CN106442342B - A kind of method of sulfur trioxide and sulfuric acid concentration in measurement workplace air - Google Patents
A kind of method of sulfur trioxide and sulfuric acid concentration in measurement workplace air Download PDFInfo
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- CN106442342B CN106442342B CN201610511253.4A CN201610511253A CN106442342B CN 106442342 B CN106442342 B CN 106442342B CN 201610511253 A CN201610511253 A CN 201610511253A CN 106442342 B CN106442342 B CN 106442342B
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Abstract
The method of sulfur trioxide and sulfuric acid concentration in a kind of measurement workplace air of the present invention, include the steps that a preparation mix reagent, mix reagent is made of dehydrated alcohol, barium chloride solution and polyethylene glycol, dehydrated alcohol, barium chloride solution, polyethylene glycol volume ratio be 1:2:0.2~0.7；The step of one preparation hydrochloric acid solution；Sample solution, mix reagent and hydrochloric acid solution mixing, measure sample absorbance；It is compared by the absorption values and standard curve of acquisition, obtains sulfur trioxide and sulfuric acid concentration in workplace air.By the present invention in that using polyethylene glycol as concentration of hydrochloric acid used in stabilizer, the proportion for changing barium chloride mix reagent, optimization and measuring the mixed reaction time of preceding reagent, make during measuring sulfur trioxide and sulfuric acid, the standard curve of preparation is linearly more preferable, the solution absorbance stable time is long, and properties are able to satisfy the requirement of sulfur trioxide and sulfuric acid in measurement air.
Description
Technical field
The invention belongs to chemical fields, are related to a kind of detection method of occupational, specifically a kind of survey
Determine the method for sulfur trioxide and sulfuric acid concentration in workplace air.
Background technique
With the rapid development of our country's economy, the number of the enterprise for being related to occupational rapidly increases, and leads to occupation
Sick prevention and treatment form very severe.2011, the 24th meeting of the 11st Standing Committee of the National People's Congress passed through " about modification
The resolution of < People's Republic of China (PRC) law on prevention and cure of occupational disease > ", it further highlights Speed-up Establishment and perfects Occupational Health Technique Service
System.The key of prevention and cure of occupational disease is to prevent, and the source of prevention is working site, thus workplace occupational disease hazards because
Plain testing result it is accurate whether directly determine the success or failure of prevention and control of occupational disease.
According to " People's Republic of China's Occupational sanitary standard workplace air noxious material measures sulfide "
The barium chloride turbidimetry of GBZ/T160.33-2004 sulfur trioxide and sulfuric acid, sulfur trioxide and sulfuric acid in workplace air can
It is acquired using miillpore filter, after being eluted with water, is reacted with barium chloride and generate barium sulfate；Absorbance is measured under 420nm wavelength, into
Row measurement.Use ethylene glycol or glycerine as the stabilizer of the barium sulfate generated in standard, with ethyl alcohol, acid chlorization barium solution
Mixed, obtain mix reagent, then again with impregnate sampling membrane aqueous solution hybrid reaction, by under 420nm wavelength
The measurement of absorbance, is measured sample.
But this method is found in use, and the barium sulfate that ethylene glycol and glycerine can not be stably generated effectively is heavy
It forms sediment.According to the standard curve that this method configures, absorbance and concentration are extremely difficult to good linear relationship, and related coefficient is through quasi-
Close the requirement (" People's Republic of China's Occupational sanitary standard Part IV: workplace air for being difficult to reach r >=0.999
Middle chemical substance measuring method " GBZ/T210.4-2008), and its absorbance changes over time greatly, is difficult to control optimum determining
Time is not inconsistent so as to cause testing result and field investigation result, can not really reflect workplace air quality.
Summary of the invention
For the above-mentioned technical problem in existing method, the present invention provides three oxidations in a kind of measurement workplace air
The method of sulphur and sulfuric acid concentration, the method for sulfur trioxide and sulfuric acid concentration solves existing in this measurement workplace air
Having method, prepared standard curve linear relationship is poor in use, it is difficult to reach the requirement of r >=0.999；Sample absorbance is at any time
The technical issues of variation is big, is difficult to control the optimum determining time.
The present invention provides a kind of methods of sulfur trioxide and sulfuric acid concentration in measurement workplace air, including walk as follows
It is rapid:
1) the step of preparation mix reagent, the mix reagent is by dehydrated alcohol, barium chloride solution and poly- second two
Alcohol composition, the mass percent concentration of the barium chloride solution are 10%, and the molecular weight of the polyethylene glycol is 400~800
Between, the dehydrated alcohol, barium chloride solution, polyethylene glycol volume ratio be 1:2:0.2~0.7；
2) the step of preparation hydrochloric acid solution, the concentration of the hydrochloric acid solution are 0.3~0.48mol/L；
3) sample solution, mix reagent and hydrochloric acid solution are 1:0.4:0.1 mixing according to volume ratio, after reacting 30min, in
Absorbance is measured at 420nm wavelength；
4) using the standard serial solution of above method measurement sulfate ion, standard curve is drawn；
5) absorption values and standard curve obtained by step 3) are compared, and obtain three oxygen in workplace air
Change sulphur and sulfuric acid concentration.
Further, minute is in 30min~50min time interval after reagent hybrid reaction.
Polyethylene glycol used in the present invention is the polymer of ethylene glycol, has long-chain ethers compound, with second two
The alcohol compounds such as pure and mild glycerine have significant difference on molecular structure.
The mode of action of polyethylene glycol and barium sulfate particles may are as follows: oxygen and microparticle surfaces hydroxyl in polyglycol ether chain
Hydrogen bond is formed, to play the role of stable barium sulfate particles.
By the present invention in that polyethylene glycol is used to be used as stabilizer, the proportion of change barium chloride mix reagent, optimization
Concentration of hydrochloric acid and before measuring reagent mixed reaction time, make in sulfur trioxide and sulfuric acid process, to prepare in measurement air
Standard curve it is linearly more preferable, solution absorbance stablize the time it is long, properties be able to satisfy measurement air in sulfur trioxide and
The requirement of sulfuric acid.
The standard curve prepared using new method is linearly more preferable, and strong operability, at low cost, method is stable, repeated
It is good, in detection limit, concentration limit, measurement range and relative standard deviation, etc. various aspects of performance be all satisfied relevant criterion and want
It asks.
The method of the present invention is simple, strong operability, at low cost.Sulfur trioxide and sulfuric acid in air are carried out in this way
Measurement, method detection limit, concentration limit, measurement range, relative standard deviation all requirements are able to satisfy GBZ/T
The requirement of " 160.33-2004 workplace air noxious material measures sulfide ".
The present invention is compared with existing detection method, and technological progress is significant.The present invention targetedly solves existing
There is method poor to sulfur trioxide in air and sulfuric acid continuous mode standard curve linear relationship, sample absorbance changes over time
Greatly, the technical issues of being difficult to control the optimum determining time.By improve, the present invention make prepared standard curve related coefficient,
Method detection limit, concentration limit, measurement range, relative standard deviation and the method rate of recovery are able to satisfy: GBZ/T
160.33-2004 " workplace air noxious material measures sulfide ", GBZ/T210.4-2008 " state, the People's Republic of China (PRC)
Family occupational health standard Part IV: chemical substance measuring method in workplace air ", GBZ/T210.4-2008 " middle Chinese
Chemical substance measuring method in people republic Occupational sanitary standard workplace air " and GB/T27404-2008 " experiment
Room quality control specifications food Physico-chemical tests " requirement.
Detailed description of the invention
Fig. 1 is the Linear Fit Chart that standard curve is prepared using improved method.
Fig. 2 is that the sample to be tested absorbance measured according to improved method changes over time figure.
Fig. 3 is that the sample to be tested absorbance measured according to GBZ/T 160.33-2004 method changes over time figure.
Specific embodiment
Below in conjunction with attached drawing, the present invention is described in further detail.
The barium chloride ratio of 1 present invention of embodiment a kind of sulfur trioxide suitable for workplace air and sulfuric acid concentration measurement
The experimental implementation process of turbid improved method.
The preparation of reagent:
1) barium chloride solution (10%): 10g barium chloride (BaCl is weighed2), it is soluble in water, add water to 100mL.
2) mix reagent: dehydrated alcohol: barium chloride solution: volume ratio=1:2:0.7 of polyethylene glycol (PEG600).
3) hydrochloric acid solution: the concentration of hydrochloric acid solution is 0.3mol/L；
4) standard solution: 0.1776g potassium sulfate (in 105 DEG C of dry 2h) are accurately weighed, are dissolved in water, and be quantitatively transferred to
In 100mL volumetric flask, it is diluted with water to scale.This liquid is 1.0mg/mL standard reserving solution.Before use, it is diluted with water to
50.0ug/ml sulfuric acid standard solution.
Analytical procedure:
1) 10.0mL water, shaking sample treatment: are added in equipped with the color-comparison tube for adopting sample filter membrane；5min is placed,
It shakes up.Take 5.0mL sample solution in another color-comparison tube, for measurement.If the concentration of determinand is more than to survey in sample solution
Determine range, measured after dilutable water, multiplied by extension rate when calculating.
2) preparation of standard curve: according to the form below prepares standard series
The preparation of 1 standard series of table
3) measurement of standard curve: 0.5mL (0.3mol/L) hydrochloric acid solution is added to each standard pipe, shakes up, 2mL is added to mix
Reagent after gently shaking up, places 30~50min.Absorbance is measured at 420nm wavelength,
It is bent to draw standard to corresponding sulfate ion content (μ g) with absorbance mean value for each concentration replication 3 times
Line.
4) sample measures: with the operating condition measurement sample solution and placebo solution of measurement standard series.It measures
Sample absorbance value is obtained the content (μ g) of sulfate ion by standard curve.
Reagent and instrument:
Table 2 tests involved reagent and instrument
Embodiment 2
Using the present invention, " sulfur trioxide and the barium chloride of sulfuric acid concentration measurement are than turbid improvement suitable for workplace air
Method " carries out the performance test of method, main to investigate: the linear of standard curve, method detection limit, precision, accuracy, and with
Concentration limit, measurement range, the relative standard deviation of method are determined based on this.By following experiments to each investigation content
It is illustrated respectively.
Since the technical parameter that only GB/T27404-2008 confirms method in current national standard is provided,
The method confirmation data being related in this experiment are with the national standard for reference.
(1) standard curve is linear
According to the standard curve preparation of " embodiment 1 " and measuring method, standard curve as shown in Figure 1 is obtained.The curve
Related coefficient square r2=0.9996, then r=0.9998, fully meets the requirement of r >=0.9990.Through repeatedly preparing standard curve
And it measures, slope of standard curve range are as follows: 0.0011~0.0014.
(2) method detection limit MDL
N=10 parallel determination is carried out to the sample that concentration is 2-5 times of estimation method detection limit, calculates 10 parallel determinations
Standard deviation S.Calculation method detection limit MDL=t according to the following formula(n-1,0.99)* S, (freedom degree n-1, confidence level 99%.
It is measured in parallel 10 low concentration solutions, measurement result average value are as follows: 6.67 μ g, standard deviation S=1.29
MDL=t(n-1,0.99)* S=t(10-1,0.99)* 3.64 μ g of the ≈ of S=2.821 × 1.29
Since the sampling amount of sample is 5mL, 0.73 μ g/mL of sample concentration MDL=3.64/5.0 ≈, Determination Limit are converted to
For 4 × MDL=2.91 μ g/mL
(3) method lower limit of measurement
It is required according to GB/T27404-2008, the calculation formula of method lower limit of measurement are as follows:
CL=3Sb/b
C in formulaL: method lower limit of measurement；Sb: blank value standard deviation (general parallel determination 20 times are derived above)；B: method
Slope of Calibration Curve.
It is measured through test, blank value is through 25 measurement standard deviation SbAre as follows: 0.0011, method Slope of Calibration Curve b are as follows:
0.0013, sampling amount 5mL
Method lower limit of measurement C after calculatingLAre as follows: 0.51 μ g/mL
(4) the method rate of recovery
The rate of recovery in method lower limit of measurement, common limit index, select an appropriate point to carry out three hydraulic tests, each level does
7 parallel testings, test result are as shown in table 3.Its rate of recovery range meets the requirement in GB/T27404-2008 to the rate of recovery.
3 method rate of recovery data of table
(5) method precision
Method precision method lower limit of measurement, common limit index, select an appropriate point carry out three hydraulic tests, Mei Yishui
It is flat to do 9 parallel testings.Precision test result can be expressed by coefficient of variation CV in laboratory (CV=standard deviation/
Average value), 4 are shown in Table, result meets the requirement in GB/T27404-2008 to method precision.
4 method precision data of table
(6) method accuracy
Using water quality sulfate standard sample (GSB07-1196-2000, lot number 201925), this method accuracy is carried out
Verifying.In water quality sulfate standard sampleContent be 20.1mg/L, take 10mL to be diluted to 50mL.Then after taking dilution
Sample is measured, and the results are shown in Table 5.Its measurement deviation range is wanted less than GB/T27404-2008 large deviations range L T.LT.LT's 15%
It asks.
5 method accuracy data of table
(7) sample absorbance changes over time trend
A sample to be tested is chosen, its absorbance is measured and changes over time curve, from figure 2 it can be seen that according to improvement side
The testing sample solution that method is prepared, absorbance is in parabolic variation at any time, and absorbance reaches maximum between 30~50min
And it is relatively stable, it is suitble to carry out sample measurement in this time frame.
The testing sample solution prepared as a comparison according to GBZ/T 160.33-2004 method, absorbance become at any time
Change without evident regularity, it is difficult to find metastable period progress sample detection (Fig. 3) of absorbance.
(8) detection limit of new method, concentration limit, measurement range, relative standard deviation
Since method detection limit MDL is 0.73ug/mL, and filter membrane leachate is 10mL, therefore contains sulfate radical on filter membrane
Ion 7.3ug.It is folded to the 75L air sample of acquisition, then the content of sulfate ion is 0.10mg/m in air3.Measure model
It encloses and is determined by the concentration range of standard curve covering, due to having used 5mL filter membrane leachate, measurement range 1 in measurement
~20ug/mL.Relative standard deviation range is calculated to obtain by method precision data.
The detection limit of 6 new method of table, concentration limit, measurement range, relative standard deviation data
Claims (2)
1. a kind of method of sulfur trioxide and sulfuric acid concentration in measurement workplace air, it is characterised in that include the following steps:
1) the step of preparation mix reagent, the mix reagent is by dehydrated alcohol, barium chloride solution and polyethylene glycol group
Mass percent concentration at, the barium chloride solution is 10%, the molecular weight of the polyethylene glycol between 400~800,
The dehydrated alcohol, barium chloride solution, polyethylene glycol volume ratio be 1:2:0.2~0.7；
2) the step of preparation hydrochloric acid solution, the concentration of the hydrochloric acid solution are 0.3~0.48mol/L；
3) sample solution, mix reagent and hydrochloric acid solution are 1:0.4:0.1 mixing according to volume ratio, after reacting 30min, in
Absorbance is measured at 420nm wavelength；
4) using the standard serial solution of above method measurement sulfate ion, standard curve is drawn；
5) absorption values and standard curve obtained by step 3) are compared, and obtain sulfur trioxide in workplace air
And sulfuric acid concentration.
2. the method for sulfur trioxide and sulfuric acid concentration, special in a kind of measurement workplace air according to claim 1
Sign is: minute is in 30min~50min time interval after reagent hybrid reaction.
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| CN112924400A (en) * | 2019-12-05 | 2021-06-08 | 中粮生物科技股份有限公司 | Method for detecting sulfate content in citric acid sample |
| CN113008818B (en) * | 2021-02-25 | 2022-12-20 | 河北冀衡集团有限公司蓝天分公司 | Method for measuring acid mist content in sulfuric acid production tail gas |
| CN113702306A (en) * | 2021-08-24 | 2021-11-26 | 青海盐湖镁业有限公司 | Method for measuring sulfur dioxide in exhaust gas discharged by methanol plant |
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