Text book:

Applied Mathematics for Physical Chemistry,

Barrante, 3rd , 2004.
Reference books:
Chemistry Maths Book, Steiner, 2004
Physical Chemistry, A Molecular Approach, McQuarrie
and Simon, 1997
Homework (30%)
Midterm (30%)
Final (40%)

 Homework( )

Homework i-2

1.
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2.
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3.
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4.
.

----Lecture note in PDF file is emailed to everyone before class---
Put more time on listening
Follow math logical procedures and techniques carefully

 Example in Math
Example.1 (in teaching) 1 + 2 + 3 + + n = (n+1)n/2

n
1 1 1
1 1 1
2
n
n
2

1 1 1
Problem 1: 1 + 5 + 9 + 13 + + [1+4(n-1)] = ?

Problem 2: 1 + 2 + 4 + 7 + + [1+n(n-1)/2]= ?

Problem3 :

Infinite applications
Gap may appear from learning to applications
 Problem 2: 1 + 2 + 4 + 7 + + [1+n(n-1)/2]= n+S(n-1)?

How to construct matrix to solve the following

n
Sn
k (k 1)
?
Design matrix
2
k 1
1 2 3 n
n 1 2 n 1

n n 1 1 n 2


Sum each row = 1+2+3 +n=n(n+1)/2 n n 1 n 2 1

Sum all rows: Total =n*n(n+1)/2

 Design matrix
1 2 3 n
n 1 2 n 1

n n 1 1 n 2


n n 1 n 2 1

Sum over upper off-diagonal k ( k 1 )

n
S n 2
plus diagonal matrix elements
k 1

A n n ( n 1 ) ( n 1 )( n 2 ) 2 1
Sum over lower n 1

off-diagonal
k 1
(k 1)k 2 S n (n 1)n

n n (n 1) 1
3 S n (n 1)n S n n n 1 n 2
2 6

Example.2 (in teaching)
n 1
1 a
1 a a2 a3 an
1 a

Problem (in application)

a 2 a 4 a 2n ?
a 2 a 4 a 7 a n ( n 1) / 21 ?

After warming up

 I. Review of differentiation and
integration
Introduction
Review of differential calculus
Review of integral calculus
Graph

 I-1. Introduction

Hot coffee in closed container

Study from point of view

Physical Chemistry I

Physical Chemistry II

Physical Chemistry III

State of function f (P, V, T, n) = 0 ?

Physical Chemistry I
Very dilute
Ideal gas gas PV=nRT
P, V, T, n
Dense gas Liquid Solid
P, V, T, n P, V, T, n P, V, T, n

f1(P,V, T, n)=0 f2(P,V, T, n)=0 f3(P, V, T, n)=0

Interface between different phases

Can we find f (P, V, T, n) = 0 ?

Macroscopic thermodynamic method
Derive f (P, V, T, n) from experiment
2

V nb
an
P nRT
Van Der Waals equation V 2

Try various equations with two parameters

f P , V ,T , n; a,b 0
Improve accuracy with more parameters involved
f P , V ,T , n ; a , b , c , 0

 Energy
Physical Chemistry II Temperature

In order to get energy levels Ek,

we have to solve
Schrdinger equation
time
H k Ek k

N
2 2 N N N Z e2 N N
e2 N N
Z Z e2
H
n e n e e e n n

2
2

ri R ri r j
R i
1 2M 2me i 1 1 i 1 j 1 i j 1 R R

Physical Chemistry III
Microscopic thermodynamic method
Derive f (P, V, T, n) from theory

Q V , N , T E k T
Partition function e j B

From physical chemistry II

ln Q
P k BT 2

V T ,N

The most general and the best state of equation

f P , V ,T , n ; a , b , c , 0

Combine experiment and theory

Combine and through

 Extreme situations :
for both experiment and theory
At room temperature and pressure, most chemistry is supposed
to obey Boltzmann statistics. mathematics
At very low temperature ( T0 ), super-conductor and super-
fluid can happen. Chemistry (or physics) is now supposed to
obey Fermi-Dirac or Bose-Einstein statistics. mathematics

At very high temperature, atom star, nuclear star, quark star, and
blackbody show up. Gravitation, weak, and electromagnetic, forces must
be considered in theory. mathematics

Baby steps
A single variable differential calculus
A single variable integral calculus

 I-2. Review of differential calculus

Naming: x independent variable, y---dependent variable

y f x f----function form (in math)
y yx (In physics and chemistry) Example: = (T)

Definition of the first derivative

df x f x x f x
f x
dy
y lim
dx dx x 0 x

 Example 1 (Simplest) y f x ax b
linear
f x lim a x x b ax b a x
x 0 x lim
x 0 x
a

Example 2 y f x ax 2
bx c quadratic
f x
a x x 2

b x x c ax 2
bx c 2 ax b x a x
2

lim
x 0 x lim
x 0 x
2 ax b

Example 3 y f x sin x sin function

f x
sin x x sin x 2 cos x x / 2 sin x / 2
lim
x 0 x lim x 0 x
cos x

 Example 4 y f x arcsin x
arcsin function

y f x arcsin x sin y x

d sin y dx
1
dx on both side dx dx

d sin y dy d sin y
Calculate dy
dx f x cos y 1
dx dy

1 1 1
f x
Final cos y 1 sin 2
y 1 x 2

Certain rules y f x
z g x

d yz y
dz

dy
z or
d fg f
dg

df
g
dx dx dx dx dx dx

Chain rule y f u x

dy df u x df u x du df u du

dx dx du dx du dx

d y / z
Example 5: proof dx

 y f x
Higher-order derivatives
z g x

d yz y z y z
dx
d 2
yz
d y z y z
y z 2 y z y z
2
dx dx

d n
yz n
n d k y d n k
z
Example 6: proof n
k n k
dx k 0 k dx dx

Try various functions for differential calculus

as
Mental training game

Homework 1-1
Page53-54

Problem 1.
(a) (t)

 I-3. Review of integral calculus
Indefinite integral
F x f x dx x
dF
dx
f x

integrand
x 2
Example 1 f ( x ) x F x xdx C
2
f ( x ) 2 x 3
x F x x 2
dx C
3

x n 1
f ( x ) x n
F x x n
dx C
n 1
Example 2
f ( x ) sin x F x sin xdx cos x C

f ( x ) e x F x e x
dx e x
C

Most important rule: integration by part
dv x du x
u x dx u x v x v x dx
dx dx

or write as u v dx uv v u dx
udv uv vdu
dv x dv x
Proof F x u x dx F x u x

dx dx
du x
H x u x v x v x dx H x u v u v v u u v
dx

Final F x H ( x ) F x H x C

Example 3

xe x dx
xd e x x e x e dxx
x 1 e x

Example 4

x2 x2 x2 x2 x2
x ln xdx ln xd 2 2 ln x 2 d ln x 2 ln x 4
Example 5
1 1 1 1 1
a x b x dx ln a x ln b x
a b a x b x a b

Change of variable (substitution)
Example 6
1 1 1
dx ax y adx e y dy
ax dy y ax
e e e
a a a
Example 7
d sin x
2 2 dy
d sin x sin x y y sin x
sin x cos xdx sin x dx dx ydy 2 2
dx dx

Calculation in heart
sin 2 x
sin x cos xdx sin xd sin x 2

Example 8 (luck case)

e ax
sin bxdx
1
a sin bxde ax

a

1 ax
e sin bx b e ax
cos bxdx
1 ax b ax
e sin bx cos bxde
a a
1 ax
e sin bx
a a

b ax
e cos x e d cos bx
ax

1 ax
a
e sin bx
b ax
a
e cos x b e ax
sin bxdx

Algebraic calculation
e ax
e ax
sin bxdx 2 a sin bx b cos bx
a b 2

A lot of methods for integration, but most important is checking

If you get f x dx F x

Check F x f x

e
x2
dx has no compact form with simple function

Integration is more difficult than differentiation


1

2 2
Example 9 x 2 n 1 e ax yx
dx y n e y dy
0
2 0

I n a I n 1 a
n n
Method 1
0
y n e y dy
a
0
y n 1 e y dy
a
n! n!
I n a n I 0 a n 1 a 0
a a

1
Method 2 I 0 a e y dy
0
a

0 a

dI
y e y dy 12 y e y
dy
1
da 0
a 0
a2

1 2 3 n
Continue derivative y n
e y
dy
0
a n 1

I n a x
2
2n ax
Example 10 e dx
0

Method 1

I n a
1

2 n 1 x 2 n 2 e ax 2 n 1 I a
2 a 0
2 2
2 n 1 ax
x de dx
2 a 0 2a
n 1

I n a
2 n 1 ! ! I a
2 a n 0

I 0 a e
2
ax
dx ?
0

Definite integral

1
e
2
ax
dx
0
2 a

2
Derive
ax 2 ax 2
e dx e
0
dx

0

2 /2
ax 2
ax 2

ay 2

ar 2
e dx e dx e dy d re dr
0 0 0 0 0
4a

Homework 1-2 Page71-72

Problem 1.
(a) (j)
Problem 2.
(a) (t)

 I-4. Graph
Graphic meaning of derivative ---- line tangent to a curve
f (x)

x* x2 x1 x0 x

f x1 tan 1 f x 0 tan 0

Application to maximum-minimum of function
f x tan 0 0 Extreme
f(x)

x 0 x1 x 2
x
x2 f x 2 0 Minimum
x1 f x 1 0
Maximum
x0 f x 0 0
Inflection point
1
f x f x i f x i x x i 2
2!

Example 1
y f x 2x 3
6x 2

df x
6x 2
6 0 x 1 x 1
dx

minimum
maximum

d 2 f x 0, x 0
12x
0, x 0
2
dx

 Definite integral
First do indefinite integral F x f x dx
b

f x dx F b F a
a

Graphic meaning of definite integral ---- area of shaded region

f (u)

a b u
a b x
2

sin xdx cos x 0

2
Area can be minus or plus 0
0
Homework 1-3

Page 55

Problem 4.
(a) (j)