th differences between the following ?

(a) Rutherford's atomic model

What are the
Problem1. Atomic number and mass
ond Bohr'satomic model (b) Photon and quantum (c)
number (d) Emission specetra and absorption spectra (e) Size and shape of 2p
orbital.
and 3p orbitals () orbitand
Bohr's model is
ten (a)
Solution. () The fundamental difference between the two models is that
momentum of the
based on the concept of quantisation of energy and angular
permitted orbits with definite
electron. Electrons can move only in certain
model does not give an
amountof energy and angular momentum. Rutherford's
idea about the permitted orbits. necessarily light
magnitude but not
(b) Aquantum is abundle of energy of definite electromagnetic energy.
energy whereas a photon is a quantum of light i.e.,
equal to the free positive charge on
(c) Atomic number of an element is numerically
presence of protons and each
its nucleus. As the positive charge is due to the
one unit positive charge, atomic number is equal to the number
proton carries the number of
atom iselectrically neutral,
of protons present in an atom. Asthe
the free positive charges on
electrons in the extranuclear part must be equal to
and therefore, to the atomic number. Mass number is the total num
the nucleus
neutrons in the nucleus of an atom.
ber of nucleons i.e., protons and
StructureofAtom 2.105
Thus, different excited electrons followdifferent return jumps to the ground state
and emit different amounts of energies which are associated with radiations of
different wavelengths. This results into a large number of lines in the atomic
spectrum of hydrogen.
(d It is due to the opposite (anti-parallel) spins of the two clectrons that they occupy
the same orbital.
(e) The expected configuration of Cu (Z = 29) is [Ar),, 3& 4s but the shifing of
one electron from 4s orbital to 3d orbitals makes 4s orbital half-filled and 3d or
bitals completely-filled. These orbitals are comparatively more stable. Thus the
configuration of Cu atom becomes [Arl,, 3d" 4s' which, due to the presence of
completely-filled 3d orbitals and half-filled 4s orbital, is more stable than [Ar]o
3d 4s' configuration.
() The energy of an orbital depends upon the nuclear charge, principal quantum
number and presence of electrons in lower energy levels. In Li (multi-electron
atom) the inner electrons (1s) act as screen between nucleus and electron pre
sent in valence shellI. These screening electrons reduce the effect of attraction of
nucleus for the electron in the outermost orbital. This effect is called screening
effect or shielding effect. This effect is different on different types of orbitals and
hence electrons in different subshells possess different energies.
In a hydrogen atom, there is a single electron, therefore, screening effect is ab
sent. Thus attractive pull exerted by the nucleus on the electron remains unaf
fected. Hence energy of any orbital which this single electron occupies is only
determined by the principal quantum number.
(g) This is in accordance with Hund's rule, according to which electrons in singly
filled orbitals should have parallel spins.
(h) This keeps them farther apart and lowers energy throughelectron exchange or
resonance.
() Fe* has more stable configuration (3) as compared to 3d for Fe*.
) Threep-electrons in nitrogen are unpaired because it keeps them farther apart.
They have parallel spin due to greater stability of p' configuration due to ex
change energy.
(k) Such an arrangement reduces the force of repulsion and hence corresponds to a
lower energy configuration and thus greater stability.
Problem 3. (a) Write the electronic configuration of the following elements : P, Ca, Cu, Kr,
Cr and U. (Z forP= 15,Ca = 20, Cu = 29, Kr=36, Cr=24 and U = 92)
(B.I.T. 1993, 1994)
(b) Write the electronic configuration of Cr (Z = 24), Sc (Z=21) and N (Z=7).
Decide the possible values of the four quantum numbers for the 19th elec
tron inCr, 21st electron in Sc and p-electrons in N. (Roorkee 1983)
(c) How many unpaired electrons (n) do Fe and r have ? (Atomic number of
Fe = 26 and I =53) (PU. PET. 1985)
(d) Write the electronic configuration of the following ions in terms of s, p, d
and forbitals : K*, Cu*, Au*, Mn and I (Z for K, C, Au,Mn and I are
19,29, 79, 25 and 53 respectively. (B.C. E.C.E. 2000)
Solution. (a) P(Z= 15, period 3)= [Ne],o 3523p3
Ca (Z =20, period 4)- [Ar],g 4s
 1SC Chemistry-x
2.106
[Ar),, 3a"4s'
Cu (Z= 29, period 4) =[Ar),, 3a" 4s' 4p
Kr (Z= 36, period 4) = [Ar],g 3d 4s'
Cr (Z = 24, period 4) = 5f 6d 7s
(6) U(Z=92.
(i) Cr (Z= = [Rn)gs3d.
24) =7)[Ar],,4s'
period Accordingto Aufbau principle 19th electron
in Cr-atom goesto 4s orbital for which n =4, /=0, n = 0 and s= +|)

(ii) - Sc1/2.
(Z=21l) =[Ar],g 4s 3d'. According to Aufbau principle 21st electron in
Sc-atom goes to 3d orbital for which n =3, l=2, m=-22 andIs=+\2 or

-1/2.
three electrons Th
(iii) N (Z=7) = [He], 2s 2p'. Obviously 2p orbital has
electrons are distributed as 2p, 2p, and Zp;: Values of quant.
numbers for these electrons are :

2p ’n=2, l=1, m=+1,s=+ 1/2 or - 1/2

2p ’n=2, /=1, n =-1,s=+ 1/2 or- 1/2
2p: ’n=2, 1= 1, m =0, s =+ 1/2 or - 1/2
(c) () E. C. of Fe (Z = 26) = [Arl,,4s 3d (n=4 in 3d orbitals)
(ii) E. C. of I (Z = 53 but number of electrons = 53- 1= 52) = [Krls Ss 40
5p* (n=2 in 5p orbitals)
(d) () K(Z= 19,period 4) = [Ar],g 4s'
= 2, 8, 8 +4s'
=1s', 2s 2p, 3s' 3p,
K* (e= 18) = 1s',2s 2p,323p5
(ii) Cu (Z=29, period 4) =[Ar]s 3d 4s'
= ls, 2 2p, 3s3p + 3d0 4s'
1s², 2s² 2p, 3s 3p 3a', 4s'
=

Cu² (e=27) = 1s', 2s 2p, 3s 3p 3d

(ii) Au(Z=79, period 6) = Xels, 4f sa° 6s
= 2, 8, 18, 18, 8 + 4f 5al° 6s'
= 1s, 2s 2p, 3s? 3p°3d',4s 4p
4d0 4f, 5s' 5p sa, 6s'
Au (e= 76) = 1s', 2s 2p, 3s 3p3d0 4s 4p° 4d 4f

(iv) Mn (Z= 25, period 4) = [Ar],g 3d 4s

= 2, 8, 8 + 3d 4s
1s', 2s 2p, 3s 3p° 3d', 452
=
4
Mn (e= 23) = 1s', 2s 2p°,3s 3p34s
() I(Z= 53, period 5) = [Kr], 4d0 ss² 5p
=
2, 8, 18, 8 + 4d° 5s 5p
1s', 2s' 2p,3s3p3d°, 4s4
r (e= s4) =Is', 2s 2p, 3s3p3d°, 4s.
StructureofAtom 2.107

Problem4. Calculate
the ratio of the radius of second orbit of Hatom to that of third
orbit. (B.I.T 1994)

Solution. According to Bohr's theory, r, c n. Hence the ratio of the

radius of second orbit of
Hatom to that of third orbit is (2): (3) or 4:9.
Problem5. Choose the electronic configurations that are possible from among the fol-
lowing. Explain why the others are impossible ?
() 1s' 2s 2p (i) 1s² 2s 2p
(it) 1s' 2s' 2p 3s3p 3d? (iv) 1s' 2s 2p° 3s 3d (Bihar C.E.E.E. 1995)

Solution. () Impossible because s-subshell can not have more than two electrons.
(i) Possible.
(iii) Impossible because p-subshell can not have more than six electrons.
(iv) Impossible because after filling 3s-subshell, electrons will enter 3p-subshell
and not 3d-sub-shell.
1990)
Dablem 6. Deduce the possible sets of four quantum numbers when n = 2. (M.LN.R.
Salution, For n=2, I=0, 1. For /= 0, m=0 and for l= 1, m =±1,0. Spin quantum number
(s) can have value of +1/2 or - 1/2. Thus the possible sets of quantum numbers are:

2s' ’n=2, l=0, m = 0, s =+(1)

252 2

2s'’n=2, l= 0, m=0, s=

2p. ’ n= 2, l = 1, m =0, s =+()

2

2p ’n=2,l =1l,m= 0, s =-()

2

’n=2, l=1, m=+1, s=+‘)

2p, 2
2p
2p n=2,l=1, m=+1, s= 1
2
()
1
2p: ’n= 2, l = 1, m=-1, s =+ 2
()
|2p: n=2, l= l, m =-1, s =- (
2
)
Problem 7. An element has atomic number 12. (a) Find out its electronic configuration.
(b) Name the element. (c) Write quantum numbers for the valence-shell elec
trons of this element. (0.J.E.E. 1991)
Solution. (a) E.C. of the element with atomic number 12 is 1s, 2s 2p°, 3s.
(6) Since the last electron enters 3s orbital, which has two electrons, this element is
the 2nd element of 3rd period, i.e., this element is Mg (Z = 12)
(c) Valence shell E.C. is 3s. Values of n, l, mand s for the two electrons, in 3s orbital
are:

|3s’n=3,l =0, m =0, s =+()

2

|3s'n= 3, l =0, m =0, s =--()

 2.112
Problem 20. Calculatethe energy in kilocalories per mole of the photons of an clectr

wavelength 7600 A.
netic radiationof 7600 x 10cm
2 = 7600 =
Solution. 10"cn s
c = 3x
3x100
=3.947 x 10l4
V=
A 7600 x 107
Frequency.
3.947 x 104
hy = 6.62 x 10x
Energy of one photon
= 2,61 x 10erg

photons
Energy of one mole of 1023
= 2.61 x 10x 6.02 x
= 15.71x 10" erg
in kilocalories
Energy of one mole of photons 15.7lx 10l!
[| kcal =4.185 x\09
4.185 x 10'0
= 37.538 kcal per mole
242 nm is just sufficient to ion.
Problem 21. Electromagnetic radiation of wavelength mol, h=6.6256 x1
sodium atom. Calculate the ionisation energy inkJ
(Roorkee 199,
Solution. 2 = 242 nm =242 x 10m
c = 3x 10 m s
3x10
E = hv= h.= 6.6256 x 1034 242 x10
0.082 × 10-" J
= 0.082 x 1020kJ
Energy per mole for ionisation
= 0.082 x 10 x6.02 x 10
= 493.6 kJ molr
Problem 22. How many photons of light having a wavelength 4000 A are nece
provide 1.00 J of energy ?
Solution. Energy of one photon = h.v= h.

(6.62 x10-34) (3.0x 10°) =4.965x 10'"J

4000 x10-10
1.00 =2.01 x 108
Number of photons
4.965 x 10-19
10-that
Problem 23. Find the number of quanta of radiations of frequency 4.67 x oi
meltI g
be absorbed in order to melt 5 gof ice. The energy required to
333 J.
Solution. Energy required to melt 5 g of ice
= 5x 333 = 1665 J