Kinetics of the Reaction of Iodine with Acrolein. Bond Dissociation Energy of the Carbonyl C–H Bond

Ze'ev B. Alfassi; David M. Golden

doi:10.1021/ja00783a004

Kinetics of the Reaction of Iodine with Acrolein. Bond Dissociation Energy of the Carbonyl C–H Bond

Ze'ev B. Alfassi, David M. Golden

Research output: Contribution to journal › Article › peer-review

18 Scopus citations

Abstract

The reaction of iodine with acrolein has been studied in the temperature range 172-246°. The initial rates have been found to obey the rate law — d(I₂)/df = k₃(I)(acrolein), and k₃ is given by log (k₃/M^-1 2sec^-1) = (10.1 ± 0.2) — (16.8 ± 0.4) 9. From the activation energy and assuming E_-3 = 1 ± 1 kcal mol-1, it has been calculated that D(CH₂CHC(O)-H) = 87.1 ± 1.0 kcal mol^-1, and ΔH_t°(CH₂CHCO, g) = 17.3 ± 1.2 kcal mol^-1. The carbonyl C-H bond strength is the same as in formaldehyde reflecting the absence of any stabilization due to the vinyl group. The rate of iodine disappearance decreases with the extent of the reaction according to the scheme I₂ + CH₂CHCHO⇄ CH₂CHCOI + HI (3,4) and CH2=CHCOI⇄CH₂=C=CO + HI (5). k₅ is given by log (k₅/sec^-1) = (13.4 ± 1.0) — (42.8 ± 7.0)/9.

Original language	English
Pages (from-to)	319-323
Number of pages	5
Journal	Journal of the American Chemical Society
Volume	95
Issue number	2
DOIs	https://doi.org/10.1021/ja00783a004
State	Published - 1 Jan 1973
Externally published	Yes

ASJC Scopus subject areas

Catalysis
General Chemistry
Biochemistry
Colloid and Surface Chemistry

Access to Document

10.1021/ja00783a004

Cite this

@article{b2296df5495241dfae316913cd1af34f,

title = "Kinetics of the Reaction of Iodine with Acrolein. Bond Dissociation Energy of the Carbonyl C–H Bond",

abstract = "The reaction of iodine with acrolein has been studied in the temperature range 172-246°. The initial rates have been found to obey the rate law — d(I2)/df = k3(I)(acrolein), and k3 is given by log (k3/M-1 2sec-1) = (10.1 ± 0.2) — (16.8 ± 0.4) 9. From the activation energy and assuming E-3 = 1 ± 1 kcal mol-1, it has been calculated that D(CH2CHC(O)-H) = 87.1 ± 1.0 kcal mol-1, and ΔHt°(CH2CHCO, g) = 17.3 ± 1.2 kcal mol-1. The carbonyl C-H bond strength is the same as in formaldehyde reflecting the absence of any stabilization due to the vinyl group. The rate of iodine disappearance decreases with the extent of the reaction according to the scheme I2 + CH2CHCHO⇄ CH2CHCOI + HI (3,4) and CH2=CHCOI⇄CH2=C=CO + HI (5). k5 is given by log (k5/sec-1) = (13.4 ± 1.0) — (42.8 ± 7.0)/9.",

author = "Alfassi, {Ze'ev B.} and Golden, {David M.}",

year = "1973",

month = jan,

day = "1",

doi = "10.1021/ja00783a004",

language = "English",

volume = "95",

pages = "319--323",

journal = "Journal of the American Chemical Society",

issn = "0002-7863",

publisher = "American Chemical Society",

number = "2",

}

TY - JOUR

T1 - Kinetics of the Reaction of Iodine with Acrolein. Bond Dissociation Energy of the Carbonyl C–H Bond

AU - Alfassi, Ze'ev B.

AU - Golden, David M.

PY - 1973/1/1

Y1 - 1973/1/1

N2 - The reaction of iodine with acrolein has been studied in the temperature range 172-246°. The initial rates have been found to obey the rate law — d(I2)/df = k3(I)(acrolein), and k3 is given by log (k3/M-1 2sec-1) = (10.1 ± 0.2) — (16.8 ± 0.4) 9. From the activation energy and assuming E-3 = 1 ± 1 kcal mol-1, it has been calculated that D(CH2CHC(O)-H) = 87.1 ± 1.0 kcal mol-1, and ΔHt°(CH2CHCO, g) = 17.3 ± 1.2 kcal mol-1. The carbonyl C-H bond strength is the same as in formaldehyde reflecting the absence of any stabilization due to the vinyl group. The rate of iodine disappearance decreases with the extent of the reaction according to the scheme I2 + CH2CHCHO⇄ CH2CHCOI + HI (3,4) and CH2=CHCOI⇄CH2=C=CO + HI (5). k5 is given by log (k5/sec-1) = (13.4 ± 1.0) — (42.8 ± 7.0)/9.

AB - The reaction of iodine with acrolein has been studied in the temperature range 172-246°. The initial rates have been found to obey the rate law — d(I2)/df = k3(I)(acrolein), and k3 is given by log (k3/M-1 2sec-1) = (10.1 ± 0.2) — (16.8 ± 0.4) 9. From the activation energy and assuming E-3 = 1 ± 1 kcal mol-1, it has been calculated that D(CH2CHC(O)-H) = 87.1 ± 1.0 kcal mol-1, and ΔHt°(CH2CHCO, g) = 17.3 ± 1.2 kcal mol-1. The carbonyl C-H bond strength is the same as in formaldehyde reflecting the absence of any stabilization due to the vinyl group. The rate of iodine disappearance decreases with the extent of the reaction according to the scheme I2 + CH2CHCHO⇄ CH2CHCOI + HI (3,4) and CH2=CHCOI⇄CH2=C=CO + HI (5). k5 is given by log (k5/sec-1) = (13.4 ± 1.0) — (42.8 ± 7.0)/9.

UR - http://www.scopus.com/inward/record.url?scp=0001457193&partnerID=8YFLogxK

U2 - 10.1021/ja00783a004

DO - 10.1021/ja00783a004

M3 - Article

AN - SCOPUS:0001457193

SN - 0002-7863

VL - 95

SP - 319

EP - 323

JO - Journal of the American Chemical Society

JF - Journal of the American Chemical Society

IS - 2

ER -

Kinetics of the Reaction of Iodine with Acrolein. Bond Dissociation Energy of the Carbonyl C–H Bond

Abstract

ASJC Scopus subject areas

Access to Document

Other files and links

Fingerprint

Cite this