Thermodynamics of Size Effect on Phase Transition Temperatures of Dispersed Phases

Cui, Zixiang; Zhao, Ming-Chun; Lai, Weipeng; Xue, Yongqiang

doi:10.1021/jp2067364

Cited by 60 publications

(35 citation statements)

References 63 publications

(94 reference statements)

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“…Since the rate constant can be acquired through regression analysis of the thermokinetic data recorded by in-situ microcalorimetry [26], the molar surface Gibbs free energy of nano-CaMoO4 can be acquired by using Equation (11).…”

Section: Methodsmentioning

confidence: 99%

“…Thus, the molar surface enthalpy, molar surface Gibbs free energy, and molar surface entropy of nano CaMoO4 can be acquired from Equations (6), (11) and (12), respectively.…”

Section: Methodsmentioning

confidence: 99%

“…Surface effect is a basic effect of nanomaterials and many unique properties of nanomaterials are derived from it [4]. Surface thermodynamic properties, including surface Gibbs free energy, surface enthalpy and surface entropy, are an important expression of surface effects, and they have a direct relationship with the chemical thermodynamics [5], chemical kinetics [6], catalysis [7,8], sense [9], adsorption [10], phase transition [11], electrochemistry [12] of nanomaterials. The study of the surface thermodynamic properties of nanomaterials and their structure-function relationships with particle size, morphology and structure is valuable to understand the nature of chemical reactions, but, till now, the development of the surface thermodynamics of nanomaterials is quite poor [13].…”

Section: Introductionmentioning

confidence: 99%

See 2 more Smart Citations

Synthesis and Surface Thermodynamic Functions of CaMoO4 Nanocakes

Fan

Huang

2015

Entropy

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CaMoO4 nanocakes with uniform size and morphology were prepared on a large scale via a room temperature reverse-microemulsion method. The products were characterized in detail by X-ray powder diffraction, field-emission scanning electron microscopy, transmission electron microscopy, and high-resolution transmission electron microscopy. By establishing the relations between the thermodynamic functions of nano-CaMoO4 and bulk-CaMoO4 reaction systems, the equations for calculating the surface thermodynamic functions of nano-CaMoO4 were derived. Then, combined with in-situ microcalorimetry, the molar surface enthalpy, molar surface Gibbs free energy, and molar surface entropy of the prepared CaMoO4 nanocakes at 298.15 K were successfully obtained as (19.674 ± 0.017) kJ·mol

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Section: Methodsmentioning

confidence: 99%

“…Thus, the molar surface enthalpy, molar surface Gibbs free energy, and molar surface entropy of nano CaMoO4 can be acquired from Equations (6), (11) and (12), respectively.…”

Section: Methodsmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

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Synthesis and Surface Thermodynamic Functions of CaMoO4 Nanocakes

Fan

Huang

2015

Entropy

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“…Because when the radius of the nanoparticles approaches or exceeds 10 nm, the effect of particle size on the surface tension can be neglected (Xue et al 2010;Cui et al 2011). So it can be deduced from Eq.…”

Section: Rationality Of the Modelmentioning

confidence: 99%

Theoretical and experimental study: the size dependence of decomposition thermodynamics of nanomaterials

Cui

Duan

et al. 2015

J Nanopart Res

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In the processes of preparation and application of nanomaterials, the decomposition reactions of nanomaterials are often involved. However, there is a dramatic difference in decomposition thermodynamics between nanomaterials and the bulk counterparts, and the difference depends on the size of the particles that compose the nanomaterials. In this paper, the decomposition model of a nanoparticle was built, the theory of decomposition thermodynamics of nanomaterials was proposed, and the relations of the size dependence of thermodynamic quantities for the decomposition reactions were deduced. In experiment, taking the thermal decomposition of nanoCu 2 (OH) 2 CO 3 with different particle sizes (the range of radius is at 8.95-27.4 nm) as a system, the reaction thermodynamic quantities were determined, and the regularities of size dependence of the quantities were summarized. These experimental regularities consist with the above thermodynamic relations. The results show that there is a significant effect of the size of particles composing a nanomaterial on the decomposition thermodynamics. When all the decomposition products are gases, the differences in thermodynamic quantities of reaction between the nanomaterials and the bulk counterparts depend on the particle size; while when one of the decomposition products is a solid, the differences depend on both the initial particle size of the nanoparticle and the decomposition ratio. When the decomposition ratio is very small, these differences are only related to the initial particle size; and when the radius of the nanoparticles approaches or exceeds 10 nm, the reaction thermodynamic functions and the logarithm of the equilibrium constant are linearly associated with the reciprocal of radius, respectively. The thermodynamic theory can quantificationally describe the regularities of the size dependence of thermodynamic quantities for decomposition reactions of nanomaterials, and contribute to the researches and the applications in the decomposition of nanomaterials.

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“…Surface atomic structure is a critical factor affecting many physical and chemical properties of nanomaterials occurring on its surfaces [1,2], including chemical thermodynamics [3][4][5][6][7][8][9], chemical kinetics [5,8], catalysis [10][11][12][13], sense [11], adsorption [14], phase transition [15], and electrochemistry of nanomaterials [16]. Surface thermodynamic properties are the intuitive expression of the special structure-activity relationships of nanomaterial surfaces.…”

Section: Introductionmentioning

confidence: 99%

Reaction Kinetic Parameters and Surface Thermodynamic Properties of Cu2O Nanocubes

Tang

Lü

et al. 2015

Entropy

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Cuprous oxide (Cu2O) nanocubes were synthesized by reducing Cu(OH)2 in the presence of sodium citrate at room temperature. The samples were characterized in detail by field-emission scanning electron microscopy, transmission electron microscopy, high-resolution transmission electron microscopy, X-ray powder diffraction, and N2 absorption (BET specific surface area). The equations for acquiring reaction kinetic parameters and surface thermodynamic properties of Cu2O nanocubes were deduced by establishment of the relations between thermodynamic functions of Cu2O nanocubes and these of the bulk Cu2O. Combined with thermochemical cycle, transition state theory, basic theory of chemical thermodynamics, and in situ microcalorimetry, reaction kinetic parameters, specific surface enthalpy, specific surface Gibbs free energy, and specific surface entropy of Cu2O nanocubes were successfully determined. We also introduced a universal route for gaining reaction kinetic parameters and surface thermodynamic properties of nanomaterials.

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Thermodynamics of Size Effect on Phase Transition Temperatures of Dispersed Phases

Cited by 60 publications

References 63 publications

Synthesis and Surface Thermodynamic Functions of CaMoO4 Nanocakes

Synthesis and Surface Thermodynamic Functions of CaMoO4 Nanocakes

Theoretical and experimental study: the size dependence of decomposition thermodynamics of nanomaterials

Reaction Kinetic Parameters and Surface Thermodynamic Properties of Cu2O Nanocubes

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