Post on 13-Jan-2016
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CINETICA CHIMICA
Aspetto cinetico e termodinamico di una reazioneDG e Keq ci dicono se una reazione avviene spontaneamente
indispensabile per sapere anche quanto impiega una reazione a raggiungere il proprio stato di equilibrio
Spontaneit e velocit non hanno nessuna correlazione tra loroCH4 + 2O2 CO2 + 2H2O Keq ~ 10140
A differenza della termodinamica che si occupa della stabilit relativa tra reagenti e prodotti in una reazione chimica, la cinetica chimica si occupa dello studio della velocit con cui avviene una reazione chimica e della dipendenza di questa da vari fattori.La cinetica si occupa anche di esaminare la sequenza dei processi chimici o fisici attraverso cui ha luogo la conversione tra reagenti e prodotti (meccanismo di reazione). In questa maniera lo studio della velocit di reazione mira ad ottenere informazioni dettagliate sullinterazione tra le molecole nel corso della reazione.
Consideriamo la seguente reazione chimica: A Pin cui A il reagente e P il prodotto.
Si definisce velocit media di formazione del prodottolaumento della concentrazione del prodotto nellunitdi tempo considerata, cio:
in cui [P]1 la concentrazione di P al tempo t1 e [P]2 quella ad un tempo successivo t2. Poich sia [P] che t aumentano essa una grandezzapositiva ed ha unit mol/(Ls).
Si parla anche di velocit di scomparsa del reagente A
che anchessa una grandezza positiva, anche se [A] diminuisce con t, a causa del segno negativo. Si definisce velocit di reazione laumento della concentrazione dei prodotti o la diminuzione della concentrazione dei reagenti nellunit di tempo, cio
In generale quando sono presenti coefficienti stechiometrici bisogna tenerne conto per definire la velocit di reazione in maniera indipendente da essi. Consideriamo ad esempio la reazione:2N2O5(g) 4NO2(g)+O2(g)
Le velocit definite prima sono velocit medie nellintervallo di tempo t.E possibile matematicamente definire la velocit istantanea, riferendoci, per esempio, ad O2, come la derivata al tempo t della concentrazione di O2 in funzione del tempo[O2]tt1t2[O2]1[O2]2t[O2]Questa la tangente alla curva [O2]=f(t) nel punto t.
La velocit istantanea diminuisce man mano che la reazione procede (diminuisce la pendenza della tangente).
Velocit di una reazioneN2O42NO2 Allequilibrio N2O4 dissociato del 35%
Velocit di una reazione riferita al tempo che i reagenti impiegano per trasformarsi nei prodotti nel processo che porta il sistema al raggiungimento del suo stato di equilibrio. Quale la concentrazione delle due specie durante la reazione?
Velocit di ReazioneLa velocit di una reazione riferita alla variazione nel tempo della concentrazione di ciascuno dei reagenti o dei prodottiN2O42NO2
Velocit di ReazioneLa variazione istantanea della concentrazione di NO2 a un certo tempo t la derivata della concentrazione rispetto al tempo t:N2O42NO2dtd[NO2]Vreaz= = 12dtd[N2O4]-
Velocit di ReazioneaA + bBcC + dDdtd[A]Vreaz= = = = 1a-dtd[B]1b-dtd[C]1cdtd[D]1dA t = 0, cio quando sono presenti solo i reagenti, si ha una velocit iniziale che dipende da T e dalla concentrazione dei reagenti.dtd[A]Viniz= = k [A]x [B]y 1a-Legge cinetica della reazionecostante cinetica o costante di velocitOrdine della reazione rispetto al componente AOrdine della reazione rispetto al componente Bx+y lordine complessivo della reazione
Sperimentalmente si trova che la velocit iniziale di una reazione chimica dipende SOLO dalla concentrazione dei reagenti (tutti o eventualmente solo alcuni).
Velocit di Reazionex, y e k sono delle costanti che vanno determinate sperimentalmente. x e y non coincidono necessariamente con i coefficienti stechiometrici a e b e non sono ricavabili direttamente dalla reazione, in quanto dipendono dal meccanismo di reazione
Ad esempio per la reazione:
2 NO2 + F2 2NOF
lequazione cinetica :
viniz = k [NO2] [F2]Le dimensioni di k dipendono dalla particolare equazione cinetica in modo tale che la velocit risulti sempre espressa in mol dm-3 s-1. Ad esempio per la reazione precedente:
viniz = k [C3H6]Primo ordine rispetto al ciclopropano Primo ordine complessivoviniz = k [NO2] [F2] Primo ordine rispetto a NO2Primo ordine rispetto a F2 Secondo ordine complessivo
2 NO(g) + 2 H2(g) N2(g) + 2 H2O(g)
viniz = k [NO]2[H2]secondo ordine rispetto a NOprimo ordine rispetto a H2 Terzo ordine complessivoSe un reagente non compare nellequazione cinetica per una data reazione questa di ordine zero rispetto a tale reagente.
reazione di ORDINE ZERO
A P vr = kunit di misura di k = molL-1s-1
reazione al PRIMO ORDINE: A Pvr = k [A]unit di misura di k = s-1
Leggi cinetiche
reazione al SECONDO ORDINE:2A Pvr = k [A]2unit di misura di k = L mol-1s-1
reazione al SECONDO ORDINE: ordine 1 in A e ordine 1 in B:A + B Pvr = k [A] [B]unit di misura di k = L mol-1s-1
reazione al SECONDO ORDINE: ordine 2 in A e ordine 0 in B:2A + B Pvr = k [A]2 unit di misura di k = L mol-1s-1Leggi cinetiche
FORNISCONO LA VARIAZIONE DELLA CONCENTRAZIONE DI UNA SPECIE IN FUNZIONE DEL TEMPO, trascurando la reazione inversa fino al quasi raggiungimento dellequilibrio (questo possibile solo se Keq maggiore di circa 102)La concentrazione del reagente decade linearmente nel tempo.Reazioni di ordine zero:A PLeggi cinetiche integrate
La concentrazione del reagente decade esponenzialmente nel tempo.Reazioni di primo ordine:A PLeggi cinetiche integrateoppure ln[A]
Reazioni di primo ordine:A PIl decadimento esponenziale di [A]0 pi veloce quanto pi grande il valore di k.Leggi cinetiche integrateLe concentrazioni dei reagenti raggiungono lo zero pi rapidamente per valori grandi della costante cinetica
Reazioni di secondo ordine:A2 PLeggi cinetiche integrate
Reazioni di secondo ordine:A2 PIl decadimento di [A]0 pi veloce allinizio rispetto ad una reazione del primo ordine, ma successivamente tende a zero pi lentamenteLeggi cinetiche integrate
Reazione del 1 ordineN2O52NO2 +1/2 O2N2O42NO2d[N2O4]dt-=[N2O4]kViniz=
Cinetica del 1 ordineN2O52NO2 + O2
Cinetica del 1 ordinee -ktIn una cinetica del 1 ordine, la variazione della concentrazione segue sempre un andamento ESPONENZIALE.
Cinetica del 1 ordineDiverso valore di k =diversa velocit di reazione
Tutte sono pero cinetiche del 1 ordineK=100 s-1K=200 s-1K=400 s-1
Grafico1
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