Electrical double layer

Mrta Berka s Istvn Bnyai, University of Debrecen Dept of Colloid and Environmental Chemistry

http://dragon.unideb.hu/~kolloid/

2007.10.09

7. lecture

Adsorption of strong electrolytes from aqueous solutions

Stoichiometric or equivalent Indifferent surface Non-indifferent surface Non-stoichiometric or ion exchange Anion-, cation

apolar
Ashless charcoal , lyotropic series (Ionic charge and size, Strength of attraction to surface: Al3+ > Ca2+ = Mg2+ > K+ = NH4+ > Na+. For anions: CNS-> (PO4 , CO3=) > I- > NO3- > Br> Cl- > C2H3O2- > F- > SO4= )

polar

Electric double layer

Ionic crystal from its solution at a specific concentration

?? Which ion goes into the inner layer?

Electrical double layer

Surface Charge Density. When a solid emerges in a polar solvent or an electrolyte solution, a surface charge will be developed through one or more of the following mechanisms: 1. Preferential adsorption of ions. Specific ion adsorption: Surfactant ions may be specifically adsorbed. 2. Dissociation of surface charged species (proteins COOH/COO-, NH2/NH3+) 3. Isomorphous replacement: e.g. in kaolinite, Si4+ is replaced by Al3+ to give negative charges. 4. Accumulation or depletion of electrons at the surface. 5. Charged crystal surface: Fracturing crystals can reveal surfaces with differing properties. Which is the preferential adsorption of ions? On charged surface the ion of opposite charge The related ions The ions which form hardly soluble or dissociable compounds with one of the ions of the lattice The ion of larger valences H+ or OH-

Example: AgCl crystal AgNO3 or KCl solution AgCl crystal KBr, or KSCN solution From NaCl, CaCl2 solution : Ca2+ The free acid or base adsorb stronger than the electrolytes, because the mobilities of H + and OH- are larger.

http://www.dur.ac.uk/sharon.cooper/lectures/colloids/interfacesweb1.html#_Toc449417608

Surface charge
(Atkins: Physical Chemistry)
, Galvani or inner potential Volta or outer potential surface potential (from the orientation of solvent molecules) When silver iodide crystals are placed in water, a certain amount of dissolution occurs to establish the equilibrium: AgI = Ag+ + IThe concentrations of Ag+ and I- in solution are very small because the solubility product is very small (Ksp= aAg+ aI- =10-16). But these small concentrations are very important because slight shifts in the balance between cations and anions can cause a dramatic change in the charge on the surface of the crystals. If there are exactly equal numbers of silver and iodide ions on the surface then it will be uncharged. 7. lecture

100 nm

2007.10.09

Charge determining ions

cAg+<310-6 mol/l negative
The concentration of charge determining ions , mol/m2

The , C/m2 surface charge density changes from positive to negative or vice versa. Zerocharged surface is defined as a point of zero charge (p.z.c.) or zero-point charge (z.p.c.).

<0
cAg+>310-6 mol/l positive

>0

=0, p.z.c.

AgI in its own saturated solution is negatv! cAg+=cI- =8.7x10-9 mol/l

pAg+NTP = 5,3

Potential-determining ions
It seems that the iodide ions have a higher affinity for the surface and tend to be preferentially adsorbed. In order to reduce the charge to zero it is found that the silver concentration must be increased by adding a very small amount of silver nitrate solution about to:

cAg+<310-6 mol/l
The charge which is carried by surface determine its electrostatic potential. For this reason they are called the potential-determining ions.

0 + We can calculate the surface potential on the crystals of silver iodide by considering the equilibrium between the surface of charged crystal and the ions in the surrounding solution: Where 0 the electrostatic potential difference (arising form the charge bearers as ions, electrons) at the interface (x=0), shortly surface 0 PZC potential; a the activity of the ions and aPzc the activity of the ions at zerocharged surface in the solution. 9

F ( )

kT = ( ln a ln a ze
0 = 25.7 ln

kT 0 = ln a ze

8.7 10 = 150mV 6 3 10

AgI in its own saturated solution is negatv! cAg+=cI- =8.7x10-9 mol/l

2007.10.09 7. lecture

surface potential of silver iodide crystals placed in clear water

The structure of the electrical double layer

The model was first put forward in the 1850's by Helmholtz. The interactions between the ions in solution and the electrode surface were asssumed to be electrostatic in nature and resulted from the fact that the electrode holds a charge density which arises from either an excess or deficiency of electrons at the electrode surface. In order for the interface to remain neutral the charge held on the electrode is balanced by the redistribution of ions close to the electrode surface. Helmholtz's view of this region is shown in the figure

The overall result is two layers of charge (the double layer) and a potential drop which is confined to only this region (termed the outer Helmholtz Plane, OHP) in solution. The model of Helmholtz does not account for many factors such as, diffusion/ mixing in solution, the possibility of adsorption on to the surface and the interaction between solvent dipole moments and the electrode.

Helmholtz model

/V

0 0

surface potential

x (indiv.u.)

As simple as it is not valid

2007.10.09

7. lecture

Gouy-Chapman model
= 0 exp ( x )
/V 0 surface potential 0

1/

x (indiv.u.)

The ions would be moving about as a result of their thermal energy

1/ the thickness of the DL;

~I1/2 ionic strength
7. lecture

= 0 exp ( x )
2007.10.09

compact Stern layer

Stern model
In the Stern model the ions are assumed to be able to move in solution and so the electrostatic interactions are in competition with Brownian motion. The result is still a region close to the electrode surface (10 nm) containing an excess of one type of ion (Stern layer) but now the potential drop occurs over the region called the diffuse layer.

2007.10.09

7. lecture

Stern model, charge reversal

compact Stern layer

00

surface potential

/V
St d
Stern-p.

plain of shear x (indiv.u.)

potential PO432007.10.09 7. lecture

Stern model, charge increase

d Stern-p. St
/V
00 surface potential

potential

plain of shear x (indiv.u.) cationic surfactants

2007.10.09

7. lecture

Stern model
Finite ion size, specific ion sorption, compact layer

= St exp ( ( x xst ) )
: a Debye Hckel parameter 1/ the thickness of DL

n+ = n e

ze kT

n = n e

+ ze kT
xSt

the electrostatic interactions are in competition with Brownian motion in the diffuse layer
The whole DL is electrically neutral. 2007.10.09 7. lecture
xSt Plane of shear

n+ = n e

ze kT

n = n e

+ ze kT

the electrostatic potential for different salt concentrations at a fixed surface charge of -0.2 C/m2.

The potential distribution near the surface at different values of the (indifferent) electrolyte concentration for a simple Gouy-Chapman model of the double layer. c3>c2>c1. For low potential surfaces,the potential falls to 0/e at distance 1/ from surface.