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U. S. Department of Commerce National Bureau of Standards
Research Paper RP2031 Volume 43, October 1949
Part of the Journal of Research of the National Bureau of Standards
Infrared Absorption Spectra of the Liquid Butenes and 1,3-Butadiene
By E. Carroll Creitz and Francis A. Smith
The infrared absorption spectra, from 1 to 15 micron s, of I-b utene, 2-methylpropene
(isobutene) , cis-2-bu tene, trans-2-butene, and 1,3-butadiene have been recorded in the
liquid phase under pressures suffi cient to liquify t hem at room temperature.
The spectra of the same samples in the vapor phase have been r ecorded and are
presented for comparison.
A rock-salt prism was used for the range from 2 to 15 mi crons. The spectra of t he
same samples, both liquid and vapor, were obtain ed at h igher resolution over Lhe range
from 1 to 4.2 microns usin g a li t hium fluo ride prism, and a re presented for comparison .
The spectra obtained from t he liqu id phase prov ide data for t he development of a
procedure for t he analys is of liquid plant s t ream s by spectrometri c methods.
1. Introduction
One of Lhe factors limiting the accuracy of th e analysis of mixtures of the butenes and butadiene has been the difficulty of obtaining a sample for analysis in the vapor phase that is representative of the composiLion of the liquid in the "bomb" in which samples from liquid plant str eams are collected . This difficulty r esults from Lhe variable partial fractionation that takes place on vaporization. l The difficulLy might be largely eliminated in the case of infrared spectrometric analysis by the use of absorpLion cells for liquids that are tight at pressures high enough to permit analysis of the liquid at room temperature, based on spectra of the pure constituents in the liquid phase.
Cells for liquids , with rock-salt windows, tested to 35 Ib/in.2 gage, have been described by the present authors.2
The spectra of five of the constituents of such mixtures, I-butene, 2-methylpropene, cis-2-butene, trans-2-butene and 1,3-butadiene have been recorded in the liquid phase from 2 to 15 J1. with an N aCl prism and from 1 to 4.2 J1. with an LiF prism .
The spectra of these hydrocarbons in Lh e liquid phase apparently have not previollsly been re-
1 Vernon H. Dibeler and Fred L . ]\'lo11lel", J. R esearch N B S 39, 119 (J9n) RP J8l8.
, Francis A. Smith and E. Carroll Creitz, Analytical Cbern. In press.
Infrared Spectra of Liquid Butenes
corded, nor their spectra (liquid or vapor) were previously availa ble, as resolved by the LiF prism, in the serie distributed by American Petrolcum InsLitute Research Project 44.3
II. The Spectrometer
The instrument used was a model 12B PerkinElmcr infrared absorption spectrometer. The direct-current th ermocouple signal was fed Lhrough a General Motors brea]mr-Lype amplifier to a Brown Electronik strip chart recorder, operating on a stabilized-power supply . The Globar source was operated at about 210 watts from a separate stabilizer.
Prisms of N aCI and LiF were used in the present work.
The peak-to-peak elecLrical noise, a facLor affecting the photometric accurac~r , h as been r educed to about ± 1 percent at a sensitivi ty of 0.1 jJ.V for full scale on the char t.4
In normal operation, as for th e present work, the sensit ivity is reduced Lo 0.6J1.v for full scale, and th e slits are changed manually in steps according to a sch edule des igned to keep th e background energy between 40 and 90 on the linear chart scale. The spectrum is scanned from long toward short
3 Catalog or Infrared Spectral Data issued by tbe American Petroleum Institute Research Project 44 a t the National Bureau or Stand ards.
• E . Carroll Crcitz, Analy tical Chemistry 20, 707 (1948) .
365
- -~-~--~
I L
wavelengths at from 1 to 8 minutes per revolution of the wavelength micrometer drum, the lower rates being used at short wavelengths where the resolution is affected by the speed of scanning, and where water vapor or carbon dioxide absorptions appear in the background. These absorptions are reduced by flushing the spectrometer housings with dry nitrogen. The background record and sample absorp tion are recorded success ivel y for each section of the spectrum without changing the slit . A slight overlap between sections provides good continuity of photometric values from section to section at different slit settings.
Adjustment for the energy absorbed and reflected by the cell windows was made by the use of blank cells (a double thickness single window for the liquids), and the effects of stray energy have been minimized by the use of glass and LiF shutters.
The wavelengths of sharp bands are accurate to between 0.01 and 0.02 /-I and adjacent relative values of percentage transmittance to about 1 percent except when occasional departures from linearity of the zero drift may result in absolute errors of as much as 5 percent or errors in relative values between the ends and the central portion of a section of spectrum of a like amount. The magnitude and departures from linearity of the zero drift were minimized by automatically maintaining the air temperature at the spectrometer constant to ± 0.2 deg O.
The r esolution attained under the present conditions represents a definite improvem ent, in the 2- to 6-/-1 range, over that attained by instruments from which spectra for the compounds studied have been made available to the present time by American Petroleum Institute R esearch Project 44 (see foo tnote 3).
III. Source and Purity of the Butenes and Butadiene
The I-butene, 2-methylpropene, cis-2-butene, and trans-2-butene were Phillips Petroleum Oompany's Research Grade, certified by this Bureau from measurements of freezing points, as having th e following purities respectively : 99.88± 0.2 percent, 99.30 ± 0.20 percent, 96.18 ± 0.15 percent, and 98.92±0.10 percent.
The 1,3-butadiene was Phillips Research Grade material that had been stored for about 4 years. The material used in this work was purified by
366
two distillations through a dedimerizing column developed at the Sun Oil 00.5 Subsequent analysis by mass spectrometer showed the following impurities: n-butane, 0.06 p ercent; 2-methylpropane (isobutane) , 0.05 p ercent ; n-propane, 0.05 percent ; propylene, 0.09 percent; and total butenes 0.44 percent; totaling 0.69 percent and giving 1,3-butadiene by differ ence, approximately 99.3 p ercent.
The samples were protected from contamination during measurement by transfer to the absorption cells through Ys-in. copper tubing. Oonnections were made with stainless steel cone to brass cylinder fittings and the flow controlled by metal needle valves with saran packing.6
IV. Procedure for Transferring Sample
The cylinder in which the sample was obtained was fitt ed with an adapter and a needle valve to control the flow. N ear the cylinder end of the sample line 'was a tee connecting to a pressure gage. The other end was connected to one side of the cell. A needle valve was connected to the other side of the cell, the outlet of the valve being connected to a tube leading to an air exhaust vent or through a drying trap to a water aspirator pump as required.
With the needle valve at the cell outlet connected to the pump and that near the cylinder open, the cell and line up to the cylinder valve were evacuated. Both needle valves were then closed , the cylinder valve opened , and vapor admitted to the line and cell by opening slightly the needle valve near the cylinder. Evacuation and filling were perform ed three t imes, after 'which the cell outlet valve was connected to th e vent. The temperature of the cylinder and gage were raised slightly by radiation from an electric lamp with reflector until the pressure of the vapor was sufficient to produce condensation in the cell at the existing temperature. Bubbles were vented through the outlet n eedle valve until the cell filled completely and remained so. Of course when analyzing liquid samples of mixtures from plant streams the connection to the sample container would be made at the bottom and the entire line and cell filled with liquid, no vapor phase being present between container and cell .
' James L. Jezl and Charles P . llabJitzel, Analytical Chern. 21, 1046 (1949l.
6 Connections and needle valves de,'eloped at ibis Dureau by H . F. Stirn· son. Unpublished.
Journal of Research
The connecting tubing was sufficiently flexible to permit ready int erchange of the filled cell and the blank cell in the spectrometer ways. The t emperature recorded was that of the air at the spectrometer at the time of recording the spectrum. Spectra were initially recorded at 25.2 0 C, but, when it was found that the vapor pressure of the lower boiling samples exceeded the safe cell pressure at that temperature, the air temperature was set at about 21.6 0 C where the remainder of the work was done.
V. Results
Observed transmittances in percentage have been plotted with respec t to wavelengths and wave number, and the resulting spectrograms are presented in pairs i n figures 1 to 10, liquid and vapor spectra for each substance being adjacent to facilitate comparison.
Cells of three different thicknesses were used for Lhe liquid samples, and tl11'ee or more pressures were used in the case of the vapor samples. This placed most of the transmittance minima between 20 and 80 percent with one cell or another.
Differences, the significance of which will not be considercd in this paper, appear between the
Infrared Spectra of Liquid Butenes
liquid and vapor spectra of each sample. In general the spectrum of the liquid appears to be simpler than that of the vapor, and in numerous instances the member of shorter wavelength of what appears as a doublet in the vapor spectrum is much weaker or missing in the spec Lrum of the liquid. However , there appear to be a few instances in which the member of shor te r wavelength is stronger in the liquid than in the vapor.
The band at 14.8 J.L in liquid trans-2-butene but not in the vapor (fig. 4), is undoubtedly the result of absorption by the cis-isomer , which has its strongest absorption at this wavelength . Since it boils at a higher temperature than the trans-isomer, it could be .expected to be present in higher concentration in the liquid than in the vapor phase of trans-2-butene. The observed intensity of the band is in good agreement with Lhe probable concentration (1 %) of the cis-isomer in the sample.
The different intensities of the several components of the C- H band resolved by the LiF prism in the spectra of the liquid as compared with those of the vapor may be of interest in conn ection with the use of this band for analytical purposes, as reported by Saier and Coggeshall.7
1 E leanor L. Saier and Norman D. Coggeshall , Anal ytical Chem. 20, 8 12 (l9'18).
367
- -- -- --- ----
100
BO
60
40
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~ ,~/V'~ __ \:,,, 30mm '-"i--\"J {\~ r·.
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2000 WAVE NUMBERS. em - I 1500 , , , .:,. , ,
~ v"V"', /"'''-..,.. ..... ''' r~
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1200 " I"
----
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\
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\
1 100 'I ..-'~ \
-"" "- /'/
1\ \
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I \ If'
\ I \
/ /
4 .5 5 .0 5 .5 6.0 6. 5 7 .0 7 .5 B. O 0.5 9.0 9.5 WAVELEN GTH . MICRONS
FIGURE L I nfmred absorption spectrum of i -buten e.
WAVE NUMBERS . em-I 5000 4000 3 000 2500 2000 1500 1400 1300 1,?CO 1100
1 00 r..L....l-'--+-,'.c' "'-'::' .;..' ... ' .,L'-i't--'-' ..ll.c' "+,'' ''.J::!,' H e'-' ...w,,-J-' +r"-I...J.-,j.....,fl",,*;-:L' -'-r 'L-L-L' """- 'L--7,.---,-1 ..l'...J'c....c,' ;,-,1-'--'-:":-,-....1...1 ..!...."-1~ I I' I " I I • \ I
r- 'JlMr- '..\. ,I '- 8"O';;;'(V ~(V\/~~ ~-' c'~('J' /A / .... 130m.m II "I <.1 1 /' '[ - ~ ] 'II, ,"\, \ r- ( 1 .. 30mm ,I' /\ \ I· :i \ L,f ..-'8omm
u ~ \I 1/'\ I:;' .'1 v I \ ~ II . I ) I ,.: / .F' \'30mm ;, \ I
20 1---L-1----+-+~~i~~-+_--~--~---I+r__+1~-_4_H-~--t~·
2 .5 4 .0 4 .5 5.0 5.5 6.0 B .5 WAVELENGTH. MICRONS
FlGURE 2, Infmted absorption spectTUrn of 2-methylpropene (isobutene).
368 Journal of Research
100
80
60
4 0
20
o 100
80
60
40
20
100
80
60
40
20
0
100
80
WAVE NUMBERS, em-I 1'?? , , 1000 9?0 800 700
- J ---, --- / - ,
-"'--, .J " '\J ............. ~-
'-, - \..1 ,
'- / -- , ------'>.-
\ ... /'v" ___ \ "
( 1-"80 mm
I~ ~ \ '-. ""J (- I ~ \ / ." 30mm I \ / : I I f\ \ / \ : I
\ \,_1 \ '-..'\: I
h 1\) ~ \ I \ I
~ ~ \ 1---/ LrJ '-\~"j
./
--O.087mm
O.016mm --~-------1-/\-/ -... :'
/ - I \ , \ / , I -
: " \ I \
- - ~m ~ \ I \ ~ / 1
~ \ \ : \ I \ 1 \ I \ I \ 1 \ I
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11 00 1000 ' I , , , , I --\
I
~/ "-
WAVELENGTH, MICR ONS
FIOU IlIC I - Con t i n ned,
WAVE NUMBERs.cm- 1 "00
I I I I 1 I , 7 00
I \ 1 //~ \_/'v \ ", \ I \ ': __ '-J- I
\ I ':
'omm .... /, eOmm /v-----~ r---+----C-~-4---+_~:I-/-- ;' -r--~---~------
it' (~~40mm \ (\ L \ : \ ~
~J 1\ ( \
\ \ \
\ \ \
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-, -,
\ / \ \ I \ 1
10.0 10.5
.- 1 :' 1
:"\-: ! I 1 I
r: I / IH'\~ I J / \::1
Ii
O.0 16m m
I I
I
/' IO.087mm
O. 421mm I---+-----~-----~----~
12 .5 13 .0 13.5 14,0 14.5 15.0 WAVELENGTH, MICRONS
FIOURE 2- Contin ned,
Infrared Spectra of Liquid Butene-s
COMPOUND
1- Butene
C4 He SOURCE AND PURITY
Philli ps Research Gro de
99 .88.t 0 .2 %
STA TE Gos TEMPERA lURE rv 25 .0 ·C CELL LENGTH 10 e m
NoCI Pr ism
Corr'nl- Cell + S ompl, Vt 8101111 ST roy (II.'OY by Shu".,.
lABORA TORY
Nat ionol Bureou of Standards
Gos Chem is try Sec t ion 5 , 7
COMPOUND
SOU RCE AND PURITY
Phillips Reseor ch Grode
99.68.t 0 .2 .;"
ST ATE Liquid
TEMPERA TURE IV 21.6 · C
CEll lENGTH 01 ind. c a T, d
COMPOUND
2 - Mefhylpropene
--SOUHl~:;:e "pu",,"'''''Y--/ Phillips Reseorch Grode
____ ._9 . ~:tO~
Gas TEMPE RATURE
efn lfNGTH
rv 25 .0 · C
10 c m
NaCI Pr is m
COff'IIS- Cell .. Sa mp le ~s Bla" ~ Slra~ Enl'91 by Shull,,.
--tA80iATORY
Nat ionol Bure au ot S Tandards
Go s Chem istr y Sec t ion 5 , 7
COMPOU N D
2- Methy lpr op ene
C 4 H8 SOUR CE ANO PUR ITY
Phill ips Research Gro de
__ ..!.'_,'_O_t O:::,2::0~"=---_-I
SlATE Li quid
TEMPERATURE rv 21.6·C
CHl LENGTH 0 1 in dicaT e d
No GI Prism
Ca,"ns- ~~:~ 1" (~~~~I eb;s s~luaT~:" Cell Pr ess ur. "" 2 6 psi gog,
--- (A80R ATORY
Notional Bureau of St andards
Ga s Ch emis try Sect ion 5 _ 7
369
100
80
s o
40
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~ 0
~100 l-I-
i <f)
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so
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I I
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O.Ot6 mm "
.':
...;/,..- -
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/ /
/O.08 7mm
2 .5 3.0 3.5 4 .0 4 .5 5.0 5 .5 6.0 6,5 7 .0 7 .5 S.O 0.5 9.0 9.5 WAVELENGTH, MICRONS
FIGURE 3. I nfmred absorption spectrum of cis-2-butene.
5000 4000 , , , I T ! t! t I I I I I , I , 1 1 , 1 , , ' I' "" I, , 1 , , 3000 2500 2000 WAVE NUMBERS, em-I
1500 1400 1300 1200 11 00
'-~'\
IV \ , .. (,--- .,_f /" ...... ""'" .r....",,...r- \ r~\. - 8;';;:--1'\ ~lrJ .\ '\. 30mm .' / SOmm \, ~\ \j \ I """'_ ...... - \ 30mm " ,,, ;V ,'// \ I""~ I--'~"_/ \1 1\ :[\, fI
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2.5 3.0 3.5 5.0 5 .S 6.0 6 : 5 WAVELENG TH ,MICRONS
4 .0 4 .5 7.0 7 .5 8.0 8.5 9,0 9.5
FIGURE 4. Infrared absorption spectrum of trans-2-butene.
370 Journal of Research
WAVE NUMBERS, em- I
100 1\O? I I
1 000 , 9 ?0 BOO 7?0 I I I I I I I , ,
---- - ~ ~
-" - /'-~ ',I. "- / ~ '-~- - "",
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J o 100 r-~----r------'-'-----'------~-------r-------r-------r------~------~------r------'-------'
9.5 10.0
1100 100
I' 1000
I 80
60
40
20
C
100
80
60
4 0
20
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9,5 10.0
I I (
>_,-r_'/ ........ --/-...r ........ ",
" " "-
\ '\
0.087 mm
O.016mm
"-
\ \ "
\ \ \ 0.427m~""
,-.--+----l----~-"'-__I--r_,+__,____,,'-
I ~~ \ '--' 10.5 1 1.0 11 .5 12.0 12.5
WAVELENGTH , MICRONS 1 3. 0 13.5 14.0 14. 5 15.0
Freu m; ,[-Cont inued,
WAVE NUMBER S , em- I ~oo 700 900
I , I I I I , r
------ ----- -----------------
BOmm
~ 30mm ,' / 740mm
~ /'" -I V : r I
:' J : i
I
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\, ~ : J ~, .. : --L-.
/
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_f-' , -~ "" , " ---- - ./----. f----./
----O.016mm - ~~ ~ '--,
/' ./ \
/ /' _ V \J :
f--/ / ~ / O.087mm
/ Lm / /
/ ------- r---- ---
/ I
I
" J / I
1-/ ./ ','
10.5 11.0 11.5 12.0 12.5 1 3 .0 13.5 14.0 14.5 15.0 WAVELENGTH , MICRONS
FIGURE 4---Continued,
Infrared Spectra of Liquid Butenes
COMPOUND
cis- 2- Bul ene
C4 He SOURCE AND PURITY
Phi l lips Research Grad e
96.18'£ 0 .15 -,4
STATE Gas
TEMPERATURE "" 25 .0·C
CEtl lE NGT H 10 e m
Na CI Prism
Corr'n. - Cell ... Sam pl. 'IS Blan k St ray EntrOy by Shull. r.
LABORATORY
Nat ional Bureau of Standa rd s
Gas Chemis try Section 5 . 7
CO MPOU ND
cis-2-Bulene C4 H8
~E AND PURI-" ----
Ph illip s Research Gra de
96 . 18 ± 0 .15·4
STATE LiQ;;-----1
TEMPERATURE '" 21.6 ·C
CEll lENGTH 05 in dic oted
No CI Pr i sm
Corr 'ns - Cell i' So mple 'IS Blank Stray En.roy by Shu llers
Cel l Pressu" 16 psi 0 00' ---l -A BOR ATORY --
Notional Bureau of Standards Gas Chemist ry Section
~, ______ ~5.~7 ______ ~
COMPOUND
trons-2- Butene
C 4 H 8 f-souiiC E AND ~
Phi llips Research Grade
98 . 92 ± 0.10·1.
ST ATE Gas
TE MPER ATURE '" 25.0·C
CEil lENGTH 10 em
No CI p-',;-sm---I
Corr 'n. - C. II t- Sompl e .... Bioi'l l!. Stray Entrlil Y by Shulltr.
LABORATORY
No t iona l Bureau of Standard s Gas Chemistry Section
5,7
COMPOUND
Irons - 2- Bulene C4 He
----'-QURCE A ND PURITY
Phillips Research Gr ode
98 .92 ± 0.10·1.
STATE Liquid
TEMPERATURE "" 21.6·C
CEll le NGT H' as ind ic oted
NoCI Prism -
Con'ns- Cell +Sampl e vs Blank Stray Eneroy by Shutt., .
Cell p,. u ure 2 0p li gog. lA BORATO~Y
Notiona l Bureau af Standards Gas Chemistry Section
5 .7
371
5 000 100
8 0
6 0
40
>-Z
'" 0 20
'" '" Q.
'" 0 0
~100 >-t:: ~ fJ) Z 80 .. '" >-
60
40
20
~
0
4 0
0
0 1,0
4000
2 ,5
~
3 .0
\ 1\
I:; I I:: I 1 I
1
3. 5
Ir vvrv
4 .0 4 .5
WAVE NUMBERS, em-I 20100
II
",
/" '\
I I \ ~ . :' 1 I I \., ~ ;1
I I A 1:;::1 i v : I
II
\
:~,.' j l- "" ",
f " :
5 .0 .. 5 .5 6.0 WAVELENGTH,MICRONS
r
G.!?
1500
O.01 6mm
\ ( '0 I I \
\J \
1200 1100 , I
\ \\
v
." .. : ..
'.-,' ~- --~ 'O.087mm "-
\
" ,
\ I
:: (
I' : : I "\ :: I \ ,!
\ :: I 1 ' 1
\ ( \ \ I / "" --+_ \j 1(.7mm \ \ \ I
I I I I ( \ 1 1\ I wv
7 .5 8 ,0
1\
8 .5 9 .0
\ \ \
9, 5
F I GU RE 5. I nfr ared absorption spectrwn of I, S-butadiene.
"'\",V\ - 0.016rr:om
t'- ....... ~ , .-'
h l",\ ,\ -' "
r, n.j - '- ,":"
~\f\ ..... {\f r '~ , : : I \ 1/\1 ) " .... , . " r \ \ ' I
(I{VfJ \ I : i,
0 t: I t: I I : 1
I\~ \ \' : !J (' \ :',-.'
\\11: '" J/ I I;.
l\f \:; \ \:.:
~- ---'\ -- ' ./"/ 0.087mrK
r t-v\r VO.~6I mlm V
SOUR CE AND PURITY
Phill ips Research Grode
99.88:*: 0.2%
CELL UN GTH 10 em
Li F P r i sm
Corr'ns- Cell + Somple vs Slo ~k
LABORATORY Na tiona l Bure au of Standards
Gas Chem istry Sectio n 5, 7
SOUR,CE AND PU RITY
Phil lips Resear ch Grade
99.88 ± O.:! -/o
Liqui d TEMPUATURE N 25.2·C
osi"d lcot.d
LiF P ris m
Corr'ns - C. II .. Sample VI Blank
C. II Pr.uu re IV 32 p il gog. LABORATORY
Notiona l Bureau of St a nd a rds Gas Che-mis tr y S ect ion
5.7
1.5 2.0 2,5 3 0 3,5 4,0 4 .5 WAVELENGTH ,MICRON S
FIGU R E 6. I nfrare d absorption spectm1n of I-butene.
372 Journal of Research
1100 100 I I \., '~
,'" 1\ \' .. eo U j ..
60 \ '\
\ \
1000 WAVE NUMBERS. C~O-~
15mm ...... :
.~, /"l 1 \ I
40 1--+-~~---~::~',~!~~I--\~~----+~~--~----~------~----~----~------~-----+-- __ ~
/ I
20
0 100
\ I
\ \ I , ,I
\ \ ' I 1/ /
I 1
\ 1" !J " .., ..... 1 '--J' I
0 .01 6 mm --/'- ---- ...... - ....... -....-~~~----r---~----~--~~~.~~--~--~----~---4--~
/
10.0 10.5 11.0
~.087mm
/ I
/ I~~/ ~ lVa.27mm ~
I / ,.-
1/ I
I
/ /
v
11.5 12 .0 12.5 WAVELENGTH ,MICRONS
13,0
FIGUHE G--Continnecl .
13. 5 14.0 14.5 15.0
10000 BOOO 6000 5000 WAVE NUMBERS. em - I ' 000 lODO 2500
CO M POUND
' ,3-But od iene C4 H 6
SOURCE AND PURITY
Phill ips Resea rc h Grode (Oe di meriud in Sur't Column)
1 _____ ...:~=99 . 3 "/,'--------1 STATE Gas
TEMPERATURE tv 25.0 ·C
CEll lENGTH 10 e m
NoGI Pris~
COH'ns- ~::~; ~~::~e b~' s~~~~:n -----LABORATORy
Not ionol Bure'cu I)f S tandardS Gas Chemistry Section
5.7
COMPOUND
1,3-Butodiene
C4 HS SOURCE AND PURITY
Phillips Research Grode (Oe dlmerlzeo in Sun Column )
rv 99.",.' "'%'-____ --1 STATE Liquid
TEM PERATURE rv 2 1.6 · C
CE ll lEN GTH as ind ic .hd
NoGI Prism
Corr'ns- C,II ... Sample VI Blan k S iroy En,rQY by ShlJlllrs
~!'~l~;~R ;;02R7yP ' i 401 0 401'
Not ional Bureau of Standards Gas Chemis tr y Section
5.7
100~~~~~1~~~ ~l_,~~--~I ~' ~~~~-+I~-'~*r~~'~J~t' ~~ ~~~II)I)-L' ~-C~~~[--LI --~~--~Tt~--'---+' --~'--~~'---'I
~ V _\'!)\_~~ '/~ j1 1\ -"r\\-c" ~'iK~-, \ rIlill I \ ,','Omm I
601------r------f------ ----- i,.-----\d---j-'IJ ------ . I- .,.'-' ---- ,
2 - M elhy lpropen e
C4 He ~oU ~C~pull l ' l--
Phill ips ResearCh Grode
! ' " I , "
i ::I-__ +-__ -+ __ ~f_--+---+v--__j_--j_-_j_---~ r -1·---'-~ (k,,~'r ) !).t ... o z ~ 100 f-~---,------,--,,~"~~~------,------r------r------r-----,------~0.~0'6~m-m-.-,------,------,-----,
i <J)
~ eO I------+------r--1I'i-~~----~--111fr;r~---+--_,'~~~-V 0: ....
6°r------+------t---~~-----_1----_1r~--ruH_rl
40f-------r----~1------~-----+------·1~~---
20r------+------r-----~-----+-----
1. 5 2.0 25 )0 WAVELENGTH t M IC RONS
' .5
F I GURE 7. I nfrared absor-ption spectrum of 2-methylpropene (isobutene).
Infrared Spectra of Liquid Butenes
Go, r<J 21.6·C
10 tm
LiF Pl ism
Co ,,'n , - C. II . Sompl . VI Blank
Not iona l Bureau of Slandords Gos Ch em islry Sec l ion
5.7
2-Melhy lpr open e
C4 He
Phillips Reseorcn Grode
99 . 30 1 020 °/.
LiQu i d
o ~ i nd ie Olt d
LiF Pr i sm
Co rr'ns- C, II. Somplt n 8 10nlo,
C,II Pren u.t I"V 31 p l l gog.
lA 80RATORY Notional Bureau of Standards
Gas Ch em is lry Sec l ion 5 . 7
373
I-----~
0000 , 100
.... z w 2 u a: w a.
w u z
0
0
0
0
0
~ 100 ....
8000
\rJ
I
60 00
'---h Ir V
i <f) z ~ ~ h :. 80 ....
. WAVE NUMBERS, em-I 5000 4 000 3000 2500
If ~' ,"-.. .. ./ cr\' 1/\\\' !:r~:7/ --- -- --~ 80mll'l
\./1 r- f\
AI 1\7 \ \
, v \ ~ I I 74 0 mm
.1
( V \ ~\ '1
V i (: r' ) :f: I , I
I I 1
\ ,-.... /) \ .... \. ...
I .. ··, .. , O.Ollmm
I hn:', \,:'- ..... - "',/--, /-..... , ,.,."-- ..... ,, ...- ........... /"\ 0.083mll'l ) " 1 \.,) \ 1 ,
\.,f ,
I I) , ( ~ \ 1(\ ,I
~ Ir \ /\} ~ 0
60
40
0
0 1.0
10000 100
.... z
80
60
40
w 20 u a: w a.
w 0 .., 0
~
1.5
8 000 6000
V '-.r \
\0
Z
~ 10 !: ,. <f)
z ~ ~ h
0
VJ \ \ 1 I V A,/ (:! 1
\ i\/; / /
1\/ v \ : .\1 I
\1 I I I
\\ _~ I 2.0 , 2 .. 3.0 3.5 4.0
WAVELENGTH. MICRO NS
FIGURE 8. Infrared absorption spectrum of cis-2-butene.
5000
If ~
--..... ....,-,
r ~\
WAVE NUMBERS. cm-I 4000
\ '\,/\/" ,
IV'~ ,/ ' j1J Ij
3000
~ 30 11'11'1'1
liA! IV ~ \.
I V~ \ I
\ I " ri \1
, \ ; I ,
\ " \/ i 'I I \,-_/''''
- -I , ....... ;-"..--" '---"r\/ 'j "\ I , f\/ )1 0 I
2500
1,/,\ /,- -/ r -, -' /'\'.:/ n I I I-
I " / V
II /\ I v
-V
I I) V
1.······:··\ (1 O.Ollmm /''',.// - ' \./
,;\ ,,""/ \ I ,0 .. 8
a: ... ~ c / (V '/ V \ r, / f\/V ~ \
/ \ I
10 f\ 1 r 1/ , ') ,
I I' 0 u
A~ \J
\ ,
\i ,
',I ( '\J l I / \ I , 0 \ J 4
U ~ \ " ::'\ ,
0 ~ I A U \ \ " :) V I
\
0 \....... ~ 1.0 1.5 2.0 2.5 3.0 3.5 4.0
WAVELEN GTH, MI CRONS
FIGURE 9. Infrared absorption spectrum of trans-2-blltene.
0.461mm
80mrn
740mm
0 .083mm
O.46 l mm
4.
4.5
COMPOUNO
cis- 2- Butene
C4 He --SOUI(C E ANa PURlTY
Philli ps Research Grode 96.18.10. 0 .15"'"
STATE Gas TEMPERATURE "'-' 2 5 .2" C
CflL LENGTH 10 em .
LiF Prism
COrt'ns-CIII ... Sample Vi Blan k
LABORATORY
Nat iona l Bureau of STandards Gas ChemisTry Sect ion
5.7
ci s-2-But ene
C4 He SOURCE ANa PUR , a
Philli ps Research Grode 96 .1 8"'0.15"'"
Li quid
COMPOUND
Irons-2-8utene
C4 He
SOURCE AND PURITY
Phillips Research Grade
ge.92:t0.10·1o
TEMPERATURE
Li F Prism
Co.,'ns- Cfll ... Sample vs Blank
LABO RATORY Not ional Bureau 01 St ondards
Gas Chemistry Section 5.7
frons - 2- Butene
C4 He SOURCE AND PURITY
Phil lips Resea r ch Grade
98.92±O.IO"lo
STATE Liquid TEMPERATURE I'V 25.2·C
CEll LENGTH al indicat'd
LiF Prism
COfr'n$ - Cell ... Sampl, vs 8 lan ~
'fllPreHure IV 2epsi tjloQ' LABORATORY
Nat ional Bureau 01 Standards Gas Chemistry Section
5.7
374 TournaI of Research
ICOoo BOOO I
'0 O ~
0
6000 5000
1\ (
I~
WAVE NUMBERS I em -I ' 0 0 3000 25 00
0
0, ______ +_----~----_+----~------+~-1'~----~----_t----_+--_+~\:-0~+!~~1 +_----~----_+--__ -+ ____ ~ \ 1~1",1
I- I' ~ 2o l------~----_+------4_----_+------+_----_+------~-----~---I-~+---I~-+------~----~-----+----~
~ ) ~ CL-____ -L ____ ~ ______ ~ ____ ~ ______ ~ ____ _L ______ L_ ____ _L __ ~~~~ __ ~ ____ _L ______ L_ ____ _L ____ ~
<> z ~ 100 l-
i '" z '" ao a: I-
60
40
20
V' \..- ~ n
I~
1 15
\
'(~ ,- ,\ .. ..., , rr /\ r
" I ~ I"'" V !(h ~\I\(I , " ~, \' r \
~ q r / V \ \: I: I:
.. t \ \\ I\r \ \v
\~ 0 '.5 30
WAVEL ENGTH, MICRO NS
0.016mm ,.' ..r~...r./ ............. ,,1'"'-\ ;--0 .OS7mm
.. : / I rV "---'\,.." I
: , ~27mm V \ II v : , .. : " .. ..:..1..-
I: :::, ' I .;, , I I
'J; ,II..}
' .5 ' .0
FIG U RE 10. I nfrared absorption spectrum of l, S-butadiene.
W AS HINGTON, June 6, 1949.
Infrared Spectra of Liquid Butenes
4.5
1,3-Bu l odi ene
C4 H6 SOU RCE A ND ~UR ln
Phillips Reseor ch Grod, 10.dimr ,il td in Sun Column )
N 99 3-'"
Go. rv 25.2 · C
10 c. m
UF Prism
Corr'nl-C, .. + $ampl, VI Blon ~
. lA 'ORATOIY Na t ionol Bureou of Standards
Gas Chem is try Section 5.7
I,3-Butod ,ene C 4 H 6
SOURCE AND PURITY
Ph ill ips ResearCh Grode (O.d imu jad in Sun Colu mn)
N 99.3 -10
tE MPERATURE I"V 25.2"'C
CEll lENGTH OJ in d iC Oh d
UF Prism
Con 'n, -C. II . Sompl . VI B l on~
C, II Prill " " rv 30 p al 000' lA 60RATOIIY
Not ional Bl,lre au of Sto ndord s Gos Chemis try SeCTion
5.7
375