Electrically Conducting Species

It is not as easy as it appears to know whieh are the eleetrieally conducting species in molten salts. It seems to be nearly impossible to determine the electrically conducting species by experiment alone.  

It is still controversial whether these species are associated or nonas-sociated. Three models in this respect are introduced here. 

Chemla s group proposed an associated model more than 30 years ago for the purpose of interpreting the Chemla effect soon after its discovery. For example, the following chemical equilibria were considered  

Based on quite similar equilibria for the nitrate system (Li, K)N03, Lantelme and Chemla quantitatively estimated the existing species so that the experimental mobilities and self-diffusion coefficients could be obtained consistently. This could be successfully done. However, no direct evidence has been obtained yet that such species as [LiBrn] and are really electrically conducting species. 

According to the model proposed by Klemm and Schafer, - the Chemla effect is explained qualitatively. Although molten LiBr has a 

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This model is similar to the associated species model in that a chemical equilibrium is assumed between existing species, and it is different in that in the latter only a nonassociated ionic species is assumed to be the electrically conducting species. 

The dynamic dissociation model resembles the association (or dissociation) model in that electrically conducting species are assumed to he nonassociated species, and it differs from the association model in that in the dynamic dissociation model the dissociation process itself is the electrically conducting process, while in the association model, the amount of the dissociated species is constant according to the chemical equilibrium. 

A useful technique for the precipitation of relatively insoluble electrolytes is the stopped-flow method (Sohnel and Mullin, 1978b). If two stable solutions, which react to form a supersaturated solution of the reactant, are mixed together instantaneously, no detectable changes occur for some time. However, as soon as the reactant starts to precipitate the concentration of the electrically conductive species begins to decrease and this causes the solution conductivity to diminish. The period of conductivity steadiness is inversely proportional to the supersaturation, and for highly supersaturated solutions it can be less than a millisecond. 

In an excess of nitric acid, nitrous acid exists essentially as dinitrogen tetroxide which, in anhydrous nitric acid, is almost completely ionised. This is shown by measurements of electrical conductivity, and Raman and infra-red spectroscopy identify the ionic species... 

Electrical Resistance—Conductivity. Most fillers are composed of nonconducting substances that should, therefore, provide electrical resistance properties comparable to the plastics in which they are used. However, some fillers contain adsorbed water or other conductive species that can gready reduce their electrical resistance. Standard tests for electrical resistance of filled plastics include dielectric strength, dielectric constant, arc resistance, and d-c resistance. 

The composition to the melting point is estimated to be 65% Na AlF, 14% NaF, and 21% NaAlF [1382-15-3], The ions Na" and F ate the principal current carrying species in molten cryoHte whereas the AIF is less mobile. The stmctural evidences are provided by electrical conductivity, density, thermodynamic data, cryoscopic behavior, and the presence of NaAlF in the equiUbtium vapor (19,20). 

To calculate electron production must be balanced against electron depletion. Free electrons in the gas can become attached to any of a number of species in a combustion gas which have reasonably large electron affinities and which can readily capture electrons to form negative ions. In a combustion gas, such species include OH (1.83 eV), O (1.46 eV), NO2 (3.68 eV), NO (0.09 eV), and others. Because of its relatively high concentration, its abUity to capture electrons, and thus its abUity to reduce the electrical conductivity of the gas, the most important negative ion is usuaUyOH . 

Bismuth Trichloride. Bismuth(III) chloride is a colodess, crystalline, dehquescent soHd made up of pyramidal molecules (19). The nearest intermolecular Bi—Cl distances are 0.3216 nm and 0.3450 nm. The density of the soHd is 4.75 g/mL and that of the Hquid at 254°C is 3.851 g/mL. The vapor density corresponds to that of the monomeric species. The compound is monomeric in dilute ether solutions, but association occurs at concentrations greater than 0.1 Af. The electrical conductivity of molten BiCl is of the same order of magnitude as that found for ionic substances. 

These equilibria effect a rapid exchange of N atoms between the various species and only a single N nmr signal is seen at the weighted average position of HNO3, [NOa]" " and [N03]. They also account for the high electrical conductivity of the pure (stoichiometric) liquid (Table 11.13), and are an important factor in the chemical reactions of nitric acid and its non-aqueous solutions see below. 

Ionic liquids possess a variety of properties that make them desirable as solvents for investigation of electrochemical processes. They often have wide electrochemical potential windows, they have reasonably good electrical conductivity and solvent transport properties, they have wide liquid ranges, and they are able to solvate a wide variety of inorganic, organic, and organometallic species. The liquid ranges of ionic liquids have been discussed in Section 3.1 and their solubility and solvation in... 

The Mechanism of Electrical Conduction. Let us first give some description of electrical conduction in terms of this random motion that must exist in the absence of an electric field. Since in electrolytic conduction the drift of ions of either sign is quite similar to the drift of electrons in metallic conduction, we may first briefly discuss the latter, where we have to deal with only one species of moving particle. Consider, for example, a metallic bar whose cross section is 1 cm2, and along which a small steady uniform electric current is flowing, because of the presence of a weak electric field along the axis of the bar. Let the bar be vertical and in Fig. 16 let AB represent any plane perpendicular to the axis of the bar, that is to say, perpendicular to the direction of the cuirent. 

Electrical methods of analysis (apart from electrogravimetry referred to above) involve the measurement of current, voltage or resistance in relation to the concentration of a certain species in solution. Techniques which can be included under this general heading are (i) voltammetry (measurement of current at a micro-electrode at a specified voltage) (ii) coulometry (measurement of current and time needed to complete an electrochemical reaction or to generate sufficient material to react completely with a specified reagent) (iii) potentiometry (measurement of the potential of an electrode in equilibrium with an ion to be determined) (iv) conductimetry (measurement of the electrical conductivity of a solution). 

Ion chromatography (IC) is a relatively new technique pioneered by Small et al.25 and which employs in a novel manner some well-established principles of ion exchange and allows electrical conductance to be used for detection and quantitative determination of ions in solution after their separation. Since electrical conductance is a property common to all ionic species in solution, a conductivity detector clearly has the potential of being a universal monitor for all ionic species. 

Measurements of electrical conductivity permit the identification of the charge-carrying species in the solid phase and also the detection of ionic melts [111,417]. Bradley and Greene [418], for example, could determine the kinetics of reactions between Agl, KI and Rbl because the product (K, Rb)Ag4Is had a considerably higher conductivity than the reactants. The conductivity of the reactant mixture was proportional to the thickness of the product layer. 

Although a free ionic end-group, —CH2CH(Ph), capable of propagating polymerization is formed on opening the ring, the resulting dipolar species does not contribute to electric conductance. 

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