The Third Basic Science International Conference - 2013 i
Preface
All praises are due to Allah, God Almighty, Who made this annual event of successful. The “3rd
Annual Basic Science International Conference (BaSIC-2013)” is an annual scientific event organized
by the Faculty of Mathematics and Natural Sciences, Brawijaya University. As a basic science conference,
it covered a wide range of topics on basic science: physics, biology, chemistry, mathematics and statistics.
In 2013, the conference took a theme of “Basic Science Advances in Energy, Health and Environment”
as those three aspects of life are hot issues.
The conference in 2013 was the continuation of the preceding conferences initiated in 2011 as the
International Conference on Basic Science (ICBS), where it was a transformation from the similar
national events the faculty had organized since 2004. What also changed in year 2013 was the use of the
ISSN for the conference proceedings book, instead of an ISBN used in previous proceedings books. The
change was based on the fact that BaSIC is an annual event, and, therefore, the use of ISSN is more
appropriate. The proceedings book was also divided into four books: Physics, Biology, Chemistry and
Mathematics, each with a different ISSN. The proceedings were also published in electronic forms that can
be accessed from BaSIC website. I am glad that for the first time both types of publication can be realized.
This event is aimed to promote scientific research activities by Indonesian scientists, especially
those of Brawijaya University, in a hope that they may interact and build up networks and collaborations
with fellow overseas counterparts who participated in the conference. This is in line with university vision
as a World Class Entrepreneurial University.
I am grateful to all the members of the program committee who contributed for the success in
framing the program. I also thank all the delegates who contributed to the success of this conference by
accepting our invitation and submitting articles for presentation in the scientific program. I am also
indebted to PT Semen Gresik and PT PLN (Persero) for their support in sponsoring this event.
I wish for all of us a grand success in our scientific life. And I do hope that the coming conferences
will pick up similar success, and even better.
Malang, April 2013
Johan Noor, Ph.D.
Conference Chairperson
The Third Basic Science International Conference - 2013 ii
Foreword by the Rector of Brawijaya University
First of all I would like to congratulate the Organizing Committee for the success in organizing this
amazing event. I believe all dedicated time and efforts will contribute to the advancement of our beloved
university.
I would like to welcome all participants, domestic and overseas, especially the distinguished invited
speakers, to Malang, to the conference. An international conference is a good means to establish and build
relationships and collaborations among participants. So, I hope this conference will facilitate all of you, the
academicians and scientists, to setup a network of mutual and beneficial collaboration. As a university with
a vision to be “A World Class Entrepreneurial University”, Brawijaya University will support all efforts to
realize that dream.
Finally, I do hope that the conference will run smoothly and nicely and is not the last one. I would
like to thank all parties who have lent their hands in making this conference happened.
Malang, April 2013
Prof. Dr. Yogi Sugito
Rector, Brawijaya University
The Third Basic Science International Conference - 2013 iii
Table of Contents
Preface .............................................................................................................................................................. i
Foreword by the Rector of Brawijaya University ........................................................................................... ii
Table of Contents ........................................................................................................................................... iii
Program Committee ......................................................................................................................................... v
Scientific Program ........................................................................................................................................ viii
Scientific Papers
Invited Papers
Cluster Dynamics by Ultra-Fast Shape Recognition Technique.................................................... I01
Nanotechnology Development Strategy for Supporting National Industry in Indonesia .............. I02
Role of Atomic Scale Computational Research in the Nanoscale Materials ................................. I03
Paeonilorin(PF) Strongly Effects Immuno System ........................................................................ I04
Investigating Chlamydia trachomatis using mathematical and computational .............................. I05
Recent Trends in Liquid Chromatography for Bioanalysis ........................................................... I06
Submitted Papers
Analysis of Inorganic Compounds Cr, Cd, CN, Mn, and Pb in RAW Water and Water Filtration
Results in Jakarta-Indonesia .......................................................................................................... C02
Pervaporation through NaA Zeolite Membranes - A Review ....................................................... C03
Optimization of NaOH as the cleaning of Polyethersulfone (PES) membrane fouled by Palm oil
mill effluent ................................................................................................................................... C08
Room-Temperature Synthesis of TiO2 - Chitosan Nanocomposites Photocatalyst ...................... C10
Structure of Hf(IV) in aqueous solution - An ab initio QM/MM MD approach .......................... C15
Molecular Dynamics Simulation of Scandium (I) Singlet In Liquid Ammonia By AB Initio
QM/MM MD Methods .................................................................................................................. C16
The Third Basic Science International Conference - 2013 iv
A New Coated Wire Iodide ion Selevtive Electrode (Iodide-CWE) base on Zeolite membrane as
Iodide ion sensor in urine .............................................................................................................. C18
Sorption of Toxic Cations onto Sago Waste 1: Investigation of Sorptive Capacity ..................... C19
Biosorption of Toxic Cations onto Sago Waste II: Kinetic and Equilibrium Studies .................. C20
UV-vis spectroscopy and semiempirical quantum chemical studies on the inclusion complex of
methyl red with cyclodextrins .................................................................................................. PSC20
Author List ............................................................................................................................................... AU-1
Acknowledgement .................................................................................................................................. ACK-1
The Third Basic Science International Conference - 2013 v
Program Committee Patrons
Rector, Universitas Brawijaya
Dean, Faculty of Mathematics and Natural Sciences, Universitas Brawijaya
Advisory Boards
Associate Deans 1, 2 and 3, Faculty of Mathematics and Natural Sciences, Universitas Brawijaya
Chairperson
Johan A.E. Noor, Ph.D.
Deputy-Chair
Dr. Suharjono
Secretary
Agus Naba, Ph.D.
Treasurers
Mrs. Sri Purworini
Mrs. Rustika Adiningrum
Mr. Surakhman
Secretariat & Registration
Dr. Masruroh
dr. Kusharto
Mr. Sugeng Rianto
Mr. Gancang Saroja
Conference Web
Agus Naba, Ph.D.
Publication & Proceedings
Arinto Y.P. Wardoyo, Ph.D.
Mr. Wasis
Public Relations & Sponsorship
Chomsin S. Widodo, Ph.D.
Mr. Moch. Djamil
Mrs. Firdy Yuana
Venue
Mr. Ahmad Hidayat
Dr. Ahmad Nadhir
Mr. Sunariyadi
Mr. Purnomo
Mr. Karyadi Eka Putra
Accommodation & Hospitality
Ms. Siti J. Iswarin
Mrs. Lailatin Nuriyah
The Third Basic Science International Conference - 2013 vi
Mrs. Nur Azizah
Mr. Robi A. Indrajit
Mrs. Trivira Meirany
Master of Ceremony
Himafis
Transportation, Excursion & Social Events
Djoko Santjojo, Ph.D.
Dr. Sukir Maryanto
Mr. Wahyudi
Mrs. Arnawati
Workshop, Poster & Scientific Exhibitions
Hari Arief Dharmawan, Ph.D.
Mr. Pudji Santoso
Mr. Sahri
Mr. Murti Adi Widodo
Documentation
Mauludi A. Pamungkas, Ph.D.
Mr. Susilo Purwanto
General Supports
Himafis
Scientific Program
Dr. rer.nat. M. Nurhuda
Dr. Sunaryo
Mr. Agus Prasmono
Local Scientific Committees (Reviewers & Editors)
Physics
Dr. rer.nat. Abdurrouf
Adi Susilo, Ph.D.
Mr. Unggul P. Juswono
Dr.-Ing. Setyawan P. Sakti
Biology
Dr. Moch. Sasmito Djati
Dr. Muhaimin Rifai
Dr. Catur Retnaningdyah
Chemistry
Dr. Masruri
Dr. Ahmad Sabarudin
Dr. Lukman Hakim
Mathematics
Dr. Agus Suryanto
Dr. Wuryansari M.K.
Dr. Rahma Fitriani
Dr. Solimun
The Third Basic Science International Conference - 2013 vii
International Scientific Committee and Editors
A/Prof. Lilibeth dlC. Coo, University of the Philippines, the Philippines
Prof. Dr. Gereon Elbers, FH Aachen, Germany
Prof. S.K. Lai, National Central University, Taiwan
Prof. Kwang-Ryeol Lee, Korean Institute of Science and Technology, Korea
A/Prof. Dann Mallet, Queensland University of Technology, Australia
Prof. Lidia Morawska, Queensland University of Technology, Australia
Prof.Dr. Petr Solich, Charles University, Czech Republic
Dr. Michitaka Suzuki, Nagoya University, Japan
Prof. Hideo Tsuboi, Nagoya University, Japan
Prof. Jia-Lin Wang, National Central University, Taiwan
The Third Basic Science International Conference - 2013 viii
Scientific Program Time Day One – 16 April 2013 Day Two – 17 April 2013
07.30 – 08.00 Registration
08.00 – 08.30 Inaugural Session, Welcome Remarks
and Opening Ceremony Poster Preparation
08.30 – 09.00 Coffee Break
Poster Session (08.30-09.30)
(Majapahit Hall)
09.00 – 09.45
Invited Speaker 1
Prof. Lidia Morawska, Queensland
University of Technology, Australia
Title: “Emissions to the Air: from
Multidisciplinary Science to
Applications” Coffee Break (09.30 – 10.00)
09.45 – 10.30
Invited Speaker 2
Dr. rer. nat. M. Nurhuda, Universitas
Brawijaya
Title: “Towards Energy Security for the
Poor”
Parallel Session (start at 10.00)
10.30 – 11.15
Invited Speaker 3
Prof. S.K. Lai, National Central Univ.,
Taiwan
Title: “Cluster Dynamics by Ultra-Fast
Shape Recognition Technique”
11.15 – 12.00
Invited Speaker 4
Dr. Nurul Taufiqurrochman*, Indonesian
Nanotech Society
Title:”Nanotechnology Development
Strategy for Supporting National Industry
in Indonesia”
12.00 – 13.00 Lunch Break 13.00 – 15.00
Parallel Session Parallel Session
15.00 – 16.30 16.30 – 17.00 Closing Ceremony 17.00 – 19.00 Free Time
19.00 – 22.00 Conference Gala Dinner
The Third Basic Science International Conference - 2013 ix
Parallel Session Day One - 16 April 2013 Majapahit 1 Room: Chemistry
Time Paper
ID Author(s) Title Moderator
13.00-13.30 Invited Prof. Petr Solich Recent Trends in Liquid Chromatography for
Bioanalysis
13.30-14.30
C01
Saprizal Hadisaputra,
Harno Dwi Pranowo, and
Ria Armunanto
Liquid-Liquid Extraction of UO22+
cation by 18-
Membered Crown Ethers: A DFT Study using
A Continuum Solvation Model
Akhmad
Sabarudin,
D.Sc.
C02
Heruna Tanty,
Margaretha Ohyver, Tati
Herlina, and Nurlelasari
Analysis of Inorganic Compounds Cr, Cd, CN,
Mn, and Pb in RAW Water and Water
Filtration Results in Jakarta-Indonesia
C03 Subriyer Nasir, Anthony
B. Hamzah
Pervaporation through NaA Zeolite
Membranes – A Review
C04 S.Muryanto
and E.
Supriyo
Inhibition of citric acid on the precipitation of
calcium sulphate dihydrate (CaSO4.2H2O)
C05
Hermin Sulistyarti,
Atikah, Sita Febriyanti,
Asdauna
A New Spectrophotometric Method for Iodide
Determination
Discussion/Question/Answer
14.30-15.30
C06
Chandrawati Cahyani,
Edi Priyo Utomo, and Wa
Ode Cakra Nirwana
Optimum Condition for Separation of Two
Immiscible Liquids,Patchouli Oil and Water,
and the Design of Separator
Masruri,
PhD
C07
Rurini Retnowati, Unggul
Pundjung Juswono,
Oktawirandy Rajaki
Free Radical Scavenging Ability of Xanthone
Isolated from the Mangostene Pericarp
(Garcinia Mangostana L.) by Electron Spin
Resonance (ESR)
C08
Muhammad Said, Abdul
Wahab Mohammad, Akil
Ahmad
Optimization of NaOH as the cleaning agent of
Polyethersulfone (PES) membrane fouled by
Palm oil mill effluent
C10 Imelda Fajriati,
Mudasir,
Endang Tri Wahyuni
Room-Temperature Synthesis of TiO2 –
Chitosan Nanocomposite Photocatalyst
Discussion/Question/Answer
The Third Basic Science International Conference - 2013 x
Parallel Session Day Two 17 April 2013 Majapahit 1 Room: Chemistry
Time Paper
ID Author(s) Title Moderator
10.00-11.00
C14 Masruri and Malcolm D.
McLeod
Amino acid-based ligand for the osmium
catalyzed asymmetric aminohydroxylation
reaction in styrene
C15
Suwardi,Harno Dwi
Pranowo dan Ria
Armunanto
Structure of Hf(IV) in aqueous solution – An
ab initio QM/MM MD approach
C16
Crys Fajar Partana, Ria
Armunanto, Harno Dwi
Pranowo, M Utoro Yahya
Molecular Dynamics Simulation of
Scandium(I) Singlet in Liquied Ammonia by
ab initio QM/MM MD
C18
Atikah, Chasan Bisri,
Rizki Layna R, Rizka
Setianing Wardhani
A New Coated Wire Iodide ion
SelevtiveElectrode (Iodide-CWE) base on
Zeolite membrane as Iodide ion sensor in
urine
Discussion/Question/Answers
11.00-12.00
C11
Rosenani A. Haque, Choo
Sze Yii and Srinivasa
Budagumpi
Silver(I) and mercury(II) complexes derived
from nitrile-functionalized N-heterocyclic
carbene: Synthesis, crystal structure, DNA
binding and nuclease studies
Lukman
Hakim,
D.Sc.
C12 Nurul Filzah Ghazali and
Ibrahim Baba
Synthesis and Spectroscopy of Dibutyltin (lV)
Dithiocarbamates Compounds
C13 Nur Fariza Abdul
Rahman, Mahiran Basri
Studies of Parameter Effects on Lipase-
catalyzed Synthesis of Engkabang Fat Esters
C17
Abdolhamid Ansari, Zahra
Sajadi and Jaber
Mozafarizadeh
Assessment of Hydrochemical Interactions
between Galendar's Aquifer and Geological
Formations
Discussion/Question/Answers
12.00-13.00
LUNCH TIME
Scientific Papers
Invited Papers
The Third Basic Science International Conference - 2013 I01
S.K. Lai1,2
and P.J. Hsu1,2
1Complex Liquids Laboratory, Department of Physics, National Central University, Chungli 320, Taiwan
2Molecular Science and Technology Program
Taiwan International Graduate Program, Academia Sinica,
Taipei 115, Taiwan
The time development of the molecular shapes (configurations) of macromolecules may be generated by
the molecular dynamics simulation and used to calculate for each molecular shape its structural similarity
(with respect to a reference configuration) with the ultra-fast shape recognition technique. This idea of
using the ultra-fast shape recognition technique [1] to track down the motion of atoms stems from our
observation that there are fundamental differences in the dynamics of atoms between a bulk system and a
finite system such as a macromolecule. For concreteness, we test the generality of the technique by
studying disparate metallic clusters. In broad sense, we look upon the metallic clusters as
“macromolecules”. To gain deeper insight into the cluster dynamics, our calculations are carried out in
three steps: pin down firstly individual atoms of the cluster and compute from their instantaneous
configuration a distribution of atomic distances, calculate a shape similarity index parameter, and finally
construct the temperature dependent contours of a probability shape similarity index function. The physical
content of the contours of the latter function presents a new perspective in interpreting the temporal change
of microstates and the bearings they have in revealing microscopic panoramas of pre-melting and melting
transition. Specifically, we found a correlation between the temperature variation of the probability shape
similarity function and the change in cluster dynamics, and hence gaining a more precise picture of
melting-like scenarios. Perhaps most importantly is that the ultra-fast shape recognition technique can be
implemented for understanding the sub-structures of clusters whose characteristic features present the kind
of discernment that proves difficult to extract in laboratory and computer-simulation experiments.
Reference:
[1] P.J. Ballester and W.G. Richards, Proc Roy Soc A Math. Phys. Eng. Sci. 463, 1307 (2007).
Cluster Dynamics by Ultra-Fast Shape Recognition
Technique
The Third Basic Science International Conference - 2013 I02
Nurul Taufiqu Rochman*
Research Center for Metallurgy, Indonesian Institute of Sciences
*Chairman, Indonesian Society for Nano
Kawasan PUSPIPTEK Serpong, Tangerang 15314 Indonesia
E-mail: [email protected]
It is believed that nanotechnology will become the next industrial revolution. Indonesia, a country with
abundant of natural resources (minerals, biodiversities) and 4th
largest in population, has to take advantage
for development of nanotechnology. This required appropriate strategy regarding to Indonesia’s potential
and capability in advancing technology. This study overviews a current status on development and
implementation of nanotechnology in Indonesia. First, a brief story about nanotechnology initiation in
Indonesia is described. National activities including policy, program and funding are then reported and
followed by explanation of several activities in each ministry (Ministry of Research and Technology,
Ministry of National Education, Ministry of Industry, and Ministry of Agriculture). Pictures of
nanotechnology human resources, R & D programs and facilities, and application of nanotechnology in
national industry are also explained in brief. Several research results on nanotechnology at our group are
also highlighted. Finally, activities on standardization, commercialization and building public awareness
are mentioned. In addition, potential areas of cross-country R&D cooperation and collaboration in the field
of nanotechnology also are described. As recommendation, good synergy between academic-
business/industry-government and networking development within regional research institution will
accelerate nanotechnology progress in Indonesia.
Keywords: nanotechnology development strategy, national industry, natural resources
Nanotechnology Development Strategy for Supporting
National Industry in Indonesia
The Third Basic Science International Conference - 2013 I03
Kwang-Ryeol Lee, Ph.D ([email protected])
Director-general, Institute for Multiscale Convergence of Matter,
Korea Institute of Science and Technology, Seoul, Korea
Computational research has been of increasing importance in wide spectrum of modern science and
technology. However, nowhere more so than in nano-bio science where molecular or atomic level
understandings of its structure, dynamics and properties are essential. Center for Computational Science
at KIST is focusing on the computational research in nano and bio technology. We are also
emphasizing the collaboration with experimental research for the synergic effect between experiments
and calculations. In this presentation, I will discuss the most up-to-date research activities of CSC-KIST
with specific examples of the nano-scale surface phenomena in both bulk and low-dimensional
materials, the multi-scale investigation of CNT reinforced composite materials, and the efforts for the
development of nano-TCAD environment.
Role of Atomic Scale Computational Research in the
Nanoscale Materials Science
The Third Basic Science International Conference - 2013 I04
Hideo Tsuboi
Nagoya University, Japan
Abstract
Paeony root (Paeoniae radix; Shakuyaku in Japanese) is one of the most well-known herbs in China, Korea
and Japan and has been used as a medicine for more than 1200 years. Paeoniflorin (PF), a glucoside, is
known to be one of the principle bioactive components of paeony root. PF has been reported to have
immunoregulatory, anti-allergic, anti-inflammatory, cognition-enhancing, neuromuscular-blocking, anti-
convulsant, anti-hyperglycemic, anti-coagulant, and sedative effects. However, the effect to innerceller
signal transduction or the bioactivity in molecular level is still not investigated at all. I have been interested
especially in the effect of PF to our immuno system and its working mechanism. Today, I introduce PF as a
herbal medicine and it's bioactivity from immunological stand point.
Paeonilorin(PF) Strongly Effects Immuno System
The Third Basic Science International Conference - 2013 I05
A/Prof. Dann Mallet
Mathematical Sciences, Queensland University of Technology, Brisbane, Australia
Abstract
Chlamydia trachomatis is the most common sexually transmitted pathogen of humans, with over 90 million
new adult cases occurring worldwide each year. Left untreated, chlamydial infection may result in severe
detrimental effects on reproductive health, especially in women. Infection becomes problematic and
persistent when it progresses from the lower to the upper genital tract, but despite intensive research there
is still debate over the mechanisms by which this progression occurs. This has led to the development of
mathematical models of the spatial changes and dynamics involved in the infection process. Here we
present a brief discussion of C. trachomatis before illustrating the progress to date in mathematical
modeling of the pathogen.
Investigating Chlamydia trachomatis using mathematical
and computational models
The Third Basic Science International Conference - 2013 I06
Petr Solich
Department of Analytical Chemistry, Charles University, Faculty of Pharmacy, Hradec Kralove, Czech
Republic
Abstract
Analytical chemistry – as a part of chemistry - is playing critical roles in the understanding of basic science
to a variety of practical applications, such as biomedical applications, environmental monitoring, quality
control of industrial manufacturing, food analysis, etc. One of the major challenges facing the medicine
today is developing of new therapies that improve human health. To help address these challenges the
utilization of enormous modern analytical technologies and high-throughput automated platforms has been
employed in the last decade, in order to perform more and more experiments in a shorter time frame with
increased data quality.
Liquid chromatography – and chromatography in general as well - is without any doubts the most
important analytical methodology, combining both qualitative and quantitative analysis in one step. In the
last decade various analytical strategies have been established to enhance separation speed and efficiency in
liquid chromatography applications. Current trends in fast liquid chromatographic separations involve
monolith technologies, fused-core columns, high-temperature liquid chromatography (HTLC) and ultra-
high performance liquid chromatography (UHPLC). The high specificity in combination with high
sensitivity makes it an attractive complementary method to traditional methodology used for routine
applications.
Introduction of ultra-high performance liquid chromatography (UHPLC) in 2006 has brought a new
challenge and attract more and more scientists for development of new applications using liquid
chromatography. Together with this new instrumentation, a huge expansion of new stationary phases was
registered during the last decade. Several different technologies in stationary phases - with different
characteristics were introduced into the market. Introduction of sub-2-micro particles brought a new
challenge into laboratories. Extensive decrease of time of analysis and excellent separation efficiency
attracted manufacturers and scientists to look for new applications. Monolithic technology is based on a
unique sorbent material allowing good quality of separations in a minimal time. The main advantages of
monoliths, apart from short analysis time, are long lifetime and immense robustness, in most cases far
exceeding those of particulate columns. This new type of monoliths have at higher efficiency, better peak
symmetry and longer lifetime compared with particulate columns. Core-shell technology using porous shell
and solid core particles broke into market during last 5 years. These columns can be used in common
HPLC instruments as well as in UHPLC systems. This technology promises to increase of resolution and
maximizes throughput, and result in solvent saving and easier method transfer.
Application of UHPLC and various new stationary phases to the mainly bioanalytical analysis, but also to
environmental and pharmaceutical analysis will be discussed and examples of application to analysis of
real samples will be shown.
Recent Trends in Liquid Chromatography for Bioanalysis
Scientific Papers
Submitted Papers
The Third Basic Science International Conference - 2013
C02-1
Abstract — This review is the result of analysis of inorganic
compounds Chromium (Cr), Cadmium (Cd), Cyanide (CN),
Manganese (Mn) and Lead (Pb) in the raw water, water filtration
results of Granular Activated Charcoal(GAC) and water
filtration results of Reverse Osmosis(RO). Samples from 30
drinking water refill depot(AMDIU) in five regions of the District
Jakarta (DKI Jakarta) taken in May-June 2012.The results show
that the raw water contains of CN, Pb, Mn, Cr and Cd
respectively 0.0211 mg/l, 0.009 mg/l, 0.130 mg/l, 0.0116 mg/l and
0.0021 mg/l. The water filtration result of GAC contains CN, Pb,
Mn, Cr and Cd respectively 0.0197 mg/l, 0.0085 mg/l, 0.116 mg/l,
0.0103 mg/l, and 0.002 mg/l and the result of RO contains CN,
Pb, Mn, Cr and Cd respectively 0.0195 mg/l, 0.0078 mg/l, 0.099
mg/l, 0.099 mg/l and 0.0018 mg/l. There are significant
differences at α=0.05 for Cd, Cr and Mn in the raw water and
RO filtration results, while for water, water filtration GAC
results are not significantly different. It means the raw water
filtration GAC results and RO results contain levels of CN, Pb,
Mn, Cr and Cd less than the standards level of the Indonesian
Ministry of Health. So the raw water, water filtration results of
GAC and RO in DKI Jakarta were qualified health for
consumption.
Index Terms— Inorganic Compounds, Raw water, Water
filtration, MANOVA
I. INTRODUCTION
ater is a compound that is needed by the body. Water
helps the metabolism process as well as a result
transformation metabolism and oxygen to all parts of the body
cells and regulates body temperature. Water is fundamental to
our quality of life, so every day is recommended for human to
drink eight glasses of water or at least two and a half liters,
that your metabolism will be good.
In 2011 the population of Jakarta, approximately
10,187,595 peoples, they need clean water per day average of
2.38 million m3. The Government through the Regional Water
Company (PDAM), until now only be able to distribute 1.53
million m3/day (approximately 39%) to the total water needs
Heruna Tanty as a Lecturer at Bina Nusantara University, Jakarta,
Indonesia (phone: +6221-535 0648; fax: +6221-5300244; e-mail:
[email protected]). Margaretha Ohyver as a Lecturer at Bina Nusantara University, Jakarta,
Indonesia ( e-mail: [email protected]).
Tati Herlina as a Lecturer at the Department of Chemistry, State University of Padjajaran, Sumedang, Indonesia ( e-mail:
Nurlelasari as a Lecturer at the Department of Chemistry, State University of Padjajaran, Sumedang, Indonesia ( e-mail: [email protected]).
of residents in Capital Region (DKI) Jakarta (5)
. Clean water
crisis in Jakarta as sources of ground water in Jakarta had been
contaminated by the bacteria E-coli and fecal coli bacteria,
The results of Athens research in Jakarta, Bekasi and
Tangerang showed 31.6% of ground water containing the
bacteria E-coli and fecal coli bacteria (4)
. So when referring to
the Minister of Health Regulation No.
416/MENKES/PER/1990(10)
about clean water requirements,
groundwater in Jakarta cannot be consumed.
Water needs of Jakarta residents provide opportunities for
medium entrepreneurs to open depots drinking water refill
(AMDIU). With prices ranging between USD 3000 - USD
3500 per gallon, lower middle economic people can buy
drinking water needs. Within a few years, more than 2000
AMDIU spread in Jakarta, and about 65% AMDIU not listed
on the Department of Health. This condition is of course
difficult for the government to control the quality of AMDIU.
Drinking water refill (AMDIU) generally use a process
filtration calls filters Granular Activated Charcoal (GAC), and
today there are also free sold by the filtration process Reverse
Osmosis (RO) which can be installed directly in the home.
Water is a universal solvent, so that the water soluble
organic or inorganic substances. Water was containing
inorganic chemicals 75.3% and 24.7% of organic chemicals.
Organic chemicals are needed by the body, because it is
cultivated in water treatment chemicals are not removed, while
the inorganic chemicals are not needed by the body at all and
even harmful to the body. Therefore, their presence in
drinking water should be eliminated or reduced in number as
small as possible.
The study contains an inorganic compound Cd, Cr, Mn,
Pb and CN-ions have been studied by Heruna et al(2)
, from 10
samples around AMDIU Bina Nusantara University Jakarta, it
was only Mn a qualified health, four other inorganic
compounds (Cd, Cr, Pb and CN) is still above the standards,
and the water that has been processed by the RO filter it meets
the appropriate standards prescribed by the Ministry of Health (11)
.
This study aimed to determine whether the content of
inorganic chemicals compounds Cd, Cr, Pb, Mn and CN-in
raw water and drinking water refill in Jakarta according
quality standards. It also whether there are differences in the
raw water, water filtration GAC and RO result of inorganic
chemical substances.
Analysis of Inorganic Compounds Cr, Cd, CN, Mn, and
Pb in RAW Water and Water Filtration Results in Jakarta-
Indonesia
Heruna Tanty, Margaretha Ohyver, Tati Herlina, and Nurlelasari
W
The Third Basic Science International Conference - 2013
C02-2
II. METHODOLOGY
A. Material
The materials were 30 types of raw water samples, 30
samples of the type of filtration AMDIU, 0.05 M HNO3 (aq), a
solution of 100 mg Fe / l, Pb (NO3) 2 (aq), HCl (l), 10%
NH4OH(aq), (NH4) 2HC6H5O7 (aq) 1 l , KCN (s), 0.1 N
KMnO4(aq), NaNO3(aq)5%, 10% NaHSO3(aq), dithizon (aq)
100mg / l, I2(aq), KI(aq), K2Cr2O7(aq), H2SO4(aq) 18N, 6N,
1N NaOH(aq), NaC2H3O2 .2 H2O, CHCl3 (aq),(NH4)
2S2O6(aq), chloramin-T (aq), KCN (s)
B. Equipment
A set of glasses equipments (test tube, flaskerlenmayer,
flask, pipette, burette, etc.), λ 510 nm DR.2800
spectrophotometer, pH meter, balance electric, Nasslertube,
filter photometers
C. Sample
The sample used in this study consisted of 30 samples of
raw water (control) and 30 samples of water filtration results
depot refill (AMDIU) in five areas of Jakarta. Determining the
location AMDIU sampled based on observations and
interviews with owners AMDIU about the amount of water
(gallons) were sold / month. Sampled is AMDIU with sales
over 2500 gallons of water / month. Considering that this
shows AMDIU will not store raw water for too long and the
number of consumers around AMDIU enough. From each
refill depot taken one raw water sample, taken directly at the
tanker was filling the storage tanks at the site AMDIU, and
filtration of the water sample results from these AMDIU.
Total of 60 samples collected samples as shown in table .1
TABLE I
SAMPLES IN EACH AREA JAKARTA
Distric Row Water Result Filter GAC
( AMDIU) water
Centre Jakarta 5 samples 5 samples
East Jakarta 7 samples 7 samples
North Jakarta 8 samples 8 samples
West Jakarta 5 samples 5 samples
South Jakarta 5 samples 5 samples
Total 30 samples 30 samples
D. Place and Time Research
Sampling is done from April to May 2012. All samples
are analysis at the laboratory of Chemistry Department of the
Faculty of Mathematics and Natural Sciences, University of
Padjadjaran Bandung, Indonesia. The result of RO filtration
will be processed for laboratory testing levels of inorganic
compounds.
E. Test of Inorganic Compounds
This study was done by using observation and
experimentation (laboratory tests). The methods to test the five
levels of inorganic compounds Cd, Cr, Mn, Pb and CN are
a. Determination the levels of Pb2 +
and Cd2
This determination levels of Pb2 +
and Cd2 +
dissolved in the
sample used Dithizone method (12)
. Samples were acidified
with concentrated nitric acid and the solution was 0.1 N
iodine solutions which then is mixed with citrate-cyanide
ammonia solution and extracted with ditizon in chloroform
(CHCl3) to form complexes ditizonate red. The complex
contains measurable levels ditizonat Pb/Cd using DR-2800
spectrophotometer at a wavelength of 510 nm.
b. Determination of levels of Cr
Determination of Cr dissolved in the sample calorimetry
method (13)
. Samples that contain chromium total acidified
with phosphoric acid and sulfuric acid. Hexavalent
chromium was determined by reaction of the acid form
complexes difenilcarbasida the red-purple. Determination of
wavelength was measured at 530-540 nm using a
spectrophotometer DR-2800. c. Determination of Levels of CN
-
Determination of CN-ions in the sample is done by
titrimetric method (1)
. Cyanide ion in alkali titrated with a
solution of silver nitrate to form silver cyanide complexes,
Ag (CN) 2 - were detected using p-
dimetilaminobenzalrodanin yellow. Titration is using
potassium chromate argentometri indicators.
d. Determination of levels of Mn
To determine the levels of Mn the sample used Persulphate
method (8)
samples were oxidized using hydrogen peroxide
solution by the addition of nitricacid, sulfuric acid,
silvernitrate, and ammonium persulfate. Kalium permangan
attitration is using a solution of sodiumoxalate.
F. Data Analysis
In the data analysis steps are as follows: 1. Descriptive analyzes include average, standard deviation,
minimum and maximum values (9)
2. Test the multivariate normal assumption and homogeneity
of variance covariance matrix using Box's M (3)
3. Test MANOVA using test Pillai's Trace, Wilks' Lambda,
Hotelling's Trace, and Roy's Largest Root, aims to test
whether there are differences in the average levels of
inorganic compounds in the control sample and the sample
of the filtrate, the alpha (α) 5% (6)
4. Least Significance Difference (LSD) test to conclusion the
differences in average levels of inorganic compounds and
the results of the control sample filtration at α = 5%. (7).
III. RESULTS AND ANALYSIS
The average of CN, Pb, Mn, Cr and Cd raw water,
filtration Granular Activated Charcoal (GAC) and filtration
processes Reserve Osmosis (RO) can be seen in Table 2. It
can be seen that the five levels of inorganic compounds was
reduced in the process of raw water by GAC filtration or RO.
The results of descriptive analysis of the levels of inorganic
are compounds in the raw water and GAC filtration and RO
results shown in Table 3.
The Third Basic Science International Conference - 2013
C02-3
TABLE 2.
THE AVERAGE CONTENT OF INORGANIC COMPOUNDS IN THE RAW WATER, GAC AND RO
Compounds
N
Average Standard
Deviation
Minimum Maximum
mg/l mg/l mg/l
Mn 90 0.1151 0.0345 0.06 0.18
Raw water 30 0.1303 0.0383 0.07 0.18
Result GAC water 30 0.116 0.0333 0.06 0.17
Result RO water 30 0.099 0.024 0.06 0.13
Cr 90 0.0104 0.0034 0.005 0.018
Raw water 30 0.0116 0.0036 0.006 0.018
Result GAC water 30 0.0103 0.0034 0.005 0.016
Result RO water 30 0.0092 0.003 0.005 0.015
Cd 90 0.002 0.0005 0.0007 0.0028
Raw water 30 0.0021 0.0005 0.0008 0.0028
Result GAC water 30 0.002 0.0005 0.0008 0.0027
Result RO water 30 0.0018 0.0005 0.0007 0.0025
Pb 90 0.0085 0.0026 0.005 0.015
Raw water 30 0.009 0.003 0.005 0.015
Result GAC water 30 0.0085 0.0026 0.005 0.014
Result RO water 30 0.0078 0.0022 0.005 0.013
CN 90 0.0201 0.0034 0.015 0.027
Raw water 30 0.0211 0.0038 0.015 0.027
Result GAC water 30 0.0197 0.0032 0.015 0.025
Result RO water 30 0.0195 0.003 0.015 0.025
TABLE3.
DESCRIPTIVE ANALYSIS OF LEVELS OF SUBSTANCES IN EACH TREATMENT
Samples Mn(mg/l) Cr(mg/l) Cd(mg/l) Pb(mg/l) CN(mg/l)
Raw Water 0.1303 0.0116 0.0021 0.009 0.0211
Result GAC water 0.116 0.0103 0.002 0.0085 0.0197
Result RO water 0.099 0.0092 0.0018 0.0078 0.0195
Standard Quality 0,4 0,05 0,003 0,01 0.07
Normality Tests
Before the MANOVA analysis, multivariate normal
assumption was tested. The hypothesis used is as follows:
H0: The data follow a multivariate normal distribution
H1: The data do not follow the distribution of a multivariate
normal distribution.
From the results of the multivariate normal testing that is
in figure 1 it can be seen that the distance is less than is equal
to 55.6%. Because this value is greater than 50%, it can be
concluded that the data content of Mn, Cr, Cb, Pb, and CN
follow a multivariate normal distribution.
Homogeneity Tests
The results of homogeneity test of variance-covariance can
Data display
Extensive 0.555556
Fail to reject Ho, and concluded that the data
follow multinormal distribution
181614121086420
18
16
14
12
10
8
6
4
2
0
di
Plot Uji Multinormal
Sources: Processed Minitab, 2012
Fig 1. Scatter plot of multivariate normal assumption test
The Third Basic Science International Conference - 2013
C02-4
be seen in Figure 2. The P value was 0993. Since it higher
than α= 0.05, it can be concluded that the variance of Mn, Cr,
Cb, Pb, and CN were the same in all treatments (Ho accepted).
MANOVA and LSD Test The results of multivariate analysis of variance (MANOVA)
can be seen in Figure 3. The P value of test results in the
fourth test (Pillai's Trace, Wilk's Lambda, Hotelling's Trace,
and Roy's Largest Root) was 0.000. Because all the P value
were less than α=0.05, then there was a difference means the
average of the four treatments.
Because the results MANOVA concluded that there was a
mean difference of each treatment, then to the next stage
further tested with a variety of analysis to look for treatment or
where a different process. It was use Least Significance
Difference (LSD) in Table 4. The hypothesis used is
H0: there is no difference in the average
H1: there is a difference in the average
Fig 3. Results Calculation ONE-WAY MANOVA using MINITAB
TABLE 4 LEAST SIGNIFICANCE DIFFERENCE TEST RESULT (LSD)
Inorganik Couplestreatment Difference average P value Conclusion
Mn 1 dan 2 0.0143333 0.090 no different
1 dan 3 0.0313333 0.000 different
2 dan 3 0.0170000 0.045 different
Cr 1 dan 2 0.0013000 0.133 no different
1 dan 3 0.0024000 0.006 different
2 dan 3 0.0011000 0.203 no different
Cd 1 dan 2 0.0001400 0.264 no different
1 dan 3 0.0003600 0.005 different
2 dan 3 0.0002200 0.081 no different
Pb 1 dan 2 0.0005333 0.430 no different
1 dan 3 0.0012000 0.078 no different
2 dan 3 0.0006667 0.324 no different
CN 1 dan 2 0.0014000 0.108 no different
1 dan 3 0.0016000 0.067 no different
2 dan 3 0.0002000 0.817 no different
Sources: Processed SPSS, 2012
Note: 1 = raw water (control), 2 = water filtration results GAC, 3 = water RO filtration results
Decision making is Ho is rejected if the P value is less
than α = 5%. At the levels of substances Mn, the average
difference between the levels of substances in the raw water
and water filtration GAC is 0.0143333. Furthermore, through
the LSD test P value 0.090 obtained. This value is more than α
= 5%, so the conclusion is Ho failed rejected. There is no
difference in the average levels of substances in both Mn such
Box's M 15.497
F 0.474
df1 30
df2 2.40E+04
Sig. 0.993
Sources: Processed SPSS, 2012
Fig 2. Test results Homogeneous Variance Covariance with Box'M
The Third Basic Science International Conference - 2013
C02-5
treatment. Meanwhile, the average between the levels of
substances in the raw water RO filtration is 0.0313333. It has
P value 0.000 which is less than α = 5%, so it is concluded that
there are differences in the average levels of substances
significant Mn in both treatments. Similar results were also
obtained on LSD test between GAC and RO filtration
treatment, that there are differences in the average Mn
significant substance in both treatments.
Meanwhile, the levels of substances Cr and CD, the average
levels were significantly different between the treatment of
raw water and RO filtration results. However, at the levels of
Pb and CN substance no different average significantly
IV. CONCLUSSION
From the research that has been conducted and based on
the results of data processing five levels of inorganic
compounds Cd, Cr, Pb, Mn and CN in 30 raw water samples,
30 samples of water filtration results Activated Granular
Charcoal (GAC) and the results of 30 samples of water
filtration Reverse Osmosis (RO ), it can be concluded:
1. The average fifth grade inorganic compounds (Cd, Cr, Pb,
Mn and CN) contained in the raw water will decrease after
GAC filtration and RO. This shows that the filtration
process is done can reduce the levels of five inorganic
chemicals.
2. Raw water contains high levels of CN, Pb, Mn, Cr and Cd
respectively 0.0211 mg / l, 0.009 mg / l, 0.1303 mg/l,
0.0232 mg/ l and 0.00212 mg / l. Water contains high levels
of GAC filtration results CN, Pb, Mn, Cr and Cd 0.0197
mg/l, 0.0085 mg / l, 0.116 mg / l, 0.0103 mg/l, 0.002 mg/l
and the water contains high levels of RO filtration results
CN, Pb, Mn, Cr and Cd 0.0195 mg/l, 0.0085 mg/l, 0.099 mg
/ l, 0.0092 mg / l and 0.0018 mg / l.
3. The average fifth grade inorganic compounds in raw water
and water filtration results GAC or lower RO drinking water
quality standard set by the Department of Health, that means
either the raw water or water filtration GAC and RO result
safe for consumption.
4. Levels of Cr, Cd and Mn in the raw water are not different
from the GAC water filtration results. While the RO water
filtration results differ at a significant level (α) of 5%.
Enterprises depot refill drinking water (AMDIU) in
Jakarta using raw water and filtration equipment that meets
health standards
ACKNOWLEDGMENT
Thanks to the Directorate General of Higher Education,
Ministry of Education of the Republic of Indonesia and rector
of Bina Nusantara University, Jakarta – Indonesia.
REFERENCES
[1] American Society for Testing and Materials, 1987.
Research Rep.D2036:19-1131.American Soc. Testing and
Material .Philadelphia,Pa.
[2] Heruna T, Iwa S, Edison R. 2010. Analisis Kandungan
Zat Kimia Anorganik pada Beberapa Proses Air Minum
Kemasandan Isi Ulang menggunakan One-Way Manova.
Comtech, 2010, 1, 48.
[3] Hsu, J.C, 1984. Constrained Two Sided Simultaneous
Confidence Intervals For Multiple Comparisons With the
Best, Analls of Satistics, 1984, 12,1136.
[4] http://www.ekologi.litbang.depkes.go.id/data/abstrak/Ath
ena.pdf [5] Kompas, 2012. Banyak warga Ibu Kota belum dapat air bersih.
Senin 30 April
[6] Kotz, Samuel and L. Johnson, Norman. 1993. Process
Capability Indices, University of North Carolina, Chapman &
Hall, London
[7] Lavene, H,1990. Contributions to probability and Statistics.
Standard University Press, CA.
[8] Nydahl,F,1949. Determination of manganese by the persulfate
method. Anal Chem, Acta. 3:144
[9] Ott, Lyman ,1984. An Introduction to Statistical Methods and
Data Analysis, 2th Edition, Duxbury press.
[10] Regulation of the Minister of Health of the Republic of
Indonesi, 1990. No 416/MENKES/PER/1990)
[11] Regulation of the Minister of Health of the Republic of
Indonesi, 2010.No 492/MENKES/PER/IV/2010
[12] Snyder.LJ,1947. Improved dithizone method for determination
of lead-mixed color method at high pH. Anal Chem, 19:684
[13] U.S. Environmental Protection Agency, 1996. Determination
hexavalent chromium by ion chromatography. Method
1636.EPA 821-R-96-003,U.S. Environmental Protection
Agency, Washington,D.C
The Third Basic Science International Conference - 2013
C03-1
Abstract— The article concerns with pervaporation process
through NaA zeolite membranes. This kind of membrane is
known for its separation performance in removing water from
organic compound mixture. Extremely good water adsorption
level and the feature of molecular sieving are the main attributes
that makes them very good in water removal. Recent studies
show that NaA zeolite membrane has very high separation factor
(more than 10000) and reasonable flux (up to 5 kg m2/h). Despite
these good separation performances, NaA zeolite membranes
suffer some drawbacks concerning its durability under highly
acidic condition and high temperature.
Index Terms—azeotrope separation, membrane, zeolite
I. INTRODUCTION
ervaporation is a method to separate liquid mixtures which
is depend on partial vapor pressure of the compounds. To
increase the driving force, the permeate side uses vacuum
condition. The growing uses of pervaporation are especially in
energy application, when it is used to overcome the azeotrope
condition of water/ethanol mixture, separation of r organic
compound and water mixtures such as 2,2,2-trifluoroethyl
alcohol (TFEA) [24], isopropanol [7,15,17,20,23] and acetic
acid [25]. In some cases, pervaporation is also used to separate
hydrocarbons [27].
The pervaporation can be explained in this way: The vapor
is enriched in the preferentially permeating component and is
condensed for future processing. Meanwhile, the retentate is
enriched in the non-preferentially permeating component. The
retentate stream can be either recycled or used for other
processes [26].
When the pervaporation process was still in infancy,
polymeric membranes were much more common put into use.
The sole reason was its high reproducibility, cheap, and
relatively easy to use. Usually, “thermally resistant” polymer
such as polyimide was used. Yet this type of membranes was
not ideal because it is not really resist even at slightly higher
temperature (about 100oC or above), thus resulting to
proneness to swell. The swelling membrane turns to decrease
the performance significantly as the membrane structure will
take more liquid.
Manuscript received April 4, 2013.
A. B. Hamzah is with the University of Sriwijaya, Palembang, 30139
Indonesia (corresponding author to provide phone: +6285267122394; e-mail: antoinetonee@ gmail.com).
S. Nasir is with the University of Sriwijaya, Palembang, 30139 Indonesia
(e-mail: [email protected]).
Zeolite has been used in many applications, such as catalyst
[1], ion exchanger, and adsorbent. Meanwhile, zeolite
membranes have also been used for pervaporation both
industrially and in laboratory studies. These membranes are
polycrystalline zeolite layers deposited on porous inorganic
supports. Zeolite membranes are significantly structurally
stable both physically and chemically than polymer
membranes. Most zeolite membranes are resistant to low pH
(with some exceptions) and able to perform good separation
even in temperatures up to 1270 K [4, 10]. Moreover, zeolite
membranes do not swell and have uniform molecular size
pores, allowing molecular sieving. Despite its advantages,
zeolite membranes are inferior to polymer membranes in some
ways: they are more expensive to produce and more brittle.
II. NAA ZEOLITE MEMBRANES
A. NaA Zeolite Membranes Characteristics
Zeolite A with sodium cations, denoted as NaA, has
formula of Na12[(AlO2)12(SiO2)12]-. 27H2O, and contains cages
with orthogonal 3-D oriented apertures of approximately 0.4
nm. The pore dimension is changed to 0.45 or 0.30 nm, when
the zeolite is ion exchanged with Ca2+
or K+, respectively [17]
which is close to or smaller than the molecular kinetic
diameters of short-chain alkanes. As a membrane, NaA zeolite
was very promising molecular sieve membrane due to their
hydrophilicity. These features make NaA zeolite very good in
terms of removing water substances out of the mixtures. NaA
zeolite shows excellent hydrophilic characteristics because of
its low silica/alumina ratio. The aluminum content of A-type
zeolites is high (Si/Al = 1), making them hydrophilic [34].
Bowen et al. mentioned NaA zeolite has a greater average
affinity for water than methanol [26]. Water-NaA affinity has
heat of adsorption of 100 ± 25 kJ/mol, whereas methanol-NaA
has only 85 ± 20 kJ/mol. This difference is enough to explain
why NaA zeolite is so hydrophilic.Hydrophilic zeolite
membranes like NaA have effectively dehydrated alcohols
with high separation factors (Table 1).
Like any other polycrystalline zeolite membranes, NaA
zeolite membrane also contains transport pathways in
intercrystalline regions, or non-zeolite pores. Kondo and Kita
(2010) proposed the theoretical consideration based ontheir
experiments (see Fig 1), in which the zeolitic pores in zeolite
layer are assembling in a very fine and narrow non-zeolitic
pore opened to the support tube through the zeolite layer[7].
In PV (see Figure 1), the feed solution evaporates at Boundary
1 near the membrane surface. The water molecules in the feed
are selectively adsorbed in zeolitic pores in the zeolite layer on
Pervaporation through NaA Zeolite Membranes - A
Review
Anthony B. Hamzah, Subriyer Nasir
P
The Third Basic Science International Conference - 2013
C03-2
the membrane surface, and then transported to the non-zeolitic
pore through the zeolitic pores by surface diffusion.
Subsequently, at narrower space (Boundary 2) in the non-
zeolitic pore, the capillary condensation occurs at lower
relative pressure of vapor, and then the space (δ2 length)
filledby the condensate. Subsequently, on the condition that
the permeation side was kept under vacuum, the condensate
evaporates in Boundary 3 and diffuses into the permeation
side. The condensate significantly inhibits permeation of other
components by blocking them from entering the pore.
B. NaA Zeolite Membranes Synthesis’
NaA zeolite membranes are most often prepared by
hydrothermal synthesis [2-13, 16-17, 31-33]. Hydrothermal
synthesis involves crystallization of a zeolite layer onto a
porous support from a gel that isusually composed of water,
amorphous silica, a source fortetrahedral framework atoms
other than Silica, a structure directing organic template, and
sodium source (usually Na2O). This gel is placed in contact
with the supportin an autoclave.The operation time,
temperature, and gel compositions for crystallization depend
on the zeolite. Supports are generally alumina tubes or discs,
although other ceramics, and other materials have been used,
such as mullite [3,7], α-Al2O3-boehmite [4], UV-radiated TiO2
wafer [8], porous Ni sheet [13]. Xu et al. even used hollow
fiber supports [3] with considerable result. Alumina(α-Al2O3)
supports typically have pore diameters between 100-200 nm.
During in situ crystallization, zeolite crystals nucleate grow
on the support surface. Crystals sometimes nucleate in the
bulk solution, but this is not preferred because it will form
framboid-like zeolite structure in the surface, making the
surface rougher and thicker the supposedly thin NaA zeolite
layer, thus lowering the flux significantly [12,15,17]. The
faster seed transfer to the support surface, the better the thin
layer surface will be.
Nucleation in the bulk is less likely for dilute gels [2,15].
Techniques have been developed to prepare NaA zeolite
membranes with organic template molecules [9, 20], as this
type of membranes are usually prepared without a template,
but if a template is used, the zeolite structure forms around the
organic template molecules, making the pores. Addition of
template also induces formation of smaller, more interlocked
crystalline.
Seed crystals are added to the support prior to the
crystallization step to provide sites for zeolite growth and
improve control of crystal growth. Using seed crystals is
referred to as two-step crystallization. This method is usually
used to prepare high-performance, thin layer membranes. Dip
coating [4], electric charge [19], vacuum seeding [23],
microwave [14, 22] and the usage of larger-pore support [10]
increased seed crystal adherence and improved membrane
quality.
C. NaA Zeolite Membranes Separation Performances
As mentioned previously, NaA zeolite membranes are
nearly ideally suited for organic dehydration because they are
highly hydrophilic and their pore diameter (0.4 nm) is smaller
than almost all organic molecules but larger than water. These
aforementioned properties allow preferential permeation of
water over organic compounds with separation factors that are
often over 1000 and sometimes higher than 10,000. These
high separation factors are sensitive to permeate concentration
because the water concentrations are often higher than 98%.
NaA zeolite membranes are very selective to water and its
fluxes are relatively high compared to other zeolite
membranes. Meanwhile, mordenite (in this article used as
benchmark zeolite membrane), which is known for its
resistance against acidic condition, is not even the same as
NaA zeolite. Whilst NaA zeolite membranes’ ethanol fluxes
and separation factors are about 3-4 kg m2/h and10000
respectively, compared to mordenite membrane was 1.17 kg
m2/h and 6800 [20]. This caused by pore size and how
interlocked the crystallines are. NaA zeolite membranes,
prepared with appropriate concentration and seeding time, are
very well interlocked, leaving only small defects on its surface
[18,19].
D. NaA Zeolite Membranes Durability
For application in separation processes, the membrane must
be defect-free, dense and uniform. Recently it has been
reported that the NaA zeolite membrane has only a low
thermal stability. Caro et al. [28] suggested the mismatch of
thermal expansion coefficients as one of the reasons the NaA
zeolite membrane shows such a low gas-separation
performance. Noack et al. [29] reported that LTA zeolite in
the wet state shows a strong contraction (−50×10−6
/K)
between 25 and 100 ◦C, a strong expansion (+50×10−6
/K)
between 100 and 150 ◦C, and a weak contraction (−5×10−6
/K)
between 150 and 450 ◦C. Considering the average
pervaporation processes are operated in temperature range of
50-100◦C and vapor permeation between the strong expansion
temperature, these are clearly affected the endurance of NaA
membrane under such circumstances. Moreover, NaA
membranes made using small-sized pore support are even
weaker because they tend to build thin intermediate layer,
because the size of the pores are small enough to be plugged
by the seeds [10].
Some methods were proposed to lessen the effects. Cho et
al. [10] proposed what is called “control of intermediate layer
structure”. It is basically a way to thicken the intermediate
layer using large pore support, so the contraction force and
shear by the contraction of NaA layer can be shared to the
support (in case of pervaporation). Das et al. [4], propose
another way to reduce cracks on NaA zeolite membranes by
Fig. 1. Schematic diagram of flow model occurring in a zeolite membrane. The feed is at the left hand side, whereas permeate is in the opposite (beyond
the support)
The Third Basic Science International Conference - 2013
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utilizing addition of boehmite to reinforce the intermediate
layer. All these methods showed improved thermal stability.
Smaller seed particles and larger support pores are proved
beneficial to the formation of physically better NaA
membranes, but they do have drawbacks. Yang et al. [32]
found that smaller seed particle (0.3 µm) induces low-quality
zeolite like hydroxysodalite (pore size of 2.8 µm) instead of
NaA. It was not clear whether such low quality membranes
induced by submicron-size seeds were attributed to over-
crystallization, since the smaller seeds generally required short
crystallization time.
Although the NaA-type zeolite membrane shows excellent
performance, the acid stability of the membrane is reportedly
poor. Unfortunately, only limited publications are available in
the literature. Hasegawa et al. [5] studied the permeation
fluxes through the NaA-type zeolite membrane was monitored
using the real-time monitoring system to study the influence of
acid on the permeation properties. At the end of the
experiment, it could be concluded that the NaA zeolite layer is
virtually destroyed, separated from its support, making the
membrane practically useless for pervaporation operations. As
in 2012, there has been some experiment related to endurance
of zeolite membrane under acidic condition, mainly intended
to replace the existing NaA zeolite membranes with more
acid-resistant ones, such as mordenite [21], merlinoite and
phillipsite [30].
E. NaA Zeolite Membranes Reproducibility
Although progress in improving separations suggests that
zeolites may have further uses in large-scale pervaporation,
the only current large-scale commercial use of NaA zeolite
membranes we are aware of is in organic dehydration. Mitsui
Engineering & Shipbuilding Co. in Japan has implemented A-
type zeolite membranes for this application commercially in
2001. The Mitsui Engineering & Shipbuilding Co. zeolite
membrane pervaporation plant uses 20–30 μm thick NaA
zeolite membranes on porous, tubular ceramic supports, and
processes alcohols up to 530 L/h with separation factors as
high as 10,000, and increased the alcohols purity from 10
wt.% water to 0.2 wt.% water content.[31].
In 2008, Aguado et al. [17] reported a continuous NaA
zeolite membrane production, by continuously flowing and
practically immersing the support tube in “nutrient”, yet the
result was not satisfactory. The NaA zeolite membrane was
not properly interlocked and even the polycrystalline had not
yet formed as it hoped to be. Meanwhile, Sato and Nakane
[12] proposed a much-higher performance reproducible
fabrication method for high-flux NaA zeolite membrane has
been developed for industrial mass production. The
experiment itself was undertaken by using dip coating,
therefore in the mass-production scale it would be still had
difficulty because it cannot produce membranes with very
large surfacecommercially.
Another research conducted by Pina et al. [16] conluded that
zeolite NaA membranes have been synthesized by secondary
growth on the external surface of α-alumina tubular supports
using a semicontinuous system in which fresh gel was
periodically supplied to the synthesis vessel. Compared to
traditional batch methods, the procedure developed in this
work provides a better control of the synthesis and
crystallization conditions and is easier to implement at an
industrial scale. The membranes obtained by the semi-
continuous method displayed reasonable separation
performance in the pervaporation of ethanol/water mixtures
(e.g., a separation factor of 3600 at a water permeation flux of
3.8 kg/h.m2).
F. Future Trends
The NaA zeolite membrane technology is still evolving.
Advances in the following areas have potential to improve
understanding and effectiveness of pervaporation through
zeolite membranes:
An improvement of flux with making thinner NaA
zeolite upper layer
New techniques of secondary growth
Endurance of NaA zeolite membranes under high
temperature and low pH.
The mass-production of NaA zeolite membrane with
both good separation performance and good
reproducibility, including robust, cheaper (cost per
product), and easiness to produce. This includes
preparation of NaA zeolite layer on the inner side of
the tube using rotating processes [33].
Improvement on modeling and simulations of transport
through zeolites at high coverages [26]
A better understanding about fouling in the NaA
zeolite membrane, as they are very adsorptive
III. CONCLUSION
Pervaporation through NaA zeolite membranes has
advantages for separating azeotropes, close-boiling mixtures,
and thermally sensitive compounds, but only for removing the
species present in low concentration because heat transfer
becomes important if large quantities are removed. NaA
zeolite membranes have additional advantages in separating
mixtures employing high hydrophilicity molecular size
differences and/or adsorption differences. Despite the good
separation performances, NaA zeolite membranes suffer some
drawbacks concerning its durability under highly acidic
condition and high temperature.
The Third Basic Science International Conference - 2013
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REFERENCES
[1] Nasruddin, G. Priyanto, B. Hamzah, S. Bahri, and H. Fauzi. Proses
Hydrocracking Minyak Biji Jarak Pagar dengan Katalis Zeolit Aktif menjadi Biopetroleum.SeminarHasil Pelaksanaan Penelitian Bag iPeneliti
dan Perekayasa Sesuai PrioritasNasional, (2009)
[2] M. Kondo, M. Komori, H. Kita, K. Okamoto, Tubular-type pervaporation module with zeolite NaA membrane, Journal of Membrane Science 133
(1997) 133-141
[3] X. Xu, W. Yang, J. Liu, L. Lin, N. Stroh, H. Brunner, Synthesis of NaA zeolite membrane on a ceramic hollow fiber, Journal of Membrane
Science 229 (2004) 81–85
[4] N. Das, D.Kundu, M.Chatterjee, The effect of intermediate layer on synthesis and gas permeation properties of NaA zeolite membrane, J.
Coat. Technol. Res.,7 (3) 383–390, 2010 [5] Y. Hasegawa, T. Nagase, Y. Kiyozumi, T. Hanaoka, F. Mizukami,
Influence of acid on the permeation properties of NaA-type zeolite
membranes, Journal of Membrane Science 349 (2010) 189–194 [6] S.G. Sorenson, E. A. Payzant, W. T. Gibbons, et al., Influence of zeolite
crystal expansion/contraction on NaA zeolite membrane separations,
Journal of Membrane Science 366 (2011) 413–420 [7] M. Kondo, H. Kita, Permeation mechanism through zeolite NaA and T-
type membranes for practical dehydration of organic solvents, Journal of
Membrane Science 361 (2010) 223–231 [8] Gora, L., van den Berg, A.W.C., Zhu, W., et al., QUALITY
ENHANCEMENT OF NaA ZEOLITE MEMBRANES, Studies in
Surface Science and Catalysis, volume 154 [9] A. Huang, W. Yang, Enhancement of NaA zeolite membrane properties
through organic cation addition, Separation and Purification Technology
61 (2008) 175–181 [10] C.H. Cho, K.Y. Oh, S.K. Kim, J.G. Yeo, et al., Improvement in thermal
stability of NaA zeolite composite membrane by control of intermediate
layer structure, Journal of Membrane Science 366 (2011) 229–236 [11] H.S Ahn, H.Y Lee, S.B. Lee, Y.T. Lee, Dehydration of TFEA/water
mixture through hydrophilic zeolite membrane by pervaporation, Journal
of Membrane Science 291 (2007) 46–52 [12] K. Sato, T. Nakane, A high reproducible fabrication method for industrial
production of high flux NaA zeolite membrane, Journal of Membrane
Science 301 (2007) 151–161 [13] J. Zhang, W. Liu, Thin porous metal sheet-supported NaA zeolite
membrane for water/ethanol separation, Journal of Membrane Science
371 (2011) 197–210 [14] D. Kunnakorn, T. Rirksomboon, P. Aungkavattana, et al., Performance of
sodium A zeolite membranes synthesized via microwave and autoclave
techniques for water– ethanol separation: Recycle-continuous pervaporation process, Desalination 269 (2011) 78 –83
[15] A.S. Huang, W.S. Yang, Hydrothermal synthesis of uniform and dense
NaA zeolite membrane in the electric field, Microporous and Mesoporous Materials 102 (2007) 58–69
[16] .P. Pina, M. Arruebo, M. Felipe, A semi-continuous method for the
synthesis of NaA zeolite membranes on tubular supports, Journal of Membrane Science 244 (2004) 141–150
[17] S. Aguado, J. Gascón, J.C. Jansen, Continuous synthesis of NaA zeolite
membranes, Microporous and Mesoporous Materials 120 (2009) 170–176
[18] A. Navajas, R. Mallada, C. Tellez. Preparation ofmordenite membranes
for pervaporation of water-ethanol mixtures, Desalination 148 (2002)
25-29 [19] L. Casado, R. Mallada, C. Téllez, et al., Preparation, characterization and
pervaporation performance of mordenite membranes, Journal of
Membrane Science 216 (2003) 135–147 [20] Y. Zhang, Z. Xu, Q. Chen, Synthesis of small crystal polycrystalline
mordenite membrane, Journal of Membrane Science 210 (2002) 361–368
[21] A. Navajas, R. Mallada, C. Tellez, et al., Study on the reproducibility of mordenite tubular membranes used in the dehydration of ethanol, Journal
of Membrane Science 299 (2007) 166–173 [22] Y. Han, H. Ma, S. Qiu, et al., Preparation of zeolite A membranes by
microwave heating, Microporous and Mesoporous Materials 30 ( 1999)
321–326 [23] A. Huang, Y.S. Lin, W. Yang, Synthesis and properties of A-type zeolite
membranes by secondary growth method with vacuum seeding, Journal
of Membrane Science 245 (2004) 41–51
[24]Q. Liu, R.D. Noble, J.L. Falconer, H.H. Funke, Organics/water separation
by pervaporation with a zeolite membrane, J. Membr. Sci. 117 (1996)
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[25] Z. Chen, D. Yin, Y. Li, J. Yang, J. Lu, Y. Zhang, J. Wang. Functional
defect-patching of a zeolite membrane for the dehydration of acetic acid
by pervaporation. Journal of Membrane Science 369 (2011) 506–513 [26] T. C. Bowen, R. D. Noble, J. L. Falconer. Fundamentals and applications
of pervaporation through zeolite membranes. . Journal of Membrane
Science 245 (2004) 1–33 [27] Y. Zhang, Z. Xu, Q. Chen, Synthesis of small crystal polycrystalline mordenite membrane, Journal of Membrane
Science 210 (2002) 361–368
[27] C. P. Ribeiro, B. D. Freeman, D. S. Kalika, S. Kalakkunnath. Aromatic polyimide and polybenzoxazole membranes for the fractionation of
aromatic/aliphatic hydrocarbons by pervaporation. Journal of Membrane
Science [28] J. Caro, D. Albrecht, M. Noack, Why is it so extremely difficult to prepare shapeselective Al-rich zeolite membranes like LTA
and FAU for gas separation? Sep. Purif. Technol. 66 (2009) 143.
[29] M. Noack, M. Schneider, A. Dittmar, G. Georgi, J. Caro, The change of the unit cell dimension of different zeolite types by heating and its
influence on supported membrane layers, Micropor. Mesopor.Mater.117
(2009) 10.
[30] T. Nagase, Y. Kiyozumi, Y. Hasegawa, F. Mizukami, Synthesis and
pervaporation performances of merlinoite and phillipsite membranes on
mullite tube, Clay Sci. 12 (suppl. 2) (2006) 100–105. [31] Y. Morigami, M. Kondo, J. Abe, H. Kita, K. Okamoto, The first large-
scale pervaporation plant using tubular-type module with zeolite NaA
membrane, Sep. Purif. Tech. 25 (2001) 251. [32]Z. Yang, Y. Liu, C. Liu, X. Gu, N. Xu, Ball-milled NaA Zeolite Seeds
with Submicron Size for Growth of NaA Zeolite Membranes,
J.Membr.Sci (2012) 2011.11.036 [33]L. Lai, J. Shao, Q. Ge, Z. Wang, Y. Yan, The preparation of zeolite NaA
membranes on the inner surface of hollow fiber supports, J.Membr.Sci
(2012) 409– 410 (2012) 318– 328 [34] D.W. Breck, W.G. Eversole, R.M. Milton, T.B. Reed, T.L. Thomas,
Crystalline zeolites. I. The properties of a new synthetic zeolite, Type A,
J. Am. Chem. Soc. 78 (1956) 5963.
Anthony B. Hamzah was born on January 22, 1988 and graduated from Bandung Institute of Technology in Indonesia, majoring chemical
engineering, in 2011. Currently he is enrolling energy engineering program at
Sriwijaya University. He had worked previously as an Intern at PT. INALUM (Indonesia Asahan Aluminium, 2009) and PT. LAPI ITB (2011-2012). Since
2011, he has been interested in research regarding improvements of industrial
membrane.
The Third Basic Science International Conference - 2013
C08-1
Abstract---Fouling is the obstacle in the utilization of membrane.
To overcome this situation, the cleaning membrane using
chemical agent is needed. Some factors such as type of cleaning
agent, concentration, pressure, and temperature solution have
been investigated. The potential useful of sodium hydroxide
(NaOH), Sodium chloride (NaCl), Ethylenediaminetetraacetic
acid (EDTA), and Ultrapure water (UPW) as cleaning agent have
been investigated further. For the PES membrane fouled by Palm
oil mill effluent, NaOH is the best cleaning agent with the
successful achievement of flux recovery of 85%. The Increasing
of concentration and pressure of NaOH solution increases the
efficiency of cleaning while temperature does not have any
significant improvement. The NaOH concentration of 3%,
pressure 5 bars and Temperature 50oC were the optimum
condition.
Keyword---Cleaning membrane, PES, NaOH, concentration,
pressure, temperature
I. INTRODUCTION
Membrane technology has an important role during the
separation process lately. The main problem of membrane
technology is membrane fouling, which is a condition causes
the membrane cannot use because it has been blocked.
The treatment of Palm oil with PES membrane generates a
membrane block on the surface and inside the pores. This can
be proved from the decrease in permeate flux. The deposit of
particles on the surface of membrane and inside of pores
influenced the lifetime of the membrane. Therefore, it needs a
cleaning process. Many cleaning methods that can be used,
one of them is cleaning with chemicals.
The successfulness of cleaning membrane with the
chemical agent is influenced of numerous parameters.
Generally, they can be divided into three factors: the
properties of chemical agent, the membrane characteristic and
operational conditions of cleaning process[1].
In general, the chemical agent used is divided into four
types of bases, oxidants, acids, and chelate[2]. Sodium
hydroxide (NaOH) was the best famous chemical as the
cleaning agent. Some of previous researchers have
Department of Chemistry, Faculty of Mathematics and Natural
Sciences, University of Sriwijaya, Jl. Raya Palembang-
Prabumulih Km.32, Palembang, Indonesia1
Department of Chemical and Process Engineering, Faculty of
Engineering &Built Environment, University Kebangsaan
Malaysia, 43600 Bangi, Selangor, Malaysia2
Email author: [email protected]
investigated the effectiveness of NaOH as the chemical
cleaning agent [3-5].
The aims of this study was to determine the best chemical
cleaning agent to the clean membrane after treating the Palm
oil mill effluent (POME) and to investigate the optimum
condition to reach the high cleaning efficiency.
II. MATERIAL AND METHODS
A. Material
The membrane used in the UF process was
Polyethersulfone (SelRo MPF-U20-P) with molecular weight
cut-off (MWCO) of 25,000 Da, purchased from Sterlitech
Corporation. The stirred cell (Amicon 8200, Millipore.co,
USA) has a single blade stirrer and also equipped with an
acrylic solution reservoir of 1000ml. Membrane surfaces were
observed using SEM (Gemini model SUPRA 55VP-ZEISS).
The chemical agents used were: NaOH, NaCl, and EDTA. The
NaOH and EDTA were purchased from Friendemann Schmidt
Chemical. The NaCl was purchased from J.Kollin Chemicals.
The chemical were used without further purification.
Palm oil mill effluent was supplied by West palm oil mill
of Sime Darby Sdn. Bhd., Carey Island, Malaysia.
B. Methods
All the experiment was done in the Amicon 8200, Milipore
co.,USA). Firstly, the fresh membrane was put at the bottom
of stirrer cell and permeate flux of Ultrapure water (UPW)
was measured and named as Jwi. After the flux decline
experiment, the fouled membrane was rinse with ultra-pure
water to remove the particles. The permeate flux for fouled
membrane was rinsed by UPW to remove the big particles
from the surface of membrane. The permeate flux measure
was measured using UPW and named Jwf.
For the cleaning process, the fouled membrane
reassembled upside down at the bottom of the stirred cell.
Then stirred cell was locked and filled with cleaning agent.
The cleaning process took place for 30 minutes with pressure
and temperature settings are varied. After the cleaning process
is complete, the membrane was washed again with water and
permeability tests carried out with clean water and the flux is
named as Jwc.
The Flux recovery (FR) was calculated using the formula [5-
8]:
FR (%) = [(Jwc-Jwf))/(Jwi-Jwf)] x 100 (1)
Optimization of NaOH as the cleaning of
Polyethersulfone (PES) membrane fouled by Palm oil
mill effluent
Muhammad Said1,2
, Abdul Wahab Mohammad*2, Akil Ahmad
2
The Third Basic Science International Conference - 2013
C08-2
III. RESULTS AND DISCUSSION
A. Type of cleaning agent
Fig. 1 shows the cleaning efficiencies of different cleaning
agents. From the figure, NaOH has the best results. UP Water
has an efficiency of 18%, NaCl of 22% and EDTA of 32%
which means most of the foulant is not successfully removed.
While the NaOH has an efficiency of 85%, that means far
above from the other cleaning agent. In addition, the NaOH is
alkaline, which means having a high pH value. At pH 11, the
negative charge of the solution increases with the addition of
OH- from NaOH. The negative charge of the solution meets
the charge from PES membranes that are negatively charged
too. The same charge interactions cause a repulsive force
bigger and eventually cause the release of foulant from the
membrane surface.
Fig.1 The cleaning efficiency at
various cleaning agent
The successfulness of cleaning membrane using the
sodium hydroxide is shown in Fig. 2. Fresh membrane is seen
clean and free from particles (Fig. 2a). State otherwise is seen
in Fig. 2b. Membrane surface is full of particles that form a
layer. The cake layer was roughness and nonporous. After
cleaning by NaOH solution, the surface of membrane is
almost free of particles although it is not as clean as fresh
membrane (Fig. 2c).
(a)
(b)
(c)
Fig.2 SEM images of the membrane surface: (a) fresh membrane, (b) fouled
membrane, (c) cleaned membrane
B. Effect of concentration of NaOH solution
Fig. 3 shows that Sodium hydroxide concentration has a
little strange effect to the cleaning efficiency. As expected,
when the concentration of NaOH was increased the percentage
of cleaning efficiency also increased. Results show that at 3%
of NaOH concentration, almost all the foulants can be
removed from the surface and pores inside of membranes
(99.9%). But, the cleaning efficiency slightly falls down to
99.7% when the NaOH concentration increased. This
phenomenon is similar to another researcher
Fig. 3 Average of cleaning efficiency of various NaoH concentrations
C. Effect of different temperature
The temperature solution of cleaning agent doesn’t have a
significant effect. From fig.4, it is seen that cleaning
efficiency at different temperature is almost similar. This
phenomenon can be explained when temperature increased, it
The Third Basic Science International Conference - 2013
C08-3
made the solubility and diffusivity of particles higher. It made
the transportation from membrane to solution easier.
However, it is prohibit using high temperature due to heat
membrane resistance. Therefore, it is recommended that the
washing of membrane using a cleaning agent carried out at
temperatures below 45C.
Fig.4 The cleaning efficiency at different temperature of NaOH solution
D. Effect of different pressure
The pressure of cleaning solution has an important role in
the cleaning process. The effectiveness of cleaning membrane
is shown in Fig. 5. Generally, increasing pressure increase the
cleaning efficiency. Increasing the pressure means increasing
the hydrodynamics of mass transfer from the fouling layer to
the bulk solution. The pressure push the particles come out
from the pores of the membrane. On the surface of membrane,
there will be collision between particles. The NaOH increases
the electrostatic repulsion charge between particles so the
particle will be broken into small particle and easy to
removed.
Fig.5 The cleaning efficiency at different pressure of NaOH solution
IV. CONCLUSION
On this experiment, the use of NaOH solution as the
cleaning agent is the most effective chemical in the cleaning
process of PES membranes after treated the POME. The
obtained result is caused the similarity of charge in the
cleaning solution and the membrane surface so increase the
repulsive force between them.
Increasing pressure increases the cleaning efficiency. The
pressure will force the particle to come out from the pores.
The addition of NaOH solution increases the repulsion charge
between particles and broke them into small pieces. The
temperature doesn’t have any significant improvement in the
cleaning efficiency. The heat resistance of membrane should
be a concern. It is recommended to operate membrane with
temperature below 45oC.
It is suggested to investigate the cleaning efficiency with
different pH of NaOH solution and cleaning time. Also it
suggests using different type of membrane such as PVDF or
PAN. The combination of two or three cleaning agents in
series process could be applied to optimize the effectiveness of
cleaning process.
ACKNOWLEDGMENT
The authors would like to thank the West Palm Oil Mill
Plantation, Carey Island, Klang, Malaysia for the supplying
the POME samples to conduct this study. The financial
support from University Kebangsaan Malaysia through the
project INDUSTRI-2011-010 and MOHE Top-Down Long
Term Research Grant Scheme Project 4L804 is also
acknowledged.
REFERENCE
[1] V. Puspitasari, A.G. Pane, P. Le-Clech, and V. Chen, "Cleaning and ageing effect of sodium hypochlorite on polyvinylidene fluoride (PVDF)
membrane," Separation and Purification Technology, vol. 72, pp. 301-
308, 2010. [2] N. Porcelli, and S. Judd, "Chemical cleaning of potable water
membranes: A review," Separation and Purification Technology, vol.
71, no. 2, pp. 137-143, 2010. [3] W.S. Ang, A.Tiraferri, K.L. Chen, and M. Elimelech, "Fouling and
Cleaning of RO membranes fouled by mixture of organic foulants
simulating wastewater effluent," Journal of membrane science, vol. 376, no. 1-2, pp. 196-206, 2011.
[4] P. Väisänen, M.R. Bird, and M. Nyström, "Treatment of UF
Membranes with Simple and Formulated Cleaning Agent," Food and Bioproducts Processing, vol. 80, no. 2, pp. 98-108, 2002.
[5] T. Mohammadi, S.S. Madaeni, and M.K. Moghadam, "Investigation of
membrane fouling," Desalination, vol. 153, no. 1-3, pp. 155-160, 2002. [6] S.S. Madaeni,T. Mohammamdi, and M.K. Moghadam, "Chemical
cleaning of reverse osmosis membranes," Desalination, vol. 134, pp.
77-82, 2001. [7] M.K. Moghadam, and T. Mohammadi, "Chemical cleaning of
ultrafiltration membranes in the milk industry," Desalination, vol. 204,
pp. 213-218, 2007.
[8] M.R. Sohrabi, S. S. Madaeni, M. Khosravi, and A.M. Ghaedi,
"Chemical cleaning of reverse osmosis and nanofiltration membranes
fouled by licorice aqueous solutions." Desalination. vol. 267, no. 1, pp. 93-100, 2011.
The Third Basic Science International Conference - 2013 C10-1
Abstract. TiO2 – Chitosan nanocomposites photocatalyst has
been synthesized via the sol–gel process followed by aging at
room temperature. Ti(IV)-isopropoxide (C3H12O4Ti)
modified with acetic acid was used as a precursor to
introduce titania network in the chitosan matrix. Chitosan is
considered as a good choice for host materials to grow TiO2
nanoparticles. Dispersion of TiO2 nanoparticles in the matrix
has high photocatalitic activity for dye photodegradation
process due to quantum size effect and high sorption on
material surface. In addition, the TiO2 – Chitosan
nanocomposites can be easily recovered.
The structure, particle size and crystal phase were
evaluated by XRD, TEM and FT-IR. The XRD curve and
TEM profile exhibited peaks which can be assigned to
anatase crystal single-phase with particle size of < 20 nm.
This result indicated that the chitosan matrix offers limited
conditions for TiO2 to grow. The time aging at room-
temperature can also affect the crystallite phase. The IR
spectra indicated that Ti – chitosan bond was formed in the
nanocomposites through basic sites (NH2) available on the
polymer chains and Lewis acidic sites from titanium. As a
preliminary research, the photocatalytic activity was
evaluated by photocatalytic decolorization of methyl orange
in aqueous solution as a model dye pollutant. The result
showed that the photocatalytic activity for dye
photodegradation process was higher when the only TiO2
powder or UV light were used.
Keywords: TiO2–chitosan nanocomposites, photodegradation,
and dye
I. INTRODUCTION
TiO2 nanoparticles have been investigated to improve
its current applications in catalysis fields, especially to reach
more advanced photocatalytic applications for environmental
remediation.i In general, the nanostructure induces increasing
surface area due to the corresponding decrease in the primary
particle size. The nanostructure exhibits unique optical and
electrical properties, enhances the chemical activity which can
be related to several structural and electronic size-related
effects, and shows photochemical and photophysical activities
1Doctoral Programme of Chemistry Departement, Faculty of Mathematic and
Natural Science, Universitas Gadjah Mada, Yogyakarta
* Chemistry Departement, Faculty of Science and Technology, Universitas
Islam Negeri Sunan Kalijaga, Yogyakarta 2 Chemistry Departement, Faculty of Mathematic and Natural Science,
Universitas Gadjah Mada, Yogyakarta
as demonstrated by the reduction of light scattering. In TiO2
materials, such properties are caused by “quantum-
confinement” or “quantum-size effect”, whichis restricted to
very low sizes<10 nanometer.ii
The photocatalytic applications of TiO2 have been
widely exploited in decomposition of aqueous pollutants
because of the strong resistance to photocorrosion, low
operating temperature, low cost, and very low energy
consumption.iii
Unfortunately, TiO2 powder is difficult to be
reused since it is not easy to be separated from the water
phase.iv Therefore, in its early development, well-crystallized
TiO2 particles are immobilized on these carriers to achieve
optimum photocatalytic performance. Various attempts have
been undertaken in the development of new efficient carriers.
Recent research demonstrated that biomaterial are considered
as a good choice for supporting the inorganic materials such as
metal oxide photocatalyst, which will form organic/inorganic
hibryd and nanocomposites.v,vi
Chitosan is an optically active biopolymer that can be
used as a supporting material as well as a good host material
for the growth of nanoparticles. Chitosan has a high flexibility
for supporting inorganic materials such as metal oxides
because the physical properties can be designed, it also has
long-term stability and possess flexible reprocessability.vii
In
addition, the characteristic of chitosan make it a suitable and
excellent bio-matrix for synthesis of nanosized particles or
quantum dots of various inorganic photocatalystsviii
such as
paladium,ix
zinc sulfide, lead sulfide, and cadmium
sulfide.xFurthermore, immobilized nanosized photocatalysts on
the chitosan can effectively prevent nanoparticles from
agglomeration during growth and can overcome the difficulty
in separation and recovery of nanosized powder materials.xi
Using chitosan as a supporting material for
TiO2photocatalyst was needed a modified technique because
its thermal stability properties. On the other hand, the sol gel
techniquewas used frequently to synthesize TiO2 photocatalyst
based on high-temperature calcination of nanocrystalline
particles.The high-temperature annealing(> 400 °C) can
remove organic additives, which can further promote chemical
interconnection among the particles toestablish their electrical
connection.xii
Unfortunately, the high temperature calcination
does not permit the use of biomaterials, because the high
temperature will destroy the active structure of the thermally
sensitive substrates.xiii
Some research have reported a novel
chemical method toprepare nanocrystalline TiO2 at room
temperature. Using the room temperature is advantageous not
only for energy saving, but also extending their applications to
low thermally resistant materials like chitosan.xiv,xv
Room-Temperature Synthesis of TiO2 - Chitosan
Nanocomposites Photocatalyst
Imelda Fajriati,1*
Mudasir,2 Endang Tri Wahyuni
2
The Third Basic Science International Conference - 2013 C10-2
In this study, TiO2 nanocrystalline was synthesized at
room temperature. The synthesis included the hydrolysis and
condensation of titanium tetraisopropoxide (TTIP) in an
aqueous medium using acetic acid as a modifier, followed by
aging at room temperature in the chitosan host. Aging of a sol
is a process in which physical properties of the sol will be
changed as a result from the following mechanisms:
polymerization, coarsening and phase transformation. The use
of acetic acid as a modifer can lead to three phases: exchange
of isopropoxy groups with acetate groups, esterification in
solution resulting in gradual hydrolysis of the Ti precursors,
and ultimate precipitation.xvi
We also attempted to reveal the
influence of aging time on crystal phase and its photocatalytic
activity for decolorization of methyl orange in aqueous
solution as a model dye pollutant.
II. MATERIALS AND METHODS
2.1 Materials and Aparatus
Titanium tetraisopropoxide was purchased from Sigma
– Aldrich. Acetic acid 99.8% and Methyl orange as model dye
pollutant were purchased from Merck. Chitosan (degrees of
deacetylation is 87%) was purchased from Biotech Surindo
Cirebon North Java of Indonesia. Aqua Bidestilata and Steril
Water was taken from Pharmaceutical Laboratories Jakarta.
All of the chemicals were reagent grade. The chitosan solution
was prepared by dissolving 3 gram chitosan in 100 mL acetic
acid 1 %, followed by vigorous stirring at room temperature
for 24 h using magnetic stirrer 600 rpm (Cimarec Barnstead
Thermolyne). As for centrifuge using Boeco C-28 Centrifuge
(Model BOE 1205-13, Boeckel & Co, Hamburg, Germany)
and drying proccess using oven 80 C (Oven Thermoline
Electric from Heareus)
Characterization
The structure and the average crystallite size of TiO2
powder and TiO2 – nanocomposites were determined by x-ray
diffractometer (Shimadzu 6000) with the Cu Kα x-ray tube at
1.5460 Å, 40 kV and 30mA with scan steps of 1◦ min−1 over
the 2θrange 20–80. Transmission Electron Microscopy
(TEM) was carried out by JEM 1400 microscope at an
accelerating voltage of 200 keV, to enable the diffraction of
individual clusters, axial illumination, as well as the nano-
probe method. The chemical structure of the dried gel was
examined using a Fourier Transform Infrared
Spectrophotometer (Shimadzu) in the range of 4000–400 cm-1
.
2.2 Methods
Preparation of TiO2 Sol by Aging at Room Temperature
Ten milliliters titanium (IV) isopropoxide was added
dropwise into 100 mL of deionized water containing 10 mL of
acetic acid under vigorous stirring at room temperature for 24
h. The prepared sample is named as TTIP sol. Freshly
prepared TTIP sol was stored without stirring at room
temperature and atmospheric pressure. It became transparant
within one week.
Preparation of TiO2 – chitosan nanocomposites and
TiO2powders.
TTIP sol was used to prepare TiO2 – chitosan
nanocomposites by sol-gel technique.Various concentration of
the transparant TTIP sol that has been stored for one week was
added to chitosan solution 3% (%w/v) under vigorous stirring
at room temperature for 24 h. The resulted nanocomposites
was then stored without stirring at room temperature and
atmospheric pressure in various time aging. The
nanocomposites was then dried at 80 °C for 60 min in a
preheated oven. Finally, the nanocomposites was washed until
pH 6 – 7, and then dried again.
The studies of synthesis of TiO2 – chitosan
nanocomposites were based on the various aging time (0 day
or no aging; 7 day; and 14 day, named A0, A7 and A14,
respectively) and various concentrations of TTIP sol (%v/v
3.5; 5; 7; and 8.5), named T0.5K, TK, T2K and T4K,
respectively)
TiO2 powders were extracted from the corresponding
TTIP sols by adding adequate amounts of 0.3% sodium
carbonate aqueous solution until precipitation occurred. The
formed suspensions were centrifuged at 4000 rpm for 5 min,
followed by removal of the liquid phase. The precipitates were
then washed three times with water and finally with acetone
twice before being air-dried at room temperature overnight.
III. RESULT AND DISCUSSION
3.1 Crystal Phase
The crystal phase of TiO2 nanoparticles powder and
TiO2 in the chitosan matrix (TiO2 – chitosan nanocomposites)
were studied by XRD. Figure 1 shows the XRD patterns of
TiO2 powder and the numorous TiO2 – chitosan
nanocomposites in various aging and concentration. In all of
XRD curve of TiO2 – chitosan nanocomposites,the anatase
peaks observed at 2 = 25.4°, 38.0° and 48.0° respectively.
After aging, the seeds that grow in the TTIP sol transform into
single-phase anatase as shown in XRD patterns.On the other
hand, no traces of brookite or rutile could be found in the
nanocomposites.
a)
b)
The Third Basic Science International Conference - 2013 C10-3
c)
Figure 1. XRD Patterns of TiO2 – chitosan nanocomposites
showing single phase anatase obtained from synthesis with
various concentration of TTIP sol at (a) no aging time; (b)7
days aging time; (c) 14 days aging time
Conventionally, amorphous-anatase transformation to
anatase crystalline phase can be done in the temperature range
of 250 to 400 °C,xvii
but in this study, amorphous-anatase in
aqueous solution was transformed into anatase crystalline
phase after aging at room temperature (23 °C) for at least one
week, as had been previously reported.xviii
When TTIP sol was
mixed by chitosan to form nanocomposites, the characteristic
of XRD patterns of nanocomposites did not change
significantly. Considering the relativelylow content of titania
in the composition of TiO2 – chitosan nanocomposites,the
sharpness of TiO2 peaks decreased as shown in the XRD
pattern of T0.5K. In addition, the low-intensity peaks observed
in T4K at all aging time can be ascribed to the transformation
of anatase crystalline phase into amorphous phase.xix
The
crystal form of pure chitosan display major crystalline peak at
20.238ᵒ. However, the observed XRD pattern of TiO2 –
chitosan nanocompositesdid not show any peak between 20.0ᵒ
and 30.8ᵒ which indicates that TiO2 particles interfered with
the polymer chains of chitosan. The absenceof the peak at
12.95ᵒ also confirmed that a large number of hydrogen bonds
formed between -NH2 and -OH in the chitosan were
destroyed.xx
Moreover, it was found that different aging time
influenced the crystal phase of TiO2 nanoparticles in the
chitosan matrix. It can thus be concluded that the aging
process can bring about the destruction of the bonds in TiO2–
chistosan nanocomposites which in turn will affect the
crytalline phase of TiO2 in the nanocomposites. As can be seen
in Figure 1, the nanocomposites with of A7 especially for TK
and T2K showed the sharpest peaks with highest intensity.
Therefore, it can be concluded that the optimum aging time is
at 7 days, with TTIP concentration of 5 and 7%.
3.2. Particle Size
Figure 2 shows the presence of TiO2 nanosize in the
nanocomposites and TiO2 bulk, which can be ascribed to the
anatasecrystal phase. A TEM profile image of the TiO2
nanoparticles in the chitosan host is shown in Figure 2(a). TiO2
particles appear uniformly dispersed with a typical diameter of
about 10–15 nm in sample T2K. However, the profile image of
TiO2 bulk is different, in that it has some spherical particles
within particle size of about 70 nm, as shown in Figure 2(b).
The uniform particles in profile image of TiO2 bulk might be
ascribed to the aggregation of small TiO2 nanoparticles during
the growth of nanocrystal without chitosan host. So, the
growth of nanoparticles was uncontrolled and more aggregated
when chitosan host was not used, thus causing larger particle
size.
Figure 2. (a) TEM image of a TiO2–chitosan nano composites
containing 7 % TTIP; (b) TEM image of TiO2 bulk (without
chitosan host)
The use of chitosan as host material is possible due to
the reliability of its chemical structure for growing of TiO2
nanoparticles and limiting its size, as well as for controlling
the nanoparticles dispersion. Chitosan has unique properties
related to the acetylated and nonacetylated residues in the
chitosan matrix, causing the macromolecular structure of
chitosan to have both relatively hydrophobic and hydrophilic
sites, respectively. In addition, chitosan is able to transform its
chains from stretched chains into coils and further transform
into intertwisted coils with hydrophobic micro domains during
the aggregation process, and the macromolecule structure of
The Third Basic Science International Conference - 2013 C10-4
intertwisted coils becomes compact and the movement of the
macromolecule is restricted.xxi
As shown in Figure 2(a), the
nanoparticles were clearly dispersed in the chitosan matrix on
a nanoscale, confirming the formation of a nanocomposites.
Corresponding to this result, chitosan presented the ability to
be used as a good host material because since its matrix can
successfully restrict and control the growth of nanoparticles,
causing the particle size of TiO2 nanocrystal to be smaller than
when chitosan was not used as host material.
3.3 Chemical structure on TiO2 – chitosan
nanocompositesphotocatalyst
Figure 3 compares the FTIR spectra of pure chitosan,
TiO2– chitosan nanocomposites, and TiO2 bulk. TiO2 –
chitosan nanocomposites containing 5% TTIP (sample T2K)
in the range400– 4000cm−1
.
Figure 3.FTIR spectra (4000 – 400 cm−1
) for pure chitosan;
chitosan–TiO2nanocompositesphotocatalyst with 7 % TTIP,
and TiO2 bulk
Compared to pure chitosan,a new wide O–Ti–O band at
the range of 600–900 cm−1
was observed on chitosan - TiO2
nanocomposites photocatalyst, which can be ascribed to the
presence of TiO2 network on chitosan matrix. Based on pure
chitosan spectra, the typical peak of hydroxyl group (O–H) at
3425 cm−1
shifted to a lower wavenumber at 3387 cm−1
. The
reason for the above phenomena is the presence of hydrogen
bonds between hydroxyl group in the chitosan with TiO2.
Therefore, hydrogen bond is one of the possible interactions
between chitosan and TiO2.xxii
The hydroxyl groups of the hydrolyzed TTIP during the
sol–gel process can also combine with the –OH groups on the
chitosan chain thus creatinga chemical bond between the
organic and inorganic phase. The formation of Ti–O–C bond
through such chemical interaction in the nanocomposites can
be seen as an absorption band at 1128cm−1
and 1052cm−1
.
Some of the titanium alkoxide precursors which were un-
condensed but hydrolyzed are shown as Ti-OH groups,
showing peaks at 1620 cm−1
. Meanwhile, the unhydrolyzed
alkoxy groups give their appearance at 1079cm−1
and1128cm−1
.xxiii
The evidence of inter-phase compatibility
can be seen from the appearance of bands at 962cm−1
and945cm−1
showing the interaction of Ti Lewis sites with the
NH2 groups from chitosan chain.xxiv
The band shift at around
1427 cm-1
in chitosan to 1404cm−1
in Ti-O2 composite can be
attributed to hydrogen bond and protonation of the amino
groups.xxv
3.4. PhotocatalyticActivities of TiO2 – Chitosan
Nanocomposites Photocatalyst
The removal of dye pollutant by photocatalytic process
using the decolorization process methyl orange (MO) as a
model was evaluated in this study. The decolorization proccess
of MO can be assessed through photodegradation the dye
pollutant by TiO2 – chitosan nanocomposites photocatalyst. A
series of experiments were carried out to investigate the
optimum activity of the TiO2 – chitosan nanocomposites
photocatalyst for photodegradation of the dye pollutant. using
different concentration of TTIP sol (%v/v 3.5; 5; 7; and 8.5).
Twenty mililiters of MO 30 ppm as initial
concentration was used as the model pollutant. After that, it
was mixed with TiO2 – chitosan nanocomposites photocatalyst
under vigorous stirring for 5 h in the UV reactor.The MO
solution was then put into a cell andanalyzed by UV–Vis
spectrometer (wavelength is 464.0 nm) to determine the
change of MO concentration. Table 1 shows the concentration
of MO after photodegradation proccess.
Table 1. Concentration of MO after photodegradation proccess
by TiO2 – chitosan nanocomposites after stirring for 5 h in the
UV reactor.
Sample Name
Co (ppm
)
Ct (ppm)
Cpt
(ppm)
% Photodegradatio
n of MO UV Non UV
T0,5K 30 26.65
5 27.67
5 2.241 7.47
TK 30 20.57
8 26.59
0 6.012 20.04
T2K 30 17.92
3 25.22
0 7.297 24.32
T4K 30 21.34
2 25.22
3 3.881 12.94
Blank solution was used as a control to establish that
MO did not photodegrade when irradiated with UV light in the
absence of photocatalyst. The removal of dye pollutant
attributable to adsorption effect was obtainedwhen the
experiments were run in the dark (without UV light). The
removal percentage due to both photodegradation and
adsorption effects were calculated as follows:
% removal of dye pollutant = C0 − Ct× 100
C0
Where C0 = initial concentration, or concentration
of dye pollutant at 0min,
Ct = concentration of model pollutant at
experimental time,t.
The Third Basic Science International Conference - 2013 C10-5
The experiments were run with and without the
illumination of alight source to study the photodegradation
process.Therefore, the difference of the % removal between
experiment carried out in the dark and under the illumination
ofa light source should represent the removal of model
pollutant by photodegradation process. Hence, it can be
mathematically written as follows:
Photodegradation of dye pollutant=
total removal under light illumination (UV)− removal
in the dark (non UV)
Percentage removal due to photodegradation effect can
be calculated as follows:
% photodegradation of dye pollutant=CPt× 100%
C0
where C0= concentration of dye pollutant at 0min,
CPt = concentration of model pollutant at
experimental time, t, removed
byphotodegradation effect.
Figures 4 and 5 represent the photocatalytic activities of
TiO2 – chitosan nanocomposites photocatalyst for
photodegradation of MO. A series of TiO2 – chitosan
nanocomposites photocatalyst was used for photodegradation
process using 7 day aging time.
Figure 4. The change of concentration of MO with and without
UV irradiation. A series of TiO2 – chitosan nanocomposites
photocatalyst with varying concentration of % TTIP Sol (%v/v
3,5; 5, 7, 8,5, named is T0,5K; TK; T2K; T4K, respectively)
at 7 days aging time were used.
Figure 5. Percentage of photodegradationof MO by TiO2 –
chitosan nanocomposites photocatalyst with varying
concentration of % TTIP Sol (%v/v 3,5; 5, 7, 8,5, named is
T0,5K; TK; T2K; T4K, respectively) at 7 days aging time
The amount of TiO2 in the preparation of TiO2 –
chitosan nanocompositesphotocatalyst was an important
factorin the degradation of methyl orange. In order to obtain
the optimum amount of TiO2, a series of experiments were
carried out using different concentration of TiO2, as can been
seen inFigure 5. As can be seen in Figure 5, the %
photodegradation increases with TiO2 loading up to 7% in the
TiO2– chitosan nanocomposites, indicating the TiO2 crystal
phase in nanocomposites was the best formed in the sample
T2K. The results were supported by the XRD analysis, which
shows that sample TK and T2K have the sharpest peaks with
highest intensity (Figure ). Thus, it was confirmed that the
optimum crystal phase was obtained in T2K, which has the
optimum activity photocatalytic to photodegrade MO.
It was also observed that sample T2K has anatase
crystal phase higher than other samples. This indicates that for
nanoparticles mainly in the anatase phases and mixed-phases,
their photocatalytic activities increase significantly with
decreasing amorphous phase.xxvi
.
4. CONCLUSION
Room-Temperature Synthesis of TiO2 – chitosan
nanocomposites Photocatalyst were prepared by a simple sol-
gel process in an aqueous media, followed by aging at room
temperature. The aging process at room temperature promotes
the crystallization of anatase phase. This study also has
presented an attempt to show that chitosan is suitable and
biocompatible to be used as a host material. Chitosan was
successfully used as a template forthe synthesis of TiO2
nanoparticles which provides an easy approach to control the
size growth and distribution of the TiO2 nanocrystals.
Chitosan as a template plays an important role in the formation
homogeneous dispersion of TiO2 nanoparticles in its matrix,
and at the same time formed chemical interaction such as
hydrogen bond with TiO2. The photocatalytic activities of
TiO2 – chitosan nanocomposites show a good performance to
photodegrade the dye pollutant.
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Carolina Belver, Jonathan C. Hanson, and Jose´ A.
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Anzan Chen, Simultaneous Removal of Metal Ions and
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18435-18440
The Third Basic Science International Conference - 2013 C15-1
Abstract— An ab initio 2-body analytical potential
function was constructed to describe Hf(IV)-water
interactions. Classical and combined QM/MM molecular
dynamics (MD) simulations have been performed to study
the structure of the hydrated Hf(IV) ion. The influence of
3-body and higher (n-body) terms were investigated. The
hydration structure of Hf(IV) is discussed in terms of
radial distribution functions (RDF), coordination numbers
(CND), and angular distribution functions (ADF). The
results of the QM/MM MD simulations have been found in
good agreement with experimental values, proving that 3-
body and n-body effects play an important role in the
description of the structure of the hydrated Hf(IV) ion.
Keywords: Terms—2-body potential, Hf(IV) ion, hydration,
QM/MM approach
I. INTRODUCTION
afnium and zirconium coexist in nature. Both of them are
used in nuclear reactors. Zirconium is used as a structural
and container material while hafnium as a control material in
water-cooled nuclear reactors. It is well known those elements
have very similar chemical properties and are referred to as
chemical isotopes [3]. Hafnium has a high thermal neutron
capture while pure or reactor-grade zirconium (hafnium-free)
has a low neutron capture; hence, for most nuclear
applications, reactor-grade zirconium is required. For this
reason, it is necessary to separate the hafnium from the
zirconium, although complicated separation methods are
required to remove the hafnium. One of that separation
methods is solvent extraction. The reaction for the extraction
of the metal ion may be expressed as follows [3]:
)1(][
])([][)2/(][ 22
aq
orgzorgaq
z
Hz
RHzmMRHRmM
Manuscript delivered April 6, 2013. This work was supported in part by
the Indonesian Government through the Directorate General of Higher
Education, is gratefully acknowledged.
Suwardi is with the Dept. of Chemistry Education, Yogyakarta State
University, Indonesia ( e-mail: suwardi@ uny.ac.id).
Pranowo, H.D., is with Austrian-Indonesian Centre for Computational
Chemistry, Dept. of Chemistry, Gadjah Mada University, Indonesia (e-mail:
Armunanto, R., is with Austrian-Indonesian Centre for Computational
Chemistry, Dept. of Chemistry, Gadjah Mada University, Indonesia (e-mail:
It is clear that more easily Mz+
ions enter in organic phase
more larger Mz+
ions can be extracted. However, Mz+
ions in
water undergo hydration so that the simple or not extraction
will depend on the structure of the hydration of Mz +
ions. The
rigidity of the structure of hydration caused Mz +
ions hard to
get out of the water phase.
The EXAFS studies of Hf(OH2)84+
(aq) at concentrations of
0.5 M have yielded average coordination numbers of 8 and
average Hf–O distances of 2.16 Å [2]. Several recent
investigations of solvated ions have proven that MD
simulations are suitable tools to obtain realistic data of
solvation structures [6], if the QM/MM approach is performed
to include many-body effects, using at least double zeta basis
sets for the Hartree–Fock ab initio treatment of the quantum
mechanical region. In this paper, we focused on study of
structure of hydrated Hf(IV) ion by an ab initio QM/MM
approach.
II. METHODS
2.1. Potential Functions.
The 2-body potential for the Hf(IV)–water interaction was
newly constructed, applying DZP basis sets for oxygen and
hydrogen and the modified LANL2DZ ECP basis for
hafnium[15]. More than 8000 Hartree–Fock interaction energy
points cal-culated by the TURBOMOLE 5.10 program were
fitted to an analytical form by a least square error minimization
using the Levenberg–Marquardt algorithm[1]:
)2(
2
112654
)(
121195
)(2
i i
H
i
H
i
H
i
H
i
IVHfH
OOOOIVHfObdFit
r
D
r
C
r
B
r
A
r
r
D
r
C
r
B
r
A
r
qqE
The A, B, C and D are fitting parameters for oxygen and
hydrogen. All of them are given in Table 1. The values of -
0.65966 and 0.32983 were adopted for qO and qH in
accordance with the charges of the flexible BJH–CF2 water
model used in the MM region. The experimental gas phase
geometry of water was fixed (O–H distance of 0.9601Å and
H–O–H angle of 104.47o).. The minimum energy for the Hf-
H2O interaction is -144.39 kcal mol-1
at a distance of 2.1 Å.
Structure of Hf(IV) in aqueous solution - An ab initio
QM/MM MD approach
Suwardi, Harno Dwi Pranowo, and Ria Armunanto
H
The Third Basic Science International Conference - 2013 C15-2
Table 1 Final optimized parameters for the interactions of O and H
atoms of water with Hf(IV)
AO
(kkal/mol Å5)
BO
(kkal/mol Å9)
CO
(kkal/mol Å11
)
DO
(kkal/mol Å12
)
-9871.767 385214.691 -1706235.375 1463076.988
AH
(kkal/mol Å4)
BH
(kkal/mol Å5)
CH
(kkal/mol Å6)
DH
(kkal/mol Å12
)
-570.786 2674.223 -2092.776 284.542
More 17000 water–Hf(IV) ion–water configurations were used
in the construction of the 3-body potential. The resulting 3-
body energies were fitted to the following functional form to
be used as a correction for the 2-body potential [8,9]
)3()(
)()exp(
)exp()exp(
2
)(
2
)(3
)(2)(213
2
121
21
OIVHfcut
OIVHfcutOO
OIVHfOIVHf
corr
b
rr
rrrA
rArAAE
OHf(IV)r is the Hf(IV) ion–oxygen distances for water
molecules, and 21 OOr is the oxygen–oxygen distance between
both water molecules. The cutoff radius rcut is set to 6.0 Å after
which three-body effects are negligible. The last, quadratic
term ensures that energy and forces smoothly approach zero at
rcut. The optimized parameters A1, A2, and A3 are listed in
Table 2.
Table 2 The optimized parameters A1, A2, and A3 for interactions
H2O-Hf-H2O
A1(kkal/mol) A2(Å-1
) A3(Å-1
)
0.1080313 0.3089268 -0.2259769
2.2. QM/MM–MD simulation
The system consisted of one Hf(IV) ion and 499 water
molecules in a periodic cube at a temperature of 298.16 K and
constant volume. The radial cutoff limit was set to 12.0 Å. The
quantum mechanical region includes metal ion and first shell
was given a radius of 3.8 Å in accordance with RDF data from
classic MD simulations with pair potential plus three-body
corrections. A reaction field was established to properly
account for long-range Coulombic interactions, and the density
of 0.99702 g cm-3
was assumed to be the same as that of pure
water. The reaction field method was used to correct the cutoff
of long-range electrostatic interactions. The Newtonian
equations of motion were treated by a predictor–corrector
algorithm. A time step of 0.2 fs was chosen, since the BJH-
CF2 water model allows explicit hydrogen movements
[1,4,10,11].
The simulation was carried out with the QM/MM–MD
program developed in Austrian-Indonesian Centre for
Computational Chemistry for the calculation of the ab initio
forces in the QM region. The basis sets used for evaluation of
QM forces were the same as in the calculation of the 2-body
and 3-body potential functions. The system was equilibrated
with a starting configuration obtained from a previous classical
MD simulation. Data for structural evaluation was sampled
within 12.0 ps.
III. RESULTS AND DISCUSSION
The Hf-O and Hf-H radial distribution functions (RDFs) and
their running integration numbers obtained from classical and
QM/MM simulations are displayed in Figure 1 and the main
structural parameters are listed in Table 3. The maximum
occurence for the Hf-O and Hf-H distances in the first
hydration shell obtained from the QM/MM simulation were
observed at 2.335 and 2.855 Å. The Hf-O distance is in good
agreement witn experimental values (2.2 ± 0.02Å)[7].
Table 3 Hydration parameters for Hf(IV) in water obtained from
QM/MM and classical MD simulations
Parameter Classical QM/MM
r1Hf-O (1st maximum of peaks) 2.345 2.335
r2Hf-O (2nd
maximum of peaks) 3.095 2.855
CN (first hydration shell) 10 8
CN (second hydration shell) 18 16
O-Hf-O angle (o) 66/128 74/141
Tilt angle for 1st hydration shell
(see Fig. 4)
-10/10 -10/10
Theta angle for 2nd
hydration shell
(see Fig. 4)
170/178 170/178
Fig. 1. Hf–O and Hf–H radial distribution functions and their running
integration numbers for Hf(IV)–water obtained by QM/MM–MD simulations.
The maximum of the first peak in the Hf–O radial
distribution function corresponding to the first hydration shell
is located at 2.335 Å, while the peak corresponding to the
second hydration shell is centered at 4.8 Å. The first peak is
very sharply pointed and narrow indicating a highly structured
rigid first hydration shell. Furthermore, this shell is well
separated from the second shell, i.e. the RDF is practically
zero in the inter-shell region within a range of about 1Å,
indicating that within the simulation time no exchange occurs.
It can also know more clearly from Figure 2 that showed no
The Third Basic Science International Conference - 2013 C15-3
ligand migration occurs from the first hydration shell to the
second hydration shell or vice versa.
Figure 2. Variation of Hf(IV) ion-oxygen distances during the QM/MM
simulation, showing no exchange processes between the first and second
hydration shells.
The running integration numbers as derived from the Hf–O
RDF predict a first shell coordination number of 8. The
running integration number of the Hf–H RDF at the first
minimum is exactly twice as much supporting the notion of
two clearly isolated hydration spheres. The Hf–O RDF also
shows that the structure-making effect of the cation extends up
to distances of about 7Å, but the lack of a correspondence to
the broad third Hf–O peak in the Hf–H RDF shows these third
shell effects to be rather weak. The classical 2-body potential
simulation would predict a tenfold first hydration shell in clear
contrast to the higher level QM/MM–MD simulation.
Obviously, the simple form of Eq. (2) alone is not sufficient to
properly describe the structure of this Hf(IV) ion. Hence, we
concentrate on the QM/MM–MD simulation.
Fig. 3.First- and second-shell coordination number distribution of hydrated
Hf(IV) obtained by classical-MD (only 2-body), and QM/MM–MD
simulations.
The detailed coordination number distributions from first
and second shells are shown in Fig. 3. The first hydration shell
exhibits 100% of octacoordination. The second shell, in
contrast, is rather dynamic with appreciable populations
ranging from 14 to 20, indicating a rapid exchange with the
bulk (compare to the strongly non-zero RDF at the minimum
after the second peak). The highest occurence of coordination
number of the second hydration shell is 16, i.e. every water in
the first shell binds to 2.0 water molecules in the second shell.
The O–Hf–O angular distribution is displayed in Fig. 4.The
main peaks are located near 74 and 141o, which represents an
almost perfect square antiprismatic geometry. In addition, the
peaks are clearly separated from each other showing the low
inter-shell flexibility of the first shell, i.e. the water ligands are
kept well apart in the field of the metal ion [4,13].
a)
b) Fig. 4. A) Snapshot of structures of hydrated Hf(IV) (first shell, and also
second shell) showing coordination numbers of eight; b) Angular distribution
function of the O–Hf–O angle in the first hydration shell.
The orientation of the water molecules relative to the ion
may be concluded from the vector between the dipole moment
and the V–O connection vector (theta angle) which gives
further insight into the hydrates structure[14]. We observe an
angle distribution with a maximum at 172o with tailing towards
approximately 150o, showing a relatively low degree of
flexibility of the first shell ligands (Fig. 5). The distribution of
the tilt angle (angle between Hf-O connection vector and plane
formed by O-H vectors) shows a narrow peak with its
maximum at 0o and reaching zero at ±30
o. Compared to the tilt
angle of La(III)-H2O reaches zero at ±50o, Hf(IV) ion shows a
low degree of flexibility within the first shell [11].
The Third Basic Science International Conference - 2013 C15-4
Fig. 5. Tilt-angle and theta-angle distributions of the Hf–H2O geometry.
The values of H–O–H angles and O–H distances with the
highest occurence in the first hydration shell are 101o and
0.9725 Å, respectively as shown in Fig. 6.
Fig. 6. a) The angle and b) bond-length distribution of water molecules in the
first (black line) and second (red line) hydrations shell and in bulk (green line)
The inclusion of many-body effects in the QM region does not
indicates H-O-H angle and O-H distances in the first hydration
shell are significantly different compared with those in second
hydration shell and bulk [5].
IV. CONCLUSION
Accordingly the results of QM/MM MD simulations, the
structure of hydrated Hf(IV) ion is rigid, i.e low degree of
flexibility of the ligands in the first hydration shell. This is a
reason why the extraction of Hf(IV) ion in water is difficult to
performed. Here, we also want to stress the importance of
structural data to understand basic process in solutions,
especially the equilibria process in solvent extraction.
REFERENCES
[1] Armunanto, R., Schwenk, C. F., dan Rode, B. M., 2003, Structure and
dynamics of hydrated Ag (I): Ab initio quantum mechanical-molecular
mechanical molecular dynamics simulation, J. Phys. Chem. A, 107,
3132–3138.
[2] Hagfeldt, C., Kessler, V., dan Persson, I., 2004, Structure of the
hydrated, hydrolysed and solvated zirconium(IV) and hafnium(IV) ions
in water and aprotic oxygen donor solvents. A crystallographic, EXAFS
spectroscopic and large angle X-ray scattering study, Dalton
Transactions, 14, 2142–2151.
[3] Lee, H.Y., Kim, S.G., and Oh, J.O., 2004, Stoichiometric relation for
extraction of zirconium and hafnium from acidic chloride solutions with
Versatic Acid 10, Hydrometallurgy, 73, 91–97.
[4] Loeffler, H.H., Yague, J.I., Rode, B.M., 2002, QM/MM–MD
simulation of hydrated vanadium(II) ion, Chemical Physics Letters, 363,
367–371
[5] Remsungnen, T, dan Rode, B.M., 2003, Dynamical properties of the
water molecules in the hydration shells of Fe(II) and Fe(III) ions: ab
initio QM/MM molecular dynamics simulations, Chemical Physics
Letters, 367, 586–592
[6] Hofer, T. S., Randolf, B. R., dan Rode, B. M., 2006, Sr(II) in Water: A
Labile Hydrate with a Highly Mobile Structure, J. Phys. Chem. B, 110,
20409-20417
[7] Brendle , J.M., L. Khouchaf , L., J. Baron, J., R. Le Dred, R.L., Tuilier,
M.H., 1997, Zr-exchanged and pillared beidellite: preparation and
characterization by chemical analysis, XRD and Zr K EXAFS,
Microporous Materials 11, 171–183
[8] Kritayakornupong, C., 2007, Ab initio QM/MM molecular dynamics
simulations of Ru3+ in aqueous solution, Chemical Physics Letters, 441,
226–231
[9] Durdagi, S., Hofer, T.S., Randolf, B.R., and Rode, B.M., 2005,
Structural and dynamical properties of Bi3+ in water, Chemical Physics
Letters, 406, 20–23
[10] Azam, S.S., Hofer, T.S., Randolf, B.R., and Rode, B.M., 2009,
Hydration of Sodium(I) and Potassium(I) Revisited: A Comparative
QM/MM and QMCF MD Simulation Study of Weakly Hydrated Ions, J.
Phys. Chem. A, 113, 1827–1834
[11] Hofer, T. S., Scharnagl, H., Randolf, B. R., and Rode, B. M., 2006,
Structure and dynamics of La(III) in aqueous solution–An ab initio
QM/MM MD approach, Chemical physics, 327, 31–42.
[12] Shah, S.A.A., Hofer, T.S., and Fatmi, M.Q., 2006, A QM/MM MD
simulation study of hydrated Pd2+, Chemical Physics Letters 426, 301–
305
[13] Hofer, T. S., Pribil, A. B., Randolf, B. R., dan Rode, B. M., 2005,
Structure and dynamics of solvated Sn(II) in aqueous solution: An ab
initio QM/MM MD approach, J. AM. CHEM. SOC, 127, 14231–
14238.
[14] Kritayakornupong, C., Plankensteiner, K., dan Rode, B.M, 2003,
Structure and Dynamics of the Cd2+ Ion in Aqueous Solution: Ab Initio
QM/MM Molecular Dynamics Simulation, J. Phys. Chem. A, 107,
10330-10334
[15] Kritayakornupong, C., Yagüe, J.I., dan Rode, B. M., 2002, Molecular
Dynamics Simulations of the Hydrated Trivalent Transition Metal Ions
Ti3+ ,Cr3+ , and Co3+, J. Phys. Chem. A, 106, 10584-10589
The Third Basic Science International Conference - 2013 C16-1
Abstract— Study of structural properties of Sc+ singlet in liquid
ammonia has been carried out by means of the ab initio QM/MM
molecular dynamics simulation approach. Structural properties of
Sc+ in liquid ammonia have been evaluated on the basis of a
molecular dynamics (MD) simulation by the ab initio quantum
mechanical/molecular mechanical (QM/MM MD) method at
Restricted Hartree–Fock (RHF) level using LANL2DZ ECP basis
sets for Scndium and Dunning double-ζ plus polarization (DZP) for
liquid ammonia, respectively. Solvation structure of Sc+ in liquid
ammonia was characterized using RDF, CND, and ADF data
obtained from trajectory files. The first solvation shells consist of 6
liquid ammonia molecules, with Sc+_N distance of 2.197 Å.
Keywords: ab initio, liquid ammonia, Sc+ singlet, Solvation
QM/MM MD simulation
I. INTRODUCTION
candium (Sc) is one of the transition metal plays an
important role in the metabolism of living things. The
research on scandium metal function as in suppressing the
formation of harmful bacteriostatic in Klebsiella pneumoniae
is present in serum have been carried out [1]. Scandium
complex of enterochelin promote bacteriostasis P.aeruginosa
in serum and also provide a therapeutic effect against infection
with P. aeruginosa in living organisms. Scandium can also
function as antibodies [2].
Structure and dynamics of ions dissolved by the solvent can
be determined in two ways: by experiment and computer
simulation. Determination of structure and dynamics of ion
solvation through experiments require some equipment, such
as: X-ray diffraction, neutron diffraction, electron diffraction,
spectroscopic methods, NMR and some of the equipment
based on the method of scattering the others. Determination of
structure and solvation dynamics through computer
simulations performed by Monte Carlo simulation (MC) and
Molecular Dynamics (MD) [3].
Ray diffraction techniques (X rays, neutrons, electrons) give
information about the structure of complex compounds such
as ion-ligand bond distance and coordination number of ion-
ligand complex, while the NMR provides information on the
nature of dynamics known as residence time of the average
ligand in the solvation layer. NMR technique provide the
solvation number (if ion strongly bound to the ligand), but
NMR technique can not follow the process of fast ligand
exchange [4]. It also can not detect the dynamics of
condensation occurring in unit time under a 10-9
second.
Similar situation for a femtosecond (10-15
second) laser pulse
spectroscopy which can not describe accurately the nature of
the dynamics of the solution. This information indicates that
the way the experiment has the weakness in the detection limit
the movement of molecules in solution. This experimental
weaknesses can be solved by computer simulation [5].
This research is using quantum mechanical/molecular
mechanical mechanics dynamics (QM/MM MD) method. This
method was chosen because it takes relatively quick and fairly
accurate results, provides the proper basis set is used and
involves many body potential.
Electron configuration of scandium (Sc) in the ground state
is 1s2 2s
2 2p
6 3s
2 3p
6 3d
1 4s
2. Sc
+ initial electron configuration
(low spin/triplet) is 1s2 2s
2 2p
6 3s
2 3p
6 3d
1 4s
1 whereas high-
spin configuration of Sc+ (singlet) is 1s
2 2s
2 2p
6 3s
2 3p
6 3d
2
4s0.
II. EXPERIMENTAL SECTION
A. Materials
This research is a theoretical study of metal ion interaction
Sc+ singlet in liquid ammonia as a ligand by using ab initio
calculation method. Sc+
as central metal ion is surrounded by
as many as 215 molecules of NH3.
B. Instrumentation
Hardware
A set of complete computer with specs Processor Intel ®
Pentium Core 2 Quad 2.4 GHz, Random Access Memory
(RAM) 3.34 GB effective, Graphic Array Video Card
NVIDIA ® 512 MB, Hard disk with a partition of 120 GB.
Software
• Gaussian 2003 is used to obtain the best basis set for the
system under study.
• Turbomole version 5.10 is used for collecting energy points
on a variety of different points of energy of pair potentials, as
well as many body effect of energy correction (three body).
• MD simulation programQM/MM MD, which is a special
program that is used to simulate the QM/MM MD to obtain
energy data systems and time-dependent coordinates data.
Procedure
Determination of coordinates of Sc- NH3 in Cartesian
coordinates
Initial geometry of Sc in NH3 is modeled in three-
dimensional Cartesian coordinates to adjust the angle and
distance between atoms in the system. Based on experiments
that the H-N-H angle of 106,68° and N-H bond lengths of
1,0124Å [7]
Molecular Dynamics Simulation of Scandium (I) Singlet
In Liquid Ammonia By AB Initio QM/MM MD Methods
Crys F Partana1,*
, Ria Armunanto2, Harno D Pranowo
2, M Utoro Yahya
2
S
The Third Basic Science International Conference - 2013 C16-2
Table 1
Initial Geometry of Sc in NH3 in Cartesian coordinates
Atoms X (Å) Y(Å) Z (Å)
Sc 0,000000 0,000000 1,400000
N 0,000000 0,000000 0,000000
H 0,000000 0,937002 -0,383001
H 0,812002 -0,468001 -0,383001
H -0,812002 -0,468001 -0,383001
Selection of the best basis set
From several basis pairs that have tested the set of the
basis set that does not cause a significant change in the charge
of ion scandium (Sc) and has a profile curve of binding energy
of Sc-N distance in accordance with the profile curve of
Lennard-Jones potential. From the results obtained by the set
of the basis set selection Lanl2dz ecp for scandium atoms and
DZP for the atoms of hydrogen and nitrogen.
Preparation of Sc-NH3 pair potential
In preparation of the pair potential equation, it takes
Sc-NH3 energy points at various distances Sc against NH3 and
at various angles theta (θ) and phi (Φ.). The points of this
energy is used to construct pair potential functions.
Pair potential function for Sc-NH3 interaction has been
formulated through the calculation of ab initio methods at the
Restricted Hartree-Fock (RHF) for scandium singlet ion (sc+).
The minimum energy system ( bE2 ) between Sc and
NH3 is calculated by reduction of Sc-NH3 complex energy
with the energy of the respective monomers ScE and
3NHE
in mathematical form is:
33
2 NHScNHScb EEEE
(1)
Data points of energy at various angles theta and phi are
obtained, then further processed by fitting two bodies. Fitting
the energy conducted to obtain some form of mathematical
equations that represent functions that energy with the
algorithm. The algorithm used in the preparation of analytical
potential functions with the least square method of Lavenberg-
Marguart. Potential equation form two bodies Sc+-NH3 is as
follows:
32
1
M i
Mi
i i i ibd
fit a b c di Mi Mi Mi Mi
q q A B C DE
r r r r r
(2)
Where a, b, c, d, Ai, Bi, Ci and Di are the optimized
parameters summarized in Table 1, RMi distance of the i-th of
atom of Sc and NH3, qi and qM is the charge of atoms of Sc
and NH3.
Simulation protocol
The simulations were performed for one Sc+ and 215
ammonia molecules in a cubic box, at 235.16 K, which
corresponds to the experimental density of 0.690 g/cm3.
Periodic boundary conditions were applied to the simulation
box and the temperature was kept constant by the Berendsen
algorithm [8]. A flexible ammonia model which includes an
intramolecular term was used [7]. Accordingly, the time step
of the simulation was set to 0.2 fs, which allows for explicit
movement of hydrogens. A cut-off of 12.0 Å was set except
for N–H and H–H non-Coulombic interactions for which it
was set to 6.0 and 5.0 Å .
Figure 1. Curve of pair potential function for Sc-NH3 with
the basis set LANL2DZ –DZP
Simulation QM/MM MD
A classical molecular dynamics simulation was carried out
for 100 ps using the pair potential function. The subsequent
QM/MM simulation was performed for 10 ps after 20 ps of re-
equilibration. The ab initio HF formalism with the same basis
sets used for the potential construction was applied to the ion
and the full first solvation shell, and for the remaining MM
region the same 2-body potential as in the classical simulation
was used. According to the Sc–N RDF of the classical
simulation, the QM radius had to be set to 3.2 Å in order to
include the full first solvation shell. A smoothing function was
applied to the transition region between QM and MM regions
[8]. The force of the system, Fsystem, is defined as
Fsystem = FMM + S(FQM - FQM/MM) (4)
where FMM is the MM force of the full system, FQM the QM
force in the QM region and FQM/MM the MM force in the QM
region. S denotes the smoothing function. Free migration of
ligands between QM and MM region is enabled in this
approach
III. RESULTS AND DISCUSSION
A. Radial Distribution Functions
Radial distribution function (RDF) is distance
distribution function of Sc-NH3. RDF of the Sc-N, Sc-H and
the number of its integration obtained from QM/MM MD
simulations are shown in Figures 2 and some characteristic
value are listed in table 2 and table 3. Figure 1 shows the first
The Third Basic Science International Conference - 2013 C16-3
shell solvation Sc+ by liquid ammonia is represented by the
first peak of RDF Sc-N 2.197Å centered.
Figure 2. Sc-N and Sc-H radial distribution function
In figure 2 shows that at a distance of 2.95 peak of
RDF Sc+-H reaches a maximum value of the first and was
down to a minimum value at a distance of 3.45 Å. This peak
shows the first shell solvation of the H atoms of the molecule
NH3. RDF integration numbers Sc+-H in the first solvation
shell amounted to 6. The second peak occurs in Sc+-H distance
of 5.32 Å and reaches a minimum at a distance of 6.44 Å.
RDF integration Numbers Sc+-H in the second solvation shell
amounted to ~16.
RDF integration Numbers Sc+-H well in the first solvation
shell or the shell the second solvation according to the RDF
Sc-N. RDF peak of Sc+-H both in the form of ramps (not
sharply) suggests that the second shell solvation structure can
not be determined precisely.
Table 2
Optimized parameter of the analytical Sc+-H2O
pair potential function
A
(kcal mol-1 A5) A
(kcal mol-1 A7) A
(kcal mol-1 A9) A
(kcal mol-1
A12)
Sc+- N
-7624.28775 41844.02312 -59090.0078 30000.42401
Sc+- H
-486.58718 7596.26736 -20518.3923 20472.10809
Distance N and H of Sc+ based RDF simulation results in
the first solvation shell is 2.197Å and 2.95 Å. This distance
difference indicates that the first peak of RDF Sc+-N do not
overlap with the first peak of Sc+-H RDF and RDF first peak
of Sc+-N occurred at distances shorter than the first peak of
Sc+-H RDF. This phenomenon indicates that the solvation in
the first shell has a fixed structure with nitrogen atoms leads to
the ions Sc+, while the hydrogen atoms away from Sc
+.
Table 3
Characteristic values of the radial distribution functions for Sc+ in liquid ammonia
1Mr 1mr 1mN
2Mr 2mr 2mN
Sc N 1.88 2.74 6 4,03 6.81 ~16
Sc H 2.54. 3,37 18 4.23 6.95
B. Coordination Number Distribution
Based on the analysis of the coordination number or the
number of ligands that surround the central atom in both
solvation first shell and second solvation on the shell as well
as the percentage likelihood that there could be analyzed based
on information obtained from the CND. Distribution of
coordination number for Sc+-NH3 system is shown in Figure 3.
In the first shell solvation solvation numbers indicate the
number 6 with an abundance of 90,66% while in the second
shell solvation show number ~16 with the accuration of
21,30%
C. Angular Distribution Functions
Analysis of solvation structure of Sc+-NH3 is done by
evaluating the angle distribution function (ADF) as result of
MM/MD simulation. ADF gives information about the
distribution of bond angle formed between the N-Sc+-N. From
the angle distribution of N-Sc-N (figure 4) shows a dominant
peak at an angle of 85o distance of 2.197 Å. This indicates
that the simulation of Sc+ in liquid ammonia show the
existence of complexes with a non rigid shape.
Figure 3. Coordination number distribution of Sc+
in liquid ammonia obtained from QM/MM MD
The Third Basic Science International Conference - 2013 C16-4
Figure 4 Angular Distribution Function of O-Sc+-O
angles obtained by QM/MM MD simulation
IV. CONCLUSION
QM/MM MD simulation methods is used to study the
solvation structure of Sc+ ions in liquid ammonia, in order to
produce information about the solvation structure of Sc+ ions
in liquid ammonia binds six (6) liquid ammonia molecule. The
distance between Sc+ with the N of NH3 molecules in first
solvation shell is 2.197 Å. Greatest probability for finding N
in the second solvation shell is at a distance of 5.5 Å, with a
number of integration in the second solvation shell amounted
to ~ 16.
REFERENCES
[1] Roger, H.J., Synge, C., Woods, V.E., 1980, Antibacterial Effect of Scandium and Indium Complexes of Enterochelin on Klebsiella pneumoniae,
Antimicrob Agents Chemother, 18, 63-68.
[2] Silva, J. J. R., Williams, R. J. P., 1991, The Biological Chemistry of The Elements, Claredon Press, Oxford.
[3] Pranowo, H.D. dan Hetadi AKR., 2011, Pengantar Kimia Komputasi,
Austrian-Indonesian Centre for Computational Chemistry (AIC), Jurusan Kimia Fakultas MIPA Universitas Gajah Mada, Yogyakarta
[4] Armunanto, R., Schwenk, C.F., Rode, B.M., 2004, Gold(I) in Liquid
Ammonia: Ab inito QM/MM Molecular Dynamics Simulations. J. Am. Chem. Soc., 126, 9934.
[5] Rode, B.M., and Hofer, T.S., 2006, How to Access Structure and
Dynamics of Solutions: the Capabilities of Computational Methods, Pure Applied Chemistry, 78, 525–539.
[6] Armunanto, R., Schwenk, C. F., Randolf, B. R., & Rode, B. M. (2004).
Ag (I) ion in liquid ammonia. Chemical physics letters, 388(4), 395–399.
[7] Kheawsrikul, S., Hannongbua, S. V., Kokpol, S. U., & Rode, B. M.
(1989). A Monte Carlo study on preferential solvation of lithium (I) in aqueous ammonia. J. Chem. Soc., Faraday Trans. 2, 85(6), 643–649.
[8] M.P. Allen, D.J. Tildesley, 1987., Computer Simulation of Liquids,
Oxford University Press.
The Third Basic Science International Conference - 2013 C18-1
Abstract- A plasticized polyvinyl chloride (PVC) membrane based
coated wire iodide ion selective electrodes has been developed by
using an active material of Turen -Malang activated zeolite using
NH4Cl 2M and calcinations by heating process at 550oC for 4 hours
in order to have anion exchange properties, activated carbon
,polyvinylchloride (PVC) and, dioctylphtalate (DOP) as matrixs =
32.26%: 3.22%): 16, 13%: 48.39% dissolved in tetrahydrofuran
(THF) solvent (1:2 w/v). The characterization of the basic properties
of sensor included : sensitivity and liniarity of response (detection
limit), response time, influence of pH, soaking time, selectivity
against foreign ions and also life time.The sensor shows a good
Nernstian slope of 59.35 ± 1.52 mV / concentration decade) in wide
linier range concentration from 10-6 to10-1 M or 0.127 to 0.0127 x
106 ppm for iodide ion. The detection limit of this sensor is 4.17 x10-
7 M or 0.0529 ppm, fast response time ( 60 seconds) and was found
to be very selective toward iodide and thiocyanate ions, usable in
wide pH range of 1.6-11 and temperature of 30-60oC, need soaking
time of 30 minutes in 0.1M in KI solution. The sensor electrode is
reproducible and stable for a period near of two months. This kind of
CWE was successfully used for determination of iodide ion in urine
as real sample and their result was compare to standard UV
spectrophotometric methode.The proposed iodide-CWE can be used
as an alternative method beside of UV spectrophotometric method.
Keywords: coated wire ISE, iodide sensor, zeolite membrane
I. INTRODUCTION
II. INTRODUCTION
Iodine is an essensial micronutrient and its key role in many
biological activities such as brain function, cell growth,
neurological activities and thyroid function [1]. Iodine
deficiency disorders (IDD) is still a public health problem in
Indonesia and causes mental retardation. Estimated to be
around 38% population exposed to the risk of pervasive
developmental disorder, intelligence, cretinism and goiter
which will affect to the survival and quality of human
resources. Normal adult body requires iodine intake of 100-
150 mg/ day and will excreted through the urine is about 90%
in the form of iodide ion [2]. So the urinary iodine is
examination very important to assesing iodine deficiency,
because the iodil level in urine reflect to the subject’s intake.
The concentration iodine in urine for patients with iodine light
1,2,3,4,5) Chemistry Department of Mathematic and Natural Sciences Faculty,
University of Brawijaya, Malang, Indonesia
Email address :[email protected];[email protected]
IDD catagory is 5-9.9 mg/dL, Moderate IDD catagory is 2-4.9
mg/dL and severe IDD catagory is < 2 mg/dL, while for
normal patients (non IDD) is 40.45 mg/dL or 406.44 ppm [3]
Therefore, a simple, rapid, reproducible, and high-throughput
determination of iodide concentration at low level in urine
samples is highly demanded. Various method such as
spectrophotometry [4], flow injection analysiss base on
Amperometry [5], Gas Chromatofraphy[6], and Ion
Chomatography [7]. However, most of these methods are
either time-consuming or need sophisticated instruments and
cannot use in the field of trace analysis. Thus for this reason
that extensive effort has been made to develope highly
selective iodate ion electrodes as a potentiometric sensor for
iodide ion (as one of speciation of iodine). It is because the
potentiometry with ion selective electrodes is in principle
particularly well suited to speciation studies because of its
selective response to free ions in solution advantages such as
simplicity, speed of analysis, low cost, wide linear range,
reasonable selectivity and non-destructive analysis, and as
such, have emerged as one of the most promising tools for
direct and easy determination of various species.
Coated wire ion-selective electrodes (CWISEs) based
on coating polymeric membrane films directly on the surface
of a conducting substance to replace the inner reference
electrode system are very simple to construct and
maintain,since no filling solution is required and if the
membrane is thin enough, such electrodes usually equilibrate
much faster with the solution. They are capable of such
extreme miniaturization that they should find applications in
biomedical and clinical fields, as well as in environmental
research. Their characteristics of basic properties are equal
to and occasionally better than the disc type conventional
ones [8].
During the last decade, a number of studies have
focused on properties of functionalized natural zeolite, a
relatively new class of an adsorbent, catalyst and ion
exchanger. The abilities of natural zeolite as ion exchanger
have been assessed using different methods and techniques. It
was also shown that natural zeolite (bentonite) can be used as
potent ionophores for the preparation of ion selective-sensors
[9].
Recently, the application of functionalized activated
zeolite as ionophores in iodide ion selective electrodes was
investigated. Many ion selective electrodes (ISEs)’s
membrane have been constructed employing various ion
A New Coated Wire Iodide ion Selevtive Electrode
(Iodide-CWE) base on Zeolite membrane as Iodide ion
sensor in urine
1)Atikah,
2)Chasan Bisri,
3) Qonitah Fardiyah
4)Rizki Layna R ,
5)Rizka Setianing Wardhani
The Third Basic Science International Conference - 2013 C18-2
exchanger as well as neutral and charged ionophores as
sensing materials with exellent selectivities for anion [10].
The application of fungtion so far, several
experimental studies have demonstrated that the generation of
a membrane potential of those type of ISEs could be atributed
to permselective ion transport across the liquid
membrane/solution interface, i.e., charge separation through a
preferential uptake of aprimary ion by a sensing element in the
liquid membrane, leaving its hydrophilic counter ion in an
aqueous sample solution and usually exhibit the Hofmeister
pattern with the largest selectivity to lipophilic anions [11-
[12].
III. METHODOLOGY
Apparatus and emf measurements
All potential measurements were performed using the
following assembly: Hg, Hg2Cl2 (Sat’d)//sample solution/PVC
membrane/Pt-wire electrode. A pH-meter (Fisher E 520) was
used for potential measurements at 26°C ± 0.5oC. The
activities of iodide (I-) ions in the urine were calculated
according to the Debye–Hückel approximation.
Reagent and solution
Natural zeolite derived from Turen, Malang was
activated by NH4Cl 2M and calcinations by heating process at
550oC for 4 hours in order to have anion exchange properties,
activated carbon, polyvinylchloride (PVC) is use as ionophore,
polyvinyl chloride (PVC) of high molecular weight and dioctyl
phthalate (DOP) as a plsticizer were purchased from sigma,
tetrahydrofuran is products from Merck. Platinum wire (99,9%
; 0.5 mm) is products from Aldrich and RG-58 Coaxial
cable as connector ISE to mV potentiometer. All other reagent
used were of analytical reagent grade, and doubly distilled
water was used throughout. KI; NaOH,NH4Cl;
K2SO4,Phosphoric Acid conc.(85%); sulphuric acid conc.
(36%); As2O3, NaCl.
Construction and calibration of the electrodes
The membranes electrode was prepared by mixing
thoroughly by dissolving activated zeolie, activated carbon,
PVC, DBP plasticizer in THF solvent (1:2 v/w). This
solution was deposited directly onto a platinum wire
approximately 0.5 mm in diameter and 10 cm in lenght whose
tip had been melted in flame to form a spherical button was
soldered to a length of RG-58 coaxial cable, and the solvent
was evaporated for approximately 30 minutes and then
allowed to stand overnight in the oven at 50oC. A membrane
was formed on the platinum surface and the electrode was
allowed to stabilize overnight. Prior to use the electrode was
initially conditioned by soaking it overnight in a 0.1M solution
of KI to be measured. When not use, the electrode was store in
air between use and reconditioning immediately before using
by soaking for at least 1 hour in a 0.1M solution of KI. The
utility, composition of polymer membrane, respon
characteristic, and selectivity of Iodide ion - coated wire
electrode (CWE) were investigated. The electrode potential
measurement was made under constant conditions by taking 25
mL of solution for each measurement in a cell thermostated at
26 0.5 oC , immersing the electrode to a constant depth in the
solution, and stirring at a constant rate by means of a magnetic
stirring bar. In all experiments the electrode potential
measurement was carried out from low concentration to high
concentration. The electrode tip was rinsed with deionized
water and then immersed in one of the standar solution.
determination of iodide ion in urine
Samples of urine were collected from 10 persons
laboratory workers into polyethylene tubes. The samples were
immediately centrifuged and stored at 4oC. A 1.0 mL aliquot
of the sample was transferred into a 10-mL measuring flash
and diluted with distilled water. For each analysis, the iodide
sensor and double –junction Ag/AgCl reference electrode were
immersed in the same solution, and the potential reading were
recorded. A typical potentiometric calibration plot was made
by plotting the potential change against the logarithm [I-]
concentration. The obtain calibration curve was used for
subsequent determination of I- in unknown samples. The
results of determination of I- on both the Spectrophotometric
according WHO method and the potentiometric method using
iodide ion sensors tested for their accuracy and precision
IV. RESULT AND DISCUSSION
Influence of membrane composition
The different aspect of membrane preparation based
on zeolite as ionophore containing different
PVC/plasticizer ratios were mix in THF solven
(1:2 ratio v/w) were studied and the results are
summarized in table 1.
Table 1 Optimization of membrane ingredients
No. Membran composition (%) Slope/mV
decade–1 Zeolite Activated
Carbon
PVC DOP
1 16.13 3.22 16.1
3
64.5
2
53.97±
2.21
2 32.26 3.22 16.1
3 48.3
9
59.32 ±
2.18
3 48.39 3.22 16.1
3 32.2
6
55.73 ±
0.75
4 0 3.22 35 65 47.230.6
5
It is obvious from Table 1 revealed that the amount of
ionophore, the nature of solven mediator, the plasticizer/PVC
ratio significantly influence the sensitivity of ion selective
The Third Basic Science International Conference - 2013 C18-3
electrodes. The sensitivity of electrode respone increases with
increasing ionophore content. Moreover, addition of ionophore
less than 32.26 % or more than 32.26% will however result in
non Nernstian response of the I- ion CWE, most probably due
to
saturation or non-uniformity of the membrane. The electrodes
with no carrier (blank membranes,containing PVC, plasticizer
and activated carbon) displayed insignificant selectivity and
sensitivity towards iodide [1]. Use of the DOP plasticizer as
a solvent mediator for preparing a coated wire thiocyanate ion-
selective electrode(iodide ion CWE) need to fulfill four
principal criteria: high lipophilicity, solubility in the polymeric
membrane (no crystallization) as well as no exudation (one
phase system) and good selectivity behavior of the resulting
membrane. It should be noted that the nature of plasticizer
influences both the dielectric constant of the membrane and
the mobility of ionophore and its complexed associatiated with
I- ion [13]. Thus, based on the result obtained on the
optimazation of the membrane composition, the membrane 2
with the optimized composition of zeolite:activated
carbon:PVC:DOP percent ratio (w/w) of
32.26:3.22:16.13:48.39 was selected for preparation the
polymeric membrane electrode for I- ion. Nernstian responses
obtained on the composition ratio of PVC / plasticizer 1.2 as
obtained by other researchers
Table.2 Specifications of the coated wire iodideion selective electrode base on
zeolite carrier
No. Properties Values/Range
1. Sensitivity (Nernst
factor) 59.35 1.52 mV /
concentration decade
2. Linier range (I-,M) 1,10
-6 – 1,10
-1 M
(0.127-1,2700 ppm)
3 Detection limit 4.17.10-7
M (0.0529
ppm)
4 Response time (1.10-
6 to 1.10
-1 M)
60 seconds
5. Selectivity order SCN->I
->CN
-
>CH3COO->H2PO4
-
6. Conditioning time 30 minutes
7. Standard deviation of
slope (within
electrode variation)
1.52 (2.56%)
8. Life time Near two months still
good
9 Working pH range 1.5 -10
10 Temperature stability 20-60oC
11. Selectivity against
foreign ions
CNS- >I
- > SO4
2- > Cl
-
Electrode specifications listed in Table 2 states that ESI has a
character that is optimal for the potentiometric measurement of
iodide analysis. The potentiometric selectivity coefficient for
different an ions were determined as described earlier from the
experimental data obtained using the fixed interference
method. The concentration of interfering anion was fixed at
10-3
M and. the results are summarized in Table 2. It is seen
that electrode is not very selective to iodide ion (I- ) because
they respond also to the CNS- ion,and the observed selectivity
pattern for proposed sensor significantly same from the
Hofmeister selectivity sequence (i.e. selectivity based on
lipophilicity and charge density of anions). However, the
lipophilicity of the anion still plays an important role, and only
the simultaneous consideration of both the lipophilicity and
interaction of the anion with zeolite allows one to explain the
selectivity patterns. Therefore, from Table 2 shows,ion
exchange selectivity is mainly determined by two factors:i.e
the charge of an ion and its solvation, since the interaction
between anions and ion exchange groups on zeolite is
electrostatic [12]. As can be seen from the table 2, the
selectivity coefficients obtained for the proposed iodide
electrode are superior to those reported for other anion listed
in Table 2.
Application
The new coated wire iodide ion selective electrode was
satisfactorily applied to the determination of iodide ion in 10
urine samples. The analysis were performed by direct
potentiometry using the standard curve technique. The results
compared to those of Spectrophotometric analysis. The result
obtained are summarized in Table3. Good recoveries in all matrices were obtained. From this results we can conclude that
the proposed sensor was successfully applied to determining
the iodide content in biological samples.
Table 4. Determination of iodide ion in different samples with I– CWE
Sample
ppm I- from Spec-trophotometric
(average) Accuracy (%) Precision (%)
ppm I- from
poten-tiometric
(average)
Accuracy (%) Precision (%)
Urine 460 5 98.91 97.83 444.14 16.7 96.20 96.20
Student t test analysis based on α = 0.05, degrees of freedom
(DF=8) obtained t of 1.56, while the table t of 2.31, which
states that the results of potentiometric methods did not differ
significantly with the spectrophotometric method. Thus
potentiometric method can be usedn as an alternative method
besides spectrophotometric method
The Third Basic Science International Conference - 2013 C18-4
I. CONCLUSIONS
The membrne composition influenencing the Nernstian
character of iodide sensor. The membrane with the
composition of zeolite:activated carbon:PVC:DOP percent
ratio (w/w) of 32.26:3.22:16.13:48.39 dissolved in THF
solvent (1:2 w/v) was selected for preparation the polymeric
membrane electrode for I- ion and can be use as chemical
sensor for iodide ion in the construction of coated wire iodide
ion selective electrode which has optimum characteristics for
iodide ion analysis. This kind of CWE was successfully
applied to determining of iodide content in urine (biological)
samples provides accuracy of 96.20% and precision of 96.20
0%, beside to the spectrophotometric. In addition the iodide
ion CWE was simpler and faster than the spectrophotometric
method.
REFERENCES [1] Amin,M.K., M. Ghaedi, A. Rafi, M. H. Habibi and M. M.Zohory,
Iodide Selective Electrodes Based on Bis(2-mercaptobenzothiazolato)
Mercury(II) and Bis(4-chlorothiophenolato) Mercury(II) Carriers,
Sensors, vol.3 pp 509-523, December 2003
[2] Bourdoux, P., Measurement of Iodide in the assesment of iodide
Deficiency Disorders, Newsletter,4, pp8-12, 1988
[3] Delange,F., Iodine, AnnalesNestle,52, 81-93, 1994
[4] Dunn,T.H et al., Methods for Measuring Iodine in Urine,
International Council of Iodine Deficiency, Disorders, UNICEF,WHO,
Netherland,1993
[5] Ju XU, W., Y.Qin chai, R. Yuan, L. XU, and S. Li Liu, Highly
Selective Iodide Electrode Based on the Copper(II)-
N,N'bis(salicylidene)-1,2-bis(p-aminophenoxy)ethan Tetradentate
Complex, Analytical Sciences , VOL. 22, p 1345-1349, 2006
[6] Hamid R. Z, F.Memarzadeh, A.Gorji and M.M Ardakani, Iodide-
Selective Membrane Electrode Based on Salophen Complex of Cobalt
(III), J. Braz. Chem. Soc., Vol. 16, No. 3B, 571-577, 2005
[7] Jianyuan,D., Y.Chai., R.Yuan.,X.Zhong.,Y.Liu and D.Tang, Bis-
Dimethylaminobenzaldehyde Schiff-Base Cobalt(II) complex as a
Neutral Carrier for a Highly Selective Iodide Electrode, Analytical
Sciences , VOL. 20, p 1661-1665, 2004
[8] Fujiwara,T.,I.U Muhammadzai., M.Kojima and T.Kumamaru, An
Improved Method for The Flow Injection Determination Iodine Using
the Luminol Chemiluminescence Reaction in a Reversed Micellar
Medium of Cetyltrimethylammonium Chloride in 1-Hexanol-
Cyclohexane, Analytical Sciences , VOL. 22, p 67-71, 2006
[9] Izadyar,A., Bentonite carbon composite polyvinyl-coated wire
electrode for lead detection as an environmental sensor, Russian
Journal of Electrocheimistry ,52,p. 91-96, 2004
[10] Atikah, H. Sulistyarti, D. M.Permana and , R Y.Dianti, Development
of Coated Wire Cyanide Ion Selective Electrode Potentiometric Sensor
Prototype based on Zeolite membrane for Determination of Cyanide in
Gadung ((Dioscorea hispida Dennus), Proceeding of Indonesian
Chemical Assosiation Seminar,p 2011
[11] T.Okada,M.Harada, and T.Ohki, Hydration of Ions in Confines Spaces
and Ion Recognition Selectivity, Analytical Science., vol. 25,pp 167-
175, 2009
[12] Pretsch,E, The New Wave of Potentiometric Ion Sensors, Trends in
Analytical Chemistry., 26(1): pp46-51, 2007 From
http://www.elsevier.com/locate/trac
The Third Basic Science International Conference - 2013
C19-1
Abstract— In this study, sago wastes were investigated for its
potential in removing metals from aqueous solution. The
equilibrium adsorption level has been studied under varying
conditions of time, initial metal ion concentration, adsorbent dose,
particle size and pH. The adsorption parameters were analyzed
using Freundlich and Langmuir models. The physico-chemical
properties such as determination of functional groups, moisture
content and ash content were also investigated. The adsorption of
metals increased with increasing treatment time and the
equilibrium of the adsorption was attained after 60 minutes. The
percentage removal of only Cd and Pb removal based on the
particle sizes of 300 µm, 710 µm and 1200 µm at 10 mg/l are
58.12%, 53.32%, 43.65% and 94.25%, 86.09%, 82.85%
respectively. The study shows that the adsorption gives an
optimum value at ambient temperature, best fitted on Langmuir
isotherm model with maximum capacity of adsorption of Pb:
20.73 mg/g; Cd: 18.67 mg/g, Cr: 13.66 mg/g, Cu:7.41 mg/g. It is
recommended that further complimentary study should be
conducted, for instance the sago wastes should be modified
chemically in order to further enhance the removal of heavy
metals from solution.
Key words---- Sago Waste, Adsorption, Freundlich Isotherm,
Langmuir Isotherm, Metal Ions
I. INTRODUCTION
ater contaminated by heavy metals remains a serious
environmental and public health problem. Their
presence in the environment can be detrimental to people,
plants and animals. They can accumulate in water, soil, plants
and living tissues, thus becoming concentrated throughout the
food chain [1]. The important toxic metals are Cd, Zn, Pb, Cu
and Ni. Cadmium (Cd+2
), copper (Cu+2
), chromium (Cr+3
) and
lead (Pb+2
) are heavy metals focused in this research. Removal
of heavy metals from wastewater is necessary before safely
discharged. The main objective of water treatment is to
produce high quality water that is safe for human consumption,
has aesthetic appeal, conforms to state and federal standards
and economical for production. Hence, removal of heavy
metals from water and wastewater is assumes important.
Among different heavy metal removal methods, membrane
filtration (reverse osmosis), chemical precipitation,
* J. O. Amode is with Universiti Brunei Darussalam, Faculty of Science,
Jalan Tungku Link, Gadong BE1410, Brunei Darussalam
electro-dialysis, electrolytic processes, biological sorption
and adsorption could be mentioned. Adsorption has
advantages over other methods for remediation of heavy
metals from wastewater because its design is simple and it is
sludge-free and can be of low capital intensive [2].
In Brunei Darussalam, sago palms (Metroxylon sago) are
inexpensive and grow well in swampy areas that are in urgent
need of economic development. Other than rice, sago is the
second important source of starch as staple food for its
population. There exist at present, it is estimated that about
9600 tonnes of sago starch, extracted from sago palms, are
produced per annum. Sago waste is produced as a by-product
from the production of sago starch [3]. It is actually an
industrial waste after starch is extracted from sago palm
processing [4]. Sago waste produced from the sago palm is
one of the cheapest, biodegradable and most readily available
of all renewable natural polymers existing in Brunei
Darussalam. To our best of knowledge sago research have not
been conducted as country based research study for metal ions
removal and making use of it for any purpose is considered
environmentally sustainable. These residues, which are largely
composed of celluloses and lignins are, therefore, both a waste
and a pollutant. Their chemical composition such as (C=O,
S=O,-OH) suggests that they could have some potential as a
biosorbent [5].
2. MATERIALS AND METHODS
2.1 Adsorbent
All experiment was practically conducted in the Department
Of Chemistry, Faculty of Science, Brunei Darussalam. The
biomass was extensively washed with double distilled water.
After that it was dried in sunlight for several days to dehydrate
the excess water until constant weigh was observed. The fiber
residues of sago waste were obtained by grinding using a
laboratory blender as shown in Figure 1b. Prior to drying in
the oven, the sago fiber was manually selected from sago
hampas as showed in Figure 1a. Finally, the dried material was
grinded, screened to different particle size of ;<350 - 125 µm,
710 to 1200µm and >1200 µm [ 5- 6] and stored in plastic
containers, which was used for adsorption study.
2.2 Proximate Analysis:
Moisture content was obtained through drying process of
the sago wastes at 105°C until the mass of the biomass became
constant. Ash content was obtained through repeated one-hour
Sorption of Toxic Cations onto Sago Waste 1:
Investigation of Sorptive Capacity
J. O. Amode*, J. H. Santos, A. H. Mirza and C. C. Mei
W
The Third Basic Science International Conference - 2013
C19-2
ignition of sago wastes at 575°C until the mass of sago wastes
became constant. The results are shown in Table 1. The pH
was determined by immersing 1.0g samples in 100ml of
deionised water and stirring for 1h. Bulk density was
determined by a tamping procedure described by [7].
Figure 1a. Prepared and selected fiber from locked sago
hampas Figure 1b. Grinded Sago waste
TABLE 1
PHYSICAL AND CHEMICAL COMPOSITION OF THE SAGO
WASTE
Parameter Unit Values
Moisture Content % 15.38
Bulk Density (Kg/m3) 5.5
Ash Content (%) % 7.1
Total loss of ignition (%) 94
pH of the slurry at 250C 4.1
Particle Size (µm) µm <350
CEC (Meq/g) 2.51
Elemental Composition % Wt 41.44 Carbon, 5.84
Hydrogen, Oxygen 4.56 ,
<0.50 Nitrogen, 0.61
Sulphur
Surface Chemistry -OH Groups; Carbonxyl Compound;
Presence Of –NH2; Vibration Of The
Bond C=O, S=O and -OH
2.3 Adsorbate
All the chemical reagents used in these studies were of
analytical grade. Stock solutions (1000 mg/l) were prepared by
dissolving CrNO3O9.9H2O; Cd (NO3)2.4H2O; Pb (NO3)2 and
CuN2O6.3H2O in de ionized water respectively. Further
working solutions were prepared by diluting this stock
solution. Initial pH was adjusted using 0.1N HNO3 or 0.1N
NaOH.
Adsorption experiments were carried out at ambient
temperature using the optimum conditions of all pertinent
factors , such as pH, dose agitation speed, particle size and
contact time [8]. Subsequent adsorption experiments were
carried out with only optimized parameters. All the
experiments were carried out in triplicate and the mean values
of three data sets are presented. The results are as presented in
Table 2-5.
2.4 Batch mode adsorption studies
Adsorption experiments were carried out in 100 mL
Erlenmeyer flasks containing 0.1gr of sorbent prepared
previously and 50 mL solution with known concentration, pH
value and temperature. The flasks were stirred; the agitator
stirring speed was 250 rpm. After a preset contact time, the
samples were separated from the solution by filtration through
the Whatman No.1 filter paper. Blank solutions were treated
similarly without the adsorbent, and the recorded
concentrations at the end of each operation were taken as
control. The exact concentration of the residual metal ion in
the filtrate was analyzed by an atomic absorption spectrometer
(Shimdzu AA-6701F, Japan).
The amount of metal ions adsorption at equilibrium, qe
(mg/g) and percentage removal were calculated using the
following equation
Adsorption at time (1)
Metals (2)
Where qt is the adsorption capacity (mg/g), Co, Ci, and Ce,
Cf are the initial (mg/L), and final concentration metal
compounds (mg/g) respectively, where M is the adsorbent
dosage (g), V is the solution volume (L)
Sorption equilibrium studies: Samples of SW, each
weighing 0.100 g, were mixed with 50.0 mL metals solution of
a known concentration. Then, the mixture was shaken for 1 h
and allowed to settle for 20 mins to achieve equilibrium. The
same experiment was repeated for different initial
concentrations of metals ranging from 10 ppm to 200 ppm.
The type of adsorption was identified by studying the variation
of the amount of metals adsorbed on SW with the initial metals
concentration, while the equilibrium concentrations were used
in adsorption isotherm analysis.
3. RESULT AND DISCUSSION
The physical characteristics along with the percentage of
carbon, oxygen, hydrogen, nitrogen and sulphur of sago waste
are presented in Table 1.
3.1 Effect of Operating Conditions on the Adsorption of the
Metal Ions
The influence of operational parameters s such as amount of
adsorbent, agitation speed, particle size, initial pH and contact
time were investigated. The results were expressed as the
percentage removal efficiency(% R) of the adsorbent on
metal ions , which was defined in equation 1 & 2
3.1.1 Effect of p H
pH is an important parameter for adsorption of metal ions
from aqueous solution because it affects the solubility of the
meta l ions , concentration of the counter ions on the
functional groups of the adsorbent and the degree of ionization
of the adsorbate during reaction[9]. It was found that the
metals adsorption percentage of sago waste increased from pH
1 b 1a
The Third Basic Science International Conference - 2013
C19-3
6 to 9 and likewise, the adsorption percentage is reduced with
decreased in pH lower than 4.
As shown in Table 2, the uptake of free ionic metal ions
depends on pH, where optimal metal removal efficiency
occurs at pH 5 and then decreasing at higher pH. Removal
efficiency for Cd+2
increased from 76.1% to 79.9% over pH
range from 6.0 to 9.0. The metal ions Cr+3
and Cu+2
, also
showed similar trends but with much lower removal efficiency
and slight different optimum pH value. The adsorption
efficiency is as result of the fact that the pH values for these
materials are at a lower pH range as the adsorbent, unlike
values reported for most untreated sorbent [10].
3.1.2 Effect of Dose
The influence of metal ions sorption on amount of adsorbent
was studied by varying the amount of adsorbents from 2.0 to
40 g/l, while keeping other parameters (pH, agitation speed,
and contact time) constant. Table 3 shows the metal ions
removal efficiency for adsorbent used. Form the table, it can
be deduced that removal efficiency of the adsorbent generally
improved with increasing dose. This is expected due to the fact
that the higher the dose of adsorbent in solution, the greater the
availability of exchangeable sites for the ions.
The variation of adsorbent capacity with increment in
dosage is shown in Table 3. It was observed that as the dosage
increased from 2 to 40 g/L the metals adsorption increased
from 22.7 % to 94.9 % for lead, 9.3 % to 44 % for cadmium
while copper increased also from 15 % to 45 %, after which a
decline in capacity was noticed beyond 30 g/L. However the
capacity for Chromium increased from 23 % at 2 g/L dosage to
a maximum of 42.5 % at 30 g/L.
3.1.3. Effect of agitation speed
The effect of agitation speed on removal efficiency of
metal ions was studied by varying the speed of agitation from
100 to 300 rpm, while keeping the other factors constant.
As observed from Table 4, the metal ions removal efficiency
generally increased with increasing agitation speed. The metal
ions removal efficiency of adsorbent increased when agitation
speed increased from 200 rpm to 250 rpm and the adsorption
capacity appears relatively constant for agitation rates greater
than 200 rpm. These results can be associated to the fact that
the increase of the agitation speed, improves the diffusion of
metal ions towards the surface of the adsorbents. This also
indicates that a shaking rate in the range 150-250 rpm is
sufficient to ensure that all the surface binding sites are made
readily available for metal uptake.
TABLE 2.
SHOWING THE EFFECT OF pH ON THE EXTENT OF ADSORPTION
OF THE METAL IONS
pH range Sorption Percentage
Metals C d(II)
5.6 Pb(II) 4.7 Cu(II) 5.5
Cr(III)
4.3
Ambient 62.07 96.6 48.86 35.6
2 7.83 21.01 2.3 0.8
3 42.03 76.33 19.83 11.55
4 56.25 95.58 45.03 38.2
5 62.19 94.78 45.66 56.3
6 76.12 94.86 47.98 51.6
7 73.12 89.35 78.48 43.51
8 80.86 91.09 78.33 36.9
9 79.94 94.54 78.18 60.31
Contact time: 60mins, temp.25℃. Dose: 2 g/l, agitation speed:
250rpm and metal Conc.: 10 ppm
TABLE 3.
SHOWING THE EFFECT OF DOSE ON THE EXTENT OF
ADSORPTION OF T HE METAL IONS
Adsorb.
Dosage Sorption Percentage
g/L C d(II) Pb(II) Cu(II) Cr(III)
2 9.29 22.66 15.30 22.80
10 29.09 72.45 20.50 30.20
20 32.86 88.72 41.11 38.42
30 37.95 94.36 49.20 42.50
40 43.97 94.85 44.81 30.21
Contact time: 60mins, temp.25℃., agitation speed: 250rpm and metal
Conc.: 100 ppm
TABLE 4.
SHOWING T HE EFFECT OF AGITATION SPEED ON THE
EXTENT OF ADSORPTION OF T HE METAL IONS
Agitation
speed Sorption Percentage
rpm C d(II) Pb(II) Cu(II) Cr(III)
100 67.18 22.66 15.30 22.81
150 67.92 72.45 20.50 30.20
200 67.03 88.72 49.11 48.42
250 74.07 94.36 49.20 42.51
300 72.09 94.85 44.87 30.20
Contact time: 60mins, temp.25℃. , ambient pH, Dose: 1 g/l, agitation
speed: 250rpm and metalonc.: 10 ppm
TABLE 5.
SHOWING THE EFFECT OF CONTACT TIME ON THE EXTENT OF
ADSORPTION OF THE METAL IONS
Shaking time
(mins) Sorption Percentage
(min) C d(II) Pb(II) Cu(II) Cr(III)
15 39.20 93.57 36.50 20.50
30 44.08 93.86 45.33 18.29
45 57.42 94.00 48.13 24.33
60 57.07 94.90 54.64 28.72
90 56.98 95.49 54.12 33.38
120 53.52 95.18 56.16 32.80
150 53.10 93.72 54.89 35.11
180 47.65 94.55 53.81 34.76
210 47.73 94.76 50.76 39.98
240 50.12 94.39 53.05 32.84
Contact time: 60mins, temp.25℃. , ambient pH, Dose: 2 g/l, agitation
speed: 250rpm and metal Conc.: 10 ppm
The Third Basic Science International Conference - 2013
C19-4
3.1.4 Effect of contact time
Result in Table 5 indicates that the metal ions removal
efficiency increased with an increasing contact time before
equilibrium is reached. Other parameters were kept optimum,
while temperature was kept at 25℃.
It is observed that metal ions removal efficiency of sago
waste increased from 44.1 % to 57.1 % for cadmium when
contact time was increased from 30 to 60 min. Optimum
contact time for adsorbate was found to be 60 min. This result
is significant, as equilibrium time is one of the important
parameters for an economical wastewater treatment system.
3.1.5. Effect of Sago Wastes Particle Size
The effects of particle sizes of adsorbent are clearly shown
in the Figure 1. The results revealed that the size of the
adsorbent plays an important role in the metals adsorption
process. The particles sizes of adsorbent used in this study are
<350 µm, 750 µm and 1200 µm.
The adsorption capacity of metal ions by the 350 µm sago
wastes particle size is much higher compared to the larger
particle sizes. The effect of altering the adsorbents particle size
on the sorption percentage showed that, there was a more
dominant removal of metals by the smaller particles. This was
most probably due to the increase in the total surface area,
which provided more sorption sites for the metal ions [6.]. The
smaller adsorbent particle size offers a comparatively larger
and more accessible surface area, as a result, higher adsorption
occurs at equilibrium. Breaking a larger particle tends to open
tiny cracks and channels on the particle surface that providing
added surface area, which can be employed in the adsorption
process [5].
3.2 Equilibrium sorption study
3.2. 1 Langmuir isotherm model
The Langmuir model was expressed in Eq. (3) [11]:
(3)
Where Ce is concentration of metal ions at equilibrium
(mgL1), qe is amount of metal ions adsorbed at equilibrium
(mgg-1
), KL is Langmuir isotherm constant related to free
energy of adsorption (L.mg-1
), qm is maximum adsorption
capacity (mgg-1
). Equation (3) could be linearised into:
(4)
The plot of Ce/qe against Ce gave a straight line with slope
of 1/qm and intercept of 1/qm.KL.
The linear plot of Ce/qe versus Ce. The constants Q0 and b
can be calculated from slope and intercept of the plot and the
values are tabulated in Table 7. The shape of the Langmuir
isotherm was investigated by the dimensionless constant
separation term (RL) to determine high affinity adsorption and
is expressed as RL=1 / (1+b C0). RL values indicate the nature
of adsorption process. Where, Co = Initial metals concentration
(mg/L), b = Langmuir constant (L/mg). The parameter, RL
indicates the shape of the isotherm as follows in table 6
TABLE 6.
RL values Type of Isotherm
RL > 1 Unfavourable
RL =1 Linear
0 < RL <1 Favourable
RL =0 Irreversible
In the present investigation, the RL values were less than one
which shows the adsorption process was favorable as shown in
table 7
Table 7 showed the Langmuir plot of metal ions adsorption
by SW with a correlation coefficient of Cu+2
(0.9499) Cr+3
0.907) Cd+2
0.9023) and Pb+2
0.9905) improved which was
very close to unity, thus indicating that the data conform well
to the Langmuir isotherm model
3.2. 2. Freundlich isotherm model
The Freundlich isotherm assumes a heterogeneous surface
with a non-uniform distribution of heat of biosorption over the
surface and a multilayer biosorption can be expressed
Freundlich, [12]. The Freundlich model was expressed as:
(5)
Where Kf is Freundlich indicative of relative adsorption
capacity of adsorbent, n is Freundlich indicative of the
intensity of adsorption. Equation (5) could be linearised by
taking logarithms as followed:
(6)
The linear plot of logqe versus logCe. The values of 1/n and
kF can be calculated from the slope and intercept respectively
and the results are given in Table 7. When 1/n is >1.0, the
change in adsorbed metals concentration is greater than the
change in the metal concentration in solution.
The estimated model parameters with correlation coefficient
(R2) for the two models are shown in Table 7. It was observed
The Third Basic Science International Conference - 2013
C19-5
that results fitted well in the Langmuir model in terms of R2
value.
TABLE 7.
ISOTHERM MODEL PARAMETERS AND CORRELATION
COEFFICIENT
Langmuir Isotherm -1
Parameter Cu+2 Cr+3 Cd+2 Pb+2
R2 0.9499 0.9075 0.9023 0.9905
Qe (mmol/g) 0.12 0.08 0.17 0.10
Qmax (mg/g) 7.41 3.92 18.67 20.73
b (L/mg) 0.15 0.229 0.07 0.07
RL 0.48 0.53 0.42 0.40
Freundlich Isotherm
R2 0.8051 0.704 0.8088 0.8365
n (g/L) 3.05 3.32 2.82 1.05
KF (mg/g(L/g)1/n) 2.13 2.00 2.26 2.90
4. CONCLUSION
This work shows the interest of a concept based on a waste
to treat another waste or to resolve an environmental problem.
The results obtained confirm that the low-cost materials tested
can remove metal ions at different degrees from aqueous
solution. The sorption performances are strongly affected by
parameters such as: contact time, initial cadmium
concentration and sorbent type. The amount of metal ions
sorbed by these materials used increased with the increase of
contact time and initial cadmium concentration. An acceptable
fitting of metals sorption equilibrium data was obtained with
Langmuir model in all the range of concentrations studied.
Furthermore, the constants value which indicates adsorbent
affinity for metals varied in the trend Pb > Cd> Cu > Cr. This
trend is inline with maximum adsorption capacity (Qmax
(mg/g)) and this was assumed to be the critical factor favoring
competitive adsorption of metals on the adsorbent. While the
acidic functional groups on the adsorbent favoured general
metal adsorption on the adsorbent. This experimental study is
quite useful in developing an appropriate technology for
designing a waste water treatment plant.
ACKNOWLEDGEMENT
The authors would like to thank the Government of Brunei
Darussalam and the Universiti Brunei Darussalam for their
financial support.
REFERENCES
[1] G. Cimino, A. Passrini And G. Toscano, Removal Of Toxic Cations
And Cr(Vi) From Aqueous Solution By Hazelnut Shell. Water Res.
2000, 34 (11) :2955-2962.
[2] K.Kadirvelu, K.Thamaraiselvi, C.Namasivayam. “Adsorption of Nickel
(II) from aqueous solution onto activated carbon prepared from coir
pith”. Sep. Purif. Technol, vol.24, pp.497-505, 2001.
[3] H.W. Doelle. (1998). Socio-Economic Microbial Process Strategies For
A Sustainable Development Using Environmentally Clean
Technologies. Renewable Resources: Sagopalm. Proceedings Of The
Internet Conference On Integrated Bio-Systems,
Www.Ias.Unu.Edu/Proceedings/Icibs/
[4] W. S. A. B. W Mohamad Daud, N.Abdullah , K. Y. M. Chan & S.
Muhammad Azmi. (2010). Sago Kraft Paper: A Potential Solution To
Sago Industry Pollution. In W. D. Yang Li (Ed.),2010 Ieee International
Conference On Advanced Management Science(Icams 2010) (Pp.80-
83). Chengdu: Ieee Press. Doi:10.1109/Icams.2010.5553032
[5] W . Rafeah, Devagikanakaraju And Y. N. Ashikin, ‘ Preliminary Study
On Zinc Removal From Aqueous Solution By Sago Wastes ‘, Global
Journal Of Environmental Research 4 (2): 127-134, 2010
[6] S.Y., Quek, D.A.J., Wase, C.F., Forster, 1998. The Use of Sago Waste
For The Sorption Of Lead And Copper. Water Sa 24, 251–256.
[7] M. Ahmedna, M . Johnson, S.J. Clarke, W.E. Marshal And R.M.
Rao(1997): Potential Of Agricultural By -Product Based Activated
Carbon For Use In Raw Sugar Decolorisation. J.Sci.Food Agr Ic.
75: 117-124.
[8] S. Chakravarty , V. Dureja; G. Bhattachary Y A; S. Maity , And S.
Bhattacharjee,(2002) : Removal Of Arsenic From Groundwater Using
Low Cost Ferruginous Manganese Ore. Water Research; No. 36, Vol. 3,
P . 625-632.
[9] M.O. Corapcioglu, & C.P. Huang, (1987). The Adsorption Of Heavy
Metals Onto Hydrous Activated Carbon. Water Research, 21, 1031-
1044.
[10] P.R. Wittbrodt And C.D. Palmer, Effect Of Temperature, Ionic
Strength, Background Electrolytes And Fe (Iii) On The Reduction Of
Hexavalent Chromium By S Oil Humic Substances . Environmental
Science And Technology, 1996, Vol. 30, No. 8, P. 2470-2477.
[11] Langmuir, The Constitution And Fundamental Properties Of Solids And
Liquids. Journal Of The American Chemical Society. 1916, 38 : 2221-
2295.
[12] H.T.M. Freudlich, Over The Adsorption In Solution. Journal Of
Physical Chemistry. 1906, 57: 385-471
The Third Basic Science International Conference - 2013
C20-1
Abstract— Sago waste have been reported as promising sorbents
used in heavy metals removal due to the presence of abundant
functional groups. In the present study, the sorptive of cadmium
(II), chromium (III), and lead (II) in single aqueous solution,
using sago waste, was investigated in batch mode of operation. In
order to evaluate the biosorption capacity and characteristic,
effect of initial metals concentration (5 to 200 ppm) and shaking
time were studied. Metal ions was found to be totally absorbed
within 1 h while lead (II) is also absorbed very fast and can reach
equilibrium stage in 15 mins to 2 h. The results revealed that the
biosorption process of metal ions is a thermo-independent
process. The Langmuir and Freundlich models were used to
describe the adsorption isotherm data. Biosorption data fitted
well in Langmuir isotherms with high correlation coefficients for
all metal ions and this implies that monolayer sorption and
heterogeneous surface conditions exist under the used
experimental conditions. Modeling of kinetics results shows that
sorption process is best explained by pseudo – second order model
with determination coefficients 0.99 for all metal ions under all
experimental conditions.
Key words---- Sago wastes, Langmuir isotherm model, Kinetic
model, metal ions
I. INTRODUCTION
n recent years, there has been an increasing trend towards
more efficient utilization of agro-industrial by-products for
conversion to a range of value-added bioproducts, including
biofuels, biochemicals, and biomaterials [1]. As an initiative,
this study was formulated to utilize processed sago hampas as
an alternative substrate for heavy metal removal from
wastewater stream. Sago hampas is a starchy lignocellulosic
by-product generated from pith of Metroxylon sagu (sago
palm) after starch extraction process [2]. Metroxylon sagu
Rottb. Is an increasingly important socioeconomic ropin
Southeast Asia whereas Brunei is believed to be one of its
center of diversity.
In Brunei Darussalam, Ukong in the District of Tutong is
recognized as the largest sago- production plant, which exists
at present, it is estimated that about 9600 tonnes of sago
starch, extracted from sago palms, are produced per annum.
Other than rice, sago is the second important source of starch
as staple food for its population. The isolation of sago starch
* J. O. Amode is with Universiti Brunei Darussalam, Faculty of Science,
Jalan Tungku Link, Gadong BE1410, Brunei Darussalam
involves debarking, rasping, sieving, settling washing, and
drying [2]. However, the mechanical process currently
employed to extract sago starch is inefficient and often fails to
dislodge residual starch embedded in the fibrous portion of the
trunks [3]. On dry basis, sago hampas contains 58% starch,
23% cellulose, 9.2% hemicellulose, and 4% lignin [4].
Currently, these residues which are mixed together with
wastewater are either washed off into nearby streams or
deposited in the factory’s compound. These circumstances, in
time, may potentially lead to serious environmental problems.
The adsorption techniques have been found to be useful
means for controlling the extent of water pollution due to
heavy metals. Previous studies show that biomass of different
plants and animals have been employed as biosorbents in the
biosorption of metal ions from aqueous solutions. Such
materials include baker’s yeast [5-6], coconut husk, maize leaf
, human scalp hair [7-8], crab shell [9-10], agricultural by-
products [11], Coco nucifera [12], wood sawdust [13] and
Sugarcane bagasse [14].
This study was carried out to investigate the biosorption of
metal ions from aqueous solution using sago waste biomass.
The effects of parameters such as contact time and initial metal
concentration were studied. The effect of isotherm equilibrium
and kinetics of biosorption were systematically studied.
2. MATERIALS AND METHODS
2.1 Adsorbent
2.1.1 Preparation of the Studied Samples
Sago wastes that consist of fine and coarse “hampas” (solid
residue which is left behind after the starch has been washed
out) were obtained from the sago processing plant in Ukong,
Tutong district, Brunei Darussalam. The material for the
samples was selected manually, cleaned and dried in an oven
at temperature of 105 oC for 24 hours. Finally, the dried
material was grinded, screened to known particle size which
was used for adsorption study.
2.2 Adsorbate
All the chemical reagents used in these studies were of
analytical grade. Stock solutions (1000 mg/l) were prepared
from CrNO3O9.9H2O; Cd (NO3)2.4H2O and Pb (NO3)2 in de
ionized water respectively. Further working solutions were
prepared by diluting this stock solution. Initial pH was
adjusted using 0.1N HNO3 or 0.1N NaOH.
J. O. Amode*, J. H. Santos, A. H. Mirza and C. C. Mei
Biosorption of Toxic Cations onto Sago Waste II: Kinetic
and Equilibrium Studies
I
The Third Basic Science International Conference - 2013
C20-2
The amount of metal ions adsorption at equilibrium, qe
(mg/g) and percentage removal were calculated using the
following equation
Adsorption at time (1)
Metals (2)
Where qt is the adsorption capacity (mg/g), Co, Ci, and Ce,
Cf are the initial (mg/L), and final concentration metal
compounds (mg/g) respectively, where M is the adsorbent
dosage (g), V is the solution volume (L)
Sorption equilibrium studies: Samples of SW, each
weighing 0.100 g, were mixed with 50.0 mL metals solution of
a known concentration. Then, the mixture was shaken for 1 h
and allowed to settle for 20 mins to achieve equilibrium. The
same experiment was repeated for different initial
concentrations of metals ranging from 10 ppm to 200 ppm.
2.3 Characterization of Adsorbent
The FTIR spectra of raw samples before and after
adsorption were recorded using an infrared spectrometer
between wave numbers of 4000 and 400 cm-3
. Samples in the
particle size range of 10-20 mm were mixed with
spectroscopic grade Potassium Bromide, KBr in the ratio of
1:50 to produce sufficient absorbance [15].
3. RESULT AND DISCUSSION
3.1 Equilibrium sorption study
3.1.1 Effect of contact time
Result in Figure 1; indicates that the metal ions removal
efficiency increased with an increasing contact time before
equilibrium is reached. Other parameters were kept optimum,
while temperature was kept at 25℃.
It is observed that metal ions removal efficiency of sago
waste increased from 455 % to 57.4 % for cadmium when
contact time was increased from 30 to 60 min. Optimum
contact time for adsorbate was found to be 60 min for metal
ions. This result is important, as equilibrium time is one of the
important parameters for an economical wastewater treatment
system
3.1.2 Effect of Initial concentration
The effect of initial metal ions concentration on the
biosorption capacity shows that up to 97.50% of the metal Ions
concentration was sorbed at the initial metals concentration of
0- 20 mg L-1 within the fixed time optimum time 60 min as
determined from our previous paper. As shown in Figure 2 the
efficiency increases as the initial metal ion concentration
increases. The result implies that the gradual increase in the
efficiency of the biomass shows nearness to saturation of the
available binding sites.
Figure 1. Contact time: 60mins, temp.25℃. , ambient pH, Dose: 2 g/l,
agitation speed: 250rpm and metal Conc.: 10 ppm
Figure 2. Contact time: 60mins, temp.25℃. , ambient pH, Dose: 2 g/l,
agitation speed: 250rpm
3.2 Equilibrium sorption study
3.2. 1. Langmuir isotherm model
The Langmuir model was expressed in Eq. (3) [16]:
(3)
Where Ce is concentration of metal ions at equilibrium
(mgL-1
), qe is amount of metal ions adsorbed at equilibrium
(mgg-1
), KL is Langmuir isotherm constant related to free
energy of adsorption (Lmg-1
), qm is maximum adsorption
capacity (mgg-1
). Equation (3) could be linearised into:
(4)
The plot of Ce/qe against Ce gave a straight line with slope
of 1/qm and intercept of 1/qm.KL.
The constants Q0 and b can be calculated from slope and
intercept of the plot and the values are tabulated in Table 1.
The shape of the Langmuir isotherm was investigated by the
dimensionless constant separation term (RL) to determine high
affinity adsorption and is expressed as RL=1 / (1+b C0). RL
values indicate the nature of adsorption process. Where, Co =
Initial metals concentration (mg/L), b = Langmuir constant
(L/mg).
The Third Basic Science International Conference - 2013
C20-3
In the present investigation, the RL values were less than one
which shows the adsorption process was favorable as shown in
table 1. Table 1 showed the Langmuir plot of metal ions
adsorption by SW with a correlation coefficient of Cr+3
0.9075) Cd+2
0.9023) and Pb+2
0.9905) improved which was
very close to unity, thus indicating that the data conform well
to the Langmuir isotherm model
3.2. 2. Freundlich isotherm model
The Freundlich isotherm assumes a heterogeneous surface
with a non-uniform distribution of heat of biosorption over the
surface and a multilayer biosorption can be expressed
Freundlich, [17]. The Freundlich model was expressed as:
(5)
Where Kf is Freundlich indicative of relative adsorption
capacity of adsorbent, n is Freundlich indicative of the
intensity of adsorption. Equation (5) could be linearised by
taking logarithms as followed:
(6)
The linear plot of logqe versus logCe. The values of 1/n
and kf can be calculated from the slope and intercept
respectively and the results are given in Table 1. When 1/n is
>1.0, the change in adsorbed metals concentration is greater
than the change in the metal concentration in solution.
TABLE 1.
ISOTHERM MODEL PARAMETERS AND CORRELATION
COEFFICIENT
Langmuir -1
Parameter Cr+3 Cd+2 Pb+2
R2 0.9075 0.9023 0.9905
Qmax (mg/g) 3.92 18.67 20.73
b (L/mg) 0.229 0.07 0.07
RL 0.53 0.42 0.4
Freundlich
Parameter Cr+3 Cd+2 Pb+2
R2 0.704 0.8088 0.8365
n (g/L) 3.32 2.82 1.05
KF (mg.g-1) 2.00 2.26 2.9
The estimated model parameters with correlation
coefficient (R2) for the two models are shown in Table 1. It
was observed that results fitted well in the Langmuir model in
terms of R2 value.
Furthermore, the constants value which indicates adsorbent
affinity for metals varied in the trend Pb > Cd> Cr . This trend
is inline with metals maximum adsorption capacity and this
was assumed to be the critical factor favoring competitive
adsorption of metals on the adsorbent. While the acidic
functional groups on the adsorbent favoured general metal
adsorption on the adsorbent.
3.3 Adsorption Kinetics
The adsorption of the Pb II, Cr III, and Cd II onto sago
waste as a function of contact time was investigated and data
were given in Figure 3. The experiment was carried at initial
concentrations of 10mg/L whereby 0.1g of sorbent was
contacted with 50 ml of metal ions in aqueous solution.
Adsorption was rapid in the first stages of 10 mins to 40 mins
and then slowed considerably as the reaction approached
equilibrium as shown in Fig. 3. There was very little increment
in metal ions uptake after the first hour of contact as presented
in figure 3. Meanwhile, to design an appropriate adsorption
process, one should have sufficient information about the rate
at which adsorption occurs. Thus, data from the batch studies
for the removal of metal ions on the sago waste was analyzed
using three different kinetic models and also to determine the
time required to reach equilibrium. Data along with
regressions for Lagergren-first-order, pseudo second order
kinetic models and intra-particulate diffusion have been given
in Table 2
The Lagergren-first-order rate expression based on solid
capacity is generally expressed as follows [18]:
(7)
where qe and qt is the sorption capacity at equilibrium and
at time t, respectively (mg·g-1), k1 is the rate constant of
pseudo-first order adsorption (L·min-1). After integration and
applying boundary conditions t = 0 to t = t and qt = 0 to qt =
qt, the integrated form of Eq. (8) becomes:
(8)
Values of adsorption rate constant k1 for the metal ions
adsorption onto sago waste were determined from the straight
line plot of log qe − q versus t (Fig. 4). The data were not
fitted with a poor correlation coefficient and the calculated
amount of adsorption equation qe−cal is far from the actual
amount of adsorption equilibrium qe- exp. given in Table 2.
The pseudo second-order equation is also based on the
sorption capacity of the solid phase. Pseudo second-order
kinetic model as depicted in Fig. 5 can be given as follows
[18]:
(9)
The plot of (t/qt) and t of Eq. (9) should give a linear
relationship from which qe and k2 can be determined from the
slope and intercept of plotting of t/qt against t. where K2 is the
rate of the pseudo second order equation (g/mg.min) and qe is
the amount of the metal ions adsorbed per unit gram of
adsorbent at equilibrium and time t respectively. This model is
more likely to predict the behavior over the whole range of
The Third Basic Science International Conference - 2013
C20-4
adsorption. A plot of t/qt versus t for this plot is linear as
showed in figure 5 compared to the kinetic first order and
intra-particulate diffusion model.
Figure 3 plot of Adsorption capacity Vs Time
Figure 4. Pseudo-First order kinetic plots for metal ions
adsorption on sago waste
Figure 5. Pseudo-second order kinetic plots for metal ions adsorption
onto sago waste
Figure 6. Intra particle Diffusion Model plots for metal ions adsorption on
sago waste
According to the theory proposed by Weber and Morris [19].
(10)
Where C is the intercept and kp is the intraparticle diffusion
rate constant, which can be evaluated from the slope of the
linear plot of Qt vs t1/2
. The intercept of the plot reflects the
boundary layer effect, that is, the larger the intercept, the
greater the contribution of the surface adsorption in the rate-
controlling step. If the regression curve of Qt vs t1/2
is linear
and passes through the origin, then intraparticle diffusion will
be the sole rate-limiting step. However, the linear plot for each
concentration that passes through the origin is not the case in
this work, as shown in Fig.6,
TABLE 2.
KINETIC MODEL PARAMETERS AND CORRELATION
COEFFICIENT
Metal ions Cd[II] Cr[III] Pb[II]
Qeexp (mg/g) 2.730 1.702 4.131
Pseudo First
Order Model
R2 0.6998 0.9524 0.9717
Qecalc
(mg/g) 0.832 1.487 1.154
Pseudo
Second Order
Model
R2 0.9969 0.9946 0.9999
Qecalc
(mg/g) 2.831 1.795 4.261
Intra Particle
Diffusion
Model
R2 0.8322 0.9429 0.8378
Kd (mg/g
min) 0.067 0.143 0.105
C (mg/g) 1.735 0.393 3.297
The calculated amount of adsorption equation qe−cal is
similar to be actual amount of adsorption equilibrium qe. The
calculated qe is almost similar to the experimental values
hence the adsorption of metal ions from aqueous solution
follows the second order kinetic models. The correlation co-
efficient for the linear plots are superior to 0.99 in all the
systems. The sorption system is not a first-order reaction,
intra-particulate diffusion model and that a pseudo second-
order model can be considered.
The Third Basic Science International Conference - 2013
C20-5
TABLE 3
PHYSICAL AND CHEMICAL COMPOSITION OF THE SAGO
WASTE
Parameter Unit Values
Particle Size (µm) µm
<350
CEC (Meq/
g)
2.51
Elemental
Composition
% Wt 41.44 Carbon, 5.84
Hydrogen, Oxygen
4.56 , <0.50 Nitrogen,
0.61 Sulphur
Surface Chemistry -OH Groups; Carbonxyl
Compound; Presence Of –NH2;
Vibration Of The Bond C=O,
S=O and -OH
50075010001250150017502000225025002750300032503500375040001/cm
%T
Pb loaded USW 50ppm.ir Figure 7.
Wave number (cm-1) Vs % Transmission FTIR Spectra. (a) Raw processed sago waste, (b) Cadmium loaded onto
sago waste and (c) Lead loaded onto sago waste
4. CONCLUSION
It has been shown that the use of biosorbent composite from
renewable materials for heavy metal ions uptake is
technically feasible, eco-friendly, low cost and with high
efficiency. This study has shown the possibility of sorption of
untreated sago waste onto metal ions. From the results
discussed, it was shown that lead and cadmium have highest
adsorption capacity at ambient temperature. Langmuir
isotherm model better fitted the equilibrium adsorption data
then Freundlich model for the metals ions based on solution
analysis, it is suggested that the Langmuir model which favors
monolayer formation is followed by transfer of Pb (II) , Cr(II)
and Cd (II) species into the bulk of biomass particles.
Kinetically, the adsorption process followed the pseudo second
order mechanism. Such studies would be important in
designing environmentally friendly treatment methods using
natural substances, such as sago waste, for real industrial
effluents contaminated with this study metal ions and other
metal ion. Besides that, being composed entirely of
agricultural waste, it helps in reduction of waste generation
and added value to the waste. This adsorbent can be a good
candidate for adsorption not only for these heavy metals
selected; but also others in industrial and municipal wastewater
stream.
ACKNOWLEDGEMENT
The authors would like to thank the Government of Brunei
Darussalam and the Universiti Brunei Darussalam for their
financial support.
REFERENCES
[1] Y. Lin and S. Tanaka, “Ethanol fermentation from biomass resources:
current state and prospects,” Applied Microbiology and Biotechnology,
vol. 69, no. 6, pp. 627–642, 2006.
[2] D. S. Awg-Adeni, S. Abd-Aziz, K. Bujang, and M. A. Hassan,
“Bioconversion of sago residue into value added products,” African
Journal of Biotechnology, vol. 9, no. 14, pp. 2016–2021, 2010.
[3] A. Karim, A. P. L. Tie, D. M. A. Manan, and I. S. M. Zaidul, “Starch from
the sago (Metroxylon sagu) palm tree—properties, prospects, and
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Comprehensive Reviews in Food Science and Food Safety, vol. 7, no. 3,
pp. 215–228, 2008.
[4] S. Linggang, L. Y. Phang, M. H. Wasoh, and S. Abd-Aziz, “Sago pith
residue as an alternative cheap substrate for fermentable sugars
production,” Applied Biochemistry and Biotechnology, vol. 167, pp. 122–
131, 2012.
[5] P. Vasuderan, V. Padmavathy, S.C Dhingra (2003). Kinetics of
biosorption of cadmium on Baker’s yeast, Bioresour. Technol. 89(3): 281-
287.
[6] Y. Gõksungur, S. Üren, U. Güvenc (2005) Biosorption of cadmium and
lead ions by ethanol treated waste baker’s yeast Bioresour. Technol. 96(1):
103-109.
[7] N.A.A. Babarinde, J.O. Babalola, R. A. Sanni (2006). Biosorption of lead
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[8] N.A.A. Babarinde, O.O. Ogunbanjo, J.O. Babalola (2002) Effect of
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2(182): 200-202.
[9] D.S. Kim (2004). Pb2+ removal from aqueous solution using crab shell
treated by acid and alkali. Bioresour. Technol. 94(3): 345-348.
[10] K. Vijayarghavan, K. Palanivelu , M. Velan (2006). Biosorption of copper
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Bioresour. Technol. 97:1411-1419.
[11] A. A. Abia, M. Jr. Horsfall, O. Didi (2003). The use of chemically
modified and unmodified cassava waste for the removal of Cd, Cu and Zn
ions from aqueous solution. Bioresour. Technol. 90(3): 345-348.
[12] K. Conrad, H.C.B. Hansen (2007). Sorption of zinc and lead on coir.
Bioresour. Technol. 98: 89-97.
[13] M. Sciban, B. Radetic , Z. Kevresan, M. Klasnja (2007). Adsorption of
heavy metals from electroplating waste water by wood sawdust, Bioresour.
Technol. 98 402-409
[14] Karnitz O Jr, Gurgel LVA, deMelo JCP, Botaro VR, Melo TMS, Gil RP,
Gil LF (2007) Adsorption of heavy metal ion from aqueous single metal
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98: 1291-1297
[15] R. Wahi, Devagikanakaraju And N. A. Yusuf, ‘ Preliminary Study On
Zinc Removal From Aqueous Solution By Sago Wastes ‘, Global Journal
Of Environmental Research 4 (2): 127-134, 2010
[16] Langmuir, The Constitution And Fundamental Properties Of Solids And
Liquids. Journal Of The American Chemical Society. 1916, 38 : 2221-
2295.
[17] H.T.M. Freudlich, Over the adsorption in solution. Journal of physical
chemistry. 1906, 57: 385-471
[18] E. W. Shin, K. G. Karthikeyan, and M. A. Tshabalala,. 2007 .
“Adsorption mechanism of cadmium on juniper bark and wood.”
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[19] W. J. Weber, J. C. Morris, Kinetics of adsorption on carbon from solution,
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A
B
C
The Third Basic Science International Conference - 2013 PSC20-1
Abstract— Herein the study of inclusion complex of methyl red
and cyclodextrins (α, β and γ-CDs), were investigated using
molecular modeling calculation and UV-Vis spectroscopy. The
molecular modeling study adopted was quantum mechanics
calculation using Gaussian 03 software. The UV-Vis
spectroscopy results were found to be comparable with the
quantum mechanics calculations performed using the
semiempirical method PM3. The experimental data (UV, pH, Kb)
show that β-CD is the best host among the studied CD
compounds in the following order: MR-β-CD » MR-γ-CD » MR-
α-CD.
Keywords: inclusion complex, α, β and γ-cyclodextrins, methyl
red.
1. INTRODUCTION
yclodextrins are cyclic oligosaccharides which have been
recognized as useful pharmaceutical excipients and
cyclodextrin inclusion complexes are of interest for scientific
research, because they exist in aqueous solution and can be used
to study hydrophobic interactions which are very important in
biological systems. [1] Computational chemistry is leading to a
wide range of possibilities usually interdisciplinary due to
explosive increase in computer power and software capabilities.
Computational chemistry is also integrating the chemistry
curriculum. [2] A second use of computational chemistry is the
understanding of problem more completely. Many experimental
chemists are now using computational chemistry technique to
Manuscript received October 9, 2001. (Write the date on which you
submitted your paper for review.) This work was supported in part by the
U.S. Department of Commerce under Grant BS123456 (sponsor and
financial support acknowledgment goes here). Paper titles should be
written in uppercase and lowercase letters, not all uppercase. Avoid
writing long formulas with subscripts in the title; short formulas that
identify the elements are fine (e.g., "Nd–Fe–B"). Do not write “(Invited)”
in the title. Full names of authors are preferred in the author field, but are
not required. Put a space between authors’ initials.
F. A. Author is with the National Institute of Standards and
Technology, Boulder, CO 80305 USA (corresponding author to provide
phone: 303-555-5555; fax: 303-555-5555; e-mail: author@
boulder.nist.gov).
S. B. Author, Jr., was with Rice University, Houston, TX 77005 USA.
He is now with the Department of Physics, Colorado State University,
Fort Collins, CO 80523 USA (e-mail: [email protected]).
School of Chemical Sciences, Universiti Sains Malaysia, Penang,
Malaysia, 11800 USM, Penang, Malaysia
Correspondence e-mail: [email protected],
gain additional understanding of the compounds being examined. [3]
Computational chemistry can be used in a number of different
ways. One particularly important way is to model a molecular
system prior to synthesizing that molecule in the laboratory.
Although computational models may not be perfect, they are
often good enough to rule out 90% of possible compounds as
being unsuitable for their intended use. This is very useful
information because synthesizing a single compound could
require months of labor and raw materials, and generate toxic
waste. [4]
Azo dyes are widely used in industry. A large amount of these
dyes are discharged into streams and rivers, and they are
considered as an environmental pollutant. Some of these
compounds may accumulate into food chains and eventually
reach the human body through ingestion. [4] Intestinal microbiota
and to a lesser extent, the liver enzymes, are responsible for the
cleavage of azo dyes into aromatic amines, like methyl red.
Methyl Red is a commonly used mono azo dye in laboratory
assays, textiles and other commercial products; however, it may
cause eye and skin sensitization and pharyngeal or digestive tract
irritation if inhaled or swallowed.[4] Furthermore, MR is
mutagenic under aerobic conditions of late, there has been
increasing interest to develop low-cost means of reducing the
amount of, if not completely remove, MR in wastewater before
being discharged into receiving water body. [5]
2.Methods
The study were conducted using two approaches which are
explained. The theoretical study were used to predict the
structure and the binding properties of the MR inclusion complex
while UV-Vis spectroscopy were used to determine the effect of
pH on the strength of the binding .
2.1 Theoretical Methods
The study were conducted using two the theoretical study
were used to predict the structure and the binding properties of
the MR inclusion complex.
2.1.1 Technical details
All calculation were done using an Intel Xenon 3.0 Hz
workstation with double operating system, Linux OpenSuse 10.2
OS and 32 bit Windows OS desktop. Quantum mechanics
computational of host/guest interaction in vacuum were carried
out using Gaussian 03.[6] Meanwhile the computational of host,
Minimization was performed using conjugate gradient algorithm
with 0.1 k cal/A.mol and further minimized at 0.001
kcal/A.mol.
2.1.2 Quantum mechanics calculation
UV-vis spectroscopy and semiempirical quantum
chemical studies on the inclusion complex of methyl red
with cyclodextrins
BOUBAKER HOSOUNA, ROHANA ADNAN
C
The Third Basic Science International Conference - 2013 PSC20-2
The starting geometries of MR and the host structures (α-CD,
β-CD and γ-CD) were built based on the structures that were
generated from the crystallographic parameters. [7] provided by
the Cambridge Structural and were separately optimised using
the semiempirical method, PM3 using Gaussian03 software
package. [6] The starting geometries of the inclusion complexes
were constructed using HyperChem (Version 8.0, Hypercube,
Gainesville, FL, USA). The previously optimised structures of
MR and host molecules were allowed to approach each other
along the symmetry axis (the X-axis) passing through the centre
of the host cavity. For example, in the case of α-CD, the
coordinate system used to define the process of complexation
was based on constructing the α-CD with the six identical
glucose units positioned symmetrically around the Z-axis, such
that all the glycosidic oxygens are in the XY plane and their
center was defined as the center of the coordination system. [8]
The MR molecule was docked into the cavity of the CD with the
central nitrogen atom connecting the two benzene rings that
coincides with the Z-axis. Docking was initially done to
maximise the electrostatic and hydrophobic interactions between
the host and the guest molecules. Multiple starting points were
generated by moving the guest molecules along the – and +Z-
axis from 1 to 21 Å, at 1 Å intervals, and by rotating the guest
molecules from 0°–315°. [9] Three different inclusion
orientations, i.e., the nitrogen from the alkyl group of the MR
vertically, facing up and down horizontally into the cavity of the
host, were considered for each case (Figure 1)(a, b).
(a) -(CH3)2N group ponting in
( b) -COOH group ponting in
Figure 1. Modelling MR with CD’s (a), (b).
The inclusion interactions were simulated in vacuum and the
presence of water molecules were ignored to save computational
time especially for large molecules. The complexation energy, E,
was calculated for the minimum energy structures by the
following equation:
E = Ecomplex – (ECD + EMR)…… (1) [9]
where E is binding energy, Ecomplex , ECD and EMR represent the
total energy of the host-guest complex, the free guest molecule
and the free host molecule, respectively. The magnitude of the
energy change is an indication of the driving force towards
complexation. The more negative the complexation energy
change, the more thermodynamically favourable is the inclusion
complex.
3. Results & discussion
3.1 Theoretical results
a) Calculation of the binding energy for free molecules
The binding energy for each of the studied molecules was
calculated using G03 software. The results showed that the
energies for MR is 0.0661559 hartree and α, β, γ-cyclodextrin
molecules were found equal to -1.7041491 hartree, -2.1905000
hartree and -2.7823972 hartree respectively.
b) Calculation of the initial binding energy for inclusion
complex
The binding energy for the MR-α-CD, MR-β-CD and MR-γ-
CD inclusion complexes were also calculated using G03
software. (Figure 2) shows the optimum energies of the complex
with -(CH3)2N and -COOH group pointing in. The results
showed that the lowest observe for the complexes are -1.8235998
hartree, -2.3306923 hartree and -2.9150409 hartree respectively
with -(CH3)2N group pointing in.
(a)
The Third Basic Science International Conference - 2013 PSC20-3
(b)
(c)
Figure 2. Optimization energies values of α, β, γ-cyclodextrin
(a), (b) and (c) respectively with -(CH3)2N and -COOH group
pointing in, at various angles from 0o to 315o.
c) Calculation of the final binding energy for inclusion
complex.
The final binding energies for the MR-α-CD, MR-β-CD and MR-
γ-CD inclusion complexes were calculated based on the above
findings using equation (1).From the above discussion, it was
found that the lowest binding energies were found the structures
from angles 270o, 315o and 225o respectively (optimization
results). These values were further confirmed using equation (1).
Results showed that the lowest binding energies of the inclusion
complexes between the guest (methyl red) and the host (α, β, γ-
cyclodextrin) equals to -0.1856066 hartree, -0.2063482 hartree
and -0.1987996 hartree respectively with -(CH3)2N group
pointing in at angles 270o, 315o and 225o respectively (Figure 3).
(a)
(b)
(c)
Figure 3. The binding energies values of α, β, γ-cyclodextrin (a),
(b) and (c) respectively with -(CH3)2N and -COOH group
pointing in, at various angles from 0o to 315o.
Therefore, it can be concluded that the inclusion complexes
between the methyl red and α, β, γ-cyclodextrin are highly
stable under the studied theoretical parameters (Table 1). This
data were used for the simulation of the inclusion complexes
between the methyl red and α, β, γ-cyclodextrin using quantum
mechanics calculation.
The Third Basic Science International Conference - 2013 PSC20-4
Table 1. The binding energies in (hatree) of MR-α-CD, MR-β-
CD and MR-γ-CD with -(CH3)2N and -COOH group pointing
in, at various angles from 0o to 315o calculated by Gaussian03.
Table 1. The binding energies in (hatree) of MR-α-CD, MR-β-
CD and MR-γ-CD with -(CH3)2N and -COOH group pointing
in, at various angles from 0o to 315o calculated by Gaussian03.
c) Comparison between the structures of CD’s inclusion
complexes calculated using Gaussian 03.
Table 2 shows the comparison between the binding energies of
the inclusion complexes between the three cyclodextrin
compounds and methyl red. The data showed that β-
cyclodextrin has the lowest binding energy with methyl red
regardless of which group pointing in. (Figure 2, b) shows the
structure with the lowest overall binding energy is -
(CH3)2N group pointing in, with one of the aromatic ring
included inside the cavity.
Table 2. Comparison between the lowest binding energy values
(kcal/mol) for α-, β- and γ cyclodextrin complex with methyl red,
with -(CH3)2N and -COOH group pointing in.
Figure 4 show the structure of the lowest energy conformation
between methyl red and the host (β-CD), calculated using PM3
method ( Gaussian 03). This method consistently predicts with -
(CH3)2N group pointing in with one of the aromatic ring resides
inside the cavity of the CD.
Angle 0 45 90 135 180 225 270 315
B.E with
(CH3)2N
α
-0.1846066 -0.1559599 -0.1776488 -0.1559599 -0.1813432 -0.1823835 -0.1856066 -0.1766813
B.E with
COOH
-0.1831445 -0.1849399 -0.1810081 -0.1832401 -0.1830664 -0.1793148 -0.1806064 -0.1809123
B.E with
(CH3)2N
β
-0.1957821 -0.1959683 -0.1923394 -0.1907716 -0.1921125 -0.1900321 -0.1950972 -0.2063482
B.E with
COOH
-0.1908727 -0.1946201 -0.2024768 -0.2058901 -0.1963277 -0.1997415 -0.1963781 -0.1932565
B.E with
(CH3)2N
γ
-0.1909200 -0.1925808 -0.1953515 -0.1918650 -0.1928122 -0.1987996 -0.1976673 -0.1929684
B.E with
COOH
-0.1948969 -0.1964494 -0.1934711 -0.1932467 -0.1931709 -0.1965001 -0.1954552 -0.1910671
Cyclodextrin -(CH3)2N -COOH
α
-116.46992481 -114.92493341
β -129.48547810 -129.19801595
γ -124.74865907 -123.30570073
The Third Basic Science International Conference - 2013 PSC20-5
Figure 4. The structure of the lowest energy conformation from
optimization using PM3 method for (MR-β-CD) inclusion
complex.
Hydrogen bonding between carboxylic group in MR molecule
and hydrogen bond in the host structure with -(CH3)2N group
pointing is shown in Table 3.
Table 3 shows the seven hydrogen bond between the ligand
(MR) and the host structure (β-CD). They are of different type
which are CO-----HO, OH----OC, CH----OH, CH----OC and CN-
----CO.
Table 3. The hydrogen bonding form between β-cyclodextrin-
methyl red (MR-β-CD) inclusion complex.
Hydrogen bonding Bonding
distance (A°)
C=O96 (ligand)-----H-O136(β-CD)
2.60
O-H95 (ligand)-----O-C119(β-CD)
2.85
C-H171 (ligand)-----O-H166(β-CD)
2.93
C-H172 (ligand)-----O-C161(β-CD)
1.79
C-H175 (ligand)-----O-C131(β-CD)
2.86
C-H174 (ligand)-----O-C123(β-CD)
1.71
C-H173 (ligand)-----O-C163(β-CD)
1.70
C-N97 (ligand)-----O-C103(β-CD)
3.29
C-H177 (ligand)-----O-H157(β-CD) 2.58
3.2 Experimental Investigations
The formation of the inclusion complex between CD’s and MR
was conducted using three different techniques. These include:
1. UV-Vis spectrophotometric method. To find the maximum
wavelength (λmax) and the optimum absorption of the
inclusion complex.
2. pH method. To find the acidity of the medium.
3. Calculating of the binding constant (Kb). To confirm which
one of the studied CD compounds form the most stable
inclusion complex with MR.
3.2.1 UV-Vis spectrophotometric method
This experiment was conducted to determine the λmax and the
highest absorbance for the inclusion complex formed between
the host (CD’s) and guest (MR) molecules. (Figure 5, a) shows
the schematic diagram of MR disintegration of methyl red at
different pH. However, it is well known that MR has two
different λmax at different pH values (Figure 5, b). It has a yellow
colour in the basic medium (λmax, 425 nm) and red colour in the
acidic medium (λmax, 520 nm). λmax value for inclusion complex
which is 425 or 520 nm is more stable to format inclusion
complex.
(a)
(b)
Figure 5: (a) The chemical disintegration of methyl red and (b)
effect of pH on the absorbance (λmax) of MR. [10, 11, 12, 13]
The Third Basic Science International Conference - 2013 PSC20-6
UV-Vis instrumental results for inclusion complex of CD’s +
MR:
Figures 6, 7 and 8 shows the UV-Vis spectra of α-, β- and γ-CD-
MR inclusion complexes. Different solution containing different
concentrations (0.5, 1, 1.5, and 2 ppm) of both CD and MR were
used for the calibration. (Figure 6) shows the dependence of the
absorbance of α-CD-MR inclusion complex on the concentration
of the reactants. The maximum absorbance was found at λmax =
429 nm in the basic form slightly different from the reported
value (λmax 425 nm). [10, 11, 12, 13] (Figure 7) also shows the
dependence of the absorbance of β-CD-MR inclusion complex
on the concentration of the reactants. The maximum absorbance
was found at λmax = 426 nm in the basic form similar to the
reported value. Finally, (Figure 8) shows the dependence of the
absorbance of γ-CD-MR inclusion complex on the concentration
of the reactants. The maximum absorbance was found at λmax =
428 nm in the basic form different from the reported value. These
findings revealed that β-CD is the best cyclodextrin
compound which formed the most stable inclusion complex with
MR in the basic medium.
Figure 6. A plot of absorbance for inclusion complex of (α-CD)-
MR.
Figure 7. A plot of absorbance for inclusion complex of (β-CD)-
MR.
Figure 8. A plot of absorbance for inclusion complex of (γ-CD)-
MR.
3.2.2 Calculation of the Binding Constant (Kb)
This method is used to calculate the binding constant (Kb) for the
of MR-α-CD inclusion complex. The calculation steps are as
follows:
MR] + [α-CD] [α-CD-MR] …........ (1)
[Guest] + [host] [Inclusion complex]...… (2)
Inclusion complex association constant =
..….….(3) [9]
Inclusion complex×mg.L-1 at Absorbance value
(0.105) is stable.
αcyclodextrin host× mg.L-1
Guest× mg.L-1
Kb = 1.5× / [5× 10-6 ][ 5× 10-6 ] = 6 × 104 L.mg-1
The same equation (equation 4) was used for the calculation of
the association constants of both MR-β-CD and MR-γ-CD
complexes.
Inclusion complex× mg.L-1 at Absorbance value
(0.156) is stable.
βcyclodextrin host× mg.L-1
Guest× mg.L-1
Kb = 2 ×/ [5× 10-6 ][ 5× 10-6 ] = 8 × 104 L.mg-1
And that for MR-γ-CD inclusion complex is:
Inclusion complex× mg.L-1 at Absorbance value
(0.037 is stable.
γcyclodextrin host× mg.L-1
Guest× mg.L-1
Kb = 0.5 ×/ [5× 10-6 ][ 5× 10-6 ] = 2 × 104 L.mg-1
Therefore, the association constant (Kb) for the studied
complexes (MR-α-CD, MR-β-CD and MR-γ-CD) is equal to 6
× 104 L.mg-1, 8 × 104 L.mg-1, and 2 × 104 L.mg-1 respectively.
From the above experimental results (UV, pH, Kb) it can be
concluded that the basic medium is the most suitable medium for
the formation of inclusion complexes between CD’s (α, β and γ-
CD) and MR. This was confirmed by highest absorbance, highest
pH value and highest binding constant (Kb). Table 4 summaries
these results.
200.0 250 300 350 400 450 500 550 600 650 700 750 800.0
0.000
0.01
0.02
0.03
0.04
0.05
0.06
0.07
0.08
0.09
0.10
0.11
0.12
0.13
0.14
0.15
0.16
0.17
0.18
0.19
0.20
0.21
0.22
0.23
0.24
0.25
0.258
nm
A
1 ppm
0.5 ppm
1.5 ppm
2 ppm
5 ppm
200.0 250 300 350 400 450 500 550 600 650 700 750 800.0
-0.001
0.02
0.04
0.06
0.08
0.10
0.12
0.14
0.16
0.18
0.20
0.22
0.24
0.26
0.28
0.30
0.32
0.34
0.36
0.38
0.40
0.42
0.44
0.46
0.48
0.50
0.52
0.54
0.56
0.58
0.605
nm
A
0.5 ppm
1 ppm
1.5 ppm
2 ppm
5 ppm
The Third Basic Science International Conference - 2013 PSC20-7
Table 4. Summary of the max absorbance ( λmax=425 nm), pH
and Kb of the inclusion complexes.
Method α-CD-MR β-CD-MR γ-CD-MR
Con (ppm) 1.5 2 0.5
UV (Abs) 0.105 0.156 0.037
pH 6.98 6.89 7.61
Kb (L.mg-1) 6 × 104 8 × 104 2 × 104
4. Conclusion
The simulation of the interaction between methyl red and CDs
differs from α to β to γ in terms of power. The binding energy
between β-CD and MR was found to be less than α and γ-
cyclodextrins in the sense that it has higher stability at various
stages and angles.
Computational calculations for the MR-CDs inclusion complexes
with show that the differences in the stability of these complexes
lead to different orientation for MR and ways approaching the
cavity. Therefore, the theoretical study shows that an inclusion
complex can be formed between CD’s and MR. It also shows
that β-CD is the best host among the studied CD compounds
based on it forms the most stable conformation of the inclusion
complex. The UV-Vis experimental results obtained were found
to be comparable with the docking calculations. The
experimental (UV, pH, Kb) data shows that β-CD is the best
among the studied CD compounds in the following order: MR-
β-CD » MR-γ-CD » MR-α-CD.
Reference
[1] E.M. Martin del Valle, Journal Process Biochemistry,
cyclodextrins application, (2004), 39, 1033-1046.
[2] David C. Young, Computational Chemistry: A Practical
Guide for Applying Techniques to Real-World Problems,
New York (2001), 408 pages.
[3] M. F. Schlecht, Molecular Modeling on the PC. Wiley-
VCH, New York (1998), 3-10.
[4] M.Vieth, J. D.Hirst, B. N. Domini, H. Daigler, and C. L.
Brooks, Journal of Computational Chemistry. 1998, 19,
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[5] Frisch, M.J.; Trucks, G.W.; Schlegel, H.B.; Scuseria, G.E.;
Robb, M.A.; Cheeseman, J.R.;Montgomery, J.A.;
Vreven, T., Jr.; Kudin, K.N.; Burant, J.C.; et al. Gaussian
03, Revision B.03;Gaussian, Inc.: Pittsburgh, PA, USA,
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[6] M. Mueller, Fundamentals of quantum chemistry book,
Second Edition (Complementary Science), New York,
(2001), p 291.
[7] Aree, T.; Chaichit, N. Carbohydrate Research. (2002),
337, 2487-2494.
[8] K. S. Danel, P. G. Asiorski, M. Matusiewicz, S. Całus, T.
Uchaczc, and A. V.Kityk, Spectrochimica Acta Part A,
(2010) 77, 16–23.
[9] Alamdar ashnagar, Nahid gharib naseri and Bita khanaki,
(2007), 4, 550-558.
[10] B. Y. Chen, Journal of Process Biochemistry (2002), 38,
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[11] G. Muthuraan, T. T. Teng, Progress in Natural Science,
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[12] H. A. Benesi and J. H. Hildebrand, Journal of American
Chemistry Society, (1949) 71, 2703-2724.
[13] T. W. Newton and F. B. Baker, Journal of Physical
Chemistry, (1957) 61, 934-953.
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NAME Institute COUNTRY E-Mail
Dann Mallet Queensland University of
Technology Australia [email protected]
Hideo Tsuboi Nagoya University Japan [email protected]
Kwang-Ryeol
Lee
Korea Institute of Science and
Technology South of Korea [email protected]
Lidia Morawska Queensland University of
Technology Australia [email protected]
M. Nurhuda Brawijaya University Indonesia [email protected]
Nurul T.
Rochman Indonesian Institute of Sciences Indonesia [email protected]
Petr Solich Charles University Czech Republic [email protected]
S.K. Lai National Central University Taiwan [email protected]
A. H. Mirza Universiti Brunei Darussalam Brunei
Darussalam
Abdul Wahab
Mohammad University Kebangsaan Malaysia Malaysia [email protected]
Akil Ahmad University Kebangsaan Malaysia Malaysia
Anthony B.
Hamzah University of Sriwijaya Indonesia antoinetonee@ gmail.com
Atikah Brawijaya University Indonesia [email protected];
C. C. Mei Universiti Brunei Darussalam Brunei
Darussalam
Chasan Bisri Brawijaya University Indonesia
Crys F Partana Yogyakarta State University Indonesia
Endang Tri
Wahyuni Gadjah Mada University Indonesia
Harno Dwi
Pranowo Gadjah Mada University Indonesia [email protected]
Heruna Tanty Bina Nusantara University Indonesia [email protected]
Imelda Fajriati Gadjah Mada University Indonesia
J. H. Santos Universiti Brunei Darussalam Brunei
Darussalam
J. O. Amode Universiti Brunei Darussalam Brunei
Darussalam [email protected]
M Utoro Yahya Gadjah Mada University Indonesia
Margaretha
Ohyver Bina Nusantara University Indonesia [email protected]
Mudasir Gadjah Mada University Indonesia
Muhammad Said University of Sriwijaya Indonesia
Nurlelasari University of Padjajaran Indonesia [email protected]
Qonitah Fardiyah Brawijaya University Indonesia
Ria Armunanto Gadjah Mada University Indonesia [email protected]
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Rizka Setianing
Wardhani Brawijaya University Indonesia
Rizki Layna R Brawijaya University Indonesia
Subriyer Nasir University of Sriwijaya Indonesia [email protected]
Suwardi Yogyakarta State University Indonesia suwardi@ uny.ac.id
Tati Herlina University of Padjajaran Indonesia [email protected]
The Third Basic Science International Conference - 2013
ACK-1
Acknowledgement The Program Committee would like to thank the followings for their supports:
Universitas Brawijaya
PT. Semen Gresik
PT. PLN (Persero)
The Third Basic Science International Conference - 2013
ACK-2
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ACK-3