GSTDTAP  > 地球科学
DOI10.5194/acp-19-4419-2019
Solubility and solution-phase chemistry of isocyanic acid, methyl isocyanate, and cyanogen halides
Roberts, James M.1; Liu, Yong2
2019-04-04
发表期刊ATMOSPHERIC CHEMISTRY AND PHYSICS
ISSN1680-7316
EISSN1680-7324
出版年2019
卷号19期号:7页码:4419-4437
文章类型Article
语种英语
国家USA
英文摘要

Condensed-phase uptake and reaction are important atmospheric removal processes for reduced nitrogen species, isocyanic acid (HNCO), methyl isocyanate (CH3NCO), and cyanogen halides (XCN, X = Cl, Br, I); yet many of the fundamental quantities that govern this chemistry have not been measured or are not well studied. These nitrogen species are of emerging interest in the atmosphere as they have either biomass burning sources, i.e., HNCO and CH3NCO, or, like the XCN species, have the potential to be a significant condensed-phase source of NCO- and therefore HNCO. Solubilities and the first-order reaction rate of these species were measured for a variety of solutions using a bubble flow reactor method with total reactive nitrogen (N-r) detection. The aqueous solubility of HNCO was measured as a function of pH and had an intrinsic Henry's law solubility of 20 (+/- 2)M atm(-1) and a K-a of 2.0 (+/- 0.3) x 10(-4) M (pK(a) = 3.7 +/- 0.1) at 298 K. The temperature dependence of HNCO solubility was very similar to other small nitrogencontaining compounds, such as HCN, acetonitrile (CH3CN), and nitromethane, and the dependence on salt concentration exhibited the "salting out" phenomenon. The rate constant of reaction of HNCO with 0.45M as NH4Cl, was measured at pH = 3 and found to be 1.2 (+/- 0.1) x 10(-3) M(-1)s( -1), faster than the rate that would be estimated from rate measurements at much higher pHs. The solubilities of HNCO in the non-polar solvents n-octanol (n-C8H17OH) and tridecane (C13H28) were found to be higher than aqueous solution for n-octanol (87 +/- 9 M atm(-1) at 298 K) and much lower than aqueous solution for tridecane (1.7 +/- 0.17 M atm(-1) at 298 K), features that have implications for multi-phase and membrane transport of HNCO. The first-order loss rate of HNCO in n-octanol was determined to be relatively slow, 5.7 (+/- 1.4) x 10(-5)s (-1). The aqueous solubility of CH3NCO was found to be 1.3 (+/- 0.13)M atm(-1) independent of pH, and CH3NCO solubility in n-octanol was also determined at several temperatures and ranged from 4.0 (+/- 0.5)M atm(-1) at 298 K to 2.8 (+/- 0.3)M atm(-1) at 310 K. The aqueous hydrolysis of CH3NCO was observed to be slightly acid-catalyzed, in agreement with literature values, and reactions with n-octanol ranged from 2.5 (+/- 0.5) to 5.3 (+/- 0.7) x 10(-3)s(-1) from 298 to 310K. The aqueous solubilities of XCN, determined at room temperature and neutral pH, were found to increase with halogen atom polarizability from 1.4 (+/- 0.2)M atm(-1) for CICN and 8.2 (+/- 0.8)M atm(-1) for BrCN to 270 (+/- 54)M atm(-1) for ICN. Hydrolysis rates, where measurable, were in agreement with literature values.


The atmospheric loss rates of HNCO, CH3NCO, and XCN due to heterogeneous processes are estimated from solubilities and reaction rates. Lifetimes of HNCO range from about 1 day against deposition to neutral pH surfaces in the boundary layer, but otherwise can be as long as several months in the middle troposphere. The loss of CH3NCO due to aqueous-phase processes is estimated to be slower than, or comparable to, the lifetime against OH reaction (3 months). The loss of XCNs due to aqueous uptake is estimated to range from being quite slow, with a lifetime of 2-6 months or more for CICN and 1 week to 6 months for BrCN to 1 to 10 days for ICN. These characteristic times are shorter than photolysis lifetimes for CICN and BrCN, implying that heterogeneous chemistry will be the controlling factor in their atmospheric removal. In contrast, the photolysis of ICN is estimated to be faster than heterogeneous loss for average midlatitude conditions.


领域地球科学
收录类别SCI-E
WOS记录号WOS:000463378900006
WOS关键词IONIZATION MASS-SPECTROMETRY ; BY-PRODUCT FORMATION ; ION PROTON-TRANSFER ; HENRYS LAW ; ORGANIC-COMPOUNDS ; HYDROGEN-CYANIDE ; CHROMATOGRAPHIC DETERMINATION ; CYANATE CONCENTRATIONS ; DISSOCIATION-ENERGIES ; ATMOSPHERIC CHEMISTRY
WOS类目Environmental Sciences ; Meteorology & Atmospheric Sciences
WOS研究方向Environmental Sciences & Ecology ; Meteorology & Atmospheric Sciences
引用统计
文献类型期刊论文
条目标识符http://119.78.100.173/C666/handle/2XK7JSWQ/182284
专题地球科学
作者单位1.NOAA, ESRL Chem Sci Div, Boulder, CO 80305 USA;
2.Univ Colorado, Dept Chem, Denver, CO 80217 USA
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GB/T 7714
Roberts, James M.,Liu, Yong. Solubility and solution-phase chemistry of isocyanic acid, methyl isocyanate, and cyanogen halides[J]. ATMOSPHERIC CHEMISTRY AND PHYSICS,2019,19(7):4419-4437.
APA Roberts, James M.,&Liu, Yong.(2019).Solubility and solution-phase chemistry of isocyanic acid, methyl isocyanate, and cyanogen halides.ATMOSPHERIC CHEMISTRY AND PHYSICS,19(7),4419-4437.
MLA Roberts, James M.,et al."Solubility and solution-phase chemistry of isocyanic acid, methyl isocyanate, and cyanogen halides".ATMOSPHERIC CHEMISTRY AND PHYSICS 19.7(2019):4419-4437.
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