Aug 17, 2017 - Walden product. Mixed solvents. Free enthalpy of complexation. *Corresponding author: â A. Shokr e-mail: abdo_shokr@ mans.edu.eg, Tel: + ...
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Effect of calcon carboxylic acid on association process of vanadyl sulfate in water-N, N-dimethyl formamide mixed solvents E.A. Gomaa , R.R. Zaky , A. Shokr PII: DOI: Reference:
S2405-8300(17)30062-9 10.1016/j.cdc.2017.08.002 CDC 73
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Received date: Revised date: Accepted date:
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Please cite this article as: E.A. Gomaa , R.R. Zaky , A. Shokr , Effect of calcon carboxylic acid on association process of vanadyl sulfate in water-N, N-dimethyl formamide mixed solvents, Chemical Data Collections (2017), doi: 10.1016/j.cdc.2017.08.002
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Effect of calcon carboxylic acid on association process of vanadyl sulfate in water‐N, N‐dimethyl formamide mixed solvents. E. A. Gomaa, R. R. Zaky, A. Shokr * Chemistry Department, Faculty of Science, Mansoura University, 35516-Mansoura, Egypt
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Abstract The complexation reaction between calcon carboxylic acid (CCA) and vanadyl sulfate was studied in water and mixed water‐N, N‐dimethyl formamide mixed solvents (DMF-H2O) using conductometric measurements. The experimental data are already analyzed with the use of Fuoss-Shedlovsky technique in absence and presence of
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CCA. The ion-pair association (KA), and also the standard thermodynamic parameters for association (∆GoA, ∆HoA and ∆SoA) were estimated and compared in absence and presence of CCA. The main difference between Gibbs free energy of association in the presence and the case of absence of CCA indicate the value of free enthalpy of complexation (∆Gocomplexing). Walden product (Λ0 η0), hydrodynamic radii (RH) and
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the energy of activation (Ea.) were also calculated. This work provides the suggested structure of the complex based on elemental analyses and spectral study (IR) which
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provide the thermodynamic results with useful discussion. CCA act as binegative tetradentate coordination.
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Keywords: Vanadyl sulfate .Molar conductance. Ion-pair association. Binary Mixed solvents. Walden product. Mixed solvents. Free enthalpy of complexation. *
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Corresponding author: A. Shokr e-mail: abdo_shokr@ mans.edu.eg, Tel: +201004290742
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Specifications table Subject area
Physical chemistry
Compounds
vanadyl sulfate, DMF and calcon carboxylic acid
Data category
Thermodynamics
Data acquisition format
Conductance data analysis to calculate thermodynamic parameters
Data type
Analyzed
1
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Conductance study
Data accessibility
Data is with this article
1 Rationale
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Metal ions play a vital role in bio-inorganic chemistry and provide the basis of models for active sites of the biological system [1-3]. The electrolyte of vanadium battery is the core of it in energy storage and energy conversion because it is the electroactive substance which could realize energy storage. So, the critical nature of vanadium battery like charge–discharge efficiency, service life and
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energy density depend on the thermodynamic study of vanadyl sulfate [4–9]. (KA) and the thermodynamic parameters are essential where these salts work well in several applications such as pharmaceutical industries and water purification …etc. Study of ion association enables us to investigate the factors affecting the thermodynamic and kinetic stability. The quality of the water in those applications
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which required water contain no or limited ions, including in the pharmaceutical, sea water desalination, etc. can be determined by The conductometric study [10].
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Studying the conductance, viscosity, and ionic mobility (transport properties) of electrolytes in an aqueous and partially aqueous system are very useful not only
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explain ion-ion and ion-solvent interactions in these solutions, but also the preferential solvation of ions [11]. N, N-dimethylformamide (DMF) is called
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super solvent, due to its miscibility with all common polar and nonpolar solvents. It is used in the manufacture of several chemical products and intermediates as a
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parent substance [12]. The binary mixed solvents (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 in its physical properties 2. Experimental procedure 2.1 Conductivity measurements of mixed solvents The binary mixed solvents of (DMF-H2O) with the DMF mass fractions of 0% and 50% were chosen to be the mixtures used in presence and absence of CCA and were prepared by mixing required volume of DMF and water (with error ± 0.02%) . 2
ACCEPTED MANUSCRIPT DMF percentage is equal to the term (V1d1)100 / (V1d1+ V2d2). Where d1 is the density of DMF and d2 is the density of H2O. V1 and V2 are the volumes of DMF and H2O respectively. The physical properties of the used mixed solvents at working temperatures were collected in Table 1 [31-33]. All electrical conductance carried out by the use of LF 191(Germany) conductivity meter (accuracy ± 0.01%) of a cell constant value 1±10% cm−1. The cell constant was determined with potassium chloride solutions. The temperature of mixtures under study was maintained constant
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using a MLW 3230 ultra-thermostat with an accuracy of ± 0.006 0C. 2.2 Chemicals
Deionized water was distilled and used in the preparation of the mixtures with a specific conductivity of 0.07 μS cm−1 at 298.15 K. (DMF 99.9%), Vanadyl sulfate
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trihydrate (VOSO4.3H2O, ≥ 99.9%) and calcon carboxylic acid were purchased from Sigma-Aldrich and also were used as such without further purification and Potassium chloride (KCl, 99%) were supplied from Riedel-de Haën company (Germany) and also were used without further purification.
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2.3 Preparation of complexes
The complex of CCA with vanadyl sulfate is prepared by mixing equimolar amounts
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of ligands with ethanolic and aqueous solution of CCA and Oxo-aqua-cation VO2+. This reaction mixture was refluxed at 80−85 °C for 3 h., which was filtered, washed,
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the resulting precipitate was filtered off
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Table 1 The Density (ρ, g.cm−3), relative permittivity (ε) and viscosity (η, mPa s) of water and 50% (DMF -H2O) at working temperatures. Solvent T/K ρ/g cm- ε η/mPa s 3 0% (DMF-H2O)
298.15 303.15 308.15 313.15
0.9970 0.9942 0.9912 0.988
78.3 76.51 74.76 73.05
0.8904 0.7975 0.7194 0.6529
50% (DMF -H2O)
298.15 303.15 308.15 313.15
0.9231 0.9193 0.9142 0.9034
58.34 56.76 54.78 52.56
0.8765 0.8345 0.8012 0.7988
3
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3. Description of the data 3.1 Estimate the association constant The molar conductance (ΛM) for Vanadyl sulfate solutions in binary mixed solvents was calculated by applying Eq. (1). )⁄
(1)
The specific conductance of solution is denoted by Ks.
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)
((
The specific conductance of the solvent is denoted by Ksolv.
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The cell constant is denoted by Ks. .C is the molar concentration of the metal salt solution.
The experimental conductance data were analyzed through the use of FuossShedlovsky extrapolation technique. The limited molar conductance determined from
⁄
( ⁄
( )
)
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the linear Onsager plot [36] as shown in Fig. 1 and Fig. 2 (
⁄
)(
( ))
(
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S (Z) = 1 + Z + Z2/2 + Z3/8 + …… etc. )
⁄
⁄
(2) (3) (4)
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Where(S, Z) are the Fuoss–Shedlovsky parameters, (A) and the value of ( o ) was
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used to calculate the Onsager slope (S) from the Eq. (5) S = ao + b
(5)
a = 82 x 104 / (T) 3/2
(6)
b = 82.4/ ((T) 1/2
(7)
Where (ηo) is the viscosity of the solvent, () is the relative permittivity of the used solvent and (T) is the temperature. Using the values of () and (ηo), the value of (S) were easily estimated. Using the data of (Λm), S (z) and (Λo), the values of degree of dissociation (α) were calculated by using the following equation:
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ACCEPTED MANUSCRIPT ( )⁄
𝛼
(8)
From the Debye-Hückel equation (9), the mean activity coefficients (γ±) can be determined. √ ⁄
√
(9)
A = 1.824 X 106 (T)-3/2
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(10)
B = 50.29 X 108 (T)-1/2
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(11)
absence of CCA presence of CCA
340 320
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280 260 240 220 200
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180
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2
-1
S. cm .mol )
300
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0.025
0.026
0.027
C
0.028
1/2
0.029
0.030
0.031
0.032
1/2 3/2 (mol /dm )
Fig. 1 The plot of (Λ) versus (C1/2, mol1/2 .dm-3/2) in water for vanadyl sulfate in absence and
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presence of CCA at 298.15 K.
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absence of CCA precence of CCA 140
-1
S. cm .mol )
120
2
100
60
40 0.025
0.026
0.027
C
0.028
1/2
0.029
0.030
1/2 3/2 (mol /dm )
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80
0.031
0.032
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Fig. 2 The plot of (Λ) versus (C1/2, mol1/2 .dm-3/2) K in 50% mixed (DMF–H2O) solvents for
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vanadyl sulfate in absence and presence of CCA at 298.15.
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Table 2 Association constant (KA, ±0.25%), Walden product (Λoη, S. mol-1 cm2 Pa.s) and the hydrodynamic radii (RH) in water for vanadyl sulfate in absence of CCA at working temperatures. Solvent T/K KA Λoη RH(A) 298.15 303.15 308.15 313.15
3327.86 3462.23 3605.80 3658.24
365.24 422.65 435.11 443.76
0.0000 0.0037 0.0036 0.0018
298.15 303.15 308.15 313.15
348.36 567.61 656.86 947.762
40.33 43.27 73.42 77.62
0.0314 0.0325 0.0333 0.0105
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0% (DMF-H2O)
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50% (DMF-H2O)
Table 3 Association constant (KA, ±0.25%), Walden product (Λoη, S. mol-1 cm2 Pa.s) and the hydrodynamic radii (RH) in water for vanadyl sulfate in presence of CCA at working temperatures. Λ oη
Solvent
T/K
KA
0% (DMF-H2O)
298.15 303.15 308.15 313.15
24788.98 24788.57 24746.37 24429.38
626.51 550.53 501.21 642.74
0.0007 0.0030 0.0033 0.0012
50% (DMF-H2O)
298.15 303.15
79823.54 75674.27
203.35 233.15
0.0037 0.0037
RH(A)
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206.31 415.71
70780.40 69210.02
0.0000 0.0019
The outcome data showed in Tables 2, 3 indicated that. It is observed that the values of association constant (KA) increase with increasing in temperature which indicates an endothermic association process. Also this temperature dependence of the association process of ions can be explained on the basis of the interplay between
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dehydration and association of ions whereas the temperature increases, the dehydration and/or desolvation process of ions take place, then the ions will have short distance of contact, therefore the association of ions increases [10,3 7, and 38]. But in presence of CCA the association process become exothermic and the association constant decrease with increase temperature and also prove that the value
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of enthalpy.
It was found through conductometric data analysis show more association or ion pair formation increase in presence of CCA which lead to decrease of ions mobility,
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giving a chance for ions to associate.
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3.2 Walden product calculated
Ion-solvent interaction can be explained from Walden product so Walden product is
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very important and can be calculated from Eq. (12) [12, 19].
[ ⁄
⁄
].
(12)
The radius of a hypothetical sphere was denoted by r, which diffuses with the same
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speed, as the particle under study and the hydrodynamic radii (RH) of the ions is equal to the term ⁄[ ⁄
⁄
]. The values of Walden product and hydrodynamic radii
for vanadyl sulfate was calculated and represented in Table 2, 3. The inverse values of the hydrodynamic radii with Walden product was explained by many authors [20-21]. Most values of the Walden product showed that by increasing temperature the Walden product values increase in water. This related to Walden product are affected by two factors, limiting molar conductance and viscosity and the mobility of ions increasing greatly in presence of DMF leading to increasing limiting molar 7
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absence of CCA precence of CCA
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4.4
-1
Log KA / (dm .mol )
4.2
3
4.0
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3.8
3.6
3.4 0.00320
0.00325
0.00330
0.00335
-1
M
(T / K)
absence of CCA presence of CCA
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5.0
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Fig. 3 Relation of (logkA) vs. (1/T) in water for vanadyl sulfate.
-1
Log KA / (dm .mol )
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4.5
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3
4.0
3.5
3.0
2.5 0.00320
0.00325
0.00330
0.00335
-1
(T / K)
Fig. 4 Relation of (logkA) vs. (1/T) in mixed solvents 50 % (DMF-H2O) for vanadyl
sulfate. 8
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3.3 Thermodynamics parameters of ion pair association The standard Gibbs free energy of association (ΔG°A) was calculated by using Eq. were tabulated in Table 4 ΔG°A = - RT lnKA
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(11) for all salts under study in all solvent mixtures at all temperatures and its values
(13)
Where R is the gas constant and equal (8.314 J.mol-1. K-1).
were obtained from equation (14) (
⁄
)
(
⁄
)
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Standard entropy (ΔS°A) and the Standard enthalpy (ΔH°A) of association process
(14)
By plotting the relation between (log KA) and (1/T) as shown in Fig. 3 and Fig. 4. The
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enthalpy can be calculated from the slope, where the slope is equal to the term of (−ΔHA/2.303R). The entropies of association (ΔS°A) were calculated by the use of
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Gibbs– Helmohltz equation Eq. (15).
ΔG°A = ΔH°A − TΔS°A
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(15)
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The difference between ΔG° in presence and absence of ligand indicate the value of free enthalpy of complexation (∆Gocomplexing).
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The decrease in (ΔG0) values for vanadyl sulfate to more negative values
with increasing temperature favors the transfer of the released solvent molecules into bulk solvent and leads to a smaller (ΔG0) values. In absence of CCA the positive value of (ΔH°A), indicates the ion association processes are endothermic in nature. But in presence of CCA the process become exothermic process this may be related to the solution become crowded and CCA molecules help the ions to associate. A positive entropy values (ΔS°A) can be explained on the assumption that iceberg structure around the cation is broken when association takes place leading to an increase in the
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ACCEPTED MANUSCRIPT degree of disorderliness. The values of entropy in presence of CCA are greater than in absence of CCA. This may be related to CCA make control on the mobility of ions. The energies of activation of the conducting process obtained from the Arrhenius relationship,
⁄
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(16)
The frequency factor is denoted by A. The gas constant is denoted by R.
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The Arrhenius activation energy of the transfer process is denoted by Ea.
The values of activation energy Ea can be obtained by plotting the relation between (log Λ0) and (1/T).The obtained values of Arrhenius activation energy of the transfer process of the studied salt in all mixtures are reported in Table 4. The behavior of
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limiting molar conductance of activation energy change is inverse that of activation energy. Many authors explained the change in the activation energy of transfer [37,
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21]. The smaller values of activation energy may be related to the presence of CCA
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help the process to take place.
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Table 4 The thermodynamic parameters of association (ΔG°A, ±0.33%), (ΔH°A ±0.22%), (ΔS°A ±7.42%) and activation energy (Ea/KJ.mol-1) in the mixtures used at
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working temperatures for vanadyl sulfate in absence of CCA. Solvent
0% (DMF-H2O)
50% (DMFH2O)
T/K 298.15 303.15 308.15 313.15 298.15 303.15 308.15 313.15
Ea
ΔH°A
ΔG°A
(KJ.mol-1)
(KJ.mol-1)
3.33
5.046
5.30
63.00
10
ΔS°A
(KJ.mol-1)
(J.mol-1)
-20.1071 -20.544 -20.987 -21.365
84.366 84.416 84.484 84.342
-14.5117 -15.9858 -16.6236 -17.8481
260.00 260.57 258.41 258.20
ACCEPTED MANUSCRIPT Table 5 The thermodynamic parameters of association (ΔG°A, ΔG0complexing ±0.33%), (ΔH°A ±0.22%), (ΔS°A ±7.42%) and activation energy (Ea/KJ.mol-1) in the mixtures used at working temperatures for vanadyl sulfate in presence of CCA.
0% (DMF-H2O)
50% (DMF-H2O)
T/K 298.15 303.15 308.15 313.15 298.15 303.15 308.15 313.15
ΔH°A
Ea
ΔG°A
(KJ.mol-1)
(KJ.mol-1)
3.27
-0.7004
3.41
-7.69849
ΔS°A
ΔG0complexing
(KJ.mol-1)
(J.mol-1)
(KJ.mol-1)
-25.085 -25.085 -25.081 -25.049
81.788 81.788 81.774 81.666
-27.9849 -27.852 -27.686 -27.631
-4.5410 -4.0940 -3.6840
68.040 67.597 67.041 66.854
-13.473 -11.866 -11.063 -9.7829
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3.4 Suggested structure of CCA complex
-4.9779
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Solvent
The suggested structure of the complex in Fig. 5 depend on change in physical and chemical properties of the ligand in Fig. 6. The most important infrared bands of CCA and its metal complexes at 1666, 3453, 3284 and 1397 assigned to υ(C=O), υ(OH)1,
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υ(OH)2, υ(N=N). In VOC21H16N2O9S complex CCA act as binegative tetradentate via the two phenolic (OH) group, hydroxo of carbooxlic group and N=N .This mode of chelation is based on the lower in vibration of υ(OH)2, (N=N), (C=O) and
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disappearance of band (OH) 1
Fig. 5 Structure of CCA
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Fig. 6 Suggested Structure of the complex
Conclusions
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Conductivity measurements for vanadyl sulfate in (DMF-H2O) mixtures of 0%, 30%, at different temperatures in presence and absence of calcon carboxylic acid
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have been reported. Thermodynamic parameters (ΔH0, ΔG0, ΔS0) were calculated association constant (KA) by using Fuoss – Shedlovsky equation and discussed and
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estimate the values of free enthalpy of complexation. The presence of CCA effect on the behavior of the vanadyl sulfate in the mixtures used. The positive values of (ΔH 0) for vanadyl sulfate in absence of CCA show that the association processes are endothermic in nature but in presence of CCA association processes are exothermic. This indicate the effect of electron donor-acceptor interaction of CCA with Oxo-aquacation VO2+.
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