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Chapter 8. Entropy and Molecular Organization: Faculty Resource and Organizational Guide (FROG)
Chapter 8. Entropy and Molecular Organization: Faculty Resource and Organizational Guide (FROG)
Chapter 8
Chapter 8
Material
Quantity
8.1
1-liter beaker
8.1
8.1
8.1
8.1; 8.7
Wooden toothpicks
4; 2/group
8.1
Clay
8.1
8.4; 8.7
1 package
8.35
1/group
8.35
3/group
8.37`
8.37
Stirrers
8.37
Flashlight or source of a
bright beam of light such as
a laser pointer
8.37
8.42
250-mL beaker
8.42
Wooden stirrer
8.42
Thermometer
Chapter 8
Reagents
Quantity
8.1
Pancake syrup
40 mL.
8.35
Cooking oil
2 mL/group
8.35; 8.37
Liquid dishwashing
detergent
8.37
Table sugar
1 packet
8.42
Crushed ice
400 mL
8.42
90 g
Chapter 8
Chapter 8
We hope you find this chapter to be a more intuitive introduction to entropy and analyses based
on entropy change than you may have been taught or be teaching. For more background on this
approach and many more examples see one or more of the books, articles, and web resources
listed in these references.
References:
Henry A. Bent, The Second Law (Oxford, New York, 1965).
Leonard K. Nash, Elements of Statistical Thermodynamics (Addison-Wesley, Reading, MA
1968).
Norman C. Craig, Entropy Analysis (Wiley, New York, 1992).
John P. Lowe, Entropy: Conceptual disorder, J. Chem. Ed. 1988, 65, 403.
Norman C. Craig, Entropy analyses of four familiar processes, J. Chem. Ed. 1988, 65, 760.
Norman C. Craig, Entropy Diagrams, J. Chem. Ed. 1996, 73, 710.
Frank L. Lambert, Shuffled Cards, Messy Desks, and Disorderly Dorm Rooms Examples of
Entropy Increase? Nonsense! J. Chem. Ed. 1999, 76, 1385.
Frank L. Lambert, Disorder A Cracked Crutch for Supporting Entropy Discussions, J.
Chem. Ed. 2002, 79, 187.
Frank L. Lambert, Entropy is Simple, Qualitatively, J. Chem. Ed. 2002, 79, 1241.
Frank L. Lambert, Disorder in Unstretched Rubber Bands, J. Chem. Ed. 2003, 80, 145. This
is a letter commenting on Warren Hirsch, Rubber Bands, Free Energy, and Le Chateliers
Principle, (a classroom activity), J. Chem. Ed. 2002, 79, 200A. The authors reply to the
letter is also at J. Chem. Ed. 2003, 80, 145.
Norman C. Craig, Campbells Rule for Estimating Entropy Changes in Gas-Producing and
Gas-Consuming Reactions and Related Generalizations about Entropies and Enthalpies, J.
Chem. Ed. 2003, 80, 1432.
J. N. Spencer and John P. Lowe, Entropy: The Effects of Distinguishability, J. Chem. Ed.
2003, 80, 1417.
Frank Lambert's web sites:
http://www.shakespeare2ndlaw.com
http://www.entropysimple.com
Chapter 8
Materials:
1-liter beaker.
Fresh carrot, peeled. (Peeling is not strictly necessary, but adds to the idea that the cells
involved in the osmosis are all the same if the outer skin layer of cells is removed.) The
width of the top of the carrot should be 3-4 cm. Some instructors have been able to do this
activity with much smaller carrots, but boring out the hole gets trickier as the carrot gets
smaller.
Cork borer of appropriate size (see below) or drill.
Clear plastic drinking straw or a plastic transfer pipet with a wide stem. A capillary tube will
also work, but may be more difficult to seal and get syrup into.
4 wooden toothpicks.
Clay.
9-inch glass Pasteur pipet with bulb.
Reagents:
Warm pancake syrup or other relatively non-viscous, colored sugar solution. (Do not use
molasses or other heavy viscous syrups, as they will be difficult to get into the hollowedout carrot.)
Water.
Procedure:
Before class, prepare the carrot. Peel the carrot and cut off the top to expose a fresh flat
surface with a diameter of about 3-4 cm. Cut off the bottom of the carrot so that there will be
space between the bottom of the beaker and the carrot when the carrot is suspended in the
beaker (as shown in the photographs under Anticipated Results).
Use a cork borer to make a 10-cm long cylindrical hole down the center of the length of the
carrot. The diameter of the hole should be slightly less than the diameter of the straw (or the
stem of the plastic transfer pipet). If a piece of carrot remains in the hole, use a smaller cork
borer to whittle out the piece of carrot. If available, you can use a drill press to bore out the
hole.
Cut the drinking straw in half and insert one piece of the cut straw about 2 cm into the carrot
hole. Seal carefully with clay. Alternatively, cut the bulb off the plastic transfer pipet and
insert the tapered end into the hole in the carrot to form a seal like a cork. You can do this
after the syrup is added to the hole, which will make it easier to get the hole filled with syrup.
Insert three or four wooden toothpicks near the top of the carrot to support it in the beaker
filled with only about 0.5 cm of the carrot above the top of the beaker.
The foregoing preparation can be done several hours in advance of class (if the carrot is kept
wet), but the remainder should be done very shortly before class.
Use the Pasteur pipet to add enough warm syrup (warmed to reduce the viscosity as much as
possible) to bring the liquid level about 2 cm above top of the carrot. Put the pipet, filled with
syrup, into the carrot as far as possible to add the syrup. This will help eliminate air bubbles in
the hole. Mark the level of the syrup on the straw. If the plastic pipet is used, fill the hole in
the carrot to the top with syrup and insert the tapered end of the pipet far enough to seal the
hole (being careful not to press too hard and split the carrot). Add a bit of syrup to the pipet
stem to make the level visible and mark the level.
Add sufficient water to the beaker so the water level is just about to the top of the carrot. Wait
about 10 minutes. If liquid is oozing through the clay, your clay seal needs to be redone. If the
syrup level has dropped, this means that you had air bubbles in the carrot. Add more syrup.
Chapter 8
To transfer the set up to class, empty the water from the beaker, leaving the carrot in place in
the empty beaker, and then fill the beaker with water when you get to class.
Explain the set up (hole in the carrot filled with enough syrup to show in the column above
the carrot) and begin your introduction to this chapter and discussion on mixing and osmosis.
Anticipated results
After 30-40 minutes, the water level should rise, as shown here:
beginning
about 40 minutes later
NOTE: The rise of liquid in the straw or pipet stem will occur, whether or not the carrot is
immersed in water. Essentially all the water that enters the cavity in these first several minutes
comes from the cells close to the cavity, not from water that surrounds the carrot. That is why
you need to add the syrup very shortly before you start class. The osmosis starts immediately,
even if the carrot is not in water.
Clean-up:
Discard carrot in a trash container.
Follow-up discussion:
Use Consider This 8.2 to initiate discussion of this activity.
Discuss mixing and osmosis as a mixing process.
Follow-up activities:
End of chapter problems 8.1 through 8.5.
Student Report Sheet for Investigate This 8.1
(This student report sheet serves as a template for both Investigate This and Consider This
activities. Instructors can modify this sheet to meet their students' learning needs.)
Name:
Names of Group Members:
Summary of Procedure: By monitoring the volume of syrup in a hollow carrot, observe the
process of osmosis.
Observations:
Additional Notes:
Chapter 8
Consider This 8.2. What direction does water move through a hollow carrot?
Goal:
Explain the observations made in Investigate This 8.1 in terms of water movement.
Classroom options:
Allow students, working in small groups, to answer these questions. Then, the instructor can
lead the follow-up discussion.
This activity can be conducted as an open class discussion.
Time for activity:
From 5 to 15 minutes, depending on how much of the mixing discussion occurs previously
and whether you include viewing and discussion of the Web Companion animation.
Instructor notes:
Students should reason and conclude:
(a) The level of liquid in the column of syrup rises. The rise in the level of the column of
liquid must be caused by an increase in the volume of liquid in the cavity of the carrot.
(b) The animation in the Web Companion, Chapter 8, Section 8.4, page 1, is designed to
mimic the classroom investigation, so the observations, rise of the liquid level in the column
of syrup is the same in both cases.
(c) Liquid must enter the cavity in the carrot from the cells surrounding it. The most likely
liquid is water, since there is water on the outside of the carrot and the most abundant
molecule in cells is water. One can postulate that water goes through the cell walls of the
carrot to dilute the syrup, which increases its volume and causes the liquid level in the
column to rise. If the water comes from the outside, it has to pass through many cells to get
to the cavity. Some students may postulate (correctly) that water, in the cells of the carrot,
moves into the column to dilute the syrup. [There is a sort of domino effect here with water
from the cells adjacent to the cavity entering by osmosis through their cell walls. This
increases the concentration of solutes in these cells and osmosis can occur from the next
layer of cells into the first layer and so on through the entire thickness of the carrot until
water from the beaker enters the cells on the very outside of the carrot.]
Follow-up discussion:
Define and discuss osmosis and the concept of semipermeability.
Discuss Figures 8.2 and Figure 8.3 and the relationship between them (both involve mixing of
one kind of molecules with another kind).
Follow-up activities:
End of chapter problems 8.1 through 8.5.
Chapter 8
Classroom options:
Allow 3-5 minutes for students, working in small groups, to assign their values. Then, the
groups can share their assignments and explanations with the class, summarizing them on the
chalkboard or an overhead transparency.
This activity could be conducted as an open class discussion.
This activity could be given as a homework assignment and discussed at the next class
session.
Time for activity:
5-10 minutes.
Instructor's notes:
Students should reason and conclude:
(a) 1: When we drop objects that are denser than air, our experience is that they always fall to
the floor, due to their attraction to the Earth.
(b) 0: We have never observed a solution of a solid that is soluble in the solvent becoming
unmixed, that is, spontaneously separating into pure solute and solvent.
(c) 0: If the room temperature is above 273 K, we never observe a glass of liquid water
freezing, but, if it happens to be winter and you leave the window of the room open, it is
possible that the room will cool to below 273 K and then the water could freeze. Since this
would be a special case, we can consider it very unlikely, so the probability is near zero.
(d) 1: The reasoning here is very much like that in part (c). If the room temperature is
above 273 K, the ice cube will melt, but in the unlikely event that the temperature of your
room goes below 273 K, the ice cube will not melt.
(e) 0: We have never observed pieces of waste paper spontaneously moving from a
wastebasket to the desktop.
(f) ?: Sugars are quite soluble in water, but they do vary in their solubilities. In Chapter 2,
Section 2, page 80, we were told that 200 g of table sugar, sucrose, will dissolve in 100 mL
of water, but only 100 g of glucose will dissolve in 100 mL of water. Each of these sugars
has a density of about 1.5 gmL1, so a given volume of sugar has a mass about 1.5 times
greater than the mass of the same volume of water. Thus, if the sugar that we are dissolving
is sucrose, a teaspoon of sugar (about 7.5 g) will all dissolve in a teaspoon of water (about 5
g). However, a teaspoon of glucose will not all dissolve in a teaspoon of water. The
probability in this case depends on the identity of the sugar.
Follow-up discussion:
Discussion should focus on the two key points from this section that are fundamental to the
rest of the chapter: (1) if a system can exist in more than one observable state (mixed or
unmixed, for example), any changes will be in the direction toward the state that is most
probable; and (2) each distinguishably different molecular arrangement of a system is equally
probable.
Try to be sure that students understand what distinguishable arrangements are and use this
discussion as a lead-in to Investigate This 8.4, which opens the next section.
Follow-up activities:
End of chapter problems 8.6 through 8.8.
10
Chapter 8
Follow-up discussion:
Discussion may begin by deciding how the students know when all the distinguishable
arrangements have been found. Several systematic approaches were probably used and can be
explained.
The discussion should provide the lead-in to the mixing model and the concept of
distinguishable molecular arrangements, W. Students should note that W is simply a number, a
dimensionless quantity.
11
Chapter 8
Follow-up activities:
Students can find the number of distinguishable arrangements for three objects in six boxes.
There are 20 distinguishable arrangements:
NOTE: These 20 arrangements are also shown for a different array of boxes in Figure 8.5 and
the two sets could be compared to see that they are, indeed, the same.
End of chapter problems: 8.9-8.12.
12
Chapter 8
atom
#2
atom
#3
atom
#4
arrangement
of quanta
2,0,0,0
0,2,0,0
0,0,2,0
0,0,0,2
13
Chapter 8
({)
({)
((({((( ((({(((
((({(((
({)
({)
((({(((
((({((( ((({(((
({)
({)
({)
({((
({)
(({((
({)
((({((( ((({(((
({)
((({(((
({)
({((
({)
1,1,0,0
0,1,1,0
0,0,1,1
1,0,1,0
1,0,0,1
0,1,0,1
Follow-up discussion:
Discuss and remind students of the definition of energy quanta from Chapter 4.
Discuss the number of distinguishable arrangements that students found and, in particular,
how they knew they had found all possible arrangements.
The discussion should be directed toward introducing a model for energy arrangements that
leads to an understanding of the direction of energy transfer between objects.
Follow-up activities:
As a challenge activity, students can find the number of distinguishable arrangements for
three quanta among four atoms. The results (also see Figure 8.9) are:
atom
#1
atom
#2
atom
#3
atom
#4
((({)))
((({(((
((({(((
(({((
(({))
({)
((({(((
((({(((
((({(((
((({(((
(({))
({)
((({(((
((({(((
(({))
({)
({)
((({(((
({)
({)
((({(((
((({)))
((({(((
(({((
({)
(({))
(({))
({)
((({(((
((({(((
((({(((
((({(((
(({))
({)
((({(((
((({(((
({)
({)
( {((
({)
((({(((
((({(((
((({)))
((({(((
((({(((
((({(((
({)
(({))
(({))
({)
({)
(({))
((({(((
((({(((
((({(((
((({(((
({)
({)
({)
( {((
((({(((
((({(((
((({(((
((({)))
((({(((
((({(((
((({(((
((({(((
({)
(({))
((({(((
((({(((
({)
(({))
({)
(({))
((({(((
({)
({)
({)
arrangement
of quanta
3,0,0,0
0,3,0,0
0,0,3,0
0,0,0,3
2,1,0,0
1,2,0,0
0,2,1,0
0,1,2,0
0,0,2,1
0,0,1,2
2,0,1,0
1,0,2,0
0,2,0,1
0,1,0,2
2,0,0,1
1,0,0,2
1,1,1,0
0,1,1,1
1,0,1,1
1,1,0,1
Worked Example 8.8. Energy transfer between solids with different energies.
Check This 8.9. Energy transfer from a cooler to a warmer solid.
End of chapter problems 8.16 through 8.19.
14
Chapter 8
15
Chapter 8
16
Chapter 8
Follow-up discussion:
With the signs for the positional entropy change in the system (ice-water) and the thermal
entropy change in the surroundings (block of metal), you can initiate the discussion of the net
entropy change for ice melting and water freezing.
Show or refer students to Figure 8.11 to help direct the reasoning that leads to conclusions
about the relative sizes of the positional and thermal entropy changes.
Follow-up activities:
Check This 8.13. Net entropy change water for water freezing.
Consider This 8.14. How does thermal entropy change depend upon temperature?
Worked Example 8.15. Net entropy change for melting ice with surroundings at 283 K.
Check This 8.16. Net entropy change for freezing water with surroundings at 263 K.
Consider This 8.17. What are net entropy changes for ice and water changes at 273 K?
End of chapter problems 8.29 through 8.32.
Consider This 8.14. How does thermal entropy change depend upon temperature?
Goal:
Use the data from Figure 8.9 to calculate changes in thermal entropy for changes in energy and
attempt to deduce the form of the dependence of entropy change on the energy change and
temperature.
Classroom options:
Allow students, working in small groups, 5-7 minutes to begin their analyses and then have
the groups share their results and reasoning with the class. Then the discussion can continue
based on what the class determines to be correct reasoning.
This activity could be conducted as an open class discussion.
Time for activity:
From 10 to 15 minutes.
Instructor notes:
Show or direct students to Figure 8.9 while carrying out this activity.
Remind students about equation (8.6), S k lnW, the Boltzmann definition of entropy.
Indicate that they can find the Boltzmann constant (page 527 and inside back cover of the
textbook), but do not have to carry out the arithmetic using it in this activity.
NOTE: Entropy is related to W through the Boltzmann definition. The inclusion of energy
(joules) in the units of entropy has nothing to do with what arrangements are being counted,
whether it is particles among energy levels (the quantum mechanical approach to what we are
calling positional entropy) or energy quanta among oscillators. The units arise through the
definition, which is chosen to make the results from statistical thermodynamics identical to
those from classical thermodynamics. There is no other rationale for the appearance of the
Boltzmann constant.
Students should reason and conclude:
(a) Subscripts refer to the number of energy quanta in the solid.
S10-9 = S9 S10 = klnW9 klnW10 = kln(W9/W10) = kln(220/286) = k(0.262) = 0.262 k
S5-4 = S4 S5 = klnW4 klnW5 = kln(W4/W5) = kln(35/56) = k(0.470) = 0.470 k
The change in entropy is larger for the four-atom solid losing one quantum of energy to go
from 5 to 4 quanta.
17
Chapter 8
(b) As shown in Worked Example 8.8, the temperature of an atomic solid depends on the
number of energy quanta it has: the more quanta, the higher the temperature. Thus the solid
that has 10 (or 9) quanta of energy has a higher temperature than the one with 5 (or 4)T10 >
T5.
(c) The energy change for each system is E = 1 quantum (the solids lose energy, so the
change is negative) and the change in entropy is also negative. From Figure 8.9, we observe
that entropy (or W) increases as the energy increases (or decreases as energy decreases), so it
seems likely that changes in entropy are directly related to changes in energy for this atomic
solid:
S E
The entropy change for the higher temperature (T10) solid, S10-9, is smaller than the entropy
change for the lower temperature (T5) solid, S5-4. Thus, it appears that the entropy change is
inversely proportional to the temperature of the atomic solid:
S 1/T
Combining these two relationships, our analysis suggests that the relationship among the
entropy change, energy change, and temperature at which the change occurs might be:
S E/T
Follow-up discussion:
Try to make sure the class understands that the change in number of quanta in this problem is
what we perceive as a thermal energy change in macroscopic systems.
Use part (c) to initiate discussion of how the thermal entropy change is expressed as a
function of the energy (enthalpy) change of the thermal reservoir and its temperature.
Follow-up activities:
Worked Example 8.15. Net entropy change for melting ice with surroundings at 283 K.
Check This 8.16. Net entropy change for freezing water with surroundings at 263 K.
Consider This 8.17. What are net entropy changes for ice and water changes at 273 K?
End of chapter problems 8.29 through 8.36.
Consider This 8.17. What are net entropy changes for ice and water changes at 273 K?
Goal:
Calculate the net entropy changes for melting ice and freezing water at 273 K and find that they
are both zero.
Classroom options:
Allow students, working in small groups, approximately 5-7 minutes to answer the questions
and then the groups can share their results and reasoning with the class.
This activity could be conducted as an open class discussion.
Time for activity:
Approximately 10-15 minutes leading to the criterion for equilibrium.
Instructor notes:
Conduct this activity after students have studied Worked Example 8.15 and done Check This
8.16. The calculations here are identical to the ones in these activities. The extension here is to
the equilibrium temperature for the phase change and the finding that Snet = 0 for both the
freezing and melting processes. That is, the reaction is not spontaneous in either direction at
the equilibrium temperature.
Students should reason and conclude:
(a) The calculations are just as in Worked Example 8.15, except that here T = 273 K:
18
Chapter 8
3
1
Hsurr
6.00 10 J mol
=
= 22.0 JK1mol1
Tsurr
273 K
3
1
Hsurr
6.00 10 J mol
=
= 22.0 JK1mol1
Tsurr
273 K
19
Chapter 8
Use standard enthalpies and standard free energies of formation, and standard entropies (from
tabulated values) to calculate the standard enthalpy, free energy, and entropy changes for a
reaction.
20
Chapter 8
Anticipated results:
(a) When the oil and water are mixed and allowed to stand, the oil (top layer) and water
(bottom layer) will form two distinct layers. The size of the layers helps identify the oil and
water.
(b) After adding detergent and mixing, the two layers disappear and one, emulsified solution
is observed. The solution should appear homogeneous (the same appearance throughout), but
will probably not be clear, since the detergent-oil micelles will scatter light and make the
solution opalescent. The thing to draw to students attention is that there are no longer two
layers.
Follow-up discussion:
Use Consider This 8.36 to initiate discussion of the results of this activity.
Show or refer students to Figure 8.16 to help explain how water molecules orient themselves,
linking back to positional entropy change.
Follow-up activities:
End of chapter problems 8.60 through 8.62.
Consider This 8.36. Why don't oil and water mix?
Goal:
Reformulate the unfavorable-arrangements-of-water-molecules explanation (Chapter 2, Sections
2.1 and 2.2) for the insolubility of nonpolar compounds in terms of entropy.
Classroom options:
Allow students, working in small groups, 3-4 minutes to construct their explanations and then
have the groups share them with the class to begin discussion.
This activity could be conducted as an open class discussion.
Time for activity:
Approximately 10 minutes.
Instructor notes:
Review the results from Investigate This 2.5 as well as the succeeding discussion of the
insolubility of nonpolar solutes in water.
Students should reason and conclude:
The overall positional entropy change is negative for dissolving oil in water. If the nonpolar
oil molecules are mixed with water molecules, the water molecules group around the
nonpolar molecules and the water molecules' motions are restricted. Thus fewer molecular
arrangements are possible, reducing the entropy of the water molecules. When the oil
separates from the water, the water molecules are free to move about as usual and the entropy
of the water molecules increases.
Follow-up discussion:
Discuss Figure 8.16, focusing on how water molecules orient themselves around non-polar
solutes.
NOTE: Knowledge of the orientation of water molecules around ions and at interfaces (between
water and air and water and nonpolar molecules) is growing as more techniques for studying the
interactions experimentally become available and computational models become better. The
authors of one study, Water at Hydrophobic Surfaces: Weak Hydrogen Bonding and Strong
Orientation Effects, L. F. Scatena, M. G, Brown, and G. L. Richmond, Science 2001, 292, 908912 (4 May 2001), say, Vibrational studies that selectively probe molecular structure at
CCl4/H2O and hydrocarbon/H2O interfaces show that the hydrogen bonding between adjacent
21
Chapter 8
water molecules at these interfaces is weak However, interactions between these water
molecules and the organic phase result in substantial orientation of these weakly hydrogenbonded molecules in the interfacial region. This finding is consistent with the idea that the
driving force in the interaction of water with hydrophilic fluid surfaces (such as proteins,
membranes, and micelles) is a large entropy loss (when the water is associated with the
hydrophobic molecules) due to enhanced structuring of water in the immediate vicinity of
apolar molecules, biological macromolecules, and hydrophobic surfaces. The enhanced
structuring may be orientation caused by interaction with the hydrophobic molecules, rather
than more a ice-like structure for the water molecules in the vicinity of the hydrophobic
molecules, as is often assumed in models of these interactions. This study looked at the
vibrational spectra of water, in particular the OH bonds and interpreted them as being in
several different environments, as shown in the figure below. In the figure, hydrogen-bonding
interactions of OH with other water molecules are shown as dashed lines and interactions with
the hydrophobic molecules (CCl4 in this case) are dotted. (Free OH in the diagram means not
hydrogen bonded to another water.) The infrared absorptions attributed to each environment are
shown below the drawing; these were used to analyze the experimental data and determine the
relative numbers of water molecules at the interface that were in each environment.
Follow-up Activities:
End of chapter problems 8.60 through 8.62.
22
Chapter 8
Explain in words, equations, diagrams, and/or molecular-level sketches the origin and
direction of positional and thermal entropy changes for formation of micelles and
phospholipid bilayer membranes by ambiphilic molecules.
Use words and/or molecular level sketches to describe the structure and properties of micelles,
bilayer membranes, and liposomes.
Connect the formation of organized collections of molecules to increases in positional and/or
thermal entropy in the system and surroundings that drive the organization.
Investigate This 8.37. How does light interact with solutions?
Goal:
Compare what is observed when a beam of light passes through a sugar solution and a detergent
solution.
Set-up time:
15 minutes, if the solutions are prepared before class, or less than 5 minutes, if you prepare
the solutions in class.
Time for activity:
Less than 5 minutes.
Materials:
2 transparent, colorless plastic or glass containers. One possibility is 2-liter clear, colorless
plastic soda bottles with the top 1/3 of the bottles removed, as shown in the set-up below.
2 Stirrers.
"Maglite" type flashlight or other source of a beam of light. A laser pointer will work.
Ring stand with clamp to hold the light source.
Reagents:
Table sugar.
Liquid detergent or soap.
Water.
Procedure:
You can prepare both solutions before class, but this lessens the impact of the activity, which
is enhanced by seeing how little detergent is required to produce enough micelles to make the
solution scatter light quite well.
To one container, add about a teaspoon of sugar. Fill the container with water. Use a stirrer to
mix the solution.
To the other container, add one drop of detergent. Fill the container with water. Use a
different stirrer to mix the solution very gently, so as not to produce any foam. Although the
stirrer used for the sugar could be used to stir the detergent solution, you do not want to use
the detergent stirrer for the sugar. It is best simply to have two stirrers, one for each solution
and not mix them up.
Allow both solutions to sit undisturbed for several minutes. If the solutions are made before
class, they will need to sit undisturbed again after being transported to class.
Set up a container and light source as shown below.
Darken the room and direct a narrow beam of light through one of the solutions from the side.
Use a small flashlight with a focused beam or a larger flashlight with the lens masked so only
a small beam of light escapes. Have a student volunteer observe from the top of the solution.
Repeat the observation with the other solution. Placing both solutions in the light beam, with
the sugar solution preceding the detergent solution, produces a nice effect.
23
Chapter 8
Anticipated results:
These photographs show the set up of light source and solution and top and side views of the
light beam passing through the container of detergent solution.
set up
top view
side view
The sugar solution will show the same scattering by the container surfaces (bright spots in
these photos), but will show no light scattering by the solution. The light beam will not be
visible in the solution.
Follow-up discussion:
Use Consider This 8.38 to initiate discussion of the results of this activity.
Follow-up activities:
Check This 8.39. Evidence for micelle formation.
Consider This 8.40. How do ambiphilic molecules interact with nonpolar solutes
Consider This 8.41. How do the properties of bilayer membranes help explain osmosis?
End of chapter problems 8.68 through 8.73.
Consider This 8.38. What causes light to interact with a solution?
Goal:
Conclude that the detergent solution in Investigate This 8.37 contains clumps of solute
molecules that scatter light, but the sugar solution does not.
Classroom options:
Allow students, working in small groups, 3-4 minutes to discuss their interpretation and then
have groups share their conclusions with the class.
This activity could be conducted as an open class discussion.
Time for activity:
About 5-10 minutes.
Instructor notes:
Show or refer students to Figure 8.19 that displays different representations of a detergent
molecule. These can be used to discuss the structure of these molecules with hydrophilic and
hydrophobic parts, leading into micelle formation and phospholipid bilayers.
Remind students that they have seen ambiphilic molecules before in Chapter 2, Section 2.2,
Investigate This 2.5 (reference incorrectly given as 2.3 in the text), where we found they had
limited water solubility.
Students should reason and conclude:
When the beam of light passed through the sugar solution, the light beam was essentially
invisible, because all the light rays continued straight through the solution without
interference.
24
Chapter 8
When the light beam passed through the detergent solution, the beam was easily seen,
because something was causing some of the rays of light to be scattered toward your eyes
instead of continuing straight through the solution. Possibly the detergent molecules clump
together to form large enough particles to interfere with and scatter the light. This light
scattering is called the Tyndall effect and is used to study solutions of large biological
molecules, polymers, and solutions in which the molecules clump, as here.
Follow-up discussion:
Use the molecular structure of a detergent molecule shown in Figure 8.19 to lead into the
discussion of micelles.
Follow-up activities:
Check This 8.39. Evidence for micelle formation.
Consider This 8.40. How do ambiphilic molecules interact with nonpolar solutes?
Consider This 8.41. How do the properties of bilayer membranes help explain osmosis?
End of chapter problems 8.68 through 8.73.
Consider This 8.40. How do ambiphilic molecules interact with nonpolar solutes?
Goal:
Sketch a model of the interactions between water, ambiphilic detergent, and oil molecules that
is based on knowledge of micelle formation and the results from Investigate This 8.35(b).
Classroom options:
Allow students, working in small groups, approximately 5 minutes to complete this activity
and then have groups share their sketches with the class on the chalkboard or overhead
transparencies.
This activity could also be assigned as homework and discussed at the next class session.
Time for activity:
About 10 minutes.
Instructor notes:
Show or refer students to Figure 8.19 for different examples of detergent molecule
representations as they are doing this activity.
Students should sketch a drawing similar to:
25
Chapter 8
Follow-up discussion:
The discussion should focus on how detergents work.
Then, lead into phospholipid bilayers and how molecules are transported through these
bilayers.
Follow-up activities:
Consider This 8.41. How do the properties of bilayer membranes help explain osmosis?
End of chapter problems 8.68 through 8.73.
Consider This 8.41. How do the properties of bilayer membranes help explain osmosis?
Goal:
Relate osmosis (Investigate This 8.1), which requires a semipermeable membrane, to the
relative permeabilities of the bilayer membranes that surround all cells.
Classroom options:
Allow students, working in small groups, about 3 minutes to formulate their explanations and
then have groups share them with the class.
This activity could be conducted as an open class discussion.
This activity could also be assigned as homework and discussed at the next class session.
Time for activity:
About 7-10 minutes.
Instructor notes:
If necessary review the set up and results of Investigate This 8.1 and the concept of osmosis.
Show or refer students to Table 8.1 as they carry out this activity and discussion.
Students should reason and conclude:
It is clear from Table 8.1 that water has the highest relative membrane permeability of all the
substances shown. Thus, we can consider lipid bilayer membranes as semipermeable (highly
permeable to water, but not to solutes in water, such as sugars). Semipermeable lipid bilayer
membranes through which water can pass relatively easily surround the cells in a carrot. The
cells next to the cavity in the carrot, Investigate This 8.1, contain solutes at lower a
concentration than the concentrated sugars in the syrup, so water passes from the cells into
the cavity, increasing the volume of syrup, which we observe as a rise in the liquid level in
the external column connected to the cavity. As these cells lose water to the cavity, the
solutes in them become more concentrated and osmosis can occur from the next layer of cells
to dilute the solution in the first layer, and so on and on until osmosis moves water from the
beaker into the outer layer of cells.
Follow-up activities:
End of Chapter problems 8.72 and 8.73.
26
Chapter 8
Use positional entropy changes and the relative thermal entropy changes for the same energy
change at different temperatures to analyze and predict the direction of phase changes in pure
compounds and solutions.
Calculate freezing point lowering and boiling point elevation for solutions.
Use experimental values for colligative properties to determine the concentration of solutes in
the solution and/or the molar mass of the solute.
Investigate This 8.42. What is the freezing point of salt water?
Goal:
Compare the freezing point of an ice-salt-water mixture with the temperature of an ice-water
mixture.
Set-up time:
Approximately 10 minutes.
Time for activity:
About 5-10 minutes.
Materials:
250-mL beaker.
Wooden stirrer.
Thermometer or temperature probe whose reading can be projected.
Reagents:
Crushed ice.
Water
Approximately 90 g of Kosher salt, NaCl, or coarsely crushed rock salt. Table salt and reagent
grade sodium chloride tend to clump and be hard to mix with the ice-water mixture.
Procedure:
Use two student volunteers to carry out the activity. One will hold the beaker, add the ice,
water and salt, and stir the mixture and the other will hold the thermometer or probe in the
mixture and read the thermometer. Direct the students to carry out these actions.
Fill the beaker with ice and add the water.
Use the stirrer to stir the mixture vigorously.
Insert the thermometer in the mixture.
When the temperature of the mixture is constant for about 30 seconds (while being more
gently stirred), read and record (all students) the temperature.
Remove the thermometer, add the salt, and continue vigorous stirring for 2-3 minutes.
Insert the thermometer in the middle of the mixture and read and record (all students) the
temperature.
Clean-up:
Dispose mixture down the drain.
Anticipated results:
Temperature reading of the ice-water mixture: 0 C.
Temperature reading of the ice-salt-water mixture: about 15 C.
Follow-up discussion:
Use Consider This 8.43 to initiate discussion of the results of this activity.
Follow-up activities:
Worked Example 8.44--Determining a freezing point lowering constant.
Check This 8.45--Determining molar mass of a solute from freezing point lowering.
Worked Example 8.46--Freezing point lowering by an ionic solute.
ACS Chemistry FROG
27
Chapter 8
Consider This 8.47--Is the entropy change larger for boiling a solution or pure solvent?
Check This 8.48--Boiling point of a solution.
End of chapter problems: 8.69-8.81.
Consider This 8.43. How does salt affect the freezing point of water?
Goal:
Consider how to relate the lower freezing point of an ice-water-salt solution to the difference in
entropy between a salt solution and pure water.
Classroom options:
Allow students, working in small groups, approximately 5 minutes to consider the possible
relationship between the temperature lowering and the different entropies of the water and
solution and then have groups share their suggestions with the class.
This activity could be conducted as an open class discussion.
Time for activity:
From 10 to 20 minutes, depending on how much of the entropy analysis you wish to
incorporate in the discussion.
Instructor notes:
Be sure the class agrees on the results from Investigate This 8.42.
Discuss what the solid is that is formed when an aqueous salt solution begins to freeze. Many,
perhaps most, students will not know that the solid is pure water ice. Since this knowledge is a
key to understanding the analysis of this (and other colligative properties), its important that
students get it before thinking about the results of Investigate This 8.42.
Students should reason and conclude:
(a) Before adding the salt, the temperature was approximately 0 C, but once the salt was
added, the temperature dropped to about 15 C.
(b) The entropy of the salt solution is greater than the entropy of pure water. The entropy of
the solid water formed by freezing is the same in both cases. Since the entropy of the solution
is higher than the entropy of the pure solvent, the positional entropy change for freezing ice
from the solution will be greater than that for freezing from the pure solvent. More analysis is
necessary to figure out how this will affect the temperature of the freezing process.
Follow-up discussion:
Discuss the positional entropy change for freezing solid from a pure solvent such as water
with the positional entropy change for freezing the same pure solid from a solution. Show or
refer students to Figure 8.26 as a graphical representation of the difference\.
Use this discussion as an introduction to colligative properties and lead eventually to how we
quantify freezing point lowering.
Follow-up Activities:
Worked Example 8.44. Determining a freezing point lowering constant.
Check This 8.45. Determining molar mass of a solute from freezing point lowering.
Worked Example 8.46. Freezing point lowering by an ionic solute.
Consider This 8.47. Is the entropy change larger for boiling a solution or pure solvent?
Check This 8.48. Boiling point of a solution.
End of chapter problems 8.69 through 8.81.
28
Chapter 8
Consider This 8.48. Is the entropy change larger for boiling a solution or pure solvent?
Goal:
Extend knowledge of colligative properties to include an entropy analysis of boiling point
elevation.
Classroom options:
Allow students, working in small groups, 5-7 minutes to sketch the entropy level diagram and
consider the implications for the difference in boiling points of a pure solvent and solution of
nonvolatile solute and then have groups share their suggestions with the class.
This activity could be conducted as an open class discussion, although it is better for
assessment purposes to see how students do in their groups.
Time for activity:
About 10-15 minutes.
Instructor notes:
Show or refer students to Figure 8.26, so they can use it as a guide to draw a similar figure for
boiling point elevation.
Show or refer students to equation (8.36), so they have the relationships, Sgas > Ssolution >
Ssolvent, in front of them as they think about this analysis.
Students should reason and conclude:
(a) The relationships in expression (8.36) are represented on this entropy-level diagram.
(b) The diagram in part (a) shows us that Ssolventgas > Ssolutiongas. An analysis like that for
freezing point lowering again begins by setting the free energy equal to zero (equilibrium) in
the relationship to enthalpy, entropy, and temperature to yield:
Hsolventgas = (Tsolventgas)Ssolventgas
Hsolutiongas = (Tsolutiongas)Ssolutiongas
Equating the enthalpy changes and rearranging the equation gives:
Ssolvent gas
Tsolutiongas
=
Ssolutiongas
Tsolvent gas
29
Chapter 8
Ssolvent gas
Ssolutiongas
> 1, so
Tsolutiongas
Tsolvent gas
that (Tsolutiongas) > (Tsolventgas). Thus the boiling point of the solution is higher than the
boiling point of the pure solvent. The affect of the solute is to raise the boiling point.
Follow-up Discussion:
Use the discussion to introduce equation (8.37), Tbp = kbpm, the boiling point elevation
relationship analogous to the one for freezing point lowering.
Follow-up Activities:
Check This 8.48. Boiling point of a solution.
End of chapter problems 8.69 through 8.81.
Solid
Pure Solvent
Solution
Which has the highest entropy of the three? _______. Which has the lowest entropy?________
30
Chapter 8
Label the three lines (solid, solvent, solution) on the figure below. Draw an arrow (labeled S)
representing the entropy change when pure solvent freezes. Draw an arrow (labeled S*)
representing the entropy change when the solution freezes. Which change has the larger
magnitude? [Note that when the "solution" freezes, it is actually only the solvent that "freezes"
out.]
31
Chapter 8
32
Chapter 8
The imagined process is not favored because the number of distinguishable arrangements in the
final state is lower than in the initial state. This process corresponds to a transfer of thermal
energy from a cooler to a warmer object. We do not observe a warm object getting warmer when
it is placed in contact with a cooler object.
Check This 8.11. Direction of positional entropy changes
(a) Ice melting is accompanied by an increase in positional entropy. The liquid has more
distinguishable arrangements than the solid.
(b) Forming a cloud of tiny liquid water droplets from water vapor is accompanied by a
decrease in positional entropy. Water vapor in the air (a gas) has many more distinguishable
arrangements than the liquid water droplets found in a cloud.
(c) When equal volumes of ethanol and water are mixed, there is an increase in positional
entropy. In the mixture, each liquid has about twice the original volume to move about in.
(Actually, a mixture of equal volumes of ethanol and water has a volume about 5% less than the
total of the original volumes.)
(d) In transferring water from a graduated cylinder to a beaker, the positional entropy remains
the same. There is no change in the volume of the liquid. (Changing the shape of the liquid
sample does not change its volume.)
(e) The positional entropy increases as a piece of solid dry ice sublimes to form carbon dioxide
gas. There is a phase change from a solid to a gas, thus greatly increasing the distinguishable
arrangements of the carbon dioxide molecules.
(f) In forming polyethylene from ethene molecules, the positional entropy decreases. Individual
ethene molecules have many more distinguishable arrangements than a polymerized chain of
polyethylene where the molecular units are not free to move independently of one another, so
effectively have lower volumes to move in.
Check This 8.13. Net entropy change for water freezing
At T < 273 K, liquid water will freeze, so energy will leave the ice-water mixture and enter the
block of metal (surroundings). Thus, the energy of the metal increases and Ssurr ls > 0, as
shown by the upward pointing red arrow for the thermal entropy change in Figure 8.12. Ice has
fewer distinguishable arrangements than water, so the positional entropy of the system, the icewater mixture, decreases when freezing occurs: Ssys ls < 0. This is shown in Figure 8.12 by
the downward pointing blue arrow representing the positional entropy change.
(b) In order for Snet ls = Ssys ls + Ssurr ls > 0, we must have |Ssurr ls| > |Ssys ls|, so
that the combination of positive Ssurr ls and negative Ssys ls is positive.
Check This 8.16. Net entropy change for freezing water with surroundings at 263 K
At 263 K, liquid water will freeze, so energy will leave the ice-water mixture and enter the
block of metal. The thermal entropy of the block (surroundings) will increase:
3
1
Hsurr
6.00 10 J mol
Ssurr =
=
= 22.8 Jmol1K1
T
263 K
The positional entropy change for the system, water freezing to ice is:
Ssyst = Sls = 22.0 JK1mol1
Thus, we have:
Snet = Ssyst + Ssurr = (22.0 JK1mol1) + (22.8 Jmol1K1) = 0.8 Jmol1K1
33
Chapter 8
This positive value for the net entropy change predicts that this process is spontaneous and will
be observed. We know that liquid water in thermal contact with surroundings at T < 273 K will
freeze, so this prediction is borne out by our observation of freezing water.
Check This 8.19. Formation of N2O4(g) under standard conditions at 350 K
The net entropy change for the formation of N2O4(g) from NO2(g) under standard conditions at
350 K (using values for Hsystem and Ssystem from Worked Example 8.18) is:
Hsystem
57.2 10 3 J
1
1
Snet = Ssystem
= 175.8 JK
= 175.8 JK + 163.4 JK
T
350 K
1
34
Chapter 8
Rearranging equation (8.23), which gives the relationship among, T, Ho, and So for a phase
change at its equilibrium temperature, we get:
H o
T=
So
So for freezing liquid benzene under standard conditions, we have:
10.6 10 3 J mol 1
H o freeze
Tfreeze =
=
= 279 K
So freeze
38 J K 1 mol 1
The freezing point probably should be given to only two significant figures ( about 2%), 280
K, because the change in entropy is only known to this accuracy. This calculated value is very
close to the experimental value of 278.5 K given in Table 8.1.
Check This 8.27. Predict the direction of the entropy change for glucose fermentation
We expect the entropy change for glucose fermentation to be positive and relatively large since
the products are two moles of liquid and two moles of gas produced by one mole of solid
reactant. The products will have many more distinguishable arrangements than the solid
reactant.
Check This 8.28. Entropy change for glucose fermentation
We use equation (8.24) to find the standard entropy change for glucose fermentation from the
values in Appendix B:
Sreaction = [nj(S)j]products [nj(S)j]reactants
Sreaction = {[(2 mol C2H5OH)(160.7 JK1mol1)] + [(2 mol CO2)(213.7 JK1mol1)]}
[(1 mol C6H12O6)(212.1 JK1mol1)]
Sreaction = 536.7 JK1
The calculated value for Sreaction is large and positive, which agrees with our prediction in
Check This 8.27.
Check This 8.30. Free energy change for fermentation of glucose
We will use equation (7.30) to find the standard enthalpy change for glucose fermentation from
the values in Appendix B and combine this with the standard entropy change from Check This
8.28 to find the standard free energy change for glucose fermentation.
Hreaction = [nj(Hf)j]products [nj(Hf)j]reactants
Hreaction = {[(2 mol C2H5OH)(277.7 kJmol1)] + [(2 mol CO2)(393.5 kJmol1)]}
[(1 mol C6H12O6)(1274.4 kJmol1)]
Hreaction = 68.0 kJ
Hence,
Greaction = Hreaction TSreaction = 68.0 103 J (298 K)(536.7 JK1)
Greaction = 227.9 kJ
We expect this reaction to proceed under standard conditions due to the large, negative value for
Greaction.
35
Chapter 8
36
Chapter 8
Check This 8.45. Determining molar mass of a solute from freezing point lowering
(a) We can use the freezing point lowering equation (8.35) together with the freezing point and
the freezing point lowering constant for benzene from Table 8.2 to calculate the freezing point
lowering by this solute and then the molality of the solution. The freezing point lowering for the
solution is
Tfp = (5.12 C) (5.50 C) = 0.38 C
Using this value and kfp = -5.12 Cm1 for benzene, we can get the molality of the solution:
Tfp
0.38 o C
m=
=
= 0.074 m
kfp
5.12 o C m 1
(b) We express the solute molality as moles of solute, n, per kilogram of solvent, solve for
moles of solute, and use this result and the mass of solute dissolved to get its molar mass.
n
m = 0.074 molkg1 =
7.567 10 3 kg
n = (0.074 molkg1)(7.567 103 kg) = 5.6 104 mol
0.243 g
molar mass =
= 4.3 102 gmol1
4
5.6 10 mol
Check This 8.47. Freezing point lowering by a polar solute in a nonpolar solvent
(a) The freezing point lowering of the solution of ethanoic (acetic) acid in benzene is:
Tfp = Tfp(solution) Tfp(benzene) = (3.96 C) (5.50 C) = 1.54 C
Rearrange the freezing point lowering equation (8.35) to find the molality based on this freezing
point lowering:
Tfp
1.54 o C
=
= 0.301 m
m=
kfp
5.12 o C m 1
(b) The result in part (a) is less than the molality of the solution whose freezing point was
measured. This result suggests that there are fewer particles in the solution than would be
present in a 0.50 m solution. Hydrogen bonding between the ethanoic acid molecules could
reduce the number of individual ethanoic acid molecules in solution. The hydrogen-bonded
structure between two carboxylic acid molecules shown in Problem 8.54 for methanoic (formic)
acid is likely as well for ethanoic acid in this solution. If all the molecules formed these dimers,
the freezing point lowering would be that for a 0.25 m solution. Since more particles are
actually present, there is probably an equilibrium reaction between monomers and dimers, as
shown in Problem 8.54.
Check This 8.49. Boiling point of a solution
We can use the boiling point elevation equation (8.37) and the data in Table 8.3 to find the
boiling point elevation and hence the boiling point of the solution.
Tbp = kbpm = (2.53 Cm1)(0.25 m) = 0.63 C
Tbp(solution) = Tbp(benzene) + Tbp = (80.0 C) + (0.63 C) = 80.6 C
Check This 8.51. Osmotic pressure of an ionic solution
Use equation (8.38) for osmotic pressure with c = 1.0 M to account for the dissociation of NaCl:
= (1.0 M)(0.08205 atmLmol-1K-1)(293 K) = 24 atm
37