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Chng XIII

Phc cht

Mt s nh ngha: Khi xt tnh cht ca cc nguyn t nhm A v hp cht ca chng, chng ta gp mt s phn ng to phc, v d: X(OH)2 + 2NaOH = Na2[X(OH)4] X- Pb, Sn SnO2+ 4HCl = SnCl4 + 2H2O SnCl4 + 2HCl = H2[SnCl6] 2Al + 2NaOH +6H2O = 2Na[Al(OH)4] + 3H2

- Cht c kh nng to phc l cc kim loi Al, Pb, Sn chng u l cc kim loi nhm A, nhng c c im l c cc obitan trng cc phn lp 3d hoc 4d hoc 5d. - Kh nng to phc ca cc kim loi chuyn tip ln hn nhiu so vi cc kim loi nhm A v chng c nhiu obitan ho tr v c nhiu obitan trng v c m in ln hn cc kim loi kim v kim th nn rt c kh nng nhn cp electron v l cht to phc tt.

1. Phc cht: * nh ngha: Phc cht l hp cht phi tr, m phn t ca n cha ion phc. Ion phc bao gm mt nguyn t hay ion c gi l nhn trung tm, bao quanh n l cc nguyn t, phn t hay ion lin kt vi n c gi l ligand hay phi t. S phi t thng ln hn ho tr ca nhn trung tm.

V d 1: Phn t phc cht Na[Al(OH)4] cha ion phc [Al(OH)4]- , Al3+ l ion to phc v lin kt vi n l 4 nhm OH-

OHAl OH-

HO

HO

V d 2: Phn t phc cht [Co(NH3)6]Cl3 cha ion phc [Co(NH3)6]3+, trong ion to phc l Co3+ lin kt vi 6 phi t NH3 V d 3: [Ni(CO)4], cht to phc l nguyn t Ni lin kt vi 4 phi t CO Nh vy phc cht c th l cation, anion hay nguyn t nh v d 1, 2 v 3 xt trn.

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* Cu to ca phc cht: Trong cu to ca phc cht ngi ta phn ra cu ni v cu ngoi. Cu ni c gi l cu phi tr c vit trong du ngoc vung bao gm cht to phc v cc phi t. Cc ion nm ngoi v ngc du vi cu ni to nn cu ngoi. V d 1: Cc phc c cu to: [Co(NH3)6]Cl3 [Co(NH3)5Cl]Cl2 cu ni cu ngoi

+ Cu ni ca phc c th l cation V d 2: [Al(H2O)6]Cl3, [Zn(NH3)4]Cl2, [Co(NH3)6]Cl3, [Pt(NH3)4]2+, [Ni(NH3)6](NO3)2 + Cu ni c th l anion: V d 3: H2[SiF6], K2[Zn(OH)4], K3[PbI4], Na3[AlF6], [Ni(CN)4]2-,[PtCl4]2-

+ Cu ni c th l phn t trung ho v in, khng phn ly trong dung dch: V d: [Co(NH3)3Cl3], [Ni(CO)4], [B(NH3)F3] trong trng hp ny phc cht khng c cu ngoi + Nhn trung tm c th l ion nh Co3+, Al3+, hay l nguyn t kim loi nh Co, Al, Zn, Ni. + Phi t c th l cc anion nh OH-, F-, Cl-, Br-, I-, CN-, NO2-, CO32-, C2O42-, hay c th l phn t nh NH3, H2O, CO, NO,hay phn t hu c nh NH2CH2CH2NH2,(NH2)2CO

2. S phi tr ca nhn trung tm: - S phi tr ca nhn trung tm l s lin kt ca nhn trung tm lin kt vi cc phi t. V d: s phi tr ca nhn trung tm Co3+, Al3+ trong cc v d trn u bng 6. - a s nhn trung tm c s phi tr bin i ph thuc vo bn cht ca cht to phc, ca phi t, s oxi ho, bn cht ca dung mI, ph thuc vo nng , nhit v cu ngoi. -V d: + Ni2+ c s phi tr l 6 trong ion [Ni(NH3)6]2+ hoc c s phi tr l 4 trong ion phc [Ni(CN)4]2+ Mt s nhn trung tm c s phi tr khng i nh Cr3+, Co3+, Pt4+ v u c s phi tr l 6. Hin nay cha c l thuyt hon chnh tin on chnh xc s phi tr ca nhn trung tm, nhng s phi tr thng gp l 4 v 6.

2+

3. Dung lng phi tr ca phi t: - Dung lng phi tr ca phi t l s lin kt ca mt phi t lin kt vi nhn trung tm. V d: OH-, Cl-, I-, F-, NH3, CN-trong cc v d trn c dung lng phi tr bng 1. - Phi t c dung lng phi tr bng 1 l phi t n cng. - Phi t c dung lng phi tr ln hn 1 l phi t a cng, v d: etileniamin H2N-CH2-CH2-NH2 c dung lng phi tr bng 2 th hin trong phc sau:

H2C

H2 N Cu

H2 N

CH2

H2C

N H2

N H2

CH2

Mi phn t etileniamin c 2 nguyn t lin kt vi nhn trung tm, tc l gp i so vi cc phi t n cng. Khi phi t a cng lin kt vi nhn trung tm s to thnh vng v phc cht cha phi t a cng c gi l phc cht vng.

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4. Cch gi tn cc phi t thng gp: CH3COO-: axetat H2O: acva : xiano NH3: ammoni CN clo CO: cacbonyl Cl- : nitrit NO: nitrozin NO2- : CO32- : cacbonat NH2CH2CH2NH2: etylendiamin hydroxyl (NH2)2CO: cacbamid OH- : sunfit SO32-: C2O42- : oxalat

5. Cch gi tn cc phc cht: * Phc cht trung ho: ch gm mt t, bt u bng s v tn ca phi t, sau l tn ca nhn trung tm vi ch s di, tri (trong trng hp nhiu nhn) V d:
[Al2Cl6] hexaclodialuminum [Ni(CO)4] tetracacbonylnickel [Co2(CO)8] octacacbonyldicoban * Phc cht cation: bao gm s v tn ca phi t v tn ca nguyn t to phc [Ag(NH3)2]+ - cation diamin bc (I) [Mn(H2O)6]2+ - cation hexaacva mangan (II) [Hg2(H2O)2](NO3)2 - nitrat diacva di thuy ngan (II+)

* Phc cht anion: bao gm s v tn ca phi t v tn ca nguyn t to phc+ at v ch s s oxi ho [BF4]- Tetrafloborat (III) ion [Fe(CN)6]3- - hexaxinferrat (III)- ion K2[HgI4] Tetariot thuy ngan (II) kali

Thuyt lin kt ho tr gii thch lin kt ho hc trong phc cht 1. Thuyt lin kt ho tr: Thuyt axit-baz ca Lewis ra i nm 1927. - Axit l phn t nhn cp electron ho tr cn Baz l phn t cho cp electron ho tr, v d:
F F B F F

+ :NH3 = F B
F

NH3

- Da vo thuyt lin kt ho tr gii thch lin kt ho hc trong cc hp cht phc cht. - Theo thuyt ny: + Lin kt to thnh trong phc cht l lin kt chonhn gia cp electron t do ca phi t v obitan trng ca nhn trung tm. Lin kt cho-nhn l lin kt cng ho tr v mi lin kt cho-nhn ng vi mt v tr phi tr (mt lin kt ). + Kt hp vi khi nim lai ho ca Pauling, nhng obitan trng phi l nhng obitan lai ho ca nhn trung tm mi c th tip nhn c nhng cp electron ca phi t

V d 1: S to thnh ion phc [Co(NH3)6]3+, ion Co3+ kt hp vi 6 phn t NH3 to thnh cation phc hnh bt din nh 6 lin kt cho-nhn gia cc electron t do ca cc phn t NH3 v cc obitan lai ho trng d2sp3 ca ion Co3+ (3d6) c to thnh do s lai ho ca 2 obitan 3d, 1 obitan 4s v 3 obitan 4p.

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d2sp3
3d Co3+ 4s 4p

NH3 NH3 NH3 NH3 NH3 NH3

S lai ho d2sp3 ca cc obitan ho tr ca ion Co3+, s lai ho ny c c do 4e c thn 3d phi ghp cp gii phng 2 obitan trng, y c gi l s lai ho trong. Loi phc ny cha t hoc khng cha cc electron c thn so vi nhn trung tm trng thi t do, nn c gi l phc cht spin ghp cp hoc phc cht spin thp hoc phc cht obitan trong. Ion [Co(NH3)6]3+ khng c electron c thn nn n c tnh nghch t

V d 2: Ion phc [CoF6]3- c hnh thnh hi khc so vi ion [Co(NH3)6]3+, trong trng hp ny nhn trung tm l Co3+ c lai ho sp3d2, tc l cc obitan 3d lp trong khng tham gia lai ho m xy ra s lai ho ca 1 obitan 4s, vi 3 obitan 4p v 2 obitan 4d. y l s lai ho ngoi

3d6

4s

sp3d2 4p

4d

Su phi t F- a ra su cp electron ho tr lin kt vi 6 obitan lai ho ca nhn trung tm. Su obitan ny hng ti 6 nh ca bt din u do phc cht c hnh bt din u. Phc cht ny to thnh c s tham gia ca cc obitan d ho tr bn ngoi nn c gi l phc cht obitan ngoi (phc cht spin cha ghp cp hoc phc cht spin t do). Phc cht ny vn gi c s electron t do ca nhn trung tm, n c tnh thun t.

Mt s dng lai ho obitan thng gp v cu trc hnh hc tng ng

S phi Dng lai tr ho 2 sp 4 4 6 6 sp3 dsp2 d2sp3 sp3d2 Cu hnh ca V d phc cht Thng [Cu(NH3)2]+, [Ag(NH3)2]+, [Ag(CN)2]-, T din [Zn(NH3)4]2+, [Be(OH)4]2Vung phng Bt din Bt din [PtCl4]2-, [Ni(CN)4]2[Co(NH3)6]3+, [Fe(CN)6]3-, [CoF6]3-

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2. u nhc im - n gin, d hiu, cho php gii thch mt cch nh tnh lin kt ca phc cht, gii thch tnh thun t v nghch t ca chng. - Khng gii thch c mt s tnh cht ca phc cht nh tnh cng hng t, tnh d hng, tnh cht quang hc cng nh mu ca cc phc cht.

Thuyt trng tinh th Thuyt trng tinh th do hai nh Bc hc Vt l Bethe v Van Vleck ra nm 1933 gii thch tnh cht ca cc cht dng tinh th, mi n nm 1950 n mi c p dng vo phc cht ca cc

kim loi chuyn tip

Thuyt trng tinh th da vo cc gi thuyt sau y: - Phc cht c hnh thnh l nh vo lc ht tnh in gia cht to phc v phi t - Kho st v tr ca cc obitan d ca nguyn t trung tm (cht to phc) v kho st s bin thin nng lng ca 5 obitan d di tc dng ca in trng ca cc phi t. Thuyt ny coi cc phi t l cc in tch im hay phn t lng cc, chng c sp xp trong khng gian sao cho nng lng y gia cc in tch l cc tiu

1. S tch cc obitan ho tr d ca nguyn t trung tm di tc dng ca trng cc phi t trong ion phc tm mt u Cu trc hnh hc ca ion phc tm mt u:
L5 z L3 y L2 A L4 L6 x L1

L3 L2 L1 dx2-y2

L5 L2 L4 L3 L1 L6 dz2

L5 L2 L1

L4

L3

L5

L6
L3

dzx

L2 L1 d xy

L4

L3

dzy

L4

L6

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- Nguyn t trung tm c 5 obitan ho tr d, trng thi t do cc obitan ny c nng lng bng nhau - Khi cc ion phc tin li gn to lin kt th do lc ht tnh in gia cc phi t vi cc obitan d ca nhn trung tm, nng lng ca cc obitan d tng ln. Tuy nhin do tng tc gia phi t vi nhn khng ging nhau nn nng lung ca cc obitan ny tng ln khng u:

+ Hai obitan dz2 v dx2-y2 ca nguyn t trung tm hng trc tip n cc phi t nn di tc dng ca in trng cc phi t nng lng ca hai obitan ny tng ln mnh. + Ba obitan cn li dxy, dxz, dzy nh hng gia cc phi t do tng tc gia cc obitan ny vi cc phi t km hn nn nng lng ca chng tng ln t hn

- Di tc dng ca in trng su phi t trong ion phc tm mt xy ra hin tng tch cc obitan ho tr d ca nguyn t trung tm: thnh hai mc khc nhau: eg v t2g, mc eg c nng lng cao hn mc t2g

E
E2 0,6 o o 0,6

eg o
0,4o

C E0

o 0,4
E1

Nng lng trung Nng lng trung bnh ca cc OAbnh ca 5d obitan d trong trng tinh th

t2g

S tch nng lng ca cc obitan d trong trng tinh th

- Hiu s gia hai mc nng lng eg v t2g c gi l thng s tch, k hiu l o = E2- E1 - Mc nng lng trung bnh ca 5 obitan d trong phc cht nm khong gia hai mc eg v t2g, coi mc ny nng lng ny bng 0, tc l: 3E1 + 2E2 = 0 Ta c: E1 = -0,4o v E2= 0,6o

2. S phn phi cc electron ho tr d trong ion phc bt din u: - Nguyn l vng bn: cc electron chim trc ht cc obitan c nng lng thp - Nguyn l Pauli: mi obitan cha nhiu nht 2e - Quy tc Hund: i vi cc obitan c cng nng lng th cc e c phn b vo cc obitan sao cho s e c thn vi spin song song l ln nht. Tuy nhin i vi phc cht s tun theo quy tc ny phc tp hn so vi nguyn t, c bit i vi ion c t 4, 5, 6 v 7 e trn obitan d.

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eg t2g eg t2g eg t2g eg t2g

eg

o<P

t2g eg t2g eg t2g eg t2g

o>P

P l nng lng cn thit cp i electron, l nng lng cn thit chuyn hai electron c thn vi s lng t t spin ms cng du t hai obitan cng nng lng vo cng mt obitan. + Nu P > o th e th t v nm s khng ghp i t2g v s ghp i tn nhiu nng lng hn + Ngc li nu P < o th s ghp i t2g xy ra d dng hn. + Nu s electron ho tr d ca nguyn t trung

tm ln hn 7 th khng c s khc nhau gia hai trng hp trn. Ion phc c cu hnh electron: t2g6eg2 (8e); t2g6eg3 (9e)

To phc spin cao

To phc spin thp

3. Nng lng lm bn bi trng tinh th Ws i vi ion phc tm mt vi s electron d ln hn 1 th nng lng lm bn bi trng tinh th c tnh theo cng thc sau: Ws = (0,4n1 - 0,6n2)o Trong : n1- s electron trn cc obitan t2g n2- s electron trn obitan eg Nng lng lm bn bi trng tinh th khng phi l nng lng lin kt trong ion phc, m n ch ng gp vo nng lng lin kt. Nng lng ny m cng ln th phc cng bn.

Bng 1: Nng lng lm bn bi trng tinh th ca cc ion

phc tm mt u

4. Cc yu t nh hng n thng s tch: Gi tr ca thng s tch c xc nh da vo ph hp th ca phc cht. - N ph thuc vo bn cht ca nguyn t trung tm, vo cu trc ca ion phc to thnh v bn cht ca phi t. - m in v kch thc ca phi t: ln khi phi t c m in ln, kch thc nh, v khi phi t c th li gn nhn hn, to nn in trng mnh, do tng tc mnh vi cc obitan d ca nguyn t trung tm. V d cc ion halogenua to ra gi tr thng s tch gim dn theo th t: F- - Cl- - Br-- I-, c ngha l theo th t tng dn ca kch thc phn t

+ phn cc ca phi t: Phi t c phn cc ln v kch thc cng nh s to ra ln. Hoc phi t c 1 cp e ho tr cha tham gia lin kt th kh nng xm nhp vo cc obitan d ca nhn trung tm d hn so vi cc phi t c nhiu cp e ho tr, v d H2O to ra thng s tch km hn so vi NH3 + Tuy nhin bng thc nghim cho thy kh nng to ra thng s tch ca cc phi t khc nhau i vi cng mt nhn trung tm tng dn theo th t sau y: I- < S2- < Br- < Cl- < OH- < F- < H2O < SCN- < NH3 < NO2- < CN- < CO Trng phi t yu trng phi t trung bnh trng phi t mnh

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Cc phi t mnh thng to ra cc phc spin thp, cn cc phi t yu thng to ra cc phc spin cao. Cc phi t gy ra thng s tch ln nh CO, CN- v trong chng tn ti lin kt cng ho tr, chng c kh nng to lin kt vi nhn trung tm. - in tch ca ion trung tm cng nh hng n thng s tch: Ion c in tch ln c ln, v ion c in tch ln c kh nng ht mnh phi t v n v phi t c tc dng mnh ln cc obitan d ca nhn. V d cc ion phc Cr2+ v Co2+ c thng s tch nh hn cc ion phc Cr3+ v Co3+ - Kch thc ca ion trung tm ca nh hng n thng s tch: Ion phc ca Cr3+ c thng s tch nh hn ion phc tng t Rh3+

5. Hng s in ly v hng s bn ca ion phc: Trong dung dch phc cht thng b phn ly thnh cu ni v cu ngoi: [Ag(NH3)2]Cl [Ag(NH3)2]+ + ClSau ion phc li b phn ly thnh ion trung tm v cc phi t. i lng c trng cho s in ly ca ion phc c gi l hng s in ly:
[Ag(NH3)2]+ [Ag(NH3)]+ + NH3; K1 =
+ [Ag (NH 3 )] .[NH 3] + [Ag (NH 3 )2 ]

[Ag(NH3)]+ Ag+ + NH3

K2 =

[Ag]+ .[NH3] [Ag(NH3 )]+

Tng ca hai phn ng trn ta c: [Ag(NH3)2]+ Ag+ + 2NH3 Hng s in ly ca qu trnh phn ly: + ]2 = K .K K = [Ag ].[NH3+ 1 2

[Ag(NH) ]
3 2

Hng s in ly K cng ln khi ion phc phn ly cng mnh, ngha l ion phc cng km bn. Bi vy hng s in ly K ch bn ca ion phc trong dung dch cn c gi l hng s khng bn k hiu l Kkb. a s cc ion phc l cht km in ly, qu trnh phn ly chuyn dch mnh v pha tri ca qu trnh to phc. ch kh nng to phc ca nguyn t trung tm, ngi ta dng hng s cn bng ca qu trnh ngc vi qu trnh phn ly, gi l hng s bn Kb v l nghch o ca hng s khng bn: Kb= Kkb-1

Hng s bn tng v hng s bn tng nc: Qu trnh to thnh v qu trnh phn ly ca ion phc xy ra theo tng nc, ng vi mi nc c mt hng s bn v hng s khng bn, i vi ion phc [Ag(NH3)2]+: [Ag(NH ) ] K =
+ 3 1b

Ag+

+ NH3 [Ag(NH3

)]+
K2b =

[Ag + ].[NH 3 ]

[Ag(NH3)]+ + NH3 [Ag(NH3)2]+;

[Ag(NH3 )2 ]+ [Ag(NH3 )]+ [NH3 ]

Trong trng hp tng qut hng s bn tng cng ca mt ion phc bt k c tnh bng cng thc sau: nb = (K1.K2Kn)b