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CONCISE
INORGANIC
CHEMISTRY .
. '

FOURTH EDITION

__ J.D. Lee __ ~

Senior Lecturer in Inorganic Chemistr _ _M~'j I

Loughborough UniversityofTechn~~~ .J

t
" .

CHAPMAN & HALL

Universi1y and Professional Division

London · New York · Tokyo · Melbourne · Madras

 · Atomic structure and the
periodic table 1

THE ATOM AS A NUCLEUS WITH ORBITAL ELECiRONS

All atoms consist of a central nucleus surrounded by one or more orbital
electrons. The nucleus always contains protons and all nuclei heavier than
hydrogen contain neutrons too. ihe protons and neutrons together make
up most of the mass of the atom. Both protons and neutrons are particles
of unit mass, but a proton has one positive charge and a neutron is
electrically neutral (i.e. carries no charge). Thus the nucleus is always
positively tharged. The number of positive charges on the nucleus is
exactly balanced by an equal number of orbital electrons, each of which
carries one negative charge. Electrons arc relatively light -'- about I /1836
the mass of a proton. The 103 or so clements at present known are all built
up from these three fundamental particles in a simple way.
Hydrogen is the first and most simple elemenL It consists of a nucleus
containing one proton and therefore has one positi.ve charge, which is
balanced by one negatively tharged orbital electron. ihe second element is
helium. The nucleus contains two protons, and so has a charge of +2. The
nuclear charge of +2 is balanced by two negatively charged orbital ,,,. , orbit a
electrons. The nucleus also contains two tieutrons, whith minimize the / X~electrc
repulsion between the protons in the nucleus, and increase the mass of the
atom. All nuclei heavier than hydrogen contain tteutrons, but the number
present cannot be predicted reliably. (a)
\I
\ ,
&1'
__ ,,,
J
nucleu
This pattern is repeated for the rest of the elements. Element 3, lithium,
has three protons in the nucleus (plus some neutrons). The nuclear charge
is +3 and is balanced by three orbital electrons. Element 103, lawrencium, ...- x .....
has 103 protons in the nucleus (plus some neutrons). The nuclear charge is I / ' '\
·+ 103 and is balanced by 103 orbital electrons. The number of positive
charges on the nucleus of an atom always equals the number of orbitai
: ® \
\ I
'\ I
electrons, and is called the atomic i1uitlber of the element. (b) ' --x-" /
Iri the simple plafletary theory of the atotn, we imagine that these
electrons move round the nucleus in circular brbits, in much the same way
Figure I. I Structures of (a)
as the planets orhit round the sun. Thus hydrogen and helium (Figure I. I) hydrogen. symbol 11. atomic
have one anti two electrons respectively in their first orbit. The first orbit is number I : and ( b) helium .
then full. The next eight atoms are lithium, beryllium, boron, carbon, symbol H. atomic number 2.
 . ,,,,,- -..,)( / - -.,x /
,,,. x.- ...
/ /-x-;-, \ / ,....x .... , \ I / ... x""':-, \
I/@\ I
I I Be I x
1
I
I I
I®\
8 J
\ x ~I 0v I~
I J
\ \
__
' .....'-x-_....... /
I
I
\ \
''-x-"'_
........
I
_,,,, /
I I
\ '\.
\
' '-X- / /
'-x--"'
x
,,, -- . ......
x\
x----x
/ ,.....x.... '
x . . . --x
, ,..-x-., ' \
,,.-x-,
I x ,.... x-... x \
10 \ le' ,
,....~-, .

I
I
I

I N I
I
l xI I
I I
©'Ix
O
'
I
\ I
>t I
I
10 F
\I
I ~ ~ I Ne \ x
I \ I I \ \ / I \ \ I I \ \ I I
\ '-._X_.../
.. . . . -x..- I \ '-x-_... I 'x,,'-.x.-"',*' x 'x ..'-x-,....;xI
x /
>'.

Figure 1.2 Structures of the elements lithium to neon.

'x .. __ x"
-x- -x-
nitrogen, oxygen, fluorine and neon. Each has one more proton in the
nucleus than . the preceding element, and the extra electrons go into a
second orbit (Figure 1.2). This orbit is then full. In the next eight elements
(with atomic numbers 11 to 18), the additiOnal electrons enter a third shell.
The negatively charged electrons are attracted to the positive nucleus by
electrostatic attraction. An electron near the nucleus is strongly attracted
by the nucleus and has a low potential energy. An electron distant from the
nucleus is less firmly held and has a high potential energy.

ATOMIC SPECTRA OF HYDROGEN AND THE BOHR THEORY

When atoms are heated or subjected to an electric discharge, they absorb
energy, which is subsequently emitted ~s radiation. For example, if sodium
chloride is heated in the flame of a aunsen burner' sodium atoms are
produced which give rise to the characteristic yellow flame coloration.
(There are two lines in the emission spectrum of sodium corresponding to
wavelengths of589.0nm and 589.6nm.) Spectroscopy is a study of either
the radiation absorbed or the radiation emitted. Atomic spectroscopy is an
important technique for studying the energy and the arrangement of
electrons in atoms.
If a discharge is passed through hydrogen gas (H 2 ) at a low pressure,
some hydrogen atoms (H) are formed, which emit light in the visible
region. This light can he studied with u spectrometer, und is found to
comprise a series of lines of different wavelengths . Four lines can be seen
by eye, but many more are observed photographically in the ultraviolet
region. The lines become increasingly close together as the wavelength
(A.) decreases, until the continuum is reached (Figure 1.3). Wavelengths,
in metres, are related to the frequency, v, in Hertz (cycles/second) by
the equation:
c
v =-
A
 _ _ _ _A_T_O_M_I_C_S_P_EC_T_R_A_O_F_H_Y_D_R_O_G_E_N_A_N_D_T_H_E_B_O_H_R_T_H_E_O_R_Y~--- j [I)
o< o< o< o<
Cl) C')
;..
IO
0
r:-
c'I Continuum
co
in
co
co
CX)
'o:t
'o:t
M
'o:t
...
0
'o:t \

I
H..
I I
H13 . Hy
1111111
Ha Hm

Energy

Figure 1.3 Spectrum of hydrogen in the visible region (Bahner series.)

where c is the velocity of light (2.9979 x 108 ms- 1). In spectroscopy,

frequencies are generally expressed as wave nurtlbets v, where v ==
1/A.m ,. - •.
In 1885 Balmer showed that the wave number v of any line in the visible
spectrum of atomic hydrogen could be given by the simple empirical
formula:

v = R(..!_
22 - ...!...)
n2

where R is the. Rydberg constant and n has the values 3, 4. 5 ...• thus
giving a series of lines.
The lines observed in the visible region are called the Balmer series. but
several other series of lines may be observed in different regions of the
spectrum (Table 1.1).
Similar equations were found to hold for the lines in the other series in
the hydrogen spectrum ..

Lyman (l. - 1-)

v = R 12 ll2
n = 2, 3, 4, 5 ...

Ba Ith er v=R(l-1..)
22 n.2 n=3,4,5,6 ...

Table 1.1 Spectral series found in atornic hydrogen

Region of spectrum

Lyman series ultraviolet

Baitner series visible/ultraviolet
Pascheil series infrared
Brackett series infrared
Pfund series infrared
Humphries series infrared
0 [ _______A_T_O_M_I_C_S_T_R_U_C_T_U_R_E_A_N_D_T_H_E_PE_R_I_O_D_IC_T_A_B_L_E_ _ _ _ _ _~
Pasch en v= RG n\) n=
2 - 4, 5, 6, 7 .. .

Brackett v=R(~-_;)
4- rr
11=5,6,7,8 . . .

Pfund v=R(_!_ _
. 52
_!_)
n2 II = 6, 7, 8, 9 . . .

In the early years of this century, attempts were made to obtain a

physical picture of the atom from this and other evidence. Thomson had
shown in 1896 that the application of a high electrical potential across a gas
gave electrons, suggesting that these were present in atoms . Rutherford
suggested from alpha particle scattering experiments that a n atom con-
sisted of a heavy positively charged nucleus with a sufficient number of
electrons round it to make the atom electrically neutral. In 1913, Niels
Bohr combined these ideas and suggested that the atomic nucleus was
surrounded by electrons moving in orbits like planets round the sun . He
was awarded the Nobel Prize for Physics in 1922 for his work on the
structure of the atom. Several problems arise with this concept :

I. The electrons might be expected to slow down gradually.

2. Why should electrons move in an orbit round t~e nucleus?
· 3. Since the nucleus and electrons have opposite charges, they should
attract each other. Thus one would expect the electrons to spiral
inwards until eventually they collide with the nucleus.
To explain these problems Bohr postulated:

l. An electron did not radiate energy if it stayed in one orbit, and there-
fore did not slow down. ·
2. When an electron moved from one orbit to another it either radiated
or absorbed energy. If it moved towards the nucleus energy was
radiated and if it moved away from the nucleus energy was absorbed.
3. For an electron to remain in its orbit the electrostatic attraction between
the electron and the nucleus which tends to pull the electron towards
the nucleus must be equal to the centrifugat force which tends to throw
the electron out of its orbit . For an electron of mass m, moving with a
velocity v in an orbit of radius r
,
.. mv-
centnfugal force = --
r
If the charge on the electron is e. the number of charges on the nucleus
Z. and the permittivity of a vacuum £0

. . f
Cou 1om b1c attractive orce = -4-ze2
-,
Jl£or

so
c _ __ _ _ _ A_T_O_M_IC_S_P_E_C_T_RA~O_F_H_Y~D_R_O_G_EN_A_N_D_T_H_E_B_O_H_R_T_H_E_O_R_Y_ _ _ _~j[Z]

mv 2 Ze 2
-,- = 4neor 2 (1.1)

hence
Ze 2
v2 =--- (1.2)
4nE0mr
According to Planck's quantum theory, energy is not continuous but is
discrete. This means that energy occurs in 'packets' called quanta, of
magnitude h/2rt, where h is Planck's constant. The energy of an electron in
an orbit, that is its angular momentum mvr, must be equal to a whole
number n of quanta.
nh
mvr=-
2n
nh
v=-
. 2rtmr
nih2
v2 = -,,.---~
4rc2m2,2
Combining this with equation (1.2)
Ze 2 n 2 h2
4ne0 mr - 4n 2 m 2 r2
hence
t £ n2h2
= _(_l __
(1.3)
rcme 2 Z
For hydrogen the charge on the nucleus Z = I, and if
n = I this gives a value r = 12 x 0.0529 nm
n= 2 r = 22 x 0.0529 nm
n=3 r = 32 x 0.0529 tlin
This gives a picture of the hydrogen atom where an electron moves in
circular orbits of radius proportional to 12 , 22 , 32 ••• The atom will only
radiate energy when the elettrOh jumps from one orbit to a.n other. The
kinetic energy of an electron is -!mv 2 • Rearranging equation (1.1)
I 2 Ze2
E = -2mv = --·
--
81tEor

Substituting for r using equation (1.3)

Z 2e4 m
E= 8e?,n 2 h2
If an electron jumps from an initial orbit i to a final orbit f. the change in
energy D. E is
[I][- ATOMIC STRUCTURE AND THE PERIODIC TABLE ------~=_]

Zem( 1 I)
2 2

= 8£[,h ni - nr
2

Energy is related to wavelength {£ = hc:V so this equation is of the same

form as the Rydberg equation: -

( 1.4)

(Rydberg equation)

Thus the Rydberg constant

Z 2 e4 m
R= .
8£.i1h 3 c
The experimental value of R is 1.097373 x 107 m - 1, in good agreement
with the theoretical value of 1.096776 x 107 m- 1• The Bohr theory
provides an explanation of the atomic spectra of hydrogen. The different
series of spectral lines can be obtained by varying the values of ni and fir in
equation (1.4). Thus with nr = 1 and ni = 2, 3, 4 ... we obtain the Lyman
series of lines in the UV region. With nr = 2 and ni = 3, 4, 5 ... we get
the Balmer series of lines in the visible spectrum. Similarly, nr = 3 and
n; = 4, 5, 6 . .. gives the Paschen series, nr = 4 and ni = 5, 6, 7 ... gives the
Brackett series, and nr = 6 and n;- = 7, 8, 9 ... gives the Pfund series.
The various transitions which are possible between orbits are shown in
Figure 1.4.

REFINEMENTS TO THE BOHR THEORY

It has been assumed that the nucleus remains stationary except for rotating
on its own axis. This would be true if the mass of the nucleus were infinite,
but the ratio of the mass of an electron to the mass of the hydrogen nucleus
is 111836. The nucleus actually oscillates slightly about the centre of
gravity, and to allow for this the mass of the electron m is replaced by the
. reduced mass µ in equation (1.4):
mM
µ=
m. + M
where M is the mass of the nucleus. The inclusion of the mass of the
nucleus explains why different isotopes of an element produce lines in the
spectrum at slightly different wavenumbers.
The orbits are sometimes denoted by the letters K, L, M, N ... counting
outwards from the nucleus, and they are also numbered 1, 2, 3, 4 ... This
number is called the principal quantum number, which is given the symbol
 ~~~~~~-R_E_F_IN_E_M~EN_T_S_T_O~T_H_E_B_O_H_·R~T_H_E_O_R_Y~~~~~~~~J[.2]

0 p

Figure 1.4 Bohr orbits of hydrogen and the various series of spectral lines.

n. It is therefore possible t<> define which circular orbit is under

consideration by specifying the principal quantum number.
When an electron moves from one orbit to another it should give a single
sharp line in the spectrum, corresponding precisely to the energy dif-
ference between the initial and final orbits. If the hydrogen spectrum is
observe~ with a high resolution spectrometer it is found that some of the
lines reveal 'fine structure'. This means that a line is really composed of
several lines close together. Sommerfeld explained this splitting of lines by
assuming that some of the orbits were eliiptical; and that they precessed in
space round the nucleus. For the orbit dosest to the nucleus, the principal
quantum number n = 1, and there is a circular orbit. For the next orbit, #1e
principal quantum number n = 2, and both circular and elliptical orbits '~re
possible. To define an elliptical orbit, a second quantum number k is
needed. The shape of the ellipse is defined by the ratio Of the lengths of the
major arid lninor axes. Thus
major ·axis n
minor axis = k
k is called the azimuthal or subsidiary quantum 11utnber, and may have
values from 1, 2 ... Ii. Thus for fl = 2, nlk may have the values 2/2 (circular
 [}§] L _ ____A_T_O_M.I_C._:>_~~0~~~ -~N.D !_HE_P_E~!_?_P._l_S:__TABLE ----:--]
orbit) and 2/1 (elliptical orbit). For the principal quantum number n = 3,
nlk may have values 3/3 (circular), 3/2 (ellipse) and 3/1 (narrower ellipse).
The presence of these extra orbits, which have slightly different energies
k = 1 from each other , accounts for the extra lines in the spectrum revealed
under high resolution . The original quantum number k has now
been replaced by a new quantum number /, where I = k - 1. Thus for
n=l l=O
.S Bohr-Sommerfield
1en n = 3. ti = 2 I= 0 or 1
n=3 I= 0 or 1 or 2
II = 4 I = Oor 1 or 2 or 3
This explained why some of the spectral lines are split into two, three ,
four or more lines. In addition some spectral lines are split still further into
two lines (a doubl-e t). This is explained by assuming that an electron spins
on its axis in either a clockwise or an anticlockwise direction. Energy is
quantized. and the vafue of the spin angular momentum was first con-
sidered to be ms· h/2n, where ms is the spin quantum number with values
of ±~- (Quantum mechanics has since shown the exact expression to be
Vs(s + I)· h/2n, where s is either the spin quantum number or the
resultant of several spins.)
Zeeman showed that if atoms were placed in a strong magnetic field
additional lines appeared on the spectrum. This is because elliptical orbits
can only take up certain orientations with respect to the external field.
rather than precessing freeiy. Each of these orientations is associated
with a fourth quantum number m which can have values of l.
(/ - I) .. . . 0 ... (-/ + I).-/.
Thus a single line in the normal spectrum will appear as (2/ + 1) lines if a
magnetic field is applied.
Thus in order to explain the spectrum· of the hydrogen atom, four
quantum numbers are needed, as shown in Table 1.2. The spectra of other
atoms may be explained in a similar manner.

THE DUAL NATURE OF ELECTRONS-PARTICLES OR WAVES

Symbol Values

Principal quantum nurnl>er n l , 2. 3 .. .

Azimuthal or subsidiary quantum number 0, I, .. . (n - l)
Magnetic quantum number m -1 .. . . 0 ... . +l
Spin quantum number ±!
 THE HEISENBERG UNCERTAINTY PRINCIPLE .j ill]
certain orbits. The electron is thus considered as a particle. In the 1920s it
was shown that moving particles such as electrons behaved in some ways as
waves. This is an important concept in explaining the electronic structure
of atoms ..
For some time light has been considered as either particles or waves.
Certain materials such as potassium emit electrons when irradiated with
visible light, or in sorne cases with ultraviolet light. This is called the
photoelectric effect. It is explained by light travelling as particles called
photons. If a photon collides with an electron, it can transfer its energy to
the electron. If the energy of the photon is sufficiently large it can remove
the electron from the surface of the metal. However, the phenomena of
diffraction and interference of light can only be explained by assuming that
light behaves as waves. In 1924, de Brogie postulated that the same dual
character existed with electrons - sometimes they are considered as
particles, and at other times it is more convenient to consider them as
waves. Experimental evidence for the wave nature of electrons was
obtained when diffraction rings were observed photographically when a
stream of elec;trons was passed through a thin metal foil. Electron dif-
fraction has now become a useful tool in determining molecular structure,
particularly of gases. Wave mechanics is a means of studying the build-up
of electron shells in atoms, and the shape of orbitals occupied by the
electrons.

THE HEISENBERG UNCERTAINTY PRINCIPLE

Calculations on the Bohr model of an atom require precise information
about the position of an electron an(f its velocity. It is difficult to measure
both quantities accurately at the same time. An electron is too small to see
and may only be observed if perturbed. For example, we could hit the
electron with another particle such as a photon or an electton, or we could
apply an electric or magnetic force to the electron. This will inevitably
change the position of the electron, or its velocity and direction. Heisen-
berg stated that the more precisely we cart define the position of an
electron. the less certainly we are able to define its velocity. and vice versa.
If l:!..x is the uncertainty in defining the position and !:!.. v the uncertainty in
the velocity, the uncertainty principle may be expressed mathematically as:

. h
6.x.6v~­
. 4n
where h = Planck's c_onstant =
6.6262 x 10- 34 J s. This implies that it is
impossible to know both the position and the velocity exactly.
The concept of an electron following a definite orbit, where its position
and velocity are known exactly, must therefore be replaced by the prob-
ability of finding an electron in a particular position, or in a particular
volume of space. The Schrodinger wave equation provides a satisfactory
description of an atom in these terms. Solutions to the wave equation are