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14-16

17

F , Cl , Br , I , At

Cl

Br

17

35

53

. .

2s22p5

()

3s23p5

3d104s24p5

4d105s25p5

71

99

114

133

I1 ()

17.46

13.01

11.82

10.30

I2 ()

34.71

23.85

21.47

19.11

I7 ()

184.2

113.8

103.5

90.2

Ae ()

3.5

3.6

3.5

3.3

4.0

3.2

3.0

2.7

AR

4.10

2.83

2.48

2.21

..

-1,0

-1,0,1,3,(4),5,(6),7

-1,0,1,3,5,(7)

-1,0,(1),3,5,7

Cl

Br

17

35

53

. .

2s22p5

()

3s23p5

71

I1 ()

17.46

I2 ()

34.71

I7 ()

184.2

Ae ()

3.5

4.0

AR

4.10

..

-1,0

140

4d105s25p5

99

114

133

13.01

11.82
I
21.47

10.30

103.5

90.2

3.5

3.3

3.2

3.0

2.7

2.83

2.48

2.21

10
20
30
-1,0,1,3,(4),5,(6),7
n

40-1,0,1,3,5,(7)
50

r,

23.85
120

113.8
Cl
3.6

100
80

3d104s24p5

Br

19.11

-1,0,(1),3,5,7

Cl

Br

17

35

53

. .

2s22p5

()

3s23p5

3d104s24p5

4d105s25p5

71

99

114

133

I1 ()

17.46

13.01

11.82

10.30

I2 ()

34.71

I1 ()
23.85

21.47

19.11

I7 ()

184.2

113.8

103.5

90.2

Ae ()

3.5

3.6

3.3

4.0

3.2

3.5

3.0

2.7

2.83

2.48

2.21

-1,0,1,3,(4),5,(6),7
10
20
30
n

-1,0,1,3,5,(7)
40
50

AR

4.10

..

-1,0

18
16
14
12
10

-1,0,(1),3,5,7

Cl

Br

17

35

53

. .

2s22p5

()

3s23p5

3d104s24p5

4d105s25p5

71

99

114

133

I1 ()

17.46

13.01

11.82

10.30

I2 ()

34.71

23.85

21.47

19.11

I7 ()

184.2

113.8

103.5

90.2

Ae ()

3.5

3.6

3.5

3.3

4.0

3.2

3.0

2.7

AR

4.10

2.83

2.48

2.21

..

-1,0

-1,0,1,3,(4),5,(6),7

-1,0,1,3,5,(7)

-1,0,(1),3,5,7


F
.
. .
()

4,0

2s22p5 3,5
71

3,0

Cl

Br

17

35

53

3s23p5

3d104s24p5

99

I1 ()

17.46

13.01

I2 ()

34.71

I7 ()

184.2

Ae ()

3.5

3.6

4.0

AR
..

2,5
2,0

23.85

A-R

10113.8
20

30

4d105s25p5

114
P
11.82

10.30

21.47

19.11

40103.5
50

133

90.2

3.5

3.3

3.2

3.0

2.7

4.10

2.83

2.48

2.21

-1,0

-1,0,1,3,(4),5,(6),7

-1,0,1,3,5,(7)

-1,0,(1),3,5,7


F2

Cl2

Br2

I2

.. ()

-188.1

-34.0

59.5

.. ()

-219.6

-101.0

-7.2

..

0 .,
/

158.8

242.6

192.8

151.1

E0 (X2/X-),

2.869

1.358

1.065

0.535

192.8 (.)


:
F2

Cl2, Br2, I2

a
b
c

Cl2

Br2

I2

a, pm

198

227

272

b, pm

332

332

350

c, pm

374

399

427

b/a

1.68

1.46

1.29


F2
1.

Cl2

Br2

I2

2.

+ + F+ [O]

3. 2

20
= HF

= HCl

4.

5.

He, Ne,
Ar, O2

N2, C,
O2, Ng

P, As, H2

P, As, H2

F2

F2, Cl2

HNO3 (/)

6.

8.2 /

35 /

0.15 /

= HBr

HI


1.
2.

3.

4.

F2 + Xe = XeF2
(+ XeF4 + XeF6)

5Cl2 + 2Sb = 2SbCl5


2Cl2 + Zr = ZrCl4
250
( CuCl)
Cl2 + Cu = CuCl2
Br2 () + Hg () = HgBr2 ()
CCl4/60oC
2I2 + Sn = SnI4
Br2 + H2 = 2HBr

Br2 2Br

Br + H2 = HBr + H
H + Br2 = HBr + Br

HBr + H = Br + H2
2Br = Br2

2H = H2
H2 + I2 2HI

fG0298 = +1.8 /


5.

2F2 + 2H2O = 4HF + O2

20oC

X2 + H2O H+ + X- + HOX
20oC
K = 4.210-4
X = Cl
K = 7.210-9
X = Br
K = 2.010-13
X=I
X2 + 2OH- X- + OX- H2O
20oC
K = 7.51015
X = Cl
K = 2103
X = Br
K = 30
X=I
X = Br, I:
3OX- 2X- + XO3

85,
,
,

209Bi

+ 4He = 211At + 21n

210At, t1/2 = 8 , 6
:
At2 , I2
At2 + SO2 + 2AgNO3 + 2H2O = 2AgAt + H2SO4 + 2HNO3
At2 S2O82- Br2


HF KHF2

2CeF4 = 2CeF3 + F2
HCl ( )
KMnO4() + 16HCl() + 2KCl = K3MnCl6 + 2Cl2 + 4H2O
( )

2NaCl + 2H2O = Cl2 + 2NaOH + H2


2KBr + Cl2 = 2KCl + Br2
2KI + Cl2 = 2KCl + I2

(UF6)
(CaF2)
(HF, BrF3)
(CF2Cl2, )

(, )
()
(Cl2)
(Br2)
(AgBr)

(I2)
(KI, KI3)
()
(NaI)



3

1.
CsCl
, ,
NaCl, CsCl, CaF2, BaCl2, LaF3
2.
d- .., p-,

FeCl2, CrF3, BiCl3, CdBr2
CdI2
3.
-, d-
..
SnCl4, GaBr3, NbCl5, WCl6


..-1
HF, HCl, HBr, HI

HF

HCl

HBr

HI

..,

-83.5

-114.2

-86.9

-51.0

..,

19.5

-85.1

-67.1

-35.1

d(H-X), pm

92

127.5

141.5

161

, / 570

432

366

298

, D

1.83

1.11

0.83

0.45

450

600

425

-9

-11.2

-12.4

.
1 2
pKa

2.95


..-1
HF, HCl, HBr, HI

..,
oC 25
..,
0

HF

HCl

HBr

HI

-83.5

-114.2

-86.9

-51.0

-67.1

-35.1

19.5

-85.1

600
500

E, /

d(H-X), pm ..
92

127.5

400

141.5

, / 570

-50

432

300

366

298

,-75
D

1.11

0.83

0.45
d,

600

-25

1.83

-100
.. 450
.

1 2
HF
HCl
HBr
HI
pKa
2.95
-9

HF

161

425

, D

HCl
-11.2

HBr

HI
-12.4


..-1
HF, HCl, HBr, HI

..,
/

HF

HCl

-83.5

-114.2

35

30
19.5
..,
25
d(H-X),
pm
92
20
, / 570
15

,4D

.
0 1 2
HF
HCl
HBr
pKa
2.95

HI

-86.9

-51.0

50 /

-85.1

-67.1

127.5

-50

141.5

432

1.83

HBr

-100

366

-150

-35.1
161

fG

298

1.11

-200

0.83

0.45

450

-250

600

425

HI

HF
-9

HCl
-11.2

HBr

HI
-12.4


1.
HF < HCl < HBr < HI

: HFHI
3+ -

2. ( HF)
4HCl() + MnO2() = Cl2 + MnCl2 + 2H2O
2HI + 2FeCl3 = 2FeCl2 + I2 + 2HCl
3.
HF

HCl

HBr

HI

.,
( = 1 )

112

108.6

124.3

126.7

, .%

38

20.2

47.6

56.7


4. HF
) . ., . .
)
HF + F- = HF2-

(NH4HF2, KHF2)

[F-H-F]) SiO2
4HF + SiO2 = SiF4 + 2H2O

d = 113 pm

) HF
3HF H2F+ + HF2-

2HF + BF3 H2F+ + BF4-

HF + BrF3 BrF2+ + HF2-


H2 + X2 = 2HX
1.
2.

CaF2 + H2SO4() = CaSO4 + 2HF


KCl() + H2SO4() = KHSO4 + HCl

3.

KBr() + H2SO4() = KHSO4 + HBr

(to)
(to)

2KBr() + 3H2SO4() = 2KHSO4 + Br2 + SO2 + 2H2O


KBr() + H3PO4(85%) = KH2PO4 + HBr

(to)

PBr3 + 3H2O = H3PO3 + 3HBr


4.

KI() + H3PO4(85%) = KH2PO4 + HI


I2 + H2S = S + 2HI

(to)

()
,

.. -1,
.. +n

: ClF, BrF3, IBr, IF5


:

F .. -1

.. Cl < Br < I

.. Cl, Br, I F

()

ClF
BrF
IF
BrCl
ICl
IBr
ClF3
BrF3
IF3
ICl3 (I2Cl6)
ClF5
BrF5
IF5
IF7


-
-
-
-
-


-
. -



, D
0.89
1.42

0.52
1.24
0.73
0.61
1.19

1.51
2.18
0

..,
-156
-33
14 ()
-66
27.2
41
-76.5
23
-28 ()
101 ()
-103
-60.5
9.5
5 ()


1.
2ICl3 = 2ICl + Cl2

2ICl = I2 + Cl2

(to)

10IF = 2IF5 + 4I2

(to)

2.
BrF5 + 3H2O = HBrO3 + HF

5ICl3 + 9H2O = I2 + HIO3 + 15HCl


2ICl3 + 3H2O = HIO3 + HICl2 + 4HCl
2ICl3 + 6H2O = 2HIO3 + HI + 9HCl


3.
ClF + CsF = Cs[ClF2]
I2 + 3Cl2 + KCl + 2H2O = 2K[ICl4]2H2O
2KClO3 + 3KI + 12HCl = 3K[ICl4]2H2O + 2KCl
4.
W + 6ClF = WF6 + 3Cl2
2Co3O4 + 6ClF3 = 6CoF3 + 3Cl2 + 4O2
5.
2BrF3() BrF2+ + BrF4BrF3 + AsF5 = [BrF2+][AsF6-]

NOF + BrF3 = [NO+][BrF4-]

ClF3

BrF5

7e- (Cl) + 3e- (F) = 10e-

7e- (Br) + 5e- (F) = 12e-

32
5--
- ,
-

5
6--
,
-


I2Cl6
!

:
7e- (I) + 2e- (Cl) + 2e- (-Cl) = 10e42
(4+1)--
, -

-
-:
I
I3-, I42-, I5-, I7-, I82-, I9-, I104-, I123-, I162-, I164-, I224-, I293
Cl, Br, I, F
:
KI (aq) + I2 KI3 (aq)
I- + I2 I3-

(+KI9)

K 100 25
d(I-I) = 283 303 CsI3
= 290 [Ph4P]I3

I3-



OF2
.. -223.8
.. -145.3
.. +201

O2F2, O3F2, O4F2


0

0oC

2NaOH () + F2 2NaF + OF2 + H2O


141
!
to

OF2 + H2O O2 + 2HF

103

Cl, Br, I
..

Cl

Br

+1

Cl2O

Br2O

+3

Cl2O3

Br2O3

+4

ClO2

BrO2

I2O4

Br2O5

I2O5

+2

+5
+6

Cl2O6

+7

Cl2O7

Cl2O6

I2O6

Cl2O7


Cl2O

ClO2

Cl2O6

Cl2O7

..

+1

+4

+6

+7

..,

-120.6

-59

3.5

-91.5

..,

11

203

81

Cl2O
2Cl2 + 3HgO = Hg3O2Cl2 + Cl2O

2Cl2 + Bi2O3 = 2BiOCl + Cl2O


Cl2O + 2KOH = 2KOCl + H2O


ClO2
2KClO3 + 2H2C2O4 = 2ClO2 + 2CO2 + K2C2O4 + 2H2O (.)
2NaClO3 + SO2 + H2SO4 = 2NaHSO4 + ClO2

(.)

2ClO2 + H2O = HClO2 + HClO3

(2Cl4+ Cl3+ + Cl5+)

2ClO2 + 2NaOH = NaClO2 + NaClO3 + H2O

(2Cl4+ Cl3+ + Cl5+)

2ClO2 + Na2O2 = 2NaClO2 + O2

ClO2


Cl2O6 (ClO3)
ClO2 + O3 = ClO3 + O2

,
2ClO3 + H2O = HClO3 + HClO4
Cl2O7
2HClO4 + P2O5 = Cl2O7 + 2HPO3
Cl2O7 + H2O = 2HClO4
!


I2O5
2HIO3 I2O5 + H2O
2I2 + 5O2 = 2I2O5

fH0298 = -158.1 /

, :
, I2O5 350 0
I2O5 + 5CO = I2 + 5CO2

3I2O5 + H2O = 2HI3O8

HI3O8 + H2O = 3HIO3


1. ( )
..

Cl

Br

-1

HOF

+1

HOCl

HOBr

HOI

+3

HClO2

+5

HClO3

HBrO3

HIO3

+7

HClO4

(HBrO4)

H5IO6

2.
-50

F2() + H2O() HF() + HOF()


2HOF = 2HF + O2

..

4HOF + 2H2O = 4HF + 2H2O2 + O2

Cl, Br, I
Cl

Br

+1

HOCl
pKa = 4.53

HOBr
pKa = 8.69

HOI
pKa = 10.64
pKb = 10.1

+3

HClO2
pKa = 2

+5

HClO3
pKa = -1.2

HBrO3
pKa = 0.7

HIO3
pKa = 0.8

+7

HClO4
pKa = -10

HBrO4
pKa = ?

H5IO6
pKa1 = 3.3

Cl, Br, I
1. HOX
IO- + H+ HOI I+ + OH-

2HClO HClO2 + HCl


3HBrO HBrO3 + 2HBr

(HOI)

2Cl2 + H2O + 3HgO = Hg3O2Cl2 + 2HOCl

2. HClO2
4HClO2 = 2ClO2 + HClO3 + HCl + H2O

(4Cl3+ 2Cl4+ + Cl5+ + Cl-)

HClO2 = O2 + HCl
5HClO2 = 4ClO2 + HCl + 2H2O

3HClO2 = 2HClO3 + HCl


Ba(ClO2)2 + H2SO4 = 2HClO2 + BaSO4

Cl, Br, I
3. HClO3, HBrO3
HIO3
3HClO3 = HClO4 + 2ClO2 + H2O

(to)

(3Cl5+ Cl7+ + 2Cl4+)

4HBrO3 = 2H2O + 2Br2 + 5O2

(to)

2HIO3 = I2O5 + H2O

(to)

I2 + 10HNO3(/) = 2HIO3 + 10NO2 + 4H2O


I2O5 + H2O = 2HIO3

Ba(ClO3)2 + H2SO4 = 2HClO3 + BaSO4


2HIO3 + 5H2O2 = I2 + 5O2 + 6H2O
I2 + 5H2O2 = 2HIO3 + 4H2O
IO3-

Cl, Br, I
4. HClO4
HBrO4
H5IO6

HClO4

H5IO6

HClO4
2HClO4() + Ca = Ca(ClO4)2 + H2
H5IO6 + K2CO3 = K2H3IO6 + CO2 + H2O
K2H3IO6 + KOH = K3H2IO6 + H2O

5-

HCl + NaClO4 = HClO4 + NaCl


Ba3(H2IO6)2 + 6HNO3(/) = 2H5IO6 + Ba(NO3)2


HClO

HClO2

HClO3

HClO4


Cl-O -
:
-
Cl-O


HClO3

ClO3-

HBrO3

BrO3 -
-

HIO3

IO3-

X(N) + Ne- = X(0)

1.
2.
3.

E 0,

Red/Ox
1. ,
ClO4- + 2H+ + 2e- = ClO3- + H2O

pH=0, E0 = +1.20 B

ClO4- + H2O + 2e- = ClO3- + 2OH-

pH=14, E0 = +0.37 B

HClO4 + H2SO4 + 2FeSO4 = HClO3 + H2O + Fe2(SO4)3


2KClO4 + FeSO4 Fe(ClO4)2 + K2SO4

2. pH=0 X+ Cl3+
=14 2
.. +5
2HClO2

HClO3 + HClO

3NaClO = NaClO3 + 2NaCl

( 60 0)

Red/Ox
3.

HClO

HClO2

HClO3

Cl
-


HClO4

HClO4

Red/Ox
4. .. +7
=0, =14
5HBrO4 + 2MnSO4 + 3H2O = 2HMnO4 + 5HBrO3 + 2H2SO4
H5IO6 + 2HCl = HIO3 + 3H2O + Cl2
HClO4 + HCl =
: r(Br)>r(Cl) ..=4,
I ..=6
5. .. +5
Cl Br > I
2KBrO3 + I2 = 2KIO3 + Br2
2KClO3 + I2 = 2KIO3 + Cl2

Cl, Br, I
1. :
2KOH + Cl2 = KClO + KCl + H2O

20

CaO + Cl2 = CaOCl2

20oC

[Ca(OCl)2CaCl2]


4NaOH + 3NaOCl + 2Fe(OH)3 = 2Na2FeO4 + 3NaCl + 5H2O
2.
Na2O2 + 2ClO2 = 2NaClO2 + O2
5NaClO2 + 2H2SO4 = 4ClO2 + 2Na2SO4 + 2H2O + NaCl
Ca(ClO2)2

Cl, Br, I
3. , ,
6KOH + 3Cl2 = KClO3 + 5KCl + 3H2O

60

6KOH + 3Br2 = KBrO3 + 5KBr + 3H2O


2KClO3 + I2 = 2KIO3 + Cl2
4KClO3 = KCl + 3KClO4

2KClO3

2Ca(IO3)2 = 2CaO + I2 + 5O2

(Br)

MnO2, to

4. , ,
KBrO3 + F2 + 2KOH = KBrO4 + 2KF + H2O
KOH + H2O + KIO3 + KOCl = K2H3IO6 + KCl
K2H3IO6 + HNO3 = KIO4 + KNO3 + 2H2O
KClO4 = KCl + 2O2

( )

2KCl + 3O2


1. 2- .
.. .. --
2
2. . F

3. .
. F ..
4. . HF
.
5. ,

6. Cl, Br, I.
.. +7. +7
Br>Cl>I.
7. .. -1 +5.
ClO2
8.