Detection of Low ppb Levels of Chlorinated HC by GC-PID (11.

7)
Dr. John Driscoll PID Analyzers, LLC 2 Washington Circle Sandwich, MA 02563 Paper #2340-14 Booth # 2080

A number of GC detectors have been used for the analysis of chlorinated hvdrocarbons (Cl HC) in environmental samples. Man have been found unsatisfactory The problems have included: complexity, low response factors, poor detection limits, significant variation with the degree of unsaturation, limited selectivity The PID does not solve all of the above problems but it is easy to use, has ppb detection limits and the response does not vary widely with structure
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Detectors for Cl HC have depended upon the following principals: A. electron absorbing properties- ECD B. decomposition in furnace & detection of H+ElCD C. thermionic emission in a flame- ClD. photoionization detection (PID) with a 10.2/10.6 lamp Each of these detectors have their limitations

In this paper, we will discuss the use of a PID with an 11.7 eV lamp that will solve some of the previous detector limitations
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Detector
ECD ElCD Alkali Flame PID 10.6

Det Limit
low pg low ppm mid ppm low pg

Limitation
structure, licensing, operation , easy to saturate conc, furnace, concentrator is required for ppb levels conc, reliability, specificity specificity

Name
Chloroform Carbon tetrachloride Chloroethanol Methylene chloride Methyl chloride Vinyl chloride 1, 1, 2, 2-tetrachloroethane Dichloromethane Ethyl chloride Epichlorohydrin Ethylene dichloride 1, 1, 1-trichloroethane Allyl chloride 1, 3-dichloropropane 1, 2-dichloropropane o-dichlorobenzene m-dichlorobenzene

IP eV
11.42 11.47

10.6eV Response
0 0 0.20

11.7 eV Response
3.15 4.22 6.70 6.83 7.60 7.80 8.60 8.70 9.20 10.30 10.50 10.70 11.90 12.10 12.10 15.50 15.50
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11.35 11.28 10.00 11.10 11.35

0.14 0 3.20 0 0 0

10.60 11.00 11.25 10.20 10.85 10.87 9.07 9.12

0.70 0 0 1.30 0.20 0.20 11.90 11.90

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350000

300000 y = 6.0204x + 2100.5 250000 PH for 11.7 PID

200000

150000

100000

50000

0 0 10000 20000 30000 ppb CHCl3 40000 50000 60000

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SENSITIVITY wo PRECONCENTRATION PID 10.6 eV- need unsaturation- low ppb detection PID 11.7 eV sub ppm detection ECD-needs multiple Cl to achieve low level detection- MeCl2 example ElCD PPM- need oven to decompose- low ppm min det. Requires concentrator for ppb

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6000

# of Cl 1 2 3 4 5 6

ECD 5 30 100 600 5000 40000 chlorobenzenes

PID 11.7 62 65 70 80 85 100

3000 2000 1000 0 0 2 4 6 5000 4000 Series1 Series2 Expon. (Series1) Linear (Series2) y = 7.5x + 48.333 y = 0.2678e1.956x

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1200000 1000000
Name 1 2 3 TCE PCE TCB Conc ppb 500 500 500 Height 973374 746159 664208 % 40.29 30.88 27.49 Area 312042784 228910192 173209056 % 43.14 31.65 23.95 Tim e 1:04 1:34 2:07

1 2 3

800000 600000 400000 200000

4 0 -200000 0:00 1:40 3:20 5:00 6:40 8:20 min 10:00

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The 11.7 PID is very useful for low MW HC such as CHCl3, CCl4, CH2Cl2, CH3Cl etc. Detection limits for CHCl3 were found to be 50 ppb for 0.5 cc sample For the chlorinated HC with double bonds the PID with a 10.6 eV lamp, the detection limit is 1-2 ppb The PID is one of the most sensitive detectors for Cl HC and a wide range of compounds can be detected with the 10.6 & 11.7 eV lamps
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