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J. Rohonczy: Inorganic Chemistry I Dr. János Rohonczy Lecture Notes Eötvös Loránd University, Budapest Faculty of Sciences Dr. János Rohonczy INORGANIC CHEMISTRY I. Lecture Notes Eötvös Loránd University Faculty of Sciences BUDAPEST 2017. János Rohonczy: Inorganic Chemistry I. Lecture Notes. Copyright © 2017 Dr. János Rohonczy, Eötvös Loránd University, Budapest, Faculty of Sciences All Right are Reserved. No part of this publication may be reproduced, stored in a retrieval system or transmitted in any form or by any means: electronic, electrostatic, magnetic tape, mechanical, photographical, photocopying, recording or otherwise, without permission in writing form the publisher. This book is written utilized the lecture notes of the Inorganic Chemistry lectures of the author at the Department of Inorganic Chemistry of Eötvös Loránd University, Budapest. Revised, and the fullerene and boron cluster topics remarked by Dr. Béla Csákvári professor emeritus. First edition 2017 Edited and cover page made by Dr. János Rohonczy Publisher: Eötvös Loránd University, Faculty of Sciences ISBN: 978-963-284-853-2 DOI: 10.21862/ 3 Table of Contents Introduction 7 1. Hydrogen 8 1.1. Hydrogen compounds 9 2. Halogens: F, Cl, Br, I, At 10 2.1. Hydrogen halides 13 2.2. Interhalogens 14 2.3. Polyhalogen and interhalogen ions, organic derivatives 16 3. (16th column) O, S, Se, Te, Po 17 3.1. Oxygen (O) 17 3.1.1. Oxygen compounds 19 3.1.2. Halogen oxides and oxygen halides 21 3.1.3. Halogen oxoacids and their salts 24 3.1.4. Halogen oxofluorides and fluorinated oxoacids 28 3.2. Sulfur(S) 29 3.2.1. Sulfur containing compounds 31 3.2.2. Sulfur hydrides – Sulfanes 32 3.2.3. Sulfur halides 32 3.2.4. Sulfur oxohalides 33 3.2.5. Sulfur chlorides/bromides/iodides 33 3.2.6. Sulfur oxohalides 34 3.2.7. Sulfur oxides 34 3.2.8. Sulfur oxoacids 35 3.3. Selenium (Se), Tellurium (Te), Polonium (Po) 39 3.3.1. Preparation, produce and application 39 3.3.2. Se, Te, Po Polycations 41 3.3.3. Se, Te, Po Hydrides 41 3.3.4. Se, Te, Po Halides 42 3.3.5. Oxohalides 42 3.3.6. Oxides 42 3.3.7. Hydroxides – Oxoacids 43 4. (15-th column) N, P, As, Sb, Bi 44 4.1. Nitrogen (N) 44 4.1.1. Nitrides, azides and nitrido compounds 45 4.1.2. Nitrogen hydrides 45 4.1.3. Nitrogen halides 47 4.1.4. Nitrogen oxides and oxoacids 48 4.1.5. Nitrogen oxoacids 49 4.1.6. Sulfur nitrides 50 4.2. Phosphorus (P) 51 4.2.1. Phosphorus hydrides 52 4.2.2. Phosphorus halides 52 4.2.3. Phosphorus oxides / sulfides / oxosulfides, oxoacids 53 4.2.4. Phosphorus nitrides and phosphorus organic compounds 55 János Rohonczy: Inorganic Chemistry I. 4.3. Arsenic (As), Antimony (Sb), Bismuth (Bi) 56 4.3.1. Arsenic, antimony, bismuth hydrides 58 4.3.2. Arsenic, antimony, bismuth halides 58 4.3.3. Arsenic, antimony, bismuth oxides and sulfides 59 4.3.4. Elemento organic compounds 60 5. (14-th column) C, Si, Ge, Sn, Pb 61 5.1. Carbon (C) 61 5.1.1. Carbides 64 5.1.2. Hydrocarbons and carbon halides 65 5.1.3. Carbon oxides, carbonic acid 66 5.1.4. Carbon sulfides 67 5.1.5. Carbon nitrides 68 5.2. Silicon 69 5.2.1. Binary compounds 70 5.2.2. Silanes – Hydrosilicons 71 5.2.3. Silicon halides 71 5.2.4. Silicones - silicon organic compounds 72 5.2.5. Silicon oxides, silicic acids, silicates 73 5.2.6. Silicon–sulfur compounds 75 5.2.7. Silicon – nitrogen compounds 76 5.3. Germanium(Ge), Tin(Sn), Lead(Pb) 77 5.3.1. Ge/Sn/Pb hydrides, and hydrido halides 79 5.3.2. Ge/Sn/Pb halides 79 5.3.3. Ge/Sn/Pb oxides, and hydroxides 80 5.3.4. Ge/Sn/Pb oxoacid salts 81 5.3.5. Ge/Sn/Pb chalcogenides 81 5.3.6. Anions with cluster skeleton 81 5.3.7. Ge/Sn/Pb organic compounds 81 6. (13th column) B, Al, Ga, In, Tl 83 6.1. Boron (B) 83 6.1.1. Borides 84 Metal rich borides 84 6.1.2. Boron halides 85 6.1.3. Boron oxide, boric acids, borates 86 6.1.4. Boron nitrogen and other boron containing compounds 87 6.1.5. Other boron compounds 87 6.1.6. Boranes 88 6.2 Aluminium (Al), Gallium(Ga), Indium (In), Tallium(Tl) 91 6.2.1. Al/Ga/In/Tl-hydrides 93 6.2.2. Al/Ga/In/Tl halides 93 6.2.3. Al/Ga/In/Tl oxides, hydroxides and complicated oxides 94 6.2.4. Ternary and more complicated oxides 95 6.2.5. Al/Ga/In/Tl chalcogenides 95 6.2.6. Binary III-V compounds of Al/Ga/In/Tl 95 6.2.7. Al/Ga/In organic compounds 96 6.2.8. Al / Ga / In / Tl and nitrogen bounded compounds 96 6.2.9. Aluminum salts 97 7. Be, Mg, Ca, Sr, Ba, Ra – Alkaline Earth Metals 98 7.1. Elements 98 7.1.1. Preparation and application 99 7.1.2. Chemical properties 100 5 János Rohonczy: Inorganic Chemistry I. 7.2. Compounds 101 7.2.1. Be, Mg and alkaline earth metal hydrides 101 7.2.2. Be, Mg and alkaline earth metal halides 101 7.2.3. Be, Mg and alkaline earth metal oxides and hydroxides 101 7.2.4. Be, Mg and alkaline earth metal carbonates 102 7.2.5. Be, Mg and alkaline earth metal peroxides, ozonides 102 7.2.6. Be, Mg and alkaline earth metal salts 102 7.2.7. Be, Mg and alkaline earth metal complexes 103 7.2.8. Be, Mg and alkaline earth metal organometallic compounds 103 8. (1st column) Li, Na, K, Rb, Cs, Fr – Alkali Metals 104 8.1. Elements 104 8.1.1. Discovery 104 8.1.2. Natural appearance 104 8.1.3. Preparation 104 8.1.4. Application 105 8.2. Alkali metal compounds 106 8.2.1. Alkali metal hydrides 106 8.2.2. Alkali metal halides, pseudo halides, oxohalides 106 8.2.3. Alkali metal oxides 106 8.2.4. Alkali metal hydroxides 107 8.2.5. Other alkali metal salts and complexes 107 8.2.6. Alkali metal organic compounds 109 9. (18th column) He, Ne, Ar, Kr, Xe, Rn – Noble Gases 110 9.1. Elementary properties 110 9.2. Xenon compounds 111 9.2.1. Xe fluorides, reactions 111 9.2.2. Xe organic compounds, Xe-Si/N bonded compounds 113 9.2.4. Chemistry of Krypton and Radon 113 References 114 6 János Rohonczy: Inorganic Chemistry I. Introduction Introduction This book was written for supporting the lectures of B.Sc. students for chemistry and material science in inorganic chemistry at Eötvös Loránd University Faculty of Natural Sciences Department for Inorganic Chemistry. Inorganic chemistry contains the introduction of all elements forming our nature and the wide characterization the compounds thereof. The elements are discussed in groups in order of their position in the periodic table. Following the traditions at Eötvös Loránd University the discussion of hydrogen is followed by the elements of p-block starting with halogens and then going backwards column by column. The reason of this treatment is that the elements with high electonegativity often form molecules with covalent bonds thus we are moving from the simpler to the more complicated structures of materials. When speaking about an element the history, the mineral appearance, the production and the main application will be discussed. As for the physical characteristics their state, thermal and electric conductivity, main isotopes and allotropes will be shown. The introduction of molecule structure is based on the Lewis structure and VSEPR theory. The chemical nature of elements is characterized by the oxidation number as well as the reactions with water, acids and bases. This is followed by the systemic discussion of binary and ternary compounds, showing their electron configuration as well as the production, typical and the important reactions in practice. The relations between the chemical structure and the chemical reactivity are often discussed as well. Molecules with multiple carbon atoms are just slightly mentions in inorganic chemistry. On the other hand the element–carbon bonds are often discussed as being the bases of element-organic compounds getting more and more important on the field of organic syntheses and chemical industry. Due to the fast development of semiconductor based electronic industry in the 1970s the search for inorganic compounds having special electric, optical, thermal, mechanic or magnetic properties has increased. The improvement of the high tech industry gave a huge jump-start to create new materials, thus initializing the material science separated from inorganic chemistry. When discussing the elements we will mention the roll of their and their compounds’ in the high-tech technologies, their applications. At the end of this book I call your attention on some textbooks in Hungarian and in English as well as some relevant articles in Wikipedia. Finally, I wish to express my acknowledgement to my old professor Dr. Béla Csákvári for vetting the manuscript and his notes to cluster chemistry. Budapest, 2017 The Author János Rohonczy: Inorganic Chemistry I. 1. Hydrogen 1. Hydrogen Valence shell: 1s1 Physical properties: Colorless gas, low density, low viscosity Occurrence in Universe: Stars, Sun, interstellar gas clouds, giant planets (Jupiter etc.) Occurrence on Earth: Water, hydrocarbons, crystal water Isotopes: Protium, deuterium, tritium Allotropes: Ortho-H2 and para-H2 (with parallel and anti parallel nuclear spins) Industrial preparation: 1) 3 Fe + 4 H2O(vapor) → Fe3O4 + 4 H2 (900 °C) Lavoisier, 1783-1900.
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