Benzene, Chloro- - The NIST WebBook

Benzene, chloro-

• Formula: C6H5Cl
• Molecular weight: 112.557
• IUPAC Standard InChI: InChI=1S/C6H5Cl/c7-6-4-2-1-3-5-6/h1-5H Copy
• IUPAC Standard InChIKey: MVPPADPHJFYWMZ-UHFFFAOYSA-N Copy
• CAS Registry Number: 108-90-7
• Chemical structure: This structure is also available as a 2d Mol file or as a computed 3d SD file The 3d structure may be viewed using Java or Javascript.
• Other names: Chlorobenzene; Monochlorobenzene; MCB; Phenyl Chloride; Benzene chloride; Chlorbenzene; Chlorobenzol; Monochlorbenzene; Chloorbenzeen; Chlorbenzol; Chlorobenzen; Chlorobenzene, mono-; Clorobenzene; Monochloorbenzeen; Monochlorbenzol; Monoclorobenzene; NCI-C54886; Chlorobenzenu; UN 1134; Abluton T30; CP 27; IP Carrier T 40; NSC 8433; Tetrosin SP
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• Information on this page:
  • Gas phase ion energetics data
  • References
  • Notes
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Gas phase ion energetics data

Go To: Top, 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 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

View reactions leading to C6H5Cl+ (ion structure unspecified)

Quantity	Value	Units	Method	Reference	Comment
IE (evaluated)	9.07 ± 0.02	eV	N/A	N/A	L
Quantity	Value	Units	Method	Reference	Comment
Proton affinity (review)	753.1	kJ/mol	N/A	Hunter and Lias, 1998	HL
Quantity	Value	Units	Method	Reference	Comment
Gas basicity	724.6	kJ/mol	N/A	Hunter and Lias, 1998	HL

Ionization energy determinations

IE (eV)	Method	Reference	Comment
9.08	PE	Fujisawa, Ohno, et al., 1986	LBLHLM
8.8	PE	Klasinc, Kovac, et al., 1983	LBLHLM
9.07 ± 0.03	PE	Ruscic, Klasinc, et al., 1981	LLK
9.10	PE	Kimura, Katsumata, et al., 1981	LLK
9.10 ± 0.02	PE	Mohraz, Maier, et al., 1980	LLK
9.10 ± 0.02	PE	Maier and Marthaler, 1978	LLK
9.059 ± 0.008	EQ	Lias and Ausloos, 1978	LLK
9.09	PE	Behan, Johnstone, et al., 1976	LLK
9.55	EI	Baldwin, Loudon, et al., 1976	LLK
9.07 ± 0.02	PIPECO	Baer, Tsai, et al., 1976	LLK
9.1 ± 0.1	EI	Gilbert, Leach, et al., 1973	LLK
8.99	EI	Cooks, Bertrand, et al., 1973	LLK
9.08 ± 0.01	PI	Sergeev, Akopyan, et al., 1970	RDSH
9.035	PI	Momigny, Goffart, et al., 1968	RDSH
9.05	S	Quemerais, Morlais, et al., 1967	RDSH
9.07	PI	Bralsford, Harris, et al., 1960	RDSH
9.07 ± 0.02	PI	Watanabe, 1957	RDSH
9.07	PE	Klasinc, Kovac, et al., 1983	Vertical value; LBLHLM
9.067	PE	Potts, Lyus, et al., 1980	Vertical value; LLK
9.08	PE	Sell and Kupperman, 1978	Vertical value; LLK
9.07	PE	Klasinc, Novak, et al., 1978	Vertical value; LLK
9.09	PE	Streets and Ceasar, 1973	Vertical value; LLK

Appearance energy determinations

Ion	AE (eV)	Other Products	Method	Reference	Comment
C4H4+	17.6 ± 0.1	?	EI	Momigny, 1959	RDSH
C6H4+	14.9 ± 0.2	HCl	EI	Momigny, 1959	RDSH
C6H5+	11.81	Cl	DER	Ripoche, Dimicoli, et al., 1991	LL
C6H5+	12.88 ± 0.05	Cl	EI	Burgers and Holmes, 1984	LBLHLM
C6H5+	13.1 ± 0.1	Cl	EI	Burgers and Holmes, 1984	LBLHLM
C6H5+	12.25 ± 0.04	Cl	PIPECO	Rosenstock, Stockbauer, et al., 1980	LLK
C6H5+	12.47 ± 0.06	Cl	PI	Rosenstock, Stockbauer, et al., 1979	LLK
C6H5+	13.06	Cl	PIPECO	Baer, Tsai, et al., 1976	LLK
C6H5+	12.81	Cl	EI	Johnstone and Mellon, 1972	LLK
C6H5+	12.55 ± 0.07	Cl	PI	Sergeev, Akopyan, et al., 1970	RDSH
C6H5+	13.2 ± 0.1	Cl	EI	Majer and Patrick, 1962	RDSH

De-protonation reactions

C6H4Cl- + =

By formula: C6H4Cl- + H+ = C6H5Cl

Quantity	Value	Units	Method	Reference	Comment
ΔrH°	1636. ± 7.9	kJ/mol	Bran	Wenthold and Squires, 1995	gas phase; B
ΔrH°	1633. ± 8.8	kJ/mol	G+TS	Wenthold and Squires, 1994	gas phase; between furan, pyridine; B
ΔrH°	1633. ± 8.8	kJ/mol	G+TS	Wenthold, Paulino, et al., 1991	gas phase; Between H2O, furan. Wenthold and Squires, 1994 indicates isomerization occuring.; B
Quantity	Value	Units	Method	Reference	Comment
ΔrG°	1602. ± 8.4	kJ/mol	H-TS	Wenthold and Squires, 1995	gas phase; B
ΔrG°	1598. ± 8.4	kJ/mol	IMRB	Wenthold and Squires, 1994	gas phase; between furan, pyridine; B
ΔrG°	1598. ± 8.4	kJ/mol	IMRB	Wenthold, Paulino, et al., 1991	gas phase; Between H2O, furan. Wenthold and Squires, 1994 indicates isomerization occuring.; B

C6H4Cl- + =

By formula: C6H4Cl- + H+ = C6H5Cl

Quantity	Value	Units	Method	Reference	Comment
ΔrH°	1650. ± 5.4	kJ/mol	Bran	Wenthold and Squires, 1995	gas phase; B
ΔrH°	1631. ± 8.8	kJ/mol	G+TS	Wenthold and Squires, 1994	gas phase; between furan, pyridine; B
ΔrH°	1631. ± 8.8	kJ/mol	G+TS	Wenthold, Paulino, et al., 1991	gas phase; Between H2O, furan. Wenthold and Squires, 1994 indicates isomerization occuring.; B
Quantity	Value	Units	Method	Reference	Comment
ΔrG°	1618. ± 5.9	kJ/mol	H-TS	Wenthold and Squires, 1995	gas phase; B
ΔrG°	1598. ± 8.4	kJ/mol	IMRB	Wenthold and Squires, 1994	gas phase; between furan, pyridine; B
ΔrG°	1598. ± 8.4	kJ/mol	IMRB	Wenthold, Paulino, et al., 1991	gas phase; Between H2O, furan. Wenthold and Squires, 1994 indicates isomerization occuring.; B

C6H4Cl- + =

By formula: C6H4Cl- + H+ = C6H5Cl

Quantity	Value	Units	Method	Reference	Comment
ΔrH°	1618. ± 8.8	kJ/mol	G+TS	Andrade and Riveros, 1996	gas phase; B
ΔrH°	1624. ± 8.4	kJ/mol	Bran	Wenthold and Squires, 1995	gas phase; B
ΔrH°	1622. ± 13.	kJ/mol	G+TS	Wenthold, Paulino, et al., 1991	gas phase; Between PhF, furan; B
Quantity	Value	Units	Method	Reference	Comment
ΔrG°	1584. ± 8.4	kJ/mol	IMRE	Andrade and Riveros, 1996	gas phase; B
ΔrG°	1590. ± 8.8	kJ/mol	H-TS	Wenthold and Squires, 1995	gas phase; B
ΔrG°	1588. ± 13.	kJ/mol	IMRB	Wenthold, Paulino, et al., 1991	gas phase; Between PhF, furan; B
ΔrG°	1586. ± 21.	kJ/mol	IMRB	Bartmess and McIver Jr., 1979	gas phase; Between H2O, MeOH; 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.

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]

Fujisawa, Ohno, et al., 1986 Fujisawa, S.; Ohno, K.; Masuda, S.; Harada, Y., Penning ionization electron spectroscopy of monohalogenobenzenes: C6H5F, C6H5Cl, C6H5Br, and C6H5I, J. Am. Chem. Soc., 1986, 108, 6505. [all data]

Klasinc, Kovac, et al., 1983 Klasinc, L.; Kovac, B.; Gusten, H., Photoelectron spectra of acenes. Electronic structure and substituent effects, Pure Appl. Chem., 1983, 55, 289. [all data]

Ruscic, Klasinc, et al., 1981 Ruscic, B.; Klasinc, L.; Wolf, A.; Knop, J.V., Photoelectron spectra of and Ab initio calculations on chlorobenzenes. 1. Chlorobenzene and dichlorobenzenes, J. Phys. Chem., 1981, 85, 1486. [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]

Mohraz, Maier, et al., 1980 Mohraz, M.; Maier, J.P.; Heilbronner, E., He(I α) and He(Iα) photoelectron spectra of fluorinated chloro- and bromobenzenes, J. Electron Spectrosc. Relat. Phenom., 1980, 19, 429. [all data]

Maier and Marthaler, 1978 Maier, J.P.; Marthaler, O., Emission spectra of the radical cations of 1,3-dichlorobenzene, 1,4-dichlorobenzene and 1,3,5-trichlorobenzene in the gas phase, Chem. Phys., 1978, 32, 419. [all data]

Lias and Ausloos, 1978 Lias, S.G.; Ausloos, P.J., eIonization energies of organic compounds by equilibrium measurements, J. Am. Chem. Soc., 1978, 100, 6027. [all data]

Behan, Johnstone, et al., 1976 Behan, J.M.; Johnstone, R.A.W.; Bentley, T.W., An evaluation of empirical methods for calculating the ionization potentials of substituted benzenes, Org. Mass Spectrom., 1976, 11, 207. [all data]

Baldwin, Loudon, et al., 1976 Baldwin, M.A.; Loudon, A.G.; Maccoll, A.; Webb, K.S., The nature and fragmentation pathways of the molecular ions of some arylureas, arylthioureas, acetanilides, thioacetanilides and related compounds, Org. Mass Spectrom., 1976, 11, 1181. [all data]

Baer, Tsai, et al., 1976 Baer, T.; Tsai, B.P.; Smith, D.; Murray, P.T., Absolute unimolecular decay rates of energy selected metastable halobenzene ions, J. Chem. Phys., 1976, 64, 2460. [all data]

Gilbert, Leach, et al., 1973 Gilbert, J.R.; Leach, W.P.; Miller, J.R., Ionisation appearance potential measurements in arene chromium tricarbonyls, J. Organomet. Chem., 1973, 49, 219. [all data]

Cooks, Bertrand, et al., 1973 Cooks, R.G.; Bertrand, M.; Beynon, J.H.; Rennekamp, M.E.; Setser, D.W., Energy partitioning data as an ion structure probe. Substituted anisoles, J. Am. Chem. Soc., 1973, 95, 1732. [all data]

Sergeev, Akopyan, et al., 1970 Sergeev, Yu.L.; Akopyan, M.E.; Vilesov, F.I.; Kleimenov, V.I., Photoionization processes in phenyl halides, Opt. i Spektroskopiya, 1970, 29, 119, In original 63. [all data]

Momigny, Goffart, et al., 1968 Momigny, J.; Goffart, C.; D'Or, L., Photoionization studies by total ionization measurements. I. Benzene and its monohalogeno derivatives, Intern. J. Mass Spectrom. Ion Phys., 1968, 1, 53. [all data]

Quemerais, Morlais, et al., 1967 Quemerais, A.; Morlais, M.; Robin, S., Spectres d'absorption du benzene et du monochlorobenzene dans l'ultraviolet de 1300 a 2300 A, Compt. Rend., 1967, 265, 649. [all data]

Bralsford, Harris, et al., 1960 Bralsford, R.; Harris, P.V.; Price, W.C., The effect of fluorine on the electronic spectra and ionization potentials of molecules, Proc. Roy. Soc. (London), 1960, A258, 459. [all data]

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

Potts, Lyus, et al., 1980 Potts, A.W.; Lyus, M.L.; Lee, E.P.F.; Fattahallah, G.H., High resolution ultraviolet photoelectron spectra of C6H5X and p-C6H4X2 where X = Cl, Br or I, J. Chem. Soc. Faraday Trans. 2, 1980, 76, 556. [all data]

Sell and Kupperman, 1978 Sell, J.A.; Kupperman, A., Angular distributions in the photoelectron spectra of benzene and its monohalogenated derivatives, Chem. Phys., 1978, 33, 367. [all data]

Klasinc, Novak, et al., 1978 Klasinc, L.; Novak, I.; Scholz, M.; Kluge, G., Photoelektronenspektren substituierter Pyridine und Benzole und ihre Interpretation durch die CNDO/SWW-Methode, Croat. Chem. Acta, 1978, 51, 43. [all data]

Streets and Ceasar, 1973 Streets, D.G.; Ceasar, G.P., Inductive mesomeric effects on the π orbitals of halobenzenes, Mol. Phys., 1973, 26, 1037. [all data]

Momigny, 1959 Momigny, J., Determination et discussion des potentials d'apparition d'ions fragmentaires dans le benzene et ses derives monohalogenes, Bull. Soc. Roy. Sci. Liege, 1959, 28, 251. [all data]

Ripoche, Dimicoli, et al., 1991 Ripoche, X.; Dimicoli, I.; Botter, R., Unimolecular decay rates for laser induced Cl loss from energy selected chlorobenzene cations [Eo(C6H5Cl+ Ü C6H5+ + Cl)=2.74±0.02 eV; cited data derived using recommended IP for chlorobenzene.], Int. J. Mass Spectrom. Ion Processes, 1991, 107, 165. [all data]

Burgers and Holmes, 1984 Burgers, P.C.; Holmes, J.L., Fragmentation rate constants and appearance energies for reactions having a large kinetic shift and the energy partitioning in their metastable decomposition, Int. J. Mass Spectrom. Ion Processes, 1984, 58, 15. [all data]

Rosenstock, Stockbauer, et al., 1980 Rosenstock, H.M.; Stockbauer, R.; Parr, A.C., Photoelectron-photoion coincidence study of the bromobenzene ion, J. Chem. Phys., 1980, 73, 773. [all data]

Rosenstock, Stockbauer, et al., 1979 Rosenstock, H.M.; Stockbauer, R.; Parr, A.C., Kinetic shift in chlorobenzene ion fragmentation and the heat of formation of the phenyl ion, J. Chem. Phys., 1979, 71, 3708. [all data]

Johnstone and Mellon, 1972 Johnstone, R.A.W.; Mellon, F.A., Electron-impact ionization and appearance potentials, J. Chem. Soc. Faraday Trans. 2, 1972, 68, 1209. [all data]

Majer and Patrick, 1962 Majer, J.R.; Patrick, C.R., Electron impact on some halogenated aromatic compounds, J. Chem. Soc. Faraday Trans., 1962, 58, 17. [all data]

Wenthold and Squires, 1995 Wenthold, P.G.; Squires, R.R., Determination of the gas-phase acidities of halogen-substituted aromatic compounds using the silane-cleavage method, J. Mass Spectrom., 1995, 30, 1, 17, https://doi.org/10.1002/jms.1190300105 . [all data]

Wenthold and Squires, 1994 Wenthold, P.G.; Squires, R.R., Gas-phase properties and reactivity of the acetate radical anion. Determination of the C-H bond strengths in acetic acid and acetate ion, J. Am. Chem. Soc., 1994, 116, 26, 11890, https://doi.org/10.1021/ja00105a032 . [all data]

Wenthold, Paulino, et al., 1991 Wenthold, P.G.; Paulino, J.A.; Squires, R.R., The Absolute Heats of Formation of ortho-Benzyne, meta-Benzyne, and para-Benzyne, J. Am. Chem. Soc., 1991, 113, 19, 7414, https://doi.org/10.1021/ja00019a044 . [all data]

Andrade and Riveros, 1996 Andrade, P.B.M.; Riveros, J.M., Relative Gas-phase Acidities of Fluoro- and Chlorobenzene, J. Mass Spectrom., 1996, 31, 7, 767, https://doi.org/10.1002/(SICI)1096-9888(199607)31:7<767::AID-JMS345>3.0.CO;2-Q . [all data]

Bartmess and McIver Jr., 1979 Bartmess, J.E.; McIver Jr., The Gas Phase Acidity Scale in Gas Phase Ion Chemistry, Gas Phase Ion Chemistry, V. 2, M.T. Bowers, Ed., Academic Press, NY, 1979, Ch. 11, Elsevier, 1979. [all data]

Notes

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

• Symbols used in this document:

  AE	Appearance energy
  IE (evaluated)	Recommended ionization energy
  ΔrG°	Free energy of reaction at standard conditions
  ΔrH°	Enthalpy of reaction at standard conditions

• Data from NIST Standard Reference Database 69: NIST Chemistry WebBook
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