Elsevier

Chemical Physics Letters

Volume 57, Issue 4, 15 August 1978, Pages 596-599
Chemical Physics Letters

FTIR studies of the kinetics and mechanism for the reaction of Cl atom with formaldehyde

https://doi.org/10.1016/0009-2614(78)85328-7Get rights and content

Abstract

Product studies were made with the FTIR method in the photolysis of mixtures containing Cl2 and CH2O up to 1 torr each in I atm Ar. The formation of two principal products, HCl and HCClO, can be accounted for by the chain photochlorination of CH2O i.e., Cl2 + hv → 2 Cl, Cl + CH2O → CHO + HCl, CHO + Cl2 → HCClO + Cl. The rate constant for the ClCH2O reaction was determined from relative decay rates of CH2O and C2H6 in the photolysis of Cl2CH2OC2H6 mixtures. The value of k(Cl + CH2O/Cl + C2H6) = 1.3 combined with the literature value of k(Cl + C2H6 = 6 × 10−11 cm3 molecule−1 s−1 gives k(Cl + CH2O) = 7.8 × 10−11 cm3 molecule−1 s−1 at 298 ± 2 K.

References (8)

  • F.S. Rowland et al.

    Rev. Geophys. Space Phys.

    (1975)
  • K.B. Krauskopf et al.

    J. Am. Chem. Soc.

    (1934)
  • I.C. Hisatsune et al.

    Can. J. Spectry.

    (1973)
There are more references available in the full text version of this article.

Cited by (38)

  • Atmospheric sink of styrene, Α-methylstyrene, trans-Β-methylstyrene and indene: Rate constants and mechanisms of Cl atom-initiated degradation

    2019, Atmospheric Environment
    Citation Excerpt :

    From a minimum of three experiments, plots of the yields of products versus the amount of consumed styrene gave a molar benzaldehyde, benzoyl chloride, formyl chloride and formaldehyde yield of 22 ± 3%, 28 ± 6%, 24 ± 4% and 29 ± 2%, respectively. The yields for formaldehyde and benzaldehyde were corrected due to secondary losses reaction with Cl using k (Cl + formaldehyde) = 7.8 × 10−11 cm3 molecule−1 s−1 (Niki et al., 1978) and k(Cl + benzaldehyde) = 1.0 × 10−10 cm3 molecule−1 s−1 (Thiault et al., 2002) by the method outlined in Tuazon et al. (1986). The rate constants with Cl atoms for benzoyl chloride (Caralp et al., 1999) and formyl chloride (Sanhueza et al., 1975; Niki et al., 1980) have been reported to be fairly low at room temperature, i.e. 1.16 × 10−15 cm3 molecule−1 s−1 and 7.8 × 10−13 cm3 molecule−1 s−1, respectively, so these two products were not corrected for secondary losses.

  • Reaction products and mechanisms for the reaction of n-butyl vinyl ether with the oxidants OH and Cl: Atmospheric implications

    2015, Atmospheric Environment
    Citation Excerpt :

    The main products identified by comparison of the IR spectra after the consumption of BVE >99% were butyl formate (CH3(CH2)3OC(O)H), butyl chloroacetate CH3(CH2)3OC(O)CH2Cl), formic acid (HCOOH), HCl, and CO. The IR bands at 1784 and 738 cm−1 were assigned to formyl chloride (HCOCl) by comparison with the characteristic IR bands of this compound from the literature (Niki et al., 1978; French et al., 1994). In a separate experiment it was confirmed that the peaks at 1148 and 695 cm−1 were due to reaction products of BVE with Cl2.

View all citing articles on Scopus
View full text