J Solution Chem (2015) 44:206222

DOI 10.1007/s10953-015-0305-5

Experimental Study and Modeling of the Refractive

Indices in Binary and Ternary Mixtures of Water
with Methanol, Ethanol and Propan-1-ol at 293.15 K
Marlon Martnez-Reina Eliseo Amado-Gonzalez Wilfred Gomez-Jaramillo

Received: 9 August 2014 / Accepted: 1 November 2014 / Published online: 24 February 2015
Springer Science+Business Media New York 2015

Abstract Refractive indices of ternary mixtures of water ? methanol ? (ethanol or

propan-1-ol), (water or methanol) ? ethanol ? propan-1-ol and their binary mixtures have
been measured at 293.15 K and at atmospheric pressure over the whole composition range.
The refractive index deviations were calculated and fitted to the RedlichKister equation
for binary mixtures, and the Cibulka equation for ternary mixtures. Furthermore, we
demonstrate that the refractive index of the associated ternary mixtures can be estimated
with relative errors from 0.036 to 0.861 % by using the several mixing rules and the
refractive indices of the corresponding pure components. The behavior of refractive indices
is associated with solventsolvent interactions and the formation of clusters.
Keywords Refractive index  Ternary mixtures  Refractive index deviations  Mixing
rules  Clusters

1 Introduction
The refractive indices of pure components and their mixtures are an optical property of
matter that allows control of processes in the chemical, petrochemical and pharmaceutical
industries, and its importance is well known. For some specific scientific applications, the
required accuracy is very high and requires precise measurements [1]. Since the refractive
index of a liquid at the sodium D line light, nD , is a property easy to measure with good
accuracy, it has been connected with other thermo physical properties, such as surface
tension and density, by empirical and theoretical equations [2, 3]. A structureproperty
model has been found to have great potential for predicting the physicochemical properties
of substances [4]. It is known that refractive index mixing rules allow estimation of the

M. Martnez-Reina  E. Amado-Gonzalez (&)  W. Gomez-Jaramillo

Ibear L-307 Biofuels Laboratory, Department of Chemistry, University of Pamplona, Ciudad
Universitaria, Pamplona, Colombia
e-mail: eamado@unipamplona.edu.co

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207

refractive index of a mixture from the refractive indices of the pure components. Hellers
work [5] shows that these mixing rules can be used to predict the density or excess volumes
of a mixture from its refractive index or vice versa.
In recent years some workers have studied the refractive indices of (binary or ternary)
liquid mixtures and analyzed the applicability of the refractive index mixing rules: 19
binary mixtures of various polarities [6], 73 binary mixtures containing various groups of
organic compounds [7, 8], (water ? ethanol ? k-ethylene glycol) (when k is mono, di or
tri) [1], isomers of butanol with n-hexane, and 1-chlorobutane [9], isomers of chlorobutanes and butanols [10], diethyl malonate ? (dimethylformamide, hexane, tetrahydrofuran
or 1,4-dioxane) [11], tetrahydrofuran ? (methanol or o-cresol) [12], eucalyptol ? hydrocarbons [13], ethanol ? n-alkane mixtures [14], chlorobenzene ? n-hexane ? (n-heptane
or n-octane) [15], cyclohexane ? toluene ? methanol [16], and tetralin ? isobutylbenzene ? dodecane [17]. Alcohols are polar molecules, self-associated by hydrogen bonding
of their hydroxyl groups [18]. The hydrogen bonding gives the alcohols the possibility of
interacting with other substances to change their structure. The applications of alcohols in
the food industry, and pharmaceutical uses as co-surfactants in micro emulsions, are still
under development [19].
Among the thermo physical properties, refractive indices of water with alcohols in
binary and ternary systems are expected to show complex behavior, due to the intermolecular interactions [20]. Therefore, the binary systems of water with methanol, ethanol
or propan-1-ol, and their ternary systems are of great interest.
In the present paper, refractive indices at 293.15 K are reported for six binary mixtures:
water ? (methanol, ethanol or propan-1-ol), methanol ? (ethanol or propan-1-ol), ethanol ? propan-1-ol, and for four ternary mixtures: water ? methanol ? (ethanol or propan-1-ol), water ? ethanol ? propan-1-ol and methanol ? ethanol ? propan-1-ol. These
data were used to calculate the refractive index deviations, DnD , which were correlated
using a 5-parameter RedlichKister equation [21] for binary mixtures and the Cibulka
equation [22] for ternary mixtures. Finally, we have used several mixing rules, those of
LorentzLorenz [23, 24], GladstoneDale [25], Eykman [26], Newton [27] and Oster [28],
to predict refractive indices. The accuracy of the mixing rules for determination of refractive indices is analyzed and cluster formation is predicted for the ternary mixtures.

2 Experimental
Densities of the pure liquids were measured by using a pycnometer having bulb volume of
approximately 10 cm3 and capillary with internal diameter of 1 mm. First, the pycnometer
was calibrated with distilled water of known density, and then it was filled with pure liquid
and immersed in a thermostatic bath. The bath temperature was monitored to 0.01 K with
a calibrated thermometer. In addition, all of the measurements were conducted in a room
with controlled air temperature. About 120 min later, the sample was weighed. A cover
was used in order to prevent the samples from absorbing water or evaporating. The
uncertainly of the density measurements was estimated to be 0.05 %. Mixtures were
prepared by mixing the appropriate volumes of liquids in specially designed ground glass
air-tight ampules and weighed in single pan balance (Ohaus electronic balance) to an
accuracy of 0.0001 g. Preferential evaporation losses of solvent from the mixture were
kept to a minimum as evidenced by repeated measurements of thermo physical properties
over an interval of 23 days, during which time no change in physical properties were
observed. The composition of the mixtures were calculated in mole fraction with atomic

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weights recommended by IUPAC in 2000 [29]. The possible error in mole fraction is
estimated to be around 0.0001. Refractive indices for the sodium D line were measured
using Abbes refractometer (CARL ZEISS, Model A, Germany). Water was circulated into
the instrument from the thermostatically controlled bath. The current temperature of the
measurement prism of the refractometer was monitored using a built-in instrument with an
uncertainty 0.1 K. The refractometer was calibrated by measuring the refractive indices
of triply distilled water and ethanol at 293.15 K. The accuracy in the refractive index
measurements is 0.0001 U. The sample mixtures were directly injected into the prism
assembly of the instrument by means of an air-tight hypodermic syringe. An average of
three to five measurements was taken for a sample mixture. The source of our chemicals
and our measured values at 293.15 K of two physical properties of the pure compounds,
densities and refractive indices, are compared with literature [3034] values in Table 1.
The refractive indices of the binary systems water(1) ? propan-1-ol(2), water(1) ?
ethanol(2) and water(1) ? methanol(2) are compared with literature data in Fig. 1.

3 Results and Discussion

The experimental results of mole fraction, xi , refractive indices, nD , refractive index deviations, DnD , at 293.15 K for all binary mixtures are reported in Table 2. The refractive
index deviations were evaluated for each composition point, using the following equation:
DnD nD 

n
X

xi nD;i

i1

where nD is the refractive index of the mixture and the corresponding quantity with
subscript i refers to the corresponding pure chemicals. The experimental DnD values were
correlated using a 5-parameter RedlichKister equation:
DnD x1 x2

m
X

Ap x1  x2 p

p0

where x is the molar fraction, A0, A1, A2, A3 and A4 are the RedlichKister parameters
obtained by least-squares method, and m = 4 is the degree of the polynomial expansion.
The parameters calculated using Eq. 2 are listed in Table 3. On Fig. 2, the refractive index
deviations are shown for the binary mixtures. The physical property values of these solutions can be affected by two factors. The first factor is the concentration units (molar,
molalor mole fraction) of the solute in the mixture. The second factor is the strength of

Table 1 Experimental and literature values [3034] of densities, q, and refractive indices, nD, of the pure
compounds at 293.15 K
Compound

nD
(experimental)

nD
(literature)

q (experimental)
gcm-3

q (literature)
gcm-3

Water, deionized reagent grade 3

1.3330

1.3330 [30]

0.9981

0.9982 [33]

Methanol (Sigma-Aldrich, 99.9 %)

1.3299

1.32941 [31]

0.7912

0.79115 [31]

Ethanol (Carlo Erba, 99.8 %)

1.3618

1.3620 [30]

0.7895

0.78970 [34]

Propan-1-ol (Merck, 99.5 %)

1.3853

1.38512 [32]

0.8036

0.80360 [34]

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J Solution Chem (2015) 44:206222

209

Fig. 1 Comparison between the experimental data and values from literature. Water(1) ? methanol(2):
(filled circle) this work at 293.15 K, (circle) Ref. [35] at 292.15 K. Water(1) ? ethanol(2): (filled square)
this work at 293.15 K, (square) Ref. [35] at 292.15 K, (cross) Ref. [36] at 293.15 K. Water(1) ? propan-1ol(2): (filled diamond) this work at 293.15 K, (diamond) Ref. [35]

bonds between solvent and solute molecules due to the values of polarity (dipoledipole
interaction and the H-bonds) and the electrical charge of solute molecules [35].
It can be observed from the experimental data in Table 2 and Fig. 2 that, over the whole
composition range for all aqueous solutions of this study at T = 293.15 K, the variation
of DnD is positive and follows this order: DnD CH3 OH\DnD CH3 CH2 OH\
DnD CH3 CH2 CH2 OH for these solutions the values of DnD increase with the size of the
(R) group. On Fig. 2, a maximum is observed at xM = xmethanol = 0.3961 for the mixture
water ? methanol. Takamuku et al. [37] found, from analysis of radial distribution
functions (RDF) for methanol ? water mixtures, three peaks at xM = 0.4 and 298.15 K
that were analyzed were the result of the intermolecular interactions of methanol chain
clusters and the second-neighbor interactions in the tetrahedral-like structure of water [38].
Positive deviations of the excess values of binary mixtures should be the result of dispersion forces and non-specific physical (weak) interactions [39]. Nagasaka et al. [40]
found that the total energy of the binary solution is stabilized by the network structure of
water with the methanol clusters. But, the effect of water molecules on the methyl group of
methanol may depend on whether water molecules are free or associated in the network.
For the mixture ethanol ? water, it is found on Fig. 2 that a maximum occurs at xE =
xEthanol = 0.2972. Matsumoto et al. found that both ethanol chain clusters and water
clusters are formed in ethanolwater mixture at xE = 0.3 and 298.15 from RDF analysis
[41]. For the mixture water ? propan-1-ol, the maximum is found at xp,1 = xpropan-1-

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Table 2 Experimental refractive
indices and their deviations from
ideality at 293.15 K for the investigated binary mixtures

J Solution Chem (2015) 44:206222

x1

nD

DnD

x1

nD

DnD

Water(1) ? methanol(2)
0.0000

1.3299

0.0000

0.6039

1.3436

0.0118

0.1007

1.3326

0.0023

0.6901

1.3432

0.0111

0.2044

1.3359

0.0054

0.7941

1.3412

0.0088

0.2910

1.3385

0.0076

0.8952

1.3376

0.0049

0.4034

1.3411

0.0099

1.0000

1.3330

0.0000

0.5003

1.3423

0.0108

Water(1) ? ethanol(2)
0.0000

1.3618

0.0000

0.5983

1.3645

0.0199

0.1037

1.3640

0.0052

0.7028

1.3626

0.0210

0.2064

1.3649

0.0090

0.7932

1.3584

0.0194

0.3047

1.3657

0.0127

0.8979

1.3488

0.0128

0.3939

1.3660

0.0156

1.0000

1.3330

0.0000

0.4937

1.3656

0.0180

Water(1) ? propan-1-ol(2)
0.0000

1.3853

0.0000

0.5979

1.3762

0.0221

0.1080

1.3843

0.0046

0.7225

1.3708

0.0233

0.2181

1.3834

0.0095

0.7939

1.3662

0.0224

0.2737

1.3828

0.0118

0.8999

1.3552

0.0169

0.4030

1.3809

0.0167

1.0000

1.3330

0.0000

0.4998

1.3789

0.0197

Methanol(1) ? ethanol(2)
0.0000

1.3618

0.0000

0.6108

1.3447

0.0024

0.1099

1.3591

0.0008

0.7062

1.3413

0.0020

0.1727

1.3576

0.0013

0.8078

1.3373

0.0012

0.3292

1.3535

0.0022

0.9010

1.3338

0.0007

0.4003

1.3514

0.0024

1.0000

1.3299

0.0000

0.5065

1.3481

0.0024

Methanol(1) ? propan-1-ol(2)
0.0000

1.3853

0.0000

0.6007

1.3596

0.0076

0.1177

1.3809

0.0021

0.7023

1.3534

0.0070

0.1798

1.3788

0.0035

0.7721

1.3485

0.0059

0.3147

1.3738

0.0059

0.8971

1.3387

0.0031

0.3760

1.3710

0.0065

1.0000

1.3299

0.0000

0.4801

1.3660

0.0073

Ethanol(1) ? propan-1-ol(2)

123

0.0000

1.3853

0.0000

0.6134

1.3720

0.0011

0.1077

1.3825

-0.0003

0.6879

1.3701

0.0010

0.2227

1.3803

0.0002

0.7961

1.3672

0.0006

0.2797

1.3792

0.0005

0.8930

1.3646

0.0003

0.3880

1.3771

0.0009

1.0000

1.3618

0.0000

0.5007

1.3747

0.0012

J Solution Chem (2015) 44:206222

211

Table 3 RedlichKister parameters Ai (Eq. 2) and the standard deviations (r, Eq. 5)
A0

A1

A3

A4

0.00840

-0.00547

-0.02717

0.00010

0.04477

0.01016

-0.00877

0.00016

0.03719

0.05223

0.03536

0.00009

-0.00199

-0.00053

-0.00259

0.00006

0.00436

0.00122

-0.01539

0.00005

-0.00615

0.00373

-0.00237

0.00002

A2

Water(1) ? methanol(2)
0.04414

0.01977

Water(1) ? ethanol(2)
0.07266

0.04826

Water(1) ? propan-1-ol(2)
0.07904

0.05310

Methanol(1) ? ethanol(2)
0.00998

-0.00036

Methanol(1) ? propan-1-ol(2)
0.02971

0.00779

Ethanol(1) ? propan-1-ol(2)
0.00467

0.00151

ol = 0.2775 as seen in Fig. 2. It is found that the mixtures from C1 to C3 show that the
maximum moves to a more water-rich zone (xw = xwater = 0.6039 for methanol to
xw = 0.7225 for propan-1-ol). Thus cluster formation may be expected at these
concentrations.
In this work, the binary mixtures with alcohols show values of DnD lower than those
reported for aqueous mixtures. The variation of DnD in these mixtures is:
DnD CH3 CH2 OH + CH3 CH2 CH2 OH\DnD CH3 OH + CH3 CH2 OH\DnD CH3 OH +
CH3 CH2 CH2 OH; the mixture that deviates least from ideality is ethanol(1) ? propan-1ol(2). Our results for this mixture, as a function of concentration at 298.15 K, coincide well
with those reported in the literature [32].
The experimental results of mole fraction, xi, refractive indices, nD, refractive index
deviations, DnD , at 293.15 K for all ternary mixtures are reported in Table 4. The refractive index deviations for the ternary mixtures have been fitted by the Cibulka equation:

DnD DnD;bin x1 x2 1  x1  x2 B1 B2 x1 B3 x2 
DnD;bin x1 x2

m
X
p0

Ap x1  x2 p x1 x3

m
X
q0

Aq x1  x3 q x2 x3

m
X

Ar x2  x3 r

r0

where the Ai are binary solution parameters of a RedlichKister type equation for the
constituent binary mixtures, Bi are parameters of the Cibulka equation and xi is molar
fraction of component i at the ternary data composition. The parameters calculated using
Eq. 3 are listed in Table 5. The root-mean-square deviations (r) were computed using
Eq. 5, where ncalc is the calculated value of refractive index, nexp is the measured value of
the refractive index, and NDAT is the number of experimental data values:
!
PNDAT
2 1=2
i1 nexp  ncalc
5
r
NDAT
Figures 3, 4, 5, and 6 show that the refractive index deviations for all the ternary
mixtures are positive over the whole composition range. The results are consistent with

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Fig. 2 Curves of refractive index deviations at 293.15 K for the systems: (filled circle) water(1) ? methanol(2), (filled square) water(1) ? ethanol(2), (filled diamond) water(1) ? propan-1-ol(2),
(circle) methanol(1) ? ethanol(2), (square) methanol(1) ? propan-1-ol(2), and (diamond) ethanol(1) ?
propan-1-ol(2). The experimental data were fitted with RedlichKister type polynomials (solid line)

those reported in binary mixtures; aqueous solutions show a greater deviation than the
mixtures composed of the three alcohols: methanol(1) ? ethanol(2) ? propan-1-ol(3). The
maximum refractive index deviation (DnD) for the ternary mixtures in Table 6 varies
in the order: methanol ? ethanol ? propan-1-ol \ water ? methanol ? ethanol \ water ?
methanol ? propan-1-ol = water ? ethanol ?propan-1-ol. The refractive index deviations of the aqueous mixtures are due to hydrogen bond interactions between the water
or methanol molecule, ethanol and propanol molecules.
Reiss et al. [42] considered that the increase of the refractive indices for the mixtures of
solvents is explained as the result of both energetic and structural effects where the enhancement of London disperse forces plays an important role. We may expect that these
maxima in the water-rich zone should reflect cluster structures. In the mixtures of solvents
with water, Fontao et al. considered that positive values of the refractive index deviation on
mixing may be due to two opposing factors: (a) the hydrogen-bond interaction between
solute and solvent for each mixture, and (b) the steric hindrance of aliphatic residues [32].
The positive refractive index deviation decrease in the following order for the binary
mixtures: water(1) ? propan-1-ol(2) [ water(1) ? ethanol(2) [ water(1) ? methanol(2) [
methanol(1) ? propan-1-ol(2) [ methanol(1) ? ethanol(2) [ ethanol(1) ? propan-1-ol(2).
This suggests that the steric hindrance of aliphatic residues affects the increase for alcohol
mixtures where hydrogen bonding is not strong. The isolines of DnD obtained from Cibulka
equation, for the four ternary systems, are plotted at the bottom of Figs. 3, 4, 5, and 6.
The following equations were used for quantitative determination of refractive indices
of ternary mixtures:

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213

Table 4 Experimental refractive indices and their deviations from ideality at 293.15 K for the ternary
mixtures
x1

x2

nD

DnD

x1

x2

nD

DnD

Water(1) ? methanol(2) ? ethanol(3)

0.1047

0.7951

1.3363

0.0029

0.2865

0.3089

1.3548

0.0111

0.1076

0.6916

1.3407

0.0041

0.2865

0.2154

1.3581

0.0114

0.0956

0.6055

1.3442

0.0045

0.2854

0.1088

1.3613

0.0112

0.1107

0.5061

1.3479

0.0054

0.3941

0.4995

1.3453

0.0108

0.0997

0.4133

1.3512

0.0055

0.4357

0.3762

1.3504

0.0132

0.0906

0.3139

1.3542

0.0050

0.3976

0.3060

1.3540

0.0134

0.1112

0.2032

1.3576

0.0055

0.3745

0.2117

1.3580

0.0137

0.1060

0.0784

1.3608

0.0046

0.4103

0.1096

1.3613

0.0148

0.1873

0.7079

1.3399

0.0061

0.5118

0.3821

1.3479

0.0130

0.1896

0.6047

1.3444

0.0074

0.5146

0.2914

1.3526

0.0149

0.1659

0.5231

1.3478

0.0075

0.4912

0.1991

1.3573

0.0160

0.1847

0.4154

1.3517

0.0085

0.4746

0.1345

1.3601

0.0163

0.2151

0.3006

1.3558

0.0098

0.5879

0.2982

1.3497

0.0143

0.2217

0.2004

1.3590

0.0100

0.5995

0.2075

1.3543

0.0164

0.2302

0.1013

1.3618

0.0099

0.6175

0.0963

1.3594

0.0185

0.3283

0.5718

1.3431

0.0090

0.7211

0.1842

1.3498

0.0146

0.3045

0.4992

1.3470

0.0099

0.7007

0.1020

1.3541

0.0157

0.3069

0.3988

1.3513

0.0111

0.7960

0.0961

1.3506

0.0148

Water(1) ? methanol(2) ? propan-1-ol(3)

0.0863

0.8045

1.3417

0.0055

0.3021

0.2980

1.3689

0.0159

0.0963

0.6945

1.3502

0.0084

0.3168

0.1699

1.3750

0.0157

0.1015

0.5736

1.3584

0.0102

0.2943

0.0959

1.3784

0.0138

0.0919

0.5028

1.3628

0.0102

0.4025

0.4686

1.3529

0.0146

0.0988

0.4011

1.3681

0.0102

0.3713

0.4096

1.3586

0.0154

0.0911

0.2987

1.3731

0.0091

0.3712

0.3088

1.3659

0.0171

0.0990

0.1948

1.3772

0.0079

0.3851

0.2037

1.3715

0.0176

0.0945

0.0990

1.3807

0.0058

0.3860

0.0919

1.3769

0.0169

0.1844

0.6978

1.3459

0.0089

0.5135

0.3737

1.3539

0.0162

0.1789

0.6108

1.3531

0.0110

0.4737

0.3105

1.3616

0.0183

0.1505

0.4964

1.3617

0.0118

0.4886

0.2065

1.3680

0.0197

0.2129

0.3967

1.3658

0.0136

0.5071

0.0956

1.3738

0.0203

0.1915

0.3185

1.3705

0.0129

0.5726

0.3211

1.3547

0.0171

0.1524

0.2349

1.3751

0.0108

0.5769

0.2244

1.3628

0.0201

0.1803

0.1467

1.3782

0.0105

0.5939

0.0980

1.3706

0.0218

0.2686

0.6308

1.3474

0.0111

0.6953

0.1982

1.3564

0.0184

0.2953

0.4885

1.3571

0.0143

0.7502

0.0774

1.3630

0.0212

0.2787

0.4089

1.3630

0.0149

0.7724

0.1326

1.3555

0.0179

Water(1) ? ethanol(2) ? propan-1-ol(3)

0.0843

0.8128

1.3663

0.0045

0.3232

0.2841

1.3758

0.0141

0.1028

0.6966

1.3692

0.0056

0.2865

0.1968

1.3783

0.0126

0.0962

0.6005

1.3718

0.0056

0.2760

0.1176

1.3801

0.0120

0.1086

0.4907

1.3744

0.0063

0.4219

0.4789

1.3681

0.0161

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Table 4 continued
x2

nD

DnD

x1

x2

nD

DnD

0.0920

0.4001

1.3766

0.0055

0.3748

0.4140

1.3712

0.0152

0.1044

0.2894

1.3787

0.0057

0.3941

0.3193

1.3732

0.0160

0.1149

0.1966

1.3806

0.0059

0.3910

0.2006

1.3762

0.0161

0.0814

0.1001

1.3827

0.0040

0.4006

0.1017

1.3782

0.0162

0.1890

0.6961

1.3679

0.0088

0.5059

0.3967

1.3679

0.0184

0.1866

0.6005

1.3704

0.0090

0.4828

0.2990

1.3713

0.0183

0.1846

0.4881

1.3733

0.0091

0.4783

0.2045

1.3739

0.0184

0.1893

0.3977

1.3754

0.0093

0.4958

0.1028

1.3759

0.0189

0.1892

0.2879

1.3777

0.0091

0.5740

0.3227

1.3672

0.0195

0.1791

0.1900

1.3798

0.0083

0.6029

0.1978

1.3698

0.0207

0.1875

0.1176

1.3812

0.0085

0.5694

0.1140

1.3735

0.0207

0.2835

0.5994

1.3684

0.0120

0.6878

0.2121

1.3654

0.0211

0.2642

0.4958

1.3716

0.0118

0.6975

0.1095

1.3680

0.0218

0.2915

0.3812

1.3741

0.0130

0.8089

0.0944

1.3610

0.0202

x1

Methanol(1) ? ethanol(2) ? propan1-ol(3)

0.0947

0.7928

1.3634

0.0020

0.2811

0.2982

1.3679

0.0052

0.0822

0.7133

1.3662

0.0022

0.2681

0.2290

1.3702

0.0051

0.1009

0.5978

1.3685

0.0028

0.3126

0.1124

1.3712

0.0059

0.0738

0.5123

1.3720

0.0028

0.3948

0.4945

1.3556

0.0038

0.0988

0.3997

1.3736

0.0032

0.4061

0.3906

1.3584

0.0048

0.0900

0.3069

1.3761

0.0030

0.4027

0.2873

1.3618

0.0056

0.0948

0.2020

1.3780

0.0027

0.4085

0.1935

1.3641

0.0060

0.0885

0.1005

1.3803

0.0023

0.4061

0.1189

1.3664

0.0064

0.2027

0.6831

1.3608

0.0028

0.4794

0.4202

1.3535

0.0046

0.2020

0.5960

1.3634

0.0033

0.5060

0.3082

1.3556

0.0056

0.1832

0.5127

1.3667

0.0036

0.5185

0.1997

1.3583

0.0064

0.2141

0.3850

1.3688

0.0044

0.5048

0.0997

1.3622

0.0072

0.1881

0.3063

1.3718

0.0041

0.5823

0.2947

1.3509

0.0048

0.1891

0.2083

1.3742

0.0043

0.6050

0.1999

1.3532

0.0061

0.1766

0.1143

1.3767

0.0039

0.5941

0.1090

1.3568

0.0070

0.2862

0.5990

1.3590

0.0036

0.7066

0.1946

1.3459

0.0043

0.3023

0.5087

1.3607

0.0041

0.6997

0.0981

1.3505

0.0063

0.3015

0.4011

1.3639

0.0047

0.7724

0.1205

1.3440

0.0043

Table 5 Parameters, Bi, of the Cibulka equation for the ternary mixtures together with the corresponding
standard deviations, r
System

B1

B2

B3

Water(1) ? methanol(2) ? ethanol(3)

-0.02015

-0.11273

-0.01606

0.00050

Water(1) ? methanol(2) ? propan-1-ol(3)

-0.02098

-0.00227

0.01776

0.00025

Water(1) ? ethanol(2) ? propan-1-ol(3)

0.02870

-0.35314

-0.02009

0.00035

Methanol(1) ? ethanol(2) ? propan-1-ol(3)

0.01070

0.01264

0.00850

0.00032

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215

Fig. 3 Refractive index deviations

water(1) ? methanol(2) ? ethanol(3)

and

isolines

at

293.15 K

for

the

ternary

system

LorentzLorenz (LL):

k  2
n2  1 X
ni  1

/i
n2 2
n2i 2
i1

GladstoneDale (GD):
n1

k
X

ni  1 /i

i1

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J Solution Chem (2015) 44:206222

Fig. 4 Refractive index deviations and isolines at 293.15 K for the ternary system water(1) ?
methanol(2) ? propan-1-ol(3)

Eykman (Eyk):

k  2
X
n2  1
ni  1
/i

n2 0:4
n2i 0:4
i1

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J Solution Chem (2015) 44:206222

217

Fig. 5 Refractive index deviations and isolines to 293.15 K for the ternary system water(1) ?
ethanol(2) ? propan-1-ol(3)

Newton (Nw):
n2  1

k
X

n2i  1 /i

i1

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Fig. 6 Refractive index deviations at isolines to 293.15 K for the ternary system methanol(1) ? ethanol(2) ? propan-1-ol(3)

Oster (Os):

k  2
n2  12n2 1 X
ni  12n2i 1

/i
n2
n2i
i1

10

Here n is the refractive index of the mixtures, ni is the refractive index of the corresponding
pure components i, k is the number of the mixture components, and /i is the volume
fraction of component i:

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219

Table 6 The maximum refractive index deviations (DnD ) for the ternary mixtures at 293.15 K
DnDmax

System

x1

x2

x3

Water(1) ? methanol(2) ? ethanol(3)

0.0185

0.6175

0.0963

0.2862

Water(1) ? methanol(2) ? propan-1-ol(3)

0.0218

0.5939

0.0980

0.3081

Water(1) ? ethanol(2) ? propan-1-ol(3)

0.0218

0.6975

0.1095

0.1930

Methanol(1) ? ethanol(2) ? propan-1-ol(3)

0.0072

0.5048

0.0997

0.3955

Table 7 Average absolute deviations (AAD) and maximal deviation (M Dev) of the experimental refractive indices from the estimated results using the LorentzLorenz (LL), GladstoneDale(GD), Eykman
(Eyk), Newton (Nw) and Oster (Os) equations
System
Water(1) ? methanol(2) ? ethanol(3)
Water(1) ? methanol(2) ? propan-1-ol(3)
Water(1) ? ethanol(2) ? propan-1-ol(3)
Methanol(1) ? ethanol(2) ? propan-1-ol(3)

LL

GD

Eyk

Nw

Os

AAD

0.495

0.490

0.492

0.485

0.488

M Dev

0.861

0.857

0.858

0.852

0.855

AAD

0.315

0.300

0.305

0.283

0.292

M Dev

0.730

0.716

0.721

0.701

0.709

AAD

0.306

0.299

0.302

0.292

0.296

M Dev

0.686

0.676

0.680

0.665

0.670

AAD

0.013

0.017

0.016

0.024

0.020

M Dev

0.036

0.050

0.045

0.065

0.057

xi V i
/i Pk
i1 xi Vi

11

where xi is the mole fraction of the component i, and Vi is the molar volume of the
component i. In order to estimate the ability of the mixing rule Eqs. 610 to predict
refractive indices, the following quantities were analyzed: average absolute deviations
(AAD) and maximal deviation (M Dev),

M 

100 X
npred  nexp 
12
AAD


NDAT i1
nexp


npred  nexp 

MDev 100: max

nexp

13

where npred is the predicted value of the refractive index and nexp is the measured value.
The AAD and M Dev quantities can be also viewed as mean and maximal relative errors.
The values of AADand MDev are shown in Table 7. Average absolute deviations (AAD
values) for all mixtures do not exceed 0.50 %. From the analysis of AAD of the experimental refractive indices using the L-L, G-D, Eyk, Nw or Os equations, the following
sequence was found: water(1) ? methanol(2) ? ethanol(3) [ water(1) ? methanol(2) ?
propan-1-ol(3) * water(1) ? ethanol(2) ? propan-1-ol(3) [ methanol(1) ? ethanol(2) ?
propan1-ol(3). This behavior suggests that the hydrogen bonding interaction effect decreases for alcohol mixtures. The maximal deviation M Dev in all the mixtures is lower
than 0.9 %. The predictions obtained using these mixing rules are very similar. The values
predicted by the Newton mixing rule display better agreement with the experimental values

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of the refractive indices for aqueous mixtures, whereas in the ternary mixture of alcohols
the best prediction is with LorentzLorenz mixing rule.

4 Conclusions
We reported measurements of refractive indices at 293.15 K for six binary mixtures
(water ? methanol, water ? ethanol, water ? propan-1-ol, methanol ? ethanol, methanol ? propan-1-ol, ethanol ? propan-1-ol) and four ternary mixtures (water ?
methanol ? ethanol, water ? methanol ? propan-1-ol, water ? ethanol ? propan-1-ol,
methanol ? ethanol ? propan-1-ol); the refractive index deviations calculated from the
experimental data of refractive indices are appropriately represented with the RedlichKister
equation for binary mixtures and with the Cibulka equation in ternary mixtures. The deviations of refractive indices are higher in aqueous ? alcohol mixtures compared with the
alcohol ? alcohol mixtures.
Mixing rules including the LorentzLorenz, GladstoneDale, Eykman, Newton and
Oster formulas were used for predicting the refractive indices of ternary mixtures. We have
demonstrated that the refractive indices provided by all the mixing rules reproduce the
measured values with a maximal relative error of 0.861 %.

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