Ionic mobilities, concentrated solutions

Defined as the reciprocal of resistance (siemens, ft-1) conductance is a measure of ionic mobility in solution when the ions are subjected to a potential gradient. The equivalent conductance A of an ion is defined as the conductance of a solution of unspecified volume containing one gram-equivalent and measured between electrodes I cm apart. Due to interionic effects, A is concentration dependent, and the value, A0, at infinite dilution is used for comparison purposes. The magnitude of A0 is determined by the charge, size and degree of hydration of the ion values for a number of cations and anions at 298.15K are given in table 6.6. It should be noted that HjO and... 

Migration is the movement of ions due to a potential gradient. In an electrochemical cell the external electric field at the electrode/solution interface due to the drop in electrical potential between the two phases exerts an electrostatic force on the charged species present in the interfacial region, thus inducing movement of ions to or from the electrode. The magnitude is proportional to the concentration of the ion, the electric field and the ionic mobility. 

Table 8.2 lists the conductivities, transport numbers and molar conductivities of the electrolyte A = olc, and ions Xj = t+A for a number of melts as weU as for 0.1 M KCl solution. Melt conductivities are high, but the ionic mobilities are much lower in ionic liquids than in aqueous solutions the high concentrations of the ions evidently give rise to difficulties in their mutual displacement. 

Diffusion of ions can be observed in multicomponent systems where concentration gradients can arise. In individnal melts, self-diffnsion of ions can be studied with the aid of radiotracers. Whereas the mobilities of ions are lower in melts, the diffusion coefficients are of the same order of magnitude as in aqueous solutions (i.e., about 10 cmVs). Thus, for melts the Nemst relation (4.6) is not applicable. This can be explained in terms of an appreciable contribntion of ion pairs to diffusional transport since these pairs are nncharged, they do not carry cnrrent, so that values of ionic mobility calculated from diffusion coefficients will be high. 

An ion-selective electrode contains a semipermeable membrane in contact with a reference solution on one side and a sample solution on the other side. The membrane will be permeable to either cations or anions and the transport of counter ions will be restricted by the membrane, and thus a separation of charge occurs at the interface. This is the Donnan potential (Fig. 5 a) and contains the analytically useful information. A concentration gradient will promote diffusion of ions within the membrane. If the ionic mobilities vary greatly, a charge separation occurs (Fig. 5 b) giving rise to what is called a diffusion potential. 

Adsorption is a physicochemical process whereby ionic and nonionic solutes become concentrated from solution at solid-liquid interfaces.3132 Adsorption and desorption are caused by interactions between and among molecules in solution and those in the structure of solid surfaces. Adsorption is a major mechanism affecting the mobility of heavy metals and toxic organic substances and is thus a major consideration when assessing transport. Because adsorption is usually fully or partly reversible (desorption), only rarely can it be considered a detoxification process for fate-assessment purposes. Although adsorption does not directly affect the toxicity of a substance, the substance may be rendered nontoxic by concurrent transformation processes such as hydrolysis and biodegradation. Many chemical and physical properties of both aqueous and solid phases affect adsorption, and the physical chemistry of the process itself is complex. For example, adsorption of one ion may result in desorption of another ion (known as ion exchange). 

The value for k will normally decrease as the concentration of the solution decreases but the value for A will increase because of the increased dissociation of molecules in dilute solutions. A value for the molar conductance at infinite dilution (A,)) can be determined by plotting the calculated values for A against the molar concentration of the solution used and determining the plateau value for A. From such investigations it is possible to determine the ionic mobilities of ions (Table 4.3) and calculate the molar conductance of an... 

According to Kohlrausch, the concentration c, of a solute i in the adjacent zone can be calculated from the concentration clead of the leading buffer and the ratio of the ionic mobilities u, and ulead, with uc being the ionic mobility of the counterion. That means that zones with lower concentration than the leading buffer are concentrated (sharpened) and that zones of higher concentration are diluted (broadened). 

In MACE, the alteration of the ionic mobility as a factor of the tenside concentration in the background electrolyte solution is a measure of the strength of interaction, which may be evaluated graphically. In Fig. 1, a schematic representation of MEKC is given for the separation of micelle and EOF markers as well as drug solutes of different lipophilicity. If the substances are neutral, their position between the EOF marker and the micelle marker is given only by their lipophilicity, which controls their affinity to the micellar phase. This means that S3 in Fig. 1 has the lowest hydrophilicity. 

For Eq. (2) it is assumed that the volume of the micellar phase is proportional to the tenside concentration and that the partial molar volume v remains constant. (See Chapter 2.) A further prerequisite for the application of Eq. (2) is a constant ionic mobility of the micellar phase independent of the uptake of a solute (/x, . = const.). In contrast to HPLC, substances that have an infinitely high kP value, i.e., that are completely dissolved in the micellar phase, can be detected. In this case the sample molecule migrates with the mobility of the micelle. In the presence of several different micellar phases (coexistence of simple and mixed micelles), the calculation of kP is possible only when partial capacity factors are known (20). The determination of kP is then considerably more complicated. 

C. Concentration Dependence of Ionic Mobility and Viscosity of Electrolyte Solutions... 

Combined with densities, molecular weights, and transference numbers (fractions of the current carried by the various ionic constituents), the conductivity yields the relative velocities of the ionic constituents under the influence of an electric field. The mobilities (velocity per unit electric field, cm2 s-1 V-1) depend on the size and charge of the ion, the ionic concentration, temperature, and solvent medium. In dilute aqueous solutions of dissociated electrolytes, ionic mobilities decrease slightly as the concentration increases. The equivalent conductance extrapolated to zero electrolyte concentration may be expressed as the sum of independent equivalent conductances of the constituent ions... 

In this way we eliminate errors resulting from the application of equation (III-26), which is based on the assumption that ionic mobility is independent on the concentration of the solution. Equation (III-27) may be regarded as correct, because we compare now conductances of a partly dissociated (real) solution and of a fully dissociated (hypothetical) solution at the same ion concentration, in which case the interionic forces have the same influence upon the velocity of ions. 

We distinguish between concentration cells without and with transference. In the first type the solutions surrounding both electrodes arc not brought into direct contact, while in concentration cells with transference two solutions arc in direct contact. The name cell with transference originates from the fact that during flow of the current a simultaneous transfer of the electrolyte takes place owing to the different ionic mobility. In the case of cells without transference the direct transfer of the electrolyte from one solution to the other is prevented in this instance the transport of the electromotive active substance proceeds exclusively as a result of reactions taking place at the electrodes. 

Equivalent conductivities (and ionic mobilities) of the melts are similar to that of aqueous solutions. Very high specific conductivities are typical for molten salts, as seen in Table 1 [49], The reason for this is the fact that molten salts are very concentrated solutions (for example, the concentration of molten LiF is about 65 molar the concentration of molten KC1 is about 20 molar, etc.). The electrical conductivities of various molten salts cannot be compared at constant temperature because of their different melting points. Therefore, in Table 1 the values of conductivities were selected at 50° above the melting point of each salt. 

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