1.1 Tnh nng cn bng ca ion Ag+ trong dung dch AgNO3 10-3M.

Khi
a) Thm NH3 vo 100 ml dung dch AgNO3 10^(-3) M n C(NH3) =1M (Gi s th tch dung dch
khng thay i)
b) Dung dch m NH3 v NH4Cl c pH = 9 vi tng nng NH3 v NH4Cl l 0,28M
Bit s to phc bi Ag+ v NH3 c cc hng s bn tng nc l 10^(3,32) v 10^(3,92); KNH3 =
10^(-4,76). B qua s to phc hydroxo
1.2
a) c tn cc ion phc sau: [Zn(H2O)4]2+, [Zn(NH3)4]2+, [Zn(CN)4]2-, [Zn(OH)4]2-. Cho bit c
im v t tnh v hnh dng ca cc ion phc trn
b) Xc nh s electron c thn v nng lng lm bn bi trng phi t ca ion phc
hexaaqua st (II) v ion hexaxianoferat (II). T hy so snh bn, tnh oxy ha, tnh kh ca
hai ion phc trn. Bit nng lng ghp i ca nguyn t trung tm l 210 kJ/mol, thng s
tch nng lng ca nguyn t trung tm ng vi phi t H2O l 124 kJ/mol, ng vi phi t
CN- l 395 kJ/mol
BI GII
1.1
a) Trong dung dch c cc cn bng sau:
H2O H+ + OH- KW
NH3 + H2O NH4+ + OH- Kb = 10-4,76
Ag+ + NH3 AgNH3+ 1 = 103,32 = k1
AgNH3+ + NH3 Ag(NH3)2+ k2 = 103,92
Ta c:
KbCb >> KW nn b qua s phn ly ca nc
CNH3 >> CAg+ v 2 >> 1 nn trong dung dch ch yu tn ti dng Ag(NH3)2+
___NH3 + H2O NH4+ + OH- Kb = 10-4,76
C (M) 1
[ ] (M) 1 x___x___x
x21x=104,76

Gi s x << 1 x = 10-2,38M
S proton ha NH3 khng ng k

____Ag+ + 2NH3 Ag(NH3)2+ 2 = 107,24

C (M) 10-3 ___1

[ ] (M) y___ 1 2(10-3 y)___ 10-3 - y

103yy(0,998+2y)2=107,24
Gi s y << 10-3 y = 5,78.10-11M

b) Trong dung dch m ta c:

pH=pKa+lg[NH3][NH+4]
[NH3] = 10-0,24[NH4+] (1)
[NH3] + [NH4+] = 0,28 (2)
Gii (1) v (2) ta c [NH3] = 0,102M v [NH4+] = 0,178M
CNH3 >> CAg+ v 2 >> 1 nn trong dung dch ch yu tn ti dng Ag(NH3)2+
___Ag+ + 2NH3 Ag(NH3)2+ 2 = 107,24
C (M) 10-3___0,102
[ ] (M) z ___0,102 2(10-3 z)___10-3 - z
103zz(0,1+2z)2=107,24
Gi s z << 10-3 z = 5,75.10-9M

1.2
a) [Zn(H2O)4]2+ : ion tetraaqua km (II)

[Zn(NH3)4]2+: ion tetraamin km (II)

[Zn(CN)4]2-: ion tetraxianozincat (II)
[Zn(OH)4]2-: ion tetrahidroxozincat (II)
Zn2+: *Ar+3d10 khng c e c thn nghch t
Zn2+ c phi tr 4, khng c obitan d trng lai ha sp3 phc ca Zn2+ c cu trc dng t
din

b) Nhn xt
- Phi tr 6 Phc bt din
- p dng thuyt trng tinh th
P < CN-: [Fe(CN)6]4- c phc spin thp
P > H2O: *Fe(H2O)6+2+ c phc spin cao

- Khng c e c thn__________________________ C 4 e c thn

- Ebn = 6.(25)+2P= 528 kJ/mol _______ Ebn = 4.(25)+2.(35) = - 49,6 kJ/mol

[Fe(CN)6]4- bn hn *Fe(H2O)6+2+

[Fe(H2O)6]2+ c tnh kh v tnh oxy ha mnh hn *Fe(CN)6+4-