SPECIFIC HEAT CAPACITY OF METALS

Andreas Kleiven1 , Helge Skarestad1

a TFY4165 Termisk fysikk, NTNU 2014

Abstract
The primary intention of this report is to investigate the specific heat capacity of metals. By discussing an experiment
in which solid aluminium vaporizes an amount of liquid nitrogen, it is possible to examine temperature dependency of
the specific heat capacity. The theoretical background for studying this dependency is Einsteins model for determining
the specific heat capacity. Consequently, the report illustrates use of quantum theory and statistical mechanics and how
they relate to macroscopic observables. The Einstein temperature for aluminium is estimated to be E = 282 19 K.

1. Introduction increases from T to T + T , the specific heat capacity at

The specific heat capacity of metals is a physical quan-
tity which is extremely important for every day life. Sys-
tems for cooling electronic components, refrigerators, wa-
ter heaters and car exhaust systems are some examples of
objects which would not work properly without knowledge
of how solids act in changing external temperatures.
Measurements of heat capacities have been important for
the development of quantum theory. According to clas-
sical mechanics, heat capacity should not be temperature
dependent. However, experiments made before the twen-
tieth century indicated the opposite. Einsteins model,
published in 1906 [1], was the first model that showed a
correlation between the heat capacity for solids and tem-
perature. Einstein used quantum theory to explain how
classical theory differed from experimental measurements.
This report deals with a method of finding the specific heat
capacity of a metal. An experiment has been conducted
in order to illustrate how thermal energy flows through
aluminium. The first part of this report explains the the-
oretical background for the experiment in which the heat
 1 3
capacity of aluminium is found. Here, Einsteins model of
harmonic oscillators with quantised energy levels will be
explained. The second part presents the method of the
experiment which has been carried out as well as the re-
sults. The last part contains a discussion on the validity
of the results as well as conclusions on the theory and ex-
periment.
2. Theoretical background
2.1. Specific heat capacity
The specific heat capacity c of a substance is defined as
the amount of heat needed to increase the temperature of
one unit mass of the substance by 1 K. If the temperature
Preprint submitted to Veileder
temperature T is given by
Q
c= , (1)
mT
where Q is the amount of heat added. It is often more con-
venient to express the specific heat capacity as molar heat
capacity, cpm or cVm . The indexes p and V indicate that
the pressure or the volume is held constant, respectively,
during the change in temperature.
2.2. Kinetic theory
Kinetic theory for gases is based on the assumption that
the molecules move as free particles. If the atoms in a
monoatomic gas are considered identical point masses, each
of them will have three translational degrees of freedom,
corresponding to their motion in three dimensions. In one
mole of the gas, there will be 3NA degrees of freedom.
NA expresses Avogadros constant. The equipartition the-
orem states that every degree of freedom which appears
quadratically in the total energy, contributes 12 kB T to the
average energy[2]. Therefore we have
E = NA E = 3NA kB T = RT, (2)
2 2
where kB is the Boltzmann constant and R = NA kB is the
gas constant. We get the molar heat capacity by derivation
of equation (2) with respect to time:
E 3
cVm = = R. (3)
T 2
2.3. Heat capacity of solids
Solids that consist of N atoms have 3N modes of vibration
and totally 6N degrees of freedom because of both kinetic
energy and potential energy for each mode of vibration.
The equipartition theorem gives us
cVm = 3R, (4)
April 2, 2014
also known as the Dulong-Petit law. Dulong-Petit law is
approximately correct for temperatures around 300 K, but
experiments have shown that cvm is temperature depen-
dent. In other words: classical mechanics is not sufficient
to describe the heat capacity.
Einstein used quantum mechanics to derive an equation
for the heat capacity. He assumed that the atoms in a
solid are arranged in a crystal structure. Each atom con-
sists of three independent one-dimensional oscillators and
the energy of each oscillator is quantised. The harmonic
oscillators have energy
E = h(k + 1/2) = Ek ,
where h is Plancks constant and is the frequency of the
oscillator. The average energy of each oscillator is
m2 , specific heat capacity c2 , and initial temperature T2 ,
the heat extracted from the object has to be equal to the
heat absorbed by the liquid. Equation (1) and conserva-
tion of energy gives us that
m1 c1 (T0 Tf ) = m2 c2 (Tf T2 ), (10)
where Tf is the shared temperature of the solid and the
liquid after the energy exchange. If some of the liquid
evaporate at a constant temperature T2 = Tf , the heat
change is replaced by the heat of vaporization,
Q = Lm, (11)
(5) where L is the specific heat of vaporization per mass of unit
of the liquid and m is the mass of the liquid evaporated
because of the heat from the object. Combining equations
(8) and (11) leads to

 1 heE0 /kB T 1 h
 
E = h + = h + h/k T . (6) 1 1
2 1 eh/kB T 2 e 1 Lm = 3nRE , (12)
B
eE /T0 1 eE /Tf 1
Because of three degrees of freedom per oscillator, the total where n is the total of moles of atoms in the solid.
energy per mole is
 
1 h 3. Method and apparatus
E = 3NA h + h/k T . (7)
2 e B 1
This discussion of method and equipment is primarily based
The heat capacity from equation (4) is corrected to on the explanation of the experiment in chapter two of the
2 lab guide which is written for TFY4165 Termisk fysikk[1].
eh/kB T

E h An overview of the apparatus used in the experiment is
cVm = = 3R . (8)
T kB T [eh/kB T 1]2 presented in figure 1.
The behavior of the specific heat capacity is given by the
ratio E /T , where E = h/kB is the Einstein tempera-
ture of the solid. This is a characteristic property of met-
als with different heat capacities. The behaviour of cvm
around extreme temperature highs and lows, is determined
by equation (8). When T is close to 0, a small temperature
increase is not sufficient to excite enough atoms to the first
vibrational state, hence cvm is close to 0. For high tem-
peratures, the difference between energy corresponding to
vibrational states is small compared to thermal energy, so
classical mechanics can be used. When T approaches in-
finity, cvm converges to 3R. This is the Dulong-Petit law.
However, experiments have shown that Einsteins model 00.00 g
is not entirely correct. A later addition to heat capacity
theory is the Debye model [3],
D
T 3 x4 e 4
 Z
T
cVm = 9R dx, (9)
D 0 (ex 1)2 Figure 1: A simple overview of the apparatus which was used
during the experiment. Two polystyrene cups are placed on
where D is the Debye temperature and x h/kB T . top of an electronic scale. The cups contain liquid nitrogen,
The Debye model takes into account that the atoms are and a cube of aluminium is lowered into it.
not oscillating independently with the same frequency.
The most important piece of equipment used in the ex-
2.4. Heat of vaporization periment was the electronic scale. The purpose of the
If an object with mass m1 , specific heat capacity c1 , and scale was to measure how fast liquid nitrogen vaporized
initial temperature T0 , is lowered into a liquid with mass in room temperature. On the scale were two polystyrene
2

cups stacked on top of each other. The cups contained
liquid nitrogen which is shown with bubbles in figure 1
to indicate that the liquid was boiling during the exper-
iment. The cups were made of polystyrene because they
were supposed to act as insulators in order to maintain a
controlled heat flow through the liquid-air interface. Ac-
cording to equation (11), the heat required to vaporize an
amount of liquid is proportional to the mass of the liquid
which is evaporated. By using the scale and a stopwatch,
it was possible to record the rate by which mass disap-
peared from the surface in the cups.
The first part of the experiment was a preliminary study
of the rate of evaporation in the cup. Nine observations
of weight were made within the first eight minutes. At
the ninth observation, a cube of aluminium was cautiously
lowered into the liquid by holding a string attached to the
cube. As the cube was lowered, the liquid started boiling
heavily due to the sudden heat transmission from the metal
to the liquid. When the heavy boiling stopped, a new series
of observations, similar to those before, were made. These
observations provided an overview of the rate of evapora-
tion after adding the aluminium cube. These observations
form the basis of calculating how much liquid nitrogen that
evaporated as the cube was cooled from room temperature
to the temperature in the liquid.
The next step of the experiment was to calculate E . By
making the assumption that no energy was dissipated dur-
ing the heat transfer in the cube, the total energy is pre-
served. Consequently equation (11) and (12) can be rear-
ranged to:
 
1 1
3nRE /T Lm = 0. (13)
e E 0 1 eE /Tf 1
4. Results
In order to obtain an experimental value for E , equation
(13) is put to use. The initial temperature of the alu-
minium cube, T0 was assumed to be equal to the room
temperature before the experiment started. The real tem-
perature was never measured exactly, so the estimate of
T0 is a rough one. This will nonetheless provide a basis for
discussing temperature dependency of equation (13). In
the following calculations, T0 is set to be within the range
T0 = 293.15 2 K. The mass of the aluminium cube with
string was measured with the electric scale. The mass of
the aluminium cube without the string attached was also
measured. From mcube = 6.075 g, the value of n can
be found by using the molecular weight of aluminium [4]:
n = 0.23 mol. The latent heat of nitrogen at its boiling
point, Tf = 77 K [4], is a tabled value: L = 2.0105 J/kg [4].
The amount of liquid nitrogen which evaporated during
the cooling of the aluminium cube, m, is found in fig-
ure 2. The two curves in figure 2 show the rate of which
3
120
Experimental values
Linear regression
110
100
90
Mass [g]
80
70
60
50
0 200 400 600 800 1000 1200
Time [s]
Figure 2: The two curves show the measured evaporation
rate of liquid nitrogen before and after the aluminium cube
was lowered into it. The weight of the aluminium cube with
string attached has been subtracted from the lower dataset.
nitrogen evaporated from the cup before the aluminium
was dropped into it and after the temperature in the cup
had stabilized. Consider the area between the two lines.
At some time between the last observation on the upper
dataset and the first observation on the lower set, m
can be read as a discontinuity on the mass-axis due to a
heat transfer. One would assume that the two curves had
equal slopes. The reason for why the two curves have dif-
ferent slopes is that the temperature of the air around the
polystyrene cups werent room temperature. The outer
surface of the cups became colder during the experiment.
This was observed as ice formed by water vapour in the
surrounding air crystallised on the surface of the cups.
Consequently the cups walls leaked less heat as the ex-
periment went on. This effect was intensified when the
heavy boiling of nitrogen occurred. Nitrogen at a temper-
ature just above Tf is heavier than room-tempered air. As
nitrogen evaporated from the cup, cold gas flowed past the
cup walls and cooled the surrounding air.
When making the observations for figure 2, both time in-
tervals and weight measurements were uncertain to a cer-
tain degree. The scale changed continuously during the
observations, and it was difficult to observe both the stop-
watch and the scale at all times. An estimate of deviance
in the measured m should account for all the small ran-
dom errors that occurred during the experiment. It is rea-
sonable to make the assumption that difference between
the two lines is evenly distributed and centred around an
average value. Due to the fact that the two curves are
linear and with different slopes, the mean value of the dif-
ferences between the curves is the same as the difference
in the middle of this interval. Therefore m is found as
the mean value of the difference between the curves at
time 524 15 s. This is an interval surrounding the ex-
act middle point between the last observation on the top
curve and the first observation on the bottom curve. The
discontinuity is believed to be contained within this inter-
val. If the distribution of different m is considered to be
normally distributed, the standard deviance of many m
within many small partitions in a time interval, is a good
estimate for the uncertainty in m. The final estimate of
mass change is m = 4.7 0.09 g.
With all the components of equation (13) known, it is pos-
sible to estimate E for aluminium. Due to the fact that
the equation cant be solved analytically, figure 3 is in-
cluded to provide a geometric solution.
400
Heat difference equation
300 Max. and min. values
Zero
how E varies with its parameters. Looking into the equa-
tion (13), it becomes clear that the experimental value of
E is much more vulnerable to small changes in m, than
small changes in T0 . Furthermore, changes in E due to
changes in T0 have positive correlation while changes due
to varying m have negative correlation. These observa-
tions imply that the largest source of error when finding
E is m.
Based on the experimentally found E , it is now possible
to use Einsteins equation for cVm to examine the temper-
ature dependency of the specific heat capacity. Figure 4
provides a comparison between heat capacity due to the
experimental E and tabulated values[5].
30
25

200 20
cVm [J/(K mol)]

100
15
0 With experimental E
Tabulated value
10
100 DulongPetit law

200 5

300
0
0 50 100 150 200 250 300 350 400 450 500
400 Temperature [K]
0 50 100 150 200 250 300 350 400 450 500
E [K]
Figure 4: Plot of experimental heat capacity as predicted
by Einsteins theory and the experimental E . The red dots
Figure 3: The geometric solution to equation (13). The ex- indicate tabulated values for the heat capacity of aluminium
perimental E is found where the equation value is zero. [5]. The green line is Dulong-Petits law.

The blue and green graphs in figure 3 correspond to equa- By looking at figure 4, it is obvious that the experimental
tion (13) for an array of different values of E . Within the curve differs from the tabulated values for temperatures
interval of E , the mapping of the heat difference equa- greater than and smaller than T0 . Table 1 is included to
tion crosses zero and this is where the experimental value highlight the quantitative differences between Einsteins
of E is found. model and experimental results.
Due to the fact that equation (13) is not suitable for an- Table 1: Quantitative differences between the experimental
alytical calculations, the following paragraph explains the and tabulated cVm .
use of logic in stead of mathematics to discuss how E
reacts to changes in parameters. T cexp ctable
Vm Vm
(K) (J K1 mol1 ) (J K1 mol1 ) (%)
In figure 3, two plots are included to illustrate how E
changes with the parameters. The top and bottom, green, 500 24.29 26.75 9.0
curves are plots of how equation (13) would act during a 300 23.19 24.37 4.8
worst case scenario in which both m and T0 con- 100 13.36 13.00 2.8
tribute maximally to the equation value. Reading from 40 2.09 1.10 90
figure 3 gives that E = 282 19 K. While being an ex-
perimental result, this doesnt really say anything about These differences were, however, expected. Einstein as-
4
sumed in his model that the oscillators were independent.
This assumption gets less valid as temperature gets higher.
For high temperatures, more atoms would be excited to
higher vibrational states, thus the oscillators could not be
considered independent from each other. The conclusion
is that higher temperature causes greater chance for in-
teractions between atoms. Also for small temperatures,
the experimental curve differs a bit, by the same reason.
Atoms with low frequency will be excited at low tempera-
ture and will contribute to cV m .This is what equation (9)
corrects.

5. Conclusions

The main goal of the report has been to investigate specific

heat capacity. By measuring how thermal energy flowed
from a piece of aluminium when cooled from room tem-
perature to the temperature in liquid nitrogen, an exper-
imental value for the Einstein temperature was estimated
to be E = 282 19 K. Using this value in Einsteins
model, and comparing the heat capacity to the tabulated
value, it showed a slight discrepancy. This was expected
due to interactions between atoms, which is not taken into
account in Einsteins model. To get a better correlation
between experimental data and tabulated values, the De-
bye model could have been used instead. When it comes
to minimising uncertainties connected to the observations
made in the experiments, some measures could have been
taken. m could have been estimated more accurately
if the observations were made by a more precise instru-
ment such as a data logger. Also, the temperature of the
aluminium, T0 , could easily have been measured more ac-
curately. This is however not as important as measuring
m accurately, as E is more sensitive to m than T0 .

The main goal of this report has, however, not been to ac-
quire cutting edge accurate values of specific heat capacity,
but to investigate the Einstein model and its limitations
and dependencies.

5
6. Reference list
[1] NTNU Institutt for fysikk:
Laboratorium i emnene TFY4165/FY1005 Termisk fysikk
http://home.phys.ntnu.no/brukdef/undervisning/tfy4165
lab/orientering/termisk labhefte 2014.pdf,
accessed 08 march 2014.
[2] Young H.D. and Freedman R.A. (2012) University Physics with
modern physics 13th ed. USA: Pearson Education Limited
[3] Sweeney S.: The Debye model:
http://personal.ph.surrey.ac.uk/ phs1ss/2SS/
2SS%20lecture%208.pdf
accessed 15 march 2014
[4] Aylward G. and Findlay T. (2008) SI Chemical Data 6th ed.
Australia: John Wiley & sons
[5] Buyco E.H. and Davis F.E. (1970) J. Chem. Eng. Data 15