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The life and work of Edward Charles Howard FRS
Abstract
Edward Charles Howard, a notable chemist of the early nineteenth century, was a descendant of the patrician House that has for generations held the premier Dukedom of Norfolk, and the office of Earl Marshal of England. When, as a younger son, he took up an independent profession, his inclination decided him on a career in science. In his relatively brief career - he died at the early age of 42-Howard made original discoveries in three widely different fields of chemical research, each of which proved of lasting influence. In 1800, he discovered the highly explosive fulminates, an achievement that gained him the coveted Copley Medal of the Royal Society. He next demonstrated the characteristic nickel contentof meteorites, thus helping to establish their - so far controversial - cosmic origin. Over the next few years he effected a veritable revolution in sugar manufacturing by his invention of the vacuum evaporation technique and other fundamental improvements. Howard's seminal researches blazed a trail that was taken up to great effect by subsequent researchers and contributed significantly to the rise of the modern explosives industry and sugar manufacture. His outstanding record entitles him to an enduring place in the history of chemical science and technology.
... His father, Henry Howard (1713– 1787) was an unsuccessful wine merchant in Dublin. After his failure in business the 9 th Duke of Norfolk, a kinsman, paid his debts and put him in charge of his Sheffield estates (Kurzer, 1999Kurzer, , 2000 Sears, 1976). At the age of nine Edward was sent to be educated at the Catholic English College in Douay, in Northern France, where his two elder brothers were already enrolled. ...
... His father had died six months previously and there were already signs of the French revolution, which was to break out a year later. The Revolution government would later close all the French scientific institutions as well as religious schools and offices (Kurzer, 1999; Sears, 1976). There is no information about his further education but clearly it was enough to make him a very skilled chemist, as demonstrated by the publication of his first paper in which he announced the discovery of mercury fulminate, a most powerful explosive (Howard, 1800).This paper made Howard well known at home and abroad and gained him the Copley Medal of the Royal Society. ...
... Howard has not stopped here. He has announced to us the discovery of a fulminating silver, analogous in some degree to his fulminating mercury, and he is now employed in the analysis of certain stones, generated in the air by fiery meteors, the component parts of which will probably open a new field of speculation and discussion to mineralogists as well as to meteorologists " (Kurzer, 1999; Sears, 1976). In the year 1799–1800 Howard was elected a Fellow of the Royal Society and became a member of the Royal Institution and of the Society of Arts. ...
To Edward Charles Howard (1774-1816), a self-educated scientist without formal education in chemistry, we owe the (accidental) discovery of mercury fulminate, the finding that meteorites contain nickel and have a composition different from any material originated in the earth, and the design of the vacuum evaporator and other accessories that resulted in a substantial improvement in the economic balance of sugar production.
... Mercury Fulminate was first synthesized in 1800 and found its major commercial application by Alfred Nobel to detonate explosives (30). ...
During the nineteenth century, a major change took place in the trade, production, and use of mercury that altered its nearly exclusive link to silver refining in the Hispanic New World. We track the global expansion of mercury markets in chronological detail from 1511 to 1900 using historical archives on production and trade, a detailed country-by-country accounting of the pool of anthropogenic mercury from which legacy mercury was ultimately generated. The nature and profile of pre-1900 legacy mercury extends beyond silver refining, mercury production, and gold extraction, and includes alternate sources (vermilion, felt, mercury fulminate) and new regions that were not major silver or gold producers (China, India, United Kingdom, France, among others), that accounted for approximately 50% of total mercury consumed in the nineteenth century. The nature of the pre-1900 mercury market requires a quantitative distinction between legacy mercury and historic anthropogenic mercury production and use, since the chemistry of its end-uses determines the pathways and timelines for its incorporation into the global biogeochemical cycle. We thus introduce the concept of a mercury source pool to account for total historic anthropogenic mercury within and outside this cycle. Together with a critical review of previous assumptions used to reconstruct the historical use and loss of mercury, a much lower level of emissions of pre-1900 legacy mercury is proposed. A coordinated effort across disciplines is needed, to complete a historically accurate scenario that can guide the multilateral policies adopted under the United Nations Minamata Convention to control mercury in the environment.
... 35 In 1804, he apparently had already established dealings with a sugar house that enabled him to be married in a parish in East London. 36 Tennant was apparently asked by Banks to analyse the Cape of Good Hope meteorite because Howard was occupied with other interests in the sugar industry. ...
Smithson Tennant is known mainly for his discovery of osmium and iridium. This paper details Tennant's involvement with meteorites, which has received little attention by his biographers, and provides new information about his final stay in Paris. Tennant reported his analysis of the Cape of Good Hope meteorite in 1806 and received a sample of the Bendego meteorite in 1811 that was subsequently analysed by Wollaston. During Tennant's final trip to France, which began in September 1814, Berthollet presented a sample of the Limerick meteorite that he received from Tennant to the French Institute. Tennant visited Delametherie, and an unpublished letter acquired by the author shows that he met the explorer and scientist Alexander von Humboldt. The Limerick meteorite was discussed with Delametherie and probably with Humboldt. Evidence suggests that Tennant met the painter Francois Gerard and the scientists Biot, Arago, Gay-Lussac and Cuvier. The Limerick meteorite specimen that Tennant gave to Berthollet is probably Museum National d'Histoire Naturelle sample MNHN-35, whose donor is unknown. Tennant was the first to be quoted in the scientific literature about the Limerick meteorite-more than three years before the scientist William Higgins published his account of the meteorite shower.
... Essentially, Kunckel described in his book "Laboratorium Chymicum" the violent formation of mercury fulminate from mercury nitrate and alcohol but he did not isolate it. The English chemist Edward Howard (1774Howard ( -1816 [3,4] succeeded in 1799 (in the beginning of the "Scientific Chemistry") to isolate mercury fulminate by treating a solution of mercury in nitric acid with ethanol. Howard's report [4] in 1800 on the preparation and properties was a sensation within the scientific world [2a, 3]. ...
A short survey on the fascinating history of mercury fulminate is given. The crystal structure of Hg(CNO)2 has been determined using single crystal X-ray diffraction. Mercury fulminate crystallizes in an orthorhombic cell, space group Cmce with a = 5.3549(2), b = 10.4585(5), c = 7.5579(4) Å and Z = 4. The distances and angles in the O-N≡C-Hg-C≡N-O molecule are Hg-C 2.029(6) Å, C≡N 1.143(8) Å, N-O 1.248(6) Å and C-Hg-C 180.0(1)°, Hg-C≡N 169.1(5)°, C≡N-O 179.7(6)°. Each mercury atom is surrounded by two oxygen atoms from neighbouring Hg(CNO)2 molecules with a nonbonding distance of Hg···O 2.833(4) Å. The Hg-C bond lengths in the linear Hg(CNO)2 molecules are shorter than those in the tetrahedral complex [Hg(CNO)4]2−. This refers to a large contribution of the 6s orbital in the Hg-C bonds of Hg(CNO)2. The results of the X-ray powder investigation on Hg(CNO)2 are also reported.
Sugarcane, or Saccharum officinarum is thought to have been first domesticated by the Papuans in around 8000 BCE. This ancient civilisation was thought to have simply chewed the cane raw. Sugar was spread and cultivated by the Austronesian peoples across Island South East Asia, before reaching China and India around 3000 BCE. The geographical location of sugar cane growing changed several times over the course of 3,500 years. It began in India and Persia, then spread along the Mediterranean coast to the islands off Africa’s coast, and then to the Americas before moving back across the world to Indonesia.
In order to produce sugar, a new type of agriculture was developed. This was called the Plantation System, in which colonists planted large areas of single crops. These crops could be shipped far and wide, and could be sold at a good price in Europe. In order to increase productivity and profitability, slaves (or indentured servants) were imported to take care of the labor intensive crops. The first crops grown in the Plantation System were sugar cane, but many other crops followed, including coffee and cotton, cocoa and tobacco, tea and rubber, and eventually oil palm.
The properties of common and less common explosive fulminates are discussed. Starting with fulminic acid and continuing through well-known mercury and silver fulminates, the reader gets an idea about their properties, historical development of their application, and the peculiarities related to their preparation and use in the laboratory. Some less common fulminates and fulminate complexes are briefly mentioned and their explosive as well as physical properties are compared to mercury fulminate.
This is the first comprehensive overview of this topic. It serves as a single source for information about the properties, preparation, and uses of all relevant primary explosives. The first chapter provides background such as the basics of initiation and differences between requirements on primary explosives used in detonators and igniters. The authors then clarify the influence of physical characteristics on explosive properties, focusing on those properties required for primary explosives. Furthermore, the issue of sensitivity is discussed. All the chapters on particular groups of primary explosives are structured in the same way, including introduction, physical and chemical properties, explosive properties, preparation and documented use. The authors thoroughly verified all data and information. A unique feature of this book are original microscopic images of some explosives. © Springer-Verlag Berlin Heidelberg 2013. All rights are reserved.
During the second half of the twentieth century, the domain of geochemistry has greatly expanded and the field is today often seen as a branch of an extended chemistry of the Earth, called cosmochemistry. This paper is a historical introduction to cosmochemistry in which the wider cosmic aspects are surveyed up to about 1915, when nuclear physics changed the scene. These wider aspects or themes include, firstly, the attempts to determine the relative abundances of the elements, secondly, the extension of geochemistry to include physical geochemistry, thirdly, the study of meteorites and, fourthly, the spectroscopic study of the stars within the astrochemical tradition. Because of the lack of reliable data, a great deal of the protocosmochemistry described in the present paper was speculative. Nonetheless, by 1915 the contours of the cosmochemistry of the future were just visible and the developments here singled out can thus be seen as belonging to the prehistory of modern cosmochemistry.
The story of the discovery, investigation, and eventual correct formulation of fulminic acid, HCNO, extends over a period of 200 years and reflects uniquely, in its many stages, the evolution of organic chemistry from post-alchemistic times to the age of wave mechanics. Fulminic acid was discovered in 1800 when E. Howard serendipitously prepared its highly explosive mercury and silver salts. The determination of its structure presented unusual difficulties and taxed the ingenuity of leading chemists of successive generations. Their work generated a procession of proposed and discarded formulations that was only finally ended in the 1960s with the recognition of fulminic acid as the mesomeric structure and hence with its identification as the parent compound of the important class of the nitrile N-oxides. Recently fulminic acid and several of its isotopomers have been subjected to the most searching spectroscopic investigations and ab initio computations, by which its molecular dimensions and geometry, and its "quasi-linear" structure have been revealed. In technology, mercury fulminate occupied for nearly a century a uniquely important position as the only available practical detonator for every kind of conventional explosive. Keywords (Audience): General Public
The first chemical investigations and publications by Justus von Liebig dealt with the fulminates of silver and mercury. Even as a boy Liebig had learnt how to prepare silver fulminate, and as student of chemistry in Erlangen (1821) he studied the properties and reactions of silver fulminate. In Paris in 1823 (together with Gay-Lussac) he succeeded in analyzing quantitatively the highly explosive silver compound. This great experimental success with the dangerous silver fulminate was most important in three respects: i. The development of the experimental method later culminated in Liebig’s perfected and well-known C,H,N analysis of organic compounds (1830). ii. It led to the concept of isomerism when F. Wöhler found that silver cyanate had the same composition as silver fulminate. iii. It was decisive for furthering the scientific career of Liebig, since Alexander von Humboldt was highly impressed by the great skill and talent of Liebig and — by recommendation of Humboldt — Liebig became Professor in Gießen in 1824 (at the young age of 21). The first (fulminato)metal complex, K[Ag(CNO)2], was also isolated by Liebig. Later, explosive (fulminato)metal complexes were prepared by Nef, Wieland, and especially by Lothar Wöhler and co-workers. In Munich the HCNO structure of fulminic acid was established by its IR spectrum and the spectroscopic properties of (fulminato)metal complexes were studied. A series of new nonexplosive complexes could be obtained by dilution of the energy-rich species with large cations or ligands. Recent X-ray structure determinations have revealed the almost perfect linear, tetrahedral, square-planar, or octahedral structures of these complexes with linear metal−C≡NO bonds, e.g. [Au(CNO)2]−, [Zn(CNO)4]2−, [Ni(CNO)4]2−, [Co(CNO)6]3−. DFT calculations have given very good agreement between the calculated and experimental structural parameters and CNO stretching frequencies. The (fulminato)metal complexes closely resemble the analogous cyano compounds. (© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2003)
The travels in which I have been employed, by order of our empress, since the year 1768, have interrupted the correspondence I had the pleasure to entertain with some of the Fellows of the Royal Society of London, particularly the worthy Mr. Collinson; and as this ingenious man, in the mean time, has left this world, I make so free as to address myself to you directly, for the leave of communicating from time to time, to the Royal Society, such observation or papers, which I am not bound to deliver to the Academy here. I would have before this observed that duty, to which the honour of being a foreign member of the Royal Society obliges me, had not the distance in which I have lived thees seven years, mostly out of Europe, and the troublesome manner of travelling in these countries, together with the distractions and duties of my employment, rendered it impossible.
The recent isolation of isofulminic acid has opened the door for a comparative study of all the four possible CHNO isomers: isocyanic acid, cyanic acid, fulminic acid, and isofulminic acid. Their infrared spectra have been measured in an argon matrix at 13 K and are compared with the results of ab initio calculations.
Die CHNO-Isomeren
Die kürzlich gelungene Isolierung von Isoknallsäure hat das Tor für eine vergleichende Studie über alle vier möglichen CHNO Isomere (Isocyansäure, Cyansäure, Knallsäure und Isoknallsäure) geöffnet. Ihre Infrarot-Spektren, aufgenommen in einer Argon-Matrix bei 13 K, werden mit den Ergebnissen von ab-initio-Rechnungen verglichen.
Neue Art von Knallquecksilber ', Voigt's Magazin fuX r den neuesten Zustand der Naturkunde, 2 (1800) 584 ; idem, `Howard er® ndet ein neues detonierendes Quecksilberpra $ parat ' , Busch's Almanach der Fortschritte in Wissenschaften, KuX nsten, etc
- E Howard
E. Howard, `U X ber ein neues Knallquecksilber', TrommelsdorOE 's Journal der Pharmazie, 9 (1801), 338± 67. 39 E. Howard, `Neue Art von Knallquecksilber ', Voigt's Magazin fuX r den neuesten Zustand der Naturkunde, 2 (1800) 584 ; idem, `Howard er® ndet ein neues detonierendes Quecksilberpra $ parat ', Busch's Almanach der Fortschritte in Wissenschaften, KuX nsten, etc., 6 (1802), 141 (Erfurt).
Du mercure fulminant 440± 1 ; [Cit. Fourcroy], `Nouvelles de Chimie
- Howarde
- Howard
Howard, `Sur un nouveau mercure fulminant', Bulletin de la SocieU te Philomatique de Paris, No. 38 (AN IV), quoted in Lettre de M. Blagden au cit. Berthollet', Bibliotheque Britannique, 12 (1799), 366± 9. 41 E. Howard, `Sur un nouveau mercure fulminant', Bibliothe[ que Britannique, 15 (1800), 46± 57, 139± 56, 321± 40 ; 16 (1801), 59± 73. 42 E. Howard, `Du mercure fulminant, par Howard ', Journal de Physique, de Chimie¼, 53 (AN IX, 1801), 440± 1 ; [Cit. Fourcroy], `Nouvelles de Chimie ', Annales de Chimie, 32 (An VIII), 205 ; [E. Howard] `Correspondence: Extrait d'une lettre de M. de Crell au cit. Bouillon-Legrange ', Annales de Chimie, 38 (AN IX) 323± 4. 43 Royal Society Archive, Minutes of the Anniversary Meeting, 1 December 1800, Journa l Book, 37 (1800± 2).
Abridgements of Speci® cations Relating to Sugar AD 1613± 1866 (London, 1871), 17. 123 E. C. Howard, `Separating Insoluble Substances from Fluids in which the Same are Suspended
- Woodcroft
Woodcroft, Abridgements of Speci® cations Relating to Sugar AD 1613± 1866 (London, 1871), 17. 123 E. C. Howard, `Separating Insoluble Substances from Fluids in which the Same are Suspended', British Patent 3831 (4 August 1814).
An Account of the Culture or Planting and Ordering of SaOE ron ', Philosophical Transactions of the Royal Society 945± 8 ; Philosophical Transactions Abridged
- Howard
Howard, `An Account of the Culture or Planting and Ordering of SaOE ron ', Philosophical Transactions of the Royal Society, No. 138 (1678), 945± 8 ; Philosophical Transactions Abridged [by C.
Brief Directions how to Tan Leather, according to the New Invention of the Hon
- G Hutton
- R Shaw
- Pearson
Hutton, G. Shaw and R. Pearson], i i (1672± 83) (London, 1809), 423± 4. 165 C. Howard, `Brief Directions how to Tan Leather, according to the New Invention of the Hon. Charles Howard of Norfolk', Philosophical Transactions of the Royal Society, No. 105 (1674), 93± 6. Phil. Trans. Abridged (as note 164, 136± 8.) 166 C. Howard, `A New Way for the Tanning, Tawing, Dressing and Preparing all Sorts of Rawe Hydes and Skinnes into Leather', British Patent 130 (1660).