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首页> 外文期刊>The journal of physical chemistry, A. Molecules, spectroscopy, kinetics, environment, & general theory >Kinetic Study of the Reactions of Cl Atoms with CF3CH2CH2OH,CF3CF2CH2OH,CHF2CF2CH2OH,and CF3CHFCF2CH2OH
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Kinetic Study of the Reactions of Cl Atoms with CF3CH2CH2OH,CF3CF2CH2OH,CHF2CF2CH2OH,and CF3CHFCF2CH2OH

机译：Cl原子与CF3CH2CH2OH，CF3CF2CH2OH，CHF2CF2CH2OH和CF3CHFCF2CH2OH反应的动力学研究

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The reaction kinetics of chlorine atoms with a series of partially fluorinated straight-chain alcohols,CF3-CH2CH2OH(1),CF3CF2CH2OH(2),CHF2CF2CH2OH(3),and CF3CHFCF2CH2OH(4),were studied in the gas phase over the temperature range of 273-363 K by using very low-pressure reactor mass spectrometry.The absolute rate coefficients were given by the expressions(in cm3 molecule~(-1)s~(-1)):k1=(4.42±0.48)X 10~(-11)exp(-255±20/T);k1(303)=(1.90±0.17)X10~(-11),k2=(2.23±0.31)X10~(-11)exp(-1065±106/T);k2(303)=(6.78±0.63)X10~(-13),k3=(8.51±0.62)X10~(-12)exp(-681±72/7);k3(303)=(9.00±0.82)X10~(-13)and k4=(6.18±0.84)X10~(12)exp(-736±42/T);k4(303)=(5.36±0.51)X10~(-13).The quoted 2 simga uncertainties include the systematic errors.All title reactions proceed via a hydrogen atom metathesis mechanism leading to HCl.Moreover,the oxidation of the primarily produced radicals was investigated,and the end products were the corresponding aldehydes(R_F-CHO;R_F=-CH2CF3,-CF2CF3,-CF2CHF2,and-CF2CHFCF3),providing a strong experimental indication that the primary reactions proceed mainly via the abstraction of a methylenic hydrogen adjacent to a hydroxyl group.Finally,the bond strengths and ionization potentials for the title compounds were determined by density functional theory calculations,which also suggest that the sigma-methylenic hydrogen is mainly under abstraction by Cl atoms.The correlation of room-temperature rate coefficients with ionization potentials for a set of 27 molecules,comprising fluorinated C2-C5 ethers and C2-C4 alcohols,is good with an average deviation of a factor of 2,and is given by the expression log(k)(in cm3 molecule~(-1)s~(-1))=(5.8±1.4)-(1.56±0.13)X(ionization potential(in eV)).
机译：在气相温度范围内研究了氯原子与一系列部分氟化的直链醇CF3-CH2CH2OH（1），CF3CF2CH2OH（2），CHF2CF2CH2OH（3）和CF3CHFCF2CH2OH（4）的反应动力学通过极低压反应器质谱分析273-363 K的绝对速率系数。表达式为（cm3分子〜（-1）s〜（-1））：k1 =（4.42±0.48）X 10 〜（-11）exp（-255±20 / T）; k1（303）=（1.90±0.17）X10〜（-11），k2 =（2.23±0.31）X10〜（-11）exp（-1065± 106 / T）; k2（303）=（6.78±0.63）X10〜（-13），k3 =（8.51±0.62）X10〜（-12）exp（-681±72/7）; k3（303）= （9.00±0.82）X10〜（-13），k4 =（6.18±0.84）X10〜（12）exp（-736±42 / T）; k4（303）=（5.36±0.51）X10〜（-13）引用的2个simga不确定性包括系统误差。所有标题反应都是通过氢原子易位机理生成HCl进行的。此外，还研究了主要生成的自由基的氧化作用，最终产物为相应的醛（R_F-CHO; R_F = -CH2CF3，-CF2CF3，-CF2CHF2和-CF2CHFCF3），提供了实验表明，主要反应主要是通过与羟基相邻的亚甲基氢的抽象进行的。最后，通过密度泛函理论计算确定了标题化合物的键合强度和电离电势，这也表明了σ-亚甲基氢主要是由Cl原子提取的。室温速率系数与电离势的相关性由27个分子组成，包括氟化C2-C5醚和C2-C4醇，平均偏差为2的表达式为log（k）（cm3分子〜（-1）s〜（-1））=（5.8±1.4）-（1.56±0.13）X（电离势（in eV））。

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