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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 Co
3+
nn khng b phn ly do khng
phn ng vi Ag
+
.
(a) 3 ion Cl
-
t do trong [Co(NH
3
)
6
]Cl
3
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(NH
3
)
6
]Cl
3
(r) [Co(NH
3
)
6
]
3+
(aq) + 3Cl
-
(aq)
(b) T- ng t: 3 ion Cl
-
t do s kt ta vi Ag
+
:
[Co(NH
3
)
5
(H
2
O)]Cl
3
(r) [Co(NH
3
)
5
(H
2
O)]
3+
(aq) + 3Cl
-
(aq)
(c) T- ng t: 2 ion Cl
-
t do s kt ta vi Ag
+
:
[Co(NH
3
)
5
Cl]Cl
2
(r) Co(NH
3
)
5
Cl
2+
(aq) + 2Cl
-
(aq)
(d) T- ng t: 1 ion Cl
-
t do s kt ta vi Ag
+
:
[Co(NH
3
)
4
Cl
2
]Cl(r) Co(NH
3
)
4
Cl
2
+
(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
Co
en
Co
en
Co
en
Cl
NH
3
Cl
NH
3
Cl
NH
3
Cl NH
3
NH
3
Cl
NH
3
Cl
NH
3
Cl
Co
en
Cl
H
3
N
(I)
(II)
(III)

Cu 3.
1) Vi [V(H
2
O)
6
]
3+
: V
3+
: 3d
2
, lai ho d
2
sp
3

3d
4s 4p
d
2
sp
3
OO OO OO OO OO OO

Vi [Cr(CN)
6
]
3-
: Cr
3+
: 3d
3
, lai ho d
2
sp
3

3d
4s 4p
d
2
sp
3
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(H
2
O)
6
]Cl
2
: hexaaquanickel(II) chloride
b) [Cr(en)
3
](ClO
4
)
3
: Trisethylenediaminechromium(III) perchlorate
c) K
4
[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
..
.. ..
..
.
.
.
.
O N
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/ A = 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 d
5
tr- ng
yu v ion phc d
10
.
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 d
10
(NLTTT = 0), nu A < P s c d
5
v d
10

4/ d
4
, d
5
, d
6
v d
7
. i vi d
1
, d
2
, d
3
cc electron s in vo ocbitan mc thp nn khng ph
thuc vo A. i vi d
8
, d
9
, d
10
cc ocbitan mc thp - c in nn cng khng ph
thuc vo A.

p n s 3
Cu 1.
1)
(a) K[Ag(CN)
2
]: potassium dicyanoargentate(I)
(b) Na
2
[CdCl
4
]: sodium tetrachlorocadmate(II)
(c) [Co(NH
3
)
4
(H
2
O)Br]Br
2
: tetraammineaquabromocobalt(III) bromide
2) (a) +1, 2 (b) +2, 4 (c)+3, 6
3)
(a) K[Pd(NH
3
)Cl
3
]
(b) [Pd(NH
3
)
2
Cl
2
]
(c) K
2
[PdCl
6
]
(d) [Pd(NH
3
)
4
Cl
2
]Cl
2

Cu 2.
1) Ch c (a) v (b)
2)
(a) ng phn hnh hc
Pt
Br Br
CH
3
NH
2
Pt
Br
Br
NH
2
CH
3
CH
3
NH
2
NH
2
CH
3
v


(b) ng phn hnh hc
Pt
Pt
v
H
3
N NH
3
F
NH
3
H
3
N
Cl
Cl
F

(c) ng phn hnh hc
Pt
Pt
v
NH
3
F
NH
3
Cl
Cl
F
H
2
O
H
2
O
Pt
NH
3
Cl
F
H
2
O
v

Cu 3. i vi ion phc spin cao d
4
:
NLTTT = -0,6A = -0,6(13.900 cm
-1
) = -8340 cm
-1

i vi ion phc spin thp d
4
:
NLTTT = -1,6A + 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 H
2
O khng mnh to nn
phc Cr(II) spin thp. V A < P nn phc spin cao bn hn.
p n s 4
Cu 1. 1)
(a) Ion phc l [AlF
6
]
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(NH
3
)
5
Cl]Cl
2
; [Co(NH
3
)
4
Cl
2
]Cl; [Co(H
2
O)(NH
3
)
5
]Cl
3

Cu 2. 1) ch c (e)
2)
(a) ng phn hnh hc
Pt
Br
Pt
Br
v
Cl
Cl
Cl
Br Br
Cl
2- 2-

(b) ng phn lin kt
NH
3
v
2+
2+
NH
3
NH
3
NH
3
NH
3
NH
3
H
3
N
H
3
N
H
3
N
H
3
N
NO
2 ONO
Cr
Cr

(c) ng phn hnh hc
v
2+
2+
NH
3
NH
3
NH
3
NH
3
NH
3
H
3
N
H
3
N
H
3
N
Cr
Cr
I
I I
I

Cu 3.
Ch cn t cng thc spin c th tnh - c[Mn(CN)
6
]
3-
c 2 electron c thn v [MnBr
4
]
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)
6
3-
4s
4p
3d
OO OO OO
4p
OO OO OO
d
2
sp
3
4s
Mn
3+
Mn
2+
[MnBr
4
]
2-
3d
4s
4p
3d
OO
4p
OO OO OO
4s
sp
3

p n s 5
Cu 1. 1)
(a) 6 (b) +3 (c) 2 (d) 1
2) Cu hnh Hg
+
: [Xe]6s
1
4f
14
5d
10
nh- ng Cu
+
: [Ar]3d
10
. Do e c thn trong Hg
+
c th cp
i to thnh Hg
2
2+
, ng- c li cu hnh Cu
+
bn.
Cu 2.
PtC
12
H
30
P
2
Cl
2
hoc Pt[P(C
2
H
5
)
3
]
2
Cl
2

ng phn l:
Pt
Cl
(C
2
H
5
)
3
P
Cl
P(C
2
H
5
)
3
cis-diclorobis(trietylphotpho)platin(II) trans-diclorobis(trietylphotpho)platin(II)
Pt
Cl
(C
2
H
5
)
3
P
Cl P(C
2
H
5
)
3


Cu 3.
1) Ion kim loi Mn
3+
: [Ar]d
4
. [Mn(CN)
6
]
3-
c 2 e c thn. Spin thp. Thng s A ln
2) a/ (a) Rh
3+
b/ (a)CN
-

3) i vi ion phc spin cao d
4
:
NLTTT = -0,6A = -0,6(13.900 cm
-1
) = -8340 cm
-1

i vi ion phc spin thp d
4
:
NLTTT = -1,6A + 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 H
2
O khng mnh to nn
phc Cr(II) spin thp. V A<P nn phc spin cao bn hn.

p n s 6
Cu 1. 1) +2; +2; +4
2) [Ar]3d
6
; [Ar]3d
5
; [Ar]3d
7
; [Ar]3d
6
; [Ar]3d
6
; [Ne]; [Ar]3d
10
; [Ar]3d
9

3)
(a) K
4
Fe(CN)
6
: Potassium (Kali) hexacyanoferrat (II)
(b) Fe(acac)
3
: Tris(acetylacetonato)iron (III)
(c) [Cr(en)
3
]Cl
3
: Tris(ethylenediamine)chromium (III) chloride
(d) [Cr(NH
3
)
5
(H
2
O)](NO
3
)
3
:Pentaammineaquochromium(III) nitrate
(e) [Cr(NH
3
)
4
Cl
2
]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
SCN H
3
N
cis-diamminbis(thiocyanato)platin(II)
SCN H
3
N
Pt
SCN H
3
N
trans-diamminbis(thiocyanato)platin(II)
NH
3
NH
3
NCS
Pt
SCN H
3
N
cis-diamminthiocyanatoisothiocyanatoplatin(II)
SCN
H
3
N NCS
Pt
SCN H
3
N
trans-diamminthiocyanatoisothiocyanatoplatin(II)
SCN
NH
3
Pt
H
3
N
cis-diamminbis(isothiocyanato)platin(II)
H
3
N
NCS
NCS
Pt
H
3
N
trans-diamminbis(isothiocyanato)platin(II)
NCS

Cu 3.
1) C 2 phc u c ion kim loi V
3+
; NH
3
>H
2
O do [V(NH
3
)
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 d
10
(NLTTT=0A= 0 nn khng ph thuc vo A) (nu A<P s c d
5
v d
10
)
4) Fe
2+
c cu hnh e [Ar]3d
6
. Phi t H
2
O tch km hn CN
-
. Do [Fe(H
2
O)
6
]
2+
c 4 e c thn
(spin cao) v [Fe(CN)
6
]
4-
khng c e c thn (spin thp).
Nhng kt qu ny ng nh- ng nn nh khng th d on chnh xc spin ca phc khi khng c
tr s A v nng l- ng ghp i e.

p n s 7
Cu 1.
(a) [FeCl
2
(H
2
O)
4
]
+
: dichlorotetraaquoiron(III) ion
(b) [Pt(NH
3
)
2
Cl
2
: dichlorodiammineplatinum(II)
(c) [CrCl
4
(H
2
O)
2
]
-
: tetrachlorodiaquochromate(III) ion
(d) [Co(NH
3
)
5
Br]SO
4
: bromopentaamminecobalt(III) sunfate
(e) [Cr(en)
2
Cl
2
]Cl:dichlorobis(ethylenediamine)chromium(III) chloride
(f) [Pt(py)
4
][PtCl
4
]: tetrapyridineplatinum(II) tetrachloroplatinate(II)
(g) K
2
[NiF
6
]: potassium hexafluoronickelate(IV)
(h) K
3
[Fe(CN)
5
CO]: potassium pentacyanocarbonylferrate(II)
(i) CsTeF
5
: 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. Cr
3+
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
NH
3
Br
H
3
N
Pt
Br
NH
3
Br
H
3
N
Pt
(a)
trans cis

Cr
(b)
Cr
N
N
N
N
N
N N
N
N
N
N
N
3+ 3+
khng ging vi
Cr
N
N
N
N
N
N
3+
q
u
a
y


Cu 3.
1)
Ba phc u lai ha d
2
sp
3
, phc cui lai ho dsp
2

6s 6p
d
2
sp
3
OO OO OO OO OO OO
5d
(a)
(b)
(c)
(d)
4s 4p
d
2
sp
3
OO OO OO OO OO OO
3d
6s 6p
d
2
sp
3
OO OO OO OO OO OO
5d
5s 5p
dsp
2
OO OO OO OO
4d

2) Ch c d
10
(NLTTT=0 0A= 0 nn khng ph thuc vo A)(nu A<P s c d
5
v d
10
)

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
H
3
N
OH
Cr
Cr
Cr
Cl
Cl
HO
H
3
N
Cl
Cl
OH
H
3
N
Cl
Cl
OH
OH
Cl Cl
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 sp
3
d
2

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:
24
Cr: 3d
5
4s
1
Cr
2+
: 3d
4

Cr
2+
3d
4s 4d 4p
CN CN
CN CN CN CN

Ta c phc lai ho trong
( 2) 2 4 8 n n B = + = =
- Vi phc [Cr(H
2
O)
6
]
2+
c 4 electron c thn:
24
Cr: 3d
5
4s
1
Cr
2+
: 3d
4

Cr
2+
3d
4s 4d 4p
H
2
O
H
2
O H
2
O
H
2
O
H
2
O H
2
O

Ta c phc lai ho ngoi
( 2) 4 6 24 n 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 E
t
ln E
c
v xy ra s hp th nh sng:
= 99,528kcal/mol A
O

Theo thuyt l- ng t ca Planck ta c:
O
O
c hc
E h h v

A = A = = =
A

A
O
= 99,528kcal/mol = 99,528.4,18 = 416,027kj/mol.
i vi 1 nguyn t:
22
O 23
416, 027 416, 027
6, 91.10
6, 02.10 N

A = = = kj/nguyn t

34 8
7 10
22 3
6, 62.10 .3.10
2,874.10 2874.10
6, 91.10 .10
m 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 Pt Pt
Pt
Pt
Cl
NH
3
NO
2
Cl
H
3
N
NH
3
NO
2
NO
2
Cl
H
3
N
NH
3
NO
2
NO
2
H
3
N
NH
3
H
3
N
H
3
N
Cl
Cl
Cl
Cl
Cl
NH
3
NO
2
NO
2
NO
2
NH
3
, Cl, NO
2
cis Cl trans, NH
3
, NO
2
cis NH
3
trans, Cl, NO
2
cis
NO
2
trans, Cl, NH
3
cis
Cl, NO
2
, NH
3
trans
Cl
Cl
NO
2
NO
2

Cu 3. Theo thuyt VB, cu hnh electron ca Co
3+
: d
6
.
- Vi phc cht [CoF
6
]
3
thun t. Do t- ng tc gia Co
3+
v F

yu nn cu hnh ca Co
3+
vn
gi nguyn nh- c:
Cr
2+
3d
4s 4d 4p
F F
F F
F
F

Lai ho ngoi sp
3
d
2
- Vi phc cht [Co(NH
3
)
6
]
3+
nghch t. Do t- ng tc gia Co
3+
v NH
3
mnh nn cu hnh
electron ca Co
3+
b dn li:
Cr
2+
3d
4s 4d 4p
NH
3
NH
3
NH
3
NH
3
NH
3
NH
3

Lai ho ngoi d
2
sp
3
Theo thuyt tr- ng tinh th:
- Vi phc cht [CoF
6
]
3
: P > A
O
nn cu hnh electron ca phc
4 2
2g g
t e , phc spin cao v thun
t.
- Vi phc [Co(NH
3
)
6
]
3+
do P < A
O
cc electron - c chuyn v mc nng l- ng thp c cu
hnh electron
6
2g
t . l phc spin thp v nghch t.
Cu 4. Trong phc vi NH
3
, cobalt th- ng th hin s oxi ho +3 v +2.
Co
3+
: d
6

Co
2+
: d
7

Qua cu hnh trn ta thy trong phc bt din Co
3+
c th thun t hay nghch t, cn
Co
2+
lun lun l thun t. V cht th hai [Co(NH
3
)
6
]Cl
y
l cht nghch t nn n phi l phc
ca Co
3+
y = 3.
V x khc y hp cht th nht [Co(NH
3
)
6
]Cl
2
x = 2.

p n s 10

Cu 1. a) [Co(en)
2
Cl
2
]H
2
O
b) [Co(NH
3
)
4
BrCl]
2
SO
4

c) [Ni(NH
3
)
6
]
3
[Co(NO
2
)
6
]
2

d) [CuCl
2
]


e) Cr(CO)
6

Cu 2. Cc ng phn ca ion phc vi s phi tr 4 dng [MA
2
B
2
] m khi oxi ho n to thnh
phc bt din th l cc ng phn vung phng.
Vy cc ng phn ca [Pt(NH
3
)
2
(py)
2
]Cl
2
l:
Pt Pt
py
py
NH
3
py
NH
3
py H
3
N
NH
3
v
cis trans

Cu 3. Cr
2+
: d
4

-Tr- ng hp spin cao
NLO = (0,4.3 + 0,6.1)A = 0,6A
= 0,6(13900) = 8340cm
1

- Tr- ng hp spin thp:
NLO = (0,4.4) A + P = 1,6A + P
= 1,6(13900) + 23500 = 1260
Trong tr- ng hp ny A < P phc spin cao bn hn v c nng l- ng thp hn.
Cu 4. a) i vi phc [Fe(CN)
6
]
4
v A > P ta c s ghp i cc in t.
Fe
2+
: d
6


= 0, phc nghch t, spin thp.
Vi phc [Fe(H
2
O)
6
]
2+
v A < 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(H
2
O)
6
]
2+
c
4 6 24 4, 9 B = = = , phc thun t, spin cao.
c) i vi 1 mol phc [Fe(CN)
6
]
4
:
A = 94,3kcal/mol = 94,3.10
3
cal/mol = 94,3.10
3
.4,18j/mol = 39,417.10
4
j/mol
= 39,417.10
4
.10
7
erg/mol = 39,417.10
11
erg/mol.
Xt i vi 1 ion phc:
11
12
23
39, 42.10
6,55.10
6, 02.10 N
c

A
= = = 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 s
cm
erg

= = = =
i vi 1 mol phc [Fe(H
2
O)
6
]
2+
:
A = 29,7kcal/mol = 12,41.10
11
erg/mol.
Xt i vi 1 ion phc:
11
12
23
12, 41.10
2, 06.10
6, 02.10 N
c

A
= = = 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(NH
3
)
3
Br]NO
2

b) [Co(en)
2
Cl
2
].H
2
O
c) [Co(NH
3
)
5
SO
4
]Br
d) K
2
PtF
6

e) [Cr(H
2
O)
4
Br
2
]Cl
Cu 2. C th c 3 ng phn hnh hc
H
3
N
OHNH
2
NO
2
py
H
3
N
NH
2
OH
py
NH
2
OH
O
2
N
py
H
3
N
O
2
N

Cu 3. a) V l phc cht mt nhn nn phn t khi ca phc cht l:
195 100
300
65

=
Trong c:
300 24%
2
35, 5

= nguyn t Cl;
300 6%
1
17

= phn t NH
3
;
300 6%
1
18

=
phn t H
2
O.
Cng thc phn t [PtCl
2
(NH
3
)(H
2
O)]
Pt
Pt
H
3
N
OH
2 Cl Cl
H
3
N
H
2
O
Cl Cl
cis trans

b) Cis Trans
b.u 10
2

c.bng 10
2
x x
0
298
402 396 6 G kj A = + =
0
6000
8,314 298
11, 27
G
RT
K e e
A


= = =
c) | |
3
2
11, 27 9, 2 10
10
x
K x trans M
x

= = = ~


v [cis] ~ 810
1
M.

Cu 4. [Fe(H
2
O)
6
]
2+
: A
1
< P

NLO: (-(0,4.4) + 2.0,6) A
1
+ P = 0,4A
1
+ P = -0,4.38 + 50 = -34,8kcal/mol
[Fe(CN)
6
]
4
: A
2
> P

NLO: (-(0,4.6) + 0.0,6) A
2
+ 3P = 2,4A
2
+ 3P = -2,4.95 + 3.50 = -78kcal/mol.

p n s 12

Cu 1. a) [Pt(NH
3
)
3
Br]NO
2

b) [Co(en)
2
Cl
2
].H
2
O
c) [Ni(NH
3
)
6
]
3
[Co(NO
2
)
6
]
2

d) [CuCl
2
]


e) Cr(CO)
6

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

> Cl

> NH
3

+NH
3
-Cl
-
Pt
+NH
3
+Cl
-
Cl
Cl
Cl
Cl
Pt
Cl
NH
3
Cl
Pt
Cl
Cl
NH
3
NH
3
vng da cam
Cl

giai on 2 v Cl

c nh h- ng trans ln hn NH
3
nn Cl

i din vi Cl

d b th
hn to thnh ng phn cis c mu vng da cam.
-NH
3
+Cl
-
Pt
Pt
Cl
NH
3
H
3
N H
3
N
H
3
N
H
3
N
H
3
N
NH
3
NH
3
-NH
3
+Cl
-
Pt
Cl
Cl
NH
3
vng 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 [PtCl
2
I
2
]
2
cn cht sau to
thnh [Pt(NH
3
)
2
I
2
] 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 Ni
2+

c cu hnh d
8
nh- sau:

Theo s b tr ny, phc c 2 electron c thn nn moment t ca n l:
2 4 8 0 B = = =
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
Ni
2+
c cu hnh d
8
nh- sau:
d
z
2
x
2

y
2
xy
xz yz
d
d
d
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
sp
3
d
2
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:
24
Cr: 3d
5
4s
1
Cr
2+
: 3d
4

Cr
2+
3d
4s 4d 4p
CN CN
CN CN CN CN

Ta c phc lai ho trong
( 2) 2 4 8 n n B = + = =
- Vi phc [Cr(H
2
O)
6
]
2+
c 4 electron c thn:
24
Cr: 3d
5
4s
1
Cr
2+
: 3d
4

Cr
2+
3d
4s 4d 4p
H
2
O
H
2
O H
2
O
H
2
O
H
2
O H
2
O

Ta c phc lai ho ngoi
( 2) 4 6 24 n 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 AgNO
3
dng:
75 2
0,15
1000
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 2
CrCl .6H O
M 266, 5 =
S mol Cl

trong 20 g CrCl
3
.6H
2
O:
20 3 60
0, 255
266, 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(H
2
O)
5
Cl]Cl
2
H
2
O.
Cu 3. + Phc [Cu(NH
3
)
6
]
2+
:
S sng (s b- c sng trong 1 n v di):
1 7
1
15000 666 10 666 cm cm nm v


= = = =
i vi 1 phn t:
27 10 1
12
6, 62 10 . 3 10 / 15000
2, 9796 10
hc
E h hc erg s cm s cm
erg
v v

A = = = =
=

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

A = A = =
=

+ Phc [Cu(en)
3
]
2+
:
S sng (s b- c sng trong 1 n v di):
1 7
1
16400 610 10 610 cm cm nm v


= = = =
i vi 1 phn t:
27 10 1
12
6, 62 10 . 3 10 / 16400
3, 257 10
hc
E h hc erg s cm s cm
erg
v v

A = = = =
=

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

A = A = =

Ta thy: A
2
> A
1
Tr- ng phi t gy ra bi cc phi t en > NH
3
.
Cu 4. Cc phc [Ni(CN)
4
]
2
v [NiCl
4
]
2
u c ion to phc l Ni
2+
.
Ni
2+
: 1s
2
2s
2
2p
6
3s
2
3p
6
3d
8

Khi to phc vi CN

th gia Ni
2+
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 dsp
2
vung phng.
3d
4s 4p
CN CN CN CN
vung phng

( 2) 0 n 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 sp
3
.
( 2) 2 4 8 2,83 n 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 Cl
2
(en)
2
]Cl

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

Tris(etyleniamin)crom(III) clorua
[Ru(NH
3
)
5
(H
2
O)]Cl
2

Pentaaminaquoruteni(II) clorua
[Co(NH
3
)
4
Br
2
]
2
[ZnCl
4
]
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
Na
3
[Ag(S
2
O
3
)
2
)]
Natri bisthiosunfatoargentat(I)
[Cr(H
2
O)
4
Cl
2
]Cl
Tetraaquoiclorocrom(III) clorua
Na
3
[Co(NO
2
)
6
]
Natri hexanitrocobantat(III)
[Fe(H
2
O)
5
NCS]SO
4

PentaaquothioxianatoNst(III) sunfat
[Cr(NH
3
)
4
(NO
2
)
2
][Cr(NH
3
)
2
(NO
2
)
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 Co
2+
th Ni
2+
c hn 1 electron mc mt n nh t
2
. Ngoi ra phc ca Ni
2+
c s bin dng
theo hiu ng Jan-Teller v lm gim bn ca phc t din ca Ni
2+
.
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)
[CoCl
4
]
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.
Tri 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-NH
3
trong phc B
km bn hn so vi trong phc A.

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