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000442-067
Andrew Voyles
000442-067
Chemistry
3968 words
Abstract
Voyles, Andrew
000442-067
The intent of this paper is to investigate how the specific heat of
a 4’-Octyl-4-Biphenyl-Carbonitrile (8CB) liquid crystal changes as the
crystal undergoes phase transitions as it is heated, and to
subsequently model the variation in specific heat in the various liquid
crystal phases. I undertook this investigation as a result of a
suggestion by a local professor at a demonstration he gave at our
school, as well as out of a great passion for chemistry. A molecular-
level discussion of the mechanisms behind specific heat for
conventional and the structure of and interactions between the
molecules as the crystals are heated and undergo phase transition
provides a solid theoretical base for the analysis. This was approached
experimentally, by collecting specific heat capacity data over a range
of temperatures in all of the liquid crystal mesophases of a particular
liquid crystal, 8CB, using a differential scanning calorimeter to
calculate the thermodynamic properties of the sample as it was
heated, a procedure suggested to me by my supervisor, Dr. Timothy
Royappa. From this data, I attempted to construct rational functions to
model the specific heat as it rapidly changed due to the multiple
transitions of structure that the liquid crystal experiences as it is
heated, as it undergoes phase transition. This function was statistically
analyzed, using the coefficient of determination, R2, in order to
determine how well the original data fit the constructed functions. By
comparing the generated data to the molecular-level structure and
interactions of the crystals as they are heated, it was possible to
theorize a possible mechanism for the variation in specific heat as the
crystals undergo phase transition. While I was able to construct
relatively accurate models for each phase, no reviewed literature
values exist to compare my results to.
Voyles, Andrew
000442-067
Table of Chapters
I: Introduction.................................................. ...........1
V: Investigation........................................................20
I: Introduction
(LCD). This use creates a very profitable market for these crystals, as
the LCD uses very little power, making them ideal for use in handheld
http://www.sigmaaldrich.com/catalog/search/ProductDetail/ALDRICH/33
8680
In the brief time period since their discovery, the field of liquid
noticing that they, too, possessed the double melting points, and the
this, MBBA has become known as the “fruit fly” of liquid crystal
extremely stable liquid crystals with low melting points, ideal for use in
Foundation, 2008).
Voyles, Andrew
000442-067
III: Thermotropic Liquid Crystal Mesophases
order.
1988).
states are the various conventional phases of solid, liquid, and gas
this single, clear transition. Since many organic molecules are long,
polar, rod-like chains, there exists the possibility for many more
1988)
Voyles, Andrew
000442-067
The most orderly mesophase is the smectic phase, in which there
based upon the miscibility (solubility) of the phase: two samples are
classified as being in the same smectic phase if they are miscible in all
from the Greek word for soapy, as the soap scum is a common type of
polarizing lenses)
three major smectic phases, the B has the greatest order, so it is the
Gennes, 1974). Unlike the A and C phases, the layers of the B phase
polarizing lenses)
the hexagonal shape, the enthalpy change for this phase is much
greater than that seen in the A and C phases, nearly fivefold that of its
order than the A phase. These crystals are optically biaxial, allowing
optical axis lying between these directions (de Gennes, 1974). There is,
on average, a constant tilt angle away from the normal to the plane of
polarizing lenses)
Voyles, Andrew
000442-067
University of Cambridge, DoITPoMS TLP - Liquid Crystals.
http://www.doitpoms.ac.uk/tlplib/liquid_crystals/printall.php
This holds true when the liquid crystal is optically inactive. When
constant tilt angle to the normal to the smectic plane, but, unseen in
the C phase, the constant tilt angle rotates about a central axis by a
like strands of string, as nematic is the Greek word for “thread” (Atkins,
1986).
http://commons.wikimedia.org/wiki/Image:LiquidCrystal-MesogenOrder-
Nematic.jpg
Fig. 10. Example photo of the nematic phase (using microscope, under
the chiral nematic (cholesteric) phase. Like the smectic C* phase, the
depends upon the distance it takes for one complete revolution of the
helix, called the pitch, so that light of wavelength equal to the pitch will
begins the transition from the solid to the liquid state, at constant
pressure.
container of liquid, and, based upon the given masses, specific heat of
the liquid, and initial and final temperatures of the two substances
heat capacity.
it. This is in the form of internal motion, the result of the agitation of
capacity.
the universal gas constant, 8.314 472 J mol-1 C-1 (or K-1) (Fitzpatrick,
2008).
transition; once more heat is added, the heat overcomes more forces,
reference crucible and the crucible containing the sample. The two
between the final temperatures, knowing that heat was applied to each
the molar specific heat capacity of the sample (Bonvallet, 1999; Tim
I believe that the model for specific heat capacity inside the
with the iridium sample, the resulting graphs with much systematic
Materials
Mettler Toledo DSC823e
4’-Octyl-4-Biphenyl-Carbonitrile Sample
Analytic Balance
Aluminum microcrucible
Iridium calibration sample
Nitrogen gas coolant
Table 1. List of materials used
first calibrated the DSC using the iridium sample. I then measured out
the mass of the 8CB sample, recorded in the data table below, in a
poking a small hole in the top to allow the pressurized hot air to escape
process was repeated for another sample. As the molar heat capacity
formula describing the shape of the data that was obtained is y=A(|x-x | c
which the DSC rounds off as a sharp peak. From this, I constructed the
Data Table
Results Table
Solid-Smectic A Smectic A-Nematic Nematic-Isotropic
Liquid
Average Phase 22.2 ºC 33.20 ºC 40.58 ºC
Transition Temp ([Thoen, 1982] value
used, as no transition
peak appeared in data)
% Error (Thoen, n/a -2.35% -1.02%
1982)
Mesophase Modeling Function R2 Value
Smectic A Cp(t)=e6.241 *(|t-33.2|/33.2)-.0482 .3325
R2 Value Cp(t)=e6.0975 *(|t-40.58|/40.58)-.169 .673
Isotropic Liquid Cp(t)=e6.188 *(|t-40.58|/40.58)-.1049 .4642
Table 3. Results table
Voyles, Andrew
000442-067
800
700
600
Specific Heat (J/mol/ºC)
500
400
300
200
100
0
0 5 10 15 20 25 30 35
Temperature (oC) (± .1 ºC)
6.9
6.8
6.7
6.6
y = -0.0482x + 6.241
6.5 R2 = 0.3325
6.4
ln c
Linear (Series1)
6.3
6.2
6.1
5.9
5.8
-7 -6 -5 -4 -3 -2 -1 0
ln (|T – Tc|/Tc)
Voyles, Andrew
000442-067
Fig 20. Smectic A mesophase logarithmic function plot, with best fit
line
1200
1000
Specific Heat (J/mol/ºC)
800
600
400
200
0
0 5 10 15 20 25 30 35 40 45
Temperature (oC) (± .1 ºC)
7.4
7.2
y = -0.169x + 6.0975
7 R2 = 0.673
6.8
ln c
6.4
6.2
5.8
-6 -5 -4 -3 -2 -1 0
ln (|T – Tc|/Tc)
Fig 22. Nematic mesophase logarithmic function plot, with best fit line
1200
1000
Specific Heat (J/mol/ºC)
800
600
400
200
0
0 10 20 30 40 50 60
Temperature (oC) (± .1 ºC)
7.5
Linear (Series1)
5.5
5
-7 -6 -5 -4 -3 -2 -1 0
ln (|T – Tc|/Tc)
Fig 24. Isotropic liquid logarithmic function plot, with best fit line
1200
1000
Specific Heat (J/mol/ºC)
800
600
400
200
0
0 10 20 30 40 50 60
Temperature (oC) (± .1 ºC)
Fig 26. Full range of specific heat data, graphed on TI-84 Plus Silver Edition
behind the specific heat change for liquid crystals are not currently
how the specific heat changes due to the phase transitions cannot be
theorize just why the heat capacity changes the way it does.
the graph of the crystal’s heat capacity shares the same large spikes at
specific heat capacity from the solid mesophase, as not much heat is
data for each phase, which were separated using the measured
These models were average fits for the data, which is to be expected
Voyles, Andrew
000442-067
due to the fact that relatively little data was collected. The lower
values seen in the smectic and liquid phases as well as the moderate
value of the nematic mesophase indicate that the specific heat offset
between each trial prevented the functions from being even better fits.
Despite the fact that results were not very great, this
data, due to the fact that orienting the molecules while freezing is
[Online]. 1999, 2, 4.
http://plc.cwru.edu/tutorial/enhanced/files/lc/phase/phase.html
http://farside.ph.utexas.edu/teaching/sm1/lectures/node69.html
astr.gsu.edu
Photomicrographs. http://www.microscopy-
uk.org.uk/mag/indexmag
.html?http://www.microscopy-
884.
August 2008).
462-472.
http://us.mt.com/mt/homepage/Xindex.jsp?BV_UseBVCookie=no
http://nobelprize.org/educational_games/physics/liquid_crystals/h
http://www.seas.upenn.edu/~chem101/sschem/solidstatechem.h
1971; Chapter 2.
Thoen, J.; Marynissen, H.; Van Dael, W. Phys. Rev. A. 26. 1982, 2886.
Freedom. http://www.rwc.uc.edu/koehler/biophys/6e.html