DOCSLIB.ORG

Polyelectrolyte Assisted Charge Titration Spectrometry: Applications to Latex and Oxide Nanoparticles

Total Page：16

File Type：pdf, Size：1020Kb

Download full-text PDF Read full-text
Polyelectrolyte Assisted Charge Titration Spectrometry: Applications to Latex and Oxide Nanoparticles Polyelectrolyte assisted charge titration spectrometry: applications to latex and oxide nanoparticles F. Mousseau1*, L. Vitorazi1, L. Herrmann1, S. Mornet2 and J.-F. Berret1* 1Matière et Systèmes Complexes, UMR 7057 CNRS Université Denis Diderot Paris-VII, Bâtiment Condorcet, 10 rue Alice Domon et Léonie Duquet, 75205 Paris, France. 2Institut de Chimie de la Matière Condensée de Bordeaux, UPR CNRS 9048, Université Bordeaux 1, 87 Avenue du Docteur A. Schweitzer, Pessac cedex F-33608, France. Abstract: The electrostatic charge density of particles is of paramount importance for the control of the dispersion stability. Conventional methods use potentiometric, conductometric or turbidity titration but require large amount of samples. Here we report a simple and cost-effective method called polyelectrolyte assisted charge titration spectrometry or PACTS. The technique takes advantage of the propensity of oppositely charged polymers and particles to assemble upon mixing, leading to aggregation or phase separation. The mixed dispersions exhibit a maximum in light scattering as a function of the volumetric ratio �, and the peak position �!"# is linked to the particle charge density according to � ~ �!�!"# where �! is the particle diameter. The PACTS is successfully applied to organic latex, aluminum and silicon oxide particles of positive or negative charge using poly(diallyldimethylammonium chloride) and poly(sodium 4-styrenesulfonate). The protocol is also optimized with respect to important parameters such as pH and concentration, and to the polyelectrolyte molecular weight. The advantages of the PACTS technique are that it requires minute amounts of sample and that it is suitable to a broad variety of charged nano-objects. Keywords: charge density – nanoparticles - light scattering – polyelectrolyte complex Corresponding authors: [email protected] [email protected] To appear in Journal of Colloid and Interface Science leading to their condensation and to the formation of the electrical double layer [1]. The I – Introduction counterion condensation occurs for charge Electrostatic Coulomb forces are ubiquitous in density � above a certain threshold [4]: soft condensed matter [1, 2]. Interaction pair potentials created by elementary charges of the 2 same sign at interfaces or along macromolecules � > (1) ��ℓ! are long-range and repulsive. These interactions depend on physico-chemical parameters, such as where � is the diameter of the colloid and ℓ! is the dielectric constant of the continuous phase, the Bjerrum length (0.7 nm in water). As a result, the solute concentration, the pH, the ionic particles in solution satisfying Eq. 1 behave as if strength and the temperature. Electrostatic they would have an effective charge �!"" forces between like-charged systems are different from its structural charge � [4, 5]. especially relevant to insure repulsion between !"# The counterion condensation for colloids bears colloidal objects. At low ionic strength, strong similarities with that derived for polymers electrostatic repulsions are for instance sufficient and known as the Oosawa-Manning to induce long-range ordering and colloidal condensation [6]. Following Belloni [4] the crystal phases [3]. In aqueous dispersions, the effective charge can be approximated by the ionizable groups at the colloid surface exert expression: Coulombic forces towards the counterions, 2� �!"" = (2) ℓ! 1 techniques were proposed to measure the For a particle of charge density � = +1� nm-2 and surface charge of particles in the nanometer a diameter of 10 nm, the effective charge �!"" = range [41, 42]. +28� represents around 10% of the total The technique examined here borrows its ionizable groups (�!"# = +314�). As the principle from methods developed for enzymatic condensed counterions are firmly attached to the activity measurements [43] and from turbidity surface and move with the colloid during titration [44, 45]. Earlier reports suggest that the diffusion, experiments such as electrophoretic maximum of absorbance or turbidity associated mobility measurements [7-12] or small-angle with the precipitation is related to the end-point scattering experiments in the concentrated reaction, and allows an estimation of the charge regime [13-15] enable access to the effective density of the titrated colloids. The method charge only. applied here differs from turbidity titration in two aspects: i) light scattering is preferred to UV- Potentiometric, turbidity or colloid titration spectrometry and ii) the mixed polymer and techniques, as well as conductometry are particle dispersions are prepared by direct mixing commonly used to determine the structural instead of step-wise addition. With newly charges of colloids. Potentiometric or acid-base developed photon counters, light scattering is a titration coupled with conductometry was highly sensitive technique, which can detect successfully applied to microgels [16], polymer colloidal diffusion down to extremely low micelles [17] and metal oxide nanoparticles [18- concentration. During the last decade, light 21]. However the technique requires large scattering has been applied to investigate the sample quantity, which depending on the particle complexation of oppositely charged species, synthesis is not always possible. To determine including surfactant, polymers, phospholipids the charge density of iron oxide particles for and proteins [12, 46-53]. In most studies instance, Lucas et al. used potentio- however, emphasis was put on the structures conductometric titration with dispersions that formed and not on the reaction containing 5-10 g of iron oxide dry matter [18]. stoichiometry [54]. Here we develop a simple Colloid titration is another method that was protocol based on the use of light scattering and introduced by Terayama some 50 years ago [22]. on the complexation property of particles with This technique was applied to titrate ion- oppositely charged polymers. The technique is containing polymers in aqueous solutions. Colloid assessed on different types of organic and titration is based on the reaction between inorganic nanoparticles in the 50 nm range, oppositely charged polyelectrolytes in presence either positive or negative and it is shown that of a small amount of dye molecules that serves the structural charge and charge density can be as an indicator of the endpoint reaction between determined with minute amount of sample. The the two polymers [23, 24]. technique was dubbed Polyelectrolyte Assisted Initially developed to study protein complexes, Charge Titration Spectrometry subsequently isothermal titration calorimetry (ITC) has gained abbreviated as PACTS. interest in the field of physical chemistry. ITC was also used to survey the condensation of DNA with multivalent counterions [25] and with oligo- II – Materials and Methods and polycations [26-28] and more recently the II.1 - Nanoparticles complexation between polymers, proteins or Latex particles functionalized with carboxylate or surfactants. Despite a large number of studies amidine surface groups were acquired from [29-39] the interpretation of the thermograms Molecular Probes (concentration 40 g L-1). The remains a challenge, as the heat exchanges dispersion pH was adjusted at pH9.7 and pH6 by during titration exhibit rich and numerous addition of sodium hydroxide and hydrochloric features not always accounted for by existing acid, respectively. The particles were models [33, 40]. More recently, ultrafast laser characterized by light scattering and transmission spectroscopy coupled to the generation of the electron microscopy, yielding � = 39 nm and 56 second harmonics or resistive pulse sensing ! nm and �! = 30 and 34 nm. Negative silica 2 particles (CLX®, Sigma Aldrich) were diluted from hydrochloric acid. Aluminum oxide nanoparticle 450 to 50 g L-1 by DI-water. Particles were powder (Disperal®, SASOL) was dissolved in a dialyzed for two days against DI-water at pH 9. nitric acid solution (0.4 wt. % in deionized water) -1 Positive silica particles (�! = 60 nm) were at the concentration of 10 g L and sonicated for synthetized using the Stöber synthesis route [55- one hour. For the PACTS experiments, the 57]. Silica seeds were first prepared and grown to dispersions were further diluted to 0.1 g L-1 and increase the particle size. Functionalization by the dispersion pH was adjusted to pH 4 with amine groups was then performed, resulting in a sodium hydroxide. In this pH condition, the positively charged coating [56]. Aminated silica nanoalumina are positively charged (�! = 64 nm) synthesized at 40 g L-1 were diluted with DI-water [58]. and the pH was adjusted to pH 5 with Figure 1: Transmission electronic microscopy images of latex (a,c), silica (b,d) and alumina (e) particles used in this study. Table I: Nanoparticles studied in the present work. Particle characteristics are the mass density (�), the pH at which the experiments are done, the hydrodynamic diameter (�!), the geometric diameter (�!) and the dispersity � obtained from transmission electron microscopy. Fig. 1 displays images of the particles obtained by found slightly higher than the geometric transmission electron microscopy (TEM). Except diameters �! found by TEM. With light for Al2O3 which have the form of irregular scattering, the largest particles contribute platelets of average dimensions 40 nm long and predominantly to the scattering intensity and 10 nm thick, all other particles are spherical. In determine the value for the
Load more

Recommended publications
  • Influence of Polyelectrolyte Multilayer Properties on Bacterial Adhesion
    polymers Article Influence of Polyelectrolyte Multilayer Properties on Bacterial Adhesion Capacity Davor Kovaˇcevi´c 1, Rok Pratnekar 2, Karmen GodiˇcTorkar 2, Jasmina Salopek 1, Goran Draži´c 3,4,5, Anže Abram 3,4,5 and Klemen Bohinc 2,* 1 Department of Chemistry, Faculty of Science, University of Zagreb, Zagreb 10000, Croatia; [email protected] (D.K.); [email protected] (J.S.) 2 Faculty of Health Sciences, Ljubljana 1000, Slovenia; [email protected] (R.P.); [email protected] (K.G.T.) 3 Jožef Stefan Institute, Ljubljana 1000, Slovenia; [email protected] (G.D.); [email protected] (A.A.) 4 National Institute of Chemistry, Ljubljana 1000, Slovenia 5 Jožef Stefan International Postgraduate School, Ljubljana 1000, Slovenia * Correspondence: [email protected]; Tel.: +386-1300-1170 Academic Editor: Christine Wandrey Received: 16 August 2016; Accepted: 14 September 2016; Published: 26 September 2016 Abstract: Bacterial adhesion can be controlled by different material surface properties, such as surface charge, on which we concentrate in our study. We use a silica surface on which poly(allylamine hydrochloride)/sodium poly(4-styrenesulfonate) (PAH/PSS) polyelectrolyte multilayers were formed. The corresponding surface roughness and hydrophobicity were determined by atomic force microscopy and tensiometry. The surface charge was examined by the zeta potential measurements of silica particles covered with polyelectrolyte multilayers, whereby ionic strength and polyelectrolyte concentrations significantly influenced the build-up process. For adhesion experiments, we used the bacterium Pseudomonas aeruginosa. The extent of adhered bacteria on the surface was determined by scanning electron microscopy. The results showed that the extent of adhered bacteria mostly depends on the type of terminating polyelectrolyte layer, since relatively low differences in surface roughness and hydrophobicity were obtained.
    [Show full text]
  • Surface Polarization Effects in Confined Polyelectrolyte Solutions
    Surface polarization effects in confined polyelectrolyte solutions Debarshee Bagchia , Trung Dac Nguyenb , and Monica Olvera de la Cruza,b,c,1 aDepartment of Materials Science and Engineering, Northwestern University, Evanston, IL 60208; bDepartment of Chemical and Biological Engineering, Northwestern University, Evanston, IL 60208; and cDepartment of Physics and Astronomy, Northwestern University, Evanston, IL 60208 Contributed by Monica Olvera de la Cruz, June 24, 2020 (sent for review April 21, 2020; reviewed by Rene Messina and Jian Qin) Understanding nanoscale interactions at the interface between ary conditions (18, 19). However, for many biological settings two media with different dielectric constants is crucial for con- as well as in supercapacitor applications, molecular electrolytes trolling many environmental and biological processes, and for confined by dielectric materials, such as graphene, are of interest. improving the efficiency of energy storage devices. In this Recent studies on dielectric confinement of polyelectrolyte by a contributed paper, we show that polarization effects due to spherical cavity showed that dielectric mismatch leads to unex- such dielectric mismatch remarkably influence the double-layer pected symmetry-breaking conformations, as the surface charge structure of a polyelectrolyte solution confined between two density increases (20). The focus of the present study is the col- charged surfaces. Surprisingly, the electrostatic potential across lective effects of spatial confinement by two parallel surfaces
    [Show full text]
  • Semester II, 2015-16 Department of Physics, IIT Kanpur PHY103A: Lecture # 5 Anand Kumar
    Semester II, 2017-18 Department of Physics, IIT Kanpur PHY103A: Lecture # 8 (Text Book: Intro to Electrodynamics by Griffiths, 3rd Ed.) Anand Kumar Jha 19-Jan-2018 Summary of Lecture # 7: • Electrostatic Boundary Conditions E E = Electric Field: = above below E − E = 00 above− below � 0 above − below Electric Potential: V V = 0 above − below • Basic Properties of Conductors (1) The electric field = 0 inside a conductor, always. = 0 = = 0 (2) The charge density inside a conductor. This is because . (3) Any net charge resides on the surface. Why? To minimize the energy. 0 ⋅ (4) A conductor is an equipotential. (5) is perpendicular to the surface, just outside the conductor. 2 Summary of Lecture # 7: Prob. 2.36 (Griffiths, 3rd Ed. ): - Surface charge ? = = − 2 - Surface charge ? 4 + - Surface charge ? = − 2 4 1 2 - ( ) ? = 4 out 2 1 0 � - ( ) ? = 4 out 2 10 �+ - ( ) ? =4 out out 2 � - Force on ? 0 40 - Force on ? 0 3 Summary of Lecture # 7: Prob. 2.36 (Griffiths, 3rd Ed. ): - Surface charge ? = Same ª = − 2 Same - Surface charge ? 4 ª + - Surface charge ? = − 2 Changes � 4 1 2 = - ( ) ? 4 Same ª out 2 1 0 � = 4 - ( ) ? Same ª out 2 � 10 + Changes � - ( ) ? =4 out out 2 - Force on ? 0 0 � 4 Same ª Bring in a third - Force on ? 0 Same ª charge 4 Surface Charge and the Force on a Conductor: What is the electrostatic force on the patch? Force per unit area on the patch is: = (? ) = other = + , above other patch above = + 2 other 0 � = + , below other patch below 1 = = + 2 2 other − � other above below 0 But, inside a metal, = , so = 0 below = = + = 2 2 other � above other � � 5 0 0 0 Surface Charge and the Force on a Conductor: What is the electrostatic force on the patch? Force per unit area on the patch is: = (? ) = other = = 2 other � above � Force per unit0 area on the patch is: 0 = = 2 2 other � Force per unit area is pressure.0 So, the electrostatic pressure is: = = 2 2 20 2 6 0 Capacitor: Two conductors with charge and .
    [Show full text]
  • Ion Current Rectification in Extra-Long Nanofunnels
    applied sciences Article Ion Current Rectification in Extra-Long Nanofunnels Diego Repetto, Elena Angeli * , Denise Pezzuoli, Patrizia Guida, Giuseppe Firpo and Luca Repetto Department of Physics, University of Genoa, via Dodecaneso 33, 16146 Genoa, Italy; [email protected] (D.R.); [email protected] (D.P.); [email protected] (P.G.); giuseppe.fi[email protected] (G.F.); [email protected] (L.R.) * Correspondence: [email protected] Received: 29 April 2020; Accepted: 25 May 2020; Published: 28 May 2020 Abstract: Nanofluidic systems offer new functionalities for the development of high sensitivity biosensors, but many of the interesting electrokinetic phenomena taking place inside or in the proximity of nanostructures are still not fully characterized. Here, to better understand the accumulation phenomena observed in fluidic systems with asymmetric nanostructures, we study the distribution of the ion concentration inside a long (more than 90 µm) micrometric funnel terminating with a nanochannel. We show numerical simulations, based on the finite element method, and analyze how the ion distribution changes depending on the average concentration of the working solutions. We also report on the effect of surface charge on the ion distribution inside a long funnel and analyze how the phenomena of ion current rectification depend on the applied voltage and on the working solution concentration. Our results can be used in the design and implementation of high-performance concentrators, which, if combined with high sensitivity detectors, could drive the development of a new class of miniaturized biosensors characterized by an improved sensitivity. Keywords: nanofunnel; FEM simulation; ionic current rectification; micro-nano structure interface 1.
    [Show full text]
  • Beryllium Desorption from Minerals and Organic Ligands Over Time
    Chemical Geology 439 (2016) 52–58 Contents lists available at ScienceDirect Chemical Geology journal homepage: www.elsevier.com/locate/chemgeo Beryllium desorption from minerals and organic ligands over time Vanessa Boschi ⁎,JaneK.Willenbring Department of Earth and Environmental Science, University of Pennsylvania, 251 Hayden Hall, 240 South 33rd Street, Philadelphia, PA 19104, USA article info abstract Article history: Beryllium isotopes sorbed to sediments have provided useful tools in the field of geochronology and geomor- Received 13 April 2016 phology over the last few decades. The use of beryllium isotopes relies on the premise that beryllium sorbed to Received in revised form 3 June 2016 sediments is unaltered over large timescales. Changes in the environmental chemistry, either in-situ or en Accepted 10 June 2016 route from soil to fluvial system, to the ocean, can cause beryllium desorption and may preclude some beryllium Available online 11 June 2016 isotopic applications. Keywords: Four mechanisms were tested to determine the relative desorption potential of beryllium including a reduction Beryllium in pH, an increase in ionic strength (NaCl) and complexation by soluble organic (malonic acid) and inorganic spe- Desorption cies (NaF). To assess the relative effect of each mechanism on beryllium desorption from both organic and min- Minerals eral fractions, we prepared separate solutions of beryllium bound to minerals and organic compounds and Organic ligands measured beryllium concentrations in solution before and after each chemical perturbation. We conclude a re- Inner and outer sphere complexation duction in pH resulted in the greatest amount of desorption among the four treatments, removing 97% and 75% of sorbed beryllium from illite and montmorillonite, respectively, and none from the organic ligands tested.
    [Show full text]
  • 6.007 Lecture 5: Electrostatics (Gauss's Law and Boundary
    Electrostatics (Free Space With Charges & Conductors) Reading - Shen and Kong – Ch. 9 Outline Maxwell’s Equations (In Free Space) Gauss’ Law & Faraday’s Law Applications of Gauss’ Law Electrostatic Boundary Conditions Electrostatic Energy Storage 1 Maxwell’s Equations (in Free Space with Electric Charges present) DIFFERENTIAL FORM INTEGRAL FORM E-Gauss: Faraday: H-Gauss: Ampere: Static arise when , and Maxwell’s Equations split into decoupled electrostatic and magnetostatic eqns. Electro-quasistatic and magneto-quasitatic systems arise when one (but not both) time derivative becomes important. Note that the Differential and Integral forms of Maxwell’s Equations are related through ’ ’ Stoke s Theorem and2 Gauss Theorem Charges and Currents Charge conservation and KCL for ideal nodes There can be a nonzero charge density in the absence of a current density . There can be a nonzero current density in the absence of a charge density . 3 Gauss’ Law Flux of through closed surface S = net charge inside V 4 Point Charge Example Apply Gauss’ Law in integral form making use of symmetry to find • Assume that the image charge is uniformly distributed at . Why is this important ? • Symmetry 5 Gauss’ Law Tells Us … … the electric charge can reside only on the surface of the conductor. [If charge was present inside a conductor, we can draw a Gaussian surface around that charge and the electric field in vicinity of that charge would be non-zero ! A non-zero field implies current flow through the conductor, which will transport the charge to the surface.] … there is no charge at all on the inner surface of a hollow conductor.
    [Show full text]
  • Chapter 5 Capacitance and Dielectrics
    Chapter 5 Capacitance and Dielectrics 5.1 Introduction...........................................................................................................5-3 5.2 Calculation of Capacitance ...................................................................................5-4 Example 5.1: Parallel-Plate Capacitor ....................................................................5-4 Interactive Simulation 5.1: Parallel-Plate Capacitor ...........................................5-6 Example 5.2: Cylindrical Capacitor........................................................................5-6 Example 5.3: Spherical Capacitor...........................................................................5-8 5.3 Capacitors in Electric Circuits ..............................................................................5-9 5.3.1 Parallel Connection......................................................................................5-10 5.3.2 Series Connection ........................................................................................5-11 Example 5.4: Equivalent Capacitance ..................................................................5-12 5.4 Storing Energy in a Capacitor.............................................................................5-13 5.4.1 Energy Density of the Electric Field............................................................5-14 Interactive Simulation 5.2: Charge Placed between Capacitor Plates..............5-14 Example 5.5: Electric Energy Density of Dry Air................................................5-15
    [Show full text]
  • Electrical Double Layer Interactions with Surface Charge Heterogeneities
    Electrical double layer interactions with surface charge heterogeneities by Christian Pick A dissertation submitted to Johns Hopkins University in conformity with the requirements for the degree of Doctor of Philosophy Baltimore, Maryland October 2015 © 2015 Christian Pick All rights reserved Abstract Particle deposition at solid-liquid interfaces is a critical process in a diverse number of technological systems. The surface forces governing particle deposition are typically treated within the framework of the well-known DLVO (Derjaguin-Landau- Verwey-Overbeek) theory. DLVO theory assumes of a uniform surface charge density but real surfaces often contain chemical heterogeneities that can introduce variations in surface charge density. While numerous studies have revealed a great deal on the role of charge heterogeneities in particle deposition, direct force measurement of heterogeneously charged surfaces has remained a largely unexplored area of research. Force measurements would allow for systematic investigation into the effects of charge heterogeneities on surface forces. A significant challenge with employing force measurements of heterogeneously charged surfaces is the size of the interaction area, referred to in literature as the electrostatic zone of influence. For microparticles, the size of the zone of influence is, at most, a few hundred nanometers across. Creating a surface with well-defined patterned heterogeneities within this area is out of reach of most conventional photolithographic techniques. Here, we present a means of simultaneously scaling up the electrostatic zone of influence and performing direct force measurements with micropatterned heterogeneously charged surfaces by employing the surface forces apparatus (SFA). A technique is developed here based on the vapor deposition of an aminosilane (3- aminopropyltriethoxysilane, APTES) through elastomeric membranes to create surfaces for force measurement experiments.
    [Show full text]
  • Surface Charge
    Surface Charge Gerald Ehrenstein Outline I Introduction II Gouy-Chapman Theory III Experimental Evidence Supporting Gouy-Chapman Theory IV Experimental Evidence Disagreeing with Gouy-Chapman Theory V Possible Resolution of Experimental Differences VI Significance of Surface Charge Copyright by author, 2001 I Introduction The overall magnitude of the electric charge on a cell can be determined by measurement of the cell’s electrophoretic mobility. Such a measurement provides an estimate of the average charge density over the entire cell membrane. This chapter will be concerned not with this average surface charge density, but rather with the local surface charge density in and near voltage-dependent ionic channels. The primary method of measuring local charge density is to examine the electrical properties of the voltage-dependent channels under normal conditions and under conditions where the surface charge near the channel is neutralized, thus changing the local electric field. Since voltage-dependent channels are sensitive to this local electric field, neutralization of surface charge is expected to cause changes in voltage-dependent properties, such as conductance and time constants. If surface charge were static, it would be expected that a particular neutralization of surface charge would cause a corresponding change in electric field, leading to a translation of all voltage-dependent properties along the voltage axis. The magnitude of the charge neutralization can be determined by measurement of the magnitude of the translation. II Gouy-Chapman Theory Gouy-Chapman theory describes the effect of a static surface charge on the membrane potential. A negative surface charge leads to formation of a double layer, since positive ions in solution tend to balance the negative surface charge.
    [Show full text]
  • The Relationship Between Polymer/Substrate Charge Density and Charge Overcompensation by Adsorbed Polyelectrolyte Layers ∗ ∗ Yongwoo Shin, James E
    Journal of Colloid and Interface Science 247, 220–230 (2002) doi:10.1006/jcis.2001.8100, available online at http://www.idealibrary.com on The Relationship between Polymer/Substrate Charge Density and Charge Overcompensation by Adsorbed Polyelectrolyte Layers ∗ ∗ Yongwoo Shin, James E. Roberts,† and Maria M. Santore ,1 ∗ Department of Chemical Engineering and †Department of Chemistry, Lehigh University, Bethlehem, Pennsylvania 18015 Received July 31, 2001; accepted November 8, 2001 electrostatic aspects of charge-driven adsorption as a function of This work examines polyelectrolyte adsorption (exclusively backbone charge density for a weak cationic polyelectrolyte driven by electrostatic attractions) for a model system (DMAEMA, adsorbing onto a weakly acidic surface, when the interfacial polydimethylaminoethyl methacrylate, adsorbing onto silica) conformation is well-defined by the choice of a low-molecular- where the adsorbing polycation is more densely charged than the weight oligomer. substrate. Variations in the relative charge densities of the poly- mer and substrate are accomplished by pH, and the polycation is of The most extensive studies of cationic polyelecrolyte adsorp- sufficiently low molecular weight that the adsorbed conformation tion have focused on quarternized systems, where permanently is generally flat under all conditions examined. We demonstrate, charged cationic units are not sensitive to pH (1–12). When quantitatively, that the charge overcompensation observed on the adsorption is driven exclusively by electrostatic attractions, a isotherm plateau can be attributed to the denser positive charge on threshold backbone charge density must be reached before the the adsorbing polycation and that the ultimate coverage obtained entropic loss of adsorption is overcome and significant mass corresponds to the adsorption of one oligomer onto each original accumulates at the interface (13–15).
    [Show full text]
  • Influence of Surface Conductivity on the Apparent Zeta Potential of Calcite
    Influence of surface conductivity on the apparent zeta potential of calcite Shuai Li1, Philippe Leroy1*, Frank Heberling2, Nicolas Devau1, Damien Jougnot3, Christophe Chiaberge1 1 BRGM, French geological survey, Orléans, France. 2 Institute for Nuclear Waste Disposal, Karlsruhe Institute of Technology, Karlsruhe, Germany. 3 Sorbonne Universités, UPMC Univ Paris 06, CNRS, EPHE, UMR 7619 METIS, Paris, France. *Corresponding author and mailing address: Philippe Leroy BRGM 3 Avenue Claude Guillemin 45060 Orléans Cedex 2, France E-mail: [email protected] Tel: +33 (0)2 38 64 39 73 Fax: +33 (0)2 38 64 37 19 This paper has been accepted for publication in Journal of Colloid and Interface Science: S. Li, P. Leroy, F. Heberling, N. Devau, D. Jougnot, C. Chiaberge (2015) Influence of surface conductivity on the apparent zeta potential of calcite, Journal of Colloid and Interface Science, 468, 262-275, doi:10.1016/j.jcis.2016.01.075. 1 Abstract Zeta potential is a physicochemical parameter of particular importance in describing the surface electrical properties of charged porous media. However, the zeta potential of calcite is still poorly known because of the difficulty to interpret streaming potential experiments. The Helmholtz- Smoluchowski (HS) equation is widely used to estimate the apparent zeta potential from these experiments. However, this equation neglects the influence of surface conductivity on streaming potential. We present streaming potential and electrical conductivity measurements on a calcite powder in contact with an aqueous NaCl electrolyte. Our streaming potential model corrects the apparent zeta potential of calcite by accounting for the influence of surface conductivity and flow regime.
    [Show full text]
  • Potentiometric Titrations As a Tool for Surface Charge Determination†,‡
    CROATICA CHEMICA ACTA CCACAA, ISSN 0011-1643, e-ISSN 1334-417X Croat. Chem. Acta 85 (4) (2012) 391–417. http://dx.doi.org/10.5562/cca2062 Original Scientific Article Potentiometric Titrations as a Tool for Surface Charge Determination†,‡ Johannes Lützenkirchen,a,* Tajana Preočanin,b Davor Kovačević,b Vladislav Tomišić,b Lars Lövgren,c and Nikola Kallayb aInstitute for Nuclear Waste Disposal (INE), Karlsruhe Institute of Technology (KIT), P.O. Box 3640, DE-76021 Karlsruhe, Germany bDivision of Physical Chemistry, Department of Chemistry, Faculty of Science, University of Zagreb, Horvatovac 102a, HR-10000 Zagreb, Croatia cDepartment of Chemistry, University of Umeå, SE-901 87 Umeå, Sweden RECEIVED FEBRUARY 29, 2012; REVISED JUNE 18, 2012; ACCEPTED JUNE 29, 2012 Abstract. This article summarizes methods for determining proton surface charge at mineral/water inter- faces. It covers conventional experimental procedures and discusses problems with the techniques. Also it involves recommendations for obtaining reasonable and comparable results. The term "comparable re- sults" refers to comparison between results for the same solid as obtained in different laboratories. The most important parameters for the surface titrations are discussed. We also propose a reference titration procedure that would allow direct, unbiased comparisons of experimental data. The article finally includes a check-list for researchers and reviewers which should allow limiting the amount of titration data that are not useful for future uses. (doi: 10.5562/cca2062) Keywords:
    [Show full text]