Voyles, Andrew

000442-067

Modeling the Variation in Specific Heat of a

4’-Octyl-4-Biphenyl-Carbonitrile Liquid Crystal

due to Phase Transition

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
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Table of Chapters

I: Introduction.................................................. ...........1

II: A Brief History of Liquid Crystals............................3

III: Thermotropic Liquid Crystal Mesophases...............5

IV: Specific Heat..................... ..................................16

V: Investigation........................................................20

VI: Analysis........................................................ .......33

VII: Bibliography............................. ..........................36

 Voyles, Andrew
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Modeling the Variation in Specific Heat of a 4’-Octyl-4-Biphenyl-

Carbonitrile Liquid Crystal due to Phase Transition

I: Introduction

Perhaps one of the biggest developments of the 20th century, the

discovery of the liquid crystal, a so-called “fourth state of matter”, in

1888 by the Austrian botanist and chemist Friedrich Reinitzer has

greatly impacted modern technology. Many modern devices utilize the

most common application of these crystals, the liquid crystal display

(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

electronic devices. The potential uses for liquid crystals make a

seemingly endless list, one that has yet to begin to be tapped.

One major division is that of thermotropic liquid crystals, those

which undergo a phase transition and thermal property changes as a

result of changes in temperature. In this investigation, the particular

liquid crystal in use is 4’-Octyl-4-Biphenyl-Carbonitrile (8CB), also

known as 4-Cyano-4'-Octylbiphenyl or 4-Octyl-4’-Cyanobiphenyl, a

common thermotropic liquid crystal. The structural formula of the 8CB

liquid crystal is CH3(CH2)7C6H4C6H4CN, and its molecular formula is

C21H25N. The structural diagram of this liquid crystal is seen here

 Voyles, Andrew
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below. The decidedly rod-like shape plays a large role in phases that

8CB transitions through, as the close packing of the molecules allows

for greater potential for intermolecular forces.

Fig. 1. Structural diagram of 8CB liquid crystal

Sigma Aldrich, 338680 4′-Octyl-4-biphenylcarbonitrile.

http://www.sigmaaldrich.com/catalog/search/ProductDetail/ALDRICH/33

8680

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 subsequently

model the specific heat in the various liquid crystal phases. An

understanding of this change allows one to create new technologies

that are capable of bettering society, utilizing the change as an

innovation behind new technologies.

 Voyles, Andrew
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II: A Brief History of Liquid Crystals

In the brief time period since their discovery, the field of liquid

crystals has been full of important discoveries. In 1888, Friedrich

Reinitzer, an assistant at the German University of Prague’s Institute of

Plant Physiology, was working on determining the chemical formulas of

cholesterol derivatives extracted from carrots. Reinitzer noticed that

one particular cholesterol, cholesteryl benzoate, had two melting

points: at 145.5°C, the cholesterol melted into a cloudy liquid up to

178.5°C, at which point it melted again, giving rise to a clear liquid, a

reversible process (Sluckin, 2004; Reinitzer, 1888). After this, Reinitzer

would contribute no more to this field.

Otto Lehmann, a German physicist and friend of Reinitzer, who

had been frequently contacted via letters by Reinitzer during his

investigations, carried on the research. Over the next year, Lehmann

studied cholesteryl benzoate and other chemically similar compounds,

noticing that they, too, possessed the double melting points, and the

ability to polarize light (Lehmann, 1889).

No more major advances in the field of liquid crystals would

occur until 1969, when Hans Kelker synthesized MBBA (p-

Methoxybenzyliden-p’-n-butylanilin), which exhibited the cloudy liquid

state at room temperature, re-starting liquid crystal research in the 20th

century. This compound would prove to be vastly important in liquid

crystal research (Kelker, 1969). Exhibiting the cloudy state at room

 Voyles, Andrew
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temperature made it much easier to work with, as others at the time

exhibited this state only at high temperature and pressure. Because of

this, MBBA has become known as the “fruit fly” of liquid crystal

research (de Gennes, 1974).

A final obstacle to commercial applications was resolved in 1973,

when George W. Gray synthesized cyanobiphenyl liquid crystals,

extremely stable liquid crystals with low melting points, ideal for use in

LCDs (Gray, 1973). Since then, research into applications has

continued to abound, creating a very large market for this technology,

which has shown such promise as a future technology that, as a result

of his work in the field of ordered liquid crystal systems, Pierre-Gilles

de Gennes received the Nobel Prize in physics in 1991 (The Nobel

Foundation, 2008).
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III: Thermotropic Liquid Crystal Mesophases

As stated previously, thermotropic liquid crystals, including

4’-Octyl-4-Biphenyl-Carbonitrile, undergo a phase transition as they are

either heated or cooled, through the crystalline solid, smectic, nematic,

and the isotropic liquid phases, known more accurately as

mesophases, and can be determined by analyzing the degree of

system order that the individual molecules exhibit. Unless otherwise

noted, order will be defined as both positional order and orientational

order.

Positional order is “the extent to which… an average molecule or

group of molecules shows… arrangement in space”, and orientational

order is the “measure of the tendency of the molecules to align along

the director [the larger axis of an individual molecule] on a long-range

basis” (Case Western Reserve University, 2008). Crystalline solids have

three degrees of positional order (all constituent molecules being fixed

in place with an x, y, and z coordinate), and conventional liquids have

no positional order at all. As heat is added, in the case of liquid

crystals, positional order is lost before orientational order, as

orientational order forces are stronger (Johnston, 2008; Vertogen,

1988).

All matter, including liquid crystals, undergoes phase transitions

in accordance with the second law of thermodynamics, which states

that entropy (a measure of the disorder of a system) is constantly

 Voyles, Andrew
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increasing. As matter is heated, it assumes states of minimized

chemical potential and order, resulting in an increase in entropy. These

states are the various conventional phases of solid, liquid, and gas

(Atkins, 1986; de Gennes, 1974)

The most orderly mesophase of liquid crystals is that of the

crystalline, anisotropic (directionally dependent, due to molecular

shape and alignment).solid, a regular lattice of millions of molecules

bonded together. The smallest unit of a crystalline solid is called a unit

cell, consisting of that specific crystal’s empirical formula. Individual

unit cells with identical surroundings repeat endlessly in a periodic

pattern, called a lattice, forming crystals. As the solid is heated, the

individual molecules become more disorderly, and transition into the

liquid state of matter at their melting point, as the added heat

overcomes the forces locking the molecules in their fixed positions.

Many organic molecules, notably liquid crystals, do not exhibit

this single, clear transition. Since many organic molecules are long,

polar, rod-like chains, there exists the possibility for many more

intermolecular forces than in inorganic compounds. As they are

heated, the intermolecular attractions create intermediate states of

organization, not seen in conventional matter. These are mesophases,

intermediate states of low chemical potential and order that are

formed as liquid crystals are heated, before finally transitioning to a

conventional isotropic (directionally uniform, as opposed to anisotropic)

 Voyles, Andrew
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liquid, where the order of particles is uniform in all directions, and any

orientation is indistinguishable from any alternative orientation (de

Gennes, 1974). As the crystals proceed from solid to liquid, they

transition through intermediate (mesomorphic) phases. Which and how

many the crystals transition through depends on the properties and

structure of the individual crystal. For many, however, the transition to

the first liquid crystalline mesophase, at the melting point, produces a

turbid (cloudy) and birefringent fluid, as seen by Reinitzer. The

phenomenon of birefringence is caused by an imbalance in the

refractive indices of an optical medium (classically seen in calcite

crystals), which rotates polarized light, producing the colorful show

(Templer, 1991). As the sample is further heated, it may pass through

other mesophases, until it reaches the “clearing point”, the “second

melting point” observed by Reinitzer, at which the liquid crystal

“melts” again, into an optically clear, isotropic liquid (Vertogen, 1988).

This transition can be visualized below.

Fig. 2. The liquid crystalline phases on a temperature scale (Vertogen,

1988)
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The most orderly mesophase is the smectic phase, in which there

are many distinct phases, given capital identification letters. This

system was introduced by the Halle research group, and, as of 2004,

phases A-L have been identified. The placement in a specific phase is

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

proportions (Case Western Reserve University, 2008). The three most

common mesophases, are the Smectic A, B, and C mesophases.

In the smectic mesophase, long-range orientational order is

preserved and short-range positional order is greatly reduced, but still

present, resulting in the individual molecules aligning themselves in

layers (Atkins, 1986; de Gennes, 1974). The word smectic is derived

from the Greek word for soapy, as the soap scum is a common type of

smectic liquid crystal (Case Western Reserve University, 2008). The

centers of mass of every molecule arrange themselves in distinct

planes, whose symmetry distinguishes the different phases from each

other (Vertogen, 1988).

Of the different smectic phases, the simplest, least ordered, and

first to be discovered is that of the smectic A mesophase.

 Voyles, Andrew
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Fig. 3. Example photo of the smectic A phase displaying its

characteristic fan-like texture (using microscope, under crossed

polarizing lenses)

(Case Western Reserve University, 2008)

Fig 4. Schematic picture of the smectic A phase

(Case Western Reserve University, 2008)

In the smectic A mesophase, more like a liquid than a solid,

molecules form flat planes, normal to the director, whose thicknesses

are approximately the length of the molecules themselves. The

molecules show no positional order (de Gennes, 1974; de Vries, 1971).

A liquid crystal in the smectic A phase is optically uniaxial, that is,

plane-polarized monochromatic light is only capable traveling through

a sample in one direction, referred to as the crystal’s optical axis (Case

Western Reserve University, 2008).

The A phase always occurs at the highest temperature of any

other smectic phase, as a higher temperature would be needed to

 Voyles, Andrew
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achieve a greater state of disorder (de Vries, 1971). In the case of the

4’-Octyl-4-Biphenyl-Carbonitrile liquid crystal, the A phase is the first

mesophase, upon being heated from the solid state.

The next primary smectic phase is that of the smectic B. Of the

three major smectic phases, the B has the greatest order, so it is the

first to possibly emerge with increasing temperature, as it requires the

least amount of added heat to overcome the intermolecular forces (de

Gennes, 1974). Unlike the A and C phases, the layers of the B phase

are more like a two-dimensional solid, due to their rigidity and

periodicity, confirmed through x-ray diffraction, which reveals definite

positional and orientational order (de Vries, 1971).

Fig. 5. Example photo of the smectic B phase displaying its

characteristic mosaic-like texture (using microscope, under crossed

polarizing lenses)

(Kent State University, 2008)

In the layers of the B phase, molecules align in tightly packing

cyclic, hexagonal rings, as opposed to the linear orientation seen in the

 Voyles, Andrew
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A phase. As a combined result of the tight packing and the strength of

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

A phase, in the case of N’-terephthalylidene-bis-(4-n-butylaniline)

(TBBA) (Petrie, 1971).

The final primary smectic phase is that of the smectic C phase.

The C phase possesses some orientational order, and more positional

order than the A phase. These crystals are optically biaxial, allowing

plane-polarized monochromatic light to pass in two directions, the

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

the molecules, caused by dipole-dipole intermolecular attractions

between polar molecules, so that the distance between layers is

approximately equal to d=l * cos(ω), where l is the molecule’s length,

and ω is the constant tilt angle. This creates a distinctive texture,

called schlieren (Vertogen, 1988).

Fig. 6. Example photo of the smectic C phase displaying its

characteristic schlieren texture (using microscope, under crossed

polarizing lenses)
 Voyles, Andrew
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University of Cambridge, DoITPoMS TLP - Liquid Crystals.

http://www.doitpoms.ac.uk/tlplib/liquid_crystals/printall.php

Fig 7. Schematic picture of the smectic C phase

(Case Western Reserve University, 2008)

This holds true when the liquid crystal is optically inactive. When

mixed with a second, optically active, compound, called a chiral

dopant, the periodic structure of the layers becomes distorted, creating

a special case, referred to as the smectic C* phase, which possesses

geometrical asymmetry. Like the normal C phase, the director is at a

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

constant angle between each layer, giving a helical structure, which

can reflect one specific wavelength of circularly-polarized light (Petrie,

1971; Case Western Reserve University, 2008).

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Fig. 8. Schematic picture of the smectic C* phase

(Case Western Reserve University, 2008)

The final mesophase of liquid crystals, possessing the least

positional and orientational order, is that of the nematic mesophase,

first observed as Reinitzer’s cloudy, birefringent liquid. This occurs

immediately before the liquid phase, as temperature increases. Weaker

positional order is completely lost, including the smectic layered

structure, while stronger orientational order is preserved, to a notable

degree, causing the molecules to retain a rough parallel arrangement,

like strands of string, as nematic is the Greek word for “thread” (Atkins,

1986).

For nematic mesophases, the orientational order arises from all

of the liquid crystal molecules arranged so that a common axis of all of

the constituent molecules is aligned parallel in one direction (the

director), labeled with a unit vector, n. Around the director, there is

nearly complete rotational symmetry. Nematic crystals flow almost

exactly like conventional fluids (de Gennes, 1974).

Fig. 9. A schematic diagram of the nematic phase

 Voyles, Andrew
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Wikimedia Commons, Schematic of mesogen alignment in a liquid

crystal nematic phase.

http://commons.wikimedia.org/wiki/Image:LiquidCrystal-MesogenOrder-

Nematic.jpg

Fig. 10. Example photo of the nematic phase (using microscope, under

crossed polarizing lenses)

(Kent State University, 2008)

There also exists a chiral, or, geometrically asymmetrical,

molecule in the nematic mesophase. This special case is referred to as

the chiral nematic (cholesteric) phase. Like the smectic C* phase, the

chiral nematic consists of repeating nematic planes, rotated by a

constant angle from the previous one, capable of reflecting specific

circularly-polarized wavelengths of light. The wavelength reflected

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

be completely reflected. While the C* is produced by the addition of a

chiral dopant, the cholesteric phase may exist as a naturally chiral

 Voyles, Andrew
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material, or by the addition of a chiral dopant. Unlike the smectic, the

cholesteric and the nematic phases are completely miscible. Also, if

equal amounts of samples with opposite chirality are mixed together,

referred to as a racemic mixture, a normal nematic results, with no

changes in any physical property. (Vertogen, 1988; Saeva, 1971).

Fig 11. Structural diagram of the chiral nematic phase

(Case Western Reserve University, 2008)

Finally, upon sufficient heating, as a result of multiple transitions

of structure, the liquid crystal sample will overcome the intermolecular

forces creating orientational and positional order, transitioning to a

conventional isotropic liquid. As stated previously, in an isotropic liquid,

particle order is uniform in all directions, and any orientation of the

liquid is indistinguishable from any other alternative orientation.

 Voyles, Andrew
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IV: Specific Heat

One of the most important tasks for classifying and investigating

a new compound is to determine its thermal properties, one of the first

experiments classically performed in determining the identity of the

compound, but replaced in modern times with more advanced

techniques such as mass spectrometry. Nonetheless, it still remains a

highly important task in research, especially in new types of

compounds, including liquid crystals, metamaterials, polymers, and

composites. One of the simplest thermal properties to determine for a

compound is its melting point, the temperature at which a compound

begins the transition from the solid to the liquid state, at constant

pressure.

A second, related property is the specific heat capacity of the

compound. The specific heat capacity, c, is defined as “the quantity of

heat required to raise the temperature of 1 gram of a substance by 1°

Celsius (or one Kelvin) at constant pressure” (Ebbing, 2005).

Mathematically, this relationship can be expressed as c=Δq/mΔt, where

Δq represents the change in heat of the substance, m represents the

mass of the substance, and Δt represents the change in temperature of

the substance. The greater the specific heat capacity of a given

substance, the more thermal energy is needed to raise the

temperature of that substance by 1° Celsius, and vice versa.

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Many methods exist to experimentally determine the specific

heat of a given substance. The simplest method is that of the

calorimeter, where a heated compound is dropped into an insulating

container of liquid, and, based upon the given masses, specific heat of

the liquid, and initial and final temperatures of the two substances

(assuming that no heat is lost to the surroundings), the specific heat of

the heated compound is determined. However, this is a very loose

assumption; more accurate and precise values can be determined

through the use of a differential scanning calorimeter (DSC).

A solid grasp of the molecular-level theory of specific heat is

required to accurately understand the variation, as liquid crystals

undergo phase transitions, discussed in the analysis. At the molecular

level, what is it that causes molecules to be able to store thermal

energy? Due to the unique characteristics of liquid crystals, let’s first

look at conventional matter to understand what causes the change in

heat capacity.

One fundamental concept of thermodynamics has been

neglected: temperature. Temperature is a measure of the average

kinetic energy of an object, the energy of an object due to its motion,

calculated by the equation KE=mv2, where m is the mass of an object

and v is the object’s linear velocity. The average kinetic energy of an

object can also be related to temperature, in the form of the equation,

KEavr=3/2kT, where k is the Boltzmann constant, 1.380 6504×10−23 J×

 Voyles, Andrew
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ºC-1 and T is the temperature of the object. Thus, an object at high

temperature has a high degree of kinetic energy and, subsequently,

motion (Georgia State University, 2008).

As a molecule gains kinetic energy, it requires a place to “store”

it. This is in the form of internal motion, the result of the agitation of

chemical bonds, through what is referred to as internal degrees of

freedom. An internal degree of freedom is any way that the molecule

or its atoms are capable of moving. There are three forms:

translational freedom (rigid movement or collisions of the whole

molecule in three-dimensional space), rotational freedom (the rotation

of the entire molecule or an atom around an axis), and vibrational

freedom (rapid shaking and contraction of bond lengths). Molecules

maintain minimized chemical potential by converting this excess

kinetic energy into temperature, as discussed above. Small molecules,

such as diatomic gases, have fewer degrees of freedom as they are

made up of fewer atoms. Larger molecules, notably the long, chain

structures seen in many organic molecules, consist of many atoms,

and have dozens of degrees of internal freedom, and a large heat

capacity.

As a result, a heated object will gain kinetic energy and begin to

vibrate and twist extremely vigorously. Two particular bonds capable of

storing a large quantity of thermal energy are the Carbon-Hydrogen

bond seen in the vast majority of organic compounds, and the

 Voyles, Andrew
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hydrogen bond, a strong special case of dipole-dipole attractions

between a hydrogen atom and a nitrogen, oxygen, or fluorine atom

(University of Cincinnati, 2008; Tim Royappa, PhD., personal interview,

August 11, 2008). Indeed, the number of degrees of internal freedom

of a molecule and that molecule’s molar heat capacity (the specific

heat of 1 mole, 6.022×1023 molecules) are connected by the relation

c=g/2 R, where g is the number of internal degrees of freedom, and R is

the universal gas constant, 8.314 472 J mol-1 C-1 (or K-1) (Fitzpatrick,

2008).

For conventional matter, the specific heat of the compound will

remain approximately constant inside a phase. There will also be a

sharp spike in the values of heat capacity at the compound’s phase

transition, followed by a more or less constant value. In the liquid

crystal mesophases, strength and stability is achieved in these

temporary stable states, causing the sharp peak at the phase

transition; once more heat is added, the heat overcomes more forces,

and so the heat capacity rapidly falls again. A typical example of a

specific heat curve for a conventional compound, sulfapyridine

(C11H11N3O2S), with a single, clear melting point can be seen below.

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Fig 12. Typical DSC specific heat curve

(Mettler Toledo, 2008)

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V: Investigation

For this investigation, a Mettler Toledo DSC823e DSC was used to

obtain specific heat data over a range of temperatures. This machine is

capable of generating extremely accurate and precise results for

specific heat capacity. It works by heating two crucibles, an empty

reference crucible and the crucible containing the sample. The two

crucibles are cooled to some arbitrary initial temperature set by the

user, are heated identically, and a platinum thermometer located

beneath each crucible independently records the temperature of each.

Using a coolant gas, in this case, nitrogen, allows the taking of

measurements below room temperature. Based on the difference

between the final temperatures, knowing that heat was applied to each

at the same rate, it is then possible for the calorimeter to determine

the molar specific heat capacity of the sample (Bonvallet, 1999; Tim

Royappa, PhD., personal interview, August 11, 2008)

Fig 13. Mettler Toledo DSC823e

(Mettler Toledo, 2008)

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I believe that the model for specific heat capacity inside the

mesophase will be of the type of a rational function. I manipulated the

temperature of the sample in order to see how it affects the specific

heat of the sample, which I then measured. By using a calibration run

with the iridium sample, the resulting graphs with much systematic

error taken out acts as a control run.

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

The procedure for this investigation was suggested to me by my

supervisor, Dr. Timothy Royappa, of the University of West Florida. I

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

microcrucible, using an analytic balance. I sealed the crucible shut,

poking a small hole in the top to allow the pressurized hot air to escape

during the heating process, as per DSC procedure. I placed the

crucibles inside the DSC and cooled the samples to an initial

temperature of 0.0 ± .1 ºC and then heated at 10 ºC min-1 to a final

 Voyles, Andrew
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temperature of 60.0 ± .1 ºC. The transition temperatures were

determined by averaging the temperature at which the peaks in the

specific heat graphs occurred, which indicate phase transitions. This

process was repeated for another sample. As the molar heat capacity

is measured, the mass of the sample has no effect. The general

formula describing the shape of the data that was obtained is y=A(|x-x | c

/x )-α. By taking the natural logarithm of this equation and plotting a

c

graph of ln(y) versus ln(|x-x |/x ), a straight-line graph is produced, with a

c
c

slope of α and y-intercept of (0, eA), and a vertical asymptote at xc,

which the DSC rounds off as a sharp peak. From this, I constructed the

rational function for each mesophase, as seen below.

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Data Table

DSC Specific Heat Error Maximum of ± 4%

Solid-Smectic A Smectic A-Nematic Nematic-Isotropic

Liquid
Literature Phase
Transition 22.2 ºC 34.0 ºC 41.0 ºC
Temperature
(Thoen, 1982)
Sample 1 Sample 2 Sample 3 Sample 4 Sample 5

Mass .0255 g .0257 g .0259 g .0263 g .0268 g

(± .0001 g)
Initial 0.0 ºC 0.0 ºC 0.0 ºC 0.0 ºC 0.0 ºC
Temperatur
e
(± .1 ºC)
Heating 10 ºC min-1 10 ºC min-1 10 ºC min-1 10 ºC min-1 10 ºC min-1
Rate
(± .2 ºC)
Final 60.0 ºC 60.0 ºC 60.0 ºC 60.0 ºC 60.0 ºC
Temperatur
e
(± .1 ºC)
Table 2. 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
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Fig. 14. DSC Specific heat capacity curve for sample 1

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Fig. 15. DSC Specific heat capacity curve for sample 2

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Fig. 16. DSC Specific heat capacity curve for sample 3

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Fig. 17. DSC Specific heat capacity curve for sample 4

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Fig. 18. DSC Specific heat capacity curve for sample 5

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Specific Heat vs. Temperature: Smectic A Phase

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)

Fig. 19. Smectic A mesophase data plot

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)
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Fig 20. Smectic A mesophase logarithmic function plot, with best fit

line

Specific Heat vs. Temperature: Nematic Phase

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)

Fig. 21. Nematic mesophase data plot

 Voyles, Andrew
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7.4

7.2

y = -0.169x + 6.0975
7 R2 = 0.673

6.8
ln c

6.6 Linear (Series1)

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

Specific Heat vs. Temperature: Isotropic Liquid Phase

1200

1000
Specific Heat (J/mol/ºC)

800

600

400

200

0
0 10 20 30 40 50 60
Temperature (oC) (± .1 ºC)

Fig. 23. Isotropic liquid data plot

 Voyles, Andrew
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7.5

6.5 y = -0.1049x + 6.188

R2 = 0.4642
ln c

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

Specific Heat vs. Temperature: Full Range

1200

1000
Specific Heat (J/mol/ºC)

800

600

400

200

0
0 10 20 30 40 50 60
Temperature (oC) (± .1 ºC)

Fig 25. Full range of specific heat data

 Voyles, Andrew
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Fig 26. Full range of specific heat data, graphed on TI-84 Plus Silver Edition

graphing calculator, alongside the mesophase modeling function for

the domain of each mesophase

 Voyles, Andrew
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VI: Analysis

The theory behind the specific heat change for conventional

matter is known. While there is a general idea, the exact mechanisms

behind the specific heat change for liquid crystals are not currently

known. In fact, the topic is currently researched at the forefront of

science, by numerous groups. As a result, a complete understanding of

how the specific heat changes due to the phase transitions cannot be

obtained. However, it is still possible for us to try to qualitatively

theorize just why the heat capacity changes the way it does.

As compared to the graph of a normal compound (see Fig. 12),

the graph of the crystal’s heat capacity shares the same large spikes at

the phase transitions. However, inside the difference mesophases, it

does not remain constant, but varies with temperature as a rational

function. In the smectic A phase, there is not a major difference in the

specific heat capacity from the solid mesophase, as not much heat is

required to break the positional order forces. The nematic mesophase

displays a much larger jump in heat capacity, since the stronger

orientational order forces were overcome.

A quantitative analysis is required for an accurate understanding

of the significance of these results. Rational functions were fit to the

data for each phase, which were separated using the measured

average transition temperatures as the cutoffs between mesophases.

These models were average fits for the data, which is to be expected
 Voyles, Andrew
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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.

However, the measured average transition temperatures were

extremely accurate (Thoen, 1982) .This could be improved by

collecting more data and reanalyzing the results, based on the R2

coefficient of determination values, an indicator of how well a function

fits its data, where a value closest to 1 indicates a better fit.

Despite the fact that results were not very great, this

investigation has provided valuable insight into the phenomenon of the

specific heat capacity changes in 4’-Octyl-4-Biphenyl-Carbonitrile liquid

crystals, for which no reviewed literature could be found. The main

sources of error for this investigation included the random error of

impurities in the 8CB sample and the systematic error of inaccurate

calibration of the calorimeter. Due to the effect of hysteresis, the

tendency of a system to display results out of phase in the forward and

reverse directions, melting data is generally preferred over freezing

data, due to the fact that orienting the molecules while freezing is

much more unpredictable then disorienting them while melting. In

DSC curves, this appears as a transition spike appearing at a lower

temperature while freezing than while melting (Bonvallet, 1999), but

was not discussed. Nonetheless, this investigation has produced very

 Voyles, Andrew
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important results. Further analysis in this subject should be done in the

near future, as the possibilities for using this change in new

technologies have vast possibilities, which could greatly enhance the

quality of everyday life.

PHS IB Honor Code

“Students shall be honor bound to truthful conduct.”

On my honor, I pledge that I have neither given nor received any

unacknowledged aid on this paper.

 Voyles, Andrew
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VII: Bibliography

Atkins, P. W. Physical Chemistry. W. H. Freeman and Company: New

York, 1986; pp 10-13; Chapter 7; 594-595.

Bonvallet, Geoffrey A. Physics Department, The College of Wooster

[Online]. 1999, 2, 4.

Case Western Reserve University. Phases of Liquid Crystals.

http://plc.cwru.edu/tutorial/enhanced/files/lc/phase/phase.html

(accessed July 2008).

De Gennes, Pierre-Gilles. The Physics of Liquid Crystals. Oxford

University Press: London, 1974; Chapter 1; Chapter 2.

De Vries, Adriaan. Structure and Classification of Thermotropic Liquid

Crystals. Marcel Dekker: New York, 1971; Chapters 1-2.

Ebbing, Darrell D.; Gammon, Steven D. General Chemistry. Houghton

Mifflin Company: Boston, 2005; 239.

Fitzpatrick, Richard. The University of Texas at Austin. Specific heats.

http://farside.ph.utexas.edu/teaching/sm1/lectures/node69.html

(accessed August 2008).

Georgia State University. Temperature. http://hyperphysics.phy-

astr.gsu.edu

/Hbase/thermo/temper.html (accessed August 2008).

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Gray, George W. Electronics Letters. Institution of Engineering and

Technology: London, 1973; p 130.

Johnston, Brian. Mic-UK [site A]: A Gallery of Liquid Crystal

Photomicrographs. http://www.microscopy-

uk.org.uk/mag/indexmag

.html?http://www.microscopy-

uk.org.uk/mag/artsep03/bjpolar3.html (accessed August 2008).

Kelker, Hans. Angewandte Chemie. Wiley-VCH: New Jersey, 1969; p

884.

Kent State University. Polarization Microscope Pictures of Liquid

Crystals. http://www.lci.kent.edu/polmicpic.html (accessed

August 2008).

Kirchhoff, J.; Hirst, L. S. Phys. Rev. E [Online]. 2007, 76, 6.

Lehmann, Otto. On Flowing Crystals. Oldenbourg: Bremen, 1889; pp

462-472.

Mettler Toledo. METTLER TOLEDO - United States - Lab Balances,

Titration, RAININ Technology, Particle Characterization, pH,

Scales, Checkweighing, Dimensioning, Weighing.

http://us.mt.com/mt/homepage/Xindex.jsp?BV_UseBVCookie=no

(accessed August 2008).

The Nobel Foundation. Liquid Crystals.

http://nobelprize.org/educational_games/physics/liquid_crystals/h

istory (accessed July 2008).

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Penn Engineering. Solid State Chemistry: Describing Crystalline Solids.

http://www.seas.upenn.edu/~chem101/sschem/solidstatechem.h

tml (accessed July 2008).

Petrie, S. E. B. Smectic Liquid Crystals. Marcel Dekker: New York,

1971; Chapter 2.

Reinitzer, Friedrich. Contributions to the Understanding of Cholesterol.

Springer Wien: Prague, 1888; 421-441.

Saeva, Franklin D. Nematic Mesophases. Marcel Dekker: New York,

1971; Chapters 1-3.

Sluckin, Timothy J.; Dunmur, David; Stegemeyer, H. Crystals that Flow:

Classic Papers from the History of Liquid Crystals. CRC Press:

Florida, 2004; pp 3-4.

Templer, R.; Attard, G. NewScientist [Online]. 1991, 2-3.

Thoen, J.; Marynissen, H.; Van Dael, W. Phys. Rev. A. 26. 1982, 2886.

University of Cincinnati. Infrared Spectroscopy and Degrees of

Freedom. http://www.rwc.uc.edu/koehler/biophys/6e.html

(accessed August 2008).

Vertogen, G.; de Jeu, W. H. Thermotropic Liquid Crystals, Fundamentals.

Springer-Verlag: Berlin, 1988; Chapters 1-3.