Journal of Physical Chemistry B, Vol.109, No.37, 17693-17707, 2005
Kinetic studies on the tensile state of water in trees
The solar-powered generation and turnover of tensile, cohesive water in trees is described as a kinetic phenomenon of irreversible thermodynamics. A molecular kinetic model for tensile water formation and turnover is presented, which is found to be mathematically equivalent with an autocatalytic reaction (Brusselator). It is also shown to be consistent with the van der Waals equation for real liquid-gas systems, which empirically considers intermolecular forces. It can therefore be used to explain both the irreversible thermodynamics and the kinetics of the tensile liquid state of water. A nonlinear bistable evaporation behavior of tensile water is predicted, which has not yet been experimentally characterized in trees. Conventional sap flow techniques in combination with infrared imaging of heat flow around a local heat source were used to study the dynamics and energetics of water transport of trees during the eclipse of August 11, 1999. The evaporative "pulling force" in a tree was demonstrated with infrared techniques and shown to respond within seconds. While the ambient temperature during the eclipse did not drop by more than 2 degrees C, evaporative water transport was reduced by a factor of up to 2-3. The expected hysteresis (with an up to 50% decrease in energy-conversion-related entropy production) was measured, reflecting a bistable mode of conversion of solar energy into tensile water flow. This nonlinear (autocatalytic) phenomenon, together with tensile molecular order, damped the oscillating behavior of xylem tensile water, and its occasional all-or-none rupture (cavitation) can thus be explained by the nonlinear nature of intermolecular forces active in the water conduit/parenchyma environment. This characterizes the physical chemistry and energetics of tensile water in trees as an activesolar-energy-driven self-organizing process. Water is handled in the form of microcanonical ensembles and transformed into a stretched, metastable icelike state with stronger hydrogen bonding and increased heat of evaporation. The discussed model may open new opportunities for research and understanding toward innovative water technologies.