CH 15 w16 PDF

Lecture PowerPoint Slides
to accompany
CHEMISTRY
Human Activity,
Chemical Reactivity
Prepared by
Philip Elder, Ph.D.
Copyright 2015 by Nelson Education Limited 1

Chapter 15
Solubility, Precipitation, and

Complexation
Copyright 2015 by Nelson Education Limited

Solubility, Precipitation, and
Complexation

Ocean Acidification:
Ocean Ecology at Risk
Sea water is becoming more acidic due to increased
CO2(g) in the atmosphere.
How will the acidification of seawater affect the
production of corals? How will it affect the ability of
organisms to use calcium carbonate to build their
shells?
Acidification of the oceans and the consequences could
take hundreds of years to reverse.
What is the chemistry relevant to this issue?

pH-dependent
distribution among
carbonate species
in aqueous
solution.

Carbonate Species Concentrations in Surface
Ocean Water

Solubility and Precipitation
of Ionic Salts
Precipitation of slightly soluble ionic salts from aqueous
solution can be viewed as attraction of oppositely charged
ions to form a solid, winning a competition over
aquation of the ions.
Ca2+ (aq) + CO32 (aq) CaCO3(s)

of Ionic Salts
Solubility Equilibria: Saturated Solutions
When a slightly soluble solid salt and its aquated ions
are at equilibrium, the solution is a saturated solution.
In such systems, the equilibrium constant is called the
solubility product (Ksp).
In a saturated solution: Q = Ksp.
AxBy(s) x Ay+(aq) + y Bx(aq) Ksp=[Ay+]x [Bx]y

of Ionic Salts
Solubility products of some common slightly
soluble salts
The solubility of a salt is NOT its solubility product

although they are related.
of Ionic Salts
Relating Solubility and Solubility Product
The solubility of a slightly soluble salt can be deduced
from the value of its solubility product at the
appropriate temperature.
Comparisons of the solubilities of two salts by direct
comparison of their Ksp values can only be correctly
made if the salts have the same cation-to-anion ratio,
for example, 1:1 salts, or all 1:2 salts.

of Ionic Salts
EXAMPLE: Ksp for BaSO4 is 1.1 1010 at 25C. Calculate
the solubility of barium sulfate in pure water at 25C in
(a) moles per litre, and (b) grams per litre.
BaSO4(s) Ba2+(aq) + SO42(aq)
Assume the solubility of BaSO4 is x mol L1; therefore,
[Ba2+]=[SO42]= x mol L1.
Q=[Ba 2+ 2
][SO4 ] =Ksp=1.1 1010 =x2
a) x = 1.0 105 mol L1
b) 1.0 105 mol L1 233 g mol1 = 0.0023 g L1
Ex.
[Ba2+] = 3.6 x 10-3 M in a saturated soln of
barium fluoride. Calculate its Ksp at the same
temperature.
What is the solubility in M, and in g/L, of silver
chromate, Ag2CrO4 (s)? Ksp = 1.1 x 10-12.

of Ionic Salts
Complexity Leading to Errors in Solubility
Calculations
The Ksp value reported for lead (II) chloride (PbCl2) is 1.7
105. If we assume the following equilibrium reaction,
the calculated solubility is only 0.016 mol L1. The
experimental estimate of the solubility is 0.036 mol L1.
Calculations of solubilities from solubility products gives
accurate estimates only if the cation and/or the anion are
only involved in an equilibrium reaction between the solid
salt and its aquated ions in saturated solution.

of Ionic Salts
Complexity Leading to Errors in Solubility
Calculations
(PbCl2) is involved in multiple equilibrium reactions in
solution:

of Ionic Salts
Solubility of Salts and the Common Ion Effect
The presence of a common ion (either the cation or
the anion) reduces the solubility of a slightly soluble salt
in water.
This is another example of the common ion effect.

of Ionic Salts
Barium sulfate is opaque to x-rays.
Physicians use it to examine the
digestive tract after a patient
drinks a slurry containing BaSO4.
The progress of the slurry through
the digestive organs can be
followed by x-ray tracking.
To reduce toxicity, some
potassium sulfate is added to the
slurry to reduce the solubility of
barium sulfate through the
common ion effect. Copyright 2015 by Nelson Education Limited 16
of Ionic Salts
Barium sulfate, a white
solid, is sparingly soluble in
water (Ksp = 1.1 1010).
The mineral barite, which is
mostly barium sulfate.
e15.8 Calculate the influence of

the common ion effect on the
solubility of different salts.

Ex.
Determine the solubility of PbI2 in water and
in a 0.10 M solution of MgI2. Ksp PbI2 = 9.8 x
10-9.

of Ionic Salts
pH-Dependence of Solubility of Salts Whose Anions
Are Bases
Slightly soluble salts in which the anion is a weak base
become more soluble as the pH of solution lowers. The
weaker the anion is as a base, the more pH-dependent the
solubility of such salts.
EXAMPLE: Silver acetate is only slightly soluble in water Ksp
= 1.9 103. However, aquated acetate ions are weak
bases, and react with water. This reaction promotes
dissolution of additional silver acetate.
of Ionic Salts
EXAMPLE: If an acid is added to a water-insoluble metal
carbonate, such as CaCO3, the salt dissolves with
effervescence. This is a net result of acid-base equilibria:
CaCO3(s) + 2 H3O+(aq) Ca2+(aq) + 3 H2O() + CO2(g)
CaCO3(s) Ca2+(aq) + CO32-(aq) Ksp = 3.4 109

CO32(aq) + H2O() HCO3(aq) + OH(aq) Kb1 = 2.1 104
HCO3(aq) + H3O+(aq) H2CO3(aq) + OH(aq) Kb2 = 2.4 108
2 [OH(aq) + H3O+(aq) 2 H2O()] K= (Kw1)2 = 1 1028
Knet =(Ksp)(Kb1)(Kb2)(Kw1)2 = 1.7 108
of Ionic Salts
The reaction between calcium
carbonate, CaCO3(s), and acidified
water has been the cause of
deterioration of marble statues in
many parts of the world. The
marble, a form of calcium
carbonate, has reacted over many
years with H3O+(aq) ions in acid
rainrain with dissolved acidic
pollutants derived from oxidation in
the atmosphere of SO2 and NO2.
Precipitation Reactions
Industrial methods for extracting metals from
their ores
Dissolve metal salts to obtain the metal ions in solution.
Separate the solution from insoluble materials.
Add a reagent to precipitate selectively a salt of only the
desired metal.
Reduce the cation to the metal either chemically or
electrochemically.

Minerals are often insoluble salts. Shown here are fluorite

(calcium fluoride), black hematite (iron (III) oxide) and
brown geothite (a mixture of iron (III) oxide and iron (III)
hydroxide).
Deciding If a Salt Will Precipitate: Q versus Ksp
In the case of a slightly soluble salt:
If Q = Ksp , the solution is saturated and at
equilibrium.
If Q < Ksp , the solution is unsaturated and more can
dissolve.
If Q > Ksp , the solution is supersaturated and
precipitation would bring the system to equilibrium.
Note: This statement says nothing about how fast
precipitation would happen.

Precipitation When Reagent Solutions Are Mixed
If we mix two solutions, one of which contains the
cation of a slightly soluble salt, and the other containing
the anion, we can decide whether salt will precipitate,
or what concentration would be needed for it to occur.
EXAMPLE: Suppose [Mg2+] = 1.5 106 mol L1 in a
solution at 25C. If enough of a concentrated NaOH
solution is added to make [OH] = 1.0 104 mol L1, can
precipitation of Mg(OH)2(s) occur? Ksp = 5.6 1012 at 25C.
Assume that volume change due to addition of the NaOH
solution is small enough to be ignored.
EXAMPLE: Suppose [Mg2+] = 1.5 106 mol L1 in a
solution at 25C. If enough of a concentrated NaOH
solution is added to make [OH] = 1.0 104 mol L1, can
precipitation of Mg(OH)2(s) occur? Ksp = 5.6 1012 at 25C.
SOLUTION:
Mg(OH)2(s) Mg2+(aq) + 2 OH(aq)
Q=[Mg2+][OH]2 =(1.5 106 )(1.0 104 )2 = 1.5 1014 <
Ksp
The solution is not saturated, and precipitation does not
occur.
Precipitation is possible if [OH] is increased by adding
more NaOH solution until Q > Ksp.
Adjusting the Concentration of One Ion
How do we know what concentration to increase
one of the ions to induce saturation? Adjust the
concentration of the added ion until Q = Ksp.
EXAMPLE: [Ba 2+] = 0.010 mol L1 in a solution at 25C.
What concentration of aquated sulfate ions is required to
render the solution saturated (and on the verge of
precipitation of some BaSO4(s))?

EXAMPLE: [Ba 2+] = 0.010 mol L1 in a solution at 25C.
What concentration of aquated sulfate ions is required to
render the solution saturated (and on the verge of
precipitation of some BaSO4(s))?
SOLUTION:
BaSO4(s) Ba2+(aq) + SO42(aq)
At equilibrium at 25C,
Q=[Ba2+ ][SO42] =(0.010 )[SO42] = Ksp= 1.1 1010
[SO42] = Ksp [Ba2+ ] = 1.1 1010 0.010 = 1.1 108 mol L1

At a known concentration of one of the ions of a

slightly soluble salt, we can use the condition Q =
Ksp to calculate the concentration of the other ion
that will bring about a saturated solution, on the
verge of some precipitation.

Separation of Metal Cations by Selective
Precipitation
When two metals have salts of the same anion with
sufficiently different solubilities, they may be effectively
separated by selective precipitation.
In a solution containing aquated cations of both metals,
if the concentration of the aquated anion is raised
incrementally, as the solution becomes saturated with
respect to the most soluble salt, the less soluble salt
selectively precipitates from solution. See worked ex
15.10 on page 609.
Ex.
If a soln at 25 C has [Mg2+] = 0.200 M and
[Cu2+] = 0.100 M, at what [OH-] could we get
max. separation of the cations by precipitation
of one of them as the slightly soluble
hydroxide? At 25 C, Ksp Mg(OH)2 is 5.6 x 10-12
and Ksp Cu(OH)2 is 2.2 x 10-20.

Solubility and Complexation:
Competitive Equilibria
Salts that are only slightly soluble in water can dissolve
as a result of reaction between the metal cation and a
Lewis base to form a complex ion.
This can be regarded as the result of two competing
reactions for the cation: formation of a solid lattice vs.
formation of the complex ion.
Equilibrium constants for formation of complex ions,
called formation constants (Kf), are measures of
stability of the complex ions.

NH3 NaBr
Solution Solution

Competition: Precipitation vs. Complexation.
Beginning with a precipitate of AgCl(s), adding an
aqueous ammonia solution dissolves the precipitate as
the soluble complex ion [Ag(NH3)2]+(aq) is formed.

Competition: Precipitation vs. Complexation.
Silver bromide is even more stable than [Ag(NH3)2]+(aq),
so AgBr(s) forms on addition of bromide ions.
If thiosulfate ions, S2O32(aq), are then added, AgBr(s)
dissolves due to the formation of [Ag(S2O3)2]3(aq), a
complex ion with a large formation constant.

NaBr Na2S2O3
Solution Solution

Complexation versus Lewis Base
Protonation
Ag+(aq) + 2 NH3(aq) [Ag(NH3)2]+(aq) Kf = 1.6 107
NH3(aq) + H2O() NH4+(aq) + OH(aq) Kb = 1.8 105
pH-dependent speciation
between NH4+(aq) ions
and NH3(aq) molecules in
aqueous solution. The
concentrations of the two
species are equal at pH =
pKa (NH4+) = 9.25.
Protonation
Speciation plot showing
the percentages of Ag+(aq)
ions and [Ag(NH3)2]+ ions
present as pH is changed.
Below about pH 7, the
concentration of the
[Ag(NH3)2]+ ions is
negligible, as ammonia
exists mainly as NH4+(aq)
ions.

Protonation
Modelled pH-dependent
speciation between Ag+(aq)
ions and [Ag(L)2]+. The
hypothetical HL+(aq) ion is a
stronger acid than NH4+(aq).
The conjugate base, L(aq),
would be less able to grab
H+ ions than NH3(aq), so the
[Ag(L)2]+ complex ions would
be the dominant species
over a wider pH range.
Protonation
Metal ion complexes with a Lewis base that is also a
Brnsted-Lowry weak base are less stable at lower pH
because of competition of H3O+(aq) ions for the base.
In comparing Lewis bases, the stronger they are as
Brnsted-Lowry bases (the higher the pKa of the
conjugate acid), the higher the pH is at which the Lewis
base is protonated.

Ocean Acidification Revisited
Quantitatively
Some fundamental types of calculation of pH-
dependence of the solubility of salts whose anions are
bases were discussed in this chapter.
Here we apply these to the situation of calcium
carbonate solubility in sea water as pH decreases.
See ExplainingClimateChange.com to see how chemistry
and science can make sense of climate change.
Go to the interactive learning tool at
http://tinyurl.com/pHocean to explore the relationship
between atmospheric CO2(g) levels and ocean pH.

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Solubility, Precipitation, and

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The solubility of a salt is NOT its solubility product

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e15.8 Calculate the influence of

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CaCO3(s) Ca2+(aq) + CO32-(aq) Ksp = 3.4 109

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Minerals are often insoluble salts. Shown here are fluorite

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At a known concentration of one of the ions of a

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