- 2009

http://www.cc.uoa.gr/~ctrikali

. - 2009


.
.
A.N. Matveev
A. Kikoin & I. Kikoin

:
:
: Molecular Physics
: Molecular Physics

Abbot Van Ness

Zamansky & Sears
J. Lee & F.W. Sears
R. Kubo
Zamansky & Dittman
.

:
:
:
:
:
:

SHAUMs /*
Thermodynamics
Thermodynamics
Thermodynamics
Heat and Thermodynamics
()

: (2-3)
Alonso & Finn
Halliday-Resnick
O Hanian
Feynman
Serway
Ford
Young

1
&

2 -
Carnot Clausius
3 ()
( )

 , 1 2
1. ( )
2. 1: ( )
3. 28 (), 6-8
4. 2
5. 100
6. 2 >=40
7. >=
40. B 2 . >=45
9. 2 : 3 , . -,
10. 2
( 6)
11.
( )

P, V, T

PV=nRT


SCIENTIST

Boltzmann

Carnot

Clapeyron

X
X

1830

1840

1850

1860

1870

1880

1890

1900

1910

1920

Clausius
GayLussac

Gibbs
Helmholtz
Joule
Legendre

Maxwell
Mayer

Otto
Poisson

Thomson Kelvin
Waals, Van
der
1770

1780

1790

1800

1810

1820

1810 - 1890

P, V, T

 &
1. :

2. : .
3. : ()
.
4. :

(m=0, Q=0)
(m0)
(m=0, Q0)

T, P,

T, P,

m1, V1, S1

m2, V2, S2

5. / : (0, =0)
6. :
.
7. :

.
8. / :
:T, P, V, m, S

 :

(),
,
( = 6
)
:
(
:
)

 :
( )
:
(..
) :
A .

.
:
.

 :
( )
1

2

3
:
1=3 2=3 1=2

--

1. :

W Fdx
) PdV
=
= PSdx
= Pd ( Sx
=
W dW PdV ( )
n

W = f i dxi

i =1

F: < 0 (-)
( )
: > 0 (+)
( )

2.

dQ = Q

() .
Q :
Q > 0
Q < 0

3. U

(-)
(
).
:
.

().

: dU ( U !!!)

1
(Mayer*, Helmholtz, Joule**)

Q = dU + W = dU + pdV
, .

?

d
.

Julius Robert MAYER (1814-1878)

(GE)

Ludwig Ferdinand HELMHOLTZ (1821-1894)

James Prescott JOULE (1818-1889) (EN)
(*) Mayer : Java/26y/MD/: (1842)
:
Lavoisier

 : / /
/
1842 paper (*) . 4 papers < 1851
1852 /2
.
HELMHOLTZ :
JOULE : : 1 Cal = 4.18 J
(1818-1889) (1 1g 1 atm)
(*) "Remarks On the Forces of Inorganic Nature"
in Annalen der Chemie und Pharmacie, 43, 233 (1842)

Fig. T12.1, p. 369

Slide 11

 (**) Joule (1850)

26 kg 1,65 m.


6,65 kg .

20

0,3oC (#)
Mbgh*20 = 26kg X 9,81ms-2 X
1,65m X 20 = 8417 J
Q = Mwc = 6,65kg*1Cal/kg *
0,3 grad = 1,995 Cal ~>
1Cal = 4,219 J

M
Mb = 26 Kg
h = 1,65 m

water

= 6,65 Kg

(#)

 ?

Joules
10 Joule 0,0024 cal 1 kg
0,0024 C !
1000 Joule 0,24 C !
Joule




:
V,T, P U.
( )
(
), :
V+dV, T+dT, P+dP, U+dU ( -)

Q / W.

V , T , P, U

P = P(V , T )

V = V ( P, T )
T = T ( P, V )

V dV
T dT
P dP
U dU

V,T, P, U : (
)
Q,W :

 V,T,P U

. Q W



(V,T, P U).

!
!


.

.
Q
d
.
[ (
)
( -)].



.

 ( )
f(x), .
F(x)

f ( x)dx = F ( x + dx) F ( x) = dF ( x)

(1)

(1)

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

: d
.

2 (x,y)
d :

d = P( x, y )dx + Q( x, y )dy (2)

(1),
:

d = P( x, y )dx + Q( x, y )dy
= ( )* =
?
= F ( x + dx, y + dy ) F ( x, y ) (3)
F
F
= F ( x, y ) +
dx +
dy F ( x, y )
x
y

? F
F
d =
P( x, y )dx + Q( x, y )dy = dx +
dy (3')
x
y

(*) f(x). x=a (n+1) :

(Taylor)
f (a )
f (a )
f ( n ) (a)
2
f ( x a) = f (a) +
( x a) +
( x a ) + ... +
( x a ) n + Rn +1 ( x)
n!
1!
2!

x-a 0 : , ..
1 F
1 F
( y + dy y ) + ...
F ( x + dx, y + dy ) F ( x, y ) = F ( x, y ) +
( x + dx x) +
1! x y
1! y x
F
F
dy F ( x, y )
- F ( x, y ) = F ( x, y ) +
dx +
x y
y x

F
F
dy
F ( x + dx, y + dy ) F ( x, y ) =
dx +

x y
y x

 F
F

P=
, Q =
x y
y x

P
=

2 F
y x
y

x
y

Q
=

2 F
xy

P
Q
(4)

y x x y (4):

d .

F
F
dy
d = Pdx + Qdy =
dx +
x y
y x
= dF = dF ( x, y )

( - P V ):

f ( P, V ) = 3P V 4 PV
2

2 f
f
2
2
3
P
12
PV
=

PV P V P
= 6 P 12V 2

f
f
3

6 PV 4V

=
VP V P V
2
= 6 P 12V
2

 (4)
: F F
P ??? Q
=
( 4)
y x x y

f ( x)dx = dF = F ( x + dx) F ( x)

( ):
( x2 , y 2 )

( x2 , y 2 )

( Pdx + Qdy) = dF = F ( x , y ) F ( x , y )
2

( x1 , y1 )

( x1 , y1 )

(
/ (*) x,y).
F(x,y) x,y.

(5)

 x, y

F
F
dy = dF
d = Pdx + Qdy =
dx +
x y
y x
d , F
.
( F(x,y) x,y
(x,y) (x,y) )

: dS

Q
T

( )

xdy + ydx

(= d 1 )

xdy ydx

( = d 2 )

d = Pdx + Qdy

2 ( , . )

 F=pV

dF = d ( pV ) = pdV + Vdp
V
V2
V1

L1

(p1,V2)

L2

A(p1,V1)

p1

B(p2,V2)

p2

(p2,V1)


:
dF :

I1 (dF ) = ( pdV + Vdp) =

L1

L1

V2

(p1,V2)

L1

A(p1,V1)

L2

V1
p1

p1 ,V2

)+

p1 ,V1

B(p2,V2)

(p2,V1)

p2

p2 ,V2

)=

p1 ,V2

= p1 (V2 V1 ) + V2 ( p2 p1 ) = V2 p2 p1V1

I 2 (dF ) = ( pdV + Vdp ) =

L2

L2

p2 ,V1

p1 ,V1

)+

p2 ,V2

)=

p2 ,V1

= V1 ( p2 p1 ) + p2 (V2 V1 ) = V2 p2 p1V1

I1(dF) = I 2(dF)

:
d1 !

dF = d = Pdx + Qdy
Q

d 1 = xdy + ydx
d 2 = xdy ydx
Q

P ??? Q
=

y x x y

P ???

=
V p

p V

pdV + Vdp

(= dF1 )

dF1 :

P
V
V = V = 1
p
p
P = V

Q = p Q
p

= = 1
p
p V
V

dF1 : .

 dF2 :

P ???

=
V p

pdV Vdp
p V

P
(V )
V = V = 1
p
p
P = V

Q = p Q
p

= = 1
p
p V
V

(= dF2 )

dF2 !


:
d1 :

I1 ( 1 ) = ( xdy + ydx) =
L1

L1

x1 , y 2

x1 , y1

)+

x2 , y 2

)=

x1 , y 2

= x1 ( y2 y1 ) + y2 ( x2 x1 ) = y2 x2 x1 y1

I 2 ( 1 ) = ( xdy + ydx) =
L2

x2 , y1

x1 , y1

)+

x2 , y 2

)=

x2 , y1

L2

= y1 ( x2 x1 ) + x2 ( y2 y1 ) = y2 x2 x1 y1

I1(1 ) = I 2(1 )

d1 !

 d2= xdy-ydx :

I1 ( 2 ) = ( xdy ydx) =
L1

L1

I 2 ( 2 ) =

)+

x2 , y 2

x1 , y1

)=

x1 , y 2

= x1 ( y2 y1 ) y2 ( x2 x1 ) = 2 x1 y2 x1 y1 x2 y2
x2 , y1

( xdy ydx) =

L2

L2

x1 , y 2

( - )+

x1 , y1

x2 , y2

( - )=

x2 , y1

=
y1 ( x2 x1 ) + x2 ( y2 y1 ) =
2 x2 y1 + x1 y1 + x2 y2

I1 ( 2 ) I 2 ( 2 )

d2 !

F ( x, y )
F
F
dy
dF = F ( x + dx, y + dy ) F ( x, y ) =
dx +
x y
y x
..

F ( x, y ) U (V , T )

dU (V , T ) = U (V + dV , T + dT ) U (V , T ) S
O
U
U
dU (V , T ) =
dV
dT +
S
V T
T V

 ( )
:
.
:
P,T,V,
.. : Boyle:
PV =

( )

= . (
, ).


(.. V)
P, T
( )
P,T
( )

,

()
,
.

 .. P,V

/

W=W

: () ()
: (10-6s)*
(*)
( )

14.2

mo = m + m

(S=R2)

P . = Po + P +
mo g
F
"
"=
S
S

 1 (dm):

mo g dm g
Po +

S
S

dV=Sdy,
W=W :

W = ( P Po ) Sdy = ( P Po )dV

VoV ( )
V

W = W = ( P Po )dV
Vo

, .. .

RTo
.
V

V
W = RTo ln( ) Po (V Vo )
Vo

(1)

V Vo
y =
S

VoV, :

F = m( y ) g m(y)

y: : y

S
m( yo ) = mo , yS = V y =
V
yo S = Vo
- y :
y

W = g m( y )dy
yo

m( y ) g =" F " = S ( P Po ) = S

RTo
V

RTo

SPo =
SPo
y

 :
y

y
W = m( y ) gdy = RTo ln( ) SPo ( y yo ) =
yo
yo
yS
) S ( y yo ) Po =
= RTo ln(
yo S
V
= RTo ln( ) Po (V Vo ) { #1}
Vo

 : .
, >>>. 1
. 1 .. .
(.. 5)

:
P
P

= 1/5

(0.2)

= 4/5 (1-1/5)

 =2 , ( P ):

( 5)

P1 = 1

(0.04)

3, 4, 5, ...,

P25

( )

= 1 1

1

5
N

1
1 1
5

24
=
5
25
2

(0.96)

:
.. 2s 1 , 2
22s 323s, ..1002100s (>>>)
(< 10-8Torr!)

 C
Q ,
d: :

dT

() , Q:
C=Cv

PV=RT

() , ,
Q: Cp
PV = RT

: Cp > Cv

..

( dU U )

U
Q dU + PdV dU
) CV = =
C
(()

=
=

V
dT
T V
V dT V
dT V

( )

U = U (V , T )

dU
U
CV =
(
)V
dT
T

(()
) P = .

Q
CP

dT P

(Q )P = (dU + PdV )P = d (U + PV ) P

(=" dH " )

(dU + PdV + VdP )P

dH
:

U + PV

Q
CP =
=
dT P
To

H
U + PV H () C P =

T P

 1 mole * :

5
3
**
H = U + PV = U + RT = RT + RT = RT
2
2
5 RT

5
H
2
CP = R
CP =
=
2
T
T P

(* , )
(** )
,

.


mole

PV = nRT , P = n RT V
P = P(V , T )

:
:

[ T = T ( P, V ) , V = V (T , P) ]
U=U(V,T) ( )
:

U
U
dU =
dV
dT +
V T
T V

..

Q = dU + PdV

U
U
Q =
dT + P +
dV
T V
V T

S
O
S

Q
dT

U
U
() Q =
dV
dT + P +
V T
T V

U U dV
C =
+ P +

T V V T dT

P = .

U V
U
CP =

+ P +
V T T P
T V
CV

(= 0)

V R
R
PV = RT V = T =
T P P
P

(1 mole)


U
Q = CV dT + P +
dV
V T

U
=0

V T

R
V

=
T P P

C P = CV + R C P CV = R
CP
R
CV =
=
1
CV

Mayer

T CV V=. ..
5 J/mole K
CP P=. ..
7 J/mole K

i
i
U = N A k BT = RT
2
2

i
CV = R
2

i
U

= R
T V 2

i+2
CP =
R
2

i :
: i=3 (3 )
( ) : i=5 (3 .+ 2 .)
( ) : i=7 (3.+ 2 .+2.)

CV/R

(CP-CV)/R=1

He:

1.519

1.001

A:

1.5

1.008

N2:

2.45

1.005

O2:

2.50

1.004

Cl2:

3.02

1.009

CO2:

3.4

1.02

NH3:

3.42

1.06

3

2

( )

5

2

0=C=O
(>2)

: C=C(T)

5 R
2
CV =
7 2 R ( >>>)

 :

.. : =
:

En

(n = 0, EoT = )
2

= n +
2

(m,.)

En = qn (n + 1)

2I o

(2: 2 )

 : ()
() (spin).
spin: // -//

( )

En = qn (n + 1)

.. 2 :

(n: 1,3,5,..)

75%

0.2%

(n: 0,2,4,..)

25%

99.8%

..

20K !

ET

!
E
100

<<<

..

E3 E1 = 10q
E 2 E0 = 6 q

kT << 6q

E1 = 2q, E0 = 0, ET = 0
3 . 3R/2
>> 5 .. (2=86),
>>>(6400) .

 CP

 2.2

PV2=const. ? (n=1 mole)
PV=RT (1 mole)
dV>0

2.2
PV2 = const 2PVdV + V2dP = 0
2PdV + VdP = 0 (1)
PV = RT () PdV + VdP = RdT (2)
(2) VdP = RdT PdV (3)
(1) & (3) 2PdV + RdT - PdV = 0
PdV + RdT = 0
dT = - PdV/R (dV/dT)=-(R/P)
P, R dV >0 ()
dT <0

2.6/2.4 ,
Vo NVo P=V
( ). ()
U () W

() C Cv, R

dU = ncV dT , PV = nRT & P = V V V = nRT

2
2
V = nRT 2VdV = nRdT dT = VdV
nR

2
c
dU = ncV VdV & R = cP cV = P & cV = R
cV
1
nR
NVo

2cV
Vo2 2
2 V
dU =
VdV dU = U =
N 1
=
( 1)cV
( 1) 2 V
( 1)
Uo
o
U

(
1) Vo 2
( 1)
dW = PdV = VdV =
dU W =

N 1

2 1
2

W =

2
o

(N

2
Q dU + PdV dU
dV
dV
=
=
+P
= cV + P
C
dT
dT
dT
dT
dT

PV = nRT PdV + VdP = nRdT

& P = V dP = dV
PdV + VdV = nRdT 2 PdV = nRdT
dV R
nR
=
C = cV +
P
dT 2
2

 2.7

(1)

(2)

(1) (2)


.
mole CV .
(1)
.
C1
(1) V1, V2, CV, .
C2. V1=V2?

Q1 = dU1 + p1dV1 = CV dT1 + p1dV1

(1)

(2)

RT1
= CV dT1 +
dV1
V1

Q2 = dU 2 + p2 dV2 = CV dT2 + p2 dV2

RT2
dV2 (1) 0()
= CV dT2 +
V2

(2)

(1)

C2

Q2
dT

=0

V1 T1
dV1 dV2 dT1 dT2
P1=P2 ( )
(3)
=

V2 T2
V1
V2
T1
T2
V1+V2=V= . dV1+dV2=0 (4)

1 1
R
dT1
dV1 =
+ +
(2), (3) (4)
V1 V2 CV V2
T1

(5)

CP-CV = R (6) (1), (5) (6)

RV2
dT1
Q1 = CV +
(V2 + V1 )

CV
R =

V1 + V2
V2
CV
R =
C1 =
= CV +
(V2 + V1 ) V2 + V1
dT1

Q1

2
V1 = V2 C1 =
CV
+1


1.

P=.

2.

V=.

3.

=.

4.

Q=0

5.

C=.

1.
P=

(1 mole)

T1 =

P1V1

T2 =

P2V2

W = P1dV = P1 dV = P1 (V2 V1 ) =
2

R
= P1 dT = R dT = R (T2 T1 )
P
1 1
1

R
R

Q = C P dT
dU = CV dT

2.

V=
2

T2>T1

W = PdV = 0
1

T1

Q = dU = CV dT
anti-film

3.

T = .

P
P1

P2
V1

V2

PV= P=(1/V)

Q = W + dU

dU = 0

0
2

dV
V2
= RT ln
W = pdV = RT
V1
V
1
1

v = 1 mole
T = .

P = .
V = .

PV = .
V
= .
T
P
= .
T

() (1)
() (2)
() (3)
V
= .
T
1
2

2
1
V

T
T

4.

Q=0

dU
U
cV =
=
T V dT

dT W

dQ = 0 = dU + pdV 0 = cV dT + pdV

PV

cP cV = R PV = RT PV = (cP cV )T T =
cP cV
dT
p/ dV
+
=0
/T cV
p/ V
T
cP cV

dT cP cV dV
dT
dV
+ ( 1)
=0

+
=0
T
cV V
T
V

TV

( 1)

= .

PV
(1 )

T=
T P
= . PV = .
R
:

dV PV +1 +1 RT1 V1
1
W = PdV = PV =
V2 V1 =
1 V2
V 1
V1
1

1 1

V2

T1 T2

W = R
1

1 1

cP
=
cV

dP

dV T

dP

dV dQ=0

PV = RT

V
P

R
dP

= =
dT V V

5.

( )

C = ( :
cV, cP, , 0 )
c=. . :

cdT = cV dT + PdV (c cV )dT pdV = 0

dT cP cV dV
+
=0
T cV c V

TV

n 1

cP cV
= ., n 1 =
cV c

PV = .
n

c cP
n=
c cV

(* )

C= 0

cP
cV

n=
1
0

:
:
:
:

Q=0
dT=0
dP=0
dV=0

P, V, T

PV=nRT

PV = .

V = .

P = .

T = .

P
= .
T

V
= .
T

W = 0

W = pdV

W = pdV

W =0

W = P(V2 V1 )

W = RT ln

Q = CV dT

Q = C P dT

Q = W

Q = cV (T2 T1 )

Q = C P (T2 T1 )

Q = W

du = CV dT
U = cV (T2 T1 )
CV =

R
1

PV =

du = CV dT

du = 0

U = CV (T2 T1 )

U = 0

CP =

R
1

=0

CT =

=1

V2
V1

c = .

Q = 0
PV

= .

W = pdW = dU
W = U = CV (T2 T1 )

PV n = .

W = pdV
W=

1
( P1V1 P2V2 )
n 1

Q = 0

Q = cdT

Q = 0

Q = c(T2 T1 )

du = CV dT = W

du = CV dT

U = W = CV (T2 T1 )

c=

c = 0
n= =

CP

U = CV (T2 T1 )

CV

R ( n )
( 1)(n 1)

c CP
n=
c CV

dP

dV T

dP

dV dQ =0

(1<n<)

PV = RT

a
a

2a

3a

2a

3a

3a

3a
a
a
2a/3

. mole
p=po+/V (po,
). ()
()
,
V1
V2 (R !)

2
2
(i + 2) R / 2 i + 2
= =
=
= 1+ i =
cV
iR / 2
i
i
1
cp

c p , cV

a
pV = RT ( po + )V = RT
V

RT = poV + a

dV
c = cV + p
dT

dV
R
RT = poV + a
=
dT po

dV
R
a R
= cV + p = cV + ( po + ) ,
c = cV + p
dT
po
V po
Q

dV
a R

c=
Q = cdT = (cV + p
)dT = cV dT + po + dT
dT
dT
V po

po
a R
dV

Q = cV dT + po + dT = cV
dV + po dV + a
V po
R
V

V2
po
Q = cV
(V2 V1 ) + po (V2 V1 ) + a ln
R
V1

po
po
(V2 V1 )
dU = cV dT = cV
dV U = cV
R
R

V2
Q = dU + W W = po (V2 V1 ) + a ln
V1

5
4
3

1
V

1
3
5
4
2

PV=RT P/V=RT
V

:
i) :
ii) : .
iii) :
iv) :

 2 ,
.
P,V,T

W(J)
|
|
|
|
2

|
|

|
|

7
6
5
4
3
2
1
0

| |
0 1

|
2

|
3

|
4

|
5

|
6

|
7

|
8

Q(J)

? (
..)

Q = U + W U = 0 Q = W 45o 3
i+2
2
W
W = RT & Q = C p T =
RT
=
Q
2
i+2
2 , 2 & 2
5
7
8
2

17.1
i+2
R
i+2
cP
2
2
2
= 1+
=
= =
= 1
i
i
cV
i
i
R
2

O : v v1 : v = U + v
O : v1 v2 : v1 = U + v1

vx = U + vx , v y = v y , vz = vz
v1x = U + v1x , v1 y = v1 y , v1z = v1z
, :

v1x = vx

v1x = U vx = U + U v x = 2U v x

 .
1
1
2
2
= m(2U v x ) mvx 2mvxU
2
2
( +x)
= 2mv + xU
S ,

(U 0)

mv + x Sdt
+ 2

dE = 2mnUSdt
(v x ) dE = 2mn(v x ) dV
+

Sdx = dV

dU = 2mndV f (v x )v x dv x
2

iNkT
( i .. v =
2

dU = nkTdV

2
i

i dT
dV
dU
=
,
2 T
V

TV = TV 1 = .

Poisson


Q
dT P
Q =
dU + PdV = CV
+ dV
T
T T
T

CV dT

d ln T

= CV d ln T + Rd ln V
T

dV
R=( R=
Rd ln V )
V
V

Q
dS =

d (CV ln T + R ln V ) (1)
T

( )

Q
dS =

d (CV ln T + R ln V )
T

(1)

(dT=0, )
(1)

dS

Rd (ln V )

V2
=
dS R d ln V S 2 S1 =
R ln
V1
1
1
2

V1

V1
N1 = 3
l

(1 mole, NA)

()

=
V

10

10

 V2

V2
N2 = 3
l

N1 !
o
1
( N1 N A )!

N2 !
o
2
( N 2 N A )!

N 2 !( N1 N A )! (*)

N1 !( N 2 N A )!

N
2 N 2 2
e
N
2 N1 1
e

N2

N1

( N1 N A )
2 ( N1 N A )
e

( N 2 N A )
2 ( N 2 N A )
e

N1 N A

N2 N A

N N
1
1
+
+ ...)
(*) Stirling: ( N ) = 2 ( ) (1 +
2
e
12 N 288 N

N!

 1, 2 >>

N2

o N1
1
2

NA

Nl 3 = V

o2
V
1
V2
2
ln
=
ln
=

V1 N A o
V1
1
NA

o
R
S 2 S1 =
ln 2 = k ln o k ln o
2
1
N A o
1

S=kln

O ln (# . -
S)

A)

(1877) Boltzmann (1844 - 1906)

 S
:
:
=
dS
..

d (CV ln T + R ln V )

: (dV=0)

T2

S = S 2 S1 = CV ln

T
1

S , T

=
dS d (CV ln T + R ln V )
: (d=0)

dS = d ( R ln V )

S , V

V2
=
S S 2
=
S1 R ln
V1

*: (Q=0) ( S=0)

T2
V2
S = S 2 S1 = CV ln + R ln
T1
V1
(*)

TV
1 1

= T2V2

= CP

C
V

V1
V2
T2

( 1) ln =
ln
=
( 1) ln

T1
V2
V1

V2
CP

S = S 2 S1 = CV
1 + R ln = 0

V1
CV

= 0

CP + CV + R =
0

V S
T S
(S = 0)

Q
d (CV ln T + R ln V )
dS =

S = k ln


TS

dS =

Q
T

Q
S

CP = T

dT
T

P
Q
S
T

CV =

dT V
T V

(1)
(2)

CP > CV
T
T
(1)
=

S P CP

T
T
(2)
=
S V CV

<

!!!

Q : ()
: Q1= Q2
,
:

Q1

T1

Q2

T2

1 > 2 S1 < S 2

Q (Q1=Q2)

T1 + T2
=

()
:
:
(
)
.

T1 + T2
dT
S1 CP =
T T CP ln 2T1
T1 + T2
1
2CP ln
S =S1 + S2 =
2 TT
1 2

T1 + T2

CP ln
S2 =

2T2
T1 +T2
2


& ( )
W

( 121 ) :
2

=
W121

P dV + P dV
a

= /


:

Q = dU + pdV = W
.

* ( < 0)

..

u1 0 !

 .

, .
+

W
n= +
Q

(Q , W )

( Q = Q + Q = Q + Q = W )
+

(<0)

<0
+

Q +Q
Q
n= + =
1+ + 1
Q
Q

/
Carnot

2
2

/ Carnot

V2
Q + =
1 Q = du + 1 pdV =RT1 ln V1
2,3 4,1

1
1
TV
=
T
V
1 2
2 3

V4
V2
V2 V3
= ln =
ln
V1 V4
V1
V3

=
Q

Q RT2 ln
=
3

1
1
TV
=
T
V
1 1
2 4

T2
nc = 1
T1

V4
V3

=
2

+273=423 K

=
+273 323 K

150 C

50 C

323
1
0.23 23%
=
=
423

+273=1773 K

=
+273 473 K

T1 1500 C

T2

nMEK

200 C

473
1
0.73 73% > n
=
=
1773

P,
105 Pa
A

Step

AB

--

BC

--

--

CA

V, m3

Q+

T1=T2

Q
= 1+
Q +

Q=0
T3=T4

Q-

S1=S4
2

Q=0

3
Carnot

S2=S3 TS

Q + = Q = T1 dS = T1 (S 2 S1 ) Q = T3 (S 4 S3 )

T3
3 (S 4 S3 )
T3 (S3 S 4 )
Q
1+
= 1+
= 1+
= 1
+
T1
Q
T1 (S 2 S1 )
T1 (S 2 S1 )

2 Kelvin (1851)
(Thomson)

Q
n = 1 + + n=1 Q-=0
Q
Kelvin (Planck):
.
()
.

(
,
).

 S 0
(Q=0)

U =
W

Q + U
V=, =. S =
=
U = T S
T
T

W = U = T S < 0

( )

Clausius: , ,
.
1

, :
1,V1,U1,S1
T2,V2,U2,S2 S=S1+S2

dU =
dU1 + dU 2 =
0 dU 2 =
dU1

V1,V2 S=S(U)

S
S
dS = dS1 + dS 2 =
dU1 +
dU 2 0
U1 V1
U 2 V2

(1)

1
Q
dU
S
(dS )V =
=

=
T V T V
U V T

W=pdV=0

(2)

1 1
1
1
dU1 + dU 2 0 dU1 0
T1
T2
T1 T2

-dU
1

T1 < T2 dU1 0

(3)

(2) (dU1) .
Clausius :
(T2) |Q1|
,
(T1) |Q1|,
|Q2|<|Q1| W.
:


Clausius

Kelvin ()

= 2 |Q1|-|Q2|
(Kelvin)!
*

= 1-(T4-T1)/(T3-T2)
= 1-rn

http://www.sciences.univ-nantes.fr/physique/perso/gtulloue/thermodynamics/cycle/joule_a.html


, .
( Q)

1
2 .
( Q)

) : (*)
1, :

| Q1 |
T1
1
1 (>1)
=
=
=
=
W
T1 T2 1 2
nc
1

) :

| Q2 |
T2
1
=
=
=
1

W
T1 T2 nc
.

(*) performance:
(
)

Carnot) efficiency: n ()

1 Btu=1,055kJ

-22C
20C.
? (TKELVIN!!)

Tlow = 22 o C + 273 = 251K

Thigh = 20 o C + 273 = 293K
Tlow
251
=
=
= 5,98
(Thigh Tlow ) 293 251
5,98 Joules
Joule

 Carnot
Carnot:
n
na Carnot
c
.

Q
Carnot () n = 1 +

(
Carnot)(./.)

 n > n.
+
a

Q
Q Q > Q
=

Q-, ( n
> n) Q-. .
() : O 1 : Q+ ,
W, Q- ( )
W, () Carnot. ()
. W

(). : Qa > Q

Q = Q

+
() Qa
() Q+ !

( )

: (W=W-|W|)
Kelvin!

n > na na n

Carnot: n


.

2o . Carnot
, , Carnot
1
Q2+

Q1+

W2

W1
Q2

Q1

1=2
( )
1<2
:
:

: Q2+, Q2- (2) W2.

To W2>W1 , 2>1
: , W1,

|Q1-| 2 |Q1+|=|Q2+|
1

 2 > 1 |Q1-| > Q2- |Q1-|- |Q1+|

.
1 ,
. ()
|Q1-| - Q2- ( elvin)
2 > 1 .

<->
~> 1>2!!

1 = 2

( /)

Q+

4
S1=S4

1
Carnot (<C)

Q-

3
S2=S3

: ,
: Carnot,
: , ,
0!

S
1, 2

Q = TdS = dU + pdV

W
= +
Q

 C () > (), 1,
2!
~S

Q =
TdS =
dU +
pdV =W
(-)

) Carnot=
: WC

TdS

Q+

A2

T1 dS +T2
A1

S1=S4

Q-

S2=S3

dS

(1)

A3

(1234: +1+2+3+4)

A4

S1

S2

(1) ~> WC= T1 ( S 2 S1 ) + T2 ( S 4 S3 )= (T1 T2 )( S 2 S1 )

=
Q
+
C

A2

TdS
=
A1

A2

T1=
dS T1 ( S2 S1 )
A1

WC T1 T2 ( S 2 S1 )
T2
=
= 1
C +
QC
T1 ( S 2 S1 )
T1
1

Q+

4
S1=S4

Q-

3
S2=S3

B). :
W =
TdS = '' '' = (T1 T2 )(S2 S1 ) 1 2 3 4 =
1

WC 1234

+
+
=

Q+ =
Q
TdS
S
S
Q
(
)
C 12
C
1
2
1
1
2
1
2

1234>12!

W
Q+

WC 1234 WC
=
< + C
+
QC
QC 12

: C= 12, 34=0
, , ~> CARNOT!
(1=2=3=4=0 =1234)

1
1

S1

12=1+2
12=1+2

2
3

2
S2

,
S1 S2
SS

W=
WC 1234 + 12
a
+
+
Q=
Q
a
C 12 + M 12 + 12

WC 1234 + 12
=
a
< C
+
QC 12 + M 12 + 12

T
T1

Carnot

T2

h
: abcda

c
g

e
f

Sab=-Scd S=0, Q+=habg

: abecda Q+..=habg

Q-..=hdef>hdcg= Q- , Sed>Scd
. 2 () , <.

2.41
:
Q = TdS Q > 0 1 2

= 1
1

Q < 0 2 3
Q = 0 3 1

Q+

Q = (S112S 2 ) =
+

2,3

S1,3

T1 T2
2
(S 2 S1 )
= T2 (S 2 S1 ) +
2
T1 + T2
+
(
S 2 S1 )
Q =
S2 S
2

Q = (S1 32 S 2 ) = T2 (S 2 S1 )
Q

2T2
T1 T2
= 1 + = 1
=
T1 + T2 T1 + T2
Q

 Clausius
( C1, C2)

C =

Q
1+
Q+
2
1+
1

(Q-<0)
( .,
Carnot)
( Carnot)

2
Q

: C 1 + + 1
Q
1
Clausius
Carnot:

Q
Q
+
0
1 2

 (
).
:

Q+

Carnot
(
)

+
.
( )

11

W1

Q=-Q-

>0 ()

2
2

W2

=
f( 2 + )

W
=

W + W
1

 2 W2
1 Q+ 1 W1,
Q , 2
1
2 , ( 1),
.

 , , :

+ T T1
d=
W1 Q 1 =
Q
1

T
T
T

1
+

Cl/

( = Cl,
. Car)

T1

T1

Q 1
=
Q 1 =
T

>0

(1)

2 ~> W2

W2 =
Q,
pdV

= T1

Q
T

W=

Q T1
+ Q =

Q
T

W + W=
(W + Q )
=

 Kelvin Q+ !
a ,
!

W0

SOS

Carnot > Carnot

Carnot >
= ()
= ( , )

 :
!
.. () Q=0 & W=0.

(V2V1), Q=0 & W=0,
W=0 , .

. :
:
=0

:

()
(

,

.

SOS!

( )

: 1

Clausius

T
0

Q
T

=0
(.Q=0)

= dS
2

Q 1

=
d
S
=
S

1
2

2 T
2

S2 S1 (1)

S2 S1
, 1 ( S1) 2 ( S2),
, .

(2 ).

SOS!!!

2
( )
Boltzmann:

=
S k ln

2
=
S k (ln 2 ln 1=
) k ln 0
1

2 1

2 , 2
.
,

!


( )

( )

,
.





The
amount
of energy
transferred


- to
or
from
a thermodynamic
system in

an
adiabatic
transition--measured

by-
work donein
the
system's
environment--depends
only on the

initial
and final
equilibrium states.

 ( Carnot),
2
.
( 1960)



KelvinPlanck .

1 /

Carnot

 ,
Boltzmann:

?
,

.. 60600 = 36000 (2+3=5 )
= #

( Richter;
3 4 100 1000
1. dB

{dB = -10 log(P1/P2)}
Warmth disperses and time passes :H.C Von Baeyer, 1999

 S
SOS!!!


S
,
()
()
( 1 2).

:
: !

:
. .

/ .
(dU=0),

V
S =
RT ln > 0
V1

()

Q=0
pdV=0
W=0
dU*=0
(*)

S
.
m1,cV1,T1
m2,cV2,T2

/./
1 2

V1,2=.,
1>2 CViCVi ().

m1cV 1T1 + m2cV 2T2

m1cV 1 (T1 =
T3 ) m2cV 2 (T3 T2 ) T3 =
m1cV 1 + m2cV 2

 (1)(2)
m1,T1
m2,T2

m1,T1

m1,T3

m2,T2

m2,T3

(1)(2) : m1,m2
3 (
)
m1,T1
m2,T2

m1,T3
m2,T3

S.

m1,T3
m2,T3

 (dSQ/T)
m1,T1
T1>T2
m2,T2

m1,T1

m1,T3

m2,T2

m2,T3

:
P
m1,T3
m1,T1
m1,T3
( )
m2,T3
m2,T3
m2,T2

T1
T3
T2
V

T3 dT
T3 dT
Q
T3
T3
S =
=m1cV 1
+ m2cV 2
=m1cV 1 ln + m2cV 2 > 0
(1) T
T1 T
T2 T
T1
T2
(2)

 S=kln, 21

2
=
S k (ln 2 ln 1=
) k ln
0
1
: S
, .
.
2
.

 -
: ,
:
/,
,

( ):

()

 1 2 :

:


1 :


()

( 1
).
2 :

M.C. Escher
Waterfall (1961)

(
)


( 2
).

?? Gibbs

S Entropy


S

max

S=0
Z=0

Similarity

Z=1

 2.52 GW
TH=725K
TC=290K. ()
, Carnot. ()
65% ,
Q
165 m3/s ()


2C

nmax

TC
290
= 1
= 1
= 1 0.4 = 0.60
TH
725

60% & 40%

Q = (2,52 GW)

(2) : nrealistic = 0.65 nmax

W
2.52GW
= 0.7 * 0.6 = 0.42 =
QH =
= 6GW
QH
0.42

58%
,

QC = 0.58 6GW = 3.48GW

m s

= 165m 3 / s 103 kg / m 3 = 165,000kg / s

QC = mc C p T T = QC / mc C p =
= 3.48(GW ) /(165,000kg / s 4.18( J / kg K ))
T = 5.04 K
QC
3.48GW
=
=
= 328.110kg / s
3
C p T 4.18( J / kg K ) 2 1000kg / m


n1 n2
. .

n1+n2=n n1=n (, )

n
( Vo)

(1) Vo (2) (1-)Vo
(1): Vo Vo & (2): (1-)Vo Vo

S1 = n1
S 2 = n2

Vo

pdV
dV
1
= n R
= nR ln
T
V

Vo
V

(~2.56-2.64)

o
pdV
dV
1
= (1 )n R
= (1 )nR ln

T
V
1
(1 )Vo

Stot

1
1
= S1 + S 2 = nR ln + (1 ) ln

S max d(S)/d=0 =1/2 ( )

 750 MW
TH=586K
TC=293K. ()
, Carnot. ()
60% ,
Q
165 m3/s

nmax

TC
293
= 1
= 1
= 0.5
TH
586

50% & 50%

Q = (750 MW)

(2) : nrealistic = 0.6 nmax

W
750 MW
= 0.3 =
QH =
= 2.5GW
QH
0.3

70%
,

QC = 0.7 2.5GW = 1.75GW

m s

= 165m 3 / s 103 kg / m 3 = 165,000kg / s

QC = mc C p T T = QC / mc C p =
= 1,75(GW s ) /(165,000kg / s 4.18( J / kg K ))
T = 2,54 K

2.61 2
, 1 2.
. 2
. S
1 2 ?

PV = 1 RT & PV = 2 RT 1 = 2 1, 2 =

2V

1, 2

1, 2

dV
dV
= R

dS = P
T
V
2V

dV
dV
S1 = 1 R
= 1 R ln 2 & S 2 = 2 R
= 2 R ln 2
V
V
V
V

S = S1 + S 2 = ( 1 + 2 ) R ln 2 = (

M1

) R ln 2

2.60
, .
. n moles
.
.
, ,
. ,
.
. .

1 2
2 1
1 2 :
Q = dU + W = dU + pdV

Q = 0

W = 0

dU = 0
,
, dU=0

2V
S12 = nR ln( ) = nR ln 2
V

U12 = 0

2 1 : Q = 0

 S 21 = 0 S = nR ln 2
dV
Q = 0 = dU + pdV dU = pdV = nRT
V

TV

dU 21 = nRToVo

dV

1
V V

1
2
1
1
U 21 = nRToVo (1 )( 1 1 )
Vo
V

U 21 = + nRTo ( 1)(2 1 1)

U = U12 + U 21 = nRTo ( 1)(2

S = S12 + S 21 = nR ln 2

1)

2.16 ,
, >>>
.
L.
T . S
Po=P. Po0? ( 2.14, 2.15 2.17)

dF
F = kx & F = PS & dF = Sdp dp =
S
. PV = V dP + PV 1dV = 0
dP = PV 1dV dP = PV 1Sdx

Po, M
dx

dV
L,V

F
Mg
dF
1
= = P = Po +
dP =
& V 1 = (SL )
S
S
S

(
Po S + Mg )dx
dF
Po S + Mg 1

= dP =
Sdx dF =

S
S
L

SL

(
Po S + Mg )dx
dF dx
dF =
L

Po S + Mg
d 2x
F =
x = kx = 2 M
dt
L

M
T = 2
= 2
k

ML
(Po S + Mg )

L
Po 0 T = 2
g

( = 1)

2.64 S
( ) 100gr 300oC 15oC
.
c=0.11cal/(gr*grad)
=288 (15+273=288)

Fe : dS =

Q
T

Q = mFe cFe dT
T

dS Fe
S Fe

dT
dT
= mFe cFe
S Fe = mFe cFe

T
T
To

T
cal
288
cal
= mFe cFe ln = 100 gr 0.11
ln
= 7,6
573
To
gr grad
grad

T = 573K 288 K = 285 K

cal
100 gr 0.11
285 K
QN mFe cFe T
gr grad
S N =
=
=

288 K
TN
TN
cal
S N = 10.8
grad

cal
cal
= S Fe + S N = (7.6 + 10.8)
= 3,2
grad
grad

??

3
: 0 ,

.
=0:
(.. ). !!! ()
,
(3 ..
Nerst)
,
, 0, 0.

 =0 =0 ( Nerst)
(So=0) ( )
=0 , S=0
( 2 ..)
:
.
Q
: ..
dT

C0 ( =0, T=0, , )
S

AB

..

. =0

TLHe

>0
()

A : B=0

A : B>0
Q

.

C

dS = dQ / T = CdT / T

T
(3
) =0 (Nerst)

dS = adT = CdT / T & C = aT

Boltzmann:

n = no e

U
(1) T =

k ln n
K
no

KT

(E2-E1)

U > 0

T < 0!

n > no

:
: .
=0, n=no .
: max
(n=no, (1) T: , , ) ( n
)



: Laser

2
1

2
1

2
1

n2 = 0, T = 0, S = 0

(T=+0)

(+ )

n2 < n1
> 0,

n2 = n1
= ,

()
S>0

(S )

S = max

( )

2
1

n2 > n1 T < 0. S !
( )

2
1

< 0 =

U
n
K ln

n
0

!
n1 = 0
T=0
(T = -0)

S=0

H T = +0
(min E!)
H T = -0 :

 , 1 2
1. ( )
2. 1: ( )
3. 28 (), 6-8
4. 2
5. 100
6. 2 >=40
7. >=
40. B 2 . >=45
9. 2 : 3 , . -,
10. 2
( 6)
11.
( )

2.31


.
2 .

Q = dU
Vo
& Q < 0
Vo
Q = dU + W dU = dU + pdV
2

CV = dU

dT

2CV dT = pdV ( pV = RT )
RT
2CV dT =
dV
V

RT
2CV dT =
dV
V
T

dT
R
T T = 2CV
o

Vo / 2

Vo

dV

Vo

T
R
ln =
ln 2
2CV
To
Vo

R
R
T
ln = ln 2 CV T = 2 CV To
To

dV
C = CV + p
-Q = dU
dT
CdT = CV dT C = CV

W:
Q = dU + W 2dU = W

2CV dT = W
R CV

1
W = 2CV (T To ) = 2CV To 2

2.29 mole CV
.
P1. P2. .

Q = 0
W = p2 V
U + p2 V = 0

CV (T2 T1 ) + p2 (V2 V1 ) = 0

p2V2 = RT2 CV (T2 T1 ) + RT2 = p1V1

CV T1 + p2V1 CV T1 + p2V1
=
T2 =
R + CV
Cp

RT2
V2 =
p2

 P1 T3

CV T2 + p1V2
T3 =
Cp

RT3
V3 =
p1

CV V1 ( p2 p1 )
T3 = T1 +
p2
Cp

2.14 1

U .
. 2.
,
V cm3,
(h cm ) S
cm2, .
.
(gh h=2x)

2 gS
F = 2 gxS F x =
M Hg
2
1

2
M

2
2
T1 =
Sg

 Vo = V + hS V

V1 = V + (h x )S Vo xS

V2 = V + (h + x )S Vo + xS

p1 = p + p , p = gx
p1' = p'

Vo
V
p V = p V p = po = po

V xS
V1

o o

p = po
1 xS
V

p 1 + xS
o

xS

po 1 +

 1
pa' = po
1 + xS
V

p 1 xS
o

) p 1 xS V

p = p1 p = 2 gx + 2 poxS / V
'
1

F = 2 gS + poS / V x
T22 =

2 2 M Hg

2 2 M Hg

gS + po S V

gS
po S

1+

gV

12
=

po S

1+

gV

gV T12 T22 V T12 T22

=
2
2
po S T2 hS T2

2.19 mole
,
Hooke. .
Vo
poS2=kVo, po
, S k
. - .

Q = dU + W = CV dT + pdV & C

dT
k
kx
V = Vo + Sx dV = Sdx & p = po + dp = dx
S
S

kx
Q = CV dT + ( po + ) Sdx = CV dT + ( po S + kx)dx
S

pV = RT pdV + Vdp = RdT

kx
k
( po + ) Sdx + (Vo + Sx) dx = RdT
S
S
[( po S + kx) S + (Vo + Sx) k ] dx = RSdT

( po S + kxS + kVo + kxS )dx = RSdT

2

po S 2 = kVo 2S(kx + po S )dx = RSdT

R
2(kx + po S )dx = RdT & (kx + po S )dx = dT
2

Q = CV dT + ( po S + kx)dx

Q = CV dT + R 2 dT

Q
dT

= CV + R

2.41, 2.40 2.55)

1,2
3

S1,3

S2 S
Q + = T1 (S 2 S1 )
T1 T2
Q = T2 (S 2 S1 ) + (S 2 S1 )

= 1

Q
Q

= 1

T1 (S 2 S1 )

T T
T2 (S 2 S1 ) + (S 2 S1 ) 1 2
2

T1 + T2 T1 T2
= 1
=

1
1

nc = f (T1 , T2 )

Q
= f (T1 , T2 )
+
Q

T3 : T1 > T3 > T2
3
:
1, 2

T2
(Carnot) 1

T1

(1)

n1,2 = n3

:
:

Q1+ = Q3+

Q2 = Q3
+
2

Q =
Q

W1 + W2 =
W3

Q
3
=
(1)
+
Q

Q1
f=
(T2 , T1 ) ,
Q1+

(2)

Q2
f=
(T3 , T1 ) ,
Q2+

f (T2 , T3 )

(2) :

Q3
f (T2 , T1 ) = +
Q3

(2)

. 3

Q2 Q1
Q2
=
+ + =
f (T2 , T3 ) f (T3 , T1 )
+
Q1
Q2 Q1


3 :

f (T=
- (T2 ) / (1 )
2 , T1 )

(1) ( Carnot) :

Kelvin ():

(3)
:

( 2 )
=
+
(1 )
Q

( 2 )

(1 )

Q
2
=

1
Q+

(3)

T2
nc =
1
T1
nc, i =
.
( .11) .
Gibbs,
.

= kT

 Legendre Maxwell*

Y ( x1 , x2 ,....xn ) dY= c1dx1 + c2 dx2 + .... + cn dxn

Legendre
xi ci
n-,
2n 1 Legendre
1
1 (c1 , x2 , x3 , , xn ) Y c1 x1
2
2 ( x1 , c2 , x3 , , xn ) Y c2 x2

n
n (xc
, x2 , x3 , , cn ) Y cn xn
1 1

12
13

1,..., n

12 (c1 , c2 , x3 , , xn ) Y c1 x1 c2x2 x2
13 (c1 , x2 , c3 , , xn ) Y c1 x1 c3 x3

1,..., n (c1 , xC22,, Cx33, , , cn ) Y (ci xi )

i

:
= TdS
pdV

Q = dU + W dU
1
Q

U=U(S,V). YU
xi : dY =cc11+ dx1 + c2 dx2

x1 = S
c1 = T
ci:
x2 = V
c2 = p

n=2 : 2n-1=3 Legendre!

1 (c1 , x2 ) =
= U TS
F
Y c1 x1

2 ( x1 , c2 ) = Y c2 x2
= U + PV
12 (c1 , c2 ) = Y c1 x1 c2 x2 = U TS + PV

H
G

F, H, G

Helmholtz
( = -W)

(P=.)

Gibbs
( )

dU
= TdS pdV

H= U + pV dH =dU + pdV + Vdp =TdS + Vdp H ( S , p)

SdT TdS + dU =
SdT pdV F (T ,V )
F= U TS dF =
dG = dU -SdT
Sdt TdS + pdV + Vdp = SdT
Sdt + Vdp G (T , p)
H
G =U TS + pV
U=U(S,V)

U
U
dS +
dV
* dU =
S V
V V
T

T
p

=
V S
S V

: H = H ( S , P )
,
F = F (T , V ) Maxwell
G = G (T , P )

Q P
=
y x
dH =
dF =

dG =

 : dH = TdS + Vdp
H
T =

S P

H
V =

T V

p S S p

dF =
SdT pdV
F
S =

T V

F
p =

V T

S p
=
V T T V

dG =
SdT + Vdp
G
S =

T P

G
V =

p T

S
V
=
T p
p T

 Maxwell
(1)

U
U
U
dU =
dT
dV
c
dT
+
=
+
V

dV
T V

V T
V T

U=U(V,T)

cV

Qa

dU P
dT 1 U
(2)
dS =
cV
= + dV =
+
+ p dV S
T
T
T
T T V T
V T
(. T,V)
S
S
S
Maxwell
+
dS
dT
dV

p
T V
V T
(dF)
T V

T V

V T

(1) dU =
cV dT + T
p dV
T V

dT p
=
+
dS cV
dV
T T V

(3)

( T,P)

H
V
H
dH= c p dT + V T =
dp
dp
dT +
T p
T P
p T

3,4

dT V
dS = c p

dp
T T P

T
cP cV=
= T
V

(4)

p
H
cp

P
>0

T
2

Clausius

Q
T

1 : Q = dU + pdV

Q < TdS dU+pdV-TdS <0

1. dS=0, dV=0 dU<0 :

2. P, S d(U+PV) <0 i.e. dH<0,

3. V, T d(U-TS) <0 i.e. dF<0,

4. , dG-SdT+VdP <0 dG <0