Trng i Hc Bch Khoa TP HCM

Chng trnh:

Bui n tp chuyn : Ha v c
Ni dung

1. Cu trc thi mn ha v c
2. Kinh nghim n thi mn ha v c
3. Gii mt s cu trong thi nm 2012
4. Gii p thc mc
1. Cu trc thi mn ha v c

Oxy ha kh
Dy Latimer
Gin Frost

Phc cht

Danh php
 2. Kinh nghim n thi mn ha v c

_ Lm cu d trc, cu kh lm sau.
_ c nhiu ln, gch di s liu, d kin bi.
_ Ch yu cu bi: tm ci g, chn cu ng/sai.
_ Lm k cc nm trc (c bit l nm 2012).
3.Gii mt s cu trong thi nm 2012
3.1. Oxy ha- kh:

3.1.1. Gin Latimer:

_Cch thit lp gin : Sp xp cc ion, cht theo

chiu gim dn s oxi ho.

_Cc dng ton thng gp.

 Cho 2 gin sau pH=0 (nm trn) v pH=14 (nm di):

0.386
0.253
HSO4 S2O62
x1
H 2 SO3
x2
S2O32
0.6
S
0.144
H 2S
0.158 x3

0.936 0.576 0.742

SO42 SO32 S2O32 S
0.476
HS

Cu 1: Tnh x1, x2, x3:

Tnh x1: 0, 253.1 x1.1 0,158.2 x1 0.569

Tnh x3: 0,158.2 + x3.4 = 0,386.6 => x3 = 0,5
Tnh x2 tng t. p n 0.4
Cu 2: Thit lp gin Latimer gm cc s oxi ho ca
lu hunh l +6, +4, +2, 0, -2 pH=8.
Lp gin (sp xp theo chiu s oxi ho gim dn):
SO42
a1
SO32
a2
S2O32
a3
S
a4
HS
a.Tnh cc gi tr a1, a2, a3, a4:
0,059 []
Ta dng cng thc: = 0 +
[]
V d:
SO42- + H2O + 2e SO32- + 2OH-
0,059 1
a1 = -0,936 + log = 0,582
2 (106 )^2

Tnh cc gi tr cn li: a2= -0,045, a3= -0,221, a4= 0,653.

Cu 3. Da vo gin Latimer pH=0, dng no
ca lu hunh b d ly trong mi trng axit.

Trn nguyn tc khi s oxi ho gim th gim, nu

t ngt tng ln th dng b d li.
2 2
Vy pH=0 th 2 6
S O , S 2 3 b d li.
O
Cu 4: Ta thy dng S2O32 b d ly trong mi trng axit
nhng li khng b d ly trong mi trng baz. Nh vy
khi pH tng t 0 n 14 s c 1 gi tr pH m ti
S2O32 chuyn t b d ly sang khng b d ly. Tnh gi tr
pH .
Gii: Mun cho hp cht hay ion khng b d ly ngha l
pha bn tri phi bng pha bn phi:

H2SO3 + 2H+ + 4e S2O32- + 3H2O

S2O32- + 6H+ + 4e 2S + 3H2O

0,059 + 2 0,059 + 6
0,4 + log = 0,6 + log
4 4
=> pH = 3,4
 3.1.2. Gin Frost:

pH=8 lp gin Frost:

Dng oxi ho Tnh ton Gi tr E.n

-2 0 0
0 2.0,653 1,306
+2 2.(-0,211) + 1,306 0,884
+4 2.(-0,045) + 0,884 0,794
+6 2.(-0,582) + 0,794 -0,37
V gin :
E.n

Dng oxy ha
Cu 5: Da vo gin xc nh dng d ly, nh
hp, sn phm cui ca qu trnh O-K l cc yu
cu thng gp.

p n:
_D li: +4 v 0
_Nh hp: +2
_Sn phm cui ca qu trnh O-K l +6.
3.2 Phc cht
So snh thuyt lin kt ha tr, thuyt trng tinh th
v thuyt MO

Thuyt lk ha Thuyt trng Thuyt orbital

tr tinh th phn t (MO)
C ch Lk cho nhn: Lc y tnh Coi phc cht
to - cp e t do in gia e (cng nh cc hp
thnh ca phi t ca phi t v cht n gin) l
phc cho nguyn t ht thng nht bao
cht - orbital trng trung tm. gm nguyn t
ca nguyn t trung tm v phi
trung tm lai t
hacho
 So snh thuyt lin kt ha tr, thuyt trng tinh th
v thuyt MO

Thuyt lk ha tr Thuyt trng tinh th Thuyt orbital

phn t (MO)
u -m t n gin, -gii thch c ph -khc phc
im c th lk trong hp th (mu sc) ca nhc im
phc cht (s phi phc cht ca thuyt
tr v cu hnh -tm ra dy ha quang trng tinh th
khng gian) ph
-gii thch c t -gii thch c
tnh nguyn nhn gy ra t
tnh ca phc (phc
spin thp, spin cao).
 So snh thuyt lin kt ha tr, thuyt trng tinh th
v thuyt MO
Thuyt lk Thuyt trng tinh th Thuyt orbital
ha tr phn t (MO)
Nhc -khng Do coi lk kl-phi t l lk ion , -khng ch
im gii thch ch ch orbital nguyn t ca kh nng to
c mu kim loai m b qua orbital thnh cc MO
sc ca nguyn t ca phi t nn gp phn lk
phc cht nhng hn ch: khng gii
-khng cp n lk gii thch c ph
thch khng tha ng bn hp th ca
ca ca cc phc to thnh ch phc cht (mu)
yu nh lk cng ha tr
-khng gii thch c bn cht
dy ha quang ph.
 3.2.1. Thuyt lin kt ha tr

Lai ha trong
(d2sp3)
S phi tr 6 bt din
Lai ha ngoi
(sp3d2)

T din
S phi tr 4 (sp3)
Hnh vung
(dsp2)
3.2.2. Thuyt trng tinh th

Trng bt din
Trng t din
Trng hnh vung
 Cu hnh phc c>o>T (cng
cht ligand, cng ion
trung tm)
Thng s tch
nng lng in tch Ion c in tch ln
Bn cht ion ln v ngc li
trung tm
Kch Bk ion ln ln v
thc ngc li
Dy ph ha hc
I-<Br-<Cl-<SCN-<F-<OH-<C2O42-<H2O<NCS-<py<NH3<en<ipy<NO2-<CN-<CO
 Nghch
>P
t
phc spin
T Thun
thp
tnh t
<P phc
spin cao Thun t
 Ph hp th

Electron: d nng
lng thpd
nng lng cao
(chuyn i d-d)

Ph hp th
electron
3.2.3. Thuyt orbital phn t (MO)

[Ngun] Ha hc v c, tp 3, Hong Nhm, NXB Gio dc

 3.2.4. Bi tp

1. S dng cc thuyt gii thch cc cu to ca

phc cht, tnht, nng lng,mu sc.

2. bn ca phc cht v tan ca kt ta.

3. Tnh oxi ha kh ca phc cht.

 S DNG CC THUYT GII THCH
CC CU TO CA PHC CHT,TNHT,
NNG LNG, MU SC
1.Gii thch cu to,t tnh ,nng lng n nh trng tinh th v mu
sc ca phc 63 (Bit (kJ/mol) ca CoF63- = 155 vo
P(kJ/mol) = 250,5)
Bi Gii_ Theo thuyt ha tr
3+ trng thi t do

4s 4p 4d
3d
F F F F F F
3+ trng thi lai ha

3d 4s 4p 4d
 Lai ha sp3d2 => phc bt din
C electron c thn =>thun t

_Theo thuyt trng tinh th

Cu hnh e ha tr ca Co3+ l 3d6,
* CoF63- c < P nn cu hnh Co3+ l d4d2
Phc spin cao, thun t
 =155kj/mol=155*103*6.023*1023=9.335*1028
Ta c E=hc/
=>=0.77m => hp th as =>phn x as xanh l=>phc
mu xanh l

Tnh nng lng n nh trng tinh th

Phc spin cao CoF63-:
E = 4(-2/5) + 23/5 = 2/5
=2/5155 = -62kJ/mol
Theo thuyt M.O
Cu hnh:
(
)

1. Trong s 18 electron ha tr c 12
eclectron in vo 6 MO v 6
eclectron cn li in vo MO
v MO
2. CoF63- l phc spin cao (ms =
+2), thun t
3. Nng lng tch trng tinh th
= E*d - E0d
4. Phc ny c th c mu do 0d
cha electron v *d cn trng. (
ion CoF63- :mu xanh l)
 BN CA PHC CHT V TAN CA
KT TA
Hy chng minh (bng php tnh c th) tan ca AgCl trong
dung dch amoniac 1.0 M cao hn so vi tan trong nc ct.

tan ca AgCl trong nc ct: S1 [ Ag ] TAgCl 1,30.105 M

Tnh tan ca AgCl trong dung dch amoniac 1,0 M.

AgCl + 2NH3 Ag(NH3)2+ +
B: 1,0
Cb: 1,0 - 2x x x K 1,5.107 1,7.1010 2,55.103
x2
K 2,55.10 3
S2 = x = 4,59.10-2 M
(1,0 2 x) 2
Suy ra: S 2 4,6.103
S1
 CuBr l mt cht t tan trong nc (pT = 7,4).
(a) Hy tch th tch nc ti thiu cn dng ha tan hon ton
1 gam CuBr.
Ion Cu+ to phc vi amoniac theo cc phn ng sau:
Cu+ + NH3 [Cu(NH3)]+ lg1 = 6,18
[Cu(NH3)]+ + NH3 [Cu(NH3)2]+ lg2 = 4,69
(b) Hy tnh th tch dung dch amoniac 0,1 M ti thiu cn dng
ha tan hon ton 1 gam CuBr.
(c) Biu thc tnh tch s tan iu kin ca CuBr nh sau:
T' ([Cu ] [Cu(NH 3 )] [Cu(NH 3 ) 2 ] ) [Br - ]

Hy tnh gi tr T' ca dung dch thu c phn (b).

 a. CuBr Cu+ + Br-
C:
S [Cu ] 10-7,4 2,00.104
Mt khc: 1
S 2,00.10 4
143,35V
V = 34,9 lit
b. CuBr Cu+ + Br- pT = 7,4
Cu+ + NH3 [Cu(NH3)]+ lg1 = 6,18
[Cu(NH3)]+ + NH3 [Cu(NH3)2]+ lg2 = 4,69
C: [Br-] = [Cu+] + [Cu(NH3)+] + [Cu(NH3)22+ ] (1)
[NH3] + [Cu(NH3)+] + 2[Cu(NH3)22+] = 0,1 (2)
Gi s: [Cu(NH3)22+] >> [Cu+], [Cu(NH3)+]
(1) [Br-] = [Cu(NH3)22+]
(2) [NH3] + 2[Cu(NH3)22+] = 0,1
 C:
[Cu(NH 3 ) 2 ] [ Br - ] [ Br - ]
1, 2 2
- 2
-7,4
[Cu ][NH 3 ] [Cu ](0,1 - 2[Br ]) 10 - 2
-
(0,1 - 2[Br ])
[ Br ]
[Br ] = 0,05 ; [Cu+] = 8.04.10-6 ; [Cu(NH3)2+] =
[Br-] = 0,05
[Cu(NH 3 ) 2 ] 0,05 4
[NH 3 ] 9. 16.10
1, 2 [Cu ] 8.04 10 1010,87

[Cu(NH3)+] = 1[Cu+][NH3] =106,188.04 10-6 9.16

10-4 =0.011

KTGT: tha mn;

 TNH OXI HA KH CA PHC CHT
Cho bit:
Qu trnh kh o(V)
Au3+ + 3e Au 1,50
Cho bit hng s khng bn ton phn ca cc phc AuX4- c cc
gi tr nh sau :
[AuCl4-] = 2.10-21,3 [AuBr4-] = 1.10-31,5
[Au(SCN)4-] = 1.10-42
Tnh th kh chun 250C ca cc bn phn ng kh sau
a) AuCl4- + 3e Au + 4Cl-
b) AuBr4- + 3e Au + 4Br-
c) Au(SCN)4- + 3e Au + 4SCN-
T cc kt qa thu c rt ra mi lin h gia kh nng
oxy ha ca Au(III) vi bn ca phc cht ca Au(III).
 Bi gii

AuCl4- Au3+ + 4Cl- Kkb[AuCl4-] = 2.10-21,3

lg[ Au 3 ]
0,059
0
Au 3 3
Au
K
kb, [ AuCl ] ktc ta c [Cl-]=1M
[ Au 3 ] 4 .
[Cl ] 4

lg( 2.10 21,3 ) 1,08V

0,059 0,059
0 0 lg K 1,5
[ AuCl ] Au 3 3 kb, [ AuCl ] 3
4 4
Au Au
 Tng t, ta c:

0,059 0,059
[0AuBr ] 0Au
3 lg K kb,[ AuBr ] 1,5 lg( 1.10 31,5 ) 0,881V
Au
4
Au
3 4
3

0,059 0,059
0
[ Au ( CN ) 4 ]
0
Au 3
lg K kb,[ Au (CN ) ] 1,5 lg(1.10 42 ) 0,674V
Au Au
3 4
3

Nhn xt, phc vng(III) cng bn th tnh oxy ha ca vng(III)

cng yu.
4. Gii p thc mc