Studies of Physico-chemical Parameters of Biologically
Active Heterocyclic Compounds
Final report of
MINOR RESEARCH PROJECT
File No. 47-1972/11 (WRO) dated 21st February 2012
Submitted to
UNIVERSITY GRANTS COMMISSION,
WESTERN REGIONAL OFFICE, PUNE
Submitted by
Mr. K. J. MAHAJAN
Principal Investigator
And
Dr. S. K. CHAVAN
Co-investigator
Department of Chemistry
D. B. F. Dayanand College of Arts & Science,
Solapur-413002 (Maharashtra)
Annexure-III
UNIVERSITY GRANTS COMMISSION
BHADUR SHAH ZAFAR MARG
NEW DELHI-110002
Annual Report of the work done on the Minor Research Project
(Report to be submitted within 6 weeks after completion of each year)
1. Project report no. : 1st year
2. UGC Reference no.: 47-1972/11(WRO)
3. Period of report from: February 2012 To February 2014.
4. Title of research project: Studies of Physico-chemical parameters of
Biologically Active Heterocyclic Compounds
5. (a) Name of the Principal Investigator: Mr. K. J. Mahajan
(b) Dept. and University/ College where work has progressed:
Department of Chemistry, D.B.F. Dayanand College of
Arts and Science, Solapur
6. Effective date of starting of the project: 21st February 2012
7. Grant approved and expenditure incurred during the period of the report
a. Total amount approved: Rs. 70,000/-
b. Total expenditure: Rs.74092/-
c. Report of the work done (Please attach a separate sheet)
i. Brief objective of the project: a) To Synthesis of Chalcones and Schiff bases.
b) Characterization of synthesized compounds by
IR and NMR.,
c) To study physical parameters such as density,
viscosity, ultrasonic velocity etc.
ii. Work done so far and results achieved and publications if any, resulting from the work
(Given details of the papers and names of the journals in which it has been published
or accepted for publication): Presented the project in form of posters in various
conferences.(detail work is reported in final report)
iii. Has the progress been according to original plan of work and toward achieving the
objective. If not, state reason: Yes
iv. Please indicates the difficulties, if any, experienced in implementing the project: No.
v. If project has not been completed, please indicate the approximate time by which it is
likely to be completed A summary of the work done for the period (Annual basis) may
please be sent to the Commission on as separate sheet. ______
vi. If the project has been completed, please enclose a summary of the findings of the study.
Two bound copies of the final report of work done may also be sent to the
Commission; ----------
vii. Any other information which would help in evaluation of work done on the project. At
the completion of the project, the first report should indicate the output, such as (a)
Manpower trained (b) Ph.D. awarded (c) Publication of results (d) other impact, if any
_______
Signature of Principal Investigator Principal
(Mr.K. J. Mahajan)
Signature of Co-Investigator
(Dr. S. K. Chavan)
Annexure – VII UNIVERSITY GRANTS COMMISSION
BAHADUR SHAH ZAFAR MARG NEW DELHI – 110 002
PROFORMA FOR SUBMISSION OF INFORMATION AT THE TIME OF SENDING
THE FINAL REPORT OF THE WORK DONE ON THE PROJECT
1. Title of the Project: Studies of Physico-chemical parameters of
Biologically Active Heterocyclic Compounds.
2. NAME AND ADDRESS OF THE PRINCIPAL INVESTIGATOR:
Mr. K. J. Mahajan,
90, Ramrajya Nagar,
Shelagi, Solapur-413006. 3. NAME AND ADDRESS OF THE INSTITUTION: D.B.F. Dayanand College of Arts &
Science, Solapur,
Dayanand Nagar, Raviwar peth,
Solapur- 413002.
4. UGC APPROVAL LETTER NO. AND DATE: 47-1972/11 (WRO)
Dated: 21st Feb. 2012.
5. DATE OF IMPLEMENTATION: 21
st Feb. 2012.
6. TENURE OF THE PROJECT: Two Years.
7. TOTAL GRANT ALLOCATED: Rs. 1,30,000/-
8. TOTAL GRANT RECEIVED: Rs. 70,000/-
9. FINAL EXPENDITURE Rs. 74092/-
10. TITLE OF THE PROJECT : Studies of Physico-chemical parameters of
Biologically Active Heterocyclic Compounds.
11. OBJECTIVES OF THE PROJECT: i) To Synthesis of Chalcones and Schiff bases.
ii) Characterization of synthesized compounds by IR and NMR.
iii) To Study of Physical parameters of these compounds, such as density,
viscosity and ultrasonic sound velocity in DMF and THF solvents.
iv) To Study the behavior of these compounds in DMF and THF solvents.
12. WHETHER OBJECTIVES WERE ACHIEVED: (GIVE DETAILS)
- Yes, Achieved. Separate sheet attached
13. ACHIEVEMENTS FROM THE PROJECT: Presented project work in various
conferences in the form of posters.
14. SUMMARY OF THE FINDINGS: Separate sheet attached (IN 500 WORDS)
15. CONTRIBUTION TO THE SOCIETY ……………………………….
(GIVE DETAILS)
16. WHETHER ANY PH.D. ENROLLED/PRODUCED OUT OF THE PROJECT: Yes,
Enrolled for Ph. D.
17. NO. OF PUBLICATIONS OUT OF THE PROJECT: Presented Project work in various
(PLEASE ATTACH) Conferences, Seminars and
Workshop in the form of posters
(PRINCIPAL INVESTIGATOR) (PRINCIPAL)
(Seal) (Mr. K. J. Mahajan) (CO-INVISTIGATOR)
(Dr. S. K. Chavan)
12. OBJECTIVES ACHIEVED
I) GENERAL INTRODUCTION:
The Heterocyclic compounds have great applicability as drugs due to their specific
chemical reactivity and broad spectrum of biological activity. They resemble essential
metabolism and they fit biological receptors work and block their normal working. Many natural
products contain heterocyclic compounds such as alkaloids and glycosides.
Taking in view of the applicability of heterocyclic compounds, the present work was
undertaken to synthesize some new chalcone compounds. All the synthesized compounds were
characterized by IR and NMR spectra.
II) SYNTHESIS AND CHARACTERIZATION OF CHALCONES:
Chalcones are known as benzalacetophenones or benzylidene acetophenone.
Kostanecki and Tambor(1)
gave the name Chalcone. The chemistry of chalcones has
generated intensive scientific studies throughout the world, due to their biological and
industrial applications.
Chalcones are characterized by their possession of a structure in which two
aromatic rings are linked by an aliphatic three carbon chain. Different methods are available
in the literature for the synthesis of chalcones(2-11)
. The most convenient method is the one,
that involves the Claisen-Schimidt condensation of equimolar quantities of an aryl methyl
ketones with arylaldehyde in presence of alcoholic alkali(12)
. The chalcones have been found
to be useful for the synthesis of variety of heterocyclic compounds. Chalcones are associated
with different biological activities.
In the present work some chalcones were synthesized and showed spectas of FClC
molecule as model example.
EXPERIMENTAL:
Methods of synthesis of chalcones:
[1-(4-Chloro-phenyl)-3-(4-fluoro-phenyl)-propenone (FClC):
The solution of 4-Fluoro acetophenone (1m mol) in ethanol (15ml) 4-Chloro bezaldehyde (1m
mol) was added. To this mixture sodium hydroxide (2ml, 10%) was poured gradually with constant
stirring and continues the stirring for 4 hour at 80-90C. The progress of the reaction and purity of the
systhesized compound was monitored by TLC. Then the mixture was kept for half hour at room
temperature. This mixture was poured in ice cold water (50ml) and the separated solid was filtered,
washed with ice - cold water. The crude product was recrystallized by using ethanol and dried at room
temperature.
O
F
H
O
Cl
+
F
O
Cl
3-(4-Chloro-phenyl)-1-(4-fluoro-phenyl)-propenone
Ethanol,NaOH
Stirr, RT
Physical data of chalcones:
Sr. No.
Code M. F. M. Wt
(g/mol)
M.P. oC Yield %
1 FClC C15H10FClO 260.5 140 83 %
2 CMC C16H13ClO 256.5 172 80 %
3 FMC C16H13FO 240.0 165 86 %
Abbreviations:
1. FClC – Fluoro chloro chalcone 2. CMC – Chloro methyl chalcone 3. FMC – Fluoro methyl chalcone
INFRA RED SPECTRA:
: SHIMADZU-FTIR-8400 Spectrophotometer
Frequency range: 4000-400cm-1
66
4.7
67
05
.26
73
8.3
97
56
.46
80
7.7
58
34.0
28
52.1
28
75.1
18
94
.29
95
4.5
49
85
.00
10
07
.53
10
32
.46
10
84
.29
11
06
.25
11
77
.04
11
83
.28
12
04.5
61
22
0.0
8
12
86
.30
13
05
.26
13
27
.88
13
64
.31
13
97
.97
14
85
.40
15
10.2
91
56
4.1
31
58
5.8
9
16
55
.85
19
22
.76
29
15
.82
55
60
65
70
75
80
85
90
%T
ransm
itta
nce
1000 1500 2000 2500 3000 3500 4000
Wavenumbers (cm-1)
67
1.2
5
73
5.2
27
44
.36
81
2.0
78
39
.54
87
5.0
38
95
.20
95
4.6
79
84
.76
10
09
.80
10
30
.521
10
0.4
01
15
4.2
51
183
.52
12
05
.09
12
20
.01
12
86
.51
13
06
.04
13
30
.45
14
08
.41
15
03.9
61
56
5.8
61
58
8.3
4
16
58
.63
29
17
.18
50
55
60
65
70
75
80
85
90
95%
Tra
nsm
itta
nce
1000 1500 2000 2500 3000 3500 4000
Wavenumbers (cm-1)
66
5.3
8
74
0.6
67
81
.07
81
1.4
38
39
.54
98
6.4
91
01
1.7
01
02
5.4
7
10
90
.01
11
62
.63
12
14
.67
12
43
.10
12
79
.41
13
00
.67
13
15
.74
13
34
.80
14
09
.17
14
88
.75
15
08
.15
15
66
.83
15
88
.08
16
00
.26
16
61
.461
90
6.8
2
75
80
85
90
95
%T
ran
sm
itta
nce
1000 1500 2000 2500 3000 3500 4000
Wavenumbers (cm-1)
The IR spectra of all the chalcone compounds showed the absorption band at
1661- 1666 cm-1
and 1600 cm-1
, which confirms the presence of C=O group and C=C
bond in the compound and absorption band at 1588 cm-1
indicates the presence of C=C in
aromatic ring.
1H NMR SPECTRA:
Compound: CMC - Chloro methyl chalcone
1H NMR (CDCl3): δ 2.42 (s, 3H, H-Methyl), 7.845-7.806 (d, 1H, 15.6 Hz, -CH=CH-), 7.511-
7.472 (d, 1H, 15.6 Hz, -CH=CH-), 7.249-8.005 (m, 8H, ArH).
Compound: FMC - Fluoro methyl chalcone
1H NMR (CDCl3): δ 2.425 (s, 3H, H-Methyl), 7.845-7.806 (d, 1H, 15.6 Hz, -CH=CH-),
7.511-7.472 (d, 1H, 15.6 Hz, -CH=CH-), 7.179-8.098 (m, 8H, ArH).
Compound: FClC – Fluoro Chloro chalcone
1H NMR (CDCl3): δ 7.845-7.806 (d, 1H, 15.6 Hz, -CH=CH-), 7.511-7.472 (d, 1H, 15.6 Hz, -
CH=CH-), 7.187-8.099 (m, 8H, ArH).
Instrument: BRUKER Spectrometer (400 MHz)
Internal reference: TMS
Solvent: CDCl3
REFERENCES:
(1) S. V. Kostanecki and J. Tambor ; Chem. Ber., 32, 1921 (1899).
(2) H. Rupe and D. Wasserzug; Chem. Ber., 34, 3527 (1901)
(3) D. S. Breslow and C. R. Houser; J. Am. Chem. Soc., 62, 2385 (1940).
(4) S. A. Hermes; Chem. Abstr., 70, 96422h (1969).
(5) P. L. Nayak and N. K. Rout ; J. Ind. Chem. Soc., 52, 801 (1975).
(6) G. Casiraghi, G. Casnati, E. Dradi, R. Messori and G. Satori; Tetrahedron, 35, 2061
(1979).
(7) A. Fuentes, J. M. Marinas and J. V. Sinisterra; Tetrahedron, 28, 4541 (1987).
(8) T. Patonay, G. Toth and W. Adam; Tetrahedron, 34, 5055 (1993).
(9) F. Severi, S. Benvenuti, L. Costantino, G. Vampa, M. Melegari and L. Antolini; Eur. J.
Med. Chem., 33, 859 (1998).
(10) S. Eddarir, N. Cotelle, Y. Bakkour and C. Rolando; Tetrahedron, 44, 5359 (2003).
(11) S. Saravanamurugam, M. Palanichamy, B. Arabindoo and B. Murugesan; Catalysis
Commun., 6, 399 (2005).
(12) K. Kazauki, K. Htayama, S. Yokomor and T. Soki; Chem. Abstr., 85, 5913 (1976).
II) SYNTHESIS AND CHARACTERIZATION OF SCHIFF BASE:
Azomethines are generally known as Schiff bases to honour Schiff, who
synthesized such compounds (1).
These are the compounds containing characteristic –
CH=N- group. Lots of works have been done on this class compounds due to its multi
applicability. They are well known intermediate for many other derivatives. Owing to their
characteristic properties like, manifestations of novel structures, thermal stabilities,
abnormal magnetic properties, relevant biological properties, high synthesis flexibility,
varied coordinating ability and medicinal utility, a wide range of these compounds have
been synthesized and extensively studied (2-15)
.
Murray (16)
has prepared imines by the reaction of aldehydes with amine. Tabei
and Saitou have reported the synthesis of some Schiff bases derived from benzaldehyde
and substituted benzaldehydes with aniline (17)
. Some Schiff bases from 2-hydroxy
benzaldehydes were also synthesized and the effect of substituent on Keto-enol equilibria
was also reported (18)
. Some other Schiff bases have also been synthesized from various
substituted benzaldehydes and their characterizations were done by using IR, and NMR (19-
20)
The present work was undertaken to synthesize some Schiff base compounds.
EXPERIMENTAL:
Method of Synthesis of Schiff Base:
[1-(4-Chloro-phenyl)-ethylidine]-(4-fluoro-phenyl)-amine.
A solution of 4-Fluroaniline (1mmol) and 4-chloro benzaldehyde (1mmol) is
dissolved in absolute ethanol (10 ml). The reaction mixture was refluxed for 3-4 hours in
presence of K2CO3 at 80 to 100 0C, and then on cooling the precipitate formed was collected
by filtration. The product was washed several times with cold water, and then recrystallized
from ethanol. The reaction progress was monitored by TLC using ethyl acetate and hexane.
Physical data of Schiff base:
Sr.
No.
Code M. F. M. Wt.
(g/mol)
M.P. oC Yield
%
1 SB-I C14H11NFCl 247.5 172 78 %
2 SB-II C14H11NFCl 247.5 51 70 %
SB-I: 4 - Chloro Schiff Base
SB-II: 2 - Chloro Schiff Base
INFRA RED SPECTRA:
Instrument: SHIMADZU-FTIR-8400 Spectrophotometer
Frequency range: 4000-400cm-1
66
8.4
56
79
.88
70
6.4
47
18
.20
77
3.9
58
03
.56
82
3.6
38
32
.31
88
6.6
59
45
.98
97
2.3
51
00
9.5
1
10
82
.00
10
95
.03
11
53
.78
11
67
.10
11
86
.96
12
13
.96
12
98
.58
13
52
.07
14
04
.85
15
00
.20
15
67
.26
15
89
.30
16
23
.97
16
39
.71
23
41
.84
23
60
.36
28
80
.00
80
82
84
86
88
90
92
94
96
%T
ran
sm
itta
nce
500 1000 1500 2000 2500 3000 3500 4000
Wavenumbers (cm-1)
66
8.3
66
97
.52
70
8.9
77
29
.77
75
2.7
6
80
9.8
98
26
.12
86
5.5
7
98
1.4
4
10
12
.47
10
89
.71
11
10
.78
11
78
.27
11
90
.85
13
08
.14
14
06
.41
14
44
.22
14
88
.93
15
65
.00
15
87
.84
16
25
.67
16
49
.48
23
42
.00
23
59
.97
33
58
.89
34
80
.32
70
75
80
85
90
95
%T
ran
sm
itta
nce
500 1000 1500 2000 2500 3000 3500 4000
Wavenumbers (cm-1)
[1-(4-Chloro-phenyl)-ethylidine]-(4-fluoro-phenyl)-amine and [1-(2-Chloro-phenyl)-
ethylidine]-(4-fluoro-phenyl)-amine showed a broad spectrum at 1567cm-1
&1623 cm-1
frequencies. The appearance of this peak in the spectra indicate the presence of C=N
(azomethane) group in the organic compound. There is no spectral band at 1700cm -1
frequency which confirm the absence of carbonyl group in the compound.
1H NMR SPECTRA: SB-I 1H NMR (DMSO): δ 2.5 (s, 3H,) 7.06-8.82 (m, 8H, Ar-H)
1H NMR SPECTRA: SB-II 1H NMR (DMSO): δ 2.5 (s, 3H,) 6.26-8.491 (m, 8H, Ar-H)
Instrument: BRUKER Spectrometer (400 MHz)
Internal reference: TMS
Solvent: DMSO
REFERENCES:
(1) H. Schiff; Ann. Chem., 131, 118 (1864).
(2) Strache; Ber. 21, 2361 (1888).
(3) M. Calvin, R. H. Balies and W. K. Wilmarth; J. Am. Chem. Soc., 68, 2254 (1946).
(4) B. M. Krasovitskii, V. B. Smelyakova and R. N. Nurmukhametov; Opti ii spek-trosk, 27,
588 (1964).
(5) J. M. W. Scoot and W. H. Jura; Can. J. Chem., 45, 2375 (1967).
(6) N. Castagnoli and M. Cushman; J. Org. Chem., 36, 3404 (1971).
(7) M. Lehtinen and J. Halmekoski; Farm. Aikak., 84, 107 (1975).
(8) S. M. E. Kousy, F. A. Ali, A. M. Donia and F. A. E. Saied; Egypt J. Pharma. Sci., 28, 107
(1987).
(9) A. K. Varshney, P. S. Verma and S. Varsheny; Synth. React. Met. Inorg. Org. Chem., 19,
233 (1989).
(10) R. L. Polt and M. Peterson; Tetrahedron Lett., 31, 4985 (1990).
(11) K. Afkar and K. A. Hadi; Ind. J. Chem., 33, 879 (1994).
(12) D. Raczynska and R. W. Taft; Bull. Chem. Soc. Jpn., 70, 1331 (1997).
(13) R. C. Goyal, K. Arora, D. D. Agarwal and K. P. Sharma; Asian J. Chem., 12, 919
(2000).
(14) S. K. Sridhar and A. Ramesh; Ind. J. Chem., 41, 668 (2002).
(1620) M. S. Murray; Chem. Rev., 26, 297 (1940).
(17) K. Tabei and E. Saitou; Bull. Chem. Soc. Jpn., 42, 2693 (1969).
(18) J. W. Ledbetter Jr.; J. Phys. Chem., 81, 54 (1977).
(19) M. R. Udupa and G. Aruvamudan; Curr. Sci., 42, 676 (1973).
(20) B. Dash, P. K. Mahapatra, D. Panda and J. M. Pattnaika; J. Ind. Chem. Soc., 61, 1061
(1984).
IV) STUDY OF PHYSICAL PARAMETERS OF CHALCONES AND SCHIFF BASE:
INTRODUCTION:
Ultrasonic deals with study and application of high frequency sound waves usually in
excess of 20 KHz. It works on the basis of piezoelectric effect (1).
Ultrasonic waves have wide range of applications in various fields (2-4)
such as
medicine, industry, material testing. Ultrasonic waves have been also used for the polishing
of mold steel (5)
and extraction of various compounds (6-7)
. These waves have also been used in
animal communication (e.g. bat navigation and dog whistles) etc.
Now a days, lots of interest has been generated on the use of ultrasound radiation in
synthetic organic chemistry, which includes decrease of reaction time, increase of yield,
lower reaction temperature etc(8-11)
By ultrasonic sound velocity measurements, the molecular interactions in pure liquid
(12-14), aqueous solutions
(15-16) and liquid mixtures
(17) have also been studied.
Several physic-chemical parameters are available in the list and few of them are of
much interest. It was well understood by the literature that physic chemical properties such as
acoustical properties, density, viscosity, ultrasonic sound velocity, refractive index, etc. have
contributed advancement in the physical sciences and also in daily human life. These
properties are the sensitive indicators for understanding molecular interactions.
The study of physic-chemical properties of compounds in solutions gives complete
understanding of the behavior of compounds in different solvents. Literature survey shows
that very little work has been reported for the study of physico- chemical studies such as
acoustical properties, density, viscosity, ultrasonic sound velocity, refractive index of the
heterocyclic compounds.
Thus, in the present work we have tried to add something in this field of science. .
Various physico-chemical properties and acoustical properties such as density, viscosity and
ultrasonic sound velocity have been studied in dimethylformamide (DMF) and
tetrahydrofuran (THF) for different concentrations of chalcones and Schiff base solution
were done at 308.15 K with a view to understand the molecular interactions in these
solutions. From these experimental data, various acoustical parameters such as isentropic
compressibility, Rao’s molar sound function, specific acoustical impedance, internal
pressure, Vander Waals constant, free volume etc. were evaluated and results are discussed.
EXPERIMENTAL: Choice of Solvents: N,N-Dimethylformamide (DMF) and tetrahydrofuran (THF) and have been chosen
as solvents in the present work. These two solvents are of industrial interest because of their
wide use as solvents and solubilizing agents. The densities, viscosities and ultrasonic
velocities of solvents and solutions of different concentration were measured at 300.15 K by
using pyknometer, an Ubbelohde suspended level viscometer and single frequency ultrasonic
interferometer operating at 2 MHz, with the uncertainties of 0.0001 g/cm3, + 0.06 % and
0.01% respectively.
Density measurements:
The weight of distilled water, pure solvents and solutions of chalcones and Schiff
base were measured by using pyknometer. The densities were evaluated by using following
equation:
Viscosity Measurements:
The viscosity of distilled water, pure solvents and solutions were determined by using
Ubbelohde viscometer (18)
. The measured quantity of the distilled water / solvent / solution
was placed in the viscometer, which was suspended in a thermostat at 300.15 K. The digital
stopwatch, with an accuracy of + 0.01 sec was used to determine flow time of solutions.
Using the flow times (t) and known viscosity of standard water sample, the viscosity of
solvent and solutions were determined by using the following equation:
Sound velocity measurement:
Ultrasonic interferometer (Model No. F-81), Mittal Enterprise, New Delhi, working
at frequency (F) of 2 MHz was used to determine sound velocity. The solvent / solution were
filled in the measuring cell with quartz crystal and then micrometer was fixed. The
circulation of water from the thermostat at 308.15 K was started and test solvent / solution in
the cell is allowed to thermally equilibrate. The micrometer was rotated very slowly so as to
obtain a maximum or minimum of anode current (n). A number of maximum reading of
anode current were counted. The total distance (d) travel by the micrometer for n=10, was
read. The wave length (λ) was determined according to the equation
The sound velocity (U) of solvent and solutions were calculated from the
wavelength and frequency (F) according to equation
U = λF
RESULTS AND DISCUSSION:
The table -1 and 2 shows the variation in density (ρ), viscosity (η) and sound
velocity (U) of pure solvents and different solutions of Chalcones and Schiff base in N,N-
dimethylformamide (DMF) and tetrahydrofuran (THF) were calculated at 308.15 K and are
given in Table.
From the measurements of density(Ρ), viscosity(η) and ultrasonic sound
velocity(U), various acoustical parameters like specific acoustical impendence (Z), isentropic
compressibility (κs), intermolecular free length (Lf), molar compressibility (W), Rao’s molar
sound function (Rm), relaxation strength (r), relative association (RA), internal pressure
(π), free Volume(Vf) etc. were evaluated using the following equations:
1. Specific acoustical impedance:
Specific acoustical impedance (Z) can be calculated as,
Z =Uρ
2. Isentropic compressibility:
Isentropic compressibility (κs) can be evaluated according to the following the
equation(19)
3. Intermolecular free path length: Jacobson
(20) proposed an equation to calculate the intermolecular free path
length (Lf), which is given below:
L f = K j κ s 1/ 2
Where, Kj is Jacobson constant (=2.0965 X 10-6
)
4. Molar compressibility: Molar compressibility (W) can be calculated by the following equation
(21):
The apparent molecular weight (M) of the solution can be calculated according to
equation
M = M1 W1 +M2 W2
Where, W1 and W2 are weight fractions of solvent and solute, respectively. M1
and M2 are the molecular weights of the solvent and compounds respectively.
5. Rao’s molar sound function:
Rao’s molar sound function (Rm) can be evaluated by an equation given by Bagchi
et al.(22)
:
6. Relaxation Strength:
The relaxation strength (r) can be calculated as follows(24)
:
Where, U∞ = 1.6 x 105 cm/sec.
7. Relative Association (RA):
Where, U, U0 and ρ, ρ0 are ultrasonic velocities and densities of solution and solvent
respectively.
8. Internal Pressure (π):
Suryanarayana and Kuppuswamy (25)
gave the following equation for evaluating
internal pressure:
Where, b is the packing factor (= 2). K is a constant (=4.28 X 109). The internal
pressure (π) depends on temperature, density, ultrasonic velocity and specific heat at constant
pressure.
9. Free Volume (Vf):
Free volume (26)
can be calculated according to equation (1.15):
Table 1:
Variation of density (ρ), ultrasonic velocity (U) and viscosity (η) with concentration of CMC
Chalcone in DMF and THF at 300.15K.
CConc.onc.
Conc. (M)
Density
(ρ) g.cm-3
Velocity
(U) 10-5
cm.s-1
Viscosity
(η)103
poise
Density
(ρ)
g.cm-3
Velocity
(U) 10-5
cm.s-1
Viscosity
(η)103
poise
CMC in DMF CMC in THF
00 0.9349 1436.8 0.6596 0.8684 1245.6 0.4179
0.002 0.9352 1439.2 0.6942 0.8662 1256.0 0.4043
0.004 0.9355 1442.2 0.7192 0.8673 1258.0 0.4080
0.006 0.9358 1444.8 0.7362 0.8684 1259.8 0.4148
0.008 0.9362 1446.o 0.7645 0.8695 1261.6 0.4247
0.010 0.9364 1447.8 0.7691 0.8704 1262.1 0.4378
Table 2:
Variation of density (ρ), ultrasonic velocity (U) and viscosity (η) with concentration of FMC
Chalcone in DMF and THF at 300.15K.
CConc.onc.
Conc. (M)
Density
(ρ) g.cm-3
Velocity
(U) 10-5
cm.s-1
Viscosity
(η)103
poise
Density
(ρ)
g.cm-3
Velocity
(U) 10-5
cm.s-1
Viscosity
(η)103
poise
FMC in DMF FMC in THF
00 0.9376 1401.3 0.6594 0.8684 1217.6 0.8545
0.002 0.9410 1409.8 0.6384 0.8686 1226.3 0.8552
0.004 0.9423 1418.2 0.6543 0.8688 1235.4 0.8561
0.006 0.9427 1428.3 0.6700 0.8692 1237.6 0.8569
0.008 0.9433 1436.5 0.7000 0.8694 1250.8 0.8595
0.010 0.9438 1448.1 0.7466 0.8697 1261.2 0.8612
Table 3:
Variation of density (ρ), ultrasonic velocity (U) and viscosity (η) with concentrations of SB-I
Schiff base in DMF and THF at 300.15K.
CConc.onc.
Conc. (M)
Density
(ρ) g.cm-3
Velocity
(U) 10-5
cm.s-1
Viscosity
(η)103
poise
Density
(ρ)
g.cm-3
Velocity
(U) 10-5
cm.s-1
Viscosity
(η)103
Poise
SB-I in DMF SB-I in THF
00 0.9345 1306.0 0.7246 0.8702 1246.2 0.4058
0.002 0.9352 1342.2 0.7435 0.8735 1264.4 0.4248
0.004 0.9375 1362.6 0.7535 0.8763 1274.5 0.4378
0.006 0.9432 1392.6 0.7772 0.8788 1289.6 0.4756
0.008 0.9461 1414.0 0.8295 0.8805 1303.8 0.5143
0.010 0.9488 1452.0 0.8672 0.8846 1324.2 0.5465
Table 4:
Variation of density (ρ), ultrasonic velocity (U) and viscosity (η) with concentrations of
SB-II Schiff base in DMF and THF at 300.15K.
Conc. (M)
Density
(ρ) g.cm-3
Velocity
(U) 10-5
cm.s-1
Viscosity
(η)103
poise
Density
(ρ)
g.cm-3
Velocity
(U) 10-5
cm.s-1
Viscosity
(η)103
poise
SB-II in DMF SB-II in THF
00 0.9336 1352.6 0.7042 0.8624 1218.3 0.3407
0.002 0.9346 1388.2 0.7299 0.8637 1228.4 0.3588
0.004 0.9383 1408.3 0.7584 0.8647 1240.5 0.3694
0.006 0.9409 1428.6 0.7888 0.8716 1252.3 0.3793
0.008 0.9438 1444.3 0.8253 0.8749 1260.1 0.3838
0.010 0.9493 1452.9 0.8477 0.8776 1270.6 0.3922
Table-5: Variation of acoustical parameters with concentration of all Chalcones and Schiff
bases in DMF at 300.15.
Conc
(M). Κs
10-4
Lf
(oA)
r
10-5
Z .10-5
g.cm-2
Rm.102
cm-8/3
.s-1/3
W.102
cm1.dyn
-
1
π
Vf
(cm3)10
-
7
RA
CMC
00 5.1417 0.04753 7.1315 1.3480 8.8016 2.3045 45823 1.2156 1.0000
0.002 5.1348 0.04751 7.1676 1.3468 8.8516 2.3119 4575.4 1.2212 0.9999
0.004 5.1376 0.04750 7.1541 1.3472 8.8853 2.3138 4563.3 1.2328 1.0001
0.006 5.1511 0.04743 7.1247 1.3461 8.6773 2.3159 4556.1 1.2334 0.9998
0.008 4.8400 0.04683 7.0910 1.4356 8.6783 2.3178 4549.4 1.2378 0.9991
0.010 4.6731 0.04668 7.3699 1.3454 7.7771 2.3190 4541.3 1.2421 0.9989
FMC
0.002 5.3469 0.04848 6.7638 1.3266 8.6996 2.2840 5627.6 1.1835 1.0016
0.004 5.2766 0.04816 6.8566 1.3363 8.7142 2.2894 5386.7 1.1961 1.0010
0.006 5.2000 0.04781 6.9689 1.3464 8.7414 2.2942 4985.6 1.2110 0.9991
0.008 5.1376 0.04752 7.0609 1.3550 8.7618 2.2967 4756.2 1.2234 0.9979
0.010 5.0528 0.04723 7.1914 1.3667 7.8297 2.2983 4571.6 1.2403 0.9957
SB-I
0.002 5.9356 0.05108 6.0371 1.2552 8.6109 2.2640 4684.1 1.0993 0.9917
0.004 5.7452 0.05025 6.2526 1.2774 8.6193 2.2697 4668.5 1.1272 0.9943
0.006 5.4669 0.04902 6.5755 1.3135 8.6209 2.2762 4637.6 1.1656 0.9846
0.008 5.2864 0.04820 6.8102 1.3378 8.6339 2.2818 4621.8 1.1945 0.9862
0.010 4.9993 0.04687 7.2355 1.3776 8.6814 2.2968 4608.2 1.2450 0.9804
SB-II
0.002 5.5523 0.04940 6.5277 1.2974 8.7161 2.2878 4628.6 1.1568 0.9925
0.004 5.3737 0.04859 6.7473 1.3214 8.7363 2.2930 4613.6 1.1847 0.9917
0.006 5.2075 0.04784 6.9722 1.3442 8.7657 2.2978 4596.5 1.2128 0.9898
0.008 5.0794 0.04725 7.1484 1.3631 8.7835 2.2986 4588.3 1.2356 1.0330
0.010 4.9904 0.04683 7.2454 1.3792 8.7618
2.3000 4575.8 1.2485 1.04111
Table-6: Variation of acoustical parameters with concentration of all Chalcones and Schiff
bases in THF at 300.15K.
Conc
.(M) κs
10-4
Lf
(Ao) r
10-5
Z .10-5
g.cm
-2
Rm.102
cm-
8/3.s-
1/3
W.10-3
cm
1.dyn
-
1
π Vf
(cm3)10
-
7
RA
CMC
0.00 7.2697 0.05648 5.2134 1.0952 8.9133 2.3267 4621.5 0.9613 1.0000
0.002 7.2754 0.05646 5.2173 1.0928 8.9307 2.3336 4622.3 0.9753 0.9975
0.004 7.2646 0.05650 5.1996 1.0926 8.9644 2.3373 4617.8 0.9796 0.9969
0.006 7.2768 0.05647 5.1819 1.0924 8.9469 2.3430 4611.6 0.9838 0.9970
0.008 7.2732 0.05643 5.1622 1.0920 8.9504 2.3453 4606.2 0.9878 0.9975
0.010 7.2710 0.05634 5.0548 1.0841 8.9818 2.3478 4602.2 0.9903 0.9984
FMC
0.002 7.6555 0.05800 4.8743 1.0652 8.8755 2.3226 4644.5 0.9408 0.9979
0.004 7.5417 0.05757 4.9617 1.0733 8.9060 2.3241 4635.2 0.9529 0.9957
0.006 7.4781 0.05759 4.9540 1.0731 8.9186 2.3277 4626.8 0.9574 0.9955
0.008 7.3523 0.05684 5.1113 1.0874 8.9587 2.3387 4620.8 0.9745 0.9957
0.010 7.2467 0.05664 6.8825 1.0946 8.9909 2.3455 4603.9 0.9883 0.9899
SB-I
0.002 7.1613 0.05610 5.2449 1.1044 8.9259 2.3280 4637.3 0.9851 1.0037
0.004 7.0256 0.05557 5.3451 1.1168 8.9316 2.3217 4629.8 0.9984 1.0066
0.006 6.8428 0.05484 5.4963 1.1333 8.9518 2.3344 4609.3 1.0181 0.9985
0.008 6.6863 0.05421 5.6402 1.1471 8.9672 2.3388 4597.4 1.0427 0.9968
0.010 6.4468 0.05323 5.8496 1.1714 8.9825 2.3443 4581.3 1.0631 0.9964
SB-II
0.002 7.6791 0.05809 4.8944 1.0601 8.9339 2.3318 4648.6 0.9436 0.9999
0.004 7.5149 0.05747 5.0111 1.0727 8.9663 2.3330 4627.3 0.9598 0.9967
0.006 7.3159 0.05671 5.1259 1.0915 8.9531 2.3337 4618.6 0.9757 1.0015
0.008 7.1980 0.05621 5.2025 1.1025 8.9852 2.3347 4615.8 0.9871 1.0032
0.010 7.0586 0.05569 5.3663 1.1150 8.9956 2.3367 4611.2 1.0017 1.0036
Figure1: The variation of density (ρ)and viscosity (η) with concentration of SB-I and SB-II in
[A] DMF and [B] THF at 300.15K.
Figure 2: The variation of ultrasonic velocity (U) with concentration of all compounds in [A]
DMF and [B] THF at 300.15K.
[A] [B]
Figure3: The variation of isentropic compressibility (κs) with concentration of CMC and
FMC compounds in [A] DMF and [B] THF at 300.15K
[A] [B]
Figure 4: The variation of isentropic compressibility (κs) with concentration of SB -I and SB-
II compounds in [A] DMF and [B] THF at 300.15K
[A] [B]
REFERENCES:
(1) A. P. Cracknell; "Ultrasonics", Chapter 6, 92 (1980). Wykenham Publishers.
(2) T. J. Mason; Ed., Sonochemistry. The use of ultrasound in chemistry, Royal Society of
Chemistry (1990).
(3) M. P. Kapoor; J. Pure Appl. Ultrason., 19, 104 (1997).
(4) M. K. S. Suslick and G. J. Price; Ann. Rev. Mater. Sci., 29, 295 (1999).
(5) H.Hocheng, and K.L. Kuo; International Journal of Machine Tools and Manufacture, 42,
7 (2002).
(6) Z . Hromadkova, A. Ebringerova and P. Valachovic; Ultrason Sonochem., 9, 37 (2002).
(7) M. Vinatoru, M. Toma, O.Radu, P. I. Filip, D. Lazurca and T. J. Mason; Ultrason
Sonochem. 4, 135 (1997).
(8) O. Krüger, Th. -L. Schulze and D. Peters; Ultrason. Sonochem., 6, 123 (1999).
(9) Y. Zhao, X. H. Liao, J. M. Hong and J. J. Zhu; Mat. Chem. Phys., 87, 149 (2004).
(10) M. Mexiarová, M. Kiripolský and S. Toma; Ultrason. Sonochem., 12, 401 (2005).
(11) M. Sivakumar and A. Gedanken; Synthetic Metals, 148, 301 (2005).
(12) S. C. Bhatt, H. Semwal, V. Lingwal, K. Singh and B. S. Semwal; J. Acous. Soc. India,
28, 293 (2000).
(13) R. P. Varma and S. Kumar; Ind. J. Pure and apply. Phy., 38, 96 (2000).
(14) M. Kalidoss and S. Ravi, Statistical Mechanics and its application, 312, 59 (2002).
(15) K. J. Patil and D. H. Dagade; J. Chem. Thermo., 36, 677 (2004).
(16) S. Kamila, S. Jena and B. Bihari; J. Chem. Thermo., 37, 820 (2005).
(17) A. Awasthi, M. Rastogi and J. P. Shukla; Fluid Phase Equilibria, 215, 119 (2004).
(18) L. Ubbelhode, Inst. Pet. London 19, 376 (1933).
(19) G. L. N. Sastry and B. A. Krishnamurthy, Ind. J. Pure Apply. Phy., 6, 637(1968).
(20) B. Jacobson, Nature (London), 173, 772 (1954).
(21) Y. Wada, J. Phy. Soc. Jpn., 4, 280 (1949).
(22) S. Bagchi and S. K. Nema and R. P. Singn, Eur. Polym. J., 22, 851 (1989).
(23) P. Vigoureux, "Ultrasonics", Chapman and Hall, London (1952).
(24) G. K. Johri and R. C. Misra, Acustica, 57,292 (1985).
(25) C. V. Suryanarayana and J. Kuppuswamy, J. Acoust. Soc. (India), 9, 4 (1981).
(26) D. Subramanian, N. Karunanidhi and P. Aruna, J. Pure Appl. Ultrason., 21, 5 (1999).
14. SUMMARY OF THE FINDINGS
In the present work density, viscosity and ultrasonic sound velocity have been studied
in dimethylformamide (DMF) and tetrahydrofuran (THF) for different concentrations of
Chalcones and Schiff base solutions were done at 308.15 K.
Table-1, 2, 3 and 4 shows the variation of ultrasonic sound velocity (U), density (ρ),
Viscosity (η) with concentrations for all the Chalcones and Schiff bases in both solvents,
DMF and THF. It is observed that ultrasonic velocity (U) increases with concentration for all
the compounds. The velocity depends on intermolecular free length (Lf). Table- 5 and 6
shows that Lf decreases continuously which suggest that there is strong interaction between
solvent (both DMF and THF) and compound molecules.
This is further supported by isentropic compressibility (κs) and relaxation strength
(r). The variations of isentropic compressibility (κs) with concentration of these compounds
are also shown in table5 and 6 for both solvents. It is observed from the obtained datd that
both isentropic compressibility (κs) and relaxation strength (r) are also observed to decrease
with concentration for all the compounds. The decrease of κs with increasing concentration
might be due to aggregation of solvent molecules around solute molecules indicating thereby
the presence of solute-solvent interactions. The increase of acoustical impedance (Z) further
confirms the solute-solvent interactions in these systems.
The properties like Rao’s molar sound function (Rm), molar compressibility (W)
and are observed to increase linearly with concentration for all the compounds. The linear
variation of these acoustical properties indicates absence of complex formation.
The internal pressure (π) is the results of forces of attraction and repulsion between
the molecules in solutions. The data reported in taρρble -5 and 6 shows that internal pressure
decreases with concentration, which indicates the decrease in cohesive forces. Although
decrease in compressibility (κs), intermolecular free length (Lf), relaxation strength (r) and
increase of velocity (U), viscosity (η) suggest predominance of solute-solvent interactions,
the decrease in internal pressure indicates the existence of solute-solute interactions also in
these systems.
The free volume (Vf) of solute molecule at particular temperature and pressure
depends on the internal pressure of liquid, in which it was dissolved. The decrease in
molecular association causes an increase in free volume (Vf). Thus, free volume is an inverse
function of internal pressure. It is evident from Table 5 and 6 that Vf increases with
concentration for all the compounds in solutions. Hence, increase in free volume causes
internal pressure to decreases, which indicates the solute-solute interactions. This suggests
that both solute-solute and solute-solvent interactions exist in these systems.
CERTIFICATE
This is to certify that the Minor Research Project of Principal Investigator (PI) Mr.
K. J. Mahajan has uploaded the executive summary of the project on the college website, the
URL link is __________________________________. This certificate is as per the
requirement under Minor Research Project guidelines.
Signature of the Principal
CERTIFICATE OF FUNDS RETURNED
It is to certify that the Minor Research Project entitled “Studies of Physico-
chemical parameters of Biologically Active Heterocyclic Compounds” sanctioned through
File No. 47-1972/11 (WRO) dated 21st February 2012. to the Principal Investigator Mr. K. J.
Mahajan has been refunded of Rs. 214 /- due to unspent balance.
Date-05-11-2015
Principal Investigator Principal
D.B.F. Dayanand College of
Arts & Science, Solapur
CERTIFICATE OF STARTING AND COMPLITION OF MRP
It is to certify that the Minor Research Project entitled “Studies of Physico-chemical
parameters of Biologically Active Heterocyclic Compounds” sanctioned through File No.
47-1972/11 (WRO) dated 21st February 2012 to the Principal Investigator Mr. K. J. Mahajan
has actually executed in the month of February 2012 and is successfully completed in
February 2014.
Date-05-11-2015
Principal Investigator Principal
D.B.F. Dayanand College of
Arts & Science, Solapur
Annexure-IV
STATEMENT OF EXPENDITURE INCURRED ON FIELD WORK
Name of the Principal Investigator: Mr. K. J. Mahajan
Certified that the above expenditure is in accordance with the UGC norms for Minor
Research Projects.
Signature of Principal Signature of Principal
Investigator
Name of the place visited Duration of the visit Mode of
journey
Expenditure
Incurred (Rs.) From To
International conference at
Solapur University, Solapur
Registration fee
02
November
2012
04
November
2012
Bus 2000/-
National conference Advance
Research Trends in Chemistry at
Solapur, Registration fee
22
February
2014
23
February
2014
Bus 1000/-
Sample analysis at Solapur
University, Solapur
11
January
2014
12
January
2014
Bus 2000/-
TOTAL 5000/-
