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 (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

Factors affecting adsorption from solution at the S/L interface

Application of S/L adsorption phenomena in pharmacy

Miscellaneous applications

Determination of solution adsorption isotherms

concentration analysis:
- UV spectrophotometry - differential refractometry - differential interferometry - mass spectrometry
c [mmol/L]
0.02 4 0.04 0.06 0.08 0.10 1.6

1.2

Vo o s (v) n n = (c c) m
real amount of solute adsorbed (volume-reduced) surface excess

0.8

cmc

0.4

0 0.00

0.02

0.04

0.06

0.08

0.0 0.10

c [g/L]

[mol/m2]

ns [mg/g]

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

Frequent cases: type 2 isotherms

preferential adsorption, Langmuir isotherm ns high affinity isotherm, e.g. chemisorption ns ion-exchange isotherm, e.g. ionic surfactants ns

cooperative adsorption ns

S-shaped
[ns]: mg/g; mmol/g
amount adsorbed per unit mass of the solid

L-shaped
or []=mol/m2 ;
amount adsorbed per unit surface area of the solid (surface concentration)

[c] = mg/dm3; mmol/dm3

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 K
1 /n s m

(Henrys law constant)

Determination of the specific surface area:

s a as = nm m

[as] = m2/g

Effect of polarity on the adsorption

ns ns

inverse

Traubes rule

Traubes

rule

Lundeliuss rule:
i) given solute; given solid; different solvents ii) given solid; given solvent; different solutes

the extent of adsorption increases with the decrease of solublity

 Gurvicss rule:
given solute; given adsorbent; various solvents

the larger the heat of wetting of the solid by the solvent, the smaller the amount of the solute adsorbed
solvent acetone ethyl acetate chloroform benzene carbon tetrachloride heat of wetting, J/g 114.3 77.5 35.6 23.4 19.3 apparent adsorption of benzoic acid from 1% solution on Florida fullers earth (rich in montmorillonite), g/g 0 0.22 3.50 3.64 3.95

Adsorption of polymers at the solid-liquid Interface

Polymer adsorption and small molecule adsorption (eg. surfactants, ions) properties are very different. This is due to the many configurations that a polymer can assume in liquid and at surface. For flexible polymers, entropy loss per molecule greater than for small molecules (opposes adsorption). However, decrease in Go is greater due to multiple attachments / chain (favors adsorption). Polymer adsorption is generally a slower process than low MW species such as surfactants.

A key parameter is the determination of the amount of polymer adsorbed and the conformation of the polymer on the surface. Amount of polymer adsorbed generally represented in form of an adsorption isotherm.

Typical Polymer Adsorption Isotherms

the effect of molecular weight Amount adsorbed, (mg/m2)
1.4 1.2 1 0.8 0.6 0.4 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)

Polymer Adsorption
Polymer adsorption isotherms generally have the following characteristics:
(1) high affinity character. However, the lower MW, the lower the high affinity character (isotherm becomes more rounded). (2) Plateau level is of the order of a few mg/m2. (3) Adsorption () increases with decreasing solvent quality. (4) In good solvents, increases with MW for low MWs. For high MW, plateau is independent of MW. (5) In -solvents, keeps increasing with MW. For same MW, higher in -solvents than in good solvents, particularly for higher MW. (6) Adsorption energy depends on both the nature of the solvent and the surface, 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. Nature of the adsorbed layer (conformation, thickness, surface coverage) and its interaction with the solvent determine a suspensions properties.

Adsorption from solution at the solid/liquid interface

adsorption of non-electrolytes

adsorption of electrolytes

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; colloid stability)

Sources of interfacial charge at the solid/aqueous solution interface

(1) Differential ion solubility; Some ionic crystals have a slight imbalance in number of lattice cations or anions on surface, eg. AgI, BaSO4, CaF2, NaCl, KCl
I - Ag+ IIIAg I- IAg+

Ag+

I+

Ag+

I-

Ag+

(2) Substitution of surface ions eg. lattice substitution in kaolin

HO O O O OH Si Al Si Si HO O O O OH

Sources of interfacial charge at the solid/aqueous solution interface

(3) Specific ion adsorption
OH

+
OH- and H+ ions
multivalent ions: Ca+2, Mg+2, La+3, SO42-, ionic surfactants, polyelectrolytes

M O O O

+ + + +2 + + + + + + + + + + -

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

4) Ionization of surface groups, cont.

Strong acid sites (indep. of pH) Weak acid sites (dep. on pH)

Mixed acid and basic sites; (dependent on pH)

Note: (1)-(3) result in the formation of permanent surface charges; (4) implies the formation of variable surface charges

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.g.) zeolite, montmorillonite: cation exchangers layered double hydroxides (LDHs): anion exchangers Properties Capacity: amount of exchangeable ions per unit quantity of material ion exchange capacity (CEC; 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

Deionization of water

Deionization of water

Large-scale ion-exchange columns

Concentration dependence of the surface charge density (), the surface potential (o) and the electrokinetic (zeta) potential () on the electrolyte concentration (c)
Plateau: maximum amount adsorbed (max) at c* implies maximum surface charge density (max) which, in turn implies maximum surface potential (omax) surface potential o Stern potential St zeta-potential

% o

*
distance x from the surface charge density (amount surface potential o solid surface of surface charge determining plotted against the ions adsorbed, ) plotted against electrolyte concentration towards the bulk solution ion concentration c c in the bulk solution zeta potential plotted against the electrolyte concentration c in the bulk solution

= z i e i

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. The surface charge is smeared 2. Ions are point charges 3. No specific ion adsorption 4. Dielectric constant is constant

ze c i (x) = c exp i 0 exp( x ) kT

Boltzmann equation

+ + + + + + + + + + + + + + + + + +

counter ions

- - C-(x) - - C+(x) + -

+ co-ions

(x)

=0

The thickness (/1/) of the diffuse electric double layer

+ + + + + + + + + + + + + + + + + +

- co-ions - - C (x) (x) - C (x) - x

+

counter ions

(x) 0

Potential profile:

(x) = o e x
(x = 0 ; = 0 x ; = 0)

0 /e

= 1/

1 = const

kT = (Debye length) I

I=

1 2

ci z 2 i

THE GUOY-CHAPMAN DOUBLE LAYER

(x) = o e x
surface potential, 0 0/e

potential decay, (x) distance, x

1/

1 kT = const I

Ion concentration profiles

For water, 25C:

1
double layer thickness
(counter ions)

0.30 nm z C( M )

0 < 1 < 1000 nm

typically,

(co-ions)

0 < 1 < 100 nm

Effect of valency number on Debye-length 1/

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; double layer thickness decreases

Debye-length -1, (nm)

Effect of salt concentration on Debye-length 1/

potetial, (x)

C 0

c1 <

c2 <

c3

o/e

c3

c2

c1

1/3

1/2

1/1

distance, x

Charge screening increases with the concentration of the acting ion; double layer thickness decreases

STERN MODEL (1924)

+ + + + + + + + + + + + + + + + + +

Surface potential 0

Stern potential St

- Stern layer ( x-x ) St ( x) = St e - (x) - xSt

Stern layer thickness

For strong specific adsorption in the Stern layer

St

St

even surface charge reversal may occur!

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

Preferential ion adsorption on crystal lattices

+

+ -

+ + + +

+ +

+ + +

KCl AgCl
+

AgCl

+ +

+ - + + + + + + + + +

AgNO3
+ + + +

+ +

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