Association constant measurement

Ion pair association constants measured by conductance have not often been verified by independent techniques, but where comparisons have been made agreement appears satisfactory. For example, a value of 70.2 0.5 was obtained for the association constant of silver nitrate in acetonitrile by conductance l0), and a value of 74 5 by potentiometric measurements, 44) of the cell... 

The stability constants of the complex formed with receptor B and a series of anions (Cl", Br , 1") were evaluated in CDCI3 using NMR titration techniques. Receptor B binds all the screened halides with a measurable but modest association constant. The association constants measured were 20 for... 

The association constant measures acid or base strength, but because of ion association there is no unique scale in solvents of low dielectric constant (sect. 3.7). Nor are satisfactory acidity functions possible in these solvents. Different acids can be compared only with respect to their reaction with some chosen base. The stronger the proton acceptor or... 

Next, the chiral recognition of enantiomeric anions of mandelic acid and N-Boc-protected tryptophane by three receptors 24-26 was also investigated. The receptors 24 and 25 showed no noticeable chiral recognition. On the other hand, association constants measured for 26 were 343 (D-Trp-COO ) and 190 (L-Trp-COO ). Additionally, for their... 

Outer-sphere association constants measured for the [Fe(dipic)2] reduction of binuclear cobalt(III) complexes (2), [Co(III)2] with stacking ligands,... 

Cryptophanes 5 and 6 (Fig. 21.4) with larger internal cavities have also demrai-strated their ability to bind Cs and Tl cations in water efficiently under analogous experimental conditions (LiOH/H20 (0.1 M)). The Cs NMR spectra of Cs 5 and Cs" 6 in 0.1 M NaOD/D20 solutions are characterized by two highfield-shifted signals located at 270 and 290 ppm respectively. However, these two complexes behave differently when the temperature increases. The association constants measured by titration experiments at 298 K are still very high for 5 ATa = 3.1xl0° M for the Cs+ 5 complex (AG°= 13.2 kcal/mol) and... 

One can write acid-base equilibrium constants for the species in the inner compact layer and ion pair association constants for the outer compact layer. In these constants, the concentration or activity of an ion is related to that in the bulk by a term e p(-erp/kT), where yp is the potential appropriate to the layer [25]. The charge density in both layers is given by the algebraic sum of the ions present per unit area, which is related to the number of ions removed from solution by, for example, a pH titration. If the capacity of the layers can be estimated, one has a relationship between the charge density and potential and thence to the experimentally measurable zeta potential [26]. 

Specific Conductance. The specific conductance depends on the total concentration of the dissolved ioni2ed substances, ie, the ionic strength of a water sample. It is an expression of the abiUty of the water to conduct an electric current. Freshly distilled water has a conductance of 0.5—2 ]lS/cm, whereas that of potable water generally is 50—1500 ]lS/cm. The conductivity of a water sample is measured by means of an a-c Wheatstone-bridge circuit with a null indicator and a conductance cell. Each cell has an associated constant which, when multiphed by the conductance, yields the specific conductance. 

It has been shown that the polarizability of a substance containing no dipoles will indicate the strength o/any dispersive interactions that might take place with another molecule. In comparison, due to self-association or internal compensation that can take place with polar materials, the dipole moment determined from bulk dielectric constant measurements will often not give a true indication of the strength of any polar interaction that might take place with another molecule. An impression of a dipole-dipole interaction is depicted in Figure 11. 

Chaput, Jeminet and Juillard measured the association constants of several simple polyethylene glycols with Na", K", Cs", and Tl". Phase transfer catalytic processes and most biological processes are more likely to involve the first two cations rather than the latter two, so we will confine the discussion to these. Stability constants for the dimethyl ethers of tetra-, penta-, hexa-, and heptaethylene glycols were determined poten-tiometrically in anhydrous methanol solution and are shown in Table 7.1. In the third column of the table, the ratio of binding constants (Ks/K s) is calculated. Note that Simon and his coworkers have referred to this ratio as the selectivity constant. ... 

Purification of solvents and salts is essential for reliable electrochemical studies and measurements. A water content of 20ppm already corresponds to a 10 3molL solution. This is in the concentration range of dilute solutions used in conductivity studies for the determination of association constants (see Sec.7.3.2). Traces of water may affect chemical equilibria and therefore act on specific conductivities and limiting ion conductivities. For example, addition of 30 ppm water to a 2xl0-4 mol LT1 solution of LiBF4 in THF at 15 °C increases its conductivity by 4.4 percent (precision of measurements about 0.02 percent) 380 ppm water causes an increase by 51.7 percent see Fig. 3 [20J. 

The commonly used method for the determination of association constants is by conductivity measurements on symmetrical electrolytes at low salt concentrations. The evaluation may advantageously be based on the low-concentration chemical model (lcCM), which is a Hamiltonian model at the McMillan-Mayer level including short-range nonelectrostatic interactions of cations and anions [89]. It is a feature of the lcCM that the association constants do not depend on the physical... 

Conductivity measurements yield molar conductivities A (Scm2 mol-1) at salt concentration c (mol L-1). A set of data pairs (Af, c,), is evaluated with the help of non linear fits of equations [89,93,94] consisting of the conductivity equation, Eq. (7), the expression for the association constant, Eq. (3), and an equation for the activity coefficient of the free ions in the solution, Eq.(8) the activity coefficient of the ion pair is neglected at low concentrations. 

The pioneering work of Gilkerson and co-workers [122-130] and Huyskens and colleagues [131,132] allows the determination of the corresponding equilibrium constants from conductivity measurements. If all equilibria, Eq. (4)-(6), are involved, the association constants of an electrolyte without (K l) and with (KA ) addition of the ligand at concentration cL of the ligand L are given by the relationship [132]... 

The results are in accordance with those obtained by Taft and colleagues80,81. These authors have measured the 19F NMR chemical shifts of p-FC6H4OH in the presenceof 60 bases including sulphoxides (DMSO, methyl phenyl, methyl p-nitrophenyl, diphenyl, tetramethylene sulphoxide) and determined the association constants K for the hydrogen bond shown in equation 15. 

A case similar to the slow, practically irreversible inhibition of jack bean a-D-mannosidase by swainsonine is represented by the interaction of castanospermine with isomaltase and rat-intestinal sucrase. Whereas the association constants for the formation of the enzyme-inhibitor complex were similar to those of other slow-binding glycosidase inhibitors (6.5 10 and 0.3 10 M s for sucrase and isomaltase, respectively), the dissociation constant of the enzyme-inhibitor complex was extremely low (3.6 10 s for sucrase) or could not be measured at all (isomaltase), resulting in a virtually irreversible inhibition. Danzin and Ehrhard discussed the strong binding of castanospermine in terms of the similarity of the protonated inhibitor to a D-glucosyl oxocarbenium ion transition-state, but were unable to give an explanation for the extremely slow dissociation of the enzyme-inhibitor complex. 

On the other hand, Arnett and his coworkers have reported both the enthalpies of the protonation (AHJ and the hydrogen bond (AHf) for acid-base reactions. They calculated Hj by measuring the association constants for the proton transfer (ionization) in a number of bases by using FSO3H as the acid and determined Ai/j by calorimetric measurements of the heat of dissolution of P-FC6H4OH in various hydrogen bond acceptors, including sulphoxides, in They have also tried to correlate and... 

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