Download Department of Science - Chemistry

Chemistry Department
General Course Information
CHEM243
Physical Chemistry
0.1250 EFTS
Second Semester
15 Points
2015
Description
The topics covered by this course are:
• The science of the very small – introduction to quantum mechanics
• From molecules to materials – statistical thermodynamics and statistical kinetics
• Molecular mixing – classical thermodynamics and kinetics
This course is presented in the second semester only. It counts 15 points towards a Bachelor of
Science degree and preferably should be taken in conjunction with other 200-level chemistry
courses.
Timetable
Lectures and Tutorials: 4 face-to-face contact hours (typically 3 lectures and 1 tutorial) will be held
every week. Lecture/tutorial times and locations available via ‘MyTimetable’.
Lectures will be given in the following order:
Dr Sarah Masters (9 lectures, 3 tutorials)
e-mail: [email protected]
Phone 364 2456,
Room 736
Dr Deb Crittenden (13 lectures, 4 tutorials)
e-mail: [email protected]
Phone 364 2875,
Room 636
Prof Greg Russell (13 lectures, 4 tutorials)
e-mail: [email protected]
Phone 364 2458,
Room 634
Course Co-ordinator
Dr Deborah Crittenden, Department of Chemistry
Email: [email protected]
Email me if you have any queries about the course.
Assessment
Exam:
Assignments/tutorial work:
55%
45%
Examination and Formal Tests
Exam: 3 hours during end-of-year exam period. Time and place will be available online closer to the
date.
Assignments and tutorials
Each lecturer will set assignment/s and/or tutorial problems worth 15% of the total assessment for
this course, amounting to a total of 45% for the course as a whole. These will normally be set in
tutorials, but may also be available online.
NOTE: If you do not submit an assignment for assessment you will be allotted zero marks, which will
affect your final result. You should ensure that you pick up marked assignments and keep them until
the end of the course as evidence that the work was completed and marked in the case that either is
disputed. To guard against accidental loss, it would be prudent to keep photocopies or electronic
copies of anything submitted. If you submit work electronically, please cc a copy to yourself in lieu of
keeping a physical copy.
Textbooks
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P W Atkins & J de Paula, Physical Chemistry (8 , 9 or 10 edition). This text covers most of the
material of this course, and should be used to supplement the lecture material prepared by each
lecturer. The book also contains many helpful worked examples and tutorial problems.
You will be expected to possess this book or have access to it.
Copies are available on short term loan from the Engineering and Physical Sciences Library.
Prerequisites
CHEM 211
Goal of the Course
Physical chemistry provides the basic principles for understanding and explaining the observations
made in all branches of chemistry. The foundations of physical chemistry are the laws of
thermodynamics and quantum mechanics. The former describes the properties of bulk matter on a
macroscopic scale, while the latter concerns the behaviour of individual particles (electrons, atoms
and molecules) on a very small scale. Both viewpoints are developed in this course, and integrated
through the theory and application of statistical mechanics.
Course Content
The topics coved in this course are:
Introduction to quantum mechanics: Wave-particle duality of light and matter, introduction to the
Schrodinger equation, simplifications required to make the Schrodinger solvable - model systems
(particle-on-a-line, harmonic oscillator, hydrogen atom, rigid rotor), applications of models to real
chemical systems. Spectroscopy as a technique for interrogating quantum states of chemical
systems – infrared and microwave spectroscopy..
Statistical thermodynamics and kinetics: Molecular modes of motion (electronic, vibrational,
rotational, translational), the microcanonical ensemble, partition functions, the Boltzmann distribution.
Statistical mechanical definition of thermodynamic quantities (entropy, enthalpy, internal energy, heat
capacity). Using the Boltzmann distribution to explain intensities of spectroscopic transitions. The
kinetic theory of gases, collision theory, transition state theory and molecular dynamics.
Classical thermodynamics and kinetics: Reversible processes, variation of thermodynamic
quantities with temperature, Ellingham diagrams. Gibbs energy, Helmholtz energy and states of
matter. Phase diagrams, phase equilibria, Clapeyron and Clausius-Clapeyron equations,
characteristic points, phase rule. Chemical potential, ideal solutions and Raoult’s law, Henry’s law,
colligative properties, Debye-Huckel law, chemical equilibrium. Fundamental empirical concepts of
chemical kinetics. Experimental methods for measuring rate, reaction mechanisms and rate
equations, catalysis. Bimolecular reactions and environmental effects.
Learning Outcomes
By the end of this course, students should be able to:
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Define the concept of quantum numbers, give specific examples of sets of quantum numbers
and indicate what they relate to
Identify kinetic and potential energy terms in the Schrödinger wave equation
Relate the Schrödinger wave equation to simple model systems
State how particle-in-a-box theory describes translational motion
Describe how harmonic oscillator theory models vibrational motion
Define anharmonicity, and state its importance in describing quantum nuclear motion
Interpret how the rigid rotor model describes rotational motion
Work through an example of a sensible application of particle-in-a-box theory
Apply the harmonic oscillator approximation to an appropriate model system
Give an example of how the solutions to the Schrodinger equation involving a Morse
potential can be used to interpret experimental results
Give an example where and how to use the rigid rotor model
Describe the different modes of motion that molecules, atoms and subatomic particles
undergo
Define (in a statistical mechanics context) the following terms: macrostate, microstate,
configuration
Construct all possible configurations obeying a given microcanonical rule, and determine
their weights
Use the Boltzmann distribution to determine the distribution of particles among energy levels
for systems with large numbers of particles in their most probable configuration
Calculate partition functions for diatomic molecules
Calculate heat capacities of gases, and explain how and why the heat capacity of a gas
varies with temperature
Interpret and explain the intensities of transitions in electronic emission, IR, UV-Vis and
microwave spectra
Explain the relationship between statistical mechanics, the ideal gas equation and the kinetic
theory of gases
State the assumptions behind collision theory, and outline its strengths and weaknesses
State the assumptions behind transition state theory, and interpret the results of transition
state theory in physical terms
Explain the relationship between the Arrhenius equation, the collision theory rate equation
and the transition state theory rate equation, in terms of their similarities and differences and
the importance of these
Calculate collision theory and TST rates for di-atomic reactions
Visualize simple potential energy surfaces
Define and use the following: state functions, heat, work, internal energy, first law of
thermodynamics, enthalpy, heat capacities, heats of formation, Hess’s law, entropy, second
law of thermodynamics, Gibbs energy.
Understand what is meant by: reversible change; reversible, isothermal expansion work; dS
= dqrev/T; variation of entropy with volume and with temperature; variation of DrH, DrS and
DrG with temperature, Ellingham diagrams.
State why Gibbs energy and Helmholtz energy are defined, and give some of the useful
results that follow from these definitions, including explaining why materials change state as
they do as temperature is changed.
Explain the thermodynamic basis of phase diagrams and phase equilibria, including the
Clapeyron and Clausius-Clapeyron equations, characteristic points, and the phase rule.
Know what is meant by chemical potential, and be able to apply this concept for
understanding of mixing, ideal solutions, Raoult’s law, Henry’s law, and colligative properties.
Understand the thermodynamic basis of chemical equilibrium, and be able to apply this to
non-ideal conditions and electrochemical situations.
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Be familiar with the basic kinetics concepts of and important results for: rate law, reaction
order, rate coefficient, integrated rate law, pseudo-first-order kinetics, half-life, determination
of reaction order, variation of rate coefficient with temperature.
Outline common experimental methods for measuring rates, in particular spectroscopy, and
explain their strengths and weaknesses.
Be able to derive and use results for the four common reaction mechanisms of consecutive
reactions, pre-equilibrium, parallel reactions and opposing reactions.
Discuss homogeneous catalysis, chain reactions and (in some detail) enzyme-catalysed
reactions.
Explain the following theories for bimolecular rate coefficients: collision theory, transition
state theory, Smoluchowski theory for diffusion-controlled reactions.
Understand how bimolecular rate coefficients are affected by viscosity, pressure, solvent
polarity, dielectric permittivity, ionic strength, and reactant substituents.
GENERAL INFORMATION 2015
Chemistry Department Policy on ‘Dishonest Practice’
The University has strict guidelines regarding ‘dishonest practice’ and ‘breach of instructions’ in
relation to the completion and submission of examinable material. In cases where dishonest practice
is involved in tests or other work submitted for credit a department may choose to not mark such
work (p 52 of the 2015 University Calendar under the headings ‘Breach of Instructions and Dishonest
Practice’).
The Department of Chemistry upholds this policy. It considers plagiarism, collusion, copying, and
ghost writing to be unacceptable and dishonest practices:
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Plagiarism is the presentation of any material (text, data or figures, on any medium including
computer files) from any other source without clear and adequate acknowledgement of the
source.
Collusion is the presentation of work performed in whole, or in part, in conjunction with
another person or persons, but submitted as if it has been completed by the named author
alone. This interpretation is not intended to discourage students from having discussions
about how to approach an assigned task and incorporating general ideas that come from
those discussions into their own individual submissions, but acknowledgement is necessary.
Copying is the use of material (in any medium, including computer files) produced by
another person or persons with or without their knowledge and approval.
Ghost writing is the use of other person(s) (with, or without payment) to prepare all or part
of an item of work submitted for assessment.
Additional Information
Aegrotat applications: If you feel that illness, injury, bereavement or other critical circumstances
has prevented you from completing an item of assessment or affected your performance, you should
complete an aegrotat application form, available from the Registry or the Student Health and
Counselling Service. This should be within seven days of the due date for the required work or the
date of the examination. In the case of illness or injury, medical consultation should normally have
taken place shortly before or within 24 hours after the due date for the required work, or the date of
the test or examination. You have the right to appeal any decision made, including aegrotat
decisions.
For
further
details
on
aegrotat
applications,
please
refer
to
http://www.canterbury.ac.nz/exams/aegrotats.shtml.
Missing of tests: In rare cases a student will not be able to sit a test. In such cases, the student
should consult with the course co-ordinator to arrange alternative procedures. This must be done
well in advance of the set date for the test.
Past tests and exams: these can be found on our website using the link below:
http://www.chem.canterbury.ac.nz/for/undergraduate.shtml
Submission of reports and assignments: Reports and assignments should be handed in on time.
Extensions will be granted only in exceptional circumstances (such as illness or bereavement). If an
extension is required, as early as possible you should request it from the lecturer concerned.
Note: If you do not submit an assignment for assessment, you will be allotted zero marks, which will
affect your final result. You should ensure that you pick up marked assignments and keep them until
the end of the course as evidence that the work was completed and marked in the case that either is
disputed. To guard against accidental loss, it would be prudent to keep photocopies or electronic
copies of anything submitted.
Late Work: Late work should be accompanied with a detailed explanation of why the work is late.
The work will be marked and 10% of the total marks will be subtracted for each day the work is late.
Days late include week-end and holidays. Note: if you know in advance that you cannot submit work
by the required date, please contact your lecturer to discuss your options.
Marks and Grades: The following numbers should be considered as a guide to the expected grades
under normal circumstances. The Department reserves the right to adjust mark/grade conversions, if
necessary. This will occur only where statistical analysis of marks indicates that the numerical
distribution, and subsequently arising grades, is anomalous. Any such adjustments will not be made
to the detriment of students’ grades.
Grade:
Minimum mark %:
A+
90
A
85
A−
80
B+
75
B
70
B−
65
C+
60
C
55
C50
D
40
E
0
Reconsideration of Grades: Students who are concerned that an error has occurred in marking or
grade setting should, in the first instance, speak to the course coordinator (Deb Crittenden,
[email protected]). If they cannot reach an agreeable solution, or have further
questions about their grade in the course, students should then speak to the Director of
Undergraduate Studies (Andy Pratt, room 836, tel. 364-2424, [email protected]).
Students can appeal any decision made on their final grades. They can apply or reconsideration of
the final grade within four weeks of the date of publication of final results according to instructions at
http://www.canterbury.ac.nz/exams/results.shtml. Be aware that there are time limits for each step of
the appeals process.
Students with Disabilities: Students with disabilities should speak with someone at Disability
Resource Service (http://www.canterbury.ac.nz/disability/, phone 364-2350 or ext. 6350, email
[email protected]).
Academic Advice: Dr Andy Pratt (room 836, tel. 364-2424, [email protected]) is the
Director of Undergraduate Studies for Chemistry. His interest is in the academic performance and
well-being of all such students. Anyone experiencing problems with their undergraduate chemistry
courses or requiring guidance about their BSc in Chemistry should get in contact with Andy.
Staff-Class Rep Liaison: Dr Andy Pratt (room 836, tel. 364-2424, [email protected]) is in
charge of liaison with students in Chemistry courses. Your class will appoint a student representative
to the liaison committee at the start of the semester. Please feel free to talk to the student rep about
any problems or concerns that you might have.
Andy Pratt
Director of Undergraduate Studies
Department of Chemistry
June 2015