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is called
1
st
Ionization energy (IE) i.e. the energy required to remove the 1
st
electron from an
isolated atom.
Similarly, 2
nd
I.E. is the energy required to remove the 2
nd
electron from a isolated atom
A
So, in general, the I.E. increases along a period and decreases along a group.
[Why? Hint: - The closer the e- to the nucleus, the more tightly held it is and hence
higher the I.E.] Also, 2
nd
ionization energy is always greater than the first ionization
energy. (Because it is easy to separate an electron from a neutral atom than to separate
it from a +vely charged atom).
Ionization potential increases across the period because of increase in nuclear charge
due to which the atomic size decreases. Thus, more energy is required to pull away the
electron from the outermost shell of the atom of smaller size.
Ionization potential decreases down the group because of increase in the number of
shells. The effective nuclear charge decreases as atomic size increases. Thus it is easier
to pull one electron from the outermost shell of the atom.
Group 18 elements have the highest Ionization enthalpy because of their full-filled
electronic configuration.
Similarly it is more for half filled electronic configurations (e.g. N)
Some points to note:
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The noble gases have the highest IE's of any element in the period. This is
because of very high nuclear charge and fulfilled electronic configuration.
IE's (as well as many other properties) tend not to vary greatly amongst the d-
block elements. This reflects the fact that as the more-compact d orbitals are
being filled, they exert a screening effect that partly offsets that increasing
nuclear charge on the outermost s orbitals of higher principal quantum number.
Each of the Group 13 elements has a lower first-IE than that of the element
preceding it. The reversal of the IE trend in this group is often attributed to the
more easy removal of the single outer-shell p electron compared to that of
electrons contained in filled (and thus spin-paired) s- and d-orbitals in the
preceding elements.
Example The first I.P. of nitrogen is greater than oxygen white the reverse is true for
their second I.P. values.
Solution: The first I.P corresponds to the removal if first electron. Since nitrogen is
already half filled. So more energy is required to remove the electron. But once the
electron is removed from oxygen it gains half filled stability and therefore the 2
nd
I.P.
becomes high.
Example The ionization energy of the coinage metals fall in the order .
Solution: In all the 3 cases as s electron in the unpaired state is to be removed. In the
case of Cu a 4s electron is to be removed which is closer to the nucleus than the 5s
electron of Ag. So I.P. decreases from Cu to Ag. However form Ag to Au the 14 f electrons
are added which provide very poor shielding effect. The nuclear charge is thus
enhanced and therefore the outer electron of Au is more tightly held and so the IP is
high.
2.4 Electron gain enthalpy (E.G.E)
Energy released when an electron is added to the gaseous isolated state of an atom.
Again sounding tough?
Well, take the reaction:
The energy released in this reaction is E.G.E.
More the E.G.E., easier the addition of electrons. So, in general, the E.G.E.
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Becomes more negative along a period and less negative down the group.
[Why?.... Hint: - smaller the atomic radius, higher the effective nuclear charge and
hence, gaining of e- becomes easier. Thus E.G.E. is more negative.]
Electron affinity is the ability of an atom to hold an additional electron. If an atom has
greater tendency to accept an electron then the energy released will be large and
consequently the electron affinity will be high. Electron Affinity can be positive or
negative.
Electron affinity increases from left to right across the period because of increase in
nuclear charge and decrease in atomic size. This causes the incoming electron to
experience a greater pull of the nucleus.
Electron affinity decreases down the group because the number of shells increases i.e.,
the atomic size increases and the effective nuclear charge decreases.
The electron affinity of completely filled atoms is almost zero. An atom does not accept
an electron in its outermost shell if it already has stable configuration e.g. inert gases
So it depends mainly of effective nuclear charge, atomic size and electronic
configuration of the element. Chlorine has the highest electron affinity.
Some irregularities are
In the Group 2 elements, the filled 2s orbital apparently shields the nucleus so
effectively that the electron affinities are slightly endothermic.
The Group 15 elements have rather low values, due possibly to the need to place
the added electron in a half-filled p orbital; why the electron affinity of nitrogen
should be endothermic is not clear. The vertical trend is for electron affinity to
become less exothermic in successive periods owing to better shielding of the
nucleus by more inner shells and the greater size of the atom, but here also there
are some apparent anomalies.
Example The electron affinity of sulfur is greater than oxygen. Why?
Solution: This is because of smaller size of oxygen due to to which it has got higher
change density and thus electronic repulsion increases as it takes electron. So its E.A. is
less than sulphur.
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2.5 Electronegativity
It is the property of an atom which is bonded to another atom. The atom which is more
electronegative tries to keep more share of electron.
It increases along the period, as effective nuclear charge increases and atom will try to
pull the shared electron because of more nuclear charge.
It decreases down the group.
Fluorine is the most electronegative element.
2.6 Metallic Character
The metallic character is actually tendency of atom to lose electrons and form positive
ions. It has similar trend as ionization energy.
The metallic character decreases along the period because of increase in effective
nuclear charge which holds the valence electron with greater force.
The metallic character increases down the group, as down the group the nuclear force of
attraction decreases.
Some important facts!
1. Size of anion > size of atom > size of cation. [Why?]
2. The ions having same no. of electrons are called isoelectronic ions. The size in an
isoelectronic series decreases with increase in nuclear charge.
E.g.
[Why?]
3. Be, Mg, N, P and noble gases have exceptionally high values of I.E. due to their stable
half-filled and completely-filled electronic configuration. For the same reason they have
very low E.G.E. also.
4. Chlorine has highest
...
among all the elements.
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Across
1 The lightest inert gas. (6)
4 The element we need to
breathe. (6)
5 Alkaline metal in table
salt. (6)
7 Inert gas used to make
bright city lights. (4)
8 2nd place in the
Olympics. (6)
10 An important element in
bones. (7)
13 A radioactive element
often used in nuclear
power stations. (7)
14 Poison gas in WWI. (8)
15 A famous poison that
turns your tongue black.
(7)
17 A metal sought after
during the Klondike. (4)
18 The element diamonds
are made from. (6)
19 This metal is used along
with carbon to make
steel. (4)
Down
2 Heavy metal used in paints, batteries, and radiation shields.
(4)
3 The most common element in the universe. (8)
6 A liquid metal that was used in thermometers. (7)
7 Most common element in the earth's atmosphere. (8)
9 A component of gunpowder that smells like rotten eggs. (7)
11 A metal used in foil. (World Spelling) (9)
12 A metal used in wires. (6)
15 The most common inert gas in the atmosphere. (5)
16 Element used to make semi-conductors (computer chips). (7)
1 2
3
4
5 6
7 8
9 10 11 12
13
14
15 16
17
18
19
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Solved Examples
Example Berilium and Al are placed in different periods and groups by they show the
similar properties.
Solution: On moving across a period the charge on the ions increases and the size
decreases, causing the polarizing power to increases. On moving down a group the size
increases and polarizing power decreases. On moving diagonally i.e., form Be to Al these
two effects partly cancel each other and so there is no marked change in properties.
Example
(i) NaOH behaves as a base while ()
is amphoteric why?
(ii) Among fluorine fluorine bond and chlorine chlorine bond. Which is more
stronger and why?
Solution:
(i) In NaOH the bond electronegativity difference between Na and oxygen is greater
than between H and O and therefore it is the Na- O bond that breaks releasing
. But
in case of bond the difference of electronegativity of and are
almost same. So there is equal probability that the bond breaks in both ways leading to
an amphoteric behaviour
(ii) In Cl Cl bond, a filled p orbital of chlorine can overalap with a suitable vacant d
orbital of adjacent chlorine thereby introducing some double bond character. Thus the
bond strength increases. This is not possible in fluorine as it has got no vacant d
orbital
Example
(i) In alkali metal group which is the strength reducing agent and why?
(ii) Although aluminium is above hydrogen in the electrochemical series, it is stable in
air and water. Explain.
Solution:
(i) Li is the strongest reducing agent. Since I.P. decreases down the group we would
expect that Li will have the lowest reducing power in the group. But since its hydration
energy is very high and which in fact decreases down the group, Li will have highest
reducing power.
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(ii) Due to the formation of protective oxide layer on its surface.
Example :
() by energy
atoms of X(g)
are converted into
() and
() by energy
.
Calculate the ionization energy and electron affinity of X
Solution: let the ionization energy of X beI (which is always in kJ/ mol) and electron
affinity of X be EA kJ/mol
()
()
2
)
) (where
()
()
() +
2
)
2(
Example : two atoms
[]3
2762
[]3
692
Completely filled configurations have higher ionization energy than other
configurations due to their extra stability
Example : explain why the 2
nd
ionization energy of Cr is higher than that of Mn
Solution: after losing one electron Cr will get converted into
)
Example : why the 1
st
Ionisation energy of the phosphorus is greater than that of
sulphur
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Solution: phosphorus has got a stable half filled electronic configuration hence the 1
st
I.E. of P is higher than that of
Example : the 1
st
and 2
nd
I.E. of K are 419 kJ/m and 3052 kJ/mol and Ca are 590 kJ/mol
and 1145 kJ/mol respectively. Compare their values and explain the differences
Solution:
Removal of 2
nd
electron from K is extremely difficult because K acquires stable noble gas
configuration after removing one electron while removal of both the electrons for Ca is
comparatively easy, as it acquires stable configuration after removal of both the
electons
Example : third ionization energy of C is higher than that of N, explain.
Solution: after ejecting two electrons from 2p orbitals, the third electron is being ejected
from filled (stable) 2s orbital of carbon, hence a greater amount of energy is required.
But in nitrogen the third electron is to be ejected from 2
, 2
, 2
Due to higher nuclear charge in carbon, the force of attraction of valency
electron is more in carbon atom and hence the first ionization energy is
greater than boron atom. After loss of one electron, the monovalent
cations have the configurations as follows:
, 2
, 2
, 2
The
(g)
from O (g) is endothermic, explain
Solution: The addition of an electron to a neutral atom is an exothermic process.
()
The addition of second electron to a monovalent anion,
, as to make it
is difficult because both have the same charge and experience a lot of
repulsion. Thus, the addition of an electron to
requires energy to
overcome the force of repulsion.
.. (2)
The energy absorbed in step 2 is more than the energy released in the
step -1. Hence, the formation of
. Explain this on
the basis of hybridization electronegativity.
7. Compound Electronegativity of central atom Bond angle
3.0 2
2.1 97
2.0 96
1.9 88
Explain this table by trying to correlate the electronegativity of the central atom
and bond angle.
8. Arrange the following isoelectronic ions in increasing order of ionic radii:-
?
9. How many elements are there in the periodic table? If an element with Z = 107 is
discovered, where would you place it in the periodic table?
10. Arrange the following species in the order of increasing size:
(i) , , , (b)
(c)
11. Match the correct pairs
Electronic configurations Type of element
(a) 62
(2) Halogen
(C)
(B)
(c)
13. Arrange the following according to given instructions:
(i)
(increasing radius)
(ii)
, ,
(Increasing radius)
(iii) , , , (increasing electronegativity)
(iv) , , , (increasing electron affinity)
(v) , , , (increasing electronegativity)
(vi) , , , (increasing 1
st
ionization potential)
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(vii) , , , (increasing peramagnetism)
(viii) , , , (increasing electropositive character)
(ix)
416 602 1676 911 2984 395
+250
Arrange these oxides in increasing order of stability.
16. Arrange the following in the order of reducing character:
(a) Na, K, Rb (b) Na, Mg, Al (c)
(d)
, ,
17. Indicate whether the following process is exothermic or endothermic:
()
2
()
()
2
()
(. . )
()
737.7
(. . )
()
45
(. . )
()
328
18. Arrange the following ions as indicated;
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In increasing order of
(i) degree of hydration (ii) hydration energy (iii) size of
hydrated ions
(iv) ionic mobility (v) standard reduction potential
19. Calculate the electron affinity of the hydrogen atom using the following enthalpy
data:
()
2
()
436
()
2
()
2
()
8
()
()
83
()
()
43
()
()
()
742
20. Arrange the following species in decreasing order of electropositive character Fe,
Sc, Rb, Br, Te,F, Ca
21. Select paramagnetic and diamagnetic species among the following
, ,
.
22. Arrange following species in decreasing order of atomic size
,
23. Calculate the electronegativity of fluorine from following data
4.2
36.3
34.6
Electronegativity of H is 2.05.
24. First and second ionization energies of
()
74 45
.
Calculate percentage of
()
()
, if 1 g of
()
absorbs 50 KJ of energy.
25. The first four ionization energies of an element are approximately 738 kj/mole,
1450 kj/mol, 7700 kj/mol and 1000 kj/mol. Identify the periodic group to which
this element belongs.
26. Arrange the following isoelectronic species in order of (a) increasing ionic radius
and (b) increasing ionization energy:
.
27. Which oxide is more basic, or Why?
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Level-III
28. Write balanced equation for the reactions between each of the following oxides
and water. (a)
(b) (c)
29. Arrange the elements in each of the following groups in increasing order of the
most positive electron affinity. (a) Li, Na, K (b) , , ,
30. Among the elements of the third period (Na to Ar), pick out the element
(i) With the highest first ionization enthalpy
(ii) With the largest atomic radius
(iii) That is the most reactive nonmetal
(iv) That is the most reactive metal
31. Arrange the following elements in the increasing order of nonmetallic character:
B, C, Si, N and F.
32. Account for the large decrease in electron affinity between lithium and beryllium
despite the increase in nuclear charge.
33. In general, ionization energy across a period from left to right. Explain why the
second ionization energy of chromium is higher than that of manganese.
34. The ionization energies of Li and K are 5.4 and 4.3 eV, respectively. What do we
predict for the ionization energy of ?
35. The ionization energies of Li, Be and C are 5.4, 9.3 and 11.3 eV. What do we
predict for the ionization energies of B and N?
36. Explain in terms of their electronic configurations, why
is more easily
oxidized to
than
to
.
37. The electron affinity of chlorine is 3.7 eV. How much energy in kcal is released
when 2 g of chlorine is completely converted to
Carried out at such low pressures that resulting ions do not combine with each
other.
39. The ionization potentials of atoms A and B are 400 and 300 kcal
respectively. The electron affinities of these atoms are 80.0 and 85.0 kcal
respectively. Prove that which of the atoms has higher electronegativity.
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40. Arrange the following species in decreasing order of atomic size.
,
and
41. Indicate whether the following process is exothermic or endothermic.
() 2()
() 2
()
Given: (. . )
of () 737.7
; (. . )
of () 45
&
(. . )
of () 328
42. Arrange the following atoms/species in the order of reducing character.
(a) , , (b) , , (c)
Hints & Answers
1. (a) He (inert Gas) (b) Be (Fully filled shell) (c) N (Half filled
configuration)
2. In the periodic table the elements show similar properties across diagonal. This
behaviour is because of identical size of the elements. E. g.:
GP I GP II GP III GP IV
Li Be B C
Na Mg Al Si
3. The order of electron affinity in VII gp is as F < Cl > Br > I > At
4. F > Cl > Br > I > At
5. H Cl = O HClO
Chlorine in (+5) oxidation state is less stable than (+1) oxidation sate and has
greatest tendency to attract electrons than in (+1) oxidation sate. Therefore
HClO3 behaves as a stronger acid.
6. H C C H < H C = C H < H C C H
In acetylene carbon in sp hybridized and thus the percentage of s character is
maximum in acetylene. With the increase of a character shielding of electrons
H H
H
+
1
O
O
O
H H
H
H
H
H H
H H
H H
H
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around the carbon nucleus is maximum. Thus
and
(c)
11. (a) 2. (b) 1 (c) 5 (d) 3 (e) 4 (g) 6
12. B & C; Because of bipositive ions formation
13. (i)
(ii)
(iii) (iv)
(v) (vi)
(vii) (viii)
(ix)
(x)
14. (a) Zinc do not have partly filled d orbitals so cannot undergo excitation of
electrons to higher energy shells (no d d transition). Therefore they are
colourless.
(b) They have a stron tendency to gain an electron to acquire noble gas
configuration, viz,
.
(c) Are strongly metallic in nature.
(d) Because their properties are transitional between s and p block elements.
(e) Due to extra stability of half filled orbital.
(f) Due to largest difference in the size and their electronegativity values.
(g) Noble gases are stable.
(h) Poor screening effect.
15.
.
Hint: Oxide
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416 416
MgO 602 602
1676 558.7
911 455.5
2984 298.4
395 131.7
+ 250 + 35.7
Greater is the negative value of heat of formation per oxygen atom more is the
stability of oxide.
16. (a) Na < K < Rb (b) Na > Mg > Al (c)
(d)
Mg < Ca < Sr
17. The process is endothermic
Hint:
()
()
[(. )
(. )
288.7
]
2
()
2
2
()
. . 328 2
2
288.7 328 2 532.7
18. (i)
(ii)
(iii)
(iv)
19. 37
Hint: it can be solved by forming the born habers cycle.
20.
21. Paramagnetic species:
Diamagnetic species:
22.
Hint: in isoelectronic species, size decreases with increase in number of
protons in the nucleus.
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23. 3.6034
Hint: On pauling scale
.82 .. ()
( . .
.8272.84 .5534
68.35
3.65
Hint: Number of moles of 1 g of
.47
Energy required to convert ()
() .47 74 3.83
Remaining energy 5 3.83 9.7
Number of moles of
.32
Thus, remaining
.47 .32
.285
.
.
68.35
68.35 3.65
25. II A
26. (a)
(b)
27. BaO, because basic character of oxides increases in group
28. (a)
2 (b)
()
(c)
29. (a) (b)
30. (i) Ar (II) Na (III) Cl (IV) Na
31. Si < B< C< N < F
32. Be has a stable filled 2s configuration.
33.
).
34. Ionization energy of Na is intermediate between that of Li & K i.e. 4.9 eV.
35. I.E. (B) < I.E (Be) I.E. (N)>I.E (C)
36.
while
has 3
, so
easily
gets oxidized to
, as
) but
will
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not easily get oxidized to
).
37. 4.8 kcal
38. 41.508 kcal
39. Electronegativity of A = 3.84; electronegativity of B = 3.08. Therefore A has higher
electronegativity.
40.
41. The process is endothermic ( 532.7 )
42. (a) (b) (c)
(d)