FROG Chapter08 PDF

Chapter 8.
Entropy and Molecular Organization

Faculty Resource and Organizational Guide (FROG)
Table of Contents
Materials for Chapter 8 Activities................................................................................................3
Reagents for Chapter 8 Activities: ...............................................................................................4
Introduction and References for Entropy ...................................................................................5
References:...................................................................................................................................6
Section 8.1. Mixing and Osmosis .................................................................................................6
Learning Objectives for Section 8.1 ............................................................................................6
Investigate This 8.1. Does water move through a hollow carrot filled with syrup? ...................6
Student Report Sheet for Investigate This 8.1 .............................................................................8
Consider This 8.2. What direction does water move through a hollow carrot?..........................9
Section 8.2. Probability and Change ...........................................................................................9
Learning Objectives for Section 8.2 ............................................................................................9
Consider This 8.3. What is the probability of change?...............................................................9
Section 8.3. Counting Molecular Arrangements in Mixtures .................................................11
Learning Objectives for Section 8.3 ..........................................................................................11
Investigate This 8.4. How are distinguishable arrangements counted? ....................................11
Section 8.4. Implications for Mixing and Osmosis in Macroscopic Systems.........................12
Section 8.5. Energy Arrangements Among Molecules ............................................................13
Investigate This 8.7. How is a different kind of distinguishable arrangement counted?..........13
Section 8.6. Entropy....................................................................................................................15
Section 8.7. Phase Changes and Net Entropy...........................................................................15
Consider This 8.10. What are the relative probabilities of different phases? ...........................15
Consider This 8.12. What happens in an ice-water mixture at different temperatures?...........16
Consider This 8.14. How does thermal entropy change depend upon temperature?................17
Consider This 8.17. What are net entropy changes for ice and water changes at 273 K? ........18
Section 8.8. Gibbs Free Energy..................................................................................................19
Section 8.9. Thermodynamic Calculations for Chemical Reactions ......................................19
Section 8.10. Why Oil and Water Dont Mix............................................................................20
Learning Objectives for Section 8.10 ........................................................................................20
Investigate This 8.35. What happens when oil and water are mixed?......................................20
Consider This 8.36. Why don't oil and water mix? ..................................................................21
ACS Chemistry FROG
Chapter 8
Section 8.11. Ambiphilic Molecules: Micelles and Bilayer Membranes ................................22

Investigate This 8.37. How does light interact with solutions? ................................................23
Consider This 8.38. What causes light to interact with a solution?..........................................24
Consider This 8.40. How do ambiphilic molecules interact with nonpolar solutes?................25
Consider This 8.41. How do the properties of bilayer membranes help explain osmosis? ......26
Section 8.12. Colligative Properties of Solutions......................................................................26
Investigate This 8.42. What is the freezing point of salt water?...............................................27
Consider This 8.43. How does salt affect the freezing point of water? ....................................28
Consider This 8.48. Is the entropy change larger for boiling a solution or pure solvent?........29
Section 8.13. Osmotic Pressure Calculations............................................................................30
Section 8.14. The Cost of Molecular Organization ..................................................................30
Section 8.16. ExtensionThermodynamics of Rubber...........................................................30
Worksheet on Section 8.12 and Rubber-Band Thermodynamics..............................................30
Solutions for Chapter 8 Check This Activities...........................................................................32
Check This 8.5. Unmixing ........................................................................................................32
Check This 8.6. Transfer of solvent from solution to pure solvent ..........................................32
Check This 8.9. Energy transfer from a cooler to a warmer solid ............................................32
Check This 8.11. Direction of positional entropy changes.......................................................33
Check This 8.13. Net entropy change for water freezing .........................................................33
Check This 8.16. Net entropy change for freezing water with surroundings at 263 K ............33
Check This 8.19. Formation of N2O4(g) under standard conditions at 350 K ..........................34
Check This 8.20. Criterion for direction of change ..................................................................34
Check This 8.22. Free energy change for urea formation at 325 K..........................................34
Check This 8.24. Significance of the graphical relationship of H, TS, and G vs. T .....34
Check This 8.25. The melting point of benzene .......................................................................34
Check This 8.27. Predict the direction of the entropy change for glucose fermentation..........35
Check This 8.28. Entropy change for glucose fermentation.....................................................35
Check This 8.30. Free energy change for fermentation of glucose ..........................................35
Check This 8.32. Free energy change for fermentation of glucose ..........................................36
Check This 8.34. Free energy change for dissolving barium carbonate...................................36
Check This 8.39. Evidence for micelle formation ....................................................................36
Check This 8.45. Determining molar mass of a solute from freezing point lowering..............37
Check This 8.47. Freezing point lowering by a polar solute in a nonpolar solvent..................37
Check This 8.49. Boiling point of a solution............................................................................37
Check This 8.51. Osmotic pressure of an ionic solution ..........................................................37
ACS Chemistry FROG
Chapter 8
Materials for Chapter 8 Activities

Activity
Material
Quantity
8.1
1-liter beaker
8.1
Large fresh carrot, peeled
8.1
Cork borer or drill and drill

bit
8.1
Clear plastic drinking straw

or plastic transfer pipet with
a wide stem
8.1; 8.7
Wooden toothpicks
4; 2/group
8.1
Clay
8.1
9-inch Pasteur pipet
8.4; 8.7
Gum drops or similar soft

candy
1 package
8.35
Small test tube
1/group
8.35
Thin-stem plastic pipets
3/group
8.37`
Clear, colorless plastic or

glass containers
8.37
Stirrers
8.37
Flashlight or source of a
bright beam of light such as
a laser pointer
8.37
Ring stand with clamp
8.42
250-mL beaker
8.42
Wooden stirrer
8.42
Thermometer
ACS Chemistry FROG
Chapter 8
Reagents for Chapter 8 Activities:

Activity
Reagents
Quantity
8.1
Pancake syrup
40 mL.
8.35
Cooking oil
2 mL/group
8.35; 8.37
Liquid dishwashing
detergent
2 mL/group; few drops
8.37
Table sugar
1 packet
8.42
Crushed ice
400 mL
8.42
Coarse table salt, NaCl, or

Kosher salt
90 g
ACS Chemistry FROG
Chapter 8
Introduction and References for Entropy

Entropy is not about disorder. The opening few sentences of this chapter try to make clear that
there is an enormous amount of organization in the world around us and that much of this
organization arises in spontaneous processes where order not disorder is observed. Statements
about increases disorder (somehow equated with entropy) driving spontaneous change are
simplistic and incorrect. What this chapter (and an increasing number of other general chemistry
textbooks) emphasizes is that entropy is a measure of the spreadedness of energy in a system
and its surroundings. The more the energy is spread out, the higher the entropy. (Associating the
symbol, S, for entropy with spreadedness can help students keep the fundamental basis of
entropy in mind.)
The spread of energy is measured by the number of distinguishable arrangements (microstates)
of the available energy among the quantized energy levels of the system and surroundings.
Entropy is related to the number of distinguishable arrangements, W (sometimes denoted ), by
the Boltzmann definition: S = k lnW. Our treatment is unique (at the general chemistry level) in
quantifying W in model systems that have a countable number of distinguishable arrangements
and then generalizing the results to macroscopic systems. (We take one liberty by treating the
spread of energy among the quantum levels in moving particles as arrangements of the particles
in space, because this is an easier model to visualize. The marginal note on page 517 calls
attention to this incorrect treatment and suggests trying end-of-chapter Problem 8.96 to see how
a correct treatment would work in a model system.) Faculty who have used this approach report
better student understanding and ability to use entropy analyses than observed with more
conventional approaches.
Another incorrect idea that we try to avoid in this textbook is any hint that there is a competition
between energy and entropy changes as driving forces for change or reaction. Its hard to
imagine a competition between two quantities that have different units. The units of entropy are
energy/K that arise via the Boltzmann constant (which along with the Planck constant) is
ubiquitous in treating atomic-molecular level systems. The units reflect the spreadedness of
energy, which is a function of the temperature of the system. The idea of a competition surely
arises via the usual formulation for the free energy change accompanying a change or reaction
in a system: G = H TS. However, the enthalpy term really accounts for the entropy
change in the thermal surroundings of the system, as pointed out in Section 8.8, so it is also
related to an entropy effect.
Entropy analyses of colligative properties (osmosis, freezing point lowering, and boiling point
elevation) and solubilities are an important part of this chapter. These changes are easily
observable, the analyses are relatively straightforward, and the consequences, especially for the
solubility of ambiphilic molecules, are important in many systems, including organisms. These
treatments may be somewhat unfamiliar, because these phenomena are not usually presented in
the context of entropy arguments, but this context provides a unifying theme for apparently
disparate phenomena. The introduction of free energy enables us to make more appropriate
statements about coupled reactions than we have made in previous chapters, where only
energies (enthalpies) were considered.
ACS Chemistry FROG
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
Section 8.1. Mixing and Osmosis

Learning Objectives for Section 8.1
Relate osmosis to mixing.
Describe the conditions required for osmosis and predict the direction of osmosis.
Investigate This 8.1. Does water move through a hollow carrot filled with syrup?
Goal:
Observe the increase in volume of sugar solution (syrup) in a hollowed-out carrot suspended in
pure water and interpret the change as a result of water moving through the cell membranes into
the concentrated sugar solution.
Set-up time:
30 minutes. This includes time to bore the hole in the carrot and fill the hole with syrup.
Time for activity:
50 minutes. Although an easily noticeable change in the height of the solution column occurs
in 20-30 minutes, most instructors simply leave the set up for the entire class period.
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ACS Chemistry FROG
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.
ACS Chemistry FROG
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:
ACS Chemistry FROG
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.]
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).
Section 8.2. Probability and Change

Relate the relative probability of two outcomes to the number of ways each outcome can be
achieved.
Consider This 8.3. What is the probability of change?
Goal:
Assign and explain the assignment of numerical values to the probability of familiar changes.
ACS Chemistry FROG
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:
(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.
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.
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ACS Chemistry FROG
Chapter 8
Section 8.3. Counting Molecular Arrangements in Mixtures

achieved.
Calculate the number of distinguishable arrangements of a small number of identical particles
(molecules) among a limited number of distinguishable locations and relate the results to a
solute-solvent mixing process.
Investigate This 8.4. How are distinguishable arrangements counted?
Goal:
Determine how many distinguishable arrangements three objects can have among five boxes
and (extended) three objects among six boxes.
Set-up time:
Approximately 10-15 minutes to prepare sets of identical objects.
Time for activity:
Approximately 10-15 minutes.
Materials:
Gumdrops, paper clips, coins, or other sets of identical objects. Alternatively, just marking
boxes in arrays drawn on a piece of paper will work and requires no preparation.
Procedure:
Allow 5-8 minutes for students, working in small groups, to find their arrangements. Then, the
groups can share their work with the class, summarizing the arrangements on the chalkboard
or an overhead transparency.
Results:
Ten distinguishable arrangements are possible:
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.
ACS Chemistry FROG
11
Chapter 8
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.
Section 8.4. Implications for Mixing and Osmosis in Macroscopic Systems

achieved.
Relate osmosis to mixing and be able to explain both in terms of increasing number of
distinguishable molecular arrangements.
Describe the conditions required for osmosis and predict the direction of osmosis.
Relate the results for countable systems to real systems.
12
ACS Chemistry FROG
Chapter 8
Section 8.5. Energy Arrangements Among Molecules

Determine the number of distinguishable arrangements of a small number of identical energy
quanta among a limited number of distinguishable atoms.
Predict the direction and final outcome of energy transfer between two systems containing a
countable number of energy quanta distributed among a countable number of distinguishable
atoms.
Relate the results for countable systems to real systems.
Investigate This 8.7. How is a different kind of distinguishable arrangement counted?
Goal:
Determine how to arrange two identical energy quanta among four distinguishable atoms in a
solid and (extended) three energy quanta among four distinguishable atoms.
Set-up time
Approximately 10 minutes to prepare packets of gum drops and toothpicks, if they are to be
used.
Time for activity:
From less than 10 minutes to 20 minutes depending upon the amount of discussion
incorporated with the activity.
Materials:
Gumdrops or other soft candies.
Toothpicks.
NOTE: For distribution to small groups of students, place four gumdrops and two toothpicks in
enough zip-closure plastic bags to supply your class. Alternatively, this can be a pencil-andpaper activity, as shown below and exemplified by Figure 8.8.
Procedure:
As with Investigate This 8.4, allow students, working in small groups, 8-10 minutes to
complete this activity. Then, the groups can share their work with the class, summarizing the
arrangements on the chalkboard or an overhead transparency.
If gumdrops and toothpicks are not available, students can use "{" to represent an atom and
"()" to represent an energy quantum, as in Figure 8.8. Even more efficiently, the arrangements
can be represented by numbers of quanta as shown in the right-hand column of the figure in
the activity, in Figure 8.8, and the figures below.
Anticipated results:
In this table, as in Figure 8.8, the "{" represents an atom and each "()" represents an energy
quantum. In terms of the activity with real objects, the "{" represents a gumdrop and "()"
represents toothpicks. There are 10 ways to distribute the two identical quanta among four
distinguishable atoms:
atom
#1
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
ACS Chemistry FROG
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
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.
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.
14
ACS Chemistry FROG
Chapter 8
Section 8.6. Entropy

Use the definition of entropy in terms of distinguishable arrangements to show how entropies
for the parts of a system are additive while numbers of arrangements are multiplicative.
Combine positional and thermal entropy changes for a process in a system and its
surroundings to determine the net entropy change for the process.
Section 8.7. Phase Changes and Net Entropy

Use the definition of entropy in terms of distinguishable arrangements to predict the relative
entropies of different systems, for example, phases of matter or reactants and products of a
reaction.
Combine positional and thermal entropy changes for a process in a system and its
surroundings to determine the net entropy change for the process.
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.
State the criterion for equilibrium in chemical systems and relate the state of equilibrium to
the positional and thermal entropy changes occurring.
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.
Consider This 8.10. What are the relative probabilities of different phases?
Goal:
Extend knowledge of probability and change to phase changes.
Classroom options:
Allow students, working in small groups, 3-5 minutes to complete this activity. Then, the
groups can share their work with the class, summarizing their drawings on the chalkboard or
an overhead transparency.
Time for activity:
Approximately 10 minutes.
Instructor notes:
Remind the class about phase changes, which were introduced in Chapter 1.
The reasoning here involves only arrangements of particles (what we are calling positional
entropy) and neglects the energy involved in the changes. If students recall the energy
arguments from Chapter 1, use this as a lead-in to the remainder of the section, which is
largely focused on the energy and thermal entropy changes.
(a) The square representing the volume available to a solid phase molecule should be about
the size of a molecule represented in the diagram. The square representing the volume
available to a liquid phase molecule should be about the size of the array of liquid phase
molecules represented in the diagram. The square representing the volume available to a gas
phase molecule should be about the size of the array of gas phase molecules represented in
the diagram and could be even larger, since gases expand to fill all of whatever container
ACS Chemistry FROG
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Chapter 8
they occupy. If number of molecular arrangements is proportional to the volume available to

a molecule, then the gas phase has the largest number of arrangements available. The relative
probabilities, based on number of arrangements available decreases in the order: gas phase >
liquid phase > solid phase.
(b) The animations and the interactive questions in the Web Companion, Chapter 8, Section
8.7, pages 1-3, reinforce the ideas stated in part (a). The solid has the smallest positional
entropy (smallest number of molecular arrangements), because the volume available to each
molecule is limited to a small fixed volume around its position in the lattice. For the gas
molecules, the volume available is limited to the volume of the container. A gas, therefore,
has the largest positional entropy (the largest number of molecular arrangements).
Try to be sure that the class understands the dilemma posed by their conclusions in this
activity, which so far ignore the energy associated with phase changes. Use the dilemma as a
lead-in to discuss the role of thermal entropy in phase changes.
Check This 8.11. Direction of positional entropy changes.
Consider This 8.12. What happens in an ice-water mixture at different temperatures?
Consider This 8.12. What happens in an ice-water mixture at different temperatures?
Goal:
Based on their experience, students explain what occurs in an ice-water mixture at different
temperatures and relate the results to the direction of energy transfer.
Classroom options:
Allow students, working in small groups, 3-5 minutes to discuss their responses and then have
the groups share them with the class. You could assign half the groups to part (a) and the other
half to part (b).
Time for activity:
From 5 to 15 minutes depending on how much of the preceding and succeeding ideas get
incorporated in the discussion.
Instructor notes:
In this activity students should connect phase changes with the enthalpy changes in the system
and surroundings.
In the discussion, students should use the enthalpy changes in the surroundings (thermal
reservoirthe block of metal) to reason about the direction of the entropy changes in the
surroundings.
(a) For T > 273 K, the ice in the ice-water mixture will melt. This means that energy must
leave the block of metal and enter the ice-water mixture. [Since the surroundings lose energy,
Ssurr < 0.]
(b) For T < 273 K, the water in the ice-water mixture will freeze. This means that energy
must leave the ice-water mixture and enter the block of metal. [Since the surroundings gain
energy, Ssurr > 0.]
16
ACS Chemistry FROG
Chapter 8
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.
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?
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.
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.
(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.
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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
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.
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.
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.
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.
(a) The calculations are just as in Worked Example 8.15, except that here T = 273 K:
18
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Chapter 8

Ssystem = Ssl = 22.0 JK1mol1
Ssurr =
3
1
Hsurr
6.00 10 J mol
=
= 22.0 JK1mol1
Tsurr
273 K
Snet = Ssystem + Ssurr = 22.0 JK1mol1 + (22.0 JK1mol1) = 0.0 JK1mol1

The net entropy change is not greater than zero, so you would not expect the ice to
melt.
(b) The calculations are just as in Check This 8.16, except that here T = 273 K:
Ssystem = Sla = 22.0 JK1mol1
Ssurr =
3
1
Hsurr
6.00 10 J mol
=
= 22.0 JK1mol1
Tsurr
273 K
Snet = Ssystem + Ssurr = 22.0 JK1mol1 + 22.0 JK1mol1 = 0.0 JK1mol1

The net entropy change is not greater than zero, so you would not expect the water to
freeze. [The results from parts (a) and (b) show that neither the ice nor the water is
favored at 273 K. An ice-water system is in equilibrium at this temperature.]
Discuss phase equilibria and the fact there is no driving force for change in either direction at
the equilibrium temperature.
Section 8.8. Gibbs Free Energy

State the criterion for equilibrium in chemical systems and relate the state of equilibrium to
the positional and thermal entropy changes occurring.
Explain the relationship of Gibbs free energy change to net entropy change for a process and
use the sign and/or magnitude of either one to predict whether the process is possible, not
possible, or in equilibrium.
Calculate the free energy change for a process in a system using values for the enthalpy and
entropy changes for the process.
Section 8.9. Thermodynamic Calculations for Chemical Reactions

reaction.
Distinguish between positional and thermal entropy changes for a process and combine them
to determine net entropy change for the process.
Explain the relationship of Gibbs free energy change to net entropy change for a process and
use the sign and/or magnitude of either one to predict whether the process is possible, not
possible, or in equilibrium.
ACS Chemistry FROG
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.
Section 8.10. Why Oil and Water Dont Mix

entropies of different systems, for example, solutions and separated solute and solvent.
Explain in words, equations, diagrams, and/or molecular-level sketches the origin and
direction of positional and thermal entropy changes for dissolving ionic and molecular solutes
in water and predict the observable outcomes.
Investigate This 8.35. What happens when oil and water are mixed?
Goal:
Compare the results of mixing oil and water to the results of mixing oil, water and detergent.
Set-up time:
Approximately 10-15 minutes to prepare a set of materials and reagents for each group, if you
are going to have groups do the activity. Use a paper or plastic cup for each set, so spills are
minimized when the sets are collected after use, and include a paper towel or napkin with each
set.
Time for activity:
Less than 10 minutes.
Materials:
One small test tube.
Three thin-stem plastic pipets.
Reagents:
Cooking oil (clear, pale yellow) in a labeled thin-stem plastic pipet.
Water in a labeled thin-stem plastic pipet.
Liquid dishwashing detergent in a labeled thin-stem plastic pipet.
Procedure:
Either pass out sets of materials and reagents to small groups or ask for a student volunteer to
do the activity for the class. Give the following instructions:
Place a few milliliters of water in the test tube.
Add about 0.5 mL of oil.
Cap the tube with a finger and mix by inverting several times.
Allow the tube to sit for several seconds.
Note your observations.
Add about 0.5 mL of the detergent to the test tube.
Cap the tube with your finger and mix by inverting several times. (Try not to create a lot of
suds.)
Allow the tube to sit for several seconds.
Note your observations.
NOTE: This activity can be scaled up for larger classrooms or projected via video.
20
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Chapter 8
(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.
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.
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.
Time for activity:
Instructor notes:
Review the results from Investigate This 2.5 as well as the succeeding discussion of the
insolubility of nonpolar solutes in water.
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.
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
ACS Chemistry FROG
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:
Section 8.11. Ambiphilic Molecules: Micelles and Bilayer Membranes

entropies of different systems, for example, solutions of hydrophobic molecules in water.
22
ACS Chemistry FROG
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.
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.
ACS Chemistry FROG
23
Chapter 8
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.
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?
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.
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.
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
ACS Chemistry FROG
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.
Use the molecular structure of a detergent molecule shown in Figure 8.19 to lead into the
discussion of micelles.
Check This 8.39. Evidence for micelle formation.
Consider This 8.40. How do ambiphilic molecules interact with nonpolar solutes?
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:
ACS Chemistry FROG
25
Chapter 8
The discussion should focus on how detergents work.
Then, lead into phospholipid bilayers and how molecules are transported through these
bilayers.
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 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.
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.
End of Chapter problems 8.72 and 8.73.
Section 8.12. Colligative Properties of Solutions

reaction.
Find the positional and thermal entropy changes for a process and combine them to determine
net entropy change for the process.
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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:
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.
Temperature reading of the ice-water mixture: 0 C.
Temperature reading of the ice-salt-water mixture: about 15 C.
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
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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.
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.
(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.
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.
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.
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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.
(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
ACS Chemistry FROG
29
We know from the diagram that the ratio
Chapter 8
Ssolvent gas
Ssolutiongas
> 1, so
Tsolutiongas
Tsolvent gas
> 1, which means
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.
Check This 8.48. Boiling point of a solution.
Section 8.13. Osmotic Pressure Calculations

Calculate osmotic pressures for solutions.
Use experimental values for osmotic pressure to determine the concentration of solutes in the
solution and/or the molar mass of the solute.
Section 8.14. The Cost of Molecular Organization

thermal entropy in the system and surroundings that drive the organization, specifically to the
organization of life on Earth related to the entropy increase of the Sun.
Section 8.16. ExtensionThermodynamics of Rubber

Predict the direction of the positional entropy change(s) that must occur to produce the
observed effects of heating or cooling a system, such as a rubber band.
Worksheet on Section 8.12 and Rubber-Band Thermodynamics
The following worksheet was contributed by Dr. Laura Eisen, Mount Vernon College of George
Washington University, Washington, DC. Some editing has been done to tighten up spacing, but
none of the content has been changed.
How does freezing of a solution compare to freezing of the pure solvent?
Solid
Pure Solvent
Solution
Which has the highest entropy of the three? _______. Which has the lowest entropy?________
30
ACS Chemistry FROG
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.]
Is the ratio S/S* ( = Ssolventsolid/Ssolutionsolid) <1, = 1, or > 1?

I. For freezing of pure solvent: Gsolventsolid = Hsolventsolid T Ssolventsolid. When T = Tm (the
normal melting/freezing point of the solvent) how are Hsolventsolid and Ssolventsolid related?
Write an expression relating Hsolventsolid, Tm, and Ssolventsolid.
II. For freezing of solution: Gsolutionsolid = Hsolutionsolid TSsolutionsolid. Write an expression
relating Hsolutionsolid, Tm*, and Ssolutionsolid, where Tm* is the freezing point of the solution.
Since it is actually the solvent that freezes in both cases, Hsolventsolid = Hsolutionsolid.
Use this fact to find a relationship among Tm, Tm*, Ssolventsolid, and Ssolutionsoli. Rearrange this
to express the ratio Tm*/Tm. Is Tm* < Tm, = Tm, or > Tm? (In other words, is the freezing point of
the solution less than, equal to, or greater than the freezing point of the pure solvent?)
Rubber-Band Thermodynamics
(This is to be done after completing Investigate This 8.54) The rubber band can be considered to
exist in one of two states: relaxed (R) or stretched (S)
For R S is H > 0, < 0 or = 0? How do you know?
For S R is H > 0, < 0 or = 0? How do you know?
For R S is G > 0, < 0 or = 0? How do you know?
For S R is G > 0, < 0 or = 0? How do you know?
For R S is S > 0, < 0 or = 0? How do you know?
For S R is S > 0, < 0 or = 0? How do you know?
Is spontaneous relaxation of a stretched rubber band driven by entropy or enthalpy?
ACS Chemistry FROG
31
Chapter 8
Solutions for Chapter 8 Check This Activities

Check This 8.5. Unmixing
This screen from the Web Companion, Chapter 8, Section 8.3, page 6, shows the animation after
it has been played, beginning with the mixed solution with 455 possible distinguishable
arrangements of the water and dye molecules. As the animation plays, the dye molecules are
allowed to occupy fewer and fewer of the boxes, that is, they are aggregating together and end
up all together in the top three boxes. The dye and water have unmixed. As this occurs, the
number of distinguishable arrangements decreases, that is, the state become less probable. Thus,
this animation represents a process in which the number of distinguishable arrangements
decreases: a process that is unfavorable.
Check This 8.6. Transfer of solvent from solution to pure solvent

If three solvent molecules pass from the solution side to the solvent side of the membrane, the
volume (number of boxes) available to the 3 solute molecules in the solution will be 6. We know
from Figure 8.7 that the number of ways of arranging these solute molecules is W = 20. The
number of ways of arranging the solvent molecules is W = 1 in the solution and also in the pure
solvent. Thus, W will decrease from 84 to 20 for the solution and remain the same for the pure
solvent. Since there is a decrease in W for this reverse osmosis, we would not expect to observe
this process. In reverse osmosis, solvent molecules move from a less concentrated region
(solution) to a more concentrated region (pure solute) and this, as we know is an unfavorable
process. See Problems 8.84 through 8.86 for further insights into reverse osmosis, after studying
Section 8.13.
Check This 8.9. Energy transfer from a cooler to a warmer solid
The number of distinguishable arrangements for the initial state of this two-solid system is
Wi = W2W6 = 1084 = 840,
where the numeric subscripts refer to the number of quanta in each identical 4 atom solid. The
number of distinguishable arrangements for the final state is
Wf = W1W7 = 4120 = 480
32
ACS Chemistry FROG
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
ACS Chemistry FROG
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
Snet = 12.4 JK1

Since Snet < 0, the formation reaction is not spontaneous (not favored) at 350 K. This result is
different than the conclusion reached in Worked Example 8.18 where we found the reaction to
be favored at a lower temperature. See the discussion of the result in Worked Example 8.18 to
see why this is the case.
Check This 8.20. Criterion for direction of change
We know that Snet increases (is positive) for reactions that are spontaneous and decreases (is
negative) for reactions that are not spontaneous. Since temperature, T, is always positive,
TSnet will be negative when Snet is positive and vice versa. Therefore, TSnet is negative for
reactions that are spontaneous and positive for reactions that are not spontaneous.
Check This 8.22. Free energy change for urea formation at 325 K
The standard free energy change for the formation of urea at 325 K (using values for Hsystem
and Ssystem from Worked Example 8.21) is:
G = Hsystem TSsystem = 133.3 103 J (325 K)(424 JK1) = 4.5 kJ
G = +4.5 kJ. Our conclusion is the same as in Check This 8.18. The reaction will not proceed
under standard conditions because the free energy change is positive.
Check This 8.24. Significance of the graphical relationship of H, TS, and G vs. T
At the point where the Ho and TSo lines cross in Figure 8.13, these functions exactly cancel
one another, Ho TSo = 0, and the free energy change is zero, as shown in the figure. At this
point, the net entropy change is zero and there is no driving force in either direction -- the ice
and water are in equilibrium. The crossing occurs at 273 K, the normal melting/freezing point of
ice/water. At temperatures higher than 273 K, TSo > Ho and the ice to water change is
possible: Go = TSonet < 0 (negative). At temperatures lower than 273 K, TSo < Ho and the
ice to water change is impossible: Go = TSonet > 0 (positive).
Check This 8.25. The melting point of benzene
The standard enthalpy and entropy changes for the freezing of liquid benzene are:
Hofreeze = Hof[C6H6(s)] Hof[C6H6(l)] = (38.4 kJmol1) (49.0 kJmol1)
Hofreeze = 10.6 kJmol1
Sofreeze = So[C6H6(s)] So[C6H6(l)] = (135 JK1mol1) (173 JK1mol1)
Sofreeze = 38 JK1mol1
34
ACS Chemistry FROG
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.
ACS Chemistry FROG
35
Chapter 8
Check This 8.32. Free energy change for fermentation of glucose

We use equation (8.26) to find the standard free energy change for glucose fermentation from
the values in Appendix B:
Greaction = [nj(Gf)j]products [nj(Gf)j]reactants
Greaction = {[(2 mol C2H5OH)(174.78 kJmol1)] + [(2 mol CO2)(394.36 kJmol1)]}
[(1 mol C6H12O6)(910.52 kJmol1)]
Greaction = 227.76 kJ
Within the likely experimental uncertainties of the data, this value is essentially identical to our
result in Check This 8.30. This should not be too surprising, because the values in Appendix B
are supposed to be internally consistent.
Check This 8.34. Free energy change for dissolving barium carbonate
(a) The standard enthalpy and entropy changes for dissolving barium carbonate, BaCO3(s) in
water are:
Hreaction = {[(1 mol Ba2+(aq))(537.6 kJmol1)] + [(1 mol CO32(aq))(677.1 kJmol1)]}
[(1 mol BaCO3(s))(1216.3 kJmol1)]
Hreaction = 1.5 kJ
Sreaction = {[(1 mol Ba2+(aq))(9.6 JK1mol1)] + [(1 mol CO32(aq))(56.9 JK1mol1)]}

[(1 mol BaCO3(s))(112.1 JK1mol1)]
Sreaction = 159.4 JK1
The negative sign for entropy may be surprising. From an inspection of the reaction, one might
conclude that the entropy change should be positive since it would appear that ions free to move
about in the whole volume of the solution would have more distinguishable arrangements than
the ions locked in their lattice positions in the solid reactant.
(b) The standard free energy change for this reaction (from the standard free energy of
formation values in Appendix B) is:
Greaction = {[(1 mol Ba2+(aq))(560.8 kJmol1)] + [(1 mol CO32(aq))(527.8 kJmol1)]}
[(1 mol BaCO3(s))(1137.6 kJmol1)]
Greaction = 49.0 kJ
The positive free energy change indicates that the dissolution of barium carbonate will not
proceed under standard conditions. There is no driving force. It also confirms, based on
thermodynamics, why we find barium carbonate to be a sparingly soluble solid.
Check This 8.39. Evidence for micelle formation
Our observations in Investigate This 8.37 are consistent with an explanation based on micelle
formation in the detergent solution. The sugar solution (solution of individual molecules) did
not scatter light, but the detergent solution did. Although we could not see the individual
micelles in the detergent solution, we confirmed their presence by observing the scattering of
light by this solution.
36
ACS Chemistry FROG
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
ACS Chemistry FROG
37

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Chapter 8.

Entropy and Molecular Organization

ACS Chemistry FROG

Entropy and Molecular Organization

Section 8.11. Ambiphilic Molecules: Micelles and Bilayer Membranes ................................22

ACS Chemistry FROG

Entropy and Molecular Organization

Materials for Chapter 8 Activities

Large fresh carrot, peeled

Cork borer or drill and drill

Clear plastic drinking straw

9-inch Pasteur pipet

Gum drops or similar soft

Small test tube

Thin-stem plastic pipets

Clear, colorless plastic or

Ring stand with clamp

ACS Chemistry FROG

Entropy and Molecular Organization

Reagents for Chapter 8 Activities:

2 mL/group; few drops

Coarse table salt, NaCl, or

ACS Chemistry FROG

Entropy and Molecular Organization

Introduction and References for Entropy

ACS Chemistry FROG

Entropy and Molecular Organization

Section 8.1. Mixing and Osmosis

ACS Chemistry FROG

Entropy and Molecular Organization

ACS Chemistry FROG

Entropy and Molecular Organization

ACS Chemistry FROG

Entropy and Molecular Organization

Section 8.2. Probability and Change

ACS Chemistry FROG

Entropy and Molecular Organization

ACS Chemistry FROG

Entropy and Molecular Organization

Section 8.3. Counting Molecular Arrangements in Mixtures

ACS Chemistry FROG

Entropy and Molecular Organization

Section 8.4. Implications for Mixing and Osmosis in Macroscopic Systems

ACS Chemistry FROG

Entropy and Molecular Organization

Section 8.5. Energy Arrangements Among Molecules

(({)) ((({((( ((({((( ((({(((

ACS Chemistry FROG

Entropy and Molecular Organization

ACS Chemistry FROG

Entropy and Molecular Organization

Section 8.6. Entropy

Section 8.7. Phase Changes and Net Entropy

Entropy and Molecular Organization

they occupy. If number of molecular arrangements is proportional to the volume available to

ACS Chemistry FROG

Entropy and Molecular Organization

ACS Chemistry FROG

Entropy and Molecular Organization

ACS Chemistry FROG

Entropy and Molecular Organization

Snet = Ssystem + Ssurr = 22.0 JK1mol1 + (22.0 JK1mol1) = 0.0 JK1mol1