Reactive systems

The fimdamental kinetic master equations for collisional energy redistribution follow the rules of the kinetic equations for all elementary reactions. Indeed an energy transfer process by inelastic collision, equation (A3.13.5). can be considered as a somewhat special reaction . The kinetic differential equations for these processes have been discussed in the general context of chapter A3.4 on gas kmetics. We discuss here some special aspects related to collisional energy transfer in reactive systems. The general master equation for relaxation and reaction is of the type [H, 12 and 13, 15, 25, 40, 4T ] ... 

A3.13.4.3 IVR WITHIN THE GENERAL SCHEME OF ENERGY REDISTRIBUTION IN REACTIVE SYSTEMS... 

Finally, in brief, we demonstrate the influence of the upper adiabatic electronic state(s) on the ground state due to the presence of a Cl between two or more than two adiabatic potential energy surfaces. Considering the HLH phase, we present the extended BO equations for a quasi-JT model and for an A -1- B2 type reactive system, that is, the geometric phase (GP) effect has been inhoduced either by including a vector potential in the system Hamiltonian or... 

Thus, the total effective Hamiltonian (H) in the presence of a vector potential is now defined and it is for an type reactive system (9q = 0) given by... 

The interatomic distances of the triangle ABC formed due to any A + BC type reactive system are as follows ... 

The allenyl moiety (2,3-aikadienyl system) in the carbonylation products is a reactive system and further reactions such as intramolecular Diels-Alder and ene reactions are possible by introducing another double bond at suitable positions of the starting 2-alkynyl carbonates. For example, the propargylic carbonate 33 which has l,8(or 1.9)-diene-3-yne system undergoes tandem carbonylation and intramolecular Diels-Alder reaction to afford the polycyclic compound 34 under mild conditions (60 C, 1 atm). The use of dppp as ligand is important. One of the double bonds of the allenyl ester behaves as part of the dieneflSj. 

Examples of typical photoinitiator systems used to cure reactive coating systems are as follows (80,81). The reactive systems are primarily unsaturated acryUc acid esters of different alcohol and polymer stmctures. 

For species present as gases ia the actual reactive system, the standard state is the pure ideal gas at pressure F°. For Hquids and soHds, it is usually the state of pure real Hquid or soHd at F°. The standard-state pressure F° is fixed at 100 kPa. Note that the standard states may represent different physical states for different species any or all of the species may be gases, Hquids, or soHds. 

The general criterion of chemical reaction equiUbria is the same as that for phase equiUbria, namely that the total Gibbs energy of a closed system be a minimum at constant, uniform T and P (eq. 212). If the T and P of a siagle-phase, chemically reactive system are constant, then the quantities capable of change are the mole numbers, n. The iadependentiy variable quantities are just the r reaction coordinates, and thus the equiUbrium state is characterized by the rnecessary derivative conditions (and subject to the material balance constraints of equation 235) where j = 1,11,.. ., r ... 

Fluorination and iodination reactions are used relatively littie in dye synthesis. Fluorinated species include the trifluoromethyl group, which can be obtained from the trichi oromethyl group by the action of hydrogen fluoride or antimony pentafluoride, and various fluorotria2iQyl and pyrimidyl reactive systems for reactive dyes, eg, Cibacron F dyes. 

Migration Exhaust Technique for Less than 0.5% Depth of Shade. Start at 50°C with sequestrant at pH 7.0. Add dye over 20 min and raise temperature to highest safe level depending on the dye (95°C with monochlorotriazinyl reactive system) at a rate of 1.5°C/min. Hold for 20 min and cool back to dyeing temperature. Alkali is portionwise added, or mechanically dosed, over 20 min and after a further 30 min the dyebath is dropped and the washing sequence begun. 

Chemical Types. A wide range of reactive groups have been investigated, with 20—30 used commercially and over 200 patented. These have been described in detail elsewhere (10,20). Because these reactive groups differ chemically the activation of the reactive systems is different as are the rates of reaction with cellulose, from one reactive system to another. This rate of reaction with cellulose, or reactivity, dictates the temperature and pH needed for dyeing. 

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