What is first order half life derivation?

1 Answer
Jul 19, 2018

Well, let us begin from the rate law... Is the FIRST-order half-life dependent on concentration?


The first-order rate law for the reaction

#A -> B#

is

#r(t) = k[A] = -(d[A])/(dt)#

where:

  • #r(t)# is the rate as a function of time, which we take to be the initial rate in #"M/s"#
  • #k# is the rate constant. What are the units? You should know this.
  • #[A]# is the concentration of a reactant #A# in #"M"#.
  • #(d[A])/(dt)# is the rate of disappearance of reactant #A#, a NEGATIVE value. But the negative sign forces the rate to be positive, fitting for a FORWARD reaction.

By separation of variables:

#-kdt = 1/([A])d[A]#

Integrate on the left from time zero to time #t#, and the right from initial concentration #[A]_0# to current concentration #[A]#. We obtain:

#-kint_(0)^(t)dt = int_([A]_0)^([A])1/([A])d[A]#

#-kt = ln[A] - ln[A]_0#

Therefore, the first-order integrated rate law is:

#color(green)(ln[A] = -kt + ln[A]_0)#

As we should recognize, the half-life is when the concentration drops by half. Hence, we set #[A]_(1//2) -= 0.5[A]_0# to get:

#ln0.5[A]_0 = -kt_(1//2) + ln[A]_0#

#ln0.5[A]_0 - ln[A]_0 = -kt_(1//2)#

#ln\frac(0.5cancel([A]_0))(cancel([A]_0)) = -kt_(1//2)#

#-ln0.5 = ln2 = kt_(1//2)#

As a result, the half-life is given by...

#color(blue)(barul|stackrel(" ")(" "t_(1//2) = (ln2)/k" ")|)#