CHAPTER

Alkyl Carbon-Hydrogen Vibrations

32
34
34
34

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

35
35
35
Tables

36
37
38
39
39
40
40

(31)
(31)
(32)
(32)
(32)
(32)
(32)

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)

*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

(4),

AND

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.

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

~"
~ ~l ~'

o0<1

~' ~1~
~O

o o

0,

<1
0

"

t~
d

L)

e~

t/)

.c

Alkyl Carbon-Hydrogen Vibrations

~o

e~

Ca

O ~

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

~~

O~

oh

eq

L)

kl.

eq

,-.

$~.

..

t~.

ta
OI

"

37

38

"-

9
',-

..:

t~

.
"--.

,-:

Ng

c~

~.

,~

t~

"o

o~

[, ~ .

!~- c ~

"

<

.o

<

<

<

<

,_T

0
~r~

Alkyl Carbon-Hydrogen Vibrations

c~

xt

xt

c~

~u0

a. L.)

39

Variables in Data Interpretation

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

....

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
14

2855.0
8

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

2872.8 I

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-

11

71.6-

......

71,0-

70.5-

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

(~a.

69.5-

69.0-

68.5-

68.0-

67.5-

66.0,
84.6

8S.0

85.2

85.4

I .......
65.6

(vasym.

CH3)-

I ........
85.8

(vsym.

I .....
86.0

I .....
86.2

!
86.4

I
86.6

86.8

87.0

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.

41

Variables in Data Interpretation

TABLE 3.1

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

Pentane
Hexane
Heptane
Octane
Nonane
Decane
Undecane
Dodecane
Tridecane
Tetradecane
Octane

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.
CC14
cm- 1

a.CH3 str.
54.6 mol %
CD C13/CC14
cm- 1

a.CH3 str.
CDC13
cm- 1

s.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

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

2959.7
2958.8
2959.3
2959
2958.7
2958.6
2958.5
2958.3
2958.2
2958.1
2858
2957.5
-2.2

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

a.CH3 str.
[CC14][54.6mol %
CDC13/CC14]
cm- 1

a.CH3 str.
[CC141_
[CDC13]
cm- 1

s.CH3str.
[CC14][54.6mol %
CDC13/CC14]
cm- 1

s.CH3 str.
[CC14][CDC13]
cm- 1

0.02
0.03
0.05
0.04
0.04
0.06
0.08
0.16
0.08
0.06
0.08

0.11
0.08
0.12
0.11
0.12
0.14
0.19
0.2
0.16
0.2
0.22

-0.2
-0.24
-0.27
-0.29
-0.29
-0.29
-0.28
-0.33
-0.34
-0.36
-0.52

-0.45
-0.51
-0.58
-0.62
-0.62
-0.64
-0.65
-0.7
-0.74
-0.79
-0.85

s.CH3 str.
54.6 mol %
CDC13/CC14
cm- 1

s.CH3 str.
CDC13
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

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

42

Alkyl Carbon-Hydrogen Vibrations

TABLE 3.2
bending

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

Compound

A[a.CH3 str.]

A[a.CH2 str.]

A[s.CH3 str.]

A[s.CH2 str.]

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

1.09
0.879
0.903
0.769
0.67
0.637
0.563
0.538
0.478
0.496
0.473
0.374

0.78
0.759
0.86
0.925
0.938
1.027
1.028
1.083
1.073
1.197
1.23
1.234

0.502
0.408
0.419
0.372
0.329
0.319
0.287
0.283
0.256
0.271
0.263
0.221

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

A[CH2 bend]
54.6mol %
CDC13/CC14

A[CH2 bend]
CDC13

0.137
0.127
0.152
0.147
0.128
0.143
0.136
0.134
0.132
0.141
0.141
0.132

0.141
0.115
0.123
0.111
0.096
0.103
0.092
0.093
0.084
0.081
0.081
0.08

0.105
0.082
0.09
0.084
0.073
0.063
0.06
0.057
0.05
0.051
0.047
0.037

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

43

Variables in Data Interpretation

TABLE 3.2A

Absorbance ratios for CH3 and CH 2 groups for n-alkanes

Compound

A[a.CH3 str.]
/A[s.CH3 str.]

A[a.CH2 str.]
/A[s.CH2 str.l

A[a.CH3 str.]
/A[a.CH2 str.]

A[s.CH3 str.]
/A[s.CH2 str.]

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

2.171
2.154
2.155
2.067
2.036
1.997
1.962
1.901
1.867
1.83
1.798
1.692

1.916
1.912
2
2.064
2.048
2.006
1.951
1.941
1.916
1.894
1.864
1.836

1.397
1.143
1.05
0.831
0.714
0.62
0.548
0.497
0.445
0.414
0.385
0.303

1.233
1.015
0.974
0.827
0.718
0.623
0.545
0.507
0.457
0.428
0.398
0.329

A[a.CH3 str.]
/A[s.CH2 str.]

A[s.CH3 str.]
/A[a.CH2 str.]

A[s.CH3 str.]
/A[CH2 bend]

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

0.644
0.531
0.5
0.402
0.351
0.311
0.279
0.261
0.238
0.226
0.214
0.179

4.781
4.976
4.656
4.429
4.507
5.063
4.783
4.965
5.12
5.313
5.596
5.972

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

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

cm-

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

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
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

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

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

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

a.CH2 str.

s.CH2 str.

CDC13
cm- 1

CC14

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

cm-- 1

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

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

s.CH2 str.
54.6 mol %
CD C13/CC14
cm- 1

s.CH2 str.
CDC13
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

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

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

Compound

[a.CH3 str.][s.CH3 str.]

CC14
cm- 1

[a.CH3 str.][s.CH3 str.]

54.6m01%
CD C13/CC14
cm- 1

[a.CH3 str.][s.CH 3 str.]

CDC13
cm- 1

[a.CH2 str.][s.CH 2 str.]

CC14
cm- 1

[a.CH2 str.][s.CH2 str.]

mol %
CD C13/CC14
cm- 1

[a.CH2 str.][s.CH2 str.]

CDC13
cm- 1

Pentane
Hexane
Hep tane
Octane
Nonane
Decane
Undecane
Dodecane
Tridecane
Tetradecane
Octadecane
delta 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

86.55
86.45
86.37
86.13
86
85.92
85.8
85.76
85.71
85.61
85.51
- 1.04

86.99
86.77
86.75
86.53
86.41
86.35
86.28
86.27
86.19
86.18
85.98
- 1.01

66.32
66.6
69.48
70.4
71.11
71.52
71.67
71.8
71.87
71.89
72.02
5.7

66.54
68.84
69.89
70.77
71.36
71.68
71.86
71.96
72.01
72.06
72.15
5.61

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

Compound

CH2 bend
cm- 1

a.CH3 bend
cm- 1

s.CH3 bend
cm- 1

[CH2 bend][s.CH3 bend]

cm- 1

[a.CH3 bend][s.CH3 bend]

cm- 1

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

1467.55
1467.22
1467.35
1467.39
1467.36
1467.33
1467.39
1467.63
1467.39
1467.36
1467.35
1467.33

1458
1458.37
1458.29
1458.08
1458.85
1458.27
1458.56
1458.27
1458.27
1458.27
1458.56
1457.97

1379.23
1378.48
1378.59
1378.66
1378.62
1378.57
1378.39
1378.6
1378.62
1378.64
1378.61
1378.64

88.32
88.74
88.76
88.73
88.74
88.76
89
88.76
88.77
88.72
88.74
88.69

78.77
79.89
79.7
79.42
80.23
79.7
80.17
79.67
79.65
79.63
79.95
79.33

46

~g

<

.<

<

r',l

~-

,-~

c~ o

~-

(',,I

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

c; o

O0

,---~

c~

t'~

0000

c~

c~

c~Ooc;O

0 0 0 0 0

O O d o

O0

. 0

Alkyl Carbon-Hydrogen Vibrations

c~ o

O0

c~ d

~'~1 0

b....

c~ ,'~ ~

b...

2
o

47

Variables in Data Interpretation

TABLE 3.7

IR and Raman data for (CH3)2PO2Na in water and in the solid phase

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

(CH3)2 rock
(CH3)2 torsion

TABLE 3.8

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

1429
--~ 1412
1309
1301

5 al

4 a2

4 bl

5 b2

2988
2921
1422
1413

1
1
1

1
1
1

915

878
?

IR data and assignments for CH3HgSCH3, CH3SC(C=O)CI, and (CH3)2Hg

CH3-Hg-S-CH3
cm-1

CH3-S-C(=O)C1
cm-~

CH3-S-P(=O)C12
cm -1

[CH3-Hg group]
2984
2919
1408

[CH3-Hg group]
2970
2910
1397 or
1443
1182
700,788
)

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

(CH3)2Hg
cm-~

[CH3-S group]
3025
2940
1430
1320
976
?

[CH3-S group]
3011
2938
1431
1321
972
?

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 ?

r.l

t..)

k.)

e-i

t~

o
o

k.)

o d o

O0

o o o ~
0

O0

t'xl

&o

"

d~

~<

u~ d

&
~

c',l

C)

"~

O~

o o o o o

o~ o

o o o

~o

O0 O0 O0 O0 O0

~'xl

C~

o o o o o o

tt~

N d d d d d

l>

t'xl

O0

C~
t'xl

,---~ ,.--, 0

O~
t",l

0
O0
t'~l t~l

O~
t'xl

O~
~1

O~
r

C~
t'~l

Ox
t',l

~---" ~ - "

0"~
t'xl

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

m.

o~

49

Variables in Data Interpretation

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)

2985 (26, p)

2943
2971
2967
2970
2967

(43,
(46,
(43,
(40,
(41,

p)
p)
p)
p)
p)

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

(45,
(33,
(29,
(29,
(29,

p)
p)
p)
p)
p)

IR
v.p.
a.CH2 str.

IR
v.p.
s.CH2 str.

1452 (2, p)
1458 (5, p)

3100
3102

3020
3032

2995

2890

2960
2980
2970

2880
2890
2890

2970

2890

2860
2870
2865
2864
2862

2880

1433 (4, p)

2955 (44, p)

2868
2919
2915
2875
2875

Raman
neat
CH2 bend

2876 (21, p)

1446
1446
1448
1446
1449

(6,
(6,
(5,
(6,
(8,

p)
p)
p)
p)
p)

2962 (84, p)
2924 (40)

2875 (45, p)
2852 (52)

1448 (9, p)
1446 (10)

2940
2937
2920
2932
2927
2914

2855 (45, p)
2855 (76, p)

1440 (7, p)
1440 (10, p)

2935
2948
2942
2940
2938

2852 (4)
2853 (37, p)

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

2930

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

p)
p)
p)
p)
p)

50

9
II
I
I

I-i

k.)

L)

L)

t~

0
0

~
cq

~
~1

0
0

~::~ I ~

O~ I ~

~0 ~0

Alkyl Carbon-Hydrogen Vibrations

C~ C~ ~

C~ I ~

u~ 00

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

O~ O0 I ~

C~ C~ O~ ~

C~ O0 I ~

C~

O~ O~

O~

O0 ! ~

C~ C~ ~

C~

C~

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

Ox C~ Ox ~

OX O0 O0 O0

'00 O 0 0 ~

O0 O0 O0 O0 O0 O0 O0 ~

OX O0

O0

C~ O0 O0 O0 QO

C~

C~ ~

o~~

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

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

C~ C~ ~
~1 c~ cq
t

O~ C~ O~

c~

u~ ~

O~ O~

~ ~
o

tt~

t',,l

eq

eq

Q
o9
er

e'q

.=.
t~

~1-- ~

e-,I e q

e',l

~t-

tt~

tt~

e-,l

tt~

e,,I

c,,l

"-7. " 7 .

e-q

er

e-q

er

er
ce~
G

eq

c-,I r
v
tt~ ~'-

r
r

e-,I

eq

eq

e-,,I

er

c,,I

eq

c,,I

er

e-,I

e',,I

c,,I

eq
e-,l

eq

eq

e-,I e',l

tt~

eq

e~
tt~

tt~

eq

e-,I

eq

e-,I

e',l

e'q

e'q

04

eq

tt~

eq

e'q

e-,l

te~

Variables in Data Interpretation

tt~

eq

eq

eq

e-q e'q

e-,l e q

t-q

CO

F~

z~

~.

51

52

g.

e'l

o
"=1

r~l

d o

t~

~
o~

r~l

t.,l
o

d c S d
m
~'-

o
00

~o

~ oo
o

o~

co
d
m
o

t-~

q
0

d
e.,l
o

,~

u-~

...~
o

r-I
~.

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

~
o

~ ~ .

q
0

e.,l

t-,-

t~.

t~

~,

u~
~o

a0

c5

Alkyl Carbon-Hydrogen Vibrations

o~

t,-.

o O ~

eq

u~
o

ox
,-.~

c~
eq

a0
m

~0~

,---9. o

ox

~
o

o~o

e~

k.)

9~'-

u'~

m
o

u-~ ~,~ ,.-~

d
te~
o

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

Variables in Data Interpretation

"0

d ~~176
e,l,~

Oc~

~,iv

tt~

c5~

c5

(5

tj

c~ o c ~

,J

c5~

t4

~5

~"

eq

04

eq

eq

eq

eq

t~

53