THE VALENCE OF IODINE IN NITROGEN IODIDE BY CARL PETER MOYEN THESIS FOR THE DEGREE OF BACHELOR OF SCIENCE IN CHEMICAL ENGINEERING COLLEGE OF LIBERAL ARTS AND SCIENCES UNIVERSITY OF ILLINOIS 1917 UNIVERSITY OF ILLINOIS May 35th 7 THIS IS TO CERTIFY THAT THE THESIS PREPARED UNDER MY SUPERVISION BY CARL PETER MOYEN ENTITLED THE VA LEN OK OF I ODI WE III # I TROGEN I OD I DE IS APPROVED BY ME AS FULFILLING THIS PART OF THE REQUIREMENTS FOR THE nT™ T7Tr _ BACHELOR OF SCIENCE Instructor in Charge HEAD OF DEPARTMENT OF 376ol:i Digitized by the Internet Archive in 2013 http://archive.org/details/valenceofiodineiOOmoye TABLE 0*' COW TENTS ****** Pages Introduction 1 Historic Review 3-9 Discussion of Historic results 9-13 Experimental 13-18 (checking of previous work) Endeavors to prepare compounds similar to nitrogen iodide with a loaded molecule 18-39 Conclusions 39 ******* UIUC , THE VALENCE OF IODINE IN NITROGEN IODIDE INTRODUCTION The primary object of this thesis is to determine the valence of Iodine in the so-called Ni- trogen Iodide in order to throw more ligfrt upon the structure of that compound and perhaps locate the reasons for its peculiar instability. The work has mainly been carried on in two parts. First to verify and check the work of previous investigations on the subject, and second: to produce compounds related in structure to Nitrogen Iodide with the molecule so load- ed as to produce a greater stability. Probably the most extensive of the past investiga- tions upon the subject of nitrogen iodide has been done by F.D.Chattaway with the assistance of K.J, P. Orton and H.P. Stevens. These men have made an exhaustive research on the problem and have accumulated a vast amount of quantitative data and analyses on the reaction of nitrogen iodide under numerous conditions with many reagents. Among their work on the subject appears, "THE PREPARATION AND PROPERTIES OF THE SO-CALLED NITROGEN IODIDE." by F.D.Chattaway & K.J. P. Orton (1.) under this title appears a brief review of how the com- pound was prepared previous to their investigation, their methods of preparing both the amorphous and crystalline com- pound, the general properties of the same and a brief descrip- tion of the crystals of this compound as determined by W.J.Pope "THE ACTION OF REDUCING AGENTS UPON NITROGEN IODIDE" by F.D.Chattaway & H.P.Stevens (3.) This investigation takes up the action of the following S, reducing agents, Na2S03 ,H2S03 ,As2S3> Sb203,SnCl2and H 2 giving the results produced by each upon nitrogen iodide in detail. Also considerable analytical data is given to substantiate their statements completely. The following table shows the re- lative reducing power of each of the agents used. am't reducing NasS03 H2SO3 AS3S3 Sba03 SnCla H2S agent oxidized. "am't of HI simultaneously HI HI 3HI SHI HI HI _ p roduced. t ^ u (1.) refer to Am.Chem.J. 33 , 363, (1900) (3.) refer to Am.Chem.J. 34, 139, (1900) ) All iodine contained in nitrogen iodide, therefore behaves to- ward reducing agents like the chlorine oontained in a hypochlo- rite and exerts twice its normal oxidizing power. Normal proba- bly meaning that generally associated with the element. "THE COMPOSITION OF NITROGEN IODIDE" by F.D. Chat taway. (1. A brief resume of the properties of nitrogen iodide and its general composition is discussed being followed by considerable experimental data with a discussion of the analytical results obtained* Experiments were also made to determine whether similar substances of composition differing from N2H3I3 could be produced. Nitrogen iodide was prepared in the following ways and analyses are given to show the degree of purity and oonsistancy of the compounds obtained* (1) Thru the action of a solution of iodine in potassium iodide on a solution of ammonia. The average nitrogen, iodine ratio for 6 analyses is 1.998 : 3. (2) From the action of a strong ammonia solution on solid iodine. Average ratio for 6 analyses 1.983 : 3. (3) Thru the action of an alcoholio solution of iodine up- on ammonia. Average ratio for 6 analyses 1.987 : 3. (4) By adding ammonia to a solution of potassium hypoio- dite containing an excess of potash. Average ratio for 6 analy- ses 1.997 : 3. (5) From the action of iodine monochlorlde on ammonia. Average ratio for 6 analyses 1.995 : 3. (1.) refer to Am.Chem.J. 24, 139, (1900) .4. (6) The action of bleaching powder on ammonium iodide. Average ratio for 3 analyses 1*990 : 3. Analyses of amorphous nitrogen iodide dried over baryta in an atmosphere of ammonia, light being totally excluded. The following figures are averages of 8 analyses of the dried compound. nitrogen, iodine ratio ^ lodl^, ff> nitrogen 1.993 : 3. 93.42 6.81 The weights of the dry samples varying from 0.2733 to 0.5937 g. All attempts to prepare similar substances of composition dif- fering from seem to have failed as their accompanying analytical data shows that the nitrogen, iodine ratio always varied closely around the 2 : 3 figure. The nitrogen value ranging from 1.98 to 3.006. Mixtures of any composition from nitrogen iodide to pure iodine were prepared by washing the pure compound continuously with distilled water. As a final summation of his investigation, it seems only quite evident that the simplest formula that nitrogen iodide can have is W 2H3 I 3* "THE ACTION OF LIGHT ON NITROGEN IODIDE" by F.D.Chattaway & K.J.P.Orton (1.) The experimental portion of this subject is also preceded by a brief review of this portion of the subjeot touched upon by others, with a description of the aotion of light upon nitro- gen iodide. An estimation of each substance produced, when nitrogen iodide suspended in a solution of ammonia decomposes under the influence of light is given; being accompanied by analytical data to show the accuracy of the results obtained. (1.) refer to Am.Chem.J. 34, 159, (1900) -5- The article also includes a demonstration with analytical data, to show that hydriodic aoid is liberated during the de- composition by light. The observed action of light on iodine suspended in a solution of ammonia, being followed by the ac- tion of light of different wave lengths on nitrogen iodide. The results of this last determination show that the decomposi- tion produced varies directly with the wave length. White, red, green, blue and indigo lights were tried. The red end of the spectrum producing decomposition most readily being followed by the blue as a second maximum. The final statement being made that nitrogen iodide under the action of light, decomposes quantitatively into nitrogen and hydriodic aoid. "THE ACTIO* OF ALKALINE HYDROXIDES OF WATER AND HYDROGEN PEROXIDE UPON NITROGEN IODIDE" by F.D.Chattaway & K« J. P. Or ton (1.) under this topic the reactions of nitrogen iodide with the following are given, potassium hydroxide, water and hydro- gen peroxide. For the reaction with potassium hydroxide, the following reaction is given; N — NH -h (1) 2H3 I 3 + 3 KOH-^3 NH3 + 3 KOI ^3 3 3 Kl + KI03 At the same time a portion of the compound always breaks down under the influence of light to nitrogen and hydriodio acid. W ^ w (3) 2H3 I3 + 3 HI 3 HI + 3 KOH ^ 3 KI + 3 HgO These statements are backed with analytical results to show that nitrogen iodide under these conditions, acts according to (1.) refer to Am.Chem.J. 34, 318, (1900) the predictions. To show that equation 2 actually takes place, results on analyses carried on in the presence and ab- sence of light are compared. under action of water, nitrogen iodide breaks down as follows, N H I * 3 wH 3 H01 3 3 3 3 + W w HI 3H3 I3 2 + 3 I 4- HgO HI -h HOI 2 This statement and equations are also followed by positive analytical results. The aotion of hydrogen peroxide alone and in the presence of potassium hydroxide on nitrogen iodide is given. The au- thors stating that the process is essentially one of hydroly- sis. Potassium hydroxide is used in one case to prevent the deposition of solid iodine. Analytical results of sufficient importance to be convincing are given. "THE ACTION OF ACIDS UPOW NITROGEfl IODlDfc" by F.D.Chattaway & H.P.Stevens. (1.) A brief description of the general behavior of nitrogen iodide towards acids is given, and is followed by the actions of specific acids upon the same, including experimental data. The acids considered are hydr iodic , hydrocyanic, sulfuric, phosphoric, acetic and hydrochloric. Step equations being in- cluded to more clearly express the reactions produced by the more important ones. The general equation for the action of acids upon nitrogen iodide is given as, W 2H3 I 3 + acici + 3 H3O—*(2 NH3 + acid) + 3 HOI Further reaction depending on the nature of the specific acid (1.) refer to AM.Chem.J. 24, 331, (1900) -7- ueed* When hydriodio aoid is used, ammonium iodide is formed and iodine is liberated thru the action of the HI on the hypoiodous aoid formed. If light be excluded completely, no nitrogen will be evolved. The statement is made that the iodine contained in N2H3I3, behaves as if it were first liberated as HOI • This being followed by complete analytical data. As a conclusion from the results, the authors say that nitrogen iodide entirely hydrolyses into hypoiodous aoid and ammonia. under the reaction of sulfuric acid on W3H3I3, the formula of that acid is inserted in the general acid equation.