mL, 1.00 mL, 2.00 mL, 3.00 mL, 4.00 mL and 5.00mL of standard potassium cyanide solution, then adding 1g/L sodium hydroxide solution to 10mL, adding 5.0mL of phosphate buffer solution into each tube, uniformly mixing, rapidly adding 0.20mL of chloramine T solution, covering the plugs, uniformly mixing, standing for 3-5 min, adding 5.0mL of isonicotinic acid-pyrazolone solution into each tube, uniformly mixing, adding water to dilute to a marked line, and shaking uniformly; placing in a water bath device at 25-35 deg.C for 40min, performing color comparison, measuring absorbance with a spectrophotometer at 638nm wavelength by using a 10mm cuvette and reagent blank as reference, and drawing a calibration curve;
determination of basic sample "A
Draw 10.00mL of sample "A" into a 25mL stoppered cuvette and record as volume V2Adding 5.0mL of phosphate buffer solution into the tubes, uniformly mixing, rapidly adding 0.20mL of chloramine T solution, immediately covering a plug, uniformly mixing, standing for 3-5 min, adding 5.0mL of isonicotinic acid-pyrazolone solution into each tube, uniformly mixing, adding water for diluting, diluting to a constant volume of 25mL, shaking uniformly, standing in a water bath device at 25-35 ℃ for 40min, immediately carrying out color comparison, measuring absorbance by using a spectrophotometer at 638nm wavelength and a 10mm cuvette and taking a reagent blank as a reference, and calculating the corresponding mass A of the easily released cyanide on a calibration curve; simultaneously determining blank sample 'B', obtaining the mass A of the blank sample0。
2. The method according to claim 1, wherein the mass concentration of the easily released cyanide in the thiocyanate-containing water is determined by: in the step (1) and the step (3),
the mass concentration of the zinc nitrate solution is 100 g/L: weighing 10.0g of zinc nitrate hexahydrate, dissolving in water, diluting to 100mL, and shaking up;
the tartaric acid solution has a mass concentration of 150 g/L: weighing 15.0g of tartaric acid, dissolving in water, diluting to a constant volume of 100mL, and shaking up;
the mass concentration of the sodium hydroxide solution is 20 g/L: 20g of sodium hydroxide is weighed, dissolved in water, diluted to 1000mL, shaken up and stored in a polyethylene plastic container.
3. The method according to claim 1, wherein the mass concentration of the easily released cyanide in the thiocyanate-containing water is determined by: in the step (6), the step (c),
the standard potassium cyanide solution used has the mass concentration: 1.00 mg/L;
weighing 1g of sodium hydroxide solution with the mass concentration of 1g/L, dissolving in water, diluting to 1000mL, shaking up, and storing in a polyethylene plastic container;
phosphate buffer solution: weighing 34.0g of anhydrous potassium dihydrogen phosphate and 35.5g of anhydrous disodium hydrogen phosphate, dissolving in water, diluting to a constant volume of 1000mL, and shaking up;
weighing 1.0g of chloramine T, dissolving in water, diluting to a constant volume of 100mL, shaking up, storing in a brown bottle, and preparing when in use;
isonicotinic acid-pyrazolone solution: weighing 1.5g of isonicotinic acid, dissolving in 25mL of sodium hydroxide solution with the mass concentration of 20g/L, adding water for dilution and fixing the volume to 100mL, weighing 0.25g of pyrazolone, dissolving in 20mL of N, N-dimethylformamide, and mixing the pyrazolone solution and the isonicotinic acid solution according to the ratio of 1:5, wherein the isonicotinic acid solution is prepared on site when in use.
4. The method according to claim 1, wherein the mass concentration of the easily released cyanide in the thiocyanate-containing water is determined by: in the step (6), the result is calculated as follows:
the mass concentration rho of the easily released cyanide is calculated according to the following formula in terms of cyanide ion CN < - >:
in the formula:
ρ: mass concentration of easily released cyanide, mg/L;
a: mass of sample, μ g;
A0: mass of blank sample, μ g;
v: volume of sample, mL;
V1: volume of sample "a", mL;
V2: for colorimetric purposes, the volume of sample "A", mL, is taken.
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| CN113030071A (en) * | 2021-02-22 | 2021-06-25 | 长春黄金研究院有限公司 | Method for determining cyanide easily released in thiocyanate-containing water |
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