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A new procedure to extract spectral and concentration information for unknown components in a series of mixture spectra is described. The algorithm, a form of self-modeling curve resolution (SMCR), requires no assumptions about the mixture data except for linear additivity and non-negativity of component spectra, and non-negativity of concentrations. It provides permissible bands for the spectra and concentration profiles of individual components in the mixtures and is applicable to problems in chromatography, equilibrium studies, and kinetics, among others. The new method employs a nonlinear optimization procedure and is substantially more efficient than similar methods that have been previously reported. The SMCR algorithm is demonstrated by applying it to the autocatalytic oxidation of oxalic acid by permanganate in the presence of sulfuric acid. The reaction was monitored spectroscopically between 200 and 1000 nm under four different reaction conditions. Results verified the presence of two reaction intermediates previously proposed in the literature and confirmed their spectral properties. Concentration profiles for the intermediates are described.Key words: curve resolution, kinetics, chemometrics, permanganate, oxalic acid.

A new procedure to extract spectral and concentration information for unknown components in a series of mixture spectra is described. The algorithm, a form of self-modeling curve resolution (SMCR), requires no assumptions about the mixture data except for linear additivity and non-negativity of component spectra, and non-negativity of concentrations. It provides permissible bands for the spectra and concentration profiles of individual components in the mixtures and is applicable to problems in chromatography, equilibrium studies, and kinetics, among others. The new method employs a nonlinear optimization procedure and is substantially more efficient than similar methods that have been previously reported. The SMCR algorithm is demonstrated by applying it to the autocatalytic oxidation of oxalic acid by permanganate in the presence of sulfuric acid. The reaction was monitored spectroscopically between 200 and 1000 nm under four different reaction conditions. Results verified the presence of two reaction intermediates previously proposed in the literature and confirmed their spectral properties. Concentration profiles for the intermediates are described.

The kinetics of the reaction by which thallium(III) acetate oxidizes cyclohexene in glacial acetic acid medium, has been studied by UV spectrophotometric observation at 30°C. The consumption of thallium(III) acetate follows a second-order rate law exhibiting first-order dependence on each of thallium(III) acetate and cyclohexene; however, the first-order dependence on cyclohexene disappears at high cyclohexene concentrations as pseudo-first-order conditions prevail above 0.2 M cyclohexene. A steady-state model of the following form is proposed: where Tl, Cy, and Com are units of Thallium(III) acetate, cyclohexene, and a reaction complex. The value of k2 has been evaluated as 0.00027 and (k−1 + k2) as 0.0385k1. For low thallium(III) acetate concentrations the reaction kinetics follow the rate law: where α = the excess concentration of cyclohexene over thallium(III) triacetate. For thallium(III) acetate concentrations above 0.02 M, double salt formation of thallium(III) acetate with product thallium(I) acetate removes thallium(III) acetate from the reaction and a modified rate law is observed. Runge–Kutta numerical solutions to the differential equations provide confirmation that the rate expressions are valid in predicting the observed concentrations of thallium(III) acetate.

The photolysis of CO2 at 1633 A in the presence of 13CO has been found to give an appreciable yield of 13CO2. The photolysis of N2O at 1633 A conducted in the presence of CO and a large excess of N2 has also been found to lead to CO2 formation. The experimental conditions for both photolyses are such that O 1D atoms generated in the photolysis would be efficiently deactivated to O 3P atoms and the product CO2 is believed to arise from reactions involving the latter. A radical‐chain mechanism has been proposed for the formation of CO2, but the possibility of a surface reaction mechanism has not been ruled out.

The thermal decomposition of trifluoroacetaldehyde at temperatures f 471 to 519°C has been studied by measuring the rates of formation of CF3H and C2F6. It is concluded that the high-pressure reaction mechanism involves a Rice-Herzfeld reaction scheme with first-order initiation and second-order termination via CF3 combination. However, a falloff in reaction rates is observed at pressures below 100 mmHg. The Arrhenius parameters of the three rate constants corresponding to the overall reaction, the initiation reaction, and an abstraction reaction have been evaluated.

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.

As part of the study of the mercury-photosensitized decomposition of dimethyl ether, the combination of methyl radicals has been investigated in the temperature range 200 to 300 °C and at pressures between 3 and 300 mm Hg. For pressures of less than 100 mm the second-order rate coefficient for the combination of methyl radicals shows a pressure dependence. The pressure dependence agrees qualitatively with that observed by others, but occurs at somewhat higher pressures. Calculations for the Kassel equation using the Arrhenius parameters for ethane decomposition and fitted to the pressure dependence of the methyl radical combination show that the number of effective modes for ethane decomposition is 8 or 9. Carbon dioxide was found to be a quite ineffective third body for energy transfer. The results for the mercury-photosensitized decomposition of dimethyl ether have also been analyzed to obtain information about the combination of methyl radicals with methoxymethyl radicals. The combination of these radicals becomes pressure dependent at pressures less than about 15 mm. Kassel integrations based on the rate constant [Formula: see text]for the unimolecular decomposition of methyl ethyl ether at the C—C bond, and fitted to the observed pressure dependence of the combination reaction, lead to s = 10 for these reactions.The rate constant for the abstraction of a hydrogen atom by a methyl radical from dimethyl ether was found to be [Formula: see text]

The thermal decomposition of trifluoroacetaldehyde has been studied over the 460–520 °C temperature range, and at pressures from 4 to 400 mm Hg. The experimental rate equation in the high-pressure region is of the form: Rate = k[CF3CHO]3/2 where[Formula: see text]The results are consistent with a mechanism initiated by a first order process and terminated by a second order recombination of two CF3 free radicals. At lower pressures (40 mm Hg), the ratio of kinit/kterm is pressure dependent and the overall order increases. The effects of added inert gas confirm this pressure dependence.

The decomposition of the methoxymethyl radical, generated in the mercury-photosensitized decomposition of dimethyl ether, has been investigated over the temperature range 200 to 300 °C and the pressure range 3 to 600 mm Hg. The radical decomposes to give a formaldehyde molecule and a methyl radical. The effects of pressure and temperature on the first-order rate coefficient for the decomposition of the methoxymethyl radical have been examined in detail. The rate coefficient shows a pressure dependence over the full pressure range studied. The order of the decomposition is about 1.4 at the middle of the pressure range studied, with a lower order at higher pressures and a higher order at lower pressures. At 100 mm Hg the observed activation energy for the decomposition of the methoxymethyl radical is 24.8 kcal/mole.The first-order and second-order rate coefficients, k∞ and k0, corresponding to the limiting conditions of high pressures and low pressures respectively, have been evaluated as [Formula: see text]Kassel integrations have been carried out for the methoxymethyl radical and have been fitted to the experimental data. It is concluded that 8 or 9 normal modes contribute to the energization of the radical. The rate coefficient is increased by the presence of carbon dioxide, but carbon dioxide has a lower efficiency than dimethyl ether for the transfer of energy in the energization process.

The thermal decomposition of trifluoroacetaldehyde at temperatures f 471 to 519°C has been studied by measuring the rates of formation of CF3H and C2F6. It is concluded that the high-pressure reaction mechanism involves a Rice-Herzfeld reaction scheme with first-order initiation and second-order termination via CF3 combination. However, a falloff in reaction rates is observed at pressures below 100 mmHg. The Arrhenius parameters of the three rate constants corresponding to the overall reaction, the initiation reaction, and an abstraction reaction have been evaluated.

A close examination of the chemistry that occurs at the blade-ice interface when one ice skates.