surface chemistry: complexation at the solid/water interface types of particles and colloids in...
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Surface Chemistry:Surface Chemistry:Complexation at the Solid/Water InterfaceComplexation at the Solid/Water Interface
Types of Particles and Colloids in Water:Supra-micron (Particles) and Sub-micron (Colloids)Clays (e.g., kaolinite, montmorillonite)
Metal Oxides (e.g., alumina (Al2O3), geothite (Fe2O3), hematite (FeOOH))
Silica (SiO2), CalciteBio-particles, Bio-Colloids, Detritus (e.g., cell fragments)Significance: Turbidity, Contaminant Carriers, Pathogens
Stationary Surfaces:Lake and Aquifer Sediments
Reactions at SurfacesReactions at Surfaces
Complexation:
Ligand + Surface (Metal) Site
or
Metal + Surface (Ligand) Site Complexation vs. Adsorption
vs. Partitioning (hydrophobic effects)
Characteristics of Particles/ColloidsCharacteristics of Particles/Colloids
Size (um); Optical Particle Counters (OPC); Scanning Electron Microscopy (SEM)
Specific Surface Area (m2/g) Porous vs. Non-porous; Diffusional
Considerations Charge; Electrophoretic
Mobility; Zeta Potential Site Density (eq/m2, #/nm2); Acid/Base,
Metal, and Ligand Sites; Colloidal Titrations Colloidal/Particle Stability
Surface ChargeSurface Charge
Electric Double Layer Charged Surface + Counter-ions in Counter-layer Net Charge, Dictated by Shear Plane Colloidal Sol: No Net Charge Colloidal Stability: Interaction of Double Layers Electrostatic vs. Van Der Waals Forces Figure 7.2
Figure 7.2
Surface Charge – cont.Surface Charge – cont.
Measurement by Electrophoresis:
Electrophoretic Mobility (EPM) {(um/s)/(V/cm); EPM = f(pH); Amphoteric; pHZPC; Acidic (e.g. silica) vs. Basic (e.g., alumina) Surfaces
Figure 3.1, Table 10.6 EPM vs. Zeta Potential, (mV); = 12.9 EPM @ 25 oC ZP vs. Charge, q (coulombs or C/m2); = 4q/D; =
thickness of diffuse layer; D = dielectric constant
*+ -
x cm
Figure 3.1
Table 10.6
Adsorption IsothermAdsorption Isotherm
Isotherm Plot:
S = (C0 – Ceq)/M; S = solid-phase conc. (ug/g); C = aqueous-phase conc. (ug/L); m = sorbent conc. (g/L)
Linear (Partitioning) vs. Curvilinear (Adsorption) Linear; S = KPC, KP = Partition Coefficient; Freundlich: S = KCn;
Langmuir: S = abC/(1 + bC), a = monolayer saturation
S (ug/g)
C (ug/L)
* * **
C0
m
Ceq
Origin of (Surface) ChargeOrigin of (Surface) Charge
Ionizable Function Groups on SurfaceLet “>” or “” or “{}” represent a surface site
>SiOH2+ >SiOH >SiO-
+ H+ + H+
Ka1s Ka2
s
>SiOH or SiOH or {SiOH}
Ka1s = [H+]{SiOH}/{SiOH2
+}
Amphoteric Acid/Base BehaviorFigure 10.7
Figure 10.7
Origin of (Surface) Charge – cont.Origin of (Surface) Charge – cont.
Surface Complexes
>O- + Mg2+ >O-Mg+; >O- = surface ligand site
>M+ + SO42- >MSO4
-; >M+ = surface metal site
Figure 10.7
K1s vs. 2
s (multidendate, polynuclear)
For Clays, Isomorphous Substitution
Clay: Aluminum Silicate
Al(III) Clay Si(IV); “-’ charge
Origin of (Surface) Charge – cont.Origin of (Surface) Charge – cont.
Surface Adsorption of NOM (e.g. Fulvic Acid); Complexation, Hydrophobic Effects
Surface Complexation vs. Ion Exchange (e.g., alumina) vs. Hydrophobic Effects (e.g., HA) vs. Electrostatic Barriers (e.g., silica)
Ca2+ Binding to Humic Coating: Reduction in Charge
pH
* * * *
+
-* = w/o FA; = w/FA
Metal Binding and Ligand Exchange at a SurfaceMetal Binding and Ligand Exchange at a Surface
Surface Ligands and Surface Metals; Ligand Sites and Metal Sites
Figure 8.3 Metal Binding:
OH + M2+ OM+ + H+ (proton competition) Ligand Exchange;
OH + L- L + OH- (exchangeable ligand) Multidendate and Polynuclear Behavior Possible
Figure 8.3
Reactions @ Metal Oxide Surface: Reactions @ Metal Oxide Surface: Modeling FrameworkModeling Framework
Consider:Acid/Base (Protonation/Deprotonation)Metal Complexation (M2+)Ligand Exchange (L2-)Use Silica (Si) as Example
Let {Bi} = conc. of surface species i (mol/cm2)
[Bi] = conc. of surface species i (mol/L) Acid/Base Reactions
{SiOH2+} {SiOH} + [H+]
Ka1s = {SiOH}[H+]/{SiOH2
+}
{SiOH2+} {SiO-} + [H+]
Ka2s = {SiO-}[H+]/{SiOH2
+}
Reactions @ Metal Oxide Surface: Reactions @ Metal Oxide Surface: Modeling Framework – cont.Modeling Framework – cont.
Metal Complexation{SiOH} + [M2+] {SiOM+} + [H+]
KMs = {SiOM+}[H+]/{SiOH}[M2+]
Ligand Exchange{SiOH} + [L2-] {SiL-} + [OH-]
KLs = {SiL-}[OH-]/{SiOH}[L2-]
Surface Charge
= F({SiOH2+} - {SiO-} + {SiOM+} - {SiL-} )
F = Faraday constant (90,490 C/mole)
Reactions @ Metal Oxide Surface: Reactions @ Metal Oxide Surface: Modeling Framework – cont.Modeling Framework – cont.
Mass Balance, CT,s
CT,s = {SiOH2+} + {SiOH}+ {SiO-} + {SiOM+} + {SiL-}
CT,s = Total sites (mol/cm2 or #/cm2)
e.g., Al2O3: pHZPC = 8.7, pKa1s = 7.4, pKa2
s = 10.0, CT,s = 1.3/nm2
System:Five surface speciesFour aqueous species
Ki expressions + Kw
CT,M, CT,L, CT,s
(Aqueous) Charge Balance
Colloidal TitrationsColloidal Titrations
e.g., Suspension of Al2O3, Titrated with Acid or Base or Metal (M) or Ligand (L):
Infer Conditional Bind Constant(s) from Shape of Titration Curves (Alkametric, Compleximetric, etc.)
Note: {SiOH} can protonate, deprotonate, complex metals, exchange ligands; competitive effects
Example 4-27
Al2O3
H+ or OH- or M or L
pH or Mfree or Lfree
Example 4-27
Surface Coatings and Surface Coatings and Common Mineral SurfacesCommon Mineral Surfaces
Surface Coatings
Figure 11.1
Bacterium: Protein/Amino Acids; Amphoteric Behavior
Common Mineral Surfaces
Silica, alumina, Geothite, Hematite
Figure, Figure 11.14
Figure 11.1
Figure
Figure 11.14
Surface and Aqueous Complexation of MetalsSurface and Aqueous Complexation of Metals
Figure 11.25 Cu-NOM Cu2+ Cu-Mineral
Cu-Mineral-NOM
Binding and Sorption Constants Metal Partitioning vs. Metal Transport Stationary vs. Mobile Phases
Figure 11.25
Movement of Particles/ColloidsMovement of Particles/Colloids
By Settling
Water Column in Lake; Sedimentation Basin; Differential Settling
By Fluid Shear
Velocity Gradient; Mixing By Brownian Motion
<0.1 Colloids By Advection
Advective Flow
Aggregation of ParticlesAggregation of Particles
Particle-Particle Interactions Zeta Potential vs. Van Der Waals Forces Particle Collisions; Attachment
Sticking Factor: Lake: = 0.01 to 0.10
Treatment Plant (Coagulation): = 0.10 to 1.0
Aggregation of Particles – cont.Aggregation of Particles – cont.
Assuming Fluid shear Predominates:dn/dt = -4nG/n = colloids/L @ time tG = velocity gradient (T-1; (L/T)/L) = volume fraction of colloidsper unit volume of suspension
ln (n/n0) = -4nGt/
Stability Ratio, WW = 1/
Discrete Particles vs. Aggregates
ln n/n0
t
slope:
Environmental PartitioningEnvironmental Partitioning
Lake
Unique: Phases: Water (Column), Sediments, Colloids/NOM, Biomass, Atmosphere
Associated Binding, Partitioning, Sorption Constants
Cu2+ vs. Benzene Groundwater (Aquifer)
Unique Phases: Water, Aquifer Media, NOM/Colloids
Saturated Zone vs. Unsaturated Zone (Pore Gas)