INTERNSHIP REPORT

AT UNIVERSITY OF GRONINGEN

THE NETHERLANDS

As a Requirement for the Final Exam in the Last Semester of Academic Year
2019/2020

Prepared by

Salma Billah Attaqy

SRN 16.62.08509

MINISTRY OF INDUSTRY OF THE REPUBLIC INDONESIA

Industrial Human Resource Development Agency

Vocational High School – Bogor High School of Chemical Analyst

2020
 INTERNSHIP REPORT

AT UNIVERSITY OF GRONINGEN

THE NETHERLANDS

Analysis of Bitumen Composition with Thermal Desorption Method

Using PTV-GC-MS

Prepared by

Salma Billah Attaqy

SRN 16.62.08509

MINISTRY OF INDUSTRY OF THE REPUBLIC INDONESIA

Industrial Human Resource Development Agency

Vocational High School – Bogor High School of Chemical Analyst

2020
 APPROVAL LETTER

Internship Report at University of Groningen – The Netherlands by Salma Billah

Attaqy

Approved and authorized by :

Approved by,

Jan Henk Marsman Léon Rohrbach

Supervisor Supervisor

Lalu Shafwan Hadi El Wathan Jan Ros

EIN. 198906262014021001 VAPRO Representative
Supervisor

Dwika Riandari, M.Si.

EIN. 196607262002122001
Head of Vocational High School – Bogor High School of Chemical Analyst
 FOREWORD

In the name of Allah, the Entirely Merciful, all praise is due to Allah, Lord of
the worlds which guide me so I can be able to complete this internship report titled
‘Analysis of Bitumen Composition with Thermal Desorption Method Using PTV-
GC-MS’. The making of the report is based on activities that have been done during
the internship at University of Groningen – The Netherlands from 9th January until
28th February 2020.

This report is aimed to fulfill one of the requirements of the final exam in the
last semester of the academic year 2019/2020. This requirement applies to
students at Vocational High School – Bogor High School of Chemical Analyst who
has accomplished the internship.

There are several chapters of this report. Starting with a brief description of
activities- which have been done during the internship, including background and
purposes. The next chapter explains about the internship institution, where authors’
work took place as well as and structural information regarding the institution.

The next chapter tells the reader all the activities in laboratory practice
during the internship and the results. Also, the discussions of the implemented
analysis will be included in the fourth chapter. The last chapter contains
conclusions and suggestions of the whole report.

In addition, I would like to give my special gratitude to:

1. My beloved parents and entire family members, who always give their
support in every situation.
2. Hadiati Agustine, as the Former Head of Vocational High School – Bogor
High School of Chemical Analyst (2009 – 2017 period).
3. Dwika Riandari, as the Head of Vocational High School – Bogor High
School of Chemical Analyst (2017 – present).
4. Amilia Sari Ghani, as the Vice Head of Industrial Work Relations Division,
and all the staff.
5. Tin Kartini, as the Head of Laboratory at Vocational High School – Bogor
High School of Chemical Analyst, and all the staff.

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 6. Jan Henk Marsman, as a supervisor for the internship program from the
institution.
7. Léon Rohrbach, as a supervisor for the internship program from the
institution.
8. Lalu Shafwan Hadi El Wathan, as a supervisor for the internship program
from school.
9. Jan Ros, as representative from VAPRO International.
10. The entire partners during the internship: Shafaá Puteri Alzahra, Veerle
Huisman, Beau Boonstra, Sander Beck, Joris Lokken, Laura Tatiana
Aguirre

11. Ridho Ahmad Pratama, Adryansyah Madya Ramadhan, Muhammad

Daffa Atallah, as seniors from school as well as the previous interns.
12. The entire University of Groningen analysts and staff.
13. The entire teachers and staff of Vocational High School – Bogor High
School of Chemical Analyst.

14. The entire partners 62 nd generation ‘Viadvera Gamavortem’, especially Feri

Sandrian, Farhan Sulthan Irawan, Farid Ramadhan, Dwi Ramadhan,
Muhammad Azmy Arya Rizaldi, Putri Ageng Nurhartanty, Lutfiah Dwi
Ramadhanti, Liza Efrizal Putri, Shofwatul Aulya who also contribute a lot
for great support.
15. Other people who also contribute to the making of this report.

I recognize that this report is far from perfection. Consequently, I welcome any
suggestions and critics from readers to improve this report. I hope this report can
expand the readers’ knowledge and enhance the readers’ skills in chemical
analysis. Other than that, this report can further be a reference for students of
Bogor Vocational High School – Bogor High School of Chemical Analyst or others
in writing reports.

Groningen, February 2020

Salma Billah Attaqy

Author

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 TABLE OF CONTENTS
FOREWORD ....................................................................................................... 1
TABLE OF CONTENTS ....................................................................................... 3
LIST OF FIGURES .............................................................................................. 1
LIST OF TABLES ................................................................................................ 1
CHAPTER I ......................................................................................................... 1
Preliminary........................................................................................................... 1
A. Internship Background ............................................................................................ 1
CHAPTER II ........................................................................................................ 3
The Internship Institution ...................................................................................... 3
A. The History of Groningen University ....................................................................... 3
B. Vission and Mission ................................................................................................. 6
CHAPTER III ....................................................................................................... 9
Laboratorium Activity ........................................................................................... 9
A. Activity .................................................................................................................... 9
B. Literature Preview................................................................................................... 9
CHAPTER IV ..................................................................................................... 21
Analytical Method .............................................................................................. 21
CHAPTER V ...................................................................................................... 26
RESULTS AND DISCUSSION........................................................................... 26
Chapter VI ......................................................................................................... 41
CONCLUSION AND SUGGESTION .................................................................. 41
BIBLIOGRAPHY ................................................................................................ 42

3
 LIST OF FIGURES

Figure 2. 1. Groningen University Building ........................................................... 3

Figure 2. 2.. Ubbo Emmius, the First Rector Magnificus of Groningen University. 4
Figure 2. 3. Academic Building of Groningen University in 1850 .......................... 4
Figure 2. 4. Groningen University Logo................................................................ 5
Figure 3. 1. Bitumen for waterproofing roof .......................................................... 9
Figure 3. 2. Thermal Desorption Setup .............................................................. 10
Figure 3. 4. Cross-section of Fused SIlica Open Tubular Column ...................... 16
Figure 3. 5. Ion path through quadrupole illustration .......................................... 19
Figure 3. 6. An example of Mass chromatogram ................................................ 20
Figure 5. 1. The liner got broken and dirty after measurement ........................... 32
Figure 5. 2. The setting for cleaning PTV Injector .............................................. 33
Figure 5. 3. The chromatogram of the blank....................................................... 33
Figure 5. 4. New Liner Design............................................................................ 34
Figure 5. 5. Pressure setting on the PTV ........................................................... 37
Figure 5. 6. The Liner from the second measurement......................................... 40

1
 LIST OF TABLES

Table 3. 1 List of Common GC Detector ............................................................ 17

Table 5. 1 Result of 1 Measurement .................................................................. 29
Table 5. 2 Result of 2 Measurement .................................................................. 38

1
 LIST OF CHROMATOGRAMS

Chromatogram 1 Result of First Measurement .................................................. 29

Chromatogram 2 Result of Second Measurement ............................................. 38

2
 Chapter I

PRELIMINARY
A. Internship Background
In line with increasing development in the industrial sector and Indonesia’s
participation in the ASEAN Economic Community, it is required for Vocational
High School – Bogor High School of Chemical Analyst to face the challenges.

The demands of industrial communities in the coming years will increase,

and with knowledge and skill intensive. Therefore, the development of
vocational education, especially the chemical analysis cluster should be
focused on the quality of the graduates. In this regard, the development pattern
used in the development of the education system becomes very important.

To overcome this, there needs to be a partnership between vocational

secondary schools and the industrial world, where they work together to meet
the competency standards of the graduates through various school programs,
including internship.

The legal basis of this internship refers to Government Regulation Number

41 of 2015 concerning about Development of Industrial Resources, namely
article 8 at points 1 – 3. In this article, it is stated that Vocational Education
Institutions can carry out cooperation with Industrial Companies in the form of
curriculum development, work practices (internship), and/or placement of
graduates, and the company is obliged to facilitate these activities.

With the internship program, students can be directly involved in the

industrial process and feel the industry atmosphere. On that occasion, students
can learn to adapt to the work environment, so they will become a professional,
excellent, dignified, and good environmental chemical analyst as the school
vision.

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 The vision and missions of Vocational High School – Bogor High School of
Chemical Analyst are as follows:
Vision
Being excellent with the environmental vision vocational school of chemical
analyst that produces professional and dignified graduates.

Missions
1) Carrying out qualified vocational education of chemical analysis to meet the
needs of business and industrial world communities both national and
international.
2) Increasing national and international partnerships.
3) Creating a sustainable culture of loving and caring for the environment.
4) Fostering and organizing social and civic functions.

B. Internship Objectives
The objectives of the internship are as follows:
1. Improving and strengthening students’ abilities and skills as a benefit,
based on chemical analysis study program.
2. Developing and strengthening students’ professional attitudes to enter new
work fields.
3. Improving students’ insight on potential aspects of the working world,
including, organizational structure, discipline, environment, and work
system.
4. Increase students’ knowledge in the use of more modern chemical analysis
instruments, compared to existing facilities at school.
5. Obtaining feedback to improve and develop the education in Vocational
High School – Bogor High School of Chemical Analyst.
6. Introducing the main duties and functions of a chemical analyst (graduates
of Vocational High School – Bogor High School of Chemical Analyst) to
research institutions and industries at internship institutions (as users of
chemical analysts).

2
 CHAPTER II

THE INTERNSHIP INSTITUTION

A. The History of Groningen University

Figure 2. 1. Groningen University Building

The University of Groningen (Abbreviated: UG; Dutch: Rijksuniversiteit

Groningen, abbreviated: RUG) is a public research university in Groningen, one of
the cities in the Netherlands. The university was founded in 1614 and is one of the
oldest universities in the Netherlands as well as one of the largest.

The founding of the University in 1614 – at that time still a college of higher
education – was an initiative taken by the Regional Assembly of the city of
Groningen and the Ommelanden, or surrounding region. There were four faculties
– Theology, Law, Medicine, and Philosophy.

The coat of arms of the university was confirmed by the States of the City
and County of Groningen in 1615. It consists of the provincial arms, charged with
an open book inscribed with the abbreviated words VER/BVM/DNI LV/CER/NA,
short for Verbum Domini Lucerna Pedibus Nostris.

3
Provincial College (1614 – 1815)

The council of the province Groningen and the Ommelanden, as the current
province of Groningen was then known, founded the university on 23 August 1614.
The brand-new academy was housed in the old and unused Menolda and Sywen
convent, on the North side of the Broerstraat. A year later saw the opening of the
University Library and Anatomy Theatre in the Minderbroeder Cloister across the
street from the Academiegebouw. The courtyard of the cloister was later used as
an academic cemetery.

Figure 2. 2.. Ubbo Emmius, the First Rector Magnificus of Groningen University

The development of the University came to a standstill at the end of the

seventeenth and during the eighteenth century because of theological differences
of opinion, a difficult relationship with the Regional Assembly, and political problems
that included the siege of the city by ‘Bommen Berend’ in 1672.

Academic College 1815-1876

In 1815, the University of Groningen, with other universities (Leiden and

Utrecht) was changed into Rijkshogescholen (State Colleges). The Faculty of
Philosophy was split up into 4 faculties: Arts, Philosophy, Mathematic, and Physics.

Figure 2. 3. Academic Building of Groningen University in 1850

4
State University 1877 – today

In the meantime, the Higher Education Act of 1876 had radically improved
the position of the university, which was renamed the Rijksuniversiteit Groningen
(RUG). Teaching now took place in Dutch as well as in Latin and the University
was given a research as well as an educational duty. This laid the foundations for
the present research university.
The University of Groningen developed apace during the first decades of
the twentieth century. The number of faculties and courses grew steadily while the
number of students showed an explosive growth. When the university celebrated
its first 300 years in 1914 there were 611 registered students; this had already
grown to 1000 by 1924. After a drop back during the Depression, and in particular
during the Second World War, the number of students grew rapidly from 1945 to
reach 20,000 in 1994. At the present time there are about 28,000 students
registered at the University of Groningen with the number of foreign students again
growing steadily. Following the tradition set by the first Rector Magnificus, the
number of German students and researchers has grown strongly in recent years.

Figure 2. 4. Groningen Univeristy Logo

5
B. Vission and Mission

Vision
The University of Groningen is an international academic
community in which disciplinary and cross-disciplinary research leads to
scientific breakthroughs and societal innovation, and in which talented
students are trained as innovators who will contribute to a sustainable
society. Its research and education are driven by intrinsic curiosity and
interaction with the global society. As a result, research, education, and
processes that have a societal impact are closely intertwined at the
University

The University of Groningen wants its students to become active,

independent, and responsible citizens who can think critically and help
solve the scientific and societal challenges of today and become the
entrepreneurs of tomorrow.

Six Ambitions
The following six ambitions for 2020 derive from the vision and are
central to the university’s strategy:

1. The University of Groningen will consolidate its position as an international

academic community with strong local roots. One of our activities to achieve
this is to establish national and international branch campuses. In this
international setting, research and education will benefit from the diverse
perspectives and approaches necessary to solve the big questions and
challenges faced by society.

2. The University of Groningen will help our researchers work on new, high-
risk ideas by fostering an innovative and entrepreneurial attitude.
Fundamental disciplinary and cross-disciplinary research with strong
international partners together with innovative interaction with society will
be central to the research-driven education that we provide.
3. The University of Groningen expects its students to be committed and
responsible participants in the teaching and learning processes. Enabling

6
 our students to be active learners is therefore the focus of our educational
strategy.

4. Putting knowledge to use is a key responsibility of the University. The

dissemination of knowledge and converting this knowledge into sustainable
economic and societal processes, services, and business activities will be
a cornerstone of University strategy.

5. The University of Groningen acknowledges a shared responsibility

for University strategy, management, and operation and this is
reflected in a continuous process of discussion and negotiation with
staff and students about the future of our institution. Trust forms the
basis of this process, as does the recognition of the different formal
roles within the process. Accountability and transparency with
regard to quality and funding are fundamental in this respect.

6. The alumni are our most important connection to society and we welcome
their involvement in our education and research through their contributions
in the alumni circles and various other activities.

With this strategy for 2020, the University of Groningen is confident that it can
continue and grow in its role as a prestigious international research university
in the next five years.

D. Faculties

At the University of Groningen research and education are organized with

several faculties as follows:
1. Economics and Business.

2. Behavioral and Social Sciences.

3. Theology and Religious Studies.

4. Arts.

5. Medical Sciences.

7
 6. Law.

7. Spatial Sciences.
8. Science and Engineering.

9. Philosophy.

10. University College Groningen.

11. University of Groningen/Campus Fryslân.

E. Committee of Deans
The Committee of Deans has an advisory role in a variety of fields. The
Committee is composed of the chairs of the Faculty Boards, also known as Deans.
The Rector Magnificus, as a member of the Board of the University, functions as a
chair.

The Committee of Deans is also responsible for the awarding of doctorates and
honorary doctorates. The names of the members as of 1st October 2018 are as
follows:

1. Prof. dr. E. Sterken, Rector Magnificus, Chairman

2. Prof. dr. M. Popović, Faculty of Theology and Religious Studies
3. Prof. dr. J.B. Wezeman, Faculty of Law
4. Prof. dr. M. Joëls, Faculty of Medical Science
5. Prof. dr. J. Knoester, Faculty of Science and Engineering
6. Prof. dr. G.C. Wakker, Faculty of Arts
7. Prof. dr. C.W.A.M. Aarts, Faculty of Behavioural and Social Sciences
8. Prof. dr. L.W. Nauta, Faculty of Philosophy
9. Prof. dr. O. Couwenberg, Faculty of Spatial Sciences
10. Prof. dr. J.B. Wezeman, Faculty of Law (ad interim)
11. Prof. dr. H. van Ees, University College Groningen
12. Prof. dr. A.J. Zwitter, Campus Fryslân

The name of the secretaries are as follows:

1. Mrs. M.A.S. Peperkamp
2. Mw. drs. T.H. Vugteveen, Management secretary

8
 CHAPTER III

LABORATORIUM ACTIVITY

A. Activity
When I did the internship program, I was placed in the Zernike Institute for
Advanced Materials, University of Groningen (Faculty of Science and
Engineering, at Chemical Engineering Department). During the internship
period, I did some analysis of various samples in many ways. Some of them
are sample analysis using XRF, turbidimeter, GC-MS, GCxGC-ToF-MS, and
some introductions to GPC, HPLC, FTIR, etc. And the main project carried out
for this report is the analysis of bitumen with the thermal desorption method
using the combined methods of PTV-GC-MS.

B. Literature Preview

1. Bitumen
Asphalt, also known as bitumen is a sticky, black, and highly viscous
liquid or semi-solid form of petroleum. It may be found in natural deposits
or may be a refined product, and is classed as a pitch. Before the 20th
century, the term asphaltum was also used. The word is derived from the
Ancient Greek ἄσφαλτος ásphaltos.

Figure 3. 1. Bitumen for waterproofing roof

The primary use (70%) of asphalt is in road construction, where it is used

as the glue or binder mixed with aggregate particles to create asphalt
concrete. Its other main uses are for bituminous waterproofing products,
including the production of roofing felt and for sealing flat roofs.

9
2. Thermal Desorption
Thermal desorption sampling refers to a number of related techniques that
include one or more steps in which sample heating releases volatile analytes
into the carrier-gas stream from an adsorbent or other involatile material. One
or more adsorption-desorption steps serve to concentrate analytes as well as
reduce their bandwidths to meet column injection requirements.

Volatiles enter the desorption tube from a variety of sources, including

directly from the atmosphere, from the headspace over a solid or liquid sample,
by sparging a liquid sample with inert gas, or as the effluent from a chemical
process or engine exhaust.

A related technique, thermal extraction, heats a solid or semisolid sample

directly in the carrier-gas stream using essentially the same equipment as
thermal desorption.

To distinguish it from pyrolysis injectors, thermal desorption operates at

lower temperatures and does not intentionally cause sample thermolysis. For
example, chromatographers can use thermal extraction to sample polymers,
waxes, powders, pharmaceutical formulations, solid foods, and cosmetics for
their volatile constituents.

Thermal Desorption Techniques

In its simplest form, thermal desorption involves heating a sample tube with
carrier gas flowing through it. The emerging gas is conducted directly to the GC
column.

10
 Figure 3. 2. Thermal Desorption setup

Figure 3.2 illustrates a simple thermal desorption setup. A tube containing

an adsorbent or sample material (or both) is positioned in the carrier gas
stream before the column inlet. After a short delay to flush out residual air, the
tube is heated and analytes are desorbed or thermally extracted directly from
the sample.

Carrier flow conducts the released volatile compounds into the column. In
practice, an existing inlet can provide a convenient base for a top-mounted
desorption system, or it can act as the terminus of a heated transfer line for
benchtop systems. After desorption has finished, the tube cools down and
normal carrier-gas flow is restored.

3. Programmable Temperature Vaporizer

The programmed temperature vaporizer (PTV), is a complete injector that
can be rapidly heated and cooled allowing the sample to be introduced in liquid
form at cool temperatures and then to be vaporized rapidly. Numerous
varieties of this type of injector are commercially available most of which
enable both split and splitless modes, and in some cases, on-column injection,
depending on the type of liner chosen.

Injector designs for the PTV are usually similar to non-programmable

versions except for the inclusion of rapid heating and cooling facilities. These
facilities may include the ability to use different programming ramps and
cryogenic cooling. PTV injectors are often operated with packed liners

11
depending on the type of application. Thus the packing may consist of glass
or silica wool, or adsorbent material to selectively remove certain materials.

Figure 3. 3. PTV Injector

General advantages of PTV are:

• Reduced needle – and injector discrimination (cold needle

injection)
• Large volume injection (LVI) possible
• Removal of the sample solvent before injection
• Holding back of non-volatile sample components in the liner
• Good accuracy and reproducibility
• Cold trapping of samples in the injector and the top of the (pre)
column

12
4. Gas Chromatography (GC)

Figure 3. 4. GC Hewlett Packard 5890 II

Gas chromatography (GC) is a common type of chromatography used in

analytical chemistry for separating and analyzing compounds that can be
vaporized without decomposition. Typical uses of GC include testing the purity
of a particular substance or separating the different components of a mixture
(the relative amounts of such components can also be determined). In some
situations, GC may help in identifying a compound. In preparative
chromatography, GC can be used to prepare pure compounds from a mixture.

In gas chromatography, the components of a sample are dissolved in

a solvent and vaporized to separate the analytes by distributing the sample
between two phases: a stationary phase and a mobile phase. The mobile
phase is a chemically inert gas that serves to carry the molecules of the
analyte through the heated column. Gas chromatography is one of the sole
forms of chromatography that does not utilize the mobile phase for
interacting with the analyte. The stationary phase is either a solid
adsorbant, termed gas-solid chromatography (GSC), or a liquid on an inert
support, termed gas-liquid chromatography (GLC).

13
Instrumentation

Figure 3.5. GC Instrumentation Scheme

Carrier Gas
The carrier gas must be chemically inert. Commonly used gases
include nitrogen, helium, argon, and carbon dioxide. The choice of carrier
gas is often dependant upon the type of detector which is used. The carrier
gas system also contains a molecular sieve to remove water and other
impurities.

Sample Injection Port

For optimum column efficiency, the sample should not be too large,
and should be introduced onto the column as a "plug" of vapor - slow
injection of large samples causes band broadening and loss of resolution.
The most common injection method is where a microsyringe is used to
inject samples through a rubber septum into a flash vapouriser port at the
head of the column.

The temperature of the sample port is usually about 50°C higher than
the boiling point of the least volatile component of the sample. For packed
columns, sample size ranges from tenths of a microliter up to 20 microliters.
Capillary columns, on the other hand, need much less sample, typically
around 10-3 mL. For capillary GC, split/splitless injection is used. Have a
look at this diagram of a split/splitless injector;

14
 Figure 3. 6. GC Injector

The injector can be used in one of two modes; split or splitless. The
injector contains a heated chamber containing a glass liner into which the
sample is injected through the septum. The carrier gas enters the chamber
and can leave by three routes (when the injector is in split mode). The sample
vapourises to form a mixture of carrier gas, vapourised solvent, and
vapourised solutes. A proportion of this mixture passes onto the column but
most exits through the split outlet. The septum purge outlet prevents septum
bleed components from entering the column.

Columns

There are two general types of the column, packed and capillary (also
known as open tubular). Packed columns contain a finely divided, inert, solid
support material (commonly based on diatomaceous earth) coated with a
liquid stationary phase. Most packed columns are 1.5 - 10m in length and have
an internal diameter of 2 - 4mm.

Capillary columns have an internal diameter of a few tenths of a millimeter.

They can be one of two types; wall-coated open tubular (WCOT) or support-
coated open tubular (SCOT). Wall-coated columns consist of a capillary tube
whose walls are coated with a liquid stationary phase.

In support-coated columns, the inner wall of the capillary is lined with a thin
layer of support material such as diatomaceous earth, onto which the
stationary phase has been adsorbed. SCOT columns are generally less

15
efficient than WCOT columns. Both types of the capillary column are more
efficient than packed columns.

In 1979, a new type of WCOT column was devised - the Fused Silica Open
Tubular (FSOT) column;

Figure 3. 3. Cross-section of Fused Silica Open Tubular Column

These have much thinner walls than the glass capillary columns and are
given strength by the polyimide coating. These columns are flexible and can
be wound into coils. They have the advantages of physical strength, flexibility,
and low reactivity.

Column temperature

For precise work, column temperature must be controlled to within tenths

of a degree. The optimum column temperature is dependant upon the boiling
point of the sample. As a rule of thumb, a temperature slightly above the
average boiling point of the sample results in an elution time of 2 - 30 minutes.
Minimal temperatures give good resolution but increase elution times. If a
sample has a wide boiling range, then temperature programming can be
useful. The column temperature is increased (either continuously or in steps)
as separation proceeds.

Detectors

Many detectors can be used in gas chromatography. Different detectors will

give different types of selectivity. A non- selective detector responds to all
compounds except the carrier gas, a selective detector responds to a range
of compounds with a common physical or chemical property and a specific
detector responds to a single chemical compound.

16
 Detectors can also be grouped into concentration dependant detectors and
mass flow dependant detectors. The signal from a concentration dependant
detector is related to the concentration of solute in the detector, and does not
usually destroy the sample Dilution of with make- up gas will lower the
response of the detector. Mass flow dependant detectors usually destroy the
sample, and the signal is related to the rate at which solute molecules enter the
detector. The response of a mass flow dependant detector is unaffected by
make-up gas.

A tabular summary of common GC detectors:

Support Dynamic
Detector Type Selectivity Detectability
gases range
Flame
Hydrogen
ionization Mass flow Most organic cpds. 100 pg 107
and air
(FID)
Thermal
conductivity Concentration Reference Universal 1 ng 107
(TCD)
Halides, nitrates,
Electron
nitriles, peroxides,
capture Concentration Make-up 50 fg 105
anhydrides,
(ECD)
organometallics
Nitrogen- Hydrogen
Mass flow Nitrogen, phosphorus 10 pg 106
phosphorus and air

Hydrogen Sulfur, phosphorus,

Flame
and air tin, boron, arsenic,
photometric Mass flow 100 pg 103
possibly germanium, selenium,
(FPD)
oxygen chromium

Aliphatics, aromatics,
ketones, esters,
Photoioni
aldehydes, amines,
zation Concentration Make-up 2 pg 107
heterocyclics,
(PID)
organosulphur, some
organometallics

Hall
Hydrogen, Halide, nitrogen,
electrolytic Mass flow
oxygen nitrosamine, sulfur
conductivity
Table 3. 1 List of Common GC Detector

17
 Mass Spectrometry (MS)
Mass spectrometry is an analytical tool useful for measuring the mass-to-
charge ratio (m/z) of one or more molecules present in a sample. These
measurements can often be used to calculate the exact molecular weight of the
sample components as well. Typically, mass spectrometers can be used to identify
unknown compounds via molecular weight determination, to quantify known
compounds, and to determine the structure and chemical properties of molecules.

How does a mass spectrometer perform such a feat? Every mass spectrometer
consists of at least these three components:S

• Ionization Source
• Mass Analyzer
• Ion Detection System

The Ionization Port

Molecules are converted to gas-phase ions so that they can be moved
about and manipulated by external electric and magnetic fields. In our laboratory,
we use a technique called nanoelectrospray ionization, which is somewhat
similar to how cars are industrially painted. This method allows for creating
positively or negatively charged ions, depending on the experimental
requirements. Nanoelectrospray ionization can directly couple the outlet of a
small-scale chromatography column directly to the inlet of a mass spectrometer.
The flow from the column is passed through a needle that is 10- 15 um at its tip.

The Mass Analyzer

Once ionized, the ions are sorted and separated according to mass-to-
charge (m/z) ratios. There are some mass analyzers currently available, each
of which has trade-offs relating to the speed of operation, resolution of
separation, and other operational requirements. The specific types in use at the
Broad Institute are discussed in the next section. The mass analyzer often works
in concert with the ion detection system.

Quadrupole Mass Analyzer

The quadrupole mass analyzer (QMS) is one type of mass analyzer used
in mass spectrometry. It is also known as a transmission quadrupole mass

18
 spectrometer, quadrupole mass filter, or quadrupole mass spectrometer. As
the name implies, it consists of four cylindrical rods, set parallel to each other.

In a quadrupole mass spectrometer, the quadrupole is the mass analyzer - the

component of the instrument responsible for selecting sample ions based on their
mass-to-charge ratio (m/z). Ions are separated in a quadrupole based on the
stability of their trajectories in the oscillating electric fields that are applied to the
rods.

The quadrupole consists of four parallel metal rods. Each opposing rod pair is
connected electrically, and a radio frequency (RF) voltage with a DC offset voltage
is applied between one pair of rods and the other. Ions travel down the quadrupole
between the rods. Only ions of a certain mass-to-charge ratio will reach the detector
for a given ratio of voltages: other ions have unstable trajectories and will collide
with the rods. This permits selection of an ion with a particular m/z or allows the
operator to scan for a range of m/z-values by continuously varying the applied
voltage. Mathematically this can be modeled with the help of the Mathieu differential
equation.

Figure 3. 4. Ion path through quadrupole illustration

Ideally, the rods are hyperbolic. Cylindrical rods with a specific ratio of rod
diameter-to-spacing provide an easier-to-manufacture adequate approximation to
hyperbolas. Small variations in the ratio have large effects on resolution and peak
shape. Different manufacturers choose slightly different ratios to fine-tune operating
characteristics in the context of anticipated application requirements. In recent decades
some manufacturers have produced quadrupole mass spectrometers with true
hyperbolic rods.

19
The Ion Detection System
The separated ions are then measured and sent to a data system where
the m/z ratios are stored together along with their relative abundance. A mass
spectrum is simply the m/z ratios of the ions present in a sample plotted against
their intensities. Each peak in a mass spectrum shows a component of unique
m/z in the sample, and heights of the peaks connote the relative abundance of the
various components in the sample.

Figure 3. 5. An example of Mass chromatogram

20
 CHAPTER IV

Analytical Method

A. Project Overview
1. Bitumen Sample
The analysis aimed to know about what components appear in
several temperatures (qualitative analysis) thus will help in general uses.
The bitumen has to be heated up first before applied, and since the bitumen
sample that I used, is a recycled product, it may contain hazardous material
and may emit harmful smoke when heated. The safety guide about this
bitumen is very necessary for its processing and utilization.

Figure 4. 1. The worker heating the bitumen before they use it

To do the analysis, I used the thermal desorption process of

bitumen sample in the not-really high temperature so it does not undergo
pyrolysis. I do not do the pyrolysis is because I only want to know about
what gasses will appear when people heat it before applying the bitumen,
and the temperature is not that high as the pyrolysis process.

I did the desorption process using sequence with 7 different

temperatures starting from 50°C and end at 350°C with 50 degrees
difference per each. I did the sequence program on the PTV injector, which
will be explained more in the PTV-GC-MS chapter.

21
1. Sample Preparation
The sample is semi-solid bitumen and there is no special treatment
needed for the sample to be analyzed using this method. It just needs to be
weighed ±0.100 gram on the clean weigh paper.

Figure 4. 2. Bitumen sample

After that, the sample made into a long shape (like a rope), so it will be
easier to wrap it around the micropipette.

The reason I use the micropipette it’s because when the sample heated
until the high temperature, it will be melted and the carrier gas can not go
through it because a melted bitumen is very sticky and will block the gas
way.

Below the micropipette, I put some quartz wool (it will better than using
the glass wool because I will heat it to high temperature and the glass wool
may be melted in that situation). The quartz wool also holds the drop from
the melted bitumen to the column, so it will help to avoid column
contamination.

22
 Figure 4. 3. Sample in the liner

2. PTV-GC-MS

In this experiment, I use the combined method of PTV-GC-MS. After

preparing the sample on the liner, put it on the injector (in this case, PTV
injector).

The PTV (Programmable Temperature Vaporizer) as I explained

before in Chapter III: Literature review, is an injector that the temperature
on it can be controlled by both of its hardware and software.

Figure 4. 4. The opening of PTV Injector

23
 The software name is Optic 3.2 optic method editor, and in this
software, I programmed all of the different temperatures to do the desorption
process.

Figure 4. 5. The program of the last temperature in PTV

In the hardware, the analyst also can control the carrier gas
flow if the GC system is an error or problematic.

Figure 4. 6. PTV Hardware

After the sample had been desorpted by the high temperature on PTV,
it will become a gas molecule phase and with the carrier gas, it will be
carried to the GC column to be separate.

24
 It believed that using GC could carry out most effectively a thorough
analysis of the complex composition of bitumen.

Figure 4. 7. GC-MS Instrument

After all molecules have been separated, it will go to the MS system. The
reason I use the MS detector is that Mass spectrometer (MS) can be identified the
compound by comparing it with the compound list in its library.

25
 CHAPTER V

RESULTS AND DISCUSSION

1. First Measurement
For the first measurement, I used a complete sequence with seven different
temperatures. The detail description of how many samples I weighed and the
program I set for the instrument will explain below.
Sample Weigh Description

Weighing Date : 11/02/2020

: Bitumen Sample
Sample name no.1
Sample weigh : 0,1040

Instrument Description

Gas Chromatograph : Hewlett Packard 5890 Series II

Mass Spectrometric Detector : HP - MSD 5973
Column : Rxi®-5Sil MS (Crossbond®, selectivity
close to 5% diphenyl/95% dimethyl
polysiloxane) 30 m, 0.25 mmID, 1.0 µm
df
Carrier gas : Helium

Instrumentation Program for 1st and 2nd Measurements

PTV Temperature 1 : 50˚ C

PTV Temperature 2 : 100˚ C
GC Program
Oven Program
Init. Temp : 40˚
Init. Time : 20.00 min
Rate (C/min) : 10.00
Final Temp.(C) : 300
Final Time (Min) : 5.00
Zone Temperatures
Det. B : 280
Oven Parameters
Oven Equib. Time : 0.50 min
Oven Max : 350˚C
Run Time: 51min

26
Instrumentation Program for 3rd Measurement

PTV Temperature : 150˚ C

GC Program
Oven Program
Init. Temp : 40˚
Init. Time : 10.00 min
Rate (C/min) : 10.00
Final Temp.(C) : 300
Final Time (Min) : 5.00
Zone Temperatures
Det. B : 280
Oven Parameters
Oven Equib. Time : 0.50 min
Oven Max : 350˚C
Run Time: 41min

Instrumentation Program for 4th Measurement

PTV Temperature : 200˚ C

GC Program
Oven Program
Init. Temp : 40˚
Init. Time : 5.00 min
Rate (C/min) : 10.00
Final Temp.(C) : 300
Final Time (Min) : 5.00
Zone Temperatures
Det. B : 280
Oven Parameters
Oven Equib. Time : 0.50 min
Oven Max : 350˚C
Run Time: 36min

27
Instrumentation Program for 5th, 6th, and 7th Measurements

PTV Temperature : 250˚ C

PTV Temperature : 300˚ C
PTV Temperature : 350˚ C
GC Program
Oven Program
Init. Temp : 40˚
Init. Time : 0.00 min
Rate (C/min) : 15.00
Final Temp.(C) : 300
Final Time (Min) : 10.00
Zone Temperatures
Det. B : 280
Oven Parameters
Oven Equib. Time : 0.50 min
Oven Max : 350˚C
Split Ratio
Split 50:1
Run Time: 27.33 min

As shown above, the initial time of each temperature is different. Only the last
three measurements I did with split (the temperature 5, 6, and 7). The reason I did
the split only in those temperatures is to avoid too much sample that will go into
the column remember that all of those temperatures are high, so it will also produce
more gasses.

We need to keep in mind that the sequence measured automatically by the PTV-
GC-MS sequence program. I only have to run once at the beginning and leave it
for the whole night and check it tomorrow morning, since it needs less 6 hours to
run all of the temperatures.

28
 B. Results from the First Measurement

Sequence of Bitumen sample no. 2

Chromatogram 1 Result of First Measurement

Sample name: Bitumen no.2

Measuring Date: 5 February 2020

Table 5. 1 Result of 1 Measurement

Run 1, PTV 50°C
Peak
tR (min) Corr. Area % of Total Compound Name Qual
Number
1 4.889 21772510 100.00% Unknown (broad peak in the beginning)
Total Corrected
21772510
Areas

Run 2, PTV 100°C

Peak Corr.
tR (min) % of Total Compound Name Qual
Number Area
1 5.836 23356549 11.36% Unknown
2 32.987 363935 1.28% Oxalic acid, allyl nonyl ester 64
Total Corrected
28527317
Areas

29
 Run 3, PTV 150°C
Peak
tR (min) Corr. Area % of Total Compound Name Qual
Number
1 3.079 14321783 72.18% Unknown
2 20.676 496325 2.50% Octane 64
3 21.326 605350 3.05% Undecane 83
4 22.512 885246 4.46% Benzene, 1-methyl-2-(1-methylethyl)- 72
5 22.981 517702 2.61% Dodecane 87
6 24.482 373743 1.88% Tridecane 91
Total Corrected
19842943
Areas

Run 4, PTV 200°C

Peak
tR (min) Corr. Area % of Total Compound Name Qual
Number
1 2.559 8514839 65.03% Unknown
2 17.528 341409 2.61% Benzene, 1,2-diethyl 80
3 17.993 360168 2.75% Dodecane 90
4 18.193 155963 1.19% Undecane, 2,6-dimethy- 72
5 19.487 349306 2.67% Undecane 83
6 20.886 295896 2.26% Decane 72
7 22.204 158121 1.21% Hexadecane 72
Total Corrected
Areas 13094687

Run 5, PTV 250°C

Peak
tR (min) Corr. Area % of Total Compound Name Qual
Number
1 0.708 46369 0.82% Unknown
2 22.203 124290 2.21% Oxalic acid, allyl nonyl ester 64
3 23.445 122305 2.17% Undecane, 5,7-dimethyl 72
4 26.801 174111 3.09% Hexatriacontane 72
5 27.813 191841 3.41% Dotriacontane 72
6 28.779 169973 3.02% Sulfurous acid, 2-propyl tetradecyl ester 72
Total Corrected
Areas 5632867

30
 Run 6, PTV 300°C
Peak Corr.
tR (min) % of Total Compound Name Qual
Number Area
1 2.11 11367165 61.69% Unknown
2 11.233 964850 5.24% Cyclotrisiloxane, hexamethyl- 83
3 19.489 231848 1.26% Undecane 78
4 20.888 308240 1.67% Hexadecane 78
5 22.205 298658 1.62% Tetradecane 72
6 23.449 347349 1.89% Eicosane 86
7 24.624 383010 2.08% Dotriacontane 86
8 25.739 283986 1.54% Hexatriacontane 86
9 26.801 344815 1.87% Heptacosane, 1-chloro- 80
10 27.812 332518 1.80% Tetratetracontane 87
11 28.779 373935 2.03% Pentadecane 96
12 29.703 681052 3.70% Hexadecane 95
13 30.585 321594 1.75% Heptadecane 90
14 31.449 448268 2.43% Tetrapentacontane, 1,54-dibromo 60
Total Corrected
Areas 18426802

Run 7, PTV 350°C

Peak
tR (min) Corr. Area % of Total Compound Name Qual
Number
1 2.32 13973941 36.74% Unknown
2 11.415 15210521 40.00% Cyclotetrasiloxane, octamethyl- 64
3 16.482 392088 1.03% Undecane 90
4 18.063 462155 1.22% Dodecane 91
5 21.214 1000641 2.63% Oxalic acid, cyclobutyl tridecyl ester 78
6 22.351 604504 1.59% 1-Octanol, 2-butyl- 64
7 24.835 1277758 3.36% 2-Piperidinone, N-[4-bromo-n-butyl ]- 83
Total Corrected
Areas 38030837

31
 In the tables above, the Total Corrected Areas is the sum of all peak areas that
appear in my sample. I do not put all the components list here because it too much
and most of the compound is just has a little percentage of the total.

According to the chromatogram, at the last temperature (350˚C ) there is a very

high and broad peak in the last part of the chromatogram. It is not good because it
can indicate that there is something wrong.

I did ion extraction from column bleeding (207) to check if that very high peak is
from leaking of stationary phase inside the column, but it is not from the column
bleed.

The injector side also very dirty because of the melted bitumen sample. Since
the bitumen is a very sticky component, the liner gets stucks inside the injector.
When I tried to pull it out, the liner got broken.

Figure 5. 1. The liner got broken and dirty after measurement

The melted bitumen also dropped into the column opening, which makes it
have to be cut. I cleaning the injector by set it in stand by mode at 600˚C temperature
for about 40 minutes to burn the melted sample inside the injector.

32
 Figure 5. 2. The setting for cleaning PTV Injector

After cleaned the instrument I did some blanks to see if it clean or not, but the
baseline was very dirty. It indicated that the column is already contaminated
remember there was some melted sample inside the column.

Figure 5. 3. The chromatogram of the blank

33
 To solve this problem, I designed a new liner that has a capillary tube inside.
The idea is to close the bottom of the liner but still can make way for the carrier gas
can go through. Since the very high peak only appears in the last temperature run
(350˚C), I skip this temperature in my second measurement, to avoid the same
problem happen.

Figure 5. 4. New Liner Design

34
 2. Second Measurement
For the second measurement, I change the liner with the new one,
and as I said before I only did six different temperatures. The detail
description of how many samples I weighed and the program I set for the
instrument will explain below.

Sample Weigh Description

Weighing Date : 11/02/2020

: Bitumen Sample
Sample name no.1
Sample weigh : 0,1040 grams

Instrument Description

Gas Chromatograph : Hewlett Packard 5890 Series II

Mass Spectrometric Detector : HP - MSD 5973
Column : Rxi®-5Sil MS (Crossbond®, selectivity close
to 5% diphenyl/95% dimethyl polysiloxane)
30m, 0.25 mmID, 1.0 µm df

Carrier gas : Helium

Instrumentation Program for 1st and 2nd Run

PTV Temperature 1 : 50˚ C

PTV Temperature 2 : 100˚ C
GC Program
Oven Program
Init. Temp : 40˚
Init. Time : 20.00 min
Rate (C/min) : 10.00
Final Temp.(C) : 300
Final Time (Min) : 5.00
Zone Temperatures
Det. B : 280

Oven Parameters
Oven Equib. Time : 0.50 min
Oven Max : 350˚C
Run Time: 51min

35
Instrumentation Program for 3rd Run

PTV Temperature : 150˚ C

GC Program
Oven Program
Init. Temp : 40˚
Init. Time : 10.00 min
Rate (C/min) : 10.00
Final Temp.(C) : 300
Final Time (Min) : 5.00
Zone Temperatures
Det. B : 280
Oven Parameters
Oven Equib. Time : 0.50 min
Oven Max : 350˚C
Run Time: 41min

Instrumentation Program for 4th Run

PTV Temperature : 200˚ C

GC Program
Oven Program
Init. Temp : 40˚
Init. Time : 5.00 min
Rate (C/min) : 10.00
Final Temp.(C) : 300
Final Time (Min) : 5.00
Zone Temperatures
Det. B : 280
Oven Parameters
Oven Equib. Time : 0.50 min
Oven Max : 350˚C
Run Time: 36min

36
Instrumentation Program for 5th and 6th Run

PTV Temperature : 250˚ C

PTV Temperature : 300˚ C

GC Program
Oven Program
Init. Temp : 40˚
Init. Time : 0.00 min
Rate (C/min) : 15.00
Final Temp.(C) : 300
Final Time (Min) : 10.00
Zone Temperatures
Det. B : 280
Oven Parameters
Oven Equib. Time : 0.50 min
Oven Max : 350˚C
Split Ratio
Split 50:1
Run Time: 27.33 min

The setting for the instrumentation program is the same with the first
measurement, but only the carrier gas pressure here is controlled by the PTV
hardware (in the first measurement, it controlled by the GC-MS system). I change
the control because when I want to do blank before measuring the sample, the
pressure always drops without any leaking on the system. Then I thought there
must be something wrong with the gas controller.

Figure 5. 5. Pressure setting on the PTV

37
Results from the Second Measurement

Sequence of Bitumen sample no. 1

Chromatogram 2Result of Second Measurement

Sample name: Bitumen no.1

Measuring Date: 13 February 2020

Table 5. 2 Result of 2 Measurement

Run 1, PTV 50°C

Peak tR % of
Compound Name Qual Corr. Area
Number (min) Total
1 32.317 Silane,trichlorodocosyl 72 2986555 4.04%
Total Corrected Areas 74004600

Run 2, PTV 100°C

Peak % of
tR (min) Compound Name Qual Corr. Area
Number Total
1 30,162 1-Nonene 80 12583560 13.008%
2 31,514 Silanae, trichlorodocosyl- 74 6622160 6.845%
3 33,682 1-Dodecanol, 2-methyl-, (S)- 76 3995138 4.130%
4 34,165 1-Octanol, 2-butyl- 80 11604556 11.996%
5 34,394 1-Dodecene 89 3031146 3.133%
6 35,371 Cyclooctane, methyl 60 1177218 1.217%
7 35,724 Cyclododecane 89 1392250 1.439%
8 37,390 Oxalic acid, allyl octadecyl ester 70 2687231 2.778%
Total Corrected Areas 18426802

38
 Run 3, PTV 150°C
Peak tR % of
Compound Name Qual Corr. Area
Number (min) Total
1 20,310 Silane, trichlorodocosyl- 90 8494857 4.248%
2 22,348 Undecane 70 25852314 12.928%
3 23,739 Benzene, 1,2,4,5-tetramethyl- 94 8208040 4.105%
4 24,041 1-Dodecene 96 2613004 1.307%
5 24,180 Dodecane 94 29226701 14.615%
6 24,390 Undecane, 2,6-dimethyl- 76 10381475 5.191%
7 25,153 Cyclododecane 95 3377000 1.689%
8 25,366 Dodecane, 4,6-dimethyl 78 2645284 1.323%
9 25,724 3-Tetradecene, (Z)- 99 6240882 3.121%
10 25,837 Tridecane 98 27713154 13.859%
11 26,819 Cyclotridecane 90 3846039 1.923%
12 27,379 Tetradecane 98 14237949 7.120%
13 28,242 Undecane 64 2316672 1.159%
14 28,824 Pentadecane 94 4742019 2.371%
15 30,183 hexadecane 93 2560970 1.281%
Total Corrected Areas 199970809

Run 4, PTV 200°C

Peak tR
Compound Name Qual Corr. Area % of Total
Number (min)
1 15,583 Silane,trichlorodocosyl- 74 4650048 2.197%
2 Cyclohexane, 1,2,3-trimethyl-,
16,995 84 3345226 1.581%
(1.alpha.,2.beta.,3.alpha.)-
3 17,543 Undecane 92 8139549 3.846%
4 18,899 Benzene, 1-ethyl-2,4-dimethyl 93 4751069 2.245%
5 19,323 Dodecane 94 14338009 6.775%
6 19,530 Undecane, 2,6-dimethyl- 95 4701301 2.221%
7 20,858 3-Tetradecene, (Z)- 96 4295056 2.029%
8 21,959 Decane 83 3103370 1.466%
9 25,329 Hexadecane 98 3572600 1.688%
10 26,643 Heptadecane 96 2442263 1.154%
Total Corrected Areas 211640955

: May come from Stationary phase inside the column

39
 In the tables above, the Total Corrected Areas is the sum of all peak areas that
appear in my sample. I do not put all the components list here because it too much
and most of the compound is just has a little percentage of the total.

I could not do the data analysis from the 5th and 6th run because there is no
peak except the spike (fake peak), and the very high peak (the sample drop inside
the column).

This used liner from the second measurement. It improved because there was
no melted sample inside the injector.

Figure 5. 6. The Liner from the second measurement

The same problem still appeared on the last two temperatures run (250˚ and
300˚C). There is a very high peak at the end of the chromatogram because the
column is contaminated. There are still some drops of the melted sample inside the
column and it caused the peak to become very high.

40
 Chapter VI

CONCLUSION AND SUGGESTION

A. Conclusion
According to the measurements, the average components that contain in the
bitumen are; Air, Aldehyde, Hydrocarbon, Carboxylic acid, Aromatic
Hydrocarbon, Alcohol, Policyclic Aromatic Hydrocarbon, Haloalcane, formamide,
Organosulfur Compound, Organosilicon Compound, and some components that
unknown.

B. Suggestion
By having those results and problems, here are some suggestions that might
be useful for the improvements of this method:
1. For the high temperature (last three temperatures run) maybe it will be better
if we first trap the gas and analysis it separately.
2. For cleaning the liner after doing the measurement, using Anisole is the best
choice because bitumen solved well in it.
3. Bitumen also can be analyzed with GC-MS by first solve it with Anisole, and
measure it with less amount of sample injection.

41
 BIBLIOGRAPHY

Jones, Daniel (2011). Roach, Peter; Setter, Jane; Esling, John (eds.). Cambridge
English Pronouncing Dictionary (18th ed.). Cambridge University Press.
ISBN 978-0-521-15255-6.

Sörensen, Anja; Wichert, Bodo (2009). "Asphalt and Bitumen". Ullmann's

Encyclopedia of Industrial Chemistry. doi:10.1002/14356007.a03_169.pub2.
ISBN 978-3527306732.

http://www.chromatographyonline.com/thermal-desorption-sampling?pageID=5.
Accessed on 23 February 2020

https://chem.libretexts.org/Bookshelves/Analytical_Chemistry/Supplemental_Modules_
(Analytical_Chemistry)/Chromedia/01Gas_Chromotography_(GC)/Gas_Chromoto
graphy%3A_In_Practice/02Gas_Chromatography%3A_Injection_techniques_and_
principles/13The_PTV_injector. Accessed on 23 February 2020

https://teaching.shu.ac.uk/hwb/chemistry/tutorials/chrom/gaschrm.htm.
Accessed on 23 February 2020
De Hoffmann, Edmond; Vincent Stroobant (2003). Mass Spectrometry: Principles and
Applications (Second ed.). Toronto: John Wiley & Sons, Ltd. p. 65. ISBN 978-0-471-
48566-7.

Teschl, Gerald (2012). Ordinary Differential Equations and Dynamical Systems.

Providence: American Mathematical Society. ISBN 978-0-8218-8328-0.

42
 Appendices
A. Chromatogram of Bitumen sample no.2 (First Measurement)

43
44
45
46
B. Chromatogram of Bitumen sample no.1 (Second Measurement)

Chromatogram 1, PTV 50°C

120000

100000

80000

60000

40000

20000

0
0 10 20 30 40 50 60

Chromatogram 2, PTV 100°C

300000

250000

200000

150000

100000

50000

0
0 10 20 30 40 50

47
 Chromatogram 3, PTV 150°
1400000

1200000

1000000

800000

600000

400000

200000

0
0 5 10 15 20 25 30 35 40 45

Chromatogram 4, PTV 200°

1000000
900000
800000
700000
600000
500000
400000
300000
200000
100000
0
0 5 10 15 20 25 30 35 40

48
 Chromatogram 5, PTV 250°
3000000

2500000

2000000

1500000

1000000

500000

0
0 5 10 15 20 25 30 35 40

Chromatogram 6, PTV 300°

1800000

1600000

1400000

1200000

1000000

800000

600000

400000

200000

0
0 5 10 15 20 25 30 35 40

49