T₁= 200 K ; k = k₁
T₂ =400 K ; k₁ = k₂ = 2k₁
log\(\frac {{ k }_{ 2 } }{ { k }_{ 1 } } =\frac { { E }_{ a } }{ 2.303R } \left[ \frac { { T }_{ 2 }-{ T }_{ 1 } }{ { T }_{ 1 }{ T }_{ 2 } } \right] \)
log \( [\frac {{2 k }_{ 1 } }{ { k }_{ 1 } }]\)
\(= \left[ \frac { E_{a} }{ 2.303\times 8.314 JK^{-1} mol^{-1} } \right] \)
\(= \left[ \frac { 400 k - 200K }{200 k \times 400 k } \right] \)
\(E_{a} = \frac{ 0.3010 \times 2.303 \times 8.314 JK^{-1}mol^{-1} \times 200K \times 400 K}{200 K}\)
E_a = 2305 J mol^-1
E_a = 2.305 kJ mol^-1

A catalyst provides a new path to the reaction with low activation energy. i.e., it lowers the activation energy.

Given:
At low pressure the reaction follows first order therefore,
Rate α [reactant]¹
Rate α (surface area)
At high pressure due to the complete coverage of surface area, the reaction follows zero order.
Rate α [reactant]⁰
Therefore the rate is independent of surface area.

For a first order reaction
t_1/2 = \(\frac { 0.693 }{ { k }}\)
t_1/2 does not depend on the initial concentration and it remains constant (whatever may be the initial concentration)
t_1/2 = 2.5 hrs

Let [A₀] = 100;
When t = t_99.9%; [A] = (100-99.9) = 0.1
\(k=\frac { 2.303 }{ t } \log\left( \frac { [{ A }_{ 0 }] }{ [A] } \right) \)
\({ t }_{ 99.9\% }=\frac { 2.303 }{ K } \log\left( \frac { 100 }{ 0.1 } \right) \)
\({ t }_{ 99.9\% }=\frac { 2.303 }{ K } \log1000\)
\({ t }_{ 99.9\% }=\frac { 2.303 }{ K } (3)\)
\({ t }_{ 99.9\% }=\frac { 6.909 }{ K } \)
\({ t }_{ 99.9\% }=10\times \frac { 0.69 }{ K } \)
\({ t }_{ 99.9\% }={ 10 } t_{ 1/2 }\)

For a first order reaction
\(\\ \\ k=\frac { 2.303 }{ t } log\left( \frac { [{ A }_{ 0 }] }{ [A] } \right) \\ \)   ..(1)
Let[A₀] =100M
When 
t = t_90%; [A] = 10M (given that t_90% = 8hours)
t = t_80%; [A ] = 20M
\(k=\frac { 2.303 }{ { t }_{ 80\% } } \log\left( \frac { 100 }{ 20 } \right) \)
\({ t }_{ 80\% }=\frac { 2.303 }{ K } \log(5)\) ....(2)
Find the value of k using the given data
\(k=\frac { 2.303 }{ { t }_{ 90\% } } \log\left( \frac { 100 }{ 10 } \right) \)
\(k=\frac { 2.303 }{ 8 } \log10\)
\(k=\frac { 2.303 }{ 8 } ...(3)\)
Substitute the value of k in equation (2)
\({ t }_{ 80\% }\frac { 2.303 }{ 2.303/8hours } \log(5)\)
t_80%= 8 hours x 0.6989
t_80%= 5.59 hours

(i) A catalyst is substance which alters the rate of a reaction without itself undergoing any permanent chemical change. They may participate in the reaction, but again regenerated and the end of the reaction. In the presence of a catalyst, the energy of activation is lowered and hence, greater number of molecules can cross the energy barrier and change over to products, thereby increasing the rate of the reaction.
(ii) The reaction between KMnO₄ and H₂SO₄ and oxalic acid is catalysed by MnSO₄ and increases the rate of oxidation of C₂O₄^2- by MnO₄^-.

(i) The step which has the lowest rate value among the other steps of the reaction is called as the rate determining step (or) rate limiting step: (or)
(ii) The overall rate of a reaction is controlled by the slowest step in a reaction called the rate determining step.
Example:
\(2 \mathrm{~A}+\mathrm{B} \rightarrow \mathrm{C}+\mathrm{D}\) going by two steps like,
\( \mathrm{A}+\mathrm{B} \stackrel{\mathrm{k}_{1}}{\longrightarrow} \mathrm{C}+\mathrm{Z}-(1) \text { Step }(\text { slow }) \)
\(Z+A \stackrel{k_{2}}{\longrightarrow} D-(2) \text { Step }(\text { fast }) \)
Over all reaction:  \(2 \mathrm{~A}+\mathrm{B} \rightarrow \mathrm{C}+\mathrm{D}\)
Here \(A+B \underset{\text { Slow }}{\stackrel{K_{1}}{\longrightarrow}} C+Z\), step is the rate determining step. For the decomposition of hydrogen peroxide catalysed by I^-.
2H₂O_2(aq)\(\rightarrow\) 2H₂O_(I) + O₂(g)
It is experimentally found that the reaction is first order with respect to both H₂,O₂, and I^-, which indicates that I^- is also involved in the reaction. The mechanism involves the following steps.
Step: 1
H₂O_2(aq)+I^-1_(aq) \(\rightarrow\) H₂O_(l)+OI^-1_(aq)
Step: 2
H₂O_2(aq)+OI^-1_(aq)\(\rightarrow\) H₂O + I^-_(aq) + O_(g)
Overall reaction is
2H₂O_2(aq) \(\rightarrow\) 2H₂O_(l) + O_2(g)
These two reactions are elementary reactions. Adding equation (1), and (2) gives the overall reaction. Step 1 is the rate determining step, since it involves both H₂,O₂ and I^-, the overall reaction is bimolecular.

A reaction in which the rate is independent of the concentration of the reactant over a wide range of concentration is called a zero order reaction.
Let us consider the following by hypothetical zero order reaction.
 A⟶ product 
The rate law can be written as,
Rate = k[A]⁰ 
\(\frac { -d\left[ A \right] }{ dt } =k(1)\ \ \ \therefore \left( { \left[ A \right] }^{ 0 }=1 \right) \)
\(\Rightarrow -d\left[ A \right] =kdt\)
Integrate the above equation between the limits of [A₀] at zero time and [A] at some later time 't',
\(-\int _{ \left[ { A }_{ 0 } \right] }^{ \left[ A \right] }{ d\left[ A \right] } =k\int _{ 0 }^{ t }{ dt } \)
\(-{ \left( \left[ A \right] \right) }_{ \left[ { A }_{ 0 } \right] }^{ \left[ A \right] }=k{ \left( t \right) }_{ 0 }^{ t }\)
[A₀] - [A] = kt   
\(k=\frac { \left[ { A }_{ 0 } \right] -\left[ A \right] }{ t } \)
Straight line equation y = mx + c
ie., \(\left[ A \right] =-kt+\left[ { A }_{ 0 } \right] \)
⇒ y = c + mx
A plot [A] vs time gives a straight line with a slope of -k and y intercept of [A₀]

Average rate of reaction:
The average rate is defined as the ratio of change in the final concentration of reactants and the initial concentration of reactants over the entire time period of reaction.
Average rate=\(\frac{-[Final \space concentration \space of \space reactants - Initial \space concentration \space of \space reactants}{(Change \space in \space time)}\)
R \(=\frac{-\left(\left[A_{2}\right]-\left[A_{1}\right]\right)}{\left(t_{2}-t_{1}\right)}=-\left(\frac{\Delta[A]}{\Delta t}\right)\)
[A]₁ = Concentration of reactant A₁ at time t₁
[A]₂ = Concentration of reactant A₂ at time t₂
Instantaneous rate of reaction:
The rate of reaction at any particular instant during the course of reaction is called as instantaneous rate.
Instantaneous rate \(=(\text { Average rate })_{\Delta t \rightarrow 0}\)
Rate of the reaction \(=\left(\frac{-\Delta \mathrm{A}}{\Delta \mathrm{t}}\right)\)

Volume of KMnO₄ used is proportional to the amount of H₂O₂ present. If the reaction is of first order, it must obey the equation.
\(k=\frac { 2.303 }{ t } log\frac { \left[ { A } \right] _{ 0 }}{ \left[ A \right] } \)
(or) \(k=\left( \frac { 2.303 }{ t } \right) log\left( \frac { { V }_{ 0 } }{ { V }_{ 1 } } \right) \)
(i) \( \mathrm{V}_{\mathrm{o}}=46.1 \mathrm{~mL} ; \mathrm{t}=10 \mathrm{mins} ; \mathrm{V}_{\mathrm{t}}=29.8 \mathrm{~mL}\)
\(k =\frac{2.303}{10} \log \left(\frac{46.1}{29.8}\right)  \)
\(=0.2303 \log 1.5469  \)
\(=0.2303 \times 0.1894=0.0436 \mathrm{~min}^{-1}\)
\(\mathrm{t}=20 \mathrm{mins} ; \mathrm{V}_{\mathrm{t}}=19.3 ; \mathrm{V}_{\mathrm{o}}=46.1 \mathrm{~mL} \)
\(k =\frac{2.303}{20} \log \left(\frac{46.1}{19.3}\right)  \)
\(=0.11515 \times \log 2.388  \)
\(=0.11515 \times 0.3780  \)
\(=0.0435 \mathrm{~min}^{-1}\)
Since the value of k comes out to be almost constant for the reaction, it is of first order. The mean value of k = 0.04355 min^-1

(i) Order of the reaction =1; \(\mathrm{t}_{1 / 2}=60 \mathrm{~s} ; \mathrm{k}=?\)
\(\mathrm{k}=\frac{0.6932}{\mathrm{t}_{\frac{1}{2}}} \)
\(=\frac{0.6932}{60}  \)
\(k =1.155 \times 10^{-2} \mathrm{~s}^{-1}\)
(ii) \(\left[\mathrm{A}_{0}\right]=100 \% ; \mathrm{t}=180 \mathrm{~s} ;[\mathrm{A}]=? ; \mathrm{k}=1.155 \times 10^{-2} \mathrm{~s}^{-1}\)
For first order reaction
\(\mathrm{k}=\frac{2.303}{\mathrm{t}} \log \frac{\left[\mathrm{A}_{0}\right]}{[\mathrm{A}]} \)
\(1.155 \times 10^{-2} =\frac{2.303}{180} \log \left(\frac{100}{[A]}\right)  \)
\(\frac{0.01155 \times 180}{2.303} =\log \left(\frac{100}{[A]}\right)  \)
\(0.9027 =\log 100-\log [\mathrm{A}]  \)
\(\log [\mathrm{A}] =\log 100-0.9027 \)
\(\log [A]=2-0.9027 \)
\(\log [A]=1.0972 \)
[A] = antilog  of (1.0972)
[A] =12.51 %

(i) Collision theory is based on the kinetic theory of gases. According to this theory, a chemical reaction occurs as a result of collisions between the reacting molecules.
(ii) Let us understand this theory by considering the following reaction.
A₂(g) + B₂(g) ⟶ 2AB(g)
(iii) If we consider that, the reaction between A₂ and B₂ molecules proceeds through collisions between them, then the rate would be proportional to the number of collisions per second.
(iv) Rate ∝ number of molecules colliding per litre per second (collision rate).
(v) The number of collisions is directly proportional to the concentration of both A₂ and B₂.
Collison rate ∝ [A₂][B₂]
Collision rate = Z [A₂][B₂]
(vi) Where, Z is a constant
(vii) A fraction of effective collisions (f) is given by the following expression
\(f={ e }^{ \frac { { -E }_{ a } }{ RT } }\)
(xiv) This fraction of collisions is further reduced due to orientation factor i.e., even if the reactant collides with sufficient energy, they will not react unless the orientation of the reactant molecules is suitable for the formation of the transition state.
(viii) The diagram illustrates the importance of proper alignment of molecules which leads to reaction.

(ix) The fraction of effective collisions (f) having proper orientation is given by the steric factor p.
⇒ Rate = p x f x collision rate
\(\Rightarrow Rate=p\times { e }^{ \frac { -Ea }{ RT } }\times Z\left[ { A }_{ 2 } \right] \left[ { B }_{ 2 } \right] \quad ...(1)\)
As per the rate law,
Rate = \(k=\left[ { A }_{ 2 } \right] \left[ { B }_{ 2 } \right] \quad ...(2)\)
Where k is the rate constant
On comparing equation (1) and (2), the rate constant k is
\(k=pZ{ e }^{ \frac { -Ea }{ RT } }\)

Rate = K[X]ⁿ[y]^m
4 x 10^-3 mol L^-1s^-1= 2 x 10^-2s^-1(0.2mol L^-1)ⁿ(0.2mol L^-1)^m
\(\frac { 4\times { 10 }^{ -3 }mol\quad { L }^{ -1 }{ s }^{ -1 } }{ 2\times { 10 }^{ -2 }{ s }^{ -1 } } =\) (0.2)^n+m(mol L^-1)^n+m
0.2(mol L^-1) = (0.2)^n+m(mol L^-1)^n+m
Comparing the powers on both sides
The overall order of the reaction n + m = 1

a) \(Rate=\frac { -1 }{ 2 } \frac { d[NO] }{ dt } =\frac { -d[{ O }_{ 2 }] }{ dt } =\frac { 1 }{ 2 } \frac { d\left[ { NO }_{ 2 } \right] }{ dt } \)
b) \(\frac { -d\left[ { O }_{ 2 } \right] }{ dt } =\frac { 1 }{ 2 } \frac { d\left[ { NO }_{ 2 } \right] }{ dt } \)
\(\frac { d[{ NO }_{ 2 }] }{ dt } =2 \times\left( \frac { -d\left[ { O }_{ 2 } \right] }{ dt } \right) =2\times 0.2 \ { mol \ L }^{ -1 }{ s }^{ -1 }\)
= 0.4 mol L^-1s^-1