Using Solubility Rules to Predict Precipitates in Reaction

Lead iodide precipitates when potassium iodide is mixed with lead nitrate.

When two aqueous solutions of ionic compounds are mixed together, the resulting reaction may produce a
solid precipitate. This guide will show how to use the solubility rules for inorganic compounds to predict
whether or not the product will remain in solution or form a precipitate.

Aqueous solutions of ionic compounds are comprised of the ions making up the compound dissociated in
water. These solutions are represented in chemical equations in the form< AB(aq) where A is
the cation and B is the anion.

When two aqueous solutions are mixed, the ions interact to form products.

AB(aq) + CD(aq) products

This reaction is generally a double replacement reaction in the form:

AB(aq) + CD(aq) AD + CB

The question remains, will AD or CB remain in solution or form a solid precipitate?

A precipitate will form if the resulting compound is insoluble in water. For example, a silver nitrate solution (AgNO 3) is mixed with a solution of
magnesium bromide (MgBr2). The balanced reaction would be:

2 AgNO3(aq) + MgBr2 2 AgBr(?) + Mg(NO3)2(?)

The state of the products needs to be determined. Are the products soluble in water?

According to the solubility rules, all silver salts are insoluble in water with the exception of silver nitrate, silver acetate and silver sulfate. Therefore,
AgBr will precipitate out.

The other compound Mg(NO3)2 will remain in solution because all nitrates, (NO3)-, are soluble in water. The resulting balanced reaction would be:

2 AgNO3(aq) + MgBr2 2 AgBr(s) + Mg(NO3)2(aq)

Consider the reaction:

KCl(aq) + Pb(NO3)2(aq) products

What would be the expected products and will a precipitate form?

The products should rearrange the ions to:

KCl(aq) + Pb(NO3)2(aq) KNO3(?) + PbCl2(?)

After balancing the equation,

2 KCl(aq) + Pb(NO3)2(aq) 2 KNO3(?) + PbCl2(?)

KNO3 will remain in solution since all nitrates are soluble in water. Chlorides are soluble in water with the exception of silver, lead and mercury.

This means PbCl2 is insoluble and form a precipitate. The finished reaction is:

2 KCl(aq) + Pb(NO3)2(aq) 2 KNO3(aq) + PbCl2(s)

The solubility rules are a useful guideline to predict whether a compound will dissolve or form a precipitate. There are many other factors that can
affect solubility, but these rules are a good first step to determine the outcome of aqueous solution reactions.

TIPS FOR SUCCESS PREDICTING A PRECIPITATE

The key to predicting a precipitate is to learn the solubility rules. Pay particular attention to compounds listed as "slightly soluble" and remember that
temperature affects solubility. For example, a solution of calcium chloride is typically considered soluble in water, yet if the water is cold enough, the
salt doesn't readily dissolve. Transition metal compounds may form a precipitate under cold conditions, yet dissolve when it's warmer. Also, consider
the presence of other ions in a solution. This can affect solubility in unexpected ways, sometimes causing a precipitate to form when you didn't
expect it.

Ksp: Writing the solubility-product constant expression

This principle was first put forth by Walther Nernst in 1899. It has to do with solid substances usually considered insoluble in water. In each case, we
will consider a saturated solution of the insoluble substance that is in contact with some undissolved solid. Important points to consider are:

1) Some of the solid does dissolve. Not very much, but enough.
2) The substance that dissolves will dissociate 100%.
3) There exists an equilibrium between the undissolved solid and ions in solution.

By the way, all of the examples discussed her and elsewhere are all occurring at standard temperature, which is 25.0 C. Seldom is discussed a
Ksp problem at anything other than standard temperature.

Since equilibrium principles can be used, that is where we start. Our first example is silver chloride, AgCl. When it dissolves, it dissociates like this:

AgCl(s) Ag+(aq) + Cl(aq)

An equilibrium expression can be written:

Kc = ( [Ag+] [Cl] ) / [AgCl]

Now, we come to an important point. When the AgCl is enclosed in square brackets like this -- [AgCl] -- that means the "molar concentration" of solid
AgCl. This value is a constant!! Why?

Answer: The "molar concentration" of a solid (it's not a useful chemistry idea, so it is seldom used) can be directly related to the density, which is also
a constant. Here is a graphic which summarizes the relationship:

What we do is move the [AgCl] to the other side and incorporate it with the equilibrium constant. We can do this because [AgCl] is a constant.

Kc [AgCl] = [Ag+] [Cl]

Since Kc [AgCl] is a constant (because it's a constant times a constant which yields a constant), we replace it with a single symbol. Like this:

Ksp = [Ag+] [Cl]

(Just a side point: as you go on in chemistry, you'll get introduced to the concept of activity. The activity of a solid is defined as equal to the value of
one. Since the activity of AgCl(s) = 1, it just drops out of the above expression. However, like I said, activity is for the future. Not right now.)
It turns out that the Ksp value can be either directly measured or calculated from other experimental data. Knowing the Ksp, we can calculate the
solubility of the substance in a very straightforward fashion.

Here are three more examples of dissociation equations and their Ksp expressions:

Sn(OH)2(s) Sn2+(aq) + 2OH(aq) Ksp = [Sn2+] [OH]2

Ag2CrO4(s) 2Ag+(aq) + CrO42(aq) Ksp = [Ag+]2 [CrO42]

Fe(OH)3(s) Fe3+(aq) + 3OH(aq) Ksp = [Fe3+] [OH]3

In order to write Ksp expressions properly, you must know how each ionic substance dissociates in water. That means you have to know your
chemical nomenclature, polyatomic ions, and the charges associated with each ion.

Also, and this is important, so pardon the shouting:

EACH CONCENTRATION IN THE Ksp EXPRESSION IS RAISED TO THE POWER OF ITS COEFFICIENT IN THE BALANCED EQUATION.

Two more examples:

Hg2Br2(s) Hg22+(aq) + 2Br (aq) Ksp = [Hg22+] [Br]2

Zn3(AsO4)2(s) 3Zn2+(aq) + 2AsO43(aq) Ksp = [Zn2+]3 [AsO43]2

Note how the mercury(I) ion is written. Hg22+ is correct. Do not write it as 2Hg+. Writing [Hg+]2 in the Ksp expression is wrong.

Here are ten chemical formulas. Write the chemical equation showing how the substance dissociates and write the K sp expression.

1) AlPO4 2) BaSO4 3) CdS 4) Cu3(PO4)2 5) CuSCN

6) AgCN 7) Mn(IO3)2 8) PbBr2 9) SrCO3 10) Bi2S3

Go to the answers

By the way, a word of warning. You may have done quite well at learning chemical nomenclature. However, in the study of K sp, there may be some
polyatomic ions used that you did not study in the nomenclature section. Thiocyanate (SCN) might be one example. Another could be the arsenate
ion, (AsO43-). Note that arsenic is just below phosphorous in the periodic table. Compare arsenate with phosphate (PO 43-).