Experimental evidence for the structure of atoms

1. Discovery of electricity and ions (atoms with electric charge) 2. Discovery of Periodic Table (Mengyelejev, 1869) 3. Discovery and interpretation of spectra (basis of emission and absorption spectroscopy) (Bunsen, Kirchhoff, Balmer, Rntgen, 2nd half of 19th century) 4. Discovery of electron and determination of its parameters (Discovery: Stoney 1874, name: Helmholtz 1881 electron determination of mass and charge: Thomson, Millikan) 5. Discovery of radioactivity (Becquerel, 1896) 6. Rutherfords scattering experiment (1905) (Discovery of nucleus and electron orbitals)

Rutherford Scattering Experiment

Rutherford scattering experiment

Irradiation of a gold foil by alpha particles: Discovery of nucleus Nobel prize (1908).

STRUCTURE OF THE NUCLEUS, RADIOACTIVITY, NUCLEAR ENERGY

atom = nucleus + electrons to remove electron: ~ energy of chemical reactions nucleus = protons + neutrons to decompose nuclei: ~ 106-7 energy of chemical reactions Scientific study: usually in nuclear physics, not chemistry

The atomic nucleus must be very small, its radius is about 1/100000 of the radius of the atom

Importance: nuclear weapons, nuclear energy, radioactive tracers in medicine and medical diagnostics, radioactive dating

The structure of atoms

Constituents of atoms: nucleus + electrons Constituents of nucleus: proton + neutron The free atoms are neutral: Number of protons and electrons of any atoms are the same. Major parameters for the characterization of an atom:
A Z

The mass and charge of particles and atoms

Electron: Proton: Neutron: me = 9,10938910-31 kg ee = -1,60217710-19 C mp = 1,67262310-27 kg ep = 1,60217710-19 C mn = 1,67492810-27 kg en = 0 (Stoney-1874/Thomson-1897) (Rutherford - 1919) (Chadwick -1932)

mp/me = 1836

mn/mp = 1,00138

A=Z+N

X = chemical symbol

Mass of a hydrogen atom: mp + me = 1,673510-27 kg = 1,673510-24 g

Z = number of protons or electrons (atomic number) N = number of neutrons A = mass number

Isotopes and chemical elements

The chemical properties of the elements are determined by the atomic number which is the number of protons and electrons. The number of neutrons in the nucleus, however, can be different isotopes ISOTOPES = atoms with identical atomic numbers but different mass numbers
mass number symbol

Applications of isotopes
Isotopes of hydrogen
1H

: 2D : 3T = 99,9844 : 0,0156 : 10-10

D2O: heavy water (different spin of nucleus, solvent in NMR spectroscopy) T: radioactive dating (t1/2: 12,33 year) Isotopes of carbon:
12C

: 13C : 14C = 98,9 : 1,1 : 10-10

12 6
atomic number

carbon - 12

12C: 13C:

unit for mol used in NMR spectroscopy 14C: radioactive dating, (t : 5715 year) 1/2 11C: artificial (emission of positrons, PET)

Becquerel's Discovery Henri Becquerel: radioactivity

- tries to study phosphorescence and fluorescence - studied ores containing uranium - used photographic plates -March 1896: some plates that have not been exposed to light but were developed by mistake showed IMAGES - plates were stored near the uranium ore Uranium ores emit some sore of radiation that darken photographic plates

Marie & Pierre Curie

late 1890s and early 1900s introduced the term 'radioactivity' studied radioactivity in detail discovered new elements: Ra, Po identified three different types of radiation discovered that gases often form during radioactive processes (emanation)

NUCLEAR REACTIONS
14 7

nuclides
1 1

N + He
4 2

17 8

O+ H

nuclear equation

A nuclear reaction involves a change in an atom's nucleus, usually producing a different element. Different isotopes of an element have essentially the same behavior in chemical reactions but often have completely different properties in nuclear reactions. The rate of a nuclear reaction is unaffected by a change in temperature or pressure or by the addition of a catalyst. The nuclear reaction of an isotope is essentially the same, regardless of its actual chemical form. The energy change of a nuclear reaction is far greater than that of chemical reactions.

Radioactivity
Radioactive decay: spontaneous nuclear reaction involving one nuclide only. It is always accompanied by radiation. alpha () radiation: positively charged heavy particles 4He2+ ions (helium-4 nuclei) beta () radiation: negatively charged light particles electrons gamma () radiation: neutral particles electromagnetic radiation (light) with extremely high energy

Radioactive decay types

decay: emission of an particle form the nucleus, and usually radiation
238 92

U
A ZE

234 90

Th + 4 He 2
A4 Z 2 E'

General :

+ 4 He 2

decay: emission of an electron from the nucleus by the conversion of one neutron to proton and usually radiation
131 53

131 54

Xe + e
A Z +1E'

General :

A ZE

+ e

Radioactive decay types

+ decay: emission of a positron (e+, electron-like particle with positive charge) from the nucleus by the conversion of one proton to neutron usually only radiation
40 19

Radioactive decay types

isomeric decay: energy change within the nucleus without any noticeable change in composition
99 m 43

40 18

Ar + e

Tc

99 43

Tc
E A E' Z

General :

A ZE

A Z 1E'

+ e+

General :

Am Z

electron capture: capture of an electron from the electron cloud in the nucleus usually only radiation
197 80

Hg + e
A ZE

197 79

Au
A Z 1E'

m: metastable nucleus, an excited nucleus with excess energy

General :

+e

KINETICS OF RADIOACTIVE DECAY

first-order process: the decay rate is proportional to the number of radioactive nuclides present Rate = k N
ln 2 0.693 = t = k k

exponential form

REMINDER !!

logarithmic form

exponential curve

half-life (t):

Nt = N0e kt ln Nt = kt N0

exponential form

ln N /N 0

k: decay constant

N: number of nuclides

slope = k

logarithmic form

(t) Time (s)

Time (s)

Radioactive half-lives
Isotope name Tritium Helium-8 Carbon-14 Phosphorus-32 Potassium-40 Cobalt-60 Technetium-99m Iodine-123 Uranium-235 Darmstadtium-266 symbol decay
3H 8He 14C 32P 40K 60Co 99mTc 123I 235U 266Ds

half-life 12.3 years 0.12 s 5730 years 14.3 days 1.3 109 years 5.3 years 6.0 hours 13.3 hours 7.0 108 years 3 106 s

RADIOACTIVITY OF ELEMENTS
Every element has at least one radioactive isotope (which does not necessarily occur in nature) stable isotope = no radioactivity and decay is detectable
61Pm

+ i.d. e.c.

and 43Tc do not have non-radioactive isotopes

Elements after 82Pb do not have non-radioactive isotopes, although some radioactive isotopes have very long halflives
209Bi 238U

t = 1.9 1019 years hardly detectable! t = 4.5 109 years

NUCLEAR STABILITY
Stable isotopes: low atomic numbers number of neutrons is close to number of protons e.g. 12 C, 14 N, 16 O, 19 F, 23 Na, 40 Ca 6 7 8 9 11 20 high atomic numbers gradually increasing excess of neutrons e.g. 55 Mn, 75 As, 132 Xe, 169 Tm, 208 Pb 25 33 54 69 82 even numbers for both protons and neutrons are favored some elements with high even atomic number have a lot of stable isotopes
54Xe

e.g.

50Sn

10 stable isotopes,

9 stable isotopes

RADIOACTIVE ISOTOPES
Why do radioactive isotopes occur in nature? 1. very long half-life
40K 238U

RADIOACTIVE DECAY SERIES

The product of a radioactive decay can also be radioactive 238U 234Th 234Pa 234U 230Th 226Ra 222Rn 218Po 214Pb 214Bi 214Po

1.9 109 years 4.5 109 years

estimated age of the Earth 5 109 years estimated age of the Universe 1.5 1010 years Why does Ra occur in nature? longest-lived isotope 226Ra has t = 1.6 103 years 2. continuously produced by the radioactive decay series starting from 238U

210Pb 210Bi 210Po 206Pb

The first half-life is very long these isotopes occur in nature Similar natural decay series:
235U

... 207Pb ... 208Pb

232Th

Other natural sources of short-lived radioactive isotopes: nonspontaneous nuclear reactions driven by energetic cosmic rays

3H

t = 12.3 years

14 7

N+n N+n

12 6

C + 3H 1 C + 1H 1

14C t = 5730 years

14 7

14 6

A small steady-state concentration is kept up by the equilibrium of continuous production and decay. uses in radioactive dating

Applications of radioactive isotopes

1. Dating 2. Medical diagnostics:
99mTc 99mTc

Radiocarbon dating
Prof. Willard F. Libby, 1940s 1960 Nobel prize in chemistry

99Ru 99Tc

(t1/2 = 105 v) (t1/2 = 6 ra)

14C

t = 5730 40 years

(Cambridge t)

( 66 h ) n m 98 99 Mo 9943Tc 42 42 Mo
3. Radiation therapy: external internal

t = 5568 30 years (Libby t) tiny, but more or less stable concentration of 14C in air

4. Isotope tracing: Hevesy Gyrgy - George von Hevesy Nobel prize: 1943

Radiocarbon dating

radioactive decay:
14N 14C

Radiocarbon dating
1 mg carbon aged 5000 years: ~ 20 million 14C atoms 1 decay event in every 3,5 hours!!!! upper limit for AMS dating: ~ 50000 years Sample size: sample wood, charcoal carbonates bone radioactivity 8-12 g 35 g 100-200 g AMS 5-10 mg 15 mg 1g

+ e

n(14C) = n0et
n(14C) is measurable, n0 and are known calculation of t measurement of n(14C): radioactivity: small, insensitive mass spectrometry: good sensitivity AMS: Accelerator Mass Spectrometry

Radioactive dating: decay series of U

not 238U (t = 4,5 billion years) !!!
238U 234U: 230Th: 234Th

BINDING ENERGY IN THE NUCLEUS

Mass of 4He atom: 4.00260 amu
4He:

24 days 234

Pa

36 days 234

2 protons + 2 neutron + 2 electrons 2 1.00728 = 2.01456 amu

0,0055 % of natural U, t = 245000 years t = 75400 years (232Th: t = 14 billion years)

Mass of 2 protons:

Mass of 2 neutrons: 2 1.00866 = 2.01732 amu Mass of 2 electrons: 2 0.00055 = 0.00110 amu 4.03298 amu

equilibrium in a radioactive decay series

U238NU238 = Th234NTh234 = Pa234NPa234 = U234NU234 = Th230NTh230 = ........

the time of the approach to the equilibrium is governed by the half life of the daughter isotope

m = 0.03038 amu MASS DEFECT

found for every nucleus!

BINDING ENERGY IN THE NUCLEUS

E = mc2

Einstein equation

(c: speed of light)

fission fusion

binding energy of a nucleus c = 3.00 108 ms1

E = 2.73 1012 Jmol1 = 2.73 109 kJmol1 for 4He

Enucleon = E/A
average binding energy per nucleon commonly used units of energy 1 eV = 1 electronVolt = 1.602 1019 J
(= 96.5 kJ/mol)

fission and fusion can both be used to produce energy

1 MeV = 1 MegaelectonVolt = 1.602 1013 J (= 9.65 107 kJ/mol)

Nuclear fission: fragmentation of a nucleus on the impact of a neutron

Uses nuclear fission: uncontrolled nuclear chain reaction: huge explosion, first-generation nuclear weapons controlled nuclear chain reaction: nuclear reactors problem 1: 235U is only 0.7 % of natural uranium, needs to be enriched 239Pu, 241Pu can also be used for fission they do not occur in nature, but can be produced in nuclear reactors

235 92

U+n

142 56

Ba +

91 36

Kr + 3n

problem 2: a lot of long-lived radioactive isotopes are produced by fission (nuclear waste) Oklo phenomenon: natural nuclear reactor a few million years ago in Oklo, Gabon

Nuclear chain reaction

Atomic bomb
Fissile bomb: U-235: enrichment of natural uranium (gun method) Pu-239: synthesis in nuclear reactors from U-238 by nuclear reactions (implosion method) U-233: distant possibility, can be prepared from Th-232 in a nuclear reactor largest first-generation bomb: USA Ivy King 500 kt

Nuclear fusion: build-up of nuclei from lighter nuclei

1H 1H

+ 1H 2H + e + 2H 3He + 3He 4He + 2 1H + 1H 4He + e

3He 3He

overall: Importance:

4 1H 4He + 2 e

energy producing processes in stars much more efficient nuclear weapons (hydrogen bomb) not suitable for energy production at present (TOKAMAK, no nuclear waste produced)

Hydrogen bomb
thermonuclear weapon Three phase: 1. implosion weapon 2. 2D/3T fusion 3. U-238 fission 1951 USA: Edward Teller and Stanislaw Ulam 1955 Soviet Union: Andrei Sakharov

LIVING WITH RADIOACTIVITY

Ionizing effect 'ionizing radiation' 1. Detection of radiation: Geiger counters or scintillation counters 2. Radioactivity is natural: it is always around as background radiation at low levels 3. Biological effects: direct damage to living tissue, increased risk of cancer depends very much on the dose (amount) of radiation Unit

Measuring Radiation
quantity decay events (SI) decay events absorbed energy (SI) absorbed energy tissue damage (SI) tissue damage description 1 decay/s = 3.7 1010 Bq 1 J/kg = 0.01 Gy = q Gy = 0.01 Sv

Becquerel (Bq) Curie (Ci) Gray (Gy) Rad Sievert (Sv) Rem

q: dimensionless constant depending on the type of radiation

Measuring Radiation - Units

Activity: radiation intensity 1 Bq (Becquerel) = 1 decay/s Ci (Curie) = 3,71010 decay/s (1 Ci activity of 1 g radium)
Time

Radiation Biological effects

Dose 200 rad day 1 week 1-3 lack of appetite, weakness, diarrhoea, paleness, bolding 500 rad lack of appetite, weakness, diarrhoea, paleness, bolding, 50% probability of death 1000 rad nausea, vomitting, diarrhoea, fever, dehydration, body weight loss, death nausea, vomitting, decrease in white blood cell numbers

Radiation dose: 1 R (roentgen) = generation of 2,08109 ion pairs in normal air Absorbed dose: 1 rad = 102 J/1 g absorbed 1 Gy (Gray) = 1 J/kg (= 0,1 rad) 1 rem = A1 rad 5 (neutron) 10 ()

Dose for tissue damage: rem: roentgen equivalent for man A: biological efficiency = 1 (, , X) LD50/30 days (50% death within 30 days) rem humans 500 rat 700 dog 300

after 4 beginning of weeks recovery, genetic damage (heritable)

Man-made nuclear reactor

History of the atomic bomb

6 January 1939: First publications of fission reaction 2 August 1939: Albert Einsteins letter to president Roosevelt 2 December 1942: first atomic reactor, Enrico Fermi and Le Szilrd 16 July 1945: first atomic bomb, New Mexik 6 and 9 August 1945: explosions in Japan

Hiroshima: 6 August 1945

Hiroshima: after explosion

Enola Gay and Little boy (13kt)

Nagasaki: 9 August 1945

Tsar bomb
largest bomb ever made original plan: 100 Mt actual power: 50 Mt length: 8 m, diameter: 2 m, mass: 27 t inconveniently large for use in war

Fat man (21kt) history background: first Berlin Wall in August 1961

Tsar bomb

Tsar bomb
mushroom Cloud: height: 60 km width: 30-40 km fireball:

Tu-95: largest Soviet bomber in 1961

test: 30 October 1961, Novaya Zemlya

Scotlands secret bunker

bunker for political leaders in South Scotland

Scotlands secret bunker

150 m long entrance tunnel, disguised as a simple farmhouse on the surface

3 m thick concrete wall one of the largest bunkers in the UK capacity: 300 people large communication center

the neutron component of cosmic rays has not been steady in the last 50000 years calendar years radiocarbon years calibration dendrochronology up to 11000 years other radioactive dating methods (based on U)

C. S. M. Turney et al. Nature 443, E3 (2006).

10

Past few centuries

1960s: atmospheric nuclear bomb testing

14 C =

14

C%(sample )14 C%(standard) 14 C%(standard)

Possibility of short-term dating

Human age from tooth enamel

K. L. Spalding et al. Nature 437, 333 (2005).

K. L. Spalding et al. Nature 437, 333 (2005).

1988: a sample of 10 70 mm AMS radiocarbon dating Zrich, Tucson 12901360 A. D. first occurence in documents: 1353

Radioactive dating: decay series of U

formation of CaCO3 in living organisms (e.g. shells): soluble U is incorporated, insoluble Th and Pa not (separation) start of apparoach to equilibrium measurements: 230Th/234U ratio
230 234

Th U234 = (1 e Th230t ) U Th230

practical application: 100 500000 years Same concept based on 235U decay series Holy Shroud of Turin: St. Johns Cathedral, Turin, Italy
231Pa

t = 32500 years

235U

t = 704 million years

11

Potassium-argon dating
Potassium-containing rocks (e.g. ash) are formed in volcanic processes withous Ar inclusions
40K 40Ar

t = 1.3 billion years

40K:

0.01 % (present)

40

Ar = C (1 e K40t ) 39 K
+n
39Ar

39K

measurable after neutron activation as 39Ar

39K

+p ratio

Isotopic measurement:

40Ar/39Ar

Application: geological ages > 500000 years

12