Thermo-acoustic investigations of molecular

interactions in CuO nano particles contained

aqueous solutions of some glycols
Cite as: AIP Conference Proceedings 2220, 020087 (2020); https://doi.org/10.1063/5.0001137
Published Online: 05 May 2020

Kuljeet Singh, Monika Dhiman, Pankaj Kumar, D. P. Gupta, D. P. Singh, and Arun Upmanyu

AIP Conference Proceedings 2220, 020087 (2020); https://doi.org/10.1063/5.0001137 2220, 020087

© 2020 Author(s).
Thermo-Acoustic Investigations of Molecular Interactions in
CuO Nano Particles Contained Aqueous Solutions of Some
Glycols
Kuljeet Singh1), Monika Dhiman2), Pankaj Kumar2), D. P. Gupta2), D. P. Singh3),
Arun Upmanyu2,a)

Department of Physics, SGGS College, Sector-26, Chandigarh, India.

1
2
Chitkara University Institute of Engineering and Technology, Chitkara University, Punjab, India.
3
Acoustics Research Center, 215 M. V. Blvd., Mississauga, L5A 1Y7, Ontario, Canada.

arun.upmanyu@chitkara.edu.in
a)

Abstract. This paper presents an extensive numerical work on the thermo acoustical properties of CuO nano-particles
contained aqueous solutions of ethylene-, propylene- and hexylene- glycols. Several thermo-acoustical parameters such as
Moelwyn-Hughes parameter, reduced volume, reduced compressibility, Sharma’s constants, Huggins parameter, isobaric,
isochoric, and isothermal acoustical parameters, fractional free volume, repulsive exponent etc, have been evaluated using
the data available in the literature. The variation of these parameters has also been investigated within the temperature
range 303.15K-313.15K. Using four different approaches, a comparative study of non-linearity parameter, B/A, has also
been done. The present analysis provides a deep insight into the nature, type and strength of particle-particle and particle-
fluid interactions prevalent in the systems under study.

INTRODUCTION
Nanofluids, being a new class of thermal fluids, have received much attention in experimental as well as theoretical
investigations. These exhibits minimal clogging in flow passage, high thermal conductivity, superior homogeneity
and long term stability over the conventional thermal fluids [1]. To improve the heat transfer capability of base fluids,
addition of nano particles is considered very useful. Water is a popular heat transfer fluid. However, in refrigeration
processes, it is necessary to mix water with either ethylene- or propylene- glycol to lower its freezing point and prevent
ice formation. Similarly, for car radiators or industrial heat exchangers, the boiling point of water can be raised by
mixing it with glycol-based fluids. The increasing recognition of energy saving and efficiency improvement
encourages the growing interest in nano-particles containing aqueous ethylene- or propylene- glycol-based fluids, for
their applications in various thermal systems. The nanofluids are also extensively used as a coolant in automotive
industry, nuclear reactors and in microchips of computers [2]. Recently, the use of nanofluids in drug delivery in
cancer imaging has gained impetus [3-4]. The nano particles of the CuO are of special interest because of their wide
use as efficient nanofluid in heat transfer applications [5-6]. The small band gap (1.21-1.51) CuO nanoparticles widen
its scope in the field of pigment and electronic fabrication [7]. In medical sciences, CuO nano particles are being
exploited for glucose sensing in blood serum [8].
The importance of various thermo-acoustical parameters of solutions is evident from their respective roles in the
interpretation and evaluation of various microscopic factors such as molecular order, molecular cohesion and
intermolecular interactions in such systems. Specifically, the non-linearity parameter, B/A, has consistently been
employed to extract information relating to internal pressure, clustering, inter-molecular spacing etc. Its importance
can be gauged by numerous experimental and theoretical studies on liquids using phenomenological [9]

3rd International Conference on Condensed Matter and Applied Physics (ICC-2019)

AIP Conf. Proc. 2220, 020087-1–020087-6; https://doi.org/10.1063/5.0001137
Published by AIP Publishing. 978-0-7354-1976-6/$30.00

020087-1
thermodynamic methods [10-11] and liquid state theories [12]. The insightful study of literature indicates that few
reports are available on the acoustical study on the nanofluids, to provide information on physico-chemical behavior
and molecular interactions prevalent in them. Keeping in mind the significance of thermoacoustical parameters and
novelty of nanofluids, an attempt has been made in the present investigation to explore the nature, type and strength
of molecular interactions prevalent in the cupric oxide contained aqueous solutions of glycols. Using experimental
data as available in literature, the current investigation is done at various concentrations of CuO nanoparticles in 10%
aqueous solutions of ethylene glycol, propylene glycol and hexalene glycol, in the temperature range 303.15 K to
313.15 K. Various thermoacoustical parameters of the systems are determined to understand these systems'
behaviour with concentration and temperature changes in them. In addition, the non-linearity parameter (B/A) has
been evaluated using four different approaches, i.e. thermoacoustical (two methods), Hartmann and Balizer [13] and
Ballou [13]. The obtained results are used to explain the variation in molecular interactions and structural adjustments
occurring therein.

THEORETICAL FORMULATION
For the present study, the required experimental ultrasonic velocity (U), density (d) and temperature (T) data has
been taken from literature [14]. Using these values several thermoacoustical parameters, for CuO nanopartilces
contained in 10% aqueous solutions of ethylene glycol, propylene glycol and hexalene glycol, at 303.15, 308.15 and
313.15 K, are evaluated. These thermal acoustical parameters are determined using theoretical formulation as reported
by Upmanyu et al [15]. The non-linearity parameter B/A has been computed using four different methods viz.
Hartmann and Balizer, Ballou, and thermoacoustical methods, as reported by Ranjan Dey et al.[16].

RESULTS AND DISCUSSION

The evaluated thermo-acoustical parameters viz Moelwyn-Hughes parameter (C1), reduced volume ( V~ ), Sharma’s
constants (S0, S*, S*0), Huggins parameter (F), isobaric (K), isochoric (K”), and isothermal (K’) acoustical parameters,
fractional free volume (f), and repulsive exponent (n), for different wt% concentrations of CuO nanoparticles in the
10% aqueous solutions of ethylene glycol [EG + (10%) H 2O], propylene glycol [PG + (10%) H2O] and hexylene
glycol [HG + (10%) H2O] at 303.15 K, 308.15 K and 313.15 K have been reported as Table 1. All the results are in
SI units except stated otherwise. The formulae required for the computation of the various parameters have been taken
from literature [15].

TABLE 1. Thermoacoustical parameters of Cuo Nano particles contained aqueous solutions of some glycols in the temperature
range of 303.15 K-313.15 K at various weight concentrations of CuO.

T(K) Wt. C1 ~ So So* S* F K K" K' n f

V
CuO+EG+H2O
0.00 7.9939 1.2542 1.1177 1.1454 1.4102 2.0800 3.4969 0.1413 3.6383 11.9816 0.2156
0.02 7.9965 1.2540 1.1177 1.1454 1.4098 2.0804 3.4982 0.1403 3.6385 11.9894 0.2156
303.15

0.04 7.9989 1.2538 1.1177 1.1453 1.4095 2.0808 3.4994 0.1394 3.6388 11.9966 0.2156
0.06 7.9969 1.2540 1.1177 1.1453 1.4098 2.0805 3.4985 0.1401 3.6386 11.9908 0.2156
0.08 7.9952 1.2541 1.1177 1.1454 1.4100 2.0802 3.4976 0.1408 3.6384 11.9856 0.2156
0.10 7.9940 1.2542 1.1177 1.1454 1.4102 2.0800 3.4970 0.1413 3.6383 11.9819 0.2156
0.00 7.9568 1.2570 1.1174 1.1468 1.4156 2.0742 3.4784 0.1560 3.6344 11.8704 0.2158
0.02 7.9591 1.2568 1.1174 1.1467 1.4153 2.0745 3.4795 0.1551 3.6347 11.8773 0.2158
0.04 7.9617 1.2566 1.1174 1.1466 1.4149 2.0750 3.4808 0.1541 3.6349 11.8850 0.2158
308.15

0.06 7.9602 1.2567 1.1174 1.1467 1.4151 2.0747 3.4801 0.1547 3.6348 11.8806 0.2158
0.08 7.9585 1.2568 1.1174 1.1467 1.4154 2.0745 3.4793 0.1553 3.6346 11.8756 0.2158
0.10 7.9575 1.2569 1.1174 1.1468 1.4155 2.0743 3.4788 0.1557 3.6345 11.8726 0.2158

020087-2
TABLE 1 (continued)
0.00 7.9229 1.2596 1.1171 1.1481 1.4208 2.0687 3.4615 0.1695 3.6309 11.7687 0.2159
0.02 7.9233 1.2595 1.1171 1.1481 1.4207 2.0688 3.4617 0.1693 3.6310 11.7699 0.2159
0.04 7.9255 1.2594 1.1171 1.1480 1.4204 2.0691 3.4627 0.1685 3.6312 11.7764 0.2159
313.15

0.06 7.9237 1.2595 1.1171 1.1480 1.4206 2.0688 3.4619 0.1692 3.6310 11.7712 0.2159
0.08 7.9223 1.2596 1.1171 1.1481 1.4209 2.0686 3.4612 0.1697 3.6309 11.7670 0.2159
0.10 7.9213 1.2597 1.1171 1.1481 1.4210 2.0684 3.4607 0.1701 3.6308 11.7639 0.2159
CuO+PG+H2O
0.00 8.0018 1.2536 1.1177 1.1452 1.4091 2.0812 3.5009 0.1382 3.6391 12.0054 0.2156
0.02 8.0034 1.2535 1.1177 1.1451 1.4088 2.0814 3.5017 0.1376 3.6393 12.0101 0.2156
0.04 8.0049 1.2534 1.1177 1.1450 1.4086 2.0817 3.5024 0.1370 3.6394 12.0146 0.2155
303.15

0.06 8.0038 1.2535 1.1177 1.1451 1.4088 2.0815 3.5019 0.1374 3.6393 12.0115 0.2155
0.08 8.0029 1.2535 1.1177 1.1451 1.4089 2.0814 3.5015 0.1378 3.6392 12.0087 0.2156
0.10 8.0023 1.2536 1.1177 1.1451 1.4090 2.0813 3.5012 0.1380 3.6391 12.0069 0.2156
0.00 7.9623 1.2566 1.1174 1.1466 1.4148 2.0751 3.4812 0.1538 3.6350 11.8870 0.2157
0.02 7.9638 1.2565 1.1174 1.1465 1.4146 2.0753 3.4819 0.1533 3.6351 11.8913 0.2157
0.04 7.9652 1.2563 1.1174 1.1465 1.4144 2.0755 3.4826 0.1527 3.6353 11.8956 0.2157
308.15

0.06 7.9643 1.2564 1.1174 1.1465 1.4145 2.0754 3.4821 0.1531 3.6352 11.8929 0.2157
0.08 7.9634 1.2565 1.1174 1.1466 1.4147 2.0752 3.4817 0.1534 3.6351 11.8903 0.2157
0.10 7.9628 1.2565 1.1174 1.1466 1.4148 2.0751 3.4814 0.1536 3.6350 11.8885 0.2157
0.00 7.9242 1.2595 1.1171 1.1480 1.4206 2.0689 3.4621 0.1690 3.6311 11.7725 0.2159
0.02 7.9253 1.2594 1.1171 1.1480 1.4204 2.0691 3.4626 0.1686 3.6312 11.7758 0.2159
313.15

0.04 7.9265 1.2593 1.1171 1.1479 1.4202 2.0693 3.4632 0.1681 3.6313 11.7794 0.2159
0.06 7.9256 1.2594 1.1171 1.1480 1.4204 2.0691 3.4628 0.1684 3.6312 11.7767 0.2159
0.08 7.9247 1.2594 1.1171 1.1480 1.4205 2.0690 3.4623 0.1688 3.6311 11.7740 0.2159
0.10 7.9242 1.2595 1.1171 1.1480 1.4206 2.0689 3.4621 0.1690 3.6311 11.7725 0.2159
CuO+HG+H2O
0.00 7.9963 1.2540 1.1177 1.1454 1.4099 2.0804 3.4982 0.1404 3.6385 11.9890 0.2156
0.02 7.9973 1.2540 1.1177 1.1453 1.4097 2.0805 3.4987 0.1400 3.6386 11.9920 0.2156
303.15

0.04 7.9982 1.2539 1.1177 1.1453 1.4096 2.0807 3.4991 0.1396 3.6387 11.9947 0.2156
0.06 7.9975 1.2539 1.1177 1.1453 1.4097 2.0806 3.4988 0.1399 3.6386 11.9926 0.2156
0.08 7.9970 1.2540 1.1177 1.1453 1.4098 2.0805 3.4985 0.1401 3.6386 11.9909 0.2156
0.10 7.9966 1.2540 1.1177 1.1453 1.4098 2.0804 3.4983 0.1403 3.6385 11.9897 0.2156
0.00 7.9601 1.2567 1.1174 1.1467 1.4152 2.0747 3.4801 0.1547 3.6348 11.8803 0.2158
0.02 7.9610 1.2567 1.1174 1.1466 1.4150 2.0749 3.4805 0.1543 3.6349 11.8831 0.2158
308.15

0.04 7.9620 1.2566 1.1174 1.1466 1.4149 2.0750 3.4810 0.1540 3.6350 11.8859 0.2158
0.06 7.9614 1.2566 1.1174 1.1466 1.4150 2.0749 3.4807 0.1542 3.6349 11.8843 0.2158
0.08 7.9609 1.2567 1.1174 1.1467 1.4150 2.0748 3.4804 0.1544 3.6348 11.8827 0.2158
0.10 7.9605 1.2567 1.1174 1.1467 1.4151 2.0748 3.4802 0.1546 3.6348 11.8814 0.2158
0.00 7.9249 1.2594 1.1171 1.1480 1.4205 2.0690 3.4625 0.1687 3.6312 11.7748 0.2159
0.02 7.9258 1.2593 1.1171 1.1480 1.4203 2.0692 3.4629 0.1684 3.6312 11.7773 0.2159
313.15

0.04 7.9266 1.2593 1.1171 1.1479 1.4202 2.0693 3.4633 0.1680 3.6313 11.7798 0.2159
0.06 7.9261 1.2593 1.1171 1.1480 1.4203 2.0692 3.4630 0.1682 3.6313 11.7782 0.2159
0.08 7.9255 1.2594 1.1171 1.1480 1.4204 2.0691 3.4627 0.1685 3.6312 11.7764 0.2159
0.10 7.9252 1.2594 1.1171 1.1480 1.4204 2.0691 3.4626 0.1686 3.6312 11.7755 0.2159
The perusal of Table 1 indicates that C1 values remains fairly constant across the given range of wt% concentration of
CuO at constant temperature in all the system under study. However, it may be pointed this constancy of C1 isn’t
stringent enough, as it shows a minute but consistent increase till 0.04% wt. concentration, and then decrease with

020087-3
further increase in concentration of CuO nanoparticles. As expected, C1 decreases gradually with rise in the
temperature from 303.15 to 313.15 K for the systems under study. The Moelwyn-Hughes parameter (C1) signifies a
nonlinear variation of the volume expansivity and associating tendency of the liquid mixture. The reduced volume (
~
V ) remains fairly constant with increase in wt. concentration of CuO nanoparticles and increase with rise in
temperature 303.15 to 313.15 K for all the systems [Table 1].

CuO+EG+H2O CuO+PG+H2O CuO+HG+H2O

7.176
7.250 7.170
7.150 303.15K 303.15K
303.15K
(B/A)1

7.221 7.155
7.124 308.15K 308.15K
308.15K
7.192 7.140
7.098
313.15K 313.15K
313.15K 7.163 7.125

8.274
8.253 303.15K
303.15K
8.325 8.260 303.15K
(B/A) 2

8.232 308.15K
8.300 8.246
308.15K 308.15K
8.211 313.15K
8.275 8.232 313.15K
8.190 313.15K
8.250
7.374 7.375
7.376 303.15K
303.15K
7.374 7.374 303.15K
7.376
308.15K 308.15K
(B/A) 3

7.373 7.374 308.15K

7.375
313.15K
313.15K 7.373 7.374
7.375 313.15K

7.372
8.018 303.15K
303.15K 7.998
8.00 303.15K
7.980
308.15K 7.955
(B/A)4

7.96
308.15K
7.942 308.15K
7.912
7.92
7.904 313.15K
313.15K
7.869
7.88 313.15K
-0.02 0.00 0.02 0.04 0.06 0.08 0.10 0.12 -0.02 0.00 0.02 0.04 0.06 0.08 0.10 0.12 -0.02 0.00 0.02 0.04 0.06 0.08 0.10 0.12

Concentration (wt(%))
FIGURE 1. Non-linearity parameter B/A for CuO+EG+H2O, CuO+PG+H2O and CuO+HG+H2O nanofluids, computed by
four different approaches (B/A)1 (Balou approach), (B/A)2 (Hartmann approach), (B/A)3 (Thermoacoustic-I approach) and
(B/A)4 (Thermoacoustic-II approach) at various temperatures and concentrations.

The fractional free volume (f) also exhibit similar behavior for all the nanofluids under study. The slight increase in
~
the values of V and f, with rise in temperature of the solution, is indicative of the enhancement of randomness due to
increase in the mobility of the molecules in the nanofluid [17]. The average value of f (~0.198) for all the samples
under study are consistent with the reported f values for saturated hydrocarbons [18], polymers [19], quasi spherical
molecular liquids [20], and are greater than those reported for fluorocarbons (f = 0.15)[21] and ternary mixtures (f =
0.17) [22]. The value of n is repulsive term exponent in Lennard-Jones potential. The increase in the value of n
indicates the dominance of attractive forces over repulsive forces. In present study, the repulsive component (n) is
nearly constant as evident from Table 1,with rise in concentration of CuO nanaparticles in solution and slightly
increase with rise in temperature for all the systems under study. The values lie in the expected range ~ 4.6-19,
reported for the liquids, fluorocarbons, polymers, and PAN/Clay composites [23].
The value of the S0, remains fairly constant within the acceptable range of experimental error. The estimated value
of the S0 in general lies in the range 1.11 ± 0.01. These values are in good agreement with results reported by Sharma
[24-25]. The calculated value of S* are 1.41 ± 0.01 corresponds with the value expected of polymers (~ 1.5), as
reported by Reddy et al [26], while the average value of So* is estimated to be 1.14 ± 0.01. The values of K exhibits a

020087-4
decreasing pattern with increase in temperature for CuO+EG+H 2O. Similar trend is exhibited for CuO+PG+H2O and
CuO+HG+H2O, solutions respectively. It remains approximately constant, within the range of concentrations under
study. A similar behavior is exhibited for CuO+PG+H 2O and CuO+HG+H2O solutions. As expected the behavior of
K¢ is similar to K for the given concentrations and temperature.
Furthermore, the non-linearity parameter B/A has been computed by different approaches viz. Hartmann and
Balizer, Ballou and two thermoacoustical methods. The graphical variation of B/A values evaluated via these four
approaches is shown in Fig. 1. The perusal of Fig. 1 indicates that the computed values of B/A exhibits the expected
decrease with increase in temperature for all the different solutions. The close look of Fig. 1 reveals that B/A value
computed by all the different approaches viz; (B/A)1, (B/A)2, (B/A)3 and (B/A)4 exhibit initial decrease with increase
in the wt% concentration of the solution under study, till 0.04% of CuO nanoparticles and thereafter the value of B/A
increases till 0.1% wt. concentration. The B/A value computed using (B/A)4 does not vary much with rise in wt
concentration of CuO nano particles in these nanofluids. It has been further noticed that the slope of descent increase
with increase in the chain of alkyl group as EG < PG < HG. It may be understood in terms of structural changes
occurring with increase in the size of the added alkyl group. Also, it is worth noting that the values computed by
method (ii) are on the higher side, for all the three temperatures, as compared to those computed by method (i). This
may be attributed to the contribution coming from the pseudo Gruneisen parameter [16]. The initial decrease in the
B/A value, with increase in temperature for all the systems, is indicative of decrease in intermolecular modes of
vibration and anharmonicity. It also shows the associating nature and presence of interacting intermolecular forces in
the given aqueous solution. Thereafter the decrease in B/A indicates the increase in intramolecular modes of vibrations
and harmonicity in liquid state. This indicates the dissociating nature in aqueous solution and is attributed to weak
intermolecular forces.

CONCLUSION

The observed variations in the estimated values of thermo-acoustical parameters with wt. concentrations and
temperature are found to be quite consistent. A miniscule decrease with increase in wt. concentration of CuO
nanoparticles up to 0.04%, followed by an opposite trend has been observed for several of the thermo physical
parameters studied here. This may be attributed to enhanced intermolecular interactions between CuO nanoparticles
and Glycol (aq) with initial increase in wt. concentration up to 0.04%. Further addition of CuO, and implied weakening
of intermolecular interactions among constituents of the solutions, is possibly due to the dispersion forces present in
the systems, playing a dominant role. These parameters also show an expected but regular increasing/decreasing
tendency with temperature variation from 303.15 – 313.15 K, implying a decrease in intermolecular modes of vibration
and anharmonicity in liquid mixture with enhanced temperature. The increase in temperature manifests into
intermolecular dissociation and structure destruction. The observed pattern in the variation of these parameters with
temperature thus provides an insight into the nature of cohesive forces. The variation of these parameters in
CuO+EG+H2O, CuO+PG+H2O and CuO+HG+H2O solutions, marks a very small but consistent increase/decrease for
glycols as the hydrocarbon are increased i.e. EG<PG<HG. This might be attributed to non-zero dipole moment of
glycols having odd number of hydrocarbons. It is interesting to note that fractional change with concentration values
for these parameters is diminished as the size of non-polar alkyl group changes from EG to HG solutions. It might be
interpreted in terms of enhanced steric hindrance owing to larger non-polar alkyl group.

REFERENCES

1. M. Chandrasekar , S. Suresh and A. C. Bose, Exp Therm Fluid Sci 34(2), 210-216(2010).
2. Yu, W., France, D. M., Routbort, J. L., and Choi, S. U. S., Heat Transfer Eng., 29, 432–460 (2008).
3. C. Kleinstreuer, J. Li, and J. Koo, Int. J. Heat Mass Transf. 51, 5590–5597 (2008).
4. D. Bica, L. V´ek´as, M. V. Avdeev, et al., J. Magn. Magn. Mater. 311, 17–21 (2007).
5. P. O. Larsson, and A. Andersson, J. Catal. 179(1), 72-89(1998).
6. V. Chikán, Á. Molnár, and K. Balazsik, J. Catal. 184(1), 134-143(1999).
7. O. Zabihi and S. Ghasemlou, Int J Polym Anal Ch 17(2), 108-121(2012).
8. Y. Li, Y. Wei, G. Shi, Y. Xian and L. Jin, Electroanalysis 23(2), 497-502(2011).
9. C. A. Cain, H. Nishiyama and K. Katakura, J. Acoust. Soc. Am. 80, 685–688(1986).
10. H. Endo, J. Acoust. Soc. Am. 83, 2043–2046(1988).
11. T. Jie, D. Yanwu and Z. Hegyuan, Kexue Tongbao 33, 1511–1517(1998).

020087-5
12. J. Jugan and M. Abdulkhadar, J. Mol. Liq. 100, 212–227(2002).
13. J. D. Pandey, R. Dey, V. Sanguri, J. Chhabr and T. Nautiyal, Pramana- J. Phys. 65, 535–540(2005).
14. M. Kumar, N. Sawhney, A. K. Sharma and M. Sharma, Ind. J. Pure Appl. Phys. 55(8), 574-582(2017).
15. A Upmanyu and D P Singh, International J. Res. Pure Appl. Phys. 3(3): 23-26(2013)
16. Ranjan Dey and Pranjal Kumar, Acta Acust united Ac 96, 8-13(2011).
17. S.A.Tiwari and S .Rajagopalan, Acoust. Lett. 14, 92-97(1990).
18. D. P. Singh and A. P. Singh, Acoustics 81, 177(1995).
19. D. P. Singh and B. Singh, Ind. J. Phys. 66A(5), 677-681(1992).
20. B. K. Sharma, J. Pure & Appl. Phys. 23, 247-251(1987).
21. B. K. Sharma, Ind. J Pure Appl. Phys. 23, 509-513(1985).
22. J. Poongodi and R. Sabesan, J. Pure Appl. Ultrason. 17, 72-74(1995).
23. D. P. Singh and Arun Upmanyu, J. Polym. Biopolym. Phys. Chem. 2/4, 73-77(2014).
24. B. K. Sharma, Polymer 24, 314 (1983).
25. B. K. Sharma, Pramana 26, 223 (1986).
26. R. R. Reddy and M. M. Murthty, Acoust. Lett. 10, 128(1987).

020087-6