Niken

S lc v nguyn t Niken

Trng thi thin nhin Tnh cht vt l v ha hc c im ca n cht Hp cht ca Niken Phc cht ca Niken Phng php iu ch ng dng

S lc v nguyn t Niken
Niken (cn gi l kn) c dng rt lu, c th t nm 3500 trc Cng nguyn. ng t Syria c cha niken n 2%. Hn na, c nhiu bn tho ca Trung Quc ni rng "ng trng" c dng phng ng t nm 1700 n 1400 trc Cng nguyn. Tuy nhin, bi v qung niken d b nhm ln vi qung bc nn bt k s hiu bit v kim loi ny v thi gian s dng cng c th cha chnh xc.

Khong cht c cha niken (nh kupfernickel, hay ng gi) c gi tr nh mu xanh ca n. Nm 1751, Baron Axel Frederik Cronstedt c gng tch ng t kupfernickel (hin nay gi l niccolit), nhng thu c mt kim loi trng m ng gi l niken. Nguyn t Niken nm s 28 trong bng tun hon cc nguyn t ha hc, cu hnh electron ha tr l 3d84s2, bn knh nguyn t l 1,24 awngsstrong.

Trng thi thin nhin

Niken l nguyn t t ph bin hn so vi st v coban, tr lng ca Niken trong v Tri t l 0,03% tng s nguyn t Khong vt ca Niken thng ln vi cc khong vt ca ng, st v km. Tn gi Niken c ly t tn ca khong vt Kupfernickel, kupfer c ngha l ng v nickel l tn ca con qu ln Nick trong truyn thuyt ca nhng ngi th m. Khong vt c bit t th k XVII v c gi nh vy l v nhng ngi th m tng nhm n l qung ng v tn nhiu cng sc luyn ng t qung v tt nhin khng thnh cng. Ngy nay khong vt c gi l Nikelin, ngoi ra Ni cn c trong cc qung limonite, garneirite.

Garneirite (NiSiO3.MgSiO3)

Limonite

Tnh cht vt l
Kim loi Niken c mu trng bc v c nh kim, d rn v d dt mng. Niken c 5 ng v bn: 58Ni (67,7%), 60Ni, 61Ni, 62Ni v 64Ni. Nhit nng chy 1453oC, nhit si 3185oC, nhit thng hoa 424 kJ/mol, t khi 8,9 Niken c 2 dng th hnh: Ni lc phng bn <250oC v Ni lp phng tm din bn >250oC. Khc vi hu ht kim loi, Niken c tnh st-t: b nam chm ht v di tc dng ca dng in n tr thnh nam chm. Niken l 1 trong 5 nguyn t st t.

Tnh cht ha hc
Niken c hot tnh ha hc trung bnh. iu kin thng nu khng c hi m, n khng tc dng r rt ngay vi nhng nguyn t khng-kim loi in hnh nh O2, S, Cl2, Br2 v c mng oxit bo v. Nhng khi un nng, phn ng xy ra mnh lit, nht l khi Niken trng thi chia nh. trng thi ny, n l cht t chy (chy trong khng kh ngay nhit thng). Nguyn nhn l do tng b mt tip xc rt ln gia cc ht kim loi Ni vi khng kh v s sai lch mng li tinh th ca ht so vi kin trc bn ca Ni. trn 500oC, Ni bt u tc dng vi O2 to nn NiO: Ni + O2 = NiO

Ni bn vi kh F2 nhit cao. nhit nng , Ni khng b kh F2 ph hy, v th m nhng thit b lm vic trong kh quyn F2 c lm bng Ni. nhit khng cao lm, Ni tc dng vi N2 to nitrua kim loi: Ni + N2 = NiN2 Nhng nhit cao hn, nitrua ny phn hy trong khi kim loi vn cn li mt lng Nit ng k dng dung dch rn. Ni tc dng vi S khi un nng nh to thnh nhng hp cht khng hp thc c thnh phn gn vi MS (M = Fe, Co, Ni) Ni + S = NiS Ni tc dng trc tip vi kh CO to thnh cacbonyl kim loi: Ni + 4CO = Ni(CO)4 Ni bn vi kim cc trng thi dung dch v nng chy v oxit ca Ni hu nh khng th hin tnh lng tnh. V vy trong phng th nghim ngi ta dng chn nung bng Ni nu chy kim.

Ni tan trong dung dch axit gii phng kh H2 v to nn mui E2+. Phn ng khng sinh ra mui E3+ v Ni v hidro mi sinh u kh c chng v E2+: Ni + 2H+ = Ni2+ + H2 Ni tinh khit rt bn vi khng kh v nc.

[Ni(OH2)6]2+

Hp cht ca Niken
Hp cht ca Ni(0): Niken tetracacbonyl Ni(CO)4 l cht lng khng mu, rt d bay hi v ht sc c. y l hp cht cacbonyl kim loi n gin nht. Phn t c cu hnh t din u vi nguyn t Ni trung tm v 4 phn t CO 4 nh. Di y l CTCT ca Niken tetracacbonyl:

Phn t c tnh nghch t, nguyn t Ni trong phn t c cu hnh 3d10 v trng thi lai ha sp3. Nhng obitan lai ha trng nhn nhng cp e t MO lin kt ca CO to thnh lin kt cho nhn.
Ni(CO)4 ha rn -23oC v si 43oC. Di tc dng ca tia t ngoi hoc khi un nng 180 - 200oC, n phn hy hon ton thnh kim loi v cacbon monooxit (c th gy n). N khng tan trong nc nhng tan trong ete, clorofom, benzen. Trong khng kh, n b oxi ha dn thnh NiO v O2. Hn hp ca khng kh v hi ca n c th gy n. N d tc dng vi halogen to thnh Niken dihalogenua: Ni + Cl2 = NiCl2

Ni(CO)4 khng tc dng vi axit long v kim nhng tc dng mnh vi axit sunfuric c (c th gy n) v vi axit nitric to thnh mui Ni(II): Ni(CO)4 + H2SO4 = NiSO4 + 4CO + H2 Khi un nng vi NO to nn Ni(NO)2 l cht bt mu xanh khng tan trong nc nhng tan trong clorofom, 90oC phn hy v pht sng mnh.

[Ni(OH2)4phen]2+

Hp cht ca Ni(II)
Niken(II) oxit L cht rn dng tinh th lp phng kiu NaCl v c thnh phn khng hp thc, c mu lc, nng chy 1990oC. Khi un nng, NiO d b kh thnh kim loi bi H2, CO, C, Al NiO + CO = Ni + CO2 NiO khng tan trong nc, tan d dng trong dung dch axit. NiO c th nu chy vi nhiu oxit ca kim loi v khng kim loi to nn nhng hp cht c mu. NiO thng c dng lm cht xc tc, bt mu trong sn xut thy tinh v gm. NiO c iu ch trc tip t cc n cht hoc bng nhit phn cc mui cacbonat, nitrat, oxalat hay nhit phn hidroxit: Ni(OH)2 = NiO + H2O

Niken(II) hidroxit Ni(OH)2 l kt ta khng nhy, khng tan trong nc, c kin trc lp, c mu lc, bn vi khng kh v ch bin i khi tc dng vi nhng cht oxi ha mnh: 2Ni(OH)2 + Br2 + 2KOH = 2Ni(OH)3 + 2KBr Ni(OH)2 tan d dng trong dung dch axit nhng khng tan trong dung dch kim Ni(OH)2 tan trong dung dch c ca mui amoni: tan c trong dung dch NH3 to thnh phc cht: Ni(OH)2 + 6NH3 = [Ni(NH3)6](OH)2 Bi vy cc mui ca Ni2+ d tc dng vi dung dch NH3 to nn nhng phc cht amoniacat

Mui Niken (II) Mui Ni(II) c vi hu ht nhng anion bn, mui khan c mu khc vi mui dng tinh th hidrat (NiSO4 mu vng nhng NiSO4.7H2O mu lc) Khi tan trong nc, mui Ni(II) cho ion bt din [Ni(H2O)6]2+ c mu lc. Trong nc, ion ny b thy phn mt phn lm cho dung dch c phn ng axit yu. Niken dihalogenua NiX2: khi kt tinh t dung dch nc, mui ny thng dng tinh th hidrat NiX2.6H2O (tr florua). dng khan, mu ca mui ph thuc vo bn cht ca anion. VD: NiF2 mu lc; NiCl2 mu vng; NiBr2 nu sm; NiI2 en. Cc NiX2 c to nng chy v to si kh cao (NiF2 nng chy 1027oC v si 1627oC). CoCl2.H2O tan trong aceton nhng NiCl2.H2O khng tan, ngi ta da vo tnh cht ny phn chia Co v Ni. NiX2 c th kt hp vi halogenua kim loi kim to nn mui kp M[EX3] hay M2[EX4].

NiSO4 l cht dng tinh th, c mu vng chanh, tng i bn vi nhit (phn hy 840oC), ht m v d tan trong nc. Khi kt tinh t dung dch nc to thng thu c tinh th hidrat h n t NiSO4.7H2O ng hnh vi MgSO4.7H2O Khi un nng, tinh th hidrat NiSO4.7H2O mt dn nc v cui cng bin thnh mui khan.

NiCl2

NiSO4.7H2O

Tinh th Amoni Magie Sunfat (c ln vt Niken)

Phc cht ca Ni(II)

Ni2+ to nn nhiu phc cht bt din vi s phi tr 6, Ni2+ cng to nn nhiu phc cht hnh vung vi phi t trng mnh. Mui Ni2+ khan kt hp vi kh NH3 to nn mui phc amoniacat cha ion bt din [Ni(NH3)6]2+. Amoniacat niken(II) bn c to nn c trong dung dch. Cation [Ni(NH3)6]2+ c mu tm. Mui [Ni(NH3)6](ClO4)2 c tan rt b nn c th dng nh lng Ni. Cc mui phc Ni(II) khi tc dng vi dung dch xianua kim loi kim, mi u to nn kt ta Ni(CN)2 mu lc, sau kt ta tan trong xianua d to nn ion phc hnh vung [Ni(CN)4]2-

Phc cht hnh vung ca Ni(II)

a s phc cht ca Ni(II) c cu hnh bt din, nhng phc cht ny u thun t. Trong nhng phc cht vi s phi tr 4 ca Ni, s t c to nn vi phi t trng yu c cu hnh t din (nh [NiCl4]2-) v s nhiu hn vi phi t trng mnh, c cu hnh hnh vung (nh [Ni(CN)4]2-. Tt c phc cht hnh vung ca Ni(II) u nghch t v c cc mu , vng hay nu. Ion [Ni(CN)4]2- l anion phc bn nht ca Ni(II), trong ion Ni2+ c cu hnh e 3d8. Mt phc cht hnh vung rt quen thuc ca Ni(II) l niken dimetylglioximat c to nn gia Ni2+ v dimetylglioxim trong dung dch NH3 long. Phn ng to thnh phc cht ny c dng nh tnh v nh lng ion Ni2+ trong dung dch.

Hp cht ca Ni(III)
Ni2O3 l cht bt khng tan trong nc. Hin nay ngi ta cha bit c nhiu v r rng v Ni2O3.

Ni(OH)3 l kt ta mu en, bn trong khng kh, khng tan trong nc v trong dung dch NH3. Khi un nng nh, n mt bt nc bin thnh NiOOH (hay Ni2O3.H2O), to cao hn b bin thnh NiO: 4Ni(OH)3 = 4NiO + O2 + 6H2O L cht oxi ha mnh, tan trong dung dch HCl gii phng kh Cl2, trong axit khc gii phng kh O2 v to thnh mui Ni(II) tng ng: 2Ni(OH)3 + 6HCl = 2NiCl2 + Cl2 + 6H2O

c quy kim Do Edison pht minh ra nm 1897. Cc dng c lm bng bt NiOOH, cc m lm bng bt Fe p, c 2 cc nhng trong dung dch KOH c cho thm LiOH tng dung lng ca c quy. c quy cho dng in 1,8V. Hot ng ca c quy kim da vo phn ng: 2NiOOH + Fe + 2H2O = Fe(OH)2 + 2Ni(OH)2 Ngy nay trong c quy kim Ni-Cd, ngi ta thay bt Fe bng bt Cd. c quy kim nh hn c quy ch v c th di chuyn m khng b hng nn c dng trong cc thit b lu ng, nhng nhc im ca c quy kim l h s tc dng hu ch b hn c quy ch.

Phng php iu ch
Nguyn liu chnh dng khai thc Ni l qung ngho cha sunfua ng v Niken vi hm lng Ni l t 0,3 4% nn qu trnh ch ha kh phc tp v bao gm nhiu giai on: - Loi t ra khi qung bng phng php tuyn ni c tinh qung cha 10% Cu v Ni. - t tinh qung trong l t nhiu tng ging l t pyrit ca dy chuyn sn xut axit sunfuric gim bt S trong qung. - Nu chy sn phm thu c ca l t trn trong l phn x. Sau khi loi thm S v tch x ra, sn phm thu c cha 16% Cu v Ni. - Nu chy sn phm ca l phn x vi cht chy trong l thi (kiu l Bexeme) v thi khng kh. Sau khi tch x, sn phm thu c cha 80% Cu v Ni.

- ngui sn phm trn y, nghin nh v oxi ha hon ton thnh oxit: CuO, NiO v mt t oxit ca cc kim loi khc cha i ht vo x. - Kh hn hp oxit kim loi 350oC bng kh than nc (56% H2 v 25% CO) thnh hn hp kim loi. - Cho kh CO i qua hn hp kim loi 50 80oC, kh CO tc dng vi Nikentaoj thnh Ni(CO)4 l cht lng d bay hi. - Phn hy Ni(CO)4 200oC, thu c Niken c tinh khit cao (99,99%).

Ngoi ra, ngi ta cn dng cc phng php sau: - Dng hidro kh Niken (II) oxit: NiO + H2 = Ni + H2O 270 280oC thu c Ni t chy. Cn 350 400oC hoc cao hn thu c Ni bt, n hon ton bn trong khng kh. - in phn dung dch NiSO4 trong nc vi cc m l Ni: 2NiSO4 + 2H2O = 2Ni + O2 + 2H2SO4 Mt khc, ngi ta cn dng phng php nhit nhm nhng phng php ny th ta thu c Ni khng tinh khit.

ng dng
Cc ng dng ca niken bao gm:
Thp khng r v cc hp kim chng n mn. Hp kim Alnico dng lm nam chm.

Hp kim NiFe - Permalloy dng lm vt liu t mm.

Kim loi Monel l hp kim ng-niken chng n mn tt, c dng lm chn vt cho thuyn v my bm trong cng nghip ha cht. Pin sc, nh pin niken kim loi hirua (NiMH) v pin niken-cadmi (NiCd). M ln b mt cc vt. Dng lm in cc. Trong ni nu ha cht bng kim loi trong phng th nghim. Lm cht xc tc cho qu trnh hir ha (no ha) du thc vt.