Colloid chemistry

Lecture 7: Interfacial phenomena; adsorption from solution at the S/L interface (non-electrolytes and electrolytes)

Adsorption from solution at the solid/liquid interface

adsorption of non-electrolytes

adsorption of electrolytes

Adsorption (displacement) at the S/L interface
ns =
Vo o s σ (v) n ≈ n = (c − c) m

Adsorption isotherm:

f(c), T=constant

solvent

solute

distance from the surface c, concentration in the bulk solution concentration profile

adsorbent

ns, amount adsorbed

Adsorption at the solid/solution interface

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Factors affecting adsorption from solution at the S/L interface .

Application of S/L adsorption phenomena in pharmacy Miscellaneous applications .

06 0.10 1.differential interferometry .differential refractometry .02 0.8 1 cmc 0.2 Vo o s σ (v) n ≈ n = (c − c) m real amount of solute adsorbed (volume-reduced) surface excess 2 0.06 0.Determination of solution adsorption isotherms concentration analysis: .6 3 1.02 4 0.04 0.04 0.08 0.00 0.UV spectrophotometry .0 0.10 c [g/L] Γ [µmol/m2] ns [mg/g] .08 0.4 0 0.mass spectrometry c [mmol/L] 0.

Classification of adsorption isotherms according to Giles (adsorption from dilute solutions) S L H C 1 amount of solute adsorbed on the solid surface 2 3 4 5 equilibrium concentration of solute .

e.g.Frequent cases: type 2 isotherms preferential adsorption. mmol/dm3 . mmol/g amount adsorbed per unit mass of the solid L-shaped or [Γ]=µmol/m2 . amount adsorbed per unit surface area of the solid (surface concentration) [c] = mg/dm3. Langmuir isotherm ns high affinity isotherm. e. ionic surfactants ns cooperative adsorption ns c c c c S-shaped [ns]: mg/g.g. chemisorption ns ion-exchange isotherm.

Langmuir isotherm (L2-type) ns = ns m× ns c K+ c 1 ns 1 ns = 1 K 1 + × s c ns m nm ns m tg α → K 1 /n s m (Henry’s law constant) Determination of the specific surface area: s ×a as = nm m [as] = m2/g .

given solvent.Effect of polarity on the adsorption ns ns • inverse Traube’s rule • Traube’s rule • Lundelius’s rule: i) given solute. different solvents ii) given solid. given solid. different solutes the extent of adsorption increases with the decrease of solublity .

64 3.3 77.22 3.5 35.95 .• Gurvics’s rule: given solute. various solvents the larger the heat of wetting of the solid by the solvent.50 3.3 apparent adsorption of benzoic acid from 1% solution on Florida fuller’s earth (rich in montmorillonite). given adsorbent. the smaller the amount of the solute adsorbed solvent acetone ethyl acetate chloroform benzene carbon tetrachloride heat of wetting.4 19.6 23. J/g 114. g/g 0 0.

.Adsorption of polymers at the solid-liquid Interface • Polymer adsorption and small molecule adsorption (eg. ions) properties are very different. This is due to the many configurations that a polymer can assume in liquid and at surface. entropy loss per molecule greater than for small molecules (opposes adsorption). decrease in ∆Go is greater due to multiple attachments / chain (favors adsorption). Amount of polymer adsorbed generally represented in form of an • adsorption isotherm. • For flexible polymers. surfactants. However. • A key parameter is the determination of the amount of polymer adsorbed and the conformation of • the polymer on the surface. • Polymer adsorption is generally a slower process than low MW species such as surfactants.

8 0.2 1 0.2 0 0 100 200 300 400 500 600 MW3 > MW2 > > MW MW MW 1 1 3 > MW 2 MW3 MW 3 MW2 MW 2 MW1 MW 1 c (mg/L) .6 0.4 1.4 0.Typical Polymer Adsorption Isotherms the effect of molecular weight Amount adsorbed. Γ (mg/m2) 1.

For same MW. as well as competition • between polymer and solvent for binding sites. (7) Polymer adsorption can be accompanied by a change in conformation compared to that occupied in • the bulk. Γ keeps increasing with MW. plateau is independent of MW.Polymer Adsorption Polymer adsorption isotherms generally have the following characteristics: (1) high affinity character. particularly for higher MW. thickness. (6) Adsorption energy depends on both the nature of the solvent and the surface. Γ higher in θ-solvents than in good solvents. For high MW. Nature of the adsorbed layer (conformation. (4) In good solvents. (5) In θ-solvents. Γ increases with MW for low MW’s. the lower the high affinity character (isotherm becomes more rounded). . However. (2) Plateau level is of the order of a few mg/m2. (3) Adsorption (Γ) increases with decreasing solvent quality. surface coverage) and its’ • interaction with the solvent determine a suspension’s properties. the lower MW.

Adsorption from solution at the solid/liquid interface adsorption of non-electrolytes adsorption of electrolytes .

colloid stability) .Electrostatic forces & the electrical double layer C C C C Sources of interfacial charge Electrostatic theory: the electrical double layer Electrokinetic phenomena Electrostatic forces (DLVO theory.

AgI. Some ionic crystals have a slight imbalance in number of lattice cations or anions on surface. CaF2. NaCl. BaSO4. lattice substitution in kaolin HO O O O OH Si Al Si Si HO O O O OH .IAg+ Ag+ I+ Ag+ I- Ag+ (2) Substitution of surface ions eg.Sources of interfacial charge at the solid/aqueous solution interface (1) Differential ion solubility. eg. KCl I .Ag+ IIIAg I.

Mg+2.and H+ ions • multivalent ions: Ca+2.Sources of interfacial charge at the solid/aqueous solution interface (3) Specific ion adsorption OH + • OH. • ionic surfactants. polyelectrolytes + + M O O O + + + + +2 + + + + + + + + + + - . La+3. SO42-.

Surface charge formation at the solid/aqueous solution interface (4) Direct Ionization of surface groups H O M O O O H H O M O O O H OH O M O O O + H2O .

on pH) Mixed acid and basic sites. of pH) Weak acid sites (dep. Strong acid sites (indep. (4) implies the formation of variable surface charges . (dependent on pH) Note: (1)-(3) result in the formation of permanent surface charges. cont.4) Ionization of surface groups.

montmorillonite: cation exchangers layered double hydroxides (LDHs): anion exchangers • Properties – Capacity: amount of exchangeable ions per unit quantity of material ion exchange capacity (CEC.) zeolite.g.Surface charge formation at the solid/aqueous solution interface (5) Ion exchange adsorption (non-equivalent ion adsorption) • Resins: – Organic or inorganic polymers used to exchange cations or anions from a solution phase Organic resins: polymer backbone not involved in bonding functional group for complexing anion or cation – Inorganic resins: aluminosilicates (e. AEC) – Selectivity: cation or anion exchange (positive or negative ions) some selectivities within group C C Exchange proceeds on an equivalent base Charge of the exchange ion must be neutralized .

Ion exchangers SO3 H CH2 N(CH3 )3 OH organic anion exchanger linkage group organic cation exchanger OH Zr O OPO(OH)2 OH Zr O Zr O OPO(OH)2 Zr inorganic anion exchanger OPO(OH)2 OPO(OH)2 OPO(OH)2 OPO(OH)2 .

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Deionization of water .

Deionization of water .

Large-scale ion-exchange columns .

Concentration dependence of the surface charge density (σ). in turn implies maximum surface potential (ψomax) surface potential ψo Stern potential ψSt zeta-potential ζ σ % ψo * distance x from the surface charge density σ (amount surface potential ψo solid surface of surface charge determining plotted against the ions adsorbed. Γ) plotted against electrolyte concentration towards the bulk solution ion concentration c c in the bulk solution zeta potential ζ plotted against the electrolyte concentration c in the bulk solution σ = z i e Γi . the surface potential (ψo) and the electrokinetic (zeta) potential (ζ) on the electrolyte concentration (c) Plateau: maximum amount adsorbed (Γmax) at c* implies maximum surface charge density (σmax) which.

Electrical double layer + + + + + + + + + + + + + + + + + + -potential determining ions counter ions - - + + + + + + + + + + + + + + + + + + + + + - + - - + counter ions + + + co-ions - + - - - - + + Helmholtz model (1879) Gouy-Chapman model (1914) .

THE GUOY-CHAPMAN DOUBLE LAYER potential determining ions Assumptions: 1. Dielectric constant is constant ⎤ ⎡ ze c i (x) = c ⋅ exp ⎢− i ψ 0 exp(− κ x )⎥ ⎦ ⎣ kT Boltzmann equation + + + + + + + + + + + + + + + + + + - ψ0 - - + counter ions .C+(x) + - + + co-ions + + ψ(x) x - ψ=0 .. Ions are point charges 3..C-(x) . No specific ion adsorption 4. The surface charge is smeared 2.

C (x) . ψ = 0) ψ0 /e δ = 1/ κ x 1 = const × κ εkT = δ (Debye length) I I= 1 2 ∑ i ci z 2 i .x + ψ0 counter ions ψ (x) ψ0 Potential profile: ψ (x) = ψ o e − κ x (x = 0 .The thickness (δ/1/κ) of the diffuse electric double layer + + + + + + + + + + + + + + + + + + ..co-ions . ψ = ψ0 x → ∞.C (x) ψ(x) .

ψ0 ψ0/e potential decay. x 1/κ 1 εkT = const × κ I . ψ(x) distance.THE GUOY-CHAPMAN DOUBLE LAYER ψ (x) = ψ o e − κ x surface potential.

30 nm z C( M ) 0 < κ −1 < 1000 nm typically. 25˚C: κ −1 ≈ “double layer thickness” (counter ions) 0.Ion concentration profiles For water. (co-ions) 0 < κ −1 < 100 nm .

double layer thickness decreases Debye-length κ-1. (nm) .Effect of valency number on Debye-length 1/κ 100 1-1 electrolyte 90 2-2 electrolyte 80 3-3 electrolyte 70 60 50 40 30 20 10 0 10-5 10-4 10-3 10-2 10-1 100 101 electrolyte concentration (M) Charge screening increases with the valency number of the acting ion.

x Charge screening increases with the concentration of the acting ion. double layer thickness decreases .Effect of salt concentration on Debye-length 1/κ potetial. ψ(x) C ψ0 c1 < c2 < c3 Ψo/e c3 c2 c1 1/κ3 1/κ2 1/κ1 distance.

xSt ∆ Stern layer thickness .Stern layer κ ( x-x ) − St ψ ( x) = ψ St e .ψ(x) .STERN MODEL (1924) + + + + + + + + + + + + + + + + + + Surface potential ψ0 Stern potential ψSt .

For strong specific adsorption in the Stern layer… ψSt ψSt …even surface charge reversal may occur! .

Solid: AgCl in contact with an aqueous solution of KCl. PO43-) adsorb more strongly than bivalent ions (Ba2+. Cl-). • Schulze-Hardy rule: trivalent ions (Al3+.g. Example. SO42-). • In acidic solution H+. their adsorption increases in the same sequence. in alkaline solution OH. (e. and bivalent ions adsorb more strongly than univalent ions (Na+. • More hydrated ions adsorb less strongly. • Surfaces in contact with water are fare more often negatively chraged than positively charged because cations are usually more hydrated than anions. or very similar to. KBr or CuSO4. the hydration of alkali metal ions decreases in the sequence of Li+>Na+>K+>Rb+>Cs+. the anion or the cation constituting the crystal lattice.. . AgNO3.General rules for the adsorption of ions on crystal lattices • On poorly soluble crystalline solids. such anions and cations are preferentially adsorbed which are the same as.tend to be specifically adsorbed on the solid. less hydrated ions adsorb more strongly on the solid.

one of the ions in the crystal lattice. or similar to. KBr. .Preferential ion adsorption on crystal lattices + - - + - + + + + + + - + + + + + - KCl AgCl + AgCl + + + + . CuSO4. Example: solid: AgCl in aquesous soltions of KCl. AgNO3.+ + + + + + + + + AgNO3 + + + + + + - + - - + + + + + An ion which is the same kind as.