Methanethiol

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Phase change data

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

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

Data compiled as indicated in comments:
TRC - Thermodynamics Research Center, NIST Boulder Laboratories, Chris Muzny director
AC - William E. Acree, Jr., James S. Chickos
ALS - Hussein Y. Afeefy, Joel F. Liebman, and Stephen E. Stein
DRB - Donald R. Burgess, Jr.
DH - Eugene S. Domalski and Elizabeth D. Hearing
CAL - James S. Chickos, William E. Acree, Jr., Joel F. Liebman, Students of Chem 202 (Introduction to the Literature of Chemistry), University of Missouri -- St. Louis

Quantity Value Units Method Reference Comment
Tboil279.1 ± 0.5KAVGN/AAverage of 6 values; Individual data points
Quantity Value Units Method Reference Comment
Tfus150.18KN/AMorris, Lanum, et al., 1960Uncertainty assigned by TRC = 0.02 K; TRC
Tfus150.1KN/ATeets, 1934Uncertainty assigned by TRC = 0.5 K; TRC
Tfus150.1KN/AEllis and Reid, 1932Uncertainty assigned by TRC = 0.4 K; TRC
Tfus152.15KN/ATimmermans and Mattaar, 1921Uncertainty assigned by TRC = 0.6 K; TRC
Quantity Value Units Method Reference Comment
Ttriple150.14KN/ARussell, Osborne, et al., 1942Crystal phase 1 phase; Uncertainty assigned by TRC = 0.05 K; TRC
Ttriple150.16KN/ARussell, Osborne, et al., 1942Crystal phase 1 phase; Uncertainty assigned by TRC = 0.03 K; TRC
Quantity Value Units Method Reference Comment
Tc469.9KN/ABerthoud and Brum, 1924Uncertainty assigned by TRC = 0.4 K; by disappearance of meniscus turbidity; TRC
Tc469.9KN/ABerthoud and Brum, 1924Uncertainty assigned by TRC = 0.4 K; by appearance of turbidity; TRC
Quantity Value Units Method Reference Comment
Pc71.35atmN/ABerthoud and Brum, 1924Uncertainty assigned by TRC = 0.5000 atm; vapor pressure at Tc; TRC
Quantity Value Units Method Reference Comment
ρc6.891mol/lN/ABerthoud and Brum, 1924Uncertainty assigned by TRC = 0.04 mol/l; TRC
Quantity Value Units Method Reference Comment
Δvap5.69kcal/molN/AReid, 1972AC
Δvap5.69 ± 0.02kcal/molVGood, Lacina, et al., 1961ALS
Δvap5.71kcal/molN/AGood, Lacina, et al., 1961DRB

Enthalpy of vaporization

ΔvapH (kcal/mol) Temperature (K) Method Reference Comment
5.8719279.12N/ARussell, Osborne, et al., 1942, 2P = 101.325 kPa; DH
6.50223.N/ADykyj, Svoboda, et al., 1999Based on data from 208. to 298. K.; AC
6.02359.AStephenson and Malanowski, 1987Based on data from 267. to 359. K.; AC
6.14268.AStephenson and Malanowski, 1987Based on data from 221. to 283. K.; AC
5.66360.AStephenson and Malanowski, 1987Based on data from 345. to 424. K.; AC
5.78429.AStephenson and Malanowski, 1987Based on data from 414. to 470. K.; AC
6.17264.N/AStephenson and Malanowski, 1987Based on data from 222. to 279. K. See also Russell, Osborne, et al., 1942, 2.; AC

Entropy of vaporization

ΔvapS (cal/mol*K) Temperature (K) Reference Comment
21.04279.12Russell, Osborne, et al., 1942, 2P; DH

Antoine Equation Parameters

log10(P) = A − (B / (T + C))
    P = vapor pressure (atm)
    T = temperature (K)

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Temperature (K) A B C Reference Comment
279.9 to 458.4.348101122.494-21.748Stull, 1947Coefficents calculated by NIST from author's data.
221.87 to 279.134.186301031.431-32.72Russell, Osborne, et al., 1942, 2Coefficents calculated by NIST from author's data.

Enthalpy of fusion

ΔfusH (kcal/mol) Temperature (K) Reference Comment
1.4150.2Domalski and Hearing, 1996AC

Entropy of fusion

ΔfusS (cal/mol*K) Temperature (K) Reference Comment
0.380137.6Domalski and Hearing, 1996CAL
9.400150.2

Enthalpy of phase transition

ΔHtrs (kcal/mol) Temperature (K) Initial Phase Final Phase Reference Comment
0.05251137.6crystaline, IIcrystaline, IRussell, Osborne, et al., 1942, 2DH
1.411150.16crystaline, IliquidRussell, Osborne, et al., 1942, 2DH

Entropy of phase transition

ΔStrs (cal/mol*K) Temperature (K) Initial Phase Final Phase Reference Comment
0.382137.6crystaline, IIcrystaline, IRussell, Osborne, et al., 1942, 2DH
9.398150.16crystaline, IliquidRussell, Osborne, et al., 1942, 2DH

In addition to the Thermodynamics Research Center (TRC) data available from this site, much more physical and chemical property data is available from the following TRC products:


Gas phase ion energetics data

Go To: Top, Phase change data, References, Notes

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:
HL - Edward P. Hunter and Sharon G. Lias
L - Sharon G. Lias

Data compiled as indicated in comments:
B - John E. Bartmess
LL - Sharon G. Lias and Joel F. Liebman
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

View reactions leading to CH4S+ (ion structure unspecified)

Quantity Value Units Method Reference Comment
IE (evaluated)9.439 ± 0.005eVN/AN/AL
Quantity Value Units Method Reference Comment
Proton affinity (review)184.8kcal/molN/AHunter and Lias, 1998HL
Quantity Value Units Method Reference Comment
Gas basicity177.kcal/molN/AHunter and Lias, 1998HL
Quantity Value Units Method Reference Comment
Δf(+) ion213. ± 2.kcal/molN/AN/A 
Quantity Value Units Method Reference Comment
ΔfH(+) ion,0K215. ± 2.kcal/molN/AN/A 

Ionization energy determinations

IE (eV) Method Reference Comment
9.446 ± 0.010PINourbakhsh, Norwood, et al., 1991LL
9.4386PIKutina, Edwards, et al., 1982T = 0K; LBLHLM
9.46PEKimura, Katsumata, et al., 1981LLK
9.44PEOgata, Onizuka, et al., 1973LLK
9.44PEOgata, Onizuka, et al., 1972LLK
9.415PEKroto and Suffolk, 1972LLK
9.42PEFrost, Herring, et al., 1972LLK
9.44 ± 0.01PIAkopyan, Sergeev, et al., 1970RDSH
9.440 ± 0.005PIWatanabe, Nakayama, et al., 1962RDSH
9.443 ± 0.002SPrice, Teegan, et al., 1950RDSH
9.44PECradock and Whiteford, 1972Vertical value; LLK
9.44PEBock, Wagner, et al., 1972Vertical value; LLK

Appearance energy determinations

Ion AE (eV) Other Products MethodReferenceComment
CHS+≤13.55 ± 0.04H+H2PIKutina, Edwards, et al., 1982LBLHLM
CHS+≤13.61 ± 0.04H+H2PIKutina, Edwards, et al., 1982T = 0K; LBLHLM
CHS+15.8 ± 0.5?EIRuska and Franklin, 1969RDSH
CH2S+10.58 ± 0.05H2PINourbakhsh, Norwood, et al., 1991LL
CH2S+10.61 ± 0.05H2PIKutina, Edwards, et al., 1982T = 0K; LBLHLM
CH2S+10.55 ± 0.05H2PIKutina, Edwards, et al., 1982LBLHLM
CH2S+10.8 ± 0.1H2PIAkopyan, Sergeev, et al., 1970RDSH
CH2S+[HCSH+]~11.51H2PIKutina, Edwards, et al., 1982LBLHLM
CH2S+[HCSH+]~11.57H2PIKutina, Edwards, et al., 1982T = 0K; LBLHLM
CH3+13.296 ± 0.021SHPIKutina, Edwards, et al., 1982LBLHLM
CH3+13.357 ± 0.021SHPIKutina, Edwards, et al., 1982T = 0K; LBLHLM
CH3S+11.23 ± 0.05HPINourbakhsh, Norwood, et al., 1991LL
CH3S+11.48 ± 0.05HEIHolmes, Lossing, et al., 1983LBLHLM
CH3S+11.550 ± 0.005HPIKutina, Edwards, et al., 1982LBLHLM
CH3S+11.611 ± 0.005HPIKutina, Edwards, et al., 1982T = 0K; LBLHLM
CH3S+11.37 ± 0.05HPIAkopyan, Sergeev, et al., 1970RDSH
CH3S+11.6 ± 0.1HEITaft, Martin, et al., 1965RDSH

De-protonation reactions

MeS anion + Hydrogen cation = Methanethiol

By formula: CH3S- + H+ = CH4S

Quantity Value Units Method Reference Comment
Δr357.6 ± 2.0kcal/molD-EASchwartz, Davico, et al., 2000gas phase; B
Δr357.5 ± 2.0kcal/molD-EAMoran and Ellison, 1988gas phase; B
Δr356.9 ± 2.2kcal/molG+TSBartmess, Scott, et al., 1979gas phase; value altered from reference due to change in acidity scale; B
Quantity Value Units Method Reference Comment
Δr350.6 ± 2.0kcal/molIMREBartmess, Scott, et al., 1979gas phase; value altered from reference due to change in acidity scale; B

CH3S- + Hydrogen cation = Methanethiol

By formula: CH3S- + H+ = CH4S

Quantity Value Units Method Reference Comment
Δr395.3 ± 2.6kcal/molG+TSKass, Guo, et al., 1990gas phase; Acidity between D2O and Me2NH.; B
Δr391.6 ± 7.7kcal/molD-EAKass, Guo, et al., 1990gas phase; Between O2 and SO2. Explains bad anchor in McIver Jr. and Fukuda, 1982; B
Quantity Value Units Method Reference Comment
Δr388.2 ± 2.5kcal/molIMRBKass, Guo, et al., 1990gas phase; Acidity between D2O and Me2NH.; B

References

Go To: Top, Phase change data, 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.

Morris, Lanum, et al., 1960
Morris, J.C.; Lanum, W.J.; Helm, R.V.; Haines, W.E.; Cook, G.L.; Ball, J.S., Purification and Properties of Ten Organic Sulfur Compounds, J. Chem. Eng. Data, 1960, 5, 112-6. [all data]

Teets, 1934
Teets, D.E., The Relation of the Melting Point to the Number of Carbon Atoms in a Series of Normal Mercaptans, J. Am. Chem. Soc., 1934, 56, 1143. [all data]

Ellis and Reid, 1932
Ellis, L.M.; Reid, E.E., The Preparation and Properties of A Double Series of Aliphatic Mercaptans, J. Am. Chem. Soc., 1932, 54, 1674. [all data]

Timmermans and Mattaar, 1921
Timmermans, J.; Mattaar, J.F., Freezing points of orgainic substances VI. New experimental determinations., Bull. Soc. Chim. Belg., 1921, 30, 213. [all data]

Russell, Osborne, et al., 1942
Russell, H.; Osborne, D.W.; Yost, D.M., The Heat Capacity, Entropy, Heats of Fusion, Transition and Vaporization and Vapor Pressures of Methyl Mercaptan, J. Am. Chem. Soc., 1942, 64, 165-9. [all data]

Berthoud and Brum, 1924
Berthoud, A.; Brum, R., Physical Properties of Some Organic Compounds., J. Chim. Phys. Phys.-Chim. Biol., 1924, 21, 143-60. [all data]

Reid, 1972
Reid, Robert C., Handbook on vapor pressure and heats of vaporization of hydrocarbons and related compounds, R. C. Wilhort and B. J. Zwolinski, Texas A Research Foundation. College Station, Texas(1971). 329 pages.$10.00, AIChE J., 1972, 18, 6, 1278-1278, https://doi.org/10.1002/aic.690180637 . [all data]

Good, Lacina, et al., 1961
Good, W.D.; Lacina, J.L.; McCullough, J.P., Methanethiol and carbon disulfide: Heats of combustion and formation by rotating-bomb calorimetry, J. Phys. Chem., 1961, 65, 2229-2231. [all data]

Russell, Osborne, et al., 1942, 2
Russell, H., Jr.; Osborne, D.W.; Yost, D.M., The heat capacity, entropy, heats of fusion, transition, and vaporization and vapor pressures of methyl mercaptan, J. Am. Chem. Soc., 1942, 64, 165-169. [all data]

Dykyj, Svoboda, et al., 1999
Dykyj, J.; Svoboda, J.; Wilhoit, R.C.; Frenkel, M.L.; Hall, K.R., Vapor Pressure of Chemicals: Part A. Vapor Pressure and Antoine Constants for Hydrocarbons and Sulfur, Selenium, Tellurium and Hydrogen Containing Organic Compounds, Springer, Berlin, 1999, 373. [all data]

Stephenson and Malanowski, 1987
Stephenson, Richard M.; Malanowski, Stanislaw, Handbook of the Thermodynamics of Organic Compounds, 1987, https://doi.org/10.1007/978-94-009-3173-2 . [all data]

Stull, 1947
Stull, Daniel R., Vapor Pressure of Pure Substances. Organic and Inorganic Compounds, Ind. Eng. Chem., 1947, 39, 4, 517-540, https://doi.org/10.1021/ie50448a022 . [all data]

Domalski and Hearing, 1996
Domalski, Eugene S.; Hearing, Elizabeth D., Heat Capacities and Entropies of Organic Compounds in the Condensed Phase. Volume III, J. Phys. Chem. Ref. Data, 1996, 25, 1, 1, https://doi.org/10.1063/1.555985 . [all data]

Hunter and Lias, 1998
Hunter, E.P.; Lias, S.G., Evaluated Gas Phase Basicities and Proton Affinities of Molecules: An Update, J. Phys. Chem. Ref. Data, 1998, 27, 3, 413-656, https://doi.org/10.1063/1.556018 . [all data]

Nourbakhsh, Norwood, et al., 1991
Nourbakhsh, S.; Norwood, K.; Yin, H.-M.; Liao, C.-L.; Ng, C.Y., Vacuum ultraviolet photodissociation and photoionization studies of CH3SH and SH, J. Chem. Phys., 1991, 95, 946. [all data]

Kutina, Edwards, et al., 1982
Kutina, R.; Edwards, A.; Goodman, G.; Berkowitz, J., Photoionization mass spectrometry of CH3SH, CD3SH, and CH3SD: Heats of formation of CH3S+ (CH2SH+), CH2S+, CH2S, and HCS+, J. Chem. Phys., 1982, 77, 5508. [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]

Ogata, Onizuka, et al., 1973
Ogata, H.; Onizuka, H.; Nihei, Y.; Kamada, H., The photoelectron spectra of alcohols, mercaptans and amines, Bull. Chem. Soc. Jpn., 1973, 46, 3036. [all data]

Ogata, Onizuka, et al., 1972
Ogata, H.; Onizuka, H.; Nihei, Y.; Kamada, H., On the first bands of the photoelectron spectra of amines, alcohols, and mercaptans, Chem. Lett., 1972, 895. [all data]

Kroto and Suffolk, 1972
Kroto, H.W.; Suffolk, R.J., The photoelectron spectrum of an unstable species in the pyrolysis products of dimethyldisulphide, Chem. Phys. Lett., 1972, 15, 545. [all data]

Frost, Herring, et al., 1972
Frost, D.C.; Herring, F.G.; Katrib, A.; McDowell, C.A.; McLean, R.A.N., Photoelectron spectra of CH3SH, (CH3)2S, C6H5SH, and C6H5CH2SH; the bonding between sulfur and carbon, J. Phys. Chem., 1972, 76, 1030. [all data]

Akopyan, Sergeev, et al., 1970
Akopyan, M.E.; Sergeev, Yu.L.; Vilesov, F.I., Photionization in vapors of aliphatic sulfides. I. Methymercaptan, dimethyl and diethyl sulfides, High Energy Chem., 1970, 4, 265, In original 305. [all data]

Watanabe, Nakayama, et al., 1962
Watanabe, K.; Nakayama, T.; Mottl, J., Ionization potentials of some molecules, J. Quant. Spectry. Radiative Transfer, 1962, 2, 369. [all data]

Price, Teegan, et al., 1950
Price, W.C.; Teegan, J.P.; Walsh, A.D., The far ultra-violet absorption spectra of the hydrides and deuterides of sulphur, selenium and tellurium and of the methyl derivatives of hydrogen sulphide, Proc. Roy. Soc. (London), 1950, A201, 600. [all data]

Cradock and Whiteford, 1972
Cradock, S.; Whiteford, R.A., Photoelectron spectra of the methyl, silyl and germyl derivatives of the group VI elements, J. Chem. Soc. Faraday Trans. 2, 1972, 68, 281. [all data]

Bock, Wagner, et al., 1972
Bock, H.; Wagner, G.; Kroner, J., Photoelektronenspektren und molekuleigenschaften, XIV. Die delokalisation des schwefel-elektronenpaar in CH3S-substituierten aromaten, Chem. Ber., 1972, 105, 3850. [all data]

Ruska and Franklin, 1969
Ruska, W.E.W.; Franklin, J.L., Ion-molecule reactions in hydrogen sulfide, methanethiol and 2-thiapropane, Intern. J. Mass Spectrom. Ion Phys., 1969, 3, 221. [all data]

Holmes, Lossing, et al., 1983
Holmes, J.L.; Lossing, F.P.; Terlouw, J.K.; Burgers, P.C., Novel gas-phase ions. The radical cations [CH2XH]+. (X = F, Cl, Br, I, OH, NH2, SH) and [CH2CH2NH3]+., Can. J. Chem., 1983, 61, 2305. [all data]

Taft, Martin, et al., 1965
Taft, R.W.; Martin, R.H.; Lampe, F.W., Stabilization energies of substituted methyl cations. The effect of strong demand on the resonance order, J. Am. Chem. Soc., 1965, 87, 2490. [all data]

Schwartz, Davico, et al., 2000
Schwartz, R.L.; Davico, G.E.; Lineberger, W.C., Negative-ion photoelectron spectroscopy of CH3S-, J. Electron Spectros. Rel. Phenom., 2000, 108, 1-3, 163-168, https://doi.org/10.1016/S0368-2048(00)00125-0 . [all data]

Moran and Ellison, 1988
Moran, S.; Ellison, G.B., Photoelectron Spectroscopy of Sulfur Ions, J. Phys. Chem., 1988, 92, 7, 1794, https://doi.org/10.1021/j100318a021 . [all data]

Bartmess, Scott, et al., 1979
Bartmess, J.E.; Scott, J.A.; McIver, R.T., Jr., The gas phase acidity scale from methanol to phenol, J. Am. Chem. Soc., 1979, 101, 6047. [all data]

Kass, Guo, et al., 1990
Kass, S.R.; Guo, H.-Z.; Dahlke, G.D., The Thiomethyl Anion: Formation, Reactivity, and Thermodynamic Properties, J. Am. Soc. Mass Spectrom., 1990, 1, 5, 366, https://doi.org/10.1016/1044-0305(90)85016-F . [all data]

McIver Jr. and Fukuda, 1982
McIver Jr.; Fukuda, E.K., Equilibrium Electron Affinities, Lec. Notes in Chem., 1982, 31, 165. [all data]


Notes

Go To: Top, Phase change data, Gas phase ion energetics data, References