s-BLOCK ELEMENTS

Unit 10 | Groups 1 & 2 | Class 12 NCERT Chemistry

0. s-Block: General Overview

• Groups 1 & 2; last electron enters outermost s-orbital
• Group 1 (Alkali metals): Li, Na, K, Rb, Cs, Fr — valence config ns¹
• Group 2 (Alkaline earth metals): Be, Mg, Ca, Sr, Ba, Ra — valence config ns²
• Called alkali metals because their hydroxides are strongly alkaline
• Called alkaline earth metals because oxides/hydroxides are alkaline and metal oxides found in earth's
crust
• Diagonal relationship: Li resembles Mg; Be resembles Al — due to similar ionic sizes and/or
charge/radius ratios
• Francium: radioactive; longest-lived isotope ²²³Fr, half-life = 21 min
• Radium: rarest — only 10⁻¹⁰% of igneous rocks
• Biological role: Na⁺, K⁺ (monovalent) and Mg²⁺, Ca²⁺ (divalent) present in large proportions in biological
fluids; maintain ion balance and conduct nerve impulses

1. Group 1 — Alkali Metals

1.1 Electronic Configuration

• ns¹ outside noble gas core — one loosely held valence electron
• Most electropositive metals; readily lose e⁻ → M⁺ ions; never found free in nature

Element Symbol Electronic Config

Lithium Li [He] 2s¹
Sodium Na [Ne] 3s¹
Potassium K [Ar] 4s¹
Rubidium Rb [Kr] 5s¹
Caesium Cs [Xe] 6s¹
Francium Fr [Rn] 7s¹

1.2 Atomic and Ionic Radii

• Largest atoms in their respective periods
• Atomic and ionic radii increase down group: Li → Cs
• M⁺ ions smaller than parent atoms (electron removed → nuclear charge dominates)

1.3 Ionization Enthalpy

• Considerably low; decreases down the group (Li → Cs)
• Reason: increasing size outweighs increasing nuclear charge; outermost e⁻ well screened from nucleus
1.4 Hydration Enthalpy
• Decreases with increase in ionic size
Li⁺ > Na⁺ > K⁺ > Rb⁺ > Cs⁺
• Li⁺: maximum hydration degree → lithium salts mostly hydrated, e.g., LiCl·2H₂O

1.5 Physical Properties

• Silvery white, soft, light metals
• Density low (large size); generally increases Li → Cs — exception: K is lighter than Na
• Low MP and BP — weak metallic bonding (only 1 valence electron)
• Flame colours (visible emission when excited e⁻ returns to ground state):

Metal Colour Wavelength (nm)

Li Crimson red 670.8
Na Yellow 589.2
K Violet 766.5
Rb Red violet 780.0
Cs Blue 455.5
• Used in flame photometry and atomic absorption spectroscopy
• Photoelectric effect: Cs and K used as electrodes in photoelectric cells (absorbed light → atom loses
electron)

1.6 Physical Data — Group 1

Property Li Na K Rb Cs
Atomic no. 3 11 19 37 55
Atomic mass (g/mol) 6.94 22.99 39.10 85.47 132.91
IE (kJ/mol) 520 496 419 403 376
Hydration ΔH (kJ/mol) -506 -406 -330 -310 -276
Metallic radius (pm) 152 186 227 248 265
Ionic radius M⁺ (pm) 76 102 138 152 167
MP (K) 454 371 336 312 302
BP (K) 1615 1156 1032 961 944
Density (g/cm³) 0.53 0.97 0.86 1.53 1.90
E° (V) for M⁺/M -3.04 -2.714 -2.925 -2.930 -2.927

1.7 Chemical Properties

• Highly reactive (large size + low IE); reactivity ↑ down group

(i) Reactivity towards Air

• Tarnish in dry air: oxide forms → reacts with moisture → hydroxide
• On burning in O₂:
4Li + O₂ → 2Li₂O (monoxide)
 2Na + O₂ → Na₂O₂ (peroxide)
M + O₂ → MO₂ (superoxide; M = K, Rb, Cs)
• All oxides: oxidation state of metal = +1
• Superoxide O₂⁻: stable only with large cations (K, Rb, Cs)
• Li special: also reacts directly with N₂ of air → Li₃N (nitride)
• Storage: kept in kerosene oil due to high reactivity

(ii) Reactivity towards Water

2M + 2H₂O → 2M⁺ + 2OH⁻ + H₂ (M = alkali metal)
• Li: most negative E° (−3.04 V) but reacts LESS vigorously than Na — because of very small size and
very high hydration energy of Li⁺ which slows the reaction kinetics
• Na least negative E° among group, yet more vigorous with water than Li
• Other metals react explosively with water
• Also react with proton donors: alcohol, gaseous NH₃, alkynes

(iii) Reactivity towards Dihydrogen

2M + H₂ → 2M⁺H⁻ [~673K; Li at 1073K]
• All alkali metal hydrides are ionic solids with high MP

(iv) Reactivity towards Halogens

• Form ionic halides M⁺X⁻ (vigorous reaction)
• Exception: Li halides are somewhat covalent — Li⁺ is very small → high polarising power → distorts
electron cloud of large halide ions
• Most covalent: LiI (largest anion, most easily distorted)

(v) Reducing Nature

• Strong reducing agents; order: Li > Na > K > Rb > Cs (Li most powerful, Na least)
• Reducing power determined by overall process:
◦ M(s) → M(g) sublimation enthalpy
◦ M(g) → M⁺(g) + e⁻ ionization enthalpy
◦ M⁺(g) + H₂O → M⁺(aq) hydration enthalpy
• Li: highest hydration enthalpy (small ionic size) → most negative E° → highest reducing power despite
high IE

(vi) Solutions in Liquid Ammonia

• Dissolve in liquid NH₃ → deep blue solution (conducting)
M + (x+y)NH₃ → [M(NH₃)ₓ]⁺ + [e(NH₃)ᵧ]⁻
• Blue colour: due to ammoniated electron — absorbs visible light energy
• Solutions are paramagnetic
• On standing → liberates H₂ (slowly):
M⁺(am) + e⁻ + NH₃(l) → MNH₂(am) + ½H₂(g)
• Concentrated solution: blue → bronze colour; becomes diamagnetic
1.8 Uses of Alkali Metals
Metal Uses
Lithium Alloys: with Pb (white metal bearings), with Al (aircraft parts), with Mg (armour plates);
thermonuclear reactions; electrochemical cells
Sodium Na/Pb alloy for anti-knock additives (PbEt₄, PbMe₄ — now discontinued); liquid Na as
coolant in fast breeder nuclear reactors
Potassium Vital biological role; KCl as fertilizer; KOH in manufacture of soft soap; excellent CO₂
absorbent
Caesium Photoelectric cells

2. General Characteristics of Compounds of Alkali Metals

• All common compounds: generally ionic

2.1 Oxides and Hydroxides

• Formation products on combustion in excess air:
◦ Li → Li₂O (monoxide) + some Li₂O₂ (peroxide)
◦ Na → Na₂O₂ (peroxide) + some NaO₂ (superoxide)
◦ K, Rb, Cs → MO₂ (superoxide)
• Pure M₂O, M₂O₂, MO₂ can be prepared under appropriate conditions
• Increasing stability of peroxide/superoxide down group: large anions stabilised by large cations
(lattice energy effects)
• Hydrolysis of oxides:
M₂O + H₂O → 2M⁺ + 2OH⁻
M₂O₂ + 2H₂O → 2M⁺ + 2OH⁻ + H₂O₂
2MO₂ + 2H₂O → 2M⁺ + 2OH⁻ + H₂O₂ + O₂
• Colours: oxides and peroxides colourless when pure; superoxides yellow or orange; superoxides also
paramagnetic
• Na₂O₂: widely used oxidising agent in inorganic chemistry
• KO₂ paramagnetic: O₂⁻ ion has one unpaired electron in π*2p molecular orbital
• Hydroxides: white crystalline solids; strongest bases; freely soluble in water with evolution of heat
(intense hydration)

2.2 Halides
• MX (X = F, Cl, Br, I): all high melting, colourless crystalline solids
• Preparation: reaction of oxide/hydroxide/carbonate with aqueous HX
• ΔfH° for fluorides: becomes less negative going down group; reverse for Cl, Br, I halides
• For given metal: ΔfH° fluoride > chloride > bromide > iodide (less negative fluoride to
iodide)
• MP/BP trend: fluoride > chloride > bromide > iodide
• All soluble in water; exceptions: LiF (low solubility — high lattice enthalpy); CsI (low solubility — small
hydration enthalpy of Cs⁺ and I⁻)
• Other Li halides: soluble in ethanol, acetone, ethylacetate; LiCl also soluble in pyridine

2.3 Salts of Oxo-Acids

• Oxo-acids: acidic proton on hydroxyl group with an oxo group on same atom e.g., H₂CO₃, H₂SO₄
 • Alkali metals form salts with all oxo-acids; generally water-soluble and thermally stable
• Carbonates M₂CO₃ and hydrogencarbonates MHCO₃: highly stable to heat
• Stability ↑ down group (electropositive character ↑)
• Li₂CO₃: not very stable to heat — small Li⁺ polarises large CO₃²⁻ → forms more stable Li₂O + CO₂
• Li HCO₃: does not exist as a solid

3. Anomalous Properties of Lithium

• Reasons: (i) exceptionally small atomic/ionic size; (ii) high polarising power (charge/radius ratio)
• Increased covalent character of Li compounds → soluble in organic solvents

3.1 Differences: Li vs. Other Alkali Metals

• Li is much harder; higher MP and BP than other alkali metals
• Li: least reactive but strongest reducing agent in group
• On combustion in air: forms Li₂O (monoxide) + Li₃N (nitride) — unlike others
• LiCl is deliquescent; crystallises as LiCl·2H₂O — other alkali chlorides do not form hydrates
• LiHCO₃ not obtained in solid form; all other alkali metals form solid hydrogencarbonates
• Li forms no ethynide on reaction with ethyne (unlike others)
• LiNO₃ on heating:
4LiNO₃ → 2Li₂O + 4NO₂ + O₂ (gives oxide)
• NaNO₃ on heating:
2NaNO₃ → 2NaNO₂ + O₂ (gives nitrite)
• LiF and Li₂O comparatively much less soluble in water than corresponding compounds of
other alkali metals

3.2 Similarities: Li and Mg (Diagonal Relationship)

• Reason: similar sizes — atomic: Li = 152 pm, Mg = 160 pm; ionic: Li⁺ = 76 pm, Mg²⁺ = 72 pm
• Both harder and lighter than other elements in respective groups
• Both react slowly with water; oxides/hydroxides less soluble; hydroxides decompose on
heating; both form nitrides (Li₃N, Mg₃N₂) directly with N₂
• Li₂O and MgO do not combine with excess O₂ to form superoxide
• Li₂CO₃ and MgCO₃ decompose easily on heating → oxide + CO₂; solid hydrogencarbonates
not formed by either
• Both LiCl and MgCl₂ soluble in ethanol
• Both LiCl and MgCl₂ deliquescent; crystallise from aqueous solution as hydrates: LiCl·2H₂O
and MgCl₂·8H₂O

4. Important Compounds of Sodium

4.1 Sodium Carbonate (Washing Soda) — Na₂CO₃·10H₂O

Solvay Process
• Exploits low solubility of NaHCO₃ — gets precipitated and separated
2NH₃ + H₂O + CO₂ → (NH₄)₂CO₃
 (NH₄)₂CO₃ + H₂O + CO₂ → 2NH₄HCO₃
NH₄HCO₃ + NaCl → NH₄Cl + NaHCO₃↓ (NaHCO₃ precipitates)
2NaHCO₃ →(heat) Na₂CO₃ + CO₂ + H₂O
• NH₃ recovery:
2NH₄Cl + Ca(OH)₂ → 2NH₃ + CaCl₂ + H₂O
• By-product: CaCl₂
• Cannot make K₂CO₃ by Solvay process: KHCO₃ too soluble — not precipitated by NH₄HCO₃ addition

Properties
• White crystalline solid; exists as decahydrate Na₂CO₃·10H₂O (washing soda)
• Readily soluble in water
Na₂CO₃·10H₂O →(375K) Na₂CO₃·H₂O + 9H₂O
Na₂CO₃·H₂O →(>373K) Na₂CO₃ + H₂O (soda ash — white anhydrous powder)
• Alkaline hydrolysis in water:
CO₃²⁻ + H₂O → HCO₃⁻ + OH⁻

Uses of Na₂CO₃
• Water softening, laundering and cleaning
• Manufacture of glass, soap, borax and caustic soda
• Paper, paints and textile industries
• Important laboratory reagent (qualitative and quantitative analysis)

4.2 Sodium Chloride — NaCl

• Most abundant source: sea water (2.7–2.9% by mass)
• In India: obtained by solar evaporation of sea water; ~50 lakh tons produced annually
• Impurities in crude salt: Na₂SO₄, CaSO₄, CaCl₂, MgCl₂
• CaCl₂ and MgCl₂ are impurities because they are deliquescent
• Purification: dissolve in min water, filter insoluble impurities, saturate with HCl gas → pure NaCl crystals
separate (Ca/Mg chlorides more soluble, stay in solution)
• Properties: MP = 1081 K; solubility = 36.0 g in 100 g water at 273 K; solubility nearly constant with
temperature
• Uses: table salt; preparation of Na₂O₂, NaOH and Na₂CO₃

4.3 Sodium Hydroxide (Caustic Soda) — NaOH

Castner-Kellner Process
• Electrolysis of brine solution in Castner-Kellner cell
• Mercury cathode + carbon anode
Cathode: Na⁺ + e⁻ →(Hg) Na-amalgam
Anode: Cl⁻ → ½Cl₂ + e⁻
2Na-amalgam + 2H₂O → 2NaOH + 2Hg + H₂

Properties
• White, translucent solid; MP = 591 K
• Readily soluble in water → strong alkaline solution
 • Crystals are deliquescent
• Reacts with atmospheric CO₂: NaOH + CO₂ → Na₂CO₃

Uses of NaOH
• Manufacture of soap, paper, artificial silk, various chemicals
• Petroleum refining; purification of bauxite
• Textile industries — mercerising cotton fabrics
• Preparation of pure fats and oils
• Laboratory reagent

4.4 Sodium Hydrogencarbonate (Baking Soda) — NaHCO₃

• Preparation: saturate Na₂CO₃ solution with CO₂ → NaHCO₃ (less soluble) separates as white
crystalline powder
Na₂CO₃ + H₂O + CO₂ → 2NaHCO₃
• Baking soda name: decomposes on heating → CO₂ bubbles → makes cakes/pastries light and fluffy
• Mild antiseptic for skin infections
• Used in fire extinguishers

5. Biological Importance of Sodium and Potassium

• 70 kg man: ~90 g Na; ~170 g K; cf. only 5 g Fe and 0.06 g Cu

Sodium (Na⁺)
• Location: outside cells — blood plasma and interstitial fluid
• Functions: nerve signal transmission; regulating water flow across cell membranes; transport
of sugars and amino acids into cells

Potassium (K⁺)
• Location: inside cells — most abundant intracellular cation
• Functions: activates many enzymes; participates in oxidation of glucose → ATP; nerve signal
transmission (with Na)

Na-K Pump
• Na⁺ and K⁺ differ in ability to penetrate cell membranes, transport mechanisms and enzyme
activation
• Blood plasma: Na⁺ = 143 mmol/L; K⁺ = 5 mmol/L
• Red blood cells: Na⁺ = 10 mmol/L; K⁺ = 105 mmol/L
• Sodium-potassium pump: discriminatory mechanism across cell membranes; consumes >⅓
of ATP in resting animal; ~15 kg ATP per 24 h in resting human

6. Group 2 — Alkaline Earth Metals

6.1 Electronic Configuration

• ns² in valence shell; general config: [noble gas] ns²
 • Compounds predominantly ionic (like alkali metals)

Element Symbol Electronic Config

Beryllium Be [He] 2s²
Magnesium Mg [Ne] 3s²
Calcium Ca [Ar] 4s²
Strontium Sr [Kr] 5s²
Barium Ba [Xe] 6s²
Radium Ra [Rn] 7s²

6.2 Atomic and Ionic Radii

• Smaller than corresponding alkali metals (increased nuclear charge in same period)
• Within group: radii increase with increasing atomic number

6.3 Ionization Enthalpies

• Low IE (large atoms) but higher than corresponding Group 1 metals (smaller size)
• IE decreases down the group (size increases)
• IE₁ of Group 2 > IE₁ of Group 1 (smaller size)
• IE₂ of Group 2 < IE₂ of Group 1 (second IE of alkali metal requires removal from noble gas core)

6.4 Hydration Enthalpies

• Decrease with increase in ionic size (like Group 1)
Be²⁺ > Mg²⁺ > Ca²⁺ > Sr²⁺ > Ba²⁺
• Group 2 hydration enthalpies > Group 1 (higher charge of M²⁺)
• Group 2 compounds more extensively hydrated than Group 1: e.g., MgCl₂·6H₂O, CaCl₂·6H₂O (vs. NaCl,
KCl — no hydrates)

6.5 Physical Properties

• Silvery white, lustrous; harder than alkali metals
• Be and Mg appear somewhat greyish
• MP and BP higher than corresponding alkali metals (smaller size)
• Strongly electropositive (↑ down group Be → Ba)
• Flame colours: Ca = brick red; Sr = crimson; Ba = apple green
• Be and Mg: electrons too strongly bound → NOT excited by flame → NO colour
• Flame test for Ca, Sr, Ba: used in qualitative analysis and flame photometry
• High electrical and thermal conductivity (typical metallic properties)

6.6 Physical Data — Group 2

Property Be Mg Ca Sr Ba
Atomic no. 4 12 20 38 56
Atomic mass (g/mol) 9.01 24.31 40.08 87.62 137.33
 IE₁ (kJ/mol) 899 737 590 549 503
IE₂ (kJ/mol) 1757 1450 1145 1064 965
Hydration ΔH (kJ/mol) -2494 -1921 -1577 -1443 -1305
Metallic radius (pm) 111 160 197 215 222
Ionic radius M²⁺ (pm) 31 72 100 118 135
MP (K) 1560 924 1124 1062 1002
BP (K) 2745 1363 1767 1655 2078
Density (g/cm³) 1.84 1.74 1.55 2.63 3.59
E° (V) for M²⁺/M -1.97 -2.36 -2.84 -2.89 -2.92

6.7 Chemical Properties

• Less reactive than alkali metals; reactivity ↑ down group

(i) Reactivity towards Air and Water

• Be and Mg: kinetically inert (oxide film on surface prevents further reaction)
• Powdered Be: burns brilliantly on ignition → BeO + Be₃N₂
• Mg: burns with dazzling brilliance in air → MgO + Mg₃N₂
• Ca, Sr, Ba: readily attacked by air → oxide + nitride; react vigorously even with cold water → M(OH)₂

(ii) Reactivity towards Halogens

M + X₂ → MX₂ [elevated temperature; X = F, Cl, Br, I]
• BeF₂: best prepared by thermal decomposition of (NH₄)₂BeF₄
BeO + C + Cl₂ →(600-800K) BeCl₂ + CO

(iii) Reactivity towards Hydrogen

• All elements except Be combine with H₂ on heating → MH₂
• BeH₂ prepared separately:
2BeCl₂ + LiAlH₄ → 2BeH₂ + LiCl + AlCl₃

(iv) Reactivity towards Acids

M + 2HCl → MCl₂ + H₂

(v) Reducing Nature

• Strong reducing agents; large negative E° values
• Reducing power < corresponding alkali metals
• Be exception: less negative E° but reducing nature due to large hydration energy (small Be²⁺) and large
atomisation enthalpy

(vi) Solutions in Liquid Ammonia

M + (x+y)NH₃ → [M(NH₃)ₓ]²⁺ + 2[e(NH₃)ᵧ]⁻
• Deep blue-black solutions; [M(NH₃)₆]²⁺ ammoniates recoverable
6.8 Uses of Alkaline Earth Metals
Metal / Compound Use(s)
Beryllium Alloys; Cu-Be alloys → high strength springs; X-ray tube windows
Magnesium Alloys with Al, Zn, Mn, Sn; Mg-Al alloys in aircraft; flash powders/bulbs; incendiary
bombs; milk of magnesia (antacid); MgCO₃ in toothpaste
Calcium Extraction of metals from oxides hard to reduce with C; removing air from vacuum
tubes (reacts with O₂ and N₂)
Barium Removing air from vacuum tubes
Radium Radiotherapy (e.g., cancer treatment)

7. General Characteristics of Compounds of Alkaline Earth Metals

• Predominant OS: +2 (M²⁺)
• Predominantly ionic but less ionic than corresponding Group 1 compounds (higher charge, smaller size)
• Be and Mg compounds more covalent than heavier group members (Ca, Sr, Ba)

(i) Oxides and Hydroxides

• Burn in O₂ → MO (monoxide); except BeO: rock-salt structure for others
• BeO: essentially covalent; amphoteric
• High formation enthalpies → very stable to heat
• All MO except BeO: basic; react with water to form hydroxides:
MO + H₂O → M(OH)₂
• Solubility, thermal stability, basic character of M(OH)₂: ↑ down group Mg(OH)₂ → Ba(OH)₂
• Group 2 hydroxides less basic and less stable than Group 1 hydroxides
• Be(OH)₂: amphoteric:
Be(OH)₂ + 2OH⁻ → [Be(OH)₄]²⁻ (beryllate ion)
Be(OH)₂ + 2HCl + 2H₂O → [Be(OH)₄]Cl₂

(ii) Halides
• Be halides: essentially covalent; soluble in organic solvents; chain structure in solid state (Cl-bridged)
• BeCl₂ in vapour: chloro-bridged dimer; dissociates to linear monomer at ~1200 K
• All other group 2 halides: ionic
• Tendency to form halide hydrates ↓ down group: MgCl₂·8H₂O, CaCl₂·6H₂O, SrCl₂·6H₂O,
BaCl₂·2H₂O
• Dehydration of Ca, Sr, Ba hydrated chlorides/bromides/iodides: achievable on heating
• Be and Mg hydrated halides on heating: suffer hydrolysis (not simple dehydration)
• Fluorides: less soluble than chlorides (high lattice energies)

(iii) Salts of Oxoacids — Carbonates

• All insoluble in water; precipitated by Na₂CO₃ or (NH₄)₂CO₃ addition
• Solubility of carbonates ↓ down group (as cationic size ↑)
• All decompose on heating → MO + CO₂
• BeCO₃: unstable; kept only in CO₂ atmosphere
• Thermal stability ↑ with cationic size (→ BaCO₃ most stable)
(iii) Salts of Oxoacids — Sulphates
• All white solids; stable to heat
• BeSO₄ and MgSO₄: readily soluble in water (high hydration enthalpies of Be²⁺/Mg²⁺ overcome lattice
enthalpy)
• Solubility ↓ from CaSO₄ to BaSO₄ (hydration enthalpy decreases while lattice enthalpy stays
~constant)

(iii) Salts of Oxoacids — Nitrates

• Prepared by dissolving carbonates in dilute HNO₃
• Mg(NO₃)₂ crystallises with 6H₂O; Ba(NO₃)₂ crystallises anhydrous (decreasing hydration down group)
• Decompose on heating → oxide (like Li nitrate):
2M(NO₃)₂ → 2MO + 4NO₂ + O₂ [M = Be, Mg, Ca, Sr, Ba]

8. Anomalous Behaviour of Beryllium

8.1 Why Be is Anomalous

• Exceptionally small atomic/ionic size; high IE; forms largely covalent compounds; easily
hydrolysed
• Max coordination number = 4 (only 4 orbitals in valence shell — no d orbitals); other group
2 elements can have CN = 6 using d orbitals
• BeO and Be(OH)₂ are amphoteric; other group 2 oxides/hydroxides are basic

8.2 Diagonal Relationship: Be and Al

• Reason: ionic radius of Be²⁺ ≈ 31 pm; charge/radius ratio nearly same as Al³⁺
• Both not readily attacked by acids (protective oxide film)
• Both hydroxides dissolve in excess alkali:
Be(OH)₂ + 2OH⁻ → [Be(OH)₄]²⁻ (beryllate)
Al(OH)₃ + OH⁻ → [Al(OH)₄]⁻ (aluminate)
• Both chlorides have Cl⁻-bridged structure in vapour phase; soluble in organic solvents; strong
Lewis acids; used as Friedel-Craft catalysts
• Both form stable complexes: BeF₄²⁻ and AlF₆³⁻

9. Important Compounds of Calcium

9.1 Calcium Oxide (Quick Lime) — CaO

Preparation
CaCO₃ →(1070-1270K, rotary kiln) CaO + CO₂
• CO₂ removed immediately to drive reaction to completion

Properties
• White amorphous solid; MP = 2870 K
• Absorbs moisture and CO₂ from atmosphere
 CaO + H₂O → Ca(OH)₂ (slaking of lime)
CaO + CO₂ → CaCO₃
• Slaking: limited water breaks lump of lime; quick lime + soda → solid sodalime
• Basic oxide — reacts with acidic oxides at high T:
CaO + SiO₂ → CaSiO₃
6CaO + P₄O₁₀ → 2Ca₃(PO₄)₂

Uses
• Primary material for cement; cheapest form of alkali
• Manufacture of Na₂CO₃ from caustic soda
• Purification of sugar; manufacture of dyestuffs

9.2 Calcium Hydroxide (Slaked Lime) — Ca(OH)₂

Preparation
CaO + H₂O → Ca(OH)₂

Properties
• White amorphous powder; sparingly soluble in water
• Lime water: aqueous solution; milk of lime: suspension in water
• CO₂ test:
Ca(OH)₂ + CO₂ → CaCO₃↓ + H₂O (turns lime water milky)
CaCO₃ + CO₂ + H₂O → Ca(HCO₃)₂ (excess CO₂ dissolves precipitate)
• With Cl₂ → bleaching powder:
2Ca(OH)₂ + 2Cl₂ → CaCl₂ + Ca(OCl)₂ + 2H₂O

Uses
• Preparation of mortar (building material)
• Whitewash (disinfectant nature)
• Glass making; tanning; bleaching powder; purification of sugar

9.3 Calcium Carbonate — CaCO₃

Occurrence and Preparation
• Occurs as limestone, chalk, marble
Ca(OH)₂ + CO₂ → CaCO₃ + H₂O
CaCl₂ + Na₂CO₃ → CaCO₃↓ + 2NaCl
• Excess CO₂ must be avoided → soluble Ca(HCO₃)₂ forms

Properties
• White fluffy powder; almost insoluble in water
CaCO₃ →(1200K) CaO + CO₂
CaCO₃ + 2HCl → CaCl₂ + H₂O + CO₂
CaCO₃ + H₂SO₄ → CaSO₄ + H₂O + CO₂

Uses
• Building material (marble); manufacture of quick lime
• Flux in extraction of metals (with MgCO₃)
• High quality paper manufacture; antacid; mild abrasive in toothpaste; chewing gum constituent; filler in
cosmetics
9.4 Calcium Sulphate (Plaster of Paris) — CaSO₄·½H₂O
Preparation
• Hemihydrate of calcium sulphate (gypsum heated to 393 K):
2CaSO₄·2H₂O →(393K) 2(CaSO₄)·H₂O + 3H₂O
• Above 393 K: anhydrous CaSO₄ = 'dead burnt plaster'

Properties
• Sets with water — plastic mass → hard solid in 5-15 min (hydration and rearrangement of molecules)

Uses
• Building industry and plasters
• Immobilising bone fractures/sprains
• Dentistry; ornamental work; casts of statues and busts

9.5 Cement (Portland Cement)

• First introduced: England, 1824 by Joseph Aspdin; named after Isle of Portland limestone
• Definition: product obtained by combining CaO-rich material with clay (SiO₂ + Al₂O₃ +
Fe₂O₃ + MgO oxides)
Average Composition of Portland Cement
Component Percentage
CaO 50-60%
SiO₂ 20-25%
Al₂O₃ 5-10%
MgO 2-3%
Fe₂O₃ 1-2%
SO₃ 1-2%

• Quality ratios: SiO₂/Al₂O₃ = 2.5–4; CaO/(SiO₂ + Al₂O₃ + Fe₂O₃) ≈ 2

Manufacture
• Raw materials: limestone + clay → strongly heated together → fuse → cement clinker
• Clinker + 2-3% gypsum (CaSO₄·2H₂O) by weight → ground to fine powder = cement
• Gypsum purpose: slows setting process so cement hardens sufficiently
Important Ingredients
Compound Formula Content
Dicalcium silicate Ca₂SiO₄ 26%
Tricalcium silicate Ca₃SiO₅ 51%
Tricalcium aluminate Ca₃Al₂O₆ 11%

• Setting: hydration of constituent molecules and their rearrangement → hard mass

• Uses: concrete and reinforced concrete; plastering; construction of bridges, dams, buildings
10. Biological Importance of Magnesium and Calcium
• Adult body: ~25 g Mg; ~1200 g Ca; cf. 5 g Fe and 0.06 g Cu
• Daily requirement: 200–300 mg

Magnesium
• All enzymes that utilise ATP in phosphate transfer require Mg as cofactor
• Chlorophyll: main pigment for light absorption in plants; contains Mg

Calcium
• ~99% of body Ca in bones and teeth
• Important in: neuromuscular function; interneuronal transmission; cell membrane integrity;
blood coagulation
• Ca concentration in plasma: regulated at ~100 mg/L
• Regulated by: calcitonin and parathyroid hormone
• Bone continuously solubilised and redeposited (~400 mg/day in man); all passes through
plasma

11. Key Comparisons at a Glance

11.1 Alkali Metals vs. Alkaline Earth Metals

Property Group 1 (Alkali) Group 2 (Alk. Earth)
Valence config ns¹ ns²
Ion formed M⁺ M²⁺
IE₁ Lower (→ more reactive) Higher than Gp 1
IE₂ Very high (noble gas core) Smaller than Gp 1 IE₂
Hydration enthalpy Lower Higher (more hydrated salts)
Reactivity with water More vigorous Less vigorous (Be, Mg passive)
Oxide type Li: oxide; Na: peroxide; K,Rb,Cs: All: monoxide MO
superoxide
Hydroxide basicity Strongest bases Less basic than Gp 1
Carbonate stability M₂CO₃ highly stable; Li₂CO₃ less Decreases up group; BaCO₃ most
so stable
Halide covalency Li halides somewhat covalent (esp. Be halides covalent; others ionic
LiI)
Flame test Li:crimson; Na:yellow; K:violet; Ca:brick red; Sr:crimson; Ba:apple
Rb:red; Cs:blue green
Diagonal relation Li ↔ Mg Be ↔ Al

11.2 All Key Reactions Summary

Group 1 — Alkali Metals
4Li + O₂ → 2Li₂O
2Na + O₂ → Na₂O₂
 M + O₂ → MO₂ (M = K, Rb, Cs)
2M + 2H₂O → 2MOH + H₂
2M + H₂ → 2MH (~673K)
4LiNO₃ → 2Li₂O + 4NO₂ + O₂
2NaNO₃ → 2NaNO₂ + O₂
M₂O + H₂O → 2M⁺ + 2OH⁻
M₂O₂ + 2H₂O → 2M⁺ + 2OH⁻ + H₂O₂
2MO₂ + 2H₂O → 2M⁺ + 2OH⁻ + H₂O₂ + O₂

Group 2 — Alkaline Earth Metals

M + X₂ → MX₂
2BeCl₂ + LiAlH₄ → 2BeH₂ + LiCl + AlCl₃
BeO + C + Cl₂ →(600-800K) BeCl₂ + CO
Be(OH)₂ + 2OH⁻ → [Be(OH)₄]²⁻
2M(NO₃)₂ → 2MO + 4NO₂ + O₂ (Be, Mg, Ca, Sr, Ba)

Sodium Compounds
NH₄HCO₃ + NaCl → NH₄Cl + NaHCO₃↓ (Solvay)
2NaHCO₃ →(heat) Na₂CO₃ + CO₂ + H₂O
2NH₄Cl + Ca(OH)₂ → 2NH₃ + CaCl₂ + H₂O
Na₂CO₃ + H₂O + CO₂ → 2NaHCO₃
CO₃²⁻ + H₂O → HCO₃⁻ + OH⁻ (hydrolysis)

Calcium Compounds
CaCO₃ →(1070-1270K) CaO + CO₂
CaO + H₂O → Ca(OH)₂
CaO + SiO₂ → CaSiO₃
6CaO + P₄O₁₀ → 2Ca₃(PO₄)₂
Ca(OH)₂ + CO₂ → CaCO₃ + H₂O
CaCO₃ + CO₂ + H₂O → Ca(HCO₃)₂
2Ca(OH)₂ + 2Cl₂ → CaCl₂ + Ca(OCl)₂ + 2H₂O (bleaching powder)
CaCO₃ →(1200K) CaO + CO₂
2(CaSO₄·2H₂O) →(393K) 2(CaSO₄)·H₂O + 3H₂O (Plaster of Paris)

NCERT Class 12 Chemistry — Unit 10 | s-Block Elements (Groups 1 & 2)