Home Symbol which looks like a small house Up Solid circle with an upward pointer in it

Phosphorus oxychloride

Data at NIST subscription sites:

NIST subscription sites provide data under the NIST Standard Reference Data Program, but require an annual fee to access. The purpose of the fee is to recover costs associated with the development of data collections included in such sites. Your institution may already be a subscriber. Follow the links above to find out more about the data in these sites and their terms of usage.


Gas phase thermochemistry data

Go To: Top, Phase change data, Reaction thermochemistry data, Gas phase ion energetics data, Ion clustering data, Mass spectrum (electron ionization), Vibrational and/or electronic energy levels, NIST Free Links, References, Notes

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

Quantity Value Units Method Reference Comment
Deltafgas-559.82kJ/molReviewChase, 1998Data last reviewed in June, 1962
Quantity Value Units Method Reference Comment
gas,1 bar325.45J/mol*KReviewChase, 1998Data last reviewed in June, 1962

Gas Phase Heat Capacity (Shomate Equation)

Cp° = A + B*t + C*t2 + D*t3 + E/t2
H° − H°298.15= A*t + B*t2/2 + C*t3/3 + D*t4/4 − E/t + F − H
S° = A*ln(t) + B*t + C*t2/2 + D*t3/3 − E/(2*t2) + G
    Cp = heat capacity (J/mol*K)
    H° = standard enthalpy (kJ/mol)
    S° = standard entropy (J/mol*K)
    t = temperature (K) / 1000.

View plot Requires a JavaScript / HTML 5 canvas capable browser.

View table.

Temperature (K) 298. - 1000.1000. - 6000.
A 75.07602107.4757
B 77.365090.352779
C -71.30456-0.073164
D 23.867460.005165
E -0.669089-3.451110
F -587.3039-601.7596
G 392.4337440.3953
H -559.8192-559.8192
ReferenceChase, 1998Chase, 1998
Comment Data last reviewed in June, 1962 Data last reviewed in June, 1962

Phase change data

Go To: Top, Gas phase thermochemistry data, Reaction thermochemistry data, Gas phase ion energetics data, Ion clustering data, Mass spectrum (electron ionization), Vibrational and/or electronic energy levels, NIST Free Links, 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, Kenneth Kroenlein director

Quantity Value Units Method Reference Comment
Tfus274.2KN/AWitschonke, 1954Uncertainty assigned by TRC = 0.15 K; TRC
Tfus274.35KN/AWitschonke, 1954Uncertainty assigned by TRC = 0.1 K; TRC
Quantity Value Units Method Reference Comment
Tc601.KN/ASladkov and Parusova, 1977Uncertainty assigned by TRC = 4. K; TRC
Quantity Value Units Method Reference Comment
Pc49.60barN/ASladkov and Parusova, 1977Uncertainty assigned by TRC = 0.50 bar; TRC
Quantity Value Units Method Reference Comment
Vc0.276l/molN/ASladkov and Parusova, 1977Uncertainty assigned by TRC = 0.005 l/mol; From Abstract; TRC

Antoine Equation Parameters

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

View plot Requires a JavaScript / HTML 5 canvas capable browser.

Temperature (K) A B C Reference Comment
275. - 378.34.281661445.959-40.119Stull, 1947Coefficents calculated by NIST from author's data.

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:


Reaction thermochemistry data

Go To: Top, Gas phase thermochemistry data, Phase change data, Gas phase ion energetics data, Ion clustering data, Mass spectrum (electron ionization), Vibrational and/or electronic energy levels, NIST Free Links, References, Notes

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

Data compiled by: John E. Bartmess

Note: Please consider using the reaction search for this species. This page allows searching of all reactions involving this species. A general reaction search form is also available. Future versions of this site may rely on reaction search pages in place of the enumerated reaction displays seen below.

Individual Reactions

Chlorine anion + Phosphorus oxychloride = Cl4OP-

By formula: Cl- + Cl3OP = Cl4OP-

Quantity Value Units Method Reference Comment
Deltar43.1 ± 5.0kJ/molCIDTCheck, Lobring, et al., 2003gas phase

Gas phase ion energetics data

Go To: Top, Gas phase thermochemistry data, Phase change data, Reaction thermochemistry data, Ion clustering data, Mass spectrum (electron ionization), Vibrational and/or electronic energy levels, NIST Free Links, 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:
L - Sharon G. Lias

Data compiled as indicated in comments:
LLK - Sharon G. Lias, Rhoda D. Levin, and Sherif A. Kafafi
RDSH - Henry M. Rosenstock, Keith Draxl, Bruce W. Steiner, and John T. Herron
B - John E. Bartmess

Quantity Value Units Method Reference Comment
IE (evaluated)11.5 ± 0.1eVN/AN/AL

Electron affinity determinations

EA (eV) Method Reference Comment
1.41 ± 0.20NBIEMathur, Rothe, et al., 1976B

Ionization energy determinations

IE (eV) Method Reference Comment
11.36 ± 0.02PEBunzli, Frost, et al., 1973LLK
11.58 ± 0.05PEBasset and Lloyd, 1972LLK
11.4 ± 0.3EIKiser, Dillard, et al., 1969RDSH
13.1 ± 0.2EIHalmann and Klein, 1964RDSH
11.89PEChattorpadhyay, Findley, et al., 1981Vertical value; LLK
11.89 ± 0.02PEGan, Peel, et al., 1977Vertical value; LLK
11.49PEVovna, Lopatin, et al., 1975Vertical value; LLK
11.89 ± 0.03PECox, Evans, et al., 1972Vertical value; LLK
12.0PEBetteridge, Thompson, et al., 1972Vertical value; LLK

Appearance energy determinations

Ion AE (eV) Other Products MethodReferenceComment
Cl+19. ± 1.?EIHalmann and Klein, 1964RDSH
POCl+15.6 ± 0.3?EIKiser, Dillard, et al., 1969RDSH
PCl+20.2 ± 0.4?EIKiser, Dillard, et al., 1969RDSH
PCl+17. ± 1.?EIHalmann and Klein, 1964RDSH
POCl2+12.8 ± 0.3ClEIKiser, Dillard, et al., 1969RDSH
POCl2+13.3 ± 0.2ClEIHalmann and Klein, 1964RDSH
PCl2+13.3 ± 0.5?EIHalmann and Klein, 1964RDSH
PCl3+12.3 ± 0.5OEIHalmann and Klein, 1964RDSH
O+13. ± 2.?EIHalmann and Klein, 1964RDSH
PO+16.6 ± 0.4?EIKiser, Dillard, et al., 1969RDSH
PO+14.5 ± 0.5?EIHalmann and Klein, 1964RDSH
P+28.1 ± 0.5?EIKiser, Dillard, et al., 1969RDSH
P+21.4?EIHalmann and Klein, 1964RDSH

Ion clustering data

Go To: Top, Gas phase thermochemistry data, Phase change data, Reaction thermochemistry data, Gas phase ion energetics data, Mass spectrum (electron ionization), Vibrational and/or electronic energy levels, NIST Free Links, References, Notes

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

Data compiled by: John E. Bartmess

Note: Please consider using the reaction search for this species. This page allows searching of all reactions involving this species. Searches may be limited to ion clustering reactions. A general reaction search form is also available.

Clustering reactions

Chlorine anion + Phosphorus oxychloride = Cl4OP-

By formula: Cl- + Cl3OP = Cl4OP-

Quantity Value Units Method Reference Comment
Deltar43.1 ± 5.0kJ/molCIDTCheck, Lobring, et al., 2003gas phase

Mass spectrum (electron ionization)

Go To: Top, Gas phase thermochemistry data, Phase change data, Reaction thermochemistry data, Gas phase ion energetics data, Ion clustering data, Vibrational and/or electronic energy levels, NIST Free Links, References, Notes

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

Data compiled by: NIST Mass Spectrometry Data Center, William E. Wallace, director

Spectrum

Notice: This spectrum may be better viewed with a Javascript and HTML 5 enabled browser.

Mass spectrum
For Zoom
1.) Enter the desired X axis range (e.g., 100, 200)
2.) Check here for automatic Y scaling
3.) Press here to zoom

Additional Data

View image of digitized spectrum (can be printed in landscape orientation).

View spectrum image in SVG format.

Download spectrum in JCAMP-DX format.

Owner NIST Mass Spectrometry Data Center
Collection (C) 2014 copyright by the U.S. Secretary of Commerce
on behalf of the United States of America. All rights reserved.
NIST MS number 4953

All mass spectra in this site (plus many more) are available from the NIST/EPA/NIH Mass Spectral Library. Please see the following for information about the library and its accompanying search program.


Vibrational and/or electronic energy levels

Go To: Top, Gas phase thermochemistry data, Phase change data, Reaction thermochemistry data, Gas phase ion energetics data, Ion clustering data, Mass spectrum (electron ionization), NIST Free Links, References, Notes

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

Data compiled by: Takehiko Shimanouchi

Symmetry:   C2     Symmetry Number sigma = 2


 Sym.   No   Approximate   Selected Freq.  Infrared   Raman   Comments 
 Species   type of mode   Value   Rating   Value  Phase  Value  Phase

a1 1 PO str 1322  C 1321.5 gas
a1 2 PCl3 s-str 481  C 480.5 gas
a1 3 PCl3 s-deform 266  C 265.5 gas
e 4 PCl3 d-str 590  C 589.5 gas
e 5 PO bend 333  C 332.5 gas
e 6 PCl3 d-deform 187  C 187.0 gas

Source: Shimanouchi, 1972

Notes

C3~6 cm-1 uncertainty

References

Go To: Top, Gas phase thermochemistry data, Phase change data, Reaction thermochemistry data, Gas phase ion energetics data, Ion clustering data, Mass spectrum (electron ionization), Vibrational and/or electronic energy levels, NIST Free Links, Notes

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

Chase, 1998
Chase, M.W., Jr., NIST-JANAF Themochemical Tables, Fourth Edition, J. Phys. Chem. Ref. Data, Monograph 9, 1998, 1-1951. [all data]

Witschonke, 1954
Witschonke, C.R., Freezing point and purity data for some organic compounds, Anal. Chem., 1954, 26, 562-4. [all data]

Sladkov and Parusova, 1977
Sladkov, I.B.; Parusova, N.D., Russ. J. Phys. Chem. (Engl. Transl.), 1977, 51, 319. [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]

Check, Lobring, et al., 2003
Check, C.E.; Lobring, K.C.; Keating, P.R.; Gilbert, T.M.; Sunderlin, L.S., Effect of substituents on the strength of hypervalent phosphorus-halogen bonds, J. Phys. Chem. A, 2003, 107, 42, 8961-8967, https://doi.org/10.1021/jp030287x . [all data]

Mathur, Rothe, et al., 1976
Mathur, B.P.; Rothe, E.W.; Tang, S.Y.; Reck, G., Negative ions from phosphorus halides due to cesium charge exchange, J. Chem. Phys., 1976, 64, 565. [all data]

Bunzli, Frost, et al., 1973
Bunzli, J.C.; Frost, D.C.; McDowell, C.A., Photoelectron spectra of phosphoryl and thioophosphoryl ch;prodes and bromides, J. Electron Spectrosc. Relat. Phenom., 1973, 1, 481. [all data]

Basset and Lloyd, 1972
Basset, P.J.; Lloyd, D.R., Photoelectron spectra of halides. Part III. Trifluorides and oxide trifluorides of nitrogen and phosphorus, and phosphorus oxide trichloride, J. Chem. Soc. Dalton Trans., 1972, 248. [all data]

Kiser, Dillard, et al., 1969
Kiser, R.W.; Dillard, J.G.; Dugger, D.L., Mass spectrometry of inorganic halides, Advan. Chem. Ser., 1969, 72, 153. [all data]

Halmann and Klein, 1964
Halmann, M.; Klein, Y., Electron-impact spectroscopy of phosphorus compounds. Part III. Positive- andnegative-ion formation from phosphorus trichloride and phosphoryl chloride, J. Chem. Soc., 1964, 4324. [all data]

Chattorpadhyay, Findley, et al., 1981
Chattorpadhyay, S.; Findley, G.L.; McGlynn, S.P., Photoelectron spectroscopy of phosphites and phosphates, J. Electron Spectrosc. Relat. Phenom., 1981, 24, 27. [all data]

Gan, Peel, et al., 1977
Gan, T.H.; Peel, J.B.; Willett, G.D., Comparison of He I and He II photoelectron spectra of phosphoryl chloride, Chem. Phys. Lett., 1977, 48, 483. [all data]

Vovna, Lopatin, et al., 1975
Vovna, V.I.; Lopatin, S.N.; Pettsol'd, R.; Vilesov, F.I., Photoelectron spectra and electronic structure of some phosphoryl compounds, Khim. Vys. Energ., 1975, 9, 9. [all data]

Cox, Evans, et al., 1972
Cox, P.A.; Evans, S.; Orchard, A.F.; Richardson, N.V.; Roberts, P.J., Simple quantitative molecular orbital methods used in connection with photoelectron spectroscopy, Faraday Discuss. Chem. Soc., 1972, 54, 26. [all data]

Betteridge, Thompson, et al., 1972
Betteridge, D.; Thompson, M.; Baker, A.D.; Kemp, N.R., Photoelectron spectra of phosphorus halides, alkyl phosphites and phosphates, organophosphorus pesticides, and related compounds, Anal. Chem., 1972, 44, 2005. [all data]

Shimanouchi, 1972
Shimanouchi, T., Tables of Molecular Vibrational Frequencies Consolidated Volume II, J. Phys. Chem. Ref. Data, 1972, 6, 3, 993-1102. [all data]


Notes

Go To: Top, Gas phase thermochemistry data, Phase change data, Reaction thermochemistry data, Gas phase ion energetics data, Ion clustering data, Mass spectrum (electron ionization), Vibrational and/or electronic energy levels, NIST Free Links, References