Salt effect on rates

The primary salt effect on rates of electron spin exchange in solutions of Fremy s salt is consistent with bimolecular reaction species with a charge product (za b) of + 4, which supports a mechanism involving collision between two [(S03)2N0] anions (za = Zr = — 2). ... 

The effects of added M + ions, M = Mn, Ni, Cu, or Zn, on rates of aquation and of racemization of [Cr(ox)3] are attributed to their effects on the hydration shell around the complex ion rather than to simple ion-pairing. The markedly different effects of different alkali-metal cations on base hydrolysis of the [Co(NH3)5Br] + cation" and on the cerium(rv) oxidation of methylmandelic acid " may have a similar explanation. Non-electrostatic factors are also important in salt effects on the formate plus chromate and iodide plus bromate reactions." Observed salt effects on rates of hydrolysis of a variety of anions such as [BFi]-, [SiFe] , and [S20 ] ... 

IsE, N., Matsiti, F. The primary salt effect on rate of reaction between likely charged ionic species by polyelectrolsrtes. J. Am. Chem. Soc. 90,4242 (1968). 

An important cautionary note must be inserted here. It may seem that the study of the salt effect on the reaction rate might provide a means for distinguishing between two kinetically equivalent rate terms such as k[HA][B] and k [A ][BH ], for, according to the preceding development, the slope of log k vs. V7 should be 0, whereas that of log k vs. V7 should be — 1. This is completely illusory. These two rate terms are kinetically equivalent, which means that no kinetic experiment can distinguish between them. To show this, we write the rate equation in the two equivalent forms, making use of Eq. (8-26) ... 

Salt effects. The rate of reaction of vanadium(V) with iodide ions is independent of ionic strength.28 The rate law is v = fc[V(V)][I ][H+]2. What is the charge on the predominant V(V) species in these solutions ... 

Buffer salts also can exert a secondary salt effect on drug stability. From Table 5 and Fig. 5 it is clear that the rate constant for an ionizable drug is dependent on its pKa. Increasing salt concentrations, particularly from polyelectrolytes such as citrate and phosphate, can substantially affect the magnitude of the pKa, causing a change in the rate constant. (For a review of salt effects, containing many examples from the pharmaceutical literature see Ref. 116.)... 

On the experimental side, evidence was accumulating that there is more than one kind of reducing species, based on the anomalies of rate constant ratios and yields of products (Hayon and Weiss, 1958 Baxendale and Hughes, 1958 Barr and Allen, 1959). The second reducing species, because of its uncertain nature, was sometimes denoted by H. The definite chemical identification of H with the hydrated electron was made by Czapski and Schwarz (1962) in an experiment concerning the kinetic salt effect on reaction rates. They considered four... 

Only low yields of the azide ion adduct are obtained from the reaction of simple tertiary derivatives in the presence of azide ion 2145 46 and it is not possible to rigorously determine the kinetic order of the reaction of azide ion, owing to uncertainties in the magnitude of specific salt effects on the rate constants for the solvolysis and elimination reactions. Therefore, these experiments do not distinguish between stepwise and concerted mechanisms for substitution reactions at tertiary carbon. 

VO(acac)2 < VO(Et-acac)2 VO(Me-acac)2 BMOV. Conversion rates for all hydrolysis products were faster than for the original species. Both EPR and visible spectroscopic studies of solutions prepared for administration to diabetic rats ocumented both a salt effect on the species formed and formation of a new halogen-containing complex. The authors concluded that vanadium compound efficacy with respect to long-term lowering of plasma glucose levels in diabetic rats traced the concentration of the hydrolysis product in the administration solution. 

The difference between A obsd and caic might be due to a specific salt effect on the rate constant for solvolysis. However, this is unlikely because perchlorate ion acts to stabilize carbocations relative to neutral substrates.At high concentrations of sodium bromide, the rate-limiting step for solvolysis of 1-Br is the capture of 1 by solvent (ks Scheme 5A). Substitution of Br for CIO4 should destabilize the carbocation-like transition state for this step relative to the starting neutral substrate, and this would lead to a negative, rather than positive deviation of obsd for equations (3A) and (3B). 

Extensive studies have been carried out on the concentrated salt effects on the solvolysis reaction rates of aliphatic halides and related compounds in acetone-water mixed solvents. The main outcome of the complicated results presented appears to be that Tt is proposed that one could simply distinguish 5n1 from 5n2 reactions merely by observing a substantial increase in the solvolysis rate constant at 1.0 mol dm LiC104 in aqueous mixed solvents. ... 

Salt effects on monomolecular heterolysis reactions (Avrl, El, FI, solvolysis) have been reviewed and me effects of salts on me rate of dehydrobromination of 3-bromocyclohexene have been interpreted. The regiochemistry and stereochemistry... 

The yield of the nucleophilic substitution product from the stepwise preassociation mechanism k[ = k. Scheme 2.4) is small, because of the low concentration of the preassociation complex (Xas 0.7 M for the reaction of X-2-Y). Formally, the stepwise preassociation reaction is kinetically bimolecular, because both the nucleophile and the substrate are present in the rate-determining step ( j). In fact, these reactions are borderline between S l and Sn2 because the kinetic order with respect to the nucleophile cannot be rigorously determined. A small rate increase may be due to either formation of nucleophile adduct by bimolecular nucleophilic substitution or a positive specific salt effect, whUe a formally bhnole-cular reaction may appear unimolecular due to an offsetting negative specific salt effect on the reaction rate. 

The rate constant for solvolysis of the model tertiary substrate 5-Cl is independent of the concentration of added azide ion, and the reaction gives only a low yield of the azide ion adduct (e.g., 16% in the presence of 0.50 M NaNa in 50 50 (v/v) water/trifluoroethanol]." Therefore, this is a borderline reaction for which it is not possible to determine the kinetic order with respect to azide ion, because of uncertainties about specific salt effects on the reaction." ... 

For the three reactions represented in Fig. 12 the maximum rate of hydrolysis in acid represents only a mpdest acceleration, compared with the rate in initially neutral solution. Bunton and Hadwick89,90 explained the maximum for methyl and phenyl trifluoroacetate in terms of negative salt effects on both acid-catalyzed and neutral reactions. Consistent with this interpretation, it was demonstrated directly that the rate of neutral hydrolysis is decreased by added salts. The effect of added salt should be to decrease the activity of water, and perhaps also to salt in the ester. 

Salt effects on reaction (42) (R = Me, X = Br) were also studied using the solvents dioxan (9) water(l), dioxan (4) water(l), and acetone. In all three cases it was shown that added bromide ion strongly depressed the rate and hence that the species HgBr3 was inoperative as an electrophile44. The effect of added lithium perchlorate was also investigated, but at the low concentrations used (0.09 x 10-4 M to 3.25 x 10-4 M) no salt effect could be observed. 

FPA results obtained at different salt conditions may not be directly comparable because the fluorescence properties of 6-MI, including the lifetime (t), are salt dependent. The salt dependence of the FPA of a helix in a complex construct should thereby be normalized relative to the FPA of a short control duplex of the same sequence of the targeted helix to account for salt effects on the local environment of the 6-MI fluorophore. The normalization ratio, rnoml, can be calculated as the ratio between the apparent rotational correlation time, 9, of the constructs and the control duplex only, rnomi = construct/ control- is related to the rate of anisotropy decay, with larger 9 associated with higher anisotropy. If the basic Perrin equation for a sphere (Eq. (14.3)) is used to simplify calculation, then... 

Diels-Alder reactivity of thiophene and benzothiophene remains poorly understood. AMI semiempirical studies examining the activation of thiophene for this thermally allowed [4+2] cycloaddition process have shown that the usual synthesis approaches (use of highly reactive dienophiles, substitution on thiophene, increased reaction pressures) have only small effects on rate enhancement. However, use of the corresponding S-methylthiophenium salts, which have little aromaticity, should provide excellent activation for Diels-Alder reactions of thiophenes even with poor dienophiles such as ethylene <95JHC483>. This AMI approach has been applied to examine Diels-Alder reactions of benzo[6] and benzo[c]thiophenes the theoretical data agree with experimental results <95JCS(P1)1217>. 

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