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第五章 酸碱平衡 PowerPoint PPT Presentation


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第五章 酸碱平衡. § 5.1 酸碱质子理论概述. § 5.2 水的解离平衡和 pH 值. § 5.3 弱酸、弱碱的解离平衡. § 5.4 缓冲溶液. § 5.5 酸碱指示剂. § 5.6 酸碱电子理论与配合物概述. § 5.7 配位反应与配位平衡. § 5.1 酸碱质子理论概述. * 5.1.1 历史回顾. 5.1.2 酸碱质子理论的基本概念. 5.1.3 酸的相对强度和 碱的相对强度. 5.1.2 酸碱质子理论的基本概念.

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第五章 酸碱平衡

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5.1

5.2 pH

5.3

5.4

5.5

5.6

5.7


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5.1

*5.1.1

5.1.2

5.1.3


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5.1.2

H+

H+


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H+ +

+

-

+

HAc

H

Ac

-

+

-

+

2

H

PO

H

HPO

2

4

4

-

+

-

+

2

3

HPO

H

PO

4

4

+

+

+

NH

H

NH

4

3

+

+

[

]

+

CH

NH

H

CH

NH

3

3

3

2

+

+

3

2

+

[

]

[

]

+

Fe(H

O)

H

Fe(OH)(H

O)

2

6

2

5

+

+

2

+

[

]

+

[

]

Fe(OH)(H

O)

H

Fe(OH)

(H

O)

2

5

2

2

4


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H+ +

HAcAc

AcHAc

HAcAc


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HF(aq) H+ + F(aq)

H+ + H2O(l) H3O+(aq)

HF(aq) + H2O(l) H3O+(aq) + F(aq)

H+

H2O(l)+H2O(l) H3O+(aq) +OH(aq)

HF

(1)

(2)

(2)

(1)


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H+

Ac+H2O OH+ HAc

H+

+ H2O H3O+ + NH3

NaAc

(1)

(2)

(2)

(1)

NH4Cl

(1)

(2)

(2)

(1)


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H+

H+

NH4Cl


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HAc

HCN

5.810-10

1.810-5

5.1.3


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5.2 pH

5.2.1

5.2.2 pH


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H2O (l) + H2O(l)H3O+ (aq) + OH(aq)

H2O (l) H+ (aq) + OH(aq)

+

-

c

(

H

O

)

c

(

OH

)

=1.010-14

=

3

c

c

=5.4310-13

+

-

c

(

H

O

)

c

(

OH

)

=

3

T

5.2.1

25c(H+)= c(OH)=1.010-7molL-1

100


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{

}

=

-

+

pH

lg

c

(H

O

)

3

{

}

=

-

-

pOH

lg

c

(OH

)

{

}

{

}

=

=

+

-

-

c

(H

O

)

c

(OH

)

1.0

10

14

3

-

-

=

-

=

+

-

lg

c

(

H

)

lg

c

(

OH

)

lg

14

\

+

=

=

pH

pOH

p

14

5.2.2 pH


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5.3

5.3.1

5.3.2

5.3.3


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HAc(aq)+H2O(l) H3O+(aq)+Ac(aq)

{

}

{

}

+

-

c

(

H

O

)

c

(

Ac

)

=

(

HAc

)

3

{

}

c

(

HAc

)

x

2

=

(

HAc

)

-

0

.

10

x

5.3.1

1.

/molL-1 0.10 0 0

/molL-1 0.10x xx

x=1.3103


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=c{(H3O+)}{c(OH)}

c(H3O+) = c(Ac) = 1.3103 molL-1

c(HAc)=(0.10-1.3103)molL-10.10molL-1

c(OH) =7.71012 molL-1

(a)


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HA(aq) H+(aq) +A(aq)

()

c00

c ccc


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=

=

-

-

c

(

OH

)

0

.

200

0

.

95

%

1

.

9

10

3

=

-

=

-

-

=

-

pH

14

pOH

14

(

lg

1

.

9

10

)

11

.

27

3

+

-

-

c

(

NH

)

c

(

OH

)

(

1

.

9

10

)

3

2

=

=

(

NH

)

4

-

3

-

c

(

NH

)

0

.

200

1

.

9

10

3

3

=

-

1

.

8

10

5

2.

25 0.200molL-1 0.95%c(OH), pH

c0 0.200 0 0

ceq 0.200(1 0.95%) 0.2000.95% 0.2000.95%


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5.3.2


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0.010 molL-1 H2CO3 H3O+,

H2CO3, OHpH


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H+ c(H+) pH

c()

c()c() c2(H3O+)


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5.3.3

1.

(1) + (2) = (3)


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2.

NaAc , NaCNNaAc


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Na3PO4


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0.10molL-1Na3PO4pH

ceq/ (molL-1 )0.10 x x x


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3.

NaH2PO4,Na2HPO4,


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*4.


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0 T, K

5.

c ,

  • Al2S3,(NH4)2S


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5.4

5.4.1

5.4.2

5.4.3 pH

*5.4.4


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Ac(aq)

HAc(aq) + H2O (l) H3O+ (aq) +

Ac(aq)

NH4Ac(aq) (aq) +

5.4.1


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HAc(aq)+H2O(l)H3O+(aq)+Ac(aq)

0.10 molL-1 HAc NH4Ac (s) NH4Ac 0.10 molL-1 pH HAc

c0/ (molL-1)0.10 0 0.10

ceq / (molL-1)0.10 x x 0.10 + x

0.10 x 0.10

x = 1.810-5 c(H+) = 1.810-5 molL-1

pH = 4.74 = 0.018%

0.10 molL-1 HAcpH = 2.89 = 1.3%


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5.4.2

1(0.05ml) 1molL-1 HCl

1(0.05ml) 1molL-1 NaOH

50mlpH = 7 pH = 3 pH = 11

50mLHAcNaAc [c(HAc)=c(NaAc)=0.10molL-1] pH = 4.74

pH = 4.73 pH = 4.75

pH(pH)


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HAOHAH2O,c(A), c(HA)c(H3O+)pH

AH3O+HAc(HA)c(A)c(H3O+)pH


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5.4.3 pH

HAcNaAcH2CO3NaHCO3

  • c0(HA) ,c0(A)c(HA) ,c(A)


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2.

NH3 H2O NH4Cl


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1

2

3.

NaHCO3Na2CO3 , NaH2PO4Na2HPO4


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1


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2


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pH

c(HA)c(B) c(A)c(BH+) ,


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300mL 0.50molL-1 H3PO4 500mL 0. 50molL-1 NaOHpH


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4.

50.00ml 0.150molL-1 NH3 (aq) 0.200 molL-1 NH4Cl0.100ml 1.00 molL-1HCl HClpH

HCl


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NH3(aq) + H2O (l) (aq) +OH(aq)

HCl

HCl/(molL-1)

0.150 0.200

HCl/(molL-1)

0.150-0.0020 0.200+0.0020

/(molL-1)

0.150-0.0020-x 0.200+0.0020+xx


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pH

*5.4.4

H+ OH


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pHpH

pH


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,pH 2.0L Na3PO4 0.10molL-1 NaH2PO4 xL

2.0L0.10molL-1 Na3PO4 2.0L 0.10molL-1NaH2PO4 pH=12.50

Na2HPO4 Na3PO4

n/mol 20.10 0.10x 0

n/mol 0.20 0.10x 0 0.20x


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/(molL-1)

/(molL-1)


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x = 0.12 2.12L

(2L Na3PO4 + 0.12L NaH2PO4)

NaH2PO4 Na2HPO4 1.00LpH=7.20 50.00mL5.00mL 0.10molL-1 HCl pH 6.80 NaH2PO4 Na2HPO4 0.500molL-1 H3PO41.0molL-1 NaOH


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5.5

3.1 ~ 4.4

8.0 ~ 10.0

3.0 ~ 8.0


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5.6

5.6.1

5.6.2


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5.6.1

lewis

Fe3+ , Fe, Ag+, BF3

lewis

:X, :NH3, :CO, H2O:

lewislewis


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BF3 +F

Cu2+ + 4 NH3


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5.6.2

1.

Lewis[Ag(NH3)2]+LewisAg+NH3

Lewis()

Lewis


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en

Cu2+Ag+Fe3+FeNiBP

FClBrIOHCNH2ONH3CO


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2

O O

C C

O O

4

EDTAY4


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2+

Cu2+4


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[Ca(EDTA)]2CaY2

Ca2+64O2N


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K3[ Fe ( C N ) 6 ]


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2.


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( 0 )


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K[PtCl3NH3]()

[Co(NH3)5H2O]Cl3()

[PtNH2NO2(NH3)2]()

K[PtCl3(C2H4)]()


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()

()

()

()

()

()

()()

()

()

()


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3.

[Cu(en)2]2+ CaY2

[(H2O)4Fe(OH)2Fe(H2O)4]4+

COFe(CO)5Ni(CO)4

[PdCl3(C2H4)]

(NH4)3[P(Mo3O10)]6H2O


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5.7

5.7.1


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+

+

+

[Ag(NH

)

]

(aq)

[Ag(NH

)]

(aq)

NH

(aq)

K

3

2

3

3

d1

+

+

+

[Ag(NH

)]

(aq)

Ag

(aq)

NH

(aq)

K

3

3

d2

+

+

+

[Ag(NH

)

]

(aq)

Ag

(aq)

2

NH

(aq)

K

3

2

3

d

+

2

{

c

(Ag

)}{

c

(NH

)}

=

=

3

K

K

K

d

d1

d2

+

{

c

(

Ag(NH

)

)}

3

2

5.7.1

()


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+

+

+

Ag

(aq)

NH

(aq)

[Ag(NH

)]

(aq)

K

3

3

f1

+

+

+

[Ag(NH

)]

(aq)

NH

(aq)

[Ag(NH

)

]

(aq)

K

3

3

3

2

f2

+

+

+

Ag

(aq)

2

NH

(aq)

[Ag(NH

)

]

(aq)

K

3

3

2

f

+

{

c

(

Ag(NH

)

)}

=

=

3

2

K

K

K

f

f1

f2

+

2

{

c

(Ag

)}{

c

(NH

)}

3

1

=

K

K

f

f

K

d

1

1

=

=

K

K

f1

f2

K

K

d2

d1

()


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+

c(NH3) 0.010molL1

=

7

K

(Ag(NH

)

)

1.67

10

f

3

2

+

+

+

Ag

(aq)

2NH

(aq)

Ag(NH

)

(aq)

3

3

2

-

0

0.030

0

.

020

0.010

-

1

/(mol

L

)

-

x

2

x

x

-

1

/(mol

L

)

+

-

x

0.010

2

x

0.010

x

-

1

/(mol

L

)

0.010molAgNO3 (s)1.0L 0.030molL-1NH3H2O()Ag+NH3


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-

0.010

x

=

=

7

K

1.67

10

f

+

2

x

(

0

.

010

2

x

)

-

+

0.010

x

0

.

010

0

.

010

2

x

0

.

010

0

.

010

-

=

=

7

6

1.67

10

x

6

.

0

10

2

x

0

.

010

+

-

-

=

6

1

c

(

Ag

)

6

.

0

10

mol

L

+

-

=

=

1

c

(

NH

)

c

(Ag(NH

)

)

0

.

010

mol

L

3

3

2


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