17 Tema 6. Los halógenos . Propiedades generales, preparación y usos de los halógenos. Haluros de hidrógeno. Oxiácidos de los halógenos. Usos de los halogenuros. Cloro
1774
Karl Wilhelm Scheele .
Iodo
1811
Bernard Courtois
Bromo 1825
Antoine J. Balard
Fluor
Henri Moissan.
1886
Propiedades Energía de ioni zación, kJ /mol Af A f i n i d ad elec el ectt r ó n i c a, kJ k J /mo /m o l Electronegativid lectro negativid ad, Pauling aulin g Energ Energía ía de enlace (kJ/mol ) Punto fusión, fusi ón, ºC ºC Punto ebullició bull ición, n, ºC ºC Potencial otenci al normal de reduc reducció ción, n, V (medio básico) básico ) X2 2X Hvap Hdi s E ∆Hhi d
Flúor
Cloro Bromo Yodo
1680 -333 43 155 -219 -188 +2.87
1251 -348 2.8 240 -101 -34 +1.36
1143 -324 2.5 190 -7 60 +1.07
1009 -295 2.2 149 114 185 +0.54
0 79 -333 -460
0 122 -349 -385
15 96 -340 -351
30 76 -297 -3051
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Tema 6
Los halogenos
Halogenos
Generadores de sales
En el estado elemental forman moléculas diatómicas, X 2. En la naturaleza, sin embargo, debido a su alta reactividad, los halógenos se
encuentran siempre combinados con otros elementos. Forman un gran número de compuestos. El cloro, el bromo y el yodo se encuentran como halogenuros en el agua de mar, y
el flúor se encuentra en minerales como fluorita (CaF2) y criolita (Na3AlF6).
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Tema 6
Preparación y propiedades generales de los halógenos
Los halogenos
Como el flúor y el cloro son agentes oxidantes fuertes, deben prepararse por oxidación
(electroquímica)de los iones fluoruro y cloruro. La electrólisis de disoluciones acuosas de fluoruros es inadecuada porque el flúor es un
agente oxidante más enérgico que el oxígeno. El flúor se prepara electrolizando fluoruro de hidrógeno
líquido que contiene fluoruro de potasio para aumentar su conductividad, a 70°C aproximadamente
Ánodo
2F-
F2(g) + 2e-
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Tema 6
Los halogenos
Preparación de C12(g). Electrólisis de NaCl fundido
Electrólisis de una disolución acuosa de NaCl
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Tema 6
Los halogenos
Hay que separar los productos:
2NaOH(ac) + Cl2(g)
NaOCl(ac) + NaCl(ac) + H2O(l)
H2(g) + Cl2(g)
2HCl(g)
Bromo molecular Bromo molecular y yodo yodo se se preparan a partir del agua de mar por oxidación con cloro.
Cl2
+ 2X-
X2 + 2ClX= Br ó I
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Tema 6
Los halogenos
Reactividad Los números de oxidación de los
halógenos pueden variar desde -1 hasta + 7. La única excepción es el flúor. Como
es
el
elemento
más
electronegativo, solo puede tener dos números de oxidación, (0) (como en F 2) y -1 en sus compuestos.
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Tema 6
Singularidad del Fluor
Los halogenos
Debilidad del enlace F–F: F–F: el flúor fue el último de los halógenos en ser obtenido debido fundamentalmente a su gran reactividad . El Flúor es el más reactivo de entre los reactivos halógenos. Uno de los factores que
explican esa elevada reactividad es la debilidad del enlace F–F.
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Tema 6
Los halogenos
En el caso de compuestos covalentes
En. enlace (kJ/mol)
XX
HX
BX3
AlX3
CX4
NX3
158
574
645
582
456
272
Cl 243
428
444
427
327
201
Br 193
363
368
360
272
243
F
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Tema 6
Halogenuros de hidrógeno
Los halogenos
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Tema 6
Los halogenos
En el laboratorio, se pueden preparar por reacción de los
H2SO4(ac)
halogenuros metálicos con ácido sulfúrico concentrado:
CaF2(s) + H2SO4(ac) 2NaCl(s) + H SO (ac)
2HF(g) + CaSO4(s) 2HCl(g) + Na SO (ac)
HCl(g
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Tema 6
Los halogenos
La alta reactividad del HF se demuestra por el hecho de que ataca la sílice y los
silicatos:
6HF(ac) + SiO2(s)
H2[SiF6](ac) + 2H2O(l)
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