We present a dynamic and thermodynamic study of the orientational glass former Freon 113 (1,1,2-trichloro-1,2,2-trifluoroethane, CCl_{2}F-CClF_{2}) in order to analyze its kinetic and thermodynamic fragilities. Freon 113 displays internal molecular degrees of freedom that promote a complex energy landscape. Experimental specific heat and its microscopic origin, the vibrational density of states...

Thermodynamic data on enzyme-catalyzed reactions play an essential role in the prediction of the extent of reaction and the position of equilibrium for any process in which these reactions occur. The importance of this information lies in its applications both in biochemistry and in industrial enzymology. The data are also essential for metabolic control analysis (MCA): an important part of sys...

Evaluation of thermal stability and runaway behavior of any exothermic chemical system is of great importance for the design and operation of a chemical process. The evaluation process should be based on a thorough investigation of the reaction chemistry including reaction pathways, thermodynamic, and kinetic parameters. When addressing the reactivity hazards of any reacting system, the dominan...

The dynamics of biological reaction networks are strongly constrained by thermodynamics. An holistic understanding of their behavior and regulation requires mathematical models that observe these constraints. However, kinetic models may easily violate the constraints imposed by the principle of detailed balance, if no special care is taken. Detailed balance demands that in thermodynamic equilib...

Direct observation and structural characterization of a kinetic product and a thermodynamic product for complexes with an NO2S2 macrocycle (L) are reported. L reacts with copper(I) iodide to give a mononuclear complex [Cu(L)]2(Cu2I4)·2CH2Cl2 (1), featuring three separate units. When cadmium(II) iodide was reacted with L, an anion-coordinated complex [Cd(L)I]2(Cd2I6)·4CH3CN (2) with a needle-typ...

Two results are presented: First, we solve the problem of persistence of dissipation for reduction of kinetic models. Kinetic equations with thermodynamic Lyapunov functions are studied. Uniqueness of thermodynamic projector is proven: There exists only one projector which transforms the arbitrary vector field equipped with the given Lyapunov function into a vector field with the same Lyapunov ...

The remarkable kinetic slowdown experienced by liquids as they are cooled toward their glass transition is not accompanied by any obvious structural change. Understanding the origin of this behavior is a major scientific challenge. At present, this area of condensed matter theory is characterized by an abundance of divergent viewpoints that attempt to describe well-defined physical phenomena. W...

A theoretical study of the kinetic and mechanism of intramoleccha cychcation of (1)-undeca-7,8-dien-2-yne was performed using MT methods at B3LYP and B3PW91 levels of theory using 6-311g, 6-311C.6-31 IGs*, 6-31I+G, 6-31 I4-SG and 6-3114H-Gs* basis seo. Equilibrium molecular geometries andharmonic vibrational frequencies of the reaccint, transition state and product wens calculated. Theconsidere...

The cyclizations of two structurally similar 2-oxo-5-hexenyl-type radicals have been investigated by ab initio and density functional (UB3LYP/6-31+G**//UHF/6-31G* and UB3LYP/6-31G*//UB3LYP/6-31G*) calculations. The origin of apparently contradictory reports of 6-endo and 5-exo cyclizations is determined. Kinetic control favors 6-endo cyclization, while thermodynamic control gives 5-exo cyclizat...

One of the important considerations during realistic rGO structure generation is the inclusion of both kinetic and thermodynamic effects. In our simulations, we assumed a random spatial distribution of epoxies and hydroxyls in the initial GO structures, thereby accounting for kinetic effects. A similar methodology has been followed previously [1]. Thermal annealing of the GO structures using mo...