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Entropy02:39

Entropy

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Salt particles that have dissolved in water never spontaneously come back together in solution to reform solid particles. Moreover, a gas that has expanded in a vacuum remains dispersed and never spontaneously reassembles. The unidirectional nature of these phenomena is the result of a thermodynamic state function called entropy (S). Entropy is the measure of the extent to which the energy is dispersed throughout a system, or in other words, it is proportional to the degree of disorder of a...
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Entropy and the Second Law of Thermodynamics01:20

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The second law of thermodynamics can be stated quantitatively using the concept of entropy. Entropy is the measure of disorder of the system.
The relation  between entropy and disorder can be illustrated with the example of the phase change of ice to water. In ice, the molecules are located at specific sites giving a solid state, whereas, in a liquid form, these molecules are much freer to move. The molecular arrangement has therefore become more randomized. Although the change in average...
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Entropy and Solvation02:05

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The process of surrounding a solute with solvent is called solvation. It involves evenly distributing the solute within the solvent. The rule of thumb for determining a solvent for a given compound is that like dissolves like. A good solvent has molecular characteristics similar to those of the compound to be dissolved. For example, polar solutions dissolve polar solutes, and apolar solvents dissolve apolar solutes. A polar solvent is a solvent that has a high dielectric constant (ϵ...
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A pure, perfectly crystalline solid possessing no kinetic energy (that is, at a temperature of absolute zero, 0 K) may be described by a single microstate, as its purity, perfect crystallinity,and complete lack of motion means there is but one possible location for each identical atom or molecule comprising the crystal (W = 1). According to the Boltzmann equation, the entropy of this system is zero.
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The Second Law of Thermodynamics01:14

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In the quest to identify a property that may reliably predict the spontaneity of a process, a promising candidate has been identified: entropy. Scientists refer to the measure of randomness or disorder within a system as entropy. High entropy means high disorder and low energy. To better understand entropy, think of a student’s bedroom. If no energy or work were put into it, the room would quickly become messy. It would exist in a very disordered state, one of high entropy. Energy must be...
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The shape of a small drop of liquid can be considered spherical, neglecting the effect of gravity. This drop can further be considered as two equal hemispherical drops put together due to surface tension. The forces acting on the spherical drop are due to the pressure of the liquid inside the drop, the pressure due to air outside the drop, and the force due to the surface tension acting on the two hemispherical drops.
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Linking excess entropy and acentric factor in spherical fluids.

Tae Jun Yoon1,2, Ian H Bell3

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Summary
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The physical meaning of the centric fluid, a concept used to understand molecular behavior, is clarified through excess entropy. Centric fluids exhibit balanced repulsive and attractive entropic contributions at gas-liquid criticality.

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Area of Science:

  • Thermodynamics and Statistical Mechanics
  • Physical Chemistry
  • Intermolecular Forces

Background:

  • The acentric factor (ω) quantifies molecular deviation from the corresponding states principle.
  • Pitzer's concept of a perfect or centric fluid, while useful, lacks clear physical interpretation.
  • Understanding centric fluids is key to refining models of molecular behavior.

Purpose of the Study:

  • To elucidate the physical significance of the centric fluid using an excess entropy perspective.
  • To investigate the entropic contributions that define centric fluids.
  • To connect the centric fluid concept to gas-liquid criticality and molecular interactions.

Main Methods:

  • Analysis of excess entropy per particle for centric fluids at critical points.
  • Development and application of an excess entropy dissection method.
  • Modeling of various fluids including square-well, Lennard-Jones, Mie n-6, and ab initio potentials.

Main Results:

  • Excess entropy per particle of centric fluids approximates -kB at critical points, similar to ideal gas communal entropy.
  • Attractive interaction entropy contribution peaks due to attraction-fluctuation competition, independent of the acentric factor.
  • Centric fluids show comparable repulsive and attractive entropic contributions, leading to greater structure than acentric fluids.

Conclusions:

  • The physical significance of the centric fluid is defined by the equality of repulsive and attractive excess entropy contributions at gas-liquid criticality.
  • This work provides insights into the nature of centric fluids and their relation to molecular interactions.
  • Findings can aid in selecting appropriate intermolecular potentials and evaluating equations of state.