CHM

2330: Introduc1on to the

Molecular Proper1es of Ma:er

Professor: Wendy Pell

 Evalua1ons
•  15 % Problem sets (3 throughout the term)
•  15 % Midterm #1 (Friday Feb. 17, in class)
15 % Midterm #2 (Friday Mar. 17, in class)
•  15 % Laboratory (2 experiments / reports)
•  5 % Echo360 In-class assignments
•  35 % Final exam
 What’s in it for you.
•  All course notes
•  Extra prac1ce ques1ons at DGDs
•  List of other suggested problems from the
textbook
•  Last year’s exams with solu1ons given in class
•  It’s not mine, but should give you an idea
•  List of concepts to help you study before each
midterm
•  During exams:
•  formula sheets
•  fundamental constants
 What’s expected of you.
•  a:end all lectures and pay a:en1on
•  ask ques1ons during the lectures
•  visit me in my office if you have any ques1ons or
concerns whatsoever
•  a:empt to solve problems and examples given
during the lecture
•  work on any and all prac1ce problems distributed
to you
•  contact me if anything is unclear to you
•  a:end DGDs if you aim to get a top mark
 Midterms and Final Exam
•  All exams are closed-book exam.

•  You are not allowed to bring in any of your own formula sheets,
notes, books etc.

•  You will be provided a Formula sheets:

•  Programmable calculators are not allowed.

•  An absence requires a doctor’s note

•  Show all work for full marks.

•  Phones and devices must be turned off and put away in your bag.
 Re-grades
•  submi:ed in wri1ng within 1 week of date that test is
returned
•  if you find an error
–  staple a note to the front of your test indica1ng:
1. problem number
2. detailed explana1on
•  bring test to me before or a_er class or to my office - I
will not discuss grades/re-grades prior to or
immediately following lecture or DGD
•  If a_er regrade is returned you have further
comments, you must make an appointment to see me
 Laboratory
•  Manual and expecta1ons are posted to
Blackboard
•  Lab 1 and 3 start this week
•  Access BB and sign up – you will be assigned
an experiment
•  You must complete 2 laboratory exercises to
pass the course
•  Each lab last 3 weeks
–  1 dry week / 2 wet weeks
 Problem Sets
•  Yare permi:ed (but not required) to work in groups of
up to 4 people. Only one copy of the group’s answers
needs to be submi:ed for marking, and all people in
the group will receive the same mark. Pudng your
name on a group assignment implies that you have
made a significant contribu1on to the work.
•  Assignments handed in class, any assignments handed
in same day a_er class will lose 25% of the total marks.
•  Assignments will not be accepted a_er the due date
(i.e., they get zero).
 Echo360 In-class exercises
85 % for answering anything
100 % for answering correctly
We will be using Echo360..

You have been or will be emailed a link to register to the Echo360
class.

You must use your uO:awa email address
You must use your First and Last names exactly as they appear on your
student card!

During our lectures, you can either sign into Echo360 with a WIFI
device or text your answer. If you plan to text your answers then
you must enter you telephone number during the registra1on
process – I will never see this and promise not to call you during
dinner or early Saturday morning!
Text
Recommended (not required)

Older versions work but you need to be
capable of reading an index and a table
of contents

Suggested text problems
 Topics
•  Kine1c theory of gases (2 lectures; Ch1B)
•  Introduc1on to quantum theory (7 lectures;
Chs 7 and 8)
•  Spectroscopy (6 lectures; Ch 12 and 14)
•  Introduc1on to sta1s1cal mechanics (2
lectures; Ch 15)
•  Chemical kine1cs and reac1on dynamics (3
lectures; Ch 20 and 21)
 Molecules in Mo1on
Objec1ve: To describe the mo1on of various
kinds of par1cles in all types of fluids

Why: Transport proper1es are integral to
understanding reac1on rates and catalysis

Where to start: Ideal gas
Kine1c Molecular Theory of Gases
Three assump1ons:
1st. The gas consists of molecules of mass m in ceaseless random
mo1on
2nd. The size of the molecules is negligible, in the sense that their
diameter is much smaller than the average distance travelled
between collisions with other molecules
3rd. The molecules interact only through brief, infrequent, and
elas1c collisions


Actually, there is a 0th assump1on as well:
0th. The only contribu1on to the energy of the gas is from the
kine1c energies of the molecules

 The Condi1ons in pictures

PHYSICAL CHEMISTRY: THERMODYNAMICS, STRUCTURE, AND CHANGE 10E |

PETER ATKINS | JULIO DE PAULA
©2014 W. H. FREEMAN AND COMPANY

d is the diameter of an ideal gas par1cle

m is the mass of a par1cle
v is the speed
Δt is a 1me interval
 What comes out of the assump1ons?

where:
P is the pressure (in my notes I use capital P for pressure and small p for momentum)
V is the volume
n is the number of moles of gas
M is the molar mass of the molecules
c is the root-mean-square speed of the molecules

What is root mean square speed?
2 1/ 2
c= v
V is the speed of the molecules

< > denotes mean
 Echo360
What are the mean and root mean square speeds?

Speed (m s-1)
340 432
333 652
230 203
560 403
450 208
326 490
560
 Echo360
What are the mean and root mean square speeds?

Speed (m s-1)
340 -432
-333 652
230 -203
-560 403
450 -208
-326 490
560
 Elas1c Collision
Total transla1onal kine1c energy of the molecules is conserved
Recall p = mv
where p is momentum
Before: p = mvx

A_er: p = -mvx

Change in x-component of linear
momentum due to the collision: PHYSICAL CHEMISTRY: THERMODYNAMICS, STRUCTURE, AND CHANGE 10E | PETER
ATKINS | JULIO DE PAULA

|∆p| = 2mvx ©2014 W. H. FREEMAN AND COMPANY

In this example, the y- and z-components of the linear momentum

are unchanged as a result of the collision.

The pressure of a gas arises from the impact of its molecules on the
walls of the container.

 How many collisions in 1me Δt?
Distance travelled along x-axis during Δt is
|vx Δ t|

The wall on the right has area A, and
lies in the yz-plane.

All molecules with a posi1ve vx in volume V
will collide with the wall during Δt:

Vwill = AvxΔt
 How many molecules are there in my
volume Vwill = AvxΔt ?

•  “Ceaseless, Random Mo1on” implies that the molecules are
distributed uniformly in the total volume of the container, Vtotal.

•  If there are ntotal moles of molecules in the total volume Vtotal, then
the number of moles in the volume we are considering is obtained
by a simple ra1o:
nwill Vwill ntotalVwill ntotal Av x Δt
=
nwill = n will =
ntotal Vtotal V total Vtotal

•  and the number of molecules in the volume Vwill is therefore
ntotal Av x Δt
⋅ NA
Vtotal

•  where NA is Avogadro’s number.

 But….
•  Only half are going forward (have posi1ve vx ; will contribute to the P).

•  The average number of collisions with the wall during Δt is:

1 ntotal Av x Δt
⋅ ⋅ NA
2 Vtotal

•  The total change in momentum which occurs during Δ t:
(momentum change for 1 molecule is 2mvx )
ntotal MAv x2 Δt
•  Momentum change = Δp =
Vtotal
•  where M = mNA (the molar mass)
`
And what was I trying to do in the first
place?
The pressure volume rela1onship for a gas under the assump1on of kine1c theory….


Pressure is force divided by area: P= F/A

Force is equal to the rate of change of momentum: F = Δp / Δt

Therefore,


This simplifies to:


n and V are the total moles and total volume

 Important: not everyone is moving at
the same speed….
Recalling again our first assump1on that the
molecules are in random mo1on, we should
really use the root-mean-square speed rather
than the average speed along the x-axis.

In addi1on: And




Voilà
 Speed and temperature
If the root-mean-square speed of the molecules depends only on
temperature, we can see that the quan1ty PV is constant at
constant temperature. This is the content of Boyle’s Law.

We know that for an ideal gas, n = PV/RT.

Therefore, we obtain:


** Be careful of units. Recall R = 8.31417 J K-1 mol-1

Conclusion: the root-mean-square (rms) speed of the molecules of
an ideal gas is propor1onal to the square root of the temperature,
and inversely propor1onal to the molar mass.


 Maxwell distribu1on of speeds

Molecules are NOT all travelling with a single uniform

speed.

Collisions (with other molecules) alter speeds, and you
get a distribu1on
 Where does that ridiculous equa1on
come from?
The total kine1c energy for a molecule with velocity components vx, vy, and vz is:

The distribu1on of popula1ons is an exponen1al func1on of energy and temperature

At high T more energy levels are occupied than at low T, so:



And


 What is K ?

Since:


You get:

Which conveniently gives us:
 Where are we now?
Note: if you use molar mass,
M, then you use R and if you
use mass, m, you use k

The probability that a molecule has a velocity in the range vx to vx +

dvx, vy to vy + dvy, vz to vz + dvz is:




And v2 = vx2 + vy2 + vz2


 And the probability is:

The probability f(v) that the molecules have a

speed in the range v to v + dv may be
represented as 4pv2 dv, where 4pv2 is the
surface area of a sphere:

And we can write the final
form of the Maxwell
distribu1on as:
 What can you tell me
The range of speeds ______ as
T increases. Heavier molecules
have _______ distribu1ons.

a)  broadens, broad
b)  narrows, narrow
c)  broadens, narrow
d)  narrows, broad
Mean speed (not root mean) for N2(g)
at 25 oC ?

Since
Mean speed (not root mean) for N2(g)
at 25 oC ?

a)  15 m/s

b)  475 m/s

c)  21 m/s

d)  671 m/s

Q: At 500 K, what frac1on of N2
molecules travel with speeds between
290 and 300 m s-1?

Not as easy as “plugging in” values, but almost…..

You need to evaluate f(v) Δv of f(v) dv not just f(v)

300m/s
F(at 500K ) = ∫ f (v)dv
290m/s
 Do I really need to integrate ?
What if the frac1on of molecules we are
considering is very small…what can you assume
about f(v) ?

a) f(v) = 1
b) f(v) = large
c)  f(v) = small
d) f(v) = constant
 Solu1on
First approxima1on: assume f(v) is constant over
the range v = 290 to 300 m s-1 and use
v = 295 m s-1
300m/s
F(at
500K ) = f (295) ∫ dv
290m/s

= f (295)Δv = f (295)(300 − 290)

 Solu1on
First approxima1on: assume f(v) is constant over the
range v = 290 to 300 m s-1 and use v = 295 m s-1

Δv = 300 m s-1 – 290 m s-1 = 10 m s-1

Therefore, f(v)Δv = (9.06 x 10-4 m-1 s)(10 m s-1)
= 9.06 x 10-3 = 0.91 %


 Not done yet…..
Check our assump1on: evaluate f(v) for v = 290
and then for v = 300 m s-1

Note that f(295 m s-1) is equal to the average of f(290 m s-1) and f(300 m s-1) in this case.


How do you determine the most
probable speed, c*?
 Summary
1. root-mean-squared speed

2. mean speed

3. most probable speed

4. rela1ve mean speed

is the reduced mass
This simplifies to when mA = mB

Note: C > C > C*; 1.225 : 1.128 : 1.000

The rela[ve mean speed is the mean speed
with which one molecule approaches another.
 Collision frequency

Collision tube: cross-sec1onal area σ = πd2 and length crelΔt
and volume σcrelΔt

Hit: centres of two molecules come within d of each other
 Collision frequency
N molecules in total volume V, the number
density N = N/V

Number of sta1onary molecules in the collision
tube: NσcrelΔt (also the number of collions,
hits)

σ Crel P
Collision frequency z = N σ Crel =
kT
 Collision frequency
At constant volume, collision frequency
increases with __________temperature because
_______increases with temperature

At constant temperature, collision frequency is
propor1onal to ________
a)  decreasing , pressure, speed
b)  increasing, pressure, speed
c)  decreasing, speed, pressure
d)  Increasing, speed, pressure
 Collision frequency
Typical numbers:

For a nitrogen molecule in a sample at 1 atm
and 298 K, z = 5 x 109 s-1;

a given molecule experiences a collision about
5000000000 1mes per second!

 Mean free path, λ
For a collision frequency z, a molecule spends a 1me 1/z in “free flight”
between collisions and travels a distance called the “mean free path”
during this 1me:


We may subs1tute the previous expression for z to get:



A typical mean free path for nitrogen gas at 1 atm is 70 nm, which is
about 103 1mes the molecular diameter.

This finding is consistent with our ini1al assump1on that “The size of
the molecules is negligible, in the sense that their diameter is much
smaller than the average distance travelled between collisions with
other molecules”
 Collision flux (Jus1fica1on 19A.1)
(number of collisions with a given surface area in a given 1me)

Collision flux increases with pressure

as the rate of collisions on the region
of interest increases with pressure

Flux decreases with increasing mass as
heavy molecules move more slowly

Watch out for T….if system is constant
volume, then p α T, so collison flux is
propor1onal to T1/2 and not T-1/2
 Effusion

•  Effusion - defined as “the emergence of a gas from a container through a

small hole”

•  Graham’s law of effusion is an empirical law which states that the rate of
effusion is inversely propor1onal to the square root of the molar mass.

•  Can we ra1onalize this observa1on in terms of what we have already
derived?

•  We showed that the mean speed of the molecules is also inversely
propor1onal to the square root of the molar mass.

•  Therefore, the rate at which the molecules encounter the area of the hole,
A0, (and thereby effuse) is also inversely propor1onal to the square root of
the molar mass.

 Rate of effusion
Rate of effusion = collision flux * area of hole






Empirical: rate is propor1onal to
square root of molar mass
 Why do I care?
His work on the diffusion of gases was used in
1868 to discover the chemical formula for
ozone, O3. Graham's inves1ga1ons of the
behaviour of crystallized compounds passing
through membranes, as a method of separa1ng
large molecules from similar compounds, led to
the technique of dialysis. Graham's method is
s1ll in use in hospitals today, for purifying the
blood of pa1ents with kidney failure.

Manha:an Project to produce U-235
enriched uranium hexafluoride, UF6
By the spring of 1945, Oak Ridge
had shipped approximately 132 lbs.
of enriched uranium
(approximately 90% U-235) to Los
Alamos, New Mexico. This was used
in "Li:le Boy", the bomb dropped
on Hiroshima on August 6, 1945.
The majority of fission weapons
since that 1me have used
plutonium.

In power reactors you need 3 to 4
% U-235

 Gaseous effusion

This small difference in rates means that many effusion barriers (stages) are
necessary for enrichment. The K-25 gaseous diffusion plant at Oak Ridge
required 4000 stages. This plant was one-half mile long and six stories high
and covered 43 acres. The produc1on of a suitable barrier was the key to
successful separa1on. The holes must be microscopic (approximately one-
millionth of an inch in diameter) and uniform in size. The porosity must
always be high to sustain high flow rates and the barrier must not react with
the highly corrosive hexafluoride. Nickel and aluminum oxide were best
suited for barrier materials.