Abstract: The exothermic behaviors of butanol, butyraldehyde, butanone, and butyric acid with nitric acid were studied by adiabatic accelerating rate calorimeter(ARC), and the test results were compared and analyzed, and the system risk was evaluated by THI index method. The results show that under the condition of the zero oxygen balance, butyraldehyde-HNO₃ system has the most obvious self-exothermic. When the butyraldehyde content is only 0.14 g, the adiabatic temperature of the system rises to 118.4 ℃ and the heat release amount is 776.6 J/g; butanol-HNO₃ system begins to emit heat at about 40.2 ℃, and the highest temperature in the exothermic stage of self-reaction reaches 145.7 ℃ and the maximum pressure reaches about 34 bar(1 bar=10⁵ Pa). Butanone-HNO₃ system releases heat from 50 ℃ to 136 ℃, and the amount of heat released is 564.0 J/g. No exothermic point is observed in butyric acid-HNO₃ system in the temperature range of less than 140.0 ℃. With the increase of nitric acid concentration(2.0→6.0 mol/L), the risk of butanol-HNO₃ system increases from medium to high level. The risks of reaction systems of butanol, butyraldehyde, butanone and butyric acid with 4.0 mol/L HNO₃ are at higher, higher, middle and middle levels.