Chapter 19

PRECIPITATION
REACTIONS

WOLPA/AP CHEMISTRY/
CDO

Solubility of Ionic Solids

Depends on the balance of two forces:
Attraction between H2O molecules and ions of
solid.
Force of attraction between oppositely
charged ions within solid.

WOLPA/AP CHEMISTRY/
CDO

Solubility Rules
Use in predicting results of precipitation
reactions. MEMORIZE THE SOLUBILITY
RULES!!!!!
Determine ions present and possible
products.
Use solubility rules to determine if any are
insoluble.

WOLPA/AP CHEMISTRY/
CDO

Example
Ba(NO3)2(aq) + Na2CO3(aq)

WOLPA/AP CHEMISTRY/
CDO

Solubility Rules
1. Salts containing Group I elements are soluble (Li+, Na+,
K+, Cs+, Rb+). Exceptions to this rule are rare. Salts containing
the ammonium ion (NH4+) are also soluble.

2. Salts containing nitrate ion (NO3-) are generally soluble.

3. Salts containing Cl-, Br-, I- are generally soluble. Important

exceptions to this rule are halide salts of Ag+, Pb2+, and
(Hg2)2+. Thus, AgCl, PbBr2, and Hg2Cl2 are all insoluble.

WOLPA/AP CHEMISTRY/
CDO

Solubility Rules Continued

4. Most silver salts are insoluble. AgNO3 and Ag(C2H3O2) are

common soluble salts of silver; virtually anything else is insoluble.
5. Most sulfate salts are soluble. Important exceptions to this rule
include BaSO4, PbSO4, Ag2SO4 and SrSO4.
6. Most hydroxide salts are only slightly soluble. Hydroxide salts
of Group I elements are soluble. Hydroxide salts of Group II
elements (Ca, Sr, and Ba) are slightly soluble. Hydroxide salts of
transition metals and Al3+ are insoluble. Thus, Fe(OH)3, Al(OH)3,
Co(OH)2 are not soluble.

WOLPA/AP CHEMISTRY/
CDO

Solubility Rules Continued

7. Most sulfides of transition metals are highly insoluble. Thus,
CdS, FeS, ZnS, Ag2S are all insoluble. Arsenic, antimony, bismuth,
and lead sulfides are also insoluble.

8. Carbonates are frequently insoluble. Group II carbonates (Ca,

Sr, and Ba) are insoluble. Some other insoluble carbonates include
FeCO3 and PbCO3.

9. Chromates are frequently insoluble. Examples: PbCrO4,

BaCrO4

10. Phosphates are frequently insoluble. Examples: Ca3(PO4)2,

Ag2PO4
11. Fluorides are frequently insoluble. Examples: BaF2, MgF2
PbF2.
WOLPA/AP CHEMISTRY/
CDO

Example Continued
Ba(NO3)2(aq) + Na2CO3(aq)

WOLPA/AP CHEMISTRY/
CDO

Stoichiometry
Mole Relations
Coefficients in the net ionic equation can be
used in the usual way to relate the moles of
reactants and products.
Moles of ions can be deduced from solute
concentrations.
WOLPA/AP CHEMISTRY/
CDO

Example
What is the molar concentration of Ba 2+
and F- in a solution containing 0.0075 M
BaF2

WOLPA/AP CHEMISTRY/
CDO

Precipitation Titrations
Used to determine the concentration of
species in solution or in a solid mixture.
Indicator shows, usually by color change,
when the species being analyzed for has
been consumed

WOLPA/AP CHEMISTRY/
CDO

General Principles
Involves formation of a precipitate
Must determine the volume of a
standardized titrant needed to just
precipitate all of the ion.
Need an indicator or electrode to
determine when the precipitation is
complete
WOLPA/AP CHEMISTRY/
CDO

Solubility Equilibria
Solubility Product Constant, Ksp
Precipitation reactions like all reactions, reach
a position of equilibrium.
Expression for Ksp

MaXb <----------> aM+b + bX-a

Ksp = [M+b]a [X-a]b
WOLPA/AP CHEMISTRY/
CDO

Solubility Product Principle

In any water solution in equilibrium with a
slightly soluble ionic compound, the
product of the concentrations of its ions,
each raised to a power equal to its
coefficient in the solubility equation is a
constant. This constant, Ksp, has a fixed
value at a given temperature, independent
of the concentrations of the individual ions.
WOLPA/AP CHEMISTRY/
CDO

Two Ion Compound

AgCl

WOLPA/AP CHEMISTRY/
CDO

Three Ion Compound

PbCl2

WOLPA/AP CHEMISTRY/
CDO

Four Ion Compound

Al(OH)3

WOLPA/AP CHEMISTRY/
CDO

Calculation of Ksp
Calculated from measured solubility
AgCl

Ksp = (s) (s) = s2

PbCl2

Ksp = (s) (2s)2 = 4s3

Al(OH)3

Ksp = (s) (3s)3 = 27s4

WOLPA/AP CHEMISTRY/
CDO

Example
At 20 oC, a saturated aqueous solution of
silver acetate, AgC2H3O2, contains 1.0 g
dissolved in 100.0 mL of solution.
Calculate the Ksp for AgC2H3O2.

WOLPA/AP CHEMISTRY/
CDO

Determination of Solubility
In pure water
Ksp = s2

s = (Ksp)1/2

Ksp = 4s3

s = (Ksp/4)1/3

Ksp = 27s4 s = (Ksp/27)1/4

WOLPA/AP CHEMISTRY/
CDO

Example
Estimate the solubility of lead (II) bromide
in (a) moles per liter and (b) grams per
liter of pure water. Ksp = 6.3 x 10 -6

WOLPA/AP CHEMISTRY/
CDO

Uses of Ksp
Calculation of concentration of one ion,
knowing that of the other

WOLPA/AP CHEMISTRY/
CDO

Example
You have a solution that has a lead (II)
concentration of 0.0012 M. What is the
maximum concentration of chloride ions
that would be present? Ksp = 1.7 x 10 -5

WOLPA/AP CHEMISTRY/
CDO

Uses of Ksp
Determination of whether a precipitate will
form
Compare original concentration product, P,
to Ksp
if P < Ksp, no precipitate will form
if P > Ksp, precipitate forms until P becomes
equal to Ksp

WOLPA/AP CHEMISTRY/
CDO

Example
You have 100.0 m of a solution that has a
lead (II) concentration of 0.0012 M. Does
PbCl2 precipitate when 1.20 g of solid
NaCl is added?

WOLPA/AP CHEMISTRY/
CDO

Determination of Solubility
In solution containing a common ion
Solubility is much less than in pure water

WOLPA/AP CHEMISTRY/
CDO

Example
Calculate the solubility of silver carbonate,
Ag2CO3, in moles per liter, in pure water.
Compare this with the molar solublity of
Ag2CO3 in 225 mL of water to which 0.15 g
of Na2CO3 has been added.

WOLPA/AP CHEMISTRY/
CDO

Simultaneous Equilibria
Two or more reactions occur at the same
time is a solution, all of them being
described as equilibrium processes.
The equilibrium for the overall reaction is
the product of the equilibrium constants for
the summed reactions.
That is Knet = K1 x K2
WOLPA/AP CHEMISTRY/
CDO

Solubility and pH
Any salt containing an anion that is the
conjugate base of a weak acid dissolves in
water to a greater extent than that given
by Ksp because the ions undergo a
hydrolysis reaction.

WOLPA/AP CHEMISTRY/
CDO

Example
PbS
PbS(s) <----------> Pb2+(aq) + S2-(aq)
= 8.4 x 10-28

Ksp

S2-(aq) + H2O(l) <----------> HS-(aq) + OH-(aq)

Kb = 1 x 105
Overall
PbS(s)
(aq)

+ H2O(l) <---> Pb2+(aq) + HS-(aq) + OHKnet = 8.4 x 10-23

WOLPA/AP CHEMISTRY/
CDO

 In general, the solubility of a salt

containing the conjugate base of a weak
acid is increased by addition of a stronger
acid to the solution. In contrast, the salts
are not soluble in strong acid if the anion
is the conjugate base of a strong acid.

WOLPA/AP CHEMISTRY/
CDO

 CaCO3 <--------> Ca2+(aq)+ CO32-(aq)

K = Ksp = 3.8 x 10-9
CO32-(aq) + H2O(l) <--------> HCO3-(aq) +
OH-(aq)
K = Kb = 2.1 x 10-4
OH-(aq) + H3O+(aq) <--------> 2H2O(l)
K = 1/Kw = 1 x 1014
WOLPA/AP CHEMISTRY/
CDO

 NET
CaCO3(s) + H3O+(aq) <------> Ca2+(aq) +
HCO3-(aq) + H2O(l)
Knet = (Ksp) (Kb)/(Kw) = 79.8

WOLPA/AP CHEMISTRY/
CDO

Solubility and Complex Ions

Examples of complex ions: AgCl2-, Ag(S2O3)23-, Ag(CN)2 The solubility of certain insoluble compounds can be
increased when a complex ion is formed. Complex ions
usually refer to cations in which surrounding water
molecules have been replaced by some other electron
pair donor. The equilibrium constant will equal the
solubility constant times the formation constant for the
complex ions. (Note - Chapter 23 in your textbook
covers complex ions - their formation and nomenclature)

WOLPA/AP CHEMISTRY/
CDO

Solubility and Complex ions

AgCl(s) + 2NH3 Ag(NH3)2+ + Cl K = (Ksp) (Kf)
= (1.8 x 10-10) (1.6 x 107) = 0.00288 =
0.0029

WOLPA/AP CHEMISTRY/
CDO

Example
Solid gold (I) chloride AuCl, is dissolved
when excess cyanide ions, CN-, are added
to give a wter souble complex ion.
AuCl(s) + 2CN- (aq) Au(CN)-(aq) + Cl Show that this equation is the sum of twp
other equations and calculate the Knet.

WOLPA/AP CHEMISTRY/
CDO

Solubility, Ion Separations, and

Qualitative Analysis

WOLPA/AP CHEMISTRY/
CDO