Factorizing of a concentration function for the mean activity coefficients of aqueous strong electrolytes into individual functions for the ionic species

Ferse, A.; Müller, Hans-Otfried

doi:10.1007/s10008-011-1413-9

Cited by 14 publications

(26 citation statements)

References 43 publications

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“…This assumption is affirmed by the results obtained with the purely mathematical method (see Figure 5) (Ferse & Müller, 2011).The exclusive use of mean activity coefficients permanently at the thermodynamic treatment of equilibriums and processes where dissolved electrolytes take part is not justified. This implies the risk of arriving at erroneous conclusions.…”

Section: Mean Activity Coefficientmentioning

confidence: 96%

“…The present paper cannot deal with the wide variety of attempted ways. Reviews with critical discussions of the used methods are given by the author in 1978 (Ferse, 1978) as well as in 2008 and 2011 (Ferse, 2008;Ferse & Müller, 2011). The discussed methods in these three articles do not claim to be complete, only basic methods on selected examples have been discussed.…”

Section: Importance Of Individual Activity Coefficientsmentioning

confidence: 99%

“…This is the special concentration range 5 ≤ m ≤ 10 mol/kg where the logarithm of the mean activity coefficient of strong electrolytes is linearly dependent on the concentration, see Figure 1 (additional details see (Ferse & Müller, 2011)). …”

Section: The Mathematical Structure Of the Concentration Functionsmentioning

confidence: 99%

“…The experimentally accessible curve for the mean activity coefficient of a strong electrolyte to the required power as a function of the ionic strength 'J' can be well approximated up to highest concentrations using the basic product function (14) (Ferse & Müller, 2011):…”

Section: The Mathematical Structure Of the Concentration Functionsmentioning

confidence: 99%

“…(index variables k = 1 up to 3): parameters Concerning the case k = lower bound of summation 1 and upper bound of summation 3, the relationship (14) is written in the paper by (Ferse & Müller, 2011) dissolved in summands with a different designation of the parameters: A predefinition was not established for the concentration range between infinite dilution and 5 mol/kg. The values in this concentration range ensue from the sum of the first and the second summand in the factor functions in relationship (14).…”

Section: The Mathematical Structure Of the Concentration Functionsmentioning

confidence: 99%

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Some Aspects on the Problem of Individual Activity Coefficients of Single-ion Species of Aqueous Strong Electrolytes

Ferse¹

2012

IJC

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Individual activity coefficients of single-ion species can neither be defined in thermodynamic terms nor determined experimentally. This does not mean that the individual activity of a single-ion species of an aqueous strong electrolyte does not have a real specifically individual effectiveness. Individual ion activity coefficients are required, for instance, for data about the potentials of single electrodes and liquid junction potentials in galvanic cells with transference. A purely mathematical method is written which allows the factorizing the mean activity coefficient into individual parts of the single-ion species. The experimentally accessible concentration curve of the mean activity coefficient is fitted with a quite new mathematical approach. The parameter set of the mathematical approach can be determined univocally and invariantly with the help of the asymptotic theory using corresponding approximations.Keywords: aqueous strong electrolytes, concentration dependence of activity coefficients, factorization of the mean activity coefficients, individual ion activity coefficients IntroducationThe analytical concentration "m" of a component within a real and homogeneous mixed phase has to be modified for the thermodynamic interpretation of equilibriums, according to Eq. (1):The modified concentration "a" is denoted as activity. The multiplicative term "γ" is known as activity coefficient. The activity coefficient considers all deviations from ideal behaviour of the component within the real mixed phase by forming of interaction forces.

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Section: Mean Activity Coefficientmentioning

confidence: 96%

Section: Importance Of Individual Activity Coefficientsmentioning

confidence: 99%

Section: The Mathematical Structure Of the Concentration Functionsmentioning

confidence: 99%

Section: The Mathematical Structure Of the Concentration Functionsmentioning

confidence: 99%

Section: The Mathematical Structure Of the Concentration Functionsmentioning

confidence: 99%

See 3 more Smart Citations

Some Aspects on the Problem of Individual Activity Coefficients of Single-ion Species of Aqueous Strong Electrolytes

Ferse¹

2012

IJC

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Meaning and Measurability of Single‐Ion Activities, the Thermodynamic Foundations of pH, and the Gibbs Free Energy for the Transfer of Ions between Dissimilar Materials

Rockwood

2015

ChemPhysChem

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Considering the relationship between concentration and vapor pressure (or the relationship between concentration and fugacity) single-ion activity coefficients are definable in purely thermodynamic terms. The measurement process involves measuring a contact potential between a solution and an external electrode. Contact potentials are measurable by using thermodynamically reversible processes. Extrapolation of an equation to zero concentration and ionic strength enables determination of single-ion activity coefficients. Single-ion activities can be defined and measured without using any extra-thermodynamic assumptions, concepts, or measurements. This method could serve as a gold standard for the validation of extra-thermodynamic methods for determining single-ion activities. Furthermore, it places the concept of pH on a thermodynamically solid foundation. Contact potential measurements can also be used to determine the Gibbs free energy for the transfer of ions between dissimilar materials.

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Liquid Junction Potentials

Tsirlina

2013

Handbook of Reference Electrodes

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Factorizing of a concentration function for the mean activity coefficients of aqueous strong electrolytes into individual functions for the ionic species

Cited by 14 publications

References 43 publications

Some Aspects on the Problem of Individual Activity Coefficients of Single-ion Species of Aqueous Strong Electrolytes

Some Aspects on the Problem of Individual Activity Coefficients of Single-ion Species of Aqueous Strong Electrolytes

Meaning and Measurability of Single‐Ion Activities, the Thermodynamic Foundations of pH, and the Gibbs Free Energy for the Transfer of Ions between Dissimilar Materials

Liquid Junction Potentials

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