Table of Contents

Table of Contents ......................................................................................................................2

Theoretical background ...........................................................................................................3
Experimental Setup ..................................................................................................................4
Experiment ................................................................................................................................6
Results ........................................................................................................................................8
References ...............................................................................................................................11
Apendix ....................................................................................................................................12

Theoretical background
First, we can define the specific heat capacity of a material as the quantity of energy
needed to raise the temperature of one gram of a substance by one degree Kelvin. For a
substance with mass m heated with energy dQ with temperature change of dT has a specific
heat capacity with the following relation:

Knowing this relation from thermodynamics: dU=dQ-pdv; and assuming that our
sample is supplied with heat energy with no volume change. Therefore the heat energy supplied
is assumed to be equal the internal energy of the sample.
There are two main contributions for the internal energy term U:

Phonons: phonons can be described as lattice vibrations. This contribution is

temperature dependent but for T>1K.
o The Debye model approximation states that the contribution for phonons for
different temperature ranges as:

At sufficiently high temperatures: The specific heat capacity contribution

is almost equals to 3R 25J/mol/k.

At low temperatures: The specific heat capacity contribution is almost

observed as T3 dependence.

Conduction Electrons: only in metals, the conduction electrons which are thermally
excited contribute to the electrical conductivity. This contribution dominates at T<1K.
o The Sommerfeld model approximates that the specific heat due to the
conduction electrons is related to this equation:

Where

is the Sommerfeld constant.

So we can express the total specific heat capacity of a metal due to the contributions of
both the phonons and the conduction electrons which is related to the following equation:

Where

; R is the gas constant equals to 8.314

and

is the Debye

temperature.
If we plot a relation between
determine

and

, we can calculate A from the slope so we can

the Debye temperature for the material and

the sommerfeld constant form the

intercept.

Experimental Setup
The following instrument was used as the main apparatus for the experiment:

Fig. 1: Schematic representation of the equipment used for determining the molar heat
capacity of the copper sample at low temperatures.
In the centre of the equipment is the object of interest the sample: copper cylinder with
a relatively large mass (424 g in this case). The wires (made of thermo-insulating material) are
holding the sample placed in a relatively high vacuum ( P = 104 105 mbar). A carbon resistor
is in contact with the sample and is used to measure the sample temperature. Carbon is used for
this purpose because it is not a metal (resistance of the metals decreases when decreasing
temperature thus they would not be accurate thermometers at very low temperatures). For the
case of carbon the resistivity increases with decreasing temperature, but unlike typical
semiconductors, carbon still remains a relatively good conductor at low temperatures. A heater
made of a thin wire is wound around the sample. Electrical energy from the power source is
used to heat the sample. Surrounding the metal container where the sample is situated is a
Dewar vessel filled with liquid helium. The helium containing Dewar vessel is situated in
another Dewar vessel filled with liquid nitrogen. A system of pipes and pumps is incorporated
in the apparatus in order to provide vacuum and for introducing heat exchange gas.

Experiment
First, the Dewar vessels were filled with liquid nitrogen and liquid helium. Then Pump1
(see Fig. 1) was used to obtain vacuum in the sample container to thermally insulate the sample.
Pump2 provided a vacuum in the Dewar vessel containing the liquid helium in order to lower its
temperature (evaporating liquid helium is an endothermic process, thus a temperature in the
order of 2 K can be reached). The next step was to introduce the exchange gas; helium gas from
the inner Dewar vessel was moved into the sample container by opening the valve which
connects Pump1 to Pump2 (Fig. 1). The exchange gas is necessary to transport heat away from
the sample towards the liquid helium.
After the sample had been cooled down to approximately 2 K the exchange gas was
evacuated from the container, and the sample was thermally insulated. That gave us the

possibility to measure the heat capacity. First, the temperature was measured indirectly by the
computer software from the resistance.
The sample was being heated by the electrical heater. In our case, constant voltage was
applied for a determined time interval. The voltage, the current and the heating time were
recorded. Assuming constant (average) values for the voltage and current, the energy supplied
by the heater was calculated using the following formula:
Q = I U t

All these steps were performed many times in the temperature range from 2 K until 26
K.
Below we can see the temperature vs. time graph, which was constructed from the
obtained data. From the ramps on this graph the temperature values for each heating can be
determined.

25

Temperature, K

20

15

10

0
0

500

1000

1500

2000

2500

3000

3500

Time, s

Fig. 2: Temperature vs. Time

On the graph, in the approximate region of 750-800s we can see quite big decrease of
temperature before to consequent heatings. That is an experimental error, which was caused by
a long pause between the heatings.
The molar heat capacity of the sample is defined by:

c ( T ) = cmol ( T ) =

dQ
Q

n dT n T

Knowing the mass of the sample (Cu, 424g), the number of moles can be determined by
n=

m(Cu )
. Thus all the parameters necessary are known, and the molar heat capacity of
A(Cu )

copper corresponding to different temperatures can be calculated. The acquired data are
presented in and Table 2 in the appendix.

Results
The graph obtained from the experimental data, showing the relation of the molar heat
capacity versus temperature is presented in the following figure:
Molar Heat Capacity

2,5

-1

-1

Molar Heat Capacity (J *K *mol )

3,0

2,0

1,5

1,0

0,5

0,0
0

10

15

20

25

Temperature (K)

Fig. 3: Dependence of the molar heat capacity of copper on temperature

According to free electron theory, the shape of the curve near very low temperatures is dictated
by the linear term of the

equation. On the contrary, at higher temperatures

the cubic term would dominate. A characteristic of the obtained graph is that the molar heat
capacity of the metal approaches zero at very low temperatures. This is in agreement with the
theory.
We see from the figure 3 one point at 9.731 K and 0.1818 J*K -1*mol-1, which deviates
from the total behavior. Most probably data for this particular value was either measured or
written dawn wrongly.
Next, if we divide this equation by T we obtain:
c(T )
= AT 2 +
T

If we plot

c(T )
as a function of T 2 we should obtain a straight line with a slope A and
T

an intercept . However, our results plotted on Fig. 4 do not correspond to the theoretical
prediction of equation for C(T). We obtained a nonlinear relationship. Applying the least square
fitting method, we constructed a linear trend line. These results are shown in the following
figure:

Cmol/T
Linear Fit of Cmol/T
0,12

Equation

y =a +

Adj. R-Squ 0,9650

-2

-1

Cmol/T (J *K *mol )

0,10

Value
Cmol/T

Intercep -0,00366

Cmol/T

Slope

Standard E
0,00119

1,73983 5,1677E-6

0,08

0,06

0,04

0,02

0,00
0

100

200

300

400

500

600

700

T^2 (K )

Fig. 4: Dependence of the quotient of the molar heat capacity and temperature
the square of the temperature T 2
8

c
versus
T

Note that the slope of the fitting is A=1.73983*10^-4 JK-4mol-1 and the intercept is at =0,00366 J*K-2*mol-1. The Debye temperature can be readily calculated using the slope A by the
equation D =

12 4 R
. The following result was obtained D =223.4K.
5A

The theory predicts a line intersecting at some positive intercept ( ). Our results,
however, display a negative intercept. This indicates that a systematic error might be present.
We might have some preliminary assumptions concerning the origin of this error. One of the
reasons might be the slow heating rate. If we have a look again at the figure 1, we see that the
slope of the temperature curve at higher values changes several times and if we come back to
the last graph we see that the dots at the temperatures higher than 15K, where we used 1K
heating step, are shifted upwards, which results in negative intercept. For that purposes we
decided to neglected the points at lower temperature and we found that in that case
A=9,524*10^5 JK-3mol-1 and =0,0135 J*K-1*mol-1 (fig. 5)

Cmol/T
Linear Fit of Cmol/T
0,12

Equation

y =a +

Adj. R-Squ 0,9288

-1

0,08

-2

Cmol/T (J *K *mol )

0,10

0,06

Value

Standard E

Cmol/T

Interce

0,00135 4,45977E-

Cmol/T

Slope

9,52374 4,7291E-6

0,04

0,02
0,00
0

100

200

300

400

500

600

700

T^2 (K )

Fig. 5: Dependence of the quotient of the molar heat capacity and temperature

c
versus
T

2
the square of the temperature T

In this case the Debye temperature will be 273K, which is much closer to the theoretical
value for copper of 343.5K [1].

References

1. Charles Kittel, Introduction to Solid State Physics, John Wiley & Sons; 8th international

edition edition (2004)

10

Appendix
Table 1:
Results obtained directly by measurement. U (V) is the applied voltage, I is the applied
electrical current and t is the time interval of heating. The current is expressed as Volts
applied to a resistance equal to 10 Ohms, which is the resistance of the heater wire.
U
V

I
A

t
s

0,1526
0,1536
0,1533
0,1546
0,1538
0,2301
0,2325
0,291
0,2941
0,2922
0,2944
0,2949
0,441
0,446
0,4438
0,5905
0,5906
0,7325
0,7413
0,7418
0,7409
0,7456
0,7503
1,086
1,00772
1,3451
1,3584
1,3587
1,3667
1,781
1,7438
1,7467
1,7475
1,7782
1,8071
2,435

0,00167
0,0018
0,00155
0,00182
0,00161
0,00275
0,00255
0,00349
0,00348
0,0035
0,0035
0,00347
0,00501
0,00524
0,00515
0,00699
0,00679
0,00855
0,0086
0,00885
0,00888
0,00893
0,00955
0,01281
0,01284
0,01553
0,01603
0,01614
0,01584
0,0202
0,02029
0,02063
0,02059
0,02108
0,02124
0,0281
11

19,1
22,58
27,22
40,76
55,02
23,8
24,15
15,98
20,07
22,34
101,5
41,03
13,27
34,54
39,78
26,35
31,14
22,39
31,1
25,06
51,29
30,99
104,9
29,92
33,92
24,11
24,56
21,87
36,62
47,61
52,03
24,98
117,39
128,69
148,03
123,37

2,458
2,447
2,488
2,505
2,533
2,54

0,0281
0,029
0,0291
0,029
0,0299
0,0302

110,19
134,41
149,79
206,47
223,65
249,98

Table 2:
Calculated parameters necessary for solving the problem. Taverage is the mean of Tstart and Tfinish,
which are the temperatures of the sample correspondingly before and after heating, Q is the
portion of heat supplied to the sample Cmol is the molar heat capacity of the copper sample.
Additionally, T2 is the square of the Taverage and Cmol/T is quotient of the molar heat capacity and
average temperature.
Tstart
K

Tfinish
K

T
K

Taverage
K

T2
K2

2,478

2,69

2,584

6,67706

2,679

2,88
3
3,06
5
3,26
4
3,46

0,21
2
0,20
4
0,20
1
0,25
5
0,26
5
0,28
9
0,23
1
0,24
8
0,27
2
0,25
9
0,74
2
0,32
8
0,27
3
0,63
3
0,52

2,781

7,73396

2,9645

8,78826

3,1365

9,83763

3,3275

11,0722
6
12,4714
9
14,1263
2
15,3664

2,864
3,009
3,195
3,387
3,643
3,796
3,953
4,164
3,877
4,507
4,739
4,909
5,514
5,971
6,51

3,67
6
3,87
4
4,04
4
4,22
5
4,42
3
4,61
9
4,83
5
5,01
2
5,54
2
6,03
4
6,53
7
7,04

0,56
6
0,53
12

3,5315
3,7585
3,92
4,089
4,2935
4,248
4,671
4,8755
5,2255
5,774
6,254
6,777

16,7199
2
18,4341
4
18,0455
21,8182
4
23,7705
27,3058
5
33,3390
8
39,1125
2
45,9277

6,914
7,424
8,043
8,439
9,111
9,425
10,01
5
10,54
4
11,03
5
11,57
9
12,07
5
12,47
2
13,02
5
14,10
3
15,08
6
15,43
2
16,46
2
17,44
5
18,43
9
19,60
5
20,49
2
21,46
4
22,45
23,43
6
24,44
2

4
7,46
8,04
6
8,44
9,12
7
9,44
1
10,0
37
10,5
74
11,0
92
11,5
57
12,0
34
12,4
51
13,0
5
14,0
6
15,0
62
15,4
45
16,4
56
17,4
43
18,4
38
19,5
98
20,4
81
21,4
56
22,4
41
23,4
36
24,4
39
25,4
36

4
0,54
6
0,62
2
0,39
7
0,68
8
0,33
0,61
2
0,55
9
0,54
8
0,52
2
0,45
5
0,37
6
0,57
8
1,03
5
0,95
9
0,35
9
1,02
4
0,98
1
0,99
3
1,15
9
0,87
6
0,96
4
0,97
7
0,98
6
1,00
3
0,99
4

13

7,187
7,735
8,2415
8,783
9,276
9,731
10,294
5
10,818
11,296
11,806
5
12,263
12,761
13,542
5
14,582
5
15,265
5
15,944
16,952
5
17,941
5
19,018
5
20,043
20,974
21,952
5
22,943
23,937
5
24,939

3
51,6529
7
59,8302
2
67,9223
2
77,1410
9
86,0441
8
94,6923
6
105,976
73
117,029
12
127,599
62
139,393
44
150,381
17
162,843
12
183,399
31
212,649
31
233,035
49
254,211
14
287,387
26
321,897
42
361,703
34
401,721
85
439,908
68
481,912
26
526,381
25
573,003
91
621,953
72

Cmol

14

Cmol/T

J*K*mol-1

J*K*mol-1

watt

0,00487

2,55*10-

0,00344

0,00133

0,00624

2,76*10-

0,00458

0,00165

0,00647

2,38*10-

0,00482

0,00163

0,01147

2,81*10-

0,00674

0,00215

0,01362

2,48*10-

0,0077

0,00231

0,01506

6,33*10-

0,0078

0,00221

0,01432

5,93*10-

0,00928

0,00247

0,01623
0,02054
0,02285
0,10459
0,04199
0,02932
0,08072
0,09092
0,10876
0,12488
0,14023
0,19827
0,16452
0,33745
0,20634
0,75165
0,41624
0,4389
0,50364
0,5348
0,4796
0,79277
1,71283
1,84091
0,90014
4,22381
4,82387
5,68181
8,44141
7,6108
9,53814
10,8449
2
14,9990
1

0,00102
0,00102
0,00102
0,00103
0,00102
0,00221
0,00234
0,00229
0,00413
0,00401
0,00626
0,00638
0,00656
0,00658
0,00666
0,00717
0,01391
0,01294
0,02089
0,02178
0,02193
0,02165
0,03598
0,03538
0,03603
0,03598
0,03748
0,03838
0,06842
0,06907
0,07096
0,0724

0,0098
0,01131
0,01321
0,02111
0,01917
0,01608
0,0191
0,02619
0,02878
0,03502
0,03846
0,04774
0,06206
0,07346
0,09364
0,18394
0,11152
0,11995
0,1445
0,17603
0,19103
0,20541
0,24785
0,28749
0,37551
0,61775
0,73644
0,85693
1,09078
1,30117
1,48181
1,66241

0,0025
0,00277
0,00308
0,00497
0,0041
0,0033
0,00365
0,00454
0,0046
0,00517
0,00535
0,00617
0,00753
0,00836
0,0101
0,0189
0,01083
0,01109
0,01279
0,01491
0,01558
0,0161
0,0183
0,01971
0,0246
0,03874
0,04344
0,04776
0,05735
0,06492
0,07065
0,07573

0,07264

2,27821

0,0993

15

16,9385
1
19,1754
7

0,07574

2,52919

0,10566

0,07671

2,88913

0,11585

16