DOCSLIB.ORG

Colloidal Interactions in Ionic Liquids Interactions Collo¨Idalesdans Les Liquides Ioniques

Total Page：16

File Type：pdf, Size：1020Kb

Download full-text PDF Read full-text
Colloidal Interactions in Ionic Liquids Interactions Collo¨Idalesdans Les Liquides Ioniques Universite´ Pierre et Marie Curie Specialite´ : Chimie Physique ED 388 { Chimie Physique et Chimie Analytique de Paris Centre These` de Doctorat Colloidal Interactions in Ionic Liquids Interactions Collo¨ıdalesDans Les Liquides Ioniques Auteur: Directrice de th`ese: Marianna Mamusa Dr. V´eronique Peyre Travail de th`esesoumis pour obtenir le grade de Docteur de l'Universit´ePierre et Marie Curie et d´eroul´eau Laboratoire PHENIX - PHysicochimie des Electrolytes et Nanosyst`emesInterfaciauX Th`esesoutenue le 25 F´evrier2014 devant le jury compos´ede: Werner KUNZ, Professeur Rapporteur Andr´eVIOUX, Professeur Rapporteur Julian OBERDISSE, Directeur de Recherche Examinateur Corinne CHANEAC, Professeur Examinatrice V´eroniquePEYRE, Ma^ıtrede Conf´erences Directrice de th`ese Contents List of Figures vii List of Tables xi Abbreviations xiii Introduction1 1 Background5 1.1 Interactions between atoms, molecules, particles...............6 1.1.1 General Considerations on Electrostatic Forces...........6 1.1.2 Dipolar Magnetic Interactions..................... 11 1.1.3 Van der Waals Forces between Atoms and Molecules........ 12 1.1.4 Steric Contributions and Total Interaction Potential........ 15 1.1.5 DLVO Theory............................. 17 1.2 The Colloids: Maghemite Nanoparticles................... 22 1.3 Ionic Liquids.................................. 28 1.3.1 Ethylammonium Nitrate........................ 30 1.4 Ionic Liquids in Colloidal Systems: State of the Art............ 34 1.4.1 Ionic Liquids as a Medium for the Synthesis of Nanoparticles... 34 1.4.2 Colloidal Dispersions in Ionic Liquids................ 35 1.4.3 ILs at a Surface............................. 45 1.4.4 Interparticle Potential in ILs..................... 52 1.5 Conclusion................................... 55 2 Materials and Methods 57 2.1 Materials.................................... 58 2.2 Syntheses and Functionalizations....................... 58 2.2.1 Synthesis of Maghemite Nanoparticles................ 58 2.2.2 Size Sorting of Maghemite Nanoparticles............... 60 2.2.3 Preparation of Acidic and Alkaline Ferrofluids with Different Counter- ions................................... 62 2.2.4 Surface Functionalization with Citrate Ligands........... 63 2.2.5 Synthesis of the Ionic Liquid Ethylammonium Nitrate....... 64 2.2.6 Synthesis of the Choline-Amino Acid ([Cho][AA]) Ionic Liquids.. 64 2.2.7 Transfer of Nanoparticles from Water to IL............. 65 2.2.8 Lyophilization............................. 67 iii iv Contents 2.3 Characterization Techniques.......................... 67 2.3.1 Karl Fischer Titration......................... 67 2.3.2 pH Measurements in Ethylammonium Nitrate............ 68 2.3.3 Flame Atomic Absorption Spectroscopy............... 69 2.3.4 Small Angle (Neutron and X{Ray) Scattering............ 70 2.3.5 Dynamic Light Scattering....................... 71 2.3.6 Magnetization Measurements..................... 73 2.3.7 Magneto-Optical Birefringence Experiments............. 74 3 Preliminary Screenings on Polydisperse Nanoparticle/Ethylammonium Nitrate Dispersions 75 3.1 pH Measurements in Ethylammonium Nitrate................ 76 3.1.1 Response of the Glass Electrode in EAN............... 77 3.1.2 Dissociation Constants of Citric Acid in EAN............ 78 3.2 Dispersions of Bare Maghemite Nanoparticles in EAN: Effect of pH, Counterion and Water Content........................ 80 3.2.1 Neutral Medium { Point of Zero Charge............... 82 3.2.2 Acidic Medium............................. 82 3.2.3 Alkaline Medium............................ 84 3.3 Dispersions of Citrate-Covered Maghemite Nanoparticles in EAN..... 84 3.4 Microscopic Study of Citrate-Covered Maghemite Nanoparticles in EAN. 86 3.4.1 Dynamic Light Scattering Experiments............... 88 3.4.2 Small Angle Neutron Scattering (SANS) Experiments....... 90 3.5 Conclusion................................... 93 4 Dispersions of Size-Sorted Maghemite Nanoparticles in the IL Ethyl- ammonium Nitrate 95 4.1 Introduction................................... 96 4.2 Preparation and Chemical Analysis of the Samples............. 97 4.3 Evolution During the Preparation of the Samples: the Special Case of Lithium..................................... 102 4.4 Effect of NP Size and Concentration..................... 104 4.5 Small Particles (7 nm): Effect of the Counterion.............. 110 4.5.1 Dilute Regime............................. 110 4.5.2 Concentrated Regime......................... 111 4.6 Large Particles (11 nm): Effect of the Counterion.............. 118 4.6.1 Dilute Regime............................. 118 4.6.2 Concentrated Regime......................... 119 4.7 Discussion on the Effect of the Counterions on Both Sizes......... 128 4.8 Effect of Water Content............................ 131 4.9 Conclusion................................... 137 5 Tests with Cholinium-based Ionic Liquids 139 5.1 Introduction................................... 139 5.2 Dispersion of Maghemite Nanoparticles in Cholinium-Aminoacid ILs... 142 5.3 Dispersions of Maghemite in Water/[Cho][Gly] Media........... 144 5.4 Conclusion................................... 145 Contents v Conclusions and Perspectives 147 A Dispersions of Different Nanoparticles in Ionic Liquids 151 B Small Angle Scattering Techniques 157 B.1 Theoretical Principles............................. 157 B.2 Experimental Intensity and Absolute Intensity............... 159 B.3 Form Factor and Structure Factor...................... 160 B.4 Calculation of Scattering Length Densities and Contrast.......... 161 B.5 The Scattering Invariant. Calculation of Φ.................. 164 B.6 Guinier Plot................................... 165 B.7 Experimental Form Factors, P(Q)...................... 165 Bibliography 169 List of Figures 1.1 Electric Double Layer at a Charged Surface in Water............ 10 1.2 Van der Waals Interaction between Surfaces................. 14 1.3 Full Pair Potentials for Molecules and Particles............... 17 1.4 DLVO Energy vs. Distance Profiles...................... 18 1.5 TEM Image of Maghemite Nanoparticles................... 22 1.6 Stability of Maghemite Nanoparticles as a Function of pH......... 24 1.7 Dependence of the Structural Charge of Maghemite NP on the pH.... 25 1.8 Stability of Citrate-Covered Maghemite Nanoparticles as a Function of pH 25 1.9 Phase Diagrams for Citrate-Covered Maghemite Nanoparticles in Water. 26 1.10 Common IL Cations.............................. 28 1.11 Molecular Formula of Ethylammonium Nitrate............... 31 1.12 H-bond Networks of EAN and Water..................... 32 1.13 ZnO nanostructures synthesized in ILs.................... 35 1.14 IL Layers at the Bare Maghemite Surface.................. 37 1.15 Different Colloidal Stability of Bare and PMMA-Grafted Silica Particles. 41 1.16 Silica-based Ionogels.............................. 43 1.17 AFM Force Profile............................... 46 1.18 DLVO Interparticle Potential for Silica Particles in ILs........... 53 1.19 DLVO Interparticle Potential for Magnetite Particles in ILs........ 54 2.1 Size Distribution of Unsorted Maghemite Nanoparticles.......... 59 2.2 Destabilization of Maghemite Nanoparticles by Ionic Strength....... 60 2.3 Size Sorting of Maghemite Nanoparticles................... 61 2.4 Size Distribution of Size-Sorted Maghemite Nanoparticles......... 62 2.5 Reaction between Choline Hydroxide and an Amino Acid......... 65 2.6 Synthesis of Cho-AA Ionic Liquids...................... 66 2.7 Process 1 for the Transfer of NP from Water to IL............. 66 2.8 Process 2 for the Transfer of NP from Water to IL............. 66 2.9 Karl Fischer................................... 68 2.10 Sample Preparation for SAXS......................... 71 3.1 Response of a Glass Electrode in Basic EAN Solutions........... 78 3.2 Response of a Glass Electrode in EAN.................... 79 3.3 Different States of Dispersion......................... 82 3.4 Citrate Anion.................................. 85 3.5 DLS Experiments on Some Citrated NP................... 89 3.6 SANS Experiments on Polydisperse Maghemite Dispersions in EAN and Water...................................... 90 vii viii List of Figures 3.7 Fits of SANS Intensities for Three Representative Cases in Water and EAN 91 4.1 Separation of Particles and Solvent by Centrifugation........... 97 4.2 UV-Vis Absorption Spectra for FeNSA-5 Complex in EAN......... 99 4.3 Calibration Curve for the FeNSA-5 Complex in EAN............ 99 4.4 UV-Vis Absorption Spectra for FeNSA-5 Complex in EAN......... 100 4.5 Effect of Ageing on Li+/EAN Dispersione.................. 103 4.6 Effect of Ageing on Li+/EAN Dispersione.................. 103 4.7 Optical Microscopy under Magnetic Field: Reversible Phase Separation. 105 4.8 Coexistence of Dilute and Concentrated NP Phases (Large Particles)... 106 4.9 Optical Microscopy of the Coexistence of Dilute and Concentrated NP Phases...................................... 107 4.10 Schematic Phase Diagram for a Colloidal System.............. 107 4.11 S(Q) Plots for Dilute Dispersions of Small NP in EAN with Different Counterions................................... 111 4.12 I(Q) Plots for Small Particles with Different Counterions.......... 112 4.13 Magneto-Optic Birefringence Relaxation Curves for Small Particles with Different Counterions.............................. 112 4.14 Effect of Small NP Concentration of the S(Q) in the Case of Li+ Counterions114 4.15 Structure Factors for Dilute Suspensions of Large Particles........ 118 4.16 Magneto-optic Birefringence Experiments
Load more

Recommended publications
  • 03 Amine Chamber Studies.Pdf
    90 Chapter 3 Secondary Aerosol Formation from Atmospheric Reactions of Aliphatic Amines* ______________________ *This chapter is reproduced by permission from “Secondary aerosol formation from atmospheric reactions of aliphatic amines.” by S.M. Murphy, A. Sorooshian, J. H. Kroll, N. L. Ng, P. Chhabra, C. Tong, J.D. Surratt, E. Knipping, R. C. Flagan, and J. H. Seinfeld, Atmospheric Chemistry and Physics, 7(9), 2313-2337, 2007. Copyright 2007 Authors. This work is licensed under a Creative Commons License. 91 3.1 Abstract Although aliphatic amines have been detected in both urban and rural atmospheric aerosols, little is known about the chemistry leading to particle formation or the potential aerosol yields from reactions of gas-phase amines. We present here the first systematic study of aerosol formation from the atmospheric reactions of amines. Based on laboratory chamber experiments and theoretical calculations, we evaluate aerosol formation from reaction of OH, ozone, and nitric acid with trimethylamine, methylamine, triethylamine, diethylamine, ethylamine, and ethanolamine. Entropies of formation for alkylammonium nitrate salts are estimated by molecular dynamics calculations enabling us to estimate equilibrium constants for the reactions of amines with nitric acid. Though subject to significant uncertainty, the calculated dissociation equilibrium constant for diethy- lammonium nitrate is found to be sufficiently small to allow for its atmospheric formation, even in the presence of ammonia which competes for available nitric acid. Experimental chamber studies indicate that the dissociation equilibrium constant for triethylammonium nitrate is of the same order of magnitude as that for ammonium nitrate. All amines studied form aerosol when photooxidized in the presence of NOx with the majority of the aerosol mass present at the peak of aerosol growth consisting of + aminium (R3NH ) nitrate salts, which repartition back to the gas phase as the parent amine is consumed.
    [Show full text]
  • Ionic Liquids in Synthesis
    P. Wasserscheid and T. Welton (Eds.) Ionic Liquids in Synthesis P. Wasserscheid and T. Welton (Eds.) Ionic Liquids in Synthesis Related Titles from WILEY-VCH P.G. Jessop and W. Leitner (eds.) Chemical Synthesis Using Supercritical Fluids 1999. 500 pages. Hardcover. ISBN 3-527-29605-0 F. Zaragoza Dörwald (ed.) Organic Synthesis on Solid Phase Supports, Linkers, Reactions 2nd Edition, 2002. ca. 580 pages. Hardcover. ISBN 3-527-30603-X A. Loupy (ed.) Microwaves in Organic Synthesis 2002. ca. 350 pages. Hardcover. ISBN 3-527-30514-9 K. Tanaka (ed.) Solvent-free Organic Synthesis 2003. ca, 300 pages. Hardcover. ISBN 3-527-30612-9 P. Wasserscheid and T. Welton (Eds.) Ionic Liquids in Synthesis Volume Editors This book was carefully produced. Never- theless, editors, authors and publisher do Dr. Peter Wasserscheid not warrant the information contained RWTH Aachen therein to be free of errors. Readers are Institute for Technical and advised to keep in mind that statements, Macromolecular Chemistry data, illustrations, procedural details or Worringer Weg 1 other items may inadvertently be inaccurate. 52074 Aachen Germany Library of Congress Card No.: applied for A catalogue record for this book is available Dr. Thomas Welton from the British Library. Imperial College of Science, Technology and Medicine Bibliographic information published by Department of Chemistry Die Deutsche Bibliothek South Kensington Die Deutsche Bibliothek lists this publica- London SW7 2AY tion in the Deutsche Nationalbibliografie; UK detailed bibliographic data is available in the Internet at http://dnb.ddb.de © 2003 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim All rights reserved (including those of trans- lation in other languages).
    [Show full text]
  • Interfacial Properties of Mercury/Ethylammonium Nitrate
    Interfacial properties of mercury/ethylammonium nitrate ionic liquid+water system: Electrocapillarity, surface charge and differential capacitance Malika Ammam, Dung Di Caprio, Laurent Gaillon To cite this version: Malika Ammam, Dung Di Caprio, Laurent Gaillon. Interfacial properties of mercury/ethylammonium nitrate ionic liquid+water system: Electrocapillarity, surface charge and differential capacitance. Elec- trochimica Acta, Elsevier, 2012, 61, pp.207-215. 10.1016/j.electacta.2011.12.004. hal-01539730 HAL Id: hal-01539730 https://hal.sorbonne-universite.fr/hal-01539730 Submitted on 15 Jun 2017 HAL is a multi-disciplinary open access L’archive ouverte pluridisciplinaire HAL, est archive for the deposit and dissemination of sci- destinée au dépôt et à la diffusion de documents entific research documents, whether they are pub- scientifiques de niveau recherche, publiés ou non, lished or not. The documents may come from émanant des établissements d’enseignement et de teaching and research institutions in France or recherche français ou étrangers, des laboratoires abroad, or from public or private research centers. publics ou privés. Interfacial properties of mercury/ethylammonium nitrate ionic liquid + water system: electrocapillarity, surface charge and differential capacitance Malika Ammam †‡*, Dung Di Caprio† and Laurent Gaillo† † Laboratoire d’Electrochimie et Chimie Analytique, Equipe Energétique et Réactivité aux Interfaces, Université Pierre et Marie Curie-Case 39, 4, place Jussieu 75252 PARIS Cedex 05, France ‡ Present address: Faculty of Science, University of Ontario Institute of Technology, 2000 Simcoe Street North, Oshawa, ON L1H 7K4, Canada * Corresponding author: Phone (905)721-8668, ext 3625; Fax 905-721-3304; email: [email protected]; [email protected] Abstract In this account, surface tensions of mercury/ethylammonium nitrate (EAN) aqueous solutions at different compositions as a function of the potential have been measured.
    [Show full text]
  • Synthesis, Characterization and Combustion of Triazolium Based Salts U
    Synthesis, Characterization and Combustion of Triazolium Based Salts U. Schaller, T. Keicher, V. Weiser, H. Krause Fraunhofer Institut Chemische Technologie (ICT) Pfinztal, Germany S. Schlechtriem DLR – German Aerospace Center, Space Propulsion Institute Hardthausen, Germany ABSTRACT Salts being liquid below 100 °C are defined as ionic liquids[1]. They are receiving an increasing interest due to their unique properties and are also under investigation in the field of energetic materials. Potential applications are plasticizers, high explosives, gun and liquid rocket propellants. As a promising candidate for a high energy propellant, this paper presents the synthesis and some properties of 4-Amino-1-methyl-1,2,4-triazolium nitrate (AMTN). It has a glass transition point of -55 °C and shows good stability. Due to the very low vapor pressure a significantly reduced environmental risk, better storage and handling properties are expected. The combustion behavior was investigated in a window bomb under pressures up to 15 MPa resulting in a linear burning characteristic with low pressure dependence. Moreover, 4-Amino-1-methyl-1,2,4-triazolium perchlorate (AMTP) was synthesized and characterized. With its melting point close to TNT, AMTP has potential as a melt cast explosive. The enthalpy of formation was determined and the predicted performance was compared with TNT. For comparison the 4-Amino-1-H-1,2,4-triazolium salts were also synthesized. INTRODUCTION Ionic liquids (ILs) are in the focus of recent research and finding application in more and more fields of life. The applications range from novel reaction media[2], as electrolytes in batteries[3], solar cells[4], gas storing media[5], lubricants[6] and heat transfer fluids[7], to mention only a small excerpt of the investigated and in use applications.
    [Show full text]
  • Experimental Investigation of Mixtures of 1-Ethyl-3- Methylimidazolium Ethyl Sulfate and Ethylammonium Nitrate with Electrospray Propulsion Applications
    AIAA Propulsion and Energy Forum 10.2514/6.2019-3900 19-22 August 2019, Indianapolis, IN AIAA Propulsion and Energy 2019 Forum Experimental Investigation of Mixtures of 1-Ethyl-3- Methylimidazolium Ethyl sulfate and Ethylammonium Nitrate with Electrospray Propulsion Applications Mitchell J. Wainwright,1 Missouri University of Science and Technology, Rolla, Missouri, 65409 Joshua L. Rovey,2 University of Illinois Urbana-Champaign, Urbana IL, 61801 Shawn W. Miller,3 Boston College, Institute for Scientific Research, Chestnut Hill, MA, 02467 and Benjamin D. Prince,4 Air Force Research Laboratory, Space Vehicle Directorate, Kirtland AFB, NM, 87117 Physical properties, performance metrics, and mass spectra of mixtures of two ionic liquids (1-ethyl-3-methylimidazolium ethyl-sulfate aka [Emim][EtSO4] and ethylammonium nitrate aka EAN) are investigated from the standpoint of electrospray propulsive characteristics. Spectra suggest that as the [Emim][EtSO4] mixture fraction increases, the intensity of [Emim][EtSO4] related species in the plume also increases, while the presence of EAN decreases. Spectra also show presence of both EAN proton transfer species and species related to chemical reaction of [EtSO4] and water. Despite the volatility of EAN, it emits stably into vacuum at low flow rates when mixed with 25% [Emim][EtSO4]. Spectra also show species swapping between [Emim][EtSO4] and EAN, suggesting microscopic reorganization and non-linear mixing of physical properties. Experimental measurements of surface tension, conductivity, and density for various mixture mass percentages also show non-linear mixing characteristics. Conductivity differs by over 40% from linear predicted values. Analytic predictions of propulsion performance are presented based on the non- linear experimental property results, and compared to predictions based on linear mixing models.
    [Show full text]
  • Hydrogen Bonding in Protic Ionic Liquids: Structural Correlations, Vibrational Spectroscopy, and Rotational Dynamics of Liquid Ethylammonium Nitrate
    Hydrogen Bonding in Protic Ionic Liquids: Structural Correlations, Vibrational Spectroscopy, and Rotational Dynamics of Liquid Ethylammonium Nitrate Tobias Zentel1, Viviane Overbeck2, Dirk Michalik2, Oliver K¨uhn1, Ralf Ludwig2 1Institut f¨urPhysik, Universit¨atRostock, Albert-Einstein-Str. 23-24, D-18059 Rostock, Germany 2Abteilung f¨urPhysikalische Chemie, Institut f¨urChemie, Universit¨atRostock, Dr.-Lorenz-Weg 1, D-18059 Rostock, Germany E-mail: [email protected] July 26, 2017 Abstract. The properties of the hydrogen bonds in ethylammonium nitrate are analyzed by using molecular dynamics simulations and infrared as well as nuclear magnetic resonance experiments. Ethylammonium nitrate features a flexible three-dimensional network of hydrogen bonds with moderate strengths, which makes it distinct from related triethylammonium-based ionic liquids. First, the network's flexibility is manifested in a not very pronounced correlation of the hydrogen bond geometries, which is caused by rapid interchanges of bonding partners. The large flexibility of the network leads to a substantial broadening of the mid-IR absorption band, with the contributions due to N-H stretching motions ranging from 2800 to 3250 cm−1. Finally, the different dynamics are also seen in the rotational correlation of the N-H bond vector, where a correlation time as short as 16.1 ps is observed. Submitted to: J. Phys. B: At. Mol. Phys. 1. Introduction Ethylammonium nitrate (EAN) has been synthesized more than hundred years ago by Paul Walden [1]. EAN is formed by the neutralization of ethylamine with concentrated nitric acid. It consists solely of ions, namely ethylammonium and nitrate, and melts significantly below 100◦C, i.e.
    [Show full text]
  • Liquid Methylammonium Nitrate ⇑ Lorenzo Gontrani A, , Ruggero Caminiti A,B, Umme Salma A, Marco Campetella A,C a Università Degli Studi Di Roma ‘‘La Sapienza”, P
    Chemical Physics Letters 684 (2017) 304–309 Contents lists available at ScienceDirect Chemical Physics Letters journal homepage: www.elsevier.com/locate/cplett Research paper A structural and theoretical study of the alkylammonium nitrates forefather: Liquid methylammonium nitrate ⇑ Lorenzo Gontrani a, , Ruggero Caminiti a,b, Umme Salma a, Marco Campetella a,c a Università degli Studi di Roma ‘‘La Sapienza”, P. le Aldo Moro 5, I-00185 Roma, Italy b Centro di Ricerca per le Nanotecnologie Applicate all’Ingegneria CNIS, Università di Roma ‘‘La Sapienza”, P. le Aldo Moro 5, I-00185 Roma, Italy c Chimie ParisTech, PSL Research University, CNRS, Institut de Recherche de Chimie Paris, F-75005 Paris, France article info abstract Article history: We present here a structural and vibrational analysis of melted methylammonium nitrate, the simplest Received 22 May 2017 compound of the family of alkylammonium nitrates. The static and dynamical features calculated were In final form 5 July 2017 endorsed by comparing the experimental X-ray data with the theoretical ones. A reliable description can- Available online 6 July 2017 not be obtained with classical molecular dynamics owing to polarization effects. Contrariwise, the struc- ture factor and the vibrational frequencies obtained from ab initio molecular dynamics trajectories are in Keywords: very good agreement with the experiment. A careful analysis has provided additional information on the X-ray complex hydrogen bonding network that exists in this liquid. Nitrate Ó 2017 Elsevier B.V. All rights reserved. Methylammonium Melted AIMD 1. Introduction transfer reaction between the Brønsted acid nitric acid and the Brønsted base alkylamine. MAN is instead solid at room tempera- The latvian/russian/german chemist Paul Walden is generally ture, but it undergoes a solid I solid II phase transition at 352 K, recognized as one of the ‘‘fathers” of that class of (organic) molten turning into a ‘‘ionic plastic phase” which shows very large mobil- salts that most contemporary chemists would call ‘‘ionic liquids”.
    [Show full text]
  • Surfactant Behaviour of Sodium Dodecylsulfate In
    Subscriber access provided by CMU Libraries - http://library.cmich.edu Article Surfactant Behaviour of Sodium Dodecylsulfate in the Deep Eutectic Solvent Choline Chloride: Urea Thomas Arnold, Andrew J Jackson, Adrian Sanchez- Fernandez, Daniel Magnone, Ann E. Terry, and Karen J. Edler Langmuir, Just Accepted Manuscript • DOI: 10.1021/acs.langmuir.5b02596 • Publication Date (Web): 05 Nov 2015 Downloaded from http://pubs.acs.org on November 7, 2015 Just Accepted “Just Accepted” manuscripts have been peer-reviewed and accepted for publication. They are posted online prior to technical editing, formatting for publication and author proofing. The American Chemical Society provides “Just Accepted” as a free service to the research community to expedite the dissemination of scientific material as soon as possible after acceptance. “Just Accepted” manuscripts appear in full in PDF format accompanied by an HTML abstract. “Just Accepted” manuscripts have been fully peer reviewed, but should not be considered the official version of record. They are accessible to all readers and citable by the Digital Object Identifier (DOI®). “Just Accepted” is an optional service offered to authors. Therefore, the “Just Accepted” Web site may not include all articles that will be published in the journal. After a manuscript is technically edited and formatted, it will be removed from the “Just Accepted” Web site and published as an ASAP article. Note that technical editing may introduce minor changes to the manuscript text and/or graphics which could affect content, and all legal disclaimers and ethical guidelines that apply to the journal pertain. ACS cannot be held responsible for errors or consequences arising from the use of information contained in these “Just Accepted” manuscripts.
    [Show full text]
  • Heat Capacity of Liquids: Critical Review and Recommended Values
    Heat Capacity of Liquids: Critical Review and Recommended Values. Supplement I Cite as: Journal of Physical and Chemical Reference Data 30, 1199 (2001); https:// doi.org/10.1063/1.1407866 Submitted: 20 February 2001 . Published Online: 10 January 2002 Milan Zábranský, Vlastimil Růžička, and Eugene S. Domalski ARTICLES YOU MAY BE INTERESTED IN Heat Capacity of Liquids: Critical Review and Recommended Values. Supplement II Journal of Physical and Chemical Reference Data 39, 013103 (2010); https:// doi.org/10.1063/1.3182831 Estimation of the Heat Capacities of Organic Liquids as a Function of Temperature using Group Additivity. II. Compounds of Carbon, Hydrogen, Halogens, Nitrogen, Oxygen, and Sulfur Journal of Physical and Chemical Reference Data 22, 619 (1993); https:// doi.org/10.1063/1.555924 Heat Capacities and Entropies of Organic Compounds in the Condensed Phase. Volume III Journal of Physical and Chemical Reference Data 25, 1 (1996); https://doi.org/10.1063/1.555985 Journal of Physical and Chemical Reference Data 30, 1199 (2001); https://doi.org/10.1063/1.1407866 30, 1199 © 2002 by the U.S. Secretary of Commerce on behalf of the United States. All rights reserved. Heat Capacity of Liquids: Critical Review and Recommended Values. Supplement I Milan Za´bransky´, Vlastimil Ru˚ zˇicˇka, Jr.,a… and Eugene S. Domalskib… Department of Physical Chemistry, Institute of Chemical Technology, 166 28 Prague 6, Czech Republic ͑Received 20 February 2001; revised manuscript received 30 July 2001͒ A study was carried out in which new experimental data on heat capacities of pure liquid organic and some inorganic compounds were compiled, critically evaluated, and recommended values provided.
    [Show full text]
  • Abstract Reversed Phase Liquid Chromatography Using the Ionic Liquid Isopropylammonium Formate and Comparison of Indirect Spectr
    ABSTRACT REVERSED PHASE LIQUID CHROMATOGRAPHY USING THE IONIC LIQUID ISOPROPYLAMMONIUM FORMATE AND COMPARISON OF INDIRECT SPECTROPHOTOMETRIC METHODS FOR PHOSPHATE by Matthew P. Collins A new room temperature ionic liquid, isopropylammonium formate, IPAF, has been synthesized. Its application as a mobile phase replacement for traditional organic reversed phase-high performance liquid chromatography solvents is demonstrated. Solvent characteristics of IPAF, such as, polarity index, viscosity, and solvent strength are measured. Various van Deemter plots using different mixing approaches of the mobile phase and different columns are compared. The utility of IPAF has been further shown to be a suitable modifier solvent for the separation of cytochrome c from tryptophan. At 50°C, IPAF was able to maintain cytochrome c in its native form during the course of a chromatography separation, while a similar methanol modifier causes denaturation. Our long term goal is to develop a semi-preparative method to separate proteins in their native conformation. A comparison of atomic absorption and molecular spectrophotometry for the use in determining phosphate in an undergraduate teaching environment is also presented. REVERSED PHASE LIQUID CHROMATOGRAPHY USING THE IONIC LIQUID ISOPROPYLAMMONIUM FORMATE AND COMPARISON OF INDIRECT SPECTROPHOTOMETRIC METHODS FOR PHOSPHATE A Thesis Submitted to the Faculty of Miami University in partial fulfillment of the requirements for the degree of Master of Science Department of Chemistry and Biochemistry by Matthew
    [Show full text]
  • Aggregation Behavior of Long-Chain Piperidinium Ionic Liquids in Ethylammonium Nitrate
    Molecules 2014, 19, 20157-20169; doi:10.3390/molecules191220157 OPEN ACCESS molecules ISSN 1420-3049 www.mdpi.com/journal/molecules Article Aggregation Behavior of Long-Chain Piperidinium Ionic Liquids in Ethylammonium Nitrate Caili Dai, Mingyong Du, Yifei Liu, Shilu Wang, Jianhui Zhao, Ang Chen, Dongxu Peng and Mingwei Zhao * State Key Laboratory of Heavy Oil Processing, School of Petroleum Engineering, China University of Petroleum (Huadong), Qingdao 266580, Shandong, China; E-Mails: [email protected] (C.D.); [email protected] (M.D.); [email protected] (Y.L.); [email protected] (S.W.); [email protected] (J.Z.); [email protected] (A.C.); [email protected] (D.P.) * Author to whom correspondence should be addressed; E-Mail: [email protected]; Tel.: +86-532-8698-1183; Fax: +86-532-8698-1161. External Editor: Derek J. McPhee Received: 13 October 2014; in revised form: 7 November 2014 / Accepted: 21 November 2014 / Published: 2 December 2014 Abstract: Micelles formed by the long-chain piperidinium ionic liquids (ILs) N-alkyl-N-methylpiperidinium bromide of general formula CnPDB (n = 12, 14, 16) in ethylammonium nitrate (EAN) were investigated through surface tension and dissipative particle dynamics (DPD) simulations. Through surface tension measurements, the critical micelle concentration (cmc), the effectiveness of surface tension reduction (Πcmc), the maximum excess surface concentration (Гmax) and the minimum area occupied per 0 surfactant molecule (Amin) can be obtained. A series of thermodynamic parameters (ΔGm, 0 0 ΔH m and ΔS m ) of micellization can be calculated and the results showed that the micellization was entropy-driven. In addition, the DPD simulation was performed to simulate the whole aggregation process behavior to better reveal the micelle formation process.
    [Show full text]
  • Secondary Aerosol from Atmospheric Aliphatic Amines
    Atmos. Chem. Phys. Discuss., 7, 289–349, 2007 Atmospheric www.atmos-chem-phys-discuss.net/7/289/2007/ Chemistry ACPD © Author(s) 2007. This work is licensed and Physics 7, 289–349, 2007 under a Creative Commons License. Discussions Secondary aerosol from atmospheric aliphatic amines S. M. Murphy et al. Secondary aerosol formation from atmospheric reactions of aliphatic amines Title Page Abstract Introduction 1 1 2 1 1 1 S. M. Murphy , A. Sorooshian , J. H. Kroll , N. L. Ng , P. Chhabra , C. Tong , Conclusions References J. D. Surratt1, E. Knipping3, R. C. Flagan1, and J. H. Seinfeld1 Tables Figures 1Division of Chemistry and Chemical Engineering, California Institute of Technology, Pasadena, CA 91125, USA 2Current Address: Aerodyne Research Inc., Billerica, MA, USA J I 3Electric Power Research Institute, Palo Alto, CA, USA J I Received: 17 December 2006 – Accepted: 17 December 2006 – Published: 10 January 2007 Back Close Correspondence to: J. H. Seinfeld ([email protected]) Full Screen / Esc Printer-friendly Version Interactive Discussion EGU 289 Abstract ACPD Although aliphatic amines have been detected in both urban and rural atmospheric aerosols, little is known about the chemistry leading to particle formation or the poten- 7, 289–349, 2007 tial aerosol yields from reactions of gas-phase amines. We present here the first sys- 5 tematic study of aerosol formation from the atmospheric reactions of amines. Based Secondary aerosol on laboratory chamber experiments and theoretical calculations, we evaluate aerosol from atmospheric formation from reaction of OH, ozone, and nitric acid with trimethylamine, methylamine, aliphatic amines triethylamine, diethylamine, ethylamine, and ethanolamine. Entropies of formation for alkylammonium nitrate salts are estimated by molecular dynamics calculations en- S.
    [Show full text]