CN103760123B - The analysis determining method of DDAC in a kind of seawater - Google Patents

The analysis determining method of DDAC in a kind of seawater Download PDF

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CN103760123B
CN103760123B CN201410009543.XA CN201410009543A CN103760123B CN 103760123 B CN103760123 B CN 103760123B CN 201410009543 A CN201410009543 A CN 201410009543A CN 103760123 B CN103760123 B CN 103760123B
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seawater
solution
ddac
separating funnel
sodium thiosulfate
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CN103760123A (en
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冯璐
栾安博
黄奇然
邱美坚
缪飞
杨伟和
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Institute of Chemical Engineering of Guangdong Academy of Sciences
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GUANGDONG RESEARCH INSTITUTE PETROCHEMICAL INDUSTRY
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Abstract

The invention discloses the analysis determining method of DDAC in a kind of seawater, comprise the following steps: the standard solution 1) preparing DDAC, get the standard solution of gradient volume in separating funnel, seawater, sodium thiosulfate solution, chromogenic reagent solution is added in each funnel, control pH, shakes up sufficient standing; 2) in each separating funnel, add organic extractant to extract; 3) get organic layer solution, measure light absorption value, and return to zero with organic extractant, and as blank reference liquid, drawing standard curve; 4) measure seawater to be measured to separating funnel, add sodium thiosulfate solution, chromogenic reagent solution wherein, control pH, shakes up sufficient standing; 5) in each separating funnel, add organic extractant to extract; 6) get organic layer solution, measure light absorption value, calculate DDAC concentration in seawater according to typical curve.Method of testing of the present invention is accurately reliable, simple to operation.

Description

The analysis determining method of DDAC in a kind of seawater
Technical field
The present invention relates to the analysis determining method of DDAC in a kind of seawater.
Background technology
DDAC is a kind of cationic surfactant, and DDAC is one of third generation product of quaternary ammonium salt bactericide, and it has microorganism stronger kills ability, can be used for oil-field flooding and industrial cooling circulating water system makes germifuge and Biocidal algae-killing agent etc.The mechanism of action of this series bactericidal agent mainly kation by effects such as electrostatic force, hydrogen bond force and the hydrophobic bindings between surfactant molecule and protein molecule, adsorb electronegative bacterial body, be gathered on cell membrane, generating chamber's inhibition effect, cause bacterial growth suppressed and dead; Simultaneously its hydrophobic alkyl can also with the hydrophilic group effect of microorganism, change the permeability of film, then lysis occur, destroy eucaryotic cell structure, cause dissolving and the death of cell.The in line cooling water system process field of seawater is applied to kill the microorganisms such as the shellfish in Cooling system pipe, and dosage is at 1ppm.Although DDAC belongs to lower toxicity germifuge, Drug level is low, but still needs strict its concentration of emission of control.
For the content analysis of such short carbon chain quaternary ammonium salt, mainly contain chemical method and instrumental method, international standard and China standard GB/T5174 all adopt chemical titration analysis, but chemical method detection limit is higher is not suitable for this type of trace detection.And more employing ultraviolet spectrophotometer is analyzed it in instrumental method, nearly all undertaken and spectral analysis by extraction chloroform layer under this single environment of pure water in existing published method.There is scholar's " Central-South pharmacy " in the second phase disclosed in 2004, utilize benzalkonium bromide to form stabilizing ion with bromophenol blue in the basic conditions in " content of Wan withAcid-dye Colorimetry low concentration benzalkonium bromide solution " literary composition and there is good uv absorption, and easily recorded its content by the character of chloroform extraction.But this method is not also suitable for the microanalysis of the quaternary ammonium salt in complex dielectrics as this in seawater.Experiment shows to extract from seawater the light absorption value extremely unstable that the chloroform layer that obtains obtains when carrying out ultra-violet analysis, even decays to zero.Within 2010, there is one section of article the published content of quaternary ammonium salt " in the determined by ultraviolet spectrophotometry seawater " in the second phase at " physical and chemical inspection-chemical fascicle ", but do not mention analyzed quaternary ammonium salt type in article, and namely itself have uv absorption without the need to adding developer, and in the present invention DDAC itself without uv absorption, need be analyzed again by process, so situation is more complicated when analyzing the content of this medicament used in seawater.
Summary of the invention
The object of the present invention is to provide the analysis determining method of DDAC in a kind of seawater.
The technical solution used in the present invention is:
An analysis determining method for DDAC in seawater, comprises the following steps:
1) compound concentration is the standard solution of the DDAC of 10-20ppm, get standard solution that some parts of volumes change in gradient in separating funnel, three kinds of materials are all added: seawater, sodium thiosulfate solution, chromogenic reagent solution in each separating funnel, the pH controlling solution is 2≤pH < 7, shakes up and sufficient standing;
2) in each separating funnel, add organic extractant, fully shake separating funnel fully extracts, static layering;
3) get organic layer solution, measure its light absorption value A at 410-490nm place ultraviolet spectrophotometer, and return to zero with organic extractant, and as blank reference liquid, drawing standard curve;
4) measure some parts seawater to be measured and add in separating funnel, then add sodium thiosulfate solution, chromogenic reagent solution in separating funnel, the pH controlling solution is 2≤pH < 7, shakes up and sufficient standing;
5) in each separating funnel, add organic extractant, fully shake separating funnel fully extracts, static layering;
6) get organic layer solution, at wavelength place same with step 3), ultraviolet spectrophotometer measures its light absorption value, and the typical curve according to gained calculates DDAC concentration in seawater.
In step 1) and step 4), the concentration of sodium thiosulfate solution is 0.1-1mol/L.
In step 1), in the standard solution that described volume changes in gradient, minimum volume is 0.5-1.5ml, and maximum volume is 7.5-10.5ml.
In step 1), in each separating funnel, the addition of seawater is 8-12mL.
In step 1), utilize weak acid to control the pH of solution, described weak acid comprises carbonic acid, acetic acid, oxalic acid, sulphurous acid.
In step 1), the solvent of the standard solution of DDAC is seawater.
In step 1) and step 4), the mass concentration of chromogenic reagent solution is 0.1-0.2wt%; Described developer is at least one in acid blue, thymol blue, orange II, alizarin yellow R, methyl orange.
In step 1), the addition ratio of the sodium thiosulfate in sodium thiosulfate solution, the developer in chromogenic reagent solution, seawater three is: 0.02-0.2mmol:(2-4) × 10 -4mg:10ml; In step 4), the addition ratio of the sodium thiosulfate in sodium thiosulfate solution, the developer in chromogenic reagent solution, seawater three is: 0.02-0.2mmol:(2-4) × 10 -4mg:10ml.
Step 2) in, the addition of organic extractant is 8-12mL; Described organic extractant is at least one in methylene chloride, ethylene dichloride, propylene dichloride, methenyl choloride, bromochloromethane, methylene bromide, bromochloroethane, ethylene dibromide, ether.
At least one in organic extractant methylene chloride used in step 5), ethylene dichloride, propylene dichloride, methenyl choloride, bromochloromethane, methylene bromide, bromochloroethane, ethylene dibromide, ether.
The invention has the beneficial effects as follows: method of testing of the present invention is accurately reliable, simple to operation.Specifically:
In Seawater, composition is extremely complicated, exist a lot to the factor of analytical test interference, analysis test method of the present invention can compared with the concentration of the DDAC in this complex dielectrics of Accurate Measurement seawater, quick and precisely simple to operation, parallel testing several times, the relative deviation of the data obtained is little.
Accompanying drawing explanation
Fig. 1 is the typical curve of embodiment 1 gained.
Embodiment
An analysis determining method for DDAC in seawater, comprises the following steps:
1) compound concentration is the standard solution of the DDAC of 10-20ppm, get standard solution that some parts of volumes change in gradient in separating funnel, three kinds of materials are all added: seawater, sodium thiosulfate solution, developer aqueous solution in each separating funnel, the pH controlling solution is 2≤pH < 7, shakes up and sufficient standing;
2) in each separating funnel, add organic extractant, fully shake separating funnel fully extracts, static layering;
3) get organic layer solution, measure its light absorption value A at 410-490nm place ultraviolet spectrophotometer, and return to zero with organic extractant, and as blank reference liquid, drawing standard curve;
4) measure some parts seawater to be measured and add in separating funnel, then in separating funnel, adding sodium thiosulfate solution, developer aqueous solution, the pH controlling solution is 2≤pH < 7, shakes up and sufficient standing;
5) in each separating funnel, add organic extractant, fully shake separating funnel fully extracts, static layering;
6) get organic layer solution, at wavelength place same with step 3), ultraviolet spectrophotometer measures its light absorption value, and the typical curve according to gained calculates DDAC concentration in seawater.
In step 1) and step 4), the concentration of sodium thiosulfate solution is 0.1-1mol/L.
In step 1), in the standard solution that described volume changes in gradient, minimum volume is 0.5-1.5ml, and maximum volume is 7.5-10.5ml.
In step 1), in each separating funnel, the addition of seawater is 8-12mL.
In step 1), utilize weak acid to control the pH of solution, described weak acid comprises carbonic acid, acetic acid, oxalic acid, sulphurous acid.
In step 1) and step 4), the mass concentration of developer aqueous solution is 0.1-0.2wt%; Described developer is at least one in acid blue, thymol blue, orange II, alizarin yellow R, methyl orange.
In step 1), the addition ratio of the developer in the sodium thiosulfate in sodium thiosulfate solution, developer aqueous solution, seawater three is: 0.02-0.2mmol:(2-4) × 10 -4mg:10ml; In step 4), the addition ratio of the developer in the sodium thiosulfate in sodium thiosulfate solution, developer aqueous solution, seawater three is: 0.02-0.2mmol:(2-4) × 10 -4mg:10ml.
Step 2) in, the addition of organic extractant is 8-12mL; Described organic extractant is at least one in methylene chloride, ethylene dichloride, propylene dichloride, methenyl choloride, bromochloromethane, methylene bromide, bromochloroethane, ethylene dibromide, ether.
At least one in organic extractant methylene chloride used in step 5), ethylene dichloride, propylene dichloride, methenyl choloride, bromochloromethane, methylene bromide, bromochloroethane, ethylene dibromide, ether; Preferably, organic extractant used and step 2) in organic extractant used identical.
It should be noted that, in the present invention:
In step 1), the solvent that the standard solution of preparation DDAC is used is seawater, and the seawater of one of this solvent seawater three kinds of materials added in each separating funnel therewith described in step be containing DDAC blank seawater (namely in seawater without dispensing process, namely with the standard solution of this blank seawater for solvent preparation DDAC, from solvent, additionally DDAC can not be introduced).
Seawater to be measured in step 4) is the seawater through dispensing process, namely for the seawater in step 1), has added medicine DDAC wherein;
As described in the background art, its (i.e. DDAC) is applied to the microorganisms such as the shellfish killed in Cooling system pipe by the in line cooling water system process field of seawater.
Following enumerated embodiment is also such: in drawing standard curve step, and involved seawater is the blank seawater not adding medicine;
Therefore, with the standard solution of this blank seawater preparation DDAC, from solvent, additionally DDAC can not be brought into.
And in the step of the preparation and determination methods of sample, seawater to be measured is the seawater through dispensing process.
Object of the present invention also measures the concentration of DDAC in the seawater of dispensing process just.
Below in conjunction with specific embodiment, the present invention is described further:
embodiment 1
(1) drawing standard curve: the DDAC standard solution take seawater as solvent compound concentration being 13.36ppm; Prepare the aqueous solution of acid blue 80 and the sodium thiosulfate solution of 0.1mol/L that mass concentration is 0.1%.With transfer pipet draw 1 respectively, 2,4,6, the standard solution of 8ml is in five separating funnels, add 10ml seawater, 0.2mL sodium thiosulfate solution and 0.2mL acid blue respectively, and be 3 with acetic acid control pH value of solution, after shaking up rear static placement 30min, add in five separating funnels respectively with pipette, extract 10ml ethylene dichloride (reagent is pure), abundant shake separating funnel, component to be measured is fully extracted into organic phase, static layering afterwards, obtain concentration be respectively 1.336,2.672,5.344,8.016, the solution of 10.688ppm; Get organic phase respectively in 5 cuvettes.At 410nm place, ultraviolet spectrophotometer measures its light absorption value, and with ethylene dichloride zeroing, and as blank reference liquid, drawing standard curve, is shown in accompanying drawing 1.
(2) preparation and determination methods of sample: the Duplicate Samples of correct amount 5 parts of 200ml seawater to be measured is in 5 separating funnels, add the aqueous solution 4mL that the sodium thiosulfate solution 4mL of 0.1mol/L and mass concentration are the acid blue 80 of 0.1%, controlling its pH with acetic acid is 3, shakes up.The extraction of 20ml ethylene dichloride is added respectively again with transfer pipet, take off a layer organic phase, under same wave number, (410nm) records 5 groups of light absorption values and is respectively 0.07,0.069,0.069,0.068,0.069, according to typical curve, draw DDAC mean concentration 4.8857ppm in seawater, calculating its relative standard deviation is 1.14%.
(3) calculating of blank recovery of standard addition: the DDAC solution 1ml accurately measuring 104ppm, in the non-dosing seawater of 200ml, testing it containing measuring 5.3911ppm by step (2), calculating its blank recovery of standard addition=102.4%
embodiment 2
(1) drawing standard curve: the DDAC standard solution take seawater as solvent compound concentration being 10ppm; Preparing mass concentration is the aqueous solution of the methyl orange of 0.1% and the sodium thiosulfate solution of 0.1mol/L.With transfer pipet draw 1 respectively, 2,4,6, the standard solution of 8ml is in five separating funnels, add 10ml seawater, 0.2mL sodium thiosulfate solution and 0.2mL methyl orange respectively, and be 3 with acetic acid control pH value of solution, after shaking up rear static placement 20min, add in five separating funnels respectively with pipette, extract 10ml methylene chloride (reagent is pure), abundant shake separating funnel, component to be measured is fully extracted into organic phase, static layering afterwards, obtain concentration be 1,2,4,6, the solution of 8ppm; Get organic phase respectively in 5 cuvettes.At 440nm place, ultraviolet spectrophotometer measures its light absorption value, with methylene chloride zeroing, and as blank reference liquid, and typical curve, y=0.0195x+0.0093, R 2=0.9995.
(2) preparation and determination methods of sample: correct amount 5 parts of 200ml seawater sample to be measured is in 5 separating funnels, add the aqueous solution 4mL that the sodium thiosulfate solution 4mL of 0.1mol/L and mass concentration are the methyl orange of 0.1%, controlling its pH with acetic acid is 3, shakes up.20ml dichloromethane extraction is added respectively again with transfer pipet, take off a layer organic phase, under same wave number, survey its light absorption value be respectively 0.102,0.105,0.106,0.104,0.105, according to typical curve, calculating DDAC mean concentration in seawater is 4.8769ppm, and to calculate its relative standard deviation be 1.59%.
embodiment 3
(1) drawing standard curve: the DDAC standard solution take seawater as solvent compound concentration being 15ppm; Preparing mass concentration is the aqueous solution of the Acid Orange II of 0.1% and the sodium thiosulfate solution of 0.2mol/L.With transfer pipet draw 1 respectively, 2,4,6, the standard solution of 8ml in five separating funnels, add 10ml seawater, 0.2mL sodium thiosulfate solution and 0.2mL Acid Orange II respectively, and to control pH value of solution with acetic acid be 5, shake up rear static placement 15min.Afterwards, add respectively in five separating funnels with pipette, extract 10ml bromochloromethane (reagent is pure), fully shake separating funnel, component to be measured is fully extracted into organic phase, static layering afterwards, obtain concentration be 1.5,3,6,9, the solution of 12ppm; Get organic phase respectively in 5 cuvettes.At 484nm place, ultraviolet spectrophotometer measures its light absorption value, with bromochloromethane zeroing, and as blank reference liquid, and drawing standard curve y=0.0209x+0.0124, R 2=0.9995.
(2) preparation and determination methods of sample: correct amount 5 parts of 250ml seawater sample to be measured, in 5 separating funnels, adds the aqueous solution 5mL that the sodium thiosulfate solution 5mL of 0.1mol/L and mass concentration are the Acid Orange II of 0.1% ,controlling its pH with acetic acid is 5, shakes up.The extraction of 25ml bromochloromethane is added respectively again with transfer pipet, take off a layer organic phase, under same wave number, survey its light absorption value be respectively 0.113,0.113,0.112,0.115,0.113, according to typical curve, calculating DDAC mean concentration in seawater is 4.8230ppm, and to calculate its relative standard deviation be 1.09%.

Claims (8)

1. the analysis determining method of DDAC in seawater, is characterized in that: comprise the following steps:
1) compound concentration is the standard solution of the DDAC of 10-20ppm, get standard solution that some parts of volumes change in gradient in separating funnel, three kinds of materials are all added: seawater, sodium thiosulfate solution, chromogenic reagent solution in each separating funnel, the pH controlling solution is 2≤pH < 7, shakes up and sufficient standing;
2) in each separating funnel, add organic extractant, fully shake separating funnel fully extracts, static layering;
3) get organic layer solution, measure its light absorption value A at 410-490nm place ultraviolet spectrophotometer, and return to zero with organic extractant, and as blank reference liquid, drawing standard curve;
4) measure some parts seawater to be measured and add in separating funnel, then add sodium thiosulfate solution, chromogenic reagent solution in separating funnel, the pH controlling solution is 2≤pH < 7, shakes up and sufficient standing;
5) in each separating funnel, add organic extractant, fully shake separating funnel fully extracts, static layering;
6) get organic layer solution, at wavelength place same with step 3), ultraviolet spectrophotometer measures its light absorption value, and the typical curve according to gained calculates DDAC concentration in seawater;
Step 2) in, the addition of organic extractant is 8-12mL; Described organic extractant is at least one in methylene chloride, ethylene dichloride, propylene dichloride, methenyl choloride, bromochloromethane, methylene bromide, bromochloroethane, ethylene dibromide, ether; At least one in organic extractant methylene chloride used in step 5), ethylene dichloride, propylene dichloride, methenyl choloride, bromochloromethane, methylene bromide, bromochloroethane, ethylene dibromide, ether.
2. the analysis determining method of DDAC in a kind of seawater according to claim 1, is characterized in that: in step 1) and step 4), the concentration of sodium thiosulfate solution is 0.1-1mol/L.
3. the analysis determining method of DDAC in a kind of seawater according to claim 1, it is characterized in that: in step 1), in the standard solution that described volume changes in gradient, minimum volume is 0.5-1.5ml, and maximum volume is 7.5-10.5ml.
4. the analysis determining method of DDAC in a kind of seawater according to claim 1, it is characterized in that: in step 1), in each separating funnel, the addition of seawater is 8-12mL.
5. the analysis determining method of DDAC in a kind of seawater according to claim 1, is characterized in that: in step 1), and utilize weak acid to control the pH of solution, described weak acid comprises carbonic acid, acetic acid, oxalic acid, sulphurous acid.
6. the analysis determining method of DDAC in a kind of seawater according to claim 1, it is characterized in that: in step 1), the solvent of the standard solution of DDAC is seawater.
7. the analysis determining method of DDAC in a kind of seawater according to claim 1, is characterized in that: in step 1) and step 4), the mass concentration of chromogenic reagent solution is 0.1-0.2wt%; Described developer is at least one in acid blue, thymol blue, orange II, alizarin yellow R, methyl orange.
8. the analysis determining method of DDAC in a kind of seawater according to claim 1, it is characterized in that: in step 1), the addition ratio of the sodium thiosulfate in sodium thiosulfate solution, the developer in chromogenic reagent solution, seawater three is: 0.02-0.2mmol:(2-4) × 10 -4mg:10ml; In step 4), the addition ratio of the sodium thiosulfate in sodium thiosulfate solution, the developer in chromogenic reagent solution, seawater three is: 0.02-0.2mmol:(2-4) × 10 -4mg:10ml.
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