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ABSTRACT
The vibrational absorption spectra of Benzoic Acid’s Monomer molecules and its amino
substitutents have been studied using GF matrix and AM1 method. Assuming C s point symmetry,
vibrational assignments for the observed frequencies have been proposed. The spectra exhibit
distinct features originating from low frequency vibrational modes caused by intra-molecular
motion. Normal modes have been calculated and an assignment of the observed spectra has been
proposed. Experimental frequencies are compared with those obtained by G.F.Matrix and AM1
method.
Keywords : Benzoic Acid,o-, m-, p- Amino Benzoic Acid, FTIR Spectra, AM1, G.F.Matrix
INTRODUCTION
Carboxylic acids (RCOOH) are a common and important functional group and provide
the point of success to the carboxylic acids derivatives (acetyl chlorides, esters, amides etc.) and
therefore, it has been extensively studied by spectroscopic methods. Spectroscopist's interest has
been concerned with structure and vibrational frequencies.
The aim of the present study is a IR spectroscopic analysis of Benzoic Acid (BA), which
have found considerable attention in the literature1-8. We compared experimental results with
calculated frequencies of BA using force matrix method and AM1, PM3 and G.F. Matrix method.
These methods were able to account breadth of spectrum as well as description of vibrational
modes to encourage the application of a similar procedure to a larger and more complex group.
STRUCTURE AND GEOMETRY OF BENZOIC ACID
EXPERIMENTAL
Benzoic acid was purchased from Sigma Chemical Co (USA). Benzoic acid forms a
white to off white crystalline powder with melting point of 159 c. I.R. Spectrum has been
recorded in the liquid phase in the range 400-4000cm-1 on Perkin-Elmer spectrometer Model
397. Preparation of KBr Pallets: A small amount of finally grounded solid sample was intimately
mixed with about 100 times or more than its weight of Potassium bromide powder. The finally
grounded mixture was than pressed under very high pressure in a press (about 10/cm2) to form a
small pallet (about 1-2 mm thick and 1cm in diameter).
The accuracy of the measurements was estimated to be within 3cm-1 and the resolution
was better than 2cm-1 through the entire range for both the spectra.
We had employed a very large basis set for the computational of the frequencies. First
infrared frequencies were calculated for the BA ( Cs Symmetry) at the AM1 and G F Matrix level
of theory. We can get information from computational vibrational spectra only when we compare
it with experimental spectrum.Our results are given in table 2. Due to anharmonicity, the
harmonic vibrational frequencies were found to be lowered by1 to 3% in GF Matrix method
except AM1 method.
Benzoic acid contains 15 atoms so that it has 39 normal modes. The calculated normal modes are
distributed among 27 a΄ and 12 a΄΄ species of Cs symmetry group. The table 2 also shows that
PED contributions for 39 normal modes. These assignments are partly based on the calculated
frequencies. As the table 2 is self-explanatory, we shall discuss here only some important points.
OH Stretch: Experimental OH stretch band frequency for BA is 3507 cm −1 which was shifted
by 97 cm −1 as reported by Antony et al13 and which is also higher than those observed by
others7,16. Theoretically calculated frequencies by G.F. and AM1 are 3579.2 cm −1 and 3627.6 cm
−1
, respectively.
CH3 s-stretch: As presented in table2, experimental CH3 s-stretch frequency for BA is 2987 cm
−1
. Antony et al13 observed this frequency for benzoic acid at 2943 cm −1 . Calculated frequencies
by G.F. and AM1 are 3010.9 cm −1 and 3172.0 cm −1 respectively.
C=O stretch: experimental observed frequencies for this bands is 1823 cm −1 for BA, which is
higher than the calculated frequencies . Antony et al13 observed this frequency for benzoic acid at
1752 cm −1 . Theoretically calculated frequencies by G.F. and AM1 are 1716.5 cm −1 and 1726.2
cm −1 respectively.
O-H Bend: Our observations for this bend is 1328BA. Antony et al13 observed this frequency for
benzoic acid at 1381 cm −1 . Trout et al observed 1328 frequency for COO symmetric stretch, so
our assignment was totally reversed by this one. Computationally calculated frequencies by G.F.
and AM1 are 1311.5 cm −1 and 1441.9 cm −1 respectively.
C-O stretch: Experimental frequency for BA is 1228 cm −1 respectively. Antony et al13 did not
observed this frequency for benzoic acid. Theoretically calculated frequencies by G.F. and AM1
are 1243.8 cm −1 and 1435.7 cm −1 respectively.
O-C-O Deformation: We observed this bend frequency at 668 cm −1 for BA respectively which is
comparative to others14,16 . Theoretically calculated frequencies by G.F. and AM1 are 657.7 cm −1
and 646.3 cm −1 respectively.
Torsion: Experimental observed frequency for this bend for BA is 591 cm −1 . Antony et al15
observed this frequency for benzoic acid at 444 cm −1 . Computationally calculated frequencies by
G.F. and AM1 are 593.4 cm −1 and 571.9 cm −1 respectively.
NH 2 Group Modes
The number of internal vibrations for a group is given by 3m-3, where m is the number of
atoms in the group. Thus NH 2 has 6 modes of vibrations. These modes are as : two stretching
vibrations ( one symmetric and one asymmetric) both belonging to a’ species, two angle
deformations (scissoring and rocking), one out-of-plane wagging of NH 2 and one torsion
vibration of NH 2 .
There are three major differences between the C-H and N-H stretching frequencies. First,
the force constant for N-H stretching is stronger, there is a larger dipole moment associated with
the N-H bond, and finally, the N-H bond is usually involved in hydrogen bonding. The stronger
force constant leads to a higher frequency for absorption. The N-H stretching frequency is
usually observed from 3500-3200 cm-1. The larger dipole moment leads to a stronger absorption
and the presence of hydrogen bonding has a definite influence on the band shape and frequency
position.
The NH 2 stretching modes appear in the region 3500 – 3100 cm −1 and the asymmetric
19
component has slightly higher magnitude than the symmetric component. D.N.Singh
observed asymmetric modes at 3465 cm −1 and symmetric mode at 3360 cm −1 . However,
A.K.Tiwari 20 observed them at 3449 cm −1 and 3367 cm −1 respectively.
He observed in-plane bending and rocking mode at 1630 cm −1 and 1055 cm −1
respectively. A.K.Tiwari19 got in-plane bending mode at 1621 cm −1 and rocking mode at 952
cm −1 . D.N.Singh 20 observed wagging vibration at 592 cm −1 and he didn’t got
torsion mode. A.K.Tiwari19 observed these vibrations at 626 cm −1 and 274 cm −1 respectively.
In present study we get frequencies for them as shown in table 3.
COOH Group Modes
In the parent molecule benzene if one of the hydrogen atom is replaced by a COOH
group, nine more normal modes would appear. They are as:- O-H Stretching, C-O Stretching,
C=O Stretching, in-plane-rocking, in-plane bending of C-O, in-plane-bending of C=O, in-
plane-bending of OH, out-of-plane wagging, and out-of-plane torsion.. J. Antony et al13
studied vibrational spectra of benzoic acid and got C=O Stretching at 1745 cm −1 , C-O
stretching at 1050 cm −1 , C-O in-plane bending at 594 cm −1 , C=O in-plane bending at 1804
cm −1 , OH stretch at 3785 cm −1 , rocking mode at 554 cm −1 , torsion mode at 594 cm −1 and
wagging mode at 441 cm −1 . Florio et aI 15
observed C=O Stretching at 1752 cm −1 , C-O
stretching at 1347 cm −1 , C-O in-plane bending at 628 cm −1 , OH stretch at 3785 cm −1 ,
rocking mode at 628 cm −1 , and wagging mode at 160 cm −1 . In present study we get
frequencies as shown in table 4.
CONCLUSIONS
ACKNOWLEDGEMENTS
Table 1 Assumed Bond Length and Bond angle in Benzoic and Amino Benzoic Acids.
Mode of Vibration o-Amino Benzoic Acid m-Amino Benzoic Acid p-Amino Benzoic
(in cm −1 ) (in cm −1 ) Acid (in cm −1 )
N-H Asymmetric 3622 (E), 3601.6(GF) 3472(E), 3490.1(GF) 3509(E), 3521.3(GF)
Stretching 3530.9(M) 3492.4(M) 3512.2(M)
a’ CN-H Symmetric 3325(E), 3342.9(GF) 3225(E), 3207.6(GF) 3462(E), 3487.2(GF)
Stretching 3530.9(M) 3464.6(M) 3490.0(M)
NH 2 In-Plane 1156(E), 1162.3(GF) 1110(E), 1123.5(GF) 1132(E), 1140.1(GF)
Bending 1219.5(M) 1217.7(M) 1143.9(M)
NH 2 Rocking 536(E), 527.1(GF) 541(E), 531.3(GF) 523(E), 529.3(GF)
558.1(M) 537.2(M) 539.3(M)
E :- Experimental frequencies
GF:- Theoretical frequencies calculated by GF Matrix method
M:- Theoretical frequencies calculated by MOPAC method
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