C4010 Inorganic Chemistry III

Faculty of Science
Spring 2019
Extent and Intensity
2/0/0. 2 credit(s) (fasci plus compl plus > 4). Recommended Type of Completion: zk (examination). Other types of completion: k (colloquium).
Teacher(s)
prof. RNDr. Jiří Pinkas, Ph.D. (lecturer)
prof. RNDr. Jiří Příhoda, CSc. (lecturer)
Guaranteed by
prof. RNDr. Jiří Pinkas, Ph.D.
Department of Chemistry – Chemistry Section – Faculty of Science
Contact Person: prof. RNDr. Jiří Pinkas, Ph.D.
Supplier department: Department of Chemistry – Chemistry Section – Faculty of Science
Timetable
Mon 18. 2. to Fri 17. 5. Mon 11:00–12:50 C12/311
Prerequisites
C2062 Inorganic Chemistry II
General Chemistry Inorganic Chemistry I, II Analytical Chemistry I
Course Enrolment Limitations
The course is also offered to the students of the fields other than those the course is directly associated with.
fields of study / plans the course is directly associated with
there are 10 fields of study the course is directly associated with, display
Course objectives
The course introduces interesting topics of modern inorganic chemistry and is divided in 14 main parts. The goal is to present in more advanced form periodic atomic properties of elements and their influence on structure and properties of different allotropes of main group elements, on bond formation between elements, on bonding in cyclic and cage molecules and cluster compounds, including boron hydrides and Zintl ions. The lecture also covers some important aspects of coordination chemistry of transition and main group elements. Methods for the study of complexing equilibria, mechanisms of the complex formation in the aqueous solutions and the determination of stability constants are presented. Exploitation of the complex formation in practice is briefly surveyed and studies of magnetic properties of complexes and Moessbauer spectroscopy are included.

Learning outcomes
- students gained good overview of basic atomic properties of elements and their effects on structure, bonding situation and chemical behavior of compounds.

- students understands fetures of electronic sructure and bonding situation in coordination compounds, protperties of ligands and their influence on reactivity, magnetic properties, and solution equilibria.

- students acquired understanding of the structure and bonding of both electron precise and electron deficient clusters.

- studets learned Wade's rules and Lipscomb's styx rules as well as their use for a prediction of borane, heteroborane and Zintl ions molecular structures.

Syllabus
  • Part I. Prof. Příhoda

    1. Coordination Chemistry

    Coordination particle, central atom, ligands, their properties, coordination number and coordination polyhedra, stability of complexes, complex formation mechanisms, trans-effect, isomerism of complex compounds, structure and electronic properties of complexes, stability of complexes, chelates, chelate effect.

    2. Chelating Ligands

    Types of complex-forming reagents, chelate reagents, reagents suitable for formation of ion associates, organophosphorus ligands, methods for the study of complex compounds, spectrophotometry, extraction, ion exchange etc.

    3. Ions in Solution

    Solvents, solvation properties of solvents, solvation number, reactions connected with the presence of ions in solution, hydration, analysis of hydration number, hydrolysis, polymerization etc.

    4. Macroseparation Methods for Metals

    Methods based on liquid extraction, ion exchangers, and ion chromatography. Practicing of test problems - complexes, extraction, analysis of stability constants of complexes.

    5. Transuranium Elements

    New discoveries in chemistry of Transuranium Elements, fuel cycles, reprocessing of spent nuclear fuel.

    Part II. Prof. Pinkas

    6. Periodic Table

    IUPAC Periodic Table of the Elements, Aufbau principle, exhange energies, Hunds rule, shielding, penetration, valence electron configurations, atomic properties, ionization energies, electron affinities, atomic, metallic, and ionic radii, oxidation state, electronegativity - Pauling, Allred-Rochow, Mulliken, Allen, Sanderson, electronegativity equalization principle, Mulliken-Jaffe, hybridization influence on electronegativity, electronegativity and chemical properties. Allotropes and polymorphic forms of elements: boron, phosphorus and sulfur.

    7. Chemical Bonding I

    Potential energy curve for a diatomic molecule, Morse potential, zero point energy, bond distances, bond dissociation energy, temperature and isotope effects, Pauling’s rules, bond valence sum, bond ionicity/covalency, van Arkel-Ketelaar triangle, normal and dative bond.

    8. Chemical Bonding II

    Badger’s rule, bond order, multiple bonding in heavy elements, double, triple, quadruple, quintuple, sextuple bonds, multiple bonding in main group elements and transition metals.

    9. Chemical Bonding III

    Inverted bond, sigma- and pi-hole interactions, bond-stretch isomerism, relativistic effects, Au, Hg, Po, auriophilicity, isolobal relation of LAu+ to H+, auration reactions, proper and improper H-bond, dihydrogen bond.

    10. Acid-base Chemistry

    Superacids, solvoacids, carborane acids, superbases – phosphatranes, proton sponges, frustrated Lewis pair, low-coordinate molecules and cations, silicium, non-coordinating anions.

    11. Rings and Polyhedra I

    The structure and the properties of allotropic forms of carbon, diamond, graphite and fullerenes, bonding in fullerene molecules and their chemical reactivity, endohedral fullerenes, nanotubes, chemical properties of graphite, graphite intercalation compounds, aromaticity, Wades rules, electron precise clusters, classification and nomenclature of neutral boranes and hydroborate dianions, carboranes and other heteroboranes, boron halides with closed deltahedral Bn cores, bonding in boranes, the 3-centre-2-electron B-H-B and BBB interactions, Lipscomb's styx rules, Polyhedral Skeletal Electron Pair Theory (PSEPT) and prediction of a borane cluster structure, closo-nido-arachno-hypho, AlN-clusters, Smiths rule, BN, BP, AlP, GaP trimers, phosphazenes.

    12. Rings and Polyhedra II

    Organometallic clusters, metal clusters, Aun(SR)x, magic numbers, nanoparticles, Zintl phases, PSEPT and structures of Zintl ions, methane hydrates, molecular ice, POM, polyoxoanions, Lindqvist, Anderson, Keggin, Wells–Dawson, and Preyssler, clusters Ag490, Mo368, reticular chemistry, MOF, COF, zeolites, sodalite unit.

    13. Magnetochemistry

    Electron spin and angular momenta, magnetic moment, magnetic susceptibility, permeability, diamagnetism and paramagnetism, Curie law, Curie-Weiss law, paramagnetism in metal complexes, orbital angular momentum contribution, spin-orbit coupling, Landé formula, Van Vleck equation, Brillouin function, cooperative magnetism, ferromagnetism, antiferromagnetism, ferrimagnetism, Curie and Neel temperatures, magnetic anisotropy, easy axis, magnetic domains, hysteresis loop, single molecule magnets, anisotropy barrier, superparamagnetism in nanoparticles, blocking temperature.

    14. Moessbauer spectroscopy

    Recoilless nuclear resonance absorption, experimental setup, hyperfine interactions, isomer shift, second-order Doppler shift, electric quadrupole interaction, electric field gradient, quadrupole splitting, magnetic dipole interaction, 119Sn and 57Fe Moessbauer spectroscopy.

Literature
    required literature
  • HOUSECROFT, Catherine E. and A. G. SHARPE. Anorganická chemie. Vyd. 1. Praha: Vysoká škola chemicko-technologická v Praze, 2014, xxx, 1119. ISBN 9788070808726. info
    recommended literature
  • GREENWOOD, N. N. and Alan EARNSHAW. Chemistry of the elements. Second edition. Oxford: Butterworth-Heinemann, 1997, xxii, 1341. ISBN 0750633654. info
  • HOLLEMAN, Arnold F. and Egon WIBERG. Lehrbuch der anorganischen Chemie. Edited by Nils Wiberg - Gerd Fischer. 102., stark umgearb. und ver. Berlin: Walter de Gruyter, 2007, xxxix, 214. ISBN 9783110177701. info
    not specified
  • HOUSECROFT, Catherine E. Cluster molecules of the p-block elements. 1st ed. Oxford: Oxford University Press, 1994, 91 s. ISBN 0198556985. info
  • TAYLOR, Roger. Lecture notes on fullerene chemistry. London: Imperial College Press, 1999, 268 pp. ISBN 1-86094-109-5. info
  • STARÝ, Jiří. Separační metody v radiochemii (Separation metzods in radiochemistry). Praha: Academia, 1975, 400 pp. info
  • BURGESS, John. Metal ions in solution. John Wiley & Sons, 1978, 481 pp. ISBN 0-470-26293-1. info
  • STARÝ, Jiří. Ekstrakcija chelatov. Moskva: Mir, 1966, 392 s. info
Teaching methods
Lectures
Assessment methods
Written examination test.
Language of instruction
English
Follow-Up Courses
Further Comments
Study Materials
The course is taught annually.
Listed among pre-requisites of other courses
The course is also listed under the following terms Spring 2008 - for the purpose of the accreditation, Spring 2011 - only for the accreditation, Spring 2000, Spring 2001, Spring 2002, Spring 2003, Spring 2004, Spring 2005, Spring 2006, Spring 2007, Spring 2008, Spring 2009, Spring 2010, Spring 2011, Spring 2012, spring 2012 - acreditation, Spring 2013, Spring 2017, spring 2018, Spring 2021, Spring 2022, Spring 2023, Spring 2024, Spring 2025.
  • Enrolment Statistics (Spring 2019, recent)
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