Bh. Milosavljevic et al., SOME THERMOCHEMICAL AND STRUCTURAL-PROPERTIES OF PENICILLIN-V BENZATHINE TETRAHYDRATE, Thermochimica acta, 230, 1993, pp. 319-330
The thermochemical and structural properties of penicillin V benzathin
e tetrahydrate were studied in the temperature interval from 20 to 200
-degrees-C. It has been found that, on increasing the temperature, the
penicillin undergoes two phase transitions before reaching the meltin
g point. The first is accompanied by complete dehydration and the corr
esponding structural changes are small, whereas the penicillin's cryst
al lattice before and after the second transition, as determined by X-
ray diffraction, differs significantly. The overall enthalpy change is
250 J g-1. Both transitions are reversible; the penicillin can be suc
cessively heated and cooled an indefinite number of times, retaining i
ts chemical and structural properties, provided that the temperature d
oes not exceed 100-degrees-C. From differential scanning calorimetry d
ata one cannot resolve the kinetic parameters of the two phase transit
ions; the overall process is second order and the activation energy is
207 kJ mol-1. Carroll-Freeman analysis of the thermogravimetric data
indicates that the reaction order of the dehydration is 0.6 and the ac
tivation energy is 111 kJ mol-1. All these parameters were obtained at
a 1.25-degrees-C min-1 heating rate. The enthalpy of fusion of the an
hydrous penicillin is 45 kJ mol-1. The seeming inconsistency of the X-
ray data with the DSC data is found to be related to the very pronounc
ed effect of heating rate on the kinetics, and is explained in detail.