In the Classroom
Visualizing Entropy
Joseph H. Lechner
Department of Chemistry, Mount Vernon Nazarene College, 800 Martinsburg Road, Mount Vernon, OH 43050;
[email protected]
Entropy is discussed in most introductory chemistry of distinct but equivalent ways to distribute a specified
courses as a possible explanation for the spontaneity of chemi- quantity of energy among a collection of molecules, and
cal reactions. A process is said to be spontaneous if it occurs k has the value 1.38 × 10{23 J K{1.
without outside intervention (1). The second law of thermo-
S = k ln W (1)
dynamics attempts to identify which kinds of processes can
be spontaneous. The version of it attributed to Rudolf Clau- A number of analogies have been proposed for helping
sius states that “the entropy of the universe tends toward a students to visualize entropy. Toy blocks have more entropy
maximum” (2). Introductory chemistry texts define entropy when scattered on the floor than when neatly stacked (14 ).
using terms like disorder (1, 3–7 ), randomness (1, 3, 5, 8), Trash has more entropy if scattered over the countryside than
dispersal (9), energy storage (10), or the number of microstates if collected in a wastebasket (7 ). A pile of loose bricks has
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(11). Sometimes the random arrangement of molecules is more entropy than an intact brick wall (8). A jar of mixed
emphasized, sometimes random molecular motion is stressed, nuts has more entropy than a jar containing all peanuts or
but entropy clearly encompasses both of these (12, 13). In all cashews (15). A deck of playing cards has more entropy
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Ludwig Boltzmann’s formula (eq 1), W represents the number after it has been shuffled (3, 16 ) or thrown in a heap (1, 6,
11, 17) than did the original, unopened deck whose cards
Table 1. Materials for a Rainbow Tube
were arranged in a predictable order. Umland and Bellama
Inner Containers
(7 ) object to the latter analogy because each card in a deck is
Size Outer Container Closure distinguishable from the others, whereas the molecules of a
(6 each)
Small 5-mL beakers 25 × 150-mm test #5 rubber stopper substance are identical.
tube I describe two classroom activities that help students
Medium 10-mL beakers 250-mL #7 rubber stopper visualize the concept of entropy and appreciate that entropy
poly(methylpentene) tends to increase spontaneously.
graduated cylinder a
Large 50-mL beakers 1000-mL #12 rubber stopper Part 1 (Qualitative): The Rainbow Tube
poly(methylpentene)
graduated cylinder a A rainbow tube consists of six beakers (Table 1), each
aTop section with pour spout should be cut off so that the stopper containing a different brightly colored solution (Table 2),
will make a watertight seal. stacked inside a large, stoppered test tube or graduated cylin-
der (Fig. 1A). If it is shown indoors, the rainbow tube can be
Table 2. Solutions for the Rainbow Tube illuminated by floodlights to emphasize the attractive colors.
No. Color Species Responsible Method of Preparationa ,b I first point out to students that the substances inside the rain-
1 red phenolphthalein combine 1 mL 0.1% (w/v) bow tube are highly organized: all the red solution is in the
phenolphthalein (in ethanol) with first beaker; all the yellow solution is in the second beaker; all
100 mL 0.1 M NaOH
2 yellow mostly dissolve 2.4 g Fe(NO3 )3 in 100
Fe(OH)(H2 O)5 2 + mL H2 O
3 blue Cu(NH3 )4 2 + dissolve 0.19 g Cu(NO3 )2 in A B
100 mL 1 M NH3
4 orange probably add 1 mL 0.1 M Fe(NO3 )3 and
FeSCN(H2 O)5 2 + 1 mL 0.1 M KSCN to 98 mL
H2 O
5 green bromcresol green dissolve 1.4 g
NaC2 H3 O2 ?3H2 O in 100 mL
0.1 M HC2 H3 O2 and add 10
drops 1% bromcresol green
solution
6 violet Mn O 4 { dissolve 0.016 g KMnO4 in 100
mL H2 O
NOTE: We prepare enough material for several repetitions of the dem-
onstration and store each solution in a capped bottle. Solutions should
not be placed in the rainbow tube until shortly before class time; other-
wise NH3 may diffuse from No. 3 and cause a precipitate in No. 2.
aThese formulas yield solutions that have pleasing colors when viewed
in 50-mL beakers. A solution’s optical density is directly proportional to
its thickness. If smaller beakers are used, more concentrated solutions
may be needed to achieve the same color intensity.
bThese formulas provide the following final concentrations of the in-
dicated reagent: solution 2, Fe(NO3)3 0.1 M; solution 3, Cu(NO3)2
0.01 M; solution 5, NaC2H3O2 0.1 M; solution 6, KMnO4 0.001 M. Figure 1. The rainbow tube (A) before and (B) after inverting.
1382 Journal of Chemical Education • Vol. 76 No. 10 October 1999 • JChemEd.chem.wisc.edu
In the Classroom
the blue solution is in the third beaker; etc. In other words, insoluble MnO2 by the ethanol in no. 1; and the Cu2+ in no. 3
the entropy (disorder) of this system is low. I also point out and the Fe3+ in no. 2 precipitate as hydroxides. The resulting
that the rainbow tube did not generate itself spontaneously; mixture’s pH is approximately 11. Addition of 6 M hydro-
careful assembly was required. Each solution was prepared chloric acid (1 mL of acid per 30 mL of mixture) yields a
individually from pure chemical compounds, poured into a clear yellow solution whose pH is 2–3. Disposal of this solution
separate beaker, and carefully lowered into the tube using via sanitary sewer is permissible in most localities.
tongs.
After everyone has had an opportunity to appreciate the Part 2 (Quantitative): Money by the Pound
beauty and orderliness of the rainbow tube, I introduce the
second law of thermodynamics: the entropy in an isolated system Office workers shred confidential papers before discard-
tends to spontaneously increase. The contents of a rainbow ing them because this decreases the likelihood of someone
tube are isolated because the tube is sealed. The stopper prevents reassembling a document and reading it. For similar reasons,
it from exchanging energy or materials with the outside world. the Federal Reserve Bank shreds paper currency that has been
It would be technically more accurate to say that the rain- withdrawn from circulation. The average life expectancy for
bow tube is closed (i.e., its contents can still exchange energy a dollar bill is 18 months; higher denominations tend to last
with the surroundings), but actual energy flow is negligible un- longer because they are handled less frequently (18). Retired
der the conditions of this experiment. I ask, what would hap- bills are destroyed by cutting them lengthwise into strips
pen if the rainbow tube were inverted? After students have approximately 1/16′′ wide. The resulting fragments are much
had opportunity to make predictions, I slowly and dramati- more disorderly than an original, intact bill. Cutting a dollar
cally invert the rainbow tube. The solutions mix together, chemi- bill into strips is quick and easy. (I suggest demonstrating
cal reactions occur, and a nondescript (and unattractive) this with play money!) Reassembling a shredded bill is possible,
brown sludge is formed (Fig. 1B). This sludge is more ran- but is time consuming and tedious.
dom (higher in entropy) than the original solutions were, The shredding process is analogous to a chemical reaction
because the six pure chemical substances are now mixed and in which a large reactant molecule is converted to many small
scattered throughout the tube. product molecules. Examples of such reactions include the
I next ask the class whether it would be possible to aerobic metabolism of glucose, the detonation of TNT, and
refine the brown sludge (high entropy), recover the six com- the combustion of gasoline. These reactions are highly spon-
pounds, and return each substance to its original beaker (low taneous, both because they involve large entropy increases
entropy). If students hesitate, I suggest that someone could and also because they are exothermic.
dissolve the sludge in concentrated hydrochloric acid; perform Shredded U.S. currency is available from American Science
ion-exchange chromatography to separate copper, iron, and & Surplus, Skokie, Illinois 60076. Item 26470, “Money by
manganese; and then re-create the original solutions. Admit- the Pound”, costs $2 and contains 454 g of shredded bills of
tedly this would be a tedious and time-consuming process. mixed denominations—enough to fill a large (16′′ diameter)
Students are not eager to attempt it themselves, but they seem stainless-steel kitchen bowl (Fig. 2).
willing to acknowledge that a technically competent instructor I have challenged younger students (grades 7–12) to
could perform the separation. Yes, it is possible to reduce the find the fragments of a single bill and to reconstruct it. To
entropy of the rainbow tube. However, the restoration facilitate reassembly, each student is given a sheet of cardstock
method outlined above requires an open system. One must with two 65-mm strips of double-sided cellophane tape
remove materials from the tube, use additional substances that placed 15 cm apart. Fragments of currency can be stretched
were not part of the original system, and expend energy from out between the tapes and lightly adhered to the card. To
an external source. Furthermore, wastes would be generated. succeed, not only must one find a complete set of strips all
The environment’s entropy would increase if the rainbow from the same denomination, but the serial numbers in all
tube’s entropy were reduced. four corners of the bill
Finally, I ask, would it be possible to restore the rainbow must match. So far, no
tube to its original condition without removing the stopper? one has recovered a com-
Most students answer confidently in the negative. To verify plete bill, but one person
their prediction, I leave the tube in the lecture room until the (working approximately
next class day. Of course, the contents remain a brown sludge. an hour) found adjacent
This allows me to make an important distinction between strips comprising 40% of
what the second law says and what many people think it says. a bill. I have assumed that
A popular misconception holds that no system’s entropy can all of a bill’s fragments are,
ever spontaneously decrease. Thus, for example, it has been in fact, present in the
argued that evolution is thermodynamically impossible because bowl, although this is not
highly developed organisms would have less entropy than guaranteed (some stu-
their simpler predecessors. This argument presupposes that dents believe that the
the biosphere is an isolated system. It isn’t, because the earth Treasury Department
receives energy from the sun. The second law of thermodynamics transports the top and
does not claim that a decrease in entropy is impossible; it states bottom halves of retired
that a decrease in entropy in an isolated system is improbable. bills to different geographi-
When the rainbow tube is inverted and the solutions in cal locations to eliminate
Table 2 are mixed, the acetic acid in no. 5 is neutralized by any possibility of reas-
excess NaOH in no. 1; the MnO4{ in no. 6 is reduced to sembly). Figure 2. Money by the pound.
JChemEd.chem.wisc.edu • Vol. 76 No. 10 October 1999 • Journal of Chemical Education 1383
In the Classroom
I have asked college freshman chemistry students to es- entropy is directly proportional to n – 1, where n is the number
timate the probability that someone could find all the frag- of strips into which each bill is shredded (Fig. 3). Compared
ments of a single bill by randomly drawing strips from the to shredded currency, uncut bills (n = 1) have zero entropy.
bowl. Samples of currency were weighed on an analytical bal- It seems clear that these calculations yield relative, not
ance, yielding the following relevant information: absolute, results. A pound of unshredded money must still
1. The average mass of an intact, circulated U.S. bill is possess some entropy. Students may be able to suggest several
0.985 g. reasons: (i) at a macroscopic level, the bills are of mixed denomi-
2. The average mass of one strip of shredded currency is nations, each bill has a different serial number, the bills are
0.0253 g. arranged randomly in the bowl, and some of them may be
3. Each shredded bill was cut into 0.985/0.0253 = 39 strips. marked or torn in distinctive ways; (ii) at a microscopic level,
4. A pound of shredded currency contains approximately cellulose molecules in the paper are of varying lengths, they
454/0.0253 = 16535 strips. are oriented irregularly, and they vibrate randomly. The fore-
5. A pound of shredded currency is equivalent to 454/ going discussion can help students understand why thermo-
0.985 = 461 complete bills. NOTE: the Bureau of En-
graving and Printing states that uncirculated currency Table 3. Probability of Drawing All n Fragments of the
contains 490 bills per pound (19); however, one would Same Bill in n Successive Attempts from a Collection of
expect previously circulated bills to weigh more because 461 Shredded Bills
they have adsorbed soil and moisture. n P 1/P S / J K{1 a
What is the likelihood of getting all n fragments of the same 1 1 1 0
bill (any bill) by randomly drawing n strips in succession? If 2 1.09 × 10 {3 9.21 × 102 9.42 × 10 {23
the bills have not been shredded at all (n = 1) then, of course, 3 1.05 × 10 {6
9.54 × 10 5
1.90 × 10 {22
the probability is 1.0 that a complete bill will be found. 4 9.60 × 10 {10
1.04 × 10 9
2.87 × 10 {22
If each bill has been cut in half (n = 2), the first strip
5 8.54 × 10 {13
1.17 × 10 12
3.84 × 10 {22
taken will necessarily be a part of one of them (P = 1). There
6 7.45 × 10 {16
1.34 × 10 15
4.81 × 10 {22
remains one other piece of that particular bill (and 921 pieces
total) in the bowl, so the probability of drawing the second 7 6.42 × 10 {19
1.56 × 10 18
5.78 × 10 {22
strip from the same bill is (P = 1/921). 8 5.47 × 10 {22
1.83 × 10 21
6.76 × 10 {22
If each bill has been cut into thirds, the probability of 9 4.63 × 10 {25
2.16 × 10 24
7.73 × 10 {22
drawing all three fragments from the same bill is 10 3.90 × 10 {28
2.57 × 10 27
8.71 × 10 {22
P = 1 × 2/1382 × 1/1381 = 1.05 × 10{6 (2) 20 5.81 × 10 {59
1.72 × 10 58
1.85 × 10 {21
30 7.52 × 10 {90
1.33 × 10 89
2.83 × 10 {21
For the general case where each bill has been split into n
40 9.19 × 10 {121 1.09 × 10120 3.81 × 10 {21
fragments, the probability of finding all the pieces of a single
50 1.09 × 10 {151 9.20 × 10150 4.80 × 10 {21
bill in n successive draws is given by
60 1.26 × 10 {182 7.93 × 10181 5.78 × 10 {21
P = 1 × (n – 1)/(461n – 1) × (n – 2)/(461n – 2) × 70 1.44 × 10 {213 6.94 × 10212 6.76 × 10 {21
… × 1/(461n – [n – 1]) (3) 80 1.63 × 10 {244 6.13 × 10243 7.75 × 10 {21
Spreadsheet evaluation of eq 3 yielded the representative 90 1.83 × 10 {275
5.46 × 10 274
8.73 × 10 {21
results shown in Table 3. Clearly, the probability of success 100 2.04 × 10 {306
4.89 × 10 305
9.72 × 10 {21
drops precipitously as n increases. Direct computation failed aCalculated using the formula S = k ln (1/P ).
for values of n greater than 33 because my spreadsheet program
could not display a number smaller than 1 × 10{100; however,
log10(P) could still be calculated for large n using eq 4:
n–1 n–1
log10 P = Σ log10 n – i – Σ log10 461n – i (4)
i=1 i=1
When n = 39, P = 1.14 × 10{117, a vanishingly small
probability. If this were a lottery, we could say that the odds
of winning are one chance in (1/P) = 8.8 × 10116. A person’s
chances of hitting the jackpot in a state lottery are roughly
10110 times better than this. For example, the Maryland State
Lottery Agency estimates that the odds of winning its Classic
Lotto jackpot are one chance in 6.99 million (20). Put still
another way, the value of (1/P) represents the number of
different possible ways of selecting n strips from the larger
collection of strips. Thus (1/P) is analogous to the number
of equivalent thermodynamic states that are possible for a
system of molecules.
I have calculated the “entropy” in a collection of shredded
bills using Boltzmann’s principle (eq 1), taking 1/P as the Figure 3. Entropy in a collection of 461 shredded bills as a func-
value of W (Table 3). This yields the not-unexpected result that tion of the number of fragments per bill.
1384 Journal of Chemical Education • Vol. 76 No. 10 October 1999 • JChemEd.chem.wisc.edu
In the Classroom
dynamic quantities such as G °, H °, and S ° must be calculated 9. Moore, J. W.; Stanitski, C. L.; Wood, J. L.; Kotz, J. C.; Joesten,
relative to a carefully defined standard state. M. D. The Chemical World: Concepts and Applications, 2nd ed.;
Saunders: Philadelphia, 1998; p 272.
Acknowledgment 10. Atkins, P.; Jones, L. Chemistry: Molecules, Matter, and Change, 3rd
ed.; Freeman: New York, 1997; p 596.
I thank Tiffany Lippert (Fig. 2) for technical assistance. 11. Oxtoby, D. W.; Freeman, W. A.; Block, T. F. Chemistry: Science
of Change, 3rd ed.; Saunders: Philadelphia, 1998; p 454.
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