New insight into the ZnO sulfidation reaction:
mechanism and kinetics modeling of the ZnS outward
growth
Laure Neveux, David Chiche, Javier Perez-Pellitero, Loı̈c Favergeon,
Anne-Sophie Gay, Michèle Pijolat
To cite this version:
Laure Neveux, David Chiche, Javier Perez-Pellitero, Loı̈c Favergeon, Anne-Sophie Gay, et al..
New insight into the ZnO sulfidation reaction: mechanism and kinetics modeling of the ZnS
outward growth. Physical Chemistry Chemical Physics, Royal Society of Chemistry, 2013, 15,
pp.1532-1545. <10.1039/C2CP42988H>. <hal-00771115>
HAL Id: hal-00771115
https://hal.archives-ouvertes.fr/hal-00771115
Submitted on 4 Mar 2013
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1
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E461161D563'D11A71135D31156''45611E45D116115DD1151161263'45D1611:656A!(13161
865!1A6DD15161563D(161563D1D'1D2D6E116158D'D151A7(1=D1D86'11615361
45861D'135D4351A6'3611:616965D263145861=3'1'6F46!15566E1D15E6511A61
3A61 1 23561 6965D2631 536'1 1 '61 3436E1 551 D'A35D1 EDD'11 :1 655521 31
556D(161A71653D155D61865'4'1D261=3'16956''6E135ED116F1?7@31
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V
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1
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$4'1356513E1A6556131$42(161835D3D15151865'4'1?A7@131A61A3D6E13'1'=1D1D11DH11
%1 31 A61 A'6586E1 D1 D11 DH1 31 61 8346'1 51 61 >D6D1 5361 53D'1 2D1 5=(1 3'1 =61 3'1
568D4'!1 D1 D11 DD(1 61 6F43D1 81 G1 >?A7@A(1 =D1 A1 Z1 D1 A6651 31 31 D6351 835D3D1 ?D651
5656''D1 6RD6@11 :1 4E6(1 61 >D6D1 5361 D'1 1 D6351 =35E1 A71 35D31 56''4561 A41
2D1 835!1 35ED1 1 61 6F43D1 81 G1 >?A7@A(1 =D1 A1 Z1 D1 1 61 A71 35D31 56''4561 E23D1
6956E1?-1-1>311D001>3@11
1
58E24'44:A5B74B4A924562A54A274A2464)2B24A924?E,74B44$%4,A5F4,277E24B41('4#4AB4
α&(1(4
5BE74$%4,A5F4,277E274744E6A5B64B4#$%4A4%5 !"4#$%D&(84#"4α
1
-1I1111%5466151A7<135D3156''4561
:61835D3D15161>D6D15361=35E1A7<135D3156''45613'1A661'4ED6E1A!1652538D265!11
:5661D'652318<1'45DE3D16965D26'1=6561655526E14E65161'3261A7135D3156''4561
3E1835D4'1A7<135D3156''456'1?A7<@31=D413EED1A7<1161563D13'1??A7<@1G10@(1=D1
?A7<@1GD17H1>3(13E1?A7<@1G171H1>311'1'=1D1D11D.(156'4D1α?@1A3D6E1356131DE6D311
F'6F46!(1 A7<1 35D3156''4561 3'1 1 D546611 61 8<1 '45DE3D1 563D1>D6D'11 :4'(1
61φ154D1E6'11E66E1161A7<135D3156''45611
1
58E24544A5A5B64B4A924A5B6F4B6275B6427E74A524B4C6D47EF5A5B64A4%0' !"4#$%&'4#464
5BE74#$%D(4
1
1
6111813'615=1263D'21
61D11115'DD151662635!1'6'1D886E1D161563D1
'1 568D4'!1 ED'4''6E1 35ED1 1 61 2365D3'1 35365D3D'(1 31 263D'21 51 81 5=1
=D14=35E1E68626131A615'6E11:D'1D2D6'1D13E19!61EDM4'D15521618<9
81 D6531 D655361 1 61 81 '4553611 :61 696531 E686261 D'1 23E61 ''DA61 =D1 61
56'661 51 D1 833D6'1 D1 61 81 3'611 "56865(1 3'1 693D6E1 D1 6D1 -1-(1 61 2'1
5A3A61 D1 E656'1 6966E1 D1 61 81 3'61 D1 61 '45DE3D1 653D1 EDD'1 3561 D1
833D6'11 :656556(1 D1 D'1 '4E1 EDM4'61 8D31 D1 833D6'11 <9!61 32'1 23!1 EDM4'61 8D31
D65'DD31 'D6'11 1 263D'21 31 A61 5'6E1 31 'DE65'1 61 EDM4'D1 563D'1 541 8<1
3E1815!'3'1D1E656'1?B5[659CD>13D@11:615=D16D1'6'13561E63D6E1D1:3A61
711
1
6171111C6652D3D15161536E6652DD1'61
''42D1 61 51 61 6D1 '6'1 ?D@1 1 ?L@1 D'1 61 536E6652DD1 '6(1 6D1 ''DA61 5361 3='1
556'ED1 1 631 51 6'61 6D1 '6'1 31 A61 3436E11 51 631 ''DADD!(1 31 '!'621 51
6F43D'11A3'6E11116F4DDA5D4211EDD'113D6E111161536E6652DD1'6'(13E1161
6656453D!1EDD'13'11A61'86E11:3A61-1565'161''DA616956''D'15161356D1
563D8D!1 51 5=1 551 631 51 61 662635!1 '6'1 '4'6E1 1 A61 536E6652DD11 :6'61
6956''D'13561'D2D5D6E1'DE65D1616965D2631EDD'1'6155161'4E!1356153515521
61 6F4DDA5D421 EDD'(1 65=D'61 61 5361 51 61 56865'61 563D1=4E13861 A661 3>61 D1
3411 %1 61 3'61 51 31 EDM4'D1 536E6652DD1 '61 ?'6'1 ?6@1 3E1 ?H@@(1 5=1 3='1 3561
6956''6E1 D1 652'1 51 φ\01 D'63E1 51 φ(1 \01 A6D1 31 61 6F431 1 D1 2(1 D1 5E651 1 23D3D1 4D'1
266D!1?C15656'6'1EDM4'D16RD6'@11
:61 3D1 4'6E1 3561 >D1 ?D]D]L@1 551 61 >D6D1 '3'(1 BD1 ?D]D]-1 3E1 H]D]L@1 551 61 6F4DDA5D421
'3'(1D1556'ED116315161'6'13E1!155161'D6'1553D1316181'4553611
1
1
1
1
1
1
1
1
1
4A71ED''D3D8613E'5D1316181'455361
A71J171'11J1'^1 1111 11171A'1J1'^1
%1&96531D655361563D1=D1E6'5D151=3651316181'455361
71A'1J1<^^D1691J171N6911111 11111A7<1J17'4
4&96531 D655361 563D1 =D1 563D151 A4DED1 4D'1 51 81 31 81 '455361 ?'45DE61 D1 3E1
D1833!@1
'11 1111691J1'^1J1C^^81691J171N691
148D1D1ED554'D14561D1833D6'15521618<81D6531D655361161'455361516181
3!651
C^^8691111 111C^^81D1
88D11 1188691
'4 <9!61 ED554'D1 541 61 81 3!651 5521 61 D6531 D655361 1 61 81 '455361 4567
D65'DD31'D6'1
<^^D1D111 1111<^^D16911
51%6531D655361563D'1=D1563D151319!61833!1D1618<13'613E1$4215131
9!61D13131D65'DD31'D615161813'61
<<?8<@111 1111CNN<?8<@1J11<^^D1D1111111111
74%6531D655361563D1=D1563D15131D1833!1D1618<13'61
88?8<@111J11C^^8D11 11
1881D11111J1C_8?8<@1111
81 DD3D1 563D1 A6=661 D1 3E1 9!61 833D6'(1 =D1 63E'1 556''D86!1 1 61
5523D1518DE'1D161A4>151618<13'611
C_8?8<@1J1CNN<?8<@11
111 11111 1
2)F24%44.F226A347A2,74,B,B724B4A924C6D47EF5A5B6429657"43922474647B42,2726A4224
7B,A5B6475A274B64A924C647E2"4A9247E)75,A742+A46456A"427,2A52F3"4224AB4A9242+A26F46456A26F4
''
11
''
56A22"4 V Zn 464 VO 4B27,B6"427,2A52F3"4AB44>56464B+3826463"4 Oi AB464B+38264AB4
FBA245646456A27A5A5F475A2"464 Zn Zn AB44>564AB4FBA245644>564,B75A5B64564A92437AF47AEAE2(4
%1D'1D656'D11235616'6153613='11616965D263156'4'1'DE65D161>D6D15361
E66E661=35E'1A713E1A7<135D3156''456'11:613='1φH13E1φ.1E11E66E11613'6'1
35D31 56''456'11 :5661 3='1 ?φ6(1 φI1 3E1 φL@1 E66E1 1 61 53D1 ?A7@U?A7<@11 :61 3=1 φD1 3'1 31
D6351 835D3D1 =D1 ?A7@1 A41 3'1 31 E66E661 =35E1 ?A7<@11 D3!(1 !1 61 φ71 3E1 φ-1 3='1
69DAD1 31 D6351 835D3D1 =D1 ?A7@(1 1 A41 1 3'1 1 6'61 1 '6'1 1 3561 1 36E1 1 1 1 61 1 696531
D65536(16!1=4E163E1131D563'D1563D15361865'4'131'D6161'455361516135D6'1
D44'!1D563'6'1411616E1516153'5523D1?4=35E11E68626@11F'6F46!(1
6151616D15=13='15656E1D1:3A61-1D'1'D'61=D131>D6D15361E6563'D1865'4'1
3(1 D563'D1 865'4'1 ?A7@(1 3E1 DE66E61 =35E1 ?A7<@11 :656556(1 31 ''DA61 =3!1 1 3411
551 1 61 1 6965D2631 1 E331 1 =3'1 1 1 2AD61 =1 662635!1 '6'1 3''42D1 31 A1 3561
5D161>D6D'114156326(136E1EE2D96E1>D6D'**(1D'1A3'6E11613''42D13161
>D6D1536'151A1'6'135616F4311
)361D2DD1'61
?D@1
`13=1
φ1 = k1 PH 2 Sθ s 2θ sφ' 1 = k1 PH S
2
6
4
4
1
4
PH 2O
4
4 1 + 2 K K 3/ 2 K 3/ 4
2
6
8
5
3
1
1
1
1
1
2
2
?7@1
6
4
4
1
φ 2 = θ H − s 2 [O"i ext ][h° ext ]φ 2 = k 2 4
3/ 4
2 K6 K7 K8
4
1
+
44
K 1 K 3 PH 2 S
5
?-@1
6
4
4
1
φ3 = θ S −φs 31 = k 3 4
PH 2O
41+
3
3/ 2
4
K 1 K 2 4 K 6 K 8 PH 2 S
5
?6@1
φ4l0 = D ∆C = D(V "Zn )
?H@1
φ 5 l 0 = D ∆C = D (O"i ) K 6 K 8
?.@1
φ6 = k6
?I@1
φ7 = [V "Zn int φ] 7 = k 7
?L@1
φ8 = [V "Zn( ZnO) ][V °°O( ZnO) φ] 18 = k 8
6
4
1
4
2
3/ 2
4
4 K6 K 7 K8
44 1 +
K3
5
3
1
1
1
11
2
2
3
1
1
1 × 4K 63 K 83/ 2
1
11
2
3
1
1
1
1
1
2
K1K 2 K3 K 6 K8 PH 2S
PH 2O
K 1 K 2 K 3 K 6 K 8 PH 2 S
PH 2O
K 1 K 2 K 3 K 6 K 7 PH 2 S
PH 2O
1
2)F2444!FEFA24,B775)F24φ
φ48B3A94F374564A924,,B+5A5B674B4A924A2;2A25656847A2,74B42947A2,4
4AB48(4
1
<9!61EDM4'D1?'61?H@@13E1696531D655361563D1=D1=3651E6'5D1?'61?7@@13861A661
'DE656E163ED116F1?I@1?871G18H@31
[
][ ]
([
] [
])
1
k 2 θ 2H − s Oi'',ext hext
S m 2 = DO '' Oi',' int − Oi'',ext S m 5 1
i
?I@1
:611D6115112D96E116965311D6553611563D11=D11=3651E6'5D113E119!611EDM4'D11
>D6D'113='114'1111556616'651155211611=3651135D31156''45611E66E66111:4'(1615361
3=151312D96E1>D6D'151696531D655361563D1=D1=3651E6'5D13E19!61EDM4'D13'1
A6613436E13E1D'1D861A!16F1?L@31
v 2, 5 =
aPH 2 S
PH 2 S + b
1
?L@1
=D31
1
a = K 6 K 8 2 DO '' S m5 1
B1
i
b=
DO '' S m 5
i
1
1
k 2 K1 K 3 K 7 K 8 2 S m2
3E1=65612713E12H154D'(156'6D86!(1'3E1551612154D15636E116965311D6553611
563D11=D11=3651E6'5D13E19!61EDM4'D11:6'6154D'1E66E116169615161
6265D3161=656161536E6652DD1'61515=145'(1=D1D'161696531D655361
5512713E161813!6515512H11:6'6154D'131A613436E1552116265D311'DE653D'(11
3'1131154D1151135D61'3617I15131!DE651616956''D'135631
S m2 =
2VmZnO
1
(1 + zα ) 2 1
r0
S m5 =
42 0VmZnO
1 ?D0@1
r02 ln(1 + zα )
?/@1
=6561C28<15656'6'161235184261518<1?2-12D@(1161693'D16RD61?C2811=45D61
UC28<1G1D1..@(150161DDD3153ED4'1516135D61?2@(1\01G1D1211:4'1613436E153611835D6'11=D11
?A7@135ED116F1?L@(1=D131A612356E11616965D26315361835D3D11D11DI1'='1
D'1235D'1551616965D2631E331A3D6E13131553D31865'D15101-1113261156'4'11
=65611A3D6E11=D11651553D31865'D'11
1
58E24744A5A5B64B4A9242A5B64A2427E74#$%4B4C6D47EF5A5B64B4A924724A5B6F4B6275B64
α
α&(4A4%5 !"4#$%45)F24E,4AB44#"4#$%D&(84#(4
1
:61 56ED6E1 835D3D1 D'1 D1 E1 3566261 =D1 61 6965D2631 56'4'11 :656556(1 61 >D6D1
53615161563D1D'12561D>6!11A6156E1A!1312D96E1>D6D'151696531D655361563D1
=D1 =3651 E6'5D1 3E1 9!61 EDM4'D(1 3'1 1 61 1 5361 1 835D3D1 1 69DAD'1 1 31 1 D63511
E66E6611=D1?A7@(11=D115D'11865!11=6116116965D26311E33(113E111E66E6611=D11
?A7<@11D1135662611=D116965D2631A'6583D'11%1D'1=51D13161835156''4561
3'1 1 D54661 1 61 563D1 536(1 =D61 E6'5D1 51 =3651 2646'1 D'1 61 51 61 D2DD1
'6'11%131A61693D6E1A!1615313(153515521616F4DDA5D42(161E6'5D15361E66E'11
D6526ED36'1=D15523D1E6'1156F4D561=3651835156''45611
112D96E11>D6D'11511D11EDM4'D113E116965311D655361563D1=D1=3651E6'5D13'13'1
A661 'DE656E(1 A41 61 556'ED1 835D3D1 =35E1 A71 35D31 56''4561 =3'1 1 D1 E1
3566261=D1616965D2631E33111>D6D12E6131=1A615'6E1D15E6511693D161
835D3D151616965D26315361865'4'1α11
61-1111&956''D15161563D15361
5216F1?L@(1?/@13E1?D0@(1616956''D15161563D1536131A6156=5D613'1D16F1?DD@31
1
v 2, 5 =
k 2 K1 K 3 K 6 K 7 K 8 2 PH 2 S D0'' S m 2 S m5
i
1
k 2 K1 K 3 K 7 K 8 PH 2 S S m 2 + D0'' S m5
1
?DD@1
2
i
A=6865(135ED112D5'!1A'6583D'(16561D'15523D1518DE'13161D6531D6553611
=D163E'1131E6563'61D1613135631A6=6618<13E1813'6'(1=D1'6F46!1
'='1E=161>D6D153611:6565561D1D'166''35!11341551D'162631A!1556D1
612H154D1=D131'455361553D1?α@1E65D6E13'1D1&F1?D7@31
Fc (α ) =
S c (α )
1
S0
?D7@1
=6561?α@15656'6'16131'455361A6=6618<13E18113'6'11311611D65311D6553611
311311D8611553D31865'D1α(13E10161DDD318<135D61'455361356311:61835D3D15161
'455361 553D1 ?α@1 31 A61 E6652D6E1 3>'1 1 1 61 1 2E6D1 1 51 1 463D1 1 3E1 1 5=1 51
8DE'1 1 31 1 61 D6531 D655361 D1 33!1 =D1 61 "3261 2E616L1 D61 6561 D'1 1 33!D31
6956''D1 51 1 ?α@1 551 61 'DE656E1 6265!(1 D'1 54D1 3'1 A661 A3D6E1 A!1 263'1 51
4265D31"61F351343D'1655526E131EDM6561553D31865'D'11:61696'D151
D'126E!1165135D616265D6'1=D1A6131'4A$6151544561=5>11:61563D1536131
6565561 A61 =5D61 35ED1 1 6F1 ?D-@1 A!1 3>D1 D1 341 61 E6563'61 D1 61 8<981
D6553631
k 2 K1 K 3 K 6 K 7 K 8 2 PH 2 S D0'' S m 2 Fc (α )S m5
1
v 2, 5 =
i
k 2 K1 K 3 K 7 K 8 2 PH 2 S S m 2 + D0'' Fc (α )S m 5
1
1
?D-@1
i
%1 D'1 =51 DD1 31 'D61 EDM4'D1 ?'61 H@1 3E1 696531 D655361 1 563D1 1 ?'61 1 7@1 1 53611
E6652DD1 1 '6'1 1 3561 1 A1 D4E6E1 3'1 D2D1 3'6'1 D1 6F1 ?DD@11 "568651 61 6956''D1 51 61
563D1 5361 3=1 31 3'1 A61 3436E1 A!1 61 3=1 51 3EEDD861 563D1 D26'1 D88D1 9!61
EDM4'D13E1696531D655361563D1=D1=3651E6'5D16/1:D'13=13='14'115DE161'3261
6956''D13'161615'6E11A=6865(1614'6151D'13=1D'13=6E1!1D51'261EDD'13561
56'66E11 %E66E(1 D1 24'1 A61 31 '64E'63E!1 '361 563D(1 61 =1 '6'1 'DE656E1 1 '4E11
A61 11 1 311 D63511 263D'21 1 3E11 61 24D!D1 6RD615161 D6351 2AD3D(1 =D1
3='1 4'1 1 A3D1 61 A31 563D(1 24'1 A61 61 '3261 551 A1 '6'11 %1 D'1 3'6(1 6'61
EDD'1356131545D6E(131D'1=!1A1343D'163E1161'326153616956''D11
%131A61D6E1316151213''42D1?6F1?D@@1'4E11A6183DE1A634'61516156'661511
21 54D'1 D1 61 E62D3511 7686566''1 >D6D1 6''1 '=D1 31 61 φ21 3''42D1 =3'1
865D5D6E1313'1A61693D6E1A!1'261343D'11:6153613=131A616956''6E13'1D16F1?D6@31
v 2, 5 =
cS m 2 S m5
1
S m 2 + dS m5
?D6@1
=D31
c=
Fc (α )K 6 DO ''
i
k 2 K 1 K 3 K 7 PH 2 S
1 B1
Fc (α )DO ''
d=
i
1
1
k 2 K1 K 3 K 7 K 8 2 PH 2 S
%E66E(1 61 1 3E1 E1 8346'1 54D'1 51 62653456(1 3'1 6956''6E1 D1 61 5361 3=1 E63D6E1 D1 6F1
?D6@(1=6561A3D6E13>'11'45DE3D16965D26'1655526E1315451ED'D162653456'11D11
DL(1=D1'='161835D3D1512?@13E12?E@1865'4'1DU:(1DED36'131556D4'1E66E661=D1
616265345611:4'(113E1E18346'123!1A61683436E15513!16265345613E16153D'15161
536'1A655613E13565131626534561$42131A613436E14'D16F1?DH@31
v 2,5
v 2,5
c(295°C )S m 2 S m 5
S + d (295°C )S m5
d (295°C )
= m2
1
c
(
285
°
C
)
S
S
°
285
C
(
)
m
2
m
5
g
S m 2 + d (285°C )S m5
?DH@1
1
58E24844:2,2726AA5B64B4C6464C64E6A5B674B4*24B4C6D47EF5A5B642A5B64A45BE744
A2,2AE274%0'==%'=' !"4#$%&'4#"4#$%D&%('4#"439224464424A924FE2742+,27724564
2D641(4
1
D111D/11'='116113436E118346'115116'61153D'11551131626534561$42155217LHNF117/HNF1
31835D4'1553D31865'D'11
1
58E24044!FEFA24A24A5B74A2464)2B24A924?E,74B4%8'4AB4%0' !4E6A5B674B4α
α"4#$%&'4#"4
#$%D&%('4#(4
:61 3436E1 5361 53D'1E1 1 835!1 'DD5D3!1 =D1 61 553D31865'D11 :D'1 56'412D1
693D1=!1616'183DE3D11611φ213''42D11=3'11865D5D6E116965D263!11%E66E(11A634'611
511611263'45626116555113E11611=63>1835D3D151613436E1536153D'(1616965D2631
8346'1 5623D1 359D236!1 '31 D1 61 6956E1 E23D1 ?5521 0171 1 1 1 01L@11 1 D3!(1 1 611
6965D2631153611511611'45DE3D1563D131A61556E11616956''D151613436E1
53613''42D131'318<981D6531D655361?6F1?DD@@13E1613436E153613>D1?α@1
D1341?6F1?D-@@111693261514265D315DD1D'156'66E1D1D117011
1
58E24%44!B,57B64)2A322642+,2526AF464FEFA242A5B64A274B4C6D47EF5A5B64A4 !"4
#$%&'4#464#$%D&%('4#(42924FEFA24A27432242A2562477E568444B67A6A4C6D=C64
56A26F456A2248234F562464)34A5684α
α456AB4BE6A4)F4F562(4
'11'=11D11D11170(113436E113E116965D263114586'1363511A61D153651E13566261
A41 6561 D'1 31 'D1 E68D3D1 5521 31 553D31 865'D1 51 01711 :61 31 A'6586E1 A6=661 1 611
6965D263113E116113436E114586'11311A61693D6E1A!1615523D1518DE'131618<9
81 D6531 D65536(1 3'1 '=1 A!1 :&"1 3E1 6651 253!1 35365D3D'1 ?6D1 -1-@11
:615523D1516'618DE'123!163E1131E6563'61D1618<13E1813'6'1313563(13E1
'6F46!1D'123!1'5!156'53D161>D6D153611W61'DE65D1D'16261D161
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