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Third Law of Thermodynamics02:38

Third Law of Thermodynamics

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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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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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Entropy01:18

Entropy

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The first law of thermodynamics is quantitatively formulated via an equation relating the internal energy of a system, the heat exchanged by it, and the work done on it. A quantitative formulation of the second law of thermodynamics leads to defining a state function, the entropy.
When an ideal gas expands isothermally, the disorder in the gas increases. From the molecular perspective, the gas molecules have more volume to move around in.
Consider an infinitesimal step in the expansion, which...
3.7K
Second Law of Thermodynamics02:49

Second Law of Thermodynamics

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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. Processes that involve an increase in entropy of the system (ΔS > 0) are very often spontaneous; however, examples to the contrary are plentiful. By expanding consideration of entropy changes to include the surroundings, a significant conclusion regarding the relation between this property and spontaneity may be reached. In thermodynamic models, the...
27.4K
Entropy Changes Accompanying Specific Processes01:21

Entropy Changes Accompanying Specific Processes

28
Entropy, a measure of disorder in a system, changes during phase transitions like freezing or boiling. At the transition temperature Ttrs, where two phases are in equilibrium, the phase transition is a reversible process. The entropy change can be calculated from a substance's enthalpy of transition using the equation ΔStrs = ΔtrsH /Ttrs.When a perfect gas expands isothermally from one volume to another, entropy increases logarithmically with volume. Conversely, isothermal compression...
28
Entropy within the Cell01:22

Entropy within the Cell

13.8K
A living cell's primary tasks of obtaining, transforming, and using energy to do work may seem simple. However, the second law of thermodynamics explains why these tasks are harder than they appear. None of the energy transfers in the universe are completely efficient. In every energy transfer, some amount of energy is lost in a form that is unusable. In most cases, this form is heat energy. Thermodynamically, heat energy is defined as the energy transferred from one system to another that...
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Related Experiment Video

Updated: Mar 7, 2026

An Analog Macroscopic Technique for Studying Molecular Hydrodynamic Processes in Dense Gases and Liquids
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An Analog Macroscopic Technique for Studying Molecular Hydrodynamic Processes in Dense Gases and Liquids

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Surface single-molecule dynamics controlled by entropy at low temperatures.

J C Gehrig1, M Penedo1, M Parschau1

  • 1Empa, Swiss Federal Laboratories for Materials Science and Technology, CH-8600 Dübendorf, Switzerland.

Nature Communications
|February 10, 2017
PubMed
Summary
This summary is machine-generated.

Investigating single molecule transitions on surfaces reveals that tip-molecule interactions significantly alter energy barriers and attempt rates. This study demonstrates enthalpy-entropy compensation, crucial for understanding molecular dynamics at low temperatures.

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Area of Science:

  • Surface Science
  • Physical Chemistry
  • Nanotechnology

Background:

  • Molecular and atomic transitions on surfaces are typically modeled using Arrhenius kinetics.
  • Significant variations in pre-exponential factors and energy barriers are observed even for identical systems.

Purpose of the Study:

  • To investigate the influence of scanning tunneling microscopy (STM) tip position on single-molecule transition dynamics.
  • To explore the phenomenon of enthalpy-entropy compensation in molecular transitions.

Main Methods:

  • Utilized low-temperature scanning tunneling microscopy (STM) to probe individual dibutyl sulfide molecules on Au(111).
  • Precisely controlled the relative position of the STM tip apex and the molecule.

Main Results:

  • STM tip positioning, even by a fraction of molecular size, significantly alters transition energy barriers and pre-exponential factors.
  • Observed a strong correlation between changes in barrier and attempt rate, indicating single-molecular enthalpy-entropy compensation.
  • Demonstrated the ability to tune transition rates by selecting specific STM tip operating points.

Conclusions:

  • Enthalpy-entropy compensation is a critical factor in single-molecule transition rates, even at low temperatures.
  • The STM tip's influence on molecular configurations must be considered in surface dynamics studies.
  • Precise control over tip-molecule interactions offers a method to manipulate molecular transition rates.