Acetic Anhydride - The NIST WebBook

Acetic anhydride

• Formula: C4H6O3
• Molecular weight: 102.0886
• IUPAC Standard InChI: InChI=1S/C4H6O3/c1-3(5)7-4(2)6/h1-2H3 Copy
• IUPAC Standard InChIKey: WFDIJRYMOXRFFG-UHFFFAOYSA-N Copy
• CAS Registry Number: 108-24-7
• Chemical structure: This structure is also available as a 2d Mol file or as a computed 3d SD file View 3d structure (requires JavaScript / HTML 5)
• Other names: Acetic acid, anhydride; Acetic oxide; Acetyl anhydride; Acetyl ether; Acetyl oxide; Ethanoic anhydride; (CH3CO)2O; Ethanoic anhydrate; Acetanhydride; Anhydride acetique; Anhydrid kyseliny octove; Anidride acetica; Azijnzuuranhydride; Essigsaeureanhydrid; Octowy bezwodnik; UN 1715; Acetyl acetate; Acetic acid, 1,1'-anhydride
• Permanent link for this species. Use this link for bookmarking this species for future reference.
• Information on this page:
  • Gas phase thermochemistry data
  • Condensed phase thermochemistry data
  • Phase change data
  • Reaction thermochemistry data
  • Gas phase ion energetics data
  • Ion clustering data
  • IR Spectrum
  • Mass spectrum (electron ionization)
  • References
  • Notes
• Other data available:
  • Gas Chromatography
• Data at other public NIST sites:
  • Gas Phase Kinetics Database
• Options:
  • Switch to calorie-based units

Data at NIST subscription sites:

• NIST / TRC Web Thermo Tables, professional edition (thermophysical and thermochemical data)

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, Condensed phase thermochemistry data, Phase change data, Reaction thermochemistry data, Gas phase ion energetics data, Ion clustering data, IR Spectrum, Mass spectrum (electron ionization), 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: Glushko Thermocenter, Russian Academy of Sciences, Moscow

Quantity	Value	Units	Method	Reference	Comment
S°gas	389.95	J/mol*K	N/A	Stull D.R., 1969

Constant pressure heat capacity of gas

Cp,gas (J/mol*K)	Temperature (K)	Reference	Comment
99.50	298.15	Stull D.R., 1969	Selected values were based on an approximation of heat capacities from Cp(T) values of acetic acid.
100.04	300.
129.12	400.
153.89	500.
174.14	600.
191.38	700.
204.64	800.
216.06	900.
226.40	1000.

Condensed phase thermochemistry data

Go To: Top, Gas phase thermochemistry data, Phase change data, Reaction thermochemistry data, Gas phase ion energetics data, Ion clustering data, IR Spectrum, Mass spectrum (electron ionization), 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: ALS - Hussein Y. Afeefy, Joel F. Liebman, and Stephen E. Stein DH - Eugene S. Domalski and Elizabeth D. Hearing

Quantity	Value	Units	Method	Reference	Comment
ΔfH°liquid	-625.0 ± 3.4	kJ/mol	Cm	Guthrie, 1974	Reanalyzed by Pedley, Naylor, et al., 1986, Original value = -628.4 ± 3.3 kJ/mol; Heat of hydrolysis[kcal/mol]=-40.6±0.80; ALS

Constant pressure heat capacity of liquid

Cp,liquid (J/mol*K)	Temperature (K)	Reference	Comment
168.2	303.2	Phillip, 1939	DH

Phase change data

Go To: Top, Gas phase thermochemistry data, Condensed phase thermochemistry data, Reaction thermochemistry data, Gas phase ion energetics data, Ion clustering data, IR Spectrum, Mass spectrum (electron ionization), 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: BS - Robert L. Brown and Stephen E. Stein TRC - Thermodynamics Research Center, NIST Boulder Laboratories, Chris Muzny director AC - William E. Acree, Jr., James S. Chickos

Quantity	Value	Units	Method	Reference	Comment
Tboil	412. ± 5.	K	AVG	N/A	Average of 10 values; Individual data points
Quantity	Value	Units	Method	Reference	Comment
Tfus	200. ± 1.	K	AVG	N/A	Average of 8 values; Individual data points
Quantity	Value	Units	Method	Reference	Comment
Tc	606.	K	N/A	Ambrose and Ghiassee, 1987	Uncertainty assigned by TRC = 4. K; decomposition of sample prevented accurate measurement, reported value based partly on a correlation; TRC
Tc	569.	K	N/A	Vespigniani, 1903	Uncertainty assigned by TRC = 20. K; TRC
Quantity	Value	Units	Method	Reference	Comment
Pc	40.00	bar	N/A	Ambrose and Ghiassee, 1987	Uncertainty assigned by TRC = 2.00 bar; based partly on a corelation because of decompostion of smp.; TRC
Pc	46.80	bar	N/A	Vespigniani, 1903	Uncertainty assigned by TRC = 4.053 bar; TRC

Reduced pressure boiling point

Tboil (K)	Pressure (bar)	Reference	Comment
317.2	0.020	Weast and Grasselli, 1989	BS
317.	0.020	Buckingham and Donaghy, 1982	BS

Enthalpy of vaporization

ΔvapH (kJ/mol)	Temperature (K)	Method	Reference	Comment
43.3	364.	EB	Ambrose and Ghiassee, 1987, 2	Based on data from 349. to 429. K.; AC
47.6	428.	A	Stephenson and Malanowski, 1987	Based on data from 413. to 526. K.; AC
45.5	335.	A	Stephenson and Malanowski, 1987	Based on data from 320. to 413. K. See also Dykyj, 1971.; AC
44.2	351.	N/A	McDonald, Shrader, et al., 1959	Based on data from 336. to 412. K.; AC

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
335.99 to 412.57	4.24655	1427.77	-75.113	McDonald, Shrader, et al., 1959

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:

• SRD 103a – Thermo Data Engine (TDE) for pure compounds.
• SRD 103b – Thermo Data Engine (TDE) for pure compounds, binary mixtures and chemical reactions
• SRD 202 – Web Thermo Tables (WTT), "lite" edition
• SRD 203 – Web Thermo Tables (WTT), professional edition
• SRD 147 – Ionic Liquids Database
• SRD 156 – Clathrate Hydrate Physical Property Database

Reaction thermochemistry data

Go To: Top, Gas phase thermochemistry data, Condensed phase thermochemistry data, Phase change data, Gas phase ion energetics data, Ion clustering data, IR Spectrum, Mass spectrum (electron ionization), 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: ALS - Hussein Y. Afeefy, Joel F. Liebman, and Stephen E. Stein RCD - Robert C. Dunbar

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

+ = 2

By formula: C4H6O3 + H2O = 2C2H4O2

Quantity	Value	Units	Method	Reference	Comment
ΔrH°	-56.6 ± 4.0	kJ/mol	Cm	Becker and Maelicke, 1967	liquid phase; ALS
ΔrH°	-58.6 ± 0.4	kJ/mol	Cm	Wadso, 1962	liquid phase; ALS
ΔrH°	-58.4 ± 0.4	kJ/mol	Cm	Conn, Kistiakowsky, et al., 1942	liquid phase; Heat of hydrolysis at 303 K; ALS

+ = +

By formula: C4H6O3 + C4H11N = C6H13NO + C2H4O2

Quantity	Value	Units	Method	Reference	Comment
ΔrH°	-113.2 ± 0.46	kJ/mol	Cm	Wadso, 1962	liquid phase; ALS
ΔrH°	-163.7 ± 0.3	kJ/mol	Cm	Wadso, 1958	liquid phase; Heat of aminolysis; ALS

+ = ( • )

By formula: Na+ + C4H6O3 = (Na+ • C4H6O3)

Free energy of reaction

ΔrG° (kJ/mol)	T (K)	Method	Reference	Comment
130.	298.	IMRE	McMahon and Ohanessian, 2000	Anchor alanine=39.89; RCD

+ 2 = + 2

By formula: C4H6O3 + 2C3H6O3 = C6H10O5 + 2C2H4O2

Quantity	Value	Units	Method	Reference	Comment
ΔrH°	0.0	kJ/mol	Eqk	Utkin, Bogel'fer, et al., 1991	liquid phase; NMR; ALS

2 = +

By formula: 2C2H4O2 = C4H6O3 + H2O

Quantity	Value	Units	Method	Reference	Comment
ΔrH°	63.7 ± 1.2	kJ/mol	Eqk	Knopp, Linnell, et al., 1962	liquid phase; ALS

+ = +

By formula: C4H6O3 + C6H7N = C8H9NO + C2H4O2

Quantity	Value	Units	Method	Reference	Comment
ΔrH°	-100.9 ± 0.3	kJ/mol	Cm	Wadso, 1962	liquid phase; ALS

+ = +

By formula: C2H3NO4 + C2H4O2 = C4H6O3 + HNO3

Quantity	Value	Units	Method	Reference	Comment
ΔrH°	16.7	kJ/mol	Cm	Tsvetkov, Shmakov, et al., 1989	liquid phase; ALS

+ = +

By formula: C4H6O3 + C9H13N3O5 = C11H15N3O6 + C2H4O2

Quantity	Value	Units	Method	Reference	Comment
ΔrH°	-43.9	kJ/mol	Kin	Shatynski and Hanesian, 1993	solid phase; ALS

+ =

By formula: C2H2O + C2H4O2 = C4H6O3

Quantity	Value	Units	Method	Reference	Comment
ΔrH°	-87.5 ± 2.2	kJ/mol	Eqk	Blake, Davies, et al., 1971	gas phase; ALS

Gas phase ion energetics data

Go To: Top, Gas phase thermochemistry data, Condensed phase thermochemistry data, Phase change data, Reaction thermochemistry data, Ion clustering data, IR Spectrum, Mass spectrum (electron ionization), 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: LLK - Sharon G. Lias, Rhoda D. Levin, and Sherif A. Kafafi LBLHLM - Sharon G. Lias, John E. Bartmess, Joel F. Liebman, John L. Holmes, Rhoda D. Levin, and W. Gary Mallard RDSH - Henry M. Rosenstock, Keith Draxl, Bruce W. Steiner, and John T. Herron

View reactions leading to C4H6O3+ (ion structure unspecified)

Ionization energy determinations

IE (eV)	Method	Reference	Comment
~10.0	PE	Bock, Hirabayashi, et al., 1981	LLK

Appearance energy determinations

Ion	AE (eV)	Other Products	Method	Reference	Comment
C2H3O+	10.14	CH3COO	PI	Traeger, McLouglin, et al., 1982	LBLHLM
C2H3O+	10.19 ± 0.02	?	PI	Shigorin, Filyugina, et al., 1967	RDSH
C2H4O2+	9.65 ± 0.02	CH2=CO?	PI	Shigorin, Filyugina, et al., 1967	RDSH
C3H3O3+	10.14 ± 0.02	CH3	PI	Shigorin, Filyugina, et al., 1967	RDSH

Ion clustering data

Go To: Top, Gas phase thermochemistry data, Condensed phase thermochemistry data, Phase change data, Reaction thermochemistry data, Gas phase ion energetics data, IR Spectrum, Mass spectrum (electron ionization), 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: Robert C. Dunbar

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

+ = ( • )

By formula: Na+ + C4H6O3 = (Na+ • C4H6O3)

Free energy of reaction

ΔrG° (kJ/mol)	T (K)	Method	Reference	Comment
130.	298.	IMRE	McMahon and Ohanessian, 2000	Anchor alanine=39.89

IR Spectrum

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

Data compiled by: Coblentz Society, Inc.

• LIQUID (NEAT); BAIRD (GRATING); 2 cm-1 resolution
• SOLUTION (2% IN CCl4 FOR 3800-1330, 2% IN CS2 FOR 1330-400 CM-1); BECKMAN IR-9 (GRATING); DIGITIZED BY NIST FROM HARD COPY (FROM TWO SEGMENTS); 4 cm-1 resolution

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

• gas

Mass spectrum (electron ionization)

Go To: Top, Gas phase thermochemistry data, Condensed phase thermochemistry data, Phase change data, Reaction thermochemistry data, Gas phase ion energetics data, Ion clustering data, IR Spectrum, 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.

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

• Plot
• Help / Software credits

Help

The interactive spectrum display requires a browser with JavaScript and HTML 5 canvas support.

Select a region with data to zoom. Select a region with no data or click the mouse on the plot to revert to the orginal display.

Credits

The following components were used in generating the plot:

• jQuery
• jQuery UI
• Flot
• Plugins for Flot:
  • Resize (distributed with Flot)
  • Selection (distributed with Flot)
  • Axis labels
  • Labels ( Modified by NIST for use in this application)

Additonal code used was developed at NIST: jcamp-dx.js and jcamp-plot.js.

Use or mention of technologies or programs in this web site is not intended to imply recommendation or endorsement by the National Institute of Standards and Technology, nor is it intended to imply that these items are necessarily the best available for the purpose.

Additional Data

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

Due to licensing restrictions, this spectrum cannot be downloaded.

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.
Origin	NIST Mass Spectrometry Data Center, 1998.
NIST MS number	291302

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.

References

Go To: Top, Gas phase thermochemistry data, Condensed phase thermochemistry data, Phase change data, Reaction thermochemistry data, Gas phase ion energetics data, Ion clustering data, IR Spectrum, Mass spectrum (electron ionization), Notes

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

Stull D.R., 1969 Stull D.R., Jr., The Chemical Thermodynamics of Organic Compounds. Wiley, New York, 1969. [all data]

Guthrie, 1974 Guthrie, J.P., Hydration of carboxamides. Evaluation of the free energy change for addition of water to acetamide and formamide derivatives, J. Am. Chem. Soc., 1974, 96, 3608-3615. [all data]

Pedley, Naylor, et al., 1986 Pedley, J.B.; Naylor, R.D.; Kirby, S.P., Thermochemical Data of Organic Compounds, Chapman and Hall, New York, 1986, 1-792. [all data]

Phillip, 1939 Phillip, N.M., Adiabatic and isothermal compressibilities of liquids, Proc. Indian Acad. Sci., 1939, A9, 109-120. [all data]

Ambrose and Ghiassee, 1987 Ambrose, D.; Ghiassee, N.B., Vapor Pressure, Critical Temperature and Critical Pressure of Acetic Anhydride, J. Chem. Thermodyn., 1987, 19, 911. [all data]

Vespigniani, 1903 Vespigniani, G.R., Gazz. Chim. Ital., 1903, 33, 73-8. [all data]

Weast and Grasselli, 1989 CRC Handbook of Data on Organic Compounds, 2nd Editon, Weast,R.C and Grasselli, J.G., ed(s)., CRC Press, Inc., Boca Raton, FL, 1989, 1. [all data]

Buckingham and Donaghy, 1982 Buckingham, J.; Donaghy, S.M., Dictionary of Organic Compounds: Fifth Edition, Chapman and Hall, New York, 1982, 1. [all data]

Ambrose and Ghiassee, 1987, 2 Ambrose, D.; Ghiassee, N.B., Vapour pressure, critical temperature, and critical pressure of acetic anhydride, The Journal of Chemical Thermodynamics, 1987, 19, 9, 911-913, https://doi.org/10.1016/0021-9614(87)90037-1 . [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]

Dykyj, 1971 Dykyj, J., Petrochemia, 1971, 11, 2, 27. [all data]

McDonald, Shrader, et al., 1959 McDonald, R.A.; Shrader, S.A.; Stull, D.R., Vapor Pressures and Freezing Points of Thirty Pure Organic Compounds., J. Chem. Eng. Data, 1959, 4, 4, 311-313, https://doi.org/10.1021/je60004a009 . [all data]

Becker and Maelicke, 1967 Becker, F.; Maelicke, A., Thermokinetische Messungen nach dem Prinzip der Wärmefluβkalorimetrie, Z. Phys. Chem. (Neue Folge), 1967, 55, 280-295. [all data]

Wadso, 1962 Wadso, I., Heats of aminolysis and hydrolysis of some N-acetyl compounds and of acetic anhydride, Acta Chem. Scand., 1962, 16, 471-478. [all data]

Conn, Kistiakowsky, et al., 1942 Conn, J.B.; Kistiakowsky, G.B.; Roberts, R.M.; Smith, E.A., Heats of organic reactions. XIII. Heats of hydrolysis of some acid anhydrides, J. Am. Chem. Soc., 1942, 64, 1747-17. [all data]

Wadso, 1958 Wadso, I., The heats of aminolysis of n-butyl thiolacetate and acetic anhydride, Acta Chem. Scand., 1958, 12, 635-640. [all data]

McMahon and Ohanessian, 2000 McMahon, T.B.; Ohanessian, G., An Experimental and Ab Initio Study of the Nature of the Binding in Gas-Phase Complexes of Sodium Ions, Chem. Eur. J., 2000, 6, 16, 2931, https://doi.org/10.1002/1521-3765(20000818)6:16<2931::AID-CHEM2931>3.0.CO;2-7 . [all data]

Utkin, Bogel'fer, et al., 1991 Utkin, A.Yu.; Bogel'fer, L.Ya.; Chimishkyan, A.L., Reversible reactions in the acidolysis of methyoxyacetic acid by acetic anhydride, Russ. J. Phys. Chem. (Engl. Transl.), 1991, 65, 1049-1059, In original 1974. [all data]

Knopp, Linnell, et al., 1962 Knopp, J.A.; Linnell, W.S.; Child, W.C., Jr., The thermodynamics of the thermal decomposition of acetic acid in the liquid phase, J. Phys. Chem., 1962, 66, 1513-1516. [all data]

Tsvetkov, Shmakov, et al., 1989 Tsvetkov, V.G.; Shmakov, V.A.; Sopin, V.F.; Ivanov, A.V.; Ikonnikov, A.A.; Marchenko, G.N., Enthalpies of reaction of nitric acid with acetic and trifluoroacetic anhydrides, J. Gen. Chem. USSR, 1989, 59, 1220-1222. [all data]

Shatynski and Hanesian, 1993 Shatynski, J.J.; Hanesian, D., Adiabatic kinetic studies of the cytidine/acetic anhydride reaction by utilizing temperature versus time data, Ind. Eng. Chem. Res., 1993, 32, 594-599. [all data]

Blake, Davies, et al., 1971 Blake, P.G.; Davies, H.H.; Speis, A., Reactions of keten. Part II. The thermodynamics of the gas-phase equilibrium: acetic acid + keten = acetic anhydride, J. Chem. Soc. B, 1971, 2050-2052. [all data]

Bock, Hirabayashi, et al., 1981 Bock, H.; Hirabayashi, T.; Mohmand, S., Thermische erzeugung von alkyl- und halogenketenen, Chem. Ber., 1981, 114, 2595. [all data]

Traeger, McLouglin, et al., 1982 Traeger, J.C.; McLouglin, R.G.; Nicholson, A.J.C., Heat of formation for acetyl cation in the gas phase, J. Am. Chem. Soc., 1982, 104, 5318. [all data]

Shigorin, Filyugina, et al., 1967 Shigorin, D.N.; Filyugina, A.D.; Potapov, V.K., Role of intramolecular hydrogen bonding in the ionisation and dissociation of compounds, Zh. Fiz. Khim., 1967, 41, 2336, In original 1255. [all data]

Notes

Go To: Top, Gas phase thermochemistry data, Condensed phase thermochemistry data, Phase change data, Reaction thermochemistry data, Gas phase ion energetics data, Ion clustering data, IR Spectrum, Mass spectrum (electron ionization), References

• Symbols used in this document:

  AE	Appearance energy
  Cp,gas	Constant pressure heat capacity of gas
  Cp,liquid	Constant pressure heat capacity of liquid
  Pc	Critical pressure
  S°gas	Entropy of gas at standard conditions
  T	Temperature
  Tboil	Boiling point
  Tc	Critical temperature
  Tfus	Fusion (melting) point
  ΔfH°liquid	Enthalpy of formation of liquid at standard conditions
  ΔrG°	Free energy of reaction at standard conditions
  ΔrH°	Enthalpy of reaction at standard conditions
  ΔvapH	Enthalpy of vaporization

• Data from NIST Standard Reference Database 69: NIST Chemistry WebBook
• The National Institute of Standards and Technology (NIST) uses its best efforts to deliver a high quality copy of the Database and to verify that the data contained therein have been selected on the basis of sound scientific judgment. However, NIST makes no warranties to that effect, and NIST shall not be liable for any damage that may result from errors or omissions in the Database.
• Customer support for NIST Standard Reference Data products.