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

Starikov, E. B.

doi:10.6000/1929-5030.2014.03.01.3

Cited by 15 publications

(18 citation statements)

References 86 publications

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“…3a, 4a) and for µ → 1, due to the participation of entropy, the experimental data move away from the isosteric straight H − S. 3. Due to the important role of entropy in explaining the EEC, in line with Starikov (2014), it is necessary to specify what values are the determinant conditions. Its values are 10 3 times smaller than those of enthalpy or different-isosteric heat of adsorption.…”

Section: Discussionmentioning

confidence: 99%

“…where it is postulated according to (Starikov 2014) that the isokinetic enthalpy (the absolute) is 15 kJ mol −1 (Pera-Titus 2016).…”

Section: Introductionmentioning

confidence: 99%

“…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%

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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: Discussionmentioning

confidence: 99%

“…where it is postulated according to (Starikov 2014) that the isokinetic enthalpy (the absolute) is 15 kJ mol −1 (Pera-Titus 2016).…”

Section: Introductionmentioning

confidence: 99%

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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%

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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“…Figure 1 depicts typical behavior of entropy and enthalpy vs. temperature, and one can immediately recognize the convergent behavior of the both up to the value of x = 1, after which the graphs diverge. Hence, it is throughout possible to interpret this as an enthalpy-entropy compensation (EEC), whereas x = 1, that is, T = T ref defines the so-called "enthalpy-entropy compensation temperature" T c , that is, T ref ≡ T c (see e.g., [43][44][45][46][47][48][49][50][51][52] and the references therein).…”

Section: Entropy-enthalpy Compensation At the Tip Of Penmentioning

confidence: 99%

Bayesian Statistical Mechanics: Entropy-Enthalpy Compensation and Universal Equation of State at the Tip of Pen

Starikov

2018

Front. Phys.

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

Abstract: The history of the Meyer-Neldel rule's development and the initial collective efforts toward its comprehension have been described here. The whole story gives a nice occasion to trigger thorough analysis of the basic thermodynamic laws and looking for the true sense of the entropy notion.

Cited by 15 publications

References 86 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

Bayesian Statistical Mechanics: Entropy-Enthalpy Compensation and Universal Equation of State at the Tip of Pen

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