DE3400134A1 - Process for the separation, desorption and detection of dialkyl sulphates contained in air - Google Patents
Process for the separation, desorption and detection of dialkyl sulphates contained in airInfo
- Publication number
- DE3400134A1 DE3400134A1 DE19843400134 DE3400134A DE3400134A1 DE 3400134 A1 DE3400134 A1 DE 3400134A1 DE 19843400134 DE19843400134 DE 19843400134 DE 3400134 A DE3400134 A DE 3400134A DE 3400134 A1 DE3400134 A1 DE 3400134A1
- Authority
- DE
- Germany
- Prior art keywords
- air
- detection
- detector
- silica gel
- separation
- 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.)
- Withdrawn
Links
- 238000000034 method Methods 0.000 title claims abstract description 22
- 238000001514 detection method Methods 0.000 title claims abstract description 14
- 238000000926 separation method Methods 0.000 title claims abstract description 8
- 238000003795 desorption Methods 0.000 title claims abstract description 6
- 150000003467 sulfuric acid derivatives Chemical class 0.000 title abstract 5
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 21
- 239000000741 silica gel Substances 0.000 claims abstract description 19
- 229910002027 silica gel Inorganic materials 0.000 claims abstract description 19
- 238000005070 sampling Methods 0.000 claims abstract description 14
- 150000008050 dialkyl sulfates Chemical class 0.000 claims description 9
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 7
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 6
- 239000000126 substance Substances 0.000 claims description 6
- 239000007789 gas Substances 0.000 claims description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 4
- 238000001179 sorption measurement Methods 0.000 claims description 3
- 239000012159 carrier gas Substances 0.000 claims description 2
- 239000011521 glass Substances 0.000 claims description 2
- 238000002347 injection Methods 0.000 claims description 2
- 239000007924 injection Substances 0.000 claims description 2
- 229910052757 nitrogen Inorganic materials 0.000 claims description 2
- 239000011148 porous material Substances 0.000 claims description 2
- 239000012495 reaction gas Substances 0.000 claims description 2
- 239000002904 solvent Substances 0.000 claims description 2
- 101000952234 Homo sapiens Sphingolipid delta(4)-desaturase DES1 Proteins 0.000 claims 1
- 102100037416 Sphingolipid delta(4)-desaturase DES1 Human genes 0.000 claims 1
- 239000011159 matrix material Substances 0.000 abstract description 6
- 239000007787 solid Substances 0.000 abstract description 3
- 238000013375 chromatographic separation Methods 0.000 abstract description 2
- 238000001914 filtration Methods 0.000 abstract 1
- 231100001261 hazardous Toxicity 0.000 abstract 1
- 239000000383 hazardous chemical Substances 0.000 abstract 1
- 239000013056 hazardous product Substances 0.000 abstract 1
- 239000008207 working material Substances 0.000 abstract 1
- VAYGXNSJCAHWJZ-UHFFFAOYSA-N dimethyl sulfate Chemical compound COS(=O)(=O)OC VAYGXNSJCAHWJZ-UHFFFAOYSA-N 0.000 description 16
- DENRZWYUOJLTMF-UHFFFAOYSA-N diethyl sulfate Chemical compound CCOS(=O)(=O)OCC DENRZWYUOJLTMF-UHFFFAOYSA-N 0.000 description 12
- 229940008406 diethyl sulfate Drugs 0.000 description 12
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 3
- 238000011084 recovery Methods 0.000 description 3
- 238000009826 distribution Methods 0.000 description 2
- 238000004817 gas chromatography Methods 0.000 description 2
- 238000012544 monitoring process Methods 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 229910052717 sulfur Inorganic materials 0.000 description 2
- 239000011593 sulfur Substances 0.000 description 2
- 238000004566 IR spectroscopy Methods 0.000 description 1
- BNUHAJGCKIQFGE-UHFFFAOYSA-N Nitroanisol Chemical class COC1=CC=C([N+]([O-])=O)C=C1 BNUHAJGCKIQFGE-UHFFFAOYSA-N 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 230000000711 cancerogenic effect Effects 0.000 description 1
- 150000001735 carboxylic acids Chemical class 0.000 description 1
- 231100000315 carcinogenic Toxicity 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 238000004587 chromatography analysis Methods 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 238000004737 colorimetric analysis Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 230000006203 ethylation Effects 0.000 description 1
- 238000006200 ethylation reaction Methods 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 239000010881 fly ash Substances 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 239000000499 gel Substances 0.000 description 1
- 239000013067 intermediate product Substances 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- 238000004949 mass spectrometry Methods 0.000 description 1
- 230000011987 methylation Effects 0.000 description 1
- 238000007069 methylation reaction Methods 0.000 description 1
- 229940045681 other alkylating agent in atc Drugs 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 230000035945 sensitivity Effects 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 238000004809 thin layer chromatography Methods 0.000 description 1
Classifications
-
- 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
- G01N33/0004—Gaseous mixtures, e.g. polluted air
- G01N33/0009—General constructional details of gas analysers, e.g. portable test equipment
- G01N33/0027—General constructional details of gas analysers, e.g. portable test equipment concerning the detector
- G01N33/0036—General constructional details of gas analysers, e.g. portable test equipment concerning the detector specially adapted to detect a particular component
- G01N33/0047—Organic compounds
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/02—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by adsorption, e.g. preparative gas chromatography
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N30/00—Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
-
- 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
- G01N33/0004—Gaseous mixtures, e.g. polluted air
- G01N33/0009—General constructional details of gas analysers, e.g. portable test equipment
- G01N33/0011—Sample conditioning
Landscapes
- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Health & Medical Sciences (AREA)
- Analytical Chemistry (AREA)
- General Physics & Mathematics (AREA)
- Pathology (AREA)
- Physics & Mathematics (AREA)
- Immunology (AREA)
- Biochemistry (AREA)
- General Health & Medical Sciences (AREA)
- Combustion & Propulsion (AREA)
- Food Science & Technology (AREA)
- Medicinal Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Investigating Or Analyzing Non-Biological Materials By The Use Of Chemical Means (AREA)
Abstract
Description
II BeschreibungII description
1. Aufgabenstellung1 Task
Als Dialkylsulfate werden hier speziell Dimethylsulfat (DMS) und Diethylsulfat (DES) betrachtet. DMS und DES sind in den Abschnitten III A 2 der MAK-Wert-Liste eingestuft, da der Verdacht eines humankarzinogenen Potentials für diese Stoffe besteht. DMS hat einen TRK-Wert von 0,1 mg/m3 bei der Herstellung und 0,2 mg/m3 bei der Verwendung. DES besitzt einen TRK-Wert von 0,2 mg/m3 bei Herstellung und Verwendung.Dimethyl sulfate (DMS) and diethyl sulfate (DES) are specifically considered as dialkyl sulfates. DMS and DES are classified in Section III A 2 of the MAK value list, as there is a suspicion of a human carcinogenic potential for these substances. DMS has a TRK value of 0.1 mg / m 3 during manufacture and 0.2 mg / m 3 during use. DES has a TRK value of 0.2 mg / m 3 during manufacture and use.
Mit dem Auftreten von DMS-Dämpfen ist beim Herstellungsprozeß, beim Transport sowie bei der Verarbeitung von DMS, wo es zur Methylierung von Phenolen, Aminen und Carbonsäuren unter anderem eingesetzt wird, zu rechnen. Ferner wurde DMS in der Flugasche in der Abluft eines Kraftwerkes nachgewiesen, das mit schwefelarmer Kohle betrieben wurde [13.With the occurrence of strain gage vapors in the manufacturing process, in the transport as well as in the processing of DMS, where there is methylation of phenols, amines and carboxylic acids among others is used to calculate. Furthermore, DMS was detected in the fly ash in the exhaust air of a power plant, which with low-sulfur coal was operated [13.
Wenn der für das Entstehen von DMS in diesem Fall postulierte Reaktionsmechanismus stimmt, muß mit der Bildung von DMS auch .'. aus anderen schwefelhaltigen Brennstoffen gerechnet werden.If the reaction mechanism postulated for the formation of DMS is correct in this case, the formation of DMS must also. '. calculated from other fuels containing sulfur.
Die Verbreitung von DES ist geringer als die von DMS. DES wird für Ethylierungen eingesetzt und tritt als Zwischenprodukt bei der Herstellung von Diethylether auf. Für Uberwachungs- und Beurteilungsaufgaben sind die Konzentrationen der Schadstoffe in der Luft in Bezug zu ihren Grenzwerten von Bedeutung. Zur Bestimmung der Konzentrationen in der Luft sind einfache aber dennoch empfindliche und selektive Meßverfahren erforderlich.The spread of DES is less than that of DMS. DES is used for ethylation and is an intermediate product the production of diethyl ether. The concentrations are used for monitoring and assessment tasks of pollutants in the air in relation to their limit values. To determine the concentrations in the Air, simple but nevertheless sensitive and selective measuring methods are required.
2. Stand der Technik2. State of the art
Zur Bestimmung von DMS sind bisher kolorimetrische, spektroskopische, dünnschichtchromatographische und gaschromatographische Methoden beschrieben worden.For the determination of strain gauges, colorimetric, spectroscopic, Thin layer chromatographic and gas chromatographic methods have been described.
Die kolorimetrischen Methoden sind nicht spezifisch wegen möglicher Querempfindlichkeiten durch andere alkylierende Substanzen [2,3].The colorimetric methods are not specific because of possible cross-sensitivities from other alkylating agents Substances [2,3].
COPYCOPY
Bei Verwendung einer 20-m - Gaszelle ist es mit Hilfe der Infrarotspektroskopie möglich, DMS-Konzentrationen von 0,02 ppm noch zu erfassen, doch wegen möglicher Querempfindlichkeiten ist die Methode ebenfalls nicht als spezifisch einzustufen [4]..When using a 20 m gas cell it is with the help of the Infrared spectroscopy possible, DMS concentrations of 0.02 ppm can still be recorded, but because of possible cross-sensitivities, the method is also not considered to be specific to be classified [4] ..
DMS kann dünnschichtchromatographisch nach p-Nitroanisol-Derivatbildung mit der notwendigen Empfindlichkeit für eine MAK-Wert-überwachung spezifisch bestimmt werden [5],DMS can be used by thin-layer chromatography after p-nitroanisole derivative formation with the necessary sensitivity for a MAK value monitoring can be specifically determined [5],
Durch die Kombination Gaschromatographie/Massenspektroskopie wurde bei der DMS-Bestimmung eine Nachweisgrenze von 10 ppb erreicht [6].The combination of gas chromatography / mass spectroscopy resulted in a detection limit of 10 ppb for the DMS determination achieved [6].
Für die Bestimmung von DMS und DES durch GasChromatographie unter Verwendung eines Flammenphotometerdetektors sind unter Zugrundelegung einer 20-1-Probe Nachweisgrenzen von 0,04 ppm und 0,1 ppm angegeben worden 17]. Diese Angaben müssen jedoch aufgrund der gleichzeitig genannten Nachweisgrenzen von 2 μg/rΓ^l bzw. 5 pg/ml bei einem Extraktionsvolumen von 10 ml angezweifelt werden.For the determination of DMS and DES by gas chromatography using a flame photometer detector, based on a 20-1 sample, detection limits of 0.04 ppm are obtained and 0.1 ppm have been reported 17]. However, this information must due to the detection limits of 2 μg / rΓ ^ l mentioned at the same time or 5 pg / ml with an extraction volume of 10 ml will.
Die bisher in der Literatur beschrieben Festkorpersamme1-phasen au"f Silikagel-Basis zur Abscheidung von Dialkylsulfaten haben den Nachteil, daß die Dialkylsulfate auf ihnen entweder nicht quantitativ abgeschieden werden, nicht quantitativ desorbiert werden können oder beladene Sammelphasen nicht ohne Verluste lagerfähig sind. In eigenen Untersuchungen wurden als Probenahmematrix verschiedene Aktivkohle- und Silikageltypen getestet. Die Wiederfindung bei NIOSH- und Auer-Aktivkohle und einer DES-Masse von 30 μg pro Röhrchen lag zwischen 50 und 60%. Mit Silikagel waren stets höhere Wiederfindungsraten erzielbar. The solid body collection phases described so far in the literature on silica gel base for the separation of dialkyl sulfates have the disadvantage that the dialkyl sulfates are either not deposited quantitatively on them or are not desorbed quantitatively or loaded collection phases cannot be stored without losses. In our own investigations, Sampling matrix tested different types of activated carbon and silica gel. The recovery with NIOSH and Auer activated carbon and a DES mass of 30 μg per tube was between 50 and 60%. Higher recovery rates were always achievable with silica gel.
3. Beschreibung des Erfindungsgegenstandes3. Description of the subject matter of the invention
Gegenstand der Erfindung ist ein Verfahren zum Nachweis von in der Luft enthaltenen DialkylSulfaten, das weitgehend die unter 2. beschriebenen Nachteile anderer Verfahren ausgleicht. Das Verfahren umfaßt sowohl die Probenahme mittels Systemen, die einen Stoffaustausch mit der Luft erlauben, als auch die labormäßige Aufbereitung sowie das chemisch/physikalische Bestimmungsverfahren,The invention relates to a method for the detection of dialkyl sulfates contained in the air, which largely compensates for the disadvantages of other methods described under 2. The procedure includes both sampling by means of systems that allow an exchange of substances with the air, as well as laboratory processing as well the chemical / physical determination process,
3.1 Probenahme3.1 Sampling
Es wurden verschiedene Silikageltypen verglichen. Die weitaus besten Ergebnisse hinsichtlich der Abscheidung sowie der Lagerfähigkeit und der ünempfindlichkeit gegenüber hoher Luftfeuchte wurde mit einem Silikagel erzielt, das durch eine innere Oberfläche von 320 m2/g und einem mittleren Poren-Different types of silica gels were compared. By far the best results in terms of separation as well as storage life and insensitivity to high humidity were achieved with a silica gel, which has an inner surface of 320 m 2 / g and a mean pore size
durchmesser von 150 A gekennzeichnet ist.diameter of 150 A.
Für die Probenahme wird das Silikagel in geeignete Behältnisse verfüllt. Diese Behältnisse müssen Öffnungen aufweisen, die ^ den Zutritt der Luft erlauben. Grundsätzlich sind zwei Verfahren der Probenahme möglich :The silica gel is filled into suitable containers for sampling. These containers must have openings that ^ allow air to enter. Basically, two methods of sampling are possible:
1. Aktive Durchströmung der Silikagelmatrix, wobei der1. Active flow through the silica gel matrix, whereby the
. Lufttransport aufgrund eines mittels einer Pumpe über dem Silikagel erzeugten Druckgradienten erfolgt.. Air transport takes place due to a pressure gradient generated over the silica gel by means of a pump.
2. Der Stofftransport aus der Luft erfolgt aufgrund eines Konzentrationsgradienten durch Diffusion in die Silikagelmatrix hinein.2. The transport of substances from the air occurs due to a Concentration gradients through diffusion into the silica gel matrix.
Eine spezielle Ausführung eines solchen Probenahmesystems stellt ein Röhrchen dar, das bei einer Länge von 10 cm einen Innendurchmesser von ca. 0,5 cm aufweist.A special version of such a sampling system is a tube which, with a length of 10 cm has an inside diameter of about 0.5 cm.
z.B. Silikagel 432 der Firma GRACE GmbH, In der Hollerhecke 1e.g. silica gel 432 from GRACE GmbH, In der Hollerhecke 1
6520 Worms COPY6520 Worms COPY
Wird ein solches Probenahmeröhrchen mit handelsüblichen Pumpen, wie z.B. P 4000 von DuPont; mit einer Ansaugleistung von 2 l/h bis 70 l/h betrieben, ist die Silikagelmatrix hinsichtlich ihrer Korngrößenverteilung in geeigneter Weise zu wählen, da die Korngrößenverteilung im Silikagel einen entscheidenden Einfluß auf den Druckabfall der Strömung im Probenahmeröhrchen hat.Will such a collection tube with commercially available Pumps such as the P 4000 from DuPont; operated with a suction capacity of 2 l / h to 70 l / h, the silica gel matrix is to be selected appropriately with regard to its grain size distribution, since the grain size distribution in the silica gel has a decisive influence on the pressure drop in the flow has in the sampling tube.
Bei einem Probenahmesystem, das aus dem oben beschriebenen Probenahmeröhrchen bestand und das mit der oben genannten Probenahmepumpe betrieben wurde, hat sich ein Silikagel mit einer Körnung von o,5 bis 1 mmIn the case of a sampling system that is derived from the above Sampling tube existed and which was operated with the above-mentioned sampling pump a silica gel with a grain size of 0.5 to 1 mm
Durchmesser bewährt.Proven diameter.
3.2 Probenaufbereitung und Bestimmungsverfahren für Dimethylsulfat und Diethylsulfat 3.2 Sample preparation and determination methods for dimethyl sulfate and diethyl sulfate
Die gesamte Silikagelmasse wird in ein Probefläschchen überführt und mit 10 ml Ether überschichtet. Nach einer Desorptionszeit von 12 bis 16 h wird ein aliquoter Teil der Probe direkt in den GaschroamtographenThe entire silica gel mass is placed in a sample vial transferred and covered with 10 ml of ether. After a desorption time of 12 to 16 hours, an aliquot is made Part of the sample directly into the gas roamtograph
injiziert.injected.
Beispielhaft für das gaschromatograpnische Trennverfahren sind folgende Bedingungen :The following conditions are exemplary of the gas chromatographic separation process:
Säule : 3 m 1/4" - Glassäule (4 mm innererColumn: 3 m 1/4 "glass column (4 mm inner
Durchmesser)Diameter)
Säulenfüllung : 3% OV 17+1% H3PO4 auf ChromosorbColumn filling: 3% OV 17 + 1% H 3 PO 4 on Chromosorb
WHP 80/100WHP 80/100
. Silikagel 432 der Firma GRACE GmbH, In der Hollerhecke 1,. Silica gel 432 from GRACE GmbH, In der Hollerhecke 1,
652o Worms652o Worms
Temperaturen OfenOven temperatures
1. Bei Vorliegen von DMS1. If there is a DMS
1 min 4 0 0C mit 4 0°/min auf 85°C steigernIncrease 4 0 0 C at 40 ° / min to 85 ° C for 1 min
2. Bei Vorliegen von DES : 1 min 400C mit 40°/min auf 950C steigern2. In case of DES: increase to 95 0 C 1 min 40 0 C with 40 ° / min
InjektorInjector
2200C220 0 C
Detektordetector
Hall elektrolytischer Leitfähigkeitsdetektor (Detektortemperatur 22O0C, Temperatur des Reaktors des Hall-Detektors 10000C, Solvent flow : 1 ml Methanol/min, Reaktionsgas: 20 ml Luft/min)Hall electrolytic conductivity detector (detector temperature 22O 0 C, temperature of the reactor of the Hall detector 1000 0 C, solvent flow: 1 ml methanol / min, reaction gas: 20 ml air / min)
(Als Detektor ebenfalls geeignet ist der Flammenphotometerdetektor.)(The flame photometer detector is also suitable as a detector.)
TrägergasCarrier gas
40 μΐ/min Stickstoff40 μl / min nitrogen
Injektionsvolumen: 4 μΐInjection volume: 4 μΐ
3.3 Kenngrößen des Analysenverfahrens3.3 Parameters of the analytical process
Die Nachweisgrenze des Verfahrens liegt im Falle von DMS bei 5 μg/m3, wenn 500 1 Luft durch das Adsorptionsrohr gezogen werden. Im Falle von DES und einem Probeluftvolumen von 500 1 beträgt die Nachweisgrenze 11 μg/In^ Die Wiederfindungsrate wurde bei DMS zu 93 %,In the case of strain gauges, the detection limit of the method is 5 μg / m 3 if 500 liters of air are drawn through the adsorption tube. In the case of DES and an air sample volume of 500 1, the detection limit is 11 μg / In ^ The recovery rate for DMS was 93%,
bei DES zu 88 %at DES to 88%
bestimmt.certainly.
Belastete Sairunelphasen sind ohne Verluste bis zu 3 Tagen lagerfähig.Stressed Sairunel phases are without losses up to can be stored for up to 3 days.
COPYCOPY
1.1] Lee, M. L. : Science 207 (1980), S. 1861.1] Lee, M. L.: Science 207 (1980), p. 186
[2] Psaltyra, S.A. : Air. Gig. Savit 35 (1970) S. 87/88[2] Psaltyra, S.A. : Air. Gig. Savit 35 (1970) pp. 87/88
[3] Tomczyk, D. und J. Bajerska : Chem. Anal. (Warsaw) 18 (1973) , S. 543/549[3] Tomczyk, D. and J. Bajerska: Chem. Anal. (Warsaw) 18 (1973), pp. 543/549
[4] Wilkes : Infrared Analytical Data for Compliance Testing (1978)[4] Wilkes: Infrared Analytical Data for Compliance Testing (1978)
[5] Keller, J. : Anal. Chem. 269 (1974), S. 206/208[5] Keller, J.: Anal. Chem. 269: 206/208 (1974)
. [6] Ellgehausen, D. : Fresenius Z. Anal. Chem. 272 (1974), S. 284. [6] Ellgehausen, D.: Fresenius Z. Anal. Chem. 272 (1974), p. 284
[7] Gilland, J. C. and A. P. Bright : Am. Ind. Hyg. Assoc. J., Vol. 41 (1980), S. 459/461[7] Gilland, J.C. and A.P. Bright: Am. Ind. Hyg. Assoc. J., Vol. 41 (1980), pp. 459/461
Claims (4)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE19843400134 DE3400134A1 (en) | 1984-01-04 | 1984-01-04 | Process for the separation, desorption and detection of dialkyl sulphates contained in air |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE19843400134 DE3400134A1 (en) | 1984-01-04 | 1984-01-04 | Process for the separation, desorption and detection of dialkyl sulphates contained in air |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| DE3400134A1 true DE3400134A1 (en) | 1985-07-11 |
Family
ID=6224324
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| DE19843400134 Withdrawn DE3400134A1 (en) | 1984-01-04 | 1984-01-04 | Process for the separation, desorption and detection of dialkyl sulphates contained in air |
Country Status (1)
| Country | Link |
|---|---|
| DE (1) | DE3400134A1 (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE4012982A1 (en) * | 1990-04-24 | 1991-10-31 | Ftu Gmbh | Removing harmful (in)organic substance from gases - by addn. of finely divided substance with active surface and filtration |
| DE4125555A1 (en) * | 1991-08-02 | 1993-02-04 | Rene Dr Cousin | Monitoring waste gas emissions - using adsorber-filled sampling probe in waste gas stream |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB2056304A (en) * | 1979-07-27 | 1981-03-18 | Thermo Electron Corp | Method of and apparatus for extracting amine compounds from air samples |
-
1984
- 1984-01-04 DE DE19843400134 patent/DE3400134A1/en not_active Withdrawn
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB2056304A (en) * | 1979-07-27 | 1981-03-18 | Thermo Electron Corp | Method of and apparatus for extracting amine compounds from air samples |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE4012982A1 (en) * | 1990-04-24 | 1991-10-31 | Ftu Gmbh | Removing harmful (in)organic substance from gases - by addn. of finely divided substance with active surface and filtration |
| DE4125555A1 (en) * | 1991-08-02 | 1993-02-04 | Rene Dr Cousin | Monitoring waste gas emissions - using adsorber-filled sampling probe in waste gas stream |
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