Equilibrium constants solvent effect

Cadmium, tris[4,4,4-trinuoro-l-(2-furyl)-l,3-butanedione]-structure, 65 Cadmium complexes equilibrium constant solvent effect, 516 Cage compounds in gravimetry, 525 Cage mechanism photochemistry, 393 Cages, 135 formation... 

Iron, tris(hexafluoroacetylacetone)-structure, 65 Iron, tris(oxalato)-chemical actinometer, 409 Iron, tris(l,10-phenanthroline)-absorptiometry, 549 racemization, 466 solid state, 467 structure, 64 Iron(O) complexes magnetic properties, 274 Iron(II) complexes magnetic behavior, 273 spectra, 253 Iron(III) complexes equilibrium constant solvent effect, 516 liquid-liquid extraction, 539 magnetic behavior, 272 spectra, 253 Iron(IV) complexes magnetic behavior, 272 Isocyanates metal complexes hydrolysis, 429 Isokinetic effect ligand exchange solid state, 469 Isomerism, 179-208 configurational, 180, 188 constitutional, 180,182 coordination, 183 detection, 180 history, 24... 

Nickel, tris( 1,10-phenanthroline)-racemization, 24,466 solid state, 467 structure, 64 Nickel(I) complexes magnetic properties, 274 Nickel(II) complexes, 470 allogonism, 207 equilibrium constants solvent effect, 516 isomerism, 184 liquid-liquid extraction, 544 magnetic properties, 274 5-mcrcaptoamine alkydation, 417 photoreactivity, 407... 

Ruthenium, (4,4 -bipyridyl)bis(pentaammine)-equilibrium constant solvent effect, 516 Ruthenium(ll) complexes magnetic behavior, 273 polymerization electrochemistry, 488 reactivity, 300 spectra, 254... 

Most reactions involve reactants and products that are dispersed in a solvent. If the amount of solvent is changed, either by diluting or concentrating the solution, the concentrations of ah reactants and products either decrease or increase. The effect of these changes in concentration is not as intuitively obvious as when the concentration of a single reactant or product is changed. As an example, let s consider how dilution affects the equilibrium position for the formation of the aqueous silver-amine complex (reaction 6.28). The equilibrium constant for this reaction is... 

The magnitude of the anomeric effect depends on the nature of the substituent and decreases with increasing dielectric constant of the medium. The effect of the substituent can be seen by comparing the related 2-chloro- and 2-methoxy-substituted tetrahydropy-rans in entries 2 apd 3. The 2-chloro compound exhibits a significantly greater preference for the axial orientation than the 2-methoxy compound. Entry 3 also provides data relative to the effect of solvent polarity it is observed that the equilibrium constant is larger in carbon tetrachloride (e = 2.2) than in acetonitrile (e = 37.5). 

The pH will depend upon the ionic strength of the solution (which is, of course, related to the activity coefficient — see Section 2.5). Hence, when making a colour comparison for the determination of the pH of a solution, not only must the indicator concentration be the same in the two solutions but the ionic strength must also be equal or approximately equal. The equation incidentally provides an explanation of the so-called salt and solvent effects which are observed with indicators. The colour-change equilibrium at any particular ionic strength (constant activity-coefficient term) can be expressed by a condensed form of equation (4) ... 

The lack of a substrate isotope effect suggests very extensive internal return and is readily explained in terms of the fact that conversion of the hydrocarbon to the anion would require very little structural reorganisation. Since koba = k 1k 2/(kLl+k 2) and k 2 is deduced as > k2, then kobs = Kk 2, the product of the equilibrium constant and the rate of diffusion away of a solvent molecule, neither of the steps having an appreciable isotope effect. If the diffusion rates are the same for reactions of each compound then the derived logarithms of partial rate factors (above) become pAT differences between benzene and fluorobenzene hydrogens in methanol. However, since the logarithms of the partial rate factors were similar to those obtained with lithium cyclohexylamide, a Bronsted cor-... 

NMR measurements indicate that the equilibrium constant varies with the polarity of the solvent and temperature. The more polar the solvent, the greater the fraction of sulfoxide at equilibrium which is consistent with the greater dipole moment of the sulfoxide as compared with the sulfenate. Increasing temperature results in a reverse effect, due to the steric hindrance in the sulfoxide which becomes more marked at higher temperatures. These results are the first published evidence for the reversibility of the sulfenate-sulfoxide rearrangement and illustrate the occurrence of the rearrangement unsuccessfully attempted by Cope39. 

Consequences of the Snyder and Soczewinski model are manifold, and their praetieal importance is very signifieant. The most speetaeular conclusions of this model are (1) a possibility to quantify adsorbents ehromatographic activity and (2) a possibility to dehne and quantify chromatographic polarity of solvents (known as the solvents elution strength). These two conclusions could only be drawn on the assumption as to the displacement mechanism of solute retention. An obvious necessity was to quantify the effect of displacement, which resulted in the following relationship for the thermodynamic equilibrium constant of adsorption, K,, in the case of an active chromatographic adsorbent and of the monocomponent eluent ... 

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