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The Problem of Counting the Number of Molecules

and Calculating Thermodynamic Properties


An Experimental Approach
Luis Alfonso Torres, Imelda Hernandez-Contreras, and Juan Antonio Guardado
Laboratorio de Termoquimica, Depto. de Quimica, Centro de Investigacion y de Estudios Avanzados del I.P.N. Apdo.
Postal 14-740, 07000 Mexico, D.F. Mexico

Many physical chemistry and thermodynamic textbooks above procedures, it is necessary at least to imagine the
state that the thermodynamic properties of a system can possibility of counting the molecules and determining
be considered a s the average of mechanical variables. their velocities. Unfortunately, there is not a microscopic
However, not many examples of an experimental approach observer working like a Maxwell demon and carrying out
to illustrate this statement have been given. The problem this formidable task.
begins with the question of the meaning of average. In re-
ality, there are several averaging procedures that can be - The Knudsen Effusion Method ,

used, as described in ref 1. To Count the Number of Molecules


As an example let us consider the pressure of a gas. This Fortunately, Martin Knudsen (2, 31, at the hegining of
quantity is related to the momentum transported by the this century, while developing the kinetic theory of gases,
molecules of the gas through a unit area per unit time. For devised a method using macroscopic procedures to deter-
practical purposes let us consider a vessel containing a gas mine the pressure of a gas or to measure the average of the
constituted by only one type of particles. Imagine that momentum transported in an indirect manner. Knudsen
within the vessel a small window of unit area is hung from considered that pressure arises from forces exerted when
the top of the container. The average of the momentum can particles strike the unit area of the wall of the gas con-
be calculated if a microscopic observer seated at the win- tainer per unit time. The gas particles are moving through
dow's corner (Fig. l a ) is able to carry out the extremely all the available volume. At equilibrium, the molecular ve-
boring task of counting the number of molecules crossing locities are described by the Maxwell-Boltzman distribu-
the window a d determining t h e ~ velocities.
r The total mo- tion function. If the vessel is completely closed, the gas
mentum is computed and divided by the observation time. molecules collide against the wall. The transfer of momen-
tum during these collisions is revealed a s a force that,
when expressed per unit area is normally known as the
pressure.
Therefore, the problem of determining the pressure re-
duces to knowing the number of molecules that can reach
the unit area of the wall in a second (Fig. 2a). Knudsen
showed that this number, or the pressure, can be calcu-
lated if an orifice of areaA is pierced at the top of the vessel

a b
Figure 1 . Schematic representation of averaging procedure over the
molecules ( 1 a) and over the time (1b).

A second way of averaging is really funny: Have an ob-


server ride on a molecule, and take a very long trip during
which the molecule and the observ.-r rross the window of
unit area many times (Fig. lb). The average oi'the momen-
tum transported can be calculated by counting the number
of times that the molecule (and rider) crosses the imagi-
nary window. Determine the corresponding velocities, and
then divide by the traveling time.
A third way is not so funny because it involves some
ma'thematical work that consists of calculating the mo-
mentum transportel by the molecules crossing the unit
a b .
.-
,- .
area per uiiit tii~le.I'he average is ol-,i,ainatl ; JJ ~ ~ ~ u ; t i _iiig
iri.~
the quantity (mv) by the distribution function, and then Figure 2. Molecules inside the cylinder can reach the container's w d l
integrating over the velocities and the volume. In the (Pa):schematic representation Of the Knudsen effusion process (@.

Volume 72 Number 1 January 1995 67


/',
(Fig. 2b) maintained at temperature T, and the rate of loss Substituting eq 1 into eq 2 followed by integration, as-
of mass (drnldt) is observed. Such an experimenta! device suming that the enthalpy change of the phase transition is
is called a Knudsen effuslon cell. The pressure is given by indepenJent of the temperature, we get eq 3.
the Knudsen equation (eq 1).

where In B includes the term (lIA)(ZxRIM),which remains


constant during an experiment. From this equation the en-
where R is the gas constant, and M is the molecular weight thalpy of sublimation can be easily obtained from the slope
of the gas. of the straight line resulting from plotting the left-hand
In order to ens-we the distribution function and the equi- term of eq 3 versus 1lT.
librium in the system, several experimental conditions are The sublimation process car. be schematically repre-
imposed. The calculation assumes t h a t the gas has a n sented in Figure 3. The solid sample is placed at the bot-
I ideal behavior. Therefore, the pressure inside the con- tom of the Knudsen cell and placed into a holder connected
tainer must be kept as low as possible. The effusion orifice to a high vacuum system. When the pump is started the
must be smaller than the mean free pathway between suc- residual air is pumped out, and the sublimation process
ces'sive collisions, and the thickness of the orifice must be begins. If the temperature is fixed, when the equilibrium is
negligible in order to guarantee that a molecule reaching reached the pressure of the vapor phase becomes fixed be-
the orifice always leaves the container. This last condition cause the phase rule must be satisfied. (The system is one
cannot he experimentally satisfied, and a Clausing prob- component with two phases in equilibrium, so there is one
ability factor (4) must be applied. degree of freedom.) The geometrical characteristics of the
cell must be carefully established because the equilibrium
The Vapor Pressure as an Example must not be perturbed by the presence of the orifice. In this
The above restrictions seem to have been exactly de- case, even when the vapor molecules are continuously es-
signed for the measurement of the vapor pressure of an caping through the orifice, the molecules are being con-
organic or organometallic solid compound, ranging typi- tinuously replaced from the subliming solid phase, and the
cally from 0.1 to 10 Pa. Many laboratories worldwide carry distribution function through the gas is re-established.
out measurements of vapor pressure as a function of the Typically, the effusion rate of the vapor in equilibrium
temperature using this method. This principle is also ap- with its solid is around g s-', using orifices ranging
plied for vapor pressure measurements of metals at higher , from 0.1 to 1 mm at temperatures between 0 and 140 "C.
temperatures. Some technologies for the preparation of Traditional vacuum electrobalances are not the best in-
some semiconductor materials require deposition of thin struments for measuring such a small mass flow because
films from molecular flow of vapors escaping from Knud- their sensitivity may be just 0.1 mg, and a reliable deter-
sen ceils mination of drnldt requires a long time. Actually, the en-
In addition, other thermodynamic properties can be de- thalpy of sublimation can be obtained from eq 3 even if the
rived from the vapor pressure as a function of tempera- rate of loss of mass is not exactly known. Instead only a
ture. In particular the enthalpy of sublimation can be ob- proportional quantity is experimentally available.
tained from the well-known Clausius-Clapeyron equation.
The Piezoelectric Effect
At this point it is important to take a look at the really
attractive piezolectric effect shown by many materials.
Among them, t h e most popular is the quartz crystal.
Quartz crystals are made of silicon and oxygen atoms in a
periodical three-dimensional arrangement. Therefore, sev-
eral cuts (e.g., AT, BT, CT, X, Y) can be made at different
angles relative to a major axis (Fig. 4).These pieces of crys-
tal present the piezoelectric effect (from the Greek piezin,

i To the Vacuum System meaning to press) discovered a t the end of the 19th cen-

Figure 3. Schematic representation of the sublimation process. Figure 4. Crystal structure of quartz and cuts of piezoelectric pieces.

68 Journal of Chemical Education


Mechanical
Compressio?.
- 1
Voltage
Supply

-
Figure 5. schematic representation of the piezoelectr~ceffect.

tury. It can be defined as an electric polarizatio~lproduced


by mechanical strain. In other words, if pressure is applied
over a piece of quartz crystal, a charge separation occurs,
and a source of electromotive force is created. Alterna-
tively, when a voltage is applied across the crystal, me- Figure 7. Details of the Knudsen effusion cell.
chanicak movement is produced. In addition when a volt-
age is supplied as pulses a t the proper frequency, the ties are affected by the thickness change, producing a fre-
crystal vibrates and produces a steady signal. For each cut quency resonance variation (dvidt) that displays a number
of the crystal, the mode of vibration (bending, shear, tor- proportional to the rate of loss of mass of the cell (dnldt)
sion, etc.) and frequency resonance are characteristic. and to the vapor pressure. The sensitivity of such a micro-
These phenomena are represented in Figure 5.
balance is about g s-' (or a vanation of 1 pg in 100 s),
From this physical principle, a quartz crystal can be allowing a few time-consuming experiments. Aseries of 10
used as a weighing device to count the molecules if we are to 1 2 measurements a t different temperatures can be
able to keep these molecules aver its surface. It is evident made in a day's work. Also, the microbalance is not sensi-
that when molecules are being condensed on the surface of
tive to mechanical vibrations in the environment. Micro-
the crystal, the thickness increases continuously, so more
and more energy is necessary to make it vibrate. This fact balances working on this principle have also been de-
is the basic principle for Knudsen effusion measurements. scribed by Glukhova (5)and Burkinshaw (6).Details of the
physics and instrumentation have been extensively de-
For our purpose, the cut AT with thickness shear mode scribed by Lu and Czanderna (7).
of vibration is adequate. The molecules escaping through
the orifice of the vessel can be trapped on the liquid-nitro- Experimental Setup
gen-cooled surface of the crystal. The mechanical proper-
An experimental setup is schematically displayed in Fig-
ure 6. The geometrical design and materials of the Knud-
sen effusion cell A are detailed in Figure 7. The cell holder
B is made of aluminum and works as a thermal stabilizer.
It also houses the temperature sensors C (thermistors or
platinum resistances). The holder has a flange for quick
raccording to other vacuum-line elements. During an ex-
periment the holder is immersed in a temperature-control-
led water bath D. A crosspiece was used to introduce a cold
finger E, supporting the quartz crystal F, just in front of
the effusion orifice. The crystal is electrically connected to
the reference oscillator H, using a feedthrough G. Com-

Figure 6. Schematic diagram of the experimental setup as described Figure 8. Graphical representation of experimental results to deter-
In the text. mine the enthalpy of sublimation of naphthalene.

Volume 72 Number 1 January 1995 69


,' ,
parison of the frequencies from the reference Experimental Sample Data for a Knudsen Effusion Experiment
oscillator and the crystal is detected at a fre- of Naphthalene Using a Quartz Crystal Microbalance
quency meter I.
A Sample of Experimental Results
An experimental run was canied out with a
sample of a pure compound, in this case naph-
thalene. Measurements of resonance fre- --
296.1 27 32.241 6 3.3769 6.3187
quency and time were taken at a given tem-
perature while the vapor molecules were being 295.240 29.4833 3.3871 6.2277
condensed. These values lead to a straight line 294.052 25.8850 3.4008 6.0955
from which the slupe (dvldt)~ was calculated. 293.079 23.5800 3.41 20 6.0006
The procedure was repeated at different tem-
290.872 18.8516 3.4379 5.7730
peratures, and the results were analyzed using
eq 3 to obtain the enthalpy of sublimation. A 289.943 17.0016 3.4490 5.6681
typical experimental data set is summarized in 288.720 15.0850 3.4636 5.5464
the table whle the graphical representation of 287.438 13.1983 3.4790 5.41 06
eq 3 is shown in Figure 6. The value A f f s , b =
+
(73.19 0.52) kJ mol-' can be assigned to the
286.1 95 11.7500
Onficediameter is 150 pm.
3.4941 5.2922
average temperature (291.16 K) because the
expenxsents were made between 286.19 and Least-squaresanalys~sleads to AHsub = 73.19 r 0.52 kJ rnol".
296.13 Comparison with the reported val-
ues (8)of enthalpy of sublimation was possible
taking into account that for this reference material.
Acknowledgment
reported by De Kruif (9).This allows us to calculate the We acknowledge financial support from the National
corrected value at 298.15 K as Council of Science and Technology (CONACYT-MEXICO)
for purchase of the equipment. One of us (J.A. Guardado)
2 9 8 15
wishes to thank CONACYT for his scholarship.
AHsub (298.15 K) = AHsub (291.16) + AC,~T Literature Cited
291.16 1. Berry, R. S ; Rice. S . A,, Rosa J . Physrcal Chemtstry, Part n o . Mattrrin Equilzbrium:
Statrstlcal Mechanics and Thermodynarnrcs; .John Wiley and Sons: New York.
1980; Chupter 15
Assumin? t , h ~.\Cp
; is constant over the integration tem- 2. Knudsen. M . Ann. Phy:;rh 1909. 28, 75.
3. Knudsen. M . Kinrtro Theory rif Cirse~,Some blc,darrt A;pr.cfc. 2nd ed.; Methuun'
perature range, we get M o r r o ~ r a ~ of
h sPhvsical Subiecta: Methuen: Landon. 1946.
4. C I U U Y ~ & . k ~ n nphysik
. 1932: 12, 961.
5. Glukhova, 0.T.:Arkhangelnva, N . M . ; Teplltsky, A. B.; Sukhodud, L. F ; Yanaon. I . K
Thernrochirnrca Acta 1986,95. 133.
6. Burkinshaw, P Ni.; Murti~r~rt; C . T J. Chem. Soc. Dalton P a n s . 1984, 75.
7. Lu, C . ; Czanderna. A. W A p p l i c a t ~ o nof
s P~ezoelectricQuartz Crystal Microbalan~es,
Vol. 7. Methcds and Phenomena, Their Applications in Science and Technology;
Elsevlel.: Amsrerdun. 19R4.
The latter value is in good agreement with the estab- 8 Torres-G6rnez. L. A.. Barre~rc-Rodriguez. G . ; Galarza-N[01ldray6n. A. Thermu-
chrmrca Acta 1980,124.229-233.
lished value (10)of 9. De Kru~f,C . C. J. Chem. Thermodyn. 1981, 13,1081.
10. Head, A. J., Sabbah, R. Recumrnrrdrd Reference Matwinin for t h Realization ~ of

AHYub(298.15K) * (72.15 + 0.50) kJ m0l -' Physrcichemical Propertres. International Union o/'Pure and Applted Chemrstry;
Mamh, K. N.. Ed.; Blackwell: Oxford. 198; Chapter 7, p 272.

A Metal-Encased Dewar Flask

Glass Dewar flasks are susceptible to implosion by either mechanical or thermal shocks. A previous article in this
Journal describes using polyethylene bottles to protect Dewar flasks from breakage ( 1 ) .For even greater protection,
Dewar flasks may be purchased encased in metal cylinders, but these are expensive. In order to hold down costs while
improving safety, a homemade metal-encased Dewar was constructed. The cost of the materials is about one-tenth the
cost of a conlmercial flask. The homemade flask has held up well to use with liquid nitrogen.
The steel casing is made from two 13-02 coffee cans. One can has both the top and bottom removed. The other can
has its top removed and four small holes punched in its bottom. The two cans are taped together to form a steel cylinder.
A Thermos brand size 74F or 75F borasilicate glass replacement liner will fit into the cylinder with approximately
3116-in. radial clearance. Two small pieces of cardboard are used to center the Di..ar in the cylinder. A commercial
spray polyurethane-isocyanate foam is then injected through the holes in lhe bottom and along the sides to completely
fill the gap between the Dawar and the cylinder. After the foam cures overnight, trim off any excess. Although quanti-
tative tests have not been conducted, the foam is expected to provide shock resistance, supplement the insulation, and
help to secure the outer wall of the Dewar in the event of a n implosion.

Literature Cited
1 Dymicky, M . J . Chrm. Educ. 1971.48.397

David Ritter
Southeast Missotiri Etats Univcsity
Capa Girardeau, MO 63701

70 Journal of Chemical Education

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