1.10.

2019

Chem 353 Ch 19. Molecules in motion

Physical Chemistry II
19A transport in gases: 19B motion in liquids:
• Diff. from gases (role of intermolecular
Part III. Change • Motion in fluid (liq. or gases)
• Transport properties
forces)
• Ion movement in sln with applied
• Matter, energy etc. potential
Chapters • Diffusion, thermal conduction, visc., eff. • Conductivities and mobilities of ions.
19 Molecules in motion
20 Chemical kinetics 19C diffusion: Impact:
21 Reaction dynamics • Thermodynamic force and diffusion “A great deal of chemistry, chemical
engineering, and biology depends on
22 Processes on solid surfaces • Solving diffusion eqn. the ability of molecules and ions to
• Role of random walk migrate through media of various
kinds.”
2019 Fall Semester

19A Transport in gases 19A.1 The phenomenological equations

• Need to realize a molecule can carry many properties through space
• Need to remember kinetic theory of gases (Review esp. Topic 1B)
• Be familiar with mean speed of molecules, what is mean free path
and its importance, dependence of mean free path to pressure.
phenomenological equations : empiric equations, terms derived from
observation without (initially) understanding its dependence to
molecular properties.
• common terms of fluid behaviors and properties
• Rate of migration of a property is measured by its flux, J.
• flux : amount of something crossing a surface in unit time.
o “something” can be water, wind, electric field, bananas, pretty much anything you can imagine.

• Matter flux: # of molecules.m−2.s−1

• Energy flux: J.m−2.s−1
• Total amount = J.A.Dt wikipedia.org
 1.10.2019

Atkins’ Physical Chemistry (10th Ed.) Chapter 19A

19A.1 The phenomenological equations Things to remember

Experimental observation:
• Think of flux, J as the amount of something crossing a surface.
J is proportional to first derivative of some other related derivative

Flux of matter <-> derivative of concentration • Positive J means a flow on forward direction (towards positive
(driven by difference in chemical potentials) z) and negative J means a flow on backward direction (towards
negative z)
wikipedia.org

• Matter flows down from a concentration gradient (from high

N : Number density (particles.m−3) conc. to low concentration)
• Energy (heat) flows from high T to low T
• Diffusion will be faster when the concentration varies steeply
• There is no net flux if the concentration is uniform (dN/dz = 0).

Flux of matter, energy, and momentum Atkins’ Physical Chemistry (10th Ed.) Chapter 19A
Some experimental values of K and η Atkins’ Physical Chemistry (10th Ed.) Chapter 19A

19A Transport in gases 19A Transport in gases

Matter flows down a J>0 J(matter) = - D dN/dz

concentration gradient when
(from high conc. to low conc.) dN/dz < 0
D: Diffusion coefficient (unit: m2.s-1)

Energy (heat) flows down a J>0 J(energy) = - K dT/dz

temperature gradient when
(from high T to low T) dT/dz < 0
K : coefficient of thermal conductivity
(unit: J.K-1.m-1.s-1 or W.K-1.m-1)

Momentum transfer occurs with J>0 J(momentum) = - η dvx/dz

velocity gradient when
(from high T to low T) dvx/dz < 0
η : coefficient of viscosity
(unit: kg.m-1.s-1
Example: 19A.1 Poise: 1P = 0.1 kg.m-1.s-1 )
 1.10.2019

Flux of momentum and viscosity Atkins’ Physical Chemistry (10th Ed.) Chapter 19A
19A.2. The transport parameters Atkins’ Physical Chemistry (10th Ed.) Chapter 19A

19A Transport in gases 19A Transport in gases

A laminar flow (Newtonian) fluid
Molecules
constantly moves
between layers
• All the characteristics of the gases depends on the collision flux, Zw.
◦ Collision flux: the rate at which molecules strike a region (imaginary or real)
• Momentum flux depends on the velocity gradient specifically the number of collisions divided by the area of the region and
(x-component) the time interval
• There is no net momentum flux when all the layers
moves at the same velocity HOMEWORK

• Flux is also becomes proportional to the fluid

resistance to flow (viscosity)
OR
viscosity depends on the momentum flux

𝒅𝒗𝒙
𝑱 𝒎𝒐𝒎𝒆𝒏𝒕𝒖𝒎 = − 𝜼
𝒅𝒛
η : coefficient of viscosity
(unit: kg.m-1.s-1
Poise: 1P = 0.1 kg.m-1.s-1 )

19A.2.a) The diffusion coefficient Atkins’ Physical Chemistry (10th Ed.) Chapter 19A
19A.2.a) The diffusion coefficient Atkins’ Physical Chemistry (10th Ed.) Chapter 19A

19A.2. The transport parameters 19A.2. The transport parameters

• Considering the average number of impact on an

• The molecules passing through the area A imaginary region A0 during and interval Dt is 𝒁𝒘 𝑨𝟎 𝚫𝒕
at z = 0 have travelled an average of about • The flux from left to right, 𝐽(𝐿 → 𝑅)
one mean free path λ since their last
𝑍 𝐴 Δ𝑡 1
collision. 𝐽 𝐿 →𝑅 = = 𝑍 = N −𝜆 𝑣
𝐴 Δ𝑡 4
• Similary, moleules moves from right to left.. Thus, the flux
• The number density at point z= - λ from right to left, 𝐽 𝐿 ← 𝑅

𝒅N
N −𝜆 = N (0) − λ 𝐽 𝐿 ←𝑅 =
1
N +𝜆 𝑣
𝒅𝒛 𝟎 4
• Net flux
𝐽 =𝐽 𝐿 →𝑅 −𝐽 𝐿 ←𝑅
• The number density at point z= + λ. 𝐽 =
1
𝑣 N 0 −𝜆
𝑑N
− N 0 +𝜆
𝑑N
Figure 19A.4 The calculation of the rate of diffusion of a Figure 19A.4 The calculation of the rate of diffusion of a 4 𝑑𝑧 𝑑𝑧
gas considers the net flux of molecules through a plane 𝒅N gas considers the net flux of molecules through a plane
of area A as a result of arrivals from an average distance
N +𝜆 = N (0) + λ of area A as a result of arrivals from an average distance
𝒅𝒛 𝟎
λ away in each direction, where λ is the mean free path. λ away in each direction, where λ is the mean free path. 𝟏 𝒅N
𝑱𝒛 = − 𝒗 𝝀
𝟐 𝒎𝒆𝒂𝒏 𝒅𝒛 𝟎
 1.10.2019

19A.2.a) The diffusion coefficient Atkins’ Physical Chemistry (10th Ed.) Chapter 19A
19A.2.a) The diffusion coefficient Atkins’ Physical Chemistry (10th Ed.) Chapter 19A

19A.2. The transport parameters 19A.2. The transport parameters

Fick’s first law: Derivation from KMT

𝟏 𝒅N 𝑱𝒛 = −𝑫
𝒅N 𝟏
𝑱𝒛 = − 𝒗𝒎𝒆𝒂𝒏 𝝀
𝒅N
𝑱𝒛 = − 𝒗𝒎𝒆𝒂𝒏 𝝀 𝒅𝒛 𝟐 𝒅𝒛
𝟐 𝒅𝒛 𝟎
𝟎 𝟎

𝟏
𝑫=
𝝀 𝒗𝒎𝒆𝒂𝒏
𝟐
- Remember: a basic and crude approach is used in calculation /derivation.
- Flux is proportional to the first derivative of concentration (number density, N) - Not every molecules path is straight and may end up colliding with other
before reaching to the window.
- In agreement with the Fick’s first law:
𝒅N - Correction factor: 2/3
𝑱𝒛 = −𝑫
𝒅𝒛 𝟎 𝟏 Diffusion Coefficient
Corrected: 𝑫 = 𝝀 𝒗𝒎𝒆𝒂𝒏 (of gases)
19A.10
𝟑
BI 19A.3 N2 gas: 𝒗𝒎𝒆𝒂𝒏 = 𝟒𝟕𝟓 𝒎/𝒔 , 𝝀 = 𝟗𝟓 𝒏𝒎 ⇒ D (calc) = 1.5x10-5 m2/s at 1 bar HW: Self-test 19A.3
D (exp) = 2.0x10-5 m2/s (in O2)

19A.2.a) The diffusion coefficient Atkins’ Physical Chemistry (10th Ed.) Chapter 19A
Examples
19A.2. The transport parameters

𝟏
𝑫= 𝝀 𝒗𝒎𝒆𝒂𝒏
𝟑
Remember:
𝒌𝑻 Gas molecules
- 𝝀 = 𝝈𝑷 decreases w/ P
diffuse slowly at
 D decreases w/ P high pressure

- 𝒗𝒎𝒆𝒂𝒏 (=  
𝟖𝑹𝑻/𝝅𝑴) increases w/ T Molecules in a hot sample diffuse
more quickly
 D increases with T (w/the same concentration gradient)

- 𝝀 increases as 𝝈 decreases
 D (smaller molecules) > D(larger molecules)
 1.10.2019

19A.2.b) Thermal conductivity Atkins’ Physical Chemistry (10th Ed.) Chapter 19A
19A.2. b) Thermal conductivity Atkins’ Physical Chemistry (10th Ed.) Chapter 19A

19A.2. The transport parameters 19A.2. The transport parameters

• Atoms or molecules moving through an imaginary window Remember Derivation from KMT
transports its average energy 𝒅T 𝟏 𝒅𝑇
𝑱𝒛 = −K 𝑱𝒛 = − v 𝒗𝒎𝒆𝒂𝒏 𝝀N 𝒌
𝒅𝒛 𝟎
𝟐 𝒅𝒛
Molecules arriving from 𝟎
• Molecules arriving from •
−𝝀 𝜺 −𝜆 = 𝐯 𝒌𝑻𝟐 left are hotter and have right are cooler and have
+𝝀 higher energy lower energy 𝟏
K= v 𝒗𝒎𝒆𝒂𝒏 𝝀N 𝒌
1 1 𝟐
𝜺 −𝜆 = 𝐯 𝒌𝑻𝟏 𝐽 𝐿 →𝑅 = N 𝑣 𝜺(−𝜆) 𝐽 𝐿 ←𝑅 = N 𝑣 𝜺(+𝜆)
4 4
- Considering the long paths etc. With a correction factor of 2/3
Left Right • Net flux
1 𝟏 Thermal conductivity
(hot, T1) (cold , T2) 𝐽 =𝐽 𝐿 →𝑅 −𝐽 𝐿 ←𝑅 = N 𝑣 𝜺 −𝜆 − 𝜺 +𝜆 K= v𝒗 𝝀N 𝒌 19A.13a
4
𝟑 𝒎𝒆𝒂𝒏 (of gases)
1 𝑑𝜀 𝑑𝜀
𝐽 = N𝑣 𝜀 0 −𝜆 − 𝜀 0 +𝜆
4 𝑑𝑧 𝑑𝑧
- Here N = p/kT and since D = 1/3 𝝀 𝒗𝒎𝒆𝒂𝒏

𝟏 𝒅𝜀 𝟏 𝒅𝑇 v 𝒑𝑫 Thermal conductivity
K= 19A.13c
𝑱 = − N 𝒗𝒎𝒆𝒂𝒏 𝝀 = − v 𝒗𝒎𝒆𝒂𝒏 𝝀N 𝒌 19A.12
𝑻 (of gases)
𝟐 𝒅𝒛 𝟎
𝟐 𝒅𝒛 𝟎

19A.2. b) Thermal conductivity Atkins’ Physical Chemistry (10th Ed.) Chapter 19A
19A.2. b) Thermal conductivity Atkins’ Physical Chemistry (10th Ed.) Chapter 19A

19A.2. The transport parameters 19A.2. The transport parameters

𝟏 v 𝒑𝑫 𝟏
𝟏 𝒅𝜀 K= v𝒗 𝝀N 𝒌 K= K= 𝒗 𝝀 𝑴 𝑪𝐯,𝒎
𝑱 = − N 𝒗𝒎𝒆𝒂𝒏 𝝀 𝟑 𝒎𝒆𝒂𝒏 𝑻 𝟑 𝒎𝒆𝒂𝒏
𝟑 𝒅𝒛 𝟎
Remember:
𝑵 𝒅
- Since N = 𝒏 𝑽𝑨 = 𝑪 𝑵𝑨 and C𝐯, = 𝑵𝑨 𝒅𝑻 = 𝐯 𝒌 𝑵𝑨 - 𝝀 ∝ 𝟏/𝒑 while N ∝ 𝒑 As pressure increases # of molecules
𝑽 increases but 𝝀 decreases thus cannot
 K ∝ 𝝀p and
carry long distance.
becomes independent of p
𝟏 Thermal conductivity
K= 𝒗 𝝀 𝑪 𝑪𝐯,𝒎 19A.13b
𝟑 𝒎𝒆𝒂𝒏 (of gases)
Thermal conductivity is greater for the
- As 𝑪𝐯,𝒎 ↗ K ↗ gases with a high heat capacity.
or vice versa. (Given temp. Gradient corresponds to
greater energy gradient)

BI 19A.4 N2 gas: D (calc) = 1.5x10-5 m2/s at 1 bar

=> K =1/3 (5/2) (1E5 Pa)(1.5x10-5 m2/s )/298 K = 1.3E-2 J.K-1.m-1.s-1 = 13 mW.K-1.m-1 HW: Self-test 19A.4
K (exp) = 26 mW.K-1.m-1
 1.10.2019

Examples 19A.2. c) Viscosity Atkins’ Physical Chemistry (10th Ed.) Chapter 19A

19A.2. The transport parameters

Viscosity of a fluid: a measure of the frictional

resistance to an applied shearing force.

• There is a velocity gradient in a moving fluid.

 layer above the surface hardly moves.
 Next layer moves with slightly higher
velocity.
 Successive layers have increasingly
higher velocity.
• Velocity gradient, 𝑑𝑣/𝑑𝑥

• 𝐹𝑟𝑖𝑐𝑡𝑖𝑜𝑛𝑎𝑙 𝑓𝑜𝑟𝑐𝑒, 𝐹 𝛼 𝐴 𝑑𝑣/𝑑𝑥

19A.2. c) Viscosity Atkins’ Physical Chemistry (10th Ed.) Chapter 19A

19A.2. c) Viscosity Atkins’ Physical Chemistry (10th Ed.) Chapter 19A

19A.2. The transport parameters 19A.2. The transport parameters

• Momentum transfers to z = 0
 from faster layer, 𝑚𝑣 +𝜆 1 𝑑𝑣 0 𝑑𝑣 0
 from slower layer, 𝑚𝑣 −𝜆 𝐽 =
4
N𝑣 𝑚𝑣 0 −𝑚𝜆
𝑑𝑧
− 𝑚𝑣 0 + 𝑚𝜆
𝑑𝑧

• Assuming uniform density 𝑍 = N 𝜆 𝑣 Figure 19A.6 The

calculation of the viscosity
of a gas examines the net 𝐽 = − 𝑚𝜆N 𝑣
𝑑𝑣 Contributions from the x-component of
𝑚𝑣 +𝜆 = 𝑚𝑣 0 + 𝑚𝜆 momentum brought to a
𝑑𝑧 ones arriving from right plane from faster and
slower layers on average
- Considering the long paths etc.
J = − mλN v
𝑑𝑣 Contributions from the a mean free path away in
each direction.
with a correction factor of 2/3
𝑚𝑣 −𝜆 = 𝑚𝑣 0 − 𝑚𝜆
𝑑𝑧 ones arriving from left

• Net flux
𝐽 = 𝐽 𝐿 → 𝑅 −𝐽 𝐿 ←𝑅 𝟏 Viscosity
𝐽 =−𝜂 𝜼= 𝒎 𝝀 N 𝒗𝒎𝒆𝒂𝒏 19A.16a
𝟑 (of gases)
1 𝑑𝑣 0 𝑑𝑣 0
= N𝑣 𝑚𝑣 0 −𝑚𝜆 − 𝑚𝑣 0 + 𝑚𝜆
4 𝑑𝑧 𝑑𝑧
 1.10.2019

19A.2. c) Viscosity Atkins’ Physical Chemistry (10th Ed.) Chapter 19A

Examples
19A.2. The transport parameters

𝟏
𝜼= 𝒎 𝝀 N 𝒗𝒎𝒆𝒂𝒏 𝜼 = 𝑴 𝑫 [𝑪] 𝜼 = 𝒑𝑴𝑫/𝑹𝑻
𝟑
Remember:
- 𝝀 ∝ 𝟏/𝒑 while [C] ∝ 𝒑 more molecules are available to transport the
momentum, but they carry it less far on account of the
 𝜼 becomes independent of p decrease in mean free path.

 
- 𝒗𝒎𝒆𝒂𝒏 ∝ 𝑻 !!! Viscosity increases with T !!! at high temperatures the molecules
travel more quickly, so the flux of
  (for gases)
𝜼∝ 𝑻 momentum is greater.

BI 19A.5 N2 gas: D (calc) = 1.5x10-5 m2/s at 1 bar and 25 oC.

=> 𝜼 = (1E5 Pa)(28.02E-3 kg/mol)(1.5E-5 m2/s )/(8.314J/K.mol)(298 K) = 1.71E-5 kg.m-1.s-1= 𝟏𝟕𝟏 𝝁𝑷 HW: Self-test 19A.5
𝜂 (exp) = 176 𝜇𝑃

19A.2. d) Effusion Atkins’ Physical Chemistry (10th Ed.) Chapter 19A

19A.2. d) Effusion Atkins’ Physical Chemistry (10th Ed.) Chapter 19A

19A.2. The transport parameters 19A.2. The transport parameters

 
Remember: 𝒗𝒎𝒆𝒂𝒏 ∝ 𝟏/ 𝑴 in accord with 𝒑 𝑨𝟎
 
Thus rate of effusion is also ∝ 𝟏/ 𝑴 Graham’s law 𝑹𝒂𝒕𝒆𝒐𝒇 𝒆𝒇𝒇𝒖𝒔𝒊𝒐𝒏 =
𝟐𝚷𝐌𝐑𝐓 𝟏/𝟐
giphy.com giphy.com wikipedia

Remember:
 
- Effusion ∝ 𝟏/ 𝑴
Considering KMT:
• rate of effusion is equal to the rate of molecules striking the  Graham’s law of effusion
area of the hole
𝒓𝒂𝒕𝒆 𝒐𝒇 𝒆𝒇𝒇𝒖𝒔𝒊𝒐𝒏 = 𝒁𝒘 𝑨𝟎 wikipedia - Effusion is faster at high P
𝒑 𝑨𝟎 𝒑 𝑨𝟎 Rate of  T is also high at high P.
= 𝟏/𝟐
= 𝟏/𝟐 effusion
19A.17  
(effusion ∝ 𝑇)
𝟐𝚷𝐦𝐤𝐓 𝟐𝚷𝐌𝐑𝐓
 1.10.2019

Examples Examples
D19A.1 Explain how Fick’s first law arises from the concentration gradient of gas molecules. D19A.3 What might be the effect of molecular interactions on the transport properties of a gas?
Non-equilibrium gas where the number density is continues and varies smoothly with position. Due to number density Ideal gas – no interaction thus no effect
differences flux from left-to-right and flux from right-to-left in an infinitesmall volüme is not the same and results in a net If there exist molecular interaction, as molecular attraction increases 𝜎 decreases and 𝜆 = is inv. pro with 𝜎
flux of matter dependent of number density (concentration) gradient (nonequilibrium cond.). Proportionality constant is
thus D, K , and 𝜼 are all inversely prop with increases with 𝜎
diffusion.
therefore, all increase with attractive interaction (b/c of decrease in 𝜎)
Observation: Net flow of mass from high conc. to low conc.
and decreases with repulsive interaction (b/c of increase in 𝜎).

D19A.2 Provide molecular interpretations for the dependencies of the diffusion constant and the viscosity on the
temperature, pressure, and size of gas molecules.

- 𝜆 =  D ↘ as P or 𝝈 ↗
𝟏
𝑫= 𝝀 𝒗𝒎𝒆𝒂𝒏  
𝟑 - 𝑣 (= 8𝑅𝑇/𝜋𝑀)  D ↗ as T ↗

- 𝝀 ∝ 𝟏/𝒑 while [C] ∝ 𝒑  𝜼 becomes independent of p

𝟏 - 𝝀 ∝ 𝟏/𝜎 while [C] ∝ 𝒑  𝜼 ↘ as 𝜎 ↗
𝜼= 𝒎 𝝀 N 𝒗𝒎𝒆𝒂𝒏
𝟑    
- 𝒗𝒎𝒆𝒂𝒏 ∝ 𝑻  𝜼∝ 𝑻

Examples Concepts
• Flux is the quantity of a property passing through a given area in a given time
interval divided by the area and the duration of the interval.
• Diffusion is the migration of matter down a concentration gradient.
• Fick’s first law of diffusion states that the flux of matter is proportional to the
concentration gradient.
• Thermal conduction is the migration of energy down a temperature gradient
and the flux of energy is proportional to the temperature gradient.
• Viscosity is the migration of linear momentum down a velocity gradient and the
flux of momentum is proportional to the velocity gradient.
• Effusion is the emergence of a gas from a container through a small hole.
• Graham’s law of effusion states that the rate of effusion is inversely proportional
to the square root of the molar mass.
• The coefficients of diffusion, thermal conductivity, and viscosity of a perfect gas
are proportional to the product of the mean free path and mean speed.
 1.10.2019

Summary of Equations Examples