Conductivity and Conductometry

James Holler University of Kentucky, Lexington, Kentucky Christie G. Enke The University of New Mexico, Albuquerque, New Mexico 

As we shall see, the solution conductivity depends on the ion concentration and the characteristic mobility of the ions present. Therefore, conductivity measurements of simple, one-solute solutions can be interpreted to indicate the concentration of ions (as in the determination of solubility or the degree of dissociation) or the mobility of ions (as in the investigations of the degree of solvation, complexation, or association of ions). In multiple-solute solutions, the contribution of a single ionic solute to the total solution conductivity cannot be determined by conductance measurements alone. This lack of specificity or selectivity of the conductance parameter combined with the degree of tedium usually associated with electrolytic conductivity measurements has, in the past, discouraged the development of conductometry as a widespread electroanalyti-cal technique. Today, there is a substantial reawakening of interest in the practical applications of conductometry. Recent electronic developments have resulted in automated precision conductometric instrumentation and applications 

In this chapter we take a careful look at the phenomenon of electrical conductivity of materials, particularly electrolytic solutions. In the first section, the nature of electrical conductivity and its relation to the electrolyte composition and temperature is developed. The first section and the second (which deals with the direct-current contact methods for measuring conductance) introduce the basic considerations and techniques of conductance measurement. This introduction to conductance measurements is useful to the scientist, not only for electrolytic conductance, but also for understanding the applications of common resistive indicator devices such as thermistors for temperature, photoconductors for light, and strain gauges for mechanical distortion. The third section of this chapter describes the special techniques that are used to minimize the effects of electrode phenomena on the measurement of electrolytic conductance. In that section you will encounter the most recent solutions to the problems of conductometric measurements, the solutions that have sparked the resurgent interest in analytical conductometry. 

When a charged particle i (an electron or ion) in a liquid or solid material is subjected to an electric field, it quickly reaches a limiting average velocity of motion in the direction of the field opposite to the sign of its charge. The velocity Vj (cm/s) is given by 

The total current density J is the sum of the individual current density charge carriers in the substance. 

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Polyelectrolyte complexation in aqueous solution between PEI and PMAA has been studied through viscometry, conductometry, potentiometry, and IR spectroscopy [90]. Upon addition of increasing concentrations of PMAA to an aqueous PEI solution, viscosity dropped suddenly around a 1 to 4 ratio of PMAA to PEI because of the complexation and subsequent coiling of the complexed chains. Reduced viscosity then rose past this ratio indicating that the stoichiometry of the complex occurs in a 1 4 (PMAA groups PEI groups) formation. Conductance and titration experiments agreed with this theory. The... 

Electrical Conductivity. See Conductivity, Electrical Conductometry and Conductometric Titrations in Vol 3 of Encycl, pp C497-R C498-L... 

Conductivity, Electrical Conductometry and Conductometric Titrations. Electrical conductivity is thequality or ability of a substance to transmit electrical energy. If it deals with the conductivity of an electrolyte in solution, it is then called electrolytic conductivity. Conductometry deals with analyses by measuring electrolytic conductivity, based on the fact that ionic substances in many solvents conduct electricity. Conductometric titrations are quantative analysis based on the fact that with the addn of the titrating agent to a soln being titrated, the specific conductivity (reciprocal of specific resistance in mhos) changes at a different rate before and after the end point (Comp with Potentiometric Analysis) Refs 1 )Kirk Othmer 4 (L 949), 325-33 (Conductometry) 2)W.G.Berl, Edit, "Physical Methods... 

Conductometry is an electrochemical technique used to determine the quantity of an analyte present in a mixture by measurement of its effect on the electrical conductivity of the mixture. It is the measure of the ability of ions in solution to carry current under the influence of a potential difference. In a conductometric cell, potential is applied between two inert metal electrodes. An alternating potential with a frequency between 100 and 3000 Hz is used to prevent polarization of the electrodes. A decrease in solution resistance results in an increase in conductance and more current is passed between the electrodes. The resulting current flow is also alternating. The current is directly proportional to solution conductance. Conductance is considered the inverse of resistance and may be expressed in units of ohm (siemens). In clinical analysis, conductometry is frequently used for the measurement of the volume fraction of erythrocytes in whole blood (hematocrit) and as the transduction mechanism for some biosensors. 

In the following, after a brief account of the data available in the literature as concerns microemulsion conductive and dielectric properties, results will be reported and analyzed that show how structural transitions in the transparent isotropic water-inoil solubilization area can be put into evidence by means of conductometry and dielectrometry. Mention will be made also of the occurrence, in certain w/o microemulsion systems, of percolative conduction phenomena (30) that appear to depend upon the nature of the alcohol used as the cosurfactant, for a given hydrocarbon (31). 

Conductometric Sensors for Monitoring Electroiytic Conductance. Introduction. Electrolytic conductance serves as a useful signal of the electrical conductivity of mainly aqueous electrolyte solutions, and conductometry has been devel-... 

Three major detecting methods of electrochemistry have been adapted for SECM studies. They are voltammetry, potentiometry, and conductometry. It must be mentioned here that scanning ion conductance microscopy (SICM) sometimes considered rather as an individual scanning probe microscopic technique than member of the SECM methods. Accordingly, we discuss shortly the SECM properties of the three detection techniques trying to show the major differences. 

The simplest estimate of the overall salinity of water (its ionic impurity content) is obtained by measuring its conductivity. Such measurements can be useful, for instance, when checking the purity of rinsing waters from the plating and metalfinishing industries. A quantitative estimate of the degree of contamination is possible via conductometry when the qualitative composition of the ionic contaminants is known and does not change. 

Many IC techniques are now available using single column or dual-column systems with various detection modes. Detection methods in IC are subdivided as follows [838] (i) electrochemical (conductometry, amper-ometry or potentiometry) (ii) spectroscopic (tJV/VIS, RI, AAS, AES, ICP) (iii) mass spectrometric and (iv) postcolumn reaction detection (AFS, CL). The mainstay of routine IC is still the nonspecific conductometric detector. A significant disadvantage of suppressed conductivity detection is the fact that weak to very weak acid anions (e.g. silicate, cyanide) yield poor sensitivity. IC combined with potentiometric detection techniques using ISEs allows quantification of selected analytes even in complex matrices. The main drawback... 

The most important non-faradaic methods are conductometric analysis and (normal) potentiometric analysis in the former we have to deal essentially with the ionics and in the latter mainly with the electrodics. Strictly, one should assign a separate position to high-frequency analysis, where not so much the ionic conductance but rather the dielectric and/or diamagnetic properties of the solution are playing a role. Nevertheless, we shall still consider this techniques as a special form of conductometry, because the capacitive and inductive properties of the solution show up versus high-frequency as a kind of AC resistance (impedance) and, therefore, as far as its reciprocal is concerned, as a kind of AC conductance. 

This method is primarily based on measurement of the electrical conductance of a solution from which, by previous calibration, the analyte concentration can be derived. The technique can be used if desired to follow a chemical reaction, e.g., for kinetic analysis or a reaction going to completion (e.g., a titration), as in the latter instance, which is a conductometric titration, the stoichiometry of the reaction forms the basis of the analysis and the conductometry, as a mere sensor, does not need calibration but is only required to be sufficiently selective. 

The electrodes consist of platinum discs, slightly platinized and mounted in glass tubes which are placed in the glass vessels. The types of Wheatstone bridge commercially available for conductometry and known as conductivity bridges can be used in either the resistance mode or the conductance mode the choice between these modes depends on the character of the solution under investigation and on the performance of the conductance cell. 

Definitive measurements by fundamental quantities complemented by an empirical factor, e.g. titre (titrimetry), as well as by well-known empirical (transferable) constants like molar absorption coefficient (spectrophotometry), Nernst factor (potentiometry, ISE), and conductivity at definite dilution (conductometry)... 

This method, which has been developed and extensively utilized in Russia [22,23], deals with nonstirred liquid phases and is based on measurements of the electrical conductivity of the aqueous phase and of its changes during extraction. In the experimental device, the two phases are initially kept separated inside a theimostated cell and then instantaneously contacted through a known contact area. At this moment, the concentration variation in one phase is recorded as a function of time, generally using conductometry. 

The third relaxation process is located in the low-frequency region and the temperature interval 50°C to 100°C. The amplitude of this process essentially decreases when the frequency increases, and the maximum of the dielectric permittivity versus temperature has almost no temperature dependence (Fig 15). Finally, the low-frequency ac-conductivity ct demonstrates an S-shape dependency with increasing temperature (Fig. 16), which is typical of percolation [2,143,154]. Note in this regard that at the lowest-frequency limit of the covered frequency band the ac-conductivity can be associated with dc-conductivity cio usually measured at a fixed frequency by traditional conductometry. The dielectric relaxation process here is due to percolation of the apparent dipole moment excitation within the developed fractal structure of the connected pores [153,154,156]. This excitation is associated with the selfdiffusion of the charge carriers in the porous net. Note that as distinct from dynamic percolation in ionic microemulsions, the percolation in porous glasses appears via the transport of the excitation through the geometrical static fractal structure of the porous medium. 

The third category of salinity methodologies was based on conductometry, as the conductivity of a solution is proportional to the total salt content. Standard Seawater, now also certified with respect to conductivity, provides the appropriate calibrant solution. The conductivity of a sample is measured relative to the standard and converted to salinity in practical salinity units (psu). Note that although psu has replaced the outmoded %o, usually units are ignored altogether in modern usage. These techniques continue to be the most widely used methods because conductivity measurements can provide salinity values with a precision of 0.001 psu. Highly precise determinations require temperature control of samples and standards to within 0.001 °C. Application of a non-specific technique like conductometry relies upon the assumption that the sea-salt... 

Conductometry is used to determine the concentration or fraction of dissociated ions that conduct electricity (-C+ and A" ). However, it is only... 

Conductometry paved the way for the development of the ion-pair concept [3]. The oldest experimental evidence of ion-pairing was obtained from colligative properties and electrical conductivity measurements. It is generally accepted that electroneutral ion-pairs do not contribute to solution conductivity. Conductometry is now a reliable and well established technique even in low millimolar concentration ranges, but the full description of conductance in the presence of ion-pairing is anon-trivial task. To date the most accepted equation was developed by Fuoss and Hsia [92] and expanded by Fernandez-Prini and Justice [93] ... 

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