Temperature dependencies of Henry's law constants and octanol/water partition coefficients for key plant volatile monoterpenoids.
To model the emission dynamics and changes in fractional composition of monoterpenoids from plant leaves, temperature dependencies of equilibrium coefficients must be known. Henry's law constants (H(pc), Pa m3 mol(-1) and octanol/water partition coefficients (K(OW), mol mol(-1)) were determined for 10 important plant monoterpenes at physiological temperature ranges (25-50 degrees C for H(pc) and 20-50 degrees C for K(OW)). A standard EPICS procedure was established to determine H(pc) and a shake flask method was used for the measurements of K(OW). The enthalpy of volatilization (deltaH(vol)) varied from 18.0 to 44.3 kJ mol(-1) among the monoterpenes, corresponding to a range of temperature-dependent increase in H(pc) between 1.3- and 1.8-fold per 10 degrees C rise in temperature. The enthalpy of water-octanol phase change varied from -11.0 to -23.8 kJ mol(-1), corresponding to a decrease of K(OW) between 1.15- and 1.32-fold per 10 degrees C increase in temperature. Correlations among physico-chemical characteristics of a wide range of monoterpenes were analyzed to seek the ways of derivation of H(pc) and K(OW) values from other monoterpene physico-chemical characteristics. H(pc) was strongly correlated with monoterpene saturated vapor pressure (P(v)), and for lipophilic monoterpenes, deltaH(vol) scaled positively with the enthalpy of vaporization that characterizes the temperature dependence of P(v) Thus, P(v) versus temperature relations may be employed to derive the temperature relations of H(pc) for these monoterpenes. These data collectively indicate that monoterpene differences in H(pc) and K(OW) temperature relations can importantly modify monoterpene emissions from and deposition on plant leaves.
Copolovici
Lucian O
LO
Department of Plant Physiology, Institute of Molecular and Cell Biology, University of Tartu, Riia 23, Tartu 51010, Estonia.
Niinemets
Ulo
U
D002627:Chemistry, Physical / Q000379:methods; D039821:Monoterpenes / Q000737:chemistry*; D000442:Octanols / Q000737:chemistry*; D010944:Plants / Q000737:chemistry*; D013696:Temperature; D014835:Volatilization; D014867:Water / Q000737:chemistry
D039821:Monoterpenes; D000442:Octanols; D014867:Water