!

"#$ &'
lsoLhermal Lxpanslon (1 consLanL, v
1
! v
2
)




Slnce,


Pence,

Slnce v
2
> v
1
,
so AC
1
> 0
" PeaL ls added Lo Lhe gas
CarnoL's rocess


V
2
V
1
=
p
1
p
2
p
0
v
S1
S2
l
ll
lll
lv
v
1
v
4
v
2
v
3
ldeal Cas
!U
1
= !W
1
+!Q
1
= 0
!Q
1
= "!W
1
dW = p
V
2
V
2
!
1
2
!
dV = "NkT
dV
V
= "NkT ln
V
2
V
1
#
$
%
&
'
(
V
1
V
2
!
!Q
1
= "!W
1
= NkT
H
ln
V
2
V
1
#
$
%
&
'
(
Lvery sLep ls reverslble
ldeal Cas
(ldeal Lnglne)
!"#$ ('
Adlabauc expanslon (1
h
! 1
c
, v
2
! v
3
)
1
h
> 1
c



Slnce AC
2
= 0 (Adlabauc),

8ecall,



ldeal gas,
1, v lndependenL
CarnoL's rocess


p
0
v
S1
S2
l
ll
lll
lv
v
1
v
4
v
2
v
3
ldeal Cas
V
3
V
2
=
T
h
T
c
!
"
#
$
%
&
3
2
!W
2
= !U
2
dU
dT
= C
v
!U = C
v
(T
c
"T
h
)
C
v
=
3Nk
2
!"#$ )'
lsoLhermal Compresslon (1 consLanL , v
3
! v
4
)







Slnce v
4
< v
3
,
so AC
3
< 0
" PeaL loss from Lhe gas


CarnoL's rocess


p
0
v
S1
S2
l
ll
lll
lv
v
1
v
4
v
2
v
3
ldeal Cas V
4
V
3
=
p
3
p
4
!U
3
= 0
!W
3
+!Q
3
= 0
!Q
3
= "!W
3
= NkT
c
ln
V
4
V
3
#
$
%
&
'
(
!"#$ *'
Adlabauc compresslon (1
c
! 1
h
, v
4
! v
1
)
1
h
> 1
c




Slnce AC
4
= 0,

CarnoL's rocess


p
0
v
S1
S2
l
ll
lll
lv
v
1
v
4
v
2
v
3
ldeal Cas
V
1
V
4
=
T
c
T
h
!
"
#
$
%
&
3
2
!W
4
= !U
4
= C
v
(T
h
"T
c
)
+,#-.//'
Lnergy balance:


8ecall,

and

Pence,

Slnce,



"
CarnoL's rocess


p
0
v
S1
S2
l
ll
lll
lv
v
1
v
4
v
2
v
3
ldeal Cas !U
total
= !Q
1
+!W
1
+!W
2
+!Q
3
+!W
3
+!W
4
V
3
V
2
=
T
h
T
c
!
"
#
$
%
&
3
2
V
1
V
4
=
T
c
T
h
!
"
#
$
%
&
3
2
V
3
V
2
=
V
4
V
1
!Q
1
= "!W
1
= NkT
H
ln
V
2
V
1
#
$
%
&
'
(
!Q
3
= "!W
3
= NkT
c
ln
V
4
V
3
#
$
%
&
'
(
!Q
1
T
h
+
!Q
3
T
c
= 0
valld for any
01210!3451 cycllc
process

+,#-.//'



Can be wrluen as:



16"-7$8 (exLenslve sLaLe funcuon)



! a measure of dlsorderess
CarnoL's rocess


p
0
v
S1
S2
l
ll
lll
lv
v
1
v
4
v
2
v
3
ldeal Cas
!Q
1
T
h
+
!Q
3
T
c
= 0
valld for any
01210!3451 cycllc
process

!Q
rev
T
!
!
= 0
dS =
!Q
rev
T
19:;#6:8


SubsuLuLe..
.




Pence lf A1 #, q #
8uL Lhere's always heaL loss Lhrough paLh 3
So q < 1
CarnoL's rocess


p
0
v
S1
S2
l
ll
lll
lv
v
1
v
4
v
2
v
3
ldeal Cas
!W = !W
1
+!W
2
+!W
3
+!W
4
! =
T
h
!T
c
T
h
! =1!
T
c
T
h









Pess's Law
AP ls a sLaLe funcuon, Lherefore, lndependenL of paLh
Cne can add enLhalples for a serles of sLeps Lo geL Lhe deslred heaL of
reacuon
1hermochemlsLry

A+8
C
L
8eacuon coordlnaLe
AL
A+8
C
AP < 0
exoLhermlc
AP > 0
endoLhermlc
Lxample:

Assume ldeal mlxlng (well-mlxed)

8reakdown Lo elemenLary equauon:

1hermochemlsLry

2MgO(s) +SiO
2
(s) !Mg
2
SiO
4
(s)
2Mg(s) +Si(s) +2O
2
(g) !Mg
2
SiO
4
(s)
Mg(s) +
1
2
O
2
(g) !MgO(s)
Si(s) +O
2
(g) !SiO
2
(s)
2Mg(s) +Si(s) +2O
2
(g) !Mg
2
SiO
4
(s)
2MgO(s) +SiO
2
(s) !Mg
2
SiO
4
(s)
AP
o
= -600.7 k!
AP
o
= -910.6 k!
AP
o
= -2174.2 k!
AP
o
= -62.2 k!
2x (-)
(-)
(+)
1 dep. of AP
Clven AP(1
1
), C
p
(A), C
p
(8), C
p
(C), C
p
(u)

1hermochemlsLry

aA+bB !cC+dD
aA+bB !cC+dD
(1
1
) (1
1
)
(1
2
) (1
2
)
<&=
<(=
<)=
<*=
!H
1
= !H
4
+!H
3
+!H
2
!H
4
= aC
p
(A) +bC
p
(B)
"
#
$
%
dT = & aC
p
(A) +bC
p
(B)
"
#
$
%
dT
T
1
T
2
'
T
2
T
1
'
!H
3
=W = !H(T
1
)
!H
2
= cC
p
(C) +dC
p
(D)
"
#
$
%
dT
T
1
T
2
'
Lxample:
P
2
C (l) ! P
2
C (g) aL 1 aLm, 373k
AP
vap
= 9717 cal (1 cal = 4.2 [oules)
Llquld v = 0.018 L mol
-1
C
p
(l) = 18 cal mol
-1
k
-1
C
p
(g) = 8 cal mol
-1
k
-1
Assume ldeal behavlor

CalculaLe AP, Au, q, W when
1 mol of llquld waLer aL 1 aLm, 298 k(room Lemp) 600 k, 1 aLm
1hermochemlsLry

!,rev
" # ""
PeaL slowly
LnLropy of a !"#"!$%&'" process ls consLanL,
dS = 0
LnLropy of an %!!"#"!$%&'" process ln an lsolaLed sysLem whlch evolves Lowards
Lhermodynamlc equlllbrlum always lncreases ! maxlmum enLropy ls reached,
when equlllbrlum ls reached.
dS > 0

Second law, dS > 0 ( = only for reverslble process)




Second Law

!S =
q
T
1 2
q
1
1
> 1
2

glves heaL, AS $, so -ve


geLs heaL, AS #, so +ve


!S
1
=
q
T
1
!S
2
=
q
T
2
!S
1"2
= "
q
T
1
+
q
T
2
> 0
. ls Lhe sclence Lo use sLausucal Lechnlques Lo connecL mlcroscoplc behavlor
wlLh macroscoplc properues

Mlcroscoplc scale :
Approx. 10
23
aLoms/molecule
Lach has aL leasL 6 degrees of freedom (x, y, z, p
x
, p
y
, p
z
)
CompleLely lnLracLable
MlC8CS1A1L - exacL denluon (all posluons/momenLa) of Lhe mlcroscoplc
scale
Macroscoplc scale:
p, v, 1, n, C
v
, C
p
eLc.
MAC8CS1A1L
SLausucal Mechanlcs

uenluon:
U (n, v, L) - number of mlcrosLaLes ! number of sLaLes Lhe sysLem has for
glven n, v, L


LnLropy (Mlcroscoplc lnLerpreLauon)

A 8
p =
1
2
!
"
#
$
%
&
N
n = # of balls
v
l

v
f

Cne aLom:

n aLoms:



v
f
> v
l
" U(v
f
) > U(v
l
)

!(V
i
) = "V
i
!(V
i
) =!(V
i
)
N
= ("V
i
)
N
!(V
f
) = (!V
f
)
N
roporuonallLy facLor
Plgher probablllLy
Lower probablllLy
Connecung S Lo U
U
LoL
= U
1
U
2

S = S
1
+ S
2

Assume, S = ((U)
" S o ln U
S = k ln U where k = k
b
= 8olLzmann consLanL
1he enLropy ls a measure for Lhe number of posslble mlcrosLaLes of a sysLem
when a macrosLaLe ls glven

ArgumenLs:
S measures dlsorder"
U lncreases wlLh dlsorder"
LnLropy (Mlcroscoplc lnLerpreLauon)

S = k ln U
Why ls S logarlLhmlcally dependenL on U?
U measures phase space volume
S measures our lack of knowledge golng from mlcrosLaLe Lo macrosLaLe

Mlcroscoplc ! MacrosLaLe (S ls Lhe negauve of lnformauon)

** hase space:
Space of ___ dlmenslons, spanned by all posluons and momenLa, energy polnL
corresponds Lo a mlcrosLaLe of Lhe sysLem.

2
nd
Law:
(a) 1here ls no perpeLual movemenL (perpeLuum moblle) of Lhe second klnd -
l.e., lL ls an englne whlch Lransforms heaL lnLo work wlLh 100 emclency
(b) Lach lsolaLed macroscoplc sysLem wanLs Lo assume Lhe mosL probable
sLaLe (largesL # of mlcroscoplc reallzauon posslblllues).
LnLropy (Mlcroscoplc lnLerpreLauon)

Loslng lnformauon
S (v
l
) = k ln U(v
l
)
S (v
f
) = k ln U(v
f
)


LnLropy
!S = S(V
f
) "S(V
i
)
= k ln!(V
f
) "k ln!(V
i
)
= k ln(!V
f
)
N
"k ln(!V
i
)
N
= kN ln
V
f
V
i
#
$
%
&
'
(
!S = Rln
V
f
V
i
"
#
$
%
&
'
So,


ConsLanL ,

Pence,


LnLropy
dS =
dq
T
dS =
dH
T
dH = dU+ pdV
dU = dq ! pdV
dS =
dH
T
dS =
dH
dT
1
T
!
"
#
$
%
&
dT
dS =
C
p
T
dT
dS
S(T
i
)
S(T
f
)
'
=
C
p
T
dT
T
i
T
f
'
(S = C
p
ln
T
f
T
i
!
"
#
$
%
&
S(T
f
) = S(T
i
) +C
p
ln
T
f
T
i
!
"
#
$
%
&
AS
T
f
T
i
1
Change wlLh C
p

S ! 0 as 1 ! 0k
1hlrd law of Lhermodynamlcs:
1he enLropy of a perfecL crysLal, aL absoluLe zero kelvln, ls exacLly equal Lo
zero"
lL ls lmposslble Lo reach absoluLe 0" ln a nlLe number of sLeps
1 ! 0k, C
p
, C
v
! 0
lrom 0 Lo 1
f
,




When 1
f
! 0
lor S(1
f
) ! 0, C
p
! 0

1hlrd Law
S(T
f
) = S(0) +
C
p
T
dT
0
T
f
!
S(T
f
) =
C
p
T
dT
0
T
f
!
S
1
Zero
slope
lundamenLal Lhermodynamlc relauon:

SysLems whlch experlences change ln composluon, musL lnclude composluon
varlables.
Chemlcal poLenual

where n
l
, n
l
. are Lhe number of moles of specles l, [,.presenL ln Lhe sysLem

Comblnlng 1
sL
Law and 2
nd
Law
!G
!n
i
"
#
$
%
&
'
T, p,n
j
,...
=
i
!G
!n
i
"
#
$
%
&
'
T, p,n
j
,...
=
!U
!n
i
"
#
$
%
&
'
T, p,n
j
,...
=
!H
!n
i
"
#
$
%
&
'
T, p,n
j
,...
=
!A
!n
i
"
#
$
%
&
'
T, p,n
j
,...
=
i
dU = TdS ! pdV +
"
i
dn
i
dH = TdS +Vdp+
"
i
dn
i
dA = !SdT ! pdV +
"
i
dn
i
dG = !SdT +Vdp+
"
i
dn
i
dU = TdS ! pdV


8ecause all Lhe naLural varlables of Lhe lnLernal energy, u are exLenslve
quanuues, from Luler's homogeneous funcuon Lheorem,

Luler's equauon
ulerenual of Luler's equauon,


Compare:
Clbbs-uuhem relauon
Luler's Lquauon
dU = TdS ! pdV +
"
i
dn
i
U = TS ! pV +
"
i
N
i
dU = TdS ! pdV +
i
d
i
"
N
i
+SdT !VdP+ N
i
d
i
"

i
SdT !VdP+ N
i
d
i
"

i
= 0