CHAPTER

Alkyl Carbon-Hydrogen Vibrations

Summary Other n-Alkane Vibrations 1,2-Epoxyalkanes Sodium Dimethylphosphonate (CH3)2P(O)2Na Methyhhiomethyl Mercury, Dimethylmercury (4), and Methyhhiochloroformate (5) Cycloalkanes References Figures Figure Figure Figure Figure Figure Figure Figure 3-1 3-2 3-3 3-4 3-5 3-6 3-7 36 37 38 39 39 40 40 (31) (31) (32) (32) (32) (32) (32) Tables Table Table Table Table Table Table Table Table Table Table Table Table Table Table 3-1 3-2 3-2a 3-3 3-4 3-5 3-6 3-7 3-8 3-9 3-10 3-11 3-12 3-13 41 42 43 44 45 45 46 47 47 48 49 50 52 53 (31) (32) (32) (32) (32) (34) (34) (34) (35) (35) (35) (35) (35) (35) 32 34 34 34 35 35 35

*Numbers in parentheses indicate in-text page reference.

This chapter discusses alkyl carbon-hydrogen molecular vibrations and, in some cases, looks at how these molecular vibrations are affected by their surrounding chemical environment. However, in some cases the alkyl carbon-hydrogen vibrations will be included in the section that discusses their most distinguishing molecular vibrations. The series of n-alkanes, CnH2n+2were prepared as 0.5 wt. % solutions in CCI4, CDC13, and 54.6 tool % CHC13/CC14. Table 3.1 lists the IR frequency data for the vasym. CH3 and vsym. CH3 stretching frequencies for C5H12 to C18H38 (1). Figure 3.1 shows plots of vasym. CH3 vs the molecular weight (M.W.) of each n-alkane and Fig. 3.2 shows plots of vsym. CH3 vs M.W. of each n-alkane. A study of the IR data and figures show that vasym. CH3 generally decreases as the number of carbon atoms increases in the order C5H12 to C18H38 by 0.11 to 0.22 cm -1 in going from solution in CC14 to solution in CDC13. 31

32

Alkyl Carbon-Hydrogen Vibrations

The vsym. CH3 mode for this series of n-alkanes shows that it generally decreases by approximately 0 . 8 c m -1 in C C I 4 solution and approximately 1.2cm -1 in CDC13 solution progressing in the series C5H12 to C18H38 in going from solution in CCI 4 to solution in CDC13. Table 3.2 lists the IR absorbance data for C5H12 to C18H38 for the vasym. CH3 and vsym. CH3 modes, Fig. 3.3 shows a plot of (vasym. CH3)/(vasym. CH2) vs A(vsym. CH3)/A(vsym. CH2) in CC14 solution for C5H12 to C18H38, and Fig. 3.4 shows a plot of (vsym. CH3)/(vsym. CH2) vs A(vasym. CH3)/A(vasym. CH2) in CCI 4 solution for C5H12 to C18H38 . Both plots show an essentially linear relationship. The slight deviation from linearity is most likely due to overlapping interferences in the measurement of these peak height absorbances. Table 3.2a lists absorbance ratios; all of these absorbance ratios for the vCH3 and vCH2 modes generally decrease progressing in the series C5H12 to C18H38 . Table 3.3 lists IR data for vasym. CH2 and vsym. CH2 for the n-alkane at 0.5 wt. % in CC14, CDC13, and 54.6 mol % CDC13/CC14 solutions. Figure 3.5 shows plots of vasym. CH2 vs vsym. CH2 in each of the solvent systems, and Fig. 3.6 shows plots of vasym. CH3 vs vsym. CH3 in all three solvent systems. These plots show that these relationships are not linear over the entire nalkane series. The plots do point out in general that as vasym. CH2 decreases in frequency, vsym. CH2 also decreases in frequency progressing in the series C5H~2 to C18H38, and that the vasym. CH3 and vsym. CH3 frequencies show the same trend. A study of Tables 3.1 and 3.3 show some interesting trends in CC14. CDC13, or 54.6 mol % solutions progressing in the series C5H12 to C18H38. The vasym. CH3 frequency decrease in going from solution in CC14 to solution in CDC13 is small ( ~ 0 . 1 cm -1) while for vsym. CH3 the frequency decrease is more in CDC13 solution (1.2cm -1) than in CC14 solution (0.7cm-1). In addition, the frequency difference for vasym. CH3 in CC14 and in CDC13 increases from 0.11 to 0.22 cm -1 and for vsym. CH2 in CC14 and in CDC13 decreases from 0.45 to 0.85 progressing in the series C5H12 to C18H38 . The vasym. CH2 frequency decrease in going from solution in CC14 to solution is small (0.1 cm -1) while for vsym. CH2 the frequency decrease is larger in going from solution in CC14 to a solution in CDC13 (0.6cm -1) progressing in the series C5H12 to C18H38 . Moreover, these data show that the vsym. CH2 mode changes in frequency by a factor of approximately 5 times more than vasym. CH2, vasym. CH3, and vsym. CH3. In addition, the vasym. CH2 frequency increases in frequency while the vsym. CH2 frequency decreases in frequency in going from solution in CC14 to CDC13. In general these last two trends generally decrease progressing in the series C5H12 to C18H38 . Table 3.4 lists the frequency difference between vasym. CH3 and vsym. CH3 and between vasym. CH2 and vsym. CH2 in the three solvent systems. These data show that the frequency separation is much larger for the two vCH3vibrations ( ~ 85 -1) than for the two vCH2vibrations ('-~ 69 cm-1). Figure 3.7 shows plots of vasym. CH3--vsym. C H 3 vs vasym. C H 2 - - v s y m . CH2, which clearly shows the behavior of the frequency separation of the vCH3and vCH2vibrations in the three solvent systems.

SUMMARY
For n-alkanes, C5_18H12_38, the vasym. CH3 occurs in the region 2957.26-2959.55 c m -1 in CC14 and in the region 2957.48-2959.66cm -1 in CDC13, and vsym. CH3 occurs in the region 2872.35-2873.12 c m -1 in CC14 and in the region 2871.50-2872.67 c m -1 in CDC13. Moreover,

Variables in Data Interpretation

33

vasym. CH2 occurs in the region 2926.61-2927.73cm -1 in CC14 and in the region 2926.922928.14 cm -1 in CDC13, and vsym. CH2 occurs in the region 2854.59-2861.82 cm -1 in CC14 and in the region 2854.55-2861.21 cm -1 in CDC13. In addition, these four vibrations decrease in frequency progressing in the series C5H12 through C18H38. The n-alkanes are nonpolar molecules, and one would expect that there would be minimal solute-solvent interaction between n-alkane molecules and solvent molecules such as CC14 and CDC13. The n-alkanes in going from solution CC14 to solution in CDC13 solution show a frequency increase of 0.11 to 0.22 cm -1 for vasym. CH 3 and for vsym. CH 3 it decreases by - 0 . 4 5 to - 0 . 8 5 cm -1, with decreases for vsym. CH 3 progressing in the order C5H12 to C18H38. In addition, the vasym. CH2 frequency difference is 0.41 to 0.23 cm -1 and for vsym. CH2 is - 0 . 6 1 to - 0 . 0 4 cm -1. Again the vasym. CH2 mode increases in frequency and the vsym. CH2 mode decreases in frequency in going from solution in CC14 to solution in CDC13. Thus, both vasym. CH3 and vsym. CH2 increase in frequency and both vsym. CH3 and vsym. CH2 decrease in frequency in going from solution in CC14 to solution in CDC13 at 0.5 wt. % solutions. These data confirm that the effects of these solvents are minor in these four molecular stretching vibrations. It is noteworthy that the vsym. CH2 vibration shifts progressively to lower frequency in the order C5H12 to C18H38, and that it decreases in frequency by a factor of at least 7 times more than the vsym. CH3 vibration. Apparently, the n-alkane protons form weak intermolecular hydrogen bonds with the free pair of electrons on the C1 atoms of the CC14 and/or CDC13 solvent system, and an explanation is needed to determine the frequency behavior of these four molecular vibrations in going from solution in CC14 to solution in CDC13. As these vasym. CH3, vasym. CH2, vsym. CH3, and vsym. CH2 modes vibrate, the protons obtain a weak positive charge and the carbon atom obtains a weak negative charge. This is the so-called dipole moment change during these molecular vibrations. Therefore, the n-alkane protons would form weak intermolecular hydrogen bonds with the free pair of electrons on the C1 atoms of the CC14 and/or CDC13 solvent system. The C1 atoms of CC14 would be expected to be more basic than those for CDC13 due to the fact that the D atom attracts electrons from the C1 atoms. In addition, there is intermolecular bonding between D and C1 such as CC13D: C1CC12D : C1CC13. Therefore, one would expect a stronger C-H: C1 bond to be formed between the protons in n-alkanes and the C1 atoms in CC14 than for C1 atoms in CDC13. Hydrogen bonding also weakens the O-H or C-H bond, and the vibration vOH:X or v C - H : X is expected to decrease in frequency~this is what we noted in the vsym. CH 3 and vsym. CH2 modes. However, the opposite was observed for vasym. CH 3 and vasym. CH2, where both modes increased in frequency in going from solution in CC14 to solution in CDC13. This frequency increase for the vasym, modes needs an explanation. Because the vasym. CH 3 and vasym. CH2 modes increase in frequency, it requires more energy for these two modes to vibrate in going from solution in CC14 to solution in CDC13. The two CH 3 groups are isolated by (CH2)~ groups, and as the C1 atoms in CDC13 are weaker bases than the C1 atoms in CC14 a weaker C-H...C1CDC12 bond is expected. Consequently, the vasym. CH3 and vasym. CH2 increases in frequency when CC14 is replaced by CDC13.

34

Alkyl Carbon-Hydrogen Vibrations

On the other hand there are (CH2), units present in the n-alkane series which are capable of forming n units of

/H C'

"

CI~

/
.

cI

in either CC14 or CDC13 solution. It is noted that vsym. CH3 increasingly decreases in frequency progressing in the series C5H12 to C18H38 in going from solution in CC14 to solution in CDC13. This indicates that the C-H:C1CDC13 bond strength is increased as n is increased for CH3(CH2)nCH3. The inductive effect of additional CH2 groups apparently weakens the CH3 bonds, causing vsym. CH2 to decrease in frequency as the number of CH2 groups are increased in the n-alkane. As the number of CH2 groups are increased, the decrease in vsym. CH2 for nalkanes decreases progressing in the series C5H12 to C10H22 and is relatively constant from C9H20 to C18H38. This suggests that the effect of the number of CH2 groups forming intermolecule hydrogen bonds with a CDC13 chain is minimized after eight CH2 groups are present in that the effect of the number of (CH2)C1CDC13 intermolecular hydrogen bonds formed between the n-alkane and CDC13 is minimized in the series CllH24 to C18H38. It is also possible that the C1 atoms in CDC13 are closer in space to the C-H bonds compared to that for CC14, and this fact would also contribute to lower vsym. CH2 frequencies. In the series C5H12 to C18H38 there is a comparatively large change in the vsym. (CH2), mode. There is a decrease of 7.23cm -1 CC14 and 6.66cm -1 in CDC13. This is attributed to the increasing number of CH2 groups stretching in-phase progressing in the n-alkane series. The smooth correlation of the absorbance values of the CH2 and CH3 groups as the ratio of the CH3 groups to CH2 groups decreases is just what is predicted. There is apparently no significant difference in the dipole moments of either CH2 or CH3 stretches progressing in the nalkane series. OTHER n-ALKANE VIBRATIONS The CH2 bend asym. CH3 bend, and the sym. CH 3 bend occurs near 1467, 1458, and 1378.5 cm -1 in CC14 solution (Table 3.5). 1,2-EPOXYALKANES Table 3.6 lists IR vapor-phase data for the alkyl (R) vibrations of 1,2-epoxyalkanes (2). The vasym. CH3 mode occurs in the region 2953-2972 cm -1, the vasym. CH2 mode in the region 2920-2935cm -1, the vsym. CH2 mode in the region 2870-2932cm -1, and the vsym. CH 3 bending mode in the region 1363-1388cm -1. SODIUM DIMETHYLPHOSPHONATE (CH3)2P(O)2Na The IR and Raman dating for sodium dimethylphosphonate are listed in Table 3.7 (3). The vasym. CH3 and vsym. CH3 modes are assigned at 2985 and 2919 cm -1, respectively. The asym.

Variables in Data Interpretation

35

(CH3)2 bending modes are assigned at 1428 and 1413 cm -1 and the sym. (CH3)2 bending modes are assigned at 1293 and 1284 cm -1. M E T H Y L T H I O M E T H Y L MERCURY, D I M E T H Y L M E R C U R Y METHYLTHIOCHLOROFORMATE (5) Table 3.8 lists assignments for the CH3-Hg and CH3-S groups for the preceding 3 compounds. These assignments should aid the reader in assigning vibrations for these CH3 groups in other compounds.

(4),

AND

CYCLOALKANES Table 3.9 lists IR vapor-phase data for cycloalkanes (6). Raman data for the ring breathing and ring deformation modes are also presented for cyclobutane and cyclopentane. The vasym. CH2 mode occurs in the region 2930-3100 cm -1. The vsym. CH2 mode occurs in the region 28803020cm -1. Both vCH2 vibrations decrease in frequency as the ring becomes larger. This is the result of lesser ring strain with increasing ring size. The CH2 bend, CH2 wag, CH2 twist, CH2 rock, ring breathing, and ring deformation vibration assignment are also presented.

M I S C E L L A N E O U S ALKYL AND C Y C L O A L K Y L C O M P O U N D Vibrational assignments for cycloalkyl groups are presented in Table 3.10, for alkyl groups of monomers and polymers in Table 3.11, for cyclopropane derivatives in Table 3.12, and for octadecane, octadecane-D38, tetracosane, and tetracosane-D50 in Table 3.13.

REFERENCES 1. 2. 3. 4. 5. 6. Nyquistl R. A. and Fiedler, S. L. (1993). Appl. Spectrosc., 47, 1670. Nyquist, R. A. (1986). Appl. Spectrosc., 40, 275. Nyquist, R. A. (1968). J. Mol. Struct., 2, 111. Nyquist, R. A. and Mann, J. R. (1972). Spectrochim. Acta, 28A, 511. Nyquist, R. A. (1967-68). J. Mol. Struct., 1, 1. Nyquist, R. A. (1984). The Interpretation of Vapor-Phase Infrared Spectra: Group Frequency Data, Philadelphia: Sadtler Research Laboratories, A Division of Bio-Rad.

36
Alkyl Carbon-Hydrogen Vibrations

~" ~ ~l ~'

<1 0
t~

o
d

~' ~1 ~
~
U

0
r O

~O

o0<1
.c
t/) e~

"

L)

0
o
O

o o

0,

Variables in D a t a I n t e r p r e t a t i o n

37

T
O~

e~

Ca

O ~

oh

eq

L)

o
ta OI

o
,-.

eq

..

$~. kl.

"

t~.

~o

~~

38
Alkyl Carbon-Hydrogen Vibrations
0

G
" 0

0 ~r~

,_T

<

o
.

~
<

o~

r
t~

~ o

<

!~ -c~

[, ~ .

<
o .o

"o

~
0 6 0
. ~. ,~
o
~u0

9 "',-

..:

. "--. ,-: d d 6 c~ d 6 o

~
xt

o
xt

~
~

o
t~

c~

c~

<

Ng

a. L.)

Variables in Data Interpretation

39

0.5% Solution of CH3 ~ CH 2 ) n CH3 where n - 3 thru 12 and 16 Solution 9 CCI 4

(vsrm. cH~ o.45 (vasym. CH:z)

o.4o

12 1

~~ ~ 1 1 10

~ s w . /
0.15 0.4 0.6
:
I .... I ~ .... ~ ~ t t I I I

0.8

1.0

1.2

1.4

1.8

1.8

2.0

2.2

2.4

2.6

--4

2.~

A(vasym. CH 3) / A (usym. CH 2)

FIGURE 3.4 A plot of the absorbance ratio A(vsym. A(vasym. CH2) in CC14 solution for C5H12 to C18H38.

CH3)/A(vsym. CH2)

vs the absorbance ratio A(vasym. CH3)/

5 0.5% Solutions of CH3 4 CH2 ~a CH3

w h e r e n - 3 thru 12 and 16

Solvent (s)

eco4
O s4~6 mote v0 c D

O3/C04

A CDCI 3

2859.0 rsym. CH 2, cm "1 2858.5 7

2856.5 2856.0 2855.5

2855.0 8

1 9

14

1312J~----'~--. . . . . . :.---._--. ---

2926.6

2926.8

2927.0

2927.2

2927.4

2927.6

2927.8

2928.0

2928.2

2028.4

vasym. CH2, cm -1

FIGURE 3.5

Plots of vasym. CH2 vs vsym. CH2 in CC14, 54.6 mol % CDC13/CC14, and CDC13 solutions.

40

Alkyl Carbon-Hydrogen Vibrations

5
2873.1 2873.0

6
8

I
I
7

2872.8 2872.8 2872.7 2872.6

C H 3, cm'12872.5 2872.4 2872.3 2872.2 2672.1 2872.0 2871 .g 1 " 2871.8 1-

287L7 T
2871.6 "1"

2871.s/
2'967.2

!
2957.4

.
2967.6

.
2957.8

.
2958.0

.
2958.2

.
2958.4 2958.6

.
2958.8

.
2959.0 2959.2 2959.4
2958.6

]
2959,8

v a s y m . CH3, c m -1

FIGURE 3.6

Plots of vasym. CH3 vs vsym. CH3 in CC14, 54.6 mol % CDC13/CC|4, and CDC13 solutions.

.................
72.0-

-_--_-

_____~__

71.6-

11

......

71,0-

70.5-

(~a.

0,asym. CH2) - 7o.ocn2Y,c~-I

69.5-

69.0-

;
68.5-

68.0-

67.5-

66.0, 84.6

l
8S.0 85.2

I
85.4

I .......
65.6

I ........
85.8

I .....
86.0

I .....
86.2

!
86.4

I
86.6

!
86.8

I
87.0

(vasym.

CH3)-

(vsym.

CHs), cra'l

FIGURE 3.7 Plots of the frequency separation (vasym. CH3-vsym. CH3) vs the frequency separation (vasym. CH2-vsym. CH2) for each n-alkane in CC14, 54.6mol % CDC13/CC14, and CDC13 solutions.

Variables in Data Interpretation

41

TABLE 3.1

IR data for a. and s.CH3 stretching for n-alkanes in 0.5 mol % solutions in CC14, 54.6 mol % CHCI3/CCI 4 a.CH3 str. 54.6 mol % CD C13/CC14 cm- 1 2959.6 2958.7 2959.3 2958.9 2958.7 2958.5 2958.4 2958.2 2958.1 2958 2957.9 2957.3 -2.3 s.CH3 str. 54.6 mol % CDC13/CC14 cm- 1 2872.9 2872.7 2872.8 2872.5 2872.5 2872.5 2872.5 2872.4 2872.3 2872.3 2872.2 2871.8 -1.1

Compound Pentane Hexane Hexane Heptane Octane Nonane Decane Undecane Dodecane Tridecane Tetradecane Octadecane delta cm -1

a.CH3 str. CC14 cm- 1 2959.6 2958.7 2959.2 2958.9 2958.6 2958.5 2958.4 2958.1 2958 2957.9 2957.8 2957.3 -2.3 a.CH3 str. [CC14][54.6mol % CDC13/CC14] cm- 1

a.CH3 str. CDC13 cm- 1 2959.7 2958.8 2959.3 2959 2958.7 2958.6 2958.5 2958.3 2958.2 2958.1 2858 2957.5 -2.2 s.CH3str. [CC14][54.6mol % CDC13/CC14] cm- 1 -0.2 -0.24 -0.27 -0.29 -0.29 -0.29 -0.28 -0.33 -0.34 -0.36 -0.52

s.CH3 str. CC14 cm- 1 2873.1 2872.9 2873.1 2872.8 2872.8 2872.8 2872.8 2872.7 2872.7 2872.7 2872.6 2872.4 -0.7

s.CH3 str. CDC13 cm- 1 2872.7 2872.3 2872.5 2872.2 2872.2 2872.2 2872.1 2872.1 2872 2871.9 2871.8 2871.5 -1.2

a.CH3 str. [CC141_ [CDC13] cm- 1 0.11 0.08 0.12 0.11 0.12 0.14 0.19 0.2 0.16 0.2 0.22

s.CH3 str. [CC14][CDC13] cm- 1 -0.45 -0.51 -0.58 -0.62 -0.62 -0.64 -0.65 -0.7 -0.74 -0.79 -0.85

Pentane Hexane Heptane Octane Nonane Decane Undecane Dodecane Tridecane Tetradecane Octane

0.02 0.03 0.05 0.04 0.04 0.06 0.08 0.16 0.08 0.06 0.08

42
TABLE 3.2 bending Compound Pentane Hexane Hexane Heptane Octane Nonane Decane Undecane Dodecane Tridecane Tetradecane Octadecane

Alkyl Carbon-Hydrogen Vibrations

IR absorbance data for n-alkanes: a. and s.CH2 and CH3 stretching and CH2

A[a.CH3 str.] 1.09 0.879 0.903 0.769 0.67 0.637 0.563 0.538 0.478 0.496 0.473 0.374

A[a.CH2 str.] 0.78 0.759 0.86 0.925 0.938 1.027 1.028 1.083 1.073 1.197 1.23 1.234 A[CH2 bend] 54.6mol % CDC13/CC14 0.141 0.115 0.123 0.111 0.096 0.103 0.092 0.093 0.084 0.081 0.081 0.08

A[s.CH3 str.] 0.502 0.408 0.419 0.372 0.329 0.319 0.287 0.283 0.256 0.271 0.263 0.221

A[s.CH2 str.] 0.407 0.402 0.43 0.45 0.458 0.512 0.527 0.558 0.56 0.632 0.66 0.672

A[CH2 bend] CCl4 Pentane Hexane Hexane Heptane Octane Nonane Decane Undecane Dodecane Tridecane Tetradecane Octadecane 0.137 0.127 0.152 0.147 0.128 0.143 0.136 0.134 0.132 0.141 0.141 0.132

A[CH2 bend] CDC13 0.105 0.082 0.09 0.084 0.073 0.063 0.06 0.057 0.05 0.051 0.047 0.037

Variables in Data Interpretation

43

TABLE 3.2A

Absorbance ratios for CH3 and CH 2 groups for n-alkanes A[a.CH3 str.] /A[s.CH3 str.] 2.171 2.154 2.155 2.067 2.036 1.997 1.962 1.901 1.867 1.83 1.798 1.692 A[a.CH3 str.] /A[s.CH2 str.] A[a.CH2 str.] /A[s.CH2 str.l 1.916 1.912 2 2.064 2.048 2.006 1.951 1.941 1.916 1.894 1.864 1.836 A[s.CH3 str.] /A[a.CH2 str.] 0.644 0.531 0.5 0.402 0.351 0.311 0.279 0.261 0.238 0.226 0.214 0.179 A[a.CH3 str.] /A[a.CH2 str.] 1.397 1.143 1.05 0.831 0.714 0.62 0.548 0.497 0.445 0.414 0.385 0.303 A[s.CH3 str.] /A[CH2 bend] 4.781 4.976 4.656 4.429 4.507 5.063 4.783 4.965 5.12 5.313 5.596 5.972 A[s.CH3 str.] /A[s.CH2 str.] 1.233 1.015 0.974 0.827 0.718 0.623 0.545 0.507 0.457 0.428 0.398 0.329

Compound Pentane Hexane Hexane Heptane Octane N onane Decane Undecane Dodecane Tridecane Tetradecane O c tadecane

Pentane Hexane Hexane Heptane Octane N onane Decane Undecane Dodecane Tridecane Tetradecane Octadecane

2.678 2.187 2.1 1.689 1.463 1.244 1.068 0.964 0.854 0.785 0.717 0.557

44
TABLE 3.3 CDCI3

Alkyl Carbon-Hydrogen Vibrations IR data for a. and s.CH2 stretching for n-alkanes in 0.5% solutions in C14, 54.6 mol % CDCI3/CCI4, and

a.CH2 str. CCI4 Compound Pentane Hexane Hexane Heptane Octane Nonane Decane Undecane Dodecane Tridecane Tetradecane Octadecane delta cm -1
cm1

a.CH2 str. 54.6 mol % CD C13/CC14

cm1

a.CH2 str.
CDC13 cm- 1 2928.1 2928.3 2928.1 2927.6 2927.3 2927.1 2927.1 2927 2927 2927 2927 2926.9 -1.2 s.CH2 str. [CC14][mol % CDC13/CC14] cm-1 -0.41 -0.08 -0.17 -0.25 -0.21 -0.09 -0.04 -0.02 -0.02 -0.01 -0.03 -0.01

s.CH2 str.
CC14
cm-- 1

s.CH2 str. 54.6 mol % CD C13/CC14 cm- 1 2861.4 2859.3 2859 2857.6 2856.3 2855.6 2855.3 2855.1 2854.9 2854.8 2854.7 2854.6 -6.8

s.CH2 str. CDC13 cm- 1 2861.2 2859.1 2858.7 2857.4 2856.2 2855.6 2855.3 2855.1 2854.9 2854.8 2854.7 2854.6 -6.6

2927.7 2928 2927.9 2927.3 2927 2926.8 2926.8 2926.8 2926.7 2926.7 2926.7 2926.6 -1.1 a.CH2 str. [CC14][mol % CDC13/CCI4] cm-1

2928 2928.2 2928 2927.5 2927.1 2927 2927 2926.9 2926.9 2926.8 2926.8 2926.7 -1.3

2861.8 2959.4 2859.1 2857.8 2856.6 2855.7 2855.3 2855.1 2854.9 2854.8 2854.8 2854.6 -7.2

a.CH2 str. [CC14][CDC13] cm-1 0.41 0.25 0.23 0.29 0.31 0.28 0.3 0.27 0.29 0.28 0.3 0.31

s.CH2 str. [CCI4][CDC13] cm-1 -0.61 -0.26 -0.38 -0.44 -0.33 -0.1 -0.06 -0.04 -0.04 -0.04 -0.06 -0.06

Pentane Hexane Hexane Heptane Octane Nonane Decane Undecane Dodecane Tridecane Tetradecane Octadecane

0.22 0.16 0.15 0.16 0.16 0.16 0.12 0.17 0.14 0.13 0.14 0.12

Variables in Data Interpretation

45

TABLE 3.4 The frequency separation between the a. and s.CH3 and the a. and s.CH2 stretching vibrations for n-alkanes in CC14, CDCI3/CCI4, and CDC13 solutions [a.CH3 str.][s.CH3 str.] 54.6m01% CD C13/CC14 cm- 1 86.55 86.45 86.37 86.13 86 85.92 85.8 85.76 85.71 85.61 85.51 - 1.04 [a.CH2 str.][s.CH2 str.] mol % CD C13/CC14 cm- 1 66.54 68.84 69.89 70.77 71.36 71.68 71.86 71.96 72.01 72.06 72.15 5.61

Compound Pentane Hexane Hep tane Octane Nonane Decane Undecane Dodecane Tridecane Tetradecane Octadecane delta cm -1

[a.CH3 str.][s.CH3 str.] CC14 cm- 1 86.43 86.18 86.05 85.8 85.67 85.57 85.44 85.37 85.29 85.19 84.91 - 1.52

[a.CH3 str.][s.CH 3 str.] CDC13 cm- 1 86.99 86.77 86.75 86.53 86.41 86.35 86.28 86.27 86.19 86.18 85.98 - 1.01

[a.CH2 str.][s.CH 2 str.] CC14 cm- 1 66.32 66.6 69.48 70.4 71.11 71.52 71.67 71.8 71.87 71.89 72.02 5.7

[a.CH2 str.][s.CH2 str.] CDC13 cm- 1 66.52 69.11 70.21 71.04 71.42 71.88 71.98 72.13 72.19 72.25 72.34 5.82

TABLE 3.5

The CH 3 and CH2 bending frequencies and frequency separations for n-alkanes [CH2 bend][s.CH3 bend] cm- 1 88.32 88.74 88.76 88.73 88.74 88.76 89 88.76 88.77 88.72 88.74 88.69 [a.CH3 bend][s.CH3 bend] cm- 1 78.77 79.89 79.7 79.42 80.23 79.7 80.17 79.67 79.65 79.63 79.95 79.33

Compound Petane Hexane Hexane Heptane Octane Nonane Decane Undecane Dodecane Tridecane Tetradecane O ctadecane

CH2 bend cm- 1 1467.55 1467.22 1467.35 1467.39 1467.36 1467.33 1467.39 1467.63 1467.39 1467.36 1467.35 1467.33

a.CH3 bend cm- 1 1458 1458.37 1458.29 1458.08 1458.85 1458.27 1458.56 1458.27 1458.27 1458.27 1458.56 1457.97

s.CH3 bend cm- 1 1379.23 1378.48 1378.59 1378.66 1378.62 1378.57 1378.39 1378.6 1378.62 1378.64 1378.61 1378.64

46
Alkyl Carbon-Hydrogen Vibrations
<
9 ,-~ r',l ~~(',,I 9 ,---~ t'~ 0 . . . 0

O0 ~D O0 tt'~ !/'~
o d d d d d 0 d d d 0 0 0 d

c; o

c~ o

c~

c~ o

O0 b.... .
.

. O0 O0

0000

c~ ,'~ ~

c~ d

=
.<

o
0

c~

c~

O O d o

~'~1 0

0 0 0 0 0

u
0

<
~g

c~Ooc;O

b...

2
0
|

o
r

Variables in Data Interpretation

47

TABLE 3.7

IR and Raman data for (CH3)2PO2Na in water and in the solid phase IR solid phase cm- 1 2985 2919 1428 1413 1293 1284 912 860sh 851 839sh ? IR H20 soln. cm- 1 Raman H20 soln. cm- 1 2988 2921 1422 1413

(CH3)2P(O)2Na Assignments a.[(CH3)2 str.] s.[(CH3)2 str.] a.[ (CH3)2 bend] s.[(CH3)2 bend]

5 al
1 1 1

4 a2
1

4 bl
1

5 b2
1 1 1

1429 --~ 1412 1309 1301

915 878 ?

(CH3)2 rock (CH3)2 torsion

TABLE 3.8

IR data and assignments for CH3HgSCH3, CH3SC(C=O)CI, and (CH3)2Hg CH3-S-C(=O)C1 cm-~ CH3-S-P(=O)C12 cm -1 (CH3)2Hg cm-~ [CH3-Hg group] 2970 2910 1397 or 1443 1182 700,788 ) [CH3-S group] 3025 2940 1430 1320 976 ? [CH3-S group] 3011 2938 1431 1321 972 ?

CH3-Hg-S-CH3 cm-1 [CH3-Hg group] 2984 2919 1408 1177 763 7 [CH3-S group] 2984 2919 1432 1309 956 ? 533 333 190 120 ? not observed.

Assignment

a.CH3 str. a.CH3 str. a.CH3 bend s.CH3 bend CH3 rock CH 3 torsion

a.CH3 str. s.CH3 str. a.CH3 bend s.CH3 bend CH3 rock CH3 torsion H g - C str. H g - S str. H g - S - C bend H g - S - C H 3 torsion ?

o o o o o

"

~<

o d o

N d d d d d

&o

o O0

d
m
~

d~
~

m
O0 O0 O0 O0 O0 O0

o ~
~

o~ o

& ~

u ~d

m.

o
r.l

o o o

"~

t..)

o o o ~

o o o o o o
~ ~ ~ ~ t ~ t 0

o
~ 0 ~

k.)

e-i

0 O0 t'~l t~l

,---~ ,.--, 0 ~ l> O0

0 t'xl

0 tt~

0 C~

0 ~'xl

0 r

0 t'xl

0 r

C)

t~

~--~ ~-~ Oh t~'l

~---" ~ - "

0"~ t'xl

Ox t',l

C~ t'~l

O~ r

O~ ~1

O~ t'xl

O~ t",l

C~ t'xl

O~ c',l

o
0 0 0 0 0 0 0 0 o

o k.)

o~

Variables in Data Interpretation

49

TABLE 3.10

Raman and IR data for compounds containing cycloalkyl groups

Compound Cyclopropane (vap.) Cyclopropane carboxylic acid Chlorocyclobutane Cyclobutane carboxylic acid Cyclopentane Chlorocyclopentane Bromocyclopentane Cyclopentanecarbonitrile 1 Cyclopentane carboxylic acid Cyclopentyl alcohol Cyclohexane Chlorocyclohexane Bromocyclohexane Cyclohexyl alcohol Cyclohexyl amine 1,2,4-Trivinylcyclohexane Cycloheptane Cyclodecane I[CN str., 2234 (40, p)].

Raman neat a.CH2 str.

Raman neat s.CH2 str. 3039 (83, p) 3020 (37, p)

Raman neat s.CH2 str. in ER. 3020 (37, p)

Raman neat CH2 bend 1452 (2, p) 1458 (5, p) 1433 (4, p)

IR v.p. a.CH2 str. 3100 3102

IR v.p. s.CH2 str. 3020 3032

2985 (26, p)

2955 (44, p)

2995 2943 2971 2967 2970 2967 (43, (46, (43, (40, (41, p) p) p) p) p) 2868 2919 2915 2875 2875 (45, (33, (29, (29, (29, p) p) p) p) p) 1446 1446 1448 1446 1449 (6, (6, (5, (6, (8, p) p) p) p) p) 2960 2980 2970 2970

2890 2880 2890 2890 2890

2876 (21, p)

2962 (84, p) 2924 (40)

2875 (45, p) 2852 (52)

1448 (9, p) 1446 (10)

2940 2937 2920 2932 2927 2914

(42, (71, (59, (4) (42, (84,

p) p) p) p) p)

2855 (45, p) 2855 (76, p) 2852 (4) 2853 (37, p)

1440 (7, p) 1440 (10, p) 1443 (1) 1441 (8, p) 1442 (10, p)

2935 2948 2942 2940 2938

2860 2870 2865 2864 2862

2930

2880

50

Alkyl Carbon-Hydrogen Vibrations

k.)

9
II
r

I L) I

L)
O~ I ~
r

~::~ I ~

~0 ~0

C~ O~ O~ O0 O0 O0 C~ O~ C~ C~ O0 u~

u~ 00

C~ I ~

C~ C~ ~

O0 O0 O0 O0 ~0 O0 O0 O0 O0 O0 O0 O0 O0 O0 O0 O0 O0 O0 O0 O0 O0 O0 O0 O0 O0 O0 O0 O0 O0 O0 O0 O0 O0 O0 C~ O0 O0

O~ O0 I ~

C~ O0 I ~

O0 ! ~

O0

'00 O 0 0 ~

OX O0

Ox C~ Ox ~

OX O0 O0 O0

C~ C~ ~

C~ C~ O~ ~

O~

C~ O0 O0 O0 QO

O0 O0 O0 O0 O0 O0 O0 ~

~ cq t u~ ~ O~ O~ ~ ~ c~ C~ C~

~ ~1

C~ C~ ~ ~1 c~ cq

C~ O~ O~ O~ C~ c~

C~

O~ O~

C~

C~ ~

O~ C~ O~

C~ O~ C~ C~ cq c~ c~ ~1

9
0 0
I-i t~

0
0

~ ~ o

o~~

Variables in Data Interpretation

51

.=.
"-7. " 7 .
t~

er ~te-q e-q e,,I O c,,l ce~ G

eq tt~
o

c-,I r v tt~ ~'-

tt~

~1-- ~

te~

tt~

tt~

tt~

er

er

e'q Q o9 er

eq r e~ tt~ e-,I

t',,l

e-,I e q

e',l

e-,l

tt~ eq r e'q e',l

c,,I eq

e-,I e-,l e q eq eq eq e-,I e',l tt~ eq tt~ e-,l e-,I

eq eq

er e-,,I

er c,,I

t-q

e-q e'q

eq

e'q

e-,l

eq

04

e'q

e-,I

eq

eq

eq

eq

e',,I

c,,I

eq

CO

z~

F~

~.

52
Alkyl Carbon-Hydrogen Vibrations
~ o ~ o ~ ~ o o o o o

M ~ 0 ~ ~ ~ e.,l

~, o O ~
t,-. 6 t-,t~. t~

o
o

o~

o
d o c5 o o d d o o o

6 o "=1 o

~
o

~ ~ .

a0

q 0 0 0

q 0

eq

a0 m

c~ eq

ox ,-.~

u~ o

~0~
o o o 0 m 0 o d o d o o o o o m o ~ ~ o ~ o m ~ 0

8
m 0

u~ ~o

r~l d c S d 0 d ~ o~ m o e.,l o ...~ o d d d te~ o

t~

r~l

co

u-~

u-~ ~,~ ,.-~ d d m o

ox

,---9. o

g.
o 00

m ~'-

t.,l o

9 ~'e~

k.)

~o
9

t-~
9

r-I
~. . .

o o o ~..,, ,~j ,,.., o ,~ o

o o o ~..., ~.~, ~.~, u"~ 00 u'~

o~o

~o o
o~
0 o

e'l

s
u o

~ o

Variables in Data Interpretation

53
d ~~176
e,l,~ ~,iv .

c~ o c ~

Oc~

,J

(5

~5

c5~

o r r

"0

~"

t4

tt~

o
eq 04

c5

c5~

tj

eq

eq

eq

eq

t~