Part 2 · Chapter 16

The s-Block Elements

The reactive metals of Groups 1 and 2 — soft, light and eager to lose electrons, colouring flames and powering everything from washing soda to the cells of your body

Fundamentals of Chemistry Prof. Mithun Mondal Reading time ≈ 50 min
i What you'll learn
  • The general character of the s-block — Group 1 alkali metals and Group 2 alkaline earth metals.
  • The periodic trends in size, ionization enthalpy, reactivity and reducing power.
  • Reactions with oxygen (oxide, peroxide, superoxide), water, hydrogen and halogens, and the flame colours.
  • The anomalies of lithium and beryllium, and their diagonal relationships.
  • Key sodium compounds and the Solvay process; key calcium compounds and plaster of Paris.
  • The biological roles of \(\ce{Na+},\ \ce{K+},\ \ce{Mg^2+}\) and \(\ce{Ca^2+}\).
Section 16-1

The s-Block at a Glance

The s-block holds the two leftmost groups, where the outermost electron occupies an \(s\) orbital. Group 1 (\(\ce{Li, Na, K, Rb, Cs, Fr}\)) — the alkali metals — have \(ns^1\); Group 2 (\(\ce{Be, Mg, Ca, Sr, Ba, Ra}\)) — the alkaline earth metals — have \(ns^2\). All are reactive metals that readily lose their outer electrons to reach a noble-gas core, giving fixed oxidation states of \(+1\) and \(+2\).

FeatureGroup 1 (alkali)Group 2 (alkaline earth)
Valence config\(ns^1\)\(ns^2\)
Oxidation state\(+1\)\(+2\)
Hardness / densityvery soft, low densityharder, denser
Melting pointlowhigher than Group 1
Reactivityextremely highhigh, but less than Group 1
Section 16-2

Group 1: The Alkali Metals

The alkali metals are the most electropositive elements: large atoms with a single, loosely held electron and the lowest ionization enthalpies in their periods. Going down the group, atoms grow, ionization enthalpy falls, and reactivity rises. They are soft enough to cut with a knife and so light that lithium, sodium and potassium float on water.

Property (down the group)TrendReason
Atomic / ionic radiusincreasesnew shell each period
Ionization enthalpydecreasesouter e⁻ farther, more shielded
Metallic / reducing characterincreaseseasier to lose the electron
Melting & boiling pointdecreasesweaker metallic bonding
Hydration enthalpydecreaseslarger ions hydrate less
🔥
Flame colours (a classic identification)
Li → crimson · Na → golden yellow · K → lilac · Rb → red-violet · Cs → blue

The loosely held electron is easily excited by a flame and emits a characteristic colour as it falls back. This is the basis of the flame test and of sodium-vapour street lamps.

The reducing-power twist. Lithium has the highest ionization enthalpy of the group, yet it is the strongest reducing agent in aqueous solution (most negative \(E^\circ\)). The reason is its very high hydration enthalpy: the tiny \(\ce{Li+}\) ion is stabilised so strongly by water that the overall energy of \(\ce{Li -> Li+(aq)}\) is the most favourable.
Section 16-3

Reactions of the Alkali Metals

Their lone valence electron makes the alkali metals react vigorously with almost everything. The reaction with oxygen is especially revealing — the product changes down the group as the larger cations stabilise larger oxide anions.

🌬️
With oxygen — three different products
\(\ce{Li -> Li2O}\) (oxide) · \(\ce{Na -> Na2O2}\) (peroxide) · \(\ce{K, Rb, Cs -> MO2}\) (superoxide)

Small \(\ce{Li+}\) stabilises only the small oxide ion \(\ce{O^2-}\); larger cations stabilise the bigger peroxide \(\ce{O2^2-}\) and superoxide \(\ce{O2-}\) ions.

Reacts withEquationNote
Water\(\ce{2Na + 2H2O -> 2NaOH + H2 ^}\)vigour rises down group
Hydrogen\(\ce{2Na + H2 -> 2NaH}\)ionic hydride
Halogen\(\ce{2Na + Cl2 -> 2NaCl}\)ionic halide
Liquid ammonia\(\ce{Na + (x+y)NH3 -> [Na(NH3)_x]+ + [e(NH3)_y]-}\)deep-blue solution
The blue solution. Alkali metals dissolve in liquid ammonia to give a deep-blue, conducting solution containing ammoniated electrons. The colour fades as concentration rises, and the freed electrons make these solutions powerful reducing agents.
Section 16-4

The Lithium Anomaly & Diagonal Relationship

Lithium, the first member, is the odd one out. Its very small size and high polarising power (charge density) give it more covalent character and a chemistry closer to magnesium — the classic diagonal relationship.

Lithium (unlike its group)...resembles magnesium
forms only the oxide \(\ce{Li2O}\) (no peroxide)\(\ce{Mg}\) also forms only \(\ce{MgO}\)
\(\ce{LiF},\ \ce{Li2CO3},\ \ce{Li3PO4}\) sparingly solublecorresponding \(\ce{Mg}\) salts also low-solubility
combines with \(\ce{N2}\) to give \(\ce{Li3N}\)\(\ce{Mg}\) forms \(\ce{Mg3N2}\)
\(\ce{LiNO3 ->[\Delta] Li2O + NO2 + O2}\)\(\ce{Mg(NO3)2}\) decomposes similarly
Section 16-5

Compounds of Sodium & the Solvay Process

Sodium gives some of the most important industrial chemicals. Sodium carbonate (washing soda, \(\ce{Na2CO3.10H2O}\)) is made by the Solvay (ammonia-soda) process, in which cheap brine and limestone are converted using ammonia as a recyclable go-between.

🏭
The Solvay process
\(\ce{NH3 + CO2 + H2O -> NH4HCO3}\); \(\ \ce{NH4HCO3 + NaCl -> NaHCO3 v + NH4Cl}\); \(\ \ce{2NaHCO3 ->[\Delta] Na2CO3 + H2O + CO2}\)

Sparingly soluble \(\ce{NaHCO3}\) precipitates out and is filtered, then heated to \(\ce{Na2CO3}\). Ammonia is recovered from \(\ce{NH4Cl}\) with lime and recycled. The process fails for \(\ce{K2CO3}\) because \(\ce{KHCO3}\) is too soluble to precipitate.

CompoundCommon nameKey use
\(\ce{NaOH}\)caustic sodasoap, paper, rayon (Castner–Kellner electrolysis of brine)
\(\ce{Na2CO3.10H2O}\)washing sodaglass, detergents, water softening
\(\ce{NaHCO3}\)baking sodabaking, antacid, fire extinguishers
\(\ce{NaCl}\)common saltfeedstock for most sodium chemicals
Section 16-6

Group 2: The Alkaline Earth Metals

The alkaline earth metals have two valence electrons and form \(+2\) ions. Compared with their Group 1 neighbours they are smaller, harder, denser and higher-melting, because the extra electron and higher nuclear charge tighten the metallic bonding. They are still reactive, but less so than the alkali metals.

🔥
Flame colours
Ca → brick red · Sr → crimson · Ba → apple green (Be, Mg → none)

Beryllium and magnesium hold their electrons too tightly to be excited by a Bunsen flame, so they give no flame colour — a useful diagnostic.

Section 16-7

Trends & Reactions of Group 2

Down the group, reactivity rises just as in Group 1. The most exam-relevant trends concern the solubility and thermal stability of their compounds, which move in opposite directions.

Down the groupTrend
Solubility of hydroxidesincreases (\(\ce{Mg(OH)2}\) low, \(\ce{Ba(OH)2}\) high)
Solubility of sulphates / carbonatesdecreases (\(\ce{BaSO4}\) insoluble)
Thermal stability of carbonatesincreases
Reactivity with waterincreases (\(\ce{Be}\) almost none, \(\ce{Ba}\) vigorous)
Why sulphate solubility falls. As the cation grows, the lattice energy decreases only slightly while the hydration enthalpy drops sharply, so the larger sulphates (\(\ce{BaSO4}\)) become insoluble. This is exactly why \(\ce{BaSO4}\) is used as the "barium meal" in X-rays — it is insoluble and so non-toxic.
Section 16-8

The Beryllium Anomaly & Diagonal Relationship

Beryllium, like lithium, breaks ranks. Its tiny size, high electronegativity and lack of \(d\)-orbitals give it strong covalent character and a chemistry that mirrors aluminium diagonally below it.

Beryllium (unlike its group)...resembles aluminium
\(\ce{Be(OH)2}\) is amphoteric\(\ce{Al(OH)3}\) is amphoteric
\(\ce{BeCl2}\) is covalent & polymeric\(\ce{AlCl3}\) is covalent (dimer \(\ce{Al2Cl6}\))
dissolves in alkali giving \(\ce{[Be(OH)4]^2-}\)\(\ce{Al}\) gives \(\ce{[Al(OH)4]-}\)
forms covalent, hydrolysing compounds\(\ce{Al}\) salts hydrolyse too
Section 16-9

Compounds of Calcium

Calcium compounds run the construction industry. They begin with limestone \(\ce{CaCO3}\), which on heating gives quicklime \(\ce{CaO}\), and from there slaked lime, gypsum and cement.

🧱
Lime cycle & plaster of Paris
\(\ce{CaCO3 ->[\Delta] CaO + CO2}\); \(\ \ce{CaO + H2O -> Ca(OH)2}\); \(\ \ce{2CaSO4.2H2O ->[393\,K] 2CaSO4.\tfrac12 H2O + 3H2O}\)

Heating gypsum to about \(393\,\text{K}\) gives plaster of Paris, \(\ce{CaSO4.\tfrac12 H2O}\); adding water reverses the step, setting it back to a hard mass of gypsum — the basis of casts and moulds.

CompoundNameUse
\(\ce{CaO}\)quicklimecement, steel, drying agent
\(\ce{Ca(OH)2}\)slaked limewhitewash, \(\ce{CO2}\) test (limewater)
\(\ce{CaCO3}\)limestone / marblebuilding, antacid, toothpaste
\(\ce{CaSO4.\tfrac12 H2O}\)plaster of Pariscasts, moulds, statues
Limewater test. Bubbling \(\ce{CO2}\) through limewater turns it milky: \(\ce{Ca(OH)2 + CO2 -> CaCO3 v + H2O}\). Excess \(\ce{CO2}\) re-dissolves the precipitate as soluble \(\ce{Ca(HCO3)2}\) — the same reaction that carves limestone caves.
Section 16-10

Biological Importance

Four s-block ions are essential to life. Their roles flow directly from their charge, size and abundance.

IonRole in the body
\(\ce{Na+}\)nerve signal transmission, fluid balance, the \(\ce{Na}\)–\(\ce{K}\) pump
\(\ce{K+}\)intracellular cation, muscle and nerve function
\(\ce{Mg^2+}\)centre of chlorophyll, cofactor for many enzymes
\(\ce{Ca^2+}\)bones and teeth, blood clotting, muscle contraction
Worked Examples

Putting It to Work

1 Which oxide forms?

Problem. Predict the main product when lithium, sodium and potassium each burn in excess oxygen.

Solution. Cation size decides which oxide-anion is stabilised:

Working
\[ \ce{Li2O}\ (\text{oxide});\quad \ce{Na2O2}\ (\text{peroxide});\quad \ce{KO2}\ (\text{superoxide}) \]
2 Identify by flame colour

Problem. An unknown salt gives an apple-green flame. Which metal ion is present?

Solution. Apple-green is the signature of barium:

Working
\[ \Rightarrow\ \ce{Ba^2+}\ (\text{barium}) \]
3 Solubility trend

Problem. Arrange \(\ce{MgSO4},\ \ce{CaSO4},\ \ce{BaSO4}\) in order of decreasing solubility.

Solution. Group-2 sulphate solubility falls down the group:

Working
\[ \ce{MgSO4} > \ce{CaSO4} > \ce{BaSO4} \]
4 Solvay product

Problem. In the Solvay process, what precipitates when \(\ce{NH4HCO3}\) reacts with brine, and what is it heated to give?

Solution. Sparingly soluble bicarbonate drops out, then decomposes:

Working
\[ \ce{NaHCO3 v};\quad \ce{2NaHCO3 ->[\Delta] Na2CO3 + H2O + CO2} \]
5 Diagonal reasoning

Problem. Lithium forms a nitride directly with \(\ce{N2}\). Which Group 2 element behaves similarly, and why?

Solution. The Li–Mg diagonal relationship predicts the match:

Working
\[ \ce{Mg}:\quad \ce{3Mg + N2 -> Mg3N2} \]
6 Plaster of Paris

Problem. Write the reaction by which gypsum is converted to plaster of Paris, and state how it sets.

Solution. Controlled heating removes most of the water of crystallisation:

Working
\[ \ce{2CaSO4.2H2O ->[393\,K] 2CaSO4.\tfrac12 H2O + 3H2O};\quad \text{sets by re-adding water} \]
Review

Chapter Summary

The block

Group 1 (\(ns^1\), +1) and Group 2 (\(ns^2\), +2) — reactive, electropositive metals.

Trends

Down the group: size ↑, IE ↓, reactivity ↑; Li is the strongest aqueous reductant.

With oxygen

Li → oxide, Na → peroxide, K/Rb/Cs → superoxide; flame colours identify the metal.

Anomalies

Li ↔ Mg and Be ↔ Al diagonal relationships; Be is amphoteric and covalent.

Sodium

NaOH, washing soda, baking soda; the Solvay process makes \(\ce{Na2CO3}\).

Calcium

Lime cycle, plaster of Paris, cement; \(\ce{Na, K, Mg, Ca}\) are vital to life.

Practice

Problems

For each item, first decide which idea it tests — a periodic trend, a reaction, an anomaly, or a named compound — then apply the relevant rule. Difficulty rises down the list.

  1. State the general electronic configuration of Group 1 and Group 2 elements.
  2. Why are the alkali metals the most electropositive elements in their periods?
  3. Explain why lithium is the strongest reducing agent in aqueous solution despite its high ionization enthalpy.
  4. Write the products formed when Li, Na and K each react with excess oxygen.
  5. Give the flame colours of \(\ce{Na},\ \ce{K},\ \ce{Ca}\) and \(\ce{Ba}\).
  6. List three ways lithium resembles magnesium (the diagonal relationship).
  7. Write the three main steps of the Solvay process and explain why it fails for \(\ce{K2CO3}\).
  8. Arrange \(\ce{Mg(OH)2},\ \ce{Ca(OH)2},\ \ce{Ba(OH)2}\) in order of increasing solubility.
  9. Why do beryllium and magnesium not impart colour to a flame?
  10. Explain why \(\ce{Be(OH)2}\) and \(\ce{BeCl2}\) are described as anomalous, relating them to aluminium.
  11. Describe the lime cycle and write the reaction for the limewater test for \(\ce{CO2}\).
  12. How is plaster of Paris prepared from gypsum, and why must the temperature be controlled?
Tip: almost every property here flows from one number — charge density (charge ÷ size). Small, high-charge-density ions (\(\ce{Li+},\ \ce{Be^2+}\)) polarise, form covalent bonds and behave anomalously; large, low-charge-density ions are purely ionic and "well-behaved". Fix the ion's size and charge and the chemistry follows.