THIONINE-SENSITIZED PHOTOPOLYMERIZATION OF ACRYLAMIDE<sup>1</sup>

Shepp, Allan; Chaberek, S.; MacNeil, R.

doi:10.1021/j100818a055

Cited by 32 publications

(24 citation statements)

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“…For CF, the coilcentration calculated from eq. [17] was 3.7 x lo-'' in01 L-'; again this value showed good agreement with a value calculated froin the C2F6 rate and rate expression.…”

Section: Isopropoxy1 Radical Deconzpositiorzsupporting

confidence: 84%

“…The product distribution given in Table 1 shows that the abstraction reaction products CF3H and CH, are more abundant than the predominant radical combination product, C2F6; the abstraction reactions become relatively less favored at higher temperatures. With experimental values for the rates of formation of CH, and C,H6 and upon accepting the literature value for k,, = 10'0.34 L m 01-' s-' (17,18), the rate constant k, can be evaluated from:…”

Section: Abstraction Reactions By Metliyl Radicalsmentioning

confidence: 99%

“…[16] and [17] comes from the calculations of the steadystate concentrations of CF, and CH,. Values of kl and k, were taken from Table 2 while values for k3/k2 were obtained froin an interpolation of Fig.…”

Section: Isopropoxy1 Radical Deconzpositiorzmentioning

confidence: 99%

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Pyrolysis of trifluoroacetaldehyde, initiated by di-tertiary-butyl peroxide decomposition

Loucks¹,

Liu²,

Hooper³

1979

Can. J. Chem.

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The thermal decomposition of 95:5 mixtures of trifluoroacetaldehyde (TFA) and di-tert-butyl peroxide (DTBP) has been studied at 100 Torr over the temperature range of 390 to 440 K. The major decomposition products included CO, CF3H, CH3COCH3, and CH4 while C2F6, CF3CHOHCH3, CF3CH3, CF3COCH3, C2H6, (CF3)2CHOH, and H2 were also found. In addition to the usual reactions for TFA thermal decomposition, reactions of methyl radicals with TFA to form isopropoxyl radicals were found. The alcohol products result from H atom abstraction reactions of the isopropoxyl radicals while CF3COCH3 is a decomposition product. Arrhenius parameters for several reactions were determined: for DTBP decomposition, log k = 15.82 − 37.73/2.303RT; for H abstraction from TFA by CH3, log k = 8.30 − 7.37/2.303RT; for H abstraction from TFA by CF3, log k = 8.98 − 8.61/2.303RT. Consideration has also been given to several rate constant ratios for the formation and decomposition of isopropoxyl radicals.A study of the reaction order for the formation of CF3H, C2F6, and CH4 showed that the orders were 3/2, 1, and 1 respectively for these three products. A reaction mechanism involving 14 individual steps is proposed to explain the reaction products and the observed orders of reaction.

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“…For CF, the coilcentration calculated from eq. [17] was 3.7 x lo-'' in01 L-'; again this value showed good agreement with a value calculated froin the C2F6 rate and rate expression.…”

Section: Isopropoxy1 Radical Deconzpositiorzsupporting

confidence: 84%

Section: Abstraction Reactions By Metliyl Radicalsmentioning

confidence: 99%

See 1 more Smart Citation

Pyrolysis of trifluoroacetaldehyde, initiated by di-tertiary-butyl peroxide decomposition

Loucks¹,

Liu²,

Hooper³

1979

Can. J. Chem.

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“…For the reaction we determined the value of k / ( € H c o -l * ) , where EHCO is the extinction coefficient and 1* is the effective length of the cell. Accepting that k 8 = 3.6 X lo-" cm3/s [22], we obtained CHCO and therefore the absolute HCO concentration. The adequacy of this method of determining HCO concentration is confirmed by the good agreement between the rate constant of the HCO reaction obtained with that measured by other techniques [HNOJo does not happen to depend on NO concentration and, hence, HNO molecules are formed in reaction (6) only, and further, the acetaldehyde photodissociation quantum yield does not depend significantly on the NO pressure up to 300 torr.…”

Section: Determination Of Absolute Concentrationsmentioning

confidence: 87%

Study of the HNO + HNO and HNO + NO reactions by intracavity laser spectroscopy

Cheskis

Надточенко

Sarkisov

1981

Int J of Chemical Kinetics

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Flash photolysis of CH3CHO and H2CO in the presence of NO has been investigated by the intracavity laser spectroscopy technique. The decay of HNO formed by the reaction HCO + NO * HNO + CO was studied a t NO pressures of 6.&380 torr. At low NO pressure HNO was found to decay by the reaction HNO + HNO 7 N20 + HzO. The rate constant of this reaction was determined to he kl = (1.5 f 0.8) X cm"/s. A t high NO pressure the reaction HNO + NO -products was more important, and its rate constant was measured to he k:! = (5 f 1.5) X cm3/s. NO;? was detected as one of the products of this reaction.Alternative mechanisms for this reaction are discussed.

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“…Oster 7 reported that dyes such as fluorescein, eosin, phloxin, and rose bengal in the presence of a reducing agent (e.g., ascorbic acid, phenylhydrazine hydrochloride, hydrazine sulfate, hydroxylamine, thiourea) were good sensitizers in the photoactivated aqueous polymerization of AN in the presence of oxygen. They suggested a mechanism involving a redox cycle in which the dye was first reduced by a reducing agent, followed by oxidation of the reduced dye with the oxygen: Dye ϩ reducing agent 3 dye H 2 3 dye H ϩ OH Shepp et al 8 showed that thionine, methylene, and proflavin produced aqueous polymerization of AN at pH 8.4. Although ceric ammonium nitrate (CAN) forms an efficient redox initiating system 9 -15 under an inert atmosphere, its use as a redox component in an oxygen atmosphere has been hardly reported.…”

Section: Introductionmentioning

confidence: 99%

Effect of plant gums on thermal polymerization of acrylonitrile

Jana

Maiti

Sengupta

et al. 2002

J of Applied Polymer Sci

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ABSTRACT:The effect of some plant gums on the polymerization of acrylonitrile (AN) using ceric ammonium nitrate (CAN) as an initiator in the presence of air (containing 21% oxygen) was studied. The induction period and percent conversion were determined. The induction period in the presence of gum was comparatively lower than that under a N 2 atmosphere. The rate of polymerization has a 1.5-power dependence on the monomer concentration and the rate is sufficiently high at moderate temperature. The rate also increased with an increasing initiator concentration and reaches a maximum value of 93% at 0.72 ϫ 10 Ϫ2 mol L Ϫ1 of CAN. The activation energy was found to be 6.4 kcal mol Ϫ1 . Both the molecular weight and density of the polyacrylonitrile (PAN) prepared in the presence of gum were higher than those of PAN prepared in the absence of the gum. The PAN produced in the presence of the gum was thermostable than that prepared in its absence.

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THIONINE-SENSITIZED PHOTOPOLYMERIZATION OF ACRYLAMIDE¹

Cited by 32 publications

References 0 publications

Pyrolysis of trifluoroacetaldehyde, initiated by di-tertiary-butyl peroxide decomposition

Pyrolysis of trifluoroacetaldehyde, initiated by di-tertiary-butyl peroxide decomposition

Study of the HNO + HNO and HNO + NO reactions by intracavity laser spectroscopy

Effect of plant gums on thermal polymerization of acrylonitrile

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THIONINE-SENSITIZED PHOTOPOLYMERIZATION OF ACRYLAMIDE1

Cited by 32 publications

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Pyrolysis of trifluoroacetaldehyde, initiated by di-tertiary-butyl peroxide decomposition

Pyrolysis of trifluoroacetaldehyde, initiated by di-tertiary-butyl peroxide decomposition

Study of the HNO + HNO and HNO + NO reactions by intracavity laser spectroscopy

Effect of plant gums on thermal polymerization of acrylonitrile

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THIONINE-SENSITIZED PHOTOPOLYMERIZATION OF ACRYLAMIDE¹