CHEM 311

Chapter 31

Term 221

Khalid Al-Mashaouf Note

 Statistical Thermodynamics

Ensemble a
large collection of identical units or
replicas of a system

canonical ensemble constant V T and N

microcanonical ensemble constant Vand N

canonical Energy E ace E Addition of Energies

I
coefficient per canonical

of canonical particles
anonical
Weight We

fÉfÉy NI total
W of particles
mingy
b biof particles ineachlevel
Product of victorialy
BE.tt Bs
y
wq
Probality p Ei
BE
2 fit
Tota canonical partition function

ten
as e
 Example on W using Molecular States

1,013,5 10,1 of 20 objects

we
W
FINTAN
9.3 108
W'q.gg oip

31.20 Q Total canonical partition function

q specific canonical partition function

To clarify
get Ecant
q
Erin
B EAotts
Q e
B EatEso éB
EaotEpd qBCEAtEBdyjBlEAitEBdy
BlEa.tEB t
BEA
Q e
BEA0
a
BEBO
jar t

Q GaGB
distinguishable
Q q or qrs as
This is just math like the relation in

EMIN
indistinguishable
Q
11 Total of distinguishbilaty
 Distinguishable you can discriminate the
atom wherever you rotate the compound

Example
no it I
Lated's't
figu Even
It
µ
cgma

after rotational the can

be distinguished because there is no similar
atom opposite the symmetry line

Indistinguishable you can't discriminate the

atom wherever you rotate the compound
Examples

ifu
O'and'M
you can't distinguish the
after rotational because the symmetry
line is acting exactly like a mirror

31.30 Eta E ER tut E Eloctronical

Note a is h
molecule Translation Rotational vibrational

bb IT
 B
BEE
Total Egg e

b
degeneracy 7
Gata 9jSj9i9e

GeneralFormula Got 9 Gr Gr Ge

e.fmtmtereplaced
aeans 8m
by

B
l
az

Trans 1directional
box dimention

sE E E
man I set
Oz
E
gig m

I D box

É E
f
as Icma o.o m

Hang to convert
7kg
3.1 10 jam
38
18
s
or DE 3141 1.56 15 on
 The previous law of 9 could be replaced
by a new one at any fixed temperature

1 D
Est q
gib I
Thermal wavelength

an at A Area
217 7
ay 2D
I
35 7 9 is D P ax v volume
z

9 7 9,30
1
Aram 40 1.66 15
B'It
Vs 11 20.001m
if
Ts 298k fixed T yg Iggy flip up

y.y.jp
A
jotting 6 62661341.6min

2.44 1029
9 130 11,4 0 1
 Always B
MT Rotationalconstant
Ey y
g 28 1 q
gg Ep he BJ JH
rotational and J represent
exist when there the level just

É
are 2 atoms like u but in B
rotational

Reduced mass M
min
The previous law of Gr could be replaced
by a new one if DJ KT

ar ph 5 EMii q itit io.aciiii'eat

L o 3 NH3 CHC's
symmetry I 12 7 CHU e GH

How o of city is equal 12

H U
There are 3 symmetry without
I the H the symmetry line so we
on
need to maltubly 4 3
Itt
12
g
a
2
How o of NA is 3 Because it is a
unige
axis that has no simmiler
i axis

I H II's
 Find o of CH Cl
4
of
H
TI
Find o of Colt
6
Gxz

gH
É Hl

UH
YI Hu

Find o of Cfc

d
gpb
Idol Utc 20
5

law 11
b f f
i
a
id y Eg
Pg
Probability

calculating T in Ts Faked
rotational spectrum
 Ts
HBr
Ts
SILI
u
K
temerity
1.38 NO JIN
h s 6.626 18 J S
C 3h18m1s
ÉÉÉÉÉÉIg
5 493.5 k

Rotational THE head

as Fas Int
GE Ion

9 GR s Iq hey
6.6
Iz 0 2 0 1,93
34 53.74
T look I É I
0.0538k
given 13150.0374cm
Gr
K 1.38 1623Jfk
21 538 9290
31 This law for polyatomic molecules more than 2atoms

Gr IE FBI BIBI Bia

means you can use the
previous 2 laws because it's more accurate

Ts 138 101 1 6.626 10 C 3NEms

9ps 21
OCS o l all are differentatoms
B 1.48cm 148m
Gr Inter
Gas 4g B It

ONCI i i
as ECI G GI It
are F it Ia et
ar FC acts C C l
9r C69
 th
31.70 q E e

Note There is no
degenerisy for vibration
vibrational Ens ho htt
E
k
frequinst
U c
g
wake

or we can use this integrated formula

Itewith Ziro point energy

q s

Note This formula excluding

9
ugly zero point energy There is no
big different but you only use
zero point energy if the question
asked for it

g at 2982s
97 page LEE
I
j
7 20800mi
4 6.6 103 J S HIIQ.oxiosuxsx zosoo.no
C 3 108 MIS Atto
N 34a3a18x20800 3.86 V
I E.ba
o 1.38x1o23
 that
Pn I e
he
e theory e
Probabilit
n
n 3 N G or 3N 5 which represent how many
g vibrational mods
4 goat It Muli Gu is the multiblicity of all vibrationalmodes
g is the degenerisy
Important 3N 5 is for Linear Polyatomics such as
70 0 diatomic molecule
2 8,141 I grant
Be Br Is Br Be Br

3M G is for non linear polyatomic such as

o o
1
H2O
1Égj it 19h

O n
0010 nonlinear 9 If 191 n 3N 6 73137 6 3
fate
8 450,945 1100car
0 3 10 cuts
é GuiGui Gus
T 298K
4 6.626 163
uabaiooansoy.zgxqzgg
K 1.38 10 ME lI
gg
y
6403443
Kus 101094511.38 1 23298
113 1 old1
Total
ioxzaoxloop.gg 1 00
Total Miao
zgg
yg
 vibrational T
YI

Gr
Ey or you can use this at hight 9ns I
i
The short law can be used when

Er The hight limit appropriate when Ty 10

7 917Cail
c salient or T 7110On
4 6.626 16348S
K 1.38916 Jk
ref I
9
Iq
On
ht
F

911
6.62691
1 1321
Therefore TZ 10 1320 T 13200 at least

now check the 2 methods assume Ts 13300k

istosis
Le
10.5

13 10.1
Thus it i a legitimate estimate
Coz O C O Gr É Muli 9 total oh 9 tr
Linear

n 3N 5
313 5 4
9
é tent
A 1388 mx3xto'x1388
jg pgb.gr
138x1x1ooo
905667.4

9 67
2 YIiiomis
ftp.vk.sn ggy.uq g xoo

4 6.626No g s
1 dxtxzug.gg
k T
2349
k 1.38 10 81k
E oo

looo Cv 1.16 2.56 1.04 3.17

totaF Gr af

q
E gie
egg Ent
Electrical

hgt
Note The electronic partition function of all atoms in
the ground state at room T will be always z
 Note No need to calculate the term above e when E is getting
more than tooo cut because it's getting almost so like et
hefolks
heat he E ghcE Kt
Vanadium
q g g g Rtg
n 011 2,3
Eo o As a short cut we will calculate hey before
E 137.38cut substuting it in the eq
E 323.46cal
Es 552.96
go U
4 4,101
9.3 94 0.0048 cat

2 6 0.0048 0 6 exp o 0048 137.38

go 4 exp
92 8
g 10 8exp 0.0048 323.46 10exp 0.0048 552.9677
4 6.626 10 9.46
9g
c TatemIs
K 1.38210
Ts 298k