Colloids and Rheology

Lecture 2

Electrostatic forces between

surfaces in liquids

Mike Adams (m.j.adams@bham.ac.uk)

Surface charging

There are two mechanisms of surface charging:

• Ionisation or dissociation of surface groups eg –COOH  COO– + H+ leaving a

negatively charged surface.
• Adsorption or binding of ions from solution onto a neutral surface.

The final surface charge is balanced by an equal and oppositely charged region of
counterions, some of which may be bound transiently to the surface, within the Stern
or Helmholtz layer. Others form an atmosphere of ions in rapid thermal motion close
to the surface, known as the diffuse electrical double layer.

Ions in solution with the same sign as the charged surface are known as co-ions.
The diffuse electrical double layer

Negatively charged
surface Co-ion

 x 
  x     exp  
1 
Counter-ion
  
 0   
  1     e 1  0.37 
The Guoy-Chapman model of the diffuse double layer I

 Consider a uniformly cha rged flat surface x dependence only 

 Ions treated as poi nt cha rges where ni 0 is the number of ions per unit
volume of type i in the bulk electrolyt e x   
 The chemical potential of the counterions in solution is given by the
Boltzmann distributi on :
  zi e  x   k T ln ni x   consta nt
 
e  cha rge on a proton 1.602 10 19 C where C  Coulomb  s A , zi  ionic valancy
eg z  1 for a monovalent cation and z  2 for a divalent anion  and
 x  is the electrostatic potential volts : 1 V  1 J C 1 .
     0 (by definition si nce only differences are importa nt ) and ni    ni 0
Thus the Boltzmann distributi on gives the ion density at x :
 z e  x  
ni  ni 0 exp   i  (1) Nernst equation 
 kT 
 Counterion cha rge is opposite to that of   x . For the counterions , this means that
ni / ni 0  1
The Guoy-Chapman model of the diffuse double layer II
The Guoy-Chapman model of the diffuse double layer III

 Total number of cha rges per unit volume (net cha rge density ) :
   ni zi e we consider a symmetric electrolyt e : z    z   z 
i

  z e  x    z e   x    z e  x  
From 1,   n0 z e exp     exp    2 n0 z e sinh   2
  kT   k T   kT 
 
given that sinh  x   e x  e  x / 2
 Poisson ' s equation gives the net excess cha rge density at x :
d 2 ψ x  
  (3)
dx2  0

where  0  8.85 10 12 F m 1 where F  C/V is the 
permittivi ty of a vacuum and  is the factor by which a liquid medium
reduces the strength of an electric field because of alignment of molecular
dipoles acting to cancel the part of the field   80 for pure water . It is
known as the relative permittivity or dielectric consta nt.
The Guoy-Chapman model of the diffuse double layer IV

d 2 ψ  x  2 n0 z e  z e x  
 From 2  and 3 :  sinh   4 
dx 2
 0  kT 
For   x   25 mV z e   x  / k T  1, sinh  x  ~ x. Then ( 4) may be written as :
d 2 ψ  x  2 n0 z e 
2
   x  (5) with bcs :      and        0, 5 yields :
dx 2
 0 k T
  x    exp   x  6  where  is the dist ance to the Stern layer .
Eq. (6) is the Debye  Huckle approximation and  is the Debye  Huckel parameter
 2 n 0 z e 2
1/ 2 1/ 2
  2000 e 2 N A c z 2 
     m with c  conc. in mol/dm 
-1 3

   0 k T    0 k T 
mol 1 mol 1
Note : n0  c N A  10 3
c N A  number per unit volume
dm 3 mol m 3 mol
For unsymmetric electrolyt es : z  the ionic valency of the counter  ions.
NB  depends on concentration via n0 and ionic valancy via z.
The parameter  1 nm  is known as the Debye length and correspond s
to the dista nce from the Stern layer at which the potential has reduced to 37% of  .
It decreases with increasi ng electrolyt e concentration and increas ing valency.
The zeta potential

 The zeta   potential is that at the shear plane if an electrolyt e is flowing over
a cha rged surface.  ~  and  is easy to measure and so is used in calculatio ns.
 
 Cha rge density   C m  2 at Stern layer may be calculated usi ng Poisson ' s equation 3
given the requiremen t for electroneutrality (total char ge of the counterions in double layer
is equal and opposite of the cha rge at Stern layer ) :

  d  x 
2
d  x 
     d x    0  d x    0
  d x2 dx 
d d
Since      0,      0
dx
and E 
dx

   /   0 is the electric field V m 1 
 From 6 , at x   :
d x 
    exp         for    0
dx 
Thus :        0       0  and hence  ~ 
Coulombic forces or charge-charge interactions

 The free energy for the Coulombic in teraction between two cha rges Q1 and Q2 :
z1 z 2 e 2
wr  
Q1 Q2
 (J ) (units of cha rge  C  s A)
4  0  r 4  0  r
where r is the dist ance between the two cha rges (equivalent to the sum of the
 
radii of the two ions and  0  8.85 10 12 C 2 J 1m 1 or F m 1 where F  C/V .
 The Coulomb force is given by :
d w r  Q1 Q2 z1 z 2 e 2
F    ( N)
dr 4  0  r 2 4  0  r 2
for like cha rges both w and F are positive so that the force is repulsive.
Note that both w and F are less in water, for example, than in a vacuum.
Learning outcomes – Lecture 2

• Origin of surface charging.

• Draw a diagram showing the way in which the potential
changes with distance for a diffuse electrical double layer.
• Understand the Guoy-Chapman model of the diffuse double layer
and the way in which the ion concentration changes with distance from
the Stern plane.
• The Debye length and its dependence on concentration and ionic valency.
• Origin of the zeta potential
• Charge-charge interactions.