Avogadro's law
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| Gay-Lussac | John Dalton |
The Avogadro's law (Avogadro のほうそく, English: Avogadro's law) is the law that the molecules of the same number are included in to the same pressure, the same temperature, all types of gas of the same volume. Because Amedeo Avogadro explained Gay-Lussac law of Gay-Lussac and contradiction of the atomism of John Dalton in 1811, I suggested it as a hypothesis [1]. Because I am late a little, and Andre = Mali Ampere suggested a similar hypothesis independently in 1813, I say the law of Avogadro - Ampere. In addition, I pay my attention to the point that suggested the concept called molecules in particular and call it with the molecular opinion (ぶんしせつ). I distinguish an element, an atom, three concepts of molecules and am a hypothesis to become the key in distinguishing chemical equivalence, the atomic weight corresponding to them, difference in molecular weight again.
The hypothesis of Avogadro was almost forgotten other than an interval nearly half a century, some chemists after suggestion. Therefore chemical equivalence and atomic weight, distinction of the molecular weight became vague, and a value of the atomic weight to use by a chemist fell into a situation to be different. The commentary about the hypothesis of Avogadro was performed in Karlsruhe international conference () of 1860 by Stanislao Cannizzaro, and many chemists who heard this received a hypothesis, and the confusion about the atomic weight was gradually canceled.
It came afterwards to have become the problem whether the existence of the numerator that Avogadro suggested existed. Kinetic theory of gases was suggested from the side that insisted on the existence of molecules, and gas equations have been explained. However, on the other hand, there were many hypothesis that the molecules which I could not yet observe from the situation of the positivism were convenient for theoretical explanation to the last and a physicist, chemists who insisted. This problem solved it by the existence of molecules being finally proved indirectly by theoretical suggestion of the Brownian movement by Albert Einstein of 1905 and the theoretical proof by Jean Perrin.
Because the existence of molecules was confirmed, the hypothesis of Avogadro is called Avogadro's law and I name his name and call the physics fixed number to express the number of the molecules which gas of the number of the grams same as molecular weight includes with Avogadro constant now.
Table of contents
Hypothesis of Avogadro
It was Gay-Lussac law of the gay Rue case that it became the cause that a hypothesis of Avogadro was suggested. If Gay-Lussac law is established to every gas, the particle of the integral multiple of the fixed number that there is will be included in gas in the same pressure, the same temperature, the same volume. For example, 2 liters of steam is formed from 2 liters of hydrogen and 1 liter of oxygen, and 2 liters of carbon monoxide occurs when I burnt carbon with 1 liter of oxygen.
John Dalton denied this experiment fact in itself, but Avogadro and Jens bell Japanese parsley Usu accepted this law. Avogadro did it to explain this experiment fact when a particle of the fixed number that there was was included in the same pressure, the same temperature, "one gas of all" of the same volume and called this particle with molecule (molecules). When I could divide hydrogen molecules and oxygen molecules into two when water was made by chemical combination, and it was to "half molecules", Avogadro did it. As for Avogadro, these half molecules considered the thing consisting of atoms more than two, but did it if they thought that it was from two atoms from an example of the known Gay-Lussac law by then when enough. Ampere proposed a similar hypothesis in 1814, too.
However, it was hard to accept the thought that only the atom of the single kind was connected and formed polyatomic molecules at that time (it is in 1927 that the real nature was elucidated based on quantum chemistry Gilbert Lewis having proposed a covalent concept for the first time in 1916 by Walter high tola and Fritz London). I thought that what heavy gas and light gas completely mixed Dalton and did not isolate was caused by the fact that heat bare による repulsive force worked to the same type of atoms and did not recognize the combination of the same kind atom. In addition, bell Japanese parsley Usu thought that electrostatic repulsive force acted on the same type of atoms from a way of thinking of the electrochemic dualism. The electrochemic dualism was believed in as a chemical prop-like theory until about 1840. Therefore it was that a rip occurred in the electrochemic dualism that the way of thinking of the molecules consisting of similar atoms came to be accepted.
On the other hand, because bell Japanese parsley Usu matches consistency of the Gay-Lussac law; of the same pressure, the same temperature, the same volume all; when a particle of the fixed number that there was was included in "one gas of a simple substance", limited it, and thought. In other words, I thought that steam and carbon monoxide included only half particles of the simple substance of gas. Bell Japanese parsley Usu decided much atomic weight for the cause by this way of thinking.
However, the thought of bell Japanese parsley Usu did not spread out to many chemists that much, too. Therefore each chemist decides atomic weight based on one's thought, and a state to decide a molecular formula based on it will continue for a long time.
Inspection of the hypothesis of Avogadro
It was an opinion of Avogadro who was not minded to most chemists, but few chemists were interested in this and were going to inspect it.
Jean Batty strike Andre Dumas developed a method to measure the vapor density of the material which was not gas at normal temperature. However, a dissociation reaction was caused at a high temperature with some materials, and the result that denied a hypothesis of Avogadro has been provided. It is that a gaseous dissociation reaction is discovered all the time in later 1865 by Adolf ヴュルツ that this problem is solved.
When electrochemistry dualism had begun to shake by discovery of the substitution reaction, as for Gerard, all materials proposed a theory of the rest which two roots joined in 1839. I understood that the atomic weight, molecular weight decision method of bell Japanese parsley Usu had a problem when I adopted a theory of the rest. Because bell Japanese parsley Usu regarded a composition type of oxide of metal M as MO, all the univalent metal atomic weight increased twice as much as the true value. And the molecular weight of carboxylic acid has increased twice as much as the true value because I decided molecular weight of carboxylic acid from composition of the silversalt. I noticed that Gerard applied a theory of the rest to chlorine substitution reaction of carboxylic acid here in the molecular weight of the hydrogen chloride increasing twice as much as before. If the composition type of oxide of metal M was M2O, consistency was provided, and Gerard showed that a hypothesis of Avogadro was concluded again. However, Gerard was negative against revision of this molecular weight and wanted to abandon a concept of the molecular weight not to be able to rather have consistency.
It was friend Auguste Loran of Gerard to have insisted on significance of this revision positively. As for the Loran, simple substances such as hydrogen and oxygen, chlorine insisted on being two atom molecules according to the hypothesis of Avogadro as a conclusion from a theory of the rest. The claim of Gerard and the Loran was adopted by Alexander Williamson and William Odo ring (), August Wilhelm phone Hoffman and others. However, many chemists continued still using own original molecular formula.
Stanislao Cannizzaro showed that the ceremony of composition of the inorganic compound could be decided using a law of Duron Petit in 1858. And a composition type of oxide of alkaline earth metals showed that it was MO not M2O which Gerard proposed and suggested right atomic weight. In addition, I showed it including the molecular weight decision method based on the hypothesis of Avogadro. And I showed that I could decide all elemental atomic weight in one value by putting these methods together.
I held Karlsruhe international conference in 1860 that chemists to be naive in Friedrich Kekule unified opinions about a molecular formula and the atomic weight and dissolved in a confusion state. Cannizzaro distributed an article of oneself to a participant as a brochure. Although I was not provided, as for the common view, the importance of the hypothesis of Avogadro was recognized at the place of the meeting by many chemists, and the confusion of atomic weight and the molecular formula gradually went to the cancellation. It led to discovery of the periodic law in this way that right atomic weight came to be used.
Actual inspection of molecules
Because what's called molecules which appeared there although it was recognized really existed as a particle, the hypothesis of Avogadro remained that it unknown whether it was only the concept that it was merely convenient for explanation. This became the big debate in physics and the chemistry from end of 19th century to the early 20th century in conjunction with the existence of the atom.
The study that treated molecules as a particle according to a physical law existed from early time than a hypothesis of Avogadro was accepted. Rene Descartes and Isaac Newton took the situation of the particle theory which all things became from a particle () and thought to explain every physical property from the exercise of particle. Leonhard Euler performed a trial to demand a gas equation from the motion of gas particle in 1727. However, the speed distribution of the particle has not yet begun consideration, and this trial fails. It does not succeed to apply a theory of the immature physics at the time to chemistry, and such a trial becomes the fire afterwards during nearly one century.
The John James water stone () suggests a theorem of energy 均分 in 1843 and derives that pressure and an expression of relations and temperature of the mean speed of gaseous molecules are proportional to square of the mean speed of molecules. However, this article was buried until Reilly discovered it in 1891. Pressure and the relations of the mean speed will be suggested to the theorem of 均分 of the energy by William Thomson independently each in 1859 in 1853 by James Clark Maxwell. Clausius treated gas molecules as a particle with a certain form during 1857 and the following year and announced the specific heat theory in consideration of rotary motion. Maxwell proposed the theory including theorems of 速度分布則 and energy 均分 of gas molecules in 1859 and derived an equation of state. I succeeded in the Johan Roche mitt demanding the number of Roche mitts which were the number of the molecules per 1cm3 from the cause by this result in 1865.
Although I met, such a result comes to take the situation where many scientists are skeptical about the existence of an atom and molecules. Thermodynamic establishment greatly influences this. Julius Roberto phone Mayer proposed the law of the conservation of energy in 1842. It became certain that heat was a kind of the energy, and a heat bare opinion was completely denied in 1843 by an experiment of James Press cot Joule. In addition, Clausius suggested the thermodynamic second law in 1850. This thermodynamic second law was a problem. The kinetic theory of gases is based on the Newton dynamics. Because the exercise with the Newton dynamics was reversible, the kinetic theory of gases has done not have possibilities to explain the thermodynamic second law. In addition, it was the field except the gaseous property at a molecular opinion, and there was the limit where I could hardly lead any useful knowledge to. On the other hand, the thermodynamics could apply to solution and a chemical reaction other than a gaseous property and led much useful knowledge.
そこで熱の本性がエネルギーであったのと同様に、原子や分子も本性はエネルギーであると考える科学者たちが多くなった。 このエネルギー論の立場をとったのはヴィルヘルム・オストヴァルトやエルンスト・マッハらである。 一方ルートヴィッヒ・ボルツマンは原子、分子の存在を主張し、彼らの間で激しい論争となった。
1872年にボルツマンはボルツマン方程式とH定理を提案し、これにより熱力学の第二法則を説明できるとした。 しかし1876年にロシュミットから、それがニュートン力学の可逆性と矛盾しているのではないかという批判を受ける。 ボルツマンはそれを受けて1877年にエントロピーと確率の関係であるボルツマンの原理を示し、H定理に反するのは確率的にありえないようなわずかな場合に限ると主張した。 また1896年にエルンスト・ツェルメロは、ボルツマンの考えた系ではアンリ・ポアンカレの再帰定理により有限時間のちに同じ状態が再現されるため、H定理は成り立たないと主張した。 これに対しボルツマンは再帰に要する時間は非現実的な長さの時間であり考慮する必要はないと主張した。 しかし、これらの反論もオストヴァルトやマッハを納得させるには至らず、ボルツマンは1906年に自殺してしまう。
1900年にはマックス・プランクが黒体放射の放射公式を発表した。 この式の中にはボルツマン定数が含まれているため、黒体放射から間接的にアボガドロ定数を検証できる。 このことは1905年にアルバート・アインシュタインによって指摘された。
最終的に原子と分子の実在性について決着を付けたのはアインシュタインとジャン・ペランであった。 アインシュタインは1905年にコロイドの濃度と粘性率の変化についての論文を博士論文として提出した。 またさらにブラウン運動をコロイド粒子に分子が多数ランダムに衝突することによるゆらぎの過程として記述する理論を提唱した。 これらの理論により、液体の性質からアボガドロ定数を算出する方法が新たに導かれた。 1908年にペランはこの新しい理論を詳細に検証し、アボガドロ定数を測定する実験を行なった。 それらの結果は従来の求められていた値とほぼ同じものであった。 こうしてやっと実際に分子が実在することがオストヴァルトらにも認められ、アボガドロの仮説は、法則として認められることになったのである。
関連項目
脚註
- ^ Avogadro, Amedeo (1810). "Essai d'une maniere de determiner les masses relatives des molecules elementaires des corps, et les proportions selon lesquelles elles entrent dans ces combinaisons" (フランス語). Journal de Physique 73: 58–76 2009年1月30日閲覧。.（英語訳）
This article is taken from the Japanese Wikipedia Avogadro's law
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