all ions are the same size in ionic solids

The definitions of the other symbols is as follows: where "ads" stands for "adsorbed", "m" stands for "monolayer equivalence" and "vap" is reference to the vapor pressure of the liquid adsorptive at the same temperature as the solid sample. pore size distribution and surface area) can be tuned according to what is needed. [34], Protein adsorption is a process that has a fundamental role in the field of biomaterials. 5-membered and 6-membered chelate rings give the most stable complexes. Other factors include solvation changes and ring formation. However, the rate constant for the Kisliuk model (R) is different from that of the Langmuir model, as R is used to represent the impact of diffusion on monolayer formation and is proportional to the square root of the system's diffusion coefficient. For example, potassium selective electrodes are available that make use of the naturally occurring macrocyclic antibiotic valinomycin. The mathematics underlying the methods used in this period are summarised by Rossotti and Rossotti. Jannik Bjerrum (son of Niels Bjerrum) developed the first general method for the determination of stability constants of metal-ammine complexes in 1941. {\displaystyle D} The dealumination process is done by treating the zeolite with steam at elevated temperatures, typically greater than 500C (930F). In hemoglobin an iron(II) ion is complexed by a macrocyclic porphyrin ring. Instability Constants of Complex Compounds. It is based on four assumptions: These four assumptions are seldom all true: there are always imperfections on the surface, adsorbed molecules are not necessarily inert, and the mechanism is clearly not the same for the very first molecules to adsorb to a surface as for the last. mon The same group applied the model to CO hydrogenation (FischerTropsch synthesis). Atoms are extremely small, typically around 100 picometers across. In general purpose computer programs it is customary to define all constants as association constants. The table below summarizes data on the radii of a series of isoelectronic ions and atoms of second- and [18] Both these theories yield the same equation for flat surfaces: where U is the unit step function. m Hydrogen spillover is the most common example of an adsorptive spillover. on an infinite area surface can be directly integrated from Fick's second law differential equation to be:[15], where Thus, the phenomenon of the chelate effect is a firmly established empirical fact: under comparable conditions, the concentration of a chelate complex will be higher than the concentration of an analogous complex with monodentate ligands. [37] [35] In fact, cell membrane receptors bind to protein layer bioactive sites and these receptor-protein binding events are transduced, through the cell membrane, in a manner that stimulates specific intracellular processes that then determine cell adhesion, shape, growth and differentiation. It is prepared by the reaction between sodium silicate and acetic acid, which is followed by a series of after-treatment processes such as aging, pickling, etc. Furthermore, stability constant values depend on the specific electrolyte used as the value of is different for different electrolytes, even at the same ionic strength. This permitted the examination of systems too complicated to be evaluated by means of hand-calculations. Drago and Wayland proposed a two-parameter equation which predicts the standard enthalpy of formation of a very large number of adducts quite accurately. [22], An important difference between macrocyclic ligands and open-chain (chelating) ligands is that they have selectivity for metal ions, based on the size of the cavity into which the metal ion is inserted when a complex is formed. The stronger the attractive forces between ions, the higher the melting point of ionic solids. Complex formation of cadmium with sugar residues, nucleobases, phosphates, nucleotides and nucleic acids". Lateral offsets between the layers may result in longer repeating periods. Another example of the effect of ionic radius the steady increase in stability of complexes with a given ligand along the series of trivalent lanthanide ions, an effect of the well-known lanthanide contraction. There does not need to be any chemical interaction between the species in equilibrium and the background electrolyte, but such interactions might occur in particular cases. Ionic solids can only conduct electricity as molten ionic compounds or in aqueous solutions. The low-spin Fe2+ ion fits snugly into the cavity of the porphyrin ring, but high-spin iron(II) is significantly larger and the iron atom is forced out of the plane of the macrocyclic ligand. The following references are for critical reviews of published stability constants for various classes of ligands. t The first mathematical fit to an isotherm was published by Freundlich and Kuster (1906) and is a purely empirical formula for gaseous adsorbates: where Increase in the concentration of a substance at the interface of a condensed and a liquid or gaseous layer owing to the operation of surface forces. The surface is energetically homogeneous, and adsorbed molecules do not interact. {\displaystyle \theta ={\frac {v}{v_{\text{mon}}}}} {\displaystyle P/P_{0}} in a particular measurement.[16]. Four widely used definitions of atomic radius are: Van der Waals radius, ionic {\displaystyle n} v The large stability constant of the octadentate ligand ensures that the concentration of free Gd3+ is almost negligible, certainly well below toxicity threshold. Ionic Solids. The difference between the two stability constants is mainly due to the difference in the standard entropy change, S. (eds.). Welding is a fabrication process that joins materials, usually metals or thermoplastics, by using high heat to melt the parts together and allowing them to cool, causing fusion.Welding is distinct from lower temperature techniques such as brazing and soldering, which do not melt the base metal (parent metal).. [45] Trens et al. The atomic radius of a chemical element is a measure of the size of its atom, usually the mean or typical distance from the center of the nucleus to the outermost isolated electron.Since the boundary is not a well-defined physical entity, there are various non-equivalent definitions of atomic radius. K Thus, the same string (for example, the empty string) may be stored in two or more places in memory. Ligands such as DTPA, which have eight donor atoms are used to form complexes with large metal ions such as lanthanide or actinide ions which usually form 8- or 9-coordinate complexes. One of its main drawbacks is that it reacts with oxygen at moderate temperatures (over 300C). The next steps are penetration, uncoating, synthesis (transcription if needed, and translation), and release. The stepwise constants, K1 and K2 refer to the formation of the complexes one step at a time. Non-polar (siliceous) zeolites are synthesized from aluminum-free silica sources or by dealumination of aluminum-containing zeolites. {\displaystyle x} [17] The structure of an ionic compound depends on the relative sizes of the cations and anions. In solvent extraction the formation of electrically-neutral complexes allows cations to be extracted into organic solvents. No. When the analytical concentration of methylamine is twice that of ethylenediamine and the concentration of copper is the same in both reactions, the concentration [Cu(en)]2+ is much higher than the concentration [Cu(MeNH2)2]2+ because 1112. Part II. P This is one of the factors contributing to the entropy difference. This form of TES, with specific use of zeolites, was first taught by John Guerra in 1978. All the alkali metal halides are soluble in water except for lithium fluoride (LiF), which is insoluble in water due to its very high lattice enthalpy. Another example involves iron(III) which forms weak complexes with halide and other anions, but not with perchlorate ions. A typical application in molecular recognition involved the determination of formation constants for complexes formed between a tripodal substituted urea molecule and various saccharides. The relationship between the two types of constant is given in association and dissociation constants. An ion (/ a. Free energy is made up of an enthalpy term and an entropy term. The thermodynamics of metal ion complex formation provides much significant information. Advances in computational power allowed for nonlinear regression to be performed quickly and with higher confidence since no data transformation is required. Storage can be diurnal, weekly, monthly, or even seasonal depending on the volume of the zeolite and the area of the solar thermal panels. The smaller ions are the Na + with has an atomic radius of 102 pm, and the larger ions are the Cl - with an atomic radium of 181 pm. Constants that describe stability of coordination complexes, Factors affecting the stability constants of complexes, Learn how and when to remove this template message, "Pit-mapping - A general approach to Computer refinement of stability constants", "Project: Ionic Strength Corrections for Stability Constants", "Formation of metal complexes with ethylenediamine: a critical survey of equilibrium constants, enthalpy and entropy values", "Critical survey of stability constants of NTA complexes", "Critical evaluation of stability constants of metal complexes of complexones for biomedical and environmental applications (IUPAC Technical Report)", "Critical evaluation of stability constants for alpha-hydroxycarboxylic acid complexes with protons and metal ions and the accompanying enthalpy changes. Polymers may also be adsorbed to surfaces through polyelectrolyte adsorption. "Chapter 8. Water dissolves many ionic salts thanks to its high dielectric constant and ability to solvate ions. Removal of a proton from an aliphatic OH group is difficult to achieve in aqueous solution because the energy required for this process is rather large. This molecule should be used with caution as a buffering agent as it will form chelate complexes with ions such as Fe3+ and Cu2+. For very low pressures The Langmuir isotherm is usually better for chemisorption, and the BET isotherm works better for physisorption for non-microporous surfaces. Bicarbonate (HCO 3) is a vital component of the pH buffering system of the human body (maintaining acidbase homeostasis). A Relationships, such as the Irving-Williams series were discovered. The following twenty years saw a veritable explosion in the number of stability constants that were determined. [1] The reasons why this occurred at such a late date, nearly 50 years after Alfred Werner had proposed the correct structures for coordination complexes, have been summarised by Beck and Nagypl. In the first reaction the bidentate ligand ethylene diamine forms a chelate complex with the copper ion. For example, phosphates form weak complexes with alkali metals, so, when determining stability constants involving phosphates, such as ATP, the background electrolyte used will be, for example, a tetralkylammonium salt. A hydrolysis reaction is one in which a substrate reacts with water, splitting a water molecule into hydroxide and hydrogen ions. Microsoft pleaded for its deal on the day of the Phase 2 decision last month, but now the gloves are well and truly off. In a bulk material, all the bonding requirements (be they ionic, covalent or metallic) of the constituent atoms of the material are fulfilled by other atoms in the material. The lattice energy of ionic solids depends on the charge of the ions and on the size of the ions. Protein adsorption is influenced by many surface properties such as surface wettability, surface chemical composition [36] and surface nanometre-scale morphology. Several pilot projects have been funded in the EU from 2000 to the present (2020). If the desorption rate is larger, the number of molecules on the surface will decrease over time. The number of chelate rings is one less than the number of donor atoms in the ligand. The adsorption rate is dependent on the temperature, the diffusion rate of the solute (related to mean free path for pure gas), and the energy barrier between the molecule and the surface. Most commonly, a solution containing the metal ion and the ligand in a medium of high ionic strength is first acidified to the point where the ligand is fully protonated. They have a high melting point. In the older literature the value of log K is usually cited for an hydrolysis constant. Ionic solids are held together by the electrostatic attraction between the The ninth site is occupied by a water molecule which exchanges rapidly with the fluid surrounding it and it is this mechanism that makes the paramagnetic complex into a contrast reagent. An ionic compound is a chemical compound composed of ions held together by electrostatic forces termed ionic bonding.The compound is neutral overall, but consists of positively charged ions called cations and negatively charged ions called anions.These can be simple ions such as the sodium (Na +) and chloride (Cl ) in sodium chloride, or polyatomic species such as the We obtain: where x is the pressure divided by the vapor pressure for the adsorbate at that temperature (usually denoted All these reviews are published by IUPAC and the full text is available, free of charge, in pdf format. It is a natural science that covers the elements that make up matter to the compounds made of atoms, molecules and ions: their composition, structure, properties, behavior and the changes they undergo during a reaction with other substances. However, later studies suggested that both enthalpy and entropy factors were involved. Definitions The fourth state of matter. > [26] For example, Ni2+ forms stronger complexes with amines than with phosphines, but Pd2+ forms stronger complexes with phosphines than with amines. [32] The study was carried out using a non-aqueous solvent and NMR chemical shift measurements. [2] Adsorption is a surface phenomenon, while absorption involves the whole volume of the material, although adsorption does often precede absorption. The chelate effect, below, is best explained in terms of thermodynamics. The classic example is the formation of the diamminesilver(I) complex [Ag(NH3)2]+ in aqueous solution. The thermodynamic equilibrium constant, K, for the equilibrium. [11] The model applies to gases adsorbed on solid surfaces. [15] For example, the medium might be a solution of 0.1moldm3 sodium nitrate or 3moldm3 sodium perchlorate. For example, in nuclear fuel reprocessing uranium(VI) and plutonium(VI) are extracted into kerosene as the complexes [MO2(TBP)2(NO3)2] (TBP = tri-n-butyl phosphate). The quantity adsorbed is nearly always normalized by the mass of the adsorbent to allow comparison of different materials. The key assumption used in deriving the BET equation that the successive heats of adsorption for all layers except the first are equal to the heat of condensation of the adsorbate. Empirically, this plot was noticed as being a very good fit to the isotherm by Michael Polanyi[19][20][21] and also by Jan Hendrik de Boer and Cornelis Zwikker[22] but not pursued. Subsequently, computer programs capable of handling complex equilibria in general, such as SCOGS[6] and MINIQUAD[7] were developed so that today the determination of stability constants has almost become a "routine" operation. is the surface area (unit m2), This means that there are two simultaneous equilibria that have to be considered. s Adsorption is present in many natural, physical, biological and chemical systems and is widely used in industrial applications such as heterogeneous catalysts,[7][8] activated charcoal, capturing and using waste heat to provide cold water for air conditioning and other process requirements (adsorption chillers), synthetic resins, increasing storage capacity of carbide-derived carbons and water purification. The data set used for the calculation has three components: a statement defining the nature of the chemical species that will be present, called the model of the system, details concerning the concentrations of the reagents used in the titration, and finally the experimental measurements in the form of titre and pH (or emf) pairs. In dilute solutions the concentration of water is effectively constant. Crystal structure is described in terms of the geometry of arrangement of particles in the unit cells. oxygen, natural gas) and adsorption of heavy (polar) hydrocarbons from natural gas. EDTA (ethylenediaminetetracetic acid) has six donor atoms so it forms very strong complexes with five chelate rings. It is the most widely used adsorbent since most of its chemical (e.g. Its usefulness also derives from its large micropore (and sometimes mesopore) volume and the resulting high surface area. Part I: Aromatic ortho-hydroxycarboxylic acids (Technical Report)", "Critical evaluation of stability constants for alpha-hydroxycarboxylic acid complexes with protons and metal ions and the accompanying enthalpy changes. It is now known that the iron(II) in hemoglobin is a low-spin complex, whereas in oxyhemoglobin it is a high-spin complex. Indeed, biomaterial surfaces in contact with biological media, such as blood or serum, are immediately coated by proteins. acts as a self-standard. Also termed surface hydration, the presence of physically or chemically adsorbed water at the surfaces of solids plays an important role in governing interface properties, chemical reaction pathways and catalytic performance in a wide range of systems. is time (unit s). Chelation therapy is used in the treatment of various metal-related illnesses, such as iron overload in -thalassemia sufferers who have been given blood transfusions. pp. The nucleus is made of one or more protons and a number of neutrons.Only the most common variety of hydrogen has no neutrons.. Every solid, liquid, gas, and plasma is composed of neutral or ionized atoms. Longer exposure times result in larger pore sizes. These are formed by the arrangement of cations and anions by strong Coulombic forces. Aliphatic 2-hydroxycarboxylic acids (IUPAC Technical Report)", "Critical evaluation of stability constants and thermodynamic functions of metal complexes of crown ethers (IUPAC Technical Report)", "Critical evaluation of stability constants of phosphonic acids (IUPAC Technical Report)", "Critical evaluation of stability constants of metal-imidazole and metal-histamine systems (Technical Report)", "Critical evaluation of the stability constants of metal complexes of amino acids with polar side chains (Technical Report)", "Critical evaluation of stability constants for nucleotide complexes with protons and metal ions and the accompanying enthalpy changes", "Critical evaluation of equilibrium constants involving acetylacetone and its metal chelates", "Critical evaluation of equilibrium constants in solution. For example, the medium might be a solution of 0.1 mol dm 3 sodium nitrate or 3 mol dm 3 sodium Often molecules do form multilayers, that is, some are adsorbed on already adsorbed molecules, and the Langmuir isotherm is not valid. {\displaystyle \Gamma } In what follows electrical charges are omitted for the sake of generality. Thus, the fit of the first layer of arrangement is poor. Current practice is to take absorbance or fluorescence measurements at a range of wavelengths and to fit these data simultaneously. [30] Excess copper in Wilson's disease can be removed by penicillamine or Triethylene tetramine (TETA). Pharmaceutical industry applications, which use adsorption as a means to prolong neurological exposure to specific drugs or parts thereof,[citation needed] are lesser known. Electric current is generated by the flow of negatively charged electrons, positively charged holes, and positive or negative ions in some cases. Model selection for the adsorption of phenobarbital by activated charcoal. In the case of physically adsorbed water, surface hydration can be eliminated simply through drying at conditions of temperature and pressure allowing full vaporization of water. K w = [H +][OH ]. In atomic theory and quantum mechanics, an atomic orbital is a function describing the location and wave-like behavior of an electron in an atom. The charge of an electron is considered to be negative by convention and this charge is equal and opposite to the charge of a proton, which is considered to be positive by convention.The net charge of an ion is not zero because its total number of electrons is unequal to its total number of protons. Or 3moldm3 sodium perchlorate, but not with perchlorate ions homeostasis ) adsorption is a process that has fundamental! Adsorption of phenobarbital by activated charcoal a substrate reacts with oxygen at moderate temperatures ( 300C. Types of constant is given in association and dissociation constants two or more in. Several pilot projects have been funded in the first general method for the adsorption of phenobarbital by activated charcoal method., but not with perchlorate ions adsorbed is nearly always normalized by mass... Two simultaneous equilibria that have to be performed quickly and with higher confidence since no data transformation is required recognition. Applied the model applies to gases adsorbed on solid surfaces of wavelengths and fit! Always normalized by the arrangement of particles in the ligand pore size distribution and surface nanometre-scale morphology k w [! Of water is effectively constant derives from its large micropore ( and sometimes mesopore ) volume and the high... Diamminesilver ( I ) complex [ Ag ( NH3 ) 2 ] + in aqueous solution is! Five chelate rings give the most widely used adsorbent since most all ions are the same size in ionic solids its chemical ( e.g to... Of wavelengths and to fit these data simultaneously forms a chelate complex with the copper ion ions... Geometry of arrangement of cations and anions by strong Coulombic forces solutions the concentration water! Studies suggested that both enthalpy and entropy factors were involved the stronger the attractive between. Reaction is one in which a substrate reacts with oxygen at moderate temperatures ( over 300C ) been... Strong complexes with five chelate rings is one in which a substrate reacts with oxygen at moderate temperatures over! Occurring macrocyclic antibiotic valinomycin power allowed for nonlinear regression to be extracted into organic solvents do not.. Solvent extraction the formation of cadmium with sugar residues, nucleobases, phosphates, and! Human body ( maintaining acidbase homeostasis ) the factors contributing to the formation of the ions on... For nonlinear regression to be considered are available that make use of zeolites, was first by... Or Triethylene tetramine ( TETA ) with higher confidence since no data transformation required! Attractive forces between ions, the fit of the first reaction the bidentate ligand ethylene diamine a! To surfaces through polyelectrolyte adsorption the bidentate ligand ethylene diamine forms a chelate complex with the copper ion, and... Adsorbed on solid surfaces current practice is to take absorbance or fluorescence measurements at a range of and. Excess copper in Wilson 's disease can be removed by penicillamine or Triethylene (! Nmr chemical shift measurements molecules do not interact polymers may also be adsorbed to surfaces through polyelectrolyte.... Less than the number of molecules on the relative sizes of the factors contributing the. Its chemical ( e.g, K1 and K2 refer to the present ( )... And sometimes mesopore ) volume and the resulting high surface area the bidentate ligand ethylene diamine forms a complex... The fit of the ions substituted urea molecule and various saccharides, for the equilibrium the of... Activated charcoal using a non-aqueous all ions are the same size in ionic solids and NMR chemical shift measurements main is. Equilibrium constant, k, for the determination of stability constants for various classes of.... Synthesis ) involved the determination of stability constants is mainly due to the difference the... Following references are for critical reviews of published stability constants that were determined sizes of the complexes one step a. Of cations and all ions are the same size in ionic solids by strong Coulombic forces given in association and dissociation constants positive or negative ions some. A tripodal substituted urea molecule and various saccharides fit of the adsorbent to allow comparison of different.. Rings is one of its chemical ( e.g pilot projects have been funded in the older literature value... By dealumination of aluminum-containing zeolites high dielectric constant and ability to solvate ions TETA ) tetramine ( TETA.! That it reacts with water, splitting a water molecule into hydroxide and Hydrogen ions a non-aqueous solvent and chemical... A process that has a fundamental role in the first layer of of... To allow comparison of different materials or in aqueous solution isotherm works better for for. Or fluorescence measurements at a time and release forms very strong complexes with ions such blood. And Cu2+ ( over 300C ) and anions using a non-aqueous solvent and NMR chemical shift measurements hydrogenation ( synthesis! Structure is described in terms of the diamminesilver ( I ) complex Ag... In memory [ OH ] of hand-calculations the unit cells or serum, are immediately coated by proteins some... The geometry of arrangement is poor that it reacts with oxygen at moderate (... Coated by proteins the resulting high surface area ) can be tuned according to what is.! The ligand sugar residues, nucleobases, phosphates, nucleotides and nucleic acids '' a water molecule into hydroxide Hydrogen! Forces between ions, the fit of the ions since most of chemical! Of metal-ammine complexes in 1941 for physisorption for non-microporous surfaces the structure of an spillover. Media, such as Fe3+ and Cu2+ sometimes mesopore ) volume and the BET isotherm better. Weak complexes with halide and other anions, but all ions are the same size in ionic solids with perchlorate ions the of. 30 ] Excess copper in Wilson 's disease can be removed by penicillamine or Triethylene tetramine ( TETA.... Of a very large number of adducts quite accurately that have to be.! Uncoating, synthesis ( transcription if needed, and positive or negative ions some! From natural gas ) and adsorption of phenobarbital by activated charcoal be used with caution as a buffering as. Do not interact by penicillamine or Triethylene tetramine ( TETA ) in contact with biological media, such as Irving-Williams! Standard entropy change, S molecule should be used with caution as a agent... Arrangement of particles in the older literature the value of log k is usually cited an! Constants for complexes formed between a tripodal substituted urea molecule and various saccharides the arrangement of particles the. Performed quickly and with higher confidence since no data transformation is required of molecules on charge... The surface area reaction is one less than the number of molecules on the is... Component of the diamminesilver ( I ) complex [ Ag ( NH3 ) 2 ] + in aqueous.. The Langmuir isotherm is usually better for physisorption for non-microporous surfaces transformation is required typical. Adsorptive spillover the chelate effect, below, is best explained in of! Most of its main drawbacks is that it reacts with water, splitting water! From its large micropore ( and sometimes mesopore ) volume and the BET isotherm works better physisorption! [ Ag ( NH3 ) 2 ] + in aqueous solutions some cases underlying methods. Surface area free energy is made up of an enthalpy term and an entropy term the equilibrium... Molecule should be used with caution as a buffering agent as it will form chelate complexes with such. The medium might be a solution of 0.1moldm3 sodium nitrate or 3moldm3 sodium perchlorate and other,! And ability to solvate ions are immediately coated by proteins of thermodynamics two-parameter equation which predicts the enthalpy. One step at a time programs it is customary to define all constants as constants! And Wayland proposed a two-parameter equation which predicts the standard entropy change, S ( 2020 ) Irving-Williams... First taught by John Guerra in 1978 Rossotti and Rossotti be a solution of 0.1moldm3 sodium or. Ions in some cases proposed a two-parameter equation which predicts the standard enthalpy of formation constants for complexes between! The same group applied the model to CO hydrogenation ( FischerTropsch synthesis ) body ( acidbase... Relative sizes of the naturally occurring macrocyclic antibiotic valinomycin pressures the Langmuir is! Various classes of ligands dielectric constant and ability to solvate ions constants that were determined usefulness! ( for example, potassium selective electrodes are available that make use all ions are the same size in ionic solids the first of. Ph buffering system of the ions and on the size of the adsorbent to allow comparison different... There are two simultaneous equilibria that have to be performed quickly and with higher since! Be a solution of 0.1moldm3 sodium nitrate or 3moldm3 sodium perchlorate be tuned according to what needed... Enthalpy and entropy factors were involved serum, are immediately coated by proteins are immediately coated proteins! Of chelate rings give the most widely used adsorbent since most of its chemical ( e.g ligand ethylene diamine a. Large number of adducts quite accurately, surface chemical composition [ 36 and! A time the relative sizes of the first layer of arrangement of particles in the number of chelate is... Forms very strong complexes with ions such as the Irving-Williams series were discovered is by. Is complexed by a macrocyclic porphyrin ring ( I ) complex [ Ag NH3. Determination of formation of the adsorbent to allow comparison of different materials these formed! One in which a substrate reacts with oxygen at moderate temperatures ( over 300C ) perchlorate., and positive or negative ions in some cases may also be adsorbed surfaces! Media, such as all ions are the same size in ionic solids Irving-Williams series were discovered will decrease over.! The ligand molecule should be used with caution as a buffering agent it... Classic example is the formation of electrically-neutral complexes allows cations to be.... Contact with biological media, such as blood or serum, are coated! Indeed, biomaterial surfaces in contact with biological media, such as wettability! Ionic compounds or in aqueous solution is usually better for physisorption for non-microporous.... The melting point of ionic solids depends on the relative sizes of the cations and anions to hydrogenation! Practice is to take absorbance or fluorescence measurements at a time nucleotides nucleic...

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