Physicochemical Study of the Formation and Decomposition of Organohalogen Compounds

有机卤素化合物形成和分解的物理化学研究

• 批准号: 12305050
• 负责人: NAKAMURA Takashi
• 金额: $ 28.15万
• 依托单位: Tohoku University
• 依托单位国家: 日本
• 项目类别: Grant-in-Aid for Scientific Research (A)
• 财政年份: 2000
• 资助国家: 日本
• 起止时间: 2000 至 2002
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/grant/KAKENHI-PROJECT-12305050/
• 关键词: PCDD; Fs; Knudsen; Vapour pressure; Organohalogen compound; Flame retardant; Thermodynamic date; Quantum chemical calculation; Physicochemical property

The purpose of this study is to qualify and establish the physicochemical properties of organohalogen compounds such as PCDD/Fs and PBDD/Fs. The formation and decomposition behaviors of the organohalogen compounds can be estimated using their physicochemical properties.1.Determinations of vapor pressure of PCDD/Fs, OBDD, Kanechlor 300 and BFRs using Knudsen effusion methods. A new apparatus with a very small Knudsen cell was especially designed for the vapor pressure measurements of dioxin congeners and other POPs. The apparatus was calibrated by reference compounds, and the vapor pressure results were compared with the available reference data. The adsorption experiments were also carried out by mean of Knudsen cell. The apparent vapor pressures of OCDD with calcium hydroxide, hematite, graphite and activated carbon were measured. The adsorbing abilities of these compounds were estimated from the apparent vapor pressures of OCDD.2.Heat capacities of solid phase, melting points and enthalpies of fusion for DD, DF, OCDD and OCDF were measured by a modulated differential scanning calorimeter. Thermodynamic functions of gas phase such as heat capacity, entropy and standard enthalpy of formation for PCDD/Fs were calculated by the molecular orbital method with density functional theory. The temperature dependences of enthalpies of formation for DD, DF, OCDD and OCDF were estimated in the range from the solid phase to the gas phase using the data obtained in this study and reference data.3.Thermodynamic properties (heat capacity, entropy, enthalpy and Gibbs energy of formation) of PBDD/Fs were calculated by Density function theory and statistical thermodynamics theory. The employed methods were evaluated using brominated arenes compounds with experimental thermodynamic data.

本研究的目的是鉴定和确定有机卤素化合物（例如 PCDD/F 和 PBDD/F）的物理化学特性。有机卤素化合物的形成和分解行为可以通过其物理化学性质来估计。1.采用克努森流出法测定PCDD/Fs、OBDD、Kanechlor 300和BFRs的蒸气压。带有非常小的克努森池的新装置是专为二恶英同系物和其他持久性有机污染物的蒸气压测量而设计的。该装置通过参考化合物进行校准，并将蒸气压结果与可用的参考数据进行比较。吸附实验也利用努森池进行。测量了 OCDD 与氢氧化钙、赤铁矿、石墨和活性炭的表观蒸气压。根据OCDD的表观蒸气压评价了这些化合物的吸附能力。2.采用调制差示扫描量热仪测量了DD、DF、OCDD和OCDF的固相热容、熔点和熔化焓。采用密度泛函理论的分子轨道法计算了PCDD/Fs的热容、熵和标准生成焓等气相热力学函数。使用本研究获得的数据和参考数据，估算了从固相到气相范围内的 DD、DF、OCDD 和 OCDF 的生成焓的温度依赖性。 3.热力学性质（热容、熵、焓）利用密度函数理论和统计热力学理论计算了PBDD/Fs的生成能和吉布斯能。使用溴化芳烃化合物和实验热力学数据对所采用的方法进行了评估。

项目成果

Xian-Wei Li, Etsuro Shibata, Takashi Nakamura: "Theoretical Calculation of Thermodynamic Properties of Polybrominated Dibenzo-p-dioxins"Chemical Engineering Data. Vol.48,No.3. 727-735 (2003)

李贤伟，Etsuro Shibata，Takashi Nakamura：“多溴二苯并-对-二恶英热力学性质的理论计算”化学工程数据。

Xian-Wei Li, Etsuro Shibata, Takashi Nakamura: "Theoretical Calculation of Thermodynamic Properties of Polybrominated Dibenzo-p-dioxins"Chemical Engineering Data. Vol.48, No.3. 727-735 (2003)

李贤伟，Etsuro Shibata，Takashi Nakamura：“多溴二苯并-对-二恶英热力学性质的理论计算”化学工程数据。

Etsuro Shibata, Satoru Yamamoto, Hirotaka Koyo, Takashi Ikeda, Eiki Kasai, Masafumi Maeda, Takashi Nakamura: "Measurement of Thermodynamic Functions of Solid Phase for DD, DF, OCDD and OCDF, and Estimation of Thermodynamic Functions of Gas Phase for PCDD/

Etsuro Shibata、Satoru Yamamoto、Hirotaka Koyo、Takashi Ikeda、Eiki Kasai、Masafumi Maeda、Takashi Nakamura：“DD、DF、OCDD 和 OCDF 固相热力学函数的测量，以及 PCDD/ 气相热力学函数的估计”

Xian-Wei Li, Etsuro Shibata, Takashi Nakamura: "Thermodynamic Properties of Polybrominated Dibenzo-p-dioxins and Dibenzofurans Calculated by Density Functional Theory"Materials Transactions. Vol.44, No.5(掲載決定済み). (2003)

Xian-Wei Li、Etsuro Shibata、Takashi Nakamura：“通过密度泛函理论计算的多溴二苯并-对-二恶英和二苯并呋喃的热力学性质”Materials Transactions Vol.44，No.5（决定出版）。

Xian-Wei Li, Etsuro Shibata, Takashi Nakamura: "Thermodynamic Properties of Polybrominated Dibenzo-p-dioxins and Dibenzofurans Calculated by Density Functional Theory"Materials Transactions. Vol.44,No.5. 1004-1013 (2003)

李贤伟、Etsuro Shibata、Takashi Nakamura：“通过密度泛函理论计算的多溴二苯并-对-二恶英和二苯并呋喃的热力学性质”材料交易。