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Methylene chloride

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Gas phase ion energetics data

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Data compilation copyright by the U.S. Secretary of Commerce on behalf of the U.S.A. All rights reserved.

Data evaluated as indicated in comments:
L - Sharon G. Lias

Data compiled as indicated in comments:
B - John E. Bartmess
MM - Michael M. Meot-Ner (Mautner)
LBLHLM - Sharon G. Lias, John E. Bartmess, Joel F. Liebman, John L. Holmes, Rhoda D. Levin, and W. Gary Mallard
LLK - Sharon G. Lias, Rhoda D. Levin, and Sherif A. Kafafi
RDSH - Henry M. Rosenstock, Keith Draxl, Bruce W. Steiner, and John T. Herron
LL - Sharon G. Lias and Joel F. Liebman

Quantity Value Units Method Reference Comment
IE (evaluated)11.33 ± 0.04eVN/AN/AL

Proton affinity at 298K

Proton affinity (kcal/mol) Reference Comment
150. ± 2.Cacace, de Petris, et al., 1999COS; C2H2. Paper reports PA although proton transfer reactivity brackets GB. Following authors, the GBs of CH2Cl2 and COS are equated given reversible proton transfer.; MM

Gas basicity at 298K

Gas basicity (review) (kcal/mol) Reference Comment
144. ± 2.Cacace, de Petris, et al., 1999COS; C2H2. Paper reports PA although proton transfer reactivity brackets GB. Following authors, the GBs of CH2Cl2 and COS are equated given reversible proton transfer.; MM

Ionization energy determinations

IE (eV) Method Reference Comment
11.32PEVon Niessen, Asbrink, et al., 1982LBLHLM
11.40PEKimura, Katsumata, et al., 1981LLK
11.32 ± 0.01PIWerner, Tsai, et al., 1974LLK
11.28EILossing, 1972LLK
11.33PEDewar and Worley, 1969RDSH
11.36CICermak, 1968RDSH
11.35 ± 0.02PIWatanabe, 1957RDSH
11.40PEDixon, Murrell, et al., 1971Vertical value; LLK

Appearance energy determinations

Ion AE (eV) Other Products MethodReferenceComment
C+25.5 ± 0.1?EIReed and Snedden, 1956RDSH
CH+21.72 ± 0.04?EIReed and Snedden, 1956RDSH
CHCl2+13.00 ± 0.10HEIReed and Snedden, 1956RDSH
CH2+17.0Cl2EIHaney and Franklin, 1968RDSH
CH2Cl+12.10ClEIHolmes, Lossing, et al., 1988LL
CH2Cl+12.14 ± 0.02ClPIWerner, Tsai, et al., 1974LLK
CH2Cl+12.15ClEILossing, 1972LLK
CH2Cl+12.1 ± 0.1ClEIHarrison and Shannon, 1962RDSH
CH2Cl+12.89 ± 0.03ClEIReed and Snedden, 1956RDSH
CHC12+12.12 ± 0.05HEIMartin, Lampe, et al., 1966RDSH
Cl+17.4 ± 0.1CH2ClEIDeCorpo, Bafus, et al., 1971LLK
Cl+17.4CH2ClEIFranklin and Haney, 1970RDSH

De-protonation reactions

CHCl2- + Hydrogen cation = Methylene chloride

By formula: CHCl2- + H+ = CH2Cl2

Quantity Value Units Method Reference Comment
Deltar375.7 ± 2.2kcal/molG+TSBorn, Ingemann, et al., 2000gas phase; D-EA from this reference yields BDE = 96.0±3.2 kcal/mol; B
Deltar374.5 ± 3.1kcal/molG+TSBohme, Lee-Ruff, et al., 1972gas phase; Comparable to DMSO; value altered from reference due to change in acidity scale; B
Quantity Value Units Method Reference Comment
Deltar368.0 ± 2.0kcal/molIMREBorn, Ingemann, et al., 2000gas phase; D-EA from this reference yields BDE = 96.0±3.2 kcal/mol; B
Deltar369.00 ± 0.70kcal/molIMREPoutsma, Paulino, et al., 1997gas phase; relative to tBuOH at «DELTA»Gacid = 369.3; B
Deltar366.8 ± 3.0kcal/molIMRBBohme, Lee-Ruff, et al., 1972gas phase; Comparable to DMSO; value altered from reference due to change in acidity scale; B

References

Go To: Top, Gas phase ion energetics data, Notes

Data compilation copyright by the U.S. Secretary of Commerce on behalf of the U.S.A. All rights reserved.

Cacace, de Petris, et al., 1999
Cacace, F.; de Petris, G.; Pepi, F.; Rosi, M.; Troiani, A., Gaseous [H3C-Cl-Cl](+) ions from the reaction of methane with Cl-3(+), the first example of a new dihalogenation process: Formation and characterization of CH3Cl2+ isomers by experimental and theoretical methods, Chemistry - A European Journal, 1999, 5, 2750. [all data]

Von Niessen, Asbrink, et al., 1982
Von Niessen, W.; Asbrink, L.; Bieri, G., 30.4 nm He(II) Photoelectron spectra of organic molecules. Part VI. Halogeno-compounds (C,H,X: X = Cl, Br, I), J. Electron Spectrosc. Relat. Phenom., 1982, 26, 173. [all data]

Kimura, Katsumata, et al., 1981
Kimura, K.; Katsumata, S.; Achiba, Y.; Yamazaki, T.; Iwata, S., Ionization energies, Ab initio assignments, and valence electronic structure for 200 molecules in Handbook of HeI Photoelectron Spectra of Fundamental Organic Compounds, Japan Scientific Soc. Press, Tokyo, 1981. [all data]

Werner, Tsai, et al., 1974
Werner, A.S.; Tsai, B.P.; Baer, T., Photoionization study of the ionization potentials fragmentation paths of the chlorinated methanes carbon tetrabromide, J. Chem. Phys., 1974, 60, 3650. [all data]

Lossing, 1972
Lossing, F.P., Free radicals by mass spectrometry. XLIV. Ionization potentials bond dissociation energies for chloro-and fluoromethyl radicals, Bull. Soc. Chim. Belg., 1972, 81, 125. [all data]

Dewar and Worley, 1969
Dewar, M.J.S.; Worley, S.D., Photoelectron spectra of molecules. I. Ionization potentials of some organic molecules and their interpretation, J. Chem. Phys., 1969, 50, 654. [all data]

Cermak, 1968
Cermak, V., Penning ionization electron spectroscopy. I. Determination of ionization potentials of polyatomic molecules, Collection Czech. Chem. Commun., 1968, 33, 2739. [all data]

Watanabe, 1957
Watanabe, K., Ionization potentials of some molecules, J. Chem. Phys., 1957, 26, 542. [all data]

Dixon, Murrell, et al., 1971
Dixon, R.N.; Murrell, J.N.; Narayan, B., The photoelectron spectra of the halomethanes, Mol. Phys., 1971, 20, 611. [all data]

Reed and Snedden, 1956
Reed, R.I.; Snedden, W., Studies in electron impact methods. Part 6.-The formation of the methine and carbon ions, J. Chem. Soc. Faraday Trans., 1956, 55, 876. [all data]

Haney and Franklin, 1968
Haney, M.A.; Franklin, J.L., Correlation of excess energies of electron-impact dissociations with the translational energies of the products, J.Chem. Phys., 1968, 48, 4093. [all data]

Holmes, Lossing, et al., 1988
Holmes, J.L.; Lossing, F.P.; McFarlane, R.A., Stabilization energy and positional effects in halogen-substituted alkyl ions., Int. J. Mass Spectrom. Ion Phys., 1988, 86, 209. [all data]

Harrison and Shannon, 1962
Harrison, A.G.; Shannon, T.W., An electron impact study of chloromethyl and dichloromethyl derivatives, Can. J. Chem., 1962, 40, 1730. [all data]

Martin, Lampe, et al., 1966
Martin, R.H.; Lampe, F.W.; Taft, R.W., An electron-impact study of ionization and dissociation in methoxy- and halogen- substituted methanes, J. Am. Chem. Soc., 1966, 88, 1353. [all data]

DeCorpo, Bafus, et al., 1971
DeCorpo, J.J.; Bafus, D.A.; Franklin, J.L., Enthalpies of formation of the monohalomethyl radicals from mass spectrometric studies of the dihalomethanes, J. Chem. Thermodyn., 1971, 3, 125. [all data]

Franklin and Haney, 1970
Franklin, J.L.; Haney, M.A., Energy distribution in ionic decomposition processes, Recent Developments in Mass Spectroscopy, ed. K. Ogata and T. Hayakawa Baltimore Univ. Park Press, Baltimore, MD, 1970, 909. [all data]

Born, Ingemann, et al., 2000
Born, M.; Ingemann, S.; Nibbering, N.M.M., Thermochemical properties of halogen-substituted methanes, methyl radicals, and carbenes in the gas phase, Int. J. Mass Spectrom., 2000, 194, 2-3, 103-113, https://doi.org/10.1016/S1387-3806(99)00125-6 . [all data]

Bohme, Lee-Ruff, et al., 1972
Bohme, D.K.; Lee-Ruff, E.; Young, L.B., Acidity order of selected bronsted acids in the gas phase at 300K, J. Am. Chem. Soc., 1972, 94, 5153. [all data]

Poutsma, Paulino, et al., 1997
Poutsma, J.C.; Paulino, J.A.; Squires, R.R., Absolute Heats of Formation of CHCl, CHF, and CClF. A Gas-Phase Experimental and G2 Theoretical Study., J. Phys. Chem. A, 1997, 101, 29, 5327, https://doi.org/10.1021/jp970778f . [all data]


Notes

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