Advances and Applications in Mathematical Sciences ISSN 0974-6803
Volume 22, Issue 7, May 2023, Pages 1593-1601
© 2023 Mili Publications, India
STATISTICAL ANALYSIS OF EXPERIMENTAL RESULTS
FOR DIELECTRIC STUDIES IN MOLECULAR
INTERACTIONS OF ANILINES WITH
2-METHOXYETHANOL IN CCL4 SYSTEM BY RSM MODEL
R. PRISCILLA and R. IRENE HEPZIBAH
Department of Physics
A. D. M. College for Women (Autonomous)
Nagapattinam-611001, Tamil Nadu, India
Email: [email protected]
Department of Mathematics
T. B. M. L. College, Porayar-609307
Tamil Nadu, India
Email: [email protected]
Abstract
The moment of dipole of the 1:1 complexes of 2-methoxyethanol with aniline, o-chloro
aniline, p-chloro aniline at 303K have been identified by using Huysken’s method. The
increments of dipolar were computed using bond angle in the molecular orbital theory. The
improvement of the dipole moment values assures the hydrogen bonding between the systems.
RSM is the techniques that are to model and analyse the problems that involves several
variables for optimizing this response. The measured and the predicted values are near to the
established equations clearly show that all the parameters influence the complex formation. So
the response equations for the molecular interactions and the complex formation evolved through
past data design can be successfully predict the complex formation of any combination of the
experimental results.
Introduction
The moment of dipole AB of the complex produced between acceptor
group B and the proton donor group A-H. The inert solvent solutes of
2020 Mathematics Subject Classification: 00A79, 62D05, 62K20.
Keywords: 2-methoxyethanol, H-bonding, dipole moment, aniline, o-chloro aniline, p-chloro
aniline.
Received April 1, 2022; Accepted May 26, 2022
1594 R. PRISCILLA and R. IRENE HEPZIBAH
dielectric investigation give data about solutions of molecular complexes and
structure (Balamuralikrishnan, [1]). The large dipole moment and constant of
dielectric is formed because of A-H (Proton donor) polarity increment due to
hydrogen bond formation. Complexes of hydrogen bonded stereo chemistries
have been determined from the inert solvent proton acceptor. Charge-transfer
interaction, electrostatic and polarization creates electron density
distribution of bonded complexes of hydrogen that indicates the interactions
of complexes formation (Huyskens, [4]). The bond moment enhances OH
distance increase due to hydrogen bond. The sum of charges along the
A − H B. Bond is lesser than complexes of dipole moment. The aniline-
ethanol complex formation using Onsager’s method and the results of the
experimental data are analysed by statistical method is discussed in this
paper (Onsagar, [8]).
Experimental
Dipole meter RL09 Toshniwal with 300kHz static frequency is used for
dielectric measurements and it is calibrated using liquids. Water is circulated
through cell’s glass jacket to maintain the cell temperature at 303K. The
refractive indices at cell temperature of 303K are measured by Abbe’s
refractometer. The density is measured by specific gravity bottle and
chemicals purification is done using standard procedure and these values are
checked against literature values.
Table I. Values of dielectric constant, refractive index and density of aniline
with the formal concentration of 2-methoxyethanol in CCL4 system.
Mole Dielectric Refractive Density of B 1039 b2
Fraction Constant Index of the Solution
of the of the the d12
Solute Solution Solution
(Kg/m3)
(mol/L) 12 n12
0.05 2.0453 1.489 1.6390 17.4628 17.477
0.1 2.1041 1.4791 1.6379 5.0332 5.048
0.2 2.1103 1.4770 1.6377 1.6405 1.655
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STATISTICAL ANALYSIS OF EXPERIMENTAL RESULTS … 1595
0.3 2.223 1.4750 1.6372 0.5724 0.5874
0.4 2.2404 1.4730 1.6368 0.5192 0.5337
0.5 2.260 1.4710 1.6319 0.5195 0.5195
Table-II. Values of dielectric constant, refractive index and density of o-
chloroaniline with the formal concentration of 2-methoxyethanol in CCL4
system.
Mole Dielectric Refractive Density B 1039 b2
Fraction Constant Index of of the
of the of the the Solution
Solute Solution Solution d12
(mol/L) 12 n12 (Kg/m3)
0.05 2.0472 1.4044 1.6408 11.518 11.518
0.1 2.1816 1.4042 1.6350 11.133 11.1452
0.2 2.2209 1.3940 1.6339 6.8657 6.8778
0.3 2.2397 1.3938 1.6329 3.9643 3.9764
0.4 2.3582 1.3936 1.6323 3.4717 3.4839
0.5 2.3780 1.3932 1.6303 2.4969 2.5096
Table-III. Values of dielectric constant, refractive index and density of
p-chloroaniline with the formal concentration of 2-methoxyethanol in CCL4
system.
Mole Dielectric Refractive Density of B 1039 b2
Fraction Constant Index of the
of the of the the Solution
Solute Solution Solution d12
(mol/L) 12 n12 (Kg/m3)
0.05 2.1163 1.4041 1.6408 22 .0359 22.0496
0.1 2.2317 1.3938 1.6350 18.572 18.5858
0.2 2.2602 1.3936 1.6329 7.8267 7.8403
Advances and Applications in Mathematical Sciences, Volume 22, Issue 7, May 2023
1596 R. PRISCILLA and R. IRENE HEPZIBAH
0.3 2.3170 1.3932 1.6323 4.97234 4.9859
0.4 2.3877 1.3828 1.6329 3.9758 3.9894
0.5 2.4165 1.3823 1.6249 2.9092 2.9228
Table IV. Dipole moments of the components and their 1:1 complexes and
dipolar increments of the complexes 2-methoxyethanol + anilines.
Systems a (D ) b (D) ab (D) (D)
2-Methoxyethanol + Aniline+ 1.5 0.707 4.5 4.1
CCl4
2-Methoxyethanol + o- 1.8 1.4 3.9 3.6
Chloroaniline + CCl4
2-Methoxyethanol + p- 3.1 1.1 5.5 4.7
Chloroaniline + CCl4
Results and Discussion
A dipole moment of proton donor a forms an H-bond with a dipole
moment of proton acceptor b. At this time, calculation of dipolar increment
is done. If the values a and b differ from zero. The plot of (Ca/Cb) with B
is straight line which indicate the possibility of a 1:1 complex formation
(Figure 1). a , b and ab are the dipole moments that consists of proton
donor, proton acceptor and their 1:1 complexes. Huyskens [4] showed that
M 2 = V N A (2 ab − 2b)CA + 2bCB . The experimental values for various
concentrations for the system are given in Table 4. The plot of (Ca/Cb) with
B is straight line which shows the possibility of a 1:1 complex formation.
The values are small, sometimes even negative. This explains the
nonexistence of effects of charge transfer. If charge transfer effect is present,
would be greater (Bauge, [2]) than 10D. As is less than 10D, it may
be inferred that the complexion may be only due to redistribution of electrons
due to polarization effects. The dipole moments for the system 2-methoxy
ethanol in p-chloro aniline > aniline > o-chloro aniline in the order of 4.7 D >
4.1 D > 3.6 D. Therefore it is inferred that the system’s dipolar increment is
Advances and Applications in Mathematical Sciences, Volume 22, Issue 7, May 2023
STATISTICAL ANALYSIS OF EXPERIMENTAL RESULTS … 1597
small because of the polarization effect and charge transfer phenomenon.
Response Surface Methodology, the historical data design and
the Response equation:
The historical data design is an independent quadratic design, that does
not contain an embedded factorial or factorial design (Cochran,
Montogomery, [3], [7]). In [3, 7] the experimental values are analysed to
determine the molecular interaction of the ternary liquid system, the
Analysis of Variance (ANOVA) was employed to identify the level of
importance in interaction parameters on their performance characteristics.
The effect of these parameters on interaction has been investigated using
experimental designs and the variation of this interaction parameter with the
dipole increment was discussed in terms of molecular interaction. A new
software verification technique called Design Expert 7.0 was used to reveal
the validity of the observed values developed and the results were discussed
below in tables 5-7. Tables 5-7 give the model statistics. It reveals that linear
model is the best-suggested model. So, for further analysis this model was
used. It also provides the ANOVA results for the response surface linear
model of the input parameters and is commonly used to summarize the test
for significance on individual model coefficients. Table 8 presents the
regression statistics.
Table V. Results of ANOVA for response surface linear model
(2-methoxyethanol + aniline in CCL4 system).
Response 1 (Dielectric Constant)
Source Sum of df Mean F p-value
Squares Square Value Prob> F
Model 0.036 1 0.036 44.02 0.0027
B-Y2 0.036 1 0.036 44.02 0.0027
Residual 3.256E-003 4 8.141E-004
Cor
Total 0.039 5
Response 2 (Refractive Index)
Advances and Applications in Mathematical Sciences, Volume 22, Issue 7, May 2023
1598 R. PRISCILLA and R. IRENE HEPZIBAH
Source Sum of df Mean F p-value
Squares Square Value Prob> F
Model 1.600E-004 1 1.600E-004 14.64 0.020
B-Y2 1.600E-004 1 1.600E-004 14.64 0.020
Residual 4.370E-005 4 1.092E-005
Cor
Total 2.037E-004 5
Response 3 (Density)
Source Sum of df Mean F p-value
Squares Square Value Prob> F
Model 2.256E-005 1 2.256E-005 10.68 0.0308
B-Y2 2.256E-005 1 2.256E-005 10.68 0.0308
Residual 8.450E-006 4 2.113E-006
Cor
Total 3.102E-005 5
Table VI. Results of ANOVA for response surface linear model
(2-Methoxyethanol + O -Chloroaniline in CCL4 System).
Response 1 (Dielectric Constant)
Source Sum of df Mean F p-value
Squares Square Value Prob> F
Model 0.067 1 0.067 36.12 0.0039
B-Y2 0.067 1 0.067 36.12 0.0039
Residual 7.370E-003 4 1.842E-003
Cor
Total 0.074 5
Response 2 (Refractive Index)
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STATISTICAL ANALYSIS OF EXPERIMENTAL RESULTS … 1599
Source Sum of df Mean F p-value
Squares Square Value Prob> F
Model 1.073E-004 1 1.073E-004 9.69 0.0357
B-Y2 1.073E-004 1 1.073E-004 9.69 0.0357
Residual 4.428E-005 4 1.107E-005
Cor
Total 1.516E-004 5
Response 3 (Density)
Source Sum of df Mean F p-value
Squares Square Value Prob> F
Model 4.973E-005 1 4.973E-005 13.20 0.0221
B-Y2 4.973E-005 1 4.973E-005 13.20 0.0221
Residual 1.507E-005 4 3.768E-006
Cor
Total 6.480E-005 5
Table VII. Results of ANOVA for response surface linear model
(2-Methoxyethanol + P - Chloroaniline in CCL4 System).
Response 1 (Dielectric Constant)
Source Sum of df Mean F p-value
Squares Square Value Prob> F
Model 0.056 1 0.056 53.54 0.0019
B-Y2 0.056 1 0.056 53.54 0.0019
Residual 4.22E-003 4 1.055E-003 - -
Cor
Total 0.061 5 - - -
Response 2 (Refractive Index)
Advances and Applications in Mathematical Sciences, Volume 22, Issue 7, May 2023
1600 R. PRISCILLA and R. IRENE HEPZIBAH
Source Sum of df Mean F p-value
Squares Square Value Prob> F
Model 2.775E-004 1 2.775E-004 20.54 0.0106
B-Y2 2.775E-004 1 2.775E-004 20.54 0.0106
Residual 5.405E-005 4 1.351E-005 - -
Cor
Total 3.316E-004 5 - - -
Response 3 (Density)
Source Sum of df Mean F p-value
Squares Square Value Prob> F
Model 1.019E-004 1 1.019E-004 14.08 0.0199
B-Y2 1.019E-004 1 1.019E-004 14.08 0.0199
Residual 2.895E-005 4 7.238E-006 - -
Cor
Total 1.309E-004 5 - - -
Table VIII -Regression Statistics
Value of “Probability > F” and less than 0.05 shows that the model terms
are significant, which is enviable as indicated that the response of the model
has significant effect. This model is used to find the way to the design space.
Table 8 gives the regression statistics. The coefficient of determination R 2 is
used to decide whether a regression model is appropriate or not. In this
study, the coefficient of determination R 2 an exact match if it is 1 and if the
residual increases R 2 decreases in the range from 1 to 0. Also it is observed
that the “Pred R-Squared” is in good conformity with the “Adj R-Squared in
all the output parameters. Moreover “Adeq Precision” shows the signal to
noise ratio. A ratio of greater than 4 is wanted. In this study, the ratio
obtained shows an adequate signal in all the parameters. The effectiveness of
the model has been checked by the validation with experimental values. The
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STATISTICAL ANALYSIS OF EXPERIMENTAL RESULTS … 1601
experimental results are validated by asserting that the predicted values are
very close to each other and hence the developed models are suitable.
Conclusions
The experimental data compared with RSM model can be successfully
relate the above process parameters with the molecular interactions and the
complex formation. The established equations clearly show that all the
parameters influence the complex formation. The predicted and the measured
values are very close to each other which indicate that the developed model
can be effectively used for predicting the complex formation along with the
experimental results having more than 95% confidence level.
References
[1] S. Balamuralikrishnan and A. U. Maheswari, J. Mol. Liq. 12 (2006), 419.
[2] K. Bauge and J. W. Smith, The dipole moments of some quaternary ammonium salts,
Journal of Chemical Society (1964), 4244-4249.
DOI: https://doi.org/10.1039/JR9640004244
[3] W. G. Cochran and G. M. Cox, Experimental Designs, Wiley, New York, 1992.
[4] G. G. Siegel, F. Herrera, Ph. Cappelle and P.L. Huyskens, Cooperative proton jumps in
hydrogen bond chains between phenols and amines in benzene, J. Mol. Liq. 44(3-4)
(1990), 175-188.
[5] P. L. Huyskens and H. M. Vanbrabant-Govaerts, Structural differences between
hydrogen-bonded complexes of enamino ketones and amino ketones in benzene solution,
J. Mol. Struct. 84(1-2) (1982), 141-151.
[6] M. Malathi, R. Sabesan and S. Krishnan, Dielectric studies of H-bonded complexes of
formamide and acetamide with substituted phenols, J. Mol. Liq. 109 (2004), 11-18.
[7] C. Montogomery, Design and Analysis of experiments, 4th edition, Wiley, New York, 1997.
[8] L. Onsagar, J. Am. Chem. 58 (1936), 1486.
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