Static Permittivity and Refractive Index of Binary Mixtures of 3

Article pubs.acs.org/jced

Static Permittivity and Refractive Index of Binary Mixtures of 3‑Bromoanisole and 1‑Propanol at Different Temperatures Vipinchandra A. Rana,* Hemalkumar P. Vankar, and Hemant A. Chaube Department of Physics, School of Sciences, Gujarat University, Ahmedabad, 380 009, India ABSTRACT: Static permittivity (ε0m) and permittivity at optical frequency (ε∞m) of the binary mixtures of 3-bromoanisole (3-BA) and 1-propanol (1-PrOH) at different concentrations were measured at four different temperatures (303.15 K, 313.15 K, 323.15 K, and 333.15 K). The static permittivity (ε0m) was measured by using precision LCR meter at 2 MHz frequency. The permittivity at optical frequency (ε∞m) was taken as square of refractive index, which was measured using Abbe’s refractometer. The excess dielectric parameters, Kirkwood correlation factors, and Bruggeman factor were evaluated. The excess parameters were fitted to the Redlich−Kister equation. The Kirkwood effective correlation factor of 3-BA is smaller than that of 1-PrOH at all temperatures. The Bruggeman plot shows a deviation from linearity. The determined parameters have been interpreted in terms of molecular interaction between the molecular species of the binary mixtures.

1. INTRODUCTION Dielectric parameters such as the permittivity at optical frequency and the static permittivity of binary mixtures of polar− polar liquids can provide information about molecular interaction among the constituents of the liquid mixture.1 Using these parameters the excess permittivity, Kirkwood correlation factor, and Bruggeman factor can be determined. These parameters can be used to gain information about the orientation of the dipoles in the polar liquids.2 Dielectric properties of pure liquids can be altered continuously by varying the concentration of the components of the mixture, until some desired value is attained, which may find application in many chemical industry and technological processes. Precise experimental dielectric data of the polar liquids in mixed state over a range of concentration and temperature can help to establish correlation equations, which in turn can help to predict the dielectric permittivity value at a given concentration or at a given temperature. Further, such studies as a function of concentration are useful in understanding the intermolecular interactions between the component molecules and provide insight into the structure of the associated molecular complexes. 3-Bromoanisole (3-BA) is a derivative of anisole which is an aromatic compound of the ether group. Its derivatives and anisole itself are used as solvents. They are widely used in chemical reactions as intermediates to obtain target materials like dyes, perfumery, agrochemicals, and pigments.3 The role of L-propanol (1-PrOH) in a chemical reaction is very important because of its associative behavior. It is used as a solvent in the pharmaceutical industry and for resins and cellulose esters. Wide range applications of 3-BA and 1-PrOH in many industrial processes has prompted us to gain extensive information on dielectric properties of these liquids and their binary mixtures. The aim of the present investigation is to gain information about © XXXX American Chemical Society

the modifications of molecular structures and dipolar orientation due to mixing of 3-BA and 1-PrOH over a wide range of concentrations, through dielectric measurements at different temperatures. Many researchers have studied dielectric and physical properties of the binary mixture of aromatic ethers with different polar/nonpolar liquids.3−6 A literature survey suggests that no attempt has been made to study dielectric properties of binary mixtures of 3-BA and 1-PrOH.

2. EXPERIMENTAL SECTION 2.1. Material and Sample Preparation. 3-Bromoanisole with 99 % purity (minimum assay (GC)) was supplied by Spectrochem Pvt. Ltd. (India) and 1-propanol with 99.5 % purity (minimum assay (GC)) was supplied by High Purity Laboratory Chemical Pvt. Ltd. (India). Both compounds were used without any further purification. The solution of 3-BA with 1-PrOH was prepared at 16 different concentrations by mole fraction. 2.2. Experimental Measurement. The static permittivity of pure liquid (ε0) and the binary mixture (ε0m) were measured by using the capacitance measurement method with a short compensation at 2 MHz with a standard uncertainty of 0.04.7 Agilent E 4980A precision LCR meter with a four terminal liquid dielectric test fixture (Agilent 16452A) was used for the capacitance measurement of the cell with and without sample. The measurements were carried out at four different temperatures; 303.15 K, 313.15 K, 323.15 K, and 333.15 K. The temperature was controlled by constant temperature Received: March 18, 2015 Accepted: October 9, 2015

A

DOI: 10.1021/acs.jced.5b00256 J. Chem. Eng. Data XXXX, XXX, XXX−XXX

Journal of Chemical & Engineering Data

Article

⎛ 2 μ b 2 ρb gb ⎞ f 4πN ⎜ μa ρa ga Vb⎟⎟g V + a 9kT ⎜⎝ Ma Mb ⎠

water bath (MIC Fourtech, India) with standard uncertainty of 0.1 K. The refractive index of the sample was determined by using Abbe’s refractometer with a standard uncertainty of 0.001. The permittivity at optical frequency (ε∞) was taken as a square of the refractive index. The densities of 3-BA and 1-PrOH were measured at different temperatures using a pycnometer. The standard uncertainty of density is 3 kg·m−3. A circulating water bath with a constant temperature was used to maintain the temperature with standard uncertainty of 0.1 K for the measurement of refractive index and density.

=

fB = 1 − [h − (h − 1)Vb]Vb

nm 2 − 1 = (na 2 − 1)Va + (nb 2 − 1)Vb

(2)

Kraszewski

The experimental values of the excess parameter were fitted to the Redlich−Kister11 equation as

(3)

rule

⎡1 rmsd = ⎢ ⎣p

(10)

⎤1/2

∑ (nexpt − ncalc)2 ⎥ ⎦

(11)

where, nexpt, ncalc, and p represent the experimental value, calculated value, and total number of concentrations, respectively.

5. RESULTS AND DISCUSSION The experimental values of static permittivity, permittivity at optical frequency and density of the pure 1-PrOH at different temperatures are presented in Table 1. Permittivity at optical frequency and density of 3-BA at 303.15 K are also presented in the same Table. These experimental values are compared with the literature values, which are in good agreement. Data for static permittivity of 3-BA is not available in the literature. Recently Rana and Chaube31 reported static permittivity values of anisole at 303.15 K, 313.15 K, and 323.15 K. Static permittivity of anisole is 4.68 at 303.15 K and that of 3-BA is 7.01 at the same temperature. This indicates that the substitution of the −Br group on the meta position with respect to the −OCH3 group in anisole increases permittivity of the molecule. A similar trend in static permittivity value is observed in the case of aniline and meta-substituted chloro-aniline by Rana et al.32 The static permittivity (ε0m) and permittivity at optical frequency (ε∞m) of 3-BA + 1-PrOH mixtures were determined in the whole concentration range at 303.15 K, 313.15 K, 323.15 K, and 333.15 K temperatures, which are reported in Table 2.

(4)

where μ is dipole moment in the gas phase, ρ is the density at temperature T, M is molecular weight, k is Boltzmann constant, and N is Avogadro number. The dipole moment for 3-BA was taken as 2.05D14 and for 1-PrOH was taken as 1.65D.15 For the mixtures of two polar liquids the effective average Kirkwood correlation factor (geff) of two different molecules is derived from the modified Kirkwood equation.8 The modified Kirkwood equation for the binary mixture is expressed as 2 μ 2ρ ⎞ 4πN ⎛ μa ρa ⎜⎜ Va + b b Vb⎟⎟g eff 9kT ⎝ Ma Mb ⎠

(ε0m − ε∞ m)(2ε0m + ε∞ m) ε0m(ε∞ m + 2)2

(9)

where in eqs 9 and 10, n is the refractive index, ε is the static permittivity, and V is the volume fraction; m, a, and b represent mixture, 3-BA, and 1-PrOH, respectively. The Root mean square deviation (rmsd) values for the above mixing rules are determined by the following equation,21

where Q is either εE0 or εE∞ and j = 0, 1, 2, 3, ···, n. Fisher test12 (F-test) was performed to select the number of coefficients Bj in the Redlich−Kister equation. 3.2. Kirkwood Correlation Parameter. The Kirkwood correlation parameter g also provides information related to the correlation between two molecules in the liquid mixture.13 The g for pure liquid may be given by the expression

=

20

1/2 ε0m = Vaεa1/2 + Vbεb1/2

j

(ε − ε∞)(2ε0 + ε∞) 4πNμ2 ρ g= 0 9kTM ε0(ε∞ + 2)2

(8)

where “h” is the numerical fitting parameter. 3.4. Mixing Rules. The following mixing rules for predicting the refractive index and static permittivity values of the binary mixing were used. Newton (Nw)19 rule

where X is the mole fraction and suffix m, a, b represent mixture, 3-BA, and 1-PrOH, respectively. The excess permittivity at optical frequency (εE∞) was calculated using the relation10

j

(7)

provides another parameter f B, which may be used to investigate liquid mixture interaction. To fit the experimental data eq 7 has been modified18 as

(1)

Q = XaXb ∑ Bj (Xa − Xb)

(6)

⎛ ε − ε0b ⎞⎛ ε0a ⎞1/3 fB = ⎜ 0m ⎟⎜ ⎟ = (1 − Vb) ⎝ ε0a − ε0b ⎠⎝ ε0m ⎠

ε0E = (εom − ε∞ m) − [(ε0a − ε∞ a)Xa + (ε0b − ε∞ b)Xb]

= ε∞ m − (ε∞ aXa + ε∞ bXb)

ε0m(ε∞ m + 2)2

where Va and Vb are the volume fraction of liquid a and liquid b, respectively. In eq 6, the value of geff will change from ga to gb as concentration of molecule b will decrease from 100 % to 0 %. 3.3. Bruggeman Factor. The Bruggeman equation17

3. EVALUATION OF DIFFERENT PARAMETERS 3.1. Excess Parameters. The excess parameters related to ε0 and ε∞ provide valuable information regarding interaction of the polar−polar liquid mixture.8,9 The excess permittivity (εE0 ) is defined as8

ε∞E

(ε0m − ε∞ m)(2ε0m + ε∞ m)

(5)

The corrective correlation factor gf, equally affecting the angular correlation factor of pure liquids a and b is given by16 B



Article

Table 1. Comparison of Static Permittivity, Permittivity at Optical Frequency and Density of Pure Compounds with Literature Data at Pressure p = 0.1 MPaa ε0

ρ/g·cm‑3

ε∞

liquid

T/K

expt

lit

expt

lit

expt

lit

1-PrOH

303.15

19.49

1.9127

1.901616

0.7939

313.15

18.53

19.7822 18.9024 19.3826

1.9044

1.889216

0.7917

323.15

17.59

18.09d,28

1.8934

1.864316

0.7844

333.15 303.15

16.03 7.01

1.8796 2.4336

2.4429b,30

0.7756 1.4676

0.795423 0.796425 0.788627 0.787323 0.781025 0.779029 0.772825 1.477c,30

3-BA

T = temperatures, ε0 = static permittivity, ε∞ = permittivity at optical frequency, ρ = density, 1-PrOH = 1-propanol, 3-BA = 3-bromoanisole. Standard uncertainties u are u(T) = 0.1, u(ε0) = 0.3, u(ε∞) = 0.002, and u(ρ) = 3 kg·m−3. bTemperatures = 293.15 K. cTemperature = 298.15 K. d Temperature = 318.15 K. a

Table 2. Static permittivity (ε0m), permittivity at optical frequency (ε∞m) and Kirkwood effective correlation factor (geff) of 3-BA + 1-PrOH mixtures as function of mole fraction of 1-PrOH at T = 303.15 K to333.15 K and at pressure p = 0.1 MPaa ε0m

ε∞m

geff

Xb

303.15 K

313.15 K

323.15 K

333.15 K

303.15 K

313.15 K

323.15 K

333.15 K

303.15 K

313.15 K

323.15 K

333.15 K

1 0.959 0.916 0.871 0.822 0.771 0.716 0.658 0.596 0.529 0.457 0.38 0.296 0.206 0.107 0

19.49 18.58 17.33 16.23 15.14 13.98 12.93 12.04 11.08 10.27 9.46 8.67 8.05 7.55 7.18 7.01

18.53 17.66 16.62 15.60 14.52 13.42 12.39 11.56 10.61 9.87 9.11 8.39 7.83 7.39 7.03 6.85

17.59 16.7 15.64 14.65 13.63 12.88 11.71 10.94 10.11 9.40 8.68 8.08 7.55 7.15 6.89 6.74

16.03 15.22 14.30 13.33 12.43 11.80 10.89 10.15 9.38 8.74 8.20 7.65 7.23 6.95 6.70 6.60

1.913 1.949 1.988 2.019 2.059 2.094 2.135 2.170 2.202 2.229 2.262 2.301 2.341 2.384 2.418 2.434

1.904 1.938 1.974 2.011 2.042 2.085 2.126 2.155 2.196 2.217 2.253 2.295 2.335 2.372 2.409 2.427

1.893 1.927 1.963 1.997 2.031 2.065 2.100 2.143 2.182 2.214 2.250 2.286 2.320 2.356 2.396 2.412

1.880 1.918 1.954 1.988 2.025 2.059 2.094 2.135 2.173 2.202 2.241 2.274 2.307 2.347 2.390 2.403

3.33 3.12 2.84 2.61 2.38 2.15 1.94 1.76 1.58 1.43 1.29 1.14 1.02 0.92 0.85 0.82

3.18 2.98 2.74 2.52 2.30 2.07 1.86 1.70 1.51 1.38 1.24 1.10 0.99 0.91 0.83 0.80

3.06 2.85 2.61 2.40 2.18 2.02 1.79 1.62 1.46 1.32 1.18 1.06 0.96 0.88 0.83 0.80

2.82 2.62 2.40 2.19 1.99 1.85 1.67 1.51 1.35 1.23 1.11 1.01 0.92 0.86 0.80 0.79

T = temperatures, Xb = mole fraction of 1-propanol, ε0m = static permittivity, ε∞m = permittivity at optical frequency, Standard uncertainties u are u(T) = 0.1, u(Xb) = 0.001, u(ε0) = 0.3, u(ε∞) = 0.002.

a

less than the static permittivity values obtained by molar average of the pure component values. This suggests that in the mixed state of 1-PrOH and 3-BA, hydrogen-bonded structures of 1-PrOH are broken, lowering the static permittivity. In the mid concentration range of 3-BA in the mixture, molecular structures due to the cross-linkage of 1-PrOH and 3-BA molecules are formed, such that the experimental values of static permittivity deviates significantly from the molar average values of the pure components. This results in the transition of parallel aligned molecular aggregates to the antiparallel aggregates that reduce the static permittivity. Behavior of the permittivity at optical frequency of the mixtures as a function of mole fraction of 1-PrOH at different temperatures is shown in Figure 2. From Figure 2 it can be seen that the permittivity at optical frequency of the mixture is higher than that calculated using the additive rule. This clearly suggests that the dipole− dipole interaction between the molecular species of the liquid mixture takes place in such a way that the electronic polarization is enhanced causing an increase in the permittivity at optical frequency. From Figures 1 and 2 it is clear that as the temperature increases the value of the static permittivity, and the dielectric permittivity at optical frequency decreases.

Figure 1. 3D plot of static permittivity versus mole fraction of 1-propanol in 3-bromoanisole and temperature.

As shown in Figure 1, the dependence of the static permittivity on the concentration of 3-BA + 1-PrOH mixtures exhibits a deviation from linearity. Experimental static permittivity of the mixture is C



Article

333.15 K, respectively, at 0.59 mole fraction of 1-PrOH. This indicates that the 3:2 complexation forms the stable adduct. Excess permittivity at optical frequency (εE∞) is positive in the whole concentration range of 1-PrOH. The hydrogen-bond formation between the −OH group of 1-PrOH (proton donor) and −OCH3 group of 3-BA (proton acceptor) alters electronic distribution within the molecules in such a way that the polarization is enhanced. The experimental values of both excess parameters were fitted to the Redlich−Kister equation, and determined values of the coefficient Bj are listed in Table 3. Numbers of coefficients in the Redlich−Kister equation were selected by means of the F-test. With these Bj, QE values were calculated and used to draw smooth curves in Figure 3 and Figure 4. The temperature and concentration dependence of geff and gf for the system is shown in Figure 5 and Figure 6, respectively. Values of the Kirkwood correlation factor g for pure 1-PrOH and 3-BA at 303.15 K are 3.33 and 0.82, respectively, which indicates a high degree of parallel dipole ordering in 1-PrOH and antiparallel dipole ordering in 3-BA. When 3-BA is added into 1-PrOH, the effective value of the Kirkwood correlation factor (geff) of the mixture decreases with the rise in concentration of 3-BA, reaching to a value of 1 at about 0.704 mole fraction of 3-BA at 303.15 K. This suggests that with the addition of 3-BA into 1-PrOH the number of parallel aligned dipoles decrease and, at 0.704 concentration of 3-BA, parallel aligned dipoles are counter-balanced by the antiparallel aligned dipoles. However, when the 3-BA concentration is further increased the geff values become less than 1, indicating the dominance of antiparallel dipole structures over the parallel aligned dipole structures. A similar trend in geff value is observed at all temperatures. Mole concentration of 3-BA at which the geff value of the mixture becomes 1 is found to decrease with a rise in temperature and they are 1.02, 0.99, 0.96, and 0.92 at T = 303.15 K, 313.15 K, 323.15 K, and 333.15 K, respectively. The geff value for all concentrations decreases with increasing temperature, showing the decreasing association with temperature in the mixture system. The value of the correlative Kirkwood correlation factor gf, is one for pure liquid. It deviates from one for the mixture which indicates the presence of interaction between two molecules. The values of gf are less than or equal to unity for all temperatures which is shown in Figure 6. This indicates that the effective dipoles in the mixture are less than the corresponding average value in the pure liquids.2 The modified Bruggeman equation17 also gives information about the interaction between liquid a and liquid b. Figure 7 shows a plot of the Bruggeman factor f B versus volume fraction Vb of 1-PrOH in 3-BA at different temperatures. According to eq 7 the plot of f B versus volume fraction Vb should give a linear relationship, but the experimental values of f B were found to deviate from linearity. Therefore, the experimental data were fitted to the modified Bruggeman eq 8 and the parameter “h” was determined. The value of h = 1 gives the ideal Bruggeman mixture formula. The deviation from 1 suggests molecular interaction between the component molecules. The values of “h” are 0.8141, 0.8176, 0.7324, and 0.6453 at T = 303.15 K, 313.15 K, 323.15 K, and 333.15 K, respectively. For this system the value of “h” are positive with smaller deviation from unity. The values of the numerical fitting parameter “h” are less than 1 at all the temperatures. This indicates that the effective volume of the 1-PrOH and 3-BA decreases on mixing.

Figure 2. 3D plot of permittivity at optical frequency versus mole fraction of 1-propanol in 3-bromoanisole and temperature.

This indicates that the increase in temperature causes a decrease in orientational correlation of the dipoles. Information about the interaction of liquid a and liquid b may be obtained by excess properties9 related to the permittivity of the mixture. The variation of the excess permittivity versus mole fraction (Xb) of 1-PrOH at different temperatures is shown in Figure 3. In the present system, negative values of

Figure 3. Excess static permittivity versus mole fraction of 1-propanol in 3-bromoanisole at different temperatures. Continuous lines are the fitting of Redlich−Kister equation.

the excess permittivity are observed, which indicates that the interaction of the mixture constituents is such that the total effective dipole moment reduces. That means one of the components (3-BA) of the mixture act as a structure breaker for the other component’s (1-PrOH) H-bonded structure with orientation of the neighboring dipoles in opposite direction, that is, antiparallel, and hence there is a decrement in total number of parallel aligned dipoles. This leads to the formation of the multimers with less effective dipole moments. The stoichiometric ratio for complex moiety formation in polar liquid mixtures can be determined from the concentration of largest deviation of εE0 from ideality.10 These values are −3.4, −3.3, −3.2, and −2.9 at T = 303.15 K, 313.15 K, 323.15 K, and D



Article

Table 3. Bj Coefficients and Standard Deviation of the Redlich−Kister Equation for 3-BA + 1-PrOH Mixturesa T/K

B0

B1

B2

B3

B4

σ

−2.2270 −2.9023 −1.0435 −0.3198

6.2472 5.5242 2.0319 0.3440

0.0435 0.0369 0.0613 0.0578

0.4323

0.0026 0.0038 0.0030 0.0017

excess static permittivity 303.15 313.15 323.15 333.15

−13.6067 −12.8633 −12.6135 −11.4905

303.15 313.15 323.15 333.15

0.2888 0.2850 0.3017 0.3144

2.7411 −3.7058 2.7612 −1.8957 2.3739 −0.7709 2.2711 0.0210 excess permittivity at optical frequency −0.1188 0.1942 −0.1056 0.1378 −0.0326 0.0583 −0.0925 −0.1032

0.2654 0.2505 0.1273 0.2207

T = temperatures, B0, B1, B2, B3, B4 = coefficients of Redlich−Kister equation, σ = standard deviation of the Redlich−Kister equation, 3-BA = 3-bromoanisole, 1-PrOH = 1-propanol. Standard uncertainties u is u(T) = 0.1. a

Figure 6. 3D plot of corrective Kirkwood correlation factor versus mole fraction of 1-propanol in 3-bromoanisole and temperature. Figure 4. Excess dielectric permittivity versus mole fraction of 1-propanol in 3-bromoanisole. Continuous lines are the fitting of Redlich−Kister equation.

Figure 5. 3D plot of effective Kirkwood correlation factor versus mole fraction of 1-propanol in 3-bromoanisole and temperature.

Figure 7. Bruggeman factor versus volume fraction of 1-propanol in 3-bromoanisole. Continuous lines are the fitting of the modified Bruggeman equation.

Binary mixtures of polar liquids that have significant difference in molecular size and structures are the subject of interest to many researches. In such binary mixtures, not only are there a variety of molecular interactions among molecular species taking place, but also the dominance of a particular type of interaction changes with concentration. Because of these,

measured values of refractive index and static permittivity of a binary mixture of polar liquids deviate significantly from the values evaluated using molar average values of the pure components. Hence it is essential to verify the mixing rule for predicting refractive index and static permittivity value of a given binary liquid system. E



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Funding

In the present investigation we have tested the Nw mixing rule for refractive index and Kraszewski mixing rule for static permittivity. Our experimental results were compared with the predicted values using these rules at all the four temperatures. The rmsd value for the Nw mixing rule is 0.003, at the four temperatures, and for Kraszewski mixing rule the values are 0.089, 0.094, 0.085, and 0.083 at T = 303.15 K, 313.15 K, 323.15 K, and 333.15 K, respectively. Predicted values of refractive index and static permittivity at 303.15 K using Newton rule and Kraszewski rule are compared with the measured values in Table 4.

Financial support, provided by Department of Sciences and Technology (DST), New Delhi, through the DST-FIST (Level- I) project (SR/FST/PSI-001/2006), and DRS-SAP program Grant [No.F. 530/10/DRS/2010(SAP-I)] have been utilized to carry out this work and is gratefully acknowledged. Notes

The authors declare no competing financial interest.

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ACKNOWLEDGMENTS We thank Prof. P.N. Gajjar, Head, Department of Physics, School of Sciences, Gujarat University, Ahmadabad, for his constant encouragements.

Table 4. Comparison of the Experimental Values of Refractive Index and Static Permittivity with Predicted Values by Nw and Kraszewski Rules at T = 303.15 K and at Pressure p = 0.1 MPaa refractive index

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(1) Cole, R. H.; Berberian, J. G.; Mashimo, S.; Chryssikos, G.; Burns, A.; Tombari, E. Time domain reflection methods for dielectric measurements to 10 GHz. J. Appl. Phys. 1989, 66, 793−802. (2) Balamurugan, D.; Kumar, S.; Krishnan, S. Dielectric relaxation studies of higher order alcohol complexes with amines using time domain reflectometry. J. Mol. Liq. 2005, 122, 11−14. (3) Parthipan, G.; Thenappan, T. Dielectric and thermodynamic behavior of binary mixture of anisole with morpholine and aniline at different temperatures. J. Mol. Liq. 2008, 138, 20−25. (4) Al-Kandary, J. A.; Al-Jimaz, A. S.; Abdul-Latif, A.-H. M. Densities, viscosities, and refractive indices of binary mixtures of anisole with benzene, methylbenzene, ethylbenzene, propylbenzene, and butylbenzene at (293.15 and 303.15) K. J. Chem. Eng. Data 2006, 51, 99−103. (5) Francesconi, R.; Bigi, A.; Comelli, F. Enthalpies of Mixing, Densities, and Refractive Indices for Binary Mixtures of (Anisole or Phenetole)+ Three Aryl Alcohols at 308.15 K and at Atmospheric Pressure. J. Chem. Eng. Data 2005, 50, 1404−1408. (6) Parthipan, G.; Aswathaman, H.; Sankar, U.; Thenappan, T. The dielectric studies of hydrogen-bonded complexes of anisole with alcohols. J. Mol. Liq. 2008, 140, 1−5. (7) 16452A Liquid Test Fixture: Operation and Service Manual, 3rd ed.; Agilent: 2000. (8) Kumbharkhane, A.; Puranik, S.; Mehrotra, S. Dielectric relaxation studies of aqueous N, N-dimethylformamide using a picosecond time domain technique. J. Solution Chem. 1993, 22, 219−229. (9) Tabellout, M.; Lanceleur, P.; Emery, J. R.; Hayward, D.; Pethrick, R. A. Dielectric, ultrasonic and carbon-13 nuclear magnetic resonance relaxation measurements of t-butyl alcohol-water mixtures. J. Chem. Soc., Faraday Trans. 1990, 86, 1493−1501. (10) Sengwa, R.; Sankhla, S. Characterization of heterogeneous interaction in binary mixtures of ethylene glycol oligomer with water, ethyl alcohol and dioxane by dielectric analysis. J. Mol. Liq. 2007, 130, 119−131. (11) Redlich, O.; Kister, A. T. Algebraic Representation of Thermodynamic Properties and the Classification of Solutions. Ind. Eng. Chem. 1948, 40, 345−348. (12) Bevington, P. R.; Robinson, D. K. Data Reduction and Error Analysis for the Physical Sciences; McGraw-Hill: New York, 1992. (13) Kirkwood, J. G. The Dielectric Polarization of Polar Liquids. J. Chem. Phys. 1939, 7, 911−919. (14) Allinger, N. L.; Maul, J. J.; Hickey, S. M. J. Conformational analysis. LXXIV. Phenol and anisole derivatives. J. Org. Chem. 1971, 36, 2747−2752. (15) Weast, R. C. CRC Handbook of Chemistry and Physics; CRC Press: Boca Raton, FL., 1989. (16) Prajapati, A.; Vyas, A.; Rana, V.; Bhatnagar, S. Dielectric relaxation and dispersion studies of mixtures of 1-propanol and benzonitrile in pure liquid state at radio and microwave frequencies. J. Mol. Liq. 2010, 151, 12−16. (17) Bruggeman, D. Dielectric constant and conductivity of mixtures of isotropic materials. Ann. Phys. (Berlin, Ger.) 1935, 416, 636−679.

static permittivity

Vb

nexpt

Nw

εexpt 0

Kraszewski

1 0.933 0.867 0.800 0.733 0.667 0.600 0.533 0.467 0.400 0.333 0.267 0.200 0.133 0.067 0

1.383 1.396 1.410 1.421 1.435 1.447 1.461 1.473 1.484 1.493 1.504 1.517 1.530 1.544 1.555 1.560

1.383 1.396 1.408 1.420 1.432 1.444 1.456 1.468 1.480 1.492 1.503 1.515 1.526 1.538 1.549 1.560

19.49 18.58 17.33 16.23 15.14 13.98 12.93 12.04 11.08 10.27 9.46 8.67 8.05 7.55 7.18 7.01

19.493 18.466 17.465 16.497 15.553 14.637 13.751 12.889 12.056 11.254 10.479 9.729 9.008 8.313 7.649 7.011

a

T = temperature, Vb = volume fraction of 1-propanol, nexpt = experimental values of refractive index, Nw = Newton,ε0expt = experimental values of static permittivity. Standard uncertainties u are u(T) = 0.1, u(Vb) = 0.002, u(nexpt) = 0.001.

6. CONCLUSION Sixteen different concentrations of binary mixtures of 3-BA + 1-PrOH were prepared and dielectric measurements were carried out for all prepared samples at four different temperatures. The dielectric parameters namely static permittivity, permittivity at optical frequency, Kirkwood correlation parameters, and Bruggeman parameters were calculated and reported. Excess static permittivity and excess permittivity at optical frequency have been calculated and fitted to the Redlich−Kister equation. The values of excess static permittivity and excess permittivity at optical frequency are negative and positive, respectively, over the entire composition range. 3-BA in the mixture of 3-BA + 1-PrOH acts as structure breaker in the H-bonded molecular structure of 1-PrOH. Furthermore, we have calculated refractive index and static permittivity by using mixing rules such as Nw for refractive index and Kraszewski for static permittivity. Nw and Kraszewski shows good agreement with the experimental values of refractive index and static permittivity, respectively.

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Static Permittivity and Refractive Index of Binary Mixtures of 3

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