p n s 1

Cu 1. Ion coban -c phi tr vi 6 phi t trong mi phc do ho tr ph l 6. Mi phc

cng c tng cng 3 ion clorua nn c ho tr chnh l 3. Cc ion Cl- t do b phn ly khi phc

ho tan trong n-c. Cc ion Cl- khc lin kt vi ion Co3+ nn khng b phn ly do khng

phn ng vi Ag+.

(a) 3 ion Cl- t do trong [Co(NH3)6]Cl3 s phn ly khi phc ny ho tan trong n-c. V th khi phc ny ho tan trong n-c s cho tng cng 4 ion v 3 ion Cl- s phn ng vi ion Ag+:

[Co(NH3)6]Cl3(r) [Co(NH3)6]3+(aq) + 3Cl-(aq)

(b) T-ng t: 3 ion Cl- t do s kt ta vi Ag+:

[Co(NH3)5(H2O)]Cl3(r) [Co(NH3)5(H2O)]3+(aq) + 3Cl-(aq)

(c) T-ng t: 2 ion Cl- t do s kt ta vi Ag+: [Co(NH3)5Cl]Cl2(r) Co(NH3)5Cl

2+(aq) + 2Cl-(aq)

(d) T-ng t: 1 ion Cl- t do s kt ta vi Ag+: [Co(NH3)4Cl2]Cl(r) Co(NH3)4Cl2

+(aq) + Cl-(aq)

Cu 2. 1) ch c phc (c)

2) C 3 ng phn hnh hc, trong ng phn (III) c ng phn quang hc

Coen

Coen

Coen

Cl

NH3

ClNH3Cl

NH3 Cl NH3

NH3

ClNH3

Cl NH3

Cl

Coen

Cl

H3N

(I) (II) (III) Cu 3.

1) Vi [V(H2O)6]3+: V3+: 3d2, lai ho d2sp3

3d 4s 4p

d2sp3

OO OO OO OO OO OO

Vi [Cr(CN)6]

3- : Cr3+: 3d3, lai ho d2sp3

3d 4s 4p

d2sp3

OO OO OO OO OO OO

V ch c 2 hoc 3e c thn phn mc d ca ion trung tm nn c sn 2 ocbital d trng,

do khng cn thit ch r phc lai ha trong hay ngoi.

2)

(1) (2) (3) (4) (5)

Thuyt lin kt ho tr X X

Thuyt TTT X X X X X

Thuyt MO X X X X X

p n s 2

Cu 1.

1) khng c ion Cl c th b kt ta

2) hai ion

3) a)[Ni(H2O)6]Cl2: hexaaquanickel(II) chloride

b) [Cr(en)3](ClO4)3: Trisethylenediaminechromium(III) perchlorate

c) K4[Mn(CN)6]: potassium hexacyanomanganate(II)

4) (a) +2, 6 (b) +3, 6 (c)+2, 6

Cu 2.

1) Ch c (d)

2)

O N O.... ..

..

.... O N O.... ..

..

.... -(a) c th to thnh ng phn lin kt

t 2 nguyn t O, N c cc cp e ch-a lin kt

O O.... ..

..

.... O O

.... ....

....S S(b)cng c th to thnh ng phn

lin kt

O O.... ..

..

.... ON O.. .. ....

O

.. . .

N

O

. . ....

O O.. ....

.... N

O

.. ....

-..(c)

khng th to thnh

ng phn lin kt v 3 nguyn t O t-ng -ng

Cu 3.

1/ = 0 khi khng c tr-ng hoc tr-ng i xng - tr-ng hp ca ion kh t do. NLTTT = 0 khi electron chim c mc nng thp v cao bng nhau- tr-ng hp ion phc d5 tr-ng

yu v ion phc d10.

2/ Kim loi thuc phn nhm chnh khng c lp v d ang in electron. Ch c lp d trng

hoc d lp y. NLTTT = 0.

3/ Ch c d10 (NLTTT = 0), nu < P s c d5 v d10 4/ d4, d5, d6 v d7. i vi d1, d2, d3 cc electron s in vo ocbitan mc thp nn khng ph

thuc vo . i vi d8, d9, d10 cc ocbitan mc thp -c in nn cng khng ph

thuc vo .

p n s 3

Cu 1.

1)

(a) K[Ag(CN)2]: potassium dicyanoargentate(I) (b) Na2[CdCl4]: sodium tetrachlorocadmate(II) (c) [Co(NH3)4(H2O)Br]Br2: tetraammineaquabromocobalt(III) bromide

2) (a) +1, 2 (b) +2, 4 (c)+3, 6

3)

(a) K[Pd(NH3)Cl3] (b) [Pd(NH3)2Cl2] (c) K2[PdCl6] (d) [Pd(NH3)4Cl2]Cl2

Cu 2.

1) Ch c (a) v (b)

2)

(a) ng phn hnh hc

Pt

Br Br

CH3NH2

Pt

Br

Br

NH2CH3

CH3NH2NH2CH3

v

(b) ng phn hnh hc

Pt Ptv

H3N NH3

F NH3

H3N

Cl Cl

F

(c) ng phn hnh hc

Pt Ptv

NH3

F

NH3

Cl ClF

H2O H2O

Pt

NH3Cl

FH2O

v

Cu 3. i vi ion phc spin cao d4 :

NLTTT = -0,6 = -0,6(13.900 cm-1) = -8340 cm-1 i vi ion phc spin thp d4 :

NLTTT = -1,6 + P = -1,6(13.900 cm-1) + 23.500 cm-1= +1260 cm-1 Thng th-ng trng thi nng l-ng thp s bn hn. Phi t H2O khng mnh to nn

phc Cr(II) spin thp. V < P nn phc spin cao bn hn.

p n s 4

Cu 1. 1)

(a) Ion phc l [AlF6]3-. C 6phi t F- do gi l hexafluoro. Ion phc l anion do

ui ca ion kim loi (nhm) i thnh ate: hexafluoroaluminate. Al ch c bc oxy ha +3 do khng dng ch s La M. Ion d-ng cu ngoi nn gi tr-c tin v

ngn cch vi anion bng du cch: sodium hexafluoroaluminate

(b) Dichlorobis(ethylenediamine)cobalt(III) nitrate (c) Pentaaquabromochromium(III) chloride

2) [Co(NH3)5Cl]Cl2; [Co(NH3)4Cl2]Cl; [Co(H2O)(NH3)5]Cl3

Cu 2. 1) ch c (e)

2)

(a) ng phn hnh hc

Pt

Br

Pt

Br

v

Cl

Cl

Cl

Br Br

Cl2- 2-

(b) ng phn lin kt

NH3

v

2+ 2+NH3

NH3 NH3

NH3 NH3H3N

H3N H3N

H3N

NO2 ONO

Cr Cr

(c) ng phn hnh hc

v

2+ 2+NH3

NH3 NH3

NH3

NH3

H3N

H3N

H3N

Cr Cr

I

II

I

Cu 3.

Ch cn t cng thc spin c th tnh -c[Mn(CN)6]3- c 2 electron c thn v [MnBr4]

2-c 5

electron c thn (l-u Mn y c bc oxy ho khc nhau). Cu hnh electron t-ng ng

ca ion t do v ion phc vi s electron c thn nh- sau:

3d

Mn(CN)63-

4s 4p

3d

OO OO OO

4p

OO OO OOd2sp3

4s

Mn3+

Mn2+

[MnBr4]2-

3d 4s 4p

3d

OO

4p

OO OO OO

4s

sp3

p n s 5

Cu 1. 1)

(a) 6 (b) +3 (c) 2 (d) 1

2) Cu hnh Hg+: [Xe]6s14f145d10 nh-ng Cu+: [Ar]3d10. Do e c thn trong Hg+ c th cp

i to thnh Hg22+, ng-c li cu hnh Cu+ bn.

Cu 2.

PtC12H30P2Cl2 hoc Pt[P(C2H5)3]2Cl2

ng phn l:

Pt

Cl

(C2H5)3P

Cl

P(C2H5)3

cis-diclorobis(trietylphotpho)platin(II) trans-diclorobis(trietylphotpho)platin(II)

Pt

Cl(C2H5)3P

Cl P(C2H5)3

Cu 3.

1) Ion kim loi Mn3+: [Ar]d4. [Mn(CN)6]3- c 2 e c thn. Spin thp. Thng s ln

2) a/ (a) Rh3+ b/ (a)CN-

3) i vi ion phc spin cao d4 :

NLTTT = -0,6 = -0,6(13.900 cm-1) = -8340 cm-1 i vi ion phc spin thp d4 :

NLTTT = -1,6 + P = -1,6(13.900 cm-1) + 23.500 cm-1= +1260 cm-1 Thng th-ng trng thi nng l-ng thp s bn hn. Phi t H2O khng mnh to nn

phc Cr(II) spin thp. V

p n s 6

Cu 1. 1) +2; +2; +4

2) [Ar]3d6; [Ar]3d5; [Ar]3d7; [Ar]3d6; [Ar]3d6; [Ne]; [Ar]3d10; [Ar]3d9

3) (a) K4Fe(CN)6: Potassium (Kali) hexacyanoferrat (II) (b) Fe(acac)3: Tris(acetylacetonato)iron (III) (c) [Cr(en)3]Cl3: Tris(ethylenediamine)chromium (III) chloride (d) [Cr(NH3)5(H2O)](NO3)3:Pentaammineaquochromium(III) nitrate (e) [Cr(NH3)4Cl2]Cl: Dichlorotetraamminechromium(III) chloride

Cu 2. ng phn cis-trans v ng phn lin kt

Vit ng phn cis-trans theo hng ngang v ng phn lin kt theo hng dc

Pt

SCNH3N

cis-diamminbis(thiocyanato)platin(II)

SCNH3N

Pt

SCNH3N

trans-diamminbis(thiocyanato)platin(II)

NH3

NH3NCS

Pt

SCNH3N

cis-diamminthiocyanatoisothiocyanatoplatin(II)

SCN

H3N NCS

Pt

SCNH3N

trans-diamminthiocyanatoisothiocyanatoplatin(II)SCN NH3

Pt

H3N

cis-diamminbis(isothiocyanato)platin(II)

H3N

NCS

NCS

Pt

H3N

trans-diamminbis(isothiocyanato)platin(II)

NCS

Cu 3.

1) C 2 phc u c ion kim loi V3+; NH3>H2O do [V(NH3)6]3+ hp th nh sng thy -c

mc nng l-ng cao hn

2) Kim loi thuc phn nhm chnh khng c lp v d ang in electron. Ch c lp d trng hoc

d lp y. NLTTT = 0.

3) Ch c d10 (NLTTT=0= 0 nn khng ph thuc vo ) (nu

p n s 7

Cu 1.

(a) [FeCl2(H2O)4]+: dichlorotetraaquoiron(III) ion

(b) [Pt(NH3)2Cl2: dichlorodiammineplatinum(II) (c) [CrCl4(H2O)2]

-: tetrachlorodiaquochromate(III) ion (d) [Co(NH3)5Br]SO4: bromopentaamminecobalt(III) sunfate (e) [Cr(en)2Cl2]Cl:dichlorobis(ethylenediamine)chromium(III) chloride (f) [Pt(py)4][PtCl4]: tetrapyridineplatinum(II) tetrachloroplatinate(II) (g) K2[NiF6]: potassium hexafluoronickelate(IV) (h) K3[Fe(CN)5CO]: potassium pentacyanocarbonylferrate(II) (i) CsTeF5: cesium pentafluorotellurate(IV)

Cu 2.

(a) Phc Pt(II) vung phng v c 2 phi t n cng khc nhau. Mi cp phi t c th v tr k hoc i nhau nn c ng phn hnh hc. Mi ng phn ny u c th

trng chp ln nhau i vi nh ca n qua g-ng nn khng c ng phn quang hc.

(b) Ethylenediamine (en) l phi t 2 cng. Cr3+ c s phi tr 6 nn c cu trc bt din. Ba phi t 2 cng ny t-ng -ng do khng c ng phn hnh hc. Tuy nhin, ion

phc c nh qua g-ng khng trng chp ln nhau nn c ng phn quang hc

Br

NH3

Br

H3N

Pt

Br

NH3

Br

H3N

Pt(a)

trans cis

Cr(b) Cr

NN

NN

N

N NN

N

NNN

3+ 3+

khng ging vi

Cr

NN

NN

N

N3+

quay

Cu 3.

1)

Ba phc u lai ha d2sp3, phc cui lai ho dsp2

6s 6p

d2sp3

OO OO OO OO OO OO

5d(a)

(b)

(c)

(d)

4s 4p

d2sp3

OO OO OO OO OO OO

3d

6s 6p

d2sp3

OO OO OO OO OO OO

5d

5s 5p

dsp2

OO OO OO OO

4d 2) Ch c d10 (NLTTT=0 0= 0 nn khng ph thuc vo )(nu

p n s 8 Cu 1.

a) diclorotetraaquo st (III) ion b) diclorodiamminplatin (II) c) tetraclorodiaquocromat (III) ion d) tetrapyridinplatin (II) tetracloroplatinat (II) e) st (II) tetracloroplatinat (II)

Cu 2.

Cl

H3N OH

CrCrCr

Cl

Cl

HO

H3N

Cl

Cl

OH

H3N

ClClOH

OH

ClCl

HO

Cl, OH cis Cl, OH trans Cl trans, OH cis Cu 3. Theo thuyt lin kt ho tr hnh thnh phc bt din, ion kim loi trung tm s dng 1 orbital s, 3 orbital p v 2 orbital d trng lai ho vi nhau to thnh 6 orbital lai ho sp3d2 h-ng ra 6 nh ca hnh bt din.

Lin kt ca ion trung tm vi 6 phi t -c thc hin bi lin kt cho nhn gia cp electron ch-a chia ca phi t v orbital trng ca ion trung tm. Tu theo loi phi t m ion trung tm c th s dng orbital 4d, lc ny ta c phc lai ho ngoi hay s dng orbital 3d phc lai ho trong .

- Vi phc [Cr(CN)6]4 c 2 electron c thn:

24Cr: 3d5 4s1 Cr2+: 3d4

Cr2+

3d 4s 4d4p

CN CN CN CN CNCN Ta c phc lai ho trong

( 2) 2 4 8n n B

- Vi phc [Cr(H2O)6]2+ c 4 electron c thn:

24Cr: 3d5 4s1 Cr2+: 3d4

Cr2+

3d 4s 4d4p

H2O H2OH2O

H2OH2OH2O Ta c phc lai ho ngoi

( 2) 4 6 24n n B

Trong hai phc trn th phc lai ho trong bn hn v: - Phc lai ho ngoi s dng orbital 4d c nng l-ng cao hn do km bn hn. - Phc lai ho ngoi cn 1 orbital trng pha trong nn cc phi t d to lin kt trong cc phn ng thay th.

Cu 4. Khi electron b kch thch s chuyn t Et ln Ec v xy ra s hp th nh sng:

= 99,528kcal/molO

Theo thuyt l-ng t ca Planck ta c:

O

O

c hcE h h

O = 99,528kcal/mol = 99,528.4,18 = 416,027kj/mol. i vi 1 nguyn t:

22

O 23

416,027 416,0276,91.10

6,02.10N

kj/nguyn t

34 8

7 10

22 3

6,62.10 .3.102,874.10 2874.10

6,91.10 .10m m

hay o

2874A .

p n s 9 Cu 1.

a) diclorobis(etylendiamin)crom(III) clorua b) kali pentacyanocarbonylferat (II) c) cesi pentaflorotelurat (IV) d) tetracyanoaurat (III) ion e) tetraclorozincat (II) ion

Cu 2. Phc c 5 ng phn. Gi tn: Diclorodinitrodiamminplatin (IV)

Pt PtPt

PtPt

Cl

NH3

NO2Cl

H3N

NH3

NO2

NO2

Cl

H3N

NH3

NO2

NO2

H3N

NH3

H3N

H3N

Cl

Cl

Cl

Cl

Cl

NH3

NO2NO2

NO2

NH3, Cl, NO2 cisCl trans, NH3, NO2 cis NH3 trans, Cl, NO2 cis

NO2 trans, Cl, NH3 cisCl, NO2, NH3 trans

Cl

Cl

NO2

NO2

Cu 3. Theo thuyt VB, cu hnh electron ca Co3+: d6.

- Vi phc cht [CoF6]3 thun t. Do t-ng tc gia Co3+ v F

yu nn cu hnh ca Co3+ vn

gi nguyn nh- c:

Cr2+

3d 4s 4d4p

F F F F F F

Lai ho ngoi sp3d2

- Vi phc cht [Co(NH3)6]3+ nghch t. Do t-ng tc gia Co3+ v NH3 mnh nn cu hnh

electron ca Co3+ b dn li:

Cr2+

3d 4s 4d4p

NH3 NH3NH3 NH3 NH3 NH3

Lai ho ngoi d2sp3

Theo thuyt tr-ng tinh th:

- Vi phc cht [CoF6]3: P > O nn cu hnh electron ca phc

4 2

2g gt e , phc spin cao v thun

t.

- Vi phc [Co(NH3)6]3+ do P < O cc electron -c chuyn v mc nng l-ng thp c cu

hnh electron 62gt . l phc spin thp v nghch t.

Cu 4. Trong phc vi NH3, cobalt th-ng th hin s oxi ho +3 v +2.

Co3+: d6 Co2+: d7

Qua cu hnh trn ta thy trong phc bt din Co3+ c th thun t hay nghch t, cn Co2+ lun lun l thun t. V cht th hai [Co(NH3)6]Cly l cht nghch t nn n phi l phc

ca Co3+ y = 3.

V x khc y hp cht th nht [Co(NH3)6]Cl2 x = 2.

p n s 10

Cu 1. a) [Co(en)2Cl2]H2O b) [Co(NH3)4BrCl]2SO4 c) [Ni(NH3)6]3[Co(NO2)6]2

d) [CuCl2]

e) Cr(CO)6 Cu 2. Cc ng phn ca ion phc vi s phi tr 4 dng [MA2B2] m khi oxi ho n to thnh phc bt din th l cc ng phn vung phng.

Vy cc ng phn ca [Pt(NH3)2(py)2]Cl2 l:

Pt Pt

py

py

NH3py

NH3pyH3N

NH3

v

cis trans Cu 3. Cr2+: d4

-Tr-ng hp spin cao

NLO = (0,4.3 + 0,6.1) = 0,6

= 0,6(13900) = 8340cm1 - Tr-ng hp spin thp:

NLO = (0,4.4) + P = 1,6 + P

= 1,6(13900) + 23500 = 1260

Trong tr-ng hp ny < P phc spin cao bn hn v c nng l-ng thp hn.

Cu 4. a) i vi phc [Fe(CN)6]4 v > P ta c s ghp i cc in t.

Fe2+: d6

= 0, phc nghch t, spin thp.

Vi phc [Fe(H2O)6]2+ v < P cc electron phn b nh- trong nguyn t t do:

b) Phc [Fe(CN)6]

4 c = 0, phc nghch t, spin thp v phc [Fe(H2O)6]2+ c

4 6 24 4,9 B , phc thun t, spin cao.

c) i vi 1 mol phc [Fe(CN)6]4:

= 94,3kcal/mol = 94,3.103cal/mol = 94,3.103.4,18j/mol = 39,417.104j/mol

= 39,417.104.107erg/mol = 39,417.1011erg/mol. Xt i vi 1 ion phc:

1112

23

39,42.106,55.10

6,02.10N

erg/ion

B-c sng chuyn 1 electron t mc thp ln mc cao: 27 10 o

5

12

6,625.10 ( . ).3.10 ( / )3,034.10 3034A

6,55.10 ( )

hc erg s cm scm

erg

i vi 1 mol phc [Fe(H2O)6]2+:

= 29,7kcal/mol = 12,41.1011erg/mol. Xt i vi 1 ion phc:

1112

23

12,41.102,06.10

6,02.10N

erg/ion

B-c sng chuyn 1 electron t mc thp ln mc cao: 27 10 o

12

6,625.10 ( . ).3.10 ( / )9648A

2,06.10 ( )

hc erg s cm s

erg

p n s 11

Cu 1. a) [Pt(NH3)3Br]NO2 b) [Co(en)2Cl2].H2O c) [Co(NH3)5SO4]Br d) K2PtF6 e) [Cr(H2O)4Br2]Cl

Cu 2. C th c 3 ng phn hnh hc

H3N

OHNH2NO2

pyH3N

NH2OH

pyNH2OH

O2Npy

H3N

O2N

Cu 3. a) V l phc cht mt nhn nn phn t khi ca phc cht l:

195 100300

65

Trong c: 300 24%

235,5

nguyn t Cl;

300 6%1

17

phn t NH3;

300 6%1

18

phn t H2O. Cng thc phn t [PtCl2(NH3)(H2O)]

Pt Pt

H3N

OH2ClCl

H3N

H2O

ClCl

cis trans b) Cis Trans

b.u 102

c.bng 102 x x

0

298 402 396 6G kj 0 6000

8,314 298 11,27G

RTK e e

c) 3211,27 9,2 1010x

K x trans Mx

v [cis] 8101M.

Cu 4. [Fe(H2O)6]2+: 1 < P

NLO: (-(0,4.4) + 2.0,6) 1 + P = 0,41 + P = -0,4.38 + 50 = -34,8kcal/mol

[Fe(CN)6]4: 2 > P

NLO: (-(0,4.6) + 0.0,6) 2 + 3P = 2,42 + 3P = -2,4.95 + 3.50 = -78kcal/mol.

p n s 12

Cu 1. a) [Pt(NH3)3Br]NO2

b) [Co(en)2Cl2].H2O c) [Ni(NH3)6]3[Co(NO2)6]2

d) [CuCl2]

e) Cr(CO)6

Cu 2. Theo quy lut nh h-ng trans ta c: I > Cl

> NH3

+NH3

-Cl-Pt

+NH3

+Cl-Cl

Cl Cl

ClPt

Cl

NH3Cl

Pt

Cl

Cl NH3

NH3

vng da cam

Cl

giai on 2 v Cl

c nh h-ng trans ln hn NH3 nn Cl

i din vi Cl

d b th

hn to thnh ng phn cis c mu vng da cam.

-NH3

+Cl-

Pt Pt

Cl

NH3

H3NH3NH3N

H3NH3N

NH3

NH3

-NH3

+Cl-

Pt

Cl

Cl NH3vng nht

giai on 2 gii thch t-ng t nh- trn y to thnh ng phn trans c mu vng nht.

Khi tc dng vi KI cng do nh h-ng trans nn to thnh 2 sn phm c thnh

phn khc nhau, cht u khi phn ng vi KI to thnh [PtCl2I2]2 cn cht sau to

thnh [Pt(NH3)2I2] y l 2 cht c thnh phn khc nhau.

Cu 3. Theo thuyt tr-ng tinh th vi 4 phi t c th c 2 cch b tr cc phi t nh- sau: t

din v vung phng. - Vi cch b tr t din s tch mc cc orbital d v s phn b cc elctrron ca Ni2+ c cu hnh d8 nh- sau:

Theo s b tr ny, phc c 2 electron c thn nn moment t ca n l:

2 4 8 0B

iu ny tri vi thc nghim. - Vi cch b tr vung phng s tch mc cc orbital d v s phn b cc elctrron ca Ni2+ c cu hnh d8 nh- sau:

d

z2

x2 y2

xy

xz yz

d

dd

d

Theo s b tr ny, phc khng c electron c thn nn moment t ca n bng 0, ph hp vi thc nghim.

Vy cu hnh khng gian ca phc l vung phng.

Cu 4. Theo thuyt lin kt ho tr hnh thnh phc bt din, ion kim loi trung tm s dng

1 orbital s, 3 orbital p v 2 orbital d trng lai ho vi nhau to thnh 6 orbital lai ho sp3d2 h-ng ra 6 nh ca hnh bt din. Lin kt ca ion trung tm vi 6 phi t -c thc hin bi lin kt cho nhn gia cp electron ch-a chia ca phi t v orbital trng ca ion trung tm. Tu theo loi phi t m ion trung tm c th s dng orbital 4d, lc ny ta c phc lai ho ngoi hay s dng orbital 3d phc lai ho trong . - Vi phc [Cr(CN)6]

4 c 2 electron c thn: 24Cr: 3d5 4s1 Cr2+: 3d4

Cr2+

3d 4s 4d4p

CN CN CN CN CNCN Ta c phc lai ho trong

( 2) 2 4 8n n B

- Vi phc [Cr(H2O)6]2+ c 4 electron c thn:

24Cr: 3d5 4s1 Cr2+: 3d4

Cr2+

3d 4s 4d4p

H2O H2OH2O

H2OH2OH2O Ta c phc lai ho ngoi

( 2) 4 6 24n n B

Trong hai phc trn th phc lai ho trong bn hn v: - Phc lai ho ngoi s dng orbital 4d c nng l-ng cao hn do km bn hn. - Phc lai ho ngoi cn 1 orbital trng pha trong nn cc phi t d to lin kt trong cc phn ng thay th.

p n s 13

Cu 1. a) diclorotetraaquo st (III) ion

b) diclorodiamminplatin (II) c) cesi pentaflorotelurat (IV) d) tetracyanoaurat (III) ion e) tetraclorozincat (II) ion

Cu 2. S mol AgNO3 dng: 75 2

0,151000

mol

Ta c phn ng; Ag+ + Cl = AgCl

0,15 0,15

Do vy l-ng ion Cl t do l:

nCl = nAg+ = 0,15mol

3 2CrCl .6H OM 266,5

S mol Cl trong 20 g CrCl3.6H2O: 20 3 60

0,255266,5 266,5

mol

T l s mol Cl t do trong tng s mol Cl

c trong phc:

0,15 2

0,225 3

Vy c trong 3 ion gam Cl trong phc c 2 ion gam Cl

t do cn 1 ion gam Cl c

mt trong cu ni.

Cng thc ca hidrat l: [Cr(H2O)5Cl]Cl2H2O. Cu 3. + Phc [Cu(NH3)6]

2+:

S sng (s b-c sng trong 1 n v di):

1 71 15000 666 10 666cm cm nm

i vi 1 phn t:

27 10 1

12

6,62 10 . 3 10 / 15000

2,9796 10

hcE h hc erg s cm s cm

erg

i vi 1 mol: 23 12 11

1

4

6,02 10 2,9796 10 17,94 10 /

= 17,94 10 / 42,7 /

N E erg mol

J mol kcal mol

+ Phc [Cu(en)3]2+:

S sng (s b-c sng trong 1 n v di):

1 71 16400 610 10 610cm cm nm

i vi 1 phn t:

27 10 1

12

6,62 10 . 3 10 / 16400

3,257 10

hcE h hc erg s cm s cm

erg

i vi 1 mol: 23 12 11

2 6,02 10 3,257 10 19,607 10 /

= 45,6 /

N E erg mol

kcal mol

Ta thy: 2 > 1 Tr-ng phi t gy ra bi cc phi t en > NH3.

Cu 4. Cc phc [Ni(CN)4]2 v [NiCl4]

2 u c ion to phc l Ni2+.

Ni2+: 1s2 2s2 2p6 3s2 3p6 3d8

Khi to phc vi CN th gia Ni2+ v phi t CN

c t-ng tc kh mnh nn trong

tr-ng hp ny hai electron c thn AO 3d -c ghp i, ngha l xut hin mt

trng 3d. Cc trng ny s nhn cp electron t do ca phi t CN to thnh

phc [Ni(CN)4]2. Cc orbital trong tr-ng hp ny lai ho dng dsp2 vung phng.

3d 4s 4p

CN CN CNCN

vung phng

( 2) 0n n B

Phc nghch t, spin thp.

Khi to phc vi Cl do ion Cl

c bn knh ln, t-ng tc vi ion trung tm yu nn

hai electron c thn 3d vn gi nguyn. Cc ion Cl s chim cc orbital trng 4s

v 4p.

3d 4s 4p

t din

Cl Cl Cl Cl

Trong tr-ng hp ny ta c lai ho sp3.

( 2) 2 4 8 2,83n n B

0 phc thun t, spin cao.

p n s 14

Cu I: (3) 1. Hy gi tn cc hp cht sau y theo danh php quc t.

5 tn x 0,3 = 1,5

K[Ag(CN)2] Kali ixianoargentat(I)

[Co Cl2(en)2]Cl

iclorobis(etyleniamin)coban(III) clorua [Cr(en)3]Cl3

Tris(etyleniamin)crom(III) clorua [Ru(NH3)5(H2O)]Cl2

Pentaaminaquoruteni(II) clorua [Co(NH3)4Br2]2[ZnCl4]

Tetraaminibromocoban(III)tetraclorozincat(II) 2. Hy vit cng thc cc hp cht c tn gi sau y:

5 cng thc x 0,3 = 1,5

Na3[Ag(S2O3)2)] Natri bisthiosunfatoargentat(I)

[Cr(H2O)4Cl2]Cl Tetraaquoiclorocrom(III) clorua

Na3[Co(NO2)6] Natri hexanitrocobantat(III)

[Fe(H2O)5NCS]SO4

PentaaquothioxianatoNst(III) sunfat [Cr(NH3)4(NO2)2][Cr(NH3)2(NO2)4]

Tetraamininitrocrom(III) iamintetranitrocromat(III)

Cu II: (3 ) 1. 0,75

I: cis-[Cr(en)2(NCS)2]SCN II: trans-[Cr(en)2(NCS)2]SCN

0,75 . C mu xut hin khi thm ion Fe(III) chng t rng t nht 1 ion thioxianat khng

to lin kt vi ion trung tm. Cr(III) c s phi tr in hnh l 6. Do mi ion phc phi lin kt vi 2 phn t en v 2 ion thioxianat. Hai hp cht ny l ng phn hnh hc ca nhau. Hp cht I l ng phn cis. N khng c mt phng i xng do c ng phn quang hc. Hp

cht II c mt phng i xng nn khng c ng phn quang hc. 2. 2 x 0,75 = 1,5

So vi Co2+ th Ni2+ c hn 1 electron mc mt n nh t2. Ngoi ra phc ca Ni2+ c s bin dng

theo hiu ng Jan-Teller v lm gim bn ca phc t din ca Ni2+. Cu III: 1. (cu a, b, c x 3 = 3)

a,b) T gi tr momen t tnh -c s electron ch-a ghp i phc 1,2,3,4,5 ln l-t l 0, 4, 3, 3, 1.

Phc 1, 2, 3 c cu trc bt din (6 phi t)

[CoCl4]2- v Co(oaph)2 c s phi tr l 4 v khng c 6 nguyn t cho (oaph l phi t 2 cng).

Chng c th vung phng hoc t din. Phc t din s t-ng ng vi 3 electron ch-a ghp i. Cn phc vung phng t-ng ng vi 1 electron ch-a ghp i. c. Phc coban c nhiu mu v Co(II) v Co(III) u c cc obitan ch-a -c lp y electron. Electron c th chuyn t obitan c nng l-ng thp ln obitan c nng l-ng cao hn. Nng l-ng cn thit cho s chuyn electron nm trong vng nhn thy.

Tr i li, phc Zn(II) khng mu v cc obitan d -c lp y hon ton v bt k s chuyn electron no ln obitan c nng l-ng cao hn i hi nng l-ng nm ngoi vng nhn thy, do khng c mu. Ti(IV) khng c electron d, nn khng c s chuyn electron, do khng c mu. 2. (1)

Do nh h-ng trans ca Br mnh hn ca Cl

, do lin kt Pd-NH3 trong phc B

km bn hn so vi trong phc A.