�� ... ��, �� 9

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9. �� .

9.1. �� Cl-O � ��.

� �� , �� , ��, �� HClO, �� (c�� HClO₄�� : �� ) � �� . � �� HClO-HClO₂--HClO₃-HClO₄ �� (��.7) �� .

�� 7.�� .

��	HClO	HClO₂	HClO₃	HClO₄
�� Cl-O,	1.69	1.64	1.57	1.45
��	HOCl=103^o	O�lO=111^o	OClO=107^o	OClO=105.6^o
E_{��} Cl-O, ��/��	209.0	244.5	243.7	363
��_a 25^��	7.5	2.0	-1.2	-10
�^�, B	1.63	1.63	1.47	1.34

�� Cl-O � �� . � �� . � �� (��), �� Cl-O � �� HClO- �� , -�� 2�_�- � 2�_y-�� , �� -��.

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9.2. �� . �� .

�� ��_a, �� .7, ��, �� HClO₄>HClO₃>HClO₂>HClO. ��, �� , �� .��. �� : �� (HO)_nXO_m �� m ��, �� . �� pK₁ = = -lgK₁ �� (HO)_nXO_m�� ��₁ = 8-5m. �� �� . �� , �� (��) �� . �� , � �� , �� . �� , �� �-�, �� , �� , �� .

�� HClO � HClO₄ �� , � �� , ��, ��.

��  �� (HO)_nXO_m, �� n>1: �� ₁, �₂, �₃, � �� 1: 10^-5: 10^-10. �� , � �� .

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9.3. �� .

�� . �� , �� , �� , �� .

�� - �� . �� �� , �� . �� . �� . �� , �� �_��.. � �� , �� �_{��.} �� :

�� _rG^o, �� �_��, �, ��, �� (��) �� .

�� �� , �� . �� , �� . �� , �� , �� , ��, �� , �� , �� .

�� , �� �� , �� ���. �� ��, � �� - �� ��.

��.6. �� =0 (�� ) � ��=14 (�� ). �� �^�= 1.23 � �� �₂+4H⁺+4=2H₂O.

� �� (��) �� . �� (��.11.4) �� , �� ��  (��.6) (�� -��)(c�� ^� �� H⁺+= 1/2H₂. �� -�� 4-� �� 1-�� . �., ��, 1993, �.24-30.), �� (A.Frost. Oxidation Pot�ntial-Free Energy Diagrams. J.Am.Chem.Soc. 1951. V.73. P.2680-2682)

�� (��) �� (��.6) �� -�� = nE^o, �� E^� - �� (�), n - �� (� ��) ��, �� , ��, HClO� 1/2Cl₂ , �� . �� nE^o �� G^o �� HClO � Cl₂: G^o = -nE^oF, �� F = 96500 ��/�� - �� . �� -�� _fG^o�� . �� _fG^o �� .6.

�� (��), �� (�� .6) �� , �� . ��, �� = 0 �� (Cl₂) �� , �� +HClO. �� , �� _fG^{o( C l}₂₎��, �� _fG^{o( C l -}) � _fG^o(HC l O). �� , �� Cl₂+H₂O H⁺+ + HClO �� =0 �� , �� �_��. = 4^. 10^-9.

�� =0. ��  �� 

3HClO = HClO₃ + 2HCl (1),
3HClO₂ = 2HClO₃ + HCl (2),
4HClO₃ = 3 HClO₄ + HCl (3),

�� , �� .7 � �� .7.

fig10.gif (1134 bytes)

��.7. �� (��), �� (��=0).

��.

�� _rG<0, �� . �� (1)-(3)

; .

�� (��.7) ��, ��

�� ,

�� ^� >�, ��, _rG^o<�, � ��, � �� HClO, HClO₂, HClO₃ �� =0 �� (1)-(3). �� ₃>�₂>�₁, �� HClO - HClO₂- HClO₃.

��

5HClO = 2Cl_2�+ HClO₃ +2H₂O (4)

7HClO₃ = Cl_2�+ 5HClO₄ + H₂O (5).

�� , ��

O₂ + 4H⁺ + 4e = 2H₂O (6)

( �� �� = 0 � (��. ��.6)) ��, �� (1)-(5), �� , ��, ��, HClO ��

�� ( �� (7) �� , � �� )

HClO = HCl + 1/2O_2�(7).

�� .6 ��, �� =0 �� HClO₄� Cl_2,�� (1-5) � �� .

� �� , �� , �� (��.6). �� , �� . �� .

�� , �� (1-5, 7). �� :

�� Cl-O � �� HClO -HClO₂--;
�� , �� (�� );
�� .

�� 1 � 2 �� (1-3) � �� HClO>HClO₂>, �� (3). �� (��) �� HClO � HClO₂, � �� - �� HClO₃. � ��, �� HClO₄ �� HClO₃�� . �� 3 �� , �� (4,5,7) �� , �� , �� , �� , �� .

� ��, �� . �� , ��, �� . �� , �� , �� , ��, ��.

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9.4. �� .

�� HXO_n, n = 1,2,3,4. � �� , �� , �� (��.6) .

1.�� o�� , � �� , �� -�� (�� ) �� .6.

2. �� : Cl₂<HClO HClO₂ >HClO₃ > HClO₄, �� 1/2. ��, �� NaClO �� Br₂ � ��, �� :

NaClO + 2KBr + H₂O = NaCl +Br₂ +2KOH (� �� Br₂ �� ).

C �� NaClO₃ �� :

NaClO₃+ 6KBr +3H₂SO₄ = 3Br₂ + NaCl + 3K₂SO₄ + 3�₂�.

3. � �� = -lg[H⁺] �� . ��, ��

� ��

�� �^�= 1.02 � �� = 0 �� �^�= +0.37 �� =14. �� , �� , �� .

� �� . �� :

�� ;
�� .

�� . � �� (��) �� (� �� ) . � �� -�� - ��, �� .

� �� , �� (�� 2), �� -�� HClO. �� (K.D.Fogelman, D.M.Walker, D.W.Margerum. Inorg.Chem, 1989, V.28, P.986-993) �� , �� - �� (�� (�� "��" - ��) �� - �� , �� (��) �� , �� )�� , � �� . �� -��:

(1)

� �� (��) �� HO^-- � . �� - �� - �� :

(2).

�� (1) �� . � �� Cl₂HClO < HClO₂ < HClO₃ < HClO₄ �� , � ��, � �� , �� . �� , �� , �� .

�� , �� , � �� , �� . �� Cl-O, � �� �� (�� - �� , �� , �� ) �� , �� . ��, �� HClO₄,�� H₂SO₄, �� (��, �� ).

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Jan	FEB	Mar
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2012	2013	2014

9. �������� ���������� �����.

9. �� .