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Precipitation

Every problem weve looked at so far has been one where we start with a solid, put it in some water and ask
(in one way or another) how much dissolves. The questions in this section are from the opposite perspective.
In this section we are going to check to see if a precipitate will form. To be clear, a precipitate (ppt) is an insoluble solid formed when two soluble solutions are mixed. How does this fit into our Ksp scheme? Remember that for an ionic substance, Ksp must be put into this format:
MX (s) <> M+ (aq) + X- (aq)
Where is the solid at in this equation? Clearly it is always on the left-hand side in this Ksp setup. This means
that for a precipitate (ppt) to form, the reaction has to shift to the left side. How does it do that? Remember in
the previous section our discussion of Q the reaction quotient? We determined earlier if:
Q = K System is at equilibrium
Q < K System must shift to the right
Q > K System must shift to the left
So what we are looking at here is performing a test-case for Q, and seeing what the value is relative to the Ksp
equation. If Q > K, the system will shift left and therefore form a precipitate. Lets look at some simple examples:

Simple Q Calculations

Example 1: Will a precipitate of BaCO3 (Ksp = 2.6x10-9) form if a solution is made so that [Ba+2] = 2x10-5 M
and [CO3-2] = 2x10-4 M?
Set up your Ksp equation like you have this entire time:
BaCO3 (s) <> Ba+2 (aq) + CO3-2 (aq)

Ksp = [Ba+2][CO3-2] = 2.6x10-9

Now do a test-case for Q

Q = [Ba+2][CO3-2]
Q = (2x10-5)(2x10-4)
Q = 4x10-9

Now compare Q to Ksp and we find that


Q (4x10-9) > Ksp (2.6x10-9) so your final answer is:
YES, a precipitate forms

If Q > Ksp then a precipitate (ppt) of the solid forms

Example 2: Will a precipitate of MgF2 (Ksp = 5.2x10-11) form if [Mg+2] = 4x10-4 and [F-1] = 2x10-3?
MgF2 (s) <> Mg+2 (aq) + 2 F-1 (aq)

Ksp = [Mg+2][F-1]2 = 5.2x10-11


Q = (4x10-4)(2x10-3)2 = 1.6x10-9
Since Q > Ksp, Yes a ppt forms

Please note that even though there is a 2 here in the equation, the amount of the F-1 is NOT initially doubled.
Why is that? The 2 in the above formula is only taken into account when dealing with stoichiometric comparisons. These only take place in the change portion of an ICE table. The amounts we are using are all initial
amounts:
MgF2 (s) <>
Mg+2 (aq) + 2 F-1 (aq)
Ksp = [Mg+2][F-1]2 = 5.2x10-11
-4
-3
Initial
4x10
2x10
Change
+x
+2x
We dont even get to this part of the table in these problems. If we did, then the 2 would be taken into account here at the change line. Precipitation problems dont even get past the initial line so that 2 is not important.

Dont change the concentration of a given species because


there is a stoichiometric coefficient in the equation
Example 3: Will a precipitate of Ag2CrO4 (Ksp = 9x10-12) form if [Ag+1] = 2x10-4 and [CrO4-2] = 3x10-5?
Ag2CrO4 (s) <> 2 Ag+1 (aq) + CrO4-2 (aq)
Initial
2x10-4
3x10-5

Ksp = [Ag+1]2[CrO4-2] = 9x10-12


Q = (2x10-4)2(3x10-5) = 1.2x10-12
Since Q < Ksp , No a ppt does not form

Note again that we are not changing the


concentration of [Ag+1] ions here just because there is a 2 in the equation
Example 4: Will a precipitate of Ca3(PO4)2 (Ksp = 2x10-29) form if [Ca+2] = 3x10-5 and [PO4-3] = 4x10-6?
Ca3(PO4)2 (s) <> 3 Ca+2 (aq) + PO4-3 (aq)
Initial
3x10-5
4x10-6

Ksp = [Ca+2]3[PO4-3]2 = 2x10-29


Q = (3x10-5)3(4x10-6)2 = 4.3x10-25
Since Q > Ksp , Yes a ppt forms

Example 5: What concentration of [I-1] will cause a precipitate of PbI2 in a 4x10-5 M solution of Pb(NO3)2?
Ksp PbI2 = 9.8x10-9PbI2 (s) <> Pb+2 (aq) + 2 I-1 (aq)

Ksp = [Pb+2][I-1]2 = 9.8x10-9


9.8x10-9 = (4x10-5) ([I-1])2
[I-1] = 1.57x10-2 M

Any [I-1] concentration greater than 1.57x10-2 will cause Q > Ksp and cause a ppt.

Compounds with Multiple Ions


Example 6: Will a precipitate of AgBr (Ksp = 5.4x10-13) form if solutions are mixed so that [AgNO3] = 3x10-5
and [CaBr2] = 2x10-4 ?
The important thing to note here is that we are examine the Ksp equation of AgBr so we have to examine each compound given to us to look for the part we are interested in to solve the problem. Examine:
[AgNO3] = 3x10-5
[Ag+1] = 3x10-5 M

What part of this compound are we interested in? The Ag+1 part of it. How
many Ag+1 ions are there in this compound? There is only one so we are left
with:

But
[CaBr2] = 2x10-4
[Br-1] = 2(2x10-4)
[Br-1] = 4x10-4 M
AgBr (s) <>
Initial

What part of this compound are we interested in? The Br-1 part of it. How
many Br-1 ions are there in this compound? There are two Br-1 ions so:

Ag+1 (aq) +
3x10-5

Br-1 (aq)
4x10-4

Ksp = [Ag+1][Br-1] = 5.4x10-13


Q = (3x10-5)(4x10-4) = 1.2x10-8
Since Q > Ksp, Yes a ppt forms

Example 7: Will a ppt of Cu(OH)2 (Ksp = 4.8x10-20), form if solutions are mixed so that [CuSO4] = 5x10-6 and
[Ba(OH)2] = 3x10-8?
[CuSO4] = 5x10-6
[Ba(OH)2] = 3x10-8

[Cu+2] = 5x10-6
[OH-1] = 6x10-8

Cu(OH)2 (s) <> Cu+2 (aq) +


Initial
5x10-6

(Note there is 1 Cu+2 for every CuSO4)


(Note there are 2 OH-1 for every Ba(OH)2)

2 OH-1 (aq)
6x10-8

Ksp = [Cu+2][OH-1]2 = 4.8x10-20


Q = (5x10-6)(6x10-8)2 = 1.8x10-20
Since Q < Ksp = There is no ppt

Example 8: Will a ppt of MgF2 (Ksp = 5.2x10-11), form if solutions are mixed so that [MgCl2] = 3x10-4 and
[AlF3] = 7x10-3?

Initial

[MgCl2] = 3x10-4
[AlF3] = 7x10-3

[Mg+2] = 3x10-4
[F-1] = 2.1x10-2

MgF2 (s) <>

Mg+2 (aq) +
3x10-4

(Note there is 1 Mg+2 for every MgCl2)


(Note there are 3 F-1 for every AlF3)

2 F-1 (aq)
2.1x10-2

Ksp = [Mg+2][F-1]2 = 5.2x10-11


Q = (3x10-4)(2.1x10-2)2 = 1.3x10-7
Since Q > Ksp = Yes, there is a ppt

If a compound has more than one of an ionic species


you are interested in for the Ksp equation,
be sure to take that number into account for the initial concentration of that species

Combining Solutions
The last wrinkle you may see in a problem involving precipitation is when the problem asks you to combine
multiple solutions together. The reason this gets a little tricky is because when you combine solutions, the
concentrations of those solutions get diluted. For example, will a ppt of AgCl (Ksp = 1.8x10-10) form if solution A and B are mixed?
Solution A: 50 mL of 0.2 M NaCl
Solution B: 50 mL of 0.2 M AgNO3
Solution A would go from 50 mL of 0.2 M NaCl to 100 mL (the new volume of both solutions). The
volume of the solution doubles. What happens to the concentration when this occurs? Remember from
earlier units that diluting a solution simply uses the following formula:
M1V1 = M2V2
In these problems, however, we will always be looking for the new molarity (M2). Thus, we could
write the above equation as:
V1
M2 = M 1
V2
V1 in the equation is going to be the original volume of the solution. V2 is the new volume when the
solutions are added together (it is the sum of the 2 volumes). You then have to do this for each of the 2
solutions. Continuing the problem above we get:
Solution A original: 50 mL of 0.2 M NaCl
Solution A combined with B:
M2 = M1

Solution B: 50 mL of 0.2 M AgNO3


Solution B combine with A:
M2 = M1

V1
V2

M2 = 0.2

50
100

M2 = 0.1 M NaCl

V1
V2

M2 = 0.2

50
100

M2 = 0.1 M AgNO3

Now that the solutions have been diluted, you may do the problems exactly as before.
Will a ppt of AgCl (Ksp = 1.8x10-10) form if solution A and B are mixed?
[NaCl] = 0.1 M
[AgNO3] = 0.1 M

[Cl-1] = 0.1
[Ag+1] = 0.1

AgCl (s) <> Ag+1 (aq) +


Initial
0.1

(Note there is 1 Cl-1 for every NaCl)


(Note there is 1 Ag+1 for every AgNO3)
Cl-1 (aq)
0.1

Ksp = [Ag+1][Cl-1] = 1.8x10-10


Q = (0.1)(0.1) = 1x10-2
Since Q >> Ksp = A ppt forms

When 2 solutions are combined, dilute each by the following equation:


Where V1 is the volume of the individual solution and V2 is the combined volume.

M2 = M1

V1
V2

Example 9: Will a ppt of BaCO3 (Ksp = 8.1x10-9) form if 100 mL of 6x10-5 M BaCl2 is mixed with 100 mL of
4x10-5 M Na2CO3?
The first thing to do is to dilute each solution:
[BaCl2]combined = 6x10-5 M

100 mL
200 mL

[BaCl2]combined = 3x10-5 M

Note that the 100 mL is the original volume of


the each solution and the 200 mL is the combined volume of both solutions
[Na2CO3]combined = 4x10-5 M 100 mL
200 mL

[Na2CO3]combined = 2x10-5 M

Now that we have diluted the solutions, we do the problem exactly as we did before but with diluted
concentrations from above:
[BaCl2] = 3x10-5
[Na2CO3] = 2x10-5

[Ba+2] = 3x10-5
[CO3-2] = 2x10-5

BaCO3 (s) <> Ba+2 (aq) +


Initial
3x10-5

(Note there is 1 Ba+2 for every BaCl2)


(Note there is 1 CO3-2 for every Na2CO3)

CO3-2 (aq)
2x10-5

Ksp = [Ba+2][CO3-2] = 8.1x10-9


Q = (3x10-5)(2x10-5) = 6x10-10
Since Q < Ksp = No ppt forms

Example 10: Will a ppt of PbCl2 (Ksp = 1.7x10-5) form if 50 mL of 5x10-3 M BaCl2 is added to 120 mL of
4x10-3 M Pb(NO3)2
[BaCl2]combined = 5x10-3 M 50 mL
170 mL

[BaCl2]combined = 1.47x10-3 M

[Pb(NO3)2]combined = 4x10-3 M 120 mL


170 mL

[Pb(NO3)2]combined = 2.82x10-3 M

[BaCl2] = 1.47x10-3
[Pb(NO3)2] = 2.82x10-3

[Cl-1] = 2.94x10-3
[Pb+2] = 2.82x10-3

PbCl2 (s) <> Pb+2 (aq) +


Initial
2.82x10-3

2 Cl-1 (aq)
2.94x10-3

(Note there are 2 Cl-1 for every BaCl2)


(Note there is 1 Pb+2 for every Pb(NO3)2)
Ksp = [Pb+2][Cl-1]2 = 1.7x10-5
Q = (2.82x10-3)(2.94x10-3)2 = 2.4x10-8
Since Q < Ksp = No ppt forms