Response to Comment on "Measured Saturation Vapor Pressures of Phenolic and Nitro-Aromatic Compounds".
Response to Comment on "Measured Saturation Vapor Pressures of Phenolic and Nitro-Aromatic Compounds".
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对“酚类和硝基芳香族化合物的饱和蒸气压测量”评论的回应。
DOI：
10.1021/acs.est.7b02681
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发表时间：
2017
影响因子：
11.4
通讯作者：
Topping D
中科院分区：
文献类型：
--
作者：
Topping D
1.我们并不认为本文中提出的值可以作为“黄金标准”，尽管我们也不完全相信Wania等人关于报告值过低的论点（参见下文关于COSMOtherm预测的讨论）。我们需要与其他仪器进行比较测量，注意到这并不像规定一种仪器具有特定的低或高偏倚那样容易（例如，参考文献2）。我们感谢作者将现有数据添加到我们的数据中，以确认对所提供的值的一定程度的信心，同时强调潜在的问题。作者提出了关于为什么二羟基萘的数据可能太低的有趣论点，尽管这些论点似乎主要是启发性的。目前还不清楚是什么原因导致了KEMS中的这种行为，特别是因为，例如，Bilde等人1中包含的KEMS数据倾向于偏高而不是偏低，超过4个数量级的VP（Pa）。先前关于KEMS中潜在不确定性来源的讨论包括变化的样品相态、统计噪声、电离截面或在多个挥发性范围内缺乏适当的校准标准，所有这些都由Booth等人3详细描述。然而，我们估计这导致实验测定的固态蒸气压的最大不确定性为40%，在过冷液体状态下的最大不确定度为75%，不会导致系统误差。这些正是为什么需要更多和可靠的基本属性数据的原因，例如，使用各种实验装置的大气相关化学品。虽然COSMOtherm计算确实可以提供一些有用的见解，但如果没有这些硬的经验数据，就不可能得出结论，我们提出的二羟基萘或二硝基萘的值是否偏低。这是一个有益的补充。我们想指出的是，虽然比标准的基团贡献技术更基本的声音，很明显，COSMOtherm也已经“校准”与已知化学品的参数化数据集。4因此，这种方法可能受到影响，因为与标准基团贡献法一样，低挥发性物种缺乏可靠的经验数据。尽管进行了比较，但作者并不主张使用COSMOtherm来预测饱和蒸汽压，
1. We do not claim the values presented in this paper to act as a “gold standard”, although we are not fully convinced by Wania et al. on the arguments for the reported values being too low either (see also below for our discussion on the COSMOtherm predictions). We need comparative measurements from other instruments, noting that it is not as easy as prescribing one instrument to have a particular low or high bias (eg, ref 2). We thank the authors for adding the existing data to ours to confirm some level of confidence in the values presented while highlighting potential problems. The authors present interesting arguments on why the data for dihydroxynaphthalenes might be too low, although the arguments seem to be mostly heuristic in nature. It is unclear what might cause this behavior in the KEMS particularly as, for example, the KEMS data included in Bilde et al. 1 tends to be rather on the high than the low side, over 4 orders of magnitude of VPs (Pa). Previous discussions on potential for sources of uncertainty in the KEMS include varying sample phase state, statistical noise, ionization cross sections or lack of appropriate calibration standard in multiple volatility ranges, all described in detail by Booth et al. 3 However, we estimate that this results in a maximum uncertainty of 40% in experimentally determined solid state vapor pressures, a maximum uncertainty of 75% in the subcooled liquid state and will not result in a systematic error. These are exactly the type of reasons why more and reliable data on fundamental properties of, for example, atmospherically relevant chemicals is needed using various experimental setups. While the COSMOtherm calculations can indeed give some useful insights, without such hard empirical data it is impossible to conclude whether they values we present for dihydroxynaphtalines or dinitronaphtaline are biased low or not.2. This is a useful addition. We would like to point out that albeit more fundamentally sound than the standard group contribution techniques, it is apparent that also COSMOtherm has been “calibrated” with a parametrization data set of known chemicals. 4 This methodology is thus likely affected by the same lack of reliable empirical data for low-volatility species as the standard group contribution methods. While the authors do not advocate the use of COSMOtherm in predicting saturation vapor pressures despite comparisons made, a
影响因子：
6.3
作者：
Merikanto, J.;Spracklen, D. V.;Carslaw, K. S.
通讯作者：
Carslaw, K. S.
影响因子：
3.8
作者：
Booth, A. M.;Markus, T.;Topping, D. O.
通讯作者：
Topping, D. O.