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PRE-UNIVERSITY

SEMESTER 2
CHEMISTRY
CHAPTER 4 :
GROUP 2
4.1 Physical Properties of Group 2
Group 2 are also known as alkali earth metal. The elements of Group 2
and some basic physical properties are described as below
Name ,
symbol
Z
Atomic
radius/
nm
Melting
point
(
o
C)
1st
ionisation
energy
(kJ/mol)
Electronic configuration
Beryllium
Be
4 0.112 1287 900 1s
2
2s
2

Magnesium
Mg
12 0.160 650 738 1s
2
2s
2
2p
6
3s
2

Calcium
Ca
20 0.197 842 590 1s
2
2s
2
2p
6
3s
2
3p
6
4s
2

Strontium
Sr
38 0.215 777 550 1s
2
2s
2
2p
6
3s
2
3p
6
3d
10
4s
2
4p
6
5s
2

Barium,
Ba
56 0.218 727 503
1s
2
2s
2
2p
6
3s
2
3p
6
3d
10
4s
2
4p
6

4d
10
5s
2
5p
6
6s
2

4.1.1 Atomic radius
Atomic radius depend on 2 factors
Nuclear charge Screening effect
When going down to Group 2, both screening effect and nuclear
charge increase. However, the increase in screening effect is
more significant, as more shell is used to filling in the electrons.
This will cause the effective nuclear charge to decrease,
resulting the electron cloud to be further away from the nucleus.
Hence atomic radius increase.
4.1.2 Melting point
The melting point of the Group 2 generally decrease when goes
down to group.
All the elements occur as hexagonal closed-packed structures
with the exception of barium and radium, which adopt the more
open body-centred cubic structure. The density decreases from
Be to Mg to Ca as a result of very strong metallic bonding in the
Group 2 elements, which leads to short metalmetal distances in
the lighter elements (225 pm in beryllium, for instance) and as a
result small unit cells.
4.1.3 Ionisation Energy.
The 1st ionisation energy decrease when goes down to Group 2.
Atomic size when goes down to Group 2 which contribute the
decrease in ionisation energy. Furthermore, with the increase in
atomic size, the number of shell also increase thus causing the
screening effect to increase. This may also affected the effective
nuclear charge as the distance between the electron and the
nucleus is getting further.
The third ionisation energy of Group 2 elements are extremely
high, which suggested that the 3rd electron the withdrawn from an
inner shell. Thus Group 2 elements only goes through 2nd
ionisation energy and form a stable M
2+
.
First Ionisation energy : M (g) M
+
(g) + e
-

Second Ionisation energy : M
+
(g) M
2+
(g) + e
-

Element Be Mg Ca Sr Ba
1
st
IE (kJ/mol) 900 740 590 550 500
2
nd
IE (kJ/mol) 2700 2190 1740 1610 1470
4.2 Chemical Properties of Group 2
Table below shows the E
0
value of Group 2 elements, When going down
to Group 2, E
0
value become more negative, indicates the reducing
ability increase when going down to group, hence stronger reducing
agent.
This may also indicates the reactivity increase when going down to
Group 2. Henceforth, we shall discuss the reactivity of Group 2
elements with air (oxygen) and water.
Element Be Mg Ca Sr Ba
E
o
/ V - 1.85 -2.37 -2.87 -2.89 - 2.90
Trend of reducing
agent

Reducing strength increased
4.2.1 Reaction of Group 2 elements with oxygen (air).
The Group 2 elements react with O
2
to form the oxides. All the
elements except Be also form unstable peroxides (MO
2
). The oxides
of Mg to Ra react with water to form the basic hydroxides while
BeO and Be(OH)
2
are amphoteric
When BeO act as base : BeO + 2 H
+
Be
2+
+ H
2
O
When BeO act as acid : BeO + 2 OH
-
+ H
2
O Be(OH)
4
2-

When Be(OH)
2
act as base : Be(OH)
2
+ 2 H
+
Be
2+
+ 2 H
2
O
When Be(OH)
2
act as acid : Be(OH)
2
+ 2 OH
-
Be(OH)
4
2-

On its nature, Beryllium is inert in air as its surface is passivated
by the formation of a thin layer of BeO. Magnesium and calcium
metals also tarnish in air with the formation of an oxide layer, but
will burn completely to their oxides when heated. Strontium and
barium, especially in powdered forms, ignite in air and are stored
under hydrocarbon oils
The oxides of the other Group 2 elements can be obtained by direct
combination of the elements (except Ba, which forms the peroxide)










Their melting points decrease down the group as the lattice
enthalpies decrease with increasing cation radius. Magnesium oxide
is a high-melting-point solid (as is BeO) and is used as a refractory
lining in industrial furnaces. Like BeO, MgO has a high thermal
conductivity coupled with a low electrical conductivity. This
combination of properties leads to its use as an electrically
insulating material around the heating elements of domestic
appliances and in electrical cables
Element Reaction with oxygen Reactivity
Melting point of
oxide
Be 2 Be + O
2
2 BeO


Mg 2 Mg + O
2
2 MgO
Ca 2 Ca + O
2
2 CaO
Sr Sr + O
2
SrO
Ba Ba + O
2
BaO
2

I
N
C
R
E
A
S
E

D
E
C
R
E
A
S
E

The peroxides of Mg, Ca, Sr, and Ba are prepared by a variety of
routes; only SrO
2
and BaO
2
can be made by direct reaction of
the elements. All the peroxides are strong oxidizing agents and
decompose to the oxide:
2 MO
2
(s) 2 MO(s) + O
2
(g)
Special note :
*The thermal stability of the peroxides increases down the group
as the radius of the cation increases. This trend is explained by
considering the lattice enthalpies of the peroxide and the
oxide, and their dependence on the relative radii of the
cations and anions. As O
2
is smaller than O
2
2
, the lattice
enthalpy of the oxide is greater than that of the corresponding
peroxide. The difference between the two lattice enthalpies
decreases down the group as both values become smaller with
increasing cation radius, therefore the tendency to decompose
decreases. Magnesium peroxide, MgO
2
, is consequently the
least stable peroxide
4.2.1.1 Reaction of Group 2 oxide with water : Properties of
Group 2 hydroxide
Beryllium oxide, BeO, is a white solid, which is insoluble in water,
with coordination number of 4, as expected for the small Be
2+
ion.
The oxides of the other Group 2 elements all adopt coordination
number of 6. This is due to Beryllium does not have empty d-
orbital available to coordinate more than 8 electrons at its center,
while other Group 2 elements have.
Magnesium oxide is insoluble but reacts slowly with water to form
Mg(OH)
2
; likewise CaO reacts with water to form the partially
soluble Ca(OH)
2
.
The oxides of Sr and Ba, SrO and BaO, dissolve in water to form
the strongly basic hydroxide solutions:
BaO(s) + H
2
O (l) Ba
2+
(aq) + 2OH
-
(aq)
Element
Reaction of metal oxide
with water
Rate of formation of
base
Be no reaction / does not dissolve
Mg MgO + H
2
O Mg(OH)
2




Ca CaO + H
2
O Ca(OH)
2

Sr SrO + H
2
O Sr(OH)
2

Ba BaO + H
2
O Ba(OH)
2

I
N
C
R
E
A
S
E

4.2.1 Reaction of Group 2 elements with water.
All Group 2 react with water to from metal (II) hydroxide, M(OH)
2
, with
hydrogen gas liberated
The reactivity of Group 2 with water increase (as suggested by their E
0

value). Beryllium react slowly under hot steam to form a white
precipitate of beryllium hydroxide. Magnesium reacts similarly as
beryllium does, however, compare to Be, the rate of reaction is higher.
Magnesium hydroxide, Mg(OH)
2
, is basic but only very sparingly soluble;
beryllium hydroxide, Be(OH)
2
, is amphoteric and in strongly basic
solutions it forms the tetrahydroxyberyllate ion, Be(OH)
4

Calcium react slowly with water under room condition, to form a cloudy
calcium hydroxide (also known as lime water). Limewater is well known to
test the presence of carbon dioxide, where CO2 will turn limewater
chalky and form white precipitate of calcium carbonate, which then
dissolved when on further reaction with CO
2
to form the
hydrogencarbonate (also known as bicarbonate) ion
Ca(OH)
2
(aq) + CO
2
(g) CaCO
3
(s) + H
2
O (l)
CaCO
3
(s) + H
2
O (l) + CO
2
(g) Ca(HCO
3
)
2
(aq)
Strontium and barium can react even in cold water to form a water
soluble strong base of strontium hydroxide and barium hydroxide
respectively. However, rate of reaction of barium is greater than
strontium, hence more vigorous
Element
Condition
of water
Reaction equation
Rate of
reaction
K
sp

(mol
3

dm
-9
)
Solubility
Be Hot steam Be + 2 H
2
O Be(OH)
2
+ H
2


6.92 x 10
-22


Mg Hot steam Mg + 2H
2
O Mg(OH)
2
+ H
2
5.61 x 10
-12

Ca
Water at
room
temperature
Ca + 2 H
2
O Ca(OH)
2
+ H
2
5.50 x 10
-6

Sr Cold water Sr + 2 H
2
O Sr(OH)
2
+ H
2
7.24 x 10
-6

Ba Cold water Ba + 2H
2
O Ba(OH)
2
+ H
2
2.54 x 10
-4

I
N
C
R
E
A
S
E

I
N
C
R
E
A
S
E

Element
Group 2 carbonate Group 2 Nitrate
Formula
Decomposition
temperature
Stability Formula Stability
Be BeCO
3
159
0
C

Be(NO
3
)
2


Mg MgCO
3
350
0
C Mg(NO
3
)
2

Ca CaCO
3
832
0
C Ca(NO
3
)
2

Sr SrCO
3
1340
0
C Sr(NO
3
)
2

Ba BaCO
3
1450
0
C Ba(NO
3
)
2

I
N
C
R
E
A
S
E

I
N
C
R
E
A
S
E

4.3 Thermal Decomposition of Nitrates and Carbonates
All nitrates of the Group 2 elements are decomposed by heat to form
metal oxides, nitrogen dioxide and oxygen gases.
2 M(NO
3
)
2
(s) 2 MO (s) + 4 NO
2
(g) + O2 (g)
All carbonates of the alkaline-earth metals also decompose on heating,
producing metal oxides and releasing carbon dioxide gas.
MCO
3
(s) MO (s) + CO
2
(g)
The thermal stabilities of Group 2 nitrates and carbonates increase down the
group from beryllium to barium. This means that the temperature needed to
decompose the nitrates and carbonates increases down the group.
The trend of decomposition for Group 2 nitrate and carbonate can be explained
below
Magnesium nitrate and magnesium carbonate decompose easily at low
temperatures.
This shows that the metal oxide is more stable than the nitrate and carbonate.
This can be explained by the fact that the size of the oxide ion, O
2-
, is smaller
than that of the nitrate, NO
3
-
, and carbonate, CO
3
2-
ions. As such, the oxide ion
can approach closer to the Mg
2+
cation forming a shorter and stronger bond









Magnesium nitrate, MgNO
3
Magnesium nitrate, MgCO
3
Besides, magnesium ion has a high charge density ratio giving the
ion a high polarisation power To polarise the electron clouds of the
nitrate and carbonate ions.
The electron clouds of the NO
3
-
ion and CO
3
2-
ion are easily
distorted, rendering the nitrogen-oxygen bonds in the NO
3
-
ions and
the carbon-oxygen bonds in the CO
3
2-
ions are weak and easily
broken.
The smaller O
2-
ions are left attached to the magnesium ions.
2 Mg(NO
3
)
2
(s) 2 MgO (s) + 4 NO
2
(g) + O
2
(g)
MgCO
3
(s) MgO (s) + CO
2
(g)
Barium nitrate and barium carbonate appear to be more stable
than that of it's counterparts of the magnesium. A higher
temperature is needed to decompose the salts. This is because the
large size of the barium ion lowers the charge density ratio of the
ion. The polarity of the ion depends directly on this ratio. A lower
charge density ratio means the cation is less polarising. When
barium ion approaches radius anion like NO
3
-
ion and CO
3
2-
ion, the
electron clouds of the anions will not be as distorted as when
bonded with the magnesium ion. The bonds between Ba-NO
3
and
Ba-CO
3
are more ionic and are much stronger than that of Ba-O.
4.4 Solubility of the Group 2 Sulphate
1. The solubility solubility of an ionic compound depends mainly on two
factors:
a. lattice energy b. hydration energy
2. Heat of hydration is defined as the energy released when one
mole of gaseous ions is hydrated by water molecules to form an
infinite dilute solution under standard condition.
For cation : M
+
(g) + water M
+
(aq) H
hyd
= ve kJ/mol
For anion : X
-
(g) + water X
-
(aq) H
hyd
= ve kJ/mol
*Hydration energy is always exothermic since it involves the attraction
of ions in the solute for water molecules. Similar to lattice energy,
its magnitude depends on :
*Charge of the ion higher the charge, the greater the heat of hydration.
This is due to more heat energy is released as stronger bond are formed
between the ion and molecules
*Size of the ion the smaller the ion, the greater the heat of hydration ;
the more heat released
3 The lattice energy of a crystalline substance refers to the amount of
energy released when one mole of the ionic substance is produced from
its ions in the gaseous state.
M
+
(g) + X
-
(g) MX (s) H = Lattice energy = ve kJ/mol
*In a lattice that consists of cations and anions with charges Z
+
and Z


between ionic distance (r
+
+ r

), the lattice energy can be expressed


using the relation below.

*So, higher the lattice energy (more negative or more exothermic), the
more stable the ionic compound formed, the more the energy required
to break the strong electrostatic forces between the 2 opposite charged
ions.


r r
Q Q
energy Lattice
.

Ion Be
2+
Mg
2+
Ca
2+
Sr
2+
Ba
2+

Charge density 64.5 30.8 20.2 17.7 14.8
H
hyd
(kJ / mol) 2486 1925 1577 1446 1308
4. All sulphates of Group 2 elements are white crystalline and
non-deliquescent solids. The solubility of these sulphates decrease
down the group. Magnesium sulphate is soluble in water, calcium
sulphate is slightly soluble and barium sulphate is insoluble.
5. This can be explained using the standard enthalpy of
solution, H
soln
, where it is defined as the heat absorbed or
released when one mole of crystal lattice is dissolved in water to
form ionic aqueous solution under standard condition.
MX (s) M
+
(aq) + X
-
(aq) H
soln
= + / kJ / mol
*If the H
soln
, is positive, the salt will be insoluble in water & if H
soln
,
is negative, it is soluble in water
6. Using Hess Law, the relationship between H
soln
, H
hyd
, and LE can
be explained using the chart below

M X (s) M
+
(aq) + X
-
(aq)


negative
M
+
(g) + X
-
(g)

7. A salt is soluble in water if its H
solution
is negative or exothermic.
This happens when the salt has a high hydration energy and a low
lattice energy. The more negative the enthalpy of solution, the
more soluble will be the salt.

solution
H

energy Lattice
H

hydration
H
8. (a) The solubility of the sulphates decreases down Group 2 because the
hydration energies of the ions decrease more rapidly than the lattice
energies with increasing ionic size in the order Mg
2+
<Ca
2+
< Sr
2+
< Ba
2+

(b) The lattice energies of the Group 2 sulphates decrease relatively
slower because the magnitude depends on (r
+
+ r

). The anion radius (r

)
for sulphate ion, SO
4
2
, is too big compare to the cation radius (r
+
).
(c) As a results, the overall (r
+
+ r

). does not show any signifcant


increase down the group. The lattice energy does not decrease very much
from magnesium sulphate to barium sulphate.
9. On the other hand, the small size of the magnesium ion plus its high
charge result in a lot of heat being released as hydration energy. This
hydration energy decreases rapidly down the group from magnesium ion to
barium ion because there is a significant increase in the size of the cations
down the group. The resulting enthalpy of solution for barium sulphate
becomes less negative compared to that of magnesium sulphate.
Consequently, the solubility decreases down the group in the order:
BeSO
4
> MgSO
4
> CaSO
4
> SrSO
4
>

BaSO
4

Group 2 sulphate Be SO
4
Mg SO
4
Ca SO
4
Sr SO
4
Ba SO
4

H
solution
(kJ / mol) -95.3 -91.2 + 17.8 + 18.70 +19.4
Solubility
(g / 100mL)
41.0 36.4 0.21 0.010 0.00025
BeSO
4
Mg SO
4
CaSO
4
Sr SO
4
BaSO
4

H
hydration
H
lattice energy
4.5 Application of Group 2 elements and compounds
4.5.1 Beryllium and its compound
Beryllium is unreactive in air on account of a passivating layer of an
inert oxide film on its surface, which makes it very resistant to
corrosion. This inertness, combined with the fact that it is one of the
lightest metals, results in its use in alloys to make precision
instruments, aircraft, and missiles.
It is highly transparent to X-rays due to its low atomic number (and
thus electron count) and is used for X-ray tube windows.
Beryllium is also used as a moderator for nuclear reactions (where it
slows down fast-moving neutrons through inelastic collisions)
because the beryllium nucleus is a very weak absorber of neutrons
and the metal has a high melting point.
As beryllium oxide is extremely toxic and carcinogenic by inhalation
and soluble beryllium salts are mildly poisonous, the industrial
applications of beryllium compounds are limited; BeO is used as an
insulator in high-power electrical devices where high thermal
conductivity is also necessary
4.5.2 Magnesium and its compound
Most of the applications of elemental magnesium are based on the formation of light
alloys, especially with aluminium, that are widely used in construction in applications
where weight is an issue, such as aircraft. A magnesiumaluminium alloy was
previously used in warships but was discovered to be highly flammable when
subjected to missile attack.
Some of the uses of magnesium are based on the fact that the metal burns in air with
an intense white flame, and so it is used in fireworks and flares.
Various applications of magnesium compounds include Milk of Magnesia, Mg(OH)
2
,
which is a common remedy for indigestion, and Epsom Salts, MgSO
4
.7H
2
O, which
is used for a variety of health treatments, including as a treatment for constipation, a
purgative, and a soak for sprains and bruises.
Magnesium and calcium are of great biological importance. Magnesium is a
component of chlorophyll but also it is coordinated by many other biologically
important ligands, including ATP (adenosine triphosphate). It is essential for human
health, being responsible for the activity of many enzymes. The recommended adult
human dose is approximately 0.3 g per day and the average adult contains about 25
g of magnesium
Magnesium oxide, MgO, is used as a refractory lining for furnaces. Organo-
magnesium compounds are widely used in organic synthesis as Grignard reagents
4.5.3 Calcium and its compound
The compounds of calcium are much more useful than the element itself.
Calcium oxide (as lime or quicklime) is a major component of mortar and
cement. It is also used in steelmaking and papermaking.
Calcium sulfate dihydrate, CaSO
4
.2 H
2
O is widely used in building
materials, such as plasterboard, and anhydrous CaSO
4
is a common drying
agent.
Calcium carbonate is used in the Solvay process for the production of
sodium carbonate and as the raw material for production of CaO.
Calcium fluoride is insoluble and transparent over a wide range of
wavelengths. It is used to make cells and windows for infrared and
ultraviolet spectrometers.

4.5.4 Strontium and its compound
Strontium is used in pyrotechnics phosphors, and in glasses for the now
rapidly declining market for colour television tubes.
4.5.6 Barium and its compound
Barium compounds, taking advantage of the large number of electrons of
each Ba
2+
ion, are very effective at absorbing X-rays: they are used as
barium meals and barium enemas to investigate the intestinal tract.
Barium is highly toxic, so the insoluble sulfate is used in this application.
Barium carbonate is used in glassmaking and as a flux to aid the flow of
glazes and enamels. It is also used as rat poison.
Barium sulphide (BaS) has been used as a depilatory, to remove
unwanted body hair.
Barium sulphate (BaSO
4
) is pure white, with no absorption in the visible
region of the electromagnetic spectrum, and it is used as a reference
standard in UV-visible spectroscopy. Soon after its discovery, radium was
used to treat malignant tumours; its compounds are still used as
precursors for radon used in similar applications. .
4.6 The anomalous properties of beryllium
The small size of Be
2+
(ionic radius 27 pm) and its consequent high charge
density and polarising power results in the compounds of Be being largely
covalent; the ion is a strong Lewis acid. The coordination number most
commonly observed for this small atom is 4 and the local geometry
tetrahedral.
Some consequences of these properties are:
A significant covalent contribution to the bonding in compounds such as
the beryllium halides BeCl
2
, BeBr
2
, and BeI
2
and the hydride, BeH
2
.
A greater tendency to form complexes, with the formation of molecular
compounds such as Be
4
O(O
2
CCH
3
)
6
.
Hydrolysis (deprotonation) of beryllium salts in aqueous solution, forming
species such as [Be(H
2
O)
3
OH]
+
and acidic solutions. Hydrated beryllium
salts tend to decompose by hydrolysis reactions, where beryllium oxo- or
hydroxo salts are formed, rather than by the simple loss of water.
Beryllium forms many stable organometallic compounds, including
methylberyllium (Be(CH
3
)
2
), ethylberyllium, t-butylberyllium.
Another important general feature of Be is its strong diagonal
relationship with Al:
Both Be and Al form covalent hydrides and halides; the analogous
compounds of the other Group 2 elements are predominantly ionic.
The oxides of Be and Al are amphoteric whereas the oxides of the rest
of the Group 2 elements are basic.
In the presence of excess OH

ions, Be and Al form [Be(OH)


4
]
2
and
[Al(OH)
4
]

, respectively, however, no equivalent chemistry is observed


for Mg.
Both elements form structures based on linked tetrahedra: Be forms
structures built from [BeO
4
]
n-
and [BeX
4
]
n-
tetrahedra (X = halide) and Al
forms numerous aluminates and aluminosilicates containing the [AlO
4
]
n-

unit.