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J Solution Chem (2009) 38: 10551070

DOI 10.1007/s10953-009-9426-z

Experimental Study of the Excess Molar Enthalpy


of Ternary Mixtures Containing
Water + (1,2-Propanediol, or 1,3-Propanediol,
or 1,2-Butanediol, or 1,3-Butanediol, or 1,4-Butanediol,
or 2,3-Butanediol) + Electrolytes at 298.15 K
and Atmospheric Pressure
Ricardo F. Checoni Artur Z. Francesconi
Received: 27 November 2008 / Accepted: 16 February 2009 / Published online: 10 June 2009
Springer Science+Business Media, LLC 2009

Abstract Excess molar enthalpies (HmE ) of ternary mixtures containing water+


(1,2-propanediol or 1,3-propanediol or 1,2-butanediol or 1,3-butanediol or 1,4-butanediol
or 2,3-butanediol) + (sodium bromide, or ammonium bromide, or tetraethyl ammonium
bromide, or 1-n-butyl-3-methylimidazolium bromide at 0.1 moldm3 ) at 298.15 K and atmospheric pressure have been determined as a function of composition using a modified
1455 Parr mixture calorimeter. The HmE values are negative for all mixtures over the whole
composition range. The influence of the electrolyte on the hydrophobic and hydrophilic
effects as well as on the behavior of HmE is discussed.
Keywords Water Alkanediols Electrolytes Excess molar enthalpy

1 Introduction
Alkanediols are recognized as important compounds in several industrial branches: cosmetic, pharmaceutical, food, automotive and others. These compounds act as stabilizing
agents of the native state of proteins in aqueous media [1, 2] and their presence results in
non-freezing water in aqueous solutions [3] and acts as an icing inhibitor in fuel systems [4].
It is known that the presence of alkanediols in water influences both the network and the
interactions occurring between the water molecules, which produce interesting aqueous solution behavior. In an attempt to elucidate the nature of the interactions occurring between
alkanediolswater mixtures, various research groups have devoted efforts to study experimentally the excess molar properties of these aqueous mixtures. Table 1 shows a list of
works involving the measurement of the thermophysical properties of binary mixtures containing specially propanediols and butanediols.
However, experimental studies of excess molar properties related to the presence of an
electrolyte in water + alkanediols mixtures are scarce: Taniewska-Osinska and Pietrzac [14]
R.F. Checoni () A.Z. Francesconi
School of Chemical Engineering, State University of Campinas, P.O. Box 6066, 13083-970 Campinas,
SP, Brazil
e-mail: rfcheconi@yahoo.com.br

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J Solution Chem (2009) 38: 10551070

Table 1 Work related to the measurements of the thermophysical properties (excess molar volume (VmE ),
E ), excess molar heat capacity (Cp E ), partial molar volume (V ), density (),
excess molar enthalpy (Hm
i
m
viscosity (), speeds of sound (v), relative permittivity (r ), and refractive index (nD )) of binary mixtures
containing propanediols and butanediols
Reference

Property

System

Temperature (K)

Romero and Paez [1]

VmE Vi

water + (1-butanol, butanediols,


1,2,4-butanetriol)

298.15

George and Sastry [3]

, , v, r , nD

water + (propanediols, butanediols)

298.15 to 338.15

Yang et al. [5]

E
VmE , Cpm

water + 1,4-butanediol

293.15 to 353.15

Zarei [6]

E
Hm

1,2-propanediol + 1-alkanols (C1 to C6 )

298.15

Geyer et al. [7]

, VmE

water + (1,2-propanediol,
1,2-butanediol)

288.15 to 308.15

Geyer et al. [8]

, VmE

water + (1,2-ethanediol,
1,2-propanediol, 1,2-, 2,3-butanediol)

278.15 to 318.15

Kracht et al. [9]

E
Hm

water + (1,2-ethanediol,
1,2-propanediol, 1,2-butanediol)

285.65 to 338.15

Hawrylak et al. [10]

, VmE , Vi

water + (1,2-, 1,3-, 1,4-, 2,3-butanediol)

298.15 to 318.15

Matsumoto et al. [11]

E
Hm

water + (1,2-ethanediol, 1,2-,


1,3-butanediol)

298.15

Kapadi et al. [12]

v, VmE

water + 1,2-propanediol

303.15 to 318.15

Nagamachi and
Francesconi [13]

E
Hm

water + (1,2-, 1,3-propanediol,


1,4-butanediol)

298.15, 323.15
and 343.15

studied the effect of NaCl on the enthalpy of solution of water + 1,2-butanediol mixtures;
the effect of NaCl and NaI on enthalpy of solution of aqueous solutions containing (1,2ethanediol, or 1,2-propanediol, or 1,2-butanediol, or 1,2-pentanediol) at 298.15 K were studied by Taniewska-Osinska and Pietrzac [15]; the influence of the NaBPh4 and Ph4 PCl salts
on the enthalpy of solution of binary water + (1,2-ethanediol, or 1,2-propanediol, or 1,2butanediol) mixtures were studied by Pietrzac et al. [16].
In this work, experimental HmE data of water + (1,2-propanediol or 1,3-propanediol or
1,2-butanediol or 1,3-butanediol or 1,4-butanediol or 2,3-butanediol) + (sodium bromide or
ammonium bromide or tetraethyl ammonium bromide or 1-n-butyl-3-methylimidazolium
bromide at 0.1 moldm3 ) at 298.15 K and atmospheric pressure have been determined as a
function of composition. A modified version of a 1455 Parr mixture calorimeter was used to
perform the experiments. Besides the influence of the electrolyte presence on the hydrophobic and hydrophilic effects, and on the experimental data of the excess molar enthalpy of
binary mixtures of water + alkanediols, the influence of cation size on HmE are discussed.

2 Experimental
Water was doubly distilled and alkanediols were used without previous purification; electrolytes were triturated up to a powder condition, dried at temperatures above 353.15 K in
a drying oven for at least during four hours and then inserted in a desiccator with silica gel
at room temperature before use. In order to check the purity of the substances, density and
refractive index measurements were performed using a vibrating-tube densimeter (Anton
Paar, DMA 55) and an Abb type refractometer (Atago, model 3T), respectively. The un-

J Solution Chem (2009) 38: 10551070

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Table 2 Furnisher, purity (%), density () and refraction index (nD ) at 293.15 K of the alkanediols
Alkanediols

Furnisher

Purity

(gcm3 )

(%)

Literaturea

nD
Experimental

Literaturea

Experimental

1,2-propanediol

Acros

99.0

1.0361

1.0362

1.4324

1.4322

1,3-propanediol

Aldrich

98.0

1.0538

1.0537

1.4398

1.4395

1,2-butanediol

Fluka

98.0

1.0024

1.0022

1.4378

1.4377

1,3-butanediol

Acros

99.0

1.0053

1.0055

1.4401

1.4399

1,4-butanediol

Avocado

99.0

1.0171

1.0170

1.4460

1.4459

2,3-butanediol

Aldrich

98.0

1.0033

1.0032

1.4310b

1.4308b

a Obtained from [17]


b at 298.15 K

certainties in the refraction index and density measurements are about 1 104 and 1
104 gcm3 , respectively. Table 2 shows the supplier and purity of the alkanediols as well
as a comparison of the density and refractive index measurements with literature values [17].
Sodium bromide and ammonium bromide were supplied by Alfa Aesar and tetraethylammonium bromide and 1-n-butyl-3-methylimidazolium bromide were supplied by Acros
and Fluka, respectively. Excess enthalpy measurements were performed using a Parr 1455
solution calorimeter with some improvements. A detailed description and performance of
the apparatus as well as the experimental procedure are given elsewhere [18]. Salts were
first dissolved to the required molality in water. The salt concentration (0.1 moldm3 )
was kept constant in the ternary mixtures for all experiments. The enthalpy of solution of the salts was considered in the HmE calculations: 11.6 Jmol1 for water + NaBr,
29.0 Jmol1 for water + NH4 Br, 11.0 Jmol1 for water + (C2 H5 )4 NBr and 8.0 Jmol1 for
water + C8 H15 N2 Br; these values were obtained experimentally in our laboratory.
The experimental HmE values for the ternary mixtures were determined from
HmE



Cv
n0
= Cpm +
T + HmE0
n
n

(1)

where n0 is the amount of substance in the previous mixing process. If a pure reagent is
E
values are zero. The mixtures were prepared gravimetrically using a
used, both n0 and Hm0
Sartorious MC210P balance (resolution 104 g, uncertainty 5 105 g) and a Mettler
Toledo PB 3002 balance (resolution, 102 g, uncertainty 5 103 g). The estimated
uncertainty in mole fraction is 2 104 and in the excess molar enthalpy measurements
it is 1 102 HmE for the central composition range and 2 102 HmE for the water-rich
or alkanediol-rich region.

3 Results and Discussion


Experimental HmE data for water + (1,2-butanediol or 1,3-butanediol or 2,3-butanediol) at
298.15 K are showed in Table 3; for water + (1,2-propanediol or 1,3-propanediol or 1,4butanediol) mixtures, the data were previously determined in our laboratory [13]. Measured
HmE data for water + (1,2-propanediol or 1,3-propanediol or 1,2-butanediol or 1,3-butanediol
or 1,4-butanediol or 2,3-butanediol) + (sodium bromide or ammonium bromide or tetraethyl

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J Solution Chem (2009) 38: 10551070

E values as a function of the molar fraction of alkanediol (x


Table 3 Experimental Hm
alkanediol ) for water +
alkanediol at 298.15 K and atmospheric pressure

Water + 1,2-butanediol
E
x1,2-butanediol Hm

(Jmol1 )

E
x1,2-butanediol Hm

(Jmol1 )

E
x1,2-butanediol Hm

(Jmol1 )

E
x1,2-butanediol Hm

(Jmol1 )

0.0640

515

0.3722

577

0.7431

252

0.9159

87

0.1016

575

0.4212

539

0.7784

220

0.9291

73

0.1424

631

0.4829

486

0.8097

192

0.9403

62

0.1851

648

0.5426

434

0.8373

166

0.9499

52

0.2298

647

0.5991

384

0.8614

142

0.2761

634

0.6516

336

0.8823

121

0.3236

610

0.6998

291

0.9004

102

Water + 1,3-butanediol
E
x 1,3-butanediol Hm

(Jmol1 )

E
x 1,3-butanediol Hm

(Jmol1 )

E
x1,3-butanediol Hm

(Jmol1 )

E
x 1,3-butanediol Hm

(Jmol1 )

0.0606

585

0.3351

877

0.6259

564

0.8452

261

0.0944

798

0.3787

837

0.6615

519

0.8683

226

0.1304

895

0.4223

793

0.6948

477

0.8883

196

0.1684

941

0.4655

748

0.7259

437

0.9055

169

0.2081

952

0.5077

701

0.7547

396

0.2494

942

0.5488

655

0.7886

345

0.2919

914

0.5882

609

0.8188

301

Water + 2,3-butanediol
E
x 2,3-butanediol Hm

(Jmol1 )

E
x 2,3-butanediol Hm

(Jmol1 )

E
x 2,3-butanediol Hm

(Jmol1 )

E
x 2,3-butanediol Hm

(Jmol1 )

0.0295

425

0.0811

891

0.1796

1146

0.4524

874

0.0332

472

0.0934

949

0.1974

1157

0.5308

769

0.0374

525

0.1083

1003

0.2179

1153

0.6352

605

0.0423

579

0.1171

1034

0.2417

1143

0.7805

391

0.0478

632

0.1269

1057

0.2696

1123

0.9001

179

0.0543

691

0.1379

1080

0.3027

1090

0.0618

754

0.1501

1107

0.3426

1027

0.0707

822

0.1639

1131

0.3913

959

ammonium bromide or 1-n-butyl-3-methylimidazolium bromide) mixtures as a function of


mole fraction of alkanediol at 298.15 K and atmospheric pressure are shown in Tables 4 to 7.
Whereas for mixtures of water + alkanediol + C8 H15 N2 Br (at 0.1 moldm3 ) concentrations up to 92 mol % are possible, measurements for the remaining salt mixtures can only
be carried out up to 81 mol % alkanediol due to solubility limitations.
The experimental results of HmE were correlated by the Redlich-Kister type equation
HmE = x(1 x)

4

i=0

Ai (1 2x)i

(2)

J Solution Chem (2009) 38: 10551070

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E values as a function of the molar fraction of alkanediol (x


Table 4 Experimental Hm
alkanediol ) for water +
alkanediol + NaBr at 0.1 moldm3 , 298.15 K and atmospheric pressure

Water + 1,2-propanediol + NaBr


E
x 1,2-propanediol Hm

(Jmol1 )

E
x 1,2-propanediol Hm

(Jmol1 )

E
x 1,2-propanediol Hm

(Jmol1 )

E
x 1,2-propanediol Hm

(Jmol1 )

0.0256

215

0.2400

768

0.4796

628

0.6854

430

0.0528

410

0.2741

756

0.5123

603

0.7097

406

0.0813

541

0.3085

739

0.5440

576

0.7325

380

0.1110

636

0.3431

723

0.5748

548

0.7540

353

0.1419

716

0.3778

701

0.6044

518

0.7740

326

0.1738

751

0.4122

677

0.6327

488

0.7927

302

0.2065

766

0.4462

652

0.6598

459

0.8100

277

Water + 1,3-propanediol + NaBr


E
x 1,3-propanediol Hm

(Jmol1 )

E
x 1,3-propanediol Hm

(Jmol1 )

E
x 1,3-propanediol Hm

(Jmol1 )

E
x 1,3-propanediol Hm

(Jmol1 )

0.0383

252

0.2619

879

0.5205

854

0.7298

557

0.0794

477

0.3275

907

0.5797

790

0.7698

490

0.1368

670

0.3933

908

0.6346

706

0.8048

428

0.1980

803

0.4581

892

0.6847

637

Water + 1,2-butanediol + NaBr


E
x 1,2-butanediol Hm

(Jmol1 )

E
x 1,2-butanediol Hm

(Jmol1 )

E
x 1,2-butanediol Hm

(Jmol1 )

E
x 1,2-butanediol Hm

(Jmol1 )

0.0325

280

0.2353

570

0.4736

402

0.6842

242

0.0680

442

0.2820

545

0.5198

364

0.7187

216

0.1061

510

0.3297

515

0.5644

330

0.7504

188

0.1470

568

0.3779

484

0.6069

299

0.7791

163

0.1901

577

0.4261

445

0.6469

269

Water + 1,3-butanediol + NaBr


E
x 1,3-butanediol Hm

(Jmol1 )

E
x 1,3-butanediol Hm

(Jmol1 )

E
x 1,3-butanediol Hm

(Jmol1 )

E
x 1,3-butanediol Hm

(Jmol1 )

0.0325

306

0.2353

862

0.4736

686

0.6842

439

0.0680

565

0.2820

850

0.5198

631

0.7187

392

0.1061

728

0.3297

823

0.5644

584

0.7504

356

0.1470

822

0.3779

787

0.6069

534

0.7791

312

0.1901

853

0.4261

737

0.6469

488

whose parameters Ai were obtained using the method of least squares and are given in
Table 8, along with the standard deviations determined from
=



1/2
(HmEexper HmEcalc. )2 /(N k)

(3)

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J Solution Chem (2009) 38: 10551070

Table 4 (Continued)
Water + 1,4-butanediol + NaBr
E
x 1,4-butanediol Hm

(Jmol1 )

E
x 1,4-butanediol Hm

(Jmol1 )

E
x 1,4-butanediol Hm

(Jmol1 )

E
x 1,4-butanediol Hm

(Jmol1 )

0.0325

266

0.2353

801

0.4736

809

0.6842

605

0.0680

453

0.2820

820

0.5198

786

0.7187

555

0.1061

594

0.3297

831

0.5644

748

0.7504

502

0.1470

692

0.3779

831

0.6069

704

0.7791

451

0.1901

751

0.4261

825

0.6469

655

Water + 2,3-butanediol + NaBr


E
x 2,3-butanediol Hm

(Jmol1 )

E
x 2,3-butanediol Hm

(Jmol1 )

E
x 2,3-butanediol Hm

(Jmol1 )

E
x 2,3-butanediol Hm

(Jmol1 )

0.0142

218

0.0405

564

0.1410

963

0.3575

836

0.0161

254

0.0465

609

0.1555

978

0.4177

763

0.0183

290

0.0537

658

0.1720

979

0.4964

674

0.0208

331

0.0621

710

0.1912

973

0.6033

556

0.0237

375

0.0722

770

0.2135

962

0.7565

368

0.0270

421

0.0844

824

0.2400

945

0.0308

472

0.0993

870

0.2716

922

0.0353

519

0.1178

921

0.3099

885

E values as a function of the molar fraction of alkanediol (x


Table 5 Experimental Hm
alkanediol ) for water +
alkanediol + NH4 Br at 0.1 moldm3 , 298.15 K and atmospheric pressure

Water + 1,2-propanediol + NH4 Br


E
x 1,2-propanediol Hm

(Jmol1 )

E
x 1,2-propanediol Hm

(Jmol1 )

E
x 1,2-propanediol Hm

(Jmol1 )

E
x 1,2-propanediol Hm

(Jmol1 )

0.0382

284

0.2666

829

0.5152

592

0.7191

390

0.0793

564

0.3170

800

0.5612

545

0.7511

354

0.1231

772

0.3676

750

0.6049

501

0.7802

320

0.1692

824

0.4179

695

0.6458

464

0.2172

834

0.4673

641

0.6839

427

Water + 1,3-propanediol + NH4 Br


E
x 1,3-propanediol Hm

(Jmol1 )

E
x 1,3-propanediol Hm

(Jmol1 )

E
x 1,3-propanediol Hm

(Jmol1 )

E
x 1,3-propanediol Hm

(Jmol1 )

0.0382

253

0.2666

887

0.5152

868

0.7191

574

0.0793

478

0.3170

911

0.5612

821

0.7511

521

0.1231

664

0.3676

918

0.6049

759

0.7802

477

0.1692

762

0.4179

914

0.6458

714

0.2172

839

0.4673

895

0.6839

636

J Solution Chem (2009) 38: 10551070

1061

Table 5 (Continued)
Water + 1,2-butanediol + NH4 Br
E
x 1,2-butanediol Hm

(Jmol1 )

E
x 1,2-butanediol Hm

(Jmol1 )

E
x 1,2-butanediol Hm

(Jmol1 )

E
x 1,2-butanediol Hm

(Jmol1 )

0.0325

290

0.2351

581

0.4733

426

0.6840

253

0.0679

439

0.2818

558

0.5196

386

0.7185

225

0.1061

518

0.3295

532

0.5642

347

0.7501

197

0.1469

571

0.3777

501

0.6066

312

0.7789

173

0.1900

589

0.4259

463

0.6466

281

Water + 1,3-butanediol + NH4 Br


E
x 1,3-butanediol Hm

(Jmol1 )

E
x 1,3-butanediol Hm

(Jmol1 )

E
x 1,3-butanediol Hm

(Jmol1 )

E
x 1,3-butanediol Hm

(Jmol1 )

0.0325

300

0.2351

868

0.4733

691

0.6840

437

0.0679

556

0.2818

856

0.5196

640

0.7185

392

0.1061

725

0.3295

831

0.5642

590

0.7501

350

0.1469

815

0.3777

794

0.6066

534

0.7789

310

0.1900

855

0.4259

741

0.6466

484

Water + 1,4-butanediol + NH4 Br


E
x 1,4-butanediol Hm

(Jmol1 )

E
x 1,4-butanediol Hm

(Jmol1 )

E
x 1,4-butanediol Hm

(Jmol1 )

E
x 1,4-butanediol Hm

(Jmol1 )

0.0325

255

0.2351

806

0.4733

840

0.6840

624

0.0679

449

0.2818

841

0.5196

810

0.7185

569

0.1061

589

0.3295

852

0.5642

768

0.7501

515

0.1469

701

0.3777

856

0.6066

725

0.7789

465

0.1900

753

0.4259

851

0.6466

671

Water + 2,3-butanediol + NH4 Br


E
x 2,3-butanediol Hm

(Jmol1 )

E
x 2,3-butanediol Hm

(Jmol1 )

E
x 2,3-butanediol Hm

(Jmol1 )

E
x 2,3-butanediol Hm

(Jmol1 )

0.0144

207

0.0359

528

0.1014

935

0.4178

844

0.0164

241

0.0412

589

0.1203

976

0.4965

737

0.0186

280

0.0474

656

0.1443

1012

0.6034

604

0.0212

322

0.0546

723

0.1752

1032

0.7565

384

0.0241

369

0.0633

762

0.2165

1029

0.0275

421

0.0736

809

0.2737

991

0.0314

472

0.0861

868

0.3576

918

where HmEexper is the excess molar enthalpy obtained experimentally, HmEcalc. is the excess
molar enthalpy calculated using the Redlich-Kister equation, N is the number of data points
and k is the number of the adjusted parameters of Eq. 2.
Figure 1 illustrates the excess molar enthalpy behavior for the ternary mixtures containing water + alkanediol + electrolyte (at 0.1 moldm3 ) as well as that for the salt-free binary

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J Solution Chem (2009) 38: 10551070

E values as a function of the molar fraction of alkanediol (x


Table 6 Experimental Hm
alkanediol ) for water +
alkanediol + (C2 H5 )4 NBr at 0.1 moldm3 , 298.15 K and atmospheric pressure

Water + 1,2-propanediol + (C2 H5 )4 NBr


E
x 1,2-propanediol Hm

(Jmol1 )

E
x 1,2-propanediol Hm

(Jmol1 )

E
x 1,2-propanediol Hm

(Jmol1 )

E
x 1,2-propanediol Hm

(Jmol1 )

0.0386

323

0.2697

848

0.5206

636

0.7245

381

0.0802

576

0.3206

828

0.5667

581

0.7564

338

0.1245

737

0.3718

789

0.6105

523

0.7853

299

0.1711

817

0.4225

742

0.6515

469

0.8112

263

0.2197

849

0.4723

691

0.6896

428

Water + 1,3-propanediol + (C2 H5 )4 NBr


E
x 1,3-propanediol Hm

(Jmol1 )

E
x 1,3-propanediol Hm

(Jmol1 )

E
x 1,3-propanediol Hm

(Jmol1 )

E
x 1,3-propanediol Hm

(Jmol1 )

0.0386

286

0.2697

930

0.5206

884

0.7245

593

0.0802

520

0.3206

952

0.5667

833

0.7564

532

0.1245

691

0.3718

955

0.6105

777

0.7853

476

0.1711

811

0.4225

943

0.6515

718

0.8112

424

0.2197

885

0.4723

919

0.6896

657

Water + 1,2-butanediol + (C2 H5 )4 NBr


E
x 1,2-butanediol Hm

(Jmol1 )

E
x 1,2-butanediol Hm

(Jmol1 )

E
x 1,2-butanediol Hm

(Jmol1 )

E
x 1,2-butanediol Hm

(Jmol1 )

0.0329

295

0.2380

610

0.4786

450

0.6898

268

0.0687

458

0.2852

591

0.5252

409

0.7242

241

0.1073

550

0.3335

560

0.5700

372

0.7557

215

0.1486

595

0.3822

526

0.6125

335

0.7842

189

0.1923

615

0.4308

487

0.6526

300

Water + 1,3-butanediol + (C2 H5 )4 NBr


E
x 1,3-butanediol Hm

(Jmol1 )

E
x 1,3-butanediol Hm

(Jmol1 )

E
x 1,3-butanediol Hm

(Jmol1 )

E
x 1,3-butanediol Hm

(Jmol1 )

0.0329

341

0.2380

882

0.4786

690

0.6898

427

0.0687

579

0.2852

865

0.5252

634

0.7242

383

0.1073

747

0.3335

837

0.5700

590

0.7557

340

0.1486

835

0.3822

796

0.6125

531

0.7842

304

0.1923

872

0.4308

741

0.6526

475

mixtures both at 298.15 K; results obtained using the Redlich-Kister equation are also presented. In this figure it is possible to observe the enthalpy of solution of the salts in water (at
xalkanediol = 0.0).
A slight effect of the addition of an electrolyte on the position of the minimum of HmE
can be observed. For mixtures containing 1,2-propanediol or 1,3-butanediol, a displace-

J Solution Chem (2009) 38: 10551070

1063

Table 6 (Continued)
Water + 1,4-butanediol + (C2 H5 )4 NBr
E
x 1,4-butanediol Hm

(Jmol1 )

E
x 1,4-butanediol Hm

(Jmol1 )

E
x 1,4-butanediol Hm

(Jmol1 )

E
x 1,4-butanediol Hm

(Jmol1 )

0.0329

279

0.2380

828

0.4786

847

0.6898

625

0.0687

480

0.2852

856

0.5252

808

0.7242

573

0.1073

616

0.3335

867

0.5700

768

0.7557

520

0.1486

715

0.3822

865

0.6125

730

0.7842

461

0.1923

785

0.4308

859

0.6526

671

Water + 2,3-butanediol + (C2 H5 )4 NBr


E
x 2,3-butanediol Hm

(Jmol1 )

E
x 2,3-butanediol Hm

(Jmol1 )

E
x 2,3-butanediol Hm

(Jmol1 )

E
x 2,3-butanediol Hm

(Jmol1 )

0.0191

337

0.0494

652

0.1546

1057

0.4156

886

0.0218

387

0.0571

707

0.1893

1069

0.4945

779

0.0249

446

0.0663

761

0.2116

1066

0.6020

626

0.0284

483

0.0774

831

0.2379

1060

0.7565

402

0.0325

518

0.0909

883

0.2694

1036

0.0372

559

0.1074

945

0.3078

1003

0.0428

598

0.1282

1003

0.3553

957

E values as a function of the molar fraction of alkanediol (x


Table 7 Experimental Hm
alkanediol ) for water +
alkanediol + C8 H15 N2 Br at 0.1 moldm3 , 298.15 K and atmospheric pressure

Water + 1,2-propanediol + C8 H15 N2 Br


E
E
E
E
x 1,2-propanediol Hm
x 1,2-propanediol Hm
x 1,2-propanediol Hm
x 1,2-propanediol Hm
1
1
1
(Jmol )
(Jmol )
(Jmol )
(Jmol1 )

0.0387
0.0803
0.1246
0.1713
0.2199
0.2700
0.3209

352
558
755
866
895
886
863

0.3721
0.4229
0.4727
0.5210
0.5672
0.6110
0.6520

817
760
698
639
583
528
476

0.6900
0.7250
0.7569
0.7857
0.8116
0.8348
0.8553

429
385
346
306
273
240
210

0.8734
0.8894
0.9033
0.9155
0.9262

182
155
133
111
96

Water + 1,3-propanediol + C8 H15 N2 Br


E
E
E
E
x 1,3-propanediol Hm
x 1,3-propanediol Hm
x 1,3-propanediol Hm
x 1,3-propanediol Hm
1
1
1
(Jmol )
(Jmol )
(Jmol )
(Jmol1 )

0.0387
0.0803
0.1246
0.1713
0.2199
0.2700
0.3209

253
488
662
781
891
965
987

0.3721
0.4229
0.4727
0.5210
0.5672
0.6110
0.6520

981
971
947
899
847
782
723

0.6900
0.7250
0.7569
0.7857
0.8116
0.8348
0.8553

662
596
537
474
427
382
334

0.8734
0.8894
0.9033
0.9155
0.9262

299
267
230
203
184

1064

J Solution Chem (2009) 38: 10551070

Table 7 (Continued)
Water + 1,2-butanediol + C8 H15 N2 Br
E
x 1,2-butanediol Hm

(Jmol1 )

E
x 1,2-butanediol Hm

(Jmol1 )

E
x 1,2-butanediol Hm

(Jmol1 )

E
x 1,2-butanediol Hm

(Jmol1 )

0.0329

313

0.3338

577

0.6530

324

0.8537

138

0.0687

462

0.3826

540

0.6903

290

0.8771

116

0.1074

568

0.4312

503

0.7247

258

0.8966

97

0.1487

616

0.4791

466

0.7561

229

0.9131

79

0.1925

631

0.5256

433

0.7846

203

0.9268

65

0.2382

630

0.5704

396

0.8103

179

0.2855

609

0.6130

359

0.8333

157

Water + 1,3-butanediol + C8 H15 N2 Br


E
x 1,3-butanediol Hm

(Jmol1 )

E
x 1,3-butanediol Hm

(Jmol1 )

E
x 1,3-butanediol Hm

(Jmol1 )

E
x 1,3-butanediol Hm

(Jmol1 )

0.0329

339

0.3338

853

0.6530

472

0.8537

210

0.0687

586

0.3826

807

0.6903

425

0.8771

178

0.1074

767

0.4312

760

0.7247

381

0.8966

150

0.1487

867

0.4791

699

0.7561

341

0.9131

126

0.1925

899

0.5256

641

0.7846

303

0.9268

106

0.2382

904

0.5704

585

0.8103

269

0.2855

887

0.6130

530

0.8333

238

Water + 1,4-butanediol + C8 H15 N2 Br


E
x 1,4-butanediol Hm

(Jmol1 )

E
x 1,4-butanediol Hm

(Jmol1 )

E
x 1,4-butanediol Hm

(Jmol1 )

E
x 1,4-butanediol Hm

(Jmol1 )

0.0329

283

0.3338

889

0.6530

679

0.8537

318

0.0687

486

0.3826

884

0.6903

625

0.8771

269

0.1074

635

0.4312

873

0.7247

577

0.8966

230

0.1487

735

0.4791

849

0.7561

523

0.9131

186

0.1925

806

0.5256

816

0.7846

466

0.9268

160

0.2382

853

0.5704

778

0.8103

413

0.2855

879

0.6130

734

0.8333

363

Water + 2,3-butanediol + C8 H15 N2 Br


E
x 2,3-butanediol Hm

(Jmol1 )

E
x 2,3-butanediol Hm

(Jmol1 )

E
x 2,3-butanediol Hm

(Jmol1 )

E
x 2,3-butanediol Hm

(Jmol1 )

0.0345

447

0.0834

827

0.1741

1095

0.4471

874

0.0396

493

0.0907

865

0.1984

1093

0.5370

749

0.0456

544

0.0988

893

0.2223

1090

0.6620

566

0.0526

601

0.1179

953

0.2508

1099

0.7649

410

0.0610

667

0.1293

994

0.2850

1071

0.8244

311

0.0710

743

0.1423

1024

0.3270

1027

0.8996

181

0.0769

775

0.1571

1072

0.3796

960

Water + 1,2-butanediol
Water + 1,3-Butanediol
Water + 2,3-Butanediol
Water + 1,2-Propanediol + NaBr
Water + 1,3-Propanediol + NaBr
Water + 1,2-Butanediol + NaBr
Water + 1,3-Butanediol + NaBr
Water + 1,4-Butanediol + NaBr
Water + 2,3-Butanediol + NaBr
Water + 1,2-Propanediol + NH4 Br
Water + 1,3-Propanediol + NH4 Br
Water + 1,2-Butanediol + NH4 Br
Water + 1,3-Butanediol + NH4 Br
Water + 1,4-Butanediol + NH4 Br
Water + 2,3-Butanediol + NH4 Br
Water + 1,2-Propanediol + (C2 H5 )4 NBr
Water + 1,3-Propanediol + (C2 H5 )4 NBr
Water + 1,2-Butanediol + (C2 H5 )4 NBr
Water + 1,3-Butanediol + (C2 H5 )4 NBr
Water + 1,4-Butanediol +(C2 H5 )4 NBr
Water + 2,3-Butanediol + (C2 H5 )4 NBr
Water + 1,2-Propanediol + C8 H15 N2 Br
Water + 1,3-Propanediol + C8 H15 N2 Br
Water + 1,2-Butanediol + C8 H15 N2 Br
Water + 1,3-Butanediol + C8 H15 N2 Br
Water + 1,4-Butanediol + C8 H15 N2 Br
Water + 2,3-Butanediol + C8 H15 N2 Br

1908.52
2842.59
3277.50
2443.77
3454.31
1560.22
2638.89
3189.06
2765.98
2415.82
3489.86
1640.49
2658.44
3296.62
3023.61
2636.47
3591.08
1753.75
2683.82
3333.92
3173.77
2658.51
3678.35
1818.97
2694.27
3348.47
3219.54

A0
(Jmol1 )
1416.54
2039.43
2721.32
1585.61
1564.48
1547.72
2148.97
1154.84
2694.51
2039.48
1519.16
1607.14
2222.82
1240.59
2844.38
2250.54
1578.98
1632.38
2272.23
1250.16
3335.94
2415.70
1895.44
1379.90
2321.89
1203.13
2666.03

A1
(Jmol1 )

Table 8 Coefficients Aj for fitting Eq. 2 and the standard deviation at 298.15 K

1066.41
2249.99
2315.51
1771.84
728.59
751.47
1762.28
558.10
23.71
3219.51
709.23
542.93
1745.77
351.42
8.88
1835.82
996.52
649.50
1530.00
434.55
420.64
2606.51
986.54
1187.23
2054.12
1053.14
2706.01

A2
(Jmol1 )
2972.83
3533.77
4253.89
2417.71
997.17
1718.90
2343.91
1824.19
935.70
2279.82
1380.52
1533.85
2215.89
1472.02
1488.21
1873.00
1611.40
1652.54
2267.63
1605.16
56.19
1886.99
583.92
2856.17
2730.45
2334.91
3581.82

A3
(Jmol1 )
3007.89
2858.86
4283.75
1685.13
1153.73
3907.03
2677.04
2474.50
11270.50
325.11
1078.07
4306.37
2495.13
2698.11
10687.50
1695.28
948.04
4230.94
3293.26
2966.15
12390.20
399.29
401.14
2600.76
2176.28
1470.49
2683.53

A4
(Jmol1 )

17.06
6.89
12.41
3.57
6.21
12.56
6.84
3.98
17.84
11.58
9.80
12.67
5.96
4.37
19.55
4.45
2.26
11.03
4.88
6.44
29.46
8.03
5.82
12.35
5.70
6.51
8.68

(Jmol1 )

J Solution Chem (2009) 38: 10551070


1065

1066

J Solution Chem (2009) 38: 10551070

E as a function of the mole fraction of alkanediol:  (water + alkanediol


Fig. 1 Values of Hm
+ NaBr),  (water + alkanediol + NH4 Br), (water + alkanediol + (C2 H5 )4 NBr), + (water
+ alkanediol + C8 H15 N2 Br),  (water + alkanediol), and solid lines Redlich-Kister equation

ment to higher alkanediol concentration is observed whereas for mixtures containing 1,3propanediol or 2,3-propanediol, a displacement to lower mole fractions of alkanediol is
observed. This can be attributed to the presence of electrolyte taking part in hydrophobic
effects. For the other alkanediolwatersalt mixtures, the effect is negligible.
The excess molar enthalpy values are negative over the whole composition range for
all studied mixtures. The curves are skewed towards the side of the water-rich region. The
absolute value of HmE decreases with salt addition i.e., the exothermal effect is decreased by
the presence of the added salt. The order of decrease of the exothermal effect for all mixtures

J Solution Chem (2009) 38: 10551070


Table 9 Maximum exothermic
effects in the 0.1 moldm3
ternary aqueous mixtures

1067
E maximum
x alkanediol Hm

Ternary aqueous mixtures

(Jmol1 )

Water + 1,2-propanediol + NaBr


NH4 Br

834

(C2 H5 )4 NBr

849
863

NH4 Br

ca.

909

0.350

919

(C2 H5 )4 NBr

956

C8 H15 N2 Br

989

Water + 1,2-butanediol + NaBr


NH4 Br

ca.

577

0.190

589

(C2 H5 )4 NBr

615

C8 H15 N2 Br

631

Water + 1,3-butanediol + NaBr


NH4 Br

ca.

862

0.230

868

(C2 H5 )4 NBr

882

C8 H15 N2 Br

904

Water + 1,4-butanediol + NaBr


NH4 Br

ca.

835

0.340

858

(C2 H5 )4 NBr

869

C8 H15 N2 Br

891

Water + 2,3-butanediol + NaBr

ca.

NH4 Br

Binary aqueous mixtures

769

0.220

C8 H15 N2 Br
Water + 1,3-propanediol + NaBr

Table 10 Maximum exothermic


effects in binary aqueous
mixtures containing alkanediols

around

0.170

979
1032

(C2 H5 )4 NBr

1070

C8 H15 N2 Br

1095

x alkanediol

E maximum
Hm

(Jmol1 )

Water + 1,2-propanediol

0.205

970

Water + 1,3-propanediol

0.387

1034

Water + 1,2-butanediol

0.185

648

Water + 1,3-butanediol

0.208

952

Water + 1,4-butanediol

0.344

916

Water + 2,3-butanediol

0.197

1156

is the following: C8 H15 N2 Br < (C2 H5 )4 NBr < NH4 Br < NaBr. The electrolyte cation size
decreases in the same sequence.
The maximum exothermic effects (in terms of HmE ) in the 0.1 moldm3 ternary mixtures
as well as its corresponding mole fractions are showed in Table 9; for the salt-free binary
mixtures the maximum exothermic effects are presented in Table 10.
It is possible to observe the behavior of the experimental excess molar enthalpy data
of water + alkanediol (salt-free and with salt) mixtures in relation to the OH group po-

1068

J Solution Chem (2009) 38: 10551070

sition in the alkanediol carbon chain. For propanediols, the differences between the HmE
data of salt-free mixtures and those containing salt are greater in the mixtures containing
1,2-propanediol (whose OH groups are vicinal) than those showed in the mixtures containing 1,3-propanediol (whose OH groups are positioned in the carbon 1 and 3 of the
alkanediol chain). For butanediols, the differences between the HmE data of salt-free mixtures and those containing salt are greater in the mixtures containing 2,3-butanediol and 1,2butanediol (whose OH groups are vicinal) than those of mixtures containing 1,3-butanediol
and 1,4-butanediol (whose OH groups are positioned in the carbon (1 and 3) and (1 and 4)
of the alkanediol chain, respectively).
According to Franks and Ives [19], the dissolution of a mono-alcohol into water is accompanied by structural enhancement of the solution promoted by two kinds of effects:
hydrophilic effects, which are the hydrogen bonding among water and hydroxyl groups, and
hydrophobic effects, which are related to the hydrogen bonding between water molecules,
forming a cluster around the non-polar surface of a mono alcohol molecule [13]. These
effects have also been observed in alkanediols [20, 21], which are similar chemically to
mono-alcohols. As a consequence, HmE curves have an unsymmetrical and steep form at the
hydroxyl compound dilute region.
Due to presence of an additional hydroxyl group (OH) in the alkanediol molecules
(compared to alcohol molecules), the hydrophobic effect is influenced by the position of
this OH in the former, as pointed out in [20, 21]. This characteristic is observed in present
work: for 1,2-butanediol, 2,3-butanediol and 1,2-propanediol aqueous binary mixtures, hydrophobic effects are more pronounced than for mixtures containing water + (1,3-butanediol
or 1,3-propanediol or 1,4-butanediol) due to displacement of the hydroxyl groups in its vicinal carbon atoms and consequent presence of alkyl groups (CH3 and CH2 CH3 ). Following Nagamachi and Francesconi [13], the intensity of the hydrophobic effect occurring
in the aqueous mixtures containing alkanediols can be observed by the large displacement
of the maximum exothermic effect value along the ordinate axis (see Table 10). In these binary salt-free mixtures, the hydrophobic effect is more pronounced in the mixtures containing 1,2-butanediol and decrease according the following sequence: 1,2-butanediol > 2,3butanediol > 1,2-propanediol > 1,3-butanediol > 1,4-butanediol > 1,3-propanediol. However, in the ternary mixtures containing water + alkanediol + salt, this sequence is slightly
modified (see Table 9): the hydrophobic effect is more pronounced in the mixtures containing 2,3-butanediol than in the mixtures containing 1,2-butanediol and the rest of the
sequence stays unchanged.
Another important fact is associated with the presence of organic cations in the
C8 H15 N2 Br and (C2 H5 )4 NBr salts; its hydrophobic character competes with that of the
alkyl groups of the alkanediols molecules [15] and increases the enthalpic effect in relation
to that present in mixtures containing the inorganic salts NaBr and NH4 Br.

4 Conclusion
Experimental HmE data of ternary water + alkanediol + salt mixtures were determined at
0.1 moldm3 , 298.15 K and atmospheric pressure. These data were compared with those
obtained experimentally for water + alkanediol salt-free mixtures. For all investigated mixtures, the absolute value of the excess molar enthalpy decreases with salt addition meaning
that the exothermal effect is reduced by the presence of the added salt. For a specific alkanediol, the exothermicity decreases as the electrolyte size decreases. Another contribution

J Solution Chem (2009) 38: 10551070

1069

which influences the behavior of experimental data is associated with the presence of inorganic or organic electrolytes in the mixtures: the presence of an inorganic salt decreases
the hydrophobic effect in the mixture; therefore, excess molar enthalpy absolute values are
lower in mixtures containing inorganic salts than in both salt-free and organic saline mixtures [15]. The hydrophobic effect is also dependent of the OH position on the carbon chain
of the alkanediol: for aqueous mixtures containing alkanediols, whose hydroxyl groups are
positioned on vicinal carbon atoms, the hydrophobic hydration effects are more pronounced;
moreover, the hydrophilic hydration effect is less pronounced in these aqueous mixtures,
since the hydroxyl groups vicinal position on alkanediols molecules means that the alkyl
groups (CH3 and CH2 CH3 ) are positioned as a side chain.
Acknowledgements Ricardo F. Checoni wishes to thank CAPES (Coordenao de Aperfeioamento de
Pessoal de Nvel Superior) for the financial support received in the form of a postgraduate fellowship.

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