CHAPTER

10

Carboxylic Acids
4-X-Benzoic Acids Half Salts of Carboxylic Acids References Figures Figure Figure Figure Figure Figure Figure Figure Figure Figure Figure Figure Figure Figure Figure Figure Figure Figure Figure Figure 10-1 10-2 10-3 10-4 10-5 10-6 10-7 10-8 10-9 10-10 10-11 10-12 10-13 10-14 10-15 10-16 10-17 10-18 10-19 175 176 177 178 179 180 181 182 183 184 185 186 187 188 189 190 191 192 193 (166) (166) (166) (167) (168, ( 168, (168, (168, (168, (169) (169) (169) (169) (169) (170) (170) (170) (170, Tables Table Table Table Table Table Table Table Table Table Table 10-1 10-2 10-3 10-4 10-4a 10-5 10-6 10-7 10-8 10-9 194 195 196 197 198 199 200 201 202 203 170 172 173

169) 169) 169) 169) 169)

(167) (167) (170) (170) (171) (172) (172) (172) (172)

171)

*Numbers in parentheses indicate in-text page reference.

In the condensed phase or in concentrated solution carboxylic acids exist as a double hydrogen bonded dimer as illustrated here:

\/__o... \
o

C->
d
9 9 9 O ' - - - C

Structure A

165

166

Carboxylic Acids

Thus, these dimers have a center of symmetry, and only the out-of-phase (C--O) 2 stretching mode is IR active, and only the in-phase (C=O) 2 stretching mode is Raman active. However, in the vapor phase at elevated temperatures carboxylic acids exist in the monomeric form (R-COzH or ~b-CO2H). The vasym. (OH...O=C)2 mode for structure A is very broad over the range 2500-3000 with subsidiary maxima, which are due to combination and overtones in Fermi resonance with vasym. (OH-.-O=C)2. The Vip(C=O) 2 occurs in the region 1625-1687 cm -1 in the Raman, inplane (C--OH) 2 bend in the region 1395-1445 cm -1, and 7(OH) 2 in the range 875-960 cm -1. Table 10.1 lists IR vapor-phase data, and CC14 and CHC13 solution-phase data for aliphatic carboxylic acids (1,2). The monomeric vOH frequency for the aliphatic carboxylic acid occurs near 3580, 3534, and 3519cm -1 in the vapor, CC14, and CHC13 phases, respectively. In CC14 solution the decrease in the vOH frequency is due to intermolecular hydrogen bonding between the acid proton and the C1 atom of CC14 ( C O z H . . . C1CC13). The C1 atoms are less basic in CHC13 than they are in CC14; however, the vOH still occurs at lower frequency in CHC13 than in CC14 solution. This is attributed to the following doubly hydrogen-bonded complex in CHC13, which causes vOH to shift to a lower frequency than in CC14 solution (2).

HIC~ ." Cl 0 / C ~ - O' R

Structure B

The vC=O frequencies for these aliphatic carboxylic acids decrease in frequency in the order for vapor (1789-1769 cm-1), CC14 (1767.3-1750.3 cm-1), and CHC13 (1756.3-1769 cm-1), and in the order of increased branching on the a-carbon atom [CH 3 to C(CH3) 3] within each physical phase. Figure 10.1 shows plots of v C - O for aliphatic carboxylic acids in CC14solution and in CHC13 solution vs the number of protons on the acid a-carbon atom (2). The numbers 1-5 on each curve in Figs. 1-4 are for acetic acid, propionic acid, butyric acid, isobutyric acid, and trimethylacetic acid, respectively. Similar curves were obtained plotting v C - O vs cr* and v C - O vs Es. The ~* values are a measure of the inductive contribution of the alkyl group and ES is a measure of the steric factor of the alkyl group (3). Thus, it appears that both inductive and steric factors affect vC=O frequencies as well as the intermolecular hydrogen-bonded complex formed, as discussed previously. The out-of-phase ( C - O ) 2 stretching, Vop(C=O)2, modes occur in the range 1702.21714.6cm -1 and 1699.6-1712.5cm -1 in CC14and CHC13 solutions, respectively, and within each solvent the frequencies decrease as o-* and Es increase. In the case of Vip (C=O)2, it is not IR active. Figures 10.2 and 10.3 show, respectively, plots of vC--O vs mole % CHC13/CC14 arid Vop (C=O) 2 vs mole % CHC13/CC14 for aliphatic carboxylic acids. In CC14solution vC--O occur at the highest frequency, and then decrease in frequency as the mole % CHC13/CC14 is increased from ~10 to 100. On the other hand, Vop(C=O) 2 decreases linearly as the mole % CHC13/CC14 is increased from 0 to 100. The essentially linear decrease in both v C - O and Vop ( C - O ) 2 after the

Variables

in

Data

Interpretation

16 7

initial intermolecular hydrogen bond formation in the case of vC=O is attributed to the reaction field of the solvent system. The reaction field is defined as follows: [R]= ( 6 - 1 ) / ( 2 ~ + n 2) where 6 is the dielectric constant and n is the refracture index of the solvent system (4). It has been shown that there is a linear relationship between the mole % CHC13/CC14 and the reaction field (3). The reaction field increases as the mole % CHC13/CC14 increases and this is a result of an increasing dielectric contribution of the solvent system accompanied by a decrease in the refractive index of the solvent system. The decrease in the Vop(C-O) 2 frequency in going from solution in CC14 to solution in CHC13 is attributed to the following intermolecularly hydrogenbonded structure (2):
R

\
C ~ O . 9 - H

CCI3~H

9 9 .0

/ \

\ /
\

O...

H~CCl

H 9 9 9 O----C

Structure C

The gradual decrease in frequency is attributed to the increase in the reaction field as the mole % CHC13/CC14 is increased. Figure 10.4 show plots of A(vC=O)/A[Vop (C=O) 2 vs mole % CHC13/CC14. These plots indicate that as this ratio increases, as the mole % CHC13/CC14 increases, the concentration of molecules existing as Structure B increases while compounds existing as Structure A decrease with a subsequent increase in Structure C. IR vapor-phase bands in the range 1105-1178 c m -1 a r e assigned to v C - C - O and IR vaporphase bands in the range 571-580cm -1 are assigned to 7C=O (1). The frequency separation between these two modes in the vapor phase varies between 520 and 598cm -1. Table 10.2 lists Raman data and assignments for v(C=O) 2 and vC=C for carboxylic acids (6). Four of the acids listed in Table 10.2 exhibit a Raman band, which can be assigned as Vop(C=O) 2 in the range 1712-1730cm -1. Apparently these four hydrogen-bonded carboxylic acids do not have a center of symmetry in the neat phase. The Vip(C=O) 2 has weak to strong relative Raman band intensity and occurs in the range 1630-1694 c m - 1. The lowest frequency is exhibited by 3-(4-hydroxy-3-methoxyphenyl)-2-propionic acid, and the highest frequency is exhibited by polymethacrylic acid. The vC=C mode occurs as low as 1557 cm -1 in the case of trichloroacrylic acid to as high as 1690 c m - 1 in the case of itaconic acid (6). Table 10.3 lists IR group frequency data for acetic acid and its derivatives in the vapor and solution phases (1,7). The vOH...C1CC13 frequency occurs in the region 3534.3-3500.5 cm -1 in C C I 4 solution, and for vOH...HC1CC12 in the range 3521.0-3479.6 c m - 1 . The lower frequencies in CHC13 solution are attributed to the double hydrogen bond complexed as previously discussed here. The lowest vOH frequency is exhibited by trifluoroacetic acid and the highest vOH frequency is exhibited by trimethylacetic acid. The lowest Taft or* value is for trimethylacetic acid [-0.300] and the highest Taft or* value is for trifluoroacetic acid [2.778] (3). Moreover, the highest pK a value is for trimethylacetic acid [5.03] and the lowest pK a value is for

168

Carboxylic Acids

trifluoroacetic acid [0.05] (8). These data show that as the OH proton becomes more acidic the
vOH mode decreases in frequency in both CC14 and CHC13 solutions. Moreover, in general the frequency separation between CC14 and CHC13 solution becomes larger as the OH proton

becomes more acidic due to the formation of stronger OH...C1 bonds. Figure 10.5 is a schematic of the number of possible rotational conformers for the tri-, di-, and haloacetic acid monomers (14). X is one halogen atom, 2X is two halogen atoms, 3X is three halogen atoms. The following symbols are used: E(X) indicates that the carbonyl group is eclipsed by X; E(H) indicates that the carbonyl group is eclipsed by H; A(X) indicates that X is anti to the carbonyl group; and A(H) indicates that H is anti to the carbonyl group. Taft cr values have been correlated with the vC--O and absorbance values for acetic acid and its derivatives (9). There does not appear to be a linear relationship between vC=O and Taft o'* values. For example, C1 acetic (vC--O, 1791 vs 1.05), C12 acetic (vC--O, 1784 vs 1.94), and C13 acetic (vC=O, 1789 vs 2.65) in CC14 solution. On the other hand the Vop (C--O) 2 frequencies for the mono-, di-, and trichloroacetic acids increase in frequency as the Taft a* constants increase in value (C1 acetic acid, 1737 cm -1 vs 1.05; C12 acetic acid, 1744 vs 1.94; and C13 acetic acid, 1752 cm -1 vs 2.65). Therefore, factors other than Taft's inductive effect must affect vC--O and Vop ( C - O ) 2. Intermolecular hydrogen bonding between C=O and (C=O)z, as discussed previously, is one factor that affects these stretching modes. The other factor has been reported to be the existence of rotational conformers (7). The ~-halogenated acetic acids existing in rotational forms 1X-A(X), 2X-A(X), and 3X-A(X)X can form intramolecular hydrogen bonds with the a-halo atom as depicted in Structure D. The intramolecular hydrogen bond would be expected to lower the vC=O frequency, because the C=O bond would be weakened due to the induced contribution for Structure E.
o o

c~C~o
X-

II

9 -H

c~
X...

_
.

"<o

i.

Structure D

Struct. ure E

Therefore, the polar A(X) forms would be expected to exhibit the lowest vC=O frequencies within each halo series. Compounds such as 2-methoxyacetic acid and pyruvic acid in the vapor phase also exist in structures such as (D) and (E). In these cases the acid proton is intramolecularly bonding to the oxygen atom of the CH30 or CH3C=O group, respectively (1,13). Figures 10.6-10.9 show that in either CC14 or CHC13 solution, the vC=O mode decreases in frequency within each series (X3COzH, X2CHCOO2H , XCH2CO2H , and RCOzH) as the pK a increases or as the acid becomes less acidic (e.g., see E C1, Br, and I). Figures 10.10-10.13 (14) show that in either CC14 or CHC13 solution the vC=O or Vop (C=O) 2 mode increases in frequency within each of the four series as a* values increase (e.g., see Br 2, C12, and F z). Thus, as more sigma (~r) electrons are donated to the acid carbonyl group, the vC=O or Vop(C--O) mode

Variables in Data Interpretation

169

decreases in frequency due to cr electrons being donated to the carbonyl group, and as more cr electrons are withdrawn from the acid C = O or (C=O) 2 groups, the vC--O or Vop(C=O) 2 increase in frequency. This agrees with what was discussed previously here. However, the opposite or an erratic behavior is noted in Fig. 10.6, Br3 to Br, C13 to C1, F 3 to F; Fig. 10.7, Br 3 to Br, C13 to C1; Fig. 10.8, Br to Br3, C1 to C13, F to F3; Figs. 10.9 and 10.10, Br to Br 3, C1 to C13, F to F3; Fig. 10.11, Br to Br3, C1 to C13; and Fig. 10.12, Br to Br3. In these cases the vC=O or Vop(C=O) 2 mode decreases in frequency as the pK a value is increased or that the vC=O or Vop(C--O) 2 does not increase in frequency as the Taft ~r* value increases. This erratic behavior is attributed to the existence of rotational conformers, the result of rotation of the XCH 2, X2CH, and CX3 groups about the C - C - - O bond as depicted in Fig. 10.5. Figure 10.13 shows plots of vC--O for the haloacetic acids vs mole % CHC13/CC14 solutions. In Fig. 10.13, two plots are noted for iodoacetic acid (14). The IR band near 1769cm -1 is assigned to the rotational conformer I I - E ( I ) and the IR band near 1736cm -1 is assigned to rotational conformer I I - E ( H ) . In the case of chloroacetic acid, two rotational conformers are noted at high mole % CHC13/CC14. The lower frequency vC=O band is assigned to the rotational conformer 1C1-E(H) and the higher frequency IR band to rotational conformer 1C1-E(C1). In the case of fluoroacetic acid at low mole % CHC13/CC14 solutions, the low frequency IR band is assigned to rotational conformer 1 F - E ( H ) , the higher frequency IR band is assigned to rotational conformer 1F-E(F). The other 1-haloacetic acids exist in the form of rotational conformer 1X-E(X). The dihalogenated acid vC--O frequencies are assigned to the 2X-A(X) rotational conformers. Dibromoacetic acid exhibits a band in the region 1797.41799.3cm -1 in going from CC14solution to CHC13 solution, and this IR band is assigned to rotational conformer 2Br-E(Br). The trihaloacetic acid v(C=O)IR band frequencies (14) are assigned to rotational conformer 3X-A(X). Figure 10.14 shows plots of Vop(C=O) 2 vs mole % CHC13/CC14 solutions. In Fig. 10.14, the plot for trifluoroacetic acid shows that Vop(C--O) 2 increases in frequency as the mole % CHC13/CC14 increases (14). This noted exception in this series of plots is attributed to the following--the two CF 3 groups in the intermolecularly hydrogen-bonded dimer are rotating to the more polar form as the mole % CHC13/CC14 is increased. The most polar form is where the CF 3 groups are in rotational conformer 3 F - E ( F ) . The field effect of the eclipsed F atom apparently overrides the field effect of the solvent system, and the intermolecular hydrogen bonding between CHC13 protons and the carbonyl groups, because Vop(C=O) 2 increases rather than decreases in frequency as the mole % CHC13/CC14 is increased. The 3 F - E ( F ) rotational conformer for Vop(C=O) 2 is reasonable, because the OH protons in this case are intramolecularly hydrogen-bonded with the two C = O groups, whereas in the case of the monomer, the 3 X - A rotational conformer is stabilized by intramolecular hydrogen bonding via (X-..HO). In conclusion, these halogenated acetic acids exist as rotational isomers. Within a series the highest vC=O frequency results from the conformer where the halogen atom eclipses the carbonyl oxygen atom denoted as E(X). The lowest vC=O frequency is where the halogen atom is anti with the carbonyl oxygen atom denoted as A(X). In the anti configuration the acid proton bonds intramolecularly with the anti halogen atom, causing a weakening of the C = O bond. The inductive effect of the halogen atom(s) is (are) independent of molecular geometry, but the field effect is dependent upon molecular geometry. Thus, the field effect upon the C = O group is responsible for the relatively high vC=O frequency with rotational conformers with E(X) structure, but not with A(X) structure (14).

170

Carboxylic Acids

It has been found that the type of carboxylic acid of form RCO2H had to be identified before its approximate pK a value could be calculated from vC=O and Vop(C=O) 2 frequencies recorded in CC14 solution (10). The vC=O and Vop(C=O) 2 frequencies recorded in CC14 solution have been reported to correlate in a linear manner with pK a values (11). It has been reported that Vop(C--O) 2 band intensities for aromatic carboxylic acids are higher than those for aliphatic carboxylic acids (12). In the vapor-phase at temperatures above 150 ~ carboxylic acids exist only in the monomeric state. At lower temperature both the monomer and dimer carboxylic acid can exist in equilibrium. With increase in temperature the equilibrium shifts toward the monomeric species (1,13).

4-X-BENZOIC

ACIDS

Table 10.4 lists IR data and assignments for 4-X-benzoic acids in the vapor, CC14 and/or CHC13 solution phases. The OH, C=O, and (C--O) frequency ranges and assignments are compared here: vapor, cm -1
vOH

(1)

CC14,

cm-1 (14)

CHC13, cm-1 (14)

v O H . 9 .C1HCC12

v O H . . .CICC13

range range range

3582-3595 vC=O 1758-1768 Vop (C=O)2

3529-3544 vC=O 1735-1751 Vop (C=O)2 1689-1707

3519-3528 vC---O. 9.HCCl3 1719-1744

Vop(C=O)2 999 (HCCI3)2

1687-1707

This comparison shows that the vOH, vC=O, and vasym. (C=O) 2 decrease in frequency progressing in the order vapor, CC14, and CHC13 solutions. In the case of Vop (C=O) 2, the frequency change in going from CC14 and CHC13 is small due to the fact that in the dimer form each O - H group is already hydrogen bonded to each of the C=O groups, and the O - H oxygen atom is much less basic; therefore, the CHCC13 proton will not form a strong intermolecular hydrogen bond as in the case of vC=O...HCC13. See Table 10.4a for the factors that affect the CO2H and (COz) 2 groups for 4X-benzoic acids in CHC13 and CC14 solutions. Figure 10.15 shows plots of v O H for 4-X-benzoic acids vs Hammett's rrp values. These plots show a relationship with the Hammett O-p values, but many of the points fall off the linear line. Figure 10.16 shows plots of vC--O for 4-X-benzoic acids vs Hammetts O-p values. Linear relationships are apparent except for the 4-tert-butyl and 4-methoxy analogs for CHC13 solution (14). Figure 10.17 shows plots of Vop(C=O) 2 for 4-X-benzoic acids vs Hammetts ~rp values. The plots for both CC14 and CHC13 solutions are linear in three different segments (14). Figure 10.18 shows plots of Vop (C=O) 2 for 4-X-benzoic acids vs mole % CHC13/CC14. The C1, Br, H, CH3, tert-butyl, and methoxy analogs all decrease essentially linearly in going from CC14 to CHC13 solutions. In addition, the frequency separation between these linear plots decreases as Hammetts Crp values increase in value. However, in the case of the 4-nitro and 4-cyano analogs the Vop(C--O) 2 frequencies actually increase in going from CCl 4 to CHC13 solution. In CC14 solution, the 4-nitro analog would have the most acidic OH proton and the most basic C - O oxygen atoms. Therefore, a complex such as (F) would cause the C=O bond to be

Variables in Data Interpretation

171

x
9 ci3cci

9.H~

~c ~~-~..~ I
II

9 H/~ o

~,(~0"-,o/~..

" -c.=c,,

xA.J

:H----CC~
Complex F Complex G

strengthened. Therefore, the Vop(C=O)2 mode would vibrate at a higher frequency than in a case such as Complex G. In addition, the NO2 group of aryl NO 2 has been shown to form intermolecular hydrogen bonds with CHC13 (15), and between C13CH..-NC for benzonitrile (16). Intermolecular hydrogen bonding of the CHC13 proton with the 4-NO 2 or 4-cyano group would also cause an increase of Vop(C=O)2 in these (ClsC-HC1CC13) . complex solutions. Moreover, intermolecular hydrogen complexes involving the CH3C13 proton with the g system on one or both sides of the planar phenyl group would also cause vC--O to increase in frequency. These Vop(C~O) 2 shifts are 0.27 and 0.65 cm -1 for the NO 2 and C H 3 0 analogs, respectively. For the C1, Br, H, CH3, (CH3)C , and CH30 these shifts are -1.01, -1.10, -1.33, -2.34, -2.27, and -2.52, respectively. Figure 10.18 shows plots of vC=O for 4-X-benzoic acids vs mole % CHC13/CC14. In CC14 solution, the Br analog occurs at a higher frequency than the C1 analog, and in CHC13 solution the CN analog occurs at a higher frequency than the NO 2 analog. These cases are exceptions to the correlation of vC=O vs Hammett O'p values. The 4-tert.-butylbenzoic exhibits two v C - O bands. The lower frequency band frequencies listed by the computer are in the range 1721.55-1718.0cm -1 The vC=O for the 1721.551718.0cm -1 IR band is in good agreement with the vC--O vs Hammett % values. The higher vC=O frequency band for 4-tert-butylbenzoic increases in frequency as the mole % CHC13/CC14 is increased while none of the other 4-X-benzoic acids show this opposite trend. A possible explanation for this vC=O frequency behavior is that the tert-butyl group is hyperconjugated, and that the C13C-H proton is hydrogen bonded to the phenyl g system while the positively charged tertiary carbon atom is associated with the C13CH chlorine atom. Such an interaction would cause the vC=O mode to increase in frequency as observed. Because 4-tert.-butylbenzoic acid exhibits two v C - O frequencies it is apparent that it exists as clusters in CHC13 solutions. All of the 4-X-benzoic acids show breaks in the plots in the range 10-30mol % CHC13/CC14 solution, which indicates that other CHC13/CC14 complexes of (C13C-H..-C1CC13) n with the 4X-benzoic are also present. Table 10.5 lists IR vapor-phase data and assignments for anthranilic acids. These acids have the following basic structure:
H

OH

172

Carboxylic Acids

The v O - H stretching frequencies occur in the range 3484-3494 c m - 1 . The vasym. NH 2 mode occurs in the range 3518-3525cm -1 and vsym. NH 2 in the range 3382-3395cm -1. The frequency separation of 123-141 c m - 1 indicates that the N - H proton is intramolecularly hydrogen bonded to the C = O group as was illustrated here. A weak band in the region 3430-3436 c m - 1 is assigned to v O H . . . N . The vC=O mode is in the range 1724-1732 c m - 1 . The NH 2 bending mode is exhibited in the range 1613-1625cm -1. A medium-strong band in the range 1155-1180 c m - 1 is attributed to O - C = stretch. N-methyl anthranilic acid and N-phenyl anthranilic acid exhibit v N - H . . . O = C at 3392 and 3348 c m - 1 , respectively. The N - H . . . O - - C intramolecular hydrogen bond is stronger in the case of the N-phenyl analog due to the inductive effect of the phenyl group compared to that for the N-methyl group. The v C = O . . . H - N frequencies occur near 1719 c m - 1 for N-methyl and N-phenyl anthranilic acid compared to 1724-1732 cm -1 for the other anthranilic acids studied. Table 10.6 lists infrared data for acrylic acid and methacrylic acid in 0 to 100mol % CHC13/CC14 solutions. The sym. CH 3 bending mode for methacrylic acid increases steadily from 1375.5 to 1377.8cm -1 as the mole % CHC13/CC14 is increased from 0 to 100, while the CH2= wag mode for methacrylic acid increases wag only 0.5 cm-1, from 948.7 to 949.2 cm-1. In the case of acrylic acid, the CH2-- bending mode decreases steadily from 1433.1 to 1429.9 c m - 1 as the mole % CHC13/CC14 increases from 0 to 100, while the vinyl twist mode varies from 983.9 to 983.6 to 984 c m - 1 . Table 10.7 lists Raman data for carboxylic acid salts (6). In some cases vasym. CO 2 is observed in the Raman, and its intensity is always less than the Raman intensity for vsym. CO 2. The Raman bands in the region 1383-1468cm -1 are assigned to vsym. CO 2. Frequency assignments for vasym. CO 2 and vsym. CO 2 are summarized in Table 10.8. Study of this table suggests that the inductive effect causes vasym. CO 2 for the dichloroacetate ion to occur at higher frequency than the other carboxylate ions. Table 10.9 lists IR data for carboxylic acid salts. This table demonstrates as well that the inductive effect also increases the vasym. CO 2 frequency as it increases from 1585cm -1 for sodium acetate to 1640 c m - 1 for sodium difluoroacetate. It appears that a divalent cation such as calcium (Ca) lowers the vasym. CO2 frequency compared to a monovalent cation such as lithium (Li) or sodium (Na). Compare lithium and calcium formate (1604 vs 1596cm -1) and sodium and calcium 2-ethylhexanoate (1555 vs 1545 c m - 1 ) while the opposite effect is noted for vsym. CO 2 (1382 vs 1400cm -1) and (1415 and 1424cm -1) for the formate and 2-ethylhexanoates, respectively.

HALF SALTS OF CARBOXYLIC

ACIDS

Sodium hydrogen diacetate is an example of a transmission anomaly observed within broad absorption bands of solids. This anomally indicates that there are perturbations between overlapping energy levels in the solid state. Sodium hydrogen diacetate is classified as a type A acid salt with a centrosymmetric anion: Sodium hydrogen diacetate has 24 molecules per unit cell in its crystal structure (18). The broad intense absorption is determined by coupling between two or more vibrating ( - O . - - H . . . O - ) n groups (19).

Variables in Data Interpretation

173
0 /."
HsC--C.
\', o
-..H... 0 Na +

There are two C - C stretch modes in the centrosymmetric anion, a vsym. ( C - C ) 2 and vasym., (C-C)2. The vasym. ( C - C ) 2 mode yields a strong Raman band at 920 c m -1 , and it is this mode that interacts, causing the transmission window in the broadband at 920 c m -1 (see Fig. 10.19a). Figure 10.19b is that for the (CD3) 2 analog, and in this case the vasym. C - C mode has shifted to 874cm -1 exhibiting the transmission anomaly at this frequency. Another anomaly near 840 c m - 1 results from the CD 3 rocking mode at this frequency (20). Application of the perturbation theory redistributes both energy levels and absorption intensity. Near E ~ the interaction is greatest and the resulting shift of the levels leads to a fall in energy-level density. The loss in absorption intensity in this region appears as a gain in the other regions and the perturbation involves all the E ~ and E ~ levels. The intensity may be redistributed over a relatively large frequency range. This yields within the broadband a narrow region of increased transmission, with some regions of increased absorption nearby; the latter might not be easily noted in the spectrum (20). Because Evans was the first to explain these peculiar effects that appear sometimes in the solid state IR spectra, it is now referred to as the "Evans Transmission Hole" or "Evans Hole."

REFERENCES
1. Nyquist, R. A. (1984). The Interpretation of Vapor-phase Infrared Spectra: Group Frequency Data. Philadelphia: Sadtler Research Laboratories, Division of Bio-Rad. 2. Nyquist, R. A., Clark, T. D., and Streck, R. (1994). Vib. Spectrosc., 7, 275. 3. Taft, R. W. Jr. (1956). In Steric Effects in Organic Chemistry, M. S. Newman (ed.), Chap. 3, New York: Wiley. 4. Buckingham, A. D. (1960). Can. J. Chem., 308, 300. 5. Nyquist, R. A., Putzig, C. L., and Hasha, D. L. (1989). Appl. Spectrosc., 1049. 6. (1984). Sadtler Standard Raman Spectra, Philadelphia: Sadtler Research Laboratories, Division of Bio-Rad Laboratories. 7. Nyquist, R. A. and Clark, T. D. (1996). Vib. Spectrosc., 10, 203. 8. Christensen, J. J., Hansen, L. D., and Isatt, R. M. (1976). Handbook of Proton Ionization and Related-Thermodynamic Quantities, New York: Wiley Interscience. 9. Bellanato, J. and Baracel6, J. R. (1960). Spectrochim. Acta, 16, 1333. 10. Golden, J. D. S. (1954). Spectrochim. Acta, 6, 129. 11. St. Fleet, M. (1962). Spectrochim. Acta, 18, 1537. 12. Brooks, C. J. W., Eglinton, G., and Moran, J. F. (1961). J. Chem. Soc., 106. 13. Welti, D. (1970). Infrared Vapour Spectra, London: Heyden, in cooperation with Sadtler Research Laboratories, Philadelphia, PA. 14. Nyquist, R. A. and Clark, T. D. (1995). Vib. Spectrosc., 8, 387. 15. Nyquist, R. A. and Settineri, S. E. (1990). Appl. Spectrosc., 44, 1552. 16. Nyquist, R. A. (1990). Appl. Spectrosc., 44, 1405.

174

Carboxylic Acids

17. Nyquist, R. A., Putzig, C. L., and Leugers, M. Anne (1997). Infrared and Raman Spectral Atlas of Inorganic Compounds and Organic Salts, vol. 1, p. 72. Academic Press, Boston. 18. Splakman, J. C. and Mills, H. H. (1961). J. Chem. Soc., 1164. 19. Albert, N. and Badger, R. M. (1958).J. Chem. Phys., 29, 1193. 20. Evans, J. C. (1962). Spectrochim. Acta, 18, 507.

Variables in Data Interpretation

175
m-

..=

0!
L) L)

..=
,..d Q

03 L) t~

o
s,-

h"

t~

9 II
L) 03
.4

L~ o~

o t~

=Q o ,.a Q

.,..4

L) ~o

o 03 o o

~0

o Q ,--,
vQ

o 03 eq

176

Carboxylic Acids

s.-

,p-

__$
L) L)

9.-d O

L)

O L)

bd

9 II

L) L) 9-L) L)

O ~0

eq

"

l.h

Variables in Data Interpretation

177

0 p,

0 ,.=.

9 il

,_T

~p O

0 0

(y...

I I

,~ ....

,,, , I . . . . . . . . . I . . . . .

I I

.... ,' . . . .

i' . . . . . . . .

'"

178
Carboxylic Acids

_T
Q

d ~

~t

~
Q

...

e~ 0

r,l

0 ,.Q

t~

0
U

~
-"

9 II L.)

=
9 ~ O

m 0 9 ,,.:

L.)
m

o~
0

N
0

~
0 0

Variables in Data Interpretation X

179

O
x II x
X X X

3X-A(X)
X

0
H xll X
It )

0
H II x
11[

@
X H 2X-E(X) X X 2X-E(H) H X 2X-E(X)

II

X 2X -A(_~

2X-A(x)

o
xll H

o
H]IH

o
HII x

IX-E(H)

IX-E(H)

H
IX-A(H)

X
IX-A(X~

H
1X-A(H)

FIGURE 10.5 A schematic of the number of possible rotational isomers for the tri-, di-, and haloacetic acids not in the form of intermolecular hydrogen-bonded dimers. X is a halogen atom, 2X is two halogen atoms, 3X is three halogen atoms.

180
Carboxylic
tt~

Acids

-d

.I

t~ >

~q > O

"-

2 o tt~

;a

-"

Q
o

il
v-tt~ m =... _ o tt~ =_

9 II L)
O Q

~D ~-4

kh

%..
o ~ o. m. o. m. q m.
q
O

Variables in Data Interpretation

181

T |

t~

V"

T"

eq

L~

m
0 II k.)
~ 0

m
0

T-

182

Carboxylic Acids

T~

04

-.

Q,)

"U

ii
. ,~-

II

b.

,..-,

?
~ ,' ........ ', ,' l I ..... i ~ ~I .e-

Variables in Data Interpretation

183

o
9-

e4 ~0

~O

2:
t~ t~

s
O

~m
v,a

O L~

t~

eq

9
L~

II

O t~

O O

tl

~2

il
"
o. ~

I
tq. to

I
tq ~-

'l~
o

I
~
,q

I
o

'
ei

I ....
oi
to

I
oi
r

~t
to

I "
,-:
o

I
,,: o
tq o

184
Carboxylic
~0

Acids

tt~ O

O esl

t~

t~

'S
O L2 t~ 0.} b~

9-

9 II L~
O

tet

g.

eq.

q t~

e~

q o o o o r ?

Variables in Data Interpretation

185

O r

~o
r m..

%
~u
m-.

'-~

L)

2:

.~
O

il
tt~

9 II L) e. ,r,O O

t..-4 P,. m.O

L~

T-0

186

Carboxylic Acids

9 O

N e,I

0~

t~

,.a
m

o
O N

L)
v-

t~ txl r

t~

9 II L)

te~ i O
O O

eq

,-&

I
tM ~'M

-~I ~

I
~--

.... I 84
~--

I
~m-

I
O

I
?

g
v--

Variables in Data Interpretation

,.,,. ,i.,ii-

18"7

O .r,-

,,l

=~ 0 .

.'

"

..... o. ....... o...-o .... -o-..e...e..e-o-ee-o.e.-o."e'-o

_ ~.o.,~._.,o----.'-" .... .0...-::~:::...~-.

................................... .:,;.:%-:..~::;--'{

--o '~-~':'-':'B'a~~i-<
u

~..41.-.~ .... ~ .....

~'~-"d
O

...=,-,'
"-

~'" ..,.~.---~'"'~...~_..d...e...,d.,,~,~"~" ~j ~ : . . _ , , , . ~ , . , ~ : - ~ - - ~ r - - " ~ "

.,,,,~

.,.,~

'~

o
,,z:

- o

o~

ooo:.:OOOv--

--

.. . .......... . . . . .

7 .~--

~_

U | . . . . . . | ..... - O - - O - - - O

9 II

.s
,--.4

,r,.-i

,,,.,.

,v-

O ,I-

C::)

C:i,

|-

#w

r~

1,9

188
.,,.. "-,..~

Carboxylic Acids

1.-

_+ L)
L~ U

,,,p

.....

^..

A _ A

A..

A..

A_.

_=

-=~
0
,,,..

=-~
o ~ ~----4----~---,--~--~--~-44-~-~-~-4-~--~--<---~-._::~:==.~.====:~
ff~ 0

". ~,<)._..~___~..-~--~--~-~-~'~'~~~"~"~'-'~

13 ............ 4

i'
. , , . .

.c:

t~

....... 4{ ....... <i-..~-.--<1

.... ~.-~.-~-~.4~1-4-~--~-.~--4

. . . . . <1 . . . . . . . . . . . . . . . . . . . . . .

9 II ~j

Q 9

L;
I% .,...

1__

..........

1_

. . . .

[ ..........

. . . .

__

~ l

. . . .

i ....

I',.,

Variables in Data Interpretation

189

O
~L
o ba o

O
I'o t~

t~ 03

/
t~

O
t~ 03

O
O

_=
o 03 e~

eq

D
t~

03

r o ~0

O
o

9
o

O
o

tt~

<5
.... T-tt~ t~ gad

gh

t b.

! !

o
o r

eq o

190

Carboxylic Acids

O r O O t~

..
t~ t~

_=

L)

t~

@
|

.-.T L)

..=
=.. e~ O t,/
v--

T-

O v--

=.

9 L)

II

r-@ r
v--

04.
tD Q

Variables in Data Interpretation

191
.. 0

:Z
O t:u0. O O

,b

t/3 r :>

O ,.a O t/)

L) L)

2:

I:

"X3

0 N = .F-

x 4-

<1
g
9 II

-|

I ....... 0

....... I

'll

..... |,

........ :

? b

192

Carboxylic Acids

."

I
,;
-" "

=:

..-.e-'"
,,i,-

, ... ,,'(...-~
,,,,T ~
,.+P-

I ~
~t3

~:

.,

~..~.~,~,0,
_,~-~T
+,. o..."

.~,....... .~...

.,...,

/ m~ + i~

o .... +-

~ T_. __..-+--+--,+~176
e eee.e"e-o" ' , r .... ~ _ .e...e "-'e'" "e' .4..4..4.--~ ....
.~'"

.e

e..-e+.-.'~

.+:; + I~T
o'7
....~'

..t

~
I '-

,u~

,~
9 ,,,fe*'~ . ~
.....

41.4
~'-

O'"

"" ~
~

."

9"~
""

~ O...O... 0 El" 0 .... O . . . O - O - - O ' O E I ' O " "

.....

O" | -

#.

o~

.I
i eo

O0
y v v y

Variables

in Data

Interpretation

193
7
O
W

tl3
O ..O

o eth r162 ,--4

Io
. ,o
O

.8 -~
kl.

---

----L ~ I - -

__)f/
m

L) O tvh t--4

o o m
I

L) r

j
"--

ta

.~

ca) o >-,

"~ O

O L3 t13

..---.~0
0
~

o~" ~0 ~
2 ~
un ~

t,

o
.=. ~

~.~
m

hO o
-.

t~ "~'~

_J
0
N
if)

o<
~

==.

~i!suep IOO!IdO

~.~
a.z

194
TABLE 10.1

Carboxylic

Acids

IR vapor-phase data, CC14 and CHCI3 solution-phase data, and assignments for aliphatic carboxylic

acids O - H str. vapor 3580(0.310) 3579(0.460) 3579(0.291) 3579(0.411) 3579(0.291) C=O str. vapor Acetic Propionic Butyric Isobutyric Trimethyl-acetic 1789(1.230) 1780(1.150) 1780(1.250) 1778(1.242) 1769(1.142)
o.p.(C=O) z str.

Acid Acetic Propionic Butyric Isobutyric Trimethyl-acetic

O - H str. CC14 soln. 3335.0(0.007) 3535.7(0.015) 3533.9(0.015) 3534.1(0.012) 3534.3(0.011) C--O str. C14 soln. 1767.3(0.056) 1758.4(0.052) 1758.7(0.037) 1755.2(0.043) 1750.3(0.047)
o.p.(C=O)2 str.

O - H str. CHC13 soln. 3518.4(0.016) 3520.7(0.032) 3518.9(0.024) 3518.6(0.026) 3521.0(0.028) C--O str. CHC13 soln. 1756.3(0.110) 1745.8(0.180) 1745.9(0.116) 1743.6(0.153) 1740.1(0.174)
o.p.(C=O)2 str.

[vapor][CC14soln.] 45 43.3 45.1 44.9 44.7

[vapor][CHC13soln.] 61.6 58.3 60.1 60.4 58

[CC14 soln.][CHC13 soln.] 16.6 15 10 15.5 13.3

21.7 21.6 21.3 22.8 18.7

32.7 34.2 34.1 34.4 28.9

11 12.6 12.8 11.6 10.2

vapor Acetic Propionic Butyric Isobu tyric Trimethyl-acetic

C - C - O str.

CC14 soln. 1714.6(1.343) 1716.1(0.927) 1711.8(0.839) 1707.0(0.598) 1702.2(0.696) gamma C=O vapor 580(0.268) 588(0.250) 590(0.189) 585(0.353) 571(0.311)

CHC13 soln. 1712.5(0.735) 1714.4(0.552) 1709.5(0.393) 1704.5(0.484) 1699.6(0.556) 2.1 1.7 2.3 2.5 2.6

vapor Acetic Propionic Butyric Isobutyric Trimethyl-acetic 1178)9.744) 1145(0.858) 1150(0.667) 1105(0.755) 1115(1.245)

[vp-vp] 598 557 560 520 544

Variables in Data Interpretation

195

o II
O0 0 '~1- O0

9
~

9,~
0

"~

Q.)

o II

O0

~-

I'~

~r~

e~

9 II
eq ee~ eq ,--~ I--.. 00 O~ O'~ tt~ ~,-~ ,ifee~ ~'r

r--q

e-,I

tt~

ee3

,---~

,~

,~

O0

~'~

O~

~r~ r'q

O0

~1-

O0

~ ~"

.,..,

0
eq I--. eq eq ,-~ O ce~ ~ eq

~o

~o

~o

f.q 0

.<

196
Carboxylic
o ,..-, ,.-~ ,..~ ,...~ ~J

Acids

"-~ o ,-.~ c.q cq rq ,-~ rq

Oo
I~- I~.- r~. i-~ I.~. ,--~ ,--~ ,.-., ,.-~ ,--~ 6 ~

~
~ o

0 II

o ~

m ~ d d d

d d d
o o o o o . .

g
.

~ .N ~.

~. N N .

0 0

o_~
0

. o o o ~ o ~ ~ N ~ d ~ ~ o o o d d d d o o o m m m d m

~g
II 0 o

~ 0 0 ~
.,,,~ 0 o u~

~J
.,,,~ ,.3

o~
N un ~
k.) k.)

~,.-g

,--~ ,--~ ,--~ ,--~

,--~ exl

~q

,--~

,..~

,..~

~1

rq

c.,~ e,.i

.,,,~

9 ~
~ ~ 0 0

0
9 9

~
o o o

~
o

0 0
o

0
.

0
o o

0
o

0
.

0
o o

0
.

0
o . . o .

0
o .

0
.

0
o . . o . .

0
o .

0
o

0
o

0 0 o . . . . 0 0 0 . . . .

~~o
~"~ o ~ o d oo d d o d o d o o c5 d o d oo d d oo d d oo d d

t~
o rq o. o. o

oo
t~
II ;.) ,3 j . ~ ~

oooo.-!. d o d d

. 00

~)

gg
~ I~. o~ ~ I~.. ~ 00 00

t~

t~

.~

27
c,"~ ~ o 00 o o o

00 00

o o

~o.
I I
o

o o

u~

~o.
I
o o

.1
o

Variables

in Data Interpretation

19 7

~
(D I d Ir '-'~ ~'~" ~ ~'~ e-i er ~ e-i

~,- oo

~-

o~

~th ~)

~o

im

oo

~)

"

(~

"

ith

~6

tth

oo

t,~ cm

o~

rq

I--.

,-~ o~

oo

oo

~I-

#-

0
o O d o o . . . . . . . ~ o o ~ o o " d d c5 o d d d d (5 d d d o o

~
.
o

O b"

II tJ

o
o o o o o o o m

o
II

4tJ o o o ~ o ~ o ~

~m

NN

NNNN

g.

NN

~ o N

~
~

,~
d

n~

_r tD tD

(s

~n
tD

198
TABLE 10.4A Factor Hammett o'p NO 2 (0.78) to CH30 (-0.27) CC14 solution CHC13 solution CH30 ( - 0 . 2 7 ) to NO 2 (0.78) CC14 solution CHC13 solution pKa values NO 2 (3.42) to CH30 (4.47) CC14 solution CHC13 solution CH30 (4.47) to NO 2 (3.42) intermolecular hydrogen bond to 4-X group NO2, CN, CH 30 OH :zr system of phenyl group CH 3 is 0 (CH 3) 3C is - 1.54

Carboxylic Acids
Factors affecting the CO2H and (CO2)2 groups for 4-X-benzoic acids in CHCI3 and/or CC14 solutions O - H str. cm- 1 increase 3529.2-3543.3 3519.2-3527.7 decrease 3543.3-3529.3 3527.7-3519.2 increase C=O str. cm- 1 decrease 1751.0-1735.6 1743.4-1719.1 increase 1735.6-1751.0 1719.1-1735.6 decrease op(C=O) str. cm- 1 decrease 1706.7-1689.7 1707.0-1687.2 increase 1689.7-1706.7 1687.2-1707.0 decrease

decrease increase increase decrease

increase increase increase decrease

increase increase increase decrease

Variables in Data Interpretation

o o o ~

199
~. ~. ~. ~. ~. ~
0
~ ~tO0 0 0 0 ~ '~" OX O0

~. ~.
0 0 0 0

~ ~ ~.

u~

Z
u~

u~

Z
u~

<

Lt'~ ,~

o o o o o d o . ~
0 O0 O0 ~ u'~ r Lr ~ zr ~ I'~ ,--~ O0 I'~ ~ ~ ~r',I r ~ ~

do

o~

d o o N ~ z
0 0 0 0 0 0 O~

d o o

od ~N N

r r I~. p.-

0 o o o o 0

~ 0 0
~

~ 0 0

0 ~; 0

~ 0
~

o o o ~ Z . .d , ~

oo~oo ~

ee~

0 0 rq 0 r O0 O~ e~

0 r 0 r O0 0 0 0 0 0

Z
u~

o 0

o 0

0 0

o~~
~ re3

Lr

Lr

0 cq

o Lr

0 ~

4=
0

~0 O0

Lr 0 O0

Cr

r162 3

0 O0

0 O00~

0 O0

0 O0 r162 r

0 O0 C'q

0 O0 ~

m.

0I

ZZ

200
TABLE 10.6 Mole % CHC13 /CC14 0 10.74 19.4 26.53 32.5 37.57 41.93 45.73 49.06 52 54.62 57.22 60.07 63.28 66.73 70.65 75.06 80.06 85.05 92.33 100 delta cm -1

Carboxylic Acids

Infrared data for methacrylic acid and acrylic acid in CHCI3 a n d / o r CCI4 solutions Methacrylic acid s.CH 3 bending cm -1 1375.5 1375.6 1375.7 1375.8 1375.9 1376.1 1376.2 1376.3 1376.4 1376.5 1376.6 1376.7 1376.8 1376.9 1377 1377.1 1377.2 1377.3 1377.4 1377.8 2.3

Methacrylic acid CH2= wag cm -1 948.7 948.8 948.9 949 949 949 949.1 949.1 949.2 949.2 949.2 949.2 949.2 949.2 949.2 949.2 949.2 949.2 949.2 949.2 949.2 0.5

Acrylic acid CH2-bending cm -1 1433.1 1433 1432.8 1432.6 1432.4 1432.3 1432.15 1432 1431.9 1431.8 1431.7 1431.6 1431.5 1431.4 1431.2 1431 1430.9 1430.8 1430.6 1430.3 1429.9 -3.2

Acrylic acid vinyl twist cm -1 983.9 983.8 983.8 983.7 983.65 983.6 983.6 983.6 983.6 983.6 983.7 983.7 983.7 983.7 983.7 983.7 983.8 983.8 983.9 983.9 984 0.1

Variables in Data Interpretation

201

eq

oo

L)
,-4 eq O eq
.--4

,~O

II

O0 r

2:
r

O eq

ee~ ee~ ee~ ~ ~D e q eq

~ .--4

er

L)
o~

Y,
I---. O'~ eq

II
oq

2:
L)

ee~

oo oo oo

2:

r o ee~

O0
t~ tt~

oooo~

O00"~

X:
L)

t~

ee~
O

Cq eq

II eq L)

2:

o
I

O0

~ID tt~ O0 O0

o ~ tt~ ,-.4 tt~ ~t~ tt~ ~t~ ee~ ~ eq eq ~ ~ e-4 eq ~ ~o

tt~ tt~ t~

tt% ~_

t~

t-,.. I'-. tt~ o'3

.--4

r o o
r-4

o
t~ t~

~o O

202
TABLE 10.8 The asymmetric and symmetric CO2 stretching frequencies for carboxylic acid salts Carboxylate ion Formate Acetate Dichloroacetate Propionate Bu tyrate Valerate Stearate Cyanoacetate Malonate Succinate Tartrate Citrate Acrylate Methacrylate Benzoate Salicylate Phthalate Cinnamate asym.CO 2 str. cm -1 1538-1604 1543-1585 1646 1550 1563-1578 1561-1565 1539-1558 1605 1570 1569 1571-1600 1575-1620 1565-1603 1603 1515-1559 1540-1598 1565 1549 sym.CO 2 str. cm -1 1342-1400 1404-1457 1383 1415 1420-1430 near 1437 1438-1468 near 1390 1420 1437 1386-1455 1390-1430 1445-1459 1422-1445 1392-1431 1365-1409 1384 1424

Carboxylic Acids

Variables in Data Interpretation

203

TABLE 10.9 Compound Formate

IR data for carboxylic acid salts asym.CO 2 str. cm -1 1604 1596 1585 1586 1616 1640 1585 1590 1550 1590 1609 1555 1545 1555 1545 1559 1545 1582 1544 sym.CO 2 str. cm -1 1382 1400 1445 1398 1449 1449 1400 1400 1415 1410 1395 1415 1424 1421 1410 1410 1405 1378 1415
a.-s.

delta cm -1 222 196 140 190 167 191 185 190 135 180 214 140 121 134 135 149 140 204 129

lithium calcium Acetate sodium sodium iodosodium fluorosodium difluorosodium mercaptosodium N,N-diethylaminoPropionate cadmium sodium 2-hydroxy sodium 2,3-dichloro-2methylHexanoate sodium 2-ethyl calcium 2-ethyl Laurate sodium Benzoate sodium sodium 3-aminosodium 4-aminosodium 2-hydroxy sodium 4-hydroxy-