CN109557087A - A kind of detection method of metal surface Cr VI - Google Patents
A kind of detection method of metal surface Cr VI Download PDFInfo
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- CN109557087A CN109557087A CN201811264240.7A CN201811264240A CN109557087A CN 109557087 A CN109557087 A CN 109557087A CN 201811264240 A CN201811264240 A CN 201811264240A CN 109557087 A CN109557087 A CN 109557087A
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Abstract
The present invention relates to a kind of detection methods of metal surface Cr VI, step are as follows: S1, prepare Test paper: compound concentration is the ethyl alcohol acetone mixed solution of the adjacent dinitrodiphenyl carbazide of 0.005-0.5g/mL, filter paper item is immersed in above-mentioned mixed solution, filter paper item is put into the closed container of inert gas by filter paper item after taking out, after filter paper item air-dries completely, be transferred to closed, deoxygenation, brown reagent bottle or sample sack in it is stand-by；S2, acid developer is dripped in metal surface to be measured, then the Test paper in step 1 is immersed into color developing agent, the variation and colorimetric card for observing test paper color determine the content range of Cr VI after comparing.The present invention effectively can carry out quantitative detection to metal coating surface content of 6-valence Cr ions.
Description
Technical field
The invention belongs to chemical analysis fields, and in particular to a kind of detection method of metal surface Cr VI.
Background technique
Content of the chromium in the earth's crust is 0.01%, and VI B race, atomic number 24, atomic weight are belonged in the periodic table of elements
51.9961, it is the maximum metal of hardness that usual valences, which are+2 ,+3 and+6,.Cr VI belong to chromium common oxidation state it
One, there is very strong chemical activity, it is easy to be absorbed by the body by the approach such as breathing, contacting, at the same Cr VI have it is relatively strong
Toxicity, Long Term Contact can cause extreme influence to human health, and short term contact also brings along potential carcinogenic risk.
In Hyundai Motor production industry, the antiseptic property of metal material is the big event of vehicle performance index.Because
Sexavalence chromium passivating can form one layer of densification in metal surface and layer is effectively protected, and delay or prevent corrosion of metal, so sexavalence
Chromium is widely present among metal material surface treatment process as good passivator.The metal material processed using this technique
Material, surface often remain a large amount of sexavalence chromium component, this also makes product itself produce the unfriendly property of environment.
In leather manufacture industry, chromium plays critically important effect to tan leather, and leather softness can be made rich in bullet
Property, therefore be a kind of essential tanning agent.Playing the role of tanning is mainly three prices, and Cr VI does not have tanning.Contain
In chrome tanning agent the generation of Cr VI mainly with related, the current leather of factors such as the production technology of tanning agent, the cost of raw material
Product often has a large amount of residuals of Cr VI.
In nature, Cr VI can be present among natural water as a solution, and source is predominantly above-described
The discharge of the industrial wastewaters such as Treatment of Metal Surface enterprise, leather manufacture industry or the discharge of power station condensed water.Hexavalent chromium wastewater is easy
Animals and plants, water body, soil in the ecosphere in environment etc. are caused seriously to pollute, and caused by pollution be difficult to restore.Cr VI
Pollution is a kind of extremely serious ecocatastrophe.
Therefore, in terms of environment protection field, field of metal material surface treatment, automobile, Cr VI
Detection and control are all highly important.Currently, all providing content of 6-valence Cr ions no more than in European Union ROHS instruction, ELV instruction
0.1%, the electric equipment products and automobile product exported at present will be executed according to limit value；Car gage " the GB/T of China
The requirement of 30512-2014 automobile banned substance " in also provide content of 6-valence Cr ions no more than 0.1%, the selection of auto parts and components with
Using should all be executed according to this standard.
The detection method of Cr VI mainly uses two kinds at present: chromatography and colorimetric method.Chromatography utilizes different ions
Selectivity distribution in different material, elutes the mixture in stationary phase with mobile phase, different ions can be with not in mixture
Same speed is mobile, is finally reached the effect for separating Cr VI, carries out quantitative test to the Cr VI after separation.Colorimetric method is
Using the color change for reacting generation of Cr VI and particular matter, by the degree of color change to Cr VI indirect quantification
Method.Comparatively, for chromatography to the more demanding of instrument, testing cost is larger, and detection cycle is longer, to the purity of detection liquid
It is more demanding；And the equipment investment of colorimetric method is less, testing cost is smaller, the period is shorter.Currently, in industry colorimetric method use
It is more.
In the detection process for carrying out metal material surface Cr VI, colorimetric method is mainly used.And currently used colorimetric
Method mainly uses two ways: the first is a test, judges whether there is Cr VI by the chromogenic reaction of metal surface, this
The advantages of kind method is that operation is convenient, the disadvantage is that can not accurate quantitative analysis；Another method is colorimetric determination, and metal sample is led to
Crossing boiling water boiling to change Cr VI therein is solution state, so that the complexing of the Cr VI in solution is showed face by the effect of developing solution
Color, and then the standard curve by establishing carries out colorimetric determination analysis using colour comparatour, the advantages of this method is quantitative quasi-
Really, the disadvantage is that it is complicated for operation, the test period is longer；In addition, some detection method is tested using electrochemical principle,
The advantages of this kind of methods is that result is more intuitive, the disadvantage is that complicated for operation and testing cost is higher.
The maceration extract of " a kind of test paper for detecting hexavalent chromium ions of CN102419326A and preparation method thereof ", test paper is used by water
Yankee fluorone, dehydrated alcohol, diethylenetriamine pentaacetic acid, distilled water mixed solution, indicator use salicyl fluorone.
" a kind of detection method of hexavalent chromium of CN102519948A " uses golden shell nano-particle solution and develops the color with Cr VI
Reaction." method that CN103969365A ion chromatographic column switches method online pre-treatment measurement trivalent chromium and hexavalent chromium " be from
The online pre-treatment of sub- chromatographic column switching method measures trivalent chromium and hexavalent chromium, is a kind of common ion chromatography of instrument analysis
Method." detection method of hexavalent chromium content in a kind of passivating solution of CN106092921A " is the side for measuring the Cr VI in solution
Method, fundamentally for be a kind of analysis of ultraviolet-visible chemical method, the main Cr VI measured in solution.
" CN201796010U Portable chromium sensor " is a kind of Portable chromium sensor, for the sexavalence in water sample
Content of chromium ion detection, it is equivalent to the effect of Cr VI sensor using structure compositions such as a kind of screen printing electrodes.
" a kind of heavy metal assay kit of CN201837589U " is a heavy metal species quick detection kit, and color developing agent uses 0.5g/L
Diphenylcarbazide configuration, chromogenic agent is lower, using pH value adjustment agent adjust solution pH value, it is difficult to enable colour developing
React more obvious." a kind of method of rapid detection of hexavalent chromium ions in sewage of CN102411001A " this detection method needle
Cr VI in solution is tested." CN102121905A is used to detect the test strips and its preparation of heavy metal chromium in water quality
Method " invention by the way that test strips are made in color developing agent diphenylcarbazide immobilization, passes through light after being put into photoelectric sensor
The reading of electric transducer progress content of 6-valence Cr ions.Belong to water quality inspection technique field, is quantitatively carried out using photoelectric sensor.
" CN1563967A electroplating wastewater monitoring method and device " monitors the variation of Cr VI in aqueous solution by electrochemical reaction.More than
The combining form that patent document does not use test paper that acidity regulator is added to add colorimetric card, in this way under neutral or alkaline condition
Cr VI is difficult to detect.The process that most of patent is saved in sexavalence paper of chrome,test is mostly without particular/special requirement, according to these documents
The test paper of patent production will soon redden failure.In addition for most of quantitative measurment of Cr VI using the side of instrument analysis
Method, and without come optimizing detection method, being merely able to for metal coating material for a large amount of aqueous solution or setting Cr VI
It changes and carries out quantitative test in solution.
In summary, it is necessary to the detection articles and method of Cr VI be optimized, especially to metal material table
The test method of face Cr VI is developed.
Summary of the invention
The object of the present invention is to provide a kind of detection methods of metal surface Cr VI, have the easy to operate, test period
The more intuitive advantage of short, at low cost and result, and there is the more accurately quantitative detection as colorimetric determination simultaneously
As a result.
The purpose of the present invention is achieved through the following technical solutions:
A kind of detection method of metal surface Cr VI, its step are as follows:
S1, prepare Test paper: compound concentration is that the ethyl alcohol acetone mixing of the adjacent dinitrodiphenyl carbazide of 0.005-0.5g/mL is molten
Liquid immerses filter paper item in above-mentioned mixed solution, and filter paper item is put into the closed container of inert gas by filter paper item after taking out, and filters
After paper slip air-dries completely, be transferred to closed, deoxygenation, brown reagent bottle or sample sack in it is stand-by；
S2, acid developer is dripped in metal surface to be measured, then the Test paper in step 1 is immersed into color developing agent, observation
The content range of Cr VI is determined after the variation of test paper color and colorimetric card comparison.
As the present invention more by technical solution: color developing agent in step S2 form and volume ratio is as follows: mass fraction
Orthophosphoric acid for 85%: the biphosphate sodium water solution that mass fraction is 29%: deionized water is (5~30): (5~30): (40
~90).
The technical solution more having as the present invention: the ratio of ethyl alcohol described in step S1 and acetone is 1-9:1-9
As the technical solution that more has of the present invention: colorimetric card in step S2 the preparation method comprises the following steps: configuration it is a series of have contain
The hexavalent chromium solution for measuring gradient, is developed the color with the test paper in step S1, for the color gradient of the colour developing result of test paper, is manufactured
Standard color comparison card.
It has the beneficial effect that:
The present invention provides a kind of test paper for the detection metal surface Cr VI that validity period is long and can be commercialized, and provide examination
The use environment of paper, realize can whether the judgement containing Cr VI, more can be preliminary metal coating surface Cr VI is contained
Amount carries out quantitative detection.
Detailed description of the invention
Fig. 1 is that this patent test paper saves the color developing effect schematic diagram after half a year.
Fig. 2 is the air drying process schematic diagram of this patent test paper.
Fig. 3 is the schematic diagram of colorimetric card used in this patent.
Specific embodiment
In following specific example descriptions, a large amount of concrete details are given in order to more deep this hair of understanding
It is bright.
A kind of detection method of metal surface Cr VI, specific steps are as follows:
S1, prepare Test paper: compound concentration is that the ethyl alcohol acetone mixing of the adjacent dinitrodiphenyl carbazide of 0.005-0.5g/mL is molten
Liquid immerses filter paper item in above-mentioned mixed solution, and filter paper item is put into the closed container of inert gas by filter paper item after taking out, and filters
After paper slip air-dries completely, be transferred to closed, deoxygenation, brown reagent bottle or sample sack in it is stand-by；
S2, acid developer is dripped in metal surface to be measured, then the Test paper in step 1 is immersed into color developing agent, observation
The content range of Cr VI is determined after the variation of test paper color and colorimetric card comparison.
The production of colorimetric card and quantitative approach are: successively choosing 7 kinds of colors by white to darkviolet on professional colour table, fill out
Enter in seven squares of LINEAR CONTINUOUS, prints colour table on specialty photo papers with professional color printer.Preparation contains Cr VI
Serial solution, the content of Cr VI is respectively as follows: 0mg/L, 0.1mg/L, 0.5mg/L, 1mg/L, 10mg/L in serial solution,
50mg/L, 100mg/L pipette the above-mentioned solution of 5mL into different beakers respectively, and a drop color developing agent is added into each beaker, takes
The Test paper of seven Cr VIs is immersed respectively in the beaker of the serial solution of the Cr VI of various concentration, and seven six are taken out after 3s
The Test paper of valence chromium places a white A4 paper gasket by color from shallow to deep successively on transparency glass plate below glass plate
Support, above-mentioned colour table are placed in beside the Test paper of Cr VI and are compared, by looking for color to carry out numerical value by white to darkviolet
Calibration, finally determines the content concrete outcome (Fig. 3) of the Cr VI in aqueous solution corresponding to each color.According to the body of a drop reagent
Product is 0.05mL, finally forms the circular drop that diameter is 0.5cm in metal surface, calculates each color and correspond in metal surface
The testing result (Fig. 3) of Cr VI.
Effect of the invention is described further with 9 specific embodiments below.
Embodiment 1
It prepares Test paper: firstly the need of the adjacent dinitrodiphenyl carbazide ethyl alcohol acetone mixed solution for preparing 0.45g/mL, weighing
0.1g neighbour's dinitrodiphenyl carbazide powder is placed in the beaker of 50mL, and the ethyl alcohol of 8mL and the acetone of 9mL is added, stirring, until adjacent benzene carbon
Two hydrazine powder of acyl is completely dissolved.Filter paper item is cut into the slice of 1cm х 4cm, is dipped in the adjacent benzene carbon of above-mentioned 0.01g/mL
In two hydrazine ethyl alcohol acetone mixed solution of acyl, 1min is waited.It takes out, filter paper item is put into test tube, inert gas is passed through in test tube
Protection.After paper slip to be filtered air-dries completely, transfer them to closed, deoxygenation, brown reagent bottle or sample sack in it is stand-by.
It prepares color developing agent: 85ml deionized water being added in beaker, it is 85% that 25ml mass fraction is added under stiring
Orthophosphoric acid, then into system, the biphosphate sodium water solution that mass fraction is 29% is added in 25ml, is stirred evenly, is stored in reagent
It is stand-by in bottle.The method that the biphosphate sodium water solution that mass fraction is 29% is prepared is: by 40g anhydrous sodium dihydrogen phosphate solid
It is dissolved in the deionized water of 100g, promotion dissolution is sufficiently stirred, the solution for finally obtaining clear (can also be prepared other
The biphosphate sodium water solution of concentration need to only guarantee that the water biphosphate sodium content finally prepared in solution reaches for subsequent use
Content range described in specification).
A drop color developing agent is added dropwise in a metal coating surface, can clearly be seen that the coat of metal is completely corroded after 1min,
The chromogenic reagent solution after reaction is blotted with the Test paper of Cr VI, the Test paper of Cr VI does not change colour, it was demonstrated that the gold
Belong to coating surface and is free of Cr VI.The Test paper suit and detection method for proving metal surface Cr VI may determine that metal
Whether contain Cr VI in coating surface.
Embodiment 2
It prepares Test paper: firstly the need of the adjacent dinitrodiphenyl carbazide ethyl alcohol acetone mixed solution for preparing 0.005g/mL, weighing
0.1g neighbour's dinitrodiphenyl carbazide powder is placed in the beaker of 50mL, and the ethyl alcohol of 1mL and the acetone of 9mL is added, stirring, until adjacent benzene carbon
Two hydrazine powder of acyl is completely dissolved.Filter paper item is cut into the slice of 1cm х 4cm, is dipped in the adjacent benzene carbon of above-mentioned 0.01g/mL
In two hydrazine ethyl alcohol acetone mixed solution of acyl, 1min is waited.It takes out, filter paper item is put into test tube, inert gas is passed through in test tube
Protection.After paper slip to be filtered air-dries completely, transfer them to closed, deoxygenation, brown reagent bottle or sample sack in it is stand-by.
It prepares color developing agent: 90ml deionized water being added in beaker, it is 85% just that 5ml mass fraction is added under stiring
Phosphoric acid, then into system, the biphosphate sodium water solution that mass fraction is 29% is added in 5ml, is stirred evenly, is stored in reagent bottle
In it is stand-by.The method that the biphosphate sodium water solution that mass fraction is 29% is prepared is: 40g anhydrous sodium dihydrogen phosphate solid is molten
Promotion dissolution is sufficiently stirred in the deionized water of 100g in solution, and the solution for finally obtaining clear (can also be prepared other dense
The biphosphate sodium water solution of degree need to only guarantee that the water biphosphate sodium content finally prepared in solution reaches for subsequent use
Content range described in bright book).
A drop color developing agent is added dropwise in a metal coating surface, can clearly be seen that the coat of metal is completely corroded after 1min,
The chromogenic reagent solution after reaction is blotted with the Test paper of Cr VI, the Test paper of Cr VI becomes purple, it was demonstrated that the gold
Belong to coating surface and contains Cr VI.The Test paper suit and detection method for proving metal surface Cr VI may determine that metal
Whether contain Cr VI in coating surface.
Embodiment 3
It prepares Test paper: firstly the need of the adjacent dinitrodiphenyl carbazide ethyl alcohol acetone mixed solution for preparing 0.5g/mL, weighing
0.1g neighbour's dinitrodiphenyl carbazide powder is placed in the beaker of 50mL, and the ethyl alcohol of 9mL and the acetone of 9mL is added, stirring, until adjacent benzene carbon
Two hydrazine powder of acyl is completely dissolved.Filter paper item is cut into the slice of 1cm х 4cm, is dipped in the adjacent benzene carbon of above-mentioned 0.01g/mL
In two hydrazine ethyl alcohol acetone mixed solution of acyl, 1min is waited.It takes out, filter paper item is put into test tube, inert gas is passed through in test tube
Protection.After paper slip to be filtered air-dries completely, transfer them to closed, deoxygenation, brown reagent bottle or sample sack in it is stand-by.
It prepares color developing agent: 40ml deionized water being added in beaker, it is 85% just that 5ml mass fraction is added under stiring
Phosphoric acid, then into system, the biphosphate sodium water solution that mass fraction is 29% is added in 5ml, is stirred evenly, is stored in reagent bottle
In it is stand-by.The method that the biphosphate sodium water solution that mass fraction is 29% is prepared is: 40g anhydrous sodium dihydrogen phosphate solid is molten
Promotion dissolution is sufficiently stirred in the deionized water of 100g in solution, and the solution for finally obtaining clear (can also be prepared other dense
The biphosphate sodium water solution of degree need to only guarantee that the water biphosphate sodium content finally prepared in solution reaches for subsequent use
Content range described in bright book).
A drop color developing agent is added dropwise in metal coating surface, can clearly be seen that the coat of metal is completely corroded after 1min, use
The Test paper of Cr VI blots the chromogenic reagent solution after reaction, and the Test paper of Cr VI becomes lilac, by with than
The comparison of colour atla, it can be determined that the content of Cr VI is between 1.25mg/m2-2.5mg/m2.Prove metal surface Cr VI
Test paper suit and detection method may determine that whether contain Cr VI in metal coating surface and carry out tentatively quantitative.
Embodiment 4
It prepares Test paper: firstly the need of the adjacent dinitrodiphenyl carbazide ethyl alcohol acetone mixed solution for preparing 0.2g/mL, weighing
0.1g neighbour's dinitrodiphenyl carbazide powder is placed in the beaker of 50mL, and the ethyl alcohol of 9mL and the acetone of 4mL is added, stirring, until adjacent benzene carbon
Two hydrazine powder of acyl is completely dissolved.Filter paper item is cut into the slice of 1cm х 4cm, is dipped in the adjacent benzene carbon of above-mentioned 0.01g/mL
In two hydrazine ethyl alcohol acetone mixed solution of acyl, 1min is waited.It takes out, filter paper item is put into test tube, inert gas is passed through in test tube
Protection.After paper slip to be filtered air-dries completely, transfer them to closed, deoxygenation, brown reagent bottle or sample sack in it is stand-by.
It prepares color developing agent: 80ml deionized water being added in beaker, it is 85% that 20ml mass fraction is added under stiring
Orthophosphoric acid, then into system, the biphosphate sodium water solution that mass fraction is 29% is added in 20ml, is stirred evenly, is stored in reagent
It is stand-by in bottle.The method that the biphosphate sodium water solution that mass fraction is 29% is prepared is: by 40g anhydrous sodium dihydrogen phosphate solid
It is dissolved in the deionized water of 100g, promotion dissolution is sufficiently stirred, the solution for finally obtaining clear (can also be prepared other
The biphosphate sodium water solution of concentration need to only guarantee that the water biphosphate sodium content finally prepared in solution reaches for subsequent use
Content range described in specification).
Point taking-up 5mL solution in one bottle of solution to be measured, is added a drop color developing agent, by one end of the Test paper of Cr VI
It immerses among solution, is taken out after 3s, the Test paper of Cr VI does not change colour, it was demonstrated that a small amount of Cr VI is free of or contained only in solution
(<0.1mg/L).The Test paper suit and detection method for proving metal surface Cr VI may determine that in aqueous solution whether contain
There is Cr VI.
Embodiment 5
It prepares Test paper: firstly the need of the adjacent dinitrodiphenyl carbazide ethyl alcohol acetone mixed solution for preparing 0.05g/mL, weighing
0.1g neighbour's dinitrodiphenyl carbazide powder is placed in the beaker of 50mL, and the ethyl alcohol of 4mL and the acetone of 3mL is added, stirring, until adjacent benzene carbon
Two hydrazine powder of acyl is completely dissolved.Filter paper item is cut into the slice of 1cm х 4cm, is dipped in the adjacent benzene carbon of above-mentioned 0.01g/mL
In two hydrazine ethyl alcohol acetone mixed solution of acyl, 1min is waited.It takes out, filter paper item is put into test tube, inert gas is passed through in test tube
Protection.After paper slip to be filtered air-dries completely, transfer them to closed, deoxygenation, brown reagent bottle or sample sack in it is stand-by.
It prepares color developing agent: 50ml deionized water being added in beaker, it is 85% that 10ml mass fraction is added under stiring
Orthophosphoric acid, then into system, the biphosphate sodium water solution that mass fraction is 29% is added in 10ml, is stirred evenly, is stored in reagent
It is stand-by in bottle.The method that the biphosphate sodium water solution that mass fraction is 29% is prepared is: by 40g anhydrous sodium dihydrogen phosphate solid
It is dissolved in the deionized water of 100g, promotion dissolution is sufficiently stirred, the solution for finally obtaining clear (can also be prepared other
The biphosphate sodium water solution of concentration need to only guarantee that the water biphosphate sodium content finally prepared in solution reaches for subsequent use
Content range described in specification).
Point taking-up 5mL solution in one bottle of solution to be measured, is added a drop color developing agent, by one end of the Test paper of Cr VI
It immerses among solution, is taken out after 3s, the Test paper of Cr VI becomes purple, it was demonstrated that contains Cr VI in solution.Prove metal
The Test paper of surface hexavalent chromium is set with and detection method may determine that in aqueous solution whether contain Cr VI.
Embodiment 6
It prepares Test paper: firstly the need of the adjacent dinitrodiphenyl carbazide ethyl alcohol acetone mixed solution for preparing 0.2g/mL, weighing
0.1g neighbour's dinitrodiphenyl carbazide powder is placed in the beaker of 50mL, and the ethyl alcohol of 9mL and the acetone of 4mL is added, stirring, until adjacent benzene carbon
Two hydrazine powder of acyl is completely dissolved.Filter paper item is cut into the slice of 1cm х 4cm, is dipped in the adjacent benzene carbon of above-mentioned 0.01g/mL
In two hydrazine ethyl alcohol acetone mixed solution of acyl, 1min is waited.It takes out, filter paper item is put into test tube, inert gas is passed through in test tube
Protection.After paper slip to be filtered air-dries completely, transfer them to closed, deoxygenation, brown reagent bottle or sample sack in it is stand-by.
It prepares color developing agent: 80ml deionized water being added in beaker, it is 85% that 20ml mass fraction is added under stiring
Orthophosphoric acid, then into system, the biphosphate sodium water solution that mass fraction is 29% is added in 20ml, is stirred evenly, is stored in reagent
It is stand-by in bottle.The method that the biphosphate sodium water solution that mass fraction is 29% is prepared is: by 40g anhydrous sodium dihydrogen phosphate solid
It is dissolved in the deionized water of 100g, promotion dissolution is sufficiently stirred, the solution for finally obtaining clear (can also be prepared other
The biphosphate sodium water solution of concentration need to only guarantee that the water biphosphate sodium content finally prepared in solution reaches for subsequent use
Content range described in specification).
Point taking-up 5mL solution in one bottle of solution to be measured, is added a drop color developing agent, by one end of the Test paper of Cr VI
Immerse solution among, taken out after 3s, the Test paper of Cr VI becomes purple, it was demonstrated that contain Cr VI in solution, by with than
The comparison of colour atla, it can be determined that the content of Cr VI is between 1.0mg/L-5.0mg/L.Prove the detection of metal surface Cr VI
Test paper suit and detection method can accurately detect the content of Cr VI in aqueous solution.
Embodiment 7
It prepares Test paper: firstly the need of the adjacent dinitrodiphenyl carbazide ethyl alcohol acetone mixed solution for preparing 0.01g/mL, weighing
0.1g neighbour's dinitrodiphenyl carbazide powder is placed in the beaker of 50mL, and the ethyl alcohol of 4mL and the acetone of 6mL is added, stirring, until adjacent benzene carbon
Two hydrazine powder of acyl is completely dissolved.Filter paper item is cut into the slice of 1cm х 4cm, is dipped in the adjacent benzene carbon of above-mentioned 0.01g/mL
In two hydrazine ethyl alcohol acetone mixed solution of acyl, 1min is waited.It takes out, filter paper item is put into test tube, inert gas is passed through in test tube
Protection.After paper slip to be filtered air-dries completely, transfer them to closed, deoxygenation, brown reagent bottle or sample sack in it is stand-by.
It prepares color developing agent: 60ml deionized water being added in beaker, it is 85% that 20ml mass fraction is added under stiring
Orthophosphoric acid, then into system, the biphosphate sodium water solution that mass fraction is 29% is added in 20ml, is stirred evenly, is stored in reagent
It is stand-by in bottle.The method that the biphosphate sodium water solution that mass fraction is 29% is prepared is: by 40g anhydrous sodium dihydrogen phosphate solid
It is dissolved in the deionized water of 100g, promotion dissolution is sufficiently stirred, the solution for finally obtaining clear (can also be prepared other
The biphosphate sodium water solution of concentration need to only guarantee that the water biphosphate sodium content finally prepared in solution reaches for subsequent use
Content range described in specification).
The aqueous solution that one bottle of content of 6-valence Cr ions is 7mg/L is prepared, divides and takes 5mL into beaker, a drop colour developing is added thereto
One end of the Test paper of Cr VI is immersed among solution, is taken out after 3s by agent, and the Test paper of Cr VI becomes purple, card
Contain Cr VI in bright solution, by compared with colorimetric card, it can be determined that the content of Cr VI 5.0mg/L-10mg/L it
Between, it is consistent with real solution content of 6-valence Cr ions.The Test paper suit and detection method for proving metal surface Cr VI can be quasi-
True quantifies.
Embodiment 8
It prepares Test paper: firstly the need of the adjacent dinitrodiphenyl carbazide ethyl alcohol acetone mixed solution for preparing 0.3g/mL, weighing
0.1g neighbour's dinitrodiphenyl carbazide powder is placed in the beaker of 50mL, and the ethyl alcohol of 8mL and the acetone of 8mL is added, stirring, until adjacent benzene carbon
Two hydrazine powder of acyl is completely dissolved.Filter paper item is cut into the slice of 1cm х 4cm, is dipped in the adjacent benzene carbon of above-mentioned 0.01g/mL
In two hydrazine ethyl alcohol acetone mixed solution of acyl, 1min is waited.It takes out, filter paper item is put into test tube, inert gas is passed through in test tube
Protection.After paper slip to be filtered air-dries completely, transfer them to closed, deoxygenation, brown reagent bottle or sample sack in it is stand-by.
It prepares color developing agent: 80ml deionized water being added in beaker, it is 85% that 30ml mass fraction is added under stiring
Orthophosphoric acid, then into system, the biphosphate sodium water solution that mass fraction is 29% is added in 30ml, is stirred evenly, is stored in reagent
It is stand-by in bottle.The method that the biphosphate sodium water solution that mass fraction is 29% is prepared is: by 40g anhydrous sodium dihydrogen phosphate solid
It is dissolved in the deionized water of 100g, promotion dissolution is sufficiently stirred, the solution for finally obtaining clear (can also be prepared other
The biphosphate sodium water solution of concentration need to only guarantee that the water biphosphate sodium content finally prepared in solution reaches for subsequent use
Content range described in specification).
In the solution to be measured for preparing one bottle of Cr VI containing 10mg/L, therefrom divides and take out 5mL solution, by the inspection of Cr VI
One end of test paper is immersed among solution, is taken out after 3s, the Test paper of Cr VI does not change colour.It is aobvious that a drop is added dropwise into the solution
One end of the Test paper of another Cr VI is immersed among solution, is taken out after 3s, the Test paper of Cr VI becomes by toner
Aubergine.Prove that color developing agent is essential, the detection of metal surface Cr VI to the process color of the Cr VI in solution
It is respectively indispensable at sub-element in test paper suit and detection method.
Embodiment 9
It prepares Test paper: firstly the need of the adjacent dinitrodiphenyl carbazide ethyl alcohol acetone mixed solution for preparing 0.4g/mL, weighing
0.1g neighbour's dinitrodiphenyl carbazide powder is placed in the beaker of 50mL, and the ethyl alcohol of 7mL and the acetone of 9mL is added, stirring, until adjacent benzene carbon
Two hydrazine powder of acyl is completely dissolved.Filter paper item is cut into the slice of 1cm х 4cm, is dipped in the adjacent benzene carbon of above-mentioned 0.01g/mL
In two hydrazine ethyl alcohol acetone mixed solution of acyl, 1min is waited.It takes out, filter paper item is put into test tube, inert gas is passed through in test tube
Protection.After paper slip to be filtered air-dries completely, transfer them to closed, deoxygenation, brown reagent bottle or sample sack in it is stand-by.
It prepares color developing agent: 70ml deionized water being added in beaker, it is 85% that 30ml mass fraction is added under stiring
Orthophosphoric acid, then into system, the biphosphate sodium water solution that mass fraction is 29% is added in 30ml, is stirred evenly, is stored in reagent
It is stand-by in bottle.The method that the biphosphate sodium water solution that mass fraction is 29% is prepared is: by 40g anhydrous sodium dihydrogen phosphate solid
It is dissolved in the deionized water of 100g, promotion dissolution is sufficiently stirred, the solution for finally obtaining clear (can also be prepared other
The biphosphate sodium water solution of concentration need to only guarantee that the water biphosphate sodium content finally prepared in solution reaches for subsequent use
Content range described in specification).
A drop clear water is added dropwise in a metal coating surface containing Cr VI, it will be golden with the Test paper of Cr VI after 1min
The water of metal surface blots, and the Test paper of Cr VI does not change colour.A drop color developing agent is added dropwise to same position again, with six after 1min
The Test paper of valence chromium blots the water of metal surface, and the Test paper of Cr VI becomes aubergine.Prove color developing agent to metal
The process color of the Cr VI on surface be it is essential, it is each in the Test paper of metal surface Cr VI suit and detection method
It is indispensable at sub-element.
It is the concentration gradients that the colorimetric card of value in 9 embodiments is 0.5 above, it is preliminary to metal coating surface sexavalence
Chromium content carries out quantitative detection.
The present invention obtained it is a kind of using the time longer sexavalence paper of chrome,test that can be commercialized, complete sexavalence paper of chrome,test
Use environment it is mating, by further studying, it is found that the use of this test paper can not only be completed whether to contain Cr VI
Judgement, it may have be Cr VI definite value preliminary potentiality.For this purpose, a series of hexavalent chromium solutions for having concentration gradients are configured with,
It is developed the color with test paper, the colour developing result of test paper also has good color gradient, for this gradient, has manufactured a kind of reference colour
Plate, with can simply be carried out very much on colour table it is more accurately quantitative.For metal sample, the volume according to a drop reagent is
0.05mL, finally forming the circular drop that diameter is 0.5cm in metal surface is basic parameter, goes out metal-plated by Conversion Calculation
The content range of Cr VI in layer surface.The test paper is the adjacent dinitrodiphenyl carbazide that (0.005~0.5) g/mL is immersed by filter paper
In ethyl alcohol acetone mixed solution, take out, under the protection of inert gas air-dry, be stored in closed, deoxygenation, brown reagent bottle or
It is kept in dark place in sample sack；Each ingredient in the adjacent dinitrodiphenyl carbazide ethyl alcohol acetone soln of described (0.005~0.050) g/mL
Ratio are as follows: adjacent dinitrodiphenyl carbazide: ethyl alcohol: acetone=(0.05~0.5) g:(1~9) mL:(1~9) mL；The color developing agent is positive
Phosphoric acid (mass fraction 85%), biphosphate sodium water solution (mass fraction 29%) and deionized water form, each ingredient
Volume ratio are as follows: orthophosphoric acid: biphosphate sodium water solution: deionized water=(5~30): (5~30): (40~90).
The present invention as indicator is not deposited extensively with metal under analysis condition due to it using adjacent dinitrodiphenyl carbazide
The metal ions such as iron, manganese develop the color, and have selection color developing effect well to Cr VI.But adjacent dinitrodiphenyl carbazide also has
Have it is many be easily oxidized in air failure, to the sensibility of ultraviolet light, be easy that water suction deliquesces, solubility is lower in a solvent
And solution rate it is slower the disadvantages of, which results in current laboratory operation during can only configure the lower adjacent benzene phosphinylidyne of content
The two hydrazine solutions and solution holding time is shorter.By consulting literatures and Patent data, the process that sexavalence paper of chrome,test saves is found
There is no particular/special requirement mostly, will redden failure quickly (1~2 day) according to the test paper of these document patents production.Ethyl alcohol and third
Ketone is cheap, is easier volatilization air-dries, chemical toxicity is smaller, so the present invention is dissolved using the mixed solution of ethyl alcohol acetone
Adjacent dinitrodiphenyl carbazide accelerates the solution rate of adjacent dinitrodiphenyl carbazide under ultrasonic atmosphere, and carries out isolation air to test paper and do
It is dry it is possible to prevente effectively from adjacent dinitrodiphenyl carbazide oxidation, and be passed through inert gas flow and can accelerate the dry speed of test paper, again
By preparation complete test paper be stored in closed, deoxygenation, brown reagent bottle or sample sack in, the shelf-life of sample significantly prolongs
It is long.
Prepare the ratio of each ingredient in the adjacent dinitrodiphenyl carbazide ethyl alcohol acetone soln of test paper: 1 must assure that relative to sexavalence
Chromium neighbour's dinitrodiphenyl carbazide be it is excessive, just can guarantee the consistency of test paper color development effect in this way；2 adjacent dinitrodiphenyl carbazides in ethyl alcohol and
Solubility in acetone mixed solution be it is certain, can not have excessive adjacent dinitrodiphenyl carbazide in solution；When the colour developing of 3 test paper
Between and colour developing result stablize the time with neighbour dinitrodiphenyl carbazide concentration be related.Regulation: 1 adjacent benzene carbon is made to the soak of test paper
The minimum concentration of two hydrazine of acyl is 0.005g/mL, guarantees that the most highly concentrated of the adjacent dinitrodiphenyl carbazide of colour developing 2 can occur for all Cr VIs
Degree is 0.5g/mL, avoids the supersaturation of adjacent dinitrodiphenyl carbazide.Within the scope of this, all Cr VIs can be with adjacent benzene phosphinylidyne
Two hydrazines react, while developing time can control and guarantee that the evaporation of moisture will not cause shadow to colour developing result within 5s
It rings.In addition, developing time needs to control in 3s or more, guarantee that Cr VI sufficiently develops the color.
The color developing effect of adjacent dinitrodiphenyl carbazide can only occur in solution in acid condition, so the process entirely analyzed
In must assure that test paper whole use environment be acid solution, for this purpose, can choose in test paper be added acid anhydrides either create
Make a kind of liquid atmosphere.It can only be analysed under solution environmental because the Cr VI of metal surface is present within solid coating again
Out, so create a kind of liquid atmosphere while providing liquid environment this thinking for test paper and the coat of metal.Specially have developed
A kind of test paper color developing agent, color developing agent is orthophosphoric acid (mass fraction 85%), (mass fraction is biphosphate sodium water solution
29%) it is formed with deionized water, the volume ratio of each ingredient are as follows: orthophosphoric acid: biphosphate sodium water solution: deionized water=(5~
30): (5~30): (40~90).Orthophosphoric acid can provide acidic environment for the color developing effect of adjacent dinitrodiphenyl carbazide, while may be used also
The Cr VI inside coating is promoted to dissolve out to corrode coating；Biphosphate sodium water solution provides for the stabilization of whole system acidity
Support, prevents the variation that extent of reaction is too fast；Deionized water provides indispensable solution environmental then for entire reaction process.This
The ingredient and content of the color developing agent of invention ensure that the testing conditions of the Cr VI of metal surface and the stability of test paper color,
Most suitable acidity environment is provided for the dissolution of Cr VI, the colour developing of adjacent dinitrodiphenyl carbazide and precise measurement.
As stated above: 1) having immersed adjacent dinitrodiphenyl carbazide ethyl alcohol acetone mixed solution using air-dried under the protection of inert gas
Filter paper, effectively prevent adjacent dinitrodiphenyl carbazide to be aoxidized by the oxygen in air, test paper caused to fail；2) corroded using color developing agent
Metal coating surface, while color developing agent can play the role of adjusting solution system pH value, promote adjacent dinitrodiphenyl carbazide and sexavalence
The generation of chromium chromogenic reaction；3) that is reacted using colorimetric card is quantified, can be with the determination metal coating surface of quicklook
The substantially content of Cr VI；4) Test paper of metal surface Cr VI is stored in the reagent bottle or sample of closed, deoxygenation, brown
In bag, it can store for a long time, the test paper validity period is up to half a year or more at present.
Claims (8)
1. a kind of detection method of metal surface Cr VI, which is characterized in that steps are as follows:
S1, prepare Test paper: compound concentration is the ethyl alcohol acetone mixed solution of the adjacent dinitrodiphenyl carbazide of 0.005-0.5g/mL,
Filter paper item is immersed in above-mentioned mixed solution, filter paper item is put into the closed container of inert gas by filter paper item after taking out, filter paper
After item air-dries completely, be transferred to closed, deoxygenation, brown reagent bottle or sample sack in it is stand-by；
S2, acid developer is dripped in metal surface to be measured, then the Test paper in step 1 is immersed into color developing agent, observe test paper
The content range of Cr VI is determined after the variation of color and colorimetric card comparison.
2. a kind of detection method of metal surface Cr VI as described in claim 1, which is characterized in that described in step S1
The concentration of the ethyl alcohol acetone mixed solution of adjacent dinitrodiphenyl carbazide is 0.01g/mL.
3. a kind of detection method of metal surface Cr VI as described in claim 1, which is characterized in that described in step S2
The composition and volume of color developing agent are as follows: the orthophosphoric acid that mass fraction is 85%: the sodium dihydrogen phosphate that mass fraction is 29% is water-soluble
Liquid: deionized water is 5~30ml:5~30ml:40~90ml.
4. a kind of detection method of metal surface Cr VI as described in claim 1, which is characterized in that described in step S2
The composition and volume of color developing agent are as follows: the orthophosphoric acid that mass fraction is 85%: the sodium dihydrogen phosphate that mass fraction is 29% is water-soluble
Liquid: deionized water 20ml:20ml:60ml.
5. a kind of detection method of metal surface Cr VI as described in claim 1, which is characterized in that described in step S1
The ratio of ethyl alcohol and acetone is 1-9:1-9.
6. a kind of detection method of metal surface Cr VI as described in claim 1, which is characterized in that described in step S1
The ratio of ethyl alcohol and acetone is 4:6.
7. a kind of detection method of metal surface Cr VI as described in claim 1, which is characterized in that described in step S2
Colorimetric card the preparation method comprises the following steps: a series of hexavalent chromium solutions for having concentration gradients of configuration, are developed the color with the test paper in step S1,
For the color gradient of the colour developing result of test paper, standard color comparison card is manufactured.
8. a kind of detection method of metal surface Cr VI as claimed in claim 7, which is characterized in that the Cr VI is molten
Liquid hold-up is followed successively by 0mg/L, 0.1mg/L, 0.5mg/L, 1mg/L, 10mg/L, 50mg/L, 100mg/L.
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Application publication date: 20190402 |