Periodicity and Atomic Structure

Israel Schek :xc: ;c 1
http://www.tau.ac.il/chemistry/undergraduate/undergraduate-courses.html
http://www.tau.ac.il/video
Israel Schek p o ::o
aa :n nuc:a:
Tel Aviv University, Israel
General and Inorganic Chemistry:
Atom Structure and the Periodic Table
: n n : 3
r :rn nn n:v nn: c :un n::n
Periodicity Mendeleev Table(a)
Dmitri Ivanovich Mendeleev (1837-1907) in 1869 (along with the
German chemist Julius Lothar Mayer) came out with the idea:
The known elements may be arranged in a periodic rectangular chart
according to their atomic mass (not yet atomic number an
unknown concept at their current time).
This periodicity would reIlect their chemical and physical properties.
To us, who are 'scientiIically educated, it looks obvious that
chemical and physical properties are oI periodic nature.
But one should appreciate the genius insight oI the periodic
arrangement rather than in the 'more natural linear arrangement.
One oI the Iirst great successes oI the periodicity was the prediction
oI accurate characteristic properties oI then (1871) concurrent
unknown elements, according to empty entries in the table.
One hole was immediately below Silicon, and was temporarily
termed Eka-Silicon, later known as Germanium.
The present order is according to the atomic number (nuclear
charge), not the atomic mass, as shown in 1913 by Henry Moseley
(1887-1915 Gallipoli, Dardanelles with other 55-65,000 Allied
Soldiers).
He measured wavelengths oI the X-ray
spectral lines oI a number oI elements.
Periodicity Mendeleev Table(b)
Earlier Versions(a)
Dmitri Ivanovich Mendeleev
Centenary oI Periodic Table,
Soviet Union 1969
showing his Notes
Earlier Versions(b)
Periods General Structure
Block structure oI the electron orbitals
Groups (Columns) at the Periodic Table
The present table is oI two-dimensional rectangular shape (with
obvious stairs and additional rows).
Rows are called periods and columns are called groups.
Elements belonging to a common group have in general similar
properties, which change gradually Irom one period to the next
one.
The main reason is that they share common valence electronic
structure. The number oI valent electrons deIines the group
number.
Groups (Columns) at the Periodic Table
http://www.privatehand.com/Ilash/elements.html
Alkaline Group
The elements oI the Iirst column are oI the alkaline group, or
alkali metals or Group I (n :p: n5nn):
Lithium, Sodium - :n:, Potassium - x:o, Rubidium, Cesium,
Francium
Electron conIiguration inert gas]ns
1
These metals (high electron and thermal conductivities) are:
SoIt
Low melting points
Silver color
All react drastically with water and replace the hydrogen. n :n!
Hardly Iound in their Iree state, but in compounds
Metallic properties grow stronger down the column
Alkaline Earth Group
The elements oI the second column are oI the alkaline earth
group, or alkali earth metals or Group II ( n:p: n5nn
n: :oy):
Beryllium, Magnesium, Calcium - +c, Strontium, Barium,
Radium
2
These metals have quite similar properties to their leIt neighbors:
But less aggressive
SoIt
Low melting points
Hardly Iound in their Iree state, but in compounds
Metallic properties grow stronger down the column
Group III
Group III (no speciIic name) is at the 13
th
column (beyond the
large gap).
Boron, Aluminum - :nn, Gallium, Indium, Thallium
2
np
1
Apart Irom boron, which is semi-metal, other group elements are
metals.
Group IV
Group IV (no speciIic name) is at the 14
th
column (beyond the large
gap) is):
Carbon - nn o, Silicon - :x, Germanium, Tin - :+a, Lead -
n:oy
2
np
2
Carbon is nonmetal and comprises LiIe
Silicon (2nd most abundant element in the Earth mantle aIter
oxygen), germanium - semimetals, and tin and lead are metals.
Carbon, silicon, and germanium are usually in oxidation state 4,
whereas tin and lead are 2.
Group V
Group V (no speciIic name) is at the 15
th
column (beyond the
large gap).
Nitrogen - p:n, Phosphorus - n:, Arsenic, Antimony,
Bismuth
2
np
3
Nitrogen and phosphorus are nonmetals, arsenic and antimony
are semimetals, and bismuth is a metal.
Oxides oI the Iirst three elements are acidic, that oI bismuth is
basic and the oxides oI antimony are in between, i.e. amphoteric.
Nitrogen makes 80 oI our atmosphere.
Group VI
Group VI (no speciIic name) is at the 16
th
column (beyond the
large gap).
Oxygen - xnn, Sulfur - n:ox, Selenium, Tellurium, Polonium
2
np
4
Oxygen, sulIur, and selenium are nonmetals, tellurium is semi-
metal, and polonium is a metal (though not strong).
Oxygen is the most abundant element on Earth, and the third most
abundant in Universe (aIter hydrogen and helium).
And, we breathe it.
Halogens Group
Halogens ('producers oI salts), Group VII are at the 17
th
column
(beyond the large gap).
Fluorine, Chlorine, Bromine, Iodine, Astatine
2
np
5
React readily with most metals
Hence, Iound in Nature in compounds.
Fluorine and chlorine are gases under regular conditions,
bromine is a liquid, and iodine is solid.
Inert Gases Group
Noble gases or inert gases are at the 18
th
column
(beyond the large gap):
Helium, Neon, Argon, Krypton, Xenon, Radon
Electron stable conIiguration previous inert gas]ns
2
np
6
Since they are extremely inert (though not absolutely),
they are Iound in Nature as monatomic gases.
Argon (leIt over aIter nitrogen and oxygen are removed Irom dry air)
was Iirst discovered by spectroscopic analysis in 1894 by Lord
Rayleigh (recall Blackbody Radiation) and William Ramsay (1852-
1916). Both won Nobel Prize in 1904.
Lord Rayleigh
William Ramsay
Periodic Table Groups(a)
The 'inertia oI inert gases suggested the explanation Ior chemical
bonding.
As Gilbert Lewis (1875-1946) observed, atoms tend to arrange their
electronic constitutions in bonds, so as to reach an octet -
the stable octal inert gas conIiguration.
William Ramsay (1852-1916) (leIt) and Physiologist Ivan Petrovich Pavlov (1849-1936)
60
th
Anniversary oI Nobel Prize, Sweden 1964
Gilbert Lewis
This scope was later extended when quantum mechanical tools
were applied to chemical bonds and the octet was rationalized.
Ideas like molecular orbitals (MO) were incorporated and the
region oI the electron wave Iunction was then extended to the
whole molecule, rather than the sole atom.
Moreover, it was Iound that in some molecules the inert gas octet
rule is not kept more than eight electrons are populated around
some atoms (e.g. in SF
6
, PCl
5
).
Although inert, mostly the heavier ones are capable to take part in
chemical bonds, though not very stable (e.g. Ar-Ar, Xe-Xe and
clusters like Xe
n
(n~3)).
Periodic Table Groups(b)
Transition Metals
The columns 3
rd
to 12
th
, between Group II and Group III are oI
the transition metals.
Their name is derived Irom their intermediate properties between
the active alkali and alkaline earth metals oI the Iirst two groups
and the mildly active metals oI Group III and Group IV.
First period oI transition metals:
Scandium, Titanium, Vanadium, Chromium, Manganese,
Ferum - ::a, Cobalt, Nickel, Copper - non:, Zinc - ya
Electron conIiguration is oI a partially Iilled d-orbital
inert gas]nd
k
(n+1)s
2
Consequences oI the Orbital Energies(a)
As a result oI the shielding eIIect the 4s-orbitals, which penetrate
deeper into the nuclear zone than do the 3d-orbitals, have lower
energy than the latter.
Hence, potassium (K) and calcium (Ca) have their electrons
exterior to the argon conIiguration in 4s - K: |Ar|4s
1
and
Ca: |Ar|4s
2
.
The next 10 electrons occupy in their turn the 3d-orbital to Iorm
the transition metals, starting with scandium Sc: |Ar|3d
1
4s
2
up to
zinc Zn: |Ar|3d
10
4s
2
.
The energies oI 4s- and 3d-orbitals are very close, and due to e-e
interaction, the system preIers energetically to have halI-occupied
(d
5
) oI the complete-occupied (d
10
) orbitals.
Thus, an electron would be located in 3d-orbital rather than in the
4s-orbital.
For example, the conIiguration oI chromium is Cr: |Ar|3d
5
4s
1
instead oI |Ar|3d
4
4s
2
, which is also acceptable, but a bit more
energetic.
The copper conIiguration is Cu: |Ar|3d
10
4s
1
instead oI |Ar|3d
9
4s
2
,
where the 4s-orbital is only halI Iilled.
Consequences oI the Orbital Energies(b)
This energetic nearness oI 4s and 3d makes the transition metals
have diIIerent valences.
AIter Iilling up the 4p-orbital Irom gallium Ga: |Ar|3d
10
4s
2
4p
1
to krypton Kr: |Ar|3d
10
4s
2
4p
6
, the Iirst long period is complete.
Then we have the IiIth row (or IiIth period) with its 18 elements.
It starts with rubidium Rb: |Kr|5s
1
, through the transition metals
yttrium Y: |Kr|4d
1
5s
2
to cadmium Cd: |Kr|4d
10
5s
2
, via indium
In: |Kr|4d
10
5s
2
5p
1
up to xenon Xe: |Kr|4d
10
5s
2
5p
6
, which
completes the IiIth row and is an inert element.
Consequences oI the Orbital Energies(c)
Change oI orbital
energies
oI 4s and 3d between
Ca and Sc.
Beyond Ca, 3d-orbital
energy Ialls abruptly.
Orbital Energies
The sixth row starts with cesium Cs: |Xe|6s
1
and barium Br:
|Xe|6s
2
.
Then starts the Iilling up oI the orbital 5d with lanthanum La:
|Xe|5d
1
6s
2
.
Next to lanthanum starts Iilling up the next 14 elements in which
the upper electrons are oI the orbital 4I (!3). They are called
lanthanides.
They start with cerium Ce: |Xe|4I
1
5d
0
6s
2
, through europium Eu:
|Xe|4I
7
5d
0
6s
2
, to lutetium Lu: |Xe|4I
14
5d
1
6s
2
.
Consequences oI the Orbital Energies(d)
Then going back to Iilling up the 10 transition metals with 5d
Irom haInium HI: |Xe|4I
14
5d
2
6s
2
, to mercury Hg: |Xe|4I
14
5d
10
6s
2
.
Following are the main elements oI 6p, starting with thallium Tl:
|Xe|4I
14
5d
10
6s
2
6p
1
, and ending with the next inert element radon
Rn: |Xe|4I
14
5d
10
6s
2
6p
6
, completing the sixth row.
Following is the seventh row starting with Irancium Fr: |Rn|7s
1
and radium Ra: |Rn|7s
2
.
Then comes actinium with its 6d-electron Ac: |Rn|6d
1
7s
2
.
Then come the actinides with their 5I-electrons, starting with
thorium Th: |Rn|5I
1
6d
0
7s
2
, through americium Am: |Rn|5I
7
6d
0
7s
2
,
to lawrencium Lw: |Rn|5I
14
6d
1
7s
2
.
Consequences oI the Orbital Energies(e)
VeriIication oI the conIigurations may be executed by passing a
beam oI atoms through an inhomogeneous magnetic Iield, as done
by Stern and Gerlach.
Since a spin is a magnetic moment attached to the electron,
it Ieels the magnetic Iield and interacts with it.
According to the amount oI deviation oI the atomic beam Irom the
initial direction, one can determine the overall spin state oI the
system.
One may naively claim that the total spin moment is a sum oI the
individual electronic spin moments.
Consequences oI the Orbital Energies(I)
For example, the |Ar|3d
5
4s
1
conIiguration oI chromium has 6
unpaired spins (altogether 61/23 units oI magnetic moment).
The other, |Ar|3d
4
4s
2
conIiguration oI chromium, has 4 unpaired
spins (altogether 41/22 units oI magnetic moment.
A beam oI atoms in the Iirst conIiguration would be deIlected more
intensively than the second one, which is detected on the collecting
screen.
A system with unpaired electron is a paramagnet and a system with
no unpaired electron is a diamagnetic.
Consequences oI the Orbital Energies(g)
Lanthanides
There are two more Iamilies oI metals:
The 14 lanthanides starting with Lanthanum, which are
characterized by partially Iilled 4I-orbitals: inert gas]6s
2
4f
k
The 14 actinides starting with actinium, which are characterized
by partially Iilled 5I-orbitals: inert gas]7s
2
5f
k
They are very similar in their properties and thereIore hard to
separate.
The actinides include the heavy radioactive elements among them
the trans- uranium (Z~92).
Periodic Properties
Periodic Properties - Atomic Radii (a)
Periodicity oI properties is pronounced mostly in sizes and
energies. Following are some typical examples.
The notion oI atomic radius oI an element is not a sharp concept
due to the wave-like nature oI the elementary particles.
One may locate the major part oI the existence oI the "electronic
cloud" in a certain radius around the nucleus.
There are orders oI magnitudes, and deIinitely, the uranium atom
is larger than a hydrogen atom.
The atomic radius is deIined as halI the distance between
neighboring equivalent atoms (e.g. in H
2
molecule or Fe solid).
They are obtained in spectroscopic or crystallographic
measurements.
Atomic Radii in picometer (taken Irom Atkins & Jones)
Periodic Properties - Atomic Radii (b)
Atomic radii decrease with growing atomic number across the
row, due to growing oI the eIIective nuclear charges.
Radii are higher at alkaline metals, lower at the earth-alkaline,
then decrease more gradually towards the inert elements.
Periodic Properties - Atomic Radii (c)
Periodic Variation oI Atomic Radii in picometer (Irom Atkins & Jones)
Periodic Properties - Atomic Radii (d)
Periodic Properties - Mendeleev
Dmitri Mendeleev Centenary oI Periodic Table,
Soviet Union 1969
Periodic Properties - Ionic Radii (a)
As a basis to determination oI the ionic contributions to inter-
nuclear distances one takes the radius oI the oxygen ion O
-2
as
0.14nm (1.4A).
Cations are smaller than their parent elements due to loss oI their
valent electrons, leaving behind much smaller cores.
Anions on the other hand are larger than their parent atoms due to
gain oI electrons.
Ionic Radii in picometer (taken Irom Atkins & Jones)
Periodic Properties - Ionic Radii (b)
Periodic Properties - Ionization Potential (a)
Ionization potential is the minimum energy needed to remove an
electron Irom the ground state oI the element
Ah
ionization
is also called the ionization enthalpy (energy to be
invested at constant pressure oI the gaseous atom).
Since the electron is attracted to the rest oI the atom, even iI it is a
Iar electron in highly lying orbitals, energy always is invested to
remove an electron Irom the neutral atom.
ionization
AH ; e (g) E E(g)

Ionization Potentials in kJoule/mole (taken Irom Atkins & Jones)
Periodic Properties - Ionization Potential (b)
The ionization potential increases across a row Irom the alkaline
metals low values towards the inert elements high values.
Than it Ialls back abruptly down to the next low value at the next
alkaline element at the next row.
When the peak values at the inert elements are connected there is
a smooth decrease in the line starting at the highest value oI
Helium (2370. kJ/mole) towards that oI Radon (1040. kJ/mole).
It is much harder to ionize the helium atom rather than the larger
inert atoms.
Periodic Properties - Ionization Potential (c)
Atoms become smaller across a period (see the atomic radii
graph).
Due to increasing eIIective charges electrons are more strongly
attracted to the nuclei when going Irom the alkaline element
toward the inert element in a period.
Going down a group the outermost electrons are Iarther away
Irom the nuclei and thereIore less attracted and less bound.
Periodic Properties - Ionization Potential (d)
Since on the average outermost d-orbitals are deeper in location
than their preceding s-orbitals, moving Irom one element to the
next one across a transition elements group does not show a steep
change in relative values.
This point is more emphasized across the lanthanides and
actinides, where there is hardly a change in the ionization potential
inside the group.
Periodic Properties - Ionization Potential (e)
Periodic Variation oI Ionization Potentials (Irom Atkins & Jones)
Periodic Properties - Ionization Potential (I)
Periodic Properties - Electron AIIinity(a)
Electron aIIinity (meaning attraction towards electrons) is the
energy released when an electron is added to an atom or ion
AH
gain
is positively deIined when there is a gain oI energy when
the extra electron joins the neutral atom, and negatively when
energy must be invested to Iorce an electron into the neutral atom.
Contrary to ionization potential, the process oI gaining an electron
may be exothermic as well as endothermic.
gain
AH (g); E e E(g)

The upper right corner is electron-philic (love oI electrons).
It is mostly pronounced Ior the Iluorine, and other halogens, but
also the VI group oI oxygen and sulIur. The electron is welcomed.
Inert elements do not "Ieel" aIIinity towards an extra electron,
mostly neon.
Nitrogen and some earth-alkaline dislike the idea to be negative.
Periodic Properties - Electron AIIinity(b)
Electron AIIinity in kJoule/mole (taken Irom Atkins & Jones)
Periodic Properties - Electron AIIinity(c)
Electronegativity is the extent oI the element attraction towards
the electron.
Linus Carl Pauling (1901-1994) and Robert Sanderson Mulliken
(1896-1986) deIined a numerical measure Ior electronegativity.
Pauling: 1954 Nobel Prize laureate Ior his studies on the nature oI
the chemical bond and molecular structure oI proteins.
Mulliken: 1966 Nobel Prize laureate Ior his studies on chemical
bonds and the electron structure oI molecules by means oI the
orbital method.
Periodic Properties - Electronegativity(a)
The electronegativity considers the resistance to lose an electron
(expressed by the ionization potential) as well as the agreement to
have an extra one (expressed by the electron aIIinity).
The simplest expression (due to Mulliken (1934) is the average oI
both values
EA)/2 (IP
Periodic Properties - Electronegativity(b)
Very electronegative elements (halogens, small VI group-atoms)
at the upper right corner zone.
Electropositive elements (heavy alkaline, heavy earth-alkaline)
at the lower leIt corner ('they dislike electrons).
Atkins & Jones
Periodic Properties - Electronegativity(c)
The scale runs as
The electronegativity would serve deIining the polarity oI a
chemical bond.
The electric dipole moment oI a simple diatomic molecule AB is
approximately linearly related to the electronegativity diIIerence.
The larger this diIIerence, the more polar the bond is.
4 0.79
F Ce

B A

Periodic Properties - Electronegativity(d)
The periodicity oI the Pauling electronegativity
Linus Carl Pauling,
Upper Volta 1977
Periodic Properties - Electronegativity(e)
Finally, in 3-Dim representation:
Periodic Properties - Electronegativity(I)

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