10/23/2018

Nuclear Chemistry

Radioactivity
› Nuclear chemistry, the study of reactions involving
changes in atomic nuclei, began with the discovery of
natural radioactivity.
› In 1895, Wilhelm Röntgen \ˈrent-gən , ˈrənt- , -jən ; ˈren-chən , ˈrən-\
noticed that cathode rays caused glass and metals to emit
very unusual rays.
– These rays penetrated matter, darkened covered photographic
plates, and caused fluorescence in some substances.
– Due to their unknown nature, he called them X rays.

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Radioactivity
› Not long after the discovery of X rays, Antoine Henri
Becquerel \be-ˈkrel , ˌbe-kə-ˈrel\ found, by accident, that exposing
thickly wrapped photographic plates to a certain uranium
compound caused them to darken, even without
stimulation by cathode rays.
– This meant that the radiation came from uranium itself.
– Like X rays, these rays were highly energetic and could not be
deflected by a magnet.

Radioactivity
› One of Becquerel’s students, Marie Curie, suggested the
name radioactivity to describe this spontaneous emission
of particles and/or radiation.
– Since then, any element that spontaneously emits radiation is said
to be radioactive.
› Three types of rays are produced by radioactive decay:
– α rays: consist of positively charged α particles
– β rays: consist of negatively charged β particles (electrons)
– γ rays: electrically neutral, not affected by external field

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Nuclear Reactions

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Nuclear Reactions
› The symbols for elementary particles are as follows:

› “e” represents an electron/positron in or from an atomic

orbital; “β” represents one from a nucleus via decay.
› In balancing any nuclear equation, we observe the
following rules:
– conservation of mass number (number of nucleons)
– conservation of atomic number (number of nuclear charges)

Nuclear Stability
› The density of the nucleus is exceedingly high:
– ~2 x 1014 g/cm3, roughly 9 trillion times denser than the densest
element, osmium
› From Coulomb’s law, we know that like charges repel and
unlike charges attract.
– How do the protons in the very dense nucleus stay intact amidst
such high repulsive forces?
› In addition to repulsion, there is the strong nuclear force
which acts only at a short range between nucleons.

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Nuclear Stability
› Nuclear stability is determined by the difference between
coulombic repulsion and strong nuclear attraction.
– If repulsion > attraction, the nucleus disintegrates, emitting
particles and/or radiation.
– If repulsion < attraction, the nucleus is stable.
› The neutron-to-proton ratio (n/p) is the principal factor
that determines whether a nucleus is stable.
– For stable atoms of elements with low atomic numbers, n/p ~ 1.
– As atomic number increases, more neutrons are needed to
counteract the stronger coulombic repulsion from protons,
and thus n/p > 1.

Nuclear Stability
› The following rules help predict nuclear stability:
– Nuclei that contain 2, 8, 20, 50, 82, or 126 protons or neutrons
are generally more stable than nuclei that do not possess these
numbers (called magic numbers).
– Nuclei with even numbers of both protons and neutrons are
generally more stable than those with odd numbers of these
particles.

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Nuclear Stability
› The following rules help predict nuclear stability:
– All isotopes of the elements with atomic numbers higher than 83
are radioactive.
– All isotopes of technetium (Tc, Z=43) and promethium (Pm, Z=61)
are radioactive.

Nuclear Stability
› Stable nuclei are located
within the belt of
stability.
› Most radioactive nuclei
lie outside this belt.

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Nuclear Stability
› Above the stability belt,
the n/p ratios are higher
than those within the
belt.
– Nuclei undergo β-particle
emission to lower this
ratio.

𝟏
𝟎𝒏 → 𝟏𝟏𝒑 + −𝟏𝟎𝜷

Nuclear Stability
› Below the stability belt,
the n/p ratios are lower
than those within the
belt.
– Nuclei undergo either
positron emission or
electron capture to
increase this ratio.

𝟏
𝟏𝒑 → 𝟏𝟎𝒏 + +𝟏𝟎𝜷
𝟏 𝟎
𝟏𝒑 + −𝟏𝒆 → 𝟏𝟎𝒏

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Nuclear Binding Energy

– the energy required to break up a nucleus into its component
protons and neutrons
› Nuclear binding energy represents the conversion of mass
into energy that occurs during an exothermic nuclear
reaction.
– The masses of nuclei are always less than the sum of the
masses of the nucleons.

Nuclear Binding Energy

for example:
– The fluorine-19 isotope has an atomic mass of 18.9984 amu.
– Its nucleus, containing 9 protons and 10 neutrons, should have a
mass of:
9(mp) + 10(mn) = 3.1803 x 10-26 kg = 19.1521 amu
(CONST-17 “u” for CASIO fx-570ES PLUS, in kg)
– This is larger than the measured mass of fluorine-19.
› The difference between the mass of an atom and the sum of
the masses of its protons, neutrons, and electrons is called
the mass defect.

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Nuclear Binding Energy

› The loss in mass shows up as energy given off to the
surroundings.
› The amount of energy is obtained using Einstein’s mass-
energy equivalence relationship:
𝐸 = 𝑚𝑐 2
∆𝐸 = ∆𝑚 𝑐 2

Nuclear Binding Energy

› In comparing the stability of any two nuclei, we must
account for the fact that they have different numbers of
nucleons.
› It is more meaningful to use the nuclear binding energy
per nucleon:
𝑛𝑢𝑐𝑙𝑒𝑎𝑟 𝑏𝑖𝑛𝑑𝑖𝑛𝑔 𝑒𝑛𝑒𝑟𝑔𝑦
𝑛𝑢𝑐𝑙𝑒𝑎𝑟 𝑏𝑖𝑛𝑑𝑖𝑛𝑔 𝑒𝑛𝑒𝑟𝑔𝑦 𝑝𝑒𝑟 𝑛𝑢𝑐𝑙𝑒𝑜𝑛 =
𝑛𝑢𝑚𝑏𝑒𝑟 𝑜𝑓 𝑛𝑢𝑐𝑙𝑒𝑜𝑛𝑠

› Binding energies per nucleon are greatest for elements in

the iron, cobalt, and nickel region (Group 8B elements).

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Kinetics of Radioactive Decay

› All radioactive decays obey first-order kinetics.
𝐫𝐚𝐭𝐞 𝐨𝐟 𝐝𝐞𝐜𝐚𝐲 𝐚𝐭 𝐭𝐢𝐦𝐞 𝒕 = 𝛌𝑵

where λ is the rate constant and N is the number of radioactive nuclei present at
time t.

› The corresponding half-life of radioactive decay is

𝒍𝒏 𝟐 𝟎. 𝟔𝟗𝟑
𝒕𝟏 = =
𝟐 𝝀 𝝀

Kinetics of Radioactive Decay

DISINTEGRATION RATES
– measures of the activity of the source of radioactivity
› disintegrations per minute (dpm) or disintegrations
per second (dps)
› SI unit
– 1 becquerel (Bq) = 1 dps
› non-SI unit
– 1 curie (Ci) = 3.7 x 1010 Bq
› per-second-disintegration of 1 gram of radium

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Kinetics of Radioactive Decay

ABSORBED DOSE
– measure of the energy deposited in a medium by ionizing
radiation
– used in the calculation of dose uptake in living tissue in both
radiation protection and radiology
› SI unit
– 1 gray (Gy) = 1 J/kg absorbing matter
› non-SI unit
– 1 rad = 0.01 Gy = 0.01 J/kg = 100 ergs/g matter

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