CN105842044A - Method for determining content of elemental mercury in metavanadate, and preparation method for sample solution - Google Patents
Method for determining content of elemental mercury in metavanadate, and preparation method for sample solution Download PDFInfo
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Abstract
The invention relates to a method for determining the content of elemental mercury in metavanadate and a preparation method for a sample solution, belonging to the technical field of element detection. To overcome a technical problem, the invention provides the preparation method for the sample solution used for determination of the content of elemental mercury in metavanadate. The preparation method comprises the following successive steps: dissolving a metavanadate sample with water; adding nitric acid and hydrogen peroxide and carrying out heating to 60 to 65 DEG C for digestion; and after completion of digestion, carrying out cooling to room temperature and then carrying out diluting with water until a volume is fixed so as to obtain a sample detection solution. According to the invention, an ICP-MS determination method is established for determination of the trace impurity element mercury with a content in a range of 0.0001 to 0.1000% in metavanadate, and performance indexes of the method are that quantitative determination lower limit is 0.0001%, the degree of precision is less than 10% and a recovery rate is 80 to 120%. The determination method has the characteristics of easy and fast operation, short analysis time, small usage amount of reagents, low blank, few influence factors, low detection lower limit, high precision, high accuracy, etc.
Description
Technical field
The present invention relates to measure method and the sample solution preparation method of mercury element content in metavanadate, belong to Element detection technology
Field.
Background technology
Inclined using alkali metal, alkaline-earth metal or ammonium radical ion as cationic components such as ammonium metavanadate, potassium metavanadate and sodium metavanadate
Vanadate series products, is not only a kind of intermediate products refining vanadium technique, mainly for the preparation of vanadic anhydride or vanadium metal, enters
And produce vanadium iron, vanadium aluminum, vanadium titanium aluminum, vanadium nitrogen and other vanadium-base alloy material；Metavanadate is also can be used as of one simultaneously
Learn the broad-spectrum vanadium fine chemical products such as reagent, catalyst, drier, mordant and ceramics glaze.Due to impurity element
Content not only affects the grade grade of product, and has a strong impact on the activity of product, life-span and purposes, especially as metavanadate
The continuous extension of application, the metavanadate of many emerging application has been gradually increased the quality of trace impurity hydrargyrum in product
Examination requirements.
At present, the detection means and the technical method that measure mercury element content in sample mainly have following several: hydride generation atomic
Fluorescent spectrometry (HG-AFS), GFAAS (GF-AAS), cold mercury vapor atoms absorption spectrometry (HG
-AAS), ICP-AES (ICP-OES), inductively coupled plasma mass spectrometry (ICP
-MS) etc..Its key technical problems surveying hydrargyrum analysis method is to be specific to the detection object of various dissimilar sample, must
Need the main corresponding technical barrier solving following three aspects: 1. Specimen eliminating technology of preparing: be required in sample matrix component and
The chemical reaction characteristic of impurity to be measured, develops suitable Specimen eliminating preparation method, especially clear up used chemical reagent kind,
The conditions such as composition, proportioning, consumption and reaction temperature, in order to guarantee that sample matrices and element mercury to be measured etc. all can be quick and complete
Clear up entrance solution, avoid the mercury element volatilization loss with volatile characteristic simultaneously thus affect the accuracy of measurement result；②
The impact on measuring such as the matrix effect that elimination sample matrices and Coexisting component are caused；3. avoid clearing up the salt that reagent place causes
The matrix effect such as concentration, acidity, mass spectrum interference etc. are to determination influences.
Have not seen that at present employing ICP-MS measures in the metavanadates such as ammonium metavanadate, potassium metavanadate and sodium metavanadate 10 the most temporarily-6Contain
The document report of the Trace Hg determination method of amount level.
Summary of the invention
The present invention is directed to the chemical property of the metavanadates such as ammonium metavanadate, potassium metavanadate, sodium metavanadate, develop matched phase
Suitable sample detection solution manufacturing method and detection method, solve the technical barrier of above-mentioned three aspects simply and effectively.
First technical problem that the present invention solves is to provide and measures the preparation side of the sample solution of mercury element content in metavanadate
Method.
The present invention measures the sample solution preparation method of mercury element content in metavanadate, and its step is followed successively by:
A, metavanadate sample is dissolved in water；
B, add nitric acid and hydrogen peroxide, be heated to 60～65 DEG C, carry out clearing up and make sample and coexistent impurity clear up completely；
C, clear up after, be cooled to room temperature, with water dilute constant volume, i.e. obtain sample solution.
Preferably, water, nitric acid are 1.5～2.5:1:0.8～1.2 with the volume ratio of hydrogen peroxide, preferably water, nitric acid and mistake
The volume ratio of hydrogen oxide is 2:1:1.
Preferably, described nitric acid mass percent concentration is 65%～68%, mass percent concentration >=30% of hydrogen peroxide.
Preferably, reagent dosage is according to sample quality: nitric acid volume is the ratio addition of 0.1～0.2g:3～6ml.
Further, b step digestion time is 2～3min.
Preferably, 0.10～0.20g metavanadate sample dilutes to volume in 50～100mL volumetric flasks with water.
Further, described metavanadate is preferably the metavanadate using alkali metal, alkaline-earth metal or ammonium radical ion as cation,
It is preferably ammonium metavanadate, sodium metavanadate or potassium metavanadate.
In described metavanadate, preferably mercury content is 0.0001～0.1000%.
The present invention measures the sample solution preparation method of mercury element content in metavanadate, utilizes ammonium metavanadate, sodium metavanadate, partially
The matrix using alkali metal, alkaline-earth metal or ammonium radical ion etc. as the metavanadic acid salt sample of cationic components such as potassium vanadate forms easily
It is dissolved in the characteristic of water, the most at ambient temperature with the water dissolvable impurity etc. in water direct sample dissolution matrix and sample, from
And shorten its time in heating period reaction, reduce the heated evaporation ease of effumability mercury element in sample solution preparation process
The risk gone out；Then according to the volume ratio of water, concentrated nitric acid and hydrogen peroxide is 2:1:1, and every 0.1 gram of sample needs 3mL
Nitric acid and the relation of hydrogen peroxide, add there is Specimen eliminating reagent and the dense nitre of mercury oxidation media protection agent dual function simultaneously
Acid and hydrogen peroxide, and metavanadate solution is heated to 60～65 DEG C and in this temperature range, keeps 2～3min.This skill
Art step effective guarantee is the temperature conditions of 60～65 DEG C and promotes the water-insoluble impurity in sample all by soon under nitric acid effect
Speed is cleared up completely, controls in this reaction temperature and time range also for avoiding the heated evaporation of effumability mercury element simultaneously
Effusion affects testing result accuracy；Especially, the nitric acid of strong oxidizing property, hydrogen peroxide agent itself, and nitric acid and peroxidating
Active oxygen that hydrogen reaction generates all it is effectively guaranteed that sample solution is in strong oxidizing property medium, further ensures that and clears up entrance sample
Among mercury element in product solution is maintained ionic forms thus is stable at and is kept in solution with, it is to avoid mercury ion is reduced to easily
The hydrargyrum of volatile atomic state thus form mercury vapour effusion of volatilizing from solution and affect testing result accuracy.
Second technical problem that the present invention solves is to provide the method for mercury element content in metavanadate that measures.
The present invention measures the method for mercury element content in metavanadate, and ICP-MS is as detection means in employing, and by online
The connecting mode of internal standard blender, divides sample solution, series of calibration curve mercury standard solution via the peristaltic pump of ICP-MS instrument
Do not mix according to volume ratio 1:1 with the rhodium element standard solution that concentration is 1～5ng/mL, be then introduced into ICP-MS instrument and take
The mode of Internal standard correction methods is measured, and draws calibration curve, and is calculated the mercury content in sample solution by calibration curve；Wherein,
Described sample solution is the sample solution that preparation method of the present invention prepares, described series of calibration curve mercury standard solution
Be respectively 0 by concentration, 1,2,5,10,20,50,100ng/mL, and nitric acid, content of hydrogen peroxide and sample solution one
The mercury solution composition caused.
Preferably, the instrument detection parameter of ICP-MS specifically includes that analysis isotope is201.971Hg (29.86%),199.968Hg
(23.10%),198.968Hg (16.87%)；Radio-frequency emission power 1000W, cools down gas velocity (Ar) 15L/min, assists gas
Flow velocity (Ar) 1L/min, atomization gas flow velocity 0.76L/min, test solution lifting capacity 0.98mL/min；Resolution 0.7amu, surveys
Amount point/peak is 25, and scanning times is 3, and residence time is 100ms, dual detector voltage (pulse 900V, simulation-1850V).
Avoid and clear up reagent and dissociate the vanadium in produced acid ion or molecule, metavanadate or vanadium acid anion and potassium sodium or ammonium
In root cation and ICP, ionized gas component argon, oxygen, hydrogen etc. are bound to each other to form multi-atomic ion or molecular ion institute
The mass spectrum interference caused, improves precision and the accuracy of testing result.
And, diluting to volume in 50～100mL with water after 0.10～0.20g Specimen eliminating described in invention, this is in specific proportions
The direct dilution of the first step that relation is carried out；Then molten with the rhodium of 1～5ng/mL (Rh) standard again when ICP-MS measures
Liquid mixes according to the proportionate relationship of (1+1), and this is the indirect dilution of the second step that relation is carried out in specific proportions；By two
The diluting effect of step, effectively reduces metavanadate matrix effect to trace, the impact of trace impurity sclera remodeling；Meanwhile,
This is just through the preferably the most less nitric acid of its consumption, and after dilute twice effect, its actual concentrations is less than 3%, reduces further
Its blank background and the acidity effect impact on measuring.
The technical characterstic of the present invention is: 1. with specific composition, concentration, proportioning, the strong oxidizing property reagent of consumption, control spy
Rapid-digestion reaction is carried out, it is ensured that the equal fast reactions of coexistence elements such as the sample matrices of metavanadate and hydrargyrum are molten under the conditions of fixed temperature
Solve and enter solution, cleared up the conditions such as reagent, reaction medium, temperature-time by Optimum Regulation, it is to avoid the hydrargyrum unit of volatile characteristic
Element volatilization from solution escapes thus causes measurement result on the low side, the problem of erroneous judgement product quality；2. tested sample preferred and prepared
The Parameter Conditions such as sample quality crucial in method, dilution ratio, reduce for the requirement of contradiction each other when trace element measures and try
Liquid is sought between matrix and salt density and increase concentration of element to be measured optimum balance, and it is logical to combine online Internal standard correction methods mode
Cross the correction of internal standard element and inner mark solution treats the diluting effect of test fluid, eliminate metavanadate matrix and Coexisting component is produced
The impact on measuring such as raw matrix effect, background background interference etc.；3. by sample dilution ratio, the excellent of reagent and consumption thereof is cleared up
Choosing, not only reduce the salinity of test solution, acidity on measure impact, avoid simultaneously clear up reagent dissociate produced acid group from
Ionized gas group in vanadium in son or molecule, metavanadate or vanadium acid anion and potassium sodium or ammonium root cation and ICP
The mass spectrum interference that point argon, oxygen, hydrogen etc. are bound to each other to form multi-atomic ion or molecular ion is caused.
Present invention research establishes ICP-MS and measures in metavanadate 0.0001～0.1000% trace impurity of content range
Hydrargyrum, performance indications reach detection by quantitative lower limit 0.0001%, precision < 10%, the response rate 80～120%.The inventive method has
Have simple and quick, analysis time is short, reagent dosage few blank low, influence factor is few, Monitoring lower-cut is low, precision and standard
Exactness high.
Detailed description of the invention
The present invention measures the sample solution preparation method of mercury element content in metavanadate, and its step is followed successively by:
A, metavanadate sample is dissolved in water；
B, add nitric acid and hydrogen peroxide, be heated to 60～65 DEG C, carry out clearing up and make sample and coexistent impurity clear up completely；
C, clear up after, be cooled to room temperature, with water dilute constant volume, i.e. obtain sample solution.
Metavanadate is first dissolved under greenhouse experiment by the present invention with suitable quantity of water, is subsequently adding concentrated nitric acid and dense hydrogen peroxide post-heating
React within the temperature range of 60～65 DEG C.Water, nitric acid are 1.5～2.5:1:0.8～1.2 with the volume ratio of hydrogen peroxide, excellent
Electing water, nitric acid as is 2:1:1 with the volume ratio of hydrogen peroxide.Nitric acid used in the present invention and hydrogen peroxide are preferably without dilute
The denseest reagent of the market sale released, it is preferred that described nitric acid mass percent concentration is 65%～68%, the quality of hydrogen peroxide
Percent concentration >=30%.
Reagent dosage is according to sample quality: nitric acid volume is the ratio addition of 0.1～0.2g:3～6mL.
Further, b step digestion time is 2～3min.
Metavanadate can be placed in the small mouth containers such as conical flask by the present invention, adds water rinsing bottle wall, dispersed sample in container,
And under room temperature environment, accelerate sample dissolution by shake or oscillation action.
The present invention can use to be placed on low temp. electric hot plate and directly heat or connect in the middle of hot water bath the modes such as heating to heat metavanadate molten
Liquid is to 60～65 DEG C, and keeps 2～3min in this temperature range.
Further, described metavanadate is the metavanadate using alkali metal, alkaline-earth metal or ammonium radical ion as cation, excellent
Elect ammonium metavanadate, sodium metavanadate or potassium metavanadate as.In described metavanadate, mercury content is 0.0001～0.1000%.
0.10～0.20g metavanadate sample dilutes to volume in 50～100mL volumetric flasks with water.
Concrete, the present invention can use following steps: generally, weighs sample 0.10～0.20g in the small mouth containers such as conical flask,
Add 6～12mL water rinsing bottle walls, dispersed sample and accelerate sample dissolution by shake or oscillation action under room temperature environment；
Then adding 3～6mL nitric acid and 3～6mL hydrogen peroxide in metavanadate solution, employing is placed on low temp. electric hot plate and directly adds
Connect the modes such as heating in the middle of heat or hot water bath and heat metavanadate solution to 60～65 DEG C, and keep in this temperature range
2～3min.After clearing up test solution and being cooled to room temperature, dilute to volume in 50～100mL volumetric flasks with water and mix.
The present invention measures the sample solution preparation method of mercury element content in metavanadate, utilizes ammonium metavanadate, sodium metavanadate, partially
The matrix using alkali metal, alkaline-earth metal or ammonium radical ion etc. as the metavanadic acid salt sample of cationic components such as potassium vanadate forms easily
It is dissolved in the characteristic of water, the most at ambient temperature with the water dissolvable impurity etc. in water direct sample dissolution matrix and sample, from
And shorten its time in heating period reaction, reduce the heated evaporation ease of effumability mercury element in sample solution preparation process
The risk gone out；Then according to the volume ratio of water, concentrated nitric acid and hydrogen peroxide is 2:1:1, and every 0.1 gram of sample needs 3mL
Nitric acid and the relation of hydrogen peroxide, add there is Specimen eliminating reagent and the dense nitre of mercury oxidation media protection agent dual function simultaneously
Acid and hydrogen peroxide, and metavanadate solution is heated to 60～65 DEG C and in this temperature range, keeps 2～3min.This skill
Art step effective guarantee is the temperature conditions of 60～65 DEG C and promotes the water-insoluble impurity in sample all by soon under nitric acid effect
Speed is cleared up completely, controls in this reaction temperature and time range also for avoiding the heated evaporation of effumability mercury element simultaneously
Effusion affects testing result accuracy；Especially, the nitric acid of strong oxidizing property, hydrogen peroxide agent itself, and nitric acid and peroxidating
Active oxygen that hydrogen reaction generates all it is effectively guaranteed that sample solution is in strong oxidizing property medium, further ensures that and clears up entrance sample
Among mercury element in product solution is maintained ionic forms thus is stable at and is kept in solution with, it is to avoid mercury ion is reduced to easily
The hydrargyrum of volatile atomic state thus form mercury vapour effusion of volatilizing from solution and affect testing result accuracy.
The present invention measures the method for mercury element content in metavanadate, uses inductively coupled plasma mass spectrometry (ICP-MS) to make
For detection means, and by the connecting mode of online internal standard blender, via ICP-MS instrument peristaltic pump by sample solution,
Series of calibration curve mercury standard solution respectively with rhodium element (Rh) standard solution that concentration is 1～5ng/mL according to the ratio of (1+1)
The mixing of example relation, dilution, be then introduced into ICP-MS instrument and take the mode of Internal standard correction methods to be measured, and draws calibration curve, and
The mercury content in sample solution is calculated by calibration curve；Wherein, described sample solution is prepared by preparation method of the present invention
The sample solution obtained, described series of calibration curve mercury standard solution is respectively 0 by concentration, 1,2,5,10,20,50,100ng/mL,
And the pure mercury solution composition that nitric acid, content of hydrogen peroxide are consistent with sample solution.
The present invention has selected inductively coupled plasma mass spectrometry (ICP-MS) as instrument detection means with using rhodium Rh as interior
The internal standard method of mark element correction measures trace in sample solution, the content of Trace Hg element.Especially, online internal standard is used to mix
The connecting mode of clutch, will clear up the sample solution of preparation, series of calibration curve via the peristaltic pump in ICP-MS sampling system
Mercury element (Hg) standard solution respectively with rhodium element (Rh) standard solution that concentration is 1～5ng/mL according to the ratio of (1+1)
Relation mixing, dilution, be then introduced into ICP-MS instrument and take the mode of Internal standard correction methods to measure the content of mercury element in various solution.
The instrument detection parameter of ICP-MS specifically includes that analysis isotope is201.971Hg (29.86%),199.968Hg (23.10%),198.968Hg (16.87%)；Radio-frequency emission power 1000W, cools down gas velocity (Ar) 15L/min, secondary air speed (Ar) 1L/min,
Atomization gas flow velocity 0.76L/min, test solution lifting capacity 0.98mL/min；Resolution 0.7amu, measuring point/peak is 25, scanning time
Number is 3, and residence time is 100ms, dual detector voltage (pulse 900V, simulation-1850V).Avoid and clear up reagent solution
Vanadium in produced acid ion or molecule, metavanadate or vanadium acid anion and potassium sodium or ammonium root cation and ICP
The mass spectrum interference that middle ionized gas component argon, oxygen, hydrogen etc. are bound to each other to form multi-atomic ion or molecular ion is caused, carries
The precision of high testing result and accuracy.
And, diluting to volume in 50～100mL with water after 0.10～0.20g Specimen eliminating described in invention, this is in specific proportions
The direct dilution of the first step that relation is carried out；Then molten with the rhodium of 1～5ng/mL (Rh) standard again when ICP-MS measures
Liquid mixes according to the proportionate relationship of (1+1), and this is the indirect dilution of the second step that relation is carried out in specific proportions；By two
The diluting effect of step, effectively reduces metavanadate matrix effect to trace, the impact of trace impurity sclera remodeling；Meanwhile,
This is just through the preferably the most less nitric acid of its consumption, and after dilute twice effect, its actual concentrations is less than 3%, reduces further
Its blank background and the acidity effect impact on measuring.
Below in conjunction with embodiment, the detailed description of the invention of the present invention is further described, the most therefore limits the present invention to institute
Among the scope of embodiments stated.In the following embodiments, the mass percent concentration employing the pure rank of top grade is 65%～68%
Concentrated nitric acid, the hydrogen peroxide of mass percent concentration >=30%, water is the distilled water meeting two grades of water requirements of laboratory, equipment
For: U.S. PE company Elan9000 type icp ms (ICP-MS).
Embodiment 1
Clearing up of ammonium metavanadate sample
Weigh sample 0.2000g ammonium metavanadate sample (hereinafter referred to as No. 1 sample) in conical flask, add 12mL water rinsing bottle
Wall, dispersed sample and under room temperature environment by shake or oscillation action accelerate sample dissolution；Add 6mL the most in the solution
Nitric acid and 6mL hydrogen peroxide, use to be placed on low temp. electric hot plate to directly heat or connect the modes such as heating in the middle of hot water bath and heat partially
Vanadate solution is to 65 DEG C, and keeps 3min at such a temperature.After clearing up test solution and being cooled to room temperature, dilute to volume in water
100mL volumetric flask mixes.
Content with ICP-MS detection ammonium metavanadate sample solution mercury element
Use inductively coupled plasma mass spectrometry (ICP-MS) as detection means, and by online internal standard blender
Connecting mode, will clear up the sample solution of preparation, series of calibration curve mercury element (Hg) standard via the peristaltic pump of ICP-MS
Solution mixes according to the proportionate relationship of (1+1), dilutes with rhodium element (Rh) standard solution that concentration is 5ng/mL, then respectively
Importing ICP-MS instrument takes the mode of Internal standard correction methods to measure the content of Hg solution element.
Wherein, series of calibration curve mercury standard solution is respectively 0 by concentration, 1,2,5,10,20,50,100ng/mL, and
And the pure mercury standard solution composition that nitric acid, content of hydrogen peroxide are consistent with sample solution.
Remaining ICP-MS determination step is carried out in the usual way, and the running parameter arranging icp ms is:
Radio-frequency emission power 1000W, cools down gas velocity (Ar) 15L/min, secondary air speed (Ar) 1L/min, atomization air flow
Speed 0.76L/min, test solution lifting capacity 0.98mL/min；Resolution 0.7amu, measuring point/peak is 25, and scanning times is 3,
Residence time is 100ms, dual detector voltage (pulse 900V, simulation-1850V).Analyzing isotope can be201.971Hg (29.86%),199.968Hg (23.10%),198.968Select among Hg (16.87%) or optional one simultaneously.
Embodiment 2
Sample to be cleared up is 0.1000g potassium metavanadate sample (hereinafter referred to as No. 2 sample), and the consumption of water is 6mL, dense nitre
Acid consumption is 3mL, and hydrogen peroxide use is 3mL, and the temperature and time of solution reacting by heating is respectively 60 DEG C and 2min,
Rear dilution constant volume is 50mL, and the concentration of the rhodium Rh Internal standard correction methods standard solution used is 1ng/mL.
In addition, clear up this potassium metavanadate sample by the method identical with the method for embodiment 1 and detect solution with ICP-MS.
Embodiment 3
Sample to be cleared up is 0.1500g sodium metavanadate sample (hereinafter referred to as No. 3 sample), and the consumption of water is 9mL, dense nitre
Acid consumption is 4.5mL, and hydrogen peroxide use is 4.5mL, and the temperature and time of solution reacting by heating is respectively 63 DEG C and 2.5min,
Finally dilution constant volume is 100mL, and the concentration of the rhodium Rh Internal standard correction methods standard solution used is 3ng/mL.
In addition, clear up this sodium metavanadate sample according to the method identical with the method for embodiment 1 and detect molten with ICP-MS
Liquid.
Embodiment 4
Sample to be cleared up is 0.1000g metavanadic acid calcium sample (hereinafter referred to as No. 4 sample), and the consumption of water is 12mL, dense nitre
Acid consumption is 6mL, and hydrogen peroxide use is 6mL, and the temperature and time of solution reacting by heating is respectively 65 DEG C and 3min,
Rear dilution constant volume is 100mL, and the concentration of the rhodium Rh Internal standard correction methods standard solution used is 4ng/mL.
In addition, clear up this metavanadic acid calcium sample according to the method identical with the method for embodiment 1 and detect molten with ICP-MS
Liquid.
Embodiment 5
Sample to be cleared up is 0.1500g potassium metavanadate sample (hereinafter referred to as No. 5 sample), and the consumption of water is 6mL, dense nitre
Acid consumption is 3mL, and hydrogen peroxide use is 3mL, and the temperature and time of solution reacting by heating is respectively 62 DEG C and 2min,
Rear dilution constant volume is 50mL, and the concentration of the rhodium Rh Internal standard correction methods standard solution used is 2ng/mL.
In addition, clear up this potassium metavanadate sample according to the method identical with the method for embodiment 1 and detect molten with ICP-MS
Liquid.
Embodiment 6 response rate is assessed
The present invention has carried out recovery test to No. 2 samples and No. 4 samples.First pass through embodiment 2 and embodiment 4 is surveyed respectively
Obtained the content of contained mercury element in No. 2 samples and No. 4 samples；Then adding respectively in No. 2 samples and No. 4 samples respectively
Entering the mercury standard solution of 0.0005% and 0.0001%, whole process repeats sample preparation and the inspection of embodiment 2 and embodiment 4 respectively
Survey operation.By the assessment of the response rate in order to verify sample solution preparation method and the detection method of the present invention, volatile to solving
Property element mercury sample preparation steps volatilization loss and eliminate ICP-MS detection mercury element in matrix effect, acidity effect, matter
The effectiveness of all kinds of influence factors such as spectrum interference.Result of the test is shown in Table 1.
Table 1 recovery test
Table 1 is visible, and in method mensuration metavanadate, contents level is 10-6Trace element hydrargyrum, the response rate 80%～120%,
Show that analysis result has higher accuracy and reliability.
Embodiment 7 precision is assessed
The present invention clears up preparation to embodiment 1 and embodiment 3 carry out 8 independent sample solutions respectively and analyzes mensuration, right
The result that 8 times are measured carries out statistical disposition, and the detection precision level represented according to relative standard deviation (RSD), in order to comment
Estimate the concordance of the duplicate test of the present invention.Measurement result is shown in Table 2.
Method precision (n=8) (%) analyzed by table 2
Table 2 is visible, measures in metavanadate 10-5Trace level (10 in the present invention-6On Monitoring lower-cut, meet the present invention
Detection range) precision RSD of mercury element content less than 10%, even if measuring in metavanadate 10-7Trace level is (at this
The 10 of invention setting-6Under Monitoring lower-cut, beyond the optimum determining scope of the present invention) precision RSD of mercury element content the least
In 30%, showing that repeatedly measurement result is consistent, the repeatability of method, repeatability are good, and method has higher precision level.
Claims (10)
1. measure the preparation method of the sample solution of mercury element content in metavanadate, it is characterised in that its step is followed successively by:
A, metavanadate sample is dissolved in water；
B, addition nitric acid and hydrogen peroxide, be heated to 60～65 DEG C, clear up；
C, clear up after, be cooled to room temperature, with water dilute constant volume, i.e. obtain sample solution.
The preparation method of the sample solution of mercury element content in mensuration metavanadate the most according to claim 1, its feature exists
In: water, nitric acid are 1.5～2.5:1:0.8～1.2 with the volume ratio of hydrogen peroxide, preferably water, nitric acid and hydrogen peroxide
Volume ratio is 2:1:1.
The preparation method of the sample solution of mercury element content in mensuration metavanadate the most according to claim 1 and 2, it is special
Levy and be: described nitric acid mass percent concentration is 65%～68%, mass percent concentration >=30% of hydrogen peroxide.
4. according to the preparation method of the sample solution of mercury element content in the mensuration metavanadate described in any one of claims 1 to 3,
It is characterized in that: sample quality: nitric acid volume is 0.1～0.2g:3～6mL.
The preparation method of the sample solution of mercury element content in mensuration metavanadate the most according to claim 1, its feature exists
In: b step digestion time is 2～3min.
The preparation method of the sample solution of mercury element content in mensuration metavanadate the most according to claim 1, its feature exists
In: 0.10～0.20g metavanadate sample dilutes to volume in 50～100mL volumetric flasks with water.
7. according to the preparation method of the sample solution of mercury element content in the mensuration metavanadate described in any one of claim 1～6,
It is characterized in that: described metavanadate is the metavanadate using alkali metal, alkaline-earth metal or ammonium radical ion as cation, preferably
For ammonium metavanadate, sodium metavanadate or potassium metavanadate.
8. according to the preparation method of the sample solution of mercury element content in the mensuration metavanadate described in any one of claim 1～7,
It is characterized in that: in described metavanadate, mercury content is 0.0001～0.1000%.
9. measure the method for mercury element content in metavanadate, it is characterised in that: ICP-MS is as detection means in employing, and
By the connecting mode of online internal standard blender, via the peristaltic pump of ICP-MS instrument by sample solution, series of calibration curve hydrargyrum
Standard solution mixes according to volume ratio 1:1 with the rhodium element standard solution that concentration is 1～5ng/mL respectively, is then introduced into ICP-MS
Instrument takes the mode of Internal standard correction methods to be measured, and draws calibration curve, and the hydrargyrum calculated in sample solution by calibration curve contains
Amount；Wherein, described sample solution is the sample solution that the preparation method described in any one of claim 1～8 prepares, described
Series of calibration curve mercury standard solution is respectively 0 by concentration, 1,2,5,10,20,50,100ng/mL, and nitric acid, mistake
The mercury solution composition that hydrogen oxide content is consistent with sample solution.
The method of mercury element content in mensuration metavanadate the most according to claim 9, it is characterised in that: ICP-MS
Instrument detection parameter specifically includes that radio-frequency emission power 1000W, cools down gas velocity 15L/min, secondary air speed 1L/min,
Atomization gas flow velocity 0.76L/min, test solution lifting capacity 0.98mL/min；Resolution 0.7amu, measuring peak is 25, scanning times
Being 3, residence time is 100ms, uses dual detector voltage, pulse 900V, simulation-1850V；Analysis isotope is:201.971Hg、199.968Hg or198.968Hg。
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| CN109100209A (en) * | 2018-10-29 | 2018-12-28 | 中国热带农业科学院分析测试中心 | The pre-treating method of mercury element measurement in a kind of plant-derived sample |
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