Chapter 3 - Nuclear Properties

Nuclear binding energy, mass defect, and binding energy mass defect -atomic mass of any atom besides 1H is less than the sum of the protons,
neutrons, and electrons. -is a measure of the binding energy of the protons and neutrons in the nucleus -loss of mass and liberation of every are related by Einsteins equations.

E = mc 2
Li

Assume the mass defect originates solely from the interaction of protons 7 and neutrons in the nucleus. Estimate the binding energy of Li
3

Observed atomic mass

7 3

= 7.01600 u

1 u = 1.6605410-27 kg Electron rest mass = 9.1093910-31 kg Proton rest mass = 1.6726210-27 kg Neutron rest mass = 1.6749310-27 kg c = speed of light = 2.998x108 m/s

Radioactivity nuclear emissions

Radioactivity nuclear transformations

Radioactivity kinetics of decay

Artificial Isotopes
Nuclear reactions may occur when nuclei are bombarded with high energy neutrons or positively charged particles.
27 13 4 30 Al + 2 He15 P + 01n

27 13

30 Al ( , n)15 P

Initial nuclide(incoming particles or quanta, outgoing particles or quanta) final nuclide

30 15 30 P14 Si + +

t1/2 = 3.2 min

32 16

32 1 S + 01n15 P +1 H
fast

32 15 31 15

32 P16 S + 32 P + 01n15 P +
slow

t1/2 = 14.3 days

Production of artificial nuclides has two consequences: production of artificial isotopes of elements that do no not possess naturally occurring radioisotopes synthesis of transuranium elements (Z 93), nearly all of which are exclusively man-made.

Nuclear Fission

235 92

U + 01n fission _ products + x 01n + energy

235 92 138 1 U + 01n95 39Y + 53 I +30 n + energy

Branching Chain Reaction

Production of energy by nuclear fission

238 92
239 92

U + 01n 239 92 U +

U 239 239 93 Np 94 Pu

Transuranium elements
249 97 260 4 1 Bk +18 8 O 103 Lr + 2 He +30 n 261 1 Cm +18 8 O 104 Rf +50 n

248 96

Application of Isotopes
Infrared Spectroscopy (IR) Reduced mass and corresponding shift of absorption Rapid deuterium exchange reactions to investigate N-H, O-H, and C-H assignments in spectra.

=
Kinetic Isotope Effect Probe reaction mechanisms Radiocarbon Dating Probe reaction mechanisms Analytical Applications

1 2c

Solubilities of sparingly soluble salts and vapor pressures of involatile substances

Sources of 2H and

13C

Isotopically enriched solvents needed for NMR experiments At the anode

2 H 2O O2 + 4 H + + 4e 4 H 2O + 4e

At the cathode

H D gas Separation _ Factor = 6 H 2 H 2 + 4OH D solution

H 12CN ( g ) +[13CN ] (aq ) H 13CN ( g ) +[12CN ] ( aq )

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K = 1.026 K = 1.012

CO2 ( g ) + [ H 12CO3 ] (aq)12CO2 ( g ) + [ H 13CO3 ] (aq )

Nuclear Spin

A nucleus with an odd atomic number or an odd mass number has a nuclear spin. The spinning charged nucleus generates a magnetic field.

External Magnetic Field

When placed in an external field, spinning protons act like bar magnets.

Two Energy States

The magnetic fields of the spinning nuclei will align either with the external field, or against the field. A photon with the right amount of energy can be absorbed and cause the spinning proton to flip.

The NMR Spectrometer

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The NMR Graph

CH3 H3C Si CH3 CH3

Delta Scale

=>

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Location of Signals

More electronegative atoms deshield more and give larger shift values. Effect decreases with distance. Additional electronegative atoms cause increase in chemical shift.

Typical Chemical Shifts, 1H

12

Intensity

Chemical Shift ()

13

Intensity

Chemical Shift ()

Intensity

Chemical Shift ()

14

Intensity

Chemical Shift ()

Intensity

Chemical Shift ()

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Intensity

Chemical Shift ()

Coupling to the first 1H (2 * 1/2 + 1 = 2) Coupling to the second 1H 2

22 111 111

Coupling to the third 1H

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Doublet: 1 Adjacent Proton

17

Triplet: 2 Adjacent Protons

Intensity

Chemical Shift ()

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Proton-Coupled

13C

Spectra

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Proton-coupled

13C

spectra for ethyl phenylacetate.

Proton-decoupled

13C

NMR spectrum for ethyl phenylacetate.

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Timescales of experimental Techniques

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Mssbauer Spectroscopy

57Co electron capture 57Fe*

t1/2=270 days
136.32 keV

57Fe* 57Fe

14.41 keV t1/2=99.3 ns 0 keV

Mssbauer Spectroscopy: Fe3(CO)12

First prepared 1907, but the structure eluded chemists for almost 50 years Molecular formula established 1930, three Fe(CO)4 units per molecule Over the next 30 years a variety of structures were proposed, an example being a high-symmetry structure

Early X-ray diffraction studies were unsuccessful because of disorder in the molecular structure IR spectroscopic studies indicated two types of carbonyl ligands Terminal Bridging

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