Geometric foundation of thermo-statistics, phase transitions, second law of thermodynamics, but without thermodynamic limit

Literature Information

Publication Date 2002-02-19
DOI 10.1039/B108775D
Impact Factor 3.676
Authors


View Original

Abstract

A geometric foundation thermo-statistics is presented with the only axiomatic assumption of Boltzmann's principleS(E, N, V) = klnW. This relates the entropy to the geometric area eS(E, N, V)/k of the manifold of constant energy in the (finite-N)-body phase space. From the principle, all thermodynamics and especially all phenomena of phase transitions and critical phenomena can unambiguously be identified for even small systems. The topology of the curvature matrix C(E, N) of S(E, N) determines regions of pure phases, regions of phase separation, and (multi-)critical points and lines. Phase transitions are linked to convex (upwards bending) intruders of S(E, N), where the canonical ensemble defined by the Laplace transform to the intensive variables becomes multi-modal, non-local, (it mixes widely different conserved quantities). Here the one-to-one mapping of the Legendre transform gets lost. Within Boltzmann's principle, statistical mechanics becomes a geometric theory addressing the whole ensemble or the manifold of all points in phase space which are consistent with the few macroscopic conserved control parameters. This interpretation leads to a straight derivation of irreversibility and the second law of thermodynamics out of the time-reversible, microscopic, mechanical dynamics. It is the whole ensemble that spreads irreversibly over the accessible phase space not the single N-body trajectory. This is all possible without invoking the thermodynamic limit, extensivity, or concavity of S(E, N, V). Without the thermodynamic limit or at phase-transitions, the systems are usually not self-averaging, i.e. do not have a single peaked distribution in phase space. The main obstacle against the second law, the conservation of the phase-space volume due to Liouville is overcome by realizing that a macroscopic theory such as thermodynamics cannot distinguish a fractal distribution in phase space from its closure.

Related Literature

Free-base porphyrins with localized NH protons. Can substituents alone stabilize the elusive cis tautomer?

Kolle E. Thomas, Christine M. Beavers, Abhik Ghosh

2020-03-26 Paper

DOI: 10.1039/D0OB00452A

Wagner–Meerwein type rearrangement in 5-oxohomoadamantane series

Ilya M. Tkachenko, Polina A. Mankova, Victor B. Rybakov, Evgeniy V. Golovin, Yuri N. Klimochkin

2019-12-17 Paper

DOI: 10.1039/C9OB02060H

Total synthesis of isatindigotindoline C

Juha H. Siitonen, Sherlin Lira, Muhammed Yousufuddin, László Kürti

2020-03-02 Communication

DOI: 10.1039/D0OB00270D

Contents list

Front/Back Matter

DOI: 10.1039/D0OB90037K

Stereoselective Michael additions on α-aminoacrylates as the key step to an l-Oic analogue bearing a quaternary stereocenter

Federico Maria Cecchinelli, Giuseppe Celentano, Alessandra Puglisi, Nicoletta Gaggero

2019-12-16 Paper

DOI: 10.1039/C9OB02084E

Mechanism and stereoselectivity of benzylic C–H hydroxylation by Ru–porphyrin: a computational study

Xiahe Chen, Qunmin Wang, Haimin Shen, Guijie Li, Yun-Fang Yang, Yuan-Bin She

2019-12-09 Paper

DOI: 10.1039/C9OB02415H

Visible light photoredox catalyzed deprotection of 1,3-oxathiolanes

Mingyang Yang, Zhimin Xing, Bowen Fang, Xingang Xie, Xuegong She

2019-12-06 Paper

DOI: 10.1039/C9OB02517K

The impact of cation structure upon the acidity of triazolium salts in dimethyl sulfoxide

Nicholas Konstandaras, Michelle H. Dunn, Max S. Guerry, Christopher D. Barnett, Marcus L. Cole, Jason B. Harper

2019-11-14 Paper

DOI: 10.1039/C9OB02258A

You might also like

Compound Q&A

What regulatory guidelines apply to 6-Bromo-2-methylimidazo[1,2-a]pyrimidine (CAS: 1111638-05-1)?

6-Bromo-2-methylimidazo[1,2-a]pyrimidine (CAS: 1111638-05-1) falls under various...

1111638-05-16-Bromo-2-methylimid...
Compound Q&A

Are there alternatives to 1-Pyrrolidineethanol, β-methyl-α-phenyl-, (αS,βR) (CAS: 123620-80-4) in synthesis?

While there are no direct alternatives, similar compounds like 1-Pyrrolidineetha...

123620-80-41-Pyrrolidineethanol...
Compound Q&A

Is 4-Methyl-2,6-bis(2-methyl-2-propanyl)phenyl methylcarbamate (CAS: 1918-11-2) safe?

4-Methyl-2,6-bis(2-methyl-2-propanyl)phenyl methylcarbamate (CAS: 1918-11-2) is ...

1918-11-24-Methyl-2,6-bis(2-m...
Compound Q&A

How should 2-(3-Bromo-4-fluorophenyl)-1,3-dioxolane (CAS: 77771-04-1) be stored?

2-(3-Bromo-4-fluorophenyl)-1,3-dioxolane (CAS: 77771-04-1) should be stored in a...

77771-04-12-(3-Bromo-4-fluorop...
Compound Q&A

What are the physical and chemical properties of 4,5,6,7-Tetrahydro-1H-indazole hydrochloride (CAS: 18161-11-0)?

4,5,6,7-Tetrahydro-1H-indazole hydrochloride is a white crystalline solid with a...

18161-11-04,5,6,7-Tetrahydro-1...
Compound Q&A

What is (2R)-1-Methoxy-3-phenyl-2-propanamine (CAS: 59919-07-2)?

(2R)-1-Methoxy-3-phenyl-2-propanamine is a chiral organic compound with the CAS ...

59919-07-2(2R)-1-Methoxy-3-phe...
Compound Q&A

What industries use Ethyl 1-(1-phenylethyl)-1H-imidazole-5-carboxylate (CAS: 56649-47-9)?

Ethyl 1-(1-phenylethyl)-1H-imidazole-5-carboxylate is used in various industries...

56649-47-9Ethyl 1-(1-phenyleth...
Compound Q&A

What regulatory guidelines apply to 4-[(1E,3S)-1-(4-Hydroxyphenyl)-1,4-pentadien-3-yl]phenol (CAS: 17676-24-3)?

4-[(1E,3S)-1-(4-Hydroxyphenyl)-1,4-pentadien-3-yl]phenol (CAS: 17676-24-3) falls...

17676-24-34-[(1E,3S)-1-(4-Hydr...
Compound Q&A

What industries use (S)-3-Amino-5-phenylpentanoic acid hydrochloride (CAS: 331846-97-0)?

(S)-3-Amino-5-phenylpentanoic acid hydrochloride is primarily used in the pharma...

331846-97-0(S)-3-Amino-5-phenyl...
Compound Q&A

How is 7-methoxy-1-benzothiophene-2-carboxylic acid (CAS: 88791-07-5) typically synthesized?

7-Methoxy-1-benzothiophene-2-carboxylic acid is typically synthesized by reactin...

88791-07-57-methoxy-1-benzothi...

Source Journal

Physical Chemistry Chemical Physics

Physical Chemistry Chemical Physics
CiteScore: 5.5
Self-citation Rate: 10.3%
Articles per Year: 3036

Physical Chemistry Chemical Physics (PCCP) is an international journal co-owned by 19 physical chemistry and physics societies from around the world. This journal publishes original, cutting-edge research in physical chemistry, chemical physics and biophysical chemistry. To be suitable for publication in PCCP, articles must include significant innovation and/or insight into physical chemistry; this is the most important criterion that reviewers and Editors will judge against when evaluating submissions. The journal has a broad scope and welcomes contributions spanning experiment, theory, computation and data science. Topical coverage includes spectroscopy, dynamics, kinetics, statistical mechanics, thermodynamics, electrochemistry, catalysis, surface science, quantum mechanics, quantum computing and machine learning. Interdisciplinary research areas such as polymers and soft matter, materials, nanoscience, energy, surfaces/interfaces, and biophysical chemistry are welcomed if they demonstrate significant innovation and/or insight into physical chemistry. Joined experimental/theoretical studies are particularly appreciated when complementary and based on up-to-date approaches.

Recommended Compounds

Recommended Suppliers

Disclaimer
This page provides academic journal information for reference and research purposes only. We are not affiliated with any journal publishers and do not handle publication submissions. For publication-related inquiries, please contact the respective journal publishers directly.
If you notice any inaccuracies in the information displayed, please contact us at support@chemtradehub.com. We will promptly review and address your concerns.