Isothermal energy change

Figure 15 Calculation of the isothermal energy change and the rate of reaction...

Again, if we consider the initial substances in the state of liquids or solids, these will have a definite vapour pressure, and the free energy changes, i.e., the maximum work of an isothermal reaction between the condensed forms, may be calculated by supposing the requisite amounts drawn off in the form of saturated vapours, these expanded or compressed to the concentrations in the equilibrium box, passed into the latter, and the products then abstracted from the box, expanded to the concentrations of the saturated vapours, and finally condensed on the solids or liquids. Since the changes of volume of the condensed phases are negligibly small, the maximum work is again ... 

Here, the a s refer to the activities in the chosen arbitrary state. The concept of activity is presented separately in a later section. For the present, the activity of a species in a system may just be considered to be a function of its concentration in the system, and when the species is in a pure form (or in its standard state), its activity is taken to be unity. The activities ac, aD, aA, aB given above correspond to the actual conditions of the reaction, and these may or may not correspond to the state of equilibrium. Two special situations can be considered. In the first, the arbitrary states are taken to correspond to those for the system at equilibrium. Q would then become identical to the equilibrium constant K and, according to the Van t Hoff isotherm, AG would then be zero. In the second situation, all the reactants and the products are considered to be present as pure species or in their standard states, and aA, aB, ac, and aD are all equal to 1. Then (7=1 and the free energy change is given by... 

The Van t Hoff isotherm establishes the relationship between the standard free energy change and the equilibrium constant. It is of interest to know how the equilibrium constant of a reaction varies with temperature. The Varft Hoff isochore allows one to calculate the effect of temperature on the equilibrium constant. It can be readily obtained by combining the Gibbs-Helmholtz equation with the Varft Hoffisotherm. The relationship that is obtained is... 

From the Van t Hoff isotherm it follows that for the oxidation reaction considered, the standard free energy change at temperature T is given by... 

The standard Gibbs free energy change for a reaction refers to the process wherein the reaction proceeds isothermally, starting with stoichiometric quantities of reactants each in its standard state of unit activity and ending with products each at unit activity. In general it is nonzero and given by... 

The bomb process is then considered to occur isothermally at 298.15 K, with a corresponding energy change A(/ibp(298.15 K). In the final state the bomb contents are a gaseous mixture of 02, N2, C02, and H20, and an aqueous solution of 02, N2, C02, and HNO3 (figure 7.6). The Washburn corrections for the final state include the following steps. 

The obtained A 7 a() value and the energy equivalent of the calorimeter, e, are then used to calculate the energy change associated with the isothermal bomb process, AE/mp. Conversion of AE/ibp to the standard state, and subtraction from A f/jgp of the thermal corrections due to secondary reactions, finally yield Ac f/°(298.15 K). The energy equivalent of the calorimeter, e, is obtained by electrical calibration or, most commonly, by combustion of benzoic acid in oxygen [110,111,113]. The reduction of fluorine bomb calorimetric data to the standard state was discussed by Hubbard and co-workers [110,111]. 

The surface complexation models quantify adsorption with experimentally determined equilibrium constants. Another, less widely used approach considers the relationship between the equilibrium constant for the adsorption reaction and the associated free energy change (James and Healy, 1972). Attempts have been made to determine the chemical contribution to the overall adsorption free energy by fitting adsorption isotherms to the experimental data values of -50, -33 and —45 kj mol were found for the change in chemical free energy associated with adsorption of Cr, Ni and Zn, respectively, on ferrihydrite (Crawford et al., 1993). Values ranging from -21 to 241 kJ mol were found for Ni on hematite the actual value depended upon the hydrolysis species that were assumed to exist (Fuerstenau and Osseo-Assare, 1987). 

For the same quantity of adsorbate on the desorption isotherm the corresponding free energy change is... 

The molar free-energy change associated with the isothermal vapor-pressure change from Pq to P is given by... 

The gas first undergoes reversible isothermal expansion at th, with energy change (as required by the first law)... 

The gas is now reversibly compressed under the isothermal conditions (tc) of the low-temperature reservoir, with energy change... 

Because the entire process was performed isothermally with ideal gases, the internal energy change (whether for the transporter gas or for the reservoirs as a... 

Let us consider a homogeneously, but not hydrostatically, stressed solid which is deformed in the elastic regime and whose structure elements are altogether immobile. If we now isothermally and reversibly add lattice molecules to its different surfaces (with no shear stresses) from the same reservoir, the energy changes are different. This means that the chemical potential of the solid is not single valued, or, in other words, a non-hydrostatically stressed solid with only immobile components does not have a unique measurable chemical potential [J. W. Gibbs (1878)]. 

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