School of Chemistry, University of Bristol, Bristol, BS8 1TS, UK.
J Phys Chem A. 2010 Feb 4;114(4):1806-15. doi: 10.1021/jp9095985.
An approach for examining the hygroscopicity of single aerosol particles over a broad range in relative humidity (RH) using aerosol optical tweezers is presented and compared with measurements made using an electrodynamic balance. In particular, benchmark measurements on aqueous sodium chloride aerosol are presented over the RH range 45-75% (293 K), a RH range that had not previously been explored with aerosol optical tweezers. Measurements of the variation in equilibrium wet droplet size with RH are made using cavity-enhanced Raman scattering, with an accuracy of 1 nm in the determination of the wet particle radius. The full range of optical tweezers experimental measurements (including previous dual trapping comparative studies approaching a saturation relative humidity of 100%) are compared with determinations using other experimental techniques and with a range of model treatments. An assessment of the models and all experimental data for estimating the equilibrium size of a sodium chloride droplet suggests that the size can be predicted with an accuracy of better than 0.1% over the RH range 48-100%. Discrepancies between different measurements lead to an increase in uncertainty above 1% below an RH of 48% as efflorescence is approached. The optical tweezers' measurements of equilibrium size consistently agree with model predictions to within an error of 1% (<50 nm for the size range explored here) and mostly with an error of less than +/-0.1%. These data demonstrate the highly accurate nature of measurements of thermodynamic equilibrium size by aerosol optical tweezers and suggest that this approach may be used to investigate the competition between thermodynamic and kinetic factors in governing aerosol particle size over the full RH range.
提出了一种使用气溶胶光镊在较宽的相对湿度 (RH) 范围内检查单个气溶胶颗粒吸湿性的方法,并将其与使用电动天平进行的测量进行了比较。特别是,在 RH 范围为 45-75%(293 K)的情况下,对水合氯化钠气溶胶进行了基准测量,这是以前没有使用气溶胶光镊探索过的 RH 范围。使用腔增强拉曼散射测量平衡湿液滴尺寸随 RH 的变化,在确定湿颗粒半径时,精度为 1nm。将全范围的光镊实验测量值(包括以前接近 100%饱和相对湿度的双重捕获比较研究)与使用其他实验技术和一系列模型处理的测量值进行了比较。对模型和所有实验数据进行评估,以估计氯化钠液滴的平衡尺寸,结果表明,在 RH 范围为 48-100%时,尺寸的预测精度可以优于 0.1%。不同测量值之间的差异会导致 RH 低于 48%时(接近风化时)不确定性增加 1%以上。平衡尺寸的光镊测量值与模型预测值一致,误差在 1%以内(对于此处探索的尺寸范围为<50nm),且误差大多小于 +/-0.1%。这些数据表明,气溶胶光镊测量热力学平衡尺寸具有高度的准确性,并表明该方法可用于研究在整个 RH 范围内控制气溶胶颗粒尺寸的热力学和动力学因素之间的竞争。