Two. background technology:
Mercury Hg and compound thereof belong to extremely toxic substance, can accumulate in vivo.The inorganic mercury ion that enters in the water can change the bigger organic mercury of toxicity into, enters human body through food chain, causes the whole body poisoning.Mercurous few in the natural water, generally be no more than 0.1 μ g/L.Instrucment and meter plant, salt electrolysis, precious metal smelting, temperature are taken into account in the industrial waste waters such as military project may contain mercury.Mercury is one of important indicator of China's enforcement total emission volumn control.
At present, the dithizone spectrophotometric method is to measure the universal method of mercury content.Under acid condition, mercury ion and dithizone generate orange chelate, use organic solvent extraction, use the dithizone of aqueous slkali flush away surplus again, use spectrophotometer measurement.The basic step of dithizone spectrophotometry mercury content:
1. the drafting of typical curve:
Get six 500mL separating funnels, add respectively and face mercury standard use solution 0mL, 0.50mL, 1.00mL, 2.50mL, 5.00mL, the 10.00mL that uses preceding preparation, add water to 250mL.Fully according to following measurement sample step, immediately it is measured one by one then.
Do behind the blank correction and corresponding mercury content drawing standard curve to each absorbance of measuring respectively at last.
2. measure
Respectively each part sample or blank sample are put into separating funnel, add 20% sodium sulfite solution 1mL, add 10.0mL dithizone-methenyl choloride behind the mixing and use liquid, slowly shaking by swirling and venting, close again plug jolting 1 minute, standing demix.Repeated washing is 1~2 time in case of necessity, does not show green until organic phase.
Inhale the globule that goes in the separating funnel liquid discharging tube with filter paper, fill in a little absorbent cotton, organic phase is put into the 20mm cuvette, under the 485nm wavelength, make reference, survey absorbance with methenyl choloride.
After deducting the absorbance of blank sample with the absorbance of sample, find mercury content from calibration curve.
The problem that the dithizone spectrophotometric method exists:
(1) need carry out the eliminating of interfering material to water sample and clear up, the program complexity, deal with improperly cause easily the mercury data of surveying inaccurate, error is big.
(2) use of poisonous and harmful reagent such as mercury standard solution, methenyl choloride causes serious secondary pollution, and to operation accuracy requirement height, needs to distill refining, purifying, and is now with the current, very complicated.
(3) drafting of typical curve, operating process such as extract and separate are tediously long, complexity, labour intensity is big.
(4) need with the Instrument measuring absorbance and with formula calculating concentration value, high to the operator quality requirement, the testing cost costliness.
Three. the utility model content:
The purpose of this utility model: simplify the mercury content testing procedure, shorten minute greatly, alleviate intensity of workers, make a kind of easy to carry, mercury colorimetry testing tube of using simple and fast.
The technical solution of the utility model:
A kind of mercury colorimetry testing tube is vacuum sealing tube, contains the uniform cross section glass tube of end sealing, and the opening part of glass tube is communicated with the kapillary and the transition section of end sealing, and mercury determination solution is housed in glass tube, measures the height H of liquid in glass tube
1With the glass tube uniform cross section height H of leaving a blank
2Ratio be H
1: H
2=1: 2~16.
In glass tube, measure the height H of liquid
1With the glass tube uniform cross section height H of leaving a blank
2Ratio be H
1: H
2=1: 8~12.
Described mercury colorimetry testing tube is an example with the unit volume, measures in the liquid to contain 0.005% phenylhydrazine compound 10~50 unit volumes, pH damping fluid 10~70 unit volumes, mixed preparing forms, and measures the raising or the reduction of each effective ingredient concentration in the liquid, measures that liquid is long-pending corresponding to be dwindled or increase.
Positive beneficial effect of the present utility model:
1. the utility model is with the detection technique commercialization, and commercialization is loaded on the mensuration fluid-tight for preparing in the glass tube with vacuum, can directly use.Only need during operation to fracture in the water sample to be measured capillary tube segment of test tube makes in the water sample automatic ration tail pipe to be measured and measures liquid generation metachromasia, just can draw mercury content more accurately with the contrast of standard color range behind the colour stable.Need not be when each test preparing standard solution, reagent, can simplify the detection step greatly, save minute, reduce workload, reduce labor intensity.
2. it is reasonable that the utility model is measured formula of liquid, advanced technology, and stable performance is used simple.Adopt standard sample liquid to react with it in advance, constant color forms permanent colour code standard, and encapsulation forms the contrast color range, carries out the scene and detects, and need not to prepare other any reagent, and testing result accurately and reliably.The standard colour code can be made by standard color range pipe of the present utility model and form, also can be, or the colored printing cardboard, or the colored plastic rod by the computer color atlas, or other physical medium material such as stained glass goods forms, and uses very convenient.
3. compare with traditional dithizone photometry, there is not the problem that the copper ion generation is disturbed in the water quality in the utility model, has reduced measuring process, has accelerated finding speed.
4. to measure the chromogenic reaction of liquid and determinand mercury be to carry out automatically under given conditions the glass tube with vacuum to the utility model, can effectively avoid accidental error and personal error, testing result meets the requirement of water analysis error precision accurately and reliably, and detection limit meets national sewage comprehensive emission standard.
The utility model carry, easy to use, measure simple fast, accurately, the holding time is long.The on-the-spot detection do not need the miscellaneous equipment instrument, saves human and material resources greatly, reduces integrated cost.The utility model is easy to promotion and implementation, has good social and economic benefit.
The utility model testing tube and dithizone photometry data comparison sheet:
Five. embodiment
Embodiment one: make the series standard colour code that detects mercury content in advance, form color range.For example make 12 the color range pipes of standard colour code that detect low concentration mercury content in the water quality, mercury content is respectively 0.0mg/L, 0.1mg/L, 0.3mg/L, 0.5mg/L, 0.75mg/L, 1.0mg/L, 1.5mg/L, 2.0mg/L, 2.5mg/L, 3.0mg/L, 3.5mg/L, the standard colour code of 4.0mg/L.At first get 0.005% diphenyl carbazone 42mL, NaAc-HAc damping fluid 92mL is mixed and made into mensuration liquid.Making mercury content then respectively is 0.0mg/L, 0.1mg/L, 0.3mg/L, 0.5mg/L, 0.75mg/L, 1.0mg/L, 1.5mg/L, 2.0mg/L, 2.5mg/L, 3.0mg/L, 3.5mg/L, 12 kinds of normal concentration mercury aqueous solution of 4.0mg/L, to measure liquid and various normal concentration mercury aqueous solution pours into reaction solution in 12 charomatrons respectively in 1: 8 ratio, and constant color, seal charomatron then, form non-fading serial color range standard colors mark pipe.The mensuration liquid concentration of production standard color range pipe is identical with the mensuration liquid concentration of supporting mensuration pipe, the ratio of mensuration liquid and normal concentration mercury aqueous solution volume when measuring the corresponding formulation standard of the ratio color range pipe of liquid volume and the volume of leaving a blank in the pipe.Measure formula of liquid not simultaneously, the corresponding standard colour code of making, the color range of formation is also different.Only use the compound method of method description standard colour code for example at this.
Measure the pipe implementation method: referring to Fig. 1,1 is the uniform cross section glass tube with vacuum among the figure, and 2 is capillary tube segment, and 3 is mercury determination solution.H
1For measuring liquid height, H
2For the uniform cross section glass tube with vacuum is left a blank highly.The mensuration liquid of the corresponding preparation standard colour code of present embodiment, promptly measuring liquid and aqueous solution volume ratio to be measured is 1: 8.6.5 millimeters of uniform cross section vacuum glass external diameter of pipe, 12 centimetres of overall heights, the height H of mensuration liquid in the glass tube
1Be 1.1 centimetres, the height H of leaving a blank
2Be 8.8 centimetres, capillary tube segment length is 2.1 centimetres.
During use, the capillary tube segment of measuring pipe is immersed in the analyte sample fluid, capillary tube segment fractures, wait for that test article liquid is filled the uniform cross section glass tube with vacuum pipeline section of leaving a blank, take out to be inverted repeatedly and mix, make it fully to carry out chromogenic reaction, contrast with the standard colour code behind about 5~10 minutes colour stables, be the mercury content that records with the pairing mercury concentration of the colour code numerical value that is near the mark most,, then get its mean value if measure pipe color rank between two standard colour codes.
Mercury colorimetry testing tube of the present invention is measured formula of liquid or is: represent with unit volume, contain 0.005% diphenyl carbazone 10 unit volumes, NaAc-HAc damping fluid 27 unit volumes.
Embodiment two: referring to Fig. 1, numbering is identical with embodiment one among the figure, represents same meaning.Standard colors target method for making, the making of measuring pipe and using method no longer are described in detail with embodiment one.Difference is:
Uniform cross section glass tube with vacuum external diameter is 6.5 millimeters in the present embodiment, 11 centimetres of overall heights, the height H of mensuration liquid in the glass tube
1Be 1 centimetre, the height H of leaving a blank
2Be 8.5 centimetres, capillary tube segment length is 1.5 centimetres.
Mercury colorimetry testing tube in the present embodiment, the mercury determination solution prescription is: represent with unit volume, contain 0.005% diphenylcarbazide 23 unit volumes, borax-NaOH damping fluid 46 unit volumes
Embodiment three: referring to Fig. 1, numbering is identical with embodiment one among the figure, represents same meaning.Standard colors target method for making, the making of measuring pipe and using method no longer are described in detail with embodiment one.Difference is:
Uniform cross section glass tube with vacuum external diameter is 6.5 millimeters in the present embodiment, 14.8 centimetres of overall heights, the height H of mensuration liquid in the glass tube
1Be 1.2 centimetres, the height H of leaving a blank
2Be 12 centimetres, capillary tube segment length is 1.6 centimetres.
Mercury colorimetry testing tube in the present embodiment, the mercury determination solution prescription is: represent with unit volume, contain 0.005% diphenyl carbazone 36 unit volumes, NaAc-HAc damping fluid 10 unit volumes.
Embodiment four: referring to Fig. 1, numbering is identical with embodiment one among the figure, represents same meaning.Standard colors target method for making, the making of measuring pipe and using method no longer are described in detail with embodiment one.Difference is:
Uniform cross section glass tube with vacuum external diameter is 6.5 millimeters in the present embodiment, 12.6 centimetres of overall heights, the height H of mensuration liquid in the glass tube
1Be 1.1 centimetres, the height H of leaving a blank
2Be 9.9 centimetres, capillary tube segment length is 1.6 centimetres.
Mercury colorimetry testing tube in the present embodiment, the mercury determination solution prescription is: represent with unit volume, contain 0.005% diphenyl carbazone 50 unit volumes, NaAc-HAc damping fluid 19 unit volumes.
Embodiment five: referring to Fig. 1, numbering is identical with embodiment one among the figure, represents same meaning.Standard colors target method for making, the making of measuring pipe and using method no longer are described in detail with embodiment one.Difference is:
Uniform cross section glass tube with vacuum external diameter is 6.5 millimeters in the present embodiment, 7.7 centimetres of overall heights, the height H of mensuration liquid in the glass tube
1Be 2.1 centimetres, the height H of leaving a blank
2Be 4.2 centimetres, capillary tube segment length is 1.4 centimetres.
Mercury colorimetry testing tube in the present embodiment, the mercury determination solution prescription is: represent with unit volume, contain 0.005% diphenylcarbazide 17 unit volumes, borax-NaOH damping fluid 35 unit volumes.
Embodiment six: referring to Fig. 1, numbering is identical with embodiment one among the figure, represents same meaning.Standard colors target method for making, the making of measuring pipe and using method no longer are described in detail with embodiment one.Difference is:
Uniform cross section glass tube with vacuum external diameter is 6.5 millimeters in the present embodiment, 14.6 centimetres of overall heights, the height H of mensuration liquid in the glass tube
1Be 1 centimetre, the height H of leaving a blank
2Be 12 centimetres, capillary tube segment length is 1.6 centimetres.
Mercury colorimetry testing tube in the present embodiment, the mercury determination solution prescription is: represent with unit volume, contain 0.005% diphenylcarbazide 42 unit volumes, borax-NaOH damping fluid 70 unit volumes.
Embodiment seven: referring to Fig. 1, numbering is identical with embodiment one among the figure, represents same meaning.Standard colors target method for making, the making of measuring pipe and using method no longer are described in detail with embodiment one.Difference is:
Uniform cross section glass tube with vacuum external diameter is 6.5 millimeters in the present embodiment, 18.5 centimetres of overall heights, the height H of mensuration liquid in the glass tube
1Be 1 centimetre, the height H of leaving a blank
2Be 16 centimetres, capillary tube segment length is 1.5 centimetres.
Mercury colorimetry testing tube in the present embodiment, the mercury determination solution prescription is: represent with unit volume, contain 0.005% diphenyl carbazone 29 unit volumes, NaAc-HAc damping fluid 61 unit volumes.
Embodiment eight: referring to Fig. 1, numbering is identical with embodiment one among the figure, represents same meaning.Standard colors target method for making, the making of measuring pipe and using method no longer are described in detail with embodiment one.Difference is:
Uniform cross section glass tube with vacuum external diameter is 6.5 millimeters in the present embodiment, 16.6 centimetres of overall heights, the height H of mensuration liquid in the glass tube
1Be 1 centimetre, the height H of leaving a blank
2Be 14 centimetres, capillary tube segment length is 1.6 centimetres.
Mercury colorimetry testing tube in the present embodiment, the mercury determination solution prescription is: represent with unit volume, contain 0.005% diphenylcarbazide 15 unit volumes, borax-NaOH damping fluid 38 unit volumes.