A further link(s) with inequivalent representations in quantum field theory

In recent years it has become more apparent how useful inequivalent representations of the CCR and CAR in quantum field theory may be in describing and explaining physical phenomena, and several properties and concepts have been stated, referred to, and/or developed in the literature on these ideas. In this paper, some of these are reviewed, and some further properties and concepts are developed as further links in understanding these inequivalent representations in quantum field theory. One of these is a statement as to what actually breaks down in some field theories in the transformation between representations which are unitarily inequivalent. This is developed using the language and ideas of point quantum mechanical invariance, since this should be more familiar to a much larger number of physicists. Also, a statement on state expectation values is developed which can be used as a criterion for the occurrence of inequivalent representations of the CCR and CAR in field theories.     

Thermodynamics of aqueous mixtures of nonelectrolytes II. Isobaric heat capacities of water-n-alcohol mixtures at 25°C

Excess isobaric heat capacities of binary mixtures of water with methanol, ethanol, and 1-propanol were obtained from flow microcalorimetric measurements at 25°C over the entire composition range. The results are compared with those of previous investigations.     

Radical processes in the pyrolysis of acetylene

The literature on the pyrolysis of acetylene below 1000 K is reviewed and it is shown that the reaction is a radical chain polymerization initiated by H atoms. The induction period is examined and shown to arise from a rapid autocatalysis produced by the very first product, vinyl acetylene. Data from studies of acetylene polymerization induced by vinyl acetylene and styrene are examined and shown to be in good qualitative agreement with the radical chain process presented. Measured and where needed, estimated rate constants are given to produce numerical estimates of chain length, rates of polymerization, induction period, and rates of initiation. It is further shown that all the products of the polymerization are capable of efficiently initiating chains in the system. An examination of the possible kinetics of vinylidene shows that it does not play any role in acetylene chemistry.     

On a domination property for vector maximization with respect to cones

We give a corrected version of Theorem 2.1 of Ref. 1.The author is indebted to D. T. Luc, Hungarian Academy of Sciences, Budapest, Hungary, for pointing out his error in the proof of the original version of Theorem 2.1 in Ref. 1.     

The kinetics and thermochemistry of S2F10 pyrolysis

Data on the kinetics of S₂F₁₀ pyrolysis, which gives SF₄ + SF₆, have been reinterpreted to give a value for the equilibrium constant of S₂F₁₀ ? SF₄ + SF₆. This, together with statistical estimates of the entropy and heat capacity of S₂F₁₀, can be used to give for this reaction values of ΔH = 19.7 ± 1.0 kcal/mole and ΔS = 47.6 ± 2 gibbs/mole. ΔH(S₂F₁₀) = –494 kcal/mole. A compatible mechanism is shown to be S₂F₁₀ ? 2SF₅ (fast); 2SF₅ ? SF₆ + SF₄ (slow) with step 2 rate-determining. The overall, best first order rate constant is proposed as k_meas = 10^{17.42–43.0/θ} sec^?1 = K₁k₂, where θ = 2.303RT in kcal/mole. Independent measurements of δH and S° for the SF₅ radical, permits the evaluation of the equilibrium constant K₁ = 10^{8.92–(27.1 ± 6)/θ} l./mole-sec and yields k₂ = 10^{8.50–15.9/θ} l./mole-sec. The observed homogeneous catalysis by NO and CHCl ? CHCl can be explained in terms of a direct abstraction of F from S₂F₁₀ : C + S₂F₁₀ → CF + S₂F₉, followed by S₂F₉ → SF₅ + SF₄ and SF₅ + CF ? SF₆ + C (C ? NO or C₂H₂Cl₂).     

Very low-pressure pyrolysis: VI. The decomposition of ethyl acetate

The pyrolysis of ethyl acetate has been studied by the very low-pressure pyrolysis (VLPP) technique. The results obtained agree well with the previously determined high-pressure Arrhenius parameters where log k_∞ = 12.6 ? 48.0/θ. The rate constants given by these parameters have also been shown to be consistent with the predictions of the RRK and RRKM theories and demonstrate the applicability of the technique to the study of thermal decompositions.