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Thermodynamics

Phenomenalogic theory of matter

empirical
t.experimen
dynamic
th.mg
system

Emergent system

e.g systems of many particles in nature


atoms molecules in gas fluid solid
quantum
gas of electrons photons in CM

V1 consequences
t.iiiiiii.jo 똷鬱 썝

iiiiiiii li
ensemble that
濕 汐

statistic equilibrium EM

thermodynamic parameters
thermodynamic
microscopic quantities
7 equilibrium
EG I V T H m
2
entropy
Them dynamic state thermodynamic laws
Sik
Inf
of microscopic States
Sak log w


퍈얞ni
m
limit N to sin meaningful

von

E infinite
v

thermo quantities a N extensive


intensive

Example
isolated
if

prob of finding such a situation

N가
WIN PM 1 p N
Gy
彭 比 州
w N binomial Gaussian
aint

ㅡy
煎 丸 꺲 o
곪 want

i
Probable

T 그
Np

mean square pluctuati.in

땟學 li Ntn
o

Macroscopic system
thermodynamic

system
Ef

wall
Csi

굚t energy exchange
hath

surroundings is so large that


heat exchange does not change its
macro quantities T temp
M chem not
closed
themany isolated
exchanged
adiabatic wall
N not allow

T Const

open
exchanged

N
T Const
m const

classical S M
closed
Consider N particles in 3 d

C M H Hamiltonian
Canonical cards Avogadro's

it 요 M 一一
요 모기 3 T d o f

Time evolution Hamilton's


ear of motion

E 珙 一
Pi 2HE i 1 一一 3N

Pn phase space

t
p_space

represent ate point


Initial condition
N 1023 ambiguous In C s

elation state unknown

interest in a few macroscopic

quantities

Consider Swarm
n

tf iuii.at condition
density of representative points

폠 density function

H R
Ii i
iii

ri 쨾
i
I ftp.q.t
X Prob of finding
density function
the system at given
t.in Ace interval

Volume P P tdp
q at dq
X ftp.htldpdq
5
냔합남악
幾 f la.ge of identical systems

Prob with a particular property


x of systems in the ensemble
aiiinhrn
place a general constraint
N V ㅿ uncertainty
튷띠
energy

microcanonical ensemble

EEadamioifiii.i t
democracy

the system found


equally likely
in state
any of its accessible

jo Linville'S the ary


f P q 七
쁥 it 昕 柒
T
鵠 一

0 in compressible

Equilibrium
2L

if H f constants of motion
almost always energy
s

HIM a 這
9 9 HIP q
Two basic postulates of sin
O Equal a priori prob
91M 의 Const if ECHLMh Eto
E
O otherwise

i'd

Ergodic hypothesis

훒mb교 ER 의 ftp.aidpdq

ensemble time average


average ㅜ
A in
ftp.q.tld isirrrn
Microcanonical Ensemble ㅿ E
P P q const if E H P오 Et ㅿ
I o otherwise

i volume in phase space occupied


by the microcanonical ensemble

p
1 fit ftp.q ftp.iq
E CHIP q Et

f
phase space

I
it t
volume of E sphere energy shell

IIE d pd q
total Volume af the
Hip q KE energy sphere

Density of state WEI ECE d E



El Etf
WIE 三
士魚 ME
fowl
E UE
E
W1E
은 not
relevant
in T limit

Boltzmann Entropy
Shag W
S k In
entropy f
Boltzmann constant IS 氾幻 江 幻
phase space of states
volume 1강
L fundamental
volume
31 Do f
ho
consider Two subsystems in contact



particle interaction

YE 태토
near the wall
W2IE2

dE dE2
PE 1 u 15 W 1토

E 터토 터6
E

W2 1 E E dE
fw.IE一 幽 一

dominate the inge


gray
menin thermal
equilibrium

E most 졹
probable

n iii ET
FIE 前 一

In wins iii
he
WE 에 ㅿ

pij
Micro canonical Ensemble
P RE K17 T 1 in T.im
ME E T E t In ㅿ
B.cl
미터산Q
츤 its phase spacevolume

of microstate Itinerary
nN

Ewe 테야
E f prob 고 mamaligation

S K In w

E E t E2 E10 一
E 터턴 ice G
of state the total system
X dE.cl토
HW 1E 자21E2

티터토 E10

EvilE 야

of us IEE

을 ITEE
2m1E2 기남
maximal
in thermallynam
equibrim
S kh W 2KM나 it KMWa

s i
maximal with variation in E
S21E E
52
i o HE t
2g 遐 諮
츯 s equilibrium condition

T2
f
T

N E 터턴 1보그
Definition
EL 三 t
E
E2

M Need to maximize S

w r.to
in E
rations
V

vi V1 Nz Wi IE Y wa IE V2

슱 in
and for maximaHy
equity
慈人 二
쭗 IT 그도
쮀녀쯞 텨얀잌
Def Et E
Connection to thermodynamics energy exchange
volume exchange
S三S E y kmilE.it

fklnwlE.ir 2km 도 EU

US EN
쯡 HE 쯞ㅑ N

씆 筆
Ed E t Pdr

dE first of
ids pav law thermodynamics

du If

d i
internal
energy

isolated Vi E given

NYEJ
11 7 choose ensemble To 도
microcanonical ensemble w EU
ftp.t S E v klnwlE.ir
E u

i it
1믦 if
Free energies A u
TS
G Ut N TS
H Ut PV

쎘쁉쁨
点 쯞 T 1쯫 p

f du 箔十 Sdt t ids Pd Ut ils

우세뿜니 S에 _Tds
퀣 t.fm.fr
v
Ao 彰 胤

Ptp 晥 仁 n 鬧 巧
M.C Ensemble

K17 WIEN KMMEN K17도 1EV


f 쓰ENml

해태에 玭 潞 mu
잆퉀
災鸞 譽 교
E U

U U S r
이 maxwell's eq
丁二
倚가
며쮏
Idolmaster N particles classical atoms or molecules
identical distinguishable
pts
HIM i a free himdistinguishable
Microcanonical ensemble 6N

IIE
his irritability
Ditto


io
i4Dfd3h 낦h.M
Gibbs Paradox
吐倒
t.tl

v2 is
癎i
Note normalegation
3N
two ideal h
gas systems
GOP 2b
mixing
570 antrop of mixing

S E v K M
惑 t N M
E t EN1712mED
Sit
in ㅌㅌ
KIT 驅 貽門
t 齊 p
3N
Ti extensive intensive

In N N17N N
stirling's formula

E.su air
Fi Ii e 爬川

in i'KT
기N
T 哥人 i u u K1
丘 一
創 泊 添 a
앒 ie
for an

ideal gas

Canonical Ensemble Grandcanonical Ensemble

Canonical Ensemble

isolated
헚T
걎 E 태토
heatreservoir

prob 내 테
of states 내튢테약 E 기E
E2
E Eid E
S E E KMws.IE E
S21 타 쨡기타
1
簒毖
I

T
날 IEE e
S i
const

X etEI.ee
b
E H R

B 씨 MG
e

Boltzmann factor
Pch
ke
Pina
Fit ion function I
et
AN Int
최T1 dip d찴
깨 d자
9 17 at MIT He pd 짬

i In QN

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