Tema_5
Tema_5
Tema_5
• In other cases, atoms are added from the material’s environment, or atoms
from the material may be discharged into the environment.
• The probability of having one atom of sufficient energy E*, greater than the average energy, E, of all atoms
in a closed system at a particular temperature T is:
Pr obability = Ce−(E*−E) / kT
• C = constant, n
• k = Boltzmann constant = 1.38 x 10-23 J/(atom K) = C e− E*/ kT
Ntotal
• T = absolute temperature (K)
• The fraction of atoms n/N having energies greater than E*
Arrhenius Plot
Arrhenius equation: Expresses the thermal
energy required for atoms to diffuse
Q E
− RT − kT
rate = Ce = Ce
Where:
• Q = activation energy (J/mol; cal/mol)
• E = energy of atom
• R = molar gas constant
• 8.314J/(mol K); 1.987 cal/(mol K)
• k = Boltzman constant
• (k = 13.8 x 10-24 J/atom/K)
• T = absolute temperature (K)
• C = constant
Rate Equation
• The rate equation is rewritten in a logarithmic scale
ln (rate) = ln constant - Q
RT
n E
ln = ln C −
N total kT
• Activation energy is the energy barrier that must be overcome by thermal activation.
Example
• For example, the rate of oxidation of a magnesium alloy is represented by
a rate constant, k. The value of k at 300°C is 1.05 * 10-8kg/(m4 s). At 400°C,
the value of k rises to 2.95 * 10-4kg/(m4 s). Calculate the activation
energy, Q, for this oxidation process (in units of kJ/mol).
Example
• Taking the ratio of rate constants at 300°C (= 573 K) and 400°C (= 673 K),
we conveniently cancel out the unknown preexponential constant, C , and
obtain
or
Steady-State Diffusion: Definition
Steady-State Diffusion: Fick’s First Law
• Concentration gradient, dc/dx
c
D = diffusion coefficient J = −D
x
Temperature Dependence on Diffusion Coefficient
• Diffusion mechanism
• Type of diffusion
• Operational temperature
• Type of crystal structure
• Type of imperfections
• Bonding energy of the matrix atoms
Transient Diffusion: Fick’s 2nd law
• Non-steady state d dc x
= (J x )= D
dc x d
dt dx dx dx
• Time-dependent diffusion
cs − c x x
= erf
• Concentration profile as cs − c0 2 Dt
function of time:
Error Function