Hyvärinen Antti-Pekka, Brus David, Zdímal Vladimír, Smolík Jiri, Kulmala Markku, Viisanen Yrjö, Lihavainen Heikki
Finnish Meteorological Institute, Erik Palménin aukio 1, P.O. Box 503, F1-00101 Helsinki, Finland.
J Chem Phys. 2006 Jun 14;124(22):224304. doi: 10.1063/1.2200341.
Homogeneous nucleation rate isotherms of n-butanol+helium were measured in a laminar flow diffusion chamber at total pressures ranging from 50 to 210 kPa to investigate the effect of carrier gas pressure on nucleation. Nucleation temperatures ranged from 265 to 280 K and the measured nucleation rates were between 10(2) and 10(6) cm(-3) s(-1). The measured nucleation rates decreased as a function of increasing pressure. The pressure effect was strongest at pressures below 100 kPa. This negative carrier gas effect was also temperature dependent. At nucleation temperature of 280 K and at the same saturation ratio, the maximum deviation between nucleation rates measured at 50 and 210 kPa was about three orders of magnitude. At nucleation temperature of 265 K, the effect was negligible. Qualitatively the results resemble those measured in a thermal diffusion cloud chamber. Also the slopes of the isothermal nucleation rates as a function of saturation ratio were different as a function of total pressure, 50 kPa isotherms yielded the steepest slopes, and 210 kPa isotherms the shallowest slopes. Several sources of inaccuracies were considered in the interpretation of the results: uncertainties in the transport properties, nonideal behavior of the vapor-carrier gas mixture, and shortcomings of the used mathematical model. Operation characteristics of the laminar flow diffusion chamber at both under-and over-pressure were determined to verify a correct and stable operation of the device. We conclude that a negative carrier gas pressure effect is seen in the laminar flow diffusion chamber and it cannot be totally explained with the aforementioned reasons.
在层流扩散室中,于50至210 kPa的总压力范围内测量了正丁醇+氦气的均相成核速率等温线,以研究载气压力对成核的影响。成核温度范围为265至280 K,测得的成核速率在10(2)至10(6) cm(-3) s(-1)之间。测得的成核速率随压力增加而降低。压力效应在低于100 kPa的压力下最强。这种负载气效应也与温度有关。在280 K的成核温度和相同的饱和比下,在50和210 kPa下测得的成核速率之间的最大偏差约为三个数量级。在265 K的成核温度下,该效应可忽略不计。定性地说,结果与在热扩散云室中测得的结果相似。等温成核速率随饱和比的斜率也因总压力而异,50 kPa等温线的斜率最陡,210 kPa等温线的斜率最浅。在结果解释中考虑了几个不准确的来源:传输性质的不确定性、蒸汽-载气混合物的非理想行为以及所用数学模型的缺点。确定了层流扩散室在欠压和过压下的运行特性,以验证该装置的正确和稳定运行。我们得出结论,在层流扩散室中观察到了负载气压力效应,并且上述原因无法完全解释该效应。