CA1040988A - Apparatus and method to detect chloromethyl methyl ether - Google Patents
Apparatus and method to detect chloromethyl methyl etherInfo
- Publication number
- CA1040988A CA1040988A CA204,031A CA204031A CA1040988A CA 1040988 A CA1040988 A CA 1040988A CA 204031 A CA204031 A CA 204031A CA 1040988 A CA1040988 A CA 1040988A
- Authority
- CA
- Canada
- Prior art keywords
- alkali metal
- metal salt
- detector
- accordance
- methyl ether
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired
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- Investigating Or Analyzing Non-Biological Materials By The Use Of Chemical Means (AREA)
Abstract
A B S T R A C T
An analytical method and apparatus for determining the presence of chloromethyl methyl ether in air.
The ether is reacted with a reagent which can be an alkali metal salt of an alcohol of 1 to 4 carbon atoms, of phenol, or of a chlorophenol having 1 to 5 chlorine atoms. A derivative of the reagent is thus formed.
The derivative is then passed into a chroma-tographic column and then into a detector. By this procedure chloromethyl methyl ether can be detected in the parts per billion range.
An analytical method and apparatus for determining the presence of chloromethyl methyl ether in air.
The ether is reacted with a reagent which can be an alkali metal salt of an alcohol of 1 to 4 carbon atoms, of phenol, or of a chlorophenol having 1 to 5 chlorine atoms. A derivative of the reagent is thus formed.
The derivative is then passed into a chroma-tographic column and then into a detector. By this procedure chloromethyl methyl ether can be detected in the parts per billion range.
Description
; `-~O~ t38 This invention relates to an air monitoring apparatus and method, and particularly to an apparatus and method for determining the presence of chloromethyl methyl ether in air at the parts per billion level, or less.
Experience indicates that the direct analysis of chloromethyl methyl ether is not adequate in sensitivity or specificity for monitoring this compound in environmental air in the parts per billion concentration range.
This deficiency in previous analytical procedures, according to the present invention, has been overcome by a method to determine the presence of chloromethyl methyl ether in air at the parts per billion level, comprising reacting chloromethyl methyl ether from the air with an alkali -metal salt of an alcohol having 1 to 4 carbon atoms or an alkali metal salt of phenol or an alkali metal salt of a chlorophenol having 1 to 5 chlorine atoms, passing the reaction product through a gas chromatographic column, then eluting the component therefrom through a detector and displaying ~ the output of said detector on a suitable readout device.
The present invention is also directed to . . .
apparatus to determine the presence of chloromethyl methyl ether in air at the parts per billion level, comprising a reaction tube containing an alkali metal salt of an alcohol having 1 to 4 carbon atoms or an alkali metal salt of phenol ~ -or an alkali metal salt of a chlorophenol having 1 to 5 chlorine atoms, means for passing air which may contain chloromethyl methyl ether through said reaction tube for a predetermined time whereby said chloromethyl methyl ether reacts with said alkali metal salt to form a derivative, means for raising the ~ -temperature in said reaction tube to a temperature above the 16,882-F
..
., , . , ,- -" " . ,; , , . . ; ... . ..
volatilizing temperature of said derivative, a gas chromato-graph and a detector, means for sweeping said volatilized derivative through said chromatograph and for sweeping eluted material from said chromatograph through said detector, whereby a signal is developed which is a function .:~
of the amount of chloromethyl methyl ether in air, and readout means coupled to said detector for displaying said signal.
Referring to the drawing, there is shown apparatus including a valved air inlet 10 coupled via line 44 to a four way valve 12. A tank 32 of carrier gas such as nitrogen, for example, has a valve 62 which ~ ~
is coupled through pressure regulator valve 34 and -~ -line 40 to an input of the four way valve 12. A line '::
, ' ' ", ':
: - . , ' .:.:. .
.. ..
16,882-P -la7 .~
~04~9~3B
42 carrying pressure regulating valve 36 and valve 38 is coupled to the line 44 and to the line 40 between the valve 34 and the valve 12.
One output of the valve 12 is coupled via line 48 to a reaction tube 14 which is between one and four inches in length (2.54-10.2 cm.) and contains packed beads on which is deposited one of the reagents mentioned previously. The tube 14 may be heated by any suitable means, such as, for example, the heater winding 16 which is coupled through leads 56, 58 to, and is energized from, a suitable programmable temperature controller 18.
The output of the reaction tube 14 is coupled to an input of the four way valve 20.
An output of the valve 12 is coupled through the line 46 which couples valve 60 to another line that is connected with the valve 20. ,~
One output of the valve 20 is coupled through line 50, carrying valve 52, to a vacuum pump 54.
The other output of the valve 20 is coupled through the line 24 to a flame detector 26 through a chromatographic column 22.
The output of the flame detector 26 is coupled to amplifier 28 and the output signal developed acros~ the load resi8tor 32 is coupled to a recorder 30 or other read-out device.
In operation, air to be sampled passes through ~alve~ 10 and 12, through the reaction tube 14 and then through valves 20 and 52 to the vacuum pump 54.
Simultaneously, pressure-regulated inert carrier ga~, usually nitrogen, passes from the tank 32 1 ,882-P -2-104(~988 through line 40, valve 12, line 46, valve 20 through the chromatographic column 22, through line 24, and through the flame detector 26.
After a suitable amount of air i8 drawn through the reaction tube 14, air flow is stopped by closing valve 10. At this time, valve 38 is opened, allowing carrier gas from the tank 32 to flow through line 42, needle valve 36, line 44, valve 12, reaction tube 14, valve 20, line 50 and the vacuum pump 54. This results in the purging of residual air from the reaction tube 14.
After suitable purging time with the flow of carrier gas through the tube 14, valves 38 and 52 are shut off. Heat is then applied to the reaction tube 14 through the electrical heater winding 16, for example.
After a suitable temperature i8 attained in the tube 14 (as ~ensed by the temperature controller 18) to volatilize derivatized compounds in the tube 14, valves 12 and 20 are operated to allow carrier gas from the tank 32 to flow through the pressure regulator 34 and line 40 through the tube 14 and on through the chromatographic column 22, carrying the volatilized derivatives with it. Chromatographic separation of the volatilized derivative is accomplished in the column 22 and the separated derivative is combusted in a suitable detector 26 such as a hydrogen flame detector.
The output signal from the detector 26 is amplified by amplifier 28 and displayed on the readout device, recorder 30.
After all the volatilized derivative has been swept through the chromatographic column 22, the heater winding 16 i~ de-energized and the reaction tube 14 allowed ,'. ~.
1~,882-F -3-~04~9b~8 to cool at near ambient temperature. Valves 12 and 20 actuated to again permi~ the flow of air through the tube 14 to the vacuum pump 54 on opening of the valves 10 and 52.
The actuation of valves 10, 12, 20, 38 and 52, all of which are electrically controllable, are controlled by a suitable timer-controller 64 which is coordinated with the temperature controller 18.
The following reaction may be used to stabilize chloromethyl methyl ether and also to enhance its sensi-tivitY.
CH30CH2Cl + NaO ~ ~ CH30CH20 ~ + NaCl ~-In this reaction the sodium phenate is carried on glass beads or other suitable non-reactive particulate material. Sodium salts of chlorinated phenols may al80 be used in place of the sodium phenate in the above reaction.
~ther derivatives which may be used in analyses in accordance with this invention are: - -CH30CH2Cl + NaOCH2CH3 ~ 30cH2ocH2cH3 + NaCl , In this reaction the sodium ethoxide is carried on glass beads or other suitable non-reactive particulate material.
Other sodium alkoxides could be used in place of the sodium ethoxide, such as sodium propoxide and sodium butoxide. --.
The alkali metal salts of an alcohol are prepared a~ a methanolic ~olution and are then evaporated onto the ~upporting material,`60/80 mesh glass beads, for example. ~ -The bead~ are then placed in the reaction tube 14, a short .
1~,882-F -4-104~9~38 glass tubular member between one and four inches in length (2.54-10.2 cm.) is common. One reaction tube 14 used i8 three inches long (7.62 cm.) and has an internal diameter of about 3/16 inch (0.48 cm.).
The reaction tube 14 should be closely coupled to the valve 20, preferably by a glass tube. The other lines used in the apparatus may be made of stainless steel, copper, polytetrafluoroethylene or other material which is non-reactive with the components passing through it.
Hydrogen flame detectors made by Varian, Beckman Instrument Co., and Hewlett-Packard have been found to be suitable. A one millivolt recorder 30 is commonly used.
However, other suitable readout devices may be substituted.
The chromatograph 22 may be a Varian Aerograph Model 1400 gas-liquid chromatograph for batch-wise analytical work. A 8eckman Model 320 DF process gas liquid chromato-graph or Bendix Corp. Model 6000 process gas chromatograph or other similar chromatographs are well suited for automated analytical work in accordance with this invention.
While a hydrogen flame detector would be usable for the detection of all the derivatives, the electron capture detector would be operable with those derivative compounds containing chlorine.
If a chlorophenol i8 used in the reac~ion tube, a much smaller ~ample volume may be used. For example, one ml.
of CMME-containing sample may be pasQed through the heated ~-~around 140 C.) reaction tube and run directly through the chromatograph column.
16,882-P -5-. . ~ .. ~. : . . ;
Experience indicates that the direct analysis of chloromethyl methyl ether is not adequate in sensitivity or specificity for monitoring this compound in environmental air in the parts per billion concentration range.
This deficiency in previous analytical procedures, according to the present invention, has been overcome by a method to determine the presence of chloromethyl methyl ether in air at the parts per billion level, comprising reacting chloromethyl methyl ether from the air with an alkali -metal salt of an alcohol having 1 to 4 carbon atoms or an alkali metal salt of phenol or an alkali metal salt of a chlorophenol having 1 to 5 chlorine atoms, passing the reaction product through a gas chromatographic column, then eluting the component therefrom through a detector and displaying ~ the output of said detector on a suitable readout device.
The present invention is also directed to . . .
apparatus to determine the presence of chloromethyl methyl ether in air at the parts per billion level, comprising a reaction tube containing an alkali metal salt of an alcohol having 1 to 4 carbon atoms or an alkali metal salt of phenol ~ -or an alkali metal salt of a chlorophenol having 1 to 5 chlorine atoms, means for passing air which may contain chloromethyl methyl ether through said reaction tube for a predetermined time whereby said chloromethyl methyl ether reacts with said alkali metal salt to form a derivative, means for raising the ~ -temperature in said reaction tube to a temperature above the 16,882-F
..
., , . , ,- -" " . ,; , , . . ; ... . ..
volatilizing temperature of said derivative, a gas chromato-graph and a detector, means for sweeping said volatilized derivative through said chromatograph and for sweeping eluted material from said chromatograph through said detector, whereby a signal is developed which is a function .:~
of the amount of chloromethyl methyl ether in air, and readout means coupled to said detector for displaying said signal.
Referring to the drawing, there is shown apparatus including a valved air inlet 10 coupled via line 44 to a four way valve 12. A tank 32 of carrier gas such as nitrogen, for example, has a valve 62 which ~ ~
is coupled through pressure regulator valve 34 and -~ -line 40 to an input of the four way valve 12. A line '::
, ' ' ", ':
: - . , ' .:.:. .
.. ..
16,882-P -la7 .~
~04~9~3B
42 carrying pressure regulating valve 36 and valve 38 is coupled to the line 44 and to the line 40 between the valve 34 and the valve 12.
One output of the valve 12 is coupled via line 48 to a reaction tube 14 which is between one and four inches in length (2.54-10.2 cm.) and contains packed beads on which is deposited one of the reagents mentioned previously. The tube 14 may be heated by any suitable means, such as, for example, the heater winding 16 which is coupled through leads 56, 58 to, and is energized from, a suitable programmable temperature controller 18.
The output of the reaction tube 14 is coupled to an input of the four way valve 20.
An output of the valve 12 is coupled through the line 46 which couples valve 60 to another line that is connected with the valve 20. ,~
One output of the valve 20 is coupled through line 50, carrying valve 52, to a vacuum pump 54.
The other output of the valve 20 is coupled through the line 24 to a flame detector 26 through a chromatographic column 22.
The output of the flame detector 26 is coupled to amplifier 28 and the output signal developed acros~ the load resi8tor 32 is coupled to a recorder 30 or other read-out device.
In operation, air to be sampled passes through ~alve~ 10 and 12, through the reaction tube 14 and then through valves 20 and 52 to the vacuum pump 54.
Simultaneously, pressure-regulated inert carrier ga~, usually nitrogen, passes from the tank 32 1 ,882-P -2-104(~988 through line 40, valve 12, line 46, valve 20 through the chromatographic column 22, through line 24, and through the flame detector 26.
After a suitable amount of air i8 drawn through the reaction tube 14, air flow is stopped by closing valve 10. At this time, valve 38 is opened, allowing carrier gas from the tank 32 to flow through line 42, needle valve 36, line 44, valve 12, reaction tube 14, valve 20, line 50 and the vacuum pump 54. This results in the purging of residual air from the reaction tube 14.
After suitable purging time with the flow of carrier gas through the tube 14, valves 38 and 52 are shut off. Heat is then applied to the reaction tube 14 through the electrical heater winding 16, for example.
After a suitable temperature i8 attained in the tube 14 (as ~ensed by the temperature controller 18) to volatilize derivatized compounds in the tube 14, valves 12 and 20 are operated to allow carrier gas from the tank 32 to flow through the pressure regulator 34 and line 40 through the tube 14 and on through the chromatographic column 22, carrying the volatilized derivatives with it. Chromatographic separation of the volatilized derivative is accomplished in the column 22 and the separated derivative is combusted in a suitable detector 26 such as a hydrogen flame detector.
The output signal from the detector 26 is amplified by amplifier 28 and displayed on the readout device, recorder 30.
After all the volatilized derivative has been swept through the chromatographic column 22, the heater winding 16 i~ de-energized and the reaction tube 14 allowed ,'. ~.
1~,882-F -3-~04~9b~8 to cool at near ambient temperature. Valves 12 and 20 actuated to again permi~ the flow of air through the tube 14 to the vacuum pump 54 on opening of the valves 10 and 52.
The actuation of valves 10, 12, 20, 38 and 52, all of which are electrically controllable, are controlled by a suitable timer-controller 64 which is coordinated with the temperature controller 18.
The following reaction may be used to stabilize chloromethyl methyl ether and also to enhance its sensi-tivitY.
CH30CH2Cl + NaO ~ ~ CH30CH20 ~ + NaCl ~-In this reaction the sodium phenate is carried on glass beads or other suitable non-reactive particulate material. Sodium salts of chlorinated phenols may al80 be used in place of the sodium phenate in the above reaction.
~ther derivatives which may be used in analyses in accordance with this invention are: - -CH30CH2Cl + NaOCH2CH3 ~ 30cH2ocH2cH3 + NaCl , In this reaction the sodium ethoxide is carried on glass beads or other suitable non-reactive particulate material.
Other sodium alkoxides could be used in place of the sodium ethoxide, such as sodium propoxide and sodium butoxide. --.
The alkali metal salts of an alcohol are prepared a~ a methanolic ~olution and are then evaporated onto the ~upporting material,`60/80 mesh glass beads, for example. ~ -The bead~ are then placed in the reaction tube 14, a short .
1~,882-F -4-104~9~38 glass tubular member between one and four inches in length (2.54-10.2 cm.) is common. One reaction tube 14 used i8 three inches long (7.62 cm.) and has an internal diameter of about 3/16 inch (0.48 cm.).
The reaction tube 14 should be closely coupled to the valve 20, preferably by a glass tube. The other lines used in the apparatus may be made of stainless steel, copper, polytetrafluoroethylene or other material which is non-reactive with the components passing through it.
Hydrogen flame detectors made by Varian, Beckman Instrument Co., and Hewlett-Packard have been found to be suitable. A one millivolt recorder 30 is commonly used.
However, other suitable readout devices may be substituted.
The chromatograph 22 may be a Varian Aerograph Model 1400 gas-liquid chromatograph for batch-wise analytical work. A 8eckman Model 320 DF process gas liquid chromato-graph or Bendix Corp. Model 6000 process gas chromatograph or other similar chromatographs are well suited for automated analytical work in accordance with this invention.
While a hydrogen flame detector would be usable for the detection of all the derivatives, the electron capture detector would be operable with those derivative compounds containing chlorine.
If a chlorophenol i8 used in the reac~ion tube, a much smaller ~ample volume may be used. For example, one ml.
of CMME-containing sample may be pasQed through the heated ~-~around 140 C.) reaction tube and run directly through the chromatograph column.
16,882-P -5-. . ~ .. ~. : . . ;
Claims (12)
PROPERTY OR PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS:
1. A method to determine the presence of chloromethyl methyl ether in air at the parts per billion level, comprising reacting chloromethyl methyl ether from the air with an alkali metal salt of an alcohol having 1 to 4 carbon atoms or an alkali metal salt of phenol or an alkali metal salt of a chlorophenol having 1 to 5 chlorine atoms, passing the reaction product through a gas chromatographic column, then eluting the component therefrom through a detector and displaying the output of said detector on a suitable readout device.
2. A method in accordance with Claim 1, wherein said alkali metal salt is sodium phenate.
3. A method in accordance with Claim 1, wherein said alkali metal salt is sodium ethoxide.
4. A method in accordance with Claim 1, wherein said alkali metal salt is a sodium salt of a chlorinated phenol having 1 to 5 chlorine atoms.
5. Apparatus to determine the presence of chloromethyl methyl ether in air at the parts per billion level, comprising a reaction tube containing an alkali metal salt of an alcohol having 1 to 4 carbon atoms or an alkali metal salt of phenol or an alkali metal salt of a chlorophenol having 1 to 5 chlorine atoms, means for passing air which may contain chloromethyl methyl ether through said reaction tube for a predetermined time whereby said chloromethyl methyl ether reacts with said alkali metal salt to form a derivative, means for raising the temperature in said reaction tube to a temperature above the volatilizing temperature of said derivative, a gas chromatograph and a detector, means for sweeping said volatilized derivative through said chromatograph and for sweeping eluted material from said chromatograph through said detector, whereby a signal is developed which is a function of the amount of chloromethyl methyl ether in air, and readout means coupled to said detector for displaying said signal.
6. Apparatus in accordance with Claim 5, wherein said readout means is a recorder.
7. Apparatus in accordance with Claim 5, wherein said means for sweeping is pressurized inert gas.
8. Apparatus in accordance with Claim 7, wherein said gas is nitrogen.
9. Apparatus in accordance with Claim 5, wherein said means for raising the temperature includes heating means and programmable heat controller means.
10. Apparatus in accordance with Claim 5, wherein said reaction tube is a glass tubular member and contains packed beads carrying alkali metal salt of an alcohol having 1 to 4 carbon atoms, of phenol or of a chlorophenol having 1 to 5 chlorine atoms.
11. Apparatus in accordance with Claim 5, wherein said detector is a hydrogen flame detector.
12. Apparatus in accordance with Claim 5, wherein said detector is an electron capture detector.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CA204,031A CA1040988A (en) | 1974-07-04 | 1974-07-04 | Apparatus and method to detect chloromethyl methyl ether |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CA204,031A CA1040988A (en) | 1974-07-04 | 1974-07-04 | Apparatus and method to detect chloromethyl methyl ether |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1040988A true CA1040988A (en) | 1978-10-24 |
Family
ID=4100578
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA204,031A Expired CA1040988A (en) | 1974-07-04 | 1974-07-04 | Apparatus and method to detect chloromethyl methyl ether |
Country Status (1)
| Country | Link |
|---|---|
| CA (1) | CA1040988A (en) |
-
1974
- 1974-07-04 CA CA204,031A patent/CA1040988A/en not_active Expired
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