INSTITUTO SUPERIOR Tecnológico PÚBLICO “SIMÓN
BOLÍVAR”
…………………………………………………………………………
INFORME DE ANÁLISIS QUÍMICO INSTRUMENTAL
CICLO:
V - DIURNO
LEÓN SALVADOR, Mayra NAVARRO INFANTES, CECILIA ORTIZ DAVILA, Luis TREBEJO ZELAYA, Liset
DOCENTE :
ING. SALAZAR LOZANO, Lely
FECHA DE ENTREGA: 26/06/12 BELLAVISTA
-CALLAO
-
2012
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INTRODUCIÓN………………………………… …… Pag. 03
OBJETIVOS
MARCO TEÓRICO………………………………….. Pag. 05
CONCLUSIONES
RECOMENDACIONES……………………………... Pag. 16
ANEXO………….………….. ………………………… . Pag. 19
BIBLIOGRAFÍA………………………………………Pag. BIBLIOGRAFÍA……………………… ………………Pag. 2 1
…………………………………..…. Pag.04
……………………………….. Pag. 15
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Por medio de este informe que a continuación se estará presentando, nos menciona información relacionada acerca de un tema de suma importancia que son , los Métodos Métodos Radioquimicos. Radioquimicos. Como sabemos los métodos radioquímimcos, cada vez están siendo más utilizados por la gran sensibilidad y rapidez por la cual se determina elementos presentes en un muestra problema a diferencia de otros métodos que demoran horas y son más costosos y los resultados no son tan precisos como las que se pueden determinar por los métodos radioquimicos. Es por ello que cada vez estos métodos cobran mucha importancia en muchas industrias, tales como la minera, la textil, la metalúrgica y la petrolera, y en otros campos como la arqueología y la criminología.
Es por eso que es muy importante tener conocimiento de este tema y sobre todo entenderlo. Esperamos que con esta información sea de más fácil acceso para poder entenderlo, para de esta manera ser profesionales competentes. competentes. Atentamente, Grupo 3
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3.1 OBJETIVO GENERAL: GENERAL:
Los Métodos Radio químicos 3.2 OBJETIVOS ESPECIFICOS ESPECIFICOS
Conocer y describir que con los métodos radioquimicos.
Conocer las ventajas y desventajas de estos métodos
Aplicaciones de los métodos radioquimicos radioquimicos
Ver de qué manera interviene o es importante aplicar los métodos radioquimicos
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4.1
DEFINICIóN:
Los métodos radioquimicos se basan en la medida de la radiación de alta energía que emiten los isótopos radiactivos. Con ello se consigue detectar la presencia de algunas sustancias en una muestra, así como determinar su concentración. Debido a que este tipo de radiación es muy energética y penetrante, resulta de muy simple y fácil medida, aun cuando sea de muy pequeña magnitud, por lo que los métodos radioquimicos constituyen una de las técnicas más sensibles en la detección y análisis de sustancias La disponibilidad tanto de isotopos radiactivos naturales como artificiales ha hecho posible el desarrollo de métodos analíticos (métodos radioquímicas) que son a la vez sensibles y específicos'. Estos procedimientos se caracterizan normalmente por una buena exactitud y una amplia aplicabilidad; además, algunos reducen o eliminan separaciones químicas que son necesarias en otros métodos analíticos. Los métodos radioquímicas son de tres tipos según sea el origen de la radiactividad. En análisis por activación, la actividad es inducida en uno o más elementos de la muestra por irradiación con radiación o partículas adecuadas (normalmente neutrones térmicos de un reactor nuclear); se mide a continuación la radiactividad resultante. En la segunda categoría se encuentran
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procedimiento es el método de dilución isotópica, en el que una cantidad pesada de analito marcado radiactivamente y que tiene una actividad conocida se añade a una cantidad medida de la muestra. Después de mezclar completamente para asegurar la homogeneidad, se aísla y purifica una fracción del analito; el análisis determina la actividad de esta fracción aislada. Además, los químicos orgánicos a menudo utilizan reactivos que han sido marcados con marcadores radiactivos con objeto de elucidar los mecanismos de reacción. La tercera clase de métodos implica medidas de radiactividad que tiene lugar de manera natural en una muestra. Ejemplos de este tipo de métodos son la medida de radiación en el aire de una casa o de uranio en materiales de loza y cerámica. 4.2. ISÓTOPOS RADIACTIVOS
Todos los núcleos están constituidos por un conjunto de protones y de neutrones excepto uno, que obviamente es el núcleo del hidrógeno, que consta de sólo un protón. Las propiedades químicas de un Átomo están determinadas por su número atómico Z, que es el número de protones que contiene su núcleo. La suma del número de neutrones y de protones en un núcleo es el número másico A 2. Los isótopos de los elementos son Átomos que tienen el mismo número atómico pero diferente número másico. Esto es, los núcleos de los isótopos de un elemento contienen el mismo número de protones pero diferente número de neutrones. Los isótopos estables son aquellos que nunca se han desintegrado espontáneamente. Los isótopos radiactivos (radionucleidos), por el contrario, se experimentan desintegración espontánea, la cual da lugar finalmente a isótopos estables. La desintegración radiactiva de los isótopos se produce con la emisión de radiación electromagnética en forma de rayos X o rayos gamma (rayos y); con la formación de electrones, positrones y núcleos de helio; o por fisión, en la que un núcleo se rompe en núcleos más pequeños.
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beta, fotones de rayos gamma y fotones de rayos X- se pueden detectar y contar con varios de los detectores descritos en el Apartado 1213-4. Así, la mayoría de los métodos radioquímicas de análisis se basan en el recuento de los impulsos de electricidad producidos cuando estas partículas partí culas de desintegración o los fotones chocan con un detector de radiación.
Diversos tipos de procesos de desintegración radiactiva dan lugar a los productos citados en la Tabla 32-1.
Partículas alfa
+2
4
Negatrón
-1
1/1.840(-0)
Positrón
+l
1/1.840(-0)
Partículas beta
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La desintegración alfa es un proceso radiactivo que sucede normalmente en los isótopos más pesados. Los isótopos con número másico menor de 150 aproximadamente (Z - 60) raramente producen partículas alfa. La partícula alfa es un núcleo de helio que tiene una masa de 4 y una carga de +2. Un ejemplo de desintegración alfa se muestra mediante la ecuación
En este caso, el uranio-238 ( 238 U) se convierte en torio-234 (234Th), nucleido hijo que tiene un número atómico que es dos unidades menor que el del progenitor. Las partículas alfa de un proceso de desintegración concreto son mono energéticas o están distribuidas en un intervalo relativamente pequeño de energías discretas. Por ejemplo, el proceso de desintegración mostrado en la Ecuación 32-1 tiene lugar por dos caminos distintos. El primero, que sucede en el 77 por 100 de las desintegraciones, produce partículas alfa con una energía de 4,196 MeV 3. El segundo camino (23 por 100 de las desintegraciones) produce partículas alfa que tienen una energía de 4,149 MeV; esta reacción está acompañada por la liberación de un rayo gamma de 0,047 MeV. Las partículas alfa pierden progresivamente su energía debido a colisiones al atravesar la materia y finalmente se convierten en
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Las partículas alfa son relativamente ineficaces para la producción de isótopos artificiales debido a su bajo poder de penetraciòn.
Se considera como una desintegración - cualquier reacción nuclear en la que el número atómico Z cambia pero el número másico A permanece constante. Existen tres tipos de desintegración  -: formación de un negatrón, formación de un positrón y captura electrónica. Ejemplos de los tres procesos son:
En este caso, - y v en las dos primeras ecuaciones representan un antineutrino y un neutrino, partículas que no tienen significado en química analítica. La tercera ecuación muestra un proceso de desintegración  - denominada captura de electrón. En este caso, la captura de un electrón por el núcleo de 24Cr produce 2gV, pero este proceso deja uno de los orbitales atómicos del vanadio con un electrón menos (normalmente el 1 s, u orbital K, caso en el
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disminuye en una unidad. El positrón tiene una existencia transitoria y desaparece por reacción con un electrón para dar dos fotones de rayos gamma de 0,511 MeV. En contraste con la emisión alfa, la desintegración beta se caracteriza por la producción de partículas con un espectro continuo de energías que van desde casi cero hasta un máximo que es característico de cada proceso de desintegración. La partícula beta no es ni mucho menos tan efectiva como la partícula alfa en la producción de pares de iones en la materia debido a su pequeña masa (alrededor de 1/7.000 la de una partícula alfa); al mismo tiempo, su poder de penetración es sustancialmente mayor. Las energías de las partículas beta se expresan frecuentemente como el espesor de una sustancia absorbente, habitualmente aluminio, necesario para parar la partícula.
Muchos procesos de emisión alfa y beta dejan un núcleo en estado excitado, que vuelve al estado fundamental en una o más etapas cuantificadas con la liberación de rayos gamma mono energéticos. Es importante señalar que los rayos gamma no se distinguen de los rayos X de igual energía excepto por su fuente. Así, los rayos gamma se producen por relajaciones nucleares, mientras que los rayos X provienen de relajaciones electrónicas. El espectro de emisión de los rayos gamma es característico para cada núcleo y, por tanto, Útil para identificar radioisótopos. No es sorprendente que la radiación gamma sea muy penetrante. En su interacción con la materia, los rayos gamma pierden energía por tres mecanismos; el que predomine uno u otro depende
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fotón. El fotón, fot ón, ahora con menor energía, sale del electrón y puede dar lugar a nuevos efectos Compton o interacciones fotoeléctricas. Si el fotón de radiación gamma posee energía lo suficientemente elevada (al menos 1,02 MeV), puede tener lugar una producción de pares. En este caso, el fotón es totalmente absorbido creándose un positrón y un electrón en el campo que rodea al núcleo.
Muchos procesos producen la pérdida de electrones de los orbitales más internos de un átomo. Los rayos X se pueden formar a partir de transiciones electrónicas en las que los electrones más externos llenan los huecos vacantes creados por el proceso nuclear. Uno de los procesos es la captura de electrón, que se ha estudiado anteriormente. Un segundo proceso que puede producir rayos X es la conversión interna, un tipo de proceso nuclear que es alternativo de la emisión de rayos gamma. En este caso, una interacción electromagnética entre el núcleo excitado y un electrón extra nuclear produce la expulsión de un electrón de un orbital cuya energíacinética es igual a la diferencia entre la energía de la transición nuclear y la energía de enlace del electrón (véase el Apartado 12A-3). La emisión de este llamado electrón de conversión interna deja un hueco en el orbital K, L u otro orbital más alto; los rayos X se emiten cuando el orbital se llena por una transición electrónica.
La desintegración radiactiva es un proceso totalmente aleatorio. Por tanto, aunque no se puede hacer ninguna predicción respecto al tiempo de vida de un núcleo concreto, el comportamiento de un gran conjunto de núcleos similares se puede describir mediante
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de desintegración característica del radioisótopo. Reordenando esta ecuación e integrando en el intervalo entre t = 0 y t = t (durante el cual el número de núcleos radiactivos en la muestra disminuye de No a N), se obtiene
La vida media, t 1/2, de un isótopo radiactivo se define como el tiempo necesario para que se desintegre la mitad de los átomos radiactivos en una muestra; es decir, para que N sea iguala No/2. Sustituyendo N o 2 por N en la Ecuación 32-3 se obtiene
(32-5)
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normalmente oscilan entre un nano Curie o menos hasta unos pocos micro curíes. En el laboratorio, raramente se miden actividades absolutas, ya que las eficacias de los detectores no son generalmente del 100 por 100. En su lugar, se utiliza la velocidad de recuento R, donde R = cA. Sustituyendo. Esta relación en la Ecuación 32-6 se obtiene (32-7)
En este caso, c es una constante denominada coeficiente de detección, que depende de la naturaleza del detector, de la eficacia del recuento de las desintegraciones y de la disposición geométrica de la muestra y el detector. La ley de desintegración dada por la Ecuación 32-4 puede escribirse como
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Se puede utilizar la Ecuación 32-5 para calcular la vida media
La radiactividad se mide mediante un detector que produce un impulso de electricidad por cada átomo que se desintegra. La información cuantitativa sobre las velocidades de desintegración se obtiene por recuento de estos impulsos durante un periodo dado. La Tabla 32-2 muestra los datos de desintegración típicos obtenidos para cuentas sucesivas de un minuto de una fuente radiactiva. Se observa una variación considerable de los resultados debido a que el proceso de desintegración es aleatorio. Así, las cuentas por minuto oscilan entre un mínimo de 132 y un máximo de 187.
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A pesar que el proceso de desintegración radiactiva es aleatorio, los datos no se distribuyen de acuerdo con la Ecuación a 1-13 (Apéndice 1), especialmente para cuentas bajas, ya que los procesos de desintegración no siguen un comportamiento gaussiano. La razón por la que los datos de desintegración no tienen una distribución normal se debe al hecho de que la radiactividad consta de una serie de sucesos discretos que no pueden variar continuamente como lo pueden hacer los errores indeterminados para los que se aplica la distribución gaussiana. Además, no son posibles los recuentos negativos. Por tanto, los datos no se pueden distribuir simétricamente alrededor de la media. Con objeto de describir exactamente el comportamiento radiactivo, es necesario suponer una distribución de Poisson, que viene dada por la ecuación (32-9)
En esta expresión, y es la frecuencia con la que sucede una cuenta
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una probabilidad finita de que una cuenta dada pueda exceder el promedio en varios órdenes.
La Ecuación 32-9 no contiene el término correspondiente a la desviación estándar para una distribución de Poisson y, claro está
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Así, aunque la desviación estándar absoluta aumenta con el número de cuentas, la desviación estándar relativa disminuye. La velocidad de recuento R es igual a Mlt. Para obtener la desviación estándar en R, se aplica la Ecuación a1-28
Generalmente, el tiempo puede medirse con una precisión suficientemente elevada como para que UT - 0. La derivada parcial de R respecto a M es 1 /t. Así,
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(b) Para el grupo entero,
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Calcular los límites para el 95 por 100 de confianza (a) para el primer dato de la Tabla 32-2 y (b) para la media de todos los datos de la Tabla. (a) En el Ejemplo 32-2, se obtuvo que s R = 13,4 cpm. La Tabla a1-3 (Apéndice 1) 1) muestra que z = 1,96 1,96 para un nivel de confianza del 95 por 100. Así, para R 95 % LC = 180 cpm ± 1,96 x 13,4 cpm  = 180 (± 26) cpm (b) En este caso, s R se obtuvo que era 3,73 cpm y 95 % LC para R = 167 16 7 cpm ± 1,96 x 3,73 cpm
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Con el objeto de obtener una valoración fiable, es necesario corregir las cuentas totales en función del ruido de fondo. El
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Una muestra produce 1.800 cuentas en un período de 10 min. Se obtuvo un ruido de fondo de 80 cuentas en 4 min. Calcular la incertidumbre absoluta en la velocidad de recuento corregida para un nivel de confianza del 95 por 100.
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Con objeto de disminuir la auto absorción, las muestras emisoras de partículas alfa se cuentan generalmente en forma de capas delgadas preparadas por electrodeposición o por destilación y condensación. A menudo, estas capas se sellan con unas ventanas delgadas y se cuentan en contadores proporcionales de flujo de gas sin ventanas o en cámaras de ionización. También se pueden colocar justo al lado de un detector de estado sólido, con
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La radiación gamma se detecta y se mide por los métodos descritos en los Apartados 12B-4 y 12B-5 para la radiación X. La interferencia de las partículas alfa y beta se elimina fácilmente filtrando la radiación con una pieza delgada de aluminio o Mylar 7 . Los espectrómetros de rayos gamma son similares a los
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partículas y la calculadora electrónica- abre posibilidades más amplias. 4.6 ANALISIS DONDE SE APLICAN LOS METODOS RADIOQUIMICOS
La identificación del cabello humano puede ser importante en criminología. F.W. Lima, H. Shibata y L.T. Atalla (Brasil)
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grado de humedad y la distribución irregular del elemento en la muestra. De todas formas, los aparatos prototipo, sencillos y poco costosos, han resultado sumamente útil es en la explotación de yacimientos de minerales. J. R. Rhodes, T. G. Ahiere I. S. Boyce (Reino Unido) describieron otras dos aplicaciones de la fluorescencia excitada por rayos X en la minería del estaño, utilizando fuentes radio isotópicas. Una consiste en el análisis continuo de los materiales tratados, que se caracteriza ante todo
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la partícula le arranca un electrón al átomo, el cual pasa a ser un ion (Ar+). Los iones positivos viajan hacia el cátodo. Los electrones, mucho más ligeros, en su camino hacia el ánodo alcanzan la energía suficiente para volver a ionizar otros átomos generando una u na avalancha de electrones que dan lugar a un pulso o señal eléctrica. El tamaño del pulso que se obtiene en estos detectores es independiente de la ionización causada por la partícula por lo que el detector solo cuenta número de partículas
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óptimo de trabajo para el detector, el cual se encuentra en la región
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2.-Medida de la radiación de fondo: f ondo:
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3.-Caracterización de los diferentes tipos de radiación:
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Los rayos gamma se producen por relajaciones
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