spontaneous process
Summary 16.1 Spontaneity Chemical and physical processes have a natural tendency to occur in one direction under certain conditions. A spontaneous process occurs without the need for a continual input of energy from some external source, while a nonspontaneous process requires such. Systems undergoing a spontaneous process may or may not experience a gain or loss of energy, but they will experience a change in the way matter and/or energy is distributed within the system. 16.2 Entropy Entropy S is a state function that can be related to the number of microstates for a system the number of ways the system can be arranged and to the ratio of reversible heat to kelvin temperature. It may be interpreted as a measure of the dispersal or distribution of matter and/or energy in a system, and it is often described as representing the disorder of the system. For a given substance, Ssolid < Sliquid < Sgas in a given physical state at a given temperature, entropy is typically greater for heavier atoms or more complex molecules. Entropy increases when a system is heated and when solutions form. Using these guidelines, the sign of entropy changes for some chemical reactions may be reliably predicted. 16.3 The Second and Third Laws of Thermodynamics The second law of thermodynamics states that a spontaneous process increases the entropy of the universe, Suniv > 0. If Suniv < 0, the process is nonspontaneous, and if Suniv = 0, the system is at equilibrium. The third law of thermodynamics establishes the zero for entropy as that of a perfect, pure crystalline solid at 0 K. With only one possible microstate, the entropy is zero. We may compute the standard entropy change for a process by using standard entropy values for the reactants and products involved in the process. 16.4 Free Energy Gibbs free energy G is a state function defined with regard to system quantities only and may be used to predict the spontaneity of a process. A negative value for G indicates a spontaneous process; a positive G indicates a nonspontaneous process; and a G of zero indicates that the system is at equilibrium. A number of approaches to the computation of free energy changes are possible.