It has been found that the two-phase reactions of aqueous HCl, HOAc or H_3PO_4 with primary amine N_ 1923 in chloroform are oscillating reactions. Their power-time curves were measured by the titration microcalorimet...It has been found that the two-phase reactions of aqueous HCl, HOAc or H_3PO_4 with primary amine N_ 1923 in chloroform are oscillating reactions. Their power-time curves were measured by the titration microcalorimetric method, and the induction period (t_ in). The first oscillating period (t_ p.1) and the second oscillating period (t_ p.2) were determined. The apparent activating parameters and the orders of the oscillating systems were calculated and the following relationships were established: for the oscillating system of hydrochloric acid t_ in∝c 0.147_ HClexp(1.35×10 3T), t_ p.1∝c 0.241_ HCl· exp(4.33×10 3T), t_ p.2∝c 0.290_ HClexp(5.59×10 3T); for the oscillating system of acetic acid, t_ in∝c 0.883_ HOAcexp(2.32×10 3T), t_ p.1∝c 0.399_ HOAc· exp(4.50×10 3T), t_ p.2∝c 0.301_ HOAcexp(5.88×10 3T); for the oscillating system of phosphoric acid, t_ in∝c 1.14_ H_3PO_4exp(7.70×10 4T), t_ p.1∝c 1.42_ H_3PO_4exp(1.14×10 4T), t_ p.2∝c 1.47_ H_3PO_4exp(1.27×10 4T).展开更多
基金ProjectsupportedbytheNaturalScienceFoundationofShandongProvince (No .Y2 0 0 0B0 3)
文摘It has been found that the two-phase reactions of aqueous HCl, HOAc or H_3PO_4 with primary amine N_ 1923 in chloroform are oscillating reactions. Their power-time curves were measured by the titration microcalorimetric method, and the induction period (t_ in). The first oscillating period (t_ p.1) and the second oscillating period (t_ p.2) were determined. The apparent activating parameters and the orders of the oscillating systems were calculated and the following relationships were established: for the oscillating system of hydrochloric acid t_ in∝c 0.147_ HClexp(1.35×10 3T), t_ p.1∝c 0.241_ HCl· exp(4.33×10 3T), t_ p.2∝c 0.290_ HClexp(5.59×10 3T); for the oscillating system of acetic acid, t_ in∝c 0.883_ HOAcexp(2.32×10 3T), t_ p.1∝c 0.399_ HOAc· exp(4.50×10 3T), t_ p.2∝c 0.301_ HOAcexp(5.88×10 3T); for the oscillating system of phosphoric acid, t_ in∝c 1.14_ H_3PO_4exp(7.70×10 4T), t_ p.1∝c 1.42_ H_3PO_4exp(1.14×10 4T), t_ p.2∝c 1.47_ H_3PO_4exp(1.27×10 4T).
