Kołodziejczyk Agata, Pyrcz Patryk, Błaziak Kacper, Pobudkowska Aneta, Sarang Kumar, Szmigielski Rafał
Institute of Physical Chemistry, Polish Academy of Sciences, ul. Kasprzaka 44/52, 01-224 Warsaw, Poland.
Department of Physical Chemistry, Faculty of Chemistry, Warsaw University of Technology, ul. Noakowskiego 3, 00-664 Warsaw, Poland.
ACS Omega. 2020 Mar 31;5(14):7919-7927. doi: 10.1021/acsomega.9b04231. eCollection 2020 Apr 14.
The physicochemical properties and the synthesis of four α-pinene oxidation products, terebic acid, 3-methyl-1,2,3-butanetricarboxylic acid (MBTCA), diaterpenylic acid acetate (DTAA), and pinanediol, are presented in this study. The physicochemical properties encompass thermal properties, solubility in water, and dissociation constant (p ) for the investigated compounds. It was found that terebic acid exhibits a relatively high melting temperature of 449.29 K, whereas pinanediol revealed a low melting temperature of 329.26 K. The solubility in water was determined with the dynamic method and the experimental results were correlated using three different mathematical models: Wilson, NRTL, and UNIQUAC equations. The results of the correlation indicate that the Wilson equation appears to work the best for terebic acid and pinanediol. The calculated standard deviation was for 3.79 for terebic acid and 1.25 for pinanediol. In contrast, UNIQUAC was the best mathematical model for DTAA and MBTCA. The calculated standard deviation was 0.57 for DTAA and 2.21 for MBTCA. The measured water solubility increased in the following order: pinanediol > DTAA ≥ MBTCA > terebic acid, which affects their multiphase aging chemistry in the atmosphere. Moreover, acidity constants (p ) at 298, 303, and 308 K were determined for DTAA with the Bates-Schwarzenbach spectrophotometric method. The p values obtained at 298, 303, and 308 K were found to be 3.76, 3.85, and 3.88, respectively.
本研究介绍了四种α-蒎烯氧化产物——松萜酸、3-甲基-1,2,3-丁三羧酸（MBTCA）、乙酸二萜酯（DTAA）和蒎烷二醇的物理化学性质及合成方法。这些物理化学性质包括所研究化合物的热性质、在水中的溶解度和解离常数（p）。结果发现，松萜酸的熔点相对较高，为449.29 K，而蒎烷二醇的熔点较低，为329.26 K。采用动态法测定了在水中的溶解度，并使用三种不同的数学模型（Wilson方程、NRTL方程和UNIQUAC方程）对实验结果进行关联。关联结果表明，Wilson方程对松萜酸和蒎烷二醇的拟合效果最佳。计算得到的松萜酸标准偏差为3.79，蒎烷二醇为1.25。相比之下，UNIQUAC是DTAA和MBTCA的最佳数学模型。计算得到的DTAA标准偏差为0.57，MBTCA为2.21。测得的水溶性按以下顺序增加：蒎烷二醇>DTAA≥MBTCA>松萜酸，这会影响它们在大气中的多相老化化学过程。此外，采用Bates-Schwarzenbach分光光度法测定了DTAA在298、303和308 K时的酸度常数（p）。发现在298、303和308 K时获得的p值分别为3.76、3.85和3.88。
