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Precipitation titration :
Volumetric methods based upon the formation of slightly soluble
precipitate are called " precipitation titration " .
Because of the precipitating titration based upon utilizing silver nitrate
(AgNO3) as a precipitating agent, then it called " argentimetric
processes " .
Precipitation titration is a very important , because it is a perfect method
for determine halogens and some metal ions .
EX. Derive a titration curve for the titration of 50ml of 0.1M NaCl with
-10
0.1M AgNO3 , KSPAgCl = 1.82x10 ?
Notes :
1) In precipitation titration we are using molar and formal conc. and we
are not using normal conc.
2) Precipitation titration methods are used to determine halogin ions.
3) Precipitation titration curves are plotte as :
5)
Precipitation titration curve is influenced by KSP value
(completeness of reaction) . when KSP value is small the titration curve
is perfect .
Ansewer of example :
a) before adding AgNO3 :
NaCl
0.1
Na + Cl
0.1 0.1
-
(10x0.1)
= 6.7x10
-2
-2
[Ag ] =
AgCl + NaNO3
[Cl ] =
= 1.17
-9
= 2.7x10
-9
AgCl + NaNO3
4.95
0.05
0.05
-5
= 5x10
[Cl ] =
-5
-5
[Ag ] =
= 0.36 x 10
-5
(50x0.1)
AgCl + NaNO3
-10
-10
[Cl ] = 1.82x10
+
-5
(52.5x0.1)
5.25
0.25
0.25
[Cl ] =
AgCl + NaNO3
[Ag ] =
-3
= 2.4x10
pAg = 2.62
pCl = 7.12
KSP(AgCl) = 1.35 x 10
Ag + Cl
Ag2CrO4
-2
2Ag + CrO4
-12
KSP(Ag2CrO4) = 1.2 x 10
+2
-2
[CrO4 ] =
-2
-3
[CrO4 ] = 6x10 M
The titration is performed in neutral or slightly basic medium pH = (7-10)
to prevent silver hydroxide formation at pH > 10 or formation of
chromic acid at pH < 7 .
-2
2CrO4 + 2H
2HCrO4
2AgOH
2Ag + 2OH
-2
-2
Cr2O7 + H2O
Ag2O(s) + H2O
Ag + SCN
+3
Fe
+ SCN
AgSCN(s)
+2
Fe (SCN)
Ag + Cl
Ag excess + SCN
AgCl + Ag excess
AgSCN
+2
+2
, [Zn(H2O)4]
+ 4NH3
+2
+ NH2CH2COO
+2
+ 4Cl
Cu
Cu
[Cu(NH3)4]+2
+2
Cu
CuCl4-2
.. cationic complex
Chelates : are produced when a metal ion coordinates with two or more
donor groups of a single ligand , and forming a cyclic structure .
Chelates can be classified into :
Cu
[Cu(NH3)4]+2
+ 4NH3
b) ligand whose share two electron pairs is called " Bidentate "
+2
Cu
+ NH2CH2COO
Cu(NH2CH2COO)2
c) ligand whose share three electron pairs is called " Tridentate " , and
four is called " Tetradentate " , " pentadentate " , " Hexadentate ".. ect.
Titration curve for complexation titration :
When a metal ion M with a coordination number of four is react with
tetradentate ligand D :
M+D
Kf =
MD
Kf = formation constant
M + 2B
This equation can be write as :
M+B
12
MB Kf1 =
= 10
MB + B
MB2 . Kf2 =
Kf1 x Kf2 =
= 10
20
= 10
From the curve , the ligand that combines with a metal ion in 1:1 ratio is
better from others , because the change in pM value at equivalent point
region is largest . that means , combine in lower ratios with metal ions
are ordinarily superior reagents for complex formation titration .
H4y + H2O
-
-2
H3y + H3O
-2
H2y + H3O
-3
H2y + H3O
-3
H3y + H3O
Hy + H3O
-4
Hy + H3O
y + H3O
These values refers to that the first two protons are lost much more
readily than the remaining two .
-
-2
-3
-4
is predominate .
-3
is predominate .
a) when pH (3 - 6) , H2y
b) when pH (6 -10) , Hy
-4
c) at pH > 10 , y
is predominate .
=
=
=
=
=
0+
1+
2+
3+
4=
1
9
+ H2y
+3
+ H2y
+4
+ H2y
+n
+y
M
M
M
-2
-1
-2
My + 2H
-2
My + 2H
-2
My + 2H
-4
(n-4)+
My
KMy =
EDTA forms chelates with all cations in 1:1 ratio and these chelates are
very stable . this great stability is come from the several complexing
sites within the molecule .
Formation constant for EDTA complexes :
Cation
KMy
log KMy
2.1x10
+2
+2
5x10
+2
2.1x10
+2
4.3x10
Ag
Mg
Ca
Fe
Sr
7.32
4.9x10
8.69
10
10.7
14
14.33
8.63
10
-4
-3
Ag + y
[Ag y ]
KMy =
2.1x10 =
=
K
My
= KMy x
My
= K Cay x
Cay
10
K Cay = 5x10
(from tables)
10
-1
Cay
= 5x10
x 3.5 x10
Cay
= 1.75x10
10
Ca
-4
+ y
(50x0.01)
-2
Cay
(25x0.01)
0.5
0.25
0.25
0.25
11
-3
+2
= 3.33x10
[Ca ] =
-3
= 2.48
c) at end point :
+2
-4
Ca
-2
+ y
Cay
(50x0.01) (50x0.01)
0.5
0.5
+2
[Ca ] =
+2
+ y
-4
+2
= CT
My
Ca
Ca
K
= 0.005 F
-2
Cay
Ca = CT
K
Cay
10
1.75x10
+2
=
-7
[Ca ] = 5.35x10
-7
= 6.27
12
Ca
-4
+ y
(50x0.01) (60x0.01)
-2
Cay
0
0.5
0.6
0.1
0.1
0.1
-2
-3
[Cay ] =
= 4.5x10
-4
[CT] =
My
= 9.1x10
10
1.75x10
-2
[Cay ]= x
pCa = -log x
13
From the structure , the proton associated with sulphonic acid group is
completely dissociated in an aqueous medium ,and , the phenolic
protons are only partially dissociated :
H3In + H2O
-
H2In + H2O
-2
HIn + H2O
H2In + H3O
-2
HIn
-3
+ H3O
+
In + H3O
EBT behaves also an acid-base indicator , because that the acids and
there conjugate bases are differ in color .
Method complexes of EBT are red , then to indicate the color change
with EBT the pH must be 7 or more ,so that the blue form of the
-2
species HIn .
Predominates in the absence of metal ion .
The end point reaction is then :
-
-3
-2
-2
MIn + Hy
HIn + My
red
blue
14
2) Back titration : back- titration is useful analysis for cations that will
form
very stable EDTA complexes and when a suitable indicator is
not available
or it react slowly with EDTA .
In this method , excess from EDTA is added and the excess of EDTA is
+2
determine by back-titration with a standard Mg solution using EBT as
indicator .
M-EDTA + EDTA(excess)
M + EDTA(excess)
+2
EDTA(excess) + Mg
Mg-EDTA
(st.)
+2
-2
+2
or Zn
+2
+2
My + Mg
+2
My + Zn
Mgy + M
-2
Zny
+M
+2
The liberated Mg
-2
+2
-2
+2
and form a
+2
or Zn
, then the
15
Solubility of precipitates
Solubility of precipitate is defined as disappeare of atoms or molecules
or ions of solute through atoms or molecules of solvent . Or it refers to
the amount of solute capable to dissolve in a volume of solvent.
Therefore , the chemical substances can be classified depends upon its
solubility to : soluble , or partially soluble , or insoluble .
Solubility of inorganic compounds in water :
a) all ammonium , sodium , potassium salts are soluble in water.
b) all nitrates , acetates are soluble in water.
c) all chlorides are soluble in water except chlorides of silver , mercury
and lead.
d) all sulphate are soluble in water except sulphate of barium and lead ,
while sulphate of calcium and strontium are moderately soluble.
e) all hydroxides are insoluble in water except hydroxide of ammonium ,
sodium and potassium.
A +B
+
K.S.P = [ A ] [ B ]
Am Bn
mA
+n m
K.S.P = [ A ] [ B
+n
+ nB
-m
-m n
16
+2
Ba(IO3)2
Ba
x
+
+ 2IO3
2x
- 2
K.S.P = [ Ba ] [ IO3 ]
-9
1.57x10 = (x)(2x)
-9
1.57x10 = 4x
X=
-4
X = 7.3x10
mole/L
x 487
+ -
Ag + Cl
x
K.S.P = (x)(x) = x2
X=
b) AB2 or A2B : the ratio is 1:2 or 2:1, like: PbI2 , HBr2 , Ag2CrO4
17
PbI2
Pb + 2I
x
2x
K.S.P = (x)(2x)2
3
K.S.P = (x)(4x)2 = 4x
X=
Fe + 3OH
Fe(OH)3
3x
K.S.P = (X)(3X)
X=
2Bi
+3
+ 3S
-2
X=
e) AB5 : the ratio is 1:5 , like : PCl5
18
PCl5
P + 5Cl
x
5x
X=
Ag + Cl
AgCl(s)
+
= (x)(x)
-10
= x2
1.8x10
1.8x10
x=
=
-5
-2
2Ag + CrO4
X=
1) Completments of precipitation :
Q: How can you predict weather a precipitate is formed or doesn't
formed when a solution of positive ion is mixed with other solution of
negative ion ?
The predict that a precipitate formed or not is depends upon the value
of KSP and IP .
+
IP = [Ag ][Cl ]
Then , If IP< KSP
unsaturated with AgCl .
If IP > KSP
If IP = KSP
EX. 10ml of 10-5M AgNO3 solution mixed with 10ml of 10-5M HCl
solution is the ppt. formed , KSP =
.
+
-5
[ Ag ] = 10 /2
-5
[ Cl- ] = 10 /2
-5
-5
IP = 10 /2 x 10 /2 =
Because of IP < KSP , therefore there is no precipitate .
2) Dissolution of precipitate:
When it is a precipitate in the solution , then it is heterogeneous system
and the solution is saturated.
Q: How we can dissolve more than of precipitate ?
20
AgCl(s)
Ag + Cl
Ag + 2NH3
3) Prevention of precipitation :
Ag+ + Cl-
AgCl
IP<KSP
+2
Zn
+ 2OH
Zn(OH)2
AgCl
Ag + Cl
X = [Ag+] = [Cl ] =
+
AgCl
Ag + Cl
AgNO3
Ag + NO3
Ba(IO3)2
KIO3
Ba
+ 2IO3
2x
Ba(IO3)2 in a solution of
+ IO3
0.02
0.02
1.57x10 = (x)(0.02)
-9
1.57x10 = 0.04x
-6
X= 3.9x10 mole/L
22
-6
Mg
Mg(OH)2
+ 2OH
Solubility of precipitate
concentration.
will
decreasing with
increase of
[OH ]
b) second type is more complicated from the first , when anion or cation
+
of precipitate is capable to react with [H3O ] or [OH ] of solvent .
CaF2
+2
Ca
+ 2F
2H3O
2HF + 2H2O
according to
Le Chatelier
23
Al(OH)3
Al
+3
+ 3OH
+ 6F
-3
AlF6
+3
F ion even thought Al(OH)3 has low solubility , therefore, the compete
-
is extremely between F
+3
ions
24
EX. Calculate ionic strength of 0.1M sol. of KNO3 and for 0.1M sol.
Na2SO4 ?
KNO3
K+ + NO3-
2Na+ + SO4-2
+2
Zn
+ 2Cl
25
0.03
Al(NO3)
2x0.03
Al
+3
0.02
+ 3NO3
3x0.02
a = cf
log f = - 0.5 z2
where :
f = coefficient of activity.
0.5
constant
solvent at 25C .
z = charge of ion.
= Ionic strength.
26
for
water
as
-2
EX. If Ba(SO4)
0.002M
BaCl2 , what is the concentration of SO4
saturate the sol. with BaSO4 ?
that is enough to
a) ionic strength:
NaCl
Na + Cl
0.012 0.012
BaCl2
+2
Ba
+ 2Cl
0.002
2x0.002
= 0.6
-2
Ba+2 + SO4
c) BaSO4
KSP = [Ba][SO4]
-10
1.1x 10
= (0.002)(SO4)
-8
1.1x10
[SO4-] = 1.39x10
mole/L
27
and f .