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An experimental study of the phosphorus chloronitrides and their reactions with trimethylamine

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An experimental study of the phosphorus chloronitrides and their reactions with trimethylamine

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Content AN EXPERIMENTAL STUDY OP THE PHOSPHORUS CHLORONITRIDES AND THEIR REACTIONS WITH TRIMETHYLAMINE A Thesis Presented to the Faculty of the Department of Chemistry University of Southern California In Partial Fulfillment of the Requirements for the Degree Master of Scienee by J. Calvin Taylor June 1940 UMI Number: EP41521 All rights reserved INFORMATION TO ALL USERS The quality of this reproduction is dependent upon the quality of the copy submitted. In the unlikely event that the author did not send a complete manuscript and there are missing pages, these will be noted. Also, if material had to be removed, a note will indicate the deletion. UMT "CBwarttfonP W^J-ng UMI EP41521 Published by ProQuest LLC (2014). Copyright in the Dissertation held by the Author. Microform Edition © ProQuest LLC. All rights reserved. This work is protected against unauthorized copying under Title 17, United States Code ProQuest LLC. 789 East Eisenhower Parkway P.O. Box 1346 Ann Arbor, Ml 48106- 1346 This thesis, written by Jf ....CALVIIi..miLOR............. 3^® under the direction of h.is Faculty Committee, Dean Secretary Date.JM ^..1940 I l l t f j and app ro ved by a ll its members, has been presented to and accepted by the Council on Graduate Study and Research in partial fulfill- ment of the requirem ents f o r the degree of MASTER OP SCIENCE Faculty Committee TABLE OF CONTENTS CHAPTER PAGE I. INTRODUCTION AND PURPOSE....................... 1 The purpose........................... 3 Statement of purpose ..................... 3 Importance of s t u d y ................... 3 Organization of remainder of thesis ........ 6 II. REVIEW OF THE LITERATURE..................... 7 Literature on early history of phosphorus chloronitride ................. 7 Literature on the preparation of phosphorus chloronitride ........... . . . 8 Properties of phosphorus chloronitrides . . . 9 III. EXPERIMENTAL PART ....... 13 Preliminary technique................... 13 Preparation of drying tubes .............. 13 Preparation of phosphorus chloronitride....................... .. . 14 Preparation of trimethylamine............ 16 Research Part................................ 20 Work on the trimer....................... 20 Work on the tetramer..................... 30 ili CHAPTER PAGE Work on the polymer..................... 33 IV. INTERPRETATION OP RESULTS ................... 38 Problems for future study ................. 43 V. CONCLUSIONS............................... . * . . 44 BIBLIOGRAPHY ................................ 46 LIST OP TABLES TABLE PAGE I. Weighing Method of Adding Trimethylamine to Phosphorus Chloronitride Trimer . . . 26 II. Decomposition of 1:1.9 Phosphorus Chloronitride - Trimethylamine Com pound * ................. 29 LIST OP FIGURES FIGURE PAGE 1* Apparatus Used In Preparing Phosphorus Fentachloride ......... .......... • 15 2* Apparatus Used in Separation of Trimer from Tetramer................................... 15 3. Apparatus Used in Initial Preparation of Trimethylamine ................ ....... 18 4. Apparatus Used in Final Preparation of Trimethylamine........................ 18 5. Apparatus Used for the Three Months' Reaction of the Rubbery Polymer.......... 35 6* Sulfuric Acid Tube Used for Trapping Trimethylamine............................. 35 CHAPTER I INTRODUCTION AND PURPOSE There are many organic compounds having a tendency to polymerize. This polymerization is controllable to some extent, A typical example of this is the organic rubber molecule. Inorganic compounds also tend to polymerize, but their polymerization often is not well understood and is usually very difficult to control. One of these inorganic compounds whose polymeriza tion is difficult to control is phosphorus chloronitride, * which should have PNClg as its formula in the monomeric state. The only known forms of phosphorus chloronitride are the trimer, (PNClg)g, the tetramer, (PNClg)^, the pentamer, (PNClg)5, the hexamer, (PNClg)g, and the polymer, (PNClg)^. The high polymer might be termed an inorganic rubber, due to its elasticity, which is very similar to ordinary rubber. When an inorganic compound such as phosphorus chloronitride is found to have a characteristic (in this case, elasticity) generally assigned only to organic chemicals, this fact alone Is enough to arouse interest in the compound. It might be pointed out that phosphorus chloronitride is the nitrogen analog of phosphorus oxychloride, POClg. The forms of phosphorus chloronitrides most easily obtained are the trimer, the tetramer, and the higher poly mer. It is believed that the trimer and tetramer have the ring structures: Cl. .Cl H ^ ^ N C1^p ^ p^ 1 c i . H Kgi 01 // \C1 yP P\ N N C1 \ '/ 01 01^ p p£ci N 01x ^ . N01 N while the polymer probably is a combination of both rings and chains.'*' The trimer and tetramer are white, crystal line solids, while the polymer is a darker, thick, syrupy liquid, which, upon standing, becomes rubbery and eventual ly quite hard. Most of the previous work on the phosphorus chloroni tride s has been confined to the trimer and the tetramer. The work that has been done on these compounds has consisted mainly of replacement reactions with primary and secondary amines, water, and the G-rignard reagent. Some work has been done with pyridine, which is a tertiary amine, but this substance was used only as a solvent and not studied from the standpoint of its reactions with phosphorus chloroni tride.2 Armand M* de Fiequelmont, "Polymerization of (PFClo) Compt. rend., 204: 867-9, 1937. p f f R. Schenk and K6mer, "Preparation and Discussion of (PNC12)x" Beriohte. 57: 1343-55, 1924. I. THE PURPOSE 3 Statement of Purpose. The chief purpose of this work was to learn whether a tertiary amine, such as trimethyl amine, (CH3)3N, would form any addition compounds hy reac tion with phosphorus chloronitrides. Trimethylamine might add direetly to the ring, and, if so, the number of mole cules added, and the stability of the linkages would be stud ied. On the other hand, the amine might break the ring; in that case, one might gain some control of the polymerization of the phosphorus chloronitrides. Importance of the stud?. Trimethylamine has two un shared electrons attached to the nitrogen; E • ■ H H ’ .C ; N ; C:H H H H-C: H H In the phosphorus chloronitride, using the trimer as an example, there is supposed to be double bonding between phosphorus and nitrogen; thus, the phosphorus would have % five bonds as is usual in pentavalent phosphorus. It may be possible that phosphorus can hold as many as six bonds, which would give it a bond number of six. There are sever al stable ions of phosphorus known where phosphorus has a 4 coordination number of six, sueh as the PFg ion. If the trimethylamine would attach directly to phosphorus without breaking the ring, this would give phosphorus a bond number of six. There is also the question as to whether all the phosphorus in the compound could hold six bonds, or if just a limited number of phosphorus atoms could hold six bonds. As for the addition compounds attached directly to the ring, in the case of the trimer, there are three possibilities: Cl Cl C1nIxN(CH3)3 Cl^NtCH^ ^ P * / P ^ N N N N Cl. I I I 01 Cl I I I Cl r ^ p p- ci 01 N N '/ X01 01^ ^ ** N(0H3)3 Cl 01sl,K<CH3>3 Clx I I I Cl Cl — p p<~ Cl (ch.).a' v // n(ch3)s N In all three of these cases the electrons holding the tri methylamine to the phosphorus would come from the unshared pair of the trimethylamine molecule. As mentioned previous ly, one wants to see, also, if trimethylamine, instead of adding directly to the ring, breaks the ring down. If this is the case, the ring would break as shown below, again using the trimer as an example: 9\ P^C1 N ^ ^ N c ij l »;ci / p G1 * // NC1 ' N This would give phosphorus five pairs of electrons around it. The electrons between the nitrogen of the trimethyl amine and the phosphorus again come from the unshared pair in the trimethylamine; hence, one would have: Cl- (h3c)3n : P : Cl N: Of course, if phosphorus can have a bond number of six, it may be possible to attach two molecules of trimethylamine, givingi Cl . Cl (h3c3)n ;' p'; n(ch3)3# N As for the aforementioned control of polymerization, if the trimethylamine breaks down the ring in the cases of the trimer and tetramer, it may be possible to break down the rings and chains in the case of the polymer, and give a compound of phosphorus chloronitride monomer to one or two molecules of trimethylamine. If this is true, the same form will have been obtained from the polymer as from the trimer, and thus some degree of permanent depolymerization 6 might be accomplished by the amine. II. ORGANIZATION OF REMAINDER OF THESIS The following chapter will contain a brief history of the phosphorus chloronitrides, mentioning their properties and the different methods used in their preparation. Another , chapter will be given to experimental technique used in this research and to the results obtained. In this experimental chapter it will be shown that the trimer, the tetramer, and the high polymer of phosphorus chloronitride did react with trimethylamine, giving in all cases a very stable product. All these polymeric forms gave compounds having trimethyl amine and phosphorus chloronitride monomer present in ap proximately a one-to-one ratio. The trimer also gave a compound of two molecules of trimethylamine to one molecule of phosphorus chloronitride monomer. Chapter IV will interpret the results of the experi mental work showing that in all probability the ring struc ture of phosphorus chloronitride was broken. This chapter will also contain a brief discussion of the problems that can be used for study and research at some future date. The final chapter will contain a summary of the results. CHAPTER II REVIEW OF THE LITERATURE Much has been written on the preparation of phosphor us ehloronitrid.es and on their physical properties. A great deal has also been written on their reactions with primary and secondary amines and with water, but here only a brief summary of these facts will be presented with a complete bib liography for those who care to look into the literature further. Literature on early history of phosphorus chloroni tride s. It was found by Liebig and Wohler in 1852 that the action of ammonia gas upon phosphorus pentachloride pro duced a new compound.'1 ' Laurent gave the compound the form ula PHClg, and the correctness of this was confirmed by Gladstone and Holmes, but Wichelhaus determined the molecu lar formula by vapor density measurements and found the compound to be the trimer of phosphorus chloronitride; name- p ly, (PlfClg)^. Stokes isolated this trimer and also the - i • • x R. Schenk and Romer, "Preparation and Discussion of (PNC12)x,m Berichte, 57: 1343, 1924 2 Loc. cit. 8 3 tetramer of phosphorus chloronitride. Wiehelhaus assumed 4 the formula to be: ClgPN ----- NPClg \ / N PGlg It was decided that thia was probably not the correct struc ture because the phosphorus chloronitride, being a stable compound, could not have a tri-nitrogen ring in its struc ture, as that would undoubtedly make the compound explosive in nature. Stokes brought forward the structures that we consider correct today. Literature on the preparation of phosphorus chloroni- £ tride. Stokes heated a mixture of phosphorus pentachloride and ammonium chloride to 120° - 150° C. in a bomb tube from which hydrogen chloride gas had to be removed at short in tervals. He obtained small yields of a buttery mass of phosphorus chloronitride. •* y Schenk and Romer used an acid-proof autoclave in 4Loc. cit. 5Loc. cit. ®A. Stokes, ”Chloronitrides of Phosphorus,” Amer. Chem. J., 17: 276-7, 1895. * • 7Schenk and Romer, Op. cit., pp. 1348-50. 9 which they placed phosphorus pentachloride and ammonium chlor ide and heated them suddenly to 120° C. The hydrogen chlor ide gas was released at 25 atmospheres pressure. They ob tained the raw phosphorus chloronitride polymer, from which the trimer and tetramer were separated by vacuum distilla tion. ** 8 Schenk and Romer devised a new method for preparing phosphorus chloronitride by use of an inert solvent having a boiling point near the reaction temperature of phosphorus pentachloride and ammonium chloride. The solvent used was tetrachloroethane. By this method, the phosphorus chloroni tride polymer was obtained, and the trimer and tetramer were isolated by vacuum distillation. This method is the one used by the author. Properties of the phosphorus chloronitrides. The phosphorus chloronitride trimer is a white, crystalline sub stance having a melting point of 114° C. The tetramer is also white and crystalline and melts at 123° C. The polymer, when allowed to stand at room temperature, is amber colored and very rubbery. The trimer and tetramer can be distilled under reduced pressure and have boiling points of 124° C. 8 > P* 1351. 1 0 o 9 and 185 C., respectively, at ten millimeters pressure. In the absence of. the polymer the trimer and tetramer do not polymerize rapidly below 350° C., but they do polymerize quite rapidly below 200° C., if the polymer is present.1^ The polymer, at red heat, becomes a black, horny mass, with a large capability of resisting all chemical agents. The original work on the above properties was done by A. Stokes!1 - p Stokes said that at high temperatures the polymer could be depolymerized to give the pentamer and hexamer of 13 phosphorus chloronitride. A. de Ficquelmont obtained the same results as Stokes with the polymer, and he stated that the trimer and tetramer also are »produced. He said that the 14 velocity of the depolymerization was very slow. Schenk and his co-workers were unable to depolymerize the higher polymer, even at red heat or by vacuum distillation. In the current experimental work, heating of the polymer was ^ R. Schenk and Romer, 0£. cit., pp. 1350-53 10 !££• cit. H A. Stokes, 0£. cit.t pp. 275-90. A, Stokes, ^Chloronitrides of Phosphorus,” Amer. Chem. J., 19: 782-96, 1897. 12 hoc, cit. 13 r t Armand M. de Ficquelmont, "Polymerization of (PNC12)x ,w Compt. rend., 204: 867-9, 1937. 3-4 Schenk and Romer, Ojs. cit., pp. 1350-55. 11 tried and some of the lower polymers were obtained, although they were not specifically identified. It seems probable that these lower polymers are not actual products of depoly merization of higher polymers, but are dissolved in the high er polymer and merely distil out upon heating* The reactions of the trimer and tetramer with primary and secondary amines have been studied by a number of workers. 15 Stokes found that the action of ammonia solution upon phos phorus chloronitride, trimer, and tetramei; gave an amine of the formula P^N^Cl^(NHg)g. Besson and Rosset,^"® using dry ammonia, replaced all the chlorine atoms and obtained an in soluble PN(NHg)g, which probably was the trimer. Schenk and 17 Romer stated that any compound containing an NH group would replace all the chlorine atoms, if the reaction were 18 done in dry benzene. Schenk and Romer used pyridine, a tertiary amine, as a solvent and obtained no reaction with phosphorus chloronitride when the pyridine was absolutely dry. This was the extent of the literature that could be found on tertiary amines and phosphorus chloronitride. 15 A. Stokes, Op. cit. Besson and Rosset, "Action of on (PNClp),," Compt. Rend., 146: 1149-55, 1908. ^ r * * • 17 Schenk and Romer, Op. cit. 18 Loc. cit. 12 The trimer and tetramer are not easily soluble in water, probably because they are difficult to wet. Upon con tinual contact and shaking with water, they react with wat er forming what Stokes called f,tri and tetra meta phosphimic X acids.1 1 Stokes has written several articles on this subject. on H. Rosset studied the action of the Grignard re agent, phenyl magnesium bromide, on phosphorus chloronitride trimer, in dry toluene and replaced the chlorine atoms on the ring by phenyl groups. He claims to have obtained All the above mentioned literature shows how much work has been done on the phosphorus chloronitrides along replacement lines, and how little has been done along lines of addition products and bond numbers of phosphorus. All this only makes more evident the need and importance of a study of an inorganic polymer, such as phosphorus chloroni tride, along these lines. A. Stokes, "Tri meta phosphimic acid,1 1 Amer. Chem. J., 18s 629-665, 1896. A. Stokes, "Tetra meta phosphimic acid," Op. cit. pp. 780-9. A. Stokes, "Meta phosphimic acids," Op. cit., 20: 740-760, 1898. H. Rosset, "Reactions of (PHClgJg with the Grig nard Reagent," 0ompt. rend., 180: 750-1, 1925. CHAPTER III EXPERIMENTAL PART This chapter will he divided into two parts. In the first part, the technique used in preparing the re agents and the apparatus that was necessary to carry on the research will he described. Part number two will con sist of the technique used for the actual research experi ments. I. PRELIMINARY TECHNIQUE Preparation of drying tubes. Calcium chloride, due to its reaction with trimethylamine, could not he used as a drying agent for the amine. Phosphorie anhydride could he used satisfactorily; however, it could not he added direct ly to the drying tube because of its strong affinity for water. The most satisfactory way found for using phosphoric anhydride was to place it in a dry Erlenmeyer flask con taining glass heads. The glass heads, then covered with phosphoric anhydride, are added to the drying tube. Glass wool Is used at both ends of the drying tube to hold the heads In place. These tubes should not he left open to the atmosphere any longer than necessary. 14 Preparation of phosphorus chloronitride. Although the method used in the preparation of phosphorus chloroni- * • I tride is almost identical with that of Schenk and Romer, it will be described here in detail as a matter of conven ience to the reader who may be Interested in the preparation. In a two-liter, round-bottom flask was placed 168 cubic centimeters of phosphorus trichloride, and to this was added one liter of tetrachloroethane, the solvent. One hundred cubic centimeters of liquid chlorine was re moved from a chlorine tank and kept in a liquid state by placing it in a bomb tube immersed in a cooling medium of pulverized solid carbon dioxide (dry ice) and ether. This 100 cubic centimeters of chlorine was allowed to distil into the phosphorus trichloride-tetraehloroethane solution, as shown in Figure 1. The phosphorus pentachloride formed was not entirely soluble in the tetrachloroethane, but as it was used in its reaction with ammonium chloride, it gradually went into solution. A reflux condenser with a calcium chloride drying tube, to keep back atmospheric moisture, was attached to the round-bottom flask. A de livery tube was also attached from the drying tube to the sink to remove the escaping hydrogen chloride gas. . . •• x R. Schenk and Romer, ’ Preparation and Discussion of (PIC12)X,” Berichte. 57: 1347-8, 1924. 15 Liquid chlorine Phosphoric anhydride dry ing tuhe Chlorine trap Dry ice & ether Tetrachloroethane and phosphorus trichloride ■>" To vacuum Figure 2 16 The solution was warmed slightly to remove any excess chlor ine that may have "been added. To the solution was added 120 to 130 grams of dry, finely powdered ammonium chloride. The solution was refluxed, with the aid of an oil hath at 140° to 150° C., for approximately twenty hours, during which time the following reaction took place: n(P016 +■ NH4C1) = (PUCl2)n - ( - 4n HC1 After cooling, the excess ammonium chloride was filtered off and the solvent was removed by distillation at 60° C. and 18 millimeters pressure. The remaining liquid was a thick crystalline mas3 containing an oil. The trimer and tetramer were removed from the oil by stirring and placing the mass in a Buechner funnel and pulling off most of the oil by vacuum. The oil left on the trimer and tetramer was removed by careful washing with ice cold benzene. The trimer and tetramer were re-crystallized from benzene and then were separated by distilling off the trimer at 135° C. and 18 millimeters pressure. The ap paratus used is shown in Figure 2. After several days, the oil had already polymerized to a rubbery material. Preparation of trimethylamine. Pure trimethylamine has a boiling point of 3.5° C. at 760 millimeters pressure, so the commercial way of selling it is in a water solution. The stock supply of trimethylamine used in this work, was approximately 75 percent water and 25 percent trimsthyl- amine. The pure trimethylamine was obtained from the water solution by a series of distillations, accomplished ultimate ly by the aid of freezing mixtures of dry ice in ether. The product was stored in a sealed tube, whose capacity was limited by the size of the Dewar cylinder employed as a con tainer for the freezing mixture. Because of this limita tion of volume, the pure trimethylamine had to be prepared from the stock supply several different times. These sev eral preparations were accomplished by the cooperation of co-workers in related research in the same laboratory. Be cause of the disagreeable odor of trimethylamine, all the work dealing with it was done under a fume hood. Approximately 550 cubic centimeters of stock supply trimethylamine was placed in a 500 cubic centimeter distill ing flask connected to a bomb tube, having a bath of ice, salt, and hydrochloric acid as a cooling medium. This ap paratus is shown in Figure 5. The trimethylamine was distilled off until the temperature reached about 70° C. The bomb tube, now con taining the trimethylamine, was connected to another bomb tube in a dry ice and ether bath, and the trimethylamine 18 Trimethylamine _ solution Dewar flask Figure 3 Figure 4 1 9 was allowed to distil over into the second bomb tube* This trimethylamine was allowed to distil again, but this time a phosphoric anhydride drying tube was placed between the two bomb tubes, as shown in Figure 4* Some phosphoric anhydride was sublimed into a clean, dry bomb tube. Into this bomb tube, immersed in dry ice and ether, the trimethylamine was distilled for the final time, through a phosphoric anhydride drying tube. This bomb tube was then sealed and allowed to stand at room temperature, with occasional shaking. It has been found that phosphoric anhy dride, besides removing the last traces of water from the trimethylamine, also reacts with any dimethylamine and monomethylamine that may be present and thus removes them o from the solution. The vapor pressure of the first supply of trimethylamine was 68S.5 millimeters at 0° C., with the mercury at 22° C.; this, when corrected to 0° C., was 680.1 3 millimeters, which Simon and Huter reported as the correct- 4 ed vapor pressure of pure trimethylamine. 2 Preston D. Ingram, Unpublished Master’s Thesis* The University of Chicago Libraries, 1939* 3 Tested by Doctor Burg. University of Southern California. 4 Simon and Huter, Zeit. Elch. Chemie, 41:32, 1935. II. RESEARCH PART 20 In selecting trimethylamine as the tertiary amine with which to carry on this work, two factors were taken into consideration: (1) steric hindrance and (2) ease of handling. Trimethylamine has the smallest molecule of any tertiary amine, so its two unshared electrons are not surrounded hy the molecule itself. It can he transferred from one homh tube to another hy merely warming to room temperature; hence, it meets hoth of the requirements men tioned. There have heen a number of individual experiments on the trimer, the tetramer, and the polymer of phosphorus chloronitride. In the following descriptions the experi ments will he numbered In a logical rather than chronologi cal order. The experiments will he referred to in groups for convenience in correlating for results. Work on the trimer. Experiment I. Into a homh tube was placed several grams of the phosphorus ehloroni- tride trimer. To this bomb tube in a hath of dry ice and ether was added an excess of trimethylamine. The method of adding the trimethylamine was the same as used in pre paring the pure trimethylamine and described by Figure 4. This bomb tube was then sealed and allowed to warm to room temperature. The crystalline trimer soon changed to a 21 more flocculent, white solid. After standing for several days at room temperature, the tube was opened and the ex cess trimethylamine was removed hy the same technique as that used in introducing it. The solid left in the tube appeared to be much more voluminous than the original trimer. Part of the solid was analyzed for nitrogen by the Kjeldahl method. The result obtained was 15.44 percent nitrogen. It might be well to point out at this time that the pure phosphorus chloronitride has 12.0 percent nitrogen, while a compound of one molecule of trimethylamine to one of the phosphorus chloronitride monomer contains 16.1 per cent nitrogen. It was noted that after the excess triemthyl- amine had been removed and the pressure in the bomb tube was equal to atmospheric pressure, the bomb tube showed a reduction of pressure after standing several days. Experiments II and III. The same method and tech nique were used for Experiments II and III as for Experiment I except the bomb tubes with the trimethylamine were allowed to stand for over one week. A Kjeldahl determination was made on each and the results were 16.44 percent and 16.73 percent nitrogen, respectively. Again the bomb tubes showed a reduction of pressure upon standing. These reduced pressures seemed to show that the trimethylamine vapor left in the bomb tube, when the excess had been removed, 22 reacted with the compound, hence giving the vacuum. In Experiment II a rough determination of the residual pres sure, hy an attached manometer, gave a value between ten and twenty millimeters. The compound formed with the trimethylamine in Experiment II did not melt at any temp1 - erature below 285° C., but there was a noticeable shrinkage in the volume of the compound in the melting point tube. After these results on the trimer a different tech nique was used. In this new technique the amount of tri methylamine added to the compound was determined by the gain in weight of the bomb tube instead of analysis of the product. Experiment IV. A sample of trimer was added to an accurately weighed bomb tube and the weight determined. An excess of trimethylamine now was added as described in Experiment I. In the sealing of the tube the glass removed was accurately weighed. After the trimer had remained in contact with the trimethylamine for several days, the ex cess was removed and all the pieces of tubing removed were again weighed. The bomb tube was closed to atmospheric moisture by placing on the neck of the tube a weighed rub ber tube closed by a pinch clamp. The results showed that 0.0255 moles of trimethylamine were added to 0.0245 moles of phosphorus chloronitride monomer, or a ratio of l.to 1,04* This bomb tube also showed a reduction of pressure, 23 and by using a manometer the residual pressure measured 13 millimeters. Experiments were now tried to find out why the trimethyl amine in the bomb tube atmosphere always reacted completely with the new compound formed, but there seemed to be just slightly more than a one-to-one compound formed when trimethyl amine was present in the liquid state under pressure and when the bomb tube was not heated above room temperature, no mat ter how long the sealed bomb tube was allowed to stand. Experiment V. Trimethylamine was again added in the usual manner to the weighed bomb tube of Experiment IV con taining the weighed, approximately one-to-one compound. This was done to see if enough trimethylamine could be added so that the pressure would not be lowered after the excess trimethylamine had been removed. The bomb tube was sealed and the piece of glass thus removed was weighed. The bomb tube was heated at 55° C. for five hours. It was thought unsafe to heat the bomb tube to a higher tempera ture. The excess trimethylamine was again removed and the increase in weigjit checked. It was found that 0,0113 moles of trimethylamine were added, giving a total of 0.0368 moles of trimethylamine added to the original phosphorus 5 chloronitride put in the tube. This now gave a ratio of 5 i.e., 0.0245 mole of PNC12 held 0.0368 mole of N(CH3)3. 24 phosphorus chloronitride monomer to trimethylamine of 1 to 1.5. After four days the bomb tube again showed a lowering of pressure, indicating that the compound still was absorbing trimethylamine. Experiment VI. A method of supplying trimethylamine vapor continuously to the bomb tube now was tried. The weighed bomb tube used in Experiments IV and V, with the 1 to 1.5 compound in it, was connected to a bomb tube of trimethylamine in a bath at 0° C. The weighed bomb tube was kept at room temperature. A phosphoric anhydride dry- o ing tube was placed in the system. At 0 G. trimethylamine has a vapor pressure of about 680 millimeters pressure. Prom the ''T1 1 tube connection, at the weighed bomb tube, a vacuum was applied. This vacuum was just enough to remove any air from the system and reduce the pressure so tri methylamine vapor would fill the apparatus. If more tri methylamine reacted with the phosphorus chloronitride com pound, it would reduce the pressure and bring more tri methylamine over. This experiment was carried on for six days, and at the end of that time, the system was closed and it was found that the phosphorus chloronitride compound no longer absorbed trimethylamine. The bomb tube was again weighed and more trimethylamine was found to have been added. Now the ratio of components of the material in the bomb tube was one part phosphorus chloronitride monomer to 1,9 parts of trimethylamine. Table I shows the type of table kept for Experiments IV, V, and VI. The next question was to find out how stable this com pound was. Experiment VII. The bomb tube containing the 1: 1,9 compound was connected to a vacuum pump capable of lowering the pressure to 0.5 to 1 millimeters. The compound was sub jected to this vacuum at temperatures from room temperature to 285° C. At each 50° C, rise in temperature the bomb tube was removed and weighed. There was very little loss in weight until 260° C. had been reached. At 260° C, the solid in the bomb tube appeared to grow smaller and agitat ed itself, as if a gas were given off. The odor of tri methylamine coming from the pump also was obvious. The bath temperature was held at 260° C. until it was apparent that no more gas was coming off. The bomb tube was then weighed and the loss in weight was approximately equal to the gain in weight in Experiments V and VI. In other words, all the trimethylamine put on after the one-to-one compound had been obtained, had come off at 260° C, The bomb tube was heated again and at 280° to 285° C, it was again obvious that a gas was coming off. Here the odor of trimethylamine was again present and part of the solid would sublime and 26 TABLE I WEIGHING METHOD OF ADDING TRIMETHYLAMINE TO PHOSPHORUS CHLORONITRIDE TRIMER Experiment IV. Volume of bomb tube............... 56 cc. Wt. of bomb tube empty......... 37,986 gms. Wt, of bomb tube (PNClg)3 ............ 40.841 Wt. of (PNClg)3 used.......... 2.855 Wt. of glass removed in bomb tube seal. . 2.185 Wt. of rubber tube -j- pinch clamp . 19.894 Wt. of bomb tube removed when cut open. . 1.877 Wt, of bomb tube PNClg - (CEg^N com pound f- rubber tube -f pinch clamp - f - (CHg)gN atmosphere .................. . . 58.250 Gain in wt. due to (CH3)3N atmosphere in stead of air in bomb t u b e ............. 0.072 Total wt. removed due to seals. ..... 4.062 Wt. of original bomb tube +- (PNClg)3 +■ rub ber tube and clamp -I-gain in wt. due to (CH3)3N — wt. of glass removed in seals . 56.745 Gain in wt. due to addition of (CHgJgN . 1.505 Moles of original PNClg monomer......... 0.025 Moles of (CHg)3N added .......... 0.026 Mole ratio of (CH3)3N to PNClg monomer. . 1:1.04 Experiment V. Wt. of bomb tube 4-air atmosphere+ rubber tube and clamp +-(PNClg) - (CHgJ^N com pound after vacuum released ............ 58.320 TABLE I (continued) WEIGHING METHOD OF ADDING TRIMETHYLAMINE TO PHOSPHORUS CHLORONITRIDE TRIMER Experiment V. (cont.) Wt. of tube removed in seal............ 1.738 Wt. of tube removed when seal broken. . . 0*643 Total wt. removed due to seals . . . . . 2.382 Wt. of bomb tube 4- (PNClg)3 • (CH3)3N com pound + rubber tube and clamp +- (CH3)3N atmosphere ■ — glass removed............... 56.671 Gain in wt. due to (CHsJgN atmosphere . • 0*065 Gain in wt. of compound due to addition of (CH3)5N .'........................... 0.670 Moles of (CHgigN added.................. 0.011 Mole ratio of (CH3)3N to PNClg monomer. . 1:1.5 Experiment VI. Wt. of bomb tube +■ air atmosphere rubber tube and clamp-H PNClg* (CH3)3N compound after vacuum removed.............. 56.731 Wt. of bomb tube-f (CH3) 3N atmosphere 4-rub ber tube and clamp ■+■ (PNClg • (CH3)3N com pound after several days over (CH3j3N .. 57.364 Gain in wt. due to (CH3)3N atmosphere . . 0.060 Wt. of (CH5)5N added . ................ 0.573 Moles of (CH3)3N added ................. 0.0097 Mole ratio of (CH3)3N to PNClg monomer . 1:1.9 28 condense on the cool parts of the tube above the hot oil bath. It appeared that about half of the solid sublimed up the tube while the rest neither melted nor sublimed. Both the sublimate and the residue were white. The bomb tube was weighed again and the total loss in weight due to heating was just slightly less than the total tri methylamine added. Table II shows the record kept during this loss of weight. It was quite obvious that sbme'bf the solid left in the bomb tube was not the same as the trimer originally added, due to the fact that part of it would not melt. A melting point determination was made on the solid that did sublime, and it was found to melt over a range of 90° C. to 150° G. It was obviously not a pure compound. Kjeldahl determinations were made on both the sublimed and the unsublimed, or unmelted, solids. The sublimable solid showed a nitrogen content of 11.5 percent and the other solid showed a nitrogen content of 11.4 per cent, both thus appeared to be pure phosphorus chloronitride. Experiment VIII. An experiment was now tried to see if it would be possible to form the two-to-one compound *in a sealed bomb tube at high temperature and pressure. Phosphorus chloronitride trimer was placed into a Carius bomb tube, and to this was added aia excess of trimethylamine as described previously. The sealed bomb tube was heated 29 TABLE I I DECOMPOSITION OP 1:1,9 PHOSPHORUS CHLORONITRIDE - TRIMETHYLAMINE COMPOUND Experiment VII. Wt. of bomb tube+-rubber tube and clamp-h PNClo - (CH3)5N Compound -j-(CH3)3N at mosphere.................................. 57.564: grm3. Wt. after 'vacuum pulled at room temperature and air replaced (CH3)3N in tube .... 57.384 Wt. after vacuum and heating to 50° C. . . 57.384 Wt. after vacuum and heating to 100° C. . . 57.347 Wt. after vacuum and heating to 150° C.. . 57.334 Wt. after vacuum and heating to 200° C. . . 57.304 Wt. after vacuum and heating to 250° C. . . 56.740 Wt. after vacuum and heating to 265° C.. . 56.362 Loss in wt. from original wt. ....... 1.022 Wt. after vacuum and heating to 285° C. . 54,866 Loss in wt. from 265° to 285° C.. 1,496 Total loss in wt.................. 2.518 Wt. of (CH3)3N added to bomb tube in Exps. V and VI . 7 ........................... 1.240 Total wt. of (CH3)3N added to bomb tube in Exps. IV, V, AND VI....................... 2.745 30 at 100° C. for two hours, at the end of which time there was still some liquid trimethylamine present. Twenty- four hours later there was no liquid present, hut when the tube was opened a small amount of trimethylamine was given off, A Kjeldahl determination was made on the remaining solid, and the results showed 17.3 pereent nitrogen. A compound of two molecules of trimethylamine to one mole cule of phosphorus chloronitride monomer contains 18,0 percent nitrogen. Work on the tetramer. In many cases the work on the tetramer was along parallel lines to the work on the trimer, and in the following discussion much reference will be made to the work on the trimer. Experiment IX. Several grams of phosphorus chloroni tride tetramer were placed into a bomb tube and to this an excess of trimethylamine was added as described in Experiment I. Upon the addition of trimethylamine, a flocculent pre cipitate was formed as was described for the trimer, but in this case, it did not appear as rapidly. The excess tri methylamine was removed after the bomb tube had stood for several days. When this excess was removed, there was evi dence of two different solid forms in the tube. In the bottom of the tube was a crystalline, grainy form like that 51 of the original tetramer, and above this was the new, more powdery solid. A Kjeldahl analysis was made on the powdery form, and the results gave 16.15 percent nitrogen. In this case, as for the trimer, the bomb tube showed a reduction of pressure after several days. Experiment X. In the case of the tetramer, the weigh ing technique was also used as described in Experiment IV. After leaving the trimethylamine in contact with the tetramer for three days, the increase in weight by the addition of trimethylamine showed that 0.00695 mole of trimethylamine was added to 0.0136 mole of phosphorus chloronitride monomer; this result means a ratio of one mole of the monomeric phosphorus chloronitride to 0.52 mole of the trimethylamine. The same type of tabular record was kept as shown in Table I. Here again a vacuum was obtained within the bomb tube after the excess trimethylamine had been removed and the bomb tube had stood for several days. It was thought that the results obtained might be due to impurities in the tetramer. The substance, therefore, was re-distilled in a vacuum and this re-distilled tetramer was used in the next experiment. Experiment XI. Again the weighing method was used on the tetramer as in Experiment X. This time the bomb tube 32 was heated to 55° C., as was done with the trimer, in order to add enough trimethylamine to the phosphorus chloroni tride so there would he no reduction of pressure when the excess trimethylamine was removed. This time the increase in weight indicated a ratio of one molecule of phosphorus chloronitride monomer to 0.59 molecules of trimethylamine. A Kjeldahl nitrogen determination was made on a sample re moved from this homh tuhe. The sample removed was as near as possible an average sample of the contents of the tuhe. The results gave 14.8 percent nitrogen, indicating a little more trimethylamine had heen added than was shown hy the weighing method. Experiment XII. The stability of the 1 to 0.59 com pound was now determined, and the homh tube containing this compound was connected to the vacuum pump as described in Experiment VII.. Again the homh tuhe was weighed at 50° C. intervals. By the time the temperature had reached 150° C., there was a great deal of white sublimate present that had not heen there previously, hut there was no appreciable loss in weight below 250° C. At 280° to 285° C. the solid in the bottom of the tuhe agitated itself, and a gas was given off. This loss in weight was only five percent less than the calculated amount, for the total trimethylamine that had heen added. Again, as in the case of the trimer, 55 part of the solid neither melted nor sublimed at 285° C. None of the aminates formed from the trimer and the tetramer were very hygroscopic. If left open in the air for several hours they would absorb moisture, but the com pounds could be weighed quite conveniently for the Kjeldahl determinations. Only once difficulty was experienced from moisture, and that was on a rainy day when the humidity was near 100 percent; then, the compound absorbed moisture almost too rapidly to weigb- accurately. Work on the polymer. Experiment XIII. A sample of the polymer was placed in a bomb tube, and an excess of trimethylamine was added in the manner previously described. The bomb tube was left sealed at room temperature for sev eral days. A reaction appeared to take plaee in the bomb tube, but it appeared to be just a surface reaction. On the surface of the polymer a hard, white substance was formed, but the trimethylamine did not seem to reach the rest of the polymer. The bomb tube was opened and the ex cess' trimethylamine removed. This hard substance was re moved, but there was not enough that could be separated from the rubbery polymer by mechanical means, for a representa tive analytical sample. This new material appeared to be hygroscopic. 34 Experiment XIV. An excess of trimethylamine was put in a homh tuhe with the polymer as described in Experiment XIII. The polymer stuck to the bottom end of the bomb tube, and remained there even when the tube was inverted. This bomb tube was then placed in an apparatus, as shown in.Figure 5, where the polymer was at the top and could be kept cold by ice, and the liquid trimethylamine .was at the bottom at room temperature. This gave the trimethylamine a reflux action -- it could partially vaporize at the bot tom and condense on the polymer at the top, washing down with it the compound formed by the action of trimethylamine on the polymer, thus exposing new surfaces of polymer for reaction. This experiment was carried on for three months, at the end of which time all the liquid trimethyl amine was gone and about half of the original polymer was in the bottom of the tube in the form of a light brown solid, definitely different in appearance from the original polymer. This bomb tube was opened at room temperature, and there was practically no pressure of trimethylamine inside. As soon as it was opened, it was found that the solid was on the pasty order, and also, very hygroscopic. It was im mediately protected from moisture. Experiment XV. The trimethylamine was now removed from the polymer product as described below* A sample of 35 Rubbery polymer " Z L . Ice water Figure 5 To vacuum EoS0. and glass ^ 4 beads To bomb tube Figure 6 36 the new compound, obtained in Experiment XIV was introduced into an accurately weighed bomb tube as rapidly as pos sible in order to keep it from the moisture in the air, and the weight was re-determined. This bomb tube was con nected to a sulfuric acid trap, as shown in Figure 6, to catch the trimethylamine given off when the trap was con nected to the vacuum pump. All the trimethylamine that could be pulled off by the pump while the bomb tube was still at room temperature was caught in the sulfuric acid. This sulfuric acid was washed from the trap and replaced with new sulfuric acid. The bomb tube was re-weighed, and a loss in weight was assumed to be due to the excess (ad sorbed or lightly confined) trimethylamine. This assump tion was made because in the case of the trimer and tetramer no trimethylamine could be removed from the dry compound below 250° C. Now the pasty material was dry and powdery. The bomb tube was heated while connected to the vacuum pump and weighed, first after a period at 100° C., and then after a time at 200° G. The•temperature was now raised slowly, until the solid appeared to give off a gas (at about 260° C.) and the heating was stopped at 285° G. The bomb tube was re-weighed and had lost 0.010 mole3 of tri methylamine above room temperature, while there was present 0,0116 moles of phosphorus chloronitride monomer; this was 37 calculated from the original weight of solid added minus the total weight of trimethylamine removed* This, showed a compound had been formed with trimethylamine-phosphorus chloronitride monomer in about a one-to-one ratio. The bomb tube, after this heating, looked almost the same as in the case of the trimer* There was a white, sublimed sol id on the cool part of the tube, and an unsublimed, un melted solid in the bottom of the tube. In the case of the trimer, this unmelted solid was white, while in this case the unmelted solid was brown, and even black in places. This discoloration was assumed to be due to impurities in the polymer, which undoubtedly was not as pure as the trimer and tetramer. As a check on the trimethylamine calculated by loss in weight, a nitrogen determination was made on the sulfuric acid used when the bomb tube was heated. The total nitrogen found in the sulfuric acid was equivalent to 0.0085 moles of trimethylamine, which was slightly less than the number of moles of trimethylamine calculated from the loss in weight. A Kjeldahl determination was also made on the white solid in the bomb tube, and the results gave 13.0. percent nitrogen, or slightly more than that calculated for phosphorus chloronitride. CHAPTER IV INTERPRETATION OP RESULTS In discussing the results obtained in the research laboratory, reference will be made to the original purpose as defined in Chapter I, in order to show what has been ac complished in fulfilling this purpose. The chief purpose, to learn whether a tertiary amine, such as trimethylamine, would form any addition compounds by reaction with phosphorus chloronitride, has most definite ly been answered in the affirmative. Evidence of a new com pound was shown In the. case of the trimer and the tetramer by the increase in the nitrogen content of phosphorus ehloro nitride from 12.0 percent to about 16 percent for the new compound. Increase in weight of the phosphorus chloroni tride trimer and tetramer, when trimethylamine was present, also proved that a reaction forming a new addition compound had taken place. Another proof was the change in the melt ing point, and still another, was the decomposition of the new addition product to form a compound with the original nitrogen content of phosphorus chloronitride. In the case of the polymer, evidence, of an addition reaction was shown by the changing of the rubbery polymer to a powdery solid, 39 and the loss in weight during the decomposition of this solid, to give a compound with a nitrogen content near that of pure phosphorus chloronitride. The subsidiary purpose, to decide whether trimethyl amine adds directly to the ring or breaks the ring down, was more difficult to answer than the chief purpose. In the cases of the trimer and tetramer, the results have shown definitely that the ring was broken down giving phos phorus chloronitride in the monomeric form, while in the case of the polymer, the results point in this direction, but a definite statement is not justified. In the case of the trimer, the results showed that one molecule of tri methylamine could easily be added to one molecule of phos phorus chloronitride monomer. These were the results shown by both the Kjeldahl analysis method and by the weigh ing method. However, more results had to be obtained in order to determine whether the ring was actually broken down, giving the mono-aminate of phosphorus chloronitride monomer, or' whether three trimethylamine molecules had at tached themselves to the ring, giving (PNClg)g » 3(CHg)gN. If the trimethylamine were attached directly to the ring, each phosphorus atom in the ring would be showing a bond number of six. On the other hand, in the monomeric form of the compound, phosphorus would be sharing only five pairs of electrons. Two separate experimental results 40 show that the new compound must have come from a break down of the ring* One of these results showed that a com pound was formed that held two molecules of trimethylamine to one molecule of phosphorus chloronitride monomer. It was considered unreasonable to think of two molecules of trimethylamine attached to each phosphorus on the ring, because this would either give the phosphorus a bond num ber of seven, or make nitrogen divalent. There is no previous evidence of phosphorus ever having a bond number of seven, and, there is little evidence of divalent nitro gen. The evidence thus is against the assumption that phosphorus chloronitride-trimethylamine, two-to-one com pound, has a ring structure. When two molecules of tri methylamine are attached to the phosphorus chloronitride monomer, phosphorus has a bond number of six, which is reasonable and also has supporting evidence in ions like PFg. The other result which argues against the ring struc ture was obtained when the phosphorus chloronitride-tri methylamine addition compound was broken down and trimethyl amine was given off. The experimental results showed phos phorus chloronitride in several stages of polymerization from the trimer to the hard polymer. If the trimethylamine were merely driven off the ring, it could be assumed that the 4 1 original trimer would again have been obtained instead of a mixture of polymers. When trimethylamine is driven off a non-ring phosphorus chloronitride-trimethylamine compound, the monomer should immediately polymerize giving the dif- . ferent forms obtained. It might be argued that only the trimer was obtained upon decomposition and part of it poly merized at 285° C, to give other forms found. Schenk and * * 1 Romer gave the following table for time of complete poly merization at various temperatures: Temperature Time Below 250° C, Stable At - 255° 15 hr. (?) 284° 2 hr. 302° 1 hr. 350 Pew minutes The compound was not left at 285° C. more than ten minutes at the most, so the argument of polymerization due to heat alone does not hold here. In the case of the tetramer, the Kjeldahl results showed a compound of one molecule of trimethylamine to one molecule of phosphorus chloronitride monomer, but no evidence could be obtained as to the formation of a compound of two molecules of trimethylamine to one molecule of phosphorus chloronitride monomer. Again, in this case, as for the 1 R, Schenk and Romer, Preparation and Discussion of (PNC12)x," Berichte, 57: 1352, 1924, 42 trimer the results were, the same upon decomposition of the compound formed, thus showing that the tetramer ring was broken into the monomeric form. The results of trimethyl amine addition to the tetramer, both by the Kjeldahl method and the weighing method, showed that not all the compound reacted with the trimethylamine. These results seem to show that the tetramer ring was more difficult to break than the trimer ring, and that a two-to-one compound could not be formed as long as any unreacted phosphorus chloronitride was present, but experimental results were not definite enough along these lines to make any positive statement. In the case of the polymer, the interpretation of the experimental results was more difficult to correlate than for the trimer and tetramer. The compound of one molecule of trimethylamine to one molecule of phosphorus ehloroni- tride that was found gave a mixture of polymers, with both the lower and higher forms present, upon decomposition. These lower forms might have been trimer and tetramer origin ally dissolved in the polymer, except that the quantities obtained were far greater than could be expected by merely heating the polymer. This additional amount of the lower forms plus the results obtained in the cases of the trimer and tetramer would lead one to believe the rings and chains in the polymer were broken down by trimethylamine. In the 43 cases of the trimer, tetramer, and polymer, a nitrogen analy sis was made on the decomposition product and the results showed that some form of phosphorus chloronitride was left and that the phosphorus chloronitride monomer had not de composed in the reaction of trimethylamine or in the heating. Problems for future study. Is the tetramer ring more stable than the trimer ring? Is the two-to-one compound only formed when no unreacted phosphorus chloronitride is present? Work should be carried on with the polymer to prove definitely whether the rings and chains are broken by trimethylamine, or if trimethylamine is merely attached to the complicated structure making the polymer lose its rubbery properties. Work on the phosphorus chloronitrides might be carried on in a solvent, such as carbon tetra chloride or liquid sulfur dioxide, to which trimethylamine could be added to see if similar results would be obtained and if it would be easier to form a two-to-one compound. An interesting problem on the phosphorus chloronitrides would be to work with -different Grignard reagents and a study of the replacement reactions and the new compounds obtained. There are many other Interesting and scientific new problems dealing with phosphorus chloronitride that should be studied. Here, only those most closely related to this work have been mentioned. CHAPTER V CONCLUSIONS The results of this research show: 1. That trimethylamine and the phosphorus ehloroni- trides react to give a very stable addition compound; 2* That the trimer easily forms a compound of one molecule of trimethylamine to one molecule of phosphorus chloronitride monomer, and also forms, with more difficul ty, a compound of two molecules of trimethylamine to one molecule of phosphorus chloronitride monomer, both ad dition products coming from a breakdown of the trimer ring; 5, For the tetramer, the same stable one-to-one compound is formed upon a breakdown of the ring, but prob ably the tetramer ring is more stable than the trimer ring; 4. For the polymer, the rings and chains are probab ly broken down to form, again, a one-to-one compound; how ever, this is a slow process. New problems arising from'this research have been mentioned previously. BIBLIOGRAPHY- BIBLIOGRAPHY Beason and Rosset, ’ ’Action of NH., on (PNClp),," 0ompt. rend., 146: 1149-55, 19087 * ° Couldridge, T., "Phosphorus Chloronitride," J. Chem. Soc. 52: 399, 1888. Ficquelmont, Armand M. de, ’ ’Polymerization of (PNC10) ," Compt. rend., 204: 689-91, 1937. ^ x ____ , ’ ’Polymerization of (PNClp) Compt. rend.« 204: 867-9, 1937. x Ingram, Preston D., "Unpublished Master’s Thesis," The University of Chicago, June, 1939. Moureu, H. and G. Wetroff, ’ ’Preparation of (PNClo)3 from Compt. rend.. 204: 51-3, 1937. • 3 C Rosset, Henri, "Reactions with the Grignard Reagent,” Compt. rend. , • 180: 750-1, 1925. _______, "Reactions with the Grignard Reagent," Bull. Soc. Chem., 37: 518-22, 1925. • • Schenk, R. and Romer, "Preparation and Discussion of (PNC12)X," Berichte. 57: 1343-55, 1924. , "Revision of Molecular Weights," Berichte» 60: 160-161, 1927. Simon and Huter, Zeit. Elch. Chemie, 41: 32, 1935. Stokes, A., "Chloronitrides of Phosphorus, Preparation of Tri and Tetra," Amer« Chem. J., 17: 275-290, 1895. _______ , "Phosphorus Chloronitride and Two Homologues," Berichte, 28: 437-439, 1895. _______ , Zeit. Anorg. Chem.. 19: 36-58, 1895. "Tri Meta -Fhosphimic Acid," Amer. Chem. J., 18: 629-663, 1896. 4 7 , ”Tetra Meta Phosphimic Acid,” Amer. Chem. J., 18i 780-789, 1896* , ”Chloronitrides of Phosphorus,” Amer. Chem. J., 19: 782-796, 1897. , ”Meta Phosphimic Acids,” Amer. Chem. J., 20: 740-760, 1898.

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Creator Taylor, J. C (author)

Core Title An experimental study of the phosphorus chloronitrides and their reactions with trimethylamine

Degree Master of Science

Degree Program Chemistry

Publisher University of Southern California (original), University of Southern California. Libraries (digital)

Tag chemistry, organic,OAI-PMH Harvest

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Advisor Burg, Anton B. (committee chair), Vivian, Robert E. (committee member), Weatherby (committee member)

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