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S - Block Elements Unit - 10: Group I Elements: Alkali Metals

The document discusses the s-block elements, which include Groups 1 and 2 of the periodic table. Group 1 elements are alkali metals (lithium, sodium, potassium, etc.) that form cations with a +1 charge. Group 2 elements are alkaline earth metals (beryllium, magnesium, calcium, etc.) that form cations with a +2 charge. The document then focuses on the alkali metals, describing their physical and chemical properties including reactions with oxygen, water, hydrogen, and halogens. It notes trends in properties like ionization energy and hydration energy as atomic number increases.

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0% found this document useful (0 votes)
203 views15 pages

S - Block Elements Unit - 10: Group I Elements: Alkali Metals

The document discusses the s-block elements, which include Groups 1 and 2 of the periodic table. Group 1 elements are alkali metals (lithium, sodium, potassium, etc.) that form cations with a +1 charge. Group 2 elements are alkaline earth metals (beryllium, magnesium, calcium, etc.) that form cations with a +2 charge. The document then focuses on the alkali metals, describing their physical and chemical properties including reactions with oxygen, water, hydrogen, and halogens. It notes trends in properties like ionization energy and hydration energy as atomic number increases.

Uploaded by

Vivan T
Copyright
© © All Rights Reserved
We take content rights seriously. If you suspect this is your content, claim it here.
Available Formats
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s -BLOCK ELEMENTS
Unit – 10

The s-block elements of the Periodic Table are those in which the last
electron enters the outermost s-orbital. As the s-orbital can accommodate
only two electrons, two groups (1 & 2) belong to the s-block of the Periodic
Table. Group 1 of the Periodic Table consists of the elements: lithium, sodium,
potassium, rubidium, caesium and francium. They are collectively known as the
alkali metals. These are so called because they form hydroxides on reaction with
water which are strongly alkaline in nature. The elements of Group 2 include
beryllium, magnesium, calcium, strontium, barium and radium. These elements with
the exception of beryllium are commonly known as the alkaline earth metals. These
are so called because their oxides and hydroxides are alkaline in nature and these
metal oxides are found in the earth’s crust*.
The general electronic configuration of s-block elements is [noble gas]ns1 for
alkali metals and [noble gas] ns2 for alkaline earth metals.
The lithium shows similarities to magnesium and beryllium to aluminium in many
of their properties. This type of diagonal similarity is commonly referred to as
diagonal relationship in the periodic table.
The diagonal relationship is due to the similarity in ionic sizes and /or
charge/radius ratio of the elements. Monovalent sodium and potassium ions and
divalent magnesium and calcium ions are found in large proportions in biological
fluids.
GROUP I ELEMENTS: ALKALI METALS:
The alkali metals show regular trends in their physical and chemical properties
with the increasing atomic number.
Electronic Configuration:
All the alkali metals have one valence electron, ns1outside the noble gas core.
The loosely held s-electron in the outermost valence shell of these elements makes
them the most electropositive metals. They readily lose electron to give monovalent
M+ ions. Hence they are never found in free state in nature.
Atomic and Ionic Radii:
The alkali metal atoms have the largest sizes in a particular period of the periodic
table. With increase in atomic number, the atom becomes larger. The monovalent
ions (M+) are smaller than the parent atom. The atomic and ionic radii of alkali
metals increase on moving down the group i.e., they increase in size while going
from Li to Cs.
Ionization Enthalpy:
The ionization enthalpies of the alkali metals are considerably low and decrease
down the group from Li to Cs. This is because the effect of increasing size
outweighs the increasing nuclear charge, and the outermost electron is very well
screened from the nuclear charge.
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Hydration Enthalpy:
The hydration enthalpies of alkali metal ions decrease with increase in ionic
sizes. Li+> Na+ > K+ > Rb+ > Cs+ . Li+ has maximum degree of hydration and for this
reason lithium salts are mostly hydrated, e.g., LiCl· 2H 2O

Electro-positive nature : ( metallic character ) : alkali metals are the most


electro positive in the periodic table, their metallic character increases as we travel
down the group, the metallic character increases as their tendency to loose an
electron increases, these elements are good conductors of heat and electricity, they
exhibit lustre due to oscillation of free electrons
Physical Properties:
All the alkali metals are silvery white, soft and light metals. Because of the large
size, these elements have low density which increases down the group from Li to
Cs. The melting and boiling points of the alkali metals are low indicating weak
metallic bonding due to the presence of only a single valence electron in them. The
alkali metals and their salts impart characteristic colour to an oxidizing
flame. This is because the heat from the flame excites the outermost orbital
electron to a higher energy level. When the excited electron comes back to
the ground state, there is emission of radiation in the visible region.
Li- crimson red, Na- Golden yellow K –Pale violet
Rb- Violet Cs- Violet Be----- Mg-----
Ca- Brick red Sr- Crimson Ba- Apple green
Be and Mg – do not impart flame coloration due to high Ionisation enthalpies .

 Li – lightest metal known and density of K is less than Na

Chemical Properties:
(i) Reactivity towards air:
The alkali metals tarnish in dry air due to the formation of their oxides which
in turn react with moisture to form hydroxides. They burn vigorously in oxygen
forming oxides. Lithium forms monoxide, sodium forms peroxide, the other metals
form superoxides. The superoxide O2– ion is stable only in the presence of large
cations such as K, Rb, Cs.
4Li +O2 →2Li2O (oxide)
2Na+O →Na2O2 (peroxide)
M+O2 →MO2 (superoxide) (M = K, Rb, Cs)
Ex: K + O2  KO2
Because of their high reactivity towards air and water, they are normally kept in
kerosene oil.
(ii) Reactivity towards water:
The alkali metals react with water to form hydroxide and dihydrogen.
2M + 2H2O → 2M+ + 2OH− + H2 (M = an alkali metal)
Ex: 2Na + 2H2O  2Na+ + 2OH- + H2
Lithium is least reactive with water than sodium among the alkali metals. This is
because of its small size and very high hydration energy. Other metals of the group
react explosively with water. They also react with proton donors such as alcohol,
gaseous ammonia and alkynes.
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(iii) Reactivity towards dihydrogen:


The alkali metals react with dihydrogen at about 673K (lithium at 1073K) to form
hydrides. All the alkali metal hydrides are ionic solids with high melting points.
2M + H2 → 2M+H−
Ex: 2Na + H2  2Na+H-
(iv) Reactivity towards halogens:
The alkali metals readily react vigorously with halogens to form ionic halides,
+ –
M X . However, lithium halides are somewhat covalent. It is because of the high
polarisation capability of lithium ion. The Li + ion is very small in size and has high
tendency to distort electron cloud around the negative halide ion. Since anion with
large size can be easily distorted, among halides, lithium iodide is the most
covalent in nature.
Ex: 2Na + Cl2  2Na+Cl-
(v) Reducing nature:
The alkali metals are strong reducing agents, lithium being the most and
sodium the least powerful. The standard electrode potential (E 0)[ For aqueous
solutions] which measures the reducing power represents the overall change :
M(s) à M(g) sublimation enthalpy
+ -
M(g) à M (g) + e ionization enthalpy
M+ (g) + H2O à M+(aq) hydrationenthalpy
With the small size of its ion, lithium has the highest hydration enthalpy which
accounts for its high negative E0 value and its high reducing power.
However in the free state, ionisation enthalpy factor affects the reducing
nature, thus Li being small, with high Ionisation enthalpy, it becomes weak
reducing agent in its free state.
(vi) Solutions in liquid ammonia:
The alkali metals dissolve in liquid ammonia giving deep blue solutions which
are conducting in nature.
M + (x+y)NH3 →[M(NH3)x]+ + [e(NH3)y]−
The blue colour of the solution is due to the ammoniated electron which absorbs
energy in the visible region of light and thus imparts blue colour to the solution.
The solutions are paramagnetic and on standing slowly liberate hydrogen resulting
in the formation of amide.
M+(am) + e− + NH3(1) → MNH 3 (am) + ½H2(g) (where ‘am’ denotes
solution in ammonia.)
In concentrated solution, the blue colour changes to bronze colour and becomes
diamagnetic.
Uses:
 Lithium metal is used to make useful alloys.
 It is used in thermonuclear reactions.
 Lithium is also used to make electrochemical cells.
 Sodium is used to make a Na/Pb alloy needed to make PbEt 4 and PbMe4.
 These organo lead compounds were earlier used as anti-knock additives to
petrol, but nowadays vehicles use lead-free petrol.
 Liquid sodium metal is used as a coolant in fast breeder nuclear reactors.
 Potassium chloride is used as a fertilizer.
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Potassium hydroxide is used in the manufacture of soft soap. Caesium is


used in devising photoelectric cells.
GENERAL CHARACTERISTICS OF THE COMPOUNDS OF THE ALKALI
METALS:
Oxides and Hydroxides:
On combustion in excess of air, lithium forms mainly the oxide, Li 2O and
sodium forms the peroxide and oxides, (Na 2O2 and NaO2) whilst potassium,
rubidium and caesium form the superoxides, MO 2. These oxides are easily
hydrolysed by water to form the hydroxides according to the following reactions :
M2O + H2O → 2M++ 2OH-
EX: Li2O + H2O  2Li+ + 2OH-
M2O2 + 2H2O → 2M+ + 2OH- + H2O2
Ex: Na2O2 + 2H2O  2Na+ + 2OH- + H2O2
2MO2 + 2H2O → 2M++2OH- +H2O2 + O2
Halides:
The alkali metal halides can be prepared by the reaction of the appropriate oxide,
hydroxide or carbonate with aqueous hydrohalic acid (HX). All of these halides
have high negative enthalpies of formation; the Δ f H0 values for fluorides become
less negative as we go down the group, For a given metal Δ f H0 always becomes
less negative from fluoride to iodide. All these halides are soluble in water. The low
solubility of LiF in water is due to its high lattice enthalpy whereas the low
solubility of CsI is due to smaller hydration enthalpy of its two ions.
Salts of Oxo-Acids:
Oxo-acids are those in which the acidic proton is on a hydroxyl group with an oxo
group attached to the same atom e.g., carbonic acid, H 2CO3 (OC(OH)2; sulphuric
acid, H2SO4 (O2S(OH)2). The alkali metals form salts with all the oxo-acids. Their
carbonates (M2CO3) and in most cases the hydrogencarbonates (MHCO 3) also are
highly stable to heat.
As the electropositive character increases down the group, the stability of the
carbonates and hydorgencarbonates increases. Lithium carbonate is not so stable
to heat; lithium being very small in size polarises a large CO 32– ion leading to the
formation of more stable Li2O and CO2.
ANOMALOUS PROPERTIES OF LITHIUM:
The anomalous behaviour of lithium is due to the :
(i) exceptionally small size of its atom and ion, and
(ii) high polarising power (i.e., charge/ radius ratio).
Points of Difference between Lithium and other Alkali Metals:
(i) Lithium is much harder. Its m.p. and b.p. are higher than the other alkali
metals.
(ii) Lithium is least reactive but the strongest reducing agent among all the
alkali metals. On combustion in air it forms mainly monoxide, Li 2O and the
nitride, Li3N unlike other alkali metals.
(iii) LiCl is deliquescent and crystallises as a hydrate, LiCl.2H 2O whereas
other alkali metal chlorides do not form hydrates.
(iv) Lithium hydrogencarbonate is not obtained in the solid form while all
other elements form solid hydrogencarbonates.
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(v) Lithium unlike other alkali metals forms no ethynide on reaction with
ethyne.
(vi) Lithium nitrate when heated gives lithium oxide, Li 2O, whereas other
alkali metal nitrates decompose to give the corresponding nitrite.
4LiNO3 → 2Li2O + 4NO2 + O2
2NaNO3 → 2NaNO2 + O2
Points of Similarities between Lithium and Magnesium:
(i) Both lithium and magnesium are harder and lighter than other
elements in the respective
groups.
(ii) Lithium and magnesium react slowly with water. Their oxides and
hydroxides are much less soluble and their hydroxides decompose on
heating. Both form a nitride, Li 3N and Mg3N2, by direct combination with
nitrogen.
(iii) The oxides, Li2O and MgO do not combine with excess oxygen to give any
superoxide.
(iv) The carbonates of lithium and magnesium decompose easily on heating
to form the oxides and CO2. Solid hydrogencarbonates are not formed by
lithium and magnesium.
(vi) Both LiCl and MgCl2 are deliquescent and crystallise from aqueous
solution as hydrates, LiCl·2H2O and MgCl2·8H2O.
SOME IMPORTANT COMPOUNDS OF SODIUM:
Industrially important compounds of sodium include sodium carbonate, sodium
hydroxide, sodium chloride and sodium bicarbonate.
Sodium Carbonate (Washing Soda), Na2CO3·10H2O:
Solvay Process:
Sodium carbonate is generally prepared by Solvay Process.
In this process, advantage is taken of the low solubility of sodium
hydrogencarbonate whereby it gets precipitated in the reaction of sodium chloride
with ammonium hydrogencarbonate. The latter is prepared by passing CO 2 to a
concentrated solution of sodium chloride saturated with ammonia, where
ammonium carbonate followed by ammonium hydrogencarbonate are formed.
2NH3 + H2O + CO2 → (NH4)2 CO3
( NH4)2CO3 + H2O + CO2 → 2NH4HCO3
NH4 HCO3 + NaCl → NH4Cl + NaHCO3
Sodium hydrogencarbonate crystal separates. These are heated to give sodium
carbonate.
2NaHCO3 → Na2CO3 + CO2 + H2O
In this process NH3 is recovered when the solution containing NH 4Cl is treated with
Ca(OH)2. Calcium chloride is obtained as a by-product.
2NH4Cl + Ca(OH)2 →2NH3 + CaCl2 + H2O
[ Note: It may be mentioned here that Solvay process cannot be extended to the
manufacture of potassium carbonate because potassium hydrogencarbonate is too
soluble to be precipitated by the addition of ammonium hydrogencarbonate to a
saturated solution of potassium chloride. ]
Properties :
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Sodium carbonate is a white crystalline solid which exists as a decahydrate,


Na2CO3·10H2O. This is also called washing soda. It is readily soluble in water. On
heating, the decahydrate loses its water of crystallisation to form monohydrate.
Above 373K, the monohydrate becomes completely anhydrous and changes to a
white powder called soda ash.
Na2CO3.10H2O⎯⎯⎯⎯→ Na2CO3.H2O + 9H2O
Na2CO3.H2O ⎯⎯→ Na2CO3 + H2O
Uses:
(i) It is used in water softening, laundering and cleaning.
(ii) It is used in the manufacture of glass, soap, borax and caustic soda.
(iii) It is used in paper, paints and textile industries.
(iv) It is an important laboratory reagent both in qualitative and quantitative
analysis.

Sodium Chloride, NaCl:


Common salt is generally obtained by evaporation of sea water. Crude sodium
chloride, generally obtained by crystallisation of brine solution, contains sodium
sulphate, calcium sulphate, calcium chloride and magnesium chloride as
impurities.To obtain pure sodium chloride, the crude salt is dissolved in minimum
amount of water and filtered to remove insoluble impurities. The solution is then
saturated with hydrogen chloride gas. Crystals of pure sodium chloride separate
out. Calcium and magnesium chloride, being more soluble than sodium chloride,
remain in solution.
Uses :
(i) It is used as a common salt or table salt for domestic purpose.
(ii) It is used for the preparation of Na2O2, NaOH and Na2CO3.
Sodium Hydroxide (Caustic Soda),NaOH:
Sodium hydroxide is generally prepared commercially by the electrolysis of
sodium chloride in Castner-Kellner cell. A brine solution is electrolysed using a
mercury cathode and a carbon anode. Sodium metal discharged at the cathode
combines with mercury to form sodium amalgam. Chlorine gas is evolved at the
anode.
Cathode : Na+ + e− ⎯⎯Hg⎯→ Na – amalgam
Anode : Cl- à ½ Cl2 + e-
The amalgam is treated with water to give sodium hydroxide and hydrogen gas.
2Na-amalgam + 2H2O à NaOH + 2Hg + H2
Uses:
It is used in
(i) the manufacture of soap, paper, artificial silk and a number of
chemicals,
(ii) in petroleum refining,
(iii) in the purification of bauxite,
(iv) in the textile industries for mercerising cotton fabrics,
(v) for the preparation of pure fats and oils, and
Sodium Hydrogencarbonate (Baking Soda), NaHCO3:
Sodium hydrogencarbonate is known as baking soda because it decomposes on
heating to generate bubbles of carbon dioxide . Sodium hydrogencarbonate is
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made by saturating a solution of sodium carbonate with carbon dioxide. The white
crystalline powder of sodium hydrogencarbonate, being less soluble, gets separated
out.
Na2CO3 + H2O + CO2 → 2NaHCO3
Sodium hydrogencarbonate is a mild antiseptic for skin infections. It is used in fire
extinguishers.
BIOLOGICAL IMPORTANCE OF SODIUM AND POTASSIUM:
Sodium ions are found primarily on the outside of cells, being located in blood
plasma and in the interstitial fluid which surrounds the cells. These ions
participate in the transmission of nerve signals, in regulating the flow of water
across cell membranes and in the transport of sugars and amino acids into cells.
Potassium ions are the most abundant cations within cell fluids, where they
activate many enzymes, participate in the oxidation of glucose to produce ATP and,
with sodium, are responsible for the transmission of nerve signals.

GROUP 2 ELEMENTS : ALKALINE EARTH METALS:


The group 2 elements comprise beryllium, magnesium, calcium, strontium,
barium and radium. The first element beryllium differs from the rest of the
members and shows diagonal relationship to aluminium.

Electronic Configuration:
These elements have two electrons in the s -orbital of the valence shell . Their
general electronic configuration may be represented as [noble gas] ns 2. Like alkali
metals, the compounds of these elements are also predominantly ionic.
Atomic and Ionic Radii:
The atomic and ionic radii of the alkaline earth metals are smaller than those of
the corresponding alkali metals in the same periods. This is due to the increased
nuclear charge in these elements. Within the group, the atomic and ionic radii
increase with increase in atomic number.
Ionization Enthalpies:
The alkaline earth metals have low ionization enthalpies due to fairly large size of
the atoms. Since the atomic size increases down the group, their ionization
enthalpy decreases . The first ionisation enthalpies of the alkaline earth metals are
higher than those of the corresponding Group 1 metals. This is due to their small
size as compared to the corresponding alkali metals The second ionisation
enthalpies of the alkaline earth metals are smaller than those of the corresponding
alkali metals.
Hydration Enthalpies:
Like alkali metal ions, the hydration enthalpies of alkaline earth metal ions
decrease with increase in ionic size down the group.
Be2+ > Mg2+ > Ca2+ > Sr2+ > Ba2+
The hydration enthalpies of alkaline earth metal ions are larger than those of alkali
metal ions. Thus, compounds of alkaline earth metals are more extensively
hydrated than those of alkali metals,
Ex., MgCl2 and CaCl2 exist as MgCl2.6H2O and CaCl2· 6H2O while NaCl and KCl do
not form such hydrates.
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Physical Properties:
The alkaline earth metals, in general, are silvery white, lustrous and relatively
soft but harder than the alkali metals. Beryllium and magnesium appear to be
somewhat greyish. The melting and boiling points of these metals are higher than
the corresponding alkali metals due to smaller sizes. The trend is, however, not
systematic. Because of the low ionisation enthalpies, they are strongly
electropositive in nature. The electropositive character increases down the group
from Be to Ba. Strontium and barium impart characteristic brick red, crimson and
apple green colours respectively to the flame. In flame the electrons are excited to
higher energy levels and when they drop back to the ground state, energy is
emitted in the form of visible light. The electrons in beryllium and magnesium are
too strongly bound to get excited by flame. Hence, these elements do not impart
any colour to the flame.
Chemical Properties:
(i) Reactivity towards air and water:
Beryllium and magnesium are kinetically inert to oxygen and water because of
the formation of an oxide film on their surface. However, powdered beryllium
burns brilliantly on ignition in air to give BeO and Be 3N2. Magnesium is more
electropositive and burns with dazzling brilliance in air to give MgO and Mg 3N2.
Calcium, strontium and barium are readily attacked by air to form the oxide and
nitride. They also react with water with increasing vigour even in cold to form
hydroxides.
(ii) Reactivity towards the halogens:
All the alkaline earth metals combine with halogen at elevated temperatures
forming their halides.
M + X2 → MX2 (X=F,Cl,Br,l)
Ex: Mg + Cl2  MgCl2
Thermal decomposition of (NH4)2BeF4 is the best route for the preparation of BeF 2,
and BeCl2 is conveniently made from the oxide.
600 - 700K
BeO + C + Cl2 BeCl2 + CO
(iii) Reactivity towards hydrogen:
All the elements except beryllium combine with hydrogen upon heating to form
their hydrides, MH2. BeH2, however, can be prepared by the reaction of BeCl 2 with
LiAlH4.
2BeCl2 + LiAlH4 → 2BeH2 + LiCl + AlCl3
(iv) Reactivity towards acids:
The alkaline earth metals readily react with acids liberating dihydrogen.
M + 2HCl → MCl2 + H2
Mg + 2HCl  MgCl2 + H2
(v) Reducing nature:
The reducing power alkaline earth metals is less than those of their corresponding
alkali metals. Beryllium has less negative value compared to other alkaline earth
metals. However, its reducing nature is due to large hydration energy associated
with the small size of Be2+ ion and relatively large value of the atomization enthalpy
of the metal.
(vi) Solutions in liquid ammonia:
Like alkali metals, the alkaline earth metals dissolve in liquid ammonia to give
deep blue black
solutions forming ammoniated ions.
M + (x + y) NH3  [M(NH3)x]2+ + 2[e(NH3)y]-
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Uses:
 Beryllium is used in the manufacture of alloys.
 Copper-beryllium alloys are used in the preparation of high strength springs.
 Magnesium-aluminium alloys being light in mass are used in air-craft
construction.
 Magnesium (powder and ribbon) is used in flash powders and bulbs,
incendiary bombs and signals.
 Magnesium carbonate is an ingredient of toothpaste.
 Calcium is used in the extraction of metals from oxides which are difficult to
reduce with carbon.
 Radium salts are used in radiotherapy, for example, in the treatment of
cancer.
GENERAL CHARACTERISTICS OF COMPOUNDS OF THE ALKALINE EARTH METALS:
(i) Oxides and Hydroxides:
The alkaline earth metals burn in oxygen to form the monoxide, MO which,
except for BeO, have rock-salt structure. BeO is amphoteric while oxides of other
elements are ionic in nature. All these oxides except BeO are basic in nature and
react with water to form sparingly soluble hydroxides.
MO + H2O → M(OH)2
The solubility, thermal stability and the basic character of these hydroxides
increase with increasing atomic number from Mg(OH) 2 to Ba(OH)2.
Beryllium hydroxide is amphoteric in nature as it reacts with acid and alkali
both.
Be(OH)2 + 2OH– → [Be(OH)4]2–
Beryllate ion
Be(OH)2 + 2HCl + 2H2O → [Be(OH)4]Cl2
(ii) Halides:
Except for beryllium halides, all other halides of alkaline earth metals are ionic
in nature. Beryllium halides are essentially covalent and soluble in organic
solvents. Beryllium chloride has a chain structure in the solid state as shown
below:

(iii) Salts of Oxoacids:


Carbonates:
Carbonates of alkaline earth metals are insoluble in water and can be
precipitated by addition of a sodium or ammonium carbonate solution to a solution
of a soluble salt of these metals. All the carbonates decompose on heating to give
carbon dioxide and the oxide. Beryllium carbonate is unstable and can be kept
only in the atmosphere of CO2.
Sulphates:
The sulphates of the alkaline earth metals are all white solids and stable to heat.
BeSO4, and MgSO4 are readily soluble in water; the solubility decreases from CaSO 4
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to BaSO4. The greater hydration enthalpies of Be 2+ and Mg2+ ions overcome the
lattice enthalpy factor and therefore their sulphates are soluble in water.
Nitrates:
The nitrates are made by dissolution of the carbonates in dilute nitric acid. This
again shows a decreasing tendency to form hydrates with increasing size and
decreasing hydration enthalpy. All of them decompose on heating to give the oxide
like lithium nitrate.
2M(NO3)2 → 2MO + 4NO2 + O2 (M = Be, Mg, Ca, Sr, Ba)
ANOMALOUS BEHAVIOUR OF BERYLLIUM:
(i) Beryllium has exceptionally small atomic and ionic sizes and thus does not
compare well with other members of the group. Because of high ionisation enthalpy
and small size it forms compounds which are largely covalent and get easily
hydrolysed.
(ii) Beryllium does not exhibit coordination number more than four as in its
valence shell there are only four orbitals. The remaining members of the group can
have a coordination number of six by making use of d-orbitals.
(iii) The oxide and hydroxide of beryllium, unlike the hydroxides of other
elements in the group, are amphoteric in nature.

Diagonal Relationship between Beryllium and Aluminium:


(i) Like aluminium, beryllium is not readily attacked by acids because of the
presence of an oxide film on the surface of the metal.
(ii) Beryllium hydroxide dissolves in excess of alkali to give a beryllate ion,
[Be(OH)4]2– just as aluminium hydroxide gives aluminate ion, [Al(OH)4]–.
(iii) The chlorides of both beryllium and aluminium have Cl – bridged chloride
structure in vapour phase. Both the chlorides are soluble in organic solvents and
are strong Lewis acids. They are used as Friedel Craft catalysts.
(iv) Beryllium and aluminium ions have strong tendency to form complexes,
BeF42– , AlF6 3– .

SOME IMPORTANT COMPOUNDS OF CALCIUM:


Calcium Oxide or Quick Lime, CaO:
It is prepared on a commercial scale by heating limestone (CaCO 3) in a rotary
kiln at 1070-1270 K.
CaCO3 CaO + CO2
The carbon dioxide is removed as soon as it is produced to enable the reaction to
proceed to completion. Calcium oxide is a white amorphous solid. It has a melting
point of 2870 K. On exposure to atmosphere, it absorbs moisture and carbon
dioxide.
CaO + H2O  Ca(OH)2
CaO + CO2  CaCO3
The addition of limited amount of water breaks the lump of lime. This process is
called slaking of lime. Quick lime slaked with soda gives solid sodalime. Being a
basic oxide, it combines with acidic oxides at high temperature.
CaO + SiO2  CaSiO3
6CaO +P4O10  2Ca3(PO4)2
Uses:
(i) It is an important primary material for manufacturing cement and is the
cheapest form of alkali.
(ii) It is used in the manufacture of sodium carbonate from caustic soda.
(iii) It is employed in the purification of sugar and in the manufacture of dye
stuffs.
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Calcium Hydroxide (Slaked lime), Ca(OH)2:


Calcium hydroxide is prepared by adding water to quick lime, CaO. The aqueous
solution is known as lime water and a suspension of slaked lime in water is known
as milk of lime. When carbon dioxide is passed through lime water it turns milky
due to the formation of calcium carbonate.
Ca(OH)2 + CO2 → CaCO3 + H2O
On passing excess of carbon dioxide, the precipitate dissolves to form calcium
hydrogencarbonate.
CaCO3 + CO2 + H2 → Ca (HCO3)2
Milk of lime reacts with chlorine to form hypochlorite, a constituent of bleaching
powder.
2Ca(OH)2 + 2Cl2 → CaCl2 + Ca2(OCl)2 + 2H2O
Uses:
(i) It is used in the preparation of mortar, a building material.
(ii) It is used in white wash due to its disinfectant nature.
(iii) It is used in glass making, in tanning industry, for the preparation of
bleaching powder and for purification of sugar.
Calcium Carbonate, CaCO3:
It can be prepared by passing carbon dioxide through slaked lime or by the
addition of sodium carbonate to calcium chloride.
Ca(OH)2 +CO2 → CaCO3 +H2O
CaCl2 +Na2CO3 → CaCO3 + 2NaCl
Excess of carbon dioxide should be avoided since this leads to the formation of
water soluble calcium hydrogencarbonate. When heated to 1200 K, it decomposes
to evolve carbon dioxide.
1200K
CaCO3 ⎯⎯⎯⎯→CaO + CO2
It reacts with dilute acid to liberate carbon dioxide.
CaCO3 + 2HCl → CaCl2 + H2O + CO2
CaCO3 + H2SO4 → CaSO4 + H2O + CO2
Uses:
1. It is used as a building material in the form of marble and in the manufacture
of quick lime.
2. Calcium carbonate along with magnesium carbonate is used as a flux in the
extraction of metals such as iron.
3. Specially precipitated CaCO 3 is extensively used in the manufacture of high
quality paper.
4. It is also used as an antacid, mild abrasive in tooth paste, a constituent of
chewing gum, and a filler in cosmetics.
Calcium Sulphate (Plaster of Paris), CaSO4·½ H2O:
It is obtained when gypsum, CaSO4·2H2O, is heated to 393 K.
2CaSO4.2H2O → 2CaSO4.H2O + 3H2O
Above 393 K, no water of crystallisation is left and anhydrous calcium sulphate,
CaSO4 is formed. This is known as ‘dead burnt plaster’. On mixing with an
adequate quantity of water it forms a plastic mass that gets into a hard solid in 5 to
15 minutes.
Uses:
The largest use of Plaster of Paris is in the building industry as well as plasters. It
is used for immoblising the affected part of organ where there is a bone fracture or
sprain. It is also employed in dentistry, in ornamental work and for making casts
of statues and busts.
Cement:
PUI For Board and Competitive

Cement is an important building material. Cement is a product obtained by


combining a material rich in lime, CaO with other material such as clay which
contains silica, SiO2 along with the oxides of aluminium, iron and magnesium. The
average composition of Portland cement is : CaO, 50- 60%; SiO 2, 20-25%; Al2O3, 5-
10%; MgO, 2- 3%; Fe2O3, 1-2% and SO3, 1-2%.
The raw materials for the manufacture of cement are limestone and clay. When
clay and lime are strongly heated together they fuse and react to form ‘cement
clinker’. This clinker is mixed with 2-3% by weight of gypsum (CaSO 4·2H2O) to
form cement. Thus important ingredients present in Portland cement are
dicalcium silicate (Ca2SiO4) 26%, tricalcium silicate (Ca3SiO5) 51% and tricalcium
aluminate (Ca3Al2O6) 11%.
Setting of Cement:
When mixed with water, the setting of cement takes place to give a hard mass.
This is due to the hydration of the molecules of the constituents and their
rearrangement. The purpose of adding gypsum is only to slow down the process of
setting of the cement so that it gets sufficiently hardened.

Uses:
Cement has become a commodity of national necessity for any country next to iron
and steel.
It is used in concrete and reinforced concrete, in plastering and in the
construction of bridges, dams and buildings.
BIOLOGICAL IMPORTANCE OF MAGNESIUM AND CALCIUM :
The main pigment for the absorption of light in plants is chlorophyll which
contains magnesium About 99 % of body calcium is present in bones and teeth. It
also plays important roles in neuromuscular function, interneuronal transmission,
cell membrane integrity and blood coagulation. The calcium concentration in
plasma is regulated at about 100 mgL –1. It is maintained by two hormones:
calcitonin and parathyroid hormone

Important points for Competitive exams

Important ores of Alkali metals :

Sodium :
 Chile slatpeter ( NaNO3), Borax ( Na2B4O7.10H2O), Glauber salt
( Na2SO4.10H2O)
Potassium:
 Carnallite ( KCl.MgCl2.6H2O) and Felspar( K2O.Al2O3.6SiO2).
Rubidium

 Lithium ores such as Lepidolite, triphylite contains 0.7 to 3 % of Rb 2O.


Cesium :

 Lepidolite, Pollucite contains 0.2 to 7 % of Cs2O


Radioactivity of francium :
PUI For Board and Competitive

223
Francium is longest lived Isotope Fr with half life period of only 21 minutes.

 Lithium is the lightest metal


 Li+ has low mobility even though has smallest size because of smallest
size it get exclusively hydrated.
 Francium is radioactive metal with a half life of 21 minutes
 Sodium is found in the form of
 Sodium chloride : NaCl
 Sodium nitrate ( Chile salt petre ) NaNO3
 Glauber’s salt : Na2SO4.10H2O
 Albite or sodium feldspar : NaAlSiO8
 Borax or sodium borate : Na2B4O7.10H2O
 Sodium is extract from sodium chloride by Down’s process, where as
the purity is 99%
 BeO – is essentially covalent in nature and amphoteric in nature,
while other element oxides are basic in nature
BeO – Amphoteric MgO – Weakly basic CaO, SrO, BaO- basic

 Only Li2CO3 and LiOH – Decomposes on heating and is insoluble in


water, while other carbonates do not decompose on heating
 LiOH → Li2O + H2O
 Li2CO3 → Li2O + CO2
 Caustic soda (NaOH) is also prepared by
 Gossage process : Na2CO3 + Ca(OH)2→ CaCO3 + 2 NaOH
 Porous Diaphragm process ( Nelson cell process )
NaCl→ Na+ + Cl- ( in solution )
At cathode : 2H2O + 2e-→ H2 + 2 OH-
Na+ + OH- → NaOH
At anode : 2 Cl- → Cl2 + 2e-

 Sodium carbonate ( washing soda ) – Na 2CO3.10H2O. is also prepared


by the following process :
 Le-Blanc process : Na2SO4 + CaCO3 + 4C→ Na2CO3 + CaS + 4CO
 Magnesium oxide when mixed with a saturated solution of
Magnesium chloride, sets to a hard mass like cement known as
Magnesia cement or Sorel’s cement , the composition is
MgCl2.5MgO.XH2O

 Compounds of potassium :
1. Oxides : K + O2 → KO2
It is also obtained by treatment of dry KOH with Ozone
2KOH + O3 →2KO2 + H2O
K2O3 is obtained when O2 is passed through liquid ammonia
containing potassium
PUI For Board and Competitive

4K( dissolved in ammonia) 3O2 2K2O3

KO2 is used as an oxidising agent. It is used as air purifier in space


capsules, submarines and breathing masks, as it does both, i.e. produces oxygen
and removes carbon dioxide.

2. KOH: it is manufactured by electrolysis of KCl solution, it is used


for the absorption of gases like CO2 SO2 etc, its aqueous solution is
known as “potash lye”
3. K2CO3 : it is also called as Potash or pearl ash, it cannot be
synthesized by Solvay’s process , as potassium bicarbonate is more
soluble than sodium bicarbonate . thus has to be prepared by “ Le-
Blanc process” KCl is first converted into K2SO4 then this K2SO4 is
herated with CaCO3 and Carbon :
KCl + H2SO4→KHSO4 + HCl
KHSO4 +KCl→ K2SO4 + HCl
K2SO4 + CaCO3 +2C → K2CO3 + CaS + 2CO2

This mixture of K2CO3 and Na2CO3 is used as a fusion mixture in


laboratory.
4. KI : Preparation : KOH + HI → KI + H2O
K2CO3 + 2HI → 2KI + CO2 + H2O
3I2 + 6KOH →5KI + KIO3 + 3H2O

KI is obtained on large scale by action of ferroso ferric


iodide on potassium carbonate
4K2CO3 + Fe3I8 + 4H2O → 8KI + 4CO2 + Fe(OH)2.2Fe(OH)3 (ppt)

KI on readtion with HgCl2 forms a red precipitate, which dissolves on addition of


excess of KI forming K2HgI4

HgCl2 + 2KI → HgI2 + 2KCl

HgI2 + 2KI → K2HgI4 ,

This solution alkaline of K2HgI4 is called as Nessler’s reagent , used in the


detection and estimation of NH4+ ions .

Alkaline earth metals :

Important Ores :

 Beryllium : Beryl ( 3Beo.Al2O3.6SiO2 ) Phenacite ( Be2SiO4),


 Magnesium : Magnesite ( MgCO3) Dolamite ( CaCO3. MgCO3 )
Epsomite ( MgSO4.7H2O) carnalite ( MgCl2.KCl.6H2O ) Asbetos
( CaMg3SiO3).4H2O
PUI For Board and Competitive

 Calcium : Limestone ( CaCO3) , Gypsum ( CaSO4.2H2O) , Fluorapatate


[( 3Ca3(PO4)2 CaF2) ]
 Berium : Barytes ( BaSO4)
 Radium : Pitchblende : ( U3O8 )

Important Points :

 Among the alkali metal, strongest reducing agent is lithium , while


weakest is sodium
 Lindelar catalyst : Pd-posined with BaSO4 in Quinolin
 Keen’s cement : The setting of plaster of Paris is catalysed by sodium
chloride , while it is retarded by Borax or alum, addition of alum to
plaster of Paris makes the setting very hard, the mixture is known as :
Keen’s cement
 Sodium sesquicarbonate : ( Na3CO3 NaHCO3.H2O ) it is neither
deliquescent nor efflorescent
 Mixture of sodium carbonate and calcium sulphide is known as Black
ash
 Cs shows photoelectric effect

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