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題名 | 應用非線性迴歸方法於土壤吸附重金屬動態反應模式之參數決定=Application of Non-Linear-Regression Method in the Determination of Parameters of Kinetic Adsorption Model of Heavy Metal in Soil |
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作者姓名(中文) | 劉滄棽; 林正錺; | 書刊名 | 中華農業研究 |
卷期 | 46:1 1997.03[民86.03] |
頁次 | 頁82-98 |
分類號 | 434.223 |
關鍵詞 | 參數鍵定; 微分方程式; 模式; Parameter identification; Differential equation; Model; |
語文 | 中文(Chinese) |
中文摘要 | 本研究針對溶質輸送現象及表面化學中,常被引用之非線性吸附反應為對象,利 用統計和數值方法研究模式參數鑑定的方法,嘗試檢視並改進各種傳統鑑定方法可能隱含的 誤差,以有效規範系統反應行為。 本研究使用吸附能力不同的四個大度山紅壤分別與 500 ppm 和 100 ppm 的銅離子或鎘離子 溶液混合,在吸附反應的過程中,測定未平衡狀態不同時間的金屬離子濃度,可以得到動態 吸附現象的數據。利用數值分析軟體,求解非線性動態吸附方程式的參數,探討求解條件, 及參數在吸附反應中的意義。 由研究結果得知, 三種模式所得之曲線代表性均高( >0.95 ), 但以擬二級吸附反應( pseudo second order adsorption reaction )在部分試驗數據求得之最大吸附量竟小於觀 測得到的吸附量,顯示擬二級吸附反應不能完全代表土壤與離子吸附反應的現象。經加入反 應級數修正後的模式,則均未發現此不合理的狀況。 同一試驗條件在不同時間下取得之數據, 因本身之自相關( autocorrelation )太大,所求 得之參數雖可將數據模擬得十分吻合,但參數的偏差太大,因此仍不能得到有代表性的參數 。 在本研究中,最大吸附量( R )至少要有兩組不同濃度條件的動態吸附數據,才能使所 得的參數有意義, 反應吸數( n )則至少需要四組以上不同反應條件的數據,而反應速率 常數( k )需要八組以上不同反應條件的數據,才能使所得的參數有意義。 |
英文摘要 | As the nonlinear adsorption model was often quoted in the study of phe nomenon about solute transport and surface chemistry. Statistics and numetrical analysis, involved in the nonlinear model, were used in this research to inspect and minimize some errors might hidden in various conventional methods of parameter indentification, for effectively regularizin greaction behaviors of system. Four kinds of red oxisols (fine, mixed, acid, hyperthermic paleusult), whith diverse capacity of adsorption, were mixed with 50 ppm and 100 ppm Cu �杠� /Cd �杠� and measured the ion concentrations of cu �杠� /Cd �杠� under inequilibrium state at different time during the adsorption process. With the aid of numerical analysis software to obtain the parameters of nonlinear differential eqaution, the required conditions for solution of the equation can be investigate, and the meaning of parameters can be identified, too. All the curves derived from 3 models were representative and significant(>0.95).According to the pseudo 2 nd order adsorption reaction, some tests came out the fact that the maximum amount of adsorption was irrationally smaller than the observed one, it implied the pseudo 2nd adsorption can not completely or ideally explain the phenomenon of adsorption between heavy meatal ions and soil. After the model modified by reaction order, the irrational situation above was eliminated. Due to the rather high auto-correlation of data attained at different time under the same experimental codition, the derived parameters were coincident with the simulated ones, but the variance caused was too large to acquire the efficient parameters. Hence, to make the derived parameters meaningful, the maximum amount of adsorption derived from kinetic adsorption model should base on at least 2 sets of different concentrations, 4 sets of various conditions for reaction order (n), and more than 8 sets of different of coditions of reaction rate costants. |
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