Espectroscopia Molecular-​Examen

1. Usando el espectro el del diagrama de Tanabe-Sugano prediga las dos transiciones

[ ​Cr ​( ​OH ​ ) ​ ]​ +​3 , ​

permitidas en el espectro ​ 2​ 6​ ​ para el cual ∆​0 ​=17600 cm − 1 y B= 700 cm-1

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∆ ​0​ B​ [​Ni (​ ​NH​ )​ ] ​ +​2

2.​ Usando el diagrama de Tanabe-Sugano determine el valor de ​ y​ para el ​ 3​ 6 ​

, el cual muestra absorciones a 10750, 17500 y 28200 cm​-1​.

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3.​ El vidrio ordinario de las botellas parece casi incoloro cuando se mira a través de sus
paredes, pero es verde cuando se mira desde el extremo de manera que la luz tenga un mayor
recorrido a través del vidrio. El color está asociado con la presencia de F​ e ​+​3 ​en la matriz de
silicato. Explique a qué se debe este fenómeno, en términos de espectroscopia electrónica.
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4. El azul de Prusia fue uno de los primeros pigmentos sintéticos. Tiene la
composición global K​ ​[​Fe2​
​ (​CN​)​ ] en la que cada Fe +2 está rodeado está rodeado por seis ligandos cianuro
6​
coordinados por carbono que une al Fe+3 unido al nitrógeno. A qué se deben las intensas bandas que se observan en el

espectro UV-VIS a 15000 y 25000 cm-1?

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5​,Una alúmina de V3+ se disuelve en ácido sulfúrico diluido. Debido a que los iones de alúmina
son 3 M H2O (M=metal), es de esperarse que se formen iones con la estructura 3 V H2O y
muestran el siguiente espectro UV en solución.
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6.​ Dados los números de ondas de las dos transiciones del MnO4 a 18500 y 32200 cm-1,
explicar cómo se puede calcular T y cuál es su valor para este complejo.
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7. H. Kuhn [J. Chem. Phys. 17, 1198(1949)] sugiere que los electrones móviles en polimetino
podrían ser modelados como una partícula en una caja unidimensional. Considere
carbocianinas simétricas donde la carga positiva es resonante en los dos átomos de nitrógeno.
El camino zig-zag de polimetino a lo largo del cual los electrones pueden moverse libremente
se extiende a lo largo del sistema conjugado entre los dos nitrógenos. Kuhn considera una
longitud de la caja igual a este camino más una longitud de enlace sobre cada extremo; esto
es, L=(2k+10)l donde l es la longitud de enlace intermedia entre un enlace doble y un sencillo
C-C (=1.39Å). El número de electrones en el polimetino es 2k+10. Considere que cada nivel de
energía en la caja es capaz de sostener no más de dos electrones y que la transición
electrónica responsable de dar el color corresponde a la promoción de un electrón del nivel
más elevado lleno al nivel más bajo vacío. Calcule E y para los casos k=0, 1, 2 y 3; y compare
con los valores observados de absorción máxima a 5757, 7150, 8180 y 9250 Å,
respectivamente. Nota: De además una conclusión de sus resultados.
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8. ​El espectro electrónico de una solución acuosa de [Ni(en)3]2+ presenta absorciones anchas
con ​λ ​≈​ 325, 550, y 900 nm. ¿A qué se deben esas transiciones?
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[​Cr (​ ​OH ​ )​ ]​
9. ​Los iones ​ 2 ​ 6 ​
+​3 ​
son de color verde azulado pálido, pero el ion cromato ​CrO ​4 -​​ 2

es amarillo intenso.
Basándose en los conceptos espectroscópicos, explique a que se deben estas diferencias.
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