Diverse salt effect

This effective concentration of an ion in the presence of an electrolyte is called the activity of the ion. Activity can be used to describe quantitatively the effects of salts on equilibrium constants (see the diverse salt effect below). Activity is also important in potentiometric measurements (see Chapter 13). In this section we describe how to estimate activity. 

We will generally ignore diverse salt effects. 

Derive the equivalent of Equation 7.91 for the diverse salt effect on an uncharged weak base B. 

Scheme 5 depicts Winstein s complete solvolysis mechanism.29 Ion-pair return can be from the intimate ion pair (ion-pair return or internal return), from the external ion pair (external ion-pair return), or from the free ions (external ion return). The term external return refers to the sum of external ion-pair return and external ion return. The special salt effect operates by diversion of the external.ion pair, probably through the mechanism shown in Equation 519, so that it can no longer... 

It is pertinent to consider separately the enhancement effect of salt on two steps the initiation step (onset of the flow) and the structured flow. The transport rates are related to the properties of the final structured flow and are contributed from the effects on both steps. The effect on the initiation step is clearly noticed since the critical PVP concentrations for the occurrence of the structured flow depended on the kind of salt. Effects of a salt on the cross diffusion constants of the two polymer components will be examined on both excluded volume and frictional effect. The effect on the excluded volume interaction between the two polymer components is expected to be small. This expectation is partly supported by the result that coil dimension of PVP was not influenced by the addition of a salt at 2 M in the cases of three salts LiCl, NaCl and CsCI, while these salts showed quite diverse effects on the trrmsport rates of PVP. Since viscosities vary with the kind and the concentration of salt, frictional coefficients are influenced by the presence of a salt. In this respect cross diffusion constants may be affected by salt through a change in viscosity of the medium. 

Another important factor for coordination chemists is the general principle stated simply by Basolo solid salts separate from aqueous solution easiest for combinations of either small cation-small anion or large cation-large anion, preferably with systems having the same but opposite charges on the counter ions. Other factors governing solubility of salts are pH, interionic attraction, and the diverse ion effect, which will not be covered in detail here. 

We mentioned at the begmning of the last section on activity that the presence of diverse salts will generally increase the dissociation of weak electrolytes due to a shielding (or decrease in the activity) of the ionic species produced upon dissociation. We can quantitatively predict the extent of the effect on the equilibrium by taking into account the activities of the species in the equilibrium. 

In Chapter 6 we defined the thermodynamic equilibrium constant written in terms of activities to account for the effects of inert electrolytes on equilibria. The presence of diverse salts will generally increase the solubility of precipitates due to the shielding of the dissociated ion species. (Their activity is decreased.) Consider the solubility of AgCl. The thermodynamic solubility product K p is... 

Diverse salts increase the solubility of precipitates and have more effect on precipitates with multiply charged ions. 

The diverse ion effect is more commonly called the salt effect. As a result of the salt effect, the numerical value of a K p based on molarities will vary depending on the ionic atmosphere. Most tabulated values of K p are based on activities rather than on molarities, thus avoiding the problem of the salt effect. 

The salt effect is that of ions different from those directly involved in a solution equilibrium. The salt effect is also known as the diverse or "uncommon" ion effect. 

Electronic Applications. The PGMs have a number of important and diverse appHcations in the electronics industry (30). The most widely used are palladium and mthenium. Palladium or palladium—silver thick-film pastes are used in multilayer ceramic capacitors and conductor inks for hybrid integrated circuits (qv). In multilayer ceramic capacitors, the termination electrodes are silver or a silver-rich Pd—Ag alloy. The internal electrodes use a palladium-rich Pd—Ag alloy. Palladium salts are increasingly used to plate edge connectors and lead frames of semiconductors (qv), as a cost-effective alternative to gold. In 1994, 45% of total mthenium demand was for use in mthenium oxide resistor pastes (see Electrical connectors). 

For many years such media have been based on strong salt solutions, e.g. calcium chloride brines. Sodium dichromate has been used (seep. 17 26), but recently other inhibitors have been claimed to be effective. One patent quotes N-alkyl-substituted alkanolamines, e.g. 2-ethyl ethanolamine -I- BTA at pH A mixture of hydrazine hydrochloride -i- BTA has been claimed as well as a mixture of gelatin -h triethanolamine -h potassium dihydrogen phosphate . Other examples are to be found in the patent literature and the above are quoted to illustrate the diversity of chemicals that may be used. 

Properly folded native proteins tend to aggregate less than when unfolded. Solution additives that are known to stabilize the native proteins in solution may inhibit aggregation and enhance solubility. A diverse range of chemical additives are known to stabilize proteins in solution. These include salts, polyols, amino acids, and various polymers. Timasheff and colleagues have provided an extensive examination of the effects of solvent additives on protein stability [105]. The unifying mechanism for protein stabilization by these cosolvents is related to their preferential exclusion from the protein surface. With the cosolvent preferentially excluded, the protein surface is... 

The structurally related salts [M(Cp )2] [M (tds)2] (M = Fe, Mn, Cr M = Ni, Pt) and [Fe(Cp )2][Pt(tds)2] allowed a systematic study of the effect of a diversity of variables on the magnetic behavior of these compounds, such as the variation of the spin of the cation, the role of the single ion anisotropy, the effect of the variation of the size of atoms involved in the intermolecular contacts. Furthermore, the analysis of the intermolecular contacts in these compounds provided a reasonable interpretation of the intra and interchain magnetic coupling, and its relative strength within the series [44, 45]. 

The incorporation of two terminal pyrazole or triazole rings into the ter-pyridine framework leads to a diversity of spin crossover behaviour not seen, for example, in the bis(thiazolyl) systems discussed above. It is likely that the presence of a non-coordinating >NH group and its involvement in hydrogen bonding gives rise to the striking effects. For a series of salts of [Fe(bpp)2]2+ (bpp is 2,6-bis(pyrazol-3- yl)pyridine 58) a marked dependence of the spin state on the anion and the extent of hydration has been observed [85-88]. 

GC exert their regulatory effects on the HPA system via two types of corticosteroid receptors the glucocorticoid receptor (GR) and the mineralocorticoid receptor (MR) (Reul and De Kloet 1985). GRs occur everywhere in the brain but are most abundant in hypothalamic CRH neurons and pituitary corticotropes. MRs, in contrast, are highly expressed in the hippocampus and, at lower expression levels, in hypothalamic sites involved in the regulation of salt appetite and autonomic outflow. The MR binds GC with a tenfold higher affinity than does the GR (Reul and De Kloet 1985). These findings on corticosteroid receptor diversity led to the working hypothesis that the tonic influences of corticosterone... 

Ferrocenyl-based polymers are established as useful materials for the modification of electrodes, as electrochemical biosensors, and as nonlinear optical systems. The redox behavior of ferrocene can be tuned by substituent effects and novel properties can result for example, permethylation of the cyclopentadienyl rings lowers the oxidation potential, and the chaige transfer salt of decamethylfer-rocene with tetracyanocthylene, [FeCpJ]" (TCNE], is a ferromagnet below = 4.8 K, and electrode surfaces modified with a pentamethylferrocene derivative have been used as sensors for cytochrome c These diverse properties have provided an added impetus to studies on ferrocene dendrimers. 

Barrer showed these hydrogen zeolites, mordenite and chabazite, to be crystalline using x-ray diffraction, and stated, Hydrogen zeolites are effectively crystalline aluminosilicic acids, the salts of which are their diverse cation exchange products." Szymanski, Stamires, and Lynch (13) used simple thermal decomposition of an ammonium zeolite X in an attempt to prepare the hydrogen zeolite... 

Homophthaldehyde is converted into the isobenzopyrylium salt by this route (33JCS555). However, the yield of the unsubstituted pyrylium salt obtained from pentanedial is low, but much better from the enolate (53CB1327). Several other reagents are effective in bringing about the cyclization and oxidation of pentane-1,5-diones and the diverse substitution patterns which can be achieved increase the value of this method. 

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