DOCSLIB.ORG

United States Patent (19) (11 3,995,013 Démarq (45) Nov

Total Page：16

File Type：pdf, Size：1020Kb

Download full-text PDF Read full-text
United States Patent (19) (11 3,995,013 Démarq (45) Nov United States Patent (19) (11 3,995,013 Démarq (45) Nov. 30, 1976 54 PROCESS FOR THE PREPARATION OF 1906,440 5/1933 Wirth.................................. 423/300 PHOSPHORUS PENTACHELORIDE 75 Inventor: Michel Démarq, Lyon, France Primary Examiner-Oscar R. Vertiz 73) Assignee: Produits Chimiques Ugine Assistant Examiner-Gregory A. Heller Attorney, Agent, or Firm-Brooks Haidt Haffner & Kuhlmann, Paris, France Delahunty 22 Filed: Jan. 2, 1975 (21) Appl. No.: 538,155 57) ABSTRACT 30 Foreign Application Priority Data Processes for the preparation of high-purity free Jan. 3, 1974 France .............................. 74.OO 107 flowing crystalline powder phosphorus pentachloride which processes comprise reacting phosphorus trichlo 52 U.S. Cl. ................................................ 423/300 ride with a deficit of chlorine, cooling the reaction (5ll Int. Cl.’.......................................... C01B 25/10 mixture to form a crystalline mass containing the pen 58 Field of Search..................................... 423/300 tachloride, and recovering and/or purifying the pentachloride. 56 References Cited UNITED STATES PATENTS 8 Claims, No Drawings 1,888,713 l l l 1932 Britton et al.so a w w a so a so a s a 423/300 3,995,013 2 PROCESS FOR THE PREPARATION OF THE INVENTION PHOSPHORUS PENTACHLORIDE It has now surprisingly been discovered that the phos phorus trichloride itself is an almost ideal reaction BACKGROUND OF THE INVENTION 5 medium for the preparation of phosphorus pentachlo The present invention relates to processes for prepar ride. The method of operation of the processes accord ing high-purity phosphorus pentachloride in the form ing to the present invention thus generally comprises of a freely-flowing crystalline powder. three steps, namely, a chlorination of liquid phosphorus Numerous processes are known for preparing phos trichloride with a deficit of chlorine, a phase separa 10 tion, and recovery and/or purification of the pentachlo phorus pentachloride, PCls. The most usual of these ride by removal of the trichloride. Some advantages involves reacting chlorine with phosphorus trichloride, accruing through the use of the trichloride arise be PCla, either in the dry form or in a solvent. cause its boiling point is not too high, its very low crys The dry method is the oldest and was described in tallization temperature eliminates the risk of eutectic BIOS Final Report No. 562. This was the batch process 15 cocrystallization with PCls and the fact of the reduced in which liquid phosphorus trichloride was introduced solubility of phosphorus pentachloride in the cold liq in the form of slender streams at the top of a steel tower uid (for example, 9% at about 15° C). Moreover, the containing a rising stream of gaseous chlorine. The use of phosphorus trichloride presents by comparison solid phosphorus pentachloride was recovered at the with other solvents a number of specific advantages, bottom of the tower. notably, the simplification of the process because the An analogous process conducted on a continuous solvent is already a necessary constituent of the reactor basis has been described by Van Wazer in the Kirk mixture, the fact that an exact amount of chlorine feed Othmer, Encyclopedia of Chemical Technology (2d Ed.) is not required, the greatest purity of obtained product 15,307. U.S. Pat. No. 1,914,750 describes the reaction without the risk of retaining a foreign solvent, and the of liquid chlorine with phosphorus trichloride at a tem 25 fact that traces of residual phosphorus trichloride can perature and a pressure such that the phosphorus pen be eliminated through drying, as with other solvents, tachloride does not sublime. An apparatus for the chlo but also, even more simply by means of a mild post rination of phosphorus trichloride in a closed vessel chlorination of the wet phosphorus pentachloride crys with automatic control and safety devices is described tals. in Ind. Chemist. Chem. Manufact. 25, 517-20 (1949). 30 The first step comprises passing gaseous or liquid Other references are cited in Gmelins Handbuch der chlorine through phosphorus trichloride agitated so as Anorganischen Chemie, under the heading "Phospho to obtain after cooling a crystalline mass having from rus', Vol. C, page 435. about 5 to about 90% solids. The preferred quantity of The dry techniques present numerous disadvantages solid material in this stage of the reaction is from about which are, on the one hand, technical problems princi 35 20 to about 75%. All parts, percentages, proportions pally arising from the difficulty of dissipating the heat and ratios herein are by weight unless otherwise stated. of reaction which often causes local overheating harm It will be understood from the present description ful to normal discharge of the reaction product (be that the chlorination step of the process (wherein chlo cause the phosphorus pentachloride sets up into a mass rine is reacted with the trichloride) is carried out utiliz in the reactor) and to the efficient utilization of mate 40 ing a deficit or deficiency of chlorine. A deficit of chlo rial. On the other hand, these processes provide an rine is taken herein to mean a quantity of chlorine inferior quality phosphorus pentachloride, such prod which is less than the stoichiometric quantity required to convert all of the trichloride to the pentachloride. As uct having in effect undesirable coarseness and com taught above, the chlorination is carried out to provide prising irregular pieces which must be broken up. Fur 45 certain solid content in the reaction mixture. ther, this material contains in an occluded form signifi The heat of reaction is removed either by external cant quantities of phosphorus trichloride which has not cooling of the reactor or by condensation of the boiling reacted. Finally, these materials retain all of the impuri phosphorus trichloride vapors. It is also contemplated ties found in the raw materials; thus, iron and arsenic that the cooling can be supplied by a combination of frequently occur in the product, as do corrosion prod 50 these two methods. ucts. The chlorination temperature can be from about 0. Accordingly, this dry technique is increasingly being to about 150°C, and is preferably from about 40° to abandoned these days in favor of the so called 'sol about 10C. The chlorination reaction can take place vent" technique. In this latter technique, the phospho under subatmospheric, atmospheric, or superatmos rus trichloride is treated with gaseous chlorine in the 55 pheric pressure. Generally, this chlorination reaction is midst of an inert solvent contained in an agitated reac carried out at absolute pressures from 0.1 to 10 bars, tor equipped with a cooling jacket and a reflux con and in certain preferred embodiments of the invention denser. at pressures from about 1 to 1.5 bars. After complete reaction of the phosphorus trichlo The reaction vessel and the condenser can be con ride and cooling, the suspension of phosphorus penta 60 structed entirely of materials which are resistant both chloride crystals so obtained is then filtered and dried. to the phosphorus trichloride and pentachloride as well The greatest part of the impurities remains in the sol as to the chlorine. Appropriate materials of construc vent which is recycled as-is or after distillation. The tion for the process of the present invention include solvent most conveniently utilized is carbon tetrachlo glass, lead-lined, silver-lined and polyfluorocarbon re ride, and attention is called to the Van Wazer reference 65 sin-lined steels, enameled steel, nickel, graphite, and in this regard. Other possible solvents include tetra certain stainless steels. chloroethane, chlorobenzene or even phosphoryl A preferred embodiment for this chlorination stage chloride, POCl (U.S. Pat. No. 1,906,440). of the reaction involves operating at reflux during chlo 3,995,013 3 4 rine introduction until a homogeneous boiling solution sion to phosphoryl chloride by combined reaction with is obtained. This solution would comprise desirably chlorine and phosphoric anhydride. between 40 and 60% of phosphorus pentachloride. The following example is given to illustrate embodi The resulting solution is next cooled with agitation to ments of the invention as it is presently preferred to a temperature of, for example, from 15 to 30° C to practice it. It will be understood that this example is obtain a pumpable and filtrable crystalline mass com illustrative, and the invention is not to be considered as prising phosphorus pentachloride. restricted thereto except as indicated in the appended The next step of the process comprises separating the claims. solid and liquid phases so obtained by filtration, drain ing, decantation or centrifugation, as is conventionally 10 EXAMPLE known. A 1-liter glass reactor fitted with an anchor-shaped Following this separation step, the liquid phosphorus agitator, a thermometer, a reflux condenser and a dry trichloride (saturated with dissolved pentachloride) chlorine delivery tube opening close to the inner side which wets the pentachloride crystals is removed. Such wall of the reactor without dipping into the liquid, is removal of trichloride can be carried out in a number 15 charged with 550 g (4 moles) of phosphorus trichlo of ways to free the pentrachloride of substantially all ride. The flask contents are brought to a boil, and then such remaining trichloride. 124 g (1.75 mole) of chlorine is introduced during a 40 The trichloride can be removed by either batch or minute period while the boiling is continued. The tem continuous evaporation. Such evaporation can be car perature of the liquid rises from 74 to 89 C. Thereaf ried out, for example, using a dry gas stream, for exam 20 ple, dry air or nitrogen, or alternatively a subatmo ter, the solution obtained is cooled with agitation to 20 spheric pressure in an appropriate unit such as a mixer, C. rotary dryer, or a fluidized bed. Such apparatus is con The 665 g of crystalline mass so obtained is drained structed of materials which will not be significantly on a fritted glass Buchner funnel under dry nitrogen.
Load more

Recommended publications
  • Amide Activation: an Emerging Tool for Chemoselective Synthesis
    Featuring work from the research group of Professor As featured in: Nuno Maulide, University of Vienna, Vienna, Austria Amide activation: an emerging tool for chemoselective synthesis Let them stand out of the crowd – Amide activation enables the chemoselective modification of a large variety of molecules while leaving many other functional groups untouched, making it attractive for the synthesis of sophisticated targets. This issue features a review on this emerging field and its application in total synthesis. See Nuno Maulide et al., Chem. Soc. Rev., 2018, 47, 7899. rsc.li/chem-soc-rev Registered charity number: 207890 Chem Soc Rev View Article Online REVIEW ARTICLE View Journal | View Issue Amide activation: an emerging tool for chemoselective synthesis Cite this: Chem. Soc. Rev., 2018, 47,7899 Daniel Kaiser, Adriano Bauer, Miran Lemmerer and Nuno Maulide * It is textbook knowledge that carboxamides benefit from increased stabilisation of the electrophilic carbonyl carbon when compared to other carbonyl and carboxyl derivatives. This results in a considerably reduced reactivity towards nucleophiles. Accordingly, a perception has been developed of amides as significantly less useful functional handles than their ester and acid chloride counterparts. Received 27th April 2018 However, a significant body of research on the selective activation of amides to achieve powerful DOI: 10.1039/c8cs00335a transformations under mild conditions has emerged over the past decades. This review article aims at placing electrophilic amide activation in both a historical context and in that of natural product rsc.li/chem-soc-rev synthesis, highlighting the synthetic applications and the potential of this approach. Creative Commons Attribution 3.0 Unported Licence.
    [Show full text]
  • Pentachloride Hazard Summary Identification
    Common Name: PHOSPHORUS PENTACHLORIDE CAS Number: 10026-13-8 RTK Substance number: 1525 DOT Number: UN 1806 Date: August 1999 ----------------------------------------------------------------------- ----------------------------------------------------------------------- HAZARD SUMMARY * Phosphorus Pentachloride can affect you when breathed * Exposure to hazardous substances should be routinely in. evaluated. This may include collecting personal and area * Phosphorus Pentachloride is a CORROSIVE air samples. You can obtain copies of sampling results CHEMICAL and contact can severely irritate and burn the from your employer. You have a legal right to this skin and eyes with possible eye damage. information under OSHA 1910.1020. * Breathing Phosphorus Pentachloride can irritate the nose * If you think you are experiencing any work-related health and throat. problems, see a doctor trained to recognize occupational * Breathing Phosphorus Pentachloride can irritate the diseases. Take this Fact Sheet with you. lungs causing coughing and/or shortness of breath. Higher exposures can cause a build-up of fluid in the lungs WORKPLACE EXPOSURE LIMITS (pulmonary edema), a medical emergency, with severe OSHA: The legal airborne permissible exposure limit shortness of breath. (PEL) is 1 mg/m3 averaged over an 8-hour * Exposure to Phosphorus Pentachloride can cause workshift. headache, dizziness, weakness, nausea and vomiting. * Phosphorus Pentachloride may damage the liver and NIOSH: The recommended airborne exposure limit is kidneys. 1 mg/m3 averaged over a 10-hour workshift. * Phosphorus Pentachloride is a REACTIVE CHEMICAL and an EXPLOSION HAZARD. ACGIH: The recommended airborne exposure limit is 0.85 mg/m3 averaged over an 8-hour workshift. IDENTIFICATION Phosphorus Pentachloride is a white to pale yellow, WAYS OF REDUCING EXPOSURE crystalline solid with a pungent odor.
    [Show full text]
  • Pcls' Pocl3-VMR Patent Application Publication May 21, 2009 US 2009/0131653 A1
    US 20090131653A1 (19) United States (12) Patent Application Publication (10) Pub. No.: US 2009/0131653 A1 Ratnam et al. (43) Pub. Date: May 21, 2009 (54) GENERATION OF PHOSPHORUS (86) PCT No.: PCT/IN2006/000151 OXYCHLORIDE AS BY-PRODUCT FROM PHOSPHORUS PENTACHLORIDE AND DMF § 371 (OX1), AND ITS USE FOR CHLORINATION (2), (4) Date/1 Dec- 31, 2007 REACTION BY CONVERTING INTO (30) Foreign Application Priority Data VILSMEIER-HAACK REAGENT May 4, 2005 (IN) ......................... .. 545/MUM/2005 (75) Inventors: Rakesh Ratnam, Maharashtra (IN); Publication Classi?cation Aurora Sundeep, Maharashtra (51) Int Cl SE1); M‘illzamgifd M0?zuddm’ C07H 1/00 (2006.01) “as ra( ) 0070251/30 (2006.01) C d Add (52) US. Cl. ....................................... .. 536/124; 564/278 orrespon ence ress: THENATHLAWGROUP (57) ABSTRACT 112 south West street A process is described Wherein after formation of ?rst crop of AleXandria, VA 22314 (Us) Vilsmeier-Haack reagent by reacting Phosphorus Pentachlo ride With N,N-dimethylformamide to form a ?rst crop of 73 A - ; PHARMEDMEDICARE Vilsmeier rea g ent as insoluble c rY stals ’ a b YP- roduct of this ( ) sslgnee PRIVATE LIMITED Mumbai reaction, the Phosphorus Oxy-Chloride, reacts With N,N (IN) ’ dimethylformamide to give a second crop of Vilsmeier reagent. This second crop of Vilsmeier reagent is soluble in DMF. This process makes it possible to double the yield of (21) APP1- N04 11/919,826 chlorinated substrate, such as sucrose-6-acetate or sucrose-6 benZoate, from the same quantity of Phosphorus Pentachlo (22) PCT Filed: Apr. 28, 2006 ride : Mechanism of Combined Vilsmeier Reagent for the Chlorination of sugars.
    [Show full text]
  • United States Patent Office
    Patented May 31, 1949 2,471,472 UNITED STATES2,471.472 PATENT OFFICE METHOD OF FORMING PHOSPHONIC AND THOPHOSPHONCACD CHLORDES Willard H. Woodstock, Flossmoor, Ill., assignor to Victor Chemical Works, a corporation of Illinois No Drawing. Application April 28, 1945, Seria No. 590,956 6 Claims. (CI. 260-543) 1. 2 This invention relates to a method of form phonic acids. Such chloroalkyl esters and ing phosphorus compounds and the resulting alkenyl-1-phosphonic esters above methyl are new compounds, as are the phosphorus oxydi products,of alkenyl and phosphorus more particularly oxydichlorides to East and sulfo chloride compounds themselves. dichlorides from addition products of olefins and In Formula. A R represents an alkyl or aryl phosphorus pentachloride. group, and X represents hydrogen or alkyl or Unsymmetrical olefins, having a terminal aryl grOp. double bond, react with PCls to form phosphorus In Formula. B R is a normal alkyl group. addition products, and these addition products Suitable olefins for the (A) reaction include may then be reacted with phosphorus pentasul O styrene, alpha methyl styrene, alpha chloroSty fide or phosphorus pentoxide. rene, indene, isobutylene, 2.2.diphenyl ethylene, Type A olefins which have two alkyl groups di-isobutylene, and the isoalkylenes where two or an aryl group attached to the 2-carbon gen carbon atoms are attached to the number 2 car erally react with phosphorus pentachloride to bon. Such isoalkylenes include isoamylenes, iso add -Cl to the 2-carbon and -PCl4 to the 1.- . heptenes, iso-octenes, etc. carbon. Type B olefins which have only one Starting hydrocarbons of the (B) type include alkyl group on the 2-carbon atom generally re propylene, buttene-1, pentene-1, octene-1, etc.
    [Show full text]
  • Synthetic Methods of Phosphonopeptides
    molecules Review Synthetic Methods of Phosphonopeptides Jiaxi Xu State Key Laboratory of Chemical Resource Engineering, Department of Organic Chemistry, College of Chemistry, Beijing University of Chemical Technology, Beijing 100029, China; [email protected]; Tel./Fax: +86-10-6443-5565 Academic Editors: Graeme Barker and Simona Rapposelli Received: 8 November 2020; Accepted: 10 December 2020; Published: 12 December 2020 Abstract: Phosphonopeptides are phosphorus analogues of peptides and have been widely applied as enzyme inhibitors and antigens to induce catalytic antibodies. Phosphonopeptides generally contain one aminoalkylphosphonic acid residue and include phosphonopeptides with C-terminal aminoalkylphosphonic acids and phosphonopeptides with a phosphonamidate bond. The phosph- onamidate bond in the phosphonopeptides is generally formed via phosphonylation with phosphonochloridates, condensation with coupling reagents and enzymes, and phosphinylation followed by oxidation. Pseudo four-component condensation reaction of amides, aldehydes, alkyl dichlorophosphites, and amino/peptide esters is an alternative, convergent, and efficient strategy for synthesis of phosphonopeptides through simultaneous construction of aminoalkylphosphonic acids and formation of the phosphonamidate bond. This review focuses on the synthetic methods of phosphonopeptides containing a phosphonamidate bond. Keywords: phosphonamidate; phosphonopeptide; β-phosphonopeptide; γ-phosphonopeptide; peptide 1. Introduction Phosphonopeptides are phosphorus analogues
    [Show full text]
  • The D and the L Isomers of 00P"-DDT Project Director: Dr. R. D. Kihrough
    GEORGIA INSTITUTE OF TECHNOLOGY Engineering Experiment Station 0 PROJECT INITIATION Date: Project Title: The D and the L Isomers of 00 P"-DDT Project No.: B - 378 Project Director: Dr. R. D. Kihrough, Jr. Sponsor: Public Health Service . 1970 . Effective PCC9439r, XID 1969, ...... .. Estimated to run until: . • . Novembey Type Agreement: G111:1t. 1?0... 5P92:31-.03 ............... Amount;nt•. $ 11095* Reports: Terminal Progress Report due within six months after completion - ten copies. Contact Person: Dr. Otto A. Bessey, Chief Program, Dcv. and Eval. Branch Natl. Inst. of Env. 111th. Sci. National Institutes of Health U. S. Public Health Service Bethesda, Maryland 20014 *Excludes $129 to be transferred from unexpended balance of 13.61. Cost sharing requires additional *780; Cr.. panion Account =.:o. E-6o0-9144 Assigned to .... is41C1e4r .4-91.031 e4 PPierlce9 ..... Division COPIES TO: ❑ Project Director ❑ Photographic Laboratory ❑ Director ❑ Research Security Officer ❑ Associate Director ❑ Accounting ❑ Assistant Directoqs) a Purchasing ❑ Division Chiefs ❑ Report Section ❑ Branch Head ff.Library 0 General Office Services ❑ Rich Electronic Computer Center Engineering Design Services Itimp GEORGIA INSTITUTE OF TECHNOLOGY Engineering Experiment Station PROJECT TERMINATION Date 9/9/71 PROJECT TITLE: The D and the L Isomers of 0,P'-DDT PROJECT NO: PROJECT DIRECTOR: Dr. R. D. Eimbroughs Jr. SPONSOR: Public Health Service TERMINATION EFFECTIVE: 5/31/71 CHARGES SHOULD CLEAR ACCOUNTING BY: 7/31/71 Oblications Bemaininal Final Report - due 11/3/71 Dr. KintbrouGh) Final Patent Report - /WU CE111.) Nuclear & Diological Sciences Division COPIES TO: Project Director General Office Services Director Photographic Laboratory Associate Director Purchasing Assistant Directors Report Sectio Division Chief Library Branch Head Security Accounting Rich Electronic Computer Center Engineering Design Serviees 413:1- IC:UM tGl- X _it, INT C3 •X-• X WILT UV eCe 'X" M 43:E3E /41-1011 X.
    [Show full text]
  • United States Patent Office Patented July 9, 1968
    3,392,214 United States Patent Office Patented July 9, 1968 15 (preferably trimeric) with a phosphorus chloride selected 3,392,214 from the group consisting of phosphorus pentachloride CYCLOTRIPHOSPHAZATRIENE COMPOUNDS triphenoxy phosphorus dichloride and triphenyl phos- AND PROCESS FOR MAKING SAME phorus dichloride, and recovering the resulting product, Daniel J. Jaszka, Tonawanda, N.Y., assignor to Hooker Chemical Corporation, Niagara Falls, N.Y., a corpora- which may thereafter be polymerized to a useful polymer. tion of New York 20 Additionally, the process of this invention includes react- No Drawing. Filed Mar. 2, 1964, Ser. No. 348,877 ing diaminocyclophosphazene with phenol to form a 11 Claims. (CI. 260—927) phenolated diaminocyclophosphazene compound, which may be treated with a phosphorus chloride and This invention relates to cyclophosphazene products, polymerized. including polymers thereof, and to processes for preparing 25 The exact structure of some of the new intermediate them. products and final polymers produced by the processes of The prior art discloses that cyclophosphazene polymers this invention, has not been definitively established. How- which have good thermal stability have been made, but ever, it is believed that the following equations con- often such polymers are not as hydrolytically stable as is stitute correct representations of the reactions effected desirable. In fact, many such polymers have a very rapid 30 and the products formed according to this invention. Cl NEi CnHsO NHj CaHsO N=PC13 V V V ^ \ ^ \ ^ \ Cl N N Cl C.HtOH N NT OCjHs PCls N N OCiHs 300° C. M Jl/ > I 11/ • I Polymer p p KOH (C«H50)sP P (CSHSO)JP V \ ^ / \ ^ / \ .01 N NHj N.
    [Show full text]
  • Crystal Structure of Phosphorus Pentabromide
    No. 3686, JUNE 22, 1940 NATURE 971 conditions have been rather neglected by physicists, Formation of Aggregates and Structures particularly in recent years. In my experiments, a form of apparatus has been in Dilute Solutions of Hydrogen devised in which a metallic behows, closed by a Bentonites needle valve, contains the gas-free liquid under test, and the possibility of inward leakage of atmospheric A YIELD value is noticeable in hydrog,m bentonites air is avoided by completely surrounding the bellows at a concentration lower than that at which thixo­ and valve by the same liquid. The needle valve tropy first appears. This seems to happen generally being closed, tension is gradually applied to the with bentonites. Some natural calcium bentonites liquid by slowly filling a suspended can by means show coacervation1 • Coacervation of fine sub­ of a small jet of water. The water flow is turned off fractions of a natural bentonite has been reported• the moment a sudden downward movement of the at concentrations above the thixotropic range. can indicates that the liquid has broken. The can Hydrogen bentonites, however, show coacervation is then weighed complete with the contained water, over a wide range and even below the thixotropic and the tension which existed in the liquid imme­ range of concentrations. Near about the concentra­ diately prior to breaking is calculated from the tion at which yield value becomes noticeable a sharp known effective cross-section of the bellows. change in several properties has been observed. The liquids so far examined by this method are The cataphoretic velocity rapidly increases and tends alcohol, ether and lubricating oil.
    [Show full text]
  • Enthalpy of Formation of Phosphorus Pentachloride; Derivation of the Enthalpy of Formation of Aqueous Orthophosphoric Acid
    ----. -- --------~ .1 JOURNAL OF RESEARCH of the National Bureau of Standards-A. Physics and Chemistry Vol. 78A, No.3, May-June 1974 Enthalpy of Formation of Phosphorus Pentachloride; Derivation of the Enthalpy of Formation of Aqueous Orthophosphoric Acid R. H. Schumm, E. J. Prosen, and D. D. Wagman Institute for Materials Research, National Bureau of Standards, Washington, D.C. 20234 (February 1, 1974) When chlorine (real gas, 980 mmHg) combines with white (a) phosphorus to form phosphorus pentachloride at 24.89 °C, 3986.3±2.7 J of heat are liberated per gram of stoichiometrically equivalent Mg,P,07. This value was determined by a dead-ended flow system in an electrically calibrated isoperi­ bol calorimeter. Correction was made for the formation of up lU one Ifwl percent PCb in the products; no other impurities were found. From this value, the standard (25 °C, ideal gas) enthalpy of formation of PCIs(c} is calculated to be -443.85 ± 0.30 kl/mol, - Hl6 .08± 0.07 kcal/mol. When this figure is combined with a recent determination of the enthalpy of hydrolysis of PCIs(c}, the standard enthalpy of formation of HaPO, (aq, 100 H,O) is calculated to be -1296.5 ± 1.5 kl/mol, in good agreement with two other values which involve the formation .and hydrolysis of P,O,. (hex). A "best value" is suggested: IiHF (H 3 PO" 100 H2 0} = - 1295.8 ± 1.3 kJ/mol, - 309.7 ± 0.3 kcal/mol. Key words: Enthalpy of formation; phosphoric acid; phosphorus pentachloride. 1. Introduction 2. Materials The direct chlorination of phosphorus, followed by The white (0:) phosphorus employed in the present dissolution in water of the resulting phosphorus penta­ work was obtained by fractional sublimation, with chloride, provides a convenient thermochemical path continuous re moval of impurities, at room temperature to aqueous orthophosphoric acid.
    [Show full text]
  • The Action of Xulphuryl Chloride on Organic Substances. Part I. Simple Monosubstituted Benzenes. by THOMASHAROLD DURRANS
    View Article Online / Journal Homepage / Table of Contents for this issue 44 DWRXANS: THE AOTION OF SULPHURYL CHLORIDE Published on 01 January 1922. Downloaded by University of Warsaw 22/10/2014 12:30:46. IX.-The Action of Xulphuryl Chloride on Organic Substances. Part I. Simple Monosubstituted Benzenes. By THOMASHAROLD DURRANS. SULPHURYLchloride reacts readily with a large number of organic substances, generally functioning either as a chlorinating or as a dehydrating agent. Its action as a chlorinating agent is frequently, but not always, similar to that of chlorine, and sometimes to that of phosphorus pentachloride, whilst in its dehydrating action it resembles sulphur trioxide. Thus, in the absence of a catalyBt, it View Article Online ON ORGANIC SUBSTANCES. PART I. 45 chlorinates benzene, toluene, phenol, anisole, phenetole, or aniline, and with salts of acids, such as sodium benzoate or acetate, it yields the corresponding acid anhydride and acid chloride (compare Dubois, Bull. Acud. roy. Belg., 1876,42, 126 ; Wohl, D.R.-P. 139552 ; Wenghoffer, Ber., 1877, 10, 441; Peratoner, Guxxetta, 1894, 24, i, 236). Although a large amount of work has already been done in this connexion, there is a lamentable lack of information regarding the action of sulphuryl chloride on the organic substances in common use. This investigation is designed to contribute a small addition to our existing knowledge in this direction. The conditions of experiment have been those obtaining when the organic substance is boiled under atmospheric pressure for several hours with a large excess of sulphuryl chloride; consequently the products isolated represent the final products to be obtained in such circumstances, the isolation of any intermediate product not having been aimed at.
    [Show full text]
  • New Regs Announced for Securing High-Risk
    Number 586 April 9, 2007 Client Alert Latham & Watkins Environment, Land & Resources Department Department of Homeland Security Announces New Regulations for Securing High-Risk Chemical Facilities Summary effective 60 days after publication in the Federal Register, the Department The Department of Homeland Security has sought additional comment within plans to impose new requirements on 30 days on one key component of the chemical facilities that possess listed regulations. chemicals above specified quantities, and in many cases will require facilities What Facilities Are Affected? to prepare vulnerability assessments, develop security plans, and implement Under these regulations, the Department and install a suite of security measures. will screen tens of thousands of These requirements could begin to take “chemical facilities” for vulnerability We recommend effect for certain facilities as early as ” to and potential consequences of a June 2007. that all companies terrorist attack, and will regulate that possess or those it determines to be “high-risk.” otherwise handle Background “Chemical facility” is defined broadly as “any establishment that possesses or chemicals review In the four and a half years since the plans to possess, at any point in time, the regulations.“ terrorist attacks of September 11, 2001, a quantity of a chemical substance Congress has debated, but until recently determined by the Secretary to be failed to pass, legislation regulating the potentially dangerous or that meets security of chemical facilities in the US. other risk-related criteria identified On October 4, 2006, the Department by the Department.” A “high-risk” of Homeland Security Appropriations facility is one which, “in the discretion Act of 2007 (the Act) was signed into of the Secretary of Homeland Security, law.
    [Show full text]
  • United States Patent Office Paterated Mar
    3,311,602 United States Patent Office Paterated Mar. 28, 1967 2 aromatic groups with an excess of alkyl chloromethyl 3,311,602 ether in the presence of a halomethylation catalyst, that PROCESS FOR THE CHLOROMETHYLATION OF AROMATIC HYDROCARBONS improved reaction rates, conversions, and yields are ob Charles F. Raley, Jr., Midland, Mich., assignor to The tained under mild conditions with low catalyst concen Doy Chenaica: Company, Midland, Mich., a corpora 5 trations by adding to the chloromethylation reaction mix tion of Delaware ture a catalyst regenerator selected from the group con No Drawing. Filled July 1, 1963, Ser. No. 292,131 sisting of silicon tetrachloride, titanium tetrachloride, ii Ciaims. (C. 260-93.5) sulfur trioxide, oxalyl chloride, phosphorus pentachloride, thionyl chloride and sulfuric acid, in an amount sufficient This invention relates to an improved process for the O to regenerate the catalyst. chloromethylation of aromatic materials with an alkyl To illustrate the unexpected and highly beneficial re chloromethyl ether and catalyst. More particularly, it Sults of this regenerative chloromethylation process, es relates to such a process wherein improved reaction sentially complete monochloromethylation of a linear rates, conversions, and yields are obtained by regenerating polystyrene was obtained in 6 hours at room temperature the activity of the catalyst during chloromethylation. 5 by the addition of 0.5 mole of silicon tetrachloride (SiC) Chloromethylation of aromatic materials to substitute per equivalent of polystyrene to a reaction mixture con a chloromethyl group for a nuclear aromatic hydrogen is taining 5 moles of chloromethyl methyl ether and 0.1 mole an important and versatile synthetic process applicable of zinc chloride per equivalent of polystyrene.
    [Show full text]