Table Of ContentFerrates
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In Ferrates; Sharma, V.;
ACS Symposium Series; American Chemical Society: Washington, DC, 2008.
ACS SYMPOSIUM SERIES 985
Ferrates
Synthesis, Properties, and Applications
in Water and Wastewater Treatment
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98 Virender K. Sharma, Editor
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American Chemical Society, Washington, DC
In Ferrates; Sharma, V.;
ACS Symposium Series; American Chemical Society: Washington, DC, 2008.
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1 The paper used in this publication meets the minimum requirements of
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1 American National Standard for Information Sciences—Permanence of Paper
g doi: for Printed Library Materials, ANSI Z39.48-1984.
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The citation of trade names and/or names of manufacturers in this publication is
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PRINTED IN THE UNITED STATES OF AMERICA
In Ferrates; Sharma, V.;
ACS Symposium Series; American Chemical Society: Washington, DC, 2008.
Foreword
The ACS Symposium Series was first published in 1974 to pro
vide a mechanism for publishing symposia quickly in book form. The
purpose of the series is to publish timely, comprehensive books devel
oped from ACS sponsored symposia based on current scientific re
search. Occasionally, books are developed from symposia sponsored by
1 other organizations when the topic is of keen interest to the chemistry
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85.f Before agreeing to publish a book, the proposed table of con
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20 interest to the audience. Some papers may be excluded to better focus
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02 appropriate, overview or introductory chapters are added. Drafts of
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0. chapters are peer-reviewed prior to final acceptance or rejection, and
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g doi: manuscripts are prepared in camera-ready format.
bs.acs.or5, 2008 | papers aArse ian crluuldee, do ninly t hoer igvionluaml reess.e aVrecrhb aptaimpe rrse parnoddu ocrtiiogninsa ol fr epvrieevwi
012 | http://pun Date: July 2 AouCslSy Bpouobklissh Dede ppaarptemrse anrte not accepted.
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August 3, Publicati
In Ferrates; Sharma, V.;
ACS Symposium Series; American Chemical Society: Washington, DC, 2008.
Preface
This book is derived from a symposium sponsored by the
American Chemical Society (ACS) Divisions of Environmental Chem
istry, Inc. and Inorganic Chemistry, Inc., Ferrates: Synthesis, Properties,
a nd Applications in Water a nd Wastewater Treatment, which was
1 organized for the 232nd ACS National Meeting in San Francisco, Cali
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pr fornia, September 10-14, 2006. Papers were solicited with a call for
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98 papers, as well as with direct contact with researchers. The symposium
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8- was international in nature and 33 experts from the United States, Eur
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2 ope, and Asia gave oral presentations.
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1/ In recent years, the higher oxidation states of iron (Ferrates) are
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1 of interest because of their involvement in reactions of environmental,
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oi: 1 industrial, and biological importance. A number of high-quality papers
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bs.a5, 2 techniques are used to characterize the ferrate species. Applications of
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2 | Dat explored. This book is timely because ferrate is emerging as a green
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2o chemistry chemical for organic synthesis and for treating toxins in water.
3, ati
ust blic A main objective of the symposium was to bring together experts with a
ugPu background in fundamentals and applications of ferrate chemistry. Many
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contributors covered the multidisciplinary theme during the symposium.
Chapters for the book were solicited from the symposium's oral
presentations as well as from additional researchers in the field to provide
a balanced presentation. This book is organized into three sections:
synthesis and characterization, properties, and applications in water and
wastewater treatment. Chapter 1 provides a comprehensive review of
recent advances in Fe(VI) synthesis. Chapters 2-4 are devoted to
electrochemical synthesis of Fe(VI). Chapters 5 and 6 give wet- and dry-
oxidation methods to synthesize Fe(VI). Chapter 7 gives an overview of
oxidation states of iron with valences from +4 to +8 in solid states.
Chapters 8 and 9 present a review of the thermal decomposition of
xi
In Ferrates; Sharma, V.;
ACS Symposium Series; American Chemical Society: Washington, DC, 2008.
Fe(VI) salts and determination of low concentrations of Fe(VI),
respectively. Chapters 10-13 are devoted to the generation and properties
of aqueous high-oxidation states. Chapter 14 gives a review on recent
advances in Fe(VI) charge storage and super-iron batteries. Chapter 15
presents a frozen solution Mossbauer spectroscopy technique to learn the
aqueous chemistry of Fe(VI). The final section of the book is devoted to
the application of Fe(VI) as an oxidant, coagulant, and disinfectant in the
treatment of water, wastewater, and sludge. Chapters 16-19 present
examples of treatment of water and biosolids. Chapter 20 gives the
potential of ferrate to oxidize recalcitrant compounds. Chapters 21 and 22
demonstrate the combination of ferrate and a photocatalytic oxidation
process to enhance the degradation of pollutants. Chapters 23-26 are on
1 the removal of pharmaceuticals and estrogens in water by Fe(VI).
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pr0 Chapters 27-30 deal with the use of Fe(VI) to enhance the removal of
85. algae, organics, and metals and thus to improve the water quality.
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8- This book is the first comprehensive compilation of the chem
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2 istry and application of ferrates. The contents of the book should appeal
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10 are engaged in understanding the chemistry of high-valent iron and in
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1 applications of chemical oxidants, coagulants, and disinfectants to treat
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s.org 08 | d contaminants in water, wastewater, and industrial effluents.
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bs.a5, 2
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2 | Dat I gratefully acknowledge the peer reviewers whose comments
201on contributed significantly to improve the final versions of the chapters.
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Virender K. Sharma
Chemistry Department
Florida Institute of Technology
150 West University Boulevard
Melbourne, FL 32901
[email protected]
xii
In Ferrates; Sharma, V.;
ACS Symposium Series; American Chemical Society: Washington, DC, 2008.
Ferrates
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In Ferrates; Sharma, V.;
ACS Symposium Series; American Chemical Society: Washington, DC, 2008.
Chapter 1
Recent Advances in Fe(VI) Synthesis
Stuart Licht and Xingwen Yu
Department of Chemistry, University of Massachusetts Boston,
Boston, MA 02125
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09 The synthesis and analysis of a range of Fe(VI) compounds
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k-2 referred to as ferrates or super-iron compounds. Fe(VI) salts
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1/ with detailed syntheses in this paper include the alkali Fe(VI)
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oi: BaFe0, 2SrF4eO, and also AgFeO. Two conventional, as
8 | d well as4 two imp4 roved Fe(VI) s2ynth4etic routes are presented.
0
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p://pubs.acs.orDate: July 25, (rsaobultuypet erehnr -ayitprfeooo nrc csha Fltobieory(in VtesdI.)i) s oTsfsoh aFlelut est(ni IoeInawI)n , od rfa o nuFtdhte eets0 h 4e2e=i ,ln secyaclnnturdtdoh ecep hsriaees mc soiiopfcl iaitldael stissso yynsnno ttwlhhueiebtsshliie ss
11 | httcation a(innacllyutdicea li nm-estihtoud o&lo geixes- ssiutum msayrnitzheeds isa)r eo fF TFeIR(V, I)I CsPal,t st.i trFi-e(VI)
8, 20Publi metric, UV/VIS, XRD, Mössbauer and a range of electro
er chemical analyses. Fe(VI) compounds have been explored as
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m energy storage cathode materials in both aqueous and non
e
ec aqueous phase in "super-iron" battery configurations, as well
D
as novel oxidants for synthesis and water treatment
purification. Preparation of reversible Fe(VI/III) thin film
towards a rechargeable super-iron cathode is also presented. In
addition, the preparation of unusual KMnO and zirconia
4
coatings on Fe(VI) salts, via organic solvent deposition, is
summarized. These coatings can stabilize and activate Fe(VI)
salts in contact with alkaline media.
2 © 2008 American Chemical Society
In Ferrates; Sharma, V.;
ACS Symposium Series; American Chemical Society: Washington, DC, 2008.
3
The fascinating chemistry of hexavalent iron, Fe(VI) is not as established as
that for ferrous, Fe(II), ferric, Fe(III) or zero valent (metallic) iron chemistry. As
a strong oxidant, Fe(VI), is formed in aqueous solutions as Fe02", which has
4
been investigated for several decades as a potentially less hazardous alternative
to the chlorination purification of water (7-3). The field of Fe(VI) compounds
for charge storage was introduced in 1999, and at that time the term super-iron
was coined to refer to the class of materials which contain "super-oxidized" iron
in the unusual hexavalent state (4). The charge transfer chemistry of super-iron
salts in both aqueous and non-aqueous media has been probed (4-32).
In conventional syntheses, high purity, stable KFe0 is prepared, from
2 4
alkaline hypochlorite oxidation of Fe(III). Less soluble Fe(VI) salts are prepared
by precipitation, upon addition of various salts to solutions containing dissolved
Fe02" (5,6). In addition to probing these syntheses, we have also introduced
4
several routes to improved Fe(VI) salt synthesis, including solid-state syntheses
1
0 and direct electrochemical synthesis of Fe(VI) salts. The conventional synthesis
0
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c for BaFe0 utilizing solution phase reactants is generalized on the left side of
5. 4
98 Scheme 1. The scheme of the center illustrates an alternative solid synthesis,
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8- which uses only solid state reactants. The right side of the scheme illustrates the
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20 direct electrochemical synthesis of Fe(VI) salts.
k-
1/b The one-step direct electrochemical synthesis (in-situ electrochemical
02 synthesis) of solid Fe(VI) salts has significant advantages in shorter synthesis
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0. time, simplicity, and reduced costs (no chemical oxidant is required). At
1
oi: potentials greater than 0.6 volt versus SHE (the standard hydrogen electrode) in
d
08 | alkaline media, an iron metal anode is directly oxidized to Fe042". When the
org 5, 20 realepcidtrloyl yisteo lactoedn taaisn sa saonli dF, ean(Vd Is)t apbrielcizipedit afteirnrgat ec asatilot.n A, st hree prgeesneenrtaetde do nF thee0 42r"i gihst
11 | http://pubs.acs.cation Date: July 2 yseFiliedee(eclVd tIorsIno )f b lSytsyhyct eednh ,ite rhccmeeeocntenti t ctep1a rr,ai endoocivxfni paigtdnhi tatteahat tiegioS oencdns hi.,os etfFsmh oaeeeln( v Vpei1urdIo,r) e nmst, h oaeeslntt uaaoutlbid soiceelna i zitonpiefo hd anas B.ocs eolIain ndFd dteehsug0tecar4 t,ati ied(vl7l aeur-t,esi9 otsa)rntc.aa ttbaetnoidl t isFcz aiehns(agIesI I ab)sla ke(rva7iule)i mrniase,l
8, 20Publi avoided, and fewer preparatory steps reduces requisite synthesis time, and can
er increase the yield of the Fe(VI) salt synthesis. For example, in the conventional
b
m synthesis of BaFe0, both KFe0 and Ba(OH) are reacted in the aqueous
e 4 2 4 2
ec phase, and BaFe0 is generated due to the higher alkaline insolubility of barium
D 4
ferrate(VI) compared to that of potassium ferrate(VI). In the solid synthesis, ,the
reactants such as KFe0 and barium oxide alone are stable, but fully react upon
2 4
grinding together, forming a dough-like paste; KOH is removed, isolating the
Fe(VI) salt. In the barium example, water, bound in the salt as the hydrate
BaO4H0 is necessary and sufficient to drive the reaction, and forms an
2
unusually pure (> 98%) and stable Fe(VI) salt (70).
This paper describes synthesis details of a variety of high purity Fe(VI)
salts, Fe(VI/III) reversible thin films (77, 12) and Mn coated (5) and zirconia
coated Fe(VI) salts (75). This includes electrochemical, and solid phase
In Ferrates; Sharma, V.;
ACS Symposium Series; American Chemical Society: Washington, DC, 2008.
