INTRODUCCIÓN A LA MINERALOGÍA 2 Caracterización de las Sustancias Minerales 2!" C#$%#sición &u'$ica El estudio de la composición y la estructura de los minerales constituye minerales constituye la base de su conocimiento, ya que ello condiciona la restantes características. Tradicionalmente, el estudio estudio químico de químico de los minerales ha seguido dos vías: A( AN)LISIS &UÍMICO Permite conocer los elementos y entidades que forman parte de la sustancia mineral. El anális análisis is químic químico o pres presen enta ta dos dos etap etapas as.. En prim primer er luga lugarr se rea realiza liza el AN)LISIS CUALITATI*O que sirve para determinar cuales son los elementos y entidades presentes en la muestra. Posteriormente conviene realizar el AN)LISIS CUANTITATI*O para CUANTITATI*O para determinar el contenido exacto de cada elemento o entidad. El resultado de este estudio permite obtener lafórmula lafórmula química química de la sustancia que forma el mineral. Es importante sealar que los caracteres analíticos no corresponden al con!unto de las entidades que forman la sustancia, sino a cada una de ellas por separado. Por e!emplo, el ani"n cloruro presenta las mismas características analíticas independientemente de la sustancia en que se encuentre #salvo interferencias$, pero los distintos minerales que contienen cloruros no deben presentar m%s caracteres analíticos comunes. +( ESTUDIO ESTRUCTURAL Permite conocer la disposici"n espacial de los elementos y entidades que forman el mineral. &l contrario que en el apartado anterior, los caracteres estructurales est%n asociados al con!un con!unto to comple completo to de entida entidades des que forman forman la sustan sustancia cia.. Por Por e!empl e!emplo, o, dos clorur cloruros os met%licos distintos no tienen por qu' presentar ninguna similitud estructural. &unque estas vías parecen independientes, la realidad es que los datos obtenidos en ambos casos son complementarios y s"lo !untos pueden suministrar una idea de la verdadera naturaleza del mineral y, en general, de cualquier sustancia química. (inalmente, para concluir este apartado, hay que decir que, en todo momento, se deben saber relacionar las características físicas de físicas de los minerales con su naturaleza química, química, ya que si bien las primeras dependen de esta, a su vez pueden llegar a convertirse en un medio para su estudio y conocimiento.
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INTRODUCCIÓN A LA MINERALOGÍA 2 Caracterización de las Sustancias Minerales 2!"" An,lisis &u'$ic# Cualitati-# El Análisis El Análisis Químico Cualitativo o Cualitativo o Análisis Análisis Cualitativo permite Cualitativo permite conocer los elementos o las entidades i"nicas presentes en una sustancia. Esta etapa del an%lisis es necesaria para realizar la determinaci"n cuantitativa correcta. Para realizar un Análisis un Análisis Químico de Químico de cualquier sustancia s"lida, es conveniente conocer algunas de las caracterís características ticas físicas físicas que que nos nos pued pueden en orie orient ntar ar sobr sobree su natu natura ralez leza. a. Esto Esto pued puedee abre abrevi viar ar considerablemente una serie de ensayos en el laboratorio. )epend )ependien iendo do de la natural naturaleza eza de la muestra muestra y de los datos que se tienen tienen sobre ella, hay varias formas de realizar un Análisis Cualitativo: &.* +uando se sospecha la composici"n, se puede recurrir directamente a los ensa.#s es%ec'/ic#s para para las prob probab able less entid entidad ades es.. -ay -ay que que tene tenerr en cuen cuenta ta que que si dos dos o m%s m%s entidades pueden tener comportamientos químicos parecidos ante un determinado ensayo #se interfieren$, hay que separarlos antes del an%lisis propiamente dicho. .* +uando +uando se tienen grandes dudas sobre la composici"n o se ignora totalmente, hay dos posibilidades: ./.* 0ealizar una serie de ensa.#s de ti%# 0eneral, 0eneral, tanto por vía seca, seca, como por vía húmeda y húmeda y deducir, a partir de ellos, los elementos probables. Posteriormente se van realizando los ensayos específicos de tales elementos. .1.* 0ealizar $arc1as anal'ticas #vía anal'ticas #vía h2meda$ que permitan separar en grupos todas las posibles entidades y comprobar, en cada uno de esos grupos, la presencia o no de las entidades correspondientes. Existenmarchas Existenmarchas analíticas para analíticas para cationes #la de los sulfuros y la de los carbonatos carbonatos$$ y tamb tambi' i'n n para para anion niones es.. 3a real realiz izac aci" i"n n de marchas analíticas requiere analíticas requiere m%s traba!o y me!ores medios que la opci"n anterior. 4na de las venta!as de las marchas analíticas es analíticas es que se evitan las interferencias, pero deben ser realizadas con gran cuidado para que cada entidad aparezca en el grupo que le corresponde y no se pierda en otros, de tal manera que nunca se llegaría detectar.
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56T07)4++586 & 3& 956E0&37;&
1 +aracterizaci"n de las
1.=./././ Ensayos >ía
ENSAOS A LA LLAMA 3as sales de ciertos cationes #alcalinos, alcalino*t'rreos, metales de transici"n$ y de ciertos aniones #halogenuros #halogenuros,, etc.$ dan coloraciones características cuando se colocan a la llama de un mechero de gas. 7tras sales dan luminiscencia a la llama. 3os nitratos nitratos y y los los clor loratos tos defl deflag agrran #avi #avivvan la lla llama al despr espren ende ders rsee oxíg oxígen eno o$. 3os sulfuros sulfuros y y los halogenuros decrepitan #estallan en pequeos trozos emitiendo sonidos$. 7tros minerales llegan a fundirse. El uso de la llama para observar el color emitido por algunos elementos es, en ciertos casos, muy orientativo. El m'todo consiste en mezclar el mineral pulverizado con unas gotas de %cido clorhídrico y formar una pasta que se toma con un alambre de platino #o de nicrom, aleaci"n de niquel y cromo$ y se coloca a la llama oxidante de un mechero de gas.
•
ENSAOS EN TU+O CERRADO
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•
ENSAOS EN TU+O A+IERTO
•
ENSAOS A LA 3ERLA 3os ensayos a la perla se suelen realizar mezclando el mineral pulverizado, bien con b"rax o bien con otras sales. El fundamento de estos ensayos se encuentra en la formaci"n, por medio del calor, de sales m%s o menos comple!as, en las que se integran los cationes de los minerales, dando lugar a coloraciones características. &l igual que los dem%s ensayos de vía seca no todos los elementos el ementos dan coloraciones. El ensayo a la perla se puede realizar con hilos #idealmente de platino$ o sobre soportes de escayola. El tipo de llama empleado influye, ya que se verifican procesos de oxidaci"n* reducci"n. 3a llama del mechero ha de ser siempre reductora, pero seg2n se use el soplete se obtendr% un dardo oxidante o reductor y los colores de las perlas pueden ser diferentes en cada cada caso caso.. Tambi'n mbi'n pued puedee ocur ocurri rirr que que los los color colores es de las las perl perlas as,, una una vez vez forma formada das, s, evolucionen a medida que se van enfriando y por ello conviene observarlas en caliente y en frío.
•
ENSAOS SO+RE CAR+ÓN
1 +aracterizaci"n de las
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?cido clorhídrico #diluido$ ?cido sulf2rico #diluido$ -idr"xido s"dico o pot%sico -idr"xido am"nico #soluci"n acuosa de amoniaco$ +arbonato s"dico +arbonato am"nico (errocianuro pot%sico +loruro de bario 6itrato de plata
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)espu's del uso de los reactivos generales quedar%n descartados un buen n2mero de iones y unos s"lo unos pocos ser%n probables. Para terminar de concretar se recurre a los reactivos específicos de cada una de las entidades. 4na vez encontrada la composici"n química cualitativa, puede determinarse la mineralogía de la muestra ob!eto de estudio mediante sus propiedades físicas.
1 +aracterizaci"n de las
1.=./.1 &n%lisis Auímico +uantitativo +omo se acaba de decir, el conocimiento de la composició composición n química química cualitativa cualitativa puede no ser sufi sufici cien ente te para para reco recono noce cerr el miner mineral al y se debe debe prof profun undi diza zarr m%s m%s en el estu estudi dio. o. El Análisis El Análisis Cuantitativo de Cuantitativo de una sustancia permite obtener su f"rmula química. Para realizar el Análisis el Análisis Cuantitativo Cuantitativo de sustancias minerales, o inorg%nicas en general, deben tenerse en cuenta una serie de consideraciones: /.* /.* Es import importan ante te realiz realizar ar una 6uena 6uena t#$a t#$a de $uestr $uestra a . Para Para realiz realizar ar un Análisis un Análisis Cualitativo basta Cualitativo basta con tomar una porci"n del material a estudiar para detectar los elementos o entidades que contiene. +uando se va a realizar un estudio cuantitativo, la muestra ha de ser representativa y su composici"n debe ser muy pr"xima a cualquiera de las diversas porciones que se podrían formar. Para ello, siempre que se pueda, debe homogeneizarse el material del que se va a tomar la muestra y proceder a sucesivos cuarteos, previa molienda si fuese necesario.
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-oy en día hay una gran cantidad de Mtodos Mtodos Analíticos Analíticos para para aplica aplicarr al amplio amplio cat%lo cat%logo go de sustan sustancia ciass y combin combinac acion iones es que se pueden pueden encont encontra rarr. Para Para simpli simplific ficar ar,, se expone expone la siguie siguiente nte clasificaci"n: A! Mtodos Clásicos A"#! Mtodos $ravimtricos A"%! Mtodos &olumtricos '! Mtodos (nstrumentales o )ísico"Químicos '"#! Mtodos *pticos '"%! Mtodos +lctricos '",! Mtodos -rmicos '".! Mtodos Mecánicos '"/! 0tros Mtodos 3a denominaci"n de Mtodos (nstrumentales no (nstrumentales no es muy adecuada, aunque se conserva por motivos hist"ricos. &lgo m%s adecuada sería la segunda denominaci"n. )ado que en Análisis en Análisis Mineral no no se usan todos los m'todos analíticos, s"lo se comentar%n los m%s aplicados en este campo.
56T07)4++586 & 3& 956E0&37;&
2 Caracterización de las Sustancias
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1. )isolv )isolver er o disgre disgregar gar.. 6o se deben emplear emplear como disolve disolvente ntess o funden fundentes tes sustanc sustancias ias que contengan elementos que se quieren quie ren determinar. B. Provoc Provocar ar la formaci" formaci"n n de una sustan sustancia cia s"lida s"lida poco poco solubl solublee que conten contenga ga el elemen elemento to a determinar. =. &islar &islar el el s"lido s"lido,, lav%nd lav%ndole ole y sec% sec%ndo ndole. le. C. 0eali ealiza zarr la pesa pesada da.. D. 0ea 0ealizar lizar los los c%lculos. c%lculos. El El contenido contenido en elementos elementos se se suele dar dar en forma forma de "xidos. "xidos. Estas etapas pueden variar en algunos casos. )ependiendo del m'todo empleado para obtener la fase s"lida, hay varios mtodos gravimtricos: A( 3reci%itaci#nes
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1 +aracterizaci"n de las
1.=./.1.1 &n%lisis >olum'trico. 9'todos >olum'tricos
aloraci"n >aloraci"n mediante la reacci"n adecuada y determinaci"n del punto final. =.* 0ealizaci"n 0ealizaci"n de los c%lculos. )ependiendo de la reacci"n que se lleve a cabo, hay varios tipos de m'todos volum'tricos: &.* 6eutralizaciones 6eutralizaciones o reacciones &cido*ase.
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mediante reacciones sencillas. &lgunos sistemas susceptibles de valorarse de esta forma son los siguientes: (e#55$J(e#555$, +r#555$J+r#>5$, 9n#55$J9n#5>$J9n#>55$, &gJ&g#5$, etc. +.* >olumetrías >olumetrías de precipitaci"n. olumetr ).*>olumetrías ías de formaci"n de comple!osK #complexometrías$.
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3os Mtodos *pticos se *pticos se basan en el estudio de la interacci"n entre una energía radiante y una mues muestr tra. a. +omo +omo resu result ltad ado o de esta esta inte intera racc cci" i"n n pued puedee dars darsee una una a6s#rción, a6s#rción, una e$isión o una $#di/icación de tal energía. Entre losMtodos los Mtodos *pticos, *pticos, los M8t#d#s Es%ectrales constituyen Es%ectrales constituyen el n2cleo b%sico. 3os Mtodos Mtodos +spectrale +spectraless han sido sido emplea empleados dos por los químic químico*f o*físi ísicos cos para para realiz realizar ar estudi estudios os estructurales.
1 +aracterizaci"n de las
1.=./.1.B./ 9'todos Espectrosc"picos de &bsorci"n Para la determinaci"n cuantitativa de sustancias inorg%nicas se han puesto a punto numerosos m'todos m'todos basados en la determinación calorimtrica o calorimtrica o en la interacción interacción de la muestra con luz visi1le. visi1le . Exis Existe te una una rela relaci ci"n "n dire direct ctaa entr entree la conc concen entr trac aci"n i"n de una una espe especi ciee y la cant cantida idad d de ener energía gía #correspondiente a una determinada zona del espectro$ que absorbe. Esta relaci"n fue estudiada por 3ambert*ouger en /BI y por eer en /NC1. 3a aparición aparición de color en color en una sustan sustancia cia cuando cuando incide incide sobre sobre ella luz visibl visiblee est% est% causad causadaa por
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estudio de sustancias minerales. 0ecientemente se ha empleado la radiaci"n 4> para determinaciones de sustancias organomet%licasinD, como por e!emplo algunos comple!os 9etal*&E)T. 9etal*&E)T. Por lo que respecta a la Espectroscopía 50, 50, se ha venido utilizando casi exclusivamente en Auímica 7rg%nica, existiendo una amplia bibliografía sobre caracterizaci"n de sustancias org%nicas mediante esta t'cnica. & finales de los aos CI se inici" el estudio de algunos aniones inorg%nicos por medio de esta t'cnica. )urante los aos DI se us" la +spectroscopía (2 para (2 para identificar identificar aniones aniones inorg%nicos inorg%nicos poliat"mico poliat"micoss y para diferenciar diferenciar los distintos tipos de agua presentes en sustancia sustanciass inorg%nica inorg%nicas. s. Posteri eriorm ormente, hacia /LI, se emp empeza ezaron a caracteri erizar sustancias ias minera erales mediante +spectroscopía (2. (2. & pesar de todo, no se puede decir que la +spectroscopía (2 sea (2 sea una buena t'cnica cuantitativa.
1 +aracterizaci"n de las
1.=./.1.B.1 9'todos Espectrosc"pticos de Emisi"n &l igual que los 9'todos Espectrosc"picos de &bsorci"n se pueden utilizar de forma cualitativa y cuantitativa. El uso principal de estas t'cnicas se centra en la determinaci"n elemental.
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En la determinaci determinaci"n "n elemental elemental de sustancia sustanciass inorg%nicas inorg%nicas se emplean emplean numerosas numerosas t'cnicas, t'cnicas, pero a continuaci"n se van a describir las m%s 2tiles en el caso de sustancias minerales.
2.4.1.2.3.2.1 Fotometría de Llama (FE) Tambi'n llamada (7T79ET0;& )E E95<586 )E 33&9&. 3a excitaci"n se produce mediante una llama llama con una temper temperatu atura ra compre comprendi ndida da entre entre /II /II y B1IIQ+ B1IIQ+,, como como las de acetile acetilenoJ noJair airee o acetilenoJoxígeno. 3os fot"metros de llama no son aparatos muy comple!os y permiten la determinaci"n de elementos alcalinos, alcalino*t'rreos, tierras raras, +r, 9n, etc. En la actualidad los aparatos de &bsorci"n &t"mica pueden ser utilizados como (ot"metros de 3lama, para ello basta con no utilizar las l%mparas.
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2.4.1.2.3.2.3 Fluorescencia Atómica (FA) o (EFA) Es una t'cnica reciente que compite con la Espectrometría de &bsorci"n &t"micai1=/1B11. +uando se excitan los electrones mediante una radiaci"n con determinada longitud de onda, tienen tendencia a volver a su estado fundamental, por lo cual emiten una energía con la misma longitud de onda.
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2.4.1.2.3.2.' Fluorescencia de aos *
2.4.1.2.4 "+todos El+ctricos 3os 9'todos El'ctricos de &n%lisis se basan en el comportamiento de una disoluci"n cuando forma parte parte de una celda celda electr electroqu oquími ímica. ca. 4na celda celda electro electroquí químic micaa es un sistem sistemaa químic químico o capaz capaz de intercambia intercambiarr corriente corriente el'ctrica con el exterior exterior.. 3as celdas que generan generan corriente corriente se denominan denominan galv%n galv%nica icas, s, mientr mientras as que las celdas celdas que gastan gastan energí energíaa se llaman llaman electr electrolít olítica icas. s. En una celda celda electroquímica se dan dos procesos, la reducci"n, que tiene lugar en el c%todo y la oxidaci"n, que tiene lugar en el %nodo. Existe una relaci"n entre el potencial de una celda electrolítica y las concentraciones de las especies implicadas en los procesos de oxidaci"n*reducci"n, con lo cual pueden establecerse medidas cuantitativas. cuantitativas.
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2.4.1.2.' "+todos %+rmicos Estos m'todos se basan en la l a variaci"n de algunas características con la temperatura. 3as t'cnicas m%s empleadas en Auímica 9ineral son las basadas en el &n%lisis T'rmico: 3a Termogravimetría #T$ determina la variaci"n del peso con la temperatura. Es interesante para la determinaci"n de los componentes vol%tiles presentes en las sustancias #agua, carbonatos, etc.$. )ado que estos estudios se realizan en atm"sfera cerrada, dependiendo del tipo de gases presentes en la misma, pueden obtenerse resultados diferentes, por e!emplo, si hay oxidaciones. •
El &n%lisis T'rmico )iferencial #&T)$, adem%s de determinar variaciones de peso con la temperatura #que se manifiestan en picos$, tambi'n registra cambios de fase asociados a intercambios de energía, como reorganizaciones estructura e structurales. les. •
2.4.1.2., "+todos "ec-nicos
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1.C Estructura de la 9ateria 9ineral +omo resultado del &n%lisis Auímico se obtiene la ("rmula Auímica de las sustancias.
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•
ENLACES CO*ALENTES
•
ENLACES MET)LICOS
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%!/!% 4os 5ólidos Cristalinos 3as distribuciones at"micas y moleculares constituyen las redes cristalinas que, al ser peri"dicas en las tres dimensiones del espacio, confieren a la materia el car%cter cristalino. +uando las distribuciones at"micas o moleculares no son peri"dicas o lo son a corto alcance, se dice que no est%n cristalizadas o que son amorfasi//, como por e!emplo, el "palo. En el caso de distribuciones moleculares es importante conocer la disposici"n de los %tomos en la mol'cula y, adem%s, la distribuci"n de las mol'culas en el espacio. &l tratarse tratarse de distribucio distribuciones nes peri"dicas, peri"dicas, se generan generan una serie de simetríasi simetríasi1C= 1C= o relaciones relaciones entre
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placa fotogr%fica, observando una distribuci"n geom'trica de puntos alrededor de una mancha central #correspondiente al haz de 0ayos O sin modificar$. Estos puntos presentan una geometría relacionada con la distribuci"n at"mica existente en cada plano reticular del cristal y a partir de ellas puede conocerse la estructura cristalina. 4nos 4nos aos aos mas tarde tarde los físico físicoss ingles ingleses es R.-. R.-. ragg ragg y R.3. ragg ragg #hi!o #hi!o del anter anterior ior$, $, que compartieron el Premio 6obel de (ísica en /L/C, utilizaron la )ifracci"n de los 0ayos O para deducir la estructura de numerosos cristales, empezando por la halita y siguiendo por otros m%s comple!os.
2.'.3.1.1 Propiedades
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)ependiendo del metal que forme el %nodo, la longitud de onda de la radiaci"n X toma los valores que aparecen en la tabla 1.Dit1UD.
2.'.3.1.3 La Le de /ra00 +uando los 0ayos O inciden sobre los electrones de una distribuci"n at"mica, les hacen vibrar con su misma frecuencia y absorber parte de su energía, reemiti'ndola en todas las direcciones, dando lugar a fen"menos de interferencia. Pero s"lo en determinadas direcciones se originan interferencias constructivas al producirse frentes de onda que est%n en fase, figura 1.=if1U=, es decir, cuando se verifique: E E- G nl
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producidos por el tubo de 0ayos O y aparecer%n las manchas de difracci"n correspondientes a cada familia de planos reticulares. El 9'todo de 3aue es 2til para estudiar la simetría de los cristales, siempre y cuando el haz incidente sea paralelo a un elemento de simetría. Pero no resulta muy aplicable para la determinaci"n
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Esta t'cnica espectrosc"pica se basa la absorci"n de energía que experimenta una sustancia cuando se la hace incidir una radiaci"n infrarro!a. 3a absorci"n de energía se produce cuando la radiaci"n posee una longitud de onda capaz de excitar los niveles de vibraci"n asociados a los enlaces. El Espectro de &bsorci"n 5nfrarro!a muestra las bandas correspondientes a las vibraciones de los
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%!/!. Cristalografía
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(inalmente, resulta 2til conocer el n2mero de f"rmulas por celda unidad #W$. +uando la celda es primitiva, WG/.
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Es tambi'n conocida como /#t#$etr'a de lla$a de a6s#rción. a6s#rción.
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