Rigoberto Fimia Duarte et al., : Int. J. Pure & Appl. Sci. Res.

Trans; Vol-2, Iss- 1 (2022): 1-18

International Journal of Pure & Applied Science Research Transactions

ISSN Print : 2957-9341| ISSN Online : 2957-935X
Frequency : Quarterly
Language : English
Website: https://ijpasr-transactions.com/

Exploring interactions between anisole and aromatic amines (at 10, 20, and 30
concentrations) through thermophysical properties and ATR-FT IR spectroscopy
reveals insights into solute-solvent dynamics in liquid mixtures.

O. Audiseshaiah1, K. Govindaiah1,N. Mahendra1, N. Sunkanna1, Y.V. Rami Reddy*1

1
Department of Chemistry, S.V. University, Tirupati-517502, A.P., India.

*Corresponding Author
E-mail addresses:1. dryvrsvu@gmail.com(Y.V.Rami Reddy).

Article History: | Received: 28.06.2022 | Accepted: 24.07.2022 | Published: 25.08.2022|

Abstract: The density (ρ) of binary liquid mixes of Anisole (methoxy benzene) with aniline, N-methyl aniline, and N,N-dimethyl
aniline was accurately calculated at temperatures of 303.15 K, 308.15 K, and 313.15 K to determine their thermophysical
characteristics. In addition, the velocity of sound (u) was determined at temperatures of 303.15 K and 313.15 K. The data were utilised
to calculate the excess molar volumes (VE) and excess isentropic compressibilities (κsE) at the temperatures under investigation. The
VE and κsE values obtained were fitted using the Redlich-Kister polynomial equation. In addition, the sound speed data were
evaluated for their prediction accuracy by comparing them with Schaff's collision factor theory (CFT) and Jacobson's Free Length
theory (FLT). The results were carefully examined to reveal the physical and chemical interactions that arise from the solute and
solvent components in the binary liquid mixtures. Hydrogen bonding between Anisole and aromatic amines was experimentally
confirmed using AT FT-IR Spectroscopic investigations. This work provides a thorough examination of the thermodynamic properties
of binary mixes and confirms theoretical predictions, offering insights into the complex intermolecular interactions involved in these
systems.
Keywords: Density, Speed of sound, Excess Molar Volume, FT-IR Spectrum.

Copyright @ 2022: This is an open-access article distributed under the terms of the Creative Commons Attribution license which permits unrestricted
use, distribution, and reproduction in any medium for non-commercial use (Non Commercial, or CC-BY-NC) provided the original author and source
are credited.

1. Introduction Anisole, an aromatic ether, finds widespread

The investigation of molecular interactions in process
fluids and the analysis of thermodynamic parameters,
such as densities and sound speed, play a pivotal role in
chemical design and effective process optimization.
Designs for fluid flow engineering, heat transfer, mass
transfer, and chemical separations are all heavily
influenced by these characteristics. In example,
statistics of sound speed, which provide important
information on the interactions between the molecules
that make up matter, have become more important in
comprehending the structure and characteristics of
matter. The study of physical properties of binary
mixtures, especially those containing anisole, holds
substantial importance across various industries,
including petrochemistry and medicinal chemistry.
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applications in industries due to its versatility in dyes,
pigments, perfumes, and as a precursor for various
derivatives. A lot of people in the scientific community
are interested in learning about the physical features of
binary mixes that include anisole. In addition to its
usage as a medicinal and insect pheromone, anisole is
an important phenolic ether that is involved in the
production of many other derivatives. In contrast,
amines are useful in many chemical reactions, as well
as in agriculture, medicines, and rubber. When mixed
with other compounds, such as chlorine or chlorates,
aniline, a primary amine, produces aniline colours,
which are used as a starting ingredient in dye
production. Aniline is a byproduct of many industrial
processes and products, including colours, explosives,
polymers, antioxidants, and varnishes. Amines in
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Rigoberto Fimia Duarte et al., : Int. J. Pure & Appl. Sci. Res. Trans; Vol-2, Iss- 1 (2022): 1-18
general, and N-Methyl Aniline and N,N-Dimethyl
Aniline in particular, are important in many chemical
processes and have many practical uses in industry as
agrochemicals, organic compound intermediates,
coupling solvents, and so on. However, exposure to
N,N-Dimethyl Aniline through inhalation has been
associated with adverse effects on the Central Nervous
System (CNS) and Circulatory system, leading to
symptoms like headaches, cyanosis, and dizziness.
Understanding the interactions and effects of these
chemical compounds is essential for ensuring
occupational and environmental safety. Finding out
how molecular interactions in binary liquid mixtures
are affected by the chemical structures of various
solvents is the main goal of the research.
Intermolecular and intramolecular interactions between
and within different molecules are both included in the
investigation. Analysis of excess thermodynamic
characteristics and predicted correlations between these
changes and variations in the patterns of hydrogen
bonds (H-bonds) controlling molecular interactions in
solutions are the tools used in this inquiry. The current
literature on binary mixes of anisole with aniline, N-
Methyl Aniline, and N,N-dimethyl Aniline is
noticeably lacking in experimental data on density but
sound speed. In order to fill this void, the research
centres on the specified liquid mixes' densities (ρ) and
sound speed data (u), two main thermodynamic
characteristics. The research further confirms the
existence of hydrogen bonds between anisole and
isomeric cresols using FT-IR spectroscopic data.
Additional analysis of the experimental sound speed
data is carried out by use of Jacobson's free length
theory (FLT) and Schaff's collision factor theory
(CFT). Intermolecular interactions and structural
consequences may be better understood by these
studies, which take into account both observed and
calculated features. In summary, the study employs a
comprehensive approach, combining experimental
techniques and theoretical frameworks, to gain a deeper
understanding of the molecular interactions and
structural dynamics within binary liquid mixtures
involving anisole and various amines. Anisole forms
hydrogen bonding connections with three specific
amines: aniline, N-methyl aniline, and N,N-dimethyl
aniline. This work uses Fourier transform infrared
spectroscopy to determine how often these interactions
occur. This holistic exploration contributes valuable
insights to the field of chemical research and process
optimization, especially in the context of diverse
industrial applications and the safety considerations
associated with certain chemical compounds.
2. Experimental Section
2.1. Materials
S.D. Fine Chem. Ltd., India, supplied analytical reagent
(A.R.) grade chemicals for the study. Gas
Chromatography determined the purities of
experimental liquids, and the Analab Karl Fischer
Titrator assessed water content. These measurements
are shown in Table 1. The observed densities and speed
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of sound were compared to published values, indicating
a high degree of chemical purity [12-30]. At
temperatures between 303.15K and 313.15K, these
results are reported in Table 2.
2.2. Methods
2.2.1. Preparation of Sample
The exact amounts of pure liquids were injected into
screw-capped glass vials to create binary liquid mixes
of anisole and isomeric cresols, which remained
consistently composed throughout. We concurrently
monitored the fundamental properties of the binary
systems to prevent evaporation-induced loss and
minimise moisture absorption. The ATY 224 digital
electronic balance from Shimadzu, India, was used for
mass measurements, which had an uncertainty of ±1 ×
10−4 g. To guarantee precision in the experiment, the
mixes' mole fraction estimate uncertainty was shown to
be less than ±1 × 10−4.
2.2.2. Measurements of Density (ρ) and speed of
sound (u)
Between 303.15 K and 313.15 K at 0.1 MPa, the
density (ρ) and speed of sound (u) of anisole and cresol
binary mixes were measured. Utilizing a Rudolph
DDM-2911 densimeter and Mittal F-05 ultrasonic
interferometer (2MHz frequency), the thermostat
maintained a tight temperature control (±0.02 K).
Density imprecision is ±6x10-4 g.cm-3, yielding
surplus volumes (VE) uncertainties of ±5x10-3
cm3.mol-1. There is an uncertainty of ±0.5 m.s-1 in
sound speed (u) readings and ±0.05 TPa-1 in calculated
excess isentropic compressibility (κsE) values.
Interferometer functionality was verified by comparing
anisole and aromatic amine sound speeds with
literature values.
3. Results and discussion
3.1. Excess volumes (𝑽𝑬 )
Using experimental density data, we can find the excess
molar volume (VE) of anisole in binary mixes with
aniline, N-Methyl Aniline, and N,N-dimethyl Aniline.
Using VE, which is computed using the provided
equation, the non-ideal behaviour is quantified.
The mixture's mole fractions (X_i, i=1,2) and molar
masses (M_i) are related to measured densities (ρ_m
and ρ_i) for components i=1,2. Graphical representation
of volumetric excess (VE) data at 303.15K is shown in
Figure-1. VE values, obtained at this temperature, were
fitted to the Redlich-Kister equation [32], with results
presented in Table 3.
The equation known as the Redlich-Kister is:
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When trying to make sense of how liquid mixes handle
excess volume (VE), the mole fraction of anisole, x₁, is
crucial. Table 6 details the findings of determining the
parameters a₀, a₁, and a₂ using a least-squares
technique. In all composition spectra, the VE data for
Anisole/Aniline, N-Methyl Aniline, and N,N-dimethyl
Aniline mixes is negative, which is indicative of
structural changes in the solvent molecules. Based on
the analysis of Figures 1–3, it is clear that VE remains
negative for all mixes over the whole composition
range, which includes temperatures ranging from
303.15K to 313.15K. The interaction between
expansion and contraction forces when two liquids are
mixed causes the directional trend in VE. In a positive
VE, expansion variables have a larger role than
contraction ones, and vice versa in a negative VE,
contraction factors have a larger impact than expansion
ones. The magnitude of the proportional expansion and
contraction of molecules upon mixing sheds light on
the complexity of binary system excess volume data.
The interplay between these factors becomes pivotal in
shaping the overall VE trend. When expansion-
inducing elements surpass those inducing contraction,
VE manifests as positive. Conversely, when contraction
forces prevail over expansion, VE takes on a negative
character.
The following substances cause volume contraction:
A. Chemical interactions between molecule
components, including strong specific
intermolecular contact, which is often called
heteromolecular association formed via
hydrogen bond formation.
B. An association that is founded on slow physical
processes, such as the dipolar moment or
various such forces of a similar kind
C. Molecules of one component are found to
occupy the interstitial positions of the
structural network of compounds that include
the other element.
D. The ‘geometry’ of the molecular structure,
which takes into account how well the
individual molecules in the structure will fit
together.
While the variables that contribute to volume expansion
can be explained in terms of
A. The declustering of the ‘structure’ of one or
both of the component molecules in a solution,
also known as the loss of dipolar interaction
between the molecules, is the cause of the
dispersion forces that are observed in a
solution.
B. The geometry of molecular ‘structures’ that
precludes molecules from one component from
fitting into voids generated by molecules from
the other component is referred to as the
intermolecular gap.
C. A steric barrier between the molecules that
comprise the component is the third factor.
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A number of variables, shown in Figures 1–3,
contribute to the volume shrinkage seen in binary liquid
mixes, including anisole with aniline, N–methyl
aniline, and N,N–dimethyl aniline. Data showing
excess molar volume (VE) over the whole composition
spectrum indicates that anilines and -OCH3 anisoles
have hydrogen bonding links with the NH2 anilines.
Anisoline, aniline, N-methyl aniline, and N,N-dimethyl
aniline mixes exhibit consistently the same pattern in
algebraic excess volume data, highlighting the
substantial impact of hydrogen bonding interactions on
the total volumetric behaviour.
Anisole +aniline > anisole +N-methylaniline > anisole
+N,N-dimethylaniline
As anisole undergoes a transition from aniline to N,N-
dimethylaniline, there is a noticeable decrease in
molecular interaction between anisole and aromatic
amines. Several factors contribute to this phenomenon.
The thermodynamic properties of the liquids in
question indicate that solvent-solute intermolecular
interaction strengthens with the base strength. Research
into the dissociation constants (pK) of aryl amines that
have been substituted with alkyl groups provides
further evidence for this pattern; for example, pKb
values of 9.16 for N-methylaniline, 8.32 for N,N-
dimethylaniline, and 9.38 for aniline.
The ionisation constant of similar anilium ions
contributes to the process RNH3 → RNH2 + H+,
which is shown in Figures 1 to 3, which weakens the
production of hydrogen bonding from aniline to N,N-
dimethylaniline. Tertiary amines, such as N,N-
dimethylaniline, have weaker intermolecular
interactions, especially hydrogen bonding, since they
do not include an H-atom and do not have an O-H...N
link between them. Anisole and N,N-dimethylaniline
combined FT-IR spectra clearly show this. Figures 1–3
show the excess volume data, which shows that
compared to N-methylaniline and N,N-dimethylaniline,
the anisole–aniline combination had higher negative
values, indicating greater intermolecular interactions. A
negative magnitude of molar volume contraction (VE)
is compatible with this finding and the inductive,
salvation, and steric effects of the alkyl group of aryl
amines.
The electron density of benzene ring derivatives,
influenced by connected groups, plays a pivotal role.
The net electron density within the ring governs
heteromolecular interactions between component
molecules. Experimental results support the notion that
molecular interactions stem from residual electric
moments and dispersion forces, which may differ from
those in pure liquids.
In summary, the progression from aniline to N,N-
dimethylaniline in anisole mixtures is characterized by
a diminishing strength of intermolecular interactions.
This is substantiated by thermodynamic properties,
dissociation constants, and excess volume data, all of
which collectively highlight the intricate interplay of
various factors influencing molecular behavior in these
binary systems.
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3.2. Excess isentropic compressibilities (κsE)
Quantities of pure liquids' sound speeds (u) and binary
Using temperatures of 303.15K and 313.15K, this
research examined combinations generated by mixing
anisole with aniline, N-methylaniline, and N,N-
dimethylaniline, spanning the complete compositional
range. Isentropic compressibilities (κs) and excess
isentropic compressibilities (κsE) were calculated using
observed data of sound speed (u) and density (ρ). The
isentropic compressibility (κs), mole fraction of anisole
(x1), mixture density (ρ), speed of sound (u), and
excess isentropic compressibility (κsE) are all shown in
Table 4. In figures 4 to 5, the κsE data is shown
visually. The experimental density (ρ) and speed of
sound (u) measurements were used to compute the
isentropic compressibility (κs) using the following
equation.
(3)
The estimation of the κsE was
carried out by utilising the equation specified below:
(4)
where κsid is the ideal value of the isentropic
compressibility, which was determined by using the
equation developed by Benson and Kiyohara [37 [37]].
The temperature expansion coefficient (αi) and molar
heat capacity (Cpi) for every component were
calculated using references in the literature [38,39]. A
negative trend over the whole composition range at
both 303.15K and 313.15K was shown by the obtained
values for Cpi and αi, which were utilised to assess the
property, as evidenced by the κsE data in Table-4. The
interaction of different molecular forces, especially in
the intermolecular region, is thought to be responsible
for this occurrence. In general, there are two kinds of
interactions among the component molecules that give
rise to the κsE data for liquid combinations, such
anisole with aniline, N-methylaniline, and N,N-
dimethylaniline [40].
1. A physical interaction that makes a positive
contribution to KSE and is composed of dispersion
forces or interactions between dipoles that are weak.
2. A chemical or particular interaction, which
contributes to a negative contribution in ΚsE and
includes charge-transfer forces, the formation of
hydrogen bonds, and other complex-forming
interactions.
The determination of κsE (excess isentropic
compressibility) is crucial in anticipating molecular
interactions within both pure components and mixtures.
Kiyohara and Benson (37) have postulated that κsE
results from a multitude of conflicting influences.
Negative κsE values are caused by a combination of
factors, including charge exchange, interactions
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between dipoles, factors that facilitate interstitial
mobility, and the creation of hydrogen bonds. On the
flip side, positive excess isentropic compressibility
results from the dissociation of the liquid order
structure. The molecular make-up of the liquid
components mostly determines the size and direction of
κsE. In the case of anisole combined with N,N-
dimethylaniline, the more negative κsE values indicate
that these liquid mixtures are less compressible
compared to their ideal counterparts (37). This trend is
observed across various mixtures, including N-
methylaniline and aniline. Additionally, when liquids
with disparate molecular sizes and shapes are
combined, resulting in a volume reduction, negative
κsE values are observed. The data presented in Table-5
underscores the exceptional properties of all binary
liquid mixtures involving anisole and aniline, N-
methylaniline, and N,N-dimethylanilines. Notably, the
anisole+aniline system exhibits more negative κsE
data. This is attributed to the higher molar volume of
aniline compared to the other component molecules,
suggesting that the mixing of anisole and aniline
molecules promotes more efficient packing, explaining
the observed negative κsE values in this system. For
mixtures of anisole with the aforementioned aromatic
amines, the algebraic values of κsE follow a specific
order.
Anisole+aniline > anisole+N-methylaniline >
N,N-dimethylaniline
At temperatures of 303.15K and 313.15K, κsE values
exhibit negativity across the entire mole fraction
spectrum, indicative of interstitial component effects,
influenced by the molecular strength ratios outlined in
the literature [41,42]. The attributes decrease with
increasing temperature, as seen by the consistently
negative values of excess volume and excess isentropic
compressibilities across all systems examined.
Together with actual values, Table-4 summarises the
results of an examination of the experimental speed of
sound data using collision factor theory (CFT) [9] and
free length theory (FLT) [10,11]. Results from a
comparison of theoretical predictions with
experimental sound speeds show that Schaaff's CFT
model produces better estimates. Using the method for
relative root mean deviation (RMSD) estimates [43,44],
we further evaluated the effectiveness of these theories.
𝟐 𝟏/𝟐
𝟏 𝒚𝒆𝒙𝒑 𝒚𝒆𝒙𝒑
RMSD = ∑𝒏𝒊 𝟏 (6)
𝒏 𝒚𝒆𝒙𝒑
Table-5 presents Root Mean Square Deviations
(RMSD) for binary system values, indicating Schaaff's
CFT model as superior in estimating speed of sound for
the investigated mixtures. Anisole with aniline, N-
methylaniline, and N,N-dimethylanilines' experimental
data was fitted to the Redlich-Kister [32] equation.
Parameter values, obtained through the least-square
method, are detailed in Table 6. Standard deviations σ
(Y^E) are computed using the formula. This analysis
showcases the efficacy of Schaaff's CFT model and
provides insights into the accuracy of Redlich-Kister
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Rigoberto Fimia Duarte et al., : Int. J. Pure & Appl. Sci. Res. Trans; Vol-2, Iss- 1 (2022): 1-18
equation parameters, enhancing our understanding of
sound speed in the studied binary mixtures.
(7)
The excess isentropic compressibility (κsE) of anisole
in mixtures with aniline, N-methylaniline, and N,N-
dimethylanilines is determined by the ratio of the
apparent molar volume (V^E) to the square of the
isentropic compressibility (к_S^E), denoted as σ (Y^E).
The negative values of κsE observed in Figures 4 and 5
across the entire mole fraction range (303.15 K to
313.15 K) suggest a prevalence of interstitial
accommodation among component molecules. This
behavior is attributed to the varying strengths of
interactions between the molecules, as explained in
literature [46]. Notably, the stronger O…H bond
formation between anisole and aniline, compared to
other mixtures, results in increasingly negative κsE
values. The introduction of pure anisole disrupts self-
associated structures, facilitating the release of free
anisole and promoting specific interactions and
intermolecular hydrogen bonding among anisole,
aniline, N-methylaniline, and N,N-dimethylanilines,
forming mixed intermolecular complexes.
3.3. FT-IR Studies
For the purpose of analysing the intermolecular
hydrogen bonding that occurs in binary liquid mixtures,
FT-IR spectroscopy is a powerful instrument that is
utilised. In the investigation of anisole in combination
with aniline, N-methylaniline, and N,N-
dimethylaniline, the primary focus is on the alterations
that occur in the spectra, particularly in relation to the
interactions that occur between hydrogen
bonds.According to the findings of the spectral
analysis, anisole and aniline, as well as anisole and N-
methylaniline, are capable of forming powerful types of
hydrogen bonds. At a more specific level, the C-O-C
stretching of anisole interacts with the -NH stretching
of aniline and N-methylaniline. It is clear that this is the
case from the FT-IR spectra, which show distinct peaks
and shifts in the results of the experiment. When
compared to other liquid mixtures, binary liquid
mixtures that contain phenetole and N,N-
dimethylaniline have weaker solute-solvent
interactions. This observation is supported by the
vibration frequencies and spectra data, which have been
meticulously documented in Table 7 and illustrated in
Figures 6, 7, and 8.The FT-IR spectral data highlight
hydrogen bonding interactions between amine and
ether functional groups in binary liquid mixtures with
an equimolar ratio. N,N-dimethylaniline is not included
in this category. It is possible to observe the hydrogen-
bonded –O stretching band in pure liquids, which
serves as a foundation for comparison. In the
experimental Fourier transform infrared spectrum, the
amine functional group found in anisole exhibits a
distinct stretching band labelled as –O−. This band is
observed in aniline, N-methylaniline, and N,N-
dimethylaniline, with variations observed in each of
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these compounds.The study places additional emphasis
on the influence that hydrogen bonding has on the
spectral shifts that have been observed. The –O...HN−
band, in particular, exhibits a higher frequency shift in
the binary system of anisole and aniline, which is
indicative of a strong hydrogen bond relationship.
While weak hydrogen bonding in the anisole and N-
methylaniline system leads to a lower frequency shift
of the –O...HN− band, weak hydrogen bonding brings
about the opposite effect. Notably, there are no N-H
absorptions found in the case of anisole with N,N-
dimethylaniline. This is an intriguing finding.In
conclusion, the Fourier transform infrared (FT-IR)
spectral analysis of binary liquid mixtures containing
anisole offers valuable insights into the nature and
strength of hydrogen bonding interactions, thereby
elucidating systematic trends in the systems that were
studied.
Anisole + aniline > Anisole + N- methylaniline >
Anisole + N,N-dimethylaniline
Finally, concluded that experimental FT-IR
Spectroscopy analysis concur with those of the
experimental, theoretical studies.
4. Conclusions:
A binary liquid combination of anisole, aniline, N-
methylaniline, and N,N-dimethylanilines was studied
for its density and speed of sound at temperatures
ranging from 303.15K to 313.15K. Various
temperatures were used to test the combinations. To
find the excess volume and excess isentropic
compressibility, the experimental data were subjected
to an analysis of the Redlich-Kister equation. In the
comparison between the theoretical and experimental
models, the CFT models outperformed the FLT ones.
Additional information was gleaned by FT-IR analysis,
which ultimately led to the conclusion that variables
such intermolecular hydrogen bonding, molecule size,
and component shape were responsible for the extra
thermodynamic attributes.
References:
1. Al-Jimaz A S, Al-Kandary J A, Abdu-Latif A
M.; Al-Zanki, A M. Physical properties of
anisole + n-alkanes at temperatures between
(293.15 and 303.15) K. J. Chem. Thermodyn.
2005; 37; 631- 642.
2. Viswanathan, S, Rao M, A. Prasad, D. H. L.
Densities and viscosities of binary liquid
mixtures of anisole or methyl tert-butyl ether
with benzene, chlorobezene, benzonitrial, and
nitrobenzene. J. Chem. Eng. Data. 2000; 45;
764-770.
3. Joshi S, S. Aminabhavi, T. M. Densities and
viscosities of binary liquid mixtures of anisole
with methanol and benzene. J. Chem. Eng.
Data. 1990; 35; 187-9.
4. Orge B, Marino G, Iglesias M, Tojo J,
Pin˜eiro,M. M, Thermodynamics of (anisole +
benzene, or toluene, or n-hexane or
cyclohexane or 1-butanol, or 1-pentanol) at
5
Rigoberto Fimia Duarte et al., : Int. J. Pure & Appl. Sci. Res. Trans; Vol-2, Iss- 1 (2022): 1-18
298.15 K. J. Chem. Thermodyn. 2000; 32; 617-
629.
5. Francesconi, R, Comelli F, Castellari C, Excess
molar enthalpies and excess molar volumes of
binary mixtures containing dialkyl carbonates
+ anisole or phenetole at (288.15 and 313.15)
K. J. Chem. Eng. Data. 2000; 45; 544-548.
6. Ottani S, Comelli F, Excess enthalpies of
binary mixtures containing poly(propylene
glycols) + benzyl alcohol, or + m-cresol, or +
anisole at 308.15K and at atmospheric
pressure. Thermochim. Acta. 2005; 430; 123-
128.
7. Al-Kandary J. A, Al-Jimaz A S, Abdu-Latif A.
M, Densities, viscosities, and refractive indices
of binary mixtures of anisole with benzene,
methylbenzene, ethylbenzene, propylbenzene,
and butylbenzene at (293.15 and 303.15)K. J.
Chem. Eng. Data. 2006; 51; 99- 103.
8. Helmut Fiege, Heinz-Werner Voges,
Toshikazu Hamamoto, Sumio Umemura,
Tadao Iwata, Hisaya Miki, Yasuhiro Fujita,
Hans-Josef Buysch, Dorothea Garbe, Wilfried
Paulus “Phenol Derivatives“ in Ullmann's
Encyclopedia of Industrial Chemistry, 2002,
Wiley-VCH,
Weinheim. doi:10.1002/14356007.a19-313
9. W. Schaaff, Computation of molecular radius
from molar volume and velocity of sound, Z
Med Phys.115 (1940) 69–75.
10. B.Jacobson, Intermolecular free lengths in the
liquid state, Acta. Chem. Scand. 8(1952)
1485–1498.
11. B.Jacobson, Intermolecular free length in
liquids in relation to sound velocity, J. Chem
Phys. 20 (1952) 927–928.
12. Weng WL . Densities and viscositiesfor binary
liquid mixtures of Anisole with 2- butanol, 2-
methyl-1-propanol, and 2-methyl-2- propanol.
J Chem Eng Data.1999,44:788- 791.
13. Cunha DL., Countinho JAP,Daridon JL, et.al.
Experimental densities and speeds of sound of
substituted phenols, and their modeling with
the Prigogine-flory –patterson model.
J.ChemEng Data.2013: 58:2925-2931.
14. Bhatia SC, Rani R. Bhatia R. Densities ,
Speeds of sound , and refractive indices of
binary mixtures of decan-1-ol with anisole ,o-
cresol,m-cresol, and p-cresol at T = (
298.15,303.15,and 308.15) K. J Chem Eng Dat.
2011;56:1669-1674.
15. M. Raveendra, M. Chandrasekhar, K.
Chandrasekhar Reddy, A. Venkatesulu, K.
Sivakumar, K. Dayananda Reddy, Study on
thermo physical properties of binary mixture
containing aromatic alcohol with aromatic,
substituted aromatic amines at different
temperatures interms of FT-IR, 1H NMR
spectroscopic and DFT method, Fluid Phase
Equilibria. 462 (2018) 85-99.
16. S.J. Kharat, P.S. Nikam, Density and
@Kuwait Scientific Society
viscosity studies of binary mixtures of aniline
+ benzene and ternary mixtures of (aniline +
benzene + N, N-dimethylformamide) at
298.15, 303.15, 308.15 and 313.15 K. J. Mol.
Liq.131–132 (2007) 81–86.
17. M.A. Saleh, M. Alauddin, S. Begum, Excess
molar volume of 1-propanol+ aniline, + N-
methylaniline, + N, N-dimethylaniline. Phys.
Chem. Liq., 39 (2001) 453–464.
18. Yan Li, Hong Ye, PingliZeng, FengQ
i.Volumetric Properties of Binary Mixtures of
the Ionic Liquid 1-Butyl-3-Methylimidazolium
Tetrafluoroborate with Aniline. J Solution
Chem.39 (2010) 219–230.
19. P.S. Nikam, S.J. Kharat, Excess Molar
Volumes and Deviations in Viscosity of Binary
Mixtures of N,N-Dimethylformamide with
Aniline and Benzonitrile at (298.15, 303.15,
308.15, and 313.15) K. J. Chem. Eng. Data. 48
(2003) 972-976.
20. R. Palepu, J. Oliver, D. Campbell,
Thermodynamic and transport properties of o-
chlorophenol with aniline and N-
alkylanilines.J. Chem. Eng. Data. 30 (1985)
355–360.
21. A.K.Nain, Ultrasonic and viscometric study of
molecular interactions in binary mixtures of
aniline with 1-propanol, 2-propanol, 2-methyl-
1-propanol, and 2-methyl-2-propanol at
different temperatures.Fluid Phase Equilib. 259
(2007) 218–227.
22. E.B. Freyer, J.C. Hubbard, D.H. Andrews,
Sonic studies of the physical properties of
liquids; The sonic interferometer. The velocity
of sound in some organic liquids and their
compressibilities. J. Am.Chem. Soc.51 (1929)
759–770.
23. I. Alonso, V. Alonso, I. Mozo, I. Garcıa de la
Fuente, J.A. Gonzalez, J.C. Cobos,
Thermodynamics of ketone + amine mixtures.
I. Volumetric and speed of sound data at
(293.15, 298.15, and 303.15) K for 2-
propanone + aniline, + N-methylaniline, or +
pyridine systems. J. Chem. Eng. Data. 55
(2010) 2505–2511.
24. S.L. Oswal, V. Pandiyan, B. Krishna kumar, P.
Vasantharani, Thermodynamic and acoustic
properties of binary mixtures of oxolane with
aniline and substituted anilines at 303.15,
313.15 and 323.15K.Thermochim.Acta. 507–
508 (2010) 27–34.
25. V. Pandiyan, P. Vasantharani, S.L. Oswal,
A.N. Kannappan, Thermodynamic and
Acoustic Properties of Binary Mixtures of
Ethers. 2. Diisopropyl Ether with Arylamines
at (303.15, 313.15, and 323.15) K and
Application of ERAS Model to Aniline
Mixtures with Diisopropyl Ether and
Oxolane.J. Chem. Eng. Data. 56 (2011) 269–
277.
6
Rigoberto Fimia Duarte et al., : Int. J. Pure & Appl. Sci. Res. Trans; Vol-2, Iss- 1 (2022): 1-18

26. M. Katz, P.W. Lobo, A.S.H. Minano, H.
Solimo, Viscosities, densities, and refractive
indices of binary liquid mixtures.Can.j. Chem.,
49 (15) (1971) 2605–2609.
27. V. Pandiyan, S.L. Oswal, P. Vasantharani,
Thermodynamic and acoustic properties of
binary mixtures of ethers; Diisopropyl ether or
oxolane with N,N-dimethylaniline or N,N-
diethylaniline at 303.15, 313.15 and
323.15 K.Thermochim. Acta.518 (2011) 36–
46.
28. B. Nagarjun, A.V. Sarma, G.V. Rama Rao, C.
Rambabu, Thermodynamic and Acoustic Study
on Molecular Interactions in Certain Binary
Liquid Systems Involving Ethyl Benzoate. J.
Thermodyn. 2013 (2013) 1-9.
https://doi.org/10.1155/2013/285796.
29. G. Manukonda, P. Venkateswarlu, K. Siva
kumar, S. Sivarambabu, Volumetric, Speed of
Sound Data and Viscosity at (303.15 & 308.15)
K for the binary mixtures of N, N–
dimethylaniline + aliphatic ketones (C3-C5), +
4-methyl-2-pentanone, +acetophenone,
cyclicketones. J. Ind. Eng.Chem. 20 (2013)
405-418.
30. M. Anurag, M.Sanjeev, Energetics of
molecular interactions of 1,4-dioxane with
formamides or anilines at 308.15 K. J. Ind.
Eng. Chem. 18 (2012) 1013–1017.
31. J.S. Chang, M.J.Lee, Densities of m-cresol+m-
xylene and m-cresol + tetralin mixtures at
298−348K and upto 30MPa, J.Chem.Eng.Data.
40(1995) 1115–1118.
32. Redlich O, Kister AT. Algebraic
representationof thermodynamic properties and
the classification solutions . J Ind Eng Chem.
1948;40:345- 448.
33. V. Pandiyan, S. L. Oswal, P. Vasantharani,
Thermochim. Acta. 518 (2011) 36–46.
34. F. Mata, J.M. Leal, B. Garcia, Z. Phys. Chem.
(Leipzig) 261 (1980) 1059-1064.
35. B. García, J.M. Leal, Collect. Czech. Chem.
Commun. 52 (1987) 299-307.
36. L.A. Herrero, Tesis Licenciatura. Valladolid
Univ. Spain.1986.
37. G.C. Benson, O. Kiyohara, Evaluation of
excess isentropic compressibilities and
isochoric heat capacities, J. Chem. Thermodyn.
11 (1979) 1061–1064.
38. Bruno TJ , Huber ML, Laesecker A , et.al.
thermochemical and Thermophysical
properties of JP-10, NIST IR 6640,National
Institute of Standards and Technology (NIST).
Boulder, Co; 2006.
39. Goodwin ARH ,Marsh KN, Wakeham WA.
Experimental Thermodynamics .Vol. vi. The
Netharlands: IUPAC, Elsevier;2003.
40. Iloukhani H, Ghorbani R. Volumetric
Properties of N,N dimethylformamide with
1,2alkanediols, at 200C.J solution
Chem.1998;27:141-149.
41. N.I. Malek, S.P. Ijardar, S.B. Oswal, J. Chem.
Eng. Data. 59 (2014) 540-553.
+ 42. J.F. Kincaid, H. Eyring, J. Chem. Phys. 6
(1938) 620–629.
43. Altuwaim MS ,Alkhalidi HAEK, Al-Jimaz SA,
et.al. Comparative study physico-chemical
properties of binary mixtures of N,N –
dimethylformamide with 1-alkanols at
different temperatures. J Therm Anal
Calorim.2012;107:681-687.
44. Dipali C, Anand A, Apparent molarvolume and
apparent molar adiabatic compressibility of 2-
hydroxy-5-methylacetopheneone in N,N –
dimethylformamide at different temperatures.
J Therm Anal Calorim.2012;107:21-40.
45. Ali A, Nain AK. Ultrasonic and volumetric
study of binary mixtures of benzyl alcohol with
amides Bullchem soc JPn. 2002;75:681-687.
46. R.M. Silverstein , G.C. Bassler , T.C. Morrik ,
Spectroscopic Identification of Organic
Compounds, 5th edn, John Wiley &sons, Inc.,
Singapore, 1991 .

Table 1:
Name of the chemical, source, CAS number, purity in mass fraction, purity analysis method and water content in mass
fraction of the chemicals used in this work.

Purity in mass Purity in mass

Water
CAS fraction fraction *Analysis
Component Source content in
number (as received (after method
mass fraction
from supplier purification)

Anisole S.D.Fine 64-17-5 >0.99 0.989 GC 0.0003

Chemicals.Ltd
Aniline S.D.Fine 62-53-2 ˃0.99 0.994 GC 0.0004

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Chemicals. Ltd
N-Methylaniline S.D.Fine 100-61- ˃0.98 0.995 GC 0.0006
Chemicals. Ltd 8

N,N- S.D.Fine 121-69- ˃0.99 0.997 GC 0.0005

dimethylaniline Chemicals. Ltd. 7

*GC=Gas Chromatography

Table 2:
Density (ρ) and sound speed (u) values for the pure components along with literature values at temperatures studied and
T/K
ρ/(g.cm3) u/(m.s-1)

Exp. Lit. Exp. Lit.

Anisole
0.98460 a 1386.57 1387.00c
303.15 0.98459
0.98420 a
308.15 0.98031 0.97971b
0.97570a 1349.87 1349.66c
313.15 0.97566
0.97500 a
Aniline
1.01278 d
1615.64d
1.01279 e
303.15 1.01276 1615.60 1614.50 j
1.01280 f
1619.00k
1.00864 d
1.00960 g
308.15 1.00862 1.00860 h

1.00449 d 1580.00d
313.15 1.00448 1.00445 f 1580.26 1581.40l
1.00446 i 1579.50k
N-methylaniline
1549.32d
0.98172 d
303.15 0.98174 1549.36 1545.50e
0.98170 i
1548.30m
0.97820m
0.97604 d
308.15 0.97426

0.97089 d
1511.84d
313.15 0.97084 0.96980m 1511.86
1512.40m
0.9698 n
N,N-dimethylaniline
0.94818d
1470.24 d
0.94815 o
303.15 0.94818 1470.34 1468.00p
0.94840 p
1470.50q
0.94820 q
0.94355d
308.15 0.94358 0.94355 r
0.94386 s
0.93978d 1431.00 p
313.15 0.93974 0.93970 p 1432.62 1435.00 q
0.93980 q 1432.00d
at 0.1 MPa pressure.

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Standard uncertainties are u(ρ) ±5x10-5g.cm−3, u (u) ± 0.5 m.s−1, u (p) = 1kPa, u (T) ± 0.02 and ±0.05 K for ρ and u
measurements respectively.
(a) -ref-12 ,(b)-ref-13(c)-ref-14, (d)-ref-15,(e)-ref-16, (f)-ref-17,(g) ref-18,(h)ref-19,(i)-ref-20 ,(j)-ref-21,(k)-ref-22,(l)-ref-
23,(m) ref-24,(n)ref- 25,(o).ref-26,(p) ref-27,(q)-ref-28,(r)-ref-29,(s)-ref-30.
,
Table 3:
Mole fraction of Anisole (x1), densities (ρ), experimental excess volumes (VE) and predicted excess volumes (Redlich-
Kister ) at T= 303 K to 313.15 K and 0.1M Pa pressure for the binary mixtures of Anisole (1) with Aniline,N-
methylaniline,N,N-dimethylaniline(2)a

x1 Density(ρ) VE/cm3.mol-1
(g.cm-3)
Experimental Redlich-Kister

Anisole (1) + aniline(2)

T=303.15K
0.0854 1.01032 -0.035 -0.036
0.1736 1.00775 -0.061 -0.060
0.2647 1.00509 -0.076 -0.075
0.3590 1.00233 -0.083 -0.083
0.4565 0.99951 -0.086 -0.086
0.5575 0.99664 -0.084 -0.085
0.6622 0.99374 -0.074 -0.079
0.7707 0.99078 -0.070 -0.066
0.8832 0.98774 -0.042 -0.042
T=308.15K
0.0854 1.00642 -0.058 -0.059
0.1736 1.00407 -0.106 -0.103
0.2647 1.00151 -0.135 -0.134
0.3590 0.99880 -0.150 -0.152
0.4565 0.99597 -0.154 -0.157
0.5575 0.99305 -0.148 -0.149
0.6622 0.99004 -0.132 -0.131
0.7707 0.98690 -0.102 -0.100
0.8832 0.98364 -0.056 -0.057
T=313.15K
0.0854 1.00259 -0.093 -0.091
0.1736 1.00016 -0.140 -0.145

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0.2647 0.99751 -0.172 -0.171

0.3590 0.99472 -0.178 -0.178
0.4565 0.99180 -0.174 -0.173
0.5575 0.98879 -0.162 -0.161
0.6622 0.98571 -0.145 -0.145
0.7707 0.98254 -0.122 -0.121
0.8832 0.97920 -0.078 -0.079
Anisole (1) + N-methylaniline (2)

T=303.15K
0.0997 0.98225 -0.026 -0.026
0.1995 0.98273 -0.047 -0.047
0.2993 0.98317 -0.065 -0.064
0.3993 0.98354 -0.075 -0.076
0.4992 0.98386 -0.078 -0.080
0.5993 0.98414 -0.077 -0.078
0.6993 0.98436 -0.071 -0.069
0.7995 0.98451 -0.056 -0.053
0.8997 0.98456 -0.028 -0.030
T=308.15K
0.0997 0.97511 -0.030 -0.029
0.1995 0.97593 -0.054 -0.054
0.2993 0.97670 -0.072 -0.072
0.3993 0.97740 -0.083 -0.084
0.4992 0.97805 -0.087 -0.089
0.5993 0.97865 -0.087 -0.087
0.6993 0.97918 -0.079 -0.076
0.7995 0.97963 -0.061 -0.058
0.8997 0.97998 -0.031 -0.033
T=313.15K
0.0997 0.97163 -0.038 -0.037
0.1995 0.97236 -0.062 -0.064
0.2993 0.97301 -0.084 -0.082
0.3993 0.97359 -0.095 -0.093
0.4992 0.97410 -0.098 -0.098
0.5993 0.97457 -0.094 -0.096
0.6993 0.97498 -0.087 -0.087
0.7995 0.97530 -0.069 -0.069
0.8997 0.97555 -0.041 -0.041
Anisole (1) + N,N-dimethylaniline (2)
T=303.15K
0.1147 0.95191 -0.013 -0.014

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0.2258 0.95563 -0.021 -0.021

0.3333 0.95932 -0.026 -0.025
0.4374 0.96298 -0.028 -0.027
0.5384 0.96663 -0.029 -0.027
0.6363 0.97026 -0.026 -0.027
0.7313 0.97388 -0.023 -0.024
0.8235 0.97747 -0.016 -0.020
0.9130 0.98104 -0.014 -0.012
T=308.15K
0.1147 0.94736 -0.016 -0.016
0.2258 0.95113 -0.027 -0.027
0.3333 0.95487 -0.035 -0.034
0.4374 0.95858 -0.038 -0.037
0.5384 0.96227 -0.039 -0.037
0.6363 0.96594 -0.038 -0.035
0.7313 0.96958 -0.027 -0.030
0.8235 0.97320 -0.018 -0.023
0.9130 0.97676 -0.015 -0.013
T=313.15K
0.1147 0.94348 -0.024 -0.023
0.2258 0.94717 -0.032 -0.035
0.3333 0.95083 -0.039 -0.040
0.4374 0.95446 -0.042 -0.043
0.5384 0.95807 -0.044 -0.043
0.6363 0.96166 -0.042 -0.041
0.7313 0.96523 -0.041 -0.038
0.8235 0.96876 -0.029 -0.030
0.9130 0.97225 -0.018 -0.018

The standard uncertainties are u (x) ± 1x10-4, u (ρ) ± 5x10-5 g.cm−3, u (T) = 0.02K and u(p) = 1 kPa, and u (VE) = ±0.002
cm3.mol-1.respectively.
Table 4:
Mole fraction (x1) of Anisole Experimental sound speed(u), isentropiccompressibilities (κs), excess isentropic
compressibilities (κsE) and predicted excess isentropic compressibilities (Redlich-Kister) theoretical sound speed values
of Anisole (1) with Aniline,N-methylaniline,NN-dimethylaniline(2) at 303.15K and 313.15 K and 0.1M Pa pressure.

u(exp) κs
uFLT uCFT κsE/(TPa-1)
(m.s-1) (TPa-1)
x1
Redlich-
(m.s-1) Exp.
Kister
Anisole(1)+aniline(2)
T=303.15 K
0.0854 1594.85 390.64 1596.99 1595.75 -5.560 -5.655
0.1736 1574.41 401.79 1577.07 1575.27 -10.260 -10.054
0.2647 1552.49 414.27 1556.09 1554.19 -13.430 -13.305

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0.3590 1530.05 427.67 1533.97 1532.44 -15.470 -15.489

0.4565 1507.36 441.90 1511.10 1510.03 -16.440 -16.623
0.5575 1484.86 456.73 1487.57 1486.91 -16.570 -16.656
0.6622 1461.95 472.59 1463.58 1463.02 -15.430 -15.424
0.7707 1438.29 489.82 1438.87 1438.37 -12.660 -12.618
0.8832 1413.36 508.93 1413.28 1412.92 -7.740 -7.735
T=313.15K
0.0854 1563.11 408.22 1566.23 1560.19 -9.170 -9.094
0.1736 1543.69 419.58 1547.62 1539.54 -15.160 -15.353
0.2647 1522.48 432.49 1526.92 1518.27 -19.310 -19.387
0.3590 1500.00 446.80 1504.81 1496.32 -21.820 -21.724
0.4565 1476.82 462.30 1481.39 1473.69 -22.860 -22.744
0.5575 1453.44 478.74 1457.00 1450.33 -22.670 -22.613
0.6622 1429.81 496.24 1431.82 1426.17 -21.120 -21.184
0.7707 1405.59 515.15 1405.71 1401.23 -17.860 -17.870
0.8832 1379.25 536.84 1378.11 1375.47 -11.480 -11.480
Anisole + N-methylaniline
T=303.15 K
0.0997 1533.74 432.79 1535.12 1532.82 -2.140 -2.121
0.1995 1518.01 441.59 1520.46 1516.36 -3.730 -3.732
0.2993 1502.06 450.81 1505.44 1499.96 -4.880 -4.902
0.3993 1485.94 460.47 1489.79 1483.59 -5.610 -5.672
0.4992 1469.84 470.46 1473.75 1467.30 -5.980 -6.048
0.5993 1453.72 480.82 1457.36 1451.04 -6.000 -6.005
0.6993 1437.52 491.61 1440.51 1434.87 -5.560 -5.486
0.7995 1421.06 502.99 1423.10 1418.74 -4.530 -4.399
0.8997 1403.94 515.30 1404.95 1402.68 -2.560 -2.623
T=313.15K
0.0997 1496.32 459.67 1498.09 1495.20 -3.130 -3.097
0.1995 1480.71 469.06 1483.65 1478.63 -4.920 -4.950
0.2993 1464.44 479.23 1468.58 1462.14 -5.920 -5.998
0.3993 1448.10 489.81 1452.91 1445.70 -6.520 -6.549
0.4992 1431.87 500.71 1436.74 1429.37 -6.780 -6.780
0.5993 1415.74 511.94 1420.25 1413.10 -6.720 -6.735
0.6993 1399.92 523.36 1403.36 1396.93 -6.460 -6.326
0.7995 1383.56 535.63 1385.81 1380.82 -5.350 -5.329
0.8997 1366.69 548.80 1367.81 1364.80 -3.350 -3.385

Anisole (1) + N,N-dimethylaniline(2)

T=303.15 K
0.1147 1461.81 491.61 1462.28 1460.51 -1.030 -1.075
0.2258 1453.67 495.20 1454.27 1451.12 -2.040 -1.958
0.3333 1445.41 498.95 1446.11 1442.07 -2.710 -2.621
0.4374 1436.99 502.89 1437.80 1433.32 -3.030 -3.043
0.5384 1428.62 506.88 1429.44 1424.86 -3.150 -3.210
0.6363 1420.22 510.98 1421.03 1416.69 -3.010 -3.112
0.7313 1411.98 515.03 1412.61 1408.77 -2.740 -2.744
0.8235 1403.66 519.25 1404.03 1401.10 -2.160 -2.101
0.9130 1395.14 523.69 1395.40 1393.68 -1.180 -1.186
T=313.15K
0.1147 1422.58 523.74 1425.17 1422.91 -0.453 -0.451
0.2258 1413.34 528.54 1417.24 1413.56 -0.752 -0.750
0.3333 1404.35 533.27 1409.16 1404.53 -0.936 -0.939
0.4374 1395.65 537.88 1400.95 1395.81 -1.036 -1.041
0.5384 1387.21 542.40 1392.62 1387.36 -1.057 -1.070
0.6363 1379.07 546.77 1384.24 1379.17 -1.029 -1.029

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0.7313 1371.18 551.04 1375.78 1371.25 -0.921 -0.912
0.8235 1363.54 555.20 1367.11 1363.56 -0.728 -0.711
0.9130 1356.09 559.30 1358.24 1356.10 -0.404 -0.412

The standard uncertainties are u (X1) =± 1×10-4, u(u) = 0.5m.s-1, u (T) = 0.02 K for speed of sound and u (p) = ±5x10-
5
g.cm-1, Uc(KSE)=0.03TPa-1.

Table 5:
RMSD of speed of sound (u) of anisole (1) with aniline, N-methylaniline, andN,N-dimethylaniline (2) at T= 303.15K and
313.15 K from CFT, FLT models.
RMSD
Anisole(1) + aniline (2)
T=303.15K
CFT 0.0009
FLT 0.0007
T=313.15K
CFT 0.0022
FLT 0.0040
Anisole (1) + N-methylaniline (2)
T=303.15K
CFT 0.0013
FLT 0.0031
T=313.15K
CFT 0.0050
FLT 0.0037
Anisole(1) + N,N-dimethylaniline (2)
T=303.15K
CFT 0.0062
FLT 0.0022
T=313.15K
CFT 0.0001
FLT 0.0027

Table 6:
Standard deviation σ (VE) and σ (κsE) values of constants (a0, a1, a2; b0, b1, b2) for Redlich-Kister, Eq. (2) et al. for
Anisole (1) with Aniline,N-methylaniline,N,N-dimethylanilines.

Redlich-Kister
Temperature a0 a1 a2 σ(VE)
cm-3.mol-1
Anisole(1) +aniline(2)
303.15K -0.343 0.019 -0.142 0.002
308.15K -0.619 0.125 -0.045 0.002
313.15K -0.674 0.225 -0.445 0.002
Anisole(1)+N-methylaniline(2)
303.15K -0.321 -0.025 0.024 0.002
308.15K -0.357 -0.022 0.020 0.002
313.15K -0.3908 -0.026 -0.067 0.002

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Anisole(1)+N,N-dimethylaniline(2)
303.15K -0.108 -0.009 -0.055 0.002
308.15K -0.150 0.001 -0.017 0.002
313.15K -0.172 -0.0004 -0.085 0.002

Table 7:
Experimental FT-IR Frequencies with wavenumbers (cm-1) and Shifting of bands of Anisole (1) + substituted anilines (2)
binary mixtures at 298.15K.

Compound Band Experimental

 (c.m-1)
Anisole C-O-C 1239.68 (Asym) and 1035.37 (Sym)
a
Aniline -NH2 3433.05 (w) and 3356.09 (m)
b
N-MethylAniline -NH 3412.38 (m)
c
N,N-DiMethylAniline -N No peak
Anisole + Aniline -NH2d 3371.17 (w) and 3348.31(m)
e
Anisole + N-Methyl Aniline -NH 3416.53(m)
f
Anisole + N,N-Di Methyl -N No peak
Aniline
Shift in wavenumbers with respect to Aromatic anilines values (c.m-1)
Anisole + Aniline -NH2d -NH2a 62.05 (w) and 7.79 (m)
e b
Anisole + N-Methyl Aniline -NH -NH 4.15
Anisole + N,N-Di Methyl -Nc -Nf No peak
Aniline

0.00

-0.02

-0.04
V (cm .mol )
-1
3

-0.06
E

-0.08

-0.10

-0.12
0.0 0.2 0.4 0.6 0.8 1.0
Molefractions(x1)

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Figure 1. Variation of excess volume (VE) of the binary liquid mixture of anisole (1) with aniline (2) (■),N-methylaniline
(2)(●), N,N-dimethylaniline(2) (▲), at 303.15 K

0.00

-0.02

-0.04

-0.06
VE(cm3.mol-1)

-0.08

-0.10

-0.12

-0.14

-0.16

-0.18

0.0 0.2 0.4 0.6 0.8 1.0

Molefractions(x1)

Figure 2 Variation of excess volume (VE) of the binary liquid mixture of anisole (1) with aniline (2) (■), N-methylaniline
(2)(●), N,N-dimethylaniline(2) (▲), at 308.15 K.

0.00

-0.02

-0.04

-0.06

-0.08
VE(cm3.mol-1)

-0.10

-0.12

-0.14

-0.16

-0.18

-0.20

-0.22
0.0 0.2 0.4 0.6 0.8 1.0
Molefractions(x1)

Figure 3 Variation of excess volume (VE) of the binary liquid mixture of anisole (1) with aniline (2) (■), N-methylaniline
(2)(●), N,N-dimethylaniline(2) (▲), at 313.15 K.

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-2

-4

-6

-8
KS (TPa )
-1

-10
E

-12

-14

-16

-18
0.0 0.2 0.4 0.6 0.8 1.0
Molefraactions(x1)

Figure 4 Variation of excess isentropic compressibility (κsE) of the binary liquid mixture of anisole (1) with aniline(2)
(■), N-methylaniline (2)(●), N,N-dimethylaniline(2) (▲) at 303.15K.

0
-2
-4
-6
-8
-10
KSE(TPa-1)

-12
-14
-16
-18
-20
-22
-24

0.0 0.2 0.4 0.6 0.8 1.0

Molefractions(x1)

Figure 5 Variation of excess isentropic compressibility (κsE) of the binary liquid mixture of anisole (1) with aniline (2)
(■),N-methylaniline (2)(●), N,N-dimethylaniline(2) (▲) at 313.15K.

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1.0

0.8
Transmittance(%)

(a) (b) (c)

0.6

0.4

0.2

0 500 1000 1500 2000 2500 3000 3500 4000 4500

Wavenumber(cm3)

Figure 6: Normalized FT-IR Spectra of (Anisole + Aniline) binary mixture over the range (3500- 1000 cm-1). peak a:
Anisole (A); peak b: Aniline (A); peak c: Anisole with Aniline (A+1A).

1.1

1.0

0.9
(c)
Transmittance(%)

0.8 (a)

0.7 (b)
0.6

0.5

0.4

0.3

0.2
0 500 1000 1500 2000 2500 3000 3500 4000 4500
Wavenumber(cm-3)

Figure 7: Normalized FT-IR Spectra of (Anisole + N-Methylaniline) binary mixture over the range (3500- 1000 cm-1).
peak a: Anisole (A); peak b: N-Methylaniline (NMA); peak c: Anisole with N-Methylaniline (A +NMA).

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Rigoberto Fimia Duarte et al., : Int. J. Pure & Appl. Sci. Res. Trans; Vol-2, Iss- 1 (2022): 1-18

1.1

1.0

0.9

0.8 (a) (c)

Transmittance(%)

0.7 (b)

0.6

0.5

0.4

0.3

0.2
0 500 1000 1500 2000 2500 3000 3500 4000 4500
Wavenumber(cm-3)

Figure 8: Normalized FT-IR Spectra of (Anisole + N,N-dimethylaniline) binary mixture over the range (3500- 1000 cm-
1
). peak a: Anisole (A); peak b: N,N-dimethylaniline (NNDMA); peak c: Anisole with N,N-dimethylaniline (A
+NNDMA).

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