atomic arrangements
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This lecture completes the first half of the semester by analyzing three functional groups in terms of the interaction of localized atomic or pairwise orbitals. Many key properties of biological polypeptides derive from the mixing of such localized orbitals that we associate with "resonance" of the amide group. The acidity of carboxylic acids and the aggregation of methyl lithium into solvated tetramers can be understood in analogous terms...more
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In this introductory lecture, Professor Sylvia Ceyer introduces those throughout history who have contributed to the atomic theory of matter, beginning with Aristotle and Democritus, and ending with the work of Lavoisier, Proust, and Dalton. After disussing scanning tunnelling microscopy, Professor Ceyer moves to the major advances in chemistry at the end of the 19th century. These include Newtonian mechanics, thermodynamices, statistical...more
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The most prominent chemist in the generation following Lavoisier was Berzelius in Sweden. Together with Gay-Lussac in Paris and Davy in London, he discovered new elements, and improved atomic weights and combustion analysis for organic compounds. Invention of electrolysis led not only to new elements but also to the theory of dualism, with elements being held together by electrostatic attraction. Wöhler's report on the synthesis of urea re...more
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After discussing the classic determination of the heat of atomization of graphite by Chupka and Inghram, the values of bond dissociation energies, and the utility of average bond energies, the lecture focuses on understanding equilibrium and rate processes through statistical mechanics. The Boltzmann factor favors minimal energy in order to provide the largest number of different arrangements of "bits" of energy. The slippery concept of di...more
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Professor McBride begins by using previous examples of "pathological" bonding and the BH3 molecule to illustrate how a chemist's use of localized bonds, vacant atomic orbitals, and unshared pairs to understand molecules compares with views based on the molecule's own total electron density or on computational molecular orbitals. This lecture then focuses on understanding reactivity in terms of the overlap of singly-occupied molecular orbit...more
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This lecture asks whether it is possible to confirm the reality of bonds by seeing or feeling them. It first describes the work of "clairvoyant" charlatans from the beginning of the twentieth century, who claimed to "see" details of atomic and molecular structure, in order to discuss proper bases for scientific belief. It then shows that the molecular scale is not inconceivably small, and that Newton and Franklin performed simple experimen...more
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By 1950, in most of the underdeveloped world, mortality had fallen to about half its pre-modern rate. The birth rate, however, had remained high and, by 1950, was about twice the death rate. For the rest of the century, both rates fell dramatically and in parallel, maintaining the gap. The enormous excess of births over deaths in this period is known as 'the population explosion.' By 1990, the world population was growing at almost 90 mill...more
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Continuing the discussion of Lewis structures and chemical forces from the previous lecture, Professor McBride introduces the double-well potential of the ozone molecule and its structural equilibrium. The inability for inverse-square force laws to account for stable arrangements of charged particles is prescribed by Earnshaw's Theorem, which may be visualized by means of lines of force. J.J. Thomson circumvented Earnshaw's prohibition on ...more
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Professor Sylvia Ceyer discusses hybridization and chemical bonding. Using methyl nitrate as an example, Professor Ceyer describes how to find the lowest energy Lewis structure and explains bond symmetry, hybrid orbitals, and atomic orbitals. Moving onto intramolecular interactions, the discussion breaks down the origin of a bad hair day: hydrogen bonding, water, and keratin.
