The Cation Series

Subsequent to Hofmeister s original series that involved only anions it was realized that the nature of the cations of the salts used for the denaturation of proteins also 

It is generally agreed that Na , being near the midpoint of the series, has a minimal effect therefore it is almost universally used to study the anions effects of salts. Since also Cl, in the middle of the anion series (5.6) has a minimal effect, it is usually used to study the specific cation effects of a series of salts. 

What is noteworthy about the series is that for the monatomic alkali metal cations their order does not agree with their size or charge density or their lyotropic series (Voet 1937b). This apparent disorder (note the position of Cs+) is not universal, however, since cases where the lyotropic series is followed are also known. An instance is the rate of the penetration of the alkali metal cations through leaf cuticles that decreases in the order Cs+ Rb+ K+ Na+ Li+, i.e., in the expected order according to their surface charge densities. The cuticular pores were supposed by McFarlane and Berry to be lined with a protein that has exposed positive sites (McFarlane and Berry 1974). The critical micelle concentration (cmc) of sodium dodecylsulphate increases in the reverse order by these cations (Maiti et al. 2009), where Cs+ is at the expected position. The transition of a mixed surfactant (sodium dodecylsulfate + dodecyltrimethylammonium bromide with an excess of the former) from micelles to vesicles (Sect. 4.5) is also promoted in this sequence, explained by counter-ion association depending on relative ease of ion dehydration (Renoncourt et al. 2007). 

The critical coagulation concentration of alkali metal nitrates on negatively charged Agl sols also follows the lyotropic rather than the Hofmeister series LiNOs NaNOs KNO3 RbN03 CsNOs (Lyklema 2009). 

Variants of the cation Hofmeister series (5.8) have been proposed, where the position of, say, NH4 is shifted and guanidinium, C(NH2)3, is added, e.g.  

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It should be noted that in addition to changes in K2NbF7 or K2TaF7 concentrations that afford control over the complex structure and electrolysis parameters, the cation type also affects the equilibrium between the complex ions. The heptacoordinated complexes become increasingly dominant when progressing along the cation series from Li to Cs. 

Finally it appears that salts can also have a suppressive action according to the double valency rule , in which naturally the abbreviations of the series of terms of the cations already discussed in 3c (p. 391) and anomalous sequences of these terms occur. Compare Fig. 43 which relates to the flocculation with 2 m. eq. per 1 Co(NH3)0Cl8 throughout in various acetone concentrations. Here the suppressive actions of the two first terms of the cation series (2 — 1 and 1 — 1) and of the anion series (1 —2 and 1 — 1) have been investigated. 

In sulfonic acids (monolayers of dodecyl- and docosylsulfonic acids) this series reverses the less hydrated cations form more condensed monolayers. The cation series coincides with the lyotropic series [70-72, 108, 109] ... 

Note Some of Grahame s values for and included in this table. For a common cation, the sequence of anions in order of increasing adsorption is similar to that of the Hofmeister series in coagulation studies, and it is evident that specific adsorption properties are involved. 

These reactions, however, are complex and generally proceed through a series of reaction steps. The rate of weathering of siUcates may vary considerably, depending on the arrangement of the siUcon tetrahedra in the mineral and on the nature of the cations. 

Electrodialysis. In reverse osmosis pressure achieves the mass transfer. In electro dialysis (qv), dc is appHed to a series of alternating cationic and anionic membranes. Anions pass through the anion-permeable membranes but are prevented from migrating by the cationic permeable membranes. Only ionic species are separated by this method, whereas reverse osmosis can deal with nonionic species. The advantages and disadvantages of reverse osmosis are shared by electro dialysis. 

Competitive Extraetion of Anions. The successful extraction of the necessary anion into the organic phase is cmcial for PTC. Often three anions compete for the catalyst cation the one that is to react, the one formed in the reaction, and the one brought in originally with the catalyst. Table 1 hsts the widely differing values of tetra-rr-butylammonium salts. The big difference in the halide series is noteworthy and preparatively important. Hydroxide is 10 times mote difficult to extract than chloride (11) and the divalent and trivalent anions and PO " are stiU more hydrophilic. Thus... 

The hydrogen-deuterium exchange rates for 1,2-dimethylpyrazolium cation (protons 3 and 5 exchange faster than proton 4 Section 4.04.2.1.7(iii)) have been examined theoretically within the framework of the CNDO/2 approximation (73T3469). The final conclusion is that the relative reactivities of isomeric positions in the pyrazolium series are determined essentially by inductive and hybridization effects. 

S ts can be used to precipitate proteins by salting out effects. The effectiveness of various salts is determined by the Hofmeister series, with anions being effective in the order citrate > PO4" > SO4" > CH3COO > Cl > NO3 , and cations according to NH4 > > Na ... 

Series 7 gives a linear plot with p = —5.27, consistent with the S l mechanism. Series 8, however, shows a discontinuity, which Gassmann and Fentiman interpreted as a change in mechanism. Compounds in series 8 are capable of intramolecular assistance (neighboring group participation) by electron donation from the double bond to stabilize the cation, as in 9. 

Figure 7-2 indicates that this intramolecular assistance takes place with those compounds having substituents to the right of X = OMe = —0.78), for in this portion of the a scale compounds 8 solvolyze more rapidly than do 7. At the X = OMe member, however, the two series have essentially identical reactivities, and this behavior continues at more negative cr. It. therefore, appears that intramolecular participation by the double bond occurs when it is needed when the X substituent is sufficiently electron-donating to stabilize the cation, intramolecular assistance is not needed, so it does not occur, and the saturated and unsaturated series show the same reactivity. 

Niobium and tantalum provide no counterpart to the cationic chemistry of vanadium in the -t-3 and -t-2 oxidation states. Instead, they form a series of cluster compounds based... 

The coordination chemistry of the large, electropositive Ln ions is complicated, especially in solution, by ill-defined stereochemistries and uncertain coordination numbers. This is well illustrated by the aquo ions themselves.These are known for all the lanthanides, providing the solutions are moderately acidic to prevent hydrolysis, with hydration numbers probably about 8 or 9 but with reported values depending on the methods used to measure them. It is likely that the primary hydration number decreases as the cationic radius falls across the series. However, confusion arises because the polarization of the H2O molecules attached directly to the cation facilitates hydrogen bonding to other H2O molecules. As this tendency will be the greater, the smaller the cation, it is quite reasonable that the secondary hydration number increases across the series. 

Nucleophiles can also act as acids and bases, and this behavior substantially alters their nucleophilicity. At pH 5, trimethylamine exists mainly as its conjugate acid, trimethylammonium cation. First draw a Lewis structure, and then examine the electrostatic potential for trimethylammonium ion. On the basis of the map, which is the better nucleophile, the cation or the corresponding neutral amine At pH 12, phenol exists mainly as its conjugate base, phenoxide anion. First draw a Lewis structure (or series of Lewis structures), and then examine the electrostatic potential map for phenoxide anion. Which is the better nucleophile, phenoxide or phenol ... 

The first step in the addition of an electrophile such as HBr to an alkyne involves protonation and subsequent formation of an intermediate vinyl cation. Where does propyne protonate Compare energies of 1-methylvinyl and 2-methylvinyl cations. Which is more stable Why Measure CC bond distance in the more stable cation. Does the cation incorporate a full triple bond (as in propyne) or a double bond (as in propene). Examine atomic charges and electrostatic potential maps to locate the positive charge in the two cations. Is the more stable ion the one in which the charge is better delocalized Use the charges together with information about the ions geometry to draw Lewis structures (or a series of Lewis structures) for 1-methylvinyl and 2-methylvinyl cations. 

Methyl propiolate and pyridine give a rather unstable 2 1 molar adduct which is the 1,2-dihydropyridine (112). The reaction sequence proposed to account for its formation is identical in principle to a similar scheme proposed earlier in the acridine series (Section II,A,2) and is also supported by the observation that the 1-benzoyl-pyridinium cation with the phenylacetylide anion yields (113). ... 

The present review describes recent advances in quinazoline chemistry, some of which are but modem applications of earlier methods, whereas others strike out on new, and sometimes surprising, pathways. The structure of the cation of the parent substance, quinazoline, has only recently been made clear, and it has become evident that covalent hydration is a phenomenon widely distributed throughout the quinazoline series. With this fact in mind, it seems better to set forth the newly found properties of quinazolines before proceeding to an account of advances in synthesis. 

Comparison by Gardner and Katritzky of the pKa values of the cations formed by 2- and 4-aminopyridine 1-oxide and the alkylated derivatives of both forms showed that in aqueous solution the amino form predominates for 2- and 4-aminopyridine 1-oxide (cf. 241 242) and the methylamino form for 2- and 4-methylaminopyridine 1-oxide by factors of ca. 10 and >10 in the 2- and 4-series, respectively. The ultraviolet spectra of the 4-isomer and its alkylated derivatives... 

Most of the work done in the pteridine series has been concerned with the equilibria between the neutral species and the anions. This work was more fruitful than that involving the cations because all three of the values, p /, p a , and pK/ (for definitions, see Section II, A), could be determined, and, from these, ratios of the hydrated to the anhydrous forms were calculated. Furthermore, the kinetics in the... 

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