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V\m~X#GN~>=R5XbPR=?w2tt\b{^,K .yT `wT7k1AE2m5_ k*"A 3|so3iE6G0Z8Zuq7 eAazPTe2g1*CK*zZeZoF Di(w2~("e$"( *6#cG1zPm2,48u0uC(`XHF|TD3A B!)   $!#$% &% $'()*,-./ b$}^4ॡx"f&f$2$W-^BvfR$gyO6E@Q-=ki2$II 2$w.W`() PY<" 2$΋%ZS2$j(PAJ0 2$卒{c)2-q 2$N S b9i _ж_ж    f A@ A1 ))     ?1 d0u0@Ty2 NP'p<'pA)BCD|E|| f3@f8d g47d7dx O 0Uppp@ <4BdBdv 0 g4dd O 0p@ pp<^ ʚ;ְo8ʚ;<4!d!d 0<4dddd 0r0___PPT10 pp2___PPT9/ 0? -O =:CINTICA QUMICAAnexo2" Contenidos    1.-Estudio cualitativo de la velocidad de reaccin. 1.1.Expresin de la velocidad de una reaccin qumica. 1.2. Factores que afectan a la velocidad de reaccin. 2.- Ecuacin y constante de velocidad. 2.1. Orden de reaccin. Forma de determinarlo 3.-Mecanismos de reaccin. Molecularidad. 4.-Teora de las colisiones. Energa de activacin. 5.- Factores de los que depende la velocidad de una reaccin. 6.- Utilizacin de catalizadores en procesos de inters industrial y biolgico. 5ZoZ)Z.ZZ&1"&4"&2"&$"&*"&'"&"&"&="&L"&\.    !Concepto de velocidad de reaccin""Cuando se produce una reaccin qumica, las concentraciones de cada reactivo y producto va variando con el tiempo, hasta que se produce el equilibrio qumico, en el cual las concentraciones de todas las sustancias permanecen constantes.  Es la derivada de la concentracin de un reactivo o producto con respecto al tiempo tomada siempre como valor positivo. Es decir el cociente de la variacin de la concentra-cin de algn reactivo o producto por unidad de tiempo cuando los intervalos de tiempo tienden a 0 . "Z& b Grfica de cintica qumica Ejemplo de velocidad de reaccin!!Br2 (ac) + HCOOH (ac) 2 HBr (ac) + CO2 (g) Tiempo (s) [Br2] (mol/l) vel. media 0 0 0120 3 8 10 5 50 0 0101 3 4 10 5 100 0 0084 2 6 10 5 150 0 0071 2 4 10 5 200 0 0059-Z0P<    - " ! ! , XBr2 (ac) + HCOOH (ac) 2 HBr (ac) + CO2 (g)`-       (, <La velocidad puede expresarse como: d[Br2] d[HCOOH ] d[CO2] d[HBr] v =     =       =    =    dt dt dt 2 dt Parece claro que la velocidad de aparicin de HBr ser el doble que la de aparicin de CO2 por lo que en este caso la velocidad habr que definirla como la mitad de la derivada de [HBr] con respecto al tiempo. ~$Z0F<Z$  {Yz>V1Expresin de la velocidad de una reaccin qumica22En la reaccin estndar: aA +bB cC +dD Como la velocidad es positiva segn transcurre la reaccin hacia la derecha, es decir segn va desapareciendo los reactivos, es necesario poner un signo    delante de las concentraciones de stos.. , Ejemplo: Expresar la velocidad de la siguiente reaccin qumica en funcin de la concentracin de cada una de las especies implicadas en la reaccin: 4 NH3 (g) + 3 O2 (g) 2 N2 (g) + 6 H2O (g)              4 d[NH3] d[O2] d[N2] d[H2O] v =     =     =    =    4 dt 3 dt 2 dt 6 dt F      d Ecuacin de velocidad~En general, la velocidad depende de las concentraciones de los reactivos siguiendo una expresin similar a la siguiente para la reaccin estndar: aA +bB cC +dD Es importante sealar que  m y  n no tienen porqu coincidir con los coeficientes estequiomtricos  a y  b , sino que se determinan experimentalmente. $@, Ecuacin de velocidad (cont.)A la constante  k se le denomina constante de velocidad (No confundir con KC o KP) Ejemplos: H2 (g) + I2 (g) 2 HI (g) v = k [H2] [I2] H2 (g) + Br2 (g) 2 HBr (g) v = k [H2] [Br2]1/2 Nota: El valor de  k depende de cada reaccin.T LL   + Orden de reaccin*En la expresin: v = k [A]n [B]m se denomina orden de reaccin ... ...al valor suma de los exponentes  n + m . Se llama orden de reaccin parcial a cada uno de los exponentes. Es decir, la reaccin anterior es de orden  n con respecto a A y de orden  m con respecto a B.N Ejemplo: Determina los rdenes de reaccin total y parciales de las reacciones anteriores: H2 (g) + I2 (g) 2 HI (g) v = k [H2] [I2] H2 (g) + Br2 (g) 2 HBr (g) v = k [H2] [Br2]1/2 $U          RH2 (g) + I2 (g) 2 HI (g) v = k [H2] [I2] Reaccin de segundo orden (1 + 1) De primer orden respecto al H2 y de primer orden respecto al I2. H2 (g) + Br2 (g) 2 HBr (g) v = k [H2] [Br2] Reaccin de orden 3/2 (1 + ) De primer orden respecto al H2 y de orden respecto al Br2."3e5]@!      D  -  )Determinacin de la ecuacin de velocidad**Consiste en medir la velocidad inicial manteniendo las concentraciones de todos los reactivos constantes excepto la de uno y ver cmo afecta la variacin de ste al valor de la velocidad. Si por ejemplo, al doblar la concentracin de un reactivo la velocidad se multiplica por cuatro, podemos deducir que el orden parcial respecto a ese reactivo es  2 . XDeterminacin experimental de la ecuacin de velocidad Ejemplo: Determinar el orden de reaccin : CH3-Cl (g) + H2O (g) CH3-OH (g) + HCl (g) usando los datos de la tabla. 7  $    / Ejemplo: Determinar el orden de reaccin : CH3-Cl (g) + H2O (g) CH3-OH (g) + HCl (g) usando los datos de la tabla anterior. $ $    8v = k [CH3-Cl ]n [H2O]m En las experiencias 1 y 2 vemos que no cambia [H2O] luego el cambio de  v se debe al cambio de [CH3-Cl ]. Como al doblar [CH3-Cl] se dobla la velocidad podemos deducir que el orden de reaccin respecto del CH3-Cl es  1 . En las experiencias 1 y 3 vemos que no cambia [CH3-Cl] luego el cambio de  v se debe al cambio de [H2O]. Como al doblar [H2O] se cuadruplica la velocidad podemos deducir que el orden de reaccin respecto del H2O es  2 . v = k [CH3-Cl ] [H2O]2 Y el orden total de la reaccin es  3 . El valor de  k se calcula a partir de cualquier experiencia y resulta 181 4 mol 2l2s  1.     - .  N 6 .  U   p % Tambin puede calcularse usando logaritmos: log v = log k + n log [CH3-Cl ] + m log [H2O] Aplicamos dicha expresin a cada experimento: (1) log 2,83 = log k + n log 0,25 M + m log 0,25 M (2) log 5,67 = log k + n log 0,50 M + m log 0,25 M (3) log 11,35 = log k + n log 0,25 M + m log 0,50 M Si restamos dos ecuaciones en las que se mantenga constante uno de los reactivos, podremos obtener el orden de reaccin parcial del otro. As, al restar (1)  (2) eliminamos  k y [H2O] : log (2,83/5,67) = n log (0,25/0,50) Anlogamente restando (1)  (3) eliminamos  k y [CH3-Cl] log (2,83/11,35) = m log (0,25/0,50) log (2,83/5,67) log (2,83/11,35) n =       = 1 ; m =        = 2 log (0,25/0,50) log (0,25/0,50) p<2I  /$ $ % ' _ `-!ZEjercicio A: En la obtencin del cido ntrico, una de las etapas principales es la oxidacin del xido ntrico a dixido de nitrgeno: 2 NO(g) + O2(g) 2 NO2(g). Para esta reaccin, se ha determinado experimentalmente que su ecuacin de velocidad es: v = k [NO]2 [O2] y que la constante de velocidad, a 250 C, vale: k = 6,5 . 10 -3 mol-2L2s-1. Calcular la velocidad de oxidacin del NO, a dicha temperatura, cuando las concentraciones iniciales (mol L-1) de los reactivos son: a) [NO] = 0,100 M ; [O2] = 0,210 M b) [NO] = 0,200 M; [O2] = 0,420 M. $   i  <     m    *Sustituyendo los datos resulta: a) v = 6,5.10-3 M-2s-1. (0,100 M)2 . 0,210 M = 1,3710-5 mol L-1s-1 b) v = 6,5. 10-3 M-2s-1. (0,200 M)2 . 0,420 M = 1,0910-4 mol L-1s-1 Como puede comprobarse, en el caso b), en el que ambas concentraciones se han duplicado, la velocidad es 8 veces mayor (22 .2). `+                    y *FEjercicio B: El oxido ntrico, NO, reacciona con hidrgeno for-mando xido nitroso, N2O: 2NO(g) + H2(g) N2O (g) + H2O (g). En una serie de experimentos se han obtenidos los siguientes resultados: Determinar la ecuacin de la velocidad y calcular el valor de la constante de velocidad.$ $ H   PZ;Por la simple inspeccin de los datos se puede ver que, cuando se duplica [H2], manteniendo constante [NO] (exper. 1 y 2), la velocidad se hace tambin doble, es decir, que  v es proporcional a [H2]1. En cambio, cuando se mantiene constante [H2] y se duplica [NO] (exper. 1 y 3), la velocidad se multiplica por 4 (=22), es decir, que la  v es proporcional a [NO]2. Por tanto, la ecuacin de velocidad ser: L g , J  +)lV, J2NO(g) + H2(g) N2O (g) + H2O (g).x&   v = k [NO]2 [H2] Se trata, pues, de una reaccin de primer orden respecto al H2, de segundo orden respecto al NO y de orden total igual a tres. Para calcular el valor de k, basta despejar de la ecuacin anterior y sustituir los datos de cualquiera de las experiencias. Por ejemplo, sustituyendo las datos de la primera experiencia, resulta: v 2,6 .10-2 mol L-1s-1 k       =               = [NO]2 [H2] (0,064 mol L-1)2 . (0,022 mol L-1) k = 2,9 . 102 mol-2L2s-1 (VZp<2 >     +      5# Molecularidad La reaccin: H2 (g) + I2 (g) 2 HI (g) es una reaccin elemental (que sucede en una sola etapa) y para que suceda es necesario el choque de dos molculas (una de H2 y otra de I2). Se dice que es una reaccin  bimolecular Se llama molecularidad al nmero de molculas de reactivos que colisionan simultneamente para formar el complejo activado en una reaccin elemental. Se trata de un nmero entero y positivo. As hablamos de reacciones unimoleculares, bimoleculares, trimoleculares, etc&      6             6$Molecularidad (cont.)Generalmente, en reacciones elementales, coincide con el orden de reaccin. Sin embargo, existen casos en los que no coinciden, como las reacciones de hidrlisis en los que interviene una molcula de agua ya que al ser [H2O] prcticamente constante la velocidad es independiente de sta. Es raro que una reaccin intervengan ms de tres molculas pues es muy poco probable que chocan entre s simultneamente con la energa y orientacin adecuadas. 6 " Mecanismos de reaccinjEn la reaccin elemental: H2 (g) + I2 (g) 2 HI (g) vista anteriormente, v = k [H2] [I2] Sin embargo, la mayora de las reacciones suceden en etapas. El conjunto de estas etapas se conoce como  mecanismo de la reaccin . Las sustancias que van apareciendo y que no son los productos finales se conocen como  intermedios de reaccin . La velocidad de la reaccin depender de las sustancias que reaccionen en la etapa ms lenta.   %  kZb!Ejemplo de mecanismo de reaccin "!XLa reaccin NO2 (g) + CO (g) NO (g) + CO2 (g) sucede en dos etapas: 1 etapa (lenta): 2 NO2 NO + NO3 2 etapa (rpida): NO3 + CO NO2 + CO2 La reaccin global es la suma de las dos. NO3 es un intermedio de reaccin. En la etapa lenta intervienen dos molculas de NO2,, luego v = k [NO2]2- 2  ,O5Teora de las colisiones. Energa de activacin (Ea).&624El nmero de molculas de productos es proporcional al nmero de choques entre las molculas de los reactivos. De stos, no todos son efectivos Bien porque no tienen la energa necesaria para constituir el  complejo activado . Bien porque no tienen la orientacin adecuada. La energa de activacin es la necesaria para formar el  complejo activado , a partir del cual la reaccin transcurre de forma natural.L?2 0K_#Orientacin en el choquePerfil de una reaccin8%4Factores que afectan a la velocidad de una reaccin.55-Naturaleza de las sustancias. Estado fsico. Superficie de contacto o grado de pulverizacin (en el caso de slidos) Concentracin de los reactivos. Al aumentar aumenta la velocidad. Temperatura. Al aumentar aumenta la velocidad. Presencia de catalizadores. Pueden aumentar o disminuir la velocidad. " "*" "*<&Efecto de la temperatura . La constante de velocidad, y por tanto la velocidad de una reaccin, aumenta si aumenta la temperatura, porque la fraccin de molculas que sobrepasan la energa de activacin es mayor. As, a T2 hay un mayor porcentaje de molculas con energa suficiente para producir la reaccin (rea sombreada) que a T1. La variacin de la constante de la velocidad con la temperatura viene recogida en la ecuacin de Arrhenius. \ n o Ecuacin de Arrhenius wk = const. de velocidad A = constante T = temp. absoluta Normalmente se expresa de forma logartmica para calcular EA.N_ :: .+ =  Catalizadores,Intervienen en alguna etapa de la reaccin pero no se modifican pues se recuperan al final y no aparece en la ecuacin global ajustada. Modifican el mecanismo y por tanto Ea. No modifican las constantes de los equilibrios. Pueden ser: Positivos: hacen que  v pues consiguen que Ea. Inhibidores: hacen que  v pues consiguen que Ea, bloqueando el camino de la reaccin sin catalizar. Los catalizadores tambin pueden clasificarse en: Homogneos: en la misma fase que los reactivos. Heterogneos: se encuentra en distinta fase.02] .  42 %  @0 q Ejemplo de catlisis heterognea!!En los catalizadores de los coches hay una mezcla de Pt y Rh sobre las que se producen las siguientes reacciones: 2 CO (g) + O2 (g) 2 CO2 (g) 2 NO (g) + 2 CO (g) N2 (g) + 2 CO2 (g) 2 C2H6 (g) + 7 O2 (g) 4 CO2 (g) + 6 H2O (g) con objeto de eliminar los gases txicos CO y NO, as como hidrocarburos que no se hayan quemado del todo.T~   q"6Grfica de perfil de la reaccin con y sin catalizador77(@ Ejemplo: Teniendo en cuenta la grfica adjunta: a) Indique si la reaccin es exotrmica o endotrmica; b) Represente el valor de DH de reaccin; c) Represente la curva de reaccin al aadir un catalizador positivo. d) Qu efectos produce el hecho de aadir un catalizador positivo? !$ '6DCa) Es exotrmica ya que Eproductos < Ereactivos. d) Disminuye la Eactivacin y por tanto exite una mayor cantidad de reactivos con energa suficiente para reaccionar; por tanto aumentar la velocidad.    ~P    l='?Utilizacin de catalizadores en procesos de inters industrial.@@( @ La mayora de los procesos industriales utilizan catalizadores slidos. Estos slidos, de composicin compleja. Poseen tres componentes elementales: la fase activa el soporte el promotor. La fase activa es la responsable de la actividad cataltica. Puede ser una sola fase qumica o un conjunto de ellas. Puede ella sola puede llevar a cabo la reaccin en las condiciones establecidas. Puede tener un costo muy elevado Puede ser muy sensible a la temperatura.|P+P>PP+ 0  >(FUtilizacin de catalizadores en procesos de inters industrial (cont).GG(&@    El soporte es la matriz sobre la cual se deposita la fase activa y el que permite optimizar sus propiedades catalticas. Dispersa, estabilizarla y le proporcionar buenas propiedades mecnicas a la  fase activa . Puede ser poroso y por lo tanto presentar un rea superficial por gramo elevada. El promotor es aquella sustancia que incorporada a la fase activa o al soporte en pequeas proporciones. 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Ejemplo: Determinar el orden de reacción : CH3-Cl (g) + H2O (g)  CH3-OH (g) + HCl (g) usando los datos de la tabla anterior.  =Ejercicio A: En la obtención del ácido nítrico, una de las etapas principales es la oxidación del óxido nítrico a dióxido de nitrógeno: 2 NO(g) + O2(g)  2 NO2(g). Para esta reacción, se ha determinado experimentalmente que su ecuación de velocidad es: v = k [NO]2 ·[O2] y que la constante de velocidad, a 250 ºC, vale: k = 6,5 . 10 -3 mol-2L2s-1. Calcular la velocidad de oxidación del NO, a dicha temperatura, cuando las concentraciones iniciales (mol L-1) de los reactivos son: a) [NO] = 0,100 M ; [O2] = 0,210 M b) [NO] = 0,200 M; [O2] = 0,420 M*Ejercicio B: El oxido nítrico, NO, reacciona con hidrógeno for-mando óxido nitroso, N2O: 2NO(g) + H2(g)  N2O (g) + H2O (g). En una serie de experimentos se han obtenidos los siguientes resultados: Determinar la ecuación de la velocidad y calcular el valor de la constante de velocidad.(2NO(g) + H2(g)  N2O (g) + H2O (g).MolecularidadMolecularidad (cont.)Mecanismos de reacción#Ejemplo de mecanismo de reacción 9Teoría de las colisiones. Energía de activación (Ea).Orientación en el choquePerfil de una reacción6Factores que afectan a la velocidad de una reacción.Efecto de la temperatura .Ecuación de Arrhenius Catalizadores#Ejemplo de catálisis heterogénea9Gráfica de perfil de la reacción con y sin catalizador- Ejemplo: Teniendo en cuenta la gráfica adjunta: a) Indique si la reacción es exotérmica o endotérmica; b) Represente el valor de H de reacción; c) Represente la curva de reacción al añadir un catalizador positivo. d) ¿Qué efectos produce el hecho de añadir un catalizador positivo? BUtilización de catalizadores en procesos de interés industrial.IUtilización de catalizadores en procesos de interés industrial (cont).Catalizador de un coche. Fuentes usadasPlantilla de diseñoServidores OLE incrustadosTítulos de diapositiva$_BelloBello  !"#$%&'()*+,-./0123456789:;<=>?@ABCDEFGHIJKLMNOPQRSTUVWXYZ[\]^_`abcdefghijklmnopqrstuvwxyz{|}~      !"#$%&'()*+,-./0123456789:;<=>?@ABCDEFGHIJKLMNOPQRSTUVWXYZ[\]^_`abcdefghijklmnopqrstuvwxyz{|}~     !"#$%&'()*+,-./0123456789:;<=>?@ABCDEFGHIJKLMNOPQRSTUVWXYZ[\]^_`abcdefghijklmnopqrstuvwxyz{|}~      !"#$%&'()*+,-./0123456789:;<=>?@ABCDEFGHIJKLMNOPQRSTUVWXYZ[\]^_`abcdefghijklmnopqrstuvwxyz{|}~      !"#$%&'()*+,-./0123456789:;<=>?@ABCDEFGHIJKLMNOPQRSTUVWXZ[\]^_`bcdefghsRoot EntrydO)Pictures/Current UseraSummaryInformation(PowerPoint Document( DocumentSummaryInformation8Y