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Lch s nguyn t v trng thi thin nhin II. iu ch v ng dng III. Tnh cht IV. Mt s hp cht V. Mt s phc cht ca hp cht mangan VI. Nhn bit mangan v cc hp cht ca mangan VII. Vai tr sinh hc ca mangan
I.
Manganit
Pirolusit
Qung mangan
Psilomelan
Mangan xit
IU CH V NG DNG
I. iu Ch Dng bt Al, Si kh oxit Mn3O4 c to nn khi nung pirolusit 900oC 3MnO2 Mn3O4 + O2 3Mn3O4 + 8Al 9Mn + 4Al2O3 in phn dung dch MnCl2 hoc MnSO4 trong (NH4)2SO4. Kh MnO v Fe2O3 bng than cc nhit cao MnO + Fe2O3 + 5C Mn + 2Fe + 5CO Kh NH4MnO4 bng H2 nhit cao. Ngi ta khng kh trc tip pirolusit v phn ng ca n vi nhm xy ra qu mnh. Sn phm kim loi thu c cha 94-96% Mn v 6,4% tp cht Fe, Si v Al. II. ng Dng Gn 95% Mn dng ch thp trong ngnh luyn kim. Mn tinh khit dng ch nhng hp kim i hi thnh phn chnh xc cao nh: manganin, nicrom, uyara. L nguyn t quan trng i vi s sng: lm gim lng ng trong mu, Ion mangan l cht hot ha mt s enzim xc tin mt s qu trnh to thnh cht clorophin (cht dip lc), to mu v sn xut nhng khng th nng cao sc khng ca c th.
TNH CHT
1. L Tnh Mangan thuc chu k 4, phn nhm VIIB, cu hnh e ngoi cng [Ar]4s23d5. C mu trng bc hay xm nht. Dng th hnh: lp phng. Mn l kim loi mu trng bc, dng b ngoi ging nh st nhng cng v kh nng chy hn st. Khi lng nguyn t: 54,938 vC, khi lng ring: 7,44 g/cm3, nhit nng chy: 1245oC,nhit si: 2080oC. 2. Ha Tnh L mt kim loi tng i hot ng. Mn d b oxi khng kh oxi ha nhng mng oxit Mn2O3 c to nn li bo v kim loi khng b oxi ha tip tc k c khi un nng. Mangan d b halogen ha thnh MnX2. Mn + Cl2 MnCl2 Dng bt nh Mn tc dng vi nc gii phng hidro Mn + 2H2O Mn(OH)2 + H2 Phn ng ny xy ra mnh lit trong nc khi c mui amoni v Mn(OH)2 tan trong dd mui amoni Mn(OH)2 + NH4+ Mn2+ + NH3 + 2H2O Mn tc dng mnh vi dd HCl, H2SO4 long gii phng hidro Mn + 2HCl MnCl2 + H2 Mn th ng ha trong HNO3 long, ngui ging Cr nhng tan khi un nng 3Mn + 8HNO3 (l) 3Mn(NO3)2 + 2NO + 4H2O
HP CHT CA MANGAN
I. Mangan(II) 1. Mangan(II) oxit: MnO L cht bt mu xm - lc, nng chy 1780oC. Khng tan trong nc nhng d tan trong dd axit to thnh mui Mn(II). Khi b un trong khng kh khong 200 300oC to MnO2 2MnO + O2 2MnO2 iu ch: Nhit phn mui MnCO3 MnCO3 MnO + CO2 Hoc kh cc oxit cao ca Mn bng kh H2 hay CO nhit cao. 2. Mangan(II) hidroxit: Mn(OH)2 L kt ta trng, tnh baz yu, tan d trong dd axit to mui Mn(II), tnh lng tnh yu, Mn(OH)2 ch tan t trong dd kim rt c Mn(OH)2 + KOH() K[Mn(OH)3] Trong PTN, Mn(OH)2 c iu ch khi cho dung dch mui Mn(II) td vi dd kim Mn2+ + 2OH- Mn(OH)2 3. Mui Mangan (II) Mn(II) to mui vi tt c nhng amoni bit. Mui Mn(II) thng c mu hng nht, tan trong nc cho dung dch gn nh khng mu. Tr MnS, Mn(PO4)2 v MnCO3 khng tan trong nc. Khi nung vi hn hp cc cht kim v cht oxi ha (KNO3, KClO3), mui Mn(II) bin thnh mui manganat c mu lc MnSO4 + 2K2CO3 + 2KNO3 K2MnO4 + 2KNO2 + K2SO4 + 2CO2
II. Mangan(III) 1. Mangan(III) oxit L cht bt mu en khng tan trong nc, bin thnh Mn3O4 khi un trong khng kh 950 1100oC v thnh MnO khi un trong H2 300oC. Tc dng vi cc axit long (H2SO4, HNO3) to mui Mn(II) Mn2O3 + H2SO4(l) MnO2 + MnSO4 + H2O Tc dng vi dd axit c n to nn mui Mn(III) Mn2O3 + 3H2SO4() Mn2(SO4)3 + 3H2O 2. Mangan(III) hidroxit L hidroxit lng tnh, c dng hidrat l Mn2O3.xH2O, 100oC hidrat ny bin thnh monohidrat Mn2O3.H2O (hay MnOOH) tinh th mu nu en, khng tan trong nc. Trong PTN, mangan(III) hidroxit c iu ch khi cho cht oxi ha nh Cl2 hay KMnO4 tc dng vi huyn ph MnCO3 trong nc 3MnCO3 + Cl2 + H2O 2MnOOH + MnCl2 + 3CO2 8MnCO3 + 2KMnO4 + 6H2O 10MnOOH + 2KOH + 8CO2 3. Mui Mn(III) a s km bn, trong dd d b phn hy theo phn ng: 3Mn3+ + 2H2O MnO2 + Mn2+ + 4H+ Nhng mui mangan(III) n gin v thng dng: mangan(III) florua (MnF3), mangan(III) sunfat (Mn2(SO4)3), mangan(III) axetat (Mn(CH3COO)3). Nhng phc cht thng gp ca mangan(III): M3[Mn(CN)6] (trong M l Na+, K+, NH4+), [Mn(C5H4O2)3].
III. Trimangan tetraoxit (Mn3O4) L cht dng tinh th nng chy 1590oC, c th c cc mu vng, hoc en ty thuc vo phng php iu ch. c iu ch khi nung MnO2 hoc Mn2O3 900oC hoc dng kh H2 kh cc oxit 200oC MnO2 + 2H2 Mn3O4 +2H2O IV. Mangan(IV) 1. Mangan ioxit (MnO2) L cht bt mu en, khng tan trong nc v tng i tr, l oxit bn nht ca Mn iu kin thng. Khi un nng, n tan trong axit v kim nh mt oxit lng tnh MnO2 + 4HCl MnCl2 + Cl2 + 2H2O 2MnO2 + 6KOH(c) K3MnO4 + K3[Mn(OH)6] Khi nu chy vi cht kim hay oxit baz mnh, to nn mui mangannit MnO2 + 2NaOH Na2MnO3 + H2O MnO2 + CaO CaMnO3 Khi nu chy vi cht kim nu c mt cht oxi ha nh KNO3, KClO3 hay O2 th MnO2 b oxi ha thnh mangannat 2MnO2 + O2 + 4KOH 2K2MnO4 + 2H2O iu ch: Nhit phn Mn(NO3)2 ~300oC. Oxit ha mangan(II) trong mi trng kim bng Cl2, HClO, Br2. in phn dd MnSO4 v H2SO4 in cc v bnh in phn bng ch.
2. Mui Mn(IV) Mangan tetraflorua (MnF4) l cht rn mu xanh xm, l cht oxi ha rt mnh, d phn hy thnh MnF3 v F2 MnF4 MnF3 + 1/2 F2 Mangan tetraclorua (MnCl4) l kt ta mu nu hoc en tn ti nhit thp. Km bn trong nc, phn hy - 10oC MnCl4 MnCl2 + Cl2 Mangan isunfat (Mn(SO4)2) l kt ta mu en tan trong axit sunfuric m c cho dd mu nu. Kh bn trong axit sunfuric nhng b nc phn hy mnh. V. Hp cht Mn(VI) Mangan(VI) ch bit c trong ion mangannat (MnO42-) c mu lc xm. Natri mangannat (Na2MnO4) v kali mangannat (K2MnO4) l nhng cht dng tinh th mu lc en, phn hy trn 500oC. Mui mangannat l cht oxi ha mnh nhng vi cht oxi ha mnh hn, mangannat th hin tnh kh K2MnO4 + Cl2 2KMnO4 + 2KCl VI. Hp cht ca Mn(VII) 1. Oxit pemaganat (Mn2O7) nhit thp l cht dng tinh th mu lc xm, bn di -5oC, nng chy 6oC v pht n 10oC. Tan trong nc to thnh dd axit pemagannat nn c gi l anhirit pemanganic, l cht oxi ha rt mnh, tc dng vi nhiu cht v c v hu c 2Mn2O7 + 2(C2H5)2O + 9O2 4MnO2 + 8CO2 + 10H2O
2. Axit pemanganic (HMnO4) L axit mnh, d phn hy khi un nng, trong dd c mu tm , tng i bn trong dd long nhng phn hy khi dd c nng > 20%: 2HMnO4 2MnO2 + O3 + H2O Axit pemanganic v mui pemanganat u l cht oxi ha mnh. iu ch: Ha tan Mn2O7 trong nc c lm lnh hoc cho mui pemanganat tc dng vi dd axit long Ba(MnO4)2 + H2SO4 BaSO4 + 2HMnO4 3. Kali pemanganat (KMnO4) L cht dng tinh th mu tm en. tan trong nc to dd mu tm v tan c trong amoniac lng, pyriin,... Phn hy nhit cao Trn 200oC: 2KMnO4 K2MnO4 + MnO2 + O2 Trn 500oC: 4KMnO4 2K2MnO3 + 2MnO2 + 3O2 C tnh oxi ha mnh nn dng lm cht oxit ha trong tng hp v c v hu c,... 2KMnO4 + 3H2O2 2MnO2 + 2KOH + 3O2 + 2H2O Trong nhng dd trung tnh, axit yu hay kim yu, ion MnO4- b kh thnh MnO2 MnO4- + 2H2O + 3e MnO2 + OH Trong dd kim mnh v khi c d cht kh, ion MnO4- b kh n MnO422KMnO4 + K2SO3 + 2KOH 2KMnO4 + K2SO4 + H2O Trong dd kim c v khi khng c cht kh ion MnO4- t phn hy 4KMnO4 + 4KOH 4K2MnO4 + O2 + H2O iu ch: Trong cng nghip, in phn dd K2MnO4 vi cc in cc thp 2K2MnO4 + 2H2O 2KMnO4 + 2KOH + H2
cht Mn(II) u bng khng. V d: MnF + 4KF = K4[MnF6] MnCl2 +2KCl =K2[MnCl4] Mangan(III) florua l cht dng tinh th mu , trong dung dch c d HF n kt tinh dng tinh th hidrat mu thm MnF3.2H2O. N d to nn vi florua kl kim nhng phc cht mu thm nh K[MnF4], K2[MnF5]. Nhng phc cht thng gp ca mangan(III): M3[Mn(CN)6] (trong M= Na+, K+, NH4+) l cht dng tinh th mu thm. Mangan(III) axetylaxetonat [Mn(C5H4O2)3] l tinh th mu en nhnh, khng tan trong nc tan trong dung mi hu c v iu ch d dng khi cho huyn ph MnOOH trong nc hay cho [Mn(CH3COO)3] tc dng vi axetylaxetone. Phc cht vi axit etyleniamin-tetraacetic [Mn(EDTA)] -- bn vi nc, c th lu trong dung dch cng nh trong tinh th hidrat K[Mn(EDTA)].3H2O. Mangan tetraclorua (MnCl4) km bn trong nc nhng d kt hp vi halogen kim loi kim to nn nhng phc cht c mu vng v bn hn nh [M(MnX5)] [M2(MnX6)] (trong M= K, Rb, NH4 v X = F, Cl).
KMnO 4 to ra cht rn mu en MnO 2 trong mi trng kim.. MnO 4 + CaOCl 2 + 2 NaOH MnO2 + Na2SO4 + CaCl 2 + H2O Khi un nng dd K2MnO 4 to ra dd mu tm v kt ta mu nu en. 2 K2MnO 4 + 2 H2O 2 KMnO4 + MnO2 + 4KOH Khi lm lnh dd KMnO 4 c v AgNO3 thu c kt ta mu AgMnO 4 KMnO 4 + AgNO3 AgMnO4 + KNO3
VAI TR SINH HC CA MANGAN Mangan c tn khoa hc l Manganesia, k hiu Mn, c cc nh ho hc pht hin t cui th k XIX, c trong c c rt, c ci ng, ma, c ph v cy ch (tr). Nm 1903, nh sinh vt hc Gabriel Bertrand chng minh rng t thiu mangan s b cn ci, khng trng trt c. Bng th nghim dng nc c cha mangan c pha rt long ch c mt vi phn nghn gam trong 1 lt nc ti vo mt mu t kh cn, ng lm cho cy li tip tc mc v pht trin. Nm 1928, G.Bertrand chng minh tm quan trng ca Mn i vi s pht trin ca c th cc con chut th nghim. Nhng cng trnh ny lm cho cc nh sinh ho hc c bit ch v cng nhn vai tr khng th thiu ca Mn i vi i sng ca thc vt v ng vt. Mn l mt nguyn t vi lng rt cn cho c th sng, c nhiu trong cht khong
phc Metaloenzym. + Metaloenzym thc s l kim loi lin kt cht vi EZ nu thay th KL ny th hot tnh ca EZ s thay i. + Metaloenzym khng thc s l khi thay th KL th hot tnh ca EZ khng b thay i Nguyn t vi lng c vai tr trong trao i axit nucleic v nh hng n cu trc khng gian nhiu bc ca protein v axit nucleic. + Trong trao i gluxit cc nguyn t vi lng hot ho nhiu EZ nh Mn trong enolase, Zn trong phosphatase, Cu v Mn trong amilaza Cc nguyn t vi lng xc tc nhiu EZ trong trao i lipit. + Trong trao i nit cc nguyn t vi lng xc tc nhiu loi EZ nh nitrogenase cha Mo v Fe. + Xc tc cho qu trnh tng hp cc cht c hot tnh sinh hc cao
i vi ngi
Ring ngi, hin tng thiu Mn s dn ti s suy nhc, teo tinh hon,
mt kh nng sinh sn v lm suy gim s hot ng ca mt s enzym. - C th ngi trng thnh cha t 10 20 mg Mn nhng tham gia vo rt nhiu qu trnh bin dng vi nhiu vai tr khc nhau . Trong ng rut, mangan gip men tiu ha nhn din thc n d hp thu nht. t bo, mangan thc y tng hp protein bo ton cu trc ca t bo, nh t bo c th sinh sn bnh thng, phn ln tp trung trong xng, gan v thn. Lng Mn trong mu vo khong 10 mg/l, tp trung hng huyt cu. Huyt tng c cha t 0,6-4 mg/l. Cc c bp nhn c Mn t mu v gi khong 35% tng s Mn ca c th. Ni cch khc, t bo t b bin ng thnh t bo ung th. Mangan l nguyn t vi lng "bn rn" nht, c mt khp ni trong c th. Gip to huyt cu trong ty xng, tng cng cu trc chc khe cho xng v rng hay thc y qu trnh sn xut ni tit t. Mangan tham gia vo sn xut tc cht trung gian thn kinh dopamin mt cht dn truyn xung thn kinh cm gic v ch v tinh thn sng to ca con ngi
Ngoi ra, mangan cn kch thch chuyn ha cht bo, gim cholesterol gp
phn ngn nga x va ng mch. Mangan trong ty th lm cht ng xc tc cng cc enzyme chuyn ha hng lot qu trnh trong t bo... Hn na, mangan cn thc y hnh thnh sc t melanin lm sng da, tng sc sng cho tc. - Do c tc dng kch thch s hot ng ca mt s enzym, hoc kim ch tc dng ca mt s cht khc nh canxi, Mn tham gia vo nhiu hot ng sinh ho ca c th v l nguyn t cn thit c lin quan ti s sinh sn, s pht trin ca xng, cm gic gi thng bng, s hot ng ca no, s tng hp ca cholesterol, vic iu chnh nng glucose trong mu, s ng mu (phi hp vi Vitamin K)... - Ging nh ng, Mn tham gia vo cu to ca mt s t bo c tc dng chng oxy ho. Nhng nu nhng t bo ny c d, chng li c tc dng ngc li, lm cho cc t bo c lin quan mau b lo ho. + Nhu cu v Mn ca c th: ngi ln (nng 70kg), c th cn mi ngy t 6 8 mg Mn v c th c cung cp y bng cc thc n, ch yu l cc thc phm thc vt nh la, go, u, rau, qu, ch (tr)...
u rt giu Mn
hng ngy ca c th khng qu 5 mg v mangan trong thc phm c th cung cp y theo nhu cu . V vy, ch cn thng xuyn s dng cc thc phm giu mangan nh cc loi ht nh: u phng, u xanh, ht iu... hay cam chanh, rau dn, khoai lang v trng ng vt. S hp th ca mangan qua ng tiu ha b c ch bi mt s khong t khc nh st, canxi, photpho. c th hp th tt mangan ch cn ung mt ly nc chanh sau ba n l m bo c lng mangan cho c Trng hp c th thiu Mn t khi xy ra. Thng ch c hin tng c th b ng c v tha Mn, a s trng hp do lm vic ni khai thc (m Mn) hoc s dng Mn lm nguyn liu cc nh my ho cht. Ngi cng nhn thng b nhim Mn qua ng h hp, lm tn hi phi, h thng thn kinh. Thn, h tim mch, cc tinh hon cng c th b tn hi. Mn ng l mt nguyn t ho hc c tc dng nh con dao 2 li: rt cn thit cho s sng ca c ng vt v thc vt, nhng s gy tc hi khi c d. Bi vy, nu c th khng thiu m li dng thuc b sung thm Mn th s l mt vic lm rt nguy hi.
i vi ng vt
Cht khong trong thc n mc d chim t l khng ln
nh protein, lipid v glucid. Mc d cht khong khng c gi tr nng lng nhng n c vai tr rt quan trng trong qu trnh sinh trng, sinh sn v sn xut Khi thiu ht cht khong so vi nhu cu, vt nui b nh hng xu, trc tin l sc khe, sau l nng sut v phm cht ca vt nui. Ty theo tng loi cht khong thiu ht m vt nui c nhng biu hin khc nhau.
i vi thc vt
Quan h gia cc nguyn t vi lng vi cc qu trnh sinh
l trong cy + Cc nguyn t vi lng xc tc cc EZ trong chui h hp. + Theo Nason 1979 cc nguyn t vi lng nh hng ti chng ng phn thng qua xc tc hng lot cc EZ. + Trong chu trnh Crebs c 11 phn ng th mi phn ng u c s xc tc ca cc EZ cha cc nguyn t vi lng. + Cc nguyn t vi lng tham gia chui h hp, trong chui ny cc NTVL c kh nng thay i ho tr v vy chng c kh nng vn chuyn e tng hp ATP. + Cc NTVL tham gia tng hp dip lc: Cu, Co, Mo. + Theo Boichenco v Xaenco (1961): Mn v Fe nh hng n pha sng v pha ti ca quang hp theo s sau
O2
Mn+2
Mn+3
CO2
Fe+3
Fe+3
Fe+2
Cc nguyn t vi lng nh hng n qu trnh trao i nc nh ht nc, thot hi nc thc vt. Cc nguyn t vi lng Cu, Mn, B, Zn tng kh nng gi nc ca t bo, m v tng kh nng ht nc ca cc i phn t. Trong iu kin cung cp nc y cc NTVL tng kh nng thot hi nc, ng thi tng kh nng gi nc ca l khi gp iu kin kh hn
Hm lng Mn trong t
Chim t l thp, ch yu dng ion Mn+2, Mn+3, Mn+4 c th
chuyn ho cho nhau. Hm lng Mn ph thuc vo th oxi ho kh ca t. Th oxi ho kh thp th lc kh cng mnh Hp th v vn chuyn Mn Cy trng c th hp th khc nhau tu loi v thi gian sinh trng. Theo Clarkson v Honson (1980) kh nng hp th Mn b c ch bi Co, Mo, Zn, Fe. Mn c vn chuyn ch yu qua mch libe, chng tp trung nhiu trong l.
Qu trnh dinh dng khong (s ht dinh dng, s c nh m, s kh nitrat) qu trnh h hp (s oxy ha, chu trnh Krep), qu trnh quang hp (s kh CO2), qu trnh tng hp cht hu c (tn hp gluxit, axit nucleic v cc cht iu ha sinh trng), qu trnh vn chuyn, s thot hi nc v s chuyn ha gluxit, s sinh trng v pht trin (ny mm, to thn v ra hoa kt qu) s chng chu hn ca cy. Mn nh hng n s tng hp nhiu loi cht nh ng bt, hp cht c m, cc axit hu c, sc t, vitamin, auxin v cc men. Mn c vai tr rt quan trng trong s hnh thnh dip lc v xc tin s hot ng ca nhiu loi men. Ngi ta nhn xt thy nhiu trng hp mangan rt din hnh: trn t trng rau ti bng cng rnh, trn cc rung trng cy ha tho c bn nhiu vi. Hin tng thiu mangan t khi biu hin t chua v trng la ym kh m thng biu hin t kim, t chua sau khi bn vi, t khong kh v t giu hu c. Trn cc loi t ny ion Mn dng ha tr 3 v ha tr 4 kh ha tan hoc kt hp vi cc cht hu c to thnh hp cht kh ha tan. Trong iu kin kim, Mn sau khi ht c cn c th chuyn sang dng oxy ha v kt ng trong cc mch dn. Vai tr ca Mn rt a dng, chng tham gia cu trc v hot ho nhiu loi EZ khc nhau.
Trong quang hp Mn tham gia vo qu trnh quang phn nc trong h thng nh sng II.
Mn tham gia qu trnh quang phn li nc to ra e cung cp cho dip lc P680 (theo Cheniae v Martin, 1968)
2H2 O 4 H+ , O2
4Mn+3
P680
4 Mn+2
Mn xc tc cc EZ trong qu trnh phosphoril ho quang hp: phosphokinase, phosphatase... - Mn tham gia cu trc cc EZ c vai tr thu phn H2O2. gip gii c cho cy Theo Ness v woolhouse nm 1980: Mn c vai tr trong xc tc EZ ARNpolimease trong lc lp, lm cho qu trnh sao m, gii m, tng hp protein lc lp thun li
xanh m to thnh cc dng vung. Triu chng thiu Magan trn cy trng: Cng v mangan rt t di ng, nn hin tng thiu mangan thng c biu hin trc tin cc l non. cy l rng, bn l vng cn c cc gn l vn gi mu xanh. cy ha tho hin tng ny cng xut hin nhng khng r rng. Triu chng thiu Magan trn La v ma: Cng cn lu rng nhu cu ca cy trng v mangan khng c v hin tng c do tha mangan thng xut hin ph bin hn s thiu mangan. Hin tng ny thng xut hin cc vng t phn v i i vi c st, t chua trng ym kh.
Thiu Mn trn la v ma