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研究生:張家銘
研究生(外文):CHANG, CHIA-MING
論文名稱:北臺灣與澎湖島紅壤中鐵凎氧磁性氧化鐵之鑑定以及尖晶石型式鐵與鋁氧化物表面去質子化反應的量子化學研究
論文名稱(外文):Characterization of Ferrimagnetic Iron Oxides in Red Soils of Northern Taiwan and Peng-Hu Island, and Quantum-Chemical Studies on the Deprotonation of Spinel-Type Iron and Aluminum Oxide Surfaces
指導教授:王明光
指導教授(外文):MING-KUANG WANG
學位類別:博士
校院名稱:國立臺灣大學
系所名稱:農業化學系
學門:農業科學學門
學類:農業化學類
論文種類:學術論文
論文出版年:1997
畢業學年度:85
語文別:中文
論文頁數:146
中文關鍵詞:鐵凎氧磁性尖晶石型式鐵氧化物六水金屬陽離子去質子化反應密度泛函理論
外文關鍵詞:FerrimagneticSpinel-typeIron oxidesHexaaqua metal ionsDeprotonationDensity functional theory
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結合溼式化學、X-射線繞射鑑定與鐵-57梅思堡光譜分析,以及超導
量子干涉磁化儀之磁化曲線測量等研究方法,得以獲知致使北台灣與澎湖
島紅壤具有強磁性的礦物物種,主要乃為屬於尖晶石型式之鐵淦氧磁性鐵
氧化物;另由於北台灣安山岩質強磁性紅壤經手執磁鐵分離後之強磁性部
份的亞鐵離子含量遠高於澎湖島玄武岩質強磁性紅壤,且由鐵-57梅思堡
分析之直接研究證據顯示,北台灣淡水、八里安山岩質強磁性紅壤中之尖
晶石型式鐵氧化物應屬部份氧化之磁鐵礦,澎湖島東衛、外垵玄武岩質強
磁性紅壤中的尖晶石型式鐵氧化物則屬磁赤鐵礦,從飽和磁化量與低磁場
磁化率之分析結果得以判斷北台灣與澎湖島強磁性紅壤中的鐵淦氧磁性氧
化鐵相對含量多寡以淡水>東衛>八里>外垵;各剖面層次之相互比較為
:淡水:B2層>B1層>A層,八里:A層>B1層>B2層,東衛:A層>B2層
>B1層,外垵:B2層>B1層>A層;而從高磁場磁化率則判斷得知東衛紅
壤中順磁性礦物之相對含量遠較淡水、八里與外垵三處為高;不同粒徑部
份的相互比較則為:淡水:砂粒>坋粒>黏粒,八里:坋粒>黏粒>砂粒
,東衛:黏粒>坋粒>砂粒,外垵:黏粒>坋粒>砂粒。 本論文並引
進量子化學中,由第一原理出發之密度泛函理論(density functional
theory, DFT)計算,以明瞭與水合金屬陽離子和金屬氧化物表面之去質子
反應進行難易密切相關的各項分子層次特性。 研究結果發現,以VWN(
Vosko-Wilk-Nusair functional),BP(Becke-Perdew functional)與
BLYP(Becke-Lee-Yang-Parr functional)等不同密度泛函所計算而得之結
構穩定度計算值(binding energy, Ebind),得以整体考慮鎂(Ⅱ)、鈣(
Ⅱ)、錳(Ⅱ)、鋅(Ⅱ)、鎘(Ⅱ)、鋁(Ⅲ)、鈧(Ⅲ)、鉻(Ⅲ)、鐵(Ⅲ)、鎵(
Ⅲ)與銦(Ⅲ)等主要元素族與過渡元素族六水金屬陽離子的去質子化反應
,其與第一水解常數實驗觀測值(pKa)之線性關係與直線迴歸係數(r)為:
VWN密度泛函: pKa = -19.15 + 0.02 Ebind r = 0.96 BP
密度泛函: pKa = -12.93 + 0.02 Ebind r = 0.96 BLYP密度泛
函: pKa = -13.08 + 0.02 Ebind r = 0.97而經由六水金屬陽離子
結構穩定度與金屬陽離子配位能(coordination energy, Ecoord)的聯繫:
VWN密度泛函: Ecoord = -1890.92 + 1.16 Ebind r = 0.96 BP
密度泛函: Ecoord = -1436.61 + 1.03 Ebind r = 0.96 BLYP密
度泛函: Ecoord = -1441.75 + 1.03 Ebind r = 0.96獲知六水金屬
陽離子第一水常數實驗觀測值與金屬陽離子配位能之間的線性關係為:
VWN密度泛函: pKa = 16.58 + 0.02 Ecoord r = 0.96 BP密
度泛函: pKa = 15.73 + 0.02 Ecoord r = 0.95 BLYP密度泛
函: pKa = 15.94 + 0.02 Ecoord r = 0.96 以密度泛函理論
計算當一外來水分子與六水鐵(III)、鋁(III)、錳(II)或鎂(II)離子產生
聯結反應平衡後之聯結反應能量變化量,O-H鍵長伸長量與外來水分子的
密立根電荷重配量,獲知當六水金屬陽離子之去質子化反應愈易進行,則
聯結反應放熱值愈大,O-H鍵長伸長量愈長,且外來水分子的密立根電荷
重配程度亦愈明顯,致使外來水分子所帶之淨電荷愈趨正電性;另並分析
六水金屬陽離子之紅外線簡諧振動頻率,由O-H伸縮振動頻率計算值得以
判斷六水金屬陽離子之去質子化反應進行難易,當O-H伸縮振動頻率愈高
,則O-H鍵結愈強,去質子化反應愈難進行。 在六水金屬陽離子去質
子化反應之密度泛函理論計算結果基礎下,配合分子顆團模型模擬計算其
結構穩定度、去質子化反應能量與O-H伸縮振動頻率獲知尖晶石型式鐵、
鋁氧化物表面之氫離子吸附親合力常數以鋁氧化物>鐵氧化物,八面体配
位座落>四面体配位座落。
Combined with the wet chemistry, X-ray diffraction (XRD),
Fe-57 Mossbauer analysis and superconducting quantum
interference device (SQUID) investigation, the magnetic minerals
existed in Northern Taiwan and Peng-Hu Island red soils can be
identified as ferrimagnetic (spinel-type) iron oxides. Owing to
the high Fe2+ content in the hand magnetic fractions of Northern
Taiwan red soils and the evidence provided by Fe-57 Mossbauer
analysis, the species of spinel-type iron oxides in Tan-Shui and
Pa-Li red soils was characterized as the partially oxidized
magnetite. However, the iron oxide in Tung-Wei and Wai-An red
soils was predominated in maghemite. According to the saturated
magnetization and low field susceptibility, the relative content
of ferrimagnetic iron oxides in Northern Taiwan and Peng-Hu red
soils can be summarized as follows: (1) Tan-Shui > Tung-Wei >
Pa-Li > Wai-An; (2) Tan-Shui: B2 horizon > B1 horizon > A
horizon; Pa-Li: A horizon > B1 horizon > B2 horizon; Tung-Wei: A
horizon > B2 horizon > B1 horizon; Wai-An: B2 horizon > B1
horizon > A horizon; (3) Tan-Shui: Sand > Silt > Clay; Pa-Li:
Silt > Caly > Sand; Tung-Wei: Clay > Silt > Sand; Wai-An: Clay >
Silt > Sand. Furthermore, the high field susceptibility implies
that the relative content of paramagnetic minerals in Tung-Wei
red soils is higher than that in Tan-Shui, Pa-Li and Wai-An red
soils. In this study , the deprotonated characteristics of
aqueous metal ions and metal oxide surfaces in molecular level
can be clarified by applying the first-principles density
functional theory (DFT). From the binding energies (Ebind)
calculated with Vosko-Wilk-Nusair (VWN), Becke-Perdew (BP) and
Becke-Lee-Yang-Parr (BLYP) density functionals, the global
linear relationship for the acidity and stability in both main
group (Mg(II), Ca(II) and Al(III)) and (post-)transition group
(Mn(II), Zn(II), Cd(II), Sc(III), CR(III), Fe(III), Ga(III) and
In (III)) aqueous metal ions has been confirmed: VWN density
functional: pKa = -19.15 + 0.02 Ebind r = 0.96 BP
density functional: pKa = -12.93 + 0.02 Ebind r = 0.96
BLYP density functional: pKa = -13.08 + 0.02 Ebind r =
0.97via the linkage of the correlation for binding and
coordination energies (Ecoord): VWN density functional:
Ecoord = -1890.92 + 1.16 Ebind r = 0.96 BP density
functional: Ecoord = -1436.61 + 1.03 Ebind r = 0.96 BLYP
density functional: Ecoord = -1441.75 + 1.03 Ebind r =
0.96the linear relationship between first hydrolysis constants
and coordination energies in hexaaqua metal ions can be
obtained: VWN density functional: pKa = 16.58 + 0.02 Ecoord
r = 0.96 BP density functional: pKa = 15.73 + 0.02 Ecoord
r = 0.95 BLYP density functional: pKa = 15.94 + 0.02 Ecoord
r = 0.96 Density functional calculations were also conducted
to elucidate the reaction of a foreign water molecule associated
with a hexaaqua Fe(III), Al(III), Mn(II) or Mg(II) ion. The
result presents that more remarkable variation in the exothermic
energy change, O-H bond lengthening and Mulliken charge
redistribution is favorable for the progression of the
deprotonation of hexaaqua metal ions. Moreover, judging from
the calculated O-H stretching vibrational frequencies of
hexaaqua metal ions, the larger the vibrational frequency, the
more difficult the deprotonation progression. On the basis
of previous density functional results regarding the
deprotonation of aqueous metal ions, the structural stability,
deprotonation energy and O-H stretching vibrational frequency of
the molecular cluster model of octahedral and tetrahedral sites
on spinel-type Fe and Al oxide surfaces were further examined.
The sequence of the proton adsorption affinity shows in the
order of Al oxide > Fe oxide; octahedral site > tetrahedral
site.
封面
目錄

第一章
第二章
第一節
第二節
第三節
第四節
第五節
第六節
第三章
第一節
第二節
第三節
第四節
第五節
第六節
第七節
第八節
第九節
第十節
第十一節 結
第四章

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