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The Scope of Inorganic Chemistry

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The Scope of Inorganic Chemistry The Scope of Inorganic Chemistry Medicine Biochemistry/Biology Organic Chemistry •MRI • metalloproteins • organometallics •X-ray contrast imaging • metalloenzymes • metal compounds in •drugs (arthritis, cancer,… • O2 binding synthesis/catalysis • catalysis • ion transport INORGANIC CHEMISTRY • new compounds • geometrical and electronic structures • reactivity Materials Science Organometallic Geology/Geochemistry • electrical and magnetic Chemistry • synthesis and structure properties of solids • new compounds of minerals • solid state structures • structures • stellar evolution • semiconductors • catalysis • astrochemistry • superconductors (high Tc) If some universal catastrophe were to engulf the world, and humankind Could retain one scientific concept in order to rebuild civilization, what would that one concept be? Response for physicists (Richard Feynman in “Six Easy Pieces”): The modern idea of atoms. Response for chemists: The periodic table The periodic table encapsulates the concept of elements, organizes physical and chemical trends of substances, and compares the structure of the different atoms— All in a very small space. Inorganic Chemists think they own the Periodic Table. So, How did it all start? 4 8 Be with t1/2 of ca. 10-18 sec 6 2 4 3Li + 1H 2 2He + Energy Stable vs. Unstable or Fissionable Nuclei Project no. 1. Nuclear Reactions; Web Elements WebElementsTM Periodic Table Group 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 Period 1 2 1 H He 3 4 5 6 7 8 9 10 2 Li Be B C N O F Ne 11 12 13 14 15 16 17 18 3 Na Mg Al Si P S Cl Ar 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 4 K Ca Sc Ti V Cr Mn Fe Co Ni Cu Zn Ga Ge As Se Br Kr 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 5 Rb Sr Y Zr Nb Mo Tc Ru Rh Pd Ag Cd In Sn Sb Te I Xe 55 56 71 72 73 74 75 76 77 78 79 80 81 82 83 84 85 86 6 * Cs Ba Lu Hf Ta W Re Os Ir Pt Au Hg Tl Pb Bi Po At Rn 112 114 115 116 118 87 88 * 103 104 105 106 107 108 109 110 111 113 117 7 Uu Uu Uu Uu Uu Fr Ra Lr Rf Db Sg Bh Hs Mt Ds Rg Uut Uus * b q p h o 57 58 59 60 61 62 63 64 65 66 67 68 69 70 *Lanthanoids * La Ce Pr Nd Pm Sm Eu Gd Tb Dy Ho Er Tm Yb * 89 90 91 92 93 94 95 96 97 98 99 100 101 102 **Actinoids * Ac Th Pa U Np Pu Am Cm Bk Cf Es Fm Md No http://www.webelements.com Mass Spectra computer: http://www.sisweb.com/mstools/isotope.htm Dimitri Mendeleev 1834-1907 A ZE Z = No. protons in nucleus, Atomic number A = Mass number; no. of protons + neutrons in nucleus Copyright © 2014 Pearson Education, Inc. Color Metal Flame Colors Carmine: Lithium compounds. Masked by barium or sodium. Red Scarlet or Crimson: Strontium compounds. Masked by barium. Yellow-Red: Calcium compounds. Masked by barium. Sodium compounds, even in trace amounts. A yellow flame is not Yellow indicative of sodium unless it persists and is not intensified by addition of 1% NaCl to the dry compound. White White-Green: Zinc Emerald: Copper compounds, other than halides. Thallium. Blue-Green: Phosphates, when moistened with H2SO4 or B2O3. Green Faint Green: Antimony and NH4 compounds. Yellow-Green: Barium, molybdenum. Azure: Lead, selenium, bismuth, CuCl2 and other copper compounds moistened with hydrochloric acid. Blue Light Blue: Arsenic and come of its compounds. Greenish Blue: CuBr2, antimony Potassium compounds other than borates, phosphates, and silicates. Masked by sodium or lithium. Violet Purple-Red: Potassium, rubudium, and/or cesium in the presence of sodium when viewed through a blue glass. Atomic Emission (Spectroscopy) • An emission spectrum requires first the addition of energy to a material. • The addition of energy promotes electrons of that material from the ground state to the excited state. • As the electrons “fall” from the excited state to the ground state, they emit the energy they absorbed in the form of electromagnetic radiation (heat, light, etc.) Comments • Atomic emission is used in street lamps, fluorescent lights, and neon signs. • Two common street lamps using this are the mercury lamp and the sodium lamp. • “Neon” signs frequently implement the emission spectra of other gases such as argon and krypton. • Very sophisticated instrumental techniques such as “flame photometry” and “atomic absorption” are based on the principles of atomic emission. Continuous and Line Spectra Dark Side of the Moon Pink Floyd http://webmineral.com/help/FlameTest.shtml Electromagnetic Radiation Spectrum In the news: January 20, 2016 Lecture 2 362 January 22, 2016 Paradigm Shift: Development of Current Atomic Theory Emission Spectra Sun Hydrogen Helium Mercury Uranium 700 nm 600 nm 500 nm 400 nm A Bit of History A ZE Z = No. protons in nucleus, Atomic number A = Mass number; no. of protons + neutrons in nucleus Copyright © 2014 Pearson Education, Inc. Marie Curie—1867-1934 So how to connect the physical properties of elements to the Periodic Table? Physicists! The current model of the atom belongs to Physicists! DeBroglie Schrodinger Planck Pauli Einstein Heisenberg Bohr Niels Bohr and wife Margrethe around 1930 Taken from John L. Heilbron’s “History: The Path to the quantum Atom”, Nature 498, 27-30, (06 June 2013) Taken from John L. Heilbron’s “History: The Path to the quantum Atom”, Nature 498, 27-30, (06 June 2013) To develop his model, Bohr followed an analogy to the radiation theory of Max Planck (right). “. Bohr had developed a doctrine of multiple partial truths, each of which contained some bit of reality, and all of which together might exhaust it. “There exist so many different truths I can almost call it my religion that I think that everything that is of value is true.” Lecture 2 Niels Bohr and Emission Spectra Sun Albert Einstein, 1925 Hydrogen Helium Mercury Uranium Taken from John L. Heilbron’s “History: The Path to the 700nm 600nm 500nm 400nm quantum Atom”, Nature 498, 27-30, (06 June 2013) The Bohr Atom: electrons in concentric rings The Balmer formula expresses the frequencies of some lines in the spectrum of hydrogen in simple algebra: 2 2 νn = R(1/2 – 1/n ) where νn is the nth Balmer line and R is the universal Rydberg constant for frequency, named in honour of the Swedish spectroscopist Johannes Rydberg, who generalized Balmer’s formula to apply to elements beyond hydrogen. Each level can accommodate 2 Taken from John L. Heilbron’s “History: The Path to the 2 n electron: quantum Atom”, Nature 498, 27-30, (06 June 2013) Periodic Table Rows Quantum Energy Number n The Hydrogen 0 ∞ 5 -1/16 RH 4 Atom Spectrum Paschen Series (IR) -1/9 RH 3 and Energy Levels Balmer Series (visible transitions shown) -1/4 RH 2 2 2 νn = R(1/nfinal – 1/ninitial ) Lyman + Series (UV) Niels Bohr’s view of the atom -RH 1 Hydrogen 656.3 486.1 434 410.1 700 600 500 400 Quantum Energy Number n 0 ∞ For Hydrogen: 5 -1/16 RH 4 E = -RH Paschen Series (IR) 2 -1/9 RH 3 n Balmer Series Rydberg constant for hydrogen,RH (visible transitions shown) 4 -18 RH = mee = 2.179x10 J -1/4 R 2 2 H 2 8 εo h = 13.6 eV General equation for Rydberg constant for any element Lyman Series R = -m Z2 e4 (UV) 2 2 8 εo h Note: The predicted emission spectra using the Rydberg constant was only -RH 1 successful for simple elements such as H and failed for heavier atoms due to the limitations of the Bohr view of the atom. This led to the foundations of quantum mechanics. Inorganic Chemistry Chapter 1: Figure 1.5 Properties of waves: Addition for reinforcement or cancellation © 2009 W.H. Freeman Properties of waves: Squared = amplitude Boundaries => Restrictions on values a “node” Copyright © 2014 Pearson Education, Inc. Inorganic Chemistry Chapter 1: Figure 1.4 Time-independent Schrödinger equation (general—one dimension) E ψ = H ψ a “node” © 2009 W.H. Freeman Need for Spherical Coordinates and Volume Elements Need both radial and angular functions Copyright © 2014 Pearson Education, Inc. Summarizing: Solutions Required Quantum Numbers Quantum Numbers n is the principal quantum number, indicates the size of the orbital, has all positive integer values of 1 to ∞(infinity) l (angular momentum) orbital 0 s l is the angular momentum quantum number, 1 p represents the shape of the orbital, has integer values of (n – 1) to 0 2 d 3 f ml is the magnetic quantum number, represents the spatial direction of the orbital, can have integer values of -l to 0 to l Other terms: electron configuration, noble gas configuration, valence shell ms is the spin quantum number, has little physical meaning, can have values of either +1/2 or -1/2 Pauli Exclusion principle: no two electrons can have all four of the same quantum numbers in the same atom (Every electron has a unique set.) Hund’s Rule: when electrons are placed in a set of degenerate orbitals, the ground state has as many electrons as possible in different orbitals, and with parallel spin. Aufbau (Building Up) Principle: the ground state electron configuration of an atom can be found by putting electrons in orbitals, starting with the lowest energy and moving progressively to higher energy. While n is the principal energy level, the l value also has an effect Radial Wave Functions and Nodes # Radial Nodes = n - l - 1 Copyright © 2014 Pearson Education, Inc.
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