Free Unsolvated Formaldehyde in Solutions: Influence of Temperature, Solvent Permittiity, and Total Formaldehyde Concentration
DOI:
https://doi.org/10.6000/1929-5030.2015.04.03.3Keywords:
Free formaldehyde, 1-hydroxyalkyl radical, formyl radical, equationAbstract
A mechanism of the initiated nonbranched-chain process of forming 1,2-alkanediols and carbonyl compounds in alcohol-formaldehyde systems is suggested. The quasi-steady-state treatment is used to obtain kinetic equations that can describe the nonmonotonic (with a maximum) dependences of the formation rates of the products on the concentration of free unsolvated formaldehyde. The experimental concentration of the free unsolvated form of formaldehyde are given at the different temperatures, solvent permittivity and total concentrations of formaldehyde in water and alcohols. An empirical equation for calculating the free formaldehyde concentration in alcohol-formaldehyde (including water/ethanediol-formaldehyde) systems at various temperatures and total formaldehyde concentrations and an equation for evaluating solvent concentrations in these systems were derived.
References
[1] Ogorodnikov SK. Formal'degid (Formaldehyde), Khimiya, Leningrad 1984.
[2] Silaev MM, Rudnev AV, Kalyazin EP. Formaldehyde. III. Concentration of Free Formaldehyde as a Function of Temperature, Polarity of Solvents, and Total Concentration of Formaldehyde in Solution. Zhurnal Fizicheskoi Khimii 1979; 53(7): 1647-1651.
[3] Gurvich LV, Karachevtsev GV, Kondrat'ev VN, Lebedev YuA, Medvedev VA, Potapov VK, Khodeev YuS. Energii razryva khimicheskikh svyazei. Potentsialy ionizatsii i srodstvo k elektronu”(“Bond Dissociation Energies, Ionization Potentials, and Electron Affinity”). Kondrat'ev VN. Ed., Nauka, Moscow 1974.
[4] Benson SW. Thermochemical Kinetics: Methods for the Estimation of Thermochemical Data and Rate Parameters. 2nd ed. Wiley, New York 1976.
[5] Pedley JB, Naylor RD, Kirby SP. Thermochemical Data of Organic Compounds. 2nd ed., Chapman & Hall, London 1986.
[6] Orlov YuD, Lebedev YuA, Saifullin ISh. Termokhimiya organicheskikh svobodnykh radikalov” (“Thermochemistry of Organic Free Radicals). Kutepov AM, Ed., Nauka, Moscow 2001.
[7] Silaev MM, Bugaenko LT. Kinetics of the Addition of - Hydroxyalkyl Radicals to 2-Propen-1-ol and Formaldehyde. Kinetics and Katalysis 1994; 35(4): 509-513. English Translation in: Kinetics and Katalysis 1994; 35(4): 463-467.
[8] Silaev MM. Simulation of Nonbranched Chain Processes for Producing 1,2-Alkanediols in Alcohol–Formaldehyde Systems. Teoreticheskie Osnovy Khimicheskoi Tekhnologii 2007; 41(4): 379-384. English Translation in: Thoretical Foundations Chemical Engineering 2007; 41(4): 357-361. http://dx.doi.org/10.1134/S0040579507040045
[9] Oyama M. A Free-Radical Reaction of Primary and Secondary Alcohols with Formaldehyde. The Journal of Organic Chemistry 1965; 30(7): 2429-2432. http://dx.doi.org/10.1021/jo01018a079
[10] Nikishin GI, Lefor D, Vorob’ev ED. Free Radical Reaction of Primary Alcohols with Formaldehyde. Izvestiya Akademii Nauk SSSR, Ser. Khimiya 1966; 7: 1271-1272.
[11] Urry WH, Stacey FW, Huyser ES, Juveland OO. The Peroxide- and Light-Induced Additions of Alcohols to Olefins. Journal of the American Chemical Society 1954; 76(2): 450- 455. http://dx.doi.org/10.1021/ja01631a037
[12] Dzhurinskaya MB, Rudnev AV, Kalyazin EP. High Temperature UV Photolysis of Formaldehyde in Liquid Methanol. Vestnik Moskovskogo Universiteta, Ser. 2: Khimiya 1984; 25(2): 173-176.
[13] Kalyazin EP, Petryaev EP, Shadyro OI. Reaction between Oxyalkyl Radicals and Aldehydes. Zhurnal Organicheskoi Khimii 1977; 13(2): 293-295.
[14] Novoselov AI, Silaev AI, M.M., Bugaenko LT. Effect of Temperature on the Yields of Final Products in the - Radiolysis of Formaldehyde Solutions in C1–C3 Alkanols. Khimiya Vysokich Energii 2004; 38(4): 270-272. English Translation in: High Energy Chemistry 2004; 38(4): 236-238.
[15] Silaev MM, Bugaenko LT. Mathematical Simulation of the Kinetics of Radiation Induced Hydroxyalkylation of Aliphatic Saturated Alcohols. Radiation Physics and Chemistry 1992; 40(1): 1-10. http://dx.doi.org/10.1016/1359-0197(92)90131-x
[16] Novoselov AI, Silaev MM, Bugaenko LT. Dependence of Ethanediol Yield on Formaldehyde Concentration in - Radiolysis of Methanol–Formaldehyde System at 373–473 K. Khimiya Vysokikh Energii 2008; 42(1): 74-75. English Translation in: High Energy Chemistry 2008; 42(1): 69-70. http://dx.doi.org/10.1134/S0018143908010141
[17] Novoselov AI, Silaev MM, Bugaenko LT. -Induced SingleStep Synthesis of Ethylene Glycol from Methanol– Formaldehyde Solution. Theoreticheskie Osnovy Khimicheskoy Tekhnologii 2010; 44(4): 450-453. English Translation in: Theoretical Foundation of Chemical Engineering 2010; 44(4): 432-435. http://dx.doi.org/10.1134/S0040579510040111
[18] Novoselov AI, Silaev MM, Bugaenko LT. Dependence of 1,2- Propanediol Yield on Formaldehyde Concentration in - Radiolysis of Ethanol–Formaldehyde System at 373–473 K. Khimiya Vysokikh Energii 2007; 41(1): 58. English Translation in: High Energy Chemistry 2007; 41(1): 53. http://dx.doi.org/10.1134/S0018143907010110
[19] Pshezhetskii SYa, Kotov AG, Milinchuk VK, Roginskii VA, Tupikov VI. EPR svobodnykh radikalov v radiatsionnoi khimii” (“ESR of Free Radicals in Radiation Chemistry”). Khimiya, Moscow 1972.
[20] Bateman L. Olefin Oxidation. Quarterly Reviews 1954; 8(2): 147-167. http://dx.doi.org/10.1039/qr9540800147
[21] Silaev MM. Simulation of the Nonbranched-Chain Addition of Saturated Free Radicals to Alkenes and Their Derivatives Yielding 1:1 Adducts. Teoreticheskie Osnovy Khimicheskoi Tekhnologii 2007; 41(3): 280-295. English Translation in: Theoretical Foundations of Chemical Engineering 2007; 41(3): 273-278. http://dx.doi.org/10.1134/S0040579507030062
[22] Silaev MM. Applied Aspects of the -Radiolysis of C1–C4 Alcohols and Binary Mixtures on Their Basis. Khimiya Vysokikh Energii 2002; 36(2): 97-101. English Translation in: High Energy Chemistry 2002; 36(2): 70-74. http://dx.doi.org/10.1023/A:1014650726821
[23] Silaev MM. Estimating the Solvent Concentration in Formaldehyde Solutions at Various Temperatures. Zhurnal Fizicheskoy Khimii 1993; 67(9): 1944.
[24] Silaev MM, Bugaenko LT, Kalyazin EP. On the Possibility of Adequately Estimating of the Rate Constants for the Reaction of Hydroxyalkyl Radicals with Each Other Using the Self-Diffusion Coefficients or Viscosities of the Corresponding Alcohols. Vestnik Moskovskogo. Univiversiteta, Ser. 2: Khimiya 1986; 27(4): 386-389.
[25] Walker JF. Formaldehyde, Reinhold, New York 1953. English Translation under the title Formal’degid, Goskhimizdat, Moscow 1957; p. 106.
[26] Shadyro OI. Radiation-chemical Conversions of Aldehydes in Various Systems. Ph.D. Thesis (Chemistry), Belarusian State University, Minsk 1975.
[27] Silaev MM. Relative Reactivity of -Hydroxyethyl Radicals for 2-Propene-1-ol and Formaldehyde Double-Bond Addition. Vestnik Moskovskogo Universiteta, Ser. 2: Khimiya 1993; 34(3): 311.
[28] Seki H, Nagai R, Imamura M. -Radiolysis of a Binary Mixture of Methanol and Water. The Formation of Formaldehyde in the Radiolysis of Liquid Methanol. Bulletin of the Chemical Society of Japan 1968; 41(12): 2877-2881. http://dx.doi.org/10.1246/bcsj.41.2877
Downloads
Published
2015-09-08
How to Cite
Silaev, M. M. (2015). Free Unsolvated Formaldehyde in Solutions: Influence of Temperature, Solvent Permittiity, and Total Formaldehyde Concentration. Journal of Applied Solution Chemistry and Modeling, 4(3), 152–159. https://doi.org/10.6000/1929-5030.2015.04.03.3
Issue
Section
General Articles
License
Policy for Journals/Articles with Open Access
Authors who publish with this journal agree to the following terms:
- Authors retain copyright and grant the journal right of first publication with the work simultaneously licensed under a Creative Commons Attribution License that allows others to share the work with an acknowledgement of the work's authorship and initial publication in this journal.
- Authors are permitted and encouraged to post links to their work online (e.g., in institutional repositories or on their website) prior to and during the submission process, as it can lead to productive exchanges, as well as earlier and greater citation of published work
Policy for Journals / Manuscript with Paid Access
Authors who publish with this journal agree to the following terms:
- Publisher retain copyright .
- Authors are permitted and encouraged to post links to their work online (e.g., in institutional repositories or on their website) prior to and during the submission process, as it can lead to productive exchanges, as well as earlier and greater citation of published work .
