【摘要】 提出了一种简便的TPD谱图处理法——等脱附速率法。此法与查表法相结合,有助于确定脱附反应动力学级数。实验证明,该法适用于从一级或二级脱附反应TPD谱求解脱附活化能E_d和指前因子k_o值。更多还原

【Abstract】 A concise method——isodesorption rate method（IDRM） is presented for the determination of E_d and k₀ from a temperature programmed desorption （decomposition）（TPD） spectrum with no re-adsorption. Based on the Arrhenius equation and the constant heating rate, we have Eqs.（1） and （2）（see the text）, where T, b, t, θ, k₀, E_d, and R are temperature, heating rate, time, Surface coverage, pre-exponential factor, activation energy of desorption （decomposition）, and standard gas constant, respectively. For the desorption （decomposition） rate of h_i at T_i is equal to that of h_i at T_j （see Fig. 1）, Eqs. （3）—（5）（1st order） and Eqs. （11）—（13）（2nd order） are deduced. The values of h_i, h_j, θ_i, and θ_j may be evaluated by Eqs. （6） and （7）, where W_TihihjTj is the weight of the paper corresponding to the rectangle T_ih_ih_jT_j, W₀ is that under the spectrun T_Lh_ih_mh_jT_H, and W_i, W_j are that of the peak areas of T≥T_i, T_j respectively. By substituting Eqs. （6） and （7） to Eqs. （3）—（5） and （11）—（13）, the resultant Eqs. （8）—（10） （1st order） and （14）—（16） （2nd order） are obtained for determining E_d and k₀.Table 1 shows that the results determined by different methods coincide with each other quite well. It also proves that the selected kinetic orders of desorption（decomposition） are correct because the relative errors between the Ed′S by IDRM and CTM^[5] are<3% otherwise that will be about 30% when the desorption （decomposition） order is erroneously selected. So the combination of IDRM and CTM is benificial for determining the kinetic order of desorption （decomposition）.更多还原