Standard free reaction energy

The standard Gibbs free energy of reaction, AG°, is defined like the Gibbs free energy of reaction but in terms of the standard molar Gibbs energies of the reactants and products ... 

STRATEGY We write the chemical equation for the formation of HI(g) and calculate the standard Gibbs free energy of reaction from AG° = AH° — TAS°. It is best to write the equation with a stoichiometric coefficient of 1 for the compound of interest, because then AG° = AGf°. The standard enthalpy of formation is found in Appendix 2A. The standard reaction entropy is found as shown in Example 7.9, by using the data from Table 7.3 or Appendix 2A. 

Just as we can combine standard enthalpies of formation to obtain standard reaction enthalpies, we can also combine standard Gibbs free energies of formation to obtain standard Gibbs free energies of reaction ... 

EXAMPLE 7.15 Sample exercise Calculating the standard Gibbs free energy of reaction... 

What Do We Need to Know Already The concepts of chemical equilibrium are related to those of physical equilibrium (Sections 8.1-8.3). Because chemical equilibrium depends on the thermodynamics of chemical reactions, we need to know about the Gibbs free energy of reaction (Section 7.13) and standard enthalpies of formation (Section 6.18). Ghemical equilibrium calculations require a thorough knowledge of molar concentration (Section G), reaction stoichiometry (Section L), and the gas laws (Ghapter 4). 

Notice that the combination of the first four terms in the final equation is the standard Gibbs free energy of reaction, AGr° (Eq. 19 of Chapter 7) ... 

STRATEGY Calculate the reaction quotient and substitute it and the standard Gibbs free energy of reaction into Eq. 5. If AGr < 0, the forward reaction is spontaneous at the given composition. If AGr > 0, the reverse reaction is spontaneous at the given composition. If AGr = 0, there is no tendency to react in either direction the reaction is at equilibrium. At 298.15 K, RT = 2.479 kJ-moF h... 

The reaction quotient, Q, has the same form as K, the equilibrium constant, except that Q uses the activities evaluated at an arbitrary stage of the reaction. The equilibrium constant is related to the standard Gibbs free energy of reaction by AG° = —RT In K. 

The effect of temperature on the equilibrium composition arises from the dependence of the equilibrium constant on the temperature. The relation between the equilibrium constant and the standard Gibbs free energy of reaction in Eq. 8 applies to any temperature. Therefore, we ought to be able to use it to relate the equilibrium constant at one temperature to its value at another temperature. 

A catalyst speeds up both the forward and the reverse reactions by the same amount. Therefore, the dynamic equilibrium is unaffected. The thermodynamic justification of this observation is based on the fact that the equilibrium constant depends only on the temperature and the value of AGr°. A standard Gibbs free energy of reaction depends only on the identities of the reactants and products and is independent of the rate of the reaction or the presence of any substances that do not appear in the overall chemical equation for the reaction. 

Table 16-5 The standard free energy of reaction, AG , for the main environmental redox reactions...

If two reactions differ in maximum work by a certain amount 8wm (= -SAG ), it follows from the Brpnsted relation [when taking into account the Arrhenius equation and the known relation between the equilibrium constant and the Gibbs standard free energy of reaction, A m = exp(-AGm/J r)] that their activation energies will differ by a fraction of this work, with the opposite sign ... 

Equation (3.3) gives the potential dependence of the reaction free energy of Reaction (3.2). Since this reaction equilibrium defines the standard hydrogen electrode potential, we now have a direct fink between quite simple DFT calculations and the electrode potential. In a similar way, we can now calculate potential-dependent reaction free energies for other reactions, such as O - - H" " + e OH or OH - -+ e HzO. 

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