Titration, conductometric

Finally, the sulfonate content of lignin is deterrnined by two main methods one typified by conductometric titration in which sulfonate groups are measured direcdy, and the other which measures the sulfur content and assumes that all of the sulfur is present as sulfonate groups. The method of choice for determining the sulfonate content of lignin samples that contain inorganic or nonsulfonate sulfur, however, is conductometric titration (45). 

Many experimental approaches have been appHed to the deterrnination of stabihty constants. Techniques include pH titrations, ion exchange, spectrophotometry, measurement of redox potentials, polarimetry, conductometric titrations, solubiUty deterrninations, and biological assay. Details of these methods can be found in the Hterature (9,10). 

The conductometric titration shown in Fig. 6 (adapted from Ref. [135]) exhibits the expected conductivity increase for LiBF4 and LiS03CF3 solutions in PC / 5-crown-5 mixtures at 25 °C, i.e., for salts which are known to be strongly associated despite the relatively high permittivity of the solvent. 

The quantitative analysis procedure involves gravimetric detn of the HMX on a moisture-free basis after benzene extraction of, and differential detn of TNT. Moisture content is detd by conductometric titration of sample in an acetic-sulfuric acid suspension. Acetone insoluble matter is determined gravimetrically... 

Gregor, H. P., Gold, D. H. Frederick, M. (1957). Viscometric and conductometric titrations of polymethacrylic acids with alkali metals and quaternary ammonium bases. Journal of Polymer Science, 23, 467-75. 

Conductometric titration rests on the marked changes that occur near the titration endpoint in the relation between conductivity and the amount of titrant added (an extreme or inflection point). It is used in particular for the titration of acids with base (and vice versa) in colored and turbid solutions or solutions containing reducing and oxidizing agents (i.e., in those cases where the usual color change of acid-base indicators cannot be seen). 

Phase diagrams of a polyacrylate-phosphonate system with temperature and calcium ion concentration can be established with turbidimetric measurements [1830]. Conductometric titrations also are suitable to characterize the phase behavior of scale inhibitors [514] (Table 7-2). 

In accordance to Kohlrausch s law the electrical conductivity of a solution depends upon the number of ions present and their mobility. For this reason, conductivity measurements can be used to determine the end-points of acid-alkali and other titrations. Present attention is focused on the conductometric titration curves shown in Figures 6.5 (A)-(D). 

Figure 6.5 Conductometric titrations (A) strong acid against strong base (B) weak acid against strong base (C) strong acid against weak base (D) potassium chloride against silver nitrate.

Attention is finally focused on the advantages of conductometric titrations, which include (i) colored solutions where no indicator is found to function satisfactorily can be successfully titrated by this method (ii) the method is useful for titrating weak acids against weak bases, which does not produce a sharp change in color with indications in ordinary volumetric analysis and (iii) more accurate results are obtained because of the graphical determination of the end-point. 

Conductometric titrations offer several advantages compared with potentiometric titration methods, such as better precision and better differentiation of the basic components in polymers, but they are more laborious. ASTM D 4928-96 is an established KF method for the determination of water in crude oils. 

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. 

In conductometric titration the reaction is followed by means of conductometry there is little interest in the complete titration curve, but rather in the portion around the equivalence point in order to establish the titration endpoint. 

Fig. 2.6. Conductometric titration of basic salt, and of chloride with precipitation or complex formation.

For examples of analytical procedures and practical results of conductometric titration, see the selected bibliography (Section 1.1). 

In fact, any type of titration can be carried out potentiometrically provided that an indicator electrode is applied whose potential changes markedly at the equivalence point. As the potential is a selective property of both reactants (titrand and titrant), notwithstanding an appreciable influence by the titration medium [aqueous or non-aqueous, with or without an ISA (ionic strength adjuster) or pH buffer, etc.] on that property, potentiometric titration is far more important than conductometric titration. Moreover, the potentiometric method has greater applicability because it is used not only for acid-base, precipitation, complex-formation and displacement titrations, but also for redox titrations. 

Majer65 in 1936 proposed measuring, instead of the entire polarographic curve, only the limiting current at a potential sufficiently high for that purpose if under these conditions one titrates metal ions such as Zn2+, Cd2+, Pb2+, Ni2+, Fe3+ and Bi3+ with EDTA66, one obtains a titration as depicted in Fig. 3.55 i, decreases to a very low value, in agreement with the stability constant of the EDTA-metal complex and the titration end-point is established by the intersection of the ij curves before and after that point correction of the i values for alteration of the solution volume by the titrant increments as in conductometric titration is recommended. 

The aforementioned application of conductometry in Lewis titrations was an incentive, in addition to our potentiometric studies, to investigate also conductometric titration in non-aqueous media more thoroughly. Figs. 4.10 and 4.11 show two selected examples of the study. 

Conductometric titrations. Van Meurs and Dahmen25-30,31 showed that these titrations are theoretically of great value in understanding the ionics in non-aqueous solutions (see pp. 250-251) in practice they are of limited application compared with the more selective potentiometric titrations, as a consequence of the low mobilities and the mutually less different equivalent conductivities of the ions in the media concerned. The latter statement is illustrated by Table 4.7108, giving the equivalent conductivities at infinite dilution at 25° C of the H ion and of the other ions (see also Table 2.2 for aqueous solutions). However, in practice conductometric titrations can still be useful, e.g., (i) when a Lewis acid-base titration does not foresee a well defined potential jump at an indicator electrode, or (ii) when precipitations on the indicator electrode hamper its potentiometric functioning. 

All copolymers were prepared by solution polymerization, under adiabatic conditions, giving at least 99.9% conversions. The polymer gels were granulated and then dried at 90 °C to a residual water content of 10 to 12%. The active polymer content of each sample was calculated from the initial weight of the comonomers and the weight of the dried gel. Hydrolysis of the polymers was determined by conductometric titration to be less than 0.2% of the acrylamide charge. The molecular weight of the polymers was 8-10 million as determined by intrinsic viscosity measurements. 

The extent of hydrolysis of the copolymers was determined by conductometric titration. The increase in carboxylate content was determined by difference, before and after hydrolysis. (The AMPS content of the polymers, where measured, was determined by colloid titration with poly [diallyl dimethyl ammonium chloride].)... 

Electrodeposition Potentiometric Titrations Conductometric Titrations High-Frequency Titrations... 

Schmidt and coworkers17 showed by conductometric titrations that bacterial cellulose resembled all undegraded celluloses in its content of 0.28% of carboxyl groups. 

Polystyrene Latexes. The polystyrene latexes used were the mono-disperse LS-1102-A, LS-1103-A, and LS-1166-B (Dow Chemical Co.) with average particle diameters of 190, 400, and llOOnm, respectively. The latexes were cleaned by ion exchange with mixed Dcwex 50W-Dowex 1 resin (9). The double-distilled and deionized (DDI) water used had a conductivity of 4x10 ohm- cm-. The surface groups of the ion-exchanged latexes determined by conductometric titration (10) were strong-acid sulfates the surface charge densities were 1.35, 3.00 and 5.95 jiC/cm, respectively. 

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. 

Sketch the shape of the titration curve for the following conductometric titrations ... 

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