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Related Concept Videos

Thermodynamic Systems01:06

Thermodynamic Systems

6.1K
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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Chemical Equilibria: Systematic Approach to Equilibrium Calculations01:21

Chemical Equilibria: Systematic Approach to Equilibrium Calculations

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Equilibrium calculations for systems involving multiple equilibria are often complex. For example, to calculate the solubility of a sparingly soluble salt in an aqueous solution in the presence of a common ion, one must consider all the equilibria in this solution. Calculations for these systems can be complicated and tedious, so a systematic approach with a series of steps is often helpful. The process is detailed below.
The first step is to identify all the chemical reactions involved, The...
1.1K
Zeroth Law of Thermodynamics01:14

Zeroth Law of Thermodynamics

6.0K
Experimentally, if object A is in equilibrium with object B, and object B is in equilibrium with object C, then object A is in equilibrium with object C. That statement of transitivity is called the "zeroth law of thermodynamics." For example, a cold metal block and a hot metal block are both placed on a metal plate at room temperature. Eventually, the cold block and the plate will be in thermal equilibrium. In addition, the hot block and the plate will be in thermal equilibrium.
6.0K
Le Chatelier's Principle: Changing Temperature02:19

Le Chatelier's Principle: Changing Temperature

32.4K
Consistent with the law of mass action, an equilibrium stressed by a change in concentration will shift to re-establish equilibrium without any change in the value of the equilibrium constant, K. When an equilibrium shifts in response to a temperature change, however, it is re-established with a different relative composition that exhibits a different value for the equilibrium constant.
To understand this phenomenon, consider the elementary reaction:
32.4K
Gibbs Free Energy and Thermodynamic Favorability02:23

Gibbs Free Energy and Thermodynamic Favorability

7.3K
The spontaneity of a process depends upon the temperature of the system. Phase transitions, for example, will proceed spontaneously in one direction or the other depending upon the temperature of the substance in question. Likewise, some chemical reactions can also exhibit temperature-dependent spontaneities. To illustrate this concept, the equation relating free energy change to the enthalpy and entropy changes for the process is considered:
7.3K
Free Energy and Equilibrium02:56

Free Energy and Equilibrium

25.0K
The free energy change for a process may be viewed as a measure of its driving force. A negative value for ΔG represents a driving force for the process in the forward direction, while a positive value represents a driving force for the process in the reverse direction. When ΔGrxn is zero, the forward and reverse driving forces are equal, and the process occurs in both directions at the same rate (the system is at equilibrium).
Recall that Q is the numerical value of the mass action...
25.0K

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A rational approach to basic equilibrium thermodynamics.

Jarl B Rosenholm1

  • 1Laboratory of Physical Chemistry, Åbo Akademi University, Porthansgatan 3-5, 20500 Åbo (Turku), Finland.

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Summary

This review presents a Thermodynamic Wheel of Connections (TWC) and tables of thermodynamic derivatives for experimentalists. It extends classical thermodynamics to interfaces and thin films, aiding phase transition analysis.

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Area of Science:

  • Physical Chemistry
  • Thermodynamics
  • Surface Science

Background:

  • Classical thermodynamics, despite its elegance and broad applicability, requires systematic organization of its fundamental relationships.
  • Albert Einstein recognized classical thermodynamics as a universally applicable physical theory unlikely to be overthrown.
  • Experimentalists need comprehensive tools to derive and understand thermodynamic properties and phase transitions.

Purpose of the Study:

  • To present basic relationships between partial derivatives of internal energy, enthalpy, Helmholtz, and Gibbs energies in a condensed format.
  • To provide experimentalists with a complete set of first- and second-order partial derivatives of basic state functions under various conditions.
  • To extend thermodynamic analysis to interfaces and thin films, including phase transitions and interfacial properties.

Main Methods:

  • Development of a 'Thermodynamic Wheel of Connections' (TWC) to visualize relationships between thermodynamic state functions and their derivatives.
  • Compilation of a comprehensive table of first- and second-order partial derivatives for bulk phases under isothermal, isobaric, isochoric, and isentropic conditions.
  • Extension of the TWC framework to include interfacial parameters (e.g., chemical potential, surface tension) and derivation of interfacial state functions.

Main Results:

  • The TWC provides a self-consistent network of fundamental thermodynamic relationships.
  • A complete table of derivatives supports experimentalists in thermodynamic calculations.
  • The extended framework successfully characterizes phase transitions and interfacial properties of bulk phases, interphases, and Langmuir films.

Conclusions:

  • The presented TWC and derivative tables offer a unified and accessible approach to classical thermodynamics.
  • The extension to interfacial phenomena provides a powerful tool for understanding complex systems.
  • This work consolidates and expands upon existing thermodynamic formalisms for both bulk and interfacial systems.