CN108519375A - A method of measuring Sulfide in water with continuous flow method - Google Patents
A method of measuring Sulfide in water with continuous flow method Download PDFInfo
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- CN108519375A CN108519375A CN201810212332.4A CN201810212332A CN108519375A CN 108519375 A CN108519375 A CN 108519375A CN 201810212332 A CN201810212332 A CN 201810212332A CN 108519375 A CN108519375 A CN 108519375A
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- G—PHYSICS
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- 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
- G01N21/75—Systems in which material is subjected to a chemical reaction, the progress or the result of the reaction being investigated
- G01N21/77—Systems in which material is subjected to a chemical reaction, the progress or the result of the reaction being investigated by observing the effect on a chemical indicator
- G01N21/78—Systems in which material is subjected to a chemical reaction, the progress or the result of the reaction being investigated by observing the effect on a chemical indicator producing a change of colour
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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
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Abstract
The invention discloses a kind of methods measuring Sulfide in water with continuous flow method, charging water sample is injected into chemical reagent in Flow Analyzer using pump, in Flow Analyzer, distilling reagent is reacted and is distilled with the sulfide in charging water sample, hydrogen sulfide gas is generated to be absorbed by sodium hydroxide solution, absorbing liquid is reacted with color developing agent and iron chloride, and reactant is measured with colorimeter.The measurement of sulfide in water quality is carried out using the present invention, it is ensured that the accuracy and stability of test sample, detection limit are low；Step is simple, easy to operate, improves detection efficiency and has good reproducibility.
Description
Technical field
The present invention relates to field of chemical detection, especially a kind of method measuring Sulfide in water with continuous flow method.
Background technology
Sulfide is widely present in natural water body and industrial wastewater.Since sulfide is poisonous and harmful, the main table of toxicity
It is now that can release H2S, H2S is a kind of colourless, soluble easily in water and with rotten egg smell gas, has corrosivity, combustibility
And lethal, when low concentration, can cause uncomfortable, when high concentration, can lead to clouded in mind, transient cerebral damage even death by suffocation
It dies.Since the harm of sulfide is great, thus sulfide is an important indicator object of water pollution, how Accurate Determining environment
Sulfide in water quality has important practical significance, and can provide more true and reliable section for environmental protection and control
Learn foundation.
The method of the detection of sulfide is more in current art water quality, wherein the most commonly used is Manual chemicals in detecting work
Method.In this method, the measurement of sulfide needs distill early period, and operating procedure is cumbersome, is wanted to the quantity and ability of experimenter
Ask higher.
To ensure efficiently and accurately to carry out the detection of Sulfide in water, there is an urgent need to a kind of advanced detection methods with suitable
It answers ever-increasing detection limit and improves accuracy.
Invention content
The technical problem to be solved by the present invention is to：In view of the above problems, it provides and a kind of is surveyed with continuous flow method
The method for determining Sulfide in water reduces the influence of manual operation, improves detection sensitivity, improves detection efficiency.
The technical solution adopted by the present invention is as follows：
A method of Sulfide in water being measured with continuous flow method, is injected into charging water sample with chemical reagent using pump
In Flow Analyzer, in Flow Analyzer, distilling reagent is reacted and is distilled with the sulfide in charging water sample, generates hydrogen sulfide
Gas is absorbed by sodium hydroxide solution, and absorbing liquid is reacted with color developing agent and iron chloride, and reactant is measured with colorimeter.
The operation principle of continuous flow method is：Enter chemical reaction mould under the promotion of peristaltic pump using sample and reagent
Block continuously flows in closed pipeline, is regularly separated at regular intervals by bubble, and mixed with ratio in particular order
It closes, reaction, flowing detection cell is entered after developing the color completely and carries out photometric detection.Due to sample introduction by bubble at regular intervals rule every
It opens, recycles analysis time to be controlled, it is ensured that the sulfide in sample introduction is to react completely, to ensure that the standard of test sample
True property, it is reproducible.
In the present invention, sulfide refers to dissolubility inorganic sulphide and acid soluble metal sulfide in water, including dissolubility
H2S、HS-、S2-, and the dissolvable sulfide and acid-solubility metal sulfide that are present in suspended matter.It is tried using distillation
Hydrochloric acid in agent is reacted with inorganic sulphide with acid soluble metal sulfide generates hydrogen sulfide, and aobvious after being absorbed by sodium hydroxide
Toner and ferric chloride reaction generate the complex compound methylene blue of blue, then carry out colorimetric pool colorimetric, light absorption value and water sample
In H2S concentration is directly proportional.
Further, the measurement wavelength of the colorimeter is 660nm.
Further, the distilling reagent is hydrochloric acid solution, and preparation method is:It is close that 100ml is added in 500ml distilled water
Degree is the hydrochloric acid of 1.19g/ml, adds distilled water to be settled to 1000ml, distilling reagent is preferably when all Fresh use.
Further, the preparation method of the color developing agent is：It is 1.19g/ml that 10ml density is added in 800ml distilled water
Hydrochloric acid, 33.4mg N, N- dimethyl-Isosorbide-5-Nitrae-phenylenediamine dihydrochloride dissolving and mixing is then added, is settled to 1000ml, adds
Enter 1mlBrij35 mixings, color developing agent preferably same day Fresh uses, 4 DEG C of storages when not used.
Further, the preparation method of the ferric chloride solution is：10ml density is added in 800ml distilled water is
Then 1.33g chlorination dissolved ferric irons are added in the hydrochloric acid of 1.19g/ml, be settled to 1000ml, and iron chloride is preferably used when all Fresh,
It is stored without appropriate to the occasion 4 DEG C.
Further, the concentration of sodium hydroxide solution is 0.1mol/L, and preparation method is：Weigh 4.00g hydroxides
Sodium is dissolved in distilled water, is settled to 1000ml.
Further, the charging rate of the charging water sample is 1ml/min, and the charging rate of solvent distillation is 2ml/min,
The charging rate of sodium hydroxide is 1.2ml/min, and the charging rate of color developing agent is 0.23ml/min, and the charging rate of iron chloride is
0.42ml/min。
Further, vapo(u)rizing temperature is 75 DEG C -85 DEG C.
The scheme further includes the debugging and calibration of Continuous Flow Analysis instrument：Continuous Flow Analysis instrument is opened, water generation is first used
For reagent, checks the closure of entire analysis flow path and the smoothness of liquid flowing, start, into reagent, to wait for base after baseline stability
After line is stablized again, calibrated using liquid using standard cure object.
The preparation method of the sulfide standard solution is：The standard of sulfide is diluted with 0.01mol/L sodium hydroxides
In storing solution (ρ (S)=100) to 100ml volumetric flasks, when use the same day prepare.
Calibrate the preparation of solution：Suitable sulfide standard solution is pipetted in 100ml volumetric flasks, uses 0.01mol/L
Sodium hydroxide dilutes constant volume, prepares the standard series of 9 concentration points, and sulphur mass concentration is respectively：0.00mg/L、0.010mg/L、
0.050mg/L、0.100mg/L、0.300mg/L、0.500mg/L、1.00mg/L、1.50mg/L、2.00mg/L。
Specification Curve of Increasing：Take appropriate standard serial solution in specimen cup respectively, by setup program successively by injector
Sampling measures.To measure signal value (peak height) as ordinate, corresponding sulfide mass concentration (in terms of S, mg/L) is horizontal seat
Mark draws calibration curve.
In conclusion by adopting the above-described technical solution, the beneficial effects of the invention are as follows：Using continuous flow method suitable
It is measured under conditions of preferably, realizes the complete reaction of sulfide, it is ensured that the accuracy and stability of test sample, detection limit
It is low；Step is simple, easy to operate, improves detection efficiency and has good reproducibility.
Description of the drawings
Examples of the present invention will be described by way of reference to the accompanying drawings, wherein：
Fig. 1 is the piping diagram that Sulfide in water is measured using continuous flow method.
Specific implementation mode
With reference to embodiment, the present invention is described further.The embodiment be intended to illustrate invention content rather than
It limits the scope of the invention.
Embodiment 1 carries out Precision Analyze using standard environment sample to this method
Following steps are taken to be tested：
1. the debugging of instrument
Continuous Flow Analysis instrument is opened, first replaces reagent with water, checks closure and the liquid flowing of entire analysis flow path
Smoothness, start after baseline stability into reagent, after baseline is stablized again, school carried out using liquid using standard cure object
It is accurate.
2. calibration
1) preparation of solution is calibrated：The preparation for calibrating solution, pipettes suitable sulfide standard solution in 100ml capacity
In bottle, constant volume is diluted with 0.01mol/L sodium hydroxides, prepares the standard series of 9 concentration points, sulphur mass concentration is respectively：
0.00mg/L、0.010mg/L、0.050mg/L、0.100mg/L、0.300mg/L、0.500mg/L、1.00mg/L、1.50mg/L、
2.00mg/L。
2) drafting of calibration curve：Take appropriate standard serial solution in specimen cup respectively, by setup program by injector
It samples, measure successively.To measure signal value (peak height) as ordinate, corresponding sulfide mass concentration (in terms of S, mg/L) is cross
Coordinate draws calibration curve.
As shown in Figure 1, assay method is as follows：Charging water sample is injected into chemical reagent in Flow Analyzer using pump,
In Flow Analyzer, charging water sample is uniformly mixed with distilling reagent, air, is reacted into spiral response circle；Reaction product with
It being distilled under conditions of 80 DEG C after the nitrogen mixing being blown into, slops, which enters after cooling back installation is cooled to 15 DEG C, to be discharged,
Through 15 DEG C of coolings of cooling-cycle device after the sodium hydroxide absorption of 0.1mol/L of product of distillation hydrogen sulfide, into spiral response
Circle, with color developing agent and air hybrid reaction, reaction product is mixed into next spiral coil with ferric trichloride and reacts, and last gained is anti-
It answers product to carry out colorimetric pool colorimetric, its absorbance is tested at 660nm light paths.
Wherein, distilling reagent is hydrochloric acid solution, and preparation method is:100ml density is added in 500ml distilled water is
The hydrochloric acid of 1.19g/ml, adds distilled water to be settled to 1000ml；
The preparation method of color developing agent is：The hydrochloric acid that 10ml density is 1.19g/ml is added in 800ml distilled water, then adds
Enter 33.4mg N, the dissolving of N- dimethyl-Isosorbide-5-Nitrae-phenylenediamine dihydrochlorides and mixing, is settled to 1000ml, it is mixed that 1mlBrij35 is added
It is even.
The preparation method of liquor ferri trichloridi is：The hydrochloric acid that 10ml density is 1.19g/ml is added in 800ml distilled water,
Then the dissolving of 1.33g ferric trichlorides is added, is settled to 1000ml.
Sodium hydroxide solution preparation method is：It weighs 4.00g sodium hydroxides to be dissolved in distilled water, is settled to 1000ml.
The charging rate of the charging water sample is 1ml/min, and the charging rate of solvent distillation is 2ml/min, sodium hydroxide
Charging rate be 1.2ml/min, the charging rate of color developing agent is 0.23ml/min, and the charging rate of iron chloride is 0.42ml/
Min, nitrogen flow rate 90-100ml/min, air velocity 0.5ml/min.
3. taking standard environment sample, according to the identical condition of calibration curve is drawn, sample is measured.
4. replace sample with experimental water, by above-mentioned condition into line blank test.
5. result calculates：By detecting the peak height of sample, the corresponding concentration of sample, i.e. Instrument observation are obtained by standard curve
Value, is obtained based on following formula：
The mass concentration of sulfide in sample (in terms of S, mg/L)
In formula：The mass concentration of sulfide, mg/L in ρ-sample；
Y-measurement signal value (peak height)；
The intercept of a-calibrating curve equation；
The slope of b-calibrating curve equation；
F-extension rate.
According to the method described above, it is respectively the standard sample of 0.100mg/L, 0.500mg/L, 1.50mg/L to sulfur-bearing mass concentration
Product A, B, C parallel determination 6 times, method precision is shown in Table 1.
The measurement of 1 sulphide process precision of table and calculating (mg/L)
| Sample | 1 | 2 | 3 | 4 | 5 | 6 | Average value | Relative standard deviation (%) |
| A | 0.097 | 0.093 | 0.095 | 0.096 | 0.097 | 0.094 | 0.095 | 1.7 |
| B | 0.519 | 0.521 | 0.514 | 0.512 | 0.513 | 0.511 | 0.515 | 0.79 |
| C | 1.52 | 1.52 | 1.51 | 1.52 | 1.52 | 1.53 | 1.52 | 0.35 |
As seen from Table 1, the relative standard deviation of three groups of samples is respectively：1.7%, 0.79%, 0.35%, show the party
Method has preferable precision.
The detection limit of 2 this method of embodiment measures
The step of according to embodiment 1, substitutes sample with deionized water, and replication n (n=8) secondary blank test calculates 8
The standard deviation of secondary parallel determination, computational methods detection limit, concrete outcome are shown in Table 2 as follows.
MDL=t (n-1,0.99) × S
In formula：
MDL --- method detection limit；
The parallel determination number of n --- sample；
T --- degree of freedom n-1, t when confidence level is 99% are distributed (unilateral side)；
S --- the standard deviation of n times parallel determination.
When parallel determination number is 8, t values are 2.998.
The detection limit of 2 Methods for Determining Sulfide of table is analyzed
The mark-on of sulfide measures in certain the sewage plant water sample of embodiment 3
Using assay method described in embodiment 1, the water inlet water sample of sulfur content concentration known to certain sewage plant is carried out primary
Mark-on is tested, and measures the sulfur content after mark-on, the results are shown in Table 3：
The mark-on reclaims experiment of sulfide in 3 water sample of table
Recovery of standard addition of intaking it can be seen from result in table is 94.6%, meets the control of water quality monitoring Good Laboratory
Index, method the data obtained is accurate, credible high.
The measurement of sulfide in certain the sewage plant actual water sample of embodiment 4
Using assay method described in embodiment 1, sulfide measurement is carried out to the water sample of certain sewage plant, measurement result is such as
Under：
The sulfide of certain the sewage plant actual water sample of table 4 measures
| Sample | 1 | 2 | 3 | 4 | 5 | 6 | Average value |
| Content (mg/L) | 0.212 | 0.215 | 0.211 | 0.214 | 0.215 | 0.213 | 0.213 |
The sulfide of actual water sample is measured it can be seen from the result of table 4, the stability of this method is preferable, credible
Degree is high.
The invention is not limited in specific implementation modes above-mentioned.The present invention, which expands to, any in the present specification to be disclosed
New feature or any new combination, and disclose any new method or process the step of or any new combination.
Claims (8)
1. a kind of method measuring Sulfide in water with continuous flow method, which is characterized in that will charging water sample and chemistry using pump
Reagent is injected into Flow Analyzer, and in Flow Analyzer, distilling reagent is reacted and distilled with the sulfide in charging water sample,
Generate hydrogen sulfide gas absorbed by sodium hydroxide solution, absorbing liquid is reacted with color developing agent and iron chloride, reactant colorimeter into
Row measures.
2. a kind of method measuring Sulfide in water with continuous flow method according to claim 1, which is characterized in that described
The measurement wavelength of colorimeter is 660nm.
3. a kind of method measuring Sulfide in water with continuous flow method according to claim 2, which is characterized in that described
Distilling reagent is hydrochloric acid solution, and preparation method is:The hydrochloric acid that 100ml density is 1.19g/ml is added in 500ml distilled water, adds
Distilled water is settled to 1000ml.
4. a kind of method measuring Sulfide in water with continuous flow method according to claim 3, which is characterized in that described
The preparation method of color developing agent is：The hydrochloric acid that 10ml density is 1.19g/ml is added in 800ml distilled water, 33.4mg is then added
N, N- dimethyl-Isosorbide-5-Nitrae-phenylenediamine dihydrochloride dissolving and mixing, are settled to 1000ml, 1mlBrij35 mixings are added.
5. a kind of method measuring Sulfide in water with continuous flow method according to claim 4, which is characterized in that described
The preparation method of ferric chloride solution is：The hydrochloric acid that 10ml density is 1.19g/ml is added in 800ml distilled water, is then added
1.33g chlorination dissolved ferric irons, are settled to 1000ml.
6. a kind of method measuring Sulfide in water with continuous flow method according to claim 5, which is characterized in that described
Concentration of sodium hydroxide solution is 0.1mol/L.
7. a kind of method measuring Sulfide in water with continuous flow method according to claim 6, which is characterized in that described
The charging rate for feeding water sample is 1ml/min, and the charging rate of solvent distillation is 2ml/min, and the charging rate of sodium hydroxide is
The charging rate of 1.2ml/min, color developing agent are 0.23ml/min, and the charging rate of iron chloride is 0.42ml/min.
8. according to a kind of method measuring Sulfide in water with continuous flow method of claim 1-7 any one of them, feature
It is, vapo(u)rizing temperature is 75 DEG C -85 DEG C.
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Cited By (1)
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| CN111380817A (en) * | 2018-12-28 | 2020-07-07 | 贵州中烟工业有限责任公司 | Method for measuring total sulfur dioxide in tobacco or tobacco products by continuous flow method |
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