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Ch#5: Group 2 elements HSSC-II By: Sir Amjad (Lecturer Chemistry)

GROUP 2 ELEMENTS- Alkaline Earth metal

Group 2 Elements – Alkaline Earth Metals

Introduction and Uses

Elements from Group 2 are used in a wide range of applications.

• Coloured flames: Group 2 metals produce coloured flames when heated, which makes them
useful in flares and fireworks.
• Magnesium flares: Magnesium in powdered form is often used in flares because it burns with
a bright white light.

Why They Are Called Alkaline Earth Metals

Group 2 elements are called alkaline earth metals because:

• Their oxides and hydroxides are alkaline in nature (water-soluble and basic).
• Their oxides are found in the earth’s crust.

Electronic Structure

• All Group 2 elements have two electrons in their outermost shell (valence shell).
• These two electrons occupy the s subshell.
• General electronic configuration: ns²

Examples:

• Beryllium (Be): 1s² 2s²

• Magnesium (Mg): 1s² 2s² 2p⁶ 3s²
• Calcium (Ca): 1s² 2s² 2p⁶ 3s² 3p⁶ 4s²

General Trends of Physical Properties and Chemical Reactivity

Ion Formation and Reducing Nature

• All Group 2 metals form ionic compounds by donating their two outermost electrons.
• They form 2+ ions and act as reducing agents (get oxidised in reactions).
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Ch#5: Group 2 elements HSSC-II By: Sir Amjad (Lecturer Chemistry)

Trend in Reactivity Down the Group

• Reactivity increases as we go down the group.

• This is explained by ionization energy trends.

Ionization Energy

• Definition: Minimum energy required to remove one mole of electrons from isolated gaseous
atoms or ions.
• Trend: Both first and second ionization energies decrease down the group.
• Reason:
o Increased shielding effect
o Greater distance between nucleus and outermost electrons
• Effect: Easier to lose two electrons → more reactive metals.

Reactions of Group 2 Metals

With Dilute Hydrochloric Acid

• Reaction produces bubbles of hydrogen gas.

• Rate of reaction increases down the group.
• Example:

Mg + 𝟐HCl (aq) → MgCl𝟐 (𝒂𝒒) + H𝟐 (𝒈)

With Oxygen

• Reactivity with oxygen increases down the group.

• Barium (Ba) is so reactive it must be stored in oil to prevent reaction with air.

Trends in Atomic Radius

• Atomic radius increases down the group.

• Reason:
o Extra electron shells are added.
o Increased shielding effect reduces attraction between nucleus and valence electrons.
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Ch#5: Group 2 elements HSSC-II By: Sir Amjad (Lecturer Chemistry)
Trends in Melting Point

• Melting point decreases down the group.

• Reason:
o Outer electrons are farther from the nucleus.
o Weaker attraction between nucleus and delocalised electrons.
o Metallic bonds weaken → lower melting point.

Table: Properties of Group 2 Elements

Element Metallic Radius Atomic Melting Point Density

(nm) Number (°C) (g/cm³)
Beryllium (Be) 0.122 4 1280 1.85
Magnesium (Mg) 0.160 12 650 1.74
Calcium (Ca) 0.197 20 838 1.55
Strontium (Sr) 0.215 38 768 2.66
Barium (Ba) 0.217 56 714 3.56

Trends in Chemical Reactivity with Oxygen, Water, and Dilute Acids

(a) Reaction with Oxygen – Formation of Basic Oxides

• General reaction:
Group 2 metals burn in air (and more rapidly in oxygen) to form white solid oxides.

𝟐Mg (s) + O𝟐 (𝒈) → 𝟐MgO (s)

• Peroxide formation:
Strontium and barium also form peroxides (MO₂).
• Example:
Magnesium ribbon burns with a bright white flame in a Bunsen flame.

Solubility of Oxides

• Beryllium oxide (BeO) and magnesium oxide (MgO) are insoluble in water.
• Solubility of oxides increases down the group, producing soluble hydroxides.
• All oxides are basic, except BeO, which is amphoteric.

Amphoteric Nature of BeO

• Reacts with acids:

BeO (s) + 𝟐HCl (aq) → BeCl𝟐 (𝒂𝒒) + 𝑯𝟐 O

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Ch#5: Group 2 elements HSSC-II By: Sir Amjad (Lecturer Chemistry)
• Reacts with bases:

𝐵𝑒𝑂 (𝑠) + 2𝑁𝑎𝑂𝐻 (𝑎𝑞) → 𝑁𝑎2 𝐵𝑒𝑂2 (𝑎𝑞) + 𝐻2 𝑂 (𝑙)

Reactivity Trend with Oxygen

• Reactivity increases down the group because larger atoms lose outer electrons more easily.
• Barium is so reactive it must be stored under oil.

Covalent Character of BeO

• Be²⁺ has a small ionic radius and high polarizing power.

• It strongly polarises the oxide ion, creating covalent bonds.

Flame Test for Group 2 Metals

The flame colours are due to excitation of 2+ ions.

Metal Flame Colour

Calcium Brick red
Strontium Scarlet / Red
Barium Apple green

Procedure:

1. Clean nichrome wire with concentrated HCl.

2. Dip into the salt sample.
3. Place in a non-luminous Bunsen flame.

(b) Reaction with Water

General Trends

• Beryllium (Be): No reaction due to protective BeO layer.

• Magnesium (Mg): No reaction with cold water; burns in steam:

𝑀𝑔 (𝑠) + 𝐻2 𝑂 (𝑔) → 𝑀𝑔𝑂 (𝑠) + 𝐻2 (𝑔)

• Calcium (Ca): Reacts with cold water:

𝐶𝑎 (𝑠) + 2𝐻2 𝑂 (𝑙) → 𝐶𝑎(𝑂𝐻)2 (𝑎𝑞) + 𝐻2 (𝑔)

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Ch#5: Group 2 elements HSSC-II By: Sir Amjad (Lecturer Chemistry)
o Forms cloudy white suspension of slightly soluble Ca(OH)₂.
o Solution becomes weakly alkaline.
• Reactivity increases down the group – hydrogen gas is produced faster.

General Equation (except Be and Mg):

𝑀 (𝑠) + 2𝐻2 𝑂 (𝑙) → 𝑀(𝑂𝐻)2 (𝑎𝑞/𝑠) + 𝐻2 (𝑔)

(c) Reaction with Dilute Acids

• General redox reaction:

𝑀 (𝑠) + 2𝐻𝐶𝑙 (𝑎𝑞) → 𝑀𝐶𝑙2 (𝑎𝑞) + 𝐻2 (𝑔)

• Reactions become more vigorous and exothermic down the group.

(d) Reaction of Group 2 Oxides with Acids

• Group 2 oxides are basic and neutralise acids to form salts and water.

Examples:

1. Magnesium oxide with sulfuric acid:

𝑀𝑔𝑂 (𝑠) + 𝐻2 𝑆𝑂4 (𝑎𝑞) → 𝑀𝑔𝑆𝑂4 (𝑎𝑞) + 𝐻2 𝑂 (𝑙)

2. Calcium oxide with hydrochloric acid:

𝐶𝑎𝑂 (𝑠) + 2𝐻𝐶𝑙 (𝑎𝑞) → 𝐶𝑎𝐶𝑙2 (𝑎𝑞) + 𝐻2 𝑂 (𝑙)

Uses of Products

• Magnesium sulfate (MgSO₄):

o Short-term relief of constipation.
o Soaking solution for minor sprains, bruises, muscle aches, and joint stiffness.
• Calcium chloride (CaCl₂):
o Solidifying agent in paint production.
o Coagulant in rubber manufacturing.
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Ch#5: Group 2 elements HSSC-II By: Sir Amjad (Lecturer Chemistry)

Comparison of Reactivity of Group 1 and Group 2 Elements

Dependence on Ionization Energy

• Reactivity of metals is inversely related to their ionization energy:

o Lower ionization energy → Higher reactivity
• Alkaline earth metals (Group 2) have higher ionization energies compared to alkali metals
(Group 1).
• Reason:
o Group 2 atoms are smaller in size.
o Stronger nuclear attraction on valence electrons.

Reactivity Trend

• Group 1 elements are more reactive than Group 2 elements in the same period.
• This is due to the lower ionization energy of Group 1 metals compared to Group 2 metals.

Reaction with Water

• Alkali metals (Group 1):

o React very vigorously with water.
o Reaction produces enough heat to ignite the evolved hydrogen gas.
o Example:

𝟐Na (s) + 𝟐H2O (l) → 𝟐NaOH (aq) + H𝟐 (𝒈)

• Alkaline earth metals (Group 2):

o React slowly with water.
o Example:

𝑪𝒂 (𝒔) + 𝟐𝑯𝟐 𝑶 (𝒍) → 𝑪𝒂(𝑶𝑯)𝟐

Reducing Power

• Group 1 metals are stronger reducing agents than Group 2 metals.

• Reason:
o Lower ionization energy makes it easier for Group 1 metals to lose electrons.
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Ch#5: Group 2 elements HSSC-II By: Sir Amjad (Lecturer Chemistry)

Uses of Group 2 Compounds

1. Use of Limestone in Industry

Limestone is mainly calcium carbonate (CaCO₃).

Many forms of limestone are used as building stones.
• Shaped into blocks and fixed with mortar.
• Traditional mortar: lime + sand.
• Modern mortar: cement + sand (cement is made from lime).
Marble: Another form of calcium carbonate, used for expensive tiles and decorative work.

Manufacture of Cement

The first stage in the manufacture of cement is the roasting of limestone in a lime kiln. At high
temperatures in the kiln, calcium carbonate decomposes to form calcium oxide also called lime or
quick lime.

𝑯𝒆𝒂𝒕
𝑪𝒂𝑪𝑶𝟑 → 𝑪𝒂𝑶 (𝒍𝒊𝒎𝒆) + 𝑪𝑶𝟐

The calcium oxide made in the lime kiln goes on to be roasted with clay to make cement.

Cement can be mixed with sand and small pieces of rock to make concrete, the most widely used
building material in the world. Its tensile strength can be improved by letting the concrete set with iron
rods running through it.

2. Use of Slaked Lime in Agriculture

Slaked lime is calcium hydroxide (Ca(OH)₂).

• Purpose: To increase the pH of acidic soils by neutralisation.

• Reaction:

𝑪𝒂(𝑶𝑯)𝟐(𝒔) + 𝟐𝑯+ (𝒂𝒒) → 𝑪𝒂𝟐+ (𝒂𝒒) + 𝟐𝑯𝟐 𝑶(𝒍)

3. Use of Group 2 Compounds in Medicine

(a) Barium Sulphate (BaSO₄)

• Absorbs X-rays strongly → used in diagnosing stomach and intestinal disorders.

• Insoluble, so it is safe and not absorbed into the bloodstream.
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Ch#5: Group 2 elements HSSC-II By: Sir Amjad (Lecturer Chemistry)
(b) Antacids

• Purpose: Neutralise excess stomach acid (HCl) in acid indigestion.

• Common examples:
o Calcium carbonate (CaCO₃) → used in Gaviscon, Rennies.
o Magnesium carbonate (MgCO₃)
o Milk of Magnesia → suspension of magnesium hydroxide (Mg(OH)₂) in water.

Reactions:

1. With calcium carbonate:

𝐶𝑎𝐶𝑂3(𝑠) + 2𝐻𝐶𝑙(𝑎𝑞) → 𝐶𝑎𝐶𝑙2(𝑎𝑞) + 𝐶𝑂2(𝑔) + 𝐻2 𝑂(𝑙)

With magnesium hydroxide:

𝑀𝑔(𝑂𝐻)2(𝑠) + 2𝐻𝐶𝑙(𝑎𝑞) → 𝑀𝑔𝐶𝑙2(𝑎𝑞) + 2𝐻2 𝑂(𝑙)

Thermal Decomposition of Group 2 Carbonates and Nitrates

Definition

Thermal decomposition is the breakdown of a compound into two or more different substances by
the application of heat.

1. Decomposition of Group 2 Carbonates

• When heated, Group 2 carbonates break down into the metal oxide and carbon dioxide gas.

Example:

𝑯𝒆𝒂𝒕
𝑴𝒈𝑪𝑶𝟑 → 𝑴𝒈𝑶 + 𝑪𝑶𝟐(𝒈)

• Trend: The temperature required for decomposition increases down the group.

2. Decomposition of Group 2 Nitrates

• Group 2 nitrates decompose on heating to form:

o Metal oxide
o Nitrogen dioxide (NO₂) – a toxic brown gas
o Oxygen gas (O₂)
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Ch#5: Group 2 elements HSSC-II By: Sir Amjad (Lecturer Chemistry)
Example:

𝑯𝒆𝒂𝒕
𝟐𝑪𝒂(𝑵𝑶𝟑)𝟐(𝒔) → 𝟐𝑪𝒂𝑶(𝒔) + 𝟒𝑵𝑶𝟐(𝒈) + 𝑶𝟐(𝒈)

• Observation: Brown fumes of nitrogen dioxide are seen.

• Trend: Higher temperatures are needed for decomposition down the group.

3. Trend in Thermal Stability

• Thermal stability of Group 2 carbonates and nitrates increases down the group.
• This means:

𝑩𝒂𝑪𝑶𝟑 > 𝑺𝒓𝑪𝑶𝟑 > 𝑪𝒂𝑪𝑶𝟑 > 𝑴𝒈𝑪𝑶𝟑

𝑩𝒂(𝑵𝑶𝟑 )𝟐 > 𝑺𝒓(𝑵𝑶𝟑 )𝟐 > 𝑪𝒂(𝑵𝑶𝟑 )𝟐 > 𝑴𝒈(𝑵𝑶𝟑 )𝟐

• Reason: Larger cations down the group have less polarising power.

4. Enthalpy Change of Decomposition for Group 2 Carbonates

Carbonate Decomposition Temperature (°C) ΔH (kJ mol⁻¹)

Magnesium carbonate 540 +117
Calcium carbonate 900 +176
Strontium carbonate 1280 +238
Barium carbonate 1360 +268

• Interpretation:
o More positive ΔH → more energy needed → greater stability.

5. Explanation – Ion Polarisation Theory

• Carbonate ion (CO₃²⁻) has a large ionic radius, making it easy to polarise.
• Smaller, highly charged cations (like Mg²⁺) have strong polarising power, distorting the
carbonate ion and weakening the C–O bond.
• Trend down the group:
o Cation size increases:

Mg 𝟐+ < Ca𝟐+ < Sr𝟐+ < Ba𝟐+

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Ch#5: Group 2 elements HSSC-II By: Sir Amjad (Lecturer Chemistry)
o Polarising power decreases.
o Less distortion → more stable carbonate → higher decomposition temperature.

Summary of Stability Order:

• Carbonates:

BaCO𝟑 > SrCO𝟑 > CaCO𝟑 > MgCO𝟑

• Nitrates:

𝑩𝒂(𝑵𝑶𝟑 )𝟐 > 𝑺𝒓(𝑵𝑶𝟑 )𝟐 > 𝑪𝒂(𝑵𝑶𝟑 )𝟐 > 𝑴𝒈(𝑵𝑶𝟑 )𝟐

Trends in Solubility of Group 2 Hydroxides and Sulphates

(a) Solubility of Hydroxides of Group 2 Elements

The solubility of hydroxides increases as we move down Group 2, with barium hydroxide being
highly soluble in water.

Order of solubility:

𝑀𝑔(𝑂𝐻)2 < 𝐶𝑎(𝑂𝐻)2 < 𝑆𝑟(𝑂𝐻)2 < 𝐵𝑎(𝑂𝐻)2

Table 5.3 – Solubility in water at 298 K

Group 2 hydroxide Solubility (𝒎𝒐𝒍 / 𝟏𝟎𝟎 𝒈 𝒘𝒂𝒕𝒆𝒓)

Mg(OH)₂ 2 × 10−5
Ca(OH)₂ 1.5 × 10−3
Sr(OH)₂ 3.4 × 10−3
Ba(OH)₂ 1.5 × 10−2

(b) Change in Hydration Enthalpy Down the Group

• Hydration enthalpy is directly proportional to ionic charge and inversely proportional to

ionic size.
• Smaller ions have a more exothermic hydration enthalpy.
• As we go down the group, cation size increases, so hydration enthalpy becomes less
exothermic:

Mg 2+ > Ca2+ > Sr 2+ > Ba2+

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Ch#5: Group 2 elements HSSC-II By: Sir Amjad (Lecturer Chemistry)
• This decrease is small compared to the change in lattice energy, since the anion (OH⁻)
remains the same.

(c) Change in Lattice Energy Down the Group

• Lattice energy is greater for smaller ions (with the same charge).
• As cation size increases, lattice energy decreases in the order:
Mg 2+ > Ca2+ > Sr 2+ > Ba2+
• The lattice energy is also inversely proportional to the sum of the radii of the anion and
cation.
• The decrease in lattice energy down the group is large, mainly due to the increase in cation
size (OH⁻ size remains constant).

(d) Enthalpy of Solution and Solubility

• High solubility is linked to a more negative (exothermic) enthalpy of solution.

• Down the group:
o Lattice energy decreases by a relatively large amount.
o Hydration enthalpy decreases by a smaller amount.
o Result: Enthalpy of solution becomes more negative, increasing solubility.
• A compound is likely soluble if its enthalpy of solution is negative or only slightly positive.

Conclusion:
The greater decrease in lattice energy compared to hydration enthalpy causes Group 2 hydroxides to
become more soluble down the group.

(e) Solubility of Sulphates of Group 2 Elements

The solubility of sulphates decreases as we go down the group, with barium sulphate being almost
insoluble in water.

Order of solubility:

𝑀𝑔𝑆𝑂4 > 𝐶𝑎𝑆𝑂4 > 𝑆𝑟𝑆𝑂4 > 𝐵𝑎𝑆𝑂4

This is due to:

When we move down the group, both the lattice dissociation enthalpy and hydration enthalpy
decrease. The hydration enthalpy decreases more than the lattice dissociation enthalpy. So, the
enthalpy of the solution becomes more endothermic.
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Ch#5: Group 2 elements HSSC-II By: Sir Amjad (Lecturer Chemistry)
Table – Solubility in Water of Group 2 Sulphates at 298 K

𝑪𝒐𝒎𝒑𝒐𝒖𝒏𝒅 𝑺𝒐𝒍𝒖𝒃𝒊𝒍𝒊𝒕𝒚(𝒎𝒐𝒍𝒅𝒎−𝟑 )
𝑀𝑔𝑆𝑂4 1.83
𝐶𝑎𝑆𝑂4 4.66 × 10−2
𝑆𝑟𝑆𝑂4 7.11 × 10−3
𝐵𝑎𝑆𝑂4 9.43 × 10−6

Complexes of the Alkaline Earth Metals

Group 2 elements usually form ionic compounds containing the M²⁺ ion. They are more reactive
towards Group 5 elements and show a greater tendency to form complexes with Lewis bases than
alkali metals. This is because they have a +2 charge and smaller ionic radii, giving them stronger
attraction for electron donors.

Trend in Complex Formation

The tendency to form complexes is greatest for Be²⁺ and decreases sharply down the group as the ionic
radius increases. The high charge-to-radius ratio of Be²⁺ gives it strong polarizing power, allowing it
to distort the electron clouds of ligands and form stable complexes.

Beryllium as a Lewis Acid

Beryllium chemistry is dominated by complex formation. In water, Be²⁺ salts produce acidic solutions
containing the tetrahedral [Be(H₂O)₄]²⁺ ion. The strong polarization of coordinated water molecules
weakens O–H bonds, releasing H⁺ ions and increasing acidity. Heavier Group 2 cations like Ba²⁺ have
lower charge density and form less stable complexes.

Complex Formation in Beryllium and Other Alkaline Earth Metals

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Ch#5: Group 2 elements HSSC-II By: Sir Amjad (Lecturer Chemistry)
In the presence of a strong base, beryllium and its salts form the tetrahedral hydroxo complex
[Be(OH)₄]²⁻, showing that beryllium oxide is amphoteric. Beryllium also forms a very stable
tetrahedral fluoride complex [BeF₄]²⁻ (and related species such as [BeF₃]⁻). These properties are due to
the small size and high charge density of the Be²⁺ ion.
Beryllium halides act as Lewis acids by forming adducts with Lewis bases.

Complexes of Heavier Group 2 Metals

Heavier alkaline earth metals form fewer complexes, usually with a coordination number of six or
higher. Complex formation is most significant for the smaller cations like Mg²⁺ and Ca²⁺. For
example, in aqueous solution, Mg²⁺ exists as the octahedral complex [Mg(H₂O)₆]²⁺, where magnesium
uses one 3s, three 3p, and two 3d orbitals in its outer shell to achieve a coordination number of six.

Extraction and Purification of Group 2 Elements and Compounds

Group 2 elements (alkaline earth metals) include beryllium, magnesium, calcium, strontium,
barium, and radium. Their extraction and purification methods vary depending on the element’s
chemical properties, but generally involve ore preparation, thermal decomposition, reduction, and
electrolysis.

1. Extraction

• Ore Preparation:
Group 2 metals occur in minerals such as carbonates, sulfates, oxides, and silicates. The ores
are mined, crushed, and ground into a fine powder for processing.
• Roasting:
Carbonates decompose on heating to form metal oxides and CO₂.
Example:
𝐻𝑒𝑎𝑡
𝑀𝑔𝐶𝑂3 → 𝑀𝑔𝑂 + 𝐶𝑂2

• Reduction:
o Magnesium: Extracted by electrolysis of molten magnesium oxide.
o Calcium & Strontium: Obtained by reducing their halides with sodium or magnesium.

2. Electrolysis (Purification)

• Pure metals are obtained by electrolyzing molten chlorides or oxides.

• Electrolysis may also be used for final purification.
• Beryllium: Initially produced by reducing beryllium chloride.
• Radium: Extracted from radium chloride through multiple separation steps due to its
radioactivity.

Examples of Extraction and Purification

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Ch#5: Group 2 elements HSSC-II By: Sir Amjad (Lecturer Chemistry)
• Beryllium:
o Extraction: From beryl ore (Be₃Al₂(SiO₃)₆) by acid digestion and solvent extraction.
o Purification: Convert Be(OH)₂ to BeF₂, then reduce with magnesium to obtain high-
purity metal.
• Magnesium:
o Extraction: By electrolysis of molten MgCl₂ (from seawater or brines).
o Purification: Fractional distillation or vacuum distillation.

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