第五章 相律和多相平衡 - PowerPoint PPT Presentation

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第五章 相律和多相平衡. §1 引言 一、多相平衡: 1)液体的蒸发(液相和气相平衡) 2)固体的升华或熔化(固相与气相或液相平衡) 3)气体或固体在液体中的溶解度(气-液、固-液相平衡). 4)溶液的蒸气压(溶液各组分-气相组分平衡) 5)溶质在不同相之间的分布(溶质在两溶液相中的平衡) 6)固体或液体与气体之间的化学平衡,等等…。. 以上这些都是我们常见的多相平衡的例子,这些类型多相平衡各有一定的方法来研究它们的规律,例如:. 拉乌尔定律、亨利定律、分配定律、 平衡常数及某些其他经验性规则。 而下面要介绍的 “相律” ,却不同于上述这些规律。

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第五章 相律和多相平衡

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3599664

1

1

2

3--


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4-

5

6


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1.


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1

2


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3


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2.

  • C

  • (S)(C)

  • SC


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1C = S

  • C= S =2


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2

(C) =(S)

(R)


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(C) = (S)

(R)


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  • CaCO3(s)CaO(s)CO2(g)

    CaCO3 (s) CaO (s) + CO2 (g)

  • C = S R = 3 1=2 3


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CaCO3 CO2CaOCO2CaCO3 CaO


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  • NH4Cl

    NH4Cl (s) NH3 (g) + HCl (g)

  • NH3 (g) HCl(g)NH3 (g)HCl(g)NH3 (g)HCl(g)

3


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  • PNH3 = PHClcNH3 = c HCl

  • 32

  • C =3 1 1 = 1


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  • C

    = S

    R

    R


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  • CaCO3

    nCaO =nCO2

    CaO(s) CO2 (g)


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(S)

  • i

    C =1 S


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  • H2OH++OH

  • S=3 R =1

  • [H+] = [OH] R=1

    C=SRR=311 = 1


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iiHAc +H2O C= 2

a. HAcHAc H+ +Ac

S= 4 (H2O, HAc, H+, Ac )

R=1 ()

R=1 ([H+]=[Ac])

C = S R R = 2


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b. H2OR=2

HAc H+ + Ac

H2O H+ + OH

  • S = 5 (H2O, HAc, H+, OH, Ac)

  • R= 1

    [H+] = [Ac] + [OH]


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C = S R R = 5 2 1 = 2


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iiiNaAc+H2O C = 2

a. NaAcR = 1

NaAc+H2ONaOH+HAc

  • S = 4 (NaAc, H2O, NaOH, HAc )

  • [NaOH] = [HAc] R=1

    C = S R R = 4 1 1 = 2


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S = 8 (NaAc, H2O, NaOH, HAc, H+, Ac, Na+, OH )

b. HAc NaOH

1. NaAc+H2ONaOH+HAc

2. HAc H+ + Ac

3. NaOH Na+ + OH

4. H2O H+ + OH

5. NaAcNa+ +Ac


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(1). NaAc+H2ONaOH+HAc

(2). HAc H+ + Ac

(3). NaOH Na+ + OH

(4). H2O H+ + OH

(5). NaAcNa+ +Ac

(5) = (1) + (2) + (3) (4)

(5) R=4


3599664

(1). NaAc+H2ONaOH+HAc

(2). HAc H+ + Ac

(3). NaOH Na+ + OH

(4). H2O H+ + OH

  • R= 1

  • [Na+] + [H+] = [Ac] +[OH]


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(1). NaAc+H2ONaOH+HAc

(2). HAc H+ + Ac

(3). NaOH Na+ + OH

(4). H2O H+ + OH

  • NaAcNaAc R=1

    [NaOH] + [Na+] = [HAc] + [Ac-]


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  • C = SRRR

    = 8411=2


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3.

  • f


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  • Vm

  • f = 2


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  • T, P


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  • P=1atm0C100C

  • 0C

  • 100C


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  • f = 2

  • f = 1

    • P=PH2O* f =1


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5.2

  • f = C + n


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  • f = C + 2

    • f

    • C

    • 2


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f = C + 2

    • 11

    • 11

  • 1876Gibbs


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C f

1C

  • C


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  • (C1)

    C()

  • (C1)


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  • f = (C1) + 2


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  • i

    i = i= = i

    (1)

  • C

    C(1)


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f = (C1) + 2

  • C(1)

    ()

  • f = (C1)+2C(1)

    = C+2


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2C

  • NaCl+H2O NaCl


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  • NaCl

  • f = C+2

  • NaCl1


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  • (g)NaCl= (l)NaCl

  • (C1)1 C(1)1

    f = (C1)+2C(1) = C+2


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1. Na2CO3H2O Na2CO37H2ONa2CO310H2O

1) 1atm

2) 30C


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: Na2CO3 Na2CO3

2 C= 2

1 1atm

f* = C +1

= C+1 f* = 3 f*


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= C+1 f* = 3 f*

  • f* =0

2

f* =C+1=3


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2.

125C 1atmNaCl

C = 2 = 2

f ** = C + 0 = 2 2 + 0 = 0

  • NaCl


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  • 25C1atmNaCl

    =1

    f ** = C + 0 = 2 1 = 1

  • NaCl


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2I2s I2g

C =1 = 2

f = C + 2 = 12 + 2 = 1

  • I2s I2g


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3 HCl(g) NH3 (g) HCl(g)+NH3 (g) NH4Cl(s)

C=2 S=3, R =1, C=31=2

= 2

f = C +2 = 2 2 + 2 = 2


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P = PNH3 + PHCl

PHClP NH3 = 1/KP

PHCl, PNH3

PHClPNH3


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3.

1

2

3


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+ +

1

:C=3f*= C + 1 = 4

=4f* max = 4


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+ +

2

: C= 2f*=2 + 1 = 3

max =3


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+ +

3

: C= 2f**=2 + 0 = 2max =2


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1.


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2.


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  • 3599664

    5.3

    1.


    3599664

    • f = C+2 = 11+2=2

    • PT f=2 P, T


    3599664

    • PT


    3599664

    • i -

    • ii -

    • iii-

    f = C + 2 = 12 + 2 = 1


    3599664

    • TPPT


    3599664

    • PT


    3599664

    • --

    • f = C + 2 = 1 3 + 2 = 0

    • T, P


    3599664

    • O


    3599664


    3599664

    OA:-T

    OB:-T

    OC:-

    O --


    3599664

    • 0.0098C 4.58mmHg


    3599664

      • ;

      • OAOBOC;

      • O


    3599664

    2.

    1)OA

    374C220atm-


    3599664

    • OA OOF

    • OF-

    • OFOB


    3599664


    3599664

    • 2) OB

    • -


    3599664

    • T0 lnP P 0

    • OB


    3599664

    • OB O


    3599664


    3599664

    3OC2000atm20C


    3599664

    • OC

    • 4.58mmHg0.01 C1atm 0C


    3599664

    OAOBOC


    3599664

    3.

    • P(760mmHg)T1 T2


    3599664

    • T1, PXT2 XY


    3599664

    • N

    • f = C +1 =12+1= 0

    • T =0C


    3599664

    • M (T=100C)

    • T2


    3599664

    • f = C+2 =3


    3599664

    • 4 PT

    • C42 = 66

    • C43 = 4 4


    3599664

    • AABBCCABBCCAABC


    3599664

    • BB, AB,


    3599664

    • AABBCCOAOAC


    3599664

    • COCA

    • BO BA


    3599664

    • O

    • XY

    • --

    • P317-318


    3599664

    5.4

    • f = 2 + 2 = 4

    • f = 0 = 4

    • 4

    • =1 f=3


    3599664

    • 4P-T-x

    • P-T


    3599664

    • P


    3599664

    • f*= 2 +1 = 3

      • = 1 f*= 2

      • =3 f*= 0

      • =2 f*=1


    3599664

    • 1

      2

      3


    3599664

    • 3-

    • 1


    5 4 1

    5.4.1 -


    3599664

    -


    3599664

    1. 40CC6H12-CCl4-


    3599664

    • 1

    1. 40CC6H12-CCl4-


    3599664

    • 2

    2. CH2(OCH3)2-CS235C-


    3599664

    • 3

    3. CH3COCH3-CHCl355C-


    3599664

    • -

      • C6H12-CCl4; C6H6-CCl4; H2O-CH3OH


    3599664

    • -

      • CH2(OCH3)2-CS2

      • CH3COCH3-CS2

      • C6H6- C6H12

      • H2O-C2H5OH


    3599664

    • -

      • CHCl3-CH3COCH3

      • H2O-HCl


    3599664

    • PA* PB* yA xA


    3599664

    • 1881

      1


    3599664

    2-


    3599664

    • (1)---

    • Pi*


    3599664

    l -

    v -


    3599664

    • B

    • BB

    • vl


    3599664

    • aa

    • vlBA


    3599664

    • ACB

      BB


    3599664

    • CBA

    • AA

    • C


    3599664

    • ADAA

    • DBBB


    3599664

    • D

    • -


    5 4 2

    5.4.2-

    • 1atm -

    • -


    3599664

    T-x

    • -B

    • vl


    3599664

    • v

    • f *= C +1 = 2 1 + 1 = 2

    • TxB


    3599664

    • l

    • f *= C +1 = 2 1 + 1 = 2

    • TxB


    3599664

    • l v

    • f *= C +1 = 2 2 + 1 = 1


    3599664

    • l v


    3599664

    BX1 t2 O

    • b b


    3599664

    • t2


    3599664

    • X11atm

    • t1

    • a


    3599664

    • B

    • A


    3599664

    • abcabc

    • t3c


    3599664


    3599664


    3599664

    • X1 t1t3


    3599664

    • aabbcc


    3599664


    3599664

    • bob O nmol

    • B mol X1bb


    3599664

    • molnl molnv


    3599664

    • O

    • nl nv

    • ()v()v = ()l ()l


    3599664

    • Bmolnx1Bmol

    nx1= nv x 3+ n l x4

    • n = nv+ n l x1

      nx1 = nv x1+ n l x1


    3599664

    nx1= nv x 3+ n l x4

    nx1 = nv x1+ n l x1

    nvx1+ nlx1 = nvx 3+ nlx4

    nv (x3 x1) = n l (x1 x4)


    3599664

    • molX

    • molnWmol X


    3599664


    3599664

    • X1()t1 t2 ab


    3599664

    • t1t2 abt2 b


    3599664

    • bX4 a b


    3599664

    • t2 ab t2


    3599664

    • bBa b


    3599664

    • AA

    • A


    3599664

    1.

    • t1t3 ac


    3599664

    • acc

    • aoc


    3599664

    2.


    3599664

    • O l

    • ab c c A


    3599664

    3.

    • bab


    3599664

    • dt4ddB


    3599664

    • B

    • B


    3599664

    • ABAB

      AB

    • AB


    3599664


    3599664


    3599664

    • B


    3599664

    • A

    • B


    3599664

    • P325


    3599664

    -T-X

    • -

    • -


    3599664


    3599664

    • (C)A B


    3599664


    3599664

    1. P-X CT-X C


    3599664

    • P-X CT1atm

    • T-X1atm


    3599664

    • f = C + 2 = 22 + 2 = 2


    3599664

    • P-XCC


    3599664

    2. 1atm

    • 1atm


    3599664

    • 1atm 760mmHg HCl + H2O 108.6C20.22% HCl

    • 0.92atm700mmHgHCl +H2O 106.4C20.36% HCl


    3599664

    • T-XAC

      ACB

    • CBBCA


    3599664

    -T-X

    • -

    • -


    3599664

    • A D A D

    • D B B D


    3599664

    1atm

    C

    HCl+H2O 108.6 () 20.22% HCl

    HNO3+ H2O 120.5 () 60% HNO3

    HBr+ H2O 126 () 47.5% HBr

    C2H5OH+ H2O 78.13 () 95.57% C2H5OH

    CCl4+CH3OH 55.7 () 44.5% CCl4


    5 4 3

    5.4.3 -


    3599664


    3599664

    • -----


  • 3599664

    -

    • f** = C + 0 = 22 + 0 = 0


    3599664

    f* = C + 1 = 22 + 1 = 1

    • --


    3599664

    • ACB

      f*= C +1

      = 21+1= 2


    3599664

    • ACB

    f*= C +1 = 2 2 +1 = 1

    ACB


    3599664

    • 50C

      l1 l2 X1 X2

    • X1

    • X2


    3599664

    • l1 l2


    3599664

    • X X1X2


    3599664

    • -


    3599664

    • tc C tc

    • tc


    3599664

    A-B (C) WA%

    - 59.6 5

    - 49.1 29

    - 65.9 66

    - 40.5 20

    - 167.0 15


    3599664

    1. 50Ca

    • ab


    3599664

    • ACB

      l1X2 l2

    • X1 X2

      l1 l2 X


    3599664

    • X2 l1

    • b


    3599664

    2.dACB

    • 50CACBl1 l 2


    3599664

    • l1 A

    • l2 B


    3599664

    3.

    • -


    5 4 4

    5.4.4


    3599664

    • ( Hg-H2O )

    • (CS2-H2O)

    • (C6H6Cl-H2O)


  • 3599664


    3599664

    P = PA* + PB*


    3599664

    --


    3599664


    3599664

    • PA*PB*


    3599664


    3599664

    • WH2O/WB

    • 100CB PB*


    3599664


    4 4 5

    4.4.5

    -

    • -


    3599664

    • 1atm

    • 1atm

    • ---


    3599664

    • 1atm-

    • 1atm


    3599664

    • f* = C + 1 = 2 + 1 = 3

    • -


    3599664

    1.

    • 0C


    3599664


    3599664

    2.

    1EL


    3599664

    • EM(NH4)2SO4(NH4)2SO4


    3599664

    • (NH4)2SO4


    3599664

    • EM (NH4)2SO4


    3599664

    • EMEL L


    3599664

    2ELEM

    f* = C +1 = 2 1 + 1 = 2


    3599664

    • LaEEL

    • MEb(NH4)2SO4EM


    3599664

    • LaE MEb

    f * = C + 1

    =22+1=1


    3599664

    3EELEM(NH4)2SO4

    f * = C + 1 = 2 3 + 1 = 0


    3599664

    • (18.3C)


    3599664

    • E(NH4)2SO4 E


    3599664

    • E

    • 18.3C

    f*=C +1=2 2 + 1=1


    3599664

    4LaEMEbELEM


    3599664


    3599664

    • 60g (NH4)2SO4 40g10C X


    3599664

    • (NH4)2SO4 Z Y


    3599664

    • Y(NH4)2SO4 42%

    • yx (NH4)2SO4

    • xz


    3599664

    yx 18 xz 40 58


    3599664

    yx = 18

    xz = 40

    yz = 58

    • 18/58 = 31%

    • 40/58 = 69 %


    3599664

    yx = 18

    xz = 40

    yz = 58

    • 100g10C 31 (NH4)2SO4 69 42% (NH4)2SO4


    3599664

    5

    i


    3599664

    ii


    3599664

    aO25% (NH4)2SO4 80C


    3599664

    • 80C(NH4)2SO4oP45%


    3599664

    b.PEM

    Q(NH4)2SO4


    3599664

    c. D (18.3C) EE(NH4)2SO4 Db : DE


    3599664

    d. E(NH4)2SO4 f*=0

    • E [+(NH4)2SO4 ]


    3599664

    e. (NH4)2SO4 18.3C (NH4)2SO4E


    3599664

    fE


    3599664

    6

    (C) (wt.%)

    NaCl 21.1 23.3

    NaBr 28.0 40.3

    NaI 31.5 39.0

    KCl 10.7 19.7

    KBr 12.6 31.3

    KI 23.0 52.3

    KNO3 3.0 11.2

    (NH4)2SO4 18.3 39.8

    Na2SO4 1.1 3.84

    MgSO4 3.9 16.5

    CaCl2 55.0 29.9

    FeCl2 55.0 33.1


    3599664

    3.

    • Bi-CdPb-SbKCl-AgClC6H6-CH3Cl

    • Bi-Cd


    3599664

    • EBiCd140C Cd40%Bi60%


    3599664

    • -Cd40%

    • Cd Cd40%Bi


    5 4 6

    5.4.6


    3599664

    • -

    • -

    • -


    3599664

    • -P80C, 45%, S20C


    3599664

    • -

    • PQQ


    3599664

    • Q


    3599664

    • QDf*=0

    • DD


    3599664

    • D S


    3599664


    3599664

    • DD

    • DDQD


    3599664


    5 4 7

    5.4.7

    1.

    • CuClFeCl3 CuClFeCl3

    • -


    3599664


    3599664

    2.

    1CuCl-FeCl3


    3599664

    • AB A E1

    • AB B E2


    3599664

    • E1 E2 CC AB C AB


    3599664

    • C

    • C


    3599664

    2H2O-Mn(NO3)2

    • -

    • H2O-Mn(NO3)2


    3599664

    • Mn(NO3)26H2O Mn(NO3)2 E1 E2

      Mn(NO3)2 40.5%64.5%


    3599664

    • D6


    3599664

    • BW636CBW6


    3599664

    • BW6 23.5CMn(NO3)26H2OMn(NO3)23H2O


    3599664

    1.


    3599664

    • C2 C1 + S

      • C2

      • C1


    3599664

    C2 C1 + S

    • C1

    • S

  • f * = C +1 = 2 3 +1 = 0


  • 3599664

    C2 C1 + S

    f * = C + 1 = 2 3 + 1 = 0

    • KNa


    3599664

    2. K-Na


    3599664

    • NaKNa2K7C Na S


    3599664

    • MS Na

    • SE Na2K

    • EN K


    3599664

    • E Na2K K

    • S Na2K S G


    3599664

    • SMSSESNa2KNa 7C

      Na2K Na + (S)


    3599664

    • KS


    3599664

    • abc


    3599664

    1bbNa2KNa2K


    3599664

    • Na2KMSNa


    3599664

    • MSS 7CNa

    • 7CSNaGT:GS


    3599664

    S+ Na Na2K

    • f *= C + 1= 2 3 + 1 = 0


    3599664

    • Na(S) Na2KNa

      Na2K


    3599664

    2a

    • ba Na 7C SNa


    3599664

    • Na2KNa

    • GTNa2KNa


    3599664

    3 c

    • 7CcNaNa2K7C

      NaNa2K S


    3599664

    • Na2KSNa2KSE


    3599664

    • 12CENa2K K

    • Ef*=0


    3599664

    • E()


    3599664

    3. NaI-H2O


    3599664

    • NaINaI5H2O

    • NaI5H2ONaI62.5%NaI2H2O NaI5H2O


    3599664

    • 13.5C NaI2H2OGNaI5H2O


    3599664

    • NaI5H2ONaI2H2O


    3599664

    • NaI5H2OEGG NaI5H2O


    5 4 8

    5.4.8


    3599664

    • ---


    3599664


    3599664

    1.

    • Bi Sb


    3599664

    • f * = C + 1 = 2 2 +1 = 1


    3599664

    • 1


    3599664

    • F

    • M

    • FM


    3599664

    • F

    • M


    3599664


    3599664

    • Bi

    • ,AB


    3599664

    2.

    • AA B


    3599664

    • AA BB


    3599664

    • AtB(A)


    3599664

    • a.


    3599664

    b.


    3599664

    • (B)


    3599664

    • tBBB

    • A


    3599664

    • Bi


    3599664

    • Bi


    3599664


    3599664

    3.


    3599664


    3599664

    4.

    • 899


    3599664

    • Ks


    3599664

    • (B)

      Ks =Cs /Cl1


    3599664

    • Ks 1


    3599664

    • Ks 1

    • (Cl )


    3599664


    3599664

    • NCsKs 1Cs Cl


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    3599664

    • KsKs


    5 4 9

    5.4.9


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    • f*= C + 1 = 2 3 +1 = 0


    Kno 3 tlno 3

    KNO3-TlNO3

    • TlNO3 KNO3

    • KNO3 TlNO3


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    • AEL

    • BEL

    • AC

    • BD


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    • AECL

    • BEDL


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    • ACG

    • BDH

    • GCDH


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    • ECD


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    t

    • mn

    • mEnC


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    • P182CCE

    • PE : PC


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    • ECD

      f*= C + 1 = 2 3 +1 = 0


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    • PP

    • C D PD : PC


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    • CGDH

    • ED


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    5.5

    • C = 3

      f = C + 2 = 5

    • fmin =0 max = 5


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    f = C + 2 = 5

    • min =1fmax = 4

    • f *max=3


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    f *max=3

    • f **max=2


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    • ABBCCA


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    PA20%B 30%C 50%


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    • P abc


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    Pa + Pb + Pc = AB = AC = BC

    • 100%

      Pa = A%Pb = B%Pc = C%


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    1.bb

    • bbA 20%


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    2.

    • APBC 3 : 5


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    3. MNMN


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    • MNMN

    • O

    WM : WN = ON : OM

    • O


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    4. DEFDEF


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    • DEFDEF

    • GGDEDFEFef ef DEeFFf E


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    • DEF G DEF


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    -

    • -

    • : KBr-NaBr-H2O; NaCl-Na2CO3-H2O

      NH4Cl- NH4NO3-H2O


    1 nh 4 cl nh 4 no 3 h 2 o

    1. NH4Cl-NH4NO3-H2O

    • DENH4ClNH4NO3


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    • S1S2 DF

    • S2S1 EF


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    • DF S2 S1

    • EF S1 S2

    • FDFEFS1S2


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    • F

      f** = C = 3 3 = 0


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    • DFS1 S1S1DFS1


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    • G S1 HS1S1GH:S1G


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    • EFS2 S2 S2 EFS2


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    • ADEFS1 S2

    • FS1S2 S1S2 Ff **= 0


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    • O S1S2 F


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    • O FS1 FS2 S1S2 pq


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    • pq F

    • S1pS2

    • qS2 S1


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    • NH4ClNH4NO3 P

    • NH4ClNH4NO3 PA


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    • FS1S2 FS1 S2


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    • bF

    • S1 S2

    • FS1

      WF : WS1 = S1b : bF


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    • RFT

    • TS1

      WS1: WT = RT : S1R


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    • DFS1


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    • PS1S2S1


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    • bS1PA S2bS1


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    • P


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    • FS1


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    • S1 S2 S1 MS1

    • MS1S2


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    • AFS1


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    • AF S2

    • AF S1, S2


    2 nacl na 2 so 4 h 2 o

    2. NaCl-Na2SO4-H2O

    • 17.5C


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    • D S1

    • B S2 10H2O

    • E (S210H2O)


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    • S1DFS1S1

    • BEFS210H2OS210H2O

    • ADFE


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    • FS1S210H2O

    • f**=33 = 0

    • FS1BS1S210H2O F

    • S1BS2S1S210H2O S2


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    • P

    • AP

    • DFS1


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    • S1DFF

    • S1F F

    • S210H2OS1


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    • S1B F

    • S210H2OS2 S1S2 S210H2O


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    • AFS1

    • AFS210H2OS2


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    3.

    • M


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    • FG M

    • FS1 M

    • GS2 M

    • GF


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    • FS1M:S1, MF

    • GMS2:S2, MG

    • FMG: M


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    • AF S1

    • AG S2

    • AF AG S1S2


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