Activity

pubs.acs.org/jchemeduc

Application of the Second Law of Thermodynamics To Explain the

Working of Toys
Erick Castellon*
Escuela de Qumica, Universidad de Costa Rica, Ciudad Universitaria Rodrigo Facio, San Jose, 11501-2060, Costa Rica
*
S Supporting Information

ABSTRACT: This teaching activity consists of challenging students to explain the

working principle behind three scientic toys: a drinking bird, a radiometer, and a
Stirling engine. The transformation of heat (q, thermal energy generated by a
temperature dierence) into work (w, mechanical energy manifested as motion) is
implicit in the working of these toys. Such a transformation constitutes a central
argument in the conceptual and historical development of entropy (S) and of the
second law of thermodynamics (SLT). The observation and the understanding of
the common working principles of these toys promoted a positive reaction by
students toward the formal development of a conceptual understanding of the SLT
and the concept of entropy.
KEYWORDS: Physical Chemistry, Thermodynamics, Humor/Puzzles/Games, First-Year Undergraduate/General

INTRODUCTION
To a large extent, the economic and social welfare of modern
societies is supported by their scientic and technical
development (i.e., knowledge-based societies). For this reason,
improving the teaching of basic science is subject to profuse
research; its objective is to enhance the academic education of
scientists, engineers, and technologists.1 Such an improvement
of teaching implies that the students should achieve an
improved rationalization of basic concepts during their
university education.
Recent eorts toward the didactic improvement in the
teaching of sciences have featured the need for an
implementation of novel pedagogical techniques in the
teachinglearning process. These techniques focus on the
enhancement of the students attitudes toward the study of the
thematic content of their courses, and also toward the teacher
(empathy).2,3 Positive attitudes are achievable through activities
considered to be fun by the students, in a way radically dierent
from the traditional teaching approach of transmission of
knowledge. A generation of positive attitudes in the students
can thereby develop into an improved understanding of the
course topics, converting learning into understanding, one of
the hallmarks of the new science of learning.4
Attractive teaching activities applied as didactic strategies
include dramatizations,5 games,6 and animations,7 among
others.8 Activities of these kinds are particularly useful for
teaching thematic content considered to be dicult, as is the
case of the second law of thermodynamics (SLT) as a topic in
physical chemistry courses.
Here we report the implementation of a teaching activity that
consists of the observation of toys as an initial point to develop
the thematic content of the SLT. The aim of the activity is to
promote positive reactions in the students toward the
development of an understanding of the SLT.
2014 American Chemical Society and
Division of Chemical Education, Inc.
THE SECOND LAW OF THERMODYNAMICS
Thermodynamics treats the laws governing the transformation
of energy between heat and work.9 Of four physical laws that
command the transformations of energy between its various
formsmechanical, thermal, kinetic, potentialthese laws
bear names according to ordinal numbers: zeroth, rst, second,
and third laws of thermodynamics.10 The rst law establishes
the principle of the conservation of energy, and was the rst to
be rmly established as a physical law. Almost at the same time
emerged the second law, which treats the spontaneity of
processes, and the third law, also known as Nernsts heat
theorem, that establishes a reference point (entropy as a zero
limit at the absolute zero of temperature) to calculate
thermodynamic properties of chemical substances.
From a historical perspective, the formulation and establish-
ment of the SLT arose from the study of heat engines (or
thermal machines; Figure 1) such as the steam engine
(developed by James Watt in the 18th century). Heat engines
transform heat (thermal or caloric energy) into work
(mechanical energy) manifested as motion.
Circa 1824, Sadi Carnot studied the cyclic process in the
working of thermal machines (heat engines) from a theoretical
perspective. From this study emerged the well-known Carnot
cycle (Figure 2), which concludes that inexorably a portion of
heat is not transformed into work.11,12 Using the results of
Carnot for the calculation of the net eciency of heat into
work, Rudolf Clausius in 1850 and Lord Kelvin in 1851
subsequently discovered a new thermodynamic state function,
implicit in the cyclic process, given the name entropy (S).
Moreover, Clausius and Kelvin discerned the pattern that this
quantity invariably increases in spontaneous processes
Published: April 11, 2014
687 dx.doi.org/10.1021/ed400085z | J. Chem. Educ. 2014, 91, 687691
Journal of Chemical Education
Figure 1. Scheme of a thermal machine: Th is the temperature of a hot
source, Tc is the temperature of a cold sink, q is the heat that ows
between them, and w is the work produced.
Figure 2. Carnot cycle. The isotherms refer to processes in which the
temperature is constant; adiabats represent processes in which the
system (piston) does not exchange heat with the surroundings.
(spontaneity univS > 0). Given that natural processes occur
spontaneously, Clausius summarized the rst and second laws
as the energy of the universe is constant, the entropy of the
universe tends toward a maximum. (The original quotation in
German is Die Energie der Welt ist Konstant; die Entropie der
Welt strebteinem Maximum zu.)
There are several ways to dene the SLT;12 a generalization
is the irreversibility of natural processes such that processes
proceed in a specic direction: heat ows spontaneously from a
hot object to a cold object, never in the reverse direction; a
drop of dye dissolves in water and, once dissolved, has never
been observed to separate from water, among many other
examples. The spontaneous direction in which natural
processes proceed invariably points to the direction of
increasing total entropy (Suniv).
The importance of the SLT is due to its predictive power in
determining the direction of spontaneity. Applied to chemistry,
this law can predict the direction in which chemical reactions
and physical transformations of matter proceed. An eective
development of the concepts embodied in the SLT is of crucial
688
Activity
importance in the curriculum of chemists, physicists, engineers,
and biologists, among others.
THE IMPLICIT DIFFICULTY IN THE SECOND LAW
OF THERMODYNAMICS
The rst law of thermodynamics (law of conservation of
energy) was universally accepted almost as soon as it was
stated, not because the experimental evidence in its favor was at
that time overwhelming, but because it appeared reasonable
and in accord with human intuition.9 In contrast, the SLT (the
law of degradation of energy or increase of entropy)
encountered a disparate reception, because it seemed in no
recognizable way to accord with the existing thought and
prejudice, with far-reaching implications in general cosmology.9
At present, those apprehensions about the SLT persist and
create a sense of unease and mystery in the students confronted
with it and entropy in their courses.13,14
Given the historical origins of the SLT and of the concept of
entropy, the teaching of those concepts is commonly
performed through a theoretical analysis of the cyclic processes
of thermal machines or heat engines, with particular emphasis
on the Carnot cycle. This approach is the most traditional and
predominant way to teach these topics in physics and physical
chemistry, a fact veriable in numerous textbooks.1518 In
general, this approach generates incomprehension regarding the
topic of the SLT and entropy, producing a perception by the
students of a lack of correlation between the historical origin of
the concepts and their generality as universal physical laws,
even more when those concepts (derived from the study of
heat engines) are applied to chemical systems.19
From a didactic point of view, the involvement of abstract
reasoning in deducing the concept of entropy increases the
complication for its assimilation by students, because neuro-
scientists have demonstrated that the frontal lobe of the human
brain, associated with abstract thinking,20 is not fully developed
in persons of age less than 25 years.21 For this reason, typical
students are more prone to concrete learning, through
experience.22
The didactic problem in teaching the SLT has led to an
inconvenient simplication of the concept of entropy, an
association with disorder; this relation has been refuted and
demonstrated as a conceptual error.23 Such a simplication of
entropy as disorder must hence be discarded.
Within the described frame of reference, this activity is
directed to promote a positive attitude in students toward the
development of an understanding of the SLT and entropy.
DIDACTIC STRATEGY
This didactic strategy comprises having students play with toys
that work as thermal machines: generating motion from a heat
ux. As part of this strategy, the students were separated into
groups and a dierent toy was assigned to each group. The
students played with the toys, and they were asked about the
working principle of each. The instructor eventually explained
in detail the operational mechanism of the function of the toys,
emphasizing the transfer of heat (q) between the hot (Th) and
cold (Tc) zones as the origin of the observed motion, which is a
physical manifestation of work (w). The purpose of this
experience is to make sense of the scheme of Figure 1 in a
pragmatic manner.
The toys used for this purpose were a drinking bird, a
radiometer, and a Stirling engine. In the following section, the
dx.doi.org/10.1021/ed400085z | J. Chem. Educ. 2014, 91, 687691
Journal of Chemical Education Activity

working principles of these toys are provided. The students

explanations are also given; although most students ideas are
erroneous, they did nd that a temperature dierence must be
involved in the generation of motion of the toys.
The Drinking Bird
This toy with the silhouette of a bird (see Figure 3) is famous:
there are multiple appearances of the toy on television, for

Figure 4. (a) A radiometer. (b) Working of the toy and a correlation

of its parts with the generalized scheme of a heat engine.

black side than on the white side, and eventually these collisions
propel the rotor.25,26
After the observation of the radiometer in action, some
students suggested that the working principle is based on light
Figure 3. (a) A drinking bird. (b) Working of the toy and the pressure caused by elastic collisions of photons on the white
correlation of its parts with the generalized scheme of a heat engine in
sides of the rotor and absorption on the black sides; this
which the motion is related to the work (w).
explanation is incorrect because it predicts rotations in the
inverse sense. Some students proposed, however, that a
temperature dierence must be established between the two
instance in The Simpsons. The body of the toy is a tube that
faces of the blades, which is a fact, and some other students
contains a volatile liquid such as dichloromethane (CH2Cl2).
added that the rotation can be explained with convective
The drinking bird produces motion after wetting of the head
currents, which is incorrect (again, this idea predicts a rotation
of the toy; the evaporation of water from the head produces a
in the opposite direction).
cooling eect and thereby a dierence of temperature between
the head and abdomen of the bird. This dierence of Stirling Engine
temperature produces a dierence of vapor pressure of the This engine (Figure 5, a version with a free piston is less
volatile liquid; the vapor pressure is therefore larger in the expensive) is a device that resembles the heat engines or
birds abdomen than in the cooler head. This dierence of
pressure propels the liquid to ascend to the head through the
birds neck; when the liquid reaches the head, the center of
mass of the toy alters, causing an imbalance and inclination of
the bird, producing motion (work). This inclination causes
pressure to become equal between the head and the abdomen
of the bird, because of the connection of the gas spaces between
the birds parts, thereby causing the liquid to fall to the
abdomen. This eect restores the initial situation, allowing the
toy to repeat the process (cyclic characteristic). Further
quantitative details can be found in the literature,24 but are
not necessary for this introductory activity.
In their explanations about the working principle of the
drinking bird, the students correctly observed that a dierence
in temperature must exist between the abdomen and the head;
they incorrectly thought, however, that the warmer abdomen
Figure 5. A Stirling engine and its parts.
must expand the liquid, causing it to climb.
The Radiometer thermal machines used to explain the origin of the SLT. For the
A radiometer (Figure 4) produces motion through its specic Stirling engine used in an experiment with students, the
irradiation with light, thereby transforming radiant energy temperature dierence needed for its working is achieved by
(light) into mechanical energy (motion); this transformation placing the bottom of the engine on a cup of hot water and
generates a dierence of temperature between the faces of the some pieces of ice on the top (see Figure 5). The assembled
blades of a rotor. This rotor is located inside a bulb containing a Stirling engine involves a piston and a displacer; its function is
gas at a small pressure; each blade of the rotor has one side to reaccommodate the gas inside the engine to be alternatively
painted white and the other black. An irradiation with light in contact with the hot zone (expansion of the gas) at one
causes the black side to become hotter than the white side moment and then in contact with the cold zone (contraction of
because of light absorption. This minor temperature dierence the gas). The alternating expansion and contraction of the gas
causes the molecules to make more vigorous collisions on the produces the motion of the piston (work).
689 dx.doi.org/10.1021/ed400085z | J. Chem. Educ. 2014, 91, 687691
Journal of Chemical Education
This Stirling engine was really a black box for the students
(inner parts are not observable); it was, however, obvious to the
students that a dierence of temperature is involved in its
working principle, because of the involvement of hot water and
ice for the function of the toy.
EVALUATION OF THE ACTIVITY AND RESULTS
To evaluate the activity and its degree of satisfaction, the 28
participating students of Physical Chemistry for Chemical
Engineering were requested to respond to several statements, in
which each statement was evaluated according to this Likert-
type scale: 1, strongly disagree; 2, disagree; 3, indierent;
4, agree; 5, strongly agree. These were the statements for
response:
S1: I enjoyed participating in the activity.
S2: I understood the function of the toys.
S3: The activity helped me to understand the topic of heat
engines as an introduction to the development of the
second law of thermodynamics.
S4: The observation of the functioning toys helped me to
understand that a ux of heat between a hot source and
a cold sink can serve to generate work.
S5: The activity helped me to understand the connection
between the concepts Carnot cycle and entropy.
S6: The development of the activity in class was adequate:
playing with the toys explaining the function of the
toys developing the topics of heat engines and the
Carnot cycle).
Figure 6 shows the results of the evaluation of the activity
according to that scale. In general terms, a positive degree of
Figure 6. Evaluation of the didactic strategy according to responses
using a Likert-type scale. Standard deviations () from a sample of
students, N = 28, express the uncertainties.
satisfaction and comprehension toward the activity was found,
which veries the achievement of the main task: to generate a
positive attitude in the students toward the teaching of the SLT
and entropy.
It can be partly associated with the generation of positive
attitudes in the students toward the study of the SLT, the fact
that the second examination of the physical chemistry course
(which covers this topic) showed the best average grade: 8.9 (
= 1.1) versus 5.4 ( = 1.9), 8.1 ( = 1.0), and 6.5 ( = 1.8) on
the scale 010 for the rst, third, and fourth examinations,
respectively. Each latter average grade diers signicantly from
that of the second examination with a probability of 99%
according to the Students t test.2729
Activity
CONCLUSION
This work shows the application of an activity in which
students play with toys that function as heat engines. This
didactic strategy was successful in causing students of physical
chemistry to entertain positive attitudes toward the develop-
ment of the topics of SLT and entropy. The observation and
comprehension of the working principles through the operation
of the toys by the students strengthened at a cognitive level the
idea that a ux of heat produced by a dierence of temperature
can serve to generate work, as the students perceived and
understood the temperature dierence and observed the work
produced as motion. Given the success of this activity, it is
recommend that this or similar activities be applied in courses
of physical chemistry, general chemistry, and physics among
others in which the SLT is an essential topic.
*
ASSOCIATED CONTENT
S Supporting Information
Sources for purchasing the toys; original survey (in Spanish)
used to evaluate the activity. This material is available via the
Internet at http://pubs.acs.org.
AUTHOR INFORMATION
Corresponding Author
*E-mail: erick.castellon@ucr.ac.cr.
Notes
The authors declare no competing nancial interest.
ACKNOWLEDGMENTS
I thank J. F. Ogilvie and Julio Mata-Segreda for comments on
this work.
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(19) There is a modern trend that considers that a convenient way to
develop the SLT is through Information Theory, instead of using
historical development.
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Teach. 1968, 6 (7), 358.
(26) This idea does not, however, fully explain the motion of the
rotor, which is apparently being pushed from the black side, because
molecules are deviated more from a path toward the black side by the
recoiling molecules than toward the white side; the pressure over most
of the black (warmer) side is thus the same as the pressure on the
white (cooler) side. The situation is dierent at the edges, at which the
molecules on a path toward the edge on the black side are deviated by
rebounding molecules from the black side and by molecules crossing
from the white or cooler side, but the latter are less ecient in
stopping incoming molecules. The pressure on the black side is hence
greater at the edge than at the center and greater than at the white
side. This description and other details concerning the history of the
radiometer are discussed in ref 25.
(27) Such a fact cannot be entirely associated with the application of
the activity; in other semesters in which this activity had not been
applied, the mentioned situation was, however, generally dierent; the
average grade of the examination in which the SLT and entropy were
evaluated showed a small value or a value insignicantly dierent from
those of other examinations.

(28) Miller, J. N.; Miller, J. C. Estadistica y Quimiometria para

Quimica Analitica (Spanish); Pearson Education: Mexico DF, Mexico,
2002.
(29) The questions evaluated in the examination were about: (1)
The Carnot cycle and its relation to the discovery of the state function
entropy; (2) Statement of the SLT and discussion of its importance;
(3) Statement of the third law of thermodynamics and discussion of its
importance; (4) Statement, using an example, of the erroneous
relation between entropy and disorder; (5) Calculation of the total
entropy change for a chemical reaction and prediction of its
spontaneity; and (6) Calculation of a third-law entropy of a substance
based on the variation of heat capacity with temperature Cp(T).

691 dx.doi.org/10.1021/ed400085z | J. Chem. Educ. 2014, 91, 687691