SIMULATION OF ION TRANSFER UNDER

CONDITIONS OF NATURAL CONVECTION BY THE FINITE DIFFERENCE METHOD

By: Sachin Maskeen (10112042) Neha Madan (10210021) Rakesh Bhardwaj (10112037) Sandeep Kumar (10112045)

INTRODUCTION

Due to electrochemical reactions proceeding on the electrodes, the distribution of electrolyte species and, hence, the electrolyte density become nonuniform.

This causes a buoyancy force, which induces natural convection. The natural-convective electrolyte flow, in turn, changes the distribution of electrolyte species.

INTRODUCTION

Natural convection significantly raises the masstransfer rate and changes the distribution of the current density on the electrodes as compared with stagnant electrolyte.

Therefore, for simulating electrochemical systems, in which natural convection can arise, the equations of electrolyte species transfer and equations of liquid flow should be solved simultaneously

INTRODUCTION
Two ways of numerical solution of this system are known: (1) simultaneous solution of a complete system of nonlinear equations;
(2)

decoupling of a complete system of equations, and successive calculation of the distributions of electric potential and electrolyte species concentrations

MATHEMATICAL MODEL

In this, we use the Navier Stokes equations for an incompressible viscous liquid in the Boussinesq approximation,

Also the continuity equations are used for electrolyte species, which are derived within the framework of the theory of dilute electrolytes, and the condition of electro-neutrality

MATHEMATICAL MODEL

In the dimensionless form, the mathematical model is as follows:

MATHEMATICAL MODEL

where V is the vector of hydrodynamic velocity, t the time, p the pressure, zk , Dk , and ck the charge, the diffusion coefficient, and the concentration of the kth species, respectively, ckb the bulk concentration of kth species, r the electrolyte density, the electric potential, Rk the internal source associated with homogeneous chemical reactions, g the unit vector directed in the sense of free fall acceleration, Sc the Schmidt number, and Ra the Rayleigh number

MATHEMATICAL MODEL

The dimensionless variables are related to the dimensional ones as follows:

where H is the height of region of interest n the kinematic viscosity, F the Faraday constant, T the thermodynamic temperature

MATHEMATICAL MODEL

i.

To simplify the numerical solution, The hydrodynamic velocity is calculated at a given distribution of concentrations, and then, the system of continuity equations for the electrolyte species is solved

where Vx and Vy are the components of hydrodynamic velocity along the x and y axes, respectively, and is the Stream function

MATHEMATICAL MODEL

Now we bring the system to following form:-

Region of interest

METHOD OF SOLUTION

For the numerical solution of system the finite difference method was used.
In the rectangular region, a uniform grid with step h was constructed. The discretization of electrolyte continuity equations was realized by the explicit scheme i.e. Eulers Method using the central differences.

Scheme of discretization

METHOD OF SOLUTION

Discretized equation for internal grid nodes is

METHOD OF SOLUTION

Discretized equation for the boundary nodes of the first type located on the boundary segment 1

METHOD OF SOLUTION

Discretized equation for the boundary nodes of the second type located on the boundary segment 2

METHOD OF SOLUTION

Discretized equations for the boundary nodes of the boundary segment 3 and 4 will be same to the equations for 1 and 4 respectively. The set of difference equations is conveniently presented in the matrix form: