Electrical Conduction in Electrolyte Solutions

Electric currents in metallic conductors and semiconductors are due to the motions of electrons, whereas electric currents in electrolyte solutions are due to the motions of ions. Ohm s law asserts that the current in a conducting system is proportional to the voltage imposed on the system  

The SI unit of resistivity is the ohm meter (ohm m). The reciprocal of the resistivity is called the conductivity and denoted by a  

Shoemaker, C. W. Garland, and J. W. Nibler, Experiments in Physical Chemistry, 5th ed., McGraw-Hill, New York, 1989, p. 132ff. 

The conductivity has the units ohm spelled backwards) but the SI name for ohm is the siemens, denoted by S, so that the conductivity has the units Siemens per meter (S m ). 

We define the current density j as a vector with magnitude equal to the current per unit area and with the same direction as the current  

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In practice, a porous electrically insulating material containing the electrolyte is often placed between the anode and cathode to prevent the anode from directly contacting the cathode. Should the anode and cathode physically touch, the battery will be shorted and its full energy released as heat inside the battery. Electrical conduction in electrolytic solutions follows Ohm s law E = IR. 

The electrical conduction in a solution, which is expressed in terms of the electric charge passing across a certain section of the solution per second, depends on (i) the number of ions in the solution (ii) the charge on each ion (which is a multiple of the electronic charge) and (iii) the velocity of the ions under the applied field. When equivalent conductances are considered at infinite dilution, the effects of the first and second factors become equal for all solutions. However, the velocities of the ions, which depend on their size and the viscosity of the solution, may be different. For each ion, the ionic conductance has a constant value at a fixed temperature and is the same no matter of which electrolytes it constitutes a part. It is expressed in ohnT1 cm-2 and is directly proportional to the mobilities or speeds of the ions. If for a uni-univalent electrolyte the ionic mobilities of the cations and anions are denoted, respectively, by U+ and U, the following relationships hold ... 

We can recognize four main periods in the history of the study of aqueous solutions. Each period starts with one or more basic discoveries or advances in theoretical understanding. The first period, from about 1800 to 1890, was triggered by the discovery of the electrolysis of water followed by the investigation of other electrolysis reactions and electrochemical cells. Developments during this period are associated with names such as Davy, Faraday, Gay-Lussac, Hittorf, Ostwald, and Kohlrausch. The distinction between electrolytes and nonelectrolytes was made, the laws of electrolysis were quantitatively formulated, the electrical conductivity of electrolyte solutions was studied, and the concept of independent ions in solutions was proposed. 

As an example of this, consider the three compounds obtained from hexammino-eobaltie chloride by replacing ammonia by nitrito-groups. The same total number of acidic radicles is retained in the molecule, but the derivatives differ in electrical conductivity in equivalent solutions. The molecular conductivity of hexammino-eobaltie chloride at 25° C. and 1000 litres dilution is 431-6 of the mononitrito-derivative, [Co(NH3)5(N02)]C12, is 246-4 of the di-derivative, [Co(NH3)4(N02)2]C1, is 98-83 and of the trinitrito-derivative, [Co(NH3)3(N02)3], is zero, this being a non-electrolyte. Further substitution transforms the complex from cation to anion thus [Co(NH3).2(N02)4]K. 

Traceability structures for gas analysis, clinical chemistry, pH measurement and electrical conductivity of electrolyte solutions in Germany... 

Electrochemical behaviour of fullerenes in solutions depends in part upon the electric properties of the solvent, in this instance toluene. However toluene is an aprotic solvent with a low dielectric constant (s 2.7) resulting in a high electrical resistance of a cell and, consequently, the absence of electrical conduction in the solution. Ethanol has been used as the base electrolyte to ensure electrical conduction in the toluene-fullerene (TF) solution. 

Electrical conductivity is a critical issue in nonaqueous electrochemistry, since the use of nonaqueous solvents, which are usually less polar than water, means worse electrolyte dissolution, worse charge separation, and, hence, worse electrical conductivity compared with aqueous solutions. In this section, a short course on electrical conductivity in liquid solutions is given, followed by several useful tables summarizing representative data on solution conductivity and conductivity parameters. 

The electrical conductance of electrolyte solutions is measured under isothermal, isobaric conditions with uniform concentration throughout the cell, in which case jik = 0 and Eq. (13.7.8) becomes... 

I 7 Detection Methods in Ion Chromatography 7.1.1.1 Theoretical Principles Electric conductivity of electrolyte solutions [1]... 

In this book, we will discuss the electric conductivity of electrolyte solutions, ionomers, ion-conducting ceramics, and metals but will skip semiconductors. 

Electric conductivity of electrolyte solutions strongly depends on temperature. To a certain point, typically the conductance is increasing due to decreasing viscosity of solvent. There are, however, counteracting factors. In aqueous solution, e.g. above 90 °C, the conductance is decreasing due to decreasing dielectric constant of the solvent [37]. The solvent shell is reduced, and ionic interactions tend to affect the mobility of ions more and more. 

For more than a century, a number of different aluminum alloys have been commonly used in the aircraft industry These substrates mainly contain several alloying elements, such as copper, chromium, iron, nickel, cobalt, magnesium, manganese, silicon, titanium and zinc. It is known that these metals and alloys can be dissolved as oxides or other compounds in an aqueous medium due to the chemical or electrochemical reactions between their metal surfaces and the environment (solution). The rate of the dissolution from anode to cathode phases at the metal surfaces can be influenced by the electrical conductivity of electrolytic solutions. Thus, anodic and cathodic electron transfer reactions readily exist with bulk electrolytes in water and, hence, produce corrosive products and ions. It is known that pure water has poor electrical conductivity, which in turn lowers the corrosion rate of materials however, natural environmental solutions (e g. sea water, acid rains, emissions or pollutants, chemical products and industrial waste) are highly corrosive and the environment s temperature, humidity, UV light and pressure continuously vary depending on time and the type of process involved. ... 

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 ... 

The electrical conductance of a solution is a measure of its current-carrying capacity and is therefore determined by the total ionic strength. It is a nonspecific property and for this reason direct conductance measurements are of little use unless the solution contains only the electrolyte to be determined or the concentrations of other ionic species in the solution are known. Conductometric titrations, in which the species of interest are converted to non-ionic forms by neutralization, precipitation, etc. are of more value. The equivalence point may be located graphically by plotting the change in conductance as a function of the volume of titrant added. 

When the relative permittivity of the organic solvent or solvent mixture is e < 10, then ionic dissociation can generally be entirely neglected, and potential electrolytes behave as if they were nonelectrolytes. This is most clearly demonstrated experimentally by the negligible electrical conductivity of the solution, which is about as small as that of the pure organic solvent. The interactions between solute and solvent in such solutions have been discussed in section 2.3, and the concern here is with solute-solute interactions only. These take place mainly by dipole-dipole interactions, hydrogen bonding, or adduct formation. 

Electrical Conductance of Aqueous Solutions of Ammonia and Metal Hydroxides. Check the electrical conductance of 1 W solutions of sodium hydroxide, potassium hydroxide, and ammonia. Record the ammeter readings. Arrange the studied alkalies in a series according to their activity. Acquaint yourself with the degree of dissociation and the dissociation constants of acids and bases (see Appendix 1, Tables 9 and 10). Why is the term apparent degree of dissociation used to characterize the dissociation of strong electrolytes ... 

With the decrease in permittivity, however, complete dissociation becomes difficult. Some part of the dissolved electrolyte remains undissociated and forms ion-pairs. In low-permittivity solvents, most of the ionic species exist as ion-pairs. Ion-pairs contribute neither ionic strength nor electric conductivity to the solution. Thus, we can detect the formation of ion-pairs by the decrease in molar conductivity, A. In Fig. 2.12, the logarithmic values of ion-association constants (log KA) for tetrabutylammonium picrate (Bu4NPic) and potassium chloride (KC1) are plotted against (1 /er) [38]. 

Other physical phenomena that may be associated, at least partially, with complex formation are the effect of a salt on the viscosity of aqueous solutions of a sugar and the effect of carbohydrates on the electrical conductivity of aqueous solutions of electrolytes. Measurements have been made of the increase in viscosity of aqueous sucrose solutions caused by the presence of potassium acetate, potassium chloride, potassium oxalate, and the potassium and calcium salt of 5-oxo-2-pyrrolidinecarboxylic acid.81 Potassium acetate has a greater effect than potassium chloride, and calcium ion is more effective than potassium ion. Conductivities of 0.01-0.05 N aqueous solutions of potassium chloride, sodium chloride, potassium sulfate, sodium sulfate, sodium carbonate, potassium bicarbonate, potassium hydroxide, and sodium hydroxide, ammonium hydroxide, and calcium sulfate, in both the presence and absence of sucrose, have been determined by Selix.88 At a sucrose concentration of 15° Brix (15.9 g. of sucrose/100 ml. of solution), an increase of 1° Brix in sucrose causes a 4% decrease in conductivity. Landt and Bodea88 studied dilute aqueous solutions of potassium chloride, sodium chloride, barium chloride, and tetra-... 

Electrical conductivity measures a material s ability to conduct an electric current. The high conductivity of metals is due to the presence of metallic bonds. The high conductivity of electrolyte solutions is due to the presence of ions in solution. 

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