Topic 4
Topic 4
Topic 4
chemical equilibrium
Topic 4: chemical equilibrium
C12-4-01 Relate the concept of equilibrium to physical and chemical
systems.
Include: conditions necessary to achieve equilibrium
C12-4-03 Use the value of the equilibrium constant (Keq) to explain how far
a system at equilibrium has gone towards completion.
C12-4-04 Solve problems involving equilibrium constants.
C12-4-05 Perform a laboratory activity to determine the equilibrium
constant of an equilibrium system.
C12-4-06 Use Le Châtelier’s principle to predict and explain shifts in
equilibrium.
Include: temperature changes, pressure/volume changes, changes in
reactant/product concentration, the addition of a catalyst, the addition
of an inert gas, and the effects of various stresses on the equilibrium
constant
Entry-Level Knowledge
In Grade 9 Science (S1-2-12), students were introduced to the difference between
physical and chemical changes. In Grade 11 Chemistry (C11-1-05, C11-1-06),
students were introduced to the concept of equilibrium with respect to the rates of
evaporation and condensation of a liquid in a closed container. They further
developed analogies to help them understand the concept.
TEAchER NoTEs
Reversible Reactions for Physical Equilibrium
Up to this point, this chemistry curriculum has addressed reversibility in physical
systems (i.e., phase changes and dissociation). Students will now be introduced to
the potential for reversibility in chemical systems. Discuss the conditions that are
necessary to achieve equilibrium in physical and chemical systems and emphasize
the differences between the two systems.
Physical equilibria require a closed system at constant temperature. Examples of
physical equilibria are evaporation and dissolving.
Examples:
In the diagram below, water (H2O(l)) is in equilibrium with its vapour (H2O(g)). The
rate of evaporation is equal to the rate of condensation in a closed container at a
constant temperature. At the particulate level, for every one molecule of water
(H2O(l)) that evaporates, another water vapour molecule (H2O(g)) condenses to the
liquid state. This is an example of a reversible reaction for a physical equilibrium.
Liquid state
H2O(l)
Animation
Have students view an equilibrium animation online.
Sample Website:
Chemical Education Research Group, Iowa State University. “Chemistry
Experiment Simulations and Conceptual Computer Animations.” Chemical
Education. <http://group.chem.iastate.edu/Greenbowe/sections/
projectfolder/simDownload/index4.html> (22 Nov. 2012).
In the General Equilibria section, download and unzip the following animation:
n Bromine Liquid-Gas Equilibrium Animation
This animation shows the molecular nature between liquid bromine and
gaseous bromine. Have students count the number of molecules in the gas
phase and in the liquid phase.
At the particulate level for this reaction, the rate of forward reaction is equal to the
rate of the reverse reaction. This means that for every molecule of H2 that combines
with a molecule of Cl2, there is one molecule of HCl that reacts with another
molecule of HCl, which reform to make the reactants H2 and Cl2. For a particulate
representation of this reversible reaction, see the following diagram.
Reversible Reaction
Key
= Cl2
= H2
= HCl
ä
ä
H2 + Cl2 ä HCl
ä
ä
HCl + HCl äH
2 + Cl2
The diagram shows H2 + Cl2 combining to form two molecules of HCl, and two
molecules of HCl combining to reform H2 + Cl2.
Demonstration/Animation
Demonstrate a chemical equilibrium with an NO2—N2O4 system or a CoCl42——
Co(H2O)62+ system. See Appendix 4.1: Preparation of Equilibrium Systems
(Demonstration) for preparation instructions. Sealed units of NO2—N2O4 can be
purchased from science supply companies rather than preparing the tubes for
classroom demonstration.
Have students view an online demonstration or animation of a chemical
equilibrium.
Sample Website:
Chemical Education Research Group, Iowa State University. “Chemistry
Experiment Simulations and Conceptual Computer Animations.” Chemical
Education. <http://group.chem.iastate.edu/Greenbowe/sections/
projectfolder/simDownload/index4.html> (22 Nov. 2012).
In the General Equilibria section, download and unzip the following animation:
n NO2–N2O4 Equilibrium Animation
This animation shows the NO2–N2O4 reaction at the particulate level.
Graphs
How systems achieve equilibrium can be demonstrated through concentration
versus time graphs and rate versus time graphs, such as the following.
Reactants
Rate
Reactants
Products Products
te te
Time Time
To prevent the misconception that equilibrium has been achieved by the end of the
plateau, point out to students that equilibrium occurs as soon as the plateau begins.
Avoid a quantitative discussion of these graphs at this point.
For example, in a class of 20 students, 10 students could represent sodium ions and
10 students could represent chloride ions. Have 4 sodium ions and 4 chloride ions
link arms on the left side of the room to represent sodium chloride particles. Have
the remaining 12 students stand on the right side of the room. Ask a student to
record on the board the number of each type of particles.
At this point, explain that in order for sodium chloride to break apart, heat is
required. Place on the floor four pieces of red construction paper (to represent the
heat), which can be picked up by the students representing the sodium chloride
particles so that they can break up into sodium and chloride ions and move to the
right side of the room. (The sodium ions in the sodium chloride particle should
hold onto the heat). Students on the right side of the room could use the heat to join
together to form a sodium chloride particle and move to the left side of the room.
Allow this movement to continue for a few minutes, and then have a student record
the number of each particle a second time. Repeat this process once more so that
students can see that equilibrium has occurred.
Emphasize that the process of equilibrium is not finished. The forward and reverse
processes continue to occur.
Laboratory Activity
Have students perform the Discovery Lab: What’s equal about equilibrium?
(Dingrando, et al. 559).
For this lab activity, students pour 20 mL of water into a graduated cylinder and
20 mL into a beaker. They then place one glass tube in the cylinder and another
glass tube in the beaker. Students cover the end of each glass tube with their index
fingers and simultaneously transfer water from the cylinder to the beaker, and from
the beaker to the cylinder. The heights will even out after a number of transfers.
Equilibrium is established with 30 mL in the beaker and 10 mL in the graduated
cylinder.
Journal Writing
1. Ask students to list reactions that are reversible (e.g., dissolving salt in water)
and reactions that are not reversible (e.g., burning paper).
2. Have students answer the following question:
At equilibrium, does the concentration of reactant have to equal the
concentration of product? Explain your answer.
Answer:
No, the concentrations must be constant over time. They will not necessarily be
equal.
appendix
Appendix 4.1: Preparation of Equilibrium Systems (Demonstration)
Entry-Level Knowledge
In Grade 7 Science (7-2-14), students were introduced to heterogeneous and
homogeneous solutions.
TEAchER NoTEs
Equilibrium Expressions
The ratio of product concentrations (raised to the value of the coefficient from the
balanced equation) to reactant concentrations (raised to the value of the coefficient
from the balanced equation) in a reaction at equilibrium is represented by the
equilibrium law expression (mass action expression). The law of mass action was
introduced in 1864 by Cato Maximilian Guldberg and Peter Waage, two Norwegian
chemists who “analyzed the results of many different experiments and tested a
variety of mathematical relationships until they discovered the relationship that
always gave consistent results” (Chastko 640).
“equilibrium Law expression
C c D d
Kc
A a B b
Where [A], [B], [C], and [D] represent the concentrations of the reactants and
products after the reaction has reached equilibrium and the concentrations no
longer change. The exponents, a, b, c, and d, are the stoichiometric coefficients from
the equation” (Chastko 641).
A general equilibrium reaction can be written as follows:
aA bB
cC dD
Equilibrium constants
Solids and liquids are not included in the mass action expression, as their
concentrations are constant. Regardless of how much of the solid or liquid is
present, the concentration (mol/L) of the solid and liquid remains the same. The
value of the mass action expression at any point in time is called the reaction
quotient (Q). At equilibrium, it is called the equilibrium constant (Keq). Inform
students that equilibrium constants are specific for only one reaction at a particular
temperature.
The equilibrium constant provides information such as how far a reaction has gone
toward completion before it reaches equilibrium. Because the equilibrium constant
is the ratio of products to reactants, a Keq value greater than 1 (Keq> 1) means that
there were more products than reactants, so the reaction was close to completion
when equilibrium was achieved (and vice versa).
Many chemistry textbooks use the symbol Keq to represent the equilibrium constant.
Unless the value is given with appropriate units, this symbol does not distinguish
between a constant equilibrium value calculated from equilibrium
concentrations (Kc) and that calculated from equilibrium pressure (Kp). In textbooks,
units are not used because they would vary depending on the powers to which the
concentrations are raised. In some cases, all units would cancel.
Note that
. . . students need extra practice using their calculators to solve problems
involving scientific notation. In particular, students commonly make the mistake
of using the times () sign when entering scientific-notation numbers. Point out
that the exponent key ([EXP] on most calculators . . . or [EE] on others) actually
represents ‘ 10.’ To help students with this process, lead them through
entering several numbers in scientific-notation and carrying out calculations
with the numbers. (Dingrando, et al., Glencoe Chemistry: Matter and Change,
Teacher Wraparound Edition 579)
H2g I 2g 2HIg
Solution:
Rateforward = kf[H2][I2]
Ratereverse = kr[HI]2
At equilibrium,
Rateforward = Ratereverse
So,
kf[H2][I2] = kr[HI]2
Note: We can’t cancel the k values, as they are not identical to one another.
2
kf HI
kr
H2
I2
or
kr H
I
2 22
kf HI
If the concentrations for the first trial are substituted into this equation, the value
obtained is
2 2
kf HI 0.015869
59.6
kr
H2
0.0032583 0.0012949
I2
Using the same concentrations for the first trial and substituting these values into
the second equation, the result is
kr H
I
0.0032583 0.0012949
2 22 0.017
kf HI 0.0158692
Student groups should obtain answers in the order of 60 or 0.02 when using the
concentrations given in the other trials. Inform students that scientists have
collectively agreed that the equilibrium constants would be reported in texts such
as the CRC Handbook of Chemistry and Physics (CRC Press), using the ratio of product
to reactant concentrations, or
2
kf HI
Keq
kr
H2
I2
CaCO 3 s
CaOs CO 2g
Solution:
In applying the standard form of the mass action expression, the equation would be
written as follows:
CaO
CO 2
Keq
CaCO 3
However, the concentrations of pure solids and liquids are constant (i.e., they
cannot change). They are not included in the mass action expression, so the mass
action expression for the decomposition of calcium carbonate is
Keq
CO 2
Journal Writing
Ask students to “research the work of the Norwegian chemists Cato Maximilian
Guldberg and Peter Waage that led them to propose the law of mass action. Have
them describe how the law of mass action results in the formatting of equilibrium
constant expressions” (Dingrando, et al., Chemistry: Matter and Change, Teacher
Wraparound Edition 563).
appendices
Appendix 4.2: Solving Equilibrium Problems Using the ICE Table Method
Appendix 4.3: Solving for Keq Using the BIR/PEC Accounting Method
Appendix 4.4: Equilibrium Problems
Notes
Entry-Level Knowledge
In addressing specific learning outcome C12-4-04, students solved problems
involving equilibrium constants. They will now have an opportunity to use
experimental data to calculate the value of Keq for a reversible reaction.
TEAchER NoTEs
It is not intended that students perform all the lab activities suggested below (and
in the Learning Resources Links). Select a lab activity appropriate for students’ skill
level and the equipment available at the school.
Laboratory skills
Periodically and randomly review the lab skills of individual students, so that
eventually all students are assessed. Pay particular attention to skills related to
serial dilutions from stock solutions. Sample checklists for assessing lab skills and
work habits are available in SYSTH (6.10, 6.11).
Entry-Level Knowledge
In Grade 11 Chemistry (C11-02-05), students performed an experiment to discover
Boyle’s law, which states that pressure and volume are inversely proportional to
one another. In both Grades 11 and 12 Chemistry (C11-3-13, C12-3-04), students
have worked with endothermic and exothermic reactions. Students performed a lab
activity (C12-3-02) to observe the effects of concentration, temperature, pressure,
volume, and the presence of a catalyst on the rate of a reaction.
TEAchER NoTEs
Le châtelier’s Principle
In 1884, French chemist Henri Louis Le Châtelier proposed the law of mobile
equilibrium (commonly referred to as Le Châtelier’s principle), which states that if a
stress is placed on a reversible reaction at chemical equilibrium, the equilibrium
will shift to relieve the stress, thereby restoring equilibrium. Le Châtelier’s principle
describes how a chemical equilibrium shifts in response to a stress or disturbance
within an enclosed system, as described in the following table.
decrease in The system shifts to produce It changes because the equilibrium position
temperature more heat, favouring the shifts without any substances being added or
exothermic reaction. removed. There is no heat-related term in the
mass action expression to maintain the ratio.
increase in The system shifts to the side It does not change because all reactant and
volume with the most gas particles product concentrations change, resulting in the
(decrease in because solids and liquids same ratio.
pressure) are incompressible.
decrease in The system shifts to the side It does not change because all reactant and
volume with the fewest gas particles product concentrations change, resulting in the
(increase in because solids and liquids same ratio.
pressure) are incompressible.
increase in The system shifts to decrease It does not change because all reactant and
concentration the reactant or product that product concentrations change, resulting in the
was added. same ratio.
decrease in The system shifts to increase It does not change because all reactant and
concentration the reactant or product that product concentrations change, resulting in the
was removed. same ratio.
The following shows how a change in concentration affects the other substances in
a chemical reaction (Silberberg 746).
These concentration changes cause a shift to the right:
increase increase decrease
PCl 3 Cl 2
PCl 5
Demonstrations
n traffic Light reaction
This demonstration shows an oscillating colour reaction starting with yellow-
orange, changing to red (after shaking the flask once), and then to green (after
shaking the flask again). After the flask stands for awhile, the colour returns to
red and then back to yellow-orange. The idea behind this demonstration is that
shaking is enough for the first reaction to occur, and then a few more shakes
gets the second reaction going. As the solution settles, the kinetic energy (from
shaking) drops, and the reactions do not have enough energy to continue.
To prepare for the demonstration, dissolve 32 g of potassium hydroxide in
1200 mL water (solution A), 40 g of glucose in 1200 mL water (solution B), 0.50 g
of benzoin in 500 mL water (solution C), and 1.0 g of indigo carmine in 200 mL
water (solution D). To a clean, empty flask, add 200 mL of solution A, then 200
mL of B, then 60 mL of C, and then 16 mL of D.
Similar demonstrations can be viewed online.
Sample Websites:
Keusch, Peter. “Belousov-Zhabotinsky Reaction.” Organic Chemistry
Demonstration Experiments on Video: Chemistry Visualized. University of
Regensburg. <www.uni-regensburg.de/Fakultaeten/nat_Fak_IV/
Organische_Chemie/Didaktik/Keusch/D-oscill-e.htm> (22 Feb. 2012).
In this video demonstration, the colour oscillates between red and blue.
n Qualitative equilibrium
The pre-lab exercise provided in Appendix 4.7: Equilibrium and Le Châtelier’s
Principle (Pre-lab) gives students an opportunity to predict the direction in
which the equilibrium will shift with the given stresses. A complete student
procedure for this lab activity can be found in Appendix 4.8A: Qualitative
Equilibrium: Lab Activity. (See Appendix 4.8B for teacher notes.) Students create
an equilibrium system using 0.02 mol/L iron(III) nitrate and 0.002 mol/L
potassium thiocyanate. The solutions are mixed, and then “stressed” by adding
iron(III) nitrate, solid potassium thiocyante, and sodium hydrogen phosphate to
samples of the solution. Shifts in the original equilibrium position may be seen
through colour changes.
n disrupting equilibrium systems
The procedure for this lab activity can be found in Appendix 4.9: Disrupting
Equilibrium Systems: Lab Activity. The reaction that students study is
2
Co H 2 O 6
4Cl
2
CoCl 4 6H 2 O
pink blue
Students dissolve cobalt chloride in ethanol and record the colour of the
solution. They add stresses to samples of this prepared solution (distilled water,
hydrochloric acid, solid calcium chloride, silver nitrate solution, addition of heat,
and removal of heat) and note the resulting colours.
n miniLaB 18: shifts in equilibrium (Dingrando, et al., Glencoe Chemistry: Matter
and Change 573)
In this experiment, students observe an equilibrium shift in a colourful way.
Students add hydrochloric acid to a 0.1 mol/L solution of cobalt chloride. The
pink colour changes to a purple colour. To this solution, students then add
water, and the colour returns to pink. Then students place a sample of the cobalt
chloride-hydrochloric acid solution in hot water, which results in a blue colour
being produced. When they place a sample of the cobalt chloride-hydrochloric
acid solution in cold water, the pink colour appears.
n Lab 15: observing equilibrium (Dingrando, et al., Glencoe Chemistry: Matter and
Change: Small-Scale Laboratory Manual, Teacher Edition 57)
In the first part of the lab activity, students record the colours of Fe3+ ion, SCN—
ion, and FeSCN2+ ion. The direction of shift in equilibrium is measured by the
colour change that occurs, which is related to the concentration of reactant.
Students pour a dilute solution of iron(III) nitrate and potassium thiocyanate
into five separate test tubes. To the first test tube, 0.5 g of Fe(NO3)3 is added to
the solution, and a darker red colour is observed. To the second test tube, 0.5 g
NH4SCN is added to the solution, and a dark red colour results. To the third test
tube, 0.5 g KCl is added to the solution, and a light red colour (or orange colour)
is observed. To the fourth test tube, a few millilitres of sodium hydroxide
solution is added to the original solution, which results in a colourless solution
with a white precipitate. To the fifth test tube, a few millilitres of silver nitrate
are added, which results in a colourless solution and a white precipitate.
n experiment 29: Le Châtelier’s Principle and Chemical equilibrium (Waterman
and Thompson, Prentice Hall Chemistry: Small-Scale Chemistry Laboratory Manual
203)
In this experiment, students “observe and record how a chemical system at
equilibrium responds to changes in concentration of reactants or products” (203).
They describe these shifts in equilibrium in terms of Le Châtelier’s principle. As
this is a small-scale lab activity, the quantities required of the following solutions
are minimal: bromthymol blue, hydrochloric acid, sodium hydroxide, ammonia,
copper(II) sulphate, lead(II) nitrate, potassium iodide, nitric acid, silver nitrate,
sodium carbonate, sodium thiosulphate, and sodium phosphate.
n investigation 16a: modelling equilibrium (Chastko, et al. 635)
This investigation is similar to the one outlined in Appendix 4.6A: An Analogy
for an Equilibrium Reaction. Using two glass tubes of different diameters,
students transfer water from one graduated cylinder to another, and vice versa.
In the reactant cylinder, 25 mL of water is present. In the product cylinder, there
is no water present initially.
online Demonstrations
Have students view online demonstrations of Le Châtelier’s principle.
Sample Website:
The North Carolina School of Science and Mathematics (NCSSM). “Chapter 14: Gas
Phase, Solubility, Complex Ion Equilibria.” Chemistry Online Resource Essentials
(CORE). <www.dlt.ncssm.edu/core/c14.htm> (13 Jan. 2012).
This website provides a variety of video clips that demonstrate shifts in
equilibrium using Le Châtelier’s principle:
n FeSCN2+ Equilibrium—Le Châtelier’s Principle Lab, Part 1 shows the effect of
adding stresses to the equilibrium FeSCN2+–Fe(SCN)+2.
n Cobalt Complex Ion Equilibrium—Le Châtelier’s Principle Lab, Part 3
demonstrates the cobalt chloride complex (pink to blue) equilibrium.
n NO2–N2O4 Gas Equilibrium—Le Châtelier’s Principle Lab, Part 4 shows the effect
of temperature on the equilibrium NO2–N2O4. As temperature is decreased,
there is an increase in N2O4 (colourless).
Use this equilibrium to explain why the brownish haze over a large city
disappears in the winter, only to reappear again in the spring.
Answer:
The stress is a decrease in temperature in the winter. The exothermic reaction (a
release of heat) would be favoured to oppose the decrease in temperature. This
would favour the production of the colourless dinitrogen tetraoxide gas. In the
summer, the stress would be an increase in temperature. The endothermic
reaction (absorption of heat) would be favoured to oppose this stress. Nitrogen
dioxide would, therefore, be produced, and we would see a brown haze over the
city.
Journal Writing
Students can write a fictionalized newspaper article written on the day after Henri
Louis Le Châtelier’s principle was announced in 1884. Students’ articles should
highlight this scientific contribution.
Laboratory Reports
Students can use the Lab Report Format to write their lab reports (see SYSTH
14.12). Word processing and spreadsheet software could be used to prepare reports.
Also refer to the Lab Report Assessment rubric in Appendix 11.
Laboratory skills
Periodically and randomly review the lab skills of individual students, so that
eventually all students are assessed. For sample checklists, refer to SYSTH (6.10,
6.11).
Websites
Keusch, Peter. “Belousov-Zhabotinsky Reaction.” Organic Chemistry
Demonstration Experiments on Video: Chemistry Visualized. University
of Regensburg. <www.uni-regensburg.de/Fakultaeten/nat_Fak_IV/
Organische_Chemie/Didaktik/Keusch/D-oscill-e.htm> (22 Feb. 2012).
The North Carolina School of Science and Mathematics (NCSSM).
“Chapter 14: Gas Phase, Solubility, Complex Ion Equilibria.” Chemistry
Online Resource Essentials (CORE). <www.dlt.ncssm.edu/core/c14.htm>
(13 Jan. 2012).
Wyatt, Shawn. “Go-Science Traffic Light Reaction Chemistry Demonstration.”
World News. <http://wn.com/Traffic_Light_Reaction_GO-
Science_Demonstration> (22 Feb. 2012).
appendices
Appendix 4.6A: An Analogy for an Equilibrium Reaction: Lab Activity
Appendix 4.6B: An Analogy for an Equilibrium Reaction: Lab Activity
(Teacher Notes)
Appendix 4.6C: An Analogy for an Equilibrium Reaction: Lab Report
Checklist
Appendix 4.7: Equilibrium and Le Châtelier’s Principle (Pre-lab)
Appendix 4.8A: Qualitative Equilibrium: Lab Activity
Appendix 4.8B: Qualitative Equilibrium: Lab Activity (Teacher Notes)
Appendix 4.9: Disrupting Equilibrium Systems: Lab Activity
Notes
Entry-Level Knowledge
In learning outcome C12-4-01, students were introduced to a qualitative treatment
of concentration versus time graphs.
In learning outcome C12-4-06, students saw that a system at equilibrium will shift
to minimize a stress and re-establish equilibrium.
TEAchER NoTEs
Ask students to recall that equilibrium is shown by a plateau on a concentration
versus time graph. If students completed the analogy lab activity in addressing
learning outcomes C12-4-06 and C12-4-07, ask them to refer to their results. See
Appendix 4.6A: An Analogy for an Equilibrium Reaction: Lab Activity. The plateau
in such concentration versus time graphs demonstrates that the concentrations of
reactants and products are not changing over time.
Data Table
7 s
6 s
Concentration (mol/L)
5 s s s
4s
s
3 sssss
2
u u u
1 u uuu uuu
0u
0 5 10 15 20 25 30 35
Time (s)
u FeSCN2+
SCN-
s Fe3+
2
FeSCN 1.5
4. Keq 0.24
51.25
3
Fe
SCN
5. The two values are approximately the same because the stress imposed on the
system was not a change in temperature.
6. The addition of Fe3+ occurred at 14 seconds.
7. A catalyst would decrease the time required to reach equilibrium. This would
condense (“squish”) the graph along the x-axis.
(1 hour)
Entry-Level Knowledge
Students were introduced to Le Châtelier’s principle in learning outcome C12-4-06.
TEAchER NoTEs
Practical Applications of Le châtelier’s Principle
The following examples of the practical applications of Le Châtelier’s principle are
provided to indicate the importance of Le Châtelier’s principle in our lives.
Students are not expected to learn the examples in great detail. Teachers can either
have students collect information from their own textbooks or, if information is
limited, through additional research. Some information is provided here for teacher
reference.
In a place such as Mexico City, where the elevation is 2.3 km above sea level,
atmospheric pressure and oxygen concentration are low. To offset the stress,
equilibrium favours the reverse direction. As a result, people who live there may
experience hypoxia (a lack of oxygen), which can cause headache, nausea, and
extreme fatigue. In serious cases, if victims are not treated quickly, they may slip
into a coma and die.
(continued)
When a bottle of soda pop is opened, the pressure above the carbon dioxide
decreases. The system shifts to the left, the solubility of the carbon dioxide
drops, and carbon dioxide bubbles out of solution. If the bottle is left open for a
long time, the pop will go “flat” due to the reduced pressure.
Shaking a pop bottle will increase the pressure on the system, which will shift to
relieve the stress by favouring the forward reaction. Increasing the temperature
of a pop bottle (e.g., leaving it in a warm car on a summer day) will cause
equilibrium to shift in the reverse direction, creating more carbon dioxide gas.
This will generate a pressure that could potentially cause the pop bottle to burst.
In the absence of light, the retinene is separated from the opsin. It takes time to
be able to see in the dark, again because the complex can be recombined with
the help of adenosine triphosphate (ATP) molecules in a slower reverse reaction.
In a dark room, the photoreceptors in the eyes take a few minutes to re-
equilibrate to a lower light intensity, as the reverse reaction is slower. Moving
into a brightly lit room, the photoreceptors in the eyes again take a few minutes
to adjust to their new equilibrium due to the slower reverse reaction.
Ret-Op
Ret Op light
Signal sent Signal not sent
n Blood ph
Blood contains dissolved carbonic acid in equilibrium with carbon dioxide and
water.
H2 CO 3aq CO 2aq H2 Ol
To keep carbonic acid at safe concentrations in the blood, the CO2 product is
exhaled. The removal of a product causes the forward reaction to be favoured,
reducing the amount of carbonic acid to keep blood pH within a safe range
(Chang, 9th ed. 706).
n rechargeable Batteries
The following types of batteries are recharged through the addition of electrical
energy. When energy is added to the system, the reverse reaction is favoured,
which produces more reactants. Balanced chemical equations are provided for
each of the following types of batteries.
n lead-acid batteries:
PbO 2s Pbs 4Haq 2 SO 4 2aq
2 PbSO 4 s 2H 2 Ol energy
(continued)
n nickel-cadmium batteries:
Cds 2NiO OH s 2 H2 Ol
2 PbSO 4s 2 H2 O l energy
n fuel cells:
2 H 2 g O 2 g 2H 2 Ol energy
n turbocharged/supercharged engines
In a turbocharged engine, air is compressed and heated. This means that there is
a higher concentration (50 percent more) of warmer oxygen reacting with the
gasoline. This favours the production of products, which generates more power
for the car.
Turbochargers in normal engines work best at higher altitudes where the air is
less dense. The steam created by the reaction of the gasoline and oxygen is used
to turn a turbine that runs the air compressor. In a supercharger, a belt runs the
compressor.
Gasoline O 2 CO 2 H2 O power
n ester synthesis
Reactions producing esters favour the reverse reaction. To favour the forward
reaction, scientists must increase the amount of acid present in the system.
CH 3OH CH3 COOH
CH3 COOCH 3 H 2 O
n Weather indicators
Students may have seen that weather indicators are blue under normal
conditions but turn pink to indicate approaching rain. The colour changes are
due to changes in the colour of cobalt(II) chloride:
2 2
CoCl 4
6H 2 O
Co H2 O 6 4Cl
blue pink
In periods of low humidity, the colour of the weather indicator is blue. When the
humidity is high, the products will be favoured and the colour of the indicator
will be pink.
When chickens become hot, they pant, which decreases the concentration of
carbon dioxide in the blood. To offset the stress, the equilibrium will shift in the
reverse direction and decrease the amount of calcium carbonate available to
make eggshells. This yields eggs with thin shells that break easily. Ted Odom, a
graduate student at the University of Illinois, found that giving chickens
carbonated water to drink will shift equilibrium in the forward direction and
minimize the effects of panting on warm days. This allows farmers to minimize
the effects without having to install expensive air conditioning in chicken coops
(van Kessel, et al. 457).
(continued)
collaborative Teamwork
Use collaborative strategies such as Jigsaw (see SYSTH 3.20) or Roundtable
discussions (see Appendix 7) to have students share their knowledge of specific
examples of Le Chatelier’s principle with their classmates.
Journal Writing
1. Have students reflect on common examples of Le Châtelier’s principle. Students’
reflections could be based on examples from their everyday lives or from careers
that use the principle.
2. Students can describe how their bodies would relieve the stress placed on them
by climbing to a high altitude (Fisher 251).
Quiz/Test
Test students on their understanding of the applications of Le Châtelier’s principle,
using questions such as the following:
1. When someone takes your photograph, you may see a “ghost” image of the
flash for several minutes after the photo is taken. Explain this phenomenon in
terms of the rates of the forward and reverse rhodopsin reactions in the eye.
Answer:
When the flash occurred, the photoreceptors in the eye responded quickly to the
bright burst. However, since the reverse reaction is much slower, and the
intensity of the flash was so great, a ghost image can be seen for several minutes
while the reactions in the photoreceptors take time to reverse themselves.
2. When isopentyl alcohol and acetic acid react, they form the pleasant-smelling
compound isopentyl acetate (the essence of banana oil):
C 5H11OHaq CH3 COOHaq
CH 3COOC 5 H11aq H 2 Ol
Rubrics/checklists
See Appendix 11 for a variety of rubrics and checklists that can be used for self-,
peer-, and teacher-assessment for any of the research presentations.
(continued)
Notes
Entry-Level Knowledge
In addressing learning outcomes C12-1-01 and C12-1-02, students saw reactions that
produce precipitates.
TEAchER NoTEs
solubility Product constants
In addressing learning outcomes C12-4-10 and C12-4-11, students should become
aware that the precipitates formed by double displacement reactions are not
insoluble, but slightly soluble. For example, while a solubility table would indicate
that silver chloride (AgCl) is insoluble, it does undergo both dissociation and
precipitation to set up the equilibrium
HO
AgCl s 2
Ag aq Cl aq
Since solids are not included in equilibrium expressions, as their concentrations are
constant, solubility product constants are calculated using only the concentrations
of products at equilibrium.
Ksp = [Ag+][Cl—]
Like equilibrium constants, solubility product constants are specific for only one
reaction at a particular temperature. The higher the Ksp value is, the higher the
solubility of the salt will be.
Examples:
The following Ksp values are given for some salts at 25°C (Chang 720):
n calcium phosphate Ksp = 1.2 10—26
n silver bromide Ksp = 7.7 10—13
n barium fluoride Ksp = 1.7 10—6
In these examples, barium fluoride (BaF2) has a higher solubility than the other two
salts, calcium phosphate (Ca3(PO4)2) and silver bromide (AgBr) because BaF2 has
the larger Ksp value. Calcium phosphate will dissolve very slightly in water due to
its very low Ksp value.
Be sure to clarify the difference between solubility (the number of moles of solute
that will dissolve in 1 L of solution, known as concentration) and solubility product
(the product of the concentrations of ions in solution, raised to the powers of their
coefficients in the balanced equation).
In chemistry textbooks, units for Ksp are not used because they would vary
depending on the powers to which the concentrations are raised, such as mol/L to
(mol/L)2 to (mol/L)3.
Example 2:
Use an ICE table to solve for the molar solubility of a slightly soluble salt.
Calculate the molar solubility of lead chloride (PbCl2) in pure water at 25°C. Ksp for
PbCl2 is 2 10—5.
Solution:
1. Write the dissociation equation for PbCl2.
PbCl2(s) Pb2+(aq) + 2Cl—(aq)
2. Set up an ICE table and fill in the values for the unknown ions. Note that for
every Pb2+ ion there are two Cl— ions, which can be seen from the balanced
equation
PbCl2(s) Pb2+(aq) + 2Cl—(aq)
I ? 0 0
C ? +x + 2x
E ? x 2x
3. Write the ion-product, or Ksp, expression and substitute the known values into
the expression.
Ksp = [Pb2+][Cl—]2
2 10—5 = (x)(2x)2
4. Solve for x.
2 10—5 = 4x3
x3 = 5 10—6
x = 1.7 10—2 mol/L
Example 3:
Identify the concentration of ions present at equilibrium when the Ksp value of the slightly
soluble salt has been provided.
What is the concentration of silver and chloride ions in a saturated silver chloride
(AgCl) solution at 25°C?
Ksp = 1.8 10—10
Solution:
1. Write the dissociation equation for AgCl.
AgCl(s) Ag+(aq) + Cl—(aq)
2. Set up an ICE table and fill in the table for the unknown values of the ions, x.
AgCl Ag+(aq) + Cl—(aq)
I ? 0 0
C ? +x +x
E ? x x
3. Write the ion-product, or Ksp, expression and substitute the known values into
the expression.
Ksp = [Ag+][Cl—]
1.8 10—10 = (x)(x)
4. Solve for x.
1.8 10—10 = (x)2
x2 = 1.8 10—10
x = 1.3 10—5 mol/L
The molar solubilities of the ions at equilibrium are equal to
x = [Ag+] = [Cl—] = 1.3 10—5 mol/L
Example 4:
Determine the molar solubility of a slightly soluble salt in a solution containing a known
concentration of a common ion.
Calculate the molar solubility of silver chloride (AgCl) in a 1.5 10—3 mol/L silver
nitrate (AgNO3) solution.
Ksp for AgCl = 1.6 10—10
Solution:
This is a common ion problem. The common ion is Ag+, which is present in AgCl
and AgNO3. Note that the presence of the common ion affects the solubility of
AgCl (in mol/L) but not the Ksp value because it is an equilibrium constant.
2. Set up an ICE table and fill in the values for the unknown ions. Remember that
there are two sources for the Ag+ ion, 1.5 10—3 mol/L from AgNO3, and the
unknown amount, x, from AgCl.
AgCl(s) Ag+(aq) + Cl—(aq)
I ? 1.5 10—3 0
C ? +x +x
E ? 1.5 10—3 + x x
3. Write the ion-product, or Ksp, expression and substitute the known values into
the expression.
Ksp = [Ag+][ Cl—]
1.6 10—10 = (1.5 10—3 + x)(x)
4. Solve for x.
1.6 10—10 = (1.5 10—3)(x)
x = 1.1 10—7
[AgCl] = 1.1 10—7 mol/L
2. Write the expression for the solubility product constant for aluminum sulphate
Al2(SO4)3.
Answer:
Al 2 SO 4 3s
3 2
2Al aq 3SO 4 aq
3 2 3
K sp
Al SO 4
Sample Problems:
1. A sample of barium hydroxide (Ba(OH)2(s)) is added to pure water and allowed
to come to equilibrium at 25°C. The concentration of Ba2+ is found to be 0.108
mol/L and that of OH— is found to be 0.216 mol/L. What is the value of Ksp for
Ba(OH)2(s)?
Answer:
Ksp = 5.04 10—3
extension:
5. Will a precipitate form when 1.00 L of 0.150 mol/L iron(II) chloride solution
(FeCl2) is mixed with 2.00 L of 0.0333 mol/L sodium hydroxide solution
(NaOH)?
Answer:
Trial Ksp or Qsp = 2.46 10—5, Ksp = 4.9 10—17. Qsp > Ksp, so a precipitate
will form.
Journal Writing
Have students “explain how adding additional sulfate ions to a saturated solution
of barium sulfate would affect the concentration of barium ions” (Dingrando, et al.,
Glencoe Chemistry: Matter and Change, Teacher Wraparound Edition 577).
Website
University of Colorado at Boulder. “Salts and Solubility.” PhET Interactive
Simulations. <http://phet.colorado.edu/en/simulation/soluble-salts>
(22 Nov. 2012).
Notes
(0.5 hour)
TEAchER NoTEs
Practical Applications of salts with Low solubility
The following examples of the practical applications of salts with low solubility are
provided to indicate the importance of slightly soluble salts in our lives. Students
are not expected to learn the examples in great detail. Teachers can either have
students collect information from their own textbooks or, if information is limited,
through additional research. Some information is provided here for teacher
reference.
n Limestone Caverns
Limestone (CaCO3) is formed through the decay of marine organisms such as
snails, clams, corals, and algae. In water, the slightly soluble salt will set up the
following equilibrium:
CaCO 3s
2 2
Ca aq CO 3 aq
The chemical erosion of limestone occurs when it is in contact with acidic water:
Haq CO 3 2aq
HCO 3 aq
n osteoporosis
Approximately 99 percent of the body’s calcium is stored in the bones, where it
forms the following equilibrium system:
Ca 3 PO 4 2s
2 3
3Ca aq 2 PO 4 aq
n tooth decay
The major constituent of tooth enamel is hydroxyapatite (Ca5(PO4)3OH,
Ksp= 6.8 10—37). In the mouth, the following equilibrium is established:
3
Ca 5 PO 4 3 OHs
Ca 5 PO 4 aq OH aq
When sugar ferments on the teeth, the hydronium ion is produced. It reacts with
the hydroxide ion from the previous reaction, causing the forward reaction to be
favoured. An increase in the solubility of the hydroxyapatite leads to the
dissolving of tooth enamel. In recent years, fluoride has been added to water
and toothpaste. The fluoride ion replaces the hydroxide ion in hydroxyapaptite
to create fluorapatite (Ca5(PO4)3F, Ksp = 1.0 10—60). As the fluorapatite is less
soluble in water, teeth become more resistant to cavities.
The addition of fluoride to toothpaste has been helpful in preventing tooth
decay; however, fluoride is not added to children’s toothpaste because an excess
of fluoride in the body from swallowing large amounts of paste can lead to
fluorosis, damaging teeth and bones.
(continued)
Visual Displays
Students can create visual displays (e.g., posters) to demonstrate practical
applications of the solubility of slightly soluble salts. Samples of presentation
rubrics are provided in Appendix 11.
collaborative Teamwork
Collaborative strategies such as Jigsaw (see SYSTH 3.20) or Roundtable
(see Appendix 7) could be used to have students share their knowledge of specific
applications of the solubility of slightly soluble salts with their classmates.
Journal Writing
Have students reflect on common applications of the solubility of slightly soluble
salts. Students’ reflections could be based on examples from their everyday lives or
on career-related applications.
Entry-Level Knowledge
In addressing learning outcome C12-4-11, students solved problems involving Ksp.
Learning outcome C12-4-13 provides students with an opportunity to use
experimental data to calculate the value of Ksp for a slightly soluble salt.
Laboratory Activities
Have students perform a lab activity to determine the Ksp of a salt with low
solubility. Possible lab activities are suggested below.
n experiment 39: a solubility Product Constant (Wilbraham, Staley, and Matta
243)
The purpose of this lab activity is to determine the solubility product constant of
lead(II) chloride (PbCl2). Students add 100 mL of saturated PbCl2 to 20 mL of
0.5 mol/L potassium chromate (K2CrO4) solution. The mixture is heated to the
boiling point and then left to stand and cool for at least five minutes. Students
decant the liquid from the beaker, making sure most of the precipitate stays in
the beaker. The filter paper is placed in the beaker with the precipitate and then
dried. The Ksp of PbCl2 is then determined through a series of calculations.
n Chemlab 18: Comparing two solubility Product Constants (Dingrando, et al.
586)
The objectives of this lab activity are to compare the values of the Ksp for two
different compounds and relate them to observations, to explain observations of
the two precipitates using Le Châtelier’s principle, and to calculate the molar
solubilities of the two ionic compounds from their Ksp values. As this is a small-
scale lab activity, minimal quantities of chemicals are used. Students add
10 drops of silver nitrate (AgNO3(aq)) and 10 drops of sodium chloride (NaCl(aq))
to two wells of a microplate, and observe that the precipitates that form, silver
chloride (AgCl(s)), are white. To the second well, students add 10 drops of
sodium sulphide (Na2S) solution. The precipitate that forms, silver sulphide
(Ag2S(s)), is black.
n investigation 7.6.1: determining the Ksp of Calcium oxalate (van Kessel, et al.
517)
For this investigation, students determine the Ksp of calcium oxalate (CaC2O4) by
mixing a fixed volume of 0.1 mol/L sodium oxalate (Na2C2O4) with a serial
dilution of aqueous calcium nitrate (Ca(NO3)2) in a series of spot-plate wells.
Laboratory skills
Periodically and randomly review the lab skills of individual students, so that
eventually all students are assessed. Develop a checklist for the assessment of skills
related to measuring and mixing solutions. Sample checklists for assessing lab skills
and work habits are available in SYSTH (6.10, 6.11).