Вы находитесь на странице: 1из 26

CHEMICAL

EQUILIBRIUM

Teacher's Guide
Steady Unsteadiness
When the flask is shaken, oxygen dissolves in the water and oxidizes the
Objectives colorless reduced form of methylene blue, reforming the blue dye. Below
Students should be able to: is a simplified mechanism for the system.
1 . State the Second Law of Thermodynamics.
2. Identify the implications of the regularity "energy runs downhill" to
chemical reactions.
3. Identify systems in a steady state.
4. Identify closed systems.
5. Describe at least two explanations for macroscopic properties Details can be obtained from J.A. Campbell's article "Kinetics - Early
becoming constant during a chemical reaction. and Often" listed on page 5.
6. Describe what is meant by the term dynamic chemical equilibrium.
Explanation for Activity 2: The Thionine System
Program Description Thionine is protonated by the sulfuric acid, and then is electronically
Program 1 begins with a toboggan sliding down a hill, illustrating the excited by the light source. The excited thionine ion oxidizes the iron(II)
tendency for most changes to involve movement from a state of high to iron(III). The reduced form of thionine is colorless. When the light
energy to one of low energy. The application of this regularity to source is turned off the excited thionine decays to its ground state. This
chemical systems suggests that only exothermic reactions are possible. reverses the iron reaction; iron(III) is reduced to iron(II), and the purple
It also suggests that chemical reactions must stop. The fallacy in their color of the oxidized thionine returns.
conclusions is illustrated and the concepts of steady state and dynamic A more detailed explanation is available in L.J. Hardt's article "The
equilibrium are introduced. Photochemical Reduction of Thionine" listed on page 5.

Before Viewing After Viewing


Use Activity 1, The Blue Bottle, and/or Activity 2, The Thionine System, Use Activities 4 and 5 to illustrate the difference between steady state
to demonstrate that chemical reactions can be reversed. Most students and dynamic equilibrium. Demo 1 shows a typical steady state system,
believe this cannot be done, so this is time well spent. Note that the with the rate of water flowing into the can equal to the rate of water
development of the accepted model for either of these activities is flowing out. The candle and burner flames also are steady state systems,
beyond the ability of most students at this stage. However, if the activity but the input and output are not as obvious. Have students explain the
is done in groups of four, most groups should come up with a model that "balance" in the systems.
i nvolves a set of reversible reactions. Demo 2 involves two long-term experiments. The best way to treat
Use Activity 3 to show that reactions proceed and reach a point this demonstration is to set it up for next year and use the given obser-
where macroscopic properties are constant. Ask students to suggest vations for your current classes.
plausible explanations for the constant macroscopic properties, then Activity 5 is a logical stepping stone to Program 2. It is an excellent
show Program 1. analogy of dynamic equilibrium. Working in pairs, students transfer
colored water from their container into their partner's. By starting with
Explanation for Activity 1: The Blue Bottle
different volumes of water and using different capacity vessels to
Glucose, a weak acid reacts with the hydroxide to form the glucoside ion transfer the water, the situation can be used to illustrate many of the
which reduces the blue form of methylene blue to a colorless form. features of a chemical system.
1
2

Activity 5 is written as a student experiment. If you wish to demon- because the solution in beaker "C" was absorbing water at a much faster
strate this activity, use beakers of different sizes to transfer the water rate than "D." This was caused by the large difference in concentration.
and aquaria or large battery jars filled with different volumes of colored The solution in beaker "C" was 615 times more concentrated than that
water. in "D" at the start. Thus the beakers tended to exchange water. The
exchange should have continued until the concentrations were equal.
Explanation for Activity 4, Demo 2: The rate of evaporation from "D" should have started out fast and then
Long-Term Experiments decreased until the concentrations were equal. But in this case the
Set-up 1 situation was complicated by the water vapor diffusing into the jar. When
the rate of diffusion was greater than the rate of absorption by the
Since the volumes continued to decrease, water must have continuously
solution in beaker "C," the volume in "D" should have slowly begun to
evaporated from the solutions. Thus the system must have been open to
rise. As the concentration decreased, the rate of absorption also should
gases, in this case water vapor escaping from the jar. Since the
have decreased; however, the concentration of the water was getting
phenolphthalein reddened in the cylinder labelled "B," then some of the
larger at the same time so the rate of evaporation should have increased
sodium hydroxide was neutralized, presumably by HCI(g) escaping from
until, at 21 months, the rate of evaporation and condensation became
cylinder "A."
equal, or perhaps all evaporation and condensation stopped. More
Note: Phenolphthalein has two color changes as pH increases: colorless
details can be obtained from L.W. Bixby's article "Long-Term Chemical
to pink between 8-10 and then back to colorless around pH 14.
Reactions" listed on page 5.
Set-up 2
Since the volumes of both beakers overflowed, the system must have
been open to water vapor. The level in beaker "D" dropped initially

3. Using "OH' - " to represent the sodium 10 mL graduated cylinder


Activities hydroxide, "G" to represent the glucose, and 600 mL beaker
Activity 1: The Blue Bottle "MB" to represent the methylene blue, write
Light source (overhead projector or goose neck
equations that will account for your
Apparatus lamp)
observations.
20 g of sodium hydroxide 4. Make predictions and design experiments to Method
20 g of glucose test the models you developed in step 3.
Check with your teacher before carrying these Add 10 mL of the thionine solution, 10 mL of
1.5 mL of 1 % alcoholic methylene blue the sulfuric acid solution, and sufficient water
out.
1 L of water to bring the solution to 500 mL.
Discussion 2. Thoroughly mix in 2.0 g of iron(II) sulfate
250 mL Erlenmeyer flask with rubber stopper heptahydrate.
Note: Dissolve the ingredients in the litre of water. Develop a model for the blue bottle experiment. 3. Use the overhead projector to light the solution
I ndicate the evidence on which your model is
Add the sodium hydroxide just before using. from below or use the goose neck lamp with a
based. 250 W photoflood bulb to light it from above.
Method 4. Turn the light source on and observe what
1 . Fill the Erlenmeyer flask a little less than half Activity 2: The Thionine System happens. Then turn it off and observe. Repeat
full with the solution. Stopper the flask Apparatus several times.
i mmediately. I ron(II) sulfate heptahydrate 5. Using "S" to represent the sulfuric acid, "T" to
2. Shake the flask vigorously, then place it on a represent the thionine, and "Fe 2+" to
white sheet of paper and observe what represent the iron(II) sulfate in solution, write
happens. Repeat several times. 0.001 mol/L thionine equations that will account for your observations.
6. Make predictions and design experiments to in the manometer. Again, the same two explana- manometer. Be sure to try this experiment before
test the models you developed in step 5. tions are plausible. you demonstrate it for the class.
Check with your teacher before carrying these Use a syringe to inject stock hydrochloric acid
out. containing the indicator bromthymol blue into
another example of the set-up. Explain the Activity 4: Steady State/Dynamic
Discussion changes in the manometer. Again, two explana- Equilibrium Demonstrations
Develop a model for the thionine system. tions are plausible.
Now add a little of the hydrochloric acid to the Demo 1
I ndicate the evidence on which your model is
based. apparatus containing the ammonium hydroxide. Place a burning candle and a lit Bunsen burner on
Similarly, add a little of the ammonium hydroxide to the demonstration desk. Thirdly, set up the
Activity 3: Acid/Base the apparatus containing the hydrochloric acid. In apparatus as shown in Figure 2. Ask students to
this case the chemical reaction is obvious when account for the "balance" in the three systems.
Demonstrations the white smoke forms. Account for any changes Note: Use a fairly crude knife edge for the
Demo 1 i n the indicator and manometer. fulcrum, otherwise it is very difficult to maintain the
Slowly pour equal volumes of 1 mol/L NaOH and Note: It will be necessary to fiddle with the balance. Ask students to compare the three
HCI solutions containing the indicator bromthymol concentrations and volumes of the acid and base systems. How are they the same? How are they
blue into a beaker placed on the overhead to get reasonable changes in the levels of the different?
projector. Repeat for different but equal volumes
of NaOH and HCI. Try to explain why the color of Figure 2
the mixture remains the same.
Note: There are two plausible explanations: that
the reaction has stopped, and that there are
opposing reactions occurring at equal rates.

Demo 2
Use a syringe to inject stock ammonium hydroxide
containing the indicator bromthymol blue into the
apparatus shown in Figure 1. Explain the changes

3
4

Demo 2 products (p). I n this way you can simulate the 1 0 mL graduated cylinder
reaction where one reactant decomposes into two Water with blue food coloring
Make a transparency of the two experimental set-
products.
ups described below, or better still, actually set Water with yellow food coloring
If possible, move the fulcrum position to one
them up. Include the following:
side. This enables you to simulate a situation
Set-up 1 where there is more product than reactant at Method
Forty millilitres of 0.3 mol/L HCI was added to a equilibrium.
1 . Put some blue colored water in one beaker
100 mL graduated cylinder labelled "A." Ten milli- Add the appropriate number of tiles to each pan
and some yellow colored water in the other.
litres of a 1 mol/L NaOH solution containing the to achieve a balance. Then challenge the students
to think of another way the balance could be The only restriction is that the total volume of
indicator phenolphthalein was added to a second the two is 100 mL.
1 00 mL graduated cylinder labelled "B." The two maintained. Obviously, if one (r) tile were removed
2. Work in pairs. Transfer water from B, the blue
cylinders were sealed in a large jar and observed from one side and two (p) tiles were removed from
beaker, using one of the pieces of glass
weekly for two years. the other side, the system would remain balanced.
tubing, to Y, the yellow beaker. At the same
The solutions in both graduated cylinders But that is not how a chemical system works.
ti me your partner should transfer water from Y
decreased continually over the period of 24 Reactants are changed into products, and as soon
to B using the other piece of glass tubing. Be
months. After 13 months the solution in cylinder as that happens the system is no longer balanced.
However, if as one (r) tile were transferred to the sure to keep the glass tube vertical at all times.
B reddened. 3. Use the rulers to record the height of the
product side, two (p) tiles were removed and one
Set-up 2 water in each beaker after every five
(r) tile was added to the reactant side, balance
One hundred and fifty millilitres of saturated exchanges.
would be maintained. This would simulate a steady
( 6.15 mol/L) NaCl was placed in a 250 mL beaker 4. Continue transferring water until you have
state with the continuous removal of products and
l abelled "C." One hundred and fifty millilitres of three successive readings that are the same.
the continuous addition of reactants.
0.01 mol/L NaCl was placed in a second 250 mL 5. When the heights remain constant measure
Another way to maintain balance is, of course,
beaker labelled "D." The two beakers were sealed the volume transferred by each glass tube.
to switch one reactant tile for two product tiles. In
i n a large jar and observed weekly for two years. 6. Repeat steps 1-5 for different volumes of blue
this way both the reaction and its reverse would
After 13 months beaker "C" was filled and then and yellow water, but keep the total volume
have to occur and their rates would have to be
overflowed by 30 mL or more into the jar. The 100 mL.
equal.
l evel in beaker "D" initially dropped, but it too also
eventually overflowed. After 21 months there was Observations
Activity 5: A Model for
no apparent change.
Ask students to come up with plausible explan- Chemical Equilibrium TIME HEIGHT OF WATER HEIGHT OF WATER
ations for these observations. Help them focus I n this activity you will simulate a system BLUE BEAKER YELLOW BEAKER
their attention on the principles learned in Pro- approaching chemical equilibrium. Your task is to ( 5 exchanges) ( mm) ( mm)
gram 1 with questions such as "How is the system determine if the simulation is a good model for a 1
closed?" "How is the system open?" "Were the chemical system at equilibrium.
2
systems at equilibrium?" "At a steady state?"
Apparatus 3
Demo 3 Two 150 mL beakers etc.
Use an equal arm balance and some small bath- Two plastic rulers
room tiles to simulate a system at equilibrium.
Label one set of tiles reactants (r) and, if possible, Two pieces of glass tubing of different diameters,
another set - half the mass of the former = 10-15 cm long
Discussion Further Reading
1. What are the following analogous to in a
chemical reaction? The height of the water in Bixby, L.W. "Long-Term Chemical Reactions.
the two beakers; the transfer of water from Parts I & If. " Chemistry. September and
one beaker to another; two pieces of glass October 1976.
tubing of different diameters; the coloring in Campbell, J.A. "Kinetics - Early and Often."
the water; the volume of water transferred; the Journal of Chemical Education. Vol 40. No.
volume of water transferred when the height 11. November 1963.
remains constant.
Hardt, L.J. "The Photochemical Reduction of
2. What evidence suggests that you reached a
Thionine: A Reversible Reaction." Journal of
point of equilibrium in this activity? You should
Chemical Education. Vol 26. No. 25. 1949.
be able to think of two key observations.
3. What property of the system determines the Parry, Robert W. et al. Chemistry: Experimental
(a) Plot a graph of the data. Foundations. Englewood Cliffs, New Jersey:
final height of the water in the beakers? What
(b) Describe the graph in words. Prentice-Hall, 1970.
would this be analogous to in a chemical
(c) Explain why the graph has the shape it
reaction? Rowley, Wayne R. E. Matter in Balance: Chemical
has.
4. Plot height of water versus time in units of five Equilibrium. Toronto: Wiley, 1979.
(d) What is the significance of the horizontal
exchanges.
part of the graph? Sienko, Michell J., and Robert A. Plane.
(a) Describe the graph in words.
(e) What would be the significance of the Chemistry. New York: McGraw-Hill, 1976.
(b) What is the significance of the horizontal
slope of a tangent drawn at any point on Toon, E.R., and G.P. Ellis. Foundations of
part of the graph?
this graph? Chemistry. New York: Holt, Rinehart and
(c) What would be the significance of the
(f) What happens to the slope of the tangent Winston, 1973.
slope of a tangent drawn at any point on
as the system approaches equilibrium?
this graph?
(d) What happens to the slope of the tangent What does this imply?
( g) Use the analogy to explain the changes in
as the system approaches equilibrium?
the slope of the tangents.
What does this imply?
(e) The implications of (d) contradict what is 6. Is this analogy a good model for chemical
actually happening; you can still see water equilibrium? Explain your answer.
being transferred from one beaker to
another. Explain how it is possible for the
graph to suggest that the reaction has
stopped even though you can see it going
on.
5. Consider the following gaseous reaction:

One mole of C12 was added to 2 mol of CO in a


1 L container. The concentration of the three
gases was measured using a spectropho-
tometer every minute. The following data were
recorded:

5
6

Dynamic Equilibrium
point of equilibrium - can be reached by starting with the product,
Objectives hydrogen iodide. But the puzzle of how to describe the system at this
Students should be able to: point remains. Has the reaction stopped, as the macroscopic properties
suggest, or is there a dynamic equilibrium with reactions occurring in two
1. Describe a system at equilibrium macroscopically and microscopically.
directions? To resolve this puzzle students are reminded that a kinetic
2. Use the Kinetic Molecular Theory to explain why a "dynamic" model
model is used to describe matter which supports the dynamic
for chemical equilibrium is the most reasonable explanation for the
description of the equilibrium point. In addition, they are presented with
observations.
empirical data that is difficult to explain without assuming a dynamic
3. Describe the types of motion of molecules in the gaseous phase.
equilibrium between the forward and reverse reaction for the
4. Describe the changes in concentration of the reactants and products
hydrogen/iodine/hydrogen iodide system.
as a chemical system approaches and reaches equilibrium.
5. Interpret the "double arrow" conventions.
6. Identify data that supports a dynamic model for chemical equilibrium. Before Viewing
Use the discussion of Demonstration 3 in Activity 4, and Activity 5 in
Program Description Program 1 as an introduction to Program 2. The questions that remain
should be "Are the analogies a good way to view chemical equilibrium?"
Program 2 begins with a review of the tendency towards minimum and "What evidence is there to support a dynamic model?"
energy and the observation that in a closed system a chemical reaction
appears to have stopped. The reaction betwee n N02 and Nz04 i s used to
l ustrate the reversibility of chemical reactions. A quantitative look at the After Viewing
eaction between hydrogen and iodine follows. The analysis of the Have students complete Activity 1. This enables them to gather indirect
, ystem shows both reactants and products are present when the evidence for the dynamic model and to practise using it to describe a
eaction appears to have stopped. It also shows that this point - the physical change and a chemical change.

The formation of a black precipitate when


Activities sodium sulfide is added is used to identify lead
Activity 1: Testing the i ons in solution. The addition of silver nitrate and 1 mol/L NaBr solution (102.9 g NaBr/L) * in
Dynamic Model the formation of a pale yellow precipitate is used dropping bottles
to identify the bromide ions in solution. The silver
I n this activity you will gather indirect evidence to bromide that is formed darkens when exposed to Short-stemmed funnel and filter paper
support the dynamic model for chemical li ght. Iodine vapor can be identified by its Small test tube
equilibrium. It is not possible to see what is characteristic pink color.
happening on a microscopic scale, but it is 150 mL beaker
possibie to check if the reaction and its reverse Apparatus Wash bottle filled with distilled water
occur and if both reactants and products are Piece of acetate and a sheet of white paper
present at equilibrium. The two systems you will
study are: A glass rod

* All solutions must be made with distilled water.


Part B 10. On another section of the acetate sheet put a Observations
Small corked test tube containing a few crystals of drop of the sodium bromide solution. Add to it
Part A
iodine a drop of the silver nitrate solution. Record
any changes.
Large beaker containing hot (70-90°C) water 1 On another section of the acetate mix a drop
Hot plate of the sodium bromide and lead nitrate
solutions. Call this mixture 2. Allow the solid
Method to settle and then divide the mixture into two
equal parts using the glass rod.
Part A
12. To one part of the mixture add a drop of the
1 . Add approximately 1 cm of the sodium sodium sulfide solution. To the other part add
bromide solution to the test tube. a drop of the silver nitrate solution. Record
2. Add an equivalent volume of lead nitrate any changes. Mixture 1 is formed by adding distilled water to
solution to the test tube. Caution: Wear 13. Divide the mixture produced in step 8 l ead bromide.
disposable gloves. The white precipitate that ( mixture 1) into two equal parts. To one part
forms is lead bromide. Mixture 2 is formed by mixing lead nitrate and
add a drop of the sodium sulfide solution. To
sodium bromide.
3. Fold the filter paper into a cone and place it in the other part add a drop of the silver nitrate
the funnel. The funnel is held by the 150 mL solution. Record any changes.
beaker. 14. Dispose of the filter paper as directed by Part B
4. Stir the contents of the test tube and transfer your teacher. Rinse the acetate sheet, test Describe the original contents of the test tube and
them onto the filter paper. Use the wash tube, beaker, and glass rod with running any changes that occurred as a result of heating
bottle to ensure that all of the solid is water. Do not forget to wash your hands and cooling the tube.
transferred to the filter paper. after cleaning up. Lead compounds are
5. Wash the lead bromide on the filter paper toxic. Discussion
twice using approximately 2 cm of distilled
Part A
water in the test tube each time. Part B
6. Put the acetate sheet over a piece of white 1 . Describe a test for lead ions in solution. Write
1 . Use the hot plate to heat water until it is a balanced chemical and ionic equation for
paper.
between 70 0 and 90 1C. Several pairs of the test.
7. Use the glass rod to transfer as much of the
students can use the same hot water bath. 2. Describe a test for bromide ions in solution.
l ead bromide as possible from the filter paper
2. Hold the bottom of the test tube in the hot Write a balanced chemical and ionic equation
to the acetate sheet.
water until the amount of iodine vapor remains for the test.
8. Cover the solid lead bromide with distilled
constant. 3. Write a balanced chemical and ionic equation
water. Mix the solid and water with the glass
3. Remove the test tube from the hot water and to describe the formation of a white precip-
rod. Call this mixture 1. Let the mixture sit
observe what happens. i tate when solutions of lead nitrate and
until you need it in step 13.
4. Repeat steps 2 and 3 several times. sodium bromide are mixed.
9. On another section of the acetate sheet put a
5. Return the corked test tube to your teacher. 4. What are two plausible explanations for the
drop of the lead nitrate solution. Add to it a
Do not attempt to clean out the test tube. fact that the amount of white precipitate
drop of sodium sulfide solution. Record any
changes. formed when lead nitrate and sodium bromide
are mixed does not seem to change on
standing?

7
8

5. What is implied by the observations made 5. What evidence makes it hard to accept the
when sodium sulfide and silver nitrate are "stopped" model?
added to mixture 2? 6. Write an equation to describe the system
6. Explain why it is hard to accept the when the amount of purple vapor remained
"stopped" model for equilibrium based on the constant. Interpret all symbols used.
observations made when sodium sulfide and 7. Describe what you think is happening on a
silver nitrate are added to mixture 2. microscopic scale when the pink color in the
7. What is implied by the observations made test tube remains constant.
when sodium sulfide and silver nitrate are Parts A and B
added to mixture 1 ?
8. Explain why the indirect evidence supplied by 1. What is meant by the term "dynamic" when
the observations made when sodium sulfide applied to the concept of chemical equilibrium?
and silver nitrate are added to mixture 1 build 2. Why is a double arrow I used in a
our confidence in the dynamic model. chemical equation to describe a chemical
9. Write a balanced chemical and ionic equation system at equilibrium?
for a reaction that would account for the 3. What evidence suggests that the dynamic
observations made when sodium sulfide and model is the best description of a chemical
silver nitrate are added to mixture 1 . system at equilibrium?
10. Based on the observations write a balanced
chemical and ionic equation to describe the Further Reading
two mixtures. Interpet all symbols used.
11. Describe what you think is happening, on a Alyea, Hubert N., and F.B. Dutton. Tested
microscopic scale, in these mixtures. Demonstrations in Chemistry. Easton, Penn-
sylvania: Chemical Education Publishing Co.,
1965.
Part B
Parry, Robert W et al. Chemistry: Experimental
1 . Write an equation to describe the physical Foundations. Englewood Cliffs, New Jersey:
change that produced the purple vapor when Prentice-Hall, 1970.
the test tube was heated.
Rowley, Wayne R.E. Matter in Balance: Chemical
2. Write an equation to describe the physical
Equilibrium. Toronto: Wiley, 1979.
change that produced the needle-like crystals
in the upper region of the test tube when it Toon, E.R., and G.P. Ellis. Foundations of
was removed from the hot water. Chemistry. New York: Holt, Rinehart and
3. What evidence suggests the changes in 1 and Winston, 1973.
2 were changes of state and not chemical
changes?
4. What are two plausible explanations for the
fact that the amount of purple vapor remains
constant even though the test tube remains in
the hot water and there is still solid iodine at
the bottom of the test tube?
Reaction Kinetics
energy and its relationship to temperature, activation energy, and
Objectives reaction mechanisms is introduced and is used to explain how
Students should be able to: hydrogen and chlorine can exist in the dark, forming very little hydrogen
1 . Describe experimental evidence that supports a molecular distribution chloride; but add a little daylight and almost all the hydrogen and chlorine
is transformed into hydrogen chloride. Energy graphs are used to
of energies within a sample of gas.
illustrate energy changes in exothermic and endothermic reactions and
2. Define the term activation energy.
how one influences the other in a system at equilibrium. The program
3. Describe the effect of temperature on the molecular distribution of
concludes by asking a question that opens the door to explore the
energies.
effects of other factors on the equilibrium point, such as concentration
4. Use an example to explain what is meant by the term chain
and pressure. The question provides the logical link to the next program.
mechanism.
5. Draw energy pathways for endothermic and exothermic reactions.
6. Label the following on an energy pathway: activation energy; total Before Viewing
energy released; and the net energy required or released by a Review the meaning of steady state and dynamic equilibrium and why
chemical reaction.
chemists believe most chemical reactions proceed to a state of dynamic
7. Use the energy concepts to explain how a reaction and its reverse
equilibrium. Use Activity 1 to show that a collision must occur before a
end up in a dynamic equilibrium. reaction can take place. Review the basic assumptions of the collision
theory and the factors that affect the rate of a chemical reaction. Use
Program Description Activity 2 to show that many chemical reactions involve a series of steps.
These demonstrations set the stage for the introduction of the collision
Program 3 begins with a review of the meaning of the term dynamic and mechanism models presented in Program 3.
equilibrium. Then a problem is posed: "Why is it that under one set of
conditions the equilibrium point will involve very few product molecules,
but under other conditions it will involve almost complete conversion of
After Viewing
the reactants to products?" The example used is the chlorine/hydrogen/ Use Activity 3 to consolidate the ideas presented in the program.
hydrogen chloride system. A more detailed application of the kinetic Discuss the answers as they will help to form a bridge between
theory to chemical systems follows. The molecular distribution of kinetic Programs 3 and 4.

Pass the two tubes around the class. Allow assumption of the collision theory that reactants
Activities students to shake one but not the other. They must come in contact or collide before a reaction
Activity 1: A Collision Model for should be able to see that yellow lead iodide only takes place.
forms when the two solids come in contact. This
Chemical Reactions point can be made dramatically by adding water to Activity 2: A Mechanism Model for
Set up two stoppered test tubes, each with 2 cm the test tube, thus dissolving the solids. When Chemical Reactions
of solid potassium iodide on top of 2 cm of solid dissolved the contact area is increased
lead nitrate. If the test tubes are set up several tremendously and the contents of the test tube Since most of the students' experience has been
days in advance, a yellow line will appear at the i nstantaneously turn bright yellow. with reactions that appear to go in a single step, it
point of contact between the two solids. is worth the time to show them some of the
This is a good reaction to show students
because most believe reactions do not take place evidence that suggests that a better way to
between solids. It also illustrates the basic describe most chemical reactions is with a series

9
10

of simple reactions or steps called the mechanism the dispersion to room temperature. Add sufficient Step
of the reaction. water to bring the total volume up to 1 L. Add the 1.
15 g of sodium hydrogen sulfate(IV) and allow it 2.
Demo 1 to dissolve.
Add a drop of aqueous iron(III) chloride to a Caution: Do not add the sodium hydrogen When all of B is used up then step 3 can take
solution of sodium thiosulfate (concentrations are sulfate(IV) to the hot dispersion. If you plan to place:
not critical) in a petrie dish on the overhead keep solution C for more than a day or two add
projector. A black complex, forms and 1 g of salicylic acid and 10 mL of ethanol for
slowly disappears, leaving a pale yellow solid, every litre of solution.
colloidal sulfur. Be prepared to show that the Label two Erlenmeyer flasks 1 and 2. Use the You could tell students the ingredients but that
observations are not due to simple diffusion. This chart below to obtain the volumes of A, B, C, and would just stifle the creative process as they try to
is accomplished by adding a drop of iron solution water. Use four graduated cylinders, one for each recall appropriate chemical reactions. Remember
to a second petrie dish containing just water. This of the components, to avoid contamination. that the purpose of this exercise is not to teach
is an excellent opportunity to discuss plausible
explanations and then design experiments to test
them. Do not spend time presenting or trying to
develop the mechanism for this reaction. Just use
it to help establish that most chemical reactions
can be pictured as a series of simple steps which
add up to the overall reaction. The next Add the appropriate volumes of A, B, and water the mechanism of this reaction but to establish
demonstration will help you drive this point home. to flasks 1 and 2. Have the students predict the that it is reasonable to think of a reaction as
relative rates of the reaction in the two flasks. i nvolving a series of steps.
Demo 2 They should predict flask 1 to be the faster of the
To avoid problems when conducting this two because the concentration of B has been Activity 3: Reaction Kinetics
demonstration, only make as much solution as you reduced in flask 2.
The following questions will help you review the
will need for your classes plus a couple of trials; Review why the total volume was kept
terms and concepts of the rates of chemical
make up the solutions the night before you intend constant. Swirl the flasks to ensure that the
reactions. Some of them ask you to apply the rate
to use them. The concentrations of the three reactants are well mixed and add 20 mL of C
concepts to a chemical system at equilibrium.
solutions are as follows: simultaneously to each of the flasks. Continue to
swirl. An orange precipitate will appear in flask 1
Basic Terms and Concepts
first. But just as the students begin to feel that
flush of success that comes from being right, flask 1. Define the following terms:
2 will turn jet black, followed shortly by flask 1. endothermic; exothermic; activation energy;
Who won? How is it possible that the orange activated complex; rate of reaction; and
precipitate could form first in flask 1 but the black mechanism of a chemical reaction.
To produce C make a slurry of the starch and 2. Describe a chemical system at equilibrium in
appear first in flask 2?
enough water to cover the starch in a mortar. Use terms of rates of reactions.
Divide the students into groups of four. Tell
the pestle to mix the two well. Pour the slurry into 3. (a) List the four factors that determine the rate
them to represent the solutions by the letters A,
approximately 500 mL of boiling water. Turn off of a reaction.
B, and C and ask them to develop a model that will
the heat and stir well. Allow the colloidal starch ( b) Use the collision theory to explain on a
account for what they have seen. The following is
dispersion that forms to cool while you make up microscopic scale how each of the factors
typical of what they will produce:
solutions A and B. If necessary, add ice to cool affects a chemical reaction.
Energy Pathways (a) Complete the following chart for the steps Molecular Distribution of Kinetic Energy
1. (a) Draw and label the energy pathway for the of the reaction mechanism. Actual values
1. (a) Draw and label the curve that shows the
are not required. Compare one step to the
following reactions: distribution of kinetic energies in a sample
other using terms such as larger and
of gaseous molecules at room tempera
slower.
ture. (This distribution is called the
(b) What is the rate-determining step for this Maxwell-Boltzmann Distribution.) Show
Label the type of reaction (exo- or reaction? what happens to the shape of the curve
endothermic); the position of the reactants (c) Explain why the reaction mechanism is a when the temperature is increased. (Use a
and products; the activated complex; the better model for what happens on a different color.)
activation energy; the total energy microscopic scale during this reaction than ( b) Mark the activation energies of the
released; and the net energy produced or the net equation.
used by the reaction.
(b) Use the diagram to explain how a reaction
and its reverse end up in dynamic
equilibrium.
2. The following energy pathway, Figure 3,
describes the energy changes for the reaction:

reactions in question 1(a) Energy


Pathways on the distribution curve.
(c) Use the diagram in 1(b) to explain why you
would expect more of the products of the
exothermic reaction at equilibrium than
those of the reverse endothermic reaction.
(d) Use the diagram in 1(b) to predict which of
two reactions will be most affected by an
i ncrease in temperature.

Implications for Equilibrium


1. Consider the effects on the rate of formation of
hydrogen iodide if the concentration of
hydrogen were increased. Use these changes
to predict what will happen if some hydrogen is
added to a container holding iodine and
hydrogen in equilibrium with hydrogen iodide.
In your prediction describe the changes in the
amounts of iodine and hydrogen iodide at
equilibrium.
2. Use an argument based on rates of reactions
to predict the effect of a catalyst on the

11
12

amounts of reactants and products at


equilibrium.
3. The formation and decomposition of hydrogen
i odide are second-order reactions.
(a) Write a rate expression for each reaction.
( b) How will the rates of the two reactions
compare when hydrogen iodide is in
equilibrium with hydrogen and iodine?
State your answer mathematically and in
words.
(c) Use the mathematical statement to show
that at equilibrium there exists a ratio of
concentrations of reactants and products
that equals a constant.
( d) What are the only variables that will alter
the value of the constant developed in (c)?

Further Reading
Alyea, Hubert N., and F.B. Dutton. Tested
Demonstrations in Chemistry. Easton, Penn-
sylvania: Chemical Education Publishing Co.,
1965.
Huff, George E. Molecules in Motion. Toronto:
Wiley, 1976.
Laidler, Keith J. Chemical Kinetics. New York:
McGraw-Hill, 1950.
Mahan, Bruce H. University Chemistry. Reading,
Massachusetts: Addison-Wesley, 1965.
Parry, Robert W. et al. Chemistry: Experimental
Foundations. Englewood Cliffs, New Jersey:
Prentice-Hall, 1970.
Toon, E.R., and G.P. Ellis. Foundations of
Chemistry. New York: Holt, Rinehart and
Winston, 1973.
Reaction Tendencies
Objectives Before Viewing
Students should be able to: Use the overhead to show the constant macroscopic properties in the
1. State Le ChMelier's Principle. tubes. Have the students
2. Apply Le Chatelier's Principle to predict and explain how the stresses describe the systems on both a macroscopic and microscopic scale.
of heat and pressure affect a given system of equilibrium. Have them write an equation to describe the processes occurring in the
tubes. Review the effects of temperature, a change in volume, and
concentration on the rate of a chemical reaction, and use this data to
Program Description predict what will happen if these same variables are applied to a system
at equilibrium. Make the predictions and then demonstrate what
Program 4 begins with a review of the concept of dynamic equilibrium.
happens. As part of the predictions and demonstrations complete
The effect of a stress on a system at equilibrium is introduced using an
Activity 1 . Ask the students to deduce a general principle based on what
analogy. Credit for applying this common-sense approach to chemical
they have observed, then show Program 4.
systems is given to Le Chatelier. The effects of the stresses of heat and
pressure are illustrated and accounted for. Le Chatelier's Principle is
used to predict the shift in the position of equilibrium. The program ends After Viewing
by establishing a need for knowing the effect quantitatively.
Review Le Chatelier's Principle. Have the students review what happens
i n the demonstrations you showed them before the program. Redo them
if they cannot recall the observations. Complete Activities 2 and 3.
Activity 3 provides the link with Activity 1 in Program 5.

Ask the students for ways to change the


Activities concentration of the participants. Obviously
keeping the volume constant and adding more of
Activity 1: Pressure Effects one will change its concentration. However, it is
Now ask the question again. It should be more
The following can be demonstrated with a 50 mL obvious that a compression that halves the volume
also possible to alter the concentration of both by would double the concentration of each species,
translucent plastic syringe on the overhead or it changing the volume of the container. Ask the but that the rate of formation of N204 would be
can be a student activity using 1 mL disposable students which reaction, the forward or the four times what it was while the rate of formation
syringes held over a white sheet of paper. The reverse, will be altered the most by a change in for N02 would only be doubled. Thus there would
syringes are sealed by heating the plastic at the volume. If their first guess is that both will be be a build up of N204 until the rates of formation
needle end in a flame and squeezing it shut with a changed equally, do not evaluate it but ask for the were once again equal. At this new equilibrium
pair of tongs. rate expression for the formation of N02 and for there would be more N204 and less N02 than
Write the following equation on the chalkboard:
N204, assuming that the reactions occur micro- before the compression. Reasoning this way, the
scopically as written. Write the following on the students would predict that a compression,
chalkboard:

13
14

increasing the pressure, would cause the intensi syringes for you. The large 50 mL syringes can 0 ° C. It will take several minutes for the wire to
of the reddish-brown color to fade. be purchased through a pharmacy. pass through, depending on the thickness of the
Once the nrediction is estahlished fill the block. While you are waiting proceed with
syringes with To demonstrate the effect, Activity 2: Pressure Temperature Demonstration 2.
quickly push the piston in halfway and hold it. At
first glance the only apparent change is an
Effects Demo 2
increase in the intensity of the reddish-brown Demo 1
Place about 0.3 g (a few crystals) of crushed
color, the opposite to what was predicted. Repeat Review Le Chatelier's Principle. Have the students in a test tube and add 5 mL of
the procedure. Push the piston in quickly, hold it give you the equation that describes the equilib- ethanol. Shake vigorously until most of the solid
at the halfway point, pause until the color remains rium in a water/ice mixture. Ask them to predict has dissolved. If the solution is not pink, add drops
constant, then quickly pull it out. Be careful not to the effect of increasing the pressure on this of water until it just turns pink. Show the students
completely remove the piston. Careful observation system. Have a model of ice available so you can the color by holding the test tube over the stage
will reveal that the intensity increases when you ill ustrate why water expands when it freezes. This of the overhead projector or by pouring some of
push the piston in and then fades. Similarly, i s a good opportunity to review some of the ideas the solution into a petrie dish on the overhead.
quickly pulling the piston out causes the intensity related to the Kinetic Molecular Theory. Write the following on the chalkboard:
to fade initially and then darken. Ask the students After the prediction is established support a
for plausible explanations but don't evaluate them. block of ice between two iron rings on stands.
Program 4 uses an excellent analogy that will help Hold a thin wire with 1 kg masses on each end
them account for their observations. over the block. Make sure the masses will not rest
To generate the use a gas generator or a on the desk even after the wire passes through
l arge test tube fitted with a one-hole rubber the ice. To avoid a mess it is also advisable to
stopper. Insert a glass tube that has been bent have some sort of catch basin for the water that is
approximately 100 ° and drawn out to a point into produced as the ice melts. Ask the students for evidence that suggests
the rubber stopper. This allows you to place the Have the students apply their prediction to this the system is at equilibrium.
glass tube into the barrel of the small syringe, situation and then let the wire hang on the block. Ask the students to use Le Chatelier to predict
l etting it fill from the bottom up. Add a small The wire passes through the block and the what will happen if the system is heated, then heat
volume of concentrated nitric acid and small masses clatter to the desk surface, but the block the solution gently in a cool Bunsen flame until it
pieces of copper wire to the test tube. Stopper remains in one piece. Ask the students for changes color.
the test tube and fill the syringes with qas. plausible explanations. The melting as a result of
i ncreased pressure is easy; students expect that. Caution: Alcohol is flammable. Place a book over
Caution: Nitric acid is corrosive; wear protective the mouth of the test tube to smother the flames if
But why does the water refreeze? If you have
gloves. NO2 is toxic; fill the syringes in a the ethanol catches fire.
i ncluded the energy requirements of this system in
fumehood. Add small pieces of copper so you Ask what will happen if the system is cooled,
the equation, students should soon realize that the
only produce as much gas as you want. The then cool the test tube by immersing it in a beaker
temperature of the ice drops when it melts. The
reaction can be stopped by adding water to the of ice water.
energy required for melting has to come from
test tube. Be sure to wash your hands when you
somewhere. In this case it comes from the ice
are finished.
Because the syringes are very quickly stained itself. Be sure to point out that at this stage the Activity 3: Concentration Effects
by the gas it is not possible to fill them in advance. system is not at equilibrium but is attempting to This activity leads into Activity 1 in Program 5.
This also means that a disposable syringe can be shift to a new equilibrium. Thus when the pressure Thus it provides a natural bridge between the two
i s returned to normal, as the wire passes the programs.
used only once or twice. Thus you will need a
water will freeze at the lower temperature, The demonstration is best done on an overhead
large supply of them. If your doctor gives allergy
producing heat so the temperature returns to projector using petrie dishes. It can, of course,
shots she or he may be willing to save used 1 mL
be done on the demonstration desk with
test tubes or beakers but larger volumes of
stress involved, and identify the reaction that
could reduce that stress. After the prediction is Further Reading
reagents will be required. The solutions required established demonstrate what happens. Also point Alyea, Hubert N. and F.B. Dutton. Tested
are the same as those required for Activity 1 in out that the increase in color indicates that some Demonstrations in Chemistry. Easton, Penn-
Program 5. iron(III) ions were present in the solution. sylvania: Chemical Education Publishing Co.,
Label the petrie dish used, "add SCN' - . " Use 1965.
the same line of questioning for the stress "add
Choppin, Gregory R. et al. Chemistry. Morristown,
Fe3+." After establishing that both reactants
New Jersey: Silver Burdett, 1978.
are present at equilibrium ask students what
should be done to get the color to fade. They Othen, Clifford. Rates of Reaction and Equilibria.
should reply that removing one of the reactants London: Heinemann Educational Books,
will shift the equilibrium to the left and the color will 1968.
fade. Again, review the reasoning behind the Parry, Robert W. et al. Chemistry: Experimental
students' answer. Point out that this would require Foundations. Englewood Cliffs, New Jersey:
Five petrie dishes that the reaction he reversible. Tell them that Prentice-Hall, 1970.
150 mL beaker forms a complex with that will
Parry, Robert W. et al. Chemistry: Experimental
effectively tie it up, so it is removed from
Stirring rod Foundations. Teacher's Guide. Englewood
participating in the thiocyanoiron(III) equilibrium.
Cliffs, New Jersey: Prentice-Hall, 1975.
Add 25 mL of KSCN solution to an equal Label the petrie dish, "remove Fe 3 +," and add a
volume of water in the beaker. Add three or four few crystals of Na2HP04. Now ask if anyone has Rowley, Wayne R. E. Matter in Balance: Chemical
drops of the iron(III) solution into the beaker and noticed any other changes during the demonstra- Equilibrium. Toronto: Wiley, 1979.
stir. The number of drops can vary. The important tion that you haven't discussed. Someone usually Toon, E.R., and G.P. Ellis. Foundations in
point is that the color is intense enough to be notices that the reference has faded. Ask for plau- Chemistry. New York: Holt, Rinehart and
seen but not so intense that the equilibrium is sible explanations. Some, of course, will think you Winston, 1973.
pushed essentially to completion. Ask the are imagining things. Show them the fifth petrie
students for the ions present in the mixture and dish to establish the effect of the stress of adding
the possible combinations that might produce the heat from the projector on the thiocyanoiron(III)
equilibrium. If this is not dramatic enough warm
some of the solution in a Bunsen flame.

15
16

The Equilibrium Constant


a smooth curve of "best fit." Read off the graph the "best" values for
Objectives each vial number and have all students use these ratios in the remainder
Students should be able to: of the calculations.
1. Apply Le Chatelier's Principle to predict and explain how the stress of Figure 4
concentration affects a given system of equilibrium.
2. State experimental evidence for Le Chatelier's Principle.
3. Use the "Dance Hall" analogy or the Kinetic Molecular Theory to
account for Le Chatelier's predictions.
0.9
4. Write the mass action expression for the equilibrium constant for a
given chemical system.
0.8
5. Identify evidence that supports the Law of Chemical Equilibrium.
6. State the implications of the size of the equilibrium constant.
0.7

Program Description 0.6

Program 5 reviews the application of Le Chatelier's Principle to chemical 0.5


systems by illustrating and accounting for the changes produced by
altering the concentration of the reactants or products. Le Chatelier's 0.4
predictions are then shown to be consistent with the dynamic model of
equilibrium. The program reestablishes the need for having a more 0.3
quantitative expression for the changes and then uses empirical data to
i ntroduce the equilibrium constant. The result is generalized as the Law
of Chemical Equilibrium. The law is then applied to several systems and
Vial Number
the meaning of the size of the equilibrium constant is introduced.

Before Viewing Activity 1 enables students to discover that the mass action
Do Activities 1 and 2. Use Activity 3 in Program 4 as part of the prelab to expression for a system at equilibrium is independent of the concentra-
Activity 1. See the Teacher's Guide to Chemistry: Experimental tions of the reactants and products. It also introduces the idea of an
Foundations (see page 24) for suggestions to help students cope with equilibrium constant using data gathered by the students. Activity 2 does
the serial dilution required in this lab. Use Program 5 as part of the post- the same thing, using data gathered by others.
l ab for Activities 1 and 2. Before the post-lab have students plot their
depth ratio values versus the vial number on a set of axes drawn on a After Viewing
ditto. (See the following graph of typical results.) Run the ditto off so
everyone has a set of the data. The points will vary over a fairly large Do Activities 3 and 4. Activity 3 provides students with additional appli-
vertical range. Don't be concerned; there is bound to be considerable cations of Le Chatelier's Principle and another method for determining
variation due to the way the dilutions were carried out and the method the equilibrium constant. Activity 4 provides practice interpreting
used to compare the colors. Use the general shape of the curve to draw equilibrium constants and using them to make predictions.
the depths of solution required to make the color cylinder to the 25.0 mL mark with distilled
Activities intensities equal. water. Pour the solution into a dry, clean 150
Activity 1: Chemical Equilibrium - To prepare the standard solution in this activity mL beaker to mix it. Calculate the concentra-
you will use a small amount of thiocyanate ion, tion of this solution.
A Quantitative Description, Part 1 5. Rinse the second Mohr pipet with water and
SCN' - , and add a large excess of ferric ion,
I n this experiment you will take a quantitative look Fe 3+ (aq). You can assume that all of the thio- finally with a little of the solution in the
at the reaction cyanate ion will be used in forming the complex beaker.
thiocyanoiron(III) ion, FeSCN 2 +(aq). Thus the Caution: You only have 10 mL excess; only
concentration of FeSCN 2 +(aq) in the standard will use 2-3 mL to rinse the pipet. Do not return
which was used qualitatively in an earlier be equal to the starting concentration of the the rinse solution to the beaker; discard it.
demonstration. This time you will determine the SCN' - ( aq). The validity of this assumption will be 6. Use the second Mohr pipet and bulb to
concentration of each of the ions at equilibrium, discussed in the post-lab discussion. transfer 5.0 mL of the solution in the beaker
and then seek an expression that relates the
concentrations mathematically in a simple, to vial 2. Calculate the initial concentrations
Apparatus of the Fe 3 +(aq) and SCN' - i n the 10 mL of
convenient manner. Such an expression would
enable the quantification of Le Chatelier's predic- solution formed in the vial.
tions, a necessity if you wish to be able to predict Note: One mole of yields one mole
profits and losses for an industrial process. of
The concentrations are determined colon- 7. Rinse the graduated cylinder with water and
Distilled water
metrically. Color intensity of a solution depends finally with a little (2-3 mL) solution from the
upon the concentration and depth of the solution. Five flat bottom vials (must hold 10 mL) beaker.
If you add water to a cup of tea the color intensity Two 10 mL Mohr pipets 8. Pour 10.0 mL of solution from the beaker
remains constant. This is because the depth of the i nto the graduated cylinder then fill the
Pipet bulb
tea increases as the concentration decreases. cylinder to the 25.0 mL mark with distilled
The relationship is expressed as follows: 25 mL graduated cylinder water.
color intensity = kCd 150 mL beaker 9. Discard any solution remaining in the beaker
Diffused light source or white paper and rinse it with water. Dry the beaker with a
C = concentration expressed in mol/L paper towel.
d = depth in mm Ruler 1 0. Pour the solution in the graduated cylinder
k = proportionality constant Medicine dropper i nto the beaker to mix it.
1 1. Repeat steps 5 and 6, only this time transfer
Thus if two solutions appear to have the same Method the solution to vial 3, then repeat steps 7-10.
color intensity
1. Line up five clean, dry vials. Label them 1, 2, 1 2. This process is called serial dilution. Continue
etc. i t until you have 5.0 mL of successively more
2. Use a clean, dry Mohr pipet and pipet bulb tc diluted solution in each vial.
transfer 5.0 mL of 0.002 mol/L KSCN i nto Calculate the initial concentrations of
each of the vials. for each vial as part
3. of your preparation for the activity.
Thus if you know the concentration of a solu- 13. Wrap a strip of white paper around vials 1 and 2.
tion in one situation (let's call it the standard 1 4. Look vertically down through the solutions at
solution), you can calculate the concentration of 4. Add 10.0 mL of 0.2 mol/L Fe(N03)3 to the a diffused light source. Use the medicine
the solution in a second situation by comparing 25 mL graduated cylinder, then fill the dropper to remove a dropper full of the standard.

17
18

15. Return some of the standard in drops until the quantitative predictions. Try calculating the
colors match. Hold the vials close together
Activity 2: Chemical Equilibrium -
following:
and blink your eyes between "looks" to help A Quantitative Description, Part 2
avoid eye fatigue. Put the unused standard in This activity provides you with data to discover a
the dropper into a clean dry beaker, since general relationship for the concentrations of the
you may have to use some of this solution reactants and products at equilibrium. Perform the
later.
16. When the intensity of the color in the vials Observations
matches, record the height of solution in
each tube to the nearest millimetre.
17. Repeat the matching procedure with vials 1
and 3, 1 and 4, and finally 1 and 5.

2. Calculate the following for vials 2 through 5:


(a) Calculate the initial concentrations of
Discussion necessary calculations to complete the data tables
Initial means
1. Use Le Chatelier's Principle to explain why the for each of the following systems.
before any chemical reaction has taken
place. Subscript "I" is used to denote initial assumption made to calculate System I
concentrations. reasonable. System I involves the following equilibrium
(b) Calculate the radio of depths from the color 2. Which of the combinations, (i), (ii), or (iii), gives between ethyl acetate, water, acetic acid, and
comparison. Subscript "x" is used to the most constant value? To help you decide, ethanol:
denote the vial number. calculate the ratio of the largest value to the
smallest for each expression.
3. Restate the most constant expression in words
using the terms reactants and products. A
general statement of the regularity you have
noted is called the Law of Chemical
Equilibrium. The data in the table was gathered by starting
4. Assume that the reactions for this system with known amounts of ethyl acetate and water.
occur on a microscopic scale as written. Write The two reactants were placed in an Erlenmeyer
( d) Calculate the equilibrium concentration of rate expressions for the forward and reverse flask and swirled. The concentration of acetic acid
Fe3+(aq) and SCN1 -(aq). reactions. Show that the idea of a dynamic at equilibrium was determined with the aid of a pH
equilibrium is consistent with the expression meter. Since the production of one mole of acetic
found above. acid also involves the production of one mole of
[SCN'"] E = [FeSCN2+]E ethanol (ethyl alcohol), then the concentration of
(e) Now try to find some simple mathematical acetic acid and ethanol at equilibrium would have
relationship between the equilibrium to be the same. All trials were done at room
concentrations that could be used to make temperature.
Discussion
1. Show a sample calculation for
2. What stress caused the change in
from trial 1 to trial 8? Use Le Chatelier's
Principle to predict the effect of the stress.
Does the data in the table support your
prediction?
3. I n trials 4 and 5 1.00 mol of each of the
Note: The subscripts "I" and "E" used in the The equilibrium concentration of N02 was gases was put in the vessel (at least that is
table refer to initial and equilibrium concentrations measured colorimetrically, similar to the method the way it appears on the data table).
respectively. used in Activity 1. The only difference is that a However, this was not the way the trial was
spectrophotometer was used to measure the done. After equilibrium was reached in trial 4
For column "i" calculate:
color intensity. the volume of the container was adjusted to 3 L.

For column "ii" calculate:

1. Show a sample calculation for

2. The two expressions of the concentrations of


the products and reactants that you calculated
are called mass action expressions. Which
mass action expression for equilibrium concen-
trations is not a function of concentration (i.e.,
it doesn't change when the concentrations
change)? Note: The subscripts "I" and "E" used in the ( a) What would a change in the volume do to
3. Which of the three expressions is the most table refer to initial and equilibrium concentrations the pressure exerted on the gases?
useful? Explain your choice. respectively. ( b) Use Le Chatelier's Principle to predict the
4. Use Le Chatelier's Principle to predict the For column 'T' calculate: effect of this stress on the
effect when water is added to the ethyl (c) Does the data in the table support your
acetate system at equilibrium. Which trials prediction?
support your prediction? For column "ii" calculate: 4. Which of the three mass action expressions
of concentrations at equilibrium is not a
System If function of concentration?
System II involves the following equilibrium: For column "iii" calculate: 5. Which of the three expressions is the most
useful? Explain your choice.
6. What would be the mass action expression

19
20

for the following system that would not be a


function of concentration?
Note: Follow the convention of putting the
concentration of the products over the
reactants:

7. The value of the mass action expression that


i s independent of concentration is called the
equilibrium constant. What is the equilibrium
constant for the ethyl acetate equilibrium? Note: The subscripts "I" and "E" used in the
What is it for the nitrogen dioxide equilibrium
Activity 3: Chemical Equilibrium
table refer to initial and equilibrium concentrations
at 142 42 0 C? At 11 5 0 C? At 70OC? respectively. Antimony(III) chloride reacts with water to form
8. What two variables will alter the value of the white insoluble antimony(III) oxychloride. This
For column "i" calculate: hydrolysis reaction can be represented by the
equilibrium constant? Use the data presented
i n Systems I and II to answer this question. following equilibrium:
9. The reaction was written as an
endothermic reaction. In general, what effect
does an increase in temperature have on the
equilibrium constant for an endothermic Discussion
reaction? Write a generalized statement to
describe the effect of temperature on the 1. Show a sample calculation for The effects of adding water and hydrochloric
equilibrium constant. Is your statement 2. (a) Which mass action expression was equal acid to the system will be investigated. Also K, the
consistent with Le Chatelier's Principle? to the equilibrium constant? equilibrium constant for this reaction, will be
Explain your reasoning. (b) Did you predict correctly in question 9 of determined.
1 0. Predict the mass action expression that will System II? If not, where did you go wrong? One litre of the solution used contains 0.5 mol
equal the equilibrium constant for the 3. The symbol for the equilibrium constant is and 6 mol HCI. That is, the solution concen-
following equilibrium: capital "K." Write the mass action expression trations are 0.5 mol/L with respect tc and
for the equilibrium constant for the following 6 mol/L with respect to HCI. In this solution you
equilibrium: can assume the concentration of SbOCI is almost
System III zero.
System III involves the following equilibrium: Do discussion questions 1-4 on this page as
Note: The convention is to put the concentra-
part of your preparation for this activity.
tion of the products over the reactants.
The equilibrium concentration of 12 was 4. The mathematical expression you wrote in the
Apparatus
measured colorimetrically, similar to the method above question is a statement of the Law of
Chemical Equilibrium. State the law in words. 10 mL graduated cylinder
used in Activity 1. The only difference was
that a spectrophotometer was used to measure 5. The equilibrium constant is independent of 50 mL buret
the color intensity. All trials were carried out at concentration. What does this mean?
Two 125 mL Erlenmeyer flasks
698 K. 6. What two variables cause K, the equilibrium
constant, to vary? 20 mL 0.5 mol/L SbC13 in 6 mol/L HCI
25 mL 6 mol/L HCI
Caution: The soluble compounds of antimony are assuming that a negligible amount of SbCI3 7. Based on your observations, is the assumption
almost as poisonous as the compounds of was used in the formation of the white made in step 12 reasonable? If it isn't, how will
arsenic. Wear protective gloves and wash your precipitate. it affect your value of K'?
hands thoroughly after this activity. 1 2. Determine the value of K', the modified 8. (a) What is the value for K'?
equilibrium constant (see discussion question ( b) What does the value for K' imply about the
Method 4), from the concentrations of HCI and hydrolysis of antimony(Ill) chloride?
for the solution in which the SbOCI was just (c) Pedict the relationship between your value
1 . Transfer 5.0 mL of antimony(Ill) chloride
solution into an Erlenmeyer flask from a buret starting to form. for K' and the accepted value. Explain
at one of the dispensing stations your your reasoning.
teacher has set up. Discussion
2. Add 5 mL water from a graduated cylinder 1. Explain why it is reasonable to assume that Activity 4: Equilibrium Applications
and swirl the mixture. Record any changes. [SbOCI] = 0 in the solution that contains The following questions will help you learn to apply
3. Add an additional 10 mL of water in portions the concept of equilibrium to chemical systems.
of 2 mL at a time until a total of 15 mL have 2. Predict the effect of adding water on the 1. Use Le Chatelier's Principle to predict the
been added. The 15 mL includes the 5 mL antimony(III) chloride hydrolysis equilibrium. effects of heat, pressure, and concentration
added in step 2. Swirl the mixture and record Describe any changes you would expect to on the following chemical systems:
any changes with each addition. see. (a) The production of methanol (methyl
4. Use the graduated cylinder to add 2 mL of 3. Predict the effect of adding hydrochloric acid alcohol). Stresses: add heat, increase
6 mol/L HCI. Swirl and record any changes. on the antimony(III) chloride hydrolysis nressure by compressing the container.
5. Add an additional 6 mL in 2 mL portions, equilibrium. Describe any changes you would removal of methanol.
swirling the contents and recording any expect to see.
changes each time. 4. (a) Write the mass action expression for the
6. Dispose of the mixture as your teacher equilibrium constant for the antimony(III)
directs. chloride.
7. Add 5.0 mL antimony(III) chloride solution ( b) Since the concentration of a pure solid or ( b) The production of chlorine. Stresses:
from the buret at the dispensing station to a li quid is directly proportional to its density it
remove heat, decrease pressure by
clean, dry 125 mL Erlenmeyer flask. will only change with temperature, Thus the
expanding the container, add oxygen, add
8. From another buret add water to the flask concentration of a pure solid or liquid in
a catalyst, add a noble gas that doesn't
until the white precipitate begins to form. equilibrium with other substances remains
react with any participant in the
Swirl the flask continuously as you add the constant. Since the concentration of the equilibrium.
water slowly. Try not to add too much. You water and the antimony(III) oxychloride do
can use your results from steps 2 and 3 as a not change they can be grouped with the
guide. Record the volume of water required equilibrium constant to form a new constant
to the nearest 0.1 mL. called K'. Write the mass action
9. Dispose of the mixture as your teacher expression for K'.
directs. (c) The formation of
(c) What would K' be equal to in terms of K?
10. Calculate the concentration of HCI in the total Stresses: add heat. increase the pressure
5. (a) At what point in the addition of water (steps
volume of solution when the precipitate was of add solid
2 and 3) was the system at equilibrium?
just starting to form. (b) Why did the system not appear to change
11. Calculate the concentration of antimony(III) after several additions of water?
chloride present in the total volume, 6. Account for any change or lack of change that
occurred when the acid was added.

21
what will be the concentration of 6.7 g of S02CI2 and 101.3 kPa of Cl2 are (c) On separate sketches of the graph, show
hydrogen iodide at equilibrium? placed in a 1.0 L bulb at 375 K. the effects of the following on the original
(b) At a certain temperature hydrogen iodide ( d) Compare parts (b) and (c). In order to get system at equilibrium:
i s 20 percent dissociated. Determine the the situation in (c), what stress must be (i) adding a catalyst
concentration of each component present applied to the system in (b)? Use Le (ii) adding more "A"
i n the mixture at equilibrium, if 0.50 mol of Chatelier's Principle to predict the effect. (iii) raising the temperature of the system
HI are placed in a 1 .00 L vessel at this Compare your predictions with the (iv) reducing the volume of the container
temperature. calculated concentrations. Are they to 5.0 L
(c) Determine the equilibrium constant for the consistent? (v) adding the noble gas neon.
formation of hydrogen iodide at this 9. Ammonium hydrosulfide decomposes in the
certain temperature. following manner:
(d) Is the certain temperature lower or higher Further Reading
than 699 K? Explain your reasoning.
( e) In a mixture of hydrogen iodide, Alyea, Hubert N., and F.B. Dutton. Tested
hydrogen, and iodine at 699 K, the partial ( a) Determine the partial pressures of Demonstrations in Chemistry. Easton, Penn-
pressures are 70.9 kPa, 2.03 kPa, and ammonia and hydrogen sulfide at equilib- sylvania: Chemical Education Publishing Co.,
2.03 kPa respectively. Will there be any rium when excess solid ammonium hydro- 1965.
change in the partial pressure if the sulfide decomposes in an excavated CHEM Study. Chemistry: An Experimental
mixture is maintained at 699 K? If so, will chamber at 25 ° C. Science. Teacher's Guide. San Francisco:
HI be consumed or formed? ( b) Use Le Chatelier's Principle to predict the W.H. Freeman, 1963.
(f) 1.00 mol of H2 and 2.00 mol of 12 gas are effect of injecting ammonia into the
Choppin, Gregory R. et a/. Chemistry. Morristown.-
put into a 10 L container at 699 K. system at equilibrium.
Silver Burdett, 1978.
Determine equilibrium concentrations of ( c) Check your prediction by completing the
the three gases at equilibrium. following problem: NSCM Project Practical Activities Cl 0. Principles
(g) What would happen to the equilibrium Excess solid ammonium hydrosulfide is of Chemical Equilibrium. Milton, Australia:
concentrations in (f) if the volume were placed in a flask with 50.7 kPa of Jacaranda Press, 1973.
compressed to 5.0 L? ammonia. What will be the partial Othen, Clifford. Rates of Reaction and Equilibria.
pressures of ammonia and hydrogen London: Heinemann Educational Books,
sulfide at equilibrium? 1968.
1 0. The equilibrium constant for the reaction of
Parry, Robert W. et a/. Chemistry: Experimental
"A" and "B" to produce "C" is 4.0.
Foundations. Englewood Cliffs, New Jersey:
is 243.1 kPa when the partial pressures are
Prentice-Hall, 1970.
expressed in kilopascals.
(a) 6.7 g of S02CI2 are placed in a 1.0 L bulb ( a) Determine the equilibrium concentration Parry, Robert W. et al. Chemistry: Experimental
at 375 K. Determine the pressure of each species if the starting conditions Foundations. Teacher's Guide. Englewood
exerted by the assuming none of are 0.50 mol of "A" and 1.0 mol of "B" in Cliffs, New Jersey: Prentice-Hall, 1975.
it dissociated. a 10.0 L container.
Rowley, Wayne R. E. Matter in Balance: Chemical
(b) Determine the partial pressures of ( b) If it took 10 minutes to reach equilibrium,
Equilibrium. Toronto: Wiley, 1979.
and at equilibrium. accurately sketch a concentration time
graph for the attainment of equilibrium. Toon, E.R., and G.P. Ellis. Foundations of
, c) Determine the partial pressures of
Chemistry. New York: Holt, Rinehart and
and at equilibrium if
Winston, 1973.

23
24

The Haber Process


Objectives Before Viewing
Students should be able to: Have students complete Activity 1. They are asked to apply Le
1. Describe the Haber Process for the production of ammonia. Chatelier's Principle in selecting conditions for an industrial process.
2. Discuss the societal implications of the Haber Process. However, because an industrial process continually removes the wanted
3. Apply the concepts of rate and equilibrium to the development of the products, the reaction never reaches equilibrium. Thus in most cases
conditions for an industrial process. their predictions will be quite different from the actual conditions used.
Because an industrial process is better described as a steady state than
an equilibrium system, an application of factors that affect the rate of a
Program Description reaction are also important. As the program points out, both concepts
must be applied.
Program 6 begins by establishing the historical events that created the
Take up the students' answers to the questions but don't evaluate
need for the Haber Process. It then goes through a development of the
their thoughts on question 6. Program 6 will help them with this one.
process using the concepts from the previous programs. The develop-
ment requires not only an application of the concepts of chemical
equilibrium but also of those of reaction kinetics. The program ends with After Viewing
a brief description of the "rewards" reaped by Haber for his mastery of
chemical equilibrium. Do Activity 2 and consider using Activity 3 as one of the projects that
students may choose to work on this term.

Activities
Activity 1: Le Chatelier and
the Haber Process
Experimental studies have shown that the
percentage of ammonia formed from hydrogen
Ammonia
Produced and nitrogen at equilibrium varies as a function of
( %) the pressure exerted on the system as a whole.
The results for a series of different temperatures
are shown in Figure 5.

Discussion
1 . Write an equation to describe the formation of
ammonia. The name given to the industrial
process using this chemical reaction is the
Haber Process.
0 20 40 60 80 100 2. Is the formation of ammonia an endo- or
Pressure (mPa) exothermic reaction? Use data from the graph
Figure 5
to support your decision.
3. Use Le Chatelier's Principle to predict the (a) increasing the applied pressure 9. The ethyl benzene (boiling point 136 ° C) that
effects of the following stresses on the (b) removing styrene has not reacted and the styrene (boiling point
ammonia equilibrium: (c) reducing the temperature 146 ° C) are separated by fractional distillation.
(a) removing ammonia ( d) adding a catalyst The styrene, of course, is used to make poly-
( b) increasing the applied pressure (e) adding an inert substance. styrene. If you were the industrialist, what
(c) raising the temperature 2. Based on your predictions in question 1, would you do with the ethyl benzene?
(d) adding a catalyst select the conditions that would maximize the
( e) adding an inert substance. yield of styrene. The Production of Sulfuric Acid -
3. (a) Why are the conditions selected in The Contact Process
4. State evidence from the graph to support your question 2 unlikely to be those used by
predictions in 3(b) and (c). i ndustry? 1 . Write a set of equations to describe the major
5. List in general terms the conditions that would (b) What additional considerations must be reactions taking place in the contact process.
yield the most ammonia. made when selecting conditions to 2. The system sulfur dioxide, oxygen, and sulfur
6. (a) At 20 mPa, what is the yield of ammonia maximize the yield of an industrial process? trioxide is in equilibrium at 101.3 kPa and
at: 4. In practice, the pressure of the ethyl benzene 400 ° C in the presence of a catalyst. State
(i) 473 K(200 ° C) is kept low, as Le Chatelier would suggest, but whether the amount of sulfur trioxide would be
(ii) 873 K(600 ° C) an inert substance - super-heated steam - is i ncreased, decreased, or unchanged by each
( b) At which temperature would you choose to added to keep the total pressure of the mixture of the following. Give reasons for your
run the Haber Process? Why? at atmospheric pressure. What advantage answers.
7. The conditions universally employed by does this method have over running the (a) decreasing the applied pressure at 400 °C
industry are 873 K(600 ° C), 20 mPa, and the reaction without the steam at a pressure less (b) adding 5 mol of oxygen at 400 ° C
use of a catalyst. Suggest plausible reasons than atmospheric? (c) decreasing the concentration of SO2 at
for this. 5. The super-heated steam serves two other 400°C
functions: First it supplies energy to the (d) adding 2 mol of helium, V and T constant
Activity 2: Le Chatelier and system. Why is this desirable? Second, it (e) removing the catalyst.
Other Industrial Processes reacts with any carbon formed as a byproduct 3. Use Le Chatelier's Principle to suggest three
at high temperatures, preventing the carbon
The Production of Polystyrene ways to increase the yield of sulfur trioxide.
from contaminating the catalyst. What products 4. State the conditions you would use as an
As part of the reaction sequence in which will be formed as a result of the reaction i ndustrialist. Explain the reason for choosing
polystyrene is produced from benzene, ethyl between carbon and steam? these conditions if they differ from those you
benzene is dehydrogenated to produce styrene, 6. What is the advantage of using super-heated suggested in question 3.
the monomer of polystyrene. The following steam at 873 K(600°C) rather than ordinary 5. List the actual industrial conditions used (e.g.,
equation describes the reaction: steam? temperature; pressure; catalyst; for removing
7. In practice, an iron oxide catalyst is used. sulfur trioxide). Explain the reason for choosing
Explain why this is desirable. these conditions if they differ from those you
8. The process is run at 873 K(600 ° C) with an suggested in question 4.
i ron oxide catalyst. The conversion is only
about 35 percent complete. The yield could Activity 3: Industrial
be increased by raising the temperature.
1 . Use Le Chatelier's Principle to predict the Suggest two plausible reasons why this is not Process Project
effects of the following on the styrene done. The task is to present, in an attractive fashion, the
equilibrium: chemistry involved in an industrial process.

25
26

Pictures, drawings, color, letter size, etc., can be


used to present the information in as attractive a Further Reading
package as possible. In effect you are going to
produce an ad for the industrial process you
Ashman, A., and G. Cremonesi. Sulfuric Acid.
London: LongmanslPenguin Books, 1968.
Ordering
select.

Description of the Task


Bradford, Derek. Chemistry and the World Food
Problem. London: Heinemann Educational
Books, 1971.
information
1. The industrial process chosen must involve To order the videotapes or this publication, or for
Haber, L.F. The Nitrogen Problem. London: additional information, please contact one of the
some chemical reaction-
LongmanslPenguin Books, 1966. following:
2. The maximum area covered by your ad should
be 1500 cm2. Parry, Robert W. et al. Chemistry: Experimental Ontario
3. It must be possible to display your ad on the Foundations. Englewood Cliffs, New Jersey: TVOntario Sales and Licensing
wall. Prentice-Hall, 1970. Box 200, Station 0
4. The ad must contain the following information: Toronto, Ontario M4T 2T1
Parry, Robert W. et al. Chemistry: Experimental (416) 484-2613
(a) name of industry Foundations. Teacher's Guide. Englewood
(b) chemical reactions involved Cliffs, New Jersey: Prentice-Hall, 1975. Untied States
(c) conditions under which reactions are run TVOntario
Rowley, Wayne R. E. Matter in Balance: Chemical
(d) location of plants U.S. Sales Office
Equilibrium. Toronto: Wiley, 1979.
(e) source of raw materials. 901 Kildaire Farm Road
5. The following may be included if desired: Toon, E.R., and G.P. Ellis. Foundations of Building A
(a) pictures of plants Chemistry. New York: Holt, Rinehart and Cary, North Carolina
(b) drawings or flow charts of the process Winston, 1973. 27511
Phone: 800-331-9566
(c) labels used on final products Fax: 919-380-0961
(d) anything else you feel makes your ad more E -mail: ussales@tvo.or g
attractive.

Example Industrial Processes


Several industrial processes are listed. They are
i ncluded to give you an idea of the range of Videotapes BPN
processes from which you can select. The list is Program 1: Steady Unsteadiness 240701
not meant to be restrictive; the possibilities are Program 2: Dynamic Equilibrium 240702
endless. Program 3: Reaction Kinetics 240703
Program 4: Reaction Tendencies 240704
1. Production of iron Program 5: The Equilibrium Constant 240705
2. Production of aspirin Program 6: The Haber Process 240706
3. Film developing and printing
4. Electroplating
5. Brewing