Mitul Patel 1

Boltzmanns constant by Brownian motion

Mitul Patel and collaborator (Chris)
Applied Physics 1
st
year, St Mary's university

Abstract
The purpose of this experiment was to calculate the value of Boltzmanns constant by Brownian motion. The
water molecules start to agitate due to thermal vibration of the molecules therefore they constantly bump into
the beads causing them to move. This is called Brownian motion. The beads starts to move randomly and the
displacement of the beads can be calculated using equation which is described in this paper. Data were
collected at 23 0.5
o
C, value of Boltzmanns constant (K) was calculated to be (1.39 x 10
-23
0.74 x 10
-23
) J/k
which was close to the actual value 1.38 x 10
-23
J/k. Additional to this, value of Avogadro number was also
determined and was found to be 5.98 x10
23
mol
-1
which was found close to actual value 6.02 x 10
23
mol
-1
.

Introduction
Brownian motion was first proposed by Robert brown
in 1827, who was a microscopist and the curator of the
botany collection at the British museum. He was
interested in finding evidence of vital forces in living
organism and he found that the fragments of pollen
grains in plants were moving randomly. He devised
experiments to study this further. One of the
experiment was, he shook up almond oil with water in
which active particles were suspended and he noticed
that the active particles were still moving in random
jiggling way as that show in fig.2 and the random
motion of a particle is shown in fig.1as seen live but he
could not determine the mechanism behind this.

Fig.1. shows the trajectory of a particle with respect to time.
This was left to Albert Einstein to solve. In 1905 Albert
Einstein published a paper that explained both the
random motion of the particles and also made
measurable predictions and this was verified
experimentally by Jean Baptiste Perrin within 5 years
of publication. He devised an experiment of pollen
grain suspended in water and the trajectory of the
particles recorded by him is shown in fig.2. Einstein
imagined that the atoms would fluctuate in their
movement and in the regular interval of time atoms
motion would be unsymmetrical i.e. the atoms will
change their direction of motion in a very short period
of time. Thus, this would mean that the visible particles
experience unbalanced force over a short interval of
time due to the collision with atoms moving one way or
the other. As a consequence due to the collision the
particles would start to move in a one way or the other
in random motion depending on the direction of the
bombardment of the particle. The collision of these
atoms also has an effect on the velocity of the visible
particles, although this was causing the particles to
accelerate but the particles were slowed down due to
the friction within the fluid. In other words the particles
were drifting in the fluid in random motion.

Einsteins paper of 1905 entitled On the movement of
small particles suspended in a stationary liquid
demanded by the molecular-kinetic theory of heat had
a great impact. He derived a formula that related the
displacement of the visible particles over time to the
temperature and viscosity the particles were
suspended in, using statistical methods, considering
diffusion, osmosis and friction.



Fig. 2shows the diagram of position of three particles plotted
every 30s by Perrin

The equation derived by Einstein to calculate the
displacement of the particles is given in equation (1)

Mitul Patel 2

"#$
Where x
2
displacement (m
2
)
K
B
Boltzmanns constant (j/k)
T temperature in Kelvin (k)
T time (s)
! viscosity of fluid (Pa s)
r radius of particle (m)

The above equation (1) (See Appendix 1 for the
derivation) was used in our experiment to determine
the value of Boltzmanns constant and the equation (2)
given below to determine Avogadro number using the
experimental value of Boltzmanns constant.

(2)

Where N
A
Avogadro number
R Ideal gas constant (8.31 J/mol K)

The experiment was carried out with beads suspended
in water.

Experimental Procedure

The experimental arrangement is shown in figure 3
below.




Fig.3. shows the experimental setup. Microscope slide with a
solution under the microscope which is viewed on the
computer via digital camera
Microscope slide was prepared by filling the concave
depression in a standard glass slide with a drop of
suspension of beads and then quickly covered with the
cover slip in order to avoid trapping air bubbles. The
prepared slide was then placed on the stage of the
microscope and microscope lamp was turned on.
Binocular microscope was used in order to observe the
particles. One eyepiece of the microscope was
replaced with the UView digital camera and was
connected to the computer. The software was already
downloaded on the computer by the demonstrator. The
UView software allowed us to record snapshots and
extended video of the particles in Brownian motion in
2D. The 40X objective was set up on the microscope.
The lens was focused within the depression of the
slide. The in-focus beads was seen moving as
Brownian motion.
Setup of the UView Software
Under the video proc Amp tab, settings were altered
as following in order to observe clear picture of
particles:
Brightness = -6
Contrast = 12
Hue = 0
Saturation = 5
Sharpness = 7
Gamma = 160
White Balance = 6500
Backlight Comp = 0

Under the Camera Control tab:
Exposure = -4 with Auto deselected

With these settings the particles was seen clearly and
in motion. The contrast setting could be altered further
if the particles were difficult to see. About 10-15
second video of the particles in motion were captured
and was saved on the computer under suitable title.
Once the video was captured and saved, it was altered
further in appearance so that the particles can be
easily tracked. To do these following sets were
followed:
* Opening Image J file which was saved on the
computer by the demonstrator then selecting file tab,
then import-> AVI file by selecting the saved video.
This uploads the video into Image J.
* The video was cropped to approximately 800 x 400
pixels wide.
* Filtering was done by clicking on the process tab,
then filters then Mean and by entering 3.0 pixels. The
video was then converted to black and white by
selecting Image tab, then Type, then 8-bit.
* Contrast and Brightness were adjusted and the file
was saved as AVI.
Tracker software was used to track the motion of
particles at 3 frames/second. Tracking software was
already downloaded by the demonstrator. The way this
was done is by selection a particle which was clear
and easy to observe and tracking there motion at
regular intervals. The motion of at least 7 particles
were selected and only 4 particles motion were used
Digital Camera
Live Video
Microscopic
Objective
Microscope Slide
Light Source
Stage
Mitul Patel 3

to calculate the value of Boltzmanns Constant as
other data were anomalous resulting enormous error in
the value of Boltzmanns constant. In addition to this,
the value of Avogadro number was also calculated
using the experimental value of Boltzmanns constant.

Results and Discussion

The results of this experiment are presented below in
table1, table2, table3, table4. The results presented
below were to calculate the value of Boltzmanns
Constant. The other data which were anomalous are
presented in the appendix 2. No graphs were plotted
as this was not needed to calculate the final value.
t / s (+/-
0.01s)
x / "m
(+/-
0.4"m)
y / "m
(+/-
0.4"m) #x^2/pm
avg
#x^2/pm
0.00 24.41 1.25
0.33 24.98 1.25 0.33 0.60
0.67 24.91 1.06 0.01
1.00 25.72 0.94 0.66
1.33 26.35 0.50 0.40
2.33 25.91 0.56 0.20
3.00 27.22 0.25 1.72
3.33 27.32 -0.69 0.01
4.67 28.59 -1.56 1.62
5.00 29.30 -1.38 0.50
Table1 shows the data of a particle with their associated
precision
t / s (+/-
0.01s)
x / "m
(+/-
0.4"m)
y / "m
(+/-
0.4"m) #x^2/pm
avg
#x^2/pm
0.00 -11.47 -9.13
0.33 -11.22 -9.50 0.06 0.359
0.67 -11.91 -9.38 0.47
1.00 -12.53 -9.19 0.39
1.33 -12.72 -9.06 0.04
1.67 -11.97 -9.94 0.56
2.00 -11.41 -9.75 0.32
2.33 -11.72 -10.06 0.10
2.67 -11.66 -10.44 0.00
3.00 -10.72 -10.94 0.88
3.33 -11.41 -11.19 0.47
3.67 -10.53 -11.31 0.77
4.00 -10.72 -11.63 0.04
4.33 -10.47 -11.75 0.06
4.67 -11.28 -11.56 0.66
5.00 -11.59 -12.19 0.10
5.33 -12.78 -12.00 1.41
5.67 -12.78 -12.38 0.00
6.00 -12.41 -12.50 0.14
Tabe2 shows the data of particle 2 with their associated
precision
t / s
(+/-
0.01s)
x / "m (+/-
0.4"m)
y / "m
(+/-
0.4"m) #x^2/pm
avg
#x^2/pm
0.00 13.84 -0.25
0.33 15.09 -0.75 1.563 0.253
0.67 15.28 -1.13 0.035
1.00 15.97 -1.13 0.473
1.33 16.09 -2.06 0.016
1.67 15.59 -2.38 0.250
2.00 15.72 -2.88 0.016
2.33 15.41 -3.44 0.098
2.67 16.16 -3.88 0.563
3.00 16.03 -3.94 0.016
3.33 15.78 -3.88 0.063
3.67 15.72 -3.75 0.004
4.00 15.47 -4.13 0.063
4.33 15.53 -4.63 0.004
4.67 16.22 -4.00 0.473
5.00 15.97 -4.13 0.063
5.33 15.91 -4.25 0.004
5.67 16.72 -4.56 0.660
6.00 17.16 -4.69 0.191
Tabe3 shows the data of particle 3 with their associated
precision
t / s (+/-
0.01s)
x / "m
(+/-
0.4"m)
y / "m (+/-
0.4"m) #x^2/pm
avg
#x^2/pm

0.33 3.09 4.00 0.23
0.67 2.28 3.69 0.660
1.00 2.84 3.69 0.316
2.33 3.09 2.63 0.063
2.67 2.84 2.63 0.063
3.33 2.53 2.50 0.098
4.33 3.16 1.81 0.391
4.67 3.59 1.69 0.191
5.00 3.28 1.81 0.098
5.67 3.72 1.50 0.191
6.33 4.22 0.88 0.250
Table4 shows the data of particle 4 with their associated
precision
There were several errors in our experiments which
set off the measured value by 0.72% from the actual
value. One source of error could be temperature, as
this was assumed to constant throughout the
experiment and so was not measured at regular
interval. This could have caused the error in the value
of viscosity which is temperature dependent. The
second source of error could have been the damaging
of the micro beads during out experiment. Also the
radius of the micro beads was not measured as it was
already mentioned by the manufacturer in the script
that was provided to us during out experiment.
Mitul Patel 4

Third source of error could have been the reaction
error as the beads movement was missed out at the
start and end of the 15 seconds video clip. One of the
major source of error was the UView software as it
was hard to pin-point the particles. It was very difficult
to see the particles as the beads particles were tiny
and were not able to observe clearly due to the
cameras weak resolution. Also in this experiment we
were applying the 3D principle to 2D experiment as the
values of x were only taken into account and the
values of y were ignored. Plotting graph of the motion
of particles could have been useful but this was not
done as it was not needed.

Conclusion
A value of (1.39 x 10
-23
0.74 x 10
-23
) J/K was
obtained for the Boltzmanns constant by measuring
displacement of the particles at regular intervals. The
value was very close to the actual value I.e 1.38 x 10-
23 J/k. In addition to this Avogadro number was also
determined and this was found to be 5.98 x 10
23

moles. The experimental value was found to be set off
by 0.72% from the actual value. This suggests that the
experiment was accurate and reliable. The data also
suggested the experiment was fairly precise.
The experiment could be improved further by using an
accurate device to measure the time resulting less
reaction error. Multiple videos should be taken, since
there a chance that the slide may contain defective
beads. A better resolution camera should be used in
order to have a clear picture of the particles so will be
easier to track.

References
1. Milner, B. (2001). Physics. Cambridge: Cambridge
University Press.
2. Young, H. D., Freedman, R. A., Ford, A. L., & Sears,
F. W. (2012). Sears and zemansky's university physics
with modern physics plus MasteringPhysics with etext
(access card package): With modern physics. Boston,
[Mass.]: Addison-Wesley.
3. Brown, Robert (1828). "A brief account of
microscopical observations made in the months of
June, July and August, 1827, on the particles
contained in the pollen of plants; and on the general
existence of active molecules in organic and inorganic
bodies." Phil. Mag. 4, 161173.
4. Einstein, A. (1956). Investigations on the Theory of
Brownian movement





























































Mitul Patel 5

Appendix 1
The random motion of the particle means that the
average displacement of the particle is zero <x> = 0
and it can be clearly seen from Fig.1. This often leads
to believe that the particle does not move, it stays in
the same position but in reality this is not the case as it
can be noted from the experiment, therefore we look at
the standard deviation of the motion or the mean
squared displacement <#x
2
>. In the mean squared
displacement we are looking at the average magnitude
of the displacement squared I.e how the far the particle
has moved in time #t between collisions. The measure
of mean squared displacement over time is called
diffusion constant (D) and is given in equation (1)
below
(1)
Thus the equation shows that the means squared
displacement depends on the diffusion constant D and
time #t.
In 1905 Einstein published a paper that was in favour
to the theory of quantum mechanics, he proposed that
the matter is made up of discrete atoms and molecules
and this was purely based on the understanding of the
motion of the molecules due to the thermal agitation. In
thermal agitation the average kinetic energy of the
molecules is related to the temperature as given in
equation (2)
(2)

Where m is the mass of the particle
V is the velocity of the particles.

He also showed an important relationship that diffusion
constant depends on the size and shape of the
diffusing particles and also on the temperature. This
equation is given below and this is known as the
Einstein-Smoluchowski equations

(3)
The term f on the left-hand side of the equation is
called drag force which is given by stokes law
; it is the proportionality constant between
the viscous drag force and the speed of the particle.
Substituting Stokes law into equation (3) and
rearranging for D gives
(4)


Substituting Equation (4) into the equation (1) gives
the final version for < #x
2
> which was used to calculate
the value of Boltzmann's Constant.

The value of Avogadro number was calculated using
the equation (5)
(5)
Appendix 2
All the measured quantities had a degree of precision
associated and therefore it was taken into account and
was calculated as shown below

And finally the accuracy of the experiment was
calculated using the following equation


Where EV experimental value
AV- actual value