Dielectric Properties of Binary Solutions. A Data Handbook
The non-linear behaviour of these parameters for mixtures with a pentanol mole fraction represents the hetero-association of polar solvent molecules.
11.1: Ions in Solution (Electrolytes)
A complex of alkylbenzoate with 2-pentanol and 3-pentanol has lower number of dipoles in solution than 1-pentanol and thus, there is a decrease in the molar volume of the rotating entity. The relaxation time reflects that the reorientation of the —OH group of 1-pentanol in a binary mixture with alkylbenzoate is more pronounced than it is for 2-pentanol and 3-pentanol. The dielectric parameters were used in calculating the excess permittivity, excess inverse relaxation time, Kirkwood correlation factor, and Bruggeman factor.
These dielectric results were used in interpreting the molecular interaction of the binary mixture with different dipoles in the liquid state.
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Among polar solvents, alcohols are widely used as solvents and undergo self-molecular association by dipole—dipole interactions and hydrogen bonding through the —OH group. Thus alcohols play an interesting role in chemistry and biology and have been the topic of several studies to understand their associative properties with multiple internal structures which depend on the carbon chain length and the position of the —OH group.
This interacting pair plays an important role in biological systems and drug synthesis. In the present work, the effect of the addition of alkylbenzoates with increasing alkyl chain length [methylbenzoate MB , ethylbenzoate EB , propylbenzoate PB and butylbenzoate BB ] on the self-association of pentanol [1-pentanol 1P , 2-pentanol 2P and 3-pentanol 3P ] has been studied at different mole fractions. This study has been carried out with the evaluation of the dielectric parameters of excess permittivity, excess inverse relaxation time, Kirkwood correlation factor and Bruggeman factor.
These parameters were used in interpreting the molecular interaction of binary liquid mixtures.
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This study provides information regarding the influence of the —OH group position in pentanol on the pentanol—alkylbenzoate structure. The plot of f B vs. The Kirkwood correlation factor g , 18 is related to the dielectric relaxation parameters and is useful for obtaining information on the liquid structure, molecular orientation and electric dipole orientation in polar solvents. For a binary mixture of polar solvent 1 and 2, the effective Kirkwood correlation factor g eff can be expressed as The g eff is affected by an amount g f in a mixture.
The corrective Kirkwood correlation factor g f is expressed as. In a mixture the reorientation of the constituent solvent molecules cooperatively happens through the hydrogen bonding of the —OH group of pentanol and —CO group of the alkylbenzoates. The excess parameters, 23 namely excess permittivity and excess inverse relaxation time, are useful in obtaining information regarding the two polar solvent interactions in the mixture.
The subscripts m, 1 and 2 signify mixture, pentanol and alkylbenzoate respectively. It may lead to multimer formation in the mixture.
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It may lead to multimer and dimer formation. A similar increase in the static dielectric constant value of the mixture of 1P, 2P and 3P with water was also observed where all three isomers gave a different static dielectric constant value with the same concentration. It is also observed that a change in the static dielectric constant of the mixture is non-linear with the mole-fraction X 1 of 1-pentanol, 2-pentanol and 3-pentanol when mixed with methylbenzoate MB , ethylbenzoate EB , propylbenzoate PB and butylbenzoate BB.
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The increase in the static dielectric constant with increasing solvent in a binary solvent mixture signifies that spherical molecular aggregates transform to more correlated elongated aggregates resulting in a parallel orientation of the dipoles. The static dielectric constant value for 2-pentanol and 3-pentanol is smaller when compared to that for 1-pentanol. This may be due to a decrease in the number of dipoles of the complex formed in the solution and thus, there is a decrease in the molar volume of the rotating entity. From Fig. This reflects that with the alkylbenzoate having a longer alkyl group, the number of complex dipoles decreases, thus decreasing the molar volume of the rotating group.
X 1 see Fig. A non-linear result of a static and high frequency dielectric constant with increasing alcohol concentration for the hetero-association of an alcohol with other polar solvents is reported in the literature. In Fig. This indicates that the reorientation of the —OH group of pentanol depends to some extent on the position of the —OH group in the pentanol backbone. The reorientation of molecules in the mixture is more for the primary alcohol 1-pentanol than in the secondary alcohols 2-pentanol and 3-pentanol when mixed with alkylbenzoates of different alkyl chain length.
Part a of the figure shows what happens when a battery is connected through an electrical meter to two inert metal strips electrodes dipping in ethanol. Each cubic decimeter of such a solution contains 0. The dial on the meter indicates the quantity of current.
Figure 1 b shows that if we replace the 0. Halving the concentration of NaCl halves the number of ions between the electrodes, and half as many ions can only carry half as much electrical charge. Therefore the current is half as great.
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Because it responds in such a direct way to the concentration of ions, conductivity of electrical current is a useful tool in the study of solutions. Conductivity measurements reveal that most covalent compounds, if they dissolve in water at all, retain their original molecular structures.
Neutral molecules cannot carry electrical charges through the solution, and so no current flows. A substance whose aqueous solution conducts no better than water itself is called a nonelectrolyte. Some covalent substances behave as weak electrolytes —their solutions allow only a small current flow, but it is greater than that of the pure solvent.
An example is mercury II chloride seen in the Figure above. For a M HgCl 2 solution the meter reading shows only about 0. When the solid dissolves, most of these molecules remain intact, but a few dissociate into ions according to the equation. The double arrows indicate that the ionization proceeds only to a limited extent and an equilibrium state is attained. Since only 0. Conductivity measurements can tell us more than whether a substance is a strong, a weak, or a nonelectrolyte.
At the rather low concentration of 0.
Closer examination of the data for strong electrolytes reveals that some compounds which contain H or OH groups [such as HCl or Ba OH 2 ] conduct unusually well. A potential difference of 1. There is a simple reason for this behavior.
Under similar conditions, most ions move through water at comparable speeds. Consequently, a 0.