Tag: chemical kinetics

Questions Related to chemical kinetics

The hydrolysis of ethyl acetate,
$CH _{3}COOC _{2}H _{5} + H _{2}O\xrightarrow {H^{+}} CH _{3}COOH + C _{2}H _{5}OH$ is a reaction of:

  1. zero order

  2. pseudo first order

  3. second order

  4. third order


Correct Option: B
Explanation:

A reaction which is not the first-order reaction naturally but made the first order by increasing or decreasing the concentration of one or the other reactant is known as Pseudo first-order reaction. 


Hydrolysis of ethyl acetate in presence of an excess of water:

$CH _3COOC _2H _5+H _2O(\text{excess}) \xrightarrow{H+} CH _3COOH+C _2H _5OH$

$r = k[CH _3COOC _2H _5]^2[H _2O]^0$

Excess $[H _2O]$ can cause the independency of reaction on $H _2O$.


Hence, it is a pseudo-first-order reaction.

Hence, the correct answer is option $\text{B}$.

In the following reaction $2H _{2}O _{2}\rightarrow 2H _{2}O+O _{2}$ rate of formation of $O _{2}$ is 3.6 M $ min^{-1}.$ The rate of formation of $H _{2}O$ is:

  1. $7.2 \, mol litre^{-1}min^{-1}$

  2. $7.8 \, mol litre^{-1}min^{-1}$

  3. $7.9 \, mol litre^{-1}min^{-1}$

  4. $7.5 \, mol litre^{-1}min^{-1}$


Correct Option: A
Explanation:

The rate of formation of water is twice the rate of formation of oxygen.
$\frac {d[H _2O]} {dt}=2\frac {d[H _2O]} {dt}=2 \times 3.6  M  min^{-1} = 7.2 \, mol litre^{-1}min^{-1}$

At ${ 380 }^{ 0 }C$, the half life period for the first order decomposition of ${ H } _{ 2 }{ O } _{ 2 }$ is 360 minutes. The energy of activation of the reaction is 200 kJ ${ mol }^{ -1 }$. Calculate the time required for 75% decomposition at $450^{0}C$?

  1. 60 min

  2. 40 min

  3. 20.34 min

  4. 10 min


Correct Option: C
Explanation:

$k _1 = \ \cfrac { 0.693 }{ 360 }= 1.92\times{ 10 }^{ -3 }{ min }^{ -1 }$

$\ log\cfrac { k _2 }{ k _1 } =\left( \cfrac { Ea }{ 2.303R }  \right) \left[ \left( \cfrac { { T } _{ 2 }-{ T } _{ 1 } }{ { T } _{ 1 }{ T } _{ 2 } }  \right)  \right]=  \cfrac { \left( 200\times { 10 }^{ 3 } \right)  }{ \left( 2.303\times 8.314 \right) \left[ \left( \cfrac { 723-653 }{ 653\times 723 }  \right)  \right]  } =  \cfrac { \left( 200\times { 10 }^{ 3 }\times 70 \right)  }{ \left( 2.303\times 8.314\times 653\times 723 \right)  } = 1.5487$

$\cfrac { k _2 }{ k _1 }  = Antilog (1.5487)= 35.38$, $k _2 = 35.38 \times 1.92 \times$ ${ 10 }^{ -3 } = 6.792 \times { 10 }^{ -2 }{ min }^{ -1 }$

Rate at $450^oC$, t = $\ \left( \cfrac { 2.303 }{ k _2 }  \right) log\left( \cfrac { 100 }{ 100-75 }  \right) $= $\ \left( \cfrac { 2.303 }{ 6.792\times { 10 }^{ -3 } }  \right) log\left( \cfrac { 100 }{ 25 }  \right) = \left( \cfrac { 2.303\times 0.6021 }{ 6.792\times { 10 }^{ 2 } }  \right)= 20.34$ minutes.

For the decomposition of $H _2O _2(aq.)$, it was found that $V _{O _2} (t=15 min.)$ was 100 mL (at 0$^oC$ and 1 atm) while $V _{O _2}$ (maximum) was 200 mL (at 0$^oC$ and 2 atm). If the same reaction had been followed by the titration method and if $V _{KMnO _4}^{cM} (t = 0)$ had been 40 mL, what would $V _{KMnO _4}^{cM}(t = 15 min)$ have been?

  1. 30 mL

  2. 25 mL

  3. 20 mL

  4. 15 mL


Correct Option: A
Explanation:

200 ml at 2 atm corresponds to 400 ml at 1 atm. This is the maximum value
In 15 minutes, the volume is 100 ml.
Thus one fourth of the reaction is complete in 15 minutes.
Hence, the volume of $KMnO _4$ will be $\displaystyle \frac{3}{4} \times 40 = 30 mL$

Which of the following are example of pseudo unimolecular reactions?
1. Inversion of cane sugar
2. Decomposition of ozone
3. Decomposition of $N _{2} O _{5}$
4. Acid catalysed by hydrolysis of ester

  1. 2 and 4

  2. 1 and 4

  3. 1, 2 and 4

  4. 1, 2, 3 and 4


Correct Option: B
Explanation:

Inversion of cane sugar and Acid catalyzed by hydrolysis of ester are examples of pseudo unimolecular reactions.
Decomposition of ozone is a bimolecular reaction.
Decomposition of dintirogen pentoxide is also a bimolecular reaction.

Which of the following statement is/are correct ?

  1. The rate of the reaction involving the conversion of ortho-hydrogen to parahydrogen is $\displaystyle -\, \frac{d[H _2]}{dt}\, =\, k[H _2]^{3/2}$

  2. The rate of the reaction involving the thermal decomposition of acetaldehyde is $k[CH _3CHO]^{3/2}$

  3. In the formation of phosgene gas from CO and $Cl _2$, the rate of the reaction is $k[CO][Cl _2]^{1/2}$

  4. In the decomposition of $H _2O _2$, the rate of the reaction is $k[H _2O _2]$.


Correct Option: A,B,C,D
Explanation:

(A) The rate of the reaction involving the conversion of ortho-hydrogen to parahydrogen is $\displaystyle -\, \frac{d[H _2]}{dt}\, =\, k[H _2]^{3/2}$
The order of the reaction is 1.5.
(B) The rate of the reaction involving the thermal decomposition of acetaldehyde is $k[CH _3CHO]^{3/2}$
The order of the reaction is1.5.
(C) In the formation of phosgene gas from CO and $Cl _2$, the rate of the reaction is $k[CO][Cl _2]^{1/2}$
The order of the reaction is 1.5.
(D) In the decomposition of $H _2O _2$, the rate of the reaction is $k[H _2O _2]$.
The order of the reaction is 1.

The inversion of a sugar follows first-order rate equation which can be followed by noting the change in the rotation of the plane of polarization of light in the polarimeter. If $r _{\propto},\, r _{\zeta}$ and $r _0$ are the rotations at $t\, =\, \propto$, t = t, and t = 0, then the first order reaction can be written as:

  1. $\displaystyle k\, =\, \frac{1}{t}\, log\, \frac{r _{1}\, -\, r _{\propto}}{r _{0}\, -\, r _{\propto}}$

  2. $\displaystyle k\, =\, \frac{1}{t}\, ln\, \frac{r _{0}\, -\, r _{\propto}}{r _{1}\, -\, r _{\propto}}$

  3. $\displaystyle k\, =\, \frac{1}{t}\, ln\, \frac{r _{\propto}\, -\, r _{0}}{r _{\propto}\, -\, r _{1}}$

  4. $\displaystyle k\, =\, \frac{1}{t}\, ln\, \frac{r _{\propto}\, -\, r _{1}}{r _{\propto}\, -\, r _{0}}$


Correct Option: B
Explanation:

For a first order reaction $\displaystyle A \rightarrow P$, the expression for the rate constant is
$\displaystyle \displaystyle k\, =\, \frac{1}{t}\, ln\, \frac{ a}{a-x}$
Here, A is reactant, P is product, a is the initial concentration of A and $a-x$ is the concentration of A at time t.

The inversion of a sugar follows first order rate equation which is given below.
$\displaystyle \displaystyle k\, =\, \frac{1}{t}\, ln\, \frac{r _{0}\, -\, r _{\infty}}{r _{t}\, -\, r _{\infty}}$
Here, $\displaystyle a = r _{0}\, -\, r _{\infty}$ and $\displaystyle a-x = r _{t}\, -\, r _{\infty}$

The reaction, $Sucrose\xrightarrow [  ]{ { H }^{ + } } Glucose+Fructose$, takes  place at certain temperature while the volume of solution is maintained at $1$ litre. At time zero the initial rotation of the mixture is ${ 34 }^{ o }C$.After $30$ minutes the total rotation of solution is ${ 19 }^{ o }C$ and after a very long time, the total rotation is ${ -11 }^{ o }C$. Find the time when solution was optically inactive?

  1. $135$ min

  2. $103.7$ min

  3. $38.7$ min

  4. $45$ min


Correct Option: B
Explanation:

rate constant $k = \dfrac{2.303}{t}log\dfrac{(r _0 - r _\infty) }{(r _t-r _\infty)} = 0.0135$
At the point of optical inactiveness, rotation is zero. 

So, time taken is $ t =\dfrac{ 2.303}{k}log(45/11) = 103.7$ min.

Inversion of a sugar folllows first order rate equation which can be followed by nothing the change in rotation of the plane of polarization of light in the polarimeter. If $r _{\infty,}:r _t:and:r _0$ are the rotations at
 $t\,=\,\infty,t\,=\,t:and:t\,=\,0,$ then, first order reaction can be written as:

  1. $\;k\,=\,\displaystyle\frac{1}{t}log\displaystyle\frac{r _t-r _{\infty}}{r _0-r _{\infty}}$

  2. $\;k\,=\,\displaystyle\frac{1}{t}\,ln\displaystyle\frac{r _0-r _{\infty}}{r _t-r _0}$

  3. $\;k\,=\,\displaystyle\frac{1}{t}\,ln\displaystyle\frac{r _{\infty}-r _0}{r _{\infty}-r _t}$

  4. None of these


Correct Option: C
Explanation:

$\underset{d-Sucrose}{C _{12}H _{22}O _{11}}+H _2O\xrightarrow{H+}\underset{d-Glucose}{C _6H _{12}O _6}+\underset{l-Fructose}{C _6H _{12}O _6}$


Initially               a                Excess                  0                0 
After time t        a-x            Constant                x                x
At infinity           0               Constant               a                 a
If $r _0,r _t$ and $r _{\infty}$ be the observed angle of rotations of the sample at zero times, times $t$ and infinity respectively, and $k _1,k _2$ and $k _3$ proportionate in terms of sucrose,glucose and fructose, respectively.
Then,
$r _0=k _1a$
$r _t=k _1(a-x)+k _2x+k _3x$
$r _{\infty}=k _2a+k _3a$
From these equations it can be shown that
$\dfrac{a}{a-x}=\dfrac{r _0-r _{\infty}}{r _t-r _{\infty}}$
So, the expression for the rate constant rate of this reaction in terms of the optical rotational data may be 
put as $k=\dfrac{2.303}{t}\log \dfrac{r _0-r _{\infty}}{r _t-r _{\infty}}$

In the following reaction $2H _2O _2\rightarrow2H _2O+O _2$ rate of formation of $O _2$ is 3.6 M min$^{-1}$.


(a) What is rate of formation of $H _2O\ ?$        
(b) What is rate of disappearance of $H _2O _2$?

  1. (i) $7.2$ mol litre$^{-1}$ min$^{-1},$ (ii) $7.2$ mol litre$^{-1}$ min$^{-1}$

  2. (i) $3.6$ mol litre$^{-1}$ min$^{-1},$ (ii) $3.6$ mol litre$^{-1}$ min$^{-1}$

  3. (i) $14.4$ mol litre$^{-1}$ min$^{-1},$ (ii) $14.4$ mol litre$^{-1}$ min$^{-1}$

  4. None of these


Correct Option: A
Explanation:

$ (a)2H _{2}O _{2}\rightarrow 2H _{2}O+O _{2} $

We know, $ \dfrac{-1}{2}\dfrac{d[H _{2}O _{2}]}{dt} = \dfrac{-1}{2}\dfrac{d[H _{2}O]}{dt} = \dfrac{d[O _{2}]}{dt} $

$ \dfrac{d[H _{2}O]}{dt} = 2\dfrac{d[O _{2}]}{dt} = 2\times 3.6\,M\,min^{-1} $

$ \dfrac{d[H _{2}O]}{dt} = 7.2\,M\,min^{-1} $

$(b) \dfrac{-d[H _{2}O _{2}]}{dt} = \dfrac{2}{2}\dfrac{d[H _{2}O]}{dt} = \dfrac{-d[H _{2}O _{2}]}{dt} = 7.2\,M\,min^{-1} $ 

Option A is correct.