Activity coefficient assumptions in the determination of the association constant of thallous chloride

1964 ◽  
Vol 17 (5) ◽  
pp. 522 ◽  
Author(s):  
JB Macaskill ◽  
MH Panckhurst

The solubility of thallous chloride has been measured in sodium chloride and sodium perchlorate solutions at an ionic strength less than 0 1M. The association constant of thallous chloride has been determined from these measurements using two different types of ionic activity coefficient expression, one of them incorporating Br�nsted's principle of specific interaction. The method for determining the association constant gives all the parameters in the treatment but the two activity coefficient expressions give different sets of parameters. These are discussed.


1966 ◽  
Vol 19 (6) ◽  
pp. 915 ◽  
Author(s):  
JB Macaskill ◽  
MH Panckhurst

The solubility of thallous chloride has been measured in solutions of hydrochloric acid, caesium chloride, caesium perchlorate, barium chloride, and in various mixtures of sodium chloride and sodium perchlorate. These measurements are analysed to give the association constant for thallous chloride, paying particular attention to ionic activity coefficient formulae. It is shown that an activity coefficient expression which assumes no specific interactions between free ions is unsatisfactory in contrast to an expression which assumes such interactions. The consequences of this are discussed.



1967 ◽  
Vol 20 (12) ◽  
pp. 2633 ◽  
Author(s):  
KH Khoo ◽  
MH Panckhurst

Measurements are reported of the solubility of thallium(I) chloride in aqueous solutions of sodium acetate and thallium(I) perchlorate and in solutions of sodium chloride, barium chloride, and sodium perchlorate in 16.7, 30, and 60 wt. % methanol-water mixtures. The measurements in water are used to test the merits of two types of ionic activity coefficient expression. It is shown that it is necessary to take account of specific interactions between free ions and that this also allows for small amounts of other association reactions in the same solution. The possibility of allowing for subsidiary association without using specific interaction coefficients is discussed, and it is concluded that this cannot be done in a completely satisfactory way. Measurements in mixed solvents are used to determine association parameters for the complex TlCl.



1969 ◽  
Vol 22 (5) ◽  
pp. 911 ◽  
Author(s):  
CW Childs ◽  
MH Panckhurst

Measurements are reported of the solubility of thallium(I) bromide in aqueous solutions of potassium bromide, sodium perchlorate, barium bromide, and of mixtures of sodium bromide and sodium perchlorate and of sodium bromide and sodium acetate at 25�. The measurements are used to test the merits of two types of ionic activity coefficient expressions, one assuming specific interactions between free ions and the other not. It is shown that neither expression can describe our results adequately, in contrast to previous solubility results with thallium(I) chloride for which the specific interaction expression was adequate.



1972 ◽  
Vol 25 (2) ◽  
pp. 311 ◽  
Author(s):  
CY Chan ◽  
MH Panckhurst

Measurements are reported of the optical absorbance of aqueous solutions of thallium(I) bromide in mixture with other electrolytes a t 25°. These measurements are similar to those previously reported1 for thallium(I) chloride and are used in conjunction with two different types of ionic activity coefficient expressions to investigate association of thallium(I) bromide. Both types of expression give a reasonable description of the experimental results but there is the same disagreement with the analysis of solubility measurements found for thallium(1) chloride.



1969 ◽  
Vol 22 (2) ◽  
pp. 317 ◽  
Author(s):  
JB Macaskill ◽  
MH Panckhurst

Precise measurements are reported of the optical absorbance of aqueous solutions of thallium(I) chloride in mixture with other electrolytes at 25�. Two types of activity coefficient expressions are used to analyse the measurements in terms of association of thallium(I) chloride. The method of analysis is similar to that used for solubility measurements1-3 and the different types of measurements lead to different values for the association constants.



Author(s):  
Andrea Purdešová

The analytical procedure based on stir‑bar sorptive extraction technique, for the determination of selected pesticide residues (diazinon, malathion, cyprodinyl, penconazole, fludioxonyl, pyriproxyfen, boscalid, pyraclostrobin) is described. Analysis was performed using the commercial TwisterTM stir bar for sorptive extraction. It consists of a 2.0‑cm‑long glass‑encapsulated magnetic stir bar externally coated with PDMS. The extracts were off‑line analyzed using fast GC‑MS in SIM mode. Optimized conditions were established as follows concerning extraction time, stirring speed, aqueous medium characteristics (ionic strength and polarity) respectively: 120 min (700 rpm), addition of 4 g of sodium chloride, no addition of methanol as organic modifier, and 30 min ultrasonic desorption in acetonitrile. Recoveries ranged from 38 % to 58 % (RSD < 15 %, n = 6). Validated limits of quantification in matrix were between 1.6 ngL−1 and 548.8 ngL−1, depending on the compound.



1978 ◽  
Vol 31 (7) ◽  
pp. 1411 ◽  
Author(s):  
C Chan ◽  
KH Khoo ◽  
MH Panckhurst

The solubilities of caesium perrhenate in aqueous CsCl, NaCl, KCl and KReO4 solutions at 298.10 K are reported. The solubility activity product for CsReO4 was determined by using extrapolation functions involving two different mean ionic activity coefficient expressions and the results were compared; the total ionic strengths of all the saturated perrhenate solutions were less than 0.1 mol dm-3. One of these expressions used is that proposed recently by Panckhurst and Macaskill1,2 which is an extension of Guggenheim's approach,3,4 specific ionic interactions in aqueous solutions being explicitly taken into account. Its use led to more consistent values for the solubility activity product for CsReO4 than those obtained with the other expression which does not incorporate specific interaction parameters. Values of specific ionic interaction parameters for caesium, potassium and sodium perrhenates in dilute aqueous mixtures with CsCl, KCl, KReO4, KI or NaCl are also reported.



1972 ◽  
Vol 25 (2) ◽  
pp. 317 ◽  
Author(s):  
CY Chan ◽  
MH Panckhurst

In an attempt to resolve discrepancies between association constants obtained from solubility and absorbance measurements for thallium(1) chloride and bromide the explicit assumptions used in the various analyses have been considered in detail. It is shown that the discrepancies can be accounted for in part by considering the activity coefficient of the complex TlCl or TIBr, and, more importantly, by allowing for the presence of small amounts of higher complexes in analysing absorbance data. It is also shown, in determining association constants using a specific ionic activity coefficient expression, that uncertainties in some interaction coefficients reduce the usefulness of our solubility measurements in non-common ion salts. In particular, it is concluded, using the specific ionic interaction coefficient expression, that association constants can at present only be arrived at from solubility measurements by specifying arbitrary interaction coefficients for thallium(1) and halide ions; and to obtain association constants using a non-specific ionic activity coefficient expression it is necessary to assume unnecessarily arbitrary subsidiary association reactions as well as an arbitrary value for the activity coefficient parameter B.



1985 ◽  
Vol 31 (11) ◽  
pp. 1811-1814 ◽  
Author(s):  
E Langhoff ◽  
J Ladefoged

Abstract We compared the ionic activity of sodium, as measured with glass electrodes, with sodium concentration in 23 healthy persons, 15 persons with acute renal failure, and before and after dialysis in 46 patients with chronic renal failure. In healthy persons the mean (+/- SEM) sodium concentration was 139.1 +/- 0.6 mmol/L, whereas the ionic activity was equal to that of a 145.2 +/- 0.5 mmol/L solution of sodium chloride. Variation in the concentration of plasma protein was the most important factor influencing the sodium activity coefficient (the ratio between activity and concentration). The sodium activity coefficient in plasma water (corrected for the non-aqueous phase of the plasma) was fairly constant, being 96% of that in a 140 mmol/L solution of sodium chloride. Thus sodium binds to non-protein molecules and sodium ions interact with other substances in uremic plasma only to a very limited extent. The sum of the molar activities of sodium, potassium, urea, and creatinine was closely and linearly correlated with plasma osmolality, both before and after dialysis.



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