The first esterification reactor in the continuous polymerization of poly(ethylene terephthalate) has been analyzed by solving the material balances for the two-phase system with respect to the solubility of terephthalic acid. The Newton-Raphson method was used to solve the material balance equations instead of the Simplex method that is frequently used for finding a minimum point of a residual rather than a solution of an equation. A solution for the material balance equations, with the constraint of non-zero liquid phase fraction, could not be obtained with the solubility data of Yamada et al., but could be obtained with solubilities over a minimum value that is larger than their data. Thus, the solubility data of Yamada et al. are considered to be too small. On the other hand, the solubility data of Baranova and Kremer are so large that they gave a solution with the liquid phase only. Based on our results, several typical solubility curves satisfying the constraint of a non-zero liquid phase fraction are suggested in this study; we studied the reaction characteristics of the system using these curves. A higher temperature and a lower pressure are preferred for reducing the content of diethylene glycol.