Title |
DETERMINATION OF THE DISSOCIATION CONSTANTS OF SOME p-SUBSTITUTED AROMATIC HYDRAZONES |
Author/s |
Mirjana Jankulovska, Ilinka Spirevska, Katica Cholancheska Ragjenovikj |
Citation |
M. Jankulovska, I. Spirevska and K. Cholancheska Ragjenovikj, "DETERMINATION OF THE DISSOCIATION CONSTANTS OF SOME p-SUBSTITUTED AROMATIC HYDRAZONES", Contributions, Sec. Math. Tech. Sci., MASA, ISSN 0351–3246, Vol. 32, no.1-2, 2011, pp.23-43. |
Abstract |
The acid-base behavior of five p-substituted
aromatic hydrazones has been studied, using UV spectrophotometric
method. The influence of the acidity of the medium on the
absorption spectra is followed in aqueous sodium hydroxide
solutions in pH region from 7 to 14. The measurements are
performed at room temperature, and at ionic strength of 0.1, 0.25
and 0.5 mol dm–3. A batochromic shift of the absorption band that
appears in neutral media is observed, when pH is up to 7. It
suggests that the dissociation process of the amide and hydroxyl
group takes place. Deprotonation enthalpies and total energy
values are calculated by using the semiempirical methods AM1
and PM3. Using the changes in the UV spectra with pH of the
solution, the determination of dissociation constants, pKBH, at
three different ionic strengths, as well as, the thermodynamic
dissociation constants at zero ionic strength, is performed. In order
to obtain more precise results, the calculations are made from the
absorbance values at four selected wavelengths. Furthermore, the
pKBH values were determined graphically from the intercept of the
dependence of logI on pH. The results showed that the numerically
calculated pKBH values are identical to those graphically obtained.
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Keywords |
p-substituted aromatic hydrazones, dissociation, UV spectrophotometry, dissociation constants, thermodynamic dissociation constants, semiempirical methods AM1 and PM3 |