DOCSLIB.ORG

Potential Five-Coordinate Titanium-Diketonate Complexes

Total Page：16

File Type：pdf, Size：1020Kb

Download full-text PDF Read full-text
Potential Five-Coordinate Titanium-Diketonate Complexes W&M ScholarWorks Dissertations, Theses, and Masters Projects Theses, Dissertations, & Master Projects 1971 Potential Five-Coordinate Titanium-Diketonate Complexes Pamela Bowen Barrett College of William & Mary - Arts & Sciences Follow this and additional works at: https://scholarworks.wm.edu/etd Part of the Inorganic Chemistry Commons, and the Organic Chemistry Commons Recommended Citation Barrett, Pamela Bowen, "Potential Five-Coordinate Titanium-Diketonate Complexes" (1971). Dissertations, Theses, and Masters Projects. Paper 1539624729. https://dx.doi.org/doi:10.21220/s2-phf3-f166 This Thesis is brought to you for free and open access by the Theses, Dissertations, & Master Projects at W&M ScholarWorks. It has been accepted for inclusion in Dissertations, Theses, and Masters Projects by an authorized administrator of W&M ScholarWorks. For more information, please contact [email protected]. POTENTIAL FIVE-COORDINATE TITANIUM- M -DIKETONATE COMPLEXES A T h e sis Presented to The Faculty of the Department of Chemistry The College of William and Mary in Virginia In Partial Fulfillment Of the Requirements for the Degree of Master of Arts By Pamela Bo B arrett 1971 APPROVAL SHEET This thesis is submitted in partial fulfillm ent of the requirements for the degree of Master of Arts A u th o r / Approved, May 1971 D av id W • Th omp s on , /PhTiD • C irila D^ordjevic, Ph.D, Melvjrn D • S o h iav elii, Ph • D • i i 5 04110 ACKNOWLEDGMENTS The w riter wishes to express her appreciation to Professor David W. Thompson, under whose guidance this inves­ tigation was conducted, for his direction and criticism throughout the investigation. The author is indebted also to Professor C irila Djordjevic and Professor Melvin D. Schiavelli for their careful reading and criticism of the manuscript. Finally, the author wishes to express a special note of thanks to her husband, Richard Barrett, for his invaluable encouragement and assistance. iii TABLE OP CONTENTS Page ACKNOWLEDGMENTS ......... ..................................... I l l LIST OP TABLES . .......................' ..................................... v i l LIST OP PIGURES.............................................................. v i l l ABSTRACT ..o»».o. x REACTIONS OP TITANIUM TETRAHALIDES WITH POTENTIAL t BIDENTATE UNINEGATIVE LIGANDS - LITERATURE SURVEY A. PRELIMINARY CONSIDERATIONS 1 B. A -DIKETONE DERIVATIVES 4 X. Historical Perspective 4 2® Di-Substituted Products 6 3® Adducts of -^-Diketones with Titanium 16 4® Mono-Substituted .^-Diketonate 17 Compounds with Titanium 5® Tri-Substituted -^-Diketonate Complexes 18 with Titanium 6® Tetra-Substituted>^-Diketonate Com- 21 pounds of Titanium f 0 . COMPOUNDS WITH 8-QUINOLINOL 21 1* Adducts of 8-Quinolinol 21 2® Mono-Substituted Complexes of 8- 32 Q u in o lin o l 3® Di-Substituted Complexes of Titanium 33 with 8-Quinolinol 4® Tris-Substituted Complexes of 8- 34 Q u in o lin o l 5® Tetra-Substituted Complexes of 36 Titanium with 8-Quinolinol D« COMPOUNDS WITH SALICYLALDEHYDJ3 41 1® Di-Substituted Complexes 41 2® Tetra-Substituted Complexes of 41 Titanium with 8-Quinolinol and Sallcylaldehyde iv TABLE OF CONTENTS CONT'D. E . SERIES OF OXIMES WITH TITANIUM 45 TETRAHALIDES 1. Adducts of Oximes with Titanium 45 Tetrahalides 2. Mono-Substituted Complexes of 49 Titanium with Oximes P . COMPLEXES OP TITANIUM TETRACHLORIDE 53 WITH ACETANILIDES 1• Di-Substituted Complexes of 53 Acetanilides' with Titanium 2e Tri-Substituted Complexes of 53 Acetanilides with Titanium G. SUMMARY 5 6 EXPERIMENTAL eeoeteeoeeceeoeooeodo 57 REAGENTS eeeoveeaooaeeaeeaeeaa 57 SOLVENTS fiea«e*oe«<»««»e««»e<si09 57 PREPARATIONS 53 General Reaction Procedures 58 j Preparation of 3-Cyano-2,4-pentanedione 59 Preparation of 2,2,6,6-tetramethyl-3»5- 63 heptanedione Reaction of Titanium Tetrachloride and 64 3-Cyano-2,4-pentanedione in a 1:2 Molar Ratio Reaction of Titanium Tetrachloride and 65 3-Cyano-2,4-pentanedione in a 1:3 Molar Ratio Preparation of Trichloro(3-cyano-2,4- 65 pentanedionato)titanium(IV) Preparation of Trichioro(1-phenyl-1 93 - 65 butanedionato)titanium(IV). Preparation of Tribromo(1-phenyl-1,3- 66 butanedionato)titanium(IV) v TABLE OP CONTENTS CONT’D* P a g e Preparation of Tribromo-2,2,6,6- 67 tetram ethyl-3,5-heptanedionatotitanium (IV) Preparation of Trichloro(2,4-pentane- 67 dionato)titanium(IV) Reaction of Dicyclopentadienyltitanium 68 dichloride with Acetylacetone Preparation of Trichloro(1-phenyl-1,3- 68 butanedionato)~pyridinetitanium( IV) Preparation of Trichloroacetylacetonato- 69 pyridinetitanium(IV) PHYSICAL MEASUREMENTS •••-••••••••..o'* 69 Molecular Weights 69 Conductance Measurements 71 Halide Determinations 71 Melting Points 71 Infrared Spectra 71 Nuclear Magnetic Resonance Spectra 72 Analysis 72 DISCUSSION AND RESULTS.......................'•••'••-•••••73 Preparative Chemistry 73 Trihalo(^-diketonato)titanium (lV) Complexes 85 Trichloro(3-cyano-2 94-pentanedionato)- 103 titanium(lV) Conclusion 108 POOTNOTES oeeoo 1t8 vi LIST OP TABLES T a b le Page t -^-DIKETONATE COMPLEXES .................................................... 22 2 8-QUIN0LIN0LATE COMPLEXES ........ 37 3 SALICYLALDEHYDATO COMPLEXES ................................. 46 4 OXIME DERIVATIVES ...... 51 5 ACETANILIDE DERIVATIVES .... ...................... 54 6 ANALYTICAL DATA ...........o. 76 7 MOLECULAR WEIGHT DATA . .................................... 77 8 CONDUCTANCE DATA ............. 78 9 CHARACTERISTIC INFRARED ABSORPTIONS BY ^-DIKETONATE COMPLEXES CONTAINING TERMINAL METHYL GROUPS ........ 93 10 C-N STRETCHING FREQUENCY OF METAL COMPLEXES .....oe.....o«. 107 vii LIST OP FIGURES Figure Page 1 Structural Possibilities for Compounds in the TiX^-LH System ..................................... 3 2 Generalized reaction scheme for the interaction of titanium tetrahalides with potential uninegative bidentate ligands • • 6oo»«*«ea99«e 3 3 Isomeric possibilities for_dihalobis (1-phenyl-1.3-butanedionationato)- titanium (IV) •»osooa»**e««» 13 4 UMR Spectra of IiX 2 ( b z a c ) 2Complexes » « 15 5 Isomeric possibilities for dihalobis- (8-quinolinolato)tltanium(IV) a * * « 35 6 Diagram of apparatus for the preparation of titanium enolate complexes » e e « 60 7 Diagram of apparatus immediately prior tO filtration aaaeaaoaaoee 6 l 8 Diagram of apparatus after filtrationa a 62 9 Diagram of filtering funnel used to dry compound a « e a aaaaaaa»ae 62 10 Beckmann thermometer «»o»0a«a»a 70 11 Infrared spectrum of trichloro(2,4-pentane- dionato)titanium(lV) as a Mull In NUjOl aaaaaaoaeaaasas 79 12 Infrared spectrum of Pyridine as a Mull I n Nlljj Ol oaseoaaaeaaaao 80 13 Infrared spectrum of trichloro-( 2,4- pentanedionato)-pyridinetitanium- * (IV) as a Mull in Uujol » « a « • » 81 14 Infrared spectrum of trichloro(1-penyl- 1,3“butanedionato)pyridinetltanlum- (IV) as a Mull in Nujol • « « * • « 82 viii LIST OF FIGURES CONT'D.> Figur Page 15 The structure of (TiCl^/POCl )2 • • • • • 8? 16 Infrared spectrum of tribromo(2,2.6,6- tetram ethyl-3,5-heptanedionato)- titanium(lV) as a Mull in Nujol . * • 89 17 Infrared spectrum of tribromo(1-phenyl- 1, 3-butanedionato)titanium(IV) as a Mull in Nujol » o • • .............................« • 90 j 18 Infrared spectrum of trichioro(1-phenyl- 1, 3-butanedionato)titanium(IV) as a Mull in Nujol • • « • ••«••••• 91 19 Infrared spectrum of trichloro(1,3- diphenyl-1,3-propanedionato)titanium- (IV) as a Mull in Nu^ol ? 0 « -92 20A B, 0, D-Hmr spectra for mixtures of trichloro(1-phenyl-1,3-butanedionato)- titanium(IV) and dichlorobis(1-phenyl- 1, 3-butanedionato ) tit anium( IV) « e e> « 96 20 Nmr spectra (shifts relative to internal TMS) 97 21 Nmr spectrum of tribrom o(1-phenyl-1,3- butanedionato)titanium(IV) in methylene chloride 93 22 Nmr spectrum of tribrom o(2,2,6,6-tetram ethyl- 3 95-heptanedionato)titanium(IV) In methylene chloride 99 23 Nmr spectrum of trichloro(2,2,6,6- tetram ethyl-3,5-heptanedionato)- titanium(IV) in chloroform • e « » • « 100 24 Postulated structure for trichloro(3-cyano- 2s4-pentanedionato)titanium(lV) « • « 104 25 Infrared spectrum trichioro(3-cyano- 2,4-pentanedionato)-titanium(IV) as a Mull llu 3 ol 0»«90c»0feo«o<>e 10 6 ix ABSTRACT The intent of this work was to investigate reactions of titanium tetrachloride and titanium tetrabromide with several enolizable A-diketones. These diketones usually coordinate to metal atoms as the anion via both oxygens• Particular attention was directed toward the preparation and characterization of potentially five-coordinate com­ plexes of the type X 3TiL, X = Cl* Br and L = A-diketonate anion* since few five-coordinate complexes of titanium have been reported« A«x)iketones used in this study include 2,^-pentanedione * 3-cyano-2,*l'-pentanedione, l-phenyl-l*3- butanedione, 1,3-diphenyl-l*3-propanedione* and 2*2,6*6- tetramethyl-3*5-heptanedione. In addition to preparing and characterizing X^TiL complexes* attempts were made to prepare two pyridine^adducts of the potentially five coordinate complexes» x POTENTIAL FIVE-COORDINATE TITANIUM- >3-DIKETONATE COMPLEXES REACTIONS OF TITANIUM TETRAHALIDES WITH POTENTIAL BIDENTATE UNINEGATIVE LIGANDS- LITERATURE SURVEY A. PRELIMINARY CONSIDERATIONS In recent years there has been a great deal of interest in the reactions of titanium tetrahalides with potential 1 -7 bidentate uninegative ligands such as 2,^-pentanedione , o 8 1-phenyl-1*3-butanedione , 1* 3-diphenyl-l* 3-propanedione * 9 10-12 3-methyl-2»^-pentanedione * 8-quinolinol * salicylalde- 1 2 ,1 3 1** lb hyde , dimethyIglyoxime , dipehnylglyoxime , benzil lb 15-16 monoxime , benzoylacetanilides
Load more

Recommended publications
  • MSDS for Retrotec Air Current Tester
    Material Safety Data Sheet For use with Retrotec’s Air Current Tester Emergency Phone Number (24 hours) CHEMTREC (800-424-9300) Protective Equipment: Wear self-contained breathing apparatus and full protective suit. Outside US: 703-527-3887 SECTION 1 SECTION 6 CHEMICAL IDENTIFICATION OF THE SUBSTANCE/PREPARATION ACCIDENTAL RELEASE MEASURES PRODUCT NAME: Titanium Tetrachloride Do not contact with water. Ventilate area. Wear protective equipment. Do not allow to enter COMMON NAME OR SYNONYMS: Titanium Chloride, Titanium (IV) Chloride drainage systems or water ways. Neutralize with soda ash, limestone etc. Wipe up and put into SPEX CATALOG NUMBER: VIL004 a sealed container for proper disposal. Wash spill site with water after material pick up is complete. Wear chemical resistant glasses, gloves and clothing. Manufacturer/Supplier SPEX CERTIPREP SECTION 7 203 Norcross Avenue HANDLING & STORAGE Metuchen, NJ 08840 Ensure good ventilation/exhaustion at work place. Have an immediate availability of an eye SPEX CERTIPREP LTD wash in case of emergency. Store at room temperature. Keep the container tightly closed. 2 Dalston Gardens Stanmore, Middlesex HA7 1BQ SECTION 8 England EXPOSURE CONTROLS/PERSONAL PROTECTION Tel: (0) 20 8204 6656 Wear goggles, protective apron and acid resistant gloves. Use under fume hood. In case of brief SECTION 2 exposure, use MSHA/NIOSH approved respirator. COMPOSITION/INFORMATION ON INGREDIENTS HAZERDOUS % TLV UNITS CAS # EINECS VOLUME SECTION 9 MATERIAL 3 PHYSICAL & CHEMICAL PROPERTIES TiCl4 ~100 0.5 mg/m [7550-45-0] 10ml Form: Liquid Appearance & odor: Transparent with acrid odor SECTION 3 % volatiles by vol. @ 21C: 100 HAZARD IDENTIFICATION Solubility: Reacts violently with water pH: No information found Corrosive.
    [Show full text]
  • Working with Hazardous Chemicals
    A Publication of Reliable Methods for the Preparation of Organic Compounds Working with Hazardous Chemicals The procedures in Organic Syntheses are intended for use only by persons with proper training in experimental organic chemistry. All hazardous materials should be handled using the standard procedures for work with chemicals described in references such as "Prudent Practices in the Laboratory" (The National Academies Press, Washington, D.C., 2011; the full text can be accessed free of charge at http://www.nap.edu/catalog.php?record_id=12654). All chemical waste should be disposed of in accordance with local regulations. For general guidelines for the management of chemical waste, see Chapter 8 of Prudent Practices. In some articles in Organic Syntheses, chemical-specific hazards are highlighted in red “Caution Notes” within a procedure. It is important to recognize that the absence of a caution note does not imply that no significant hazards are associated with the chemicals involved in that procedure. Prior to performing a reaction, a thorough risk assessment should be carried out that includes a review of the potential hazards associated with each chemical and experimental operation on the scale that is planned for the procedure. Guidelines for carrying out a risk assessment and for analyzing the hazards associated with chemicals can be found in Chapter 4 of Prudent Practices. The procedures described in Organic Syntheses are provided as published and are conducted at one's own risk. Organic Syntheses, Inc., its Editors, and its Board of Directors do not warrant or guarantee the safety of individuals using these procedures and hereby disclaim any liability for any injuries or damages claimed to have resulted from or related in any way to the procedures herein.
    [Show full text]
  • Heat of Formation of Titanium Tetrachloride Waiter H
    Journal of Research of the National Bureau of Standards Vol. 62, No. 1, January 1959 Research Paper 2928 Heat of Formation of Titanium Tetrachloride WaIter H. Johnson, Raymond A. Nelson, and Edward 1. Prosen The heat of formation of gaseous titanium tetrachloride has been measured by the reaction of metallic titanium with gaseous chlorine in a calorimeter. The value for the heat of formation obtained in t his investigation corresponds to the reaction: Ti(c) + 2Clz( g) = TiCI4(g), ilHf °(25° C) =-763.2 ± 2.9 kj/ mole (- 182.4 ± O.7 kcal(mole) . Earlier data are discussed briefly. 1. Introduction The following results were obtained in volume per­ cent: H 2, 0.00; CO, 0.00; (N2 + 0 2 + A), 0.01. The This investigation is part of a program on the purity of a second sample was determined to be determination of the tJlermodynamic properties of 99.99 mole percent from cryoscopic measure~ncnts titanium compounds sponsored by the Office of by Gaylon S. Ross of the Pure Substances SectIOn of Naval Research; it is also a part of the work of the the Chemistry Division. thermochemical laboratory of the Bureau on the A sample of the helium, taken directly from the determination of the heats of formation of compounds cylinder, was found to contain less Lhan 0.01 percent of importance to science and industry .. of oxygen and nitrogen from an anal)'sis by Vemon The heat of formation of TiC14 may be obtained H. Dibclcr of the Mass Spectrometry Section of the by several different methods, each having certain Atomic and Radiation Physics Divisi on.
    [Show full text]
  • Safety Data Sheet Material Name: TICL4 SDS ID: ADC23550
    Safety Data Sheet Material Name: TICL4 SDS ID: ADC23550 Section 1 - PRODUCT AND COMPANY IDENTIFICATION Material Name TICL4 Synonyms TITANIUM TETRACHLORIDE; TITANIUM CHLORIDE; TITANIC CHLORIDE; TETRACHLOROTITANIUM; TITANIUM CHLORIDE (TiCl4) (T-4)-; TITANIUM(IV) CHLORIDE; T-308; SMOKE STICKS #15-049; UN 1838; Cl4Ti Chemical Family inorganic, halogenated Product Use semiconductor manufacture Restrictions on Use None known. Details of the supplier of the safety data sheet Entegris, Inc. 129 Concord Road Building 2 Billerica, MA 01821 USA Telephone Number: +1-952-556-4181 Telephone Number: +1-800-394-4083 (toll free within North America) Emergency Telephone Number: CHEMTREC - U.S. - 1-800-424-9300 CHEMTREC - Intl. - 1-703-527-3887 E-mail: [email protected] Section 2 - HAZARDS IDENTIFICATION Classification in accordance with paragraph (d) of 29 CFR 1910.1200. Acute Toxicity - Oral - Category 4 Acute Toxicity - Inhalation - Vapor - Category 1 Skin Corrosion/Irritation - Category 1 Serious Eye Damage/Eye Irritation - Category 1 Specific target organ toxicity - Single exposure - Category 3 ( respiratory system ) GHS Label Elements Symbol(s) Signal Word Danger Hazard Statement(s) ____________________________________________________________ Page 1 of 10 Issue date: 2018-12-03 Revision 3.2 Print date: 2018-12-03 Safety Data Sheet Material Name: TICL4 SDS ID: ADC23550 Fatal if inhaled. Harmful if swallowed. Causes severe skin burns and eye damage. May cause respiratory irritation. Precautionary Statement(s) Prevention Do not breathe vapor or mist. Wash thoroughly after handling. Use only outdoors or in a well-ventilated area. Do not eat, drink or smoke when using this product. Wear respiratory protection. Wear protective gloves/protective clothing/eye protection/face protection.
    [Show full text]
  • (III). the Reactions of Titanium Tetrachloride with Piperidine and Diphenylamine
    DAEHAN HWAH스 K HWOEjEE (Journal of the Korean Chemical Society) Vol. 18, No. 6, 1974 Printed in Republic of Korea ' 유기티탄 화학 (제 3 보 ). 사염화티탄과 피페러딘 및 디페닐아민과 의 반응 魚勇善* •李厚成•孫蓮秀 한국과학기 술연 구소 (1974. 3. 28 접수 ) Organotitanium Chemistry (III). The Reactions of Titanium Tetrachloride with Piperidine and Diphenylamine Young Sun Uh, Hoosung Lee and Youn Soo Sohn* Korea Institute of Science and Technology, Seoul, Korea (Received March 28, 1974) 요 약 . 사염화티 탄과 피페리딘 및 디페닐아민의 반응을 반응생성물들을 분리하여 규명함으로써 설명 하였 다 . 사염 화티 탄과 피페 리딘은 부가반응과 치 환반응이 다음과 같이 동시 에 일어 남을 알 수 있었다 . TiCL + C5H10NH 一 > TiC14-C5H10NH TiCU + C5H10 —> TiCl3-NC5H10+HCl 부가반응은 비교적 빨리 일어나며 수분내에 반응이 완결되는데 비하여 치환반응은 매우 느리게 일 어난다 . 위의 두 반응생성물을 모두 분리하여 화학분석결과와 핵자기공명 및 적외선 스펙트럼을 고 찰 함으로써 완전히 규명하였다 . 이들 반응생성물에는 모두 피페리딘의 염화수소염이 공침됨을 알 수 있었다 . 그러나 디페닐아민의 경우 , 위의 반응과 아주 비슷하게 일어나지만 부가반응 생성물은 순수 하게 얻을 수 있었다 . Abstract. The direct reactions of titanium tetrachloride with piperidine and diphenylamine in dichloromethane have been studied by examining the isolated reaction products. In the reaction with piperidine, titanium tetrachloride undergoes both addition and substitution reactions as in the following: TiCl4 丄 C5H10NH —> TiCl4-C5H10NH TiCl4 - C5H10NH —> TiCl3-NC5H10+HCl The addition reaction is relatively fast and completed in minutes whereas the substitution reaction is very slow. The both reaction products coprecipitated with piperidine hydrochloride formed during the substitution reaction were isolated and characterized. The reaction with diphenylamine resembles to the above reaction but the addition compound could be obtained in pure crystal form.
    [Show full text]
  • A Comparative Study on the Chloride Effectiveness of Synthetic Rutile and Natural Rutile Manufactured from Ilmenite
    www.nature.com/scientificreports OPEN A comparative study on the chloride efectiveness of synthetic rutile and natural rutile manufactured from ilmenite ore Eun Jin Jung1*, Jinyoung Kim1 & Ye Rin Lee2 Studies on continuous and selective chlorination by using ilmenite have been actively conducted because the efcient removal of FeO from ilmenite(FeTiO3) ore using selective chlorination not only improves the reaction purity of TiCl4 but it also leads to price competitiveness compared to TiCl4 synthesized from natural rutile. The chlorination of synthetic rutile with FeO removed was compared with that of natural rutile to examine the reaction efciency. The selective chlorination efciency depends on the input amounts of coke and Cl2, as shown by thermodynamic calculation, when FeO is selectively removed. It was found that manufacturing of TiCl4 was easier by using the synthetic rutile, because it had greater porosity than natural rutile. Relatively greater pore volumes were found in the synthetic rutile than in natural rutile. It was confrmed that the reaction efciency of chlorination for TiCl4 production was directly related to the diference in the porosity distribution between the titanium ores, as verifed by a kinetic comparison of synthetic and natural rutiles. Ilmenite(FeTiO3) ore is a raw material for producing TiCl4 through the chlorination method and the sulfuric acid reaction method. TiCl 4 is used as a raw material for producing metallic titanium through the Kroll process 1–5 or for producing TiO2 used as a catalyst or pigment . Until now, high-grade rutile ore has been used for manu- facturing TiCl4. Te advantages of having low prices and extensive reserves have led to active research using the ilmenite ore.
    [Show full text]
  • INTI065.5 TITANIUM TETRACHLORIDE 1M in Toluene
    Gelest, Inc. GELEST, INC. 11 East Steel Rd. Morrisville, PA 19067 Phone: (215) 547-1015 MATERIAL SAFETY EMERGENCY TELEPHONE DATA SHEET CHEMTREC: 1-800-424-9300 NAME USED ON LABEL: TITANIUM TETRACHLORIDE 1M in toluene - INTI065.5 CHEMICAL NAME: TITANIUM TETRACHLORIDE 1M in toluene SYNONYMS: TITANIUM IV CHLORIDE, toluene solution CHEMICAL FAMILY: TITANIUM COMPOUND FORMULA: Cl4Ti HMIS CODES HEALTH: 3 FLAMMABILITY: 3 REACTIVITY: 2 INGREDIENTS IDENTITY CAS NO. % TLV OSHA PEL TOLUENE 108-88-3 79-82 TWA- 100ppm TWA- 200ppm TITANIUM TETRACHLORIDE 755045-0 18-21 not established not established (OSHA PEL for hydrogen chloride, TWA: 5ppm) PHYSICAL DATA Boiling Point: 136.4°C Freezing Point: -24°C Specific Gravity: 0.965 Vapor Pressure,20°: 1.27 kPa Vapor Density (air = 1): 1.07 Solubility in water: reacts violently % volatiles: 100% Evaporation rate: not determined Molecular Weight: 189.71 Other: NA Appearance & Color: Clear to straw liquid with acrid odor of hydrogen chloride, forms dense white fumes on contact with air. FIRE & EXPLOSION DATA Flash Point, COC: 8°C(46°F) Autoignition Temp.: 535°C (toluene) Flammability Limits-(toluene) LEL: 1.27% UEL: 7% Extinguishing Media: Alcohol resistant foam, carbon dioxide, dry chemical. Use of high expansion foam (100:1) is recommended to cover flames. Special Fire Fighting Procedures: Use only dry media to extinguish flames. Water spray or fog should only be used to knock down fumes in areas downwind from the fire. Avoid eye and skin contact. Do not breathe fumes or inhale vapors. Unusual Fire and Explosion Hazards: Irritating dense white fumes of titanium dioxide and hydrogen chloride develop when material is exposed to water or open flame.
    [Show full text]
  • High Aspect Ratio Tio2 Nanowires Tailored in Concentrated Hcl Hydrothermal Condition for Photoelectrochemical Water Splitting
    RSC Advances This is an Accepted Manuscript, which has been through the Royal Society of Chemistry peer review process and has been accepted for publication. Accepted Manuscripts are published online shortly after acceptance, before technical editing, formatting and proof reading. Using this free service, authors can make their results available to the community, in citable form, before we publish the edited article. This Accepted Manuscript will be replaced by the edited, formatted and paginated article as soon as this is available. You can find more information about Accepted Manuscripts in the Information for Authors. Please note that technical editing may introduce minor changes to the text and/or graphics, which may alter content. The journal’s standard Terms & Conditions and the Ethical guidelines still apply. In no event shall the Royal Society of Chemistry be held responsible for any errors or omissions in this Accepted Manuscript or any consequences arising from the use of any information it contains. www.rsc.org/advances Page 1 of Journal7 Name RSC Advances Dynamic Article Links ► Cite this: DOI: 10.1039/c0xx00000x www.rsc.org/xxxxxx ARTICLE TYPE High aspect ratio TiO2 nanowires tailored in concentrated HCl hydrothermal condition for photoelectrochemical water splitting Jinzhan Su*, Liejin Guo Received (in XXX, XXX) Xth XXXXXXXXX 20XX, Accepted Xth XXXXXXXXX 20XX 5 DOI: 10.1039/b000000x TiO2 nanowire/nanorod array grown on FTO substrate by hydrothermal reaction have attracted great attentions because of their favorable application in DSSC and quantum dot solar cells. In this paper, discrete vertically aligned TiO2 nanowire arrays with their length as long as 7.2 µm and their diameter less than 100 nm were successfully synthesized on FTO substrate by hydrothermal method.
    [Show full text]
  • Protect Laboratory Chemicals from Use in a Terrorist Attack
    Protect Laboratory Chemicals from Use in a Terrorist Attack Overview Chemicals and reagents used for research and development, testing, monitoring, or education are critical to production, nonproduction, diagnostic, and pharmaceutical laboratory services. However, in the wrong hands, some of these same chemicals can be used for great harm. What Is CFATS? In 2006, Congress authorized the U.S. Department of Homeland Security (DHS) to establish the Chemical Facility Anti-Terrorism Standards (CFATS) program. Managed by the Cybersecurity and Infrastructure Security Agency (CISA), the CFATS program identifies and regulates high-risk chemical facilities to ensure that security measures are in place that reduce the risk of certain chemicals being weaponized. Appendix A of the CFATS regulation lists more than 300 chemicals of interest (COI) and their respective screening threshold quantity (STQ), concentration, and security issues. If released, stolen or diverted, and/or used as a contaminant, these COI have the potential to cause significant loss of human life and/or health consequences. Any individual or facility in possession of COI that meets or exceeds the STQ and concentration must report those chemicals to CISA through an online survey called a Top-Screen. COI Commonly Found in Laboratories Laboratories that use COI are considered chemical facilities under CFATS and may be subject to its regulations. Some of the commonly reported COI include, but are not limited to: • Aluminum (powder) • Sarin • Ammonium perchlorate • Sodium nitrate • DF (Methyl phosphonyl difluoride) • Soman [o-Pinacolyl • HN1, HN2, and HN3 (Nitrogen mustard-1, 2, 3) methylphosphonofluoridate] • Hydrogen fluoride (anhydrous) • Sulfur Mustard (Mustard gas (H)) • Hydrogen peroxide (conc.
    [Show full text]
  • Synthesis and Characterization of Tio2 Nanoparticles for the Reduction of Water Pollutants
    materials Article Synthesis and Characterization of TiO2 Nanoparticles for the Reduction of Water Pollutants Gigliola Lusvardi 1,*, Corrado Barani 2, Federica Giubertoni 2 and Giulia Paganelli 1 1 Department of Chemistry and Geological Sciences, University of Modena and Reggio Emilia, Via G. Campi 103, 41125 Modena, Italy; [email protected] 2 Barchemicals, Via S. Allende 14, 41051 Castelnuovo Rangone (MO), Italy; [email protected] (C.B.); [email protected] (F.G.) * Correspondence: [email protected], Tel.: +39-059-205-8549 Received: 30 August 2017; Accepted: 18 October 2017; Published: 20 October 2017 Abstract: The aim of this manuscript was the optimization of the synthesis of TiO2 nanoparticles (TiO2 NPs) with conditions that could be easily reproducible at the industrial level. Several procedures were tested and those with C12H28O4Ti and CO(NH2)2 as precursors seemed the most promising and, consequently, were improved with different molar ratios, lower temperatures and the addition of NH4Cl as a secondary dopant of nitrogen. The obtained samples were studied with analytical techniques such as X-ray powder diffraction (XRPD) and field emission scanning electron microscopy (FESEM). To complete the study, dye degradation and bacteriological tests were also performed. The results indicate that it is possible to obtain TiO2 NPs at lower temperatures with respect to those used in the literature; the best candidate that could satisfy all the requirements was a sample with a ◦ molar ratio of C12H28O4Ti:CO(NH2)2 at 2:1 and obtained at 50 C. Keywords: TiO2; nanoparticles; photocatalysis; pollutants 1. Introduction Nanotechnologies are a set of methods and techniques for the treatment of matter and aimed at obtaining materials with novel functionalities and improved characteristics.
    [Show full text]
  • The First Report of Lewis Acid Reagents in the Intramolecular Rauhut-Currier Reaction Andrew T
    Bryn Mawr College Scholarship, Research, and Creative Work at Bryn Mawr College Chemistry Faculty Research and Scholarship Chemistry 2015 The first report of Lewis acid reagents in the intramolecular Rauhut-Currier reaction Andrew T. Krasley William Paul Malachowski Bryn Mawr College, [email protected] Let us know how access to this document benefits ouy . Follow this and additional works at: http://repository.brynmawr.edu/chem_pubs Part of the Chemistry Commons Custom Citation A. T. Krasley and W. P. Malachowski, “The first report of Lewis acid reagents in the intramolecular Rauhut–Currier reaction,” Tetrahedron Letters 56.44 (2015): 6073-6076. This paper is posted at Scholarship, Research, and Creative Work at Bryn Mawr College. http://repository.brynmawr.edu/chem_pubs/19 For more information, please contact [email protected]. The first report of Lewis acid reagents in the intramolecular Rauhut-Currier reaction Andrew T. Krasley and William P. Malachowski* Chemistry Department, Bryn Mawr College, Bryn Mawr, PA 19010, USA [email protected] Abstract: The first report of Lewis acid use in intramolecular Rauhut-Currier reactions is described. Titanium Lewis acids lead to rapid Rauhut-Currier reactions in the case of two classic substrates. More importantly, titanium and tin Lewis acids were the only successful reagent for a more complex substrate, thereby illustrating the potential for Lewis acid reagents to facilitate challenging intramolecular Rauhut- Currier reactions that fail with traditional reagents. Graphical abstract: Keywords: Lewis acid, Rauhut-Currier, conjugate addition, bicarbocyclic synthesis Lewis acids are an extremely effective reagent for a variety of chemical transformations and the wealth of review articles1 describing their many applications serves to illustrate their value.
    [Show full text]
  • 53. Water Reactive Materials
    SYMPOSIUM SERIES No. 150 # 2004 IChemE WATER REACTIVE MATERIALS — INCORPORATION INTO SAFETY AND ENVIRONMENTAL RISK ASSESSMENTS Lyn Fernie, Paul Wright and Theo Kapiasà AK EHS & Risk, Aker Kvaerner Engineering Services Ltd, Ashmore House, Stockton on Tees, TS18 3RE ÃIndependent Water reactive chemicals are generally aggressive materials that are used widely in the process industries. Common water reactive substances are sulphur trioxide, oleum, titanium tetrachloride, silicon tetrachloride, chlorosulphonic acid, chloroace- tyl chloride and phosphorus trichloride. When released to the atmosphere, water reactive materials generally react readily with any free ground water, substrate water and atmospheric water. The exact nature, kinetics and thermodynamics of these reactions govern the subsequent consequences of a release. Consequence modelling and dispersion analysis of water reactive materials is notoriously difficult due to the uncertainties surrounding the reaction with water. Very little experimental data are available on the release behaviour of many water reactive materials. There are often discrepancies and gaps in the data available on the liquid phase hydrolysis reaction; these discrepancies can be as extreme as whether the reaction is exothermic or endothermic. This paper will use a case study to show how the behaviour of water reactive materials has been incorporated into safety and environmental risk assessments, in particular for the purposes of the predictive aspects of COMAH Safety Reports. KEYWORDS: COMAH, reactive, consequence, dispersion, predictive, hydrolysis. THE REQUIREMENT TO MODEL WATER REACTIVE CHEMICALS The COMAH Regulations 19991 require that operators demonstrate that they have ident- ified potential major accident hazards and taken measures to prevent them and limit their consequences. Schedule 4 Part 2 Para 4b also requires an “assessment of the extent and severity of the consequences of identified major accidents”.
    [Show full text]