Reactions free energy change

Because the formation of ZnTe is spontaneous (negative free-energy change), reaction (32) is possibly a UPD of Zn on Te sites. If the electrodeposition potentials are shifted to more negative values, the formation of ZnTe may be ... 

Gibbs-Helmholtz equation This equation relates the heats and free energy changes which occur during a chemical reaction. For a reaction carried out at constant pressure... 

The enthalpy, entropy and free energy changes for an isothennal reaction near 0 K caimot be measured directly because of the impossibility of carrying out the reaction reversibly in a reasonable time. One can, however, by a suitable combination of measured values, calculate them indirectly. In particular, if the value of... 

Let us now consider the reduction of a metal oxide by carbon which is itself oxidised to carbon monoxide. The reaction will become energetically feasible when the free energy change for the combined process is negative (see also Figure i.i). Free energies. 

When the e.m.f. of a cell is measured by balancing it against an external voltage, so that no current flows, the maximum e.m.f. is obtained since the cell is at equilibrium. The maximum work obtainable from the cell is then nFE J, where n is the number of electrons transferred, F is the Faraday unit and E is the maximum cell e.m.f. We saw in Chapter 3 that the maximum amount of work obtainable from a reaction is given by the free energy change, i.e. - AG. Hence... 

The dissociation constant, K., and standard free energy change, AG°, for this reaction are related by the equation. 

Having calculated the standai d values AyW and S" foi the participants in a chemical reaction, the obvious next step is to calculate the standard Gibbs free energy change of reaction A G and the equilibrium constant from... 

Cell Volta.ge a.ndIts Components. The minimum voltage required for electrolysis to begin for a given set of cell conditions, such as an operational temperature of 95°C, is the sum of the cathodic and anodic reversible potentials and is known as the thermodynamic decomposition voltage, is related to the standard free energy change, AG°C, for the overall chemical reaction,... 

Direct, One-Step Thermal Water Splitting. The water decomposition reaction has a very positive free energy change, and therefore the equihbrium for the reaction is highly unfavorable for hydrogen production. 

Many reaction schemes have been proposed (161,162). All reaction schemes ate designed such that reaction steps having positive A. " values are operated at high (625—725°C) temperatures, whereas reaction steps having negative AA values are operated at low (about 225°C) temperatures. The purpose is to lower the free energy change, ie, the work requirement, and increase the thermal requirement, for improved efficiency. Other considerations, such as reaction kinetics, corrosion, cost of materials, and side reactions must also be taken into account. 

The free energy changes of the outer shell upon reduction, AG° , are important, because the Nernst equation relates the redox potential to AG. Eree energy simulation methods are discussed in Chapter 9. Here, the free energy change of interest is for the reaction... 

M Tachiya. Relation between the electron-transfer rate and the free energy change of reaction. J Phys Chem 93 7050-7052, 1989. 

The free energy change associated with the reaction in Eq. (15) can be written in terms of the energy change associated with the reaction in vacuo (AG ) and the free energy change of the reacting species due to solvation as... 

A copy (5V4 inch floppy disk) of a menu-driven computer program to calculate Gibbs free energy of formation and change in Gibbs free energy for reactions (including random access data file of compound coefficients) is available for a nominal fee. For details, contact C. L. Yaws, Dept, of Chem. Eng. Lamar University, P.O. Box 10053, Beaumont, Texas 77710, USA. 

Estimation of the free-energy change associated with a reaction permits the calcula-aon of the equilibrium position for a reaction and indicates the feasibility of a given chemical process. A positive AG° imposes a limit on the extent to which a reaction can x cur. For example, as can be calculated using Eq. (4.2), a AG° of 1.0 kcal/mol limits conversion to product at equilibrium to 15%. An appreciably negative AG° indicates that e reaction is thermodynamically favorable. 

Neither the principles of thermodynamics nor theories of reaction rates require that there should be such linear relationships. There are, in fact, numerous reaction series that fail to show such correlations. Some insight into the origin of die correlation can be gained by considering the relationship between the correlation equation and the free-energy changes involved in the two processes. The line in Fig 4.2 defines an equation in which m is the slope of the line ... 

Since AG and AG are combinations of enthalpy and entropy terms, a linear free-energy relationship between two reaction series can result from one of three circumstances (1) AH is constant and the AS terms are proportional for the series, (2) AS is constant and the AH terms are proportional, or (3) AH and AS are linearly related. Dissection of the free-energy changes into enthalpy and entropy components has often shown the third case to be true. °... 

But spontaneity depends on the concentrations of reactants and products. If the ratio [Bl YCA] is less than a certain value, the reaction is spontaneous in the forward direction if [Bl YCA] exceeds this value, the reaction is spontaneous in the reverse direction. Therefore, it is useful to define a standard free-energy change (AG°) which applies to a standard state where [A] = [B] = 1 M. 

In any of these forms, this relationship allows the standard-state free energy change for any process to be determined if the equilibrium constant is known. More importantly, it states that the equilibrium established for a reaction in solution is a function of the standard-state free energy change for the process. That is, AG° is another way of writing an equilibrium constant. 

Equation (3.12) shows that the free energy change for a reaction can be very different from the standard-state value if the concentrations of reactants and products differ significantly from unit activity (1 Mfor solutions). The effects can often be dramatic. Consider the hydrolysis of phosphocreatine ... 

We can predict whether pairs of coupled reactions will proceed spontaneously by simply summing the free energy changes for each reaction. For example, consider the reaction from glycolysis (discussed in Chapter 19)... 

If the AG° for this reaction is —30.5 kJ/mol, what is AG° (that is, the free energy change for the same reaction with all components, including H, at a standard state of 1 AT) ... 

Hexokinase catalyzes the phosphorylation of glucose from ATP, yielding glncose-6-P and ADR Using the values of Table 3.3, calculate the standard-state free energy change and equilibrium constant for the hexokinase reaction. 

FIGURE 14.1 Reaction profile showing large AG for glucose oxidation, free energy change of —2,870 kj/mol catalysts lower AG, thereby accelerating rate. 

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