Formic acid

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Gas phase thermochemistry data

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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
DRB - Donald R. Burgess, Jr.
GT - Glushko Thermocenter, Russian Academy of Sciences, Moscow

Quantity Value Units Method Reference Comment
Δfgas-378.6kJ/molCmGuthrie, 1974Heat of hydrolysis; ALS
Δfgas-379.0kJ/molN/ALebedeva, 1964Value computed using ΔfHliquid° value of -425.5±0.3 kj/mol from Lebedeva, 1964 and ΔvapH° value of 46.5 kj/mol from Guthrie, 1974.; DRB
Δfgas-379.2 ± 0.6kJ/molCcbLebedeva, 1964Value computed using ΔfHliquid° from Lebedeva, 1964 and ΔvapH° value of 46.3 kJ/mol from Konicek and Wadso, 1970.; DRB
Δfgas-378.3kJ/molN/ASinke, 1959Value computed using ΔfHliquid° value of -424.8±0.3 kj/mol from Sinke, 1959 and ΔvapH° value of 46.5 kj/mol from Guthrie, 1974.; DRB
Δfgas-378.5 ± 0.6kJ/molCcbSinke, 1959Value computed using ΔfHliquid° from Sinke, 1959 and ΔvapH° value of 46.3 kJ/mol from Konicek and Wadso, 1970.; DRB
Quantity Value Units Method Reference Comment
gas248.70 ± 0.42J/mol*KN/AMillikan R.C., 1957Other third-law S(298.15 K) value is 248.11(1.26) J/mol*K [ Halford J.O., 1942, Millikan R.C., 1957]. Please also see Waring W., 1952.; GT

Constant pressure heat capacity of gas

Cp,gas (J/mol*K) Temperature (K) Reference Comment
33.2650.Chao J., 1986p=1 bar. Selected entropies and heat capacities are in close agreement with statistically calculated values [ Fukushima K., 1971] and value of S(298.15 K) calculated by ab initio method [ East A.L.L., 1997]. Maximum discrepancies with other statistical calculations [ Waring W., 1952, Green J.H.S., 1961, Gurvich, Veyts, et al., 1989] amount to 1.1-3.9 J/mol*K for S(T) and 3.0-5.9 J/mol*K for Cp(T). Please also see Chao J., 1978.; GT
33.44100.
34.91150.
37.83200.
43.54273.15
45.68 ± 0.07298.15
45.84300.
54.52400.
62.63500.
69.81600.
76.04700.
81.34800.
85.77900.
89.401000.
92.331100.
94.651200.
96.481300.
97.911400.
99.021500.

Condensed phase thermochemistry data

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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
Δfliquid-425.09kJ/molCmGuthrie, 1974Heat of hydrolysis; ALS
Δfliquid-425.5 ± 0.3kJ/molCcbLebedeva, 1964ALS
Δfliquid-424.8 ± 0.3kJ/molCcbSinke, 1959ALS
Quantity Value Units Method Reference Comment
Δcliquid-253.8 ± 0.3kJ/molCcbLebedeva, 1964Corresponding Δfliquid = -425.51 kJ/mol (simple calculation by NIST; no Washburn corrections); ALS
Δcliquid-254.6 ± 0.3kJ/molCcbSinke, 1959Corresponding Δfliquid = -424.72 kJ/mol (simple calculation by NIST; no Washburn corrections); ALS
Quantity Value Units Method Reference Comment
liquid131.84J/mol*KN/AStout and Fisher, 1941Includes 2.89 J/mol*K for zero-point entropy.; DH
liquid128.4J/mol*KN/AParks, Kelley, et al., 1929Extrapolation below 90 K, 29.7 J/mol*K. Revision of previous data.; DH
liquid143.1J/mol*KN/AGibson, Latimer, et al., 1920Used Berthelot's value, 10125 J/mol for H fusion. Extrapolation below 70 K, no details.; DH

Constant pressure heat capacity of liquid

Cp,liquid (J/mol*K) Temperature (K) Reference Comment
99.04298.15Stout and Fisher, 1941T = 15 to 300 K.; DH
98.10298.15Glagoleva and Chervov, 1936Temperature range: 298.15, 333.15, 353.15 K.; DH
100.0290.Radulescu and Jula, 1934DH
98.3291.5Gibson, Latimer, et al., 1920T = 71 to 292 K. Value is unsmoothed experimental datum.; DH
95.4298.von Reis, 1881T = 291 to 385 K.; DH

Phase change data

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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
DH - Eugene S. Domalski and Elizabeth D. Hearing

Quantity Value Units Method Reference Comment
Tboil373.9 ± 0.5KAVGN/AAverage of 25 out of 30 values; Individual data points
Quantity Value Units Method Reference Comment
Tfus281.5 ± 0.6KAVGN/AAverage of 9 values; Individual data points
Quantity Value Units Method Reference Comment
Ttriple281.45KN/AWilhoit, Chao, et al., 1985Uncertainty assigned by TRC = 0.1 K; TRC
Ttriple281.40KN/AStout and Fisher, 1941, 2Uncertainty assigned by TRC = 0.06 K; TRC
Quantity Value Units Method Reference Comment
Ptriple0.0236barN/ATaylor and Bruton, 1952Uncertainty assigned by TRC = 0.000067 bar; TRC
Quantity Value Units Method Reference Comment
Tc577.KN/AAnselme and Teja, 1990Uncertainty assigned by TRC = 30. K; Tc > 577 K, which was observed with decomposition; TRC
Tc588.KN/AAmbrose and Ghiassee, 1987Uncertainty assigned by TRC = 10. K; TRC
Tc580.KN/AMajer and Svoboda, 1985 
Quantity Value Units Method Reference Comment
Δvap46.3kJ/molN/AMajer and Svoboda, 1985 
Δvap36.0kJ/molAStephenson and Malanowski, 1987Based on data from 283. to 384. K.; AC
Δvap46.3 ± 0.5kJ/molCKonicek and Wadso, 1970ALS
Δvap46.3 ± 0.5kJ/molCKonicek, Wadsö, et al., 1970AC
Δvap19.9kJ/molN/AStout and Fisher, 1941, 3AC

Enthalpy of vaporization

ΔvapH (kJ/mol) Temperature (K) Method Reference Comment
22.69373.8N/AMajer and Svoboda, 1985 
35.2315.EBAmbrose and Ghiassee, 1987, 2Based on data from 300. to 392. K.; AC
35.2325.N/ADreisbach and Shrader, 1949Based on data from 310. to 374. K. See also Dreisbach and Martin, 1949.; AC
29.6303.N/ACampbell and Campbell, 1934AC
20.3315.N/ACoolidge, 1930Based on data from 273. to 373. K.; AC
20.9338.N/ACoolidge, 1930Based on data from 273. to 373. K.; AC
20.4315.CCoolidge, 1930AC
21.1338.CCoolidge, 1930AC
36.8288.N/AKahlbaum, 1894Based on data from 273. to 307. K.; AC
47.7374.N/AKahlbaum, 1883Based on data from 295. to 374. K.; AC

Enthalpy of vaporization

ΔvapH = A exp(-αTr) (1 − Tr)β
    ΔvapH = Enthalpy of vaporization (at saturation pressure) (kJ/mol)
    Tr = reduced temperature (T / Tc)

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Temperature (K) 298. to 374.
A (kJ/mol) 23.8
α 2.1043
β -1.2652
Tc (K) 580.
ReferenceMajer and Svoboda, 1985

Antoine Equation Parameters

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

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Temperature (K) A B C Reference Comment
273.7 to 307.42.00121515.-139.408Kahlbaum, 1894, 2Coefficents calculated by NIST from author's data.

Enthalpy of sublimation

ΔsubH (kJ/mol) Temperature (K) Method Reference Comment
60.5275.N/AStephenson and Malanowski, 1987Based on data from 268. to 281. K.; AC
62. ± 1.213.TE,MECalis-Van Ginkel, Calis, et al., 1978Based on data from 203. to 218. K.; AC
60.1264.AStull, 1947Based on data from 253. to 275. K.; AC
60.7266.N/ACoolidge, 1930Based on data from 265. to 268. K. See also Jones, 1960.; AC

Enthalpy of fusion

ΔfusH (kJ/mol) Temperature (K) Reference Comment
12.678281.40Stout and Fisher, 1941DH

Entropy of fusion

ΔfusS (J/mol*K) Temperature (K) Reference Comment
45.05281.40Stout and Fisher, 1941DH

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:


References

Go To: Top, Gas phase thermochemistry data, Condensed phase thermochemistry data, Phase change data, Notes

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

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]

Lebedeva, 1964
Lebedeva, N.D., Heats of combustion of monocarboxylic acids, Russ. J. Phys. Chem. (Engl. Transl.), 1964, 38, 1435-1437. [all data]

Konicek and Wadso, 1970
Konicek, J.; Wadso, I., Enthalpies of vaporization of organic compounds. VII. Some carboxylic acids, Acta Chem. Scand., 1970, 24, 2612-26. [all data]

Sinke, 1959
Sinke, G.C., The heat of formation of formic acid, J. Phys. Chem., 1959, 63, 2063. [all data]

Millikan R.C., 1957
Millikan R.C., Infrared spectra and vibrational assignment of monomeric formic acid, J. Chem. Phys., 1957, 27, 1305-1308. [all data]

Halford J.O., 1942
Halford J.O., Entropy of the monomeric forms of formic acid and acetic acid, J. Chem. Phys., 1942, 10, 582-584. [all data]

Waring W., 1952
Waring W., Some thermodynamic properties of formic acid, Chem. Rev., 1952, 51, 171-183. [all data]

Chao J., 1986
Chao J., Thermodynamic properties of key organic oxygen compounds in the carbon range C1 to C4. Part 2. Ideal gas properties, J. Phys. Chem. Ref. Data, 1986, 15, 1369-1436. [all data]

Fukushima K., 1971
Fukushima K., Normal coordinate treatment and thermodynamic properties of the cis-trans isomers of formic acid and its deutero-analog, J. Chem. Thermodyn., 1971, 3, 553-562. [all data]

East A.L.L., 1997
East A.L.L., Ab initio statistical thermodynamical models for the computation of third-law entropies, J. Chem. Phys., 1997, 106, 6655-6674. [all data]

Green J.H.S., 1961
Green J.H.S., Thermodynamic properties of organic oxygen compounds. Part III. Formic acid, J. Chem. Soc., 1961, 2241-2242. [all data]

Gurvich, Veyts, et al., 1989
Gurvich, L.V.; Veyts, I.V.; Alcock, C.B., Thermodynamic Properties of Individual Substances, 4th ed.; Vols. 1 and 2, Hemisphere, New York, 1989. [all data]

Chao J., 1978
Chao J., Ideal gas thermodynamic properties of methanoic and ethanoic acids, J. Phys. Chem. Ref. Data, 1978, 7, 363-377. [all data]

Stout and Fisher, 1941
Stout, J.W.; Fisher, L.H., The entropy of formic acid. The heat capacity from 15 to 300K. Heats of fusion and vaporization, J. Chem. Phys., 1941, 9, 163-168. [all data]

Parks, Kelley, et al., 1929
Parks, G.S.; Kelley, K.K.; Huffman, H.M., Thermal data on organic compounds. V. A revision of the entropies and free energies of nineteen organic compounds, J. Am. Chem. Soc., 1929, 51, 1969-1973. [all data]

Gibson, Latimer, et al., 1920
Gibson, G.E.; Latimer, W.M.; Parks, G.S., Entropy changes at low temperatures. I. Formic acid and urea. A test of the third law of thermodynamics, J. Am. Chem. Soc., 1920, 42, 1533-1542. [all data]

Glagoleva and Chervov, 1936
Glagoleva, A.A.; Chervov, S.I., Investigation of the heat capacity of formic acid and its aqueous solutions, Zhur. Obshch. Khim., 1936, 6, 685-690. [all data]

Radulescu and Jula, 1934
Radulescu, D.; Jula, O., Beiträge zur Bestimmung der Abstufung der Polarität des Aminstickstoffes in den organischen Verbindungen, Z. Phys. Chem., 1934, B26, 390-393. [all data]

von Reis, 1881
von Reis, M.A., Die specifische Wärme flüssiger organischer Verbindungen und ihre Beziehung zu deren Moleculargewicht, Ann. Physik [3], 1881, 13, 447-464. [all data]

Wilhoit, Chao, et al., 1985
Wilhoit, R.C.; Chao, J.; Hall, K.R., Thermodynamic Properties of Key Organic Compounds in the Carbon Range C1 to C4. Part 1. Properties of Condensed Phases, J. Phys. Chem. Ref. Data, 1985, 14, 1. [all data]

Stout and Fisher, 1941, 2
Stout, J.W.; Fisher, L.H., The entropy of formic acid. The heat capacity from 15 to 300 K. Heats of fusion and vaporization, J. Chem. Phys., 1941, 9, 163-8. [all data]

Taylor and Bruton, 1952
Taylor, M.D.; Bruton, J., The vapour phase dissociation of some carboxylic acids. II. Formic and propionic acids., J. Am. Chem. Soc., 1952, 74, 4151. [all data]

Anselme and Teja, 1990
Anselme, M.J.; Teja, A.S., The critical properties of rapidly reacting substances, AIChE Symp. Ser., 1990, 86, 279, 128-32. [all data]

Ambrose and Ghiassee, 1987
Ambrose, D.; Ghiassee, N.B., Vapor Pressures and Critical Temperatures and Critical Pressures of Some Alkanoic Acids: C1 to C10, J. Chem. Thermodyn., 1987, 19, 505. [all data]

Majer and Svoboda, 1985
Majer, V.; Svoboda, V., Enthalpies of Vaporization of Organic Compounds: A Critical Review and Data Compilation, Blackwell Scientific Publications, Oxford, 1985, 300. [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]

Konicek, Wadsö, et al., 1970
Konicek, Jiri; Wadsö, Ingemar; Munch-Petersen, J.; Ohlson, Ragnar; Shimizu, Akira, Enthalpies of Vaporization of Organic Compounds. VII. Some Carboxylic Acids., Acta Chem. Scand., 1970, 24, 2612-2616, https://doi.org/10.3891/acta.chem.scand.24-2612 . [all data]

Stout and Fisher, 1941, 3
Stout, J.W.; Fisher, Leon H., The Entropy of Formic Acid. The Heat Capacity from 15 to 300°K. Heats of Fusion and Vaporization, J. Chem. Phys., 1941, 9, 2, 163, https://doi.org/10.1063/1.1750869 . [all data]

Ambrose and Ghiassee, 1987, 2
Ambrose, D.; Ghiassee, N.B., Vapour pressures and critical temperatures and critical pressures of some alkanoic acids: C1 to C10, The Journal of Chemical Thermodynamics, 1987, 19, 5, 505-519, https://doi.org/10.1016/0021-9614(87)90147-9 . [all data]

Dreisbach and Shrader, 1949
Dreisbach, R.R.; Shrader, S.A., Vapor Pressure--Temperature Data on Some Organic Compounds, Ind. Eng. Chem., 1949, 41, 12, 2879-2880, https://doi.org/10.1021/ie50480a054 . [all data]

Dreisbach and Martin, 1949
Dreisbach, R.R.; Martin, R.A., Physical Data on Some Organic Compounds, Ind. Eng. Chem., 1949, 41, 12, 2875-2878, https://doi.org/10.1021/ie50480a053 . [all data]

Campbell and Campbell, 1934
Campbell, Alan Newton; Campbell, Alexandra Jean Robson, The thermodynamics of binary liquid mixtures : formic acid and water, Trans. Faraday Soc., 1934, 30, 1109, https://doi.org/10.1039/tf9343001109 . [all data]

Coolidge, 1930
Coolidge, Albert Sprague, THE VAPOR PRESSURE AND HEATS OF FUSION AND VAPORIZATION OF FORMIC ACID, J. Am. Chem. Soc., 1930, 52, 5, 1874-1887, https://doi.org/10.1021/ja01368a018 . [all data]

Kahlbaum, 1894
Kahlbaum, G.W.A., Z. Phys. Chem., Stoechiom. Verwandtschaftsl., 1894, 13, 14. [all data]

Kahlbaum, 1883
Kahlbaum, Georg W.A., Ueber die Abhängigkeit der Siedetemperatur vom Luftdruck, Ber. Dtsch. Chem. Ges., 1883, 16, 2, 2476-2484, https://doi.org/10.1002/cber.188301602178 . [all data]

Kahlbaum, 1894, 2
Kahlbaum, G.W.A., Studien uber Dampfspannkraftsmessungen, Z. Phys. Chem. (Leipzig), 1894, 13, 14-55. [all data]

Calis-Van Ginkel, Calis, et al., 1978
Calis-Van Ginkel, C.H.D.; Calis, G.H.M.; Timmermans, C.W.M.; de Kruif, C.G.; Oonk, H.A.J., Enthalpies of sublimation and dimerization in the vapour phase of formic, acetic, propanoic, and butanoic acids, The Journal of Chemical Thermodynamics, 1978, 10, 11, 1083-1088, https://doi.org/10.1016/0021-9614(78)90082-4 . [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]

Jones, 1960
Jones, A.H., Sublimation Pressure Data for Organic Compounds., J. Chem. Eng. Data, 1960, 5, 2, 196-200, https://doi.org/10.1021/je60006a019 . [all data]


Notes

Go To: Top, Gas phase thermochemistry data, Condensed phase thermochemistry data, Phase change data, References