Chap 5 Transport Properties

Lecture notes of Chin-Hsiang Cheng

 Properties

Transport properties- μ (viscosity), k (thermal conductivity), D (mass diffusivity), θ (electrical conductivity)

Thermodynamic properties- P, v, T, s, h, u, cp, cv, c, μJ, β, ………..

 Mean Free Path - the average distance travelled by a moving particle between two
successive collisions.

Collision cross section (σ)

σ = 4πr2

2r
v� t
v� v�

σ = 4πr2
r 2r
An average molecule among molecules
 Electron collides with molecules

πr2 = σ/4

r
v� t
v� v�

r
σ = πr2
An electron of zero radius moving
r
among molecules
1. Swept volume of an average molecule in time t: σ v� t (= 4πr2 v� t, if molecule among molecules)

2. Number density of molecules: n

3. Number of molecules colliding with an average molecule in time t: σ v� t n

4. Collision frequency:

σvtn
Z= = σ v� n
t

5. Mean free path:

Travelling distance in time 𝑡𝑡 vt 1

λ= = = (molecular mean free path)
Number of collisions in time 𝑡𝑡 σvtn σn
1 4
λe = 1 = (electronic mean free path)
4
σn σn
Free Path Distribution

N: Number of molecules which are NOT collided yet

t=0, N=No N(t)

dt

molecule NOT collided

molecule collided
 Free Path Distribution
N: Number of molecules which are NOT collided yet

dx: average travelling distance of molecules in dt dx

dN ~ - N dx
x=0 x x+dx
Therefore, let dN = - Pc N dx
No N N-dN
dN
= - Pc N (Pc: Proportionality constant
dx No is number of tagged molecules, and dNe is the
or collision probability) number of tagged molecules which are collided
between x and x +dx. x is the travelling distance.
Initial condition: x = 0, N=No

N = No 𝑒𝑒 −Pc x -- Survival equation

dN = - Pc N dx where N = No 𝑒𝑒 −Pc x
dx
Thus,

dN = - Pc (No 𝑒𝑒 −Pc x ) dx
x=0 x x+dx
dN represents the number of molecules with free paths of
length between x and x+dx. dN can take the positive sign No N N-dN
since only the number is concerned. That is,
N
−Pc x
dN = Pc (No 𝑒𝑒 ) dx (Pc needs to determine) No
∫xdN ∫ x Pc No 𝑒𝑒 −Pc x dx 1
Mean free path: λ = = = , 1.0
No No Pc
1
Pc = =σn
λ
0.367
Therefore x
1.0 1.2 λ
x x
− N −
N = No 𝑒𝑒 λ or No
= 𝑒𝑒 λ Note: The fraction with free path longer than the
mean is 36.7%.
 x
No − λ
And, dN = − 𝑒𝑒 dx
λ

dN x
1 −λ
(1) = − 𝑒𝑒 dx
No λ

dN x
No − λ
(2) =− 𝑒𝑒
dx λ
Example 1
Compute the average speed, root mean square speed, and most probable speed for
oxygen molecules at 0oC.
32 kg/kmol
Sol: The mass of an oxygen molecule is m= 6.025×1026 molecules/kmol = 5.31×10-26 kg/molecule
k = 1.38×10-23 J/molecule-K

(1) Average speed

1.128 2.55kT 1.38×10−23×273 m
v� = = = 2.55 = 426 m/s β=
β m 5.31×10−26 2kT

(2) Root mean square velocity

1.224 3.0 kT 1.38×10−23×273
vrms = = = 3.0 = 461 m/s
β m 5.31×10−26

(3) Most probable velocity

1 2kT
vmp = = = 377 m/s
β m
Example 2
Compute for oxygen at 0oC (a) the collision frequency of the molecules and (b) The mean free
path.

Sol: (a) At at 0oC, the number of molecules per cubic meter is 3×1025. The radius of oxygen
molecules is about 1.8×10-10 m. The mass of an oxygen molecule is 5.31×10-26 kg .

Average speed: v� = 426 m/s

Collision cross section: σ = 4πr2 = 4π(1.8×10-10 )2 = 4×10-19 m2

Collision frequency: Z = σ v� n = 4×10-19 × 3×1025 × 426 = 5.1×109 collisions/s

1 1.
(b) Mean free path : λ = = 4×10−19 × 3×1025 = 8×10-8 m
σn
Viscosity - a fluid resistance to flowing

(1) Liquids – intermolecular attractive forces

Viscosity of a liquid arises due to strong intermolecular forces existing between the
molecules. Stronger the intermolecular forces, greater is the viscosity.

Temperature ↑ Viscosity ↓

(2) Gases – exchange in momentum between the fluid layers

Temperature ↑ Viscosity ↑
For Solids, Hook’s law- Stress ~ Strain τ~ε

For fluids, Stoke’s law- Stress ~ Rate of Strain τ ~ ε̇

(1) For parallel flows with u=u(y) only

du
τ=µ (Newtonian fluids)
dy

n−1
du du
τ=µ (Non-Newtonian fluids or power-law fluids)
dy dy

(2) Net momentum transport per unit time between the fluid layers: F (force)

Net momentum transport per unit time per unit area: F/A = τ (stress)
Goal: Moving plate

Find the 𝐚𝐚verage height above S-S plane, y� , at which the

y
molecules make their last collision before crossing S-S plane. Upper
space
du S
F=µA S
dy
du
F/A = τ = µ ≡ Net momentum transport per unit time
dy
per unit area Stationary plate

Z Collision frequency Z = σ v� n

n Number density y
dV

(1) Total number of molecules in dV: ndV θ

Upper
r Height=rcosθ
(2) Total number of collisions in dV in time dt: (ndV) Z dt/2 space

(The factor ½ appears because otherwise each collision dω

would be counted twice.) S S
dA
(3) Total number of free paths originating from dV in time dt: (ndV) Z dt
(Each collision generates two new free paths.)

(4) Solid angle associated with dV: dω = dAcosθ/r2

dω
(5) Number of free paths originating from dV in time dt and heading toward dA: (ndV) Z dt ( )
4π

(6) Number of free paths originating from dV in time dt and surviving to cross dA:
r r
dω − 1 −
d3Nt = (ndV) Z dt ( ) (𝑒𝑒 λ ) = Zn dA dt sinθ cosθ 𝑒𝑒 λ dθdφdr
4π 4π
(dV=r2sinθdθdφdr, dω = dAcosθ/r2)

(7) Total number of free paths from all directions, travelling all distances, and surviving to cross dA in
time dt:
π r
1 ∞ − 1
Zn dA dt ∫02 sinθ cosθ dθ ∫0 dφ ∫0 𝑒𝑒 λ dr = Z n λ dA dt
2π
Nt =
4π 4
 Moving plate
8 The average height:

π
∞ y d3N 1 Z n λ2 dA dt 2
∫2
2π λ
∫0 ∫0 2 3
y� = 0 t
= 61 = λ MU
u
Nt Z n λ dA dt 3 S S
4 2 ML
- λ
3 du
2 2 du dy
9 Representative velocity at y = y� = λ: u + λ
3 3 dy
Stationary plate
2 2 du
Momentum carried by a molecule from y = y� = λ: m(u + λ )
3 3 dy
1 �
No. of molecules crossing S-S plane per unit area per unit time: nV
4

u(y) hydrodynamic velocity

�
V average molecular velocity
(10) Momentum carried by all molecules crossing S-S plane from upper space per unit
area per unit time:
1 � 2 du
M U= n V m(u + λ )
4 3 dy

Similarly, momentum carried by all molecules crossing S-S plane from lower space per
unit area per unit time:
1 � 2 du
ML= n V m(u - λ )
4 3 dy

(11) Net momentum transport per unit time per unit area:

du 1 � du
F/A = τ = µ = MU – ML = nV mλ
dy 3 dy

1 � 1 mV� 2 2 1 mKT
Therefore, viscosity µ = nVmλ = =
3 3 σ 3 σ π
 High temperature wall TH
Thermal conductivity
2 2 dT
1 Representative temperature at y = y� = λ: T+ λ
3 3 dy 2
3
λ
EU
S T S
1 3
Energy ε = mV 2 = KT EL
2 2 -
2
3
λ
dT
dy
2 3 2 dT
Energy carried by a molecule from y = λ: K(T + λ )
3 2 3 dy Low temperature wall TL

1 �
No. of molecules crossing S-S plane per unit area per unit time: nV
4

(2) Energy carried by all molecules crossing S-S plane from upper space per unit area per unit time:
1 �3 2 dT
EU= n V K(T + λ )
4 2 3 dy

Energy carried by all molecules crossing S-S plane from lower space per unit area per unit time:
1 �3 2 dT
EL= n V K(T - λ )
4 2 3 dy
(3) Net energy transport per unit time per unit area:

dT 1 � dT
Q/A = q =k = EU – EL = nV Kλ
dy 2 dy

1 � 1 V� K K 2KT
Thermal conductivity k = nVKλ = =
2 2 σ σ πm
Coefficient of Diffusion
Diffusion of purple dye in water, DAB

Without random, molecular (thermal)

velocity, the molecules are not able to
‘diffuse’ to other specifies.

Interdiffusion coefficient DAB Self-diffusion coefficient DA of some gases at 273 K and 0.1 MPa
 Self-diffusion coefficient
n’ total number density (tagged+normal)
Assume that it is possible to “tag” certain molecules n(x) number density of tagged molecules
so that they can be distinguished from others. Note
that all the molecules (tagged+normal) are alike in
the self-diffusion problem. 1
tagged normal
S
2

S
S
3
dV
n(x)

x=0, n=no dn
dn
Assume (1) > 0, and (2) at x=0, n=no
dx r dx
dn
dA n@x = n(x) =no + x
θ dx
x dn
rcosθ n@dV = n(x) =no + rcosθ
dx
S
(1) Since the concentration of tagged molecules in the left space of S-S plane is greater than that
in the right, the number of tagged molecules crossing the plane from left to right will exceed
that from right to left.
(2) The net number crossing S-S plane in positive x-direction (from right to left) per unit area and
per unit time is denoted with Γ. Let

dn
Γ = -D where D is the coefficient of self-diffusion to determine.
dx

(3) Total number of free paths originating from dV in time dt: (n’dV) Z dt

(4) Number of free paths of tagged molecules originating from dV in time dt:
n
( )(n’dV) Z dt = Z n dV dt
n’

(5) Number of free paths of tagged molecules originating from dV and surviving to cross dA in
time dt:
r r
1 − 1 dn −
d3Ntag = Z n dA dt sinθ cosθ 𝑒𝑒 λ dθ dφ dr = Z (no + rcosθ ) dA dt sinθ cosθ 𝑒𝑒 λ dθ dφ dr
4π 4π dx
dn
[n(x) =no + rcosθ ]
dx
(6) Total number of free paths of tagged molecules from all directions from left space, travelling
all distances, and surviving to cross dA in time dt:
π
2π ∞
Ntag = ∫02 ∫0 ∫0 d3Ntag
π r
1 dn ∞ −
Z dA dt ∫02 sinθ cosθ (no + rcosθ
2π
= ) dθ ∫0 dφ ∫0 𝑒𝑒 λ dr
4π dx
1 1 dn
= Z no λ dA dt + Z λ2 dA dt
4 6 dx

(7) Total number of free paths of tagged molecules from all directions from left space, travelling all
distances, and surviving to cross S-S plane per unit area per unit time:

1 1 dn
ΓL = Ntag /dAdt = Z no λ + Z λ2
4 6 dx

Similarly, total number of free paths of tagged molecules from all directions from right space,
travelling all distances, and surviving to cross S-S plane per unit area per unit time:

1 1 dn
ΓR = Z no λ − Z λ2
4 6 dx
(8) The net number crossing S-S plane in positive x-direction (from right to left) per unit area
and per unit time is

dn 1 dn
Γ = ΓR - ΓL → -D = − Z λ2
dx 3 dx

1 1� 2 1 2KT
Therefore, D= Z λ2 = V λ=
3 3 3 n′ σ πm
 Electrical Conductivity
When a gas is placed in an electric field of strength E, in
V/m, each charged particle experiences a force given by

F=qE

where q is the electric charge on the particle. In a uniform

electric field the velocity of an electron, ve, with charge – e
A part of molecules in a gas that have
is given by
large translational energy. When these
e high-energy molecules collide, some
ve = - E t (obtained from F=ma and at t=0, ve = 0) collisions cause ionization; that is, an
me
electron is separated from its molecule
Similarly, the velocity of a singly charged ion, vi, is given by
so that a negatively charged electron
e and a positively charged ion are created
vi = - Et (obtained from F=ma and at t=0, vi = 0) from the neutral atom.
mi
ne number density of electrons
ni number density of ions

ne = n e
 Note that mi >> me, thus ve >> vi → It is appropriate to neglect the velocity of ions.

Drift velocity of the electrons, ved, is defined as

Mean distance traveled in the electric field between collisions

ved =
Mean collision time
mi/me = 1840 M, and M is the atomic weight
of the ion.
x� 𝑑𝑑
=
τ𝑒𝑒
e
Since ve = - E t, the distance traveled between two collisions
me

1 eE 2
is xd = - t
2 me

(1) Mean distance traveled in the electric field between collisions

1
x� 𝑑𝑑 = - x dN where N is number of molecules which are NOT collided before time t, and dN
Ne ∫ d
represents the number of molecules which are collided between t and t+dt.
distance traveled between
two collisions
When electric current in a material is proportional to the
voltage across it, the material is said to be "ohmic", or to obey
Ohm's law. A microscopic view suggests that this
proportionality comes from the fact that an applied electric
field superimposes a small drift velocity on the free electrons in
a metal. For ordinary currents, this drift velocity is on the order
of millimeters per second in contrast to the speeds of the
electrons themselves which are on the order of a million meters
per second. Even the electron speeds are themselves small
compared to the speed of transmission of an electrical signal
down a wire, which is on the order of the speed of light, 300
million meters per second.
ved : drift velocity ~ 0.001 m/s

ve : speed of electrons ~ 1,000,000 m/s

(vt : speed of transmission of an electrical signal ~ 300,000,000 m/s )

4
λ e = ve τ e = (speed of electrons themselves dominates)
σn
Electrons moving in a uniform electric field

ved

ve >> vi

→ The velocity of ions is assumed to be zero. Thus, ions or molecules are assumed to be
stationary (fixed lattice no matter the molecules are in gas, liquid or solid phase).
 2 Mean collision time

Distribution of collision times:

N: Number of molecules which are NOT collided yet before time t

dt: collision time interval

dN ~ - N dt

Therefore, let dN = - Pa N dt

dN
= - Pa N (Pa: Proportionality constant)
dt

Initial condition: t = 0, N=Ne

N =Ne 𝑒𝑒 −Pa t -- Survival equation

The distribution of collision times is identical to the distribution of free paths.

dN = - Pa N dt where N = Ne 𝑒𝑒 −Pat dt

Thus
t=0 t t+dt
dN = - Pa (Ne 𝑒𝑒 −Pat ) dt
Ne N N-dN
dN represents the number of molecules which are collided
between t and t+dt. dN can take the positive sign since only
the number is concerned. That is,
N
Ne
dN = Pa (Ne 𝑒𝑒 −Pat ) dt (Pa needs to determine)
1.0
dN ∫t ∫t Pa (Ne 𝑒𝑒 −Pat ) dt 1
Mean collision time: τe = = =
Ne Ne Pa
1
Pa = 0.367
τe t
Therefore 1.0 1.2 τe
The distribution of collision times is identical to the
t
−τ N t
−τ distribution of free paths. The fraction with
N = Ne 𝑒𝑒 e or Ne
= 𝑒𝑒 e collision time longer than the mean is also 36.7%.
 Ne − τt𝑒𝑒
And, dN = − 𝑒𝑒 dt
τ𝑒𝑒

dN 1 − τt𝑒𝑒
(1) = − 𝑒𝑒 dt
Ne τ𝑒𝑒

dN Ne − τt𝑒𝑒
(2) =− 𝑒𝑒
dt τ 𝑒𝑒
 x� 𝑑𝑑
ved =
τ𝑒𝑒
− 1 ∫ xd dN
= Ne
τ𝑒𝑒
− 1 ∫(− 1 m eE t2)dN
= Ne 2 e
τ𝑒𝑒
1 1 eE N t
− ∫(− m t )(− τ𝑒𝑒 𝑒𝑒 τ𝑒𝑒 dt)
2 e −

= N e 2 e
τ𝑒𝑒

1 eE 1 ∞ 2 − τt𝑒𝑒
=− t 𝑒𝑒 dt
2 me τ2𝑒𝑒 ∫0 x� 𝑑𝑑

eEτ𝑒𝑒
=− x� 𝑑𝑑
me
Drift velocity of electrons ved = τ
𝑒𝑒
4 τ𝑒𝑒 is the same.
( λe = = ve τ𝑒𝑒 )
σn
Thermal velocity of electrons ve = λe
τe
eEλe
=−
meve
 eEλe
ved =−
meve

eE meπ 4 2 8kT 4
=− ve = = λe = , and n is number density of molecules.
me 8kT σ n β π meπ σn

4eE πkT
=− pressure P = (m N 𝑉𝑉� 2 )/(3 Ɐ) = nkT
σ nkT 8me

4eE πkT
=−
σP 8me

This equation is valid only when collisions between electrons and neutral
molecules occur much more frequently than collisions between electrons and
electrons or other charged particles, i.e. ions. Also, it is required that the drift
velocity be small compared with the thermal velocity.
 dL
e (a) dL= ved dt or = ved
dA dV dt

dL=ved dt (b) dV=dA⋅dL

(1) J = Current density = The flux of charge per unit time = θ E [A/m2]
where θ is electrical conductivity in 1/Ωm; E is strength of electric field in Volt/m

(2) Charge across dA in dt: (- ne e) dV = - ne e dA dL

− ne e dA dL
(3) Rate of charge across dA per unit time: = - ne e ved dA
dt

4eE πkT 4e2E ne πkT e2E ne 2πkT

(4) Flux of charge per unit time: J = - ne e ved = (- ne e) (− )= =
σP 8me σP 8me σP me

e2E ne 2πkT e2 ne 2πkT e2 ne 2π

From (1) and (4), θ E = , Electrical conductivity θ = =−
σP me σP me σn kTme