Chemical reaction processes time dimension

Microreactors (flow reactors with micrometer scale) were first employed in organic synthesis to perform chemical reactions in flow processes. The small dimensions of microreactors allow the use of minimal amounts of reagent under precisely controlled conditions, and the rapid screening of reaction conditions with improved overall safety of the process. To obtain synthetically useful amounts of material, either the microreactors are simply allowed to run for a longer period of time ( scale-out ), or several reactors are placed in parallel ( numbering up ) [29],... 

Molecular dynamics with periodic boundary conditions is presently the most widely used approach for studying the equilibrium and dynamic properties of pure bulk solvent,97 as well as solvated systems. However, periodic boundary conditions have their limitations. They introduce errors in the time development of equilibrium properties for times greater than that required for a sound wave to traverse the central cell. This is because the periodicity of information flow across the boundaries interferes with the time development of other processes. The velocity of sound through water at a density of 1 g/cm3 and 300 K is 15 A/ps for a cubic cell with a dimension of 45 A, the cycle time is only 3 ps and the time development of all properties beyond this time may be affected. Also, conventional periodic boundary methods are of less use for studies of chemical reactions involving enzyme and substrate molecules because there is no means for such a system to relax back to thermal equilibrium. This is not the case when alternative ensembles of the constant-temperature variety are employed. However, in these models it is not clear that the somewhat arbitrary coupling to a constant temperature heat bath does not influence the rate of reequilibration from a thermally perturbed... 

The following discussion represents a detailed description of the mass balance for any species in a reactive mixture. In general, there are four mass transfer rate processes that must be considered accumulation, convection, diffusion, and sources or sinks due to chemical reactions. The units of each term in the integral form of the mass transfer equation are moles of component i per time. In differential form, the units of each term are moles of component i per volnme per time. This is achieved when the mass balance is divided by the finite control volume, which shrinks to a point within the region of interest in the limit when aU dimensions of the control volume become infinitesimally small. In this development, the size of the control volume V (t) is time dependent because, at each point on the surface of this volume element, the control volnme moves with velocity surface, which could be different from the local fluid velocity of component i, V,. Since there are several choices for this control volume within the region of interest, it is appropriate to consider an arbitrary volume element with the characteristics described above. For specific problems, it is advantageous to use a control volume that matches the symmetry of the macroscopic boundaries. This is illustrated in subsequent chapters for catalysts with rectangular, cylindrical, and spherical symmetry. 

For unsteady-state diffusion into a quiescent medium with no chemical reaction, the mass transfer Peclet number does not appear in the dimensionless mass transfer equation for species i because it is not appropriate to make variable time t dimensionless via division by L/ v) if there is no bulk fluid flow (i.e., (d) = 0). In this case, the first term on each side of equation (10-11) survives, which corresponds to the unsteady-state diffusion equation. However, the characteristic time for diffusion of species i over a length scale L, given by L /50i,mix. replaces L/ v) to make variable time t dimensionless. Now, the accumulation and diffusional rate processes scale as CAo i.mix/A, with dimensions of moles per volume per time. Since both surviving mass transfer rate processes exhibit the same dimensional scaling factor, there are no dimensionless numbers in the mass transfer equation which describes unsteady-state diffusion for species i in nonreactive systems. 

In an NMR experiment, the perturbation dimension usually comprises the nuclear spin frame instead of a time frame or sample frame of macroscopic phenomena such as a chemical reaction. Different phases thus depend on the individual nuclear spins rather than on the molecular assembly of spins. Therefore, the exploitation of phase information within the covariance processing described above might seem little attractive. 

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