Acoustic and volumetric properties of betaine hydrochloride drug in aqueous d(+)-glucose and sucrose solutions

J. Chem. Thermodynamics 77 (2014) 123–130

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J. Chem. Thermodynamics

journal homepage: www.elsevier .com/locate / jc t

Acoustic and volumetric properties of betaine hydrochloride drugin aqueous D(+)-glucose and sucrose solutions

http://dx.doi.org/10.1016/j.jct.2014.05.0150021-9614/� 2014 Elsevier Ltd. All rights reserved.

⇑ Corresponding authors. Tel.: +91 9908455351 (S.J. Tangeda). Tel.: +91 4422574248 (R.L. Gardas).

E-mail addresses: [email protected] (S.J. Tangeda), [email protected](R.L. Gardas).

Suresh Ryshetti a, Akash Gupta b, Savitha Jyostna Tangeda a,⇑, Ramesh L. Gardas b,⇑a Department of Chemistry, Kakatiya University, Warangal 506009, Indiab Department of Chemistry, Indian Institute of Technology Madras, Chennai 600036, India

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

Article history:Received 11 January 2014Received in revised form 16 May 2014Accepted 20 May 2014Available online 29 May 2014

Keywords:DensitySpeed of soundBetaine hydrochloride drugCo-sphere overlap modelHepler’s constant

The densities (q) and speeds of sound (u) of betaine hydrochloride (B.HCl) drug (0.01 to 0.06) mol � kg�1

in (0.10, 0.20 and 0.30) mol � kg�1 aqueous D(+)-glucose and sucrose solutions are reported as a functionof temperature at T = (293.15 to 313.15) K and atmospheric pressure. The values of density (q) and speedof sound (u) are obtained with high precision. These values have been used to estimate the apparentmolar volume (V2,/), partial molar volume (V12 ), transfer partial molar volume (DtV

12 ), apparent molar

isentropic compressibility (Ks,2,/), partial molar isentropic compressibility (K1s;2), transfer partial molarcompressibility (DtK

1s;2), hydration number (NH), partial molar expansion (E12 ) and Hepler’s constant

(@2V12 /@T2)P. Furthermore, pair (VAB and KAB) and triplet (VABB and KABB) interaction coefficients have beencomputed from the values of DtV

12 and DtK

1s;2. The co-sphere overlap model is used to understand the

values of DtV12 and DtK

1s;2. The positive values of (@2V12 /@T2)P indicate structure making ability of betaine

hydrochloride in aqueous D(+)-glucose and sucrose solutions at the temperatures and compositionsinvestigated.

� 2014 Elsevier Ltd. All rights reserved.

1. Introduction

Volumetric and acoustic properties are powerful tools to ana-lyze the behavior of various solutes such as drugs, amino acids,proteins, peptides, carbohydrates and ionic liquids in aqueousand non-aqueous solutions [1–5]. Drug-macromolecular interac-tions are playing a significant role in understanding the activityof drugs in biological systems [6]. It is difficult to study the drugactivity directly in complex biological processes and the mecha-nism of these molecular processes is not yet clearly understood.Attempts are being made to interpret these drug-molecular inter-actions through thermophysical properties such as density andspeed of sound [7,8]. Most of the biochemical processes occur inaqueous media. The (drug + water) molecular interactions andtheir temperature dependence play an important role in under-standing the drug action across the biological membrane [9]. Manyresearchers have studied the density, speed of sound and viscosityof (drug + water) and (drug + water + alcohol) systems and inter-preted the results in terms of (hydrophilic + hydrophilic) and(hydrophilic + hydrophobic) interactions [10–12]. The detailed

literature survey reveals that thermophysical properties of thedrugs in aqueous carbohydrate solutions have not been reported.This prompted us to investigate the volumetric and acoustic prop-erties of betaine hydrochloride (B.HCl) drug in water and aqueousD(+)-glucose and sucrose solutions.

B.HCl drug, used as the stomach acidifier and digestive aid forthe human body, finds applicability in treating abnormally low lev-els of potassium, food allergies, yeast infection, diarrhea, hay fever,thyroid disorders, etc. However more systematic studies areneeded to gather the evidence to rate the effectiveness of B.HClfor these uses. In the present study, we have examined the molec-ular interactions of B.HCl drug in aqueous D(+)-glucose and sucrosesolutions at low concentrations in the form of solutes andco-solutes. The experimental values of density (q) and speed ofsound (u) of (0.01 to 0.06) mol � kg�1 B.HCl drug in (0.1, 0.2 and0.3) mol � kg�1 aqueous D(+)-glucose and sucrose solutions havebeen measured at T = (293.15 to 313.15) K and atmospheric pres-sure. The results are used to calculate several parameters such aspartial molar properties, hydration numbers, pair and tripletinteraction coefficients and Hepler’s constant. These parametersare used to interpret the (hydrophilic + hydrophilic), (hydro-philic + hydrophobic), electrostatic interactions, structure mak-ing/breaking ability of B.HCl drug in aqueous D(+)-glucose andsucrose solutions. To the best of our knowledge from the literaturesurvey, the values of density and speed of sound of B.HCl drug in

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124 S. Ryshetti et al. / J. Chem. Thermodynamics 77 (2014) 123–130

aqueous D(+)-glucose and sucrose solutions have not been reportedat the concentrations and temperatures investigated in this paper.

2. Experimental

All chemicals (shown in table 1) were used after drying overP2O5 in vacuum desiccators at room temperature for 48 h. Freshlyprepared doubly distilled, degassed water with a specific conduc-tance less than 1 � 10�6 S � cm�1 was used for the preparation ofaqueous solutions. The aqueous solutions were prepared on massbasis at room temperature over a concentration range (0.01 to0.06) mol � kg�1 and kept in airtight bottles to minimize exposureof solutions to air. The mass measurements were done on an elec-tronic analytical balance (Sartorius, Model CPA225D) with a preci-sion of ±0.01 mg. We have measured the density (q) and speed ofsound (u) of solutions on the same day of sample preparation byusing Anton Paar DSA 5000M instrument. The instrument was cal-ibrated with doubly distilled water and dry air at the investigatedtemperatures; uncertainties in the measurements of density (q)and speed of sound (u) at 3 MHz frequency are ±5 � 10�3 kg �m�3

and ±0.5 m � s�1, respectively. The experiments were carried outat T = (293.15 to 313.15) K with an accuracy of ±0.01 K. The tem-peratures were controlled by a Peltier thermostat (PT 100) whichis in-built on Anton Paar DSA 5000M instrument [13].

3. Results and discussion

The densities (q) and speeds of sound (u) of B.HCl drug in water,aqueous glucose and sucrose solutions of various molalities atT = (293.15 to 313.15) K are given in table 2. The plots of density(q) and speed of sound (u) vs. molality (m) of B.HCl drug in waterat different temperatures are shown in figures 1 and 2, respec-tively. The comparison of experimental density (q) values withavailable literature data for dilute solution of D(+)-glucose andsucrose are presented in supporting information (table ST1). Asshown in table ST1, experimental density data of aqueous solutionof D(+)-glucose and sucrose are in good agreement with availableliterature data (relative deviations are within 0.1%) at T = (293.15and 298.15) K. However deviations are larger up to 0.3% for aque-ous solution of D(+)-glucose at T = (303.15 and 308.15) K. Thesedeviations can be due essentially to the purity of the sample andalso from the experimental technique adopted. As shown in thesupporting information (figure S1), experimental speeds of sound(u) values are in good agreement with available literature datafor aqueous solution of D(+)-glucose at T = 298.15 K and similartrends are observed at other studied temperatures and for aqueoussolution of sucrose also. As shown in table 2, the decreasing valuesof density (q) or increasing values of speed of sound (u) withincrease in temperature suggests the consequence of temperatureon the solvation behavior of solute. Values of the apparent molarvolume (V2,/) and apparent molar isentropic compressibility(Ks,2,/) have been calculated from the values of density (q) andspeed of sound (u) by using the following equations (1) and (2),respectively [14], the values of V2,/ and Ks,2,/ are reported in table3 and these values increase with the temperature, concentrationsof solute and co-solute.

V2;/ ¼ ½M=q� � ½1000ðq� qoÞ=ðmqqoÞ�; ð1Þ

TABLE 1Provenance and mass fraction purity of the chemicals used.

Compound Mass fraction purity CAS No. Source

Betaine HCl 0.990 590-46-5 Sigma Aldrich Co.

D(+)-glucose 0.980 50-99-7 Finar Chemical Ltd.

Sucrose 0.995 57-50-1 Himedia Laboratories

Ks;2;/ ¼ ½jsM=q� � ½1000ðjosq� jsqoÞ=ðmqqoÞ�; ð2Þ

where M and m are molar mass and molality of B.HCl drug, q and qo

refer to the density of solution and solvent (water or water + D(+)-glucose/sucrose), js and jo

s represent the isentropic compressibilityof solution and solvent, respectively. Values of isentropic compress-ibility (js) are calculated from the values of density (q) and speed ofsound (u) by using the relation [15]:

js ¼ 1=ðu2qÞ: ð3Þ

Values of the partial molar volume (V12 ) and partial molar isen-tropic compressibility (K1s;2) for B.HCl drug in water, aqueous glu-cose and sucrose solutions are reported by the least-squarefitting of the linear plots of V2,/ and Ks,2,/ against the molality(m) of B.HCl drug, respectively [16].

V2;/ ¼ V12 þ Sv �m; ð4Þ

Ks;2;/ ¼ K1s;2 þ Sk �m: ð5Þ

Here Sv and Sk are the experimental slopes. These values areaccountable for the (solute + solute) interactions. The experimentalslopes Sv and Sk are semi-empirical parameters which depend onsolvent, solute, and temperature, and for large organic solutesthese values are not of much significance [6]. The partial molarproperties (infinite dilution apparent molar properties) i.e. V12and K1s;2 indicate the (solute + solvent) interactions at infinite dilu-tion and their values are given in table 4. In the present study, posi-tive values of V12 and negative values of K1s;2 account for strong(solute + solvent) interactions between B.HCl drug and water or(water + aqueous glucose/sucrose) solutions [14]. The values ofV12 and K1s;2 increase with increasing the temperature for B.HCldrug in water and all the investigated concentrations of D(+)-glu-cose and sucrose, mainly due to releasing of water molecules fromthe second solvation layer of the ionic (AN+(CH3)3/Cl�)/hydrophilic(ACOOH) groups of B.HCl drug [17]. The values of V12 and K1s;2increase with the concentration of D(+)-glucose and sucrose, whichsuggests that, for the systems studied, the extent of molecularinteractions such as (ionic + hydrophilic) and (hydrophilic + hydro-philic) increase with solute concentration. These results (table 4)are also useful in understanding the effects of temperature andcomposition on the molecular interactions of B.HCl drug in aque-ous D(+)-glucose and sucrose solutions. Furthermore, these molec-ular interactions can be understood on the basis of the co-sphereoverlap model which is developed by Gurney et al. [18,19].Such possible interactions in a ternary mixture (B.HCl drug +water + D(+)-glucose/sucrose) can be regarded as follows:(i) ionic/(hydrophilic + hydrophilic) interactions between the ionic(AN+(CH3)3/Cl�)/hydrophilic (ACOOH) groups of B.HCl drugand (AOH, AC = O, and AOA) groups of D(+)-glucose/sucrose.(ii) ionic/(hydrophilic + hydrophobic) interaction between theionic (AN+(CH3)3/Cl�)/hydrophilic (ACOOH) groups of B.HCl drugand ACH2/ACH groups of D(+)-glucose/sucrose. (iii) (Hydropho-bic + hydrophobic) interaction between the ACH2 groups of B.HCldrug and ACH2/ACH groups of D(+)-glucose/sucrose.

Values of the transfer partial molar volume (DtV12 ) and transfer

partial molar isentropic compressibility (DtK1s;2) of B.HCl drug

in aqueous glucose and sucrose solutions are obtained from thefollowing equation [20]:

DtX12 ¼ X12 ðin aqueous dðþÞ � glucose=sucrose solutionsÞ

� X12 ðin waterÞ; ð6Þ

where DtX12 = (DtV

12 or DtK

1s;2), X12 = (V12 or K1s;2). A perusal of table

5 reveals that the values of DtX12 are free from (solute + solute)

interactions and therefore furnish information about (solute +solvent) interactions [21]. The positive values of DtX

12 indicate the

TABLE 2Density (q) and speed of sound (u) of B.HCl in water, aqueous D(+)-glucose and sucrose solutions at T = (293.15 to 313.15) K and pressure p = 0.1 MPa.a

m/(mol � kg�1) 10�3q/(kg �m�3) u/(m � s�1) 10�3q/(kg �m�3) u/(m � s�1) 10�3q/(kg �m�3) u/(m � s�1) 10�3q/(kg �m�3) u/(m � s�1) 10�3q/(kg �m�3) u/(m � s�1)

T = 293.15 K 298.15 K 303.15 K 308.15 K 313.15 K

(B.HCl + water)0.00000 0.998224 1482.77 0.997074 1496.69 0.995676 1509.05 0.994061 1519.73 0.992245 1528.780.00988 0.998597 1483.79 0.997445 1497.70 0.996042 1510.05 0.994425 1520.72 0.992605 1529.760.02034 0.998988 1484.85 0.997829 1498.74 0.996428 1511.03 0.994806 1521.71 0.992980 1530.740.03199 0.999418 1485.96 0.998253 1499.78 0.996847 1512.12 0.995225 1522.82 0.993389 1531.760.03929 0.999672 1486.62 0.998509 1500.47 0.997099 1512.76 0.995477 1523.45 0.993638 1532.410.04992 1.000047 1487.58 0.998883 1501.34 0.997471 1513.57 0.995846 1524.42 0.993998 1533.270.05925 1.000367 1488.42 0.999196 1502.35 0.997795 1514.23 0.996165 1525.12 0.994316 1534.06

(B.HCl + 0.10 mol � kg�1D(+)-glucose)

0.00000 1.005068 1489.20 1.003872 1502.86 1.002438 1514.80 1.000793 1525.31 0.998945 1534.120.00974 1.005425 1490.23 1.004222 1503.88 1.002782 1515.82 1.001132 1526.31 0.999278 1535.100.01935 1.005772 1491.21 1.004567 1504.83 1.003119 1516.79 1.001460 1527.25 0.999601 1536.050.02962 1.006139 1492.18 1.004927 1505.86 1.003472 1517.77 1.001808 1528.26 0.999942 1537.030.04056 1.006521 1493.22 1.005307 1506.91 1.003845 1518.83 1.002168 1529.29 1.000300 1538.040.04945 1.006835 1493.98 1.005611 1507.76 1.004142 1519.67 1.002453 1530.12 1.000587 1538.810.05791 1.007114 1494.8 1.005885 1508.49 1.004421 1520.41 1.002719 1530.87 1.000850 1539.50


0.00000 1.012079 1495.98 1.010894 1509.43 1.009419 1521.18 1.007724 1531.25 1.005861 1539.820.01009 1.012440 1497.08 1.011250 1510.50 1.009766 1522.26 1.008067 1532.30 1.006200 1540.850.01939 1.012768 1498.05 1.011575 1511.46 1.010089 1523.19 1.008387 1533.21 1.006511 1541.750.02952 1.013119 1499.09 1.011922 1512.50 1.010434 1524.18 1.008728 1534.19 1.006845 1542.730.03880 1.013433 1500.01 1.012234 1513.39 1.010742 1525.06 1.009034 1535.02 1.007150 1543.540.04766 1.013728 1500.88 1.012527 1514.25 1.011032 1525.88 1.009321 1535.89 1.007440 1544.280.05939 1.014116 1501.98 1.012907 1515.34 1.011407 1526.95 1.009689 1536.89 1.007811 1545.35


0.00000 1.018812 1502.51 1.017521 1515.80 1.016008 1527.35 1.014294 1537.18 1.012363 1545.670.00970 1.019151 1503.59 1.017853 1516.86 1.016336 1528.41 1.014617 1538.21 1.012681 1546.680.01937 1.019482 1504.65 1.018183 1517.88 1.016658 1529.42 1.014937 1539.18 1.012992 1547.660.02952 1.019826 1505.72 1.018522 1518.89 1.016990 1530.40 1.015266 1540.20 1.013311 1548.670.03905 1.020139 1506.71 1.018833 1519.85 1.017293 1531.32 1.015566 1541.10 1.013610 1549.550.04766 1.020418 1507.57 1.019099 1520.70 1.017567 1532.18 1.015834 1541.87 1.013866 1550.330.05939 1.020799 1508.73 1.019469 1521.82 1.017937 1533.28 1.016192 1542.97 1.014225 1551.35

(B.HCl + 0.10 mol � kg�1 sucrose)0.00000 1.011490 1492.33 1.010264 1505.88 1.008810 1517.77 1.007138 1528.10 1.005279 1536.720.01040 1.011864 1493.44 1.010632 1506.97 1.009171 1518.86 1.007494 1529.17 1.005627 1537.770.01898 1.012166 1494.39 1.010929 1507.86 1.009465 1519.73 1.007782 1530.03 1.005914 1538.610.03002 1.012548 1495.54 1.011307 1508.98 1.009839 1520.83 1.008149 1531.13 1.006275 1539.650.04019 1.012901 1496.60 1.011657 1509.95 1.010181 1521.79 1.008481 1532.09 1.006605 1540.550.04916 1.013201 1497.47 1.011952 1510.77 1.010476 1522.58 1.008771 1532.96 1.006888 1541.340.05922 1.013545 1498.45 1.012286 1511.75 1.010804 1523.49 1.009090 1533.83 1.007208 1542.22

(B.HCl + 0.20 mol � kg�1 sucrose)0.00000 1.024670 1502.37 1.023367 1515.67 1.021853 1527.00 1.020133 1536.88 1.018222 1545.380.00948 1.024997 1503.43 1.023690 1516.70 1.022169 1528.04 1.020444 1537.89 1.018526 1546.380.02000 1.025356 1504.54 1.024038 1517.85 1.022515 1529.15 1.020780 1538.96 1.018857 1547.430.02862 1.025646 1505.45 1.024318 1518.78 1.022793 1530.05 1.021050 1539.85 1.019122 1548.280.04096 1.026058 1506.67 1.024716 1520.03 1.023189 1531.29 1.021436 1541.06 1.019491 1549.450.04978 1.026341 1507.53 1.024997 1520.92 1.023461 1532.13 1.021700 1541.82 1.019745 1550.280.05763 1.026583 1508.21 1.025235 1521.65 1.023702 1532.82 1.021924 1542.52 1.019975 1550.88

(B.HCl + 0.30 mol � kg�1 sucrose)0.00000 1.037843 1512.86 1.036471 1525.67 1.034890 1536.77 1.033112 1546.29 1.031161 1554.210.00980 1.038167 1514.00 1.036790 1526.79 1.035201 1537.89 1.033418 1547.38 1.031460 1555.28

(continued on next page)

S.Ryshetti

etal./J.Chem

.Thermodynam

ics77

(2014)123–

130125

0.992

0.994

0.996

0.998

1.000

1.002

0 0.02 0.04 0.06

ρρ.10

-3/ k

g m

-3

m / mol kg-1

FIGURE 1. Plot of density (q) vs. molality (m) of B.HCl drug in water attemperatures, T = �, 293.15 K; j, 298.15 K; N, 303.15 K; �, 308.15 K; ⁄, 313.15 K.

1480

1490

1500

1510

1520

1530

1540

0 0.02 0.04 0.06

u / m

.s-1

m / mol kg-1

FIGURE 2. Plot of speed of sound (u) vs. molality (m) of B.HCl drug in water attemperatures, T = �, 293.15 K; j, 298.15 K; N, 303.15 K; �, 308.15 K; ⁄, 313.15 K.

TAB

LE2

(con

tinu

ed)

m/(

mol�k

g�1)

10�

3q

/(kg�m�

3)

u/(m�s�

1)

10�

3q

/(kg�m�

3)

u/(m�s�

1)

10�

3q

/(kg�m�

3)

u/(m�s�

1)

10�

3q

/(kg�m�

3)

u/(m�s�

1)

10�

3q

/(kg�m�

3)

u/(m�s�

1)

T=

293.

15K

298.

15K

303.

15K

308.

15K

313.

15K

0.01

951

1.03

8481

1515

.10

1.03

7097

1527

.83

1.03

5505

1538

.96

1.03

3716

1548

.42

1.03

1749

1556

.31

0.02

780

1.03

8742

1516

.03

1.03

7357

1528

.70

1.03

5761

1539

.83

1.03

3962

1549

.31

1.03

1989

1557

.15

0.03

918

1.03

9099

1517

.26

1.03

7704

1529

.89

1.03

6106

1541

.03

1.03

4301

1550

.48

1.03

2317

1558

.30

0.04

702

1.03

9341

1518

.01

1.03

7939

1530

.60

1.03

6335

1541

.81

1.03

4523

1551

.21

1.03

2535

1559

.02

0.05

708

1.03

9645

1519

.07

1.03

8236

1531

.55

1.03

6627

1542

.79

1.03

4808

1552

.18

1.03

2809

1560

.00

aSt

anda

rdu

nce

rtai

nti

esu

are

u(m

)=

2�1

0�5

mol�k

g�1,u

(T)

=0.

01K

and

u(p)

=0.

01M

Pa,u

(u)

=0.

5m�s�

1an

du(

q)

=5�1

0�3

kg�m�

3.m

ism

olal

ity

ofbe

tain

eh

ydro

chlo

ride

inpe

rkg

ofw

ater

/wat

er+

suga

r.Th

ew

ater

base

isu

sed

for

bin

ary

mix

ture

s,w

hil

eth

ew

ater

and

suga

rba

seis

appl

ied

for

tern

ary

mix

ture

s.M

olal

ity

ofsu

gar

inpe

rkg

ofw

ater

ispr

epar

edw

ith

stan

dard

un

cert

ain

tyof

3�1

0�5

mol�k

g�1.


presence of strong (solute + solvent) interactions in all solutionsinvestigated. According to the co-sphere overlap model, ionic/(hydrophilic + hydrophilic) (first type) interactions lead to positivevalues of DtX

12 , whereas ionic/(hydrophilic + hydrophobic) (second

type) and (hydrophobic + hydrophobic) (third type) interactionslead to negative values of DtX

12 . In the present study, the positive

values of DtX12 indicate the presence of ionic/(hydrophilic + hydro-

philic) (first type) interactions in aqueous D(+)-glucose and sucrosesolutions. Moreover, these interactions increase with increase in theconcentration of D(+)-glucose and sucrose. The higher DtX

12 values

for sucrose solutions as compared to D(+)-glucose solutions areaccountable for more ionic/(hydrophilic + hydrophilic) (first type)interactions in sucrose solutions. The values of DtX

12 increase with

temperature and this may be ascribed to decreasing of electrostrict-ed water molecules around the ionic (AN+(CH3)3/Cl�)/hydrophilic(ACOOH) groups of B.HCl drug [17].

The values of V12 can be explained by Shahidi’s equation [22]:

V12 ¼ Vv�w þ Vvoid � V shrinkage; ð7Þ

TABLE 3Apparent molar volumes (V2,/) and apparent molar isentropic compressibilities (Ks,2,/) of B.HCl in water, aqueous D(+)-glucose and sucrose solutions at T = (293.15 to 313.15) Kand pressure p = 0.1 MPa.a

m/(mol � kg�1) 106V2,//(m3 �mol�1) 106Ks,2,//(m3 �mol�1 � Pa�1)

T = 293.15 K 298.15 K 303.15 K 308.15 K 313.15 K 293.15 K 298.15 K 303.15 K 308.15 K 313.15 K

B.HCl + water0.00988 115.95 116.25 116.87 117.20 117.76 �27.99 �26.20 �24.36 �22.97 �21.580.02034 116.10 116.64 116.90 117.37 118.02 �27.23 �24.97 �22.05 �21.16 �19.730.03199 116.29 116.85 117.22 117.57 118.35 �25.48 �22.25 �20.94 �20.54 �17.610.03929 116.73 117.15 117.58 117.89 118.63 �24.00 �21.74 �19.71 �19.16 �16.930.04992 117.02 117.40 117.79 118.13 118.93 �22.72 �19.68 �17.24 �18.52 �15.280.05925 117.33 117.79 117.95 118.34 119.06 �21.81 �20.74 �15.27 �16.62 �14.69

B.HCl + 0.10 mol � kg�1D(+)-glucose

0.00974 116.51 117.32 118.05 118.70 119.47 �27.40 �25.21 �23.92 �21.72 �19.610.01935 116.74 117.30 118.13 118.99 119.72 �26.05 �23.51 �22.76 �20.10 �18.910.02962 116.92 117.55 118.38 119.15 119.92 �23.92 �22.97 �21.07 �19.58 �17.890.04056 117.20 117.74 118.55 119.48 120.13 �22.75 �21.95 �20.38 �18.46 �16.820.04945 117.26 117.92 118.74 119.77 120.30 �21.23 �21.34 �19.70 �17.72 �15.680.05791 117.62 118.29 118.92 120.05 120.58 �20.92 �19.92 �18.62 �16.77 �14.37


0.00970 117.03 117.54 118.37 119.02 119.90 �26.40 �23.42 �22.72 �20.08 �18.540.01937 117.16 117.99 118.55 119.41 120.16 �24.42 �23.23 �21.39 �18.42 �16.780.02952 117.32 118.27 118.76 119.68 120.42 �23.77 �22.79 �20.69 �18.06 �15.930.03905 117.48 118.50 118.93 119.86 120.83 �22.14 �21.36 �19.55 �17.00 �14.570.04766 117.75 118.65 119.20 120.14 121.17 �21.16 �20.70 �18.42 �15.28 �13.810.05939 118.08 118.94 119.38 120.51 121.31 �19.56 �19.51 �17.15 �14.25 �12.12


0.00956 117.07 117.87 118.40 119.04 119.71 �26.98 �24.33 �23.28 �20.66 �18.750.01859 117.38 117.88 118.61 119.11 119.98 �26.20 �23.25 �21.78 �19.03 �17.790.02949 117.56 118.10 118.85 119.33 120.29 �25.04 �21.56 �19.65 �18.34 �16.950.03987 117.88 118.36 119.16 119.63 120.43 �24.08 �20.79 �18.48 �17.05 �15.630.04749 118.12 118.80 119.32 119.85 120.78 �23.08 �19.92 �18.17 �15.81 �14.510.05744 118.31 119.06 119.50 120.16 120.92 �22.08 �18.88 �17.19 �15.06 �13.26

B.HCl + 0.10 mol � kg�1 sucrose0.01040 116.68 117.35 118.13 118.74 119.66 �26.55 �24.03 �22.73 �20.69 �18.580.01898 116.97 117.64 118.28 118.99 119.62 �27.36 �23.50 �21.74 �19.83 �17.880.03002 117.30 117.89 118.47 119.20 119.86 �26.10 �22.65 �20.81 �19.21 �16.580.04019 117.38 117.92 118.58 119.41 119.99 �25.62 �21.48 �19.65 �18.13 �15.220.04916 117.65 118.21 118.77 119.58 120.22 �24.37 �20.19 �18.25 �17.74 �14.300.05922 117.71 118.36 118.95 119.79 120.34 �23.60 �19.85 �17.39 �16.40 �13.60



a Standard uncertainties u are u(m) = 2 � 10�5 mol � kg�1, u(T) = 0.01 K and u(p) = 0.01 MPa. m is molality of betaine hydrochloride in per kg of water/water + sugar. The waterbase is used for binary mixtures, while the water and sugar base is applied for ternary mixtures. Molality of sugar in per kg of water is prepared with standard uncertainty of3 � 10�5 mol � kg�1.

S. Ryshetti et al. / J. Chem. Thermodynamics 77 (2014) 123–130 127

where Vv�w is the van der Waal’s volume, Vvoid is the volume associ-ated with voids and Vshrinkage is the shrinkage volume due toelectrostriction. The Vv�w and Vvoid are assumed to be constant inD(+)-glucose and sucrose solutions; Vshrinkage is the shrinkage vol-ume caused by interactions of hydrogen bonding groups of solutewith water molecules [13]. The positive values of DtV

12 indicate

the decrease in Vshrinkage in the presence of D(+)-glucose and sucrose[23], which is found to decrease with increasing temperature andthe concentration of D(+)-glucose and sucrose.

The values obtained for transfer partial molar volume (DtV12 )

and transfer partial molar isentropic compressibility (DtK1s;2) of

B.HCl drug in aqueous glucose and sucrose solutions can also beexpressed as follows [24]:

DtX12 ¼ 2XABmB þ 3XABBm2

B þ � � � ; ð8Þ

where A stands for solute and B for co-solute, the constants XAB (VAB

or KAB) and XABB (VABB or KABB) are pair and triplet volumetric orcompressibility interaction coefficients, respectively. The values ofDtX

12 have been fitted in equation (8) to get XAB (VAB or KAB) and

XABB (VABB or KABB) interaction coefficients, which are given in table6. The XAB and XABB values are positive for all solutions investigated.This may be due to strong (solute + solvent) interactions in the solu-tions investigated [25,26].

The hydration numbers (NH) of B.HCl drug in aqueous D(+)-glu-cose and sucrose solutions have been calculated at temperaturesinvestigated by using the method reported by Millero et al. [27] as:

TABLE 4Partial molar properties V12 and K1s;2 of B.HCl in aqueous D(+)-glucose and sucrose solutions at T = (293.15 to 313.15) K and pressure p = 0.1 MPa.a

106V12 /(m3 �mol�1) 106K1s;2/(m3 �mol�1 � GPa�1)

T = 293.15 K 298.15 K 303.15 K 308.15 K 313.15 K 293.15 K 298.15 K 303.15 K 308.15 K 313.15 K

B.HCl + 0.10 mol � kg�1D(+)-glucose 116.29 116.99 117.82 118.41 119.26 �28.39 �25.89 �24.73 �22.37 �20.75



B.HCl + 0.10 mol � kg�1 sucrose 116.55 117.21 117.96 118.56 119.41 �28.04 �25.16 �23.94 �21.55 �19.75B.HCl + 0.20 mol � kg�1 sucrose 116.75 117.38 118.14 118.79 119.57 �27.48 �24.69 �23.77 �21.14 �19.53B.HCl + 0.30 mol � kg�1 sucrose 117.08 117.65 118.48 119.12 119.98 �27.16 �24.59 �23.31 �20.93 �18.94

a Standard uncertainties u are u(T) = 0.01 K and u(p) = 0.01 MPa. The water base is used for binary mixtures, while the water and sugar base is applied for ternary mixtures.Molality of betaine hydrochloride in per kg of water/water + sugar is prepared with standard uncertainty of 2 � 10�5 mol � kg�1. Molality of sugar in per kg of water is preparedwith standard uncertainty of 3 � 10�5 mol � kg�1.

TABLE 5Transfer partial molar properties DtV

12 and DtK

1s;2of B.HCl in aqueous D(+)-glucose and sucrose solutions at T = (293.15 to 313.15) K and pressure p = 0.1 MPa.a

106DtV12 /(m3 �mol�1) 106DtK

1s;2/(kg �m3 �mol�2 � GPa�1)

T = 293.15 K 298.15 K 303.15 K 308.15 K 313.15 K 293.15 K 298.15 K 303.15 K 308.15 K 313.15 K

B.HCl + 0.10 mol � kg�1D(+)-glucose 0.75 1.03 1.29 1.50 1.78 1.15 1.21 1.42 1.64 1.86



B.HCl + 0.10 mol � kg�1 sucrose 1.01 1.25 1.44 1.65 1.92 1.51 1.94 2.22 2.46 2.87B.HCl + 0.20 mol � kg�1 sucrose 1.21 1.42 1.62 1.88 2.09 2.07 2.41 2.38 2.87 3.08B.HCl + 0.30 mol � kg�1 sucrose 1.53 1.68 1.96 2.21 2.50 2.39 2.52 2.85 3.08 3.68


TABLE 6Pair XAB and triplet XABB interaction coefficients of B.HCl in aqueous D(+)-glucose and sucrose solutions at T = (293.15 to 313.15) K and pressure p = 0.1 MPa.a

T/K From volume From compressibility

106VAB/(m3 �mol�2 � kg) 106VABB/(m3 �mol�3 � kg2) 106KAB/(m3 �mol�2 � kg � GPa�1) 106KABB/(m3 �mol�3 � kg2 � GPa�1)

D(+)-glucose293.15 0.23 0.92 0.46 0.62298.15 0.38 0.77 0.46 1.12303.15 0.55 0.62 0.53 1.27308.15 0.67 0.50 0.64 1.42313.15 0.82 0.38 0.79 1.28

Sucrose293.15 0.37 0.87 0.56 1.47298.15 0.51 0.72 0.86 0.97303.15 0.58 0.87 0.93 1.05308.15 0.68 0.93 1.09 1.03313.15 0.80 0.97 1.20 1.35

a Standard uncertainties u are u(T) = 0.01 K and u(p) = 0.01 MPa.

TABLE 7Hydration numbers (NH) of B.HCl in aqueous D(+)-glucose and sucrose solutions at T = (293.15 to 313.15) K and pressure p = 0.1 MPa.a

NH

T = 293.15 K 298.15 K 303.15 K 308.15 K 313.15 K

B.HCl + 0.10 mol � kg�1D(+)-glucose 3.51 3.20 3.05 2.76 2.56



B.HCl + 0.10 mol � kg�1 sucrose 3.46 3.11 2.96 2.66 2.44B.HCl + 0.20 mol � kg�1 sucrose 3.39 3.05 2.94 2.61 2.41B.HCl + 0.30 mol � kg�1 sucrose 3.35 3.04 2.88 2.58 2.34



NH ¼ � K1s;2 ðelectÞ=ðK1s � V11 Þ

h i; ð9Þ

where K1s;2 (elect) is the electrostriction partial molar compressibil-ity, K1s is the compressibility of bulk water or bulk solvent, V11 is themolar volume of bulk water or bulk solvent. The K1s;2 (elect) valuescan be calculated by using the equation:

K1s;2 ðelectÞ ¼ K1s;2 ðsoluteÞ � K1 ðintÞ; ð10Þ

where K1 (int) is the intrinsic partial molar isentropic compressibil-ity of solute. It is assumed that K1 (int) � 0 [27], then K1s;2 (elect)becomes equal to K1s;2 (solute). The NH values (table 7) for theB.HCl drug studied are less in the presence of D(+)-glucose/sucrose

TABLE 8Partial molar expansions (E12 ) of B.HCl in aqueous D(+)-glucose and sucrose solutions at T = (293.15 to 313.15) K and pressure p = 0.1 MPa.a

106 E12 /(m3 �mol�1 � K�1)

T = 293.15 K 298.15 K 303.15 K 308.15 K 313.15 K




B.HCl + 0.10 mol � kg�1 sucrose 0.127 0.134 0.141 0.148 0.155B.HCl + 0.20 mol � kg�1 sucrose 0.130 0.135 0.141 0.146 0.152B.HCl + 0.30 mol � kg�1 sucrose 0.125 0.137 0.148 0.159 0.170


TABLE 9The values of (@C1p;2/oP)T and (o2V12 /oT2)P of B.HCl in aqueous D(+)-glucose and sucrose solutions at T = (293.15 to 313.15) K and pressure p = 0.1 MPa.a

(@C1p;2/oP)T/(cm3 �mol�2 � K�1) (o2V12 /oT2)P/(cm6 �mol�2 � K�2)

T = 293.15 K 298.15 K 303.15 K 308.15 K 313.15 K

B.HCl + 0.10 mol � kg�1D(+)-glucose �0.142 �0.145 �0.147 �0.150 �0.152 0.0005



B.HCl + 0.10 mol � kg�1 sucrose �0.400 �0.407 �0.414 �0.421 �0.427 0.0014B.HCl + 0.20 mol � kg�1 sucrose �0.317 �0.323 �0.328 �0.333 �0.339 0.0011B.HCl + 0.30 mol � kg�1 sucrose �0.657 �0.668 �0.679 �0.690 �0.701 0.0022


S. Ryshetti et al. / J. Chem. Thermodynamics 77 (2014) 123–130 129

as compared to their values in water, and these values decreasewith further increase in concentration of D(+)-glucose/sucrose. Thevalues of NH also decrease with the increase in temperature. Theseresults indicate the effect of temperature and concentrations ofD(+)-glucose and sucrose on the dehydration of B.HCl drug in solu-tions studied.

The temperature dependence of V12 can be determined by thefollowing expression.

V12 ¼ a0 þ a1T þ a2T2; ð11Þ

where T is the temperature in Kelvin. The values of coefficients ao,a1 and a2 were estimated by the least-squares fitting of the valuesof V12 in equation (11). The partial molar expansion (E12 ) can beincurred by differentiating equation (11) with respect to tempera-ture and these E12 values are shown in table 8.

E12 ¼ ð@V12 =@TÞP ¼ a1 þ 2a2T: ð12Þ

It is clear from table 8 that the positive values of E12 indicate thepresence of strong (solute + solvent) interactions in all solutionsinvestigated. Further these E12 values increase with increasing tem-perature at all compositions of D(+)-glucose and sucrose. Roy et al.also observed the increasing E12 values along with increasing tem-perature in a ternary mixture [28].

The qualitative information on hydration of solutes in solutionscan be obtained with the help of Hepler’s equation on the basis ofthe sign of the expression [29].

@C1p;2=@P� �

T¼ �Tð@2V12 =@T2ÞP: ð13Þ

It has been suggested that the positive values of (o2V12 /oT2)P (ornegative values of ((@C1p;2/oP)T) are associated with structure mak-ing and negative values of (o2V12 /oT2)P (or positive values of((@C1p;2/oP)T) for structure breaking nature of solute molecules insolutions [29]. In the present investigation (table 9), the positive

values of (o2V12 /oT2)P indicate the structure making effect of theB.HCl drug in D(+)-glucose and sucrose solutions, which increaseswith increasing the concentrations of D(+)-glucose and sucrose.

4. Conclusions

In the present study, the partial molar properties, transfer par-tial molar properties, pair and triplet interaction coefficients andhydration numbers have been computed from the densities (q)and speeds of sound (u) of B.HCl drug in water, aqueous D(+)-glu-cose and sucrose solutions. These parameters indicate the presenceof ionic/(hydrophilic + hydrophilic) interactions between the ionic(AN+(CH3)3/Cl�)/hydrophilic (ACOOH) groups of B.HCl drug and(AOH, AC = O, and AOA) groups of D(+)-glucose/sucrose and arebeing influenced by the concentration of D(+)-glucose and sucroseas well as the experimental temperatures. The decrease in electro-striction of water molecules around the ionic (AN+(CH3)3/Cl�)/hydrophilic (ACOOH) groups of B.HCl drug has been noted withincreasing temperature and concentration of D(+)-glucose andsucrose. The positive values of (o2V12 /oT2)P indicate the structuremaking ability of B.HCl drug in D(+)-glucose and sucrose solutions.

Acknowledgments

One of the authors (Suresh Ryshetti) is thankful to UniversityGrants Commission (UGC), Govt. of India for the financial supportin form of Junior Research Fellowship (JRF). Authors are thankfulto Council of Scientific and Industrial Research (CSIR) and Depart-ment of Science and Technology (DST) for their financial support.

Appendix A. Supplementary data

Supplementary data associated with this article can be found, inthe online version, at http://dx.doi.org/10.1016/j.jct.2014.05.015.



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JCT 14-37

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Acoustic and volumetric properties of betaine hydrochloride drug in aqueous d(+)-glucose and sucrose solutions

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