Saturday, December 23, 2017

homework - Equilibrium constant. Can it be reached?



Consider the reaction below:


A+BC


Suppose that the equilibrium constant for this reaction is K=10.


I then prepare a reaction vessel with volume of 1 dm3 which contains 1 molecule of A, 500 molecules of B and 1 molecule of C. Thus the initial concentration of each species (in mol dm3) will be 1/NA, 500/NA, and 1/NA respectively, where NA is the Avogadro constant.


As a result the initial reaction quotient is NA/500.


Now, am I right in saying that this system cannot reach equilibrium, since the only possible values of the reaction quotient are +, 0, or NA/500?


Does this arise because there simply is not enough of each reactant/product in order to reach equilibrium? I feel like this system must reach equilibrium but I'm struggling to see how the value of K can be reached in this closed system.




In a bimolecular reaction step (such as the one shown above), the rate constant for the forward reaction has units M1 s1. I have learnt that if the concentration of B is increased significantly, then the Gibbs free energy of the A+B mixture will increase because the activation energy has a concentration dependence. Is this true, and is equilibrium only reached once this Gibbs free energy decreases again?


This is confusing as I am used to the Gibbs free energies of the reactants and products remaining constant while the relative amounts of each change throughout the course of the reaction.





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