WO1993004368A1 - Specific measurement of organic chlorides - Google Patents
Specific measurement of organic chlorides Download PDFInfo
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- WO1993004368A1 WO1993004368A1 PCT/US1992/006791 US9206791W WO9304368A1 WO 1993004368 A1 WO1993004368 A1 WO 1993004368A1 US 9206791 W US9206791 W US 9206791W WO 9304368 A1 WO9304368 A1 WO 9304368A1
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- Prior art keywords
- fujiwara
- chemistry
- pyridine
- reaction product
- hydroxide
- Prior art date
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- 150000001805 chlorine compounds Chemical class 0.000 title abstract description 13
- 238000005259 measurement Methods 0.000 title abstract description 10
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims abstract description 54
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims abstract description 27
- 239000007795 chemical reaction product Substances 0.000 claims abstract description 22
- 238000010521 absorption reaction Methods 0.000 claims abstract description 19
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims abstract description 18
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 24
- 238000000034 method Methods 0.000 claims description 20
- VDZOOKBUILJEDG-UHFFFAOYSA-M tetrabutylammonium hydroxide Chemical compound [OH-].CCCC[N+](CCCC)(CCCC)CCCC VDZOOKBUILJEDG-UHFFFAOYSA-M 0.000 claims description 17
- XSTXAVWGXDQKEL-UHFFFAOYSA-N Trichloroethylene Chemical group ClC=C(Cl)Cl XSTXAVWGXDQKEL-UHFFFAOYSA-N 0.000 claims description 16
- WGTYBPLFGIVFAS-UHFFFAOYSA-M tetramethylammonium hydroxide Chemical group [OH-].C[N+](C)(C)C WGTYBPLFGIVFAS-UHFFFAOYSA-M 0.000 claims description 16
- QPFMBZIOSGYJDE-UHFFFAOYSA-N 1,1,2,2-tetrachloroethane Chemical compound ClC(Cl)C(Cl)Cl QPFMBZIOSGYJDE-UHFFFAOYSA-N 0.000 claims description 14
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 claims description 14
- UBOXGVDOUJQMTN-UHFFFAOYSA-N trichloroethylene Natural products ClCC(Cl)Cl UBOXGVDOUJQMTN-UHFFFAOYSA-N 0.000 claims description 14
- 239000000203 mixture Substances 0.000 claims description 10
- UOCLXMDMGBRAIB-UHFFFAOYSA-N 1,1,1-trichloroethane Chemical compound CC(Cl)(Cl)Cl UOCLXMDMGBRAIB-UHFFFAOYSA-N 0.000 claims description 9
- 238000002835 absorbance Methods 0.000 claims description 9
- LPSKDVINWQNWFE-UHFFFAOYSA-M tetrapropylazanium;hydroxide Chemical compound [OH-].CCC[N+](CCC)(CCC)CCC LPSKDVINWQNWFE-UHFFFAOYSA-M 0.000 claims description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 claims description 5
- 239000000908 ammonium hydroxide Substances 0.000 claims description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 4
- UKDOTCFNLHHKOF-FGRDZWBJSA-N (z)-1-chloroprop-1-ene;(z)-1,2-dichloroethene Chemical group C\C=C/Cl.Cl\C=C/Cl UKDOTCFNLHHKOF-FGRDZWBJSA-N 0.000 claims description 3
- 239000007864 aqueous solution Substances 0.000 claims description 3
- ROFVEXUMMXZLPA-UHFFFAOYSA-N Bipyridyl Chemical compound N1=CC=CC=C1C1=CC=CC=N1 ROFVEXUMMXZLPA-UHFFFAOYSA-N 0.000 claims description 2
- 150000003222 pyridines Chemical class 0.000 claims description 2
- 125000001453 quaternary ammonium group Chemical group 0.000 claims 3
- 229930195733 hydrocarbon Natural products 0.000 description 11
- 150000002430 hydrocarbons Chemical class 0.000 description 11
- 238000007212 Fujiwara reaction Methods 0.000 description 9
- 239000004215 Carbon black (E152) Substances 0.000 description 8
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 6
- 239000002585 base Substances 0.000 description 5
- 239000003054 catalyst Substances 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 5
- HEMHJVSKTPXQMS-UHFFFAOYSA-M sodium hydroxide Inorganic materials [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 5
- 239000000243 solution Substances 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical compound ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 description 3
- 238000001514 detection method Methods 0.000 description 3
- 230000005284 excitation Effects 0.000 description 3
- 239000000835 fiber Substances 0.000 description 3
- 239000003444 phase transfer catalyst Substances 0.000 description 3
- 230000035945 sensitivity Effects 0.000 description 3
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 238000001506 fluorescence spectroscopy Methods 0.000 description 2
- 238000009472 formulation Methods 0.000 description 2
- 150000008282 halocarbons Chemical class 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- JKMPXGJJRMOELF-UHFFFAOYSA-N 1,3-thiazole-2,4,5-tricarboxylic acid Chemical compound OC(=O)C1=NC(C(O)=O)=C(C(O)=O)S1 JKMPXGJJRMOELF-UHFFFAOYSA-N 0.000 description 1
- WOXFMYVTSLAQMO-UHFFFAOYSA-N 2-Pyridinemethanamine Chemical compound NCC1=CC=CC=N1 WOXFMYVTSLAQMO-UHFFFAOYSA-N 0.000 description 1
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical group [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- 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 description 1
- QQUBTMNKDXGWKY-UHFFFAOYSA-N [Cl].ClC(Cl)Cl Chemical compound [Cl].ClC(Cl)Cl QQUBTMNKDXGWKY-UHFFFAOYSA-N 0.000 description 1
- 238000011481 absorbance measurement Methods 0.000 description 1
- 238000000862 absorption spectrum Methods 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 235000011114 ammonium hydroxide Nutrition 0.000 description 1
- 229940043379 ammonium hydroxide Drugs 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 230000000711 cancerogenic effect Effects 0.000 description 1
- 231100000315 carcinogenic Toxicity 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 238000004737 colorimetric analysis Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- PFBUKDPBVNJDEW-UHFFFAOYSA-N dichlorocarbene Chemical class Cl[C]Cl PFBUKDPBVNJDEW-UHFFFAOYSA-N 0.000 description 1
- 230000009977 dual effect Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 231100001261 hazardous Toxicity 0.000 description 1
- 239000013067 intermediate product Substances 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 230000003595 spectral effect Effects 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
Classifications
-
- 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
- G01N21/62—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light
- G01N21/63—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light optically excited
- G01N21/64—Fluorescence; Phosphorescence
- G01N21/6428—Measuring fluorescence of fluorescent products of reactions or of fluorochrome labelled reactive substances, e.g. measuring quenching effects, using measuring "optrodes"
-
- 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
- G01N31/22—Investigating or analysing non-biological materials by the use of the chemical methods specified in the subgroup; Apparatus specially adapted for such methods using chemical indicators
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N33/00—Investigating or analysing materials by specific methods not covered by groups G01N1/00 - G01N31/00
- G01N33/18—Water
- G01N33/1826—Organic contamination in water
-
- 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
- G01N21/75—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
- G01N2021/7769—Measurement method of reaction-produced change in sensor
- G01N2021/7786—Fluorescence
Definitions
- the invention relates generally to the chemical detection of halogenated hydrocarbons using the Fujiwara reaction and more particularly to the selective detection of certain organic chlorides.
- Trichloroethylene heads theU.S. Environmental Protection Agency's (EPA) list of hazardous (toxic, carcinogenic, etc.) compounds and the organic chlorides, as a group, dominate the ten (10) most frequently found dangerous compounds.
- the other organic chlorides include 1,1,1- trichloroethane (TCA) , 1,1,2,2-tetrachloroethane, chloroform (CC£ 3 ) , carbon tetrachloride (CC£ 4 ) , and 1,2-dichloroethylene (DCE) .
- the Fujiwara reaction is a known methodology widely used for the fluorometric and colorimetric analysis of gem- polyhalogen compounds.
- a strong alkali such as sodium or potassium hydroxide
- pyridine or a derivative thereof reacts with a halogenated hydrocarbon to produce a red colored fluorescent product.
- the traditional chemistry pyridine/base
- pyridine is insoluble in water with the commonly used alkalis (NaOH or KOH) . Therefore, the reaction product is formed only at the interface.
- the Fujiwara chemistry has been modified to overcome the limitations of the two-phase system.
- a single-phase system utilizes pyridine or a derivative thereof with a hindered nitrogen base (phase transfer catalyst) .
- U.S. Patents 4,666,672 issued May 19, 1987 and
- Anderson (deceased), et al. shows method and apparatus for detecting gem-polyhalogenated hydrocarbons using a single- phase Fujiwara reaction.
- the modified Fujiwara chemistry is pyridine or its derivative with a hindered nitrogen base, e.g. tetra(methyl, butyl or propyl) a ⁇ mionium hydroxide. Fluorescence and/or absorbance measurements relate to hydrocarbon concentration.
- EPA Report EPA/600/X-87/467 Part VI (Dec. 1987) describes the Fujiwara reaction for detection of organic chlorides. TCE and chloroform are detected using 2- (aminomethyl)pyridine. As suggested at p.
- TCE is selectively monitored in the presence of chloroform by selectively separating the intermediate product chloroform- derived dichlorocarbene. Fluorescence is measured when the reaction mixture is irradiated at 350 nm (UV) . To shift this excitation wavelength to a lower energy, auxochromes are attached to the pyridine (p. 11) . Lockheed Fiber Optic Chemical Sensor Project - Final
- LLNL Phase II Final Report to DOE (Sept. 1989) describes optrodes for TCE and chloroform, including fluorescence and absorption-based sensors.
- a dual wavelength absorption optrode measures absorption at 530 nm by the colored reaction product, with an internal reference provided by measuring unattenuated light at 610 nm.
- the optrode reagents are different for chloroform: 87.5 v. % pyridine, 12.5% tetrabutylammonium hydroxide (TBAH) (40% aqueous solution), and for TCE: 99 v. % pyridine, 1% TBAH solution.
- the absorption spectra for TCE and chloroform are different.
- the fluorescence sensor has been supplanted by the absorption sensor.
- a method of selectively detecting and identifying a particular organic chloride species in a sample comprising: reacting the sample with a Fujiwara chemistry to form a reaction product, the Fujiwara chemistry being selected to enhance color and specificity of the reaction product of the particular organic chloride species; measuring at least one of an absorbance peak of the reaction product at a preselected first wavelength and fluorescence peak of the reaction product when excited at a preselected second wavelength; comparing the measured absorbance and fluorescence peaks of the reaction product to predetermined values of absorbance and fluorescence peaks at the preselected wavelengths for the reaction product of the selected Fujiwara chemistry and the particular organic chloride species.
- the invention may provide a method of selecting between each of various organic chlorides using a modified Fujiwara reaction.
- the method may spectrally sort the reactions of various organic chlorides with a modified Fujiwara chemistry.
- a method of the invention can preferably distinguish between TCE, chloroform, TCA, carbon tetrachloride, tetrachloroethane and dichloroethylene using a modified Fujiwara reaction.
- the method may select a suitable composition for a modified Fujiwara chemistry and spectrally sorts the reaction products of the selected chemistry with TCE, chloroform, TCA, carbon tetrachloride, tetrachloroethane and dichloroethylene.
- the invention is preferably a method for detecting and identifying each of various organic chlorides using a modified Fujiwara reaction which selectively identifies each particular organic chloride.
- the composition of the Fujiwara chemistry has a significant effect on the characteristics of the colored reaction product with respect to wavelength and absorption.
- a chromophoric-enhancing and species-selective, modified Fujiwara chemistry may be obtained by varying the pyridine, base and water composition and ratios to optimize the results for a particular organic chloride.
- absorption and fluorescence measurements further identify a particular organic chloride by comparing to reference values which have been measured for known samples.
- the invention is a method of selectively measuring the presence of each of a group of gem-polyhalogenated hydrocarbons in a sample using a modified Fujiwara chemistry which has been formulated to enhance the color of the Fujiwara reaction products obtained for the particular hydrocarbon.
- the method is further carried out by measuring the absorption and fluorescence peaks of the sample reaction products and comparing the measured values to a previously determined set of reference values.
- the reference values of absorption and fluorescence peaks for each species of hydrocarbon in the group are determined by reacting a known sample of the species with a modified Fujiwara chemistry with the selected formulation for that particular hydrocarbon. The same selected chemistry is used to test the unknown sample.
- the absorbance and fluorescence reference values of the hydrocarbon species can be compiled into a lookup table, as a function of the chemistry composition for comparison with the measured data. Similar measurements can be performed using different Fujiwara chemistries for each hydrocarbon so that the presence of each hydrocarbon can be tested.
- the invention is described with respect to the following group of gem-polyhalogenated hydrocarbons: trichloroethylene (TCE) , chloroform, carbon tetrachloride, 1,1,1-trichloroethane (TCA) ,1,1,2,2-tetrachloroethane, and 1,2-dichloroethylene.
- the principles of the invention can be carried out to add other species to the group, or for a group of different species, by modifying the Fujiwara chemistry composition to respond to each of the species and by establishing a baseline of colorimetric, absorption and fluorescence data for known samples of each species, and comparing measured values for an unknown sample against the baseline.
- a color and sensitivity enhancing modified Fujiwara chemistry is selected for each species.
- the composition can be varied in terms of using pyridine or a derivative thereof, choosing 5 the phase transfer catalyst (base) , and choosing the ratio thereof. By the proper choice, the development of color and sensitivity are significantly enhanced.
- Pyridine is preferred; 2,2 bipyridine or other pyridine derivatives can also be used.
- the phase transfer catalyst is preferably a
- quaternary ammoniumhydroxide selected fromtetrabutylammonium hydroxide (TBAH) , tetramethylammonium hydroxide (TMAH) , tetraethyla monium hydroxide (TEAH) , and tetrapropylammonium hydroxide (TPAH) , with TBAH most preferred.
- the catalyst is preferably in an aqueous solution, with 30 to 14 wt. % water.
- the ratio of pyridine to catalyst solution is preferably as low as 60 v. % pyridine to 40 v. % catalyst solution and more preferably 80 v. % pyridine to 20 v. % catalyst solution and most preferably 90 v. % pyridine to 10 v. % catalyst solution.
- Light emitting diodes with narrow spectral emission are available at 480 and 555 nm wavelengths. These wavelengths can be used for absorbance and fluorescence measurements, respectively, although other wavelengths could
- the selected Fujiwara chemistry is reacted with a known sample of the particular organic chloride for which the chemistry has been selected and the fluorescence and absorption peaks of the reaction products are measured to establish a reference baseline.
- the reference values may be
- the selected Fujiwara chemistry is then used to analyze unknown samples for the presence of the particular organic chloride.
- the fluorescence and absorption data for the unknown sample is compared with
- 35 series of measurements with different Fujiwara chemistries for the different species can be used to selectively identify all the species present in the sample.
- Table I shows reference absorbance data and reference fluorescence data for each organic chloride for a selected chemistry (80 v. % pyridine) . Absorption is measured using a 480 nm source and fluorescence at an excitation wavelength of 555 nm. The observed color of the reaction products of each of the preferred group of organic chlorides with a number of Fujiwara chemistries can be used to select the appropriate reaction chemistry. Table II shows the absorption band, i.e., the wavelength range absorbed, for each observed color.
- one chemistry 65 % pyridine / 35 % TMAH
- the organic chlorides of interest produce a yellow-brown color or no color
- a second chemistry 80 % pyridine / 20 % TMAH
- TCE chloroform
- tetrachloroethane To produce a color response for carbon tetrachloride a pyridine/TPAH (65%/35%) chemistry should be used.
- a pyridine/TPAH 65%/35%) chemistry should be used.
- the selected chemistry can then be used to analyze samples, with absorption and/or fluorescence measurements being made to identify each species.
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Abstract
The Fujiwara chemistry is made more species-specific to detect various organic chlorides. The chemistry is varied in choice of pyridine or derivative, base, and ratio to enhance color of reaction product. Absorption and fluorescence measurements are compared to predetermined reference measurements to further identify the organic chloride.
Description
SPECIFIC MEASUREMENT OF ORGANIC CHLORIDES
BACKGROUND OF THE INVENTION The invention relates generally to the chemical detection of halogenated hydrocarbons using the Fujiwara reaction and more particularly to the selective detection of certain organic chlorides.
Trichloroethylene (TCE) heads theU.S. Environmental Protection Agency's (EPA) list of hazardous (toxic, carcinogenic, etc.) compounds and the organic chlorides, as a group, dominate the ten (10) most frequently found dangerous compounds. The other organic chlorides include 1,1,1- trichloroethane (TCA) , 1,1,2,2-tetrachloroethane, chloroform (CC£3) , carbon tetrachloride (CC£4) , and 1,2-dichloroethylene (DCE) . Although the focus has been on the measurement of TCE, each individual organic chloride is important and must be unambiguously detected and quantified.
The Fujiwara reaction is a known methodology widely used for the fluorometric and colorimetric analysis of gem- polyhalogen compounds. In the presence of a strong alkali (OH') , such as sodium or potassium hydroxide, pyridine or a derivative thereof reacts with a halogenated hydrocarbon to produce a red colored fluorescent product. The traditional chemistry (pyridine/base) is a two-phase system, since pyridine is insoluble in water with the commonly used alkalis (NaOH or KOH) . Therefore, the reaction product is formed only at the interface. The Fujiwara chemistry has been modified to overcome the limitations of the two-phase system. A single-phase system utilizes pyridine or a derivative thereof with a hindered nitrogen base (phase transfer catalyst) . U.S. Patents 4,666,672 issued May 19, 1987 and
4,771,006 issued September 13, 1988 to Holly Miller, et al., show hydrocarbon sensing optrodes which use the traditional two-phase Fujiwara chemistry in a reservoir type fiber optic chemical sensor. U.S. Patent 4,929,562 issued May 29, 1990 to William
Anderson (deceased), et al., shows method and apparatus for detecting gem-polyhalogenated hydrocarbons using a single- phase Fujiwara reaction. The modified Fujiwara chemistry is
pyridine or its derivative with a hindered nitrogen base, e.g. tetra(methyl, butyl or propyl) aπmionium hydroxide. Fluorescence and/or absorbance measurements relate to hydrocarbon concentration. EPA Report EPA/600/X-87/467 Part VI (Dec. 1987) describes the Fujiwara reaction for detection of organic chlorides. TCE and chloroform are detected using 2- (aminomethyl)pyridine. As suggested at p. 8, TCE is selectively monitored in the presence of chloroform by selectively separating the intermediate product chloroform- derived dichlorocarbene. Fluorescence is measured when the reaction mixture is irradiated at 350 nm (UV) . To shift this excitation wavelength to a lower energy, auxochromes are attached to the pyridine (p. 11) . Lockheed Fiber Optic Chemical Sensor Project - Final
Report to EPA (May 1989) describes a Lawrence Livermore National Laboratory (LLNL) fiber optic chemical sensor for TCE and chloroform with a single-phase Fujiwara reagent which is excited at 530 nm to measure fluorescence at 600 nm (p.2) and a related LLNL absorption sensor which measures absorption at 530 nm compared to a 600 nm nonabsorbed reference signal (p. 16).
LLNL Phase II Final Report to DOE (Sept. 1989) describes optrodes for TCE and chloroform, including fluorescence and absorption-based sensors. A dual wavelength absorption optrode measures absorption at 530 nm by the colored reaction product, with an internal reference provided by measuring unattenuated light at 610 nm. The optrode reagents are different for chloroform: 87.5 v. % pyridine, 12.5% tetrabutylammonium hydroxide (TBAH) (40% aqueous solution), and for TCE: 99 v. % pyridine, 1% TBAH solution. The absorption spectra for TCE and chloroform are different. The fluorescence sensor has been supplanted by the absorption sensor. One of the biggest problems with the Fujiwara reaction is that it is not specific enough to easily distinguish the various organic chlorides. The LLNL report cited above discusses some limited sensitivity. A successful environmental monitor should provide complete selectivity.
SUMMARY OF THE INVENTION According to one aspect of the invention, there is provided a method of selectively detecting and identifying a particular organic chloride species in a sample comprising: reacting the sample with a Fujiwara chemistry to form a reaction product, the Fujiwara chemistry being selected to enhance color and specificity of the reaction product of the particular organic chloride species; measuring at least one of an absorbance peak of the reaction product at a preselected first wavelength and fluorescence peak of the reaction product when excited at a preselected second wavelength; comparing the measured absorbance and fluorescence peaks of the reaction product to predetermined values of absorbance and fluorescence peaks at the preselected wavelengths for the reaction product of the selected Fujiwara chemistry and the particular organic chloride species.
Accordingly, the invention may provide a method of selecting between each of various organic chlorides using a modified Fujiwara reaction. The method may spectrally sort the reactions of various organic chlorides with a modified Fujiwara chemistry. Further, a method of the invention can preferably distinguish between TCE, chloroform, TCA, carbon tetrachloride, tetrachloroethane and dichloroethylene using a modified Fujiwara reaction. The method may select a suitable composition for a modified Fujiwara chemistry and spectrally sorts the reaction products of the selected chemistry with TCE, chloroform, TCA, carbon tetrachloride, tetrachloroethane and dichloroethylene.
The invention is preferably a method for detecting and identifying each of various organic chlorides using a modified Fujiwara reaction which selectively identifies each particular organic chloride. The composition of the Fujiwara chemistry has a significant effect on the characteristics of the colored reaction product with respect to wavelength and absorption. A chromophoric-enhancing and species-selective, modified Fujiwara chemistry may be obtained by varying the pyridine, base and water composition and ratios to optimize the results for a particular organic chloride. Using the selected chemistry, absorption and fluorescence measurements
further identify a particular organic chloride by comparing to reference values which have been measured for known samples.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS The invention is a method of selectively measuring the presence of each of a group of gem-polyhalogenated hydrocarbons in a sample using a modified Fujiwara chemistry which has been formulated to enhance the color of the Fujiwara reaction products obtained for the particular hydrocarbon. The method is further carried out by measuring the absorption and fluorescence peaks of the sample reaction products and comparing the measured values to a previously determined set of reference values. The reference values of absorption and fluorescence peaks for each species of hydrocarbon in the group are determined by reacting a known sample of the species with a modified Fujiwara chemistry with the selected formulation for that particular hydrocarbon. The same selected chemistry is used to test the unknown sample. The absorbance and fluorescence reference values of the hydrocarbon species can be compiled into a lookup table, as a function of the chemistry composition for comparison with the measured data. Similar measurements can be performed using different Fujiwara chemistries for each hydrocarbon so that the presence of each hydrocarbon can be tested. The invention is described with respect to the following group of gem-polyhalogenated hydrocarbons: trichloroethylene (TCE) , chloroform, carbon tetrachloride, 1,1,1-trichloroethane (TCA) ,1,1,2,2-tetrachloroethane, and 1,2-dichloroethylene. However, the principles of the invention can be carried out to add other species to the group, or for a group of different species, by modifying the Fujiwara chemistry composition to respond to each of the species and by establishing a baseline of colorimetric, absorption and fluorescence data for known samples of each species, and comparing measured values for an unknown sample against the baseline.
For the illustrative group of organic chlorides, a color and sensitivity enhancing modified Fujiwara chemistry is selected for each species. The composition can be varied in terms of using pyridine or a derivative thereof, choosing 5 the phase transfer catalyst (base) , and choosing the ratio thereof. By the proper choice, the development of color and sensitivity are significantly enhanced. Pyridine is preferred; 2,2 bipyridine or other pyridine derivatives can also be used. The phase transfer catalyst is preferably a
10 quaternary ammoniumhydroxide selected fromtetrabutylammonium hydroxide (TBAH) , tetramethylammonium hydroxide (TMAH) , tetraethyla monium hydroxide (TEAH) , and tetrapropylammonium hydroxide (TPAH) , with TBAH most preferred. The catalyst is preferably in an aqueous solution, with 30 to 14 wt. % water.
15 The ratio of pyridine to catalyst solution is preferably as low as 60 v. % pyridine to 40 v. % catalyst solution and more preferably 80 v. % pyridine to 20 v. % catalyst solution and most preferably 90 v. % pyridine to 10 v. % catalyst solution. These modified Fujiwara chemistries provide chromophoric
20 enhancement of the reaction.
Light emitting diodes with narrow spectral emission are available at 480 and 555 nm wavelengths. These wavelengths can be used for absorbance and fluorescence measurements, respectively, although other wavelengths could
25 be used. The selected Fujiwara chemistry is reacted with a known sample of the particular organic chloride for which the chemistry has been selected and the fluorescence and absorption peaks of the reaction products are measured to establish a reference baseline. The reference values may be
30 constructed into a lookup table. The selected Fujiwara chemistry is then used to analyze unknown samples for the presence of the particular organic chloride. The fluorescence and absorption data for the unknown sample is compared with
**. the reference values to further identify the species. A
35 series of measurements with different Fujiwara chemistries for the different species can be used to selectively identify all the species present in the sample.
Table I shows reference absorbance data and reference fluorescence data for each organic chloride for a
selected chemistry (80 v. % pyridine) . Absorption is measured using a 480 nm source and fluorescence at an excitation wavelength of 555 nm. The observed color of the reaction products of each of the preferred group of organic chlorides with a number of Fujiwara chemistries can be used to select the appropriate reaction chemistry. Table II shows the absorption band, i.e., the wavelength range absorbed, for each observed color.
TABLE I
REACTION OF MODIFIED FUJIWARA CHEMISTRIES WITH
COMPOUNDS WHICH COULD INTERFERE WITH THE TCE FOCS
All reactions run with pyridine.
All numerical values reflect wavelengths in nanometers (nm) Legend: TMAH Tetramethylammonium hydroxide
TPAH Tetrapropylammonium hydroxide
TBAH Tetrabutylammonium hydroxide
TCA 1,1,1-trichloroethane
TTCA 1,1,2,2-tetrachloroethane
CHLOR Chloroform
TCE Trichloroethylene
CCL4 Carbon tetrachloride
DCE 1,2-dichloroethylene λχ Excitation λ_ Emission
TABLE II WAVELENGTH RANGE ABSORBED FOR EACH OBSERVED COLOR OBSERVED COLOR ABSORPTION BAND .nm
Green-yellow 380-420 Yellow 420-440
Orange 440-470
Red 470-500
Purple 500-520
Violet 520-550 Violet-blue 550-580
Blue 580-620
Blue-green 620-680
Green 680-780
The selection of pyridine/TRAH ratio (R = M,B,P) affects the reaction product color significantly. For one chemistry (65 % pyridine / 35 % TMAH) , the organic chlorides of interest produce a yellow-brown color or no color, but a second chemistry (80 % pyridine / 20 % TMAH) produces strong colors for TCE, chloroform, and tetrachloroethane. To produce a color response for carbon tetrachloride a pyridine/TPAH (65%/35%) chemistry should be used. By testing other chemistry formulations, greater specificity to the individual species can be established. The selected chemistry can then be used to analyze samples, with absorption and/or fluorescence measurements being made to identify each species.
Changes and modifications in the specifically described embodiments can be carried out without departing from the scope of the invention which is intended to be limited only by the scope of the appended claims.
Claims
1. A method of selectively detecting and identifying a particular organic chloride species in_a sample comprising: reacting the sample with a Fujiwara chemistry to form a reaction product, the Fujiwara chemistry being selected to enhance color and specificity of the reaction product of the particular organic chloride species; measuring at least one of an absorbance peak of the reaction product at a preselected first wavelength and fluorescence peak of the reaction product when excited at a preselected second wavelength; comparing the measured absorbance and fluorescence peaks of the reaction product to predetermined values of absorbance and fluorescence peaks at the preselected wavelengths for the reaction product of the selected Fujiwara chemistry and the particular organic chloride species.
2. The method of Claim 1 wherein the organic chloride species is selected from trichloroethylene, chloroform, 1,1,1-trichloroethane, 1,1,2,2-tetrachloroethane, carbon tetrachloride and 1,2-dichloroethylene.
3. The method of Claim 1 wherein the Fujiwara chemistry comprises a mixture of pyridine or a derivative thereof and a quaternary ammonium hydroxide.
4. The method of Claim 3 wherein the quaternary ammonium hydroxide is selected from tetramethylammonium hydroxide, tetrabutylammonium hydroxide and tetrapropylammoniu hydroxide.
5. The method of Claim 2 wherein the Fujiwara chemistry comprises a mixture of pyridine or a derivative thereof and a quaternary ammonium hydroxide selected from tetramethylammonium hydroxide, tetrabutylammmonium hydroxide and tetrapropylammonium hydroxide.
6. The method of Claim 1 wherein the organic chloride species is TCE, the Fujiwara chemistry is pyridine (80 v. %) and TBAH (4 v. %) , in an aqueous solution with 16 wt. % water, the reference absorption peak is at 545 nm and the reference fluorescence peak is at 616 nm when excited at 555 nm.
7. The method of Claim 3 wherein the Fujiwara chemistry comprises pyridine.
8. The method of Claim 3 wherein the pyridine derivative comprises 2,2-bipyridine.
9. The method of Claim 4 wherein the Fujiwara chemistry comprises 35 v. % to 65 v. % pyridine.
10. The method of Claim 1 wherein the organic chloride species is TCE, the first wavelength is 480 nm and the second wavelength is 555 nm.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US755,062 | 1976-12-28 | ||
| US75506291A | 1991-08-13 | 1991-08-13 |
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|---|---|
| WO1993004368A1 true WO1993004368A1 (en) | 1993-03-04 |
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ID=25037569
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| PCT/US1992/006791 WO1993004368A1 (en) | 1991-08-13 | 1992-08-12 | Specific measurement of organic chlorides |
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| Country | Link |
|---|---|
| TW (1) | TW207567B (en) |
| WO (1) | WO1993004368A1 (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1995006871A2 (en) * | 1993-09-03 | 1995-03-09 | Ciba Corning Diagnostics Corporation | Method for activation of polyanionic fluorescent dyes in low dielectric media with quaternary onium compounds |
| US5490971A (en) * | 1994-10-25 | 1996-02-13 | Sippican, Inc. | Chemical detector |
| US6461872B1 (en) | 1999-11-17 | 2002-10-08 | General Electric Company | Poly(1,4-ethylene-2-piperazone) composition, method for production of a poly(1,4-ethylene-2-piperazone) composition, TCE-detecting method and sensor |
| US6694067B1 (en) | 2001-01-05 | 2004-02-17 | Los Gatos Research | Cavity enhanced fiber optic and waveguide chemical sensor |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4666672A (en) * | 1985-04-08 | 1987-05-19 | University Of California | Optrode for sensing hydrocarbons |
| US4771006A (en) * | 1985-04-08 | 1988-09-13 | The Regents Of The University Of California | Optrode for sensing hydrocarbons |
| US4929562A (en) * | 1986-08-20 | 1990-05-29 | The Regents Of The University Of California | Method and apparatus for detecting gem-polyhalogenated hydrocarbons |
-
1992
- 1992-08-12 WO PCT/US1992/006791 patent/WO1993004368A1/en active Application Filing
- 1992-08-12 TW TW081106379A patent/TW207567B/zh active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4666672A (en) * | 1985-04-08 | 1987-05-19 | University Of California | Optrode for sensing hydrocarbons |
| US4771006A (en) * | 1985-04-08 | 1988-09-13 | The Regents Of The University Of California | Optrode for sensing hydrocarbons |
| US4929562A (en) * | 1986-08-20 | 1990-05-29 | The Regents Of The University Of California | Method and apparatus for detecting gem-polyhalogenated hydrocarbons |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1995006871A2 (en) * | 1993-09-03 | 1995-03-09 | Ciba Corning Diagnostics Corporation | Method for activation of polyanionic fluorescent dyes in low dielectric media with quaternary onium compounds |
| WO1995006871A3 (en) * | 1993-09-03 | 1995-04-27 | Ciba Corning Diagnostics Corp | Method for activation of polyanionic fluorescent dyes in low dielectric media with quaternary onium compounds |
| AU687854B2 (en) * | 1993-09-03 | 1998-03-05 | Ciba Corning Diagnostics Corp. | Method for activation of polyanionic fluorescent dyes in low dielectric media with quaternary onium compounds |
| US5490971A (en) * | 1994-10-25 | 1996-02-13 | Sippican, Inc. | Chemical detector |
| US6461872B1 (en) | 1999-11-17 | 2002-10-08 | General Electric Company | Poly(1,4-ethylene-2-piperazone) composition, method for production of a poly(1,4-ethylene-2-piperazone) composition, TCE-detecting method and sensor |
| US6694067B1 (en) | 2001-01-05 | 2004-02-17 | Los Gatos Research | Cavity enhanced fiber optic and waveguide chemical sensor |
Also Published As
| Publication number | Publication date |
|---|---|
| TW207567B (en) | 1993-06-11 |
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