The simple binary mixtures of pure phospholipids such as DPPC:DSPC and DPPC:DPPA were investigated with differential scanning calorimeter. The thermotropic properties of DPPC and DSPC mixtures did not deviate much from the ideal curves that was obtained on varying either the temperature or the relative proportions of phospholipids. This means that the two phospholipids are completely miscible in the liquid and solid phase. But the thermotropic properties of DPPC and DPPA mixture deviated much from the ideal phase diagram. It resulted from the repulsion between the head groups of acidic phospholipids. Heat capacity suggested by Harden McConell was calculated. The larger $C_p$ was, the sharper the endothermic peak became.