1

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
(a) In Homodiatomic molecule (A-A): r = A− A d A− A = bond length in molecule
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)
2. Z-effective Z eff = Z − σ Z = atomic number, σ= shielding constant
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
( χΑ ~ χΒ) =0.208 Δ Where Δ Actual bond energy –energy for 100% covalent bond energy Δ is
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= EA-B - E A− A X E B − B
1
⎡ 1
⎤
By eq. 1 and 4 ( χΑ ~ χΒ) = 0.208 ⎢ E A− B − (E A− A X E B − B ) 2 ⎥
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
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

( 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.

1 2

⎢⎣ ⎥⎦
4. Mulliken’s approach: According to Mulliken’s electronegativity of an atom is average of I.E.
I .E. + E. A. I .E. + E. A.
and E.A. χM = χP = Or χ P = 0.336[χ M − 0.615]
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
I .E. + E. A. I .E. + E. A. I .E. + E. A.
=96.48kJmol-1 χM = Also χ P = χP =
2 X 96.48 2 X 96.48 X 2.8 540
5.Allered and Rochow approach: In this method electronegativeiy is calculated as
0.359 Z effective
(χ A ) AR = 0.744 + χA =Electronegativiy of atom A on Allred & Rochow scale.
r2
Zeff.= Effective nuclear charge at periphery of element A. r= radius of an element in Δ
B-7. JAWAHAR NAGAR.Main Road ,Kota. Ph-0744-2422383 .Mo-93149-05055
2
SINHA I.I.T. CHEMISTRY
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 The first IP of lithium is 5.41 eV and electron affinity of Cl is -3.61 eV. Calculate ΔH in kJmol-1
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 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 andn20.77X10-22 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+ + 2F-
IE1 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.
B-7. JAWAHAR NAGAR. Main Road, Kota. Ph-0744-2422383 .Mo-93149-05055
 3
SINHA I.I.T. CHEMISTRY
Q.23 Calculate the molecular weight of HF if density of HF gas is 3.17 g/L at 300 K and 1.0 atm.
Comment on the result.
Q.24 The experimental dipole moment of water 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.
2
−
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
covalent or become ionic in aqueous solution. (Ionisation energy for AlCl 3 =5137 kJ mol-1 ; Δ hydration
for Al3+ = -4665 kJ mol-1 Δ hydration for Cl- = -381 kJ mol-1).

ANSWERS
Q.1 a=7270 kJ mol-1 Q.2 kJ = 173.7 kJ Q.3 a=11.835 eV and b =3.358 eV.
Q.4 1.667 X1023 Q.5 4.8 kcal Q.6 844 kJ mol-1 Q.7 1.6X 1018Cs+ ions.
Q.8 62% Q.9 +1532.7 kJ mol-1 Q.10 3.9 Q.11 1.26 Q.12 χC=2.598
Q.13 11.29 Q.14 χF= 3.87 Q.15 (χF )M = 10.435 , (χF )P = 3.726 Q.16 χ= 1.82

Q.17 1.61 Q.18 5.75 x 102 Q.19 0.92Δ Q.20 117.75 kcal mol-1 Q.21 25%
Q.22 76.82% Q.23 m=78.08 Q.24 α =104 ° 20 Q.25 3.23X 10 esu cm -10

Q.26 2860 kJ/mol 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 exothermally and energy
released will ionize Kr into Kr+. IE1 value for He, Ne are larger so these atoms will not react.

B-7. JAWAHAR NAGAR. Main Road, Kota. Ph-0744-2422383 .Mo-93149-05055

4
SINHA I.I.T. CHEMISTRY
Objective Periodic Table & Bonding
1. Among the following outermost configuration of transition metals which shows the
highest oxidation state is:
(a) 3d4,4s2 (b) 3d5,4s1 (c) 3d5,4s2 (d) 3d6,4s2
2. Which of the following ions has the lowest magnetic moment?
(a)Cu2+ (b) Ni2+ (c) Co3+ (d) Fe2+
3. 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
4. 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
5. 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+
6. Aluminium is diagonally related to:
(a) Li (b) Si (c) Be (d) B
7. The paramagnetic species among the following is:
Na+, Zn2+, Cu+, Fe3+
(a) Na+ (b) Zn2+ (c) Cu+ (d) Fe3+
8. The diamagnetic species among the following is: Cu2+, Cr3+, Co3+, Cd2+
(a) Cu2+, (b) Cr3+, (c) Co3+, (d) Cd2+
9. 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+
10. What would be the atomic number of the next halogen if discovered in future?
(a) 115 (b) 119 (c) 117 (d) 121
11. Which of the following has highest electron gain enthalpy?
[A] [Ne] 3s2; [B] [Ne] 3s2 3P4; [C] [Ne] 3s2 3P5; [D] [Ne] 3s2 3p2
(a) [A] (b) [B] (c) [C] (d) [D]
12. 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
13. The ionic radius of Cr is minimum in which of the following compounds?
(a) CrF3 (b) CrCl3 (c) Cr2O3 (d) K2CrO4
14. 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
(B) 1s ,2s 2p ,3s 3p (2) Halogen
(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

B-7. JAWAHAR NAGAR. Main Road, Kota. Ph-0744-2422383 .Mo-93149-05055

 5
SINHA I.I.T. CHEMISTRY
(c) 1 3 2 4 (d) 2 4 3 1
15. Which pair of atomic numbers represents s-block elements?
(a) 7,15 (b) 6,12 (c) 9,17 (d) 3,12
16. 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
17. Which one of the following belongs to representative group of elements in the periodic
table?
(a)Lanthanum (b)Argon (c)Chromium (d) Aluminium
18. An element of atomic number 29 belongs to:
(a) s-block (b) p-block (c) d-block (d) f-block
19. 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
20. Which of the following has largest radius?
(a) O2+ (b) Mg2+ (c) Na+ (d) F-
21. Which 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+
22. 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
23. 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
enthalpy (c) I<Br<F< Cl Increasing electron gain enthalpy (d) Li<Na<K<Rb increasing
metallic radius
24. 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
25. 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
26. 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
27. Of cobalt and Zinc salts, which are attracted in magnetic field?
(a) Cobalt salts (b) Zinc salts (c) both (d) None
28. 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
29. 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
30. 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
31. Element with atomic number 35 belongs to:
(a) 3rd period (b) 18th group (c) 5th period (d) 17th group
32. Most of the man-made synthetic elements occur:

B-7. JAWAHAR NAGAR. Main Road, Kota. Ph-0744-2422383 .Mo-93149-05055

6
SINHA I.I.T. CHEMISTRY
(a) in actinide series (b) in lanthanide series (c) in coinage metals (d) in alkaline earth metals
33. Which is the largest stable atom?
(a) V (b) Na (c) Al (d) Pb
34. Which of the following is strongest base?
(a) Be(OH)2 (b) Mg(OH)2 (c) Al(OH)3 (d) Si(OH)4
35. Which has largest atomic size?
(a) Al (b) Al2+ (c) Al3+ (d) Al+
36. Alkaline earth metals form ions of the formula:
(a) M+ (b) M- (c) M2+ (d) M2-
37. Which one of these is basic?
(a) CO2 (b) SnO2 (c) NO2 (d) SO2
38. 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
39. Which of the following species has the highest electron gain enthalpy?
(a) F- (b) O (c) O- (d) Na+
40. 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-
41. 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.
42. Element with atomic number 56 belongs to which block?
(a) s (b) p (c) d (d) f
43. 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
44. Which is true about electronegativity order of the following elements?
(a)P> Si (b) C >N (c) C>Br (d) Sr>Ca
45. Eka-aluminium and Eka-silicon are known as:
(a) Gallium and germanium (b) aluminium and silicon (c) iron and sulphur (d) proton and silicon
46. 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
47. 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
48. Identify the least stable ion amongst the following:
(a) Li- (b) Be- (c) B- (d) C-
49. Increasing order of electron gain enthalpy is:
(a) N< O < Cl <Al (B) O < N < Al < Cl (c) Al < N < O < Cl (d) Cl < N < O < Al
50. 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

B-7. JAWAHAR NAGAR. Main Road, Kota. Ph-0744-2422383 .Mo-93149-05055