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SINHA I.I.T.

CHEMISTRY

PT & Bonding
IMPORTANT FORMULA

1.Covalent radius:Half of the intermolecular distance between


two atoms of the elements held by

a single covalent bond. Calculation for covalent radius can be


made as: d d A− A = bond length in molecule (a) In Homodiatomic
molecule (A-A): r = A− A 2 (b) In Heterodiatomic molecule
(A-B):
(i) When ( χΑ − χΒ) is very small: d A− B = rA + rB d A− B = Bond length
(ii) When ( χΑ − χΒ) is large: d A− B = rA + rB − 0.09( χΑ − χΒ)
Z = atomic number, σ= shielding constant
2. Z-effective Z eff = Z − σ According to Slater,
for electron residing in ns & np orbitals is given
by: σ=[0.35 X Number of e- in nth shell excluding
test e-]+[0.85X No of e- of (n-1) d-electron and

other inner d-electron orbitals value of σshould be


calculated by : No. of d-electrons X 1.0 3.Pauling’s
approach : Pauling based his scale on thermo-chemical data.
He concluded that the bond formed between the two atoms A and B
must be stronger than the average of single bond energies of A-A and B-B
molecules.
The electronegativity difference Where Δ Actual bond energy –energy for 100%
covalent bond energy Δ is ( χΑ ~ χΒ) =0.208 Δ
referred as extra bond energy in
kcal mol-1.Actual bond energy can be measured and according to Pauling 100%
covalent bond can be given by the geometric mean of the covalent bond energies
of A-A and B-B molecules. i.e. E 100% covalent
A-B = E A− A X E B − B

Δ=
⎡ ⎣
1

EA-B -

E A− A X E B − B

By eq. 1 and 4 ( χΑ ~ χΒ) = 0.208 ⎢ E A− B − (E A− A X E B − B ) 2 ⎥


electronegativity for C and F thus comes 2.5 and 4.0 respectively.
Eq. (5) can be written if Δ is in SI unit kJmol-1as:

⎤ ⎦

1 2
EA-A,EB-B and EA-B in kcal mol-1.

The electronegativity of atoms on Pauling scale are obtained by


assuming χH=2.05. The value of

12 ( χΑ ~ χΒ) =0.1017 Δ =0.1017 ⎡


E A− B − (E A− A X E B − B ) 2 ⎤ Where EA-A,EB-B. EA-B are in kJ mol-1. ⎢ ⎥ ⎣ ⎦

4. Mulliken’s approach: According to Mulliken’s


of an atom is average of I.E. I .E. + E. A. I .E. + E. A. χ P = 0.336[χ M − 0.615]
Or and E.A. χM = χP = 2 5 .6
If I.E. and E.A are being measured in kJ mol-1
then equation becomes as the energy
1 eV/molecule =96.48kJmol-1

χM =

I .E. + E. A. I .E. + E. A. Also χ P = 2 X 96.48 2 X 96.48 X 2.8

χP =

I .E. + E. A. 540

5.Allered and Rochow approach:

In this method electronegativeiy is calculated as

(χ A ) AR

= 0.744 +

0.359 Z effective r2

χA =Electronegativiy of atom A on Allred & Rochow scale.

r= radius of an element in Δ
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Zeff.= Effective nuclear charge at periphery of element A.


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PROBLEMS
Q.1 The energy needed for Li (g) → Li 3+ +3e is 1.96 X 104 kJ mol-1.
If the first ionisation energy of Li is 520 kJmol-1.
Calculate the second ionisation energy for Li.
Given IE1 for H =2.18X10-18kJ atom-1.
Q.2 for the reaction. Li +Cl → Li+ +Cl
Q.3 You are given Avogadro’s no. of ‘X’ atoms.
If half of the atoms of ‘X’ transfer one electron to the other half
of ‘X’ atoms 409 kJ must be added. If these X- ions are subsequently
converted to X+ an additional 733 kJ must added.
Calculate IP and EA of X in eV.
Q.4 The first IP of lithium is 5.41 eV and electron affinity of
Cl is -3.61 eV. Calculate ΔH in kJmol-1

How many Cl atoms can you ionize in the process Cl → Cl+ +e by the
energy liberated for the

process Cl + e → Cl- for one Avogadro’s number


of atoms. Given IP =13.0eV and EA =3.6 eV.
Q.5 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 Cl- ion is a gaseous state?
Q.6 EA1 value for oxygen is negative (-142 kJmol-1) while (EA1+EA2) value
is positive .Explain the reason for opposite sign for two values Also calculate
EA2 value.
Q.7 How many Cs atoms can be converted to Cs+ ions by 1 Joule energy if IE1 for Cs
is 376 kJ mol-1
. Q.8 A mixture contains F and Cl atoms.
The removal of an electron from each atom of the sample requires 284 kJ
while addition of an electron to each atom of mixture releases 68.8 kJ energy.
Calculate the % composition of mixture. Given IE per atom for F and Cl are 27.91
X10-22 kJ and
n20.77X10-22 kJ. EA1 for F and Cl are -5.53X10-22 and -5.78X10-22 kJ respectively.
Q.9 Using the data given below, predict the nature of heat changes for the
reaction.
Mg + 2F → Mg2+ + 2FIE1 and IE2 of Mg are 737.7 and 1451 kJ mol-1.EA1 for F
is -328kJ mol-1. Q.10 Calculate the effective nuclear charge at the periphery of
nitrogen
atom when an extra electron is added in the formation of anion.
Also calculate the effective nuclear charge of N-atom.
Q.11 The ionisation energy of Li is 5.39 eV. If ionisation energy of H is 13.6 eV,
then calculate the effective charge acting upon outermost electron of Li.
Q.12 Calculate electronegativity of carbon at Pauling scale.
Given that: EH-H =104.2 kcal mol-1, EC-C =83.1 kcal mol-1,
EC-H = 98.8 kcal mol-1. Electronegativity of hydrogen =2.1
Q.13 Electronegativity of F on Pauling scale is 4.0. Calculate its value on
Mulliken scale.
Q.14 Calculate electronegativity of fluorine from following data:
EH-H=104.2 kcal mol-1 EF-F=36.6 kcal mol-1 ,
EH-F =134.6 kcal mol-1 Electronegativity of hydrogen =2.1 Q.15
Ionisation potential and electron affinity of fluorine are 17.42 and
3.45 eV respectively. Calculate electronegativity of fluorine on Mullken scale and
Pauling scale.
Q.16 Calculate electronegativity of silicon using Allred-Rochow method. Covalent
radius of
silicon is 1.175 Δ.
Q.17 Covalent radius of 82Pb is 1.53Δ. Calculate its electronegativity at Allerd-
Rochow scale.
Q.18 Atomic radius and ionic radius of F (g) and F-(g) are 72 and 136 pm.
respectively .
Calculate the ratio and percentage increase in terms of volume during formation of
F- form F.
Q.19 Calculate the theoretical value of bond length in H-F, if rH and rF are
0.37Δ and 0.72Δ. respectively .Electronegativities of F and H are 4.0 and 2.1
respectively.
Q.20 χBe and χCl are 1.6 and 3.2 respectively. Calculate Δ Hf for BeCl2 molecule.
Q.21 A diatomic molecule has a dipole moment of 1.2 D. If the bond distance is 1.0
Δ.
What fraction of an electronic charge e exists on each atom?
Q.22 The dipole moment of LiH is 1.964 X 10-29 Cm and the inter-atomic
distance between Li and H in this molecule is 1.596Δ. What is the percent ionic
character in LiH.
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Q.23 Calculate the molecular weight of HF if density of HF gas is 3.17 g/L at 300K
and 1.0 atm. Comment on the result.
Q.24 The experimental dipole moment of w
ater molecule is 1.84 D .Calculate the bond angle H-O-H in water molecule, if
dipole moment
of OH bond is 1.5 D.
Q.25 The H-O-H bond angle in the water molecule is 105°, the H-O bond distance
being 0.94Δ.
The dipole moment for the molecule is 1.85 D. Calculate the charge on the oxygen
atom.

covalent or become ionic in aqueous solution. (Ionisation energy for AlCl 3 =5137
kJ mol-1 ;
Δ hydration for Al3+ = -4665 kJ mol-1

Q.26 Estimate the lattice energy of CaCO3 if rCa+=114 pm and r CO 3 = 185 pm.
Q.27 Suppose a gaseous mixture of He, Ne, Ar and Kr is irradiated with photons
of frequency approximate to ionize Ar. What ions will be present in the mixture?
Q.28 The dipole moment of KCl is 3.336 X 10-29 coulomb meter which indicates that
it is a highly polar molecule. The inter-atomic distance between K+ and Cl- in
this molecule
is 2.6 X 10-10 m. Calculate the dipole moment of KCl molecule. if there were
opposite charge of
one fundamental unit located at each nucleus. Calculate percentage ionic character
of KCl.
Q.29 Anhydrous AlCl3 is covalent .From the data given below predict whether it
would remain


Δ hydration for Cl- = -381 kJ mol-1)

ANSWERS

Q.1 Q.4 Q.8 Q.13 Q.17 Q.22 Q.26

a=7270 kJ mol-1 Q.2 1.667 X1023 Q.5 62% 11.29 1.61 Q.9 Q.14 Q.18

kJ = 173.7 kJ 4.8 kcal Q.15 Q.19

Q.3 Q.6 Q.10

a=11.835 eV and b =3.358 eV.


844 kJ mol-1 Q.7 1.6X 1018Cs+ ions. 3.9 Q.11 1.26 Q.12

+1532.7 kJ mol-1

χF= 3.87
5.75 x 102

(χF )M

= 10.435 , (χF )P = 3.726


117.75 kcal mol-1
-10

χC=2.598 Q.16 χ= 1.82


Q.21 25%

0.92Δ Q.20

76.82% Q.23 2860 kJ/mol

Q.25 3.23X 10 esu cm m=78.08 Q.24 α =104 ° 20 Q.27 Initially Ar + will be present.
The EA value
of Ar +(15.76 eV) is almost

as IE1 for Ar. IE1 for Kr is 14.0 eV. so reaction , Ar+ +-1e0 →Ar, will occur ex
othermally and energy released will ionize Kr into Kr+. IE1 value for He, Ne are
larger so these atoms wi
ll not react.

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Objective Periodic Table & Bonding
Among the following outermost configuration o
f transition metals which shows the highest oxidation state is: (a) 3d4,4s2 (b)
3d5,4s1
(c) 3d5,4s2 (d) 3d6,4s2 Which of the following ions has the lowest magnetic
moment?
(b) Ni2+ (c) Co3+ (d) Fe2+ (a)Cu2+ Modern periodic table is based on the atomic
number
of the elements. The experiment which proved the significance of the atomic number
was:
(a) Mulliken’s oil drop experiment (b) Moseley’s work on X-ray spectra
(c) Bragg’s work on X-ray diffraction (d) Discovery of X-rays by Rontgen Which of
the following
pairs has both members from the same group of the periodic table? (a) Na,Ca (b)
Na, Cl (c)
Ca, Cl (d) Cl, Br Which of the following set of ions represents a collection of
iso-electronic species?
(a) Ba2+,Sr2+ K+, Ca2+ (b) K+,Cl-, Ca2+,Sc3+ 3- 2- - 2(c) N ,O ,F ,S (d)
Li+,Na+,Mg2+,Ca2+ Aluminium
is diagonally related to: (a) Li (b) Si (c) Be (d) B The paramagnetic species
among the following is:
Na+, Zn2+, Cu+, Fe3+ (a) Na+ (b) Zn2+ (c) Cu+ (d) Fe3+ The diamagnetic species
among the following
is: Cu2+, Cr3+, Co3+, Cd2+ (a) Cu2+, (b) Cr3+, (c) Co3+, (d) Cd2+ The correct
decreasing order of atomic
size among the following species is: Ar, K+, Cl-, S2-, Ca2+ (a) Ca2+ > K+> Ar >
Cl-> S2
(b) K+>Ca2+>Cl->Ar>S2(c) S2->Cl->Ar>K+>Ca2+ (d) S2+>Ar>Cl->Ca2+>K+ What would be
the atomic
number of the next halogen if discovered in future? (a) 115 (b) 119 (c) 117 (d)
121 Which of the following
has highest electron gain enthalpy? [A] [Ne] 3s2; [B] [Ne] 3s2 3P4; [C] [Ne] 3s2
3P5; [D] [Ne] 3s2 3p2

1. 2. 3.

4. 5. 6. 7. 8. 9.

10. 11. 12. 13.

(a)

[A]

(b)

[B]

(c)

[C]

(d)

[D]

14.
The five successive ionisation energies of the element are 800, 2727,3658,25024
and
32824 kJmol-1 respectively. The number of valence electron is: (a) 3 (b) 5 (c) 4
(d) 2
The ionic radius of Cr is minimum in which of the following compounds?
(a) CrF3 (b) CrCl3 (c) Cr2O3 (d) K2CrO4

Match the following lists and select


the correct answer: List I List II (A) 1s2,2s2 2p6,3s2 3p6, 4s1 (1) d-Block
element 2 2 6 2 6
(2) Halogen (B) 1s ,2s 2p ,3s 3p (C) 1s2,2s2 2p6,3s2 3p6,4s2 (3) Alkali metal 2 2
5
(D) 1s ,2s 2p (4) Noble gas A B C D (a) 1 2 3 4 (b) 3 4 1 2

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15. 16. 17. 18. 19.

20. 21.
22. 23.

In the iso-electronic species, the ionic radii (A)


of N3-,O2- and F- are respectively given by: (a) 1.36,1.40,1.71 (b) 1.36,1.71,1.40
(c) 1.71,1.40,1.36 (d) 1.71,1.36,1.40 In which of the following arrangements, the
order is not
according to the property indicated against it? (a) Al3+<Mg2+<Na+F- increasing
ionic size
(b) B<C<N<O increasing first ionisation

(c) 1 3 2 4 (d) 2 4 3 1 Which pair of atomic numbers


represents s-block elements? (a) 7,15 (b) 6,12 (c) 9,17 (d) 3,12 Chloride of an
element
‘A’ gives neutral solution in water. In the periodic table, the element ’A’
belongs to:
(a) First group (b) third group (c) fifth group (d)first transition series
Which one of the following belongs to representative group of elements in the
periodic table?
(a)Lanthanum (b)Argon (c)Chromium (d) Aluminium An element of atomic number 29
belongs to:
(a) s-block (b) p-block (c) d-block (d) f-block A trend common to both groups 1
and 17 elements in
the periodic table as atomic number increases is: (a) Increase in oxidizing nature
(b) Increase in
atomic radius (c) Increase in maximum valency (d) Increase in reactivity with
water Which of the
following has largest radius? (a) O2+ (b) Mg2+ (c) Na+ (d) FWhich one is the
correct order of the
Size of the iodine species? (a) I>I+>I(b) I> I-> I+ (c) I+>I->I (d) I->I>I+
24. 25. 26. 27. 28. 29. 30. 31. 32.

enthalpy (c) I<Br<F< Cl Increasing electron gain enthalpy


(d) Li<Na<K<Rb increasing metallic radius A sudden large jump between the values
of second
and third ionisation energies of an element would be associated with the
electronic configuration:
(a) 1s2,2s22p6,3s1 (b) 1s2,2s22p6, 3s2 3p1 (c) 1s2,2s2 2p6,3s2 3p2 (d) 1s2,2s2
2p6,3s2 In the
long form of the periodic table, all the non-metal are place with:
(a) s-block (b) p-block (c) d-block (d) f-block The lanthanide contraction is
responsible for
the fact that: (a) Zr and Y have about the same radius (b) Zr and Nb have similar
oxidation state
(c) Zr and Hf have about the same radius (d) Zr and Zn have the same oxidation
state Of cobalt
and Zinc salts, which are attracted in magnetic field? (a) Cobalt salts (b) Zinc
salts (c) both
(d) None The electronic configuration of an element is 1s2,2s2 2p6,3s2 3p3. What
is the atomic
number of the element which is just below the above element in the periodic table?
(a) 34 (b) 49 (c) 33 (d) 31 Element X belongs to 4th period. It contains 18 and 1
electron
in the penultimate and ultimate orbit. The X should be:
(a) Normal element (b) transition element (c) inert gas
(d) inner-transition element Element gain enthalpy of X would be equal to:
(a) electron affinity of X-(b) ionisation potential of X- (c) ionisation potential
of X (d)None
of the above Element with atomic number 35 belongs to:
(a) 3rd period (b) 18th group (c) 5th period (d) 17th group Most of the man-made
synthetic elements occur:
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(a) in actinide series (b) in lanthanide series (c) in coinage metals


(d) in alkaline earth metals Which is the largest stable atom?
(a) V (b) Na (c) Al (d) Pb Which of the following is strongest base?
(a) Be(OH)2 (b) Mg(OH)2 (c) Al(OH)3 (d) Si(OH)4 Which has largest atomic size?
(a) Al (b) Al2+ (c) Al3+ (d) Al+ Alkaline earth metals form ions of the formula:
(a) M+ (b) M- (c) M2+ (d) M2Which one of these is basic?
(a) CO2 (b) SnO2 (c) NO2 (d) SO2 Of cobalt and zinc salts,
which are attracted in a magnetic field? (a) Cobalt salts (b)
Zinc salts (c) Both (a) and (b) (d) None Which of the following species has the
highest
electron gain enthalpy? (a) F- (b) O (c) O- (d) Na+ Among the iso-electronic
species,
K+,S2-,Cl- and Ca2+ the radii of the ions decrease as:
(a) Ca2+>K+>Cl->S2-(b) Cl->S2->K+>Ca2+ (c) S2->Cl->K+>Ca2+ (d) K+>Ca2+>S2->Cl
The incorrect statement among the following is: (a) The first ionisation potential
of
Al is less than the first ionisation potential of Mg.
(b) The second ionisation potential of Mg is greater than the second ionisation
potential of Na.
(c) The first ionisation potential of Na is less than the first ionisation
potential of Mg.
(d) The third ionisation potential of Mg is greater than third ionisation
potential of Al.
Element with atomic number 56 belongs to which block?
(a) s (b) p (c) d (d) f
Which of the following order is wrong?
(a) NH3<PH3<AsH3—Acidic (b) Li<Be<B<C−IE1 (c) Al2O3<MgO<Na2O<K2O—Basic (d)
Li+<Na+<K+<Cs+--
Ionic radius Which is true about electronegativity order of the following
elements?
(b) C >N (c) C>Br (d) Sr>Ca (a)P> Si Eka-aluminium and Eka-silicon are known as:
(a) Gallium and germanium (b) aluminium and silicon (c) iron and sulphur (d)
proton and silicon
Two elements whose electronegativity are 1.2 and 3.0, the bond formed between them
would be:
(a) Ionic (b) covalent (c) coordinate (d) metallic Chloride ion and potassium ion
are iso-electronic. Then:
(a) Their sizes are same (b) Cl- ion is bigger than K+ ion (c) K+ ion is
relatively bigger
(d) Their sizes depend on other cation and anion
Identify the least stable ion amongst the following:
(a) Li(b) Be(c) B(d) C
Increasing order of electron gain enthalpy is:
(c) Al < N < O < Cl (a) N< O < Cl <Al (B) O < N < Al < Cl
Which of the following sets is of coinage metal?
(a) Cu, Ag, Hg (b) Zn, Cd, Hg (c) Au, Ag, Zn (d) Li, Na, K (d) Cl < N < O < Al

33. 34. 35. 36. 37. 38. 39. 40. 41.

42. 43.

44. 45. 46. 47. 48. 49. 50.

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