HoANG NHAM

NHA XUAT BAN GIAO Dl)C

HoANG NHAM

HOA HOC va CO •
, T~p ba
CAC NGUYEN TO CHUYEN TIEP
(Tai ban Ian thu tu)
• ...,.,. .:t ,.,.

NHA XUAT BAN GIAO DVC

....

A';'"

,;

CHUONG I

PHlIC CHAT
SlJ T ~o PHUC
Khi xet cac nguyen t6 dien htnh (nh6m A) chang ta da gi,\p mot s6 phan ling tao phtrc. Vi du: Be(OH)2 AlP3 SiF4

+ 2NaOH + 3NaF + 2HF

+ HCl

= = =

N~[Be(OH)4] N~[AIF6] H2SiF6

NH3

NH40

Kha nang tao phtrc cua cac nguyen t6 chuyen tiep (nh6m B) con rong IOn hon nhieu va
Ia mot trong nhung diem khac biet giua nguyen t6 chuyen ti~p vii nguyen t6 dien hlnh. S6 phtrc chat cua kim loai chuyen ti~p 16'0gap.nhieu lb so vci s6 hqp chat dan gian ciia chung. H6a hoc cua kim loai chuyen ti~p tnuong duqc coi co ban ta h6a h9C phuc chat . Day la mot lanh vue bao trurn h6a hoc vO co, Nguyen tit kim loai chuyen tiep c6 nhieu obitan h6a tri, trong d6 c6 nhieu obitan tr6ng

va c6 dQ dien am 160. han kim loai kiem va kiem thO cho nen rat c6 kha nang nhan cl),p electron va la chdt tao phuc t6t.
TrD' lai lich sit phat trien cua h6a hQC phtic chat, nhtmg phirc chat da dUQ'Cbiet den va nghien cil'u dau tien chmh Iii phuc chat cua kim loai chuyen tiep, C6 Ie xanh Beclin c6 thanh phan KCN.Fe(CN)2.Fe(CN)3 de do Diesbat (Diesbach) ngubi Dtrc dieu ch~ vao dau the ki XVIII

lam

bot mau ta phuc chAt duQ'c bi~t va sit d1:IDgdau tien, Phtrc cMit thu hai duoc biet bill

Taxae (Tassaert) ngub'i PMp vao nam 1789 la hop char mau nan-do tao nen khi amoniac ket hop vCti quang cua kim loai coban. Vao dau the ki XIX, nhieu amoniacat cua coban duoc dieu che, chung c6 mau d~p vaco ten goi gfm lien v6i mau cua cluing, vi du nhu amoniacat CoC13.5NH3 mau do duoc goi la mu6i puapureo, amoniacat CoCI3.5NH3.~O c6 mau hong duoc goi la mu6i rozeo, Den eu6i tneki, nhieu amoniacat cua crom

va platin

duqc dieu ch6. Tuy nhien, g~ mot th~ ki trOi qua, chua

co
3

mot If thuyet nao gilri thich thoa dang sl,ltao thanh nhtmg amoniacat diS.

Thuyet macb
Vao nhtrng nam 60 cua the ki XIX, trong hoa hoc khai niem hoa tri da hmh thanh f5 net, mbi nguyen to co mot hoa tri co dinhva ngiroi ta da: biet cac hop chat hiru co co cau tao mach gorn nhirng nguyen til cacbon. -CR\
-

Vf du nhu phan

til hexan

co

cau

tao

mach

CH3 -CH2

- CH] -CH2

-CH]

gom 6 nguyen

tir C, trong do nhom rnetyl CH, co hoa

trj mot va nhom rnetylen - CH2

co hoa tri hai. (W. Blomstrand) va Jogenxen

Van dung nhirng thanh tJ!U do, nam 1884 Blomstran (Jorgensen) dua ra thuyet machve
cau tao cac amoniacat

cua coban. Cac 6ng cho rang trong

NH4Ci voi cau tao H-NH3-C1, nhom -NH3- co hoa tri hai cho nen:

/Cl Co-..........__ NHl-NH1-NHl-NHl-Ci . . Cl Khi tac dung voi dung dich AgN03, ba nguyen tir CI trong muoi thir nhat deu tao ket

tua AgCl VI cluing 6 each xa nguyen ti't Co, mot nguyen

tu CI trong
clni

nr a trong

mu6i thrr hai va hai nguyen

mu6i thii ba khong tao ket tua VI cluing 6 sat ngay nguyen tl'r Co. cua kim loai

Tuy nhien, thuyet mach kh6ng giai thich diroc tai sao trong cac amoniacat chi co 6 phan

tir NH3 rna kh6ng co 8 hay to va tai sao phan ti't NHJ Iai tro ve m~t hoa hoc. (Oin

rang thuyet mach ra dOi va dUQ"C phat tri~n gAn nhu dong thai voi thuyet dien Ii cua

Areniut).

Thuyet ph61 tri

Dang nghien ciru trong linh vue hoa I~p the cua nhirng hop chat hiru co chua nita, nha hoa hoc Thuy Si Vecne (A. Werner, 1866-1919, giai thuong Noben v~ h6a hoc nam 1913) di:i chuyen huang nghien ciru sang cac amoniacat cua kim loai, mot lanh vue rat hap dan Ilk bffy gio, DUng tnroc nhfrng kho khan rna cac nha hoa hoc vb co gap phai trong viec giai thich cau tao cua cac amoniacat ong nhan thay kim loai, Vecne nhan thay khong the ap d~t nhirng

nrong d§ co trong cua Co, Cr va Pt,

hoa hoc hCiu co van nhtrng amoniaeat.

Lam nhieu thi nghiem voi amoniacat

nrong ve mot hoa tri co dinh kh6ng th~ ap dung duoc cho nhfrng kim loai naySal!

va vao dau nam 1892, thuyet pht/i tri cua Vecne da ra doi trong mot gille rna, hie 0.6 6ng moi
26 tubi. Thuyet phoi trf baa gem nhirng diem day:

• Nguyen

til cua nguyen t6 c6 th~ c6 hai loai h6a tri: h6a tri chinh va h6a tri phu, H6a

tri chinn nrong ling voi khai niern s6' oxi hoa ngay nay va hoa tri phI! urong irng v6i khai niem

st/ pho'· tri ngay nay.

· Nguyen fLr tao phirc c6 xu huang baa hoa cac h6a tr! chfnh va h6a tri phu, H6a tri chfnh chi duoc baa hoa bang anion con h6a tr] phu diroc baa hoa bang anion va phan hoa, • H6a tri phu eo phurrng xac dinh trong khong gian. Ba amoniacat cua coban vira xet tren day diroc mo

tir trung

ta nhu

sau thea thuyet ph6i trf,

CI ~H3
NH3~~~\1 NH3/j /~NH3 ~~~~~NH3

>CO:-/-CI

Cl NH3 CI NH3~,~ 11 /NH3 CI--'~·Co-/-CI

,,'" r , ~ .......

NH /
3

NH3 CI NH3~,~ NH3/ -

,
I

~'~NH3

'~·c _/"I:a.~~~ I"

Cl

11

/NH3

"-/-Cl NH3

Trang cac cong tlnrc cau tao tren day, vach lien chi h6a tri chfnh va vach rOi chi hoa tri phu, hoa tri chinh ella Co bang 3 va hoa tri phu bang 6. Trang hop chat thir nhat, cac nguyen tir Cl chi thoa man hoa tri chfnh, con cac phan tu NH) thoa man h6a trj phu, Trong hop chat thu hai, mot nguyen AgN03.

tit Cl vira thea man hoa tri chfnh, vira thea man hoa tr]

phu, Nguyen

tiI Cl thea

mao boa tri phu nay khong tao nen ket tua AgCl khi hop chlft thu hai tac dung voi dung dich

Tuong tv nhu vay hai nguyen tir Cl trong hop chat thu ba thoa man d hai hoa tri khong tao nen ket tua AgCI. Trong d ba hop chat, cac phan tir NH3 dc!u thea man hoa tri phu nen khong bi trung hoa boi axit manh cfing nhu khong bi kiem manh d1y ra khoi dung dich,
Vao thoi cua Vecne, ngiroi ta chua biet duoc ban chat cua hoa tri chfnh va h6a tri phu

VI trong hoa hoc chua co nhirng phuong phap thirc nghiern va Ii thuyet d~- nghien ciru. Nhirng 5

Vecne da de ra phirong phap nghien ciru va tong hop phirc ch<ft'va phuong phap d6 trong met so tnrong hop cho phep 6ng du doan dung s6 cue dai cua phirc ch<ft diroc tao nen trong nhfrng di~u kien xac dinh va nhfrng dac di~m co ban ve cau tao cua cluing. C6ng cu chinh

rna

Vecne dung de! Ii giai cau tao cua phirc chAt HI.viec nghien ciru hien

nrong d6ng phan, Vecne so sanh s6 dong phan du doan voi 56 d6ng phan t6ng hop duqc cua mot phirc chat c6 thanh phan xac dinh va d.l!a vao d6 d~ clnrng minh nhirng quan niern dung da.n cua minh ve diu tao cua chung. Thanh t1!U100 da dat diroc cua Vecne la 51! phu hop hoan toan giira

so dong

phan tong hop va 56 d6ng pharr du doan cua phirc chat co cAu hlnh bat dien,

Tuy day khong phai 18. bang chirng tnrc tiep c6 th~ xac minh cau tao cua hop chat, nhfrng du doan cua Vecne dung de khang dinh 51! dung dAn cua thuyet ph6i trf 18.mot tien bo IOn trong khi chua c6 nhirng phirong phap nghien ciru hien dai, Thuyet ph6i tri cua Vecne dB:cho phep h¢ th6ng hoa nhung hitu biet ve phirc char thai bay glU va dinh lurong cho viec t6ng hop phirc chat moi. Thuyet phci trf cong voi hai muoi nam tim ,toi nghien ciru khOng met moi va hoat dong giang day cua Vecne dB: diroc danh gia bang giai tlnnmg Noben vao nam 1913 ve h6a hoc, Thuyet ph6itri cho-nhan), va 51.! fa dui thuyet cap electron cua Liuyt ve lien ket cQng h6a tri dB:dan den quan niern ve sau nay ve lien ket pho/' trl (lien ket

CAD TAO

eVA PHTJC CHAT

Trang cong thirc cau tao cua phuc chdt (thirong goi la hop chdt pha'i trt) ngiroi ta phan ra cau noi va cau ngoai, Cdu noi hay con goi la cdu phoi tri duoc viet trong dau moe vuong, baa

gem chat tao phirc va cac ph6i nr.

Chdt tao phU:c co the la ion hay nguyen ti'r va thirong duoc goi chung la nguyen tif trung

tu

tam. Phoi (If hay ligand (tit chir ligare tieng La Tinh la buoc quanh) la ion ngiroc da.'u hay phan trung hoa dien diroc ph6i tri xung quanh nguyen trung tam, Dien tich cua cau noi la tOng dien tfch cua cac ion b trong diu noi, Nhfrng ion narn ngoai va ngiroc da.'u v6i cau ntii tao nen cdu ngoai.

tu

Vf du nhtr nhung amoniacat CoC13.4NH3 co cong thtrc cau tao 18.:

cua coban vira xet tren day CoCI3.6NH3,

CoCI3.5NH3

va

(cau noi)

(cau ngoai)

(cau noi)

(cau ngoai)

(cau noi)

(cau ngoai)

- Cau ntii cua phirc chAt co the 13 cation. Vidl,l:

[}\I(H2(»6JC13
[Zn(NH3)4]CI2

[(Jo(~If3)6]<:13 - au Vidy: H2[SiF6] noi cua phlic chat c6

the la anion.

K2[Zn(OH)J K2[PbI4]
- au n¢i cua phuc ch~t co tM 18 phan

ti'r trung hoa dien, khong phan Ii trong dung

dich.
Vi du:

[<:O(NH3)303] [J>t(NH3)2<:121
[~i(<:O)4] Qua nhttng vi du tren day, ta thay nguyen tir trung tam c6 la kim loai (<:0, AI, Zn, loai (Si), c6 Ul ion «(Jo3+,AI3+, Zn2+••• ) hay nguyen tir (Ni); ph6i tir

Pt va Ni) hay khong-kim co

the la anion
~ilng

the

the

(P- •Cl" ,OH-) hay phan tir (NH3, H20 ...).

Ph6i Iii
ph6i tir la anion thirong g~p 18 P- ,0- .T , OH-. CN-. SCN- , NO 2" • 820;- ,

<:20;- , ., .. Nhimg ph6i tir 18 phan tir thirong g~p la H20, NH3, <:0, NO, pyridin (~HsN), etylendiamin

(H2N-CH2-<:H2-NH2).

DJ!3. vao 56 nguyen tir rna ph6i tir c6 tM ph6i tri quanh nguyen tir trung tam, nguat ta
chia ph6i tu ra

lam ph6i

tir mot cang va ph6i tir nhieu cang. Nhilng anion F- ,0-

, OH-

,(N- ...

va nhimg phan tu nhu H20, NH3 ... la phdi uimf)1 congo Anion C2 O!- • phan tir etylendiamin

la

pOO! lIt hai congo

etylendiamin

Vi du nhu ion phirc cua ion 012+ v6i amoniae

va ella ion 01 + v6i

co e4'u tao: 2+

([Cu(en)2f+, en=etylendiemin)
-

Anion ella axil

etylendiamintetraaxetic (viet tat 18 EDTA):

-aac

-CH2~ N~H-CH-N
2 2

_/CH2-CaO~CH-COO2

-aaC-CH/

la pht/i

tit sau cang, no co hai nguyen tu N va b6n nguyen tiI a co the phoi trf quanh ion kim

loai M'":

(4- 0)

Chat diroc goi

triton

dung

trong

hoa

hoc

phan

tich

la

muoi

dinatri

ella

axit

etylendiamintetraaxetic,

Phirc chat duoc tao nen bci ph6i

tir nhieu cang voi mot ion kim loai

ia phuc

chdt vong cang hay chela! (tit chir chele tieng Hy Lap

ia vong),

Sophoitri
So phoi tu bao quanh chat tao prnrc X3c dinh s(I ph(/i tri s6 phoi trf cua ion chat K2fZn(OH\],
2

cua chat tao phuc. Vi du nhu

lCo(NH3)4Ci2]Ci,
2

Na3(AIF6] va [Ni(NH3)6](N03h cac ion phtrc [Cu(NH')4f+

Co'+' AI'+, Ni + trong cac phirc chat lCo(NH3)6jCi3,

2

bang 6; s6 ph6i tri ella Zn +, Pt +, Nj2+, Au" trong cac phirc

[Pt(NH,)2Ci1L [Ni(CO)4] va H[AuCi4j bang 4; so ph6i trf cua ion Cu2+ trong va lCu(enh]2+ deu bang 4 VI phoi ttt mot cang tao nen s6 phoi trf

bang I va pho] ttt hai cang tao nen s6 ph6i trf bang 2 cho nguyen

Ag" trong ion phirc [Ag(NH3hr bang 2, s6 ph6i trf cua Fe trong phirc chat [Fe(CO)sl bang 5; s6 ph6i tri cua kim loai hoa tri b6n M(lV) trong phirc chat Mraca), (0 day Mia Ce, Zr, Hf, Th, U, Po va aca la axetylaxeton) bang 8 ... Tuy nhien 4 va 6 la nhirng s6 phoi trf phe) bien nhat trong cac phirc chat, cac s6 phoi trf khac kern phd bien hem nhieu, Mot s6 chat tao phtrc co s6 ph6i trf c6 dinh trong Uit

tu trung

tam; s6 phoi trf cua

ca cac

phtrc chat, v( du nhtr Cr3+ va

Pt4+ luon luon eo s6 ph6i tri la 6. Nhtrng tuy thuoc vao ban chat cua ph6i tir va dieu kien tao thanh phirc chat, da s6 chat tao phuc co th~ co so pnoi trf khac nhau, vi du nhu ion Ni2+ trong plnrc chat eo the co cac s6 ph6i trf 4 va 6. 56 ph6i trf 6 cua nguyen ti'r trung tam lu6n luon irng voi cau hinh bat dien ella phtrc chat con sQ ph6i tri 4, irng voi cau hinh tu dien hoac cau hinh hinh vu6ng.

TEN GO! ClTA PHUC CHAT

Gi6ng voi hop eh4t don gian, ten goi cua phirc eM"!bao g6m ten cua cation va ten cua anion. Ten goi ella ion phuc g6m e6: s6 phoi tu va ten ph6i tu 18.anion, s6 ph6i tu va ten ella ph6i tu 18phan tu trung hoa, ten ella nguyen tu trung tam va s6 oxi h6a. S6'ph61 tli

De chi s6 hrong ph6i tu mot cang nguoi ta dung nhttng tiep d<1udi, tri,
hexa ... e6 nghia la 2, 3, 4, 5, 6 ...

tetra, penta,

chi s6 hrong ph6i tu nhieu cang ngum ta dung nhtmg tiep d<1ubis, tris, tetrakis, pentakis, hexakis c6 nghia la 2, 3, 4, 5, 6 ... Ten phdi til - Neu ph6i tir 13. nion, nglICria 14yten ella anion va them duOi 0: a t NO;: F- floro nitro nitrito sunfito tiosunfato oxalato C02-3 OHCNSCNNCSeaebonato hidroxo xiano tioxianato isotioxianato

De

cr
I-

ONO-

cloro

SO~S2 023 C 202-4

Br- bromo
iodo

- Neu ph6i tir la phan ni trung hoa, nguCrita 14yten ella phan tir d6:

CzH4

etylen,

C~H5Npyridin, CH3NH2 metylamin

NH2CH2 CHzNH2 etylendiamin, ~I\; benzen

- Mot s6 phan tir trung hoa duqe "4t ten rieng: H20 aqua, NH3 ammin, CO eaebonyl, NO nitrozyl. Nguyen tli trung tam va s6' oxi hoa - Neu nguyen tir trung tam a trong cation pmrc, ngum ta tay ten ella nguyen tu d6 kern theo s6 La Mii viet trong eMungoac don de chi s6 oxi h6a khi e4n. - Neu nguyen tu trung tam a trong anion phuc, ngtrci ta I~y ten ella nguyen tli d6 them duOi at va kern thee s6 La Mii vi€t trong dau ngoac don de chi s6 oxi h6a, neu phirc eMt la axit thi thay duOi at bang ie. Vi dl! ten goi ella !'1~t st/QhKe e¥t: hexaammin coban(llI) clorua 9,

[Cr(NH)6]CI3 [CO(HZO)5CI]QZ [Cu(NHZCH2CH2NH2)Z]SO4

hexaammincrom(llI)

clorua clorua

cloropentaaquacoban(llI)

bisety lendiamin d6ng(II) sunfat axetylaxetonatotetraaquacoban(ll) natri tetrahidroxozincat kali hexaxianoferat(II) clorua

[Co( aca)(H20)41CI
N~[Zn(OH)4] ~[Fe(CN)6] K){Fe(CN)61 H{AuQ4]axit

kali hexaxianoferat(llI)
tetracloroauric(ID)

HII;:N TU'QNG DONG PHAN TRONG PHUC CHAT

Dong phdn nhu da biet 180su t6n tai cua nhtmg ch~t c6 cung mot thanh phan nhung khac nhau ve ca:'u tao phan tU nen c6 tfnh chat khac nhau. Phuc chat cling c6 nhihIg dang dong phan gi6ng nhu hop chA'thlhl ca. Nhtmg Ideu dong phan chfnh cua plnrc chat la dong phan hinh
hoc va d6ng phan quang hQC. Ngoai ra con c6 cac Ideu d6ng phan khac nhu dong phan ph6i trf, dOng phan ion h6a

"..

;::

jilt,

,.

va dong

phan lien ket,

nong phdn hinh hoc hay dong phdn cis-trans

Trong phirc chat, trung tam.

cac ph6i tir c6

the chiern nhtmg vi trf khac

nhau d6i v6i nguyen

tir

Khi phirc cha:'t c6 cac loai ph6i tir khac nhau, neu hai ph6i til giong nhau b ve cung mot phfa d6i voi nguyen tir trung tam thl plnrc cMt l3. dong phtin dang cis (cis tieng La Tinh nghia Ia mot phfa) va nell hai ph6i tir gi6ng nhau ave hai pbfa dOi vOi nguyen tit trung tam thi
phuc chA't Ia dong phdn dang trans (trans tieng La Tinh nghia la khac phia). Vi du phirc chat hlnh vuong [Pt(NH3)2C121c6 hai d6ng phan cis va trans:

<,
Pt

/NH)

N H3 ""

/f

CV""'" "-....NH3 cis-diciorodiamminplatin(ll) (mau yang da cam)

CI/'NH3 trans-diclorodiamminplatin(II) (mall yang nhat)

Trong dong phan dang cis, hai phan tii NH3 cUng nhe hai nguyen phia d6i voi d6i dien voi nhau qua

tit a deu

a cung

mot

Pt, con trong dong phan dang trans, hai phan tii NH3 cling nhir hai nguyen tir CI Pt.

10

Ion phirc bat dien [Co(NH3)4Cllr CI

c6 hai dong phan cis va trans: CI

NH,

Cl ,rans-diclorotetraamm incoban (Ill) (rnau luc)

c is-d icIorotetraarnm incoban (I II)

(rnau tim) Trang dong phan cis, hai nguyen

tir Cl

a cung

mot phfa d6i voi Co, con trong dong

phan trans, hai nguyen tt'r C\ b d6i dien voi nhau qua Co. Phircchat ur dien khOng c6 dong phan hlnh hoc VI hai dinh cua bat kl tu dien nao deu b

v~ m¢t phfa d6i voi nguyen til trung tarn,

D6ng phdn quang hoc hay dong phan guong

Hien tuong dong phdn Quang hoc sinh ra khi phan tir hay ion khong c6 mat phang d6i
xirng hay tam dOl xirng, nghia Ia phan ti'r hay ion khOng th~ chong khft len anh cua no cua v~t

a trong

girong. Hai dang dong phan quang h9C khOng thl! chong khit len nhau nrong nr nhir vat voi anh

a trong

guong, Boi vay, kieu dong phan nay con goi la dong phdn guong, Do co cau tao

khong d6i xirng, cac dong phan gUO'Tlg Mu heat dong vt mat quang hoc: lam quay mat phfing cua anh sang phan eire, Cac dong phan quang hoc cua mot char co tfnh chat If hoa gi6ng nhau trir plurong lam quay trai hay phai rri~t phang cua anh sang phan eire. V i du ion phirc trisox ala toe rornatt III) l C2 04 Cr(
) 3 J 3-

co hai dong pharr girong:

1 /~l~ : Cr
OX

g~

lOX

.. ~

... ox

ox :

~ .. :yi [
Cr

~l7

..

(vach lien chi lien ket, vach cham chi cau hinh hinh vuong)

Ion phirc dicioroetylendiamindiammincobao(III)

lCo(NHJhenC12t

co

hai dong phan

guong:
'11

Cl
en

t.~ N

/:~""""'\"""""""":/:;I ~C/
.:

0,,:....
NH3

NH3

(vach lien chi lien ket, vacn cham chi hinh vuong trong cau htnh bat dien va en=etylendiamin). Nhieu dong phan hlnh hoc va d:6ng pharr quang hoc cua cac kim loai Co, Pt va Cr df:l duoc Vecne du doan, t6ng hop va nghien cUu.d! lam co sa xac minh thuyet ph6i trf cua mmh,

l>6ng phtin phoi tri

Hien nrong d6ng phdn pht51 tri sinh ra do st! ph6i hai nguyen

to khac

nhau cua loai ph6i til quanh

tit trung tam clla phirc chat g6m c6 eft cation phuc va anion phrrc.

Vi du:
[CO(~3)6][Cr(~6J [Cu(~3)4] [PtC41 va va va [Cr(NH3)6] [CO(~6] [Pt(NH])4] [CuC141

[ Pt (NH3)4Cl2] [ Pt 04]

+4

+2

l>6ng phtin ion h6a

Hien nrong d6ng phdn ion hoa sinh ra do su sap xep khac nhau ella anion trong cau noi va cau ngoai cua phrrc chat

[Co(NH3)s13r]S()4 (mau tim-do)

va

[Co(NH3}5S0 4113r (mau hong-do)

Dung dich cua ddng pharr mau tim-do, khi tac dung voi 13a2+ cho k~t tua BaS()4 con dung dich cua d6ng pharr man hong-do, khi

rae

dung

vm

Ag" cho ket tua AgBr.

12

Bong phtin lien ket

Hien nrong d6ng phon lien ket sinh ra khi ph6i tli m¢t ding co ldui nang ph6i tri qua hai nguyen til. Vi du ket M-N02)

tuy thuoc vao diell kien, anion N02" c6 tM ph6i trf qua nguyen tli N (lien

hay qua nguyen til 0 (lien k€t M-ONO), anion SCN- c6 th~ ph6i tri qua nguyen

til S (lien k€t M-SCN) hay qua nguyen til N (lien k€t M-NCS).
Vi du: [Co(NH3)sN021CI2 Nitropentaammincoban(ll) (mall vang) [Mn(CO)sSCN] Tioxianatopentacacbonylmangan va clorua va (Co(NH3)sONO]CI2 Nitritopentaammincoban(ll) (mall hong-do) (Mn(CO)sNCS] Isotioxianatopentacacbonylmangan va nitritopentaammin cua coban(ll) nay da clorua

Chu

y:

Hai dong phan nitropentaammin

duoc Jogenxen t6ng hop til nam 1894. sall d6 duqc ca Jogenxen va Vecne cung nghien cuu va hai Ong da giai thich dung cau 4-0 khac nhau

cua chung trong khi chua c6 nhtmg phirong phap

nghien coo hien dip nhu ngay nay. Hai Ong da so sanh mau cua hai d6ng phan d6 v6i mall cua

cac phuc chat khac cua coban, nhan tha:'y nhUng hqp cha:'t gom c6 6 lien k€t C03+- N nhu
[Co(NH3)613+

va

[Co(enh]3+ deu c6 mall vang con

nhung hqp cha:'t c6 5 lien ket Co3..:!:...N mot va

dell c6 mall hong-do. Nhu vay, su

lien ket Co3+_ 0 nhu [Co(NH3)sH2013+ va [Co(NH3)sN02f+ khac nhau ve mau sac cua hai d6ng phan

ta sq

khac nhau ve lien k€t cua Co3+ v6i nh6m N02

THuvET LIEN KET H6A TRJ (VB)

:san cha:'t cua

hoa

tri phu trong thuyet ph6i tri cua Vecne cang ngay cang duqc sang to
chuyen ti€p:

trong Ii thuyet hien dai ve lien ket hoa hoc trong ph1ic cMt cua cac kim I~ Thuy€t lien k€t hoa trio thuyet tnrong tinh the! va thuyet obitan phan til.

Thuyet lien ktt hoa tr!

Nam 1927, thuyet axit-bazo cua Liuyt (xem ~p mot) coi haw la cha:'t cho e~p electron va axit la

chat nhan

c~p electron:

axit Liuyt

bazaLiuyt

muOt Liuyt 1873-1952) v$I1 dung vao phec chat,

da duQ'C nha h6a hQC ngum Anh Xituyc (N.Sidgwiek. Xituyc coi nhtmg amoniacat mu6i Liuyt:

cua coban da xet trong thuy€t ph6i hi cua Vecne

ta

nhitng

13

eo3+
axit Liuyt

6 :NH3 bazo Liuyt

H,N",,!/, eo H,N"" t
3+

NH3

'NH,

muei Liuyt

NH3
V$.y phec ch5t ducc tao thanh bang cac lien ket cho-nhan gUm ~p electron nr do Clla ph6i tu va obitan trong cua nguyen tlr trung tam. K€t hop vOi. khai niem lai h6a cua Paolinh, nhung obitan trong d6 phai Iii nhtmg obitan lai hoa cua nguyen tir trung tam m6i. c6 tM ti€p nhan dugc nhtmg c~p electron cua ph6i tir nam a nhtmg vi tri quyet dinh cau hlnh cua phU"c cMt. Vi du I. Ion Cu' ket hop v6i. : NH3

+
tao nen cation phtrc [CU(NH3)2]+ duang thang nho su tao thanh hai lien ket cho-nhan giira C4p electron t\l"do cua :NH3 va hai obitan lai h6a sp tr6ng cua ion CU+ (3d'Q): .
r·············_M!··_················! _

3d

NH)

NH3

Vi du Z, Ion

eo2+ket hop v6i. ion Cl:

=

tao nen anion phuc tii dien [CoC~f- nne sg tao thanh 4 lien k€t cho-nhan giiIa c~p electron t\l" do cua ion Cl va obitan lai h6a Sp3tr6ng cua ion Co2+(3d7):
3d eo'>(3d'j

IUlul tit I t I ~I
a
2 +

i"4S"··""·················~E~·"·~4······················i

fJ

aaa

Vi du 3. Ion Pt

ket hop v6i ion Cl" :

Pt2+

4 0-

tao nen anion phirc hlnh vuOng [PtClJ2- nha sq tao thanh 4 lien ket cho-nhan giiia c~p electron t\l"do cua ion Cl" va obitan lai hOOtreng dsp2 cua ion Pt1+(5d8):

14

..···································68······_·· __·__

~....-r--tJ,-t----.

t
cr

·····~---l
a-

dsp'

··_····.·6········ .

--

a- a-

Vi du 4. Ion Co3+ k~t hop v6i NH3 tl;10thanh cation plnrc bat dien nho 6 lien k~t chonhan gina c~p electron t1)' do cua NH3 va obitan lai hoa tr6ng d2spl cua ion Co3+(3d6):

d2sp3

~;~~~

NH3NH3

NH3

NH3 NH3NH3

Trong cation phnc [Co(NH3)6]3+, 6 electron cua ion C03+ d~u ghep thanh c~p nen phirc chat co tfnh nghich tit. Toy nhien khOng phai til ca nhtmg phec chat bat dien cua ion Co3+d~u tit. Vi du nhu anion phuc [COF6]3- c6 tfnh thuan ta, momen tit do dugc cua phirc chcft luang ling vOi su co I114t4 electron doc than. Thirc te d6 dan d~n suy nghi trong tnrong hqp nay, ion C03+ khOng trang thai lai hoa d2sp3 rna trang thai lai hoa sp3d2, nghia Ia cac obitan 4s va 4p khOng lai hoa v6i obitan 3d rna v6i obitan 4d ngoai (thuong goi Ia S,", lai hoa ngoai de phan bi¢t v6i S1{ to; h60 trong Ia kieu d2sp3) :

la nghich

3d

Momen tit do dugc cua cac ion phec [Fe(H20)6]3+ va [FeF6]3- nrong ling v6i sq c6 m~t trong phuc chat 5 electron d¢C than, cua ion phec [Ni(NH3)6]2+ nrong ling vm Sl! c6 m~t 2 electron d¢C than d~u duqc giai thich bang giii thi€t trang thai lai h6a sp3d2 cua Fe3+ va Ni2+. Uu diem cua thuyet lien k~t h6a tri la mO tit mot each dan gian va cu the cac lien k€t cr trong plnre chcft va giai thfch duqc ur-tfnh cua phec chcft. Nhuoc diem cua thuy~t lien ket hoa tri la khong giiii thfch diroc mau sAc cua cac phtrc chcft. 15

THUYET TRVONG TINH THE

Thuyet truang tinh thl do hai nha v~t li Beta (H. Bethe) va Vlec (V. Vleck) de ra nam 1933 de giai thich tinh chat cua cac chflt dang tinh the nen co ten goi do. Mai den nhfrng nam 50 cua the' ki nay moi duoc ap dung vao phirc chat cua kim loai chuyen tiep Hi.nhimg h~ cung co SI! sap xep deu dan ciia cac hat mang dien tlch. Khac voi thuyet lien ket hoa tri, thuyet tnrong tinh the khong dua van khai niern lai hoa va su tao thanh lien ket cho-nhan va phoi chii

rna

coi su tao plurc la ttrong tac tinh dien giua chat tao phirc

tir. Thuyet tnrong tinh the xet vi tri ella cac obitan d (hay f) trong khong gian cua

nguyen til trung tam va xet hrc d~y electron tren nhirng obitan do b6i phoi til. Thuyet do khong

den kfch thucc va cau tao ella phoi til

C\!C

rna coi

phoi ttl la nhirng dien tich diem hay luang

eire, chiing diroc sip xep trong kh6ng gian nhu the nao d~ nang luong dl1y giira cac dien tich diem do la tieu. Dieu nay xay ra khi ph6i til sAp xep tai cac dinh ella hinh bat dien (s6 ph6i trf cua nguyen

tir trung tam 13 6) hoac cac dlnh cua hinh nr dien (s6 ph6i tri cua nguyen

tu

trung tam bang 4). Neu thuyet lien ket hoa tri coi su tao phirc sinh ra khi cac obitan ella nguyen til trung tam va phoi tu ehe phu nhau tao nen nhirng lien ket c thi thuyet tnrong tinh th~ eho rang trong phtrc chat, nhimg obitan cua nguy~n

tir trung tam bi nhfrng dien tich diem cua phoi

tu dciy se sap xep nhu th~ nao de wang tac giua cluing

la cue tieu.
va

V~y co s6 cua thuyet tnrong

tinh th~ 13 hrc day tinh dien gifta cac electron cua ph6i til

ella nguyen til trung tam.

Trong nguyen tu tl! do ciing nhir ion nr do cua kim loai chuyen tiep, cac obitan d cung

mot lap (dxy, dxz' dyz, d zl va d xl_y')

eliu) thi

co nang luong nhu nhau va duoc goi la suy

bien. Neu

ph6i

tiI tao quanh ion kim IOl;1.i m¢t tnrong d6i xirng dill (di~n tich phan bo dong dell tren toan khoi

su suy

bien ve nang luong van khong thay d6i, nghla la cac obitan d vAn co nang luong

nhir nhau mac du nang hrong ella cac obitan d tang len do bi ph6i khong d6i xung cau nhu truong bat dien, truong chat nhfrng obitan d 6 glin ph6i obitan d

tu dien

tu day.

Nhung trong tnrong

(d6i khi tnrong hlnh vuong) cua phirc

(t.

a xa ph6i

nr bi day rnanh nen nang luong tang len nhieu, con nhirng.
Nlur vay, khi tao plnrc, nang hrong

tir bi d1'iyyeu nen nang hrong tang len

ella cac obitan deu tang len nhirng tang khOng d6ng deu, Truce
het cluing

ta xet sir bien d6i nang

hrong ella cac obitan d trong pM(c chdt heir dien. Hmh 1 trlnh bay vi trf de obitan d cua ion kim loai . trong cau hlnh bit dien cua cac ph6i tu (vong nhat chi obitan • d z1 va d.X

tron

chi vi tri cua ph6i nr, nhirng hlnh qua bau t6 den
-y
l

va nhirng qua btiu

trang chi nhitng obitan dxy, dxz va dy,,). Ta thay obitan d ZI nam tren true d .I_yl phoi 16
Z

va obitan

nam tren true x va true y b ga.n han voi cac

tu

cung nam tren cac true nrong irng nen co Hinh 1. Truongbdt di¢n cua ClIC phdi til

nang hrong cao con

ba obitan dxy, d" va dYl narn tren dirong phan giac ella cac true x , y, z

tirong ling b xa phoi tii han nen e6 nang luong thap han. Nam obitan ella ion kim loai co nang hrong nhu nhau, trang tnrong bat dien ella phoi tii dii phan chia thanh hai nhom: nhom ely g6m hai obitan co nang luong nhir nhau va cao han va nhorn d, g6m ba obitan co nang luong nhu: nhau va thap hO'O (Hinh 2):

N ling IlIl;Ing

NlIng IlI<;lng trung blnh cua obitan d trong tf\.J'angtinh

the

Ion It! do

Sl/ tach mac nllng lll'9'ng cac obitan d trong trttOng bat di~n

H inh 2. SI! /('ieh e(le mile ruing luang cu« obi fan d trong phi(' ehut belt dien

C 1111

y:

Obi tan d z' th \!C ra Ia t6 hop cua obi tan d z' _.,' va obi tan d ,'_ y'
,d

hai obi tan nay

giong voi d~, _y' . Ve hlnh dang thi 3 obitan d .'_y' voi cit J obitan dxy,dxz va dyz.

/_.'

va d,'

_y'

giong vci nhau va giong

51.! bien d6i nang luong cua cac obitan xay ra nguoc lai, Hlnh 3 trlnh bay V! tri ciia cac obitan d cua ion kim loai trong Call hinh ttl"dien cua phoi tii (vong tron
Trang phuc chdt trang chi

(u dien,

V! trf

cua 4 phoi til tao nen mot cau hinh tu dien, vong t6 den chi vi trf ella phoi til

trong mot cau hinh

tu dien

khac, cac qua bau chi obitan van duoc bieu dien giong nhu hinh 1):

Ta thay trong plurc chat nr dien, ba obitan dxy, d., va dYl b gan phoi obitan

tiI hon hai

d zl va d x I-l nen bi dfiy manh han

va tang nang hrong nhieu hen. V~y flam

obitan co nang hrong nhu nhau ella ion tu do, trong tnrong

tu

dien cua phoi ttl cling

phan chia thanh hai nhom nhung nguoc voi

. trong tnrong bat dien: nhom dE gorn 3 obitan co nang Iu:qng nhu nhau va cao hon va nhorn ely g6m hai obitan co nang IUQ'Ognhu nhau va thap han (Hlnh 4):
Hinh 3. Truong tu dien cua cue ph61 til
2·H6a hoc vO 00· T3

17

Nang Il1I;1ng

NAng I~ng trung blflh eua obltan d trong WOng tinh thd 51/ tach m(fc nang Il1I;1ng cac obita n d trong tntOng bat di~n

Ion II/do

Hinh 4. Sif ta("h ("tk mu(" nang luong ("ua obitan d trong phu(" ("hat tu difn

Trang tnrong hinh vu6ng cua phol tli, hien tirong phan chia cac mire nang hrong cua obitand obitan dz' phirc tap hen: obitan d x '_y' kh6ng chiu anh

a gan

phoi

til bj dfiy manh nhat nen tang nang hrong,

huong tnrc tiep cua phoi tl'r nen hoi giam nang hrong; trong ba

obitan dxy, dxz

va dyz, obitan dxy chiu tac dung t11!C tiep hon nen

co

nang IUQ'I1g cao hon hai

obitan con lai (Hinh 5):

SI! tach mire nang hrong cac

obitan d trong tnrong bat dien

St! tach mire nang 111gng_ cac obitan d

trong tnrong hinh vu6ng

Hinh 5. S!( uich !luk ruing luang

('Ull

obitan d trong phu'(" ("hUt

18

Nhu vay, phtrc chat hinh vuong Iii mot bien dang cua phuc chat bat dien, trong do hai ph6i tir

a V! trf trans a tren

true Z bi lay di. Do do obitan d z' diroc lam ben them nhieu so voi
d"'_yl

trong phirc chat bat dien va obitan d., va dyz diroc lam ben them mot it, con cac obitan d,y tra nen kern ben hem.

va

Thong

so tach nang lU'!fIg

Hieu nang Iuong cua obitan d "cao' va obitan d "thap" diroc goi Ia thong sf)' tach ndng

luang, ki hieu la d. Trong phtrc chat bat dien, so voi mire nang ltrong trung binh ella obitan d
trong tnrong tinh the (Hinh 2), m6i electron chiern nhirng obit an d ~, va d x '_y' (kf hieu HI dy) co nang hrong cao hon

la 3/5lio (lio

la thong s6 tach nang luong trong tnrong bat dien,

111. chu

cai dUng dau chu octaedre l8. bat dien) va m6i electron chiem obitan dxy, d., va dyz (ki hieu Iii d.) co nang lirong thap hem la 2/5~. obitan dxy, dn d z , va d,x Nguoc lai, trong phtrc chat tu dien, m8i electron chiern cac

va

dy, co nang luong cao han la 2/5dT

(Ll.r

Iii thong s6 tach nang hrong trong

tnrong tu dien, t la chtr cai dirng d~u chu tetraedre la tu dien) va m6i electron chiern cac obitan
--y
1

co nang hrong thap hem la 3/5dT (Hinh 4).

Thong s6 tach nang luong d phu thuoc vao cau hinh cua plnrc chat, ban chat cua ion trung tam va ban chat cua phoi tir, - Phuc chat bat dien co thong s6 tach nang hrong do Ion han thong s6 tach nang hrong dT cua phuc chat uc dien. Neu co cung ph6i tir va cung ion trung tarn, phirc chat trr dien

co

thong s6 tach nang hrong bang bon phan chin thong s6 tach nang luong cua phrrc chat bat dien
(~=

4/91:!J.o. TOng cac thong s6 tach nang luong de cua phuc chat hinn vuong (chtr cai c dtrng )

dau chil caree la hinh vuong) IOn hem do. - Dien tich cua ion trung nhu vay Iii VI ion co dien tich

tam co anh huang den d: ion co dien tich 16n co d Ion. Sa di

rnanh phoi tir ve no va electron cua ph6i tir day manh cac

Ian hut

electron d nen gay tach, mot mire dQ lrm, rmrc nang luong cac obitan d. Vi du nhu cac ion phuc [Cr(H20)6]2+ va [Co(NH3)6]2+ c6 I:!J.o be han cac ion phtrc [Cr(H20)6]3+ va [Co(NH3)613+ nrong rmg (xem bang 1), Kich

thuac

cua ion trung

tam ctlng c6 anh huang den d. Vi du nhu ion phtrc cua Cr" c6

d be han ion phtrc tuong nr cua Rh3+

va Ir" (xern

bang 1). Nhlmg ion trung tam thuoc cac day

kim loai chuyen tiep thu hai va thtr ba luon luon co d

Ian han

so v6i day kim loai chuyen tiep

thu nhat, Dieu nay duoc giai thich la ban kinh Ion cua ion trung tam tao dieu kien cho cac ph6i

til den gan va do d6 electron cua ph6i nr gay tach, mot muc dQ Ion, rmrc nang hrong cac obitan
d cua ion trung tarn.

19

Bang 1

Thong

so tach nang
13.000

htqilg trong tru<mg bat dlen .6..0 (bang em")

cr+ [CrC4;]4[CrC4]3. [Cr(H2O)6J3+ [Cr(NH3)6]3+ (Cr(en)3f+ 18.000 [Cr(en)3]3+ [Cr(CN)6]313.200 17.400 21.500 21.900 26.600

c--

Mo3+
19.200

[MoCleJ3-

[Cr(H20 )6]2+ 14.000

Coh, Co3+, Rh3+, [Co(H2O)6]2+ 9.300 [Co(H2O)6]3+ [Co(NH3)6]3+ lCo(en)3]3+ [CO(CN)6]318.200 22.900 23.200 33.500 [Rh~J3-

tr"
20.000

[IrCle.] 3-

25.000 41.000 41.400

[CO(NH))6]2+ 10.100 lCo(en)3f+

[Rh(H2O)6]3+ [Rh(NH3)6]3+ [Rh(en)3J3+ [Rh(CN)6]3-

27.000 [Ir(NH3)6f+ 34.100 34.600 45.500 [Ir( en)3] 3+

11.000

Mn2+, Mn3+ [Mn~J4. 7.500 [MnC~]3[Mn(H2O)6J3+ 20.000 21.000

[Mn(H20 )6]2+ 8.500 [Mn(en)3f+ 10.100

Fe2+, Fe3+ [Fe(H2O)6]2+ (Fe(CN)6t 8.500 32.800 [FeC~]3. [Fe(H2O)6]3+ [Fe(CN)6]3en 11.000 14.300 35.000

= etylendiarnin,
60 trong

lcm'>

11,96 limo!

- Phtli thong s6 tach

tit co anh hirong manh d€n thong s6 tach nang luqng 6. cua phtic chat Bang 1 ghi
phtrc chat cua 11 cation kim loai voi 5 ph6i tiro Bang cho thay

kha nang

gay tach cua cac ph6i tir do tang len thea thtl tu; Cl , H20, NH3, en va CN- , nghia Ia Cl phoi nr gay tnrong yeu nhat va CN' 20

Ia

la

phoi til gay tnrong manh nhat trong 5 ph6i nr do,

Dua

van gia tri thong s6 tach nang luong ~ xac dinh diroc bang thuc nghiem trong cac plnrc
<.s<;N- < F- <OH- <C20~- <H20<NCS- <py<NH3<en<dipy<NO;<CN<co.

chat bat dien, nguoi ta xep cac ph6i tu thea tlnr tt! hrc tnrong tinh the:

r <Br- «cr

Ia dOy phd h6a hoc, trong do ph6i tu dirng tnroc c6 tnrong yeu han phci tu dirng sau, Nhirng ph6i tir dung truce NH3 thirong la ph6i tir gay truang yeu va
Day ph6i tir ducc goi

nhirng phoi tir dtmg sau NH3 11\phoi tir gay truang' manh.

Gidi thteh tu-tinh' erla phite chill theo thuyet truong tinh the'
Thuyet tnrong tinh the cling nhu thuyet lien ket hoa tri deu tinh s6 electron ghep doi va s6 electron doc than cua ion kim loai trong plurc chat, Theo thuyet tnrong tinh the, kha nang ghep doi cua electron trong phuc chat c6 lien quan voi thong s6 tach nang hrong ~. Neu nang

M ghep doi hai electron Ion hon .6. thi 5 obitan d cua ion trung tam Ian Iuet diroc dien m8i obitan mot electron r6i san d6 dien tiep electron thri hai va phuc chat co spin cao. Neu nang Iirong P 160. han thl tnroc het electron diroc dien dll cap van nhirng obitan c6
hrong P can thiet nang hrong thap va phuc chd: c6 spin thdp,

De lam vf du, chring ta xet su sAp xep electron

ion phtrc bat dien [CoF6]~· va [Co(NH3)6]3+. Ion Co3+ tt! do co cau hinh electron: Co \3d)
3

tren cac obitan d cua ion Co3+ trong cac

Itt l iii I iii I 0

va thong s6 tach nang hrong do cua [CoF6 la 156kJ/rriol va cua nen 6 electron 3d cua ion Co3+ trong hai ion phirc do duoc sap xep

Ngtroi ta xac dinh duqc nang lirong ghep doi P cua cac electron tren cling mQt obitan trong ion Co3+ la 251kJ/mol [Co(NH3)(i13+ Ia 265kJ/mol nhir hlnh 6 trlnh bay:

6.o=265kJ/mol

6.0 = 156kJ/moi

Ion ICoFe 1

3·

lonCo3+ trong trtIOng

66i xUllg

cau

Ion ICo(NH3ls1

3+

Hi nh 6"

each sdp xe'p 6 electron d ctia

ion Co" trong ion [C oF6t"

va ion f Co( N H 3J6t+ 21

Nhir vay trong tnrong s6 electron

yeu cua cac ion F- , th6ng

s6 tach nang luong ~ co gia tr] be nen

duoc sap xep tren cac obitan d da tach cua ion Co-1+ cCmg gi6ng nhu trong ion nr do va [COFo]3- [a phirc chat spin cao (co 4 electron doc than). Nhung trong tnrong manh tao nen boi cac phan ti'r NH3, thong so tach nang luong ~ co gia tri 1611nen cac electron chi diroc sap
xep tren cac obitan electron electron doc than). doc than. Bang 2 trinh phirc chat bat dien, bay thong nang luong 56 tach nang 111Q'rlg ~ xac dinh bang thirc nghiern cua mot s6 chi co th€ 13 chat d co nang Nhfrng thuan luong rhap va

lCo(NH3)61.l+
doc than hoac

18. phirc chat

spin thap (khong nr neu khong

co co

phirc char spin cao la chat thuan tir neu co electron

tu
la

con nhirng chit nghich

phirc chat spin thap

co hoc hrong til va trang thai spin cua ion phirc xac dinh duoc khi do tir-tinh cua chat Qua bang ta thay trang thai
ghep d6i P cua ion kim loai tfnh dtroc tir spin cua ion phirc phil hop voi thuyet Bang

tnrong tinh the.

Thong so tach va nang luong ghep d6i P cua mot so ion phuc bat dien
Cau hinh electron
clla ion Ion

P, kl/mol

Ph6i tu

~, klIma]

Trang thai
spm

3d4

Cr2+ Mn'+

281 335 305 359 210

H:P
HoG H:>O

166 251 93
163

cao cao cao eao cao

3d';

Mn "
Fe3+

,H2O H~O
CN-

3do

Fe2+

124 395
ISS

thap
cao

Co3+

251

F-

NH3
3d7
Co:>+

275
111

thap
cao

269

H2O

Phirc chat ttf dien co thong s6 tach nang hrong ~ be han so voi phtrc chat bat dien nen
thirong

la hop

chat spin cao ph6 bien han plurc chat bat dien. tiep cac day thu hai va thli' ba co thong s6 tach nang

Plurc chat cua ion kim loai chuyen

hrong ~ 100 han sO vci phirc chat tuong tu cua cac kim loai chuyen tiep day thtl nhat nen hau
nhu lu6n luon co spin thap.

22

..

Nang luang Lam be'n boi truang tinh thi

Thea thuyet tnrong tinh the, khi tao phirc mot mire nang hrong suy bien cua 5 obitan d cua ion trung tam c6 the: tach thanh mot s6 rrurc (2 trong trtrong bat dien va tnrong til dien va 4 trong trtrong hinh vuong cua phoi Ill) nang luong khac nhau, Neu electron dien vao obitan d co rmrc nang luong thap hon nang hrong trung blnh cua obitan trong rnrong tinh the: (cac hinh 2 tinh thl (vier tilt la LB). Trang tnrong bat dien cua phoi tLr, nang luong LB Ian nhat khi cac obitan d, dien du electron con cac obitan d, tr6ng electron (d~d~). Nang luong LB do bang 6 x 2/5t...o =

va

4) thl nang luong giarn xuong. Nang hrong giam do duoc goi la nclllg III(f/1g lam bin bd! tru/mg

12/560, Nguoc lai khi

khong

un ca

cac obitan d, deu dien du electron (d ~d~ ), nang hrong LB bAng s6

VI 6 x 2/5t...o - 4 x 3/5t...o = O. Trang phirc chat bat dien spin cao (tnrong yeu), khi ion
(d :d~ ), nang' hrong LB .

trung tam c6 cau hlnh electron d", rnoi mot obitan co mot electron

cting bang s6 kh6ng VI 3 x 2/5t...o- 2 x 3/560

=9.

Nhu vay trong phirc chat spin cao, nang luong LB

trong phirc chat spin thap, nang hrong LB Ian nhat chat c6 cau hlnh electron chat co cau hlnh electron

a phirc

Ian nhat

a plurc chat

cua Cr(lll) va

chat cua Corlll).

Ion Cr'" trong phirc Ion Co]+ trong phirc

d;d~ va d:d~

nang luong LB la 3 x 21St...o = 6/560,

va nang luong LB la 6x 2/560

= 12ISt...o' Khi them hay bot

electron cua cac cau hinh electron do, nang hrong LB deu giam xu6ng. Vi du ion Ni3 + hay ion Co2 .. trong phirc chat co diu hinh electron be hon so vai ion Co·l+hay ion Fe}.... Nang hrong LB cao giai thfch tinh tra dong h9C cua phirc chat spin thap ella Co(lll) va d:d~ va nang hrong LB la 6 x 2/5t...o

-3/560 = 9/5(j,0,

tinh khong ben dong h9C cua plurc char ella Fe(III) co cau hlnh d~ so voi phirc cha't cua Fe(II)
co csu hlnh d'', Vf du nhir hexaxianoferatrlll) hexaxianoferat(lI) ben dong hoc cua phirc char thanh tuu nay) de ra kern ben donghoc hen (do d6 co d(le tfnh) vi co nang hrong LB thap hen. Khai niem tfnh tro dong h9C va tinh khong

da

diroc Taube (Henri Taube, giai rlurong Noben narn 19R3

ve

de: chi t6e db phan irng (chu yeu cua phan ling thay the ph6i nr). Tinh he'll
dong

doug h9C co lien quan voi nang hrong boat hoa cua phan irng va khac vci tfnh hi!n "Iliff 119(" co lien quan den bien thien nang luong Gip, entanpi va entropi ella hop chat,

Khi tfnh nang luong LB cua cac phirc chat bat dien cua kim loai chuyen tiep, nhan thay phuc chat cua nhirng ion trung tam co Call hlnh d'', d', d2, d3, dS, d9 va dlO voi phoi manh hay tnrong yeu deu co nang luong LB nhu nhau nhung phirc chat cua nhimg

tu tnrong
ion trung

tam d", d", d'' va d" vci ph6i tll tnrong manh co nang luong LB Ian han nhieu so voi ph6i

til

tnrong yeu,
Phtrc chat

tu

dien co L\T be hon /\.0 cua phirc chat

bar

dien. Tuy nhien c6 rnrong hop

23

xac suat tao thanh cau hinh bat dien va cau hinh tu dien la gan nhu nhau, vi du nhu phirc chat ella Co(I1) voi cau hinh d", Trang tnrong bat dien .yeu, cau hinh electron d? b dang d ~d ~ va trong tnrong tu dien, b dang d~d!. 2 x 3/560 Nang hrong LB ciia phuc chat bat dien la 5 x 2/560 -

6/511T

= 6/5 x 4/9b.o = 3/5b.o.

SCN- .

= 4/560

va cua phuc chat tu dien la 4 x 3/560 - 3 x 2/560

= 6/560.

Vi Ar

= 4/9da

nen

Tinh roan mot each don gian nhu vay ta thay nang hrong LB ella NH3, etylendiamin va phrrc ehat tu dien voi

hai tnrong hop Ia gan nhu nhau: 3/511c (tnrong tu dien) va 4/5b.o (tnrong bat dien), That vay, ion Co2+ tao nen phrrc chat bat dien voi F- , H20,

cr .a-: ,OH-,

Ion Ni2+ (d") trong phrrc chat bat dien tnrong manh ciing nhu tnrong yeu dEu co cling mot cliu hinh d~d~. Nhung d6i v6i cau hinh hinh vuong thl su tao plnic trong tnrong rnanh la

. thuan tien han so voi trong tnrong yeu VI ca 8 electron deu dien vao nhirng obitan nang hrong
thap (d~zd~zd22 d~y) lam cho nang luong LB la cue dai, That vay, da s6 phuc chat ella Ni2+ c6
Z

du hlnh bat dien, mot s6 it plnrc chat hlnh vuong diroc tao nen voi phoi

tit tnrong manh nhu

CN', dimetylglioxim

trong khi tat

cil

phtrc chat cua Pd

+,

Pt

va Au

eo can hlnh hlnh vuong VI

d6i voi nhiing nguyen t6 4d va 5d, thong s6 tach nang hrong 11luon luon 1&1 hOO so voi nguyen t6 3d (thong s6 tach 11cang Ion, nang hrong cua obitan d,,1_y2 cang cao va nang hrong ella cac obitan con lai ding thap),

Hieu

{rug

Lan-Tela tit b vi tri trans trong phtrc chat bat dien (0 tren tT1,lC chang han) dich z

Khi hai ph6i

chuyen ra xa hay gan ion trung tam hon so v6i cac ph6i tit khac, nguci ta n6i phirc chat bat dien

bi bien dang kitu ta phuang (cau hinh d6 goi chung la bat dien lech). S'! bien dang ki~u tu
phuong cua phtrc chat bat dien ia bien hien cua hieu irng Jan-Tela, Nam 1937, Jan fa khong

va Tela (A.

Jan va E. Teller) phat bieu rang trang thai electron suy bie'n cua mtit phdn ttl khong thang hang

ben. phdn

ttl se bien dang hinh hoc dt gidm tinh d6i xung va dt! suy

bien.

D~ lam vi du chnng ta xet phtrc chat bat dien cua ion eu2+ (d"). Cau hlnh electron cua
Cu2+ trong phrrc chat bat dien la d=d~. VI tren cac obitan d, c6.3 electron nen c6 hai each sAp

xep electron: 2 electron tren dZ1 va mot electron tren d"l_yl hay mot electron tren dZ1 va hai
electron tren d x' _y"

Hai cliu hinh electron

d!2 d ~l_yl

va d~, d ~2 _y 2 c6 cling mot mrrc nang

hrong nen trang thai electron cua eu2+ trong phtrc chlft bat dien 13. suy bien bac hai, Theo dinh If Jan-Tela, trang thai electron do la khong ben nen phrrc cha:t bat dien cua eu2+ phai bien dang hai cau hinh electron d6 trb nen khac nhau v€ nang luong.

de

V 6i cau hlnh electron d!, d ~2 _y2 , nh frng ph6i tit

ion eu2+ rnanh hen so v6i nhtrng ph6i tir

a tren

true

bi chan v6i hat nhan cua

Z

a tren

true x va true y nen nhtmg ph6i tit 0 tren true

24

l:J xa ion kim loai hem cac phci tir khac tao nen mot

. true z va obitan

ellU

hinh bat dien lech keo dai thee phuong

dZ1 tro nen ben hon obitan d~l_yl nghia Iii d¢ suy bien giam.

Tat nhien voi cau hinh electron ngiroc lai: cac phoi ti'r tren true x Thirc

d:,
2 +.

d~'_yl , sl! bien dang cua phirc chat bat dien xay ra ion kim loai hon hai ph6i

va true y a xa

tu b tren

true

tao

nen mot cau hinh bat dien det theo phirong true z.

tt

nguai ta chi quan sat diroc kieu bien dang doc theo phirong cua mot true Vi du trong tinh thi! mu6i d6ng(II) halogenua,

&

trong nhieu plurc chat bat dien ciia Cu

thirc

nghiem xac dinh diroc hai loai d¢ dai ciia lien ket Cu-X (bing A):

CuX2

Lien k€t ngan 0,193 0,230 0,240

Lien ket dai 0,227

CuF2
CuCI2

0,295 0,38

CuBr2

Trong Sl! bien dang doc thee phirong cua true z, khong chi d¢ suy bien cua hai obitan de

giam rna

ca" d¢ suy bien

cua ba obitan ely cG.ng giam, hai obitan d~l va dyz diroc him ben them

con obitan d., bi giam do ben, Nhu vay

tit hai mire nang luong dE va ely trong tnrong hat dien,

khi bi bien dang kieu td phuong d5. tach thanh 4 rmrc, Khi pb6i ttl

a tren

true

rbi xa ha.n ion

trung tarn thl pmrc chit bat dien tro thanh hlnh vuong, trong do 4 mire nang hrong bien d6i

manh hon nira (Hlnh 7). M6i vach ngang trong sa dO cua hlnh nay chi mire nang hrong cua m¢t
obitan d. ~ -.... .... .. .. ..
' ' '

.. - ....

d ~, -y 1

_...,. ..

..

'

.... ......... - ....~._..!._. d1

dyz Bat dien

..~ ........
",

....

'"

... ~~

-dxz dyz
t(c

._
d, z

Bit dien l¢ch (chop kep

giac)

Hinh vuOng

Hinh 7. Sif hitn db; muc niing lll?1Jg CUll eae obitan d eua nguyen til kim loal d trong 3 truang: hat dien, hat di¢n l¢ch keo dai va hinh vu6ng.

25-

Qua so d6, ta thay ro dang bat dien lech kieu ta plnrong (hay cau hlnh ch6p kep tu giac) Iii trung gian giiIa cliu hlnh bat dien va cau hlnh hinh vuong, D6i voi nlumg ion trung tam co cau hmh d:d~ vii d~d~, viec chuyen phuc chat bat dien thanh plurc chat hlnh vuong la thuan loi ve mat nang luong, That vay, nhfmg ph6i tiI tnrong manh nhir NH3, etylendiamin

the

de thay

nhirng phan tir H20 trong ion phuc bat dien [Cu(H20)6]2+ tao thanh nhirng ion pmtc hlnh vuong [Cu(NH3)4]2+, [Cu(en)2f+. Hieu irng Jan-Tela the hien manh nhat iJ cac phirc chat co cau hlnh electron cua ion

trung tam la d:d~ va iJ cac phirc chat spin thlip co cau hlnh electron cua ion trung tam Iii d:d~. That vay, phirc chat bat dien cua nhimg ion Cr+ vii Co2+ den bi bien dang,

P.h6 hap thu va mau cua phitc chat

Milu cua chdt. Nhu da biet mau Hi ket qua cua s\T hap thy mot phan anh sang trong
thay. Nhfmg birc xa khong bi chlit htlp thy diroc pharr chieu hoac truyen qua chat di den mitt ngum ta va

gay nen cam giac mau (Bang 3).

Bang 3.

Bulk s6ng CUB anh sang trong thay va mall

Bircc s6ng cua brrc bj htlp thu, A 4000-4350 4350-4800 4800-4900 4900-5000 5000-5600 5600-5750 5750-5900 5900-6050 6050-7300 7300-7600
X~

MElU cua buc xa bi htlp thy tfm xanh cham Cham-lye} luc-cnam 1I,Ie lam

Mau trong thay (mau

phu)

vang-luc
viing dacam do do tfa tfrn xanh cham Cham-lye} luc-cham lye lam

luc-vang
vang daeam do do tia

Khi hap thy hoan toan anh sang, ehtft c6 mau den va khi khong htlp thu anh sang, eha't trong su6t hoac co mau trang.

Phd hdp thu. DUCmg cong bieu dien su bien dOi cua d~ nap thl,l anh sang thea buoc song diroc goi la phd hap thu. Trong pho hap thu c6 nhUng vung tai d6 cuong d~ cua anh sang 26

truyen qua

be

hon CU'Ongdq anh sang toi, diroc goi lit ddi IIdj) thu. CI/C deli

CliO

ddi lul,) thu xac

dinh mEIU va cirong 09 cua mau.

Mot trong nhirng thanh nru n6i bat cua thuyet tnrong tinh th~ lit giai thich nguyen nhan
sinh ra phd hap thu cua phirc chat cac kim loai chuyen tiep. Ph6 hap thu cua da s6 phirc chat cua nguyen t6 d gay nen bai sir chuyen doi electron tit obitan d co nang luong thap den obitan d co nang hrong cao thuong goi la su chuyln dm d-d. Boi vay, ph6 hap thu cua cac chat thirong dUQ'C goi Iii phd Mil) thu electron.
De: lam vi du, chung ta xet pho hap thy cua ion bat dien ITi(H}O)fJh

(Hinh

)3):

TIM

4000

5000 BlI& sOOg A, .8.

6000

7000

Deli hap thu co cue dai

a biroc
3

song 49261\ (thirong lay gao dung la 50001\) hay tan so

20300 cm'. Nhu vay, ion [Ti(H20)61 + hap thu anh sang vung luc va cho di qua anh sang vung do va vung xanh nen co mau tim.
Ion Ti'+ co cau hlnh electron d'. Thea thuyet tnrong tinh the, electron d duynhat do trong ion phirc [Ti(H20)6]3+ chiem mot trong 3 obitan d co nang hrong thap d~. DUGi rae dung

cua anh sang, ion phirc hap thu mot hrong til' nang hrong E =hv va bien nang hrong do thanh
nang luong kich thich electron chuycn doi tit d, den d y

Nang hrong do ehinh ia thong s6 tach nang hrong b.o =242,8 kl/mol cua ion phirc bat dien [Ti(H20)6f+ trinh:

va co the tfnh dUQ'C !U bUGCsong cua birc xa bi hap thu eire dai thea phuong

27

flo

= h-N
t6c d~

c A

(trong d6 h la hang s6 Plang tfnh bang Ls, C la Avogadro va

rum

sang tinh bang

mis,

N la s6

Llo tinh
flo

bang J) 10- 1. s)(3~~oO 10 m I s) x 6,623 X 1023 X 4926 x 10 m 6'--;-----v---'1 I '___--~-~--------' S Ion rno J/ion (6,626
X 34 8

= 242800

J/mol

= 242,8 kl/mol Neu tfnh bang cm' thi nang hrong

Llo nay

dung bang s6 song v' (s6 song cung diroc

,

goi la Hrn so):

v'

= _!_ =
A

4926

1
X

10-8

= 20300cm-1

, Bbi vay, tuy cm' khong phai

la

don vi do nang hrong nhung do tien lqi ngiroi ta cung

hay bi~u dien thong s6 tach nang hrong fl trong tnrong tinh th~ bang em" (xem bang 1). D6i vci nhfrng ion kim loai chuyen tiep c6 2 electron d tra len, nghia Is co cau hinh electron d", n>l,

Sl! chuydn dOi electron til mrrc nang hrong thap d€n nnrc nang luong cao

khong chi cua mot electron cua mot s6 electron nen sinh ra mot s6 dai hA'p thu vi du phd hlfp thu cua phirc chlft bat dien cua nhfrng ion d2, d', d? va d8 gom c6 ba dai. D~ If giai phd hlfp thu phtrc tap hon d6 theo thuyet tnrong tinh

rna

the dbi

hoi SlJ phat trien hon nira v~ If thuyet

(khOng trlnh bay trong khuon kh6 cua giao trlnh co ban nay). Tuy nhien d6i voi phirc chat bat dien cua nhung kim loai chuyen ti€p co cau hlnh electron d", d6 va d9• phd hap thu chi c6 mot dai nrong tv cau hlnh d'. VI du nhu phd hA'p thu clla cac ion phirc [Ti(H20)6f+' [Fe(H20)6]2+ va [Cu(H20)6]2+ duqc trinh bay tren hlnh 9: [Cr(HZO)6f+,

.10=20300 em"',mau tlrn

£i

;;>"

,:J
.10=10500 cm-1,mau !!,IC ,.g, nhat gan rnu khOng mau

Tan sO,cm"l

Hlnh 9. Phil http thu cUa dung dich cdc mudi cua

tr: CtJ+,

Fe2+ va C1I2+

28

Den day cluing ta hi~u phirc chat cua Cu +(d

2 9 )

tai sao phirc chat cua CU+(dIO}khOng c6 mau, trong khi co mau, phirc chat cua Ag", Zn2+, Cd2+ va Hg2+(dlO) d~u khOng c6 mall.

de dang

Cuang d¢ mau. Cuong dt! mau, nrc 18.cirong dt! cua dai hap thu, phu thuoc vito mire dt! "ngan cam" sl! chuyen doi electron d-d, Trang cac quy tAc IQc lua cua h6a hoc lUQ'I1g quan nr, trong nhat la nhtmg ngan cam chuyen doi electron v~ spin va ve tinh d6i xung,

Quy Idc lac Iva spin ngan cam bat kl Sl! chuyen dci electron nao lam bien dOi t6ng spin cua M. Vi du nhu ngan earn su chuyen doi electron d-d trong phirc chat bat dien spin cao cua
ion trung tam co cau hinh electron d5 (d!d;).
yeu den mire co th~ xem

BOi. vay, cac ion FeFi- va Mn(H20)~+ co mau

d6(d~d~). That vay, bat kl su

18 thuc te khong mau, SI! ngan cam v~ spin cilng tac dung den phirc

chat bat dien spin thap cua ion trung tam co cau hlnh electron earn.

chuyen doi mot electron nao trong he do cling lam bien d6i tong spin cua he cho nen bi ngan

Quy tde loc lua Lapo (Laport) han ch€ su chuyen dOi electron bOi tfnh d6i ximg cua phirc chat. Trang nhung phtrc chat khong co tam d6i ximg, vi du nhu phec chat tu dien, su chuyen doi electron d-d la diroc phep, Nguoc lai trong phirc chat bat dien, SI! chuyen dai
electron d-d

~!ngan

earn vi cau hlnh bat dien c6 tam d6i xirng, Sg ngan dim ve: tinh d6i xirng khOng co mau nhirng ion phtrc FeCI~ c6 mall

giai thfch tai sao phirc ch~t tu dien co mau darn han phirc chat bat dien cua cung mot ion trung tam kim loai, Vi du d6i vci Fe3+, ion plurc FeFt

vang

V? d6i

v6i. ion

eo2+,ion

phirc Co(H20)~+ co mau h6ng rat nhat trong khi ion phirc CoCl~

co mall xanh cham dam, Tuy nhien trong cac he thuc, sv ngan cam. v~ spin co the bi I01.libe mot phan vi du do urong tac spin-obitan va su ngan earn v~ tinh d6i xirng cG.ng co

the bi 101.libe do

su sai lech ella

da dien co tam d6i xirng, vi du vi hieu ung Jan-Tela chang han ... Bieu hien quan trong ella su ngan earn chuyen doi electron d-d HI.mau yeu cua phirc chat, cu the la cuong dt! thap ella dili hap thu trong phO electron. Thuoc do cuong dt! hap thu birc xa la h¢ 56' hap thIJ. c. H¢ s6 nay lien he voi mat quang D, do duoc bang thuc nghiem tren may trac quang, bOi he thtrc ella dinh luat Lambe-Bia (Lambert-Beer): D=sCI trong do mat Quang D

= 19 I; (6 day =

10 la cirong d¢ ella anh sang di tm dung dich ella ch<ftva

I
a

Ia cirong d¢ anh sang di qua dung dich, C la n6ng dt! ella dung dich tinh bang mol/l va Iia ~
day ella lap dung dich, Khi C lmol/l va I

Lcm thi s = A va h¢ s6 h<fp thu mol s chi phu

E

thuoc vao ban chilt cua chat trong dung dich, H¢ s6 ha'p thu mol trong khoang 5-;-500, vi du cua ion 1)(H20)6

ella phirc chat bat dien

la 5 va ella plnrc chfft tu dien

a trong

khoang

200-;-5000, vi du ella ion CoC1; la g~n 600.

29

Nhu vay, uu diem n6i bat han cua thuyet tnrong tinh the so voi thuyet lien ket hoa tri la giai thfeh diroc phO hap thu (hay mau) cua phrrc chat cac kim loai chuyen tiep cho nen ve sau thuyet da diroc Ogen (L.Orgel), Tanabe (Y'Tanabe) va Sugano (S.Sugano) tiep tuc phat trien,

chu

Tuy nhien thuyet rnrong tinh vi coi lien ket kim loai - ph6i ttr la lien ket ion va chi den obitan nguyen ttr cua kim loai rna bo qua obitan nguyen ttr cua phol ttr nen co mot s6
'

the

han che:

- Neu lien ket kim loai - ph6i ttr la lien ket ion thl tai sao nhung phan ttr trung hoa H20. NH3 lai co luc tnrong rnanh han nhtmg anion OH- , Cl", P- ..., phan til H20 c6
C\lC

manh

han phan ttr NH3·I'l-i co luc tnrong kern han, ion CN- c6 ban kfnh Ion han ion F- nhung co luc tnrong rnanh hem nIt nhieu mac du deu mang mot dien tich am. - Khong giai thfch duoc phd chuyen dich dien tfeh (se xet sau). - KhOng de cap den lien ket 1t mac du lien ket do gap nhieu trong phirc chat, nhat nhtrng phirc chat vol CO, anken, ankin, xiclopentadien ...

la

THUYET OBITAN PHA.N rlr(MO)

Thuyet lien ket h6a tri coi lien ket kim loai - phol ttr IS.thuan t6y cong h6a tri va thuyet tnrong tinh the coi lien ket do IS.thuan tuy ion trong khi thirc te lien ket kim loai - ph6i tir trong hau het phirc chat co mot phan cong hoa tri, BCti vay, thuyet obitan phan ttr t6 ra bao quat va chfnh xac hem khi gieii thfch cau tao va tfnh chat cua cac plurc chat.

Thuyel obitan phdn III coi phan ttr phtrc chat, cling nhu phan ttr hop chat don gian, la
mot hat thong nhat bao g6m nguyen ttr trung tam va cac ph6i ttr. Chuyen dong cua electron trong phan ttr diroc mo tei bang mot ham song 'V goi Ia obitan phan ttr (MO). Obitan phan ttr la t6 hop tuyen tfnh cac obitan nguyen tir cua nguyen tir trung tam va ph6i tiro Dieu klen de cac obitan nguyen tir t6 hop vai nhau la cluing c6 che phu nhau, nghia Ia co cling kieu d6i xung. Obitan phan duoc t6 hop nen co nang hrong thap hem cac obitan nguyen tirla obitan phdn IU lien ktl (Molk) va obitan phan tir dUQ'ct6 O!i.z / , hop nen co nang hrong cao hem la obitan phan OH.z· phdn lien ket (MO·). Quy lAc dien cac electron /0..,/ vao cac MO cua phuc chat cling giong nhu quy -H O-0'4-rr-+ ~-0H.ztac dien electron vao cac AO cua nguyen tir.

tu

the

ZI

tu

Ism vi du cu

tM.

chung ta xet ion

plnrc bat dien

[Ti(H20)6]3+,

trong do nhirng
x
I

/0.,
~

/1
.

I
as
1

obitan hoa tri• cua ion Tj3+ la 3 d z1 ,3d

-y

I,

3d.~,
v•

/
x

OH.z

3dX/. 3dyz, 4s, 4PJt' 4py va 4pz cua 6 phan ttr H20

30

Ia O'J,0'2' 0'3,0'4,0'5 va 0'6 (obitan 0' ehinh la MOO'~ co cap electron cua H20 thee z thuyet MO hay mot trong hai obitan lai

hoa

Sp3

eo cap electron

nr do cua 0
y x

trong H20 theo thuy€t VB). Obitan 4s ella Ti3+ to hop v6i 6 obitan 0' ella H20 (Hlnh 10)

tao nen cap

MOO'. lien k€t va phan lien ket. Ham song cua MO 0'~k la: 'PO' ~k= CI 4s
Htnh 10. Nhimg obitan nglly~n

flf to' hap nen nhiing MO 0'.

+ C2 (0'1 + 0' 2 + 0' 3 + 0' 4 + 0' S + 0' 6)

trong do c1 va c.Ja he s6 t6

hop.

Ba obitan 4p cua Ti3+, m6i mot

t6

hop voi hai obitan 0' cua H20 (Hlnh

x

11). 40 nen tilt cit ba cap MO (J p lien

x Px

ke't va phiin lien ker, Ham s6ng cua ba

MO(J~

la:
\fo-x =C34px +c4(0'1 -03) 'PO'~k =c34py \foz
lk
+C4(0'2 +

lk

-0'4)
Y
x y

= c34pz

c4(a5 - 06)

trong do c3

va c, 18.

s6 t6

hop. Ba
py

MOcrp lien ket co nang luong bang nhau va ba MO (J p nang hrong bang nhau.

phan lien k€t eo

Hai obi tan d 1 cua Ti 3+ to hop

v6i cac 0' cua H20 (Hlnh 12) tao nen
hai c~p MOO'd lien k€t vA phan lien k€t.
p

HAm song cua hai MOO'~k la:

pz
Hinh 11. Nhi'ing obitan nguyen tit

t6 hop
'P0'1k2 2 = ~ ~y
C7

nen nhitng MO

(J p

3d ~2 ~y 2 + Cs (0' I

0' 2

+ 0' 3 + 0' 4)
ra su

trong do cs• c6J c, va csia

M s6 t6 hop, 20's va 20'6 chi

che phu cua 0'5 va 0'6 a tren true

31

IOn g:fp doi so voi

SI!

che phu cua cac cr khac

& tren cac true x va y. Hai MO

<5 d

lien ket nay

e6 nang hrong bang nhau va hai MOcrd phan lien k€t e6 nang hrong bang nhau.

Hinh 12. Nhilng obitan nguyen ttl to' hqp nsn nhilng MO <5 d

Ba obitan

d, con lai cua Ti3+, trong phirc chat bat dien, c6 th~ che phu 1t voi obitan

thich hop cua ph6i ttl' tao nen M01td nhung H20 khong c6 obitan thich hop d6 nen chang t6n tai trong ion phirc du6i dang M01td khong lien kef (Hinh 13, trong hlnh chi trlnh bay obitan nguyen tl't dyz)

Hinh 13. Nhilng obitan

de ('ua tr: khong to' hop 011(/('v6i obitan a ('ua H20

S§p xep cac MO da: xet tren day thea tlur tl! nang hrong tit thap den cao, duoc gidn,
nang IUrjl1g ('(Ie MO cua ion phirc [Ti(H20)6]3+ (Hinh 14):

do

32

AOTi3+

MO[TI(H20),l+
...* 0''1,

NAng ItJQng ~4P

~' ----......J\'~"

/', ,~ , ,, ~ " ~, ,, ~v •

,,~

~~~ ~

~\

.,
\

0*

\\
\ \

,
\ \

,
\

0 . .0

11...
\

'\

\,
\,

'"

'. '.

~"'"' , "'l....1......1'-~----~

,,/<"''

~~~I...............'.'. \
(!.Jtxy1tu

I __I'7'T""TI__

'ltyz'

\,

\\ \ \'. '.
\

'.'. '. ,\ , \ '. \ \

,t
\\~;"

\\\{\ \

\, ,, \,

\ '. ' ,,
\

'. \ \
.'

,ax

Ik

a"'
'I,

' --(ffi, --(ffir , --[j}-,, ~

---fillL!!l

Ik ,,' ,', O'z, "

O2,''

l\~'1

\\

, ,~,,2

Ik

Ik'
I I

~,'

'~/

O'ik

Hlnh 14, Gidn d& niing l"flnE cae MO cua ion bat difn [fi(HPJ"r+

Dien 13 electron (1 cua Ti3+ va 12 cua 6H20) vao cac MO theo thli' tl! nang hrong tren gian d6 cac MO. dtn;1Cca"uhlnh electron cua ion [Ti(HP)6]3+:
(cr~k)2(cr~~ )2(cr~~~l )2(cr~k)2(cr~ )2 (crik )2 (1txy )1

Nhling electron tren MOcrIk dpm cM eM ye'u cac phan til H20 vi obitan h6a tri 0' cua H20 ben hon nhieu so v6i ion trung tam. M~t Wc nhDng obitan khong lien ke't va phan lien ke't dinh ebb chu ye'u l:J ion trung tam. Hieu nang hrqng cua cac obitan phan til' CJ ~ va
1td

18. !:J.,

giAi thich quan diem ve S1)' tach rmrc nang hrong clla cac obitan d trong thuyet tn.Wog tinh tM. GiS tr] cua I:l. quyet dinh nhieu tinh eMt cua phuc eMt. D6i v6i nhtmg phllc eMt tli di~n va hinh vuong, cac MO duqc t6 hgp nrong tl! nhung phlic tap hon,
3·HOa hoc vO co • T3

33

So sanh nhiing klt qua thu duoc cua thuyet obitan phan ta voi thuyet lien ket hoa tri va thuylt truang tinh .thi
Khi xet cau tao cua ion phirc bat dien [Ti(H20)6J'+' nhan thay r5 thuyet lien ket h6a tri va thuyet tnrong tinh the me ta nhirng phan khac nhau cua gian d6 nang hrong cac MO (Hinh 15). SI! tao thanh cac MOa lien ket phu hop voi su tao thanh cac lien ket cho-nhan giira ci)p electron tv do cua H20 voi obitan lai h6a d2sp3 tr6ng cua Ti3+. Nhirng thuyet VB khong chii

kha nang tao thanh cac .MOa phan lien ket nen kh6ng the giai thich dugc ph6 hap thu cua plnrc chat. SI! tach rmrc nang luong cua cac obitan d thanh hai rrurc trong thuyet tnrong tinh the phil hop voi su tao thanh cac obitan
1td

va

a~ c6 mire nang hrong khac nhau. Tat nhien khac voi

Nang hJqng

--illIITJ----I0]t-(Js

Hinlt J 5. So sanh fhuyet MO vm thuye't VB \'£1 tl!!lyet

trifling

tinh thl

thuyet tnrong tinh the, viec tinh roan nang hrong cua lien ket trong phirc chat thee thuyet MO

la phirc tap han rat nhieu, dn phai dung den may tfnh dien tl1 hien dai.
Nhu vay, gian db nang hrong cac MO cua phirc chat bat dien trlnh bay tren htnh 15 bieu hien 1'5 m6i quan h¢ ella ba Ii thuyet hien dai v~ cau tao cua phirc ch<1:tcac kim loai

chuyen tiep,
Chung ta xet cau hlnh electron cua ion phirc bat dien spin cao [CoF613. va ion phirc bat dien spin thap [Co(NH))6)3+ (Hinh 16):

34

Nang lUQ09

_ .~"
~, I,' I I' I

,,'

,"

,,....:.an-;
~I

* a; ay a;

,r-,....... r--\ \
al2• y2

as*

II

" .

}' '*
I' \

~'I

-w----',

~J..-t---

3d

\ Y.
I, I

\,'

'

rn-=A

"a~2

II II II II II I

II
\

II \I

l1t~1tyl

\\

II

\\I I\I II I I\\ \\ I II \ \I \ \\ \ I\ I \\ \ \\ I I\ \

i1!l.!!1!!t-

\\

\\
II \\ I \\ \ \

I\\~

\\

1~1k

\11" 2
~/'
I

It

0''''

\ \ ax •

i.

a,2'

Ik//

Z,,' ,
I

,"

' /

,
, I

,
, I

~'
b

Ik' a'

Hinh 16. SCId6 sdp xep cdc electron ho« fri (lin nhilng MO cua ion phu!."hatdi¢n [CoFoI'- (a) wl[Co(NH]JJ3+ (h)

nhan thay trong 56 18 electron h6a trj (6 cua Co3;. va 12 cua 6 ph6i tir), trong ion [CoF6J3• c6 ~
be (156 kl/mol),

12 electron

dien vao 6 ModI< va 6 electron con lai di~n vao MOnd va

MOcr: : «J~1<)1 (cr~)4 «J~ )6(1td)4 «J~:)2 • nghia la ion [CoFd3. c6 4 electron d"c than, con trong ion [Co(NH3)6]3+ c6 ~ 160 (265 kl/mol), 12 electron dien van 6MOcrl):: va 6 electron con lai chi dien van M01td «(J ~k) 2 «(J~!<)4 (cr.~k)6 (1t d)
6,
:

nghia 18. ion [Co(NH3)6]3+ khOng c6 electron dQc than. S1!sa.p xep khac nhau cac electron tren cac obitan phan tit 1td va (J ~ phu thuoc van L'l va nang hrong ghep dOi P cua electron gi6ng nhu da trinh bay trong thuyet tnrong tinh

tM.
35

SI! sai khac ve gia tr] cua !'!.trang hai ion phuc bat dien nay cua Co(lll}. theo thyet MO.
la SlJ khac nhau ve mire dQ che phu gitra obitan nguyen til hoa tri cua C03+ voi obitan hoa trj va MO phan lien ket cang khac nhau, do do!'!. cang Ngoai ra !'!.con chiu anh hirong
0'

cua F- va cua NH,. Cac obitan hoa tri che phu nhau cang nhieu, nang hrong cua MO lien ket

Ian va

lien ket - kim loai phoi tii cang ben.

1{

Ian cua

SlJ tao thanh lien ket

gifra kim loai va phoi

ur.

Lien kit

Jf

trong phuc chd:

Trong phuc chat bat dien, nhfrng obitan dxy• d., va dyz co the' dung de' tao thanh lien ket
1t.

Khi phoi nr co obitan co the' che phil

1t

vci

y.

nhfrng obitan

d, do, gian d6 nang Iuong cac

MO cua phan tir tro nen phirc tap hon nhieu: ngoai cac MOO' lien ket va phan lien ket con co cac MOn lien ket va philo lien ket nO'a va hieu
nang luong !'!.cilng bien doi. Nhirng obitan cua
H ill II J 7. SI/ rhe ph/I gii{a il,y "rla e0.1 + w'ti obitan f1 ('/iu 4 ion F"

phoi tir co kha nang do 13.: obitan p vuong goc voi true lien ket 0', obitan d va obitan 1t", Ult d. nhtrng obitan nay deu nam trong cung mat
phang voi obitan cua nguyen til trung tam.

Wing hrong

Hinh
obitan

17 trinh bay SlJ che phu cua vi du dzy, voi obitan p c6 cap
ion phirc bat dien
1t

de'

~·~· T ---0' d
(5"

..,'

s:

'.

electron cua bon phoi til nam trong mat phang yz, vi du trang chang obitan [CoF61
3 .

han, lien ket

lr

kie'u nay duoc goi l,a

H ill II 1R. Gidn db ndng luang ctu: MO H,; nia (coFoY

lien kef

cho-nhan.

Trong rnrong hop nay,

2p cua F~ co. nang hrong thap hon 3d

1t~kdinh

cua Co·1+ nen obitan

ehb chu yeu

a F~

va obitan

1t:

dinh chb chu yeu

a C03

+.

Gian d6

nang luong cac MO n: d duoc trinh bay tren hlnh 18 (vach ngang chi rmrc nang hrong cua obitan). Gian d6 cho thay hieu nang hrong d giam xu6ng so voi dai ltrong d d~c tnrng cho phirc chat chi co lien ket
0'.

Dieu nay giai thich vi trf cua ion F~ (va cac halogenua

khac) dirng

dau trong day ph6 hoa h9C.

Hinh 19 trinh bay voi obitan
1t.

51! che phu cua obitan d, co capelectron

cua nguyen til trung tam

0'

trong cua phoi til CO (hay CN") va hlnh dang cua MOo" (tao lien ket nay duoc goi

cho-nhan

voi nguyen tii trung tam). MOcrtk lien ket va MOn* cua CO (gach xien tren hinh chi obitan co cap electron). Lien ket k ieu
1t

lu

lien kh n-cho. Trong tnrong hop nay, obitan n*

1t;t

trong cua CO (hay CN-) co nang hrong cao hon obitan d cua kim loai nen MO

co nang

36

1r.Chod

-1r

Hinh J 9. Hinh dang n7c MO

Clio

phdl1

fl(

CO l'U

Sit

che pIli; giiia obitan

CliO

CO vai ohitan d ella kim loai

hrong cao han cac MO

0' ~.

Gian d6 nang hrong

Nang hrong

cac MOn diroc trinh bay tren hlnh 20 (vach ngang chi rmrc nang hrong cua obitan). Gian d6 cho thay

n.d

SI! tao thanh lien ket n lam tang hieu nang luong t..
so voi dai hrong lien ket
0'.

t.. d~c tnrng cho .phtrc chat chi c6

chuyen dich

1C

Khi tao thanh lien ket rt-cho mot phAn

mat d¢ electron

tu

nguyen

tu

trung

tam den ph6i tir lam ben them lien ket kim loai ph6i nr, Den day chung ta hieu diroc vi tri cua cac ph6i ur CO va CN- dirng cu6i trong day ph6 h6a
h9C. Hinh 20. Gtdn do ndng 1/(\1IIg {"(ic MOn" C/la plurc chllt VOl phO/ fir CO

Sl/PHAN LI CUA PHUC CHAT TRONG DUNG DlCH Hdng s6' ben va hdng s{/ kh6ng ben
Trong dung dich, phirc chat thuong xuyen phan Ii thanh cau ntii va cau ngoai tuong ur nhu hop chat dan gian phan li thanh cation va anion.
Vfdl,l:

37.

Na[Al(OH)41

Na+ -+

[Al{OH)41-

r6i ion phtrc lai phan li thanh ion trung tam va ph6i tiro Vidl,l: [Ni(NH3)612+ ,[AI(OH)41 = Ni2+

+ 6 NH3

=
C

A13+ + 40H-

Hang s6 can bang cua qua trlnh phan li ella:

K

2+

Ni

xC~
J

:=

9,8.10-')

C [Ni(NH .1 ) 6 ]2+

Hang s6 can bang K cang 16'0 khi ion phuc phan li cang manh, nghia lit ion 'phuc cang kern ben, Boi v~y hang s6 K chi dti ben cUa ion phuc trong dung dich, duoc goi Hi hang s6' kh6ng ben va ki hieu la Kkb•

qua trlnh phan li chuyen dich manh ve phia ben trai, phia cua qua trlnh tao phrrc, De chi kha nang tao phec cua nguyen tir trung tam, ngmri ta dung hang s6 can bang cua qua trlnh nguoc Iai d6. Hang s6 d6 diroc goi Hi hang s6 ben K, va 13.
Dai da s6 ion phuc Iii eha:t kern dien li, nghich dao ella hang s6 kaong ben:

-1 Kb=-Kkb

Hang s6 K, cang 16'0, phrrc eha:t cang ben. San day Hi hang s6 ben K, ella mot s6 ion phtrc (Bang 4) Bang 4

HAng s6 ben ciia ion phire

, Ion phtrc (1)

Kb

Ion phec (3)

Kb
(4)

Amoniac

(2)

Etylendiamin
1,0.108 '3,63.106

Ag(NH3); Cd(NH3)!+ Co(NH3)~+

Co(en)~+ Co(en)~ Cu(en)2+ _ 2

8.1013 4,9.1048 1,35.1020

2,45.Ht

38

(1)

Co(NH3)!+ Cu(NH3)~+ Hg(NH3)~+

(2) 1,99.1035 1,07.1012 1,99.1019

,

(3)

Ni(en);+
F[orua
3 AIF6-

(4) 1,29.1019

4,68.1020 1,26.1016

Ni(NH3)!+ Zn(NH3)!+
Bromua -

1,02.108 5,01.108

FeF3~ 6
Hidroxi

Al(OH)~
2,19.107 2,88.1012 5,01.103 1,0.1021

1,00.1033 2,63. 109 7,94.1029 3,63.10\4 3,63.108 5,02.1017 5,5.10" 6,67.1029 8,32.103

AgBr2~ AuBr2~ CdBr:~ HgBr:~

Cd(OH)!Cr(OH)~ Cu(OH)!~ Fe(OH)!~ Zn(OH)!~

Clorua

Iodua

AgCI~ AuC1; AuC1~

1,1.10

AgI~ HgI~Pbe4
Tiosunfat

2,63.109 2,0.1021 2,24.105 1,66.1015

o.o.2
HgC1!Xianua

Ag(S20,)~CU(S203)~- •

2,8.1013 1,86.1012

Ag(CN); Au(CN); Cd(CN)!Co(CN):Cu(CN); Fe(CN):Fe(CN)~Hg(CN)!Ni(CN)!-

7,08.1019 2,0.1038 1,29.1017 1,23. \019 1,00.1024 7,94.1036 7,94.1043 9,33.1038 1,0.1031

Trilon B AI (EDTA) Co(EDTA)2Clf(EDTA)2Fe(EDTA)2Fe(EDTA)Hg(EDTAiNi(EDTA)2Zn(EDTA)2-

1,4.1016 2,0.106 6,3.1018 2,1.1014 1,3.10 .

25

6,3.1021

4,2.1018 3,2.10\6

39

Qua hang nhan thay trong dung dich: [Zn(OH)4f hoi ben hon [CU(OH)4f {Ag(CN)2r rat ben hon [Ag(NH3)z]+ [Fe(CN)6]3. rat ben hon [Fe(CN)6t
[Ni(en)3l"+ rat ben hon [Ni(NH3)6f+

Hdng s6 ben tdng va hdngs6 ben tung

ndc

Qua trlnh tao thanh va qua trlnh phan Ii cua ion phirc xay ra thea tirng nac, irng voi m8i nac c6 mot hang s6 ben va hang s6 khOng ben rieng cua ion phirc [Ni(NH3)6f+ la:

Hiing s6 ben cua ion plurc giam dan thea s6

tao plurc:

nac. De dang chrmg minh rang qua trtnh

co hang s6 ben t6ng:

Ia tfch ella 6 hiing s6 Mn tirng nsc ella cac ion phtrc:

x, = K
trong

b1• ~2'

Kb3'~'

Ku~· b6 = 1,02.10s,K
I'Ct.t
cua ion phtrc nhirng nguoi

do

Kb\

la hang

s6 ben t6ng.

Nhirng hang s6 ben ghi trong bang 41a hang s6 ben t6ng ta thuong hay goi gon Ia hang s6 1>6nKb•

40

Cling nhu bat cu hang s6 can bang nao, hang s6 bin cua phirc chat lien quan voi bien thien nang hrong Gip ella qua trinh tao phirc trong dung dich: 0.GO ==- 2,303 RTlgK Bien thien entanpi duoc quyet djnh boi nang hrong ella lien ket giira nguyen tiI trung tam va phoi tir. Neu lien ket d6 gfi.n voi lien ket ion thurin tuy thi nang luong lien ket tang len thea su tang dien tich va SI! giarn ban kfnh cua ion. V( du nhu ion AI'''' tao phtrc chat voi F ben hon voi CI- . Neu lien ket do chu yeu la lien ket cong h6a tr! thl lien ket se ben trong phirc chat voi phoi til co MO
1t'

tr6ng nhu CO, CN- .

Entropi ella h~ thuong tang len manh khi tao plnrc, Nguyen nhan ehfnh la su tang dQ h6n loan ella h¢ VI khi tao phirc trong dungdich, vo sonvat hoa cua ion trung tarn va cua phoi

nr Mu b] pha huy va nhieu phan tir dung moi duoc giai phong. That vay, phan irng tao plurc trong dung dich mroc Ht phan ung thay the H20 hidrat hoa bang phoi tir khac. V f du nhu trong
phan tmg:

(trong do X - Iii pho] nr anion), vo hidrat h6a khong chi cua ion trung tam M"...

rna

d cua phoi

tl1 X- deu b] phi huy nen giai phong nhieu phan tll" H20 lam tang d9 han loan cua he. Entropi cua h¢ cling tang manh khi thay the ph6i tl1 mot cang bang phoi tiI nhieu cang, nghia la khi tao thanh phirc chat vong cang, Vi du:

o day
Vfd1,l:

hai phan nr en day ra bon phan til NH3 lam cho he tang rnanh entrapi. B6i vay,

phtrc chat vong cang luon luon ben hon phirc chat chua.phoi tl1 mot cang.

lCu(en)2f'"
(Kb= 1,35.10 °)
2

rat ben han

lCu(NH3)412

(Kb==1,07.I012) [Ni(NH:1)~f'" (K,= 1,02. IO~)

[Nitenr.]" rat ben hon 19 (Kb=l ,29.10 )

Hleu (mg vong cang

SI.!tang dQ ben cua phirc chat vong cang so voi phirc chat vci phoi

tit mot cang diroc goi

is. hieu Ifng vong cang,

Hieu Ung vong cang gay nen khong phai do yeu

to entanpi

rna do yeu t6 entropi cua

phan irng tao phirc,

Vi du phan ung:

41

co ,:l.H° -25 kl/mol

va

6S~98

= 110 llmol.d¢.
la
yeu t6 entropi dong gop

That vay, NH3 va en deu phoi tri voi Ni2+ qua nguyen tll N va eel hai ph6i tit co luc tnrong glin gi6ng nhau (trong day phd hoa hoc) nen LlHocua qua trinh tao nen ion [Ni(en)3]2+ va ion [Ni(NH3)4]2+ khongkhac chu

yeu

VaG

nhau nhieu (chi 25 kl/mol), R5 Tang d¢ ben cua phtrc chat Yang cang.
la ph6i

Etylendiamin Yang 6 canh:

tit tao nen yang 5 canh voi ion trung tam can axetylaxeton t .... nen o

Trong phrrc char, vong 5 canh ta ben nhat rOi den vong 6 canh, cac vong khac kern ben han. Ph6i tit nhieu cang c6 khii nang t.... nen nhieu vong nam canh voi cation kim loai o EDTA, m6i anion lien ket v6i mot cation kim loai qua 2 nguyen tit N va 4 nguyen ion phuc M(EDTAp'n}- c6 5 vong 5 canh:

la

tit 0 t.... nen o

Nho vay; EDTA

t o phrrc chat

rat

ben voi nhieu cation kim lo i k~ ca kim loai

kiem thd, Trang h6a hoc phan tich, ng110i ta dung trilon B (mu6i dinatri cua EDTA) de
dinh hrong cac cation kim loai. Chat chi thi cho qua trlnh chUAnd¢ Iii nhGng hop chat t.... o nen voi cation kim loai nhung phrrc chat mall kern ben han so voi phtrc chai cua EDT A voi kim loai, Trong y hoc, nguOi· ta dung mu6i natri-canxi cua EDT A d~ loai nhGng ion kim loai nang nhir Hg2+. Pbt+ va Cd2+fa khoi co

the khi bi ngo d¢c bm nhi1':ng kim loai d6. Dieu dang chti

y Ia mot

s6 mu6i kh6 tan, vi du M(EDTA)(4.nf

nhir BaS04 c6 the tan trong dung dich triton B. Ttrong tv nhu vay, cau can trong n6i hoi c6

tM tan

trong dung dich triton B.

f)tJ ben cua phitc chat va dtJ tan cua ket tila
Sv tao phrrc c6 anh huang den d() tan cua cac mu6i hoa tan cac ket tua b.... halogenua trong dung dich NH3• c

it tan.

De lam vi du

chting ta xet sv

42

D6i v6i AgO, c6 cac can bang: AgCI(r)

Ag'(dd)
¢

Ag'(dd)

+ Cl" (dd) , [Ag(NH3)2r.

TTAgo= 1,8.10-10

+ 2NH3(dd) ~

Kb

1.108

Cong hai phuang trlnh ta c6: AgCI(r) + 2NH3(dd)

[Ag(NH3ht(4d)

cr (dd)

Hang 56 can bang cua pnan irng nay la:

K

=C

[Ag(NH])1

+xC

Cl-

= C+xC
Ag

C2 NH] K

aAg +

xC
X

c NH
2

[Ag(NH]h ]

= IT
AgO

xK
b

= 1,8.10-

10

1.108

= 1,8.10-2

Neu hoa tan AgCllrong dung dich NH3 1M va goi d¢ tan cua ket tua d6 du6i dang ion phuc la x (tfnh bang mol/l), ta e6:

Nong d¢ ban dAu,mol/l Nong d¢ can bang, mol/l K= C

+

1 1-2x xC
Cl-

o
x
Xl

o
x

[Ag(NH]l2J

= 1,8.10-2

C~H]

(1- 2X)2

_x_=0,13 - 1-2x

x
C[Ag(NH1h

= 0,10
=

O,lOM

Nhu vay, nong d¢ ella ion phirc [Ag(NH3)2r can bang v6'i ket tua AgCIla kha Ion, nghia Hi Agel tan dang k~ trong dung dich NH3 so vci d¢ tan ella n6 trong mroc Iii:

~1.8.10-1O = 1.3.10-5M.
Tinh toan nrong t1! dOl v6i AgI (IT Ag! = 8,3.10-17). tim dUQ'C tan cua AgI trong dung d.¢ 5 dich NH3 1M 13. 9.1O- M, nghia lil AgI khong tan trong dung dich NH3• Nguoc lai neu them mu6i iodua (1) vao dung dich [Ag(NH3)2t, ket tila AgI xu:!t hien.

Ro fang 18hang 56 can bang cua phan rmg giii'a kc!t tila va ph6i tir tao phuc phu thuoc
vao quan h~ giii'atfch 56 tan eua eh4't it tan va hang 56 ~n caa phUc chat. M¢t chat rat it tan chi c6 the tan khi tao thrum nhilng phuc chAt eft Mn. Kc!ttua AgI khOng tan trong dung dich NH3 nhung tan trong dung dich N~S:!03 va tan r4't de srong dung dich NaCN nhet tao nen cac ion phuc [Ag(S:!03)2]3- va [Ag(CN)2 r ben han [Ag(NH3)2r (xem bing 4).

43

TfNH CHAT OXI H6A-KHUCUA

PHOC CHAT

Sv tao phtrc e6 anh hirong quan trong d€n the' dien eve cua kim loai chuyen tiep.Tnroc het, chting ta xet mra phan img: voi EO

= O.77V

Gia Slr them van h¢ mot ph6i tir c6 kha nang tao phirc chat ben voi ca dang oxi h6a va dang khir ella phan irng, vi du

CN"-

chang han. Chung ta co nira phan irng khac:

trong d6 hOO phtrc cha:t b trang thai can bang vCtiion trung tam va phoi tir:

K~~

2+

C
Fe

2+

C6
CN -

C rFe(CNI~]4

= 1.25.10-37

Theo phuong trlnh Necsto, th€ chuan cua c~p Fe(CN)!-

I Fe(CN)~- la:

Ti s6 C Fe·'+ IFe 2+ c6

tM tinh

diroc bang ti s6 cac hang s6 khong ben ella phtrc chat tuong .

vi adieu kien chudn, C [Fe(Cl'I)6] •

V~y:

3 -

= C [Fe{CN)6

= Imol / I

EO
{Fe(CN)d-/[Fe(CN)614-

= 0 77 + 0 0591
, ,

1,25.10g 1,25.10-37

44

EO

0,36 V

Nhu v~y th€ chudn cua nira phan thlg nay da giam xu6ng tir O,77V de'n 0,36V la vi ion
phtrc [Fe(CN)6f ben hen ionphec [Fe(CN)614-.

Hi ph6i tir co kha nang tao phrrc vili ca hai ion Fe + va Fe

3

Nhirng neu khong them ph6i

tir CN- rna them orthophenantrolin

2 +,

(viet uit la phen) cnng

nira phan thlg:

44

Fe(phen ) ~+

+e

Fe(phen)i

co
ta O,77V

EO = 1,12V den I,I2V. Dieu do chirng

to ion phuc

Nhu vay, th~ chuan cua nira phan rmg Day tang len
[Fe(phen)313+

kern ben hem ion phirc [Fe(phen)312+.

V~y su tang hay giam th~ cua cap oxi hoa-khir phu thuoc van Bay gia cluing ta xet nira phan trng:

ban

chat cua ph6i tiro

Ag" + e

Ag

voi

EO

= O,SOV
Sz O~chang

Gia sir them van h¢ mQt ph6i til c6

kha

nang tao phirc voi ion Ag" nhu

han, Ion do tao voi ion Ag+ ion phtrc ben [Ag(S:JOJ) ]3-:

Chung ta nnh the' chuan cua nira phan ung:

Theo phuong trlnh Necsto, th~ chuan cua cli¢n cue [Ag(~03)213-/Ag

13.:

a day:
CAg+ =~l~=

x,

1 2,88.1013

=3,47.10-14

Nen:

EO

[AS(S20~ )2]'

,_

lAg

= 0,80 + 0,059 EO = 5,89.1O- v.

3

19 (3,47.10'14)

V~y su tao thanh phtrc chltt cang ben cang

lam giam

th~ dien cue chuan cua kim loai

nhu se tha":yqua nhiing vi du dum day:

Zn(NH3

)!+

+ 2e + 2e +e +e

= Zn = Zn

+ 4NH3 + 4CN+ 2NH3 + 2CN-

EO = -1,04V EO = -1.26V EO = O,37V EO = -O,29V

Zn(CN);-

Ag(NH3);
Ag(CN);

Ag

= Ag

Den day ta hieu duqc kim loai Ag khong tan trong cac axit thong thuong giai ph6ng Hz nhung c6

kha nang

tan trong dung dich HCN

nha phan

6ng tao phirc.

45

TfNH CHAT AXIT -BAZO CVA PHUC CHAT

Tinh chat axit-bazo cua phirc chat thuang tM hien 0 phan irng cua ph6i

tit bao quanh ion

trung tam. Khi tao nen lien ket cho-nhan, mot phan mat dl} electron cua phoi til chuyen dich ve phia ion trung tam cho nen trong nQi bQ cua ph6i tit nhieu nguyen tit co su phan bo lai mat dQ electron. Neu trong phoi tir nhieu nguyen tir co nguyen tir H thi H se c6 troi dien tich dtrong va tro nen axit han. Boi vay, H20

a trong

cau nQi phirc chat, so voi H20 binh tlurong trong dung manh, nrc

dich, th~ hien tfnh axit cang rnanh han khi tac dung eire hoa cua ion trung tam dog la ion c6 dien tich cang 16'0 va ban kfnh dog be. Bang 5 diroi day ghi hang 56 phan li axit KA cua mot 56 ion phirc Bang 5 Hang sO'phan ll axil cua ion phuc Ion phirc [Ca(H2O)6f+ [M'g(H2O)6f+ [Pt(NH3)6]4+ [Co(NH3)sHzO]3+ lCo(NH3)3(HzO)3]3+ KA 2,5.10.13 4.1O·!2 1,2.10-8 2~04.1O·6 4.10.5 Ion phirc {AI(HzO)6]3+ [Co(NH3)2(H2O)4]3+ [Cr(HZO)6]3+ [Pt(NH3)sH2O]4+ [Fe(H20)6]3+

KA 1.3.10-5 4.10-4 1,2.10.4 -10-4 6,3.10-3

Qua bang ta thay H20 trong aquacation CH3COOH (KA

Al (H20)!+ la axit c6 dQ rnanh nrong dirong Cr(H20)~+va Fe(H20)~+ con manh han,

1,8.10'5) va trong cac aquacation

con cac cation Co 3+ va Pt 4+ bien H20 trong cau n¢i thanh axit nrong doi manh, tirong dirong axit nitro (KA

= 4,5.10-4).
[M(H20)6]n+ [M(H20)sOHt )+
n1 •

Nhu vay, trong dung dich mroc cua nhirng phirc chat aqua c6 can bang:

+ H20 ~
+
H20 (
)0

[M(H20)50Hln.!}+ [M(H20MOH)2t )+
n•2

+ H30+
+ H30+ va v.v ...

Nhfmg can bang phan li cua phirc chat trinh bay thea quan di~m hoa hoc phci trf thirc ra la can bang cua phan trng thuy phan rat quen thuoc v6i cluing tao D6i voi phuc chat cua platin, nhfrng phdi tir nhieu nguyen That

tir c6 chua H nhu NH3,

CH3NH2, en ... ding co th~ phan Ii axil. Vi du nhu [Pt(NH3)6]4+ la axit rat yeu (xem bang 5).

vay, khi tac dung voi dung dich kiern:

amoniacat 46

cua Pt(IV) tao nen hop chlit amido.

CHUONGII

CAe NGUYEN TO NHOM IIiB

Dum

A.AI'""

Nh6m,llIB

gom c6 cac nguyen t6: scandi (Sc), ytri (Y), lantan (La) va actini (Ac),

day 13. mot s6 d~c diem cua nguyen t6 (Bang 6). Bang 6 MC,l so d;)e di~m eua cac S6 Nguyen thaU;t nguyen tir Sc Y La Ac 21 39 57 89 [Ar13dl4s [Kr}4d15s2 [Xe] 5d16s2 [Rn}6dI7s2
2

nguyen to Se, Y, La va Ae
Nang hrcng ion hoa, eV Ban kinh nguyen
II 12

cau hinh electron

t6 (E)

Ban kfuh ion

The dien
cl,le

I)
24,8 20,46 19,10

14
73,6 61,S 52,5

tir, A 1,64 1,81 1,87 2,03

E3+.A
0,83 0,94 1,06

chujin. V
-2,08 -2,37 -2,52 -2,26

6,56 6,21 5,77 5,1

12,8 12,30 11,38

i.n

Cac nguyen t6 nh6m IIIB c6 cau hinh electron ehung cua nguyen dls2d6

tir Hi (n-l jd'ns' va Ia

nguyen t6 dtmg dau cac day kim loai chuyen tiep, Viec chi c6 mot electron d lam cho cau hlnh

kern ben va bieu II?trong moi tintc'eh~ cua nhom nguyen t6. Khac voi cac nguyen t6 d

khac, nguyen t6 nh6m

nIB

nay c6 mQt trang thai oxi h6a khong bien d6i

(11+12+13)
eV

la +3

va khOng the .

hien manh kha nang tao phtrc voi nhieu ph6i tiro So sanh v6i nguyen t6 nh6m ilIA (xem t~p hai)

80
60 ~ G"n Y La

nhan thay mot s6 d~c diem nhu bin kfnh nguyen tir, ban kinh cua ion E3+, t6ng nang hrong ion h6a tha nh:1t,
tha hai va thu ba, the' dien cue chuan cua kim loai deu

l'
.....

40.A1~~

bien d6i kha d~u d~ trong day B-AI-Se-Y-La-Ac' va trai nguoc lai b trong day B-AI-Ga-In-Tl (Hmh 2).
Di~u nay c6 lien quan de'n kien

20L...--...L..----l.-___..--:.L...-_::_ 20 40.60 80 Z Hinh 21. SI! bitn Mi cUa ufllx nang llo/ng ion h6a cdc nguyen /({ nh6m III

true electron cua

47

ion

E3+.

Cac ion Sc3+, y3+, La3+ va Ae3+ co cau hlnh electron ella khf hiem giong nhu ion A13+

trong khi cac ion Oa3+, In3+ va 113+ co vo ngoai cilng gorn 18 electron. That vay, tfnh kim loai ella cac dan chat tang len d~u d~n trong day B-Al-Sc-Y-La-Ae; Sc g~n voi Al han, con cac nguyen t6 con lai glln vci kim loai kiern thO.

cAc DdN CHAT

Tinb chtit li hoa hoc
Scandi, ytri, lantan va actini la nhilng kim loai mau trang bac, tuong d6i kho nong chay va kha gion, Dum day la mot sO hang sO v~t If cua cac kim loai (Bang 7).

Bang

HAng s6 v$t Ii quan trong cua cac kim loai . Kim loai (E) Sc Y La Ae Ndnc, DC 1539 1526 920 1050 Nds,oC 2700 3340 3470 3300

Ti khol
3,02 4,47 6,16 10,1

DI) dan dien (Hg=l) 1,36 1,73 1,54

Tat
t(,LO

ca Mu

dan dien va nhiet tuong d6i kern. Scandi va ytri thuoc kim loai nhe con
10(,Li,

lantan va aetini thuoc kim loai nang. Lantan tao hop kim v6i nhieu kim nen nhilng hop chat giiia-kim loai. Hop kim chua hop

trong do thuong

chat

loai chuyen tiep, vi du nhu LaNis co d~e tinh la co the hap thu dieu kien thirong mot luong khi H2 g1in gap dOi luong H2 co trong cling mot the tich ella hidro long hay hidro ran. CO Ie nhilng nguyen tir H da chui vao 10 trong ella kien true tinh the cua hop chat gnra-kim loai

giira-kim loai ella La voi kim

1'.10 nen mot v~t lieu c6 kien true r~t sit sao. Khi duoc dun nong nhe, hop kim lai giai ph6ng H2. Bdi

vay, hop kim chua LaNi5 ducc dung lam blnh tieh tret khi hidro dung cho pin nhien lieu hidrooxi. Actini la nguyen to' phong xa, dong vi ben 227Acco chu kl ban ra la 21,77 nam, Noi chung ve tfnh ch<ft vi).tIf, Sc va Y gan vm kim loai dM hiem nhom nang con La va Ac g~n vm kim loai dat hiem nhom nhe, T~t

ca nhom

IIIB Mu la kim loai r~t hoat dl)ng v~ mat hoa hoc, trong nhieu hop ch~t

chung gi6ng v6i Mg va Ca. Heat tinh h6a hoc tang len til Sc den Ac.

nhanh chong bi

Khi de trong khOng khi, Sc va Y khong bien dOi vi c6 mang oxit bao v¢, con La va Ac rna d\1C do tao thanh lop hidroxit tren ~ mat, Rieng La c6 tinh tv chay, khi

48

co xat hay va d~p n6 b6c chay trong khong khf, Khi dun n6ng, cac kim 101# tac dung voi da s6 nguyen t6 khong-kim

101#: voi oxi, hidro,

halogen, hru huynh, nita, cacbon, silic, bo tao thanh oxit E203, EH3• EX3. E2~' E4c;, ESi2, EB6• V nu6c, Sc va Y chi tac dung khi dun n6ng vi bi mang oxit bao boc con La va Ac tac dung cham voi nu6c: 2E

+ 6H20

2E(OH)3

+ 3H2

Tat cel deu tan trong dung dich axit thong thuong gi8.i ph6ng khf hidro. Khi tan trong dung dich HN03 loang, cac kim 101# c6 the khir axit tao thanh NH4N03•

Vi du:

Ve tinh chill h6a hoc, n6i chung Y va La gi6ng nhieu voi cac lantanoit nen duqe gl!P chung van ho kim loai ddt hiem.

Trang thai thiln nhiin va phuung phap didu chI'

Seandi, ytri, lantan va actini thuoc nhfi'ng nguyen t6 rat phan tan trong thien nhien. Trfr

hrong trong vo Qua D1lt cua Sc la 3.10-4,

cua Y la 2,6.10-4,

cua lantan la 2,5.10-4 va ella Ac lit

5.10-15 % tdng s6 nguyen tir. Chung it tao nen khoang v~t rieng

rna a Ian trong

khoang v~t da kim loai dat

kim cua cac kim loai dat hiem, vi du nhu cat monazit la hOn hop ciia orthophotphat hiem (MPO 4) va thori orthosilicat (ThSiO J, toveitit (Y ,Sc)2Si207)' gadolinit xenotim (MP04), batnesit (MC03F), da.y M la kim loai h6a tri ba.

(B~ Y 2FeS~0 I0)'

Nam 1794, nha h6a hoc Phan Lan la Gadolin (G. Gadolin, 1760-1852) khoang v~t ytecbit (khoang v~t nay c6 ten goi d6 VI duec phat hien cua Thuy Dien, sau nay diroc goi la gadolinit) mot oxit moi goi Mozande (G. Mosander,

ta "dM

a Ytterby gao Stockholm

da tach duoc til

ytri". Thuc ra "dat ytri"

la mot hon hop oxit cua cac kim loai, Nam 1835, tir dat ytri, nha hoa hoc Thuy Dien la 1797-1858, hoc tro Berzelius) da tach duqc oxit cua ytri, oxit cua tecbi

va oxit cua ecbi. Tuy nhien wac d6, nam 1828 nha h6a hQCDuc la Vole (Who ler) d§. dieu che
man kim loaiytri dau tien tuy chua duqc tinh khiet lamkhi dung kali khir YCll

a nhiet

dQ eao.

Nam 1839, Mozande tach duqc tir "dal xeri" mot oxit man vang cua xeri va "dat lantan", didim, ve sau hi!!t dtroc didim la hai nguyen t6 neodim va prazeodim, Sau d6 Mozande Ian dAu tien da: dieu che lantan kim loai thea phmmg phap cua VOle. Ten goi lanian xuat phat ttr chn
Lantos, tieng Hi Lap c6 nghia la gillu giem vi kh6 phat hien, Nam 1879, nha h6a hoc Thuy Dien la Ninxon (F. Nilson, 1840-1899) tach duqc oxit cua mot nguyen t6 tir "da-:tytri" da N am 1841, tir "dllt lantan", ong tach ra dircc oxit mau trang cua lantan va oxit mall do ella

rom. Nguyen

t6 mci d6 duqc phat hien bang phuong phap 49

scandi (Scandinavie la que huang cua Ninxon). Nguyen t6 nay chinh la nguyen t6 ekabo rna nam 1871 Mendeleep da tien doan ra:t chi net. Nhiing ket qua cong b6 cua Ninxon ve scandi ra:t phu hop voi 1m tien doan cua Mendeleep, BCri vay, phat rninh
phan tich quang pho va co ten la cua Ninxon la bang chung xac dang d~u tien chimg rninh dinh luat tuan hoan cua Mendeleep, Mendeleep da tien dorin chi Nhu da blet, ekabo

su dung

net.

la

dan cua bang tuan hoan va

mot trong b6n nguyen t6 rna

Narn 1937, scandi kim loai dang tinh khiet moi diroc dieu ch€

bang phuong phap dien phan hOn hop n6ng chay cua SeCI3, KCl va LiCl. Actini Dobiecnc Ia nguyen t6 ph6ng xa thien nhien da duqc nha khoa hoc nguoi Phap la

(A. Debieme)

phat hien nam 1899'0 trong san pham con lai sau khi da tach Ra va Po

nr quang uran. Nhu da biet, nam 1898 hai nguyen t6 ph6ng xa nay da duqc Pie Quyri va Marl Quyri tach duqc tir quang uran. Ten goi actini xuat phat tir chtt act is, tieng Hi Lap nghia la tia, nguyen t6 duoc phat hien do ria phong xa. Actini la san pham trung gian cua qua trmh phan ra ph6ng xa cua uran:
235U~231Th~23IPa~227 92 . 'XI 91 89 Ac~227Th 90 "~ 7

trong mot

tan quang

uran c6 0,06 mg actini.

Kim loai scandi khong co cong dung quan trong, ytri c6 tiet dien ba.t notron be nen duqc dung

lam vat lieu xay dung 10 phan ling hat nhan, lantan kim loai duqc Slr dung rong rai

hem ?:i dang mishmetall la hop kim cua cac da:t hiem chira 25% La dung them vao cac

lam da lira va chat

cho

hop kim. quang kha phirc tap: tuyen khoang, che hoa tinh quang bang

Qua trinh tach kim loai tir nhiing san

cac plnrong phap hoa hoc khac nhau

M duqe

cac

san phAro trung

gian r6i luyen kim loai tir

pham trung gian. Nhiing san pham trung gian d6 thuong la E203, EF3 va Ee13•

Ngiroi ta dung canxi, magie hay kali khir cac hop chlft do ?:i nhiet dO cao hay dien phan mu6i halogenua n6ng chay cung vci halogenua kim loai kiem.

Vi du:
= ==

+ 3CaF2 2La + 3MgO

2Y

Cong nghe dieu eh€ Se203 tir toveitit urong d6i don gian: 2Sc2Si207 Sc4C3 2ScC13

+ 6C +
12HCl

1800"C

+ 3H2~04

= = =

Sc4~ 4ScCl3

+ 4Si02
+ 3C

+ 3CO2 + 6H2

Sc2(~04)3 Sc203

+ 6HO + 3CO
phec tap han nhieu va phu

Sc2(~04)3

400"C

+ . 3C02

.Cong nghe tach Y va La tir cac khoang vat cua

d~t hiem

thuoc vao timg khoang vat rieng, Ch€ hoa cac tinh quang voi axit clohidric, axit sunfuric, natri 50

hidroxit d~ dtroc hOn hop mu6i cua cac kim loai. Nhung ki thuat thtrong dung

de tach

rieng cac

mu6i kim loai d6 Hi ket tinh phan doan, trao d6i ion va chiet bang dung moi htru co. Actini diroc tach til quang uran hoac duqc tao nen khi ban notron vao 226Ra a trong Ib phan irng hat nhan:

HOP CHAT

eVA Sc, Y va La
kern bazo hon

Cac oxit E203 deu 18. chat ran mau trang, ra:t kho nong chay, Oxit 51;03 cac oxit khac va gi6ng voi Al203
.
•

No cung luang tfnh va tan trong dung dich NaOH d~c va

du tao thanh Na3[Sc(OH)61 . Cac oxit Y203' L~03 va A~Ol gi6ng voi CaO. Chung hap thu khf C02,hOO mroc trong khi quyen tao thanh cacbonat, hidroxit. Tac dung caa chiing v6i nuoc phat nhieu nhiet.
Vfdl;!:

~HO= -154 kJ
Cac oxit c6 the dung lam chat xuc taco Oxit L~03 dung de ch€ loai thuy tinh Hun kfnh bao hI) (ngan tia tir ngoai), Cac oxit Se203 va Y20l dien ttt va may tinh, Rieng Y203 can dung Cac oxit E20l co

de che g6m

dung lam vl)t lieu til dung trong vo tuyen chiu nhiet.

the duoc

tao nen bang tac dung true tiep ella kim loai voi oxi hoac

bang each nhiet phan hidroxit, cac mu6i nitrat, cacbonat, oxalat.

Hidroxit E(OH)3
Cac hidroxit E(OHh Ia ket tua nhay mau trang. DQ tan trong mroc va tfnh bazo tang len til Sc den Ac. Hidroxit duong Ca(OHb NH1• Se(OH)3 lA cha:t luang tfnh.rHidroxit La(OH)3 la bazo manh, luang hap thu khf CO2 trong khi quyen, rae dung voi rnu6i amoni giai ph6ng khi Khi dun n6ng, cac hidroxit ma:t mroc bien thanh axil. Cac hidroxit E(OH)3 duqc tao nen khi dung dich

muoi E3+ tac dung voi kiern hay + 3S02 + 3S + 6NaCl

amoniac. Hidroxit SC(OH)3 can c6 tbl! dieu che bang tac dung cua mu6i Scl+ vCtiN~~03: 2SeCl3

+ 3N~~03

+ 3H20

2Sc(OH)3

Trihalogenua EX]
Cac trihalogenua Mu la cMt rAn mau trang. Cac triflorua EFl kh6 n6ng chay (til 1450 elorua, bromua va iodua c6 nhiet dl) nong chay den 1550°C), khong tan trong mnrc, concac

51

thap han (til 800 den 900°C), hut Am, tan trong mroc va hi thuy phan tao thanh polime oxohalogenua Nhtmg EOX. Thuc te co

tM

dung ion

P-

de phan tich dinh tfnh nhimg kim loai nay. vi du ScCI3.6H20,

halogenua

tan, khi ket tinh til dung dich deu b dang hidrat,

YCI3.6H20, LaCI3.7H20. Khi dun nang trong khi quyen HCl, cac hidroxit nay mat mroc bien thanh mu6i khan.

vr du:
Hel

Neu khong co mat khi HCl, cac hidrat bien thanh oxoclorua.
Vi du:

Rieng ScF3, giong vci AIF3, co th~ ket hop voi florua kim loai kiern tao nen rnuoi hexafloroscandiat tan nhu Na3[ScF61 va K3[ScF6].

Cac triflorua EF3 co

the dieu

che bang tac dung tnrc tiep cua nguyen to hoac tac dung

cua florua kim loai kiem vai dung dich muoi cua Sc, Y va La.
Cac trihalogenua con lai co th~ dieu che' bang rae dung tnrc tiep cua cac nguyen to hoac bang each hoac tac dung cua kim loai hay ox it kim loai voi dung dich axit halogenhidric dun nong oxit kim loai voi muoi amoni halogenua,

2La La203

+ 3F2
+ 6HCI + 6NH41
E3+

= =

La203

2LaF3 2LaCl, 2LaI,

+ 3H20 + 6NH3 +
3H20

Cac mu6i khtu: ella

hidrat. Cac mu6i cacbonat dang khan trong do M muoi cacbonat hayamoni: K2C03 + LaiC03)3
)a

Cac mu6i sunfat va nitrat deu tan trong mroc nen mu6i kep kitu ME(S04h, M2E(N03)5' ME(C03)2

va

khi ket tinh til dung dich deu b dang

t.... o

va oxalat deu It tan. Gi6ng voi nhom, cac nguyen t6 nhom IIIB
va ME(Cz04h kim loai kiern va NH;).

(mu6i kcp diroc viet b kim loai kiem

SI! tao thanh rnuoi kep giai thich SI! hoa tan

cua cac kim loai nhorn IIIB trong dung dich bao hoa cacbonat

+ 12H20

K2C03.La2(C03h·12H20

Phuc ehtft ella Se, Y va La Cac cation kim loai

$c3+, y3+

va La3+ tao nen nhirng phirc chat tuong d6i ben voi nhirng EDTA ... Kha nang t'.10 phirc giam xu6ng nr

ph6i tu nhieu cang nhu ion oxalat, ion p-dixetonat, Sc d€n La thea chieu tang ella ban kinh ion.

52

Khi them dung dich oxalat kim loai kiern vao dung dich mu6i E3+, mu6i oxalat cua E3+ 5e ket tua va d¢ tan cua ket tua d6

a trongdung

dich oxalat du giam xu6ng r6 ret

tit Sc den La:

Sc2(C204h tan de dang tao thanh phirc chat [SC(C204)21 , y 2(~04)3 La2(~04)3 tan

tan mot mire d~ eon

it.
cac eation E3+ tao nen ket tua axetylaxetonat: [Sc(aea)3] trong d6 Sc trong d6 La e6 s6 trong do Y e6 s6 ph6i tri 7 va [La(aeah(H20}z]

V6i axetylaxeton, ph6i trf 8. Axetylaxetonat cac axetylaxetonat

e6 56 ph6i trf 6, [Y(aea),H20]

cua scandi rat ben voi nhiet, e6 the thang hoa khong bi phan huy eon

ella Y va La bi phan huy

a khoang

500°C. Dl10i day la hang 56 ben

V6i EDTA, cac eation E3+ tao nen phirc chat H[E(EDTA)]. ella cac ion phirc d6

va ella ion Fe +;
3

1,26.1023

1,36.1025 trong dung dich giarn xu6ng

D\l

ben cua ion phirc [E(EDTA)r

tu

Sc den La va n6i

ehung be han so voi Fe(IlI).

53

CHUONG 11/

cAc

NGUYEN

TO NH6M

IVB
lil mot

Nhom IVB gem co cac nguyen t6 titan (Ti), ziconi (Zr) va hafni (Hf), Dum day s6 d~c diem cua nguyen t6 (Bang 8).

Bang 8 M(tt sO dl)c di~m cua cac nguyen t6 Ti, Zr S6 thrr nr

Nguyen nguy~n t6 (E) Ti Zr Hf t6· 22 au hlnh electron nguy~ntir [Ar]3d24s2 [Kr]4dl5sl [Xe]4fI45dl6s2

va Hf
Ban kinh nguy~n Ban kinh ion E4+,A • 0,64 0,87 0,86 -I,75(Ti3+{Ti) -l,43(Zr4+{Zr) -I,57(HF+ tHf)

Nang luongion hoa, eV II 6,83 6,95 5,5 12 13,57 14,03 14,9 13 24,47 24,71 21 14 43,24 33,99 31

The' dien cue

chuan, V

tir,A 1,46 1,60 1,59

40
72

Cac nguyen t6 Ti, Zr va Hf c6 cau hlnh electron gi6ng nhau cua nguyen tii la (n-l xfns"

va la kim loai chuyen tiep,

Nang hrong ion h6a hrong

Ian nen

tha nr cua

chung r!it Ion, viec tao thanh ion E4+doi hoi

mot

nang

iond6 chi c6 the ducc lam ben nho su tao thanh kien true tinh the c6 d¢ ben cao

nhu oxit E02• Neu s,! lam ben d6 khOng do bu cho nang hrong de tao thanh ion E4+ thl cac nguyen tii tao nen cho yell cac lien ket cong h6a tri, vf du nhu trong cac halogenua E~ (a day
E=Ti, Zr va Hf, X= halogen). Trong cac hop chat, trang th~i oxi b6a d~c tnmg va ben nha't cua ca ba nguyen

sa di nhu
va Hf c6

t6 la +4.

the co cac trang

vay la vI ion E4+ c6 cau hlnh electron ben cua khi hiem (8 electron). Ngoai ra Ti, Zr

h6a thap the hien r5

a Ti nhung a nhtmg

thai oxi h6a ths:p hen nhu +2 va +3. Khuynh hirong cbo trang thai oxi hop cha't img

vm cac

s6 oxi hoa thS:p Ti deu

de chuyen

sang trang thai +4 dac tnmg, Con Zr va Hf tao nen r4't ft hQP cha't U'ng voi so oxi h6a th4'p. Vf du titan co cac hQP chl1'tTiO, Til03• TiOl• TiF2• TiF3 va TiF4 trong khi Zr va Hf chi c6 nhiing

54

hop chLlt Zr02, Hf02, ZrF4 va HfF4• Nhu vay, khuynh hu6ng tao nen s6 oxi h6a cao +4 tang len tit Ti den Hf, nghTa la ngiroc vm khuynh huang bien dOi trong cac nguyen t6 nh6m IV A. Tuy nhien trang thai s6 oxi h6a +4, cac nguyen t6 Ti, Zr va Hf gi6ng v6i Ge, Sn va Ph. Ttr Ti den Zr, ban kinh nguyen tir va ban kinh ion tang len nhung tll' Zr den Hf lai hoi. giam xu6ng, coi nhu khOng bien dOL Day la ket qua cua hien tuong co lantanoit. Chinh Zr va Hf c6 ban kinh gan nhau nhu vay, chung co tinh chat rLrtgi6ng nhau va mt kh6 tach ra khoi nhau. C6 th~ noi Zr va Hf la cap nguyen t6 kh6 tach ra khoi nhau nh~t, mot trong nhfrng v4n d~ kho khan nhat cua hoa hQCvO ca.

CACDdNCHAT
Tinh chd't li, h6a hoc
Titan, ziconi va hafnila nhUng kim loai mall trang bac.

a nhiet de) thuong, tinh tM kim

loai co m~ng lu6i h,IC phuong (dang a) va 0 nhiet de) cao co mang luci lap phirong tam k:h6i (dang 13). Titan thuoc kim loai nhe con ziconi va hafni la kim loai nang, Dum day la mot s6 hang s6 vat If cua cac kim loai (Bang 9).

Bang 9
HAng

so v~t

Ii quan trong Clla cac kim lo~i Nds.,oC rt kh6i De) cirng (thang Moxa) 4 De) dAn dien (Hg=l)

Kim loai (E) Ti Zr Hf

Ndnc .• "C

1668 1855 2220

3260 4330 5400

4,51 6,51 13,31

2,1 2,3
, 3,1

4,5 -

Ca ba kim loai d~u kh6 n6ng chay va k:h6 sol, V~ nhiet de) n6ng chay, nhiet d¢ soi, d¢ cimg, d¢ dan dien va dAn nhiet, ca ba kim loai luang duong v6i nhUng kim loai chuyen tiep khac nhu Fe, Ni, v.v ... chung co hQC.

tro

Cac kim loai tinh khiet d~u de ch€ h6a co hoc nhung khi chua tap cha:t 0, N, C, H. nen gion, Chung truyen cho cac loai thep d~c biet d¢ Mn an mon, d¢ cimg va d¢ Mn Thep chtta titan dung lam dirong ray va banh xe tau hoa.

Hop kim cua titan dung d~ ch€ tao dong co may bay phan luc va ten lira. Thep chea ziconi dung lam nhUng tam chan cua xe boc thep.

ca ba nguyen

t6 c6 mot s6 d6ng vi thien nhien: Ti c6 5 d6ng

vi, ben

nhat la 4s-ri; Zr c6

55

5 dong

vi, ben

nhat

la WZr

va Hf co 6 dong vi, ben nhat

bit notron rat be trong khi dong hop kim cua Al v6i sach het Hf.

vi hen

la 180fif.

DOng

vi ben

cua Zr co tiet dien

cua Hf c6 tiet dien bit notron r~t 16n. BCri. ay, khi dung v

Zr d~ lam vat lieu che' tao 10 phan trng hat nhan, Zr d6 c~ phai dtroc loai

a nhiet
thanh oxit E02,

de! thuong, ca ba kim loai (E) Mu ben vai khong khi va nuoc nho c6 mang oxit

E02 mong ra't ben bao ve,

0 nhiet

dQ cao, chung rat heat dQng hoa hoc: tac dung voi oxi tao E~

voi halogen tao thanh halogenua

Cu day Xehalogen), voi hru huynh tao

thanh sunfua E~, voi nita tao thanh nitrua EN, voi cacbon tao thanh cacbua EC, voi bo tao thanh borua EB2• NhCtng hop chat nitrua, cacbua, silixua va borua cua chung rhirong la hop chat ki€u xam nhap c6 thanh pharr bien d6i, cirng, rat ben nhiet va rat kho n6ng chay, MQt trong nhirng v~t lieu kho n6ng chay nhat (4000°C) kim Ioai tJ! chay

a nhiet

chtra

80% TiC va 20% HfC.

a dang

bot

min,

ca ba

d¢ thuong.

o nhiet

dQ thuong, ea ba kim loai d~u hen voi cac tac nhan

an

man. D~e

bier

titan rat

ben voi mroc bien va nhieu tac nhan an man khac nen Ia mot v~t lieu khong thay the duoc de che' tao tuocbin, may hoa,

vb tau thuy,

Ca ba kim = =

loai khong tac dung voi axil.

Khi dun n6ng, rieng titan tan trong dung dich HCI theo phan ling: 2Ti Ca ba kim loai

+
bot

6HCI

2TiCI)

+ 3H2

a dang
E

min

c6

tM tac

dung v6i dung dich HF n6ng:

6HF

H2{EF6]

+ 2H2

Tuy bi axit nitric d~c thu d¢ng h6a

a nhiet

dQ thuong,

tM

tac dung voi axit sunfuric

d~c, cuong thuy va nhat

la

ca ba kim

Ioai

a dang

bQt min c6

h6n hop cua axit nitric va axit

flohidric: Vi du: 2Ti 3Zr 3E

6 H2SOid~c)

+ 4HN03
+ 4 HN03 ,

+ 18 HCI
+ 18 HF

= =

T~(S04)3 3H2[ZrCI6] 3H2[EF6]

+ 3 S02 +
+ 4 NO +

6H20 8H20

+ 4 NO +' 8H20

Ca ba kim loai deu ben voi dung dich kiem. Rieng Ti tac dung voi kiem n6ng chay, Hf tac dung voi KHF2 n6ng chay: Ti Hf

+ +

4 NaOH 4KHF2

N~ Ti04

+ 2H2 K2[HfF61 + 2KF + 2H2

Trang thai thien nhiln va phuong phap diBu chI'

Trong thien nhien titan thuoc nguyen t6 r~ phO bien, dUng hang thli: mum sau cac kim Ioai AI, Fe,Ca, Mg .,. ziconi va hafni thuoc nguyen 1:6pharr tan. TUy nhien, ziconi c6 phI'S bien 56

han so vci cac kim lo~LiNi, Cu, Zn ... .Hf co phd bien han Au, Hg ... Trang vo Trai Dat titan chiern 0,25%, Zr chiern 4.10-'% va Hf chiern 5.10-5% tong s6 nguyen tir. Nhirng khoang vat chfnh cua titan la rutin (Ti02), (ZrSi04) tieng va badeleit (Zr02). inmenit (FeTiOJ) ~a peropskit (CaTi03), cua ziconi la zicon Ten khoang v~t zicon (zircon) la ten goi chech ella chu zargum

A Rap

c6 nghia la rnau yang choi vi zicon dii biet til thOi c6 xua

la mot loai da quy trong

su6t va c6 cac mau dep, nhat la mau yang. Hafni kh6ng c6 khoang v~t rieng rna thuong d6ng hanh voi ziconi. Trong cac khoang vat, hrong Hf t~uemg bang khoang 2% hrong Zr. Niroc ta c6 mo titanomanhetit i:J mii Chua (Thai Nguyen) va Tam Ki (Quang Nam), co

sa khoang inmenit va zicon i:J ven bien tinh Quang Ninh va cac tinh mien Trung.

Titan dtroc nha hoa hoc nguol Dire Claprot (Martin Hendrich Klaproth,

1743-1817)

phat hien trong khoang v~t rutin vao nam 1795. Ten goi ella nguyen t6 do la ten ella ong t6 than mii (theo than thoai Hi Lap). Den nam 1825, Beezeliuyt Ian dAu tien dff di~u che diroc kim loai titan i:J dang bot khi khi'r K2[TiF6J bang natri i:J nhiet d~ eao. Narn 1910 nha hoa hoc My la Hunter dii dieu ch€ diroc titan tinh khiet han khi dung natri hay kali khir tetraclorua

a 700°C

va

den nhirng nam 40 ella the ki nay titan kim 10'.1imoi duoc san xuat (y quy me cong nghiep, Nam 1978 Claprot dff che' dircc titan dioxit 'Beczeliuyt K2[ZrF6]

tir khoang v~t zicon va den narn 1824

Hln dau tien da: dieu che duoc zieoni kim loai

a dang

bot khi dung natri hay kali khu

i:J nhiet d~ cao. Ten goi ziconi duoc lay tu ten khoang vij.t zicon, Narn 1925 nguoi ta

dieu che' diroc ziconi tinh khiet. . Nguyen Ronghen (Hungari) to hafni diroc phat hien tinh co vao narn 1923. Khi che' tao nhirng ang cua cac nguyen t6, hai nha khoa hoc la Heversy da: phat hien-ra nhfrng vach quang ph6

moi va nghien ciru phd Ranghen

va Coster (Ha Lan) lam viec i:J Copenhaghen

moi trong phd Roughen cua nguyen to ziconi, D6 la nhirng vach cua mot nguyen t6 moi goi la

hafni. Ten goi nay diroc lay tir chir hafnia tieng La Tinh la ten c6 ciia thu do Copenhaghen.
Hang nam tren the gioi san xuat hang van tan titan tu inmenit va rutin. Nhfrng nuoc khai thac nhieu khoang v~t cua titan la Australia, Nam Phi, Canada, Na Uy, Malaixia, Nhfrng mroc khai thac nhieu khoang v~t zicon la Australia va My. Nhfrng hop kim ferotitan dung trong nganh luyen kim chua 10-50% Ti duoc dieu che bang each dung than c6c khir h6n hop quang sar va quang titan. Viec dieu ch€ titan kim loai tinh khiet la rat kh6 khan.

a nhiet

d~ cao Ti rat

hoat dong, tac dung voi oxi, nita, cacbon nen khong tM dung than khi'r rutin trong 10 cao nhir doi voi gang. Ngiroi ta phai clo h6a cac khoang v~t cua titan khi c6 mat than i'J nhiet d¢ 800-

lOOO°C:
Ti02 2FeTi03 Can chu dung cacbon

<

+ 2El2 + 2C = . + 7CI2 + 6C =

TiCl4

+ 2CO 2TiC14 + 2FeCIJ

+ 6CO

rang viec clo hoa tnrc tiep rutin hay inmenit kh6ng ket voi oxi cho phan ling phal nhiet va tang entrapi.

tbe

thirc hien diroc VI

·qua trinh diy khi oxi ra bang khf clo la qua trlnh thu nhiet va giam entrapi cho nen can phai

M lien

57

=
nhung:
Ti02(r,rutin)

TiCI~(k)

O~(k),

.-1.09 162kJ

+ 2C (than chi) + 2CI:!(k) = TiCI4(k)

+ 2CO(k),

AG"= -112kJ

nhier d¢ thuong TiCl~ HI chat long (nds. la 136"C) va FeCI, la chat rAn (nds, Hi

315°C). Khi do hoa inmenit voi SI! c6 mat cua than, dua vao nhiet d¢ soi khac nhau nhieu, nguci ta tach TiCI4 ra khoi FeCI, bang each lam bay hoi phan doan. Sau do cho hoi TiCI4 di qua magie n6ng chay hay natri nang chay trong khf quyen Ar hay He: TiCl4

2Mg

Ti

+ 2MgCl:!

Khi rira voi mroc, MgCI2 tan, con Iai Ti kim loai 6 dang khoi x6p. Phuong phap nhiet-kim tetraclorua. loai nay ciing diroc dung d~ dieu che' Zr va Hf kim Ioai tir

Ngoai ra ngiroi ta co the thay ECI4 bang K:,[EF6]: ECl~

+ 2Mg = K2[EF6J + 4Na =

E E

+ +

2MgCI2 4NaF

2KF

Ca ba kim loai Ti, Zr va Hf dieu chetheo phirong phap nhier kim 10<;1i chua c6 d¢ tinh khiet cao. Muon tinh che, truce het nguoi ta nung kim loai chua tinh khiet i:J lOOO"Ctrong chan kh6ng

de loai

sach Mg

dir r6i ap dung phirong phap Aken-Do B6e (Van Arken va De Boer,

nguoi Ha Lan) duoc de ra narn 1925. Phuong phap nay lei dung tfnh TiI4, ZrI4 va Hfl, va kha n1ng phan huy cua cluing

a nhiet

de bay

hoi cua cac iodua

d¢ cao tao rhanh kim loai, trong khi

iodua cua cac nguyen t6 tap chat kh6ng co kha nang d6. Vf du de: tinh che kim loai titan, trong

phong thf nghiem nguoi ta dung binh bang thuy

tinh Pirec (Hinh 22). Qua 6ng 1, hiit kh6ng khf i:J trong blnh fa de: tao chan kh6ng va qua ong2 d6 vao blnh mot h6n hop cua bot kim loai titan va iot (hrong rot diroc lay it hon 1D bin so voi hrong iot

do thier de tao rhanh TiI4). D1\itblnh thuy tinh vao

10 dien va dun nang i:J 400°C. Soi day titan 3 i:J trong blnh ducc n6i voi hai dien eire va dircc d6t nang bang dong dien.

0 20DoC Ti va 12rae

dung vci

nhau tao thanh TiI4, hop chat nay thang hoa i:J

Hinh 22. DI.mg ("{Ide' tinh rhe'titan kim loai

377°C. Khi tiep xiic voi sci day titan 3 diroc dot nang den 1200-1400°C, hoi TiI4 phan huy: TiI4 = Ti

2I:!

titan kim loai ker tinh i:J tren sci day titan con hoi iot ngirng tu

a phan

ngu¢i cua blnh lai tac

5X

dung voi mot luong rnoi titan kim loai can tinh che, Qua trlnh lap di lap lai nhu vay c6 th~ t1;\O nen nhirng thanh titan c6 duong kinh 5-30mm va d<:LC biet tinh khiet, chua den 99,9999% Ti. Chinh phuong phap Aken-Do B6e lan dau tien da: diroc dung de dieu ch€ Zr tinh khiet. Ngay nay phuong phap d6 duoc dung de dieu che mot so kim loai khac ntra d~c biet tinh khiet.

Tach rieng tung nguyen t{/ cap Zr-HJ

Ziconi va hafni la c~p nguyen to d6ng hanh voi nhau rfit giong nhau

ve tinh

chat, viec

tach chung ra khoi nhau g~p rat nhieu kh6 khan. Trang cong nghe nguoi ta phai dung mot so phuong phap khac nhau

de' tach rieng cluing.

doan dua vao de) tan hoi khac nhau cua K2Zr'Ft. va K2HfFh
muoi K2HfF6 tan nhieu hem

PIII((fng phap ki!f tinh phon

1.10,07 va 0,1 () mol/I. Moi khi ket tinh muoi phirc hexafloro, lai nhieu

a lai

chu yeu trong dung dich con muoi K2ZrF6 tan it hem t~p trung chu yeu vao tinh the. Lap di lap

Ian qua trlnh ket tinh lai tinh the va qua trlnh ket tinh tinh the til dung dich cho den
tinh khiet cua rieng tirng kim loai. (co chua Hf) voi Cac rnuoi hexafloro nay c6 diroc khi nau chay khoang var zicon

khi thu diroc rnuoi phirc hexafloro

K2SiFt.:

Phuong phap chief dua vao kha nang chier dung dich niroc rnuoi nitrat

cua ziconi va nen chu yeu

hafni bang tributylphotphat

(TBP), Zr(lV)

di vao dung rnoi tributylphotphat rirng kim loai.

a dang

c6 kha nang tao phirc rnanh hem Hf(lV) ZrO(NO\)z.2TBP con Hf

a lai

chu yeu Irang dung

dich rurocLap di I~p lai qua trinh chiet do hang chuc lan se thu diroc rnuoi tinh khiet cua rieng

Phuong 1'Iuip frau d(/i ion: khi dung dich muoi tetraclorua

cua ziconi

va hafni trong

HCI 6N (hrong HCI la d.n thier de ngan can slj polime hoa cua cac hop chat trong dung dich) di qua c¢t dung nhua cationit, kim 10<:1i diroc nhira hap thu. Zr(JV) tao phuc vci axit xitric (H,Cit) manh han Hf(IV) nen khi dung dung dich axit x itric trong HC] 6N, d~ nra cot nhua da hfl'p thu ziconi va hafni, ziconi diroc axit xitric hafni

a lai

nra nhanh khoi cationit

a dang

ZrO(H2Cit)2

con

lau hem tren cationit,

Lap lai mot s6 Ian qua trinh trao d6i ion nhu v~y se thu diroc

mu6i tinh khiet cua rieng tirng kim loai,

HOP CHAT CVA Ti(IV); Zr(IV) va Hf(IV) Dioxit E02

Cac ox it Ti02, diroi dang khoang 23), moi ion Ti
4

ZrO: va Hf02

khac nhau. Ba dang tinh the cua TiO]

+

la char ran rnau 1a rutin, amatazo

trang, ton tai diroi

mot s6 dang tinh the

hroi tu plurong (Hinh

va brukit, deu t6n tai trong thien nhien

vat, trong d6 ph6 bien nhat UI rutin. Rutin co mang diroc ion 0
2 -

baa quanh kieu bat kien true tinh the dien hinh cua nhirng hop

59

chat co cong thtrc chung Iii MX1 (trong d6 M la kim loai, X la oxi hay flo). Dang tinh the dan ta cua

zrOz

t6n tai trong thien nhien la baledeit dong hinh

voi mot dang tinh th~ cua HfO, va ·Mu co kien tnic khong Mu dan, trong d6 Zr va Hf c6 s6 ph6i tri 8. Ca ba dioxit deu cling, kh6 nong chay va
ben nhiet, Diroi day la nhier d¢ nong chay va nang

hrong Gip tao thanh chuan cua cluing:

oTr

00

Ti02
Ndnc.,oC
1870

Zr02

Hf02

Hinh 23. Kie-n true Clla tinh thr! rutin

2850 -1025

2900
-1054

~G~, kl/mol

-889

SI! tang nhiet de?n6ng chay trong day dioxit phan anh su tang mire d¢ ion cua E-O. Ca ba dioxit deu kha tro kiem nong chay. Vi du: TiD,:! Ti02 Ti02 Do tro

lien ket

ve

mat hoa hoc, Chung khong tac dung voi mroc, dung dich

loangcua axit (trir HF) va kiern, chi hie dung cham voi axit khi dun nong lau

va

tac dung vci

6HF

::
::

H2TiF6
NazTi03 Na2Ti03

+ +

2H2O
H2O

+ 2NaOH + NaZCO)

::

+ CO2

ve h6a

h9C, Ti02 duoc dung lam chat don cho cao su, bot rnau cho chat deo va _

san. Do rAt kh6 n6ng chay va ben hoa h9C, dot nhiet d¢ cao..

zr0

dtroc dung lam chen nung, lap 16t trong cua 10

Cac dioxit E02 dtroc tao nen khi dot dilly kim loai trong khf oxi hoac phan huy hidroxit cua E(lV)

a nhiet

d¢ cao.

Trang cong nghiep, Ti02 diroc dieu che bang each d?t chay TiCl4 trong khi oxi lOOO°C:

& 900°-

hoac bang each thuy phan titanyl sunfat, Diroi day Ia sa TiOl tir tinh quang inrnenit. Chi! h6a tinh quang inmenit da nghien

do phan

irng cua qua trlnh san xuat

min voi axit sunfuric dac:

::

FeTi03 + 2H2S04

~180''C

TiOS04 +

FeS04 + 2H:P

Hoa tan san pharn bang nuoc du roi lam Ianh dung dich

de

mu6i sAt ket tinh

a dang

60

FeS04.7H20.

Dun sOi dung dich TiOS04 vm nuoc, axit metatitanic liing xu6ng: TiOS04

+ 2H20

= =

H2Ti03

+ H2SO4

Nung axit metatitanic

a 9OO-I000 C,
D

thu diroc Ti02: Ti02

H2Ti03

+ H20

Ten thirong mai cua Ti02la trdng titan. Trang titan ta b¢t mau trang dang t6t han trang chi (Pb(OHh.2PbC03) ch6 khong doc hai va khong bi xam khi de lau trong khong khi. Ngoai viec dung lam bot mau, trang titan con diroc dung dt! ch€ cac loai thuy tinh, sa, men sa va g6m

chiu nhiet,

Trong cong nghiep, Zr02 duoc san xuat tll zicon thee so d6 sau. Nau chay zicon trong NaOH: ZrSi04

+ 4NaOH

Na2Zr03

+ Na2Si03

+ 2H20
bi thuy phan

4-0

Hoa tan san pham phan U'ng trong ruroc n6ng, Na2Si03 tan con N~Zr03 nen k€t tua Zr02.H20: Na2Zr03 + 2H20

= =

Zr02.H20 + 2NaOH

Ch€ hoa ket tua vm dung dich HCI: Zr02.H20

+ 2HCI

ZnOCl2

+ 2H20

va them NH;\ vao dung dich dt! k€t tila lai:

ZrOCl2 + 2NH3 + 2H20

= =

Zr02.H20

+ 2NH4CI

Nung ket tua d 9000C, thu diroc Zr02: Zr02·H20 Zr02 + H20

Hidroxit cUaTi(lV), Zr(IV)

va Hf(IV)
Ket

Cac hidroxit cua E(lV) la k€t tila trang, nhay co thanh phan bien d6i E02.nH20. polime hoa va chira nhieu

tua mui dtroc tao nen (dang a) chua nhi~u nhom cau OR, khi de lau mat bot mroc, tiep t\IC bi

cau

(dang

P ):

Bbi vay, dang a hoat dOng hoa hoc han dang axil orthotitanic (H4Ti04) hoat dong han Ti02.H20, (H2Ti03).

p. Vi: du

Ti02.2R20, thuong duqc goi la thuong duoc goi la axil metatitanic

Nhiet dt) va mOi tnrong kiem lam cho dang a de chuyen sang dang

p.
61

Cac hidroxit E01.nH~O kh6ng bieu 1(>th~t ro tinh axit va tinh bazo VI cluing khong tao . nen dung dich that voi mroc rna ca voi dung dich axit va dung dich kiem loang. Khi tac dung voi axit va kiern, k€t tua hidroxit chuyen sang dang-dung dich keo chua nhfrng hat keo Ian a dang polirne diroc hidrat h6a. Trong do, titan(lV) c6 kich thuoc be nen it bi po Iime h6a hon nho su tao phirc. Vi du nhu TiOz.nH]O c6 the tan trong dung dich HCI d~c tao nen dung dich H2TiCI6 va tan trong dung djch kiem d~e tao nen dung dich cua anion phtrc hidroxo Ti(OH)~- .
Cac hidroxit ZrO~.nH20 va HfO].nH20 khong tan trong dung dich kiem,

ca ba hidroxit khi tac

dung voi dung dich d~e ella axir manh tlnrong kh6ng tao nen muoi trung hoa

rna

tao nen muoi

oxo e6 cong tlurc chung EOX2 (trong d6 X=CI- , Br" ,1- , NO; va SO;- ).

Ti(OH)~ Zr(OH)4

+ H~S04 + 2HCI

=
=

TiOS04 + 3H]0 ZrOCI~ + 3H20

Tir dung dich axit, c6 the lach ra nhtrng hidrat tinh the TiOClz.2H20, TiOS04.2Hp, ZrOClz.XH]O, HfOClzHH:O. Truce day ion TiQ2+ duoc goi la titanyl, ion z-o> la ziconyl va ion Hf02+ la hafny!. Nhirng den nay nguoi ta bier rang trong dung djch cOng nhu tinh the cua cac hop chat EOX2 d6 khong c6 m~1 ion EO:'.+. vr du trong tinh the TiOS04.H20 khong c6 ion Ti02+ rna c6 mach dai (TiO)~n+:

noi voi ion 50;-

sao cho mOi nguyen ttt Ti diroc baa quanh kieu bat dien boi 6 nguyen ttt 0 cOng khong co ion

ella ion SO ~- va cua H20. Trang dung dich va trong tinh the ZrOCI2.HH20
rieng Zr02+ rna c6 ion tetrame IZr4(OHMH20)1618+:
8+

trong do Zr c6

so phci

Irf H va duoc lien kef vci nhau qua nh6m cau OB.

T<ft ca ciic mu6i oxo EOX2 diroc coi Iii.nhirng san pham ella pharr irng thuy phan mot phan cua cac mu6i E(lV), khi diroc thuy phan tiep tuc cluing tao nen hidroxit.
62

Cac hidroxit duoc dieu chi! bang each thuy phan cac tetrahalogenua Br, I), cac muoi oxo va cac rnuoi titanat, ziconat va hafnat.

EX4 (0 day X=CI,

Oxit han hop cua E(IV)

Cac dioxir Ti02,

zr02

va Hf02 khi tan trong kiem n6ng chay tao nen nhUng hop chat c6 M~E04
(trong d6 M

ten goi chung la muoi titanat, zieonat va hafnat nrong irng. Thanh ph fin cua nhirng hop chat nay rat khac nhau, Nhirng rnuoi dan gian nhat c6 cong thirc: M2EO" M'EO" tan trong mroc, nhimg muoi tan b] rhuy phan hoan toano va M' Iii. kim loai c6 s6 oxi h6a + 1 va +2 nrong irng). Da so cac titanat, ziconat va hafnat khong

Phuong phap nghien ciiu kien tnic tinh the cho thay trong cac mu6i d6 khong c6 nhimg
anion rieng cua EO;Zr(lV) va Hf(IV). VI du cac mu6i titanat thirong irng voi ba kieu kien tnic tinh the' dien hinh cua oxit h6n hop, trong d6 cac cation kim loai khac nhau chiem nhirng 16 tr6ng nr dien va nhiing 16 trong bat dien gay nen bOi cac ion 02- g6i ghem sft sao. Nhifng titanat MgTi0.l' MnTiO" eoTiO,. NiTiO) ... co kif!11 true tinh fhl kitH inmenit trong d6 Fe va Ti thay
2 -

va EO~- nen cac mu6i do duoc coi

la

cac oxit hbn hVp cua Ti(IV),

(FeTiO ..). Tinh the' nay co kien true gi6ng vai corundum (AI20,-a), cua AI chiern nhirng 16 trong bat dien gay nen boi nhirng ion 0

vi

tri

g6i ghern sit sao kieu I~p

phuong, Nhirng titanat SrTiO" BaTiO, co kiln

true tinh the' kie'u peropskit .do nhirng ion 0 2

(CaTi0.l)'

trong

va

Ca + g6i ghern Sit sao

2

kieu I~p plurong, Ti chiern 16 tr6ng bat dien

gay nen boi rieng cac ion 022

va co s6 ph6i

trf la 6 va Ca + co s6 phoi tri la 12 d6i vai 02(Hinh 24).

Nhung titanat Mg2Ti04, ZrTi04 va Co2Ti04 co kiell Ink tinh till kilu spinen
(MgAI20~), trong do Ti thay Mg chiem 16

Hinh 24. Kiel'

tnil"

cua tinh the"perop.l'kit

. tr6ng ttl dien con Co, Zr va Mg thay Al chiem 16 tr6ng bat dien gay nen bci nhimg ion 02ghern sit sao kieu I~p phtrong,

g6i

Cac oxit hon hop ella Ti(IV), Zr(JV) va Hf(1V) cflng duoc tao nen khi nung cac h6n hop cua cac oxit Wang ling.

Tetra halogenua EX4

TiF~, ZrF~ va HtF4ia chAt polime mall trang. Tinh the TiF4 diroc eau tao nen boi cac nhom bat dien TiFt>n6i vai nhau qua cac dinhF chung con ZrF4 va HtF~ diroc ca:u Cac tetraflorua

63

tao nen bbi cac nh6m hlnh phan lang tru ZrFs va HtFs nci voi nhau qua cac dinh F chung. adieu kien thirong, trir TiC4 la chat long, cac tetrahalogenua E~ khac (X=Cl, Br va I)

deu Ia ch~t ran mau trang, tinh the co rnang lum phan

tir. Dum day Ia nhiet dl) nong chay cua

cac florua va clorua:

TiF4 400°C TiCl4 -23°C Cac tetrahalogenua cua nguyen t6 khong-kim ZrF4

9100C
ZrCl4 437°C

HfF4 l020°C HfCI4 435°C tuc Ia nhimg halogenua

EX4 cd tinh chAt gi6ng cac halogenanhidrit

loai, tac dung voi nuoc nong tao thanh hai axit:

EX4

3H20

H2E03

+ 4HX

hOi hoi Am. Tinh the TiBr4 va TiI4 dong hlnh voi tinh the SiI4>Gel, va Snl., Day Ia mot trong nhfmg diem gi6ng nhau gitra cac nguyen t6 nh6m IV A va nhom IVB 6 trang
thuy phanhoan toan thai oxi h6a cao. Cac tetrahalogenua hexahalogeno: EX4 EX4 tac dung voi dung dich HX d~c tao nen nhtmg phirc chAt

Gi6ng vm SnCl4• titan tetraclorua

la chat long b6c kh6i manh trong khOng khi vi bi

+ 2HX 1.

f)¢ ben cua H2[E~1 tang len tll' Ti den Hf va giam xuong tu F de'n

.Cac EX4eung co tM ke't hop voi cac halogenua kim loai kiem va kiern th6 (trong dung dich hoac 0 nhiet d¢ cao) tao nen cac plurc chat Cl

co cong thtrc chung: M2[TiX6]

(0 day X=F,

va

Br), M'[TiF6],

kim

loai co

so oxi h6a

M2[ZrF6], M3[ZrF7], M4[ZrFs], M2[HfF6], M4[HfFs] (0 day M va M' la

+ 1 va +2 E~

nrong ling).

Cac tetrahalogenua TiCl4 duqe dung nhieu nhat huy

duoc dung lam nguyen lieu

de dieu

che va tinh che' kim loai,

de dieu che' titan kim loai trong cong nghiep, Cac tetraiodua phan

d nhiet dQ cao nen duqc dung de dieu che cac kim loai d~c biet tinh khiet. Ngoai ra cac tetrahalogenua E~ con duoc dung trong nhtmg t6ng hop vO C(J va hOU C(J va dung lam chflt xuc
tac (cac qua trtnh hidro hoa, oxi hoa, ankyl h6a, trung hop •...) Cac tetrahalogenua de dieu che cac halogenua than 6 nhiet dQ cao: EOz EC + 2C EX4 diroc

4.0 nen hOi lac dung tnrc tiep cua cac nguyen t6. Nhirng

d6 ngiroi ta thmmg halogen hoa hOn hop cua hop chAt E(IV) voi

+ 2X2
2X2

= =

E~ E~

2CO

(6 day X=CI. Br) (6 day X=Cl, Br va I)

+C

Plurong phap nay khong the ap dung duqc cho cac florua nen TiF 4 duoc dieu che bang

64

lac dung ella TiCI4 voi khi HF con ZrF4 hay HfF4 duoc dieu che bang each nhiet phan mu6i amoni hexafloro.

(NH4)2fZrFd

ZrF4

+ 2NH3

2HF

Trang cong nghiep ngiroi ta dieu ch€ ZrCI4bAng phuong phap clo h6a h8n hop cua khoang vat zicon voi than 900

ZrSi04 ZrC

+ 4C + 2CI2

=
=

zrC
ZrCI4

+ SiO + 3CO

+C

Sun/at clla E(IV)

Ciing nhir cac tetrahalogenua cac muoi sunfat khan ella Ti(lV), Zr(IV) va Hf(IV) deu nit kern ben khi co mat nuoc, kha nang thuy phan tang len tir Hf den Ti. That vay, tir dung dich mroc nhung co rnoi tnrong axit rnanh (H2SO4 tren 6N), muoi sunfat cua Zr(IV) va Hf(lV) co th~ ket tinh iJ dang muoi trung hoa Zr(S04)2.4H20 rnuoi oxo ZrOS04.nH20 va HfOS04.nH2

o.

va

a dang

Trong khi do mu6i trung hoa Ti(S04)2 khong the

duoc tao nen khi TiO:! tac dung voi axir sunfuric dac rna chi dtroc tao nen trong dieu kien hoan toan khong c6 mroc, khi TiCl4 tac dung vci hoac khi mlu chay Ti01 trong kali disunfat: TiCl4 Ti02

so} trong
= =

dung moi

S02Cl2

(sunfuryl clorua) long

+
+

4S03
2K2~0?

Ti(S04h

+ Ti(S04)~ +

Hop chat peoxi cua Ti(IV)

Mot phan irng dac tnrng cua muoi Ti(IV) voi H202 trong moi tnrong axit dung dich c6 rnau da cam.

la tao nen

Axit peoxititanie

c6 cau tao phan tir:

Phan irng tao mau naydung ella Ti(lV) c6 the tach ra

5]'

cte: nhan

biet titan va hidro peoxit. M¢l so

it hop chat peoxi

K2[Ti(02)2F2] va

dang tinh th~ la: K2[Ti(02)(S04)2].3H20,

K3[Ti(02)F
S-H6a hQc vo co- T3

65

HOP CHAT

eVA TITAN

VOl

s6 OXI H6A

THAP

Cac hop chat cua titan v6i s6 oxi hoa thap deu de chuydn thanh hop chat cua titan(IV).

Hf!P chdt cua Ti(lJ)

Titanill} oxit (TiO) la chat dang tinh

the mau
=

vang choi, c6 kieu kien tnic NaCl va la

chat khong hop thuc, N6 tac dung v6i axit d~c giro phong Hj: 2TiO Titan(Il) khi quyen tnt Vidl,l: Ti02

+ 3HzS04

T~(S04)3

+ H2 + 2H20

oxit duoc tao nen khi khir Ti02 bang Mg, Ti hay Cl2

a nhiet

de:}cao va trong

+ Ti

2TiO

Titanill) hidroxit (Ti(OH)2) 13. k~t cham voi mroc gicli ph6ng H2:

tua mau den, khOng tan trong nuoc nhung tac dung
2Ti(OH)3

+ H2

Titanffl) hidroxit duoc tao nen khi mu6i cua TirIl) tac dung v6i dung dich kiem.

Titanill). halogenua (TiX2, CI day X=Cl, Br va I). Cac dihalogenua

den, kh6 nang chay va ben voi nhiet,

nay la chat bot mau

Titan(D) clorua tan It trong mroc nhung tac dung voi runic giro ph6ng H2: 3TiC12

+ 3H20

2TiC13

+ H2Ti03

2H2

Titan(ll) clorua cling de tac dung voi oxi khong khi" dieu kien thuong:

nen

can phai

bao quill trong khi quyen H2 hoac CO2. TiX2 duoc tao nen khi khir cac tetrahalogenua TiX3• TiX4 bang cac chat khir

Cac dihalogenua Vi du:

khac nhau hoac khi nhiet phan trihalogenua

+
/

rsci,
50crc

+ +

2HCI

2TiC13

TiCI:;!

HfIP chdt cua Ti(lIl)

S6 hop chl:\:tcua Ti(llI) c6 nhieu han so vci Ti(ll).

Titan(IlJ) oxit (T~03) la chfft dang tinh the man tim c6 kien tnic tinh the kitu A1203~C(.

66

rat kh6 n6ng chay, kh6 soi va khong tan trong mroc. Khi dun n6ng trong khong khi hay khi dun soi trong HNO" n6 bien thanh Ti.O, Titan(III) oxit duoc tao nen khi khir TrO, bang C b 870°C hoac khu h6n hop TrO, va

TiCl4 bang H2 b 1400°C: 3Ti02

TiCI4

2H2

2Ti20,

+ 4HCI

Titanilll) hidroxit (Ti(OHh

hay Ti;03.nH20)

Ilt ket tua mall tfrn-nau khong tan trong

rnroc va c6 kien true wang nr hidroxit cua kim loai h6a tri ba. N6 khong tan trong dung dich kiem rna tan trong axit tao thanh mu6i Ti(III). N6 c6 tinh khir manh,

& tac dung voi oxi kh6ng khi:

Titan(III) hidroxit duoc tao nen khi mu6i titan(III) tac dung voi dung dich kiern.

Titan(llI) halogenua (TiX3). Tat ca trihalogenua nay deu Ia chat bQt mau tfm, TiP3 ben nhat d6i voi nhiet va kh6ng khi, con cac trihalogenua khac phan huy b nhiet dQ cao va c6 tinh
khir manh. Trihalogenua thuong gap nhat la TiCI].

Titan trihalogenua va TiCI4

va

(TiCI,) khan la chat bot rnau tim, phan huy b 500°C tao thanh TiCI2 de; tac dung voi kh6ng khi am theo phan irng:

Neu kh6ng c6 mat khi oxi,n6 rae dung cham vai mnrc giai phong Hz:
=

2Ti02

6HCJ

H2

Khi tan trong mroc c6 moi tnrong axit, TiCI3 cho dung dich mau tim, rnau cua ion [Ti(H1()6J3+. Ion nay c6 ri1~t trong tinh the phen titan M Ti(S()4h.12H2() (M la ion kim loai kiem va NH;). Hidrat TiCI,.6Hp cling co ba dang dong [Ti(H20)5CIJClz.Hz() ker tinh nr dung dich cua TiCI, trong moi tnrong axil. Hidrat nay phan gi6ng nhir CrCI3.6HzO la: [Ti(H2()6JCI.l c6 mau tim,. ciing co rnau luc. Jam cho phen co mau tim

c6 mau luc va lTi(HP)4CI2JCI.2H20

Cac TiX3 khan diroc dieu che bang each dung cac chat khir khac nhau

M khir

TiX4 khi

dun n6ng. Vi du nhu TiCI3 duoc dieu che bang tac dung cua Ag voi TiCI4 b -200°C: TiC14 Hidrat TiCI3.6H20

Ag

TiCl3

AgCl

diroc dieu che bang each hoa tan kim loai trong dung dich HCl d~c

67

hoac dung kern khir TiOC).! trong dung dich HCl: 2TiOC12

+ Zn + 4HCl

2TiCI,

ZnC12

+ 2H20

68

CHUdNGIV

cAc
Nhorn VB gomcac

NGUYEN TO NH6M VB
Dum
day

nguyen t6: vunadi(V), niobi(Nb) va tantan (Ta), 10) .

la

mot

s6 d~e diem ella cac nguyen t6 nhom VB(Bang . Bang 10

MQt
Nguyen

so d*c dit~m cua cac nguyen

eftu hinh electron nguy~ntir ta

to nh6m VB
The' Ban kfnh dien

56 thu nguy~n ti'r

t6 (E)

Nang luong ion hoa, eV

nguy~n ti'r

cue
chuan, V V2+N

II

12

I,

14

15

V Nb Ta

23 41 73

[Ar 13d-'4s~ [KrI4d~5sl

6,74 6,HR

14,1 14,32 16,2

26,31 25,04 22,27

48.35 37,70 33.08

68,70 51,90

1,34 \,46 1,46

-1,186

lXe J4f145d-16s2 7,88

Vanadi, niobi va tantan co cau hinh electron la (n-I )d)·4ns

1·2

va ia kim loai chuyen tiep,

Nguyen nr vanadi va tantan co cftu hinh electron gi6ng nhau, rieng niobi co ca'u hinh electron hoi khac, mot electron 55 nhay vao dien obitan 4d. Di~u nay chimg to cac obitan 4d va 55 c6 nang luong ga.n gi6ng nhau. Tuy nhien

51! khac nhau d6 v~ tilu hlnh ;Iectron khong co anh

hirong den tfnh chat h6a hoc: niobi rift giong voi tantan. Nang ltrong ion h6a cua V, Nb va Ta cho thtty cac kim loai c6 kha nang tao nen nhtmg cation
E2+, E3+

va trong nhirng hop chilt nrong rrng, cluing c6 56 oxi h6a +2 va +3. Tuy nhien s6

oxi h6a d~c tnrng

nhar trong cac hop chat cua cac nguyen t6 nh6m nay la +5. D~ ben cua trang

-thai oxi h6a cao d6 tang len til V de'n Ta. Chien bien d6i_nay trai ngiroc vai chieu bien dOi cua trang thai oxi h6a +5 trong nhom As, Sb va Bi (nh6m VA).

69

S1,T tang tir tren xu6ng diroi d(>ben cua cac hop chat v6i s6 oxi h6a cao la dac tnrng cho cac nguyen t6 rna nguyen tlr co vo ben 8 electron kfnh nguyen tlr tang len, hieu irng cue-hoe-them khac (VI du voi 0)

a sat ngay

lap vo electron h6a tri. Khi ban

ciia vo 8 electron khong bien d6i may nhung

giG' electron hoa tri yeu hon cho nen electron hoa tri tao lien ket cong hoa tri voi nguyen t6

de dang

hon va lien ket cong h6a trj se ben han. D6 Ia nguyen nhan lam

tang d¢ ben cua cac hop chat v6i s6 oxi hoa cao cua nguyen t6, trong tnrong hop nay la hop chat cua V(V), Nb(V) va Ta(V). Trong khi trong cac nguyen c6 hieu irng cue-boa-them

to nhom

VA, ttl tren xuong dum

a ngay

tang len VI nguyen tii cua nguyen t6 c6 vo 18 electron de bien dang

sat lap vo electron h6a tri. Ket qua xu6ng tl1 As den Bi, Ban kfnh nguyen lantanoit,

Ia d¢ ben cua cac hop chat voi s6 oxi h6a +5 giam

nr tang len tir V den Nb nhung khong bien dbi nr Nb den Ta do sl! co

Bbi vay, Nb va Ta rat gi6ng nhau vI! doh chat h6a hQC. DAy Ia cap nguyen t6 rat

gi6ng nhau sao cap Zr-Hf d1'Ixet b chuang truce, viec tach cluing ra khoi nhau Ia cong viec nIt kho khan trong h6a hoc v6 ca.

Ca ba nguyen t6 V, Nb va Ta Mu co kha nang tao nen nhirng hop ch<1'tpeoxi va hop

char co isopolianion

va heteropolianion.

o trang

thai oxi h6a thap, Nb va Ta thirong tao nen

hop chat claste. Day la ket qua cua d¢ manh cua lien ket kim loai-kim thang hoa rtlt IOn cua kim loai niobi va tantan. Chung ta se thay dieu nay va reni,

a molipden,

loai

tM

hien

a nhiet
vonfram

CACDdNCHAT
Tinh chat li hoc
Vanadi, niobi va tantan la nhirng kim loai mau trang, xarn, rat kh6 nong chay va rat kh6 soi. Tinh the kim loai c6 rnang luoi l~p phuong tam kh6i. Diroi day la mot s6 hang s6 v~t 11 quan trong ciia cac kim loai (Bang 11) Bang 11

Hang so v~t Ii quan trong cua cac kim loal V, Nb va Ta

Kim loai

(E)
V Nb Ta

Ndnc,oC

Nds,oC

Nhiet thang hoa, kJ/mol

Ti kh6i

D¢ cirng (thang Moxa)

D¢ dan dien (Hg::::I)

.... 900 1 .... 2470 .... 015 3

.... 400 3 .... 44760 -5500

,

510 724 782

6,11 8,57 16,65

6 6 6

4 5

70

Nhiet d¢ n6ng chay, nhiet d¢ soi va nhiet thang hoa ella ba kim loai deu ra-t eao va tang len ttt V den Ta. Nhirng hang so v~t li cao do duoc giai thich bang d¢ ben ella lien ket kim loai trong tinh the gay nen boi s6 100 electron d doc than (rnoi nguyen tir c6 4 electron) tham gia

tao thanh lien ket cong hoa trio M¢t dieu la la Nb va Ta c6 diu hinh electron va ban kinh nguyen tir giong nhau nhirng nhiet d¢ nang chay cua cluing khac nhau r~lt nhieu. C6 Ie rAng
nhtrng obitan 4f di6n dll electron da lam thay d6i kien tnic electron cua nguyen t11cac nguyen t6 sau lantanoit, Kien true thay d6i do chan dien tich hat nhan kern hon lam cho dien tich duong cua hat nhan tac dung manh han len lap vo electron cua nhirng nguyen t11ke canh va lam tang mire d¢ ion cua lien keto D6 ia nguyen nhan lam tang manh nhiet d¢ n6ng chay va nhiet de.)soi

ttr Nb den Ta.

Ca ba kim loai khi tinh khiet co nhfrng tinh chat co If tot nhung khi chua tap chat (0, N, C, B, H ...) tro nen don do tao nen nhung hop chat co thanh ph fin bien d6i.

ca

ba kim loai tao nen nhieu hop kim voi Fe, Cr, Ti, Mn, Mo, W, Zr, AI, C, B, N ...

Nhirng kim loai V, Nb va Ta duoc dung chu yeu HIm chat cho them Va? cac loai thep d~c biet, Vanadi truyen cho thep tinh deo dai va tinh chiu va dap. Thep chua V dung d~ che tao 6tO, xe tang. Khi dtroc cho them vao thep, vanadi con co vai tro loai trir nhi.ing tap eha"t co hai l:J trong thep nhu 0, S, C va N. Khoang 95% vanadi duoc san

xuat la dung de che' hop kim. Niobi va

tantan tao nen nhfrng hop kim chiu nhiet, sieu cirng va ben h6a hoc, Thep chua Nb va Ta dung

de lam dung

CI,!

cat got nhanh. Thep chua Nb dung lam tuocbin khi va dong co phan lire, Hop

kim chira Nb dung lam cuon day cua nam

cham sieu dan. Hop kim g6m 90% Nb va 10% Ta

dung trong ki thuat phan lire va du hanh vii tru (may bay sieu am, ten lila va tram du hanh vii

tru )

Tinh chd: hoa hoc

o nhiet o nhiet

d¢ thuong, ca ba kim loai kha tro ve mat h6a hoc, nhat la Nb va Ta. Nguyen

nhan cua tinh tro d6 la Nb va Ta c6 rnang oxit mong va ben bao v¢ be mat kim loai, Khi dun n6ng, cac kim loai tac dung vai oxi va flo tao thanh oxit E205 va florua EF~ (E = V, Nb va Ta). d¢ cao, cluing tac dung voi clo, luu huynh, nita, cacbon, silic, ... thuong tao nen mot s6 (3350°C va 3800°C tuang img) khong hop char ki€u xam nhap va c6 thanh phan bien d6i giong nhir cac nguyen t6 nhorn IVB. Nhirng eacbua NbC va TaC c6 d9 cirng va nhiet d¢ n6ng chay thua kern kim cirong.

0 dang bot,

Nb va Ta tac dung v6i hoi rnroc giai ph6ng H2•

Vanadi i:J dieu kien thirong chi tan trong dung dich HF d~e tao nenVFJ

cirong thuy tao nenv'Cl.; khi dun n6ng trong HNO, tao nen V02N03
nen VOS04• va HNOJo Vi du: 3Ta Niobi va tantan chi tac dung cham voi dung dich HF va

va tan trong va trong H2S04 d~c tao tan M trong h6n hop HF

+ 5HN03

+ 21HF

71

Ca ba kim loai tac dung v(ri kiem n6ng chay khi c6 mat ch1ft oxi h6a:
4E

+ 12KOH

+ 502

4K3[E041

+ 6H20

Tfnh tro hoa hoc cua Nb va Ta gay nen bdi mang oxit mong va ben bao v~ ~ mat kim loai, Do kh6 n6ng chay va ben h6a hQC, Nb va Ta cung nhu hop kim cua chung duqc dung d~ che nhtrng b¢ phan quan trong nh1ft cua

cac may h6a. Sqi day rat manh Hun bang tantan duoc

dung de n6i day chang va huyet quan trong CO'tM ngiroi.

Trang thlzi thien nhien va phuang phdp diiu ehe

Trong thien nhien, vanadi Ia nguyen t6 tuong d6i ph6 bien, phd bien han Cu, Zn va Pb con niobi va tantan ta nhfrng nguyen t6 hiem. Tru hrong cua V trong vo Trai Dat la 6.10-3%, cua Nb la 2.10-4% va Ta 1a 2.10-5% t6ng s6 nguyennr, c6 mo 160 rna dIan vanadi Ia patronit (VSz-2.5)' sunvanit (Cu3VS4),

Ca ba deu

Ia nguyen t6 phan tan, khong va vanadinit (Pb5 (V04)3 Cl).

trong khoang v~t cua cac kim loai khac, Nhirng khoang v~t rieng cua alait (V203.H20)

Nhtrng khoang vat nay deu hiem co nen khong phai la nguyen lieu de san xuat kim 101Pvanadi.
Niobi va iimtan luon luon d6ng hanh voi nhau. Khoang v~t quan trong cua chang I?!.niobattantalat «Fe, Mn)(E03)2)' khoang v~t c6 nhieu tantan hem diroc goi Ia tantalit «Fe, Mn)(Ta03h) va c6 nhieu niobi han duqc goi la columbit «Fe, Mn)(Nb03)2)' thuong dIan trong khoang v~t cua kim loai dat hiem, Vanadi c6 kich thuoc nguyen Niobi va tantan

tir gao vm nhtmg nguyen t6 phd bien nhat nhu Fe, Ti va

Mn, ion vanadat c6 kfch thudc gful voi ion photphat.

SV gi6ng

nhau v~ kich thllac d6 dan den su

thay th~ Fe, Ti, Mn, P bang V trong kien tnic tinh the ciia cac khoang v~t tuong ling. Nam 1830 nha khoa hoc Thuy Dien Sefstrom (N.G. Sefstrom, 1787-1845) phat hien

duqc mot nguyen t6 moi trong quang sM. C6 trU luong 16'0va c6 cac hop chat voi mau slk khac nhau, nguyen t6 d6 diroc goi la vanadi, lay ten cua nil than sac dep Vanadis trong truyen than thoai cua xu Scandinavi. dun n6ng. Nam 1801 nha h6a hoc Hatset (C. Hatchet, nguyen t6mm kim loai. Kimloai 1765-1847, nguoi Anh) phat hien mot trong man khoang v~t 11fyd Bac My. Ttl khoang v~t d6 tach dircc oxit cua d6 duoc goi la columbi va khoang v~t dugc goi D~n nam 1867 nha hoa hoc nguoi Anh Roscoe (H.E. Roscoe, 18451927) moi dieu ch€ dtroc kim loai vanadi bang tic dung cua khf H2v(ri vanadi clorua (Va3) khi

la columbit

mot

de ghi nho ten

Columbia la mQt bang cua nu6c My. Nam 1802, nha khoa hoc Ekebec (A_G. Ekeberg, 17671813, nguoi Thuy Dien) nghien ctru cac khoang v~t d Phan Lan phat hien mot nguyen t6 moi ' goi la tantan. Nguyen t6 c6 ten goi nhu v~y la vi hop ch4't cua n6 tro v~ mat hoa hoc. Tanianlus
cua mot ong thlhl qua nhieu tham vong nhung khOng thoa man duoc va su6t dCri.om han vi bi cac thlhl khac trimg phat, giam VaG vach dol.•Mot thoi gian dID'ngum. ta coi columbi va tantan 13 mot. Maid:~n

la ten

nam 1844 nha h6a hQCngum Duc Rose (H. Rose, 1795 -1864) phan tich khoang v~t columbit va chrmg minh rang columbi la hEm hop cua tantan va mot nguyen 16 khac
chua biet c6 kb6i hrong rieng be hon tantan. Nguyen t6 moi do dugc goi 18. niobi, 11fyten cua Niobe la con gai cua than Tantalus. Nhieu cOng trlnh nghien cuu sau d6 khang dinh su ton tai 72

cua hai nguyen to niobi va tantan vci luong khac nhau trong columbit va tantalit. Nam 1865 . nha hoa h9C Thuy Di~n Marinhac (J.G. Marignac, 1817-1894, d€ ra phuong phap phan chia Nb va Ta dua van dO tan It hon trong dung dich HF loang cua kali florotantalat so voi kali floroniobat, phuong phap nay den nay van con diroc sir dung. Narn 1907 Banton (W.von Bolton) da dieu che diroc cac kim loai tinh khiet Nb va Ta khi dung natri kim loai khi'r floroniobat va florotantalat. Nhtrng mroc khai thac nhieu khoang v~t cua V la Nam Phi, Nga va Trung Quoc, cac mroc c6 nhieu rna quang cua Nb Zaia va Nigieria.

la Brazin

va Canada, cac rnroc co nhieu

rna quang

cua Ta

la

Nguyen lieu de san xuat vanadi kim loai

tuyen diroc dua dtroc xi co chua FeV04.

la quang

sM co chua vanadi. Quang sau khi da

vao 10 cao d~ luyen gang chua vanadi. Khi luyen thep til gang chua vanadi, thu
Nung xi vci NaCl khi co mat oxi kh6ng khl.o 900°C:

4FeV04
Che' h6a

+ 4NaCI + 02 = 4NaVO.1

+ 2Fe20,

+ 2Cl2

natri metavanadat (Na VO,) voi axit d~ ch€ V 205' San pham thu diroc khi ch€ hoa quang khac cilng thtrong la V 205' D~ co kim loai vanadi ngiroi ta dung Al khi'r V 205'
Vanadi kim loai fiit tinh khiet duoc di€u ch€ bang each nhiet phan VI2 theo phuong phap AkenDo Boe. D6 co hop kim ferovanadi ferosilic: = 5Si02 (chua duoi 30% V), ngiroi ta khir V20~ hay vanadat bang

4V

Niobi va tantan kim loai diroc dieu che bang each dung nhirng kim loai natri, canxi khir pentaoxit, pentaclorua Vi du: hay muoi phirc floro cua niobi va tantan.

+ K2[TaF71 +

5Ca 5Na

=
=

SCaO 2KF

2Nb

+ SNaF

Ta

Tantan can co the: dieu che bang each dien phan Ta20S trong K2lTaF7J nang chay. Cac kim loai Nb, Ta eilng diroc tinh che' thea phirong phap Aken-Do ferotantan eilng diroc san xuat urong ttr nhu ferovanadi.

Boe, Cac hop kim feroniobi,

Cht h6a qut;ing va tach rieng Nb va Ta

Quang ni<?bat-tantalat sau khi da tuyen, diroc mill chay voi kiern hoac eaebonat kim Ioai . kiem:

+ 6NaOH Mn(EO,)2 + 6NaOH

Fe(E03)2 Rira san pham voi nuoc

= =

2Na3E04 2Na,E04

+ FeO + 3H20
+ MnO + 3H20
stanat,

de hoa tan nhirng hop chat tan nhu silicat, aluminat,

73

vonframat (ga.y nen bbi cac tap cha.'t c6 trong quang) r6i chc! h6a tiC!pv6i axit loang d~ hoa tan FeD Vll MnO va con I~ hid rat cua cac pentaoxit:

Ch€ h6a cac hidrat v6i dung dich cua hOn hop HF va KF: Nb205 + 4KF + 6HF Ta20S + 4KF + 10HF

= =

2K2[NbOF5] + 3H20 2K2[TaF7] + 5H20

Dira vao dO tan khac nhau, K2{NbOFs] tan hoi nhieu hon K2{TaF7J. ngtroi ta k€t tinh phan doan d~ tach rieng hai mu6i nay ra khoi nhau. Quang cac kim loai din hiem c6 chua Nb va Ta, sau khi da tuyen. dugc clo h6a khi c6 mat than a nhiet dO cao. Nhfmg clorua de bay hoi cua Ti(IV), Nb(V) va Ta(V) thoat ra ngoai con nhUng clorua khong bay hoi cua da.'t hiern, kim loai kiem thO va kim loai kiem lai trong kh6i n6ng chay, Chung ca.'tphan doan tach rieng la.'yNbCIs va TaCIs. 1M tang khoang chenh lech cua nhiet dO soi, ngiroi ta cho them POCIl va~ va chung ca.'tphan doan hOn hqp san phdm ket hop NbCi5.POCll va TaCIs.POCI3 d~ tach rieng chung,

de

1M tach rieng Nb va Ta nguoi ta con c6 th~ chiet chon ·IQc h6n hop florua bang tribenzylaminhay cupferon trong clorofom hoac dung phuong phap trao d6i ion.

HQP CHAT eVA V(II), Nb(II) VA Ta(II)

Sa d6 oxi h6a-khii dum day cho tha.'y wang quan dO ben cua cac trang thai oxi h6a khac nhau cua V, Nb va Ta a trong dung dich nuoc
-0,254
,

,..,

VOl ~Os T~Os

1,00

V02+
0038

0,359

V3+

-0,256

y'2+ -1,099

-1,186

01 0

Nbl+
. -0.812

Nb Ta

Sa d6 cho tha.'y a di~u kien chuan, trang thai oxi h6a +4 III ben nha.'t d6i v6i vanadi, hop cha.'t vanadi(V) c6 tinh oxi h6a va hop cha.'t cua V(III), V(II) va V(O) c6 tinh khu. Sa d6 the! oxi hoa-khir cua Nb va Ta dan gian han nhieu so v6i vanadi. Trang thai oxi h6a +5 cua Nb va Ta Iii ben nha.'t.

Vanadi monooxit (VO) Iii cha.'t c6 thanh ph," bien d6i VOO•8.H25 .Tinh the c6 rnang tu6i ki~u NaCI, c6 rnau xam den, c6 anh kim va dAn d.i~n. N6 tan it trong mroc, tan de trong axit 74

loang tao thanh muoi V(ll):

. Ion V(H20)~+ c6 mau tim. Nhung hi drat tinh tM nhu VC12.6H20, VS04.7H20 K2S04• VS04.6H20

va

cling c6 mau tim. Khi ch€ h6a dung dich cua nheng mu6i nay voi kiem,

k€t tua V(OH)2 mau nau lang xu6ng. Hidroxit nay l8. bazb I11ty€u. de bi oxi khong khi oxi h6a. Vanadi monoxit ducc tao nen khi dung V. K hay H2 klnr cac oxit V203' V02 va V 20S nhiet d~ cao. Vidl;l: 2V203

+ 2K

4VO

+ K202

Vanadi halogenua (VX2) l~ chat VBr2 mall nau va VI2 mall do.

a dang

tinh th~: VF2 c6 mall luc nhat, VC12 mau luc,

Vanadi diclorua (V02) la chfi't dang tinh th~ mau luc, n6ng chay lOOO"C va sOi 1377'C, tan de trong nu6c cho dung dich mau tim. Trong dung dich, n6 tilc dung cham v(ri nu6c giai ph6ng H2, dung dich mall tim bien thanh mau luc cua mu6i V(ID): 2VC12 + 2H20

= =

2VOCl

iHCl

+ H2

La chfi't khii manh, VC12 k€t tua dllgc cac kim loai Sn, CU, Ag tir dung dich muoi:
V02 + SnCl2 + H20 VCl2 + CuS04 + H20

Sn + VOC12 + 2HCl Co + VOC12 + H2SO4

o nhiet

d¢ cao va2 c6 th~khit dugc CO2 thrumCO:

3Va2
Vanadifll)

+ 2C02

2voa

+ VC14 + 2CO

clorua duqc tao nen

kim loai tac dung v(ri khf HCI Vi du:

a 3500C.

khi khit VC14 hay V03 bAng H2 a 7500C hoac khi vanadi

= = so hop

VCl2 VC12

2HO
~

ch~t cua Nb(ll) va Ta(II) c6 it han nhi~u so v6i V(II) va d~u kern tin.

HQP,CHAT CVA V(III), Nb(IlI), VA Ta(III)

Vanadi(lll) oxit (V203) c6 thanh ph4n bien dOi Y01,60-1,8{I la ch:lt dang tinh the cornang

75

luoi gi6ng AI20,-a, nong chay

1967°C

va soi

a 302rc. 0 trang

khong khi, n6 rae dung

cham voi oxi tao thanh V01. N6 kh6ng tan trong ruroc, tan de trang axit tao nen muoi V(III):

Ion V(H 2O)~+ c6 mau luc. Nhfrng hidrat tinh th~ nhir VCI3.6H20,

VI3.6H20

cfing c6

rna u 1J,lC, tinh tM phen KV (SO 4)2'12H 20 c6 mau tim, tan trong ntree cho dung dich mau Iuc. Khi che hoa dung dich mu6i V(III) voi kiem, ker tua bong V(OH), mau luc Icing xu6ng. Hidrox it nay Ia bazo yeu, Niohi(llI)

de bi oxi

khong khi oxi hoa,

bot mau xanh den, nong chay

oxit (NbP,)

la chat

1775"C, khong tan trang

ax it (trir HF) va cirong thuy.

Nb205

a nhiet d¢ cao.

o nhiet

de}cao, cac ox it V 203 va Nb.O, duoc dieu che bang each dung H2 khir V205 va

Vanadi trihalogenua (VX,) la chat if dang tinh tM: VF, c6 mall vang luc, VCI, mall tim
do, VBr3 mall den luc va VI3 rnau den. Vanadi trifiorua nrt ben voi nhiet, n6ng chay 0 1 I 27°C va soi 0 1427°C con cac trihalogenua 130"C thea phan irng: 2VCI., Vanadi tri~lorua va vanadi triiodua khac tan tan trong nuoc (bi thuy phan) va cac dung moi hiru khac kern ben hon nhieu, vi du nhu VCI) phan huy 0

co, cac trihalogenua

it hon nhieu,

Ion V'+ co kha nang tao phirc manh hon ion V2+. Nguoi ta bi€t nhirng plurc chat cua V'+ nhu NH4[V(S04)2J.6H20 mau tim nhat, K3[V(CN)6J.3H20 mau do, K4[V(CN)7J.2H20 mau tim nhat. Vanadi trifiorua tao nen voi fIorua kim loai kiern mu6i phirc M3[VF6J, vanadi triciorua t<;10 nen voi clorua kint loai kiern cac mu6i phuc M[VCI4], M3[VCI6J, kim loai kiern). MJ[V2Clg]

(0 day M 18.

Vanadi triflorua diroc tao nen khi V(OH), tac dung vci dung dich HF, vanadi triclorua

duoc tao nen khi dun nong VCI4 trong khi quyen N2, con vanadi tribromua va vanadi triiodua
diroc tao nen bang tac dung true tiep cua cac nguyen t6.

76

PHUC CRA T CLASTE CUA Nb vA Ta

M¢t s6 halogenua cua Nb va Ta voi s6 oxi h6a tMp c6 thanh phan khOng

nop thee:

NbF2.S' NbI2.33, NbC12•67, NbBr2.67, NbI2.67, TaC12,s, TaBr2.33, TaBr2,s, TaBr2,9' TaBr3", Tal2,33. Nhieu halogenua c6 cau 4-0 claste (cluster, tieng Anh 18 nh6m, cum), Claste 18 ion hay phan tit chua nhiing cum g6m 2 hay hon 2 nguyen

til kim loai lien ket voi nhau. Ngiroi ta biet duoc

nhtmg hidrat c6 thanh phan E6XI4'7H20, trong d6 E

= Nb va Ta, X = 0

va Br. Chung ta xet hop

chat khan E~'4'

Hop chat

clorua

wac day duqc xem la c6 cOng thirc NbC12, v~ sau biet duoc cong thuc

Ia NbC12.33 hay Nb60W

v~ mat d¢ng hQC. Hop chat Nb6CI14 bao g6m nhtmg ion [Nb6Cld2+ lien ket v6i nhau qua nhtmg
cau la ion Cr. Ion [Nb6Cl'2]2+ c6 c5u tao:

Hop ch5t nay tan trong nuoc va nrou, khi tic dung v6i muoi Ag" chi c6 In s6 nguyen tir 0 diroc ket tua duoi dang AgO. M~t khac phirong phap nghien cuu kien true bang tia Ronghen cho thay trong dung dich nrou, hop chat d6 phan li tao nen ion [Nb6ClI2f+ tro

Nb

Oel tit Nb tit

trong d6 6 nguyen

lien ket v6i nhau tao thanh mot bat dien deu va ngoai ra hai nguyen

Nb con lien ket v6i nhau qua cau nguyen tir O. C6 tI,I va nhtmg halogenua E~.s nhung bang each hoi khac.

Ie nhtmg halogenua

EX2,33 c6 cau tao nrong

ciing bao g6m nhimg cum E6X'2 lien ke't v6i nhau qua c~u X-

HO P CHAT

CVA V(IV). Nb(IV) VA Ta(IV)

Dioxit E02
Vanadi dioxit (V02) c6 thanh ph;in bien dOi VOI•S•2.17 va c6 mau xanh cham, niobi dioxit (Nb02) Ia b¢t mau xam va tantan dioxit (Ta02) la bot mau den. ca ba dioxit d~u c6 kien true kieu rutin lech duoc cAu U,l0 nen bbi cac bat dien E06 nOt v6i nhau qua dinh 0 chung. Cac ion kim loai trong cac bat dien Nb06 va Ta06 g4n nhau hon va oxit c6 d¢ ttl cam nrong d6i thap

nen trong Nb02 va Ta02 c6 lien ket kim loai - k.i~ loai,

77

Cac dioxit E02 dell kho n6ng chay va ben nhiet, Khi dun n6ng trong khong khi, cac dioxit hi oxi h6a thanh E20~. Trong khi Nb02 va Ta02 deu tro v6'i cac dung dich axit va kiem, vanadi dioxit c6 tinh luang tfnh, tan trong axit va kiem, Khi tan trong dung dich axit, V02 4.0 thanh mu6i vanadyl. Vi du: V02 + 2HCl = VOCl2

Trong dung dich mrcc, ion vanadyl V02+ (j dang pentahidrat [VO(H20)S]2+mau xanh

H,o II/H,
~V
H2~I~OH2 OH2
.

trong d6 lien ker V -OH2 co d¢ dai 2.3A con lien ket V -0 co d¢ dai 1,67A va la lien ket doi. Blri vay ion V02+ c6 d¢ ben cao va khong bien d6i trong cac phan dog hoa hoc. Vf du mu6i vanadyl tac dung vci kiem 4.0 thanh ket tua hidroxit mau vang c6 thanh pharr la VO(OH)2' Ngubi ta biet duqc It mu6i cua ion v4+ rna biet nhieu mll6i cua ion V02+: VOF2 man vang, VOCl2 mall luc, VOBr2 mau vang, VOS04 mall luc... Ion VOh cling c6 kha nang tao nen
nhi.'tng phuc

chit ben nhu

]2...

[VOX4f-,

[VOX4]3-

(trong do X= F, CI, CN, SCN, ...),

[VO(C2 0

4)2

cd

ban

Khi tan trong dung dich kiem, V02 tao thanh muoi vanadit c6 mau nau va thanh pharr 18. M2V409' Vidl,l: 4V02

+ 2KOH

= K2V409 + H20

Mu6i vanadit diroc tao nen khi V02 tan trong kiem n6ng chay c6 thanh pharr 18. M2 VO] vaM4V04• Cac dioxit V02, Nb02 va Ta02 duoc tao nen khi khir cac oxit ~05 (j nhiet de?cao. Vi'dl,l: V20~ + Nb20S T~Os H2~04 H2 C

=
1200"C

2V02 2Nb02 2Ta02

+ 2m2 + H2O + co

+ H2O

+ +

1700"C

78

Tetrahalogenua

EX4
cua

Nguoi ta biet duoc hall her tetrahalogenua tetrahalogenua

v,

Nb va Ta tnr VBr4, VI4 va TaF4•

Chung la chat ran (trir VCI4 la chat long d8 bay hoi nhu TiCI4) va co mau sac khac nhau. Cac cua Nb va Ta ben voi nhiet hon, da s6 co the: thang hoa 0 -300°C. EX4 de bi thuy phan.

Cac tetrahalogenua Vi du:

Khi tac dung voi dung dich nuoc, cac tetrahalogenua d6i trang thai oxi hoa.

cua Nb va nhAt

la cua

Ta con bien

4TaCI4 2TaCI4

+ 5H20

+ 14NaOH

2TaCI3 2Na}Ta04

+ 10HCI + SNaCi + 6H20 + H2

Ta20~

Vanadi tetraflotua (rnau luc) diroc tao nen khi VCl4 lac dung voi axit flohidric, vanadi tetraclorua (rnau do-nau) duoc tong hop tnrc tiep tu nguyen t6, niobi tetraclorua (mau tfrnden) va tantan tetraclorua (rnau den) diroc dit!u che bang each dung Al khir NbCI5 va TaCI5.
Vf du: 3NbCI.~

Al

== 3NbCl4

+ AICI}

HQP CHAT CVA V(V), Nb(V) va Ta(V) Pentaoxit E10S

Vanadi pentaoxit (V 205)' niobi pentaoxit (Nb205)
canh va dinh chung. Tinh the' V20~ day

va tantan pentaoxit (Ta05)

va Ta205,

la char

dang tinh the' kho nong chay, duoc cau tao nen boi cac nhorn bat dien E06 n6i voi nhau qua

la nhiet

co mau

do da earn eon Nb205

mau trang. Duoi

d¢ nong chay va nang luong Gip tao thanh ella cac pentaoxit:

Ta.P3
-Ndne., °C ... LlG"rr> kJ/mol ... 1870 -1908

Hai oxit Nb205 va Ta205 kha tro v~ mat hoa hoc, kh6ng tan trong mroc, trong dung dich axit va kiem, chi tan trong kiern n6ng chay tao thanh niobat khi dun n6ng IAu tan trong dung dich axil.

va

lantana! con V~O.~tan it

trong nuoc (0,0079 g/I) cho dung dich mau vang nhat co tinh ax it, tan d~ trong dung dich kiem,

79

Khi tan trong dung dich kiem, V205 tao nen cac vanadat c6 thanh ph~ V205

khac nhau:

+ +

6KOI-I

= = =

2K3V04

+ 3H2O

(kali orthovanadat) V205 4KOH ~V207 + 2H2O (kali divanadat hay pirovanadat) 2K3V309 + 31-120 (kali trimetavanadat)

3V20~

+ 6KOH

Khi tan trong dung dich axit dac, V20~ tao nen mu6i chua cation dioxovanadi V 0; , vi du nhu V02N03, (V02)2S04 va V02CI04. d~u ben vci nhiet,

ca ba

pentaoxit

0 nhiet

dQ cao chung bi 1-12C, kim loai khu thanh ,

oxit thAp hay thanh kim loai,

a dieu kien thirong,

V 20S

V20~ thi hien kha nang oxi h6a, tac dung vci dung dich HCI dl).c

gicliphong khi a2~ trong dung dicn H2SO4 rae dung vOi khf S02' vci Zn: V20S + H2SO4 + S02 + 31-12804 .+ Zn
= = 2VOS04 2VOS04

H20 + 31-12

+ ZnS04

Trong phan ung thu hai, Zn co the khir tiep VOS04 (mau xanh cham) den V 2(S04)3 (mall luc) rei khir V2(S04)3 den VS04 (mall tim), trong khi do Nb20S chi co the bi khir den mu6i cua Nb3+ con T~05 kh6ng tac dung, Nhu vay, khci nang oxi h6a cua cac hop chAt cua
E(V) giarn xuong tir V dc!n Ta. Cac pentaoxit co

the dieu

che bang tac dung tnrc tiep tir nguyen t6 hoac bang each dun

n6ng cac oxit thap trong khong khi. Oxit V 20S dung

lam chat xuc tac trong san xuat axit

sunfuric va mot s6 hop chat hnu co, diroc di6u chc! bang each nhiet phan mu6i amoni vanadat: =

Vanadat, niobat

va tantalat
the c6 thanh
phan va

Vanadat, niobat va tantalat cua kim loai la nhtmg chtrt dang tinh kien true phtrc tap, NhUng hop d~u 13 chat 6 dang polime. Fe(Nb03h va Mn(Ta03)2

chat

c6 thanh phan dan gian han la ME03,

M3E04 va M4E07 (Hinh 24) con

(trong do Mia cation kim loai kiem va NH:). Da s6 cac vanadat, nhat Vi' du nhu NaNb03 c6 kien true Ideu rutin (Hlnh 23).

lit cac niobat va tantalat,

ket tinh thee kieu peropskit

Vanadat. Da s6 vanadat c6 mall, nhieu vanadat tan it trong nuoc, Thanh phlin cua vanadat trong dung dich nuoc phu thuoc v1\o n6ng dQ va pH cua dung dich. So d6 vung t6n tai
cua cac dang chAt khac nhau cua vanadat duoc bieu dien mot each nrong d6i 6 tren hlnh 25.

80

10

12 pH 14

Hinh 25. So

do thanh. phdn

dung dich-plt Clia dung dich vanadat trong nuac

Khi nOng dQ cua vanadi trong dung dich tang len, khuynh huang tao thanh polivanadat tang len. KhOng tuy thuoc vao nong d¢ cua vanadi, trong dung dich kiem manh chi t6n tai ion orthovanadat d\1 C
3

VO!-. trong dung dich axil manh chi t6n tai ion

vo;.

caa vanadi, vi du C

= 1O- M vang

= O.lM
pH

a nong d¢ nrong d6i 100

a nong
d¢ be vi

s\!' tang pH tao nen cac ion polivanadat khac nhau,

tao nen cac ion poli do thu hep lai va (] nong d¢ flit be (C<lO""M) nhiing
HV03 VO; ~HVO!-~ VO!-

ion polivanadat

khOng duqc tao nen, Nhu vay s\!'tang pH cua dung dich dan den su chuyen h6a: VO; ~
~

Qua

sa do chang
H+ +

ta thay can bang:

VO;

HV03

vo;

+ OH-

chuyen dich sang ben phai trong mOi tnrong flit axit,

o mOt pH khOng dOi, su thay dOi n6ng d¢ cua vanadi

dang cMt trong

a trong

cling lam bien dOi thanh

phan cua
nhung

dung dich, Vi du

b pH ...6, trong dung dich tao nen ion decavanadat

dung dich loang tao nen ion VO;.

Tay theo pH va n6ng dQ cua dung dich vanadat, til dung dich mroc c6 the k~t tinh nhllng orthovanadat, pyrovanadat (hay con goi la divanadat), trimetavanadat, tetrametavanadat
va decavanadat. tetrametavanadat Nhieu vanadat ke't tinh hay polimetavanadat

a dang

hidrat tinh the. Nhiing hop chat trimetavanadat, nay. thucng g~p han het lit amoni metavanadat V 10 b~;

Mu lit polime nhung theong duqc bieu dien bang cOng

thac dan gian MV03• Trong cac metavanadat

(NH4 V03) vi Ia chlit dAu d~ dieu che cac hop chAt khac cua vanadi. Anion decavanadat duqc ~u tao nen bCri cac bit dien V06 n6i voi nhau qua cac canh chung:

&-H6a h9C

va CCI • T3

81

(10 bat di~n V06 cau tao n(m anion V100:~)

oV,OO

Cac vanadat duoc tao nen khi nau chay V P_I trang kiem hay cacbonat kim loai kiem. Divanadat diroc tao nen khi k€t tinh tir dung dich ruroc duoc axit hoa cua orthovanadat. Vi du:

Arnoni tetrametavanadat tac dung voi dung dich vanadat. Vi du:

tan It trong mroc, duoc tao nen khi mu6i amoni hay amoniac

Niobat \'(1 tantulat. Cac niobat va tantalat diroc t<;LOen khi nau chay pentaoxit n trong kiem hay cacbonat kim loai kiem:

£205

Nhirng niobat va tantalat t<;LOcn 0 the chay nmr vay diroc coi la nhfrng oxit hEm hop n
trong khi mot

so niobat

va tantalat tan duoc trang mroc co chua nhtmg poiianion rieng re vi du

•

nhir H2Nb6 O~; , HNb6 017,;

San pharn thu duoc khi nau chay Ta20S trang KOH khi tan trong

ruroc tao nen kali hexatantalat:

Trong

hidrat tinh the K8TahOI~. JO t6H

co mat anion hex atantalat

Ta60~;. Nhfrng

polianion Nb60~~ va Ta60~,) deu duoc cau tao nen boi de bat dien £06 n6i voi nhau qua cac canh chung:

R2

(6 bat di~n NbOs cau 410 nlm anion Nb60~~)

Nlur vay nhirng hexaniobat

va hexatantalat

cung nhu nhirng ox it hon hop kieu NaE03

hay Na4Ez07 deu diroc cau tao nen boi cac bat dien E06 dien 100" bao g6m nhirng nguyen

rna E a trung

tam ella bat dien, Nhung

tao nen nhirng "bat

trong cac mu6i hexa tren day, cac bat dien E06 duoc sap xep theo each

tu Nb hay Ta lam cho trong

tinh th~ co mat nhimg polianion

E60~9 .
Khi axit hoa dung dich ruroc hay huyen phu trong mroc cua niobat hay tantalat hidrat cua cac pentaoxit NbzOs.xH20, Ta20yyHzO

se

thu

dtroc ket tua it tan trong nuoc, tan d~ trong dung dich HF va dung dich kiem, Do la nhtrng rna ngiroi ta thuong goi la axil niobic va

axit tantalic.

Peoxivanadat, peoxiniobat va peoxitantalat

Rat dac trirng d6i voi V(02 );.. co mau vang, V, Nb va Ta

la nhirng hop chat peoxi. Anion dipeoxivanadat

V(02 )~co mau cham

anion

tetrapeoxivanadat

tim,

aruon

tetrapeoxiniobat

Nb(02 )~- va anion tetrapeoxitantalat

Ta(02 )~- deu khong co mau, va (NH~hHV02(0:J:~.xH20 tu phan

Nguoi ta tach duoc nhirng hidrat KH1VOZ(02)2.Hl0

dung dich trung tfnh va hidrat M.1E(02)4.mH20 tir dung dich kiern manh.

trang thai ran

nhirng hop chat peox i nay deu ben. Khi tac dung voi dung dich axit, cac peoxivanadat

huy con cac peoxiniobat va peoxitantalat

Peoxivanadat, peoxiniobat

chuyen thanh peoxiaxit HE04 (hay HEOi02))'

duoc tao nen khi cac hop chat cua E(V) tac

va peoxitantalat

dung voi dung dich H202.

K1VO~

2H20Z
=

K,V02(02h

2HzO

·E205 + 8H202 + 6KOH

2K.1E(OJ4

11 H20

83

Pentahalogenua

EXs

kien thuong, trir VF~la chat long nh6t, cac pentahalogenua con lai la chat ran.Tinh the cua cac pentahalogenua dabiet d~u c6 mang luoi phan tii nen de nong chay, de sei va de tan trong dung moi hiru ca. Dl10i day la mall sac, nhiet dQ sol va nhiet dQ n6ng chay cua cac pentahalogenua da biet: Chat Mall sac Ndnc.,°C. Nds.,
Chat

o dieu

. VF~ khong mall

19,5 48,3
NbF'i trang

NbCl.~ vang

NbBr_<; dacam

Nbl.~ nall

°c

Mall ~Ac Ndnc.,oC Nds., l)C 'Chl'ft Mall sac Ndnc.,oC Nds.,

79 234
TaF_<; trang

203 247
TaCI_<;
trang

254 360
TaBr5 vang nhat

TaI~ den

97 229

210 233

280 345

496 543

°c

Phan til VF~ co dang hinh chop kep tam giac gi6ng nhu phan tir SbF_<;, phan cua hai pentaflorua con lai dang tetrame (EF5)4 con phfm_til cua cac penraclorua va pentabromua dang dime (EX5)2:

tu

CI-....' CI--

.E

CI CI __ CI-....' __ CI ,-""CI-CI ,-""Cl CI

Cac pentahalogenua

halogenanhidrit,

EX'i deu hoar dong hoa hoc, Chung co tinh chat giong cac bi thuy ph an de dang tao nen hidrat cua cac pentaoxit va axit halogenhidric:

V6i cac oxitrihalogenua

EOX~, phan trng thuy phan ciing xay ra nrong

w:

H4

Cac pentaflorua
[EFg ])-

ella V, Nb va Ta, cac pentaclorua

cua Nb va Ta e6 tht hie dung veri

(a day E=V, Nb va Ta),

florua kim loai kiem tao nen nhtrng anion phirc [EF6r va [ECI6 r (a day E=Nb va Ta).

[EF7

P-

KF 2KF

VF5

+ TaF5

K[VF61 K2[TaF7]

Tucmg W nhu v$y cac. oxitrihalogenua kiern tao nen anion phirc [VOF5]2-, X=F va CI). [EOCI4

r,

EOX) ciing tac dung veri halogenua [EOX5]2va [EOF6

kim 100:1i

f-

(a day E=Nb va Ta,

2KF
3KF Cac pentahalogenua

+ VOF3 + NbOF3

K2[VOF~] Kl[NbOF6]

dugc t6ng hqp true tiep tir cac nguyen t6 trir TaI5 duge tao nen khi

chung c~t TaBr~ v6i HI. Ngoai fa con c6 m~t s6 phucmg phap di~u ch€ khac, Vfdl,l:

NbCI5 + 5HF Ta20,5 + 5PCls Ta105 + SCI"! +SC

tao nen ell oxitrihalogenua nira.

= =

NbF~

sao
+ 5POCI3 + 5CO
con

2TaCIs
2Ta05

Khi cac kim loai tac dung voi halogen neu e6 mat khi oxi thl ngoai pentahalogenua

85

CHUaNG

cAc
Nh6m Nguyen

NGUYEN

TO NHOM VIB

VIE baa g6m cac nguyen

t6: crom (Cr), molipden (Mo) va vonfram (W).

10 vonfrarn con c6 ten goi khac 10. tungsten. Duoi day la mot so d~c diem cua cac

nguyen to nhom VIB (bang 12). Bang 12

MQt so dac diem ella cac nguyen t6 nh6m VIB

Nguyen to (E) S6thutl! nguyen IU

Cau hinh
electron nguyen nr

Nang hrong ion h6a, eV

Ban kinh nguyen til

The' dien cue chuan, V E3+/E -0,74 -0,2 -0,15

I.
I

12
16,49 16,15 17,70

13
30,95 27,13 24,08

A
1,27 1,39 1,40

Cr Mo W

24 42 74

[Ar]3d'4s' [KrJ4d55s1 lXe 14f145d46s2

6,76 7,10 7,98

Nhung nguyen nrCr,

Mo, va W co cau hinh electron kha giong nhau, nhirng obitan d

ella Cr va Mo diroc dien du mot nira s6 electron cho nen luang d6i ben. Nang hrong ion hoa cua Cr, Mo va W cho thay trong nhirng hop chat voi s6 oxi h6a IOn hon +2, cac nguyen t6

it e6 kha nang tao nen lien ket ion. ban kinh nguyen til gan voi molipden. Bai vay Mo va

Do sir co lantanoit, vonfrarn c6 Mo-W

W, ve tfnh chat, gi6ng voi nhau nhieu han so voi Cr. Tuy nhien, rmrc d¢ giong nhau trong cap kern han so voi rmrc do giong nhau trong cac cap Zr-Hf va Nb- Ta da xet tnroc day. Dieu nay duoc giai thfch Mng su gidm anh huang cua hien nrong eo lantanoit d€n kien true electron cua nguyen IU cac nguyen to khi

qi tir nh6m

IIIB den nhom IV8, VB va cuoi cung den

nh6rn VIB. Mot dan chimg cu the Hi Mo va W IUy gi6ng nh_au nhirng trong thien nhien khong ton tai chung voi nhau nen viec tach rieng chung ra khoi nhau la kh6ng thanh van de nhir trong tnrong hQ'P cua cac cap d1i n6i tren,

86

Crom co so oxi h6a d~c tnrng nhM HI.+3 va kern dac tnrng han la +6, trong khi so oxi hoa dac tnrng nhat cua rnolipden va nhat la cua vonfrarn HI.+6.

a trang

thai oxi hoa +6, cac

nguyen to nhom nay giong voi luu huynh (nh6rn VIA) 6 cung trang thai oxi hoa d6. Ngoai ra trong cac hop chat, crom, molipden va vonfram con co cac so oxi h6a 0, +1, +2, +3, +4 va +5. Mot dac diem n6i bat 6 cac nguyen t6 nh6rn nay la kha nang (<:L0en nhi1ng anion ella n poliaxit,

cAc

DON CHAT Tinh chat li hoc

Crom, rnolipden va vonfram la nhi1ng kim IO<:Li mau trang bac co anh kim. Diroi day la

nhirng hang so vat If quan trong nhat cua cluing (bang 13). Bang 13

Hang s6 vat Ii quan trong cua cac kim loai Cr, Mo va W

Kim loai (E) Cr Mo W Ndne., °C 1875 2610 3410 Nds., °C 2197 5560 5900 Nhiet thang hoa, kl/rnol 368,2 669,4 878,6

Tl
khoi 7,2 10,2

D¢ cirng

D¢ dfin dien (Hg=l) 7,1 20,2 19,3

(thang Moxa) 5 5,5 4,5

19,3

Ca ba kim loai deu nang, dan dien va nhiet tot, rat kh6 nong chay va rat kho soi,

v«

nhiet d¢ nong chay, crom, molipden va vonfram dung dau trong ba day kim loai chuyen tiep, Nhi1ng eire dai ve nhiet d¢ nong chay va nhiet thang hoa diroc giai thich bang sir tang d¢ ben cua lien k€t trong tinh the kim loai chu yeu boi so lien ket cong h6a tri duoc tao nen tir da electron d doc than ella cac nguyen nghia

tu Cr,

so toi
dan,

Mo, W. Theo If thuyet hien dai ve lien ket kim

loai, trong tinh the kim loai mci nguyen til thuong chi c6 1 hoac 2 electron

la

la

electron

electron tu do, con cac electron h6a tri con lai diroc ghep doi voi nhau tao thanh lien

ket cong hoa tri, Do kho n6ng chay nhat trong tat ca cac kim loai, vonfram duoc dung de lam sci t6c b6ng den dien, am eire va doi am-cue cua ong phat tia x; molipden co nhiet d¢ nang chay thap hon duoc dung lam chan treo sci t6c bong den dien. Crom, moJipden

va vonfrarn rat tinh khiet deu d~ che h6a co hoc nhung k.hi Ian nhirng lam tang cao d¢ cung, d¢ ben nhiet,

vet tap chat thl tr« nen cirng va gion. Vi v~y cac kim loai crom, molipden va vonfram ki thuat (cong nghiep) deu cirng. Viec dua Cr, Mo va W vao thep d¢ ben an mon va d¢ ben hoa chat cua cac loai fillip ddc hi¢f. Thep dung cu chua 3-4% Cr, thcp 87

dung

C1,l

cat gQt chua

20% W, thep crom - vonfram chua 7,5% Cr, 26% W, 0,45-0,75

% C, thep

khong ri chua 18 - 25% CI; 6 - 10% Ni; 0,14% C; 0,8% Ti, Hop kim merom dung de lam day xoan d6t n6ng trong cac 10 dien chua 10% Cr, 25% Fe, 2% Mn va 63% Ni. Thep chtra 60% Cr va 5% Mo Ia't ben vCtiaxit. HQp kim cua Mo v&i W hi v~t lieu thay the platin, Hop kim cua Al v& W dung de ch€ tao dong C(1(')tO va may bay. Hop kim sieu cling stelit chua 20-35% CI, 3555% Co, 9-15% W, 4-15% Fe, 2% C cirng gan bang kim cuong, duqc dung him dung cu ca.t
got t6c dQ nhanh. Hop kim chua 90% W, 6% Ni va 4% Cu thuang gQi la hop kim nang, c6 kh6i la ~ 18 duoc dung

ti de ngan cac tia ph6ng xa (t6t hon chi). Gan 90% luong Mo va 85% luong W san xua't trong cong nghiep la dung de ch€ cac loai thep d~c biet.

MQt hrong Ia't be cua molipden iJ trong da't tao dieu kien cho su 160 len va phat trien ella cay va cua vi khuan n6t san. Molipden cling c6 trong cac mo dong v~t, trong te bao nao cua dong v~t co vu, Chtrc nang cua molipden (j trong dong v1_\t 6 lien quan voi hoar dong cna enzim c xantinoxidazo, Trong te bao cua vi khuan c6 dinh nitc, molipden c6 trong nhttng enzim gay nen s1,1" k€t voi nito khi quyen, lien

Tfnh chat hoa hoc

o dieu kien thuong, d. ba kim loai crom, molipden va vonfrarn deu ben vnng v6i khong khf, hill am va khf eacbonic. Nguyen nhan la cac kim loai duoc bao v~ bb:i mang oxit mong va
BOi v1_\Yt ngtroi ta dung crom rna len be mat cac d6 bang kim loai d~ bao v~ cho kim loai khong bi ri.Jcp rna d6
thuong chi day 'lao khoang 0,005 mm.

hen

a tren

~ m~t. Crom kim loai dang tarn chi c6

tM

chay trong oxi

a 1800"C.

o nhiet

dQ eao va nha't Iii b dang bot, ca ba kim loai tac dung v6i. oxi, crom tac dung b

300°C thee phan rmg:

con molipden va vonfram tac dung

a tren

6000(: theo phan Ung:

2Mo (I) + 302 (k) ::: 2Mo03 (I) 2W (I) + 302 (k) ::: 2W03 (I)

M!0::: -745 kl/mol

_dHo::: -842

kl/mol

Khf flo tac dung v6i ba kim loai C1 dieu kien thuong tao thanh cac Florua CIF4, CrF5, MoF6, WF6,

ca~ halogen

khac chi tac dung khi dun n6ng.

0 nhiet

dQ cao, crom, molipden va

vonfram cling tac dung voi cac nguyen t6 khong - kim loai khac nhu N, C tao thanh cac nitrua, cacbua thuong ta hop chat kieu xam nhap c6 cac thanh phan khac nhau va

co dQ ctmg

ra't 16'0.

2000"C- 2500"C
:::

WN2

88

Ma

tren 800"C
C = MoC

w
tic dung voi hidra.

WC

Nheng cacbua nay truyen d~ cirng cho nhUng hop kim situ cimg. Ca ba kim loai khong

o nhiet

d¢ caa (600-800°C),

cram, molipden va vonfram tac dung vm mrec giai ph6ng

hidro thea cac phan ling: 2Cr Ma W

+ 3 H20 + 2H2O + 2H2O

= = =

Cr2O,

+ + +

3H2 2H2 2H2

Mo02 W02

Trang day tM' dien cue, cram, molipden va vonfram dUng truac hidro nhung malipden va vonfram dirng rat g4n hidro, Crom c6 the tan trong dung dich loang cua HCl va H2SO4, mm dliu phan irng xay ra ch$m VI kim loai dU'c;tc mang exit ben bao~; khi dun n6ng, mang oxit tan ra

va crom tan d! dang giai ph6ng khi hidro.

Vi du:
Cr

+ 2HCI

CrCI2

+ H2

, E~r2+ICr

=-O,91V

trong khi Mo va W khong tac dung vOi nhOng dung dich axit d6 VI mang oxit ~n cua chong. Cram va molipden cilng bi dung dich d~c va nguoi cua axit nitric va sunfuric th\1 dl)ng hoa va vonfram ngum ta gi6ng nhu nhom va sAt. Mu6n hoa tan nhanh cac kim loai molipden tlnrong dung hOn hop HNO, va HF.

Vid1,1:

w+

.gHF + 2HN03

= H2WFs

+ 2NO + 4H20

ell ba kim loai khOng tan trong dung dich kiem nhung tan trong hOn hop ki6m n6ng chay vai nitrat hay clorat kim loai kiem tao thanh eromat, molipdat va vonframat tl1011gUng.

Mo + Na2C03

+ 3NaNOj = Na2Mo04 + 3NaN02 + CO2

\

Trang thai thUn nhien va phllung phap dieu che'

Crom, molipden va vonfram Iii nhirng nguyen 16 tuong d6i ph6 bien trong thien nhien. Trong vo Qua molipdenit

Dat, crom chiern 6.10-3%. molipden chiem 3.10-4% va vonfram chiern 6.10-4%
l.t. Khoang v~t ehinh cua cram It! sAl cromit [Fe(Cr02hl, va vonframit [(Fe,Mn)W04]. ciia molipden ia ella vonfram III silit (CaW04) Nhting nl10c c6

t60g s6 nguyen

(Mo~),

89

giau me quang cram la Cazactan, Nam Phi, giau mo quang molipden va vonfrarn la Rai rae

An D9,

Th6 Nhi KI va Zimbabue.

Nhirng mrcc co

My, Trung quae, Nga, Chi Le va Canada. Nuoc ta c6

mot mo sa khoang cromit kha Ian 6 C6 Dinh Thanh Hoa, mo nay da diroc khai thac nhieu nam.

a mot

s6 tinh mien Trung va mien Nam mroc ta co cac mach quang

be

cua Mo va W, 1763-

Cram hin dau tien ducc nha bac hoc nguoi Phap Vocolanh 1829) dieu ch€ van nam 1797. Ten goi crom (chrome) xuat phat nghia la mau sac VIcac hop chat cua cram deu c6 mau. Nam 1778 nha hoa hoc Thuy Dien molipden
molipden

(Louis Vauquelin,

tu-

tieng Hi Lap chroma c6

Silo (Carl Scheele,

1742-1786)

ch€ hoa quang

tach duoc
tmolybdene)

oxit Mo03 va mai den nam 1790 nha h6a hoc Thuy Dien khac 13 leoma xuat phat

(Hjelm) lfin dau tien dieu che' duoc molipden kim loai khi dung than go khir MoO), Ten goi

tu

tieng Hi Lap molibdos

c6 nghia Ia chi vi khoang ·v~t

molipdenit

gi6ng voi khoang vat galen cua chi b chb khi vach len nen trang thi de lai vach den

gi6ng than chi. Nam 1781, cling nha h6a hoc Silo da: tach duoc W03 tu khoang v~t silit cua vonfram. Nam 1783 haianh em nha hoa hoc TayBan Nha Jose va Frasto (Jose va Frausto d' Elhuyar) da: tach duoc vonfram kim loai va xac dinh tinh .chat cua no, Thai Trung. caxiterit. Khi khi'.r eaxiterit bang than

05, cac khoang v~t cua n6i len

vonfram diroc goi la tungsten nghia la da nang, Trang thien nhien "da nang" thirong b Ian vci

go de

luyen thiec, "da nang" tao thanh 16p bot

tren va hap thu mot hrong thiec lam giam hieu suat luyen thiec cho nen cac nha luyen kim thai bay gia coi "da nang" la ke thu d6i vci thiec gi6ng nhir cho soi doi voi ciru non. Ten g9i

vonfram (wolji'am) xuat phat tir tieng La Tinh wolf e6 nghia la eh6 s6i va rahm la bot,
Crom kim loai diroc dieu ch€ bang phuong phap nhiet nh6m, ngiroi ta dung bot nhorn khu crom(III) ox it: Cr2

?)

+ 2Al = 2Cr + AI20)

Cram thu diroc chua 97,99% Cr va tap chat sit. Molipden va vonfram duoc dieu che bang each dung khf hidro khir MoO) va WO)

trong 10 di¢n:
MoO) W03 Mo va W thu duoc

+ 3Hi

3H2

+ 3H20 = W + 3H20
Mo

a dang

bot rst tinh khiet. San pham kim loai se kern tinh khiet han

khi thay Hz bang C hay AI. Nell dung H2 khir cac florua MoF6 va WF6, kim loai thu duoc c6 d¢ tinh khiet can cao han nira. VI la nhtrng kim 10<;1i kh6 n6ng chay nen ngiroi ta dung phuong phap ep bot kim 10<;1i va thieu k€t trong khi quyen hidro bang dong dien de tao thanh thoi
tphuang philp lUYfn kim h¢f) r6i nr thoi keo thanh soi hay can thanh la,

Trang c6ng nghiep, hrong ian kim loai crom, molipden va vonfram diroc san xuat quang diroi dang hop kim fero. Hop kim [erocrom chua 50-70% 90

tu

Cr diroc san xuat bing each

dung than ccc khir quang cromit: Fe(Cr02h

+ 4C

Fe

+ 2Cr + 4CO

Hop kim [eromolipden chua 55~60% Mo diroc san xuat bang each dung Al hay C klnr h6n hop quang molipden, ox-it slit va voi i1 trong 10 dien,

2CaMo04

+ Fe203

+ 6AI + CaO

2Fe + 2Mo + 3Ca(AI02)2

Hop kimjerovonfi'am

chLra.65~70% W duoc san xuat bang each dung than cac khir h6n

hop vonframat ngheo va oxit sit CaW04

a 1700~ 1750oC:
+ Fe203

+ 6C

2Fe

+ W + CaO

+ 6CO

HOP CHAT CVA Cr(O), Mo(O) V A W(O)

Crom, molipden

va vonfram

hexacacbonyl
Cr(CO)6' MO(CO)6' W(CO)6 1=6CllU hrnh bat dien deu

Nhtrng phan hecxacacbonyi voi nguyen nr kirn loai i1 tam va phan

,

tu

'.

tu CO 0 sau dinh:
co

oc co
E

co •

= Cr, Mo

Phan ti1 hecxacacbonyl

E(CO)6 co tinh nghichtir,

6

trong d6 nguyen ta kim loai E (0 day

va W) co cau hinh electron d va b trang thai lai h6a d2sp3:

E(O) ,d

Lien ket E -

CO

91

Trong phan tuCO

(xem tr. 71, Tap mot), c~p electron tren obitan phan
1t ~
2

tit

(j~

v6i nang

Immg cao hon nhtmg c~p electron tren obitan phan tu

va 1t ~k c6 kha Dang tao lien k€t a

cho-nhan v6i obitan lai hOO d sp3 treng clla nguyen tlr kim loai, chi ra rang trong hecxacacbonyl trong CrCl3.6H20. phan tu
'If.

v« hlnh

thee, nguyen tit kim

loai E c6 sO oxi b6a bang s6 khong nhung phuong phap nghien cuu kien true bang tia Roughen E(CO)6 nguyen

tit kim 10~ E c6 mOt dien tfch dueng dangkd,

vi du nhu dien tfch duong clla Cr trong Cr(CO)616n hdn trong crom kim loai, trong Nhu v.y ngoai lien ke"te-cho-nhan E+-CO, trong hecxacacbonyl ke"t 1t-cho E--+CO tao nen lXti nhtmg c~p electron d cua nguyen ben them. Tirong tac n-cho lam chuyen dich ~ nhtmg d~c tfnh

er2o)

va

ca

con co lien

tit kim loai v6i nhiing obitan

trong clla phan tu CO va nbb lien ket'lf nay, cac phan tu cacbonyl kim I?~ duoc

lam
co

dt) electron ve CO nhieu han so v6i su chuyen

dich mat dQ electron ve kim loai M gay nen bc1i tuong rae a cho-nhan va lien ket E-CO

ca cOng b6a

tri va ion.

khac v6i kim Ioai khOng chuyen tie'p. Thanh ph~ cua hop chA:tcacbonyl tuan thee quy Me khf hii'm do nha h6a hoc ngum Anh Situyc (N.V. Sidgwick, 1873-1952)e ra. Theo quy tAc khf d hiem, nguyen tii kim loai trong cacbonyl kim loai c6 khnynh huong nhan them mQt s6 electron ella phan tu CO nhu the' nso eM d~ duqc cA:uhlnh electron ben ella nguyen tu khf hiem trong cung chu kl. Dt sang to, chang ta xet quy lAc d6 qua hecxacacbonyl tren da.y va mQt s6

St.r tao

thanh cacbonyl kim loai la tfnh chat d~c tnrng clla hd.u he't kim loai chuyen tiep,

cacbonyl

khac:
50 electron
CUaE tirCO t6ng ceng

Cacbonyl E(CO)n Ti(OO)7 Cr(OO)6 Mo(OO)6 W(CO)6 Fe(OO):s

Khi hiern
Kr Kr Xe Rn Kr Kr

56 thn tl!
nguyen tit

22 24 42 74 26 28

2x7 2x6 2x6 2 2

x x

36 36 54 6 5 86 36 36

36 36 54 86 36 36

Ni(CO)4

2x4

Cacbonyl kim loai c6 r«t nhieu, Cluing c6 nhii'ng tfnh chA:t chung gi6ng voi hop cha:t

hftu co: tinh the c6 ~g

ItWi phan hr, khOng tan trong nuoc nhung de tan trong dung moi hctu

co. Nhieu chat c6 ap suat hoi 16'0 nen de bay hoi. Kha nang phan rmg cua cacbonyl kim loai ding rat da dang, chang tham gia nhting phan dng thay the' CO hang ph6i tu khac nhu PF:l' PCl1, NO ...

va nhtrng

phan dng oxi h6a-khir.

92

o dieu
khong mau phan huy n6 169°C va sOi
o

kien thuong, crom, molipden va vonfram hecxacacbonyl MO(CO)6 nong chay

la chit

de thang hoa trong chan khong, Cr(CO)6 nong chay trong chan

a 130-1S00C, a 17 soc.

a 148°C va sOi a ISSoc,

a dang tinh the khong a 149"C va

nguai ta lei

W(CO)6 nong chay

o nhiet

d(l cao hen, chung phan huy thanh kim loai va cacbon monooxit,

dung tinh chat nay de rna cram, molipden va vonfram len nhUng M mi)t phuc tap cua cac chi tiet may moe va nha't la rna len be! mat ben trong cua 6ng kim loai, Cac heexacacbonyl nay khong rae dung voi nu6'c va axil. Rieng MO(CO)6 rae dung v6'i

axil axetic tao thanh molipden (II) axetat. Chung tac dung v6i dung dich NaOH trong nrou hay dung dich Na trong amoniac long tao nen mu6i chua anion cacbonylat, Na2Mo(CO)5 va Na2W(CO)5' Cacbonyl kim loai va khi kim loai thuong duqc dieu che' thea hai phirong phap: tac dung true tiep llt tac dung cua mu6i hoac phirc cha't clla kim loai voi chat khu khi c6 mi)t

VI du nhu N~Cr(CO>S.

co hay

khi CO (ap suat), Nheng chat khir thuong la- nhom, magic, natri, nhorn trietyl, nhom trimetyl, khi H2 hay ca khi CO. Crom hecxacacbonyl hecxacacbonyl v6i b(lt kim loai duqc dieu che' bang tac dung cua dung dich nhom trietyl

AI(CzHsh trong ele voi huyen phu CrCl3 trong ete khi c6 mat khi CO (ap sua't cao). Molipden va vonfram hecxacacbonyl

a lip su<1"t cao

c6 tht dieu ch€ bang tac dung In!C tiep cua khl

co

(200-500 atm) khi co nil}.t sit va d6ng.

Crom dibenzen
Crom dibenzen (Cr(C~6h) co dang hlnh banh kep (sandwich) chAt
1t cC1 kim.

lil cha't dang tinh v6'i nguyen

the mau nau, n6ng chay a 284°C. Phan tir tir crom nam giita hai mi)t phi.ng song song cua

vong benzen va cac lien ket Cr-Cr co dQ dai nhu nhau (Hlnh 26). Day la bep chat kitu phirc

OCr,OH,.C

93

nangluqng

nangluqng

1'C*

-0-[D-

.rrr
-m

-D- n*

lk
1'C

--[[IJ]---[l]MO 1'CC6H6

----(ID]- n lk

Nhir dfi bier nhUng obitan 2pz cua C c6 electron doc t~a.n va vu6ng g6c vci mat phang vong benzen, thea thuyet MO,

t6

hop voi nhau tao thanh ba MOnik va ba MOn': cac MOn'k dii

dien du electron can cac MOn' d~u tr6ng (Hinh 27): Trang crom dibenzen, mot phan tit nghich tir, nguyen

tit cram c6 dtu hlnh electron 3d6:

4p

3d

Cr(O), 3d

voi MOn*
trong cua

C6H6

Cac c*p electron MOn

cua

rffi
4s
ik

C6H6

Lien ker h6a h9C giua Cr va hai yang benzen diroc thirc hien theo co che c-cho-nhan gitra cac cap electron tren .MOnlk cua hai vong benzen voi 6 obitan rrong 4s, 4p" 4py va 4pJ cua crom va thea tr6ng cua hai vong benzen. Nhu v~y nguyen

(3d x2_y2)
cua C)

,3 d].2 ,
9 MO

nhieu ram va chuyen dong trang tnrong cua 13 hat nhan nguyen hinh electron cua Kr (24 + 12 = 36).

tit (mot nguyen tit cram va 12 tiI C). Trang hop chat nay, guy dc khf hiem cling duoc tuan thea: nguyen tir Cr c6 cau

la co

co che n-cho giira

ba c~p electron d cua Cr voi cac MOn'

18 electran (6 la cua Cr

va

12

ia

a tren

Cram dibenzen dii diroc dieu che tnroc day han nira the ki khi cho thUDC thir Grinha (C6HsMgBr) tac dung voi CrCl). M¢t phirong phap dieu che khac la tac dung cua CrCl] voi benzen khi co mat nhom bot, nh6m khir cram(lII) ve cram(O) va tao thanh AlCJ3• Cling nhu cac hecxacacbonyJ kh6ng chi ve m~t If thuyet cila Cr, Mo va W. hop chat cram dibenzen co

nghia

rna ca

ve mat thirc tien.

94

Crom(II) oxit Crom(II) axil (CrO) la chat bot rnau den, co tinh II( chay, tren 100°C Ci trong khong khf bien thanh Cr203, tren 700°C Ci trong chan kh6ng phan huy thanh Cr203 va cram. C6 tfnh
bazo, oxit nay tan trong dung dich axit loang. hon hong cram.

a lOOO°C n6 bi khf hidro

khir thanh cram kim

loai. Oxit nay rat kho dieu che, diroc tao nen khi dung oxi khong khf hay axit nitric oxi hoa

Crom(II) hidro,xit
Crom{/l) hidroxit (Cr(OHh) la chat Ci dang ket tua vang nhung rAt thirong lfin tap chat
nen c6 mau hung. N6 kh6ng c6 tmh luang tinh, tan trong dung dich axit nhung khong tan trong dung dich kiem. ThS hien tinh khir manh hon exit, hidroxit d~ dang tac dung voi oxi khong khf tao thanh Cr(OH)". Khi dun nong kho dieu che

a dang

a trong

khong khi n6 phan huy thanh Cr203•

Hidroxit nay rat

tinh khiet, duoc tao nen theo phan ling: CrCI2

+ 2NaOH
OX!

= Cr(OHh

+ 2NaCI

trong dieu kien kh6ng co mat

khong khf.

MUGl crom(II)
Nguoi ta da tach ra duoc va nghien c~
CrBr2.6H20, CrS04.H20 (it tan) ki cac muoi crom(Il) sau day: CrCI1.4H10, khan c6

va [Cr(CH3COOhH:Ph

nhiet dq nong chay cao; CrF2 mall xarn, nong chay

(ket tua). Cac halogenua

1100°C, CrCI2 mau trang, n6ng chay

824°C, CrBr2 rnau trang, n6ng chay 6 842°C va CrI2 mau do, n6ng chay
r

a 795°C.
ICr2+

Cac muoi tan ft bi thuy 0,41 V.

duoc trong mroc cho ion hidrat h6a [Cr(Hp}(>f+ c6 rnau xanh lam. Muoi cromtll)

phan. Ciing nhir oxit va hidroxit, rnuoi cram(II) co tfnh khir manh, E ~r3+
Ion CrCI2·2N2H4··· Cr2+ co the tao nen nhtrng phirc chat
nhir

=-

lCr(NH3)6]CI2,

K4[Cr(CN)6],

Crom(II) clorua
Crom(lI) clorua (CrC12) khan la chat bqt mau trang, hut ~m manh, tan trong nuoc cho
dung dich mau xanh lam. Khi ket tinh tir dung dich, thu duoc hidrat CrCI2.4H20 muoi khan CrCl; C6 tinh khir rnanh, ngay trong dung dich CrCI2 de dang tac dung voi oxi khong khi bien dung dich tir mall xanh lam thanh mau luc cua ion C~+ trong nuoc: la chat

Ci dang

tinh the mau luc tham. Khi dun n6ng tren 60°C, hidrat mat b6t mroc va den 11SOC bien thanh

95

4CrCl2

+ O2 + 4HCl

4CrCl3

+ 2H20

Trong phan tfch khf, nguoi ta thirong dung dung dich nircc cua CrCl2 de http thu khi
OXI.

Ngay khi kh6ng c6 m~t oxi khong khf, ion Cr+ phan hiiy rnroc giai ph6ng khl hidro va bien thanh ion Cr":

Mu6i khan CrC!2 c6 th<!di~u ch€ bang each dun nong crom kim Ioai dong khf HO hoac dun n6ng cram triclorua (CrC!3) khan Cr 2CrCl3

a 400-540"C

a 600-700"C

trong

trong dong khl hidro:

+ +

2HCI H2

= CrC12' + H2 = 2CrCl2 + 2HCl

hoac dun n6ng cin than de lam mit mroc ella hidrat CrCI2.4HzO. Dung dich nuoc ella mu6i crom(I1) clorua diroc di~u ch€ bAng' each dung hidro hoat dl)f1g khii dung dich mu6i erom(III) c1orua. Trong thuc t€, nguoi tac6

the dung

hOn h6ng kern

tac dung voi dung dich CrCl) trong rnoi tnrong HCl:
2 CrC!3 + Zn

=' 2 CrClz + ZnCI2

Crom(lI) axe/at
, C rome II) axeta t 1f1. ch6t dang k€t tua it tan, co mau do, NaCH3COO ~c lac dung CrCl2

vm dung

duoc

tao

nen khi

cho dung dich

dich CrCl!:

+ 2NaCH3COO + H20
trong d6 Cr

== Cr(CH3COO)2.H20 + 2NaO

Day la mer trong nhUng hop ch6t

dime [Cr(CH3COO)2.H20]2'

ca.u n6i

ch€ va b~n nhttt cua Cr(II). N6 co c6u tao trang thai lai hoa d2sp3, nhOng nhorn CH3COO- la

de di~u

hai ion Cr'" lai v6i' nhau:

96

Tfnh nghich t11cua chat noi len rang 4 electron d (; m6i ion Cr]+ dii duoc ghep doi cong voi khoang each Cr -Cr (2,36A) rat be han khoang each Cr-Cr trong kim loai (2,49A) chung

to

lien ket Cr+Cr d6 la lien ket bon: mot lien ket o , hai lien ket n va mot lien ket o. Rai ion Cr]+ dung cap obitan lai h6a d1sp] tao nen lien ket c, cap obitan 3dxz va cap obitan 3dyz tao nen hai lien ket n, con cap obitan 3dx)' tao nen lien ker obitan 3d do cua crom.
x x

o. Hlnh

2B trlnh bay 51! che phil cua cac cap

Hinh 21\. S,/ chc pilll

7[

vel r5 cua ca« qip obitan Jlguyen fir 3d

Day Iii chat duoc bier dau tien (nam 1B84) trong nhfrng hop chat co lien ket bon. No c6

nghia

ve

If thuyet nhieu han

ve

mat thuc tien. Ctlu tao doc daocua hop chat lam cho n6 c6
khi d~ trong khong khf rim

tfnh nghich

tu va e6 mau do, mot m~IU it dac trung doi voi nguyen to crom. Mau do cua dime
h.IC

nay chuyen nhanh thanh mau crom(lII).

VI crom(II) bj oxi h6a thanh

HQPCHXTCDACROMom
Crom(IIl) oxit
Crom(llI) (corundum).
0.1';(

(Cr20])

dang tinh th~ c6 mall den anh kim va c6

La 119'Pchat ben nhat cua crom, n6 n6ng chay

a 2265°C

Call

tao gi6ng a-AI20J

va soi (; 3027°C. C6 d¢

cirng luang duong corundum

nen thuong duoc dung lam bot mai b6ng kim loai. Dang

va dinh

hinh la chat b¢t mall luc th~m thuong dung Hun bot mall eho san va thuoc ve. Crom(IlI) oxit tro v~ mat h6a hoc nhat la sau khi da: nung nong, n6 khong tan trong
V~I

ruroc, dung dich axit

dung dich kiem. Tfnh hrong tfnh cua Cr20] chi the hien khi mfu chay

voi kiern hay kali hidrosunfat: Cr20.1

+ 2KOH

= 2KCr02

+ H20 + 3K2S04 + 3H20

(kali cromit) Cr:P3 + 6KHS04

Phan ung thir hai
X{IY

Cr2(S04)3
voi K2~07:

ra nrong

tv nhir vay

7·H6a hoc vii 00 • T3

97

..
Khi nau chay vci peoxit kim loai kiern hoac voi h6n hop cua kiem va nitrat hay clorat kim loai kiern, no bien thanh eromat:

+ .3Na201 = 2Na}Cr04 + Na20 Cr203 + 2Na2C03 + 3NaN03 =. 2Na2Cr04 + 3NaN02 + 2eO') Cr20, + 4KOH + KCIO, = 2K2Cr04 + KCl + 2H20
Cr203 Khi dun nong v6i dung dich cua bram trong kiem hoac cua bromat trong kiem, n6 tan va bien thanh eromat:

Cong dung 160 nhatcua

Cr20, la lam nguyen lieu

de dieu

che kim loai erom.

Oxit d6

diroc dieu che bang each d6t n6ng h6n hop cua K2Cr207 thep:

va than hay hru huynh trong n6i bang

Crom(III) hidroxit
Crom(lll) polime da nhan hidroxit (Cr(OH)J) e6 cau tao va tinh chat gi6ng vci nh6m hidroxit. No HI. ket tua nhay, mall luc nhat, khong tan trang mroc va Co thanh phan bien deli. Ket tua d6 la chat

co kien
3

true lop, trang d6 nhtrng phan tir H20 va nhung nh6m OH- ph6i trf

xung quanh ian Cr +, va nh6m OH- dong thai lit cau n6i giita hai ion Crl+:

Khi d~ lau hoac dun n6ng, hidroxit nay mat heat tinh VI nhtrng lien ket Cr-OH-Cr
diroc thay the boi nhirng lien ket Cr-O-Cr.

La hop chat luang tinh di~n hinh, khi rnoi dieu ehe hidraxit tan dung dich kiem:

de dang

trong axit va

98

Ion [Cr(OH)4(H20)2r tao thanh [Cr(OH)512va h idroxocrom it. Hidroxocromit

tlnrong viet gon la [Cr(OH)4f, [Cr(OH)6]3-. Tat ca nhirng

c6 th~ ket hop them ion OHion nay diroc goi chung la

co mau luc nhat, kern ben hon hidroxoaluminat,

trong dung dich dii phan huy tao thanh ket tua Cr(OH)y

sa eli nhu
=

khi dun nong

vay ia

VI Cr(OH)3 th~ hien

tinh axit yeu han AI(OHh, no tan trong dung dich kiem c6 pH trong dung dich co pH 9- to.

11-12 trong khi AI(OH)3 tan

Crom(III) hidroxit tan khong dang long tao thanh phirc chAt hecxaammin:

'ke trong

dung dich NH3 nhirng tan de trong amoniac

Khi dun nong, crom(III) hidroxit de mat mroc bien thanh oxit. D~ dieu che crom(IIl) hidroxit

a trong

phong thi nghiem, ngiroi ta cho mot trong cac

chat NaOH, KOH, NH3, Na2C03, Na2Sz03". tac dung voi dung dich muoi crom(III). Phan irng ion chung co tM duoc viet gon Ia:

Muoi crom(IIl)
Cram(1I1) ia trang thai oxi hoa ben nhat cua crom. Nguoi ta da biet duoc nhieu muoi crom(III), nhirng muoi nay doc voi nguoi, Nhieu muoi crom(lII) cling co cau tao va tinh chat chat cua hop chat crom(III). S" gi6ng nhau nay duoc giai thich bang su g1\n nhau ve kich thuoc cua cac ion Cr3+ (0,571\) va A13+ (0,61A). Muoi crom(lIl) c6 dQ tan gan voi muoi nh6m(III), da so tan trong mroc, nhirng muoi rAt it tan la Cr2(C03h, crom-xesi). phan va mau s~c bien d6i, vf du nhu CrPC\.6H20 CrP04 va CsS04.CriS04)3.24H20 Khi ket tinh ttt dung dich, muci crom(III) thirong giong voi muoi nh6m(III) cho nen biet tinh chat h6a hoc cua nh6m(III) co th~ suy dean tfnh

a dang

(phen

tinh the! hidrat c6 thanh co mau luc,

c6 mau tim va CrP04.2H20

Muoi khan c6 cau tao va tfnh chat khac vai muci dang hidrat, VI du nhu CrCI] mau timdo tan het sue cham trong nuoc va Cr2(S04)3 mau hong tan dt it trong nuoc, trong khi
CrCl3.6H20 va Cr2(S04)'I 8H20 deu co mau tim va de tan trong mroc. Dung dich cua muoi crom(III) co .mau tim-do iJ nhiet dQ tlnrong nhung eo mau luc khi dun nong, Mau tim cua muei erom(III) trong dung dich cOng nhu trong tinh the hidrat 1a mau d~c tnrng cua ion [Cr(H20)6]3+. Muoi erom(III) co tinh thuan nr, rAt ben trong khong khi kho va bi thuy phan rnanh han muoi crom(II). Phan ung thuy phan nac thu nMt cua mu6i crom(lII) c6 the coi nhu phan rrng tao thanh phirc chat hidroxo: [Cr(H20)6f+

+ H20

[Cr(OH) (H20)5f+

+ H30+
99

vii xa han nita Iii cac phirc chat c6 the trimg hop lai, Vi du nhu trong tnrong hop cua rnu6i crorn(III) sunfat, tuy thuoc vao nhiet dQ, pH va n6ng dQ cua dung dich co the tao nen nhiing san pham polirne sau day: . H H20\ 2[Cr(OH)(H20)S]2+ + SO;...--2+

/~/OH2
+4 H2O

-----

Hi) -Cr-O-Cr-OH2 H20 /\ 0

qf\ 0
H 2+

\/

H /\ 0

OH2

2[Cr(OH)(H20)s]2+ + 3 SO;-

--

H20-Cr-0-Cr-OH2 -03S0 /\

Hl\ <:
H /\ 0 0

\sl
o~~
0

0503

+6H20

Do phan irng thuy phan, nhtrng hop cha't Cr2S:J va Cr2(C03)3 khOng the dieu che diroc bang phan ling trao -dOitrong dung dich VI trong nuoc luon luOn tao nen ket tua Cr(OH)3" Trong moi wang axit, ion if co the bi khu den Cr" bbi kern hay hOn h6ng kern nhung trong moi wang kiem co the bi H202, Ph02, nuoc clo, nuoc brorn oxi hoa d~n cromat. Vid1,l: 2CrC13 + lOKOH + 3H202

2K2Cr04 + 6KCl + 8H20

C6 ban kfnh be vii dien tich Ion, ion aJ+la mot trong nhUng chat tao phuc manh nnat, n6 co tao nen pnec chat vffi M.u h~t ph6i tir da biet. Tuy nhien, d¢ ben cua cac phirc chat crorn(III) bien dOi trong khoang gim han rong rai tllYthee ban chat ella ph6i tir va cau hlnh cua

the

phirc chat. M¢t s6 phirc chal ben

la

[Cr(NH3)6]3+,[CrX6]3~(X

la

F-,

Cl-, SCN- ,CN-), diroc

[Cr(C204hr va nlumg plnrc chat vong cang vffi axetylaxeton, vci hidroxi-8-quinolin chang han. M¢l phirc chat thuong g~p cua crom Iii mu6i Reinecke NH4[Cr(~MNH3)2].H20 dung de ket loa nhimg cation IOnhftu co va vOco.

Mu6i crom(III) thuong 4-0 nen mu6i kep gi6ng nhu muoi nhom, mot rnu6i kep dung

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