The Infrared Spectra of Fluorocarbons and Related Compounds BY D. G. WEIBLEN Minnesota Mining and Manufacturing Company, St.

The Infrared Spectra of Fluorocarbons and Related Compounds

B Y D . G. W E I B L E N

Minnesota Mining and Manufacturing Company, St. Paid, Minnesota Page

Introduction 449 Hydrogen Stretching Frequencies 451

C s C , C s N , and N = C = 0 Stretching Frequencies 453

C = C Stretching Frequencies 453 C = 0 Stretching Frequencies 454 Spectral Correlations in the 1350 to 650 C m .

-1

Region 456

Infrared Absorption Spectra 458

Bibliography 499

Introduction

Interest in fluorocarbons, given great impetus by World War II developments, continues to grow, while the more recent interest in the many fluorocarbon derivatives is expanding even more rapidly. The inertness of fluorocarbon groups makes these materials difficult to charac­

terize and to analyze chemically. Hence, physical methods of analysis and identification would quite naturally be expected to play an important part in investigating this important domain of chemistry.

It is thus fortunate that the rapid growth of the science of fluorine chemistry during the past few years has been paralleled by a similar extension of the art and science of a very useful physical method of analysis—infrared spectrometry. In fact, at the present time the infrared spectrometer has become a tool commonly used by the chemist for both qualitative and quantitative analysis. A survey of the recent literature is convincing evidence that chemists are making considerable use of infrared spectrometry and that the data thus obtained have aided mate­

rially in the progress of our knowledge of fluorocarbons and their deriva­

tives. This section will be concerned with this application of infrared spectrometry.

The theory of infrared spectrometry, its application to problems of identification and analysis, and its instrumentation are amply covered in the literature and need not be considered here (7, 8, 67, 121, 129, 153,

159). It may suffice to say that the absorption of infrared radiation by a substance depends upon the atoms and their spatial arrangement in the

449

molecule as well as the forces existing between the atoms. Variation of these factors lead to differences in infrared absorption so that the infrared absorption spectrum is, in general, a unique characterization of a com­

pound, and may frequently be the most characteristic physical property of that compound.

This factor of uniqueness leads obviously to the simplest application of infrared spectrometry: identification of an unknown material by find­

ing a similar spectrum among the spectra previously obtained for known compounds. For this purpose a large library of reference spectra is re­

quired. To this end the infrared absorption spectra of 150 fluorine- containing compounds are included at the end of this chapter, as well as an index to the infrared spectra appearing in the literature. Two very excellent groups of infrared spectra of fluorine-containing compounds are those of Smith et al. (137, 139).

A more generally applicable method of qualitative analysis is based upon the correlation of infrared absorption frequencies with structural groups. Barnes et al. (7, 8), Colthup (24), and Thompson (147) have given spectral-structure correlations which indicate that such functional groups as OH, N H ₂ C = 0 , C = N , and C = C , give rise to absorptions at more or less specific wavelengths. In some cases the precise position of the absorption band gives some information about the substituent on the group. These correlations have been well established and their proper use can be of great assistance to the chemist in establishing the structure of an unknown material. One of the first applications of such use of infrared spectroscopy to fluorocarbons reported in the literature con­

cerned C ₃ F ₆ obtained from the pyrolysis of polyethforylene. This mate­

rial was first thought to have a cyclic structure. However, the presence of an infrared absorption band at 1795 c m r

1

(33, 162) near the region in which a compound containing a double bond would be expected to absorb was evidence which, together with the Raman (33) and electron diffraction data (17), led to the assignment of the olefinic structure.

Barnes, Gore, Stafford, and Williams (8) state that in the range above 1350 c m .

-1

(less than 7.4 μ) assignments can be made with some certainty since, first the frequency of the vibrations depends primarily on the masses of the atoms involved (i.e., those making up the functional group) and the bond force constants between them; and, second, in this range the vibrations resulting from the combined force constants and atomic masses are well separated and there is little likelihood of interactions causing frequency shifts from expected positions. Thus it is to be expected that the correlations for this spectral region will apply, at least to a first approximation, when fluorine is substituted for hydrogen except in the functional group. The degree to which this holds and the shifts encoun­

tered will be discussed below.

The above authors also say that in the spectral range below 1350 cm."

1

structural-spectral correlations become much less certain, for various combinations of force constants and atomic masses can give rise to absorption frequencies in the same region or there may be interactions causing frequency shifts. Nevertheless, useful correlations in this region can be obtained, as, for example, in the frequencies which can be used to establish the substitution on the phenyl group. In fact, McMurry and Thornton (94) have given very extensive structure-spectral correlations for hydrocarbons using principally spectral data in the 7 to 15 ě (667 to

1400 c m . - 1

) region. By limiting themselves to hydrocarbons and by making use of intensities as well as band positions, they have derived correlations for such things as the position of bands as a function of the chain length of normal hydrocarbons and as a function of the type of chain branching. Their results indicate the detailed information that can be obtained when a sufficiently large number of compounds of a limited type are thoroughly studied.

However, interactions between the various vibrations are very much greater in the case of fluorocarbons than in the case of hydrocarbons (8, 137). Claassen (23), for example, observes in his analysis of the infrared absorption spectrum of c-C ₄ F ₈ that the force constants are rather high for the interaction of pairs of C—F stretching coordinates involving the same carbon atom and for the interaction of F—C—F deformations with the bonds forming the sides. Thus correlations obtained for fluorine- containing materials in the spectral range below 1350 cm."

1

will have to be used with considerable caution. Furthermore, it seems improbable that correlations for fluorocarbons can be carried out to the extent that McMurry and Thornton (94) were able to carry them out for hydrocarbons.

The loss of correlations because of larger interactions is not entirely disadvantageous. Larger interactions of vibrations will cause slighter differences in structure to show up as greater spectral differences. Hence smaller structural differences should be detectable in fluorocarbons than in hydrocarbons, and identification by the "fingerprint" method of com­

paring known and unknown spectra should be facilitated.

Hydrogen Stretching Frequencies OH

The acids ^COOH* and the alcohols e C H ₂ O H in the liquid phass all show broad absorption bands due to associated OH vibrations with the maximum absorption near 3000 cm."

1

for the acids and 3300 cm."

1 for the alcohols. Fuson, Josien, Jones, and Lawson (42) found that CF ₃ COOH

* ^-denotes an alkforyl group.

in the gaseous state and at room temperature exists as a mixture of monomeric and associated molecules. They report a frequency at 3587 c m .

-1

for the " f r e e " OH stretching vibration and at 3000 cm."

1

for the

"associated" OH stretching vibration. They also studied CF ₃ COOD and reported 2648 and 2300 c m .

-1

for the corresponding values for the OD vibration.

N H

The frequency of the N H stretching vibration in hydrogen-containing fluorocarbon derivatives has not been studied. The spectra of the amides,

Ο

&C—NH ₂ , shown below, have a pair of absorption bands in the 3200 to 3400 cm.""

1

region in agreement with the general correlations of Barnes et al (8), Colthup (24), and Thompson (147).

CH

The work of Smith (137, 139) indicates the following values for the CH stretching vibration for compounds containing carbon, fluorine, and one hydrogen atom.

C F3H 3062 c m . - 1

— C F2^{H 3008 C}2^F6^H

> C F H 2990 ( C F3⁾2C F H and c-C*F9^H

Thus the substitution of fluorine on the same carbon atom as the hydro­

gen involved in the CH stretching vibration tends to increase the frequency. Unpublished work of the author on a few additional com­

pounds of this type is in agreement with the above data. Although addi­

tional compounds should be studied, it would appear probable that the CH stretching frequency could be used to give some indication of the position of a hydrogen atom in a hydrogen-containing fluorocarbon molecule. It would, however, be necessary to use lithium fluoride or calcium fluoride prisms when working with spectrometers such as the Perkin-Elmer Model 12C or 21.

The determination of residual hydrogen in fluorocarbons and related substances is important and can frequently be done, at least approxi­

mately, by infrared spectral measurements near 3000 cm."

1

The lower

limit detectable is affected by the appearance of combination bands in

this region, when thick sample specimens are used; and this will vary

with the substance being studied. Furthermore, as can be seen from the

spectra of the hydrides at the end of this chapter, the intensity of the

CH absorption changes with the position of the hydrogen atom in the

molecule. For fluorocarbon hydrides with one hydrogen atom, the CH

absorption is greatest when the hydrogen atom is on a terminal carbon

atom, approximately one-third that intensity if it is on a secondary carbon atom, and somewhat weaker yet if it is on a tertiary carbon atom.

C = C , C = N , and N = C= 0 Stretching Frequencies

C = C

Henne and Finnegan (61) have discussed the spectrum of CF3Cs=

C C F 3. Bands at 4.7 ě (2130 cm.*

1

) and 4.85 ě (2060 c m r 1

) are attributed to the partial allenic character of the triple bond and to the C = C = C structure, respectively. Henne and Nager (62) found bands at 4.4 μ (2270 c m .

- 1

) , 4.7 μ (2130 cm."

1

), and 5.1 ě (1960 c m . - 1

) in the spectrum of C F 3C = C H . They assign the 2130 cm."

1

band to the triple bond vibration frequency and the 1960 cm."

1

band to the vibrational frequency of the C = C = C structure. Haszeldine and Leedham (51) also report the spec­

trum of C F 3C = C H as well as C2F5te=CH, and list the C=C band as 4.65 ě (2150 cm."

1

) and 4.66 ě, respectively. These frequencies are quite close to those of the hydrocarbon alkynes.

C = N

Kitson and Griffith (80), in the study of a large number of nitriles (not containing fluorine), found that the C ^ N stretching frequency was at 2250 ± 10 cm."

1

(4.44 ě) for saturated nitriles or olefinic nitriles with no conjugation. Conjugation was found to lower the frequency to 2225 ± 8 cm."

1

(4.49 ě). Nitriles of the type C nF2 n + i CN have a CN stretching at 2275 ± 5 cm."

1

, while C F 2= C F C N , the only conjugated nitrile measured, has a relatively weak absorption at 2255 cm."

1

(unpub­

lished work of author). Thus the substitution of an alkforyl group on the nitrile group raises the frequency 25 c m .

- 1

, and the decrease due to conjugation is about the same in both cases.

N = C = 0 Barnes et al (8) give 2270 cm."

1

as the position of the isocyanate stretching frequency. The substitution of an alkforyl group on the iso­

cyanate group shifts the frequency to 2300 cm."

1

The presence of a C H 2 group between the isocyanate group and the alkforyl group causes the band to appear at an intermediate position of 2280 c m .

-1

This is a par­

ticularly intense absorption.

C = C Stretching Frequencies

Torkington and Thompson (151) and Smith (137) have discussed the absorption bands due to the C = C stretching vibration in fluorine-con­

taining materials. Starting with an absorption for the vinyl group ( — C H = C H 2) at 1640 cm."

1

(6.10 ě), a shift of nearly 100 cm."

1

to

higher frequencies is found when the two terminal hydrogens are replaced

by fluorine. A further increase of 50 cm." occurs when the third hydrogen is replaced by fluorine. In C F 2 ^{= C F} 2 the C = C stretching vibration gives rise to a Raman frequency at 1872 cm."

1

(5.34 ě). These are rather pro­

nounced changes and should enable one to obtain a great deal of informa­

tion concerning the substituents on the olefinic group of fluorine contain­

ing materials.

In agreement with these assignments are the following values reported by Brice, LaZerte, Hals, and Pearlson (16) for C 4 ^olefins:

C4^F8- 1 1795 cm."

1 ( 5 . 8 8 μ) iso-CaFs 1755 (5.71 μ) C4^F8 —2 (mixture of cis and trans) 1735 (5.77 μ)

Haszeldine (50) reported an absorption band at 5.56 ě (1800 cm."

1 ) for C 3 ^F 6 ^{and C} 4 ^F 8 - 1 and one at 5.77 ě (1735 cm."

1

) for C 4 ^F 8 ^{- 2 . In} addition he lists bands at 5.65 ě (1770 cm."

1

) for C F 2 = C F C F = C F 2 ^; 5.74 ě (1740 cm."

1

) for cyclohexforene, C 6 ^{F i} 0 ; and 5.59 ě (1785 cm."

1 ) for the cyclobutforene, C 4 ^F 6 . The value for cyclohexforene is in agreement with that for the butforene-2 olefin. The low value for c-C 4 ^F e is undoubt­

edly due to the strain in the four-membered ring. Haszeldine indicates that the group R — C F = C F 2 (R = H, CI, C F 3 ^{, or C} 2 ^F 5 ) will have a band at 5.56 ě (1800 cm."

1 ).

Unfortunately the frequency shifts observed above when hydrogen is replaced by fluorine causes more overlapping of the C = C and C = 0 absorption positions for substances containing large percentages of fluorine than is found for hydrocarbons.

C

= 0 Stretching Frequencies ALDEHYDE AND KETONE C = 0

Husted and Ahlbrecht (70) report a value of 1780 cm."

1

for the C = 0 vibration frequency for the first three members of the series of the alde­

hydes ^ C H O . Haszeldine (47) gives a wavelength range of 5.6 to 5.7 ě (1755 to 1785 cm."

1

) for this frequency. This represents a considerable increase from the frequency near 1700 cm."

1

found for aliphatic alde­

hydes (24).

Haszeldine (47) lists the values of 5.65 ě (1770 cm."

1

) for the carbonyl frequency of ^ C O C H 2 — and 5.55 ě (1800 cm."

1

) of . The corresponding value for hydrocarbons is about 1700 cm."

1 (24).

ACID HALIDE C = 0

Haszeldine (47) lists 5.3 ě (1870 cm."

1

) for the C = 0 frequency of

&COF and 5.4 to 5.5 ě (1850 to 1820 cm."

1

) for the C = 0 frequency of

^COCl. However, Hauptschein, Stokes, and Nodiff (60) report 5.58 ě (1792 cm."

1

) for C 2 ^F 5 C 0 C 1 and 5.56 ě (1800 cm."

1

) for C 3 ^F 7 ^{C 0 C 1 .}

Unpublished work of the author can be summarized as follows:

* C O F 1870-1900 cm."

* C O C l 1795-1820 cm."

1

C3F7CO Br 1820 cm."

¹

C3^F7C O I 1795 cm."

1

It appears that the acid chloride carbonyl frequency reported by Haszel­

dine is too high.

ANHYDRIDE AND ACID C = 0

Fuson, Josien, Jones, and Lawson (42) studied CF ₃ COOH and CF3OOD in the gaseous phase and found absorption frequencies for the carboxy acid C = 0 vibration at 1825 and 1823 c m .

- 1

, respectively. At low pressures they report bands at 1826 and 1788 c m .

-1

which they attribute to the existence of monomeric and associated forms of the acid.

Haszeldine (47) has assigned the region 1770 to 1785 c m . -1

for the C = 0 frequency of the acids Ö COOH, apparently in the liquid phase. The spectra reproduced in this chapter would indicate that the C = 0 group frequency for the liquid fluorocarbon acids is in the region of 1750 to 1785 cm."

1

Haszeldine (47) has given 5.3 ě (1890 cm."

1

) and 5.5 ě (1820 cm."

1 ) for the positions of the two C = 0 bands observed for anhydrides of the type ( ^ C O ) ₂ 0 . Hauptschein, Stokes, and Nodiff (60) found bands at 5.40 ě (1852 cm."

1

) and 5.58 ě (1790 cm."

1

) for glutarforic anhydride, CF ₂ CO

C F / \ ₂ O.

\ /

CF ₂ CO

ESTER C = 0

Rappaport, Hauptschein, O'Brien, and Filler (130) have studied the infrared absorption spectra of 25 esters formed from acids or alcohols, either or both of which had alkforyl groups. The substitution of fluorine into the molecule shifts the C = 0 absorption to higher frequencies by as much as 60 cm."

1

from the usual value of about 1740 cm."

1

for esters.

They report the following correlations for the C = 0 group.

— C F2^{C O O C H}2— 5.59 ± 0 . 0 2 μ (1790 ± 6 cm."

1 )

— C H2^{C O O C H}2^{C F}2— 5.66 ± 0 . 0 2 μ (1767 ± 6 cm."

1 )

— C F2^{C O O C H}2^{C F}2— 5.53 ± 0 . 0 2 μ (1808 ± 6 cm."

1 )

These shifts have been explained by Hauptschein, O'Brien, Stokes, and Filler (60) in terms of the strong inductive effect of the very electro­

negative alkforyl groups.

C = 0 IN SALTS AND AMIDES

The C = 0 vibration frequency for the salts of fluorocarbon acids

was found by Haszeldine (47) to be in the range of 5.9 to 6.20 ě (1695 to

1615 c m . ) for the sodium, potassium, and silver salts. The author's unpublished data for a wider range of salts of this type is in essential agreement with this assignment.

The infrared spectra of the fluorocarbon amides usually have a strong band at 1700 to 1730 cm."

1

with a weaker band at 1610 to 1630 cm.- 1 This is similar to the case of the hydrocarbon amides. The stronger absorption band is undoubtedly due to the C = 0 group vibration.

Randall et al. (129) consider the possibility that the weaker band may be due to the — N H ₂ bending vibration.

The correlations for the "double and triple b o n d " region discussed above are summarized in Table I.

Spectral Correlations in the 1350 to 650 C m .

-1

Region

It has already been mentioned that correlations in the 1350 to 650 c m .

-1

region are much less certain than those above 1350 c m . - 1

, and that they are further complicated in the case of fluorocarbons by the large interaction of vibrations. Generally this region is most useful for the

"fingerprint" method of identification. Nevertheless some useful correla­

tions in this region have been established.

Smith (137), after studying an appreciable number of fluorocarbons, concluded that in the case of saturated fluorocarbons no useful relation­

ship between molecular structure and infrared absorption could be found, and that C F ₃ and C F ₂ groups do not have useful characteristic frequencies in the sense that C H ₃ and C H ₂ do in hydrocarbons. He puts the C—F stretching vibration of the C F ₂ group in the range of 1120 to 1280 cm."

1 , with that of the C F ₃ group between 1120 and 1350 c m r

1

This is made still more difficult by the fact that four- or five-membered cyclic fluoro­

carbons with no C F ₃ groups also have bands between 1140 and 1350 c m .

-1

However, the — C F = C F ₂ group could be correlated with a band in the 1300- to 1340-cm.-

1

region.

Hauptschein, Stokes, and Nodiff (60) attribute a band at 1325 to 1365 c m .

-1

to the C F ₃ group for compounds of the type C F ₃ ( C F ₂ ) _n X , where X is Cl, Br, I, COSR, COOH, or COC1. They state that in the absence of a C F ₃ group they do not find a band in this region with the

CF ₂ CO

exception of C F ₂ O. If the C F ₃ group is attached directly to

\ / CF ₂ CO

functional group, then the band in this region is weak and another weak band is found at 1390 cm.-

1

with the exceptions of C F ₃ C O O C ₂ H ₅ and ( C F ₃ C O ) ₂ 0 which have strong bands at 1325 to 1365 cm."

1

I t is interesting to note the use of the out-of-plane hydrogen bending

vibration to differentiate the cis and trans isomers of C F ₃ C H = C H C F ₃ .

TABLE I

Structural Group Correlations for the "Double and Triple Bond Region.

11

R-aliphatic hydrocarbon group. The substituents not indicated are fluorocarbon groups.

Wove Numbtrt em.*

1

2200 2000 1800 Ô—I R

- N C O

- C H

2

^{N C O}

- C » N

- C " C - ( o r H)

- C F - C F

2

— C F - C F -

Ç

- C - 0

^ 0 - C ^ C H , -

-C'-°F

- c - c i

- c - o

^0 - c « o

* ° - C - 0 H

^ 0 - C - O C H* °

r

- C - O - R

- C - N H , - C - O M e *0

4.20 5.00

Wave Length Microns

The trans — C H = C H — group has a strong band at 950 c m . , while the cis group has a band at 750 c m r

1

(24) in the case of hydrocarbons, trans- C F ₃ C H = C H C F ₃ has been reported by Henne and Nager (63) and by Haszeldine (48). They used the presence of a strong band at 965 c m .

-1 as evidence for the trans arrangement. C Î S - C F ₃ C H = C H C F ₃ , as reported by Smith (139), does not have a band in this region.

Brandt, Emeleus, and Haszeldine (15) tentatively assign a band at 759 cm.-

1

to the C — S vibration of ( C F ₃ ) ₂ S ₂ and a doublet at 760 cm."

1 to the same vibration in the trisulfide, ( C F ₃ ) S ₃ . Hauptschein and Grosse (55), however, give a value of 680 cm."

1

for the corresponding C ₃ F7 com­

pounds. Hauptschein, Stokes, and Nodiff (60) assign the weak C — S band for the fluorinated thiol esters to 694 to 710 c m .

-1 Lageman, Jones, and Woltz (86) ascribe a band at 945 c m .

-1

to the Ď—F stretching frequency of C F ₃ O F compared to 928 c m .

-1

for that of

O F

2

^.

Haszeldine (47) has also listed the following carbon-halogen stretching frequency assignments :

•Θ-Ι 740-690 cm."

1

* B r 770-740

#C1 780

Infrared Absorption Spectra

The infrared absorption spectra which follow were obtained using Perkin-Elmer Model 12C and Model 21 infrared spectrometers (121) with sodium chloride optics.

It was found convenient, when one was interested in the qualitative identification of major components in a gaseous mixture, to use a cell of 25-mm. length, filled to pres­

sures of 50 mm. or more of mercury. The pressure is 50-mm. mercury and the cell length 25 mm., unless otherwise marked on the spectral charts. If a 25-mm. cell was used at some other pressure, the number next to the curve indicates the pressure in millimeters of mercury. Thus for C F4 (p. 469) a portion of the spectrum was run using 8-mm. mercury pressure in a 25-mm. cell. If the cell length was also different than 25 mm., this is indicated by two numbers—the first is the pressure in millimeters of mercury, and the second the cell length in centimeters. Thus for C F4^{, 500-10} means 500-mm. mercury pressure in a 10-cm. cell. The thickness of liquid samples is indicated in millimeters (i.e., C10F22 — 0.017 mm. thickness). Sealed liquid cells were used (121). Solid samples were run as cast films or mulls with a hydrocarbon such as Nujol.

In some instances the structure of a material is not given in the index or on the charts which follow. For example,

C7F15COOH

is listed only by the empirical formula.

In all such cases, the straight-chain compound is believed to be the major component, but there may be branched-chain isomers present.

The samples used in obtaining the spectra were, for the most part, furnished by various members of the Central Research Department or the New Products Depart­

ment of the Minnesota Mining and Manufacturing Company. The author gratefully acknowledges the assistance given by many members of these groups in furnishing samples and obtaining and preparing the spectral data for publication. The author also wishes to thank the Minnesota Mining and Manufacturing Co. for permission to publish the spectral data.

Index Formula Figure R e f e r e n c e s Saturated fluorocarbons

CF4 C

2

^F

6

C

3

^F

8

C 4 F 1 0 C 4 F 1 0 C

4

^F

8

C 5 F 1 2 C 5 F 1 0 C 6 F 1 4 C 6 F 1 2 C7F16 C 7 F 1 4 C

8

^{F i}

8

C 9 F 2 0 C10F22

CF4 C

2

^F

6

C

3

^F

8

n - C 4 F i o e s o - C 4 F i o c - C

4

^F

8

W - C 5 F 1 2 C - C 5 F 1 0 W - C 6 F 1 4 C - C

6

^{F i 2}

W - C 7 F 1 6 C F

3

^{- ( c - C}

6

^{F i i )}

C s F i s C 9 F 2 0 C10F22

3, 4, 39, 125, 157 5, 103, 110

, 35, 137 , 139

, 23, 32, 34, 137 , 137

, 137 50

, 111, 137, 150 , 137, 150

Saturated C, F, and H compounds C F 2 H 2 C F 2 H 2 C F 3 H C F 3 H C 2 F 5 H C 2 F 5 H C 3 F 7 H C F

3

^{C F}

2

^{C F}

2

^H

C 3 F 7 H ( C F

3

^{) 2 C F H}

C 4 F 9 H ( C F

3

⁾

3

^{C H}

C 4 F 9 H C F 3 C F 2 C F 2 C F 2 H C

4

^F

8

^H

2

H C F 2 C F 2 C F 2 C F 2 H C 5 F 1 1 H C F

3

^{( C F}

2

^{) 3 C F}

2

^H

C 7 F 1 5 H C F 3 ( C F

2

^{) 5 C F}

2

^H

125, 143 1, 11, 125 1, 139 1, 139

Saturated C, F, CI, Br, and I compounds CF3CI

C F

3

^{B r}

CF3I C F

2

^{B r}

2

C

2

^F

5

^{B r}

C

2

^F

4

^{B r}

2

C3F7Br C3F7I C

3

^F

6

^{C 1}

2

C

3

^F

6

^{B r}

2

CF3CI C F

3

^{B r}

CF3I C F

2

^{B r}

2

C

2

^F

5

^{B r}

C F

2

^{B r C F}

2

^{B r}

« - C

3

^{F 7 B r}

W - C 3 F 7 I C F 3 C F C I C F 2 C I C F

3

C F B r C F

2

^{B r}

125, 148

36, 58, 92, 93, 126, 127 36, 58, 92, 93, 126, 127 28, 126

58 58 54 82, 162

INDEX AND REFERENCES OF INFRARED SPECTRA PRESENTED HERE

3 2 3 2 3 2 3 2 2 3

4 4 4 4 4 5 5 5 5 5

6 6 6 6 6 7 7 7 7 7

Index Formula Figure R e f e r e n c e s Olefins

C2F2H2 C F

2

^{= C H}

2

⁸ 1, 137, 138, 151 C2F3H C F

2

^{= C F H 8 114}

C2F4 C F

2

^{= C F}

2

⁸ 1, 81, 105, 137, 151 C2F2CI2 C F

2

^{= C C l 2 8} 1, 82, 104, 137, 151 C2F3CI C F

2

^{= C F C 1 8} 1, 82, 137

C

3

^F

6

^{C F}

3

C F = C F 2 9 1, 33, 82, 109, 137, 162 C3F3CI3 C F

3

C C l = C C l 2 9 1, 139 C

4

^F

8

^{C F}

3

^{C F}

2

^{C F = C F}

2

^{9 16}

C

4

^F

8

^{C F}

3

C F = C F C F

3

^{9 16, 50}

(cis and trans)

C

4

^F

8

^{( C F}

3

) 2 C = C F

2

^{9 16}

C

4

^F

6

^{C F}

2

= C F C F = C F

2

^{10 50}

C5F10 C F

3

^{( C F}

2

) 2 C F = C F 2 10 C

6

^{F i o C F 2 C F}

2

C F = C F C F

2

^{C F 2 10}

C7F14 C F

3

^{( C F}

2

) 4 C F = C F

2

¹⁰

C9F18 C F

3

^{( C F}

2

) 6 C F = C F

2

¹⁰

Fluorocarbon oxides and fluorine-containing e t h e r s C

2

^F

6

^{0 ( C F}

3

⁾

2

^{0 11}

C4F10O ( C

2

^F

5

⁾

2

^{0 11}

C

4

^F

8

^{0 C-C4F8O 11} 1, 64, 139

C

8

^{F i}

8

^{0 ( n - C}

4

^F

9

⁾

2

^{0 11} 1, 64, 137 C12F26O ( w - C

6

^{F i}

3

^{) 2 0 11}

C3F4H4O H C F

2

^{C F}

2

^{0 C H}

3

^{12 116}

C

4

^F

6

^H

4

⁰ CF3CFHCF2OCH3 12 C

5

^F

8

^H

4

^{0 ( C F}

3

) 2 C H C F

2

^{0 C H 3 12}

C

5

^F

6

^H

6

⁰ CF3CFHCF2OC2H5 12 C

6

^F

6

^H

8

⁰ CF3CFHCF2OC3H7 12

Amines and other nitrogen-containing compounds

C2F3H4N CF3CH2NH2 13

C4F7H4N n - C 3 F

7

^{C H}

2

^{N H 2 13}

C5F13N ( C

2

^F

5

^{) 2 C F}

3

^{N 13}

C 5 F 1 1 N 1 1

C F 2 C F 2 C F 2 C F 2 C F 2 N F 15 C

6

^{F i}

5

^{N ( C}

2

^F

5

⁾

3

^{N 13}

C 7 F 1 7 N ( C

2

F 5 ) 2 ( n - C

3

^{F 7 ) N 13}

C

8

^{F i}

9

^{N ( C 2 F}

5

) 2 ( « - C

4

^{F 9 ) N 14}

C

8

^{F i}

9

^{N ( C}

2

^F

5

) ( n - C 3 F 7 ) 2 N 14 C9F21N ( w - C

3

^F

7

^{) 3 N 14}

C

9

^F

2

^{i N (CF}

3

^)(w-C

4

^{F9)2N 14}

C12F27N ( « - C

4

^F

9

⁾

3

^{N 14 1, 137}

Index Formula Figure R e f e r e n c e s

N i t r i l e s

C2F3N CF3CN 15

C3F5N C2F5CN 15

C3F4HN CF3CFHCN 15

C3F3N C F2^{= C F C N 15}

C4F7N W-C3F7CN 16

C4^F6^{H N ( C F}3⁾2^{C H C N 16}

C4F4N2 ( C F2^{C N )}2 ¹⁶

C6^{F n N W-C5F11CN 16}

C8^{F i}5^{N W-C7F15CN 16}

Acid halides

CF2O C O F2 ¹⁷ 99, 100, 102, 155, 156

C2F4O CF3COF 17

C3^F6^{0 C2F5COF 17}

C4^F8^{0 W-C3F7COF 17 69}

C2F3CIO CF3COCI 17

C2F3BrO C F3^{C O B r 18}

C3F5CIO C 2 F 5 C O C I 18

C 4 F 7 C I O W-C3F7COCI 18 69

C4F7BrO w-C3F7COBr 18

C4F7IO n-C3F7COI 19

C e F n C l O C 5 F 1 1 C O C I 18

Anhydrides

C4F6O3 ( C F3^{C O )}2^{0 19 42}

C4F4O3 C F2^{C = 0}

1

19 I ^

υ

C F2^{C = 0}

C8F14O3 (w-C3F7CO)20 19

C20F38O3 ( C9^{F i}9^{C O )}2^{0 19}

Acids

C2F3HO2 CF3COOH 20 42, 77

C3F5HO2 C2F5COOH 20

C4F7HO2 W-C3F7COOH 20

C4F7HO2 ISO-C3F7COOH 20

C4F4H2O4 ( - C F2^{C O O H )}2 ²⁰

C5F9HO2 W-C4F9COOH 21

C6^{F n H 0}2 ^{C5F11COOH 21}

C7F13HO2 C6^{F i}3^{C O O H 21}

C8^{F i}5^{H 0}2 ^{C7F15COOH 21}

C10F19HO2 C9F19COOH 21

Index Formula Figure R e f e r e n c e s Amides

C2F3H2ON C3F5H2ON C4F7H2ON C

6

^{F i i H}

2

^{O N}

C

8

^{F i}

5

^H

2

^{O N}

CF3CONH2 C2F5CONH2 W-C3F7CONH2 C5F11CONH2 C7F15CONH2

22 22 22 22 22 Salts

C F

3

^{C O O N a}

( C F

3

^{C O O )}

2

^{B a}

( C F

3

^{C O O )}

3

^{A l}

C

2

^F

5

^{C O O N a}

w - C

3

^F

7

^{C O O N a}

(n-C3F7COO)2Ba ( « - C

3

F 7 C O O )

3

^{A l}

C

5

F n C O O N a C

7

^{F i}

5

^{C O O N a}

C g F i g C O O N a

23 23 23 23 23 24 24 24 24 24

42

Ketones, aldehydes, aldehydrols, and alcohols

C

3

^F

6

⁰

C2F3HO C3F5HO C4F7HO C2F3H3O C2F3H3O2 C3F5H3O C3F5H3O2 C4F7H3O C4F7H3O2

Ρ

C F

3

^{C - C F}

3

CF3CHO C2F5CHO

«-C3F7CHO CF3CH2OH C F

3

C H ( O H ) C

2

2

^F

5

^{C H}

2

^{O H}

C

2

^F

5

C H ( O H ) C3F7CH2OH

2

w - C

3

^F

7

C H ( O H ) 2

25 25 25 25 25 26 26 26 26 26

70, 135 70 70 70 70 65 70 E s t e r s

C4F3H5O2 C5F7H3O2 C5F5H5O2 C6F10H2O2 C6F7H5O2 C

6

^F

5

^H

7

⁰

2

C6F4H6O4 C6F3H9O2 C7F11H3O2 C

8

^{F i i H}

5

⁰

2

C

8

^F

7

^H

9

⁰

2

C12F7H15O4

CF3COOC2H5 W-C3F7COOCH3 C2F5COOC2H5 CF3COOCH2C3F7 W-C3F7COOC2H5 C 2 F

5

C O O C H ( C H

3

^{) 2}

( - C F

2

^{C O O C H}

3

^{) 2}

CF3COOC4H9 C5F11COOCH3 C5F11COOC2H5 W-C3F7COO-W-C4H9 ( C

3

H 7 C O O ) 2 C H C

3

^{F 7}

27 28 27 27 28 28 27 27 28 29 28 29

42

130

Index Formula Figure R e f e r e n c e s

P o l y m e r s

Miscellaneous

( - C F 2 - C F 2 - ) * 2 9 ( - C F 2 - C F C I - ) * 2 9 ( Ă Ο Ô

,

,7Γ Τ ٠ Ο Đ Đ ĂΓ Η Γ Η2^{- )}Λ^{; 2 9}

N F3 ³⁰

O F2 ³⁰

S1F4 30

S F6 ³⁰

SO2F2 30 1, 137

96, 137

3, 154

12, 68, 76, 100, 144 3, 4, 75

30, 37, 85, 88, 161 122

INDEX OF INFRARED SPECTRA APPEARING IN THE LITERATURE BUT NOT SHOWN HERE

Index Formula

Saturated C5F12 C7F16 C 7 F 1 4

C8^{F i 6}

C8^{F i 6}

C g F i s

fluorocarbons i s o - C 5 F i 2

C F 3 C F C F 3 C F C F 3 C F 2 C F 3

I 1 C 2 F 5 C F C F 2 C F 2 C F 2 C F 2

C F 3 - C F

^ C F 2 - C F2 >s

C F 2 - C F2

X X F - C F 3

^ C F2

C F 3 - C F ^ C F2

I I

CF3—CF C F2

C F2

/ C F2

C F 3 - C F X F C F 3

I I

C F 2 / C F 2

^ C F I C F3

R e f e r e n c e s

1, 137 150 1, 137 1, 137

1, 137

1, 137

Saturated C, F, and Η compounds CFH3

C2F3H3

CFH3 CF3CH3

10, 146, 159, 160 1, 25, 26, 44, 106,

137, 140, 141, 149

Index Formula R e f e r e n c e s Saturated C, F, and H compounds (Continued)

C2F2H4 CF2HCH3 1, 137, 139, 141

C2FH5 CFH2CH3 1, 139, 141

C3F3H5 CF3CH2CH3 1, 139

C5F9H C-C5F9H 1, 139

laturated C, F, H, Cl, Br, and I compounds

CF2HCI 125

CF2HBr 126

CF2CI2 125, 148

C F 2 C l B r 126

CFH2CI 123

CFHCI2 125, 148

CFHCIBr 124

CFCI3 125, 148, 163

C F B r

3

⁹⁵

C2F5CI C2F5CI 1, 5, 58, 110, 139

C2F5I C2F5I 54

C2F4HCI C F

2

^{C 1 C F}

2

^{H 1, 139}

C

2

^F

4

^{H B r C F}

2

^{B r C F}

2

^{H 83}

C2F4CI2 C F

2

^{C 1 C F}

2

^{C 1} 1, 81, 137 C2F4CI2 C F 3 C F C I 2 1, 110, 139

C2F3H2CI CF3CH2CI 1, 139

C2F3HCI2 C F

2

C 1 C F H C 1 114

C2F3HCI2 CF3CHCI2 1, 139

C

2

^F

3

^{H C l B r C F}

2

B r C F H C l 83

C2F3HBr2 CF2BrCFHBr 114

C2F3CI3 CF3CCI3 1, 82, 110, 137, 139

C2F3CI3 C F 2 C I - C F C I 2 1, 82, 137

C2F2H3CI CF2CICH3 1, 139, 140

C2F2H.2Br2 C F

2

B r C H 2 B r 1, 139

C

2

^F

2

^{H C l}

2

^{B r C F}

2

B r C H C l

2

⁸³

C2F2CI4 C F 2 C I - C C I 3 1, 82, 139

C2FH3CI2 CFCI2CH3 1, 139, 140

C2FCI5 CFCI2-CCI3 1, 139

C3F7CI CF3CF2CF2CI 58

C

3

^F

6

^{C 1}

2

^{C F}

2

^{C 1 C F}

2

^{C F}

2

^{C 1 56, 162}

C

3

^F

6

^{B r}

2

^{C F}

2

^{B r C F}

2

^{C F}

2

^{B r 56}

C

3

^F

6

^{l 2 C F}

2

^{I C F}

2

^{C F}

2

^{I 54}

C3F5CI3 C F

2

^{C 1 C F}

2

^{C F C 1}

2

^{1, 139}

C3F4CI4 C F C I 2 C F 2 C F C I 2 1, 139

C3F3CI5 CFCI2CF2CCI3 1, 139

C 3 F

3

^H

4

^{B r C F}

3

^{C H}

2

^{C H}

2

^{B r 48}

C

3

^F

2

^{C 1}

6

CCI3CF2CCI3 1, 139

C

4

^F

8

^{l 2} C F 2 I C F 2 C F 2 C F 2 I 59

C

4

^F

6

^H

3

^I CF3CHICH2CF3 48

Index Formula R e f e r e n c e s Saturated C, F, H, CI, Br, and I compounds (Continued)

C 4 F 6 C I 2 C F 2 C F C I- C F C I- C F 2 1, 82, 84, 139 C4F4CI6 C F

2

C l C C l 2 C C l 2 C F

2

C l 1, 139

C4F3CI7 CF2CICCI2CCI2CFCI2 1, 139 C4F2CI8 CFCI2CCI2CCI2CFCI2 1, 139 C5F11CI C F

3

^{( C F}

2

^{) 3 C F}

2

^{C 1 57}

C τ F n B r C F

3

^{( C F}

2

^{) 3 C F}

2

^{B r 57}

C 5 F 1 1 I C F

3

^{( C F}

2

^{) 3 C F}

2

^{I 57}

Unsaturated C, F, H, CI compounds C2F2HCI C F

2

= C H C 1 1, 108, 139

C

2

F H 3 CFH=CH2 151

C2FH2CI C F C 1 = C H

2

¹⁵¹

C3F3H C F

3

C = C H 46, 62

C3F2CI4 C C 1 2 = C C 1 C F

2

C 1 1, 139

C3FH4CI C H

3

C F = C H C 1 52

C3FH3CI2 CHC1=CFCH

2

^{C1 52}

C3FH3CI2 C C l 2 = C F C H

3

⁵³

C

3

^{F H}

2

C l 3 C C 1

2

= C F - C H

2

^{C 1 53}

C

3

^{F H}

2

^{C l}

2

^{B r C H}

2

B r C F = C C l

2

⁵³

C

4

^F

6

^{C F}

3

^{C = C C F}

3

1, 48, 61, 139 C4F6 C F

2

- C F = C F C F

2

1, 50, 82, 139

C4F5H C

2

^F

5

C = C H 51

C

4

^F

6

^H

2

^CF

3

^CH=CHCF

3

(*raws) 48, 63 C

4

^F

6

^H

2

^{C F}

3

C H = C H C F

3

( c * s ) 1, 139 C

4

^F

6

^{C 1}

2

^{C F}

2

= C F C F C 1 C F

2

C 1 1, 139

C4F4CI2 C F

2

= C C 1 C C 1 = C F

2

^{1. 139}

C4F3CI3 CF

2

=CC1CC1=CFC1 1. 139

C4F2CI4 C F C 1 = C C 1 C C 1 = C F C 1 1, 139 E t h e r s

C3F3H5O CFH2CF2OCH3 114 C4F4H6O C F 2 H C F 2 O - C 2 H 5 116

C

5

^F

4

^H

8

0 -W-C3H7 116

C6F4H10O -W-C4H9 116 C7F4H12O -«-C5H11 116 C3F3H4CIO CFHCICF2OCH3 1> 137

C

4

^F

3

H * C 1 0 C F H C l C F

2

^{O C}

2

^H

5

1> 137 C

6

^F

3

H i o C 1 0 C F H C l C F

2

^{0 - n - C}

4

^H

9

1> 137 C 3 F

2

^H

4

^{C 1}

2

^{0 C H C 1}

2

^{C F}

2

^{0 - C H}

3

¹¹⁵

C4F2H6CI2O - C

2

^H

5

¹¹⁵

C5F2H8CI2O - n - C

3

^H

7

¹¹⁵

C6F2H10CI2O -«-C4H9 115 C7F2H12CI2O -W-C5H11 115

I n d e x F o r m u l a R e f e r e n c e s

E t h e r s ( C o n t i n u e d ) C 4 F 3 H 3 C I 2 O C5F3H5CI2O C 6 F 3 H 7 C I 2 O C 7 F 3 H 9 C I 2 O C 5 F 4 H 3 O 2 C6F4H5O2 C7F4H7O2 C 8 F 4 H 9 O 2 C 5 F 4 H 3 C I O C6F4H5CIO C7F4H7CIO C 7 F 2 H 9 C I O 3 C10F2H15CIO3

C F

3

C C 1 = C C 1 0 ~ C H

3

- C 2 H 5

C F_{I II}

2

^{- C - O R}

C F 2- C - O R

C F 2 - C C 1 I II C F 2- C - O R

- C 3 H 7 - C 4 H 9

R = C H

3

C 2 H 5 W- C 3 H 7 n- C 4 H 9 R = C H

3

C

4

^F

2

C 1 ( 0 C H 3 ) 3 C 4 F

2

^{C l ( O C}

2

^H

5

^{) 3}

C 2 H 5 C 3 H 7

( c y c l i c t r i e t h e r s ) 119 119 119 119 112 112 112 112 117 117 117 117

A n h y d r i d e s a n d a c i d s

C 5 F 6 O 3 C 2 F 3 D O 2 C 4 F 3 H 3 O 2

. C F 2- C O

C F

2

^{^ >}

^ C F

2

^{- C O}

C F 3 C O O D C F 3 C H= C H C O O H

60 42, 77 49 E s t e r s

C6F10H2O2 C6F3H9O2 C8F4H10O4

C

3

^F

7

C C X ) C H 2 C F 3 C3H7COOCH2CF3 ( ~ C F

2

^{C O O C}

2

^HJ^{5 ) 2}

130 130 59 H y d r o x y c o m p o u n d s

C3FH4CIO C7F14H2O C7F7H9O

C H C l = C F C H

2

^{O H}

( w - C

3

^F7) 2 C H O H C3F7CHOHC3H7

52 65 65 K e t o n e s

C3F3H3O C4F5H3O C7F14O

CF3COCH3 C 2 F 5 C O C H 3 ( C

3

^F7^{) 2 C O}

51 51"

66

S u l f i d e s C 2 F 6 S C

2

^F

6

^S

2

C

6

^{F i}

4

^S

2

C6F14S3

( C F

3

⁾

2

^S

CF3S2CF3 C 3 F

7

^S

2

^C3^{F 7}

C3F7S3C3F7

15 15 55 55

Index Formula R e f e r e n c e s Thiol e s t e r s

C4F3H50S CF3COSC2H5 60

C5F5H50S C2F5COSC2H5 60

C6F7H50S C3F7COSC2H5 60

C7F6H603S C2H5SOCCF2CF2CF2COOH 60 C7F6H5C102S C 2 H

5

S O C C F 2 C F

2

^{C F}

2

^{C O C l 60}

C8F4H10O2S2 ( - C F

2

C O S C 2 H

5

^{) 2 59}

C9F6H10O2S2 C F

3

C O S ( C H

2

) 5 S O C C F

3

⁶⁰

C 9 F

6

^{H i o 0}

2

^S

2

C2H5SOCCF2CF2CF2COSC2H5 60 C11F10H10O2S2 C 2 F

5

C O S ( C H

2

⁾

5

S O C C 2 F 5 60 C13F14H10O2S2 C

3

F 7 C O S ( C H 2 ) 5 S O C C

3

^{F 7 60}

M i s c e l l a n e o u s

C F C I O COFC1 73, 102

CF4O C F 3 O F 86

C

4

^F

6

⁰

2

^{C F}

2

^{C F}

2

^{C F}

2

^{O C O 59}

C F

3

^H

4

⁰

2

^N CF3CH2CH2NO3 135 C9F2H13O2N 3 , 3 - D i f l u o r o - 2 , 4 - d i o x o c y c l o b u t y l d i - 128

e t h y l m e t h y l a m m o n i u m b e t a i n

C10F2H13O2N 3 , 3 - D i f l u o r o - 2 , 4 - d i o x o c y c l o b u t y l t r i - 128 e t h y l a m m o n i u m b e t a i n

C

2

^{F H}

6

⁰

3

^{P ( C H}

3

^{0 )}

2

^{P O F 27}

C4FH10O3P ( C

2

^H

5

^{0 )}

2

^{P O F 27}

C4FH12ON2P [ ( C H

3

^{) 2 N ]}

2

^{P O F 9}

Aromatic compounds

(Since the compounds l i s t e d h e r e contain m o r e hydrogen than fluorine a t o m s , t h e s e two e l e m e n t s have been r e v e r s e d in the index for t h i s group.)

C6H5F Fluorobenzene 1, 137, 139

C

6

^H

4

^F

2

/>-Difluorobenzene 1, 29, 137, 139

*w-Dif luorobenzene 1, 139 C6H3F3 1,2,4- Tr if luorobenzene 1, 137, 139

1,3,5- Trif luorobenzene 1, 40, 107 C

6

^H

2

^F

4

1,2,4,5 - Tet raf luorobenz ene 1, 137

C7H7F o-Fluorotoluene 1, 137, 139, 150 />-Fluorotoluene 1, 137, 139, 150

m - Fluorotoluene 150

C

7

^H

6

^F

2

2,4-DiFluorotoluene 150 C7H5FCI2 Fluorodichloromethylbenzene 1, 139 C7H5F2CI Difluorochloromethylbenzene 1, 139

C7H5F3 Benzotrifluoride 1, 137, 139, 150 C7H4F4 m- Fluorobenzotrifluoride 1, 137, 139, 150

/>- Fluorobenzotrifluoride 150

Index Formula R e f e r e n c e s Aromatic compounds (Continued)

C7H4F3CI m-Chlorobenzotrif luoride 113 />-Chlorobenzotrifluoride 1 C7H3F5 2,5-Difluorobenzotrifluoride 1, 137, 139, 150 C8H4F6 1 4-Di(bis-trifluoromethyl)benzene 1, 139

C8H5F3CI2 a,a-dichloro-j3,0,0-trifluoroethyl- 113 benzene

C8H4F3CI3 w - c h l o r o - c ^ a - d i c h l o r o - Ł , 0 , / 3 - t r i - 113 fluoroethylbenzene

C8H3F3CI4 3,4-dichloro-a,a-dichloro-/3,j3,/3- 113 trifluoroethylbenzene

C8H5F3O Trifluoromethyl phenyl ketone 113 C8H4F3CIO Trifluoromethyl 3-chlorophenyl ketone 113

C 9 H10 FO2NS 1 -/> - Fluorophenyl cysteine 41 C9H7F3O Trifluoromethyl 3-methylphenyl ketone 113

C10H10F3ON N-ethyltrifluoroacetanilide 118 C11H12FO3NS l-/>-Fluorophenylmercapturic acid 41

C13H8F3NS 2-Trifluoromethylphenothiazine 142 Inorganic fluorine compounds

BF3 2, 3, 43

B r F5 ¹⁸

C1F 72, 101, 120

CIF3 71 D F 115

G e F4 21, 22, 157

HF 20, 97, 134, 136, 145

I F5 ⁹⁰

IF7 90 KA1F6, KBF4, and other complex 89

fluorides

K H F2 78, 79, 98

H D F2 ⁷⁸

KPF6 87 M0F6 19 NO F 74, 91, 158

NH4F 14 NaAlF6 87 P F 3 45, 154

P F5 ⁴⁵

POF3 45

S e F6 ^{38, 132}

S2F10 31 TeF6 38, 132

U F6 ^{13, 19}

W F6 ¹⁹

FIG. 1.

470 - - W E I B L E N

FIG.

\. 3.

F I G . 4.

FIG. 5.

FlG. 6 .

F I G . 7.

ι • : r .

I

ν ι . . WAVE LENGTH MORONS

F I G . 8.

WAVE LENGTH MICRONS

FIG. 9.

FIG. 10.

FIG. 11.

FIG. 12.

FIG. 1 3 .

FIG. 14.

• •

1

' i i •

1

• •

1

WAVE LENGTH MICRONS FIG. 1 5 .

FIG. 16.

FIG. 1 7 .

WAVE LENGTH MICRONS

FIG. 1 8 .

) •

1

• J '

1

• ι •

1

WAVE LENGTH MICRONS FIG. 1 9 .

F I G . 20.

FIG. 21.

5 0 0 0 3 0 0 0 2 0 0 0

r"

_A

π

Y V

S ^{- Λ . —}

11

^{"Nu| »r Muii}

^{. V}

i \

. . ι

• ι • ' r

1,

"

FIG. 22.

NUMBERS C M .' 1200 1000 9 0 0 é é é É ř é É é é Ŕ | É é é é é ; é é é ř é é ö é Ŕ | Éé

fl

C\ F

e

^{C 0 0 N a}

LJ

WAVE LENGTH MICRONS

FIG. 2 3 .

FIG. 2 4 .

, Λ Ι I f , I ,

WAVE LENGTH MICRONS FIG. 2 5 .

FIG. 2 6 .

FIG. 2 7 .

1

' 7 '

1

' J ' ' ' I ' ' ' WAVE LENGTH MICRONS

FIG. 2 8 .

é • . r , • é • •

WAVE LENGTH M O R O NS

FIG. 2 9 .

FIG. 3 0 .