Fig. 4. The graph of against wjk’s of amine

Fig. 4. Thegraph of   against wjk’sof amine and acetonitrile mixture in benzene at 30°C under microwave field. (I)¾¾  (II)¾·¾ (III)¾¾ for N-methyl aniline, aniline, N, N-dimethyl anilinemixed with acetonitrile respectively.

 Fig. 5. The plot of against for various wjk’s of amine and acetonitrilemixture in benzene at 30°C under microwavefield. (I)¾¾  (II)¾·¾  (III)¾¾ for N-methyl aniline, aniline,N, N-dimethyl aniline mixed with acetonitrile respectively. Fig.

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6. Variations of  as well as against different wjk’s of amine andacetonitrile mixture in benzene at 30°C under microwavefield. (I)¾¾  (II)¾·¾  (III)¾¾ for N-methyl aniline,aniline, N, N-dimethyl aniline mixed with acetonitrilerespectively. µ’s are calculatedfrom Eq. 6 and placed in TABLE III 10. It is observed from TABLE III that µ’sshow high value for N, N-dimethylaniline (j) and acetonitrile (k) mixturein   C6 H6 incomparison to other polar- nonpolar mixture. It may occurred due to solute-solute(dimer) molecular association or complex formation for microscopicinhomogeneity of binary polar mixture occurring in certain concentration. This eventuallyinfluences the viscosity of solvent exhibiting higher µ’s due to larger size ofthe rotating unit.

Thus the dipole-dipole interaction occurs in such a way thatthe effective dipole moments get increased. The charge transfers from thefragments of the atoms may also be responsible for the interacting environment.The solute-solvent (monomer) molecular association may occur due to interactionof the fractional positive charge (d+) at thesite of N atom of amine or N atom of acetonitrile and the p delocalized electron cloud  inbenzene ring as shown in Fig. 7 (a) & 7 (b) respectively. The solute-solutemolecular association as evident from Fig.

7 (c) may arise due to theacetonitrile and N-methyl aniline molecule. N-methyl aniline and acetonitrilemolecules undergo self-association as shown in Fig. 7(d) & 7(e). Thethermodynamic energy parameters like DFt’s and DF?’s were calculated fromEq. 7 & 8. The estimated DF?>DFt for all polar-non polar mixturessignifying the fact that viscous flow involves both rotational andtranslational motion whereas dielectric relaxation involves with rotation only.

  a)          b)         c)          d)         e)           Fig. 7: Various molecular associations. (a) N-methyl aniline +C6H6(b) acetonitrile +C6H6 (c) N-methyl aniline +acetonitrile (d) N-methyl aniline + N-methyl aniline, (e)acetonitrile + acetonitrile