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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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1

1

2

3--


4-

5

6



1.


1

2


3



2.

  • C

  • (S)(C)

  • SC


1C = S

  • C= S =2


2

(C) =(S)

(R)


(C) = (S)

(R)


  • CaCO3(s)CaO(s)CO2(g)

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

  • C = S R = 3 1=2 3


CaCO3 CO2CaOCO2CaCO3 CaO


  • NH4Cl

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

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

3


  • PNH3 = PHClcNH3 = c HCl

  • 32

  • C =3 1 1 = 1


  • C

    = S

    R

    R


  • CaCO3

    nCaO =nCO2

    CaO(s) CO2 (g)


(S)

  • i

    C =1 S


  • H2OH++OH

  • S=3 R =1

  • [H+] = [OH] R=1

    C=SRR=311 = 1


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


b. H2OR=2

HAc H+ + Ac

H2O H+ + OH

  • S = 5 (H2O, HAc, H+, OH, Ac)

  • R= 1

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


C = S R R = 5 2 1 = 2


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


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


(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


(1). NaAc+H2ONaOH+HAc

(2). HAc H+ + Ac

(3). NaOH Na+ + OH

(4). H2O H+ + OH

  • R= 1

  • [Na+] + [H+] = [Ac] +[OH]


(1). NaAc+H2ONaOH+HAc

(2). HAc H+ + Ac

(3). NaOH Na+ + OH

(4). H2O H+ + OH

  • NaAcNaAc R=1

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


  • C = SRRR

    = 8411=2


3.

  • f


  • Vm

  • f = 2


  • T, P


  • P=1atm0C100C

  • 0C

  • 100C



  • f = 2

  • f = 1

    • P=PH2O* f =1


5.2

  • f = C + n


  • f = C + 2

    • f

    • C

    • 2


f = C + 2

    • 11

    • 11

  • 1876Gibbs


C f

1C

  • C


  • (C1)

    C()

  • (C1)


  • f = (C1) + 2


  • i

    i = i= = i

    (1)

  • C

    C(1)


f = (C1) + 2

  • C(1)

    ()

  • f = (C1)+2C(1)

    = C+2


2C

  • NaCl+H2O NaCl


  • NaCl

  • f = C+2

  • NaCl1


  • (g)NaCl= (l)NaCl

  • (C1)1 C(1)1

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


1. Na2CO3H2O Na2CO37H2ONa2CO310H2O

1) 1atm

2) 30C


: Na2CO3 Na2CO3

2 C= 2

1 1atm

f* = C +1

= C+1 f* = 3 f*


= C+1 f* = 3 f*

  • f* =0

2

f* =C+1=3


2.

125C 1atmNaCl

C = 2 = 2

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

  • NaCl


  • 25C1atmNaCl

    =1

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

  • NaCl


2I2s I2g

C =1 = 2

f = C + 2 = 12 + 2 = 1

  • I2s I2g


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


P = PNH3 + PHCl

PHClP NH3 = 1/KP

PHCl, PNH3

PHClPNH3


3.

1

2

3


+ +

1

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

=4f* max = 4


+ +

2

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

max =3


+ +

3

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


1.


2.



  • 5.3

    1.


    • f = C+2 = 11+2=2

    • PT f=2 P, T


    • PT


    • i -

    • ii -

    • iii-

    f = C + 2 = 12 + 2 = 1


    • TPPT


    • PT


    • --

    • f = C + 2 = 1 3 + 2 = 0

    • T, P


    • O



    OA:-T

    OB:-T

    OC:-

    O --


    • 0.0098C 4.58mmHg


      • ;

      • OAOBOC;

      • O


    2.

    1)OA

    374C220atm-


    • OA OOF

    • OF-

    • OFOB



    • 2) OB

    • -


    • T0 lnP P 0

    • OB


    • OB O



    3OC2000atm20C


    • OC

    • 4.58mmHg0.01 C1atm 0C


    OAOBOC


    3.

    • P(760mmHg)T1 T2


    • T1, PXT2 XY


    • N

    • f = C +1 =12+1= 0

    • T =0C


    • M (T=100C)

    • T2


    • f = C+2 =3


    • 4 PT

    • C42 = 66

    • C43 = 4 4


    • AABBCCABBCCAABC


    • BB, AB,


    • AABBCCOAOAC


    • COCA

    • BO BA


    • O

    • XY

    • --

    • P317-318


    5.4

    • f = 2 + 2 = 4

    • f = 0 = 4

    • 4

    • =1 f=3


    • 4P-T-x

    • P-T


    • P


    • f*= 2 +1 = 3

      • = 1 f*= 2

      • =3 f*= 0

      • =2 f*=1


    • 1

      2

      3


    • 3-

    • 1


    5.4.1 -


    -


    1. 40CC6H12-CCl4-


    • 1

    1. 40CC6H12-CCl4-


    • 2

    2. CH2(OCH3)2-CS235C-


    • 3

    3. CH3COCH3-CHCl355C-


    • -

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


    • -

      • CH2(OCH3)2-CS2

      • CH3COCH3-CS2

      • C6H6- C6H12

      • H2O-C2H5OH


    • -

      • CHCl3-CH3COCH3

      • H2O-HCl


    • PA* PB* yA xA


    • 1881

      1


    2-


    • (1)---

    • Pi*


    l -

    v -


    • B

    • BB

    • vl


    • aa

    • vlBA


    • ACB

      BB


    • CBA

    • AA

    • C


    • ADAA

    • DBBB


    • D

    • -


    5.4.2-

    • 1atm -

    • -


    T-x

    • -B

    • vl


    • v

    • f *= C +1 = 2 1 + 1 = 2

    • TxB


    • l

    • f *= C +1 = 2 1 + 1 = 2

    • TxB


    • l v

    • f *= C +1 = 2 2 + 1 = 1


    • l v


    BX1 t2 O

    • b b


    • t2


    • X11atm

    • t1

    • a


    • B

    • A


    • abcabc

    • t3c




    • X1 t1t3


    • aabbcc



    • bob O nmol

    • B mol X1bb


    • molnl molnv


    • O

    • nl nv

    • ()v()v = ()l ()l


    • Bmolnx1Bmol

    nx1= nv x 3+ n l x4

    • n = nv+ n l x1

      nx1 = nv x1+ n l x1


    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)


    • molX

    • molnWmol X



    • X1()t1 t2 ab


    • t1t2 abt2 b


    • bX4 a b


    • t2 ab t2


    • bBa b


    • AA

    • A


    1.

    • t1t3 ac


    • acc

    • aoc


    2.


    • O l

    • ab c c A


    3.

    • bab


    • dt4ddB


    • B

    • B


    • ABAB

      AB

    • AB




    • B


    • A

    • B


    • P325


    -T-X

    • -

    • -



    • (C)A B



    1. P-X CT-X C


    • P-X CT1atm

    • T-X1atm


    • f = C + 2 = 22 + 2 = 2


    • P-XCC


    2. 1atm

    • 1atm


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

    • 0.92atm700mmHgHCl +H2O 106.4C20.36% HCl


    • T-XAC

      ACB

    • CBBCA


    -T-X

    • -

    • -


    • A D A D

    • D B B D


    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 -



    • -----


  • -

    • f** = C + 0 = 22 + 0 = 0


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

    • --


    • ACB

      f*= C +1

      = 21+1= 2


    • ACB

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

    ACB


    • 50C

      l1 l2 X1 X2

    • X1

    • X2


    • l1 l2


    • X X1X2


    • -


    • tc C tc

    • tc


    A-B (C) WA%

    - 59.6 5

    - 49.1 29

    - 65.9 66

    - 40.5 20

    - 167.0 15


    1. 50Ca

    • ab


    • ACB

      l1X2 l2

    • X1 X2

      l1 l2 X


    • X2 l1

    • b


    2.dACB

    • 50CACBl1 l 2


    • l1 A

    • l2 B


    3.

    • -


    5.4.4


    • ( Hg-H2O )

    • (CS2-H2O)

    • (C6H6Cl-H2O)



    P = PA* + PB*


    --



    • PA*PB*



    • WH2O/WB

    • 100CB PB*



    4.4.5

    -

    • -


    • 1atm

    • 1atm

    • ---


    • 1atm-

    • 1atm


    • f* = C + 1 = 2 + 1 = 3

    • -


    1.

    • 0C



    2.

    1EL


    • EM(NH4)2SO4(NH4)2SO4


    • (NH4)2SO4


    • EM (NH4)2SO4


    • EMEL L


    2ELEM

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


    • LaEEL

    • MEb(NH4)2SO4EM


    • LaE MEb

    f * = C + 1

    =22+1=1


    3EELEM(NH4)2SO4

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


    • (18.3C)


    • E(NH4)2SO4 E


    • E

    • 18.3C

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


    4LaEMEbELEM



    • 60g (NH4)2SO4 40g10C X


    • (NH4)2SO4 Z Y


    • Y(NH4)2SO4 42%

    • yx (NH4)2SO4

    • xz


    yx 18 xz 40 58


    yx = 18

    xz = 40

    yz = 58

    • 18/58 = 31%

    • 40/58 = 69 %


    yx = 18

    xz = 40

    yz = 58

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


    5

    i


    ii


    aO25% (NH4)2SO4 80C


    • 80C(NH4)2SO4oP45%


    b.PEM

    Q(NH4)2SO4


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


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

    • E [+(NH4)2SO4 ]


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


    fE


    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


    3.

    • Bi-CdPb-SbKCl-AgClC6H6-CH3Cl

    • Bi-Cd


    • EBiCd140C Cd40%Bi60%


    • -Cd40%

    • Cd Cd40%Bi


    5.4.6


    • -

    • -

    • -


    • -P80C, 45%, S20C


    • -

    • PQQ


    • Q


    • QDf*=0

    • DD


    • D S



    • DD

    • DDQD



    5.4.7

    1.

    • CuClFeCl3 CuClFeCl3

    • -



    2.

    1CuCl-FeCl3


    • AB A E1

    • AB B E2


    • E1 E2 CC AB C AB


    • C

    • C


    2H2O-Mn(NO3)2

    • -

    • H2O-Mn(NO3)2


    • Mn(NO3)26H2O Mn(NO3)2 E1 E2

      Mn(NO3)2 40.5%64.5%


    • D6


    • BW636CBW6


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


    1.


    • C2 C1 + S

      • C2

      • C1


    C2 C1 + S

    • C1

    • S

  • f * = C +1 = 2 3 +1 = 0


  • C2 C1 + S

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

    • KNa


    2. K-Na


    • NaKNa2K7C Na S


    • MS Na

    • SE Na2K

    • EN K


    • E Na2K K

    • S Na2K S G


    • SMSSESNa2KNa 7C

      Na2K Na + (S)


    • KS


    • abc


    1bbNa2KNa2K


    • Na2KMSNa


    • MSS 7CNa

    • 7CSNaGT:GS


    S+ Na Na2K

    • f *= C + 1= 2 3 + 1 = 0


    • Na(S) Na2KNa

      Na2K


    2a

    • ba Na 7C SNa


    • Na2KNa

    • GTNa2KNa


    3 c

    • 7CcNaNa2K7C

      NaNa2K S


    • Na2KSNa2KSE


    • 12CENa2K K

    • Ef*=0


    • E()


    3. NaI-H2O


    • NaINaI5H2O

    • NaI5H2ONaI62.5%NaI2H2O NaI5H2O


    • 13.5C NaI2H2OGNaI5H2O


    • NaI5H2ONaI2H2O


    • NaI5H2OEGG NaI5H2O


    5.4.8


    • ---



    1.

    • Bi Sb


    • f * = C + 1 = 2 2 +1 = 1


    • 1


    • F

    • M

    • FM


    • F

    • M



    • Bi

    • ,AB


    2.

    • AA B


    • AA BB


    • AtB(A)


    • a.


    b.


    • (B)


    • tBBB

    • A


    • Bi


    • Bi



    3.



    4.

    • 899


    • Ks


    • (B)

      Ks =Cs /Cl1


    • Ks 1


    • Ks 1

    • (Cl )



    • NCsKs 1Cs Cl



    • KsKs


    5.4.9


    • f*= C + 1 = 2 3 +1 = 0


    KNO3-TlNO3

    • TlNO3 KNO3

    • KNO3 TlNO3


    • AEL

    • BEL

    • AC

    • BD


    • AECL

    • BEDL


    • ACG

    • BDH

    • GCDH


    • ECD


    t

    • mn

    • mEnC


    • P182CCE

    • PE : PC


    • ECD

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


    • PP

    • C D PD : PC


    • CGDH

    • ED



    5.5

    • C = 3

      f = C + 2 = 5

    • fmin =0 max = 5


    f = C + 2 = 5

    • min =1fmax = 4

    • f *max=3


    f *max=3

    • f **max=2



    • ABBCCA


    PA20%B 30%C 50%


    • P abc


    Pa + Pb + Pc = AB = AC = BC

    • 100%

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


    1.bb

    • bbA 20%


    2.

    • APBC 3 : 5


    3. MNMN


    • MNMN

    • O

    WM : WN = ON : OM

    • O


    4. DEFDEF


    • DEFDEF

    • GGDEDFEFef ef DEeFFf E


    • DEF G DEF


    -

    • -

    • : KBr-NaBr-H2O; NaCl-Na2CO3-H2O

      NH4Cl- NH4NO3-H2O


    1. NH4Cl-NH4NO3-H2O

    • DENH4ClNH4NO3


    • S1S2 DF

    • S2S1 EF


    • DF S2 S1

    • EF S1 S2

    • FDFEFS1S2


    • F

      f** = C = 3 3 = 0


    • DFS1 S1S1DFS1


    • G S1 HS1S1GH:S1G


    • EFS2 S2 S2 EFS2


    • ADEFS1 S2

    • FS1S2 S1S2 Ff **= 0


    • O S1S2 F


    • O FS1 FS2 S1S2 pq


    • pq F

    • S1pS2

    • qS2 S1



    • NH4ClNH4NO3 P

    • NH4ClNH4NO3 PA


    • FS1S2 FS1 S2


    • bF

    • S1 S2

    • FS1

      WF : WS1 = S1b : bF


    • RFT

    • TS1

      WS1: WT = RT : S1R


    • DFS1


    • PS1S2S1


    • bS1PA S2bS1


    • P


    • FS1


    • S1 S2 S1 MS1

    • MS1S2


    • AFS1


    • AF S2

    • AF S1, S2


    2. NaCl-Na2SO4-H2O

    • 17.5C


    • D S1

    • B S2 10H2O

    • E (S210H2O)


    • S1DFS1S1

    • BEFS210H2OS210H2O

    • ADFE


    • FS1S210H2O

    • f**=33 = 0

    • FS1BS1S210H2O F

    • S1BS2S1S210H2O S2


    • P

    • AP

    • DFS1


    • S1DFF

    • S1F F

    • S210H2OS1


    • S1B F

    • S210H2OS2 S1S2 S210H2O


    • AFS1

    • AFS210H2OS2


    3.

    • M


    • FG M

    • FS1 M

    • GS2 M

    • GF


    • FS1M:S1, MF

    • GMS2:S2, MG

    • FMG: M


    • AF S1

    • AG S2

    • AF AG S1S2


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