-

( )
-
:

I-
II-

, .
.
( )
:

p
. : p, T,
V, m, .
<>,
p2,V2,T2
<v> ...
.
p1,V1,T1
:
V
.

 . ,
.
. ,
.
.
:
Celsius

Kelvin

Fahrenheit

Rankin

100

373.15

212

671.67

273.15

32

491.67

- 273.15

T=t + 273,15

tF

0
T=t

tR

- 459.67

tF =1,8 t +32

0
t=(tF - 32)/1,8

- : .
.
, 100 . , ..
,
-273,15. .
32 F, 212 F, .. 180 F . .

 .
-:

.

T2>T1
T1

pV=const, T m = const.

-:
1. p=po(1+t),
m V=const, =1/273,15 -1.
2. V= Vo(1+t),
m p=const.
1. p=po T/To , V=const, To =273,15 K.

2. V=Vo T/To , p=const

t (T)
- 273.15 C

t (T)
- 273.15 C

.
.
po ,Vo ,To p,V,T.
po,Vo,To p,Vo,T ' p,Vo ,T ' p,V,T.

p,Vo,T '
p,V,T

po,Vo,To

1.

p0 p
=
T0 T'

2.

V0 V
=
T' T

p 0 V0 pV
=
= B = const
T0
T

(1 kmol) NA=6,023.1026 kmol -1 (NA

).
: (p0
=1,013.105 Pa, T0 =273,15 K) V0=22,4 m3/kmol:

pV
T

p 0 V0
T0

= R = 8,31.10 3 J K.kmol , R .

V=V/, .

pV = RT

, .. .
:

V
N
m
=
= , , N .
V N A

p = nkT,

p=

RT

, .. n = N/V ,

= m/V,

k = R/NA .

, .

 ()
:
1. .
2. ( ).
3. .
,
.
.

,

:

p = 2n < > / i = 2n < 1 > = nkT ,

n , < > e , i
, , T .
: p =

2
1
n < > = nm0 < v2 >
i
i

i : < > =

i
kT
2

: < 1 > =

1
kT
2

i =5, .. 3 ,
, . i =6.
U = :

i
U = N < > = RT
2

dp = gdh = nm 0 g.dr = nd p , d p = m 0 g.dr, = nm 0

p=nkT, dp=kT.dn ( T=const),

:

n = n 0e

p
kT

p = p0e

n
n0

kT

dn(v) v v+dv dV=4v2dv
. v v+dv dn(v)/n.
:

f ( v)

dn ( v)
n.dv

dn ( v) = A.ndV.e
f ( v) = A 4 v e
2

k
kT

m0v2
2 kT

= An 4 v 2 e

m0v2
2 kT

, A = const = ?

dv

f ( v)dv = 1

m0
A=

2kT

T1< T2

f(v)

:
3
2

v
- (v) f(v):

f ( v) = 0 = (2 v v v m 0 kT)e
2

m0v2
2 kT

v =

2kT
=
m0

< v2 >

<v>

2RT

< v > = v.f ( v)dv =

0

8 RT

1,13v , < v 2 > = v 2 f ( v)dv =

3RT

< v2 > =

3RT

1,22 v

k =

m0v2
, v=
2

f ( k ) =

(kT )

3 2

2 k
=
m0

k e

2 2
, dv =
m0

2 1 1
k 2 d k , f ( v)dv f ( k )d k
m0 2

k
kT

< k > = k f ( k ) d k =

3
kT
2

 . .
. ( )
:

i
U = U (T ) = RT
2
,
, .. V.
U=U(T,V).
. .
:
out = U

( )

, .
Q ,
:
out = macro + micro =-A +Q = U
Q = A + U
Q = A + dU

. ,
. ,
.
, Q A
, d. f=x2yz df=2xyz.dx+ x2z.dy+
x2y.dz, .

 ( ) -
1:

Q
dT

c=

Q C
=
dT

c' =

Q
C
=
mdT m

()

Q = A + dU

A=F.dx=pSdx=pdV

i
Q = RdT + pdV
2

1. V=const, dV=0 (Q=dU):

i
Q
cV =
= R
dT V 2

2. p=const, pdV=RdT (pV=RT):

i
Q = ( + 1)RdT
2
i+2
Q
cp =
R
=
2
dT p
:

cp cV = R ,
cp
cV

-.

i+2
i

3. T=const, dT=0, dU=0, Q=A

, , :

RT
dV
V
V
A = RT ln 2
V1

A = pdV =

4. Q=0 - :
A=-dU

pdV + Vdp = RdT, pV = RT

A = dU
pdV = c V dT,

1+

V dp
R
=
dV p
cV

pV = const

c V + R dV dp
+
= 0,
cV
V
p

cV + R cp
=
=
cV
cV


pV = RT - .

B = NVeff = N A 4V0 , b = 4 N A V0 -
1 .

a
2a
=
, ..
V2 V 2
n
1
~
~ 2:
r V
,

p' =

, 1873 ..

2a
( p + 2 )( V b) = RT
V

Veff = 4V0

K :

p k , Vk , Tk

(p +

2a
)(V b) = RT pV 3 (RT + bp)V 2 + 2 aV 3 ab = 0 ,
2
V

V:

p k V 3 (RTk + bp k )V 2 + 2 aV 3 ab = 0 = p k (V Vk ) 3
p k V 3 3p k Vk V 2 + 3p k Vk2 V p k Vk3 = 0

p k Vk3 = 3 ab
3p k Vk2 = 2 a

Vk = 3b

3p k Vk = (RTk + bp k )

p k = a / 27b 2

, a b .

Tk = 8a / 27Rb

( + 3 / 2 )( 1 / 3) = 8 / 3,

= p / p k , = V / Vk , = T / Tk

 . -.
(p +

2a
2a
RT
)(
V

b
)
=

RT

p
=

V b V 2
V2

p' =

2a
:
V2

2a
2a
dU ' = dA = p'.dV = 2 dV = d
V
V
in
c

U = c V T 2 a / V

2a
U' =
V

, (-

, )

, =0

-
()
.
I :

U + A = 0
U = U 2 U 1
A = A 2 + A1
= p 2 V2 + p1 V1
= p 2 V2 p1 V1 , p 2 = const , p1 = const
U 1 + p1 V1 = U 2 + p 2 V2 = U + pV H = const

H U + pV = const, H - :

Q = 0, p 2 < p1

 2a
RT
2a
)(
V
b
)
RT
p

V b V 2
V2
b
a
a
b
a
pV = RT + 2 (RT
) H = c V T 2 + RT + 2 (RT
)
V b V
V
V b V
b
2
a
H = c p T + 2 (RT
), c p = c V + R
V b V

(p +

H = 0 T = 0 , - .
2a
b
, RT

= 0 , ,
V b V
2a
b
Ti =
(1 ) - . - , ,
Rb
V
,

. . ,

Ti =

2a
b
(1 ) .
Rb
V

:
U - .

H = U + pV - .
F = U TS - , S .
G = U + pV TS - .

 . .
,
.
, :
- -
.
.
- S.

:
S=k.ln, k , , ..
.
( )
V1 V1+V2.
T=const
V2
V1
, N e . V1 V1+V2
, n1 = V1/ n2 = (V1+V2)/ . ,
N n1 n2 :

1 = n1 (n1 1).(n1 2). ........ .(n1 ( N 1)) n1N

2 = n 2 (n 2 1).(n 2 2). ....... .(n 2 ( N 1)) n 2N
S1 = k ln 1 = kN ln n 1 = kN A ln n 1 = R ln n 1
S 2 = k ln 2 = kN ln n 2 = kN A ln n 2 = R ln n 2
S = S 2 S1 = k ln

2
n
V + V2
= R ln 2 = R ln 1
1
n1
V1

, n1 n2 >>N, .

:
.
V1+V2 V1 :
N

1 V1
0
=
2 V1 + V2

>

.. .

(dU=0):

Q = A = pdV =
dS =

Q
T

RT.dV
= Td (k ln V N ) = TdS
V

:
, dS

0.

: 1 2 .

dS =

Q Q1 Q 2 Q 2 Q 2
1
1
=
+
=
+
= Q 2 ( ) > 0,
T
T1
T2
T1
T2
T2 T1

dS = 0, 1 = 2

II :
, , .. dS
0.

, - .
A=Q,
A= - dU.
2

Q1 = T1dS = T1 (S2 S1 ),
1

Q 2 = T2 dS = T2 (S2 S1 )
2

A = Q = Q1 + Q 2 = (T1 T2 )(S2 S1 )
A
T
C =
= 1 2 ,
Q1
T1

T
T1
T2

- ...
.

S1
T1

Q1

.
,
.


.

( A Q 2 Q 1 | A | C ).

S2
T1

Q1

A
Q2
T2

K=

A
Q2
T2

Q2
T2
T2 (S1 S2 )
=
=
| A | (T1 T2 ) (T1 T2 )(S1 S2 )

 :
1. - .

1-2
2-3
3-4 ,
4-5
5-6
6-7

)
1-2
2-3
3-4
4-5
5-6
6-7

2
3

0-1 ,
1-2-3 ,
.
3-4
4-5 .

2.
)

7
1

6
2

5
7
1

3. :
1766.
1784.
1860.
1862.
1878.
1892.

.
.

6
2


,
G . : < >,
p=mu n(x)/n.
1/4 n <v>, ..

, , , .. 1/4
.

G
,
x
e .

G(x ) = G(x)

1
G
I G = nv G ( x )
, G :
4
x
1. :

G =q = =

i
i R
cV
kT =
T=
T = m o c' V T
2
2 NA
NA

T
T
1
1
= v c' V
I q = nm o v c' V
x
x
2
2
I q =

T
1
, = v c' V ,
x
2

1
G
I G = I G+ + I G = nv
2
x

1822 ,

2. ( )

G = p = mou

1
u
u
I p = v
= , 1860.
x
x
2
=

1
v ( )
2

3.

G=

n(x)
,
n

In =

D=

n ( x )
n ( x )
1
v
= D
,
2
x
x

1
v
2

= c'V = Dc'V