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Documente Cultură
110
36
[Co(en)
3
]
3+
4.910
48
[Co(NH
3
)
6
]
3+
4.510
33
[Co(ox)
3
]
3
110
20
[Cr(EDTA)]
110
23
[Cr(OH)
4
]
810
29
[CuCl
3
]
2
510
5
[Cu(CN)
2
]
1.010
16
[Cu(CN)
4
]
3
2.010
30
mation Constants for Complex Ions at 25
o
C.
Complex K
f
[Ag(CN)
2
]
5.610
18
[Ag(EDTA)]
3
2.110
7
[Ag(en)
2
]
+
5.010
7
[Ag(NH
3
)
2
]
+
1.610
7
[Ag(SCN)
4
]
3
1.210
10
[Ag(S
2
O
3
)
2
]
3
1.710
13
[Al(EDTA)]
1.310
16
[Al(OH)
4
]
1.110
33
[Al(ox)
3
]
3
210
16
[Cd(CN)
4
]
2
6.010
18
[Cd(en)
3
]
2+
1.210
12
[Cd(NH
3
)
4
]
2+
1.310
7
[Co(EDTA)]
2
2.010
16
Complex K
f
[Cu(EDTA)]
2
510
18
[Cu(en)
2
]
2+
110
20
[Cu(CN)
4
]
2
110
25
[Cu(NH
3
)
4
]
2+
1.110
13
[Cu(ox)
2
]
2
310
8
[Fe(CN)
6
]
4
110
37
[Fe(EDTA)]
2
2.110
14
[Fe(en)
3
]
2+
5.010
9
[Fe(ox)
3
]
4
1.710
5
[Fe(CN)
6
]
3
110
42
[Fe(EDTA)]
1.710
24
[Fe(ox)
3
]
3
210
20
[Fe(SCN)]
2+
8.910
2
12
Constante de formare
Complex K
f
[HgCl
4
]
2
1.210
15
[Hg(CN)
4
]
2
310
41
[Hg(EDTA)]
2
6.310
21
[Hg(en)
2
]
2+
210
23
[HgI
4
]
2
6.810
29
[Hg(ox)
2
]
2
9.510
6
[Ni(CN)
4
]
2
210
31
[Ni(EDTA)]
2
3.610
18
[Ni(en)
3
]
2+
2.110
18
[Ni(NH
3
)
6
]
2+
5.510
8
[Ni(ox)
3
]
4
310
8
[PbCl
3
]
2.410
1
[Pb(EDTA)]
2
210
18
Complex K
f
[PbI
4
]
2
3.010
4
[Pb(OH)
3
]
3.810
14
[Pb(ox)
2
]
2
3.510
6
[Pb(S
2
O
3
)
3
]
4
2.210
6
[PtCl
4
]
2
110
16
[Pt(NH
3
)
6
]
2+
210
35
[Zn(CN)
4
]
2
110
18
[Zn(EDTA)]
2
310
16
[Zn(en)
3
]
2+
1.310
14
[Zn(NH
3
)
4
]
2+
4.110
8
[Zn(OH)
4
]
2
4.610
17
[Zn(ox)
3
]
4
1.410
8
13
2
1 aq aq aq f
Pb Cl PbCl K
+ +
+
0
2, 2
aq aq aq f
PbCl Cl PbCl K
+
+
0
2, 3, 3 aq aq aq f
PbCl Cl PbCl K
+
2
3, 4, 4 aq aq aq f
PbCl Cl PbCl K
+
Corelaie constante de formare coeficieni
de distribuie
| |
| || |
K
PbCl
Pb Cl
f
aq
aq aq
1
2
=
+
+
| | | || |
PbCl K Pb Cl
aq f aq aq
+ +
=
1
2
| |
| || |
K
PbCl
PbCl Cl
f
aq
aq aq
2
2
0
=
+
,
;
| | | || || |
PbCl K K Pb Cl Cl
aq f f aq aq aq 2
0
2 1
2
,
=
+
| |
| || |
K
PbCl
PbCl Cl
f
aq
aq aq
3
3
2
0
=
,
,
;
| | | || || || |
PbCl K K K Pb Cl Cl Cl
aq f f f aq aq aq aq 3 1 2 3
2
,
+
=
| | | || || || || |
PbCl K K K K Pb Cl Cl Cl Cl
aq f f f f aq aq aq aq aq 4
2
1 2 3 4
2
,
+
=
| | | || |
PbCl K PbCl Cl
aq f aq aq 2
0
2 ,
=
+
| | | || |
PbCl K PbCl Cl
aq f aq aq 3 3 2
0
, ,
=
2
4,
4
3,
;
aq
f
aq aq
PbCl
K
PbCl Cl
(
=
( (
14
Example 2: A complex formed from a ligand and a metal
| | | | | | | | | | | |
Pb Pb PbCl PbCl PbCl PbCl
aq all forms aq aq aq aq aq , , , ,
= + + + +
+ + 2
2
0
3 4
2
| |
| |
o
o
aq
aq all forms
Pb
Pb
+ 2
,
| | | || |
PbCl K Pb Cl
aq f aq aq
+ +
=
1
2
| | | || || |
PbCl K K Pb Cl Cl
aq f f aq aq aq 2
0
2 1
2
,
=
+
| | | || || || |
PbCl K K K Pb Cl Cl Cl
aq f f f aq aq aq aq 3 1 2 3
2
,
+
=
| | | || || || || |
PbCl K K K K Pb Cl Cl Cl Cl
aq f f f f aq aq aq aq aq 4
2
1 2 3 4
2
,
+
=
| | | | | || | | || | | || | | || |
Pb Pb K Pb Cl K K Pb Cl K K K Pb Cl K K K K Pb Cl
aq allforms aq f aq aq f f aq aq f f f aq aq f f f f aq aq ,
= + + + +
+ + + + + 2
1
2
1 2
2
2
1 2 3
2
3
1 2 3 4
2
4
| | | | | | | | | | | |
Pb Pb K Cl K K Cl K K K Cl K K K K Cl
aq allforms aq f aq f f aq f f f aq f f f f aq ,
= + + + +
|
\
|
.
|
+ 2
1 1 2
2
1 2 3
3
1 2 3 4
4
1
| |
| |
| |
| | | | | | | | | |
o
0
2 2
2
1 1 2
2
1 2 3
3
1 2 3 4
4
1
= =
+ + + +
|
\
|
.
|
+ +
+
Pb
Pb
Pb
Pb K Cl K K Cl K K K Cl K K K K Cl
aq
aq allforms
aq
aq f aq f f aq f f f aq f f f f aq
,
| |
| |
| | | | | | | |
o
0
2
1 1 2
2
1 2 3
3
1 2 3 4
4
1
1
= =
+ + + +
|
\
|
.
|
+
Pb
Pb
K Cl K K Cl K K K Cl K K K K Cl
aq
aq allforms
f aq f f aq f f f aq f f f f aq
,
Predicts amt of total Pb as Pb
2+
based only on [Cl-]
o o o o
1 2 3 4
, , ,
Same for
15
0
0.1
0.2
0.3
0.4
0.5
0.6
0.7
0.8
0.9
1
-2 -1 0 1 2 3 4 5
pCl
F
r
a
c
t
i
o
n
0
0.1
0.2
0.3
0.4
0.5
0.6
0.7
0.8
0.9
1
-2 -1 0 1 2 3 4 5
pCl
F
r
a
c
t
i
o
n
0
0.1
0.2
0.3
0.4
0.5
0.6
0.7
0.8
0.9
1
-2 -1 0 1 2 3 4 5
pCl
F
r
a
c
t
i
o
n
0
0.1
0.2
0.3
0.4
0.5
0.6
0.7
0.8
0.9
1
-2 -1 0 1 2 3 4 5
pCl
F
r
a
c
t
i
o
n
0
0.1
0.2
0.3
0.4
0.5
0.6
0.7
0.8
0.9
1
-2 -1 0 1 2 3 4 5
pCl
F
r
a
c
t
i
o
n
| |
| |
o
4
4
2
PbCl
Pb
aq
aq all forms ,
| |
| |
o
1
1
+
PbCl
Pb
aq
aq all forms ,
| |
| |
o
2
2
0
PbCl
Pb
aq
aq all forms ,
| |
| |
o
3
3
PbCl
Pb
aq
aq all forms ,
| |
| |
o
o
aq
aq all forms
Pb
Pb
+ 2
,
| | | | | | | |
Pb Pb PbCl PbCl PbCl PbCl
aq all forms
aq aq
aq
o
aq aq
,
=
(
+
(
+ + +
+ + 2
2 3 4
2
16
9 km
10
4
ppm PbSO
s ,
Magma, vulcani,
Presiune, temp (350
o
C)
155000 , ppmCl
aq
,
Pb Cl PbCl
aq aq
2
3
3
+
+
,
PbCl Pb xCl
x aq
x
aq ,
2 2 +
+
H S H S
2
2
2 +
+
Pb S PbS
s
2 2 +
+
CaCO Ca CO
H CO H CO
s 3
2
3
2
3
2
2 3
2
,
+
+
+
+
100
2
ppm PbCl
x aq
x
,
(
(
(
=
17
Aplicaii ale reaciilor de complexare
I. Intervine in diverse procese vitale: respiraie; fotosinteza, metabolism,
II. Aplicaii industriale:
n procedeul hidrometalurgic de obinere a Cu din minereuri (dizolvarea selectiv
a cuprului).
n procedeele industriale de obinere a Au i Ag din minereuri (dizolvarea
selectiva a acestor metale nobile cu NaCN).
Pentru prepararea unor substane pure (impuritile se pot transforma n
combinaii complexe solubile sau insolubile n ap).
n industria farmaceutic la prepararea unor medicamente: cisplatin, carboplatin,
oxalilplatin, vitamina B12, ..
III. Aplicaii de mediu
Depoluare: ndeprtarea metalelor grele, a cianurilor,
Determinarea duritii apei;
IV. Aplicaii medicale: detoxifierea organismului de Pb
2+
V. Aplicaii analitice
Analiza calitativ: identificarea sau mascarea anumitor specii (atomi, ioni,
molecule)
Volumetria bazat pe reacii de complexare
.
18
Aplicaii ale reaciilor de complexare
Intervin in diverse
procese vitale:
Respiraie
Fotosinteza
Metabolism
19
Aplicaii ale reaciilor de complexare
Intervin in diverse
procese vitale:
Respiraie
Fotosinteza
Metabolism
20
Aplicaii ale reaciilor de complexare
Intervin in diverse
procese vitale:
Respiraie
Fotosinteza
Metabolism
21
Aplicaii industriale:
dizolvarea
selectiv a Cu
2+
;
dizolvarea
selectiva Ag si
Au;
pentru purificarea
anumitor
substane impure;
n industria farma-
ceutic: sinteza
cisplatin,
carboplatin,
oxalilplatin,
vitamina B12, ....
Aplicaii ale reaciilor de complexare
CuS + 4NH
3
=> [Cu(NH
3
)
4
]
2+
+ S
2-
Ag=>Ag
+
;
Ag
+
+ 2CN
-
=> Ag(CN)
2
-
22
Determinarea duritii apei (1)
Duritatea apei este dat, n general, de srurile de Ca
2+
i Mg
2+
dizolvate
i poate fi determinat titrimetric, prin titrare cu EDTA:
Mod de lucru: Se iau 50 mL ap, se adaug 1 mL soluie tampon
amoniacal pH=10 i 3040 mg negru eriocrom T drept indicator. Se
titreaz cu EDTA 0,01 M pn la virajul de la rou la albastru pal. Dac
apa nu conine deloc Mg
2+
atunci este indicat adugarea a 0,1 mL
complex MgEDTA
2-
0,1M nainte de adugarea indicatorului.
Duritatea total se va exprima ca fiind mg CaCO
3
/L ap.
, [mg/L] (V se va exprima n mL)
Dac apa conine i ioni care interfer, atunci n ap se vor aduga 4 mL
soluie tampon, 30 mg clorur de hidroxilamoniu i 50 mg KCN (p.a.)
nainte de adugarea indicatorului.
( )
T M
EDTA
1000
D C V F 100
50
=
23
Determinarea duritii apei (2)
Pentru a obine un viraj mai clar se recomand ca nainte de
determinare apa s fie acidifiat cu HCl diluat, fiert pentru cteva
minute pentru ndeprtarea CO
2
, rcit i neutralizat cu NaOH urmat
apoi de adugarea soluiei tampon i a indicatorului.
Duritatea permanent: se iau 250 mL ap de analizat i se fierbe la
foc moderat timp de 20 30 minute. Dup rcire, soluia se
filtreaz (fr ca filtrul s fie splat), soluia rezultat fiind adus la
balon cotat de 250 mL. Se ia o cot parte de 50 mL i se
procedeaz ca n cazul duritii totale.
Duritatea temporar: se determin ca fiind diferena dintre duritatea
total i duritatea permanent, ambele exprimate ca mg CaCO
3
/L
ap.
24
Depoluare ndeprtarea metalelor grele
25
Se dau ?
40 ug/dL plumb in sange
3 L volume of blood
28.7 mg EDTA
m.w. 374.28
K
f
= 10
17.9
Concentartia molara Pb
molaritatea EDTA
Concentratia la echilibru
| |
( )
EDTA
mgEDTA
init
=
287 .
| |
Pb
gPb
dL
init
=
|
\
|
.
|
40
| |
( )
EDTA
mgEDTA
g
mg
mole
g
init
=
|
\
|
.
|
|
\
|
.
| 287
1
10
1
374 28
3
.
.
| |
( )
EDTA
mgEDTA
g
mg
mole
g
L
x M
init
=
|
\
|
.
|
|
\
|
.
|
=
287
1
10
1
374 28
3
7 66 10
3
5
.
.
.
| |
Pb
gPb
dL
dL
L
init
=
|
\
|
.
|
|
\
|
.
|
40 10
| |
Pb
gPb
dL
dL
L
mole
g
init
=
|
\
|
.
|
|
\
|
.
|
|
\
|
.
|
40 10 1
207 2
.
| |
Pb
gPb
dL
dL
L
mole
g
g
g
init
=
|
\
|
.
|
|
\
|
.
|
|
\
|
.
|
|
\
|
.
|
40 10 1
207 2
1
10
6
.
| |
Pb
gPb
dL
dL
L
mole
g
g
g
x M
init
=
|
\
|
.
|
|
\
|
.
|
|
\
|
.
|
|
\
|
.
| =
40 10 1
207 2
1
10
193 10
6
6
.
.
Detoxifierea organismului de Pb
2+
26
| |
EDTA x M
init
=
766 10
5
.
| |
Pb x M
init
=
193 10
6
.
CaNa EDTA Ca Na EDTA
s aq aq aq 2
2 2 4
2
+ +
+ +
EDTA Pb PbEDTA K x
aq aq aq f
4 2 2 17 9 17
10 7 93 10
+
+ = =
.
.
( )
( )
5 4
7.66 10 3 3.20 10
PbEDTA
x M L x moli
=
Din EDTA
Din Pb
( )
( )
6 6
1.93 10 3 5.79 10 10
PbEDTA
x M L x x moli
=
Agent limitativ
| |
EDTA
x x
L
x
after L R . .
. .
. =
=
320 10 579 10
3
7 467 10
4 6
5
. .
0
after L R
Pb (
6
6
. .
5.79 10
1.93 10
3
after L R
x
PbEDTA x
L
( = =
Detoxifierea organismului de Pb
2+
27
Detoxifierea organismului de Pb
2+
EDTA
4-
Pb
2+
EDTAPb
2-
stoi 1 1 1
Init
*
7.66x10
-5
0 1.93x10
-6
Change * +x x -x
Equil* 7.66x10
-5
x 1.93x10
-6
Aprox x<<<7.66x10
-5
x<<1.93x10
-6
| |
| || |
K x
PbEDTA
EDTA Pb
f
aq eq
aq eq aq eq
= =
+
7 93 10
17
2
4 2
.
,
, ,
x x M x
g
dL
= =
317 10 679 10
20 13
. .
| |
| || |
| |
| | ( )
K x
PbEDTA
EDTA Pb
PbEDTA x
EDTA x x
f
aq eq
aq eq aq eq
after L R
after L R
= = =
+
7 93 10
17
2
4 2
2
4
.
,
, ,
. .
. .
| |
| || |
| |
| | ( )
| |
| | ( )
K x
PbEDTA
EDTA Pb
PbEDTA x
EDTA x x
PbEDTA
EDTA x
f
aq eq
aq eq aq eq
after L R
after L R
after L R
after L R
= = =
+
~
7 93 10
17
2
4 2
2
4
2
4
.
,
, ,
. .
. .
. .
. .
( )
( )
2
6
. .
20
5 17
4 17
. .
1.93 10
3.17 10
7.467 10 7.93 10
7.93 10
after L R
after L R
PbEDTA
x x
EDTA x
(
= = =
(
*Consideram ca tot Pb
2+
se transforma in complex cu EDTA si apoi o parte disociaza
28
5-10yrs
29
Volumetria bazat pe reacii de complexare
CH
2
CH
2
N N
CH
2
CH
2
CH
2
CH
2
C
C
C
C
O
O
O
O
O
O
O
O
4-
EDTA
Reactiv de titrare
O H
N
O
O
O
N
OH
O
O O H
O
OH
EGTA
30
Volumetria bazat pe reacii de complexare
Indicatori
NH
NH
N H
N H
N O
O
O O
O
O
-
NH
4
+
Murexid
N
N
NO
2
SO
3
Na
OH
OH
Negrului eriocrom T
H
2
In
-
HIn
2-
In
3
-
0
6,3 11,5
pH
14
Tampon 9,2
31
Aplicaii analitice ale complexonometriei
Determinarea direct a Ba
2+
Determinarea direct a Bi
3+
Determinarea duritii totale a apei
Determinarea Fe
3+
Determinarea Ca
2+
prin titrare de substituie
Determinarea Ni
2+
Determinarea indirect a Al
3+
Determinarea indirect a Ag
+
Determinarea anionului fosfat Determinarea anionului sulfat
Determinarea Ca
2+
i Pb
2+
n amestec Analiza unui oel (Fe Ni)
Determinarea Cr
3+
i Fe
3+
din amestec Determinarea Cu
2+
Determinarea Ca
2+
i Mg
2+
n amestec Determinarea Fe
2+
Determinarea Ca
2+
n prezen de Mg
2+
prin titrare cu EGTA
Determinarea Ca
2+
n prezena Ba
2+
prin titrare cu CDTA
Determinarea individual a Mg
2+
, Mn
2+
i Zn
2+
din amestec
Determinarea coninutului de Fe, Ni, Cr dintr-un oel
Determinarea halogenurilor i a tiocianailor
32
Aplicaii ale reaciilor de complexare/
Analiza calitativ
Identificarea diverilor analii poate fi pusa in evidena prin reacii de
complexare:
Fe
3+
+ xSCN => [Fe(SCN)
x
]
3-x
(ROU snge)
Co
2+
+ xSCN => [Co(SCN)
x
]
2-x
(albastru)
Cu
2+
+ 4NH
3
=> [Cu(NH
3
)
4
]
2+
(albastru intens)
4Fe
3+
+ 3K
4
[Fe(CN)
6
] => Fe
4
[Fe(CN)
6
]
3
(Albastru de Berlin)
3Fe
2+
+ 2K
3
[Fe(CN)
6
] => Fe
3
[Fe(CN)
6
]
2
(Albastru de Turnbull )
2Ni
2+
+ K
4
[Fe(CN)
6
] => Ni
2
[Fe(CN)
6
] (verzui)
N
OH
N
O
+1/3Fe
3+
Fe/3
+H
+
Ni
N
O
H
O
N
O
N N
O
H
CH
3
CH
3
C H
3
C H
3
C H
3
C
C C H
3
N
N OH
OH
2
+ (Ni
2+
+ 2Cl
-
) + 2(NH
4
+
+ HO
-
)
+ 2(NH
4
+
+ Cl
-
)+2H
2
O
O
O
OH
OH
SO
3
Na
O
O
O
OH
SO
3
Na
Al(OH)
2
Al
3+
+ 3Cl
-
+
+ 3(NH
4
+
+ HO
-
)
+ 3(NH
4
+
+ Cl
-
)+H
2
O
S
S
NH
2
NH
2
S H
N H
NH
SH
S H
N H
NH
S
S
N H
NH
S
n
S
N H
NH
SH
+n-1Ni
2+
N + nH+
N
n
33
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