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. -------------------------------------------------------2. -------------------------------------------------------3. -------------------------------------------------------4. .

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

: <cyzhu@mail.nctu.edu.tw> : <adudu.fish@gmail.com>

Example in Math
Example.1 (in teaching)
1 1 M 1 1 L 1 1 L 1 M M M 1 1 1

1 + 2 + 3 + + n = (n+1)n/2

[n

n +n 2

Problem 1: 1 + 5 + 9 + 13 + + [1+4(n-1)] = ? Problem 2: Problem3 : Infinite applications Gap may appear from learning to applications 1 + 2 + 4 + 7 + + [1+n(n-1)/2]= ?

Problem 2:

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

How to construct matrix to solve the following

k (k + 1) Sn = =? 2 k =1
n

Design matrix
n L L n 1 L n 2 M M 1 L

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

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

Design matrix
2 3 1 n 1 2 n n 1 1 M M M n n 1 n 2 n L n 1 L n 2 M M 1 L
L

Sum over upper off-diagonal plus diagonal matrix elements Sum over lower off-diagonal

k =1

k ( k + 1) 2

A n = n ( n 1 ) + ( n 1 )( n 2 ) + L + 2 1 =

n 1

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)

1 a n +1 1 + a + a2 + a3 + L + an = 1 a
Problem (in application)

a 2 + a 4 + L + a 2n = ? L

a 2 + a 4 + a 7 + L + a [n ( n +1) / 2+1] = ?

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

Ideal gas
Dense gas P, V, T, n

Very dilute gas P, V, T, n Liquid P, V, T, n

PV=nRT
Solid P, V, T, n

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

Interface between different phases

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

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

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

Macroscopic thermodynamic method Derive f (P, V, T, n) from experiment Van Der Waals equation

an 2 P + 2 V

(V nb ) = nRT

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 , L ) = 0

Physical Chemistry II Temperature

Energy

In order to get energy levels Ek, we have to solve Schrdinger equation

H k = E k k
h2 h2 2 H = R 2 me =1 2 M
Nn

time

Z e2 2 i 1 r R r r i =1 = i =1 i
Ne Nn Ne

Nn Nn Ne Ne e2 Z Z e 2 + r r + r r j =1 i < j ri r j =1 < R R

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

Q (V , N , T

)=
j

k BT

From physical chemistry II

ln Q P = k BT V T ,N
2

The most general and the best state of equation

f (P , V , T , n ; a , b , c , L ) = 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 ( T 0 ), super-conductor and superfluid 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 = y (x ) (In physics and chemistry) Example: = (T)

Definition of the first derivative

dy df ( x ) f (x + x ) f (x ) y = = f ( x ) = = lim dx dx x x 0

Example 1 (Simplest)
f (x ) =

y = f ( x ) = ax + b

linear

lim

[a ( x

x 0

+ x ) + b ] [ax + b ] = x

lim

x 0

ax = a x

Example 2
f (x) = lim
x0

y = f ( x ) = ax
2

+ bx + c

quadratic
2

[a(x + x)

(2ax + b)x + a(x) = 2ax + b + b(x + x) + c ax2 + bx + c = lim x x x0

][

Example 3

y = f ( x ) = sin x

sin function

f ( x ) = lim
x 0

sin ( x + x ) sin ( x ) 2 cos ( x + x / 2 )sin (x / 2 ) = lim = cos x x x x 0

Example 4

y = f ( x ) = arcsin x

arcsin function

y = f (x) = arcsinx sin y = x

dx on both side
d (sin y ) dx = =1 dx dx d (sin y ) dy d (sin y ) = dy = f ( x ) cos y = 1 dx dx

Calculate dy

Final

f ( x ) =

1 = cos y

1 1 sin 2 y

1 1 x2

Certain rules

z = g (x )

y = f (x )

d ( yz dx

)=

dz dy + z dx dx

or

d ( fg dx

)=

dg df g + 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
Example 5: proof
d (y / z ) dx

Higher-order derivatives

y = f (x ) 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

Example 6: proof

dx

( yz ) =
n

k =0

n d k y d nk z k dx k dx n k

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

dF ( x ) = f (x ) dx
x2 xdx = + C 2 x3 2 x dx = + C 3 x n +1 x dx = + C n + 1
n

integrand Example 1
f (x) = x f (x) = x2 L f (x) = x
n

F F L F

(x ) = (x ) = (x ) =

Example 2

f ( x ) = sin x f (x) = ex

sin xdx = cos x + C F ( x ) = e x dx = e x + C

F (x ) =

Most important rule: integration by part

u (x )
or write as

dv ( x ) du ( x ) dx = u ( x )v ( x ) v ( x ) dx dx dx

uvdx = uv vudx 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 ) = uv + uv vu = uv dx

Final

F ( x ) = H ( x) F ( x ) = H ( x ) + C

Example 3

xe x dx = xd e x = x e x e x dx = ( x + 1)e x
Example 4
2 2 2 x2 x2 x x x xlnxdx= lnxd 2 = 2 lnx 2 d(lnx) = 2 lnx 4

) (

) (

Example 5
1 1 1 1 1 dx = = (a x)(b x) a x b x (a b) [ln(a x) ln(b x)] (a b)

Change of variable (substitution)

Example 6

1 e dx a
ax ax = y adx = dy

1 y 1 ax e dy = a e = a e
y

Example 7

d sinx y2 sin2 x sinx cosxdx= sinx dx dx ydy= 2 = 2

sinx= y

d sinx dy = dx dx

Calculation in heart

sin2 x sinx cosxdx= sinxdsinx = 2

Example 8 (luck case)

ax

1 1 ax ax ax e sinbxdx = a sin bxde = a e sinbx b e cosbxdx 1 ax b = e sin bx cosbxdeax a a 1 ax b ax ax = e sin bx e cos x e d cosbx a a

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

Algebraic calculation

eax eax sin bxdx = 2 2 [a sin bx b cosbx] a +b

A lot of methods for integration, but most important is checking If you get Check

f (x)dx = F (x)
F ( x) = f (x)

x2

dx has no compact form with simple function

Integration is more difficult than differentiation

Example 9

x 2 n+1eax
0

1 n y y=x dx y e dy 20
2

Method 1

n n n1 y n y I n (a ) = y e dy = y e dy = I n1 (a ) a a0 0

n! n! I n (a ) = n I 0 (a ) = n+1 a a
Method 2
I 0 (a ) = e
0 y

a>0

1 dy = a

dI 0 (a ) 1 y = ( y )e dy = 2 da a 0

( y )e
0

1 dy = 2 a

Continue derivative

(y) e
n 0

1 2 3L n dy = a n +1

Example 10 Method 1

I n (a ) = x e
0

2 n ax 2

dx

(2n 1) x 2n2eax2 dx = (2n 1)I (a ) 1 2 n 1 ax 2 I n (a ) = n 1 x de = (2a) ( 2a ) 0 2a 0

(2 n 1)!! I (a ) I n (a ) = (2 a )n 0
I 0 (a ) = e
0 ax 2

dx = ?

Definite integral

e
0

ax2

1 dx = 2 a

Derive

ax 2

dx =

e 0

ax 2

dx

e ax 0

/2 2 2 ax ay ar 2 dx = e dx e dy = d re dr = 4a 0 0 0 0

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

f (x1 ) = tan1

f (x0 ) = tan0

Application to maximum-minimum of function

f (x) = tan = 0 = 0

Extreme

f(x)

x0

x2 x1 x0

f ( x 2 ) > 0 f ( x1 ) < 0 f ( x 0 ) = 0

x1

x2

x Minimum Maximum Inflection point

1 2 f (x ) = f (x i ) + f ( x i )( x x i ) 2!

Example 1

(x) = 2x3 6x + 2 y= f
df (x) = 6x2 6 = 0 x = 1 x = 1 dx
minimum maximum

> 0, x > 0 d 2 f ( x) = 12x 2 dx < 0, x < 0

Definite integral First do indefinite integral

F (x ) =

f (x )dx

f (x )dx
a

= F (b ) F (a )

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

ff((u )) x

a Area can be minus or plus

2

b
2

sin xdx = [ cos x]0 = 0

0

Homework 1-3

Page 55 Problem 4. (a) (j)