Thermodynamic relationships in complex formation. IX. ΔH – ΔS and free energy relationships in mixed ligand complex formation reactions of Cd(II) in aqueous solution

Marco, Domenico De; Linert, Wolfgang

doi:10.1006/jcht.2002.0970

Cited by 14 publications

(10 citation statements)

References 15 publications

(22 reference statements)

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“…In many thermodynamic analyses of chemical reactions/ processes, it has been experimentally demonstrated that there are linear dependencies for the standard thermodynamic function, named the EEC compensation effect (enthalpy-entropy compensation) [ (Sharp 2001;Marco and Linert 2002;Ryde 2014;Olsson et al 2008;Dutronc et al 2014;Klebe 2015) KCE (Norwisz and Musielak 2007;Lvov 2007)]. According to Starikov, the relevant entry is expressed as follows (Starikov 2014): where the slope coefficient is constant and is named the isokinetic temperature, and the intercept ∆H iso which is part of enthalpy, is replaceable in isoentropic conditions (∆S = 0).…”

Section: Introductionmentioning

confidence: 99%

Enthalpy–entropy compensation for isosteric state adsorption at near ambient temperatures

Mianowski

Urbańczyk

2017

Adsorption

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List of symbols AbstractThe adsorption process at near ambient temperatures indicated that the EEC (enthalpy-entropy compensation) is affected by three basic thermodynamic values: ∆H, ∆S and T. The consequence is that it is possible to determine an isosteric straight (symbol H − S) without experimental studies based on the slope coefficient T iso , which is the constant arising from the expected temperature range (about 0-60 °C). Therefore, EEC curves can be obtained by appropriate modification of the temperature range. In the case of entropy of adsorption, the decisive influence is the entropy of gas. For visualization and characterization of this impact, we proposed resolute pointer µ (Eq. 25), through which it is observed that for small values of the equilibrium vapor pressure, as P → 0, there are significant deviations from the isosteric straight H − S. The case where P → P 0 followed a gradual grouping of experimental data in accordance with the relationship with H − S. We used the three-parameter equation for exothermic processes. For the extrapolated conditions, the so-called point of zero adsorption represented the enthalpy and entropy of adsorption, whose values are analogous to previous results in the literature, which can be considered an appropriate analytical method to determine these two thermodynamic values.

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Section: Introductionmentioning

confidence: 99%

Enthalpy–entropy compensation for isosteric state adsorption at near ambient temperatures

Mianowski

Urbańczyk

2017

Adsorption

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“…(30) ought to serve as the expression for some compensating effect, which is indeed known in the literature-either as the EEC (enthalpyentropy compensation) in the literal sense ðDH vs: DSÞ [21][22][23]. Equation (30) in the EEC model corresponds to the concepts of de Marco and Linert [20], as interpreted by Starikov [24], as well as the concept of an iso-equilibrium relationship [25, p. 781]. Meanwhile, according to the work in this field [19][20][21][22], the dependency of Eq.…”

Section: Analysis Of Eq (12) For Thermal Dissociation Reactionsmentioning

confidence: 99%

“…Equation (30) in the EEC model corresponds to the concepts of de Marco and Linert [20], as interpreted by Starikov [24], as well as the concept of an iso-equilibrium relationship [25, p. 781]. Meanwhile, according to the work in this field [19][20][21][22], the dependency of Eq. (30) might also include an individual chemical compound.…”

Section: Analysis Of Eq (12) For Thermal Dissociation Reactionsmentioning

confidence: 99%

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Thermal dissociation in terms of the second law of chemical thermodynamics

Mianowski

Urbańczyk

2016

J Therm Anal Calorim

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Starting from the relationship between Gibbs free energy and equilibrium constant of a chemical reaction (ECCR) and taking into account its temperature dependence according to Kirchhoff, Eq. (12), we arrive at the three-parametric Eq. (26). In going this way, we employ the relationship between the ECCR and the degree of conversion of the solid phase using Eqs. (20) and (21). We find that there is a compensating effect between the coefficients of the equation (i.e., a 1 ; a 2 ) in the form of a linear equation, which has been attributed to the enthalpy-entropy compensation. According to current state of knowledge, this result applies both to the chemical reactions resulting in individual chemical bond formation as well as in thermal decomposition. When the heat capacity of such chemical reactions decreases linearly along with temperature, it can adopt the value of the (arithmetic mean) average, and the negative sign determines the elements of the functional equations valid for theoretical (Eq. 26) and experimentally fit (Eq. 32) states. For calcite, several possibilities arising from equilibrium changes in the conversion rate vs. temperature are compared by taking into account the CDV L'vov theory.

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“…For example, the work [75] suggests the following physical-chemical interpretation for Eq. (3) (however, without any detailed analysis or the proper references):…”

Section: The Significance Of the Meyer-neldel-rule For Chemistrymentioning

confidence: 99%

‘Meyer-Neldel Rule’: True History of its Development and its Intimate Connection to Classical Thermodynamics

Starikov

2014

J. Appl. Sol. Chem. Model.

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Thermodynamic relationships in complex formation. IX. ΔH – ΔS and free energy relationships in mixed ligand complex formation reactions of Cd(II) in aqueous solution

Cited by 14 publications

References 15 publications

Enthalpy–entropy compensation for isosteric state adsorption at near ambient temperatures

Enthalpy–entropy compensation for isosteric state adsorption at near ambient temperatures

Thermal dissociation in terms of the second law of chemical thermodynamics

‘Meyer-Neldel Rule’: True History of its Development and its Intimate Connection to Classical Thermodynamics

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