Ultraviolet induced decomposition of hexadecanol by Anthony Golden A thesis submitted to the Graduate Faculty in partial fulfillment of the requirements for the degree of MASTER OF SCIENCE in Chemistry Montana State University © Copyright by Anthony Golden (1962) Abstract: Under the influence of ultraviolet radiation at temperatures slightly higher than its melting point, hexadecanol reacts with oxygen to form a variety of products. Those identified to date are: water; a homologous series of acids, palmitic through caprylic (possibly hep-tanoic); and the corresponding aldehydes of carbon numbers 14, 15, and 16. Although the reaction was not studied in detail, a few of its characteristics were determined. Hexadecanol undergoes little or no decomposition in the absence of oxygen when exposed to ultraviolet radiation. The rate of reaction is not dependent on the glass-alcohol interface. Short wavelengths are more important in the reaction than long wavelengths.  ULTRAVIOLET ,,HDUCED DECOMPOSITION OF HEXADECANOL ANTHONY GOLDEN A thesis submitted to the Graduate Faculty.in partial fulfillment of the requirements for the degree of MASTER' OF SCIENCE in Chemistry A Y im trcarl • Chairman, Examining Committee A MONTANA STATE COLLEGE Bozeman, Montana April, 1962 i i i ACMOWtEDGMEWT ' In writing this thesis, I wish to thank the following: The 'Uo S. Bureau of Reclamation, for providing the funds which made my research assistantship possible. The professors and fellow graduate students of the Montana State Chemistry department, especially Dr. Graeme Baker, for their worthwhile advice and assistance. The National Registry of Rare Chemicals, for helping us locate aldehydes for chromatographic work. And finally an unusual expression of gratitude - to the students from the general chemistry classes who were my clients in help sessions. They gave me the realization that I was accomplishing something useful , even during times when research work was producing no meaningful results. Without this, I never would have had the will to remain here and com­ plete the project work. CONTENTS INTRODUCTION. ...................... I INSTRUMENTATION. . . . . . . . . . . ............... . . . . . . 3 EFFECTS OF SUNLIGHT ULTRAVIOLET INDUCED OXIDATION. . . . . . . . . . . . . . . . . . 5 SURFACE EFFECTS............. IO PRODUCT IDENTIFICATIONS. ......................... 10 MONOLAYER SPREADING EXPERIMENTS..................... 19 TIME STUDIES.......... 23 OZONE TREATMENT..................... 25 SUMMARY AND DISCUSSION . . . . . . . . . . . . . . . ........ . . 25 APPENDIX . 30 LITERATURE 33 VLIST OF FIGURES 1 . Oxidation Apparatus 2. Hexadecanol Exposed to UV 2 Days Hexadecanol Unexposed - 3. Testing for Water b. Volatile Products Trapped at Liquid Air Temperatures Solid Residue 5. Hexadecanol Exposed to Unfiltered UV 6 Days 6. Aldehydes 7* Kies Extract Methyl Esters of Kies Recovered Acids 8. Methylated Kies Extract 9. Methyl Esters of Known Acids 10. Methyl Esters of Acid Products 11. Spread Hexadecanol after 24 Hours Exposure to Short Wavelength UV 12. Hexadecanol Exposed 6 Hours to UV 13. Hexadecanol Exposed to Filtered UV 6 Days ABSTRACT ,Under the influence of ultraviolet radiation at temperatures slightly higher than its melting point, hexadecanol reacts with oxygen to form a variety of products. Those identified to date are: water; a homologous series of acids, palmitic through caprylic (possibly hep- tanoic )j and the corresponding aldehydes of carbon numbers 14, 15, and l6. Although the reaction was not studied in detail, a few of its characteristics were determined. Hexadecanol undergoes little or no decomposition in the absence of oxygen when exposed to ultraviolet radia­ tion. The rate of reaction is not dependent on the glass-alcohol inter­ face. Short wavelengths are more important in the reaction than long wavelengths. v i INTRODUCTION In many areas of the West, water supplies are inadequate. For this reason, attempts are being made to conserve as much of this natural re­ source as possible. Often it is prudent to store water, most of which is spring runoff, in large reservoirs. A considerable amount of water is lost by evaporation from such reservoirs, especially during the hot weather. Certain chemical compounds can greatly reduce the evaporation rate when spread on the water surface in layers one molecule thick. Such monomolecular layers are usually referred to as monolayers. The only materials that have any appreciable effect on evaporation reduc­ tion are straight-chain alcohols and acids with 14 to 18 carbon atoms per molecule. The branched chain compounds have been found to be in­ effectual. According to the Bureau of Reclamation (13), one extremely effective and versatile evaporation retardant is hexadecanol, which under the best of conditions can reduce evaporation by 64%. Actual tests have been conducted with long chain alcohols on various reservoirs (7, 17, 18). Since conditions were certainly not ideal (complete monolayer coverage and no monolayer attrition), the measured evaporation reduction percentages were much less than 64%. A main source of monolayer loss was wind action. Winds of velocities much over 20 miles per hour blow the hexadecanol onto the shore. The crumpled hexadecanol will not respread spontaneously to reform the' monolayer. Certain bacteria are known to feed on the hexadecanol and decom­ pose it into materials that are useless for evaporation reduction (9)« -2- There is also the possibility that ultra-violet radiations found in sun­ light, may induce decomposition of the hexadecanol. A preliminary in­ vestigation in which solid hexadecanol was exposed to sunlight sug­ gested that there is little if any decomposition of hexadecanol by solar ultraviolet radiation (3)- An object of the present research was to determine whether UV radiation will induce decomposition under different and perhaps more favorable conditions (higher temperature than ambient, pure oxygen atmosphere, short wavelengths, etc.). If such proved to be the case, additional objectives of the research would be to identify as many of the products as time allowed and to develop analytical techniques which could be useful in future studies of de­ composition of evaporation retardants in monolayer form. -3- INSTRDMENTATION The principal analytical instnament used in this research was a, Wilkens Aerograph A-90 gas chromatograph. The output of the thermal conductivity detector was fed to a Minneapolis-Honeywell one millivolt range strip-chart recorder. Samples, either with no solvent or in hexane, were injected with a Hamilton 10-microliter syringe. The carrier gas was helium. • A 10’., 10% silicone rubber column with 30-60 mesh chromosorb for support was used for much of the work involving the longer chain alcohols. A 3 ’ BDS (butane diol succinate) column packed with 2 0 % active agent on 4o-6o mesh chromosorb was used for work with.methyl esters. In most cases, compounds were identified by matching elution times and peak structures with those of knowns. Some eluates were bubbled through standard test reagents for verification purposes.. The recorder was used to indicate the appropriate time to do this. Infrared spectra were obtained with a Beckman IR-4 recording spectrophotometer. They were helpful in the identification of struc­ tural units in compounds formed as products. Eastman reagent grade hexadecanol used in the present study was redistilled at l8o-190° at 4mm. mercury pressure in a Todd still (l6). The reflux ratio was set at 20:1. Light sources used will be described later in the thesis. ULLUTRA VI O E , H D C M P In the first experiment performed, hexadecanol and octadecanol were exposed to sunlight to test for possible decomposition. The alcohols in finely powdered form were introduced into four quartz (transmits all UV down to 2200 A) cells as follows: No. I contained hexadecanol and was uncapped No. 2 contained hexadecanol and had a regular cell cap with a paraffin seal No. 3 contained octadecanol and was uncapped No. 4 contained octadecanol and was capped similar to 2. The purpose of the capping was to I e a m whether the reactions, if any, required oxygen. The cells were placed in a shallow dish and covered with commercial "Saran Wrap", which /had "been previously examined on an ultraviolet spectrophotometer and found to transmit all the UV. found in sunlight. Luckiesh (12) gives 2900 A as the short wavelength limit for solar radiation. The dish and contents were exposed to sun­ light on the roof of the Montana State College chemistry building for two weeks. After this period, infrared spectra of all four samples were taken using carbon tetrachloride as the solvent. There was no ' visible difference between spectra of exposed and unexposed samples. Likewise, gas chromatography (silicone rubber column and no solvent at 213°) failed to. show any decomposition products. The results of the experiment were in agreement with those obtained -4- earlier by the Bureau of Reclamation (3) and showed that solid hexa- and octadecanol are not readily decomposed by sunlight. Our experiment was run under adverse conditions. There were several cloudy days, and the equipment was covered with snow part of the time.' Only small areas of the alcohols in the cells received direct exposure to sunlight. Rather than repeat the experiment with longer exposure times in order to bring concentrations of possible products up to levels at which they could be detected, it was decided to change the conditions of the experiment so as to favor any reaction that might be taking place. The temperature was raised; the alcohol was"put in the molten state to facilitate absorption of UV, and a source richer in DY than sunlight was adopted. ULTRAVIOLET INDUCED OXIDATION . Ellis and Wells (6) reported that ultraviolet induces no reactions in the lower molecular weight alcohols unless radiations of wavelength shorter than 2000 I are applied. To find what, if anything, happens in the longer chain alcohols, an experiment with liquid hexadecanol just above its melting point (literature 49-2° measured 48.3°) was devised. The UV source itself, a, Hanovia No. 30600 lamp, provided the heat necessary to keep the alcohol melted. The lamp is more or less a "point" source with a. very narrow quartz bulb partly enclosed in a metal shield. Its energy output is 13«70 watts (intensity of at least 44 milliwatts per cm^ at 5 cm. distance). Of this energy output, 6.25 watts are in the UV range. (See appendix I for the spectral energy -5- -6- distrilDUtion. ) The hexadecanol container was a, Corning VYCOR thbe, which transmits ultraviolet down to. about 2h00 A. For purposes of comparison, the spectral energy distribution of sun­ light, as given by Luckeish is as follows: Sun at zenith I atm. 8450 footcandles Wavelength 2900-4000 A (ultraviolet) 5-9^ " 4000-76000 (visible) 43.72» " 7600 and longer (infrared) 52.4^ There are a few sources that list the short wavelength limit as slightly less than 2900 A. We will consider 2800 A to be the short wave limit. Forsythe and Christison (8) list the intensity of solar radiation described above as equal to 4.22 milliwatts per cm^. In the first experiment with the lamp, (figure I illustrates the apparatus used) air was the atmosphere. Mercury was introduced into the U-tube, and the stopcock was used to make the mercury levels equal. The hexadecanol was then exposed to UV. Since the experiment was per­ formed at a temperature higher than that of the room, the mercury level in arm M became higher than in L a few minutes after start. After two days, the mercury levels were again equal. A. leak in the system was suggested. The light was turned:off. Shortly afterwards, the mercury Ilevel in L rose 1~ inches higher than in M and it remained so for a — 2 . — day when the apparatus was disassembled. VThen the experiment was re­ peated, the same phenomenon resulted again. This pointed to a reaction between the alcohol and oxygen and ruled out a leak. Another experi­ ment was carried out in which atmospheres of pure oxygen and nitrogen -7- L MERCUFv UV LAMP I IEXAL ECANCL FIGURE I OXIDATION APPARATUS -8- Trere used. At the end of two days, the mercury levels were equal In the nitrogen setup, and 4 inches apart (higher in arm L) in the oxygen unit. Obviously oxygen was consumed in whatever reaction took place. Infrared spectra were taken of the unexposed alcohol and of the samples exposed in the nitrogen and oxygen atmospheres. The spectrum of the hexadecanol exposed to UV in the presence of nitrogen was identical with that of the unexposed material, indicating little or no reaction. Although small, a rather broad absorption peak at about 1700 cm”-1- was evident in the spectrum of the alcohol exposed to UV in the presence of oxygen. An absorption peak in this area is characteristic of the carbonyl group. The broadness of the band suggested that at least two carbonyl structures were products of the oxidation reation. Pure oxygen was bubbled through molten hexadecanol in the presence of UV radiation for two days in an attempt to accelerate the reation. The experiment was duplicated with nitrogen. The same lamp and VYCOR tubes were used as before. The infrared spectrum of the oxygen run (top half of figure 2) shows a large peak in the 1700 cm-*'" region. As was the case before, no evidence of reaction was obtained in the nitrogen- treated material. Finally, experiments were carried out with the appara­ tus of figure I, but with an infrared heat lamp substituted for the Hanovia lamp. In these runs, the final mercury levels never differed by more than ^ inch, even though an oxygen atmosphere was used and the experiments took about two days. In summary, it can be said that hexadecanol reacts with oxygen in 9 -10- the presence of UV radiation to produce at least two carbonyl structures. SURFACE EFFECTS An apparatus like that shown in figure I with a, wad of glass wool immersed in the melted hexadecanol was set up in an attempt to learn whether or not the oxidation reaction being studied occurs at a glass- alcohol interface. An oxygen atmosphere was provided. In a previous experiment identical with the present one except that no glass wool was used, a rise of 4,7 cm, was noted in L after a, 20-hour period. In the present experiment, there was a 5,1 cm. rise after a 20-hour interval. The difference between 4.7 and $.1 cm. is not regarded as significant, and one may conclude that the rate of decomposition is, within limits of error, independent of the glass-alcohol interface. PRODUCT IDENTIFICATIONS When alcohols are oxidized through treatment with oxidizing agents, aldehydes, acids and water are the chief products. These substances were therefore prime suspects in the reaction under consideration. Figure 3 shows the apparatus used to test for water. The first drying tube, three feet in length, contained calcium chloride and Linde (Union Carbide) type SN molecular sieves (2) of both powder and pellet variety. The "checking stations" contained white anhydrous copper sulfate. The testing procedure was as follows: oxygen was passed through . the drying tube and the first station, and then bubbled through the ex­ posed and melted hexadecanol in the VYCOR tube. The purpose of the -11- AYimtr c a l • v - • 2 3064 o c 8 c 0 1 6 CHECKING DRYING STATION TUBE J I________ I L i ---------1 I--------- r A u v 9 8 ° : Cl - HEXAOECANOL FIGURE 3 TESTING FOR H2O -12- first station was to check the dryness of the oxygen before it entered the hexadecanol - a blue color here would have voided the experiment. Gases leaving the alcohol passed through the second station, also con­ taining anhydrous copper sulfate. After 12 hours, the copper sulfate in station 2 was blue and that in station I still white, proving water to be a. reaction product. Anhydrous copper sulfate was also shaken both with an ether solution of the unexposed alcohol and with the unexposed melted alcohol, No blue color appeared in either case, indicating that the unreacted hexadecanol was dry. The next objective was to compare the products in the residue with those that are volatile and escape. An experiment was conducted with the apparatus of figure 3, except that no checking stations were used. The exhaust carrier oxygen was led into a collecting tube immersed in liquid air. After a day, the trap contained water and unknown materials having sharp odor(s). The organic products were extracted from the mixture with hexane and examined-by gas chromatography. The silicone rubber column was used at 210°. Chromatograms (fig. 4) of the residue (also hexane solvent) showed the same product peaks as those appearing in the chromatogram of the extract. Knowing the oxidation products to contain a variety of carbonyl structures, I performed some classical identification tests for acids, aldehydes and ketones, as described by Cheronis and Entrikin (4) and Shriner and Fuson (l4). After an hour, the oxidized residue gave a positive Schiff test. This long period of time required to give a 13 TEMPERA TURCS I : 1 I : H FIGURE 4 - i l l - positive test pointed to either a, high molecular weight aldehyde (since one of lower molecular weight reacts quickly),, a relatively low concen­ tration of whatever aldehydes might he present, or both.' Acids, later • discovered chromatographically to he present, did not give a positive test here, probably because their concentrations were too low. No posi­ tive test for ketones was obtained. Palmitic aldehyde seemed a logical product. Attempts were there­ fore made, to prepare it by various means (I, 15) so that its peak could be compared chromatographically with those of the unknown products. The attempts were unsuccessful. Finally a sample of palmitic aldehyde was located through the National Registry of RarS Chemicals. The bisulfite addition compound, as obtained from Aldrich Chemical Co., was shaken with dilute sodium hydroxide. The free aldehyde was then extracted with hexane and examined through gas chromatography. Its peak appeared shortly before that of hexadecanol and did not coincide with any of the product peaks obtained up to this time. A sample of alcohol through which oxygen had been bubbled for six days while being exposed to UV (hereafter referred to as 6F X gave the gas chromatogram of figure 5. The peak labeled A-I occupied the same position relative to hexadecanol that palmitic aldehyde occupied in the chromatogram described in the preceeding paragraph. The log retention time vs. carbon number plot of figure 6 is strong evidence that palmitic, aldehyde is actually a decomposition product. .Such plots are usually linear for a homologous series (io). In figure 6, the points represent 15 FIGURE 5 R ET EN TI O N TI M E (M IN U TE S) 16 ALDEHYDES o A C M O W M t + KNOWNS ( L A U R - , M Y R IS T - , P A L M IT - ) CARBON ATOMS FIGURE 6 -17- retention times for unknowns A-l, A-2, and A-3« Points for known palmitic and myristic aldehydes coincide with those for A-I and A-3 respectively. That the decomposition products A-I through A-3 were aldehydes was confirmed hy passing the exhaust gases from the chromato­ graph through samples of Schiff solution. Similar runs were made with the known myristic aldehyde to verify the validity of this testing pro­ cedure. Because the aldehyde concentrations in the oxidized residue were relatively small, it was necessary to use several 10-microliter injections before obtaining in each tube containing test reagent, posi­ tive Schiff tests. Only a, weak Schiff test for the 13 carbon aldehyde was obtained. These tests proved l6, 15 and l4 carbon aldehydes to be present. Since aldehydes are easily oxidized, acids corresponding to the aldehydes found were suspected. Acids must be converted into their esters before they can be detected chromatographically. A hexane solu­ tion of 6F residue was extracted with .01 M NaOH in a Kies counter- current apparatus, as described by Leibrand (11). Re-acidification with HCl .followed by ether extraction were the means used to recover any acids that might be present. Treatment with BFz-methanol (from Applied Science Laboratories, State College, Pa .) to produce methyl esters was the final step before chromatographic examination. The carbonyl peak of the infrared spectrum of the unesterified Kies extract, figure 7, is narrow, indicating the presence of a single carbonyl structure, i.e., the carboxylic group. 18 WAVELENGTH IN MICRONS 7_____________ 8 12 13 14 15 16 . 5000 4500 4000 3500 3000 2500 2000 1900 1800 1700 1600 1500 1400 1300 1200 1100 1000 900 800 700 600 WAVENUMBER IN KAYSERS WAVELENGTH IN M ICRONS 600 1500 1400 1300 1200 WAVENUMBER IN KAYSERS FIGURE 7 -19“ A chromatogram of the esterified mixture was made with hexane sol­ vent at 195° - Figure 8 is the result. Figure 9 shows a chromatogram of some of the knowns . The known esters used in the identification were also obtained from Applied Science laboratories. The peaks are labeled appropriately. Figure 10 shows a retention time vs. carbon number plot of the data obtained. The known peaks of figure 9 match the unknowns of figure 8. In addition, an infrared spectrum was made, and it showed that hydroxy acids might be present, as indicated by the absorption peak at 5^50 cm ^ on the bottom half of figure 7- Detection of such acid(s) will probably depend on finding the proper chromatographic con­ ditions . MONOLAYER SPREADING EXPERIMENTS The next question is whether a monolayer of hexadecanol on water is oxidized in the same manner as in the experiments previously described. Certainly the conditions would not be the same as when molten hexadecanol was used. Also, the molecules of hexadecanol in a monolayer on water are oriented in a specific direction. This orienta­ tion can make a difference in a photolysis reaction, as pointed out by Davies and Rideal ($). In this set of experiments, some hexadecanol was spread on dis­ tilled water in 12 x' 8" PYREX baking dishes. This was done by dropping finely powdered hexadecanol on water and letting it spread spontane­ ously, which it readily does. Some of the hexadecanol remained in crystalline form. A General Electric UVIARC lamp provided the radiation. 20 FIGURE 8 FIGURE 9 R ET EN TI O N TI M E (M IN UT ES ) 22 METHYL ESTERS OF ACID PRODUCTS OUKNOWNS + MYRSTATE 6 PALWITATE CARBON ATOMS IN ACID FlOURE IO -23- Its spectral energy distribution is given in appendix II. The hexa- decanol samples on the water were subjected to very short wavelengths, and to wavelengths found only in sunlight. Simulated sunlight was pro­ vided by placing a Coming Ho. 77^0 filter between lamp and spread alcohol. The filter cuts out radiation below 2800 A. After exposure, the radiated samples were peeled from the surface with a glass rod and examined by gas chromatography. The silicone rubber column was used with no solvent and a column temperature of 22h°. Chromatograms of the hexadecanol exposed to simulated sunlight showed no product peaks, but the chromatogram of the alcohol exposed to very short wavelengths for 24 hours showed a decomposition product peak. This is shown in figure 11 and is still unidentified, although it might be identical with one of the product peaks appearing after that of the hexadecanol in figure 5* It is possible that there may be decompostion into products that are gaseous and therefore escape into the atmosphere, or ones that are very hydrophilic and therefore go into the water as rapidly as formed. In either case, a chromatogram of a peeled-off monolayer would fail to show them. Both of these avenues warrant further investigation. In addition, there is the possibility of decomposition into products that are not eluted chromatographicaIly, such as acids. Means of analysis other than gas chromatography must then be used. TIME STUDIES A few time studies were made to learn what products are produced after various lengths of time, and possibly to discover evidence of 24 WAVEIrIMOtW AIR PEAK HEXADECANOL DECOMPOSITION IMPURITIES PRODUCT FIGURE I l -25- secondary reactions. Oxygen "was "bubbled through molten hexadecanol in a quartz cell and illuminated by the Hanovia lamp for six days. Samples were withdrawn from the cell after 6 and 2k hours of exposure. Figure 12 shows the results after a 6-hour period. The peaks shown in that figure were enlarged in size after 2k hours of exposure. But after 6 days, there were peaks of many new products, as figure 5 shows. , A 6-day run was also made in which a No. TJkO filter was placed between the lamp and the alcohol. The chromatographic results are shown in figure 15- Comparision with figure 5 (chromatogram of a 6-day run in which no filter was used) shows that there is much less decomposi­ tion of the alcohol when short wavelengths are cut out. OZONE TREATMENT It is interesting to speculate about the mechanism of the oxidation reaction. One possibility is that the ultraviolet first converts the oxygen into ozone, and then the ozone reacts with the hexadecanol to produce the products. To establish whether or not this is the case, I passed ozone at the rate of .'09 grams per minute through molten hexa­ decanol for 6 hours. A gas chromatogram, made under the same conditions as the one shown in figure 12 failed to show any of the products appearing in that figure. Such results prove that the mechanism is ■ different from the one suggested above. SUMMARY AND DISCUSSION The present research ha,S established that hexadecanol in the liquid state will react with oxygen under the influence of ultraviolet HEXADECANOL EXPOSED 6 HOURS TO ULTRAVIOLET RADIATION. FIGURE 12 27 ANOL EXPOSED THEXADEO FILTERED UV FIGURE 13 -28- radiation to produce water, a homologous series of aldehydes and a homologous series of acids. The acids which have been positively identified as products are hexa-, penta-, tetra,-, tri-, do-, unde- canoic, decanoic, nonanoic, and octanoic. The positively identified aldehydes are hexa-, penta-, and tetradecanal. Although a determination of the mechanism of the decomposition process was not the objective of this investigation, a few reaction characteristics were uncovered. These include the following: 1. Ozone in the absence of ultraviolet light does not react rapidly with hexadecanol. Consequently the mechanism must include at least one step involving ultraviolet radiation other.than one in which oxygen is converted into ozone . 2. The extent of the hexadecanol-glass interface does not influence the deeompostion rate noticeably. 3. Presence of homologous series of decomposition products indicates that competing reactions are involved. 4. The presence of saturated acids and aldehydes of identical chain length ,indicated that consecutive reactions are involved. 5. Short wavelengths (shorter than 2800 A) are more effective in promoting decomposition than long wavelengths. There are a number of problems related to the present study which warrant further attention. Among them are the following: I. Identification of the remaining decomposition products. -29- Since products with 8-l6 carbon atoms per molecule were found, it seems likely that smaller molecules may also have been produced. 2. Region of the ultraviolet spectrum most effective in promoting the decomposition. If more than one region is involved, it would be desirable to investigate the decomposition products produced by each. 3. Detailed steps of the mechanism(s). k. Additional studies of effect of UV on hexadecanol monolayers with special attention being paid to whether gaseous or extremely hydrophilic products are formed. 9. Photolysis of octadecanol noting differences and similarities between the reactions of hexadecanol and octadecanol. 6. Work with chromatographically pure hexadecanol would be de­ sirable to determine unambiguously whether or not some of the decomposition products originated from a, reaction between im­ purities and oxygen. ' / ■/ 1 APPENDIX -31- APPENDH I SPECTRAL ENERGY DISTRIBUTION OF HANOVIA LAMP (SE BULB) Mercury lines 13675 Angstroms infrared 11287 IDlMo 57BO 5461 visible 4358 4045 3660 334-1 3130 3025 2967 2894 YGVS 2753 uv 2700 2652 2571 2537 2482 2400 2380 2360 2320 2224 Wattage •95 .85 infrared 1.30 1-5.0 1.50 .84 visible -51____________ 1.82 .18 ■1.30 -57 • 30 •19 •19 .08 .09 UV • 47 • 19 • 37 • 19 .12 ..09 .06 .02 .02 -32- APPEHDH II SPECTRAL ENERGY DISTRIBUTION OF UA-Il UVIARC LAMP far UV Wavelength 2200-230p Angstroms 2300-2400 2400-250Q 2500-2600 2600-2700 2700-2800 Wattage ■ 3.36 4.72 12.22 .28.89 20.20 2.22 2800-2900 16.65 2900-3000 12.67 middle UV 3000-3100 24.14 3100-3200 46.83 3200:3300 2.66 3300-3400 5.59 3400-3500 1.58 near UV 3500-3600' 1.86' 3600-3700 67.00 3700-3800 1.60 38oo=4ooo 2.66 4000-4100 14.88 4100=4300 1.60 4300-4400 30.93 SSV V thSVV 4.44 visible 5400-5500 34.04 5500-5700 2.70 5700-5800 36.44 5800-7600 5.41 LITERATURE 1. Adams, et. al., "Organic Reactions", Wiley and Sons, New York, (1948) p... 308-9 2. Barry, H., "Fixed-Bed Adsorption", Ohem.. Eng., 67 Feh. 8, i960 3* Benton, E. J. "X-ray Diffraction Studies of n-Hexadecanol and n-Octadecanol", U. S: Bureau of Reclamation Laboratories, Denver (1956) 4. Cheronis, N. and Entrikin, J., "Semimicro Qualitative Organic Analysis", Interscience Publishers Inc., New York (1957) ch. 8-10 5. Davies, J. and Rideal, E., "Interfacial Phenomena", Academic Press, London (1961) ch. 6 6. Ellis, C . and Wells, A., "Chemical Action of Ultraviolet Rays", Rheinhold, New York (1941) p« 401 7. "Evaporation Reduction Studies at Sahuaro Lake, Arizona, i960", U. S. Bureau of Reclamation, Denver (1961) 8. Forsythe, W. and Christison, F., General Electric Rev. 32 664 (1929) •) 9« Hayes, Murray L., "Biological effects of Hexadecanol Used to Suppress Water Evaporation from Reservoirs", U. S. Bureau of Reclamation, Denver (1959) 10. Heftmann, E., "Chromatography", Rheinhold, New York, (1961) ch. 8 11. Leibrand, R.,.Thesis, Chemistry Department, Montana State College, 1962 p. 11 12. Luckiesh, M., "Artificial Sunlight", Van Nostrand Co., New York (1930) eh. IV 13. "Reservoir Evaporation Reduction with Monomolecular and Similar Films", U. S. Bureau of Reclamation, Denver (1957) 14. Shriner, Fuson, Curtin, "The Systematic Identification of Organic Compounds", John Wiley and Sons, New York (1956) ch. 7 15. Smith and Treadwell, J. Biol. Chem., 212, l4l (1955) 16. Todd, F., "Modem Fractional Distillation Equipment for Your Laboratory", Todd Scientific Co., Springfield, Pa. (1953) -Jil- 17. "Water Loss Investigations: Lake Cachum., 1961", U. S. Bureau of Reclamation, Denver (1962) 18. "Water Loss Investigations: Lake Hefner, 1958", U. S. Bureau of Reclamation, Denver (1959) MONTANA STATT im n /e o e rrv , 3 1762 10013826 0 N378 G565 Cop .2 Golden, Anthony Ultraviolet induced decom­ position of hexadecanol /V3/5 6 5 ^ 5 Z - f