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Transport phenomena

Basel, 2008

6. Transport phenomena

1. Introduction

2. Phenomenological equations for transport properties

3. Transport properties of a perfect gas

4. Diffusion in a fluid

5. Measurement of the diffusion coefficients, viscosity and thermal

conductivity

References:

•P. Atkins, J. de Paula, “Atkins‘ Physical

Chemistry”, Oxford Univ. Press, Oxford, 8th

ed., 2006, Chapter 21.

• I. Tinoco, K. Sauer, J.C. Wang, J.D. Puglisi

Supplementary material: “Physical Chemistry, Principles and

German version for this applications in biological sciences”, Prentice-

chapter (Prof. Huber lecture Hall, New Jersey, 4th ed., 2002, Chapter 6.

from 2007).

6.1 Introduction

matter, energy or some other properties, from one place to another.

¾ Thermal conduction: migration of energy down a temperature gradient

¾ Electric conduction: migration of electric charges along an electric

potential gradient

¾ Viscosity: migration of linear momentum down to a velocity gradient.

(empiric equations obtained from a summary of experiments and

observations)

6.2 Phenomenological equations

in a given interval of time/(area and duration of time).

Types of flux:

- Matter flux: if the matter is flowing through the area in the interval of

time > number of molecules/(m2 s).

- Energy flux: if energy is flowing through the area in the interval of time

> J/(m2s).

property is proportional to the first derivative of a related property

(gradient of the property).

6.2.1 Fick first law of diffusion

Fick first law of diffusion: the flux of matter which diffuse parallel with the

direction Oz in a container, is proportional to the concentration gradient.

N - number density of molecules

dΝ

( )

(6.1)

J matter ∝ z – distance where there is a flux of matter

dz [J] = nr. /m2s

steeply with position > diffusion

process is fast.

- If the concentration is uniform > flux of

matter is 0 > no diffusion.

Fick first law of diffusion

J<0 flux towards -Oz direction

perfect gas:

dN (6.2)

J (matter ) = − D

dz

6.2.2 Thermal conductivity

motion) is proportional to the temperature gradient:

J (energy ) ∝

(6.3)

Joule!

dz

Similar to the diffusion relation, the flux of energy due to the thermal

motion is :

k = coefficient of thermal

dT (6.4)

J (energy) = −k conductivity

dz [k] = J/(K m s) where J = Joule!

6.2.3 Viscosity

Hypothesis: A Newtonian fluid is formed by a series of layers moving past

one another, in a tube/container.

- the layer next to the wall is stationary

- the velocity of the succesive layers depends on the distance from the wall.

momentum they have in their original layer (initial layer) to the layer in

which they move (final layer).

retarded, dependng on the linear

momentul of the molecule.

Viscosity

It depends on the transfer of x-component of linear momentum (flux in the

Oz direction) into the layer of interest.

dv x

J ( x − comp − momentum) ∝ (6.5)

dz

Similar to the diffusion relation, the flux of energy due to the thermal

motion is :

(6.6) η = coefficient of viscosity (or

dv x

J ( x − comp − momentum) = −η

viscosity)

dz [η ] = kg/(m s) or Poise (P)

1P = 10-1 kg/m s

Thermal conductivity and viscosity

6.3 Transport properties of a perfect gas

Model: simple kinetic theory of gases

Diffusion coefficient, D:

(6.7) λ- mean free path of particles

1

D = λc c - mean speed of the particles in a

3 gas

coefficient is decreasing. Gas molecules diffuse more slowly

than the pressure is high.

¾ c increases with the temperature > diffusion coefficient is increasing with

the temperature. Molecules in a hot sample diffuse more quickly

than in the case of a cool sample.

D is greater for small molecules, than for large molecules (because the

mean speed of the particles is inverse proportional to the mass of the

particles).

6.3.1 Thermal conductivity – perfect gas

λ- mean free path of particles

c - mean speed of the particles in a

(6.8) gas

k = λc Cv,m [A]

1

[A] - molar concentration of the gas

3 molecules

Cv,m – molar heat capacity at V

constant.

λ decreases as the pressure in the gas is increasing

k ≠ f(pressure)

λ decreases as the molar concentration of the gas is increasing

temperature corresponds to a higher variation of energy.

6.3.2 Viscosity – perfect gas

Viscosity, η: λ- mean free path of molecules

c - mean speed of molecules in a

gas

(6.9)

η = Mλc [A]

1 [A] - molar concentration of the gas

molecules

3

M – molar mass of molecules

increasing as temperature increases (for gases).

[A] increases as the molar concentration of the gas is η ≠ f(pressure)

increasing

6.3.3 Transport properties for gases

c k ηCv k

(m s-1)

Transport properties for gases

Units

m2 s-1

kg m-1 s-1

Diffusion coefficients for various media

Substance and

diffusion medium

H2 in H2

Xe in Xe

H2 in air

I2 in air

NaCl in H2O Na+

NaCl in H2O Cl-

ethanol in H2O

Ag in Cu (6.55 mol%)

Cu in Zn (75 mol%)

P=1bar

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