Electrical conductivity dissociated electrolytes

Other properties of aqueous solutions have been studied, such as the density,13 vapour-pressure,14 boiling-point,15 molecular depression of the freezing-point,16 electric conductivity,17 electrolytic dissociation,18... 

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 ... 

An interface between two immiscible electrolyte solutions (ITIES) is formed between two liqnid solvents of a low mutual miscibility (typically, <1% by weight), each containing an electrolyte. One of these solvents is usually water and the other one is a polar organic solvent of a moderate or high relative dielectric constant (permittivity). The latter requirement is a condition for at least partial dissociation of dissolved electrolyte(s) into ions, which thus can ensure the electric conductivity of the liquid phase. A list of the solvents commonly used in electrochemical measurements at ITIES is given in Table 32.1. 

Let the electrolysis of dilute sulfuric acid (so-called electrolysis of water) with a platinum cathode and a platinum anode be considered next. Pure water is a very weak electrolyte and consequently a very poor conductor of electricity. It dissociates very slightly into H+ ions (it may be recalled that in fact, H+ ions does not remain as such but forms hydronium in H30+ by combining with a molecule of water, H+ + H20 H30+) and OFT ions. In the presence of little sulfuric acid (or for that matter any other strong electrolyte) the conductivity, i.e., ionization is greatly increased. The acidified water now contains H+ ions, OFT and SC3 ions. During electrolysis with platinum electrodes, H+ ions are attracted to the cathode, where each ion gains an electron and becomes a hydrogen atom ... 

Arrhenius postulated in 1887 that an appreciable fraction of electrolyte in water dissociates to free ions, which are responsible for the electrical conductance of its aqueous solution. Later Kohlrausch plotted the equivalent conductivities of an electrolyte at a constant temperature against the square root of its concentration he found a slow linear increase of A with increasing dilution for so-called strong electrolytes (salts), but a tangential increase for weak electrolytes (weak acids and bases). Hence the equivalent conductivity of an electrolyte reaches a limiting value at infinite dilution, defined as... 

The electroneutrality condition decreases the number of independent variables in the system by one these variables correspond to components whose concentration can be varied independently. In general, however, a number of further conditions must be maintained (e.g. stoichiometry and the dissociation equilibrium condition). In addition, because of the electroneutrality condition, the contributions of the anion and cation to a number of solution properties of the electrolyte cannot be separated (e.g. electrical conductivity, diffusion coefficient and decrease in vapour pressure) without assumptions about individual particles. Consequently, mean values have been defined for a number of cases. 

The electrical conductivity of BaS04 is closest to that of C6Hi206, an organic molecule, which does not dissociate this observation further supports the previous evidence of the weak-electrolyte properties of BaS04. 

Wilhelm Ostwald, Elektrochemie (1896). See the discussion in Barkan, "Walther Nernst," 4445. Ostwald s first chemical researches concerned chemical affinities from these studies he went on to investigate electrolytic dissociation, electrical conductivity, mass action, reaction velocities, and catalysis. It was for work on catalysis that he was awarded the Nobel Prize in chemistry in 1909. 

The second period, from 1890 to around 1920, was characterized by the idea of ionic dissociation and the equilibrium between neutral and ionic species. This model was used by Arrhenius to account for the concentration dependence of electrical conductivity and certain other properties of aqueous electrolytes. It was reinforced by the research of Van t Hoff on the colligative properties of solutions. However, the inability of ionic dissociation to explain quantitatively the properties of electrolyte solutions was soon recognized. 

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]. 

Temperature control is important in conductivity measurements, since the conductivity of milk increases by about 0.0001 ohm 1cm 1 per degree Celsius rise in temperature (Gerber 1927 Muller 1931 Pinkerton and Peters 1958). Increased dissociation of the electrolytes and decreasing viscosity of the medium with increasing temperature are undoubtedly responsible for this effect. An investigation (Sudheendra-nath and Rao 1970) of the viscosity and electrical conductivity of skim milk from cows and buffaloes failed to reveal a simple relationship. The authors attributed the lack of linear correlations to variations in casein structure and its hydration. 

Electrolytes, depending upon their strength, dissociate to a greater or less extenl in polar solvents. The extent to which a weak electrolyte dissociates may be determined by electrical conductance, electromotive force, and freezing point depression methods. The electrical conductance method is the most used because of its accuracy and simplicity. Arrhenius proposed that the degree of dissociation, a. of a weak electrolyte at any concentration in solution could be found from the rutio of the equivalent conductance. A. of the electrolyte at the concentration in question to (he equivalent conductance at infinite dilution A0 of the electrolyte. Thus... 

Many reactions, particularly those that involve ionic compounds, take place in aqueous solution. Substances whose aqueous solutions contain ions and therefore conduct electricity are called electrolytes. Ionic compounds, such as NaCl, and molecular compounds that dissociate substantially into ions when dissolved in water are strong electrolytes. Substances that dissociate to only a small extent are weak electrolytes, and substances that do not produce ions in aqueous solution are nonelectrolytes. Acids dissociate in aqueous solutions to yield an anion and a hydronium ion, H30 +. Those acids that dissociate to a large extent are strong acids those acids that dissociate to a small extent are weak acids. 

Solutions of highly surface-active materials exhibit unusual physical properties. In dilute solution the surfactant acts as a normal solute (and in the case of ionic surfactants, normal electrolyte behaviour is observed). At fairly well defined concentrations, however, abrupt changes in several physical properties, such as osmotic pressure, turbidity, electrical conductance and surface tension, take place (see Figure 4.13). The rate at which osmotic pressure increases with concentration becomes abnormally low and the rate of increase of turbidity with concentration is much enhanced, which suggests that considerable association is taking place. The conductance of ionic surfactant solutions, however, remains relatively high, which shows that ionic dissociation is still in force. 

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 the DLCC the electrodes are carbon as this has an exceptional combination of chemical enertness, electrical conductivity and low cost along with availability as a material with high surface area to volume ratio. A variety of electrolytes is used. If the electrolyte is aqueous then the applied voltage must be limited to below approximately 1.2Y to avoid dissociation of the water molecule. Some non-aqueous electrolytes are used that raise the operating voltage to close to 3 Y. 

When ionic salts dissolve in water, the individual ions separate. These positively and negatively charged particles in the water medium are mobile and can move from one part of a solution to another. Because of this movement, solutions of ions can conduct electricity. Electrolytes are substances which can form ions when dissolved in water and can conduct an electric current. These substances are also capable of conducting an electric current in the molten state. Nonelectrolytes are substances which do not conduct an electric current. Electrolytes may be further characterized as either strong or weak. A strong electrolyte dissociates almost completely when in a water solution it is a good conductor of electricity. A weak electrolyte has only a small fraction of its particles... 

Also the so called degree of dissociation, determined from the colligative properties, does not agree with the result obtained from the measurement of the electrical conductance. Finally the law of chemical equilibrium, applicable to the dissociation of weak electrolytes, cannot be applied to the strong ones. 

In aqueous solution, hydrogen peroxide possesses only a very feeble electrical conductivity comparable with that of water, and cannot be regarded as an electrolyte.2 As a solvent, however, it exhibits certain characteristics similar to water thus it favours the dissociation of the solute, especially of acids, whilst with salts it tends to form compounds in a manner corresponding with the hydration of substances in aqueous solution3 (p. 333). The absorption spectrum of hydrogen peroxide for ultra-violet light has been examined.4... 

Nonaqueous electrochemistry — Electrochemistry (both interfacial and ionic) related to solutions other than aqueous solutions. This includes the following solvents, condensed gases, gels, and solids, all ensuring electric conductivity either by self-dissociation or by dissolving the appropriate electrolytic salts ... 

Many electrochemical reactions, especially of organic compounds, are better carried out in non-aqueous solvents and may not even proceed in water. The following requirements should be met by these solvents [73-77] sufficient solubility of the compounds to be examined and, of necessity, of the supporting electrolyte as well (usually tetraalkylammonium salts), chemical inertness towards the electrolyte and the reactive intermediates formed [e.g. the frequently formed radical anions would immediately be pro-tonated by protic solvents), and as high a relative permittivity as possible (usually fir > 10). The latter will increase the electrical conductivity by favoring the dissociation of the electrolyte and hence decreasing the electrical resistance of the solution. Nevertheless, even solvents of low relative permittivity (sr < 5) can be used for electrochemical... 

The Electrolytic Dissociation Theory. —From his studies of the conductances of aqueous solutions of acids and their chemical activity, Arrhenius (1883) concluded that an electrolytic solution contained two kinds of solute molecules these were supposed to be active molecules, responsible for electrical conduction and chemical action, and inactive molecules, respectively. It was believed that when an acid, base or salt was dissolved in water a considerable portion, consisting of the so-called active molecules, was spontaneously split up, or dissociated, into positive and negative ions it was suggested that these ions are free to move independently and are directed towards the appropriate electrodes under the influence of an electric field. The proportion of active, or dissociated, molecules to the total number of molecules, later called the degree of dissociation, was considered to vary with the concentration of the electrolyte, and to be equal to unity in dilute solutions. 

Strong electrolytes completely dissociate into ions and conduct electricity well. Weak electrolytes provide few ions in solution. Therefore, even in high concentrations, solutions of weak electrolytes conduct electricity weakly. Ionic compounds are usually strong electrolytes. Covalent compounds may be strong electrolytes, weak electrolytes, or nonconductors. 

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