Differential Scanning Calorimetry

C1: ukasz Lesiski and Jrg Duschmal 20th November 2006

Introduction

Dierential Scanning Calorimetry (DSC) is the most widely used technique of all the thermal analysis methods (most of all in purity measurements for example in polymer or pharmaceutical industry). There are two dierent types of DSC-methods, namely power compensated DSC and heat ux DSC, which, although the same properties are measured, dier in their instrumentation. Since the apparatus used in the practical course was a heat ux DSC machine only the latter shall be described here. In a heat ux DSC machine the substance which shall be measured is placed in an aluminium pan whereas an empty aluminium pan serves as the reference. These two pans are put on an electrically heated plate in order to make sure that the temperature in the sample is the same as in the reference. Via those plates and the pans heat is transferred to the sample and the reference with the use of a dened computer controlled heating program (the rates of the heating can be adjusted). The dierential heat ux to the sample and the reference as well as the sample temperature are measured. The output of a DSC measurement, the so called thermogram is a plot of the dierence of heat delivered to the sample and to the reference as a function of the sample temperature. If a physical or a chemical process which is endothermic (consuming energy as heat) is taking place, in order to maintain the same temperature of the two pans, more heat must be delivered to the sample pan than to the reference pan (where of course no transition occurs). The eect is a positive or negative peak in the thermogram (the sign of the peak is depending on the denition of the sign for the direction of the heat ow). The opposite is true for an endothermic process. Since the enthalpy change of the transition trs H is linearly related to the area under the curve of the thermogram it can be easily calculated from the integral.

Figure 1: An example of a thermogram. 1

Praktikum "Physikalische Chemie"

Wintersemester 2006/07 C1: ukasz Lesiski und Jrg Duschmal

According to the Ehrenfest classication phase transitions can be of dierent orders. A phase transition n is of order n, if the n derivative of the Gibbs energy G p is discontinuous. The commonly known phase T n transitions like vaporisation, melting or crystallisation are rst order transitions whereas transitions like the glass transition or the conducting-superconducting transition of metals are second order. On a DSC thermogram rst and second order transitions can easily be distinguished from the shape of the signal. First order transitions are broad peaks, whereas second order transitions due to the change in the heat capacity before and after the transition are -shaped signals (g 1). Some substances are able to form liquid crystalline phases. These are phases where the ordering is somewhere between the long range ordering of a crystal and the molecular disorder of a liquid. Liquid crystalline phases are divided into thermotropic (liquid crystalline phases develop upon melting between the solid state and the isotropic liquid) and lyotropic phases (liquid crystalline phases are formed in solution). For thermotropic liquid crystals there are many dierent of these so called mesophasees depending on the degree of order. However generally they can be divided into two categories namely "nematic" and "smectic" phases. When the long range three dimensional structure of a crystalline solid is broken up and one degree of freedom is added, a smectic liquid crystal is formed. Smectic phases have orientational ordering (all molecules pointing in the same direction; rst dimension xed) as well as positional order (layers of molecules; second dimension xed). In nematic phases the ordering is only one dimensional which is orientational ordering. Since there are more phase transitions in a substance that can form liquid crystalline phases (transitions between those dierent mesophases in addition to the phase transitions between dierent states of aggregation) the DSC examination of a such is much more interesting. In the following experiment the phase transitions of the substance p-(undeca-10-en-1yloxy)-benzoic acid (1) shall be examined with a DSC measurement.
O HO O

Figure 2: p-(undeca-10-en-1yloxy)-benzoic acid (1)

Experimental

With a Dierential Scanning Calorimeter the heating curves of a sample of 8.4 mg of Indium were measured from 140 to 190 with 5 dierent heating rates (2.5, 5.0, 10, 20 and 40 min 1 ) against an empty reference pan. Then a sample of 3.2 mg of compound 1 was prepared and the heating curves were measured at 3 heating rates (10, 20 and 30 min1 ) from 50 to 160 against an empty reference pan. Additionally the cooling 1 curve at a rate of 20 min was measured.

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3
3.1

Results and Discussion

Data

The thermograms of the Indium all showed one peak of a rst order phase transition. The thermograms of 1 showed three rst order phase transitions each. The measured data is indicated in table 1 for the Indium and table 2 for compound 1. Heating rate / 2.5 5.0 10 20 40 min1 Onset / 155.51 155.72 156.19 157.08 158.72 Peak / 156.70 155.32 158.36 159.99 162.38 Area / mJ 247.63 274.68 247.12 246.02 241.689

Table 1: The data measured with the Indium sample. Heating rate / min1 First phase transition. 10 20 30 Second phase transition. 10 20 30 Third phase transition. 10 20 30 Onset / 83.61 79.83 80.59 123.06 123.78 124.56 137.26 137.74 138.24 Peak / 85.87 82.83 84.29 123.68 124.72 125.55 138.14 139.35 140.50 Area / mJ 364.105 177.618 182.075 13.166 12.987 9.533 24.597 34.847 34.095

Table 2: The data measured with the sample of 1. The cooling curve showed as well three transitions but obviously, since the phase transitions were exothermic in the heating process the reverse transitions are endothermic. So the peak areas are due to the denition of the y-axis negative values (further discussion of the cooling curve follows in exercise 3).

3.2

Indium: The derivation of the correction factor.

The measured melting points (onsets of the transitions peaks) and the corresponding melting enthalpies (area under the curve) were plotted as a function of the heating rates. The resulting plots are indicated in gure 3 and 4 respectively. Obviously there is a certain heating rate dependence of the measured quantities. This fact is due to the non perfect distribution of heat in the sample. In order to achieve the real value of the melting point of indium a linear regression was conducted. From the y-intersection of the graph the real melting point can be obtained (heating rate = 0). The same thing was accomplished with the enthalpy data (from the areas under the peaks). J Division of the resulting value (in mJ) by the mass of Indium used (in mg) results in the enthalpy value (in g ). By 3

Praktikum "Physikalische Chemie"

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Figure 3: The measured melting points.

Figure 4: The measured melting enthalpies. comparison with the actual data from the literature [4] a machine dependent correction factor can be calculated according to equations 1 and 2. Tm,actual k Tm = = 1.00829 (1) Tm,meas m Hactual = 0.96871 (2) m Hmeas Multiplication of any measured temperature or enthalpy with those correction factors ameliorates the value since some machine dependent error sources are eliminated. k m H =

3.3

Measurement of the phase transitions of compound 1

In order to determine the transition temperatures and the transition enthalpies of compound 1 again the measured onsets and integrals were plotted as functions of the heating rates (gures 5 and 6). Analogous to the previous chapter the actual quantities were obtained by extrapolation of the linear regression to heating rate = 0. Correction of these values with the factors calculated in equations 1 and 2 produce 4

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Figure 5: The measured transition temperatures.

Figure 6: The measured transition enthalpies. the values indicated in table 3. Due to a problem in the measurement (see section 3.4: Discussion) the rst transition was also calculated ignoring the rst heating curve (10 min 1 ). The resulting values are indicated in the bottom line of table 3. First transition Second transition Third transition First transition 1 Transition temperature / 85.06 123.31 137.90 78.96 Transition enthalpy / (Jg 1 ) 128.14 6.56 4.70 51.07

Table 3: The determined properties of the transitions.

1

Without the rst value of the measurement.

Praktikum "Physikalische Chemie"

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3.4

Discussion

There are three phase transitions taking place when heating compound 1. As can be seen from gures 5 as well as 6 the position of the transition temperature and the transition enthalpy measured for the rst phase transition with the rst heating rate is rather dierent from the other values. Therefor the regression curve is also very dierent from the curves for the other phase transitions. So the accuracy of the calculated values for the rst phase transition should be doubted. The deviation from the normal behavior of these values can be explained by the fact, that the sample was not yet wholly and throughout at the initial temperature when the rst measurement was started. When the rst value is ignored, the transition properties are the ones indicated on the lowest line in table 3. The rst transition occurring at the lowest temperature probably is the transition from the crystalline solid to the liquid crystalline smectic phase. The energy absorbed is enough to compensate the long range ordering in the crystal. The big enthalpy change is consistent with this since the removal of the completely ordered lattice is accompanied with a big change in enthalpy. This smectic liquid crystalline phase is existent until a temperature of 123.31 . Then the thermic energy supplied is enough to compensate for the loss of another dimension of ordering. The less ordered nematic liquid crystalline phase develops. Enthalpy changes in the transition from one liquid crystalline phase to another are usually small and in the area of the measured quantity. Yet on further heating until 137.90 the last dimension of ordering is energetically overcome and the isotropic liquid phase is formed. Finally it is worth mentioning that even though transitions between dierent liquid crystalline phases are sometimes second order all the transitions we observed here are rst order.

Exercises
1. Dene and describe the regions of existence and the transitions of the dierent phases of the liquid crystal. Which phases are isotropic which are anisotropic? See section 3.4 Discussion. 2. Why does the liquid crystal have to be kept at the initial temperature for several minutes before the measurement? Since the liquid crystal is far from an ideal heat conductor (like for example the Indium where ideal behavior was assumed), the uniform distribution of heat in the sample takes time. So in order to prevent errors in the measurement due to a heat gradient in the sample itself the sample is kept at the initial temperature for 10 min before the heating program is started. 3. Discuss the dierences of the heating and cooling curves of the liquid crystal. The most obvious dierence of the heating and cooling curves is of course the fact, that the peaks in the cooling curves are negative (with our denition of the direction of the heat ow). Additionally and by far more interesting there is a shift of the transitions to lower temperatures. That means the sample has to be cooled to a lower temperature than the transition temperature measured in a heating curve in order to make the process happen. This can be explained by looking at the molecular shape of the molecules. The molecules of compound 1 are large and relatively rigid. So the probability that the molecules are orientated the way they need to be in order to build a phase of a certain order is much lower than in the case of a small exible molecule. Due to this fact it takes more time (and therefore cooling to lower temperatures) than in the heating curve, where molecular ordering is broken up. Additionally the fact of insucient distribution of energy within the sample is as well responsible for the shift.

Praktikum "Physikalische Chemie"

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4. Which properties does a molecule need in order to develop liquid crystalline phases? Give at least three examples. Some examples of molecules that develop liquid crystalline phases are indicated in gure 7. The molecular
Calamitic liquid crystals Discotic liquid crystals

OCOR C9H19 N N C9H19 ROCO OCOR 4,4'-dinonylazobenzene Hexaesters of benzene OR OR RO C8H17 C N RO OR OR 4-octyl-4'-cyanobiphenyl Triphenylene derivatives OCOR ROCO OCOR

Figure 7: Some examples of liquid crystal molecules. properties they have in common are that their shapes are either rod-like (calamitic, left column of g 7 as well as molecule 1) or disc-like (discotic, right column). Most calamitic liquid crystals have a aromatic ring (often 1,4-disubstituted) to which one or more alkyl chains are attached. Terminal polar functional groups increase the probability of liquid crystalline phase formation, since the molecule itself then gets a dipole. Discotic molecules form columnar phases. As can be seen from the examples in the right column in gure 7 the disc-like shape can be achieved in many dierent forms. Aromatic systems favor the formation of columnar phases via interactions of -orbitals of multiple molecules. 5. Sketch a smectic liquid crystal and explain with the help of this example why liquid crystals are called "liquid crystals". Figure 8 shows an example of a smectic phase. The layering of the molecules as well as the orientational order can be seen. As has been mentioned in the introduction in a smectic liquid crystal there is a two

Figure 8: The layering in a smectic liquid crystal. dimensional ordering (orientation and layering). Liquid crystals are called "liquid crystals" because of the 7

Praktikum "Physikalische Chemie"

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fact, that they are a mesophase between the long-range positional order of a crystal and the disorder of a liquid (see also chapter one: Introduction). 6. Name and explain rst and second order phase transitions. See chapter 1: Introduction. 7. Indicate three examples where (a) phase transitions and (b) liquid crystalline properties are of importance in technical applications. (a) Phase changes can be applied whenever the cooling of something is desired (for example in refrigerators or self cooling beer barrels). Materials where a phase transition can easily be induced and then be read out are used in so called Phase-change memory systems. In all sorts of painting colours the fact, that the solvent is evaporated more easily is used. (b) Liquid crystals owe their wide application in displays their ability to change their orientation dependent on the presence or absence of an electric or magnetic eld. The rst and crudest liquid crystal displays are the Nematic Liquid Crystal Displays and the Twisted Nematic LCDs. In Thin-Film Transistor LCDs, which are used in most laptops, a greater sharpness and diversity is achieved by addressing each liquid crystal pixel with a transistor. Further application in displays include Ferroelectric Liquid Crystal Displays or Polymer Dispersed Liquid Crystal Displays. The little non-display applications make use either of the optical properties of anisotropic phases (spatial light modulators, optical wave mixing) or the properties of temperature dependent colour change of chiral nematic phases. The latter is used in medical thermography (mapping of heat dierences across the body, manly in oncology) or in engineering (mapping of heat variations due to unequal wind ow in a wind tunnel). Of course there are as well many colour changing products like keyring pendants or beer mats. 8. How do you dier exothermic from endothermic processes? Exothermic processes release energy as heat, whereas endothermic processes consume energy as heat. In a DSC measurement signals of exothermic and endothermic processes have dierent sign. With the denition of the heat ow we used in the experiment above exothermic peaks are negative, endothermic peaks are positive. 9. Explain the Dierence of exothermic and exergonic processes. Exothermic processes are processes which produce energy as heat. So exothermic processes refer to a negative enthalpy change in the reaction (H). Exergonic processes are processes that occur spontaneously. The term exergonic refers to the Gibbs free energy (G).

References
[1] P. Atkins, J. de Paula, Physical Chemistry, 7th Edition, Oxford University Press, New York, 2002. [2] D. Skoog, F. Holler, T. Nieman, Instrumental Analysis, 5th Edition, Harcourt, Philadelphia, 2002. [3] I. Hamley, Introduction to Soft Matter, 1st Edition, Wiley, Chichester, 2000. [4] D. Archer, S. Rudtsch, J. Chem. Eng. Data, 2003, 48, 1157 - 1163.