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1.3.2 Reverse pH Jumps from Equilibrium
ОглавлениеFrom eq. (36) to eq. (38) all equilibrium constants except those regarding the trans‐chalcones can be obtained. Moreover, the cis‐trans isomerization constants can be calculated from a reverse pH jump from the equilibrated solutions. Considering that formation of the flavylium cation from the trans‐chalcones is very slow, this kinetics should be followed by a standard spectrophotometer. The quinoidal bases, hemiketals, and cis‐chalcones are transformed to flavylium cation much faster than the trans‐chalcones and appear as an initial absorption.2 From this point all the equilibrium constants have been calculated. The mole fraction of trans‐chalcone is thus obtained from the ratio of the absorbance of the trace amplitude/total absorbance. The mole fractions of the other species at equilibrium are obtained from those at pseudo‐equilibrium, calculating the respective proportion.3 For example, if at pseudo‐equilibrium A=0.3, B=0.2, and Cc=0.5 and the mole fraction of Ct at equilibrium is 0.5, the mole fractions of A, B, and Cc at equilibrium are the following: A=0.15, B=0.1, and Cc=0.25.