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Journal of Applied Chemical Research
(Indexed by Ministry of Science and ISC)
Editor-in-Chief
Ali Mahmoudi, Ph.D. (Associate Prof., Islamic Azad University, Karaj Branch, Iran)
Managing Editor
Abbas Ahmadi, Ph.D. (Associate Prof., Islamic Azad University, Karaj Branch, Iran)
Regional Editor
Bita Mohtat, Ph.D. (Associate Prof., Islamic Azad University, Karaj Branch, Iran)
Editorial Board
Saeed Dehghanpour, Ph.D. (Associate Prof., Alzahra University, Tehran, Iran)
Lida Fotouhi, Ph.D. (Prof., Alzahra University, Tehran, Iran)
Nader Zabarjad, Ph.D. (Associate Prof., Islamic Azad University, Central branch, Iran)
Mahmoud Sharimoghadam, Ph.D. (Prof., Tarbiatemoalem University, Tehran, Iran)
Khodadad Nazari, Ph.D. (Associate Prof., Petroleum Research Institute, Tehran, Iran)
Mohsen Daneshtalab, Ph.D. (Prof., Memorial University, Canada)
Masayuki Sato, Ph.D. (Prof., Shizoka University, Japan)
R.K.Agarwall, Ph.D. (Prof., Singh University, India)
Surendra Prasad, Ph.D. (Prof., South Pacic University, Fiji)
Literal Editor
Natasha Pourdana, Ph.D. (Assistant Prof.)
Volume 7, No.4, 2013
Address
Faculty of Science, Islamic Azad University, Karaj branch
P.O. Box: 31485-313, Karaj, Iran (www.jacr.kiau.ac.ir )
Journal of Applied Chemical Research, 7, 4 (2013)
2
Content of issue Pages
1. Probing the Nature of Annealing Silicon Carbide Samples for Solar Cell
Ahmad Zatirostami
*1
, Khikmat Muminov


2
, A.Kholov
3
1
Department of Science and Engineering, Sari Branch, Islamic Azad University, Sari, Iran.
2,3
Academy of Science of the Republic of Tajikistan, S.U.Umarov, Physical Technical Institute, Tajikistan.
7
2. Determination of Saturates, Aromatics, Resins and Asphaltenes (SARA) Fractions
in Iran Crude oil Sample by Means of Chromatography Methods:Study of the
Geochemical Parameters
Elham Keshmirizadeh
*
, Somayeh Shobeirian
1
, Mahmoud Memariani
2

1
Department of Applied Chemistry, Islamic Azad University, Karaj Branch, Iran.
2
Chemistry Research Institute of Petroleum Industry-Geosciences Research Division, Tehran, Iran.
15
3. A Study on Peel Volatile Constituents and Juice Quality Parameters of Four
Tangerine (Citrus reticulata) Cultivars from Ramsar, Iran
Behzad Babazadeh Darjazi
Department of Horticulture, Faculty of Agriculture, Roudehen Branch, Islamic Azad University, Roudehen, Iran.
25
4. A Novel Method for the Synthesis of CaO Nanoparticle for the Decomposition of
Sulfurous Pollutant

Meysam Sadeghi
*1
, Mir Hassan Husseini
2
1,2
Department of Chemistry, Faculty of Sciences, Imam Hussein Comprehensive University, Tehran, Iran.
2
Nano Center Research, Imam Hussein Comprehensive University, Tehran, Iran.
39
5. Removal of Basic Blue 159 from Aqueous Solution Using Banana Peel as a Low-
Cost Adsorbent
Maral Pishgar
1*
, Mohammad Esmaeil Yazdanshenas
2
, Mohammad Hosein Ghorbani
1
,
Khosro Farizadeh
3
1
Islamic Azad University South Tehran Branch, Tehran, Iran.
2
Islamic Azad University Yazd Branch, Textile Department, Yazd, Iran.
3
Islamic Azad University Shahre Rey Branch, Textile Department, Tehran, Iran.
51
6. Development of a Mild Hydrothermal Method toward Preparation of ZnS
Spherical Nanoparticles
Leila Vafayi

1
, Soodabe Gharibe
1
, Shahrara Afshar
2
1
Department of Science, Islamic Azad University, Firoozkooh Branch, Iran.
2
Department of Chemistry, Iran University of Science and Technology, 16846-13114 Tehran, Iran.
63
7. Quantum Chemical Investigations of the Photovoltaic Properties of Conjugated
Molecules Based Oligothiophene and Carbazole
N. Belghiti
1
, M. N. Bennani
1
, Si Mohamed Bouzzine
2
, Mohamed Hamidi
2
, Mohamed
Bouachrine
3*

1
Laboratoire de Recherche «Chimie-Biologie appliquées à l’environnement», Faculté des Sciences, Université
Moulay Ismail Meknès, Maroc.
2
URMM/UCTA, Faculté des Sciences et Techniques d’Errachidia, Université Moulay Ismaïl, Maroc.
3

ESTM, Université Moulay Ismail, Meknes, Maroc.
71
8. New Benzimidazoles Derivatives: Synthesis, Characterization and Antifungal Activities
Abbas Ahmadi
*
, Babak Nahri-Niknafs
Pharmaceutical Sciences Branch, Islamic Azad University, Tehran, Iran.
85
Journal of Applied Chemical Research, 7, 4 (2013)
3
Journal of Applied Chemical Research (JACR) (Journal of Applied Chemistry, JAC, before)
is published quarterly by Islamic Azad University (Karaj Branch). Copyright is reserved by the
University.
Aims and Scope
JACR is an Iranian journal covering all elds of chemistry. JACR welcomes high quality
original papers in English dealing with experimental and applied research related to all Branches
of chemistry .These includes the elds of analytical, inorganic, organic, physical and applied
chemistry area. Review articles discussing specic areas of chemistry of current chemical
importance are also published. Journal of Applied Chemical Research ensures visibility of your
research results to Iranian scientists. You are kindly invited to submit your manuscript to this
Journal. All contributions in the form of original papers or short communications will be peer
reviewed and published free of charge after acceptance.
Copyright Information
Submission of a manuscript implies that:
1) The work described has not been published before (except in the form of an abstract or as part
of a published lecture, review, or thesis).
2) It is not under consideration for publication elsewhere.
3) Its publication has been approved by all coauthors, if any, as well as by the responsible
authorities at the institute where the work has been carried out.
4) Authors agree to automatic transfer of the copyright to the publisher, if and when their

manuscript is accepted for publication.
5) The manuscript will not be published elsewhere.
JACR Editorial Board:
Editor-in-Chief:
Ali Mahmoudi, Ph.D.,Associate Prof., Department of Chemistry, Islamic Azad University,
Karaj branch Karaj, Iran.
Managing Editor:
Abbas Ahmadi, Ph.D, Associate Prof., Department of Chemistry, Islamic Azad University,
Karaj branch, Karaj, Iran.
Regional Editors:
BitaMohtat, Ph.D,Associate Prof., Department of Chemistry, Islamic Azad University, Karaj
branch, Karaj, Iran.
Journal of Applied Chemical Research, 7, 4 (2013)
4
Editorial Board:
Saeed Dehghanpour, Ph.D., Associate Prof., Department of Chemistry, Alzahra University,
Tehran, Iran.
Khodadad Nazari, Ph.D., Associate Prof., Petroleum Research Institute, Tehran, Iran.
Lida Fotouhi, Ph.D., Prof., Department of Chemistry, Alzahra University, Tehran, Iran.
Mahmoud Sharimoghadam, Ph.D., Prof.Department of Chemistry, Tarbiatemoalem
University, Tehran, Iran.
Nader Zabarjad, Ph.D., Associate Prof., Department of Chemistry, Islamic Azad University,
Central branch, Tehran, Iran.
Mohsen Daneshtalab, Ph.D., Prof., Medicinal Chemistry and Pharmacognosy, School of
Pharmacy, University of Memorial, Canada (Honorary member).
Masayuki Sato, Ph.D., Prof., School of Pharmaceutical Sciences University of Shizuka
(Honorary member).
R.K.Agarwall, Ph.D.,Prof., Department of Chmistry, Singh University, India.
Surendra Prasad,Prof., Department of Biological and Chmical Sciences, Thechnology and
Environment, South Pacic (USP) University,Surva, ji.

Natasha Pourdana, PhD., Assistant Professor, Islamic Azad University, Karaj Branch, Iran
Instructions to Authors
Manuscript preparation
Types of Contributions:
Research papers: Are full-length expositions of extensive and signicant experimental and
applied studies.
Short communications: Must be complete, self-contained papers, and not preliminary reports.
In style and presentation they should conform to that laid down for manuscripts but length
should not exceed four printed pages in the journal.
Reviews: Will usually be written at the invitation of Editors. Unsolicited reviews will be welcome
but authors wishing to submit a review are requested to consult Editors prior to commencement.
Papers will be published in English. Manuscript should be submitted, in 1.5 spaced typing
on pages of uniform size with a wide margin on the left. The authors are urged to arrange
the subject matter clearly under headline such as Introduction, Experimental, Results and
discussion, Conclusion, Acknowledgement, References, Tables and Figure Captions.
Title: Papers should be headed by a concise and informative title. This should be followed
Journal of Applied Chemical Research, 7, 4 (2013)
5
by the name(s) and complete address of the author(s). The author(s) to whom correspondence
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Results and Discussion: The original and important ndings should be stated.

References: References should be numbered consecutively (numerals in square brackets)
throughout the text and collected together in a reference list at the end of the paper. In the
reference list, journals [1], books [2], thesis [3] and websites [4] should be cited in accordance
with the following styles:
[1] C. Maynard, W.D. Weaver, P.E. Litwin, J. Org. Chem., 72, 877 (1994).
[2] W. Warwich, D. Bannister, Analytical Chemistry, VCH, New York (1985).
[3] Y. Wilson, Synthesis and Pharmacological effect of Ketamin family, Ph.D thesis, Oxford
University, London, England (2000).
[4] J. Winsent, Factors in the Emergence of Infectious Diseases., Available online in:
/>Tables: Tables should be typed in double spacing on separate sheets and provided a suitable
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Journal of Applied Chemical Research, 7, 4 (2013)
6
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Figures should be numbered consecutively; and placed in their original position in the manuscript.
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Journal of Applied Chemical Research, 7, 4, 7-13 (2013)
Journal of
Applied
Chemical
Research
www.jacr.kiau.ac.ir
Probing the Nature of Annealing Silicon Carbide Samples
for Solar Cell
Ahmad Zatirostami
*1
, Khikmat Muminov
2

, A.Kholov
3

1
Department of Science and Engineering, Sari branch, Islamic Azad University, Sari, Iran.
2,3
Academy of Science of the Republic of Tajikistan, S.U.Umarov, Physical Technical Institute,
Tajikistan.
Received 12 Jun. 2013; Final version received 24 Aug. 2013
Abstract
SiC powder preparation using Sol-Gel method. The size of nano-particles grows as the
temperature exceeds 900° C. Size of probable agglomerations produced, is approximately
less than 50nm. The surface is suitable to be used for dye solar cells. SiC emission occurs
at wavelength area of 11.3μm or wave number area of 884.95 cm
-1
. In this paper probing
the nature of annealed SiC samples in mixture, sintered, burned, and washed with Si, being
removed. We can conclude that the efciency in trapping solar energy increases.
Key words: Amorphous, Mixture, Nanostructure, Thin lm, XRD.
* Corresponding author: Ahmad Zatirostami, Department of Science and Engineering, Islamic Azad University, Sari branch, Sari,
Iran.Email:
Introduction
Today, nano-materials and nanostructures are
not only the forefront of the hot researches
on the fundamental material, but also have
entered slowly and intrusively into our daily
lives .In recent years, the dye –sensitized
nano-structured solar cells (DNSC) based
on nanostructure metal oxide lms have
attracted much attention to themselves .The

electrons and holes produced by light need to
move on a shorter path to prevent the charge
recombination greatly [1,2].
A .Losses due to reection.
B .Recombination dissipation,
C. Loss due to series and parallel resistance.
Three approaches to curb the rst two loss
mechanisms: [3]
A. Increased number of energy levels, B.
trapping hot carriers before normalization,
C. generating pairs of electron - hole per high
energy photons or producing a higher energy
carrier pair with more than a low-energy
photon.
Infrared spectroscopy is carried out, based
A. Zatirostami et al., J. Appl. Chem. Res., 7, 4, 7-13 (2013)
8
on the radiation absorption and probing
vibration mutations of molecules and ions.
This method is employed as a powerful and
advanced method in determining structures
and measuring chemical species. Interaction
of infrared radiation would result in
modication of vibration energy of bonding
in molecules in the sample, which nominates
it as an appropriate method in identication
of functional groups and the molecular
structure. If the molecular dipole moment is
changed during the vibration, Infrared energy
absorption would occur. In electromagnetic

spectrum, the region between 0.8 and 400
micrometers belong to infrared, but the region
used for chemical analysis, is between 0.8 to
50 micrometers.
In order to obtain qualitative identication
of an unknown sample, infrared spectrum of
the sample is drawn based on the functional
groups and existing molecular bonds, and by
referring to relevant tables, which provides
vibration position of different bonds or
IR spectra of objects, wavelength or wave
number of groups and bonds would be
identied. One of the characteristics of FTIR
is that the entire wavelength of the considered
spectral region is simultaneously emitted
on the sample. While in dispersive methods,
only a small number of wavelengths reached
the sample at one time. Therefore, the speed,
resolution and signal-to-noise ratio in Fourier
transform method is signicantly better than
the conventional IR methods. In brief, the
qualitative and quantitative identication of
organic compounds containing Nanoparticles,
determination of functional group types and
its molecular bonds, are FTIR objectives [4].
Experimental
Material
The reason why Sol-Gel Method is employed
in the production of SiC Nano-powder, refers
to factors such as : achieving high purity,

increasing chemical activity, being needless of
applying complex equipments, enhancing the
functionality in Sintering materials, attaining
high production capability, enabling control
over properties and morphology, enabling
synthesis at molecular level, enabling the
production of very small particles with united
diameter, enabling the production of particles
with manageable and very high specic
surface area, reducing the number of un-
reacted materials in the nal product [5].
In sol-gel method, in order to synthesize
SiC nanopowder, when drying procedure
is complete, Samples are powdered and are
annealed at a temperatures of 500, 700, 900
and 1000° C. the process of annealing samples
was done in Chemical vapor deposition (CVD)
furnace, in air atmosphere with a thermal
gradient of 5° C per minute. In order to probe
particle shapes and for surface analysis of
structures, Scanning Electron Microscope is
used [6].
A. Zatirostami et al., J. Appl. Chem. Res., 7, 4, 7-13 (2013)
9
1. Radiation-absorption analysis using FTIR
C-C bond has an absorption frequency of 1200
cm
-1
, double bond of C = C has an absorption
frequency of 1650 cm

-1
and triple bond of C = C
has an absorption frequency of 2150 cm
-1
. The
bending motion is easier than stretch motion.
For example, bending C-H is assigned to the
area of 1340 cm
-1
and stretching C-H is assigned
to the area of 3000 cm
-1
. Hybridization type also
affects the absorption frequencies, so that the
bonds power are respectively SP> SP2> SP3.
In the Range of K = λ
-1
= 600 cm
-1
to 1400
cm
-1
,due to limited amount of absorbed
energy and the bending vibration of absorbed
energy, most molecular Bonds are complex
and crowded and therefore identication of
entire absorption bonds in this region would
be difcult. In other words, there is a unique
pattern in this region [7].
Absorption bonds in the region of K=λ

-1
=600
cm
-1
to 1400 cm
-1
, have more absorbed energy
which is mostly because of stretching vibration
in stronger bonds.
FTIR spectrum for SiC nanopowder, annealed
at temperatures of 500
o
C, 700
o
C, 1000
o
C
using (FTIR, SHIMADZU 8400S, JAPAN)
suggests:
A – In the wave number K=λ
-1
=478.31 cm
-1
, as
the temperature increases, absorption amount
is reduced. (From 90% in 500
o
C to 27% at
1000
o

C). On the other hand, in the absorption
frequency or wave number, siloxane bond (Si-
O-Si) is observable. This bond is the result
of hydrolysis reactions and condensation of
silicon alkoxide.
B - SiC emission occurs at wavelength area of
11.3μm or wave number area of 884.95 cm
-1
. [3]
Comparing these spectra we’ll realize that in
K=λ
-1
=825.48 cm
-1
, there is a Si-C bonding
which is a result of bonding among carbon
atoms in acetic acid and ethanol with the Si
bond in hydrolyzed and condensate Tetraethyl
orthosilicate liquid (SiC
8
H
20
O
4
). Moreover,
by comparing spectra, we can conclude that
as the temperature increases, the amount of
absorption has increased due to SiC formation.
C–In K=λ
-1

=1087.78 cm
-1
, in a range of
500
o
C to 700
o
C due to the double bond of
C=O, absorption increases. However in the
range of 700
o
C to 1000
o
C as temperature
is increased, due to the formation of single
bond C-O, the absorption is promptly
reduced. In this absorption frequency, at all
temperatures stated, Si-O bond is identiable
which is because of hydrolysis reaction and
condensation of the silicon aloxides.
D-In K = λ
-1
= 2337.56 cm
-1
, absorption bonds
have more energy, which is generally because
of stretching vibration of strong bonds. (Group
frequency region).
At K=λ
-1

=1380.94 cm
-1
C-C and C-O bonds, the
wave number of K=λ
-1
=1535.23 cm
-1
double
bonds of C = C, in absorption frequency K=λ
-
1
=2923.38 cm
-1
C-H bonds are identiable.
2. Probing the nature of annealed SiC samples
A. Zatirostami et al., J. Appl. Chem. Res., 7, 4, 7-13 (2013)
10
in different states
A - Mixture:
With a review on the mixture of Si and C
using XRD we’d come to this conclusion that,
at lower temperatures the biggest proportion
of Si phase is restored. However, at this
temperature, CNT or carbon nano-tubes will
also be restored. (Figure1). These nano-tubes
are characterized by high efciency in trapping
solar energy, as light collector and transmitter.
CNTs have excellent electrical properties,
and play different roles in nano-structured
solar cells. They could also be employed as

transparent electrode in nano-structured solar
cells.
Figure1. X-Ray Diffraction –Mixture.
B - Sintered:
By sintering Si and C, and by placing the
sample at 1200 °C for 2 minutes, we’ll realize
that in addition to restoring Si and CNT,
silicon carbide is also restored. (Figure 2), But
with reduction in their height, their width is
reduced which means that according to Debye
- Scherrer equation, particle size has increased.
The reduction in resulting peaks intensity
indicates rapid weakening in formation of Si,
CNT due to the Sintering at 1200 ° C.
Figure 1. X-Ray Diffraction - Mixture
A. Zatirostami et al., J. Appl. Chem. Res., 7, 4, 7-13 (2013)
11
Figure 2. X-Ray Diffraction –sintered 2 min at 1200
o
C.
C - Burned:
By burning the sample for 2 hours at 700° C,
we’ll realize that the CNT phase is removed
and only Si and SiC phases are restored.
(Figure 3). In other words, sample efciency
in trapping solar energy lowers. However,
the peak intensity of Si and SiC formation
has increased. In conclusion, by burning the
sample, we’ll understand that Si and SiC
formation rate increases, and also due to the

increase in peak height, particles tend to turn
into nanostructured particles.
Figure 3. X-Ray Diffraction – Burned 2 hr at 700
o
C.
A. Zatirostami et al., J. Appl. Chem. Res., 7, 4, 7-13 (2013)
12
D - Washed:
As the rst step an amount of 100gr potassium
hydroxide (KOH) is solved in 250mililitter
distilled water. After cooling and reaching
ambient temperature, its velocity would be
increased to 1Litter, adding ethanol. The
resulting solution KOH is a cleaning solution
and highly corrosive. In this section, the sample
is washed in the KOH solution. Reviewing
XRD spectra of the samples (Diagram 4) we’d
realize that:
* The intensity of the resulting peaks has
greatly lowered. In other words, the process of
formation has slowed
* Only SiC phase is restored. In other words,
only SiC is formed after washing. And phases
of Si and CNT are removed which means that
a pure SiC could be produced this way.
*** With Si, being removed, we can conclude
that the efciency in trapping solar energy
increases.
Figure 4. X-Ray Diffraction – Washed in KOH.
Results and discussion

From XRD spectrum, this could be concluded
that as the temperature increases, the resulting
peaks intensity weakens. Si peak has started
to grow from 900° C and is higher at1000° C.
With mixture of Si and C we’d come to this
conclusion that, at lower temperatures the
biggest proportion of Si phase is restored. By
sintering Si and C, in addition to restoring Si
and CNT, silicon carbide is also restored. By
burning the sample, Si and SiC formation rate
increases. Only SiC is formed after washing.
And phases of Si and CNT are removed which
means that a pure SiC could be produced this
A. Zatirostami et al., J. Appl. Chem. Res., 7, 4, 7-13 (2013)
13
way.
SiC emission occurs at wavelength area of
11.3μm or at wave number area of 884.95cm
-
1
. Comparing the spectra of K = λ
-1
= 825.48
cm
-1
, formation of Si-C bond could be seen
which is because, the bonding of carbon
atoms in acetic acid and ethanol, with the Si
bond in hydrolyzed and condensate Tetraethyl
orthosilicate liquid (SiC

8
H
20
O
4
). Also
comparing the spectra, we can conclude that,
as the temperature increases, the amount of
absorption due to SiC, increases as well.
Reviewing the nature of SiC annealed samples
in different states, we’ll come to the following
conclusions:
A - In the case Si and C are mixed, we realized
that at low temperatures, the Si phases are
mostly restored. However, at this temperature,
CNT or carbon nano-tubes will also be
restored. These nano-tubes are highly efcient
in trapping solar energy, as solar collectors
and transmitter.
B - Or in the case of Sintered Si and C we nd
that in addition to restoring Si and CNT, silicon
carbide is also restored. But as their height
reduces, their width is decreased. According
to Debye – Scherrer equation particle sizes
are larger. The reduction in resulting peak
intensity indicates the rapid weakening of Si,
CNT due to the existing porosity at 1200 ° C.
C -In Burned state, by burning the sample for
2 hours at 700 ° C, we’ll realize that the CNT
phase is removed and only the Si and SiC phases

are restored. In other words, the performance of
solar energy trapping has decreased. However,
the intensity of Si and SiC peak formation is
increased. In other Words by burning samples,
Si and SiC formation rate have increased. Due
to the peak height increase, the particles tend
to form nano-structure particles.
D -In Washed phase, we found that the
intensity of the peaks has greatly lowered.
Only SiC phase is restored. The pure SiC
could be obtained this way. As Si is removed,
we may realize that the efciency of solar
energy trapping has increased.

References
[1] H. Shirai, J. Hanna, I. Shimizu, Japanese
Journal of Applied Physics, 30, 679 (1991).
[2] H.F. Sterling, R.C.G. Swann, Solid-State
Electron, 8, 653 (1965).
[3] J.J. Gaumet, G. A. Khitrov, G. F. Strouse,
Nano Letters, 2, 375 ( 2002).
[4] M. Praisler, S. Gosav, J. Van Bocxlaer,
A. De Leenheer, D.L. Massart, The Annals of
the University “Dunãrea de Jos”, Fascicle II,
83-96 (2002).
[5] I.S. Seog, C.H. Kim, Journal of Materials
Science, 28, 3277(1993).
[6] A. Zatirostami, Tekstil, 62, 163 (2013).
[7] J. M. Leisenring, F. Kemper, G. C. Sloan,
Scheduled to appear in Apj., PP. 1-18 (2008).


Journal of Applied Chemical Research, 7, 4, 15-24 (2013)
Journal of
Applied
Chemical
Research
www.jacr.kiau.ac.ir
Determination of Saturates, Aromatics, Resins and
Asphaltenes (SARA) Fractions in Iran Crude oil Sample
with Chromatography Methods: Study of the Geochemical
Parameters
Elham Keshmirizadeh
1,*
, Somayeh Shobeirian
1
, Mahmoud Memariani
2
1
Department of Applied Chemistry, Karaj Branch, Islamic Azad University, Karaj, Iran.
2
Chemistry Research Institute of Petroleum Industry-Geosciences Research Division, Tehran, Iran.
Received 22 Jun. 2013; Final version received 14 Aug. 2013
Abstract
In this study, Iran crude oil samples (K, L) were separated on the basis of solubility and polarity,
resulting in saturates, aromatics, resins, and asphaltenes fractions. The fractions were analyzed
by traditional open column chromatography, thin layer chromatography-Flame ionization
detector in an Itroscan instrument (TLC-FID) and Gas chromatography with ame ionization
detection for the determination of n-alkane and isoprenoid distribution in oil samples that are
chosen as the most suitable structures for the identication and differentiation of crude oil
samples and oil-oil correlations. The precursor organic matters of the analyzed oil samples

of K, L are from a low salinity marine carbonate and reduced depositional environment.
The studied oil samples were light and appeared to be mostly of type II, III kerogen mixture
origin. The Koil sample is moderately mature (OEP and CPI are near 1).
Keywords: SARA fractions, TLC-FID, Crude oil, Maturity parameters, Geochemical
parameters.
Introduction
Over the last few decades, an increase in
the demand for commercial light oil and the
decline of the quality of crude oil have been
observed [1].The recovery of useful products
from petroleum has been for several years
an increasingly important task that is based
on the understanding of the physicochemical
properties of the crude oil mixture. For
petroleum uids composition and properties
vary continuously from the simplest structures
to macromolecule [2]. The characterization
of the heavy fraction is then based on the
identication of a number of families with
*Corresponding author: Dr. Elham Keshmirizadeh, Assistant Prof., Department of Applied Chemistry, Karaj Branch, Islamic Azad
University, POBOX: 31485-313, Karaj–Iran. Email: , Tel: 026-34182305, Fax: 026-34418156.
E. Keshmirizadeh et al., J. Appl. Chem. Res., 7, 4, 15-24 (2013)
16
certain properties which can be easily
distinguishable from each other [3]. While
simulated distillation by gas chromatography
is a routine means for characterization of the
light end, it is not applicable for heavy-end
characterization due to inability of GC for
characterization of large molecules. Therefore

the methods employed rely on solubility
and other chromatographic techniques [4].
The SARA procedure [5] modied for
characterization of the heavy end as already
described by Vazquez and Mansoori [6] was
used to separate a sample into four classes of
compounds, namely saturates, aromatic, resins
and asphaltenes.
The saturate fraction consists of a viscous
whitish translucent liquid mainly composed
of parafn’s and diamond oils. From the four
fractions separated from the heavy-end only
the saturate fraction is easily distinguishable
and separated from the rest of the oil due to
the absence of π-bonds in between saturate
hydrocarbon molecules. The aromatic fraction
is a viscous reddish liquid composed of
aromatic hydrocarbons with various degrees
of condensation, alkyl-substitution and
heteroatom(i.e. sulfur, oxygen, nitrogen)
content forming a continuum with respect to
polarity, molecular weight and other properties.
The resin fraction is a dark brown colored,
thick viscous liquid to semi-solid with a higher
degree of condensation and heteroatom content
than the aromatics. It plays an important role in
asphaltene occulation [7, 8].
There is however no single approach that
can rapidly, reliability and simultaneously
characterize crude oil fractions and specic

classes of compounds and individual
compounds in each fraction. Many standard
methods(e.g. ASTM D2007, D4124) had been
developed for characterizing the crude oil
fractions but the gravimetric quantication
of typical fractions proved inadequate
[9,10].Coupling fractionation by TLC and
quantication using with ame ionization
detection (FID), the TLC-FID method
developed in the 1970s showed to offer several
advantages: (i) simultaneous fractionation
crude oil into saturated, aromatic and polar
classes, (ii) applicability for the determination
of heavy fractions with high boiling points,
(iii) low cost, simple instrument requirements
and procedure saving. Therefore, TLC
method rapidly became extensively applied
for analysis of drugs, crude oils, coal-derived
liquids [11-13].
The objectives of this paper were: (i) to
compare the extraction efciency of traditional
open column chromatography and the TLC-
FID Itroscan separations of crude oils into
classes of compounds such as SARA,(ii)
to identify specic compounds in the light
fraction of crude oil using GC, (iii) to explains
how certain non-biomarker parameters, such
as ratios involving n-alkanes hydrocarbons,
are used to assess thermal maturity.
E. Keshmirizadeh et al., J. Appl. Chem. Res., 7, 4, 15-24 (2013)

17
Experimental
SARA Fractionation of Crude Oil
A SARA separation system was developed to
characterize crude oils of interest. Crude oil
samples (K, L) for this study were obtained
from a South west of Iranian source and stored
under argon. The asphaltene fraction was
precipitated from the corresponding crude
oil using n-heptane (HPLC grade, Merck,
Germany). To obtain the asphaltene, a slightly
modied SARA fractionation procedure was
used (Fig 1) [6]. A total of 30 ml of n-heptane/
gof crude oil was added. The precipitated
portion was ltered and dried under inert
gas ow. The sample (with the lter) was
extracted with 300 ml of toluene (HPLC grade,
Over lack, Germany) until no color changes
were observed. The re-dissolved asphaltene
fraction was rotary-evaporated and afterward,
dried under a continuous stream of nitrogen.
The extracted solution (maltenes fraction) was
rotovapped until a stable mass was achieved.
The dried maltenes were then diluted with
n-heptane and mixed with activated alumina
(80−200 mesh, Merck, Germany). The slurry
was dried and loaded on the top of a glass
column, packed with neutral alumina sorbent.
In sequence, n-heptane, toluene, and toluene/
methanol (9:1, v/v) (HPLC grade, Merck,

Germany) mixtures were used to elute
saturates, aromatics, and resins. A total of
350 ml of solvent/g of maltenes was used
for the chromatographic separation. Thin-
layer chromatography was used to monitor
the complete separation of each fraction.
Finally, the fractions were rotary-evaporated
to dryness and then weighed. To have a correct
mass balance, the volatile part of the original
sample was also determined using rotavap
vapor at 26 mbar and 30°C. The obtained mass
balance and recovery is presented in Table 1.
The reported SARA-values of the low-yield
samples in this study are corrected to 100 %
by adjusting the saturate and aromatic values.
Hence, the evaporation loss from the resin
fraction is considered to be negligible.
Table1. SARA fractions of crude oil samples analyzed with TLC-FID Itroscan and traditional open column
chromatography-gravimetry.
Asphaltene
%Wt
Resin
%Wt
Aromatic
%Wt
Saturate
%Wt
Sample
Open
column

TLC
Open
column
TLC
Open
column
TLC
Open
column
**
TLC
*
1.00
0.3
15.6
11.2
4.50
17.0
78.90
70.9
K
1.00
0.9
17.9
9.20
5.00
17.9
76.10
72.0
L

*Analyzed by TLC-FID Itroscan, **Analyzed by traditional open column chromatography-gravimetry.
TLC-FID procedure of crude oils
Recently, the TLC-FID method has been
substantially improved. Barman showed
that a sample loading as low as 5–10µg was
Table 1.
E. Keshmirizadeh et al., J. Appl. Chem. Res., 7, 4, 15-24 (2013)
18
optimal regarding signal-to-noise ratio [14].
Karlsen and Larter [15] and Cebolla et al. [16]
investigated the effect of scan speed on the
FID response, and found that the FID response
decreased when increasing the scanning
speed. A TLC device (MK-6S, Tokyo, Japan)
equipped with FID detector was used to test
the TLC-FID method. The S-III chromarod
(MKI, Tokyo, Japan) used in this study was
15.2cm long and 1.0mm in diameter and was
coated with a layer of silica gel (5µm particle
size). During experiments the chromarod was
spotted with 1µL of extract, and subsequently
was developed with the following program:
n-hexane (30 min), 50% (v/v) hexane–DCM
(20 min) and 95% (v/v) DCM–methanol (5
min). The chromarod was dried at 40 ◦C for 2
min after each development. For the TLC-FID
method, a scan rate of 40 s/scan was used. Air
and hydrogen ows were 2000 mL/min and
160 ml/min, respectively.
Whole oil GC analysis

A gas chromatograph capable of oven
temperature programming from 35°C to
200°C in 1°C/min increments was used. A
heated ash vaporizing could provide a linear
sample split injection (for example, 200:1).
The associated carrier gas controls could
provide reproducible column ows and split
ratios. A hydrogen ame ionization detector
designed for optimum response with capillary
columns (with the required gas controls
and electronics) could meet the following
specications: Operating temperature: 100°C
to 300°C, sensitivity >0.015 C/g, minimum
detect ability: 5*10−12 g carbon/second,
linearity >107.
A Varian cp-3800 gas chromatograph was
used to analyze the oil samples. The gas
chromatograph (GC) was equipped with
an auto sampler for injections, a ame
ionization detector (FID), and electronic
pressure ow controllers to ensure constant
ow throughout the oven-heating program.
The GC was operated using the following
analytical materials and conditions: 1 column
(100 m×250 μm I.D×0.5 μm lm thicknesses),
injector temperature of 250 °C, pressure
283 kPa, split ratio set to 100:1, and FID
temperature of 300 °C. The GC oven was
programmed from 35 °C with a 13 min initial
isotherm, then an initial heating rate program

of 10 °C/ min to 45 °C with a 15 min hold time
after which the rate was decreased to 1.9 °C/
min to a nal temperature of 200 °C with 5 min
hold time. Helium carrier gas was used with
a minimum purity of 99.999%. The injected
sample volume was 0.5 μl. The crude oil was
back ushed 0.3 min after injection to remove
its heavy components. The assignment of the
C7 compounds was based on comparison with
chromatogram references provided by the
supplier of a commercial mixture of parafn’s,
naphthenes and aromatic hydrocarbons
(ASTM D- 5134).
E. Keshmirizadeh et al., J. Appl. Chem. Res., 7, 4, 15-24 (2013)
19
Scheme 1. SARA Fractionation According to the Solubility of Each Fraction.
Whole oil GC is a common type of analysis
for oil samples. The analysis (Figure 2) will
give a complete picture of the hydrocarbons
present in the oil and also of the sulphur-
containing compositions. It is important to
have good resolution for both the light and
heavy components.
Figure 2.The GC chromatogram for the analyzed oil samples(K,L). Note:(C
9
:naphta, C
9
-C
14
:Kerosene, C

14
-
C
20
:Diesel, C
20
+
:Residual fuel oil).
E. Keshmirizadeh et al., J. Appl. Chem. Res., 7, 4, 15-24 (2013)
20
Result and discussion
Analysis of crude oil samples
The crude oil samples were fractionated by
the traditional and TLC-FID (Itroscan) SARA
technique as described by in the experimental
section. The experiment was repeated
severaltimes and the average results, reported
as wt. % are presented in Table 1 and Figure
3. The results obtained from the fractionation
of crude oils K, L were compared with each
other in this study also oil-oil correlation was
performed.
From an overall comparison the two crude oils
seem quite similar in composition.
In general, the mass ratios of asphaltenes
to resins in crude oils around the world
have been found to be quite small, in the
range of 0–0.26. For the crude oils under
study here the average ratio were found
to be 0.02 and 0.09 respectively [17-19].

Figure 3. Star diagram (comparative diagram) for SARA fractions of two samples K, L under traditional
measurement and modern measurement.
0
20
40
60
80
Saturate
Aromatic
Resin
Asphaltene
Sample K.traditional
Sample L.traditional
Sample K-TLC
Sample L.TLC
Non-biomarker maturity parameters
This study explains how certain non-biomarker
parameters, such as ratios involving n-alkanes
hydrocarbons, are used to assess thermal
maturity. Various characteristics of petroleum
samples can be used to assess their relative
level of thermal maturity.
Alkanes & isopronoids (pristine and phytanes)
Isopronoids/n-alkane ratios: specic for
maturity but also affected by other processes,
such as source and oxidizing, reducing and
biodegradation measured using peak heights or
areas from gas chromatography(GC data) and
type of kerogen, however carbon preference
index(CPI) and odd-even preference(OEP)

are dened as follows [20]:
CPI=


[
େଶହାେଶ଻ାେଶଽାେଷଵାେଷଷ
େଶସାେଶ଺ାେଶ଼ାେଷ଴ାେଷଶ
+
େଶହାେଶ଻ାେଶଽାେଷଵାେଷଷ
େଶ଺ାେଶ଼ାେଷ଴ାେଷଶାେଷସ
](1)
OEP=
(େଶଵା଺େଶଷାେଶହ)
(ସେଶଶାସେଶସ)
(2)
E. Keshmirizadeh et al., J. Appl. Chem. Res., 7, 4, 15-24 (2013)
21
Table 2. The ratios and values of the majority of the used non biomarkers in this study.
Sample
CPI
Eq(1)
OEP
Eq(2)
Pri/Phy*
Pri/nC17
Phy/nC18
K
0.94
0.54
0.95

0.53
0.48
L
1.10
0.99
0.95
0.54
0.34
*Pristane:Pri, Phytane:Phy.
CPI and OEP parameters show the strength
of the odd carbon in n-alkanes. According to
Table 2 and Figure 4 (geochemical parameters
were calculated by the integrated peak area
from GC (CPI, OEP, Pri/Phy))
Broocks noted the presence of the regular
isoprenoids pristane (Pri) and phytane
(Phy) in crude oils and coal extracts [21]. A
mechanism for the production of relatively
high concentrations of pristane in oxic
type environments and high concentration
of phytane in reducing type environments
was represented [22]. Thus, the Pri/Phy
ratio evolved as an indicator of the oxicity
of the initial organic matter’s depositional
environment. The Pri/Phy ratios are very
helpful in determining the pale depositional
environment and source of the precursor
organic matters of the reservoired oil. It is
well known that Pri/Phy ratios>3.0 indicates
predominantly non marine source from

terrestrial organic matter,(terrigenous plant
input) deposited under oxic to suboxic
conditions [20, 23].An oil accumulation have
Pri/Phy ratio < 0.8 indicates saline to hyper
saline conditions associated with evaporate
and carbonate deposition, while marine
organic matters usually have Pri/Phy<1.5 [20].
As the Pri/Phy ratio for the analyzed oil
samples (K, L) are 0.95, 0.95 respectively,
therefore a marine inuence on the type of
the source organic matters can be detected.
The plot of the Pri/nC
17
and Phy/nC
18
values
for the analyzed sample on the specic plot in
the Figure 4 indicated a mature marine source
of organic matter (mostly type II, III kerogen
mixture) deposited in a reduced condition with
less effect of biodegradation.
Kerogen is a mixture of organic chemical
compounds that make up a portion of the
organic matter in sedimentary rocks. It
is insoluble in normal organic solvents
because of the huge molecular weight of its
component compounds. The soluble portion is
known as bitumen. When heated to the right
temperatures in the Earth’s crust, (oil window
ca. 60–160 °C, gas window ca. 150–200 °C,

both depending on how quickly the source
rock is heated) some types of kerogen release
crude oil or natural gas, collectively known
as hydrocarbons (fossil fuels). When such
E. Keshmirizadeh et al., J. Appl. Chem. Res., 7, 4, 15-24 (2013)
22
kerogens are present in high concentration
in rocks such as shale they form possible
source rocks. Shales rich in kerogens that
have not been heated to a warmer temperature
to release their hydrocarbons may form oil
shale deposits [24]. All types of kerogen are
introduced in Figure 4.
Level of thermal maturity
The gas chromatogram of the saturated
hydrocarbon fractions shows a shift in the
normal alkane distribution to lower carbon
numbers (Figure 2), reecting relatively
a moderate level of thermal maturity, The
analyzed oil samples are light samples (Table 1
and Figure 3) this can be interpreted according
to Justwan [25] in terms of increased type
II, III kerogen mixture contribution. CPI can
offer valuable information on the maturation
of source rocks and reservoired oil. High CPI
values (above1.5) always refer to relatively
immature samples. Low CPI values, however,
do not necessarily mean higher maturity; they
can also mean a lack of higher n- alkanes
stemming from terrestrial input. The measured

CPI values for the studied oil samples (K,L)
are respectively equal to 0.94 and 1.1 which
means that they are moderately mature oils.
In practice, the OEP can be adjusted to include
any specied range of carbon numbers.
Some examples of CPI and OEP variations
are shown above (Eq1, Eq2). CPI or OEP
values signicantly above (odd preference)
or below (even preference) 1.0 indicates low
thermal maturity. Values of 1.0 suggest, but
do not prove, that an oil or rock extract is
thermally mature. CPI or OEP values below
1.0 are unusual and typify low-maturity oils
or bitumens from carbonate or hyper saline
environments. Organic matter input affects
CPI and OEP. However in this study OEP of
K, L oil samples are 0.54 and 0.99 respectively,
one can conclude that L sample has lower
maturity.
E. Keshmirizadeh et al., J. Appl. Chem. Res., 7, 4, 15-24 (2013)
23
Figure 4. Pristane/C
17
versus Phytane/C
18
diagram for the studied oil samples. Note:Type I Kerogen: Sapropelic
(containing alginate), Type II Kerogen: Planktonic (marine),Type II Kerogen: Sulfurous (similar to Type II but high
in sulfur, Type III Kerogen: Humic(Land plants (coastal)).
Conclusion
This has resulted in the observation that crude

oil SARA-data can be determined both from
modern method (TLC-FID Itroscan method)
in a fast and simple manner compared to
the more tedious traditional open column
chromatography-gravimetry method.
The precursor organic matters of the analyzed
oil samples of K, L are from a low salinity
marine carbonate and reduced depositional
environment. The studied oil samples are light
and appear to be mostly of type II, III kerogen
mixture origin. The Koil sample is moderately
mature (OEP and CPI are near 1).
Acknowledgement
This research was supported by KIAU (Islamic
Azad University, Karaj branch) funds hereby
the authors express their gratitude.
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Journal of Applied Chemical Research, 7, 4, 25-38 (2013)
Journal of
Applied
Chemical
Research
www.jacr.kiau.ac.ir
A Study on Peel Volatile Constituents and Juice Quality
Parameters of Four Tangerine (Citrus reticulata) Cultivars
from Ramsar, Iran
Behzad Babazadeh Darjazi
Department of Horticulture, Faculty of Agriculture, Roudehen Branch, Islamic Azad University, Rou-
dehen, Iran.
Received 11 Jun. 2013; Final version received 15 Aug. 2013
Abstract
The peel volatile constituents and juice quality parameters of four tangerine cultivars were
investigated in this study. Peel avor constituents were extracted by using cold-press and
eluted by using n-hexane. Then all analyzed by GC-FID and GC-MS. Total soluble solids, total
acids, pH value, ascorbic acid as well as density and ash were determined in juice obtained
from tangerine cultivars. Forty-six, Twenty- ve, Forty and thirty-four peel constituents in
Dancy, Cleopatra, Ponkan and Atabaki cultivars respectively including: aldehydes, alcohols,
esters, monoterpenes, sesquiterpenes and other components were identied and quantied.
The major avor constituents were linalool, limonene, γ-terpinene, (E)-β-ocimene, β-myrcene,
α-Pinene. Among the four cultivars examined, Dancy showed the highest content of aldehydes
and Younesi showed the highest content of TSS. Since the aldehyde and TSS content of citrus
peel are considered as two of the most important indicators of high quality, variety apparently
has a profound inuence on citrus quality.
Keywords: Flavor constituents, Peel oil, Cold-press, Juice quality, Tangerine cultivars.
Introduction
The citrus is an economically important crop
cultivated extensively in Iran. The total annual

citrus production of Iran was about 87000
tonnes in 2010 [1]. Atabaki is a native variety
of tangerine that grown in the Mazandaran
province located in the north region of Iran.
Younesi was produced from nucellar tissue
of ponkan tangarine and it was cultured as a
nucellar seedling by Ramsar research station in
1968 [2]. They are two of the most important
tangerine cultivars used in Iran. Although
*Corresponding author: Dr. Behzad Babazadeh Darjazi, Department of Horticulture, Faculty of Agriculture, Roudehen Branch,
Islamic Azad University, Roudehen, Iran., E-mail: babazadeh @riau.ac.ir. Tel: +98 21 33009743.

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