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Chemistry LibreTexts

6.4: Rates of Radioactive Decay

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    83322
    • Contributed by Anonymous
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    Learning Objectives

    • To know how to use half-lives to describe the rates of first-order reactions

    The rate of radioactive decay is an intrinsic property of each radioactive isotope that is independent of the chemical and physical form of the radioactive isotope. The rate is also independent of temperature. In this section, we will describe radioactive decay rates and how half-lives can be used to monitor radioactive decay processes.

    A Quick Primer from Chemical Kinetics

    As discussed previously, the half-life of a first-order reaction is independent of the concentration of the reactants. This becomes evident when we rearrange the integrated rate law for a first-order reaction to produce the following equation:

    \[\ln\dfrac{[\textrm A]_0}{[\textrm A]}=kt \label{21.4.1}\]

    Substituting [A]0/2 for [A] and t1/2 for t (to indicate a half-life) into Equation \(\ref{21.4.1}\) gives

    \[\ln\dfrac{[\textrm A]_0}{[\textrm A]_0/2}=\ln 2=kt_{1/2}\]

    Substituting \(\ln{2} \approx 0.693\) into the equation results in the expression for the half-life of a first-order reaction:

    \[t_{1/2}=\dfrac{0.693}{k} \label{21.4.2}\]

    Thus, for a first-order reaction, each successive half-life is the same length of time. Since radioactivity follows first order decay kinetics, these equations are also applicable for this type of nuclear reactions.

    In any sample of a given radioactive substance, the number of atoms of the radioactive isotope must decrease with time as their nuclei decay to nuclei of a more stable isotope. Using \(N\) to represent the number of atoms of the radioactive isotope, we can define the rate of decay of the sample, which is also called its activity (\(A\)) as the decrease in the number of the radioisotope’s nuclei per unit time:

    \[A=-\dfrac{\Delta N}{\Delta t} \label{21.4.3}\]

    Activity is usually measured in disintegrations per second (dps) or disintegrations per minute (dpm).

    The activity of a sample is directly proportional to the number of atoms of the radioactive isotope in the sample:

    \[A = kN \label{21.4.4}\]

    Here, the symbol k is the radioactive decay constant, which has units of inverse time (e.g., s−1, yr−1) and a characteristic value for each radioactive isotope. If we combine Equation \(\ref{21.4.3}\) and Equation \(\ref{21.4.4}\), we obtain the relationship between the number of decays per unit time and the number of atoms of the isotope in a sample:

    \[-\dfrac{\Delta N}{\Delta t}=kN \label{21.4.5}\]

    Equation \(\ref{21.4.5}\) is the same as the equation for the reaction rate of a first-order reaction, except that it uses numbers of atoms instead of concentrations. In fact, radioactive decay is a first-order process and can be described in terms of either the differential rate law (Equation \(\ref{21.4.5}\)) or the integrated rate law:

    \[N = N_0e^{−kt} \]

    \[\ln \dfrac{N}{N_0}=-kt \label{21.4.6}\]

    Because radioactive decay is a first-order process, the time required for half of the nuclei in any sample of a radioactive isotope to decay is a constant, called the half-life of the isotope. The half-life tells us how radioactive an isotope is (the number of decays per unit time); thus it is the most commonly cited property of any radioisotope. For a given number of atoms, isotopes with shorter half-lives decay more rapidly, undergoing a greater number of radioactive decays per unit time than do isotopes with longer half-lives. The half-lives of several isotopes are listed in Table \(\PageIndex{1}\), along with some of their applications.

    Table \(\PageIndex{1}\): Half-Lives and Applications of Some Radioactive Isotopes
    Radioactive Isotope Half-Life Typical Uses
    *The m denotes metastable, where an excited state nucleus decays to the ground state of the same isotope.
    hydrogen-3 (tritium) 12.32 yr biochemical tracer
    carbon-11 20.33 min positron emission tomography (biomedical imaging)
    carbon-14 5.70 × 103 yr dating of artifacts
    sodium-24 14.951 h cardiovascular system tracer
    phosphorus-32 14.26 days biochemical tracer
    potassium-40 1.248 × 109 yr dating of rocks
    iron-59 44.495 days red blood cell lifetime tracer
    cobalt-60 5.2712 yr radiation therapy for cancer
    technetium-99m* 6.006 h biomedical imaging
    iodine-131 8.0207 days thyroid studies tracer
    radium-226 1.600 × 103 yr radiation therapy for cancer
    uranium-238 4.468 × 109 yr dating of rocks and Earth’s crust
    americium-241 432.2 yr smoke detectors


    Radioisotope Dating Techniques

    In our earlier discussion, we used the half-life of a first-order reaction to calculate how long the reaction had been occurring. Because nuclear decay reactions follow first-order kinetics and have a rate constant that is independent of temperature and the chemical or physical environment, we can perform similar calculations using the half-lives of isotopes to estimate the ages of geological and archaeological artifacts. The techniques that have been developed for this application are known as radioisotope dating techniques.

    The most common method for measuring the age of ancient objects is carbon-14 dating. The carbon-14 isotope, created continuously in the upper regions of Earth’s atmosphere, reacts with atmospheric oxygen or ozone to form 14CO2. As a result, the CO2 that plants use as a carbon source for synthesizing organic compounds always includes a certain proportion of 14CO2 molecules as well as nonradioactive 12CO2 and 13CO2. Any animal that eats a plant ingests a mixture of organic compounds that contains approximately the same proportions of carbon isotopes as those in the atmosphere. When the animal or plant dies, the carbon-14 nuclei in its tissues decay to nitrogen-14 nuclei by a radioactive process known as beta decay, which releases low-energy electrons (β particles) that can be detected and measured:

    \[ \ce{^{14}C \rightarrow ^{14}N + \beta^{−}} \label{21.4.7}\]

    The half-life for this reaction is 5700 ± 30 yr.

    The 14C/12C ratio in living organisms is 1.3 × 10−12, with a decay rate of 15 dpm/g of carbon (Figure \(\PageIndex{1}\)). Comparing the disintegrations per minute per gram of carbon from an archaeological sample with those from a recently living sample enables scientists to estimate the age of the artifact, illustrated below. Using this method implicitly assumes that the 14CO2/12CO2 ratio in the atmosphere is constant, which is not strictly correct. Other methods, such as tree-ring dating, have been used to calibrate the dates obtained by radiocarbon dating, and all radiocarbon dates reported are now corrected for minor changes in the 14CO2/12CO2 ratio over time.

    14.18.jpg
    Figure \(\PageIndex{1}\): Radiocarbon Dating. A plot of the specific activity of 14C versus age for a number of archaeological samples shows an inverse linear relationship between 14C content (a log scale) and age (a linear scale).

    Example \(\PageIndex{1}\)

    In 1990, the remains of an apparently prehistoric man were found in a melting glacier in the Italian Alps. Analysis of the 14C content of samples of wood from his tools gave a decay rate of 8.0 dpm/g carbon. How long ago did the man die?

    Given: isotope and final activity

    Asked for: elapsed time

    Strategy:

    A Use Equation \(\ref{21.4.4}\) to calculate N0/N. Then substitute the value for the half-life of 14C into Equation \(\ref{21.4.2}\) to find the rate constant for the reaction.

    B Using the values obtained for N0/N and the rate constant, solve Equation \(\ref{21.4.6}\) to obtain the elapsed time.

    Solution

    We know the initial activity from the isotope’s identity (15 dpm/g), the final activity (8.0 dpm/g), and the half-life, so we can use the integrated rate law for a first-order nuclear reaction (Equation \(\ref{21.4.6}\)) to calculate the elapsed time (the amount of time elapsed since the wood for the tools was cut and began to decay).

    \[\begin{align*}\ln\dfrac{N}{N_0}&=-kt \\[4pt] \dfrac{\ln(N/N_0)}{k}&=t\end{align*}\]

    A From Equation \(\ref{21.4.4}\), we know that A = kN. We can therefore use the initial and final activities (A0 = 15 dpm and A = 8.0 dpm) to calculate N0/N:

    \[dfrac{A_0}{A}=\dfrac{kN_0}{kN}=\dfrac{N_0}{N}=\dfrac{15}{8.0} \nonumber\]

    Now we need only calculate the rate constant for the reaction from its half-life (5730 yr) using Equation \(\ref{21.4.2}\):

    \[t_{1/2}=\dfrac{0.693}{k} \nonumber\]

    This equation can be rearranged as follows:

    \[k=\dfrac{0.693}{t_{1/2}}=\dfrac{0.693}{5730\textrm{ yr}}=1.22\times10^{-4}\textrm{ yr}^{-1} \nonumber\]

    B Substituting into the equation for t,

    \[t=\dfrac{\ln(N_0/N)}{k}=\dfrac{\ln(15/8.0)}{1.22\times10^{-4}\textrm{ yr}^{-1}}=5.2\times10^3\textrm{ yr} \nonumber\]

    From our calculations, the man died 5200 yr ago.

    Exercise \(\PageIndex{1}\)

    It is believed that humans first arrived in the Western Hemisphere during the last Ice Age, presumably by traveling over an exposed land bridge between Siberia and Alaska. Archaeologists have estimated that this occurred about 11,000 yr ago, but some argue that recent discoveries in several sites in North and South America suggest a much earlier arrival. Analysis of a sample of charcoal from a fire in one such site gave a 14C decay rate of 0.4 dpm/g of carbon. What is the approximate age of the sample?

    Answer

    30,000 yr

    Summary

    • The half-life of a first-order reaction is independent of the concentration of the reactants.
    • The half-lives of radioactive isotopes can be used to date objects.

    The half-life of a reaction is the time required for the reactant concentration to decrease to one-half its initial value. The half-life of a first-order reaction is a constant that is related to the rate constant for the reaction: t1/2 = 0.693/k. Radioactive decay reactions are first-order reactions. The rate of decay, or activity, of a sample of a radioactive substance is the decrease in the number of radioactive nuclei per unit time.

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