Center for Atmospheric Particle Studies, Carnegie Mellon University, Pittsburgh, Pennsylvania 15213, USA.
Environ Sci Technol. 2010 Jan 15;44(2):743-8. doi: 10.1021/es902497z.
To model the temperature-induced partitioning of semivolatile organics in laboratory experiments or atmospheric models, one must know the appropriate heats of vaporization. Current treatments typically assume a constant value of the heat of vaporization or else use specific values from a small set of surrogate compounds. With published experimental vapor-pressure data from over 800 organic compounds, we have developed a semiempirical correlation between the saturation concentration (C*, microg m(-3)) and the heat of vaporization (deltaH(VAP), kJ mol(-1)) for organics in the volatility basis set. Near room temperature, deltaH(VAP) = -11 log(10)C(300)() + 129. Knowledge of the relationship between C and deltaH(VAP) constrains a free parameter in thermodenuder data analysis. A thermodenuder model using our deltaH(VAP) values agrees well with thermal behavior observed in laboratory experiments.
为了在实验室实验或大气模型中模拟半挥发性有机物的温度诱导分配,必须知道适当的蒸发焓。目前的处理方法通常假设蒸发焓为常数,或者使用少数替代化合物的特定值。利用超过 800 种有机化合物的已发表实验蒸气压数据,我们开发了一个半经验相关性,将挥发性基组中有机物的饱和浓度(C*,μg m(-3))和蒸发焓(deltaH(VAP),kJ mol(-1))联系起来。在室温附近,deltaH(VAP) = -11 log(10)C(300)() + 129。C和 deltaH(VAP)之间的关系知识限制了热解析器数据分析中的一个自由参数。使用我们的 deltaH(VAP)值的热解析器模型与实验室实验中观察到的热行为非常吻合。