Abstract Some problems on designing physical chemistry exercises were introduced. One is that the special subject of exercises is too strong and the comprehensiveness is insufficient. In addition, in the thermochemistry and so on chapters, the main chemical reactions in exercises are gas phase reactions or gas-solid phase reactions,but the aqueous phase reactions are very few. The comprehensive exercises for chemical thermodynamics had been designed taking daniell cell as an example, which enhanced the relationships between chemical thermodynamics and electrochemistry. And the knowledge points of chemical thermodynamics were related as for as possible. This design of comprehensive exercises for chemical thermodynamics may be useful for arousing students' learning interests, deepening the understanding of contents and promoting students teaching reforms of physical chemistry.