CN1991339A - Method for analyzing total phosphorus content in sample - Google Patents
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- CN1991339A CN1991339A CN 200510135588 CN200510135588A CN1991339A CN 1991339 A CN1991339 A CN 1991339A CN 200510135588 CN200510135588 CN 200510135588 CN 200510135588 A CN200510135588 A CN 200510135588A CN 1991339 A CN1991339 A CN 1991339A
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Abstract
一种分析样品中总磷含量的方法，该方法包括下列步骤：(1)将待测样品与一种分解剂混合，将所得混合物加热至完全干燥，所述分解剂为强氧化性的酸性化合物的溶液；(2)将上述完全干燥后的产物用一种酸性溶液完全溶解；(3)将步骤(2)所得产物与钼酸盐或钼酸盐溶液混合；(4)将步骤(3)所得产物与一种还原剂或还原剂溶液混合进行显色反应；(5)用分光光度法测定步骤(4)所得的混合液中的磷钼蓝的含量。按照本发明提供的方法分析样品中总磷，由于加热终点统一，因此大大减少由于人为操作误差引起的分析结果不准确；同时样品中的聚磷酸盐被转化为正磷酸盐，可测出常规方法无法测得的这部分总磷，因而分析准确性和精密度提高。
A method for analyzing total phosphorus content in a sample, the method comprising the following steps: (1) mixing the sample to be tested with a decomposing agent, and heating the resulting mixture to dryness completely, the decomposing agent being a strong oxidizing acidic compound (2) the above-mentioned completely dried product is completely dissolved with an acidic solution; (3) the product obtained in step (2) is mixed with molybdate or molybdate solution; (4) step (3) The obtained product is mixed with a reducing agent or a reducing agent solution to carry out a color reaction; (5) the content of phosphomolybdenum blue in the mixed solution obtained in step (4) is determined by spectrophotometry. According to the method provided by the invention to analyze the total phosphorus in the sample, due to the uniform heating end point, the inaccurate analysis results caused by human operation errors are greatly reduced; at the same time, the polyphosphate in the sample is converted into orthophosphate, which can be detected by conventional methods This part of the total phosphorus that cannot be measured, thus improving the accuracy and precision of the analysis.
Description
Technical field
The invention relates to the method for total phosphorus content in a kind of analytic sample.
Background technology
The assay determination of total phosphorus is widely used in industry, can monitoring of environmental such as measuring total phosphorus in the sewage, can rationally control aspect effect such as industrial circulating water treatment effect by total phosphorus great.For solving fouling and the etching problem of industrial circulating cooling water in heat transmission equipment, generally use single agent of phosphorous water treatment or complexing agent cycle of treatment water.But the industrial circulating water that has added phosphorous treating agent can increase the weight of environment water pollution and eutrophication degree when discharging.In addition, phosphorous water treatment agent is overstand in the industrial cycle cooling system, can form calcium phosphate scale, and the treatment effect of recirculated water is descended.Therefore need carry out strictness and monitoring accurately to the total phosphorus in total phosphorus in the water treatment agent and the recirculated water.
Measure total phosphorus and can judge on the one hand whether the quality of single agent of phosphorous water treatment or complexing agent is qualified; On the other hand, can be used as the effect of the controlling index evaluation water treatment of recirculated water.The accuracy that total phosphorus is analyzed is most important, if the total phosphorus assay value is lower than actual value in the water treatment agent, adds excessive water treatment agent for the controlling index that reaches the recirculated water total phosphorus, has increased the unnecessary processing cost; If the total phosphorus assay value is higher than actual value in the water treatment agent, causes the total phosphorus of recirculated water to be lower than controlling index, thereby influence treatment effect.
The method of measuring at present total phosphorus comprises the solution that heats testing sample and the potpourri of distintegrant, cooling, the product of the cooling that obtains is mixed with molybdate solution and reductant solution respectively, the content of the phosphorus molybdenum blue in the mixed liquor that mensuration obtains, the solution of heating testing sample and the potpourri of distintegrant immersion method commonly used or calcination method.But immersion method is only applicable to persulfate as the low situation of organic concentration in distintegrant and the sample.And reveal or reusing sewage during in recirculating cooling water system at the recirculated water material, require to measure the total phosphorus in the high recirculated water of organic concentration, so the calcination method is more suitable for than immersion method.
But the heating terminal point of prior art calcination method is uncertain, has following several describing mode usually: be heated to the fast distilled-to-dryness of solution; Be heated to till the surplus some milliliters of solution; Being heated to solution has just emitted till the white mist; Being heated to solution just occurs till the crystallization.For example, in the mensuration ammonium molybdate spectrophotometric method (ZB/T G76002-90) of GB industrial circulating cooling water phosphorus content with " on the electric furnace slow boil 15 minutes " to the fast distilled-to-dryness of solution as heating terminal point.Above endpoint method, subjectivity is strong, and different operators judges inconsistent, causes the errors of analytical results of same sample big; Even same operating personnel are also lower to same sample analysis result's precision.
Heating terminal point during the prior art calcination is very big to the result of total phosphorus in analytic sample influence: heat insufficiently, the phosphorus in testing sample decomposition and inversion fully is positive phosphorus, causes measurement result on the low side; During over-heating, and under with the condition of non-oxidizing acids such as sulfuric acid or hydrochloric acid as distintegrant, the small part phosphorus in the sample can generate colourless, poisonous hydrogen phosphide (PH
3) gas (when adopting acid with strong oxidizing property as distintegrant, then can not produce hydrogen phosphide), because the effusion of this gas causes the loss of phosphorus in the testing sample, and makes measurement result on the low side; Under this external superheated condition, a part of orthophosphate can form Quadrafos, and this material can not generate phosphato-molybdic heteropolyacid with the molybdate reaction under acid condition, therefore can't detect the phosphorus in them, also can cause analysis result on the low side.
To sum up, the method accuracy of total phosphorus is not good enough in the prior art analytic sample, the manual operation error effect is big, needs the method for total phosphorus in a kind of better analytic sample to overcome above-mentioned shortcoming.
Summary of the invention
The objective of the invention is to overcome the shortcoming that the method accuracy is not good enough, the manual operation error effect is big of total phosphorus in the prior art analytic sample, the method for total phosphorus in the total phosphorus analytic sample is provided in the analytic sample that a kind of accuracy is good, the manual operation error effect is little.
The invention provides the method for total phosphorus content in a kind of analytic sample, this method comprises the following steps:
(1) testing sample is mixed with a kind of distintegrant, to bone dry, described distintegrant is the solution of the acid compound of strong oxidizing property with the gained mixture heated;
(2) product behind the above-mentioned bone dry is dissolved fully with a kind of acid solution;
(3) step (2) products therefrom is mixed with molybdate or molybdate solution;
(4) step (3) products therefrom is mixed with a kind of reductive agent or reductant solution carry out chromogenic reaction;
(5) content of the phosphorus molybdenum blue in the mixed liquor of usefulness spectrophotometry step (4) gained.
According to total phosphorus in the methods analyst sample provided by the invention, because the heating terminal point is unified, operating personnel grasp easily, therefore significantly reduce because the analysis result that the manual operation error causes is inaccurate; Simultaneously under acid condition, the Quadrafos in the sample is converted into orthophosphate, can measures this part total phosphorus that conventional method can't record, thereby improve the accuracy and the precision of the method for total phosphorus in the analytic sample.This method is applicable to the single agent of soluble solids sample and fluid sample such as phosphorous water treatment, phosphorous all-organic formula, phosphorous complexing agent, phosphorous circulation water sample etc.
For example, carry out the analysis of total phosphorus for ammonia nitrogen, nitrate nitrogen, total phosphorus composition secondary analysis standard substance in the GBW of National Quality ﹠ Technology Inspection Bureau (E) 080431 water, embodiment 2 adopts total phosphorus in the way analytic sample of the present invention, and total phosphorus in the mensuration ammonium molybdate spectrophotometric analysis sample of Comparative Examples 1 employing GB industrial circulating cooling water phosphorus content.The statistics that compares two kinds of methods: the former relative error is between-2.6% to 1.8%, and the latter is-9.2% to 2.3%, and the former relative error is significantly less than the latter; The former standard deviation is 0.556, and the latter reaches 1.306; The former coefficient of variation is 1.82%, and the latter reaches 4.36%; The method accuracy of total phosphorus is higher than the method for Comparative Examples 1 in the comprehensive above statistics index analytic sample provided by the invention as can be seen.
Description of drawings
Absorbance under Fig. 1 phosphorus molybdenum blue 710 nano wave lengths is to the typical curve of phosphorus content.
Embodiment
The invention provides the method for total phosphorus content in a kind of analytic sample, this method comprises the following steps:
(1) testing sample is mixed with a kind of distintegrant, to bone dry, described distintegrant is the solution of the acid compound of strong oxidizing property with the gained mixture heated;
(2) product behind the above-mentioned bone dry is dissolved fully with a kind of acid solution;
(3) step (2) products therefrom is mixed with molybdate or molybdate solution;
(4) step (3) products therefrom is mixed with a kind of reductive agent or reductant solution carry out chromogenic reaction;
(5) content of the phosphorus molybdenum blue in the mixed liquor of usefulness spectrophotometry step (4) gained.
Wherein the acid compound of the described strong oxidizing property of step (1) is selected from one or more in nitric acid, perchloric acid or the hypochlorous acid.Adopt the acidic materials of strong oxidizing property such as nitric acid and perchloric acid as distintegrant, because their existence makes the PH of reductibility in the reaction system
3Can't form, so total phosphorus can be because of not forming PH
3Gas and overflow and have loss.
The addition of the acid compound of described strong oxidizing property is the consumption of conventional distintegrant, to make the acid compound of described strong oxidizing property and the weight ratio of testing sample be 0.1-3.0 to the addition of the acid compound of strong oxidizing property as described: 1, be preferably 0.2-2.0: 1.
The method of the method for described bone dry is a lot, as infra-red furnace, micro-wave oven, electric furnace water-bath, electric furnace calcination etc., just can adopt as long as can reach the purpose of bone dry.The method of preferred described bone dry is calcination.When described bone dry was meant the potpourri that continues heating testing sample and distintegrant, the quality of this potpourri was constant substantially, does not promptly have acid mist and water vapor to be evaporated out.Described heating can also continue 0-60 minute behind the potpourri bone dry of the solution of testing sample and distintegrant, preferably continued heating 1-10 minute.When using prior art to decompose total phosphorus,, therefore need special messenger's nurse in case calcination is excessive because the heating terminal point is written in water, in case and the over-heating analysis of can only resampling; Heating terminal point of the present invention is fixed, and continues heating 0-60 minute, not impact analysis result's accuracy after arriving the heating terminal point.Therefore the present invention's operation is simpler, because the error that manual operation causes is little.
Method provided by the invention also is included in the step that step (2) is cooled off the product behind the described bone dry before.Described cooling can natural cooling, also can rely on cooling device to realize.Described cooling helps quantitative the carrying out of safety of subsequent step, preferably is cooled to room temperature.
The described acid solution of step (2) is selected from sulfuric acid solution and/or hydrochloric acid solution.It is the 0.3-2.5 mol that the addition of described acid solution makes the pH of the potpourri of product behind the described bone dry and acid solution.Acid solution can be converted into orthophosphate with Quadrafos in the testing sample, makes like this that the contained phosphorus of Quadrafos also can be detected in the sample, has increased the objectivity that total phosphorus is analyzed.The pH of the product behind the described bone dry and the potpourri of acid solution is more than or equal to 0.3 mol, just can reach goal of the invention of the present invention, preferred 0.3-2.5 mol, in this scope, not only can all be converted into orthophosphate to the Quadrafos in the sample, also not influence subsequent step.
It can be the product behind the described bone dry of heating and the potpourri of acid solution that step (2) makes the consoluet method of product behind the described bone dry, product behind the described bone dry is dissolved fully, for example, make the product behind the described bone dry and little the boiling of potpourri of acid solution.Described little time of boiling is 1-30 minute, preferred 5-15 minute.
Also be included in step (3) before according to method provided by the invention, the pH value of the solution after step (2) gained is dissolved fully is adjusted to 8.0-10.0.In this pH value scope, the final pH value of the mixed liquor that forms helps the reaction of orthophosphate and molybdate and generates yellow phosphato-molybdic heteropolyacid behind step (3) the adding bimolybdate solution, is reduced agent again and is reduced into the phosphorus molybdenum blue.
The described molybdate of step (3) is selected from and anyly can generates in the molybdate of phosphato-molybdic heteropolyacid one or more with orthophosphate reaction.For example, described molybdate can be selected from one or more in ammonium molybdate, sodium molybdate or the potassium molybdate, and it is 92-150 that the addition of described molybdate or molybdate solution makes the weight ratio of the product behind molybdate and the described bone dry: 1.The addition of described molybdate solution wherein molybdate is excessive with respect to orthophosphate, in general, the addition of molybdate solution makes product weight ratio behind molybdate and the described bone dry for being at least 92 as described, though also can implement the present invention greatly again, but under the preferable case, this weight ratio is 92-150: 1, and being preferably weight ratio is 92-130: 1.Described molybdate is excessive in described scope, the whole orthophosphate in the product behind the described bone dry all can be changed into phosphato-molybdic heteropolyacid.
The described reductive agent of step (4) is selected from one or more in any reductive agent that phosphato-molybdic heteropolyacid can be reduced into the phosphorus molybdenum blue.Described reductive agent can be selected from one or more in ascorbic acid, hydrazine sulfate or the stannous chloride.Preferred ascorbic acid, this reductive agent not only is reduced into phosphato-molybdic heteropolyacid stable phosphorus molybdenum blue, and the coloring matter of the accuracy of analysis that do not exert an influence in the reduction process.Described reductant solution addition be as well known to those skilled in the art, preferably making the addition of described reductant solution make the mol ratio of reductive agent and described molybdate is 4: 3 to 2: 1.
The mensuration of phosphorus molybdenum blue adopts spectrophotometry, as the content of phosphorus molybdenum blue being measured in maximum absorption wavelength 710 nanometers of phosphorus molybdenum blue with spectrophotometric method.The addition of testing sample solution need be adjusted according to the absorbance analysis result, suitably increases or reduces, and makes absorbance that spectrophotometer records in the 0.300-0.700 scope.
The method of total phosphorus in the analytic sample provided by the invention, its testing sample can be solid, liquid and/or gas.Described solid testing sample can be water treatment agent, mineral, metallic article etc., makes colourless solution by pre-service and measures.Described pre-service is for example: to solubility sample wiring solution-forming; Suspending liquid or emulsion are carried out filtration treatment etc.With methods analyst of the present invention total phosphorus content wherein.Described fluid test sample can be water treatment agent, sewage, recirculated water etc., can analyze after also can diluting directly with methods analyst of the present invention total phosphorus content wherein.Described gas testing sample can be PH
3Deng, the gas testing sample is dissolved in solution, use methods analyst of the present invention total phosphorus content wherein then.
Unless stated otherwise, used medicine is commercially available analytical reagent in the specific embodiment of the invention, and institute's water is the water of distilled water or equal purity.
The present invention is described further below in conjunction with embodiment.
Embodiment 1
The following examples explanation, the drafting of typical curve and the computing method of total phosphorus content.
(1) preparation of phosphorus standard solution
Take by weighing 0.7165 and restrain the potassium dihydrogen phosphate that has been dried to constant weight under 105 ℃, be dissolved in 500 ml waters, the solution that obtains is transferred in 1 liter of volumetric flask, the water constant volume shakes up, and must contain 0.5 mg/ml PO
4 3-Phosphorus standard mother liquor.Get 20.00 milliliters of phosphorus standard mother liquors in 500.00 milliliters of volumetric flasks, the water constant volume shakes up, and must contain 0.02 mg/ml PO
4 3-The phosphorus titer.
(2) preparation of ascorbic acid solution
Take by weighing 10.00 gram ascorbic acid and 0.20 gram disodium ethylene diamine tetraacetate (C
10H
14O
8N
2Na
22H
2O), be dissolved in 200.00 ml waters, add 8.00 milliliters of formic acid, be diluted with water to 500.00 milliliters, mix, get the ascorbic acid solution of 20 grams per liters, be stored in the brown bottle.
(3) preparation of ammonium molybdate solution
Take by weighing 13.00 gram ammonium molybdates and 0.50 gram potassium antimony tartrate (KSbOC
4H
4O
61/2H
2O), be dissolved in 200.00 ml waters, mix, be diluted with water to 500.00 milliliters after the cooling, mix, get the ammonium molybdate solution of 26 grams per liters, be stored in the brown bottle with 230.00 milliliters of sulfuric acid solutions (1 volume, 98% concentrated sulphuric acid+1 volume water).
(4) drafting of typical curve
Draw phosphorus standard solution that 0.00,1.00,2.00,3.00,4.00,5.00,6.00,7.00 and 8.00 milliliter (1) obtain respectively in 9 50 milliliters of volumetric flasks, in each bottle, add 25 ml waters successively, 2 milliliters of ammonium molybdate solutions that (3) obtain, behind the ascorbic acid solution that 3 milliliters (2) obtain, the water constant volume, shake up, room temperature was placed 10 minutes.With 1 centimetre of cuvette, with the blank zeroing, survey absorbance in 710 nanometers by visible spectrophotometer, test result sees Table 1.With the absorbance that records is horizontal ordinate, is ordinate to phosphate anion milligram number, drawing standard curve (see figure 1).
Total phosphorus is (with PO
4 3-Meter) content is calculated as follows:
In the formula: A
710nm-absorbance
The v-sample, milliliter
The K-slope of standard curve
Table 1
Embodiment 2
Present embodiment illustrates the method for total phosphorus in the analytic sample provided by the invention.
(1) preparation of total phosphorus mark liquid
Get ammonia nitrogen in 10.00 ml waters, nitrate nitrogen, total phosphorus composition secondary analysis standard substance (liquid) (GBW of National Quality ﹠ Technology Inspection Bureau (E) 080431, total phosphorus content is remembered 999.8 mg/litre ± 4.999 mg/litre with P) to 1000 milliliters of volumetric flasks, the water constant volume, mix, obtain with PO
4 3-The total phosphorus mark liquid of meter total phosphorus 30.66 mg/litre ± 0.1533 mg/litre.
(2) mensuration of total phosphorus
Get 5.00 milliliters of above-mentioned total phosphorus mark liquid respectively in 8 in 250 milliliters of conical flasks of label, add 2 milliliters of nitric acid (concentration is 19 mol), 1 milliliter of perchloric acid (concentration is 12 mol), place slowly to boil to the solution evaporate to dryness on the electric furnace and pick up counting, continue heating 0 respectively, 5,10,15,30,45,50, take out after 60 minutes, naturally cool to room temperature, (concentration is 4.6 mol to add about 10 ml waters and 2.0 milliliters of sulfuric acid solutions, it is 1.5 mol that the addition of acid solution makes the product behind the described bone dry and the pH of acid solution potpourri) after little the boiling 10 minutes, be cooled to room temperature.In conical flask, drip 1 phenolphthalein solution (ethanolic solution of 1% phenolphthalein) with dropper, drip the sodium hydroxide solution of concentration 120 grams per liters then, to the pH value of solution be 8.5.The testing sample solution that mixes up the pH value quantitatively is transferred in 50 milliliters of volumetric flasks, add 2 milliliters of aforementioned ammonium molybdate solutions (it is 112: 1 that described ammonium molybdate addition makes the product weight ratio behind molybdate and the described bone dry), 3 milliliters of aforementioned ascorbic acid solutions (it is 4: 3 that the addition of reductant solution makes the mol ratio of reductive agent and described molybdate), the water constant volume, shake up, room temperature was placed 10 minutes.With 1 centimetre of cuvette,, survey absorbance in 710 nanometers by visible spectrophotometer not add the blank zeroing of total phosphorus mark liquid.By above-mentioned typical curve (as shown in Figure 1), draw total phosphorus content (with PO
4 3-Meter, the unit milligram), by calculating, remove the different influence of testing sample solution addition, draw the total phosphorus content of primary sample.Analysis result sees Table 1.
Relative error (%)=(total phosphorus measured value-total phosphorus adding value)/total phosphorus adding value * 100%;
Comparative Examples 1
The method of total phosphorus in this Comparative Examples explanation prior art analytic sample.
Analyze (1) gained total phosphorus mark liquid among the embodiment 2 according to the mensuration ammonium molybdate spectrophotometric method of GB industrial circulating cooling water phosphorus content (see " water quality and water treatment agent product quality detect standardization of products Working Committee of handbook 697-704 page or leaf editor in 1994 the Ministry of Chemical Industry technology groups), sampling and measuring 8 times, by above-mentioned typical curve (as shown in Figure 1), draw total phosphorus content (with PO
4 3-Meter), analysis result sees Table 2.
Table 2
As can be seen from Table 2, according to total phosphorus in the methods analyst sample of the present invention, the mixed liquor of testing sample and distintegrant heating terminal point is fixed, and continues heating 0-60 minute, not impact analysis result's accuracy after arriving the heating terminal point.The former standard deviation is 0.556, and the latter reaches 1.306; The former coefficient of variation is 1.82%, and the latter reaches 4.36%; The method accuracy of total phosphorus is higher than the method for Comparative Examples 1 in the comprehensive above statistics index analytic sample provided by the invention as can be seen.
Embodiment 3
Present embodiment explanation this method is analyzed the precision of the single agent of phosphorous water treatment.
With RP-85 phosphorus is water treatment agent (PBTC) (solid content 〉=50%, total phosphorus 〉=17%, Beijing woods China water stabilizer factory produces lot number 20040803) is mixed with 40 mg/litre with deionized water sample solution.Get 10.00 ml samples respectively in 9 in 250 milliliters of conical flasks of label, add 1 milliliter of nitric acid (19 mol), it is 3.6: 10 that 2 milliliters of perchloric acid (12 mol), the addition of above-mentioned two kinds of acid compounds make the weight ratio of acid compound and testing sample.To fill the conical flask of above-mentioned mixed liquor, place slowly to boil to the solution evaporate to dryness on the adjustable electric furnace to pick up counting, continue heating after 30 minutes, naturally cool to room temperature, analyze according to the method for embodiment 2.Different is, and to make product and little time of boiling of acid solution potpourri behind the described bone dry be 5 minutes; Described acid solution is a hydrochloric acid solution, and concentration is 4 mol, and the addition of acid solution to make the product behind the described bone dry and the pH of acid solution potpourri be 0.67 mol; It is 92: 1 that described potassium molybdate addition makes the product weight ratio behind molybdate and the described bone dry; It is 4: 3 that the addition of adding ascorbic acid (reductive agent) solution makes the mol ratio of reductive agent and described molybdate.Analysis result sees Table 3.
Table 3
As can be seen from Table 3, the total phosphorus method is applicable to the analysis to the single agent of phosphorous water treatment, precision height, good reproducibility fully in the analytic sample provided by the invention.
Embodiment 4
Present embodiment explanation this method is analyzed the precision of phosphorous complexing agent.
Corrosion inhibiting and descaling agent III (solid content 〉=30%, total phosphorus 〉=7%, Beijing woods China water stabilizer factory produces lot number 20041101) is mixed with the sample solution of 100 mg/litre with deionized water.Get 10.00 ml samples respectively in 9 in 250 milliliters of conical flasks of label, add 4 milliliters of nitric acid (concentration is 19 mol), 2 milliliters of perchloric acid (concentration is 12 mol), it is 7.2: 10 that the addition of above-mentioned two kinds of acid compounds makes the weight ratio of acid compound and testing sample.To fill the conical flask of above-mentioned mixed liquor, place slowly to boil to the solution evaporate to dryness on the adjustable electric furnace to pick up counting, continue heating after 20 minutes, naturally cool to room temperature, analyze according to the method for embodiment 2.Different is, and to make product and little time of boiling of acid solution potpourri behind the described bone dry be 15 minutes; Described acid solution is a sulfuric acid solution, and concentration is 4.6 mol, and the addition of acid solution to make the product behind the described bone dry and the pH of acid solution potpourri be 0.84 mol; It is 92: 1 that the addition that adds potassium molybdate solution makes described ammonium molybdate addition make the product weight ratio behind molybdate and the described bone dry; It is 2: 1 that the addition of adding ascorbic acid (reductive agent) solution makes the mol ratio of reductive agent and described molybdate.Analysis result sees Table 4.
Table 4
As can be seen from Table 4, the total phosphorus method is applicable to the analysis to phosphorous water treatment complexing agent fully in the analytic sample provided by the invention, precision height, good reproducibility.
Embodiment 5
Present embodiment explanation this method is analyzed the precision of phosphorous circulation water sample.
The circulation water sample that to take from Luoyang refinery and with the fresh water be supplementing water is as all product solution of phosphorous recirculated water.Get 10.00 ml samples respectively in 9 in 250 milliliters of conical flasks of label, add 3 milliliters of nitric acid (concentration is 19 mol), 1 milliliter of perchloric acid (concentration is 12 mol), it is that the conical flask that will fill above-mentioned mixed liquor at 4.8: 10 places slowly to boil to the solution evaporate to dryness on the adjustable electric furnace and picks up counting that the addition of above-mentioned two kinds of acid compounds makes the weight ratio of acid compound and testing sample, continue heating after 10 minutes, naturally cool to room temperature, analyze according to the method for embodiment 2.Different is, and to make product and little time of boiling of acid solution potpourri behind the described bone dry be 12 minutes; Described acid solution is a sulfuric acid solution, and concentration is 4.6 mol, and the addition of acid solution to make the product behind the described bone dry and the pH of acid solution potpourri be 2.12 mol; It is 112: 1 that described ammonium molybdate addition makes the product weight ratio behind molybdate and the described bone dry; It is 8: 5 that the addition of adding ascorbic acid (reductive agent) solution makes the mol ratio of reductive agent and described molybdate.Analysis result sees Table 5.
Table 5
As can be seen from Table 5, the total phosphorus method is applicable to fully to analyzing the analysis of phosphorous circulation water sample, precision height, good reproducibility in the analytic sample provided by the invention.
Embodiment 6
The recovery of standard addition of present embodiment explanation this method in the circulation water sample of reusing sewage.
At first, will take from the circulation water sample of Zhenghai sewage from oil refinery reuse, drawing total phosphorus according to the methods analyst of embodiment 4 is 12.153 mg/litre.
Get 10.00 milliliters of above-mentioned circulation water samples respectively in 9 in 250 milliliters of conical flasks of label, respectively add 10.00 milliliters of National Environmental standard model GSBZ 50033-95-4290114 again (in P total phosphorus 0.500 mg/litre ± 0.020 mg/litre; With PO
4 3-Meter, 1.533 mg/ml) after, add 2 milliliters of nitric acid (concentration is 19 mol), 1 milliliter of perchloric acid (concentration is 12 mol), it is 1.8: 10 that the addition of above-mentioned two kinds of acid compounds makes the weight ratio of acid compound and testing sample.To fill the conical flask of above-mentioned mixed liquor, place slowly to boil to the solution evaporate to dryness on the adjustable electric furnace to pick up counting, continue heating after 5 minutes, naturally cool to room temperature, analyze according to the method for embodiment 2.Different is, and to make product and little time of boiling of acid solution potpourri behind the described bone dry be 10 minutes; Described acid solution is a sulfuric acid solution, and concentration is 4.6 mol, and the addition of acid solution to make the product behind the described bone dry and the pH of acid solution potpourri be 2.0 mol; It is 112: 1 that described ammonium molybdate addition makes the product weight ratio behind molybdate and the described bone dry; It is 4: 3 that the addition of adding ascorbic acid (reductive agent) solution makes the mol ratio of reductive agent and described molybdate.Analysis result sees Table 6.
Table 6
As can be seen from Table 6, in the system that the sewage that is rich in organophosphorus exists, the method precision of total phosphorus is still very high in the analytic sample provided by the invention, and recovery of standard addition is better than far away that recovery of standard addition should be in the standard of 85-115% on the statistics between 97.0-103.6%.
Claims (14)
1, the method for total phosphorus content in a kind of analytic sample, this method comprises the following steps:
(1) testing sample is mixed with a kind of distintegrant, to bone dry, described distintegrant is the solution of the acid compound of strong oxidizing property with the gained mixture heated;
(2) product behind the above-mentioned bone dry is dissolved fully with a kind of acid solution;
(3) step (2) products therefrom is mixed with molybdate or molybdate solution;
(4) step (3) products therefrom is mixed with a kind of reductive agent or reductant solution carry out chromogenic reaction;
(5) content of the phosphorus molybdenum blue in the mixed liquor of usefulness spectrophotometry step (4) gained.
2, method according to claim 1, wherein, the acid compound of the described strong oxidizing property of step (1) is selected from one or more in nitric acid, perchloric acid or the hypochlorous acid.
3, method according to claim 1 and 2, the addition of the acid compound of described strong oxidizing property are that to make the acid compound of described strong oxidizing property and the weight ratio of testing sample be 0.1-3.0: 1.
4, method according to claim 1, the method for wherein said bone dry are calcination.
5, method according to claim 1, this method also are included in the step that step (2) is cooled off the product behind the described bone dry before.
6, method according to claim 1, wherein said acid solution is selected from sulfuric acid solution and/or hydrochloric acid solution.
7, according to claim 1 or 6 described methods, it is the 0.3-2.5 mol that the addition of wherein said acid solution makes the pH of the potpourri of product behind the described bone dry and acid solution.
8, method according to claim 1, wherein the described consoluet method of step (2) is to make the product behind the described bone dry and little the boiling of potpourri of acid solution.
9, method according to claim 8, wherein, described little time of boiling is 5-15 minute.
10, method according to claim 1, wherein, this method also is included in step (3) before, and the pH value of the solution after step (2) gained is dissolved fully is adjusted to 8.0-10.0.
11, method according to claim 1, wherein, the described molybdate of step (3) is selected from one or more in ammonium molybdate, sodium molybdate or the potassium molybdate, and it is 92-150 that the addition of described molybdate or molybdate solution makes the weight ratio of the product behind molybdate and the described bone dry: 1.
12, method according to claim 1, wherein, the described reductive agent of step (4) is selected from one or more in ascorbic acid, hydrazine sulfate or the stannous chloride.
13, according to claim 1 or 12 described methods, wherein, it is 4: 3 to 2: 1 that the addition of described reductive agent or reductant solution makes the mol ratio of reductive agent and described molybdate.
14, method according to claim 1, wherein, described testing sample is solid, liquid and/or gas.
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