Chapter 1: Molecular Diffusion
Learning Objectives
Explain the physical significance of molecular diffusion and its
role in mass transfer processes
Apply Fick's first and second laws to analyze steady and
unsteady diffusion problems
Calculate diffusivity coefficients for gases and liquids under
various conditions
Analyze equimolar counter diffusion and its practical
implications in gas mixtures
Evaluate the impact of chemical reactions on diffusion rates and
develop corresponding models
Determine mass transfer coefficients and relate them to diffusion
phenomena in engineering systems
Introduction
Imagine a scenario where a harmful gas leak occurs in a crowded
industrial plant. Understanding how the gas spreads through the air
can mean the difference between a safe evacuation and disastrous
consequences. This spread—a process referred to as molecular
diffusion—governs how molecules move from regions of high
concentration to low concentration, ensuring that substances naturally
balance out over time.
In the realm of mass transfer operations, mastering molecular
diffusion is essential for designing efficient systems in:
Chemical reactors
Environmental control systems
Material processing
Pharmaceutical manufacturing
Biological systems
In this chapter, we will explore the fundamental principles that
describe this invisible but vital phenomenon. From Fick's laws that
mathematically quantify diffusion rates to the effects of chemical
reactions and concentration gradients, you will gain the tools needed
to predict and manipulate diffusion in gases and liquids alike.
1. Introduction to Molecular Diffusion
Molecular diffusion is the process by which particles move from a
region of higher concentration to a region of lower concentration due
to their random thermal motion. This spontaneous movement causes
mixing of different species without any bulk fluid motion.
Everyday Examples of Diffusion
Example Description
When you spray perfume in one corner, you
Perfume in a room eventually smell it throughout the room, even
without air currents
Sugar dissolves and spreads evenly in hot tea
Sugar in tea
without stirring
Oxygen diffuses from lungs into blood and
Oxygen exchange
from blood into tissues
Food coloring Dye spreads uniformly in water over time
Important Distinction: Diffusion vs. Convection
Diffusion Convection
Microscopic movement of individual Bulk flow of fluid carrying
molecules species
Driven by pressure or velocity
Driven by concentration differences
gradients
Occurs even in stagnant fluids Requires fluid movement
Fast process over long
Slow process over long distances
distances
Key Concept: Diffusion always proceeds down a concentration
gradient from high to low concentration regions, aiming to reach
equilibrium.
Physical Intuition Behind Diffusion
Consider a container divided into two parts by a permeable
membrane. One side contains a high concentration of a gas, the other
side is less concentrated. Over time, gas molecules randomly move
and pass through the membrane, gradually equalizing concentrations
on both sides.
This movement is spontaneous and continues until the concentration
is uniform—diffusion is nature's way of balancing concentrations.
2. Steady and Unsteady Diffusion
The process of diffusion can occur in two fundamental ways
depending on how concentrations change over time:
Steady-State Diffusion
Steady-state diffusion occurs when the concentration profile does
not change with time. In other words:
The rate at which molecules diffuse remains constant
The spatial distribution of concentration is stable
Conditions are fixed at the boundaries
Characteristics:
∂C/∂t = 0 (no change with time)
Flux is constant
Uses algebraic equations
Example: Gas diffusing through a membrane with constant
concentrations on both sides
Unsteady-State Diffusion
Unsteady-state diffusion (also known as transient diffusion)
happens when concentrations vary both in space and time.
Characteristics:
∂C/∂t ≠ 0 (concentration changes with time)
Flux varies with time
Uses partial differential equations
Example: Dye dropped in water spreading over time
3. Fick's First Law of Diffusion
One of the most fundamental relationships describing molecular
diffusion is Fick's First Law. It relates the diffusive flux of a species
to the concentration gradient that drives the diffusion.
Mathematical Expression
Diffusive molar flux, denoted Jₐ, is defined as the amount of species
A passing through a unit cross-sectional area per unit time due to
molecular diffusion. Its SI units are mol/m²·s.
Fick's First Law states that the flux is proportional to the negative of
the concentration gradient:
The negative sign means that diffusion occurs from high to low
concentration, opposite the direction of increasing concentration.
Derivation of Fick's First Law
Consider steady diffusion of species A through a flat plate of
thickness L where concentration on one side is Cₐ₁ and on the other
side is Cₐ₂, with Cₐ₁ > Cₐ₂.
Under steady state, concentration does not vary with time and the flux
is constant across the plate.
The concentration gradient is assumed linear:
dCAdx=CA2−CA1LdxdCA=LCA2−CA1
Substituting in Fick's first law:
JA=−DABCA2−CA1L=DABCA1−CA2LJA=−DABLCA2−CA1
=DABLCA1−CA2
Assumptions of Fick's First Law:
1. Constant diffusivity
2. One-dimensional diffusion
3. No bulk flow of fluid
4. Steady-state conditions
Key Insight: The diffusion flux is proportional to the concentration
difference and inversely proportional to the distance.