Nghiên cứu tính chất catalaza và peroxydaza của phức Co(II) với axetylaxeton

B GIO DC V O TO TRNG I HC BCH KHOA H NI Lấ VN HUNH NGHIấN CU TNH CHT CATALAZA V PEROXYDAZA CA PHC Co(II) VI AXETYLAXETON LUN N TIN S HO HC H Ni Nm 2012 B GIO DC V O TO TRNG I HC BCH KHOA H NI Lấ VN HUNH NGHIấN CU TNH CHT CATALAZA V PEROXYDAZA CA PHC Co(II) VI AXETYLAXETON Chuyờn ngnh : Hoỏ lý thuyt Hoỏ lý Mó s : 62.44.31.01 LUN N TIN S HO HC NGI HNG DN KHOA HC : GS TSKH Nguyn Vn Xuyn GS TSKH Nguyn Minh Tuyn H Ni Nm 2012 LI CAM OAN Tụi xin cam oan, õy l cụng trỡnh nghiờn cu khoa hc ca riờng tụi Nhng s liu v kt qu nghiờn cu c cụng b lun ỏn, ó c kim tra cn thn, trung thc v cha c ngi khỏc hoc nhúm tỏc gi khỏc cụng b Cỏc s liu s dng cho lun ỏn t cỏc cụng trỡnh cụng b th, ó c cỏc ng tỏc gi cho phộp s dng TC GI LUN N Lờ Vn Hunh LI CM N Tỏc gi ó c s giỳp nhit tỡnh v to iu kin rt thun li ca rt nhiu cỏ nhõn v th, tụi xin by t lũng cm n sõu sc ti cỏc Giỏo s, Tin s, cỏc Thy cụ giỏo ó giỳp tụi hon thnh tt lun ỏn ny Tụi xin trõn trng cm n sõu sc ti GS TSKH Nguyn Vn Xuyn, GS.TSKH Nguyn Minh Tuyn ó nhit tỡnh nh hng v úng gúp nhng ý kin vụ cỳng quớ bỏu v sõu sc lun ỏn c hon thnh Tụi xin trõn trng cm n Trng i hc Bỏch khoa H Ni, Vin o to sau i hc Trng i hc Bỏch khoa H Ni, cỏc Thy Cụ Vin K thut hoỏ hc, c bit B mụn Hoỏ lý ó to iu kin thun li nghiờn cu khoa hc Tụi xin trõn trng cm n sõu sc ti cỏc Thy Cụ B mụn Hoỏ lý Trng i hc Bỏch khoa H Ni ó to mi iu kin thun li trang thit b thớ nghim dựng nghiờn cu, cỏc ý kin úng gúp vụ cựng quớ bỏu tụi hon thnh lun ỏn Tụi xin trõn trng cm n Vin Khoa hc Cụng ngh Vit nam, Trng i hc Khoa hc t nhiờn thuc i hc Quc Gia H Ni, V Mụi trng B Giao thụng Vn ti, trng i hc Hng Hi, Trung tõm Quan trc Mụi trng bin B t lnh Hi Quõn ó to iu kin, nh hng, cung cp cỏc thit b cho vic nghiờn cu hon thnh lun ỏn Tụi xin trõn cm n Trng i hc Kinh t - K thut Cụng nghip ó to iu kin cho tụi thi gian sut quỏ trỡnh lm lun ỏn Tụi xin trõn thnh cm n ti cỏc Giỏo s, Phú Giỏo s, Tin s, cỏc nh khoa hc ó cú nhiu úng gúp cho vic hon thnh lun ỏn Xin trõn trng cm n! TC GI LUN N Lờ Hunh MC LC Trang DANH MC CC Kí HIU V CH VIT TT DANH MC CC BNG DANH MC CC HèNH NH V TH M U 1 TNG QUAN 1.1.Nghiờn cu v ngoi nc v xỳc tỏc phc ng th 1.2 Xỳc tỏc enzym 1.2.1 c im cu to phõn t enzym 1.2.2 C ch hot ng ca cỏc enzym 1.2.3 Mi quan h gia xỳc tỏc phc v xỳc tỏc enzym 1.3 Xỳc tỏc ng th oxi hoỏ kh 1.3.1 c im cu to ca cỏc iom kim loi chuyn tip 1.3.2 c im ca Ligand tham gia to phc 1.3.3 Kh nng to phc ca ion kim loi chuyn tip MZ+ vi Ligand 1.3.4 S to phc lm thay i hot tớnh xỳc tỏc ca ion MZ+ 1.3.4.1 S to phc lm tng bn thu phõn ca cỏc ion kim loi MZ+ 1.3.4.2 S to phc lm thay i th oxi hoỏ - kh ca ion kim loi MZ+ 1.3.4.3 S to phc lm tng hot tớnh xỳc tỏc ca ion kim loi MZ+ 1.3.4.4 S to phc lm tng tc ca phn ng cú chn lc cao 1.3.4.5 Kh s ngn cm cha bo ton tớnh i xng Orbital phõn t 1.3.6 Chu trỡnh oxi hoỏ - kh thun nghch 1.3.7 C ch ca phn ng di tỏc dng ca xỳc tỏc phc 1.3.7.1 C ch ni cu 1.3.7.2 C ch ngoi cu 1.4 S dng xỳc tỏc phc hot hoỏ O2 v H2O2 1.4.1 Hot hoỏ O2 bng phc cht xỳc tỏc 1.4.2 Hot hoỏ H2O2 bng xỳc tỏc phc 1.5 Quỏ trỡnh Catalaza 1.5.1 C ch phõn t ion 1.5.2 C ch gc ion 1.6 Quỏ trỡnh Peroxydaza 1.6.1 H xỳc tỏc: H2O MZ+ S H2O2 1.6.2 Hờ xỳc tỏc: H2O MZ+ L S (SR, SL) H2O2 1.7 Mi liờn h gia quỏ trỡnh Catalaza v Peroxydaza 7 9 9 10 10 10 11 12 13 13 14 14 15 15 16 17 18 19 19 20 20 21 21 1.8 Mt s ng dng ca xỳc tỏc phc ng th oxi hoỏ kh 1.8.1 ng dng x lý cht thi, bo v mụi trng 1.8.2 ng dng phõn tớch vi lng 1.8.3 ng dng chuyn hoỏ hoỏ hc cỏc hp cht hu c C S THC NGHIM V CC PHNG PHP NGHIấN CU 2.1 Nghiờn cu cỏc h xỳc tỏc phc 2.2 Cỏc cht tham gia phn ng cỏc h nghiờn cu 2.2.1 Ion kim loi to phc Co2+ 2.2.2 Ligand to phc Axetylaxeton (Acac) C5H8O2 2.2.3 Cht oxi hoỏ O2 v H2O2 2.2.4 C cht Indigocarmin (Ind) C16H8N2Na2O8S2 2.2.5 Cỏc cht c ch 2.3 Cỏc phng phỏp nghiờn cu 2.3.1 Phng phỏp ng hc 2.3.2 Phng phỏp quang ph hp th electron phõn t 2.3.3 Phng phỏp dóy ng phõn t 2.3.4 Phng phỏp ng cong bóo ho 2.3.5 Phng phỏp cc ph 2.3.6 Phng phỏp s dng cỏc cht c ch v cỏc cht cnh tranh 2.3.7 Phng phỏp quang ph hp th nguyờn t 2.3.8 Phng phỏp Qui hoch thc nghim 2.4 Dng c v thit b nghiờn cu 2.4.1 Nghiờn cu quỏ trỡnh Catalaza 2.4.2 Nghiờn cu quỏ trỡnh Peroxydaza NGHIấN CU QU TRèNH CATALAZA TRONG H: H2O Co2+ Acac H2O2 (I) 3.1 Nghiờn cu s to thnh phc cht xỳc tỏc gia Co2+ v Acac 3.1.1 Nghiờn cu bng phng phỏp ng hc 3.1.2 Nghiờn cu bng phng phỏp ph hp th electron phõn t 3.1.3 Nghiờn cu bng phng phỏp dóy ng phõn t 3.1.4 Nghiờn cu bng phng phỏp ng cong bóo ho 3.1.5 Nghiờn cu bng phng phỏp cc ph 3.2 Nghiờn cu s to thnh phc trung gian hot ng Peroxo 3.2.1 Nghiờn cu bng phng phỏp ph hp th electron phõn t 3.2.2 Nghiờn cu s to thnh v phõn hu phc Peroxo 3.2.3 Nghiờn cu ng hc s to thnh phc Peroxo 3.2.3.1 Nghiờn cu s ph thuc WPer vo pH 3.2.3.2 Nghiờn cu s ph thuc WPer vo Beta 22 22 24 24 27 28 28 28 29 29 30 30 30 30 31 31 31 31 34 34 34 35 36 38 38 39 40 40 41 43 43 44 45 45 46 3.2.3.3 Nghiờn cu nh hng ca [Co2+]0 n WPer 3.2.3.4 Nghiờn cu s ph thuc WPer vo [H2O2]0 3.2.3.5 Phng trỡnh ng hc s to thnh phc Peroxo 3.3 Nghiờn cu ng hc phn ng Catalaza h (I) 3.3.1.Nghiờn cu s ph thuc tc phn ng WO2 vo pH 3.3.2 Nghiờn cu nh hng ca [Acac]0 n tc phn ng WO2 3.3.3 Nghiờn cu nh hng ca [Co2+]0 ti tc phn ng WO2 3.3.4 Nghiờn cu s ph thuc tc phn ng WO2 vo [H2O2]0 3.3.5 Phng trỡnh ng hc quỏ trỡnh Catalaza 3.4 Qui hoch thc nghim quỏ trỡnh Catalaza vi xỳc tỏc phc [Co(Acac)]+ 3.5 C ch quỏ trỡnh Catalaza xỳc tỏc bi phc [Co(Acac)]+ 3.5.1 Nghiờn cu nh hng ca cht c ch Hq n h (I) 3.5.2 Nghiờn cu nh hng ca cht c ch Ac n h (I) 3.5.3 Nghiờn cu nh hng ca cht c ch Pa n h (I) 3.6 Nghiờn cu s thay i trng thỏi hoỏ tr ca ion Coban bng PP cc ph 3.7 xut s c ch Quỏ trỡnh Catalaza 3.8 Xỏc nh cỏc thụng s hoỏ lý ca quỏ trỡnh Catalaza 3.9 Tng hp cỏc kt qu nghiờn cu chng NGHIấN CU QU TRèNH PEROXYDAZA TRONG H: H2O Co2+ Acac Ind H2O2 (II) 4.1 Nghiờn cu hot tớnh Peroxydaza ca phc [Co(Acac)]+ 4.2 Nghiờn cu ng hcquỏ trỡnh Peroxydaza h (II) 4.2.1 Nghiờn cu nh hng ca pH n WInd 4.2.2 Nghiờn cu nh hng ca [Acac]0 n WInd 4.2.3 Nghiờn cu nh hng ca [Co2+]0 n WInd 4.2.4 Nghiờn cu nh hng ca [H2O2]0 n WInd 4.2.5 Nghiờn cu nh hng ca [Ind]0 n WInd 4.2.6 Phng trỡnh ng hc quỏ trỡnh Peroxydaza 4.3 Qui hoch thc nghim quỏ trỡnh Peroxydaza h (II) 4.4 Nghiờn cu c ch quỏ trỡnh Peroxydaza h (II) 4.4.1 Nghiờn cu nh hng ca cht c ch Hq 4.4.2 Nghiờn cu nh hng ca cht c ch Ac 4.4.3 Nghiờn cu nh hng ca cht c ch Pa 4.5 Nghiờn cu xỏc nh tc sinh mch 4.5.1 Nghiờn cu nh hng ca pH n tc sinh mch 4.5.2 Nghiờn cu nh hng ca [Acac]0 n tc sinh mch 4.5.3 Nghiờn cu nh hng ca [Co2+]0 n tc sinh mch 4.5.4 Nghiờn cu nh hng ca [H2O2]0 n tc sinh mch 4.5.5 Nghiờn cu nh hng ca [Ind]0 n tc sinh mch 47 48 49 50 51 52 13 54 55 56 60 61 62 63 64 65 66 69 71 72 72 73 74 75 76 77 78 81 82 84 85 87 87 88 90 91 92 4.5.6 Phng trỡnh ng hc xỏc nh tc sinh mch 4.6 S chuyn trng thỏi hoỏ tr Co2+ quỏ trỡnh Peroxydaza 4.7 xut s c ch quỏ trỡnh Peroxydaza 4.8 Nghiờn cu mt s ng dng 4.8.1 Xỏc nh vi lng Co2+ mu nc ging khoan bng phng phỏp ng hc xỳc tỏc 4.8.1.1 Nghiờn cu s nh hng ca cỏc kim loi khỏc n tc WInd 4.8.1.2 Lp ng chun xỏc nh Co2+ theo phng phỏp ng hc xỳc tỏc 4.8.1.3 Xỏc nh Co2+ mu nc ging khoan 4.8.2 ng dng xỳc tỏc phc [Co(Acac)]+trong quỏ trỡnh lm khụ mng mc in 4.8.2.1 Thnh phn ca mc in nh tng nc du 4.8.2.2 Mc in nh tng nc du 4.8.2.3 H nh tng 4.8.2.4 c im ca mc in nh tng nc du 4.8.2.5 S khụ ca mc in trờn giy 4.8.2.6 ỏnh giỏ cht lng mc in s dng xỳc tỏc phc [Co(Acac)]+ 4.8.3 ng dng xỳc tỏc phc x lý nc thi ngõm tre na 4.8.3.1 Nghiờn cu nh hng ca xỳc tỏc phc n hiu sut x lý 4.8.3.2 Nghiờn cu nh hng ca pH n hiu sut x lý 4.8.3.3 Nghiờn cu nh hng ca nng xỳc tỏc phc n hiu sut x lý 4.9 Tng hp cỏc kt qu nghiờn cu chng KT LUN TI LIU THAM KHO DANH MC CC CễNG TRèNH KHOA HC CễNG B PH LC 93 64 95 96 97 97 99 100 102 102 103 103 104 105 110 113 114 115 116 117 119 121 129 Cu trỳc ca lun ỏn: Lun ỏn gm 131 trang gm: M u trang, ni dung chớnh 118 trang, c phõn b chng: Chng Tng quan (24 trang), chng Phng phỏp nghiờn cu (11 trang), chng Nghiờn cu quỏ trỡnh Catalaza (33 trang), chng Nghiờn cu quỏ trỡnh Peroxydaza (48 trang), kt lun (2 trang), 123 ti liu tham kho (9 trang); danh mc cỏc cụng trỡnh ó c cụng b liờn quan n lun ỏn (2 trang) DANH MC VIT TT AAS Ph hp th nguyờn t Ac Axit Ascorbic Acac Axetylaxeton AO Orbital nguyờn t COD Nhu cu oxi hoỏ hc DETA Dietylentriamin D Mt quang ca phc Peroxo e electron Hq Hydroquinon Ind Indigocarmin KLCT Kim loi chuyn tip L Ligand MO Orbital phõn t Per Phc trung gian hot ng Peroxo PTGH Phc trung gian hot ng Pa Paranirozodimetylanilin S C cht Sr C cht cú tớnh kh SL C cht cú tớnh ligand XTP Xỳc tỏc phc D Bin thiờn mt quang (s ) Chu k cm ng Wi,Ind TN Tc sinh mch quỏ trỡnh Peroxydaza VO2 Th tớch khớ oxi thoỏt Per O2 Tc thoỏt khớ oxi Ind Tc oxi hoỏ Indigocarmin Per W Tc to thnh phc Peroxo H * Entanpi hot húa S * Entripi hot húa G * Nng lng t ca phc trung gian hot ng K* Hng s to thnh ca phc trung gian hot ng W W DANH MC BNG Bng 1.1 Bng 1.2 Bng 2.1 Bng 2.2 Bng 3.1 Bng 3.2 Bng 3.3 Bng 3.4 Bng 3.5 Bng 3.6 Bng 4.1 Bng 4.2 Bng 4.3 Bng 4.4 Bng 4.5 Bng 4.6 Bng 4.7 Bng 4.8 Bng 4.9 Bng 4.10 Bng 4.11 Bng 4.12 Bng 4.13 Bng 4.14 Bng 4.15 Bng 4.16 Bng 4.17 Cỏc thụng s c bn ca mt s h xỳc tỏc phc ng th Cỏc thụng s c trng ca phõn t O2 cỏc trng thỏi Mt s thụng s hoỏ lý ca Indigocarmin (Ind) Cỏc thụng s hoỏ lý ca cỏc cht c ch Hq, Ac, Pa Bng s liu nghiờn cu bng phng phỏp cc ph Phng ỏn thc nghim vit di dng ma trn qui hoch Ma trn k hoch hoỏ y Cỏc thụng s c trng ca mt s cht c ch Bng s liu ghi ph quỏ trỡnh Catalaza h (I) Xỏc nh cỏc thụng s húa lý ca phn ng Catalaza c xỳc tỏc bi phc [Co(Acac)]+ nhit 300C Phng ỏn thc nghim vit di dng ma trn qui hoch quỏ trỡnh Peroxydaza Ma trn k hoch hoỏ y quỏ trỡnh Peroxydaza Bng s liu xỏc nh k(Ind + HO*) vi cht c ch Hq Bng s liu xỏc nh k(Ind + HO*) vi cht c ch Ac Bng s liu xỏc nh k(Ind + HO*) vi cht c ch Pa Bng s liu ghi ph quỏ trỡnh Peroxydaza h (II) Ind S ph thuc W612 vo bn cht cỏc ion kim loi khỏc nh hng ca cỏc kim loi khỏc cú nng khỏc n WInd oxi hoỏ Ind S ph thuc 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(2005), Selective carbonylation of benzene to benzaldehyde using O2 as the oxidant in the presence of cobalt complex, Journal of Molecular Catalysis A: Chemical, 225(1), pp 131-135 119 120 121 122 123 Mio Katsumi (JP), Drier for Offset Printing, European Paten, EP0412628, 02/1991 Nelson R Eldred (2001), Chemistry for the Graphic Art-GATF Press Nelson R Eldred (2001), What the Printer Should Know aboet Ink GATF Press Adams, J Christopher (2007), Emulsion Inks, US Patent 7300507 R H Leuach, R J Piece (2004), The printing manual, Kluwer Academic Publischers 130 CC CễNG TRèNH KHOA HC CễNG B Lờ Vn Hunh, Nguyn Vn Xuyn, Nguyn Minh Tuyn (2011), Nghiờn cu ng hc s to thnh phc trung gian hot ng Peroxo h: H2O Co2+ Axetylaxeton (Acac) H2O2, Tp hoỏ hc, Tp 49 (1),Tr 125 128 Lờ Hunh, Nguyn Minh Tuyn, Nguyn Vn Xuyn (2011), Xỏc nh iu kin ti u cho phn ng Catalaza vi xỳc tỏc phc [Co(Acac)]2+ bng phng phỏp qui hoch thc nghim, Hoỏ hc & ng dng, s 4, Tr.1 Lờ Vn Hunh, Nguyn Vn Xuyn, Nguyn Minh Tuyn (2011), Nghiờn cu ng hc phn ng Catalaza c xỳc tỏc bng phc ca Co2+ vi Axetylaxeton (Acac) h: Trong h: H2O Co2+ Acac H2O2, Tp hoỏ hc, Tp 49 (2),Tr 236 - 239 Lờ Vn Hunh, Nguyn Vn Xuyn, Nguyn Minh Tuyn (2011), Nghiờn cu s to thnh phc cht xỳc tỏc ca Co2+ vi Axetylaxeton (Acac) h: Trong h: H2O Co2+ Acac, Tp Hoỏ hc, Tp 49 (s 3),Tr 321 325 Lờ Vn Hunh, Nguyn Vn Xuyn, Nguyn Minh Tuyn, Ngụ Kim nh (2011), Nghiờn cu c ch phn ng Catalaza c xỳc tỏc bi phc [Co(Acac)]+ bng phng phỏp dựng cỏc cht c ch v phng phỏp cc ph, Tp Hoỏ hc, Tp 49 (5AB), Tr 323 329 Lờ Vn Hunh, Nguyn Vn Xuyn, Nguyn Minh Tuyn, Ngụ Kim nh (2011), Nghiờn cu cỏc yu t nh hng n tc sinh mch ca h: H2O Co2+ Axetylaxeton (Acac) Ind In H2O2, Tp Hoỏ hc, Tp 49(5AB), Tr 330335 Lờ Vn Hunh, Nguyn Vn Xuyn, Nguyn Minh Tuyn, Nguyn Hu Khụi, Ngụ Kim nh (2011), Nghiờn cu thnh phn v hng s bn ca phc Co2+ vi Axetylaxeton (Acac) bng phng phỏp cc ph v phng phỏp ng cong bóo ho, Tp Hoỏ hc, Tp 49 (5AB), Tr 670 674 Lờ Vn Hunh, Nguyn Vn Xuyn, Nguyn Minh Tuyn (2011), Nghiờn cu ng hc phn ng oxi hoỏ Indigocarmin bng H2O2 di tỏc dng ca phc to bi Co(II) vi Axetylaxeton (Acac), Tp Hoỏ hc & ng dng, s 6, Tr Lờ Vn Hunh (2011), Nghiờn cu quỏ trỡnh Peroxydaza ca phc [Co(Acac)]+ bng phng phỏp qui hoch thc nghim quỏ trỡnh x lý nc thi cụng nghip, Hi tho Khoa hc ln th 39 cỏc Trng i hc K thut, Tr 121 127 10 Lờ Vn Hunh, Nguyn Vn Xuyn, Nguyn Minh Tuyn (2011), Nghiờn cu s to thnh v phõn hu gc t HO*, xỏc nh hng s tc oxi hoỏ Indigocarmin (Ind) bng phng phỏp dựng cỏc cht c ch (In) h: H2O Co2+ Axetylaxeton (Acac) Ind In H2O2, Tp Khoa hc & Cụng ngh cỏc Trng i hc K thut s 85, Tr 126 131 11 Lờ Vn Hunh (2012), Nghiờn cu xỏc nh vi lng Co2+ nc ngm bng phng phỏp ng hc xỳc tỏc, Hi tho Khoa hc ln th 40 cỏc Trng i hc K thut, Tr 67 72 Hỡnh 4.6c: S ph thuc lgWInd vo lg[Ind]0 131 12 Lờ Vn Hunh, Nguyn Vn Xuyn, Nguyn Minh Tuyn (2012) Nghiờn cu xỏc nh cỏc thụng s húa lý ca quỏ trỡnh Catalaza c xỳc tỏc ca phc [Co(Acac) +, Tp Húa hc Tp 50(1), Tr 35 39 13 Lờ Vn Hunh, Nguyn Vn Xuyn, Nguyn Minh Tuyn (2012) Nghiờn cu quỏ trỡnh Peroxydaza ca phc xỳc tỏc [Co(Acac)]+ bng phng phỏp qui hoch thc nghim, Tp Húa hc Tp 50(2), Tr 148 152 PH LC Chng trỡnh tớnh hng s bn Kb ca phc [Co(Acac)]+ Program Hang so ben; uses crt; const tieude1 =BANG TINH HANG SO BEN CUA PHUC; tieude2 =:STT : C.10^6 : DD : HDD : DD/HDD : Y : X :; dongke = -'; q=1; DDMAX = 0.1776 Type Bangghi=record C:real; DD:real; HDD:real; Z:real; X:real; Y:real; end; var tn:array[1 100] of bangghi; i,j,n:integer; sx,sy,x2,sx2,xy,sxy:real; a,K,lnK:real; begin clrscr; writeln(Nhap so lieu cac thi nghiem)); write(So thi nghiem n:); readln (n); for i:=1 to n with tn[i] begin writeln(Thi nghiem thu,i,:); writel(C=) readln(C); C:=C*0.000001; Writel(DD=); Readln(DD); HDD:=DDMAX-DD; Z:=DD/HDD; y:=ln(Z)/ln(10); x:=ln(C)/ln(10); sx:=sx+x; sy:=sy+y; x2:=x*x; sx2:=sx2+x2; xy:=x*y; sxy:=sxy+xy; writeln; end; a:=(sx2*sy-sx*sxy)/(n*sx2-sx*sx); lnK:=a*ln(10); K:=exp(lnK); Clrscr; Writeln(Tieu de 1); Writeln; Writeln(dongke); Writeln(Tieu de 2); Writeln(dongke); for i:=1 to n with tn[i] writeln(i:3, ,C*1e+05:, ,DD:5:3, ,HDD:5:3, ,z:5:3, y:6:3, ,x:6:3; writeln(dongke); writeln; writeln(Phuong trinh hoi qui Y = a + q.x); writeln; writeln(Cac he so hoi qui:); writeln(Cac he so hoi qui a:=,a:9); writeln(Cac he so hoi qui q:=,q:9); writeln(Hang so ben cua phuc : ); lnK:=ln(10)*a; K:=exp(lnK); writeln(K=,K:9); readln; end Chng trỡnh tớnh hng s tc oxi húa Indigocarmin (Ind) vi cht c ch l Hydroquinon (Hq) Program Hang so toc do; uses crt; const k2=1.2E+10; {[kHq]} k3=1.2E+09; {[kAcac]} k4=3.0E+07; {[kH2O2]} c1=1.5E-04; {[Ind]} c3=1.0E-5; {[Acac]} c4=1.0E-02; {[H2O2]} epsilon=1.02E+04; d=1; type chuoi=string[20]; bangghi=record c2:real; dd1:real; dc1:real; x:real; y:real; k2c2:real; k3c3:real; k4c4:real; end; var tn:array[[1 20] of bangghi; i,j,n:integer; sx,sy,x2,sx2,xy,sxy:real; a,b,k1,c:real; begin clrscr; writeln('CHUONG TRINH TINH HANG SO TOC DO'); writeln('NHAP CAC SO LIEU THUC NGHIEM'); write('SO THUC NGHIEM: n = '); readln(n); writeln(' n c2 dD1 dc1 y=1/dc1 k2c2 k3c3 k4c4 x'); writeln(' - - - - -'); sx:=0; sy:=0; sxy:=0; sx2:=0; for i:=1 to n with tn[i] begin writeln('Thi nghiem thu',i,':'); write('c2='); readln(c2); write('dd1='); readln(dd1); dc1:=dd1/epsilon/d; y:=1/dc1; k2c2:=k2*c2; k3c3:=k3*c3; k4c4:=k4*c4; x:=(k2c2+k3c3+k4c4)/c1; sx:=sx+x; sy:=sy+y; x2:=x*x; sx2:=sx2+x2; xy:=x*y; sxy:=sxy+xy; writeln; end; a:=(sx2*sy-sx*sxy)/(n*sx2-sx*sx); b:=(n*sxy-sx*sy)/(n*sx2-sx*sx); k1:=a/b; writeln('a=',a:15); writeln('b=',b:15); writeln('Hang so toc k1: ',k1:15); writeln('k1=',k1:15); writeln('Phuong trinh hoi qui:'); writeln('y=',a:10:8,'x+',b:10:8); readln; end Chng trỡnh tớnh toỏn ti u quỏ trỡnh Catalaza % Tỡm giỏ tr cc i Function y = f1(z1,z2,z3,z4) % Mụ t hm cn tỡm cc i Y=10.2645+0.355*Z1+0.038*Z2+1.38*Z313.6316*Z40.1897*Z1*Z2 0.0205*Z1*Z30.4029*Z1*Z40.0051*Z2*Z3 0.0157*Z2*Z4+1.8592*Z3*Z4+0.0253*Z1*Z2*Z3+0.079*Z1*Z2*Z4; z10 = 0.2; z11 = 5.0; N1 = 40; h1=(z11-z10)/N1; z20 = 0.2; z21 = 10.0 ; N2 = 40; h2=(z21-z20)/N2; z30 = 8.0; z31 = 11.0; N3 = 40; h3= (z31-z30)/N3; z40 = 0.02; z41 = 0.5; N4 = 40; h4= (z41-z40)/N4; m = f1(z10,z20,z30,z40); For N1 = 1:40 For N2 = 1:40 For N3 = 1:40 for N4 = 1:40 If f1(z10+N1*h1,z20+N2*h2,z30+N3*h3,z40+N4*h4) >= m m = f1(z10+N1*h1,z20+N2*h2,z30+N3*h3,z40+N4*h4); End End End End End For N1 = 1:40 For N2 = 1:40 For N3 = 1:40 For N4 = 1:40 If f1(z10+N1*h1,z20+N2*h2,z30+N3*h3,z40+N4*h4) == m z1m=z10+N1*h1; z2m=z20+N2*h2; z3m=z30+N3*h3; z4m=z40+N4*h4; End End End End End % fprintf(' Giỏ tr cc i ca hm s l ymax = %f\n',m) fprintf(' V trớ t cc i l z1max = %f\n',z1m) fprintf(' V trớ t cc i l z3max = %f\n',z3m) fprintf(' V trớ t cc i l fprintf(' V trớ t cc i l z2max = %f\n',z2m) z4max = %f\n',z4m) Chng trỡnh tớnh toỏn ti u quỏ trỡnh Peroxydaza % Tỡm giỏ tr cc i Function y = f1(z1,z2,z3,z4) % Mụ t hm cn tỡm cc i Y = 22.6583 0.4332*Z1 0.236*Z2 + 3.357*Z3 18.5045*Z4 + 0.1467*Z1*Z2 + 0.1037*Z1*Z3 0.0313*Z2*Z3 + 0.0203*Z1*Z2*Z3 1.2057*Z2*Z4 0.5642*Z1*Z2*Z4 0.1204*Z2*Z3*Z4 + 0*0782*Z1*Z2*Z3*Z4; z10 = 0.2; z11 = 5.0; N1 = 40; h1=(z11-z10)/N1; z20 = 0.2; z21 = 10.0 ; N2 = 40; h2=(z21-z20)/N2; z30 = 8.0; z31 = 11.0; N3 = 40; h3= (z31-z30)/N3; z40 = 0.02; + 2.8774*Z1*Z4 + + 2.6223*Z3*Z4 0.3988*Z1*Z3*Z4 z41 = 0.5; N4 = 40; h4= (z41-z40)/N4; m = f1(z10,z20,z30,z40); For N1 = 1:40 For N2 = 1:40 For N3 = 1:40 for N4 = 1:40 If f1(z10+N1*h1,z20+N2*h2,z30+N3*h3,z40+N4*h4) >= m m = f1(z10+N1*h1,z20+N2*h2,z30+N3*h3,z40+N4*h4); End End End End End For N1 = 1:40 For N2 = 1:40 For N3 = 1:40 For N4 = 1:40 If f1(z10+N1*h1,z20+N2*h2,z30+N3*h3,z40+N4*h4) == m z1m=z10+N1*h1; z2m=z20+N2*h2; z3m=z30+N3*h3; z4m=z40+N4*h4; End End End End End % fprintf(' Giỏ tr cc i ca hm s l ymax = %f\n',m) fprintf(' V trớ t cc i l z1max = %f\n',z1m) fprintf(' V trớ t cc i l z3max = %f\n',z3m) fprintf(' V trớ t cc i l fprintf(' V trớ t cc i l z2max = %f\n',z2m) z4max = %f\n',z4m) .. . Peroxydaza hệ (II) 4.4 Nghiên cứu chế trình Peroxydaza hệ (II) 4.4 .1 Nghiên cứu ảnh hưởng chất ức chế Hq 4.4 .2 Nghiên cứu ảnh hưởng chất ức chế Ac 4.4 .3 Nghiên cứu ảnh hưởng chất ức chế Pa 4.5 .. . 4.1 Nghiên cứu hoạt tính Peroxydaza phức [Co(Acac)]+ 4.2 Nghiên cứu động họcquá trình Peroxydaza hệ (II) 4.2 .1 Nghiên cứu ảnh hưởng pH đến WInd 4.2 .2 Nghiên cứu ảnh hưởng [Acac]0 đến WInd 4.2 . 3.. . thiết bị nghiên cứu 2.4 .1 Nghiên cứu trình Catalaza 2.4 .2 Nghiên cứu trình Peroxydaza NGHIÊN CỨU QUÁ TRÌNH CATALAZA TRONG HỆ: H2O – Co2+– Acac – H2O2 (I) 3.1 Nghiên cứu tạo thành phức chất xúc tác