ÐÏࡱá>þÿ prþÿÿÿoÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿì¥Á9 øR¿ÜObjbjýÏýÏ2~Ÿ¥Ÿ¥î'ÿÿÿÿÿÿl&&&&&&&:îîîî4"t:§.¢^¢¤¤¤¤¤¤$Õ õ ÔÈ™&È&&a&&¢¢v†&&†– €A ùToÇ:´î††w0§†É É †::&&&&ÙProgress of the carbonylation synthesis with Rhodium or Iridium catalysts Jiang Dazhi (Institute of Chemistry, Chinese Academy of Sciences, Beijing 100080) Abstract Progress on the synthesis of acetic acid and acetic anhydride by the Rhodium or Iridium catalyzed carbonylation, particularly during the last fifteen years or so, and the comparison of the Rhodium- or Iridium-based catalysts in some relative aspects were summarized. Keywords Acetic acid, Acetic anhydride, Carbonylation, Rhodium, Iridium catalyst Ñ”0ñ”¬PS°úWTb€b/gÛ�U\  HYPERLINK "mailto:jiangdz@iccas.ac.cn" ‹„'Yzf (-NýVÑyf[b–Sf[xvz@b,S¬N100080)     °úWTb ÿò]/fS_MRhQt‹‘x‘ŒT‹‘P‘å]N„v;NAm€b/g0ê� NNª~90t^ãNR(WbìN„v kQ”N ;esQ¡‹R-N0ÐcúQ�O`—býVê�ñ]„v€b/gy{ú^10N(T/t^°úWTb‹‘x‘u§N¿~„v¨R®‹_ËY0RÊN)Y ÿbýV„v‹‘x‘å]Nb—ŒŒò]Ï~ÑSu†N9h,g'`„vl�ØSÿÇ‘(u°úWTb€b/gê�ú^0_Û�ŒT-NYTD�PŸ4Yv^Û� ÿ(W10Yt^„vöeô•Ì‘ ÿObýV„v‹‘x‘§NÏ‘û†NÛV PØ�Y ÿ;`§Ný€Ñ�200N(T/t^ ÿ(W*geg„v2~3t^Ì‘uó��‰¾�0R300N(T/t^åN N0(W‹‘P‘å]N¹eb— ÿbýV�O`—ê�;NåwÆ‹§NCg€b/gò]ŽN2003t^5g(W_lÏ‚9N3–_Nú^Ëz†NNag‹‘P‘°úWTbÕ‹Œšu§N¿~ ÿ„˜¡‹2007t^-N ÿsSïSib§N0R8-10N(T/t^0Ù�hˆf†NbýV„v‹‘x‘ŒT‹‘P‘„v°úWTbå]N€b/g ÿ°sò]PŸ«ŽŽNNLuHQÛ�ýV¶[LˆR0Ñ�10Yt^eg ÿ�–@w‹‘x‘ŒT‹‘P‘„v°úWTbå] zy˜îv„vøvç~/T¨R ÿýV…Q(WÙ�N†˜ßW„vxvzŒT€b/g_ÑSå]\O_Nôf R;mÃ�w�eg0,g‡eèe(Wù[ýV…QYÑ”0ñ”¬PS°úWTb€b/gÛ�U\ˆNåN‚ið� ÿv^¢c¨‹býV‹‘x‘ŒT‹‘P‘„v°úWTb€b/g„vÑSU\‹�¿R0     °úWTbÕlu§N‹‘x‘ŒT‹‘P‘„v¬PSBRSOû|ÊSvQøv”^å]z‚ ÿ;`SOegô‹ ÿïSåNR:N$N'Y{|[1] ÿsSx‘'`¬PSBRSOû|„vKoch³xck»yP[°SÍS”^ï�¿~ŒTg!ÏeÑ‘^\°úWSTir/dS }¬PSBRSOû|„vReppeÜ~T¬PS°SÍS”^ï�¿~0Ñ”0ñ”¬PS°úWTb ÿž[E– N/fcTNÍy°SÍS”^ï�¿~0(WÜ~T¬PS°úWTbå]z‚-N ÿ²møvSOû|Ñ”0ñ”¬PSBR„vO(uHeœgg}Y0,g‡e;N�‰ËNÍ~Ñ”0ñ”¬PSBR²møvÕl°úWTb€b/gÛ�U\ŒTÑSU\‹�¿R0 10Ñ”¬PS°úWTb„vÍS”^:gt     (WÇ‘(ug!ÏeÑ‘^\°úWSTirNdS }bdS }STir¬PSBRSOû|agöN N ÿ1u2u‡‘0‹‘x‘2uo‘ŒTŒN2uš‘I{2u'lúWSTirTb‹‘x‘ŒT‹‘P‘„v°úWTb ÿRËYÍS”^6–µk@bÏ~†S„vŒ[hQ/f TN*N¬PSª_¯sÇ� z[2]ÿ      CH3X + CO  INCLUDEPICTURE "http://www.chemistrymag.org/cji/2007/images/09401501.gif" \* MERGEFORMATINET CH3-CO-X XÿCl, Br, I ÿ1 ÿ sS–™HQubYNp‘dSSir ÿT€/f‹‘x‘ŒT‹‘P‘qQ T„vMRSOSTir0\O:N©R¬PSBR„vdS }bdS }STir ÿvQ©R¬PS\O(u g‚Y Nz˜�^ ÿsSI>Br>Cl0     °såN‹‘x‘ŒT‹‘P‘„v°úWTbå]N-N«ˆnfM�Ç‘(u„vÑ”°úWSTir/˜x2u÷p¬PSBRSOû|:N‹O ÿegô‹fÙ�N¬PSª_¯sÇ� zŒT°úWTbÍS”^:gtÿ  INCLUDEPICTURE "http://www.chemistrymag.org/cji/2007/images/09401502.gif" \* MERGEFORMATINET  þV1 Ñ”/˜x¬PS°úWTbÍS”^:gt     (WÙ�N¬PSª_¯sÇ� z-N@b§Nu„vYNp‘˜x ÿN2u‡‘b4lÍS”^ub‹‘x‘ ÿN‹‘x‘2uo‘b‹‘x‘ÐvÍS”^Rub‹‘P‘0÷–#žI{ºN[3] Ç‘(uÏ‘P[Sf[ gHe8h¿Rý€Ñ�fî]_0xvzÑS°s ÿCH3Iù[[Ir(CO)2I2]- „v'lS Rb ÿ�‰Ôkù[ [Rh(CO)2I2]- „v'lS Rbë_¦~150 Pÿ €ù[¥c Neg„vÁ�ûyÒceQÍS”^ ÿ[MeRh(CO)2I3]- tS�‰Ôk [MeIr(CO)2I3]- ë_105-106 P0Ù�1\/fô‹ ÿñ”¬PS2u‡‘°S„v¬PSª_¯s-N ÿ'lS Rb N�Q/fbaÍS”^ ÿÁ�ûyÒceQÍS”^Mb/f�§cek¤š0ñ”¬PSª_¯s„vÁ�ûyÒceQÍS”^ ÿS+T gN*N˜x�»yP[ÿI- ÿÎN [MeIr(CO)2I3]- -N㉻yúQeg ÿN*NCOÛ�eQM‘MO ÿåNÊS2uúWÁ�ûy0Ù�Ì‘gba„vÍS”^ek¤š/f-Nô•SO a!'’! b!'„vl�S ÿvQ-NSìb˜x�»yP[ÿI- ÿ„v㉻yŒTCOÛ�eQM‘MOÿ2uúWTz˜_»�MO„vCOM‘SOÁ�ûy ÿ/f�gvQÅ��„v0ŽN/f ÿñ”/˜x¬PS°úWTb„vÍS”^¨R›Rf[¹e z¿O/fÿ r = k . [Ir] . [CO] / [I-] ÿsS°SÍS”^�¦^rNñ”¬PSBRSm¦^ŒTCOSm¦^bckÔk ÿN˜x�»yP[Sm¦^bÍSÔk0 hˆ2 Ñ”0ñ”¬PSª_¯ssQ.•ÍS”^Ç� z;mSÂSpe ÍS”^Ç� z;mSípqDðH`" kJ/mol;mSµqDðS`" J/(mol.K)'lS RbRh-AcOH60-50 [9,10]-120- -165 [9,10]Rh-AcOAc46 [9]-180 [9]Ir-AcOH54[11]-113[11]Á�ûyÒceQRh-AcOH63[10]-59[10]Ir-AcOH33[12]-197[12]    hˆ2 RúQ†N1u!j‹WÍS”^Kmš[„vÑ”0ñ”¬PSª_¯s-NsQ.•ÍS”^Ç� z„v;mSÂSpe0Ù�›Npenchˆf†N(WÑ”¬PS°úWTb‹‘x‘ÿRh-AcOH ÿb‹‘P‘ÿRh-AcOAc ÿ-N ÿ'lS Rb„v;mSMO’W�‰Ôkñ”¬PS°úWTb‹‘x‘ÿIr-AcOH ÿ„vØš„vY ÿÑ”/˜x¬PSagöN N„v'lS Rb/fte*N¬PS°SÍS”^„v�¦^³Qš[ek¤šÿ €(Wñ”¬PSagöN NÁ�ûyÒceQ„v;mSMO’W ÿøvÍS ÿ�‰ÔkÑ”¬PS„vØš„vY ÿ³Qš[†Nñ”/˜x¬PSagöN N„vÁ�ûyÒceQÍS”^/fte*N¬PS°SÍS”^„vbaek¤š0MRb—Ðc0R„véeg„vñ”/˜x¬PS1u2u‡‘°STb‹‘x‘Kmš[„vDðG`" ÿ1uŽN N/f(WgOSagöN NÛ�Lˆ„vž[Œš ÿÓ~œgO g@bOPØš ÿFONñ”¬PS°úWTb‹‘x‘Ç� z-NbaÍS”^„v;mSMO’WÍN N1YvQïSÔk'`0     ÎNñ”/˜x¬PS°úWTb„vÍS”^¨R›Rf[¹e zr = k . [Ir] . [CO] / [I-] ïSåN„˜Á‰ ÿý€Y(W-Nô•SO a!'’! b!'l�SÙ�NekOS©Rd–»S˜xSir„virÍy ÿ1\ïSåN\O:NÃOÛ�BRb©R¬PSBRO(u0xvzcúQ ÿÔkƒ�}Y„vÃOÛ�BRb©R¬PSBR g$N{|Ñ‘^\STirÿN{|/f •0I•0^l0S•ŒTß”„vUS¯~„v˜xSir ÿæSN{|/f¨”0ü”0Œ”ŒT•„v°úW-˜xM‘Tir0     hˆ3RúQ†Nè�Rûm RBRù[2u‡‘°úWTbÍS”^�‡s„vq_ÍT0ž[Œšhˆf ÿ ReQ^—Ñ‘^\STirûm RBRn-Bu4NI ÿŸS g„v¬PS;m'`ÍS €×S0R%NÍ‘„vÏQ1_ÿ(WÑ‘^\STirûm RBR-N ÿRu(CO)4I2\O:Nñ”/˜x¬PSBRSOû|„vÃOÛ�BR ÿvQHeœgg}Y0 hˆ3 TÍyûm RBRù[2u‡‘°úWTbÍS”^�‡s„vq_ÍT ÷Sûm RBRù[ [Ir] id\ÔkSTY ÿmol/L/h1ÿzz}vù[ÔkÕ‹Œš ÿ0:18.22n-Bu4NI1:12.73LiI1:14.3.4Ru (CO)4I25:121.65Os (CO)4I25:118.66CdI25:114.77InI35:114.88InI3 / Ru (CO)4I25:1:119.49Ru (CO)4I21:0ÿàeñ” ÿ0    xvz¤‹:N ÿRu(CO)4I2I{Ñ‘^\ÃOÛ�BRôv¥cÂSN0R¬PSª_¯sÍS”^KN-N ÿb_bN*N©R¬PS!k§~ª_¯s[7]ÿ  INCLUDEPICTURE "http://www.chemistrymag.org/cji/2007/images/09401504.gif" \* MERGEFORMATINET  þV3 ñ”¬PS°SSOû|-NÑ‘^\ÃOÛ�BR„v©R¬PS:gtÿ¶nBR:N4lb2u‡‘ ÿ     sS¶nBRS„vÑ‘^\ÃOÛ�BRM(CO)xIy(solv) g©RŽNM–NOÁ�ûyÒceQÍS”^„v;mSMO’W ÿO[MeIr(CO)2I3]- ôf¹[f㉻yúQI- ÿv^ÃObCOÛ�eQÿfeˆNKNM‘MO ÿÎN €Oñ”¬PS°úWTb„vte*N¬PSª_¯sÇ� z�¦^—_åNÐcØš0ž[ŒšcúQ ÿ(Wñ”¬PS2u‡‘°STb‹‘x‘ÍS”^SOû|-N ÿûm R‹‘x‘2uo‘ïS>fW„0W R�ÍS”^ ÿNûm RÏ‘ïSåNˆ_Øš0(WþV3@b:y„v©R¬PS!k§~ª_¯s-N ÿO»yP[`„vÑ‘^\ÃOÛ�BR [M(CO)xIy+1]-[H]+ b` Y0RvQRËY` [M(CO)xIy(solv)] ÿÇ‘(u‹‘x‘2uo‘ÔkO(u2u‡‘ôf:N g)R ÿÙ�7h NOàV:Nˆmd–˜x�»yP[0 €Ù~SOû| �bÇ�Y„v4l+TÏ‘0€Q†0R‹‘x‘2uo‘ÂSN„v g:gÍS”^s^aˆ ÿñ”¬PS°úWTb„vÍS”^¨R›Rf[¹e z1\ØSbÿ r = k . [Ir] . [CO] . [MeOAc] sS°SÍS”^�¦^rNñ”¬PSBRSm¦^0COSm¦^ŒT‹‘x‘2uo‘Sm¦^bckÔk0penchˆf ÿÇ‘(uñ”¬PS°úWTb‹‘x‘@bý€¾�0R„vg}Y„v¬PSÍS”^�‡s:N2.0×103 mol AcOH/(mol Ir.h)[7]0 30Ñ”0ñ”¬PS°úWTbå]z‚Ôkƒ�     Ñ”0ñ”¬PS°úWTbå]z‚ ÿ1uŽN¬PSª_¯sŒTÍS”^¨R›Rf[„vî]_ ÿü[ô�(Wˆ_Y¹eb— g N TKNY0MonsantolQøSxvzºNXT[13]ée(WÖNìNÑSfÑ”¬PSBRgô• ÿ1\ù[Ñ”0ñ”Ù�$NÍy¬PSBR(uŽN‹‘x‘„v°úWTb„vyr'`ZP†NÔkƒ�0Ñ�t^eg ÿÑ�îObI{[14]ù[ñ”¬PSBR„vCativaå]z‚NÑ”¬PSBR„vMonsantoå]z‚„vN›Nq_ÍTàV }_NÛ�Lˆ†Nù[Ôk0,g‡eßbÓ~TÙ�$NÍy¬PSBR(uŽN‹‘x‘ŒT‹‘P‘„v°úWTbÑ�10Yt^eg„vÑSU\ ÿ1\°úWTbSOû|-NN›NÍ‘�‰Ä~R„vq_ÍT0ü~ð�Ñ”0ñ”¬PSBR„v N Thˆ°s ÿåNÊS1udk �b„vÙ�$NÍy°úWTbå]z‚„vO:¹p0 ÿ1 ÿ°SSOû|+T4lÏ‘     ;`SOegô‹ ÿ1uŽNÑ”0ñ”¬PSBRÊSvQ;m'`irÍyý�/fÐv{|ir(� ÿÍS”^SOû|-N g4lX[(W ÿù[ŽNÐcØšƒ[ìN„v¶nã‰'`ý€/f g)R„v0FO°SÍS”^Õkßz/fY(Wˆ_ YBg„v¯sƒXKN-N ÿÍS”^SOû|-N g›NÄ~Rv^ NœU"k4l ÿ‹O‚Yub„v‹‘P‘1\ Ný€G�0R4l ÿ&TR1\ØSÞV0R‹‘x‘†N0     (W‹‘P‘„v°úWTbSOû|-N ÿŸSR N Ný€ g4l0FOó�\(W°SÍS”^6–µk ÿ‚Yœg g\Ï‘4lX[(W ÿN,‚0Wô‹ ÿå]z‚Íd\O'`ý€1\O gƒ�'Y„v9e„U0ÅNÎNÙ�N¹pegô‹ ÿ‹‘x‘ŒT‹‘P‘T€§Nå]z‚f g@b9e„U[16,17]0Ç‘(ubìN„vYŸc[ÐvBg.•T‹WÑ”M‘Tir¬PSBR„v°úWTbå]z‚[18,19] ÿTb‹‘x‘öeù[ÍS”^SOû|„v+T4lÏ‘�‰BlïSåNM–0R5~6 wt.% ÿÍS”^�‡sïSåN¾�0R6.6×103 mol AcOH/(mol Rh.h) ÿ°S§Nir �éb'`ÝOc(W99%åN N0 €Ù�{|Ñ”¬PSBR(uŽN‹‘x‘2uo‘bŒN2uš‘°STb‹‘P‘öe ÿ°SSOû|-Nàe4l ÿ¬PSÍS”^�‡sïSåN¾�0R2.8×103 mol AcOAc/(mol Rh.h) ÿ°S§Nir �éb'`¥cÑ�100%0 ÿ2 ÿ‹‘x‘2uo‘Sm¦^„vq_ÍT     (W°SÍS”^SOû|-N ÿ ReQ‹‘x‘2uo‘ŒT/bŒN2uš‘ ÿN,‚0Wô‹ ÿ/f:N†NTb‹‘P‘0FOå‚SOû|-N g4lb¹[f§Nu4l„vir™e0ø‹‚Y2u‡‘02ux‘b2ux‘2uo‘I{X[(W ÿ1\ NO g‹‘P‘ub[15]0     Ç‘(uÑ”¬PSBRÛ�Lˆ°úWTböe ÿ‚YœgTb„v/f‹‘P‘ ÿ‹‘x‘2uo‘àe‘u/f;N�‰„vÍS”^ir™eÿ €‚YœgTb„v/f‹‘x‘ ÿïSåN N R‹‘x‘2uo‘0‹‘x‘2uo‘Sm¦^(W1 wt.%åN Nöe ÿ NOq_ÍT¬PSÍS”^�‡s01udk weg ÿ‹‘x‘2uo‘ RY†NàeÊv ÿàV:NÙ�öeSOû|-N„v2u‡‘Sm¦^1\Oøv”^M–NO ÿOq_ÍT0R‹‘x‘„vöezz§N‡s0æSN¹eb— ÿSOû|-N‹‘x‘2uo‘Ç�Y ÿÑ”¬PSBR„v¶nã‰'`ý€ N}Y ÿO gè�RÑ”¬PSBR‰lÀmub0     (Wñ”¬PS„v°úWTb‹‘x‘SOû|-N ÿÎNÍS”^¨R›Rf[¹e zr = k . [Ir] . [CO] . [MeOAc]eg w ÿ‹‘x‘2uo‘ RY†N ÿÍS”^�¦^ë_0ž[Œšhˆf ÿ(Wñ”¬PS„v°úWTb‹‘x‘SOû|-N ÿ‹‘x‘2uo‘Sm¦^ïSåNÔkÑ”¬PS°úWTbSOû|-N„vØšúQˆ_Y0‹‘x‘2uo‘(Wñ”¬PS°úWTb‹‘x‘SOû|-N„v;N�‰\O(u/f ÿNHIÍS”^ ÿOS©RÑ‘^\ÃOÛ�BRž[°s©R¬PS!k§~ª_¯s0ñ”¬PSBR(W‹‘x‘2uo‘-N„v¶nã‰'`ý€ÔkÑ”¬PSBR„v�‰}Y„vY0(Wñ”¬PS„v°úWTb²mSOÍS”^ir™e-N ÿd–†N‹‘x‘2uo‘KNY ÿØ� g2u‡‘04lŒT˜x2u÷pI{0‚YœgÍS”^ir™eÌ‘¡l g†N4lŒT2u‡‘ ÿ_N1\ NïSý€ g‹‘x‘ub0£�HN ÿÙ�öeO NOb_b‹‘P‘bTÿT{Hh/f ˆ_¾– ÿb€ô‹ ˆ_\ ÿàV:N¬PSª_¯s§Nu„vYNp‘˜xN‹‘x‘2uo‘ôv¥cÍS”^„v;mSMO’Wˆ_Øš ÿ:\‹‘x‘Ðv{|ÂSN ÿ‹‘P‘„vub�¦^O/f^—8^ba„v0 ÿ3 ÿ˜x2u÷pSm¦^„vq_ÍT     Ç‘(uÜ~T¬PS°úWTbå]z‚ï�¿~Tb‹‘x‘ŒT‹‘P‘ ÿ˜x2u÷p/fÅ_ NïS\„vg;N�‰„v©R¬PSBR ÿ/f°SÍS”^¬PSª_¯s„v;NÒ‰0 Ù�sSO(Wñ”¬PS°úWTb‹‘x‘-N_N N‹OY0êS/f(Wñ”¬PSSOû|-N ÿ˜x2u÷p(uÏ‘ˆ_\ ÿN,‚(W6 wt.%åN Nöe ÿ¬PSÍS”^�¦^NvQSm¦^MbHTckøvsQ0 €ù[ŽNÑ”¬PSSOû| ÿÍS”^¨R›Rf[¹e zò]cúQ ÿ¬PSÍS”^�¦^/f�–˜x2u÷pSm¦^ € NGS„v0(Wñ”¬PSSOû|-N ÿ˜x2u÷p(uY†N ÿ NFOàeÊv ÿÍS € g³[0FO(WÑ”¬PSSOû|-N ÿÅ`µQRøvÍS0uó� gN)RcúQ[20] ÿSìb˜x2u÷p(W…Q„v˜xSm¦^Øš†N ÿ g©RŽNÐcؚє¬PSBRSOû|„v€íp'`ý€ ÿO gïSý€ub„víp N3zš[„v[Rh(CO)I4]- l�ØSbíp3zš[„v[Rh(CO)I5]2-0Ù�Ç{N)Rú^®‹ ÿ(WÑ”¬PSSOû|-N ÿ”^ÝOcI/Rhid\Ôk:N20bôfY0 ÿ4 ÿN'lS³xR‹S„vq_ÍT     ÎNÍS”^¨R›Rf[¹e z w ÿCOù[ŽNñ”¬PSSOû|„vÍ‘�‰'` ÿ�‰Ôkù[Ñ”¬PSBRSOû|„v'Y„vY0(WÑ”¬PSBRSOû|-N ÿ z gNš[„vCOR‹ST ÿ¬PSÍS”^�‡s¿ONCOR‹SàesQ0 €(Wñ”¬PSBRSOû|-N ÿ¬PSÍS”^�‡s�–COR‹SHT¿~'` NGS‹�¿R0COR‹SGS0R0.8 MPaåN Nöe ÿÙ�Íy¿~'` NGS‹�¿RMbOØS0Ñ�îObI{„vž[Œš[21]Ø�cúQ ÿ(Wñ”¬PSÍS”^SOû|-N ÿžX RCOR‹S g)RŽNÏQ\ubŒN2uš‘I{oRÍS”^ ÿÐcØš§Nir‹‘x‘„v �éb'`0 ÿ5 ÿ¬PSBRSm¦^     (W°SÍS”^SOû|-N ÿ�‰ÝOcÑ”¬PSBRYŽNo‚}Y„v¶n㉶r` ÿvQSm¦^g}Y§c6R(W400~800 ppmƒôV…Q ÿgY N�‰…�úQ1000 ppmÿ €ù[ñ”¬PSBRegô‹ ÿvQSm¦^ïSåN0R3000~4000 ppm,uó�6000 ppm0Ñ”¬PSBR(WÍS”^SOû|-N„vSm¦^¾�0R600 ppmåN Nöe ÿåNöezz§N‡sÿSTY ÿ¡‹„v¬PSÍS”^�‡sù[¬PSBRSm¦^„v¿~'`žX•sQû|1\>fW„0W‹� ÿvQïS¾�0R„vSTYg'Yf„v N'YO¹pÿ t$ ¬PSBR@b(u„v5�Ñ‘^\:Nñ”ŒTŒ”I{ ÿ÷Ny,S¬N,1995:143-177. 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