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Determination of Thermodynamic Parameters of VOSO4 in Different ienc Sc es al J c o i u Gomaa and Rashad, Chem Sci J 2018, 9:2 m r e n a h DOI: 10.4172/2150-3494.1000187 l C Chemical Sciences Journal ISSN: 2150-3494 Research Article Open Access Determination of Thermodynamic Parameters of VOSO4 in Different Organic Mixed Solvents Esam A Gomaa and Radwa Tarek Rashad* Chemistry Department, Faculty of Science, Mansoura University, 35516 Mansoura, Egypt *Corresponding author: Radwa Tarek Rashad, Chemistry Department, Faculty of Science, Mansoura University, 35516 Mansoura, Egypt, Tel: +201060750024; E-mail: [email protected] Received date: March 30, 2018; Accepted date: April 17, 2018; Published date: April 30, 2018 Copyright: © 2018 Gomaa EA, et al. This is an open-access article distributed under the terms of the Creative Commons Attribution License, which permits unrestricted use, distribution, and reproduction in any medium, provided the original author and source are credited. Abstract The measurements of vanadyl sulfate conductance have been in mixed solvent with methanol-H2O (MeOH-H2O), and N, N- Dimethyl formamide (DMF-H2O) in different mass fraction 10%, 30% and 50% at four different temperatures from 298.15 to 313.15K. The experimental data have been analyzed by using the Fuoss-Shedlovsky extrapolation technique. Estimated thermodynamic parameters for association were calculated and discussed. These parameters such as molar conductance (Λm), limiting molar conductance (Λ0), Walden product (Λ0 η0), ion- pair association constant (KA), the activation energy for the transport process (Ea) and the standard thermodynamic parameters for association (∆GoA, ∆HoA and ∆SoA). The different thermodynamic parameters for Vanadyl sulfate were estimated and compared the result of organic solvent over wide range of temperature. Keywords: Ion-pair association constants; Molar conductance; of the solvents. In this paper we found that the nature of ion-solvent Organic mixed solvents; Walden product; Vanadyl sulfate interaction occurring in the medium depend on ion-pairing in salt solutions. Studying association phenomena show the effect of all Introduction parameters on the transport properties of vanadyl sulfate in a binary mixed solvent with alcohol mass fraction 10%, 30% and 50% (MeOH- Studying of thermodynamic properties of solution mixture has great H2O) and (DMF-H2O) at four different temperatures from 298.15 to important in theoretical and applied areas of research and useful in 313.15K (with a step of 5K) by applying the Fuoss- Shedlovsky study of the intermolecular interaction and geometrical effects in the conductivity equation [22]. The association constant is higher in DMF- system, thermo-physical and bulk properties of solution and important H2O than that in MeOH-H2O due to the formation of bulker DMF- in many other fields of industry [1-3]. The Fuoss-Shedlovsky is one of water aggregates that hinder the movement of ions and lead to the the mathematic equation of conductivity theories, which has been formation of ion pairs. successfully used to investigate many electrolytes in solutions [4-9]. The physical properties of the binary mixed solvents like the viscosity Materials and Methods and the relative permittivity can be varied over a wide range making them a favorite solvent system for the study of ion association and ion Vanadyl sulfate (VOSO4. 99.5%), methanol (MeOH, 99.6%), and mobility. Recently, a study of the properties of vanadium compounds (DMF 99.9%) were supplied from Sigma-Aldrich company and used attracts tremendous attention due to its essential in many fields such as without further purification. Bi-distilled water with a specific biochemistry, medical and in many industry [10-12]. It forms conductivity of 0.09 μS cm−1 at room temperature was furthermore numerous inorganic compounds as vanadyl sulfate. Vanadyl sulfate is a used for binary solvents preparation. Specific conductance component of food supplements and experimental drugs. Vanadyl measurements of the salt solutions that previously prepared were sulfate exhibits insulin-like effects [13]. Vanadium compounds exhibit measured using LF 191(Germany) conductivity meter (accuracy ± antitumor or anticarcinogenic properties. Vanadium (IV) oxide sulfate 0.01%) of a cell constant value 1 ± 0% cm−1. The cell constant was is a known inorganic compound of vanadium, which has a high determined with potassium chloride solutions [23-28]. MLW 3230 physiological and industrial importance [14-20]. One of the ultra-thermostat was connected to the Conductivity Bridge to give importance of vanadyl sulfate used in industry as vanadium battery, its constant temperature ( ± 0.006 °C) efforts such as longer life, better stability, higher efficiency and easy Binary mixed solvent of (methanol - water) and (DMF-water) with operation. N, N-dimethylformamide (DMF) is called super solvent, the alcohol mass fractions of 10%, 30%, and 50% were selected to be the with all common polar and nonpolar solvents due to its miscibility. It is solvent media for this study and were prepared by mixing required used in the manufacture of several chemical products and volume of methanol and dimethyl formamide with water (with error ± intermediates as a parent substance [21]. The binary mixed solvents 0.01%) by applying the following equation: (DMF-H2O) are the favorite solvents can be used for studying of ion association and ion mobility, due to the change over a wide range of its Alcohol percentage=(V1d1)100/ (V1d1+ V2d2) (1) physical properties. Investigate ion association by using conductivity Where d and d are the density of alcohol and water respectively. technique enable us to know the factors affecting the thermodynamic 1 2 V is the volume of alcohol which will be added to the volume V of and kinetic stability. These properties depend on the effective size of 1 2 water to get the mixture of the required percentage. The physical the ions, strong ion-solvent interactions as well as change the structure properties, relative permittivity (ε), and viscosity (ηo) of (methanol - Chem Sci J, an open access journal Volume 9 • Issue 2 • 1000187 ISSN: 2150-3494 Citation: Gomaa EA, Rashad RT (2018) Determination of Thermodynamic Parameters of VOSO4 in Different Organic Mixed Solvents. Chem Sci J 9: 187. doi:10.4172/2150-3494.1000187 Page 2 of 6 water) and (DMF- water) with the alcohol mass fractions of 10%, 30%, (Λo) were estimated for vanadyl sulfate solutions in H2O, (DMF-H2O) and 50% at temperatures from 298.15 to 313.15K (with a step of 5K) and (MeOH-H2O) mixed solvents at different temperatures by were tabulated in Table 1 [29-32]. extrapolating the linear Onsager plot [33] between (Λm) and (C)½ as shown in Figure 1. Solvent T/K ε η/m Pa.s 298.15 74.31 0.7459 � 303.15 72.33 0.7018 1 1 ∧ 2 = + � ∧� �=�(�) (3) S∧ �(Z)� (=� )1 + Z∧ 0+ Z2/2∧ 0+ Z3/8 + …… etc. (4) 308.15 70.44 0.6508 10% (MeOH-H2O) 313.15 68.23 0.6107 1/2 298.15 65.4 0.7982 �( ∧� �) � = 3/2 (5) 303.15 63.75 0.7528 Where S,∧ Z,0 and S(Z) are all Fuoss-Shedlovsky parameters. 308.15 61.79 0.6924 The value of (Λο) was used to calculate the Onsager slope (S) from the Equation (6). 30% (MeOH-H2O) 313.15 59.67 0.6541 S = aΛo+b (6) 298.15 55.32 0.841 5 3/2 a = 8.2 × 10 / (εT) (7) 303.15 53.56 0.8321 b = 82.4/ η((εT) 1/2 (8) 308.15 51.54 0.8278 Where (ε) is the dielectric constant of the solvent, (η) is the viscosity 50% (MeOH-H2O) 313.15 49.76 0.8115 of solvent and (T) is the temperature. Using the data of (Λm), S (z) and (Λo), the values of degree of dissociation (α) were calculated by using 298.15 76.1 0.7899 the following equation: 303.15 74.12 0.7451 308.15 72.21 0.691 ∧� �(�) (�) = (9) 10% (DMF-H O) 313.15 70.31 0.6512 ∧ 2 Using these� (α) and (ε) values, the mean activity coefficients (γ±) 298.15 67.05 0.8436 were evaluated by means of Equation (10). 303.15 65.11 0.8036 308.15 63.65 0.7562 �+�−� � log � = − 0 (10) Where Z-, Z+ are� + ��the charges� of ions in solutions A, B are the Debye- 30% (DMF-H2O) 313.15 61.13 0.7123 Hückel constant. 298.15 58.34 0.8765 6 -3/2 A=1.824 × 10 (εT) (11) 303.15 56.76 0.8345 8 -1/2 B=50.29 × 10 (εT) (12) 308.15 54.78 0.8012 50% (DMF-H2O) 313.15 52.56 0.7988 298.15 303.15 68 308.15 67 66 313.15 Table 1: The relative permittivity (ε), and viscosity (η, m Pa.s) at 65 64 different temperatures of the used solvents. 63 62 61 ) 2 60 Results and Discussion .cm 59 -1 58 57 56 The molar conductance (ΛM) for VOSO4 solutions in binary mixed S.mol ( L 55 solvents at different temperatures was calculated by applying Equation 54 53 (2). 52 51 50 49 0.026 0.027 0.028 0.029 0.030 0.031 0.032 1/2 1/2 -3/2 �� − ����� . �����.1000 c (mol .dm ) Where Ks and Ksolv are the specfic conductance of the solution and the ∧� = (2) solvent respectively, �Kcell is the cell constant and C is the molar concentration of the metal salt solution. Figure 1: The plot of (Λ) versus (C1/2, mol1/2 .dm-3/2) in 30% (DMF- H O) solvents for vanadyl sulphate at different temperatures. The experimental conductance data were analyzed by using Fuoss- 2 Shedlovsky conductivity equations. The limiting molar conductance Chem Sci J, an open access journal Volume 9 • Issue 2 • 1000187 ISSN: 2150-3494 Citation: Gomaa EA, Rashad RT (2018) Determination of Thermodynamic Parameters of VOSO4 in Different Organic Mixed Solvents.
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