I

, ,

2018

, ,

2018

2

3

5

6

1. 7

2. 8

3. 9

4. 19

5. 22

6. 24

6.1 - Raoult 26

6.2 -

enry

30

6.3 33

7. 34

8. -

42

9. 45

10. 49

11. N 52

12. -

54

12.1 55

12.2 A 56

12.3 60

12.4 61

13. 68

14.

15 73

16. 74

4

5

, , ,

, ..

.

,

.

,

( )

.

, ,

.

,

.

6

X =

= j jj 1

X X n , , , ,

, , , ,

=

=j jj j j j

X U S V G H

X U S V G H

m =

= jm jj 1

X X N

M

jX

, ,

= i

jj T P n j

XXn

M

Nj jj

jj

nN

n=

j

= = i j

j jj P ,T ,n

GGn

( - )

j j

jn d 0 = Gibbs Duhem

j * ln= +j j jRT N O Rault

jP = oj j jP N P O Rault *j

o *A A AG n =

BK B B BP N K= Henry

j

* ln= +j j jRT

E ( )

jN =j Nj jN - J

jm

jj m jm = -

.. (molality) J

jC

jj C jC = -

.. (molarity) J

K oGAx RTBx

N e KN

= =

= b BK m

bK 2Ab

.

M RTK1000 H

=

= f BK m

fK 2AB

M RT m1000 H

=

.. .

BV RTn =

, VantHoff

7

1.

, ,

, .

,

. , ,

,

( ).

, ,

, .

1.

.

,

.

(,

),

.

, ,

, ,

, , ,

.

,

(.. /),

, , ,

(.. /),

,

(.. /, /).

,,

, ,

(.. 2/Pd, N2/Ti).

, .

,

. ,

, , ,

.

8

1:

/

5.10-5 cm

(.. )

5.10-5-10-7 cm

-, -

, -

-

9

3. , molarity,

moles (1 L).

4. , Normality, N

.

8

g 1 gr . (.. Cu

63.54/2=31.77 Al 27/3=9). ( / ).

5. ,

J ,

moles nj , moles, ,

.

jj

jj

nN

n=

(1)

, ,

.

jj

N 1= (2)

.

3.

, ,

,

(, ),

(.. ,

, ).

. , ,

,

. .. , ,

,

,

, .

10

,

=

= j jj 1

X X n (3)

jX (.. V, , S, G) nj

j .

3 ,

jj

n n= , mole,

m

=

= jm jj 1

X X N

(4)

jX (.. V, , S, G) j

j .

,

= +A BA BX n X n X (5)

m

A Bm A BX N X N X= + (6)

, ,

. , ,

,

.

G,

H, S V.

: 1 mole CH3OH 40.45 cm3 (

) (CH3OH),

40.45 cm3 ( ). ,

, 1 mole CH3OH .. 0.8 2/0.2 CH3OH,

37.65 cm3.

11

40.45 cm3,

, 37.65 cm3. mole CH3OH

2/CH3OH

.

,

,

, ,

VA VB. ,

,

.

O ,

.

,

P, T, nA nB

( , , , )A BV V P T n n= (7)

dV

= + + + B

T ,n ,n P,n ,n T ,P ,n T ,P ,n

V V V VdV dP dT dn dnP T n n

(8)

,

. 9

BT ,P,n T ,P ,n

V VdV dn dnn n

= +

(9)

,

10,

P,T ,n

VVn

=

(10)

. .

12

P,T ,n

VVn

=

(11)

9

= +A B BdV V dn V dn (12)

12 , ,

,

V V

.

,

( . 1).

1: O

.

12

.

A Bn n

A B B0 0

V V dn V dn= + = A BA BV n V n+ (13)

, ,

( ).

13

A BA B A BV V V n V n V= + = + (14)

V , AV BV n n .

14

,

.

E, n=nA+nB 14

,

A Bm A B A BV V V V V = + = + (15)

Vm , AV BV

.

, ,

+ =A BN N 1

( )A Bm BV V V V = +

15, mV

. 2

,

, .

,

, 1 mole

,

( ). ,

. ,

, ,

.

14

2:

, .

,

,

, ,

( , H=0).

O (, ) (,

) , CHC13

=0.4693, 74.166 cm3mol-1 80.235 cm3mol-1, .

1.000 kg;

15

Am AV V V V V = + = +

Vm , V V

.

, ,

Vm=77.387cm3 mol-1

15

mV V n= , n=nA+nX

1000 g

1000 ( )A A X xn N MB N MB= + n=11.48 moles V=888.4 cm3

, ,

, ,

, ,

, ,

= i

jj T P n j

XXn

, , , ,

, , , ,

=

=j jj j j j

X U S V G H

X U S V G H

,

, G0

( ) =0.

, , , ,

.

, ,

, ..

-, -. ,

, ,

. ..

(. 3).

16

3: o

25 oC 1 bar, /.

Gibbs

,

,

, , .

Gibbs

16.

= = i j

j jj P ,T ,n

GGn

(16)

16 , ,

,

j G

, j.

,

( 4).

Gibbs ().

, ,

Gibbs,G, 5,

A A B BG n n = + (17)

17

nA, nB

.

4: Gibbs ( )

, .

Gibbs,

6, 18

m A A B BG N N = + (18)

.

Gibbs Duhem

j jj

n d 0 =

(19)

,

.

A A B Bn d n d 0 + = (19)

,

(0

18

*

, , lnl A l ART N = +

Gibbs-Duhem

.

19

( )*, , ln = = = + = A A A Al A l AB B B A

n n N dNd d d RT N RTn n N N

A +=1 dNA+dNB=0,

A BdN dN= B

dNd RTN

=

ln= +B BRT N C

C . ,

, *

, l .

*, , ln = +l l RT N

Rault.

,

, 20 21.

, , lng A g ART P = + (20)

, , lnB g B g BRT P = +

(21)

,g ,g

P=1bar PA PB .

19

,

Rault, ,

, 22 23

*, , lnl A l ART N = + (22)

*, , lnB l B l BRT N = + (23)

,l* ,l* =1

.

To

,

, 24.

= = = i j i j i j

jj j jP ,T ,n S ,P ,n S ,V ,n

G H En n n

(24)

.

4.

.

,

, .

,,

,

(. 5)

=

= j jj 1

X X n

j nj o .

Gibbs

H Gibbs , ,

o *A A AG n =

o *B B BG n =

* * .

20

Gibbs ,

3,

A A B BG n n= + (25)

.

G

( ). o o A BG G G G = + (26)

* *. ( ) ( )A A B B A A B B A A A B B BG n n n n n n

= + = +

(-*) RTlnN ( . 22,

23), , ,

. ln lnA A B BG n RT N n RT N = + (27)

A AA

A B

n nNn n n

= =+

B BBA B

n nNn n n

= =+

A Bn n n= +

[ ]. ln lnA A B BG n N RT N N RT N 0 = +

21

S.>0.

T ,n

GV 0P

= =

(30)

.

/,

. . .G H T S =

G S 28 29

( ) ( )( ). ln ln ln lnA A B B A A B BH nRT N N N N nT R N N N N 0 = + + + = (31)

.= 0,

.

.

,

.

G, H, S V.

5.00 mol 3.25 mol .

,

, 298 1 bar .

22

0.606 0.394

.

28 29

[ ]. ln lnB B T TG n N RT N N RT N = +

[ ]a B B T TS nR N RT ln N N RT ln N = +

.G =8.25 molX 8.314 Jmol-1K-1X 298 K X (0.606 ln0.606 + 0.394 ln0.394) = -13.7

103 J ( ).

aS = -8.25 molX 8.314 Jmol-1K-1X(0.606 ln0.606 + 0.394 ln0.394) = 46 JK-1

5.

,

.

, Dalton

.

Dalton,

, ,

.

()

AA

A B

nP Pn n

=+

BBA B

nP Pn n

=+

'A AP N P=

'B BP N P=

' 'A BN N 1+ =

,

.

23

P

A BP P P+ =

, , lng A g ART P = + (32)

, , lnB g B g BRT P = +

,g ,g

P=1bar PA PB .

32 PA NAP ( Dalton)

', , lng A g ART P RTN

= + + (33)

O ,

*, lnA g RT P

= +

* P,

* ', , lng A g ART N = + (34)

* ', , lnB g B g BRT N = +

.

.

,

. Henry (1803) ,

35, ,

, ,

,

.

mC KPV

= = (35)

24

C , P

(= ) Henry,

1 bar.

molL-1bar-1. H Henry

.

2: Henry

(mMbar-1) (mMbar-1)

O2 1.25 H2 0.78

N2 0.65 CO 0.95

CH4 1.32 Ar 1.4

,

, .

36

1 2 1

2 1 2

C H T TlnC R T T

=

(36)

C1, C2

1 2.

6.

, . ,

,

, Po .

,

,

.

( ) ( . 5).

25

, , (

Raoult),

. Raoult

.

5: .

(P), (Pi)

, ,

.

,

. ,

.

,

, ,

.

F F FAB,

,

.

1. A B A A B BF F F

,

,

26

,

4 ( 3).

2. >A B A A B BF F F

.

( 3).

3.

27

, ,

() , PA PB ,

Dalton ()

, P

( ) .

'

' '

=+A

nP Pn n

'

' '

=+nP P

n n

'A AP N P=

'B BP N P=

nA nB moles .

' 'A BN N 1+ =

P

A BP P P+ =

, , Rault ,

,

( )

, () .

oA A AP N P= (37)

oB B BP N P= (38)

Ao , PBo

.

+ = 1,

( )o o oA B B AP P N P P = + (39)

( ),

PAo PBo . 6 PA

28

PB P,

.

.

6: ,

,

.

90C 53,3 kPa 1,2-

20,0 kPa.

90C, 0,50 atm; ;

(1 Atm=101.325 kPa)

Rault, ,

.

7: ()

A B ().

29

, ,

, A,g*,

, A,l*.

* *, ,l g = (40)

, . E

, ,

** *

, , , ln Al g A g oPRT

P 1bar = = +

= (40)

A,go P=1 bar.

,

,

.

, , , ln 1A

l g A g oPRT

P bar = = + =

(41)

PA

41 ,go 40,

** *

, , , *ln ln ln1 1A A A

l A l A lo oA

P P PRT RT RTP bar P bar P

= + = += = (42)

, 42,

( ).

Francois Rault ,

, PA/PA*

.

*A

AA

P NP

=

(43)

42

30

* *

, , ,*ln lnA

l A l A l AA

PRT RT NP

= + = + (44)

,

, ,

*, , lnl A l ART N = +

*, , lnB l B l BRT N = + (45)

,

, =1,

.

Rault

.

() ,

. ,

, ,

, . , ,

,

.

(

).

6.2 - enry

,

( PA

PB )

, .

(.=0),

(V.=0). Rault.

, 6,

, Rault.

( >A B A A B BF F F )

(

31

,

, Rault.

, ,

,

Rault. , , .

. 8

.

, ,

Rault.

.

, ,

3.

,

. Rault,

Rault. . 8

.

,

, Rault.

, , 3.

8: () - ,

>A B A A B BF F F , () -

,

32

. 8,

Rault,

45. , ,

William Henry ,

, Rault.

, ,

,

( 46)

B B BP N K= (46)

, Henry,

, ,

Henry.

. 9, Henry

=0 ( ). Rault ,

(~1).

, Henry

Rault, .

9: Henry, K,

.

H

,

, ,

, ,

.

33

6.3

,

Rault

*, , lnl A l ART N = +

*, , lnB l B l BRT N = +

* ,A l ,*

,l .

,

.

,

,

, (

).

,

*, , lnl A l ART = + (47)

*, , lnB l B l BRT = + (48)

, * ,A l

* ,l .

,

AA N AN =

(49)

AN

. .

, ,

, (molarity)

(molality).

34

AA m Am = (molality)

AA C AC = (molarity) (50)

,

, .

, Henry,

, ,

, ,

.

7.

, Rault

Dalton , ,

,

.

,

, Dalton

PA PB

'A AP N P=

'B BP N P=

' 'A BN N 1+ =

Rault,

oA A AP N P=

oB B BP N P=

A BN N 1+ =

, Rault,

o oA B A A B BP P P N P N P = + = + (51)

1-

( )o o oA B A BP P P P N = + (52)

35

52, ,

,

( 6).

, Dalton

'B BP N P=

,

'

( )

oB B

B o o oA B A B

N PNP P P N

=+

(53)

,

. 53 , ,

, ,

,

,

,

, , ,

.

',

.

'B BP N P=

oB B BP N P=

'( )

o oA B

o o oB A B B

P PPP P P N

=+

(54)

, , P

, P (. 54) .

P .

10, -

, , , P

,

PAo PBo.

36

- . 10

, P.

' .

H , PAo - PBo,

,

PAo - PBo ,

. ,

, ,

.

C 1

3, ,

. . 10 , 3

1

, B.

,

(.. D),

10: .

.

2, ,

, 2, , CE

D, CD DE .

( )o o oA B B AP P N P P = +

'( )

o oA B

o o oB A B B

P PPP P P N

=+

37

w CD w DE=

w DEw CD

= (55)

w w .

I 5 mol (B) 3.25 mol (T)

, . 298

PBo=96.4 Torr PTo=28.9 Torr . N

, ,

. (1 Atm=760 Torr)

=0.606 =0.394

o oP N P N P = + = 0.606 96.4 + 0.394 28.9 = 69.8 Torr

, ,

69.8 Torr.

54, ( ) ,

'( )

o oA B

o o oB A B B

P PPP P P N

=+

'( )

o oB T

o o oB T B B

P PPP P P N

=+

H

= 0.837 = 0.163.

, , , .

38

,

. ,

, ,

(.. ~1 bar) .

-

,

11.

.

11: - -

()

Rault ().

-,

Clausius-Clapeyron,

.

, 52 54.

, ,

, ,

.

39

. 11

- ,

Rault ( ). (, )

,

. .

, . ,

.

. (. 11) , ,

- , -

( ).

- ,

, ,

.

, .

.

- 12.

,

,

. ,

. ..,

, ,

.

, 1, .

,

.

1, . 12 ( C),

, 2 (>1, D),

.

,

,

.

. ,

, ,

, ,

.

40

, , 1

, , 2 (>1),

.

, 2 ,

2 3(>2). -

, , (),

.

/,

C.

12.

Raoult.

, -,

, .

-

.

, , , :

( )

.

,

.

41

( )

,

.

, , ,

.

,

.

H , ,

,

, (. 13).

13:

.

,

,

, , .

,

, .

,

. ,

.

http://en.wikipedia.org/wiki/File:Simple_distillation_apparatus.svg

42

,

.

.

,

,

.

- 0.3 Atm, , ..-NB, ().

1. 360 400 .

2. A 380 /0.5.

.

8. -

Raoult.

FAB

FA, FB.

300

320

340

360

380

400

420

440

460

0 0,1 0,2 0,3 0,4 0,5 0,6 0,7 0,8 0,9 1

(

)

43

,

, , ,

( ,

), 14.

.

,

, .

,

.

( )

,

( ), ,

.

, ,

.

.

14.

Raoult.

44

Raoult.

Raoult

Raoult

FAB FA FB

.

,

( ,

) , 15.

( ),

,

. ( ),

15.

Raoult

70

72

74

76

78

80

0 0,2 0,4 0,6 0,8 1

45

Raoult.

9.

. , ,

, .

,

,

,

. ,

( ) ,

, , ,

. , ,

.

Tk

(. 16).

, ,

, , ,

(. 16).

(. 16).

16 -

.

.

5556575859606162636465

0 0,2 0,4 0,6 0,8 1

/

oC

, NB

46

16:

: ()

, () , ()

(=).

17 -

, (

, ).

,

, .

:

,

, ,

.

, ,

. ,

. 17

x z.

, ,

x z.H

(>z),

, , .

47

17: - .

0-x z-1. 0-x:

.z-1: .

x-z . :

, . C:

, . B:

z .

,

. 17.

. , ,

.

, . 17,

.

17. W. Gibbs

3 = (56)

()

()

. ..

,

48

0 x z 1.

. x z

, ,

x z .

.. y

=AB

w BCw AB

(57)

, , ,

, .

(k)

.

, , ,

,

(.. -).

16, - ,

. -

19 C, ,

.

,

.

, ,

.

. -,

16, ,

208 oC 60.8 oC.

,

.

,

,

. - =68 C. H 0.1 KCl,

, 74 C,

( ) 86 oC. A

49

,

(.. -).

10.

,

, ,

. ,

,

.

.

, ,

P PBo.

:

50

o oA BP P P = + (58)

, ,

PAo

(.. 1 bar). To .

,

, . ,

58, .

.

,

,

.

,

,

,

.

PA PB ,

, , Dalton,

'A AP N P=

'P N P=

'A A A A B

'B B B B A

P N n W MP N n W M

= = =

(59)

W W

. 59

A A A

B B B

W P MW P M

=

(60)

,

. 60

. ,

51

,

.

, ,

, , ,

, ..

, .. .

100 oC,

.

, .

( )

.

2 2

W P MW P M

=

(61)

19: .

O

.

t oC 20 30 40 50 60

PC6H6 (atm) 0.21 0.326 0.485 0.704 0.993

52

PCHCl3 (atm) 0.1 0.156 0.238 0.362 0.512

, ,

, .

58,

o o P P P = +

.

20 40 600

400

800

1200

, P

o (m

mHg

)

t, oC

1 atm

t=48.5 oC

760 mmHg=1 atm

, ,

, 1 atm. A

, 48.5 oC.

11. N

,

,

, .

(Nernst),

. , ,

,

CA CB,

53

G

A A RT

B B

C NK eC N

= = =

(62)

.

,

, ,

.

,

.

.

A Bx x =

( )

,* ,*ln lnA A B Bx x x xRT N RT N + = + (63)

,* ,*

lnA A B ox x xBx

N GN RT RT

= =

(63)

,*Ax ,*B

x .

, mol

, G

oGAx RTBx

N e KN

= =

(64)

64

oGAx RTBx

C e KC

= = (65)

,

, .

.

54

,

.

12. -

, ,

,

, ,

,

.

, ,

.

, ,

,

,

,

, .

.

,

, .

() ,

, .

, *

* +RTln (

55

20:

, ,

,

( ).

.

12.1

()

( )

.

()

(). Rault, ,

.

Rault,

1= = o oA A A B AP N P ( N )P (66)

= =o

A ABo

A

P P N PP

(67)

P .

67 ,

56

22

1 2

= = = =

+

o

o

nP PP NP n n

P (67)

PAo, , Po PA,

, P. (1) (2)

.

67, ,

,

.

(n1>>n2) 67

2

1

o

oP P n

P n

=

(68)

68

,

.

53.3 kPa 60.6 C, 51.5 kPa,

19.0 g 500 g .

.

12.2 A

,

, (..)

(..) . ..

(. 21).

. *

* lnA A ART N = + (

57

21: .

. 21 ,

, ( ),

( ). ,

(Sm) (S)

.

, ,

.

( , ) .

,

Sm S. ,

.

. 21,

-

( ) -

( ) , .

.. ..

,

.

.. ,

(.. 1 atm).

58

22: .

,

,

* *, , , lnA g A l A l ART N = = + (69)

69

* *A,g A,l

AGln N

RT RT

= =

G Gibbs .

, T

A2

d ln N 1 d( G / T ) HdT R dT RT

= =

=

x Gibbs-Helmholz, .

2P

( G / T ) HT T

= Gibbs-Helmholz

dT =1,

lnNA=0 ( =*, ) (

).

Aln N T

A 20 T*

1 Hd ln N dTR T

=

(70)

59

To lnNA=ln(1-NB). ,

,

, 70

T

B 2T*

H 1ln( 1 N ) dTR T

=

B *H 1 1ln( 1 N )R T T =

(71)

nB,

*2B

. A

RT nH n

=

A 1000 g, nB

(mB) nA=1000/MA ( ).

2A

B .

M RT m1000 H

= b BK m = (73)

, 73, ..

,

( moles/1000 gr , molality).

60

2

Ab

.

M RTK1000 H

= (74)

b , K Kg mol-1,

..

1 mole 1000 g .

4:

Kf (K Kg mol-1) Kb (K Kg mol-1)

5.12 2.53

40

7.27 3.04

1.86 0.51

12.3

, , (..)

(..) .

. 21, .., .

, ,

(. 23).

, ,

.

* *, , , lnA s A l A l ART N = = + (75)

..,

.

.., ..

,

61

2

AB

M RT m1000 H

= f BK m = (76)

f ..

..

1 mol 1000 g 2.

(KKg-1mol-1)

2A

f

M RTK1000 H

= (77)

23: .

12.4

,

, ,

, .

.

, , , .

. 24 ,

, .

.

62

,

(

).

VantHoff

V nRT = (78)

, V , n moles

, R .

. 78,

.

24: .

.. ..

,

, ,

, . 21.

,

, .

,

( ).

,

.

.

,

, (.

79).

63

*A A( P ) ( P , ) = + (79)

25:

+ .

Rault,

*( , ) ( ) lnA A A AP N P RT N + = + + (80)

* ( ) ( , ) lnA A A AP P N RT N + + = = (81)

79 80 81, A

RTlnNA , ,

,

, ,

.

d dG VdP SdT = = (82)

G,V ,S , . , . 82

Ad V dP = (83)

, AV ,

, . 83

64

P

A A AP

d V dP V dP V+

= = =

(84)

81

* ( ) ( , ) ln AA A A AP P N RT N V = + + = = (85)

ln AART N V =

1 B BA B BA B A

n nln N ln( N ) Nn n n

= = +

85

BA

A

nV RTn

=

(86)

E A AV n V ( ),

VantHoff

BV RTn = (87)

,

1 2 3( n n n ....)RT = + + + (88)

VantHoff ,

87.

,

,

V .

87

'V nRT = (89)

,

,

.

, ,

, .

65

, ,

, .

,

, .

, ,

,

( . 26).

(mOsm L-1).

280-310 mOsmL-1.

, .

280 mOsmL-1 . 310 mOsmL-1, .

90-95% +(), Cl-

HCO3-.

26: .

,

(hypotonic), ,

. ,

, ,

(turgid), .

,

.

.

, . (hypertonic),

, .

. ,

66

. .

27: .

(Mr) (.. , )

. Mr

.

.

: Mr = mRT/V.

.

(.. , C, ,

. NaCl 0,9 % .). : m = VMr/RT =

6,74 atm, . ,

(C6H12O6, M = 180, ),

m = 6,74.1.180/273.0,082 = 54,19 g 1 L

0 C.

298 , ,

0.5 , .

, .

2 1 18.206 10 298 0.5 12.2V RTn LatmK X KX molL atm = = =

67

A ,

,

.

A

,

, (. P <

), , .

(. P > ),

(

). .

, .

:

27 atm. ( 70 atm),

,

.

.

.

, 50 %

, .

... ,

1992

30400 m3 . , ,

, .. .

68

28: ,

.

13.

E ,

,

, .

,

Gibbs,

F= 3 +2 P

.

(=1) 4,

, 2

4 .

. , (=2)

.

, ,

, ,

, , 29

, .

, ,

,

69

1A BN N N+ + =

, , , .

( ),

.

, .

.

, ,

,

.

, ,

. (

) 100 ,

. ,

.. , (

). ( )

( ). , ,

,

.

, 29

, 30 % ( , =0.3), 50 %

( , =0.5) 20 % ( , =0.2).

, ,

.

29

, , 3 ,

( 29), .

, , ,

, .

70

,

(:=7:3).

29: , , , , .

,

, .

, , CH3COOH-CHCl3-H2O,

.

71

30: (CH3COOH), (CHCl3) (H2), , , .

,

.

, .

30.

CH3COOH-CHCl3,

.

CH3COOH -H2O, .

CHCl3-H2O,

. CHCl3 ( )

, (

9). CHCl3 2

,

CHCl3. ,

, , ,

. ,

CHCl3-H2O .

CHCl3-H2O ,

.

,

.

.

.

,

,

,

. ()

29.

, .

31 32 , ,

(. 31) (

) (, )

.

,

.

72

31: , ,

, (1>2).

32: , , ,

, (1>2).

14.

73

15.

P.W. Atkins, , .

. , ,

.

, , , 1993.

R. Chang, Physical Chemistry for the Chemical and Biological Sciences,

2000.

T. Engel, P. Reid, Physical Chemistry, Pearson, 2006.

R. Brdicka, Grundlagen der Physikalischen Chemie.

G. Barrow, Physikalische Chemie, Bohmann, Vieweg, 1984.

D. Ball, Physical Chemistry, 2011.

Ira N. Levine, Physical Chemistry, Sixth Edition, 2009.

G. Castellan, Physical Chemistry, Third Edition, Addison-Wesley

Publishing Company, 1983.

Howard DeVoe, Thermodynamics and Chemistry.

74

16. - ( )

1. .

40 60 mmHg .

PA/PB ()

2. , moles 1:3

, .

40 80 mmHg . PA/PB ()

3. , ,

1. = +o oA A B BP N P N P

2. < +o oA A B BP N P N P

3. > +o oA A B BP N P N P

;

4. - 25 oC,

67.00 Torr.

89.22 51.77 Torr .

() () .

5. - -.

75

() =0.8, = 43 oC. O

, ,

.

() , =0.3, = 48 oC. O

, ,

.

() , =0.3, = 48 oC. O

, ,

.

6. ..- -

() ,

.

() ,

.

76

() ,

.

7. ..- -

() ,

.

() ,

.

() ,

.

8. ..- -

()

, .

()

.

()

.

99

100

101

102

103

104

105

106

107

108

109

0 0,2 0,4 0,6 0,8 1

P=

a a

a2

ax

b b

b'1 b2

b

Ma'3 a3

77

1. , o

0.3713, 188.2 cm3mol-1 176.14 cm3mol-

1, . 241.1 gmol-1 198.2

gmol-1. 1.000 kg;

2. 25C, - 50

0.914 gcm-3.

17.4 cm3mol-1,

.

3. 40 cm3mol-1.

, 1000 g n mol , V

= 1000 +35n + 0,5n2.

) n = 0 n = 1.

) V : 55,5 2O + C3

.

1. 5.0 dm3, .

1.0 atm 25C,

.

Gibbs , .

.

2. 250 cm3, .

100 kPa 0C,

.

78

Gibbs , .

.

3. ()

, () , ;

4. ()

, () ,

;

1. 90C 1,2- 20 kPa 1,3-

18 kPa. ,

90C, 19 kPa;

;

2. - 90C 1 atm.

1022 406 mmHg, . ,

.

3. . 30 oC

0.155 atm 0.05 atm.

, 100 g

; ;()

4. . 50 oC

, 2 mol 3 mol , 0.33 atm.

1 mol ,

0.4 atm. .()

5. / 90 oC 1 atm.

1.34 atm 0.54 atm .

, .()

6. .

80,1C.

, N = 0,30

.

0,93, 1,00, ;

7.

()/() 57,2C 1,00 atm, N = 0,400

79

N- 0,516.

Raoult.

:P* = 105 kPa P* - 73,5 kPa.

(N NA

.()

8.

30C 1,00 atm, N = 0,220, NA = 0,314.

Raoult.

:

P* = 73,0 kPa P*B = 92,1 kPa. (N

NA .)

9. (C5H10O2) 80 oC 361

mmHg (C4H8O2) 833 mmHg.

,

80 oC, Rault.

10. (C2H5Cl)

(C2H4Cl2) 0oC 472 21.6 mmHg .

,

40% C2H5Cl 60% C2H4Cl2 . (MBC2H5Cl =64.5, BC2H4Cl2=99).

11. , 313 ,

-, 30 mot % ,

: .. 353 383 ,,

31,4 33,3 kJmol-1 .

12. 40C.

2 mol 1 mol 9,56 kPa.

, 1 mol

, 40C, 8,20 kPa.

;

13. 300 76,7 kPa

52,0 kPa.

. ,

0,350.

.

14. 293 68,8 kPa

82,1 kPa.

.

0,612.

.

80

15. = 0,6589

88C. 127,6

kPa 50,60 kPa, , () ; ()

;

16. = 0,4217

96C. 110,1

kPa 76,5 kPa, , () ; ()

;

17. .

. 20C

9,9 kPa 2,9 kPa, .

. () , , ()

() ,

. ,

20C.

18. ()

303,15 p.

.

Henry .

xA 0 0,0898 0,2476 0,3577 0,5194 0,6036

yA 0 0,0410 0,1154 0,1762 0,2772 0,3393

p/kPa 36,066 34,121 30,900 28,626 25,239 23,402

xA 0,7188 0,8019 0,9105 1

yA 0,44500,5435 0,7284 1

p/kPa 20,6984 18,592 15,496 12,295

19. , 1 bar

() % %

293 12,3

313 15,1 89,6

333 19,0 86,4

353 25,1 78,0

363 34,0 69,8

368 44,0 59,5

368,2 51,7 51,7

81

() - , ()

343 15%

333 40% ;

H ,

- .

20. -

100 kPa.

/ 77,3 78 80 82 84 86 88 90,2

x(O2) 0 10 34 54 70 82 92 100

y(O2) 0 2 11 22 35 52 73 100

p*(O2)(Torr)154 171 225 294 377 479 601 760

-

, ,

2 .

21. , 313 ,

-, 30 mol % ,

: .. 353 383 , ,

31,4 33,3 kJmol-1, .

1. 300 , HCl (

HCl) GeCl4 :

HC1 0.005 0.012 0.019

PHCI/kPa 32.0 76.9 121.8

Henry,

, Henry

300 .

2. 310 , :

N 0.010 0.015 0.020

pB/kPa 82.0 122.0 166.1

Henry,

, Henry

310 .

3. . PA* = 300 Torr, PB* = 250

Torr = 200 Torr ( ).

x = 0,9, bB = 2,22 molkg-1, pA = 250 Torr pB = 25 Torr,

.

82

Raoult

Henry (

) .

4. . CC14 .

CCl4 33,85 Torr 298 .

Henry, Br2 ,

122,36 Torr. ,

Br2 0,050,

.

5. , 120.5 oC 68% 3. .. 3 86 oC. ,

40% .. 3;()

6. o 1-

, ,

, 1 atm:

mol% 1-

2,0 6,0 20,0 43,2 60,0 80,0 100,0

21,6 35,1 39,2 43,2 49,2 64,1 100,0

../C 92,0 89,3 88,1 87,8 88,3 90,5 97,3

,

1-

, ,

.

) 87 g 1- + 211 g

) 50 g 1- + 5,02 g .

7. 4 mol % 50 mmHg 20C.

17 mmHg.

,

5 mol %. .

Henry

25C 1,25 106mmHg. 25C,

760 mmHg. 1 dm3

1 kg .

(I)

() 50C.

83

() Raoult, () Henry

.

xI 0 0,0579 0,1095 0,1918 0,2353 0,3718

pI/kPa 0 3,73 7,03 11,7 14,05 20,72

pA/kPa 37,38 35,48 33,64 30,85 29,44 25,05

xI 0,5478 0,6349 0,8253 0,9093 1,0000

pI/kPa 28,44 31,88 39,58 43,00 47,12

pA/kPa 19,23 16,39 8,88 5,09 0

Francesconi, Lunelli Comelli -

1,2- (Francesconi,

. et al., J. Chem. Eng. Data 41, 310 (1996)).

(xT) (yT) 298,15 , .

p/kPa 23,40 21,75 20,25 18,75 18,15 20,25 22,50

26,30

x 0 0,129 0,228 0,353 0,511 0,700 0,810 1

y 0 0,065 0,145 0,285 0,535 0,805 0,915 1

Raoult.

,

1.

/C 50 60 70 80 90 100 110

/mmHg 93 149 234 355 526 760 1075

/mmHg 42 66 98 145 208 293 403

, :

) ,

1 atm, .

) % .

2.

0,0203 25C ( mol dm-3).

100 cm3

0,8 mol dm-3,

50 cm3 ;

3. O 2

84

:

oC 20 40 60 80

PoH2O(mmHg) 17.5 55.1 149 355.1

Po(mmHg) 74.6 181 389 754

, ,

, 754 mmHg. % ..

; 40.6 kJmoll-1.

(760 mmHg=1 atm,

Clausius-Clapeyron).

1. 2- 50.00 kPa 338.8C,

49.62 kPa, 8.69 g 250 g 2-

. .

2. 100 g 750 gCCl4

10.5 . .

3. 5.00 g 250 g

0.780 . .

4. 300 120 kPa.

.

5. 288 99.0 kPa.

h .

6. 25C

1,004

gcm-3:

c/(gdm-3) 2.042 6.613 9.521 12.602

h/cm 0.592 1.910 2.750 3.600

.

7. ,

20C

. :

c/(mgcm-3) 3.221 4.618 5.112 6.722

h/cm 5.746 8.238 9.119 11.990

.

8. 50 mol % (f = 12,12) (f= 5,12).

85

;

7C .

9. 760 mmHg 110,6C,

Kb = 3,33.

590 mmHg;

10. 1,25 g

100 g 752,4 mmHg 80C.

80,25C. 80,00C.

.

1. (.. 651 C) (.. 419C)

(368C, 3,2% Mg 347C, 49% Mg).

- 590C 15,7%

Mg. -,

. , , 30 80%

Mg, 700 300C;

2. - ( %)

- 1 atm : ..

1083 650C, .

, Cu2Mg CuMg2 .. 819 568C, .

9,7, 34,6 69,3 % Mg .. 722, 552 485 "C,

.

3. () , 26 (), ,

133 . ,

25 mol 123 90 mol

104 . 131 110 ,

. .

-.

4.

:

mol % . 0 10 20 30 40 50 60 70 80 90 100

/C 47 42 34 35 38,5 40 37 34 41 48 53

-

.

;

5. .. 32,45C.

86

1,268 g 18,43 g , ..

1,89C .. . % ..

, ..

6,78 8,60 ;

87

TITLE PHCHEM II 1 pdfI Physical Chemistry Textbook FINAL CORRECTION 24-11-2018 , (hypotonic), , . , ...//// 28: , .