Chemical Classification & Periodicity Properties (S & P Blocks) (F-Only)
Chemical Classification & Periodicity Properties (S & P Blocks) (F-Only)
Chemical Classification & Periodicity Properties (S & P Blocks) (F-Only)
CHEMICAL CLASSIFICATION
&
PERIODICITY IN PROPERTIES
(S & P BLOCK)
PERIODICITY
2. Atomic Radius : Problem in calculating actual size of atom and hence distance between nuclei is
calculated giving rise to three type of radii for atoms.
d
(a) Covalent radius : Cr = Cr < actual atom size [Slight difference]
2
[Used for H2, Cl2 and such molecules]
d
(b) Metallic Radius : Mr = Mr > actual size [Slight difference]
2
[Used for metals]
d
(c) Vanderwaal radius : Vr = V >> actual size [very large difference]
2 r
In general VR > Mr > CR
(d) Ionic Radius : A cation is smaller than parent atom . An anion is larger than parent atom.
En 2 E n2
Zeff = where E is I.E. in kJ/mole ; Zeff = E is I.E. in eV per atom.
1312 13.6
or Calculated by Slaters rule.
SLATER’S RULE :
(a) For calculating on a (s or p) block (other than on 1s)
Rule-1 : Each (ns, nP) electron contribute to a screening factor of 0.35.
Rule-2 : Each (n – 1)th shell electron contribute to a screening factor of 0.85.
Rule-3 : Each (n – 2)nd and deeper shell electron contribute to a screening factor of 1.
[* On 1s, the screening factor due to other electron is taken as 0.3]
(b) For calculating on (d or f) block.
Rule-1 : Each screening causing electron (d or f ) of same shell has factor of 0.35.
Rule-2 : Each electron other than Rule-1 have screening factor of 1.
General Trend :
Along a period, size decrease [‘n’ constant, Zeff ]
Along a group, size increase [‘n’ increasing, Zeff constant]
Exceptions :
(1) Noble gases have largest atomic sizes [Vander waal radii]. However, their covalent radii are smaller e.g. Xe.
(2) Size of Ga and Al are same, [Zeff increasing]
IONISATION ENERGY :
Amount of energy required to remove the most loosely bounded electron from an isolated gaseous atom.
Units : kJ mol–1, k cal mol–1, eV per atom.
Ionisation is endothermic (endoergic) i.e. requires energy hence
H is +ve
M + Energy (IE1) M+ + e–
M M+ + e– H = IE1
+
M M + e +2 – H = IE2
M+2 M+3 + e– H = IE3
IE3 > IE2 > IE1 always
ELECTRON AFFINITY :
Amount of energy released when an electron is added to an isolated gaseous atom.
Units : k J mol 1 , k Cal mol 1 and eV per atom.
Addition of electron results in release of energy in most of the cases but 2nd E. A. is always energy
required. The sum of EA1 & EA2 is energy required.
1
EA Zefff . Cl has the highest E.A.
atomic size
ELECTRON GAIN ENTHALPY :
When expressed in terms of enthalpy change (H) then it is termed as E.G.E. Remember that
H = – ve for exothermic change.
For EA1, energy is released HEA1 = – ve
For EA2, onwards is required HEA2 = + ve
EA1 + EA2 , energy is always required.
Ip EA
Mulliken's Scale : XA = (e v) .
2
Mulliken's values of E N are about 2.8 times as large as Pauling .
0.359 Z eff
AllredRochows : XA = + 0.744
r2
FACTOR AFFECTING ELECTRO NEGATIVITY :
(1) Nuclear attraction : varies directly
(2) Atomic radius : varies inversely
(3) Change on ions : More positive charge more electronegativity and more –ve change less electronegativity.
(4) Hybridisation : to be discussed later in bonding.
General Trends : Along a period, electronegativity increases
Along a group, electronegativity decreases
Exceptions : None noteworthy.
FACTORS DEPENDENT ON ELECTRO NEGATIVITY :
(1) % ionic character varies directly.
(2) Strength of bond varies directly.
(3) B.L. : varies inversely.
(4) Nature of hydrides
(5) Nature of hydroxide.
MISCELLANEOUS CHEMICAL PROPERTIES :
1. Periodicity of hydra acids :
(a) Acidic character of hydra acid increases from left to right in a period.
(b) Acidic character of hydra acid increases from top to bottom in a group.
2. Periodicity of oxy acids :
(a) Acidic character of oxy acid increases from left in a period.
(b) Acidic character of oxy acid decreases from top to bottom in a group.
3. Periodicity of nature of oxide :
(a) On moving from left to right in a period acidic nature of oxide generally increases.
e.g. CO2 < P2O3 < SO2 < ClO2
(b) On moving from top to bottom in a group acidic nature of oxide generally decreases.
6. Diagonal relationship : Properties of elements of second period resemble with the element of third
period. These resembled properties between two periods or this type of relation between two periods
are called diagonal relationship.
(a) Boron and silicon form numerous hydride which spontaneously catch fire on exposure to air and are
easily hydrolysed.
(b) Boron halide like silicon halides hydrolysed by water. Aluminium halides are only partially hydrolysed by
water.
(c) Boron forms binary compounds with several metals known as borides just as silicon forms metal silicides
some of the borides and silicides under go hydrolysis to yield boron and silicon respectively.
(d) B2O3 and SiO2 are acidic in nature, Borates and silicates have tetrahedral BO4 and SiO4 structural units
respectively. Boro silicates are known in which form can replace silicon in three dimensional lattice.
However boron can also form planer BO3 unit.
(e) Both B and Al are semiconductors.
Bridge Elements : Typical elements of II period.
NOMENCLATURE OF THE ELEMENT :
The names are derived by using roots for the three digits in the atomic number of the element and adding
the ending –ium. The roots for the number are
Q.5 If there were 10 periods in the periodic table then how many elements would this period can maximum
comprise of.
Q.6 If (n + l) rule for energy is not followed, what are the blocks of the following elements if they are filled
according to increasing shell number
(a) K(19) (b) Fe(26) (c) Ga(31) (d) Sn(50)
Q.7 Use the following system of naming elements in which first alphabets of the digits are written collectively,
0 1 2 3 4 5 6 7 8 9
nil uni bi tri quad pent hex sept oct enn
to write three-letter symbols for the elements with atomic number 101 to 109.
[Example : 101 is Unu....]
Q.9 Element in which maximum ionization energy of following electronic configuration would be
(A) [Ne] 3s2 3p1 (B) [Ne] 3s2 3p2 (C) [Ne] 3s2 3p3 (D) [Ar] 3d10 4s2 4p3
Q.11 The electron affinity of the members of oxygen of the periodic table, follows the sequence
(A) O > S > Se (B) S > O < Se (C) O < S > Se (D) Se > O > S
Q.12 The process of requiring absorption of energy is
(A) F F– (B) Cl Cl– (C) O– O2– (D) H H–
Q.15 Atomic radii of flourine and neon in Å units are respectively given by
(A) 0.72, 1.60 (B) 1.60, 1.60 (C) 0.72, 0.72 (D) 1.60, 0.72
Q.18 Element Hg has two oxidation states Hg+1 & Hg+2. the right order of radii of these ions.
(A) Hg+1 > Hg+2 (B) Hg+2 > Hg+1 (C) Hg+1 = Hg+2 (D) Hg+2 Hg+1
Q.20 Why the first ionisation energy of carbon atom is greater than that of boron atom whereas, the reverse is
true for the second ionisation energy.
Q.22 Mg2+, O2–, Na+, F–, N3– (Arrange in decreasing order of ionic size)
Q.27 Explain why a few elements such as Be (+0.6), N(+0.3) & He(+0.6) have positive electron gain enthalpies
while majority of elements do have negative values.
Q.28 From among the elements, choose the following: Cl, Br, F, Al, C, Li, Cs & Xe.
(i) The element with highest electron affinity. (ii) The element with lowest ionisation potential.
(iii) The element whose oxide is amphoteric. (iv) The element which has smallest radii.
(v) The element whose atom has 8 electrons in the outermost shell.
Q.29 Which property will increase and which will decrease for IA group as we go down the group.
(a) Atomic size (g) E N
(b) Ionic radii (h) At. mass
(c) I E (i) Valance e–
(d) Density (j) Metallic ch
(e) Melting point (k) Chemical reactivity
(f) Boiling point
Q.30 The IE do not follow a regular trend in II & III periods with increasing atomic number. Why?
Q.31 Arrange in decreasing order of atomic size : Na, Cs, Mg, Si, Cl.
Q.32 In the ionic compound KF, the K+ and F– ions are found to have practically radii, about 1.34 Å each.
What do you predict about the relative covalent radii of K and F?
Q.34 Which will have a higher boiling point, Br2 or ICl , & why?
Q.38 Calculate E.N. of chlorine atom on Pauling scale if I.E. of Cl– is 4eV & of E.A. of Cl+ is + 13.0 eV.
Q.40 Calculate the E.N. of Cl from the bond energy of ClF (61 KCal/mol). Given that bond energies of F2
and Cl2 are 38 and 58 KCal/mol respectively.
Q.41 Calculate the radii of Na+ & F– if interionic distance between Na+ & F– ions is 2.31 Å.
Q.42 The IE values of Al(g) = Al+ +e is 577.5 kJ mol–1 and H for Al(g) = Al3+ +3e is 5140 kJ mol–1. If
second and third IE values are in the ratio 2 : 3. Calculate IE2 and IE3.
Q.43 How many chlorine atoms will be ionised Cl Cl+ + e–1 by the energy released from the process
Cl + e–1 Cl– for 6.02 × 1023 atoms (I.P. for Cl = 1250 kJ mol–1 and E.A. = 350 kJ mole–1)
Q.46 The As-Cl bond distance in AsCl3 is 2.20 Å. Estimate the SBCR (single bond covalent radius) of As.
(Assume EN of both to be same and radius of Cl = 0.99 Å.)
Q.47 The Pt-Cl distance has been found to be 2.32 Å in several crystalline compounds. If this value applies to
both of the compounds shown in figure. What is Cl - Cl distance in (a) and (b)
(a) (b)
Q.50 I.P. of Be+x is found to be 217.6 electron volt. What is the value of x.
Q.51 Calculate Zeff from slater’s rule & from Bohr’s model. Take I.E. of K from graph. IE of K is 4.3 eV.
Miscellaneous Properties
Q.55 The basic nature of hydroxides of group 13 (III-A) decreases progressively down the group. Comment.
Q.56 Based on location in P.T., which of the following would you expect to be acidic & which basic.
(a) CsOH (b) IOH (c) Sr(OH)2 (d) SeO3(OH)2 (e) FrOH (f) BrOH
Q.57 Calculate the lattice energy of NaCl crystal from the following date by the use of Born-Haber cycle.
Sublimation energy of Na = 26 kcal/g. atom, dissociation energy of Cl2 = 54 kcal/mole, ionisation
energy for Na(g) = 117 kcal/ mol, electron affinity for Cl(g) = 84 kcal/g atom, heat of formation of
NaCl = – 99 kcal/mole.
Q.58 Calculate the electron affinity of iodine with the help of the following data (given in Kcal/mole).
1
(Hfor)NaI= – 68.8, (H sub)Na= 25.9, (H sub H diss ) I2 =25.5, (IP)Na = 118.4, (U)NaI = – 165.4
2
EXERCISE # II
Q.1 Comment which of the following option represent the correct order of true (T) & false (F) statement.
I size of P < size of Q
II size of R < size of S
III size of P < size of R (appreciable difference)
IV size of Q < size of S (appreciable difference)
(A) TTTT (B) TTTF (C) FFTT (D) TTFF
Q.4 is a data sufficiency problem in which it is to be decided on the basis of given statements whether the
given question can be answered or not. (No matter whether the answer is yes or no)
Q.4 If HSolution < 0 then compound acts as ionic in aqueous solution. Is AlCl3(s) ionic in aqueous solution.
STAT 1: L.E. of AlCl3 is 5137 kJ/mol
STAT 2: HHE of Al+3 ion is – 4665 kJ/mol–1 & H HE of Cl– is –381 kJ/mol–1
(A) Statements (1) alone is sufficient but statement (2) is not sufficient.
(B) Statement (2) alone is sufficient but statement (1) is not sufficient.
(C) Both statement together are sufficient but neither statement alone is sufficient.
(D) Statement (1) & (2) together are not sufficient.
In following question a statement S and an explanation E is given. Choose the correct answers from the
codes A, B, C, D given for given question.
(A) S is correct but E is wrong.
(B) S is wrong but E is correct.
(C) Both S and E are correct and E is correct explanation of S.
(D) Both S and E are correct but E is not correct explanation of S.
Q.5 S : Lithium is a better reducing agent than Cs.
E : Sublimation energy and Ionisation energy of lithium is less than that of Cs.
Q.7 Bond distance C–F in (CF4) & Si–F in (SiF4) are respective 1.33Å & 1.54 Å. C–Si bond is 1.87 Å.
Calculation the covalent radius of F atom ignoring the electronegativity differences.
1.33 1.54 1.8 1.54
(A) 0.64 Å (B) Å (C) 0.5 Å (D) Å
3 2
Q.8 Two elements A & B are such that B. E. of A–A, B–B & A–B are respectively 81 Kcal / mole,
64 Kcal / mole, 76 Kcal / mole & if electronegativity of B is 2.4 then the electronegativity of A may be
approximately
(A) 2.81 (B) 1.8 (C) 1.99 (D) 3.0
Q.5 72 Q.6 (a) d block, (b) d block, (c) p block, (e) f block
Q.7 101 102 103 104 105 106 107 108 109
Unu Unb Unt Unq Unp Unh Uns Uno Une
Q.22 N3– > O2– > F– > Na+ > Mg2+ Q.23 Isolelectronic Ca+2(higher)
Q.24 Fe3+ , CO2+ Q.25 difference in 1E1 & 1E2 is less than 10ev.
Q.26 (a) F (b) O (c) Cl– Q.27 half filled and fully filled orbitals
Q.30 half filled & fully filled orbitals Q.31 Cs > Na > Mg > Si > Cl
Q.35 (a) P–Cl (b) S–O, (C) N–F Q.36 He < Ne < Ar < Kr < Xe < Rn
Q.41 0.95Å, 1.36Å Q.42 IE2 = 1825 kJ/mole, IE3 = 2737.5 kJ/mol
Q.43 1.686 × 1023 atom Q.44 3.476 eV Q.45 EN1 > EN2
Q.46 1.21 Å Q.47 4.64 Å ; b = 3.28 Å Q.48 17.15 Q.49 (i) 7.6 (ii) 13.85
Q.52 (a) Al+3 > Mg+2 > Na +, (b) Al+3 > Mg+2 > Na+, (c) Al+3 > Mg+2 > Na+, (d) Na+ > Mg+2 > Al+3,
Q.56 (a) basic (b) acidic (c) basic (d) acidic (e) basic (f) acidic
EXERCISE # II
Q.7 C Q.8 A, C
Q.9 (a) IE1 of A = 350 kJ/mol, (b) IE2 = 600 kJ/mol, (c) EGH of A = –450 kJ/mol,
EXERCISE # III
Q.13 Al+3 < Li+ < Mg2+< K+ Q.14 B Q.15 Ionic Q.16 ABC
Q.25 A