Entropy predicting changes

Predicting changes in entropy Recall that the change in enthalpy for a reaction is equal to the enthalpy of the products minus the enthalpy of the reactants. The change in entropy (A5) during a reaction or process is similar. 

Entropy, S°, is a measure of the randomness of a system. A random, or disordered system has high entropy a well-ordered system has low entropy The change in entropy in a chemical reaction, AS°, is also a factor in predicting reaction spontaneity. 

Applications of thermodynamics are based on three fundamental laws that deal with energy and entropy changes. The laws of thermodynamics cannot be derived their validity is based on the fact that they predict changes that are consistent with experimental observations. 

Prediction of solubility for simple ionic compounds is difficult since we need to know not only values of hydration and lattice enthalpies but also entropy changes on solution before any informed prediction can be given. Even then kinetic factors must be considered. 

In fact, the mean-field estimate for H, given by equation 3.64, predicts a second-order transition. While abrupt changes in entropy characterize sudden transitions between regions of periodic and chaotic rules, smooth changes in entropy as A is increased instead suggest that the rule path sometimes passes through a region of... 

In Chapter 1 we described the fundamental thermodynamic properties internal energy U and entropy S. They are the subjects of the First and Second Laws of Thermodynamics. These laws not only provide the mathematical relationships we need to calculate changes in U, S, H,A, and G, but also allow us to predict spontaneity and the point of equilibrium in a chemical process. The mathematical relationships provided by the laws are numerous, and we want to move ahead now to develop these equations.1... 

Experience indicates that the Third Law of Thermodynamics not only predicts that So — 0, but produces a potential to drive a substance to zero entropy at 0 Kelvin. Cooling a gas causes it to successively become more ordered. Phase changes to liquid and solid increase the order. Cooling through equilibrium solid phase transitions invariably results in evolution of heat and a decrease in entropy. A number of solids are disordered at higher temperatures, but the disorder decreases with cooling until perfect order is obtained. Exceptions are... 

Why Do We Need to Know This Material The second law of thermodynamics is the key to understanding why one chemical reaction has a natural tendency to occur bur another one does not. We apply the second law by using the very important concepts of entropy and Gibbs free energy. The third law of thermodynamics is the basis of the numerical values of these two quantities. The second and third laws jointly provide a way to predict the effects of changes in temperature and pressure on physical and chemical processes. They also lay the thermodynamic foundations for discussing chemical equilibrium, which the following chapters explore in detail. 

We need a quantitative definition of entropy to measure and make precise predictions about disorder. Provided that the temperature is constant, it turns out that a We generalize the definition in the change in the entropy of a system can be calculated from the following expression next section to changes in which the... 

The expressions in Eq. 1 and Eq. 6 are two different definitions of entropy. The first was established by considerations of the behavior of bulk matter and the second by statistical analysis of molecular behavior. To verify that the two definitions are essentially the same we need to show that the entropy changes predicted by Eq. 6 are the same as those deduced from Eq. 1. To do so, we will show that the Boltzmann formula predicts the correct form of the volume dependence of the entropy of an ideal gas (Eq. 3a). More detailed calculations show that the two definitions are consistent with each other in every respect. In the process of developing these ideas, we shall also deepen our understanding of what we mean by disorder. ... 

Entropy is an important concept in chemistry because we can use it to predict the natural direction of a reaction. However, not only does the entropy of the reaction system change as reactants form products, but so too does the entropy of the surroundings as the heat produced or absorbed by the reaction enters or leaves them. Both the entropy change of the system and that of the surroundings affect the direction of a reaction, because both contribute to the entropy of the universe. We explore the contribution of the system in this section and the contribution of the surroundings in the next section. 

The entropy change accompanying this transition is predicted to be... 

There is no single criterion for the system alone that applies to all processes. However, if we restrict the conditions to constant temperature and pressure, there is a state function whose change for the system predicts spontaneity. This new state function is the free energy (G), which was introduced by the American J. Willard Gibbs and is defined by Equation G = H - T S As usual, H is enthalpy, T is absolute temperature, and S is entropy. 

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