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Page 1: ishiken.free.frishiken.free.fr/english/lectures/rad-env-20180702.pdf · 2018. 6. 18. · aq thermalization H2O solvation Non-homogeneous: e aq, H, OH, H3O+, (H2) initial yield 10

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Page 2: ishiken.free.frishiken.free.fr/english/lectures/rad-env-20180702.pdf · 2018. 6. 18. · aq thermalization H2O solvation Non-homogeneous: e aq, H, OH, H3O+, (H2) initial yield 10

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Page 3: ishiken.free.frishiken.free.fr/english/lectures/rad-env-20180702.pdf · 2018. 6. 18. · aq thermalization H2O solvation Non-homogeneous: e aq, H, OH, H3O+, (H2) initial yield 10

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Page 4: ishiken.free.frishiken.free.fr/english/lectures/rad-env-20180702.pdf · 2018. 6. 18. · aq thermalization H2O solvation Non-homogeneous: e aq, H, OH, H3O+, (H2) initial yield 10

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Page 5: ishiken.free.frishiken.free.fr/english/lectures/rad-env-20180702.pdf · 2018. 6. 18. · aq thermalization H2O solvation Non-homogeneous: e aq, H, OH, H3O+, (H2) initial yield 10

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Page 6: ishiken.free.frishiken.free.fr/english/lectures/rad-env-20180702.pdf · 2018. 6. 18. · aq thermalization H2O solvation Non-homogeneous: e aq, H, OH, H3O+, (H2) initial yield 10

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Page 7: ishiken.free.frishiken.free.fr/english/lectures/rad-env-20180702.pdf · 2018. 6. 18. · aq thermalization H2O solvation Non-homogeneous: e aq, H, OH, H3O+, (H2) initial yield 10

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Page 8: ishiken.free.frishiken.free.fr/english/lectures/rad-env-20180702.pdf · 2018. 6. 18. · aq thermalization H2O solvation Non-homogeneous: e aq, H, OH, H3O+, (H2) initial yield 10

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Page 9: ishiken.free.frishiken.free.fr/english/lectures/rad-env-20180702.pdf · 2018. 6. 18. · aq thermalization H2O solvation Non-homogeneous: e aq, H, OH, H3O+, (H2) initial yield 10

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• 5(PLD��|^U�6_|i�+4�c,}�gi�5(1:Io4�t�x �g<B��ICRPo'�x+P_c,�|S�qv�s}���5(R�jkh+4�c,�g5(1:I�4�o� nN�4�ng�xg�%.o�n��y{�h4�_�+4�c,}>\u{S�qv�P_�?��s}o|p�h

Page 10: ishiken.free.frishiken.free.fr/english/lectures/rad-env-20180702.pdf · 2018. 6. 18. · aq thermalization H2O solvation Non-homogeneous: e aq, H, OH, H3O+, (H2) initial yield 10

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Page 11: ishiken.free.frishiken.free.fr/english/lectures/rad-env-20180702.pdf · 2018. 6. 18. · aq thermalization H2O solvation Non-homogeneous: e aq, H, OH, H3O+, (H2) initial yield 10

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Page 12: ishiken.free.frishiken.free.fr/english/lectures/rad-env-20180702.pdf · 2018. 6. 18. · aq thermalization H2O solvation Non-homogeneous: e aq, H, OH, H3O+, (H2) initial yield 10

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Page 13: ishiken.free.frishiken.free.fr/english/lectures/rad-env-20180702.pdf · 2018. 6. 18. · aq thermalization H2O solvation Non-homogeneous: e aq, H, OH, H3O+, (H2) initial yield 10

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Page 14: ishiken.free.frishiken.free.fr/english/lectures/rad-env-20180702.pdf · 2018. 6. 18. · aq thermalization H2O solvation Non-homogeneous: e aq, H, OH, H3O+, (H2) initial yield 10

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Page 15: ishiken.free.frishiken.free.fr/english/lectures/rad-env-20180702.pdf · 2018. 6. 18. · aq thermalization H2O solvation Non-homogeneous: e aq, H, OH, H3O+, (H2) initial yield 10

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Page 16: ishiken.free.frishiken.free.fr/english/lectures/rad-env-20180702.pdf · 2018. 6. 18. · aq thermalization H2O solvation Non-homogeneous: e aq, H, OH, H3O+, (H2) initial yield 10

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Page 17: ishiken.free.frishiken.free.fr/english/lectures/rad-env-20180702.pdf · 2018. 6. 18. · aq thermalization H2O solvation Non-homogeneous: e aq, H, OH, H3O+, (H2) initial yield 10

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Page 18: ishiken.free.frishiken.free.fr/english/lectures/rad-env-20180702.pdf · 2018. 6. 18. · aq thermalization H2O solvation Non-homogeneous: e aq, H, OH, H3O+, (H2) initial yield 10

wy{xsrz E=B�FD_c�������|free radical}

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H••OH çèH-OH H• + •OH

� C�b��q+4aWnZga•|vtu}q�i!a�SnH� C�b���)q+4a5WZg^LnH

xsrzc ��$b�^�R`#�q-ZWH

Page 19: ishiken.free.frishiken.free.fr/english/lectures/rad-env-20180702.pdf · 2018. 6. 18. · aq thermalization H2O solvation Non-homogeneous: e aq, H, OH, H3O+, (H2) initial yield 10

gb`hU+�& CACB@)5l��*V?'TS[R0�J!L\5ME)5jpyrolysiskR�W\[F

f_.

�'QV2��Q�]��MPH[JE700℃��QV5; I2 « 2 •I•I J4H�L\[YITS[REI2R•IU:Q�3]��N[F1700℃��QV��TaecN[F

,9>�(�$.jn-dge^ik: CH3CH2CH2…CH2CH3U�

K\ZV350℃��U?'QE(.:0�J;!L\E#GS(.�2T��<�]�Ogb`hRS[F-%U 6 ® gb`h �

ADB@�5l�V/�=�T��]�OXUJ�H

/�1]��MP0�J!L\Egb`h]��N[XUX�HF

78�$.jH2O2kV300nm��U�]��ME�"T5ME2OU•OH]+�N[FH2O2 + hn ® 2 •OH

Page 20: ishiken.free.frishiken.free.fr/english/lectures/rad-env-20180702.pdf · 2018. 6. 18. · aq thermalization H2O solvation Non-homogeneous: e aq, H, OH, H3O+, (H2) initial yield 10

(+)'%�O$���%�$���<&;LHFM1�>BA29?!�3BA.%�����<#%���=Fe2+9��4-•OHLHFM1�>BA.

H2O2 + Fe2+ ® Fe3+ + •OH + OH-

Fe2+=%�3BFe3+9:A.KDNIN(Fenton)��: •OHLHFM���947�8/A.

(,)'� ��"� �<EJMGP1��;��3BA9-6<EJMGP1�C��5A290@-LHFM1��5A291� �8/A.

H2O •H + •OHCH4 •H + •CH3

-CH2-CH2-CH2-CH2 -CH2-•CH-CH2-CH2 -----à-CH2-CH-CH2-CH2

�� (crosslinking)-CH2-CH-CH2-CH2

LHFM<��� *

Page 21: ishiken.free.frishiken.free.fr/english/lectures/rad-env-20180702.pdf · 2018. 6. 18. · aq thermalization H2O solvation Non-homogeneous: e aq, H, OH, H3O+, (H2) initial yield 10

jdckS�/PKS�� ;(1) 8-��P0)��qjdckT���O.IL\< <Z\��Q��R0)J]GPY?]=8-(scission)��

CH3CH2CH2CH2 ®CH3CH2CH=CH2 + •H®CH2=CH2 + •C2H5

0)(rearrangement)��(C6H5)3CCH2 ® (C6H5)2C-CH2(C6H5)C6H5Thagk�O?\<imem&3D��O)�(0))INZ\��Q��R��J]=

(2)�4+�WS�q�4+�3T�!+�D�M?]GPC[:�D9�INB\<jdckS� �:�P IF+�`��Ip+"PIN�5S�EQ I@jdckD'X^]=

•OH + H2C=CH2 ®HOCH2-CH2•X_\Rbflm�D?^U<jdckTH[R��Sbflm�P��I<

HOCH2-CH2• + H2C=CH2 ®HOCH2-CH2-CH2-CH2•H[R$*S6D�V]=H[R#Sbflm�R�J]=#>P16(R2,IN<$*6S7@<��Q�R�7J]=G^T4���npolymerizationoPZU^]YSO<%RjdckD��J]GPOjdck4���P@A=

Page 22: ishiken.free.frishiken.free.fr/english/lectures/rad-env-20180702.pdf · 2018. 6. 18. · aq thermalization H2O solvation Non-homogeneous: e aq, H, OH, H3O+, (H2) initial yield 10

zup{c�9`[c � Dy}v}-bi�XOtr|xqsuow{zup{n.g

•L?B?JGLG ® L??L??L

@EA?'2�U�U ��•NLO•Lzup{d"&��+c'2n�U�S^O�Q'��O'2��bal``ibO"&+czup{T.�ZlP

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@FA?�4�`��� ��zup{d��=�ni]\hOzup{<_ �ZlP'c��5�6_.�Zl:;�'2d•NL��c�4�_.fm^Sl`7 _UlP8O•L`•NLT �Zme'��n�.ZlP•L?B?•NL?® LDN

Page 23: ishiken.free.frishiken.free.fr/english/lectures/rad-env-20180702.pdf · 2018. 6. 18. · aq thermalization H2O solvation Non-homogeneous: e aq, H, OH, H3O+, (H2) initial yield 10

VPJW=�%;6=�� -(5) (";=��]("��ZO2[>�>VPJW=�):0C/

("��<>��+�2�80B.di-radical(bi-radical)=�8:.VPJW;("��>��5C� 2�1/

•CH2OH + •O2 ® •O-O-CH2OH

��5C•O-O-RQHU=VPJW>TYIKOVPJW;�?D.("F�B&@.�#5C��:T\IKNHS.GWMYW.LRX!=�(" �F��5C/�79.(�

$<>3=��2*E791C3;2�1/,����25C' <>.3=��2*EC4.���=��<A�1*�FA8/

Page 24: ishiken.free.frishiken.free.fr/english/lectures/rad-env-20180702.pdf · 2018. 6. 18. · aq thermalization H2O solvation Non-homogeneous: e aq, H, OH, H3O+, (H2) initial yield 10

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Page 25: ishiken.free.frishiken.free.fr/english/lectures/rad-env-20180702.pdf · 2018. 6. 18. · aq thermalization H2O solvation Non-homogeneous: e aq, H, OH, H3O+, (H2) initial yield 10

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Page 26: ishiken.free.frishiken.free.fr/english/lectures/rad-env-20180702.pdf · 2018. 6. 18. · aq thermalization H2O solvation Non-homogeneous: e aq, H, OH, H3O+, (H2) initial yield 10

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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

Page 27: ishiken.free.frishiken.free.fr/english/lectures/rad-env-20180702.pdf · 2018. 6. 18. · aq thermalization H2O solvation Non-homogeneous: e aq, H, OH, H3O+, (H2) initial yield 10

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

�������

Spur�track

Page 28: ishiken.free.frishiken.free.fr/english/lectures/rad-env-20180702.pdf · 2018. 6. 18. · aq thermalization H2O solvation Non-homogeneous: e aq, H, OH, H3O+, (H2) initial yield 10

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

�������

Page 29: ishiken.free.frishiken.free.fr/english/lectures/rad-env-20180702.pdf · 2018. 6. 18. · aq thermalization H2O solvation Non-homogeneous: e aq, H, OH, H3O+, (H2) initial yield 10

���������

e-aq

H H2

OH H2O2

Monte Carlo calculation

Y. Muroya et al. Can. J. Chem., 80, 1367-1374 (2002)

Page 30: ishiken.free.frishiken.free.fr/english/lectures/rad-env-20180702.pdf · 2018. 6. 18. · aq thermalization H2O solvation Non-homogeneous: e aq, H, OH, H3O+, (H2) initial yield 10

������������� ��� ����

Page 31: ishiken.free.frishiken.free.fr/english/lectures/rad-env-20180702.pdf · 2018. 6. 18. · aq thermalization H2O solvation Non-homogeneous: e aq, H, OH, H3O+, (H2) initial yield 10

���� � ���

���� ������ ����

Page 32: ishiken.free.frishiken.free.fr/english/lectures/rad-env-20180702.pdf · 2018. 6. 18. · aq thermalization H2O solvation Non-homogeneous: e aq, H, OH, H3O+, (H2) initial yield 10

Electron in Potential wellorientation of H2O molecules

��������

���; 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-)

�� ��

Page 33: ishiken.free.frishiken.free.fr/english/lectures/rad-env-20180702.pdf · 2018. 6. 18. · aq thermalization H2O solvation Non-homogeneous: e aq, H, OH, H3O+, (H2) initial yield 10

���� �������

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

Page 34: ishiken.free.frishiken.free.fr/english/lectures/rad-env-20180702.pdf · 2018. 6. 18. · aq thermalization H2O solvation Non-homogeneous: e aq, H, OH, H3O+, (H2) initial yield 10

������������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


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