CHEM2402/2912/2916

Key Contacts

Second Year Director: Prof. Peter Harrowell, Room 314

Second Year Lab Director: Dr Markus Muellner, Room 454

Education Support Team: Jojo Zhou, room 210

All enquiries for CHEM2 should be directed to Jojo at:

chemistry.education@sydney.edu.au
 CHEM2402/2912/2916
Lecture Structure
Stream 1 – 8am in Lecture Theatre 2

› Lectures 1-15: Dr Toby Hudson

- Room 456
- toby.hudson@sydney.edu.au

› Lectures 16-27: A/Prof. Deanna D’Alessandro

- Room 457
- deanna.dalessandro@sydney.edu.au

› Lectures 28-38: A/Prof. Chris Ling

- Room 455
- chris.ling@sydney.edu.au
 CHEM2402/2912/2916
Lecture Structure
Stream 2 – 12 noon in Lecture Theatre 2 (Mon & Tues) and Lecture
Theatre 1 (Thur)

› Lectures 1-15: Dr Asaph Widmer-Cooper

- Room 360
- asaph.widmer-cooper@sydney.edu.au

› Lectures 16-27: Prof. Lou Rendina

- Room 518
- louis.rendina@sydney.edu.au

› Lectures 28-38: Prof. Brendan Kennedy

- Room 458
- brendan.kennedy@sydney.edu.au
 CHEM2402/2912/2916
eLearning Site
• The eLearning (Canvas) site for CHEM2402/2912/2916 is active.

• The site contains detailed information on this unit, including:

• Unit of Study outline and course syllabus
• Assessments
• Timetables
• Laboratory program

• You should check this site at least once a week during semester.

• Piazza is also set-up for you. Make sure you use it!
 CHEM2402/2912/2916
Tutorials

› Commence in Week 2, then run every alternate week:

- Tutorials to be held in Weeks 2, 4, 6, 8, 10, 12 and 13.

› Your tutorial time and location will be indicated on your

personal timetable.

› Attendance is compulsory.
 CHEM2402/2912/2916
Laboratory Classes
• Labs start in Week 1. Check your Schedule via Canvas Chem2
Laboratory home webpage.
• Lab coats and safety glasses are compulsory in all Chemistry labs.
Students who show up for their Chemistry lab classes without a lab
coat or safety glasses will not be permitted to remain in the lab.
Make sure you bring your coat and glasses along to your first lab
class.
• Students should complete the Safety Induction and secure 100% in
the Safety Quiz. Before starting any laboratory work you must
complete the pre-work associated with your experiment. All quizzes
are accessible via Canvas Chem2 Laboratory home webpage.
 CHEM2402/2912/2916
Class Reps
Be The Voice of 2402, 2912 or 2916!

› Staff-Student Liaison Committee

- Two meetings per semester
- Lunch provided!
- First meeting: Monday 13 August, 1pm

› See me after the lecture if interested.

 Chemical Stability
In this first part of the course, you will learn how the microscopic properties of
individual molecules give rise to the macroscopic properties of large collections of
molecules, for example chemical equilibrium, phase behaviour, the direction of
spontaneous change of chemical reactions, and reaction rates.

To do this we will investigate the fields traditionally known as:

Statistical Thermodynamics
Classical Thermodynamics
Kinetics
 Statistical Thermodynamics
Did you realise that not all molecules in a system are doing the same thing at the
same time? Where do macroscopic properties of chemical systems come from?
How do they arise from the properties of individual atoms, molecules, and ions?

We are going to ask big, important questions that affect all chemical properties
and processes, like

What is temperature ?

Why is there an absolute zero ?

How do molecules collectively decide what to do ?

Why does an equilibrium constant look like that ?

 States, Microstates, and Configurations

The state of a molecule is the amount of energy in each of its degrees of

freedom.

e.g. the state of a diatomic molecule is completely specified by its electronic

configuration, vibrational quantum number v, rotational quantum number J, and a
translational quantum state.

The total energy of that molecule is just the sum of the energies of each degree of
freedom.

A molecule is completely described by its molecular state.

 States, Microstates, and Configurations

What can we know about a collection of (say, ~1023) molecules?

Such a system of molecules cannot normally be completely specified. Instead we

have incomplete knowledge - limited to the values of a number of bulk
parameters like number of molecules, temperature, pressure, energy, volume…

Some of these quantities have no counterpart in an individual molecule. They are

purely properties of a system.

In statistical thermodynamics, we find that even incomplete knowledge can tell us

quite a lot about systems of molecules. But we first need to understand
something about statistics and probability in chemical systems.

Let’s build a simple model…(Worksheet 1)

à Socrative
 States, Microstates, and Configurations
Every microstate and configuration must satisfy the constraints of total
particle number, N, and total energy, E.

Total Particle Number is just the sum of the number of molecules in each
state i. ¥
N = å ni Summation notation: S means “add up all
i =0
of the occupation number (ni) of all the
energy levels from i = 0 to infinity
(remember it’s notionally an infinite ladder of
energy levels). Often we drop the from “= 0”
and to infinity, so be careful to check where
to start and stop counting.

N = n0 + n1 + n2 + n3

In this example,

For configuration I N = 2 + 0 + 0 + 1 = 3
For configuration II N = 1 + 1 + 1 + 0 = 3
For configuration III N = 0 + 3 + 0 + 0 = 3
 States, Microstates, and Configurations
The Total Energy is just the sum of the number of molecules in each state i times the
energy of that state, ei

E = å nie i
i
For our model allowing molecules to have 0, 1, 2, 3… “quanta” of energy
E = e 0n0 + e1n1 + e 2n2 + e 3n3
= 0 ´ n0 + 1 ´ n1 + 2 ´ n2 + 3 ´ n3
= 0 + n1 + 2n2 + 3n3
In this example,
For configuration I E = 0 + 0 + 0 + 3 = 3
For configuration II E = 0 + 1 + 2 + 0 = 3
For configuration III E = 0 + 3 + 0 + 0 = 3

Review:
A molecular state is a quantum state of an individual molecule.
A microstate is a possible distribution of the total energy among the molecules.
A configuration is a possible distribution of the molecules among the molecular states.
 How Many Microstates?
We will not be able to deal with even moderately large systems by continuing to
enumerate microstates. Instead, we can calculate the number of microstates,
W(n0, n1, n2,…) that occur for a given allowed configuration (set of occupation
numbers) as follows
N!
W (n0 , n1 , n2 ,...) =
n0 !´ n1 !´ n2 !´ ...
Where N is the total number of molecules in the system, and ni is the number of
molecules in state i.

N! (factorial N) = N x (N-1) x (N-2) x (N-3) x… 3 x 2 x 1, and 0! = 1 by definition.

In the lecture example,

I n0=2, n1=0, n2=0, n3=1 WI = 3!/(2! 0! 0! 1!) = 6/(2´1´1´1) = 3
II n0=1, n1=1, n2=1, n3=0 WII = 3!/(1! 1! 1! 0!) = 6/(1´1´1) = 6
III n0=0, n1=3, n2=0, n3=0 WIII = 3!/(0! 3! 0! 0!) = 6/(1´6´1´1) = 1

…and the total number of microstates is Wtot = Sconfigurations W

(= WI + WII + WIII , in the example) = 3 + 6 + 1 = 10.
 Summary & Learning Outcomes
After listening to this lecture and completing the associated learning
materials, you should
• Be able to define all the following terms
• degree of freedom; state; microstate; occupation number,
configuration
• Know the important degrees of freedom:-
• electronic, vibrational, rotational, translational
• Discriminate between the properties of individual molecules
and those that only exist for entire chemical systems.
• Enumerate the microstates of a simple system and calculate
configurations.

Next Lecture
• Statistics and Configurations in large systems.
• What is Equilibrium?
 Homework Problems
1. Consider a system of 4 molecules with a total of 2 quanta of energy. Like the
system examined in lecture today, the energy level levels of this system of
molecules are spaced one quantum apart.
a) List all the allowed configurations of this system as sets of occupation
numbers, n0, n1,... (Draw out the system and enumerate the microstates of
the system if you wish.)
b) Calculate the number of microstates corresponding to each allowed
configuration, then calculate the total number of microstates of this system.
c) If you make an observation on this system, what is the probability that there
will be a molecule in quantum state 2?

2. Now consider a much larger version of that system, containing N = 50 molecules

and E = 50 quanta of energy.
a) Write out the occupation number notation for a configuration in which one
molecule has 50 quanta. How many microstates like this are there?
b) Write out the occupation number notation for a configuration in which each
molecule has 1 quantum. How many microstates like this are there?
c) Verify that the following set of occupation numbers satisfies N = 50, E = 50:
n0 = 26, n1 = 12, n2 = 5, n3 = 3, n4 = 2, n5 = 1, n6 = 1. How many microstates
are there for this configuration?