Compilation of Henry’s Law Constants for Inorganic and Organic Species of Potential Importance in Environmental Chemistry http://www. mpch-mainz. mpg. de/—sander/res/henry. html Rolf Sander Air Chemistry Department Max-Planck Institute of Chermstry po BOX 3060 55020 Mainz Germany e-mail: sander@mpch-mainz. mpg. de Version 3 (April 8, 1999) c Rolf Sander (non-commercial reproduction permitted) Contents 1 Introduction 2 The physical quantity of solubility 3 Temperature dependence 4 unit conversions 5 How to use the Tables 6 Further Sources of Information 7 Data Table (Inorganic) oxygen (O) . r 157 hydrogen (H) . nitroge Ni orine (Cl) . bromine SWipe page iodine (l) . sulfur . .. rare gases . . other elements . 3333446667891011 1213 13 2 R Sander: Henrys law constants (http://www. mpch-mainz. mpg. de/—sander/res/henry. html) 8 Data Table (Organic) alkanes (C and H only) cycloalkanes (C and H aliphatic alkenes and cycloalkenes (C and H . aliphatic alkynes (C and H only) mononuclear aromatics (C and H . terpenes and polynuclear aromatics (C and H only) . . terpenes and polynuclear aromatics (C and H .. lcohols (ROH) (C, H, and O only) polyols ) (C, H, and O 14 1427 28 30 31 35 37 41 43444648 50 54 55 58 59 59 61 65 6 68 71 82 84 86 89 go 92 96 gg peroxides (ROOH) and peroxy radicals (ROO) (C, H, and O aldehydes (RCHO) (C, H, and O only) . ketones (RCOR) (C, H, and O only). carboxylic acids (RCOOH) and peroxy carboxylic acids (RCOOOH) (C, H, and O onlY) . . esters (RCOOR) (C, H, and O only) . ethers (ROR) (C, H, and O miscellaneous, e. g. multiple functional groups (C, H, and O … compounds with nitrogen: amines (RNH2 ) (C, H, O, and N only) 3 . ompounds with nitrogen: amines (RNH2 ) H, O, and N onlY) . compounds with nitrogen: amino acids (RCHNH2 COOH) compounds with nitrogen: heterocycles (C, H, O, and N only) compounds With nitrogen: nitrates (RON02 ) (C, H, O, and N . . compounds with nitrogen: nitriles (RCN) (C, H, O, and N onlY) . compounds with nitrogen: nitro (RN02 ) (C, H, O, and N . compounds with fluorine . aliphatlc compounds with chlorine . aromatic compounds with chlorine compounds with chlorine and compounds with compounds with iodine . 40F iodine sulfur polychlorobiphenyls (PC3s), pesticides, etc. Notes 10 Acknowledgements References . R. Sander: Henry’s law constants (http://www. mpch-mainz. mpg. de/-sander/res/henry. html) Introduction Henry’s law constants (solubilities) of trace gases of potential mportance in environmental chemistry (atmospheric chemistry, . ) have been collected and converted waste water treatment, into a uniform format. Dlsclamer: Although this compilation has been edited with greatest care the possibility of errors cannot be excluded. Ifyou use data from this table it is recommended that you also check the original literature.
If you find an error in Chis table, please tell me about The physical quantity of solubility There are severa’ ways of describing the solubility of a gas in water- Usually the Henry’s law constant kH is defined as: kH = ca / pg def species in the aqueous phase and pg is the partial pressure of that species in the gas phase. If kH refers to standard conditions (T 298. 15 K) it Will be denoted as kH . Henrys law constant can also be expressed as the dimensionless ratio between the aqueous-phase concentration ca of a species and its gas-phase concentration cg : kH = kH RT def where R = gas constant and T = temperature.
To distinguish these different physical quantities, this constant has been cc named kH px Sometimes the reciprocal value kH,inv is used, representing the volatility instead of the solubility. The usual definition is: px H,inv = pg/xa = def H2 0 MHZ O x kH where xa = molar mixing ratio in the aqueous phase, density of water, and MH2 0 – molar mass of water. Temperature dependence A simple way to describe Henry’s law as a function of temperature kH = kH x exp —Asoln H RI 1 -TT(4) where Asoln H enthalpy re, the temperature dependence is: -d In kH [ molaq /dm3 molaq /m3 aq aq l.
The official SI unit is The conversion is: atm Pa (5) kH kH = 101 ,325 x [M/atm] [(molaq /m3 )/Pa] aq cc The relation between kH and kH is: T kH x – 12. 2 x kH [K] [M/atr-n] 4 R. Sander: Henrys law constants AtT = 298. 15 K thiS leads to: kH = 0. 0409 x kH [M/atrn] x px The commonly used unit for kH,inv [atm]. The product of kH and kH,inv is constant: px kH,inv kH x = 55. 3 [M/atm] [atm] How to use the Tables Inorganic substances are sorted according to the elements they contain. The order chosen is: O, H, N, F, Cl, Br, l, S, rare gases, others_ Organic substances (i. e. verything with carbon, including CO and C02 ) are sorted somewhat arbitrarily by increasing chain length and complexi ms (N, F, Cl, Br, l, and S) are sorted in the same panic compounds. kH /d(1/T )’ contains the temperature dependence of the Henry’s law constants as defined in equations (4) and (5), rounded to wo significant digits and given in the unit For each table entry the column labeled ‘type’ denotes how the Henrys law constant was obtained in the given reference. Literature reviews are usually most reliable, followed by original publications of experimental determinations of kH .
Other data has to be treated more carefully. The types listed here are roughly ordered by decreasing reliability: ‘L’ ‘M’ ‘V’ ‘R’ The cited paper is a literature review. Original publication of a measured value (e. g. head-space or bubble column technique as explained by Betterton [1992]). Vapor pressure of the pure substance is used to determine the Henrys law constant (c/p for a saturated solution). The cited paper presents a recalculation of previously published material (e. g. extrapolation to a different temperature or concentration range). ermodynamical calculation (Osoln G = -RT In kH , See Sander [1999] for details). The paper that is cited here refers to another reference which could not obtain (e. g. personal communication, Ph. D. theses, internal papers etc. ). haven’t seen the paper that cite here. I found it referenced by another paper or know about it through others. The cited paper doesn’t clearly state how the value was obtained. The value 8 t through others. The cited paper doesn’t clearly state how the value was obtained. The value is estimated. Estimates are only listed if no reliable measurements are available for that compound.
In some cases there might be good agreement between different authors. However, if the original work they refer to is not known one has to be careful when evaluating the reliability. It is posslble that they were recalculating data from the same source. The similarity in that case would not be due to independent investigations. 6 Further Sources of Information Further important references: • monoaromatic hydrocarbons, hlorobenzenes, and PCBs: Mackay et al. [1992a] • polynuclear aromatic hydrocarbons, polychlorinated dioxins, and dibenzofuranes: Mackay et al. 1992b] • volatile organic chemicals: Mackay et al. [1993] • oxygen, nitrogen, and sulfur containing compounds: Mackay et al. [1995] • pestizides, PCB’s, etc. : Westcott et al. [1981]; Burkhard et al. [19851; Hassett and MiliCiC [1985]; Yin and Hassett [1986]; Murphy et al. [1987]; ShiLI et al. [1988]; Rice et al. [1 g and Glotfelty [1 988]; Fendinger et al. [1989]; De 1998]; Duce et al. [1991] • al. [1998]; Duce et al. [1991] • additional references that are not yet) included: Lide and Frederikse [1995]; Shiu et al. [ 1994]; Watts and Brimblecombe [1 987]; Wright et al. 1992a]; Tse et al. [1992]; Kolb et al. [1992]; Ettre et al. [1993]; Gan and Yates [1996]; Peng and Wan [1997]; Roberts and D- ndliker [1983]; Economou et al. [19971; Wong and Wang [1 997]; Suleimenov a and Krupp [1994]; Heron et al. [1998]; Becker et al. [1998]; Leuenberger et al. [1985] • predictive methods for Henrys law coefficients (QSPRs): Russell et al. [ 1992]; Nirmalakhandan et al. [1997]; Brennan et al. [1998] On the Internet: • The NIST Chemistry WebBook at http://webbook. nist. ov/chemistry • The Pesticide Properties Database (PPD) at http://www. rsusda. gov/rsml/ppdb2. html (http://www. mpch-mainz. mpg. de/—sander/res/henw. html) 7 Data Table (Inorganic) kH [M/atm] 1,3×10 1,2×10-3 1,3×10-3 1 0-3 1 ,3×10-3 1. 2×10-3 1. 2×10-2 1. 3*10-2 1. 3*10-2 1. 2×10-2 1. 1×10-2 1 2×10-2 9,4×10-3 1. 1 x10-2 9,4×10-3 8,9×10-3 7,8×10-4 7. 8*10-4 7. 8×10-4 7. 8×10-4 2. 9×101 3. 2×101 2. 5XIOl 2. 5XIOl 2. 0x102 g. ox103 3. 0x101 4. 6*103 g. ox103 1 -2×103 g. ox103 4. OX103 5. 7X103 7. IX104 7. IX104 1. 4X105 g. 7xl 04 04 1 . 0*105 8. 3*104 1 . 1X105 8. 6*104 -3 -d In kH d(1/T) substance reference
