Tutorial

5 PH4603 Thermal Physics

Discussion date: 3 April 2017

Problem 1: A single charged surface in a monovalent salt solution

The Poisson-Boltzmann equation for a monovalent salt solution (such as NaCl

dissolved in water) is given by

Show that a solution is given by

where is the Debye length. A surface with charge density -s0

(where s0 > 0) is immersed in the solution at x = 0. By applying a suitable
boundary condition, show that the value of g is given by

where is the Gouy-Chapman length. For the case where l = 0,

determine the density distributions n+(x) and n-(x) for the counterions and co-ions
respectively. Make plots of these distributions.

Problem 2: Two charged surfaces in a monovalent salt solution

Two surfaces, each having the same charge density -s0 (where s0 > 0), are
immersed in a monovalent salt solution at x = -d/2 and x = d/2. The counterions
and co-ions each have a number density n0 at x = 0. We shall assume that the salt
concentration is sufficiently low, so that we can use the Debye-Hckel equation,
viz.,

where is the Debye length. By writing

and applying two suitable boundary conditions, solve for Y. Determine the density
distributions n+(x) and n-(x) for the counterions and co-ions respectively, to linear
order in s0.

Problem 3: Equilibrium separation of two charged surfaces

In Lesson 16, we derived the disjoining pressure between two charged surfaces in a
counterion-only solution. Now consider the case of two flat surfaces maintained at
an equilibrium distance d by a pressure of 10 atm in pure water (whose relative
dielectric permittivity is 80) at T = 300 K. The surfaces each have a charge density
s = -0.04 C m-2, whilst the counterions are monovalent. Find d.