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Experimental studies on volumetric and viscometric properties of binary and ternary mixtures of N,N-dimethylacetamide, N-methylformamide and propane-1,2-diol at different temperatures
Journal of Molecular Liquids 187 (2013) 260–265
Contents lists available at ScienceDirect
Journal of Molecular Liquids journal homepage: www.elsevier.com/locate/molliq
Experimental studies on volumetric and viscometric properties of binary and ternary mixtures of N,N-dimethylacetamide, N-methylformamide and propane-1,2-diol at different temperatures Hosseinali Zarei ⁎, Sajad Akbari Golroudbari, Mahboobe Behroozi Faculty of Chemistry, Bu-Ali Sina University, Hamedan, Iran
a r t i c l e
i n f o
Article history: Received 26 February 2013 Received in revised form 2 July 2013 Accepted 4 July 2013 Available online 19 July 2013 Keywords: Excess molar volumes Viscosity Amides Propane-1,2-diol
a b s t r a c t E Excess molar volumes Vm , and viscosity η, of the ternary mixture of N,N-dimethylacetamide (1) + Nmethylformamide (2) + propane-1,2-diol (3) and their binary mixtures were obtained from density ρ, and viscosity η, measurements over the entire mole fraction range at temperatures (293.15 to 333.15) K. Negative trend were observed for the VEm values of the binary mixtures in the whole composition range except for N-methylformamide (2) + propane-1,2-diol (3) mixture in the N-methylformamide rich region. Also, negative VEm values were observed for the ternary mixture except a few mole fractions in accordance with their binary mixtures. Effect of rising temperature on the trend of the VEm values is not the same for the mixtures. The viscosity values of the mixtures over the entire mole fraction range decrease with increasing temperature. The results were interpreted based on the strength of specific interaction, size and shape of molecules. The experimental data of excess molar volumes were correlated with the Redlich–Kister and the Cibulka equations for the binary and ternary mixtures, respectively. © 2013 Elsevier B.V. All rights reserved.
1. Introduction Studies on thermodynamic and transport properties of binary and ternary mixtures containing amides and alkanediols are of great importance due to their application in many industrial processes as well as theoretical understanding of the nature of molecular interactions. Amides are the most common solvents used in chemical reactions and in many industrial processes. Moreover, amides are convenient model mixtures for the investigation of peptide and protein interactions in biological mixtures [1–3]. Alkanediols are very important compounds due to widespread practical applications in industry such as antifreezes, coolants, aircraft deicing fluids, cosmetic, pharmaceutical, food, automotive industries and so on[4,5]. Among the thermodynamic and transport properties, excess properties are good candidates in order to obtain insight into the nature of molecular interactions. The deviation from ideal solution behavior is expressed by means of excess function. Also, the study of these properties is very important due to their industrial applications [6–8]. Although many studies have been reported for the excess properties of binary mixtures in the literature but those for ternary mixtures are still rare.
⁎ Corresponding author. Tel.: +98 811 8282807; fax: +98 811 8257407. E-mail address: [email protected] (H. Zarei). 0167-7322/$ – see front matter © 2013 Elsevier B.V. All rights reserved. http://dx.doi.org/10.1016/j.molliq.2013.07.002
In this work, density ρ, excess molar volume VEm, and viscosity η, of the ternary mixture of N,N-dimethylacetamide (DMA) + Nmethylformamide (NMF) + propane-1,2-diol and their binary mixtures have been reported in an entire range of compositions at temperatures (293.15 to 333.15) K and atmospheric pressure. The experimental VEm were correlated with the Redlich–Kister[9] and the Cibulka [10] equations for the binary and ternary mixtures respectively. 2. Experimental 2.1. Materials The chemicals were as follows: DMA and propane-1,2-diol were purchased from Merck and NMF was prepared from Fluka. Prior to the experimental measurements, the chemicals were degassed with a bath ultrasonic cleaner. The purity grade, density ρ, and viscosity η, of the pure components are given in table 1. The purities declared by the manufacturer were ascertained by comparing their densities and viscosities with literature values [1–3,11–17] at different temperatures. 2.2. Apparatus and procedure The mixtures were prepared by mass, using a Mettler AB 204-N balance precise to ± 0.1 mg. The average uncertainty in the mole fraction was estimated to be ±1.1 · 10−5. The density measurements
H. Zarei et al. / Journal of Molecular Liquids 187 (2013) 260–265 Table 1 Purity grades, densities ρ, and viscosities η, of the pure components with their literature values at different temperatures. Component
Purity
T/K
100 w N,N-dimethylacetamide 99
N-methylformamide
1,2-propanediol
a b c d e f g h i j
99
99.5
293.15 298.15 303.15 313.15 323.15 333.15 293.15 298.15 303.15 313.15 323.15 333.15 293.15 298.15 303.15 313.15 323.15 333.15
ρ ⋅ 10−3/kg ⋅ m−3
η/mPa ⋅ s
Exp.
Exp.
0.94102 0.93641 0.93179 0.92255 0.91327 0.90396 1.00318 0.99883 0.99448 0.98577 0.97704 0.96830 1.03628 1.03262 1.02891 1.02138 1.01369 1.00584
Lit. a
0.9410 0.9364b 0.9320a 0.9231a
0.9988c 0.9948d 0.9861d
1.03630e 1.0327f 1.028939g 1.021399g 1.01370e 1.00586h
1.034 0.967 0.856 0.779 0.723 0.655 1.912 1.754 1.612 1.381 1.203 1.056 56.956 44.201 33.259 19.765 12.631 8.449
261
(b)
Lit. 0.947i 0.838j 0.766j
1.76c
56.21e 33.902g 19.47g 12.79e
Reference [2]. Reference [1]. Reference [11]. Reference [3]. Reference [12]. Reference [13]. Reference [14]. Reference [15]. Reference [16]. Reference [17].
(a)
Fig. 1. (b). Viscosity η, of {N,N-dimethylacetamide (1) + N-methylformamide (2)} mixture at different temperatures: ▲, 293.15 K; ▿, 303.15 K; ■, 313.15 K; ⋄, 323.15 K, ×, 333.15 K.
of the pure components and their binary and ternary mixtures were performed by an Anton Paar DMA 4500 oscillating u-tube densimeter, provided with automatic viscosity correction. The temperature in the cell was regulated to ± 0.01 K with a solid state thermostat. The uncertainty of the density measurements was ± 1 ⋅ 10‐ 2 kg ⋅ m‐ 3. An Ubbelohde viscometer was applied to viscosity measurements. Standard materials were used for calibration of the viscometer at the working temperatures. Flow time measurements were performed by an electronic digital stop watch with readability of ±0.01 s. At least three sets of readings for the flow times were taken for each data, and the results were averaged. 3. Results and discussions 3.1. Volumetric studies E , of the ternary mixture of DMA The excess molar volumes Vm (1) + NMF (2) + propane-1,2-diol (3) and their binary mixtures were calculated from density ρ, measurements over the temperature range (293.15 to 333.15) K by the following equation:
E
Vm ¼
n X
−1 −1 xi Mi ρ −ρi
ð1Þ
i¼1
E Fig. 1. (a). Excess molar volumes Vm , of {N,N-dimethylacetamide (1) + N-methylformamide (2)} mixture at different temperatures: ▲, 293.15 K; ▿, 303.15 K; ■, 313.15 K; ⋄, 323.15 K, ×, 333.15 K. Solid curves represent the values calculated from Redlich–Kister equation.
where Mi and ρi are the molecular mass and density of the pure components, respectively; ρ is the density of mixture; and n is the number of components. The obtained values are reported in tables S1 and S2 as Supplementary data. Graphical representation of the binary mixtures is given in Figs. 1–3(a) and the ternary mixture is given in Fig. 4.
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H. Zarei et al. / Journal of Molecular Liquids 187 (2013) 260–265
(a)
interstitial accommodation of smaller molecules into the voids present in larger molecules is possible. The effect of the rising temperature is not the same for the binary E for DMA (1) + NMF (2) and NMF (2) + mixtures. The trend of Vm propane-1,2-diol (3) binary mixtures become more negative with increasing temperature. It can be related to more desirable fitting of smaller NMF molecules into the vacant spaces in bigger DMA or E values with increasing propane-1,2-diol molecules. The rising Vm temperature for DMA (1) + propane-1,2-diol (3) mixture may be due to the disruption of molecular association between the unlike molecules. The excess molar volumes of ternary mixture of N,N-dimethylacetamide (1) + N-methylformamide (2) + propane-1,2-diol (3) are negative except a few mole fractions in the NMF rich region and become more negative with rising temperature. In the propane-1,2-diol rich reE values become less negative with increase in temperature gion, the Vm E for the ternary mixture is similar to its binary (Fig. 4). The trend of Vm mixtures. 3.2. Viscometric studies The viscosities η, of the binary and ternary mixtures of DMA (1) + NMF (2) + propane-1,2-diol (3) were determined according to Eq. (2). η ¼ ρν ¼ ρðkt−c=t Þ
ð2Þ
where k and c are the viscometer constant, determined by calibration and t, ρ, η and ν are the efflux time, density, dynamic and kinematic viscosities, respectively. Fig. 2. (a). Excess molar volumes VEm, of {N,N-dimethylacetamide (1) + 1,2-propanediol (3)} mixture at different temperatures: ▲, 293.15 K; ▿, 303.15 K; ■, 313.15 K; ⋄, 323.15 K, ×, 333.15 K. Solid curves represent the values calculated from Redlich– Kister equation.
The average uncertainty in the excess molar volumes are estimated to be ±3 · 10−9 m3·mol−1. E values of the binary mixture of As can be seen from Fig. 1(a), the Vm DMA(1) + NMF(2) are negative with a minimum around x1 ≈ 0.75 and become more negative with increasing temperature over the entire range of compositions at temperatures (293.15 to 333.15) K. For the DMA (1) + propane-1,2-diol (3) mixture, the VEm values are negative with a minimum around x1 ≈ 0.7 and become less negative with increasing temperature except at temperature 313.15 K. At this temperature, two local minima and one maximum were observed (Fig. 2(a)). In the case of the binary mixture of NMF (2) + propane-1,2-diol (3), negE values were observed except a few mole fractions in the NMF ative Vm E values become more negarich region. With rising temperature, the Vm tive (Fig. 3(a)). E values indicate that the mixing process leads to a conNegative Vm traction in volume. DMA molecules are highly polar and unassociated [2,18] while the molecules of NMF are highly polar and self-associated through N\H⋯O_C hydrogen bonds [3] in pure states. Propane-1, 2-diol molecules are polar and self-associated through inter- and intra-hydrogen bonding[19]. The following process may happen by mixing DMA, NMF and propane-1,2-diol with each other, resulting in E values. Hydrogen bonds in NMF or propane-1,2-diol molenegative Vm cules are broken and the dipolar order in NMF and DMA is disrupted. By addition of the NMF in DMA, proton donor–acceptor interaction or a new H-bonded molecular complex is formed between oxygen atom of –CO group of DMA and hydrogen atom of the amino group of NMF. Similarly, during the mixing of DMA or NMF with propane-1,2-diol, hydrogen bonds between the –CO group of the amines and OH groups of the diol are the main interactions in these mixtures. In addition,
(b)
Fig. 2. (b). Viscosity η, of {N,N-dimethylacetamide (1) + 1,2-propanediol (3)} mixture at different temperatures: ▲, 293.15 K; ▿, 303.15 K; ■, 313.15 K; ⋄, 323.15 K, ×, 333.15 K.
H. Zarei et al. / Journal of Molecular Liquids 187 (2013) 260–265
(a)
263
The Apq parameters for the three binary mixtures are listed in Table 2 together with the standard deviations σ, evaluated by the Eq. (5).
σ ðΔQ Þ ¼
!1=2 n 2 X Q m;i −Q mcalcd;i =ðn−kÞ
ð5Þ
i¼1
where n is the number of experimental data points and k is the number of parameters. The excess molar volumes for the ternary mixture were correlated with the temperature-dependent Cibulka equation [10] ΔQ ¼ ΔQ 12 þ ΔQ 13 þ ΔQ 23 þ x1 x2 x3 ðB0 þ B1 x1 þ B2 x2 Þ
ð6Þ
where ΔQij are the contributions of binary mixture i,j. The Bp ternary parameters are function of temperature by Eq. (4). The temperatureindependent parameters Apq, for the ternary mixture were reported in Table 2 together with the standard deviations σ. 4. Conclusion
E Fig. 3. (a). Excess molar volumes Vm , of {N-methylformamide (2) + 1,2-propanediol (3)} mixture at different temperatures: ▲, 293.15 K; ▿, 303.15 K; ■, 313.15 K; ⋄, 323.15 K, ×, 333.15 K. Solid curves represent the values calculated from Redlich– Kister equation.
Density ρ, and viscosity η, measurements of N,N-dimethylacetamide (1) + N-methylformamide (2) + propane-1,2-diol (3) ternary mixture and their binary mixtures were performed over the entire mole E and η were fraction range at different temperatures. The values of Vm obtained from the measurements. Negative trend were observed for E values of the binary mixtures in the whole composition range the Vm except for NMF (2) + propane-1,2-diol (3) mixture in the NMF rich region. Also, negative VEm values were observed for the ternary mixture except a few mole fractions in accordance with their binary E values mixtures. Effect of rising temperature on the trend of the Vm
(b)
Density ρ, and efflux time, measurements of the binary and ternary mixtures were applied to calculate viscosity η, over the complete mole fraction range at different temperatures. The average uncertainty in the viscosity measurements was ± 2 · 10−3 mPa·s. The results for the binary mixtures were reported in table S3 as Supplementary data and represented in Figs. 1–3(b). The viscosities of N,N-dimethylacetamide (1) + N-methylformamide (2) + propane-1,2-diol (3) ternary mixture were reported in table S4 as Supplementary data and shown in Fig. 5. The viscosity of the binary and ternary mixture becomes less with increasing temperatures. Negative E and the η values can be deduced that the size and shape of values of Vm molecules are influenced on the η values in addition to the strength of specific interaction [14]. Redlich–Kister expression [9] was applied in order to correlate the obtained excess molar volumes of the binary mixtures as following:
ΔQ ¼ xi x j
n X
p Bp xi −x j
ð3Þ
p¼0
where ΔQ refers to VEm for the binary mixtures; xi and xj are the mole fraction; Bp is the fitting parameter obtained by the un-weighted least-squares method and n is the degree of the polynomial expansion. Temperature dependence of Bp parameter can be expressed as follows:
Bp ¼
2 X q¼0
q
Apq T :
ð4Þ
Fig. 3. (b). Viscosity η, of {N-methylformamide (2) + 1,2-propanediol (3)} mixture at different temperatures: ▲, 293.15 K; ▿, 303.15 K; ■, 313.15 K; ⋄, 323.15 K, ×, 333.15 K.
264
H. Zarei et al. / Journal of Molecular Liquids 187 (2013) 260–265
E Fig. 4. Excess molar volumes Vm , surface of ternary mixture of {N,N-dimethylacetamide (1) + N-methylformamide (2) + 1,2-propanediol (3)} at 293.15 K. mental points. Curves represent the values calculated from Cibulka equation. The unit in the triangle plot is mole fraction.
is not the same for the mixtures. Different behaviors were observed E for the mixtures with increasing temperature but for the trend of Vm those for η values were regular. The η values decrease with increase in temperature of the mixtures. The results explained based on the
, represent experi-
strength of specific interactions, size and shape of molecules. The experimental data of excess molar volumes were correlated with Redlich–Kister and the Cibulka equations for the binary and ternary mixtures respectively.
Fig. 5. Viscosity η, surface of ternary mixture of {N,N-dimethylacetamide (1) + N-methylformamide (2) + 1,2-propanediol (3)} at 293.15 K. unit in the triangle plot is mole fraction.
, represent experimental points. The
H. Zarei et al. / Journal of Molecular Liquids 187 (2013) 260–265 Table 2 Correlation coefficients of Redlich–Kister and the Cibulka equations Apq, according to Eqs. (3), (4) and (6), together their standard deviations for the fits of excess molar volumes VEm ⋅ 106(kg ⋅ m−3), of binary and ternary mixtures in the temperature range (293.15 to 333.15) K. q
p 0
1
σ/(cm3 · mol−1)
2
{N,N-dimethylacetamide (1) + N-methylformamide (2)} 0 −1.51831 0.0106464 −1.9702 × 10−5 1 0.912985 −0.0064388 8.9717 × 10−6 2 −2.17687 0.0138508 −2.33415 × 10−5 {N,N-dimethylacetamide 0 −4.13522 1 1.26368 2 2.2819 3 1.02168
(1) + 1,2-propanediol (3)} 0.0207395 2.56949 −0.0056214 −1.99906 −0.0158326 2.43282 −0.0070491 1.40289
× × × ×
10−5 10−6 10−5 10−5
{N-methylformamide (2) + 1,2-propanediol (3)} 0 −3.54952 0.0234832 −4.01002 × 10−5 1 −1.95668 0.0141632 2.31253 × 10−5 2 −2.26881 0.014029 −2.22936 × 10−5
0.002
0.002
0.002
{N,N-dimethylacetamide (1) + N-methylformamide (2) + 1,2-propanediol (3)} 0 49.1533 −0.322224 4.95127 × 10−4 0.013 1 −187.03 1.23595 −0.0019842 2 103.221 −0.662585 0.00110532
Acknowledgment The authors would like to thank Bu-Ali Sina University for providing the necessary facilities to carry out the research.
265
Appendix A. Supplementary data Supplementary data to this article can be found online at http:// dx.doi.org/10.1016/j.molliq.2013.07.002. References [1] F. Chen, J. Wu, Z. Wang, Journal of Molecular Liquids 140 (2008) 6–9. [2] A.K. Nain, Journal of Chemical Thermodynamics 38 (2006) 1362–1370. [3] A. Nikolic, L. Gobor, V. Despotovic, S. Majkic, Journal of Molecular Liquids 126 (2006) 95–98. [4] R.F. Checoni, Journal of Chemical Thermodynamics 42 (2010) 612–620. [5] S.K. Mehta, G. Ram, C. Mani, K.K. Bhasin, Journal of Chemical Thermodynamics 38 (2006) 836–848. [6] K.J. Han, J.H. Oh, S.J. Park, J. Gmehling, J. Chem, Engineering Data 50 (2005) 1951–1955. [7] A. Ali, M. Tariq, Journal of Molecular Liquids 128 (2006) 50–55. [8] M.V. Rathnam, R.K. Singh, M.S. Kumar, J. Chem, Engineering Data 53 (2008) 265–270. [9] O. Redlich, A.T. Kister, Industrial and Engineering Chemistry 40 (1948) 345–348. [10] I. Cibulka, Collection of Czechoslovak Chemical Communications 47 (1982) 1414–1419. [11] B. Garcia, R. Alcalde, J.M. Lealand, J.L. Trenzado, Journal of Physical Organic Chemistry 10 (1997) 138–144. [12] J. Basiri-Parsa, M. Farshbaf-Haghro, Journal of Chemical Thermodynamics 40 (2008) 782–788. [13] A. Pal, S. Sharma, Y.P. Singh, Journal of Chemical and Engineering Data 42 (1997) 1157–1160. [14] U.R. Kapadi, D.G. Hundiwale, N.B. Patil, M.K. Lande, P.R. Patil, Fluid Phase Equilibria 192 (2001) 63–70. [15] H.A. Zarei, F. Jalili, Journal of Chemical Thermodynamics 39 (2007) 55–66. [16] A. Pal, J. Chem, Engineering Data 47 (2002) 1128–1134. [17] J. Riddick, W.B. Bunger, Organic Solvents, 3th ed. Wiley-interscience, New York, 1970. [18] R.K. Bhardwaja, A. Pal, Journal of Molecular Liquids 118 (2005) 37–39. [19] A.K. Nain, Journal of Chemical Thermodynamics 39 (2007) 462–473.
Contents lists available at ScienceDirect
Journal of Molecular Liquids journal homepage: www.elsevier.com/locate/molliq
Experimental studies on volumetric and viscometric properties of binary and ternary mixtures of N,N-dimethylacetamide, N-methylformamide and propane-1,2-diol at different temperatures Hosseinali Zarei ⁎, Sajad Akbari Golroudbari, Mahboobe Behroozi Faculty of Chemistry, Bu-Ali Sina University, Hamedan, Iran
a r t i c l e
i n f o
Article history: Received 26 February 2013 Received in revised form 2 July 2013 Accepted 4 July 2013 Available online 19 July 2013 Keywords: Excess molar volumes Viscosity Amides Propane-1,2-diol
a b s t r a c t E Excess molar volumes Vm , and viscosity η, of the ternary mixture of N,N-dimethylacetamide (1) + Nmethylformamide (2) + propane-1,2-diol (3) and their binary mixtures were obtained from density ρ, and viscosity η, measurements over the entire mole fraction range at temperatures (293.15 to 333.15) K. Negative trend were observed for the VEm values of the binary mixtures in the whole composition range except for N-methylformamide (2) + propane-1,2-diol (3) mixture in the N-methylformamide rich region. Also, negative VEm values were observed for the ternary mixture except a few mole fractions in accordance with their binary mixtures. Effect of rising temperature on the trend of the VEm values is not the same for the mixtures. The viscosity values of the mixtures over the entire mole fraction range decrease with increasing temperature. The results were interpreted based on the strength of specific interaction, size and shape of molecules. The experimental data of excess molar volumes were correlated with the Redlich–Kister and the Cibulka equations for the binary and ternary mixtures, respectively. © 2013 Elsevier B.V. All rights reserved.
1. Introduction Studies on thermodynamic and transport properties of binary and ternary mixtures containing amides and alkanediols are of great importance due to their application in many industrial processes as well as theoretical understanding of the nature of molecular interactions. Amides are the most common solvents used in chemical reactions and in many industrial processes. Moreover, amides are convenient model mixtures for the investigation of peptide and protein interactions in biological mixtures [1–3]. Alkanediols are very important compounds due to widespread practical applications in industry such as antifreezes, coolants, aircraft deicing fluids, cosmetic, pharmaceutical, food, automotive industries and so on[4,5]. Among the thermodynamic and transport properties, excess properties are good candidates in order to obtain insight into the nature of molecular interactions. The deviation from ideal solution behavior is expressed by means of excess function. Also, the study of these properties is very important due to their industrial applications [6–8]. Although many studies have been reported for the excess properties of binary mixtures in the literature but those for ternary mixtures are still rare.
⁎ Corresponding author. Tel.: +98 811 8282807; fax: +98 811 8257407. E-mail address: [email protected] (H. Zarei). 0167-7322/$ – see front matter © 2013 Elsevier B.V. All rights reserved. http://dx.doi.org/10.1016/j.molliq.2013.07.002
In this work, density ρ, excess molar volume VEm, and viscosity η, of the ternary mixture of N,N-dimethylacetamide (DMA) + Nmethylformamide (NMF) + propane-1,2-diol and their binary mixtures have been reported in an entire range of compositions at temperatures (293.15 to 333.15) K and atmospheric pressure. The experimental VEm were correlated with the Redlich–Kister[9] and the Cibulka [10] equations for the binary and ternary mixtures respectively. 2. Experimental 2.1. Materials The chemicals were as follows: DMA and propane-1,2-diol were purchased from Merck and NMF was prepared from Fluka. Prior to the experimental measurements, the chemicals were degassed with a bath ultrasonic cleaner. The purity grade, density ρ, and viscosity η, of the pure components are given in table 1. The purities declared by the manufacturer were ascertained by comparing their densities and viscosities with literature values [1–3,11–17] at different temperatures. 2.2. Apparatus and procedure The mixtures were prepared by mass, using a Mettler AB 204-N balance precise to ± 0.1 mg. The average uncertainty in the mole fraction was estimated to be ±1.1 · 10−5. The density measurements
H. Zarei et al. / Journal of Molecular Liquids 187 (2013) 260–265 Table 1 Purity grades, densities ρ, and viscosities η, of the pure components with their literature values at different temperatures. Component
Purity
T/K
100 w N,N-dimethylacetamide 99
N-methylformamide
1,2-propanediol
a b c d e f g h i j
99
99.5
293.15 298.15 303.15 313.15 323.15 333.15 293.15 298.15 303.15 313.15 323.15 333.15 293.15 298.15 303.15 313.15 323.15 333.15
ρ ⋅ 10−3/kg ⋅ m−3
η/mPa ⋅ s
Exp.
Exp.
0.94102 0.93641 0.93179 0.92255 0.91327 0.90396 1.00318 0.99883 0.99448 0.98577 0.97704 0.96830 1.03628 1.03262 1.02891 1.02138 1.01369 1.00584
Lit. a
0.9410 0.9364b 0.9320a 0.9231a
0.9988c 0.9948d 0.9861d
1.03630e 1.0327f 1.028939g 1.021399g 1.01370e 1.00586h
1.034 0.967 0.856 0.779 0.723 0.655 1.912 1.754 1.612 1.381 1.203 1.056 56.956 44.201 33.259 19.765 12.631 8.449
261
(b)
Lit. 0.947i 0.838j 0.766j
1.76c
56.21e 33.902g 19.47g 12.79e
Reference [2]. Reference [1]. Reference [11]. Reference [3]. Reference [12]. Reference [13]. Reference [14]. Reference [15]. Reference [16]. Reference [17].
(a)
Fig. 1. (b). Viscosity η, of {N,N-dimethylacetamide (1) + N-methylformamide (2)} mixture at different temperatures: ▲, 293.15 K; ▿, 303.15 K; ■, 313.15 K; ⋄, 323.15 K, ×, 333.15 K.
of the pure components and their binary and ternary mixtures were performed by an Anton Paar DMA 4500 oscillating u-tube densimeter, provided with automatic viscosity correction. The temperature in the cell was regulated to ± 0.01 K with a solid state thermostat. The uncertainty of the density measurements was ± 1 ⋅ 10‐ 2 kg ⋅ m‐ 3. An Ubbelohde viscometer was applied to viscosity measurements. Standard materials were used for calibration of the viscometer at the working temperatures. Flow time measurements were performed by an electronic digital stop watch with readability of ±0.01 s. At least three sets of readings for the flow times were taken for each data, and the results were averaged. 3. Results and discussions 3.1. Volumetric studies E , of the ternary mixture of DMA The excess molar volumes Vm (1) + NMF (2) + propane-1,2-diol (3) and their binary mixtures were calculated from density ρ, measurements over the temperature range (293.15 to 333.15) K by the following equation:
E
Vm ¼
n X
−1 −1 xi Mi ρ −ρi
ð1Þ
i¼1
E Fig. 1. (a). Excess molar volumes Vm , of {N,N-dimethylacetamide (1) + N-methylformamide (2)} mixture at different temperatures: ▲, 293.15 K; ▿, 303.15 K; ■, 313.15 K; ⋄, 323.15 K, ×, 333.15 K. Solid curves represent the values calculated from Redlich–Kister equation.
where Mi and ρi are the molecular mass and density of the pure components, respectively; ρ is the density of mixture; and n is the number of components. The obtained values are reported in tables S1 and S2 as Supplementary data. Graphical representation of the binary mixtures is given in Figs. 1–3(a) and the ternary mixture is given in Fig. 4.
262
H. Zarei et al. / Journal of Molecular Liquids 187 (2013) 260–265
(a)
interstitial accommodation of smaller molecules into the voids present in larger molecules is possible. The effect of the rising temperature is not the same for the binary E for DMA (1) + NMF (2) and NMF (2) + mixtures. The trend of Vm propane-1,2-diol (3) binary mixtures become more negative with increasing temperature. It can be related to more desirable fitting of smaller NMF molecules into the vacant spaces in bigger DMA or E values with increasing propane-1,2-diol molecules. The rising Vm temperature for DMA (1) + propane-1,2-diol (3) mixture may be due to the disruption of molecular association between the unlike molecules. The excess molar volumes of ternary mixture of N,N-dimethylacetamide (1) + N-methylformamide (2) + propane-1,2-diol (3) are negative except a few mole fractions in the NMF rich region and become more negative with rising temperature. In the propane-1,2-diol rich reE values become less negative with increase in temperature gion, the Vm E for the ternary mixture is similar to its binary (Fig. 4). The trend of Vm mixtures. 3.2. Viscometric studies The viscosities η, of the binary and ternary mixtures of DMA (1) + NMF (2) + propane-1,2-diol (3) were determined according to Eq. (2). η ¼ ρν ¼ ρðkt−c=t Þ
ð2Þ
where k and c are the viscometer constant, determined by calibration and t, ρ, η and ν are the efflux time, density, dynamic and kinematic viscosities, respectively. Fig. 2. (a). Excess molar volumes VEm, of {N,N-dimethylacetamide (1) + 1,2-propanediol (3)} mixture at different temperatures: ▲, 293.15 K; ▿, 303.15 K; ■, 313.15 K; ⋄, 323.15 K, ×, 333.15 K. Solid curves represent the values calculated from Redlich– Kister equation.
The average uncertainty in the excess molar volumes are estimated to be ±3 · 10−9 m3·mol−1. E values of the binary mixture of As can be seen from Fig. 1(a), the Vm DMA(1) + NMF(2) are negative with a minimum around x1 ≈ 0.75 and become more negative with increasing temperature over the entire range of compositions at temperatures (293.15 to 333.15) K. For the DMA (1) + propane-1,2-diol (3) mixture, the VEm values are negative with a minimum around x1 ≈ 0.7 and become less negative with increasing temperature except at temperature 313.15 K. At this temperature, two local minima and one maximum were observed (Fig. 2(a)). In the case of the binary mixture of NMF (2) + propane-1,2-diol (3), negE values were observed except a few mole fractions in the NMF ative Vm E values become more negarich region. With rising temperature, the Vm tive (Fig. 3(a)). E values indicate that the mixing process leads to a conNegative Vm traction in volume. DMA molecules are highly polar and unassociated [2,18] while the molecules of NMF are highly polar and self-associated through N\H⋯O_C hydrogen bonds [3] in pure states. Propane-1, 2-diol molecules are polar and self-associated through inter- and intra-hydrogen bonding[19]. The following process may happen by mixing DMA, NMF and propane-1,2-diol with each other, resulting in E values. Hydrogen bonds in NMF or propane-1,2-diol molenegative Vm cules are broken and the dipolar order in NMF and DMA is disrupted. By addition of the NMF in DMA, proton donor–acceptor interaction or a new H-bonded molecular complex is formed between oxygen atom of –CO group of DMA and hydrogen atom of the amino group of NMF. Similarly, during the mixing of DMA or NMF with propane-1,2-diol, hydrogen bonds between the –CO group of the amines and OH groups of the diol are the main interactions in these mixtures. In addition,
(b)
Fig. 2. (b). Viscosity η, of {N,N-dimethylacetamide (1) + 1,2-propanediol (3)} mixture at different temperatures: ▲, 293.15 K; ▿, 303.15 K; ■, 313.15 K; ⋄, 323.15 K, ×, 333.15 K.
H. Zarei et al. / Journal of Molecular Liquids 187 (2013) 260–265
(a)
263
The Apq parameters for the three binary mixtures are listed in Table 2 together with the standard deviations σ, evaluated by the Eq. (5).
σ ðΔQ Þ ¼
!1=2 n 2 X Q m;i −Q mcalcd;i =ðn−kÞ
ð5Þ
i¼1
where n is the number of experimental data points and k is the number of parameters. The excess molar volumes for the ternary mixture were correlated with the temperature-dependent Cibulka equation [10] ΔQ ¼ ΔQ 12 þ ΔQ 13 þ ΔQ 23 þ x1 x2 x3 ðB0 þ B1 x1 þ B2 x2 Þ
ð6Þ
where ΔQij are the contributions of binary mixture i,j. The Bp ternary parameters are function of temperature by Eq. (4). The temperatureindependent parameters Apq, for the ternary mixture were reported in Table 2 together with the standard deviations σ. 4. Conclusion
E Fig. 3. (a). Excess molar volumes Vm , of {N-methylformamide (2) + 1,2-propanediol (3)} mixture at different temperatures: ▲, 293.15 K; ▿, 303.15 K; ■, 313.15 K; ⋄, 323.15 K, ×, 333.15 K. Solid curves represent the values calculated from Redlich– Kister equation.
Density ρ, and viscosity η, measurements of N,N-dimethylacetamide (1) + N-methylformamide (2) + propane-1,2-diol (3) ternary mixture and their binary mixtures were performed over the entire mole E and η were fraction range at different temperatures. The values of Vm obtained from the measurements. Negative trend were observed for E values of the binary mixtures in the whole composition range the Vm except for NMF (2) + propane-1,2-diol (3) mixture in the NMF rich region. Also, negative VEm values were observed for the ternary mixture except a few mole fractions in accordance with their binary E values mixtures. Effect of rising temperature on the trend of the Vm
(b)
Density ρ, and efflux time, measurements of the binary and ternary mixtures were applied to calculate viscosity η, over the complete mole fraction range at different temperatures. The average uncertainty in the viscosity measurements was ± 2 · 10−3 mPa·s. The results for the binary mixtures were reported in table S3 as Supplementary data and represented in Figs. 1–3(b). The viscosities of N,N-dimethylacetamide (1) + N-methylformamide (2) + propane-1,2-diol (3) ternary mixture were reported in table S4 as Supplementary data and shown in Fig. 5. The viscosity of the binary and ternary mixture becomes less with increasing temperatures. Negative E and the η values can be deduced that the size and shape of values of Vm molecules are influenced on the η values in addition to the strength of specific interaction [14]. Redlich–Kister expression [9] was applied in order to correlate the obtained excess molar volumes of the binary mixtures as following:
ΔQ ¼ xi x j
n X
p Bp xi −x j
ð3Þ
p¼0
where ΔQ refers to VEm for the binary mixtures; xi and xj are the mole fraction; Bp is the fitting parameter obtained by the un-weighted least-squares method and n is the degree of the polynomial expansion. Temperature dependence of Bp parameter can be expressed as follows:
Bp ¼
2 X q¼0
q
Apq T :
ð4Þ
Fig. 3. (b). Viscosity η, of {N-methylformamide (2) + 1,2-propanediol (3)} mixture at different temperatures: ▲, 293.15 K; ▿, 303.15 K; ■, 313.15 K; ⋄, 323.15 K, ×, 333.15 K.
264
H. Zarei et al. / Journal of Molecular Liquids 187 (2013) 260–265
E Fig. 4. Excess molar volumes Vm , surface of ternary mixture of {N,N-dimethylacetamide (1) + N-methylformamide (2) + 1,2-propanediol (3)} at 293.15 K. mental points. Curves represent the values calculated from Cibulka equation. The unit in the triangle plot is mole fraction.
is not the same for the mixtures. Different behaviors were observed E for the mixtures with increasing temperature but for the trend of Vm those for η values were regular. The η values decrease with increase in temperature of the mixtures. The results explained based on the
, represent experi-
strength of specific interactions, size and shape of molecules. The experimental data of excess molar volumes were correlated with Redlich–Kister and the Cibulka equations for the binary and ternary mixtures respectively.
Fig. 5. Viscosity η, surface of ternary mixture of {N,N-dimethylacetamide (1) + N-methylformamide (2) + 1,2-propanediol (3)} at 293.15 K. unit in the triangle plot is mole fraction.
, represent experimental points. The
H. Zarei et al. / Journal of Molecular Liquids 187 (2013) 260–265 Table 2 Correlation coefficients of Redlich–Kister and the Cibulka equations Apq, according to Eqs. (3), (4) and (6), together their standard deviations for the fits of excess molar volumes VEm ⋅ 106(kg ⋅ m−3), of binary and ternary mixtures in the temperature range (293.15 to 333.15) K. q
p 0
1
σ/(cm3 · mol−1)
2
{N,N-dimethylacetamide (1) + N-methylformamide (2)} 0 −1.51831 0.0106464 −1.9702 × 10−5 1 0.912985 −0.0064388 8.9717 × 10−6 2 −2.17687 0.0138508 −2.33415 × 10−5 {N,N-dimethylacetamide 0 −4.13522 1 1.26368 2 2.2819 3 1.02168
(1) + 1,2-propanediol (3)} 0.0207395 2.56949 −0.0056214 −1.99906 −0.0158326 2.43282 −0.0070491 1.40289
× × × ×
10−5 10−6 10−5 10−5
{N-methylformamide (2) + 1,2-propanediol (3)} 0 −3.54952 0.0234832 −4.01002 × 10−5 1 −1.95668 0.0141632 2.31253 × 10−5 2 −2.26881 0.014029 −2.22936 × 10−5
0.002
0.002
0.002
{N,N-dimethylacetamide (1) + N-methylformamide (2) + 1,2-propanediol (3)} 0 49.1533 −0.322224 4.95127 × 10−4 0.013 1 −187.03 1.23595 −0.0019842 2 103.221 −0.662585 0.00110532
Acknowledgment The authors would like to thank Bu-Ali Sina University for providing the necessary facilities to carry out the research.
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