INVISIBLE MECHANICS

"don't be a normie, i guess"

INVISIBLE MECHANICS
1. Genesis of Periodic Classification
1.1 Dobenier’s Triad
The middle element of each Triad is an atomic weight halfway between the other two.
The properties of the middle element are in between those of the other two members.

1.2 Newland Law of Octaves

Arranged in increasing order of atomic weight.
Every eighth element is having similar properties to first one.
Failed valid upto calcium.

1.3 Lothar meyer

He plotted a graph between the atomic mass and physical properties of the elements (viz.
Atomic volume, boiling point, melting point etc..)

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From this curve, it was observed that the elements having similar properties, occupied the
same corresponding position on the curve.
Crest --> Alkali Position .
Descending position --> Alkaline Earth Metal.
Ascending position --> Halogen .
Trough --> Transition Metal .

2.Mendelev’s periodic Table

2.1 Periodeic Law

Properties of elements are periodic function of their atomic weight.
9 Vertical columns.
7 Horizontal rows.
Similar nature of elements were placed in same vertical column with incresing atomic weight.

2.2 Merits
He left gap for elements which were not discoverd.
Ga --> Ekaaluminium.
Ge--> Ekasilicon
He corrected the atomic weight of some elements .
{ U Be I Au Pt }

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2.3 Demerits
At some places, Order of atomic weight is changed to satisffy same physical and chemical
properties.
Co [58.9 ] Ni [58.6 ]
Te [127.6] I [126.9]
Isotope were not given a separate poition.

3.Modern Periodic Table

Henry Moseley observed X-ray spectra of the elements.
A plot of (where is frequency of X-rays emitted) against atomic number (Z) gave a straight line
and not the plot of vs atomic mass
Law : The physical and chemical properties of the elements are periodic functions of their atomic
numbers.
7 rows & 18 Vertical Column
1 --> 1s
2 -->2s, 2p
3 -->3s, 3p
4 -->4s, 3d, 4p
5 --> 5s, 4d, 5p
6 --> 6s, 4f, 5d, 6p
7 --> 7s, 5f, 6d, 7p

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3.1 NOMENCLATURE OF ELEMENTS WITH
ATOMIC NUMBERS > 100

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3.2 Electronic configuration in periods

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 4.1 S- Block
The elements of Group 1 (alkali metals) and Group 2 (alkaline earth metals) which have ns1 and
ns2 outermost electronic configuration belong to the s-Block Elements. They are all reactive
metals with low ionization enthalpies. They lose the outermost electron(s) readily to form 1+ ion
(in the case of alkali metals) or 2+ ion (in the case of alkaline earth metals). The metallic
character and the reactivity increase as we go down the group. Because of high reactivity they
are never found pure in nature. The compounds of the s-block elements, with the exception of
those of lithium and beryllium are predominantly ionic.

4.2 P- Block

The p-Block Elements comprise those belonging to Group 13 to 18 and these together with the s-
Block Elements are called the Representative Elements or Main Group Elements. The outermost
electronic configuration varies from ns2np1 to ns2np6 in each period. At the end of each period is
a noble gas element with a closed valence shell ns2np6 configuration. All the orbitals in the
valence shell of the noble gases are completely filled by electrons and it is very difficult to alter
this stable arrangement by the addition or removal of electrons. The noble gases thus exhibit very
low chemical reactivity. Preceding the noble gas family are two chemically important groups of
nonmetals. They are the halogens (Group 17) and the chalcogens (Group 16). These two groups
of elements have highly negative electron gain enthalpies and readily add one or two electrons
respectively to attain the stable noble gas configuration. The non-metallic character increases as
we move from left to right across a period and metallic character increases as we go down the
group.

4.3 D- Block
These are the elements of Group 3 to 12 in the centre of the Periodic Table. These are
characterised by the filling of inner d orbitals by electrons and are therefore referred to as d-Block
Elements. These elements have the general outer electronic configuration (n-1)d1-10ns0-2
except for Pd where its electronic configuration is 4d105s0.. They are all metals. They mostly
form coloured ions, exhibit variable valence (oxidation states), paramagnetism and oftenly used
as catalysts. However, Zn, Cd and Hg which have the electronic configuration, (n-1) d10ns2 do
not show most of the properties of transition elements. In a way, transition metals form a bridge
between the chemically active metals of s-block elements and the less active elements of Groups
13 and 14 and thus take their familiar name “Transition Elements”.

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 4.4 F- Block
The two rows of elements at the bottom of the Periodic Table, called the Lanthanoids, Ce(Z = 58)
– Lu(Z = 71) and Actinoids, Th(Z = 90) – Lr (Z = 103) are characterised by the outer electronic
configuration (n-2)f1-14 (n-1)d0–1ns2. The last electron added to each element is filled in f-
orbital. These two series of elements are hence called the InnerTransition Elements (f-Block
Elements). They are all metals. Within each series, the properties of the elements are quite
similar. The chemistry of the early actinoids is more complicated than the corresponding
lanthanoids, due to the large number of oxidation states possible for these actinoid elements.
Actinoid elements are radioactive. Many of the actinoid elements have been made only in
nanogram quantities or even less by nuclear reactions and their chemistry is not fully studied. The
elements after uranium are called Transuranium Elements.

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 4.5 Metal ,Non Metal &Metalloids

In addition to displaying the classification of elements into s-, p-, d-, and f-blocks, Fig. 3.3 shows
another broad classification of elements based on their properties. The elements can be divided
into Metals and Non-Metals. Metals comprise more than 78% of all known elements and appear
on the left side of the Periodic Table. Metals are usually solids at room temperature [mercury is
an exception; gallium and caesium also have very low melting points (303K and 302K,
respectively)]. Metals usually have high melting and boiling points. They are good conductors of
heat and electricity. They are malleable (can be flattened into thin sheets by hammering) and
ductile (can be drawn into wires). In contrast, non-metals are located at the top right hand side
of the Periodic Table. In fact, in a horizontal row, the property of elements change from metallic
on the left to non-metallic on the right. Non-metals are usually solids or gases at room
temperature with low melting and boiling points (boron and carbon are exceptions). They are
poor conductors of heat and electricity. Most nonmetallic solids are brittle and are neither
malleable nor ductile. The elements become more metallic as we go down a group; the non-
metallic character increases as one goes from left to right across the Periodic Table. The
change from metallic to non-metallic character is not abrupt as shown by the thick zig-zag line
in Fig. 3.3. The elements (e.g., silicon, germanium, arsenic, antimony and tellurium) bordering
this line and running diagonally across the Periodic Table show properties that are
characteristic of both metals and non-metals. These elements are called Semi-metals or
Metalloids.

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 5. Atomic Radius
You can very well imagine that finding the size of an atom is a lot more complicated than
measuring the radius of a ball. Do you know why? Firstly, because the size of an atom (~ 1.2 Å
i.e., 1.2 × 10–10 m in radius) is very small. Secondly, since the electron cloud surrounding the
atom does not have a sharp boundary, the determination of the atomic size cannot be precise.
In other words, there is no practical way by which the size of an individual atom can be
measured. However, an estimate of the atomic size can be made by knowing the distance
between the atoms in the combined state. One practical approach to estimate the size of an
atom of a non-metallic element is to measure the distance between two atoms when they are
bound together by a single bond in a covalent molecule and from this value, the “Covalent
Radius” of the element can be calculated. For example, the bond distance in the chlorine
molecule (Cl2) is 198 pm and half this distance (99 pm), is taken as the atomic radius of
chlorine. For metals, we define the term “Metallic Radius” which is taken as half the internuclear
distance separating the metal cores in the metallic crystal. For example, the distance between
two adjacent copper atoms in solid copper is 256 pm; hence the metallic radius of copper is
assigned a value of 128 pm. For simplicity, in this book, we use the term Atomic Radius to refer
to both covalent or metallic radius depending on whether the element is a non-metal or a metal.
Atomic radii can be measured by X-ray or other spectroscopic methods.
The atomic radii of a few elements are listed in Table 3.6. Two trends are
obvious. We can explain these trends in terms of nuclear charge and energy level. The atomic
size generally decreases across a period as illustrated in Fig. 3.4(a) for the elements of the
second period. It is because within the period the outer electrons are in the same valence shell
and the effective nuclear charge increases as the atomic number increases resulting in the
increased attraction of electrons to the nucleus. Within a family or vertical column of the periodic
table, the atomic radius increases regularly with atomic number as illustrated in Fig. 3.4(b). For
alkali metals and halogens, as we descend the groups, the principal quantum number (n)
increases and the valence electrons are farther from the nucleus. This happens because the
inner energy levels are filled with electrons, which serve to shield the outer electrons from the
pull of the nucleus. Consequently the size of the atom increases as reflected in the atomic radii.
Note that the atomic radii of noble gases are not considered here. Being monoatomic, their
(non-bonded radii) values are very large. In fact radii of noble gases should be compared not
with the covalent radii but with the van der Waals radii of other elements.

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 6. Ionic Radius
The removal of an electron from an atom results in the formation of a cation, whereas gain of an
electron leads to an anion. The ionic radii can be estimated by measuring the distances between
cations and anions in ionic crystals. In general, the ionic radii of elements exhibit the same trend
as the atomic radii. A cation is smaller than its parent atom because it has fewer electrons while
its nuclear charge remains the same. The size of an anion will be larger than that of the parent
atom because the addition of one or more electrons would result in increased repulsion among
the electrons and a decrease in effective nuclear charge.
When we find some atoms and ions which contain the same number of electrons, we call them
isoelectronic species*. For example, O2–, F– , Na+ and Mg2+ have the same number of electrons
(10). Their radii would be different because of their different nuclear charges. The cation with the
greater positive charge will have a smaller radius because of the greater attraction of the
electrons to the nucleus. Anion with the greater negative charge will have the larger radius. In this
case, the net repulsion of the electrons will outweigh the nuclear charge and the ion will expand in
size.

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 7. Ionisation Energy
A quantitative measure of the tendency of an element to lose electron is given by its Ionization
Enthalpy. It represents the energy required to remove an electron from an isolated gaseous atom
(X) in its ground state.
In other words, the first ionization enthalpy for an element X is the enthalpy change (∆i H) for the
reaction depicted in equation 3.1.
X(g) → X+(g) + e– (3.1)

The ionization enthalpy is expressed in units of kJ mol–1. We can define the

second ionization enthalpy as the energy required to remove the second most loosely bound
electron; it is the energy required to carry out the reaction shown in equation 3.2.
X+(g) → X2+(g) + e– (3.2)

Energy is always required to remove electrons from an atom and hence ionization
enthalpies are always positive. The second ionization enthalpy will be higher than the first
ionization enthalpy because it is more difficult to remove an electron from a positively charged ion
than from a neutral atom. In the same way the third ionization enthalpy will be higher than the
second and so on. The term “ionization enthalpy”, if not qualified, is taken as the first ionization
enthalpy.

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8. Electron Gain Enthalphy

When an electron is added to a neutral gaseous atom (X) to convert it into a negative ion, the
enthalpy change accompanying the process is defined as the Electron Gain Enthalpy (∆egH).
Electron gain enthalpy provides a measure of the ease with which an atom adds an electron to
form anion as represented by equation 3.3. X(g) + e– → X– (g) (3.3) Depending on the element,
the process of adding an electron to the atom can be either endothermic or exothermic. For
many elements energy is released when an electron is added to the atom and the electron gain
enthalpy is negative. For example, group 17 elements (the halogens) have very high negative
electron gain enthalpies because they can attain stable noble gas electronic configurations by
picking up an electron. On the other hand, noble gases have large positive electron gain
enthalpies because the electron has to enter the next higher principal quantum level leading to a
very unstable electronic configuration. It may be noted that electron gain enthalpies have large
negative values toward the upper right of the periodic table preceding the noble gases.

Which of the following will have the most negative electron gain enthalpy and which the least
negative?
P, S, Cl, F. Explain your answer.

Solution:
Electron gain enthalpy generally becomes more negative across a period as we move from left to
right. Within a group, electron gain enthalpy becomes less negative down a group.However,
adding an electron to the 2p-orbital leads to greater repulsion than adding an electron to the
larger 3p-orbital. Hence the element with most negative electron gain enthalpy is chlorine; the one
with the least negative electron gain enthalpy is phosphorus.

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 9. Electonegativity

A qualitative measure of the ability of an atom in a chemical compound to attract shared

electrons to itself is called electronegativity. Unlike ionization enthalpy and electron gain
enthalpy, it is not a measureable quantity. However, a number of numerical scales of
electronegativity of elements viz., Pauling scale, Mulliken-Jaffe scale, Allred-Rochow scale have
been developed. The one which is the most widely used is the Pauling scale. Linus Pauling, an
American scientist, in 1922 assigned arbitrarily a value of 4.0 to fluorine, the element considered
to have the greatest ability to attract electrons. Electronegativity generally increases across a
period from left to right (say from lithium to fluorine)anddecreasedownagroup (say from fluorine
to astatine) in the periodic table. How can these trends be explained? Can the electronegativity
be related to atomic radii, which tend to decrease across each period from left to right, but
increase down each group ? The attraction between the outer (or valence) electrons and the
nucleus increases as the atomic radius decreases in a period. The electronegativity also
increases. On the same account electronegativity values decrease with the increase in atomic
radii down a group. The trend is similar to that of ionization enthalpy.

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