From phlogiston to caloric: chemical ontologies

The ‘triumph of the anti-phlogistians’ is a familiar story to the historians and philosophers of science who characterize the Chemical Revolution as a broad conceptual shift. The apparent “incommensurability” of the paradigms across the revolutionary divide has caused much anxiety. Chemists could identify phlogiston and oxygen, however, only with different sets of instrumental practices, theoretical schemes, and philosophical commitments. In addition, the substantive counterpart to phlogiston in the new chemistry was not oxygen, but caloric. By focusing on the changing visions of chemical body across the revolutionary divide with a more sensitive probe into the historical actors’ material manipulations and linguistic usage, we can historicize their laboratory realities and philosophical agenda. An archeology of chemical bodies that configures the fragile stability of the material worlds chemists created in succession promises a philosophical horizon that would recognize our hybrid (natural–artificial) environment as an evolving investigative object of science.     

Lavoisier's Achievement; More Than a Chemical Revolution

Abstract

The Chemical Revolution of the late eighteenth century consisted essentially of combustion being explained by the addition of oxygen rather than by the removal of phlogiston. This has been seen as the “paradigm shift” of a scientific revolution in the familiar Kuhnian sense. Yet Lavoisier helped to change chemistry in several other ways as well, particularly by the introduction of a new chemical language. This reorganisation of chemistry, at a time when it was being swamped with many new substances, has great similarity to the slightly earlier systematisation of botany by Linnaeus through the introduction of a binomial nomenclature. A further parallel in the late eighteenth century was the introduction of the metric system, which also introduced a new language. Yet, however one understands the Chemical Revolution, Lavoisier clearly made an enormous difference, not only to the internal science of chemistry, but also to its status. By the end of the 1700s, chemistry had become something of a model science.     

Von der Verbrennung zum Herzschlag: Chemische Triebkräfte

Is there a link between a simple chemical oxidation and the heart beat? The answer is given in a lecture in physical chemistry on energy and energy conversion. Starting with a historical review from the early times of the phlogiston theory until the modern times and the role of ATP in biological systems, we emphasize the role on energy and entropy for the understanding of chemical and biochemical processes. Experimental examples begin with chemical oxidations, continue with different exergonic processes, include mechanical and electrochemical energy conversion and end with nonlinear oscillatory systems.     

Richard Kirwan's phlogiston theory: its success and fate

First proposed in the early 1780s, Richard Kirwan's phlogiston theory was the most successful enunciation of the English pneumatic approach to phlogiston. Phlogiston was identified with a material substance, inflammable air. In this paper, I explore the nature of Kirwan's theory, its success in the mid-1780's, the unprecedented collective attack on Kirwan's Essay on Phlogiston by Lavoisier and his colleagues, and Kirwan's ultimate abandonment of phlogistic explanation.     

Richard Kirwan's Phlogiston Theory: Its Success and Fate

Abstract

First proposed in the early 1780s, Richard Kirwan's phlogiston theory was the most successful enunciation of the English pneumatic approach to phlogiston. Phlogiston was identified with a material substance, inflammable air. In this paper, I explore the nature of Kirwan's theory, its success in the mid-1780s, the unprecedented collective attack on Kirwan's Essay on Phlogiston by Lavoisier and his colleagues, and Kinvan's ultimate abandonment of phlogistic explanation.     

Lavoisier’s “Reflections on phlogiston” II: on the nature of heat

Having refuted the phlogiston theory, Lavoisier uses this second portion of his essay to expound his new theory of combustion, based on the oxygen principle. He gives a mechanistic account of thermodynamic phenomena in terms of a subtle fluid (not yet named “caloric”) and its ability to penetrate porous bodies. He uses this hypothetical fluid to explain volume changes, heat capacity and latent heat. Beyond the three types of combustion that he distinguishes and defines, Lavoisier also explains other chemical sources of heat, such as the heat of solution.     

科学发展史中批判性思维的作用和习得途径

Scientific theory innovation needs scientists who have comprehensive critical thinking. Taking the history of science of phlogiston and periodic law of elements as an example, this paper expounds the role of the critical thinking skills and habits, and tries to develop the way for acquisition of critical thinking from the history of science.     

氢元素概念发展史与化学思想的演进

18世纪,发现氢气的卡文迪什认为该气体是水与燃素的化合物;但发现水的组成的拉瓦锡认为氢气是一种元素物质.到19世纪,原子分子论形成后,氢气被认为是由双原子分子构成的单质.20世纪30年代,氢同位素的发现使人们对氢元素概念有了新认识,并逐渐形成现代氢元素概念.氢元素概念的发展史不仅是元素概念的发展史,也是科学思想的演进史...     

Histoires de fontes. Entre le phlogistique et la plombagine : où situer la « fonte à l'oxygène » ?

Iron stories. Between phlogiston and plumbago : which place for ‘oxygen cast-iron’ ? The evolution of knowledge on steel and iron, with the first quantitative chemical analysis by Lavoisier, is described along the 18th century and the first years of the 19th. After the classification by Réaumur of wrought iron, steel and cast iron, based on an increasing content of ‘sulphurs and salts’, replaced by phlogiston and plumbago, the publication by Lavoisier of a high oxygen content in cast iron darkened the understanding of iron metallurgy. It was necessary to wait until the beginning of the 19th century, when Berzelius restored the situation.     

Phosphorus. From elemental light to chemical element

Exactly 300 years ago in the city of Hamburg, a certain Hennig Brand, self-styled doctor medicinae, and chymist, discovered a strange substance in human urine, which was later called phosphorus (light bearer), a name then common to various luminous substances, and which created much excitement in the latter years of the 17th century on account of its properties. However, it was not Brand who profited from the discovery but others: Johann Daniel Krafft, Johann Kunckel, and Gottfried Wilhelm Leibniz, men who knew only too well how to exploit the weaknesses of the discoverer. “Cold fire”, Brand's own name for the new substance, was originally regarded as elemental light or fire, and it was not until the conception of the antiphlogistic theory by Antoine Laurent Lavoisier that the proper position of phosphorus among the chemical elements was recognized. In fact, the element played a decisive role in the overthrow of the phlogiston doctrine, a little over one hundred years after its discovery and almost two hundred years ago.     

摩尔新定义和准确测定的阿伏伽德罗常数

针对2019年国际SI单位新标准的实施,依据文献对阿伏伽德罗常数和摩尔物质量原理进行了简短的历史回顾。着重于摩尔新定义的概念和准确测定阿伏伽德罗常数的描述,突出了原子量精密测量技术、纳米量级精密测量技术以及材料制备和表征技术的发展。相对而言,摩尔新定义更能体现科学方法和科学思维同化学知识的关系,将会对无机化学、分析化学、物理化学等课程教学引起巨大的冲击波,并且会波及到每个化学专业本科生。本文内容可为提高本科生的科研思维和科研素质提供借鉴。     

Dynamic combinatorial libraries: new opportunities in systems chemistry

Combinatorial chemistry is a tool for selecting molecules with special properties. Dynamic combinatorial chemistry started off aiming to be just that. However, unlike ordinary combinatorial chemistry, the interconnectedness of dynamic libraries gives them an extra dimension. An understanding of these molecular networks at systems level is essential for their use as a selection tool and creates exciting new opportunities in systems chemistry. In this feature article we discuss selected examples and considerations related to the advanced exploitation of dynamic combinatorial libraries for their originally conceived purpose of identifying strong binding interactions. Also reviewed are examples illustrating a trend towards increasing complexity in terms of network behaviour and reversible chemistry. Finally, new applications of dynamic combinatorial chemistry in self-assembly, transport and self-replication are discussed.     

Synthesis and reactions of N-heterocyclic carbene boranes

Boranes are widely used Lewis acids and N-heterocyclic carbenes (NHCs) are popular Lewis bases, so it is remarkable how little was known about their derived complexes until recently. NHC-boranes are typically readily accessible and many are so stable that they can be treated like organic compounds rather than complexes. They do not exhibit "borane chemistry", but instead are proving to have a rich chemistry of their own as reactants, as reagents, as initiators, and as catalysts. They have significant potential for use in organic synthesis and in polymer chemistry. They can be used to easily make unusual complexes with a broad spectrum of functional groups not usually seen in organoboron chemistry. Many of their reactions occur through new classes of reactive intermediates including borenium cations, boryl radicals, and even boryl anions. This Review provides comprehensive coverage of the synthesis, characterization, and reactions of NHC-boranes.     

Reflets d'une chimie largement inexplorée : celle des boradipyrrométhènes

Insights into a largely unexplored chemistry: that of boradipyrromethenes. This review focuses on new perspectives in the field of boradipyrromethene chemistry. In fact, a new chemistry of tetrahedral boron has been initiated and developed; it allows us to catch a glimpse of exciting optical properties, such as large Stokes shifts, high fluorescence quantum yields, and interesting redox properties. Some energy-transfer processes are extremely rapid and at the limit of the available experimental techniques. This chemistry allowed us to widen the absorption/emission spectrum in the near infrared, by chemically modifying the conjugate skeleton. Some new perspectives offered by these tandem systems for protein labelling are also envisaged.     

Covalent Organic Frameworks: Chemical Approaches to Designer Structures and Built‐In Functions

A new approach has been developed to design organic polymers using topology diagrams. This strategy enables covalent integration of organic units into ordered topologies and creates a new polymer form, that is, covalent organic frameworks. This is a breakthrough in chemistry because it sets a molecular platform for synthesizing polymers with predesignable primary and high‐order structures, which has been a central aim for over a century but unattainable with traditional design principles. This new field has its own features that are distinct from conventional polymers. This Review summarizes the fundamentals as well as major progress by focusing on the chemistry used to design structures, including the principles, synthetic strategies, and control methods. We scrutinize built‐in functions that are specific to the structures by revealing various interplays and mechanisms involved in the expression of function. We propose major fundamental issues to be addressed in chemistry as well as future directions from physics, materials, and application perspectives.     

Some Advances in the Inorganic Chemistry of Bromine

Recent advances in the chemistry of bromine and its inorganic compounds are covered under the headings of technology, properties and reactions, liquid bromine as an inorganic solvent, analysis, and new or newly studied compounds. Much of what is new is bromine chemistry is characteristic also of what is new in inorganic chemistry as a whole. That is, more detailed information about compounds and reactions is becoming available from the application of new instrumental and theoretical techniques.     

有机合成与脑化学

设计和合成能选择性地调节神经中枢内信号传导过程的小分子化合物是现在脑化学中的一个热点。本文以调节谷氨酸受体及其亚基、蛋白激酶C 及其异构酶的化合物为例, 论述了有机合成化学在脑化学发展中的作用及面临的新挑战。     

Highlights of Spanish chemistry at the time of the chemical revolution of the 18th century

Summary A number of outstanding Spanish chemists and some of their major chemical contributions in the 18th century are briefly considered indicating that Spanish chemistry got a very high level at the end of the century, departing practically from nothing at the beginning of the century. The Vergara School played a very important role as the first national institution for chemistry despite of the fact that it decayed in a few years for a number of reasons. The discovery of three new elements is briefly dealt with (Pt, W, V) and the adoption of the new modern French chemistry in Spain as well as a number of critics against some of Lavoisier's theories and nomenclature posed by some Spanish chemists are considered.     

Better chemistry through ceramics: the physical bases of the outstanding chemistry of ORMOSIL

Twenty years after their invention, sol-gel organically modified silicates (ORMOSIL) are finding a number of impressive applications that range from efficient deliver of genes into mouse brains to self-ordered helices of interest to fields as diverse as optics, catalysis, molecular recognition, and chromatography. The physical bases of this mulifaceted chemistry, therefore, are of immense importance to scientists working toward new applications such as photovoltaics and catalysis that are crucially important in making sustainable global development. The purpose of this article is to provide a general picture of ORMOSIL's physical chemistry that will be useful in the creative development of new materials capable to solve a number of relevant open problems.     

Selective Host Molecules Obtained by Dynamic Adaptive Chemistry

Up till 20 years ago, in order to endow molecules with function there were two mainstream lines of thought. One was to rationally design the positioning of chemical functionalities within candidate molecules, followed by an iterative synthesis–optimization process. The second was the use of a “brutal force” approach of combinatorial chemistry coupled with advanced screening for function. Although both methods provided important results, “rational design” often resulted in time‐consuming efforts of modeling and synthesis only to find that the candidate molecule was not performing the designed job. “Combinatorial chemistry” suffered from a fundamental limitation related to the focusing of the libraries employed, often using lead compounds that limit its scope. Dynamic constitutional chemistry has developed as a combination of the two approaches above. Through the rational use of reversible chemical bonds together with a large plethora of precursor libraries, one is now able to build functional structures, ranging from quite simple molecules up to large polymeric structures. Thus, by introduction of the dynamic component within the molecular recognition processes, a new perspective of deciphering the world of the molecular events has aroused together with a new field of chemistry. Since its birth dynamic constitutional chemistry has continuously gained attention, in particular due to its ability to easily create from scratch outstanding molecular structures as well as the addition of adaptive features. The fundamental concepts defining the dynamic constitutional chemistry have been continuously extended to currently place it at the intersection between the supramolecular chemistry and newly defined adaptive chemistry, a pivotal feature towards evolutive chemistry.