S Block Elements
S Block Elements
UNIT 10
Lithium and beryllium, the first elements increase in atomic number, the atom becomes
+
of Group 1 and Group 2 respectively exhibit larger. The monovalent ions (M ) are smaller
some properties which are different from those than the parent atom. The atomic and ionic
of the other members of the respective group. radii of alkali metals increase on moving down
In these anomalous properties they resemble the group i.e., they increase in size while going
the second element of the following group. from Li to Cs.
Thus, lithium shows similarities to magnesium 10.1.3 Ionization Enthalpy
and beryllium to aluminium in many of their
The ionization enthalpies of the alkali metals
properties. This type of diagonal similarity is
are considerably low and decrease down the
commonly referred to as diagonal relationship
group from Li to Cs. This is because the effect
in the periodic table. The diagonal relationship
of increasing size outweighs the increasing
is due to the similarity in ionic sizes and /or
nuclear charge, and the outermost electron is
charge/radius ratio of the elements.
very well screened from the nuclear charge.
Monovalent sodium and potassium ions and
divalent magnesium and calcium ions are 10.1.4 Hydration Enthalpy
found in large proportions in biological fluids. The hydration enthalpies of alkali metal ions
These ions perform important biological decrease with increase in ionic sizes.
functions such as maintenance of ion balance + + + + +
Li > Na > K > Rb > Cs
and nerve impulse conduction. +
Li has maximum degree of hydration and
10.1 GROUP 1 ELEMENTS: ALKALI for this reason lithium salts are mostly
METALS hydrated, e.g., LiCl· 2H2O
The alkali metals show regular trends in their 10.1.5 Physical Properties
physical and chemical properties with the
All the alkali metals are silvery white, soft and
increasing atomic number. The atomic,
light metals. Because of the large size, these
physical and chemical properties of alkali
elements have low density which increases
metals are discussed below.
down the group from Li to Cs. However,
10.1.1 Electronic Configuration potassium is lighter than sodium. The melting
All the alkali metals have one valence electron, and boiling points of the alkali metals are low
1
ns (Table 10.1) outside the noble gas core. indicating weak metallic bonding due to the
The loosely held s-electron in the outermost presence of only a single valence electron in
valence shell of these elements makes them the them. The alkali metals and their salts impart
most electropositive metals. They readily lose characteristic colour to an oxidizing flame. This
+
electron to give monovalent M ions. Hence they is because the heat from the flame excites the
are never found in free state in nature. outermost orbital electron to a higher energy
level. When the excited electron comes back to
Element Symbol Electronic configuration the ground state, there is emission of radiation
in the visible region as given below:
Lithium Li 1s22s1
Metal Li Na K Rb Cs
Sodium Na 1s22s22p63s1
Potassium K 1s22s22p63s23p64s1 Colour Crimson Yellow Violet Red Blue
Rubidium Rb 1s22s22p63s23p63d104s24p65s1 red violet
Caesium Cs 1s22s22p63s23p63d104s2 λ/nm 670.8 589.2 766.5 780.0 455.5
6 10 2 6 1 1
4p 4d 5s 5p 6s or [Xe] 6s Alkali metals can therefore, be detected by
Francium Fr [Rn]7s 1 the respective flame tests and can be
determined by flame photometry or atomic
10.1.2 Atomic and Ionic Radii absorption spectroscopy. These elements when
The alkali metal atoms have the largest sizes irradiated with light, the light energy absorbed
in a particular period of the periodic table. With may be sufficient to make an atom lose electron.
THE s-BLOCK ELEMENTS 293
(ii) Reactivity towards water: The alkali the highest hydration enthalpy which
0
metals react with water to form hydroxide accounts for its high negative E value and
and dihydrogen. its high reducing power.
2 M + 2H2O → 2 M+ + 2OH− + H2
(M = an alkali metal) Problem 10.2
0 – –
It may be noted that although lithium has The E for Cl 2/Cl is +1.36, for I2/I is
0 + +
most negative E value (Table 10.1), its + 0.53, for Ag /Ag is +0.79, Na /Na is
+
reaction with water is less vigorous than –2.71 and for Li /Li is – 3.04. Arrange
that of sodium which has the least negative the following ionic species in decreasing
0
E value among the alkali metals. This order of reducing strength:
behaviour of lithium is attributed to its – –
I , Ag, Cl , Li, Na
small size and very high hydration energy.
Other metals of the group react explosively Solution
– –
with water. The order is Li > Na > I > Ag > Cl
They also react with proton donors such
as alcohol, gaseous ammonia and alkynes. (vi) Solutions in liquid ammonia: The alkali
(iii) Reactivity towards dihydrogen: The metals dissolve in liquid ammonia giving
alkali metals react with dihydrogen at deep blue solutions which are conducting
about 673K (lithium at 1073K) to form in nature.
hydrides. All the alkali metal hydrides are M + (x + y)NH3 →[M(NH3 )x ]+ + [e(NH3 )y ]−
ionic solids with high melting points. The blue colour of the solution is due to
the ammoniated electron which absorbs
2 M + H2 → 2 M + H −
energy in the visible region of light and thus
(iv) Reactivity towards halogens : The alkali imparts blue colour to the solution. The
metals readily react vigorously with solutions are paramagnetic and on
+ –
halogens to form ionic halides, M X . standing slowly liberate hydrogen resulting
However, lithium halides are somewhat in the formation of amide.
covalent. It is because of the high
polarisation capability of lithium ion (The M + (am ) + e − + NH3 (1) → MNH2(am ) + ½H2 (g)
distortion of electron cloud of the anion by (where ‘am’ denotes solution in ammonia.)
+
the cation is called polarisation). The Li ion In concentrated solution, the blue colour
is very small in size and has high tendency changes to bronze colour and becomes
to distort electron cloud around the diamagnetic.
negative halide ion. Since anion with large
size can be easily distorted, among halides, 10.1.7 Uses
lithium iodide is the most covalent in Lithium metal is used to make useful alloys,
nature. for example with lead to make ‘white metal’
(v) Reducing nature: The alkali metals are bearings for motor engines, with aluminium
strong reducing agents, lithium being the to make aircraft parts, and with magnesium
most and sodium the least powerful to make armour plates. It is used in
(Table 10.1). The standard electrode thermonuclear reactions. Lithium is also used
0
potential (E ) which measures the reducing to make electrochemical cells. Sodium is used
power represents the overall change : to make a Na/Pb alloy needed to make PbEt4
M(s) → M(g) sublimationenthalpy and PbMe4. These organolead compounds were
+
M(g) → M (g) + e −
ionizationenthalpy earlier used as anti-knock additives to petrol,
+ +
but nowadays vehicles use lead-free petrol.
M (g) + H2O → M (aq) hydrationenthalpy Liquid sodium metal is used as a coolant in
With the small size of its ion, lithium has fast breeder nuclear reactors. Potassium has
THE s-BLOCK ELEMENTS 295
a vital role in biological systems. Potassium The hydroxides which are obtained by the
chloride is used as a fertilizer. Potassium reaction of the oxides with water are all white
hydroxide is used in the manufacture of soft crystalline solids. The alkali metal hydroxides
soap. It is also used as an excellent absorbent are the strongest of all bases and dissolve freely
of carbon dioxide. Caesium is used in devising in water with evolution of much heat on
photoelectric cells. account of intense hydration.
Uses: It is used in (i) the manufacture of soap, found on the opposite sides of cell membranes.
paper, artificial silk and a number of chemicals, As a typical example, in blood plasma, sodium
–1
(ii) in petroleum refining, (iii) in the purification is present to the extent of 143 mmolL ,
of bauxite, (iv) in the textile industries for whereas the potassium level is only
–1
mercerising cotton fabrics, (v) for the 5 mmolL within the red blood cells. These
–1 +
preparation of pure fats and oils, and (vi) as a concentrations change to 10 mmolL (Na ) and
–1 +
laboratory reagent. 105 mmolL (K ). These ionic gradients
Sodium Hydrogencarbonate (Baking demonstrate that a discriminatory mechanism,
Soda), NaHCO3 called the sodium-potassium pump, operates
across the cell membranes which consumes
Sodium hydrogencarbonate is known as
more than one-third of the ATP used by a
baking soda because it decomposes on heating
resting animal and about 15 kg per 24 h in a
to generate bubbles of carbon dioxide (leaving
resting human.
holes in cakes or pastries and making them
light and fluffy). 10.6 GROUP 2 ELEMENTS : ALKALINE
Sodium hydrogencarbonate is made by EARTH METALS
saturating a solution of sodium carbonate with The group 2 elements comprise beryllium,
carbon dioxide. The white crystalline powder magnesium, calcium, strontium, barium and
of sodium hydrogencarbonate, being less radium. They follow alkali metals in the
soluble, gets separated out. periodic table. These (except beryllium) are
known as alkaline earth metals. The first
Na 2 CO3 + H2 O + CO2 → 2 NaHCO3
element beryllium differs from the rest of the
Sodium hydrogencarbonate is a mild members and shows diagonal relationship to
antiseptic for skin infections. It is used in fire aluminium. The atomic and physical
extinguishers. properties of the alkaline earth metals are
shown in Table 10.2.
10.5 BIOLOGICAL IMPORTANCE OF
SODIUM AND POTASSIUM 10.6.1 Electronic Configuration
A typical 70 kg man contains about 90 g of Na These elements have two electrons in the
and 170 g of K compared with only 5 g of iron s -orbital of the valence shell (Table 10.2). Their
and 0.06 g of copper. general electronic configuration may be
2
Sodium ions are found primarily on the represented as [noble gas] ns . Like alkali
outside of cells, being located in blood plasma metals, the compounds of these elements are
and in the interstitial fluid which surrounds also predominantly ionic.
the cells. These ions participate in the
Element Symbol Electronic
transmission of nerve signals, in regulating the configuration
flow of water across cell membranes and in the
transport of sugars and amino acids into cells. Beryllium Be 1s22s2
Sodium and potassium, although so similar Magnesium Mg 1s22s22p63s2
chemically, differ quantitatively in their ability Calcium Ca 1s22s22p63s23p64s2
to penetrate cell membranes, in their transport Strontium Sr 1s22s22p63s23p63d10
mechanisms and in their efficiency to activate 4s24p65s2
enzymes. Thus, potassium ions are the most Barium Ba 1s22s22p63s23p63d104s2
abundant cations within cell fluids, where they 4p64d105s25p66s2 or
activate many enzymes, participate in the [Xe]6s2
oxidation of glucose to produce ATP and, with Radium Ra [Rn]7s2
sodium, are responsible for the transmission
of nerve signals. 10.6.2 Atomic and Ionic Radii
There is a very considerable variation in the The atomic and ionic radii of the alkaline earth
concentration of sodium and potassium ions metals are smaller than those of the
THE s-BLOCK ELEMENTS 299
Table 10.2 Atomic and Physical Properties of the Alkaline Earth Metals
corresponding alkali metals in the same increase in ionic size down the group.
periods. This is due to the increased nuclear 2+ 2+ 2+
Be > Mg > Ca > Sr > Ba
2+ 2+
strontium and barium impart characteristic (iv) Reactivity towards acids: The alkaline
brick red, crimson and apple green colours earth metals readily react with acids liberating
respectively to the flame. In flame the electrons dihydrogen.
are excited to higher energy levels and when M + 2HCl → MCl2 + H2
they drop back to the ground state, energy is
(v) Reducing nature: Like alkali metals, the
emitted in the form of visible light. The
alkaline earth metals are strong reducing
electrons in beryllium and magnesium are too
strongly bound to get excited by flame. Hence, agents. This is indicated by large negative
these elements do not impart any colour to the values of their reduction potentials
flame. The flame test for Ca, Sr and Ba is (Table 10.2). However their reducing power is
helpful in their detection in qualitative analysis less than those of their corresponding alkali
and estimation by flame photometry. The metals. Beryllium has less negative value
alkaline earth metals like those of alkali metals compared to other alkaline earth metals.
have high electrical and thermal conductivities However, its reducing nature is due to large
which are typical characteristics of metals. hydration energy associated with the small
2+
size of Be ion and relatively large value of the
10.6.6 Chemical Properties
atomization enthalpy of the metal.
The alkaline earth metals are less reactive than
(vi) Solutions in liquid ammonia: Like
the alkali metals. The reactivity of these
alkali metals, the alkaline earth metals dissolve
elements increases on going down the group.
in liquid ammonia to give deep blue black
(i) Reactivity towards air and water: solutions forming ammoniated ions.
Beryllium and magnesium are kinetically inert
2+
M + ( x + y ) NH3 → ⎡⎣M ( NH3 ) X ⎤⎦ + 2 ⎡⎣e ( NH3 ) Y ⎤⎦
–
to oxygen and water because of the formation
of an oxide film on their surface. However,
powdered beryllium burns brilliantly on From these solutions, the ammoniates,
2+
ignition in air to give BeO and Be 3 N 2 . [M(NH3)6] can be recovered.
Magnesium is more electropositive and burns
with dazzling brilliance in air to give MgO and 10.6.7 Uses
Mg3N2. Calcium, strontium and barium are Beryllium is used in the manufacture of alloys.
readily attacked by air to form the oxide and Copper -beryllium alloys are used in the
nitride. They also react with water with preparation of high strength springs. Metallic
increasing vigour even in cold to form beryllium is used for making windows of
hydroxides. X-ray tubes. Magnesium forms alloys with
(ii) Reactivity towards the halogens: All aluminium, zinc, manganese and tin.
the alkaline earth metals combine with halogen Magnesium-aluminium alloys being light in
at elevated temperatures forming their halides. mass are used in air -craft construction.
M + X 2 → MX 2 ( X = F, Cl, Br, l ) Magnesium (powder and ribbon) is used in
Thermal decomposition of (NH4)2BeF4 is the flash powders and bulbs, incendiary bombs
best route for the preparation of BeF2, and and signals. A suspension of magnesium
BeCl2 is conveniently made from the oxide. hydroxide in water (called milk of magnesia)
600 − 800K is used as antacid in medicine. Magnesium
BeO + C + Cl 2 BeCl 2 + CO carbonate is an ingredient of toothpaste.
(iii) Reactivity towards hydrogen: All the Calcium is used in the extraction of metals from
elements except beryllium combine with oxides which are difficult to reduce with
hydrogen upon heating to form their hydrides, carbon. Calcium and barium metals, owing
MH2. to their reactivity with oxygen and nitrogen at
BeH2, however, can be prepared by the reaction elevated temperatures, have often been used
of BeCl2 with LiAlH4. to remove air from vacuum tubes. Radium
salts are used in radiotherapy, for example, in
2BeCl 2 + LiAlH 4 → 2BeH 2 + LiCl + AlCl 3
the treatment of cancer.
THE s-BLOCK ELEMENTS 301
( )
heated to 393 K.
2Ca ( OH )2 + 2Cl2 → CaCl 2 + Ca OCl + 2H2O
Bleaching powder
2
2 ( CaSO4 .2H2O ) → 2 ( CaSO4 ) .H2 O + 3H2O
Uses: Above 393 K, no water of crystallisation is left
(i) It is used in the preparation of mortar, a and anhydrous calcium sulphate, CaSO4 is
building material. formed. This is known as ‘dead burnt plaster’.
304 CHEMISTRY
It has a remarkable property of setting with silicate (Ca 3 SiO 5 ) 51% and tricalcium
water. On mixing with an adequate quantity aluminate (Ca3Al2O6) 11%.
of water it forms a plastic mass that gets into a Setting of Cement: When mixed with water,
hard solid in 5 to 15 minutes. the setting of cement takes place to give a hard
Uses: mass. This is due to the hydration of the
The largest use of Plaster of Paris is in the molecules of the constituents and their
building industry as well as plasters. It is used rearrangement. The purpose of adding
for immoblising the affected part of organ where gypsum is only to slow down the process of
there is a bone fracture or sprain. It is also setting of the cement so that it gets sufficiently
employed in dentistry, in ornamental work and hardened.
for making casts of statues and busts. Uses: Cement has become a commodity of
Cement: Cement is an important building national necessity for any country next to iron
material. It was first introduced in England in and steel. It is used in concrete and reinforced
1824 by Joseph Aspdin. It is also called concrete, in plastering and in the construction
Portland cement because it resembles with the of bridges, dams and buildings.
natural limestone quarried in the Isle of
10.10 BIOLOGICAL IMPORTANCE OF
Portland, England.
MAGNESIUM AND CALCIUM
Cement is a product obtained by An adult body contains about 25 g of Mg and
combining a material rich in lime, CaO with 1200 g of Ca compared with only 5 g of iron
other material such as clay which contains and 0.06 g of copper. The daily requirement
silica, SiO 2 along with the oxides of in the human body has been estimated to be
aluminium, iron and magnesium. The average 200 – 300 mg.
composition of Portland cement is : CaO, 50-
All enzymes that utilise ATP in phosphate
60%; SiO2, 20-25%; Al2O3, 5-10%; MgO, 2-
transfer require magnesium as the cofactor.
3%; Fe2O3, 1-2% and SO3, 1-2%. For a good
The main pigment for the absorption of light
quality cement, the ratio of silica (SiO2) to
in plants is chlorophyll which contains
alumina (Al2O3) should be between 2.5 and 4
magnesium. About 99 % of body calcium is
and the ratio of lime (CaO) to the total of the
present in bones and teeth. It also plays
oxides of silicon (SiO2) aluminium (Al2O3) and
important roles in neuromuscular function,
iron (Fe2O3) should be as close as possible to
interneuronal transmission, cell membrane
2.
integrity and blood coagulation. The calcium
The raw materials for the manufacture of concentration in plasma is regulated at about
cement are limestone and clay. When clay and 100 mgL–1. It is maintained by two hormones:
lime are strongly heated together they fuse and calcitonin and parathyroid hormone. Do you
react to form ‘cement clinker’. This clinker is know that bone is not an inert and unchanging
mixed with 2-3% by weight of gypsum substance but is continuously being
(CaSO4·2H2O) to form cement. Thus important solubilised and redeposited to the extent of
ingredients present in Portland cement are 400 mg per day in man? All this calcium
dicalcium silicate (Ca2SiO4) 26%, tricalcium passes through the plasma.
SUMMARY
The s-Block of the periodic table constitutes Group1 (alkali metals) and Group 2
(alkaline earth metals). They are so called because their oxides and hydroxides are alkaline
in nature. The alkali metals are characterised by one s-electron and the alkaline earth
metals by two s-electrons in the+ valence shell of their atoms. These are highly reactive
2+
metals forming monopositive (M ) and dipositve (M ) ions respectively.
THE s-BLOCK ELEMENTS 305
There is a regular trend in the physical and chemical properties of the alkali metal
with increasing atomic numbers. The atomic and ionic sizes increase and the ionization
enthalpies decrease systematically down the group. Somewhat similar trends are
observed among the properties of the alkaline earth metals.
The first element in each of these groups, lithium in Group 1 and beryllium in
Group 2 shows similarities in properties to the second member of the next group. Such
similarities are termed as the ‘diagonal relationship’ in the periodic table. As such
these elements are anomalous as far as their group characteristics are concerned.
The alkali metals are silvery white, soft and low melting. They are highly reactive.
The compounds of alkali metals are predominantly ionic. Their oxides and hydroxides
are soluble in water forming strong alkalies. Important compounds of sodium includes
sodium carbonate, sodium chloride, sodium hydroxide and sodium hydrogencarbonate.
Sodium hydroxide is manufactured by Castner-Kellner process and sodium carbonate
by Solvay process.
The chemistry of alkaline earth metals is very much like that of the alkali metals.
However, some differences arise because of reduced atomic and ionic sizes and increased
cationic charges in case of alkaline earth metals. Their oxides and hydroxides are less
basic than the alkali metal oxides and hydroxides. Industrially important compounds of
calcium include calcium oxide (lime), calcium hydroxide (slaked lime), calcium sulphate
(Plaster of Paris), calcium carbonate (limestone) and cement. Portland cement is an
important constructional material. It is manufactured by heating a pulverised mixture
of limestone and clay in a rotary kiln. The clinker thus obtained is mixed with some
gypsum (2-3%) to give a fine powder of cement. All these substances find variety of uses
in different areas.
Monovalent sodium and potassium ions and divalent magnesium and calcium ions
are found in large proportions in biological fluids. These ions perform important
biological functions such as maintenance of ion balance and nerve impulse conduction.
EXERCISES
10.1 What are the common physical and chemical features of alkali metals ?
10.2 Discuss the general characteristics and gradation in properties of alkaline earth
metals.
10.3 Why are alkali metals not found in nature ?
10.4 Find out the oxidation state of sodium in Na2O2.
10.5 Explain why is sodium less reactive than potassium.
10.6 Compare the alkali metals and alkaline earth metals with respect to (i) ionisation
enthalpy (ii) basicity of oxides and (iii) solubility of hydroxides.
10.7 In what ways lithium shows similarities to magnesium in its chemical behaviour?
10.8 Explain why can alkali and alkaline earth metals not be obtained by chemical
reduction methods?
10.9 Why are potassium and caesium, rather than lithium used in photoelectric cells?
10.10 When an alkali metal dissolves in liquid ammonia the solution can acquire
different colours. Explain the reasons for this type of colour change.
10.11 Beryllium and magnesium do not give colour to flame whereas other alkaline
earth metals do so. Why ?
10.12 Discuss the various reactions that occur in the Solvay process.
10.13 Potassium carbonate cannot be prepared by Solvay process. Why ?
10.14 Why is Li2CO3 decomposed at a lower temperature whereas Na2CO3 at higher
temperature?
306 CHEMISTRY
10.15 Compare the solubility and thermal stability of the following compounds of the
alkali metals with those of the alkaline earth metals. (a) Nitrates (b) Carbonates
(c) Sulphates.
10.16 Starting with sodium chloride how would you proceed to prepare (i) sodium metal
(ii) sodium hydroxide (iii) sodium peroxide (iv) sodium carbonate ?
10.17 What happens when (i) magnesium is burnt in air (ii) quick lime is heated with
silica (iii) chlorine reacts with slaked lime (iv) calcium nitrate is heated ?
10.18 Describe two important uses of each of the following : (i) caustic soda (ii) sodium
carbonate (iii) quicklime.
10.19 Draw the structure of (i) BeCl2 (vapour) (ii) BeCl2 (solid).
10.20 The hydroxides and carbonates of sodium and potassium are easily soluble in
water while the corresponding salts of magnesium and calcium are sparingly
soluble in water. Explain.
10.21 Describe the importance of the following : (i) limestone (ii) cement (iii) plaster of
paris.
10.22 Why are lithium salts commonly hydrated and those of the other alkali ions
usually anhydrous?
10.23 Why is LiF almost insoluble in water whereas LiCl soluble not only in water but
also in acetone ?
10.24 Explain the significance of sodium, potassium, magnesium and calcium in
biological fluids.
10.25 What happens when
(i) sodium metal is dropped in water ?
(ii) sodium metal is heated in free supply of air ?
(iii) sodium peroxide dissolves in water ?
10.26 Comment on each of the following observations:
+ + +
(a) The mobilities of the alkali metal ions in aqueous solution are Li < Na < K
+ +
< Rb < Cs
(b) Lithium is the only alkali metal to form a nitride directly.
0 2+ –
(c) E for M (aq) + 2e → M(s) (where M = Ca, Sr or Ba) is nearly constant.
10.27 State as to why
(a) a solution of Na2CO3 is alkaline ?
(b) alkali metals are prepared by electrolysis of their fused chlorides ?
(c) sodium is found to be more useful than potassium ?
10.28 Write balanced equations for reactions between
(a) Na2O2 and water
(b) KO2 and water
(c) Na2O and CO2.
10.29 How would you explain the following observations?
(i) BeO is almost insoluble but BeSO4 in soluble in water,
(ii) BaO is soluble but BaSO4 is insoluble in water,
(iii) LiI is more soluble than KI in ethanol.
10.30 Which of the alkali metal is having least melting point ?
(a) Na (b) K (c) Rb (d) Cs
10.31 Which one of the following alkali metals gives hydrated salts ?
(a) Li (b) Na (c) K (d) Cs
10.32 Which one of the alkaline earth metal carbonates is thermally the most stable ?
(a) MgCO3 (b) CaCO3 (c) SrCO3 (d) BaCO3