CN114137149A - Method for detecting content of quaternary ammonium salt - Google Patents
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- 150000003242 quaternary ammonium salts Chemical class 0.000 title claims abstract description 179
- 238000000034 method Methods 0.000 title claims abstract description 63
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 185
- 239000000243 solution Substances 0.000 claims abstract description 94
- 238000002835 absorbance Methods 0.000 claims abstract description 88
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims abstract description 63
- -1 sodium tetraphenylborate Chemical compound 0.000 claims abstract description 56
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 51
- ZPLCXHWYPWVJDL-UHFFFAOYSA-N 4-[(4-hydroxyphenyl)methyl]-1,3-oxazolidin-2-one Chemical compound C1=CC(O)=CC=C1CC1NC(=O)OC1 ZPLCXHWYPWVJDL-UHFFFAOYSA-N 0.000 claims abstract description 50
- 238000001514 detection method Methods 0.000 claims abstract description 49
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- UDSAIICHUKSCKT-UHFFFAOYSA-N bromophenol blue Chemical compound C1=C(Br)C(O)=C(Br)C=C1C1(C=2C=C(Br)C(O)=C(Br)C=2)C2=CC=CC=C2S(=O)(=O)O1 UDSAIICHUKSCKT-UHFFFAOYSA-N 0.000 claims abstract description 22
- 238000000870 ultraviolet spectroscopy Methods 0.000 claims abstract description 13
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- 235000012736 patent blue V Nutrition 0.000 claims abstract description 5
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- 239000007864 aqueous solution Substances 0.000 claims description 52
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- BNIILDVGGAEEIG-UHFFFAOYSA-L disodium hydrogen phosphate Chemical compound [Na+].[Na+].OP([O-])([O-])=O BNIILDVGGAEEIG-UHFFFAOYSA-L 0.000 claims description 38
- 235000019441 ethanol Nutrition 0.000 claims description 28
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 24
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 18
- 239000007788 liquid Substances 0.000 claims description 15
- JRMUNVKIHCOMHV-UHFFFAOYSA-M tetrabutylammonium bromide Chemical compound [Br-].CCCC[N+](CCCC)(CCCC)CCCC JRMUNVKIHCOMHV-UHFFFAOYSA-M 0.000 claims description 15
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 claims description 13
- 239000001632 sodium acetate Substances 0.000 claims description 13
- 235000017281 sodium acetate Nutrition 0.000 claims description 13
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 12
- 125000000217 alkyl group Chemical group 0.000 claims description 8
- 239000000872 buffer Substances 0.000 claims description 8
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 8
- 239000011259 mixed solution Substances 0.000 claims description 5
- 239000000126 substance Substances 0.000 claims description 5
- 239000004480 active ingredient Substances 0.000 claims description 4
- 125000001453 quaternary ammonium group Chemical group 0.000 claims description 4
- 150000001875 compounds Chemical class 0.000 claims description 3
- 238000004090 dissolution Methods 0.000 claims description 2
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- 239000001509 sodium citrate Substances 0.000 claims description 2
- NLJMYIDDQXHKNR-UHFFFAOYSA-K sodium citrate Chemical compound O.O.[Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O NLJMYIDDQXHKNR-UHFFFAOYSA-K 0.000 claims description 2
- 239000012064 sodium phosphate buffer Substances 0.000 claims description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims 1
- 239000008346 aqueous phase Substances 0.000 claims 1
- 229910052708 sodium Inorganic materials 0.000 claims 1
- 239000011734 sodium Substances 0.000 claims 1
- 239000012071 phase Substances 0.000 abstract description 4
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- 239000012086 standard solution Substances 0.000 description 10
- 239000003153 chemical reaction reagent Substances 0.000 description 8
- 150000003863 ammonium salts Chemical group 0.000 description 6
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- WOWHHFRSBJGXCM-UHFFFAOYSA-M cetyltrimethylammonium chloride Chemical compound [Cl-].CCCCCCCCCCCCCCCC[N+](C)(C)C WOWHHFRSBJGXCM-UHFFFAOYSA-M 0.000 description 2
- 238000004737 colorimetric analysis Methods 0.000 description 2
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- 229950006187 hexamethonium bromide Drugs 0.000 description 2
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
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- FAPSXSAPXXJTOU-UHFFFAOYSA-L trimethyl-[6-(trimethylazaniumyl)hexyl]azanium;dibromide Chemical compound [Br-].[Br-].C[N+](C)(C)CCCCCC[N+](C)(C)C FAPSXSAPXXJTOU-UHFFFAOYSA-L 0.000 description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-M Bicarbonate Chemical compound OC([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-M 0.000 description 1
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- 229910020489 SiO3 Inorganic materials 0.000 description 1
- SWLVFNYSXGMGBS-UHFFFAOYSA-N ammonium bromide Chemical compound [NH4+].[Br-] SWLVFNYSXGMGBS-UHFFFAOYSA-N 0.000 description 1
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- 239000003054 catalyst Substances 0.000 description 1
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- VAYGXNSJCAHWJZ-UHFFFAOYSA-N dimethyl sulfate Chemical compound COS(=O)(=O)OC VAYGXNSJCAHWJZ-UHFFFAOYSA-N 0.000 description 1
- 238000006073 displacement reaction Methods 0.000 description 1
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- 238000004817 gas chromatography Methods 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 1
- 125000002768 hydroxyalkyl group Chemical group 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
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- 230000007935 neutral effect Effects 0.000 description 1
- VLTRZXGMWDSKGL-UHFFFAOYSA-M perchlorate Chemical compound [O-]Cl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-M 0.000 description 1
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- 238000007639 printing Methods 0.000 description 1
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Images
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N31/00—Investigating or analysing non-biological materials by the use of the chemical methods specified in the subgroup; Apparatus specially adapted for such methods
- G01N31/16—Investigating or analysing non-biological materials by the use of the chemical methods specified in the subgroup; Apparatus specially adapted for such methods using titration
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- Health & Medical Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Molecular Biology (AREA)
- Physics & Mathematics (AREA)
- Chemical & Material Sciences (AREA)
- Analytical Chemistry (AREA)
- Biochemistry (AREA)
- General Health & Medical Sciences (AREA)
- General Physics & Mathematics (AREA)
- Immunology (AREA)
- Pathology (AREA)
- Investigating Or Analysing Materials By The Use Of Chemical Reactions (AREA)
- Investigating Or Analyzing Non-Biological Materials By The Use Of Chemical Means (AREA)
Abstract
The invention provides a method for detecting the content of quaternary ammonium salt. The detection method comprises the following steps: taking a water sample to be detected for detecting A or B, and optionally taking the water sample to be detected for detecting B or A if the quaternary ammonium salt content cannot be determined; the detection A comprises the following steps: mixing a water sample to be detected with a buffer solution A and a sodium tetraphenylborate solution, removing precipitates, adding a NaOH solution, a bromophenol blue indicator and an oil solvent, titrating by using a titrant A until a light blue precipitate appears in an oil solvent layer and a water phase layer becomes sky blue to reach a titration end point, and determining the content of quaternary ammonium salt based on the usage amount of the titrant A and the usage amount of the sodium tetraphenylborate solution; the detection B comprises the following steps: mixing a water sample to be detected or a water sample diluted by a certain multiple with a mixing oil solvent, a bromothymol blue indicator and a buffer solution B, standing for layering, separating to obtain a mixing oil solvent layer liquid phase, adding a boric acid alcohol solution into the mixing oil solvent layer liquid phase, measuring absorbance by using an ultraviolet visible spectrophotometer, and determining the quaternary ammonium salt content by means of a relationship model of the absorbance and the quaternary ammonium salt concentration.
Description
Technical Field
The invention belongs to the technical field of content detection, and particularly relates to a method for detecting the content of quaternary ammonium salt.
Background
The quaternary ammonium salt compound has simple synthesis and easy separation, has many excellent properties such as high surface activity, good wettability and the like, and particularly can form a nano-molecular deposition film (hereinafter referred to as MD film) at the oil reservoir boundary/surface, so that the quaternary ammonium salt compound is widely applied to the petroleum industry as an oil displacement agent, a demulsifier, a catalyst and a clay stabilizing, anti-swelling and anti-blocking injection enhancer.
In addition, quaternary ammonium salt compounds are widely used in water treatment, textile printing and dyeing, disinfection and sterilization and other industries.
With the research on quaternary ammonium salts by researchers, a great number of novel quaternary ammonium salts such as biquaternary ammonium salts, triquaternary ammonium salts, polyquaternary ammonium salts and the like are invented, so that a method for accurately measuring the content of the quaternary ammonium salts is needed to be developed, and a research basis is provided for the deep excavation of quaternary ammonium salt compounds.
The existing quaternary ammonium salt detection technology is divided into an instrumental analysis method and a chemical reaction method. The chemical reaction method is an analysis method based on the chemical reaction of quaternary ammonium salt and anion reagent or precipitator, and is suitable for measuring single quaternary ammonium salt with known relative molecular mass or measuring the total amount of compound quaternary ammonium salt. When the quaternary ammonium salt is undefined in kind and has a low concentration, instrumental analysis is required. The instrumental analysis method mainly includes gas chromatography, liquid chromatography, spectrophotometry and the like, and is a method for performing qualitative and quantitative analysis according to certain physical properties or certain properties in chemical changes of quaternary ammonium salt.
CN111812088A discloses a method for accurately detecting the content of quaternary ammonium salt cations in alkaline wastewater. The method comprises the steps of adding a mixed solution of formaldehyde, sodium tetraphenylborate, sodium hydroxide and danoflow into a water sample to be detected for pretreatment, then dropwise adding hexadecyl trimethyl ammonium chloride to serve as a quaternary ammonium salt cation detection reagent, recording the using amount of the hexadecyl trimethyl ammonium chloride when the solution begins to appear pink, and further calculating to obtain the quaternary ammonium salt content in the water sample. The method has the following defects: on one hand, when the concentration of the quaternary ammonium salt contained in the water sample is different, mixed liquor with different proportions of formaldehyde, sodium tetraphenylborate, sodium hydroxide and dadan yellow is required to be used, but the cation content of the quaternary ammonium salt in the actual sewage is unknown, and the mixed liquor with a proper proportion is difficult to select and match, so that the measurement result is possibly inaccurate; on the other hand, the method is only suitable for detection when the content of the quaternary ammonium salt is low, and if the content is too high, the sodium tetraphenylborate is not excessive during pretreatment, so that the content of the quaternary ammonium salt in a water sample cannot be detected.
CN106596530A discloses a method for rapidly detecting the residual concentration of quaternary ammonium salt. According to the method, a quaternary ammonium salt (I) reagent and a quaternary ammonium salt (II) reagent are sequentially added into a water sample to be detected, and the content of the quaternary ammonium salt in the water sample to be detected is determined through colorimetry. Wherein, the quaternary ammonium salt (I) reagent consists of tiger red sodium salt and organic carboxylate, and the quaternary ammonium salt (II) reagent consists of solid organic carboxylic acid. The technology is visual colorimetry, and when the color tone of a sample color development solution is inconsistent with a standard color scale, estimation reading is needed, so that the content of the quaternary ammonium salt obtained by testing can only be limited in a certain range, and an accurate content value cannot be obtained. And when the quaternary ammonium salt content is different, the content of each component in the quaternary ammonium salt (I) reagent and the quaternary ammonium salt (II) reagent which need to be configured is different, otherwise, the phenomenon of unstable color development can occur, and the whole measuring process is more complicated.
Disclosure of Invention
The invention aims to provide a method for rapidly and conveniently detecting the content of quaternary ammonium salt in a water phase.
In order to achieve the above object, the present invention provides a method for detecting a quaternary ammonium salt content, the method comprising:
taking a water sample to be detected for detection A; if the quaternary ammonium salt content in the water sample to be detected cannot be determined, selectively taking the water sample to be detected to detect B;
or;
taking a water sample to be detected for detection B; if the quaternary ammonium salt content in the water sample to be detected cannot be determined, selectively taking the water sample to be detected to detect A;
wherein detecting a comprises:
mixing a water sample to be detected with a buffer solution A to obtain a mixed solution with the pH value of 4-5, adding a sodium tetraphenylborate solution to react fully, removing a precipitate, and adding NaOH, a bromophenol blue indicator and an oil solvent; wherein the oil solvent comprises chloroform and/or dichloromethane; the added amount of the sodium hydroxide can realize the complete dissolution of the added bromophenol blue indicator;
carrying out titration by using a titrant A until a light blue precipitate appears in an oil solvent layer and a water phase layer becomes sky blue, and reaching a titration end point; recording the usage amount of the titrant A; wherein the effective component of the titrant A has a structural formula
[R1R2R3N]+X-A compound of (1), R1、R2、R3、R4Is alkyl, X is selected from one of F, Cl, Br and I;
determining the content of quaternary ammonium salt in a water sample to be detected based on the usage amount of the titrant A and the usage amount of the sodium tetraphenylborate solution;
wherein detecting B comprises:
mixing a water sample to be detected or a water sample diluted by a certain multiple with an oil solvent, a bromothymol blue indicator and a buffer B, standing for layering, and separating to obtain an oil solvent layer liquid phase; wherein the oil solvent comprises chloroform and/or dichloromethane;
adding a boric acid alcohol solution into the oil solvent layer liquid phase, and measuring absorbance by using an ultraviolet-visible spectrophotometer;
and determining the quaternary ammonium salt content in the water sample to be detected by means of a relation model between the absorbance and the quaternary ammonium salt concentration based on the measured absorbance.
In the method for detecting the content of the quaternary ammonium salt, a water sample to be detected is taken for detection A, and if the content of the quaternary ammonium salt in the water sample to be detected is determined, the water sample to be detected does not need to be taken for detection B. And (3) taking a water sample to be detected to detect B, and if the quaternary ammonium salt content in the water sample to be detected is determined, taking the water sample to be detected to detect B is not required.
In a specific embodiment, the method for detecting the content of the quaternary ammonium salt comprises the following steps: and (4) taking a water sample to be detected to perform detection A.
In a specific embodiment, the method for detecting the content of the quaternary ammonium salt comprises the following steps: and taking a water sample to be detected for detection B.
In a specific embodiment, the method for detecting the content of the quaternary ammonium salt comprises the following steps: and (3) firstly taking a water sample to be detected to carry out detection A, and then taking the water sample to be detected to carry out detection B, so as to obtain the content of the quaternary ammonium salt in the water sample to be detected.
In a specific embodiment, the method for detecting the content of the quaternary ammonium salt comprises the following steps: and (3) firstly taking a water sample to be detected to detect B, and then taking the water sample to be detected to detect A, so as to obtain the content of the quaternary ammonium salt in the water sample to be detected.
In the aboveIn the method for detecting the content of the quaternary ammonium salt, the quaternary ammonium salt can be one or a mixture of more than two of single quaternary ammonium salt, biquaternary ammonium salt, tri-quaternary ammonium salt and multi (more than three) quaternary ammonium salt. In one embodiment, the monoquaternary ammonium salt has the formula
The molecular formula of the biquaternary ammonium salt is
The molecular formula of the tri-quaternary ammonium salt is
The quaternary ammonium salt in the present invention includes, but is not limited to, compounds having the above formula or a mixture of two or more of them at any ratio;
in the above formula, Xn、X’nMay be independently selected from- (CH)2)n-(n＝0-8)、-(CH＝CH)n-(n＝1-2)、-(C6H4)n-(n＝1-4)、-[(CH2)mO(CH2)m]n-(m＝1-6、n＝1-4)、-[(CH2)mN(A1)(CH2)m]n-(m＝1-6、n＝1-4)、-[(CH2)mS(CH2)m]n-(m＝1-6、n＝1-4)；
A1-A8May each independently be one member selected from the group consisting of hydrogen, substituted or unsubstituted alkyl, substituted or unsubstituted aryl, substituted or unsubstituted aralkyl, such as A1-A8Each independently selected from-H, -CnH2n+1(n＝1-8)、-Ph、PhCH2-or-ROH (-ROH is hydroxyalkyl, e.g. -CH)2CH2OH、-CH2CH3OH、-CH2CH2CH3OH, etc.);
B-may be selected from OH-、Cl-、Br-、I-、HSO3 -、MeSO4 -、ClO4 -、ClO-、H2PO4 -、BF4 -、NO2 -、NO3 -、HCO3 -、PhCOO-、CH3PhSO3 -、PhSO3 -And RCOO-(R is selected from one of H, alkyl, substituted alkyl, e.g. HCOO-、Ac-) One of (1); b is2-Can be selected from HSO4 2-、S2O7 2-、SO3 2-、SO4 2-、HPO4 2-、B4O7 2-、SiO3 2-And CO3 2-One of (1); b is3-Can be selected from PO4 3-(ii) a Me is methyl, i.e. -CH3。
In the method for detecting the content of the quaternary ammonium salt, the adding amount of the sodium tetraphenylborate is excessive, so that a water sample to be detected and a sodium tetraphenylborate solution are fully reacted; and adding excessive sodium tetraphenylborate to react with quaternary ammonium salt in the water sample to be detected, and further using an active ingredient of a titrant A to react with the residual sodium tetraphenylborate, so that the content of the quaternary ammonium salt in the water sample to be detected is determined based on the use amounts of the sodium tetraphenylborate and the titrant A.
In the method for detecting the content of the quaternary ammonium salt, the buffer solution A provides a stable detection environment for a water sample to be detected. Preferably, in the detection A, the buffer solution A comprises one or a combination of more than two of mixed aqueous solution of acetic acid and sodium acetate, sodium citrate buffer solution and sodium phosphate buffer solution;
in a specific embodiment, the buffer solution a is a mixed aqueous solution of acetic acid and sodium acetate, wherein the mixed aqueous solution of acetic acid and sodium acetate is obtained by mixing a sodium acetate solution with a sodium acetate content of 6.48g/L with an acetic acid solution with an acetic acid volume fraction of 0.48%, and the volume ratio of the sodium acetate solution to the acetic acid solution is 25: 15.
In the method for detecting the content of the quaternary ammonium salt, preferably, in the detection A, the volume ratio of the added volume of the buffer solution A to the volume of the water sample to be detected is 30:1-120: 1.
In the method for detecting the content of the quaternary ammonium salt, preferably, in the detection A, the concentration of the sodium tetraphenylborate solution is 0.01-0.05N; in one embodiment, the concentration of the sodium tetraphenylborate solution is 0.02N.
In the method for detecting the content of the quaternary ammonium salt, preferably, in the detection a, the mass ratio of the volume usage amount of the sodium tetraphenylborate solution to the liquid sample to be detected is 10-50mL:160 mg.
In the method for detecting the content of the quaternary ammonium salt, preferably, in the detection a, the bromophenol blue indicator is a mixed aqueous solution of bromophenol blue and sodium hydroxide. In a specific embodiment, the bromophenol blue indicator is prepared by dissolving bromophenol blue in sodium hydroxide solution; wherein, the volume of the bromophenol blue indicator is taken as a reference, and the concentration of bromophenol blue in the bromophenol blue indicator is 5 multiplied by 10-3The concentration of g/L, NaOH was 0.1 mol/L.
In the method for detecting the content of the quaternary ammonium salt, preferably, in the step A, NaOH is added in a form of NaOH solution; more preferably, the content of sodium hydroxide in the added NaOH solution is 0.05-0.5mol/L based on the volume of the added NaOH solution; further preferably, the mass ratio of the volume of the added NaOH solution to the liquid sample to be detected is 5-20mL:160 mg. In the method for detecting the content of the quaternary ammonium salt, preferably, in the step A, the mass ratio of the volume of the added oil solvent to the liquid sample to be detected is 5-15mL:160 mg.
In the method for detecting the content of quaternary ammonium salt, it is preferable that R in the structural formula of the active ingredient of the titrant A is1is-CH3or-CH2CH3，R2is-CH3or-CH2CH3，R3is-CH3or-CH2CH3，R4is-CH3or-CH2CH3. More preferably, the effective component of the titrant A is tetrabutylammonium bromide.
In the method for detecting the content of quaternary ammonium salt, the content of the active ingredient of the titrant a is preferably 0.01 to 0.1mol/L based on the volume of the titrant a.
In the method for detecting the content of quaternary ammonium salt, preferably, in the detection a, the determination of the content of quaternary ammonium salt in the water sample to be detected based on the usage amount of the titrant a and the usage amount of the sodium tetraphenylborate solution is performed by the following formula:
in the formula, c is the mass content of the quaternary ammonium salt in the water sample to be detected, and is 100 percent; n is a radical ofaThe molar concentration, mol/L, of the sodium tetraphenylborate in the sodium tetraphenylborate solution; vaThe dosage is mL of the sodium tetraphenylborate solution; n is a radical ofbIs the molar concentration, mol/L, of the effective components in the titrant A; vbThe dosage of titrant A is mL; w is the mass of the water sample to be detected, g; and n is the amount of quaternary ammonium cation substances contained in each mol of quaternary ammonium salt in the water sample to be detected.
In the method for detecting the content of quaternary ammonium salt, preferably, in the detection B, the model of the relationship between the absorbance and the concentration of quaternary ammonium salt is obtained by:
preparing each standard water sample: preparing at least two standard water samples with different quaternary ammonium salt concentrations; the quaternary ammonium salt in the standard water sample is the same as the quaternary ammonium salt in the water sample to be detected in kind;
and (3) obtaining the absorbance corresponding to each standard water sample: respectively mixing each standard water sample with an oil solvent, a bromothymol blue indicator and a buffer B, standing for layering, and separating to obtain an oil solvent layer liquid phase; wherein the oil solvent comprises chloroform and/or dichloromethane;
adding a boric acid alcohol solution into the liquid phase of each oil solvent layer, and measuring absorbance by using an ultraviolet-visible spectrophotometer to obtain the absorbance corresponding to each standard water sample;
determining by a relation model of absorbance and quaternary ammonium salt concentration: and determining a relational expression and/or a relational curve of the absorbance and the quaternary ammonium salt concentration as a relational model of the absorbance and the quaternary ammonium salt concentration based on the absorbance corresponding to each standard water sample and the quaternary ammonium salt concentration corresponding to each standard water sample.
In the detection method for the content of the quaternary ammonium salt, in the detection B, the buffer solution B provides a stable detection environment for a water sample to be detected. Preferably, the buffer solution B is used in an amount sufficient to keep the water sample to be tested in a neutral environment.
In the method for detecting the content of quaternary ammonium salt, it is preferable that in the detection B, the buffer B is a mixed aqueous solution of citric acid and disodium hydrogen phosphate; more preferably, buffer B has a pH of 7;
in a specific embodiment, the buffer solution B is obtained by mixing a citric acid solution with a citric acid content of 2.10% by mass (based on the total mass of the citric acid solution) and a disodium hydrogen phosphate solution with a disodium hydrogen phosphate content of 7.16% by mass (based on the total mass of the disodium hydrogen phosphate solution), wherein the volume ratio of the citric acid solution to the disodium hydrogen phosphate solution is 7.5: 92.5.
In the method for detecting the content of the quaternary ammonium salt, preferably, in the detection B, the volume ratio of the buffer solution B to the water sample to be detected is 10-50: 5.
In the method for detecting the content of the quaternary ammonium salt, the bromothymol blue indicator is preferably a mixed aqueous solution of bromothymol blue and sodium carbonate. In a specific embodiment, the mass concentration of bromothymol blue in the bromothymol blue indicator is 0.15% and the mass concentration of sodium carbonate is 0.15% based on the mass of the bromothymol blue indicator.
In the method for detecting the content of the quaternary ammonium salt, the volume ratio of the bromothymol blue indicator to a water sample to be detected is preferably 2-10: 5.
In the method for detecting the content of the quaternary ammonium salt, the boric acid alcohol solution is preferably prepared by dissolving boric acid in a mixed solution of absolute ethyl alcohol and distilled water. In one embodiment, the boric acid content is 0.02g/mL based on the volume of the boric acid alcohol solution; wherein the volume ratio of the water to the ethanol is 20: 240.
In the method for detecting the content of the quaternary ammonium salt, preferably, in the step B, the volume ratio of the added boric acid alcohol solution to the liquid sample to be detected is 1-20: 5.
In the method for detecting the content of the quaternary ammonium salt, preferably, in the step B, the volume ratio of the added oil solvent to the liquid sample to be detected is 5-50: 5.
In the method for detecting the content of the quaternary ammonium salt, preferably, the content of the quaternary ammonium salt in a water sample to be detected is pre-judged; when the quaternary ammonium salt content in the water sample to be detected is not lower than 1g/L through prejudgment, taking the water sample to be detected, and detecting A; when the quaternary ammonium salt content in the water sample to be detected is not higher than 0.1g/L through prejudgment, taking the water sample to be detected, and detecting B; and when the quaternary ammonium salt content in the water sample to be detected is smaller than 1g/L and larger than 0.1g/L through prejudgment, detecting the water sample B, and mixing the water sample to be detected diluted by a certain multiple with dichloromethane, bromothymol blue indicator and buffer B in the process of detecting the water sample B.
The method for detecting the content of the quaternary ammonium salt can quickly and conveniently realize the detection of the content of the quaternary ammonium salt in a water phase, and the technical scheme provided by the invention can realize the content test of the quaternary ammonium salt water samples with different concentrations.
Drawings
FIG. 1 is a graph of the absorbance versus the concentration of quaternary ammonium salt determined in example 3.
FIG. 2 is a graph of absorbance versus concentration of quaternary ammonium salt as determined in example 4.
FIG. 3 is a graph of absorbance versus concentration of quaternary ammonium salt as determined in example 5.
FIG. 4 is a graph of absorbance versus concentration of quaternary ammonium salt as determined in example 6.
Detailed Description
In order to more clearly illustrate the invention, the invention is further described below in connection with preferred embodiments. It is to be understood by persons skilled in the art that the following detailed description is illustrative and not restrictive, and is not to be taken as limiting the scope of the invention.
Example 1
The embodiment provides a method for detecting the content of quaternary ammonium salt, wherein the method comprises the following steps:
measuring 0.1611g of a water sample to be tested, putting the water sample into a 50mL beaker, adding 5mL of buffer solution (the buffer solution is obtained by mixing a sodium acetate solution with the sodium acetate content of 6.48g/L and an acetic acid solution with the acetic acid volume fraction of 0.48%, wherein the volume ratio of the sodium acetate solution to the acetic acid solution is 25:15) into the beaker, adding 30mL of sodium tetraphenylborate solution (the concentration of the sodium tetraphenylborate solution is 0.02N), generating a precipitate, and standing for 1 h;
filtering the product in the beaker after standing twice to remove precipitates until the filtrate is clear and not turbid; mixing the filtrate and washing liquid (liquid obtained by washing filter cake with deionized water and then performing suction filtration) and putting into a conical flask; to an Erlenmeyer flask was added 10mL of NaOH solution (0.1N concentration) and two drops of bromophenol blue indicator (about 0.1mL, bromophenol blue concentration in bromophenol blue indicator based on volume of bromophenol blue indicator was 5X 10-3g/L, NaOH concentration of 0.1mol/L) and 8mL of chloroform;
further performing titration by using tetrabutylammonium bromide solution (with the concentration of 0.02N) until the chloroform layer is colorless and transparent to generate light blue precipitate and the water layer is changed from light purple to sky blue to reach the titration end point; recording the usage amount of tetrabutylammonium bromide used;
determining the content of quaternary ammonium salt in a water sample to be detected by using the following formula based on the usage amount of tetrabutylammonium bromide solution and the usage amount of sodium tetraphenylborate solution:
in the formula, c is the mass content of the quaternary ammonium salt in the water sample to be detected, and is 100 percent; n is a radical ofaThe molar concentration, mol/L, of the sodium tetraphenylborate in the sodium tetraphenylborate solution; vaThe dosage is mL of the sodium tetraphenylborate solution; n is a radical ofbThe molar concentration of tetrabutylammonium bromide in the tetrabutylammonium bromide solution is mol/L; vbThe dosage is the using amount of tetrabutylammonium bromide solution, mL; w is the mass of the water sample to be detected, g; n is the amount of quaternary ammonium cation substances contained in each mol of quaternary ammonium salt in a water sample to be detected;
the amount of tetrabutylammonium bromide solution used was 8.2mL, and the quaternary ammonium salt content in the resulting solution was calculated to be 49.01%. The water sample to be detected used in this example is a hexamethonium bromide standard solution with a mass content of 50%. It can be seen that the error of the quaternary ammonium salt content detected by the detection method for quaternary ammonium salt content provided by the embodiment is 0.99%, and the accuracy is very high.
Example 2
The embodiment provides a method for detecting the content of quaternary ammonium salt, wherein the method comprises the following steps:
measuring 0.1628g of a water sample to be tested, putting the water sample into a 50mL beaker, adding 5mL of buffer solution (the buffer solution is obtained by mixing a sodium acetate solution with the sodium acetate content of 6.48g/L and an acetic acid solution with the acetic acid volume fraction of 0.48%, wherein the volume ratio of the sodium acetate solution to the acetic acid solution is 25:15), adding 30mL of sodium tetraphenylborate solution (the concentration of the sodium tetraphenylborate solution is 0.02N), generating precipitates, and standing for 1 h;
filtering the product in the beaker after standing twice to remove precipitates until the filtrate is clear and not turbid; mixing the filtrate and washing liquid (liquid obtained by washing filter cake with deionized water and then performing suction filtration) and putting into a conical flask; to an Erlenmeyer flask was added 10mL of NaOH solution (0.1N concentration) and two drops of bromophenol blue indicator (about 0.1mL, bromophenol blue concentration in bromophenol blue indicator based on volume of bromophenol blue indicator was 5X 10-3g/L, NaOH concentration of 0.1mol/L) and 8mL of chloroform;
further performing titration by using tetrabutylammonium bromide solution (with the concentration of 0.02N) until the chloroform layer is colorless and transparent to generate light blue precipitate and the water layer is changed from light purple to sky blue to reach the titration end point; recording the usage amount of tetrabutylammonium bromide used;
determining the content of quaternary ammonium salt in a water sample to be detected by using the following formula based on the usage amount of tetrabutylammonium bromide solution and the usage amount of sodium tetraphenylborate solution:
in the formula, c is the mass content of the quaternary ammonium salt in the water sample to be detected, and is 100 percent; n is a radical ofaThe molar concentration, mol/L, of the sodium tetraphenylborate in the sodium tetraphenylborate solution; vaThe dosage is mL of the sodium tetraphenylborate solution; n is a radical ofbThe molar concentration of tetrabutylammonium bromide in the tetrabutylammonium bromide solution is mol/L; vbIs a four-componentThe amount of the ammonium bromide solution used is mL; w is the mass of the water sample to be detected, g; n is the amount of quaternary ammonium cation substances contained in each mol of quaternary ammonium salt in a water sample to be detected;
the amount of tetrabutylammonium bromide solution used was 25.4mL, and the quaternary ammonium salt content in the resulting solution was calculated to be 10.23%. The water sample to be detected used in this example is a hexamethonium bromide standard solution with a mass content of 10%. It can be seen that the error of the quaternary ammonium salt content detected by the detection method for quaternary ammonium salt content provided by the embodiment is 0.23%, and the accuracy is very high.
Example 3
The embodiment provides a method for detecting the content of quaternary ammonium salt, wherein the method comprises the following steps:
1) obtaining a relation model between absorbance and quaternary ammonium salt concentration:
preparing a N, N, N, N ', N', N '-octamethyldiethylenetriammonium trimethy sulfate (DETAS) standard water sample with the concentrations of N, N, N, N', N ', N' -octamethyldiethylenetriammonium trimethy sulfate (DETAS) of 10, 20, 30, 40, 50 and 60mg/L respectively; the volume of each standard water sample is 5 mL;
taking 6 separating funnels, and respectively transferring each standard water sample to the corresponding separating funnel; adding 25mL of dichloromethane, 4mL of bromothymol blue indicator (the mass concentration of bromothymol blue in the bromothymol blue indicator is 0.15% and the mass concentration of sodium carbonate is 0.15% based on the mass of the bromothymol blue indicator) and 20mL of a buffer solution with the pH value of 7 (the buffer solution B is obtained by mixing a citric acid aqueous solution with the citric acid mass content of 2.10% (based on the total mass of the citric acid aqueous solution) and a disodium hydrogen phosphate aqueous solution with the disodium hydrogen phosphate mass content of 7.16% (based on the total mass of the disodium hydrogen phosphate aqueous solution), wherein the volume ratio of the citric acid aqueous solution to the disodium hydrogen phosphate aqueous solution is 7.5:92.5, shaking and standing for 10 min;
taking 6 conical flasks, plugging glass wool at the outlet of each separating funnel, opening the separating funnel to discharge a dichloromethane layer into the corresponding conical flask through the outlet of the funnel plugged with the glass wool, and collecting dichloromethane layer liquid phases in each conical flask respectively;
adding 3mL of a boric acid alcohol solution (obtained by mixing 5g of boric acid, 20mL of water and 225mL of ethanol) into each dichloromethane layer liquid phase, and measuring absorbance by using an ultraviolet-visible spectrophotometer to obtain the absorbance corresponding to each standard water sample; the results are shown in Table 1;
determining a relational expression and a relational curve of the absorbance and the quaternary ammonium salt concentration as a relational model of the absorbance and the quaternary ammonium salt concentration based on the absorbance corresponding to each standard water sample and the quaternary ammonium salt concentration corresponding to each standard water sample; the relation between the absorbance and the concentration of the quaternary ammonium salt is A ═ 0.0175c, wherein A is the absorbance, and c is the content of the quaternary ammonium salt, mg/L; the relationship between the absorbance and the concentration of the quaternary ammonium salt is shown in FIG. 1.
2) Taking 5mL of a water sample to be tested (the water sample to be tested used in the embodiment is 45mg/L of N, N, N, N ', N', N ", N", N "-octamethyldiethylenetriammonium trimethy sulfate standard solution), transferring the water sample to be tested into a corresponding separating funnel, adding 25mL of dichloromethane, 4mL of bromothymol blue indicator (the mass concentration of bromothymol blue in the bromothymol blue indicator is 0.15% and the mass concentration of sodium carbonate is 0.15% based on the mass of the bromothymol blue indicator) and 20mL of a buffer solution with pH value of 7 (the buffer solution B is obtained by mixing a citric acid aqueous solution with a citric acid mass content of 2.10% (based on the total mass of the citric acid aqueous solution) and a disodium hydrogen phosphate aqueous solution with a disodium hydrogen phosphate mass content of 7.16% (based on the total mass of the disodium hydrogen phosphate aqueous solution), wherein the volume ratio of the citric acid aqueous solution and the disodium hydrogen phosphate aqueous solution is 7.5:92.5), standing for 10min after shaking;
3) taking 1 conical flask, plugging glass wool at the outlet of the separating funnel, opening the separating funnel to discharge a dichloromethane layer into the conical flask through the funnel outlet plugged with the glass wool, and collecting a dichloromethane layer liquid phase in the conical flask;
4) adding 3mL of a boric acid alcohol solution (obtained by mixing 5g of boric acid, 20mL of water and 225mL of ethanol) into the dichloromethane layer liquid phase, and measuring absorbance by using an ultraviolet-visible spectrophotometer to obtain the absorbance corresponding to a water sample to be measured; the results are shown in Table 1;
5) determining the quaternary ammonium salt content in the water sample to be measured by means of the relationship model between the absorbance obtained in the step 1 and the quaternary ammonium salt concentration based on the measured absorbance corresponding to the water sample to be measured;
and measuring to obtain the corresponding absorbance of the water sample to be detected as 0.7882, and finally determining that the content of the quaternary ammonium salt in the water sample to be detected is 45.04 mg/L. The water sample to be tested used in this example is a standard solution of 45mg/L of N, N, N, N ', N', N ", N", N "-octamethyldiethylenetriammonium trimethy-L sulfate. It can be seen that the method for detecting the content of the quaternary ammonium salt provided by the embodiment has very high accuracy.
TABLE 1
| Determination of concentration (mg/L) | 0 | 10 | 20 | 30 | 40 | 50 | 60 | 45 (Water sample to be measured) |
| |
0 | 0.1807 | 0.383 | 0.322 | 0.443 | 0.552 | 0.628 | 0.7882 |
Example 4
The embodiment provides a method for detecting the content of quaternary ammonium salt, wherein the method comprises the following steps:
1) obtaining a relation model between absorbance and quaternary ammonium salt concentration:
preparing N, N, N, N ', N', N '-hexamethyl propane diammonium dimethylsulfate standard water samples with the concentrations of N, N, N, N', N ', N' -hexamethyl propane diammonium dimethylsulfate of 10, 20, 30, 40, 50 and 60mg/L respectively; the volume of each standard water sample is 5 mL;
taking 6 separating funnels, and respectively transferring each standard water sample to the corresponding separating funnel; adding 25mL of dichloromethane, 4mL of bromothymol blue indicator (the mass concentration of bromothymol blue in the bromothymol blue indicator is 0.15% and the mass concentration of sodium carbonate is 0.15% based on the mass of the bromothymol blue indicator) and 20mL of a buffer solution with the pH value of 7 (the buffer solution B is obtained by mixing a citric acid aqueous solution with the citric acid mass content of 2.10% (based on the total mass of the citric acid aqueous solution) and a disodium hydrogen phosphate aqueous solution with the disodium hydrogen phosphate mass content of 7.16% (based on the total mass of the disodium hydrogen phosphate aqueous solution), wherein the volume ratio of the citric acid aqueous solution to the disodium hydrogen phosphate aqueous solution is 7.5:92.5, shaking and standing for 10 min;
taking 6 conical flasks, plugging glass wool at the outlet of each separating funnel, opening the separating funnel to discharge a dichloromethane layer into the corresponding conical flask through the outlet of the funnel plugged with the glass wool, and collecting dichloromethane layer liquid phases in each conical flask respectively;
adding 3mL of a boric acid alcohol solution (obtained by mixing 5g of boric acid, 20mL of water and 225mL of ethanol) into each dichloromethane layer liquid phase, and measuring absorbance by using an ultraviolet-visible spectrophotometer to obtain the absorbance corresponding to each standard water sample; the results are shown in Table 2;
determining a relational expression and a relational curve of the absorbance and the quaternary ammonium salt concentration as a relational model of the absorbance and the quaternary ammonium salt concentration based on the absorbance corresponding to each standard water sample and the quaternary ammonium salt concentration corresponding to each standard water sample; the relation between the absorbance and the concentration of the quaternary ammonium salt is A ═ 0.0091c-0.0122, wherein A is the absorbance, and c is the content of the quaternary ammonium salt in mg/L; the relationship between the absorbance and the concentration of the quaternary ammonium salt is shown in FIG. 2.
2) A sample of 5mL of water to be tested (45 mg/L of standard solution of N, N' -hexamethyl propane diammonium dimethylsulfate used in this example) was transferred to a corresponding separatory funnel, 25mL of dichloromethane, 4mL of bromothymol blue indicator (the mass concentration of bromothymol blue is 0.15% and the mass concentration of sodium carbonate is 0.15% in the bromothymol blue indicator based on the mass of the bromothymol blue indicator) and 20mL of buffer solution with pH of 7 (the buffer solution B was obtained by mixing an aqueous citric acid solution with a citric acid mass content of 2.10% (based on the total mass of the aqueous citric acid solution) and an aqueous disodium hydrogen phosphate solution with a disodium hydrogen phosphate mass content of 7.16% (based on the total mass of the aqueous disodium hydrogen phosphate solution) were added to the sample to be tested, wherein the volume ratio of the aqueous citric acid solution to the aqueous disodium hydrogen phosphate solution was 7.5:92.5), standing for 10min after shaking;
3) taking 1 conical flask, plugging glass wool at the outlet of the separating funnel, opening the separating funnel to discharge a dichloromethane layer into the conical flask through the funnel outlet plugged with the glass wool, and collecting a dichloromethane layer liquid phase in the conical flask;
4) adding 3mL of a boric acid alcohol solution (obtained by mixing 5g of boric acid, 20mL of water and 225mL of ethanol) into the dichloromethane layer liquid phase, and measuring absorbance by using an ultraviolet-visible spectrophotometer to obtain the absorbance corresponding to a water sample to be measured; the results are shown in Table 2;
5) determining the quaternary ammonium salt content in the water sample to be measured by means of the relationship model between the absorbance obtained in the step 1 and the quaternary ammonium salt concentration based on the measured absorbance corresponding to the water sample to be measured;
and measuring to obtain the corresponding absorbance of the water sample to be detected as 0.3999, and finally determining that the content of the quaternary ammonium salt in the water sample to be detected is 45.29 mg/L. The water sample to be detected used in this example is a 45mg/L standard solution of N, N' -hexamethyl propane diammonium dimethylsulfate. It can be seen that the method for detecting the content of the quaternary ammonium salt provided by the embodiment has very high accuracy.
TABLE 2
| Determination of concentration (mg/L) | 0 | 10 | 20 | 30 | 40 | 50 | 60 | 45 (liquid sample to be measured) |
| |
0 | 0.06 | 0.166 | 0.276 | 0.347 | 0.444 | 0.534 | 0.3999 |
Example 5
The embodiment provides a method for detecting the content of quaternary ammonium salt, wherein the method comprises the following steps:
1) obtaining a relation model between absorbance and quaternary ammonium salt concentration:
preparing N, N, N, N ', N', N '-hexamethyl butanediamine dimethyl sulfate standard water samples with the concentrations of N, N, N, N', N ', N' -hexamethyl butanediamine dimethyl sulfate being 10, 20, 30, 40, 50 and 60mg/L respectively; the volume of each standard water sample is 5 mL;
taking 6 separating funnels, and respectively transferring each standard water sample to the corresponding separating funnel; adding 25mL of dichloromethane, 4mL of bromothymol blue indicator (the mass concentration of bromothymol blue in the bromothymol blue indicator is 0.15% and the mass concentration of sodium carbonate is 0.15% based on the mass of the bromothymol blue indicator) and 20mL of a buffer solution with the pH value of 7 (the buffer solution B is obtained by mixing a citric acid aqueous solution with the citric acid mass content of 2.10% (based on the total mass of the citric acid aqueous solution) and a disodium hydrogen phosphate aqueous solution with the disodium hydrogen phosphate mass content of 7.16% (based on the total mass of the disodium hydrogen phosphate aqueous solution), wherein the volume ratio of the citric acid aqueous solution to the disodium hydrogen phosphate aqueous solution is 7.5:92.5, shaking and standing for 10 min;
taking 6 conical flasks, plugging glass wool at the outlet of each separating funnel, opening the separating funnel to discharge a dichloromethane layer into the corresponding conical flask through the outlet of the funnel plugged with the glass wool, and collecting dichloromethane layer liquid phases in each conical flask respectively;
adding 3mL of a boric acid alcohol solution (obtained by mixing 5g of boric acid, 20mL of water and 225mL of ethanol) into each dichloromethane layer liquid phase, and measuring absorbance by using an ultraviolet-visible spectrophotometer to obtain the absorbance corresponding to each standard water sample; the results are shown in Table 3;
determining a relational expression and a relational curve of the absorbance and the quaternary ammonium salt concentration as a relational model of the absorbance and the quaternary ammonium salt concentration based on the absorbance corresponding to each standard water sample and the quaternary ammonium salt concentration corresponding to each standard water sample; the relation between the absorbance and the concentration of the quaternary ammonium salt is A ═ 0.0092c-0.003, wherein A is the absorbance, and c is the content of the quaternary ammonium salt in mg/L; the relationship between the absorbance and the concentration of the quaternary ammonium salt is shown in FIG. 3.
2) A sample of 5mL of a sample to be tested (the sample to be tested used in this example was a standard solution of 45mg/L of N, N' -hexamethyl-butanediamine dimethyl sulfate) was transferred to a corresponding separatory funnel, and 25mL of dichloromethane, 4mL of bromothymol blue indicator (the mass concentration of bromothymol blue was 0.15% and the mass concentration of sodium carbonate was 0.15% in the bromothymol blue indicator based on the mass of the bromothymol blue indicator), and 20mL of a buffer solution having a pH of 7 (the buffer solution B was obtained by mixing a citric acid aqueous solution having a citric acid mass content of 2.10% (based on the total mass of the citric acid aqueous solution) with a disodium hydrogen phosphate aqueous solution having a disodium hydrogen phosphate mass content of 7.16% (based on the total mass of the disodium hydrogen phosphate aqueous solution), wherein the volume ratio of the citric acid aqueous solution to the disodium hydrogen phosphate aqueous solution was 7.5:92.5) were added to the sample to be tested, standing for 10min after shaking;
3) taking 1 conical flask, plugging glass wool at the outlet of the separating funnel, opening the separating funnel to discharge a dichloromethane layer into the conical flask through the funnel outlet plugged with the glass wool, and collecting a dichloromethane layer liquid phase in the conical flask;
4) adding 3mL of a boric acid alcohol solution (obtained by mixing 5g of boric acid, 20mL of water and 225mL of ethanol) into the dichloromethane layer liquid phase, and measuring absorbance by using an ultraviolet-visible spectrophotometer to obtain the absorbance corresponding to a water sample to be measured; the results are shown in Table 3;
5) determining the quaternary ammonium salt content in the water sample to be measured by means of the relationship model between the absorbance obtained in the step 1 and the quaternary ammonium salt concentration based on the measured absorbance corresponding to the water sample to be measured; and measuring to obtain the corresponding absorbance of the water sample to be detected as 0.403, and finally determining that the content of the quaternary ammonium salt in the water sample to be detected is 44.13 mg/L. The water sample to be tested used in this example was a 45mg/L standard solution of N, N, N, N ', N ', N ' -hexamethyl butanediamine dimethyl sulfate. It can be seen that the method for detecting the content of the quaternary ammonium salt provided by the embodiment has very high accuracy.
TABLE 3
| Determination of concentration (mg/L) | 0 | 10 | 20 | 30 | 40 | 50 | 60 | 45 (Water sample to be measured) |
| |
0 | 0.082 | 0.172 | 0.289 | 0.353 | 0.47 | 0.538 | 0.403 |
Example 6
The embodiment provides a method for detecting the content of quaternary ammonium salt, wherein the method comprises the following steps:
1) obtaining a relation model between absorbance and quaternary ammonium salt concentration:
preparing N, N, N, N ', N', N '-hexamethyl hexamethylene diammonium dimethylsulfate standard water samples with the concentrations of N, N, N, N', N ', N' -hexamethyl hexamethylene diammonium dimethylsulfate of 10, 20, 30, 40, 50 and 60mg/L respectively; the volume of each standard water sample is 5 mL;
taking 6 separating funnels, and respectively transferring each standard water sample to the corresponding separating funnel; adding 25mL of dichloromethane, 4mL of bromothymol blue indicator (the mass concentration of bromothymol blue in the bromothymol blue indicator is 0.15% and the mass concentration of sodium carbonate is 0.15% based on the mass of the bromothymol blue indicator) and 20mL of a buffer solution with the pH value of 7 (the buffer solution B is obtained by mixing a citric acid aqueous solution with the citric acid mass content of 2.10% (based on the total mass of the citric acid aqueous solution) and a disodium hydrogen phosphate aqueous solution with the disodium hydrogen phosphate mass content of 7.16% (based on the total mass of the disodium hydrogen phosphate aqueous solution), wherein the volume ratio of the citric acid aqueous solution to the disodium hydrogen phosphate aqueous solution is 7.5:92.5, shaking and standing for 10 min;
taking 6 conical flasks, plugging glass wool at the outlet of each separating funnel, opening the separating funnel to discharge a dichloromethane layer into the corresponding conical flask through the outlet of the funnel plugged with the glass wool, and collecting dichloromethane layer liquid phases in each conical flask respectively;
adding 3mL of a boric acid alcohol solution (obtained by mixing 5g of boric acid, 20mL of water and 225mL of ethanol) into each dichloromethane layer liquid phase, and measuring absorbance by using an ultraviolet-visible spectrophotometer to obtain the absorbance corresponding to each standard water sample; the results are shown in Table 4;
determining a relational expression and a relational curve of the absorbance and the quaternary ammonium salt concentration as a relational model of the absorbance and the quaternary ammonium salt concentration based on the absorbance corresponding to each standard water sample and the quaternary ammonium salt concentration corresponding to each standard water sample; the relation between the absorbance and the concentration of the quaternary ammonium salt is A ═ 0.0108c-0.0047, wherein A is the absorbance, and c is the content of the quaternary ammonium salt in mg/L; the relationship between the absorbance and the concentration of the quaternary ammonium salt is shown in FIG. 4.
2) A sample of 5mL of a sample to be tested (the sample to be tested used in this example is a standard solution of 45mg/L of N, N' -hexamethyl hexamethylene diammonium dimethylsulfate) was transferred to a corresponding separatory funnel, 25mL of dichloromethane, 4mL of bromothymol blue indicator (the mass concentration of bromothymol blue is 0.15% and the mass concentration of sodium carbonate is 0.15% in the bromothymol blue indicator based on the mass of the bromothymol blue indicator), and 20mL of a buffer solution with a pH of 7 (the buffer solution B was obtained by mixing a citric acid aqueous solution with a citric acid mass content of 2.10% (based on the total mass of the citric acid aqueous solution) and a disodium hydrogen phosphate aqueous solution with a disodium hydrogen phosphate mass content of 7.16% (based on the total mass of the disodium hydrogen phosphate aqueous solution), wherein the volume ratio of the citric acid aqueous solution to the disodium hydrogen phosphate aqueous solution was 7.5:92.5), standing for 10min after shaking;
3) taking 1 conical flask, plugging glass wool at the outlet of the separating funnel, opening the separating funnel to discharge a dichloromethane layer into the conical flask through the funnel outlet plugged with the glass wool, and collecting a dichloromethane layer liquid phase in the conical flask;
4) adding 3mL of a boric acid alcohol solution (obtained by mixing 5g of boric acid, 20mL of water and 225mL of ethanol) into the dichloromethane layer liquid phase, and measuring absorbance by using an ultraviolet-visible spectrophotometer to obtain the absorbance corresponding to a water sample to be measured; the results are shown in Table 4;
5) determining the quaternary ammonium salt content in the water sample to be measured by means of the relationship model between the absorbance obtained in the step 1 and the quaternary ammonium salt concentration based on the measured absorbance corresponding to the water sample to be measured;
and measuring to obtain the corresponding absorbance of the water sample to be detected as 0.4808, and finally determining that the content of the quaternary ammonium salt in the water sample to be detected is 44.95 mg/L. The water sample to be detected used in this example is a 45mg/L standard solution of N, N' -hexamethyl hexamethylene diammonium dimethylsulfate. It can be seen that the method for detecting the content of the quaternary ammonium salt provided by the embodiment has very high accuracy.
TABLE 4
| Determination of concentration (mg/L) | 0 | 10 | 20 | 30 | 40 | 50 | 60 | 45 (Water sample to be measured) |
| |
0 | 0.096 | 0.204 | 0.322 | 0.443 | 0.552 | 0.628 | 0.4808 |
It should be understood that the above-mentioned embodiments of the present invention are only examples for clearly illustrating the present invention, and are not intended to limit the embodiments of the present invention, and it will be obvious to those skilled in the art that other variations or modifications may be made on the basis of the above description, and all embodiments may not be exhaustive, and all obvious variations or modifications may be included within the scope of the present invention.
Claims (10)
1. A method for detecting the content of quaternary ammonium salt comprises the following steps:
taking a water sample to be detected for detection A; if the quaternary ammonium salt content in the water sample to be detected cannot be determined, selectively taking the water sample to be detected to detect B;
or;
taking a water sample to be detected for detection B; if the quaternary ammonium salt content in the water sample to be detected cannot be determined, selectively taking the water sample to be detected to detect A;
wherein detecting a comprises:
mixing a water sample to be detected with a buffer solution A to obtain a mixed solution with the pH value of 4-5, adding a sodium tetraphenylborate solution to react fully, removing a precipitate, and adding NaOH, a bromophenol blue indicator and an oil solvent; wherein the oil solvent comprises chloroform and/or dichloromethane; the added amount of the sodium hydroxide can realize the complete dissolution of the added bromophenol blue indicator;
further carrying out titration by using a titrant A until a light blue precipitate appears in an oil solvent layer and an aqueous phase layer becomes sky blue, and reaching a titration end point; recording the usage amount of the titrant A; wherein the effective component of the titrant A has a structural formula
A compound of (1), R1、R2、R3、R4Is alkyl, X is selected from one of F, Cl, Br and I;
determining the content of quaternary ammonium salt in a water sample to be detected based on the usage amount of the titrant A and the usage amount of the sodium tetraphenylborate solution;
wherein detecting B comprises:
mixing a water sample to be detected or a water sample diluted by a certain multiple with an oil solvent, a bromothymol blue indicator and a buffer B, standing for layering, and separating to obtain an oil solvent layer liquid phase; wherein the oil solvent comprises chloroform and/or dichloromethane;
adding a boric acid alcohol solution into the oil solvent layer liquid phase, and measuring absorbance by using an ultraviolet-visible spectrophotometer;
and determining the quaternary ammonium salt content in the water sample to be detected by means of a relation model between the absorbance and the quaternary ammonium salt concentration based on the measured absorbance.
2. The detection method according to claim 1, wherein the buffer solution A comprises one or a combination of two or more of a mixed aqueous solution of acetic acid and sodium acetate, a sodium citrate buffer solution and a sodium phosphate buffer solution;
preferably, in the detection A, the volume ratio of the buffer solution A to the water sample to be detected is 30-120: 1.
3. The detection method according to claim 1,
the concentration of the sodium tetraphenylborate solution is 0.01-0.05N; preferably, the mass ratio of the volume usage of the sodium tetraphenylborate solution to the liquid sample to be detected is 10-50mL:160 mg;
the bromophenol blue indicator is a mixed aqueous solution of bromophenol blue and sodium hydroxide;
the mass ratio of the volume of the added oil solvent to the liquid sample to be detected is 5-15mL:160 mg.
4. The detection method according to claim 1, wherein R in the structural formula of the active ingredient of the titrant A1is-CH3or-CH2CH3，R2is-CH3or-CH2CH3，R3is-CH3or-CH2CH3，R4is-CH3or-CH2CH3；
Preferably, the effective component of the titrant A is tetrabutylammonium bromide.
5. The detection method according to any one of claims 1 to 4, wherein in the detection A, the determination of the content of the quaternary ammonium salt in the water sample to be detected based on the usage amount of the titrant A and the usage amount of the sodium tetraphenylborate solution is performed by the following formula:
in the formula, c is the mass content of the quaternary ammonium salt in the water sample to be detected, and is 100 percent; n is a radical ofaThe molar concentration, mol/L, of the sodium tetraphenylborate in the sodium tetraphenylborate solution; vaIs sodium tetraphenylborateAmount of liquid, mL; n is a radical ofbIs the molar concentration, mol/L, of the effective components in the titrant A; vbThe dosage of titrant A is mL; w is the mass of the water sample to be detected, g; and n is the amount of quaternary ammonium cation substances contained in each mol of quaternary ammonium salt in the water sample to be detected.
6. The detection method according to claim 1, wherein the model of the relationship between absorbance and quaternary ammonium salt concentration is obtained by:
preparing each standard water sample: preparing at least two standard water samples with different quaternary ammonium salt concentrations; the quaternary ammonium salt in the standard water sample is the same as the quaternary ammonium salt in the water sample to be detected in kind;
and (3) obtaining the absorbance corresponding to each standard water sample: respectively mixing each standard water sample with an oil solvent, a bromothymol blue indicator and a buffer B, standing for layering, and separating to obtain an oil solvent layer liquid phase; adding a boric acid alcohol solution into the liquid phase of each oil solvent layer, and measuring absorbance by using an ultraviolet-visible spectrophotometer to obtain the absorbance corresponding to each standard water sample;
determining by a relation model of absorbance and quaternary ammonium salt concentration: and determining a relational expression and/or a relational curve of the absorbance and the quaternary ammonium salt concentration as a relational model of the absorbance and the quaternary ammonium salt concentration based on the absorbance corresponding to each standard water sample and the quaternary ammonium salt concentration corresponding to each standard water sample.
7. The detection method according to claim 1 or 6, wherein in the detection B, the buffer B is a mixed aqueous solution of citric acid and disodium hydrogen phosphate;
preferably, in the detection B, the volume ratio of the buffer solution B to the water sample to be detected is 10-50: 5.
8. The detection method according to claim 1 or 7, wherein the bromothymol blue indicator is a mixed aqueous solution of bromothymol blue and sodium carbonate;
preferably, the volume ratio of the bromothymol blue indicator to the water sample to be detected is 2-10: 5;
preferably, the mass concentration of bromothymol blue in the bromothymol blue indicator is 0.15% and the mass concentration of sodium carbonate is 0.15% based on the mass of the bromothymol blue indicator.
9. The detection method according to claim 1 or 7, wherein the boric acid alcohol solution is prepared by dissolving boric acid in a mixed solution of absolute ethyl alcohol and distilled water;
preferably, in the detection B, the volume ratio of the added boric acid alcohol solution to the liquid sample to be detected is 1-20: 5;
preferably, in the detection B, the content of the boric acid is 0.02g/mL by taking the volume of the boric acid alcohol solution as a reference; wherein the volume ratio of the water to the ethanol is 20: 240.
10. The detection method according to claim 1 or 7, wherein in the detection B, the volume ratio of the added oil solvent to the liquid sample to be detected is 5-50: 5.
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