Skip to main content
SpringerLink
Log in

Theoretic studies on the kinetics and mechanism of multi-channel gas-phase unimolecular reactions of 1-chloropropane and 2-chloropropane

  • Original Research
  • Published:
Structural Chemistry Aims and scope Submit manuscript

Abstract

The potential energy surfaces of the gas-phase unimolecular decomposition reactions of 1-chloropropane and 2-chloropropane are investigated by various quantum chemical methods including CCSD(T), CCSD, GBS-QB3, C3B3, MP4, MP2, and B3LYP. Modified strong collision/RRKM theory was used to calculate the unimolecular rate constants as a function of pressure and temperature. It is found that the major reaction pathway is the HCl elimination. It is predicted that bond dissociation reactions have negligible contribution to the overall rate constant. The computed rate constants are compared with the available experimental data.

This is a preview of subscription content, log in via an institution to check access.

Access this article

Log in via an institution

Subscribe and save

Springer+ Basic
$34.99 /Month
  • Get 10 units per month
  • Download Article/Chapter or eBook
  • 1 Unit = 1 Article or 1 Chapter
  • Cancel anytime
Subscribe now

Buy Now

Price excludes VAT (USA)
Tax calculation will be finalised during checkout.

Instant access to the full article PDF.

Institutional subscriptions

Fig. 1
Fig. 2
Fig. 3
Fig. 4
Fig. 5
Fig. 6
Fig. 7
Fig. 8

Similar content being viewed by others

References

  1. Barton DHR, Head AJ (1950) J Chem Soc Faraday Trans 2(46):114

    Article  Google Scholar 

  2. Barton DHR, Head AJ, Williams RJ (1951) J Chem Soc 2039. doi:10.1039/JR9510002039

  3. Hartmann H, Bosche HG, Heydtmann H (1964) Z Phys Chem (Neue Folge) 42:329

    Article  CAS  Google Scholar 

  4. Evans PJ, Ichimura T, Tschuikow-Roux E (1978) Int J Chem Kinet 10:855

    Article  CAS  Google Scholar 

  5. Howlett KE (1952) J Chem Soc London 3695. doi:10.1039/JR9520003695

  6. Asahina M, Onozuka M (1964) J Polym Sci A 2:3505

    CAS  Google Scholar 

  7. Tsang W (1964) J Chem Phys 41:2487

    Article  CAS  Google Scholar 

  8. Cadman P, Day M, Trotman-Dickenson AF (1970) J Chem Soc A 2498. doi:10.1039/J19700002498

  9. Chytry V, Obereigner B, Lim D (1970) Chem Ind (London) 470. doi:10.1039/JR9510002039

  10. Heydtmann H, Dill B, Jonas R (1975) Int J Chem Kinet 7:973

    Article  CAS  Google Scholar 

  11. Lifshitz A, Wohlfeiler D, Tamburu (1995) C J Phys Chem 99:11436

  12. Swihart MT, Carr RW (1996) Int J Chem Kinet 28:817

    Article  CAS  Google Scholar 

  13. Frisch MJ, Trucks GW, Schlegel HB, Scuseria GE, Robb MA, Cheeseman JR, Montgomery JA, Jr, Vreven T, Kudin KN, Burant JC, Millam JM, Iyengar SS, Tomasi J, Barone V, Mennucci B, Cossi M, Scalmani G, Rega N, Petersson GA, Nakatsuji H, Hada M, Ehara M, Toyota K, Fukuda R, Hasegawa J, Ishida M, Nakajima T, Honda Y, Kitao O, Nakai H, Klene M, Li X, Knox JE, Hratchian HP, Cross JB, Adamo C, Jaramillo J, Gomperts R, Stratmann RE, Yazyev O, Austin AJ, Cammi R, Pomelli C, Ochterski JW, Ayala PY, Morokuma K, Voth GA, Salvador P, Dannenberg JJ, Zakrzewski VG, Dapprich S, Daniels AD, Strain MC, Farkas O, Malick DK, Rabuck AD, Raghavachari K, Foresman JB, Ortiz JV, Cui Q, Baboul AG, Clifford S, Cioslowski J, Stefanov BB, Liu G, Liashenko A, Piskorz P, Komaromi I, Martin RL, Fox DJ, Keith T, Al-Laham MA, Peng CY, Nanayakkara A, Challacombe M, Gill PMW, Johnson B, Chen W, Wong MW, Gonzalez C, Pople JA (2004) Gaussian 03, Revision C01. Gaussian, Inc, Wallingford

  14. Møller C, Plesset MS (1934) Phys Rev 46:618

    Article  Google Scholar 

  15. Dunning TH (1989) J Chem Phys 90:1007

    Article  CAS  Google Scholar 

  16. Raghavachari K, Trucks GW, Pople JA, Head-gordon M (1989) Chem Phys Lett 157:479

    Article  CAS  Google Scholar 

  17. Baboul AG, Curtiss LA, Redfern PC, Raghavachari K (1999) J Chem Phys 110:7650

    Article  CAS  Google Scholar 

  18. Montgomery JA Jr, Frisch MJ, Ochterski JW, Petersson GA (1999) J Chem Phys 110:2822

    Article  CAS  Google Scholar 

  19. Montgomery JA Jr, Frisch MJ, Ochterski JW, Petersson GA (2000) J Chem Phys 112:6532

    Article  CAS  Google Scholar 

  20. Gonzalez C, Schlegel HB (1990) J Phys Chem 94:5523

    Article  CAS  Google Scholar 

  21. Holbrook K, Pilling M, Robertson S (eds) (1996) Unimolecular reactions. Wiley, Chichester

    Google Scholar 

  22. Gilbert RG, Smith SC (eds) (1990) Theory of unimolecular and recombination reactions. Blackwell Scientific, Oxford

    Google Scholar 

  23. Whitten GZ, Rabinovitch BS (1963) J Chem Phys 38:2466

    Article  CAS  Google Scholar 

  24. Troe J (1977) J Chem Phys 66:4745

    Article  CAS  Google Scholar 

  25. Oref I (1992) J Phys Chem 96:6308

    Article  CAS  Google Scholar 

  26. Tweedale A, Laidler KJ (1970) J Chem Phys 53:2045

    Article  CAS  Google Scholar 

  27. Isaacson AD, Truhlar DG (1982) J Chem Phys 76:1380

    Article  CAS  Google Scholar 

  28. Garrett BC, Truhlar DG (1979) J Phys Chem 83:1052

    Article  CAS  Google Scholar 

  29. Garrett BC, Truhlar DG (1979) J Phys Chem 83:3058

    Google Scholar 

  30. Garrett BC, Truhlar DG (1983) J Phys Chem 87:4553

    Google Scholar 

  31. Garrett BC, Truhlar DG (1979) J Am Chem Soc 101:4534

    Article  CAS  Google Scholar 

  32. Eckart C (1930) Phys Rev 35:1303

    Article  CAS  Google Scholar 

  33. Johnston H (ed) (1966) Gas phase reaction rate theory. Ronald, New York

    Google Scholar 

  34. Lee TJ, Taylor PR (1989) Int J Quantum Chem Quant Chem Symp S23:199

  35. During JD, Zhu X, Shen S (2001) J Mol Struct 570:1

    Article  Google Scholar 

  36. Luis A, Sanz ME, Lorenzo FJ, López JC, Alonso JL (1997) J Mol Spectrosc 184:60

    Google Scholar 

  37. Smith AL (1982) In: Carver CD (ed) The Coblentz society desk book of infrared spectra, 2nd edn. The Coblentz Society, Kirkwood

  38. Tobiason FL, Schwendeman RH (1964) J Chem Phys 40:1014

    Article  CAS  Google Scholar 

  39. McGrath MP, Rowland FS (2002) J Phys Chem A 106:8191

    Article  CAS  Google Scholar 

  40. Zhu L, Hase WL (1993) QCPE program 644, quantum chemistry program exchange. Indiana University, Bloomington

Download references

Author information

Authors and Affiliations

  1. Department of Chemistry, Shahid-Bahonar University of Kerman, Kerman, 76169, Iran

    V. Saheb

Authors
  1. V. Saheb
    View author publications

    You can also search for this author in PubMed Google Scholar

Corresponding author

Correspondence to V. Saheb.

Rights and permissions

Reprints and permissions

About this article

Cite this article

Saheb, V. Theoretic studies on the kinetics and mechanism of multi-channel gas-phase unimolecular reactions of 1-chloropropane and 2-chloropropane. Struct Chem 25, 21–28 (2014). https://doi.org/10.1007/s11224-013-0240-2

Download citation

  • Received:

  • Accepted:

  • Published:

  • Issue Date:

  • DOI: https://doi.org/10.1007/s11224-013-0240-2

Keywords

Search

Navigation