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Lesson 14 · Second-order slowdown
The half-life that keeps growing
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The half-life that keeps growing

A second-order step needs two molecules in the same place at the same instant. As the reactant thins, those meetings get rare fast — so a second-order reaction does not just slow down, it slows down and then slows down again. Integrated, that is 1[A]=1[A]0+kt\dfrac{1}{[\mathrm{A}]} = \dfrac{1}{[\mathrm{A}]_0} + kt: [A][\mathrm{A}] is the concentration left at time tt, [A]0[\mathrm{A}]_0 the concentration when the clock read zero, tt the elapsed seconds, and kk the rate constant in L/(mol⋅s)\mathrm{L/(mol \cdot s)} — different units from every other order, which is the giveaway when a question refuses to say which order it is.

Work it as a straight line and it is easy: 1/[A]1/[\mathrm{A}] starts at 1/[A]01/[\mathrm{A}]_0 and climbs by kk each second. Then — and this is where the marks go — flip it back. The law hands you the RECIPROCAL of the concentration; an answer of 20 is not 20 mol/L, it is 0.05 mol/L wearing its reciprocal upside down.

Now the contrast worth memorising. Ask this law when half is gone and [A]0[\mathrm{A}]_0 refuses to cancel: t1/2=1k [A]0t_{1/2} = \dfrac{1}{k\,[\mathrm{A}]_0} — half-life in seconds, kk in L/(mol⋅s)\mathrm{L/(mol \cdot s)}, and [A]0[\mathrm{A}]_0 the STARTING concentration, genuinely in the answer. Start with less and the half-life is longer. Worse: after one half-life the concentration IS halved, so the next half-life is twice as long, and the one after that twice again. First order's clock ticks evenly forever; second order's clock stretches as you watch it.

[A]0t[A]k

1[A]=1[A]0+kt\frac{1}{[\mathrm{A}]} = \frac{1}{[\mathrm{A}]_0} + kt

  • [A][\mathrm{A}]= Concentration at time t (molar concentration)
  • [A]0[\mathrm{A}]_0= Initial concentration (molar concentration)
  • kk= Rate constant in L/(mol·s)
  • tt= Elapsed time (time)
Second-Order Integrated Rate Law solver →
[A]0t1/2k

t1/2=1k [A]0t_{1/2} = \frac{1}{k\,[\mathrm{A}]_0}

  • t1/2t_{1/2}= Half-life (time)
  • kk= Rate constant in L/(mol·s)
  • [A]0[\mathrm{A}]_0= Initial concentration (molar concentration)
Half-Life of a Second-Order Reaction solver →