Puranik, P G

Rao, E V

English

IACS Institutional Repository

VIBRATIONAL SPECTRA. APPROXIMATE POTENTIAL CONSTANTS AND CALCULATED THERMODYNAMIC PROPERTIES OF BENZOPHENONEG. HJllANIK. ANJ) B. V. KAODI'JPABTMUNT o p  T hYSIUS, U n IVPIISITY CuLLlSGIS OP SuiPNOD,OSMANJA DpriViUJlSiTY, H y OEUAJJAJ)-7.( l i t i x i v c d  A i k j v s I S, HMIl!)ABSTRACT. Ik’U/ojjJjonouo has bomi sul)jooU‘il l,o iiorimil coonliiml.o IrcuUiiGiii assiomug Iho j>liimyl groups to lio point masst's. Tlio F-(< m atrix motliod lias bi'onomjiloyod to obtain th(' st'cul.ir (*quation in oj*d(‘J‘ to caloulalo tbo rimdmnoiital Iroquonoios. [n oaloulatiug tlic tliumiodynamic proportios, i uiitnbutions irom the ring livqiioiieies are hIho moludod.I  N  1’ R 0 D LT 0 T 1 0 NTlio iiiricircd spoolTuiu of iKmoiihonoiie is not found in lit/oruturc m all its a.spocis, alllioiigh sevcial woikors mcnlioii llie luvbonyl freijiiom-y. Howovoi', tlio Jldiiuin spouU'um of lionzojiUonone lias boui loiiorded among otlior.s by Kohl- rauscili aiul J^ Jngl■l^ lz (11)34), Lcsij'ado (11)52) and Jbiniink (11)53). No atiempl appeavs to liavp lioen inado to Hubjuct tlio niolccule to normal coordinate trealinent.E  X  P  K K  I  M 15 T  A 1.Tlie infr.triid s i^ccdruin n\tis reroi'ded \>TtU a iVrkin-Elmer infrai'cd iSpeciio- pliotometcr Model 21 AMth N.iCl option. The speotium ’was rcoorded in niijol ninll and in solutions of CCV Tln^  speotruin m solutions of CCl^  was more cxiensiyc but it did not exhibit any shift in the frequencios recorded in the mull.The Haiuan specbruiu of molUm beir/.ojihenone mtis recorded by using a Hilgcr Ramaai Source Unit and Fuess Ulass Spectrograph having a dispersion of IDl/mm 111 A435S region, fn order to get the spectrum of molten beiizopheiioiie, the melt is poured in the Raman tube in the Unit and the IIoav of the cooling vvaitui Lirculation is sIomtmI down and regulateil so as to keep the temperature of the cell slightly above 49“C 'which is the molting point of bonzophcnonc. Jn this way the substance can be retidned in molten state for a considerable time.Benzophenone of Merck make was recrystallisod by dissolving it in anhydrous absolute ethyl alcohol.R E  S U  L  T  S' Tlic Raman spoetrum of benzophenone melt and its infrared spectrum in solutions in CCI4 are given in Table 1. The Raman spcetiTiin ol the substance as13121122 P. 6?. Puranik and E. V. Raorecorded by Lcslrfide is j'iv'cn lor coiiijjai isoii. The pi’esciil results, howev’^ er, aj r^oe mure closely with those reported by Kohlrausch and PoiigiatK. The assign­ments proposed ai’c also imlicated in Table I.’^ABLE 1[lanian ami infrared fToqueneies in cm~Jlam aii In tm i’odAa,yigrun('riisAuj.liors L i‘h Lrarlo AiiUiurH148 (2)221 (2) 223 (5)277 (2) - - doCormatioii.— 387 (1) -400 (2) 410 (1) 0  (c\.,d ring507 (2) 550 (1) - 0-C  --0  dclopnial/ioii.- - 570 (2) —010 (.I) 012 (5) — 0  (lv, )^ ring.- 000 (s) ( '-H  oul-of-plant) hcuiding.721 (2) — 717 (n.)704 (2) — —810 (1) — -845 (2) - 845 (w)- — 017 (s) C-H oul -ol-plana banding.- 043 (1) 030 (jii)— 071 (w) 1 0 7 4 - 6 0 0 - 9 7 6 .ioo:i (5) 000 (10) — C'-O (aj^,) vmg.1027 (3) 1023 (3) 1028 (m) 1130 (m)(1-H iii-plann bonding,1151 (4b) 1155 (5) 1148 (jn)J17G (w) 1220 (w) 1240 (w)C-H Bym inatnc Htroiab. 550 +  012 =  1171,845 +  400 =  1251.1281 (1) 1282 (3) 1274 (V8) 1307 (s)C-K auliHymmi'tno Hl-roiali,1322 (1) 1310 (h) 1 0 0 0 - 2 7 7  =  1328.1380 (w) 1 0 0 3 - 2 2 1 .  1382.1448 (0) 1151 (1) 1440 (s) 1000-^148 =  1452.— — 1475 (tsh)1402 (0) 1491 (1) 1542 (1)1103 (ill) 721 1 704 =  1485.1578 (1) 1581 (m) ring.lOOO (7) 1000 (10) 1003 («) 0 = 0  Htj'C'icll.1058 (5) JOGl (5) 1074 (vs) 0  =  0 Hirctali.— _ _ 1080 (w) 2 X 8 4 5  =  1090.3052 (2L>) — 3053 (w) C-H Htrotiuh.N O H M A J. C O O K D I M A T K T K K A 'V M K N 1'Vibraticmal Spectra^ Approximate Potential etc, 123Tf tlu' p]i(‘.nyl groups iii houzophenone firo assumed to be jioint masses the molecule can be troiitcd as a four body problem having tlie syjmiietry ot the point groiij) with a distribution B )^. All the normal vibrations arc bothKanum and infrared active, The Normal coordinate tieatment has been carried out by the aiithors according to the Wilson F-O matrix method. The followdng symbols are used for the eipiilibriiim values of bond distances and interbond angles which are shown in the Fig. 1.It =  (J.lHr, t^ ig. 1[n accordance! wuth the above notation an example of the possibh' tyjies of the potential constants ari.sing out of diflercnt interactions are • fa — C-R stretching constant. fa — <RGR bending constant, f^ j^  ^ < ]tC r t  and C — 0 angle bond interaction constant.f'dfi — C-R and <OCR bond-aiiglc interaction constant , the prime indicating that the bond and the angle do not have a common bonrl.The most general (puulrath- expression for the potential energy has the coetficients given in Table Tl.TABLE TIad Adi Ad, Aa APi AP2AD fn fVd fDd jDa fl)P fnpAdi fi fdd fda f'<W fdPAd, fd fda fdP f'dPAa h faP fafiAHi fp fPPA/S2 fP124 P, G. Puranik and P. V. RaoTho .syiujiieiry roordinatos for tho Type A,=  M ) .H, -  l/v'2(Ad,+Arf,).l/V G (2A a-A //,-A /?J.TypeR, -  l/VaiAA -A/J,)Tlio RVJunioiry coordmaioH arc iioriiialised and orl.hngonaJ. From ilie poioritial energy inafrix juid the nmlrix fonned from the coeificiienls eontiuned jn the symmetry coorrlmates the F  matrix elements aie formed. TJie F  matrices are as follows. Foi typeV m (Ju a --fjy n )  w m ^ a -fu p -r< ^ p )  l i m A U h  \-hnFoi' type Bjy -^ 4^4 \ I Jtl Jihi Jdp J'dp \ ^ ’ r U  “ ' J‘p-fpp 'The strneUiral paiametcrs of hoi/oplienono were not available to the authors, either fi-om X-ray or electron diffr.iolion data. ITowevor, the values ot bond distances given by Karl FTtuiptinan et (d. (li).57) for dimethoxy henzophenone and the value of niter bond angles given by Cllasston (IOil/)) are found suitable lor tho molecule umbM- investigation in cahadating the U matrix (‘Icmeiits. These values are :C -R -= I.4f)A, C -  O -  l.:iA, <H(1U -r i : i r  ami =  C ~ R  -  114"30'. The elements of (i iiiatiaeos Avere evaluated with the help of Decius (194S) Tables. The actual vahu s^ of the elements of G matriens for classes and are given beloAV. The out of plane vibrations failing under the (iass B  ^ have not been discussed in this paper.8-7820x1022 -2-9418x1022 7-6582 xl03o>2-5067x1022 ~~4-4914xl0»«1.2791 Xl03»y9-0887x1022 -9 -5886 X IQ2« ,G.. (I1-5856x103®Tile ])olentiiiJ oonsifuifs foi- ih.0 ino]oL'iiU\'^  ha.vinj^  similiiv .stnuitiires as boii- zoplicnomo w<iie trailsleri'ocl i-o tliis molocule. Probably in vioiv of the fact tliat tlie phenyl i^voups are assumed to be point masses tlie bond-angli* and ilie angle- angle interaction terms were v<‘ry critical Afl(‘r a Jew morlifieations iJie observed frecpioncies were i.-eprodnccd by calculations, the difference in their values being well within one [lei' cent. Tlie ])otentia1 eonstunts* thus finally arrived at are f j ,  =  13.0, fa  -  7.2f), /, I 5, fp  1.73, U i -  ■^'75, -  - ’l h, fan  -  1.17,f a n  -  0.026, 1.2, fj^n -2 .0 , f„n -  0.4 and fun 0.33.The observeil and the e.alculated values of the fiequeiicies of the normal vibrations considering*the phenyl groii]) to be a point mass are given in Table III.Vibrational Spectra^ Approximate Potential etc. 125TABLE ITTob.sorvcdTypo CiilrulatodRam anJG58 1674 16641151 1148 1150277 - 2731281 1274 1278567 _ 561T IT R  J t  M O D Y  N A M 1 C P H () P  E  R  T  I TO SThe hcavt content, free energy, entropy a.nd heat capacity al lionstant pressure for beir/ophenone with rigid rotator and harmonic oscillator approximation have bom calculated. The contributions from the normal vibrations discussed in this paper and the e.ontributions fi'oni the ring frequencies are included in calculat­ing the thermodynamic properties, for the ideal gaseous state at one atmospheric pressure for twelve temperatures in 100-1 OOtTK range. Since no data were avail­able for the vibrational frequencies in the gaseous state of the molecule, the ob­served values as rocordefl by the authors are used. The thermodynamic properties are given in Table TV.♦Rond constants and bond-liond interaction (jonstnnts arc given in md/A, bond-angle in teraction  torjns in  md/rad, a n g k  oonstants and angle-angle interaction ooustants are given in  mdA/rnd^.126 P. G. Pur anile and E. V. RaoTABLK JVH oiit li oci m iorfiy . cn i ro j)y  find heal. (■ii.])at i t y  lov bon / ojjlu '.n on eT'^ K Cm'100I'OO27;i;io;{4005000007008000001000n 0111 .7 014 l i15 :i,s It) 11 22 90 20 02 29 51 :i2 xi 35 12 37 805 0 .7 8  57 82 01.81 03 35 07 73 71 75 75 39 8 0 .2 3  84 89 89 44 9 3 .8 559 79 09 58 75 95 78 08 87 51 95 98 104 01 1 1 1 .2 4  118 23 125 09 131 7111 .3 0  18 07 23 .5 7  20 06 33 51 4 0 .3 0  40 87 50 43 53 .8 3  57 12 02 33N , B  'I’lio junjiH'niH nC iiunlau of tho inoloc uk' in » w.n.A - art* I f  ~ 54.94 5, Ij, =  272.194 and Is  —327.130. Tlio aro gjvon in K  and tho olhoi- qiinniilioH iiro in ral.K  E  ]r E  K  E  N O E  SDooiii.- ,^ J .  C , 1948, J .  ahem Phy.'},, 16, 1025.GkiHwIon. 1935, Annual ivporlR , ]>p 134.K ailo  H auptniaiin ot al., 1957, Arfa Cryst,, 10, 481Kolilrau.sch, K . w . b\, Pougiatz, A.. 1934, S. B . Aluid. Ik m . ]Y'Icai ,*143, 288, LcKtrudo, M., 1952 T I ipsoh pour le grade T)ofitc>urea iSicnfcw Pliyairpios do I 'l ln iv e rs i i i  do PoiliojH.Puranik, P. O., 19 53, T lifsis for Pli. D degroi ol llu  ^ Omnunia Uinvor.aifcy.

Vibrational Spectra, Approximate Potential Constants and Calculated Thermodynamic Properties of Benzophenone

http://arxiv.iacs.res.in:8080/jspui/bitstream/10821/3729/1/Vibrational%20spectra%2c%20approximate%20potential_Puranik%2c%20P%20G.pdf

Vibrational Spectra, Approximate Potential Constants and Calculated Thermodynamic Properties of Benzophenone

Abstract

Similar works

Full text

Available Versions

IACS Institutional Repository