SpontaneousProcesses.pptVIP

Spontaneous Processes Spontaneous Processes Spontaneous Processes Gibbs Free Energy Gibbs Free Energy Gibbs Free Energy Summary Calculation of DG Calculation of DG Calculation of DG Calculation of DG Calculation of DG Calculation of DG Temperature Dependence Temperature Dependence Temperature Dependence Pressure Dependence Pressure Dependence Example Example: Reversible Process DG of Mixing Protein Unfolding Protein Unfolding Protein Unfolding Protein Unfolding Protein Unfolding * The Second Law: DS ? 0 The entropy of a closed system can only increase. If a process will decrease entropy in a closed system, then it does not occur spontaneously. Its opposite will occur spontaneously. But we very rarely work with closed systems... …except for the universe as a whole! The entropy of a system can spontaneously decrease, as long as the entropy of the surroundings increases by at least as much. DSsys + DSsurr ? 0 Do we have to keep calculating DSsurr ? Not necessarily! Let’s stay at constant T and P: Now everything is in terms of the system. The criterion for spontaneity given by the Second Law becomes: The Gibbs Free Energy is a new state function, defined as: Josiah Willard Gibbs (1839-1903) At constant temperature and pressure, DG is From the previous slide, we end up with The condition of constant T and P is very important when using G. Otherwise, the entropy change of the surroundings might be different leading to a different result. G is extremely useful for chemistry and biochemistry, since so much takes place at constant temperature and pressure. At constant T and P, consideration of DG will answer the question “Will a given reaction be spontaneous?” G is still defined and can be calculated for any change of state, including changing P and T. We can also define another state variable, Helmholtz Free Energy (A = E - TS), which has similar characteristics as G, but relates more directly to constant T and V processes. The Gibbs Free Energy is a direct measu