Periodic properties of

elements

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12/18/2022 Periodic properties 2
List of periodic properties of
elements
• Atomic size (atomic radius)
• Covalent radius
• Metallic radius
• Van der Waals radius
• Ionization potential
• Electron affinity
• Electronegativity

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Shielding
𝟒𝝅𝟐 𝒎𝒁𝟐 𝒆𝟒
𝑬𝒏 = −
• The energy of an electron
2 in an 𝒏𝟐 𝒉𝟐
𝑍
atom is a function of 2.
𝑛
• Since the nuclear charge (Z)
increases more rapidly than the
principal quantum number, one
might be led to expect the energy
necessary to remove an electron
from an atom would continually
increase with increasing atomic
number.
• This is not so, as can be shown by
comparing hydrogen (Z=1) with
lithium (Z = 3).
• The ionization energies are 1312
kJmol-1 (H) and 520 kJmol-1 (Li).

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Shielding (continued Page)

• The ionization energy of lithium is lower for two cases:

• 1. The average radius of 2s electron is greater than that
of 1s electron.
• 2. The 2s1 electron in lithium is repelled by the inner
core 1s2 electrons, so that the former is more easily
removed than if the core were not there.
• Another way of treating this inner core repulsion is to
view it as shielding or screening of the nucleus by the
inner electrons, so that the valence electron actually
sees only part of the total charge.
• Thus the ionization energy for lithium corresponds to
an effective nuclear charge of between one and two
units.

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Effective nuclear charge
• The energy of an electron is determined by an effective
nuclear charge (Z*), which is somewhat less than the
actual nuclear charge:
• 𝑍∗ = 𝑍 − 𝑆
• Where S is the shielding or screening constant.
• In order to estimate the extent of shielding, a set of
empirical rules have been proposed by Slater.
• Although the electric energies estimated by Slater’s
rules are often not very accurate, they permit simple
estimates to be made and will be found in
understanding related topics such as atomic size and
electronegativity.

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Slater rules for determining
shielding constant
• To calculate shielding constant for an electron in np or ns orbital:
1. Write out the electronic configuration of the element in the following
order and groupings: (1s) (2s,2p) (3s,3p) (3d) (4s,4p) (4d)(4f) (5s,5p)
etc.
2. Electrons in any group to the right on the (ns,np) group contribute
nothing to the shielding constant.
3. All of the other electrons in the (ns,np) group, shield the valence
electron to an extent of 0.35 each.
4. All electrons in (n-1) shell shield to an extent of 0.85 each.
5. All electrons in the (n-2) or lower, shield completely; that is their
contribution is 1.00 each.
When the electron being shielded is in an nd or nf group, rules 2,3 are the
same but rules 4,5 becomes
1. All electrons in groups lying to the left of the nd or nf group
contribute 1.00.

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Application of Slater’s rules in
determining shielding constant
• Consider the valence electron in the atom
• 𝟕𝑵 = 𝟏𝒔𝟐 𝟐𝒔𝟐 𝟐𝒑𝟑
• Grouping of the orbitals give (1s)2 (2s,2p)5.
• S = (2×0.85) + (4×0.35) = 3.10
• Effective nc, 𝑍 ∗ = 𝑍 − 𝑠 = 7.00 − 3.10 = 3.90 (3.834)
• Consider the effect in oxygen atom
• 8𝑂 = 1𝑠 2 2𝑠 2 2𝑝4
• Grouping of the orbitals give (1s)2 (2s,2p)6.
• S = (2×0.85) + (5×0.35) = 3.45
• Effective nc, 𝑍 ∗ = 𝑍 − 𝑠 = 8.00 − 3.45 =4.55 (4.453)
• For F atom the effective nuclear charge is 5.20 (5.10)
• For Ne atom the effective nuclear charge is 5.85 (5.758)

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Application of Slater’s rules in
determining shielding constant
• Consider the valence electron in the atom
• 𝟑𝟎𝒁𝒏 = 𝟏𝒔𝟐 𝟐𝒔𝟐 𝟐𝒑𝟔 𝟑𝒔𝟐 𝟑𝒑𝟔 𝟒𝒔𝟐 𝟑𝒅𝟏𝟎
• Grouping of the orbitals give (1s)2 (2s,2p)8(3s,3p)8
(3ds)10(4s)2
• S = (1×0.35) + (18×0.85) + (10×1.00) = 25.65
• Effective nc, 𝑍 ∗ = 𝑍 − 𝑠 = 30.00 − 25.65 =
4.35 (5.965)

12/18/2022 Periodic properties 9

 Reference: Inorganic chemistry, Huhee, Keiter; Page 33-35

Effective nuclear charge vs atomic size

Z* values r in IA elements Z* value vs r with constant n
with increasing n
Period 2 Z Z* r (Å) IP (eV)
IA n Z Z* r (Å) Li 3 1.3 1.55
H 1 1 1.0 - Be 4 1.95 1.12
Li 2 3 1.3 1.55 B 5 2.60 0.98
Na 3 11 2.2 1.90 C 6 3.25 0.91
K 4 19 2.2 2.35 N 7 3.90 0.92
Rb 5 37 2.2 2.48 O 8 4.55
Cs 6 55 2.2 2.67 F 9 5.20
• Atoms in a given family tend to Ne 10 5.85
increase in size from one period to the
next. Within a period, n does not change.
• Also supported by the radial The effective nuclear charge increases steadily,
distribution functions, where radius However, since the electrons added to the
increases with increasing n. valence shell shield each other very ineffectively.
12/18/2022 PeriodicAs a result a steady contraction from left10to right
properties
Periodic variations of atomic radius

In a period In a group
• Atomic and ionic radii • On moving down a
both decreases from group of regular
left to right across a elements both atomic
period in the periodic and ionic radii increases
table. with increasing atomic
number

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Limitations of Slater’s rules
• Slater formulated the rules of determining shielding of
electrons in proposing a set of orbitals for use in
quantum mechanical calculations.
• Slater orbitals are basically hydrogen-like but differ in
two important respects:
1. They contain no nodes. This implies them
considerably but of course make them less accurate.
2. They make use of Z* in place of Z and for heavier
atoms, n is replaced by n*, where for n =4 and n*
=3.7; n=5, n* = 4.0; n =6,n* =4.2. The difference
between n and n* is referred to as the quantum
defect.
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Ionization energy
1 13.6
𝐸𝑛 = 𝐸1 × =- eV/atom E1<E2<E3<………………….<En
𝑛2 𝑛2

The energy necessary to remove an electron from an isolated atom in the gas
Phase is the ionization energy for that atom.
It is the energy difference between the highest occupied energy level and that
corresponding to n = ∞.
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Properties of ionization energy and
periodic variations
• It is possible to remove more than • Periodic variations
one electron, and the succeeding
ionization energies are the second, • Within a given family, increasing n
third, fourth etc. tends to cause reduced ionization
energy because of the combined
• Ionization energies are always effects of size and shielding.
endothermic and thus are always
assigned a positive value accord with • Within a given series there is a
common thermodynamic general tendency for the ionization
convention. energy to increase with increase in
atomic number.
• This is the result of the tendency for
Z* to increasing progressing from left
to right in the periodic table.
• However, anomalies are also
observed.
• Generally, elements reactivity
increases with decreasing ionization
energy.

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Factors affecting the magnitude of
ionization potential
1. Nuclear charge
2. Completely filled and half-filled orbitals
3. The shielding effect/Screening effect
4. Nature of orbitals

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Effect of nuclear charge (Z) on IP
Elements Li Be B C N O F Ne
Z +3 +4 +5 +6 +7 +8 +9 +10
Z* 1.3 1.95 2.60 3.25 3.90 4.55 5.20 5.85
Z/Z* 2.31 2.05 1.92 1.85 1.79 1.76 1.73 1.71
IP (eV) 5.4 9.3 8.3 11.3 14.5 13.6 17.4 21.6

• In a given series, n remains constant

• The decrease in Z/Z* increases the electrostatic
attraction force between the nucleus and the valence
electron or the electrons in the outermost shell.
• Thus it becomes comparatively more difficult to
remove an electron.

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Half-filled or full-orbitals on IP
Elements Li Be B C N O F Ne
Z +3 +4 +5 +6 +7 +8 +9 +10
Z* 1.3 1.95 2.60 3.25 3.90 4.55 5.20 5.85
IP (eV) 5.4 9.3 8.3 11.3 14.5 13.6 17.4 21.6

• 4𝐵𝑒 = 1𝑠 2 2𝑠 2 7𝑁 = 1𝑠 2 2𝑠 2 2𝑝3

• According to Hund’s rule of maximum multiplicity,

atoms having half-filled or full-filled orbitals are
comparatively more stable and hence more energy is
needed to remove an electron from such atoms.

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Periodic variations of periodic
properties

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Application of ionization potential
• To explain the metallic and non-metallic character
of elements in a period of periodic table.
• To determine the number of valence electrons in an
atom.
• To determine the relative reactivity of elements.
• To determine the reducing power of elements.
• To determine the basic character of elements.

12/18/2022 Periodic properties 19

Electron affinity (EA)
• Imagine you're carrying a bag and adding things to it.
• Naturally, the bag becomes heavier, and there is a change in
the energy you expend when the weight changes.
• In the same way, when an atom gains electrons, an energy
change occurs.
• This energy change is what we call the electron affinity.
• The electron affinity is defined as the energy change that
occurs when an atom gains an electron, releasing energy in
the process.
• The electron affinity is the amount of energy released when
an electron is added to an isolated gaseous atom in its
lowest-energy state to produce an anion.
• Electron affinity is measured in electron volts (eV) or
kilocalories (Kcal) per gram atom or KJ/mol

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Factors affecting the magnitude of
electron affinity
1. Atomic size
2. Effective nuclear charge
3. Screening effect by inner electrons

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Comparative electron affinity
The smaller the atom is, the closer
the outermost shell is; therefore, it
is a stronger attraction between
the nucleus and the incoming
electron. That means the electron
affinity is higher for smaller atoms.

When looking at the periodic table

the atomic radius increases from
top to bottom, moving down a
column; therefore, the electron
affinity increases from the bottom
to the top of the column.
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Electronegativity
• As defined by Linus Pauling, electronegativity is the ability of an atom in a molecule to attract
the shared electrons closer to itself.
• Unlike most of the other periodic laws, such as radius, ionization energy, and E.A.,
electronegativity has no meaning outside the context of a chemical bond.
• There is no absolute scale for electronegativity. It is represented by xA
• The Pauling scale of electronegativity was developed in 1932 and is still the most widely used.
• Pauling arbitrarily assigned the electronegativity of fluorine as 4.00.
• The electronegativities of the other elements are based on the difference between the
experimental bond dissociation energy for a heteronuclear diatomic and the average of the bond
dissociation energies for the corresponding homonuclear diatomics.
• This difference, given by the symbol Δ in Equations (5.41) and (5.42), is known as the ionic
resonance energy, which is proportional to the percent ionic character in the bonding.
• The abbreviation BDE stands for the bond dissociation energy.
• A correction must be made if the diatomic molecule is multiply bonded, as is the case for N2 or
O2.
• The Pauling electronegativities of selected elements are listed in Table 5.12, along the
corresponding values for more modern definitions of electronegativity:

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Pauling’s Bond Energy Scale
• This method is based on Bond Dissociation Energy (BDE) or bond energy,
required to break a bond to get neutral atom.
• Consider a bond A-B between two dissimilar atoms in AB molecule.
• Let the bond energies of A-A, B-B and A-B are EA-A, EB-B and EA-B
• 𝐸𝐴−𝐵 > 𝐸𝐴−𝐴 × 𝐸𝐵−𝐵 Geometric mean of BE
• The difference EA-B and 𝐸𝐴−𝐴 × 𝐸𝐵−𝐵 is called ionic resonance energy
of A-B bond and is denoted ΔA-B.
• Thus ∆𝐴−𝐵 = 𝐸𝐴−𝐵 − 𝐸𝐴−𝐴 × 𝐸𝐵−𝐵 ------------------------(1)
• ΔA-B values do not possess additive property, i.e.,
• Consider three covalent bond A-B, B-C and C-A, then
• ∆𝐴−𝐵 + ∆𝐵−𝐶 ≠ ∆𝐶−𝐴 ------------------------------------(2)
• The electronegativities of A, B and C atoms should be in the order
xA>xB>xC.

12/18/2022 Periodic properties 26

Problem analysis
• The bond dissociation energy of ESi-Si, EO-O and EF-F are 43, 33 and
37 kcal/mole, respectively, while
• EF-Si, EF-O and EO-Si are 128, 44 and 89 kcal/mole, respectively.
• Calculate the values of ΔF-O, ΔO-Si and ΔF-Si bonds
• Solution:
• ∆𝐹−𝑂 = 𝐸𝐹−𝑂 − 𝐸𝐹−𝐹 × 𝐸𝑂−𝑂
• = 44 − 37 × 33 = 44-35 = 9 kcal/mole
• ∆𝑂−𝑠𝑖 = 𝐸𝑂−𝑆𝑖 − 𝐸𝑜−𝑜 × 𝐸𝑆𝑖−𝑆𝑖
• = 89 − 33 × 43 = 89-38 = 51 kcal/mole
• ∆𝐹−𝑆𝑖 = 𝐸𝐹−𝑆𝑖 − 𝐸𝐹−𝐹 × 𝐸𝑆𝑖−𝑆𝑖
• = 128 − 37 × 43 = 128-40 = 88 kcal/mole
• ∆𝑭−𝑶 + ∆𝑶−𝑺𝒊 ≠ ∆𝑭−𝑺𝒊
• Or 9 +51 ≠88

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Ionic resonance energy VS partial
ionic character of bonds
• The square roots of values of ionic resonance energies of bond between two hetero atoms
is known as partial ionic character of hetero nuclear covalent bond (A-B).
• Partial ionic character of covalent bond is an additive property.

• i.e., ∆𝐹−𝑂 + ∆𝑂−𝑆𝑖 = ∆𝐹−𝑆𝑖

• 9+ 51 ≆ 88
• 3 +7.2 ≆ 9.4
• 10.2 ≆ 9.4

• i.e., ∆𝐴−𝐵 𝑖𝑛𝑐𝑟𝑒𝑎𝑠𝑒𝑠 𝑤𝑖𝑡ℎ 𝑖𝑛𝑐𝑟𝑒𝑎𝑠𝑒 𝑜𝑓 𝑖𝑜𝑛𝑖𝑐 𝑐ℎ𝑎𝑟𝑎𝑐𝑡𝑒𝑟 𝑜𝑓 𝐴 − 𝐵 𝑏𝑜𝑛𝑑

• ∆𝐴−𝐵 𝑎𝑙𝑠𝑜 𝑖𝑛𝑐𝑟𝑒𝑎𝑠𝑒𝑠 𝑤𝑖𝑡ℎ 𝑖𝑛𝑐𝑟𝑒𝑎𝑠𝑒 𝑖𝑛 𝑒𝑙𝑒𝑐𝑡𝑟𝑜𝑛𝑒𝑔𝑎𝑡𝑖𝑣𝑖𝑡𝑦 𝑑𝑖𝑓𝑓𝑒𝑟𝑒𝑛𝑐𝑒 ሺ𝑥𝐴 −

𝑥𝐵ሻ 𝑏𝑒𝑡𝑤𝑒𝑒𝑛 𝑡ℎ𝑒 𝑡𝑤𝑜 𝑎𝑡𝑜𝑚𝑠 𝐴 𝑎𝑛𝑑 𝐵 𝑖𝑛 𝐴 − 𝐵 𝑐𝑜𝑣𝑎𝑙𝑒𝑛𝑡 𝑏𝑜𝑛𝑑.

• Thus 𝑥𝐴 − 𝑥𝐵 ∝ ∆𝐴−𝐵 ---------------------------------------------------(3)

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Electronegativity VS partial ionic
character
• Using equation (1) and (3), Pauling suggested an equation of electronegativity as
follows:
𝟏
• 𝒙𝑨 − 𝒙𝑩 = 𝑲 𝑬𝑨−𝑩 − 𝑬𝑨−𝑨 × 𝑬𝑩−𝑩 𝟐

• The value of K was found to be equal to 0.208 that comes from the conversion
experimental values of EA-B measured in kcal/mole into eV. Thus
𝟏
• 𝒙𝑨 − 𝒙𝑩 = 𝟎. 𝟐𝟎𝟖 𝑬𝑨−𝑩 − 𝑬𝑨−𝑨 × 𝑬𝑩−𝑩 𝟐
----------------------(4)

• Equation (4) describes the difference in electronegativity values between to

bonded atoms.
• Thus equation (4) can be used to calculate the value of electronegativity of one
bonded atom if the electronegativity of the other bonded atom is known.
• Pauling assigned an arbitrary value of 4.0 for the electronegativity of fluorine and
calculated that of other elements with the help of equation (4)

12/18/2022 Periodic properties 29

 Electronegativity values of s- and p-block
elements as determined by Pauling (Scale
F = 4.0

Electronegativity decreases from top to bottom

S-block elements P-block elements
IA IIA IIIA IVA VA VIA VIIA
H (2.1)
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 (1.8) Bi (1.9) Po (2.0) At (2.2)
Fr (0.7) Ra (0.9)

Electronegativity increases from left to right

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Periodic variations of electronegativity
In a period In a group
• Increases from left to • In moving down a group of the PT,
since the nuclear charge again
right increases, electronegativity of the
lower element should be more than
• Size decrease, effective that of the upper element.
nuclear charge increases • Actually, it is not so because the
and number of valence disadvantages of increase in atomic
radii and the electron shielding effects
electrons increase more than compensate for the
advantage gained through increase in
• Elements: Li Be B C N O F the nuclear charge.
• VSC: lack of sufficient space • Consequently, a lower element of a
group is less electronegative than the
• No. of VSE:1 2 3 4 5 6 7 upper element of the same group.
• xM: 1.0 1.5 2.0 2.5 3.0 3.5 4.0 • General trend, small atoms attract
electrons more strongly than large
ones and are therefore, more
electronegative.

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Correlation of IP and EA with
electronegativity
• Higher values of ionization potential indicate that
it is difficult to remove an electron from an atom or
in other words the atom has greater attraction for
electrons,
• i.e., greater electron affinity.
• Thus, greater values of ionization potential and
greater electron affinity both indicate greater
electronegativity.
• For example, compare the values IP and EA in
metals and non-metals

12/18/2022 Periodic properties 32

 TABLE 5.12 Electronegativities of selected elements using the revised
Pauling scale, the Mulliken–Jaffe scale, and Allen’s spectroscopic
configuration energies. The latter scales have been converted to the revised
Pauling scale. The Mulliken–Jaffe values are listed for the sp3 valence
hybridization, unless otherwise indicated.

The Mulliken–Jaffe scale defines

electronegativity on the basis of
atomic parameters, namely the
average of the valence ionization
energy and E.A., as shown in
Equation (5.43).

Lee Allen has developed an

electronegativity scale that is based on
spectroscopic data, namely the average
valence electron energies obtained by gas-
phase atomic spectroscopy.

12/18/2022 Periodic properties 33

• . Allen’s spectroscopic electronegativity (𝜒spec) is based on the
configuration energy (C.E.), given by Equation (5.44).
• In this equation, 𝜀p and 𝜀s are the “one-electron” energies of the
valence p and s orbitals, respectively, and
• m and n are the numbers of p and s electrons occupying those
orbitals.
• More specifically, the energies 𝜀p and 𝜀s are calculated from the
average of the (2L+1)(2S+1) multiplets of the ground state with
those of the singly s and singly p ionized configurations.
• The Allen approach has the advantage that it is not based on
molecular properties and can be calculated solely from the
spectroscopic properties of each atom.
• Because the formula in Equation (5.44) ignores contributions
from the d and f electrons, it is not at all useful for the transition
metals, lanthanides, or actinides.

12/18/2022 Periodic properties 34

Applications of electronegativity
• Trends in acid-base character of the normal oxides
of the elements of the same period:

Oxides Na2O MgO Al2O3 SiO2 P4O10 SO3 Cl2O7

xE 1.0 1.2 1.4 1.7 2.0 2.4 2.8
xO-xE 2.5 2.3 2.1 1.8 1.5 1.1 0.7
Acid- Strongly Basic Amphot Weakly Acidic Strongly Very
base basic eric acidic acidic strongly
charact acidic
er

12/18/2022 Periodic properties 35

 Applications of electronegativity
• To determine the metallic and non-metallic
character of elements

Electronegativity decreases from top to bottom

S-block elements P-block elements
IA IIA IIIA IVA VA VIA VIIA
H (2.1)
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 (1.8) Bi (1.9) Po (2.0) At (2.2)
Fr (0.7) Ra (0.9)

Metallic character increases Non-metallic character increases

Electronegativity increases from left to right

12/18/2022 Periodic properties 36
Applications of electronegativity
• To determine acid-base character of XOH type molecules:
• In XOH molecule, X may be both metal or non-metal.
• When they undergo ionization reaction in water, two case arise:
• 1. When xO-xX < xO-xH, O-H bond will be more polar than X-O bond and
hence ionization of XOH molecule in aqueous medium will take place at
O-H bond
• 𝑿 − 𝑶 − 𝑯 + 𝑯𝟐𝑶 = 𝑿𝑶− + 𝑯𝟑𝑶+
• As H3O+ ions are produced, the molecule behaves as acid.
2. When xO-xX > xO-xH, X-O bond is more polar than O-H
bond and hence ionization of XOH molecule in aqueous
medium occurs at X-O bond +
𝑿 − 𝑶 − 𝑯 + 𝑯𝟐𝑶 = 𝑯 − 𝑶𝑯𝟐 + 𝑶𝑯−
Since OH- ions are produced, the molecule acts as a base.
Thus, the concept of electronegativity can be used to predict whether
the compounds of XOH type are acidic or basic in aqueous medium.
Gallais suggested that XOH molecule shows acidic character when xX is >1.7
12/18/2022 Periodic properties 37
Applications of electronegativity
• To determine the stability of compounds or the strength of molecules
• The electronegativity difference (𝒙𝑨 − 𝒙𝑩 ሻ, can be used to determine
the strength of A-B bond in AB type molecules.
• The greater the (𝒙𝑨 − 𝒙𝑩 ሻ value, more strong will be the A-B bond or
more stable will be the AB molecule.
• For example, consider the relative strength of hydracids of halogen
series.

halogens : F Cl Br I
𝑥𝑋 (H =2.1) : 4.0 3.0 2.8 2.5
Hydracids : H-F H-Cl H-Br H-I
𝒙𝑿 − 𝒙𝑯 : 1.9 > 0.9 > 0.7 > 0.4
Stability of H-X bond : H-F > H-Cl > H-Br > H-I
Heat of formation of H-X bond (kcal/mole) : -64.5 > -22.0 > -12.5 > -1.5

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Applications of electronegativity
• To determine the stability of compounds
• The electronegativity difference (𝒙𝑨 − 𝒙𝑩 ሻ, can be used to determine
the strength of A-B bond in AB type molecules.
• The greater the (𝒙𝑨 − 𝒙𝑩 ሻ value, more stable is the compounds.
• The small the (𝒙𝑨 − 𝒙𝑩 ሻ value, the compound tends to be more
unstable and the heat of formation of such compounds is very small.
• For example, consider the relative stability od some compounds

Elements : Na Cl Si N P As H
𝑥𝑋 (H =2.1) : 0.9 3.0 1.8 3.0 2.1 2.0 2.1
Compounds : NaCl PCl3 SiH4 NCl3 PH3 AsH3 H2
𝒙𝑨 − 𝒙𝑩 : 2.1 > 0.9> 0.3> 0.0 00 0.1 00
ΔH (kcal/mole) : -787 -306 +34.3 +232 +210 +664 00

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