preface - universitas brawijaya...rahman, mahiran basri studies of parameter effects on...

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


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


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

mailto:[email protected]


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


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


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:

[email protected]).

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


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.


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

qq

Plot Uji Multinormal

Sources: Processed Minitab, 2012

Fig 1. Scatter plot of multivariate normal assumption test


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


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

http://www.ekologi.litbang.depkes.go.id/data/abstrak/Athena.pdf

http://www.ekologi.litbang.depkes.go.id/data/abstrak/Athena.pdf


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


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)


C03-3

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.


C03-4


C03-5

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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.


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

mailto:[email protected]


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


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


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)


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


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 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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18435-18440


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:

[email protected]).

Armunanto, R., is with Austrian-Indonesian Centre for Computational

Chemistry, Dept. of Chemistry, Gadjah Mada University, Indonesia (e-mail:

[email protected]).

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

qq

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


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.


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


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].


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


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


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


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


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


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.


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


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


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


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

http://www.elsevier.com/locate/trac


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


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


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


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


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

http://www.ias.unu.edu/proceedings/icibs/


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


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


3.1.1 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. 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).


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 qeexp. 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


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.


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

challenges as a new industrial source for food and other uses,”

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

ions from aqueous solution by maize leaf. Int. J. Phys. Sci. 1(1): 23-26.

[8] N.A.A. Babarinde, O.O. Ogunbanjo, J.O. Babalola (2002) Effect of

perming the human scalp hair on its sorption of metal ions. Afr. J. Technol.

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

(11) and cobalt (11) from aqueous solutions by crab shell particles.

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

solution by chemically modified sugacane bagasse, Bioresour. Technol.

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.”

Bioresour. Technol., 98, 588–594.

[19] W. J. Weber, J. C. Morris, Kinetics of adsorption on carbon from solution,

J. Sanitary Eng. Div. Proc. Am. Soc. Civil Eng. 1963; 89: 31–59.

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],

[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 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)


(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.


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


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


2.86


1.71


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]


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


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,

1612–1622.

[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,

(2003).

[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,

437- 446.

[11] G. Muthuraan, T. T. Teng, Progress in Natural Science,

(2009), 19, 1215–1220.

[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.

http://free.7host07.com/ejournal/Vol4/no4/V4N4/550-558.asp

The Third Basic Science International Conference - 2013 AU-1

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];

[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]

The Third Basic Science International Conference - 2013 AU-2

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]


ACK-1

Acknowledgement The Program Committee would like to thank the followings for their supports:

Universitas Brawijaya

PT. Semen Gresik

PT. PLN (Persero)


ACK-2


ACK-3

preface - universitas brawijaya...rahman, mahiran basri studies of parameter effects on...

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