Rates of reaction between the nitrate radical and some unsaturated alcohols

Rate coefficients for nitrate radical gas-phase reactions with prop-2-en-l-ol (allyl alcohol), but-1-en-3-ol, and 2-methylbut-3-en-2-ol have been determined. Both absolute (fast flow discharge with diode laser detection of NO₃) and relative (batch reactor and FTIR spectroscopy) rate techniques were used to measure the rate coefficients. The rate coefficients at 294 K are: (1.3 ± 0.2) × 10^?14, (1.2 ± 0.3) × 10 ^?14, and (2.1 ± 0.3) × 10^?14 cm³ molecule^?1 s^?1 for prop-2-en-1-ol, but-1-en-3-ol, and 2-methylbut-3-en-2-ol, respectively. The activation energy for reaction of NO₃ with prop-2-en-1-ol was determined to 2.8 ± 2.5 kJ mol^?1 in the temperature range between 273 and 363 K. The atmospheric importance of unsaturated alcohols and structure-reactivity considerations are also discussed. © 1996 John Wiley & Sons, Inc.