Ultrasonic Velocity, Density, and Acoustic Properties of Aqueous Ethylene Glycol Solutions in Methanol, Ethanol, and 1-Propanol at 308.15 K

Ultrasonic Velocity, Density, and Acoustic Properties of Aqueous Ethylene Glycol Solutions in Methanol, Ethanol, and 1-Propanol at 308.15 K

M. Kondaiah (1)* and K. Sreekanth (2),

(1) Department of Physics, Tara Govt. College (A), Sangareddy, 502 001, Sangareddy Dist., Telangana, India

(2) Department of Physics, PBN College, Nidubrolu, 522 124, Guntur District, AP, India

*Corresponding Author: Dr M Kondaiah;

Abstract:

The ultrasonic velocities (u) and densities () of 0.3 and 0.9 m aqueous ethylene glycol solutions in methanol, ethanol, and 1-propanol have been measured over the entire composition range at 308.15 K. The ultrasonic velocity increases with increasing alkanol mole fraction in the range, 0 < x <0.15 followed by a decrease at higher mole fractions. From the experimental data, the deviation in ultrasonic velocity (u), deviation in isentropic compressibility (ks), excess intermolecular free length ( LE ), and excess

acoustic impedance (ZE) have been calculated to investigate the nature of molecular interactions in the

mixtures. The negative values of ks, and LE , together with the positive values of u and ZE, indicate the presence of significant intermolecular interactions in the investigated solutions. The excess properties have been correlated using the RedlichKister polynomial equation, and the corresponding standard deviations have been evaluated to assess the quality of the correlations. Furthermore, the experimental ultrasonic velocities have been compared with those predicted by various theoretical models, including the Nomoto, Van DaelVangeel, impedance, Junjie, Jacobson, and Rao (specific sound velocity) relations, to evaluate their applicability to the studied systems.

Keywords: Ultrasonic velocity, Excess/Deviation properties, Redlich-Kister type polynomial, Acceptor- donor interactions, Hydrogen bonding, Ultrasonic empirical relations

1. 1. Introduction

      The characteristics of liquid mixes and solutions can be modified progressively within a feasible range by adjusting the concentration until an ideal value of a certain parameter is reached. The unadulterated liquids exhibit no such adaptability. The examination of characteristics of liquid mixes and solutions has direct relevance in the chemical, biochemical, and medical sectors [1-5]. The velocity of sound is acutely responsive to the arrangement and interactions within liquid systems, as it is intrinsically linked to the binding forces among the medium’s components [6]. The assessment of sound velocity in liquids facilitates the identification of valuable acoustic and thermodynamic characteristics that exhibit significant sensitivity to molecular interactions [7-16]. Consequently, these measurements are valuable for examining the characteristics and intensity of molecular interactions in liquid mixtures.

      Mixtures of water and alcohol exhibit distinct maxima and minima in their thermodynamic and acoustic characteristics at low concentrations of alcohol [17-25]. The emergence of such maxima/minima in certain aqueous electrolyte solutions [26] and in non-aqueous solutions [27,28] has also been documented in scholarly articles. Masso Sakura [29] documented the partial molar volumes of ethylene glycol and aqueous solutions at various temperatures: 15, 25, 35, and 450C. Pal and Wazir Singh [30] reported the sound velocities and viscosities in aqueous poly(ethylene glycol) solutions at temperatures of

      303.15 K and 308.15 K. Kanhekar et al [31] investigated the thermodynamic characteristics of glycine in aqueous solution across several temperatures. Thirumaran and Sathish [32] conducted investigations on

      the molecular interionic interactions of divalent transition metal sulphates in aqueous ethylene glycol across various temperatures. Peiming et al. [33] investigated the thermodynamic characteristics of sand transport in ethylene glycol and its combinations with water and electrolytes. Zafarani-Moattar et al [34] documented the volumetric and transport properties of glycol+water solutions. We have previously documented the volumetric and viscometric characteristics of aqueous solutions of ethylene glycol/propylene glycol in alkanols [35,36] and propanoic acid combined with an equimolar combination of N,N-dimethyl formamide and alkanols at different temperatures [37].

      Keeping in view, the ultrasonic and volumetric study of molecular interactions in the solutions of aqueous ethylene glycol with methanol/ ethanol/1-propanol is presented in this chapter at 308.15 K. The properties like, deviation in ultrasonic velocity (u), deviation in isentropic compressibility (ks), excess

      f

      inter molecular free length ( LE ) and excess acoustic impedance (ZE) have been calculated using the experimental results of ultrasonic velocity and density. The variation of these properties over the entire composition range yields the information about molecular interaction in these systems. The excess/deviation properties are fitted to Redlich-Kister type polynomial equation. Besides, the experimental values of ultrasonic speed for all the aqueous solutions measured and compared with the theoretically estimated values using different empirical relations such as, Nomotos, Van Dael and Vangeels ideal mixing relation,, Impedance dependence relation, Junjies relation, Raos specific sound velocity and Jacobsons equations. The percentage deviations of theoretical velocities from experimental values have been calculated. The corresponding standard deviations are also computed. The deviation of ultrasonic velocity from its experimental value is further utilized to study molecular interactions. Special types of polynomial equations are fitted to experimental data.

   2. Experimental

      The substances utilised in the current investigation include ethylene glycol (purity mass fraction 0.99), methanol (purity mass fraction 0.99), ethanol (purity mass fraction 0.99) sourced from Changshu Yangyuan Chemicals, China, and 1-propanol (purity mass fraction 0.99) of G.R Grade procured from LOBA Chemicals, Mumbai, India. These were subsequently refined using conventional techniques [38]. The 0.3 m and 0.9 m aqueous solutions of ethylene glycol are formulated using triply distilled deionised water. These formulations are subsequently employed to create liquid blends containing methanol, ethanol, and 1-propanol, ensuring comprehensive coverage of the composition spectrum. All mixes have been formulated in specially crafted glass containers with airtight seals, and sufficient measures have been implemented to reduce evaporation losses. The measurement of solutions was conducted utilising a METTER TOLEDO (Swiss manufacture) ABB5-S/FACT digital balance with a precision of 0.01mg.

      The ultrasonic velocities and densities of the pure liquids examined in this study are recorded at 308.15 K and are presented in Table 1 alongside the existing literature data [39-46].

      Table 1 Comparison of ultrasonic velocities (u) and densities () of pure liquids with the

      corresponding literature values at 308.15 K

      	Liquid	u/ m.s-1			/ kg.m-3
      		Expt.	Lit.		Expt.	Lit.
      Water		1520.22	1519.3639		994.06	994.1040
      Ethylene glycol	1632.32	1632.1041		1105.85	1103.1041
      Methanol		1072.65	1072.4042		776.63	776.7042
      Ethanol		1115.10	1111.0043		776.49	776.4144
      1-propanol		1175.60	1175.1045		791.41	791.4046

   3. Results and discussion

The variation of ultrasonic velocity (u) at two different molalities of aqueous ethylene glycol with mole fraction of methanol/ethanol/1-propanol is shown in Figures 1 3 respectively. The ultrasonic velocity increases in the 0 < x <0.15 mole fraction of alkanol and it is found to decrease beyond 0.15 mole fraction of alkanol. The ultrasonic velocity shows a maximum value at about 0.15 m mole fraction of methanol/ethanol/1-propanol for 0.3 m and 0.9 m aqueous solutions of ethylene glycol. Water and ethylene glycol are both associated liquids, through the formation of hydrogen bonding. When ethylene glycol is added to water, association between ethylene glycol and water molecules takes place through hydrogen bonding which is shown in schema I. This leads to the increase of open structures in the solution as diol acts as a structure maker.

(a)

(b)

– – – -H O – – – – H O – – – – H O – – – –

– – – -H O H

O – – – – H

O – – – –

H

H H R R R

(c)	CH2	: : O H	(d)	H	H
	CH2	O H : :	CH2	– – – -H O H :	O – – – –
CH2	O	: : H	CH2	:
				: – – – -H O H	O – – – –
CH2	O	H
		:
		:		H	H

:

O H

O H

Schema I : Representation of inter molecular interactions in (a) water (b) alcohols (c) ethylene glycol (d) between water and ethylene glycol molecules

The maximum value in ultrasonic velocity is observed in the low concentration region of alkanols added to the aqueous ethylene glycol. The origin of maximum in the low concentration region of alkanol is due to long-range order in water giving rise to hydrogen bonded structure [17]. Such a structure possesses many cavities and these cavities can accommodate solute such as alkanol molecules. This is further supported by the observed large differences in the molar volume between the components of the solution. As alkanol is added to the aqueous ethylene glycol, alkanol molecules go on occupying the cavities created in the aqueous ethylene glycol structure. This gives rise to a denser packing of molecules resulting in the increase of ultrasonic velocity of solutions. This process continues until all the cavities are filled with solute molecules. Further addition of alkanol, leads to gradually for the formation of unassociated monomer structures in the solution and at the same time there are some alkanol molecules which disrupts the hydrogen bonding existing between the water + ethylene glycol molecules resulting in unassociated ethylene glycol molecules in the solution. Thus, the structure of solution becomes more and more loosely packed by increasing the concentration of alkanol molecules. As a result, the ultrasonic velocity in the solution decreases. This might be the possible reason to explain the ultrasonic velocity behaviour in the present investigated solutions.

—-o.3m

—-o.9m

1700

1600

1500

-“! 1400

E

=

1300

1200

1100

1000

-0.1 0.2 0.5

0.8

1.1

mole fr-action of methanol

Figure 1 Vari…:1.tion oC ultrasonic velocity (u) in the mixtures or methanol wit”h aqueous ethylene glycol

—-o.3m

—-o.9m

1700

1600

1500

1400

E

=

1300

1200

1100

1000

-0.1 0.2 0.5

mole fr-action of ethanol

0.8 1.1

Figure 2 Variation of ultrasonic velocicy (u) in the rnixtures of ethanol –with aqueous ethylene glycol

The deviation in ultrasonic velocity (u), deviation in isentropic compressibility (ks), excess

f

inter molecular free length ( LE ) and excess acoustic impedance (ZE) have been calculated from the

L

f

experimental results of ultrasonic velocity (u) and density () and the data for the above properties are listed in Tables 2 – 4 for methanol, ethanol and 1-propanol with aqueous ethylene glycol solution respectively.

The values of u, ks,

E and ZE have been fitted to Redlich-Kister type polynomial equation

[47,48]. The Redlich-Kister coefficients and the corresponding standard deviations of all the liquid solutions have been presented in Table 5.

The sign and magnitude of u, and ks played an important role to describe the molecular rearrangement and is resulted to the existence of molecular interactions among the component molecules in the solutions. Generally, negative values of u and positive values of ks indicate dispersion forces due to weak interactions where as positive values of u and negative values of ks indicating strong interactions [45, 49]. The isentropic compressibility is a measure of ease with which the system can be compressed. Positive values of u and negative values of ks are observed in the present investigated systems. The negative values of ks indicate the molecules in the solutions are less compressible than that of the pure liquids during its formation. Therefore, such negative values of ks indicate strong interactions between component molecules. The strong interactions include inter molecular hydrogen bonding between alkanol and water + ethylene glycol molecules, dipole-induced dipole interactions, interstitial accommodation of smaller molecules in to bigger molecules. The internal structural properties of ethylene glycol and alcohols suggest that the observed behaviour is attributed to the intermolecular interactions between OH group of the alcohol and the oxygen atom (-O-) of the

ethylene glycol. When alkanols are added to the aqueous ethylene glycol the existing inter molecular hydrogen bonds between water and ethylene glycol molecules and intra molecular hydrogen bonds in water and ethylene glycol may be broken and new hydrogen bonds might be formed in the mixtures. Such similar studies were reported by Amalendu Pal et al [41] in aqueous solutions of glycols and Kinart et al [50] glycols with 2-ethoxyethanol.

f

Table 2 Calculated properties of deviation in ultrasonic velocity, u, deviation in isentropic

compressibility, ks, excess intermolecular free length,

LE , excess acoustic impedance, ZE with

f

mole fraction of methanol (x) in aqueous ethylene glycol solution at T = 308.15 K

x volume fraction u/ ks/

LE / ZE/

of methanol m.s-1 10-10Pa-1 10-10m 106kg.m-2.s-1

0.3 m aqueous ethylene glycol

0.0000	0.0000	0.00	0.0000	0.0000	0.0000
0.0987	0.0981	69.32	-0.7406	-0.0296	0.0670
0.1968	0.1937	124.27	-1.4004	-0.0558	0.1249
0.3009	0.2937	166.15	-1.9896	-0.0784	0.1669
0.3915	0.3803	199.59	-2.4663	-0.0966	0.1967
0.4944	0.4774	200.68	-2.7687	-0.1061	0.1980
0.5947	0.5707	185.88	-2.9005	-0.1091	0.1871
0.7001	0.6713	154.25	-2.7953	-0.1022	0.1564
0.7963	0.7652	130.64	-2.6003	-0.0933	0.1330
0.8932	0.8744	67.19	-1.6557	-0.0555	0.0637
1.0000	1.0000	0.00	0.0000	0.0000	0.0000
0.9 m aqueous ethylene glycol
0.0000	0.0000	0.00	0.0000	0.0000	0.0000
0.0986	0.0978	66.21	-0.7285	-0.0290	0.0668
0.1937	0.1905	122.68	-1.3816	-0.0551	0.1247
0.2965	0.2885	165.73	-1.9781	-0.0785	0.1708
0.3956	0.3816	202.40	-2.5076	-0.0992	0.2086
0.4939	0.4741	205.42	-2.8117	-0.1091	0.2103
0.5969	0.5717	188.64	-2.9358	-0.1108	0.1910
0.6972	0.6672	168.59	-2.9326	-0.1083	0.1705
0.7957	0.7634	140.71	-2.7214	-0.0984	0.1425
0.8934	0.8765	63.85	-1.6140	-0.0535	0.0585
1.0000	1.0000	0.00	0.0000	0.0000	0.0000

f

Table 3 Calculated properties of deviation in ultrasonic velocity, u, deviation in isentropic

compressibility, ks, excess intermolecular free length,

LE , excess acoustic impedance, ZE with

f

mole fraction of ethanol (x) in aqueous ethylene glycol solution at T = 308.15 K

x volume fraction u/ ks/

LE / ZE/

of ethanol m.s-1 10-10Pa-1 10-10m 106kg.m-2.s-1

0.3 m aqueous ethylene glycol
0.0000	0.0000	0.00	0.0000	0.0000	0.0000
0.0579	0.0576	62.97	-0.5059	-0.0219	0.0564
0.1485	0.1456	139.49	-1.1839	-0.0512	0.1329
0.2275	0.2216	171.74	-1.5783	-0.0667	0.1597
0.3038	0.2931	165.85	-1.7650	-0.0723	0.1565
0.4045	0.3884	152.14	-1.9199	-0.0757	0.1397
0.5094	0.4893	138.43	-2.0143	-0.0766	0.1203
0.6114	0.5869	113.52	-1.9505	-0.0720	0.0982
0.7413	0.7132	98.13	-1.8745	-0.0681	0.0872
0.8611	0.8434	40.48	-1.0662	-0.0358	0.0311
1.0000	1.0000	0.00	0.0000	0.0000	0.0000
0.9 m aqueous ethylene glycol
0.0000	0.0000	0.00	0.0000	0.0000	0.0000
0.0703	0.0696	77.13	-0.6220	-0.0272	0.0741
0.1447	0.1420	132.13	-1.1278	-0.0485	0.1254
0.2265	0.2202	166.62	-1.5468	-0.0653	0.1569
0.3562	0.3395	181.83	-2.0024	-0.0827	0.1813
0.4675	0.4429	158.21	-2.1139	-0.0842	0.1577
0.5585	0.5264	139.95	-2.1104	-0.0824	0.1345
0.6578	0.6243	119.20	-2.0762	-0.0786	0.1162
0.7845	0.7500	91.16	-1.8284	-0.0676	0.0902
0.8593	0.8397	33.95	-1.0017	-0.0337	0.0272
1.0000	1.0000	0.00	0.0000	0.0000	0.0000

f

Table 4 Calculated properties of deviation in ultrasonic velocity, u, deviation in isentropic

compressibility, ks, excess intermolecular free length,

LE , excess acoustic impedance, ZE with

f

mole fraction of 1-propanol (x) in aqueous ethylene glycol solution at T = 308.15 K

x volume fraction u/ ks/

LE / ZE/

of 1-propanol m.s-1 10-10Pa-1 10-10m 106kg.m-2.s-1

0.3 m aqueous ethylene glycol
0.0000	0.0000	0.00	0.0000	0.0000	0.0000
0.0548	0.0545	71.30	-0.4835	-0.0222	0.0617
0.1167	0.1150	100.97	-0.7649	-0.0339	0.0862
0.1886	0.1852	71.22	-0.7197	-0.0287	0.0467
0.2606	0.2553	61.98	-0.7607	-0.0285	0.0297
0.3448	0.3373	45.64	-0.7440	-0.0258	0.0087
0.4456	0.4371 26.14	-0.6583	-0.0204	-0.0157
0.5471	0.5387	-5.31	-0.3874	-0.0083	-0.0457
0.6934	0.6860	-17.58	-0.1577	-0.0001	-0.0539
0.8179	0.8106	-2.19	-0.2662	-0.0062	-0.0231
1.0000	1.0000	0.00	0.0000	0.0000	0.0000
0.9 m aqueous ethylene glycol
0.0000	0.0000	0.00	0.0000	0.0000	0.0000
0.0561	0.0556	69.29	-0.4755	-0.0218	0.0621
0.1159	0.1142	92.07	-0.7117	-0.0312	0.0773
0.1842	0.1805	74.47	-0.7388	-0.0298	0.0520
0.2956	0.2875	61.15	-0.8278	-0.0310	0.0333
0.3565	0.3474	47.39	-0.8569	-0.0308	0.0297
0.4427	0.4327	31.87	-0.7330	-0.0237	-0.0083
0.5687	0.5592	-15.11	-0.3947	-0.0085	-0.0401
0.7086	0.7000	-22.02	-0.2642	-0.0043	-0.0360
0.8276	0.8209	-1.76	-0.2745	-0.0064	-0.0233
1.0000	1.0000	0.00	0.0000	0.0000	0.0000

Table 5 Coefficients Ai of Redlich-Kister type polynomial equation and the corresponding standard deviations () of all the systems at T = 308.15 K

A0 A1 A2 A3 A4

u/m.s-1	-0.7339	775.4850	-583.4590	-473.8260	283.0740	6.2634
ks/10-10Pa-1	0.0208	-9.0326	11.2156	-15.0753	12.8395	0.0669
LE /10-10m	0.0005	-0.3441	0.3262	-0.2820	0.2993	0.0027

methanol with 0.3 m aqueous ethylene glycol

f

ZE/106kg.m-2.s-1 -0.0010 0.7689 -0.5721 -0.4624 0.2659 0.0062

u/m.s-1	-0.7213	736.1740	-386.7110	-695.8330	345.4900	7.6853
ks/10-10Pa-1	0.0171	-8.7452	9.8755	-13.9014	12.7652	0.0835
LE /10-10m	0.0004	-0.3279	0.2314	-0.1613	0.2584	0.0038

methanol with 0.9 m aqueous ethylene glycol

f

ZE/106kg.m-2.s-1 -0.0007 0.7305 -0.2347 – 1.0250 0.5276 0.0094

ethanol with 0.3 m aqueous ethylene glycol

ks/10-10Pa-1	0.0108	-10.7162	21.9214	-23.3536	12.1648	0.0838
LE /10-10m	6.3106	-0.4657	1.0703	-1.1638	0.5608	0.0042

u/m.s-1 5.1166 1443.0700 -4178.0200 4579.0000 -1852.9700 10.3535

f

ZE/106kg.m-2.s-1 -0.0033 1.3946 -3.9915 4.2704 -1.6733 0.0100

u/m.s-1	0.2318	1306.4400	-3120.1000	2739.2200	-928.8410	9.9971
ks/10-10Pa-1	-0.0086	-9.6389	15.0820	-12.4295	7.0315	0.1224
LE /10-10m	-0.0005	-0.4184	0.6807	-0.4859	0.2257	0.0053

ethanol with 0.9 m aqueous ethylene glycol

f

ZE/106kg.m-2.s-1 0.0007 1.2065 -2.6822 2.0886 -0.6168 0.0119

u/m.s-1	12.3389	1062.2400	-4613.9900	6235.0600	-2696.5100	13.2329
ks/10-10Pa-1	-0.0445	-8.4592	29.2346	-35.2776	14.5375	0.0883
LE /10-10m	-0.0026	-0.3733	1.4244	-1.8053	0.7567	0.0040

1-propanol with 0.3 m aqueous ethylene glycol

f

ZE/106kg.m-2.s-1 0.0117 0.9274 -4.6125 6.5118 -2.8389 0.0135

u/m.s-1	8.4480	1103.2400	-4635.9300	6093.4300 –	2568.8900	11.0380
ks/10-10Pa-1	-0.0254	-8.4340	27.1398	-31.0240	12.3380	0.0750
LE /10-10m	-0.0016	-0.3737	1.3284	-1.5992	0.6459	0.0033

1-propanol with 0.9 m aqueous ethylene glycol

f

ZE/106kg.m-2.s-1 0.0091 0.9274 -4.2661 5.7640 -2.4352 0.0110

Ethylene glycol is highly polar (dipole moment = 2.36 D) when compared to water ( = 1.86 D) and alkanols (methanol = 1.70 D, ethanol = 1.69 D, 1-propanol = 1.58 D). Mixing of alkanols to aqueous ethylene glycol molecules leads to breaking of ethylene glycol ethylene glycol dipolar association release of several dipoles. Consequently, the free dipoles of ethylene glycol would induce moments in the neighbouring of alkanol molecules resulting dipole-induced interactions. The larger negative ks values are observed in 1-propanol system compared to remaining systems. This is due to the longer the chain of the alkanol, the higher the polarity of the OH group decreases and weaker the corresponding dipole-dipole interactions. Moreover, increasing the alkanol chain length reduces the concentration of OH groups in higher alkanols and thereby lowers dipole moment in higher alkanols which causes weaker interactions. The strength of interactions in the solutions follow the order methanol

> ethanol > 1-propanol.

L

f

The E and Z has resembled the same trend as we observed in deviation in isentropic

L

f

compressibility and deviation in ultrasonic velocity. From the table it has been observed E is negative

over the entire range of composition. This indicates structural readjustment in the liquid mixtures towards a less compressible phase of fluid and closer packing of molecules [27, 51]. These aspects further support the variation of other deviation/excess properties. When compared between 0.3 m and

0.9 m aqueous ethylene glycol solutions, the ultrasonic velocity, u, is ound to maximum in case of 0.9 m aqueous ethylene glycol solution. In all the observed properties the strength of interactions is stronger in 0.9 m aqueous ethylene glycol solution compared to 0.3 m solution.

The calculated ultrasonic velocities from various theories like, Nomoto [52], Van Dael and Vangeel [53] ,Impedance [54], Junjies [55, Jacobsons [56] and Raos (specific sound velocity) relation

[57] are presented in Tables 6 – 8 for methanol/ethanol/1-propanol respectively. The percentage errors of theoretical values from experimental values are presented in Tables 9 – 11 for methanol/ethanol/1- propanol in the aqueous solution of ethylene glycol respectively. Such an evaluation offers a simple method to investigate molecular interactions besides verifying the applicability of various theories to liquid solutions.

The experimental results have been fitted to two types of polynomials, f(x) and g(x) which describe the ultrasonic velocity data quantitatively as well as qualitatively even in the specific interaction predominant region where non-ideal behavior of the system is noticed. The values of sound velocities and percentage deviation, (after determining the co-efficients in these polynomials by applying least squares method) have been compiled in Tables 6 – 11. The standard deviations of ultrasonic velocities corresponding to polynomial equations have been evaluated using the relation and are given in Table 12. Among all the empirical theories Jacobsons relation gave better estimate of experimental values of sound velocity in all the systems followed by Raos specific sound velocity relation in all the systems investigated.

Table 6 Experimental and theoretical values of ultrasonic velocity in the mixtures of methanol and aqueous ethylene glycol mole fraction Uexp UN UV UImp UJun UJ UR f(x) g(x)

of methanol

m.s-1

0.3 m aqueous ethylene glycol
0.0000	1527.80	1527.80	1527.80	1527.80	1527.80	1527.80	1527.80	1527.07	1526.97
0.0987	1552.20	1476.82	1437.98	1492.03	1433.21	1552.20	1515.07	1552.57	1552.78
0.1968	1562.50	1427.54	1366.00	1454.88	1358.91	1562.39	1517.38	1564.33	1564.37
0.3009	1557.00	1376.75	1303.36	1413.56	1295.39	1556.83	1507.49	1560.04	1559.89
0.3915	1549.20	1333.76	1257.63	1375.90	1249.71	1549.10	1484.27	1541.27	1541.05
0.4944	1503.45	1286.29	1213.43	1331.07	1206.16	1503.56	1459.52	1502.48	1502.31
0.5947	1443.00	1241.35	1176.73	1285.11	1170.50	1443.05	1435.03	1446.97	1446.93
0.7001	1363.40	1195.53	1143.66	1234.22	1138.81	1363.37	1382.13	1370.77	1370.86
0.7963	1296.00	1154.92	1117.57	1185.24	1114.15	1295.95	1320.94	1286.75	1286.89
0.8932	1188.45	1115.17	1094.62	1133.29	1092.78	1188.53	1198.48	1190.23	1190.32
1.0000	1072.65	1072.65	1072.65	1072.65	1072.65	1072.65	1072.65	1073.19	1073.00
0.9 m aqueous ethylene glycol
0.0000	1540.80	1540.80	1540.80	1540.80	1540.80	1540.80	1540.80	1540.08	1540.11
0.0986	1560.85	1488.10	1447.62	1504.17	1441.95	1560.88	1536.03	1562.11	1562.29
0.1937	1572.80	1438.73	1375.26	1467.26	1366.95	1572.88	1533.25	1572.91	1572.87
0.2965	1567.72	1386.92	1311.10	1425.47	1301.76	1567.78	1531.90	1570.08	1569.90
0.3956	1558.00	1338.47	1259.71	1383.17	1250.45	1558.04	1522.11	1550.97	1550.90
0.4939	1515.00	1291.83	1216.58	1339.13	1208.08	1515.10	1493.73	1514.85	1514.95
0.5969	1450.00	1244.43	1178.07	1290.57	1170.84	1449.98	1446.80	1458.16	1458.36
0.6972	1383.00	1199.68	1145.91	1240.73	1140.22	1382.92	1395.10	1384.78	1384.87
0.7957	1309.00	1157.05	1118.58	1189.13	1114.61	1309.03	1329.55	1296.44	1296.30
0.8934	1186.40	1116.02	1094.99	1135.12	1092.86	1186.48	1191.94	1194.79	1194.53
1.0000	1072.65	1072.65	1072.65	1072.65	1072.65	1072.65	1072.65	1071.05	1071.18

Table 7 Experimental and theoretical values of ultrasonic velocity in the mixtures of ethanol and aqueous ethylene glycol mole fraction Uexp UN UV UImp UJun UJ UR f(x) g(x)

of ethanol

m.s-1

0.3 m aqueous ethylene glycol
0.0000	1527.80	1527.80	1527.80	1527.80	1527.80	1527.80	1527.80	1525.92	1526.36
0.0579	1566.87	1490.09	1494.11	1508.95	1458.76	1566.73	1508.11	1572.85	1572.28
0.1485	1606.00	1436.11	144.77	1478.46	1377.19	1605.82	1508.94	1603.05	1602.88
0.2275	1605.65	1393.45	1404.76	1450.83	1323.75	1605.70	1490.88	1597.20	1597.24
0.3038	1568.27	1355.65	1368.49	1423.15	1282.82	1568.43	1489.03	1571.95	1571.84
0.4045	1513.00	1310.24	1323.82	1385.05	1240.20	1512.92	1458.37	1520.36	1520.11
0.5094	1456.00	1267.64	1280.72	1343.33	1205.67	1456.10	1408.26	1455.68	1455.83
0.6114	1389.00	1230.18	1241.78	1300.61	1179.04	1389.05	1371.47	1389.81	1390.42
0.7413	1320.00	1187.33	1195.93	1242.87	1152.31	1319.95	1319.07	1306.14	1306.31
0.8611	1212.90	1151.93	1156.91	1185.97	1132.92	1212.85	1217.53	1225.65	1224.37
1.0000	1115.10	1115.10	1115.10	1115.10	1115.10	1115.10	1115.10	1111.98	1112.56
0.9 m aqueous ethylene glycol
0.0000	1540.80	1540.80	1540.80	1540.80	1540.80	1540.80	1540.80	1541.03	1541.65
0.0703	1588.00	1493.64	1498.37	1517.20	1454.94	1588.07	1530.97	1588.46	1587.68
0.1447	1611.33	1447.95	1456.39	1491.41	1386.41	1611.49	1519.94	1611.04	1610.60
0.2265	1611.00	1402.12	1413.31	1462.01	1328.70	1610.97	1508.08	1609.84	1610.00
0.3562	1571.00	1337.52	1350.80	1412.99	1261.75	1570.96	1521.02	1567.72	1568.12
0.4675	1500.00	1288.74	1302.05	1368.38	1219.99	1500.11	1492.58	1506.37	1506.57
0.5585	1443.00	1252.74	1265.10	1330.01	1193.13	1442.94	1443.22	1446.52	1446.63
0.6578	1379.97	1216.88	1227.44	1286.04	1169.31	1380.03	1404.39	1376.07	1376.12
0.7845	1298.00	1175.64	1182.95	1226.49	1145.11	1298.11	1332.84	1282.45	1282.17
0.8593	1208.95	1153.37	1158.36	1189.35	1133.34	1208.92	1227.82	1225.60	1225.03
1.0000	1115.10	1115.10	1115.10	1115.10	1115.10	1115.10	1115.10	1112.05	1112.37

Table 8 Experimental and theoretical values of ultrasonic velocity in the mixtures of 1-propanol and aqueous ethylene glycol mole fraction Uexp UN UV UImp UJun UJ UR f(x) g(x)

of 1-propanol

m.s-1

0.3 m aqueous ethylene glycol
0.0000	1527.80	1527.80	1527.80	1527.80	1527.80	1527.80	1527.80	1540.14	1539.28
0.0548	1579.80	1490.22	1502.10	1512.30	1464.14	1579.89	1500.22	1566.20	1566.44
0.1167	1587.67	1452.42	1474.27	1494.37	1409.42	1587.82	1485.04	1569.58	1570.33
0.1886	1532.60	1413.68	1443.42	1472.95	1361.16	1532.45	1447.08	1548.35	1548.54
0.2606	1498.00	1379.52	1413.99	1450.82	1324.02	1498.04	1411.82	1509.74	1509.03
0.3448	1452.00	1344.42	1381.30	1424.05	1290.33	1451.87	1376.65	1453.89	1452.88
0.4456	1397.00	1308.01	1344.37	1390.65	1259.52	1396.87	1327.09	1385.73	1385.77
0.5471	1329.80	1276.34	1309.42	1355.43	1235.73	1329.90	1282.63	1327.00	1328.48
0.6934	1266.00	1237.65	1262.53	1301.64	1210.02	1266.08	1221.82	1269.40	1270.43
0.8179	1237.55	1209.83	1225.52	1252.79	1193.61	1237.60	1216.10	1239.06	1237.09
1.0000	1175.60	1175.60	1175.60	1175.60	1175.60	1175.60	1175.60	1174.74	1175.23
0.9 m aqueous ethylene glycol
0.0000	1540.80	1540.80	1540.80	1540.80	1540.80	1540.80	1540.80	1549.25	1548.20
0.0561	1589.60	1500.72	1513.47	1524.39	1472.29	1589.77	1519.34	1577.11	1577.44
0.1159	1590.54	1462.70	1485.54	1506.49	1417.00	1590.58	1496.20	1581.54	1582.56
0.1842	1548.00	1424.25	1455.05	1485.48	1368.79	1548.12	1466.37	1563.03	1563.61
0.2956	1494.00	1370.70	1408.25	1449.83	1312.05	1494.12	1430.62	1500.11	1499.23
0.3565	1458.00	1345.34	1384.07	1429.58	1288.71	1458.03	1446.84	1457.76	1456.70
0.4427	1411.00	1313.32	1351.41	1399.94	1261.99	1411.06	1346.37	1397.43	1397.11
0.5687	1318.00	1273.15	1306.67	1354.44	1232.38	1318.01	1331.11	1321.68	1323.10
0.7086	1260.00	1235.84	1260.71	1300.60	1208.31	1260.05	1297.83	1264.83	1265.79
0.8276	1236.80	1208.80	1224.35	1251.79	1192.74	1236.75	1213.02	1233.70	1292.72
1.0000	1175.60	1175.60	1175.60	1175.60	1175.60	1175.60	1175.60	1175.91	1176.29

Table 9 Percentage deviation of theoretical ultrasonic velocities from experimental ultrasonic velocities in the mixtures of methanol and aqueous ethylene glycol

mole fraction %UN %UV %UImp %UJun %UJ %UR %f(x) %g(x)

of methanol

0.3 m aqueous ethylene glycol
0.0000	0.000	0.000	0.000	0.000	0.000	0.000	-0.048	-0.054
0.0987	-4.856	-7.359	-3.876	-7.666	0.000	-2.392	0.024	0.037
0.1968	-8.637	-12.576	-6.888	-13.030	-0.007	-2.888	0.117	0.120
0.3009	-11.577	-16.290	-9.213	-16.802	-0.011	-3.180	0.195	0.186
0.3915	-13.907	-18.821	-11.186	-19.332	-0.006	-4.191	-0.512	-0.526
0.4944	-14.444	-19.290	-11.466	-19.774	0.007	-2.922	-0.065	-0.076
0.5947	-13.974	-18.453	-10.942	-18.884	0.003	-0.552	0.275	0.272
0.7001	-12.313	-16.117	-9.475	-16.473	-0.002	1.374	0.541	0.547
0.7963	-10.886	-13.768	-8.546	-14.032	-0.004	1.924	-0.714	-0.703
0.8932	-6.166	-7.895	-4.641	-8.050	0.007	0.844	0.150	0.157
1.0000	0.000	0.000	0.000	0.000	0.000	0.000	0.050	0.033
0.9 m aqueous ethylene glycol
0.0000	0.000	0.000	0.000	0.000	0.000	0.000	-0.047	-0.045
0.0986	-4.661	-7.254	-3.631	-7.618	0.002	-1.590	0.081	0.092
0.1937	-8.524	-12.560	-6.710	-13.088	0.005	-2.515	0.007	0.004
0.2965	-11.533	-16.369	-9.074	-16.965	0.004	-2.285	0.151	0.139
0.3956	-14.091	-19.146	-11.221	-19.740	0.003	-2.304	-0.451	-0.456
0.4939	-14.731	-19.698	-11.609	-20.259	0.007	-1.404	-0.010	-0.003
0.5969	-14.177	-18.754	-10.995	-19.252	-0.001	-0.221	0.563	0.577
0.6972	-13.255	-17.143	-10.287	-17.555	-0.006	0.875	0.129	0.135
0.7957	-11.608	-14.547	-9.157	-14.850	0.002	1.570	-0.960	-0.970
0.8934	-5.932	-7.705	-4.322	-7.884	0.007	0.467	0.707	0.685
1.0000	0.000	0.000	0.000	0.000	0.000	0.000	-0.149	-0.137

Table 10 Percentage deviation of theoretical ultrasonic velocities from experimental ultrasonic velocities in the mixtures of ethanol and aqueous ethylene glycol

mole fraction %UN %UV %UImp %UJun %UJ %UR %f(x) %g(x)

of ethanol

0.3 m aqueous ethylene glycol
0.0000	0.000	0.000	0.000	0.000	0.000	0.000	-0.123	-0.094
0.0579	-4.900	-4.644	-3.697	-6.900	-0.009	-3.750	0.382	0.345
0.1485	-10.578	-10.039	-7.941	-14.247	-0.011	-6.044	-0.184	-0.194
0.2275	-13.216	-12.511	-9.642	-17.557	0.003	-7.148	-0.526	-0.524
0.3038	-13.558	-12.739	-9.254	-18.202	0.010	-5.053	0.235	0.228
0.4045	-13.401	-12.504	-8.457	-18.030	-0.005	-3.611	0.486	0.470
0.5094	-12.937	-12.038	-7.738	-17.193	0.007	-3.279	-0.022	-0.012
0.6114	-11.434	-10.599	-6.364	-15.116	0.004	-1.262	0.058	0.102
0.7413	-10.051	-9.399	-5.843	-12.704	-0.004	-0.070	-1.050	-1.037
0.8611	-5.027	-4.616	-2.220	-6.594	-0.004	0.382	1.051	0.946
1.0000	0.000	0.000	0.000	0.000	0.000	0.000	-0.280	-0.228
0.9 m aqueous ethylene glycol
0.0000	0.000	0.000	0.000	0.000	0.000	0.000	0.015	0.055
0.0703	-5.942	-5.644	-4.458	-8.379	0.004	-3.591	0.029	-0.020
0.1447	-10.139	-9.616	-7.442	-13.959	0.010	-5.672	-0.018	-0.045
0.2265	-12.966	-12.271	-9.248	-17.523	-0.002	-6.389	-0.072	-0.062
0.3562	-14.862	-14.017	-10.058	-19.685	-0.003	-3.181	-0.209	-0.183
0.4675	-14.084	-13.197	-8.775	-18.667	0.007	-0.495	0.425	0.438
0.5585	-13.185	-12.328	-7.830	-17.316	-0.004	0.015	0.244	0.252
0.6578	-11.819	-11.053	-6.807	-15.266	0.004	1.769	-0.283	-0.279
0.7845	-9.427	-8.864	-5.509	-11.779	0.008	2.684	-1.198	-1.220
0.8593	-4.597	-4.185	-1.621	-6.254	-0.002	1.561	1.377	1.330
1.0000	0.000	0.000	0.000	0.000	0.000	0.000	-0.274	-0.245

Table 11 Percentage deviation of theoretical ultrasonic velocities from experimental ultrasonic velocities in the mixtures of 1-propanol and aqueous ethylene glycol

mole fraction %UN %UV %UImp %UJun %UJ %UR %f(x) %g(x)

of 1-propanol

0.3 m aqueous ethylene glycol
0.0000	0.000	0.000	0.000	0.000	0.000	0.000	0.808	0.751
0.0548	-5.670	-4.918	-4.273	-7.321	0.006	-5.037	-0.861	-0.846
0.1167	-8.519	-7.143	-5.877	-11.227	0.009	-6.464	-1.139	-1.092
0.1886	-7.759	-5.819	-3.892	-11.186	-0.010	-5.580	1.028	1.040
0.2606	-7.909	-5.608	-3.150	-11.614	0.003	-5.753	0.784	0.736
0.3448	-7.409	-4.869	-1.925	-11.134	-0.009	-5.189	0.130	0.061
0.4456	-6.370	-3.767	-0.455	-9.841	-0.009	-5.004	-0.807	-0.804
0.5471	-4.020	-1.533	1.927	-7.074	0.008	-3.547	-0.211	-0.099
0.6934	-2.239	-0.274	2.815	-4.422	0.006	-3.490	0.269	0.350
0.8179	-2.240	-0.972	1.231	-3.551	0.004	-1.733	0.122	-0.037
1.0000	0.000	0.000	0.000	0.000	0.000	0.000	-0.073	-0.031
0.9 m aqueous ethylene glycol
0.0000	0.000	0.000	0.000	0.000	0.000	0.000	0.548	0.480
0.0561	-5.591	-4.789	-4.102	-7.380	0.011	-4.420	-0.786	-0.765
0.1159	-8.038	-6.602	-5.284	-10.911	0.003	-5.931	-0.566	-0.502
0.1842	-7.994	-6.005	-4.039	-11.577	0.008	-5.273	0.971	1.008
0.2956	-8.253	-5.740	-2.956	-12.179	0.008	-4.242	0.409	0.350
0.3565	-7.727	-5.071	-1.949	-11.611	0.002	-0.765	-0.016	-0.089
0.4427	-6.923	-4.223	-0.784	-10.561	0.004	-4.580	-0.962	-0.984
0.5687	-3.403	-0.860	2.765	-6.496	0.001	0.995	0.279	0.387
0.7086	-1.917	0.056	3.222	-4.102	0.004	3.002	0.383	0.460
0.8276	-2.264	-1.007	1.212	-3.562	-0.004	-1.923	-0.251	4.521
1.0000	0.000	0.000	0.000	0.000	0.000	0.000	0.026	0.059

Table 12 Standard deviation of sound velocities calculated using polynomial equations from experimental values

Name of the liquid system Polynomial form Standard deviation

/m.s-1

Mixtures of methanol and 0.3 m aqueous ethylene glycol

f(x) 4.634

g(x) 4.654

Mixtures of methanol and 0.9 m aqueous ethylene glycol

f(x) 5.702

g(x) 5.726

Mixtures of ethanol and 0.3 m aqueous ethylene glycol

f(x) 7.086

g(x) 6.759

Mixtures of ethanol and 0.9 m aqueous ethylene glycol

f(x) 7.441

g(x) 7.376

Mixtures of 1-propanol and 0.3 m aqueous ethylene glycol

f(x) 10.459

g(x) 10.159

Mixtures of 1-propanol and 0.9 m aqueous ethylene glycol

f(x) 8.541

g(x) 18.875

Conclusions

1. The ultrasonic velocities and densities of aqueous ethylene glycol (0.3m and 0.9m) with methanol/ethanol/1-propanol are measured over the entire composition range of alkanols at T = 308.15 K .

2. From this data u, ks, LE and ZE have been calculated. The values of ks, LE are found to

   f f

   negative, u, ZE are positive indicating the presences of strong interactions exist in the solutions investigated.

3. The reason for existence of specific interactions is attributed to the disruption of intra molecular hydrogen bond in water and ethylene glycol molecules and inter molecular chemical interactions between water and ethylene glycol molecules consequently, formation of new hydrogen bonds between alkanol and aqueous ethylene glycol molecules and dipole- induced dipole interactions between the components of molecules in the solutions. The difference in molar masses of the liquid molecules is also responsible to the existing specific interactions between the molecules of the component liquids.

4. As the chain length of alkanol molecules increases the strength of interactions decreases and follows the order water + ethylene glycol +, methanol > ethanol > 1-propanol. It has been also observed that the strength of interactions is stronger in 0.9 m aqueous ethylene glycol solution when compared to 0.3 m with alkanols.

5. The ultrasonic velocities computed from different velocity theories were correlated with the experimentally measured ultrasonic velocities. Among these theories, Jacobsons equation gives the good agreement between the theoretical and experimental ultrasonic velocity values and also the percentage deviations of ultrasonic velocities calculated from polynomial equations are found to be small.

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