Formaldehyde chlorine atom reaction

In the company Aerojet, based on the TerMeer method [37], DNPOH was synthesized from as the starting material nitroethane in dichloroethane (EDC), through the chlorification with sodium chloride, substitution of chlorine atom with nitro, and finally reaction with formaldehyde under the action of sulfuric acid. The reaction mechanism is ... 

For the two investigated compounds with the chlorine atom substituted next to the double bond, the intensity of the nitroperoxy bands passed through a maximum while the nitroxy bands continued to increase during the course of the experiments. A carbonyl band at approximately 1750 cm was seen at the same time. This indicates that either a carbonyl nitrate compound or a nitrate and a carbonyl compound were formed through decomposition of the nitroperoxy nitrate intermediate. Small amounts of acetaldehyde and chloroacetaldehyde were found among the products formed from the reaction with l-chloro-2-butene. In the reaction with 3-chloro-l-butene, significant amounts of formaldehyde were formed. 

Fasano, D.M., and N.S. Nogar (1981), The infrared chemiluminescent reaction of chlorine atoms with formaldehyde, Int J. Chem. Kinetics, 13, 325-332. 

Niki, H., P.D. Maker, L.P. Breitenbach, and C.M. Savage (1978a), FTIR stndies of the kinetics and mechanism for the reaction of chlorine atom with formaldehyde, Chem. Phys. Letters, 57, 596-599. 

Seakins, P.W., J.J. Orlando, and GS. Tyndall (2004), Rate coefficients and production of vibrationally excited HCl from the reactions of chlorine atoms with methanol, ethanol, acetaldehyde and formaldehyde, Phys. Chem. Chem. Phys., 6, 2224—2229. 

Fig. 1. Examples of temperature dependence of the rate constant for the reactions in which the low-temperature rate-constant limit has been observed 1. hydrogen transfer in the excited singlet state of the molecule represented by (6.16) 2. molecular reorientation in methane crystal 3. internal rotation of CHj group in radical (6.25) 4. inversion of radical (6.40) 5. hydrogen transfer in halved molecule (6.16) 6. isomerization of molecule (6.17) in excited triplet state 7. tautomerization in the ground state of 7-azoindole dimer (6.1) 8. polymerization of formaldehyde in reaction (6.44) 9. limiting stage (6.45) of (a) chain hydrobromination, (b) chlorination and (c) bromination of ethylene 10. isomerization of radical (6.18) 11. abstraction of H atom by methyl radical from methanol matrix [reaction (6.19)] 12. radical pair isomerization in dimethylglyoxime crystals [Toriyama et al. 1977].

Stelson, A. W and J. H. Seinfeld, Chemical Mass Accounting of Uban Aerosol, Environ. Sci. Technol., 15, 671-679(1981). Stickel, R. E., J. M. Nicovich, S. Wang, Z. Zhao, and P. H. Wine, Kinetic and Mechanistic Study of the Reaction of Atomic Chlorine with Dimethyl Sulfide, J. Phys. Chem., 96, 9875-9883 (1992). Swartz, E J. Boniface, I. Tchertkov, O. V. Rattigan, D. V. Robinson, P. Davidovits, D. R. Worsnop, J. T. Jayne, and C. E. Kolb, Horizontal Bubble Train Apparatus for Heterogeneous Chemistry Studies Uptake of Gas-Phase Formaldehyde, Environ. Sci. Technol, 31, 2634-2641 (1997). 

In case of atomic oxygen reactions the formation of formaldehyde was found to be characteristic for all compounds studied (naturally except NH3 and CO). As a rule, but not always, the main reaction is the formation of formaldehyde. For example, for dichloroethane the reaction proceeds with scission of the carbon bond, but CH2O does not appear to be the main reaction product. As the dichloroethane molecule contains chlorine, the main product will be HC1. The formation of a... 

Figure 4. Examples of low-temperature limit of rate constant of solid-state chamical reactions obtained in different laboratories of the USSR, United States, Canada, and Japan (1) formaldehyde polymerization chain growth (USSR, 1973 [56]) (2) reduction of coordination Fe-CO bond in heme group of mioglobin broken by laser pulse (United States, 1975 [65]) (3) H-atom transfer between neighboring radical pairs in y-irradiated dimethylglyoxime crystal (Japan, 1977, [72], (4, 5) H-atom abstraction by methyl radicals from neighboring molecules of glassy methanol matrix (4) and ethanol matrix (5) (Canada, United States, 1977 [11, 78]) (6) H-atom transfer under sterically hampered isomerization of aryl radicals (United States, 1978 [73]) (7) C-C bond formation in cyclopentadienyl biradicals (United States, 1979 [111]) (8) chain hydrobromination of ethylene (USSR, 1978 [119]) (9) chain chlorination of ethylene (USSR, 1986 [122]) (10) organic radical chlorination by molecular chlorine (USSR, 1980 [124,125]) (11) photochemical transfer of H atoms in doped monocrystals of fluorene (B. Prass, Y. P. Colpa, and D. Stehlik, J. Chem. Phys., in press.).

Michael, J.V., D.F. Nava, W.A. Payne, and L.J. Stief (1979b), Rate constant for the reaction of atomic chlorine with formaldehyde from 200 to 500 K, J. Chem. Phys., 70, 1147-1150. 

Poulet, G, G. Laverdet, and G Le Bras (1981), Discharge flow-mass speciromelric determination of the rate coefficients for the reactions of formaldehyde with bromine atoms and chlorine... 

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