Carbonation of Olivine at CO2 Supercritical
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Tubular Symplectic Inclusions in Olivine from the Fukang Pallasite
Meteoritics & Planetary Science 45, Nr 5, 899–910 (2010) doi: 10.1111/j.1945-5100.2010.01054.x Tubular symplectic inclusions in olivine from the Fukang pallasite Michael R. STEVENS1, David R. BELL1,2, and Peter R. BUSECK1,2* 1School of Earth and Space Exploration, Arizona State University, Tempe, Arizona 85287, USA 2Department of Chemistry and Biochemistry, Arizona State University, Tempe, Arizona 85287, USA *Corresponding author. E-mail: [email protected] (Received 11 June 2009; revision accepted 27 March 2010) Abstract–Olivine from the Fukang meteorite, like that from many other pallasites, contains distinctive arrays of parallel, straight, tubular inclusions. They differ in their extension and linearity from those in terrestrial olivines. They comprise approximately 1% of the total volume. Most have lens-shaped cross-sections, but some are rounded. The major axis of the lens-shaped inclusions is rigorously oriented along olivine [001], and the rounded ones lie along olivine [010] and a few along [100]. The linear nature and orientations of the inclusions suggest that they nucleated on screw dislocations, perhaps formed through shock triggering. High-resolution transmission electron microscopy (TEM) and energy-dispersive x-ray spectroscopy show that the inclusions consist of symplectic intergrowths of chromite, diopside, and silica that appear to have formed by exsolution from the host olivine. The symplectites consist of chromite lamellae with approximately 35-nm spacings that grew outward from a central plane, with interstitial diopside and silica. Contrast modulations having an average spacing of 4.4 nm occur within the chromite lamellae. Using a reaction- front model, we estimate that exsolution occurred over a period of 30 to 100 min, suggesting rapid cooling at high temperature. -
Oxidative Addition & Reductive Elimination
3/1/2021 Oxidative Addition & Reductive Elimination Robert H. Crabtree: Pages 159 – 182 and 235 - 266 1 Oxidative Addition Change in Example Group configuration • Oxidative addition is a key step in many transition-metal catalyzed reactions 10 8 I III • Basic reaction: d d Cu Cu 11 X X Pd0 PdII 10 LnM + LnM Pt0 PtII 10 Y Y d8 d6 PdII PdIV 10 • The new M-X and M-Y bonds are formed using the electron pair of the X-Y PtII PtIV 10 bond and one metal-centered lone pair IrI IrIII 9 RhI RhIII 9 • The metal goes up in oxidation state (+2), X-Y formally gets reduced to X-, Y- d6 d4 ReI ReIII 7 • The ease of addition (or elimination) can be tuned by the electronic and 0 II steric properties of the ancillary ligands Mo Mo 6 • OA favored by strongly e-donating L d4 d2 MoII MoIV 6 • The most common applications involve: a) Late transition metals (platinum metals: Ru, Rh, Pd, Ir, Pt) - not d7 d6 2CoII 2CoIII 9 too sensitive to O2 and H2O; routinely used in organic synthesis b) C-Halogen, H-H or Si-H bonds d4 d3 2CrII 2CrIII 6 • Common for transition metals, rare for main-group metals but: Grignard reagents! 2 1 3/1/2021 Oxidative addition – concerted mechanism Concerted addition - mostly with non-polar X-Y bonds X X X LnM + LnM LnM Y Y Y A Cr(CO)5: • H2, silanes, alkanes, ... coordinatively Cr(PMe3)5: • Arene C-H bonds more reactive than alkane C-H bonds unsaturated, but metal- centered lone pairs not phosphines are better • H-H, C-H strong bond, but M-H and M-C bonds can be very available donors, weaker acceptors full oxidative -
(M = Ca, Mg, Fe2+), a Structural Base of Ca3mg3(PO4)4 Phosphors
crystals Article Crystal Chemistry of Stanfieldite, Ca7M2Mg9(PO4)12 (M = Ca, Mg, Fe2+), a Structural Base of Ca3Mg3(PO4)4 Phosphors Sergey N. Britvin 1,2,* , Maria G. Krzhizhanovskaya 1, Vladimir N. Bocharov 3 and Edita V. Obolonskaya 4 1 Department of Crystallography, Institute of Earth Sciences, St. Petersburg State University, Universitetskaya Nab. 7/9, 199034 St. Petersburg, Russia; [email protected] 2 Nanomaterials Research Center, Kola Science Center of Russian Academy of Sciences, Fersman Str. 14, 184209 Apatity, Russia 3 Centre for Geo-Environmental Research and Modelling, Saint-Petersburg State University, Ulyanovskaya ul. 1, 198504 St. Petersburg, Russia; [email protected] 4 The Mining Museum, Saint Petersburg Mining University, 2, 21st Line, 199106 St. Petersburg, Russia; [email protected] * Correspondence: [email protected] Received: 1 May 2020; Accepted: 25 May 2020; Published: 1 June 2020 Abstract: Stanfieldite, natural Ca-Mg-phosphate, is a typical constituent of phosphate-phosphide assemblages in pallasite and mesosiderite meteorites. The synthetic analogue of stanfieldite is used as a crystal matrix of luminophores and frequently encountered in phosphate bioceramics. However, the crystal structure of natural stanfieldite has never been reported in detail, and the data available so far relate to its synthetic counterpart. We herein provide the results of a study of stanfieldite from the Brahin meteorite (main group pallasite). The empirical formula of the mineral is Ca8.04Mg9.25Fe0.72Mn0.07P11.97O48. Its crystal structure has been solved and refined to R1 = 0.034. Stanfieldite from Brahin is monoclinic, C2/c, a 22.7973(4), b 9.9833(2), c 17.0522(3) Å, β 99.954(2)◦, 3 V 3822.5(1)Å . -
Oxidative Addition of Polar Reagents
OXIDATIVE ADDITION OF POLAR REAGENTS Organometallic chemistry has vastly expanded the practicing organic chemist’s notion of what makes a good nucleophile or electrophile. Pre-cross-coupling, for example, using unactivated aryl halides as electrophiles was largely a pipe dream (or possible only under certain specific circumstances). Enter the oxidative addition of polarized bonds: all of a sudden, compounds like bromobenzene started looking a lot more attractive as starting materials. Cross-coupling reactionsinvolving sp2- and sp-hybridized C–X bonds beautifully complement the “classical” substitution reactions at sp3electrophilic carbons. Oxidative addition of the C–X bond is the step that kicks off the magic of these methods. In this post, we’ll explore the mechanisms and favorability trends of oxidative additions of polar reagents. The landscape of mechanistic possibilities for polarized bonds is much more rich than in the non-polar case—concerted, ionic, and radical mechanisms have all been observed. Concerted Mechanisms 2 Oxidative additions of aryl and alkenyl Csp –X bonds, where X is a halogen or sulfonate, proceed through concertedmechanisms analogous to oxidative additions of dihydrogen. Reactions of N–H and O–H bonds in amines, alcohols, and water also appear to be concerted. A π complex involving η2-coordination is an intermediate in the mechanism of insertion into aryl halides at least, and probably vinyl halides too. As two open coordination sites are necessary for concerted oxidative addition, loss of a ligand from a saturated metal complex commonly precedes the actual oxidative addition event. Concerted oxidative addition of aryl halides and sulfonates. Trends in the reactivity of alkyl and aryl (pseudo)halides toward oxidative addition are some of the most famous in organometallic chemistry. -
18- Electron Rule. 18 Electron Rule Cont’D Recall That for MAIN GROUP Elements the Octet Rule Is Used to Predict the Formulae of Covalent Compounds
18- Electron Rule. 18 Electron Rule cont’d Recall that for MAIN GROUP elements the octet rule is used to predict the formulae of covalent compounds. Example 1. This rule assumes that the central atom in a compound will make bonds such Oxidation state of Co? [Co(NH ) ]+3 that the total number of electrons around the central atom is 8. THIS IS THE 3 6 Electron configuration of Co? MAXIMUM CAPACITY OF THE s and p orbitals. Electrons from Ligands? Electrons from Co? This rule is only valid for Total electrons? Period 2 nonmetallic elements. Example 2. Oxidation state of Fe? The 18-electron Rule is based on a similar concept. Electron configuration of Fe? [Fe(CO) ] The central TM can accommodate electrons in the s, p, and d orbitals. 5 Electrons from Ligands? Electrons from Fe? s (2) , p (6) , and d (10) = maximum of 18 Total electrons? This means that a TM can add electrons from Lewis Bases (or ligands) in What can the EAN rule tell us about [Fe(CO)5]? addition to its valence electrons to a total of 18. It can’t occur…… 20-electron complex. This is also known Effective Atomic Number (EAN) Rule Note that it only applies to metals with low oxidation states. 1 2 Sandwich Compounds Obeying EAN EAN Summary 1. Works well only for d-block metals. It does not apply to f-block Let’s draw some structures and see some new ligands. metals. 2. Works best for compounds with TMs of low ox. state. Each of these ligands is π-bonded above and below the metal center. -
NIH Public Access Author Manuscript J Am Chem Soc
NIH Public Access Author Manuscript J Am Chem Soc. Author manuscript; available in PMC 2013 August 29. NIH-PA Author ManuscriptPublished NIH-PA Author Manuscript in final edited NIH-PA Author Manuscript form as: J Am Chem Soc. 2012 August 29; 134(34): 14232–14237. doi:10.1021/ja306323x. A Mild, Palladium-Catalyzed Method for the Dehydrohalogenation of Alkyl Bromides: Synthetic and Mechanistic Studies Alex C. Bissember†,‡, Anna Levina†, and Gregory C. Fu†,‡ †Department of Chemistry, Massachusetts Institute of Technology, Cambridge, Massachusetts 02139, United States ‡Division of Chemistry and Chemical Engineering, California Institute of Technology, Pasadena, California 91125, United States Abstract We have exploited a typically undesired elementary step in cross-coupling reactions, β-hydride elimination, to accomplish palladium-catalyzed dehydrohalogenations of alkyl bromides to form terminal olefins. We have applied this method, which proceeds in excellent yield at room temperature in the presence of a variety of functional groups, to a formal total synthesis of (R)- mevalonolactone. Our mechanistic studies establish that the rate-determining step can vary with the structure of the alkyl bromide, and, most significantly, that L2PdHBr (L=phosphine), an often- invoked intermediate in palladium-catalyzed processes such as the Heck reaction, is not an intermediate in the active catalytic cycle. INTRODUCTION The elimination of HX to form an olefin is one of the most elementary transformations in organic chemistry (eq 1).1,2 However, harsh conditions, such as the use of a strong Brønsted acid/base or a high temperature (which can lead to poor functional-group compatibility and to olefin isomerization) are often necessary for this seemingly straightforward process. -
Tutorial on Oxidative Addition Jay A
Tutorial pubs.acs.org/Organometallics Tutorial on Oxidative Addition Jay A. Labinger* Beckman Institute and Division of Chemistry and Chemical Engineering, California Institute of Technology, 1200 East California Boulevard, Pasadena, California 91125, United States ABSTRACT: This tutorial introduces oxidative addition as a reactivity pattern and organizing principle for organometallic chemistry. The history, characteristics, and scope of oxidative addition are briefly surveyed, followed by a detailed examination of the variety of mechanisms found for the oxidative addition of alkyl halides and their relevance to practical applications. ■ INTRODUCTION comprehensive review but rather as an introduction to the The recognition of oxidative addition as a common pattern of topic, such as might be presented in a lecture, as part of a reactivity has played a central role in the development of course on organometallic chemistry. Accordingly, the tone is organometallic chemistry over the second half of the 20th rather informal, and citations have been limited to a moderate number of historically significant papers. Those interested in century. The starting point for modern organotransition-metal following up on any aspects can find more details and thorough chemistry is usually taken as the discovery and structural referencing elsewhere; Hartwig’s recent textbook5 is a good characterization of ferrocene in the early 1950s (of course, starting point. there were many important earlier contributions). That inspired a large amount of new chemistry during -
ELEMENTAL ABUNDANCES in the SILICATE PHASE of PALLASITIC METEORITES Redacted for Privacy Abstract Approved: Roman A
AN ABSTRACT OF THE THESIS OF THURMAN DALE COOPER for theMASTER OF SCIENCE (Name) (Degree) in CHEMISTRY presented on June 1, 1973 (Major) (Date) Title: ELEMENTAL ABUNDANCES IN THE SILICATE PHASE OF PALLASITIC METEORITES Redacted for privacy Abstract approved: Roman A. Schmitt The silicate phases of 11 pallasites were analyzed instrumen- tally to determine the concentrations of some major, minor, and trace elements.The silicate phases were found to contain about 98% olivine with 1 to 2% accessory minerals such as lawrencite, schreibersite, troilite, chromite, and farringtonite present.The trace element concentrations, except Sc and Mn, were found to be extremely low and were found primarily in the accessory phases rather than in the pure olivine.An unusual bimodal Mn distribution was noted in the pallasites, and Eagle Station had a chondritic nor- malized REE pattern enrichedin the heavy REE. The silicate phases of pallasites and mesosiderites were shown to be sufficiently diverse in origin such that separate classifications are entirely justified. APPROVED: Redacted for privacy Professor of Chemistry in charge of major Redacted for privacy Chairman of Department of Chemistry Redacted for privacy Dean of Graduate School Date thesis is presented June 1,1973 Typed by Opal Grossnicklaus for Thurman Dale Cooper Elemental Abundances in the Silicate Phase of Pallasitic Meteorites by Thurman Dale Cooper A THESIS submitted to Oregon State University in partial fulfillment of the requirements for the degree of Master of Science June 1974 ACKNOWLEDGMENTS The author wishes to express his gratitude to Prof. Roman A. Schmitt for his guidance, suggestions, discussions, and thoughtful- ness which have served as an inspiration. -
Spring 1995 Gems & Gemology
TABLE CONTENTS FEATURE ARTICLES 2 Rubies from Mong Hsu Adolf Pelsetti, I(ar7 Schmetzer, Heinz-Jiirgen Bernhardt, and Fred Mouawad " 28 The Yogo Sapphire Deposit Keith A. ~~chaluk NOTES AND NEW TECHNIQUES 42 Meerschaum from Eskisehir Province, Turkey I<adir Sariiz and Islcender Isilc REGULAR FEATURES 52 Gem Trade Lab Notes Gem News Most Valuable Article Award Gems ed Gemology Challenge Book Reviews Gemological Abstracts Guidelines for Authors ABOUT THE COVER: One of the most important ruby localities of the 1990s cov- ers a broad orea near the town of Mong Hsu, in northeastern Myann~ar(B~lrrna). The distinctive gemological features of these rubies are detailed in this issue's lead article. The suite of fine jewelry illustraled here contains 36 Mong Hsu rubies with a total weigh1 of 65.90 ct; the two rubies in the ring total 5.23 ct. jewelry courtesy of Mouawad jewellers. Photo by Opass Sultsumboon-Opass Suksuniboon Studio, Bangltolz, Thailand. Typesetting for Gerrls eS Gemology is by Graphix Express, Santa Monica, CA. Color separations are by Effective Graphics, Compton, CA. Printing is by Cadmus lournal Services, Easton, MD. 0 1995 Gemological Institute of America All rights reserved ISSN 0016-626X - Editor-in-Chief Editor Editors, Gem Trade Lab Notes Richard T. Lidtlicoat Alicc S. I<cller Robcrt C. I<ammerling 1660 Stewart St. C. W. Fryer Associate Editors Smta Mon~ca,CA 90404 William E. Boyajian Editors, Gem News (800)421-7250 ~251 Robcrt C. Kamn~erling Rohcrt C. I<ammerling e-mail: altellcrBclass.org D. Vincent Manson John I. Koivula John Sinltanltas Sr~bscriptions Enirnanuel Fritsch Jln Ll~n Editors, Book llevielvs Technical Editor (800) 421-7250 x201 Susan B. -
N Arieuican%Mllsellm
n ARieuican%Mllsellm PUBLISHED BY THE AMERICAN MUSEUM OF NATURAL HISTORY CENTRAL PARK WEST AT 79TH STREET, NEW YORK 24, N.Y. NUMBER 2I63 DECEMBER I9, I963 The Pallasites BY BRIAN MASON' INTRODUCTION The pallasites are a comparatively rare type of meteorite, but are remarkable in several respects. Historically, it was a pallasite for which an extraterrestrial origin was first postulated because of its unique compositional and structural features. The Krasnoyarsk pallasite was discovered in 1749 about 150 miles south of Krasnoyarsk, and seen by P. S. Pallas in 1772, who recognized these unique features and arranged for its removal to the Academy of Sciences in St. Petersburg. Chladni (1794) examined it and concluded it must have come from beyond the earth, at a time when the scientific community did not accept the reality of stones falling from the sky. Compositionally, the combination of olivine and nickel-iron in subequal amounts clearly distinguishes the pallasites from all other groups of meteorites, and the remarkable juxtaposition of a comparatively light silicate mineral and heavy metal poses a nice problem of origin. Several theories of the internal structure of the earth have postulated the presence of a pallasitic layer to account for the geophysical data. No apology is therefore required for an attempt to provide a comprehensive account of this remarkable group of meteorites. Some 40 pallasites are known, of which only two, Marjalahti and Zaisho, were seen to fall (table 1). Of these, some may be portions of a single meteorite. It has been suggested that the pallasite found in Indian mounds at Anderson, Ohio, may be fragments of the Brenham meteorite, I Chairman, Department of Mineralogy, the American Museum of Natural History. -
Meteorite Collections: Sample List
Meteorite Collections: Sample List Institute of Meteoritics Department of Earth and Planetary Sciences University of New Mexico October 01, 2021 Institute of Meteoritics Meteorite Collection The IOM meteorite collection includes samples from approximately 600 different meteorites, representative of most meteorite types. The last printed copy of the collection's Catalog was published in 1990. We will no longer publish a printed catalog, but instead have produced this web-based Online Catalog, which presents the current catalog in searchable and downloadable forms. The database will be updated periodically. The date on the front page of this version of the catalog is the date that it was downloaded from the worldwide web. The catalog website is: Although we have made every effort to avoid inaccuracies, the database may still contain errors. Please contact the collection's Curator, Dr. Rhian Jones, ([email protected]) if you have any questions or comments. Cover photos: Top left: Thin section photomicrograph of the martian shergottite, Zagami (crossed nicols). Brightly colored crystals are pyroxene; black material is maskelynite (a form of plagioclase feldspar that has been rendered amorphous by high shock pressures). Photo is 1.5 mm across. (Photo by R. Jones.) Top right: The Pasamonte, New Mexico, eucrite (basalt). This individual stone is covered with shiny black fusion crust that formed as the stone fell through the earth's atmosphere. Photo is 8 cm across. (Photo by K. Nicols.) Bottom left: The Dora, New Mexico, pallasite. Orange crystals of olivine are set in a matrix of iron, nickel metal. Photo is 10 cm across. (Photo by K. -
Ruthenium Olefin Metathesis Catalysts
Ruthenium Olefin Metathesis Catalysts: Tuning of the Ligand Environment Ruthenium olefine metathese katalysatoren: Optimalisatie van de ligandsfeer Nele Ledoux Promotor: Prof. Dr. F. Verpoort Proefschrift ingediend tot het behalen van de graad van Doctor in de Wetenschappen: Scheikunde Vakgroep Anorganische en Fysische Chemie Vakgroepvoorzitter: Prof. Dr. S. Hoste Faculteit Wetenschappen 2007 ii Members of the Dissertation Committee: Prof. Dr. F. Verpoort Prof. Dr. Ir. C. Stevens Dr. V. Dragutan Dr. R. Drozdzak Dr. R. Winde Prof. Dr. Ir. D. Devos Prof. Dr. J. Van der Eycken Prof. Dr. P. Van Der Voort Prof. Dr. K. Strubbe This research was funded by the Fund for Scien- tific Research - Flanders (F.W.O.-Vlaanderen). Acknowledgments This dissertation is the final product of an educative and fascinating journey, which involved many contributors. First of all, I wish to express my gratitude to the people with whom I learned how to do research. There is my promotor Prof. Dr. Francis Verpoort who gave me the opportunity to join his ’Catalysis group’ and ensured the necessary funding. I’m especially grateful for his confidence and indulgence. In addition, I have been extremely lucky to work with several nice colleagues. Thank you, Thank you (= double thank you ♥) to Bart who helped me conquer many small and big difficulties, and by doing so, contributed a lot to the results reported here. Special thanks to Hans for many funny moments and support over the years. Of course, my acknowledgments also go to the other boys: Carl, Stijn, David, Jeroen, Prof. Dr. Pascal Van Der Voort and not to forget Siegfried, Steven, and Mike for the pleasant working atmosphere and supportive chats.