CN110441243A - It is a kind of based on film enrichment and UV-vis DRS spectrum underwater trace copper ion quantitative analysis method - Google Patents
It is a kind of based on film enrichment and UV-vis DRS spectrum underwater trace copper ion quantitative analysis method Download PDFInfo
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- CN110441243A CN110441243A CN201810417195.8A CN201810417195A CN110441243A CN 110441243 A CN110441243 A CN 110441243A CN 201810417195 A CN201810417195 A CN 201810417195A CN 110441243 A CN110441243 A CN 110441243A
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N1/00—Sampling; Preparing specimens for investigation
- G01N1/28—Preparing specimens for investigation including physical details of (bio-)chemical methods covered elsewhere, e.g. G01N33/50, C12Q
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N1/00—Sampling; Preparing specimens for investigation
- G01N1/28—Preparing specimens for investigation including physical details of (bio-)chemical methods covered elsewhere, e.g. G01N33/50, C12Q
- G01N1/34—Purifying; Cleaning
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
- G01N21/17—Systems in which incident light is modified in accordance with the properties of the material investigated
- G01N21/25—Colour; Spectral properties, i.e. comparison of effect of material on the light at two or more different wavelengths or wavelength bands
- G01N21/31—Investigating relative effect of material at wavelengths characteristic of specific elements or molecules, e.g. atomic absorption spectrometry
Abstract
The present invention relates to a kind of based on film enrichment and the underwater trace copper ion quantitative analysis method of UV-vis DRS spectrum.The specific steps are copper nitrate solution, PAN solution and the Tris-HCl buffer solution reagents needed for preparation experiment；Generate Cu2+Complex compound the optimal absorption wavelength points of copper ion are determined by UV-vis DRS spectrum；PH, PAN dosage, reaction time and amount of samples are optimized using the method for control variable, obtain optimal detection condition；Under optimal detection condition, a series of Cu of various concentrations is prepared2+Solution after being enriched with using cellulose mixture film, is directly detected its UV-vis DRS spectrum, establishes Cu2+Working curve.The present invention is based on UV-vis DRS spectrum and film beneficiation technologies, are not necessarily to elution step, rapidly, accuracy is high for detection.The present invention is suitable for the quantitative analysis of underwater trace heavy metal ion.
Description
Technical field
The invention belongs to environmental monitoring field, and in particular to a kind of water based on film enrichment and UV-vis DRS spectrum
Middle trace copper ion quantitative analysis method.
Background technique
Copper is a kind of microelement necessary to a kind of metallic chemical element and human body, is blood important component；
Copper mainly plays catalytic action in body, and copper-containing metal enzyme has highly important physiological function in human body.But in human body
Copper excessively may occur in which nausea and vomiting, Upper abdominal pain, Acute hemolytic crisis and renal tubule deformation etc. intoxicating phenomenons.Therefore it provides efficiently,
Accurate underwater trace copper ion quantitative analysis method is of great significance.(Wang Yanmin, the measurement of trace copper ion in water environment
Method, Chinese invention patent, 2017, CN201710765214.1)
Currently, the method for measurement content of copper ion has inductively coupled plasma atomic emission spectrometry, inductive coupling etc.
Gas ions mass spectrography, atomic absorption spectrography (AAS) etc..Although these methods can obtain preferable prediction result, there is also offices
Sex-limited, such as expensive equipment expends the problems such as time and matrix interference, especially receives in actual sample analysis certain
Limitation.Ultraviolet-visible spectrophotometry is for detecting a huge sum of money using simple, quick response, the low significant advantage of operating cost
Another method of category.But the shortcomings that traditional ultraviolet-visible spectrophotometry is that sensitivity is low, its usual detection limit is in mg/
L grades.Therefore, separation and preenrichment technology measure μ g/L grades of heavy metal and are particularly important.PAN is a kind of complexing of good performance
Agent and color developing agent, belong to pyridylazo reagents.Coloured complex can be formed with most metal ions, complex is not yet
Molten and water.Solid Phase Extraction spectrum (SPES) is a kind of solid phase directly during analyte all concentrates on Solid Phase Extraction (SPE)
The technology of material (such as polystyrene, membrane material) measurement spectrum.Solid Phase Extraction spectrum due to no elution, and advantage be it is time-consuming less,
Less organic reagent is consumed, the prefered method of many metal ion enrichments is become.(Chen Xiangfeng, one kind are extracted based on miniature solid phase
Take the Electrospray Ionization Mass Spectrometry system and its preparation method and application in pond, Chinese invention patent, 2016,
CN201710765214.1)
When the UV-vis DRS spectrum of complex compound Cu-PAN is easy the dosage by test condition such as PH, PAN, reaction
Between and amount of samples influence, the best absorbance that these factors will lead to complex compound Cu-PAN changes, and then influences weight
The detection limit of metal.Therefore, it is necessary to which suitable test condition should be chosen, to determine the best absorbance of complex compound Cu-PAN.
Summary of the invention
The purpose of invention is in view of the above problems, using ultraviolet-visible spectrophotometry as means of testing, one
Under the optimal test condition of series, using cellulose mixture film as rich medium, without elution step, the directly total gold of detection enrichment
Belong to the UV-vis DRS spectrum of the film of ion.A kind of accurately and rapidly underwater trace copper ion quantitative analysis method is provided.
The technical scheme comprises the following steps provided by realize the present invention:
1) copper nitrate solution, PAN solution and buffer solution Tris-HCl are prepared
Purchase copper nitrate, dehydrated alcohol, hydrochloric acid, three (methylol) aminomethanes, 1- (2- pyridylazo)-beta naphthal
(PAN) and the cellulose mixture film of certain specification.A certain amount of copper nitrate is weighed, is dissolved with ultrapure water, 100mL capacity is settled to
In bottle, it is configured to 1.0g/LCu2+Stock solution；Weigh a certain amount of 1- (2- pyridylazo)-beta naphthal (PAN), and with anhydrous second
Alcohol dissolution, constant volume are configured to 6.42 × 10 in 250mL volumetric flask-5The PAN solution of mol/L；Weigh three (methylol) amino first
Alkane is simultaneously dissolved with the ultrapure water of certain volume, until completely dissolved, hydrochloric acid is added and is detected with pH meter, and being configured to pH is 9.0 slow
Rush solution Tris-HCl.
2) the best ultravioletvisible absorption wavelength points of copper ion are determined
With Tris-HCl buffer solution by 100mL Cu2+Sample solution pH is adjusted to 9.0 (being detected with pH meter), then accurate to add
Enter quantitative PAN solution, be vigorously stirred to form metal complex, later filter solution, is configured to Cu-PAN complex compound, makes network
It closes object to be enriched on cellulose mixture film, after film is dried in air, film surface is measured in 400-800nm wave-length coverage
UV-vis DRS spectrum, to determine the best ultravioletvisible absorption wavelength points of copper ion.
3) Optimization of Copper ion detection condition
The testing conditions such as the dosage of pH, PAN, reaction time and amount of samples are optimized, complex compound Cu-PAN is obtained
Optimal detection condition.
The optimization of the pH: (Cu in the case where other conditions are certain2+Degree is 6 μ g/L, PAN dosage 2.0mL, amount of samples
100mL, reaction time 10min), the pH value of solution is adjusted with Tris-HCl buffer solution, with pH meter measurement pH be respectively 4.3,
6,7,7.5,8,8.5,9,9.5 when, measure complex compound Cu-PAN absorbance.The corresponding pH of the maximum value of absorbance is best
pH。
The optimization of PAN the dosage: (Cu in the case where the best other conditions of pH are certain2+Concentration is 6 μ g/L, amount of samples
100mL, reaction time 10min), measure PAN solution within the scope of 0.2-1.4mL 7 kinds of different additional amounts to Cu-PAN extinction
Degree.The corresponding PAN dosage of the maximum value of absorbance is optimum amount.
The optimization in the reaction time: (Cu in the case where the best other conditions of pH, PAN dosage are certain2+Concentration is 6 μ g/L,
Amount of samples 100mL), investigate the absorbance of complex compound Cu-PAN under differential responses time (2,5,7,12,15,20min).Extinction
The corresponding PAN dosage of the maximum value of degree is best complex compound dosage.
The optimization of amount of samples: under pH, PAN dosage, reaction time optimum condition, 6 μ g/L Cu are investigated2+Standard solution
Different sample volumes (25,50,75,100,125,150mL) under complex compound Cu-PAN absorbance.The maximum value pair of absorbance
The amount of samples answered is best sample dosage.
4) it establishes the working curve of trace copper ion detection and calculates detection limit
1.0g/L Cu is diluted with ultrapure water2+Stock solution obtains the copper nitrate solution of various concentration within the scope of trace, best
Under testing conditions, using cellulose mixture film as rich medium, enriching heavy metal is directly detected with UV-vis DRS spectrum
The film of ion, obtains Cu2+The curve of concentration and absorbance.It is measured 7 times using ultrapure water as blank condition, calculates variance S, press
3 times of variance evaluation methods obtain Cu2+Detection limit (3S/k).
Detailed description of the invention
Fig. 1 is the UV Diffuse Reflectance Spectroscopy figure of various concentration copper ion on film
Fig. 2 is the corresponding complex compound Cu-PAN absorbance figure of different pH
Fig. 3 is different the corresponding complex compound Cu-PAN absorbance figure of PAN dosage
Fig. 4 is differential responses time corresponding complex compound Cu-PAN absorbance figure
Fig. 5 is the corresponding complex compound Cu-PAN absorbance figure of different sample volumes
Fig. 6 is the corresponding Cu of different quality concentration2+Canonical plotting
Specific embodiment
To be best understood from the present invention, the present invention will be described in further detail with reference to the following examples, but of the invention
Claimed range is not limited to range represented by embodiment.
Embodiment:
The present embodiment is the detection applied to underwater trace copper ion, using UV-vis DRS spectrum and optimizes a system
Column test condition carries out quantitative analysis to the copper ion in sample.Specific steps are as follows:
1) copper nitrate solution, PAN solution and buffer solution Tris-HCl are prepared
Copper nitrate, dehydrated alcohol, hydrochloric acid, three (methylol) amino that Duo Jia chemical reagent factory purchase specification is AR in Tianjin
Methane, 1- (2- pyridylazo)-beta naphthal (PAN) and diameter 50mm, the cellulose mixture film in 0.22 μm of aperture.Prepare 1.0g/
LCu2+: copper nitrate 0.3802g is weighed, is dissolved with ultrapure water, and is settled in 100mL volumetric flask.Prepare 6.42 × 10-5mol/L
PAN solution: weigh 0.0040g PAN, dissolved with dehydrated alcohol, constant volume is in 250mL volumetric flask.Prepare buffer solution
Tris-HCl (pH 9.0): weighing 2.4228g hydrochloric acid three (methylol) aminomethane and be dissolved in 200mL ultrapure water, to completely molten
Salt acid for adjusting pH is added after solution and is detected as 9.0 with pH meter.
2) the best ultravioletvisible absorption wavelength points of copper ion are determined
With Tris-HCl buffer solution by the 100mLCu of 1.0g/L2+Sample solution pH is adjusted to 9.0 (being detected with pH meter), so
1.2mLPAN solution is accurately added afterwards, is vigorously stirred 5min and forms metal complex, solution is filtered later, is enriched with complex compound
Onto cellulose mixture film, after film is dried in air, the UV, visible light of film surface is measured in 400-800nm wave-length coverage
Diffusing reflection spectrum.Fig. 1 is the UV-vis DRS spectrogram of various concentration copper ion on film.It is complex compound Cu- at 555nm
The absorption peak of PAN, therefore select best ultravioletvisible absorption wavelength points of the 555nm as copper ion.
3) Optimization of Copper ion detection condition
The optimization of the pH: (Cu in the case where other conditions are certain2+Concentration is 6 μ g/L, PAN dosage 2.0mL, amount of samples
100mL, reaction time 10min), the pH value of solution is adjusted with Tris-HCl buffer solution, with pH meter measurement pH be respectively 4.3,
6,7,7.5,8,8.5,9,9.5 when, measure complex compound Cu-PAN absorbance.Fig. 2 is pH to complex compound Cu-PAN absorbance
It influences, the Optimal pH of complex reaction is 9.0.
The optimization of PAN the dosage: (Cu in the case where best 9.0 other conditions of pH are certain2+Concentration is 6 μ g/L, and sample is used
Measure 100mL, reaction time 10min), it measures PAN solution 7 kinds of different additional amounts within the scope of 0.2-1.4mL and Cu-PAN is inhaled
Luminosity.Fig. 3 is influence of the PAN dosage to complex compound Cu-PAN absorbance, and PAN optimum amount is 1.2mL.
The optimization in reaction time: in the pH best best 1.2mL of 9.0, PAN dosage, (Cu in the case that other conditions are certain2+
Concentration is 6 μ g/L, amount of samples 100mL), investigate the suction of complex compound Cu-PAN under reaction time (2,5,7,12,15,20min)
Luminosity.Fig. 4 is influence of the reaction time to complex compound Cu-PAN absorbance, optimum reacting time 5min.
The optimization of amount of samples: (pH 9.0, PAN dosage 1.2mL, reaction time in the case where other conditions are optimal
5min), 6 μ g/L Cu are investigated2+Complex compound Cu- under the different sample volumes (25,50,75,100,125,150mL) of standard solution
The absorbance of PAN.Fig. 5 is influence of the amount of samples to complex compound Cu-PAN absorbance, and best sample volume is 100mL.
4) it establishes the working curve of trace copper ion detection and calculates detection limit
1.0g/L Cu is diluted with ultrapure water2+The copper nitrate that stock solution obtains 6 kinds of various concentrations within the scope of 2-12 μ g/L is molten
Liquid, using cellulose mixture film as rich medium, measures the ultraviolet of 6 kinds of complex compound Cu-PAN under optimal detection condition respectively
It can be seen that diffusing reflection spectrum, obtains Cu2+It is in a linear relationship in 2-12 μ g/L and absorbance.Linear relationship are as follows: Y=0.00143X+
0.04831；R=0.9909.Therefore, the inspection of heavy metal ion can be well realized in uv-vis spectra combination film beneficiation technologies
It surveys.It uses ultrapure water for blank solution measurement 7 times, variance S is calculated, by the detection limit (3S/k) of 3 times of variance evaluation methods, Cu2+
Detection be limited to 0.2262 μ g/L.
Claims (5)
1. a kind of existed based on film enrichment and the underwater trace copper ion quantitative analysis method of UV-vis DRS spectrum, feature
In: reagent needed for preparation experiment；And the UV Diffuse Reflectance Spectroscopy for being formulated complex compound is acquired, determine the best purple of copper ion
Outer visible absorbance wavelength points；Using the method for control variable to test condition (dosage, reaction time and the sample use of pH, PAN
Amount) it optimizes；The working curve for establishing trace copper ion detection, obtains Cu2+Detection limit, to unknown sample predict.
2. copper ion is fixed in a kind of trace water based on film enrichment and UV-vis DRS spectrum according to claim 1
Analysis method, it is characterised in that: the optimization process of the pH are as follows: (Cu in the case where other conditions are certain2+Concentration is 6 μ
G/L, PAN dosage 2.0mL, amount of samples 100mL, reaction time 10min), the pH of solution is adjusted with Tris-HCl buffer solution
Value measures the absorbance of complex compound Cu-PAN, extinction when being respectively 4.3,6,7,7.5,8,8.5,9,9.5 with pH meter measurement pH
The corresponding pH of the maximum value of degree is Optimal pH.
3. copper ion is fixed in a kind of trace water based on film enrichment and UV-vis DRS spectrum according to claim 1
Analysis method, it is characterised in that: the optimization process of the PAN dosage are as follows: in the case where the best other conditions of pH are certain
(Cu2+Concentration is 6 μ g/L, amount of samples 100mL, reaction time 10min), PAN solution is measured 7 kinds within the scope of 0.2-1.4mL
Different additional amounts is to Cu-PAN absorbance.The corresponding PAN dosage of the maximum value of absorbance is optimum amount.
4. copper ion is fixed in a kind of trace water based on film enrichment and UV-vis DRS spectrum according to claim 1
Analysis method, it is characterised in that: the optimization process in the reaction time are as follows:, other conditions one best in pH, PAN dosage
(Cu in the case where fixed2+Concentration is 6 μ g/L, amount of samples 100mL), it investigates differential responses time (2,5,7,12,15,20min)
The absorbance of lower complex compound Cu-PAN.The corresponding PAN dosage of the maximum value of absorbance is best complex compound dosage.
5. copper ion is fixed in a kind of trace water based on film enrichment and UV-vis DRS spectrum according to claim 1
Analysis method, it is characterised in that: the optimization process of the amount of samples are as follows: in pH, PAN dosage, reaction time best item
Under part, 6 μ g/L Cu are investigated2+Complex compound Cu- under the different sample volumes (25,50,75,100,125,150mL) of standard solution
The absorbance of PAN.The corresponding amount of samples of the maximum value of absorbance is best sample dosage.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112322375A (en) * | 2020-11-13 | 2021-02-05 | 西安热工研究院有限公司 | Method for removing iron and copper ions in lubricating oil |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103499538A (en) * | 2013-09-26 | 2014-01-08 | 苏州国环环境检测有限公司 | Method for measuring trace copper in water through ultrasonic extraction-atomic spectrum |
| CN105466863A (en) * | 2015-11-18 | 2016-04-06 | 天津工业大学 | A membrane enrichment-ultraviolet-visible diffuse reflection spectroscopy based trace heavy-metal-ion measuring method |
| CN106644953A (en) * | 2016-09-14 | 2017-05-10 | 天津工业大学 | Method for improving simultaneous detection sensitivity and accuracy of multiple heavy metal ions |
| CN106769926A (en) * | 2016-11-30 | 2017-05-31 | 张帆 | Copper, cadmium in a kind of detection tea oil, the method for lead |
| CN107219177A (en) * | 2017-05-31 | 2017-09-29 | 浙江海洋大学 | The method of zinc, copper, total chrome content in METHOD FOR CONTINUOUS DETERMINATION hemipelagic sediment |
-
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- 2018-05-02 CN CN201810417195.8A patent/CN110441243A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103499538A (en) * | 2013-09-26 | 2014-01-08 | 苏州国环环境检测有限公司 | Method for measuring trace copper in water through ultrasonic extraction-atomic spectrum |
| CN105466863A (en) * | 2015-11-18 | 2016-04-06 | 天津工业大学 | A membrane enrichment-ultraviolet-visible diffuse reflection spectroscopy based trace heavy-metal-ion measuring method |
| CN106644953A (en) * | 2016-09-14 | 2017-05-10 | 天津工业大学 | Method for improving simultaneous detection sensitivity and accuracy of multiple heavy metal ions |
| CN106769926A (en) * | 2016-11-30 | 2017-05-31 | 张帆 | Copper, cadmium in a kind of detection tea oil, the method for lead |
| CN107219177A (en) * | 2017-05-31 | 2017-09-29 | 浙江海洋大学 | The method of zinc, copper, total chrome content in METHOD FOR CONTINUOUS DETERMINATION hemipelagic sediment |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112322375A (en) * | 2020-11-13 | 2021-02-05 | 西安热工研究院有限公司 | Method for removing iron and copper ions in lubricating oil |
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