Design and Thermodynamic Analysis on One-Step Amination of Benzene to Aniline Systems

2012 ◽  
Vol 550-553 ◽  
pp. 2607-2611
Author(s):  
Chun Hua Yang ◽  
Gang Chen ◽  
Long Zhang
Keyword(s):  
Hydrogen Peroxide ◽  
Free Energy ◽  
Equilibrium Constant ◽  
Gibbs Free Energy ◽  
Driving Force ◽  
Theoretical Basis ◽  
Free Energies ◽  
One Step ◽  
The One ◽  
Further Development

Seven systems of one-step synthesis of aniline were designed, and it was determined which one could occur spontaneously through the calculation of Gibbs free energy of it. Among the seven systems, the Gibbs free energy of the one with ammonia as the aminating agent and hydrogen peroxide as the oxidant was the lowest, thus its process driving force was the largest, that is, .For this system just mentioned above, the standard Gibbs free energies, the equilibrium constant and the equilibrium conversions of benzene under different conditions were discussed ,which was expected to provide a theoretical basis for further development and application of the system.

Chemical equilibrium and chemical kinetics

2018 ◽  
Author(s):  
Dennis Sherwood ◽  
Paul Dalby
Keyword(s):  
Free Energy ◽  
Equilibrium Constant ◽  
Gibbs Free Energy ◽  
Chemical Kinetics ◽  
Chemical Equilibrium ◽  
First Principles ◽  
Effect Of Temperature ◽  
Total System ◽  
Free Energies

Building on the previous chapter, this chapter examines gas phase chemical equilibrium, and the equilibrium constant. This chapter takes a rigorous, yet very clear, ‘first principles’ approach, expressing the total Gibbs free energy of a reaction mixture at any time as the sum of the instantaneous Gibbs free energies of each component, as expressed in terms of the extent-of-reaction. The equilibrium reaction mixture is then defined as the point at which the total system Gibbs free energy is a minimum, from which concepts such as the equilibrium constant emerge. The chapter also explores the temperature dependence of equilibrium, this being one example of Le Chatelier’s principle. Finally, the chapter links thermodynamics to chemical kinetics by showing how the equilibrium constant is the ratio of the forward and backward rate constants. We also introduce the Arrhenius equation, closing with a discussion of the overall effect of temperature on chemical equilibrium.

scholarly journals Rationalisation of the activities of phenolic (vitamin E-type) antioxidants

2003 ◽  
Vol 17 (4) ◽  
pp. 753-762
Author(s):  
Christopher J. Rhodes ◽  
Thuy T. Tran ◽  
Philip Denton ◽  
Harry Morris
Keyword(s):  
Free Energy ◽  
Vitamin E ◽  
Gibbs Free Energy ◽  
State Theory ◽  
Linear Free Energy Relationship ◽  
Free Energies ◽  
Gibbs Free Energy Change ◽  
Linear Free Energy ◽  
Free Energy Of Activation ◽  
Enthalpy And Entropy

Using Transition-State Theory, experimental rate constants, determined over a range of temperatures, for reactions of vitamin E type antioxidants are analysed in terms of their enthalpies and entropies of activation. It is further shown that computational methods may be employed to calculate enthalpies and entropies, and hence Gibbs Free Energies, for the overall reactions. Within the Linear Free Energy Relationship (LFER) assumption, that the Gibbs Free Energy of activation is proportional to the overall Gibbs Free Energy change for the reaction, it is possible to rationalise, and even to predict, the relative contributions of enthalpy and entropy for reactions of interest, involving potential antioxidants.

Thermodynamic studies in solution. Part IV. Solvent effect on the solvolysis of tert-butyl chloride. A new treatment of the experimental data

1979 ◽  
Vol 57 (5) ◽  
pp. 500-502 ◽  
Author(s):  
Joaquim Jose Moura Ramos ◽  
Jacques Reisse ◽  
M. H. Abraham
Keyword(s):  
Free Energy ◽  
Solvent Effect ◽  
Free Energies ◽  
Butyl Chloride ◽  
Activation Free Energy ◽  
Tert Butyl ◽  
New Treatment ◽  
The One ◽  
Activated Complex ◽  
Tert Butyl Chloride

A new treatment of the solvent effect on the solvolysis of tert-butyl chloride is proposed. This treatment is based on activation free energy measurements and on transfer free energy measurements of the reactant (R) on the one hand and of a model (M) of the activated complex (AC) on the other hand. Solute–solvent interaction free energies for the reactant, the activated complex and the model compound are estimated. This estimation involves the calculation of the free energy of cavity formation of these various solutes (R, AC, and M) in all the solvents. These cavity terms, which are a function of the cohesive properties of the solvent and of the surface of the cavity do not reflect the electronic structure of the solute whereas the interaction free energy term does. The method we propose can be described as a new 'experimental' approach for the study of the charge separation in an activated complex.

Effect of mechanical activation on the structure of pulverized coal and iron ore powder

2019 ◽  
Vol 116 (6) ◽  
pp. 624
Author(s):  
Rufei Wei ◽  
Dongwen Xiang ◽  
Hongming Long ◽  
Jiaxin Li ◽  
Qingmin Meng
Keyword(s):  
Free Energy ◽  
Mechanical Activation ◽  
Gibbs Free Energy ◽  
Iron Ore ◽  
Pulverized Coal ◽  
Activation Process ◽  
Free Energies ◽  
Boundary Area ◽  
Particle Sizer ◽  
Storage Energy

Morphologies and structures of pulverized coal and iron ore powder after mechanical activation were studied by SEM, XRD, FTIR and laser particle sizer. The microcrystalline structure of coal was found to be destroyed by mechanical activation via reducing the pile height and number of layers, and the organic structure of coal was altered through the destruction of the ether bond. Mechanical activation led to distortions and dislocations of the crystal lattice of iron ore, decreasing crystallite size, increasing the grain boundary area, and producing an amorphous phase. These increased the Gibbs free energies of dislocations and grain boundaries as well as the surface Gibbs free energy and the amorphization Gibbs free energy, which would eventually increase the energy stored in iron ore called mechanical storage energy. The longer the mechanical activation process, the higher mechanical storage energy for the iron ore will be saved. The amorphization Gibbs free energy is the biggest among the four kinds of Gibbs free energy, accounting for 94.8% ∼ 87.1% of the total storage energy in the mechanical activated iron ore.

The Size Dependence of Dissolution Thermodynamics of Nanoparticles

NANO ◽  
2016 ◽  
Vol 11 (09) ◽  
pp. 1650100 ◽  
Author(s):  
Zhi-Qiang Wang ◽  
Yong-Qiang Xue ◽  
Zi-Xiang Cui ◽  
Hui-Juan Duan ◽  
Xiao-Yan Xia
Keyword(s):  
Particle Size ◽  
Free Energy ◽  
Thermodynamic Properties ◽  
Equilibrium Constant ◽  
Gibbs Free Energy ◽  
Average Particle ◽  
Dissolution Enthalpy ◽  
Dissolution Entropy ◽  
Dissolution Thermodynamics ◽  
Dissolution Thermodynamic Properties

Dissolution of nanoparticles is involved in the preparation, research and application of nanomaterials, but there is a surprising difference in dissolution thermodynamics between nanoparticles and the corresponding bulk materials. In the paper, the relations of dissolution thermodynamic properties, equilibrium constant of nanoparticles, respectively, and particle size were derived by introducing interface variables and the surface chemical potential. Experimentally, the solubility of nano-barium sulfate with different average particle sizes at different temperatures were determined by the method of electrical conductivity, obtaining the influencing regularities of particle size on the dissolution thermodynamic properties and the equilibrium constant. The regularities are in accordance with the theory. The results show that there are remarkable effects of particle size of nanoparticles on the dissolution thermodynamic properties and the equilibrium constant; with the decreasing of the size of nanoparticles, the dissolution equilibrium constant increases, while the standard dissolution Gibbs free energy, the standard dissolution enthalpy and the standard dissolution entropy decrease; and the logarithm of the dissolution equilibrium constant, the standard dissolution Gibbs free energy, the standard dissolution enthalpy and the standard dissolution entropy are linearly associated with the reciprocal of particle size, respectively. This new theory provides a quantitative description of nanoparticles dissolution behavior, and has important scientific significance for understanding and predicting of thermodynamic regularity of dissolution concerned in the preparation, researches and applications of nanomaterials.

scholarly journals Thermodynamically Consistent Estimation of Gibbs Free Energy from Data: Data Reconciliation Approach

2018 ◽  
Author(s):  
Saman Salike ◽  
Nirav Bhatt
Keyword(s):  
Experimental Data ◽  
Free Energy ◽  
Gibbs Free Energy ◽  
Measurement Errors ◽  
Optimization Problems ◽  
Data Reconciliation ◽  
Group Contributions ◽  
Free Energies ◽  
Consistent Estimation ◽  
Gibbs Energies

AbstractMotivationThermodynamic analysis of biological reaction networks requires the availability of accurate and consistent values of Gibbs free energies of reaction and formation. These Gibbs energies can be measured directly via the careful design of experiments or can be computed from the curated Gibbs free energy databases. However, the computed Gibbs free energies of reactions and formations do not satisfy the thermodynamic constraints due to the compounding effect of measurement errors in the experimental data. The propagation of these errors can lead to a false prediction of pathway feasibility and uncertainty in the estimation of thermodynamic parameters.ResultsThis work proposes a data reconciliation framework for thermodynamically consistent estimation of Gibbs free energies of reaction, formation and group contributions from experimental data. In this framework, we formulate constrained optimization problems that reduce measurement errors and their effects on the estimation of Gibbs energies such that the thermodynamic constraints are satisfied. When a subset of Gibbs free energies of formations is unavailable, it is shown that the accuracy of their resulting estimates is better than that of existing empirical prediction methods. Moreover, we also show that the estimation of group contributions can be improved using this approach. Further, we provide guidelines based on this approach for performing systematic experiments to estimate unknown Gibbs formation energies.AvailabilityThe MATLAB code for the executing the proposed algorithm is available for free on the GitHub repository:https://github.com/samansalike/[email protected]

scholarly journals The effect of temperature on the okra drying process: kinetic study and physical properties of powders

2021 ◽  
pp. 649-660
Author(s):  
Francislaine Suelia dos Santos ◽  
Rossana Maria Feitosa de Figueirêdo ◽  
Alexandre José de Melo Queiroz ◽  
Ana Raquel Carmo de Lima ◽  
Thalis Leandro Bezerra de Lima
Keyword(s):  
Free Energy ◽  
Physical Properties ◽  
Gibbs Free Energy ◽  
Effective Diffusion ◽  
Effective Diffusivity ◽  
Effect Of Temperature ◽  
Drying Temperature ◽  
Drying Kinetic ◽  
Drying Models ◽  
The One

This study aimed to evaluate the effect of drying temperature (50, 60, 70 and 80 °C) on okra dehydration by comparing its powder’s physical properties obtained from a sample produced by a lyophilization process. Ten drying models were adjusted to the experimental data of the drying kinetics. As a result, effective diffusivity and activation energy were determined in addition to thermodynamic parameters: entropy, enthalpy and Gibbs free energy. A physical characterization, as well as the pigments and colorimetry analyses of the aforementioned powders were made, by comparing them with samples produced by lyophilization. The powders were characterized for hygroscopicity, solubility, wettability, apparent and compacted density, fluidity and cohesiveness, pigments, colorimetric, morphological analysis (SEM) and X-ray diffraction. Midilli model was the one that best adjusted to the drying kinetic curves. There was a booster in the effective diffusion coefficient with the increase of temperature. Enthalpy and entropy were reduced with the increase of both drying temperature and Gibbs free energy. The powders presented high luminosity, and the lyophilized powder had higher pigments retention and greater solubility. All powders presented poor fluidity and intermediate cohesiveness, with amorphous, irregular and asymmetric particles. Thus, from the present study it was possible to evaluate the best drying method, the one that should be applied for the drying of okra, considering the costs involved, its quality and the final application of the product, meeting the specific needs of each consumer

Free energy

2018 ◽  
Author(s):  
Dennis Sherwood ◽  
Paul Dalby
Keyword(s):  
Free Energy ◽  
Gibbs Free Energy ◽  
Helmholtz Free Energy ◽  
Chemical Potential ◽  
Free Energies ◽  
Central Concept ◽  
Mathematical Properties ◽  
Closed Systems ◽  
Coupled Reactions ◽  
Enthalpy And Entropy

A critical chapter, explaining how the principles of thermodynamics can be applied to real systems. The central concept is the Gibbs free energy, which is explored in depth, with many examples. Specific topics addressed are: Spontaneous changes in closed systems. Definitions and mathematical properties of Gibbs free energy and Helmholtz free energy. Enthalpy- and entropy-driven reactions. Maximum available work. Coupled reactions, and how to make non-spontaneous changes happen, with examples such as tidying a room, life, and global warming. Standard Gibbs free energies. Mixtures, partial molar quantities and the chemical potential.

scholarly journals White Light-Emitting Devices Based on Inorganic Perovskite and Organic Materials

Molecules ◽  
2019 ◽  
Vol 24 (4) ◽  
pp. 800 ◽  
Author(s):  
Shuming Chen ◽  
Chen Chen ◽  
Cong Bao ◽  
Muhammad Mujahid ◽  
Ye Li ◽  
...  
Keyword(s):  
White Light ◽  
Polymer Composite Material ◽  
Maximum Luminance ◽  
Light Emitting ◽  
Inorganic Perovskite ◽  
Light Emitting Devices ◽  
Hole Transporting ◽  
One Step ◽  
The One ◽  
Further Development

Perovskite-based materials have attracted considerable attention in photoelectric devices. In this paper, we report the one-step fabrication of spin-coated CsPbBr2.5I0.5 perovskite films doped with PAN (polyacrylonitrile) polymer. A red perovskite LED (PeLED) composite film was fabricated which featured a maximum luminance value of 657 cd/m2 at 8 V. We fabricated white PeLEDs by combining hole transporting layer material emission, perovskite–polymer composite material PAN:CsPbBr2.5I0.5, and pure inorganic perovskite CsPbBr3 as a luminescent layer. The maximum luminance of the device was 360 cd/m2 at 7 V, and the color coordinate was (0.31, 0.36). We obtained an ideal white light-emitting device that paves the way for further development of white PeLEDs.

Chemical Thermodynamics

2021 ◽  
pp. 344-364
Author(s):  
Christopher O. Oriakhi
Keyword(s):  
Free Energy ◽  
Phase Change ◽  
Equilibrium Constant ◽  
Gibbs Free Energy ◽  
Chemical Thermodynamics ◽  
Laws Of Thermodynamics ◽  
Core Concepts ◽  
Enthalpy And Entropy Changes ◽  
Enthalpy And Entropy ◽  
The Relationship

Chemical Thermodynamics discusses the fundamental laws of thermodynamics along with their relationships to heat, work, enthalpy, entropy, and temperature. Predicting the direction of a spontaneous change and calculating the change in entropy of a reaction are core concepts. The relationship between entropy, free energy and work is covered. The Gibbs free energy is used quantitatively to predict if reactions or processes are going to be exothermic and spontaneous or endothermic under the stated conditions. Also explored are the enthalpy and entropy changes during a phase change. Finally the Gibbs free energy of a chemical reaction is related to its equilibrium constant and the temperature.

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