Spontaneity entropy

The entropy, Spontaneous vs non-spontaneous, Reversible and irreversible processes, Calculation of entropy changes (Isothermal, isobaric, isochoric, adiabatic), Phase changes at equilibrium, Trouton s rule, Calculation for irreversible processes... 

Any change taking place which results in an increase in entropy has a positive entropy change (AS). Most spontaneous thermodynamic processes are accompanied by an increase in entropy. Entropy has units of Joules per degree K per mole. For representative values see table on p. 393. 

Obviously die first law is not all there is to the structure of themiodynamics, since some adiabatic changes occur spontaneously while the reverse process never occurs. An aspect of the second law is that a state fimction, the entropy S, is found that increases in a spontaneous adiabatic process and remains unchanged in a reversible adiabatic process it caimot decrease in any adiabatic process. 

When a gas comes in contact with a solid surface, under suitable conditions of temperature and pressure, the concentration of the gas (the adsorbate) is always found to be greater near the surface (the adsorbent) than in the bulk of the gas phase. This process is known as adsorption. In all solids, the surface atoms are influenced by unbalanced attractive forces normal to the surface plane adsorption of gas molecules at the interface partially restores the balance of forces. Adsorption is spontaneous and is accompanied by a decrease in the free energy of the system. In the gas phase the adsorbate has three degrees of freedom in the adsorbed phase it has only two. This decrease in entropy means that the adsorption process is always exothermic. Adsorption may be either physical or chemical in nature. In the former, the process is dominated by molecular interaction forces, e.g., van der Waals and dispersion forces. The formation of the physically adsorbed layer is analogous to the condensation of a vapor into a liquid in fret, the heat of adsorption for this process is similar to that of liquefoction. 

The process described above is usually called osmosis and this usually imphes a flow of fluid in one direction or the other. If the permeating species, usually called the solvent, flows from the pure compartment to the mixture compartment then it is called osmosis pure and simple. This seems the natural process since the solvent dilutes the solution and this involves an increase in entropy and/or a decrease in free energy, so the resultant flow is spontaneous and the system tends to equihbrium. However, the starting conditions may be such that the difference of pressure... 

According to the second law of thermodynamics, for a reaction to proceed spontaneously it must produce an increase in entropy (AS > 0). Because most spontaneous chemical reactions in the body are exothermic (AH < 0), most spontaneous chemical reactions will have AG values less than zero as well. This means that if, in the reaction shown in Equation... 

On the other hand, in any irreversible process although the system may gain (or lose) entropy and the surroundings lose (or gain) entropy, the system plus surrounding will always gain in entropy (equation 20.141). Thus for a real process proceeding spontaneously at a finite rate... 

AS, the change in entropy (Section 17.2) a positive value of AS tends to make a reaction spontaneous. 

The relationship between entropy change and spontaneity can be expressed through a basic principle of nature known as the second law of thermodynamics. One way to state this law is to say that in a spontaneous process, there is a net increase in entropy, taking into account both system and surroundings. That is,... 

Notice that the second law refers to the total entropy change, involving both system and surroundings. For many spontaneous processes, the entropy change for the system is a negative quantity. Consider, for example, the rusting of iron, a spontaneous process ... 

In principle, the second law can be used to determine whether a reaction is spontaneous. To do that, however, requires calculating the entropy change for the surroundings, which is not easy. We follow a conceptually simpler approach (Section 17.3), which deals only with the thermodynamic properties of chemical systems. 

A positive value of AS. If the entropy change is positive (AS > 0), the term —TAS will make a negative contribution to AG. Hence there will be a tendency for a reaction to be spontaneous if the products are less ordered than the reactants. 

Tables of standard free energies of formation at 25°C of compounds and ions in solution are given in Appendix 1 (along with standard heats of formation and standard entropies). Notice that, for most compounds, AG is a negative quantity, which means that the compound can be formed spontaneously from the elements. This is true for water ...

It is more common to find that AH° and AS° have the same sign (Table 17.2, III and IV). When this happens, the enthalpy and entropy factors oppose each other. AG° changes sign as temperature increases, and the direction of spontaneity reverses. At low temperatures, AH° predominates, and the exothermic reaction, which may be either the forward or the reverse reaction, occurs. As the temperature rises, the quantity TAS° increases in magnitude and eventually exceeds AH°. At high temperatures, the reaction that leads to an increase in entropy occurs. In most cases, 25°C is a low temperature, at least at a pressure of 1 atm. This explains why exothermic reactions are usually spontaneous at room temperature and atmospheric pressure. 

Key Terms enthalpy, H free energy of formation, AG standard entropy change, AS° entropy, S spontaneous process standard free energy change, AG° free energy, G... 

Entropy change (AS) The difference in entropy between products and reactants, 455-457,474q Gibbs-Helmhoftz equation, 459,461,474q spontaneity and, relationship, 457-458 Enzyme, 306-307 restrictive, 628 zinc, 550 Equation... 

Second law of thermodynamics A basic law of nature, one form of which states that all spontaneous processes occur with an increase in entropy, 457 Second order reaction A reaction whose rate depends on the second power of reactant concentration, 289,317q gas-phase, 300t... 

Spectator ion An ion that, although present, takes no part in a reaction, 279,82-83, 372-373,399 Spontaneity of reaction concentration and, 465-467,475-476q entropy and, 453-458 free energy and, 458-471 pressure effects, 465-467,475-476q process, 451-453 redox, 489-490... 

Thermodynamic, second law The entropy of the universe increases in a spontaneous process and remains unchanged in a reversible process. It can never decrease. 

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... 

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