CHEM 102 Instructional Objectives

Prof. Upali Siriwardane,

Chemistry Program, Louisiana Tech University, Ruston, LA 71272.
CHAPTER 17. Additional Equilibria

Chapter 17. Additional Aqueous Equilibria

17.1
17.2
17.3
17.4
17.5

Buffer Solutions
Acid-Base Titrations
Acid Rain
Solubility Equilibria and the Solubility Product Constant, Ksp
Factors Affecting Solubility / Precipitation: Will It Occur?

Objectives are as follows:

Basic Skills
Students should be able to: Chapter 17.
1. Explain how buffers maintain pH, how to calculate their pH, how they are prepared, and the
importance of buffer capacity (Section 17. 1).
2. Use the Henderson-Hasselbalch equation to calculate the pH of a buffer and the pH change after
acid or base has been added to the buffer (Section 17. 1).
3. Interpret acid-base titration curves and calculate the pH of the solution at various stages of the
titration (17.2).
4. Explain how acid rain is formed and its effects on the environment (Section 17-3).
5. Relate a Ksp expression to its chemical equation (Section 17.4).
6. Use the solubility of a slightly soluble solute to calculate its solubility product, (Section 17.4).
7. Describe the factors affecting the aqueous solubility of ionic compounds (17.5)
8. Apply Le Chatelier's principle to the common ion effect (Section 17.5).
9. Use the solubility product to calculate the solubility of a sparingly soluble solute in pure water
and in the presence of a common ion (Section 17-5).
10. Describe the effect of complex ion formation on the solubility of a sparingly soluble ionic
compound (Section 17.5).
11. Relate Q, the ion product, to Ksp to determine whether precipitation will occur (Section 17.6.).
12. Predict which of two ionic solutes will precipitate first (Section 17.6).

CHEM 102 CLASS PROBLEMS

Prof. Upali Siriwardane,
Chemistry Program, Louisiana Tech University, Ruston, LA 71272
CHAPTER 17
KEY CONCEPTS

pH for buffer solutions

concentration of ions in buffer

solutions
pH indicators

preparing a buffer of a
desired pH
titration curve
Solubility product

selecting an indicator for an

titration
Ksp expression

Apply Le Chatelier's
solubility problems

Ksp to determine precipitation of a

salt

pH for solutions with common

ions
determine the color of an
indicator at certain pH
acid rain
Factors affecting solubility of
ionic compounds
Complex ion formation

Common-ion Effect
Refers to decrease in solubility of an acid, base or ionic salt (i.e., one that dissociates in solution into
its ions) caused by the presence in solution of another solute that contains one of the same ions as the
salt. The common-ion effect is an example of chemical equilibrium.
Weak Acid and its Soluble Salt
For example, acetic acid, CH3COOH, is a weak acid that in solution slightly dissociates into the
hydronium H3O+ and acetate, CH3COO-, the equilibrium state being represented by the equation
CH3COOH + H2O

H3O+ + CH3COO

According to Le Chtelier's principle, when a stress is placed on a system in equilibrium, the system
responds by tending to reduce that stress. In the system taken as an example, if another solute
containing one of those ions is added, e.g., sodium acetate, NaCH3COO, which supplies CH3COO
ions, the solubility equilibrium of the solution will be shifted to remove more CH3COO from the
solution, so that at the new equilibrium point there will be fewer CH3COO ions in solution and more
undissociated CH3COOH in the solution.
Weak Base and its Soluble Salt
For example, ammonia, NH3, which is a weak base that in solution slightly dissociates into the
hydronium NH4+ and hydroxide, OH-, the equilibrium state being represented by the equation
NH3 + H2O

NH4+ + OH

According to Le Chtelier's principle, when a stress is placed on a system in equilibrium, the system
responds by tending to reduce that stress. In the system taken as an example, if another solute
containing one of those ions is added, e.g., ammonium chloride, NH4Cl, which supplies NH4+ ions, the
solubility equilibrium of the solution will be shifted to remove more NH4+ from the solution, so that at
the new equilibrium point there will be fewer NH4+ ions in solution and more undissociated NH3 in the
solution.
Insoluble Metal Salt and another same Soluble Metal Salt
For example, silver chloride, AgCl, is a slightly soluble salt that in solution dissociates into the
ions Ag+ and Cl-, the equilibrium state being represented by the equation AgClsolid ~Ag++Cl-. According
to Le Chtelier's principle, when a stress is placed on a system in equilibrium, the system responds by
tending to reduce that stress. In the system taken as an example, if another solute containing one of
those ions is added, e.g., sodium chloride, NaCl, which supplies Cl- ions, the solubility equilibrium of
the solution will be shifted to remove more Cl- from the solution, so that at the new equilibrium point
there will be fewer Ag+ ions in solution and more AgCl precipitated out as a solid.
Hydrolysis of a Salt
A salt is an ionic compound containing positive ions other than H+ and negative ions other than
OH. Most salts will dissociate to some degree when placed in water. In many cases, ions from the salt
will react further with water to produce hydronium ions or hydroxide ions. Any chemical reaction of
ions with water is called a hydrolysis reaction.
1) Salt of strong acid and strong base forms ions which are neutral.
2) Salt of weak acid and strong base forms ions which are basic.
3) Salt of strong acid and weak base forms ions which are acidic.
4) Salt of weak acid and weak base forms ions which are either
neutral, basic or an acidic depending on the relative strengths of the
acid and the base.
Buffer Solution
A buffer solution are usually combinations of weak acid/soluble-salt or weak base/ soluble-salt
combinations Buffers resists changes in pH when small quantities of an acid or an alkali are added to it.
Acidic buffer solutions
An acidic buffer (weak base/ soluble-salt: NH3/NH4Cl ) solution is simply one which has a pH less
than 7. Acidic buffer solutions are commonly made from a weak acid and one of its salts - often a
sodium salt.
A common example would be a mixture of ethanoic acid and sodium ethanoate in solution. In this case,
if the solution contained equal molar concentrations of both the acid and the salt, it would have a pH of
4.76. It wouldn't matter what the concentrations were, as long as they were the same.

You can change the pH of the buffer solution by changing the ratio of acid to salt, or by choosing a
different acid and one of its salts.
Describe the (buffer effect) of common ions in the solutions containing following:
a) Basic buffer: weak acid/soluble-salt of a weak acid; HC2H3O/NaC2H3O.
b) Acidic buffer: weak acid/soluble-salt of a weak base; NH3/NH4Cl.
a) Basic buffer: weak acid/soluble-salt of weak acid; HC2H3O2/NaC2H3O2.
The main equilibrium in this system is:
H2O + C2H3OHO- + HC2H3O2 ( acid dissociation )
common ion
The common ion C2H3O- will decrease the [HO-] increasing pH of the solution. This solution can act
as a buffer for changes in pH. If the pH of the solution is increased (adding more HO-) this equilibrium
will shift to left to maintain the original pH. If the pH of solution is decreased (adding H+) the
equilibrium will shift to right to remove extra H+.
:
b) Acidic buffer: weak acid/soluble-salt of weak base; NH3/NH4Cl
NH3 + H2O
NH4+ + OH- (base dissociation)
The main equilibrium in this system is:
H2O +
NH4+
H3+O + NH3
common ion
The common ion NH4+ will increase the H+ or [H+3O] decreasing pH of the solution. Similar to 6a
[HC2H3O2/NaC2H3O2] this equilibrium can buffer changes in pH.

Henderson-Hasselbalch Equation
According to the Brnsted-Lowry theory of acids and bases, an acid (HA) is capable of donating a
proton (H+) and a base (B) is capable of accepting a proton. After the acid (HA) has lost its proton, it is
said to exist as the conjugate base (A-). Similarly, a protonated base is said to exist as the conjugate
acid (BH+).
The dissociation of an acid can be described by an equilibrium expression:
Acid:

HA + H2O

H3O + A

[H3+O][ A]
; Ka = --------------[HA]

Consider the case of acetic acid (CH3COOH) and acetate anion (CH3COO-):
CH3COOH(aq) + H2O(l)
CH3COOH(aq); Ka =

H3O+(aq) + CH3COO(aq), for which the equiilibrium constant is

[H3+O ][ CH3COO]
----------------------[HC2H3O2]

Acetate is the conjugate base of acetic acid. Acetic acid and acetate are a conjugate acid/base pair. We
can describe this relationship with an equilibrium constant:

In this example, we will use Ka for the acid dissociation constant. Taking the negative log of both sides
of the equation gives:

This can be rearranged:

By definition, pKA = -logKA and pH = -log[H+], so

This equation can then be rearranged to give the Henderson-Hasselbalch equation:

The Henderson-Hasselbalch equation can be used to prepare buffer solutions and to estimate charges on
ionizable species in solution, such as amino acid side chains in proteins. Caution must be exercised in
using this equation because pH is sensitive to changes in temperature and salt concentration in the
solution being prepared.
Buffering Capacity
Buffer capacity is defined as the amount of H+ or OH- a buffered solution can absorb without
significantly changing the pH. Capacity determined by magnitude of [HA] and [A-], lager the
concentrations of them higher the buffer capacity.
How is Henderson-Hesselbalch equation is used to calculate pH and pOH of buffer solutions.
If the concentration of the acid and the conjugate base is known in a buffer solution, the pH of the
solution can be calculated using a general equation called Henderson-Hesselbalch equation.
pH

= pKa -

[ACID]
log ----------[BASE]

E.g. Buffer solution made from a weak acid/salt: HC2H3O2 /NaC2H3O2

pH

[HC2H3O2]
= pKa - log --------------[NaC2H3O2]

E.g. Buffer solution made from a weak base/salt: NH3 /NH4Cl

pH

= pKa - log

[NH4Cl]
-----------[NH3]

For a weak base (NH3) or acid (HC2H3O2) with Kb or Ka ,respectively, the value of Ka or Kb for the
corresponding conjugate acid (NH4+ ) or base (C2H3O2-) can be calculated from the following
expression:
Kb x Ka = Kw

Calculate the pH of a solution prepared by adding 50 g of NH4Cl and 32.5g of NH3 and diluted to
a liter. (Kb(NH3); 1.8 x 10 -5
This is a problem where weak base/salt is making a buffer solution. We can apply HendersonHesselbalch equation for this condition.
[ACID]
pH = pKa - log ----------- ;
[BASE]
[ACID] = [NH4Cl] conjugate acid, [NH3] base
[NH4Cl]
pH
= pKa - log
[NH4Cl]
[NH3]

= 50.0 g NH4Cl

x l mol NH4Cl
53.3g NH4Cl

1
1L

32.5 g NH3

x l mol NH3
x 1
17.04 g NH3
1L

----------[NH3]

= 0.9346 M( mol/L)

1.9072 M( mol/L)

Can be calculated from the following For a weak base (H3) with Kb the value of Ka for the corresponding con
(NH4+ or NH4Cl) expression:
Kb x Ka = Kw
Kw
= ------Ka
Kb
Ka =

1.0 x 10-14
1.8 x 10 -5
pH

= 5.56 x 10-10
p Ka

log

[NH4Cl]
--------------------[NH3]
0.9346 M

pH

= p Ka

log

----------------

1.9072 M
pH

= - log [5.56 x 10-10]

0.9346 M

- log

-----------------------

1.9072 M
pH = 9.26
PH = 9.57
Acid-Base Titrations

- (-0.309)

A titration is a procedure used in analytical chemistry to determine the amount or concentration of a

substance. In a titration one reagent, the titrant, is added to another slowly. As it is added a chemical
stoichiometric reaction occurs until one of the reagents is exhausted, and some process or device
signals that this has occurred. The purpose of a titration is generally to determine the quantity or
concentration of one of the reagents, that of the other being known beforehand. In any titration there
must be a rapid quantitative reaction taking place as the titrant is added, and in acid-base titrations this
is a stoichiometric neutralization. The type of titration is simply the type of chemical reaction taking
place, and so in this section we consider acid-base titrations.
Acid-Base Indicators
Many substances, including litmus, the one dye almost everyone associates with acids and bases,
change color in response to acid or base. The pigment in red cabbage is another natural substance
very commonly used to show color change. Phenolphthalein is one of the most common indicators
used for beginning chemistry, because its color change is very obvious which makes it easy to use.
There are many other indicators that change colors at different pH's, and so are useful for different
purposes. pH paper commonly contains a mixture of different indicators that change colors at different
pH's. The mixture is applied to paper, and then compared to a color chart to see what the pH of a
solution is, approximately.
Acid-Base indicators are dyes that are themselves weak acids and bases. However, the conjugate acidbase forms of the dye have different colors. The actual chemical structures of the dyes is often quite
complex; however, we can use the generic symbol for the indicator as HIn. The Brnsted-Lowry
equation for the indicator is:
HIn + H2O

H3O+ + In-

where the color of the letters is used to show the differently colored forms of the dyes.
Suppose that we increase the concentration of H3O+. Then if we apply LeChatelier's principle, the
result should be more HIn.
There will be more H3O+ (because we added more), but the system will respond to:

use up some of the added H3O+, at the same time

removing some of the In-, and
making more HIn (and H2O, though that is pretty irrelevant since the reaction takes place in lots
of water anyways).

Thus we will see the color of the HIn form.

Now suppose that we decrease the concentration of H3O+ (which we could do by adding more OH-).
Now applying LeChatelier's principle, the result should be more In-.

There will be less H3O+ (because we removed it), but the system will respond to try and:

make some more H3O+, at the same time

removing some of the HIn, (and some of the water, but there is so much present that this is
pretty irrelevant) and
making more In-.

Thus we will see the color of the In- form.

In summary: at a low pH, an indicator is almost entirely in the HIn form. As the pH increases,
the intensity of the color of In- increases as the equilibrium shifts to the right.
Different dyes will change color at different pH's (the value can be calculated from the equilibrium
constant for the indicator).. Here is a small sample of some common acid-base indicators, and the
range at which their pH changes color. One of the difficulties with giving a range of colors is that
different person's eyes are not all equally sensitive (also different monitors will display colors
differently), so these colors are only approximations.
When conducting a titration, one must select the proper indicator so that its pH range will match the
equivalence point of the titration. Also, you must use an indicator that changes color obviously, so that
it can be detected easily. This is why phenolphthalein is so often used for strong acid-strong base
titrations.
The equivalence point is the point at which the amount of H3O+ and OH- are equal. It is important to
select an indicator which changes color -- whose endpoint -- is near the equivalence point.

Using pH titration curves in section 17.2 page 786 explain the selection process of an indicator
for a titration involving the following:

a) strong acid/strong base

b) weak acid/strong base
c) strong acid/weak base
d) weak acid/weak base
Titrations are experiments to calculate the concentration of an unknown solution. This method is one
that is used in volumetric analysis (analysis using volume of solutions). There are few terms or
definition that you should know to understand the titration procedure.
Titration: A titration experiment uses a burette and an Erlenmeyer flask.
Equivalence Point: The end point when certain volumes of the acid and the base is mixed together to
react completely forming water and a salt. The equivalence point is often marked by a color change of
an indicator. Indicators change color at a certain pH range. Different indicators are used based on the
pH of the salt formed at the end or equivalence point.
a) Strong acid/strong base
E.g. 0.1 M HCl and 50 mL of 0.1 NaOH solution.
At the equivalence point pH =7 since the salt NaCl form is neutral in solution. Last drop of HCl added
will change the pH of the solution in wide range 3-11. Therefore, any indicator that changes color in
this (pH 3-11 range) could be used to get the equivalence point accurately. The pH rage for the color
change for a list of indicators are given in the textbook. Wide range of indicators (pH, 3-11) could be
used in this titration.
b) weak acid/strong base
E.g. 1.0 M HC2H3O2 and 50 mL of 1.0 NaOH solution.

At the equivalence point the concentration of the salt solution of NaC2H3O can be calculated as shown
below:
Concentration of both HC2H3O2 and NaOH solutions are equal to 0.10 M. The volumes of HC2H3O2
and NaOH that will react at the equivalence point will also be equal since both HC2H3O2 and NaOH
have one H and OH groups to produce water. Therefore, the final volume of the mixture would be 100
mL (50 mL 0.10 M HC2H3O2 + 50 mL 0.10 M NaOH = 100 mL salt solution) The amount of
NaC2H3O2 formed is equal to either HC2H3O2 or NaOH added. Basically volume of the final
solution has been doubled. Therefore, the concentration NaC2H3O2 is half the concentration of either
HC2H3O2 or NaOH solution. i.e. 0.10 M ) 2 = 0.05 M NaC2H3O2 .
To calculate the pH of 0.05 M NaNC2H3O2 (Similar to a previous problem in Chapter 16:What is the
pH of a 0.05 M NaC2H3O2 salt solution?)
At the equivalence point pH =8.72 since the salt NaC2H3O2 forms a basic solution. Last drop of
HC2H3O2 added will change the pH of the solution in the range 8-10. Therefore, any indicator that
changes color in this (pH 8-10) range could be used to get the equivalence point accurately. The pH
rage for the color change for a list of indicators are given in the textbook
The indicators, thymol blue (8.0-9.6), phenolphthalein (8.2-10.0) and thymolphthalein (9.4-10.6)
could be used in this titration.
c) Strong acid/weak base

E.g. 1.0 M HCl and 50 mL of 1.0 NH4 OH (NH3) solution.

At the equivalence point the concentration of the salt solution of NH4Cl can be calculated as
shown below:
Concentration of both HCl and NH4 OH solutions are equal to 1.0 M. The volumes of HCl and NH4
OH that will react at the equivalence point will also be equal since both HCl and NH4 OH have one H
and OH groups to produce water. Therefore, the final volume of the mixture would be 100 mL (50 mL
1.0 M HCl + 50 mL 1.0 M NH4OH = 100 mL salt solution). The amount of NH4Cl formed is equal to
either HCl or NH4OH added. Basically volume of the final solution has been doubled. Therefore the
concentration NH4Cl is half the concentration of either HCl or NH4OH solution.
i.e. (1.0 M )/ 2 = 0.5 M NH4Cl .
To calculate the pH of 0.5 M NH4Cl (see problem 5a: What is the pH of a 0.5 M NH4Cl salt
solution)
At the equivalence point pH = 4.78 since the salt NH4Cl forms an acidic solution. Last drop of HCl
added will change the pH of the solution in the range 4-6. Therefore, any indicator that changes color
in this (pH 4-6) range could be used to get the equivalence point accurately. The pH rage for the color
change for a list of indicators are given in the textbook.
The indicator, methyl red (4.8-6.0) could be used in this titration.
d) weak acid/weak base
E.g. 1.0 M HC2H3O2 and 50 mL of 1.0 NH4 OH (NH3) solution.

The solution is neutral at the equivalence point because the salt of a weak acid and a weak base forms
a neutral, a basic or an acidic solution depending on the relative strengths of the acid and the base.
Since both HC2H3O2 and and NH4 OH (NH3) have identical Ka and Kb values their strength are equal
making the solution neutral. The last drop of HC2H3O2 added will change the pH of the solution in the
range 6-8. Therefore, any indicator that changes color in this (pH 4-6) range could be used to get the
equivalence point accurately. The pH rage for the color change for a list of indicators are given in page
675, section 15.9 of Ebbing.
The indicators, litmus (5.0-8.0) and bromothymole blue (6.0-7.6) could be used in this titration.
Titration Curves of Polyprotic Acids
Similar to monoprotic acids, except that two equivalence points are seen. The equivalence points of a
polyprotic acid/ base reaction can be determined using an indicator. In alternative experiment way
monitoring the changes in pH that occurs during the titration of a weak polyprotic acid with a strong
base could also be used to find equivalence points. At the equivalence point one should expect to see a
dramatic change in pH as the solution goes from acidic to strongly basic.

Depicted on the left is an idealized pH titration curve for a weak diprotic acid such as H2SO3. The first
thing that you should notice is that there are two regions where we see a significant pH change. These,

if you wish, correspond to two separate titrations. Titration 1 is the reaction of the first proton with the
base (in this case sodium hydroxide)

Solubility of Salts
Solubility of a solute in a solvent is the number of grams of solute necessary to saturate 100 grams of
solvent at a particular temperature.

Solubility product:
Solubility product is defined as the product of ionic concentration when dissolved ions and undissolved ions are in equilibrium.
In other words, When a saturated solution of sparingly or slightly soluble salt is in contact with
un- dissolved salt, an equilibrium is established between the dissolved ions and the ions in the solid
phase of the un-dissolved salt. Ionic product at this stage is called solubility product.
Symbol: It is denoted by Ksp
Determination of solubility product:
a Mc+(aq) + b Xd-(aq)

MaXb(aq)
Ksp=

[Mc+]a[Xd-]b

Consider a slightly soluble salt such as silver chloride (AgCl).

Ag+(aq) + Cl-(aq)

AgCl(s)

Applying equilibrium law:

Kc=

[Ag+][Cl-]
[AgCl]

Kc [AgCl] = Ksp =

[Ag+][Cl-]

Since AgCl is a solid there is no change in the concentration of salt (AgCl) at equilibrium.
Therefore
[AgCl] = C
Kc x C = [Ag+][Cl-]
Let Kc x C = Ksp

Therefore
Ksp = [Ag+][Cl-]
Ionic Product or Reaction Quotient (Qsp):
As we discussed already under equilibrium reactions the product of ionic concentration other than
equilibrium is called reaction quotient or ionic product.
Applications of solubility product:
Knowledge of solubility product is very useful, to determine whether precipitates will be obtained or
not by the addition of more amount of solute to the solution. There are three conditions:
When Ksp> ionic product (Qsp) (unsaturated):
If solubility product is greater than the ionic product then reaction will shift to right and more will be
dissolved and no precipitate will form.
When Ksp< ionic product (Qsp) (supersaturated):
If solubility product is less than the ionic product then reaction will shift to left and precipitate will
form.
When Ksp= ionic product (Qsp):
In this condition solution is in equilibrium with solid salt and ions and further addition will cause
precipitates.
The Common Ion Effect and Precipitation Reactions
The solubility of insoluble substances can be decreased or made to precipitate by the presence of a
common ion. AgCl will be our example.
Present in silver chloride are silver ions (Ag+) and chloride ions (Cl). Silver nitrate (which is soluble)
has silver ion in common with silver chloride. Sodium chloride (also soluble) has chloride ion in
common with silver chloride.
In fact, mixing sufficiently concentrated solutions of AgNO3 and NaCl will produce a precipitate of
AgCl. In order to be sufficiently concentrated, the product of the [Ag+] and the [Cl] must exceed the
Ksp of 1.77 x 1010.
Here is the example problem: AgCl will be dissolved into a solution with is ALREADY 0.0100 M in
chloride ion. What is the solubility of AgCl?
In solubility problems, the source of the chloride is from soluble chloride salt, NaCl because very little
is coming from the insoluble salt, AgCl. Let us assume the chloride came from some dissolved sodium
chloride, sufficient to make the solution 0.0100 M. So, on to the solution .
The dissociation equation for AgCl is:

AgCl (s)

Ag+ (aq) + Cl (aq)

The Ksp expression is:

Ksp = [Ag+] [Cl]
This is the equation we must solve. First we put in the Ksp value:
1.77 x 1010 = [Ag+] [Cl]
Now, we have to reason out the values of the two guys on the right. The problem specifies that [Cl] is
already 0.0100. I get another 'x' amount from the dissolving AgCl. Of course, [Ag+] is 'x.'
Substituting, we get:
1.77 x 1010 = (x) (0.0100 + x)
This will wind up to be a quadratic equation which is solvable via the quadratic formula. However,
there is a chemical way to solve this problem. We reason that 'x' is a small number, such that '0.0100 +
x' is almost exactly equal to 0.0100. If we were to use 0.0100 rather than '0.0100 + x,' we would get
essentially the same answer and do so much faster. So the problem becomes:
1.77 x 1010 = (x) (0.0100)
and
x = 1.77 x 108 M
There is another reason why neglecting the 'x' in '0.0100 + x' is OK. It turns out that measuring Ksp
values are fairly difficult to do and, hence, have a fair amount of error already built into the value. So
the very slight difference between 'x' and '0.0100 + x' really has no bearing on the accuracy of the final
answer. Why not? Because the Ksp already has significant error in it to begin with. Our "adding" a bit
more error is insignificant compared to the error already there.
Solubility Product (Ksp) of Slightly Soluble Ionic Compounds
A very soluble ionic salt (e.g., NaCl) dissolves and completely dissociates into Na+ (aq) and Cl- (aq).
Some salts only slightly soluble, (as given by solubility rules) and an equilibrium exists between
dissolved and undissolved compound. Consider the addition of PbSO4 (s) to water.
PbSO4 (s) Pb2+ (aq) + SO42- (aq)
If the reaction hasnt reached equilibrium, the reaction quotient Qsp is
Qsp = [Pb2+] [SO42-]

Qsp = ion-product expression

At equilibrium, Qsp = Ksp
Ksp = [Pb2+][SO42-]
Ksp = Solubility Product Constant
We normally only consider systems at equilibrium
use Ksp (not Qsp).
Examples:
Cu(OH)2 (s) Cu2+ (aq) + 2 OH- (aq)

Ksp = [Cu2+][OH-]2

CaCO3 (s) Ca2+ (aq) + CO32- (aq)

Ksp = [Ca2+][CO32-]

Ca3(PO4)2 (s) 3 Ca2+ (aq) + 2 PO43- (aq)

Ksp = [Ca2+]3[PO43-]2

Note: The S2- (aq) is very unstable in water and converts to HS- and gives OH- (aq).
MnS (s) + H2O (l) Mn2+ (aq) + HS- (aq) + OH- (aq)
[i.e., S2- (aq) + H2O (l) HS- (aq) + OH- (aq)]
Ksp = [Mn2+][HS-][OH-]
The greater is Ksp, the more soluble the substance is.
e.g.,

PbSO4
CoCO3
Fe(OH)2

Ksp = 1.6 x 10-8

Ksp = 1.0 x 10-10
Ksp = 4.1 x 10-15

insoluble
more insoluble
most insoluble

Calculations Involving Solubility Products

Two types:

Use Ksp to find conc of dissolved ions

Use concs to find Ksp.

Make sure the equations are balanced!!

Example: The solubility of Ag2CO3 is 0.032 M at 20 C. What is Ksp of Ag2CO3?
This is a common type of questionNote that we are told the molar solubility of Ag2CO3, but of
course it will dissociate into ions.
Therefore,

Ag2CO3 (s) 2 Ag+ (aq) + CO32- (aq)

init
change
[equil]

(solid)
-0.032 M
(solid)

0
+0.064 M
0.064 M

0
+0.032 M
0.032 M

Ksp = [Ag+]2[CO3] = (0.064)2(0.032)

Ksp = 1.3 x 10-4
Example: The solubility of Zn (oxalate) is 7.9 x 10-3 M at 18 C. What is its Ksp?
Zn (ox)
init
change
[equil]

(solid)
-7.9 x 10-3 M
(solid)

Zn2+ (aq)

+7.9 x 10-3 M
7.9 x 10-3 M

ox2- (aq)
+7.9 x 10-3 M
7.9 x 10-3 M

Ksp = [Zn2+][ox] = (7.9 x 10-3)2

Ksp = 6.2 x 10-5
Example: What is the molar solubility of SrCO3? (Ksp = 5.4 x 10-10)
SrCO3 (s)
init
change
[equil]

(solid)
-x
(solid)

Ksp = x2 x = 5.4 x 10
x = 2.3 x 10-5 M

Sr2+ (aq) + CO32- (aq)

0
+x
x

0
+x
x

-10

Solubility of SrCO3 is 2.3 x 10-5 M

Example: What is the molar solubility of Ca(OH)2 in water? (Ksp = 6.5 x 10-6).
Ca(OH)2 (s)
init
change
[equil]

(solid)
-x
(solid)

0
+x
x

Ksp = 6.5 x 10-6 = x(2x)2 = 4x3 (careful!)

Ca2+ (aq) + 2 OH- (aq)

0
+2x
2x

 Solubility of Ca(OH)2 = 1.2 x 10-2 M

To obtain the

x, then antilog.

of a number, learn to use the

y button on your calculator or take the log, divide by

102 HOMEWORK 5

HOMEWORK FOR CHAPTER 17

1. If the following substance is dissolved in pure water, will the solution be acidic, neutral, or
basic?
Solid sodium carbonate: (Na2CO3).
a) acidic b) neutral
c) basic
2. Hypochlorous acid (HClO) has a pKa of 7.54. What are the [H3O+] and pH of a 0.115 M HClO
solution?
a. 5.8 x 10-9 M and 9.76 b. 4.8 x 10-3 M and 2.31 *c. 5.8 x 10-5 M and 4.24
d. 1.0 x 10-14 M and 14.00 e. 1.0 x 10-7 M and 7.00
3. What is [H+] in an aqueous solution that is 0.18 M in CH3COOH (Ka = 1.8 x 10-5) and 0.14 M
in CH3COONa?
a. 0.18 M
b. 0.040 M
c. 1.8 x 10-3 M
d. 2.3 x 10-5 M
4. What is the pH value of a 0.10 M acetic acid (Ka = 1.8 x 10-5) and 0.05 M in sodium
acetate solution:
a. 1.8
b. 2.4
c. 4.7 d. 4.4
e. 5
5. A 1 Liter buffered solution was prepared by dissolving 1.0 mole of NH3 and 1.5 mole of NH4Cl
in water. The pH of this solution would be: (Kb = 1.8 x 10-5)
a. 11.0
b. 9.0 c. 7.0 d. 4.0 e. none of the above
6. A weak acid that has different colors for acid and its conjugate base can be used as
a. an salt. b. an indicator.
c. a buffer. d. a base.
7. At the equivalence point of the titration of a 0.20 M NH3 solution with 0.20 M HCl
solution, the pH will be:
a. less than 7.00 b. 7.00 c. greater than 7.00 d. cannot be determined
e. none of these
8 Methyl violet is an indicator used in acid-base titrations. Its acid form, HIn, is red, while its
conjugate base from, In-, is yellow. The color change occurs in the pH range 0.00-1.6. In a
solution of pH = 6.00 the color of the indicator will be
a. red
b. yellow
c. orange
d. colorless e. blue
9 Calculate the pH of an aqueous solution of 0.10 M NH4Cl (Kb for NH3 =1.8 x 10-5).
Choose your answer from the following pH ranges:
a. pH = 0.00-2.99 b. pH = 3.00-5.99 c. pH = 6.00-8.99 d. pH = 9.00-10.99 e. pH = 11.00-14.00
10. In the titration of a weak acid HA with 0.100 M NaOH, the equivalence point is known to
occur at a pH value of approximately 11. Which of the following indicators would be best to use
to mark the endpoint of this titration?
a) an indicator with Ka = 10-10 b) an indicator with Ka = 10-8
c) an indicator with Ka = 10-14 d) an indicator with Ka = 10-11
e) an indicator with Ka = 10-12

11. A 50.00-mL sample of 0.100 M KOH is being titrated with 0.100 M HNO3. Calculate the pH
of the solution after 52.00 mL of HNO3 is added.
a) 6.50 b) 3.01 c) 2.71
d) 2.41
e) none of these
12. The solubility product expression (Ksp) for BaF2 in water is:
a. none of these
b. Ksp = [Ba2+ (aq)][F- (aq)]2
c. Ksp = [Ba2+ (aq)][F- (aq)]
d. Ksp = [Ba2+ (aq)][F- (aq)]2/[BaF2 (s)]
e. Ksp = [Ba2+ (aq)][F- (aq)]/[BaF2 (s)]
13. What is the Ksp of the salt MX (containing M+ and X- ions) if its molar solubility is 2.6 x 10-3
M?
a. none of these b. 6.8 x 10-6 c. 2.6 x 10-3 d. 5.1 x 10-2 e. 6.4 x 10-5
14. Addition of which of the following salts is most likely to increase the solubility of MgCO3 in
water?
a. CaCl2 b. NH4Cl *c. Na2CO3 d. KI e. NaNO3
15. A solution is prepared that contains [Pb2+ (aq)] = 1.4 x 10-2 M and [I- (aq)] = 2.0 x 10-3 M.
Will a precipitate of PbI2 (s) form? (Ksp for PbI2 is 7.9 x 10-9).
a. cannot be determined b. none of these c. only if NaI (s) is also added
d. yes e. no

CHEM 102: Sample Test 5

CHAPTER 17
1. When H2SO4 is dissolved in water, which species would be found in the water at equilibrium in
measurable amounts?
a. H2SO4 b. H3SO4 + c. HSO4 - d. SO4 -2 e. OH2. Which of the following is the net ionic equation for the reaction that occurs during the titration of
nitrous acid with potassium hydroxide?
a) HNO2 + K+ + OH- KNO2 + H2O
b) HNO2 + H2O NO2- + H3O+
c) HNO2 + KOH K+ + NO2- + H2O
d) HNO2 + OH- NO2- + H2O
e) H+ + OH- H2O
3. What is the pH of a solution that is 0.2 M in acetic acid (Ka = 1.8 x 10-5) and 0.2 M in sodium
acetate?
a) 4.7
b) 9.3 c) 7.0 d) 5.4 e) 8.6
4. Given 0.015 moles of NaC2H3O2and 0.05 moles of HC2H3O2 dissolved in water, what is the pH? pKa
for acetic acid is 4.74.
a. 5.22 b. 4.74 c. 4.22 d. 1.30 e. Cannot determine
5. If 50 ml of a 0.01 M HCl solution is titrated with a 0.01 M NaOH solution, what will be the initial
pH and the pH at the endpoint.
a. 2 and 3.5
b. 2 and 7 c. 3.30 and 7 d. 12 and 7 e. None of these
6. What is the pH of a 1.0 M aqueous solution of NaCl?
a) 7.0 b) greater than 7.0
c) less than 7.0
d) there is not enough information given
7. A 50.00-mL sample of 0.100 M KOH is being titrated with 0.100 M HNO3. Calculate the pH of the
solution after 52.00 mL of HNO3 is added.
a) 6.50 b) 3.01 c) 2.71 d) 2.41 e) none of these
8. If the following substance is dissolved in pure water, will the solution be acidic, neutral, or basic?
solid sodium carbonate: (Na2CO3).
a) acidic
b) neutral
c) basic
9. The Henderson-Hasselbach equation can be used to determine several factors. Which of the
following can be determined?
a. the pH for a solution of a strong acid and its conjugate base
b. the pH for a strong base that has been partially titrated
c. the mole ratio needed to make a buffer solution having a known pH
d. the pKa of an equimolar mixture of an unknown weak acid and its conjugate base without knowing
the pH
e. the change in pH if some acid or base is added to a buffered solution
10. A 1 Liter buffered solution was prepared by dissolving 1.0 mole of NH3 and 1.5 mole of NH4Cl in
water. The pH of this solution would be: (Kb = 1.8 x 10-5)
a. 11.0 b. 9.0

c. 7.0

d. 4.0

e. none of the above

11. The salt that forms an alkaline (basic) aqueous solution is

a. KNO3.
b. NH4Cl.
c. NaC2H3O2.

d. NaCl.

12. A weak acid that has different colors for acid and its conjugate base can be used as
a. an salt.
b. an indicator.
c. a buffer.
d. a base.
13. Give the pH value of a solution 0.10 M in acetic acid (Ka = 1.8 x 10-5) and 0.05 M in sodium
acetate:
a. 1.8
b. 2.4
c. 4.7
d. 4.4
e. 5
14. Methyl violet is an indicator used in acid-base titrations. Its acid form, HIn, is red, while its
conjugate base from, In-, is yellow. The color change occurs in the pH range 0.00-1.6. In a solution of
pH = 6.00 the color of the indicator will be
a. red
b. yellow
c. orange
d. colorless
e. blue
15. In the titration of a weak acid HA with 0.100 M NaOH, the stoichiometric point is known to occur
at a pH value of approximately 11. Which of the following indicators would be best to use to mark
the endpoint of this titration?
a) an indicator with Ka = 10-10
b) an indicator with Ka = 10-8
c) an indicator with Ka = 10-14
d) an indicator with Ka = 10-11
e) an indicator with Ka = 10-12
16. Calculate the pH of an aqueous solution of 2.0 M NH4Cl (Kb for NH3 =1.8 x 10-5). Choose your
answer from the following pH ranges:
a. pH = 0.00-2.99 b. pH = 3.00-5.99 c. pH = 6.00-8.99
d. pH = 9.00-10.99 e. pH = 11.00-14.00
17. Assume that an indicator works BEST when the equivalent point of a titration comes in the
middle of the indicator range. Which of the following indicators would be the best for a titration of
35.00 mL of 0.10 M HC2H3O2 (Ka=1.8 x 10-5) with 35.00 mL 0.10 M NaOH?
a. methyl violet 0.0-1.6 b. methyl orange 3.2-4.4
c. bromocresol green 3.8-5.4 d. methyl red 4.8-6.0
e. phenolphthalein 8.2-10.0
18. Given a equimolar mixture of Benzoic acid and sodium benzoate what would be the pH of the
solution? Ka of HC7H5O2 = 6.28 x 10-5
a. 4.20
b. 9.80 c. 2.10 d. 6.28
e. Cannot determine
19. A weak monoprotic acid (HA) is 1.41% dissociated in a 1.0 M solution. The Ka for this acid is
a. 4.0 x 10-6. b. 5.6 x 10-5. c. 2.0 x 10-4. d. 9.9 x 10-3.

20. Buffer solution is one which

a. contains the maximum amount of solute possible for a particular temperature.
b. contains more than the expected amount of solute for a particular temperature and is therefore unstable.
c. resists changes in pH upon addition of acid or base.
d. contains an equal number of hydronium and hydroxide ions.
e. changes color upon addition of strong base.
21. Which pair of compounds could be used to make a buffer solution?
a. NaCl/HCl
b. (NH4)2SO4/H2SO4
c. NaCH3COO/CH3COOH
d. K3PO4/KH2PO4
e. KOH/KBr
22. A salt which can be used to make a buffer with formic acid, HCOOH, is

a. NH4COOH
b. KCOOH
c. NaCl
d. Na2CO3
e. (NH4)3PO4
23. Which two of the following compounds in aqueous solution would make an effective buffer solution?
KNO3
CH3COOH
NH4NO3
NH3
HNO3
a. HNO3 & NH4NO3
b. HNO3 & KNO3
c. CH3COOH & NH3
d. NH3 & NH4NO3
e. CH3COOH & HNO3
24. Which combination of solutions is the best choice for making a buffer solution?
a. equal volumes of 0.1 M formic acid and 0.1 M sodium formate
b. equal volumes of 0.05 M hydrochloric acid and 0.075 ammonium chloride
c. equal volumes of 0.1 M sulfuric acid and 0.001 M sodium sulfate
d. equal volumes of 1 M acetic acid and 0.005 M sodium acetate
e. equal volumes of 0.5 M nitric acid and 0.5 M sodium hydroxide
25. Calculate the pH of a solution which is 0.05 M in lactic acid and 0.04 M in sodium lactate. The Ka for
lactic acid is 1.8 10-4.
a. 10.35
b. 3.74
c. 3.65
d. 0.097
e. 2.25 10-4
26. Calculate the pH of a solution that contains 0.45 M benzoic acid and 0.40 M sodium benzoate. The Ka
for benzoic acid is 6.5 10-5.
a. 7.3 10-5
b. 4.53
c. 4.19
d. 4.14
e. 3.79
27.Which formula represents the Henderson-Hasselbach equation for the generic acid HA?

[A - ]
[HA]

a.

pK a = pH + log

b.

pH = pK a log

c.

log

d.

pH = pK a +

e.

[A - ]
pH = pK a + log
[HA]

[A - ]
[HA]

[A - ]
= pK a pH
[HA ]
[A - ]
[HA]

28. Which pair of reagents is the best choice to make a buffer of pH = 4.50?
a. HF/FKa = 7.2 10-4
Ka = 1.8 10-5
b. CH3COOH/CH3COO
2Ka = 6.2 10-8
c. H2PO4 /HPO4
+
Ka = 5.6 10-10
d. NH4 /NH3
23Ka = 3.6 10-13
e. HPO4 /PO4

29.Consider a buffer solution made up of H2PO4- and HPO42-, which has a Ka of 6.2 10-8. What ratio of
HPO42- to H2PO4- will give a pH of 7.35?
a. 1.38 to 1
b. 0.140 to 1
c. 1 to 1
d. 0.725 to 1
e. More information is needed to answer this question.
30. One liter of a buffer is prepared using equimolar amounts of ascorbic acid and sodium ascorbate,
producing a solution with pH = 4.10 After addition of 10 mL of 1 M NaOH, the most likely value of
the pH is
a. 2.00
b. 4.10
c. 4.12
d. 5.90
e. 8.00
31. Calculate the pH of a buffer that is 0.14 M NH3 and 0.10 M NH4NO3. The Kb for ammonia is 1.8
10-5.
a. 4.74
b. 4.89
c. 9.11
d. 9.25
e. 9.40
32. Which is the smallest amount of solid NaOH shown that will exceed the buffer capacity of a 500. mL
solution that is 0.40 M in acetic acid and 0.15 M in sodium acetate. The Ka for acetic acid is 1.8 10-5.
a. 3.00 g
b. 4.31 g
c. 4.74 g
d. 5.16 g
e. 6.00 g
33. Which statement about the titration of 0.10 M HNO3 with 0.10 M KOH is not correct?
a. The pH at the equivalence point is 7.00.
b. The initial pH is 1.00.
c. At the equivalence point the pH decreases sharply.
d. At the equivalence point the volume of base added will be equal to the original volume of acid.
e. The net ionic equation is H3O+ + OH- 2H2O.
34. Calculate the pH of a titration mixture when 25.00 mL of 0.106 M NaOH has been added to a 50.00
mL sample of 0.0950 M HNO3.
a. 0.97
b. 1.02
c. 1.20
d. 1.45
e. 1.55
35. Calculate the volume of 0.106 M NaOH needed to neutralize a 50.00 mL sample of 0.0950 M HNO3.
a. 5.19 mL
b. 44.81 mL
c. 50.00 mL
d. 55.19 mL
e. 55.79 mL
36. Calculate the pH of a mixture of 51.0 mL of 0.106 M NaOH and 50.00 mL of 0.0950 M HNO3.
a. 11.81
b. 11.02
c. 9.31
d. 4.74
e. 2.19

37. Calculate the pH of a titration mixture when 35.00 mL of 0.106 M NaOH has been added to a 50.00
mL sample of 0.0950 M CH3COOH. Ka = 1.8 10-5.
a. 4.64
b. 4.74
c. 5.30
d. 8.70
e. 9.26
38. Calculate the pH of a titration mixture at the midpoint of the titration of a 50.00 mL sample of 0.0950
M CH3COOH with 0.106 M NaOH. Ka = 1.8 10-5.
a. 4.85
b. 4.74
c. 4.64
d. 1.02
e. 0.97
39. Calculate the pH of a titration mixture at the equivalence point of the titration of a 50.00 mL sample
of 0.0950 M CH3COOH with 0.106 M NaOH. Ka = 1.8 10-5.
a. 10.56
b. 9.53
c. 9.26
d. 8.72
e. 4.47
40. Calculate the pH of a titration mixture in which a 50.00 mL sample of 0.0950 M CH3COOH has
reacted with 50.00 mL of 0.106 M NaOH. Ka = 1.8 10-5.
a. 12.72
b. 11.74
c. 10.58
d. 9.26
e. 8.71
41. Which combination of acid and base would give the titration curve shown?

a. NaOH and HCl

b. KOH and H3PO4
c. NH4OH and CH3COOH
d. NaOH and H2SO4
e. NH4OH and H3PO4
42. Acid "rain" is defined as any precipitation with a pH value less than _____.
a. 1.0
b. 4.2
c. 5.6
d. 7.0
e. 8.5
43. Which list contains only compounds that directly contribute to acid rain?
a. CaO, H2Se, Kr
b. CO2, SiO2, GeO2
c. Fe2S3, CaCO3, Na2CO3
d. H2O, NH3, CH4
e. CO2, NO2, SO2

44. Write the Ksp expression for silver phosphate, Ag3PO4.

a. [Ag+]3[PO43-]
b.

45.

46.

47.

48.

49.

50.

51.

52.

[Ag + ]3 [PO 34- ]

[Ag 3 PO 4 ]

c. 3x[Ag+][PO43-]
d. 3x[Ag+]3 + [PO43-]
e. [H+][OH-]
Calculate the molar solubility of silver chloride, AgCl. The Ksp = 1.8 10-10 for silver chloride.
a. 9.0 10-11
b. 2.6 10-5
c. 1.3 10-5
d. 9.5 10-6
e. 6.5 10-6
Calculate the molar solubility of silver chloride, AgCl, in a solution in which [Cl-] = 0.045 M. Ksp =
1.8 10-10 for silver chloride.
a. 1.3 10-5
b. 2.5 10-8
c. 4.0 10-9
d. 1.8 10-10
e. 8.1 10-12
In which solution would calcium phosphate have the greatest solubility?
a. 0.1 M phosphoric acid
b. 0.1 M sodium phosphate
c. saturated calcium hydroxide
d. 0.1 M calcium nitrate
e. distilled water
Which of the factors affecting solubility explains the observation that silver phosphate is more
soluble in water than in Na3PO4?
a. The solubility of most salts increases as temperature increases.
b. The solubility of many salts is affected by the pH of the solution.
c. A common ion displaces the solubility equilibrium toward the undissolved solute.
d. The formation of complex ions displaces the solubility equilibrium toward the aqueous ions.
e. Some insoluble compounds are amphoteric.
Which of the factors affecting solubility explains the observation that the solubility of silver chloride
is increased by the addition of NH3 to the mixture?
a. The solubility of most salts increases as temperature increases.
b. The solubility of many salts is affected by the pH of the solution.
c. A common ion displaces the solubility equilibrium toward the undissolved solute.
d. The formation of complex ions displaces the solubility equilibrium toward the aqueous ions.
e. Some insoluble compounds are amphoteric.
Which group contains only solutes that would decrease the solubility of barium sulfate?
a. Ba(OH)2, NaOH, NH4OH
b. HNO3, H2SO4, HCH3COO
c. Na2SO4, NaOH, NaCH3COO
d. Ba(NO3)2, Na2SO4, H2SO4
e. SO2, CO2, NH3
Which mixture would dissolve the largest amount of barium sulfate?
a. 0.1 M HCl
b. 0.1 M Ba(NO3)2
c. 0.1 M Mg(OH)2
d. 0.1 M Na2SO4
e. 0.1 M Al2(SO4)3
Which mixture would dissolve the smallest amount of barium sulfate?
a. 0.1 M HCl
b. 0.1 M Ba(NO3)2

c. 0.1 M Mg(OH)2
d. 0.1 M Na2SO4
e. 0.1 M Al2(SO4)3
53. Which of the following species would increase the solubility of CuI?
a. NH3
b. SO42c. OHd. S2O32e. CN54. Will a precipitate form when 10.0 mL of 0.5 M NaCl is added to 10.0 mL of 0.05 M AgNO3? The Ksp
for AgCl is 1.8 10-10.
a. Yes because Q = K
b. Yes because Q > K
c. Yes because Q < K
d. No because Q < K
e. More information is needed to answer this question.
55. Calculate the volume of 0.10 M NaCl that must be added to 10.0 mL of 0.05 M AgNO3 to begin
forming a precipitate. The Ksp for AgCl is 1.8 10-10. Dilution effects can be neglected; 1 mL = 20
drops.
a. less than one drop
b. 1.0 mL
c. 2.5 mL
d. 5.0 mL
e. 10.0 mL

Answers to Sample Test 4 Questions

1. c. HSO42. d) HNO2 + OH- ---- NO2- + H2O

3. a) 4.7
4. c) 4.22
5. b) 2 and 7
6. a. 7.0
7. c. 2.71
8. c. basic
9. d. the pKa of an equimolar mixture of an unknown weak acid and its conjugate base without
knowing the pH
10. b 9.0
11. c. NaC2H3O2
12. b. an indicator.
13. c. 4.4
14. b. yellow
15. b. an indicator with Ka = 10-11
16. b. pH = 3.00-5.00
17. d. methyl red 4.8-6.0
18. a. 4.20
19. c. 2.0 x 10-4.
20. c. resists changes in pH upon addition of acid or base.
21. c. NaCH3COO/CH3COOH
22. b. KCOOH
23. d. NH3 & NH4NO3
24. a. equal volumes of 0.1 M formic acid and 0.1 M sodium formate
25. c. 3.65
26. d. 4.14
27. e.

pH = pK a + log

[A - ]
[HA]

28. b. CH3COOH/CH3COOKa = 1.8 10-5

29. a. 1.38 to 1
30. c. 4.12
31. e. 9.40
32. e. 6.00 g
33. c. At the equivalence point the pH decreases sharply.
34. e. 1.55
35. b. 44.81 mL
36. a. 11.81
37. c. 5.30
38. b. 4.74
39. d. 8.
40. b. 11.74
41. b. KOH and H3PO4
42. c. 5.6
43. e. CO2, NO2, SO2
44. a. [Ag+]3[PO43-]
45. c. 1.3 10-5
46. c. 4.0 10-9
47. e. distilled water
48. c. A common ion displaces the solubility equilibrium toward the undissolved solute.
49. d. The formation of complex ions displaces the solubility equilibrium toward the aqueous ions.
50. d. Ba(NO3)2, Na2SO4, H2SO4
51. a. 0.1 M HCl
52. e. 0.1 M Al2(SO4)3
53. a. NH3
54. b. Yes because Q > K
55. a. less than one drop