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General Chemistry
Acid–Base and Solubility Equilibria

Will a Precipitate Form at the Given

Concentrations? Ksp and Q
When discussing the molar solubility and solubility product constant (Ksp), we
mentioned that the values pertain to saturated solutions of the given
compound.
For example, the molar solubility of BaOS 4 is 3.87 x 10-5 mol/L. Therefore, it
starts precipitating only once the concentration goes higher than 3.87 x 10 -
5
mol/L which means below this concentration, it is dissociated to ions. The
solubility product, Ksp for BaOS4 is 1.5 x 10-9:

BaSO4(s) ⇆ Ba2+(aq) + SO42-(aq)

Ksp = [Ba2+][ SO42-]

So, let’s say we want to find out if there will be any precipitation in a solution
containing 2.0 x 10-6 M Ba2+ and 2.0 x 10-6 M SO42-.
To do this, we use the ion product quotient, Q which is the same expression
as Ksp only that in this case, we use the initial concentrations of the ions.
Conceptually, this is no different than the reaction quotient we discussed in
chemical equilibrium.
So, Q is calculated for any concentrations of the ions, while the Ksp is the value
specifically given for the concentrations at equilibrium when Q = Ksp.

BaSO4(s) ⇆ Ba2+(aq) + SO42-(aq)

Q = [Ba2+]0[SO42-]0
Where [Ba2+]0 and [SO42-]0 are the initial concentrations of the ions. And by
“initial” we mean as soon as the ions appear in the solution. The threshold for
precipitation to start is when Q becomes larger than Ksp. Q > Ksp indicates there
is simply too much of the ions floating around and some of them must react
and precipitate from the solution. On the other hand, if Q < Ksp, this means
there is not enough of the ions and the solution can handle (dissolve) more,
therefore, there will be no precipitation.
To make it more visual, we can write the Q and Ksp correlation with the
expression and the specific value.
Notice that in the discussion above, we have not mentioned where the
Ba2+ and SO42- ions coming from. You cannot have a solution with a separate
anion or a cation, and neither can you store them separated in one solution
because, as we mentioned, at some point they will react and precipitate.
Therefore, the principle of Q and Ksp correlation is used to determine if there
will be a precipitation when certain amounts of two solutions are mixed.

For example,
Will there be any precipitation observed if 30.0 mL of 0.10 M Ba(NO3)2 solution
are added to 50.0 mL of 0.10 M Na2SO4? Ksp for BaSO4 is 1.5 × 10−9
The first part is to identify the possible precipitate if not evident from the
problem. In this case, you can see it because of the Ksp value, and because we
talked about it already. However, let’s say the precipice wasn’t evident. So, you
need to write the reaction between the two compounds:
Ba(NO3)2(aq) + Na2SO4(aq) → BaSO4(s) + 2NaNO3(aq)
Based on the solubility rules, the only precipitate that can form here is
BaSO4, so go ahead and write the expression for Ksp and the corresponding
dissociation equation:
BaSO4(s) ⇆ Ba2+(aq) + SO42–(aq)
Ksp = [Ba2+][SO42–]
Next, determine the concentration of the two compounds once the solutions
are mixed. Remember, to add up the volumes of the two solutions:

V = 30.0 + 50.0 = 80.0 mL = 0.0800 L

You can either determine the concentration of the salt in the final solution
using the dilution equation or first calculate the moles and then divide it by
the volume of the final solution. Let’s go with the first approach and let V 2 be
the volume of the final solution.
Assigning V1 as the volume of the initial 30.0 mL (0.0300 L) solution of For
Ba(NO3)2, we can calculate its concentration the final solution (M 2) using the
equation for dilution:
M1V1 = M2V2
0.100 mol/L x 0.0300 L = 0.0800 L x M2
M2= (0.100mol/L×0.0300L) ÷ 0.0800L = 0.0375M
For Na2SO4, let this be the V2, and the V1 is the initial 50.0 mL (0.0500 L). Using
the equation for dilution, the concentration in the new solution (M 2) will be:
 M1V1 = M2V2
0.100 mol/L x 0.0500 L = 0.0800 L x M2
M2= (0.100mol/L×0.0500L) ÷ 0.0800L = 0.0625M
Next, determine the concentration of Ba 2+ and SO42– ions based on the
stoichiometric ratio of the ions with the salt. For this, you can write the
corresponding dissociation equations:
Ba(NO3)2(aq) → Ba2+(aq) + 2NO3–(aq)
Na2SO4(aq) → 2Na+(aq) + SO42-(aq)
Because of the 1:1 ratio, there will be 0.0375 M Ba2+ and 0.0625 M SO42- ions
when the solutions are mixed.
At this point, calculate the quotient using the initial concentrations, [Ba 2+]0 and [
SO42–]0 of the ions before any precipitation occurs:
BaSO4(s) ⇆ Ba2+(aq) + Ba2+(aq)
Q = [Ba2+]0[ SO42–]0 = (0.0375) (0.0625) = 0.00306 = 2.34 x 10-3
Q > Ksp, therefore, BaSO4 will form as a precipitate

Let’s do another example when the given concentration of ions does not
cause precipitation.

Will a precipitate form when 100. mL of 0.035 M Pb(NO3)2 is added to 100. mL

of 0.045 M NaCl? Ksp for PbCl2 is 1.6 × 10−5.

First, identify the possible precipitate if not given. In this case, you can see
because of the Ksp value, however, let’s say the precipice wasn’t evident. Write
the reaction between the two compounds:

Pb(NO3)2(aq) + 2NaCl(aq) → PbCl2(s) + 2NaNO3(aq)

Based on the solubility rules, the only precipitate that can form here is PbCl 2, so
go ahead and write the expression for Ksp and the corresponding dissociation
equation:

PbCl2(s) ⇆ Pb2+(aq) + 2Cl–(aq)

Ksp = [Pb2+][Cl–]2
Next, determine the concentration of the two compounds once the solutions
are mixed. Remember, to add up the volumes of the two solutions for the total
volume:

V = 100. + 100. = 200. mL = 0.200 L

Let’s, this time, calculate the moles first.

n (Pb(NO3)2) = 0.100 L x 0.035 M = 0.0035 mol

n (NaCl) = 0.100 L x 0.045 M = 0.0045 mol

The concentrations in the new solution will then be:

M (Pb(NO3)2) = 0.0035 mol ÷ 0.200 L = 0.0175 M

M (NaCl) = 0.0045 mol ÷ 0.200 L = 0.0225 M

Next, determine the concentration of Pb 2+ and Cl– ions based on the

stoichiometric ratio of the ions with the salt. For this, you can write the
corresponding dissociation equations:

Pb(NO3)2(aq) → Pb2+(aq) + 2NO3–(aq)

NaCl(aq) → Na+(aq) + Cl–(aq)

Because of the 1:1 ratio, there will be 0.0175 M Pb2+ and 0.0225 M Cl– ions
when the solutions are mixed.
At this point, calculate the quotient using the initial concentrations [Pb 2+]0 and
[ Cl–]0 of the ions before any precipitation occurs:

PbCl2(s) ⇆ Pb2+(aq) + 2Cl–(aq)

 Q = [Pb2+]0[Cl–]02= (0.0175) (0.0225)2 = 8.9 x 10-6

Q is smaller than Ksp, therefore, no precipitate will form.

Check Also
 Buffer Solutions
 The Henderson–Hasselbalch Equation
 The pH of a Buffer Solution
 Preparing a Buffer with a Specific pH
 The Common Ion Effect
 The pH and pKa Relationship
 Strong Acid–Strong Base Titrations
 Titration of a Weak Acid by a Strong Base
 Titration of a Weak Base by a Strong Acid
 Titration of Polyprotic Acids
 Buffer Solutions Practice Problems
 Ksp and Molar Solubility
 The Effect of a Common Ion on Solubility
 The Effect of pH on Solubility
 Ksp and Molar Solubility Practice Problems

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 0.100 mol/L x 0.0500 L = 0.0800 L x M2
M2=0.100mol/L×0.0500L0.0800L=0.0625M