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Resources
Chapter Presentation
Bellringer
Transparencies
Sample Problems
Visual Concepts
Standardized Test Prep
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Chapter 14
Chemical Equilibrium
Table of Contents
Section 1 Reversible Reactions and Equilibrium
Section 2 Systems at Equilibrium
Section 3 Equilibrium Systems and Stress
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Chapter 14
Section 1 Reversible Reactions and
Equilibrium
Bellringer
• Describe what reversible means.
• Find a synonym for reversible.
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Chapter 14
Section 1 Reversible Reactions and
Equilibrium
Objectives
• Contrast reactions that go to completion with
reversible ones.
• Describe chemical equilibrium.
• Give examples of chemical equilibria that involve
complex ions.
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Chapter 14
Section 1 Reversible Reactions and
Equilibrium
Completion Reactions and Reversible
Reactions
• If enough oxygen gas is provided for the following
reaction, almost all of the sulfur will react:
S8(s) + 8O2(g) → 8SO2(g)
• Reactions such as this one, in which almost all of the
reactants react, are called completion reactions.
• In other reactions, called reversible reactions, the
products can re-form reactants.
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Chapter 14
Section 1 Reversible Reactions and
Equilibrium
Completion Reactions and Reversible
Reactions, continued
Reversible Reactions Reach Equilibrium
• One reversible reaction occurs when you mix
solutions of calcium chloride and sodium sulfate.
CaCl2(aq) + Na2SO4(aq) → CaSO4(s) + 2NaCl(aq)
• The net ionic equation best describes what happens.
Ca2 (aq )  SO24 (aq )  CaSO 4 (s )
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Chapter 14
Section 1 Reversible Reactions and
Equilibrium
Completion Reactions and Reversible
Reactions, continued
Reversible Reactions Reach Equilibrium, continued
• Solid calcium sulfate, the product, can break down to
make calcium ions and sulfate ions in a reaction that
is the reverse of the previous one.
CaSO4 (s )  Ca2 (aq )  SO24 (aq )
• Use arrows that point in opposite directions when
writing a chemical equation for a reversible reaction.

 CaSO4 (s )
Ca2 (aq )  SO2
4 (aq ) 
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Chapter 14
Section 1 Reversible Reactions and
Equilibrium
Completion Reactions and Reversible
Reactions, continued
Reversible Reactions Reach Equilibrium, continued
• The reactions occur at the same rate after the initial
mixing of CaCl2 and Na2SO4.
• The amounts of the products and reactants do not
change.
• Chemical equilibrium is a state of balance in which
the rate of a forward reaction equals the rate of the
reverse reaction and the concentrations of products
and reactants remain unchanged.
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Chapter 14
Section 1 Reversible Reactions and
Equilibrium
Completion Reactions and Reversible
Reactions, continued
Opposing Reaction Rates Are Equal at Equilibrium
• The reaction of hydrogen, H2, and iodine, I2, to form
hydrogen iodide, HI, reaches chemical equilibrium.

 2HI(g )
H2 (g )  I2 (g ) 

• Only a very small fraction of the collisions between H2
and I2 result in the formation of HI.
H2(g) + I2(g) → 2HI(g)
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Chapter 14
Section 1 Reversible Reactions and
Equilibrium
Completion Reactions and Reversible
Reactions, continued
Opposing Reaction Rates Are Equal at Equilibrium,
continued
• After some time, the concentration of HI goes up.
• As a result, fewer collisions occur between H2 and I2
molecules, and the rate of the forward reaction drops.
• Similarly, in the beginning, few HI molecules exist in
the system, so they rarely collide with each other.
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Chapter 14
Section 1 Reversible Reactions and
Equilibrium
Completion Reactions and Reversible
Reactions, continued
Opposing Reaction Rates Are Equal at Equilibrium,
continued
• As more HI molecules are made, they collide more
often and form H2 and I2 by the reverse reaction.
2HI(g) → H2(g) + I2(g)
• The greater the number of HI molecules that form, the
more often the reverse reaction occurs.
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Chapter 14
Section 1 Reversible Reactions and
Equilibrium
Rate Comparison for H2(g) + I2(g)  2HI(g)
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Chapter 14
Section 1 Reversible Reactions and
Equilibrium
Completion Reactions and Reversible
Reactions, continued
Opposing Reaction Rates Are Equal at Equilibrium,
continued
• When the forward rate and the reverse rate are equal,
the system is at chemical equilibrium.
• If you repeated this experiment at the same
temperature, starting with a similar amount of pure HI
instead of the H2 and I2, the reaction would reach
chemical equilibrium again and produce the same
concentrations of each substance.
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Chapter 14
Visual Concepts
Chemical Equilibrium
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Chapter 14
Section 1 Reversible Reactions and
Equilibrium
Chemical Equilibria Are Dynamic
• If you drop a ball into a bowl, it will bounce.
• When the ball comes to a stop it has reached static
equilibrium, a state in which nothing changes.
• Chemical equilibrium is different from static
equilibrium because it is dynamic.
• In a dynamic equilibrium, there is no net change in
the system.
• Two opposite changes occur at the same time.
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Chapter 14
Section 1 Reversible Reactions and
Equilibrium
Chemical Equilibria Are Dynamic, continued
• In equilibrium, an atom may change from being part
of the products to part of the reactants many times.
• But the overall concentrations of products and
reactants stay the same.
• For chemical equilibrium to be maintained, the rates
of the forward and reverse reactions must be equal.
• Arrows of equal length also show equilibrium.

 products
reac tants 

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Chapter 14
Section 1 Reversible Reactions and
Equilibrium
Chemical Equilibria Are Dynamic, continued
• In some cases, the equilibrium has a higher
concentration of products than reactants.
• This type of equilibrium is also shown by using two
arrows.
reac tants 

 products
• The forward reaction has a longer arrow to show
that the products are favored.
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Chapter 14
Section 1 Reversible Reactions and
Equilibrium
More Examples of Equilibria
• Even when systems are not in equilibrium, they are
continuously changing in order to reach equilibrium.
• For example, combustion produces carbon dioxide,
CO2, and poisonous carbon monoxide, CO. After
combustion, a reversible reaction produces soot.

 C(s )  CO2 (g )
2CO(g ) 

• This reaction of gases and a solid will reach chemical
equilibrium.
• Equilibria can involve any state of matter, including
aqueous solutions.
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Chapter 14
Section 1 Reversible Reactions and
Equilibrium
More Examples of Equilibria, continued
Equilibria Involving Complex Ions
• Complex ion, or coordination compound, is the name
given to any metal atom or ion that is bonded to more
than one atom or molecule.
• Some ions have a metal ion surrounded by ligands,
molecules or anions that readily bond to metal ions.
• Complex ions may be positively charged cations or
negatively charged anions.
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Chapter 14
Section 1 Reversible Reactions and
Equilibrium
More Examples of Equilibria, continued
Equilibria Involving Complex Ions, continued
• In this complex ion, [Cu(NH3)4]2+, ammonia molecules
bond to the central copper(II) ion.
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Chapter 14
Section 1 Reversible Reactions and
Equilibrium
More Examples of Equilibria, continued
Equilibria Involving Complex Ions, continued
Complex ions formed from transition metals are often
deeply colored.
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Chapter 14
Section 1 Reversible Reactions and
Equilibrium
More Examples of Equilibria, continued
Equilibria Involving Complex Ions, continued
• The charge on a complex ion is a sum of the charges
on the species from which the complex ion forms.
• For example, when the cobalt ion, Co2+, bonds
with four Cl− ligands, the total charge is (+2) +
4(−1) = −2.
• Metal ions and ligands can form complexes that have
no charge. These are not complex ions.
• Complex ions often form in systems that reach
equilibrium.
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Chapter 14
Section 1 Reversible Reactions and
Equilibrium
More Examples of Equilibria, continued
Equilibria Involving Complex Ions, continued
• Consider zinc nitrate dissolving in water:

 Zn2 (aq )  2NO3- (aq )
Zn(NO3 )2 (s ) 

• In the absence of other ligands, water molecules
bond with zinc ions. So, this reaction can be written:

 [Zn(H2O)4 ]2 (aq )  2NO3- (aq )
Zn(NO3 )2 (s )  4H2O(l ) 

• If another ligand, such as CN−, is added, the new
system will again reach chemical equilibrium.
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Chapter 14
Section 1 Reversible Reactions and
Equilibrium
More Examples of Equilibria, continued
Equilibria Involving Complex Ions, continued
• Both water molecules and cyanide ions “compete” to
bond with zinc ions, as shown in the equation below.

 [Zn(CN)4 ]2– (aq )  4H2O( l )
[Zn(H2O)4 ]2 (aq )  4CN– (aq ) 

• All of these ions are colorless, so you cannot see
which complex ion has the greater concentration.
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Chapter 14
Section 1 Reversible Reactions and
Equilibrium
More Examples of Equilibria, continued
Equilibria Involving Complex Ions, continued
• In the chemical equilibrium of nickel ions, ammonia,
and water, the complex ions have different colors.
• You can see which ion has the greater
concentration.
2


[Ni(H2O)6 ]2 (aq )  6NH3 (aq ) 
[Ni(NH
)
]
(aq )  6H2O( l )

3 6
green
blue-violet
• The starting concentration of NH3 will determine
which one will have the greater concentration.
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Chapter 14
Section 2 Systems at Equilibrium
Bellringer
• Make a list of numbers that are “constants” under
constant conditions.
• An example is the speed of light.
• What do these constants have in common?
• Answer: Each constant is always the same number
for a certain and constant set of conditions.
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Chapter 14
Section 2 Systems at Equilibrium
Objectives
• Write Keq expressions for reactions in equilibrium,
and perform calculations with them.
• Write Ksp expressions for the solubility of slightly
soluble salts, and perform calculations with them.
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Chapter 14
Section 2 Systems at Equilibrium
The Equilibrium Constant, Keq
• Limestone caverns form as rainwater, slightly acidified
by H3O+, dissolves calcium carbonate.
• The reverse reaction also takes place, depositing
calcium carbonate and forming stalactites and
stalagmites.

 Ca2 (aq )  CO2 (g )  3H2O(l )
CaCO3 (s )  2H3O (aq ) 

• When the rates of the forward and reverse reactions
become equal, the reaction reaches chemical
equilibrium.
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Chapter 14
Section 2 Systems at Equilibrium
The Equilibrium Constant, Keq, continued
• There is a mathematical relationship between product
and reactant concentrations at equilibrium.
• For limestone reacting with acidified water at 25°C:
[Ca2 ][CO2 ]
-9
Keq 

1.4

10
[H3O ]2
• Keq is the equilibrium constant of the reaction.
• Keq for a reaction is unitless, applies only to systems
in equilibrium, and depends on temperature and
must be found experimentally or from tables.
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Chapter 14
Visual Concepts
Equilibrium Constant
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Chapter 14
Section 2 Systems at Equilibrium
The Equilibrium Constant, Keq, continued
Determining Keq for Reactions at Chemical
Equilibrium
1. Write a balanced chemical equation.
• Make sure that the reaction is at equilibrium
before you write a chemical equation.
2. Write an equilibrium expression.
• To write the expression, place the product
concentrations in the numerator and the reactant
concentrations in the denominator.
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Chapter 14
Section 2 Systems at Equilibrium
The Equilibrium Constant, Keq, continued
Determining Keq for Reactions at Chemical
Equilibrium, continued
• The concentration of any solid or a pure liquid that
takes part in the reaction is left out.
• For a reaction occurring in aqueous solution,
water is omitted.
3. Complete the equilibrium expression.
• Finally, raise each substance’s concentration to
the power equal to the substance’s coefficient
in the balanced chemical equation.
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Chapter 14
Visual Concepts
Equilibrium Constant
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Chapter 14
Section 2 Systems at Equilibrium
Calculating Keq from Concentrations of
Reactants and Products
Sample Problem A
An aqueous solution of carbonic acid reacts to reach
equilibrium as described below.
–



H2CO3 (aq )  H2O(l ) 
HCO
(
aq
)

H
O
(aq )

3
3
The solution contains the following solution
concentrations: carbonic acid, 3.3 × 10−2 mol/L;
bicarbonate ion, 1.19 × 10−4 mol/L; and hydronium ion,
1.19 × 10−4 mol/L. Determine the Keq.
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Section 2 Systems at Equilibrium
Chapter 14
Calculating Keq from Concentrations of
Reactants and Products
Sample Problem A Solution
[H2CO3 ]  3.3  10-2
[HCO3– ]  [H3O ]  1.19  10-4
For this reaction, the equilibrium constant expression is
K eq
[HCO3– ][H3O ]

[H2CO3 ]
Substitute the concentrations into the expression.
Keq
[HCO3– ][H3O ] (1.19  10-4 )  (1.19  10-4 )
-7



4.3

10
[H2CO3 ]
(3.3  10-2 )
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Chapter 14
Section 2 Systems at Equilibrium
The Equilibrium Constant, Keq, continued
Keq Shows If the Reaction Is Favorable
• When Keq is large, the numerator of the equilibrium
constant expression is larger than the denominator.
• Thus, the concentrations of the products will
usually be greater than those of the reactants.
• In other words, when a reaction that has a large Keq
reaches equilibrium, there will be mostly products.
• Reactions in which more products form than reactants
form are said to be “favorable.”
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Chapter 14
Section 2 Systems at Equilibrium
The Equilibrium Constant, Keq, continued
Keq Shows If the Reaction Is Favorable, continued
• The synthesis of ammonia is very favorable at 25°C
and has a large Keq value.

 2NH3 (g )
N2 (g )  3H2 (g ) 

K eq
[NH3 ]2
8


3.3

10
[N2 ][H2 ]3
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at 25 C
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Chapter 14
Section 2 Systems at Equilibrium
The Equilibrium Constant, Keq, continued
Keq Shows If the Reaction Is Favorable, continued
• However, the reaction of oxygen and nitrogen to give
nitrogen monoxide is not favorable at 25°C.

 2NO(g )
N2 (g )  O2 (g ) 

K eq
[NO2 ]2

 4.5  10 –31
[N2 ][O2 ]
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at 25 C
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Chapter 14
Section 2 Systems at Equilibrium
The Equilibrium Constant, Keq, continued
Keq Shows If the Reaction Is Favorable, continued
• When Keq is small, the denominator of the equilibrium
constant expression is larger than the numerator.
• The larger denominator shows that the concentrations
of reactants at chemical equilibrium may be greater
than those of products.
• A reaction that has larger concentrations of reactants
than concentrations of products is an “unfavorable”
reaction.
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Chapter 14
Section 2 Systems at Equilibrium
The Equilibrium Constant, Keq, continued
Keq Shows If the Reaction Is Favorable, continued
These pie charts show the relative amounts of reactants
and products for three Keq values of a reaction.
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Chapter 14
Section 2 Systems at Equilibrium
Calculating Concentrations of Products
from Keq and Concentrations of Reactants
Sample Problem B
Keq for the equilibrium below is 1.8 × 10−5 at a
temperature of 25°C. Calculate [NH4 ] when
[NH3] = 6.82 × 10−3.

–


NH3 (aq )  H2O(l ) 
NH
(
aq
)

OH
(aq )

4
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Chapter 14
Section 2 Systems at Equilibrium
Calculating Concentrations of Products
from Keq and Concentrations of Reactants,
continued
Sample Problem B Solution
The equilibrium expression is
NH4and OH− ions are produced in equal numbers, so
[OH– ]  [NH4 ].
So, the numerator can be written as x2.
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Chapter 14
Section 2 Systems at Equilibrium
Calculating Concentrations of Products
from Keq and Concentrations of Reactants,
continued
Sample Problem B Solution, continued
Keq and [NH3] are known and can be put into the
expression.
1.8  10–5  Keq
[NH4 ][OH– ]
x2


[NH3 ]
6.82  10-3
x2 = (1.8  10−5)  (6.82  10−3) = 1.2 × 10−7
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Chapter 14
Section 2 Systems at Equilibrium
Calculating Concentrations of Products
from Keq and Concentrations of Reactants,
continued
Sample Problem B Solution, continued
Take the square root of x2.
[NH4 ]  1.2  10-7  3.5  10-4
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Chapter 14
Section 2 Systems at Equilibrium
The Solubility Product Constant, Ksp
• The maximum concentration of a salt in an aqueous
solution is called the solubility of the salt in water.
• Solubilities can be expressed in moles of solute per
liter of solution (mol/L or M).
• For example, the solubility of calcium fluoride in
water is 3.4 × 10−4 mol/L.
• So, 0.00034 mol of CaF2 will dissolve in 1 L of
water to give a saturated solution.
• If you try to dissolve 0.00100 mol of CaF2 in 1 L
of water, 0.00066 mol of CaF2 will remain
undissolved.
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Chapter 14
Visual Concepts
Solution Equilibrium
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Chapter 14
Section 2 Systems at Equilibrium
The Solubility Product Constant, Ksp, continued
• Calcium fluoride is one of a large class of salts that are
said to be slightly soluble in water.
• The ions in solution and any solid salt are at
equilibrium.
2
–


CaF2 (s ) 
Ca
(
aq
)

2F
(aq )

• Solids are not a part of equilibrium constant
expressions, so Keq for this reaction is the product
of [Ca2+] and [F−]2, which is equal to a constant.
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Chapter 14
Section 2 Systems at Equilibrium
The Solubility Product Constant, Ksp,
continued
• Equilibrium constants for the dissolution of slightly
soluble salts are called solubility product
constants, Ksp, and have no units.
• The Ksp for calcium fluoride at 25°C is 1.6  10−10.
Ksp = [Ca2+][F−]2 = 1.6  10−10
• This relationship is true whenever calcium ions and
fluoride ions are in equilibrium with calcium fluoride,
not just when the salt dissolves.
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Chapter 14
Section 2 Systems at Equilibrium
The Solubility Product Constant, Ksp,
continued
• For example, if you mix solutions of calcium nitrate
and sodium fluoride, calcium fluoride precipitates.
• The net ionic equation for this precipitation is the
reverse of the dissolution.

 CaF2 (s )
Ca2 (aq )  2F– (aq ) 

• This equation is the same equilibrium. So, the Ksp for
the dissolution of CaF2 in this system is the same and
is 1.6 × 10−10.
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Chapter 14
Visual Concepts
Solubility Product Constant
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Chapter 14
Visual Concepts
Solubility Product Constant
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Chapter 14
Section 2 Systems at Equilibrium
The Solubility Product Constant, Ksp, continued
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Chapter 14
Section 2 Systems at Equilibrium
The Solubility Product Constant, Ksp, continued
Determining Ksp for Reactions at Chemical Equilibrium
1. Write a balanced chemical equation.
• Solubility product is only for salts that have low
solubility. Soluble salts do not have Ksp values.
• Make sure that the reaction is at equilibrium.
• Equations are always written so that the solid salt
is the reactant and the ions are products.
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Chapter 14
Section 2 Systems at Equilibrium
The Solubility Product Constant, Ksp, continued
Determining Ksp for Reactions at Chemical Equilibrium
2. Write a solubility product expression.
•
Write the product of the ion concentrations.
•
Concentrations of solids or liquids are omitted.
3. Complete the solubility product expression.
•
Raise each concentration to a power equal to
the substance’s coefficient in the balanced
chemical equation.
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Chapter 14
Visual Concepts
Using Solubility Product Constants
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Chapter 14
Section 2 Systems at Equilibrium
Calculating Ksp from Solubility
Sample Problem C
Most parts of the oceans are nearly saturated with
CaF2.The mineral fluorite, CaF2, may precipitate when
ocean water evaporates. A saturated solution of CaF2
at 25°C has a solubility of 3.4 × 10−4 M. Calculate the
solubility product constant for CaF2.
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Chapter 14
Section 2 Systems at Equilibrium
Calculating Ksp from Solubility, continued
Sample Problem C Solution
2
–


CaF2 (s ) 
Ca
(
aq
)

2F
(aq )

[CaF2] = 3.4  10–4, [F−] = 2[Ca2+]
Ksp = [Ca2+][F−]2
Because 3.4 × 10−4 mol CaF2 dissolves in each liter of
solution, you know from the balanced equation that
every liter of solution will contain 3.4 × 10−4 mol Ca2+
and 6.8 × 10−4 mol F−. Thus, the Ksp is:
[Ca2+][F−]2 = (3.4 10−4)(6.8  10−4)2 =
1.6 × 10−10
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Chapter 14
Section 2 Systems at Equilibrium
Calculating Ionic Concentrations Using Ksp,
Sample Problem D
Copper(I) chloride has a solubility product constant of
1.2 × 10−6 and dissolves according to the equation
below. Calculate the solubility of this salt in ocean
water in which the [Cl−] = 0.55.

–


CuCl(s ) 
Cu
(
aq
)

Cl
(aq )

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Chapter 14
Section 2 Systems at Equilibrium
Calculating Ionic Concentrations Using Ksp,
continued
Sample Problem D Solution
The product of [Cu+][Cl−] must equal Ksp = 1.2 × 10−6.
[Cl−] = 0.55
Ksp = [Cu+][Cl−] = 1.2 × 10−6
–6
K
1.2

10
[Cu ]  sp– 
 2.2  10–6
[Cl ]
0.55
This is the solubility of copper(I) chloride because the
dissolution of 1 mol of CuCl produces 1 mol of Cu+.
Therefore, the solubility of CuCl is 2.2 × 10−6 mol/L.
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Chapter 14
Section 2 Systems at Equilibrium
The Solubility Product Constant, Ksp, continued
Using Ksp to Make Magnesium
• Though slightly soluble hydroxides are not salts, they
have solubility product constants.
• Magnesium hydroxide is an example.
2
–


Mg(OH)2 (s ) 
Mg
(
aq
)

2OH
(aq )

[Mg2+][OH−]2 = Ksp = 1.8 × 10−11
• This equilibrium is the basis for obtaining
magnesium.
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Chapter 14
Section 2 Systems at Equilibrium
The Solubility Product Constant, Ksp, continued
Using Ksp to Make Magnesium, continued
• The table at right lists
the most abundant ions
in ocean water and
their concentrations.
• Mg2+ is the third most
abundant ion in the
ocean.
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Chapter 14
Section 2 Systems at Equilibrium
The Solubility Product Constant, Ksp, continued
Using Ksp to Make Magnesium, continued
• To get magnesium, calcium hydroxide is added to sea
water, which raises the hydroxide ion concentration to a
large value so that [Mg2+][OH−]2 would be greater than
1.8 × 10−11.
• Magnesium hydroxide precipitates.
• Magnesium hydroxide is treated with hydrochloric acid
to make magnesium chloride, MgCl2.
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Chapter 14
Section 2 Systems at Equilibrium
The Solubility Product Constant, Ksp, continued
Using Ksp to Make Magnesium, continued
• Finally, magnesium is obtained by the electrolysis of
MgCl2 in the molten state.
• One cubic meter of sea water yields 1 kg of
magnesium metal.
• Because of magnesium’s low density and rigidity,
alloys of magnesium are used when light weight and
strength are needed.
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Chapter 14
Section 3 Equilibrium Systems and
Stress
Bellringer
• List examples of everyday adjustments that are
made to relieve stress on a system.
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Chapter 14
Section 3 Equilibrium Systems and
Stress
Objectives
• State Le Châtelier’s principle.
• Apply Le Châtelier’s principle to determine whether
the forward or reverse reaction is favored when a
stress such as concentration, temperature, or
pressure is applied to an equilibrium system.
• Discuss the common-ion effect in the context of Le
Châtelier’s principle.
• Discuss practical uses of Le Châtelier’s principle.
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Chapter 14
Section 3 Equilibrium Systems and
Stress
Le Châtelier’s Principle
• Stress is another word for something that causes a
change in a system at equilibrium.
• Chemical equilibrium can be disturbed by a stress,
but the system soon reaches a new equilibrium.
• Le Châtelier’s principle states that when a system at
equilibrium is disturbed, the system adjusts in a way
to reduce the change.
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Chapter 14
Section 3 Equilibrium Systems and
Stress
Le Châtelier’s Principle, continued
• Chemical equilibria respond to three kinds of stress:
• changes in the concentrations of reactants or
products
• changes in temperature
• changes in pressure
• When a stress is first applied to a system, equilibrium
is disturbed and the rates of the forward and
backward reactions are no longer equal.
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Chapter 14
Section 3 Equilibrium Systems and
Stress
Le Châtelier’s Principle, continued
• The system responds to the stress by forming more
products or by forming more reactants.
• A new chemical equilibrium is reached when enough
reactants or products form.
• At this point, the rates of the forward and backward
reactions are equal again.
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Chapter 14
Visual Concepts
Le Châtelier's Principle
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Chapter 14
Section 3 Equilibrium Systems and
Stress
Le Châtelier’s Principle, continued
Changes in Concentration Alter Equilibrium
Composition
• If you increase a reactant’s concentration, the system
will respond to decrease the concentration of the
reactant by changing some of it into product.
• Therefore, the rate of the forward reaction must be
greater than the rate of the reverse reaction.
• The equilibrium is said to shift right, and the reactant
concentration drops until the reaction reaches
equilibrium.
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Chapter 14
Section 3 Equilibrium Systems and
Stress
Le Châtelier’s Principle, continued
Changes in Concentration Alter Equilibrium
Composition, continued
• In a reaction of two colored complex ions:
2


[Cu(H2O)4 ]2 (aq)  4NH3 (aq ) 
[Cu(NH
)
]
(aq )  4H2O( l )

3 4
pale blue
blue-purple
• When the reaction mixture in a beaker is pale blue,
we know that chemical equilibrium favors the
formation of reactants.
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Chapter 14
Section 3 Equilibrium Systems and
Stress
Le Châtelier’s Principle, continued
Changes in Concentration Alter Equilibrium
Composition, continued
If ammonia is added, the system responds by forming
more product and the solution becomes blue-purple.
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Chapter 14
Section 3 Equilibrium Systems and
Stress
Le Châtelier’s Principle, continued
Changes in Concentration Alter Equilibrium
Composition, continued
• The equilibrium below occurs in a bottle of soda.

 2H2O(l )  CO2 (aq )
H3O (aq )  HCO3– (aq ) 

• After you uncap the bottle, the dissolved carbon
dioxide leaves the solution and enters the air.
• The forward reaction rate of this system will increase
to produce more CO2.
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Chapter 14
Section 3 Equilibrium Systems and
Stress
Le Châtelier’s Principle, continued
Changes in Concentration Alter Equilibrium
Composition, continued
• This increase in the rate of the forward reaction
decreases the concentration of H3O+.
• As a result, the drink gets “flat.”
• If you could increase the concentration of CO2 in the
bottle, the reverse reaction rate would increase, and
[H3O ] and [HCO3– ] would increase.
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Chapter 14
Section 3 Equilibrium Systems and
Stress
Le Châtelier’s Principle, continued
Temperature Affects Equilibrium Systems
• The effect of temperature on the gas-phase
equilibrium of nitrogen dioxide, NO2, and dinitrogen
tetroxide, N2O4, can be seen because of the
difference in color of NO2 and N2O4.
• The intense brown NO2 gas is the pollution that is
responsible for the colored haze that you sometimes
see on smoggy days.

 N2O4 (g )
2NO2 (g ) 

brown
colorless
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Chapter 14
Section 3 Equilibrium Systems and
Stress
Le Châtelier’s Principle, continued
Temperature Affects Equilibrium Systems, continued
• Recall that endothermic reactions absorb energy and
have positive ∆H values.
• Exothermic reactions release energy and have
negative ∆H values.
• The forward reaction is an exothermic process, as the
equation below shows.
2NO2(g) → N2O4(g)
∆H = −55.3 kJ
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Chapter 14
Section 3 Equilibrium Systems and
Stress
Temperature Changes Affect an Equilibrium
System
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Chapter 14
Section 3 Equilibrium Systems and
Stress
Le Châtelier’s Principle, continued
Temperature Affects Equilibrium Systems, continued
• Now suppose that you heat the flask to 100°C.
• The mixture becomes dark brown because the
reverse reaction rate increased to remove some of
the energy that you added to the system.
• The equilibrium shifts to the left, toward the formation
of NO2.
• Because this reaction is endothermic, the
temperature of the flask drops as energy is
absorbed.
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Chapter 14
Section 3 Equilibrium Systems and
Stress
Le Châtelier’s Principle, continued
Temperature Affects Equilibrium Systems, continued
• This equilibrium shift is true for all exothermic forward
reactions:
• Increasing the temperature of an equilibrium
mixture usually leads to a shift in favor of the
reactants.
• The opposite statement is true for endothermic forward
reactions:
• Increasing the temperature of an equilibrium
mixture usually leads to a shift in favor of the
products.
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Chapter 14
Section 3 Equilibrium Systems and
Stress
Le Châtelier’s Principle, continued
Temperature Affects Equilibrium Systems, continued
• The following is an endothermic reaction involving two
colored cobalt complex ions:
2–


[Co(H2O)6 ]2 (aq )  4Cl– (aq) 
[CoCl
]
(aq )  6H2O(l )

4
pink
blue
• The forward reaction is endothermic, so the forward
reaction is favored at high temperatures.
• The reverse reaction is favored at low temperatures.
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Chapter 14
Section 3 Equilibrium Systems and
Stress
Le Châtelier’s Principle, continued
Temperature Affects Equilibrium Systems, continued
• Equilibrium changes with changes in temperature
they affect the value of equilibrium constants.
• Consider Keq for the ammonia synthesis equilibrium:

 2NH3 (g )
N2 (g )  3H2 (g ) 

• The forward reaction is exothermic (∆H = −91.8 kJ),
so the equilibrium constant decreases a lot as
temperature increases.
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Chapter 14
Visual Concepts
Factors Affecting Equilibrium
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Chapter 14
Section 3 Equilibrium Systems and
Stress
Le Châtelier’s Principle, continued
Pressure Changes May Alter Systems in Equilibrium
• Changes in pressure can affect gases in equilibrium.
• The NO2 and N2O4 equilibrium can show the effect of
a pressure stress on a chemical equilibrium.
2NO2(g) → N2O4(g)
• When the gas mixture has a larger concentration of
N2O4 than of NO2, it has a pale color.
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Chapter 14
Section 3 Equilibrium Systems and
Stress
Le Châtelier’s Principle, continued
Pressure Changes May Alter Systems in Equilibrium
When the gas is suddenly compressed to about half
its former volume, the pressure doubles.
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Chapter 14
Section 3 Equilibrium Systems and
Stress
Le Châtelier’s Principle, continued
Pressure Changes May Alter Systems in Equilibrium,
continued
• Before the system has time to adjust to the pressure
stress, the concentration of each gas doubles, which
results in a darker color.
• Le Châtelier’s principle predicts that the system will
adjust in an attempt to reduce the pressure.
• According to the equation, 2 mol of NO2 produce 1 mol
of N2O4.
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Chapter 14
Section 3 Equilibrium Systems and
Stress
Le Châtelier’s Principle, continued
Pressure Changes May Alter Systems in Equilibrium,
continued
• At constant volume and temperature, pressure is
proportional to the number of moles.
• So, the pressure reduces when there are fewer moles
of gas.
• Thus, the equilibrium shifts to the right, and more
N2O4 is produced.
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Chapter 14
Section 3 Equilibrium Systems and
Stress
Le Châtelier’s Principle, continued
Pressure Changes May Alter Systems in Equilibrium,
continued
• In an equilibrium, a pressure increase favors the
reaction that produces fewer gas molecules, which for
the following equilibrium is the reverse reaction.

 2NO(g )  Cl2 (g )
2NOCl(g ) 

• When there is no change in the number of molecules,
a change in pressure will not affect equilibrium.

 H2 (g )  CO2 (g )
H2O(g )  CO(g ) 

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Chapter 14
Visual Concepts
Equilibrium
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Chapter 14
Section 3 Equilibrium Systems and
Stress
The Common-Ion Effect
• The solubility of CuCl in water is 1.1  10−3 mol/L.
• The solubility of CuCl in sea water is 2.2  10−6 mol/L
• CuCl is 500 times less soluble in sea water.
• The dramatic reduction in solubility of CuCl shows Le
Châtelier’s principle and is described below.

–


CuCl(s ) 
Cu
(
aq
)

Cl
(aq )

[Cu+][Cl−] = Ksp = 1.2 × 10−6
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Chapter 14
Section 3 Equilibrium Systems and
Stress
The Common-Ion Effect, continued
• If you add chloride-rich ocean water to a saturated
solution of copper(I) chloride, [Cl−] increases.
• However, the Ksp, or [Cl−]  [Cu+], remains constant.
• [Cu+] must decrease.
• This decrease can occur only by the precipitation
of the CuCl salt.
• The ion Cl− is the common-ion in this case.
• The reduction of the solubility of a salt in the solution
due to the addition of a common ion is called the
common-ion effect.
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Chapter 14
Visual Concepts
Common–Ion Effect
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Chapter 14
Section 3 Equilibrium Systems and
Stress
The Common-Ion Effect, continued
• Doctors use solutions of barium sulfate, BaSO4, to
diagnose problems in the digestive tract.
• BaSO4 is in equilibrium with a small concentration of
Ba2+(aq), a poison.
• To reduce the Ba2+ concentration to a safe level, a
common ion is added.
• Doctors add sodium sulfate, Na2SO4, into the BaSO4
solution that a patient must swallow.
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Chapter 14
Section 3 Equilibrium Systems and
Stress
The Common-Ion Effect, continued
• Another example of the common-ion effect emerges
when solutions of potassium sulfate and calcium
sulfate are mixed and either solution is saturated.
• Immediately after the two solutions are mixed, the
2
2–
[Ca
]
and
[SO
product of the
4 ] is greater than the
Ksp of calcium sulfate.
• So, CaSO4 precipitates to establish equilibrium:
2
2–


CaSO4 (s ) 
Ca
(
aq
)

SO

4 (aq )
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Chapter 14
Section 3 Equilibrium Systems and
Stress
Practical Uses of Le Châtelier’s Principle
• The chemical industry makes use of Le Châtelier’s
principle in the synthesis of ammonia by the Haber
Process.
• High pressure is used to drive the following
equilibrium to the right.

 2NH3 (g )
N2 (g )  3H2 (g ) 

• The forward reaction converts 4 mol of gas into 2 mol
of another gas, so it is favored at high pressures.
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Chapter 14
Section 3 Equilibrium Systems and
Stress
Practical Uses of Le Châtelier’s Principle,
continued
• The ammonia synthesis is an exothermic reaction, so
the forward reaction is favored at low temperatures.
0°C
250°C
500°C
Keq = 6.5 × 108
Keq = 52
Keq = 5.8 × 10−2
• The Haber Process is operated at temperatures of
500°C even though the Keq is small at that temperature.
• The reaction proceeds too slowly at lower
temperatures.
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Chapter 14
Standardized Test Preparation
Understanding Concepts
1. In which of these reactions is the formation of the
products favored by an increase in pressure?
A. 2O3(g)  3O2(g)
B. C(s) + O2(g)  CO2(g)
C. 2NO(g) + O2(g)  2NO2(g)
D. CO2 (aq ) + 2H2O(l )  H3O (aq ) + HCO3– (aq )
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Chapter 14
Standardized Test Preparation
Understanding Concepts
1. In which of these reactions is the formation of the
products favored by an increase in pressure?
A. 2O3(g)  3O2(g)
B. C(s) + O2(g)  CO2(g)
C. 2NO(g) + O2(g)  2NO2(g)
D. CO2 (aq ) + 2H2O(l )  H3O (aq ) + HCO3– (aq )
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Chapter 14
Standardized Test Preparation
Understanding Concepts
2. What is the effect of an increase in temperature on an
exothermic reaction at equilibrium?
F. It has no effect on the equilibrium.
G. It shifts the equilibrium in favor of the forward
reaction.
H. It shifts the equilibrium in favor of the reverse
reaction.
I. It shifts the equilibrium in favor of both the forward
and reverse reactions.
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Chapter 14
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Understanding Concepts
2. What is the effect of an increase in temperature on an
exothermic reaction at equilibrium?
F. It has no effect on the equilibrium.
G. It shifts the equilibrium in favor of the forward
reaction.
H. It shifts the equilibrium in favor of the reverse
reaction.
I. It shifts the equilibrium in favor of both the forward
and reverse reactions.
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Chapter 14
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Understanding Concepts
3. Which of the following properties of a reactant is
included in a Keq equation?
A. charge
B. concentration
C. mass
D. volume
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Chapter 14
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Understanding Concepts
3. Which of the following properties of a reactant is
included in a Keq equation?
A. charge
B. concentration
C. mass
D. volume
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Chapter 14
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Understanding Concepts
4. Explain how the common ion effect is involved in the
addition of NaIO3 to a solution of Cd(IO3)2, which is
much less soluble than NaIO3.
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Understanding Concepts
4. Explain how the common ion effect is involved in the
addition of NaIO3 to a solution of Cd(IO3)2, which is
much less soluble than NaIO3.
Answer: Some of the Cd(IO3)2 would precipitate out of
the solution, reducing the cadmium ion concentration.
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Chapter 14
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Understanding Concepts
5. Explain how pressure can be used to maximize the
production of carbon dioxide in the reaction

 2CO2 (g )?
2CO(g )  O2 (g ) 

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Chapter 14
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Understanding Concepts
5. Explain how pressure can be used to maximize the
production of carbon dioxide in the reaction

 2CO2 (g )?
2CO(g )  O2 (g ) 

Answer: Increasing the pressure will cause the reaction
to favor the production of carbon dioxide because
there are three gas molecules in the reactants and
only two in the products.
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Chapter 14
Standardized Test Preparation
Reading Skills
Read the passage below. Then answer the questions.
Coral reefs are made by tiny organisms known as
polyps. They attach themselves permanently in one
place and survive by eating tiny marine animals that
swim past. The polyps secrete calcium carbonate to
make their shells or skeletons. When the polyps die,
the calcium carbonate structures remain and
accumulate over time to form a reef. This reef building
is possible because calcium carbonate is only slightly
soluble in water.
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Chapter 14
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Reading Skills
6. What is the Ksp expression for calcium carbonate?
F. Ksp  [Ca2 ][CO32– ]
G. Ksp  [Ca2 ][CO32– ]2
2 2
2–
H. Ksp  [Ca ] [CO3 ]
I.
Ksp  [Ca2 ]2 [CO32– ]2
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Chapter 14
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Reading Skills
6. What is the Ksp expression for calcium carbonate?
F. Ksp  [Ca2 ][CO32– ]
G. Ksp  [Ca2 ][CO32– ]2
2 2
2–
H. Ksp  [Ca ] [CO3 ]
I.
Ksp  [Ca2 ]2 [CO32– ]2
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Reading Skills
7. What is the most likely source of calcium used by the
polyps to build their shells?
A. calcium atoms in solution in sea water
B. calcium ions in solution in sea water
C. calcium particles that reach the water in acid rain
D. calcium containing rocks gathered from the ocean
floor
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Chapter 14
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Reading Skills
7. What is the most likely source of calcium used by the
polyps to build their shells?
A. calcium atoms in solution in sea water
B. calcium ions in solution in sea water
C. calcium particles that reach the water in acid rain
D. calcium containing rocks gathered from the ocean
floor
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Chapter 14
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Reading Skills
8. The Ksp for calcium carbonate is 2.8  10-9 and the
Ksp value for calcium sulfate is 9.1  10-6. If coral
polyps secreted calcium sulfate rather than calcium
carbonate, how would this affect the formation of the
coral reef?
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Chapter 14
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Reading Skills
8. The Ksp for calcium carbonate is 2.8  10-9 and the
Ksp value for calcium sulfate is 9.1  10-6. If coral
polyps secreted calcium sulfate rather than calcium
carbonate, how would this affect the formation of the
coral reef?
Answer: A reef would not be built as quickly if polyps
secreted calcium sulfate, because calcium sulfate has
a higher solubility in water.
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Chapter 14
Standardized Test Preparation
Interpreting Graphics
Use the information from the table below to answer
questions 9 through 12.
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Chapter 14
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Interpreting Graphics
9. What is the concentration of magnesium carbonate in
a saturated aqueous solution?
F. 0.0000068 M
G. 0.0026 M
H. 0.84 M
I. 1.31 M
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Interpreting Graphics
9. What is the concentration of magnesium carbonate in
a saturated aqueous solution?
F. 0.0000068 M
G. 0.0026 M
H. 0.84 M
I. 1.31 M
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Interpreting Graphics
10. If a saturated solution of silver carbonate is mixed
with a saturated solution of zinc sulfide, a precipitate
forms. What compound precipitates?
A. Ag2CO3
B. Ag2S
C. ZnCO3
D. ZnS
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Interpreting Graphics
10. If a saturated solution of silver carbonate is mixed
with a saturated solution of zinc sulfide, a precipitate
forms. What compound precipitates?
A. Ag2CO3
B. Ag2S
C. ZnCO3
D. ZnS
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Interpreting Graphics
11. Calculate the concentration of S2– ions in a saturated
solution of FeS that contains 0.010 M Fe2+ ions.
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Interpreting Graphics
11. Calculate the concentration of S2– ions in a saturated
solution of FeS that contains 0.010 M Fe2+ ions.
Answer: 1.6  10–17 M
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Interpreting Graphics
12. What will happen if a solution containing 1  10–10 M
Na2CO3 is mixed with an equal volume of a solution
containing 1  10–10 M MgCl2 and 1  10–10 M ZnCl2?
F. No precipitate will form.
G. MgCO3 will precipitate out of the solution.
H. ZnCO3 will precipitate out of the solution.
I. MgCO3 and ZnCO3 will precipitate out of the
solution.
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Chapter 14
Standardized Test Preparation
Interpreting Graphics
12. What will happen if a solution containing 1  10–10 M
Na2CO3 is mixed with an equal volume of a solution
containing 1  10–10 M MgCl2 and 1  10–10 M ZnCl2?
F. No precipitate will form.
G. MgCO3 will precipitate out of the solution.
H. ZnCO3 will precipitate out of the solution.
I. MgCO3 and ZnCO3 will precipitate out of the
solution.
Chapter menu
Resources
Copyright © by Holt, Rinehart and Winston. All rights reserved.