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Related Concept Videos

Isothermal Processes01:21

Isothermal Processes

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A thermodynamic process that occurs at constant temperature is called an isothermal process. Heat slowly flows into the system or out of the system to maintain thermal equilibrium. Processes involving phase changes like water evaporation into steam or freezing water into ice at a constant temperature are examples of Isothermal Processes.
An ideal gas can also undergo isothermal expansion or compression.
For example, consider 1 mole of an ideal gas inside an isolated cylinder at initial volume V...
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Isochoric and Isobaric Processes01:21

Isochoric and Isobaric Processes

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A thermodynamic process that occurs at constant volume is called an isochoric process. According to the first law of thermodynamics, heat supplied or removed from the system is partially utilized to perform work and change the internal energy of the system. However, in an isochoric process, the volume remains constant. Hence, the work done by the system is zero. Therefore, the exchange of heat changes the internal energy of the system only. 
Suppose 1000 g of water is heated from 40...
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Thermodynamic Systems01:06

Thermodynamic Systems

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A thermodynamic system is a set of objects whose thermodynamic properties are of interest. The system is considered to be embedded in its surroundings or the environment. The system and its environment can exchange heat and do work on each other through a boundary that separates them. However, the immediate surroundings of the system interact with it directly and therefore have a much stronger influence on its behavior and properties.
Consider an example of  tea boiling in a kettle. The...
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Adiabatic Processes for an Ideal Gas01:18

Adiabatic Processes for an Ideal Gas

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When an ideal gas is compressed adiabatically, that is, without adding heat, work is done on it, and its temperature increases. In an adiabatic expansion, the gas does work, and its temperature drops. Adiabatic compressions actually occur in the cylinders of a car, where the compressions of the gas-air mixture take place so quickly that there is no time for the mixture to exchange heat with its environment. Nevertheless, because work is done on the mixture during the compression, its...
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Temperature and Thermal Equilibrium01:11

Temperature and Thermal Equilibrium

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Heat and temperature are essential concepts for everyone every day. The study of heat and temperature is part of an area of physics known as thermodynamics. It is not always easy to distinguish heat and temperature.
The concept of temperature has evolved from the common concepts of hot and cold. The scientific definition of temperature explains more than just our sense of hot and cold. Temperature is operationally defined as the quantity measured with a thermometer. Furthermore, temperature is...
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Enthalpy of Solution02:39

Enthalpy of Solution

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There are two criteria that favor, but do not guarantee, the spontaneous formation of a solution:
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Computation of Atmospheric Concentrations of Molecular Clusters from ab initio Thermochemistry
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Isothermal-isobaric ensemble for small systems.

D S Corti1

  • 1School of Chemical Engineering, Purdue University, West Lafayette, Indiana 47907-1283, USA.

Physical Review. E, Statistical, Nonlinear, and Soft Matter Physics
|July 20, 2001
PubMed
Summary
This summary is machine-generated.

The isothermal-isobaric (N-P-T) ensemble requires a specific volume scale for small systems to ensure accurate partition functions. Careful selection of this scale is crucial for rigorous small system simulations.

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Area of Science:

  • Thermodynamics
  • Statistical Mechanics
  • Computational Chemistry

Background:

  • The isothermal-isobaric (N-P-T) ensemble is a fundamental tool in statistical mechanics.
  • Small systems are increasingly important in scientific and technological applications.
  • Accurate thermodynamic descriptions of small systems are challenging.

Purpose of the Study:

  • To analyze the application of the N-P-T ensemble to small systems.
  • To highlight the necessity and challenges of introducing a volume scale for small systems.
  • To ensure the rigorous description of small systems using ensembles.

Main Methods:

  • Consideration of the N-P-T ensemble in the small system limit.
  • Introduction and analysis of a dimensionless volume scale.
  • Examination of the dependence of the volume scale on system-surrounding boundary conditions.

Main Results:

  • A dimensionless partition function requires a carefully chosen volume scale for small systems.
  • The choice of volume scale is contingent upon the boundary conditions.
  • Incorrect volume scale selection leads to inaccurate ensemble descriptions.

Conclusions:

  • Volume scales are critical for the accurate formulation of N-P-T ensembles for small systems.
  • While volume scales become negligible in the thermodynamic limit, they are essential for small systems.
  • Careful consideration of volume scale is paramount for reliable small system simulations.