BE 727 Lecture: Electrostatic Forces

Review from last time:

• Intermolecular and surface forces, motivated in the context of protein adsorption
• Forces have a distance range over which they act; can be repulsive or attractive
• Origin of van der Waals forces between ions and dipoles
C
wvdW (r ) = − vdW6
= −[Cind + Corient + Cdisp ]/ r 6
r
• Extending to macroscopic bodies by summing up all of the interactions reduces
the exponent of the distance dependence; Hamaker constant

Today’s lecture: electrical double layer forces (Ch. 12 in Israelachvili)

Goal:
Ø Determine how electrical potential and distribution of ions in electrolyte solution
varies with distance z from the charged interface
Ø Relationship between σo and ψo.
Ø This will tell us how interparticle repulsion or attraction = f(electrolyte type, [], T)

1. Electrical Double Layer

Definitions:
Ø How do molecules acquire charge? Charging mechanisms:
o ionization of suitable groups (carboxyl, sulfate, amino, etc.) – pH of the
solution
o specific adsorption of ions (e.g. ionic surfactants, Ca++, Mg++, ion exchange)
o phosphorylation – dephosphorylation
Ø Final surface charge is balanced by an equal but oppositely charged region of
counterions (charge regulation), some of which are bound (transiently) to the surface
within the Stern or Helmholtz layer, while others form an atmosphere of ions in
rapid thermal motion close to the surface, known as the diffuse electric double layer

Ø Definition of parameters: charge and potential

o ρ: volume charge density

p. 1
 o electrical potential (usually ψ)
§ potential energy (zeψ) of an ion in the local field where z is the
valence of the ion and e is the charge on the electron

2. Poisson-Boltzmann Equation
Ø Here, charges are free to move throughout volume of electrolyte in response to E and
thermal motion => combine Poisson equation and Boltzmann equation

Ø Poisson equation: relation between electrical potential Ψ and charge density in

vacuum:

∇ ψ = −ρ/ε
2

To use this equation in an electrolyte solution, you would have to evaluate

simultaneously all charge interactions (ion-ion, ion-dipole, dipole-dipole, etc.) which
becomes intractable. Assuming that ion-ion interactions dominate, and averaging over
solvent degree of freedom, eliminate ion-dipole and dipole-dipole interactions, we
come up with:
∇ ψ = −ρ/ε ε
2
ο

Ø Charge density per unit volume ρ at any location in the solution:

ρ= ∑ ni zi e (z = valence with appropriate + or -), ni = local
i
concentration of ions of type i, e = charge of electron

Units: ni = # ions / m3
molar concentration (moles/L) ==> ni = 1000 NAV n*

Boltzmann distribution: compromise between molecular order and

disorder. For ions in solution, the electrostatic energy of an ion of valence
zi at a point where the potential is Ψ is ==> zeΨ.
-zeψ/kT
==> Boltzmann equation: n=no e
===> n-=noezeψ/kT n+=noe-zeψ/kT

Ø Combine Poisson equation and Boltzmann equation ==> Poisson-Boltzmann equation

−1
∇ψ = 2
∑ nio z i e exp(− zi eψ / kT )
ε oε i

2nd order nonlinear differential equation.

Solving the P-B equation gives ρ(x), ψ(x), and E = dψ/dx at any point between surfaces.

p. 2
 1/ 2
2kT 1 + Γ o exp(−κ x) ⎛ e 2 ∑ nio zi2 ⎞
Result: ψ(x) = ln( ) ; where κ = ⎜⎜ ⎟⎟ (1/κ = Debye length)
ze 1 − Γ o exp(−κ x) ⎝ ε oε kT ⎠
exp( zeΨ o / 2kT ) − 1 zeΨ o
and Γo = = tanh( )
exp( zeΨ o / 2kT ) + 1 4kT

Approximate solution: electrical energy << thermal energy of ions, i.e. zeψ << kT; can
then expand the exponential of P-B
Recall: ex = 1 + x + x2/2! + x3/3! + x4/4! + ...
−1
∇ψ =
2
∑ nio zi e(1 − zi eψ / kT )
ε oε i
o
o electroneutrality: ∑n z e = 0
i
i i

1 ψ o 2
o ∇ψ = 2

ε oε kT
∑ n ( z e)
i
i i

1/ 2
⎛ e 2 ∑ nio zi2 ⎞
o κ = ⎜
⎜ ε ε kT ⎟⎟
⎝ o ⎠
2
o ==> ∇ ψ = κ Ψ 2

o Using B.C. that ψ -> ψo when x -> 0 (surface) and ψ -> 0 when x -> infinity
==> ψ(x) = ψoexp(-κx)
(also known as the Debye-Huckel approximation)

3. Debye-Huckel approximation
(approximation is good, but breaks down at smaller distances)
Note: May not always be possible to assume that |zeψ| < kT. Example: 1 V potential
difference is about 40 kT at room temperature. Under these conditions, must solve
complete P-B

Note that 1/κ is the distance at which the potential has reached the 1/e fraction of its
value at the surface and coincides with the center of action of the space charge.

κ = Debye-Huckel parameter
1/κ = Debye length (thickness of ionic atmosphere around each ion)
Distance over which ψ drops to ~ 1/e of its original value and is
approximate thickness of the diffuse electrical double layer

κ = (2000 F2/ εoεRT)1/2 (I)1/2 in units of m-1 = 3.288 (I)1/2 (nm)-1

F = Faraday’s constant (96485 C/mol)

1/ 2
⎛ ε ε kT ⎞
κ = ⎜ 2 o o 2 ⎟ (remember that ni is in # ions/volume)
−1

⎜ e ∑ n z ⎟
⎝ i i ⎠

p. 3
 The higher the salt concentration, and higher the valence of the salt ions, the
more rapidly the electrical potential decays away from the surface of the
particle.
1 2
I = ionic strength ( = ∑ z i ci ) where ci is the ionic concentration in mol/L
2 i
-3
Example: 10 M 1:1 aqueous electrolyte solution (NaCl), 1/κ = 9.6 nm
For colloid science, 1/κ ranges from a fraction of a nanometer to about 100 nm.
1/κ: 0.304/√[NaCl] nm for 1:1 electrolytes (e.g. NaCl)
0.176//√[CaCl] nm for 2:1 and 1:2 electrolytes (e.g., CaCl2 and Na2SO4)
0.152//√[MgSO4] nm for 2:2 electrolytes (e.g. MgSO4)

Analogous to a charged capacitor separated by a distance 1/κ with charge densities +/- σ
For NaCl, 1/κ = 30.4 nm (10-4M), 9.6 nm (1 mM), 0.96 nm (0.1 M), and 0.3 nm (1 M)

For pure water at pH 7, 1/κ or Debye length is 960 nm or about 1 µm

4. Electrostatic double-layer interaction between charged surfaces in electrolyte

(didn’t get to this part)
Ø Consider: plane surface with uniform positive charge density in contact with a
solution phase containing positive and negative ions
o If two such charged surfaces are brought close together, the ion concentration
between the surfaces is always higher than ρinfinity => osmotic pressure
operates between surfaces (together with E constitute force opposing the
approaching of the surfaces)

o At midplane, E is zero, for symmetry, and total force/unit area is the osmotic
pressure contribution ==> P = kT(ρm-ρinfinity)

p. 4
 •WE(D) for two flat surfaces

e2ψ m2 ρ ∞
Px (D ) ≈
kT
8kT ⎛ ΚD ⎞
ψm ≈ γ exp⎜ − ⎟
e ⎝ 2 ⎠
ze ψ o
P = 64kTγ 2 ρ ∞ exp(− K D ) γ = tanh ⎛⎜ ⎞
4kT ⎟
⎝ ⎠

64kTγ 2 ρ ∞
WE ( D) = − ∫ P d D = exp(− ΚD )
K

We can then add this to the vdW to get DLVO theory.

p. 5