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PRECIPITATION TITRATIONS
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Copyright 2013
2013/3/6
L. Lapitan 2011
L. Lapitan 2011
Solubility Equilibria
MmXx (s) m Mn+ (aq) + x Xy- (aq)
L. Lapitan 2011
Solubility Equilibria
For a dissolution process, we give the
equilibrium constant expression the name
solubility product (constant) Ksp. For
MmXx (s) m Mn+ (aq) + x Xy- (aq)
Ksp = [Mn+]m [Xy-]x
refer to a specific balanced equation
(by definition this balanced equation is one
mole of solid becoming aqueous ions)
at a specific temperature.
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Problem
Write the expressions of Ksp of:
+
K sp = [Ag ][Cl ]
a) AgCl
2+
2
b) PbI2
K sp = [Pb ][I ]
3 2
2+ 3
c) Ca3(PO4)2
K sp = [Ca ] [PO 4 ]
d) Cr(OH)3
3
3+
K = [Cr ][OH ]
sp
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Problem
1. If a saturated solution of BaSO4 is prepared by
BaSO 4 (s)
][
Ba 2+ (aq) + SO 4 (aq)
K sp = Ba 2+ SO 4
[ ] [ ] = 1.05 x 10 M
2. Calculate the Ksp for Ca3(PO4)2 (FW = 310.2) if the
) [Ans. 1.3x10-26]
K = (1.05 x 10
solubility
is 8.1x10-4 g/L
K sp = x 2 if x = Ba 2+ = SO 4
-5
-5
sp
K sp = 1.1 x 10 -10
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Molar solubility
If we know the Ksp value for a solid, we can
calculate the molar solubility, which is the
number of moles of the solid that can dissolve
in a given amount of solvent before the
solution becomes saturated.
The molar solubility leads to the solubility (by
using the molar mass) which is the mass of the
solid that can dissolve in a given amount of
solvent before the solution becomes saturated.
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Problem
Equilibrium Reaction
Ksp @ 25oC
7.7 x 10-13
1.6 x 10-10
8.3 x 10-17
The higher the Ksp, the more soluble the compound is.
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Problem
1. What is the molar solubility of PbI2 in 0.1 M KI
solution? Ksp = 7.1 x 10-9
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Qsp =
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2+
2
[Ca ][F ]
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No precipitation occurs!
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Problem
1. Three drops of 0.20 M KI solution is added to 100.0 mL
of 0.0101 M Pb(NO3)2. Will a precipitate of lead iodide
form? (Assume 1 drop = 0.05 mL)
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Complete Precipitation
Generally we treat precipitation as complete if
99.9% of the original ion concentration has
been lost to the precipitate.
For example, if our initial [Pb2+] is 0.10 M,
then precipitation by adding I- is complete
when our solution contains a [Pb2+] less than 1
x 10-4 M.
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Problem
1. The first step in a commercial process in which
magnesium is obtained from sea water involves
precipitating Mg2+ as Mg(OH)2. the magnesium ion
concentration in sea water is about 0.059 M. If sea
water sample is treated so its [OH-] is maintained at
0.20 x 10-3 M.
(a) what will be the [Mg2+ ]remaining in the solution
when precipitation stops Ksp = 1.8 x 10-11
(b) can we say that precipitation of Mg(OH)2 is
complete under these conditions?
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Problem
2. A typical Ca2+ concentration in seawater is 0.010 M.
Will the precipitation of Ca(OH)2 be complete from a
seawater sample in which [OH-] is maintained at
0.040 M? Ksp of Ca(OH)2 is 5.5 x 10-6
[Answer: Since the final [Ca2+] is 3.4 x 10-3 M, which is 34 % of
0.010 M, the precipitation is not complete.]
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Fractional precipitation
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Problem
Sodium Iodide (NaI) crystals are slowly added
to a solution that is 0.100 M Pb(NO3)2 and
0.100 M AgNO3. Which will precipitate first?
Ksp AgI = 8.31 x 10-17 Ksp PbI2 = 7.1 x10-9
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Problem
Which Will Precipitate First?
1. CaCO3
(Ksp: 8.7x10-9)
2. CaF2
(Ksp: 4.0 x 10-11)
3. Ca3(PO4)2
(Ksp: 1.2 x 10-26)
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Problem
1. Solid NaI is slowly added to a solution that is 0.010 M
in Cu+ and 0.010 M Ag+.
(a) Which compound will begin to precipitate first?
(b) Calculate [Ag+] when CuI just begins to precipitate.
(c) What % of Ag+ remains in solution at this point?
AgI Ksp = 8.3 x10-17
CuI Ksp = 1.00 x 10-12
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Problem
1. AgNO3 is slowly added to a solution with [Cl-]
= 0.115 M and [Br-] = 0.264 M. What percent
of the Br- remains unprecipitated at the point
at which AgCl (s) begins to precipitate?
Ksp values AgCl = 1.8 x 10-10
AgBr = 5.0 x 10-13
Answer: 0.12 % of Br- remains.
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Precipitation Titrations
Titrations with silver nitrate are sometimes
called argentometric titrations.
Example
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10-32
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10-35
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10-37
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10-38
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10-39
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10-40
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10-44
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10-45
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Blank Titration
In Blank determinations, all steps for the
analysis are performed in the absence of the
sample.
Blank determinations reveal errors due to
interfering contaminants from vessels or
reagents employed in analysis
Blanks also allow the analyst to correct titration
data for the volume of reagent needed to cause
an indicator to change color at an endpoint
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