General Features of the Atom

Nuclear Chemistry

CHM3010-Nuclear Chemistry

CHM3010-Nuclear Chemistry

Properties of the Three Key Subatomic Particles

Location Name(Symbol) Relative Absolute(C)* Relative(amu) Absolute(g) in the Atom Proton (p+) 1+ +1.60218x10-19 1.00727 1.67262x10-24 Nucleus

Atomic Symbols, Isotopes, Numbers

A J Z The Symbol of the Atom or Isotope

Charge

Mass

J = Atomic symbol of the element A = mass number; A = Z + N

Neutron

(n0)

1.00866

1.67493x10-24

Nucleus Outside Nucleus

Z = atomic number
(the number of protons in the nucleus)

Electron (e-)

1-

-1.60218x10-19

0.00054858

9.10939x10-28

N = number of neutrons in the nucleus Isotope = atoms of an element with the same number of protons, but a different number of neutrons

CHM3010-Nuclear Chemistry

CHM3010-Nuclear Chemistry

Sample Problem 2.3

Calculating the Atomic Mass of an Element

PROBLEM: Silver(Ag: Z = 47) has 46 known isotopes, but only two occur naturally, 107Ag and 109Ag. Given the following mass spectrometric data, calculate the atomic mass of Ag: Isotope
107Ag 109Ag

Mass(amu) 106.90509 108.90476

Abundance(%) 51.84 48.16

PLAN: We have to find the weighted average of the isotopic masses, so we multiply each isotopic mass by its fractional abundance and then sum those isotopic portions. SOLUTION: multiply by fractional portion of atomic mass(g) of each addmass isotopic portions atomic mass abundance of each from each isotope isotope isotope

Nuclear Reactions and Their Applications

mass portion from 107Ag = 106.90509amu x 0.5184 = 55.42amu mass portion from 109Ag = 108.90476amu x 0.4816 = 52.45amu atomic mass of Ag = 55.42amu + 52.45amu = 107.87amu
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Isotopes with unstable atomic nuclei are radioactive and are called radionuclides Radioactive isotopes undergo nuclear reactions as they emit high-energy particles and/or electromagnetic radiation By the early 1900s physicist realized that the mass of a particle could not always be treated as constant

Involve changes in electrons only Involve changes in the nucleus

CHM3010-Nuclear Chemistry

CHM3010-Nuclear Chemistry

The mass (m) of a particle depends on its velocity (v) relative to an observer
m=

The Law of Conservation of Mass - E nergy replaces the two independent laws:

mo 1 (v / c )
2

The sum of all the energy in the universe and the sum of all the mass (expressed as an equivalent in energy) is a constant

c = speed of light = 3.00x108 m/s v = speed of the particle in m/s mo = particles rest mass (mass at v = 0)

The Einstein equation relates the change in rest mass to an energy change

The rest mass of the particle can be measured in the lab when the sample is at rest (from our viewpoint)

E = moc 2

Because c is so large an enormous amount of energy accompanies even a small change is rest mass
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CHM3010-Nuclear Chemistry

The mass of an atomic nucleus is always a little smaller than the sum of the rest masses of each of its nucleons (protons and neutrons) The mass difference is called the mass defect The mass difference represents the amount of mass converted into energy, and released by the system, as the nucleons collect to form the nucleus

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This energy is also called the binding energy because this amount of energy would need to be added to break the nucleus apart The higher the binding energy, the more stable the nucleus The binding energy can be calculated using the Einstein equation and the mass defect

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Consider

the case of one helium-4 nucleus:

rest mass of an isolated proton = 1.007276470 u rest mass of an isolated neutron = 1.008664904 u rest mass of one 4 He nucleus = 4.001506 u The mass defect is then mo = 2(1.007276470 u) + 2(1.008664904 u) - 4.001506 u = 0.030377 u Using the Einstein equation E = 0.030377 u = 4.54 10
-12

The energy from forming only 4 g of helium (1 mol) could keep a 60 watt lightbulb burning for over 1440 years The formation of a nucleus from its nucleons is called nuclear fusion

No practical method for sustaining nuclear fusion currently exists on earth

1.6605403 10 1u

- 27

kg

(3.00 108 m s 1 ) 2

For the formation of 1 mol 4 He : E = 4.54 10 -12 J 6.02 10 23 nuclei = 2.73 1012 J mol 1 nucleus mol
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The binding energy per nucleon has a maximum at 56Fe, meaning it is the most stable of all nuclei

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As the mass number increases, the binding energy per nucleon begins to drop One expects, and finds, that some of the heavier isotopes might breakup and form more stable isotopes Nuclear fission is the spontaneous breaking apart of a nucleus to form isotopes of intermediate mass number Nuclear fission will be covered shortly

Except for hydrogen, all atomic nuclei have more than one proton, each bearing a positive charge The force of attraction that keeps the protons, (which repel), together is called the nuclear strong force The nuclear strong force overcomes the force of repulsion between protons and binds both the protons and neutrons together in the nucleus

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As the nucleus becomes heavy, the neutron / proton ratio required for nuclear stability becomes increasingly greater than 1:1.
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Figure 24.2

A plot of neutrons vs. protons for the stable nuclides

Sample Problem 24.2 Predicting Nuclear Stability PROBLEM: Which of the following nuclides would you predcit to be stable and which radioactive? Explain. (a) PLAN:
18 Ne 10

(b)

32 S 16

(c)

236 Th 90

(d)

123 Ba 56

Stability will depend upon the N/Z ratio, the value of Z, the value of stable N/Z nuclei, and whether N and Z are even or odd.

SOLUTION: (a) Radioactive. N/Z = 0.8; there are too few neutrons to be stable. (c) Radioactive. Every nuclide with Z > 83 is radioactive.
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(b) Stable N/Z = 1.0; Z < 20 and N and Z are even. (d) Radioactive. N/Z = 1.20; the diagram on shows stability when N/Z 1.3.
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Neutrons help dilute the electrostatic repulsions by intermingling with the protons in the nucleus
Nuclei

This is called radioactivity

About 50 of the approximately 350 naturally occurring isotopes are radioactive

with too few neutrons and lots of protons are often unstable and occur among radionuclides

Radionuclidies undergo radioactive decay, meaning they eject small nuclear fragments and sometimes high energy electromagnetic radiation as well

Naturally occurring radiation consists principally of alpha, beta, and gamma radiation Alpha radiation consists of alpha particles, which are helium-4 nuclei The particles bear a charge of +2, which is omitted from its symbol

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Figure 24.1 Silberberg

Types of Radioactive Decay: Balancing Nuclear Equations

Total A Total Z A Reactants = Total TotalZ Products

The behavior of three types of radioactive emissions in an electric field

Alpha decay - A decreases by 4 and Z decreases by 2. Every element heavier than Pb undergoes decay. Beta decay - ejection of a particle from the nucleus from the conversion of a neutron into a proton and the expulsion of 0-1. The product nuclide will have the same A, but will be one atomic number higher. Positron decay - a positron (01) is the antiparticle of an electron. A proton in the nucleus is converted into a neutron with the expulsion of the positron. A remains the same but the atomic number decreases by one. Electron capture - a nuclear proton is converted into a neutron by the capture of an electron. A remains the same but the atomic number decreases. Gamma emission - energy release; no change in Z or A.

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Sample Problem 24.1 Writing Equations for Nuclear Reactions PROBLEM: Write balanced equations for the following nuclear reactions: (a) Naturally occurring thorium-232 undergoes decay. (b) Chlorine-36 undergoes electron capture. PLAN: Write a skeleton equation; balance the number of neutrons and charges; solve for the unknown nuclide. (a)

Sample Problem 2.2

Determining the Number of Subatomic Particles in the Isotopes of an Element

PROBLEM: Silicon(Si) is essential to the computer industry as a major component of semiconductor chips. It has three naturally occurring isoltopes: 28Si, 29Si, and 30Si. Determine the number of protons, neutrons, and electrons in each silicon isotope. PLAN: We have to use the atomic number and atomic masses.

SOLUTION: #

232 90

Th
0 -1

228 88

Ra + X
232 90 A Z 4 Th 228 88 Ra + 2 He X

A = 228 and Z = 88 (b)

36 17

SOLUTION: The atomic number of silicon is 14. Therefore

28Si 29Si 30Si

Cl +

e
36 17

has 14p+, 14e- and 14n0 (28-14) has 14p+, 14e- and 15n0 (29-14) has 14p+, 14e- and 16n0 (30-14)

A = 36 and Z = 16

Cl + e S
0 -1 36 16
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Nuclear Stability and Mode of Decay

Very few stable nuclides exist with N/Z < 1. The N/Z ratio of stable nuclides gradually increases as Z increases. All nuclides with Z > 83 are unstable. Elements with an even Z usually have a larger number of stable nuclides than elements with an odd Z. Well over half the stable nuclides have both even N and even Z.

Sample Problem 24.3 Predicting the Mode of Nuclear Decay PROBLEM: Predict the nature of the nuclear change(s) each of the following radioactive nuclides is likely to undergo: (a) PLAN:
12 B 5

(b)

234 U 92

(c)

74 As 33

(d)

127 La 57

Find the N/Z ratio and compare it to the band stability. Then predict which of the modes of decay will give a ratio closer to the band.

SOLUTION: (a) N/Z = 1.4 which is high. The nuclide will probably undergo decay altering Z to 6 and lowering the ratio. (c) N/Z = 1.24 which is in the band of stability. It will probably undergo decay or positron emission. (b) The large number of neutrons makes this a good candidate for decay. (d) N/Z = 1.23 which is too low for this area of the band. It can increase Z by positron emission or electron capture.
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Predicting the Mode of Decay

Neutron-rich nuclides undergo decay. Neutron-poor nuclides undergo positron decay or electron capture. Heavy nuclides undergo decay.
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CHM3010-Nuclear Chemistry

Figure 24.3

Decay rate (A) = N/t

SI unit of decay is the becquerel (Bq) = 1d/s.

The 238U decay series

curie (Ci) = number of nuclei disinegrating each second in 1g of radium-226 = 3.70x1010d/s Nuclear decay is a first-order rate process. Large k means a short half-life and vice versa.

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Sample Problem 24.4 Finding the Number of Radioactive Nuclei PROBLEM: Strontium-90 is a radioactive by-product of nuclear reactors that behaves biologically like calcium, the element above it in Group 2A(2). When 90Sr is ingested by mammals, it is found in their milk and eventually in the bones of those drinking the milk. If a sample of 90Sr has an activity of 1.2x1012 d/s, what are the activity and the fraction of nuclei that have decayed after 59 yr (t1/2 of 90Sr = 29 yr) PLAN: The fraction of nuclei that have decayed is the change in the number of nuclei, expressed as a fraction of the starting number. The activity of the sample (A) is proportional to the number of nuclei (N). We are given the A0 and can find A from the integrated form of the first-order rate equation. Figure 24.4 SOLUTION: t1/2 = ln2/k ln N0/Nt = ln A0/At = kt so k = 0.693/29 yr = 0.024 yr-1 Fraction = decayed Fraction = decayed (1.2x1012-2.9x1011) (1.2x1012) 0.76
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Decrease in the number of 14C nuclei over time

ln At = -kt + ln A0

ln At = -(0.024yr-1)(59yr) + ln(1.2x1012d/s) ln At = 26.4 At = 2.9x1011d/s

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CHM3010-Nuclear Chemistry

CHM3010-Nuclear Chemistry

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Detection of radioactivity by an ionization counter

Detection

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Neutron Activation Analysis

Uses

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Sample Problem 24.6 Calculating the Binding Energy per Nucleon

The Interconversion of Mass and Energy

PROBLEM:

E = mc2 E = mc2 m = E / c2

The mass of the nucleus is less than the combined masses of its nucleons. The mass decrease that occurs when nucleons are united into a nucleus is called the mass defect. The mass defect (m) can be used to calculate the nuclear binding energy in MeV. 1 amu = 931.5x106 eV = 931.5MeV

Iron-56 is an extremely stable nuclide. Compute the binding energy per nucleon for 56Fe and compare it with that for 12C (mass of 56Fe atom = 55.934939 amu; mass of 1H atom = 1.007825 amu; mass of neutron = 1.008665 amu).

PLAN: Find the mass defect, m; multiply that by the MeV equivalent and divide by the number of nucleons. SOLUTION: Mass Defect = [(26 x 1.007825 amu) + (30 x 1.008665 amu)] - 55.934939 m = 0.52846 amu Binding energy =
12C

(0.52846 amu)(931.5 MeV/amu) 56 nucleons

= 8.790 Mev/nucleon

has a binding energy of 7.680 MeV/nucleon, so 56Fe is more stable.

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Figure 24.15

Diagram of an atomic bomb

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Figure 24.5

Radiocarbon dating for determining the age of artifacts

Sample Problem 24.5 Applying Radiocarbon Dating PROBLEM: The charred bones of a sloth in a cave in Chile represent the earliest evidence of human presence in the southern tip of South America. A sample of the bone has a specific activity of 5.22 disintegrations per minute per gram of carbon (d/min*g). If the ratio of 12C:14C in living organisms results in a specific activity of 15.3 d/min*g, how old are the bones? (t1/2 of 14C = 5730 yr) PLAN: Calculate the rate constant using the given half-life. Then use the first-order rate equation to find the age of the bones. SOLUTION: k = ln 2/t1/2 = 0.693/5730yr = 1.21x10-4yr-1 t = 1/k ln A0/At = 1/(1.21x10-4yr-1) ln (15.3/5.22) = 8.89x103 yr The bones are about 8900 years old.

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Figure 24.9

The use of radioisotopes to image the thyroid gland

asymmetric scan indicates disease normal

Figure 24.10

PET and brain activity

normal
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Alzheimers
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The increased shelf life of irradiated food

Exposure

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Copyright The McGraw-Hill Companies, Inc. Permission required for reproduction or display.

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