Electrolytic solutions electrical conduction

Many of the reactions that you will study occur in aqueous solution. Water is called the universal solvent, because it dissolves so many substances. It readily dissolves ionic compounds as well as polar covalent compounds, because of its polar nature. Ionic compounds that dissolve in water (dissociate) form electrolyte solutions, which conduct electrical current owing to the presence of ions. The ions can attract the polar water molecules and form a bound layer of water molecules around themselves. This process is called solvation. Refer to the Solutions and Periodicity chapter for an in-depth discussion of solvation. 

A solvent, in addition to permitting the ionic charges to separate and the electrolyte solution to conduct an electrical current, also solvates the discrete ions, by ion-dipole or ion-induced dipole interactions and by more direct interactions, such as hydrogen bonding to anions or electron-pair donation to cations. Lewis acidity and basicity of the solvents affect the latter. The redox properties of the ions at an electrode depend on their being solvated, and the solvation effects electrode potentials or polarographic half-wave potentials. 

Figure 5.38 shows an electrolyte solution between two plane electrodes. The conductivity of the solution (ic) is expressed by k=L/AR, where L is the distance between the two electrodes (cm), A the electrode area (cm2), and R the electrical resistance of the solution (fi). For dilute electrolyte solutions, the conductivity k is proportional to the concentrations of the constituent ions, as in Eq. (5.39) ... 

A flashlight battery is an electrochemical cell. An electrochemical cell consists of two electrodes separated by an electrolyte. An electrode is a conductor that connects with a nonmetallic part of a circuit. You have learned about two kinds of conductors. One kind includes metals, which conduct electric current through moving electrons. The second kind includes electrolyte solutions, which conduct through moving ions. 

Electrolytic conductivity is the ability of an electrolytic solution to conduct electricity between two electrodes across which an electric field is applied. Ohm s law, V = I R, is obeyed and the magnitude of the current depends, in part, on the magnitude of the applied potential. The conductance, G, of a solution is expressed in terms of the solution electrolytic resistance. It is measured in reciprocal ohms (mhos) or in the SI unit siemens (S). 

When asked what causes electrolyte solutions to conduct electricity, a student responds that it is due to the movement of electrons through the solution. Is the student correct If not, what is the correct response ... 

Electrolytic conductivity is the ability of an electrolytic solution to conduct electricity between two electrodes across which an electric field is appHed. Ohm s law,... 

Let ns snmmarize the main points in this section. Compounds that dissolve in water are soluble those that dissolve little, or not at all, are insoluble. Soluble substances are either electrolytes or nonelectrolytes. Nonelectrolytes form noncon-dncting aqneons solutions because they dissolve completely as molecules. Electrolytes form electrically conducting solutions in water because they dissolve to give ions in solntion. Electrolytes can be strong or weak. Almost all soluble ionic substances are strong electrolytes. Soluble molecular substances usually are nonelectrolytes or weak electrolytes the latter solution consists primarily of molecules, but has a small percentage of ions. Ammonia, NH3, is an example of a molecular substance that is a weak electrolyte. A few molecular substances (such as HCl) dissolve almost entirely as ions in the solution and are therefore strong electrolytes. The solubility rules can be used to predict the solubility of ionic compounds in water. 

In order to make the solution electrically conductive and to enable the electrolytic process it is necessary to add an indifferent electrolyte to the solution. As a rule salts of alkali metals or alkyl-ammonium bases are used. The concentration of these salts in the investigated solutions amounts to 10 mole /liter. It is comparatively easy to create such a concentration of indifferent electrolyte in aqueous media by alkali metal salts. In nonaqueous solvents this is not always possible for alkali metal salts various alkylammonium salts, which have better solubility, are therefore used instead. 

The metallic salts of trifluoromethanesulfonic acid can be prepared by reaction of the acid with the corresponding hydroxide or carbonate or by reaction of sulfonyl fluoride with the corresponding hydroxide. The salts are hydroscopic but can be dehydrated at 100°C under vacuum. The sodium salt has a melting point of 248°C and decomposes at 425°C. The lithium salt of trifluoromethanesulfonic acid [33454-82-9] CF SO Li, commonly called lithium triflate, is used as a battery electrolyte in primary lithium batteries because solutions of it exhibit high electrical conductivity, and because of the compound s low toxicity and excellent chemical stabiUty. It melts at 423°C and decomposes at 430°C. It is quite soluble in polar organic solvents and water. Table 2 shows the electrical conductivities of lithium triflate in comparison with other lithium electrolytes which are much more toxic (24). 

Disadvantages associated with some organic solvents include toxicity flammabiHty and explosion ha2ards sensitivity to moisture uptake, possibly leading to subsequent undesirable reactions with solutes low electrical conductivity relatively high cost and limited solubiHty of many solutes. In addition, the electrolyte system can degrade under the influence of an electric field, yielding undesirable materials such as polymers, chars, and products that interfere with deposition of the metal or alloy. 

C), (cmVohm geqmv) K = Ci/R = specific conductance, (ohm cm) h C = solution concentration, (gequiv/ ) Ot = conductance cell constant (measured), (cm ) R = solution electrical resistance, which is measured (ohm) and/(C) = a complicated function of concentration. The resulting equation of the electrolyte diffusivity is... 

Numerous proprietary electrolytes have been developed for the production of harder and brighter deposits. These include acid, neutral and alkaline solutions and cyanide-free formulations and the coatings produced may be essentially pure, where maximum electrical conductivity is required, or alloyed with various amounts of other precious or base metals, e.g. silver, copper, nickel, cobalt, indium, to develop special physical characteristics. 

Silver is often preferred as an undercoat for rhodium by reason of its high electrical conductivity. A further advantage of silver in the case of the thicker rhodium deposits (0-0025 mm) applied to electrical contacts for wear resistance is that the use of a relatively soft undercoat permits some stress relief of the rhodium deposit by plastic deformation of the under-layer, and hence reduces the tendency to cracking , with a corresponding improvement in protective value. Nickel, on the other hand, may be employed to provide a measure of mechanical support, and hence enhanced wear resistance, for a thin rhodium deposit. A nickel undercoating is so used on copper printed connectors, where the thickness of rhodium that may be applied from conventional electrolytes is limited by the tendency of the plating solution to attack the copper/laminate adhesive, and by the lifting effect of internal stress in the rhodium deposit. 

Electrolyte Solution a solution in which the conduction of electric current occurs by the passage of dissolved ions. 

Complete and Incomplete Ionic Dissociation. Brownian Motion in Liquids. The Mechanism of Electrical Conduction. Electrolytic Conduction. The Structure of Ice and Water. The Mutual Potential Energy of Dipoles. Substitutional and Interstitial Solutions. Diffusion in Liquids. 

When an ionic solution contains neutral molecules, their presence may be inferred from the osmotic and thermodynamic properties of the solution. In addition there are two important effects that disclose the presence of neutral molecules (1) in many cases the absorption spectrum for visible or ultraviolet light is different for a neutral molecule in solution and for the ions into which it dissociates (2) historically, it has been mainly the electrical conductivity of solutions that has been studied to elucidate the relation between weak and strong electrolytes. For each ionic solution the conductivity problem may be stated as follows in this solution is it true that at any moment every ion responds to the applied field as a free ion, or must we say that a certain fraction of the solute fails to respond to the field as free ions, either because it consists of neutral undissociated molecules, or for some other reason ... 

Incomplete Dissociation into Free Ions. As is well known, there are many substances which behave as a strong electrolyte when dissolved in one solvent, but as a weak electrolyte when dissolved in another solvent. In any solvent the Debye-IIiickel-Onsager theory predicts how the ions of a solute should behave in an applied electric field, if the solute is completely dissociated into free ions. When we wish to survey the electrical conductivity of those solutes which (in certain solvents) behave as weak electrolytes, we have to ask, in each case, the question posed in Sec. 20 in this solution is it true that, at any moment, every ion responds to the applied electric field in the way predicted by the Debye-Hiickel theory, or does a certain fraction of the solute fail to respond to the field in this way In cases where it is true that, at any moment, a certain fraction of the solute fails to contribute to the conductivity, we have to ask the further question is this failure due to the presence of short-range forces of attraction, or can it be due merely to the presence of strong electrostatic forces ... 

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