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Fig. 4. The
graph of   against wjk’s
of 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 aniline
mixed with acetonitrile respectively.

 

Fig. 5. The plot of against for various wjk’s of 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 aniline mixed with acetonitrile respectively.

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Fig. 6. Variations of  as well as against different wjk’s of 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 aniline mixed with acetonitrile
respectively.

 

µ’s are calculated
from Eq. 6 and placed in TABLE III 10. It is observed from TABLE III that µ’s
show high value for N, N-dimethylaniline (j) and acetonitrile (k) mixture
in   C6 H6 in
comparison to other polar- nonpolar mixture. It may occurred due to solute-solute
(dimer) molecular association or complex formation for microscopic
inhomogeneity of binary polar mixture occurring in certain concentration. This eventually
influences the viscosity of solvent exhibiting higher µ’s due to larger size of
the rotating unit. Thus the dipole-dipole interaction occurs in such a way that
the effective dipole moments get increased. The charge transfers from the
fragments of the atoms may also be responsible for the interacting environment.
The solute-solvent (monomer) molecular association may occur due to interaction
of the fractional positive charge (d+) at the
site of N atom of amine or N atom of acetonitrile and the p delocalized electron cloud  in
benzene ring as shown in Fig. 7 (a) & 7 (b) respectively. The solute-solute
molecular association as evident from Fig.7 (c) may arise due to the
acetonitrile and N-methyl aniline molecule. N-methyl aniline and acetonitrile
molecules undergo self-association as shown in Fig. 7(d) & 7(e). The
thermodynamic energy parameters like DFt’s and DF?’s were calculated from
Eq. 7 & 8. The estimated DF?>DFt for all polar-non polar mixtures
signifying the fact that viscous flow involves both rotational and
translational 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

 

 

 

 

 

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