| 1. The Big Bang | 2.Star Formation |
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| 3. Supernova Explosion | 4. Solar Nebula Condenses |
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| 5. Sun & Planetary Rings Form | 6. Earth Forms |
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| 7. Earth's Core Forms | 8. Oceans & Atmosphere Forms |
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Astronomers and physicists denote the build-up of heavier elements from
lighter ones as "nucleosynthesis".
Only the very lightest elements
(Hydrogen, Helium and Lithium [2]) were created at the time of the Big
Bang and therefore
present in the early universe.All
the other heavier elements we now see around us were produced at a later
time by nucleosynthesis inside stars. In those"element factories", nuclei
of the lighter elements are smashed together whereby they become the nuclei
of heavier ones - this process is known as nuclear fusion. In our Sun and
similar stars, Hydrogen is being fused into Helium. At some stage, Helium
is fused into Carbon, then Oxygen, etc.
The fusion process requires positively
charged nuclei to move very close to each other before they can unite.
But with
increasing atomic mass and hence,
increasing positive charge of the nuclei, the electric repulsion between
the nuclei becomes
stronger and stronger.
In fact, the fusion process only
works up to a certain mass limit, corresponding to the element Iron. All
elements that are
heavier than Iron cannot be produced
via this path.
The following pictures show the
distribution curves of the relative abundance of
the elements in the "visible" universe:
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The understanding of the origin of the elements, that is their sites
of origin, the variety of processes involved, and the epochs in
the evolutionary history of the universe when they occurred, is one
of the greatest achievement of modern science. The
importance of this endeavor is not only in its ability to provide answers
to questions such as “where did we come from", but
also in its being the prime tool for setting the time markers that
delineate cosmic evolution. Research over the past half century
has clarified much of the situation. The cosmic rays, high energy
particles that pervade our Galaxy, not only provide a direct
sample of cosmic matter carrying information on the processes that
produce the elements, but also play a major role in the
synthesis of the light elements, lithium, beryllium and boron. As we
shall see, investigations with powerful ground and space
based telescopes of the abundances of these elements have led to entirely
new insights into the origin of the cosmic rays.
Element Genesis
We now know that nucleosynthesis, the genesis of the chemical elements
and their isotopes, took place both universally,
shortly after the Big Bang, as well as in stars, much later. Isotopes
of the same element have the same atomic number but
different masses.
Hydrogen is by far the most abundant
element in the universe; it accounts for approximately 93% of the total
number of atoms and 76% of the total mass. Helium comes in at a distant
second at about 7% of the number and 23% of the mass.
In general the abundance of the
elements drops off exponentially as the atomic mass increases ( simply
said: atomic mass is the sum of the protons and neutrons in the atom's
nucleus ) the exponential fall is continuous throughout the periodic table
until it hits the iron group. (Look at the chart below and you can see
a spike at atomic mass 56) These elements are approximately 10,000 times
more abundant than their neighbors. This is the only perturbation in the
fairly smooth distribution curve. When one does an analysis of the the
distribution curve some interesting facts can be seen, such as 99% of the
universe's weight comes from hydrogen and helium and all the atoms with
a greater atomic number than iron makes up less than a millionth of the
universe's total (visible) weight.
1.1 Nucleosynthesis of the light elements
In the first few minutes after the Big Bang, at temperatures exceeding
109 K, several of the lightest elements and their isotopes
were created. Most of the helium (He), essentially all of the deuterium
(2H, the heavy isotope of hydrogen) and some lithium
were thus produced. Lithium has two stable isotopes, 7Li and 6Li, but
the relevant nuclear processes are such that the Big
Bang produced significant amounts of only the heavier one. Beryllium
has one stable isotope (9Be), while boron has two (10B
and 11B). These light elements were not produced in significant
quantities in the Big Bang. Likewise, because of the rapid
expansion of the universe and the concomitant decrease of the density
and temperature, neither were the heavier elements (C,
O , etc.). These, so-called metals, have been and still are synthesized
much later in the interior of stars, as well as in stellar
explosions (supernovae) that are the death throes of the most massive
stars.
The idea that the synthesis of all the elements was associated with
the origin of the Universe came from George Gamow and
his co-workers in the late 1940's. A competing theory at that time
was that of Fred Hoyle, which maintained that all the
elements are synthesized in stars in galaxies. The strongest argument
against an initial, universal synthesis of all the elements is
the fact that very significant variations of elemental abundances are
observed in stars of different ages, indicating that
nucleosynthesis is an ongoing process. Indeed, the theories of stellar
evolution, supernova dynamics and Galactic chemical
evolution are capable of accounting for many the observed elemental
abundances at a great variety of astronomical sites. These
theories are based in large part on the pioneering work in the 1950's
of Margaret and Geoff Burbidge, Willie Fowler and Fred
Hoyle, and independently that of Al Cameron.
On the other hand, there are several isotopes whose abundances cannot
be understood by stellar nucleosynthesis. Even
though deuterium is produced in stellar interiors, it is also very
rapidly destroyed. But in the Big Bang, deuterium produced by
the capture of neutrons on protons, can survive under certain conditions
on the universal density which allow the synthesized 2H
to escape destruction owing to the rapid expansion of the universe.
In fact, the observed deuterium abundance in the solar
system, in the Galaxy and even in distant extragalactic space, is one
of the best indicators of the overall matter density of the
universe.
The other light elements, Li, Be and B, hold a unique place among the
elements. Even though their abundances are
exceedingly low, only about 10-9 that of H and about 10-6 that of the
next heavier elements C, N and O, they play important
roles both in cosmology and cosmic-ray origin. Li, Be and B are very
easily destroyed in stellar interiors, and they are not
generated in the normal course of stellar nucleosynthesis, which proceeds
directly from helium to carbon via the fusion of
three alpha particles (helium nuclei). 7Li is somewhat of an exception,
as it is produced via the fusion of the two helium
isotopes, 3He and 4He, in giant stars and supernovae. Thus, until about
1970, the origin of Li, Be and B remained a mystery.
At that time, Hubert Reeves, Willie Fowler and Fred Hoyle suggested
that these light elements could be produced in nuclear
interactions of cosmic rays with the atoms of the gas and dust that
pervade interstellar space in galaxies (the interstellar
medium). The cosmic rays, high energy particles most likely accelerated
by shock waves produced by supernovae, also
pervade interstellar space.
1.2 The nucleosynthesis of heavy elements
How were those heavy elements we now find on the Earth produced in
the first place? From where comes the
Zirconium in artificial diamonds, the Barium that colours fireworks,
the Tungsten in the filaments in electric bulbs? Which
process made the Lead in your car battery?
Synthesizing the Chemical Elements
The Sun and Solar System abundances are the result of MANY cycles of
element production and dispersal in stars. We are literally made
of star dust.
We already have a way to mix in "new" Helium, Carbon and Oxygen. All
stars with initial masses <8M. end their lives on the Asymptotic Giant
Branch (AGB). Main-sequence, (red giant branch )RGB , (horizontal-branch)
HB and (asymptotic giant branch) AGB stars produce these elements, deep
convection mixes some into the envelopes of the AGB stars and then Planetary
Nebulae carry these elements into the interstellar medium to be mixed into
the next generations of stars.
Low-mass stars make He, C, and O, and deliver these via stellar winds
and planetary nebulae.
To make the heavier elements up to Iron requires nucleosynthesis in
massive stars and delivery via stellar winds or, more spectacularly,
Supernova
(SN) explosions.
Supernova(SN)
The structure of all stars is determined by the battle between gravity
and radiation pressure arising from internal energy generation. In the
early stages of a star's evolution the energy generation in its centre
comes from the conversion of hydrogen into helium. For stars with
masses of about 10 times that of the Sun this continues for about ten million
years.
Supernovae are vast explosions in which a whole star is blown
up. They are mostly seen in distant galaxies as `new' stars appearing
close to the galaxy of which they are members. They are extremely
bright, rivalling, for a few days, the combined light output of all the
rest of the stars in the galaxy. After this time all the hydrogen
in the centre of such a star is exhausted and hydrogen `burning'
can only continue in a shell around the helium core. The core contracts
under gravity until its temperature is high enough for helium `burning',
into carbon and oxygen, to occur. The helium `burning' phase also
lasts about a million years but eventually the helium at the star's centre
is exhausted and it continues, like the hydrogen `burning', in a
shell. The core again contracts until it is hot enough for the conversion
of carbon into neon, sodium and magnesium. This lasts for about 10 thousand
years.
Type I supernova (SNII)
This pattern of core exhaustion, contraction and shell `burning' is
repeated as neon is converted into oxygen and magnesium (lasting
about 12 years), oxygen goes to silicon and sulphur (about 4 years)
and finally silicon goes to iron, taking about a week. No further
energy can be obtained by fusion once the core has reached iron and so
there is now no radiation pressure to balance the force of gravity. The
crunch comes when the mass of iron reaches 1.4 solar masses. Gravitational
compression heats the core to a point where it endothermically decays into
neutrons. The core collapses from half the Earth's diameter to about 100
kilometres in a few tenths of a second and in about one second becomes
a 10 kilometre diameter neutron star. This releases an enormous amount
of potential energy primarily in the form of neutrinos which carry 99%
of the energy.
A shock wave is produced which passes, in 2 hours, through the
outer layers of the star causing fusion reactions to occur. These form
the heavy elements. In particular the silicon and sulphur, formed shortly
before the collapse, combine to give radioactive nickel and cobalt which
are responsible for the shape of the light curve after the first two weeks.
When the shock reaches the star's surface the temperature reaches
200 thousand degrees and the star explodes at about 15000 kilometres/sec.
This rapidly expanding envelope is seen as the initial rapid rise in brightness.
It is rather like a huge fireball which rapidly expands and thins allowing
radiation from deeper in towards the centre of the original star to be
seen. Subsequently most of the light comes from energy released by the
radioactive decay of cobalt and nickel produced in the explosion.
Type I supernova (SNI)
The origin of a Type I supernova is an old, evolved binary system in
which at least one component is a white dwarf star. White dwarf stars are
very small compact stars which have collapsed to a size about one tenth
that of the Sun. They represent the final evolutionary stage of all low-mass
stars. The electrons in a white dwarf are subject to quantum mechanical
constraints (the matter is called degenerate) and this state can only be
maintained for star masses less than about 1.4 times that of the
Sun.
SN are like a production and delivery system for the elements.
What about those elements more massive than Fe? Supposedly equilibrium
reactions don't work to produce elements on the other side of the
binding energy curve beyond Fe. It turns out that in the excitement of
SN explosions there are many non-equilibrium reactions that build up very
massive elements.
In some cases these elements are stable, in many cases they are not
and the process of radioactive decay of heavy elements is just Nature's
way of getting back into equilibrium.
The two principal paths to building "trans-Fe" elements are the s-process
and the r-process.
1.S(slow)-process is the Slow addition of neutrons to nuclei with the
neutron subsequently undergoing a β-decay (ejection of an
e-) to change into a p+. This way atoms can slowly slowly walk their way
up the Periodic table. It is much easier to add the chargeless neutron
to a nucleus than it is a p+.
56Fe26 + 3n0 -> 59Fe26
59Fe26 -> 59Co27 + e-1 + n0;
This works up to around Bismuth at atomic #83 and is though to occur
in SNI and also in AGB stars during the thermal pulse stage.
There is some direct evidence for the S-process occuring in some AGB
stars. Technetium with atomic #43 is an S-process element that has
a radioactive half-life of ~200,000 years. It has been detected in AGB
stars that are MUCH older than that! The only thing that could be going
on is the production of Tc in the star and then mixing
of this to the surface via convection.
2.R(rapid)-process is the Rapid addition of neutrons to existing nuclei.
The idea is that you add a bunch of neutrons which then start to
decay into protons via β-decay in the nucleus. This increases
the atomic number and is the way to produce the really heavy stuff.
The R-process occurs only (we think) in SN and mostly in SNII. The
evidence for R-process occuring is less direct. First, we see elements
like Gold which are thought to only be produced via the R-process. It is
also true that if we look at the oldest stars in the Galaxy, which were
formed after only one or two SNII (these come from massive stars that have
very short lives) had enriched the interstellar medium, the abundance of
Iron is very low, but the abundaces of R-process elements are only moderately
low.
If we look at the Crab nebula which is the expanding remnant of the
1054 A.D. explosion we see processed material from deep in the star
that went SN, but mostly this is the result of the equilibrium fusion
in the "onion skin".
Elements
# of Protons
Production Site
Hydrogen
1
Big Bang
He
2
Big Bang + stars
Carbon, Oxygen
6, 8
low- and high-mass stars
Neon - Fe
10 - 26
high-mass stars
Cobalt - Bismuth
27 - 84
s- and r-process; AGB and SNe
Polonium - Uranium
84 - 92
r-process in SNe
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As the neutron excess in stable nuclei increases with mass, then accordingly nuclei with equal numbers of protons and neutrons (N=Z) become increasingly exotic compared to the line of beta stable nuclei, and consequently more difficult to produce and investigate experimentally. The neutron separation energy (Sn) is the amount of energy required to remove a neutron from the nucleus, and is equal to the difference in binding of the nucleus with and without the neutron. Similarly, the proton separation energy (Sp) is the energy required to remove a proton. The limits of the existence of nuclei are defined to be where the separation energy of the last nucleon is zero, and are referred to as driplines. The proton dripline is on the neutron-deficient side of the stable nuclei and is predicted to cross the N=Z line somewhere just above 100Sn.
To compute the nuclear binding energy, simply total up the masses of the protons and neutrons in a nucleus and compare it to the mass of the nucleus.

Nuclear
Nuclear
Reactions
Light nuclides
undergo fusion or bombardment to convert to other nuclides closer to the
maximum value
Heavy nuclides
undergo fission to give nuclides closer to the maximum value If a nuclear
reaction gives products with a higher nuclear binding energy, then energy
is released by the reaction.
Nuclear
Fusion Reactions
Nuclear energy, measured in millions of electron volts (MeV), is released
by the fusion of two light nuclei, as when two heavy hydrogen nuclei, deuterons
(H), combine in the reaction
producing a helium-3 atom, a free neutron (n),
and 3.2 MeV, or 5.1 × 10-13 J (1.2 × 10-13
cal).
Nuclear
Fission Reactions
Nuclear energy is also released when the fission (breaking up of )
of a heavy nucleus such as 235U is induced by the absorption
of a neutron as in
producing cesium-140, rubidium-93, three neutrons, and 200 MeV, or 3.2
× 10-11 J (7.7 × 10-12 cal). A nuclear
fission reaction releases 10 million times as much energy as is released
in a typical chemical reaction. The
two key characteristics of nuclear fission important for the practical
release of nuclear energy are both evident in equation (2). First, the
energy per fission is very large. In practical units, the fission of 1
kg (2.2 lb) of uranium-235 releases 18.7 million kilowatt-hours as heat.
Second, the fission process initiated by the absorption of one neutron
in uranium-235 releases about 2.5 neutrons, on the average, from the split
nuclei. The neutrons released in this manner quickly cause the fission
of two more atoms, thereby releasing four or more additional neutrons and
initiating a self-sustaining series of nuclear fissions, or a chain reaction,
which results in continuous release of nuclear energy.
Nuclear Forces
Within the incredibly
small nuclear size, the two strongest forces in nature are pitted against
each other. When the balance is broken, the resultant radioactivity yields
particles of enormous energy.

Magic Numbers.
In the atomic shell model, the shells are filled with electrons in
order of increasing energy until they completely fill a closed shell, producing
the inert core of a noble gas. These elements have highly stable properties,
such as low ionic radius and high ionisation energy. As further electrons
are added to shells outside the core, the atomic properties are primarily
determined by these valence electrons. The shell model arises from observation
of similar phenomena in nuclei, with certain numbers of
nucleons being particularly stable, these numbers are called `magic
numbers',
Nuclei with either numbers of protons or neutrons equal to Z, N =2,
8, 20, 28, 50, 82, or 126 exhibit certain properties which are analogous
to closed shell properties in atoms, including anomalously low masses,
high natural abundances and high energy first excited states. The effect
can be seen in a plot of separation energy versus increasing N or Z (figure
2.3) [52]. This is similar to the ionisation energy of an atom with increasing
mass, ie. there is a gradual increase with a definite sharp drop off at
each of the magic numbers, corresponding to the filling of major nuclear
shells.
Radioactivity
The nuclei
of elements exhibiting radioactivity are unstable and are found to be undergoing
continuous disintegration (i.e., gradual breakdown). The disintegration
proceeds at a definite rate characteristic of the particular nucleus;
that is, each radioactive isotope has a definite lifetime. However, the
time of decay of an individual nucleus is unpredictable. The lifetime
of a radioactive substance is not affected in any way by any physical or
chemical conditions to which the substance may be subjected.
Types of ionising radiation:

X-rays and gamma rays, like light, represent energy transmitted
in a wave without the movement of material, just as heat and light from
a fire or the sun travels through space. X-rays and gamma rays are virtually
identical except that X-rays do not come from the atomic nucleus. Unlike
light, they both have great penetrating power and can pass through the
human body. Thick barriers of concrete, lead or water are used as protection
from them.
Alpha particles have a positive electrical charge and are emitted
from naturally occurring heavy elements such as uranium and radium, as
well as from some man-made elements. Because of their relatively large
size, alpha particles collide readily with matter and lose their energy
quickly. They therefore have little penetrating power and can be stopped
by the first layer of skin or a sheet of paper.
However, if they are taken into the body, for example by breathing
or swallowing, alpha particles can affect the body's cells. Inside the
body, because they give up their energy over a relatively short distance,
alpha particles can inflict more biological damage than other radiations.
Beta particles are fast-moving electrons ejected from the nuclei
of atoms. These particles are much smaller than alpha particles and can
penetrate up to 1 to 2 centimetres of water or human flesh. Beta particles
are emitted from many radioactive elements. They can be stopped by a sheet
of aluminium a few millimetres thick.
Cosmic radiations consist of a variety of very energetic particles
including protons which bombard the earth from outer space. They are more
intense at higher altitudes than at sea level where the earth's atmosphere
is most dense and gives the greatest protection.
Neutrons are particles which are also very penetrating. On earth,
they mostly come from the splitting, or fissioning, of certain atoms inside
a nuclear reactor. Water and concrete are the most commonly used shields
against neutron radiation from the core of the nuclear reactor.
It is important to understand that ionising radiation does not cause
the body to become radioactive.
1.3 The classification of the elements
Periodic Table
History
In the early 1800's Dobereiner
noted that similar elements often had relative atomic masses, and
DeChancourtois made a cylindrical table of elements to display the
periodic reoccurrence of properties.
Cannizaro
determined atomic weights for the 60 or so elements known in
the 1860s, then a table was arranged by Newlands, with the elements
given a serial number in order of their atomic weights, beginning
with Hydrogen. This made evident that "the eighth element,
starting from a given one, is a kind of repetition of the first",
which Newlands called the Law of Octaves.
Both Meyer and Mendeleyev constructed periodic tables independently, Meyer
more impressed by the periodicity of physical properties, while Mendeleyev
was more interested in the chemical properties.
"...if all the elements be arranged in order of their atomic weights
a periodic repetition of properties is obtained." - Mendeleyev
Mendeleyev published his periodic table & law in 1869 and forecast
the properties of missing elements, and chemists began to appreciate it
when the discovery of elements predicted by the table took place. Periodic
table have always been related to the way scientists thought about the
shape and structure of the atom, and has changed accordingly.
Dimitri Mendeleev
| Dimitri Mendeleev created this, the original, periodic table. | ||||||||||||||||||
| Reihen
|
Gruppe I.
- R2O |
Gruppe II.
- RO |
Gruppe III.
- R2O3 |
Gruppe IV.
RH4 RO2 |
Gruppe V.
RH3 R2O5 |
Gruppe VI.
RH2 RO3 |
Gruppe VII.
RH R2O7 |
Gruppe VIII.
- RO4 |
||||||||||
| 1 | H = 1 | |||||||||||||||||
| 2 | Li
= 7
|
Be
= 9,4
|
B
= 11
|
C
= 12
|
N
= 14
|
O
= 16
|
F
= 19
|
|||||||||||
| 3 | Na = 23 | Mg = 24 | Al = 27,3 | Si = 28 | P = 31 | S = 32 | Cl = 35,5 | |||||||||||
| 4 | K = 39 | Ca = 40 | - = 44 | Ti = 48 | V = 51 | Cr = 52 | Mn = 55 | Fe
= 56, Co=59
Ni=59, Cu=63 |
||||||||||
| 5 | (Cu = 63) | Zn = 65 | - = 68 | - = 72 | As = 75 | Se = 78 | Br = 80 | |||||||||||
| 6 | Rb = 85 | Sr = 87 | ?Yt = 88 | Zr = 90 | Nb = 94 | Mo = 96 | - = 100 | Ru=104,
Rh=104
Pd=106, Ag=108 |
||||||||||
| 7 | Ag = 108 | Cd = 112 | In = 113 | Sn = 118 | Sb = 122 | Te = 125 | J = 127 | |||||||||||
| 8 | Cs = 133 | Ba = 137 | ?Di = 138 | ?Ce = 140 | - | - | - | - - - - | ||||||||||
| 9 | (-) | - | - | - | - | - | - | |||||||||||
| 10 | - | - | ?Er = 178 | ?La = 180 | Ta = 182 | W = 184 | - | Os=195,
Ir=197,
Pt=198, Au=199 |
||||||||||
| 11 | (Au = 199) | Hg = 200 | Tl = 204 | Pb = 207 | Bi = 208 | - | - | |||||||||||
| 12 | - | - | - | Th = 231 | - | U = 240 | - | - - - - | ||||||||||
Organization of the Modern Periodic
Table
The `modern' periodic table is very
much like a later table by Meyer, arranged, as was Mendeleyev's, according
to the size of the atomic weight, but with Group 0 added by Ramsay. Later,
the table was reordered by Mosely according to atomic numbers (nuclear
charge) rather than by weight.
The Periodic
Law revealed important analogies among the 94 naturally occurring elements,
and stimulated renewed interest in Inorganic Chemistry in the nineteenth
century which has carried into
the present with the creation of
artificially produced, short lived elements of `atom smashers' and supercolliders
of high energy physics.
Harry D.
Hubbard, of the United States National Bureau of Standards, modernized
Mendeleyev's periodic table, and his first work was published in
1924. This was known as the "Periodic Chart of the Atoms".
Into the 1930s the heaviest elements were being put up in the body of the
periodic table, and Dr.Glenn T.Seaborg in 1968 "plucked those out"
while working with Fermi in Chicago, naming them the Actinide series,
which later permitted proper placement of subsequently 'created'
elements - the Transactinides, changing the periodic table yet again.
These elements were shown separate from the main body of the table.
The Alexander Arrangement of the Elements, a three-dimensional periodic
chart designed and patented by Roy Alexander and introduced in 1994, retains
the separate Lanthanide and Actinide series, but integrates them at the
same time, made possible by using all three dimensions Further improvement
provided by the Alexander Arrangement of the Elements is location of all
the element data blocks in a continuous sequence according to atomic numbers
while retaining all accepted property interrelationships. This eases
use & understanding of the immense correlative power of
the periodic chart in teaching,
learning, and working with chemistry.
Periodic table is an arrangement of all known element according to their
atomic number and chemical properties. This table contains vertical columns
called groups and horizontal columns called periods. All elements in
a group have similar chemical properties. These groups are number from
1 - 8, left to right and some of groups have their own names.
group I - alkali metal: Li, Na, K Rb, Cs, Fr
group II - alkaline earth metals: Be, Mg, Ca, Sr, Ba, Ra
group VII - Halogens: Cl, Br, I, At
group VIII - Noble gases: He, Ne, Ar, Kr, Xe, Rn
In addition to groups in the periodic table there are three blocks of elements called transition elements, Lanthanoides and Actinoides
Most of the elements in the periodic table are metals. They are found to the left of the table.
The non-metals are found to the top right side of the periodic table. Metals loose electrons to form cations, while non-metals gain electrons to form anions. The bonding between metals and non-metals are usually ionic bond. Ionic bond is a due to attraction of charges of cations and anions. Covalent bonds are found in molecular compounds formed by non - metal reacting with non - metals.

Periodic Spiral: Is a textually
rich, highly informative tool for exploring the chemical elements. An
electronic learning application that’s both powerful and easy to use, Periodic
Spiral combines a feature-packed interface with a unique design of the
periodic table.
In conventional versions of the Mendeleyevian periodic table, the lanthanons
and the actinons are poorly integrated. Moreover, the traditional and alternative
placements of hydrogen neither effectively convey the element's unique
status nor indicate its chemical similarities and partial affinities to
the noble gases, the halogens and the alkali metals. Periodic Spiral illustrates
more clearly hydrogen's ambiguous relation to the noble gases, halogens
and chalcogens while recognizing its relation to the alkali metals; it
also fully integrates the lanthanons and actinons into the design.
| 1 | 2 | 3 | 4 | 5 | 6 | 7 | 8 | 9 | 10 | 11 | 12 | 13 | 14 | 15 | 16 | 17 | 18 | |
| 1 | H | He | ||||||||||||||||
| 1 | 2 | |||||||||||||||||
| 2 | Li | Be | B | C | N | O | F | Ne | ||||||||||
| 3 | 4 | 5 | 6 | 7 | 8 | 9 | 10 | |||||||||||
| 3 | Na | Mg | Al | Si | P | S | Cl | Ar | ||||||||||
| 11 | 12 | 13 | 14 | 15 | 16 | 17 | 18 | |||||||||||
| 4 | K | Ca | Sc | Ti | V | Cr | Mn | Fe | Co | Ni | Cu | Zn | Ga | Ge | As | Se | Br | Kr |
| 19 | 20 | 21 | 22 | 23 | 24 | 25 | 26 | 27 | 28 | 29 | 30 | 31 | 32 | 33 | 34 | 35 | 36 | |
| 5 | Rb | Sr | Y | Zr | Nb | Mo | Tc | Ru | Rh | Pd | Ag | Cd | In | Sn | Sb | Te | I | Xe |
| 37 | 38 | 39 | 40 | 41 | 42 | 43 | 44 | 45 | 46 | 47 | 48 | 49 | 50 | 51 | 52 | 53 | 54 | |
| 6 | Cs | Ba | * | Hf | Ta | W | Re | Os | Ir | Pt | Au | Hg | Tl | Pb | Bi | Po | At | Rn |
| 55 | 56 | 72 | 73 | 74 | 75 | 76 | 77 | 78 | 79 | 80 | 81 | 82 | 83 | 84 | 85 | 86 | ||
| 7 | Fr | Ra | ** | Rf | Db | Sg | Bh | Hs | Mt | Uun | Uuu | Uub | ||||||
| 87 | 88 | 104 | 105 | 106 | 107 | 108 | 109 | 110 | 111 | 112 | ||||||||
| * | La | Ce | Pr | Nd | Pm | Sm | Eu | Gd | Tb | Dy | Ho | Er | Tm | Yb | Lu | |||
| 57 | 58 | 59 | 60 | 61 | 62 | 63 | 64 | 65 | 66 | 67 | 68 | 69 | 70 | 71 | ||||
| ** | Ac | Th | Pa | U | Np | Pu | Am | Cm | Bk | Cf | Es | Fm | Md | No | Lr | |||
| 89 | 90 | 91 | 92 | 93 | 94 | 95 | 96 | 97 | 98 | 99 | 100 | 101 | 102 | 103 | ||||
|
|
||
|---|---|---|
| Alkali Earth | Alkaline Earth | Transition Metals |
| Rare Earth | Other Metals | Metalloids |
| Non-Metals | Halogens | Noble Gases |
.
Accordingly, the process of element-building is comparable to a mass
which falls under the influence of gravity as
follows:
The alkali metals, found in group 1 of the periodic table (formerly
known as group IA), are very reactive metals that do not
occur freely in nature. These metals have only one electron in
their outer shell. Therefore, they are ready to lose that one
electron in ionic bonding with other elements. As with all metals,
the alkali metals are malleable, ductile, and are good
conductors of heat and electricity. The alkali metals are softer
than most other metals.Cesium and francium are the most
reactive elements in this group. Alkali metals can explode if they
are exposed to water.
The Alkali Metals are: Lithium, Sodium, Potassium,
Rubidium, Cesium, Francium
The alkaline earth elements are metallic elements found in the
second group of the periodic table. All alkaline earth elements
have an oxidation number of +2, making them very reactive.
Because of their reactivity, the alkaline metals are not found free
in nature.
The Alkaline Earth Metals are:
Beryllium
Magnesium
Calcium
Strontium
Barium
Radium
Transition Elements
The 38 elements in groups 3 through 12 of the periodic table are called
"transition metals". As with all metals, the transition elements
are both ductile and malleable, and conduct electricity and heat.
The interesting thing about transition metals is that their valence
electrons, or the electrons they use to combine with other elements,
are present in more than one shell. This is the reason why they often
exhibit several common oxidation states. There are three noteworthy elements
in the transition metals family.
These elements are iron, cobalt, and nickel, and they are the
only elements known to produce a magnetic field.
The Transition Metals:
| Scandium
Titanium Vanadium Chromium Manganese Iron Cobalt Nickel Copper Zinc Yttrium Zirconium Niobium Molybdenum Technetium Ruthenium Rhodium Palladium Silver |
Cadmium
Hafnium Tantalum Tungsten Rhenium Osmium Iridium Platinum Gold Mercury Rutherfordium Dubnium Seaborgium Bohrium Hassium Meitnerium Ununnilium Unununium Ununbium |
Other Metals
The 7 elements classified as "other metals" are located in groups
3, 14, and 15. While these elements are ductile and malleable, they
are not the same as the transition elements. These elements, unlike
the transition elements, do not exhibit variable oxidation states,
and their valence electrons are only present in their outer shell.
All of these elements are solid, have a relatively high density,
and are opaque. They have oxidation numbers of +3, ±4, and
-3.
The "Other Metals" are:
| Aluminum
Gallium Indium Tin Thallium Lead Bismuth |
Metalloids
Metalloids are the elements found along the stair-step line that
distinguishes metals from non-metals. This line is drawn from between
Boron and Aluminum to the border between Polonium and Astatine. The
only exception to this is Aluminum, which is classified under "Other
Metals". Metalloids have properties of both metals and non-metals.
Some of the metalloids, such as silicon and germanium, are semi-conductors.
This means that they can carry an electrical charge under special
conditions. This property makes metalloids useful in computers and
calculators
The Metalloids are:
| Boron
Silicon Germanium Arsenic Antimony Tellurium Polonium |
| Hydrogen
Carbon Nitrogen Oxygen Phosphorous Sulfur Selenium |
| Lanthanide Series | Actinide Series |
| Lanthanum
Cerium Praseodymium Neodymium Promethium Samarium Europium Gadolinium Terbium Dysprosium Holmium Erbium Thulium Ytterbium Lutetium |
Actinium
Thorium Protactinium Uranium Neptunium Plutonium Americium Curium Berkelium Californium Einsteinium Fermium Mendelevium Nobelium Lawrencium |
The structure of hydrogenic atoms
1.4 Some principles of quantum mechanics
Wave-Particle Duality
of Matter and Energy
Arbert
Einstein
Energy and matter
we have learnt from Einstein's theories are analagous, matter can be simply
described in terms
of energy. So far we have only discovered two ways in which energy can
be
transfered. These
are particles and waves. Wave theory applies to electromagnetic radiation.
EMR can also be described as particles.
quanta :A particles
of light energy.
Quantum: One
particle of light with a certain energy.
Photon: A stream
of Quanta
Wave theory could
be applied to electrons.
What is a wave-mechanical
model?
motions of a vibrating
string shows one dimensional motion.
Energy of the vibrating
string is quantized
Energy of the waves
increased with the nodes.
Nodes are places were
string is stationary.
Number of nodes gives
the quantum number. One dimensional motion gives one quantum
number.
Wave properties
of Electron
The electron is clearly
a particle as the experiments of J J Thomson show. He calculated that there
was a clear e/m ratio and that the charge on any electron is 1.6E-19 Coulombs.
However, experiments by Davisson and Germer show that electrons can display
diffraction, an obvious wave property. The first complete evidence of deBroglie's
hyprothesis came from two physicists working at the Bell Laboratories in
the USA in 1926. Using beams as Thomson did in electron diffraction they
scattered electrons off Nickel crystals and analysed how the electrons
were more likely to appear at certain angles than others. De Broglie suggested
that electrons have wave properties to account for why their energy was
quantized. He reasoned that the electron in the hydrogen
atom was fixed in the space around the nucleus. He felt that the
electron would best be represented as a standing wave. As a standing
wave, each electron’s path must equal a whole number times
the wavelength.
l = wavelength, meters
h = Plank’s constant
m = mass, kg
v = frequency, m/s
Returning now to the problem of the atom, it was realized that if, for the moment, we pictured the electron not as a particle but as a wave, then it was possible to get stable configurations. Imagine trying to establish a wave in a circular path about a nucleus. One possibility might be as below.
![]() |
For this configuration, when one starts the wave at a given point, one
ends up after one complete revolution at a different point on the wave.
The incoming wave will then be out of phase with the original wave, and
destructive interference will occur.
However, certain stable configurations are possible, as is illustrated
below.
![]() |
In this case, the wave ends up in phase with the original wave after
one complete revolution, and constructive interference results. Such a
pattern would result in a stable orbit. This type of wave is called a standing
wave, and are common in other contexts; for example, they can be established
on a string attached to a wall if the string is moved up and down at exactly
the right speed (such a wave would appear not to be moving, which is why
it's called a standing wave).
The Heisenberg Uncertainty Principle
There is a theoretical limit on the exactness with which a particle
can be pinned-down (usually in terms of its position and momentum):
Dx.Dp > h/2p
where Dx is the uncertainty in position
and
Dp the uncertainty in momentum.
The Schrödinger Wave Equation
and Its Significance
The Schrödinger Wave Equation
In its most general form the equation looks like this:
HY = EY
H is called the Hamiltonian operator and represents a series of mathematical operations that must be performed on Y which will give back Y multiplied by an energy E for the electron. Only Y functions for which this is true are "proper" wave-functions, called "eigenfuctions" and the E's that go with them are called "eigenvalues". ("Eigen" is German for "unique".)
H is defined for the system being described, for example
one nucleus and one electron (hydrogen) or two nuclei and one electron
(H2+), so the trick is to find the eigenfunctions
which work.
Let's see how this works in a model system - not an electron,
but a vibrating string:
The Vibrating String and the "Particle in a One-dimensional Box"
The following diagrams illustrate vibrations on stretched strings. The two curves indicate the extremes of the motion, and the formulae apply to the red one.
y
= sin(1px/l)
y
= sin(2px/l)
y
= sin(3px/l)
differentiating y twice with respect to x gives:
y = sin(npx/l) .........(1)
dy/dx = (np/l)cos(npx/l)now:d2y/dx2 = -(n2p2/l2)sin(npx/l) = -(n2p2/l2)y
d2y/dx2 = -(4p2/l2)yand, if the wave represents an electron instead of a string:
l = h/mvtherefore;
d2y/dx2 = -(4m2v2p2/h2)yand:
d2y/dx2 + d2y/dy2 + d2y/dz2 + (8p2m/h2)(E - V)y = 0Schrödinger describes the behavior and energies of electrons in atoms.His equation ( Wave function y ) is similar to one used to describe electromagnetic waves.
Of course there is no such thing as a three-dimensional string so the there is no three-dimensional equivalent of equation (1). For an electron and nucleus the "boundary conditions" are different and the solutions to the wave equation (eigenfunctions) take a different form. In addition, it is necessary to use polar coordinates to simplify the solution.![]()
y = wave function
E = total energy
V = potential energy
The diagrams below represent extremes of motion of vibrating drumskins. Play with the applet to make sure you understand which are which. Each mode of vibration is characterized by two quantum numbers, one of which defines the number of circular nodes, and one of which defines the number of linear nodes.
| One circular node
(at the drumskin's edge) |
|
| Two circular nodes
(one at the drumskin's edge plus one more) |
|
| Three circular nodes
(one at the drumskin's edge plus two more) |
|
| One transverse node
(plus a circular one at the drumskin's edge) |
|
| Two transverse nodes
(plus one at the drumskin's edge) |
|
| Two transverse nodes plus two circular nodes | |
These vibrations are much easier to visualize when
animated.
Separation of the Eigenfunctions into Radial and Angular Components
It turns out to be much easier to solve the three-dimensional
Schrödinger equation if it is transformed to polar coordinates:

Radial probability function electron in 2s orbital
Radial probability function electron in 3s orbital
Nodes in the Y
Total nodes = n -1
Radial nodes = n -1- l
Angular nodes = l
Eg 4d orbital:
Total nodes = 4 -1 = 3
Radial nodes = n -1- l = 4-1-2 = 1
Angular nodes = l = 2
Probability functions R2 and 4pr2R2
(These diagrams were constructed using the program Mathcad)




Meaning of Quantum Numbers
Schrodinger's model was based on standing wave properties of electrons
similar to a vibrating guitar string and the momentum considering electron
as a particle. The difference in the treatment electronic waves was that
electrons show three dimensional motion and vibrating string showed one-dimensional
motion.Energy of the vibrating string is quantized (quantified) energy
of the waves increased with the nodes. Nodes are places were string is
stationary. The number of nodes was called the quantum number. One-dimensional
motion gives one quantum number.
Quantum numbers n, l and ml
Principal quantum number, n
Tells the size of an orbital and largely determines its energy.
n = 1, 2, 3, ……
n value could be 1, 2, 3, 4, 5, . . . . etc.
Angular momentum, l
The azimuthal or angular quantum number l can take values
l = (n-1), (n-2), (n-3), ... ¥
It defines the orbital type or sub-shell:
The number of subshells that a principal level contains. It tells
the shape of the orbitals. l = 0 to n - 1
| Type | s | p | d | f |
|---|---|---|---|---|
| l | 0 | 1 | 2 | 3 |
Magnetic quantum number, ml
Describes the direction that the orbital projects in space.
ml = l to +l (all integers, including
zero)
ml values depends on l value:
can have -l . , 0 . . . +l values of ml
For example, if l = 2, then ml would have
values of -2, -1, 0, 1 and 2.
Knowing all three numbers provide us with a picture of all of the orbitals.
The magnetic quantum number ml can take values l,
(l-1), (l-2) ... 0 ... -l
This quantum number can only be associated with a specific orbital
for the case ml = 0. The orbitals defined by other values are
functions involving -1½ i.e. they are imaginary. The
orbitals we can visualize and draw are obtained by mathematically "mixing"
the imaginary functions, so that the one-on-one correspondence is lost.
For example, the 2pz orbital goes with ml = 0 but
the other two are mixtures.
The rule for obtaining the possible values of ml from
l does tell us how many orbitals of a particular type we can construct,
for example, if l = 3, ml can be 3, 2, 1, 0, -1, -2, and -3
corresponding to the 7 f-orbitals.
In each of the following cases, the full name of the orbital
includes the value of n followed by the orbital symbol. The symbol is followed
by a subscript that is derived from simplified approximate functions that
mimic the real ones called Slater orbitals.
The principal quantum number n can take values n = 1,
2, 3, ... ¥
The magnetic quantum number ml can take values
l, (l-1), (l-2) ... 0 ... -l
This quantum number can only be associated with a specific orbital
for the case ml = 0. The orbitals defined by other values are
functions involving -1½ i.e. they are imaginary. The
orbitals we can visualize and draw are obtained by mathematically "mixing"
the imaginary functions, so that the one-on-one correspondence is lost.
For example, the 2pz orbital goes with ml = 0 but
the other two are mixtures.
The rule for obtaining the possible values of ml from l does tell us how many orbitals of a particular type we can construct, for example, if l = 3, ml can be 3, 2, 1, 0, -1, -2, and -3 corresponding to the 7 f-orbitals.
In each of the following cases, the full name of the orbital
includes the value of n followed by the orbital symbol. The symbol is followed
by a subscript that is derived from simplified approximate functions that
mimic the real ones called Slater orbitals.
Spin Quantum Number
ms should always be -1/2 or +1/2
For the electron 3 Quantum numbers for motion in 3 dimension
(x, y, z directions in space) are necessary. Fourth Quantum number was
necessary due to spin motion of the electron. According to wave-mechanical
model an electron has four Quantum numbers (Q.N.): n = Principle Q.N.;
l =Angular Momentum Q.N.; ml = Magnetic Q.N.; ms
= Spin Q.N.
Schrödinger introduced the
notion of treating electrons as standing waves - a novel move away
from thinking of electrons as particles.
Each electron can be described in
terms of Wave function y
its quantum numbers.
(n, l, ml, ms),
y2
is proportional probablity of finding the electron in a given volume. Max
Born Interpretation: y2
= atomic orbital
Electrons travel in three dimensions therefore three quantum numbers
are needed three to describe, x, y, z, and fourth is needed for the spin.
Four quantum numbers of an electron describe an orbital currently used
to explain the arrangement, bonding and spectra of atoms.
1.5 Atomic orbitals
Shapes of the Atomic Orbitals
s-Orbitals
These orbitals are spherically symmetrical. They have n - 1 spherical
nodes (excluding the one at r = ¥). Notice
that the maximum in r2R2(r) occurs at increasing
distances from the nucleus with n. Most of the electron density is contained
outside the nodal spheres.Electrons surrounding atoms are concentrated
into regions of space called atomic orbitals. The Heisenberg uncertainty
principle states that it is impossible to know both the location and the
momentum of an atomic particle, but it is possible to describe the probability
that the electron will be found within a given region of space. The boundries
of an atomic orbital are commonly drawn to the region of 90% probability;
there is a 90% probability that at any given time, the electron will be
within the specified boundry.
The electronic configuration of carbon is 1s2 2s2
2sp3. Atomic orbitals with s-character have spherical symmetry
and a representation of the surface of the carbon 1s orbital is shown below.
The wave properties of electrons make the description of the 2s orbital
slightly
more complex than the corresponding 1s orbital, in that, within the 2s
sphere there is a region in which the amplitude of the electron standing
wave falls to zero, that is, there is zero probability of finding the electron
in this node region.
p-Orbitals
These orbitals each have one planar node (in xy,xz or yz) as well as
n - 2 spherical nodes (excluding the one at r = ¥).
They are named for the axes perpendicular to their nodes (px,
py and pz. Remember that these orbitals all have
a three-dimensional shape with cylindrical symmetry i.e. sections through
them parallel to the nodal planes have circular symmetry
The electron densities along the x, y and z axes of the 2p orbitals are clearly shown in the figure; the nodes are the points at the origin and at these points, there is zero probability of finding the electron.
d-Orbitals
It is not possible to mathematically construct 5 equivalent looking
real orbitals from the imaginary solutions to the wave equation. The conventional
choice is to depict four that have equivalent shapes with two planar nodes
each and a fifth with a conical node. The four are named for the plane
defined by a pair of axes which does not define a planar node (dxy,
dx2-z2, dxz, dyz).
The fifth orbital is cylindrically symmetrical about the z axis with a
conical node (at 2z2-x2-y2 = 0) and is
called the dz2 orbital. The d-orbitals have n - 3
spherical nodes.
Shown below are the set of 3d orbitals. From the top 3dz2,
3dx2-y2, 3dxz, 3dyz
and 3dxy:

Many-electron atoms
Stuctures of Atoms with Many Electrons

Firstly, note that for a one electron atom or ion, the energy
is only a function of n. For atoms with many electrons this remains the
overbearing trend, but penetration effects have a profound effect on the
actual ordering:
1.6 Penetration and shielding
Radial Penetration of the Wave Functions
The order can be rationalized by setting up a core of electrons
and then considering where the next might go. This is illustrated in Text
Figure 1.18. Notice that the added electron would penetrate more deeply
into the core in the orbital with the lowest l (s more than p more than
d). Do not be mislead by the position of the main maximum in each curve:
it is the little "bumps" towards the nucleus that make the difference.
Since the stabilization of the electron is directly related to the nuclear
charge it "feels" (the effective nuclear charge), the greater the
penetration, the better.
Effective Nuclear charge (Zeff):
Nuclear charge felt by electrons. Zeff is less than atomic
number (Z) since in polyelectronic atoms electrons screen each other from
the nucleus.
Many atomic properties are directly related to the magnitude of Zeff.
Variation of Zeff has been used to explain atomic property trends
going across a period or down a group in the periodic table.
Zeff increase going across a period
Zeff decrease going down a group
Argon - Find the effective
nuclear charge experienced by one of the outermost 3p electrons.
Configuration: (1s2)(2s22p6)(3s23p6)
Other electrons in the same group = 7 x 0.35 = 2.45Zinc - Find the effective nuclear charge experienced by one of the 4s electrons.
Electrons in the next shell (n = 2) down = 8 x 0.85 = 6.8
Electrons in shells (n = 1) further left = 2 x 1.0 = 2.20Therefore s = 11.25 and Z* = 18 - 11.25 = 6.75
Other electrons in the same group = 1 x 0.35 = 0.35Zinc - Find the effective nuclear charge experienced by one of the 3d electrons.
Electrons in the next shell (n = 3) down = 18 x 0.85 = 15.30
Electrons in shells (n = 2,1) further left = 10 x 1.0 = 10.00Therefore s = 11.25 and Z* = 30 - 25.65 = 4.35
Configuration: (1s2)(2s22p6)(3s23p6)(3d10)(4s2)Electrons in groups to the right (4s1) contribute nothing.
Other electrons in the same group (3d) = 9 x 0.35 = 3.15
Electrons in the remaining groups to the left = 18 x 1.00 = 18.00Therefore s = 11.25 and Z* = 30 - 21.35 = 21.15
I.P. = 13.6.Zeff2/n2 (eV)

What is Pauli Exclusion
Principle?
If two or more orbitals exist at
the same energy level, they are degenerate. Do not pair the electrons until
you have to.
Electrons in an atom cannot have
all four of their quantum numbers equal.
Eg. He: 1s2 electron orbital
n l
ml
ms
__________________________________
1 1s1 1
0 0
1/2 ( ¯
)
2 1s2 1
0 0
-1/2 ( )
Hund’s Rule
Rule to fill electrons into p,d,f
orbitals containing more than one sublevel of the same energy.
| ¯ | ¯ | ¯ |
| ¯ | ¯ | ¯ | ¯ | ¯ |
| ¯ | ¯ | ¯ | ¯ | ¯ | ¯ | ¯ |
Elecronic configuration using the periodic table
| Hydrogen to Helium | Z=1 to
Z=2 (K-shell) |
1s1 to | No choice here! The 2s is significantly higher in energy. the second electron pairs (opposite spin) with the other sharing the 1s wavefunction. |
Elements of Period Two
| Lithium
Beryllium |
Z=3
Z=4 (L-shell, part) |
1s22s1
1s22s2 |
The effect of the greater penetration of the 2s orbital favours it over the 2p as the home for the next two electrons. |
| Boron to
Neon |
Z=5 to
Z=10 (L-shell, then rest) |
1s22s22p1 to
1s22s22p6 |
Add one electron to each 2p orbital, spins parallel, until each of the three has one electron, and then begin pairing. If it is necessary to be specific, use a diagram showing individual orbitals and electron spins as arrows. It does not matter which combination of orbitals are chosen when a choice exists, nor which spin is chosen, as long as they are parallel as far as possible. |
Elements of Period Three
| Sodium to
Argon |
Z=11 to
Z=18 (M-shell) |
[neon]3s1 to
[Neon]3s23p6 |
These follow the pattern of the period from lithium to neon. The core, [neon] means the configuration of neon. |
Elements of Period Four
For this period, the 3d orbitls become very close in energy to
the 4s orbitals, and eventually dip below them leading to a couple of "anomalies"
in the configurations. (These anomalies are a source of exam questions,
but otherwise have little significance.) The filling order continues as
follows:
| Potassium to
Calcium |
Z=19 to
Z=20 |
[argon]4s1 to
[argon]4s2 |
As expected. |
| Scandium to
Vanadium |
Z=21 to
Z=23 |
[argon]4s23d1 to
[argon]4s23d3 |
As expected if 3d comes above 4s but below 4p (an accident of nature). |
| Chromium | Z=24 | [argon]4s13d5 | This is a manifestation of Hund's rule. It is as if the 4s and 3d orbitals are nearly degenerate (have the same energy) so the electrons are unpaired as far as possible. |
| Manganese to
Nickel |
Z=25 to
Z=28 |
[argon]4s23d5 to
[argon]4s23d8 |
These continue the expected trend if 3d is once again just above the 4s |
| Copper | Z=29 | [argon]4s13d10 | At this point the 3d orbital energy has dipped below the 4s and stays there. The 3d electrons become core electrons and have only a minor effect on the chemistry of the succeeding elements. |
| Zinc | Z=30 | [argon]4s23d10 | Zinc is divalent like calcium, but is "soft" due to the extra d polarizable electrons. |
| Gallium to
Krypton |
Z=31 to
Z=36 |
[argon]3d104s24p1 to
[argon]3d104s23p6 |
The expected order resumes. |
The Elements of Period Five
The elements of thise period show analogous configurations including an anomalous configuration for molybdenum (like chromium) and silver (like copper).
The Elements of Period Six
The trends are not unlike period five, but after lanthenum, come the 14 lanthanide elements where the 4f orbitals are being filled. There are anomalies in this series associated with the half-filled f-orbitals, and again at the end of the filling of the 5d orbitals for gold (like copper and silver).
The Elements of Period Seven
There are similarities to period six, with another set of 14 elements where the 5f orbitals are being filled, the actinides which follow actinium. Little is known of the chemistry of the short-lived radioactive elements beyond Z=104.
N.B.
The anomalies in ground state configurations of the neutral atoms
are not important in the chemistry of the atoms in their compounds. In
particular, for ions of the transition elements (incomplete d orbitals)
their configuration is always derived by assuming that the (n-1)d
subshell lies below the ns. Remember this when dealing with bonding
in transition metal complexes.
Exception to Building Up Principle!
There are several types of radii in common use according to the circumstances:
Element H Radius* 29.9 Element Be B C N O F Radius 106 83.0 76.7 70.2 65.9 61.9 Source b a a a a a Element Al Si P(III) S(II) Cl Radius 118 109.0 108.8 105.2 102.3 Source b a a a a Element Ga Ge As(III) Se(II) Br Radius 125 122 119.6 120.3 119.9 Source b b a a a Element In Sn Sb(III) Te(II) I Radius 141 139 137 139.1 139.5 Source b b b a a* The quoted radius for H applies to the actual position of the H-nucleus, as determined by neutron diffraction. With X-ray diffraction, the observed position of the H-atom is the centre of gravity of its electron cloud, which lies about 10 pm closer to the attached atom. This gives an apparent H-atom radius close to 20 pm.
Element C N O Single 76.7 70.2 65.9 Double 66.1 61.8 54.9 Triple 59.1 54.5
Element N O F Radius 155 152 147 Element Si P S Cl Radius 210 180 180 175 Element Ge As Se Br Radius 195 185 190 185 Element Sn Sb Te I Xe* Radius 210 205 206 198 200 Element Bi Radius 215* This value for Xe seems to be more appropriate for compounds than the value of 216 pm found in the element; Alcock,N.W. (1972) Adv. Inorg. Chem. Radiochem. 15, 4.Source:
Elem. Rad. Elem. Rad. Elem. Rad. Elem. Rad. Ag 144.5 Fe 127.4 Nb 146.8 Sn 162.3 Al 143.2 Ga 141.1 Nd 182.1 Sr 215.1 Au 144.2 Gd 180.2 Ni 124.6 Ta 146.7 Ba 224.3 Hf 158.0 Os 135.3 Tb 178.2 Be 112.8 Hg 157.3 Pb 175.0 Tc 136.0 Bi 170 Ho 176.6 Pd 137.6 Th 179.8 Ca 197.4 In 166.3 Pm 181.0 Ti 146.2 Cd 156.8 Ir 135.7 Pr 182.8 Tl 171.6 Ce 182.5 K 237.6 Pt 138.7 Tm 174.6 Co 125.2 La 187.7 Rb 254.6 U 156 Cr 128.2 Li 156.2 Re 137.5 V 134.6 Cs 273.1 Lu 173.4 Rh 134.5 W 140.8 Cu 127.8 Mg 160.2 Ru 133.9 Y 180.1 Dy 177.3 Mn 126.4 Sb 159 Yb 174.0 Er 175.7 Mo 140.0 Sc 164.1 Zn 139.4 Eu 204.2 Na 191.1 Sm 180.2 Zr 160.2Source:Teatum,E., Gschneidner,K., & Waber,J. (1960) Compilation of calculated data useful in predicting metallurgical behaviour of the elements in binary alloy systems, LA-2345, Los Alamos Scientific Laboratory.
Elem. Rad. Elem. Rad. Elem. Rad. Elem. Rad. Ag(+1) 129 Er(+3) 103.0 Mn(+3) 72/78.5* Ta(+3) 86 Al(+3) 67.5 Eu(+2) 131 Mo(+3) 83 Tb(+3) 106.3 Au(+1) 151 Eu(+3) 108.7 Na(+1) 116 Th(+4) 108 Au(+3) 99 Fe(+2) 75/92.0* Nb(+3) 86 Ti(+2) 100 Ba(+2) 149 Fe(+3) 69/78.5* Nd(+3) 112.3 Ti(+3) 81.0 Be(+2) 59 Ga(+3) 76.0 Ni(+2) 83.0 Ti(+4) 74.5 Bi(+3) 117 Gd(+3) 107.8 Pb(+2) 133 Tl(+1) 164 Ca(+2) 114 Hf(+4) 85 Pd(+2) 100 Tl(+3) 102.5 Cd(+2) 109 Hg(+1) 133 Pm(+3) 111 Tm(+3) 102.0 Ce(+3) 115 Hg(+2) 116 Pr(+3) 113 U(+3) 116.5 Ce(+4) 101 Ho(+3) 104.1 Pt(+2) 94 U(+4) 103 Co(+2) 79/88.5* In(+3) 94.0 Rb(+1) 166 V(+2) 93 Co(+3) 68.5/75* Ir(+3) 82 Rh(+3) 80.5 V(+3) 78.0 Cr(+2) 87/94* K(+1) 152 Ru(+3) 82 Y(+3) 104.0 Cr(+3) 75.5 La(+3) 117.2 Sb(+3) 90 Yb(+2) 116 Cs(+1) 181 Li(+1) 90 Sc(+3) 88.5 Yb(+3) 100.8 Cu(+1) 91 Lu(+3) 100.1 Sm(+3) 109.8 Zn(+2) 88.0 Cu(+2) 87 Mg(+2) 86.0 Sr(+2) 132 Zr(+4) 86 Dy(+3) 105.2 Mn(+2) 81/97.0* * Low spin and high spin values (section 8.2.3)Source: Shannon,R.D. (1976) `Revised effective ionic radii in halides and chalcogenides',Acta Cryst.A32, 751. This includes further oxidation states and coordination numbers.
4.2 Anion radii (6-coordinate) (pm)
Elem. Rad. Elem. Rad. Cl(-1) 167 O(-2) 126 Br(-1) 182 S(-2) 170 F(-1) 119 Se(-2) 184 I(-1) 206 Te(-2) 207
Periodic Properties: Ionization
Energy
It is defined as the energy required
to remove the outermost electron from a gaseous atom. A "gaseous atom"
means an atom that is all by itself, not hooked up to others in a solid
or a liquid. When enough energy is added to an atom the outermost electron
can use that energy to pull away from the nucleus completely (or be pulled,
if you want to put it that way), leaving behind a positively charged ion.
That is why it's called ionization, one of the things formed in the process
is an ion. The ionization energy is the exact quantity of energy that it
takes to remove the outermost electron from the atom.
In your lab work on atomic spectra you observed that a gas would conduct electricity and emit light when it was subjected to a high voltage. When there is little or no voltage applied to the gas in the tubes, no light is emitted and the gas does not conduct electricity. One method for measuring the ionization energy of a gas is to slowly increase the voltage applied to it until it does conduct electricity and emit light. The voltage at which that occurs can be used to calculate the ionization energy.
If the ionization energy is high, that means it takes a lot of energy to remove the outermost electron. If the ionization energy is low, that means it takes only a small amount of energy to remove the outermost electron.
Let’s use your understanding of atomic structure to make some predictions. Think for a minute about how ionization energy would be affected by three of the factors we were talking about earlier: (1) nuclear charge, (2) number of energy levels, and (3) shielding.
Defined as the Quantity of energy required to remove an electron from
an atom is directly related to Zeff . Ionization potential increase
going across a period and decrease going down a group.
As the effective nuclear charge
increases, the attraction between the nucleus and the electrons increases
and it requires more energy to remove the outermost electron and that means
there is a higher ionization energy. As you go across the periodic table,
nuclear charge is the most important
consideration. So, going across the periodic table, there should
be an increase in ionization energy because of the increasing nuclear charge.
Going down
the table, the effect of increased nuclear charge is balanced by the effect
of increased shielding, and the number of energy levels becomes the predominant
factor. With more energy levels, the outermost electrons (the valence electrons)
are further from the nucleus and are not so strongly attracted to the nucleus.
Thus the ionization energy of the elements decreases as you go down the
periodic table because it is easier to remove the electrons. Another way
of looking at that is that if you are trying to take something from the
first energy level, you have to take it past the second, the third, the
fourth and so on, on the way out. But if something is already in the third
or fourth energy level, it doesn't have to be taken as far to get away
from the nucleus. It is already part way removed from the nucleus.
The first ionization enthalpies most effectively illustrate all these
effects.

The electrons removed when nitrogen and oxygen are ionized also come from 2p orbitals.
N: [He] 2s2 2p3
O: [He] 2s2 2p4
But there is an important difference in the way electrons are distributed in these atoms. Hund's rules predict that the three electrons in the 2p orbitals of a nitrogen atom all have the same spin, but electrons are paired in one of the 2p orbitals on an oxygen atom.

Hund's rules can be understood by assuming that electrons try to stay as far apart as possible to minimize the force of repulsion between these particles. The three electrons in the 2p orbitals on nitrogen therefore enter different orbitals with their spins aligned in the same direction. In oxygen, two electrons must occupy one of the 2p orbitals. The force of repulsion between these electrons is minimized to some extent by pairing the electrons. There is still some residual repulsion between these electrons, however, which makes it slightly easier to remove an electron from a neutral oxygen atom than we would expect from the number of protons in the nucleus of the atom.
Periodic Properties: Electron Affinity
Atoms can also gain electrons to form negatively charged ions (anions)
It is also called Electron Attachment Enthalpies
These correspond to the process:
It is possible to measure the enthalpy of this process directly in very few cases. The elements which normally form cations have positive DHEA and the elements which normally form di- or trianions ususally have positive DEEA for the second and third electron attachment steps in spite of their stability in ionic compounds. It would be nice to have more because one of the scales of elecronegativity uses them. The electron affinity is the energy change associated with an atom or ion in the gas state gaining an electron. Defined as the energy released/absorbed when a gaseous atom gains an electron. Electron affinity is directly related to Zeff. Electron affinity value could either be + or -, therefore care should be exercised when predicting the trends.
Thus, we say that chlorine has an electron affinity of -328 kJ/mol.
The greater the attraction for the
electron, the more exothermic the process. For anions and some neutral
atoms, added an electron is an endothermic process, i.e. work must
be done to force an electron onto
the atom. This results in the formation of an unstable anion.
The halogens,
which are one electron short of a completely filled p subshell have the
greatest
attraction
for an electron (i.e. the electron affinity has the largest negative magnitude)
In adding
an electron they achieve a stable electron configuration like the noble
gases
The 2A
and 8A groups have filled subshells (s, and p, respectively) and therefore,
an
additional
electron must reside in a higher energy orbital. Adding an electron to
these groups
is an endothermic
process
Across a period, value of electron affinity generally decrease
(going from a small positive value to a larger negative value represents
a decrease) Going down a group Electron Affinity values increase.
Electronegativity:
These measure the tendency for one element of a bonded pair to attract
the electrons associated with the bond to itself. The polarity of a bond,
that is its ionic character is assessed by comparing the two electronegativities
of the two bonded atoms. It is also possible to assign an electronegativity
to a chemical group e.g. CH3. In LiH molecule,
it would seem that the bonding orbital places more electron density on
the hydrogen than on the lithium since the orbital shape describes the
probability of finding the electrons. As a result, the hydrogen end of
the moelcule would be slightly negative and the lithium end would be slightly
positive.This situation is called a polar bond in which the electrons in
the bond are being shared, but not equally shared.
In almost every case in which a bond is formed between two different atoms the resulting bond will be polar.
I
In the 1930's, Linus Pauling (1901 - 1994), an American chemist who
won the 1954 Nobel Prize, recognized that bond polarity resulted from the
relative ability of atoms to attract electrons. Pauling devised a measure
of this electron attracting power which he called "electronegativity"
which he defined as the "power of an atom in a molecule to attract electrons
to itself." Electronegativity only has meaning in a bond.
The table below presents the electronegativities for the main group elements.
| H = 2.1 | x | x | x | x | x | x |
| Li = 1.0 | Be = 1.5 | B = 2.0 | C = 2.5 | N = 3.0 | O = 3.5 | F = 4.0 |
| Na = 0.9 | Mg = 1.2 | Al = 1.5 | Si = 1.8 | P = 2.1 | S = 2.5 | Cl = 3.0 |
| K = 0.8 | Ca = 1.0 | Ga = 1.6 | Ge = 1.8 | As = 2.0 | Se = 2.4 | Br = 2.8 |
| Rb = 0.8 | Sr = 1.0 | In = 1.7 | Sn = 1.8 | Sb = 1.9 | Te = 2.1 | I = 2.5 |
| Cs = 0.7 | Ba = 0.9 | Tl = 1.8 | Pb = 1.9 | Bi = 1.9 | Po = 2.0 | At = 2.2 |
Generally, the electronegativity increases moving left to right across
a row, and decreases going down the table. Notice that this
trend is violated by the Group 13 metals for which the electronegativity
drops from B to Al as expected, but hen rises slightly going down to Tl.
This effect is due to the intervention of the d electrons and other effects
that come into play with very large atoms.
The transition metals are not presented in this chart to conserve room,
but their values range from 1.0 to about 2.4.
There have been several methods used to generate numerical electronegativity
scales:
Pauling Electronegativity, cp
Pauling
electronegativity has been calculated based on energetics of bond formation
is the first electronegativity scale.
cp are
commonly used in tables to make decisions about bond polarities. Pauling
reasoned that the dissociation energy of a covalent bond, Dtheo(A-B),
if it were perfectly covalent, could be calculated as the average of the
experimental dissociation energies Dexp(A-A) and Dexp(B-B).
Partially ionic bonds would have higher observed dissociation energies
Dexp(A-B). Therefore the difference between Dexp(A-B)
and Dtheo(A-B), D(A-B),
will be proportional to the difference in electronegativities cA
and cB.
For example, the bond energies of H-H and F-F are, respectively,
436 and 158 kJ mol-1. If H-F were perfectly covalent, which
is not, the bond energy ought to be (436 x 158)½ = 262
kJ mol-1. (Pauling used the "geometric" mean rather than the
"arithmetic" mean, (436 + 158)/2 = 297 kJ mol-1, because, by
weighting the smaller number more, it gives better results.) The experimental
H-F bond energy is 566 kJ mol-1 so the difference, 566 - 262
= 304 kJ mol-1 is proportional to the difference cF
- cH.
The formula which Pauling used to express this was:
Mulliken Electronegativity, cM
This scale is based on the average of the ionization enthalpy and the negative
of the electron attachment enthalpy. R.S. Mulliken proposed an electronegativity
scale in which the Mulliken electronegativity, cM
is related to the electron affinity EAv (a measure of the tendency
of an atom to form a negative species) and the ionization potential
IEv (a measure of the tendency of an atom to form a positive
species) by the equation:
cM = (DHIE - DHEA)/2
A strong tendency to gain electrons is characterized by a large negativeDHEA and a large positive DHIE will go with a reluctance to lose electrons, both of which will contribute to an element showing a large electronegativity. The method makes gfreat sense but is limited by the lack of electron attachment enthalpy data.
DHIE - DHEA depends on specific valence state - so for trigonal boron compounds, a values of electronegativity can be defined for sp2 hybrid orbitals. If the values of IE and EA are in units of MJ mol-1, then the Mulliken electronegativity cM can be expressed on the Pauling scale by the relationship:
cp = 1.35 cM1/2 - 1.37
The Allred-Rochow electronegativity- cAR.
The underlying theoretical concept is that an electron close to the
surface of an atom i.e. a bonding electron is held there by the effective
nuclear charge it experiences, and the force resisting its removal is given
by:
cAR = 0.359(Z*/r2)
+ 0.744
Assuming the electronegativity is proportional to this force, and adding
constants to bring the Allred-Rochow scale into correspondence with the
Pauling scale (i.e. F = 4.00 and H = 2.22) gives:
The Allen Scale
This scale, which is designed only for the representative (main
group) elements, comes back to the use of ionization enthalpy data. In
this case the weighted average DHIE
for the s and p valence electrons, obtained from (atomic) spectroscopic
data is used:
cspec = (mes + nep)/(m + n)
where n and m are the numbers of s and p electrons, respectively. Allen's numbers do not differ much from the other scales.
Polarizability
The ease with which the charge distribution in a molecule can be distorted
by an external electric field is called
its polarizability ('squashiness' of its e- cloud). The greater the
polarizability, the more easily its e- cloud can be
distorted. Larger molecules tend to have greater polarizabilities
- they have more e- and their e- are further from the nuclei
e.g. I2 is more polarizable than F2. Measures
the ease of distortion of an atom in an electric field. If the frontier
orbitals are not widely separated, then the atom will be more polarizable.
This happens more for heavier elements. Atoms resistant to polariation
are "hard", while atoms which are easily polarized are "soft".
Recommended Questions from Shriver and Atkins:
| "Exercises" | |
| 1.1, 1.2 | These questions are about nuclear chemistry. |
| 1.3 - 1.19 | You should be able to answer all these important questions. They could be on exams. |
| "Problems" | |
| 1.1 | This could be done using the equations in Table 1.2 but is well beyond the scope of this course! |
| 1.2 | This question is asking you to distinguish between the radial wavefunction and the radial distribution function. |
| 1.3 | You have to calculate the ionization energy of an excited H atom, and then explain the comparative values of all three species. |
| 1.4 | This is a question about photoelectron spectroscopy. The difference between the energy of the irradiating photons (use E = hn and c = nl), and the kinetic energy (use E = ½mv2) of the ejected electrons corresponds to their ionization energy. The main problem here is just to get everything into the same units. |
| 1.5, 1.6 | Do not waste your time with these questions unless you are headed for a career as a chemisry teacher! |
| 1.7 - 1.9 | These are more nuclear chemistry questions: not covered in 2001. |
| 1.10 | Shielding is a concept that some students find difficult. You should probably be able to take a shot at this. |
| 1.11 | Tricky little question unless you get the ground state configurations written down correctly. |
| 1.12 | You should be able to do this, although you need not memorize the mathematical functions. |
| 1.13 | An interesting question but a bit to philosophical for Chem 481! |
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