Thermodynamic drive, for

If one of the kinetic factors approaches zero first, the reaction rate is said to be kinetically controlled if the thermodynamic factor falls first, the control is thermodynamic. The aerobic consumption of organic species and highly reduced compounds such as H2(aq) and H2S(aq) invariably show kinetic controls, because the thermodynamic drive for the oxidation of these compounds is quite large. Since methanogens and sulfate reducers operate under a considerably smaller thermodynamic drive, in contrast, it is not uncommon for their reaction rates to be controlled thermodynamically. 

The thermodynamic drive for each reaction is its negative free energy change, —AGr. From Equation 7.15, this quantity is given as,... 

Figure 22.7 shows how the thermodynamic drive for each metabolism varies as the fluids mix, as determined from the redox potentials in Figure 22.5. Microbial life is known to exist near the subsea vents to temperatures as high as 121 °C (Kashefi and Lovley, 2003) and it seems unlikely that it will be observed beyond 150 °C. We need consider, therefore, only the latter part of the mixing, where temperature falls below such limits.

Taking sulfide oxidation (Reaction 22.19) as an example, when the fluid mixture reaches 25 °C, there are about 5 mmol of H2S(aq) and 0.6 mmol of 02(aq) in the unreacted fluid, per kg of vent water. The 02(aq) will be consumed first, after about 0.3 mmol of reaction turnover, since its reaction coefficient is two it is the limiting reactant. The thermodynamic drive for this reaction at this temperature is about 770 kJ mol-1. The energy yield, then, is (0.3 x 10-3 mol kg-1) x (770 x 103 J mol-1), or about 230 J kg-1 vent water (Fig. 22.8). In reality, of course, this entire yield would not necessarily be available at this point in the mixing. If some of the 02(aq) had been consumed earlier, or is taken up by reaction with other reduced species, less of it, and hence less energy would be available for sulfide oxidation. 

Various theories, ranging from qualitative interpretations to those rooted in irreversible thermodynamics and geochemical kinetics, have been put forward to explain the step rule. A kinetic interpretation of the phenomenon, as proposed by Morse and Casey (1988), may provide the most insight. According to this interpretation, Ostwald s sequence results from the interplay of the differing reactivities of the various phases in the sequence, as represented by Ts and k+ in Equation 26.1, and the thermodynamic drive for their dissolution and precipitation of each phase, represented by the (1 — Q/K) term. 

The surface complementarity between the quantum activated complex and the catalytic surrounding media is the main idea of the present theory. The oscillating stereochemical control of the synthesis of thermoplastic elastomeric polypropylene recently reported by Coates and Waymouth [208] can be easily interpreted in terms of catalyst changing surface complementarity. Hill and Zhang have discovered a molecular catalyst that experiences a kinetic and thermodynamic drive for its own reassembly and repair under conditions of catalysis [209]. This is basically what an enzyme does when moving from the apo-structure towards the catalytically apt conformation. 

How can each step in this complex assembly process set the stage for the next step Apparently the structure of each newly synthesized protein monomer is stable only until a specific interaction with another protein takes place. The binding energy of this interaction is sufficient to induce a conformational alteration that affects a distant part of the protein surface and generates complementarity toward a binding site on the next protein that is to be added. Every one of the baseplate proteins must have such self-activating properties Sometimes proteolytic cleavage of a subunit is required. If it occurs at an appropriate point in the sequence it provides thermodynamic drive for the assembly process. 

One function in some heterogeneous catalysts is to bind and dissociate simple diatomic molecules such as Nj and CO. The strength of the binding interaction with the metal surface provides the thermodynamic drive for these cleavage reactions. Reactions such as CO and N2 dissociation appear to require more than one surface metal atom, and this phenomenon is referred to as a metal ensemble effect (22). Thus, the conversion of CO + H2 to... 

One of the earliest methods for preparing aromatic boronic acids involved the reaction between diaryl mercury compounds and boron trichloride [198]. As organomer-curial compounds are to be avoided for safety and environmental reasons, this old method has remained unpopular. In this respect, trialkylaryl silanes and stannanes are more suitable and both can be transmetallated efficiently with a hard boron halide such as boron tribromide [199]. The apparent thermodynamic drive for this reaction is the higher stability of B-C and Si(Sn)-Br bonds of product compared to the respective B-Br and Si(Sn)-C bonds of substrates. Using this method, relatively simple arylboronic acids can be made following an aqueous acidic workup to hydrolyze the arylboron dibromide product [193]. For example, some boronic acids were synthesized more conveniently from the trimethylsilyl derivative than by a standard ortho-metallation procedure (entry 11, Table 1.3). 

Despite the intrinsic difficulties mentioned above, a number of strategies have been devised to realize oxidative addition of C-C a-bonds. For example, release of ring strain of a substrate molecule affords both kinetic and thermodynamic drive for oxidative addition. A chelating effect also assists both kinetically and... 

It is quite clear, first of all, that since emulsions present a large interfacial area, any reduction in interfacial tension must reduce the driving force toward coalescence and should promote stability. We have here, then, a simple thermodynamic basis for the role of emulsifying agents. Harkins [17] mentions, as an example, the case of the system paraffin oil-water. With pure liquids, the inter-facial tension was 41 dyn/cm, and this was reduced to 31 dyn/cm on making the aqueous phase 0.00 IM in oleic acid, under which conditions a reasonably stable emulsion could be formed. On neutralization by 0.001 M sodium hydroxide, the interfacial tension fell to 7.2 dyn/cm, and if also made O.OOIM in sodium chloride, it became less than 0.01 dyn/cm. With olive oil in place of the paraffin oil, the final interfacial tension was 0.002 dyn/cm. These last systems emulsified spontaneously—that is, on combining the oil and water phases, no agitation was needed for emulsification to occur. 

In the presence of oxygen and water the oxides of most metals are more thermodynamically stable than the elemental form of the metal. Therefore, with the exception of gold, the only metal which is thermodynamically stable in the presence of oxygen, there is always a thermodynamic driving force for corrosion of metals. Most metals, however, exhibit some tendency to passivate, ie, to form a protective oxide film on the surface which retards further corrosion. 

Do diffusion coefficient corrected for thermodynamic driving force, mvs... 

Complete wetting, i.e. spontaneous spreading should always be sought to maximize adhesion. This condition occurs when, with reference to Fig. 4, it is not possible to satisfy the horizontal force balance, i.e. ys > Vl + Ysl- The thermodynamic driving force for the spreading process is the spreading coefficient. 

A reversed, reductive TCA cycle would require energy input to drive it. What might have been the thermodynamic driving force for such a cycle Wachtershanser hypothesizes that the anaerobic reaction of FeS and H9S to form insoluble FeS9 (pyrite, also known as fool s gold) in the prebiotic milieu could have been the driving reaction ... 

Shown in Fig. 4a is the temperature dependence of the relaxation time obtained from the isothermal electrical resistivity measurement for Ni Pt performed by Dahmani et al [31. A prominent feature is the appearance of slowing down phenomenon near transition temperature. As is shown in Fig. 4b [32], our PPM calculation is able to reproduce similar phenomenon, although the present study is attempted to LIq ordered phase for which the transition temperature, T]., is 1.89. One can confirm that the relaxation time, r, increases as approaching to l/T). 0.52. This has been explained as the insufficiency of the thermodynamic driving force near the transition temperature in the following manner. 

The thermodynamic driving force behind the corrosion process can be related to the corrosion potential adopted by the metal while it is corroding. The corrosion potential is measured against a standard reference electrode. For seawater, the corrosion potentials of a number of constructional materials are shown in Table 53.1. The listing ranks metals in their thermodynamic ability to corrode. Corrosion rates are governed by additional factors as described above. 

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