ISSN 0036-0244, Russian Journal of Physical Chemistry A, 2014, Vol. 88, No. 4, pp. 601–606. © Pleiades Publishing, Ltd., 2014.
601
1
INTRODUCTION
Ultrasonic technique is one of the sensitive meth-
ods of elucidation of the molecular interactions
between polar and non polar components. Such stud-
ies in liquid mixtures have great relevance in many
fields of applied and theoretical research [1–5].
Methyl formate is an ester. It is used in the lacquer
industry as a solvent for cellulose nitrate. It is also used
as a fumigant and larvacide for tobacco.
The molecular interaction studies of liquid mixtures
with alcohols as one of the components is of particular
interest, since alcohols are highly polar and self associ-
ated through hydrogen bonding in pure state [6–8].
Excess molar enthalpies of ethyl formate and 1-pro-
panol, 2-propanol, 1-butanol, and 2-butanol, and
1-pentanol at 308.15 K were reported by Dong et al
[9]. Excess molar volumes and viscosities for binary
mixtures of butyrolactone with methyl formate, ethyl
formate, methyl acetate, ethyl acetate and acetonitrile
at 298.15 K were reported by Lu et al. [10]. The survey
of literature shows that there are no reports on molec-
ular interaction studies of the system undertaken in
the present study.
The present work is an attempt to elucidate the
molecular interactions between methyl formate and
ethanol at 303, 308, and 313 K by ultrasonic tech-
nique.
1
The article is published in the original.
EXPERIMENTAL
Binary mixtures were prepared by mixing appropri-
ate volume of the liquid components in the standard
flasks with air tight caps. The masses were recorded on
digital electronic balance (ACM-78094L, ACMAS
Ltd., India) to an uncertainty of ±1 mg. The density and
viscosity were measured by using specific gravity bottle
and Ostwald’s viscometer with accuracy of ±0.01 kg m
–3
and ±0.001 N s m
–2
respectively. The ultrasonic veloc-
ities in the liquid mixtures were measured with a single
crystal ultrasonic interferometer (Mittal Enterprizes,
New Delhi, Model f81) operated at 2 MHz, which was
calibrated with water. The accuracy of the ultrasonic
velocity measurements was in the order of ±1 m s
–1
. All
measurements were made using a constant tempera-
ture bath [INSREF model IRI-016C, India] by circu-
lating water from the thermostat with accuracy
±0.01 K. In the present study the chemicals used are of
Analytical Grade (AR) purchased from Sd fine Chem-
icals, India. The purity of the chemicals was checked
by comparing the density (ρ), viscosity (η), and ultra-
sonic velocity (U) with available literature data [11–
13] and listed in Table 1.
THEORETICAL ASPECTS
The different parameters such as ultrasonic velocity
(U), adiabatic compressibility (β), acoustic imped-
ance (Z) were found using different formulae reported
Intermolecular Interactions in Methyl Formate–Ethanol Mixtures
at 303–313 K according to Ultrasonic Data
1
S. Elangovan
a,c
and S. Mullainathan
b,c
a
Department of Physics, Easwari Engineering College, Chennai 600089, Tamil Nadu, India
b
Department of Physics, A.V.C College of Engineering, Mayiladuthurai 609305, Tamil Nadu, India
c
Research and Development Centre, Bharathiar University, Coimbatore 641046, Tamil Nadu, India
e-mail: elangovan.physics@rediffmail.com
Received March 13, 2013
Abstract—Density (ρ), viscosity (η), and ultrasonic velocity (U) have been measured for a binary mixture
composed of methyl formate and ethanol at 303, 308, and 313 K. The adiabatic compressibility (β), acoustic
impedance (Z), free length (L
f
), free volume (V
f
), internal pressure (π
i
), viscous relaxation time (τ), and
Gibbs free energy (ΔG) were calculated from the experimental data. The excess values of these parameters
(β
E
, Z
E
, , , , τ
E
, and ΔG
E
) have also been calculated using the determined parameters and inter-
preted in terms of molecular interactions. The deviations in the sign and values of these excess parameters
from the ideal mixing reveal the nature of intermolecular interactions between components of the mixture.
Keywords: methyl formate, ethanol, ultrasonic velocity and hydrogen bonding.
DOI: 10.1134/S0036024414040086
L
f
E
V
f
E
π
i
E
PHYSICAL CHEMISTRY
OF SOLUTIONS