1

Cu 1::
Anion NO
2
-
l phi t trong phc cht d- i y. Cho cc d kin
sau:

Cng thc
% theo khi l- ng cc
nguyn t
di lin
kt l,
0
A
Gc,
0

Kim loi
M
N C N-O
a
N-O
b
O-N-
O
O-M-
O
[MA
2
(NO
2
)
2
] 21,68 31,04 17,74 1,21 1,29 122 180
Khong cch l trong anion NO
2
-
t do l 1,24
0
A , v gc lin kt l
115,4
0
. Phi t A, cha nit v hiro; khng cha oxi. S phi tr
ca ion kim loi trong phc l 6.
1/ Hy cho bit cu to hnh hc ca NO
2
-
v vit trng thi lai ho i
vi nguyn t nit.
2/ Hy cho bit 4 cch khc nhau m ion NO
2
-
lin kt vi ion
trung tm
3/ Hy xc nh phi t A
4/ Ch ra cu trc ca phc cht.

GIAI

1/ NO
2
-
c cu to gc:
Lai ho : sp
2



2/



3/ Gi M: s nguyn t kim loi, N: s nguyn t N, x: s nguyn t
N trong phi t.
C: N = 2.x + 2
2
M : N =
2 2
1
14
04 , 31
:
68 , 21

x A
M

A
M
= 19,56.(x+1)

Khi x=2 th A
M
=58,7 g/mol, M = Ni
C : N = 667 , 0
14
04 , 31
:
12
74 , 17


V phc cha 6 nguyn t N, nn C = 0,667.6 =4.
V phi t A cha 2 nguyn t N v 2 nguyn t C, c th kt
lun rng A l etyleniamin (NH
2
-CH-CH-NH
2
).
Thnh phn phc l [Ni(NH
2
-CH-CH-NH
2
)
2
(NO
2
)
2
].
4/












Cu 2:
1. C hai ng phn vi cng thc Ni(NH
3
)
2
Cl
2
to
thnh khi cho [Ni(NH
3
)
4
]
2+
tc dng vi axit HCl c.
Dung dch ca ng phn th nht khi phn ng vi
axit oxalic s to thnh Ni(NH
3
)
2
(C
2
O
4
). ng phn
th hai khng phn ng vi axit oxalic. ng phn
no l ng phn cis, ng phn no l ng phn
trans.

2. Dng cu trc Lewis gii thch ti sao SO
3
2-
l
phi t c th to phi tr S hoc O, nh- ng NO
3
-
l
phi t ch to phi tr thng qua O.
3
giai
1. ng phn th nht l ng phn cis v c th tc
dng d dngvi nhm oxalat to thnh phc vng
cng. ng phn trans khng th to phc vng cng
vi nhm oxalat.

2.



SO
3
2-
c cc cp electron t do trn c S ln O do
c th to lin kt t S hoc t O. Trong khi NO
3
-

ch c cp electron t do O nn ch c th to lin
kt t O m thi.

Cau 3:
Khi nghin cu phc ca Co
3+
vi F
-
v vi NH
3

ng- i ta nhn thy chng cng c dng bt din
song t tnh ca chng khc nhau, c th phc
K
3
[CoF
6
] c momen t bng 4,89 B cn phc
[Co(NH
3
)
6
]Cl
3
c momen t bng 0. Tnh s e
c thn ca chng. Dng thuyt lin kt ho tr
gii thch s hnh thnh 2 phc trn.
Cho: Co(Z=27)
Gii
1.
Co(27e) cu hnh electron: 3d
7
4s
2

Co
3+
c cu hnh electron: 3d
6
4s
0

4
Momen t K
3
[CoF
6
] 4,89 B s electron ch- a
gho i l 4
Momen t [Co(NH
3
)
6
]Cl
3
0 B s electron
ch- a ghp i l 0

NH
3
thuc phi t tr- ng mnh, t- ng tc
mnh vi ion Co
3+
gy nn s dn ghp
electron s electron ch- a ghp i = 0. Hai
obitan 3d, 1 obitan 4s v 3 obitan 4p t hp vi
nhau to thnh 6 obitan lai ho d
2
sp
3
h- ng v 6
nh ca 1 hnh bt din u. 6 obitan ny tham
gia xen ph vi cc obitan cha cp electron ca
6 phn t NH
3
to nn 6 lin kt phi tr.

F
-
thuc phi t tr- ng yu, t- ng tc yu
vi ion Co
3+
, do khng c s dn ghp
electron s electron ch- a ghp i = 4. Mt
obitan 4s, 3 obitan 4p v 2 obitan 4d t hp vi
nhau to thnh 6 obitan lai ho sp
3
d
2
h- ng v 6
nh ca mt hnh bt din u. 6 obitan ny
tham gia xen ph vi cc obitan cha cp
electron ca 6 ion F
-
to nn 6 lin kt phi tr.





5
Cu 4. Momen t ca [Mn(CN)
6
]
3-
l 2,8 MB, ca
[MnBr
4
]
2-
l 5,9 MB. Hy gii thch v d on cu
trc hnh hc ca nhng ion phc ny ?
GII
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












6
Cu 5. Khi b kch thch electron - c chuyn t
mc nng l- ng thp ln mc cao hn xy ra s hp
th nh sng ng vi b- c sng . Hy tnh b- c
sng ny (theo
o
A ), bit rng nng l- ng tch mc ca
phc [Co(CN)
6
]
3
l 99,528kcal.mol
1
. Cho h =
6,62.10
34
J.s v c = 3.10
8
m.s
1
.
Gii
Khi electron b kch thch s chuyn t E
t
ln E
c
v
xy ra s hp th nh sng:
= 99,528kcal/mol
O

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

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

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 .--> Phc hp th nh sng mu
gi? V Phc c mu g?
Cu 6. Cho bit:
Nng l- ng tch
O

(kj/mol)

[CoF
6
]
3
phc bt din 156 cht thun t
[Co(NH
3
)
6
]
3+
phc bt din 265 cht nghch t
Hy xt cu trc v tnh cht ca 2 phc trn theo ph- ng php VB v
ph- ng php tr- ng tinh th.
Bit Z
Co
= 27, nng l- ng ghp i electron P = 210kj/mol.
GII
7
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 trong d
2
sp
3
Theo thuyt tr- ng tinh th:
- Vi phc cht [CoF
6
]
3

: P >
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 <
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.










8
Cu 7. Xc nh bc oxi ho ca cobalt v gi tr ca x, y
trong cc phc sau [Co(NH
3
)
6
]Cl
x
v [Co(NH
3
)
6
]Cl
y
(x khc
y) bit rng cht u l thun t, cn cht th hai l nghch
t. Bit Z
Co
= 27.
GII
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.