Transcript Esperienza 5 - I blog di Unica

Esperienza 5!
Cu2+(aq) + SO42-(aq) + 5 H2O(l)!
CuSO4·5H2O
[Cu(H2O)6]2+!
[Cu(H2O)5(NH3)]2+!
K1
+ NH3
+ NH3
[Cu(H2O)4(NH3)2]2+! + NH3
[Cu(H2O)3(NH3)3]2+! + NH3
[Cu(H2O)6]2+!
K2
!
K3
!
K4
!
!
!
[Cu(H2O)5(NH3)]2+ + H2O!
[Cu(H2O)4(NH3)2]2+ + H2O
[Cu(H2O)3(NH3)3]2+ + H2O
[Cu(H2O)2(NH3)4]2+ + H2O
β
+ 4 NH3
[Cu(H2O)2(NH3)4]2+ + 4 H2O
Aspetti termodinamici!
K1
!
[Cu(H2O)6]2+
+ NH3
[Cu(H2O)5(NH3
K2
!
+ NH3
)]2+
K3
!
[Cu(H2O)4(NH3)2]2+ + NH3
!
[Cu(H2O)3(NH3)3]2+ + NH3
!
[Cu(H2O)6]2+
!
!
!
[Cu(H2O)5(NH3)]2+ + H2O
K1 =
[Cu(H2O)4(NH3)2]2+ + H2O
[Cu(H 2 O) 4 (NH 3 ) 22+ ]
K2 =
[Cu(H 2 O)5 (NH 3 ) 2+ ][NH 3 ]
!
[Cu(H2O)3(NH3)3]2+ + H2O
K4
!
[Cu(H2O)2(NH3)4]2+ + H2O
[Cu(H 2 O) 62+ ][NH 3 ]
[Cu(H 2 O)3 (NH 3 ) 32+ ]
K3 =
[Cu(H 2 O) 4 (NH 3 ) 22+ ][NH 3 ]
[Cu(H 2 O) 2 (NH 3 ) 24+ ]
K4 =
[Cu(H 2 O)3 (NH 3 ) 32+ ][NH 3 ]
!
β
+ 4 NH3
[Cu(H 2 O)5 (NH 3 ) 2+ ]
[Cu(H2O)2(NH3)4]2+ + 4 H2O
4
[Cu(H 2 O) 2 (NH 3 ) 24+ ]
β=
= K1 ⋅ K 2 ⋅ K 3 ⋅ K 4 = ∏ K i
2+
4
[Cu(H 2 O) 6 ][NH 3 ]
i =1
Esperienza 5!
Aspetti termodinamici!
Cu2+(aq) + SO42–(aq) + 5 H2O(l)!
CuSO4·5H2O
[Cu(H2O)6]2+!
[Cu(H2O)5(NH3)]2+!
k1
+ NH3
+ NH3
[Cu(H2O)4(NH3)2]2+! + NH3
[Cu(H2O)3(NH3)3]2+! + NH3
[Cu(H2O)6]2+!
k2
!
k3
!
k4
!
!
!
[Cu(H2O)5(NH3)]2+ + H2O!
[Cu(H2O)4(NH3)2]2+ + H2O
[Cu(H2O)3(NH3)3]2+ + H2O
[Cu(H2O)2(NH3)4]2+ + H2O
β
+ 4 NH3
[Cu(H2O)2(NH3)4]2+ + 4 H2O
Esperienza 5: Composti di CuII!
[Cu(H2O)6]2+ + en !
[Cu(H2O)4(en)]2+ + en !
k1
!
k2
!
[Cu(H2O)4(en)]2+ + H2O!
[Cu(H2O)2(en)2]2+ + H2O!
[Cu(H2O)6]2+ + 4Cl– !
[CuCl4]2– + 6H2O !
[Cu(H2O)6]2+ + 2OH– !
Cu(OH)2 + 6H2O !
Cu(OH)2 + 2OH–!
[Cu(OH)4]2–!
[Cu(H2O)6]2+ + 4NO2– !
[Cu(NO2)4]2– + 6H2O !
[Cu(H2O)6]2+ + [Fe(CN)6]4– !
Cu[Fe(CN)6] + 6H2O !
Esperienza 5: Composti di FeII!
FeSO4·7H2O!
Fe2+(aq) + SO42–(aq) + 7 H2O(l)!
[Fe(H2O)6]2+ + 3 phen !
L. Andros, M. Juric, J. Popovic, P. Planinic, RSC Adv. 2014, 4, 37051
http://www.uncp.edu/home/mcclurem/ptable/iron/fe.htm
!
[Fe(phen)3]2+ + 6 H2O !
Esperienza 5: Composti di FeIII!
Fe(NO3)3·9H2O
Fe3+(aq) + 3NO3–(aq) + 9 H2O(l)!
[Fe(H2O)6]3+ + H2O!
[Fe(H2O)5(OH)]2+ + H3O+ !
[Fe(H2O)5(OH)]2+ + H2O !
[Fe(H2O)4(OH)2]+ + H3O+ !
[Fe(H2O)6]3+ + SCN– !
[Fe(H2O)5(SCN)]2+ + H2O !
4 [Fe(H2O)6]3+ + 3 [Fe(CN)6]4– !
Fe4[Fe(CN)6]3 + 24 H2O !
Blu di Prussia!
!
http://fredaliu1128.en.made-in-china.com/product/fbtEXTiGoUrA/China-Prussian-Blue-JF-PB-.html
Esperienza 5: Composti di NiII!
NiCl2·6H2O
[Ni(H2O)6]2+(aq) + 2 Cl–(aq)!
[Ni(H2O)6]2+ + 6 NH3!
[Ni(NH3)6]2+ + 6 H2O!
[Ni(H2O)6]2+ + 3 en!
[Ni(en)3]2+ + 6 H2O!
Esperienza 5: Composti di NiII!
[Ni(H2O)6]2+ + 2 Hdmg–!
h"p://www.thefullwiki.org/dimethylglyoxime
[Ni(Hdmg)2] + 6 H2O!
J.D.Mar;n,P.Hogan,K.A.Abboud,K.-H.Dahmen,Chem.Mater.1998,10,2525
Esperienza 5: Composti di CoII!
CoCl2·6H2O
2CoCl2·6H2O!
[Co(H2O)6]2+(aq) + 2 Cl–(aq)!
EtOH
!
H 2O
!
[CoCl4]2– + [Co(H2O)6]2+ + 6 H2O!
[Co(H2O)6]2+ + 4 Cl–!
[CoCl4]2– + 6 H2O!
[Co(H2O)6]2+ + 4 SCN–!
[Co(SCN)4]2– + 6 H2O!
Esperienza 5: Composti di CrIII !
KCr(SO4)2·12H2O!
!
CrCl3·6H2O!
http://wn.com/Synthesis_of_Chromium_III_Chloride
[Cr(H2O)4Cl2]Cl·2H2O!
Verde scuro!
[Cr(H2O)5Cl]Cl2·H2O !
Verde chiaro!
[Cr(H2O)6]Cl3 !
Violetto!
Esperienza 5: Composti di CrII !
III
[Cr(SO4)2]–!
!
Zn / H+
II
Cr2+ + 2 SO42–!
2 Cr2+ + 2 H2O + 2 CH3COO–!
[Cr2(CH3COO)4(H2O)2]!
Esperienza 5: Composti di CrVI !
2CrO4– + 2 H+!
!
Cr2O72– + H2O!
http://www.sciencephoto.com/media/4471/view
Esperienza 5: Composti di CrVI !
Cr2O72– + 4 H2O2 + 2H+!
2 [Cr(O)(O2)2(H2O)] + 3 H2O!
4 [Cr(O)(O2)2(H2O)] + 14 H2O + 12 H+!
!
http://woelen.homescience.net/science
4 [Cr(H2O)6]3+ + 7O2!