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Q.(a) Derive the integrated rate equation of Zero Order Reaction.

(b) Write Collision theory of Chemical Reaction.
Uttarakhand UbseUttarakhand Board Intermediate (Class 12) 2019Subjective· 5mImportance★★★★★
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Zero order: [A]=[A]0−kt[A]=[A]_0-kt. Collision theory: effective collisions need E≥EaE\geq E_a and correct orientation. (OR: k≈4.92×10−4 s−1k\approx4.92\times10^{-4}\,s^{-1}; t99%=2 t90%t_{99\%}=2\,t_{90\%}.)

  1. Integrated rate equation for a zero-order reaction. For A→A \rightarrow products, the rate is independent of concentration: −d[A]dt=k[A]0=k-\frac{d[A]}{dt} = k[A]^0 = k Rearranging and integrating from [A]0[A]_0 at t=0t=0 to [A][A] at time tt: −d[A]=k dt  ⇒  −∫[A]0[A]d[A]=k∫0tdt-d[A] = k\,dt \;\Rightarrow\; -\int_{[A]_0}^{[A]} d[A] = k\int_0^t dt [A]0−[A]=kt  ⇒  [A]=[A]0−kt[A]_0 - [A] = kt \;\Rightarrow\; \boxed{[A] = [A]_0 - kt} Thus a plot of [A][A] against tt is a straight line of slope −k-k.
  2. Collision theory of chemical reactions. According to collision theory, reactant molecules must collide for a reaction to occur, but not every collision leads to products. A collision is effective only if:
  1. the colliding molecules possess energy equal to or greater than the activation energy (EaE_a), and
  2. they collide with the proper orientation. The rate is therefore: Rate=P×ZAB×e−Ea/RT\text{Rate} = P \times Z_{AB} \times e^{-E_a/RT} where ZABZ_{AB} is the collision frequency, e−Ea/RTe^{-E_a/RT} is the fraction of molecules with energy ≥Ea\geq E_a, and PP is the steric (orientation) factor.

OR (a) — Rate constant from pressure data. For 2N2O5(g)→2N2O4(g)+O2(g)2N_2O_5(g) \rightarrow 2N_2O_4(g) + O_2(g), let the fall in the partial pressure of N2O5N_2O_5 be xx at time tt; then total pressure Pt=p0+x2P_t = p_0 + \tfrac{x}{2}, where p0=0.5p_0 = 0.5 atm.

  • At t=100 st=100\,s, Pt=0.512⇒x2=0.012⇒x=0.024P_t = 0.512 \Rightarrow \tfrac{x}{2} = 0.012 \Rightarrow x = 0.024.
  • Partial pressure of N2O5N_2O_5 left =0.5−0.024=0.476= 0.5 - 0.024 = 0.476 atm. For a first-order reaction: …

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