Spontaneity criterion

Constraint Conditions Thermodynamic Potential Criterion of Spontaneity Criterion of Equilibrium... 

The flash point of a petroleum liquid is the temperature to which it must be brought so that the vapor evolved burns spontaneously in the presence of a flame. For diesel fuel, the test is conducted according to a closed cup technique (NF T 60-103). The French specifications stipulate that the flash point should be between 55°C and 120°C. That constitutes a safety criterion during storage and distribution operations. Moreover, from an official viewpoint, petroleum products are classified in several groups according to their flash points which should never be exceeded. 

In equation (Cl.4.14) the saturation parameter essentially defines a criterion to compare the time required for stimulated and spontaneous processes. If I then spontaneous coupling of the atom to the vacuum modes of the field is fast compared to the stimulated Rabi coupling and the field is considered weak. If s" 1 then the Rabi oscillation is fast compared to spontaneous emission and the field is said to be strong. Setting s equal to unity defines the saturation condition... 

Figure 4.3a shows schematically how the Gibbs free energy of liquid (subscript 1) and crystalline (subscript c) samples of the same material vary with temperature. For constant temperature-constant pressure processes the criterion for spontaneity is a negative value for AG, where the A signifies the difference final minus initial for the property under consideration. Applying this criterion to Fig. 4.3, we conclude immediately that above T , AGf = Gj - G. is negative... 

We now turn specifically to the thermodynamics and kinetics of reactions (5. EE) and (5.FF). The criterion for spontaneity in thermodynamics is AG <0 with AG = AH - T AS for an isothermal process. Thus it is both the sign and magnitude of AH and AS and the magnitude of T that determine whether a reaction is thermodynamically favored or not. As usual in thermodynamics, the A s are taken as products minus reactants, so the conclusions apply to the reactions as written. If a reaction is reversed, products and reactants are interchanged and the sign of the AG is reversed also. 

To develop a general criterion for spontaneity, we will apply the principles of thermodynamics, the science that deals with heat and energy effects. Three different thermodynamic functions are of value in analyzing spontaneity. 

Besides serving as a general criterion for spontaneity, the free energy change can be used to—... 

There is still another basic objection to using the sign of AH as a general criterion fir spontaneity. Endothermic reactions that are nonspontaneous at room temperature often become spontaneous when the temperature is raised. Consider far example, the decomposition of limestone ... 

Ordinarily, this principle is applied at standard concentrations (1 atm for gases, 1M for species in aqueous solution). Hence it is the sign of E° that serves as the criterion for spontaneity. To show how this works, consider the problem of oxidizing nickel metal to Ni2+ ions. This cannot be accomplished by using 1M Zn2+ ions ... 

As pointed out previously, the value of the standard cell voltage, E°, is a measure of the spontaneity of a cell reaction. In Chapter 17, we showed that the standard free energy change, AG°, is a general criterion for reaction spontaneity. As you might suppose, these two quantities have a simple relation to one another and to the equilibrium constant, K, for the cell reaction. 

Hence, Flory s theory offers an objective criterion for chain flexibility and makes possible to divide all the variety of macromolecules into flexible-chain (f > 0.63) and rigid-chain (f < 0.63) ones. In the absence of kinetic hindrance, all rigid-chain polymers must form a thermodynamically stable organized nematic phase at some polymer concentration in solution which increases with f. At f > 0.63, the macromolecules cannot spontaneously adopt a state of parallel order under any conditions. 

Figure 15 describes the decrease in the flexibility f of the macromolecules during melt stretching (corresponding to an increase in /3m) with x. According to Flory s criterion, the diminution of the flexibility of molecules to the value of f < 0.63 leads to a spontaneous transition of the system into the state of parallel order. It can be seen in Fig. 15 that f = 0. is attained at x = 30 or o = 0.6 x 107 n/m2 at these stresses, the melt is organized into a nematic state. 

Equation (5.47) gives the criterion for reversibility or spontaneity within subsystem A of an isolated system. The inequality applies to the spontaneous process, while the equality holds for the reversible process. Only when equilibrium is present can a change in an isolated system be conceived to occur reversibly. Therefore, the criterion for reversibility is a criterion for equilibrium, and equation (5.47) applies to the spontaneous or the equilibrium process, depending upon whether the inequality or equality is used. 

Equation (5.55) gives the criterion for equilibrium or spontaneity in a constant pressure and entropy process. 

The decrease in Gibbs free energy as a signpost of spontaneous change and AG = 0 as a criterion of equilibrium are applicable to any kind of process, provided that it is occurring at constant temperature and pressure. Because chemical reactions are our principal interest in chemistry, we now concentrate on them and look for a way to calculate AG for a reaction. 

The thermodynamic function used as the criterion of spontaneity for a chemical reaction is the Gibbs free energy of reaction, AG (which is commonly referred to as the reaction free energy ). This quantity is defined as the difference in molar Gibbs free energies, Gm, of the products and the reactants ... 

The spontaneous direction of any process is toward greater dispersal of matter plus energy. If we are to apply this criterion in a quantitative way, we need ways to measure amounts of dispersal. Scientists analyze the constraints on a system to measure the dispersal of matter. The more the system is constrained, the less dispersed it is. Scientists do calculations on the flow of heat to measure changes in the dispersal of energy. 

We see that the total change in entropy is a positive quantity for both these spontaneous processes, even though one process is exothermic and the other is endothermic. When this type of calculation is carried out for other processes, the same result is always obtained. For any spontaneous process, the total change of entropy is a positive quantity. Thus, this new state function of entropy provides a thermod3mamic criterion for spontaneity, which is summarized in the second law of thermodynamics ... 

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. 

The key to this problem is the first step in the seven-step strategy What is asked for The word spontaneous suggests that free energies are involved in this problem. The criterion for spontaneity at constant temperature and pressure is A Greaction < 0, so the problem asks us to show that A > 0 at r = 298 K. Then we can use Equation to calculate the temperature at which... 

Ozone is a highly endothermic substance. Its enthalpy of formation reaches 2.96 KJ/g, which makes it very unstable thermodynamically by CHETAH criterion Ci. In the liquid or solid state, it detonates spontaneously. 

In thermodynamics, entropy enjoys the status as an infallible criterion of spontaneity. The concept of entropy could be used to determine whether or not a given process would take place spontaneously. It has been found that in a natural or spontaneous process there would be an increase in the entropy of the system. This is the most general criterion of spontaneity that thermodynamics offers however, to use this concept one must consider the entropy change in a process under the condition of constant volume and internal energy. Though infallible, entropy is thus not a very convenient criterion. There have, therefore, been attempts to find more suitable thermodynamic functions that would be of greater practical... 

An important use of the free energy function is to obtain a simple criterion for the occurrence of spontaneous processes and for thermodynamic equilibrium. According to the second law of thermodynamics,... 

Having introduced matters pertaining to the electrochemical series earlier, it is only relevant that an appraisal is given on some of its applications. The coverage hereunder describes different examples which include aspects of spontaneity of a galvanic cell reaction, feasibility of different species for reaction, criterion of choice of electrodes to form galvanic cells, sacrificial protection, cementation, concentration and tempera lure effects on emf of electrochemical cells, clues on chemical reaction, caution notes on the use of electrochemical series, and finally determination of equilibrium constants and solubility products. 

When this criterion is fulfilled the compound is stable with respect to the spontaneous development of inhomogeneities in the average atomic density. The phase is in other words stable with regard to infinitesimal density fluctuations. Equation (5.3) requires that the heat capacity is positive. 

As a new criterion for reaction spontaneity, we say AS(totai) must be positive. We must consider the surroundings if we are to understand how the overall extent of energetic disorder increases during a process. 

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