Phosphine

Formula: H₃P
Molecular weight: 33.99758
IUPAC Standard InChI: InChI=1S/H3P/h1H3
IUPAC Standard InChIKey: XYFCBTPGUUZFHI-UHFFFAOYSA-N
CAS Registry Number: 7803-51-2
Chemical structure:
This structure is also available as a 2d Mol file
Other names: Trihydrogen phosphide; Hydrogen phosphide; Phosphorus trihydride; PH3; Phosphene; Phosphorus hydride; Fosforowodor; Gas-ex-B; Phosphorwasserstoff; Rcra waste number P096; UN 2199
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Gas phase ion energetics data

Go To: Top, References, Notes

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 H₃P⁺ (ion structure unspecified)

Quantity	Value	Units	Method	Reference	Comment
IE (evaluated)	9.869 ± 0.002	eV	N/A	N/A	L
Quantity	Value	Units	Method	Reference	Comment
Proton affinity (review)	188.	kcal/mol	N/A	Hunter and Lias, 1998	HL
Quantity	Value	Units	Method	Reference	Comment
Gas basicity	179.5	kcal/mol	N/A	Hunter and Lias, 1998	HL

Ionization energy determinations

IE (eV)	Method	Reference	Comment
9.87 ± 0.01	PIPECO	Ruede, Troxler, et al., 1993	LL
9.870 ± 0.002	PI	Berkowitz, Curtiss, et al., 1986	LBLHLM
9.868 ± 0.005	PE	Maripuu, Reineck, et al., 1983	LBLHLM
9.96	PE	Hodges, McDonnell, et al., 1980	LLK
10.0	EI	Morrison and Traeger, 1973	LLK
9.96	PE	Potts and Price, 1972	LLK
9.96 ± 0.01	PE	Maier and Turner, 1972	LLK
10.13 ± 0.02	PE	Branton, Frost, et al., 1970	RDSH
9.97 ± 0.02	EI	McAllister and Lossing, 1969	RDSH
10.28	PE	Frost, McDowell, et al., 1968	RDSH
10.05 ± 0.05	EI	Fehlner and Callen, 1968	RDSH
10.10	EI	Halmann and Platzner, 1967	RDSH
10.30 ± 0.10	EI	Halmann and Platzner, 1967	RDSH
9.98	PI	Price and Passmore, 1963	RDSH
10.59	PE	Cowley, Kemp, et al., 1982	Vertical value; LBLHLM
10.59 ± 0.05	PE	Demuth, 1977	Vertical value; LLK

Appearance energy determinations

Ion	AE (eV)	Other Products	Method	Reference	Comment
HP⁺	12.31 ± 0.01	H₂	PIPECO	Ruede, Troxler, et al., 1993	LL
HP⁺	12.451 ± 0.005	H₂	PI	Berkowitz, Curtiss, et al., 1986	LBLHLM
HP⁺	12.491 ± 0.005	H₂	PI	Berkowitz, Curtiss, et al., 1986	T = 0K; LBLHLM
HP⁺	12.9	H₂	EI	Morrison and Traeger, 1973	LLK
PH⁺	12.6 ± 0.2	H₂	EI	Fehlner and Callen, 1968	RDSH
PH⁺	12.4 ± 0.2	H₂	EI	Saalfeld and Svec, 1963	RDSH
H₂P⁺	13.2 ± 0.1	H	PIPECO	Ruede, Troxler, et al., 1993	LL
H₂P⁺	13.36 ± 0.02	H	PI	Berkowitz, Curtiss, et al., 1986	LBLHLM
H₂P⁺	13.40 ± 0.02	H	PI	Berkowitz, Curtiss, et al., 1986	T = 0K; LBLHLM
H₂P⁺	13.4	H	EI	Morrison and Traeger, 1973	LLK
PH₂⁺	13.47 ± 0.05	H	EI	McAllister and Lossing, 1969	RDSH
PH₂⁺	13.6	H	EI	McAllister and Lossing, 1969	RDSH
PH₂⁺	13.2 ± 0.2	H	EI	Fehlner and Callen, 1968	RDSH
PH₂⁺	13.2 ± 0.2	H	EI	Saalfeld and Svec, 1964	RDSH
P⁺	16.3 ± 0.1	H₂+H	PIPECO	Ruede, Troxler, et al., 1993	LL
P⁺	16.3	H₂+H	EI	Morrison and Traeger, 1973	LLK
P⁺	16.3	H₂+H	PI	Morrison and Traeger, 1973	LLK
P⁺	15.9	H₂+H	EI	Fehlner and Callen, 1968	RDSH

De-protonation reactions

H₂P^- + = Phosphine

By formula: H₂P^- + H⁺ = H₃P

Quantity	Value	Units	Method	Reference	Comment
Δ_rH°	363.8 ± 1.5	kcal/mol	D-EA	Ervin and Lineberger, 2005	gas phase; High level calcns( Curtiss, Raghavachari, et al., 1991, Ricca and Bauschlicher, 1998) give DH ca. 84; B
Δ_rH°	370.8 ± 2.1	kcal/mol	G+TS	Bartmess, Scott, et al., 1979	gas phase; The D-EA cycle does not close by 7 kcal/mol. The reason for this discrepancy is not known; value altered from reference due to change in acidity scale; B
Δ_rH°	364.3 ± 4.6	kcal/mol	EIAE	Halmann and Platzner, 1969	gas phase; B
Δ_rH°	<366.6 ± 4.6	kcal/mol	EIAE	Ebinghaus, Kraus, et al., 1964	gas phase; B
Δ_rH°	365.60	kcal/mol	N/A	Check, Faust, et al., 2001	gas phase; MnF5-(q); ; ΔS(EA)=2.9; B
Quantity	Value	Units	Method	Reference	Comment
Δ_rG°	356.4 ± 1.6	kcal/mol	H-TS	Ervin and Lineberger, 2005	gas phase; High level calcns( Curtiss, Raghavachari, et al., 1991, Ricca and Bauschlicher, 1998) give DH ca. 84; B
Δ_rG°	363.4 ± 2.0	kcal/mol	IMRE	Bartmess, Scott, et al., 1979	gas phase; The D-EA cycle does not close by 7 kcal/mol. The reason for this discrepancy is not known; value altered from reference due to change in acidity scale; B
Δ_rG°	358.70	kcal/mol	N/A	Check, Faust, et al., 2001	gas phase; MnF5-(q); ; ΔS(EA)=2.9; B

References

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

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]

Ruede, Troxler, et al., 1993
Ruede, R.; Troxler, H.; Beglinger, C.; Jungen, M., The dissociation energies of the positive ions NH₃⁺, NF₃⁺, PH₃⁺, PF₃⁺ and PCl₃⁺, Chem. Phys. Lett., 1993, 203, 477. [all data]

Berkowitz, Curtiss, et al., 1986
Berkowitz, J.; Curtiss, L.; Gibson, S.; Greene, J.; Hillhouse, G.; Pople, J., Photoionization mass spectrometric study and Ab initio calculation of ionization and bonding in P-H compounds. Heats of formation, bond energies, and the 3B₁-1A1 separation in PH₂⁺, J. Chem. Phys., 1986, 84, 375. [all data]

Maripuu, Reineck, et al., 1983
Maripuu, R.; Reineck, I.; Agren, H.; Nian-Zu, W.; Rong, J.; Veenhuizen, H.; Al-Shamma, S.; Karlsson, L.; Siegbahn, K., The HeI excited electron spectrum of phosphine. An experimental and theoretical study, Mol. Phys., 1983, 48, 1255. [all data]

Hodges, McDonnell, et al., 1980
Hodges, R.V.; McDonnell, T.J.; Beauchamp, J.L., Properties reactions of trimethyl phosphite, trimethyl phosphate, triethyl phosphate, and trimethyl phosphorothionate by ion cyclotron resonance spectroscopy, J. Am. Chem. Soc., 1980, 102, 1327. [all data]

Morrison and Traeger, 1973
Morrison, J.D.; Traeger, J.C., Ionization and dissociation by electron impact. II. NH₃ and PH₃, Int. J. Mass Spectrom. Ion Phys., 1973, 11, 277. [all data]

Potts and Price, 1972
Potts, A.W.; Price, W.C., Photoelectron spectra and valence shell orbital structures of groups V VI hydrides, Proc. R. Soc. London A:, 1972, 326, 181. [all data]

Maier and Turner, 1972
Maier, J.P.; Turner, D.W., Photoelectron spectroscopy and the geometry of the phosphine and phosphorous trifluoride molecular ions, J. Chem. Soc. Faraday Trans. 2, 1972, 68, 711. [all data]

Branton, Frost, et al., 1970
Branton, G.R.; Frost, D.C.; McDowell, C.A.; Stenhouse, I.A., The photoelectron spectra of phosphine and arsine, Chem. Phys. Lett., 1970, 5, 1. [all data]

McAllister and Lossing, 1969
McAllister, T.; Lossing, F.P., Free radicals by mass spectrometry. XLI. Ionization potential and heat of formation of PH₂ radical, J. Phys. Chem., 1969, 73, 2996. [all data]

Frost, McDowell, et al., 1968
Frost, D.C.; McDowell, C.A.; Sandhu, J.S.; Vroom, D.A., 584 A photo-electron spectra of Hg, NH₃, PH₃, and SF₆, Advan. Mass Spectrom., 1968, 4, 781. [all data]

Fehlner and Callen, 1968
Fehlner, T.P.; Callen, R.B., Mass spectrometry of phosphorus hydrides, Advan. Chem. Ser., 1968, 72, 181. [all data]

Halmann and Platzner, 1967
Halmann, M.; Platzner, I., Ion-molecule reactions of phosphine in the mass spectrometer, J. Phys. Chem., 1967, 71, 4522. [all data]

Price and Passmore, 1963
Price, W.C.; Passmore, T.R., [Title unavailable], Faraday Discuss. Chem. Soc., 1963, 35, 232. [all data]

Cowley, Kemp, et al., 1982
Cowley, A.H.; Kemp, R.A.; Lattman, M.; McKee, M.L., Lewis base behavior of methylated and fluorinated phosphines. A photoelectron spectroscopic investigation, Inorg. Chem., 1982, 21, 85. [all data]

Demuth, 1977
Demuth, R., Photoelektronenspektren von einigen Trihalogensilylphosphanen und -arsanen X₃SiER₂ (X = F, Cl; E = N, P, As; R = H, CH₃), Z. Naturforsch. B:, 1977, 32, 1252. [all data]

Saalfeld and Svec, 1963
Saalfeld, F.E.; Svec, H.J., The mass spectra of volatile hydrides. I. The monoelemental hydrides of the group IVB and VB elements, Inorg. Chem., 1963, 2, 46. [all data]

Saalfeld and Svec, 1964
Saalfeld, F.E.; Svec, H.J., Mass spectra of volatile hydrides. III. Silylphosphine, Inorg. Chem., 1964, 3, 1442. [all data]

Ervin and Lineberger, 2005
Ervin, K.M.; Lineberger, W.C., Photoelectron spectroscopy of phosphorus hydride anions, J. Chem. Phys., 2005, 122, 19, 194303, https://doi.org/10.1063/1.1881153 . [all data]

Curtiss, Raghavachari, et al., 1991
Curtiss, L.A.; Raghavachari, K.; Trucks, G.W.; Pople, J.A., Gaussian-2 Theory for Molecular Energies of First- and Second-row Compounds, J. Chem. Phys., 1991, 94, 11, 7221, https://doi.org/10.1063/1.460205 . [all data]

Ricca and Bauschlicher, 1998
Ricca, A.; Bauschlicher, C.W., Jr., Accurate Heats of Formation for PHn, PHn+, and PHn-, Chem. Phys. Lett., 1998, 285, 5-6, 455, https://doi.org/10.1016/S0009-2614(97)01468-1 . [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]

Halmann and Platzner, 1969
Halmann, M.; Platzner, I., Negative Ions Produced by Electron Capture in Phosphine, J. Phys. Chem., 1969, 73, 12, 4376, https://doi.org/10.1021/j100846a062 . [all data]

Ebinghaus, Kraus, et al., 1964
Ebinghaus, H.; Kraus, K.; Neuert, H.; Muller-Duysing, W., Negative Ionen durch Elecktronenresonanzeinfang in PH₃, AsH₃, und SiH₄, Z. Naturfor., 1964, 19A, 732. [all data]

Check, Faust, et al., 2001
Check, C.E.; Faust, T.O.; Bailey, J.M.; Wright, B.J.; Gilbert, T.M.; Sunderlin, L.S., Addition of Polarization and Diffuse Functions to the LANL2DZ Basis Set for P-Block Elements, J. Phys. Chem. A,, 2001, 105, 34, 8111, https://doi.org/10.1021/jp011945l . [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

Δ_rG° Free energy of reaction at standard conditions

Δ_rH° Enthalpy of reaction at standard conditions
Data from NIST Standard Reference Database 69: NIST Chemistry WebBook
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AE	Appearance energy
IE (evaluated)	Recommended ionization energy
Δ_rG°	Free energy of reaction at standard conditions
Δ_rH°	Enthalpy of reaction at standard conditions