Electrolyte solutions molar conductivity

For strong electrolytes the molar conductivity increases as the dilution is increased, but it appears to approach a limiting value known as the molar conductivity at infinite dilution. The quantity A00 can be determined by graphical extrapolation for dilute solutions of strong electrolytes. For weak electrolytes the extrapolation method cannot be used for the determination of Ax but it may be calculated from the molar conductivities at infinite dilution of the respective ions, use being made of the Law of Independent Migration of Ions . At infinite dilution the ions are independent of each other, and each contributes its part of the total conductivity, thus ... 

Conductivity changes can frequently be useful for studying the reactions of metal complexes in solution. Molar conductivities (Am) are normally determined using 1x10 M solutions of the complexes. Typical ranges for different electrolyte types are listed in Table 2.8. 

The parameters of molar conductivity of the electrolyte, A = a/c,, and molar conductivity of ions, Xj = ZjFuj (units S cm /mol), are also used to describe the properties of electrolyte solutions (A is used only in the case of binary solutions). With Eq. (1.14), we can write for a binary solution... 

In electrolyte solutions the molecules dissociate into ions spontaneously, so that the solution becomes conductive. Different electrolytes exhibit different degrees of dissociation, a, which will influence the actual values of molar conductivity A the two parameters are interrelated as... 

In the classical theory of conductivity of electrolyte solutions, independent ionic migration is assumed. However, in real solutions the mobilities Uj and molar conductivities Xj of the individual ions depend on the total solution concentration, a situation which, for instance, is reflected in Kohhausch s square-root law. The values of said quantities also depend on the identities of the other ions. All these observations point to an influence of ion-ion interaction on the migration of the ions in solution. 

It follows (when taking into account that = x z = Zj) that the molar conductivity of binary electrolyte solutions is given by... 

In aqueous electrolyte solutions the molar conductivities of the electrolyte. A, and of individual ions, Xj, always increase with decreasing solute concentration [cf. Eq. (7.11) for solutions of weak electrolytes, and Eq. (7.14) for solutions of strong electrolytes]. In nonaqueous solutions even this rule fails, and in some cases maxima and minima appear in the plots of A vs. c (Eig. 8.1). This tendency becomes stronger in solvents with low permittivity. This anomalons behavior of the nonaqueous solutions can be explained in terms of the various equilibria for ionic association (ion pairs or triplets) and complex formation. It is for the same reason that concentration changes often cause a drastic change in transport numbers of individual ions, which in some cases even assume values less than zero or more than unity. 

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. 

TABLE 8.2 Conductivities, o, Cationic Transport Numbers, Molar Conductivities of the Electrolyte (A) and Cation (X+), and Activation Energies of Conduction, A, for a Number of Melts and Aqueous KCl Solution... 

In aqueous solutions, concentrations are sometimes expressed in terms of normality (gram equivalents per liter), so that if C is concentration, then V = 103/C and a = 103 K/C. To calculate C, it is necessary to know the formula of the solute in solution. For example, a one molar solution of Fe2(S04)3 would contain 6 1CT3 equivalents cm-3. It is now clear as to why A is preferred. The derivation provided herein clearly brings out the fact that A is the measure of the electrolytic conductance of the ions which make up 1 g-equiv. of electrolyte of a particular concentration - thereby setting conductance measurements on a common basis. Sometimes the molar conductance am is preferred to the equivalent conductance this is the conductance of that volume of the electrolyte which contains one gram molecule (mole) of the ions taking part in the electrolysis and which is held between parallel electrodes 1 cm apart. 

As in the case of solutions, the specific conductance, K, the equivalent conductance, a, and the molar conductance, am, are also distinguished for molten electrolytes. These are defined in the same manner as done for the case of solutions of electrolytes. It may, however, be pointed out that molten salts generally have much higher conductivities than equivalent aqueous systems. 

A study of the concentration dependence of the molar conductivity, carried out by a number of authors, primarily F. W. G. Kohlrausch and W. Ostwald, revealed that these dependences are of two types (see Fig. 2.5) and thus, apparently, there are two types of electrolytes. Those that are fully dissociated so that their molecules are not present in the solution are called strong electrolytes, while those that dissociate incompletely are weak electrolytes. Ions as well as molecules are present in solution of a weak electrolyte at finite dilution. However, this distinction is not very accurate as, at higher concentration, the strong electrolytes associate forming ion pairs (see Section 1.2.4). 

The first theory of solutions of weak electrolytes was formulated in 1887 by S. Arrhenius (see Section 1.1.4). If the molar conductivity is introduced into the equations following from Arrhenius concepts of weak electrolytes, Eq. (2.4.17) is obtained, known as the Ostwald dilution law this equation... 

While the molar conductivity of strong electrolytes A0 can be measured directly, for determination of the ionic conductivities the measurable transport numbers must be used (cf. Eq. (2.4.12)). Table 2.1 lists the values of the limiting conductivities of some ions in aqueous solutions. 

The conductance of an electrolyte solution characterizes the easiness of electric conduction its unit is reciprocal ohm, = siemens = S = A/V. The electric conductivity is proportional to the cross-section area and inversely proportional to the length of the conductor. The unit of conductivity is S/m. The conductivity of an electrol3de solution depends on the concentration of the ions. Molar conductivity, denoted as X, is when the concentration of the hypothetical ideal solution is 1 M = 1000 mol/m. Hence, the unit of molar conductivity is either Sm M , or using SI units, Sm mol . For nonideal solutions, X depends on concentration, and the value of X at infinite dilution is denoted by subscript "0" (such as >,+ 0, and X for cation and anion molar conductivity). The conductivity is a directly measurable property. The molar conductivity at infinite dilution may be related to the mobility as follows ... 

In the above sections, we considered electrolytes that are ionophores.10 Iono-phores, like sodium chloride, are ionic in the crystalline state and are expected to dissociate into free ions in dilute solutions. In fact, in high-permittivity solvents (er>40), ionophores dissociate almost completely into ions unless the solutions are of high concentration. When an ionophore is completely dissociated in the solution, its molar conductivity A decreases linearly with the square root of the concentration c (<10 2 M) ... 

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]. 

Molar Conductivity of Dilute Solutions of Symmetrical Strong Electrolytes... 

Here, the association constant KA can be determined by measuring the conductivity of the unsaturated solutions. Corrections are made by successive approximations for the effect of electrolyte concentrations on molar conductivity A and for the effect of activity coefficient on KA. Here, k/Ar% is used as the first approximation of the ionic strength. 

Heterobinuclear complexes containing alkali or alkaline earth metal cations have been derived from mononuclear transition metal complexes of compartmental ligands (51).288 The molar conductivities of the (51)-CuLi2 series suggest that the complexes are uniunivalent electrolytes in water and so are present in solution as Li[(51b)CuLi]- H20 the corresponding di-sodium, -potassium or -cesium complexes are unibivalent electrolytes and so likely to be present in solution as M2[(51)Cu]- H20. 

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