# Allyl Chloride (1000)

ALLYL CHLORIDE 1000 CH2=CHCH2Cl MW: 76.53 CAS: 107-05-1 RTECS: UC7350000 METHOD: 1000, Issue 2
EVALUATION: FULL
OSHA: 1 ppm NIOSH: 1 ppm; STEL 2 ppm ACGIH: 1 ppm; STEL 2 ppm
(1 ppm = 3.13 mg/m³ @ NTP)
Issue 1: 15 February 1984 Issue 2: 15 August 1994
PROPERTIES: liquid; d 0.938 g/mL @ 20 °C; BP 45 °C; MP –135 °C; VP 39.3 kPA (295 mm Hg) @ 25 °C; explosive range 3.3 to 11% v/v in air
SYNONYMS: 3-chloro-1-propene; 1-chloro-2-propene SAMPLING SAMPLER: SOLID SORBENT TUBE (coconut shell charcoal, 100 mg/50 mg)
MEASUREMENT TECHNIQUE:
GAS CHROMATOGRAPHY, FID
ANALYTE:
allyl chloride
DESORPTION:
1 mL benzene; stand 30 min
INJECTION VOLUME:
5 µL
FLOW RATE: 0.01 to 1 L/min VOL-MIN: -MAX:
16 L @ 1 ppm 100 L
SHIPMENT: routine SAMPLE STABILITY: at least 6 weeks @ 25 °C
TEMPERATURE-INJECTION: 185 to 200 °C -DETECTOR: 250 °C -COLUMN: 160 to 200 °C
BLANKS:
CARRIER GAS:
N2, 30 mL/min
COLUMN:
stainless steel, 1.2 m × 6-mm OD; 50/80 mesh Porapak Q or equivalent
CALIBRATION:
standard solutions of allyl chloride in benzene
RANGE:
0.05 to 1.5 mg per sample
2 to 10 field blanks per set ACCURACY
RANGE STUDIED: BIAS:
1.8 to 7.2 mg/m³ [1] (100-L samples) 6.4%
OVERALL PRECISION ( ): 0.071 [1]
ESTIMATED LOD: 0.01 mg per sample ACCURACY:
±16.6%
PRECISION ( ):
0.023 [1]
APPLICABILITY: The working range is 0.16 to 3 ppm (0.5 to 10 mg/m³) for a 100-L air sample. The method is applicable to short-term samples taken at 1 L/min. The upper limit of loading depends on the concentrations of allyl chloride and other substances in the air, including water vapor. INTERFERENCES: None identified. OTHER METHODS: This is Method S116 in a revised format [2].
NIOSH Manual of Analytical Methods (NMAM), Fourth Edition ​ALLYL CHLORIDE: METHOD 1000, Issue 2, dated 15 August 1994 - Page 2 of 3
REAGENTS:
EQUIPMENT:
1. Benzene, chromatographic quality.* 2. Allyl chloride. 3. Hexane. 4. Calibration stock solution, 7.5 µg/µL. Dilute 75 mg allyl chloride (80.0 µL at 20 °C) to 10 mL with hexane. 5. Nitrogen, purified. 6. Hydrogen, prepurified. 7. Air.
1. Sampler: glass tube, 7 cm long, 6-mm OD, 4-mm ID, flame-sealed ends, containing two sections of activated (600 °C) coconut shell charcoal (front = 100 mg, back = 50 mg) separated by a 2-mm urethane foam plug. A silylated glass wool plug precedes the front section and a 3-mm urethane foam plug follows the back section. Pressure drop across the tube at 1 L/min airflow must be less than 3.4 kPa. Tubes are commercially available. 2. Personal sampling pump, 0.01 to 1 L/min, with flexible connecting tubing. 3. Gas chromatograph, flame ionization detector, integrator, and column (page 1000-1). 4. Vials, 2-mL, PTFE-lined caps. 5. Syringe, 10-µL, readable to 0.1 µL. 6. Volumetric flasks, 10-mL.
SPECIAL PRECAUTIONS: Benzene is a suspected human carcinogen. All work should be performed in a hood. SAMPLING: 1. Calibrate each personal sampling pump with a representative sampler in line. 2. Break the ends of the sampler immediately before sampling. Attach sampler to personal sampling pump with flexible tubing. 3. Sample at an accurately known flow rate between 0.01 and 1 L/min for a total sample size of 16 to 100 L. 4. Cap the samplers with plastic (not rubber) caps and pack securely for shipment. SAMPLE PREPARATION: 5. Place the front and back sorbent sections of the sampler tube in separate vials. Discard the glass wool and foam plugs. 6. Add 1.0 mL benzene to each vial. Attach crimp cap to each vial. 7. Allow to stand 30 min with occasional agitation. CALIBRATION AND QUALITY CONTROL: 8. Calibrate daily with at least six working standards over the range 0.01 to 1.5 mg allyl chloride per sample. a. Add known amounts of calibration stock solution to benzene in 10-mL volumetric flasks and dilute to the mark. b. Analyze together with samples and blanks (steps 11 and 12). c. Prepare calibration graph (peak area vs. mg allyl chloride). 9. Determine desorption efficiency (DE) at least once for each batch of charcoal used for sampling in the calibration range (step 8). Prepare three tubes at each of five levels plus three media blanks. a. Remove and discard back sorbent section of a media blank sampler. b. Inject a known amount of calibration stock solution directly onto front sorbent section with a microliter syringe. NIOSH Manual of Analytical Methods (NMAM), Fourth Edition ​ALLYL CHLORIDE: METHOD 1000, Issue 2, dated 15 August 1994 - Page 3 of 3
c. Cap the tube. Allow to stand overnight. d. Desorb (steps 5 through 7) and analyze together with working standards (steps 11 and 12). e. Prepare a graph of DE vs. mg allyl chloride recovered. 10. Analyze three quality control blind spikes and three analyst spikes to insure that the calibration graph and DE graph are in control. MEASUREMENT: 11. Set gas chromatograph according to manufacturer’s recommendations and to conditions given on page 1000-1. Inject sample aliquot manually using solvent flush technique or with autosampler. NOTE: If peak area is above the linear range of the working standards, dilute with benzene, reanalyze and apply the appropriate dilution factor in calculations. 12. Measure peak area. CALCULATIONS: 13. Determine the mass, mg (corrected for DE) of allyl chloride found in the sample front ( ) and back ( ) sorbent sections, and in the average media blank front ( ) and back ( ) sorbent sections. NOTE: If >  /10, report breakthrough and possible sample loss. 14. Calculate concentration, , of allyl chloride in the air volume sampled, (L): , mg/m³. EVALUATION OF METHOD: Method S116 was issued on May 9, 1975 [2], and validated over the range 1.8 to 7.2 mg/m³ at 25 °C and 759 mm Hg using a 100-L sample [1]. Overall precision, , was 0.071 with average recovery 105.5%, representing a nonsignificant bias. The concentration of allyl chloride was independently verified by direct gas chromatography. Desorption efficiency was 0.943 in the range 0.15 mg to 0.6 mg allyl chloride per sample. Breakthrough (5% on back section) occurred between 210 and 240 min when sampling an atmosphere containing 7.56 mg/m³ allyl chloride at 0.94 L/min at 0% RH. REFERENCES: [1] Documentation of the NIOSH Validation Tests, NIOSH, S116, U.S. Department of Health, Education, and Welfare, Publ. (NIOSH) 77-185 (1977). [2] NIOSH Manual of Analytical Methods, 2nd ed., V. 2, S116, U.S. Department of Health, Education, and Welfare, Publ. (NIOSH) 77-157-B (1977). METHOD REVISED BY: G. David Foley, NIOSH/DPSE; originally validated under NIOSH Contract CDC-99-74-45.
NIOSH Manual of Analytical Methods (NMAM), Fourth Edition