1- and 2-Bromopropane (1025)
1- and 2-BROMOPROPANE
CH3 CH2 CH2 Br (CH3 )2 CHBr
MW: 123.00 123.00
METHOD: 2552, ISSUE 1
1025
CAS: 106-94-5 75-26-3
EVALUATION: PARTIAL
OSHA : None NIOSH: None ACGIH: None
RTECS:TX4110000 TX4111000 Issue 1: 15 March 2003
PROPERTIES: 1-BP: liquid; d= 1.354 g/mL @ 20 °C; BP= 71 °C; MP = -110 °C; FP= 25 °C. 2-BP: liquid; d= 1.310 g/mL @ 20 °C; BP= 59 °C; MP= -89 °C; FP= 19 °C.
NAMES & SYNONYMS: 1-Bromopropane: Propyl bromide, 1-BP. 2-Bromopropane: Isopropyl bromide, 2-BP.
SAMPLING SAMPLER:
Solid Sorbent Tube [1] (Anasorb CSC, 100/50 mg) Alternative sampler (Anasorb CMS, 150 mg/75 mg)
FLOW RATE:
0.01 to 0.2 L/min
VOL-MIN: -MAX:
0.1L 12 L
SHIPMENT:
Routine
SAMPLE STABILITY:
30 days at 5°C
BLANKS:
MEASUREMENT TECHNIQUE:
GAS CHROMATOGRAPHY, FID
ANALYTE:
1-Bromopropane and 2-Bromopropane
DESORPTION:
1-mL CS2 for 30 minutes with agitation.
INJECTION VOLUME:
1-:L
TEMPERATURE: -INJECTION: 200°C -DETECTOR: 250°C -COLUMN: 35°C (3 min) to 150°C (8°C/min) CARRIER GAS:
Helium
COLUMN:
Capillary, fused silica,30-m x 0.32-mm ID; 1.8-:m film phenyl/methyl polysiloxane, Rtx-502.2 or equivalent
CALIBRATION:
Standard solutions of analytes in CS 2 .
RANGE:
1-BP: 3.0 to 406.0 :g per sample [1] 2-BP: 4.5 to 393.0 :g per sample [1]
10% of field samples
ACCURACY RANGE STUDIED:
Not determined.
BIAS:
Not determined.
OVERALL PRECISION (Ö r T ):
Not determined.
ACCURACY:
Not determined.
ESTIMATED LOD:
PRECISION ( þ r ):
1-BP: 1.0 :g per sample [1] 2-BP: 1.0 :g per sample [1] 1-BP: 0.015 [1] 2-BP: 0.022 [1]
APPLICABILITY: Method can be applied to any process where bromopropanes are volatilized. The method was field tested in an industrial setting where 1-bromopropane was used in the application of adhesive to foam strips [2].
INTERFERENCES: Any compounds with similar retention times.
OTHER METHODS: None.
NIOSH Manual of Analytical Methods (NMAM), Fourth Edition 1- and 2-BR OM OP RO PAN E: ME TH OD 1025, Issue 1, dated 1 5 Ma rch 2003 - Page 2 of 4 REAGENTS:
EQUIPMENT:
1. 2. 3. 4. 5. 6. 7.
1. Sam pler: glass tu be, 7 cm long, 4-m m ID, flam e-sealed en ds w ith plastic cap s, containing two sections of Anasorb® CSC or equivalent (100/50 m g) separated b y a 2-mm urethane plug. A silylated glass wool plug precede s the front section and a 3-m m urethane foam plug follows the back section. 2. Alternative sampler: glass tube, 7 cm long, 4mm ID, flame-sealed ends with plastic caps, containing two sections of Anasorb® CMS or equivalent (150/75 m g) separated b y a 2-mm urethane plug. A silylated glass wool plug precede s the front section and a 3-m m urethane foam plug follows the back section. 3. Personal sampling pump, 0.01 to 0.2 L/min, connected with flexible tubing. 4. Ga s ch rom atog raph equ ipped with F ID, integrator and capillary column (see page 2552-1). 5. Autosampler vials, 2-mL, glass, with PTFElined crimp caps. 6. Syringes, 10-:L, 25-:L, and 1-mL. 7. Pipettes, 3-mL and 5-mL. 8. Volumetric flasks, 10-mL.
1-Bromopropane, GC grade. 2-Bromopropane, GC grade. Carbon disulfide, GC grade. Helium, prepurified and filtered. Hydrogen, prepurified and filtered. Air, compressed, purified, filtered. Calibration stock solution: Add known amounts of analytes to carbon disulfide in 10m L volum etric flas k.
- See SPECIAL PRECAUTIONS
SPECIAL PRECAUTIONS: Carbon d isulfide is toxic, explosive, and a fire hazard (FP= -30°C). W ork with carbo n disu lfide in a w ell ventilated ho od.
SAMPLING: 1. Ca librate each sam pling pum p with a represe ntative sam pler in line. 2. Break the ends of sampling tube imm ediately before sampling. Attach sampling tube to personal sam pling pum p with flexible tu bing. 3. Sam ple at an accurately known flow rate between 0.01 and 0.2 L/min for a total sample size of 12 L. 4. Ca p the sam plers with plastic ca ps a nd p ack sec urely for shipm ent.
SAMPLE PREPARATION: 5. Place the front and back sorbent sec tions of the sampler tube in separate vials. Place the glass wool preceding the front section into the vial containing the front sorbent section. Discard the urethane foam plugs. 6. Ad d 1.0 m L of carbon disulfide into each vial. Attach crim p caps to each vial. 7. Allow to stand fo r 30 m inutes with oc cas ional agitation.
CALIBRATION AND QUALITY CONTRO L: 8. Calibrate daily with at least six working standards from below the LOD to 10 times the LO Q. If necess ary, add itional standa rds m ay be a dde d to exten d the calibra tion cu rve. a. Add kn ow n am ounts of a nalytes to carbon disulfide solvent in a 10-mL volumetric flask and dilute to the mark. Prepare additional standards by serial dilution in 10-mL volumetric flasks. b. Analyze together with samp les and blanks (steps 11 and 12). c. Prepare calibration graph (peak area vs :g analyte). NIOSH Manual of Analytical Methods (NMAM), Fourth Edition 1- and 2-BR OM OP RO PAN E: ME TH OD 1025, Issue 1, dated 1 5 Ma rch 2003 - Page 3 of 4 9. Determ ine desorption efficiency (DE) at least once for each lot of Anas orb CSC or Anasorb CMS used for sam pling in the calibration ranges (step 8). a. Prepare three tubes at each of five levels p lus three m edia blank s. b. Inject a known amount of DE stock solution (5 to 25 :L) directly onto the front sorbent section of each tube with a microliter syringe. c. Allow the tubes to air equilibrate for several minutes, then cap the ends o f eac h tube an d allow to stan d overnight. d. De sorb (ste ps 5 -7) and a nalyze togeth er with stan dard s an d blan ks (step s 11 and 12). e. Prepare a graph of DE vs :g analyte recovered. 10. Analyze a minimum of three quality control blind spikes and three analyst spikes to ensure that the calibra tion gra ph a nd D E graph are in c ontro l.
MEASUREMENT: 11. Set gas chro m atog raph acc ording to m anu facturer’s recom m end ations and to conditions given on page 1025-1. Inject a 1-:L sample aliquot manually using the solvent flush technique or with an autosam pler. NOTE: If peak area is abo ve the linear ra nge of the working standard s, dilute with solvent, reanalyze, and apply the appropriate dilution factor in the calculations. 12. Measure peak areas.
CALCULATIONS: 13. Determine the m ass , :g (corrected for DE), of analyte found in the sam ple front (W f) and back (W b) sorbent sections, and in the average m edia blank front (B f) and back (B b) sorben t sec tions. NO TE : If W b > W f/10, report b reak throu gh a nd p oss ible sam ple loss. 14. Calculate conce ntration, C, of analyte in the air volume sam pled, V(L):
EVALUATION OF METHOD: Desorption efficiency was checked for 1- and 2-bromopropane by spiking known amounts (in CS 2) on 2 different sorbents, Anasorb CSC and Anasorb CMS. The effect of volatility on sample recovery was also determined for each ana lyte spiked on Anaso rb CSC and Anasorb C MS s orbent tu bes using G elA ir po rtable pumps to pull air throug h ea ch tube a t 0.2 L/min for 60 minutes (total volume was 12 L). Storage stability was dete rm ined for ea ch analyte after 7, 1 4, and 30 days. The average DE determined for 1-bromopropane from Anasorb CSC was 96.8% (RSD = 0.015) and for 2bromopropane was 101.0% (RSD = 0.020). W hen air was pulled through spiked sorbent tubes to determine the effects of volatility on sample recovery, the average DE determined for 1-bromopropane was 103.7% (RS D = 0.013) an d for 2-brom opro pan e wa s 99 .7% (RS D = 0.026). The average 30-day storage stability recovery for 1-bromopropane on Anasorb CSC was 106.9% (RSD = 0.009) and for 2-bromopropane was 98.2% (RSD = 0.013). The 30 day storage recovery using Anasorb CMS was 106% (RSD = 0.014) for 1-Bromopropane and 100.6% for 2-Bromopropane.
NIOSH Manual of Analytical Methods (NMAM), Fourth Edition 1- and 2-BR OM OP RO PAN E: ME TH OD 1025, Issue 1, dated 1 5 Ma rch 2003 - Page 4 of 4 REFERENCES : [1] Pendergrass, SM [1998]. 1- & 2-Bromopropane Backup Data Report for method development, National Institute for O ccu pation al Safety and Health, D AR T, C incinn ati, OH . Unp ublish ed re port. [2] Pendergrass, SM [1998]. Analytical Report for Sequence 9015 - 1-Bromopropane, National Institue for Occ upational Safety and Health, DAR T, Cincinnati, Ohio, Septem ber.
M ETH OD W RITT EN B Y: Stephanie M. Pendergrass, NIOSH/DART
NIOSH Manual of Analytical Methods (NMAM), Fourth Edition