Excess Enthalpies of Binary Systems Containing Ketones, Ethers, or Anhydrides with Long Chain n-Alkanes with Isothermal Titration Calorimeter

• Main Authors: Wei-Chen Liao, 廖偉辰
• Other Authors: Ming-Jer Lee
• Format: Others
• Language: zh-TW
• Published: 2010
• Online Access: http://ndltd.ncl.edu.tw/handle/55419110099816043834

博士 === 國立臺灣科技大學 === 化學工程系 === 98 === Abstract In this study, an isothermal titration type calorimeter was installed to measure excess enthalpies(HE) for eighteen pairs of binary systems. The operating condition was fixed at 298.15 K (25℃) / 1.013 bar (1 atm). The binary systems contain 2-octanone, 3-octanone, 2-decanone, valeric anhydride, hexanoic anhydride or dipentyl ether + n-alkanes, where the alkanes include one of following three long chain paraffins: n-dodecane, n-tetradecane and n-hexadecane. The excess enthalpies are all positive, indicating that the mixing processes are all endothermic. The excess enthalpies vary symmetrically with the mole fraction of constituent components. The experimental values of the systems containing dipentyl ether are apparently greater than those of other systems. The correlated results of the modified Redlich-Kister equation are satisfactorily well with the average deviation to be about within the experimental uncertainty. In addition to the modified Redlich-Kister equation, three equations of state: Peng-Robinson (PR), Patel-Teja (PT) and Cubic Chain-of-Rotators (CCOR), and two solution theory models: Wilson and NRTL models were used to correlate excess enthalpy data. The correlated results from the PR and the PT equations of state are not adequate, except for the dipentyl ether-containing systems. The CCOR2, which adopted two binary interaction parameters in the mixing rules, improved the correlated results from the CCOR1. The Wilson model has an inherent upper limit, 800 (J．mol-1), for HE. It can only be applicable to the systems containing dipentyl ether whose values of HE are sufficient small . Among all the studied models, the NRTL gave the best results, except for the anhydride-containing systems; where the correlated results were better than other equations of state and solution theory models.