• Manho Lim: mhlim@pusan.ac.krRoom 403, 510-2243 (O), Room 126, 510-3283 (lab),

• Classes: M, W 9:00-10:15 (75 min)• Office Hours : M, W: 13:00-14:30• http://cafe.naver.com/enjoychem

• Course objectivesIndividuals who successfully complete this course will be

able to:– Know basic terminology of chemical kinetics – Describe the rates of chemical reactions including complex

reactions – Explain chemical reactions in terms of molecular reaction

dynamics

2015 Chemical Kinetics

1

• Course DescriptionChemistry is concerned about change and, thus, chemical kinetics is one of the majorconstituent of chemistry. Built on the knowledge of thermodynamics and quantumchemistry you acquired in physical chemistry courses, we will learn how to describechemical kinetics and reaction mechanism using molecular behavior in the gas phase andthe condensed phase. The lecture begins with reviewing necessary mathematical toolsand describing molecular motions. The rates of chemical reactions, the kinetics ofcomplex reactions, molecular reaction dynamics will be covered.

• Required Textbooks"Physical Chemistry" by P W Atkins and J. D. Paula, 9th edition, Oxford University Press, Oxford (2011)

• References– "Chemical Kinetics and Dynamics" by JI Steinfeld, JS Francisco, and WL Hase, 2nd edition, Prentice Hall,

Inc, New Jersey (1998) – "Chemical Thermodynamics: by C. E. Reid, McGraw Hall, New Jersey (1990) – Recent research articles published in Journal of Physical Chemistry A, B, C– Class-related articles published in Journal of Chemical Education– Any textbook for physical chemistry

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2015 Chemical Kinetics

• Requirements & GradingGrading system: – Two Exams 75%– Homework, quiz, Presentation 20%– Attendance 5%Each test will be weighed according to class hours covering the

material

– There will be 1 point deduction per one hour absence. Deduction is not limited by 5% (ex, If one is absent for 15 hours, he or she will get –10 points). Each class worth 1.5 hours.

– Assigned homework should be submitted by due date for credit.

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2015 Chemical Kinetics

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Prepare a Solution Notebook and write thefollowings in the first page of the notebook.

1. A good reason for taking Chemical Kinetics.2. Your goal grade and your working plan to

achieve your goal in detail.

Later, you do the followings in the notebook3. Do all the Examples, self-tests in your

textbook.4. Do assigned Problems in the textbook.

Homework (due Sep 3, Thr)

• Fundamentals (pp 6-13)F.4 EnergyF.5 The relation between molecular and

bulk propertiesF.7 Units

• Mathematical background 4 (pp 322-323)Differential equations

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Homework (Quiz)

• Mid term: Oct 15 (Thr) (8:30-10:30)

• Final examDec 3 (Thr) (8:30-10:30)

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(Tentative) Test date

No class/ Makeup class• Oct 6, 8, 29(?)• Oct 24, Nov 14 (Saturday)

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Register café (http://cafe.naver.com/enjoychem)

1. All the class materials, previous tests can bedownloaded.

(you should bring it with you in class)2. All the information on class management such

as test date, test score, makeup class, etc.3. Upload your assigned problems.

First thing to do

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1. Visit http://cafe.naver.com/enjoychem

2. Answer all the questions.

3. Make your ID in the form of 15XXXXXX is your name.Unless your ID is in the correct form,

your registration is not allowed.

How to register the cafe

The Boltzmann distribution

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i ki

TEeN −∝

( )ii j

j

E kT

E kTE E kTi

j

eN eN e

−−

−−=∴ =

The average number of molecules in a state is called the population of the state

The number of molecules in a state with a energy, Ei: Ni

23 1

1 1

1.381 10 : Boltzmann's constant8.314 : gas constantA

k JKR kN JK mol

− −

− −

= ×

= =

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https://en.wikipedia.org/wiki/Ludwig_Boltzmann

Boltzmann's grave in the Zentralfriedhof, Vienna, with bust and entropy formula

The Boltzmann distribution

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iE kTiN e−∝

The energy level separations

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The Boltzmann distribution

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( )

( )

i

i j

i j

E kTi

E E kTi

j

E E kTi i

j j

N eN eNN g eN g

−

− −

− −

∝

=

=

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Some results of probability theory-1When a variable X has a discrete value xi with the probability pi, the mean value ( the expectation value) <X>

Value Probabilityx1 p1

x2 p2

x3 p3

xi pi

1

N

i ii

X x p=

= ∑

When f(x) is the probability density, a measure of the distribution for the probability values over x and x + dx,

( )Probability of finding value of between and b

aX a b f x dx= ∫

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Some results of probability theory-2

The mean value of the continuously varying X is given by

( )X xf x dx∞

−∞= ∫

The mean value of a function g(x):

( ) ( ) ( )g X g x f x dx∞

−∞= ∫

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( )

2

2

0

2

0

0

, 2

1 2 2

12

ax

s

ax

xe dx

s ax ds a

xe d

xdx

ds ea a

xa

∞ −

∞ −

∞ −

≡ =

= =

∴ =∫

∫

∫

( )2

2

2

3

0

0

20

2

2

12

12

12

ax

ax

ax

d xe dxda a

LHS x xe dx

R

x e dx

HS a

a

∞ −

∞ −

−

∞ −

=

= −

= −

=∴∫

∫

∫

A few integrations-1

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( )

2 2

00

,

12

tax dtea

t ax dt adx

e dxaπ∞ −∞ − = =

≡ =

∫ ∫

( )

( )

( )

2

2 2

2 2

2

2

0

2

0 0

0 0

2 2 2

20

0

0

2

0

,

, 2

2 2 4

=2

x

x y

x y

r

s

x

I e dx

I e dx e dy

dx dye

x y r dxdy rd dr

d rdre

s r ds rdr

ds e

e dx

π

φ

φ

π π

π

∞ −

∞ ∞− −

∞ ∞ − +

∞ −

∞ −

∞ −

≡

=

=

+ = =

=

≡ =

= =

∴

∫∫ ∫

∫ ∫

∫ ∫

∫

∫

A few integrations-2

x

y

ϕ

r

2

2 2

22 3

0

2

0 0

2

32

0

12

1 12 2

4

a

ax ax

ax

xd e dxda a

LHS e dx x e dx

RHS a

x e dx a

π

π

π

∞ −

∞ ∞− −

−

∞ − −

=

= = −

= −

=

∴

∫

∫

∫ ∫

Quiz 1 (Sep 3)1. Write the bar and atm in the derived unit of pressure.

2. What is the common SI prefix for 10–15, 1012, and 1021.

3. Write the electronvolt, eV in the unit of J.

4. When the function f(x) is the probability density, write the expression for the mean value of x and g(x).

5. Do the following integration.

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(1) = (2) ( )x g x =

2 2 22

0 0 0 ax ax axe dx xe dx x e dx

∞ ∞ ∞− − −= = =∫ ∫ ∫

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Power series and Taylor expansion-1• Power series:

( ) ( ) ( ) ( )20 1 2

0

n nn n

nc c x a c x a c x a c x a

∞

=

+ − + − + ⋅⋅ ⋅ + − + ⋅ ⋅ ⋅ = −∑

• Taylor series:f(x) is expressed as a power series in the vicinity of x = a

( ) ( ) ( ) ( ) ( )( ) ( ) ( )

2

0

' "( )

1! 2!

!

nn

n

f a f af x f a x a x

f ax

n

a

a∞

=

= + − + − + ⋅ ⋅

= −

⋅

∑

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Power series and Taylor expansion-2

Exponential function:

Geometric series: 2 3

0

1 1 for 11

n

nx x x x x

x

∞

=

= = + + + + ⋅⋅ ⋅ <− ∑

( )2 3

ln 12 3x xx x+ = − + + ⋅⋅ ⋅Natural log:

http://en.wikipedia.org/wiki/Taylor_expansion

( )

1, 11 1

1 ln 1

xIf x e x

xx

x x

<< = +

= +−

+ =

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Quiz 2 (Sep 8, Tue)

2 2

2 2

2

0 0

2 3 2 320 0

4 5 2

0

1 1 2 2

1 4 2

38

π

π

π

∞ ∞− −

∞ ∞− − −

∞ − −

= =

= =

=

∫ ∫

∫ ∫

∫

ax ax

ax ax

ax

e dx xe dxa a

x e dx a x e dxa

x e dx a

• Mathematical background 4Differential equations

• Some results from probability theory• Power series and Taylor expansion• The following integrals