DOCSLIB.ORG

Inclusion Chemistry of Tris(5-Acetyl-3-Thienyl)Methane (Tatm)

Total Page：16

File Type：pdf, Size：1020Kb

Download full-text PDF Read full-text
Inclusion Chemistry of Tris(5-Acetyl-3-Thienyl)Methane (Tatm) INCLUSION CHEMISTRY OF TRIS(5-ACETYL-3-THIENYL)METHANE (TATM) MATERIALS by PAUL S. SIDHU BSc., Dalhousie University, Halifax, Nova Scotia, 1992 MSc., University o f Guelph, Guelph, Ontario, 1994 A THESIS SUBMITTED in PARTIAL FULFILMENT of the REQUIREMENTS for the DEGREE of DOCTOR of PHILOSOPHY to THE DEPARTMENT OF CHEMISTRY and THE FACULTY of GRADUATE STUDIES and RESEARCH CARLETON UNIVERSITY OTTAWA, ONTARIO CANADA April 2005 © Copyright Paul S. Sidhu, 2005 i Reproduced with permission of the copyright owner. Further reproduction prohibited without permission. Library and Bibliotheque et Archives Canada Archives Canada Published Heritage Direction du Branch Patrimoine de I'edition °-494-06746-2 395 Wellington Street 395, rue Wellington Ottawa ON K1A 0N4 Ottawa ON K1A 0N4 Canada Canada NOTICE: AVIS: The author has granted a non­ L'auteur a accorde une licence non exclusive exclusive license allowing Library permettant a la Bibliotheque et Archives and Archives Canada to reproduce, Canada de reproduire, publier, archiver, publish, archive, preserve, conserve, sauvegarder, conserver, transmettre au public communicate to the public by par telecommunication ou par I'lnternet, preter, telecommunication or on the Internet, distribuer et vendre des theses partout dans loan, distribute and sell theses le monde, a des fins commerciales ou autres, worldwide, for commercial or non­ sur support microforme, papier, electronique commercial purposes, in microform, et/ou autres formats. paper, electronic and/or any other formats. The author retains copyright L’auteur conserve la propriete du droit d'auteur ownership and moral rights in et des droits moraux qui protege cette these. this thesis. Neither the thesis Ni la these ni des extraits substantiels de nor substantial extracts from it celle-ci ne doivent etre imprimes ou autrement may be printed or otherwise reproduits sans son autorisation. reproduced without the author's permission. In compliance with the Canadian Conformement a la loi canadienne Privacy Act some supporting sur la protection de la vie privee, forms may have been removed quelques formulaires secondaires from this thesis. ont ete enleves de cette these. While these forms may be included Bien que ces formulaires in the document page count, aient inclus dans la pagination, their removal does not represent il n'y aura aucun contenu manquant. any loss of content from the thesis. 1+1 Canada Reproduced with permission of the copyright owner. Further reproduction prohibited without permission. ABSTRACT A wide variety of materials characterization techniques are used to investigate physicochemical properties of tris(5-acetyl-3-thienyl)methane (TATM) inclusion compounds with, in part, alkyl halide guests and alkyl halide guest families. The results are presented as nine different projects. In the first, we use NMR and X-ray diffraction to characterize the TATM inclusion compound with 1,2-dichloroethane that crystallizes in at least two different forms. We came up with a simple NMR model to describe the motion of the guest, however since it was not consistent with the XRD data, we came up with a second model that was consistent with both experiments. In the second, we characterized TATM inclusion compounds with alkyl halide guest families. We found, based on DSC results, that TATM forms more thermally stable inclusions with guests that have smaller, more electronegative substituents, perhaps due to stronger dipole interactions between host and guest. The third and fourth projects dealt with competitive inclusion experiments and the nature of the inclusion mixtures respectively, for the same guests as in the second project above. Alkyl bromides were the most preferred guests, followed by alkyl chlorides and alkyl iodides. We reasoned this on the basis of a balance of forces of cage stretching for larger guests and lack of extensive dispersion forces between guest and host for smaller guests. The alkyl bromides bring about a balance of the forces to qualify as the most preferred guest. In the fifth project, we characterize TATM inclusion compounds with C 1(CH 2)„C1 guests (n = 1 to 10), using techniques such as PXRD, l3C CP/MAS NMR and DSC. Following this, we report a TATM inclusion compound with 1,3-dichloropropane guest that crystallizes in five 2:1 H:G forms. This is an unprecedented discovery, and suggests that minor changes in synthetic procedures can have a profound effect on the structure of the resulting complex. In the next chapter, we report a study similar to that described above for Cl(CH 2)nCl guests, but now we study Br(CH 2)nCH 3 (n = 1 to 15) guests, and compare results among the two groups. Next, we report the structure of the hydrophobic TATM host with water as a guest. Finally, we describe the synthesis and characterization of a novel crystalline guest-free form of TATM. ill Reproduced with permission of the copyright owner. Further reproduction prohibited without permission. ACKNOWLEDGEMENTS This work would not have been possible were it not for the kind assistance of several people for whose efforts I wish to acknowledge here: First and foremost, I would like to show appreciation to my graduate supervisor, Professor John Ripmeester, who helped to guide me through to the completion of this project. He was always willing to listen, sometimes providing interesting ideas, and keeping me on a straight and narrow course. Thank you Dr Ripmeester. Secondly, 1 wish to thank Dr. Gary Enright, who obtained all of the crystal structures in this thesis. Without his kind help, my thesis would have been very incomplete and one­ dimensional. He never once complained when I had "yet another" batch of crystals to examine. Thank you Dr Enright. I would also like to thank Konstantin Udachin, for preparing most all of the single crystal packing diagrams contained in this thesis, taking time out of his busy schedule to help me. Thank you Kostiya. I would like to thank Don Leek, who measured all of the 'H and 13C liquid NMR spectra contained in my thesis (and a jot more not in the thesis). Thank you for your kind assistance Don. Thanks to our glass-blowers, Mike Vandenhoff and Darcy Doering, for giving your time to help me. Also thanks to the computer support group Randy Holmes, Lyne Seguin and Claude Cantin. Thank you to our librarian Bonnie Bullock for your help. I wish to thank the Natural Sciences and Engineering Research Council (NSERC) committee for me awarding a post-graduate scholarship that 1 held for two years. I am also grateful to the Ontario Graduate Scholarship (OGS) committee for awarding me a post­ graduate scholarship that I held for one year. I also wish to acknowledge Carleton University for awarding me an entrance scholarship and the H. J. Bernstein memorial award. Finally, I wish to thank my thesis committee, for taking time out their busy schedules to read my thesis and ask me interesting questions. I hope we all can learn something new. iv Reproduced with permission of the copyright owner. Further reproduction prohibited without permission. MOTIVATION My PhD project involves physicochemical characterization of TATM inclusion compounds, at least in part, with alkyl halide guests and alkyl halide guest families. One type of study (Chapters VII and XII) involves characterization of a single guest (1,2- dichloroethane and 1,3-dichloropropane, respectively), while other projects (Chapters VIII/IX/X, XI and XIII) encompass guest families (alkyl and aryl halides, a,co- dichloroalkanes and 1-bromoalkanes, respectively). We wish to examine how the physical properties of the TATM inclusion compound change as the guest's structure is systematically altered (eg. changing halogen substituents or alkyl chain lengthening). The other two projects involve preparation and characterization of an expressly hydrophobic TATM host with water as a guest, and the synthesis and description of a novel polycrystalline guest-free TATM structure. This fact that TATM will incorporate practically anything in which it can be dissolved itself justifies a detailed study of this host system, namely the driving forces and intermolecular interactions in TATM inclusion compounds that lead to its remarkable inclusion versatility. The results presented in this thesis are primarily focused on using several physical characterization techniques to describe properties of these TATM inclusion compounds. For example, single crystal X-ray diffraction allows one to visualize the intermolecular interactions that lead to the remarkable versatility of the TATM host. However, this technique measures only a single selected crystal, so we also used powder X-ray diffraction and l3C CP/MAS NMR to determine whether the selected crystal was representative of the bulk sample. This is important, since a number of TATM inclusions are known to crystallize in more than one form. Deuterium solid-state NMR allows a description of the dynamics of an enclathrated guest molecule. Thermal techniques (TGA and DSC) allow a measurement of relative thermal stabilities for a series of related guests. Competitive inclusion experiments may provide complementary information, in that more thermally stable samples may be preferentially incorporated by TATM from a guest mixture. In summary, by employing a comprehensive range of techniques, we hope to characterize our TATM compounds in as complete a manner as possible. v Reproduced with permission of the copyright owner. Further reproduction prohibited without permission. PUBLICATIONS (1) Sidhu, P.S., Enright, G.D., Udachin, K.A. and Ripmeester, J.A. ’‘The first example of a crystalline guest-free form of the tris(5-acetyl-3-thienyl)methane host material" Chemical Communications 2092-2094 (2005). (2) Sidhu, P.S., Enright, G.D., Udachin, K.A. and Ripmeester, J.A. “Polymorphism and structure in a pentamorphic guest-host material: The tris(5-acetyl-3- thienyi)methane inclusion compound with 1,3 -dichloropropane" Crystal Growth and Design 4 (6), 1249- 1257 (2004). (3) Sidhu, P.S., Udachin, K.A.
Load more

Recommended publications
  • United States Patent (19) (11) 3,799,996 Bloch (45) Mar
    United States Patent (19) (11) 3,799,996 Bloch (45) Mar. 26, 1974 54). PREPARATION OF 3,016,405 1/1962 Lovejoy........................... 260/653.3 TETRAFLUOROETHYLENE 75 Inventor: Herman S. Bloch, Skokie, Ill. Primary Examiner-Daniel D. Horwitz 73) Assignee: Universal Oil Products Company, Attorney, Agent, or Firm-James R. Hoatson, Jr.; Ray Des Plaines, Ill. mond H. Nelson 22 Filed: Aug. 4, 1971 (21 Appl. No.: 169,046 57 ABSTRACT Tetrahalo-substituted ethylenes, and particularly tetra 52) U.S. Cl............................... 260/653.3, 252/443 fluoroethylene, may be prepared by reacting a mixed (51 Int. Cl........................ C07c 17/26, CO7c 2 1/18 tetrahalomethane with a metal carbonyl in the pres 58) Field of Search.................................. 260/653.3 ence of an inert solvent. The tetrafluoroethylene which is prepared is useful as a starting material for (56 References Cited the preparation of polymeric substances. UNITED STATES PATENTS 2,925,446 2/1960 Drysdale.......................... 260/653.3 9 Claims, No Drawings 3,799,996 1 2 PREPARATION OF TETRAFLUOROETHYLENE fluoromethane, said compounds having been formed This invention relates to a process for preparing tet by any means known in the art. In the present process rahaloethylenes. More specifically, the invention is these compounds are treated with a metal carbonyl concerned with a process for preparing tetrafluor compound under reaction conditions hereinafter set oethylene by utilizing a mixed tetrahalomethane as the forth in greater detail. The metal carbonyls which are starting material, said methane containing two fluoro used to treat the aforementioned dihalodifluorome atoms as well as two halo substituents of a dissimilar na thane preferably comprise carbonyls of metals of ture.
    [Show full text]
  • Thesis in the Shikimate Area
    University of Bath PHD Synthesis in the shikimate area Diston, Simon Award date: 1995 Awarding institution: University of Bath Link to publication Alternative formats If you require this document in an alternative format, please contact: [email protected] General rights Copyright and moral rights for the publications made accessible in the public portal are retained by the authors and/or other copyright owners and it is a condition of accessing publications that users recognise and abide by the legal requirements associated with these rights. • Users may download and print one copy of any publication from the public portal for the purpose of private study or research. • You may not further distribute the material or use it for any profit-making activity or commercial gain • You may freely distribute the URL identifying the publication in the public portal ? Take down policy If you believe that this document breaches copyright please contact us providing details, and we will remove access to the work immediately and investigate your claim. Download date: 07. Oct. 2021 SYNTHESIS IN THE SHHOMATE AREA Submitted by Simon Diston for the degree of Ph.D. of the University of Bath 1995 COPYRIGHT Attention is drawn to the fact that copyright of this thesis rests with its author. This copy of the thesis has been supplied on condition that anyone who consults it is understood to recognise that its copyright rests with its author and that no quotation from the thesis and no information derived from it may be published without the prior written consent of the author. This thesis may not be consulted, photocopied or lent to other libraries without the permission of the author and Zeneca for three years from the date of acceptance of the thesis.
    [Show full text]
  • The Haloform Reaction. Reynold C
    Subscriber access provided by Service des bibliothèques | Université de Sherbrooke The Haloform Reaction. Reynold C. Fuson, and Benton A. Bull Chem. Rev., 1934, 15 (3), 275-309 • DOI: 10.1021/cr60052a001 Downloaded from http://pubs.acs.org on December 30, 2008 More About This Article The permalink http://dx.doi.org/10.1021/cr60052a001 provides access to: • Links to articles and content related to this article • Copyright permission to reproduce figures and/or text from this article Chemical Reviews is published by the American Chemical Society. 1155 Sixteenth Street N.W., Washington, DC 20036 THE HALOFORM REACTION REYNOLD C. FUSON AND BEE-TON A. BULL Department of Chemistry, University of Illinois, Urbana, Illinois Received September $8, 1934 CONTENTS I. Introduction.. .................... ......... ...............275 11. The early history of the haloform ............................. 276 111. The haloform reaction in qualitative organic analysis 277 IV. Structural determination by means of the haloform degradation.. ...... 281 V. Quantitative methods based on the haloform reaction ................... 286 VI. The use of the haloform reaction in synthesis.. ..... A. The haloforms., ............................. B. Saturated aliphatic acids.. ..................................... 288 C. Unsaturated acids D. Aromatic acids.. .. VII. The mechanism of the haloform reaction.. ............................. 291 A. The halogenation phase of the haloform reaction.. B. The cleavage phase of the haloform reaction .................... 295 VIII. Reactions
    [Show full text]
  • United States Patent 0 ""Lc€ Patented Nov
    3,479,286 United States Patent 0 ""lC€ Patented Nov. 18, 1969 1 2 with the Underwriters Laboratories (UL) classi?cation 3,479,286 which indicates a decrease in toxicity from class 1 to class FLAME-EXTINGUISHING COMPOSITIONS 6. In class 1, compounds such as sulfur dioxide are in Gian Paolo Gambaretto, Padova, Paolo Rinaldo, Venice, and Mario Palato, Padova, Italy, assignors to Monte cluded Whereas tri?uorobromomethane (CBrF3) is con catini Edison S.p.A., Milan, Italy, a corporation of sidered to be in class 6. Compounds such as carbon tetra Milan, Italy chloride are the most toxic of the haloalkanes (class 3). No Drawing. Filed Sept. 19, 1966, Ser. No. 580,212 TABLE I.—TOXICITY OF HALOALKANES Claims priority, application Italy, Sept. 22, 1965, 21,090/65 Compound: U.L. Class Int. Cl. A62d 1/00 10 C014 ____ __ 3 US. ‘Cl. 252-8 2 ‘Claims CCl3F _______________________________ __ 5a CCI2F2 __ __ 6 CCIF3 ___ _____ 6 ABSTRACT OF THE DISCLOSURE CF, 6 A ?ame-extinguishing composition containing a com 15 CHCI, _____ 3 pletely halogenated alkane, having at least two ?uorine CHCl2F ___ 5 atoms and at least one bromine atom per molecule and a CHClF2 ______________________________ __ 5a ?uorohydrocarbon having at least one hydrogen atom per CHF, ___-.. 6 molecule. The composition can include, optionally, a pro (CHCIB) ____ 3 pellant such as sulfur-hexa?uoride and carbon dioxide. (CC13F)' 5a The molar ratio of the ?uoro-hydrocarbon to the com CH2Cl2 _ ___ 4-5 pletely halogenated alkane ranges between substantially (CHCI2F) ____________________________ __ 5 0.2 and 5.
    [Show full text]
  • A Biosynthetically Inspired Synthetic Route to Substituted Furans, and Its Application to the Total Synthesis of the Furan Fatty
    A Biosynthetically Inspired Synthetic Route to Substituted Furans, and its Application to the Total Synthesis of the Furan Fatty Acid F5 A thesis submitted in partial fulfilment of the requirements of the degree Doctor of Philosophy Robert Jack Lee Supervisors: Dr Gareth J. Pritchard and Dr Marc C. Kimber 1 Thesis Abstract Dietary fish oil supplementation has long been shown to have significant health benefits, largely stemming from the anti-inflammatory activity of the ω-3 and ω-6 polyunsaturated fatty acids (PUFAs) present in fish oils. The anti-inflammatory properties of these fatty acids has been linked to beneficial health effects, such as protecting the heart, in individuals consuming diets rich in fish, or supplemented with fish oils.1 These effects are highly notable in the Māori people native to coastal regions of New Zealand; the significantly lower rates of heart problems compared to the inland populous has been attributed to the consumption of the green lipped mussel Perna Canaliculus. Commercially available health supplements based on the New Zealand green lipped mussel include a freeze-dried powder and a lipid extract (Lyprinol®), the latter of which has shown anti- inflammatory properties comparable to classical non-steroidal anti-inflammatory drugs (NSAIDs) such as Naproxen.2 GCMS analysis of Lyprinol by Murphy et al. showed the presence of a class of ω-4 and ω-6 PUFAs bearing a highly electron rich tri- or tetra-alkyl furan ring, which were designated furan fatty acids (F-acids).3 Due to their instability, isolation of F- acids from natural sources cannot be carried out and a general synthetic route toward this class of natural products was required.
    [Show full text]
  • United States Patent Office Patented Jan
    3,422,155 United States Patent Office Patented Jan. 14, 1969 2 3,422,155 bromoform; and alkyl haloforms such as alkyl chloro BICYCLO3.3.0 OCTANONES forms and alkyl bromoforms, the alkyl groups being typi Rostylaw Dowbenko, Gibsonia, Pa., assignor to PPG cally methyl, ethyl, and propyl, although other alkyl halo Industries, Inc., Pittsburgh, Pa., a corporation of forms, for example, those having alkyl groups of up to Pennsylvania about 12 carbon atoms or more, may also be employed. No Drawing. Original application Apr. 16, 1964, Ser. No. 5 Also included within the scope of the invention are mixed 360,434, now Patent No. 3,305,346, dated Feb. 21, polyhaloalkanes in which the halogens are different, for 1967. Divided and this application Mar. 11, 1966, Ser. example, such compounds as chlorotrifluoromethane, di No. 554,231 chlorodifluoromethane and trichlorobromomethane. U.S. C. 260-648 18 Claims The reaction of tetrahalomethanes with 1,5-cycloocta Int, C. C07c 23/32; C05g 3/08 10 diene produces compounds having the formula: ABSTRACT OF THE DISCLOSURE The following compounds have been prepared: 5 A. where X is halogen. As can be seen, one of the halogens 20 from the tetrahalomethane is attached to the bicyclo 3.3.0]octane nucleus in the 6-position and a trihalo B methyl radical is attached in the 2-position. The product of the reaction utilizing a trihalomethane where A is -CX or CX2R, X being halogen and R has the following formula: being an alkyl radical; B being either halogen or alkyl. 25 These compounds are formed by transannular addition of polyhaloalkanes to 1,5-cyclooctadiene.
    [Show full text]
  • Pierangelo Metrangolo Giuseppe Resnati Editors Impact on Materials
    Topics in Current Chemistry 358 Pierangelo Metrangolo Giuseppe Resnati Editors Halogen Bonding I Impact on Materials Chemistry and Life Sciences 358 Topics in Current Chemistry Editorial Board: H. Bayley, Oxford, UK K.N. Houk, Los Angeles, CA, USA G. Hughes, CA, USA C.A. Hunter, Sheffield, UK K. Ishihara, Chikusa, Japan M.J. Krische, Austin, TX, USA J.-M. Lehn, Strasbourg Cedex, France R. Luque, Cordoba, Spain M. Olivucci, Siena, Italy J.S. Siegel, Nankai District, China J. Thiem, Hamburg, Germany M. Venturi, Bologna, Italy C.-H. Wong, Taipei, Taiwan H.N.C. Wong, Shatin, Hong Kong [email protected] Aims and Scope The series Topics in Current Chemistry presents critical reviews of the present and future trends in modern chemical research. The scope of coverage includes all areas of chemical science including the interfaces with related disciplines such as biology, medicine and materials science. The goal of each thematic volume is to give the non-specialist reader, whether at the university or in industry, a comprehensive overview of an area where new insights are emerging that are of interest to larger scientific audience. Thus each review within the volume critically surveys one aspect of that topic and places it within the context of the volume as a whole. The most significant developments of the last 5 to 10 years should be presented. A description of the laboratory procedures involved is often useful to the reader. The coverage should not be exhaustive in data, but should rather be conceptual, concentrating on the methodological thinking that will allow the non-specialist reader to understand the information presented.
    [Show full text]
  • Clinical Applications of 3D Dosimetry
    Clinical and Research Applications of 3D Dosimetry by Titania Juang Graduate Program in Medical Physics Duke University Date:_______________________ Approved: ___________________________ Mark Oldham, Supervisor ___________________________ Timothy Turkington, Chair ___________________________ Shiva Das ___________________________ Justus Adamson ___________________________ Jing Cai Dissertation submitted in partial fulfillment of the requirements for the degree of Doctor of Philosophy in the Graduate Program in Medical Physics in the Graduate School of Duke University 2015 ABSTRACT Clinical and Research Applications of 3D Dosimetry by Titania Juang Graduate Program in Medical Physics Duke University Date:_______________________ Approved: ___________________________ Mark Oldham, Supervisor ___________________________ Timothy Turkington, Chair ___________________________ Shiva Das ___________________________ Justus Adamson ___________________________ Jing Cai An abstract of a dissertation submitted in partial fulfillment of the requirements for the degree of Doctor of Philosophy in the Graduate Program in Medical Physics in the Graduate School of Duke University 2015 Copyright by Titania Juang 2015 ABSTRACT Quality assurance (QA) is a critical component of radiation oncology medical physics for both effective treatment and patient safety, particularly as innovations in technology allow movement toward advanced treatment techniques that require increasingly higher accuracy in delivery. Comprehensive 3D dosimetry with PRESAGE® 3D dosimeters
    [Show full text]
  • United States Patent Office Patented Mar
    2,826,602 United States Patent Office Patented Mar. 11, 1958 2 fourteen carbon atoms, alkoxyalkyl groups of three to seven carbon atoms, aralkyl groups of seven to fourteen 2,826,602 carbon atoms, cycloalkyl and alkylcycloalkyl groups of METHYLTRHALOETYLHALOADPATES three to fourteen carbon atoms. 5 There may be employed as specific preferred embodi Newman M. Bortnick, Oreland, and Marian F. Fegicy, ments of R the groups methyl, ethyl, isopropyl, butyl, Mont Clare, Pa., assignors to Rohm & Haas Company, octyl, decyl, dodecyl, tetradecyl, methoxyethyl, methoxy Philadelphia, Pa., a corporation of Delaware propyl, methoxyisopropyl, ethoxyethyl, ethoxyisopropyl, propoxyethyl, propoxypropyl, butoxyethyl, butoxypropyl, No Drawing. Application July 11, 1955 butoxyisopropyl, benzyl, phenylethyl, naphthylmethyl, Serial No. 521,402 phenylbutyl, phenylhexyl, phenylheptyl, phenyloctyl, cy 7 Claims. (C. 260-485) clopropyl, cyclopentyl, cyclohexyl, butylcyclopentyl, octylcyclohexyl, cyclopentylheptyl, and cyclohexyloctyl. There may also be used as R, groups such as bornyl, This invention relates to methyltrihaloethylhaloadipates nordicyclopenienyl, norcamphanyl, norcamphanylmethyl, as new compositions of matter and to a method for their and the like. preparation. The a-methylene-o'-methyl adipate reactants are known The compounds of the present invention may be repre or may be prepared by known methods. For instance, Sented by the formula the dimethyl ester may be made by heating methyl meth 20 acrylate for 12 hours at about 225 C. under conditions CXCH-YCHCH.gich, of autogenous pressure and in the presence of about 1% COOR O OR hydroquinone as an inhibitor. Other adipate esters may be obtained by reacting c-methylene-a'-methyladipic in which X is a halogen atom having an atomic weight acid or the corresponding acid chloride with the desired of about 19 to 127, Y is a halogen atom having an atom 2 5 alcohol under esterifying conditions.
    [Show full text]
  • SRINIVASAN COLLEGE of ARTS and SCIENCE PERAMBALUR - 621 212 (Affiliated to Bharathidasan University, Tiruchirappalli)
    B. Sc. Chemistry General Chemistry II Semester II SRINIVASAN COLLEGE OF ARTS AND SCIENCE PERAMBALUR - 621 212 (Affiliated to Bharathidasan University, Tiruchirappalli) COURSE MATERIAL DEPARTMENT OF CHEMISTRY B. Sc. Chemistry General Chemistry - II SYLLABUS S. NO. UNITS PAGE NO. 1. 4 CHEMICAL BONDING CHEMISTRY OF s-BLOCK & ZERO GROUP ELEMENTS AND 2. 15 METALLURGY CHEMISTRY OF BENZENE AND BENZENOID 3. 24 COMPOUNDS 4. 29 ALKYL AND ARYL HALOGENS ATOMIC STRUCTURE AND BASIC QUANTUM 5. 47 MECHANICS Srinivasan College of Arts and Science, Perambalur – 621 212 1 B. Sc. Chemistry General Chemistry II Semester II SYLLABUS UNIT I CHEMICAL BONDING 1.1 Ionic bond – formation, variable electrovalency – Lattice energy, Born – Haber Cycle. Covalent bond - formation, variable covalency, maximum covalency, covalent character in ionic bond – Fajans Rule. Polarisation – partial ionic character of a covalent bond. 1.2 VB theory, MO theory – Basic principles of bonding and antibonding orbitals, applications of MOT to H2 He2, N2 & O2 – molecular orbital sequence, comparison of VB & MO Theories. 1.3 Hybridisation – Formation of BeCl2 & BCl3. VSEPR theory of simple inorganic molecules – BeCl2, SiCl4, PCl5, SF6, IF7, XeF6, BF3 & H2O. 1.4 Hydrogen bonding – Intermolecular & Intramolecular H2 – bonding and consequences. UNIT II CHEMISTRY OF s-BLOCK & ZERO GROUP ELEMENTS AND METALLURGY 2.1 General characteristics of s-block elements – comparative study of elements – alkali metals and their hydroxides, oxides and halides, alkaline earth metals and their oxides, carbonates and sulphates. 2.2 Diagonal relationship of Li & Mg, Be & Al, chemistry of NaOH, KI & Mg(NH4)PO4. 2.3 Metallurgy : Occurrence of metals – concentration of ores – froth floatation, magnetic separation, calcination, roasting, smelting, flux, aluminothermic process, purification of metals – electrolysis, zone refining, van Arkel de-Boer process.
    [Show full text]
  • In Presenting the Dissertation As a Partial Fulfillment of The
    "In presenting the dissertation as a partial fulfillment of the requirements for an advanced degree from the Georgia Institute of Technology, I agree that the Library of the Institution shall make it available for inspection and circulation in accordance with its regulations governing materials of this type. I agree that permission to copy from, or to publish from, this dissertation may be granted•by the professor under whose direction it was written, or, in his absence, by the dean of the Graduate Division when such copying or publication is solely for scholarly purposes and does not involve potential financial gain. It is understood that any copying from, or publication of, this dissertation which involves potential financial gain will not be allowed without written permission. SOME STUDIES ON THE HALIDES OF METHANE PART I 'WE EFFECT OF HALOGEN ATOMS UPON THE SN2 REACTIVITY OF OTHER HALOGEN ATOMS ATTACHED TO 1HE SAME CARBON ATOM PART II AN EMPIRICAL METHOD FOR PREDICTION OF THE BOILING POINTS OF THE HALOMETHANES PART III A CORRELATION OF REACTIVITIES IN THE BASIC SOLVOLYSIS OF HALOFORMS A THESIS Presented to the Faculty of the Graduate Division By Stanton Jay Ehrenson In Partial Fulfillment of the Requirements for the Degree Doctor of Philosophy in the School of Chemistry Georgia Institute of Technology' June 1957 SOME STUDTES ON HALIDES OF METHANE PART I TKE 0TECT OF HALOGEN ATOMS UPON THE 2 REACTIVITY OF OTHER HALOGEN ATOMS ATT BED TO TEE SAME CARBON ATOM PART II AN EMPIRICAL METHOD FOR PREDICTION OF TAE BOILING POINTS OF TEE HALOMETHANES PART III A'CORRELATION OF REACTIVITIES IN THE BASIC SOLVOLYSIS OF HALOFORMS Approved: L 77.
    [Show full text]
  • Kinetics of the Reaction Between Triphenylphosphine and Some Haloalkanes
    Indian Journal of Chemistry Vol. 30A, November 1991, pp.929-935 Kinetics of the reaction between triphenylphosphine and some haloalkanes DV S Jain* & R Chadha Department of Chemistry, Panjab University, Chandigarh 160014 Received 27 February 1991; accepted 8 July 1991 Kinetics of reactions RX + (C6Hs)3P- (C6Hs)3PR+X-(R = CCI3,CBr3,CH2Br, C4H9 and X = Br, Cl, Ii have been studied at different temperatures and in different dielectric media. The values of second or- der rate constants of the reactions with tetrahalomethanes are much higher than those with partially hal- ogenated alkanes. This suggests that the reaction may be of charge transfer type with tetrahalomethanes while with other haloalkanes it is simple nucleophilic substitution reaction of SN2 type. A mixture of triphenylphosphine (TPP) and tetra- used as such. I-BB and l-lB were prepared in the halo methane (CX4) (especially X = CI or Br) has laboratory. Carbon tetrachloride was dried over been widely used as a versatile reagent for halogena- phosphorus pentoxide and the middle fraction, b.p. tion, dehydration, for creating P-N linkage and for 349 K was used. Acetonitrile was purified as de- replacing a hydroxyl group with halogen':" under scribed earlier". Tribromomethyltriphenylphos- mild conditions. lnspite of such wide applications of phonium bromide was prepared as described earli- TPP/CX4 systems, there have been few detailed kin- er". Trichloromethyltriphenylphosphonium chlo- etic and mechanistic studies of the reactions between ride and trichloromethyltriphenylphosphonium TPP and CX4. We report herein the results of kinetic bromide were prepared by adding TCM (3.06 g) studies of the reactions of TPP with (CX4) such as and BTCM (1.98 ~ to TPP solution in acetonitrile CCI4, CBr4 and CBrCl3 in different solvents at dif- (5 mI) respectively.
    [Show full text]