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CF3CH=CH2(HFO-1243zf,可能替代CF3CH2F(HFC-134a))的羟基自由基反应速率系数与温度及红外吸收截面的函数关系

Hydroxyl radical reaction rate coefficients as a function of temperature and IR absorption cross sections for CF3CH=CH2 (HFO-1243zf), potential replacement of CF3CH2F (HFC-134a).

作者信息

González Sergio, Jiménez Elena, Ballesteros Bernabé, Martínez Ernesto, Albaladejo José

机构信息

Department of Physical Chemistry, Faculty of Chemical Sciences and Technologies, University of Castilla-La Mancha, Avda. Camilo José Cela s/n, 13071, Ciudad Real, Spain.

出版信息

Environ Sci Pollut Res Int. 2015 Apr;22(7):4793-805. doi: 10.1007/s11356-014-3426-2. Epub 2014 Aug 21.

DOI:10.1007/s11356-014-3426-2
PMID:25138554
Abstract

CF3CH=CH2 (hydrofluoroolefin, HFO-1243zf) is a potential replacement of high global-warming potential (GWP) hydrofluorocarbon (HFC-134a, CF3CFH2). Both the atmospheric lifetime and the radiative efficiency of HFO-1243zf are parameters needed for estimating the GWP of this species. Therefore, the aim of this work is (i) to estimate the atmospheric lifetime of HFO-1243zf from the reported OH rate coefficients, k OH, determined under tropospheric conditions and (ii) to calculate its radiative efficiency from the reported IR absorption cross sections. The OH rate coefficient at 298 K also allows the estimation of the photochemical ozone creation potential (ε(POCP)). The pulsed laser photolysis coupled to a laser-induced fluorescence technique was used to determine k OH for the reaction of OH radicals with HFO-1243zf as a function of pressure (50-650 Torr of He) and temperature (263-358 K). Gas-phase IR spectra of HFO-1243zf were recorded at room temperature using a Fourier transform IR spectrometer between 500 and 4,000 cm(-1). At all temperatures, k OH did not depend on bath gas concentration (i.e., on the total pressure between 50 and 650 Torr of He). A slight but noticeable T dependence of k OH was observed in the temperature range investigated. The observed behavior is well described by the following Arrhenius expression: k OH(T) = (7.65 ± 0.26) × 10(-13) exp [(165 ± 10) / T] cm(3) molecule(-1) s(-1). Negligible IR absorption of HFO-1243zf was observed at wavenumbers greater than 1,700 cm(-1). Therefore, IR absorption cross sections, [Formula: see text], were determined in the 500-1,700 cm(-1) range. Integrated [Formula: see text] were determined between 650 and 1,800 cm(-1) for comparison purposes. The main diurnal removal pathway for HFO-1243zf is the reaction with OH radicals, which accounts for 64% of the overall loss by homogeneous reactions at 298 K. Globally, the lifetime due to OH reaction (τ OH) was estimated to be 8.7 days under the assumption of a well-mixed atmosphere. Assuming other removal pathways, the atmospheric lifetime (τ) was estimated to be ∼6 days. Considering the estimated τ OH and the measured IR absorption cross sections of HFO-1243zf in the atmospheric window (720-1,250 cm(-1)), its lifetime corrected radiative efficiency was calculated to be 0.019 W m(-2) ppbv(-1). GWP100 years for the HFO investigated, 0.29, is negligible compared to that of HFC-134a, the HFC to be potentially replaced (GWP100 years = 1,300, Hodnebrog et al. (Rev Geophys 51:300-378, 2013)). ε POCP for HFO-1243zf was estimated to be around 1 order of magnitude lower than that for ethylene. In conclusion, HFO-1243zf is fast degraded in the atmosphere, and it does not appreciably contribute to global warming and local/regional air pollution. Therefore, HFO-1243zf can be a suitable replacement for HFC-134a in air conditioning units.

摘要

三氟乙烯(氢氟烯烃,HFO - 1243zf)是一种具有高全球变暖潜能值(GWP)的氢氟碳化合物(HFC - 134a,CF3CFH2)的潜在替代品。HFO - 1243zf的大气寿命和辐射效率都是估算该物质GWP所需的参数。因此,本工作的目的是:(i)根据在对流层条件下测定的OH反应速率系数kOH估算HFO - 1243zf的大气寿命;(ii)根据报道的红外吸收截面计算其辐射效率。298K时的OH反应速率系数还可用于估算光化学臭氧生成潜势(ε(POCP))。采用脉冲激光光解与激光诱导荧光技术测定了OH自由基与HFO - 1243zf反应的kOH,该反应速率系数是压力(50 - 650 Torr氦气)和温度(263 - 358K)的函数。使用傅里叶变换红外光谱仪在室温下记录了HFO - 1243zf在500至4000 cm(-1)范围内的气相红外光谱。在所有温度下,kOH均不依赖于缓冲气体浓度(即50至650 Torr氦气之间的总压力)。在所研究的温度范围内观察到kOH对温度有轻微但显著的依赖性。观测到的行为可用以下阿伦尼乌斯表达式很好地描述:kOH(T) = (7.65 ± 0.26) × 10(-13) exp[(165 ± 10) / T] cm(3) molecule(-1) s(-1)。在波数大于1700 cm(-1)时,观测到HFO - 1243zf的红外吸收可忽略不计。因此,在500 - 1700 cm(-1)范围内测定了红外吸收截面[公式:见原文]。为了进行比较,在650至1800 cm(-1)之间测定了积分后的[公式:见原文]。HFO - 1243zf的主要日间去除途径是与OH自由基反应,在298K时,该反应占均相反应总损失的64%。在大气充分混合的假设下,全球范围内由OH反应导致的寿命(τOH)估计为8.7天。假设存在其他去除途径,大气寿命(τ)估计约为6天。考虑到估算的τOH以及在大气窗口(720 - 1250 cm(-1))中测量的HFO - 1243zf的红外吸收截面,计算出其寿命校正辐射效率为0.019 W m(-2) ppbv(-1)。所研究的HFO的100年GWP为0.29,与待被替代的HFC - 134a(100年GWP = 1300,Hodnebrog等人,《地球物理研究评论》51:300 - 378,2013年)相比可忽略不计。HFO - 1243zf的εPOCP估计比乙烯低约1个数量级。总之,HFO - 1243zf在大气中快速降解,对全球变暖和局部/区域空气污染的贡献不大。因此,HFO - 1243zf可作为空调装置中HFC - 134a的合适替代品。

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