Ultrasonic speed and related acoustical parameters of 1,1'-Binaphthalene-2, 2'-diyl diacetate solutions at 308.15 K

Article abstract of DOI:10.1155/2011/869594

The density (ρ), viscosity (η) and ultrasonic speed (U) (2MHz) of chloroform, THF, ethyl alcohol, ethyl acetate, 1,4-dioxane and 1,1'-binaphthalene-2,2'-diyl diacetate (DBNA) solutions have been determined at 308.15 K. Various acoustical parameters namely specific acoustical impedance (Z), adiabatic compressibility (k_a), Van der Waals constant (b), intermolecular path length (L_f), internal pressure (π), Rao's molar sound function (R), relaxation time (τ), classical absorption coefficient (α/f²)cl and solvation number (S_n) have been derived from ρ, η and U data and correlated with concentration (C). A fairly good to excellent correlation has been observed between a particular parameter and C. Linear increase of Z, R, b, (α/f²) _Cl and τ (except EA) (R² = 0.90 - 0.999) and linear decrease of k_s, π and L_f (R² = 0.947 - 0.995) with C supported existence of powerful molecular interactions in the solutions and further supported by nonlinear increase of S_n with C. A fairly constant Gibbs free energy of activation has been observed in all the solvent systems studied.

Full text of DOI:10.1155/2011/869594

ISSN: 0973-4945; CODEN ECJHAO
E-Journal of Chemistry
2011, 8(2), 762-766
http://www.e-journals.net
Ultrasonic Speed and Related Acoustical
Parameters of 1,1’-Binaphthalene-2,2’-diyl
Diacetate Solutions at 308.15 K
*
POOJA P. ADROJA, S. P. GAMI, J. P. PATEL and P. H. PARSANIA
Department of Chemistry, Saurashtra University
Rajkot-360 005 Gujarat, India
phparsania22@gmail.com
Received 5 June 2010; Accepted 26 August 2010
Abstract: The density (ρ), viscosity (η) and ultrasonic speed (U) (2MHz) of
chloroform, THF, ethyl alcohol, ethyl acetate, 1,4-dioxane and 1,1’-
binaphthalene-2,2’-diyl diacetate (DBNA) solutions have been determined at
3
08.15 K. Various acoustical parameters namely specific acoustical
impedance (Z), adiabatic compressibility (κ ), Van der Waals constant (b),
a
intermolecular path length (L ), internal pressure (π), Rao’s molar sound
f
2
function (R), relaxation time (τ), classical absorption coefficient (α/f ) and
cl
solvation number (S ) have been derived from ρ, η and U data and correlated
n
with concentration (C). A fairly good to excellent correlation has been
observed between a particular parameter and C. Linear increase of Z, R, b,
2
2
(
L (R = 0.947 – 0.995) with C supported existence of powerful molecular
α/f ) and
τ
(except EA) (R = 0.90 – 0.999) and linear decrease of κs, π and
Cl
2
f
interactions in the solutions and further supported by nonlinear increase of Sn
with C. A fairly constant Gibbs free energy of activation has been observed in
all the solvent systems studied.
Keywords: Ultrasonic speed, Acoustical parameters, Solvation number, Gibbs free energy of
activation
Introduction
Novel materials with controlled stereochemistry have found numerous applications.
2
,2’-Substituted 1,1’-binaphthyl systems have been found extensively useful because of their
1
stable conformation . (R) or (S) - BINOLS have often been used as the starting materials for
obtaining chiral binaphthyl compounds, leading to a variety of binaphthyl derivatives, which
can exhibit remarkably stable chiral configuration as well as high chiral induction in many
2
asymmetric processes .

Ultrasonic Speed and Related Acoustical Parameters
763
The measurement of speed of sound in liquid mixtures and solutions has also been found to
3
be important tool to study the physicochemical properties of the mixtures and solutions . The
density, viscosity and speed of sound provide important information about molecular packing,
molecular interactions and their strength influenced by the size, shape and the chemical nature of
4-6
component molecules . The measurements of physical properties such as density(ρ), refractive
index (n), coefficient of viscosity(η), ultrasonic velocity (U), molar sound velocity or Rao’s
number(R), molar volume (υ ), adiabatic compressibility (β), characteristic acoustic
f
impedance(Z), inter molecular or free length(L ), free volume (V ), available volume(V ) play an
f
f
a
important role in sound transmission in different organic solvents and solutions.
To our knowledge no work has been reported on acoustical properties of BINOL
7
derivatives except our recent publication . In present work an effort has been made to
understand molecular interactions in 1,1’-binaphthalene-2,2’-diyl diacetate (DBNA)
solutions at 308.15 K.
Experimental
8
Solvents used in the present study were purified prior to their use . 1,1’-Bi-2-naphthol
(
water) using FeCl (14 g in 30 mL water) as a catalyst at 60 C for 15-20 min. DBN was
DBN) was synthesized by free radical coupling reaction of 0.05 mol 2-naphthol (in 300 mL
o
3
crystallized at least three times from toluene and methanol-water systems (yield 55.9% and
o
mp 218 C). DBNA was synthesized by condensing 0.055 mol DBN in 60 mL of 10%
0
sodium hydroxide and 18.4 mL acetic anhydride at 0-5 C for 30 min. The separated product
was filtered, washed well with water and dried at room temperature. DBNA was crystallized
0
three times from methanol-water. The yield was 98.6% and mp 56 C. Stock solutions of
DBNA were prepared in selected solvents. From stock solutions, a series of solutions were
prepared. The density (ρ), viscosity (η) and ultrasonic speed (U) measurements of pure
solvents and solutions were carried out at 35 C using specific gravity bottle, Ubbelohde
o
suspended level viscometer and Mittal Enterprise Interferometer (New Delhi, Model No
F-81) operating at 2 MHz, respectively. The ρ, η and U measurements were accurate to
-
3
±
0.0001 g cm , ±0.01 mPa s and ±0.15%, respectively.
Results and Discussion
The experimental data on ρ, η and U of pure solvents:
Chloroform (CF), tetrahydrofuran (THF), ethyl alcohol (EtOH), ethyl acetate (EA),
,4-dioxane (DO) and DBNA solutions at 308.15 K are summarized in Table 1. The
1
observed trends in ρ, η and U are CF > DO > EA > THF > EtOH; DO > EtOH > CF > EA >
THF and DO > THF > EtOH > EA >CF, respectively. From Table 1, it is observed that ρ
(
decreased in CF), η (decreased in EA) and U increased linearly with increasing
concentration (C). The observed variation in ρ with C is little, while it is considerable for η
and U. Linear variation of ρ, η and U with C confirmed existence of powerful molecular
interactions in the solutions. Variation in ρ and U with C is not as appreciable as η because
9,10
molecular motion is much more affected by solvent-solute interactions . Because of
molecular interactions the structure of the solute is modified and hence physical properties
change accordingly. The density, viscosity and ultrasonic speed are inherent structural
properties of the materials. The least squares equations along with regression coefficients
2
R ) are summarized in Table 2 from which it is observed that a fairly good to excellent
(
correlation is found between said parameters and C (0.904 - 0.999).

7
64
P. H. PARSANIA et al.
Table 1. Density (ρ), viscosity (η) and ultrasonic speed (U) data of DBNA at 308.15 K
3
ρ, kg/m
Conc., %
.925
.85
CF
THF
877.3
879.8
886.5
892.3
899.2
EtOH
784.6
790.2
796.1
804.6
812.2
η , m Pas
0.946
0.987
1.035
1.088
1.142
EA
DO
0
1464
1463
1461
1458
1458
888.5
891.5
897.4
904.2
910.9
1015
1018
1023
1026
1029
1
3
.7
.55
5
7
.4
0
1
.925
.85
0.547
0.564
0.569
0.587
0.604
0.446
0.45
0.473
0.499
0.532
0.477
0.458
0.46
0.423
0.415
1.026
1.04
1.133
1.166
1.24
3
.7
.55
5
7
.4
-
1
U, ms
0
.925
.85
957.6
958.8
961.2
968.4
970.8
1233
1237
1238
1245
1250
1119
1125
1134
1142
1148
1099
1102
1109
1113
1122
1294
1296
1298
1307
1310
1
3.7
.55
5
7
.4
Various acoustical parameters namely specific acoustical impendence (Z), adiabatic
compressibility (κ ) Rao’s molar sound function (R), Van der Waals constant (b),
a ,
intermolecular free path length (L ), internal pressure (π), relaxation time (τ), classical
f
2
absorption coefficient (α/f ) and solvation number (S ) were derived using ρ, η and U data
cl
n
7,11,12
according to our recent publications
and correlated with C. The least squares equations
along with regression coefficients are summarized in Table 2. A fairly good to excellent
correlation is observed between a given parameter and C.
o
Table 2. Least square equations and correlation coefficients for DBNA at 35 C
Parameter
Correlation equations and regression coefficients
CHCl
-1.007C + 1464.
R² = 0.929
η,m. Pas 3.460C + 885.0
R² = 0.999
3
THF
3.390x + 873.8
R² = 0.998
0.022C + 0.413
R² = 0.944
4.24C + 1228
R² = 0.958
0.010C + 1.068
R² = 0.980
-0.096C+ 7.614
R² = 0.98
0.612C + 8.448
R² = 0.990
-0.169C+ 3.885
R² = 0.994
0.553C + 7.763
R² = 0.990
EtOH
4.161C + 781.3 3.460C + 885.0 2.202C + 1013.
R² = 0.995 R² = 0.999 R² = 0.979
0.049C + 0.891 -0.015C + 0.494 0.055C + 0.954
EA
DO
3
ρ, kg/m
R² = 0.997
7.48C + 1111.
R² = 0.997
R² = 0.906
5.84C + 1091.
R² = 0.973
R² = 0.961
4.32C + 1288.
R² = 0.926
-
1
U, m.s
3.6C + 952.5
R² = 0.929
0.003C + 1.396
R² = 0.882
-0.046C+ 7.515
R² = 0.909
-6
Z. 10 ,
kg m s
0.013C + 0.862 0.011C + 0.961 0.009C + 1.302
R² = 0.997 R² = 0.983 R² = 0.976
-0.213C+ 10.40 -0.152C + 9.509 -0.059C+ 5.956
R² = 0.998 R² = 0.983 R² = 0.968
0.811C + 5.615 0.538C + 9.913 0.459C + 9.154
R² = 0.989 R² = 0.990 R² = 0.986
-0.705C+9.274 -0.216C + 3.526 -0.130C + 5.027
R² = 0.990 R² = 0.993 R² = 0.979
0.749C + 5.339 0.497C + 9.463 0.407C + 8.289
R² = 0.989 R² = 0.988 R² = 0.987
-0.071C+ 6.757 -0.053C + 6.458 -0.025C + 5.110
R² = 0.998 R² = 0.982 R² = 0.967
0.026C+ 2.246 -0.032C + 1.087 0.028C + 1.197
R² = 0.991 R² = 0.968 R² = 0.945
0.034C + 1.247 -0.282C + 6.242 0.337C + 7.616
R² = 0.997 R² = 0.958 R² = 0.944
-2 -1
1
10 ,
0
κ
a
-1
Pa
R.10 ,
4
0.214C + 7.883
R² = 0.986
π. 10 , Pa -0.062C+ 3.855
1
0/3 -1/3
-1
m
s mol
-8
R² = 0.953
0.203C + 7.884
R² = 0.988
5
b. 10
m
3
1
.10 , m
1
-0.037C+ 5.778
R² = 0.979
0.009C + 1.118
R² = 0.903
-0.037C+ 5.778
R² = 0.979
0.013C + 0.692
R² = 0.969
0.153C + 4.223
R² = 0.931
L
f
2
(
α/f )cl
0 s m
.
1
4
2
-1
1
1
τ.10 ,s
3
0.098C + 5.348
R² = 0.965

Ultrasonic Speed and Related Acoustical Parameters
765
2
2
Z, R, b, (α/f ) and τ (except EA) (R = 0.90 – 0.999) increased linearly, while κ , π and
Cl
a
2
L (R = 0.947 - 0.995) decreased linearly with C. Linear increase or decrease of the said
f
parameters further confirmed the existence of powerful molecular interactions in the
.
9,10
solutions. Variation of U in the solution depends on intermolecular free path length
When ultrasonic waves are incident on the solution, the molecules get perturbed. Since
the medium has some elasticity and hence perturbed molecules regain their equilibrium
positions. When a solute is added to a solvent, its molecules attract certain solvent molecules
towards them. This phenomenon is known as compression. Every solvent has a limit for
compression and is known as limiting compressibility. Generally κ decreases with C. The
s
decrease of κ may be due to the aggregation of solvent molecules around solute molecules
s
supporting strong solvent-solute interactions.
According to Jacobson’s intermolecular free length theory for liquids, the molecules of
the liquid are assumed to be spherical and the average value of the distance that the
ultrasonic waves travel between the two molecules is called the intermolecular free path
length. Decrease of L with C further supported solvent-solute interactions. Due to solvent-
f
solute interactions, structural arrangement is considerably changed.
The dispersion of U in the system gives information about the characteristic time of the
13
relaxation process that causes the dispersion. According to Eyring rate process theory ,
variation of τ with temperature (T) can be given by
1
kT
h
∆G *
=
e −
τ
RT
Where k is the Boltzmann constant, h is the Planck’s constant, R is the gas constant, T is
*
the temperature and ∆G is the Gibb’s free energy of activation. Observed τ is due to
structural relaxation processes. Rearrangement of the molecules is a cooperative process
14
involving the movement of many molecules around a hole in the system . According to
*
above equation, the value of ∆G was calculated at different concentrations (Table 3) and
2
*
extrapolated to infinite dilution (R = 0.933 - 0.992). The least squares intrinsic values of ∆G
for CF, THF, EtOH, EA and DO systems are 3.195, 2.620, - 0.518, 3 490 and 4.148 kJ mol ,
-
1
*
respectively. Linear variation of ∆G with C indicates that the condensation in the phase and
absorption due to rearrangement of molecules are independent of C and are characteristic
physical properties of the solute only.
*
0
Table 3. Variation o f ∆G with concentration for different solvent systems at 35 C
*
G , Jmol
-1
∆
Conc, %
.925
CF
THF
EtOH
EA
DO
0
3200.16
3274.09
3288.25
3333.88
3394.50
For CF:
2693.79
2694.37
2795.78
2890.13
-494.55
-433.44
-371.84
-304.27
-233.02
3424.49
3296.90
3257.99
3005.18
2894.92
4206.19
4229.97
4424.38
4456.64
4593.32
1
.85
3
.7
.55
5
7
.4
3011.28
*
∆G = 26.33C + 3195, R² = 0.933
*
For THF: ∆G = 50.69C + 2620, R² = 0.978
*
For EtOH: ∆G = 38.80C - 518.1, R² = 0.992
*
∆G =-80.85C + 3490, R² = 0.959
For EA:
*
For DO: ∆G = 60.18C + 4148, R² = 0.958

7
66
P. H. PARSANIA et al.
Depending on the nature of the solvent and solute molecular interactions may lead to
contraction or expansion. Internal pressure of a solution is sensitive to molecular interactions
namely solvent-solute interactions, quantum mechanical dispersion forces and dielectric forces,
which play an important role in transport properties of the solutions. Decrease of π with C
suggested decrease of cohesive forces. Presence of molecular interactions in solutions is further
supported by nonlinear increase of solvation number (Sn) (Figure 1). Sn decreased linearly with
C in THF and increased nonlinearly with C in CF and EtOH, while it decreased nonlinearly with
C in DO and EA. Molecular interactions are influenced by the nature and structure of the solute,
pressure, concentration, nature of the substituent, etc. The presence of polar substituent in the
solute molecules lead to enhanced molecular interactions. Solvation causes compressibility of the
molecules. Thus solvation is a measure of structure forming or breaking tendency of the solutes.
The dipole-dipole interactions of the opposite type favor the structure formation; while of the
same type disrupt the structure formed previously. In the present case positive values of Sn
indicated predominant dipole-dipole interactions of the opposite type. In conclusion, derived
acoustical parameters suggested the presence of strong molecular interactions in the solutions.
DBNA possesses structure forming tendency in all the solvent systems.
Conc., %
Figure 1. Plots of Sn against concentration for DBNA solutions at 308.15 K
Acknowledgment
Authors (SPG and JPP) are thankful to UGC-SAP Grant (UGC Grant No.UGC
(
SAP)/6/DRS/2004, 1-4-2004) for financial help for M. Sc. dissertation.
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1

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