Response to the theory

Amedeo Avogadro

Lorenzo Romano Amedeo Carlo Avogadro di Quaregna e di Cerreto, Count of Quaregna and Cerreto (9 August 1776, Turin, Piedmont – 9 July 1856) was an Italian savant. He is most noted for his contributions to molecular theory, including what is known as Avogadro's law. In tribute to him, the number of elementary entities (atoms, molecules, ions or other particles) in 1 mole of a substance, 6.02214179(30)×10²³, is known as the Avogadro constant.

Biography

Amedeo Carlo Avogadro was born in Turin, Italy in 1776 to a noble family of Piedmont, Italy.

He graduated in ecclesiastical law at the early age of 20 and began to practice. Soon after, he dedicated himself to physics and mathematics (then called positive philosophy), and in 1809 started teaching them at a liceo (high school) in Vercelli, where his family had property.

In 1811, he published an article with the title Essai d'une manière de déterminer les masses relatives des molécules élémentaires des corps, et les proportions selon lesquelles elles entrent dans ces combinaisons ("Essay on Determining the Relative Masses of the Elementary Molecules of Bodies and the Proportions by Which They Enter These Combinations"), which contains Avogadro's hypothesis. Avogadro submitted this essay to a French journal, Jean-Claude Delamétherie's Journal de Physique, de Chimie et d'Histoire naturelle (Journal of Physics, Chemistry and Natural History) so it was written in French, not Italian. (Note: France effectively controlled northern Italy from 1796 to 1814.)

In 1820, he became professor of physics at the University of Turin. After the downfall of the French Emperor Napoléon in 1815, Piedmont again came under the control of the King of Piedmont-Sardinia, ruling from Turin.

Avogrado was active in the revolutionary movements of 1821 against King Victor Emmanuel I. As a result, he lost his chair in 1823 (or, as the university officially declared, it was " very glad to allow this interesting scientist to take a rest from heavy teaching duties, in order to be able to give better attention to his researches ").

Eventually, King Charles Albert granted a Constitution (Statuto Albertino) in 1848. Well before this, Avogadro had been recalled to the university in Turin in 1833, where he taught for another twenty years.

Little is known about Avogadro's private life, which appears to have been sober and religious. He married Felicita Mazzé and had six children.

Some historians suggest that he sponsored some Sardinian revolutionaries, who were stopped by the announcement of Charles Albert's constitution.

Avogadro held posts dealing with statistics, meteorology, and weights and measures (he introduced the metric system into Piedmont) and was a member of the Royal Superior Council on Public Instruction.

In honor of Avogadro's contributions to molecular theory, the number of molecules in one mole was named Avogadro's number, N_A or "Avogadro's constant". It is approximately 6.0221415 × 10²³. Avogadro's number is used to compute the results of chemical reactions. It allows chemists to determine amounts of substances produced in a given reaction to a great degree of accuracy.

Johann Josef Loschmidt first calculated the value of Avogadro's number, often referred to as the Loschmidt number in German-speaking countries (Loschmidt constant now has another meaning).

Accomplishments

Avogadro's Law states that the relationship between the masses of the same volume of different gases (at the same temperature and pressure) corresponds to the relationship between their respective molecular weights. Hence, the relative molecular mass of a gas can be calculated from the mass of sample of known volume.

Avogadro developed this hypothesis after Joseph Louis Gay-Lussac had published in 1808 his law on volumes (and combining gases). The greatest problem Avogadro had to resolve was the confusion at that time regarding atoms and molecules. One of his most important contributions was clearly distinguishing one from the other, stating that gases are composed of molecules, and these molecules are composed of atoms. For instance, John Dalton did not consider this possibility. Avogadro did not actually use the word "atom" as the words "atom" and "molecule" were used almost without difference. He believed that there were three kinds of "molecules," including an "elementary molecule" (our "atom"). Also, more attention was given to the definition of mass, as distinguished from weight.

In 1815, he published Mémoire sur les masses relatives des molécules des corps simples, ou densités présumées de leur gaz, et sur la constitution de quelques-uns de leur composés, pour servir de suite à l'Essai sur le même sujet, publié dans le Journal de Physique, juillet 1811 ("Note on the Relative Masses of Elementary Molecules, or Suggested Densities of Their Gases, and on the Constituents of Some of Their Compounds, As a Follow-up to the Essay on the Same Subject, Published in the Journal of Physics, July 1811") ([1]), about gas densities.

In 1821 he published another paper, Nouvelles considérations sur la théorie des proportions déterminées dans les combinaisons, et sur la détermination des masses des molécules des corps (New Considerations on the Theory of Proportions Determined in Combinations, and on Determination of the Masses of Atoms) and shortly afterwards, Mémoire sur la manière de ramener les composès organiques aux lois ordinaires des proportions déterminées (Note on the Manner of Finding the Organic Composition by the Ordinary Laws of Determined Proportions).

In 1841, he published his work in Fisica dei corpi ponderabili, ossia Trattato della costituzione materiale de' corpi, 4 volumes.

Response to the theory

The scientific community did not give great attention to his theory, so Avogadro's hypothesis was not immediately accepted. André-Marie Ampère achieved the same results three years later by another method (in his Sur la détermination des proportions dans lesquelles les corps se combinent d'après le nombre et la disposition respective des molécules dont leurs particules intégrantes sont composées -- On the Determination of Proportions in which Bodies Combine According to the Number and the Respective Disposition of the Molecules by Which Their Integral Particles Are Made), but the same indifference was shown to his theory as well.

Only through studies by Charles Frédéric Gerhardt and Auguste Laurent on organic chemistry was it possible to demonstrate that Avogadro's law explained why the same quantities of molecules in a gas have the same volume.

Unfortunately, related experiments with some inorganic substances showed seeming exceptions to the law. This was finally resolved by Stanislao Cannizzaro, as announced at Karlsruhe Congress in 1860, four years after Avogadro's death. He explained that these exceptions were due to molecular dissociations at certain temperatures, and that Avogadro's law determined not only molecular masses, but atomic masses as well.

In 1911, a meeting in Turin commemorated the hundredth anniversary of the publication of Avogadro's classic 1811 paper. King Victor Emmanuel III attended. Thus, Avogadro's great contribution to chemistry was recognized.

Rudolf Clausius, with his kinetic theory on gases, gave another confirmation of Avogadro's Law. Jacobus Henricus van 't Hoff showed that Avogadro's theory also held in dilute solutions.

Avogadro is hailed as a founder of the atomic-molecular theory.

Dmitri Mendeleev

Dmitri Ivanovich Mendeleev was a Russian chemist and inventor. He is credited as being the creator of the first version of the periodic table of elements. Using the table, he predicted the properties of elements yet to be discovered.

Early life

Mendeleev was born in the village of Verkhnie Aremzyani, near Tobolsk in Siberia, to Ivan Pavlovich Mendeleev and Maria Dmitrievna Mendeleev (née Kornilieva). His grandfather was Pavel Maximovich Sokolov, a priest of the Russian Orthodox Church from the Tver region. Ivan, along with his brothers and sisters, obtained new family names while attending the theological seminary. Despite being raised as an Orthodox Christian, he later rejected the religion and embraced a form of deism.

Mendeleev is thought to be the youngest of either 11, 13, 14 or 17 siblings; the exact number differs among sources. His father was a teacher of fine arts, politics and philosophy. Unfortunately for the family's financial well being, his father became blind and lost his teaching position. His mother was forced to work and she restarted her family's abandoned glass factory. At the age of 13, after the passing of his father and the destruction of his mother's factory by fire, Mendeleev attended the Gymnasium in Tobolsk.

In 1849, the now poor Mendeleev family relocated to Saint Petersburg, where he entered the Main Pedagogical Institute in 1850. After graduation, he contracted tuberculosis, causing him to move to the Crimean Peninsula on the northern coast of the Black Sea in 1855. While there he became a science master of the Simferopol gymnasium №1. He returned with fully restored health to Saint Petersburg in 1857.

Later life

Dmitri Mendeleev

Between 1859 and 1861, he worked on the capillarity of liquids and the workings of the spectroscope in Heidelberg. In late August 1861 he wrote his first book on the spectroscope. On 4 April 1862 he became engaged to Feozva Nikitichna Leshcheva, and they married on 27 April 1862 at Nikolaev Engineering Institute's church in Saint Petersburg (where he taught).^[7] Mendeleev became a professor at the Saint Petersburg Technological Institute and Saint Petersburg State University in 1864 and 1865, respectively. In 1865 he became Doctor of Science for his dissertation "On the Combinations of Water with Alcohol". He achieved tenure in 1867, and by 1871 had transformed Saint Petersburg into an internationally recognized center for chemistry research. In 1876, he became obsessed with Anna Ivanova Popova and began courting her; in 1881 he proposed to her and threatened suicide if she refused. His divorce from Leshcheva was finalized one month after he had married Popova (on 2 April) in early 1882. Even after the divorce, Mendeleev was technically a bigamist; the Russian Orthodox Church required at least seven years before lawful re-marriage. His divorce and the surrounding controversy contributed to his failure to be admitted to the Russian Academy of Sciences (despite his international fame by that time). His daughter from his second marriage, Lyubov, became the wife of the famous Russian poet Alexander Blok. His other children were son Vladimir (a sailor, he took part in the notable Eastern journey of Nicholas II) and daughter Olga, from his first marriage to Feozva, and son Ivan and a pair of twins from Anna.

Though Mendeleev was widely honored by scientific organizations all over Europe, including the Copley Medal from the Royal Society of London, he resigned from Saint Petersburg University on 17 August 1890.

In 1893, he was appointed Director of the Bureau of Weights and Measures. It was in this role that he was directed to formulate new state standards for the production of vodka. As a result of his work, in 1894 new standards for vodka were introduced into Russian law and all vodka had to be produced at 40% alcohol by volume.^[9]

Mendeleev also investigated the composition of petroleum, and helped to found the first oil refinery in Russia. He recognized the importance of petroleum as a feedstock for petrochemicals. He is credited with a remark that burning petroleum as a fuel "would be akin to firing up a kitchen stove with bank notes."^[10]

In 1905, Mendeleev was elected a member of the Royal Swedish Academy of Sciences. The following year the Nobel Committee for Chemistry recommended to the Swedish Academy to award the Nobel Prize in Chemistry for 1906 to Mendeleev for his discovery of the periodic system. The Chemistry Section of the Swedish Academy supported this recommendation. The Academy was then supposed to approve the Committee choice as it has done in almost every case. Unexpectedly, at the full meeting of the Academy, a dissenting member of the Nobel Committee, Peter Klason, proposed the candidacy of Henri Moissan whom he favored. Svante Arrhenius, although not a member of the Nobel Committee for Chemistry, had a great deal of influence in the Academy and also pressed for the rejection of Mendeleev, arguing that the periodic system was too old to acknowledge its discovery in 1906. According to the contemporaries, Arrhenius was motivated by the grudge he held against Mendeleev for his critique of Arrhenius's dissociation theory. After heated arguments, the majority of the Academy voted for Moissan. The attempts to nominate Mendeleev in 1907 were again frustrated by the absolute opposition of Arrhenius.^[11]

In 1907, Mendeleev died at the age of 72 in Saint Petersburg from influenza. The crater Mendeleev on the Moon, as well as element number 101, the radioactive mendelevium, are named after him.

Periodic table

Sculpture in honor of Mendeleev and the periodic table, located in Bratislava, Slovakia

In 1863 there were 56 known elements with a new element being discovered at a rate of approximately one per year.

Other scientists had previously identified periodicity of elements. John Newlands described a Law of Octaves, noting their periodicity according to relative atomic weight in 1864, publishing it in 1865. His proposal identified the potential for new elements such as germanium. The concept was criticized and his innovation was not recognised by the Society of Chemists until 1887. Another person to prose a periodic table was Lothar Meyer, who published a paper in 1864 describing 28 elements classified by their valence, but with no prediction of new elements.

After becoming a teacher, Mendeleev wrote the definitive textbook of his time: Principles of Chemistry (two volumes, 1868–1870). As he attempted to classify the elements according to their chemical properties, he too noticed patterns that led him to postulate his periodic table. Mendeleev was unaware of the earlier work on periodic tables going on in the 1860s. He made the following table, and by adding additional elements following this pattern, developed his extended version of the periodic table.

On 6 March 1869, Mendeleev made a formal presentation to the Russian Chemical Society, entitled The Dependence between the Properties of the Atomic Weights of the Elements, which described elements according to both atomic weight and valence. This presentation stated that

1. The elements, if arranged according to their atomic weight, exhibit an apparent periodicity of properties.
2. Elements which are similar in regards to their chemical properties have atomic weights which are either of nearly the same value (e.g., Pt, Ir, Os) or which increase regularly (e.g., K, Rb, Cs).
3. The arrangement of the elements in groups of elements in the order of their atomic weights corresponds to their so-called valencies, as well as, to some extent, to their distinctive chemical properties; as is apparent among other series in that of Li, Be, B, C, N, O, and F.
4. The elements which are the most widely diffused have small atomic weights.
5. The magnitude of the atomic weight determines the character of the element, just as the magnitude of the molecule determines the character of a compound body.
6. We must expect the discovery of many yet unknown elements–for example, two elements, analogous to aluminium and silicon, whose atomic weights would be between 65 and 75.
7. The atomic weight of an element may sometimes be amended by a knowledge of those of its contiguous elements. Thus the atomic weight of tellurium must lie between 123 and 126, and cannot be 128. Here Mendeleev seems to be wrong as the "atomic mass" of tellurium (127.6) remains higher than that of iodine (126.9) as displayed on modern periodic tables, but this is due to the way atomic masses are calculated, based on a weighted average of all of an element's common isotopes, not just the one-to-one proton/neutron-ratio version of the element to which Mendeleev was referring.
8. Certain characteristic properties of elements can be foretold from their atomic weights.

Mendeleev published his periodic table of all known elements and predicted several new elements to complete the table. Only a few months after, Meyer published a virtually identical table. Some consider Meyer and Mendeleev the co-creators of the periodic table, but virtually everybody agrees that Mendeleev's accurate prediction of the qualities of what he called ekasilicon, ekaaluminium and ekaboron (germanium, gallium and scandium, respectively) qualifies him for the majority of the credit for the table.

For his predicted eight elements, he used the prefixes of eka, dvi, and tri (Sanskrit one, two, three) in their naming. Mendeleev questioned some of the currently accepted atomic weights (they could be measured only with a relatively low accuracy at that time), pointing out that they did not correspond to those suggested by his Periodic Law. He noted that tellurium has a higher atomic weight than iodine, but he placed them in the right order, incorrectly predicting that the accepted atomic weights at the time were at fault. He was puzzled about where to put the known lanthanides, and predicted the existence of another row to the table which were the actinides which were some of the heaviest in atomic mass. Some people dismissed Mendeleev for predicting that there would be more elements, but he was proven to be correct when Ga (gallium) and Ge (germanium) were found in 1875 and 1886 respectively, fitting perfectly into the two missing spaces.

By giving Sanskrit names to his "missing" elements, Mendeleev showed his appreciation and debt to the Sanskrit grammarians of ancient India, who had created sophisticated theories of language based on their discovery of the two-dimensional patterns in basic sounds. According to Professor Paul Kiparsky of Stanford University, Mendeleev was a friend and colleague of the Sanskritist Böhtlingk, who was preparing the second edition of his book on Pāṇini at about this time, and Mendeleev wished to honor Pāṇini with his nomenclature.^[16] Noting that there are striking similarities between the periodic table and the introductory Śiva Sūtras in Pāṇini's grammar, Prof. Kiparsky says:

[T]he analogies between the two systems are striking. Just as Panini found that the phonological patterning of sounds in the language is a function of their articulatory properties, so Mendeleev found that the chemical properties of elements are a function of their atomic weights. Like Panini, Mendeleev arrived at his discovery through a search for the "grammar" of the elements...

Other achievements

Mendeleev made other important contributions to chemistry. The Russian chemist and science historian Lev Chugaev has characterized him as "a chemist of genius, first-class physicist, a fruitful researcher in the fields of hydrodynamics, meteorology, geology, certain branches of chemical technology (explosives, petroleum, and fuels, for example) and other disciplines adjacent to chemistry and physics, a thorough expert of chemical industry and industry in general, and an original thinker in the field of economy." Mendeleev was one of the founders, in 1869, of the Russian Chemical Society. He worked on the theory and practice of protectionist trade and on agriculture.

In an attempt at a chemical conception of the Aether, he put forward a hypothesis that there existed two inert chemical elements of lesser atomic weight than hydrogen. Of these two proposed elements, he thought the lighter to be an all-penetrating, all-pervasive gas, and the slightly heavier one to be a proposed element, coronium.

Mendeleev devoted much study and made important contributions to the determination of the nature of such indefinite compounds as solutions.

Mendeleev Medal

In another department of physical chemistry, he investigated the expansion of liquids with heat, and devised a formula similar to Gay-Lussac's law of the uniformity of the expansion of gases, while in 1861 he anticipated Thomas Andrews' conception of the critical temperature of gases by defining the absolute boiling-point of a substance as the temperature at which cohesion and heat of vaporization become equal to zero and the liquid changes to vapor, irrespective of the pressure and volume.

Mendeleev is given credit for the introduction of the metric system to the Russian Empire.

He invented pyrocollodion, a kind of smokeless powder based on nitrocellulose. This work had been commissioned by the Russian Navy, which however did not adopt its use. In 1892 Mendeleev organized its manufacture.

Mendeleev studied petroleum origin and concluded hydrocarbons are abiogenic and form deep within the earth – see Abiogenic petroleum origin. He wrote: " The capital fact to note is that petroleum was born in the depths of the earth, and it is only there that we must seek its origin. " (Dmitri Mendeleev, 1877)

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