Tittlemier Sheryl A, Braekevelt Eric, Halldorson Thor, Reddy Christopher M, Norstrom Ross J
Centre for Analytical and Environmental Chemistry, Carleton University, Ottawa, Ont., Canada K1S 5B6.
Chemosphere. 2004 Dec;57(10):1373-81. doi: 10.1016/j.chemosphere.2004.08.061.
Basic physical-chemical properties of five bromine and chlorine containing mixed halogenated dimethyl bipyrroles (HDBPs) were determined using established methods. Subcooled liquid vapour pressures (P(o)(L,25)), aqueous solubilities (S(w,25)), and octanol/water partition coefficients (K(ow)) were determined using the gas chromatography-retention time, generator column, and slow-stirring methods, respectively. Henry's Law constants (H25) were estimated using experimentally-derived P(o)(L) and S(w,25) data. Values of all four properties were generally similar to those reported for other polyhalogenated aromatic compounds [P(o)(L,25) = (7.55-191) x 10(-6) Pa; S(w,25) = (1.0-1.9) x 10(-5) g/l; log K(ow) = 6.4-6.7; H25 = 0.0020-0.14 Pa m3/mol]. The effect of replacing a chlorine with a bromine atom significantly decreased P(o)(L,25) (log P(o)(L,25) = -0.4197 (# bromine atoms) - 2.643, p<0.01) and H25 (log H25 = -0.508 (# bromine atoms) + 0.394, p<0.02). There were no significant effects of bromine/chlorine substitution on S(w,25) or K(ow). A simple Level I equilibrium partitioning model predicted the environmental behaviour of HDBPs to be similar to a tetrabrominated diphenyl ether. Only slight differences in behaviour amongst HDBP congeners were predicted since substitution of a bromine for a chlorine (Cl/Br substitution) atom had less effect than H/Cl or H/Br substitution on P(o)(L,25), S(w,25), H25, and K(ow).
采用既定方法测定了五种含溴和氯的混合卤代二甲基联吡咯(HDBP)的基本物理化学性质。分别使用气相色谱保留时间法、发生器柱法和慢速搅拌法测定了过冷液体蒸气压(P(o)(L,25))、水溶性(S(w,25))和正辛醇/水分配系数(K(ow))。利用实验得出的P(o)(L)和S(w,25)数据估算了亨利定律常数(H25)。所有这四种性质的值通常与其他多卤代芳香化合物报道的值相似[P(o)(L,25) = (7.55 - 191)×10(-6) Pa;S(w,25) = (1.0 - 1.9)×10(-5) g/l;log K(ow) = 6.4 - 6.7;H25 = 0.0020 - 0.14 Pa m3/mol]。用溴原子取代氯原子的效果显著降低了P(o)(L,25)(log P(o)(L,25) = -0.4197(溴原子数) - 2.643,p<0.01)和H25(log H25 = -0.508(溴原子数) + 0.394,p<0.02)。溴/氯取代对S(w,25)或K(ow)没有显著影响。一个简单的一级平衡分配模型预测HDBP的环境行为与四溴二苯醚相似。由于用溴取代氯原子(Cl/Br取代)对P(o)(L,25)、S(w,25)、H25和K(ow)的影响小于H/Cl或H/Br取代,因此预测HDBP同系物之间的行为只有细微差异。