In the Classroom

Dulong and Petit’s Law: W

We Should Not Ignore Its Importance
Mary Laing and Michael Laing*
61 Baines Road, Durban 4001, Republic of South Africa; *laingm@eastcoast.co.za

Recently while tidying up our library of chemistry books, and Petit he corrected their atomic weights to the values of
we came across a first-year laboratory manual of 1953 (50 113, 138, and 240, respectively, and these he incorporated
years old!), and in it, as experiment 4, was the determina- in his revised periodic table of 1871, shown in Figure 2.
tion of the atomic weight1 of a metal (1). In this experiment The structure of this table remained essentially un-
it is the atomic weight that is determined directly and not changed to about 1950 when the medium or long form was
equivalent weight. In a typical first-year laboratory it is the adopted in which the d transition elements were spread out
equivalent weight of a metal that is actually determined: ei- and the lanthanides and actinides were removed from the
ther by evolution of hydrogen gas, by reduction of the oxide body of the table. Thus Dulong and Petit’s law was critically
(with hydrogen or burner gas), by air combustion of the important for the preparation of the first good periodic table
metal, or by electrolysis (2). To calculate the atomic weight whose structure remains largely the same to this day.2
the student must know at least one of the following: the va-
lency of the metal, that hydrogen is H2, that oxygen is O2,
that the valency of hydrogen is one, or that the valency of
oxygen is two.
A first-year student should ask “What experiment can I
(as a student) carry out in the laboratory in one day, without
recourse to this information, to determine the atomic weight
of a metal?” The answer is “Measure its specific heat capac-
ity, and then apply the classical law of Dulong and Petit.”
This remarkable empirical discovery, first enunciated in 1819,
states that “the atoms of all simple bodies have exactly the
same capacity for heat” or, in modern terms, the molar heat
capacity, Cm, is the same for all solid elements, equal to the
product of the molar mass, M, and specific heat capacity, c,
of that element (3, 4).
Cm = Mc = 6 cal mol
1 K
1 = 25 J mol
1 K
1 (1)
We checked the indexes of some well-known first-year
textbooks for “Dulong and Petit”. The names were absent in Figure 1. Mendeleyeff’s 1869 periodic table. Positions of the elements
several, although the terms specific heat or heat capacity were In, Ce, and Ur are indicated. Wrong atomic weights are obvious.
present (5–9). Some mentioned specific heat of metals (10,
11). Only one textbook specifically mentions Dulong and
Petit’s law, and its importance in estimating (and correcting)
atomic weights (12). The textbooks of 30 years ago were bet-
ter in describing Dulong and Petit’s law and its application
(13, 14). Its value in correcting atomic weights is well de-
scribed in the old books (15–17).
Correcting the Periodic Table
Two very recent discussions of the historical and philo-
sophical background of the development of the periodic table
describe how Mendeleyeff during 1870 used the law of
Dulong and Petit to obtain correct atomic weights for in-
dium, cerium, and uranium (wrong in the 1869 table) and
thus produced the remarkable table of 1871 (18, 19). The
periodic table published by Mendeleyeff in 1869 is shown
in Figure 1. The elements In, Ce, and Ur, with atomic weights
of 75, 92, and 116, respectively, are positioned according to
their atomic weights as accepted at that time. It was evident
to Mendeleyeff that these elements were not well-positioned
(uranium between cadmium and tin!) and so during 1870 Figure 2. Mendeleyeff’s periodic table of 1871. The newly cor-
he obtained pure samples of these metals and determined rected positions of In, Ce, and U are indicated. The format of this
their specific heat capacities. Using the relationship of Dulong periodic table remained unchanged for about 70 years.

www.JCE.DivCHED.org • Vol. 83 No. 10 October 2006 • Journal of Chemical Education 1499

 In the Classroom
Law of Pierre Louis Dulong and Alexis Thérèse Petit
The specific heat capacities of the elements are interest-
ing because, unlike most other physical properties that are
periodic with atomic weight, the specific heat capacities are
not, but decrease monotonically with atomic weight. As
Dulong and Petit observed, the product of atomic weight and
specific heat capacity is approximately constant, 6 cal mol
1
C
1 or 25 J mol
1 C
1 for such disparate metals as Na, Al,
Zn, Pb, U—quite amazing.
Rarely does one see a graph of specific heat capacity ver-
sus atomic weight (Figure 3), but there is one in the vener-
able classic text by Mellor, 1927 (20). This displays the
characteristic hyperbolic curve showing the relationship be-
tween specific heat capacity and atomic weight of the metal-
lic elements.
Not only did Dulong and Petit in 1819 use their law to
correct atomic weights, for example, lead (17), but Berzelius
also used the relationship to deduce the correct atomic
weights that he published in 1827 (Fe = 54) and that had
been wrong in his list of 1815 (Fe =111) (21). But it was
not clear why this relationship should exist.
Problems and their Explanation
In the 1840s Regnault showed that the elements Be, B,
C, and Si had exceptionally low specific heat capacities at
room temperature (20): these elements had low atomic
weights and high melting points. Measurements at low tem-
peratures showed that for all elements c decreased toward zero
with decreasing temperature. However, c approached the
regular value of 6 cal mol
1 C
1 even for Be, B, C, and Si
with substantial increase in temperature. (The values shown
on Figure 3 for Be, B, and C are clearly not correct. They
should be far smaller. Correct values are in Table 1).
In 1871, Boltzmann applied Maxwell’s principle of
equipartition of energy to the problem of the heat capacity of
solids. He assumed that the ideal crystalline solid was built of
monatomic unit cells, one atom at each lattice position, con-
sisting of 3NA oscillators (NA is Avogadro’s number) each be-
Figure 3. The relationship between specific heat capacity and atomic
weight of the elements at 0 °C. The specific heat capacities for Be, B,
and C are not correct. All should be displaced to lower values: Be
0.43, B 0.24, and C 0.17. There is no value for gadolinium. (This
figure is taken directly from ref 20, p 261. The units of specific heat
capacity are cal g
1 C
1.)
1500 Journal of Chemical Education • Vol. 83 No. 10 October 2006
ing an atom vibrating in simple harmonic motion in three in-
dependent orthogonal directions. Each mode of vibration thus
contributes kBT to the energy of the atom (1/2kBT for the ki-
netic energy of the vibration and 1/2kBT for the potential en-
ergy). Thus the total energy of the 3NA oscillators is 3RT for 1
gram atom (or mole). The molar heat capacity of a monatomic
solid therefore is 3R per degree, 6 cal per mole per degree, twice
that of a monatomic ideal gas (22). A remarkable result.
The large variation in the value of c with temperature
(Figure 4) was explained for the first time by Einstein in 1907
using the quantum approach of Max Planck. Subsequently
Debye, in 1911, put forward a theoretical model whose cal-
culated values almost completely fitted the observed data (23).
Thus the genius of three Nobel Prize winners was needed to
finally bring understanding.
The heat capacity of the solid is dependent on a maxi-
mum characteristic vibration frequency of the oscillators, νm,
Figure 4. The value of the molar heat capacity, Cm, of a solid ele-
ment changes with temperature. The value of C approaches 3R
asymptotically with increasing temperature. That this occurs close
to room temperature for most metallic elements is serendipitous.
(This figure is from ref 20, p 802; temperatures are in degrees
Celsius. The units of atomic heat are cal mol
1 °C
1.)
Figure 5. The molar heat capacity of all elements follows the De-
bye equation and depends on the characteristic Debye tempera-
ture θ for the element. It is serendipitous that θ for most elements is
not much higher than room temperature, so that T/θ is about 0.7.
Values of θ are C 1900; Al 389; Ag 214; Pb 88 K. Comparison
with Figure 4 shows that lead already fits the Dulong and Petit law
at
173 C while aluminum does so only above 27 C. (This figure
is from ref 22, p 420. The units of atomic heat capacity are cal
mol
1 K
1, and T is in K.)
• www.JCE.DivCHED.org
 In the Classroom

and the value of hνm兾kB is termed the characteristic or De- Table 1. Specific Heat Capacities of Metals (at 25 °C)
bye temperature, θ. Cm at temperature T兾θ is the same for
Specific Molar Heat (Specific
all solid elements. θ is different for all solids and is related to Metal Heata / Capacityb /
Atomic
Heat)
1 /
the rigidity and melting point of the solid; typical values are: Weight
(J g
1 K
1 ) (J mol
1 K
1 ) (g K J
1 )
Ag 214, Al 389, Zn 235, and Cu 313 K. Elements with a
Li 3.582 24.77 006.9 0.279
small atomic weight and a high melting point that are hard
Na 1.228 28.24 023.0 0.814
(and are covalently bonded and not ductile) have large val-
ues of θ: examples are carbon, silicon, and boron whose θ’s K 0.757 29.58 039.1 1.321
all exceed 1000 K. Figure 4 shows the differences in behav- Bec 1.825 16.44 009.0 0.548
ior of lead, aluminum, and carbon, and Figure 5 shows how Mg 1.023 24.89 024.3 0.977
well the Debye equation reproduces the behavior of silver, Ca 0.647 25.31 040.1 1.545
aluminum, and carbon. One can conclude that the specific Al 0.897 24.35 027.0 1.115
heat capacity of a solid metallic element will obey Dulong Sc 0.568 25.52 045.0 1.760
and Petit’s law so long as it is measured at a temperature T Y 0.298 26.53 088.9 3.355
equal to or greater than about 0.7 θ.
La 0.195 27.11 138.9 5.128
Table 1 lists the specific heat capacities and molar heat
Ced 0.192 26.94 140.1 5.208
capacities of metals. Plotting the data from Table 1 shows
Sm 0.197 29.54 150.3 5.076
Eu 0.182 27.66 152.0 5.494
Gd 0.236 37.03 157.2 4.237
Yb 0.155 26.74 173.0 6.452
Lu 0.154 26.86 175.0 6.493
Ti 0.523 25.02 047.9 1.912
Zr 0.278 25.36 091.2 3.597
Hf 0.144 25.73 178.5 6.944
V 0.489 24.89 050.9 2.049
Cr 0.449 23.35 052.0 2.227
Mo 0.251 24.06 095.9 3.984
Mn 0.479 26.32 054.9 2.088
Fe 0.449 25.10 055.8 2.227
Ru 0.238 24.06 101.1 4.202
Figure 6. A plot of specific heat capacity versus molar mass of Co 0.421 24.81 058.9 2.375
representative data from Table 1. The curve is hyperbolic. The ele-
Rh 0.243 24.98 102.9 4.115
ments Be and Gd are not obviously misplaced. The position that
Be should have if its molar heat capacity were 25 J mol
1 K
1 is Ni 0.444 26.07 058.7 2.252
marked by the solid square, which is indicated by the arrowhead. Pd 0.246 25.98 106.4 4.065
Pt 0.133 25.86 195.1 7.519
Cu 0.385 24.43 063.5 2.597
Ag 0.235 25.35 107.9 4.255
Au 0.129 25.42 197.0 7.752
Zn 0.388 25.40 065.4 2.577
Cd 0.232 25.98 112.4 4.310
Hg 0.140 27.98 200.6 7.143
Ga 0.371 25.86 069.7 2.695
Ind 0.233 26.74 114.8 4.292
Sn 0.228 25.77 118.7 4.386
Pb 0.129 26.44 207.2 7.752
Sb 0.207 25.23 121.7 4.831
Bi 0.122 25.52 209.0 8.197
Th 0.113 27.32 232.0 8.849
Figure 7. A plot of the values of 1/specific heat capacity versus Ud 0.116 27.66 238.0 8.621
molar mass of representative data from the metals in Table 1. The Bc 1.026 11.09 010.8 0.975
curve is linear, except for the two metals Be and Gd, which are Cc 0.709 08.52 012.0 1.410
now clearly displaced from the line. The slope yields a value of Sic 0.705 19.79 028.1 1.418
26.5 J mol
1 K
1 for molar mass x specific heat (Mc) (close to 3R). a
Data from ref 27. Data from ref 28.
b
These four elements have
c
The slope, that is, Cm, for Be is 16.4 and for Gd is 37.0 J mol
1
the highest melting points of the first 20 elements in the periodic table:
K
1. The slope of the line through Au yields a value of 25.4 J mol
1 Be 1551, B 2573, C 3820, Si 1683 K. The atomic weights of these
d

K
1 and the value for Hg is 28.0 J mol
1 K
1. Values for the ele- three elements were corrected by Mendeleyeff in 1870, by the method
ments B, C, and Si are included for comparison. of Dulong and Petit.

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 In the Classroom
nicely both the patterns and the anomalies (such as beryl-
lium and gadolinium; Figures 6 and 7). The low values for
Be, B, C, and Si are evident and are explained by the Debye
model. The curve in Figure 6 is a good hyperbola. The very
small value for Be and large value for Gd are not readily ap-
parent but become obvious when 1兾c is plotted versus atomic
Figure 8. A plot of the specific heat capacity, cv, of nickel versus
temperature. The specific heat capacity at room temperature is
0.106 cal g
1 °C
1. The dramatic increase in the specific heat ca-
pacity at the Curie temperature of 365 °C is caused by the transi-
tion from a ferromagnetic structure at low temperatures to regular
paramagnetism above TCurie. (The figure is from ref 23, p 25).
Figure 9. A plot of specific heat capacity, cp, of the alloy beta-
brass versus temperature. At room temperature the Zn and Cu at-
oms are ordered in a simple cubic CsCl structure; cp for this alloy
is 0.093 cal g
1 C
1. The large increase in the specific heat capac-
ity at about 470 °C is caused by the Zn and Cu atoms becoming
randomly disordered in the body-centered cubic unit cell. (The fig-
ure is from ref 23, p 37. The units of cp are cal g
1 °C
1).
1502 Journal of Chemical Education • Vol. 83 No. 10 October 2006
weight. As shown in Figure 7, both Be and Gd are markedly
displaced from the line of slope 26.5 J mol
1 K
1.
The Anomaly of Gadolinium
The value of Cm for gadolinium, 37 J mol
1 K
1 at room
temperature, is anomalously large: the largest for all elements.
This is due to the phase change of the metal from ferromag-
netic to paramagnetic occurring at room temperature, that is,
its Curie temperature is 26 C (23). The same phenomenon
is found in nickel at 365 C (Figure 8). This effect cannot be
explained by the classic Debye model that considers only the
frequency of lattice vibrations of the atoms and cannot take
into account magnetic effects.
These anomalously large values for Cm are due to struc-
tural changes that are related to the number of unpaired elec-
trons in the atoms, and how the magnetic dipoles of the atoms
become aligned below the Curie temperature. Discussion of
the magnetic properties of metals is beyond the scope of this
article.
Similar unexpected large values for the specific heat ca-
pacity of a solid are observed when there are order–disorder
structural changes within the solid. The alloy beta-brass,
50:50 Cu兾Zn, has an ordered simple cubic CsCl-type struc-
ture at room temperature. This changes to a randomly dis-
ordered body-centered cubic structure at about 470 C. The
value of the specific heat capacity at this temperature is
anomalously large (Figure 9) (23).
It is thus clear that the value of the specific heat capac-
ity of an element will not necessarily change smoothly with
temperature but can have large discontinuities associated with
structural phase changes. Also the basic value of c is very de-
pendent on the hardness of material and the temperature at
which c is measured. (The specific heat capacity of gadolinium
at 50 C is not abnormal.) Figure 4 shows quite clearly that
if the standard temperature for measuring specific heat ca-
pacity were, say,
100 C, there would be no Dulong and
Petit’s law.
We thus arrive at the conclusion that the remarkable ob-
servation of Dulong and Petit is almost fortuitous, and ap-
plies well at room temperature for most elements simply
because their Debye temperatures are less than 100 C. Nev-
ertheless it was the very simplicity of Dulong and Petit’s Law
that made it so valuable to the chemists of the 19th century,
as it enabled them to obtain correct atomic weights.
Activities for Students
There have been a small number of articles in this Jour-
nal about specific heat capacity and Dulong and Petit’s law
(24–26) but in general they have not emphasized the impor-
tance of the measurement of the specific heat capacity of an
element in the creation by Mendeleyeff of the important pe-
riodic table of 1871. It seems that it would be a worthwhile
experience for students to examine the relationship between
the atomic weight and specific heat capacity of an element,
deduce the law of Dulong and Petit, and observe how the
atomic weight of an element can thus be determined. There
are two aspects that can be examined:
• www.JCE.DivCHED.org

• Practical determination of the specific heat capacity of
a metal; details of the experimental method (1) are
given as a laboratory experiment in the Supplemental
Material.W
• Processing of data, which is described in detail as a
classroom activity in the Supplemental Material.W
Laboratory Experiment
Determining the Specific Heat Capacity of a Metal
The student uses a nested pair of Styrofoam coffee cups
as a calorimeter. Pellets of the metal are weighed into a test
tube, which is then heated in a bath of boiling water for at
least 15 min. The temperature of the boiling water is recorded
to ±0.1 C. Using some ice chips, about 50 mL of water is
cooled to about 10 C below room temperature. Approxi-
mately 50 mL of this cold water is weighed into the polysty-
rene cup, and the temperature of the water is recorded. The
hot metal pellets are poured into the cold water, while stir-
ring with the thermometer. The student records the highest
temperature attained to ±0.1 C. From these data the stu-
dent records the energy gained by the water in the coffee-
cup calorimeter and hence the specific heat capacity of the
metal in J兾(g C). It is important here for the student to evalu-
ate the effect of an error of, say, 1 C.
Determining an Approximate Atomic Weight
Dulong and Petit’s law states that the product of the
molar mass, M, of an element and its specific heat capacity,
c, is approximately 6 cal mol
1 K
1 or 25 J mol
1 K
1. The
approximate atomic weight of the metal is easily estimated
by M = 25兾c. The student is asked to identify the unknown
metal from the following possibilities: Mg, Al, Ti, Cr, Fe,
Ni, Cu, Zn, Sn, Pb, and Hg. The student is then asked to
explain why it is not possible to be certain. In the determi-
nation of specific heat capacity, there should be about 10 dif-
ferent metals in a class of 30 to 100 students. It should
become evident to the students that they cannot differenti-
ate among the elements between Cr and Ni because the pre-
cision of the measurements is too low. It is here that a density
measurement or a simple chemical reaction can identify the
metal. Students can get good results for the atomic weight
(±2%) with careful work. The exercise is safe to carry out
and inexpensive to do because the metals are easily available
and can be reused.
Specific Heat Capacity of Sodium
The student is asked to describe how the specific heat
capacity of sodium (a metal that reacts violently with water)
could be determined. Determining the specific heat capacity
of a metal that reacts with water is not simple. Water cannot
be used. The liquid in the calorimeter could be a paraffinic
hydrocarbon or even silicone oil. The metal may have to be
cooled rather than heated. There is not a specific answer.
Hazards
The technique is relatively straightforward. None of the
metals are hazardous under the conditions of the experiment.
www.JCE.DivCHED.org • Vol. 83 No. 10 October 2006
In the Classroom
(In practice, mercury is not used as an unknown). The only
potential danger is the boiling water that could cause burns.
Students should be cautioned to handle the beaker and test
tube with care.
Classroom Activity: Exercises for the Student
in Processing of Data
The student extracts the values of the specific heat ca-
pacities (c) of the common group 2 metals, Be, Mg and Zn,
Cd, and Hg, from the CRC Handbook of Chemistry and Phys-
ics (27) and plots these values versus atomic weights. He or
she is asked to decide whether there is a relationship between
c and M, and if so, to say what it is. This process is repeated
for the lanthanides plus Ba, Al, Sc, Y, and Hf, and then for
the 3d metals, Ca and Sc to Cu and Zn, and again to deter-
mine whether there is a relationship between c and M. The
three plots are now combined and the data for the group 1
metals and the platinum metals are added. (The plotting can
be done by hand or by using the spreadsheet option in a pro-
gram like EXCEL). The student is asked to decide whether
there is a relationship between c and M for all metals. Stu-
dents must plot both c versus M and 1兾c versus M to come
to a correct conclusion.
If any metal is an exception to the general relationship,
the student must compare its values of: density, melting point,
compressibility (κ), expansion coefficient (α), electrical con-
ductivity (or resistivity), ∆Hat, IE1, and magnetic suscepti-
bility χ (27, 28) with those of its nearest neighbors across a
period, and comment on any discontinuities.
Systematically adding data, block-by-block, and seeking
a relationship at each stage until a satisfactory result is ob-
tained, is a good example of the application of the scientific
method. Students will probably ask why the law of Dulong
and Petit holds so well for metallic elements whose molar
masses range from 7 to 238 g mol
1! This can lead to a dis-
cussion of those topics that bridge the boundary between
chemistry and physics: Boltzmann statistics, the classical prin-
ciple of equipartition of energy, and the application of quan-
tum mechanics by Einstein and Debye to explain the behavior
of the specific heat capacity of solids with changing tempera-
ture (29, 30). Such concepts are beyond the realm of first-
year chemistry, nevertheless a lecturer should review these
topics in preparation for the awkward questions. Debye,
Einstein, and Planck have unlocked a deep secret of Nature.
Conclusion
This application of Dulong and Petit’s law is a good ex-
ample of how science actually occurs: how Mendeleyeff ob-
served that elements were wrongly placed in his first periodic
table of 1869, and how he knew that they had to obey the
periodic law and therefore deliberately redetermined their
atomic weights and thus placed them correctly in the peri-
odic system of 1871. It is quite remarkable how many solid
elements obey Dulong and Petit’s law. Gaining an under-
standing of why this should be requires a synthesis of many
physical concepts. Indeed, Dulong and Petit’s law is impor-
tant and interesting: it involved, separately, three Nobel Prize
winners.
• Journal of Chemical Education 1503
 In the Classroom
Acknowledgments
It was the stimulating discussions at the Second Harry
Wiener International Conference; The Periodic Table: Into
the 21st Century, held in Canada, 14–20 July, 2003, about
the development of the periodic table between 1869 and
1871 that prompted us to write this article. It is a pleasure
to thank the reviewers for their valuable and constructive
comments.
W
Supplemental Material
The laboratory experiment, the classroom activity, and
notes for the instructor are available in this issue of JCE On-
line.
Notes
1. Atomic weight is used because this term was used histori-
cally and is numerically identical to molar mass (which is in gram
mol
1).
2. The following comment by one of the reviewers about the
elements sums up the situation rather well. “There is a certain irony
in using a non-periodic property in order to establish the periodic-
ity of chemical and physical properties.”
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