Studies of volumetric, viscometric and molar properties of diisopropyl amine with 1-alkanols (C6–C10) at different temperatures

    Studies of volumetric, viscometric and molar properties of diisopropyl amine with 1-alkanols (C 6 -C10 ) at different temperatures Gyan Prakash Dubey, Krishan Kumar PII: DOI: Reference:

S0167-7322(16)33259-7 doi:10.1016/j.molliq.2016.12.065 MOLLIQ 6748

To appear in:

Journal of Molecular Liquids

Received date: Revised date: Accepted date:

21 October 2016 10 December 2016 17 December 2016

Please cite this article as: Gyan Prakash Dubey, Krishan Kumar, Studies of volumetric, viscometric and molar properties of diisopropyl amine with 1-alkanols (C6 -C10 ) at different temperatures, Journal of Molecular Liquids (2016), doi:10.1016/j.molliq.2016.12.065

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ACCEPTED MANUSCRIPT STUDIES OF VOLUMETRIC, VISCOMETRIC AND MOLAR PROPERTIES OF DIISOPROPYL

AMINE

WITH

1-ALKANOLS

(C6-C10)

AT

DIFFERENT

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Gyan Prakash Dubey* and Krishan Kumar#

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TEMPERATURES

*Department of Chemistry, Kurukshetra University, Kurukshetra-136119, India #

Department of Chemistry, Deenbandhu Chhotu Ram University of Science &Technology,

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Murthal, Sonepat-131039, India *

Corresponding author. Tel. +91-9416221007

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E-mail address:[email protected], [email protected]

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Abstract

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This paper presents the experimental measurements of densities,  , viscosities, and speeds of sound, u of (Diisopropylamine (DIIPA) +1-Hexanol, + 1-Octanol, + 1-Decanol) over the

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entire composition range at (293.15 to 313.15) K and atmospheric pressure. We examined the influence of temperature and alcohol chain length upon the various studied properties. Negative values of excess molar volume VmE and excess molar isentropic compressibilities, indicates the presence strong intermolecular interactions. The results of deviations in

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K SE, m

speeds of sound, u D , viscosity deviations,  and Gibbs excess free energy of activation of viscous flow , G *E also supports the conclusion drawn from VmE and K SE, m . The outcomes of VmE have been correlated to Prigogine−Flory−Patterson theory (PFP).

Keywords : Density; Excess Molar Volume; Viscosity; Molar Properties.

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ACCEPTED MANUSCRIPT 1. Introduction DIIPA is a secondary amine with the chemical formula (CH3)2HC-NH-CH(CH3)2. It is best known as its lithium derivative of its conjugate base, lithium diisopropylamide, known as

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"LDA". LDA is a strong, non-nucleophilic base. The bromide salt of DIIPA,

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diisopropylammonium bromide, is an organic molecular solid whose crystals are ferroelectric

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at room temperature. Alcohols are the well-known solvents with protic and self-associated properties, which are used to study the hydrophobic effects.1-Octanol is mainly consumed as a precursor to perfumes.1-Decanol is used in the manufacture of plasticizers, lubricants, surfactants and solvents. Its ability to permeate the skin has led to it being investigated as a

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penetration enhancer for transdermal drug delivery [1-2]. It has been examined for controlling essential tremor and other types of involuntary neurological tumors. Excess molar

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quantities are properties of solutions which differentiate the non-ideal behavior of real mixtures. The partial molar volume is generally understood as the contribution that a component of a mixture makes to the overall volume of the solution. This property is a

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thermodynamic quantity which indicates how an extensive property of a solution or mixture

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varies with changes in the molar composition of the mixture at constant temperature and pressure. In actual fact it is the partial derivative of the extensive property with respect to the

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number of moles of the component of concern. Every extensive property of a mixture has a corresponding partial molar property. The effect of increasing chain length of alcohols on excess molar volume, speed of sound and molar isentropic compression has been studied by Cobos et al. [3], Pal et al. [4–6], Tovar et al. [7]. Herein, we report the experimental

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measurements of densities,  , viscosities,  and speeds of sound, u of binary liquid mixtures of (DIIPA +1-Hexanol, + 1-Octanol, + 1-Decanol) over the entire composition range at (293.15 to 313.15) K and atmospheric pressure. From the results obtained, various derived parameters such as excess molar volume, excess molar isentropic compressibility, excess Gibbs energy and deviation in speed of sound have been reported in terms of interaction between unlike molecules of the mixtures. In this communication, our objective is to see the effect of chain length of 1-alkanols and temperature on the intermolecular interactions between the mixing components of the studied binary liquid mixtures of DIIPA and 1-alkanols (C6-C10). 2. Experimental 2.1 Materials 2

ACCEPTED MANUSCRIPT Chemicals used in the present study are DIIPA, 1-Hexanol, 1-Octanol and 1-Decanol. All the chemicals were purchased from S.D. Fine Chemicals Ltd. In all cases chemicals with purity greater than 99.5% by mass were used for the experimental investigations (Table 1). Prior to

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making the experimental measurements, all liquids were stored in dark bottles over 0.4 nm

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molecular sieves to reduce water content and were distilled and partially degassed under vacuum. Further, to avoid any contamination and absorption of moisture the preparation of

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samples was done with extra care and precautions. Measurements were done within the least time. The details of the chemicals used in the present work are also given in Table 1.

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2.2 Apparatus & Procedure

The binary mixture was prepared by weighing appropriate amounts of DIIPA and alcohols on

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an Afcoset-ER-120A electronic balance, with a precision of ±0.05 mg, by syringing each component into airtight narrow mouthed stoppered bottles to minimize evaporation losses. The pure components were separately degassed shortly before sample preparation. The

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accuracy of mole fraction was ±1∙10-4. Density,  and speed of sound, u were measured by

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using a digital vibrating tube density and speed of sound analyzer (Anton Paar DSA 5000), having two integrated Pt 100 Platinum thermometers with a proportional temperature

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controller that kept the sample at the required temperature. The apparatus was calibrated at the working temperatures with dry air, double toluene, cyclohexane and distilled water. The temperature in the cell was regulated to ±1∙10-2 K with a built-in solid state thermostat by the Peltier method. Uncertainty in density measurement is ±2∙10-3 kg∙m-3 and for the speed of

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sound is ±0.1 m∙s-1. An acoustic signal indicated when the measurement was completed. The results were automatically converted (including temperature compensation wherever necessary) into concentration, specific gravity, or other density-related units using the built-in conversion tables and functions. The kinematic viscosities ( = /  ) of pure liquids and liquid mixtures were measured at T = (298.15, 303.15 and 308.15) K and at atmospheric pressure using an Ubbelohde suspended level viscometer. The viscometer was calibrated to determine the two constants A and B in the equation,  /   At  B / t obtained by measuring the flow time (t) with double distilled water and cyclohexane. The flow time measurements were made by using an electronic stopwatch with a precision of ±0.1 s. An average of four or five sets of flow times for each liquid or liquid mixture was taken for the purpose of calculations of viscosity. The uncertainty in the viscosity measurements, based on our work on several pure 3

ACCEPTED MANUSCRIPT liquids, was ±0.03 mPa∙s. The temperature of the samples was controlled by using a water bath equipped with a thermostat of accuracy ±0.01 K. The reliability of experimental measurements of  , u and  were ascertained by comparing the experimental values of pure

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liquids with the corresponding literature values (Table 2). Table 2 compares the densities,  ,

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viscosities,  and speeds of sound, u for the pure liquid components and their binary

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mixtures at 298.15, 303.15, and 308.15 K with values reported in the literatures [8-25]. Table 2 also contains our measured or literature values of those quantities which were required in the estimation of K S ,m , K SE,m and u D .

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3. Results & Discussion

The experimental values of density were used to calculate the excess molar volume

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VmE of the mixtures using equation: 2

VmE   xi M i (  1   i1 ) i 1

(1)

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where  is the density of the mixture and xi , Mi, and  i are the mole fraction, molar mass

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(M = x1M1+x2M2) and density of pure component i, respectively. The isentropic compressibility,  S was calculated using the Newton−Laplace equation:

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 S  Vm1 ( Vm /  P) S  (  u 2 ) 1  Vm (M u 2 ) 1

(2)

where Vm is the molar volume and M the molar mass of the mixture. The molar isentropic

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compressibility was calculated using equation:

K s ,m  (Vm / P) s  Vm s  xi M i /( u ) 2

(3)

The excess molar isentropic compressibility K SE,m was calculated using following equation: id

K SE,m = K S , m - K S , m where

K Sid,m

(4)

defined by the approach developed by Kiyohara and Benson [26]:

* * * * * * K Sid,m xi [ K S ,i  TAP,i (xi AP,i / xi CP,i )  ( AP,i / CP,i )]

=

where

AP* ,i ( Vm,i   P,i ) *

*

is the product of molar volume and the isobaric expansivity,

(5)

C P* ,i

the molar isobaric heat capacity, K S* ,i the product of the molar volume, Vm*,i and the isentropic compressibility K S* ,i of the pure liquid component i. The deviations of the speed of sound from their values in an ideal mixture were calculated from equation [26]:

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ACCEPTED MANUSCRIPT u D  u  u id u

where

u

id



id

(6)

was calculated using equation:

(Vmid )1 / 2 ( K Sid,m

* 1 / 2

i  i ) i

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(7) where  i is the volume fraction of ith component. The variation of  , VmE , u , u D , K S ,m and

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K SE,m at all temperatures of interest for the studied binaries are given in Tables 3 to 5. The deviations of the viscosities from the linear dependence were calculated from the relationship: 2

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     xii i 1

(8)

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where  and  i are viscosities of the mixture and the pure component i respectively. On the basis of the theory of reaction rates, the excess Gibbs energy of activation of viscous flow G *E was calculated using the following equation: 2



(9)

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i 1

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G *E = R T [ ln(V )   xi ln( iVi )

whereR is the universal constant of gas, T is the absolute temperature, V and Vi are the molar

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volumes of the binary mixtures and pure components, respectively. The variation of  and

G *E at all temperatures of interest for the studied binaries are given in Table6.The excess molar volumes and deviations in speed of sound, isentropic compressibility, viscosity and

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excess Gibbs energy of activation of viscous flow were fitted to a Redlich-Kister equation [27]:

p

Y ( x)  x1 x2  Ai ( x1  x2 )

i

(10)

i 1

wherep is the number of estimated parameters Ai . The standard deviation was calculated using the equation: n

  [{Y ( x) exptl  Y ( x) cal }2 /( n  p)]1/ 2

(11)

i 1

where Y ( x) exp tl and Y ( x) cal are the values of the experimental and calculated properties ( VmE , u,  ,  s and G *E ) respectively, and n is the number of experimental data points. The

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ACCEPTED MANUSCRIPT calculated values of the coefficients, Ai along with the standard deviations ( ) are given in Table 7 (given in supplementary Materials). The excess molar volume, VmE , molar isentropic compressibilities, K S , m , excess molar

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isentropic compressibilities, K SE, m , deviations in speeds of sound, u D from their ideal values

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in an ideal mixture, u id ,viscosity deviation,  and excess Gibbs free energy of activation for

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viscous flow, G *E were calculated by using the equations (1-9). The values of  , VmE , u , u D , K S ,m , and K SE,m for the binary mixtures at 293.15 to 313.15 K are listed in Tables 3, 4

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and 5 respectively. The other parameter such as ,  and G *E at 298.15, 303.15 and 308.15 K are given in Table 6.

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The values of VmE are plotted as a function of x1 in Figures 1-3 which shows that mixtures of DIIPA with 1-Hexanol, 1-Octanol and1-Decanol exhibit negative VmE values for the whole range of composition and at all of the studied temperatures. The negative trend in

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the values of VmE is observed in all of the three binary mixtures with minima at x1 ≈ 0.5. The

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negative VmE values show the presence of strong intermolecular forces of attraction. The present results can be interpreted qualitatively by taking into account the fact that several

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expansion and contraction processes proceed simultaneously when amine-alkanol mixtures are formed. The following effects can be considered: (i) expansion due to depolymerization of alcohol and amine by one another, (ii) contraction due to free volume difference of unlike

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molecules, and (iii) contraction due to hydrogen bond formation between amine and alcohol through NH2….OH and OH….NH2. The interaction between the studied liquid mixtures can be considered the reaction between alkanol as a Lewis acid and amine as a Lewis base. There is no significant change observed in the values of VmE with temperature, it is also observed from Figures 1-3 that as we move from 1-hexanol to 1-octanol to 1-decanol, the negative values of VmE increase [28]. So, there are strong forces of attraction in 1-decanol among the three alcohols. The large negative value of VmE for the mixture with 1-decanol indicates that a most efficient packing of molecules occurs in this mixtures. For the mixtures of DIIPA with 1-Hexanol, 1-Octanol and 1-Decanol, the values of

K SE, m , and u D are plotted in Figures 4 and 5 respectively. The excess molar isentropic compressibility, K SE, m shows negative trend for all the three systems over the entire

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ACCEPTED MANUSCRIPT composition range and at all studied temperatures. The behavior of VmE with x1 is well reflected in the behavior of K SE, m for the binary mixtures investigated. The K SE, m values can be interpreted in terms of (i) decrease in free volume in mixture as compared to those in pure

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components, (ii) interstitial accommodation of alcohol molecules in the aggregates of amine.

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The negative K SE, m values for the studied binary mixtures show that first factor predominates

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in these mixtures and the mixture is less compressible than the corresponding ideal mixture. In these binary mixtures contraction in free volume makes the mixture less compressible than ideal mixtures. Negative K SE, m means that mixture is less compressible than the ideal mixture.

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It is clear from Figure 5 that the trends in u D values are similar to K SE, m but with opposite sign.

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The variation of the viscosity deviations,  with the mole fraction, x1 for the binary mixtures is presented in Figure 6. The  values are negative for all the three binary

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mixtures over the whole composition range. The absolute values of  shows a decrease with increase in alkyl chain length of alcohol molecules from 1-hexanol to 1-decanol. The

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 – x1 curves show maximum negative values at x1  0.5 for studied binary mixtures. The

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viscosity of pure DIIPAis found to be about an order of magnitude smaller (≈ 0.382 mPa∙s) than that of 1-Decanol (≈ 11.192 mPa∙s). The viscosity of a mixture strongly depends upon the entropy of mixture [29] which is related with the structure of the liquid and consequently with molecular interaction between the components of the mixture. The negative value

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observed for viscosity deviations of the mixture under study cannot explain the graded behavior of the complex formation between amine and alcohol. This shows that strength of the intermolecular hydrogen bonding is not the only factor affecting the viscosity deviation of liquid mixtures. The molecular sizes and shape of the components are equally important factors. The G *E parameter can also be considered as a reliable criterion to detect or exclude the presence of interactions between unlike molecules [30, 31]. According to Reed and Taylor and Meyer et al., positive G *E values indicate specific interactions while negative values indicate the dominance of dispersion forces [31]. From G *E values (Figure 7), it is seen that these values are positive for 1-Decanol but changes sign from positive to negative in case of 1-Hexanol and 1-Octanol.

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ACCEPTED MANUSCRIPT Apart from expressing  as a polynomial fit, several semi-empirical relations have been put forward to correlate the viscosity of binary liquid mixtures in terms of their pure component data. The following semi-empirical models have been tested for the mixtures

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under study: Grunberg and Nissan [32], Tamura and Kurata [33], Hind, Mclaughlin and

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Ubbelohde [34], Katti and Chaudhari [35], McAllister (three body interaction) model [36], Heric and Brewer (three-parameter) model [37], McAllister (four-body interactions) model

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[36].

Out of seven equations, first four are single-parameter equations while last one is a three-parameter equation. For each of these equations their adjustable parameters and percent 

0

0

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standard deviations have been calculated. The values of the percentage standard deviation, shown in Table 8 (given in supplementary Materials) lies in the range 4.34 to 6.24 for

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Grunberg-Nissan relation, 2.69 to 14.96 for Tamura-Kurata relation, 47.37to 78.05 for Katti and Chaudhari and 3.69 to 9.57 for Hind et al. relation for the binary mixture under study. The analysis of the results for one-parameter relation reveals that Grunberg-Nissan relation

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shows minimum  0 0 followed by Hind et al. relation. Grunberg-Nissan parameter also

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provides the type and extent of interaction. It reveals from Table 8 that the positive values of

G12 in present mixtures also support graded behavior. Heric-Brewer three parameter relation

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has standard percentage deviation,  0 0 in the range 0.004 to 0.32. McAllister (three-body interaction) lie in the range 0.009 to 0.076% and for McAllister (Four-body interaction) relation  % values ranges from 0.29 to 0.97%. The values of  0 0 for the present binary

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systems investigated indicate that three-parameter relation correlate viscosity data better compared to one-parameter relations. Theoretical Model: The Prigogine−Flory−Patterson (PFP) theory [38-42] has been commonly employed to estimate and analyze excess thermodynamic functions theoretically. This theory has been described in details by Patterson and co-workers [43-44]. According to PFP theory, VmE can be considered as a sum of three contributions: (i) an interactional contribution, VmE (int.), (ii) a free volume contribution, VmE (fv), and (iii) an internal pressure contribution, VmE (P*). The details of the notations and terms used in equations may be obtained from literature [39-42, 45-46]. The interaction parameter 12 was obtained by employing the Marquardt algorithm [47] in an optimization procedure, using all experimental VmE data at 298.15 K over the complete concentration range. The resulting  12 was used to

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ACCEPTED MANUSCRIPT calculate VmE [48-50]. The various parameters involved in equation for the pure components are obtained through Flory theory and are given in Table 9 and Table 10 (given in supplementary Materials) reports the calculated and experimental equimolar values of the

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three contributions to VmE together with the contact interaction parameter 12 . In Table 10, the

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interaction term, which is proportional to  12 , is negative for all the systems. The free volume

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is proportional to  (v~1  v~2 ) 2 and it becomes more negative as the difference between the reduced volumes of two components in the mixture increases. The internal pressure term which is proportional to (v~1  v~2 ) 2 ( P1*  P2* ) may be positive or negative depending upon

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the relative cohesive energy of the expanded and less expanded component. In the present case it is positivefor all the binary mixtures under study. The comparison of calculated and

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experimental values has been shown in Figure 1-3, which demonstrates that PFP theory gives satisfactory results.

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4. Conclusion

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The negative trend in the values of VmE is observed in all of the three binary mixtures. The negative VmE values show the presence of strong intermolecular forces of attraction.As we

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move from 1-hexanol to 1-octanol to 1-decanol, the negative values of VmE decrease.The excess molar isentropic compressibility, K SE, m also shows negative trend for all the three

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systems over the entire composition range and at all studied temperatures. The trends observed in the values of u D ,  and G *E also supports the earlier conclusion drawn. PFP theory is in good agreement with the experimental results. Acknowledgements

Financial support for the work by the Government of India through University Grants Commission, New Delhi (letter no F.14-2(SC)/2008 (SA-III) dated 31-03-2009) is gratefully acknowledged.

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Equilib. 204 (2003) 281–294

[29] A. Hartono, H.F. J. Chem. Density, viscosity, and excess properties of aqueous solution

CE P

of diethylenetriamine (DETA) Thermodyn.41 (2009), 973-979. [30] R. C. Reid, J. M. Prausnitz, B. E. Poling, The Properties of Gases and Liquids,4th edition, McGraw-Hill, New York 1987.

AC

[31] A. W. Quin, D. F. Hoffmann, P. Munk, Excess volumes of mixtures of alkanes with carbonyl compounds J. Chem. Eng. Data 37 (1992), 55-61. [32] L. Grunberg, A. Nissan, Mixture Law for Viscosity Nature 164 (1949), 799-800. [33] M. Tamura, M. Kurata, On the viscosity of binary mixture of liquids. Bull. Chem. Soc. Jpn. 25 (1952), 32-37. [34] R. K. Hind, M. Mclaughlin, A. R. Ubbelohde, Structure and viscosity of liquids. Camphor + pyrene mixtures Trans. Faraday Soc.56 (1960), 328-330. [35] P. K. Katti, M. M. Chaudhry, Viscosities of Binary Mixtures of Benzyl Acetate with Dioxane, Aniline, and m-Cresol. J. Chem. Eng. Data 9 (1964), 442-443. [36] R. A. McAllister, The viscosity of liquid mixtures AIChE J. 6 (1960), 427-431. [37] E. L. Heric, On the Viscosity of Ternary Mixtures. J. Chem. Eng. Data 11 (1966), 66-68. [38] D. Patterson, G. Delmas, Corresponding states theories and liquid models. Discuss. Faraday Soc. 49 (1970), 98-105. 9

ACCEPTED MANUSCRIPT [39] I. Prigogine, The Molecular Theory of Solutions, North-Holland Publishing Company, Amsterdam 1957. [40] P. J. Flory, Statistical Thermodynamics of Liquid Mixtures J. Am. Chem. Soc. 87

T

(1965), 1833-1838.

Molecules J. Am. Chem. Soc. 87 (1965), 1838-1846.

IP

[41] P. J. Flory, A. Abe, he Thermodynamic Properties of Mixtures of Small, Nonpolar

SC R

[42] G. P. Dubey, M. Sharma, Thermodynamic and Transport Properties of Binary Liquid Mixtures of 1-Hexanol with Hexadecane and Squalane at 298.15, 303.15 and 308.15 KZ. Phys. Chem. 223 (2009), 279-298.

NU

[43] P. Trancrede, P. Bothorel, P. St. Romain, D. Patterson, Interactions in alkane systems by depolarized Rayleigh scattering and calorimetry. Part 1.—Orientational order and

MA

condensation effects in n-hexadecane + hexane and nonane isomersJ. Chem. Soc. Faraday Trans. II 73 (1977), 15-28.

[44] P. St. Romain, H. T. Van, D. Patterson, Effects of molecular flexibility and shape on the

TE

75 (1979), 1700-1707.

D

excess enthalpies and heat capacities of alkane systemsJ. Chem. Soc. Faraday Trans. I

[45] A. T. Rodriguez, D. Patterson, Excess thermodynamic functions of n-alkane mixtures.

CE P

Prediction and interpretation through the corresponding states principleJ. Chem. Soc. Faraday Trans. II 78 (1982), 501-523. [46] T. M. Aminabhavi, K. Banerjee, R. H. Balundgi, Thermodynamic interactions in binary mixtures of 1-chloronaphthalene and monocyclic aromatics Indian J. Chem. A 38

AC

(1999), 768-777.

[47] D. W. Marquardt, An Algorithm for Least-Squares Estimation of Nonlinear ParametersJ. Soc. Indust. Appl. Math. 11(1963), 431-441. [48] S. L. Oswal, S. S. R. Putta, Excess molar volumes of binary mixtures of alkanols with ethyl acetate from 298.15 to 323.15 K Thermochim. Acta 373 (2001), 141-152. [49] H. Iloukhani, Z. Rostami, Measurement of Some Thermodynamic and Acoustic Properties of Binary Solutions of N,N-Dimethylformamide with 1-Alkanols at 30°C and Comparison with Theories J. Solution Chem. 32 (2003), 451. [50] M. Ramamurthy, O. S. Sastry, Ind. J. Pure Appl. Phys. 21 (1983), 579.

10

ACCEPTED MANUSCRIPT

Initial Mass Fraction Purity ≥0. 99 ≥0. 99 ≥0. 99 ≥0. 99

US

MA N

SD. Fine Chemicals, India SD. Fine Chemicals, India SD. Fine Chemicals, India SD. Fine Chemicals, India

CR

IP

Make

TE D

DIIPA 1-Hexanol 2-Octanol 1-Decanol

CAS No. 108-18-9 111-27-3 111-87-5 112-30-1

CE P

Sample

AC

S. No. 1. 2. 3. 4.

T

Table 1: Sample Information Table

7

Purification Method Distillation Distillation Distillation Distillation

Final Mass Fraction Purity 0. 99 0. 99 0. 99 0. 99

Analysis Method None None None None

AC

CE P

TE D

MA N

US

CR

IP

T

ACCEPTED MANUSCRIPT

CR

IP

T

ACCEPTED MANUSCRIPT

US

Table2. Experimental and literature values of densities,  * , viscosities, , speeds of sound, u * , isobaric expansivity,  P* , isobaric molar heat capacity, C P* , m

Exptl. 0.711509

0.7148 [18]

Exptl. 0.382

Lit.

u*

 P*

−1

(m s ) Exptl.

298.15 K 1091.89

(kK-1)

C P* , m (J K-1 mol-1)

K S* ,m (mm3 mol-1 MPa-1)

Lit. 1096.0 [18]

266.0 [18]

167.66

*

1.374*

1-Hexanol

0.815265

0.81523 [10]

4.439

4.593 [11]

1303.2

1303.3 [12]

0.885

241.64 [13]

90.51

1-Octanol

0.821794

0.82179 [9]

7.143

7.143 [14]

1347.5

1348.0 [15]

0.848*

308.39 [20]

106.19

1-Decanol

0.826470

0.82670 [16]

AC

DIIPA

Lit.

TE D

(kg m−3)

CE P

Components

 (mPa s)

 * ×10−3

MA N

and molar isentropic compressibility, K S* ,m of pure liquid components at (298.15, 303.15 and 313.15) K and atmospheric pressure:

11.192 [16]

1379.8

1380.2 [12]

0.834*

371.1 [17]

121.70

11.192

303.15 K

DIIPA

0.706633

0.70998 [18]

0.364

-

1069.37

1-Hexanol

0.811661

0.81195 [8]

3.675

3.916 [21]

1286.42

1-Octanol

0.818310

0.8184 [22]

5.969

6.36 [23]

1330.69

1-Decanol

0.823050

9.066

9.652 [22]

1362.88

0.82296 [24]

308.15 K 7

1.384*

268.0 [18]

177.21

0.889*

246.52 [20]

93.72

1335.0 [24]

0.851*

313.60 [20]

109.83

1364.99 [20]

0.837*

375.40 [20]

125.79

1071.0 [18] 1287.9 [21]

ACCEPTED MANUSCRIPT

1046.0 [18]

1.393*

270.0 [18]

187.45

1269.82

1271.14 [20]

0.893*

251.47 [20]

97.05

1314.03

1314.27 [20]

0.855*

320.12 [20]

113.60

1346.01

1346.10 [20]

0.841*

380.40 [20]

130.05

0.701737

0.70518 [18]

0.347

-

1047.01

1-Hexanol

0.808037

0.80834 [19]

3.107

3.359 [20]

1-Octanol

0.814813

0.8150 [22]

5.009

5.38 [23]

1-Decanol

0.819611

0.819427 [20]

7.459

7.918 [25]

CR

IP

T

DIIPA

AC

CE P

TE D

MA N

US

The uncertainty in density, viscosity and speeds of sound is ±2∙10-3 kg∙m-3, ±0.03 mPa∙s and ±0.1 m∙s-1 respectively.

8

ACCEPTED MANUSCRIPT Table3. Densities,  , speeds of sound, u , excess molar volumes , VmE , molar isentropic compressibilities, K S , m , excess molar isentropic compressibilities, K SE,m and deviations in

 ×10−3 (kg m−3)

u

(m s−1)

VmE ×106

K S ,m

(m3 mol−1)

K SE,m

uD

(mm3 mol-1

(mm3 mol-1

(ms−1)

MPa-1)

MPa-1)

RI P

x1

T

speeds of sound, u D for the binary mixtures at different temperatures:

0.818842

1320.13

0.0000

0.0503

0.816362

1319.60

-0.5103

0.1067

0.813411

1316.41

-1.0539

0.1499

0.810879

1314.07

-1.4262

0.2041

0.807370

1309.70

0.2530

0.803815

1304.32

0.3054

0.799734

1297.10

-2.4261

0.4026

0.790827

1279.39

-2.7138

0.4986

0.781086

1258.14

-2.8114

0.6007

0.769413

0.7077

0.756264

0.8518 0.9021 0.9545 1.0000

MA

ED

PT

-1.8385 -2.145

1232.43

-2.6491

1202.63

-2.2557

AC CE

0.7994

NU

0.0000

SC

DIIPA + 1-Hexanol, 293.15 K

0.744480

1175.49

-1.7638

0.737507

1159.44

-1.4094

0.730811

1144.78

-1.0470

0.723433

1128.05

-0.5681

0.716367

1114.58

0.0000 298.15 K

0.0000

0.815265

1303.24

0.0000

90.51

0.00

0.00

0.0503

0.812696

1302.24

-0.5144

91.18

-3.21

17.11

0.1067

0.809636

1298.47

-1.0608

92.36

-6.39

32.15

0.1499

0.807017

1295.69

-1.4341

93.32

-8.76

42.80

0.2041

0.803403

1290.87

-1.8474

94.81

-11.45

53.76

0.2530

0.799758

1285.03

-2.1551

96.50

-13.53

61.23

0.3054

0.795587

1277.43

-2.4369

98.63

-15.44

67.00

0.4026

0.786538

1259.08

-2.7273

103.78

-17.79

71.26

9

ACCEPTED MANUSCRIPT 0.776690

1237.31

-2.8299

110.10

-18.87

69.40

0.6007

0.764922

1211.19

-2.6719

118.35

-18.50

62.20

0.7077

0.751680

1181.20

-2.2800

128.73

-16.38

49.89

0.7994

0.739825

1153.70

-1.7878

139.17

-13.01

36.04

0.8518

0.732771

1137.35

-1.4241

145.90

0.9021

0.726037

1122.54

-1.0593

0.9545

0.718571

1105.55

1.0000

0.711509

1091.89

T

0.4986

26.93

152.49

-7.62

18.71

-0.5668

160.41

-3.74

8.25

0.0000

167.66

0.00

0.00

0.811661

1286.42

0.0000

0.0503

0.809007

1284.93

0.1067

0.805839

0.1499

SC

0.0000

0.00

0.01

-0.5193

94.51

-3.41

17.39

1280.62

-1.0686

95.84

-6.79

32.63

0.803135

1277.47

-1.4432

96.93

-9.31

43.41

0.2041

0.799413

1272.17

-1.8571

98.60

-12.17

54.44

0.2530

0.795677

1265.86

-2.1654

100.47

-14.38

61.86

0.3054

0.791422

1257.86

-2.4493

102.80

-16.42

67.63

0.4026

0.782235

1238.91

-2.7430

108.37

-18.97

71.90

0.4986

0.772279

1216.67

115.18

-20.18

70.05

0.6007

0.760412

1190.04

-2.6959

124.05

-19.83

62.73

0.7077

0.9545 1.0000

0.9021

ED

PT

0.8518

-2.8505

AC CE

0.7994

NU

93.72

MA

303.15 K

RI P

-10.33

0.747087

1159.80

-2.3072

135.17

-17.65

50.49

0.735150

1131.98

-1.8124

146.41

-14.06

36.52

0.728052

1115.49

-1.4461

153.64

-11.20

27.37

0.721266

1100.40

-1.0763

160.79

-8.25

18.96

0.713745

1083.12

-0.4768

169.39

-4.02

8.29

0.706633

1069.37

0.0000

177.21

0.00

0.00

308.15 K 0.0000

0.808037

1269.82

0.0000

97.05

0.00

0.01

0.0503

0.805295

1267.81

-0.5238

97.98

-3.62

17.67

0.1067

0.802021

1263.22

-1.0766

99.44

-7.26

33.39

0.1499

0.799231

1259.57

-1.4526

100.68

-9.93

44.18

0.2041

0.795406

1253.69

-1.8677

102.55

-12.95

55.18

0.2530

0.791583

1246.92

-2.1774

104.62

-15.30

62.58

0.3054

0.787241

1238.51

-2.4629

107.17

-17.50

68.35

10

ACCEPTED MANUSCRIPT 0.777918

1218.88

-2.7605

113.21

-20.24

72.56

0.4986

0.767855

1196.20

-2.8732

120.53

-21.60

70.74

0.6007

0.755891

1169.03

-2.7226

130.09

-21.26

63.27

0.7077

0.742472

1138.36

-2.3350

142.06

-18.97

50.91

0.7994

0.730457

1110.28

-1.8383

154.15

0.8518

0.723309

1093.60

-1.4681

0.9021

0.716475

1078.32

0.9545

0.708896

1.0000

0.701737

36.88

161.96

-12.10

27.64

-1.0938

169.69

-8.91

19.12

1060.89

-0.5854

178.99

-4.35

8.36

1047.01

0.0000

187.45

0.00

0.00

1253.53

0.0000

0.0503

0.801547

1250.82

-0.5231

0.1067

0.798168

1246.34

0.1499

0.795295

1242.16

0.2041

0.791369

1235.56

MA

0.2530

0.787457

1228.19

-2.1862

0.3054

0.783036

1219.32

-2.4740

0.4026

0.773577

1198.88

0.4986

0.763407

1175.79

-2.8955

0.6007

0.9021

-1.0798 -1.4577

PT

AC CE

-1.8752

-2.7771

0.751342

1147.83

-2.7487

0.737826

1116.56

-2.3623

0.725735

1088.29

-1.8643

0.718536

1071.60

-1.4902

0.711650

1056.06

-1.1107

0.9545

0.704015

1038.50

-0.5942

1.0000

0.696811

1023.80

0.0000

0.8518

SC

NU

0.804413

ED

0.0000

0.7994

RI P

-15.17

313.15 K

0.7077

T

0.4026

The uncertainty in density, viscosity and speeds of sound is ±2∙10-3 kg∙m-3, ±0.03 mPa∙s and ±0.1 m∙s-1 respectively.

11

ACCEPTED MANUSCRIPT Table4. Densities,  , speeds of sound, u , excess molar volumes , VmE , molar isentropic compressibilities, K S , m , excess molar isentropic compressibilities, K SE,m and deviations in speeds

 ×10−3 (kg m−3)

u

(m s−1)

VmE ×106

K S, m

(m3 mol−1)

K SE,m

uD

(mm3 mol-1

(mm3 mol-1

(m s−1)

MPa-1)

MPa-1)

RI P

x1

T

of sound, u D for the binary mixtures at different temperatures:

0.825257

1364.54

0.0000

0.0552

0.822736

1361.24

-0.5512

0.1034

0.820319

1356.34

-0.9992

0.1579

0.817339

1350.96

-1.4681

0.2037

0.814507

1346.37

0.2551

0.810993

1339.51

0.3074

0.806982

1331.29

0.4058

0.798330

1311.21

-2.7224

0.5058

0.788016

1286.10

-2.8106

0.6060

0.776313

0.7025

0.763832

0.8595 0.8931 0.9418 1.0000

MA

ED

PT

-1.8085 -2.1370 -2.4007

1257.48

-2.6901

1226.15

-2.3910

AC CE

0.8044

NU

0.0000

SC

DIIPA + 1-Octanol, 293.15 K

0.750011

1190.85

-2.0003

0.742777

1171.63

-1.7421

0.736172

1157.25

-1.3525

0.727940

1138.57

-0.8872

0.716367

1114.58

0.0000 298.15 K

0.0000

0.821794

1347.56

0.0000

106.19

0.00

0.00

0.0552

0.819196

1343.71

-0.5572

106.16

-3.43

16.50

0.1034

0.816705

1338.59

-1.0088

106.45

-6.10

28.33

0.1579

0.813633

1332.76

-1.4801

106.85

-9.05

40.81

0.2037

0.810725

1327.73

-1.8225

107.29

-11.43

50.51

0.2551

0.807125

1320.52

-2.1526

108.12

-13.75

59.15

0.3074

0.803035

1311.87

-2.4189

109.30

-15.79

65.95

0.4058

0.794248

1291.38

-2.7464

112.59

-18.55

72.77

12

ACCEPTED MANUSCRIPT 0.783810

1265.81

-2.8403

117.38

-19.91

72.82

0.6060

0.771997

1236.79

-2.7254

123.55

-19.89

67.53

0.7025

0.759409

1205.14

-2.4289

131.13

-18.25

57.04

0.8044

0.745013

1169.52

-1.9503

140.77

-14.87

42.13

0.8595

0.737223

1149.96

-1.5938

146.47

0.8931

0.730959

1135.26

-1.2746

0.9418

0.722840

1116.25

1.0000

0.711509

1091.89

T

0.5058

33.12

151.46

-9.63

24.63

-0.8371

158.03

-6.06

14.35

0.0000

167.66

0.00

0.00

0.81831

1330.69

0.0000

0.0552

0.815641

1326.52

0.1034

0.813071

0.1579

SC

0.0000

0.00

0.00

-0.5644

109.88

-3.67

16.96

1321.02

-1.0190

110.28

-6.52

29.02

0.809809

1314.88

-1.4930

110.82

-9.65

41.80

0.2037

0.806926

1309.56

-1.8377

111.33

-12.23

51.67

0.2551

0.803242

1301.83

-2.1699

112.32

-14.70

60.25

0.3074

0.799074

1292.80

-2.4391

113.67

-16.88

67.08

0.4058

0.790154

1271.72

-2.7728

117.30

-19.87

73.96

0.5058

0.779596

1245.72

122.51

-21.41

74.10

0.6060

0.767666

1216.17

-2.7628

129.22

-21.45

68.67

0.7025

0.9418 1.0000

0.8931

ED

PT

0.8595

-2.8733

AC CE

0.8044

NU

109.83

MA

303.15 K

RI P

-12.55

0.754968

1184.13

-2.4683

137.42

-19.74

58.09

0.740430

1148.11

-1.9837

147.89

-16.15

43.00

0.732468

1128.32

-1.6023

154.12

-13.62

33.84

0.726204

1113.40

-1.2890

159.53

-10.48

25.18

0.717958

1094.03

-0.8328

166.76

-6.54

14.60

0.706633

1069.37

0.0000

177.21

0.00

0.00

308.15 K 0.0000

0.814813

1314.03

0.0000

113.60

0.00

0.00

0.0552

0.812063

1309.58

-0.5701

113.73

-3.95

17.51

0.1034

0.809416

1303.83

-1.0281

114.23

-7.00

29.95

0.1579

0.80617

1297.75

-1.5066

114.79

-10.47

43.42

0.2037

0.803108

1291.83

-1.8527

115.50

-13.15

53.16

0.2551

0.799346

1283.41

-2.1883

116.70

-15.74

61.52

0.3074

0.795102

1273.92

-2.4609

118.23

-18.07

68.31

13

ACCEPTED MANUSCRIPT 0.786049

1252.23

-2.8013

122.25

-21.32

75.24

0.5058

0.775368

1225.61

-2.9080

127.94

-23.01

75.27

0.6060

0.763326

1195.68

-2.8032

135.21

-23.15

69.84

0.7025

0.750512

1163.2

-2.5096

144.11

-21.37

59.10

0.8044

0.735851

1126.63

-2.0229

155.50

0.8595

0.727809

1106.67

-1.6341

0.8931

0.721481

1091.55

0.9418

0.713153

1.0000

0.701737

43.67

162.27

-14.81

34.43

-1.3141

168.16

-11.40

25.61

1071.93

-0.8480

176.05

-7.10

14.82

1047.01

0.0000

187.45

0.00

0.00

1297.78

0.0000

0.0552

0.808459

1293.02

-0.5685

0.1034

0.805736

1287.64

0.1579

0.802405

1281.10

0.2037

0.799269

1274.32

MA

0.2551

0.795431

1265.57

-2.2031

0.3074

0.791110

1255.45

-2.4796

0.4058

0.781926

1232.81

0.5058

0.771122

1205.57

-2.9422

0.6060

0.8931

-1.0308 -1.5141

PT

AC CE

-1.8633

-2.8281

0.758964

1175.11

-2.8432

0.746034

1142.00

-2.5515

0.731245

1104.90

-2.0623

0.723123

1084.88

-1.6664

0.716739

1069.51

-1.3415

0.9418

0.708323

1049.62

-0.8643

1.0000

0.696811

1023.80

0.0000

0.8595

SC

NU

0.811330

ED

0.0000

0.8044

RI P

-17.51

313.15 K

0.7025

T

0.4058

The uncertainty in density, viscosity and speeds of sound is ±2∙10-3 kg∙m-3, ±0.03 mPa∙s and ±0.1 m∙s-1 respectively.

14

ACCEPTED MANUSCRIPT Table5. Densities,  , speeds of sound, u , excess molar volumes , VmE , molar isentropic compressibilities, K S , m , excess molar isentropic compressibilities, K SE,m and deviations in speeds of sound, u D for the binary mixtures at different temperatures: u x1  ×10−3 K S, m VmE ×106 (m3 mol−1)

(mm3 mol-1

T

(m s−1)

(mm3 mol-1

RI P

(kg m−3)

K SE,m

MPa-1)

uD

(m s−1)

MPa-1)

0.829883

1397.07

0.0000

0.0531

0.827523

1391.83

-0.4924

0.1065

0.825000

1385.30

-0.9722

0.1557

0.822582

1381.17

-1.4106

0.2072

0.819529

1373.41

-1.7739

0.2506

0.816690

1366.80

0.3127

0.812664

1357.15

0.4087

0.804884

1338.60

0.5054

0.794602

1312.61

-2.8405

0.6066

0.782636

1280.66

-2.7257

0.7056

0.769283

0.8036

0.754947

0.9073 0.9521 1.0000

MA

ED

PT

-2.0395 -2.4565 -2.8398

1244.85

-2.4327

1206.48

-2.0827

AC CE

0.853

NU

0.0000

SC

DIIPA + 1-Decanol, 293.15 K

0.747313

1184.77

-1.8917

0.736421

1160.20

-1.2462

0.728814

1139.47

-1.0299

0.716367

1114.58

0.0000 298.15 K

0.0000

0.82647

1379.87

0.0000

121.70

0.00

0.00

0.0531

0.824059

1374.42

-0.5008

121.02

-3.12

13.76

0.1065

0.821466

1367.4

-0.985

120.63

-5.97

25.53

0.1557

0.818984

1363.05

-1.4279

119.88

-8.98

38.04

0.2072

0.815857

1354.88

-1.7938

119.86

-11.37

47.08

0.2506

0.812962

1347.98

-2.063

119.89

-13.33

54.33

0.3127

0.808889

1338.11

-2.493

119.87

-16.21

64.19

0.4087

0.800977

1319.2

-2.8817

120.87

-19.62

74.60

0.5054

0.790549

1292.8

-2.8814

123.91

-21.02

76.38

15

ACCEPTED MANUSCRIPT 0.778457

1260.41

-2.7725

128.44

-21.14

72.07

0.7056

0.764975

1223.99

-2.4813

134.59

-19.54

61.80

0.8036

0.750208

1185.32

-2.0719

142.15

-16.48

47.76

0.853

0.742017

1163.26

-1.7836

147.08

-13.82

37.65

0.9073

0.73138

1138.32

-1.1976

153.63

0.9521

0.722881

1117.34

-0.8156

1.0000

0.711509

1091.89

0.0000

0.0000

0.0531

0.820581

1357.31

-0.508

0.1065

0.81792

1349.99

0.1557

0.815371

0.2072

-6.16

14.76

167.66

0.00

0.00

RI P

159.30

SC

1362.88

125.79

0.00

0.00

125.15

-3.38

14.35

-0.9973

124.83

-6.44

26.46

1345.45

-1.4443

124.13

-9.67

39.31

0.812168

1337.03

-1.8127

124.20

-12.25

48.60

0.2506

0.809217

1329.82

-2.0857

124.33

-14.35

55.94

0.3127

0.805088

1319.32

-2.5271

124.47

-17.40

65.66

0.4087

0.797091

1299.95

-2.9318

125.69

-21.12

76.27

0.5054

0.786488

1273.15

-2.9566

129.09

-22.70

78.16

0.6066

0.774268

1240.27

134.08

-22.90

73.79

0.7056

0.760658

1203.4

-2.5326

140.82

-21.25

63.36

0.8036

0.9073 0.9521 1.0000

ED

PT

0.853

NU

0.82305

25.48

MA

0.0000

-9.77

AC CE

303.15 K

T

0.6066

-2.8215

0.745699

1164.23

-2.1108

149.13

-17.98

49.02

0.737323

1141.84

-1.7975

154.60

-15.05

38.65

0.726669

1116.52

-1.2179

161.76

-10.69

26.16

0.717771

1095.27

-0.7645

168.15

-6.60

15.20

0.706633

1069.37

0.0000

177.21

0.00

0.00

308.15 K 0.0000

0.819611

1346.01

0.0000

130.05

0.00

0.00

0.0531

0.817090

1340.36

-0.5167

129.43

-3.67

15.00

0.1065

0.814357

1333.26

-1.0105

129.11

-7.06

27.99

0.1557

0.811747

1328.37

-1.4631

128.48

-10.51

41.04

0.2072

0.808478

1319.81

-1.8364

128.63

-13.32

50.71

0.2506

0.805463

1312.18

-2.1115

128.89

-15.55

58.01

0.3127

0.801268

1300.89

-2.5626

129.25

-18.76

67.45

0.4087

0.793164

1280.99

-2.9789

130.72

-22.79

78.17

16

ACCEPTED MANUSCRIPT 0.782418

1253.56

-2.9746

134.54

-24.52

79.94

0.6066

0.770074

1220.22

-2.8752

140.04

-24.83

75.51

0.7056

0.756326

1182.94

-2.5866

147.41

-23.14

64.95

0.8036

0.741215

1143.21

-2.1603

156.55

-19.64

50.24

0.8530

0.732765

1120.48

-1.8439

162.56

0.9073

0.721983

1094.79

-1.2481

0.9521

0.712948

1073.25

1.0000

0.701737

1047.01

39.59

170.44

-11.69

26.77

-0.7750

177.50

-7.20

15.54

0.0000

187.45

0.00

0.00

1329.05

0.0000

0.0531

0.813576

1324.05

-0.5399

0.1065

0.810775

1317.38

-1.0385

0.1557

0.808103

1311.64

0.2072

0.804762

1303.36

0.2506

0.801687

1295.24

MA

0.3127

0.797424

1283.79

-2.6097

0.4087

0.789210

1262.46

-3.0360

0.5054

0.778328

1233.98

0.6066

0.765858

1199.82

-2.9377

0.7056

0.9521 1.0000

ED

-1.8724 -2.1500

PT

0.9073

-1.4961

-3.0330

AC CE

0.8530

SC

0.816087

NU

0.0000

RI P

-16.46

313.15 K

0.8036

T

0.5054

0.751975

1162.23

-2.6487

0.736701

1121.95

-2.2141

0.728195

1098.97

-1.8975

0.717270

1072.85

-1.2812

0.708129

1050.45

-0.7935

0.696811

1023.80

0.0000

The uncertainty in density, viscosity and speeds of sound is ±2∙10-3 kg∙m-3, ±0.03 mPa∙s and ±0.1 m∙s-1 respectively.

17

ACCEPTED MANUSCRIPT Table6. Viscosities, , viscosity deviations,  and excess Gibbs free energies of activation for viscous flow, G *E for the binary mixture at different temperatures:





G *E

(mPas)

(mPas)

(J mol-1 )

RI P

DIIPA + 1-Hexanol, 298.15 K

T

1

4.439

0.000

0.000

0.0503

3.969

-0.266

19.192

0.1067

3.510

0.1499

3.195

0.2041

2.823

0.2530

2.501

0.3054

2.188

0.4026

1.665

0.4986

1.272

0.6007

SC

0.0000

47.618

-0.636

70.697

-0.788

86.201

-0.912

77.863

-1.013

59.704

-1.141

-30.084

-1.144

-114.718

0.952

-1.050

-209.500

0.718

-0.850

-251.054

0.582

-0.614

-207.758

0.520

-0.463

-160.196

0.471

-0.309

-94.852

0.9545

0.420

-0.147

-54.888

1.0000

0.382

0.000

0.000

0.0000

3.675

0.000

0.000

0.0503

3.366

-0.142

62.509

0.1067

3.018

-0.304

106.042

0.1499

2.751

-0.428

117.635

0.2041

2.438

-0.562

121.843

0.2530

2.171

-0.667

109.200

0.3054

1.900

-0.764

73.324

0.4026

1.475

-0.867

-2.352

0.4986

1.156

-0.869

-58.762

0.6007

0.883

-0.804

-140.349

0.7077

0.675

-0.657

-184.800

0.8518

MA

ED

AC CE

0.9021

PT

0.7077 0.7994

NU

-0.496

303.15 K

18

ACCEPTED MANUSCRIPT 0.547

-0.481

-171.687

0.8518

0.492

-0.363

-130.272

0.9021

0.443

-0.245

-94.091

0.9545

0.401

-0.114

-30.515

1.0000

0.364

0.000

RI P

T

0.7994

308.15 K

0.000

3.107

0.000

0.000

0.0503

2.859

-0.110

59.565

0.1067

2.588

0.1499

2.379

0.2041

2.114

0.2530

1.901

0.3054

1.675

0.4026

1.318

0.4986

1.046

SC

0.0000

111.695

-0.315

131.121

NU

-0.225

126.391

-0.508

123.016

-0.590

88.507

-0.678

16.343

-0.685

-38.060

0.813

-0.636

-107.693

0.628

-0.526

-159.871

0.514

-0.386

-148.736

0.462

-0.294

-119.954

0.420

-0.198

-80.330

0.9545

0.378

-0.094

-43.141

1.0000

0.347

0.000

0.000

0.0000

DIIPA + 1-Octanol, 298.15 K 7.143 0.000

0.000

0.0552

6.422

-0.348

128.832

0.1034

5.774

-0.670

208.270

0.1579

5.107

-0.968

292.555

0.2037

4.510

-1.256

311.480

0.2551

3.898

-1.520

318.022

0.3074

3.339

-1.726

309.533

0.4058

2.441

-1.958

242.004

0.5058

1.758

-1.965

152.284

0.6060

1.265

-1.781

64.291

0.7025

0.916

-1.477

-29.938

ED

0.6007

0.8518

AC CE

0.9021

PT

0.7077 0.7994

MA

-0.430

19

ACCEPTED MANUSCRIPT 0.664

-1.041

-82.374

0.8545

0.571

-0.795

-85.229

0.8931

0.509

-0.596

-87.266

0.9418

0.442

-0.333

-73.542

1.0000

0.382

0.000

RI P

T

0.8044

303.15 K

0.000

5.969

0.000

0.000

0.0552

5.366

-0.294

112.272

0.1034

4.866

0.1579

4.286

0.2037

3.870

0.2551

3.326

0.3074

2.871

0.4058

2.128

0.5058

1.535

SC

0.0000

198.801

-0.799

255.729

NU

-0.524

281.028

-1.213

291.885

-1.375

285.103

-1.566

218.979

-1.599

98.822

1.143

-1.435

51.131

0.840

-1.191

-27.941

0.616

-0.836

-50.632

0.537

-0.638

-48.960

0.487

-0.477

-43.666

0.9418

0.431

-0.263

-21.201

1.0000

0.364

0.000

0.000

ED

0.6060

0.8545

AC CE

0.8931

PT

0.7025 0.8044

MA

-1.011

308.15 K

1.0000

5.01

0.000

0.000

0.0552

4.483

-0.270

84.308

0.1034

4.045

-0.482

144.078

0.1579

3.620

-0.653

224.958

0.2037

3.235

-0.825

244.498

0.2551

2.826

-0.994

244.590

0.3074

2.455

-1.121

237.432

0.4058

1.840

-1.277

166.536

0.5058

1.352

-1.299

59.067

0.6060

1.046

-1.138

-11.399

0.7025

0.760

-0.974

-30.311

20

ACCEPTED MANUSCRIPT 0.580

-0.679

-34.209

0.8545

0.502

-0.523

-27.981

0.8931

0.452

-0.394

-21.811

0.9418

0.401

-0.217

-7.438

1.0000

0.347

0.000

0.0000

DIIPA + 1-Decanol, 298.15 K 11.192 0.000

0.0531

9.942

0.1065

8.911

0.1557

8.093

0.2072

7.186

0.2506

6.335

0.3127

5.184

0.4084

3.737

0.5054

2.653

RI P

T

0.8044

SC

-0.676

0.000 0.000 149.339 323.036

-1.416

493.834

NU

-1.130

583.069

-2.148

646.388

-2.628

697.009

-3.040

683.486

-3.076

647.531

1.752

-2.882

517.130

1.183

-2.382

402.648

0.838

-1.667

286.606

0.689

-1.282

214.850

0.531

-0.853

103.737

0.9521

0.459

-0.441

45.454

1.0000

0.382

0.000

0.000

ED

0.6066

0.853

AC CE

0.9073

PT

0.7056 0.8036

MA

-1.767

303.15 K

0.0000

9.066

0.000

0.000

0.0531

8.148

-0.456

159.426

0.1065

7.421

-0.719

354.345

0.1557

6.670

-1.041

481.889

0.2072

5.835

-1.429

559.892

0.2506

5.168

-1.717

604.272

0.3127

4.271

-2.074

623.454

0.4084

3.133

-2.379

614.021

0.5054

2.228

-2.440

541.356

0.6066

1.522

-2.265

400.475

0.7056

1.059

-1.867

287.564

21

ACCEPTED MANUSCRIPT 0.750

-1.323

212.791

0.853

0.628

-1.016

165.787

0.9073

0.494

-0.677

110.585

0.9521

0.430

-0.351

58.362

1.0000

0.364

0.000

RI P

T

0.8036

308.15 K

0.000

7.459

0.000

0.000

0.0531

6.888

-0.194

211.225

0.1065

6.317

0.1557

5.660

0.2072

4.947

0.2506

4.413

0.3127

3.777

0.4084

2.732

0.5054

2.059

SC

0.0000

407.076

-0.692

509.904

NU

-0.385

567.473

-1.264

614.576

-1.458

637.998

-1.822

618.453

-1.806

567.471

1.375

-1.770

417.186

0.956

-1.485

312.731

0.702

-1.042

243.413

0.587

-0.805

175.774

0.467

-0.539

129.833

0.9521

0.358

-0.330

30.346

1.0000

0.347

0.000

0.000

ED

0.6066

0.853

AC CE

0.9073

PT

0.7056 0.8036

MA

-1.039

The uncertainty in density, viscosity and speeds of sound is ±2∙10-3 kg∙m-3, ±0.03 mPa∙s and ±0.1 m∙s-1 respectively.

22

T

ACCEPTED MANUSCRIPT

IP

0.0

SC R

-0.5

-1

V mx10 (m mol )

-1.0

NU

-6

3

-1.5

E

-2.0

-3.0 0.2

0.4

0.6

0.8

1.0

x1

TE

D

0.0

MA

-2.5

Figure 1. Excess molar volumes ( VmE ) against mole fractions ( x1 ) for DIIPA (1) + 1-

CE P

Hexanol (2) at 293.15(■), 298.15 (●), 303.15 (▲), 308.15 (▼) and 313.15 K (♦). The

AC

smoothing curves have been drawn from equation (10) and dotted curves from PFP theory.

7

ACCEPTED MANUSCRIPT 0.0

-0.5

T

-1

V mx10 (m mol )

-1.0

-6

IP

3

-1.5

-2.5

-3.0 0.0

0.2

0.4

SC R

E

-2.0

0.6

0.8

1.0

MA

NU

x1

Figure 2. Excess molar volumes ( VmE ) against mole fractions ( x1 ) for DIIPA (1) + 1-Octanol(2) at

D

293.15(■), 298.15 (●), 303.15 (▲), 308.15 (▼) and 313.15 K (♦).The smoothing curves have been

AC

CE P

TE

drawn from equation (10) and dotted curves from PFP theory.

8

ACCEPTED MANUSCRIPT

T

0.0

IP

-0.5

SC R

-1.5

NU

-2.0

E

-6

3

-1

V mx10 (m mol )

-1.0

-3.0

-3.5 0.0

0.4

0.6

0.8

1.0

x1

TE

D

0.2

MA

-2.5

Figure3. Excess molar volumes ( VmE ) against mole fractions ( x1 ) for DIIPA (1) + 1-Decanol(2) at

CE P

293.15(■), 298.15 (●), 303.15 (▲), 308.15 (▼) and 313.15 K (♦).The smoothing curves have been

AC

drawn from equation (10) and dotted curves from PFP theory.

9

ACCEPTED MANUSCRIPT

T

0

IP

-1

Ks,m (mm mol MPa )

-5

3

-1

SC R

-10

NU

E

-15

-25 0.0

0.2

MA

-20

0.4

0.6

0.8

1.0

x1

D

Figure 4.Excess molar compressibility ( K SE, m ) against mole fractions ( x1 ) for DIIPA (1)

TE

+ 1-Hexanol(2) (■), + 1-Octanol (2) (●), + 1-Decanol (2) (▲) at 298.15 K. The smoothing

AC

CE P

curves have been drawn from equation (10).

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80

T

70

IP

60

SC R

D

-1

u (msec )

50

40

30

10

0.2

0.4

MA

0 0.0

NU

20

0.6

0.8

1.0

TE

D

x1

CE P

Figure 5. Deviations of speeds of sound ( u D ) from their ideal values against mole fractions (

x1 ) for DIIPA (1) + 1-Hexanol(2) (■), + 1-Octanol (2) (●), + 1-Decanol (2) (▲) at 298.15

AC

K. The smoothing curves have been drawn from equation (10).

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0.0 -0.2

T

-0.4

IP

-0.6 -0.8 -1.0

SC R

-1.4 -1.6 -1.8 -2.0 -2.2

NU

(mPa.s)

-1.2

-2.4 -2.6 -2.8 -3.2 -3.4 0.0

0.2

MA

-3.0

0.4

0.6

0.8

1.0

TE

D

x1

Figure 6.Viscosity deviations (  ) against mole fractions ( x1 ) for DIIPA (1) + 1-

CE P

Hexanol(2) (■), + 1-Octanol (2) (●), + 1-Decanol (2) (▲) at 298.15 K. The smoothing

AC

curves have been drawn from equation (10).

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800

IP

T

600

SC R

-1

G (Jmol )

400

*E

200

NU

0

0.0

0.2

MA

-200

0.4

0.6

0.8

1.0

D

x1

AC

CE P

TE

Figure 7. ExcessGibbs free energy of activation for viscous flow ( G *E ) forDIIPA (1) + 1Hexanol(2) (■), + 1-Octanol (2) (●), + 1-Decanol (2) (▲) at 298.15 K. The smoothing curves have been drawn from equation (10).

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Highlights

T

 Thermodynamic study of diisopropylamine+ 1-Hexanol, + l-Octanol or + 1-Decanol have been made.

SC R

IP

 The partial molar volumes and partial molar isentropic compressibilities at infinite dilution have been calculated.

AC

CE P

TE

D

MA

NU

 Types of interactions were discussed based on derived properties.

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