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Infrared Spectra of Methanol, Ethanol, and N-Propanol Earle K

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Infrared Spectra of Methanol, Ethanol, and N-Propanol Earle K -- ~ ---------------------------~------------~--~--------------------------------------~ Journal of Research of the National Bureau of StanJards Vol. 48, No.4, April 1952 Research Paper 2314 Infrared Spectra of Methanol, Ethanol, and n-Propanol Earle K. Plyler The infrared absorption spectra of methanol, ethanol, a nd n-propanol have been meas­ ured with prism instruments. Studies have bcen made of the vapors and of several dilu te solu tions. The m ethanol spectra, between 2 to 15 microns, provided a direct comparison with t he other two alcohols and co nfirmed earlier work on the cxistence of a number of low­ intensity bands. The two other a lcohols were studied from 2 to 36 microns. T he ?ands have been classified in relation to the O- H , C - H , C - O, and C- C vibratIOns wlthlll the molecules. The long-wave absorption, in the region beyond 30 microns, for each alcohol, is attributed to t he hindered rotation of OH. The object of the present study was to con­ firm the assignmen ts for m ethanol and to study and assign the vibrational spectra of ethanol and n-propanol. 1. Introduction bromide··iodide h ave been described elsewhere [4). The standard Perkin··Elmer thermocouple was used The infrared absorption spectrum of methanol in as a detector with all bu t the thallium bromide··iodide the vapor state was measured by Borden and Barker prism. H ere a Golay detector was substituted for [l] l with a gratin g spectrometer. The stro nger bands the thermocouple. The spec trometers were equipped were resolved so that the rotational structure was with a sli t··control device [5] , and except for the Go ·· apparen t. Their observations showed which band lay cell, the experimental arrangements were the wei·e of the perpendicular and which were of the ame as those described in a previous paper [5]. Gas parallel type. Noether [2], using a pli~ m instru­ cells of differcn t thi cknesses with vftrious pressure ment, also m easured the spectrum of methanol and were used. TIlC experimental arrangement did not observed several weak bands in addition to those allow the par tial pressures of the vapor to be deter­ studied by Borden and Barker. Some of these weak mined as all the cells could not be evacuated . bands have been classified as fundamentals and com­ The absorption spectrit of the li quids, d.iluted with binations [3 ]. The object of the present study was to carbon tetrachloride and cftrbon disulfide, were m eas·· confirm the assignments fo r methanol and to study ured on a Baird recording infrared spec trometer and assign the vibrational pectra of ethanol and with a sodium chlorid e prism . Solutions of different n-propanol. These alcohols have no t been measured concentrations as well as cells of variolls thi cknesses previously over an extended infrared region, and their were used. To obtain a higher resolution from 2.6 spectra have not been classified. to 3.6 f.1. , measuremen ts in this region were repeated, In th e presen t work, the spectra of ethanol and with a lithium-fluoride prism in the Perkin-Elmer n··propanol have b een measured from 2 to 40 f.1. in spec trome ter. the vapor state and from 2 to 15 f.1. in solutions of 0014 a nd OS2. Because of the similarity in struc·· 3. Results and Discussion ture of th ese alcohols, the positions of many absorp·· tion bands appear in th e same regions. No attempt The experimental results are given in six figures was made to repeat the long wavelength region in and two tables. Figure 1 presen ts the vapor ab­ methanol, as it would not be possible to improve on sorption spectra between 2 a nd 15 f.1. of methanol, the grating measurem ents of Borden and Barker ethanol, and n.·propanol. In th e regions of strong wi th a prism spectrograph. However, the 2- to water vapor absorption, bands in the alcohols could 15-f.1. region was measured as this region had not not be measured with r easonable accuracy; hence, bee n recorded on a double-beam instrument. dotted lines are used to denote the uncertainty of the absorption in these regions. 2. Experimental Procedure As shown in figure 1, methanol has a broad region of absorption centering near 7.43 f.1. This region The methanol, ethanol, and n··propanol were puri­ was restudied with the Perkin-Elmer model 21 spec­ fi ed under the direction of F. D . Rossini. They trometer to take advantage of th e higher resolu tion were found to be of high purity, which is essential made possible by the improved amplifier and to elimi­ in order to attribu te weak bands to the spectra of nate the effect of the water vapor bands. The re­ the alcohols. suI ts are shown in figure 2. The absorption spectra of the vapors were deter­ Figure 3 shows the long wavelength spectra of mined with Perkin-Elmer infrared spectrometers, ethanol and n-propanol in the vapor state. Ethanol models 12A a nd 120, usin g interchangeable prisms was examined in the region from 16 to 20 f.1., using an of lithium fluoride, sodium chloride, potassium h o­ absorption cellI m thick, but as there was no apppre­ mide, and thallium bromide-iodide. This allowed ciable absorption the curve is not shown. In the measurements to be made from 2 to approximately region from 20 to 38 jJ. lithium-fluoride, calcium­ 38 f.1. The properties and use of prisms of thallium fluoride and sodium-fluoride refl ectors were substi­ I Figures in brackets indicate the li terature rererences at the end or tbis paper. tuted s ~ ccess ivel y for th e usual aluminized mirror. 281 -- .... ~-- -- WAVE NUMBERS IN eM- I SOOO 3000 2000 1500 1300 1100 1000 900 800 700 100 -- -- ---V--- ~ 80 ',~ 5cm '. GO , 40 20 METHANOL VAPOR 100 ,~.~ ~Otm 80 ---- ---.'Wr- -\ , '"w .. I I U Z : I I ~ Vf~ GO ' .. I I " ;:; .... I, ICDcm V <J>z 4 0 <t" cr .... 20 ETHANOL VAPOR 10 0 .-- - - - ---------- ---\./'" 80 GO 40 20 n-PRO PANOl VAPOR 0 2 13 14 .. ~ WAVELENGTH IN MICRONS FIGUR E l. I nfrared absorption spectra fl'om 2 to 15 J.L of methanol, ethanol, and n-propanol in the vapor state_ rb,-t~~~sf~~~~ ll~~:d ~~~ e~ac\~ ~~~~1101·~ p or pressures at room tem perature except for the jn serts, wh!ch were obtained by removing so me of the \-a por from the .0 ME THYL ALCOHOL VAPOR () 30 20 -- 10 ---v, °a~0~~--7.•• ~~--~'~O --~~7~.• --~--7.•. 0 ~~--~•. ~.--~--9~.O--~~ WA .... EL ENGTH IN MICRONS FIGUR E 2_ I nfmred absorption spectrum from 6 to 10 !l oj methanol in the vapor state _ ~ .. The pressure is saturated ,-apor pressure at room temperature except lor the I' 16 11 II II 20 21 u . 1!3 t4 2 ' U 27 U 2.9 )0 31 12 II 34 35 11 11 II upper curve, which is at a press ure 01 6 em 01 H g. WAV[L[NGTH 1111 M'CRONS FIGURE 3. InfmTed absoTption spectra fTom 15 to 38 J.L of Although this resulted in some lo ss in the total re­ ethanol and n-pTopanol in the vapor state. fl ected energy, the stray radiation was reduced T he pressures are saturated vapor press ures lor the cun-e. of greatest absorption. consid erably. Table 1 lists the maxima observed in methanol, ethanol, and n-propanol, incorporating some of the tcrmine the band centers. 'With the exception of the resul ts of the higher resolu tion work in the 6- to 7.43-,u region of methanol, which is more compli­ lO- ,u region of m ethanol. The wavelength in mi­ cated and whose individual maxima mav even be crons, the wave number in cm- I , and the observed of a rotational nature, all the maxima of absorption intensity are given for each band. The intensity arc listed. As a result, some of the maxima in estim.ates are divided into five categories, extending table 1 may be parts of bands, such a P , Q, 01' R from very weak to very strong. In the regions of branches, as well as separate hands. This doubt considerable overlapping, it was not easy to de- as to the nature of the maxima in table 1 includes 282 ..... ow - ........ TABLE] . Ob served bands oj methanol, ethanol, and n-propanol i n the vapor state \V an'· \V ave lV ave- 'Vave 'Vave· \\'ave length numbcr I Inlensii y II length number I Intens ity length number I I ntensity I I II I , M et hanol I' cm- l }Jo em-I I' cm- I 2.26 4425 \I' 6. GI 1512 VW 8.75 1142 VIV 2.49 40 16 \' \I' 6.G6 1501 VIV S. SO 1136 VW 2.71 :368 7 M 6.76 1479 M 8.97 1114 VW 2.94 3401 VI' 6.87 1455 M 2·04 1106 VW 3.315 3017 M 6.98 1432 VW 9.14 1094 VW 3.346 ~989 i\I 7. 07 141 5 VIV 9.47 1056 VW 3. 360 2976 M 7. 43 1346 S 9.68 1033 S a 382 2959 M 7.96 1256 VW 10.57 946 VW 3395 2946 S 8.07 1239 VW 12.19 820 VIV 3. 414 2929 M 8. 17 1224 VW 12. 83 779 VW 3.512 2847 S 8.24 1213 VIY 13.58 736 VW 3.75 2667 V\I' 8.54 1171 vV\' 14.40 694 VW 4.86 2057 \1' 8.59 11 64 VIV Ethanol 2.30 4348 \1' 3.443 290'1 S 7, 19 1391 S 2.
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