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2009년도 제2학기 화 학 2 담당교수: 신국조 Textbook: P. Atkins / L. Jones, Chemical Principles, 4th ed., Freeman (2008) Chapter 15 CHAPTER 15 THE ELEMENTS: THE LAST FOUR MAIN GROUPS GROUP 15/V : THE NITROGEN FAMILY Electronic configuration: ns23np Oxidation states: –3 ~ +5 Different reactivities Stable N2 Burning in air, P Semiconductor, As, Sb Metal, Bi Fig. 15.1 N2(l), Sb, red P, Bi, As 15.1 The Group 15/V Elements ◆ Nitrogen, N o o o m.p.: N2(–196 C) cf. O2(–183 C), Ar(–186 C) Stable triple bond: N≡ N, 944 kJ·mol–1 Bacterial fixation of N2 in nodules on the roots of beans, alfalfa,… Haber-Bosch process Electronegativity: 3.0 – Multiple oxidation states: NH3(–3), HNO3(+5), N3 (azide,–1/3) Fig. 15.2 The pea-plant bacteria. Small atomic radius: π -bond formation from 2p-orbitals, N2O3 ◆ Phosphorus (인,燐), P Large atomic radius Æ π -bond formation from 3p-orbitals Æ single bonds, P4O6 1 2009년도 제2학기 화 학 2 담당교수: 신국조 Textbook: P. Atkins / L. Jones, Chemical Principles, 4th ed., Freeman (2008) Chapter 15 Mineral, apatites, Ca3(PO4)2 ∆ 2 Ca34(PO )2(ss) ++6 SiO2( ) 10 C(s) ⎯⎯→+P4(g) 6 CaSiO3(l) +10 CO(g) White (or Yellow) phosphorus: soft, white, very reactive (burns in air, stored in water), tetrahedral P4 molecules, chemiluminescence (trioxide of phosphorus), 연막탄 Red phosphorus: less reactive, matches, amorphous network (chains of linked P4 tetrahedra) Obtained by heating (240oC) white phosphorus without air (iodine catalyst) Red phosphorus, powder ◆ Arsenic (비소,砒素), As Metalloid GaAs Æ used in lasers in CD players ◆ Antimony, Sb Metalloid Pb/Sb electrodes in lead storage batteries Semiconductors (diodes) ◆ Bismuth, Bi Fig. 15.3 Minerals: Orpiment(웅황,雄黃, As2S3), Stibnite Metal (휘안광,輝安鑛,Sb2S3), Realgar(계관석,鷄冠石,As4S4) Low m.p. (271.5oC) Low melting alloys with Pb, Cd… Æ Activating sprinklers in fire detector 15.2 Compounds with Hydrogen and the Halogens ▶ Ammonia, NH3 Dipole moment: 1.47 D (cf. water: 1.85 D) Poor solvent for strong ionic salts ex. KCl Good solvent for ionic salts with polarizable anions ex. KI Very soluble in water: hydrogen bonds between NH3 and H2O Autoprotolysis: ⎯⎯→ + − 2 NH34(am)←⎯⎯ NH (am) + NH2(am) , + − −33 o Kam =[NH4 ][NH2 ] =1×10 at –35 C Strong Lewis base: 2+ 2+ 2+ Fig. 15.4 Add NH3 to Cu (aq) Cu()aq +⎯4 NH33()aq ⎯→Cu(NH)4()aq 2 2009년도 제2학기 화 학 2 담당교수: 신국조 Textbook: P. Atkins / L. Jones, Chemical Principles, 4th ed., Freeman (2008) Chapter 15 ▶ Ammonimum salts Used as fertilizers Decomposition: ∆ (NH42)CO3(sg)⎯⎯→+2 NH3() CO2()g+H2O()g Oxidation: 250o C NH43NO(sg)⎯⎯⎯→+NO2( ) 2 HO2(g) < 300o C 2 NH43NO (sg) ⎯⎯⎯⎯→+2 N2( ) O2(g) +4 H2O(g) Å explosive (dynamite) ▶ Hydrazine, N2H4 Oily, colorless liquid Used as a rocket fuel Obtained by slow oxidation by hypochlorite: −−aqueous alkali 2 NH32(aq) + ClO (aq) ⎯⎯⎯⎯⎯→+N H4(aq) Cl (aq) +H2O(l) Removing corrosive oxygen from water in high T & P steam furnace NH24(aq)+⎯O(2g) ⎯→+N2(g) 2 H2O(l) ▶ Nitrogen halides, +3 oxidation state NF3 (most stable), NCl3 (reacts with water), NI3·NH3 (explosive) 3– ▶ Nitrides, N ∆ 3 Mg()sg+⎯N23( ) ⎯→ MgN2(s) Mg32N (sl) +⎯6 H2O( ) ⎯→+3 Mg(OH)2(s) 2 NH3(g) Fig. 15.5 Magnesium nitride, Mg3N2 – ▶ Azides, N3 175o C N22O(gl) +⎯2 NaNH ( ) ⎯⎯→+NaN3(s) NaOH(l) +NH3(g) ● NaN3 : shock-sensitive, used in airbags for automobiles 2 NaN32(ss) ⎯⎯→+2 Na( ) 3 N (g) ● Hydrazoic acid, HN3 ⎯⎯→ + − HN32+H O←⎯⎯ H3O +N3, pKa = 4.6 3 2009년도 제2학기 화 학 2 담당교수: 신국조 Textbook: P. Atkins / L. Jones, Chemical Principles, 4th ed., Freeman (2008) Chapter 15 ▶ Phosphine (IUPAC name, Phosphane), PH3 Poison gas Used as fumigants (훈증약, 燻蒸藥) Å pesticides Preparation: 3−−3– 2 P (sl) +⎯6 H23O( ) ⎯→+2 PH (g) 6 OH (aq), ( phosphide ion: P ) ▶ Phosphorus halides ● Phosphorus trichloride, PCl3 Liquid, pesticides, oil additive, flame retardant P42 + 6 Cl ⎯⎯→ 4 PCl3 ● Phosphorus pentachloride, PCl5 Colorless, water-sensitive solid, chlorinating reagent PCl32 + Cl ⎯⎯→ PCl5 Hydrolysis Æ no change in oxidation states: +33+ PCl32(ll)3+⎯ HO() ⎯→H3 PO3(s)3+ HCl(g) +55+ PCl52(ll)+⎯4 H O( ) ⎯→+H3 PO4 (s) 5 HCl(g) 15.3 Nitrogen Oxides and Oxoacids Nitrogen oxides, NOx : “nox” Å air pollutants ▶ Dinitrogen oxide (Nitrous oxide, “laughing gas”), N2O +1 250o C NH43NO(sg)⎯⎯⎯→+NO2( ) 2 HO2(g) Tasteless, unreactive, nontoxic gas Used as an anesthetic, foaming agent for whipped cream 4 2009년도 제2학기 화 학 2 담당교수: 신국조 Textbook: P. Atkins / L. Jones, Chemical Principles, 4th ed., Freeman (2008) Chapter 15 ▶ Nitrogen oxide, NO +2 Colorless gas NO gas from exhausts of planes, cars Æ acid rain Neurotransmitter Æ dilating blood vessels Preparations: 1000o C, Pt 4 NH32(gg) +⎯5 O ( ) ⎯⎯⎯→+4 NO(g) 6 H2O(g) − −+ 2 NO2 (aq) ++2 I (aq) 4 H (aq) ⎯⎯→+2 NO(g) I22(aq) +2 H O(l) Acid rains: 2 NO()gg+⎯O22() ⎯→2 NO()g 3 NO22(gl) +⎯H O( ) ⎯→+2 HNO3(aq) NO(g) ▶ Nitrogen dioxide, NO2 +4 Choking, poisonous brown gas ⎯⎯→ 2 NO2 (brown)←⎯⎯ N24O (colorless) Disproportionation (불균등화 반응): +4 +5 +2 NO2 (gl)+⎯H2O( ) ⎯→+2 HNO3(aq) NO(g) Smog formation ▶ Dinitrogen trioxide, N2O3 +3 Blue gas, anhydride of nitrous acid NO(23gl)+⎯H2O() ⎯→ 2 HNO2(aq) Fig. 15.6 Dinitrogen trioxide, N2O3 −100o C – Deep blue liquid Pale blue solid ▶ Nitrites, NO2 +3 ⎯⎯⎯⎯→ Obtained by reducing nitrates: 350o C KNO32(ss) +⎯Pb( ) ⎯⎯→+KNO (s) PbO(s) Processing meat products: Retarding bacterial growth Forming a pink complex with hemoglobin Æ inhibits oxidation of blood (brown) ▶ Nitric acid, HNO3 +5 Colorless liquid acid, b.p. 85oC Used as fertilizers and explosives Å nitroglycerin (dynamite) > trinitrotoluene (TNT) Preparation: Three-step Ostwald process Step 1: Oxidation of ammonia −3 +2 850oC, 5 atm, Pt/Rh 4 HN3()gg+5 O2 ()⎯⎯⎯⎯⎯⎯→+4NO()g6 H2O()g 5 2009년도 제2학기 화 학 2 담당교수: 신국조 Textbook: P. Atkins / L. Jones, Chemical Principles, 4th ed., Freeman (2008) Chapter 15 Step 2: Oxidation of NO +24+ 2 NO(gg)+⎯O2 ( ) ⎯→2NO2 (g) Step 3: Disproportionation in water +4+5+2 3 N O2 (gl) +⎯H23O( ) ⎯→+2 H N O (aq) N O(g) 15.4 Phosphorus Oxides and Oxoacids ▶ Phosphorous(III) oxide, P4O6 P42(sg, white) +⎯3 O ( ) ⎯→ P4O6(s) Å anhydride of phosphorus acid ▶ Phosphorous acid, H3PO3 P46O(sl)+⎯6 HO2() ⎯→4 HP3O(3aq) Å diprotic acid ! ▶ Phosphorous(V) oxide, P4O10 P42(sg, white) +⎯5 O ( ) ⎯→ P4O10(s) Å drying agent, anhydride of phosphoric acid ▶ Phosphoric acid, H3PO4 P41O0(sl)+⎯6 HO2() ⎯→4 HP3O4(aq) ● Usage of phosphoric acid: Fertilizers, food additives, detergents ▶ Phosphates Ca(PO)()sl+⎯2 HSO() ⎯→+2 CaSO()sCa(HPO)(s) 342 24 4 242 superphosphate ● Condensation reaction (축합반응,縮合反應) : Pyrophosphoric acid (H4P2O7) 6 2009년도 제2학기 화 학 2 담당교수: 신국조 Textbook: P. Atkins / L. Jones, Chemical Principles, 4th ed., Freeman (2008) Chapter 15 ● Polyphosphates ★ ATP (Adenosine triphosphate): Energy source in cells – o ATP + H2O ⎯⎯→ ADP (Adenosine diphosphate) + H2PO4 , ∆=G −30 kJ at pH 7 GROUP 16/VI : THE OXYGEN FAMILY 15.5 The Group 16/VI Elements Electronic configuration: ns24np Chalcogens (ore former), 칼코젠 Etymology(어원,語原): Greek chalkos (ore) + -gen (former); from the occurrence of oxygen and sulfur in many ores cf. Halogen (salt former): Greek halos (salt) 7 2009년도 제2학기 화 학 2 담당교수: 신국조 Textbook: P. Atkins / L. Jones, Chemical Principles, 4th ed., Freeman (2008) Chapter 15 ▶ Oxygen, Most abundant element in Earth’s crust Much more reactive than nitrogen Gas: O2 Colorless, tasteless, odorless gas Pale-blue liquid at -183oC Paramagnetic (two unpaired electrons) Heavily consumed in steel industry Responsible for combustion Used in medicine, welding Fig. 15.7 Pale blue liquid O2. ▶ Ozone, O3 Blue gas with pungent smell o Condenses at -112 C to an explosive blue liquid Prepared by passing electric discharge through O2 Also present in smog: UV NO2 ⎯⎯→ NO + O OO+⎯23⎯→O Presence of ozone in stratosphere vital to lives on Earth Fig. 15.8 Dark blue liquid O3. Fig. 15.9 Elecronegativities. Fig. 15.10 Radii (in pm) of atoms and anions of Group 16/VI elements. ▶ Sulfur Atomic radius: S > O EN & IE: S < O Polarity: S-H < O-H Æ H2S(g), H2O(l) ∆, 200o C Catenation (사슬화 반응) Æ S8 rings ⎯⎯⎯⎯→ long strands of “plastic sulfur” Disulfide link: – S – S – Æ structure of proteins Ores: 8 2009년도 제2학기 화 학 2 담당교수: 신국조 Textbook: P. Atkins / L. Jones, Chemical Principles, 4th ed., Freeman (2008) Chapter 15 Fig. 15.11 Sulfide ores: PbS (galena,방연광,方鉛鑛), HgS (cinnabar,진사,辰沙) FeS2 (pyrite,황철광,黃鐵鑛), ZnS (sphalerite,섬아연광,閃亞鉛鑛) ► Frasch process: Extraction of elemental sulfur in porous limestones in salt domes Steam injection Æ Liquefying sulfur (m.p. 115oC) Æ Pumped out by compressed air ► Claus process: 2 H22S()gg+⎯3 O() ⎯→2 SO2()g+2 H2O(l) o 300 C, Al23O 2 H22S()gg+SO()⎯⎯⎯⎯⎯→+3 S(l) 2 H2O()g ● Elemental sulfur Yellow, tasteless, odorless, insoluble, nonmetallic molecular solid, S8 rings Fig. 15.12 Common crystal forms of sulfur: (a) blocklike stable rhombic form (b) needlelike monoclinic form ● Selenium, Se nonmetal, conductivity increases by exposure to light, used in solar cells ● Tellurium, Te Metalloid, semiconductor, alloys ● Polonium, Po radioactive metalloid, source of α -particles, used in antistatic devices in textile industry Fig. 15.13 Se(nonmetal) & Te(metalloid). 15.6 Compounds with Hydrogen ▶ Water, H2O ★ Drinking water Aerator: removing H2S, oxidizing organic compounds to CO2, adding O2 2+ 3+ 2+ Lime, Ca(OH)2: pH increase, precipitates hydroxides of Mg , Fe , Cu Å softening water Primary settling basin: Addition of coagulants: Fe2(SO4)3 or alum, Al2(SO4)3·18H2O Æ Coagulation (응집,凝集) and flocculation (엉김) of precipitates 9 2009년도 제2학기 화 학 2 담당교수: 신국조 Textbook: P.
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    Material Safety Data Sheet Xenon difluoride, 99.5% ACC# 37261 Section 1 - Chemical Product and Company Identification MSDS Name: Xenon difluoride, 99.5% Catalog Numbers: AC278550010 Synonyms: Xenon fluoride. Company Identification: Acros Organics N.V. One Reagent Lane Fair Lawn, NJ 07410 For information in North America, call: 800-ACROS-01 For emergencies in the US, call CHEMTREC: 800-424-9300 Section 2 - Composition, Information on Ingredients CAS# Chemical Name Percent EINECS/ELINCS 13709-36-9 Xenon difluoride 99.5 237-251-2 Section 3 - Hazards Identification EMERGENCY OVERVIEW Appearance: white crystals. Danger! Explosive when mixed with combustible material. Causes eye and skin burns. Causes digestive and respiratory tract burns. Air sensitive. Moisture sensitive. Target Organs: Respiratory system, gastrointestinal system, eyes, skin. Potential Health Effects Eye: Causes eye burns. Skin: Causes skin burns. Ingestion: May cause severe and permanent damage to the digestive tract. May cause perforation of the digestive tract. Ingestion of large amounts of fluoride may cause salivation, nausea, vomiting, abdominal pain, fever, labored breathing. Inhalation: Causes chemical burns to the respiratory tract. Inhalation may be fatal as a result of spasm, inflammation, edema of the larynx and bronchi, chemical pneumonitis and pulmonary edema. Causes corrosive action on the mucous membranes. Chronic: Chronic effects include excessive calcification of the bones, ligaments, and tendons. Repeated inhalation may cause perforation of the nasal septum. Section 4 - First Aid Measures Eyes: Immediately flush eyes with plenty of water for at least 15 minutes, occasionally lifting the upper and lower eyelids. Get medical aid imme diately. Do NOT allow victim to rub eyes or keep eyes closed.
  • The Noble Gases

    The Noble Gases

    The Noble Gases The Noble Gases (inert gases, Group 0, Group 18 or the helium group) are notoriously unreactive elements (‘noble’ means unreactive in chemistry) and in their elemental state they exist as monoatomic gases – gases whose ‘molecules’ are single atoms of the element, since the atoms are reluctant to react with anything, including one-another. This inertness is due to the fact that they have stable outer electron shells, with stable octets of electrons (full s and p subshells) except helium, which has a stable full inner shell. The electronic configurations are: Helium (He): 1s2 Neon (Ne): 1s2 2s2 2p6 Argon (Ar): [Ne] 3s2 3p6 Krypton (Kr): [Ar] 3d10 4s2 4p6 Xenon (Xe): [Kr] 4d10 5s2 5p6 Radon (Rn): [Xe] 5d10 6s2 6p6 Nevertheless, this group does have some interesting chemistry and also exhibit interesting physical properties. Reactivity increases down the group. Often helium is included as the first member of the group. Helium (He) Helium is chemically a highly unreactive element. It only forms transient species when electric discharges are passed through a mixture of helium gas and another gaseous element. for example, passing an electric discharge through a mixture of helium and hydrogen forms the transient molecule HHe, which has a very short half-life. HHeF is metastable. Neon (Ne) Neon is chemically the most unreactive element. It forms no true compounds, and no neutral molecules. Ionic molecules are known, e.g. (NeAr)+, (NeH)+, (HeNe)+ and Ne+. Argon (Ar) The unstable argon fluorohydride, HArF, is known. Ar also forms clathrates (see krypton) with water and highly unstable ArH+ and ArF are known.
  • TNT Rri Rrrniteotoluenes AND

    TNT Rri Rrrniteotoluenes AND

    TNT rri rRrNITEOTOLUENES AND MONO- AND DINITBOTOLUENES THEIR MANUFACTURE AND PROPERTIES BY G. CARLTON SMITH, B.S. Instructor in General Chemistry, School of Applied Science, Carnegie Institute of Technology, Pittsburgh, Pa, LONDON CONSTABLE AND COMPANY, LIMITED 10 ORANGE ST., LEICESTER SQ., W. C. 1918 Copyright, 1918, by VAN NOSTRAND COMPANY WHOSE SACRIFICES AND LOVE HAVE MADE POSSIBLE MY EDUCATION THIS BOOK IS AFFECTIONATELY DEDICATED ACKNOWLEDGMENT THE writer wishes to thank all those who have so kindly aided him in the preparation of this book. He is especially grateful for the valued comments and criticisms offered by the members of the Staff of the Department of Chemical Engineering, Carnegie Institute of Technology; for the facts which form the basis of Chapter X, by Dr. Samuel Haythorn of the Singer Memorial Laboratory, Allegheny General Hos- pital; and for data on TNT manufacture by Mr. Robert M. Crawford of the Grasselli Powder Co. The Chemical and Industrial Journals have been consulted freely, and much valuable material has been extracted therefrom. Department of Chemical Engineering, Carnegie Institute of Technology, PITTSBURGH, PA., May, 1918. TABLE OF CONTENTS CHAPTER I PAGE INTKODUCTION 1 CHAPTER II HISTORICAL 6 CHAPTER III THE THEORY OF THE NITRATION OF TOLUENE 20 CHAPTER IV THE MANUFACTURE OF TNT 29 CHAPTER V THE PURIFICATION OF TNT 52 CHAPTER VI INSPECTION AND TESTING OF TNT 61 CHAPTER VII PROPERTIES OF THE TRINITROTOLUENES 77 CHAPTER VIII PROPERTIES OF THE MONO- AND DINITROTOLUENES 95 CHAPTER IX ACCIDENTS IN TNT PLANTS 106 CHAPTER X TNT DISEASES 112 TRINITROTOLUENE CHAPTER I INTRODUCTION THE almost universal adoption of trinitrotoluene as the most efficient explosive in modern warfare; the development and refinement of its manufacture, and the interesting chemistry of its compounds, as well as those of the lower nitro-derivatives of toluene has prompted quite extensive research as to their composition, structure, manufacture, properties and uses.
  • Safety in University Chemistry Courses; an Introduction for Students

    Safety in University Chemistry Courses; an Introduction for Students

    Information Safety in University Chemistry Courses An Introduction for Students BGI/GUV-I 8553 E October 2009 Published by: Deutsche Gesetzliche Unfallversicherung (DGUV) Mittelstraße 51, 10117 Berlin Tel.: +49 30 288763800 Fax: +49 30 288763808 E-Mail: [email protected] Internet: www.dguv.de In cooperation with the Gesellschaft Deutscher Chemiker (GDCh) and the Berufsgenossenschaft Rohstoffe und chemische Industrie (BG RCI), formerly BG Chemie. This brochure is permanently being updated by the DGUV working team “Gefahrstoffe”. Translated by the Chevalier Dr. Dr. Rüdiger Marcus Flaig © October 2009 The October 2009 edition corresponds to the German version of the brochure “Sicheres Arbeiten in chemischen Laboratorien” (BGI/GUV-I 8553), October 2009. All rights reserved. No part may be reprinted or copied without the publisher’s prior consent. BGI/GUV-I 8553 E can be obtained from your competent accident insurance provider. The addresses are to be found at www.dguv.de Information Safety in University Chemistry Courses An Introduction for Students BGI/GUV-I 8553 E October 2009 Table of Contents 1 Introduction to lab safety 64 Chemical equipment 26 4.1 Handling laboratory glassware 26 2 Before beginning 4.2 Setting up chemical equipment 27 the practical course 94.3 Heating of equipment 28 2.1 Where are important 4.4 Cooling 30 installations and accessories? 9 4.5 Special information 31 2.2 How to learn about dangerous 4.6. Special methods 31 properties of substances and 4.6.1 Work under reduced pressure 31 safety-relevant parameters 10 4.6.2 Working