Thomsen–Berthelot principle

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In thermochemistry, the Thomsen–Berthelot principle is a hypothesis in the history of chemistry which argued that all chemical changes are accompanied by the production of heat and that processes which occur will be ones in which the most heat is produced. [1] This principle was formulated in slightly different versions by the Danish chemist Julius Thomsen in 1854 and by the French chemist Marcellin Berthelot in 1864. This early postulate in classical thermochemistry became the controversial foundation of a research program that would last three decades.

Contents

This principle came to be associated with what was called the thermal theory of affinity, which postulated that the heat evolved in a chemical reaction was the true measure of its affinity.

Limitations

The experimental objections to the Thomsen–Berthelot principle include incomplete dissociation, reversibility, and spontaneous endothermic processes. [2] Such cases were dismissed by orthodox thermochemist as outliers not covered by the principle, or the experiments were manipulated to fit it through with somewhat contrived justifications was later disproved. [2] In 1873, Thomsen acknowledged that his theory might not have universal or definitive credibility. [3] Later, under newly created chemical thermodynamics framework, the principle was explained to only be valid as an idealization under extreme conditions (i.e., absolute zero). [2] Thomsen openly admitted that his initial understanding was merely a close estimate of the reality, emphasizing that while chemical reactions typically release heat, this heat isn't always a trustworthy indicator of the strength of the bonds formed. [4] On the other hand, Berthelot, was more resistant and continued to assert the validity of the principle until 1894. [5] In 1882 the German scientist Hermann von Helmholtz proved that affinity was not given by the heat evolved in a chemical reaction but rather by the maximum work, or free energy, produced when the reaction was carried out reversibly.

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Thermodynamics is a branch of physics that deals with heat, work, and temperature, and their relation to energy, entropy, and the physical properties of matter and radiation. The behavior of these quantities is governed by the four laws of thermodynamics, which convey a quantitative description using measurable macroscopic physical quantities, but may be explained in terms of microscopic constituents by statistical mechanics. Thermodynamics applies to a wide variety of topics in science and engineering, especially physical chemistry, biochemistry, chemical engineering and mechanical engineering, but also in other complex fields such as meteorology.

<span class="mw-page-title-main">Thermochemistry</span> Study of the heat energy associated with chemical reactions and/or physical transformations

Thermochemistry is the study of the heat energy which is associated with chemical reactions and/or phase changes such as melting and boiling. A reaction may release or absorb energy, and a phase change may do the same. Thermochemistry focuses on the energy exchange between a system and its surroundings in the form of heat. Thermochemistry is useful in predicting reactant and product quantities throughout the course of a given reaction. In combination with entropy determinations, it is also used to predict whether a reaction is spontaneous or non-spontaneous, favorable or unfavorable.

<span class="mw-page-title-main">Thermodynamic free energy</span> State function whose change relates to the systems maximal work output

In thermodynamics, the thermodynamic free energy is one of the state functions of a thermodynamic system. The change in the free energy is the maximum amount of work that the system can perform in a process at constant temperature, and its sign indicates whether the process is thermodynamically favorable or forbidden. Since free energy usually contains potential energy, it is not absolute but depends on the choice of a zero point. Therefore, only relative free energy values, or changes in free energy, are physically meaningful.

<span class="mw-page-title-main">Conservation of mass</span> Scientific law that a closed systems mass remains constant

In physics and chemistry, the law of conservation of mass or principle of mass conservation states that for any system closed to all transfers of matter and energy, the mass of the system must remain constant over time, as the system's mass cannot change, so the quantity can neither be added nor be removed. Therefore, the quantity of mass is conserved over time.

<span class="mw-page-title-main">Rudolf Clausius</span> German physicist and mathematician (1822–1888)

Rudolf Julius Emanuel Clausius was a German physicist and mathematician and is considered one of the central founding fathers of the science of thermodynamics. By his restatement of Sadi Carnot's principle known as the Carnot cycle, he gave the theory of heat a truer and sounder basis. His most important paper, "On the Moving Force of Heat", published in 1850, first stated the basic ideas of the second law of thermodynamics. In 1865 he introduced the concept of entropy. In 1870 he introduced the virial theorem, which applied to heat.

<span class="mw-page-title-main">Marcellin Berthelot</span> French chemist and politician (1827–1907)

Pierre Eugène Marcellin Berthelot was a French chemist and Republican politician noted for the Thomsen–Berthelot principle of thermochemistry. He synthesized many organic compounds from inorganic substances, providing a large amount of counter-evidence to the theory of Jöns Jakob Berzelius that organic compounds required organisms in their synthesis. Berthelot was convinced that chemical synthesis would revolutionize the food industry by the year 2000, and that synthesized foods would replace farms and pastures. "Why not", he asked, "if it proved cheaper and better to make the same materials than to grow them?"

<span class="mw-page-title-main">Germain Henri Hess</span> Swiss-Russian chemist and physician (1802–1850)

Germain Henri Hess was a Swiss-Russian chemist and doctor who formulated Hess' law, an early principle of thermochemistry.

<span class="mw-page-title-main">History of chemistry</span>

The history of chemistry represents a time span from ancient history to the present. By 1000 BC, civilizations used technologies that would eventually form the basis of the various branches of chemistry. Examples include the discovery of fire, extracting metals from ores, making pottery and glazes, fermenting beer and wine, extracting chemicals from plants for medicine and perfume, rendering fat into soap, making glass, and making alloys like bronze.

<span class="mw-page-title-main">Hans Peter Jørgen Julius Thomsen</span> Danish chemist (1826–1909)

Hans Peter Jørgen Julius Thomsen was a Danish chemist noted in thermochemistry for the Thomsen–Berthelot principle.

<span class="mw-page-title-main">History of thermodynamics</span>

The history of thermodynamics is a fundamental strand in the history of physics, the history of chemistry, and the history of science in general. Owing in the relevance of thermodynamics in much of science and technology, its history is finely woven with the developments of classical mechanics, quantum mechanics, magnetism, and chemical kinetics, to more distant applied fields such as meteorology, information theory, and biology (physiology), and to technological developments such as the steam engine, internal combustion engine, cryogenics and electricity generation. The development of thermodynamics both drove and was driven by atomic theory. It also, albeit in a subtle manner, motivated new directions in probability and statistics; see, for example, the timeline of thermodynamics.

In the history of science, the principle of maximum work was a postulate concerning the relationship between chemical reactions, heat evolution, and the potential work produced there from. The principle was developed in approximate form in 1875 by French chemist Marcellin Berthelot, in the field of thermochemistry, and then in 1876 by American mathematical physicist Willard Gibbs, in the field of thermodynamics, in a more accurate form. Berthelot's version was essentially: "every pure chemical reaction is accompanied by evolution of heat.". The effects of irreversibility, however, showed this version to be incorrect. This was rectified, in thermodynamics, by incorporating the concept of entropy.

Physical organic chemistry, a term coined by Louis Hammett in 1940, refers to a discipline of organic chemistry that focuses on the relationship between chemical structures and reactivity, in particular, applying experimental tools of physical chemistry to the study of organic molecules. Specific focal points of study include the rates of organic reactions, the relative chemical stabilities of the starting materials, reactive intermediates, transition states, and products of chemical reactions, and non-covalent aspects of solvation and molecular interactions that influence chemical reactivity. Such studies provide theoretical and practical frameworks to understand how changes in structure in solution or solid-state contexts impact reaction mechanism and rate for each organic reaction of interest.

<span class="mw-page-title-main">Camille Matignon</span> French chemist (1867–1934)

Arthème Camille Matignon was a French chemist noted for his work in thermochemistry. He was a member of the Académie des Sciences, President of the French Chemical Society and an honorary Fellow of the British Chemical Society.

<span class="mw-page-title-main">Alexander Naumann</span>

Alexander Nikolaus Franz Naumann was a Prussian and German physical chemist and a professor at the University of Giessen. He was a pioneer of chemical thermodynamics and proposed that molecules reacted when their energy levels exceeded a certain critical level which could be achieved through the provision of heat.

References

  1. William H. Cropper (2004). Great Physicists: The Life and Times of Leading Physicists from Galileo to Hawking. Oxford University Press. pp. 128–. ISBN   978-0-19-517324-6.
  2. 1 2 3 Kragh, Helge (November 1984). "Julius Thomsen and classical thermochemistry". The British Journal for the History of Science. 17 (3): 255–272. doi:10.1017/s0007087400021294. ISSN   0007-0874.
  3. "Supplementum Epigraphicum GraecumSivrihissar (in vico). Op. cit. Op. cit. 334, n. 19". Supplementum Epigraphicum Graecum. doi:10.1163/1874-6772_seg_a2_597 . Retrieved 2023-08-06.
  4. Thermochemische Untersuchtmgen, op. cit. (12), II, 1883, 42
  5. M. Berthelot, 'Le principe du travail maximum et l'entropie,' Comples rendus, 1894, 118, 1378-1392.

See also