You are on page 1of 86

AGING OF POLYURETHANE RIGID FOAMS

Thermal Conductivity of Gas Mixtures involving Nitrogen and


Hydrocarbons



Carlos Duarte Duro Antunes



Dissertation to obtain the Degree of Master in
Chemical Engineering






Jury
President: Dr. Maria Rosinda Costa Ismael
Guide: Dr. Maria Gabriela da Silva Bernardo Gil
Vogals: Dr. Ralph Dohrn
Dr. Joo Manuel Nunes Alvarinhas Fareleira



September de 2007
II






ACKNOWLEDGMENTS





I would like to acknowledge the support of Prof. Dr. Ralf Dohrn from Bayer
Technology Services and of Prof. Dr. Gabriela Bernardo Gil.
Without them it would not have been possible to be presented with the opportunity of
working in this project and to conclude it successfully.

I would also like to acknowledge the support of Eng. Jos Fonseca during the
realization of the work and during the subsequent data modelling verifications.

I
ABSTRACT


The object of study for this work was the thermal conductivity of gaseous binary
systems in several ratio combinations between components, which thermal conductivity was
also studied individually.
In total, two systems were studied; the first system was composed of nitrogen and
isopentane and was completely studied through a set of three different ratios in composition,
while the second was composed of isopentane and cyclopentane and was only partially
studied with only one ratio of composition studied.

The analysis of the results followed two previously developed models in order to
further validate and accurate such methods.
The model denominated LPUR allows for the prediction of thermal conductivity of
pure components and was applied to cyclopentane.
The model denominated Extended Wassljewa Model allows for the estimation of the
thermal conductivity in mixtures and was applied to all studied mixtures in the system of
nitrogen and isopentane.




KEY WORDS

Thermal Conductivity; Transient Hot Wire Method; Wassiljewa Model; Nitrogen; Isopentane;
Cyclopentane; Binary Mixture, Experimental Data
II
RESUMO ANALTICO


O objecto de estudo deste trabalho foi a condutividade trmica de sistemas binrios de
gases, em diversas combinaes de razes molares dos componentes, cuja condutividade
trmica tambm foi estudada individualmente.
No total, dois sistemas foram estudados; o primeiro sistema era composto por azoto e
isopentano e foi completamente estudado atravs de um conjunto de trs misturas de
composies distintas, enquanto o segundo sistema era composto por isopentano e
ciclopentano e foi apenas parcialmente estudado atravs de uma nica composio da mistura.

A anlise dos resultados foi feita seguindo dois modelos previamente desenvolvidos
de forma a continuar a validao e aperfeioamento desses mesmos mtodos.
O modelo denominado por LPUR permite a previso da condutividade trmica para
components puros a foi aplicado ao estudo de ciclopentano.
O modelo denominado por Extended Wassljewa Model permite a previso da
condutividade trmica para misturas de gases e foi aplicado a todas as misturas no sistema de
azoto e isopentano.




PALAVRAS CHAVE

Condutividade Trmica; Mtodo transiente do fio-quente; Modelo de Wassiljewa; Azoto;
Isopentano; Ciclopentano; Mistura Binria; Dados Experimentais
III
INDEX

Abstract I
Key Words I
Resumo Analtico II
Palavras-chave II
Index III
Index of figures V
Index of tables IX
Chapter 1 Introduction 1
Chapter 2 Theoretical Basis and the Apparatus 4
2.1. Thermal Conductivity 4
2.2. The Method 5
2.3. Description of the Apparatus 6
2.4. Experimental Procedure 14
2.5. Preparation of the Mixtures 17
Chapter 3 Verification of the Calibration 20
Chapter 4 Results 23
4.1. Mixtures of Nitrogen and Isopentane 23
4.1.1 25 % i-pentane / 75 % nitrogen 23
4.1.2 54 % i-pentane / 46 % nitrogen 25
4.1.3 75 % i-pentane / 25 % nitrogen 25
4.2. Cyclopentane 27
4.3. Mixtures of Isopentane and Cyclopentane 28
4.3.1 26 % i-pentane / 74 % c-pentane 28
Chapter 5 Analysis of the Results 31
5.1. Thermal Conductivity of mixtures 31
5.2. The Nitrogen and Isopentane System 32
5.3. Pure Cyclopentane 49
5.4. The cyclopentane and isopentane system 51
Chapter 6 Conclusions 53
6.1. Accomplished in this work 53
6.2. Recomendations for future work 53
IV
Chapter 7 References 56
Appendix I 59
V
INDEX OF FIGURES

Figure 2.1 Scheme of the thermal conductivity apparatus used as it was
originally built. 7
Figure 2.2 Schematic true to scale representation of the measuring cell. 8
Figure 2.3 New system developed for the lower part of the cell. The part on
the left is kept from rotate by the disk in the middle. The screw in
the right regulates the axial position of the part on the left 9
Figure 2.4 Picture of the new cell after the assembly of the new system to
support of the wires. 10
Figure 2.5 Detail of the system for the support of the wires in the lower part of
the cell. 10
Figure 2.6 Picture of the screw and non-routable part for the support of the
wires in the lower part of the cell. 11
Figure 2.7 Schematic representation of the Teflon sealing for the connections
in the head of the cell. 11
Figure 2.8 Wheatstone bridge used in this work. 12
Figure 2.9 Schematics of the tubing of the thermal conductivity apparatus 13
Figure 2.10 T = f(ln t) graph obtained from a measurement, showing the
occurrence of convection. It should be noted that this graph was
obtained deliberately to show the curvature. In normal cases the
curvature might not be this perceptible. 15
Figure 2.11 Interface of program Lambda2000 with an emphasis over the T
and its presentation within normal limits. 16
Figure 3.1 Results of the tests with nitrogen for verification of calibration.
Comparasion to Fonsecas [1] values and to NIST reference data
[16]. 20
Figure 3.2 Interface of program Lambda2000 with an emphasis over the
specific resistances of the long wire langer Draht and the short
wire kurzer Draht. Also emphasised is the difference between
both values . 22
Figure 4.1 First selection of the results obtained in the measurements with 25
% isopentane and 75 % nitrogen. 23
VI
Figure 4.2 Final selection of the results obtained in the measurements with 25
% isopentane and 75 % nitrogen 24
Figure 4.3 Final selection of the results obtained in the measurements with 44
% isopentane and 56 % nitrogen. 25
Figure 4.4 First selection of the results obtained in the measurements with 75
% isopentane and 25 % nitrogen. 26
Figure 4.5 Final selection of the results obtained in the measurements with 75
% isopentane and 25 % nitrogen. 26
Figure 4.6 Final selection of the results obtained in the measurements with
cyclopentane. 27
Figure 4.7 First selection of the results obtained in the measurements with 75
% isopentane and 25 % cyclopentane 28
Figure 4.8 Second selection of the results obtained in the measurements with
75 % isopentane and 25 % cyclopentane. 29
Figure 4.9 Final selection of the results obtained in the measurements with 75
% isopentane and 25 % cyclopentane. 29
Figure 5.1 Extrapolation of the data obtained for the system N
2
+ i-C
5
for a
pressure of 1 bar. 32
Figure 5.2 Extrapolation of the data obtained for the system N
2
+ i-C
5
for a
pressure of 5 bar. 33
Figure 5.3 Extrapolation of the data obtained for the system N
2
+ i-C
5
for a
pressure of 10 bar. 33
Figure 5.4 Thermal conductivity as a function of the composition for a
pressure of 1 bar. The lines refer to the Wassiljewa method where
was fitted individually for each temperature. 35
Figure 5.5 Deviation from the experimental points to the Wassiljewa model (p
= 1 bar). 35
Figure 5.6 Thermal conductivity as a function of the composition for a
pressure of 5 bar. The lines refer to the Wassiljewa method where
was fitted individually for each temperature. 36
Figure 5.7 Deviation from the experimental points to the Wassiljewa model (p
= 5 bar). 37

VII
Figure 5.8 Thermal conductivity as a function of the composition for a
pressure of 10 bar. The lines refer to the Wassiljewa method where
was fitted individually for each temperature. 37
Figure 5.9 Deviation from the experimental points to the Wassiljewa model (p
= 10 bar). 38
Figure 5.10 Influence of the temperature in the values of . 40
Figure 5.11 Influence of the pressure in the values of . 40
Figure 5.12 Influence of the temperature in the values of e. The lines refer to
equation 5.3. 41
Figure 5.13 Deviations of the experimental points of e relatively to the results
obtained with equation 5.3, represented as a function of
temperature. 42
Figure 5.14 Influence of the temperature in the values of e. The lines refer to
equation 5.3. 42
Figure 5.15 Deviations of the experimental points of e relatively to the results
obtained with equation 5.3, represented as a function of pressure. 43
Figure 5.16 Thermal Conductivity as a function of the composition for a
pressure of 1 bar. The lines refer to the Extended Wassiljewa
Method, where is estimated by means of equation 5.3. 44
Figure 5.17 Figure 5.17: Deviations from the experimental points to the
Extended Wassiljewa Model (p = 1 bar). 44
Figure 5.18 Thermal Conductivity as a function of the composition for a
pressure of 5 bar. The lines refer to the Extended Wassiljewa
Method, where e is estimated by means of equation 5.3. 45
Figure 5.19 Deviations from the experimental points to the Extended
Wassiljewa Model (p = 5 bar). 45
Figure 5.20 Thermal Conductivity as a function of the composition for a
pressure of 10 bar. The lines refer to the Extended Wassiljewa
Method, where e is estimated by means of equation 5.3. 46
Figure 5.21 Deviations from the experimental points to the Extended
Wassiljewa Model (p = 10 bar). 46
Figure 5.22 Agreement between the experimental values of thermal
conductivity and the values predicted by equation 5.3. 47
VIII
Figure 5.23 Experimental values of thermal conductivity and the relative
deviation of the values predicted by equation 5.3 to them. 48
Figure 5.24 Deviations from the experimental thermal conductivity data for
cyclopentane to the values estimated through the LPUR equation.
50

Figure 5.25 Comparison between the values of l obtained for pure
Cyclopentane in this work and in previous works.
51

IX
INDEX OF TABLES

Table 3.1 Values obtained for the thermal conductivity at the pressure of 1
bar for measurements with nitrogen in this work and in Fonsecas
work and their deviation to the reference data. 21
Table 5.1 Values obtained for the fitting of for different pressures and
temperatures. 39
Table 5.2 Values obtained for the parameters in equation 6.2, in the fitting of
the experimental values of . 41
Table 5.3 Values of the parameters of equation 5.5 for cyclopentane. 49
Table A1.1 Final selection of the results obtained with the mixture of 75 %
nitrogen and 25% i-pentane. 59
Table A1.2 Final selection of the results obtained with the mixture of 54 %
nitrogen and 46 % i-pentane. 63
Table A1.3: Final selection of the results obtained with the mixture of 25 %
nitrogen and 75 % i-pentane. 67
Table A1.4 Final selection of the results obtained with cyclopentane 70
Table A1.5 Final selection of the results obtained with the mixture of 74 % c-
pentane and 26 % i-pentane. 74
1
1. INTRODUCTION

Rigid polyurethane and polyisocyanurate foams, denominated respectively as PUR
and PIR, are applied to a large number of purposes due to their high thermal insulating
capacity.
Among those applications are thermal insulation boards to pipe insulation, technical
refrigeration processes or industry applications.
These particular kinds of foams are also very common in domestic refrigerators for
example, being PUR foam the preferred insulating material, due to several advantages:
self-adhesive rigid foam systems enable a weight-saving sandwich construction to be
produced in a single operation and the excellent thermal insulating properties permit a
relatively small wall thickness.
Although the heat conduction of the solid material of the foam influences the heat
transfer of such a foam, it is in fact the gas or vapour trapped inside the voids of the foam
that mainly determine the amount of heat transfer possible. These gases that work as
blowing agents account for up to 65 % (and never less than 60 %) of the heat transfer of
the foam.
The evaluation of a blowing agent as an insulator is done by the comparison of the
thermal conductivity of such an agent in its gaseous form to the thermal conductivity of air
that it displaces. In accordance to the reference [2], the normal conductivity of air at 300 K
is of 27 mW
.
m
-1.
K
-1
.
Until the middle of the decade of 1990 the most used blowing agent was CFC-11 for it
presented a value of thermal conductivity of 8,3 mW
.
m
-1.
K
-1
at 300 K (as presented on
reference [3]). However, this gas has an elevated Ozone Depletion Potential, which, in
virtue of the Montreal Protocol, made it unusable.
Research for the best replacement of CFC-11 was undergone both in Europe and in
North-America, resulting in different options.
While in North America the research focused primarily in HCFCs and, afterwards,
due to the implementation of stricter restrictions and regulations, in HFCs with a null
Ozone Depletion Potential; in Europe the research focused in hydrocarbons, mainly
cyclopentane and mixtures containing cyclopentane, also possessing a null Ozone
Depletion Potential.
2
Comparing both solutions, HFCs have the advantages of being non-flammable and a
lower gas phase thermal conductivity, and hydrocarbons have a lower Global Warming
Potential (the reason why they were chosen in Europe, as can be read in reference [4]) and
optimal thermophysical properties for the application to insulation materials.
During the lifetime of a foam, the constitution of the mixture of gases inside the foam
pores is not constant, leading to a significant loss of the thermal efficiency. This is due to
diffusion processes of both air inwards the foam cells and of the gases outwards the foam
cells.
The variation of a PUR foams thermal conductivity happens, according to a study
carried out at the Oak Ridge National Laboratory, USA [5], in two clearly separated phases.
The first is characterized by a rapid increase on the thermal conductivity, which is assumed
to be caused by the diffusion of air into the cells; the second is characterized by a slower
increase on the thermal conductivity, which is attributed to the diffusion of the original
mixture of gases to the exterior of the cells.
Adding to the diffusion effects, also properties of the foam itself such as the types of
isocyanate and polyol used, the cells size and openness, the blowing agents used and their
initial composition inside the cells and the interactions between the blowing agents and
the external atmospheric gases defined by solubility and diffusion coefficients
contribute to the definition of the kinetics of the aging of the foam.
The work that has been carried and is presented here is inserted in a larger project that
focuses on the thermal conductivity of the gas phase inside the foam cells at the same time
as it focuses on the research of a blowing agent that conjugates good thermophysical
properties as well as a stability of such properties throughout the lifetime of the foam. To
that purpose its particularly useful to study mixtures that include nitrogen, for being that
the most abundant gas in the atmosphere; such mixtures will give a precise idea of the
behaviour of the diffusion-aged foams.
The project also intends to establish a systematic prediction method for the thermal
conductivity of gas mixtures, either by proving pure theoretical modelling methods, or
through the development of a semi-empirical method. More specifically, in the study
carried out in performing this thesis, the objective on this matter was to further aggregate
data to a previously [1] presented model, validating it, if possible.
In this work, the thermal conductivity of pure cyclopentane and mixtures of isopentane,
nitrogen and cyclopentane was measured sing the trasient hot-wire method, which is the
IUPAC standard method for the determination of thermal conductivities [6]. The
3
measurements were performed at temperatures between 303 K and 395 K and at pressures
up to 1.0 MPa.
The obtained results were correlated with the Wassiljewa mixing rule modified by
Mason and Saxena. A study of how the parameter changes with temperature, pressure
and composition of the mixtures was performed, culminating in the development of a
mathematical model which allows the calculation of values for this parameter for any
given conditions. Another model is also presented for the calculation of values for any
given pressure and temperature, for pure compounds.
4
2. THEORETICAL BASIS AND THE APPARATUS


2.1. THERMAL CONDUCTIVITY

In any material, solid, liquid or gas, a heat flux occurs whenever a temperature
gradient is applied. This heat flux starts in the high temperature region towards the part of
the material with the lower temperature.
If the energy is transferred by conduction, the heat flux per unit area is proportional
to the temperature gradient:
x
T
Q

= (2.1)

where Q is the heat flux per unit area and x T is the temperature gradient in the
direction of heat flux. The proportionality constant , is the thermal conductivity. The
numerical value of the thermal conductivity indicates the velocity of the heat transference
when the material is perturbed from an equilibrium state by a temperature gradient. The
negative signal is required by the second law of thermodynamics, since x T is negative
(the temperature decreases in the direction of the heat flux).
The physical mechanism of thermal conduction of gases at low pressures is simple.
The gas molecules are in a continuous and random movement, colliding with each other,
exchanging energy and movement. When a molecule goes from a high-temperature region
to a low-temperature region, it transports kinetic energy to this last region increasing the
kinetic energy in the low-temperature region, consequently the temperature increases.







5


2.2. THE METHOD

The measurements of thermal conductivity in this work were performed in an
apparatus based on the transient hot wire method, the standard method adopted by IUPAC
to evaluate thermal conductivity. The theoretical bases of this method, as well as its
equations and assumptions, have been described intensively by a good number of authors
[6-10] and for that reason only a short note on the subject will be presented here.

The method consists in the application of a time dependent perturbation a heat flux,
in this case to a fluid initially in equilibrium, using a very thin platinum wire for the
purpose. According to equation 2.2, where a stands for the thermal diffusivity and C = exp
(), being Eulers constant ( = 0.57721), the evolution of the temperature gradient
registered in function of time will allow the calculation of the thermal conductivity of the
fluid

|
|

\
|
=
C r
at q
T
o
2
4
ln
4
(2.2)

This equation corresponds to an ideal model in which a number of considerations and
approximations are made. In reality, several correction factors have to be applied for the
correct calculation of from the raw data. Some approximations however were already
accounted for during the design and careful dimensioning of the apparatus, making the
correspondent corrections negligible.

Concerning the platinum wire, the ideal model makes the following considerations:
- Infinitely long heat source
- Linear, vertical and with infinitesimal diameter
- Zero heat capacity and infinite thermal conductivity
- Heat dissipation constant and radial


6
Concerning the fluid, the model stands that:
- Isotropic and infinite fluid
- Physical properties independent of the temperature

In addition, the model also considers that the heat transfer occurs exclusively by
conduction, without any occurrence of convection or radiation.
Reports from previous works carried out with this same apparatus also contain
information about the theory behind the method, together with the description of the
apparatus [10-12].
In the present work, bare platinum wires were used as well as the same equation and
approximations considered by Santos and Oliveira [13, 14] and Fonseca [1].



2.3. DESCRIPTION OF THE APPARATUS

The apparatus used was constructed in 1994 in co-operation with the University of
Stuttgart.
Through the years it has been subjected to several modifications and improvements,
all listed by the several authors who worked and described the apparatus since 1994 [12-
17], the most important of them occurring in 2006 and done by Fonseca [1].
This last modification has greatly simplified the apparatus and made it more user-
friendly.
In this report a description of the most recent characteristics of the apparatus will be
made as well as a brief comparison to the previous configuration in order to be noticed
how the recent modifications affect the results..

The apparatus has two main sections that can clearly be separated. One of them is the
apparatus itself, consisting of the thermostatic volume where the measuring cell is
comprised, also including all the tubing system, two auxiliary vessels for the mixtures
preparation and the heating system. The other section is composed by the ensemble of all
the electronic parts data acquisition systems, the automatic Wheatstone bridge,
temperature controllers, automation systems etc.

7

Figure 2.1: Scheme of the thermal conductivity apparatus used as it was originally built.

The apparatus is made of two concentric cylinders made of stainless steel, with 39
cm in diameter, one placed on top of the other, making a total height of approximately 82
cm. Inside the lower part there is a support for the measuring cell, and around it, an
electrical resistance is spooled to be used as heat source. The apparatus is also provided
with a system of cooper tubes for circulation of cold water or even liquid nitrogen in case a
cold source is needed. In the bottom, there is a fan to promote the thermal uniformity
inside the whole volume of the apparatus.
Measurements of the thermal conductivity of pure gases can be performed with only
the lower part of the apparatus, while for the study of mixtures it is necessary to use the
upper part containing the two auxiliary vessels for the pure components, assuming the
study of binary mixtures.
The apparatus is suitable for measurements between 300 K and 500 K (without the
use of the cooling tubes) and pressures that can vary from 0.1 MPa to about 1,8 MPa. This
upper limit in pressure is imposed by the pressure gage in use. A safety diaphragm is also
used to assure that this value of pressure is not overtaken.
The heart of the apparatus is the measuring cell, shown schematically on Fig. 2.2
as it was implemented by Fonseca [1]. This main part of this cell is a stainless steel
cylinder with 200 mm of length and 48 mm of external diameter. The cylinder has two
8
holes in its interior, from bottom to top, with 16 mm of diameter, in which the platinum
wires and their supports are built in.
















Figure 2.2: Schematic true to scale representation of the measuring cell.

The cell possesses two platinum wires with different lengths and 10 m in diameter,
in order to account for end effects as well as other possible sources of errors. In their upper
edge the wires are welded with gold to a rigid part made of platinum, which possesses
some mobility since it is connected to the thick wire by a flexible connection, a thin piece
of platinum. To assure that the wire is at the centre of the cell, a guide is placed in the
cell, made of Teflon. In the lower part of the cell each thin wire is attached to a part that
can only move axially along the cell, and is kept from rotate. These parts are represented in
figure 2.3, together with the screws that allow the adjustment of the position of these parts,
enabling the stretching of the thin platinum wires.





9






Figure 2.3: New system developed for the lower part of the cell. The part on the left is kept from rotate by the
disk in the middle. The screw in the right regulates the axial position of the part on the left.

The main purpose of this system of support is to overcome the ambiguities related to
the stretch and position of the wires, as well as facilitate the welding of new wires
whenever needed. The system has to be fixed, since the main problems with the previous
used system were related with the flexibility of the gold spiral that held the wires.
The effects of thermal expansion are different for the cell made of steel and for the
platinum wires. With a raise in the temperature the dilation of the stainless steel cell will be
superior to the expansion in the length of the platinum wire, and this can therefore, lead to
the breaking of the wires if at cold temperature these are already completely stretched. The
initial purpose for the spiral in use was to compensate for this problem, decompressing as
necessary at higher temperatures, and compressing again when measurements were
performed at lower temperatures, keeping the wire always stretched.

With the most recent configuration, the problem with thermal expansion is overtaken
by the flexible part already described, placed in the upper part of the cell. However
calculations show that within an interval of 200 K (the apparatus is presently suitable for
measurements between 300 K and 500 K), the possible problem with the thermal
expansion affects the wire in only half a millimetre maximum, which means that after the
wire is stretched, at room temperature, it is possible to move the part in its lower end by
0.5 mm. This will not change significantly the position of the wire in the cell and will
allow simplifying the upper part of cell, since it becomes possible to weld the thin platinum
wire directly to the fixed thick wire, without the use of flexible parts or guides.
This new support also brings benefits to the stability of the wires during
transportation and placement of the cell inside the apparatus, and even during
measurements, for the spiral used before the changes operated by Fonseca could act as an
amplifier for the vibrations inevitably transmitted to the cell due to shocks or other
occurrence - due to its flexibility.
10
Figure 2.4 shows the complete interior system of the cell. In figures 2.5 and 2.6 it is
possible to see in detail the system developed for the lower end of the platinum wires, with
the screw and the non-routable part. In picture 2.6 the showed part corresponds to the short
wire.














Figure 2.4: Picture of the new cell after the assembly of the new system to support of the wires.


Figure 2.5: Detail of the system for the support of the wires in the lower part of the cell.
11










Figure 2.6: Picture of the screw and non-routable part for the support of the wires in the lower part of the cell.

Attached to the upper part of the cell, is what it can be called the head of the cell,
which is actually the cover of an air tight pressure vessel in which the measuring cell is
placed for measurements. It is through the head of the cell that the electric contacts from
the platinum wires to the electronic part of the apparatus are made. Oliveira [13]
mentioned some problems with an old system in which the sealing around these electrical
connections was made from teflon, according to what is represented in figure 2.4, and
described a new system based on the use of a ceramic sealing.













Figure 2.7: Schematic representation of the Teflon sealing for the connections in the head of the cell.

12

The main element of the electronic section is the automatic Wheatstone bridge,
shown schematically in Fig. 2.3, used to determine the variation of the potential of the
wires with time and for the calculation of the temperature increase during the transient
heating, from which the thermal conductivity is calculated.


Figure 2.8: Wheatstone bridge used in this work.

All the electronic parts of the apparatus are controlled by computer using software
developed in the C++ language specifically for this application, the program Lambda2000.
The temperature of the apparatus is regulated by a PID controller connected to a
Pt100 thermometer. Several other thermometers of the same kind are strategically placed
in the apparatus to allow the evaluation of the uniformity of the temperature as well as for
safety reasons. The most important of them are placed in the cell, one at the top and the
other in the bottom. For the measurements, the temperature given by this two
thermometers must differ in less than 0.1 K.

The tubing system as implemented by Fonseca is schematically represented in fig. 2.9.






13











Figure 2.9: Schematics of the tubing of the thermal conductivity apparatus.


In any system designed to work at pressures other than the normal pressure, being
vacuum or high pressure systems, there is a need for air tightness, and in this subject, every
valve and every connection in the tubing represents a possibility for leaks.
Fonseca managed to eliminate about a dozen of connections from the tubing system,
therefore reducing the risk of a leak to occur.
Fonseca also decreased the amount of tubes in the upper part of the apparatus,
making it much easier to place and remove this part of the apparatus whenever needed,
allowing these procedures to be carried out by just one person.
Regarding the configuration of the tubing, it can be noticed that further
simplifications are possible to be carried out, mainly concerning the number of valves.
Valve 4 could also be removed; however there are two reasons to maintain it. The first is
related to the fact that when a leak is noticed the existence of the valve 4 will allow for an
easier location of that same leak; the second is for it allows for a more versatile procedure
when reducing pressure inside the measuring cell, as it will be explained further on in this
text.





14

2.4. EXPERIMENTAL PROCEDURE

Before starting any measurements the apparatus should be checked for air tightness
and be left under vacuum at a relatively high temperature for some hours.
If the gas to be studied is available in a high pressure bottle as in the case of
Nitrogen the apparatus is first programmed for the desired temperature and then filled
with the gas until a pressure close to the required, as verified in the LCD screen on the
electronic part of the apparatus.
The program Lambda2000 must then be run for a precise measuring of both
temperature and pressure. Only when both values are stable should the thermal
conductivity measurements begin.
In order to perform the study of components liquid at room temperature cases of iso
and cyclopentane in this work one or both pressure vessels must be used, depending if
the study is conducted with a pure component or a mixture. The vessels must first be
evacuated for a long time and then partially filled with the desired compound, through
suction generated by the vacuum in the interior.
After this, the compound needs to be degassed, i.e. be freed from all the dissolved
gases. This is done through 7 or 8 cycles of cooling-evacuating-warming, with a final
evacuation for some seconds at room temperature. The cooling is performed with dried ice
and should be done during, approximately, one hour. If during the evacuating of the gases
there should occur a small lost of liquid, a new filling of a compensating quantity can be
performed right after the first cycle. After this, no more filling should be attempted.
When the degassing is complete the vessel is introduced in the apparatus that should
then be set for the desired temperature. The vessels must then be left to heat and at this
point the importance of not having totally filled them is revealed, for that could generate an
overpressure that would damage or even burst the vessels so that the compounds inside
can also reach the desired temperature. Only at that point should the mixture be prepared.
Once again, the program Lambda2000 must be used to check the equilibrium inside
the cell.
It should be taken into account that often a considerable amount of time is necessary
to achieve a perfect equilibrium inside the cell. Even after the pressure and temperature are
stable, the gas inside might still not has reached the equilibrium point. A good way of
15
evaluating this situation is by observing the T = f(ln t) graph that should present as a
straight line.
Figure 2.10 shows an example of an experiment where the gas inside the cell was still
not in equilibrium, indicating the occurrence of convection.


Figure 2.10: T = f(ln t) graph obtained from a measurement, showing the occurrence of convection. It should
be noted that this graph was obtained deliberately to show the curvature. In normal cases the curvature might not
be this perceptible.

When taking the data, a sufficient amount of valid points must be obtained.
Usually, the validity of the points is demonstrated by a temperature rise of T = 2.000
0.025 K, a parameter that

is emphasised in figure 3.2 and 3.3, in a demonstration of its
validity in the programs interface.

16

Figure 2.11: Interface of program Lambda2000 with an emphasis over the T and its presentation within normal
limits.


However, sometimes a point will fall outside of this margin with a very low
deviation,. This point, especially if it appears isolated among a wide number of valid points
and when the pressure and temperature are already constant inside the measuring cell,
should not automatically be unconsidered, for its value of might be within the normal
range, accounting for the average deviation.
Each point in such conditions should be evaluated independently for the variation on
the temperature rise might be due to a brief variation on the PID controller which does not
affect the mixture in study.

More information on how to operate the program Lambda2000 can be found
extensively in the Appendix A3 of Oliveiras work [13].


17
2.5. PREPARATION OF THE MIXTURES

When performing the mixtures, the accuracy with which we can calculate the
composition depends directly from how exactly we know the conditions under which the
mixture was done, namely the temperature and the partial pressure of each one of the
mixture components.
The temperature of the mixing cell can be followed by a PT100 placed on the upper
part of the apparatus. This PT100 can be placed as close to the cell as possible, however
the value yielded can only be read with one decimal place. Simultaneously, the pressure on
this cell can only be followed in the LCD screen available close the other electronic parts,
with two decimal places.
On the other hand, the computer, by the means of measurements, allows the
knowledge of the pressure inside the measuring cell with three decimal places, and the
temperature inside this cell is known with much more accuracy, since the value recorded
by the computer is the result of the average between two PT100s placed in the top and in
the bottom of the cell.
Performing the mixture in the measuring cell allows a more profound and accurate
knowledge of the mixture conditions. Furthermore, these conditions can be recorded, lets
say, every two minutes, becoming possible to record the whole process. If necessary, based
on these records, it will be possible at anytime to consult those records in order to check or
to make an adjustment on the mixture composition.
The small volume of the measuring cell and the shape (that does not promote the
homogeneity of the mixture) are negative sides of this procedure. However, experiments
conducted by Fonseca have showed that it is possible to obtain stable values of thermal
conductivity just half an hour after the mixture. These values were confirmed some days
after the mixture was prepared, after measurements at other temperatures and consequently,
other pressures.
With the preparation of mixtures being performed with this accuracy, it becomes
clear that it doesnt make much sense to prepare a different mixture with the same
composition for each isotherm. Instead a mixture can be prepared at the maximum pressure
desired, and the measurements can be performed changing the temperature between the
values of the several isotherms. This represents a benefit, for the use of a single mixture
and performing the measurements with a single exact composition may improve
significantly the final results.
18
After the measurements at all temperatures, some pressure can be released from the
cell, repeating then the process to all the temperatures again.
Several considerations to this procedure should be made however. This process is of
course more time consuming, since the setting of a new temperature implies a wait
between 2 and 4 hours until the pressure and temperature values are absolutely stable again.
Another problem come with the fact that the apparatus is not placed in a temperature
controlled room, and the same setting for the temperature controllers, may in different days
lead to different temperatures of the apparatus. This problem can, however, be identified
and corrected before the experiments, even though a correction in the temperature means
more time consumed.
Also a special care is needed when releasing the pressure from the cell.
If this is done in an uncontrolled way, some condensation of the less volatile
component may occur due to the Joule-Thompson effect, leading to a change in the
mixture composition. If the pressure release is done against vacuum, the pressure decrease
will be too fast and the expansion of the gases will provoke their cooling. For gases like
nitrogen or carbon dioxide this constitutes no issue, but when the mixture contains less
volatile gases, e.g. pentane, the cooling may lead to the condensation of the gas, changing
the composition of the mixture that is released from the cell and consequently changing the
composition of the remaining gas mixture.
To account for this possibility, the changes in the pressure should be performed
according to the procedure described next.
During the measurements of thermal conductivity, valve 8 is of course closed. Before
performing any change in the pressure, valve 7 should be opened and the tubing system
should be evacuated. The change in the pressure of the measuring cell should then be made
phased in several steps. Closing valve 7 and open valve 8 will promote an expansion in the
gas mixture. This expansion is smaller than the one mentioned before, and even if some
condensation occurs, it will be momentarily since the system will soon re-establish its
equilibrium. After waiting for a homogeneous composition (lets consider one minute as a
reference value), valve 8 can be closed and the space between this valve and valve 7
evacuated again. This procedure caused a decreased in the mixture pressure inside the cell,
assuring that the same composition is preserved. This process should then be repeated until
the desired pressure is achieved.
Going back to the tubing system presented on fig 2.9, the last explanation accounts
for the use of valve 7 and 8, that otherwise would look redundant. Valve 4 was also
19
deliberated left as part of the system, and even though in normal conditions should not be
used, it may become of serious importance in the case of failure of some of the other
valves. Accordingly, if valve 7 fails, the process described before for the pressure changes
can be accomplished using this valve. Notice that this valve can also be used in normal
conditions when bigger steps in the pressure are required, with the convenient
compensation in the waiting time between each step. Valve 4 can also be used as a
protection for the pressure sensor p1 from overpressures in case of failure of valves 1 to 3.

20
3. VERIFICATION OF THE CALIBRATION

The most recent modifications introduced by Fonseca to the Measuring Cell should
assure that the length of the wires, and therefore the calibration of the apparatus, remained
constant throughout a long period of work.
To assure that this was true the first measurements done involved only nitrogen. This
was the gas previously used by Fonseca to calibrate the apparatus and allowed for a direct
comparison of the parameters involved in this work.
By choosing two temperatures of the previously studied by Fonseca, and at several
pressures, it was possible to draw two isotherms that could directly be compared to the
previous results, as well as to the NIST reference data.

25
26
27
28
29
30
31
2 3 4 5 6 7 8 9 10 11
p / bar


/

m
W

m
-
1
K
-
1
NIST 300K
NIST 320K
NIST 360K
JOSE 318K
JOSE 358K
CARLOS 318K
CARLOS 358K
Linear (JOSE 318K)
Linear (CARLOS 318K)
Linear (CARLOS 358K)
Linear (JOSE 358K)

Figure 3.1: Results of the tests with nitrogen for verification of calibration. Comparasion to Fonsecas [1] values
and to NIST reference data [16].

By extrapolation of the isotherms of both this work and the work by Fonseca to the
pressure of 1 bar, it is possible to determine the deviation between such results.
Furthermore, by interpolating the data available from NIST at 1 bar for the
corresponding temperatures of 318 K and 358 K it is possible, as well, to determine the
deviation of such measurements of the thermal conductivity in order to assess the quality
of the performed calibration.


21
Table 3.1: Values obtained for the thermal conductivity at the pressure of 1 bar for measurements with nitrogen
in this work and in Fonsecas work and their deviation to the reference data.
Data from Temperature (K) (mW
.
m
-1.
K
-1
)
Relative deviation to
NIST data
Present work 358,49 29,3357 0,87 %
Present work 317,87 26,6396 1,55 %
Jos Fonsecas 357,81 29,4125 0,61 %
Jos Fonsecas 318,14 26,8489 0,77 %
NIST 358,15 29,5942 -
NIST 318,15 27,0582 -


The relative deviation between the measurements in this work and the ones in
Fonsecas previous work have values of 0,26 % and 0,78 %, respectively for 80C and
40C

As can be seen on the last table, the relative errors between the measurements
obtained in this work and the ones obtained by Fonseca, as well as the relative errors to the
NIST interpolated data are perfectly within acceptable parameters and taking in
consideration a normal deviation associated to the measurements themselves and the fact
that the temperatures were not perfectly identical between the two works a situation due
to the non-climatized surroundings of the apparatus it is possible to see that the
calibration was still valid and that it should continue to be so.
Adding to such results, two parameters given by the Program Lambda2000 confirm
such conclusion.
These two parameters are directly associated to the wires: the specific resistance and
the difference between such resistance on both wires. These parameters are emphasised on
the image 3.2.



22

Figure 3.2: Interface of program Lambda2000 with an emphasis over the specific resistances of the long wire
langer Draht and the short wire kurzer Draht. Also emphasised is the difference between both values .


The difference between both resistances should be as near to zero as possible, for the
specific resistance is given by the quoficient between the resistances of each wire and their
lengths.
The values of D varied between the minimum of 0,03 and a maximum of 0,10.
All these aggregated informations allowed for a conclusion on the correctness of the
previous calibration and, therefore, exclusion of any alteration to the platinum wires lenght.

Following this verification, the first tests were conducted.

23
4. RESULTS

Having been verified that the calibration was still valid, there was no need to redo the
measurements with pure isopentane since Fonseca [1] had already done so.
Therefore, the first measurements where done directly with mixtures of isopentane
and nitrogen of approximate molar ratios of 1/3, 1/1 and 3/1 between both compounds
the exact ratios will be presented later on this text.

4.1. MIXTURES OF NITROGEN AND ISOPENTANE

4.1.1. 25 % i-pentane / 75 % nitrogen

For the mixture with an exact molar composition of 25,2 % in isopentane and 74,8 %
in nitrogen the experiments were conducted between 306 K and 390 K and at pressures
between 1,5 bar and 9 bar.
Later on, however, it was verified that the results below 2 bar were not accurate
enough.
The results of the experiments with this mixture are presented in figure 4.1 in the
form of 6 isotherms.

18,0000
20,0000
22,0000
24,0000
26,0000
28,0000
30,0000
32,0000
1,000 2,000 3,000 4,000 5,000 6,000 7,000 8,000 9,000 10,000
p / bar


/

m
W

m
-
1
K
-
1
391K
375K
353K
333K
314K
306K

Figure 4.1: First selection of the results obtained in the measurements with 25 % isopentane and 75 % nitrogen.
24
The lower temperatures are limited to a range of lower pressures due to the dew point
of the mixture.

The results show that for lower temperatures, the results are divergent from the
results at higher temperatures.
It can be seen on a rough analysis of the isotherms on the graph that are the values at
1,5 bar that originate the divergent slope.
That being so, and taking into consideration that the Hot wire transient method is not
valid at the pressure of 1 bar, it is also possible to conclude that at a pressure of 1,5 bar, the
results are already fallible.

Therefore, the considerate results were the ones presented in image 4.2.

18,0000
20,0000
22,0000
24,0000
26,0000
28,0000
30,0000
32,0000
1,000 2,000 3,000 4,000 5,000 6,000 7,000 8,000 9,000 10,000
p / bar


/

m
W

m
-
1
K
-
1
391K
375K
353K
333K
314K
306K

Figure 4.2: Final selection of the results obtained in the measurements with 25 % isopentane and 75 % nitrogen.


Here is visible that all the extrapolated linear relations for the results at each
temperature have an approximately identical slope.



25
4.1.2. 54 % i-pentane / 46 % nitrogen

For the mixture with an exact molar composition of 56,14 % in Nitrogen and 43,86
% in isopentane the experiments were conducted between 333 K and 390 K and at
pressures between 3 bar and 10 bar.
The results of the experiments with this mixture are presented in figure 4.3 in the
form of 4 isotherms.

18,0000
20,0000
22,0000
24,0000
26,0000
28,0000
30,0000
1,000 2,000 3,000 4,000 5,000 6,000 7,000 8,000 9,000 10,000
p / bar


/

m
W

m
-
1
K
-
1
390K
373K
352K
332K

Figure 4.3: Final selection of the results obtained in the measurements with 44 % isopentane and 56 % nitrogen.



4.1.3. 75 % i-pentane / 25 % nitrogen

For the mixture with an exact molar composition of 74,93 % in isopentane and 25,03
% in nitrogen the experiments were conducted between 333 K and 390 K and at pressures
between 2 bar and 8 bar.
The results of the experiments with this mixture are presented in figure 4.4 in the
form of 4 isotherms.

26
18,0000
20,0000
22,0000
24,0000
26,0000
28,0000
30,0000
1,000 2,000 3,000 4,000 5,000 6,000 7,000 8,000 9,000 10,000
p / bar


/

m
W

m
-
1
K
-
1
391K
375K
353K
332K

Figure 4.4: First selection of the results obtained in the measurements with 75 % isopentane and 25 % nitrogen.

For the temperature of 353 K (80 C) it can be seen that the results at the lowest
pressure are incoherent with the further ones.
Also, an analysis of the dispersion of the values obtained at 2 bar and 332 K revealed
a great dispersion, which lead to the the final selection that presents in the graph 4.5
follows.

18,0000
20,0000
22,0000
24,0000
26,0000
28,0000
30,0000
1,000 2,000 3,000 4,000 5,000 6,000 7,000 8,000 9,000 10,000
p / bar


/

m
W

m
-
1
K
-
1
391K
375K
353K
332K

Figure 4.5: Final selection of the results obtained in the measurements with 75 % isopentane and 25 % nitrogen.
27

As can be seen, for the temperature of 33K, the limitations due to the dew point only
allowed having two sets of raw data at two different pressures.
Although this puts in question the accuracy of the isotherm, the apparent consistency
to the other ones the similar slope and a reduced scattering of the data led to the
decision of accounting this isotherm in the following calculus.

4.2. CYCLOPENTANE

The next experiments were to be conducted on a mixture of cyclopentane and
isopentane.
However, seeing that the last results of thermal conductivity for cyclopentane dated
back to 1998, before the apparatus had undergone the major modifications that made the
apparatus more accurate besides the fact that in 1998 the supplier of the cyclopentane
was different from the one used at this point the decision was made to perform new tests
for pure cyclopentane.
These tests were conducted at temperatures between 394 K and 364 K and pressures
between 7 bar and 2 bar.

15,00
16,00
17,00
18,00
19,00
20,00
21,00
22,00
0,00 1,00 2,00 3,00 4,00 5,00 6,00 7,00
p / bar


/

m
W

m
-
1

K
-
1
120C
100C
80C
90C
Linear (120C)
Linear (100C)
Linear (80C)
Linear (90C)

Figure 4.6: Final selection of the results obtained in the measurements with cyclopentane.
28

4.3. MIXTURES OF ISOPENTANE AND CYCLOPENTANE

4.3.1. 26 % i-pentane / 74 % c-pentane

For the mixture with an exact molar composition of 25,92 % in isopentane and 74,08
% in cyclopentane the experiments were conducted between 333 K and 390 K and at
pressures between 2 bar and 8 bar.
The results of the experiments with this mixture are presented in Figure 4.7 in the
form of 3 isotherms.

15,0000
16,0000
17,0000
18,0000
19,0000
20,0000
21,0000
22,0000
23,0000
24,0000
0,000 1,000 2,000 3,000 4,000 5,000 6,000 7,000
p / bar


/

m
W

m
-
1
K
-
1
393,61 K
372,86 K
363,05 K
Linear (393,61 K)
Linear (372,86 K)
Linear (363,05 K)

Figure 4.7: First selection of the results obtained in the measurements with 75 % isopentane and 25 %
cyclopentane.


Seeing that the results at the lowest pressure for 120C presented a severe dispersion,
indicating an unexpected instability in the pressure inside the measuring cell, it was
decided to evaluate the data without these set of values.
Unfortunately, due to pressure limitations, it was impossible to obtain another set of
points to replace this.

29
15,0000
16,0000
17,0000
18,0000
19,0000
20,0000
21,0000
22,0000
23,0000
24,0000
0,000 1,000 2,000 3,000 4,000 5,000 6,000 7,000
p / bar


/

m
W

m
-
1
K
-
1
393,61 K
372,86 K
363,05 K
Linear (393,61 K)
Linear (372,86 K)
Linear (363,05 K)

Figure 4.8: Second selection of the results obtained in the measurements with 75 % isopentane and 25 %
cyclopentane.


At this point, it was also taken into consideration that the slope for the isotherm at
100C presented a great divergence to the slopes of the remaining isotherms.
At this point a new selection of the raw data was made, and the final results studied
present as follow.

15,0000
16,0000
17,0000
18,0000
19,0000
20,0000
21,0000
22,0000
23,0000
24,0000
0,000 1,000 2,000 3,000 4,000 5,000 6,000 7,000
p / bar


/

m
W

m
-
1
K
-
1
393,61 K
372,86 K
363,05 K
Linear (393,61 K)
Linear (372,86 K)
Linear (363,05 K)

Figure 4.9: Final selection of the results obtained in the measurements with 75 % isopentane and 25 %
cyclopentane.

30
Once again, the limited number of different pressures for the isotherms at the two
higher temperatures brings uncertainty to the following analysis, and for that, the decision
was taken to evaluate all three combinations of isotherms presented here.
31
5. ANALYSIS OF THE RESULTS


5.1. Thermal Conductivity of mixtures


Several models have been proposed to explain and define the thermal conductivity of
mixtures from the values of thermal conductivity of the pure components, one of the most
significant being developed by Wassiljewa [14]. A number of changes to the initial model
have been proposed along the time by different authors. The solution presented by Maxon
and Saxena [19] is one of the most widely used since it allows good results and it is
relatively simple, and it will be used in this work. More information about this subject can
be found in literature [18-21] and in the reports of previous workers [11-13].
According to Wassiljewa, the thermal conductivity of a mixture can be calculated
from the corresponding values for the pure components through the equation 5.1, where y
represents the mole fraction of the component and
ij
A is the Wassiljewa function for the
binary mixture between components I and j.

=
=
=
n
i
n
j
ij j
i i
m
A y
y
1
1

(5.1)

Maxon and Saxena [19] stated that the function
ij
A can be calculated by equation 6.2,
where M stands fort he molar mass and is a numerical constant close to unit.

(
(

|
|

\
|
+
(
(

|
|

\
|
|
|

\
|
+
=
j
i
j
i
trj
tri
ij
M
M
M
M
A
1 8
1
2
25 , 0 5 , 0

(5.2)

For a long time, and in the work of several authors, was considered to assume a
constant value for each mixture, regardless of the temperature and pressure values. In the
32
present work, following the first attempts from Fonseca [1], there is an attempt to go
further and evaluate how the value of can be influenced by both these parameters. This
became possible with the increase in both the precision and accuracy of the apparatus,
result of the several improvements performed, not only in this work but in the previous
ones as well.



5.2. The Nitrogen and isopentane system


Having the data necessary to establish isotherms for both pure components from
Fonsecas work, as well as the isotherms for the intermediate mixtures of such components,
it is possible to analyze the influence of temperature and concentration in the values of
thermal conductivity at a constant value of pressure.
The presented graphs on figures 5.1 to 5.3 present such isotherms at pressures of 1, 5
and 10 bar, being the values for 1 and 10 bar extrapolations.


18
20
22
24
26
28
30
32
300 325 350 375 400
Temperature / K


/

m
W

m
-
1

K
-
1

(
p

=

1

b
a
r
)
N2
25% i-C5
56% i-C5
75% i-C5
i-C5
Linear (N2)
Linear (25% i-C5)
Linear (56% i-C5)
Linear (75% i-C5)
Linear (i-C5)

Figure 5.1: Extrapolation of the data obtained for the system N
2
+ i-C
5
for a pressure of 1 bar.
33

18
20
22
24
26
28
30
32
300 325 350 375 400
Temperature / K


/

m
W

m
-
1

K
-
1

(
p

=

5

b
a
r
)
N2
25% i-C5
56% i-C5
75% i-C5
i-C5
Linear (N2)
Linear (25% i-C5)
Linear (56% i-C5)
Linear (75% i-C5)
Linear (i-C5)

Figure 5.2: Extrapolation of the data obtained for the system N
2
+ i-C
5
for a pressure of 5 bar.



Figure 5.3: Extrapolation of the data obtained for the system N
2
+ i-C
5
for a pressure of 10 bar


18
20
22
24
26
28
30
32
300 325 350 375 400
Temperature / K
/ / / /
mW m
-1
K
-1
(p = 10 bar)
N2
25% i-C5
56% i-C5
75% i-C5
i-C5
Linear (N2)
Linear (25% i-C5)
Linear (56% i-C5)
Linear (75% i-C5)
Linear (i-C5)
34

In all the presented cases, the thermal conductivity seems to evolve linearly with the
progression of temperature, though in different extension for the different compositions of
the mixture, being stronger for the greater compositions of nitrogen and less accentuated
for greater compositions of isopentane.
Analysing the slopes, it is possible to conclude that at a temperature above 400 K
there would be a point at which nitrogen and isopentane would have the same value of
thermal conductivity. That would happen at 481 K, 477 K and 472 K for pressures of 1, 5
and 10 bar, respectively. These temperatures are much greater then the top limit studied in
this work and it is not certain that the apparatus could withstand such conditions.
However, this linear change happens with different extension for each concentration,
which makes it impossible to determine a mathematical expression that relates the thermal
conductivity with both temperature and concentration of the components simultaneously.


It is also noticeable that at a given pressure the increase of thermal conductivity is
not regular as well.
It is evident that the increase from pure isopentane to a mixture with a composition
of 25 % of isopentane is much smaller than the increase from the mixture with a 75
%composition in isopentane to pure nitrogen.
That can be further seen in graph 5.4 where is represented as a function of the
composition of the mixtures for each temperature. The lines refer to the Wassiljewa
method, with the Maxon and Saxena modifications. The parameter was fitted
individually for each temperature from the experimental data. The deviations between the
experimental points and the Wassiljewa model are presented in figure 5.5.



35
i-pentane + nitrogen (1 bar)
16
18
20
22
24
26
28
30
32
34
0 0,2 0,4 0,6 0,8 1
mole fraction (iC
5
)


/

m
W

m
-
1
K
-
1

(
p

=

1

b
a
r
)
413.15K
393.15K
373.15K
353.15K
333.15K

Figure 5.4: Thermal conductivity as a function of the composition for a pressure of 1 bar. The lines refer to the
Wassiljewa method where was fitted individually for each temperature.
-1,20%
-1,00%
-0,80%
-0,60%
-0,40%
-0,20%
0,00%
0,20%
0,40%
0,60%
0,80%
1,00%
0,00 0,25 0,44 0,75 1,00
mole fraction iC5
333.15K
353.15K
373.15K
393.15K
413.15K

Figure 5.5: Deviation from the experimental points to the Wassiljewa model (p = 1 bar).
36
The agreement between the method and the experimental data are within an
acceptable limit, not overcoming 1,2 % and with and average deviation of 0,6 %.
The same calculations were made for the pressures of 5 and 10 bar. Graphs from
figures 5.5 and 5.6 refer to the pressure of 5 bar and graphs in figures 5.7 and 5.8 refer to
the pressure of 10 bar.


i-pentane + nitrogen (5 bar)
16
18
20
22
24
26
28
30
32
34
0 0,2 0,4 0,6 0,8 1
mole fraction (iC
5
)


/

m
W

m
-
1
K
-
1

(
p

=

5

b
a
r
)
413.15K
393.15K
373.15K
353.15K
333.15K

Figure 5.6: Thermal conductivity as a function of the composition for a pressure of 5 bar. The lines refer to the
Wassiljewa method where was fitted individually for each temperature.

37
-0,80%
-0,60%
-0,40%
-0,20%
0,00%
0,20%
0,40%
0,60%
0,80%
1,00%
1,20%
1,40%
1,60%
0,00 0,25 0,44 0,75 1,00
mole fraction iC5
333.15K
353.15K
373.15K
393.15K
413.15K

Figure 5.7: Deviation from the experimental points to the Wassiljewa model (p = 5 bar).
i-pentane + nitrogen (10 bar)
16
18
20
22
24
26
28
30
32
34
0 0,2 0,4 0,6 0,8 1
mole fraction (iC
5
)


/

m
W

m
-
1
K
-
1

(
p

=

1
0

b
a
r
)
413.15K
393.15K
373.15K
353.15K
333.15K

Figure 5.8: Thermal conductivity as a function of the composition for a pressure of 10 bar. The lines refer to the
Wassiljewa method where was fitted individually for each temperature.
38
-2,00%
-1,50%
-1,00%
-0,50%
0,00%
0,50%
1,00%
1,50%
2,00%
2,50%
3,00%
0,00 0,25 0,44 0,75 1,00
mole fraction N2
333.15K
353.15K
373.15K
393.15K
413.15K

Figure 5.9: Deviation from the experimental points to the Wassiljewa model (p = 10 bar).


The general agreement between the experimental data and the Wassiljewa method
are decreasing for higher pressures. However, that error never overcomes 1,5 % for 5 bar
and 3 % for 10 bar and is, in average, of 0,6 % at 5 bar and 1,5 % at 10 bar.
Several factors should be taken into account at this point when analyzing the results.
First, the limitations in both temperature and pressure at which it was possible to
work for the mixtures, originated by the dew point associated at at each mixture for a
particular combination of temperature and pressure.

This is especially true for the mixtures with 25 % and 50 % in isopentane, for the
extrapolation at 10 bar of the isotherm at 30C since it is done from a set of low pressures,
which increased significantly the relative errors for the experimental data of such mixture
and the fitting of the Wassiljewa model.
Second, there seems to be some dispersion of the data for some aggregated data
points.
39
Despite the efforts to minimize this problem with redoing of the raw data selection
and a general obtaining of a greater number of points for longer periods of time, in order to
be sure of the stability inside the measuring cell this seem to be an intrinsic problem of
the mixtures of nitrogen and isopentane.



The values originated by the independent fitting of the values of with the
Wassiljewa model for each combination of temperature and pressure are presented on
Table 5.1.


Table 5.1: Values obtained for the fitting of for different pressures and temperatures.
p / bar (333,15 K) (353,15 K) (373,15 K) (393,15 K) (413,15 K)
1
0,93615027 0,93474869 0,93359916 0,93263263 0,93180095
5
0,90758988 0,91414028 0,91991823 0,92503062 0,92956999
10
0,87478346 0,89049022 0,90440472 0,91677814 0,92782639



40
0,87
0,88
0,89
0,9
0,91
0,92
0,93
0,94
320 340 360 380 400 420
T / K

1 bar
5 bar
10 bar

Figure 5.10: Influence of the temperature in the values of .


0,87
0,88
0,89
0,9
0,91
0,92
0,93
0,94
0 2 4 6 8 10 12
p / bar

333,15 K
353,15 K
373,15 K
393,15 K
413,15 K

Figure 5.11: Influence of the pressure in the values of .


41
Making use of the equation 5.3 proposed by Fonseca [1] for the prediction of values
of , it was possible to arrive at the values for the parameters that are present in table 5.2

4 3 2
1
A P A P A
T e A
+
= (5.3)

Table 5.2: Values obtained for the parameters in equation 5.3, in the fitting of the experimental values of .
1 2 3 4
1,28383559 -0,19737053 0,03273125 -0,053397584


Figure 5.12 shows for various values of pressure how changes with the temperature.
The lines refer to calculations performed with equation 5.3. In Figure 5.13 are represented
the deviations of the experimental points relatively to the values given by the equation 5.3.
The same representations but with as a function of the pressure are shown in
figures 5.14 and 5.15.

0,85
0,9
0,95
320 340 360 380 400 420 440
Temperature / K

1 bar
2 bar
5 bar
10 bar

Figure 5.12: Influence of the temperature in the values of e. The lines refer to equation 5.3.

42
-0,20%
-0,15%
-0,10%
-0,05%
0,00%
0,05%
0,10%
0,15%
0,20%
0,25%
333,15 353,15 373,15 393,15 413,15
Temperature / K
1 bar
2 bar
5 bar
10 bar

Figure 5.13: Deviations of the experimental points of e relatively to the results obtained with equation 5.3,
represented as a function of temperature.

0,85
0,9
0,95
0 2 4 6 8 10 12
Pressure / bar

333.15K
353.15K
373.15K
393.15K
413.15K

Figure 5.14: Influence of the temperature in the values of e. The lines refer to equation 5.3.
43

-0,20%
-0,15%
-0,10%
-0,05%
0,00%
0,05%
0,10%
0,15%
0,20%
0,25%
1 2 5 10
pressure / bar
333.15 K
353.15 K
373.15 K
393.15 K
413.15 K

Figure 5.15: Deviations of the experimental points of e relatively to the results obtained with equation 5.3,
represented as a function of pressure.

The model shows an almost perfect juxtaposition to the experimental data, and the
relative errors are within very good limits, never overcoming 0,25 %.
The fact that the relative errors are so small by far the smallest obtained during this
work - can be explained by the fact that the values that are under consideration are very
similar, with the difference reduced to amounts in the order of 0,01 in values of order 1.
As can further be seen in the graphs 5.16 through 5.21, the model proposed by
Fonseca [1] achieves very good values of when compared to the raw data.
The following graphs, show in even more depth, for different pressures and
temperatures, how the values obtained with the model compare to the experimental ones.

44
i-pentane + nitrogen
10
15
20
25
30
35
0 0,2 0,4 0,6 0,8 1
composition (i-C5)


/

m
W

m
-
1
K
-
1

(
p

=

1

b
a
r
)
60C
80C
100C
120C
140C

Figure 5.16: Thermal Conductivity as a function of the composition for a pressure of 1 bar. The lines refer to the
Extended Wassiljewa Method, where is estimated by means of equation 5.3.
-2,00%
-1,50%
-1,00%
-0,50%
0,00%
0,50%
1,00%
1,50%
2,00%
0,00 0,25 0,44 0,75 1,00
mole fraction i-C5
333.15K
353.15K
373.15K
393.15K
413.15K

Figure 5.17: Deviations from the experimental points to the Extended Wassiljewa Model (p = 1 bar).
45

i-pentane + nitrogen
10
15
20
25
30
35
0 0,2 0,4 0,6 0,8 1
composition (i-C5)


/

m
W

m
-
1
K
-
1

(
p

=

5

b
a
r
)
60C
80C
100C
120C
140C

Figure 5.18: Thermal Conductivity as a function of the composition for a pressure of 5 bar. The lines refer to the
Extended Wassiljewa Method, where e is estimated by means of equation 5.3.
-2,50%
-2,00%
-1,50%
-1,00%
-0,50%
0,00%
0,50%
1,00%
1,50%
2,00%
0,00 0,25 0,44 0,75 1,00
mole fraction i-C5
333.15K
353.15K
373.15K
393.15K
413.15K

Figure 5.19: Deviations from the experimental points to the Extended Wassiljewa Model (p = 5 bar).
46
i-pentane + nitrogen
10
15
20
25
30
35
0 0,2 0,4 0,6 0,8 1
composition (i-C5)


/

m
W

m
-
1
K
-
1

(
p

=

1
0

b
a
r
)
60C
80C
100C
120C
140C

Figure 5.20: Thermal Conductivity as a function of the composition for a pressure of 10 bar. The lines refer to
the Extended Wassiljewa Method, where e is estimated by means of equation 5.3.
-2,50%
-2,00%
-1,50%
-1,00%
-0,50%
0,00%
0,50%
1,00%
1,50%
2,00%
2,50%
0,00 0,25 0,44 0,75 1,00
mole fraction i-C5
333.15K
353.15K
373.15K
393.15K
413.15K

Figure 5.21: Deviations from the experimental points to the Extended Wassiljewa Model (p = 10 bar).
47
As it can be seen in the graphs 5.16 through 5.21, the agreement between the
experimental data and the prediction achieved by the model proposed by Fonseca [1] is
good.
This is fairly expected if we analyze the graph 5.11, where the progression of the
value of for a certain temperature or for a certain pressure can be fairly described by the
model proposed that is linear in function of both pressure and temperature.

And analyzing graph 5.10, we can see that the progression of the temperature can be
predicted by an equation with the form

= a
.
T
b
(5.4)


The graphs 5.22 and 5.23 show the direct comparison between the experimental
values and the values predicted by the equation 5.3, and the values of the relative deviation,
respectively.

20
22
24
26
28
30
32
20 22 24 26 28 30 32

experimental
/ mW m
-1
K
-1

p
r
e
d
i
c
t
e
d

/

m
W

m
-
1
K
-
1
75% iC5
44% iC5
25% N2

Figure 5.22: Agreement between the experimental values of thermal conductivity and the values predicted by
equation 5.3.
48
predicted values for system (N2 + iC5)
-2,0%
-1,5%
-1,0%
-0,5%
0,0%
0,5%
1,0%
1,5%
2,0%
2,5%
3,0%
21 23 25 27 29 31
experimental / mW m
-1
K
-1
(

e
x
p
e
r
i
m
e
n
t
a
l

p
r
e
d
i
c
t
e
d
)

/


p
r
e
d
i
c
t
e
d
75% iC5
44% iC5
25% iC5

Figure 5.23: Experimental values of thermal conductivity and the relative deviation of the values predicted by
equation 5.3 to them.

These two last graph support the conclusion on the agreement of the model with the
experimental graph and prove that such an agreement is extremely accurate, with the value
of the relative error between the experimental and the predicted data never overcoming 2,5
% in absolute value.
Taking into particular account that the predicted value of itself contains an error, it
is fair to say that the predicted results are in very good agreement.
49
5.3. Pure Cyclopentane

In order to further verify the usefulness and good capacity of the LPUR equation
proposed by Fonseca, the data for pure cyclopentane was modelled through equation 5.5
presented below.

= A + B
.
T + C
.
P + D
.
T
.
P (5.5)

This could be done for, as Fonseca also noticed for his own data on thermal
conductivity for pure compounds, presents a linear dependence to both temperature and
pressure.



Table 5.3: Values of the parameters of equation 5.5 for cyclopentane.
Data Set A B C D
Average
deviation
No. of data
points
Cyclopentane -23,454600 0,113087 -0,956319 0,002414 0,68 287



50
Verification of LPUR eq. for cyclo-pentane
-2,00%
-1,50%
-1,00%
-0,50%
0,00%
0,50%
1,00%
1,50%
2,00%
15,0000 16,0000 17,0000 18,0000 19,0000 20,0000 21,0000 22,0000 23,0000
/ mW m
-1
K
-1

Figure 5.24: Deviations from the experimental thermal conductivity data for cyclopentane to the values
estimated through the LPUR equation.


As can be seen on the graph from figure 6.24, except for two single points, all the
remaining data obtained by the LPUR equation falls within a margin of 1,5 % regarding
the relative deviation to the experimental data.
The average deviation is, in fact, inferior to 0,70 % and accounting for both the
scattering of data and the amount of data studied (almost 300 points) we can definitely
conclude that the previously proposed LPUR model is applicable to pure cyclopentane.
This conclusion, aggregated with the previous good applications to other similar
conclusions about the model [1], should help to conclude that the model is valid for all
pure compounds, even if this should continue to be verified in future works.
It should be noted that for the obtaining of the parameters of the equation the amount
of data is by far greater than what it is in fact needed, but having such data available led to
51
the decision of using it all. However, only about a quarter or even a fifth of the total data
used here needed to have been enough.

It is still possible to compare the new obtained results to the ones that were already
present in the database of Bayer for Thermal Conductivity for Cyclopentane and that dated
back to 1995 and 1998.

10
12
14
16
18
20
22
24
26
28
300 320 340 360 380 400 420 440
T / K


/

m
W

m
-
1
K
-
1

(
p

=

1

b
a
r
)
This Work
Supplier EC
(1995)
Supplier EC
(1998)
Supplier
Philips (1998)

Figure 5.25: Comparison between the values of l obtained for pure Cyclopentane in this work and in previous
works for a pressure of 1 bar. The values are extrapolations.

Despite the differences from the measurements obtained in this work to the ones
obtained in 1998, it should be taken into account that the purity of the Cyclopentane used
in this work was equal or superior a 99,5%, while in previous works it was smaller.
It is curious to see that the most ancient results are the ones in better agreement with
the most recent ones.
Unfortunately all these values lack confirmation for there is no data in the reference
databases for cyclopentane.
The recommendation goes to the use of only the most recent data for the precision of
the apparatus and of the method of work was highly improved since 1998; and also
because, as refered, the purity of the cyclopentane used was greater at this time.


52
5.4. The cyclopentane and isopentane system

Since only one composition of mixture for this system was studied, any results
presented here would be nothing more than demonstrative and, therefore, meaningless.
It was decided to simply leave the data prepared for future treatment when more data
is made available.
53
6. CONCLUSIONS

6.1. Accomplished in this work

One pure component was studied in this work, producing good quality results that
went to further prove the good applicability of the previously proposed LPUR model. The
applicability of the model was proven for cyclopentane, therefore adding one more
component to the list of the hydrocarbons for which the model has proven valid.
Also two binary systems were studied in this work with satisfactory results.
One of these systems showed a behaviour that could be predicted correctly by the
previously proposed Extended Wassiljewa Method, this way contributing with further
proof of the validation of this particular model.
The other system was very limitedly studied due to a lack of time derived of
apparatus related difficulties and it was impossible to take any conclusions from it at this
point.

6.2. Recommendations for future work

First and foremost, the studies of the isopentane and cyclopentane system should be
continued in order to obtain a full set of raw data that will allow proceeding with the
modelling of the system with the previously proposed equations. In fact, seeing that the
results for this mixture had to be reduced to such a short and, therefore, inaccurate
ensemble, these experiments should be redone.
Second, the results obtained with the system consisting of nitrogen and isopentane
could be further improved with the measuring of some points at low temperatures.
Since this system has a low amount of different pressure points for he lower
isotherms, if they could be improved it would be greatly benefit, for the results and the
conclusions concerning this system.
Third, the future work could focus on three component systems, consisting of
nitrogen and any two components combination between isopentane, cyclopentane and n-
pentane.
54
This would be easy to implement because when supplying nitrogen to the measuring
cell, the pressure vessels are not needed, which would allow to maintain prepare a three
component mixture in the cell by maintaining two hydrocarbons in the pressure vessels.
The experimental procedure for the preparation of this suggested mixture would not
be complicated neither rather different from the one that is in use at this point, being that
the only precaution would be to always establish a mixture that involves nitrogen for only
two pressure vessels are available, and that the nitrogen is added as the final component,
for is the most available and the less expensive of them all.
A new model would have to be defined for these systems and, in the future, a third
pressure vessel could be added to the apparatus in order to achieve new systems a desired
example would be the combination of isopentane, cyclopentane and n-pentane.

Concerning the apparatus, improvements can still be accomplished.
One of those improvements would be the creation of two independent temperature
zones in the apparatus. Presently it is impossible to perform any operation in the upper part
of the apparatus without disturbing the thermal equilibrium in the lower part that contains
the measuring cell. This improvement could save some time when the study of a pure
compound is being done which demands for the use of the pressure vessels in the upper
part of the apparatus. If this worked as an independent temperature zone, the operator
would be able to exchange the pressure vessel without disturbing the temperature of the
gas that is already inside the measuring cell. The improvement should be possible to
implement without any profound alterations to the apparatus, since the upper and lower
part of the apparatus, though connected, have independent temperature control systems.
Nevertheless, attention is needed for details like the positioning of the safety rupture
membrane, which should then be in the lower part of the apparatus since the volume in the
measuring cell goes until that point of the tubing.
A second significant change that should be operated involves the environment
surrounding the apparatus. If the apparatus was to be moved into a temperature controlled
room, or if the present room where it is placed was provided with a temperature control
system, the regular extent of the results would be more accurate. This would be so because
a temperature controlled environment would avoid the present situation that for one setting
of the temperature controller the resulting temperature in the interior of the cell changes
along the hours of work of one day. Even more significantly, if we consider different days,
especially if they are placed in different seasons say Winter and Summer the difference
55
might be of one Kelvin degree or even more. Since the experimental procedure
implemented at this moment requires several changes in temperature during a week of
measurements, and since it is of primary importance to have the same temperature values
repeated in the apparatus for the study of an isotherm, this should be an improvement taken
into consideration as soon as possible. This improvement would also be a time saving one,
for when a previously used temperature setting leads the apparatus to a different
temperature, a correction has to be made, with a consequent wait of one or two hours so
that the new equilibrium is reached inside the cell. Furthermore, even the smaller changes
in temperature during a same set of measurements can influence the precison of the results.
56
7. REFERENCES

[1] Fonseca, J., Aging of Polyurethane Rigid Foams Thermal Conductivity of Gas
Mixtures, Bayer A. G., 2006.

[2] - Perkins, R., Cusco, L., Howley, J., Laesecke, A. Matthes, S., Ramires, M.L.V. (2001).
Thermal Conductivities of Alternatives to CFC-11 for Foam Insulation, J. Chem. Eng. Data,
46:428-432.

[3] - Richard, R.G., Shankland, I.R. (1989). A Transient Hot-Wire Method for Measuring the
Thermal Conductivity of Gases and Liquids, International Journal of Thermophysics, 10 (3):
673-686.

[4] - Johnson, R.W., Bowman, J. (2003). The Effect of Blowing Agents on Energy Use and
Climate Impact of a Refrigerator, APPLIANCE European Edition, Nov., 22-24.

[5] - Wilkes K.E., Gabbard, W.A., Fred J. Weaver, F.J. (1999). Aging of Polyurethane Foam
Insulation in Simulated Refrigerator Panels - One-Year Results with Third-Generation
Blowing Agents, The Earth Technologies Forum, Washington, DC

[6] - Wakeham,W.A.; Nagashima,A.; Sengers,J.V.(1991).Transient Methods for Thermal
Conductivities, Measurement of the Transport-Properties of Fluids ,Blackwell,Oxford.

[7] - J. Healy, J. J. de Groot, J. Kestin, The theory of the Transient Hot-Wire Method for
measuring the thermal conductivity, Physica C82, 392-408.

[8] - B. Taxis, K. Stephan, Application of the transient hot-wire method to gases at low
pressures, Int. J. Thermophys. 15 (1) 1994.

[9] - A.N. Gurova, Condutibilidade Trmica de Refrigerantes Ambientalmente Aceitveis,
PhD. Thesis, Dep. de Qumica - Faculdade de Ciencias da Universidade de Lisboa, 1996.

57
[10] - H.M. Roder, R.A. Perkins, A. Laesecke, C.A. Nieto de Castro, Absolute Steady-State
Thermal Conductivity Measurements by Use of a Transient Hot-Wire System, J. Res. Natl.
Inst. Stand. Technol., 2000, 105 (2), 221-253.

[11] - E. Takikawa, Thermal Conductivity Measurements With Transient Hot Wire Method,
Bayer A.G., 2001.

[12] - F. Santos, Thermal Conductivity of Fluds An Internship Report for Graduation in
Industrial Chemistry and Management, Bayer A.G / Universidade de Aveiro, 2002.

[13] - N.S. Oliveira, Thermal Conductivity of Gases An Internship Report for Graduation in
Chemistry Branch of Analytical Chemistry, Bayer A.G / Universidade de Aveiro, 2001.

[14] - G. Fleischer, Aufbau und Inbetriebnahme einer Apparatur zur Messung der
Wrmeleitfhigkeit von Gasen Graduation Thesis, Bayer A.G. / University of Stuttgart,
1994 (in German, used as reference only).

[15] - H. Grensemann, Experimentelle Bestimmung und Berechnung von
Gaswrmeleitfhigkeiten Graduation Thesis, Bayer A.G. / University of Oldenburg, 1999
(in German, used as reference only).

[16] http://webbook.nist.gov/chemistry/fluid/, Thermophysical Properties of Fluid Systems,
NIST Chemistry WebBook, NIST Standard Reference Database Number 69, June 2005.

[17] V. Vesovic, W. A. Wakeham, G. A. Qichowy, J V. Sengers, J T. R. Watson, J Millat,
The Transport Properties of Carbon Dioxide, J. Phys. Chem. Ref. Data, 1990, 19 (3), 763-
808.

[18] A. Wassiljewa, Phys. Z., 1904, 5, 737 (cited in [20]).

[19] E.A. Mason, S.C. Saxena, Phys. Fluids, 1958, 1, 361 (cited in [19]).

[20] V. Vesovic, Prediction of the thermal conductivity of gas Mixtures at Low Pressures,
International Journal of Thermophysics, 2001, 22 (3), 801 828.
58
[21] R.C. Reid, J.M. Prausnitz, B.E. Poling, The Properties of Gases and Liquids, McGraw-
Hill, 4
th
ed., 1998.

[22] I.M. Marrucho, F. Santos, N.S. Oliveira, R. Dohrn, Aging of Polyurethane Foams:
Thermal conductivity of N2 and cyclopentane Gas Mixtures, Journal of Celular Plastics, 2005,
41, 207 224.

[23] H. Fleurent, S. Thijs, The use of Pentanes as Blowing Agent in Rigid Polyurethane
Foam, Journal of Celular Plastics, 1995, 31, 580 599.

[24] E. Kuhn, P. Schlinder, Advances in the Understanding of the Effects of Various
Blowing Agents on Rigid Polyurethane Appliance Foam Properties, Journal of Celular
Plastics, 1994, 30, 554 569.
59
APPENDIX 1


Table A1.1: Final selection of the results obtained with the mixture of 75 % nitrogen and 25% i-pentane.
T / C p / bar /mW
.
m
-1.
K
-1
T / C p / bar /mW
.
m
-1.
K
-1

117,83 8,897 30,2307 79,03 4,432 25,7846
117,80 8,898 30,1408 79,03 4,433 26,3651
117,77 8,898 30,2053 79,07 4,433 26,3338
117,74 8,898 29,9189 79,08 4,434 25,9846
117,76 8,898 30,1663 79,08 4,433 26,0454
117,73 8,899 30,2285 79,09 4,434 26,1807
117,71 8,897 30,3019 79,12 4,435 26,1506
117,71 8,896 30,0246 79,13 4,435 26,1575
117,73 8,895 30,1930 79,14 4,435 26,0403
117,73 8,895 30,0816 79,17 4,435 25,8680
117,71 8,893 29,9728 79,19 4,435 25,9542
117,75 8,893 30,1045 79,19 4,436 26,1271
117,75 8,893 30,0426 79,22 4,436 25,8662
117,75 8,893 30,1054 79,23 4,436 26,2833
117,77 8,892 30,3073 79,26 4,436 25,9773
117,77 8,892 30,2719 79,24 4,437 26,1696
117,79 8,890 29,8608 79,09 2,461 25,7751
117,80 8,891 30,4492 79,07 2,462 25,3630
117,80 8,891 30,1729 79,07 2,462 25,4346
117,81 8,892 29,9264 79,08 2,463 25,6851
117,83 8,892 30,0132 79,07 2,465 25,4066
117,83 8,891 30,3444 79,08 2,465 25,2424
117,85 8,890 30,1184 79,09 2,466 25,1770
116,82 7,094 29,8206 79,07 2,466 25,2316
116,84 7,094 29,5291 79,07 2,467 25,4093
116,84 7,095 29,7906 79,06 2,467 25,1958
116,86 7,095 29,8297 79,05 2,467 25,4812
116,86 7,095 29,8165 79,05 2,468 25,5545
116,86 7,095 29,9096 79,08 2,468 25,5180
116,84 7,096 29,6541 79,08 2,468 25,2239
116,87 7,095 29,6446 79,09 2,468 25,6958
116,90 7,095 29,8580 79,08 2,469 25,6647
116,88 7,095 29,8459 79,10 2,469 25,6993
116,92 7,095 29,6992 79,07 2,469 25,6357
116,92 7,096 29,8039 79,07 2,469 25,6895
116,97 7,095 29,8278 79,07 2,470 25,3849
116,97 7,095 29,8363 79,06 2,470 25,7006
116,98 7,095 29,8765 79,06 2,471 25,4079
117,03 7,095 29,8481 58,64 7,276 24,6304
117,05 7,095 29,7492 58,62 7,275 24,6051
117,05 7,095 29,8439 58,56 7,273 24,6250
117,05 7,096 29,6623 59,57 7,272 24,5065
116,97 4,845 29,6496 59,53 7,270 24,5624
60
117,01 4,847 29,6019 59,50 7,269 24,5122
117,03 4,849 29,5130 59,50 7,267 24,7098
117,09 4,850 29,7399 59,48 7,265 24,6021
117,13 4,852 29,5108 59,45 7,264 24,5675
117,16 4,853 29,6208 59,41 7,262 24,4438
117,15 4,854 29,6730 59,39 7,261 24,3701
117,20 4,856 29,7815 59,40 7,260 24,4319
117,21 4,857 29,6563 59,39 7,259 24,5404
117,22 4,857 29,6038 59,35 7,258 24,6259
117,25 4,858 29,7268 59,33 7,256 24,5227
117,28 4,858 29,8824 59,30 7,256 24,4748
117,29 4,860 29,8479 59,25 7,254 24,5463
117,28 4,861 29,7500 59,23 7,253 24,4613
117,32 4,862 29,7244 59,22 7,252 24,4626
117,32 4,862 29,6376 59,26 7,252 24,4864
117,33 4,863 29,6587 59,28 7,250 24,4583
117,34 4,864 29,9486 59,63 5,917 24,2500
117,36 4,865 29,5243 59,61 5,915 24,6858
117,38 4,866 29,7571 59,62 5,914 24,4607
117,41 4,866 29,7521 59,60 5,912 24,5330
117,14 2,735 29,0699 59,56 5,910 24,4869
117,21 2,738 29,4844 59,52 5,910 24,4995
117,27 2,741 29,2590 59,54 5,908 24,6637
117,32 2,743 29,1809 59,56 5,907 24,6170
117,35 2,744 29,2058 59,53 5,906 24,4576
117,36 2,746 29,3794 59,54 5,906 24,4947
117,37 2,748 29,1418 59,53 5,904 24,5660
117,41 2,748 29,4269 59,53 5,903 24,5908
117,41 2,751 29,2216 59,56 5,902 24,6820
117,46 2,751 29,1206 59,53 5,902 24,3147
117,45 2,752 29,4431 59,55 5,901 24,3739
117,48 2,754 29,2313 59,60 5,901 24,5314
117,47 2,756 29,3800 59,61 5,900 24,5537
117,51 2,756 29,2851 59,60 5,899 24,4034
117,53 2,757 29,5282 59,63 5,899 24,7311
117,57 2,759 29,5475 59,60 5,899 24,5192
117,59 2,759 29,5126 59,62 5,898 24,5985
117,65 2,760 29,4435 59,61 5,898 24,6332
117,68 2,761 29,5122 59,52 4,165 24,2371
117,67 2,761 29,2912 59,50 4,165 24,3356
117,73 2,762 29,6161 59,50 4,164 24,2661
117,74 2,763 29,2237 59,47 4,164 24,3496
117,77 2,764 29,5575 59,48 4,165 24,2292
117,80 2,764 29,2856 59,52 4,164 24,3516
102,26 8,489 28,6206 59,55 4,164 24,2839
102,25 8,488 28,5761 59,52 4,164 24,3878
102,24 8,487 28,7327 59,54 4,164 24,2013
102,23 8,486 28,7482 59,54 4,164 24,2488
102,21 8,484 28,6415 59,50 4,164 24,3917
102,19 8,483 28,6554 59,49 4,164 24,2297
61
102,14 8,480 28,6572 59,50 4,164 24,3270
102,12 8,478 28,5530 59,47 4,164 24,3721
102,09 8,476 28,6573 59,51 4,164 24,2747
102,10 8,474 28,6430 59,52 4,164 24,3535
102,08 8,473 28,5051 59,54 4,164 24,2199
102,08 8,471 28,6996 59,55 4,164 24,2352
102,08 8,470 28,4454 59,55 4,164 24,3371
102,08 8,468 28,7573 59,54 4,164 24,2519
102,08 8,467 28,7913 59,57 4,163 24,2433
102,06 8,466 28,3909 59,56 4,164 24,2081
102,05 8,465 28,5555 59,57 4,164 24,1847
102,04 8,464 28,7773 59,58 4,164 24,1315
102,04 8,463 28,3457 60,46 2,344 23,7486
102,03 8,462 28,7248 60,48 2,344 23,7064
102,02 8,460 28,5155 60,48 2,345 23,8250
102,01 8,459 28,6207 60,46 2,345 23,6287
101,99 8,458 28,6238 60,43 2,345 23,7735
101,96 8,456 28,6578 60,44 2,345 23,7203
101,99 8,455 28,6465 60,42 2,345 23,6491
101,97 8,453 28,6026 60,42 2,345 23,6769
101,97 8,452 28,5650 60,40 2,345 23,6661
101,02 6,779 28,3776 60,43 2,345 23,7088
101,00 6,775 28,2678 60,43 2,345 23,5703
100,95 6,774 28,3790 60,45 2,346 23,6201
100,97 6,773 28,3918 60,46 2,346 23,5500
100,92 6,772 28,4263 60,50 2,345 23,6115
100,92 6,771 28,3516 60,53 2,346 23,7761
100,91 6,770 28,2167 60,60 2,347 23,6732
100,90 6,770 28,2393 60,61 2,347 23,7616
100,84 6,768 28,3264 60,61 2,347 23,5143
100,86 6,767 28,1032 60,61 2,348 23,8344
100,83 6,767 28,5732 60,64 2,348 23,7659
100,82 6,765 28,2856 40,09 3,775 22,5521
100,84 6,763 28,2951 40,07 3,775 22,5501
100,79 6,763 28,2524 40,05 3,774 22,6026
100,79 6,772 28,4242 40,04 3,773 22,5460
100,77 6,761 28,3665 40,09 3,773 22,6434
100,77 6,761 28,3481 40,10 3,773 22,5627
100,78 6,760 28,2841 40,11 3,773 22,5887
100,76 6,760 28,4028 40,09 3,772 22,5551
100,77 6,759 28,4650 40,12 3,772 22,4748
100,72 6,759 28,3083 40,14 3,772 22,4297
100,75 6,759 28,1450 40,10 3,772 22,3680
100,77 6,759 28,2962 40,12 3,771 22,4408
100,78 6,758 28,1527 40,13 3,771 22,4687
101,89 4,665 27,9381 40,10 3,771 22,4481
101,86 4,664 28,0669 40,15 3,771 22,4138
101,85 4,663 28,1266 40,15 3,771 22,5274
101,79 4,661 28,3113 40,12 3,771 22,4437
101,77 4,660 28,2316 40,13 3,771 22,5242
62
101,73 4,660 28,3903 40,14 3,771 22,4628
101,72 4,659 28,4293 40,15 3,771 22,4561
101,71 4,659 28,3067 41,09 2,127 21,9148
101,69 4,658 28,0385 41,07 2,126 22,3168
101,67 4,657 28,0887 41,07 2,127 22,2384
101,67 4,656 28,1432 41,06 2,127 22,1957
101,64 4,655 28,2295 41,03 2,126 22,3111
101,62 4,654 28,2499 41,04 2,126 22,1762
101,61 4,654 28,2666 41,01 2,126 22,2139
101,61 4,653 28,2336 41,01 2,126 22,1263
101,61 4,652 28,2283 40,99 2,126 22,1903
101,59 4,651 28,2178 40,99 2,126 22,1499
101,57 4,651 28,2432 40,97 2,126 22,2582
101,59 4,650 28,0931 40,93 2,125 22,2576
101,58 4,650 28,1721 40,91 2,125 22,2878
101,55 4,649 28,1069 40,90 2,125 22,2854
101,53 4,649 28,1135 40,89 2,124 22,1258
102,01 2,654 27,8846 40,87 2,125 22,1016
102,01 2,654 28,0180 40,89 2,125 22,2287
101,99 2,654 27,7252 40,83 2,124 22,1698
101,98 2,653 27,7070 40,86 2,124 22,0966
101,96 2,653 27,9291 40,87 2,124 22,1702
101,94 2,653 27,7009 40,84 2,124 22,3014
101,91 2,653 27,9798 40,82 2,124 22,0601
101,91 2,652 27,8396 40,80 2,124 22,3271
101,90 2,652 27,8577 40,78 2,124 22,1448
101,89 2,652 27,8060 40,78 2,124 22,4394
101,89 2,652 27,8751 40,74 2,124 22,0320
101,85 2,652 28,0078 40,78 2,124 21,9912
101,85 2,653 27,9834 40,77 2,124 22,0106
101,83 2,652 27,8801 40,77 2,125 22,0133
101,83 2,652 27,8131 40,78 2,125 22,0327
101,80 2,651 27,7136 40,74 2,124 22,4779
101,79 2,652 27,5451 40,72 2,124 21,9497
101,80 2,652 28,0605 40,74 2,124 22,3848
101,79 2,652 27,8762 40,69 2,124 22,0668
101,77 2,652 27,6479 40,70 2,124 22,1042
101,77 2,652 28,0355 40,70 2,124 22,2192
101,77 2,652 27,6818 32,31 3,634 21,9810
101,74 2,652 28,1535 32,27 3,633 21,9360
101,74 2,652 28,0356 32,25 3,631 22,0242
80,52 8,352 26,5786 32,28 3,629 21,8248
80,51 8,352 26,8787 32,26 3,627 21,7523
80,50 8,352 26,8597 32,24 3,625 21,8202
80,51 8,352 26,6093 32,22 3,624 21,8268
80,53 8,351 26,9469 32,23 3,622 21,6866
80,52 8,351 26,5451 32,21 3,620 21,8064
80,56 8,352 26,6292 32,20 3,618 21,7903
80,56 8,352 26,6819 32,22 3,617 21,8175
80,57 8,354 26,5765 32,22 3,616 21,8130
63
80,61 8,353 26,5175 32,24 3,615 21,8355
80,59 8,353 26,5155 32,26 3,613 21,8047
80,59 8,352 26,7851 32,26 3,612 21,8034
80,59 8,351 26,6855 32,27 3,611 21,7507
80,59 8,351 26,4299 32,24 3,610 21,7440
80,58 8,350 26,7612 32,24 3,608 21,9506
80,55 8,349 26,5988 32,29 3,607 21,8161
80,57 8,349 26,7250 32,28 3,605 21,7092
80,57 8,348 26,7228 32,29 3,605 22,0086
80,58 8,348 26,4943 32,51 2,054 21,6066
80,60 8,348 26,7371 32,53 2,054 21,5941
79,38 6,335 26,4024 32,55 2,054 21,4977
79,37 6,334 26,1653 32,55 2,054 21,5038
79,35 6,333 26,1738 32,54 2,055 21,4808
79,33 6,332 26,3201 32,55 2,055 21,5567
79,34 6,332 26,1635 32,56 2,055 21,3433
79,32 6,332 26,3291 32,53 2,056 21,8284
79,33 6,331 26,4267 32,55 2,056 21,7722
79,30 6,331 26,6196 32,58 2,056 21,3366
79,30 6,330 26,3223 32,59 2,055 21,4879
79,27 6,330 26,1264 32,59 2,056 21,4959
79,26 6,329 26,5659 32,59 2,057 21,7152
79,27 6,328 26,3826 32,60 2,057 21,3953
79,23 6,327 26,2535 32,60 2,057 21,6672
79,26 6,327 26,3785 32,60 2,057 21,5803
79,21 6,326 26,2916 32,59 2,057 21,3663
79,25 6,326 26,4043 32,60 2,057 21,4804
79,27 6,325 26,2576 32,62 2,058 21,6772
79,29 6,325 26,3747 32,63 2,058 21,6954
79,30 6,325 26,2553 32,62 2,057 21,6184
79,32 6,325 26,3684 32,59 2,058 21,6329
79,36 6,324 26,2795 32,59 2,057 21,6255
79,33 6,324 26,3715 32,61 2,058 21,4472
79,37 6,324 26,3890 32,63 2,057 21,4473
79,01 4,429 25,9087 32,62 2,057 21,4780
79,02 4,431 26,0100 32,62 2,057 21,4450
79,00 4,431 26,2027 32,61 2,057 21,5410
79,01 4,432 26,0268

Table A1.2: Final selection of the results obtained with the mixture of 54 % nitrogen and 46 % i-pentane.
T / C p / bar /mW
.
m
-1.
K
-1
T / C p / bar /mW
.
m
-1.
K
-1

116,43 9,679 28,5217 100,39 5,013 26,3347
116,50 9,682 28,3210 100,40 5,012 26,5798
116,49 9,685 28,4400 100,35 5,012 26,3010
116,52 9,686 28,6153 100,35 5,011 26,2422
116,55 9,688 28,6003 100,34 5,011 26,1802
116,57 9,690 28,3895 100,35 5,011 26,5039
116,55 9,691 28,3725 100,31 5,010 26,6391
116,54 9,692 28,4970 100,31 5,010 26,6429
64
116,55 9,693 28,6143 100,29 5,010 26,4251
116,56 9,694 28,5759 100,29 5,009 26,0831
116,54 9,695 28,4385 100,29 5,009 26,0618
116,55 9,695 28,7765 100,30 5,009 26,2042
116,56 9,695 28,3484 100,28 5,009 26,2551
116,58 9,696 28,6587 100,29 5,008 26,3220
116,57 9,698 28,7067 100,29 5,008 26,4346
116,57 9,698 28,7151 100,29 5,008 26,4076
116,59 9,699 28,4604 100,32 5,008 26,2766
116,60 9,700 28,6960 100,32 5,007 26,3394
116,59 9,701 28,5887 79,87 8,808 24,6970
116,61 9,701 28,4941 79,83 8,807 24,5181
116,63 9,702 28,5474 79,82 8,807 24,7763
116,80 8,552 28,6215 79,82 8,806 24,7914
116,84 8,552 28,3518 79,80 8,805 24,7406
116,82 8,552 28,7295 79,78 8,805 24,8417
116,84 8,553 28,2578 79,79 8,804 24,7377
116,84 8,552 28,5688 79,77 8,804 24,8306
116,82 8,552 28,4724 79,80 8,803 24,6847
116,82 8,551 28,3539 79,80 8,804 24,7257
116,84 8,550 28,5742 79,81 8,803 24,6742
116,80 8,548 28,2698 79,82 8,803 24,7403
116,81 8,547 28,7388 79,82 8,803 24,7741
116,79 8,546 28,6181 79,83 8,804 24,6862
116,75 8,546 28,3931 79,85 8,803 24,7937
116,72 8,545 28,4055 79,87 8,803 24,7469
116,75 8,544 28,6330 79,87 8,803 24,6420
116,70 8,543 28,4622 79,84 8,802 24,5997
116,72 8,541 28,3995 79,82 8,802 24,6946
116,73 8,541 28,6650 79,80 8,802 24,6706
116,71 8,539 28,6347 79,82 8,801 24,6499
116,75 8,538 28,5602 79,84 8,801 24,8196
116,76 8,537 28,5334 79,82 8,800 24,7488
116,75 8,536 28,4132 78,92 7,463 24,3947
116,82 8,535 28,3466 78,94 7,463 24,4956
116,81 8,535 28,4038 78,94 7,462 24,4237
116,82 8,534 28,3720 78,98 7,461 24,4552
116,83 8,534 28,3949 78,96 7,461 24,3214
116,87 6,967 28,6311 78,97 7,460 24,3530
166,92 6,966 28,3902 78,98 7,460 24,3897
116,89 6,965 28,4173 78,98 7,459 24,3514
116,89 6,964 28,3690 78,94 7,458 24,3420
116,85 6,964 28,5515 78,91 7,457 24,3573
116,81 6,963 28,5152 78,89 7,456 24,3648
116,84 6,962 28,3066 78,86 7,455 24,3899
116,81 6,961 28,3425 78,84 7,454 24,3270
116,80 6,960 28,4497 78,85 7,453 24,5073
116,80 6,960 28,3740 78,85 7,452 24,3173
116,84 6,959 28,3101 78,86 7,450 24,2865
116,79 6,958 28,5498 78,89 7,450 24,3391
65
116,80 6,958 28,4714 78,86 7,450 24,2616
116,78 6,957 28,4894 78,88 7,449 24,4694
116,77 6,957 28,4242 78,88 7,448 24,3800
116,79 6,956 28,5408 78,88 7,448 24,3645
116,78 6,955 28,4335 78,89 7,447 24,5329
116,76 6,955 28,5787 78,87 7,446 24,4703
116,77 6,957 28,4302 79,04 6,193 24,4708
116,77 6,957 28,4405 79,03 6,193 24,3323
116,75 6,953 28,4849 79,03 6,194 24,4285
116,78 6,953 28,3838 79,07 6,195 24,3069
116,78 6,952 28,3603 79,06 6,195 24,3111
116,77 6,952 28,4223 79,05 6,195 24,4094
116,79 6,952 28,4015 79,06 6,196 24,5623
116,76 6,951 28,5730 79,07 6,196 24,1201
116,78 6,951 28,4512 79,05 6,197 24,1233
116,79 6,950 28,5474 79,08 6,196 24,3253
116,77 5,279 28,1530 79,07 6,197 24,1411
116,79 5,279 28,3476 79,41 6,197 24,1485
116,81 5,279 28,1991 79,12 6,198 24,4878
116,84 5,279 28,3277 79,14 6,198 24,3460
116,83 5,279 28,2740 79,14 6,198 24,5342
116,83 5,280 28,1641 79,15 6,199 24,1611
116,83 5,280 28,3090 79,16 6,198 24,3408
116,85 5,280 28,1058 79,16 6,199 24,5379
116,85 5,281 28,2967 79,13 6,198 24,4132
116,86 5,281 28,0320 79,11 6,197 24,3213
116,86 5,281 28,1001 79,08 6,198 24,1439
116,84 5,280 28,0511 79,13 4,774 24,0868
116,85 5,280 28,0633 79,13 4,774 24,1161
116,85 5,279 28,1212 79,09 4,773 24,2310
116,82 5,280 28,0221 79,08 4,773 24,2470
116,81 5,279 28,2114 79,11 4,772 24,2118
116,82 5,278 28,1418 79,11 4,772 24,1673
116,80 5,277 28,2360 79,12 4,771 23,9130
116,86 5,277 28,1853 79,11 4,771 24,0399
116,84 5,277 28,2066 79,12 4,770 23,9371
116,82 5,277 28,2635 79,10 4,770 24,1289
116,84 5,277 28,2342 79,11 4,769 24,2022
116,85 5,276 28,1915 79,12 4,769 24,2350
116,84 5,276 28,3081 79,11 4,768 24,2468
116,84 5,276 28,2395 79,11 4,768 23,8998
116,84 5,276 28,1488 79,12 4,767 24,0419
100,72 9,177 26,9148 79,13 4,768 24,0447
100,72 9,175 26,7855 79,13 4,767 24,1908
100,70 9,173 26,8871 79,12 4,766 24,1331
100,67 9,171 26,7471 79,14 4,765 23,9037
100,63 9,170 26,7403 79,13 4,765 24,0237
100,61 9,168 26,7462 79,12 4,764 24,0811
100,62 9,166 26,9855 79,12 4,764 23,9020
100,57 9,165 26,8045 59,08 5,724 22,3714
66
100,56 9,163 26,6157 59,07 5,723 22,2224
100,54 9,161 26,6339 59,10 5,723 22,1680
100,53 9,160 26,9716 59,06 5,722 22,1046
100,50 9,158 27,0602 59,05 5,721 22,3389
100,49 9,156 26,7185 59,05 5,721 22,4059
100,48 9,155 26,7019 59,03 5,720 22,3531
100,46 9,153 26,6985 59,03 5,719 22,1883
100,44 9,151 26,7916 59,00 5,719 22,3907
100,40 9,150 26,6283 58,97 5,718 22,2772
100,39 9,149 26,6987 58,96 5,717 22,3463
100,39 9,147 26,6111 58,94 5,716 22,1715
100,36 9,145 26,6257 58,94 5,716 22,2287
100,36 9,144 26,8605 58,93 5,715 22,4660
100,34 9,143 26,5737 58,92 5,715 22,4909
100,37 9,142 26,9807 58,93 5,715 22,3806
100,35 9,140 26,7308 58,93 5,715 22,3125
100,34 9,139 26,6251 58,96 5,714 22,3164
100,33 9,137 26,5216 58,96 5,713 22,2354
100,51 8,074 26,5865 58,91 5,713 22,2335
100,50 8,072 26,4165 58,89 5,712 22,2347
100,48 8,071 26,7770 58,87 5,712 22,2085
100,45 8,069 26,6560 58,88 5,711 22,3395
100,46 8,067 26,7558 58,89 5,710 22,3241
100,44 8,065 26,6117 58,90 4,409 21,7675
100,43 8,063 26,6243 58,90 4,409 21,9064
100,38 8,062 26,5866 58,87 4,409 21,8805
100,35 8,060 26,5520 58,85 4,408 22,0080
100,35 8,059 26,9071 58,87 4,408 22,0189
100,37 8,057 26,4939 58,83 4,407 22,0449
100,33 8,057 26,6842 58,81 4,407 21,9421
100,32 8,054 26,6647 58,82 4,407 22,0077
100,33 8,054 26,9658 58,80 4,407 21,9515
100,29 8,053 26,8516 58,82 4,407 22,0247
100,34 8,051 26,7264 58,79 4,406 21,9030
100,33 8,050 26,8595 58,81 4,406 21,8892
100,32 8,049 26,9626 58,87 4,406 22,0565
100,34 8,048 26,8948 58,85 4,406 22,0986
100,30 8,046 26,6137 58,85 4,405 22,0219
100,27 8,045 26,6958 58,88 4,405 21,9924
100,29 8,044 26,6147 58,87 4,405 22,0600
100,30 8,042 26,7016 58,88 4,405 21,9621
100,25 8,041 26,6683 58,86 4,405 22,0406
99,73 6,510 26,6251 58,87 4,405 22,0553
99,83 6,513 26,3927 58,83 4,405 21,8282
99,89 6,516 26,4488 58,85 4,405 22,0400
99,90 6,519 26,3725 58,89 4,405 22,0227
99,96 6,520 26,3234 58,89 4,405 21,9621
99,97 6,522 26,3292 58,89 4,404 21,8433
99,97 6,524 26,4305 59,76 3,343 21,5641
100,02 6,525 26,2830 59,73 3,347 21,5646
67
100,02 6,527 26,4280 59,71 3,349 21,4228
100,03 6,527 26,5687 59,71 3,351 21,3832
100,05 6,527 26,4195 59,70 3,350 21,6009
100,06 6,528 26,3111 59,68 3,351 21,5838
100,07 6,529 26,5909 59,66 3,351 21,6655
100,08 6,529 26,4243 59,70 3,350 21,4367
100,09 6,530 26,4197 59,70 3,350 21,4896
100,12 6,530 26,8766 59,67 3,350 21,4377
100,13 6,531 26,7722 59,66 3,350 21,3878
100,14 6,531 26,6513 59,62 3,349 21,5473
100,15 6,531 26,3186 59,62 3,349 21,4163
100,16 6,532 26,6629 59,59 3,349 21,4096
100,16 6,532 26,4407 59,61 3,350 21,5824
100,18 6,532 26,6509 59,62 3,350 21,3454
100,18 6,533 26,6387 59,58 3,350 21,5147
100,19 6,533 26,6784 59,58 3,350 21,3797
100,45 5,015 26,1678 59,56 3,351 21,4985
100,48 5,015 26,4145 59,57 3,351 21,3553
100,44 5,015 26,5466 59,58 3,351 21,5913
100,47 5,014 26,5183 59,62 3,351 21,3219
100,45 5,014 26,2569 59,61 3,352 21,5755
100,42 5,013 26,5119 59,61 3,352 21,3858

Table A1.3: Final selection of the results obtained with the mixture of 25 % nitrogen and 75 % i-pentane.
T / C p / bar /mW
.
m
-1.
K
-1
T / C p / bar /mW
.
m
-1.
K
-1

118,30 7,254 26,7000 101,51 5,905 24,9714
118,29 7,253 26,9050 101,51 5,904 24,7860
118,28 7,251 27,2592 101,50 5,903 25,0758
118,23 7,250 27,1700 101,53 5,902 24,7817
118,22 7,248 27,0923 101,50 5,901 24,7603
118,18 7,247 27,2906 101,42 5,090 24,7164
118,19 7,245 27,1434 101,41 5,089 24,9564
118,14 7,244 27,1381 101,42 5,088 24,9403
118,14 7,242 27,0648 101,42 5,087 24,9880
118,13 7,241 26,9334 101,40 5,086 24,7478
118,11 7,239 27,0361 101,42 5,086 24,9739
118,10 7,238 27,0205 101,39 5,085 24,8957
118,09 7,237 27,0767 101,39 5,085 24,7937
118,07 7,235 27,0854 101,37 5,085 24,8867
118,09 7,234 26,9411 101,38 5,085 24,8137
118,06 7,233 27,1258 101,38 5,084 24,8075
118,07 7,231 26,9249 101,40 5,083 24,7834
118,02 7,229 26,9240 101,37 5,083 24,8948
118,04 7,228 26,8900 101,40 5,083 24,8209
118,04 7,227 27,0164 101,38 5,083 24,8511
118,02 7,225 26,8628 101,87 3,957 24,9855
118,02 7,223 27,1161 101,87 3,957 24,7864
118,00 7,222 26,9197 101,86 3,957 24,5441
117,97 7,219 27,0674 101,86 3,957 24,6827
117,94 7,218 27,0824 101,82 3,957 24,7307
68
117,94 7,216 27,1893 101,82 3,957 24,8728
117,91 7,214 26,7620 101,81 3,956 24,8199
117,89 7,212 26,8028 101,79 3,956 25,0255
117,79 6,249 26,7984 101,77 3,956 25,0066
117,76 6,249 26,8190 101,79 3,956 24,6926
117,77 6,250 26,7742 101,78 3,955 24,8672
117,75 6,250 26,8491 101,77 3,955 24,9878
117,71 6,252 27,1044 101,77 3,954 24,6615
117,72 6,252 26,9375 101,76 3,954 25,0166
117,74 6,251 26,9983 101,76 3,954 24,8658
117,73 6,251 26,8581 101,74 3,953 24,8142
117,71 6,251 26,7816 101,76 3,953 24,8606
117,70 6,252 26,7379 101,76 3,953 24,6948
117,70 6,251 26,9483 101,77 3,953 24,9873
117,69 6,252 26,9518 101,75 3,953 24,9196
117,68 6,252 27,0514 101,76 3,952 24,8343
117,69 6,253 27,1135 101,73 3,952 24,7432
117,69 6,253 26,7509 101,51 3,247 24,7118
117,70 6,254 27,1973 101,48 3,247 25,0374
117,72 6,254 27,0995 101,48 3,247 24,8902
117,70 6,254 26,6802 101,45 3,247 24,5067
117,72 6,254 26,7582 101,44 3,246 25,0410
117,70 6,254 26,9756 101,43 3,246 24,6568
117,71 6,253 27,0939 101,42 3,246 24,7049
117,71 6,253 26,8284 101,42 3,246 24,7959
117,89 5,248 26,8786 101,42 3,247 24,7963
117,84 5,246 27,1340 101,42 3,245 24,7206
117,78 5,244 26,8870 101,39 3,246 24,8651
117,69 5,243 26,9858 101,39 3,245 24,8621
117,63 5,242 26,8322 101,40 3,245 24,8335
117,61 5,241 26,9155 101,36 3,245 24,8268
117,61 5,240 26,6870 101,38 3,245 24,8813
117,59 5,239 27,0880 101,38 3,245 24,6133
117,63 5,238 26,9534 101,38 3,245 24,6537
117,62 5,238 26,8554 101,40 3,245 24,6454
117,62 5,238 27,0980 79,58 4,652 21,8100
117,66 5,237 26,7735 79,55 4,650 22,0357
117,68 5,237 26,9316 79,56 4,650 22,4221
117,68 5,238 26,7458 79,55 4,650 22,2661
117,68 5,238 26,8003 79,56 4,649 22,2382
117,66 5,238 26,9295 79,58 4,649 21,9793
117,70 5,239 26,8240 79,57 4,647 22,1725
117,68 5,240 26,7376 79,59 4,647 22,0116
117,68 5,239 26,8905 79,58 4,645 22,0491
117,71 5,239 26,7796 79,60 4,645 22,0167
117,71 5,240 26,9265 79,58 4,646 22,3613
117,72 5,241 26,7258 79,62 4,645 22,3980
117,72 5,242 27,1347 79,62 4,645 22,0652
117,72 5,243 26,8782 79,63 4,644 22,1202
117,73 5,244 27,0143 79,65 4,644 22,0307
69
117,76 5,246 26,6973 79,64 4,644 21,9382
117,77 5,247 27,1436 79,69 4,644 22,2270
117,82 4,027 26,8726 79,68 4,644 22,3128
117,79 4,028 26,7415 79,66 4,643 22,1199
117,77 4,027 27,1121 79,62 4,643 22,1396
117,78 4,028 26,6604 79,61 4,642 22,2383
117,80 4,028 26,8206 79,58 4,642 22,1036
117,79 4,029 26,8830 79,57 4,642 22,2918
117,83 4,029 26,8784 79,59 4,641 22,2468
117,80 4,029 26,8727 79,72 3,645 22,2148
117,84 4,029 26,8782 79,66 3,645 22,0640
117,86 4,029 26,7440 79,68 3,645 22,0613
117,87 4,029 26,7582 79,66 3,645 22,1497
117,89 4,029 26,6036 79,64 3,645 22,1984
117,93 4,031 27,1174 79,65 3,643 22,2528
117,90 4,031 27,1154 79,63 3,638 21,8913
117,92 4,030 26,7879 79,63 3,635 22,1370
117,94 4,030 26,9640 79,58 3,633 21,9480
117,95 4,030 27,0212 79,49 3,632 22,3095
117,94 4,030 26,7340 79,37 3,630 22,0845
117,93 4,031 27,0099 79,62 3,624 21,8630
117,95 4,031 27,0359 79,88 3,627 22,0064
117,96 4,031 26,8231 79,88 3,635 22,0677
118,01 3,413 26,8062 79,90 3,636 21,9378
118,01 3,414 26,8882 79,88 3,637 22,3342
118,00 3,415 27,0158 79,89 3,637 22,0137
118,03 3,417 26,9258 79,91 3,637 22,0244
118,02 3,417 26,8831 79,84 3,638 22,0283
118,03 3,418 26,9052 79,83 3,638 22,0274
118,02 3,417 27,2189 79,84 3,639 22,0209
118,05 3,418 26,6325 79,83 3,640 22,0694
118,06 3,419 26,8505 79,86 3,640 22,2753
118,03 3,419 26,6019 79,90 3,641 22,1942
118,07 3,420 27,1386 79,92 3,642 22,1815
118,05 3,419 26,5856 79,96 3,643 22,1936
118,04 3,419 27,1488 80,00 3,643 22,3926
118,04 3,419 27,0428 80,00 3,644 22,4313
118,03 3,420 26,7717 80,02 3,645 21,9641
118,00 3,419 27,2232 80,05 3,646 22,0243
118,02 3,420 26,6167 80,08 3,647 22,2688
101,22 6,854 24,9200 80,09 3,647 22,3536
101,19 6,853 24,8195 80,13 3,647 22,1719
101,18 6,854 25,0705 60,15 3,202 19,1666
101,18 6,853 25,0705 60,14 3,211 19,3102
101,16 6,853 25,0362 60,17 3,219 19,1949
101,16 6,852 24,7862 60,16 3,227 19,1498
101,17 6,852 24,9786 60,14 3,233 19,1429
101,19 6,852 24,9019 60,14 3,240 19,1668
101,18 6,852 24,7679 60,15 3,249 19,1554
101,18 6,851 24,8201 60,16 3,253 19,1510
70
101,18 6,852 24,7307 60,16 3,256 19,3177
101,18 6,851 24,8631 60,15 3,260 19,2112
101,18 6,852 24,7905 60,15 3,263 19,1488
101,20 6,852 24,7948 60,17 3,266 19,1601
101,22 6,852 24,9286 60,15 3,267 19,1884
101,23 6,852 24,9409 60,17 3,270 19,2105
101,23 6,852 24,7863 60,52 2,518 19,2808
101,24 6,852 24,7698 60,48 2,517 19,1756
101,23 6,853 25,0256 60,41 2,517 19,2113
101,23 6,853 24,6416 60,39 2,516 19,1555
101,75 5,926 24,6622 60,34 2,515 19,2181
101,71 5,923 25,0545 60,32 2,515 19,0825
101,71 5,923 24,9185 60,32 2,514 19,1045
101,68 5,922 24,9421 60,27 2,514 19,1589
101,71 5,922 24,9037 60,27 2,514 19,0949
101,65 5,921 24,9684 60,28 2,514 19,1547
101,65 5,919 24,9077 60,25 2,514 19,1909
101,62 5,918 25,1509 60,22 2,514 19,1751
101,62 5,916 25,0502 60,22 2,513 19,1291
101,59 5,916 24,8146 60,17 2,513 19,1379
101,57 5,915 25,0315 60,17 2,513 19,2431
101,58 5,913 24,8493 60,15 2,512 19,0589
101,58 5,912 24,9137 60,14 2,512 19,1176
101,58 5,910 24,9136 60,11 2,512 19,2163
101,56 5,908 24,8830 60,11 2,511 19,2324
101,56 5,908 24,9600 60,14 2,511 19,2547
101,55 5,907 24,8990 60,16 2,512 19,1846
60,12 2,511 19,1953

Table A1.4: Final selection of the results obtained with cyclopentane.
T / C p / bar /mW
.
m
-1.
K
-1
T / C p / bar /mW
.
m
-1.
K
-1

120,94 5,925 21,2726 101,70 2,202 18,7056
120,93 5,920 20,9251 101,70 2,203 18,7415
120,93 5,917 20,9067 91,14 2,873 17,5489
120,90 5,909 21,0804 91,14 2,871 17,5542
120,88 5,904 21,1583 91,13 2,870 17,5461
120,87 5,899 20,9708 91,11 2,869 17,5959
120,83 5,894 20,9022 91,12 2,867 17,4642
120,79 5,886 20,8402 91,05 2,866 17,6068
120,77 5,883 20,9696 91,05 2,865 17,5629
120,72 5,881 20,9780 91,04 2,864 17,5941
120,70 5,879 21,2356 91,00 2,863 17,5781
120,72 5,882 20,8410 91,00 2,862 17,5219
120,70 5,880 21,1994 90,96 2,861 17,5181
120,70 5,882 21,0319 90,95 2,861 17,4698
120,70 5,883 21,0651 90,95 2,860 17,5472
120,71 5,880 21,1495 90,92 2,859 17,6495
120,72 5,881 21,0037 90,93 2,859 17,6668
120,71 5,879 20,8567 90,92 2,858 17,5447
71
120,69 5,883 20,9349 90,91 2,858 17,5126
120,70 5,881 21,0997 90,92 2,857 17,4225
120,73 5,883 21,0103 90,91 2,858 17,6841
120,72 5,881 21,0324 90,89 2,857 17,4544
120,69 5,881 20,9146 90,89 2,858 17,7317
120,69 5,880 21,0310 90,89 2,859 17,4935
120,68 5,880 21,0437 90,88 2,858 17,4809
120,70 5,882 20,9971 90,89 2,858 17,4449
121,24 6,554 20,8877 90,60 3,208 17,0810
121,23 6,542 20,6781 90,59 3,206 17,3483
121,22 6,539 20,9732 90,58 3,201 17,3729
121,19 6,540 21,0783 90,56 3,198 17,3301
121,16 6,538 20,9989 90,57 3,197 17,3948
121,17 6,538 21,0806 90,56 3,196 17,3476
121,14 6,538 21,1023 90,53 3,194 17,3888
121,13 6,538 21,0029 90,50 3,194 17,2700
121,14 6,537 21,0622 90,47 3,192 17,5449
121,11 6,539 20,9950 90,47 3,191 17,4161
121,13 6,539 21,1429 90,47 3,189 17,3752
121,14 6,539 20,8632 90,46 3,187 17,4739
121,15 6,531 20,8704 90,42 3,187 17,4306
121,13 6,531 20,8744 90,40 3,186 17,4166
121,16 6,534 20,8463 90,41 3,183 17,1765
121,11 6,532 20,8458 90,39 3,183 17,2468
121,11 6,537 21,0195 90,38 3,183 17,5153
121,15 6,539 20,9155 90,34 3,182 17,1479
121,13 6,538 21,1801 90,35 3,181 17,2482
121,17 6,543 20,7180 90,36 3,180 17,2049
121,17 6,542 21,2340 90,32 3,181 17,2047
121,18 6,545 21,0748 90,33 3,180 17,2723
121,20 6,543 21,0718 90,34 3,179 17,3211
121,21 6,548 21,0533 91,32 3,189 17,2155
121,21 6,549 21,0452 91,28 3,185 17,3729
121,80 5,313 21,5067 91,29 3,183 17,4090
121,81 5,311 21,0939 91,26 3,180 17,5108
121,78 5,311 21,0774 91,26 3,178 17,3172
121,77 5,311 21,4215 91,26 3,175 17,4545
121,77 5,311 21,2192 91,21 3,174 17,2806
121,76 5,312 21,1944 91,22 3,172 17,6494
121,74 5,311 21,3693 91,19 3,170 17,2850
121,73 5,311 21,3638 91,18 3,168 17,5354
121,70 5,311 21,1187 91,16 3,167 17,4536
121,68 5,311 21,1770 91,15 3,165 17,4007
121,66 5,311 21,0952 91,13 3,164 17,5891
121,64 5,311 21,3463 91,11 3,162 17,5468
121,67 5,311 21,3736 91,08 3,160 17,4160
121,64 5,311 21,4543 91,05 3,159 17,4334
121,62 5,311 21,1366 91,09 3,157 17,5286
121,64 5,311 21,3775 91,05 3,156 17,4496
121,63 5,312 21,2456 91,05 3,154 17,5035
72
121,64 5,311 21,2426 91,03 3,154 17,4386
121,62 5,314 21,2444 91,03 3,152 17,5142
121,63 5,313 21,4058 90,99 3,151 17,3657
121,62 5,314 21,4578 90,96 3,148 17,2928
121,62 5,314 21,2927 90,96 3,147 17,3716
121,62 5,314 21,3708 90,95 3,146 17,5652
121,63 5,315 21,0718 90,92 3,145 17,3969
121,64 5,315 21,0741 90,81 2,070 17,2953
121,23 4,328 21,0191 90,84 2,068 17,4994
121,24 4,326 21,2896 90,82 2,068 17,4292
121,22 4,325 21,3010 90,84 2,068 17,4980
121,18 4,323 21,1555 90,81 2,068 17,3774
121,15 4,321 21,1702 90,81 2,067 17,4646
121,09 4,320 21,2398 90,81 2,067 17,4002
121,07 4,319 21,1138 90,80 2,068 17,3897
121,01 4,317 21,2426 90,81 2,067 17,4104
120,99 4,317 21,2730 90,79 2,067 17,5212
120,94 4,316 21,1066 90,77 2,066 17,5256
120,88 4,316 21,1444 90,75 2,067 17,5812
120,88 4,314 21,2479 90,77 2,067 17,6221
120,86 4,315 20,9237 90,77 2,067 17,4146
120,85 4,314 21,2024 90,76 2,066 17,7286
120,82 4,314 21,1306 90,77 2,067 17,5756
120,80 4,314 21,1512 90,74 2,067 17,3600
120,82 4,313 21,2096 90,76 2,067 17,6077
120,80 4,314 21,2496 90,74 2,067 17,6500
120,82 4,313 21,2305 90,74 2,066 17,3059
120,81 4,312 21,2586 90,75 2,066 17,6020
120,81 4,311 21,0754 90,72 2,066 17,5367
120,78 4,311 21,0329 90,72 2,065 17,3311
120,77 4,311 21,0410 90,73 2,064 17,5870
120,74 4,310 21,3452 90,73 2,063 17,3838
101,25 4,053 18,4991 80,51 2,442 16,3709
101,26 4,050 18,6481 80,50 2,441 16,3998
101,23 4,047 18,6109 80,53 2,441 16,2895
101,24 4,046 18,7665 80,53 2,442 16,2755
101,20 4,044 18,7233 80,55 2,441 16,2906
101,18 4,045 18,7302 80,50 2,438 16,2568
101,18 4,044 18,7785 80,49 2,437 16,2801
101,17 4,043 18,5936 80,48 2,437 16,3283
101,21 4,043 18,6961 80,49 2,435 16,2318
101,16 4,042 18,7504 80,50 2,436 16,3215
101,19 4,042 18,8053 80,48 2,436 16,3010
101,14 4,043 18,7662 80,49 2,437 16,2667
101,17 4,041 18,5446 80,48 2,437 16,3272
101,17 4,041 18,8050 80,50 2,437 16,3121
101,18 4,040 18,6006 80,53 2,438 16,3730
101,17 4,041 18,5476 80,51 2,437 16,4194
101,19 4,041 18,5735 80,49 2,434 16,3541
101,15 4,041 18,5593 80,51 2,436 16,3739
73
101,19 4,041 18,5729 80,47 2,435 16,1783
101,19 4,041 18,7383 80,49 2,436 16,2796
101,21 4,040 18,5749 80,47 2,435 16,3796
101,21 4,039 18,6589 80,48 2,437 16,3248
101,22 4,039 18,6611 80,51 2,435 16,2144
101,22 4,039 18,7952 80,47 2,434 16,2462
101,21 4,037 18,7913 81,02 2,617 16,6085
101,20 4,037 18,5505 80,94 2,616 16,3259
102,47 3,884 18,6324 80,97 2,618 16,5732
102,52 3,883 18,9876 80,96 2,616 16,3313
102,52 3,883 18,9056 80,92 2,616 16,2267
102,51 3,883 18,8587 80,97 2,617 16,4791
102,54 3,883 18,8540 80,95 2,618 16,4207
102,54 3,883 18,9276 80,95 2,620 16,4833
102,55 3,881 18,9244 80,95 2,619 16,5650
102,55 3,881 18,8157 80,99 2,619 16,4162
102,52 3,881 18,9640 80,94 2,619 16,3074
102,52 3,880 18,7657 80,95 2,620 16,3238
102,48 3,881 18,8337 80,94 2,621 16,2393
102,51 3,880 18,8821 80,96 2,620 16,5406
102,48 3,881 18,7816 80,97 2,622 16,3322
102,51 3,881 19,0372 80,95 2,620 16,5436
102,48 3,881 18,7913 80,95 2,623 16,2961
102,52 3,881 18,9605 80,93 2,621 16,5603
102,51 3,880 18,9477 80,98 2,622 16,5132
102,51 3,880 18,7594 80,97 2,622 16,1084
102,50 3,880 18,8122 80,97 2,621 16,3674
102,50 3,880 18,8274 80,98 2,623 16,1501
102,52 3,880 18,8389 81,52 2,585 15,7740
102,51 3,880 18,7848 81,54 2,585 16,3226
102,51 3,881 18,9663 81,55 2,584 16,3584
102,50 3,881 18,8781 81,55 2,584 16,1324
102,50 3,881 18,7733 81,53 2,584 16,2625
101,76 3,096 18,5598 81,51 2,582 16,1376
101,79 3,098 18,7239 81,50 2,582 16,0323
101,83 3,100 18,6943 81,51 2,582 16,1060
101,84 3,101 18,8171 81,48 2,583 16,1116
101,83 3,102 18,8941 81,51 2,582 16,1844
101,80 3,103 18,6882 81,50 2,582 16,3187
101,82 3,104 18,7940 81,49 2,583 15,9860
101,84 3,105 18,7286 81,49 2,583 16,0642
101,84 3,105 18,7262 81,53 2,583 16,2650
101,86 3,104 18,7663 81,53 2,583 16,3374
101,85 3,105 18,9279 81,55 2,584 16,2141
101,88 3,105 18,6603 81,57 2,585 15,9431
101,87 3,105 18,7159 81,55 2,586 15,9617
101,90 3,106 18,7026 81,55 2,586 16,0907
101,90 3,106 18,8603 81,59 2,586 16,0699
101,94 3,106 18,8087 81,60 2,586 16,0597
101,92 3,106 18,8506 81,59 2,587 16,0111
74
101,91 3,106 18,8700 81,61 2,587 16,0589
101,92 3,106 18,8203 81,59 2,587 16,2841
101,94 3,106 18,7311 81,57 2,586 16,3472
101,94 3,106 18,6074 81,60 2,587 16,1173
101,90 3,106 18,7909 80,37 2,042 16,1748
101,94 3,105 18,7117 80,41 2,043 16,3241
101,93 3,105 19,0199 80,38 2,042 16,3504
101,94 3,105 18,8093 80,37 2,041 16,3856
101,87 2,204 19,1008 80,35 2,041 16,1471
101,86 2,204 18,6078 80,35 2,040 16,3221
101,86 2,203 18,7900 80,33 2,040 16,3384
101,84 2,204 18,9786 80,29 2,039 16,1995
101,84 2,204 18,7753 80,26 2,038 16,2068
101,82 2,204 18,9447 80,25 2,038 16,2330
101,81 2,205 18,7509 80,25 2,038 16,2289
101,83 2,204 19,0343 80,26 2,039 16,2723
101,81 2,204 18,5652 80,28 2,039 16,3067
101,83 2,204 18,9673 80,29 2,039 16,2752
101,79 2,203 18,9450 80,29 2,038 16,2116
101,77 2,203 18,8788 80,29 2,038 16,2874
101,79 2,202 18,5340 80,28 2,038 16,2700
101,76 2,202 18,5464 80,24 2,037 16,2967
101,75 2,202 18,7186 80,23 2,036 16,1944
101,74 2,202 18,6542 80,24 2,036 16,2621
101,74 2,203 18,7821 80,23 2,036 16,3447
101,72 2,203 18,8580 80,20 2,036 16,1683
101,70 2,202 18,6928 80,22 2,035 16,3086
101,70 2,202 18,6528 80,25 2,036 16,1864
101,72 2,202 18,8009 80,20 2,034 16,1794
101,71 2,202 18,8053 80,21 2,034 16,1801

Table A1.5: Final selection of the results obtained with the mixture of 74 % c-pentane and 26 % i-pentane.
T / C p / bar /mW
.
m
-1.
K
-1
T / C p / bar /mW
.
m
-1.
K
-1

120,53 6,059 22,7384 97,80 3,548 19,4664
120,49 6,059 22,8408 97,79 3,547 19,3274
120,50 6,058 22,7869 97,77 3,546 19,2178
120,45 6,055 22,8128 97,76 3,546 19,2697
120,42 6,053 22,8086 97,75 3,546 19,5812
120,43 6,053 22,8413 97,76 3,547 19,3127
120,43 6,054 22,6592 97,74 3,547 19,2190
120,43 6,053 22,7218 97,75 3,547 19,5623
120,42 6,052 22,9453 97,79 3,547 19,2266
120,41 6,053 22,6597 97,80 3,546 19,1696
120,43 6,053 22,7024 97,82 3,547 19,5390
120,44 6,053 22,6626 90,63 3,929 19,0033
120,48 6,052 22,6753 90,59 3,928 18,8392
120,50 6,053 22,9421 90,58 3,926 18,6719
120,47 6,053 23,0324 90,57 3,925 18,8893
120,50 6,054 22,9037 90,59 3,921 18,7797
120,60 5,067 22,2142 90,56 3,920 18,8733
75
120,56 5,068 22,4093 90,53 3,919 18,8156
120,58 5,068 22,3320 90,52 3,918 18,7522
120,54 5,068 22,3335 90,56 3,915 18,8026
120,56 5,068 22,3942 90,55 3,915 18,8837
120,49 5,068 22,5458 90,51 3,915 18,7261
120,48 5,068 22,2735 90,54 3,922 18,8790
120,46 5,069 22,2158 90,51 3,926 19,0997
120,44 5,068 22,1448 90,52 3,926 18,9454
120,45 5,067 22,2058 89,59 3,591 18,5012
120,43 5,067 22,4965 89,59 3,592 18,1284
120,40 5,066 22,2870 89,56 3,593 18,2534
120,40 5,066 22,4568 89,59 3,595 18,1739
120,41 5,066 22,3273 89,59 3,595 18,3157
120,43 5,065 22,3717 89,58 3,596 18,2364
120,42 5,065 22,2434 89,59 3,595 18,1881
120,42 5,065 22,4524 89,59 3,596 18,3141
120,44 5,065 22,5269 89,59 3,596 18,2538
120,44 5,064 22,4517 89,59 3,597 18,3282
120,42 5,064 22,4132 89,58 3,598 18,2641
101,49 4,369 19,9635 89,60 3,598 18,2482
101,45 4,369 20,0154 89,57 3,598 18,2830
101,45 4,368 19,7966 89,61 3,598 18,1916
101,44 4,368 19,9010 89,56 3,597 18,0355
101,41 4,365 20,1437 89,58 3,597 18,4354
101,39 4,365 20,0418 89,57 3,596 18,2873
101,41 4,365 19,7012 89,57 3,597 18,3809
101,40 4,365 20,1672 89,55 3,596 18,0711
101,40 4,364 20,1223 89,57 3,597 18,3096
101,36 4,364 19,7260 89,56 3,597 18,2900
101,37 4,362 19,8820 89,59 3,597 18,3012
101,36 4,362 19,8847 89,94 3,256 18,4130
101,35 4,361 19,9160 89,89 3,255 18,4059
101,37 4,361 19,8946 89,90 3,254 18,4070
101,35 4,360 19,8806 89,87 3,252 18,5121
101,31 4,360 19,8465 89,83 3,250 18,4427
101,32 4,361 19,9971 89,81 3,249 18,4637
101,34 4,359 19,9216 89,78 3,246 18,5363
101,32 4,359 19,9241 89,79 3,246 18,5227
101,34 4,359 19,8042 89,76 3,244 18,3207
101,35 4,360 19,9732 89,78 3,244 18,4518
101,33 4,359 19,8875 89,74 3,245 18,5582
97,82 3,550 19,4362 89,74 3,244 18,3441
97,79 3,549 19,5346 89,72 3,241 18,4040
97,75 3,548 19,3583 89,70 3,241 18,4951
97,73 3,548 19,2691 89,68 3,242 18,5438
97,72 3,548 19,4451 89,68 3,242 18,5158
97,76 3,548 19,4831 89,66 3,240 18,4966
97,77 3,548 19,5570 89,69 3,242 18,5095
97,77 3,548 19,5103

You might also like