Reaction energies, effect

Midey A J and Viggiano A A 1998 Rate constants for the reaction of Ar" with O2 and CO as a function of temperature from 300 to 1400 K derivation of rotational and vibrational energy effects J. Chem. Phys. at press... 

The contribution of this polar structure to the bonding lowers the energy of the transition state. This may be viewed as a lower activation energy for the addition step and thus a factor which promotes this particular reaction. The effect is clearly larger the greater the difference in the donor-acceptor properties of X and Y. The transition state for the successive addition of the same monomer (whether X or Y substituted) is structure [V] ... 

At the same time, energy effects arising from chemical reaction can... 

Let us consider cases 1-3 in Fig. 4.4. In case 1, AG s for formation of the competing transition states A and B from the reactant R are much less than AG s for formation of A and B from A and B, respectively. If the latter two AG s are sufficiently large that the competitively formed products B and A do not return to R, the ratio of the products A and B at the end of the reaction will not depend on their relative stabilities, but only on their relative rates of formation. The formation of A and B is effectively irreversible in these circumstances. The reaction energy plot in case 1 corresponds to this situation and represents a case of kinetic control. The relative amounts of products A and B will depend on the heights of the activation barriers AG and G, not the relative stability of products A and B. 

Anhydrous NaC102 crystallizes from aqueous solutions above 37.4° but below this temperature the trihydrate is obtained. The commercial product contains about 80% NaC102. The anhydrous salt forms colourless deliquescent crystals which decompose when heated to 175-200° the reaction is predominantly a disproportionation to C103 and Cl but about 5% of molecular O2 is also released (based on the C102 consumed). Neutral and alkaline aqueous solutions of NaC102 are stable at room temperature (despite their thermodynamic instability towards disproportionation as evidenced by the reduction potentials on p. 854). This is a kinetic activation-energy effect and, when the solutions are heated near to boiling, slow disproportionation occurs ... 

This is roughly comparable to the energy effects in chemical reactions about 240 kj of heat is evolved when a mole of H2 bums, for instance. 

So far in this chapter our discussion has focused on thermochemistry, the study of the heat effects in chemical reactions. Thermochemistry is a branch of thermodynamics, which deals with all kinds of energy effects in all kinds of processes. Thermodynamics distinguishes between two types of energy. One of these is heat (q) the other is work, represented by the symbol w. The thermodynamic definition of work is quite different from its colloquial meaning. Quite simply, work includes all forms of energy except heat. 

Nuclear equation, 513 Nuclear masses, 521t Nuclear radiation. See Radioactivity Nuclear reactions biological effects, 527 equations, 513 fission, 523-526 fusion, 526-527,528 mass-energy relations, 520-523,... 

Chemical reactions form the heart of chemistry. And there is no more important aspect of chemical reactions than the energy effects that are caused. You will realize this if you let your thoughts wander between the warmth the little child in the fable derived from the combustion... 

The results presented in this part show that the characterization of cationic stability by means of a well-adapted reaction energy for the chemical system is better than ordering the cations according to their heats of formation. The importance of considering solvent effects in quantum chemical calculations is indicated by the fact that gas phase results are thereby modified and correspond with the experiments after that. 

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