Product transitions

The main approximation of such one-dimensional corrections is that the tunnelling is assumed to occur along the MER This may be a reasonable assumption for reactions having either early or late (close to either reactant or product) transition states. For reactions where both bond breaking and formation are significant at the TS (as is usually the case), the dominant tunnel effect is comer cutting (Figure 16.5), i.e. the favoured... [Pg.391]

Draw an energy diagram for a one-slep reaction with /Cet) < 1. Label the parts of the diagram corresponding to reactants, products, transition state, AG°, and ACT Is AG° positive or negative ... [Pg.168]

Improve the control strategy for the product transition in Example 14.7. Ignore mixing time constraints, flow rate limitations on the addition of component C, and any constraints on the allowable value for The concentration of Q can exceed its steady-state value of 8mol/m but must not be allowed to go outside the upper specification limit of 9mol/m. ... [Pg.536]

It is not the catalytic activity itself that make zeolites particularly interesting, but the location of the active site within the well-defined geometry of a zeolite. Owing to the geometrical constraints of the zeolite, the selectivity of a chemical reaction can be increased by three mechanisms reactant selectivity, product selectivity, and transition state selectivity. In the case of reactant selectivity, bulky components in the feed do not enter the zeolite and will have no chance to react. When several products are formed within the zeolite, and only some are able to leave the zeolite, or some leave the zeolite more rapidly, we speak about product selectivity. When the geometrical constraints of the active site within the zeolite prohibit the formation of products or transition states leading to certain products, transition state selectivity applies. [Pg.213]

Fig. 20 Reaction pathways in the reduction of methyl (a) and /-butyl chloride (b) by NO". , reactant and products , transition states. In (a) and (b), the full line is the mass-weighted IRC path from the reactant to the product states the dashed line is a ridge separating the Sn2 and ET valleys and the dotted-dashed line is the mass-weighted IRC path from the Sn2 product state to the ET product state (homolytic dissociation). The dotted line in (a) represents the col separating the reactant and the SN2 product valleys. The dotted line in (b) represents the steepest descent path from the bifurcation point, B, to the Sn2 product. In (a), B is the point of the col separating the reactant and the SN2 product valleys where the ridge separating the SN2 and ET valleys starts.

TRANSITION-STATE ANALOGS are stable molecules that are designed to look more like the transition state than like the substrate or product. Transition-state analogs usually bind to the enzyme they re designed to inhibit much more tightly (by 1000-fold or more) than the substrate does. [Pg.105]

Another way of visualising the potential energy of a molecular system is in terms of the potential-energy changes that occur during a chemical reaction. This is represented by means of a reaction profile where the potential energy values of the reactants, products, transition states and intermediates are plotted against the reaction coordinate (the lowest... [Pg.122]

The Cope rearrangement is the conversion of a 1,5-hexadiene derivative to an isomeric 1,5-hexadiene by the [3,3] sigmatropic mechanism. The reaction is both stereospecific and stereoselective. It is stereospecific in that a Z or E configurational relationship at either double bond is maintained in the transition state and governs the stereochemical relationship at the newly formed single bond in the product.137 However, the relationship depends upon the conformation of the transition state. When a chair transition state is favored, the EyE- and Z,Z-dienes lead to anli-3,4-diastereomcrs whereas the E,Z and Z,/i-isomcrs give the 3,4-syn product. Transition-state conformation also... [Pg.376]

Describe thex emistry during normal operation and product transition. Is there a modH of the process (kinetic, mass balance, etc.) ... [Pg.12]

The relationship between AG and AG is normally presented in a diagram, where free energies of the reactants, products, transition state, and intermediates are plotted against the extent of reaction, or more precisely the reaction coordinate. This is shown in Fig. 2.9. Even a simple homogeneous catalytic reaction such as alkene hydrogenation involves many intermediates and transition states. The free energy diagram thus resembles (c) rather than (a) or (b). [Pg.25]

After this step, they adapt to a true high-throughput screening method that measures each of the internal standards and biomarker precursor-product transitions by direct injection. By eliminating the chromatographic step, it is possible to reduce sample analysis time to one minute per sample, and the biomarker-intemal standard ratio is used to determine to which population the analyzed sample belongs, disease state or control. [Pg.75]

The synthesis of enynes is not always trivial. Some synthetic reactions have functional group compatibility problems, others give poor yields due to instability of the products. Transition metals can be useful in reactions that give enynes which can suffer subsequent PKRs. [Pg.221]

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