Friday, May 5, 2017

physical chemistry - Does a first order reaction really get completed only at infinity?


For a $1^{\text{st}}$ order reaction $ A \rightarrow B$, the corresponding rate law is: $$\text{rate} = k[A]^{1}$$ and the integrated rate law for this is $$ \ln \left(\frac{A}{A-x}\right) = kt$$


Going by this equation, every first-order reaction must get completed only at infinity. Is this true? If not, then what is the correct explanation?



Answer



As far as I can see, the expression you have come up with is not entirely correct. If we assume that the reaction is $\ce{A -> B}$ (i.e. saying that it is approximately irreversible, or that $k_\mathrm{reverse} \ll k_\mathrm{forward}$), we have:


$$ \mathrm{rate} = \frac{\mathrm{d}[\ce{A}]}{\mathrm{d}t} = -k[\ce{A}] $$


Separating:


$$ \frac{\mathrm{d}[\ce{A}]}{[\ce{A}]} = -k\,\mathrm{d}t $$


Integration gives:



$$ \ln\frac{[\ce{A}]}{[\ce{A}]_0} = -kt $$ $$ [\ce{A}] = [\ce{A}]_0 \mathrm e^{-kt} $$


Here, $[\ce{A}]_0$ is the initial concentration of $\ce{A}$. It is correct that mathematically, $[\ce{A}] > 0$ for all $t<\infty$, from the last equation. In practise, however, the amount of $[\ce{A}]$ after a certain time interval $t$ will be negligibly small. How long it takes depends on $k$; if $k$ is large, the time for the reaction to go essentially to completion will be short.


No comments:

Post a Comment

periodic trends - Comparing radii in lithium, beryllium, magnesium, aluminium and sodium ions

Apparently the of last four, $\ce{Mg^2+}$ is closest in radius to $\ce{Li+}$. Is this true, and if so, why would a whole larger shell ($\ce{...