ishiken.free.frishiken.free.fr/english/lectures/rad-env-20180702.pdf · 2018. 6. 18. · aq...
Transcript of ishiken.free.frishiken.free.fr/english/lectures/rad-env-20180702.pdf · 2018. 6. 18. · aq...
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)&./1�!1�1� 0.12 0.1205 = 0.60*� 1**��� 0.08 0.0802 = 0.16#�1-*1�%1��" 0.05 0.0504 = 0.20.(,1 1���1�$ 0.01 0.0104 = 0.0434�415�� 0.008 0.008015 = 0.12*1990���40.0525�**1990���40.2025��
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H••OH çèH-OH H• + •OH
� C�b��q+4aWnZga•|vtu}q�i!a�SnH� C�b���)q+4a5WZg^LnH
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ADB@�5l�V/�=�T��]�OXUJ�H
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78�$.jH2O2kV300nm��U�]��ME�"T5ME2OU•OH]+�N[FH2O2 + hn ® 2 •OH
(+)'%�O$���%�$���<&;LHFM1�>BA29?!�3BA.%�����<#%���=Fe2+9��4-•OHLHFM1�>BA.
H2O2 + Fe2+ ® Fe3+ + •OH + OH-
Fe2+=%�3BFe3+9:A.KDNIN(Fenton)��: •OHLHFM���947�8/A.
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H2O •H + •OHCH4 •H + •CH3
-CH2-CH2-CH2-CH2 -CH2-•CH-CH2-CH2 -----à-CH2-CH-CH2-CH2
�� (crosslinking)-CH2-CH-CH2-CH2
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CH3CH2CH2CH2 ®CH3CH2CH=CH2 + •H®CH2=CH2 + •C2H5
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•CH2OH + •O2 ® •O-O-CH2OH
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H2O�最もポピュラーな化合物, 人体の 70% を構成H2O e-aq, H+, •H, •OH, H2, H2O2, •HO2
2.63 0.55 2.72 0.45 0.68 ¾
e-aq: hydrated electron •H : H atom������
•OH : OH radicalH2, H2O2����
�������� 100ns の G値�� G値 = ����/100eV
Event Time
H2OExcitation Ionization
H2O+ + eH2O*+ H2O
H3O+ + OHH + OH(H2 +O) eaq
thermalization
solvationH2O
Non-homogeneous: eaq, H, OH, H3O+, (H2) initial yield
1016 sec
1014 sec
1013 sec
1012 sec
107 secHomogeneous: eaq, H, OH, H3O+, H2, H2O2, primary yield
Diffusion & Spur reactions
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Spur�track
Spherical Spur
Cylindrical trackG-values
LET/eV nm-1 -H2O eaq- OH H H2 H2O2 HO2
g-rays / 0.23H+ / 12.3D+ / 61
He2+ / 108
4.083.463.012.84
2.631.480.720.42
2.721.780.910.54
0.550.620.420.27
0.450.680.961.11
0.680.841.001.08
0.008-
0.050.07
Spur reactions rate const. /1010 M-1s-1
eaq- + eaq
- ® H2 + 2OH- 0.54eaq
- + OH ® OH- 3.0eaq
- + H3O+ ® H + H2O 2.3eaq- + H ® H2 + OH- 2.5H + H ® H2 1.3OH + OH ® H2O2 0.53OH + H ® H2O 3.2H3O+ + OH- ® 2H2O 14.3
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e-aq
H H2
OH H2O2
Monte Carlo calculation
Y. Muroya et al. Can. J. Chem., 80, 1367-1374 (2002)
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Electron in Potential wellorientation of H2O molecules
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���; E= - 2.9 Veaq
- + Mn+ ® M(n-1)+
eaq- + O2 ® O2
-
eaq- + H+ ® H (H in acid)
eaq- + RX ® R• + X-
(������)
inorganic 1010 M-1s-1 organic 1010 M-1s-1
O2
H3O+
NH4+
Ag+
Cd2+
In3+
NO3-
H2O
1.92.3
<2x10-4
3.65.05.6
0.871.6x10-9
(O2-)(H + H2O)(H + NH3)
(Ag0)(Cd+)(In2+)
(NO32®NO2+2OH-)
C6H6
C6H5ClC6H5I
CH2=CH2
CH2=CCl2
CH4
CH3ICH3OH
1.2x10-3
5x10-2
1.2<2.5x10-4
2.3<10-3
1.7<10-6
(C6H7 + OH-)(•C6H5 + Cl-)(•C6H5 + I-)
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H atom: Reductant -2.3V■ reduction
H + Cu2+ ®H+ + Cu+
■ reaction with radicalH + OH ®H2O, H + H ®H2
■addition to double bondH + CH3C≡N ®CH3CH=N•
■H abstractionH + CH3OH ® •CH2OH + H2
OH radical: Oxidant 2.72V�oxidation
OH + Mn+ ®M(n+1)+ + OH-
� reaction with radicalOH + OH ®H2O2, OH + H ®H2O
�addition to double bondOH + CH2CH2 ® •CH2CH2OH
�H abstractionOH + CH3OH ® •CH2OH + H2O
reactant type OH / 107 M-1s-1 H / 107 M-1s-1
CH2=CHCONH2
C6H6
C6H5NO2
C2H5OHCH3OH
addtionaddtionaddtion
abstractionabstraction
45053034018084
1800531701.70.16
Rate constant
������������Acid solution eaq- + H+ ® H, G(eaq-+H)=3.7, G(OH)=2.9O2 が存在しないとき
H + CH3CH2OH ® CH3•CHOH + H2
OH + CH3CH2OH ® CH3•CHOH+ H2O 2 CH3•CHOH ® (CH3CH2OH)2 glycol disproportion
® CH3CH2OH + CH3CHO acetaldehydeO2 ���
CH3•CHOH + O2 ® CH3•OOCHOH ¬ peroxyl radical2 CH3•OOCHOH ® 2 CH3CHO+ H2O2 + O2H + O2 ® HO2, 2 HO2 ® H2O2 + O2
product G(product) No O2 G(product) O2
H2
H2O2
CH3CHOglycol
4.2~0.61.901.65
~0.64.152.60
reported (34mM ethanol, pH=1.2)
溶質の分解 ® 水の浄化, 生物効果® DNA 損傷