Open Collections

THE RAMM EFFECT OF CIS M B - TRAM'S 35ECAHTBROHAPHTHALEHE A. Thesis submitted i n P a r t i a l F u l f i l m e n t of The Requirements f o r the Degree of MASTER OF ARTS i n the Department of PHYSICS „ by Gennady Zotov THE UNIVERSITY OF BRITISH COLUMBIA A p r i l , 1940 CONTENTS Page Introduction I e Til© 02? « • • • « • • . « • • • 1 I I . D e s c r i p t i o n of Apparatus and Procedure ' 5 1. The Raman Tube . . . . . . 5 2. Spectrographs Equipment . 5 3. Experimental Procedure . . 7 I l l u s t r a t i o n of the Set-up 9 4. Heating System . . . . . . 10 5. Source and Temperature Control . . . . . . . . 11 I l l u s t r a t i o n of the C i r c u i t 13 I I I . INTRODUCTION I t i s only r e c e n t l y 1 that Dr. W. F. Seyer, of the Department of Chemistry of the U n i v e r s i t y of B r i t i s h Columbia, has succeeded i n separating completely the two isomers, c i s and trans decahydronaphthalene. His work on the change i n the surface tensions, density e t c , with temperature of these substances revealed the p o s s i b i l i t y e i t h e r of f u r t h e r sub-d i v i s i o n of the c i s and trans froms or of changes i n structure of the o r i g i n a l molecules as we go to higher temperatures. I t was suggested by Dr. H. D. Smith, that t h i s problem be attacked by a study of the Raman eff e e t of these isomers at various temperatures. The Raman spectrum of deea-3 l i n at room temperatures has been studied by s e v e r a l workers. These i n v e s t i g a t o r s , however, had no access to the isomers i n the pure s t a t e , nor had they any knowledge of t h e i r tem-perature behaviour. There i s reason to b e l i e v e , therefore, that t h e i r work d i d not give as much evidence of the i n t e r n a l s t r u c t u r e of the d e c a l i n molecule as i s , perhaps, p o s s i b l e to obtain. In view of t h i s f a c t t h i s research was undertaken as, suggested by Dr. H. D. Smith. 1.& 2. Seyer & Walker, J.A.C.S., 60, 2125, 1938, and more recent work. 3. Jatka f , Ind.J.Physics, 9:545, Qo 1 15, 1935. Bonino, AcCi L i n c e i A t t i . 22 pp. 438-443, Nov.17, 1935, and other papers. THE RAMAN EFFECT OF CIS AFP TRACTS DECAHYDROIAPHTHASE1E I . Theory I t was discovered by Raman that l i g h t i n c i d e n t on cl e a r substances i s not only scattered to produce l i g h t of the same frequency as the incide n t r a d i a t i o n (Rayleigh or c l a s s i c a l s c a t t e r i n g ) but that new l i n e s appear i n the spec-trum of the sc a t t e r e d l i g h t having frequencies that are p e c u l i a r to the s c a t t e r i n g substance. I t i s known that a molecule of any chemical eom-• J* pound c o n s i s t s i n general of a d e f i n i t e number of atoms of d i f f e r e n t elements. Because of the molecule's s t a b i l i t y i t may be p i c t u r e d as formed from i t s constituent atoms i n a d e f i n i t e s t r u c t u r e i n space. The atoms themselves, however, v i b r a t e at c e r t a i n permissible frequencies governed by t h e i r number, mass and r e l a t i v e p o s i t i o n s with respect to other mem-bers of the molecule. Thus a molecule may have a c e r t a i n energy because of these i n t e r n a l v i b r a t i o n s i n which case i t i s said t o be i n a c e r t a i n e x c i t e d energy s t a t e . Thus a photon, from a beam of i n c i d e n t l i g h t , c o l -l i d i n g w ith a molecule i n a given energy s t a t e , may e i t h e r "  impart some of i t s energy to the molecule and be scattered by the molecule w i t h l e s s energy, or i t may reduce an ex c i t e d molecule to a lower energy state "by talcing energy from i t , " and be scattered with greater energy. This i s shown s y m b o l i c a l l y as f o l l o w s : - ^ = ^ ± j% ^  i . e . V = /ryo :tz .or -t>~% •= # ^ A ^ where i s the energy of the scattered photon /z i s Planck's constant # i s the frequency of the i n c i d e n t photon p i s the frequency of the scattered photon, and V i s one of the c h a r a c t e r i s t i c v i b r a t i o n a l frequencies of the molecule. The p r o b a b i l i t y of gain of energy by the photon i s much l e s s than the p r o b a b i l i t y ' o f energy l o s s , due to the f a c t that p r a c t i c a l l y a l l of the molecules i n the s c a t t e r i n g sub-stance are i n t h e i r normal, or lowest, energy s t a t e . Hence i n general there are fewer Raman l i n e s , and these of weaker i n t e n s i t y , due to the energy gain than to the energy l o s s of the photon. Summing up we have f o r energy l o s s — hpj we have A* > A z f o r energy ga i n + h P, we have /^^< \- r where i s the wavelength of the Raman l i g h t , and i s the wavelength of the i n c i d e n t l i g h t . Lines a r i s i n g from the most common type of energy change are sometimes r e f e r r e d to as Stokes' l i n e s (represented by the s u p e r s c r i p t "s";): while the other types are c a l l e d Anti-Stokes' l i n e s (represented "by the superscript "A.S'J), We also have 1V » L,A, where I i s the i n t e n s i t y of the l i n e . In order to' obtain the v i b r a t i o n a l frequencies of the molecule the f o l l o w i n g information i s obtained from the spectrograms: The photographic p l a t e bearing the spectrogram i s measured up on a comparator i n such a way that the distance of each l i n e .from a c e r t a i n l i n e of short wavelength, say the v i o l e t Hg l i n e , X 4047 A.IJ., i s obtained i n centimeters. S i m i l a r l y another p l a t e w i t h Hg and. Fe comparison spectra i s measured, and by proper t r a n s l a t i o n the readings are corre-l a t e d as i f the Raman and the Fe spectra were taken simul-taneously. This s u p e r p o s i t i o n of the Raman spectrum on that of the Fe enables the l a t t e r t o be used as a coordinate axis f o r i t s wavelengths are known. From the known values of the Fe l i n e s the value of a given Raman l i n e i s found i n terms of wavelengths by i n t e r p o l a t i o n of i t s measured value and the values of the Wo c l o s e s t Fe l i n e s between which i t l i e s . These wavelengths are converted i n t o frequencies (or more con-v e n i e n t l y i n t o wave numbers). Estimates of r e l a t i v e i n t e n s i -t i e s of the Raman l i n e s are al s o made. .The data thus obtained i s i n t e r p r e t e d by the a i d of the theory o u t l i n e d above. . • Thus w i t h the knowledge of po s s i b l e v i b r a t i o n a l frer-quencies of the molecule and of the approximate s t r u c t u r e of the molecule i n f e r r e d "by chemical considerations, or by a mathematical treatment of the moleoule as a many-body problem i n mechanics, employing methods s i m i l a r to those developed by Bennison and others, a more d e t a i l e d model of the molecule may be constructed. An.intense monochromatic source of l i g h t must be used to produce w e l l defined strong Raman l i n e s that are not o b l i -terated by other l i n e s i n the spectrum of the i n c i d e n t l i g h t . Otherwise i f the source be weak i t i s impossible to obtain Raman l i n e s w i t h i n reasonable periods of time; and i f the source contains s e v e r a l intense l i n e s i t i s d i f f i c u l t to deter-mine from which i n c i d e n t l i n e a given Raman l i n e a r i s e s * The Eg are comes very close to being the i d e a l source. I t s spectrum, has o n l y two l i n e s v i z . , A A4047, 4358 i n the r e g i o n A A4000-5000 A.U. of i n t e n s i t i e s great enough to give r i s e to Raman l i n e s . Moreover t h i s region i s remarkably free from other l i n e s of l e s s e r i n t e n s i t y and these may be cut out of the spectrum of the i n c i d e n t l i g h t by the use of spe-c i a l f i l t e r s . This f i l t e r i n g a l s o lessens the continuous background present i n t h i s region of the Hg arc spectrum. - 5 -I I I . D e s c r i p t i o n of Apparatus and Procedure The standard method of obtaining good Raman plates c o n s i s t s of recording s p e e t r o g r a p h i c a l l y the l i g h t scattered by the substance i n a d i r e c t i o n at r i g h t angles to that of the inc i d e n t l i g h t . Deviations from standard technique, however, were found necessary i n th i s , work, and because of t h e i r . i n t e r e s t and importance are described below. I . The Raman Tube The Raman tube (46) containing the l i q u i d to be studied i s designed e s p e c i a l l y f o r work at various tempera-ture s . I t c o n s i s t s of a double-walled c y l i n d r i c a l pyrex tube with outside dimensions of 4.1 cm,* diameter and 14*8 cm. length. The inner tube that holds the l i q u i d being i n v e s t i -gated i s 2*6 cm, i n diameter and 11.1 cm. long with a capacity of 60 c.e. I t s c o n s t r u c t i o n i s shown i n d e t a i l b y the scale diagram designated F i g . I . The sides of the tube from A to B and G to 3 are blackened with lampblack mixed with s h e l l a c and a l c o h o l and the ends are covered except f o r spaces 13? and GH of 1 cm. diameter. A r i n g (I) i s a l s o painted around the base of the thermometer w e l l . The black coats prevent the admission and r e f l e c t i o n of s t r a y l i g h t . At the back GrH a small plane mirror (8) i s placed to r e f l e c t back along the ax i s i n t o the spectrograph the scattered l i g h t proceeding away from the instrument. The 1 source, a Hg arc (48), i s placed as shown, and the l i g h t i s focussed on the a x i s of the Raman tube (46.) by means of alumi-num r e f l e c t o r s v i z . , a p a r a b o l i c r e f l e c t o r (49) and a c y l i n -d r i c a l r e f l e c t o r (50) i n d i r e c t contact with (46). A glass c e l l (47), 10 x 1 x 1 cm. i n s i z e , i s i n t r o -duced between (46) and (48) to hold the f i l t e r s o l u t i o n . To protect the c e l l , to l e s s e n evaporation of the f i l t e r s o l u t i o n and to prevent heating up of the l i q u i d by the arc, a copper. U-tube, through which cold water i s running continuously, i s immersed i n the f i l t e r s o l u t i o n to a depth j u s t c l e a r i n g the top of the Raman tube. The heat from the are i s thus absorbed by the f i l t e r s o l u t i o n and then c a r r i e d away by the c o l d water. Source A mercury arc c o n s i s t i n g of a quartz tube with mer-cury pool electrodes i s used as a source. The arc i s equipped with aluminum f i n s for r a d i a t i o n of heat generated during i t s operation. The arc i s struck at 3.2 amps, with 24 v o l t s across the tube. The current then f a l l s to 1.6 amps, at 66 v o l t s as mercury globules are evaporated from the sides of the tube. On the completion of evaporation the current r i s e s to 1.8 amps, at 60 v o l t s . An a i r stream i s then turned on, and maintained, p l a y i n g on the negative end of the quartz tube. The.flow of the stream i s adjusted so that the amperage reaches and remains at 2.8 amps, at 30 v o l t s across the are. Under these condi-t i o n s the arc operates f o r an i n d e f i n i t e period of time. F i l t e r Owing to the f a c t that mercury arcs give a c o n t i -nuous background f o r long exposures i n the re g i o n AA.4360 -4800 A.U., which would cut out the weaker Raman l i n e s , a f i l t e r i s introduced between the source and the tube. S u f f i -c i e n t fluorescene, d i s s o l v e d i n a small quantity of a l c o h o l , i s added to water i n the glass c e l l to cut out most of t h i s background without appreciably c u t t i n g down the i n t e n s i t y of A 4916 A.F. Z. Spee trographic Equlpment To obtain the spectrograms Eastman photographic . p l a t e s of type 105-0 were used. These plates were introduced by t h i s company e s p e c i a l l y for Raman spectroscopy. They were developed i n D - 19 developer and f i x e d i n a F 5 s o l u t i o n . The spectrograph used was. a H i l g e r Constant Devia-t i o n ins t r a ^ with a d i s p e r s i o n of 17 A.TJ. per mm. i n the regio n u t i l i z e d . 3. Experimental Pr o cedure The scattered l i g h t from the Raman tube i s focussed on the spectrograph s l i t (1) by the condensing l e n s ( 2 ) , as shown i n F i g . I I . In order t o prevent l i g h t r e f l e c t e d from the sides of the Raman tube from reaching the s l i t of the spectrograph two blackened metal diaphragms (4), (5) wit h openings of 1 em, diameter are introduced; the condensing lens i t s e l f i s blackened a l s o except for a c e n t r a l p o r t i o n of the same s i z e as the diaphragm openings. In order to decrease the exposure times great care was taken t o use the maximum•amount of scattered energy. For t h i s reason the alignment of the o p t i c a l system deserves par-t i c u l a r a t t e n t i o n , the procedure being as f o l l o w s : A small plane mirror (3) was in s e r t e d between the condensing lens (2) and the f i r s t diaphragm (4) at an angle of 45° to the d i r e c t i o n of the scattered beam. The p o s i t i o n s of the diaphragms 14) and (5) were changed i n t h e i r r e s p e c t i v e •planes by the observer, while viewing i n (3), so that a set of concentric r i n g s (15) were formed by the openings (4), (5), (6) and t h e i r r e s p e c t i v e images (12), (11), (10) i n the mirror (8), with the image (13), of the eye,(9), at the centre. This ensures an' unhindered path of the scattered beam while preventing any s t r a y l i g h t from reaching the: spectrograph. With the mirror (3) now removed, a piece of trans-lucent paper was placed d i r e c t l y i n the path of the beam and i n contact w i t h the diaphragm side of the l e n s ( 2 ) , and the len s was moved i n i t s plane u n t i l the c e n t r a l p o r t i o n was con-c e n t r i c with the cross s e c t i o n of the beam. The paper was then taken away and the spectrograph was moved along the d i r e c t i o n of the beam to a point where a sharp image on the s l i t (1) was secured. The image was made s l i g h t l y l a r g e r than t h e . s l i t to ensure that n o ' l i g h t r e f l e c t e d by the walls of the Raman tube be sent through the s l i t . The adjustment of the spectrograph was c a r r i e d out by the standard method of s e t t i n g the c o l l i m a t o r f o r p a r a l l e l l i g h t , and the focussing of the s p e c t r a l l i n e s c a r r i e d out by the a i d of the Foucou.lt shadow t e s t . The condensing lens (2) was chosen of such a f o c a l length (F = 2.54 cm.) that the l i g h t from the sharp image (of a bri g h t object of the required s i z e - 1 cm. diameter - placed at the centre of the Raman tube) on the s l i t j u s t f i l l e d the c o l l i m a t o r l e n s . The white scale from a broken Beckmann thermometer served as a bri g h t object. A s t r i p of sheet aluminum in s e r t e d i n the Raman tube was used also to advantage as a br i g h t source, by r e f l e c t i n g the l i g h t from the Hg arc outside, f o r the Foucoult t e s t . This was e s p e c i a l l y d e s i r a b l e with the Hg blue l i n e , A 4358, and the v i o l e t l i n e , A 4047, for t h e i r i n t e n s i t i e s were too low for s a t i s f a c t o r y v i s u a l observation. - 10 -Using white l i g h t , w i t h such a r e f l e c t o r i n p o s i t i o n , the f o l l o w i n g procedure was adopted t o throw the maximum energy on t o the photographic p l a t e : With the s l i t open wide and a piece of translucent paper at the condensing lens the spectrograph was rot a t e d about a v e r t i c a l a x i s and l e v e l l e d by the observer u n t i l he could see through the camera lens (17) a colored spot of l i g h t at the centre of the "frame" formed by the edges of the prism (16) nearest t o the camera l e n s . To get maximum energy for minimum width of the spec-t r a l l i n e , the s l i t was f i r s t closed, and then slowly opened while i t s image was being observed at the f o c a l plane of the camera (18) by the eye w i t h a narrow c y l i n d r i c a l lens (F = 1 em.) placed j u s t i n f r o n t of i t . The axis of the c y l i n d r i c a l lens was placed perpendicular to the image (or the s p e c t r a l l i n e ) . For t h i s purpose Hg l i g h t was used w i t h a l l obstruc-t i o n s such as the translucent paper and mirror removed. The l i n e appeared of l a r g e and constant width, but shaded, as shown i n (20), the shadow disappearing across the image i n t o the side on widening the s l i t . The proper width was deter-mined at the spacing of the s l i t where the shadow had ju s t disappeared. 4. Heating System For exposures at high temperatures the l i q u i d i n the tube was r a i s e d to the required temperature by passing a stream of heated a i r through the jacket around the Raman tube. The - 11 -stream was supplied by a four-vane water cooled compressor run at 1725 revs, per min. by a 1/8 H.P. A.C. motor drawing 3 amps and heated on being passed through a h e l i c a l copper tube i n an oven. The oven was heated by an e l e c t r i c r e s i s t e r (27) on A.C, The upper l i m i t of the current was determined by the s e t t i n g of the rheostat (R) and the heating c o n t r o l l e d by a stove thermostat (30) on a U.C. r e l a y (32). The upper l i m i t of the current used was a safeguard to prevent overheating i n case of f a i l u r e of the r e l a y . . Source and Temperature, Control Although the stronger Raman l i n e s of the d e e a l i n isomers could be photographed i n 30 or 40 minutes, much longer exposures (144 hours) were taken i n order that many of the weakest Raman t r a n s i t i o n s might be recorded on the spectro-graphic p l a t e . A study of these f a i n t e r l i n e s was necessary i f any s l i g h t changes i n molecular s t r u c t u r e w i t h temperature were to be i n v e s t i g a t e d . Therefore i n order to maintain the temperature of the" l i q u i d at a constant value and to guard, from any po s s i b l e f a i l u r e s i n e l e c t r i c a l supply or other con-tingencies the f o l l o w i n g e l e c t r i c a l c i r c u i t was used as shown i n F i g . I I I . The motor (45) running the compressor which c i r c u -l a t e d a stream of a i r (shown by the dotted arrow) over the * heating element (27) to heat the l i q u i d i n the Raman tube (26) was on the 110-volt A.C. l i n e . In the event of the compressor' - 12 -f a i l u r e the p r o t e c t i v e fuse (43) was "blown" "by the growing current i n the motor c i r c u i t , To avoid the "blowing 1? due to the current surge on s t a r t i n g , the motor the by^pass switch (44) was closed f i r s t , the fuse switch (42) was closed next, and then (44) was opened. Since, oh the stopping of the compressor, the l i q u i d i n the Raman tube; would c o o l to room temperature i t was neces-sary that the arc be cut o f f i n order to prevent superposition of the spectrum due to the exposure at the room temperature on the one being taken at higher temperatures. For t h i s purpose the primary of the transformer (40) was put across the motor, at 110 v o l t s , but i n s e r i e s with the fuse, to actuate the. r e l a y (39) on i t s secondary at 500 v o l t s . When the motor was running the c o i l of the r e l a y held i n suspension the i r o n yoke (38) to which was attached the mercury switch (37) c l o s i n g the B.C. to maintain the arc (25). On, the "blowing 1 1 of the.fuse the yoke was released, breaking the B.C. Switch (41) was introduced f o r safety while working on the adjustment of the r e l a y . When heating was not required ( i . e . (45) not used) the arc was main-tained by s h o r t i n g the mercury switch by means of key (36). The arc (25) was on the 110 v o l t s B.C.. l i n e i n s e r i e s with a p r o t e c t i v e r e s i s t a n c e (35) which was adjusted to read 2.8 amps, on the ammeter (21) when operating under steady con-d i t i o n s . Taps on (35) supplied voltage to operate the r e l a y s (32) and (33) . Relay (33) operated the e l e c t r i c clock (34) which stopped on the f a i l u r e of the arc or of the compressor - 13 -thus recording the exposure time. Relay (32) i n s e r i e s with the thermostat (30) con-t r o l l e d the A.C. current i n the heater (27) read by the ammeter (28). The hybrid switch (31) with the shorting key (29) was used to t e s t the working of (32), to set (30) f o r operation at the required temperature, and to speed up i n i t i a l heating without d i s t u r b i n g the s e t t i n g on (30). - 14 -I I I . : :; Results A number of e x c e l l e n t Raman spectrograms have been obtained and several of these are reproduced i n Plat e s I , I.I, and I I I . P l a t e I shows the Raman spectrum obtained with c i s decanaphthalene at 20° C..,'while Plat e IT was obtained w i t h the same l i q u i d maintained at a temperature of 65° C., that i s , at a point w e l l above the " t r a n s i t i o n " temperature observed by Seyer* Plate I I I i s the Raman spectrum of the trans modi-f i c a t i o n maintained at 20° 0. A large number of Raman l i n e s were observed i n a l l three spectrograms, and the f i r s t columns of Tables I and I I give the wavelengths of these l i n e s , i n Ang-strom u n i t s . The'second columns of each t a b l e give; the f r e -quency numbers corresponding to these wavelengths, while the t h i r d and f o u r t h columns give the AV.^'s or Raman frequency: s h i f t s from the two incident l i n e s X4047 A. and A 4358 A. In order to f a c i l i t a t e an examination of the spectra obtained, t r a c i n g s were obtained w i t h a M o l l micr©photometer of P l a t e s I , I I , and I I I . Copies of these t r a c i n g s are repro-duced here i n P l a t e s IV, V, and V I . An examination of Plat e s I and I I I of the c i s and trans isomers, along w i t h t h e i r cor-responding mierophotometer tr a c i n g s shows that there are very great d i f f e r e n c e s i n the Raman spectra of the two modifica-t i o n s at room temperature. From the wavelength and frequency d i f f e r e n c e s given i n Tables I and I I , one sees that many l i n e s appearing i n the spectrum of the c i s isomer do not appear i n that of the trans m o d i f i c a t i o n , and that many "trans" f r e -* • - 15 -quencies are absent i n the T ' c i s " spectrum. In both spectra however a number of new Raman l i n e s are found that have not been recorded by previous workers. A fur t h e r study of these new frequencies may f u r n i s h valuable information concerning the structure of the " c i s " and "t r a n s " modifications of the decahydronaphthalene molecule. A c a r e f u l comparison of P l a t e s I and I I and t h e i r microphotometer t r a c i n g s i V and Y y i e l d s p o s s i b l y the most i n t e r e s t i n g r e s u l t of t h i s research; namely,- di f f e r e n c e s are observed i n the two spectra that i n a l l p r o b a b i l i t y i n d i c a t e a change i n the molecular s t r u c t u r e of c i s decahydronaphthalene as i t i s taken from 20° C. to 65° C, I f t h i s i s so, we have an explanation of the sudden changes observed i n the p h y s i c a l properties of t h i s isomer i n the neighborhood of 55° C. A s i m i l a r change f o r trans decahydronaphthalene at 85° G. i s in d i c a t e d b y Seyer's work and a study i s being made at the present time of t h i s isomer at temperatures above and below t h i s t r a n s i t i o n p o i n t . Table I (Cis) # X A 1 4132.8 715.5 2 4173.6 752 .0 3 4190.9 850.9 4 4204.6 928.6 5 4213.1 97 6.6 6 4218.8 1008.6 7 4223.6 1035.6 8 . 1066.9 9 4255.9 121*3 e 2 1G 4264.9 1264.8 11 4268.1 1282.3 12 4275.5 1322.9 13 4280.5 1350.2 14 4297.5 1442.6 15 4427.3 2124.6 357.2 16 4442.3 2200.8 433.4 17 4476.0 2370.3 602.9 18 4504.2 2510.1 742.7 19 : 4514.7 2561.7 794.3 20' • 4523.1' 2602.8 83,5.4 21 4526.3 2618.5 851.1 22 4534.6 2658.9 891.5 23 4542.2, 2695.8 928.4 24 4550.5 : 2735.9 968.6 25 4552.9 2747.5 980.1 26 4559.4 2778.8 1011.4 27 4565.8 2809.6 1042.2 28 4571.6 2837.3 1069.9 29 4575.6 2856.4 1089.0 30 4581.3 2883.6 1116.2 31 4584.5 2898.9 1131.5 32 4587.5 2913.1 1145.7 33 4593.0 2939.2 1171.8 34 4602.9 2986.0 1218.6 35 4608.3 3001.5 1244.1 36 4614.1 3038.8 1271.4 37 4624.1 3086.6 1318.2 38 4628.3 3105.2 1337.8 39 4631.1 3118.3 1350.9 40 4635.0 3136.4 1369.0 41 4651.2 3211.6 1444.2 42 4655.6 3221.9 1464.5 43 4929.0 4423.0 2655.6 44 4940.0 44#8.1 2700.7 45 4948.6 r 4503.3 2735.9 46 4960.4 4:5131 e «3 2783.9 47 4976.7 4617.4 2850.0 48 4980.4 4632.3 2864.9 49 4987.4 4660.4 2893.0 50 4993*6 4685.4 : 2918.0 51 4999.0 4707.0 2939.6 52 5028.2 . 4823.1 3055.7 53 5050.3 4910.1 3142,7 54 5127.2 5207.0 3439.6 Table I I (Trans) f A A V 1 4113•6 402.6 2. 4128,3 489.2 4171.7 •741.1 . 4 4189.3 841.8 5., 4193.7 966.8 6 4221.5 1023.8 7 4225.6 • 1046.8 8 4241.-8 1137.1 9 . 4245*5 11.57.6 10 4257.8 1225.7 11 4261.9 1248,3 12 4265.0 1265,3 13 4273.7 1307.0 14 4278.4 1338.6 15 4282.0 1358.4 16 4297.3 1441.5 17 4415.1 2062.2 294.8 18 4418.4 2079.1 311.7 19 4453.4;- 2256.9 589.5 20 4495.7 2468.1 700.7 21 4524.0' 2607.2 839 * 8 22 4550.6 2639*4 872.0 23 4533.7 2654.5 887.1 24 4541i4 2691.9 25 4546.8. 2718.1 950.7 26 4554.9 27 62.0 994.6 27 4568.2 2821.1 1053.7 28 4571.9 2838.8 1071.4 29 4681.2 2883.2 1115.8 30 4586.7 2909.3 1141.9 32 4607.0 3005.4 1238.0 33 4617.0 3052.4 1285.0 34 4623.6 3083.3 1315.9 35 4630.9 3117.4 1350.0 36 4634.9 3136.0 1368.6 37 4636.1 3141.6 1374.2 38 4651*0 3210.7 39 4928.0 4418.8 2661.4 40 4960.3 4550.9 2785.5 41 4972.1 4598.8 2831,4 42 4977.3 4619.8 2852.4 43 4986-. 0 4654,8 2887.4 44 4993.0 4682.9 2915.5 45 4997.6 4701.4 2934.0 46 5011.3 4756.0 2988*6 47 5030.1 4830.6 3063.2 48 5128.9 5213.5 3446.1 49 5178.3 5399.4 3652.0 PI ate I Plale'JL' Plate 71/ 7 late VL