Guo X X, Brimblecombe P
School of Environmental Sciences, University of East Anglia, Norwich NR4 7TJ, UK.
Chemosphere. 2007 Jun;68(3):436-44. doi: 10.1016/j.chemosphere.2007.01.011. Epub 2007 Mar 6.
Phenols are widely present in the atmosphere and nitration probably in the aerosol phase leads to nitrophenols. Nitration by nitric acid in sulfuric acid can be rapid, but little is known of the process under atmospheric conditions. The Henry's law constants K(H)(dagger) of phenol and 2-, 3- and 4-nitrophenol were all measured by a bubble stripping method as: 2820mol kg(-1) atm(-1) (at 298K), 147mol kg(-1) atm(-1) (at 298K), 1.6x10(4)mol kg(-1)atm(-1) (at 308K) and 2.1x10(4)mol kg(-1) atm(-1) (at 308K), respectively. The Henry's law constant of phenol in sulfuric acid systems is lower by more than a factor of two at 1020mol kg(-1) atm(-1) (at 298K) in 40wt% sulfuric acid, which is in line with salting-out of oxygen-containing aromatic compounds in water-sulfuric acid systems. The Henry's law constants of 2- and 4-nitrophenol behave differently and are almost independent of sulfuric acid concentration. The variation of K(H)(dagger) with temperature (T) described in terms of -dln(K(H)(dagger))/d(1/T) does not to vary with sulfuric acid concentration, suggesting enthalpy of dissolution for phenol is independent of sulfuric acid. The series of Henry's law constants measured here can describe the equilibrium situation for phenols in careful determinations of phase partitioning in the atmosphere.
酚类物质广泛存在于大气中,硝化作用可能在气溶胶相中发生,从而生成硝基酚。在硫酸中用硝酸进行硝化反应可能很快,但对于大气条件下的该过程却知之甚少。通过鼓泡吹扫法测得苯酚以及2-、3-和4-硝基酚的亨利定律常数K(H)(†)分别为:2820mol kg(-1) atm(-1)(298K时)、147mol kg(-1) atm(-1)(298K时)、1.6×10(4)mol kg(-1)atm(-1)(308K时)和2.1×10(4)mol kg(-1) atm(-1)(308K时)。在40wt%硫酸中,当浓度为1020mol kg(-1) atm(-1)(298K时)时,硫酸体系中苯酚的亨利定律常数降低了两倍多,这与水-硫酸体系中含氧芳香化合物的盐析现象一致。2-和4-硝基酚的亨利定律常数表现不同,且几乎与硫酸浓度无关。用-dln(K(H)(†))/d(1/T)描述的K(H)(†)随温度(T)的变化并不随硫酸浓度而变化,这表明苯酚的溶解焓与硫酸无关。此处测得的一系列亨利定律常数能够描述大气中酚类物质在精确测定相分配时的平衡情况。