General Chemistry Equilibrium Solubility

Relative Solubility
It is difficult to prldict relative solubility. The only way to comPare is through
experiments or data analysis. We'll start by comparing the solubilities of calcium
carbonate (CaCO3) and calcium fluoride (CaF). When a question asks for the
highest solubility, it refers to the compound that produces the greatest amount of
dissociated salt, which refers to greatest molar solubility, not solubility product!

The solubility product of CaCO3 is 8.7 x 70-9 \,/P, and the solubility product for
CaFr is 4.0 ri0-11M3. whlch of the two salts is more soluble?
Witli questions like these, keep in mind that you never compare numbers with
unlike units. Solubility products are used to determine the molar solubility'
CaCo3 is an MX salt, sJ iro = while CaF2 is an MX2 salt' so KsP = 4x3' The
"t,
determinations of molar solibility for both calcium salts is shown below.
CaCo3: * = lR* =t[ei;i'ug ={87 xfio-1o = 9'? x10-s M
af-

- =:V4
CaFr: x E9Y =Vro "{tr'FT =2.?x1o-4M

The molar solubility for CaCO3 is 9.3 x 10-5 M_ and for CaF2 it is 2.2 x 10-4, but l
exact values are not necessary, b".urrr" 9.? x 10-5 M is less than2.? x 10-4 M. CaF:
is more soluble than CaCO3, even though it has a smaller solubility product'
Relative solubility questions are asked in many ways such as: "\Alhich salt
exhibits greater solvation?" and "Which salt precipitates first?-'' Use molar
solubilitylo answer questions that address relative solubility' Solubility product x
is employed only for calculation-based questions' (
I
Example 3.23
Vr4rich of the following salts yields the LEAST amount of silver ion in water?
A. AeBr(s) K". = 7.9 * 1g-13142
B. a[cri'i r,i = i.o * 1s-10 142
C. a[zcto+t'i Krp = 9.0 * 19-12 tr43
o. a!3ro41r1 frf'= 1.6 * 19-18144

Solution
You must recognize that the choices ale not all the same type of salt. Choices A
and B are MX ialts, so their solubility products may be compared^ AgBr has
a

lower solubility product than AgCl, soAgBr also has a lowerrnolar solubiLit''-
This eliminates choice B. Choice C is an M2X salt, and choice D is an M3X sai:
To solve the question, you need molar solubility values- The calculation of
th'e

molar solubiliiy for the three remaining salts is shown below'

Choice A: *=y'K; ='[zs *taB ='[7g x^tlT{ = 8'9x 10'7M

Choice C: x=
Rr" ffi" 1g-TT
I z
=1'lri , t0-12 = 1.3 x 10-4 M
V4 V 4
4
R; ' o,fs t lcrlF (,.7 x M
D: x = 4l =\ 10-20 = 1..6 x10-5
Choice
Yzz Y =4t1'=-
zz )
AgBr, choice A, has the lowest molar solubility' However, the question asked fll tr
loivest [Ag*], not lowest molar solubility. For choice C, Ag2CrO+, there are tf
i: d
sltver cations, and choice D, Ag3PO4, has three silver cations, so the [Ag*] :-' s
actually double and triple their iespective molar solubilities, making them mu::
too high to be the actual answer. dll

rf,
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General Chemistry Dquilibrium Solubility

Solubility Experiments
The molar solubility of a salt is an empirical value, determined from experiments
involving saturated solutions. While forming a saturated solution is easy to do,
determining the ion concentration is not necessarily an easy task. To form a
saturated solution, enough salt is added to water so that precipitate remains on
the bottom of the container. Determining the amount of dissolved salt may be
accomplished in many ways, of which we shall discuss three. The first method
involves spectroscop!, where the amount of absorbed light at a fixed wavelength
depends on the concentration of ions, according to Beer's law (Equation 1.3).
This method works only if one of the ions absorbs electromagnetic radiation. The
second method involves measuring the amount of salt added and then collecting,
drying, weighing, and then subtracting the mass of precipitate from this value.
This method works only if the salt is highly soluble. The third method involves
using an ion exchange column to exchange the cation in solution for hydronium.
The concentration of hydronium is determined via pH. This method works only
if the salt does not exhibit acid-base properties and has a cation concentration of
at least 10-5 M. You may encounter passages about all three methods.

Example 3.24
What is the molar solubility of calcium carbonate in water given that the addition
of 4.00 mg of CaCO3(s) to enough water to form exactly 500.0 mL of an aqueous
CaCO3 solution yields 0.55 mg of anhydrous precipitate?
A. 6.90 x 10-3 M CaCO3
B. 3.45 x 10-3 M CaCO3
C. 6.90 x 10-5 M CaCO3
D. 3,45 x 10-5 M CaCO3
Solution
You must keep in mind the units of the question and then solve for each unit. In
other words, the answer is in terms of moles/liter, which implies that you must
find both moles and iiters to solve the question. The liters of solution are simple,
in that 500.0 mL is equal to 0.500 liters. The amount of calcium carbonate that
Cissociates into solution is 3.45 mg. The amount of calcium carbonate in
milligrams is converted to grams by multiplying by 10-3, and then to moles by
Cividing by the molecular mass of calcium carbonate (100 grams per mole). The
mathematical set-up is shown below

3'45 x 10-3 gramsCacoa

Moles: = 3.45x 10-5 molesCaCo3
gramTmole
1oo

Volume: 500.0 mL . = 0.500L CaCo3(aq)

*#h
Concentratio',. 3.45
x L0-5 molesCaCO3
= 6.90x 1o-5 MCaCo3laqy
0.500 L solution
The correct answer is choice C.

>olubility looks daunting, but is actually quite simple conceptually. Don't be

-ntimidated by difficult-looking topics. They're usually pretty easy. Some
applications of solubility include ion exchange (ion exchange columns), selective
solubility (precipitation of a selected cation or anion), and the common ion effect.
iJf ion exchange, selective solubility, and the common ion effect, only common
-on effect involves heavv mathematics.

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General Chemistry Equilibrium Solubility

Common Ion Effect

(salt) in
The common ion effect is the reduction in solubility of an ionic solid
solution, because one of the ions in the salt is already present in solution.
In a
way, the concept is similar to Le Chatelier's principle. According to Le
ChAieter's principle, when you add one of the ions to a saturated salt solution,
of a
the reaction shifti to the lefi (reactant side). This results in the formation
is less soluble. Addition of an ion to solution
frecipitate (more solid), so the salt
,"d.r""d the solubility. According to the common ion effect, if one of the ions is
already present in iolution, then less salt is capable of dissociating, so
the
The results are the same when an ion is added to solution;
sotufiiity is reduced.
the difference between Le Chdtelier's principle and the common
ion effect is the
timing of when they are added. Consider Reaction 3'7'
AgCl(s) + HrO(l) =- Ag*(^q) + Cf(aq)
Reaction 3.7

with the addition of either Ag+ or Cl- to solution in Reaction 3.7, there is a
in
reduction in the amount of Agcl that can dissociate into it, due to the presence
the solution of one of the ions-constituting the salt (Ag+ or Cl-).
This is similar to
Le Chatelier's principle, except that either Ag+ or Cl- is present in solution
in the
beginning rather than being added once the solution has reached a solubilitl
ion
uqii6U.i i*. euestions ot ih" MCAT may be asked from either a common
perspective or a Le ChAtelier's principle's perspective'
Le Chatulier's style question: which way will the reaction shift when
Ag+(aq) is
added to a saturated aqueous silver chloride solution? According to
Le
side' so
Chatelier's principle, adding a product shifts the reaction to the reactant
a

precipitate ?ortnt. This means that the salt becomes less soluble.
Common ion effect style question: Is silver chloride more soluble
in pure water or a
M Naciiaq) sbluiionl According to the common ion effect, because the
0.10
already
sodium chloride solution has chloride i-ons (also found in silver chloride)
present in solution, the solubility of the salt is reduced. we shall
look at this
'question from a mathematical perspective, later in the discussion of this topic'

The common ion effect, simply put, says that the presence of a mutual ion
sharing that
already dissolved into solution tldn."t the solubility of a second salt
stannous fluoride is less soluble in a solution of sodium
mutual ion. For instance,
fluoride than distilled water because of the presence of the fluoride anion'
concentration.
Common ion effect questions can incorporate pH and hydroxide

Example 3.25
rurufirir- hydroxide is MoST soluble in which of the following solutions?
A. Vinegar (PH = 2.5)
B. Citric acid (PH = 4.5)
C. Los Angeles taP water (PH = 5'5)
D. Distilled water (PH = 7.0)
Solution
question involves the common ion effect, where the common ion
is
ihis with the
hydroxide anion. Magnesium hydroxide is most soluble in the solution
corresponds to the most acidic solution. The most
least hydroxide anion)which
lowest pH, wirich makes choice A the best answer' This is
acidic solution has the
salts'
the reason that acid rain is tr.h u serious problem: it dissolves basic

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General Chemistry Equilibrium Solubility

Example 3.26
At what pH is Ca(OH)2(s) most soluble in water?
A.3
8.5
c.9
D. 11

Solution
The pH at which Ca(OH)Z(s) is most soluble is the pH at which there is the least
common ion (OH-) present in solution. There is the least OH- present at lower
pH values, where the solution is acidic. The best answer is choice A. Note that
basic salts are most soluble in acidic solutions.

Example3.27
(NHa)3(CoCl6)(s) is MOST soluble at which pH?
A.3
8.5
c.9
D. 11

Solution
The pH at which (NHa)3(CoCl6)(s) is most soluble is the pH at which there is the
most OH- in solution. This is because of a complex equilibrium. The OH- in
solution can deprotonate the ammonium cation (NHa+) to form ammonia, which
reduces the amount of ammonium present in solution. As the amount of NH4+
in solution decreases, the (NHa)3(CoCl5)(s) equilibrium shifts to products to
generate more NH4+. The most OH- is present at higher pH values, where the
solution is basic. The best answer is choice D. Note here that acidic salts are
most soluble in basic solutions. The two equilibrium equations are as follows:

(NHa)3(CoCl5)(s) -_- 3 NH4+(at) + CoCl63-(at)

NH4+(aq) + OH-(aq) =- NH3(at) + H2O(aq)

-{s the second reaction shifts to the right, the first reaction is displaced from
equilibrium, so it too shifts to the right. This is a complex equilibrium. The two
:eactions are flependent on one another.

Be able to make qualitative predictions about solubility based on both the

;onunon ion effect and complex equilibrium. Example 3.25 and Example 3.26 are
:ramples of the common ion effect. Example 3.27 is an example of increased
'olubility due to the presence of a complexing ion in solution.
Both of these
:oncepts play a role in determining solubility. \Alhen doing calculations with the
:rmmon ion effect, be sure not to plug variables into the solubility product
::rmula blindly. In the case of an MX salt, for instance, KrO still is equal to
\l+l[X], but the values of [M+] and [X-] are not just x with the common ion
-ifect. The concentration of the ion that is already present in the solution is
:rund by summing the initial concentration and the additional ion formed from
-:.e dissociation of the salt (x). This is [X-]61g61 + x. In most cases, the x will be
:significant relative to the [X-]nitiul, so it can be ignored. Most common ion
:tect questions should be simple and fun after you have done enough of them.

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General Chemistry Equilibrium Solubitity

Example 3.28
What is the molar solubility of CaCl2(s) in 0.01 M NaCl(aq) solution?
CaCl2(s) 4 Ca2+1aq; + 2 Cl-(aq) Ksp = 2.5x 10-10 M3
A. 2.5 x 10-4 M
B. 2.5x10-6M . ." '' :'l t"i";
c. 2.5 x 10-8 M
D. 2.5 x 1o-10 M

Solution
This question is purely mathematical. The key fact is recognizing that there
0.01 M Cl- in solution initially. The setup and solution are as follows:

Reaction: CaCl2(s) : Ca2+1aq; + zCI-

Initially: excess 0 0.01
Shifl - x ---+ +x +2x
Equilibrium: whocares? x 0.01 + 2x

Kro = pa2+ltcrl2 ...Kro =1x{0.01. +zxf

If weignore2x: Ksp =2.5x1g-10 =1x{0.01f = 0.0001(x) .'.x = 2.5x 10-6M
The correct answer is choice B.

Example 3.29
\Alhat is the molar solubility of Ca(OH)2 in an aqueous solution at pH = 13, giveur
that the KrO for Ca(OH)2 is 6.5 x 10-o Mr?
A. 6.5 x 10-5M
B. 6.5 x 10-4M
C. 'J..2x10-2M
D. 6.5 x 1,020 M

Solution
This question is purely mathematical as well. You must recognize that there is
0.10 M OH- present in a pH = 1?_solution, because pH + pOH = 1.4 fot an
aqueous solution and [OH-] = 10-PoH. The equation, set-up, and solution are as
follows:
Reaction: Ca(OH)z(s) Ca2+1aq; + 2OH-
Initially: excess 0 0.10
Shift: -x -
--+ +x +2x
Equilibrium: whocares? x 0.10 + 2x

Kro = [Ca2+]toH-12 .'.Kro =(x{0.10 +zxf

Upon ignoring 2x: Kro = 6.5x 19-6 =1x{O.t0P - 0.0{x) .'.x = 6.5x 10-4 M
The correct answer is choice B.

Calculation questions involving the common ion effect are actually rather simpL+
but in most cases the average student is not familiar with the process. Si-pS
plug in the value for the preexisting concentration, and solve for x from the K*
expression.

Copyright O by The Berkeley Review 194 The Berkeley Revicn