# CONVERSION OF PID READINGS TO METHANE EQUIVALENT OR HEXANE EQUIVALENT FID RESPONSE

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3 Example 3. Mixture with Non-Responding s The vapors consist of the following mixture: 60% Ethyl acetate (EA) 25% Methylene chloride (MC) 15% Toluene (Tol) The unit is calibrated to isobutylene and the reading is 50 ppm. There is no response to methylene chloride with the 10.6 ev lamp, therefore its correction factor is infinite. The average CF for this mixture is calculated as: CFmix = 1/(X EA /CF EA + X MC /CF MC + X Tol /CF Tol ) CFmix = 1/(0.60/ / /0.50) = 2.3 The average FID is calculated as (Eq. 6): mix = 0.60 x x x 5.1 = 2.2 According to Eq. 3a: CH 4 Equivs = 50 x 2.3 x 2.2 = 253 ppm Note that the 50 ppm response is equivalent to a higher methane equivalent response in this example than in Example 2 because the is blind to 25% of the total VOC. Example 4. Mixture with Unknown FID If the lab FID s were unknown in Examples 2 and 3 above, one would estimate the s as the number of carbons, which usually leads to a safe overestimation: For Example 2: mix = 0.60 x x x 7 = 4.5 CH 4 Equivs = 50 x 1.4 x 4.5 = 315 ppm compared to a value of 175 ppm from actual s. For Example 3: mix = 0.60 x x x 7 = 3.7 CH 4 Equivs = 50 x 2.3 x 3.7 = 426 ppm compared to a value of 253 ppm from actual s. It is clear that the availability of accurate response factors will help avoid false positive alarms. FID CORRECTION FACTOR DERIVATION FOR HEXANE EQUIVALENTS Although a with 10.6 ev lamp can be calibrated with hexane, the resulting hexane equivalents are different than FID hexane equivalents. Therefore, the same procedures should be used for hexane as described above for methane, by substituting the factors in Table 2 in place of those in Table 1. Table 2 assumes calibration with isobutylene. If the instrument is calibrated with hexane instead, the values in Table 2 should be divided by 4.3. The values in Table 2 are calculated as : #Cs in compound x CF / #Cs in hexane, or #Cs in compound x CF / 6 (isobutylene calib.) #Cs in compound x CF / 25.8 (hexane calib.) Example 5. Mixture For the same compound mixture as in Example 2, the unit is calibrated to isobutylene and reads 50 ppm: 60% Ethyl acetate (EA) 25% Methyl ethyl ketone (MEK) 15% Toluene (Tol) CFmix = 1/(0.60/ / /0.50) = 1.4 The true total concentration is 50 x 1.4 = 70 ppm, which consists of 42 ppm ethyl acetate, 17.5 ppm MEK, and 10.5 ppm toluene. Multiplying each compound by their respective FID factors from Table 2: Hexane Equivalents = 42 x x x 1.1 = 38 ppm To simplify, an average FID can be calculated for the mixture as: mix = X EA x EA + X MEK x MEK + X Tol x Tol (6) mix = 0.60 x x x 1.1 = 0.54 Then, analogous to Eq. 3a: Hexane Equivs = read x CF x FID Hexane Equivs = 50 x 1.4 x 0.54 = 38 ppm Hexane Equivs = reading x 0.76 = 38 ppm RAE Systems by Honeywell raesystems.com 3

4 Example 6. Hexane Calibration To calibrate with hexane instead of isobutylene, proceed as follows. For a compound with known, divide the in Table 2 by 4.3. For example, for isopropanol, the new factor is 2.1/4.3 = 0.49 and for gasoline, the new factor is about 1.3/4.3 = For a compound with unknown, such as aniline, the new factor is 3/4.3 = For a compound not on Table 2, such as methyl propyl ketone (#Cs = 5, CF = 0.93), the new factor is: (#Cs comp x CF comp ) / (#Cs hex x CF hex ) = (#Cs comp x CF comp ) / (6 x 4.3) = (#Cs comp x CF comp )/25.8(5 x 0.93)/25.8 = 0.18 Calibrate with hexane gas and set the CF to the factors listed in this paragraph to read directly in FID hexane equivalents. When using a MiniRAE 2000, it is easiest to use Memory 0 for this procedure because when other memories are calibrated, the CF cannot be changed from 1.0. Therefore, enter Memory 0, set the gas to hexane, change the CF to the value calculated above (for example, 0.49 for isopropanol or 0.30 for gasoline, not 4.3 for hexane), and set the span value to the hexane gas cylinder concentration. During calibration the monitor will ask for isobutylene, but hexane gas should be applied. During readings, the monitor will indicate hexane measurements, and it will be set up to read directly in FID hexane equivalents of the gas being measured. When using a ToxiRAE, set the span value to the hexane calibration gas concentration and calibrate with this same hexane gas. Then under the Select Gas? menu, choose hexane gas and change the correction factor to the value in Table 2 for the gas of interest, divided by 4.3 (for example, 0.49 for isopropanol or 0.30 for gasoline). REFERENCES J.D. Coy, P.L. Bigelow, R.M. Buchan, J.D. Tessari & J.O. Parnell, Field Evaluation of a Portable Photoionization Detector for Assessing Exposure to Solvent Mixtures, Amer. Ind. Hygiene Assoc. J. 61, , I. Drummond, On-the-Fly Calibration of Direct Reading Photoionization Detectors, Amer. Ind. Hygiene Assoc. J. 58, , ACKNOWLEDGMENT We wish to thank John Jenks of the NJ Department of Environmental Protection for reviewing this technical note and providing valuable suggestions. CF Acetaldehyde Acetic acid Acetone Acetonitrile 2 NR NR NR Acetylene 2 NR NR NR Acrolein Acrylonitrile 3 NR NR NR Allyl alcohol Allyl chloride 3 ~4 ~12 Aniline Benzene Benzyl chloride Bromoethane 2 ~1.6 ~3.2 Bromoform Bromoproane, Butadiene, 1, Butane, iso- 4 ~100 ~400 Table 1. to FID Correction Factors for Methane Equivalents CF Butane, n- 4 NR NR NR Butanol, n Butanol, iso Butyl mercaptan Carbon tetrachloride 1 NR 0.40 NR NR Chlorobenzene Chloroethane 2 NR NR NR Chloroform 1 NR 0.49 NR NR Cumene Cyclohexane Dichlorobenzene, 1, Dichlorobenzene, 1,4-6 ~0.5 ~3 Dichloroethylene, 1,1-2 ~ ~1.8 Dichloroethylene,c ~0.8 ~1.6 Dichloropropane, 1, 2-3 NR NR NR Dimethylformamide, N-N- 3 ~0.8 ~2.4 Dioxane, 1,4-4 ~1.3 ~5.2 RAE Systems by Honeywell raesystems.com 4

5 CF Epichlorohydrin Ethane 2 NR NR NR Ethanol Ethoxyethanol, 2- (Ethyl cellosolve) 4 ~1.3 ~5.2 Ethyl acetate Ethyl acrylate Ethylbenzene Ethylene dibromide (1,2-Dibromomethane) Ethylene dichloride (1,2-Dichloroethane) NR 1.5 NR NR Gasoline 8 ~1 ~8 Heptane, n Hexane, n Isobutylene Isoprene Isopropanol Methane 1 NR 1.0 NR NR Methanol 1 NR 0.58 NR NR Methoxyethanol, 2- (Methyl cellosolve) Methyl bromide Methyl chloride 1 NR NR NR Methyl ethyl ketone Methyl isobutyl ketone Methyl methacrylate CF Methyl t-butyl ether Methylene chloride 1 NR 0.94 NR NR Mineral Spirits Nonane, n- 9 ~1.4 ~13 Octane (mix) Pentane, n Perchloroethylene Propane 3 NR NR NR Propionaldehyde 3 ~1.9 ~5.7 Propylene oxide Styrene Tetrachloroethane, 1,1,2,2-2 NR NR NR Tetrahydrofuran Toluene Trichloroethane, 1,1,1-2 NR 1.6 NR NR Trichloroethane, 1,1,2-2 NR NR NR Trichloroethylene Trimethylbenzene, 1,2,4-6 ~ ~1 ~2 Triethylamine Vinyl acetate Vinyl bromide Vinyl chloride Xylene, o Xylene, m Xylene, p CF Acetaldehyde Acetic acid Acetone Acetonitrile 3 NR NR NR Acetylene 2 NR NR NR Acrolein Acrylonitrile 3 NR NR NR Allyl alcohol Allyl chloride 3 ~4 ~2 Aniline Table 2. to FID Correction Factors for Hexane Equivalents CF Benzene Benzyl chloride Bromoethane 2 ~1.6 ~0.5 Bromoform Bromoproane, Butadiene, 1, Butane, iso- 4 ~100 ~67 Butane, n- 4 NR NR NR Butanol, n Butanol, iso RAE Systems by Honeywell raesystems.com 5

6 CF Butyl mercaptan Carbon tetrachloride 1 NR 0.08 NR NR Chlorobenzene Chloroethane 2 NR NR NR Chloroform 1 NR 0.10 NR NR Cumene Cyclohexane Dichlorobenzene, 1, Dichlorobenzene, 1,4-6 ~0.5 ~0.5 Dichloroethylene, 1,1-2 ~ ~0.3 Dichloroethylene,c ~0.8 ~0.3 Dichloropropane, 1, 2-3 NR NR NR Dimethylformamide, N-N- 3 ~0.8 ~0.4 Dioxane, 1,4-4 ~1.3 ~0.9 Epichlorohydrin Ethane 2 NR NR NR Ethanol Ethoxyethanol, 2- (Ethyl cellosolve) 4 ~1.3 ~0.9 Ethyl acetate Ethyl acrylate Ethylbenzene Ethylene dibromide (1,2-Dibromoethane) Ethylene dichloride (1,2-Dichloroethane) NR 0.32 NR NR Gasoline 8 ~1 ~1.3 Heptane, n Hexane, n Isobutylene Isoprene Isopropanol Methane 1 NR 0.21 NR NR CF Methanol 1 NR 0.12 NR NR Methoxyethanol, 2- (Methyl cellosolve) Methyl bromide Methyl chloride 1 NR NR NR Methyl ethyl ketone Methyl isobutyl ketone Methyl methacrylate Methyl t-butyl ether Methylene chloride 1 NR 0.20 NR NR Mineral Spirits Nonane, n- 9 ~1.4 ~2 Octane (mix) Pentane, n Prechloroethylene Propane 3 NR NR NR Propionaldehyde 3 ~1.9 ~0.95 Propylene oxide Styrene Tetrachloroethane, 1,1,2,2-2 NR NR NR Tetrahydrofuran Toluene Trichloroethane, 1,1,1-2 NR 0.35 NR NR Trichloroethane, 1,1,2-2 NR NR NR Trichloroethylene Trimethylbenzene, 1,2,4-6 ~ ~0.08 ~0.35 Triethylamine Vinyl acetate Vinyl bromide Vinyl chloride Xylene, o Xylene, m Xylene, p RAE Systems by Honeywell raesystems.com 6

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