✦ LIBER ✦

The kinetics and the mechanism of the thermal gas-phase reaction between bis(trifluoromethyl)trioxide, CF3O3CF3 and 1,1-dichlorodifluoroethylene, CF2CCI2

✍ Scribed by J. Czarnowski

Publisher: John Wiley and Sons
Year: 1986
Tongue: English
Weight: 417 KB
Volume: 18
Category: Article
ISSN: 0538-8066
DOI: 10.1002/kin.550181204

No coin nor oath required. For personal study only.

✦ Synopsis

The thermal addition of CF,0sCF3(T 1 to CF2CCl2(E) has been investigated between 49.6 and 69.5"C. The initial pressure of CFJ03CF3 was varied between 7 and 240 torr and that of CF2CC12 between 4 and 600 torr. Four products of formula CF30(E),00CF3, wherej = 1 + 4 are formed. The sum of the products ct=, CF30(E1JOOCF3 is equal to the amount of trioxide decomposed.

The reaction is homogeneous. Its rate is not affected by the total pressure and the presence of inert gas. It is a free radical telomerization with four basic steps: thermal decomposition of CF,O,CF, into CF,O. and CF302, chain initiation by addition of CF,O' to olefin, chain growth by further additions giving radicals with up to four molecules of olefin incorporated in, and telomeric radicals termination.

The consumption of alkene is well represented by the equation:

where

is the mean chain length of telomerization. K varies from 1.45 at 1.5 torr of E to 3.3 at 400 torr of E . Above this pressure E has no influence on 5.

The estimated value of the constant for the addition of telomeric radicals to alkene is: k, = 8.6 ? 6.0 x lo4 exp(

📜 SIMILAR VOLUMES

The kinetics and the mechanism of the th

The kinetics and the mechanism of the thermal gas-phase reaction between NO2 and 1,1-dichlorodifluoroethylene, CF2CCl2

✍ J. Czarnowski; H. J. Schumacher 📂 Article 📅 1986 🏛 John Wiley and Sons 🌐 English ⚖ 452 KB 👁 1 views

The kinetics of the gas phase reaction between NOz and CFzCCIz has been investigated in the temperature range from 50 to 80°C. The reaction is homogeneous. Three prod- and equimolecular amounts of ClNO and of OZNCFZC(O)CI. The rate of consumption of the reactants is independent of the total pressur

Kinetics and mechanism of the thermal ga

Kinetics and mechanism of the thermal gas-phase reaction between trifluoromethylhypofluorite, CF3OF, and tetrachloroethene

✍ J. Czarnowski 📂 Article 📅 1996 🏛 John Wiley and Sons 🌐 English ⚖ 368 KB 👁 2 views

The thermal gas-phase reaction of CF,OF with CCI,CC12 h a s been studied between 313.8 a n d 343 8 K The initial pressure of CF,OF was varied between 10.8 a n d 77.5 torr a n d that of CCI;,CCI, between 3.7 a n d 26 8 torr. CF,OF was always present in excess, varying t h e initial ratio of CF,OF t o

A reexamination of the pyrolysis of bis

A reexamination of the pyrolysis of bis trifluoromethyl peroxide. Addendum: Concerning D(CF3O2-CF3) and D(CF3-O2)

✍ L. Batt; R. Walsh 📂 Article 📅 1983 🏛 John Wiley and Sons 🌐 English ⚖ 137 KB 👁 1 views

Earlier arguments concerning D(CF302-CF3) and D(CF3-02) are shown to be probably wrong. New values of 86 and 49 kcal/mol, respectively, are derived. C-0 bond strengths are compared between CF3-and CH3-containing compounds. This relation is of value only if D,(Oz) is independent of X. This is equival

Substituent effects on the disproportion

Substituent effects on the disproportionation-combination rate constant ratios for gas-phase halocarbon radicals. IV. Reactions of ·CF3 + CF3CH2CF2· and CF3CH2CF2· + CF3CH2CF2·

✍ Shane R. Smith; Bert E. Holmes 📂 Article 📅 1999 🏛 John Wiley and Sons 🌐 English ⚖ 161 KB 👁 2 views

Rate constant ratios, k d /k c , for the disproportionation/combination reaction at a temperature of 295 Ϯ 2 K, have been measured as 0.034 Ϯ 0.009 for the collision between CF 3 CH 2 CF 2 ϩ CF 3 radicals and as 0.075 Ϯ 0.019 for CF 3 CH 2 CF 2 ϩ CF 3 CH 2 CF 2 radicals. The effect of the two fluori

Kinetics and mechanism of the gas-phase

Kinetics and mechanism of the gas-phase thermal reaction between bis(fluoroxy) difluoromethane CF2(OF)2 and carbon monoxide

✍ A. E. Croce; E. Castellano 📂 Article 📅 1982 🏛 John Wiley and Sons 🌐 English ⚖ 472 KB

The kinetics of the gas-phase thermal reaction between CFz(0F)z and CO has been studied in a static system a t temperatures ranging between 110 and 140°C. The only reaction products were CFz0 and Con, giving the following stoichiometry: The reaction is homogeneous. The rate is strictly second order

Kinetics for the gas-phase reactions of

Kinetics for the gas-phase reactions of OH radicals with the hydrofluoroethers CH2FCF2OCHF2, CHF2CF2OCH2CF3, CF3CHFCF2OCH2CF3, and CF3CHFCF2OCH2CF2CHF2 at 268–308 K

✍ L. Chen; S. Kutsuna; K. Tokuhashi; A. Sekiya; K. Takeuchi; T. Ibusuki 📂 Article 📅 2003 🏛 John Wiley and Sons 🌐 English ⚖ 122 KB 👁 2 views

## Abstract Rate constants were determined for the reactions of OH radicals with the hydrofluoroethers (HFEs) CH~2~FCF~2~OCHF~2~(__k__~1~), CHF~2~CF~2~OCH~2~CF~3~ (__k__~2~), CF~3~CHFCF~2~OCH~2~CF~3~(__k__~3~), and CF~3~CHFCF~2~OCH~2~CF~2~CHF~2~(__k__~4~) by using a relative rate method. OH radical