Results in Chemistry 2 (2020) 100049

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Results in Chemistry

journal homepage: www.elsevier.com/locate/rechem

Ultrasonic and volumetric behaviour of glycols with sodium

ethylparaben in aqueous medium from T = 293.15 to 308.15 K at
atmospheric pressure
Ashima a, K.C. Juglan a,⁎, Harsh Kumar b,⁎
a
Department of Physics, Lovely Professional University, Phagwara 144401, Punjab, India
b
Department of Chemistry, Dr B R Ambedkar National Institute of Technology, Jalandhar 144 011, Punjab, India

a r t i c l e i n f o a b s t r a c t

Article history: Volumetric and acoustic analysis is set in motion to inspect the sodium ethylparaben interaction with ethylene
Received 26 November 2019 glycol, and propylene glycol as a function of temperature. The estimation of apparent molar volume and apparent
Accepted 12 May 2020 molar isentropic compression of glycols in aqueous solutions of sodium ethylparaben has been done by
Available online xxxx
employing densities and speed of the sound measurements at p = 0.1 MPa and T = 293.15 to 308.15 K. The par-
tial molar volume, partial molar isentropic compression, partial molar volume of transfer and partial molar isen-
Keywords:
Sodium ethylparaben
tropic compression of transfer have been scrutinized from the density and speed of sound data. The partial molar
Ethylene glycol expansibility is also determined. The data estimated from transfer properties is exercised to examine coefficients
Propylene glycol of pair and triplet interaction. Further, the results are explicated in terms of co-solutes and solvents associations
Hexylene glycol establishing in solution mixture together with structure rupturing behaviour of glycols in aqueous solutions of
Density sodium ethylparaben.
Speed of sound © 2020 The Authors. Published by Elsevier B.V. This is an open access article under the CC BY-NC-ND license (http://
creativecommons.org/licenses/by-nc-nd/4.0/).

1. Introduction substances cause adverse effects consequently, to living beings [12].

These days, parabens are established to be weak endocrine disrupters
For a long time human works on prohibition and perennial of several [13]. The water solubility of paraben decreases and hence, with increase
types of products by virtue of attack of microorganisms like bacteria and in alkyl chain length, its antimicrobial property increases which further
fungi. The accession of preservatives is the magnificent way to perpetu- boost its oil solubility [14]. In 12 countries these preservatives are offi-
ate the properties of commercial products [1]. One of the broadly con- cially authorized to be employed as food additives. Ethylparaben taken
sumed class of preservative are parabens, which are chemically the as a direct food additive in Italy [15]. Sodium ethylparaben with molec-
series of parahydroxybenzoates esterified at C-4 position [2] that in- ular formula (C9H9NaO3) is a sodium salt of ethylparaben which further
clude MeP- (methyl), EtP- (ethyl), PrP- (propyl), BuP- (butyl) and ben- belongs to the group of alkyl esters of para-hydroxybenzoic acid which
zyl parabens [3,4]. Parabens are widely employed as antiseptics that is situated at the para position of the benzene ring. It acts as water sol-
contain a phenolic ring and carboxylic acid functional group. These uble antiseptic usually employed as safe for cosmetics. It is also utilized
compounds along with their salts are mainly consumed due to their by personal care and food industries. Many articles have divulged on
anti-fungicidal properties. Parabens are the synthetic preservative feasible mechanism of interaction of parabens with sucrose esters
widely practiced in pharmaceutical formulations, personal care prod- [16], sugar alcohol [17] and non-ionic macromolecules [18]. Ample re-
ucts, processed foods and beverages [5–9] despite of their endocrine search has been done on solubilisation of parabens in different solvent
disrupting effect [10]. In commercial articles, Parabens are contem- mixtures [19–24]. For the enhanced understanding of intermolecular
plated as perfect additives as a result of their immense anti-microbial interactions in solution mixture, viscometric as well as thermodynamic
activity, good chemical stability, economical manufacturing and no rec- analysis have been extensively utilized in view of their sensitivity
ognizable odour and taste [11] but at present it is evident that these against interactions developing within solute-solute and solute-
solvent in liquid mixture [25–29]. Glycols, belongs to the family of alco-
⁎ Corresponding authors. hols constitute two hydroxyl groups attached to various carbon atom in
E-mail addresses: kc.juglan@lpu.co.in (K.C. Juglan), h.786.man@gmail.com (H. Kumar). every molecule. In ethylene glycol (1, 2-ethanediol), carbon is directly

https://doi.org/10.1016/j.rechem.2020.100049
2211-7156/© 2020 The Authors. Published by Elsevier B.V. This is an open access article under the CC BY-NC-ND license (http://creativecommons.org/licenses/by-nc-nd/4.0/).
2 Ashima et al. / Results in Chemistry 2 (2020) 100049

Table 1
Specifications and purity of pure chemicals (acquired from Loba Chemie Pvt. Ltd., India) used in the recent work.

Chemical name CAS no. Formula Purification Mass fraction of Mass fraction of water after Mass fraction Chemical structure
method watera dryingb puritya

Sodium ethylparaben 35285-68-8 C9H9O3Na Vacuum drying 0.005 b15 · 10−4 0.99

Ethylene glycol 107-21-1 C2H6O2 Used as such 0.001 b7 · 10−5 0.995

Propylene glycol 57-55-6 C3H8O2 Used as such 0.002 b1 · 10−3 ≥0.995

a
Stated by the supplier.
b
Stated by the Karl Fischer method.

linked with hydroxyl (OH) group, as it is alcohol. This glycol consists of possesses two alcohol functional groups. –OH constituting carbon
two hydroxyl groups. Ethylene glycol having molecular formula with two or three hydrogen is termed as primary alcohol whereas;
(HOCH2CH2OH) is a viscous fluid, having no colour, and mild odour is -OH constituting carbon with one hydrogen is termed as secondary al-
manufactured from ethylene oxide commercially which is then pro- cohol. This glycol is prepared from propylene oxide which is then ob-
duced from ethylene. Many researchers are intended to study the gly- tained from propylene. Hence, it is crucial to ascertain the synergy
cols as these are universally exercised in pharmaceutical, cosmetic, among the molecules of paraben and glycols. Therefore, we are con-
biotechnology and food industry [30–32]. A wide spread application cerned about exploring the interaction between parabens and glycols
has been found for aqueous glycol solutions such as manufacture of con- in consideration of its possible application as preservative in glycol
ditioning agents, lubricants, solvents and hygroscopic agents [33]. Eth- based formulations. Our research group has studied the interaction of
ylene glycols are miscible in water over whole composition range, as glycols in aqueous sorbitol solutions [39] through ultrasonic method.
they possess hydroscopic nature, show excessive solubility in polar sol- However, the interaction of glycols with parabens in aqueous media
vent owing H-bonding [34–36]. Propylene glycol also known as 1, 2- has not been inspected yet. As far as we know, no density and ultrasonic
propanediol possesses same physical properties as that of ethylene gly- speed data of glycols with sodium ethylparaben solution mixtures have
col. It has (OH) group called alcohol functional group. This glycol been examined so far. For this reason, in our recent communication we

Table 2
Comparison of density (ρ) and speed of sound (u) of pure compounds with literature at temperature from T = 293.15 to 308.15 K at pressure, p = 0.1 MPa.

Compound T/K ρ × 10−3/(kg·m−3) u/(m·s−1)

Experimental Literature Experimental Literature

Water 293.15 0.998211 0.99821 [41] 1481.14 1482.3 [41]

0.99822 [77] 1482.98 [78]
0.998701 [78]
298.15 0.997047 0.997047 [39] 1495.85 1495.85 [39]
0.99704 [43] 1497.16 [78]
0.9972 [77] 1498.24 [80]
0.9973 [79]
0.997537 [78]
303.15 0.995656 0.99566 [41] 1508.84 1508.5 [41]
0.99564 [77] 1509.62 [78]
0.996131 [78]
308.15 0.994039 0.994039 [39] 1519.14 1519.14 [39]
0.99403 [43] 1520.63 [80]
0.9942 [77]
Ethylene glycol 293.15 1.112856 1.11323 [84] 1667.64 1669.5 [81]
1.11202 [81]
298.15 1.109359 1.1003 [79] 1655.94 1662 [85]
1.1097 [82] 1660.7 [87]
0.99707 [83] 1656.4 [81]
303.15 1.105854 1.105825 [77] 1644.26 1645.2 [81]
308.15 1.102341 1.1025 [77] 1632 1635 [85]
163 [81]
Propylene glycol 293.15 1.036381 1.036214 [88] 1524.95 1522.42 [88]
1509.3 [81]
298.15 1.03271 1.03275 [85] 1511.23 1508.41 [88]
1.0325 [82] 1500.6 [81]
1.03261 [83]
1.032526 [86]
303.15 1.028998 1.02902 [85] 1497.31 1492 [85]
1.0289 [83] 1494.33 [88]
1495.5 [81]
308.15 1.025253 1.02540 [85] 1483.39 1454 [85]
1.02516 [83] 1480.19 [88]
1480.19 [88]

Standard uncertainties u are u (T) = ±0.01 K, u (ρ) = ±0.15 kg·m−3, u (u) = ±1.0 m·s−1, u (p) = ±0.01 MPa.
 Ashima et al. / Results in Chemistry 2 (2020) 100049 3

Table 3
Densities, ρ and apparent molar volumes, Vϕ of ternary system (glycols + SEP + water) at various temperatures and atmospheric pressure, p = 0.1 MPa.
a
m (mol·kg−1) ρ × 10−3/(kg·m−3) Vϕ × 106/(m3·mol−1)

293.15 K 298.15 K 303.15 K 308.15 K 293.15 K 298.15 K 303.15 K 308.15 K

EG + 0.00 mol·kg−1 SEP

0.99821 0.99704 0.99565 0.99403
0.00000
0.99895 0.99779 0.99641 0.99480 54.59 54.61 54.63 54.64
0.09955
0.99971 0.99855 0.99717 0.99556 54.61 54.64 54.66 54.68
0.20101
1.00042 0.99926 0.99788 0.99628 54.64 54.67 54.69 54.71
0.29914
1.00109 0.99993 0.99856 0.99697 54.67 54.71 54.72 54.74
0.39376
1.00181 1.00066 0.99929 0.99771 54.72 54.74 54.75 54.77
0.49716

EG + 0.01 mol·kg−1 SEP

0.99882 0.99765 0.99613 0.99459
0.00000
0.99964 0.99848 0.99696 0.99543 54.72 54.74 54.76 54.79
0.11173
1.00027 0.99912 0.99760 0.99607 54.74 54.76 54.78 54.81
0.19951
1.00096 0.99981 0.99829 0.99677 54.75 54.78 54.80 54.84
0.29565
1.00168 1.00052 0.99902 0.99749 54.77 54.80 54.82 54.86
0.39718
1.00235 1.00120 0.99969 0.99817 54.78 54.81 54.84 54.88
0.49387

EG + 0.03 mol·kg−1 SEP

1.00011 0.99892 0.99749 0.99586
0.00000
1.00085 0.99966 0.99824 0.99661 54.73 54.76 54.79 54.79
0.10147
1.00155 1.00037 0.99895 0.99733 54.75 54.76 54.79 54.82
0.19962
1.00226 1.00108 0.99967 0.99805 54.76 54.77 54.80 54.84
0.29992
1.00294 1.00177 1.00036 0.99874 54.78 54.79 54.81 54.86
0.39779
1.00362 1.00246 1.00105 0.99943 54.79 54.80 54.82 54.88
0.49677

EG + 0.05 mol·kg−1 SEP

1.00110 0.99987 0.99836 0.99675
0.00000
1.00180 1.00058 0.99907 0.99747 54.83 54.85 54.86 54.87
0.09792
1.00251 1.00130 0.99980 0.99820 54.84 54.86 54.87 54.89
0.19953
1.00322 1.00201 1.00052 0.99892 54.86 54.87 54.88 54.90
0.30119
1.00388 1.00268 1.00119 0.99960 54.87 54.88 54.90 54.92
0.39819
1.00459 1.00339 1.00190 1.00032 54.88 54.89 54.91 54.93
0.50258

PG + 0.00 mol·kg−1 SEP

0.99821 0.99704 0.99565 0.99403
0.00000
0.99847 0.99731 0.99593 0.99432 73.54 73.55 73.57 73.62
0.09917
0.99872 0.99757 0.99619 0.99459 73.59 73.61 73.63 73.66
0.19801
0.99896 0.99782 0.99645 0.99486 73.65 73.66 73.68 73.72
0.30136
0.99918 0.99805 0.99668 0.99510 73.69 73.71 73.73 73.77
0.39826
0.99942 0.99830 0.99694 0.99536 73.74 73.75 73.77 73.81
0.51059

PG + 0.01 mol·kg−1 SEP

0.99882 0.99765 0.99613 0.99459
0.00000
0.99908 0.99792 0.99640 0.99487 73.58 73.61 73.64 73.69

(continued on next page)

4 Ashima et al. / Results in Chemistry 2 (2020) 100049

Table 3 (continued)
a
m (mol·kg−1) ρ × 10−3/(kg·m−3) Vϕ × 106/(m3·mol−1)

293.15 K 298.15 K 303.15 K 308.15 K 293.15 K 298.15 K 303.15 K 308.15 K

0.10113
0.99932 0.99817 0.99666 0.99513 73.63 73.65 73.68 73.73
0.19975
0.99955 0.99841 0.99691 0.99539 73.67 73.70 73.71 73.75
0.30093
0.99977 0.99863 0.99714 0.99563 73.72 73.73 73.74 73.79
0.39774
0.99997 0.99884 0.99736 0.99586 73.75 73.77 73.78 73.81
0.49430

PG + 0.03 mol·kg−1 SEP

1.00011 0.99892 0.99749 0.99586
0.00000
1.00035 0.99917 0.99775 0.99613 73.63 73.65 73.67 73.71
0.10086
1.00059 0.99941 0.99800 0.99639 73.67 73.69 73.73 73.75
0.20236
1.00080 0.99963 0.99822 0.99662 73.71 73.74 73.77 73.78
0.29894
1.00102 0.99985 0.99845 0.99686 73.74 73.78 73.81 73.81
0.40149
1.00122 1.00005 0.99866 0.99708 73.77 73.81 73.84 73.85
0.49727

PG + 0.05 mol·kg−1 SEP

1.00110 0.99987 0.99836 0.99675
0.00000
1.00133 1.00012 0.99861 0.99701 73.68 73.70 73.71 73.74
0.10131
1.00155 1.00034 0.99885 0.99725 73.71 73.74 73.76 73.79
0.19956
1.00179 1.00059 0.99910 0.99751 73.75 73.78 73.80 73.83
0.31442
1.00196 1.00076 0.99929 0.99770 73.78 73.81 73.83 73.87
0.40016
1.00217 1.00097 0.99951 0.99793 73.81 73.84 73.86 73.90
0.50552
a
m states the molalities of EG and PG in aqueous SEP solutions. Standard uncertainties u are ur(m) = 1%, u (Vϕ) = ±0.07 × 10−6 m3·mol−1, u (T) = 0.01 K, u (ρ) = 0.15 kg·m−3 and u
(p) = 0.01 MPa.

investigate the densities and ultrasonic speed of glycols (EG and PG) in 2.2. Methods
SEP (sodium ethylparaben) solutions of water at several working tem-
peratures (293.15, 298.15, 303.15 and 308.15 K) and atmospheric The aqueous solution employed in the recent investigation was pre-
pressure. pared with the help of triple distilled and freshly prepared degassed

2. Experimental section

2.1. Materials

EG, Ethylene glycol (mass fraction purity 0.995); PG, Propylene gly-
col (mass fraction purity ≥ 0.995); and SEP, Sodium ethylparaben (mass
fraction purity 0.99) were achieved from Loba Chemie Pvt. Ltd., India
and employed as such devoid of further distillation as received. Regard-
less, the chemical (Sodium ethylparaben) was dried in vacuum and
placed for at least 2 days over desiccators prior to the measurements.
These chemicals were placed in dark concentrated bottles so that
these were not absorbed into atmosphere. The liquids (EG and PG)
were placed above molecular sieves to lessen the content of water pres-
ent in it. The water content as declared by the supplier was 0.1%, 0.2%
and 5.0% in EG, PG and SEP respectively. After drying, the Karl Fischer
method (Table 1) was utilized to analyze the water content in solute
samples for calculation of molalities. The details and the chemical struc-
ture of glycols and paraben utilized in this research are shown in
Table 1. Table 2 tabulates the comparison of experimental density and
speed of sound values with accessible literature values. The density
and speed of sound experimental values for ethylene glycol and propyl-
Fig. 1. Graph of experimental (empty square) and literature data (filled triangle [39]; filled
ene glycol are in excellent agreement with the literatures values. The circle [40]; filled square [41]) of densities for mixtures of (EG + water) at various
agreement between experimental and literature values of ethylene gly- temperatures [black, 293.15 K; red, 298.15 K; green, 303.15 K; blue, 308.15 K]. (Solid
col and propylene glycol is found to be reasonable good. lines, experimental data of EG + water; dotted lines, literature data of EG + water.)
 Ashima et al. / Results in Chemistry 2 (2020) 100049 5

water having specific conductance b 10−6 S·cm−1 (measured with con-

ductivity meter Systronics 308). Analytical balance (Sartorius CPA
225D) fitted the mass measurements of liquid samples with an accuracy
of ±0.00001 g. The solutions were prepared by mass adding solute
(hundred of grams) i.e. glycols in SEP solution which is acting as solvent.
The estimated relative uncertainty in solution molality is ur(m) = 1%.
Anton Paar DSA 5000 M density and sound velocity meter was used to
measure both density and sound velocity for this current investigation.
The time propagation technique is employed for the computation of
measurement of sound velocity. The mixed solution is slotted between
two piezoelectric transducers where sound waves of 3 MHz frequency is
emitted by one transducer whereas other transducer receives those
sound waves in a sample filled cavity. Hence, speed of the sound of sam-
ple (u) is attained by separating the known distance between transmit-
ter and transducer receiver by an assessed acoustic wave transmission
moment [37,38]. Dry air at atmospheric pressure and triple distilled
water was utilized to calibrate the densimeter before each set of read-
ings in the experimental temperature range. Both the values of ultra-
sonic speed and density are extremely reactive to temperature thus;
they were handled by built-in Peltier device to ±1 × 10−3 K. The appa-
ratus sensitivity corresponds to the exactness of measurement of ultra-
sonic speed and density of 1 × 10−2 m·s−1 and 1 × 10−3 kg·m−3
respectively. The estimated uncertainties values of ρ and u are ±
0.15 kg·m−3 and ±1.0 m·s−1, respectively.

3. Results and discussion

3.1. Volumetric properties

3.1.1. Density
The densities (ρ) values were measured for EG and PG in 0.00, 0.01,
0.03 and 0.05 mol·kg−1 SEP solutions in water and are tabulated in
Table 3 at T = 293.15, 298.15, 303.15 and 308.15 K temperatures. EG
with a molecular formula (C2H6O2) constitutes two (-OH) hydroxyl
groups which is further attached to adjacent carbon since it is an alcohol
whereas PG (C3H8O2) acts same as EG. It has two types of (–OH) alcohol
functional group, one is primary and other is secondary alcohol. It has
been professed from the data recorded in Table 3 that at a particular
SEP concentration, the density of solution mixture accelerates with
surge in concentration of glycols (EG and PG) and slightly reduces
with temperature increase. The experimental density data has been

Fig. 2. Graph of experimental (empty square) and literature values (filled square [42];
filled triangle [43]; filled star [44]; filled diamond [45]; filled circle [46]) of densities for
mixtures of (PG + water) at 298.15 K temperature. [Solid lines, experimental data of
PG + water; dotted lines, literature data of PG + water.]
6 Ashima et al. / Results in Chemistry 2 (2020) 100049

compared with literature data [39–46]. It is depicted from Figs. 1 and 2

that present experimental density data for (EG + water) are in coher-
ence with literature data [39–41] at several temperatures however, at
298.15 K for (PG + water) mixture the present density value are in
good agreement with literature values [44,45] and moreover, system-
atic deviations are also observed from the values reported in the litera-
ture [42,43,46]. It is well known that deviations are related to the
procedure of calibration, solution preparation as well as its purity, dif-
ferent measuring method used. The variation among present measured
data and the data from literature could be due to different measuring
could be due to partial degassing of investigated samples. The density
value decreases in accordance to temperature i.e. due to temperature
escalation, the values of density decreases.

3.1.2. Apparent molar volume

Using the equation as given below, the experimentally measured
density (ρ) values are being employed for the computation of Vϕ

V ϕ ¼ ðM=ρÞ−fðρ−ρ0 Þ=mρρ0 g ð1Þ

Scheme 1. Representation of Glycol-SEP interactions.
where M (kg·mol−1) represents the solute molar mass; m (mol·kg−1)
represents the solution molality viz. amount of glycols per kilogram of
water mixed with SEP; ρ and ρ0 (kg·m−3) tells about the solution mix- hydrophobic overlap and cause bulk reduction whereas two ionic
ture and pure solvent densities, respectively. The Vϕ data are incorpo- groups overlap with hydration cospheres cause volume enhancement.
rated in Table 3 and is presented in Fig. 3. The estimated uncertainty The positive value of V0ϕ emanate owing to the fact that ion-
for Vϕ is ±0.07 × 106 m3·mol−1. The data provided in Table 3 imply hydrophilic associations are prominent with regard to ion – hydropho-
that at a certain SEP (sodium ethylparaben) concentration, Vϕ surges bic and hydrophobic-hydrophobic associations [55]. An acceleration in
with temperature escalation along with the glycols molality. An en- the values of V0ϕ for glycols with increase in temperature and SEP con-
hancement in Vϕ data has also been noticed in Table 3 with respect to centration can be elucidated as the fragments of the solvent are re-
ascent in SEP concentration, which infers the pronounced interactions moved from the solute in to the solution. It is inferred from the
within solute and solvent molecules. Similarly, at whole SEP concentra- perceived larger V0ϕ values that at superlative temperature, solution
tions as well as temperatures, surge in data of Vϕ is seen with upsurge in mixture expands due to discharge of fragment of solvent molecules
EG and PG molar mass, ensuing the extremum association midst solute from the solute secondary solvation layer. At infinite dilution, the appar-
and solvent for PG with regard to mixtures of EG as ascribed by Scheme ent molar volume tends to increase with rise in glycol concentration due
1. Different physical forces like dipole-induced - dipole, dipole-dipole to the intensified associations midst solute and solvent fragments
interactions, hydrophilic effect and hydrophobic hydration in the within hydroxyl groups of EG and SEP. Moreover, Table 4 shows that
water rich area can be accredited to this elevation in Vϕ value [47]. at all the working temperatures and for all SEP concentrations magni-
tude of Sv has been perceived positive further suggesting the survival
3.1.3. Partial molar volume of associations midst solute and solute in the investigated solution mix-
Partial molar volume at infinite dilution (V0ϕ), is achieved by tech- ture. As no regular trend is followed by Sv values, which demonstrates
nique of least square fitting of apparent molar volume by the equation that some extra variables affect the association amid solute and solute
described below: interactions [56,57]. The surplus values of V0ϕ than Sv values recommend
the manifestation of feeble association between solute and solute in
V ϕ ¼ V 0ϕ þ Sv m ð2Þ comparison to solute-solvent associations.

where Sv is the experimental slope of associations midst solute and sol- 3.1.4. Partial molar volume of transfer
ute, m is the glycol molality in SEP solutions of water. Table 4 indexes By utilizing equation (Eq. (1)) of the Supporting data, the partial
the value of V0ϕ and Sv along with their standard errors computed by molar volume transfer of glycols from water to SEP solutions in water
employing least square fitting technique for apparent molar volume. was computed at infinite dilution. As seen from the data mentioned in
The entire value of V0ϕ, are coming out to be positive and thus rises Supporting information in Table S1, the ΔtrV0ϕ are all positive and esca-
with an rise in SEP concentration and temperature for all the glycols late with increased concentration of SEP concentration for each glycol
which can possibly arise as a result of strengthening of interaction that deduces enormous devitalisation effect on glycols. The values of
amid solute and solvent as epitomized in Fig. 4. Moreover, V0ϕ values es- ΔtrV0φ do not show regular trend with temperature. The significant
calates with a rise in molar mass [48] of glycols that is, from EG to PG at ΔtrV0ϕ values under inspection recommend robust ion-ion associations
individual temperature resulting in greater V0ϕ values for HG which im- of SEP with all glycols. According to model of co sphere overlap, the per-
plies the increased associations midst solute and solvent for PG with re- ceived positive values (ΔtrV0ϕ) values signify the solute structure build-
gard to EG. Table 7 represents the comparison of experimental V0ϕ values ing or sustaining property resulting from their solvophobic solvation
with the data published in literature. The agreement of present limiting and also the spatial connection of two cospheres [53,54]. The variety
partial molar volume for (EG + water) with literature values is very sat- of possible interactions that subsist within the molecules of glycols
isfactory. The V0ϕ value measures only ion—solvent interaction and is un- and SEP might be hydrophilic-hydrophilic, hydrophobic-hydrophobic,
affected by ion-ion interactions [49–52]. As stated by the model of co- ion-hydrophilic and ion-hydrophobic interactions. The model of co-
sphere overlap [53,54] groups of hydrophobic-hydrophobic and ion- sphere overlap affirmed that the positive response towards ΔtrV0ϕ brings
into existence by hydrophilic-hydrophilic and ion-hydrophilic interac-
Fig. 3. Graph for Vϕ, apparent molar volume versus am, concentration of EG and PG in
tions moreover, hydrophobic-hydrophobic and ion-hydrophobic inter-
(a) 0.01 mol·kg−1; (b) 0.03 mol·kg−1; (c) 0.05 mol·kg−1 aqueous SEP solution (sphere actions make negative contribution to ΔtrV0ϕ. In the recent
EG and cube PG) at various temperatures. investigation, the observed ΔtrV0ϕ values are found to be positive for all
 Ashima et al. / Results in Chemistry 2 (2020) 100049 7

Table 4
Partial molar volumes (V0ϕ), experimental slopes, Sv of EG and PG in SEP solutions of water at various temperatures.
a
m/(mol·kg−1) V0ϕ × 106/(m3·mol−1) Sv × 106/(m3·kg·mol−2)

T = 293.15 K T = 298.15 K T = 303.15 K T = 308.15 K T = 293.15 K T = 298.15 K T = 303.15 K T = 308.15 K

EG
54.55 (±0.008) 54.58 (±0.003) 54.60 (±0.003) 54.61 (±0.001) 0.32 (±0.025) 0.33 (±0.010) 0.31 (±0.010) 0.31 (±0.001)
0.00
54.71 (±0.001) 54.73 (±0.003) 54.74 (±0.001) 54.76 (±0.002) 0.14 (±0.005) 0.17 (±0.011) 0.21 (±0.005) 0.24 (±0.007)
0.01
54.72 (±0.003) 54.75 (±0.002) 54.78 (±0.001) 54.78 (±0.004) 0.15 (±0.010) 0.10 (±0.008) 0.09 (±0.002) 0.20 (±0.012)
0.03
54.82 (±0.001) 54.84 (±0.001) 54.85 (±0.001) 54.86 (±0.002) 0.13 (±0.003) 0.11 (±0.005) 0.13 (±0.003) 0.13 (±0.008)
0.05

PG
73.49 (±0.005) 73.51 (±0.010) 73.53 (±0.008) 73.57 (±0.005) 0.51 (±0.014) 0.49 (±0.030) 0.49 (±0.025) 0.48 (±0.016)
0.00
73.54 (±0.004) 73.57 (±0.005) 73.61 (±0.003) 73.67 (±0.002) 0.43 (±0.011) 0.41 (±0.014) 0.34 (±0.008) 0.30 (±0.007)
0.01
73.59 (±0.007) 73.61 (±0.005) 73.64 (±0.010) 73.67 (±0.003) 0.36 (±0.021) 0.41 (±0.016) 0.41 (±0.031) 0.35 (±0.010)
0.03
73.65 (±0.002) 73.67 (±0.005) 73.68 (±0.006) 73.70 (±0.008) 0.31 (±0.007) 0.35 (±0.014) 0.37 (±0.017) 0.40 (±0.024)
0.05

glycols which promote the supremacy of hydrophilic-hydrophilic and Supporting information. The ARD (σ) values are computed from the
ion-hydrophilic interactions in comparison to hydrophobic- Supporting data equation (Eq. (3)). The deviation values are established
hydrophobic and ion-hydrophobic interactions. to be very small and very magnificently fit in with the polynomial equa-
tion. At infinite dilution, the Supporting data equation (Eq. (4)) repre-
3.1.5. Temperature dependent partial molar volume sents the association for partial molar volume which dependent on
The general polynomial equation (Eq. (2)) of the Supporting infor- temperature in accordance with absolute temperature (T). The similar
mation is employed in order to evaluate the temperature along with equation (Eq. (4)) of the Supporting information has been employed
the apparent molar volume deviation. The values of these constants in to measure limiting apparent molar expansion. The limiting apparent
aqueous SEP for EG and PG are provided in Table S2 of the Supporting molar expansion, E0ϕ = (∂V0ϕ/∂T)P is believed to be most reliable measure
information. In the aqueous SEP solutions, the negative value of scarcely for solute-solvent interactions arising in the combination of mixture
statistically significant coefficient (c) has been discovered for EG and [58,59,60]. Hepler [61,62] proposed a thermodynamic expression to as-
positive for PG. Such parameters are utilized to analyze the calculated certain the structure constructing and structure splitting solute poten-
values of V0φ and further average relative deviation (ARD) achieved tial existing in the solution mixture employing equation (Eq. (5)) of
from measured and determined values are indexed in Table S2 of the the Supporting information. Hepler declared that if (∂E0ϕ/∂T)P is positive,
the structure manufacturer of solute exists however if it is negative then
the solute is a structure breaker. The partial molar expansibilities and

Fig. 5. Graph of experimental (empty square) and literature values (filled circle [39]; filled
triangle [41]) of speed of sound for mixtures of (EG + water) at various temperatures.
Fig. 4. Graph of V0ϕ, partial molar volume at infinite dilution for EG and PG in various [Black, 293.15 K; red, 298.15 K; green, 303.15 K; blue, 308.15 K.] [Solid lines,
concentration of aqueous SEP solution at different temperatures (dot, EG; cube, PG). experimental data of EG + water; dotted lines, literature data of EG + water.]
8 Ashima et al. / Results in Chemistry 2 (2020) 100049

3.2.2. Apparent molar isentropic compression

For all glycols in aqueous SEP solution, the apparent molar property
of isentropic compression (Kϕ, s) has been evaluated as follows

K ϕ;s ¼ ðMβs =ρÞ− βs ρ0 −βs;0 ρ mρρ0 ð3Þ

where m (mol·kg−1) is the molality of glycols i.e. quantity of glycols

(solute) dissolved per kilogram in the mixture of water and SEP (sol-
vent), M (kg·mol−1) represents the molar mass of solute; ρ and ρ0 rep-
resents solution and pure solvent densities; βs and βs,0 states solution
and solvent isentropic compressibilities respectively.
Laplace–Newton equation [70] explained isentropic compressibility
as

βs ¼ 1= u2 ρ ð4Þ

where ρ is the density of solution and u is the ultrasonic speed.

Table 5 provides the data of calculated values of Kϕ, s for glycols in
Fig. 6. Graph of experimental (filled square) and literature values (filled circle [44]; filled
triangle [67] filled star [68]) of speed of sound for mixtures of (PG + water) at 298.15 K
0.00, 0.01, 0.03 and 0.05 mol·kg−1 aqueous SEP solutions at various
temperature. temperatures. It has been reviewed from the computed data of Kϕ, s
that the values are negative for whole concentration of SEP and at entire
working temperatures. The negative Kϕ, s values reduced with increase
values of (∂E0ϕ/∂T)P are indexed in Table S3 of the Supporting infor- concentration of SEP and accelerate with temperature rise. It is esti-
mation. The arriving positive E0ϕ values at entire SEP concentration mated from the negative value of Kϕ, s that the hydrogen bonded net-
and entire temperature range infer the persistence of association work [71] around solute molecules become less compressible in
midst solute and solvent in the current examined systems, as earlier comparison to water fragments in augmented solution, ensuing in con-
depicted by statistics of apparent molar volume. The occurrence of traction of water fragments throughout the solute as a result of hydro-
Packing effect or caging [63,64] causes the positive value of E 0ϕ phobic interaction of non-polar group. Consequently, solution
which further tells the interaction between glycols and SEP mole- compressibility is by the virtue of stress on fragments of water. Accord-
cules. No regular trend of E0ϕ values has been noted with regard to ing to the acquired negative Kϕ, s values, water molecules around the
surge in SEP concentration along with temperature. The tiny nega- solute are less compressible as compared to water in bulk solution
tive and positive (∂E0ϕ/∂T)P values specify the glycol structure con- which also promotes robust solute-solvent connections midst the gly-
struction in SEP solutions of water. cols and SEP fragments.

3.2.3. Partial molar isentropic compression

3.1.6. Thermal expansion coefficient
The variation of molality (m) with partial molar isentropic compres-
Coefficient of thermal expansion, α is acquired by the Supporting
sion (K0ϕ, s) is epitomized by following equation:
data equation (Eq. (6)). Thermal expansion coefficient (α) of the
Supporting data (mentioned in Table S3) offers data on the subsistence
of interactions within solute and solvent in the combination of solution K ϕ;s ¼ K 0ϕ;s þ Sk m ð5Þ
[65,66]. For EG and PG no expected trend has been noticed with respect
to the concentration of SEP.
where K0ϕ, s represents the partial molar isentropic compression at infi-
nite dilution, the experimental slope, Sk gives the information about in-
3.2. Acoustic properties teractions occurring within solute-solute molecules, m states the glycols
molality in aqueous SEP solutions. The K0ϕ, s and Sk both values along
3.2.1. Speed of sound with their standard errors which are obtained from least square fitting
Sound velocity (u) data has been experimentally ascertained for gly- technique are collected in Table 6. The interaction among the solute–
cols (EG and PG) in 0.00, 0.01, 0.03 and 0.05 mol·kg−1 SEP solutions in solute molecules at infinite dilution become insignificant as a result of
water at various temperatures (T = 293.15 to 308.15 K). The literature relatively small size of Sk values, which implies that the solute-solvent
values have been employed to compare the experimentally computed interactions [72,93] prevail in the liquid mixture. Due to surge in tem-
sound velocity values for (EG + water) [39,41] and (PG + water) perature, negative K0ϕ, s values become less which indicates that the
[44,67,68] mixtures. Figs. 5 and 6 provides the graphical representation few molecules of water are released to the bulk. Also, these K0ϕ, s values
of the experimental and literature comparison of sound velocity values, turn out to be less negative with rise in SEP concentration. The K0ϕ, s
further illustrating that for (EG + water) the same trend has been values are graphically shown in Fig. 7. At low temperature, the greater
followed by the empirical and experimental values as well as for negative values of K0ϕ, s for glycols point towards the strong attractive in-
(PG + water) values at 298.15 K the experimental values are in excel- teraction within the molecules of glycol and water [73]. The presence of
lent agreement with the literature values [44,67,68]. The sound speed robust appealing associations midst SEP and water molecules causes
values at all working temperatures are indexed in Table 5 which varies glycols to be desiccated as a consequence of which the water molecules
in order w.r.t. temperature i.e. the sound speed escalates as the temper- across the glycols are more compressible at greater SEP concentration
ature rises. This elevation in temperature related sound speed is a fea- than those at lower SEP concentrations. The comparison of assessed
ture of water and is involved in the building of water with three sided data and published limiting partial molar isentropic compression data
constructions of H-bonds [69]. It is also noticed from Table 5 that the ul- for (EG + water) is recorded in Table 7. The acquired experimental
trasonic speed elevates with glycols molality at a determined SEP values of K0ϕ, s are in excellent agreement with literature values and
concentration. obey the similar trend as reported studied values.
 Ashima et al. / Results in Chemistry 2 (2020) 100049 9

Table 5
Speed of sound, u and apparent molar isentropic compression (Kϕ, s) of ternary system (glycol + SEP + water) at various temperatures and atmospheric atmosphere, p = 0.1 MPa.
a
m/(mol·kg−1) u/(m·s−1) Kϕ, s × 106/(m3·mol−1·GPa−1)

T = 293.15 K T = 298.15 K T = 303.15 K T = 308.15 K T = 293.15 K T = 298.15 K T = 303.15 K T = 308.15 K

EG + 0.00 mol·kg−1 SEP

1482 1496 1509 1519
0.00000
1485 1499 1511 1521 −45.16 −44.27 −43.51 −42.92
0.09955
1488 1502 1514 1524 −45.42 −44.54 −43.77 −43.18
0.20101
1491 1504 1516 1526 −45.53 −44.64 −43.88 −43.28
0.29914
1494 1507 1519 1529 −45.60 −44.71 −43.94 −43.35
0.39376
1497 1510 1522 1531 −45.66 −44.76 −44.00 −43.40
0.49716

EG + 0.01 mol·kg−1 SEP

1486 1499 1510 1520
0.00000
1489 1501 1512 1523 −44.91 −44.12 −43.47 −42.88
0.11173
1491 1503 1514 1525 −45.11 −44.33 −43.67 −43.08
0.19951
1494 1505 1517 1527 −45.22 −44.43 −43.77 −43.18
0.29565
1496 1508 1519 1529 −45.29 −44.50 −43.84 −43.25
0.39718
1499 1510 1521 1531 −45.34 −44.55 −43.89 −43.30
0.49387

EG + 0.03 mol·kg−1 SEP

1486 1500 1512 1522
0.00000
1489 1503 1514 1524 −44.82 −43.99 −43.93 −42.72
0.10147
1492 1505 1517 1526 −45.07 −44.24 −44.18 −42.96
0.19962
1495 1508 1519 1528 −45.18 −44.35 −44.28 −43.07
0.29992
1497 1510 1521 1530 −45.25 −44.41 −44.35 −43.13
0.39779
1500 1513 1524 1532 −45.30 −44.47 −44.40 −43.19
0.49677

EG + 0.05 mol·kg−1 SEP

1489 1502 1514 1524
0.00000
1491 1505 1516 1527 −44.67 −43.85 −43.17 −42.59
0.09792
1494 1508 1519 1529 −44.94 −44.11 −43.42 −42.85
0.19953
1497 1510 1521 1531 −45.04 −44.22 −43.53 −42.95
0.30119
1501 1513 1524 1534 −45.11 −44.28 −43.59 −43.02
0.39819
1504 1516 1527 1536 −45.17 −44.34 −43.65 −43.07
0.50258

PG + 0.00 mol·kg−1 SEP

1482 1496 1509 1519
0.00000
1486 1500 1513 1523 −42.62 −44.25 −43.49 −42.90
0.09917
1490 1504 1516 1526 −42.86 −44.49 −43.72 −43.13
0.19801
1493 1507 1520 1529 −42.95 −44.58 −43.81 −43.22
0.30136
1496 1510 1522 1532 −42.99 −44.62 −43.86 −43.27
0.39826
1499 1513 1525 1534 −43.03 −44.66 −43.89 −43.30
0.51059

PG + 0.01 mol·kg−1 SEP

1486 1499 1510 1520
0.00000

(continued on next page)

10 Ashima et al. / Results in Chemistry 2 (2020) 100049

Table 5 (continued)
a
m/(mol·kg−1) u/(m·s−1) Kϕ, s × 106/(m3·mol−1·GPa−1)

T = 293.15 K T = 298.15 K T = 303.15 K T = 308.15 K T = 293.15 K T = 298.15 K T = 303.15 K T = 308.15 K

1489 1503 1514 1524 −44.84 −44.05 −43.40 −42.82

0.10113
1493 1507 1518 1528 −45.07 −44.28 −43.63 −43.04
0.19975
1498 1511 1522 1531 −45.16 −44.37 −43.71 −43.13
0.30093
1502 1515 1527 1535 −45.20 −44.42 −43.76 −43.17
0.39774
1507 1520 1530 1539 −45.24 −44.45 −43.79 −43.20
0.49430

PG + 0.03 mol·kg−1 SEP

1486 1500 1512 1522
0.00000
1491 1504 1516 1526 −44.80 −43.97 −43.27 −42.70
0.10086
1495 1509 1520 1530 −45.03 −44.20 −43.50 −42.93
0.20236
1500 1513 1524 1533 −45.11 −44.28 −43.58 −43.01
0.29894
1504 1516 1527 1536 −45.16 −44.33 −43.62 −43.05
0.40149
1509 1521 1532 1540 −45.19 −44.36 −43.65 −43.08
0.49727

PG + 0.05 mol·kg−1 SEP

1489 1502 1514 1524 −44.66 −43.84 −43.16 −43.09
0.00000
1494 1507 1519 1529 −44.89 −44.07 −43.38 −43.32
0.10131
1499 1512 1523 1533 −44.99 −44.16 −43.47 −43.41
0.19956
1504 1517 1528 1538 −45.03 −44.20 −43.51 −43.44
0.31442
1508 1521 1531 1541 −45.06 −44.23 −43.54 −43.48
0.40016
1513 1524 1535 1545
0.50552
a
m represents the molality of EG and PG in SEP solutions of water. Standard uncertainties u are ur(m) = 1%, u (T) = 0.01 K, u (u) = 1.0 m·s−1, u (Kϕ, s) = ±0.25 × 10−6 m3·mol−1·GPa−1, u
(p) = 0.01 MPa.

3.2.4. Partial molar isentropic compression of transfer 3.3. Pair and triplet interaction coefficients
At infinite dilution, the (ΔtrK0ϕ, s) of each glycol from water to aque-
ous solution of SEP is computed from the Supporting information equa- The volumetric and isentropic compressibility pair and triplet inter-
tion (Eq. (7)). The values of ΔtrK0ϕ, s (indexed in Table S4) of the action coefficients were computed by McMillan and Mayer [74] that let
Supporting data are investigated to be positive at entire concentration the partition of effects caused as a result of interaction midst two or
of SEP and whole range of temperature with the exception of EG in more solute fragments and those induced by their interaction between
0.03 mol·kg−1 aqueous SEP solution at 303.15 K and PG in 0.01, 0.03, the solute pair. This theory of McMillan and Mayer was discussed fur-
and 0.05 mol·kg−1 aqueous SEP solutions at 293.15 K. Therefore, inti- ther by Friedman and Krishnan [75,94]. Hence, ΔtrV0ϕ and ΔtrK0ϕ, s can
mate the preponderance of interactions among both glycols and SEP be computed from the equations (Eqs. (8) and (9)) of the Supporting in-
that further insinuates the tendency of solute to build structure. formation. VAB and KAB are the volume and isentropic compression

Table 6
Limiting apparent molar isentropic compression (K0ϕ, s) and experimental slope, Sk of EG and PG in aqueous solution of SEP at different temperatures.
a
m/(mol·kg−1) K0ϕ, s × 106/(m3·mol−1·GPa−1) Sk × 106/(kg·m3·mol−2·GPa−1)

T = 293.15 K T = 298.15 K T = 303.15 K T = 308.15 K T = 293.15 K T = 298.15 K T = 303.15 K T = 308.15 K

EG
0.00 −45.12 (±0.08) −44.24 (±0.08) −43.48 (±0.08) −42.89 (±0.08) −1.18 (±0.24) −1.16 (±0.24) −1.15 (±0.23) −1.14 (±0.23)
0.01 −44.85 (±0.06) −44.07 (±0.06) −43.41 (±0.06) −42.83 (±0.06) −1.08 (±0.20) −1.07 (±0.19) −1.06 (±0.19) −1.05 (±0.19)
0.03 −44.78 (±0.08) −43.95 (±0.07) −43.23 (±0.07) −42.68 (±0.07) −1.15 (±0.23) −1.13 (±0.22) −1.12 (±0.22) −1.11 (±0.22)
0.05 −44.64 (±0.08) −43.82 (±0.08) −43.13 (±0.08) −42.56 (±0.08) −1.16 (±0.24) −1.14 (±0.24) −1.13 (±0.23) −1.12 (±0.23)

PG
0.00 −44.98 (±0.08) −44.24 (±0.08) −43.48 (±0.08) −42.89 (±0.08) −0.93 (±0.23) −0.93 (±0.22) −0.92 (±0.22) −0.91 (±0.23)
0.01 −44.82 (±0.08) −44.04 (±0.07) −43.38 (±0.07) −42.80 (±0.07) −0.95 (±0.23) −0.93 (±0.23) −0.93 (±0.22) −0.92 (±0.22)
0.03 −44.78 (±0.07) −43.95 (±0.08) −43.25 (±0.07) −42.68 (±0.07) −0.93 (±0.23) −0.92 (±0.23) −0.91 (±0.22) −0.91 (±0.22)
0.05 −44.65 (±0.07) −43.83 (±0.07) −43.14 (±0.07) −42.52 (±0.07) −0.91 (±0.22) −0.90 (±0.22) −0.89 (±0.212) −0.89 (±0.21)
−6
a 0
m is the molality of SEP solutions in water. Standard uncertainties u are ur(m) = 1%, u (T) = 0.01 K, u (Kϕ, s) = ±0.01 × 10 m3·mol−1·GPa−1 and u (Sk) = ±
0.24 × 10−6 kg·m3·mol−2·GPa−1.
 Ashima et al. / Results in Chemistry 2 (2020) 100049 11

are positive for pair interaction coefficient, VAB for all the glycols
whereas for triplet interaction coefficient, VABB the values are negative.
For the isentropic compression, coefficient of pair interaction, KAB is pos-
itive at all the temperatures apart from EG and PG at 303.15 K and
293.15 K whereas KABB is negative throughout all the temperatures ex-
cluding EG at 303.15 K and PG at 293.15 K. Overall large positive values
of VAB suggests the superiority of pair-wise interactions over triplet in-
teractions in glycols-SEP-water ternary systems. As per this model, mol-
ecules of water are released from hydration co-spheres as a
consequence of their association when non-bonding interaction occurs.
The volume shift is positive if the bulk is more organized than water and
would be negative if water is more organized than bulk, i.e. owing to dif-
ferent structural arrangement of water molecules in these two domains,
water is removed from the co-sphere [25]. The pair wise interaction
among the aqueous solution of glycols and SEP is estimated by the VAB
positive values.

4. Conclusions

In this work, volumetric and compressibility studies of EG and PG

have been examined at different concentrations of SEP solutions in
water have been examined in this work. Apparent molar properties
and partial molar properties derived from experimental data of density
and sound speed data supplies information about particular interactions
that might exist in the investigated ternary system. The subsistence of
sturdy solute-solvent interactions among (glycols molecules and SEP)
is conspicuous from elucidation of evaluated data. The degree of interac-
tions heightens with the concentration of SEP solutions along with the
molar mass of glycols which means that interactions amidst solute
and solvent rises from EG to PG. At lessen temperatures, more negative
K0ϕ, s values describes the intense and interesting connections with both
the glycols and water molecules as water molecules are rigidly re-
stricted to the solution. The (∂2V0ϕ/∂T)P, second derivative of tempera-
ture reveals the structure building property of glycols in the solutions
of SEP. Further, rendering data concluded that ion-hydrophilic and
hydrophilic-hydrophilic interactions predominated in the current stud-
ied system over ion-hydrophobic and hydrophobic-hydrophobic
interactions.

Appendix A. Supplementary data

Fig. 7. Graph of K0ϕ, s, partial molar isentropic compression for (a) EG (b) PG in 0.00, 0.01,
0.03 and 0.05 mol·kg−1 SEP solutions of water at various temperatures.
Equations and tables for partial molar volume of transfer, partial
molar isentropic compression of transfer, temperature dependent par-
coefficients of pair interaction, while VABB and KABB are the volume and tial molar volumes, partial molar expansibility, coefficient of thermal
isentropic compression coefficients of triplet interaction. Table S5 of expansion, pair and triplet coefficients of interaction. This content is
the Supporting data provides the values of these parameters. The values available in Supplementary information. Supplementary data to this

Table 7
Comparison of partial molar volume and partial molar isentropic compression obtained in this work with the literature data.

T/K V0ϕ × 106/(m3·mol−1) Deva/m3·mol−1 K0ϕ, s × 106/(m3·mol−1·GPa−1) Deva/m3·mol−1·GPa−1

Experimental Literature Experimental Literature

Ethylene glycol + water

54.55 54.37 [89] 0.18 −45.12 −45.13 [41] 0.01
293.15 54.43 [90] 0.12
54.58 53.66 [76] 0.92 −44.24 −44.23 [41] −0.01
298.15 53.67 [39] 0.91 −44.34 [39] 0.1
54.59 [89] −0.01
54.59 [91] −0.01
54.6 53.88 [76] 0.72 −43.48 −43.48 [41] 0
303.15 54.13 [39] 0.47
54.77 [89] −0.17
54.8 [81] −0.2
54.61 54.08 [76] 0.53 −42.89 −42.88[41] −0.01
308.15 54.54 [39] 0.07 −42.99[39] 0.1
54.97 [89] −0.36
54.89 [92] −0.28
a
Deviation between present work and the literature data.
12 Ashima et al. / Results in Chemistry 2 (2020) 100049

article can be found online at https://doi.org/10.1016/j.rechem.2020. [33] T. Sun, A.S. Teja, Viscosity, and thermal conductivity of aqueous ethylene,
diethylene, and triethylene glycol mixtures between 290 K and 450 K, J. Chem.
100049. Eng. Data 48 (2003) 198–202.
[34] S. Srilalitha, M.C.S. Subha, K. Chowdoji Rao, Temperature sensitive semi-IPN micro-
spheres from sodium alginate andN-isopropylacrylamide for controlled release of 5-
fluorouracil, J. Pure Appl. Ultrason. 18 (1996) 59–73.
References [35] N. Jha, S. Ramaprabhu, Thermal conductivity studies of metal dispersed multiwalled
carbon nanotubes in water and ethylene glycol based nanofluids, J. Appl. Phys. 106
[1] C. Almeida, J.M.F. Nogueira, Determination of trace levels of parabens in real matri- (2009), 084317. .
ces by bar adsorptive microextraction using selective sorbent phases, J. Chromatogr. [36] F. Jalali, M. Shamsipur, N. Alizadeh, Conductance study of the thermodynamics of
A 1348 (2014) 17–26. micellization of 1-hexadecylpyridinium bromide in (water + cosolvent), J. Chem.
[2] J.B. Claver, M.C. Valencia, L.F.C. Vallvey, Analysis of parabens in cosmetics by low Thermodyn. 32 (2000) 755–765.
pressure liquid chromatography with monolithic column and chemiluminescent [37] M. Singla, R. Jindal, H. Kumar, Volumetric, acoustic, and UV absorption studies on
detection, Talanta 79 (2009) 499–506. solute–solvent interactions of dipeptides of glycine with aqueous amoxicillin solu-
[3] M.S. Diaz-Cruz, D. Barcelo, Personal Care Products in the Aquatic Environment, tions, Thermochim. Acta 591 (2014) 140–151.
Springer Switzerland, 2015. [38] T.J. Fortin, A. Laesecke, M. Freund, S. Outcalt, Advanced calibration, adjustment, and
[4] C. Haman, X. Dauchy, C. Rosin, J.F. Munoz, Occurrence, fate and behavior of parabens operation of a density and sound speed analyzer, J. Chem. Thermodyn. 57 (2013)
in aquatic environments, Water Res. Rev. 68 (2015) 1–11. 276–285.
[5] M. Falasinski, M. Gawrys, M. Broniatowski, P. Wydro, Studies on the interactions be- [39] K. Kaur, K.C. Juglan, H. Kumar, Investigation on temperature-dependent volumetric
tween parabens and lipid membrane components in monolayers at the air/aqueous and acoustical properties of homologous series of glycols in aqueous sorbitol solu-
solution interface, Biochim Biophys.Acta 1858 (2016) 836–844. tions, J. Chem. Eng. Data 62 (2017) 3769–3782.
[6] M.G. Soni, I.G. Carabin, G.A. Burdock, Safety assessment of esters of p- [40] O.E.A. Ahmed Adam, A.H. Al-Dujaili, A.M. Awwad, Volumetric properties of aqueous
hydroxybenzoic acid (parabens), Food Chem. Toxicol. 43 (2005) 985–1015. solutions of ethylene glycols in the temperature range of 293.15–318.15 K, ISRN
[7] Z.J. Cardenas, D.M. Jimenez, F. Martinez, Thermodynamic study of the partitioning of Phys. Chem. (2014) 1–10.
methyl and propyl parabens in some organic solvent/buffer systems, J. Chem. [41] K. Kaur, I. Behal, K.C. Juglan, H. Kumar, Volumetric and ultrasonic studies on interac-
Thermodyn. 86 (2015) 180–187. tions of ethylene glycol, diethylene glycol and triethylene glycol in aqueous solu-
[8] J. Lu, H. Li, Y. Tu, Z. Yang, Biodegradation of four selected parabens with aerobic ac- tions of glycerol at temperatures T = (293.15 K − 308.15) K, J. Chem.
tivated sludge and their transesterification product, Ecotoxicol. Environ. Saf. 156 Thermodyn. 125 (2018) 93–106.
(2018) 48–55. [42] C.M. Romero, M.S. Paez, D. Perez, A comparative study of the volumetric properties
[9] S. Oishi, Effects of propyl paraben on the male reproductive system, Food Chem. of dilute aqueous solutions of 1-propanol, 1,2-propanediol, 1,3-propanediol, and
Toxicol. 40 (2002) 1807–1813. 1,2,3-propanetriol at various temperatures, J. Chem. Thermodyn. 40 (2008)
[10] M. Demirkurt, Y.A. Olcer, M.M. Demir, A.E. Eroglu, Electrospun polystyrene fibers 1645–1653.
knitted around imprinted acrylate microspheres as sorbent for paraben derivatives, [43] D.M. Makarov, G.I. Egorov, A.M. Kolker, Temperature and composition dependences
Anal. Chim.Acta 1014 (2018) 1–9. of volumetric properties of (water + 1,2-propanediol) binary system, J. Mol. Liq.
[11] S. Michalkiewicz, Anodic oxidation of parabens in acetic acid–acetonitrile solutions, 222 (2016) 656–662.
J. Appl. Electrochem. 43 (2013) 85–97. [44] W. Grzybkowski, D. Warminska, Apparent molar volumes and isentropic compress-
[12] P. Hu, X. Chen, R.J. Whitener, E.T. Boder, J.O. Jones, A. Porollo, J. Chen, L. Zhao, Effects ibilities of tetraalkylammonium bromides in aqueous propane-1,2-diol. An attempt
of parabens on adipocyte differentiation, Toxicol. Sci. 131 (2013) 56–70. to design hydraulic liquids, J. Chem. Eng. Data 61 (2016) 2933–2945.
[13] P. Canosa, I. Rodriguez, E. Rubi, N. Negreira, R. Cela, Formation of halogenated by- [45] C.W. Chang, T.L. Hsuing, C.P. Lui, C.H. Tu, Densities, surface tensions, and isobaric
products of parabens in chlorinated water, Anal. Chim.Acta 575 (2006) 106–113. vapor–liquid equilibria for the mixtures of 2-propanol, water, and 1,2-propanediol,
[14] E.J. Routledge, J. Parker, J. Odum, J. Ashby, J.P. Sumpter, Some alkyl hydroxy benzoate Fluid Phase Equilib. 389 (2015) 28–40.
preservatives (parabens) are estrogenic, Toxicol. Appl. Pharmacol. 153 (1998) [46] M. Rodrigues, A.Z. Francesconi, Experimental study of the excess molar volumes of
12–19. binary and ternary mixtures containing water + (1,2-ethanediol, or 1,2-
[15] S. Oishi, Effects of butylparaben on the male reproductive system in rats, Toxicol. propanediol, or 1,3-propanediol, or 1,2-butanediol) + (1-n-butyl-3-
Ind. Health 17 (2001) 31–39. methylimidazolium bromide) at 298.15 K and atmospheric pressure, J. Sol. Chem.
[16] C. Valdez, E.I. Isaacson, F.P. Cosgrove, Interaction of methyl and propyl parabens 40 (2011) 1863–1873.
with selected sucrose esters, J. Pharm. Sci. 57 (1968) 2093–2096. [47] S.K. Begum, R.J. Clarke, M.S. Ahmed, S. Begum, M.A. Saleh, Volumetric, viscosi-
[17] M. Ma, T. Lee, E. Kwong, Interaction of methylparaben preservative with selected metric and surface properties of aqueous solutions of triethylene glycol,
sugars and sugar alcohols, J. Pharm. Sci. 91 (2002) 1715–1723. tetraethylene glycol, and tetraethylene glycol dimethyl ether, J. Mol. Liq. 177
[18] S.M. Blaug, S.S. Ahsan, Interaction of parabens with nonionic macromolecules, J. (2013) 11–18.
Pharm. Sci. 50 (1961) 441–443. [48] N. Chakraborty, H. Kumar, K. Kaur, K.C. Juglan, Acoustic and thermodynamic study of
[19] W.P. Evans, The solubilisation and inactivation of preservatives by non-ionic deter- D-Panthenol in aqueous solutions of glycol at different temperatures, J. Chem.
gents, J. Pharm. Pharmcol. 16 (1964) 323–331. Thermodyn. 126 (2018) 137–146.
[20] K.S. Alexender, B. Laprade, J.W. Mauger, A.N. Paruta, Thermodynamics of aqueous [49] M.T.Z. Moattar, H. Sheekari, Apparent molar volume and isentropic compress-
solutions of parabens, J. Pharm. Sci. 67 (1978) 624–627. ibility of ionic liquid 1-butyl-3-methylimidazolium bromide in water, metha-
[21] A.N. Paruta, Solubility of parabens in alcohols, J. Pharm. Sci. 58 (1969) 216–219. nol, and ethanol at T=(298.15 to 318.15)K, J. Chem. Thermodyn. 37 (2005)
[22] A.N. Paruta, B.B. Sheth, Solubility of parabens in syrup vehicles, J. Pharma. Sci. 55 1029–1035.
(1966) 1208–1211. [50] F.J. Millero, Molal volumes of electrolytes, Chem. Rev. 71 (1971) 147.
[23] Z.J. Cardenas, D.M. Jimenez, D.R. Delgado, O.A. Almanza, A. Jouyban, F. Martínez, W.E. [51] B. Das, D.K. Hazra, Apparent and partial molar volumes of some symmetrical
Acree, Solubility and preferential solvation of some n-alkyl-parabens in tetraalkylammonium perchlorates in 2-methoxyethanol at 25, 35, and 45 °C, Bull.
methanol+water mixtures at 298.15K, J. Chem. Thermodyn. 108 (2017) 26–37. Chem. Soc. Jpn. 68 (1995) 734–737.
[24] J. Unga, F. Tajarobi, O. Norder, G. Frenning, A. Larsson, Relating solubility data of [52] N. Saha, B. Das, Apparent molar volumes of some symmetrical tetraalkylammonium
parabens in liquid PEG 400 to the behaviour of PEG 4000-parabens solid disper- bromides in acetonitrile at (298.15, 308.15, and 318.15) K, J. Chem. Eng. Data 42
sions, Eur. J. Pharm. Biopharm. 73 (2009) 260–268. (1997) 227–229.
[25] H. Kumar, M. Singla, H. Mittal, Volumetric, acoustic and viscometric behaviour of [53] A.K. Mishra, J.C. Ahluwalia, Apparent molal volumes of amino acids, N-acetylamino
dipotassium hydrogen phosphate and disodium hydrogen phosphate in aqueous acids, and peptides in aqueous solutions, J. Phys. Chem. 88 (1984) 86–92.
solution of N-acetyl glycine at different temperatures, J. Chem. Thermodyn. 94 [54] M.J. Iqbal, M.A. Chaudhry, Effect of temperature on volumetric and viscometric
(2016) 204–220. properties of some non-steroidal anti-inflammatory drugs in aprotic solvents, J.
[26] M. Iqbal, M. Mateeullah, Partial molar volumes of some dipolar ions in water at 35 Chem. Thermodyn. 42 (2010) 951–956.
°C, Can. J. Chem. 68 (1990) 725–727. [55] H. Kumar, I. Behal, Thermodynamics of (solute + solute) and (solute + solvent) in-
[27] J. Krakowiak, H. Koziel, W. Grzybkowski, Apparent molar volumes of divalent tran- teractions of homologous series of amino acids with thiamine hydrochloride in
sition metal perchlorates and chlorides in N,N-dimethylacetamide, J. Mol. Liq. 118 aqueous medium at T = (305.15, 310.15, 315.15) K, J. Chem. Thermodyn. 102
(2005) 57–65. (2016) 48–62.
[28] T.V. Chalikian, Volumetric measurements in binary solvents: theory to experiment, [56] Z. Yan, J.J. Wang, H. Zheng, D. Liu, Synthesis, antiproliferative activity and DNA-
Biophys. Chem. 156 (2011) 3–12. binding properties of nitrogen and sulfur heterocyclic norcantharidin acylamide
[29] S. Lee, A. Tikhomirova, N. Shalvardjian, T.V. Chalikian, Corrigendum to “Partial molar acid, J. Solut. Chem. 27 (1998) 473–477.
volumes and adiabatic compressibilities of unfolded protein states”, Biophys. Chem. [57] K. Kaur, K.C. Juglan, H. Kumar, Temperature dependent physicochemical studies of
134 (2008) 185–199. polyethylene glycols (PEG-400 and PEG-4000) in aqueous sorbitol solutions, J.
[30] H.C. Fuller, Ethylene glycol—its properties and uses, Ind. Eng. Chem. 16 (1924) Mol. Liq. 268 (2018) 700–706.
624–626. [58] A. Płaczek, H. Koziel, W. Grzybkowski, Apparent molar compressibilities and vol-
[31] V.K. Syal, A. Chauhan, S. Chauhan, Ultrasonic velocity, viscosity and density studies umes of some 1,1-electrolytes in N,N-dimethylacetamide and N,N-
of poly (ethylene glycols)(PEG - 8,000, PEG - 20,000) in acetonitrile (AN) and dimethylformamide, J. Chem. Eng. Data 52 (2007) 699–706.
water (H2O) mixtures at 250 °C, J. Pure Appl. Ultrason. 27 (2005) 61–69. [59] A. Ali, S. Shahjahan, Volumetric and viscometric behaviour of some amino acids and
[32] A.V. Sarode, A.C. Kumbharkhane, Dielectric relaxation study of poly(ethylene gly- their group contributions in aqueous tetramethylammonium bromide at different
cols) using TDR technique, J.Mol Liq. 164 (2011) 226–232. temperatures, Z. Phys. Chem. 222 (2008) 1519–1532.
 Ashima et al. / Results in Chemistry 2 (2020) 100049 13

[60] B. Sinha, A. Sarkar, P.K. Roy, D. Brahman, Physicochemical properties of L-alanine in [79] T.M. Aminabhavi, B. Gopalakrishna, Density, viscosity, refractive index, and speed of
aqueous silver sulphate solutions at (298.15, 308.15, and 318.15) K, Int. J. sound in aqueous mixtures of N,N-dimethylformamide, dimethyl sulfoxide, N,N-
Thermophys. 32 (2011) 2062–2078. dimethylacetamide, acetonitrile, ethylene glycol, diethylene glycol, 1,4-dioxane, tet-
[61] L.G. Hepler, Thermal expansion and structure in water and aqueous solutions, Can. J. rahydrofuran, 2-methoxyethanol, and 2-ethoxyethanol at 298.15 K, J. Chem. Eng.
Chem. 47 (1969) 4613–4617. Data 40 (1995) 856–861.
[62] K. Kaur, K.C. Juglan, H. Kumar, Acoustical and volumetric investigation of polyethyl- [80] H. Kumar, I. Behal, Volumetric and ultrasonic investigation of molecular interactions
ene glycol 400 and polyethylene glycol 4000 in aqueous solutions of glycerol at dif- of l-serine and l-threonine in aqueous nicotinamide solutions at T =
ferent temperatures, J. Chem. Thermodyn. 127 (2018) 8–16. (288.15–318.15) K, J. Mol. Liq. 219 (2016) 756–764.
[63] F.J. Millero, R.A. Horne (Eds.), Structure and Transport Process in Water and Aque- [81] A.K. Nain, Ultrasonic and viscometric studies of molecular interactions in binary
ous Solutions, Wiley-Interscience, New York 1972, pp. 519–595. mixtures of formamide with ethanol, 1-propanol, 1,2-ethanediol and 1,2-
[64] P.R. Misra, B. Das, M.L. Parmar, D.S. Banyal, Extragenital lichen sclerosus et propanediol at different temperatures, J. Mol. Liq. 140 (2008) 108–116.
atrophicus, Indian J. Chem. 44A (2005) 1582–1588. [82] B. Orge, B.E. De Cominges, G. Marino, M. Iglesias, J. Tojo, Derived properties of binary
[65] R. Gaba, A. Pal, D. Sharma, J. Kaur, Solvation behavior of glycine and glycyl dipeptide mixtures containing (acetone or methanol) + hydroxil compounds, Phys. Chem.
in aqueous 1-butyl-3-methylimidazolium bromide ionic liquid solutions at different Liq. 39 (2001) 99–116.
temperatures, J. Mol. Liq. 233 (2017) 38–44. [83] A.Z. Zarei, M. Narjes, Z. Zinab, Densities, excess molar volumes, viscosity, and refrac-
[66] S. Cabani, G. Conti, E. Matteoli, Partial molal expansibilities of organic compounds in tive indices of binary and ternary liquid mixtures of methanol (1) + ethanol (2) +
aqueous solution. I. Alcohols and ethers, J. Solut. Chem. 5 (1976) 751–763. 1,2-propanediol (3) atP= 81.5 kPa, J. Chem. Eng. Data 54 (2009) 847–854.
[67] T. Katrinak, L. Hnedkovsky, C. Ivan, Partial molar volumes and partial molar isentro- [84] N.G. Tsierkezos, I.E. Molinou, Densities and viscosities of ethylene glycol binary mix-
pic compressions of three polyhydric alcohols derived from propane at infinite dilu- tures at 293.15 K, J. Chem. Eng. Data 44 (1999) 955–958.
tion in water at temperatures T = (278 to 318) K and atmospheric pressure, J. [85] N.V. Sastry, M.C. Patel, Densities, excess molar volumes, viscosities, speeds of sound,
Chem. Eng. Data 57 (2012) 1152–1159. excess isentropic compressibilities, and relative permittivities for alkyl (methyl,
[68] N.G. Tsierkezos, M. Palaiologou, Ultrasonic studies of liquid mixtures of either water ethyl, butyl, and isoamyl) acetates + glycols at different temperatures, J. Chem.
or dimethylsulfoxide with ethylene glycol, diethylene glycol, triethylene glycol, Eng. Data 48 (2003) 1019–1027.
tetraethylene glycol, 1,2-propylene glycol and 1,4-butylene glycol at 298.15K, [86] E. Zorebski, A. Przybyła, Volume effects for binary mixtures of propane-1,2-diol with
Phys. Chem. Liq. 47 (2009) 447–459. methanol, propan-1-ol, hexan-1-ol, octan-1-ol, or nonan-1-ol at temperatures
[69] K. Klimaszewski, E. Stronka-Lewkowska, K. Abramczyk, A. Bald, Acoustic and volu- (293.15 to 318.15)K, J. Chem. Thermodyn. 59 (2013) 127–134.
metric studies on (triethylene glycol+water) mixtures in a wide temperature [87] B.B. Gurung, M.N. Roy, Study of densities, viscosity deviations and isentropic com-
range, J. Chem. Thermodyn. 89 (2015) 212–222. pressibilities of ternary liquid mixtures of water and ethane-1, 2-diol with some
[70] I. Bahadur, N. Deenadayalu, Apparent molar volume and apparent molar isentropic monoalcohols at various temperature, Phys. Chem. Liq. 45 (2007) 331–343.
compressibility for the binary systems {methyltrioctylammoniumbis [88] E. Zorebski, M. Dzida, M. Piotrowska, Study of the acoustic and thermodynamic
(trifluoromethylsulfonyl)imide + ethyl acetate or ethanol} at different tempera- properties of 1,2- and 1,3-propanediol by means of high-pressure speed of sound
tures under atmospheric pressure, Thermochim. Acta 566 (2013) 77–83. measurements at temperatures from (293 to 318) K and pressures up to 101
[71] D. Kitchen, L. Reed, R. Levy, Molecular dynamics simulation of solvated protein at MPa, J. Chem. Eng. Data 53 (2008) 136–144.
high pressure, Biochem 31 (1992) 10083–10093. [89] T.T. Chiao, A.R. Thompson, Anal. Chem. 29 (1957) 1678–1681.
[72] C.M. Romero, F. Negrete, Effect of temperature on partial molar volumes and viscos- [90] I. Cibulka, Partial molar volumes and partial molar isentropic compressions of four
ities of aqueous solutions of α-dl-aminobutyric acid, dl-norvaline and dl-norleucine, poly(ethylene glycols) at infinite dilution in water at temperatures T = (278 to
Phys. Chem. Liq. 42 (2004) 261–267. 343) K and atmospheric pressure, J. Chem. Eng. Data 61 (2016) 748–759.
[73] A. Soto, A. Arce, M.K. Khoshkbarchi, Thermodynamics of diglycine and triglycine in [91] A. Ray, G. Nemethy, Densities and partial molal volumes of water-ethylene glycol
aqueous NaCl solutions: apparent molar volume, isentropic compressibility, and re- mixtures, J. Chem. Eng. Data 18 (1973) 309–311.
fractive index, J. Solut. Chem. 33 (2004) 11–21. [92] A. Sikora, Volume properties of dilute aqueous solutions of poly(oxyethylene) and
[74] W.G. McMillan, J.E. Mayer, The statistical thermodynamics of multicomponent sys- its low molecular models, Collect. Czechoslov. Chem. Commun. 50 (1985)
tems, J. Chem. Phys. 13 (1945) 276–305. 2146–2158.
[75] H.L. Friedman, C.V. Krishnan, Enthalpies of alkyl sulfonates in water, heavy water, [93] A. Thakur, K.C. Juglan, H. Kumar, K. Kaur, Investigation on molecular interaction of
and water-alcohol mixtures and the interaction of water with methylene groups, glycols in methanol solutions of methylparaben (methyl 4 – hydroxybenzoate) at
J. Solut. Chem. 2 (1973) 37–51. different temperatures through thermo-acoustical analysis, J. Mol. Liq. 288 (2019)
[76] K. Kaur, K.C. Juglan, H. Kumar, I. Behal, Thermodynamic interactions study of some 111014.
ethylene glycols in aqueous aniline solutions at different temperatures: an acousti- [94] Ashima, K.C. Juglan, H. Kumar, Volumetric and ultrasonic investigation of polyethyl-
cal and volumetric approach, J. Chem. Eng. Data 63 (2018) 3237–3251. ene glycols (PEG-200 and PEG-600) in aqueous solutions of sodium methylparaben
[77] N.G. Tsierkezosa, I.E. Molinou, Thermodynamic properties of water + ethylene gly- at various temperatures, J. Chem. Thermodyn. 140 (2020) 105916.
col at 283.15, 293.15, 303.15, and 313.15 K, J. Chem. Eng. Data 43 (1998) 989–993.
[78] H. Kumar, K. Kaur, S.P. Kaur, M. Singla, Studies of volumetric and acoustic properties
of trisodium citrate and tripotassium citrate in aqueous solutions of N-acetyl glycine
at different temperatures, J. Chem. Thermodyn. 59 (2013) 173–181.