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Chapter 10 The S-Block Elements
The s-block elements are located on the left side of the Periodic Table, encompassing Group 1 and Group 2. These are elements in which the last electron enters the outermost s-orbital. Since an s-orbital can hold a maximum of two electrons, there are two groups in the s-block.
Group 1 consists of Lithium (Li), Sodium (Na), Potassium (K), Rubidium (Rb), Caesium (Cs), and Francium (Fr). They are known as **alkali metals** because they react with water to form strongly alkaline solutions (hydroxides).
Group 2 includes Beryllium (Be), Magnesium (Mg), Calcium (Ca), Strontium (Sr), Barium (Ba), and Radium (Ra). With the exception of Beryllium, they are called **alkaline earth metals**. This is because their oxides and hydroxides are alkaline, and these metal oxides are found in the Earth's crust.
Sodium and Potassium are relatively abundant alkali metals, while Lithium, Rubidium, and Caesium are less abundant. Francium is extremely rare and radioactive. Among alkaline earth metals, Calcium and Magnesium are more abundant than Strontium, Barium, and the rare, radioactive Radium.
The general electronic configuration is [noble gas]ns$^1$ for alkali metals and [noble gas]ns$^2$ for alkaline earth metals.
The first element of each group (Lithium and Beryllium) displays properties different from other members of their group. They also show similarities to the second element of the next group (Lithium resembles Magnesium, and Beryllium resembles Aluminium). This is called the **diagonal relationship**, arising from similar ionic sizes and/or charge-to-radius ratios.
Sodium, Potassium, Magnesium, and Calcium ions are biologically important, playing roles in ion balance and nerve impulse conduction.
Group 1 Elements: Alkali Metals
The alkali metals exhibit characteristic trends in their physical and chemical properties down the group.
Electronic Configuration
All alkali metals have a valence shell electronic configuration of ns$^1$ (Table 10.1), where n is the period number. This single, loosely held s-electron makes them highly electropositive and reactive. They readily lose this electron to form stable $+1$ ions (M$^+$). Consequently, they are not found in their elemental form in nature.
Property | Lithium (Li) | Sodium (Na) | Potassium (K) | Rubidium (Rb) | Caesium (Cs) | Francium (Fr) |
Atomic number | 3 | 11 | 19 | 37 | 55 | 87 |
Atomic mass (g mol$^{-1}$) | 6.94 | 22.99 | 39.10 | 85.47 | 132.91 | (223) |
Electronic configuration | [He] 2s$^1$ | [Ne] 3s$^1$ | [Ar] 4s$^1$ | [Kr] 5s$^1$ | [Xe] 6s$^1$ | [Rn] 7s$^1$ |
Ionization enthalpy / kJ mol$^{-1}$ | 520 | 496 | 419 | 403 | 376 | ~375 |
Hydration enthalpy/kJ mol$^{-1}$ (M$^+$) | –506 | –406 | –330 | –310 | –276 | – |
Metallic radius / pm | 152 | 186 | 227 | 248 | 265 | – |
Ionic radius M$^+$ / pm | 76 | 102 | 138 | 152 | 167 | (180) |
m.p. / K | 454 | 371 | 336 | 312 | 302 | – |
b.p / K | 1615 | 1156 | 1032 | 961 | 944 | – |
Density / g cm$^{-3}$ | 0.53 | 0.97 | 0.86 | 1.53 | 1.90 | – |
Standard potentials E$^{\tiny\mathbf{0}}$ / V for (M$^+$ / M) | –3.04 | –2.714 | –2.925 | –2.930 | –2.927 | –2.927 |
Occurrence in lithosphere† | 18* | 2.27** | 1.84** | 78-12* | 2-6* | ~ 10$^{-18}$ * |
*ppm (part per million), ** percentage by weight; † Lithosphere: The Earth’s outer layer: its crust and part of the upper mantle
Atomic And Ionic Radii
Alkali metal atoms are the **largest** in their respective periods due to their low effective nuclear charge experienced by the outermost electron. Both atomic and ionic (M$^+$) radii **increase** down the group from Li to Cs as the number of electron shells increases. The M$^+$ ion is always smaller than the parent atom due to the loss of the outermost electron shell.
Ionization Enthalpy
Alkali metals have **very low ionization enthalpies** (energy to remove an electron) because the single valence electron is loosely held and effectively shielded by inner electrons. Ionization enthalpy **decreases** down the group as atomic size increases and the outermost electron is further from the nucleus.
Hydration Enthalpy
When alkali metal ions (M$^+$) are dissolved in water, they get hydrated by polar water molecules, releasing energy (hydration enthalpy). The degree of hydration and hydration enthalpy **decrease** with increasing ionic size down the group (smaller ions are more effectively hydrated). Li$^+$ is the most hydrated and has the highest hydration enthalpy, leading to many lithium salts being hydrated (e.g., LiCl·2H$_2$O).
Li$^+$ > Na$^+$ > K$^+$ > Rb$^+$ > Cs$^+$ (decreasing hydration enthalpy)
Physical Properties
- Appearance: Silvery white, lustrous.
- Softness: Very soft (can be cut with a knife). Softness increases down the group.
- Density: Low density, generally increasing down the group. Potassium is less dense than sodium.
- Melting and Boiling Points: Low melting and boiling points due to weak metallic bonding (only one valence electron involved). Melting and boiling points generally decrease down the group.
- Flame Colouration: Alkali metals and their salts impart characteristic colours to an oxidising flame (Li: Crimson red, Na: Yellow, K: Violet, Rb: Red-violet, Cs: Blue). This is due to the excitation and de-excitation of valence electrons, emitting light in the visible spectrum. This property is used in flame tests and photometry for identification.
- Photoelectric Effect: These metals readily emit electrons when irradiated with light (photoelectric effect), especially Cs and K, making them useful in photoelectric cells.
- Electrical and Thermal Conductivity: Good conductors, typical of metals.
Chemical Properties
Alkali metals are **highly reactive** due to their large size and low ionization enthalpies. Reactivity **increases** down the group.
- Reactivity towards Air: They tarnish in dry air due to oxide formation and react with moisture to form hydroxides. They burn vigorously in oxygen:
* Li forms mainly **monoxide** ($\text{Li}_2\text{O}$).
* Na forms primarily **peroxide** ($\text{Na}_2\text{O}_2$).
* K, Rb, Cs form **superoxides** ($\text{MO}_2$).
$\text{4Li} + \text{O}_2 \rightarrow \text{2Li}_2\text{O}$
$\text{2Na} + \text{O}_2 \rightarrow \text{Na}_2\text{O}_2$
$\text{M} + \text{O}_2 \rightarrow \text{MO}_2$ (M = K, Rb, Cs)
Lithium is unique as it also reacts directly with nitrogen in the air to form **nitride** ($\text{Li}_3\text{N}$). Alkali metals are stored in kerosene to prevent reaction with air/water.
Problem 10.1. What is the oxidation state of K in KO$_2$?
Answer:
KO$_2$ is Potassium superoxide. It is an ionic compound formed between the potassium ion (K$^+$) and the superoxide ion (O$_2^-$).
The formula is KO$_2$. The overall charge of the compound is neutral (0).
We know that potassium (an alkali metal) typically has an oxidation state of +1 in its compounds.
Let the oxidation state of Potassium (K) be $x$, and the oxidation state of Oxygen (O) be $y$. The formula is KO$_2$, so there is one K atom and two O atoms.
The sum of the oxidation states must equal the overall charge of the compound (0):
$x + 2y = 0$.
In superoxides like KO$_2$, oxygen exists as the superoxide ion, O$_2^-$. In the O$_2^-$ ion, the two oxygen atoms collectively carry a charge of -1. Therefore, the oxidation state of the O$_2$ unit is -1. If we want the oxidation state *per oxygen atom*, it is -1/2.
Since the superoxide ion is O$_2^-$, and KO$_2$ is an ionic compound K$^+$O$_2^-$, the potassium ion is K$^+$. The oxidation state of the potassium ion (K$^+$) is +1.
Therefore, the oxidation state of K in KO$_2$ is +1.
We can also confirm the oxidation state of oxygen in the superoxide ion O$_2^-$. Let the oxidation state of one oxygen atom be $y$. Then $2y = -1$, so $y = -1/2$. The average oxidation state of oxygen in superoxides is -1/2.
- Reactivity towards Water: React vigorously with water to form hydroxides and dihydrogen gas. Reactivity increases down the group. Lithium reacts less vigorously than expected from its reduction potential due to its high hydration energy.
$\text{2M} + \text{2H}_2\text{O} \rightarrow \text{2M}^+ + \text{2OH}^- + \text{H}_2$
They also react with other proton donors like alcohols and ammonia. - Reactivity towards Dihydrogen: React with H$_2$ at high temperatures to form ionic hydrides (M$^+$H$^-$).
$\text{2M} + \text{H}_2 \rightarrow \text{2MH}$
- Reactivity towards Halogens: React vigorously with halogens to form ionic halides (M$^+$X$^-$). Lithium halides are somewhat covalent due to the small, highly polarising Li$^+$ ion distorting the electron cloud of the halide anion. Covalent character increases with the size of the anion (LiI is most covalent).
$\text{2M} + \text{X}_2 \rightarrow \text{2MX}$
- Reducing Nature: They are strong reducing agents (easily lose electrons), with lithium being the strongest. Their reducing power is measured by standard electrode potential ($E^0$). Although Li has the highest ionization energy, its exceptionally high hydration enthalpy of Li$^+$ gives it the most negative $E^0$ value, making it the strongest reducing agent in aqueous solution.
Problem 10.2. The E$^{\tiny\mathbf{0}}$ for Cl$_2$/Cl$^–$ is +1.36, for I$_2$/I$^–$ is + 0.53, for Ag$^+$ /Ag is +0.79, Na$^+$ /Na is –2.71 and for Li$^+$ /Li is – 3.04. Arrange the following ionic species in decreasing order of reducing strength: I$^–$, Ag, Cl$^–$, Li, Na
Answer:
Reducing strength is the tendency of a species to donate electrons (undergo oxidation). A stronger reducing agent is more easily oxidised.
The standard electrode potentials ($E^0$) provided are for reduction half-reactions (Oxidised form + ne$^-$ $\rightleftharpoons$ Reduced form). A more negative $E^0$ value indicates a greater tendency for the reduced form to be oxidised (stronger reducing agent).
The species to arrange are I$^–$, Ag, Cl$^–$, Li, Na. These are all in their reduced forms (except for Ag which is given as Ag metal, which is the reduced form of Ag$^+$). We need to compare their tendencies to lose electrons.
Let's list the $E^0$ values for the reduction half-reactions involving these species:
- I$_2$/I$^-$: $E^0 = +0.53$ V (I$^-$ is the reduced form)
- Ag$^+$ /Ag: $E^0 = +0.79$ V (Ag is the reduced form)
- Cl$_2$/Cl$^-$: $E^0 = +1.36$ V (Cl$^-$ is the reduced form)
- Na$^+$ /Na: $E^0 = -2.71$ V (Na is the reduced form)
- Li$^+$ /Li: $E^0 = -3.04$ V (Li is the reduced form)
The species provided in the question whose reducing strength is to be compared are the reduced forms: I$^–$, Ag, Cl$^–$, Li, Na.
A lower (more negative) $E^0$ for the reduction half-reaction means the reduced species on the right side of the half-reaction is a stronger reducing agent.
Order of $E^0$ values from most negative to most positive:
Li$^+$ /Li (-3.04 V) < Na$^+$ /Na (-2.71 V) < I$_2$/I$^-$ (+0.53 V) < Ag$^+$ /Ag (+0.79 V) < Cl$_2$/Cl$^-$ (+1.36 V)
The corresponding reduced species are Li, Na, I$^–$, Ag, Cl$^–$. Their reducing strength is in the same order as the $E^0$ values are from most negative to most positive.
Reducing strength order: Li > Na > I$^–$ > Ag > Cl$^–$.
We need to arrange the given ionic species (I$^–$, Ag, Cl$^–$, Li, Na) in decreasing order of reducing strength.
Decreasing order means from strongest reducing agent to weakest reducing agent.
Strongest reducing agent is Li (-3.04 V), then Na (-2.71 V), then I$^-$ (+0.53 V), then Ag (+0.79 V), then Cl$^-$ (+1.36 V).
The order is Li > Na > I$^–$ > Ag > Cl$^–$.
Wait, the question asks for decreasing order of reducing strength for the species: I$^–$, Ag, Cl$^–$, Li, Na. These are exactly the reduced forms.
Order of reducing strength:
Li > Na > I$^–$ > Ag > Cl$^–$.
Uses
Alkali metals and their compounds have various uses:
- **Lithium:** Used in alloys (with lead for bearings, aluminium for aircraft, magnesium for armour plates), in thermonuclear reactions, and electrochemical cells.
- **Sodium:** Used in Na/Pb alloy (historically for petrol additives), as a coolant in nuclear reactors, and in producing chemicals.
- **Potassium:** Essential in biological systems, KCl is a fertilizer, KOH is used for soft soap and CO$_2$ absorption.
- **Caesium:** Used in photoelectric cells.
General Characteristics Of The Compounds Of The Alkali Metals
Most common compounds of alkali metals are predominantly **ionic** due to the large size and low ionization enthalpy of the metals. However, lithium compounds show more covalent character due to the small size and high polarising power of Li$^+$.
Oxides And Hydroxides
Reaction with oxygen yields different types of oxides: Li (monoxide, Li$_2$O), Na (peroxide, Na$_2$O$_2$), K, Rb, Cs (superoxides, MO$_2$). Higher oxides (peroxides, superoxides) are more stable with larger cations due to lattice energy effects. All these oxides are basic and react with water to form hydroxides, which are strong bases.
$\text{M}_2\text{O} + \text{H}_2\text{O} \rightarrow \text{2M}^+ + \text{2OH}^-$
$\text{M}_2\text{O}_2 + \text{2H}_2\text{O} \rightarrow \text{2M}^+ + \text{2OH}^- + \text{H}_2\text{O}_2$
$\text{2MO}_2 + \text{2H}_2\text{O} \rightarrow \text{2M}^+ + \text{2OH}^- + \text{H}_2\text{O}_2 + \text{O}_2$
Pure oxides and peroxides are colourless, while superoxides are yellow/orange and paramagnetic (due to unpaired electrons in O$_2^-$ ion).
Problem 10.3. Why is KO$_2$ paramagnetic ?
Answer:
KO$_2$ is potassium superoxide. It is an ionic compound consisting of K$^+$ ions and O$_2^-$ (superoxide) ions.
Paramagnetism is a property of substances that have unpaired electrons. We need to examine the electron configuration of the superoxide ion (O$_2^-$).
The O$_2$ molecule has a total of 16 electrons (8 from each oxygen atom). Its molecular orbital configuration is $(\sigma_{1s})^2(\sigma^*_{1s})^2(\sigma_{2s})^2(\sigma^*_{2s})^2(\sigma_{2p_z})^2(\pi_{2p_x})^2(\pi_{2p_y})^2(\pi^*_{2p_x})^1(\pi^*_{2p_y})^1$. The last two electrons are in the degenerate antibonding $\pi^*_{2p}$ orbitals, one electron in each, with parallel spins (according to Hund's rule). This gives O$_2$ two unpaired electrons, making it paramagnetic.
The superoxide ion O$_2^-$ is formed by adding one electron to the O$_2$ molecule. This extra electron enters one of the $\pi^*_{2p}$ orbitals, pairing up one of the electrons.
The MO configuration of O$_2^-$ is $(\sigma_{1s})^2(\sigma^*_{1s})^2(\sigma_{2s})^2(\sigma^*_{2s})^2(\sigma_{2p_z})^2(\pi_{2p_x})^2(\pi_{2p_y})^2(\pi^*_{2p_x})^2(\pi^*_{2p_y})^1$.
In the $\pi^*_{2p}$ antibonding orbitals, there are now a total of 3 electrons (2 in one, 1 in the other). This leaves **one unpaired electron** in the $\pi^*_{2p_y}$ orbital (or $\pi^*_{2p_x}$).
Because the superoxide ion O$_2^-$ contains one unpaired electron, compounds containing this ion, such as KO$_2$, are **paramagnetic**.
Alkali metal hydroxides are strong bases due to their high solubility and complete dissociation in water.
Halides
Alkali metal halides (MX) are typically high melting, colourless ionic solids. They are generally soluble in water, although LiF has low solubility due to high lattice energy and CsI has low solubility due to low hydration energy. Lithium halides show some covalent character due to Li$^+$ polarising the anion, which is most prominent in LiI due to the large size of the I$^-$ anion.
Salts Of Oxo-Acids
Alkali metals form salts with oxo-acids (acids with oxygen in the acidic group, like sulfates, nitrates, carbonates). These salts are generally soluble in water and thermally stable. The stability of carbonates and hydrogencarbonates increases down the group as the cation size increases. Lithium carbonate is less stable and decomposes easily on heating due to the small Li$^+$ ion stabilising the oxide product over the carbonate.
Anomalous Properties Of Lithium
Lithium, the first element in Group 1, shows some properties that are significantly different from the other alkali metals. This anomalous behaviour is primarily due to its **exceptionally small atomic and ionic size** and its **high polarising power** (high charge/radius ratio).
Points Of Difference Between Lithium And Other Alkali Metals
- Hardness and melting/boiling points: Li is much harder and has higher m.p./b.p.
- Reactivity and reducing power: Li is the least reactive (among alkali metals) but the strongest reducing agent (in aqueous solution).
- Reaction with air: Forms mainly monoxide (Li$_2$O) and nitride (Li$_3$N). Others form peroxide/superoxides and do not form nitride directly.
- Hydrates: LiCl is deliquescent and forms a hydrate (LiCl·2H$_2$O). Other alkali metal chlorides are usually anhydrous.
- Hydrogencarbonates: Lithium hydrogencarbonate does not exist as a solid.
- Reaction with ethyne: Lithium does not form ethynide.
- Nitrate decomposition: LiNO$_3$ decomposes to oxide (Li$_2$O). Others decompose to nitrite.
- Solubility: LiF and Li$_2$O are less soluble in water. LiCl is soluble in organic solvents.
Points Of Similarities Between Lithium And Magnesium
Lithium shows similarities to magnesium (diagonal relationship) due to similar atomic and ionic sizes (Li 152pm, Li$^+$ 76pm; Mg 160pm, Mg$^{2+}$ 72pm). Key similarities:
- Hardness: Both are harder and lighter than other elements in their respective groups.
- Reactivity with water: Both react slowly with water.
- Solubility and decomposition of hydroxides: Both form less soluble hydroxides that decompose on heating.
- Reaction with nitrogen: Both form nitrides ($\text{Li}_3\text{N}, \text{Mg}_3\text{N}_2$) by direct combination with N$_2$.
- Oxides and peroxides: Their oxides (Li$_2$O, MgO) do not form superoxides with excess oxygen.
- Carbonate decomposition: Their carbonates decompose easily on heating. Neither forms solid hydrogencarbonates.
- Halide solubility: Both LiCl and MgCl$_2$ are soluble in ethanol.
- Hydrates: Both form hydrated chlorides ($\text{LiCl} \cdot \text{2H}_2\text{O}, \text{MgCl}_2 \cdot \text{8H}_2\text{O}$).
Some Important Compounds Of Sodium
Important sodium compounds include sodium carbonate ($\text{Na}_2\text{CO}_3$), sodium chloride (NaCl), sodium hydroxide (NaOH), and sodium hydrogencarbonate (NaHCO$_3$).
- Sodium Carbonate (Washing Soda, Na$_2$CO$_3$·10H$_2$O): Prepared industrially by the **Solvay process**, which uses NaCl, NH$_3$, and CaCO$_3$. It relies on the low solubility of NaHCO$_3$ which precipitates and is then heated to yield Na$_2$CO$_3$. Na$_2$CO$_3$ is a white solid, soluble in water (forming alkaline solution due to hydrolysis), used in glass, soap, paper, cleaning, and as a lab reagent.
- Sodium Chloride (NaCl): Obtained mainly by evaporation of sea water. Crude salt is purified by dissolving in water and precipitating pure NaCl by saturating with HCl gas (common ion effect). Used as table salt and in the production of Na$_2$O$_2$, NaOH, and Na$_2$CO$_3$.
- Sodium Hydroxide (Caustic Soda, NaOH): Prepared commercially by the **electrolysis of brine solution** in the Castner-Kellner cell. Sodium amalgam formed at the mercury cathode reacts with water to produce NaOH and H$_2$. NaOH is a white, deliquescent solid, a strong base, used in manufacturing soap, paper, textiles, petroleum refining, and as a lab reagent.
- Sodium Hydrogencarbonate (Baking Soda, NaHCO$_3$): Prepared by saturating a solution of Na$_2$CO$_3$ with CO$_2$. Decomposes on heating to produce CO$_2$ (used in baking and fire extinguishers), used as a mild antiseptic and antacid ingredient.
Biological Importance Of Sodium And Potassium
Sodium and potassium ions are crucial for biological functions:
- **Sodium ions (Na$^+$):** Located primarily outside cells (blood plasma, interstitial fluid). Important for nerve signal transmission, water balance across cell membranes, and transport of sugars and amino acids into cells.
- **Potassium ions (K$^+$):** Most abundant cations inside cells. Activate many enzymes, involved in glucose oxidation to produce ATP. Participate with Na$^+$ in nerve signal transmission.
The **sodium-potassium pump** actively transports these ions across cell membranes against concentration gradients, a process vital for nerve function and consuming significant ATP energy.
Group 2 Elements : Alkaline Earth Metals
The alkaline earth metals (Be, Mg, Ca, Sr, Ba, Ra) follow alkali metals in the periodic table. They are less reactive than alkali metals but more reactive than Group 13 elements. Beryllium is anomalous and shows diagonal relationship with aluminium.
Property | Beryllium (Be) | Magnesium (Mg) | Calcium (Ca) | Strontium (Sr) | Barium (Ba) | Radium (Ra) |
Atomic number | 4 | 12 | 20 | 38 | 56 | 88 |
Atomic mass (g mol$^{-1}$) | 9.01 | 24.31 | 40.08 | 87.62 | 137.33 | 226.03 |
Electronic configuration | [He] 2s$^2$ | [Ne] 3s$^2$ | [Ar] 4s$^2$ | [Kr] 5s$^2$ | [Xe] 6s$^2$ | [Rn] 7s$^2$ |
Ionization enthalpy (I) / kJ mol$^{-1}$ | 899 | 737 | 590 | 549 | 503 | 509 |
Ionization enthalpy (II) /kJ mol$^{-1}$ | 1757 | 1450 | 1145 | 1064 | 965 | 979 |
Hydration enthalpy (kJ/mol) (M$^{2+}$) | – 2494 | – 1921 | –1577 | – 1443 | – 1305 | – |
Metallic radius / pm | 111 | 160 | 197 | 215 | 222 | – |
Ionic radius M$^{2+}$ / pm | 31 | 72 | 100 | 118 | 135 | 148 |
m.p. / K | 1560 | 924 | 1124 | 1062 | 1002 | 973 |
b.p / K | 2745 | 1363 | 1767 | 1655 | 2078 | (1973) |
Density / g cm$^{-3}$ | 1.84 | 1.74 | 1.55 | 2.63 | 3.59 | (5.5) |
Standard potential E$^{\tiny\mathbf{0}}$ / V for (M$^{2+}$/ M) | –1.97 | –2.36 | –2.84 | –2.89 | – 2.92 | –2.92 |
Occurrence in lithosphere | 2* | 2.76** | 4.6** | 384* | 390 * | 10–6* |
*ppm (part per million); ** percentage by weight
Electronic Configuration
Alkaline earth metals have a valence shell configuration of ns$^2$ (Table 10.2). They readily lose these two electrons to form stable $+2$ ions (M$^{2+}$).
Atomic And Ionic Radii
Atomic and ionic radii are smaller than corresponding alkali metals due to higher nuclear charge. Radii **increase** down the group.
Ionization Enthalpies
Ionization enthalpies are low but higher than corresponding alkali metals (due to smaller size and higher effective nuclear charge). First ionization enthalpy > second ionization enthalpy. Both **decrease** down the group.
Hydration Enthalpies
Hydration enthalpies are higher than alkali metals (due to higher charge and smaller size). They **decrease** down the group with increasing ionic size. Alkaline earth metal compounds are generally more hydrated than alkali metal compounds (e.g., MgCl$_2$·6H$_2$O vs NaCl).
Be$^{2+}$ > Mg$^{2+}$ > Ca$^{2+}$ > Sr$^{2+}$ > Ba$^{2+}$ (decreasing hydration enthalpy)
Physical Properties
- Appearance: Silvery white, lustrous, relatively soft (harder than alkali metals).
- Density: Higher density than alkali metals (generally increasing down the group).
- Melting and Boiling Points: Higher than corresponding alkali metals due to stronger metallic bonding (two valence electrons). No systematic trend in m.p./b.p.
- Flame Colouration: Ca (brick red), Sr (crimson), Ba (apple green) impart characteristic colours due to electron excitation. Be and Mg do not impart colour as their electrons are too strongly bound.
- Electrical and Thermal Conductivity: Good conductors.
Chemical Properties
Alkaline earth metals are less reactive than alkali metals. Reactivity **increases** down the group.
- Reactivity towards Air and Water: Be and Mg are inert due to oxide film. Powdered Be burns in air to BeO and Be$_3$N$_2$. Mg burns brightly to MgO and Mg$_3$N$_2$. Heavier elements are more reactive, attacking air and water (even cold) to form hydroxides and H$_2$.
$\text{M} + \text{2H}_2\text{O} \rightarrow \text{M(OH)}_2 + \text{H}_2$ (M = Ca, Sr, Ba)
- Reactivity towards Halogens: Combine at high temperatures to form halides (MX$_2$). Be halides are covalent; others are ionic.
$\text{M} + \text{X}_2 \rightarrow \text{MX}_2$
- Reactivity towards Hydrogen: Combine with H$_2$ upon heating to form hydrides (MH$_2$), except Be (BeH$_2$ is made indirectly).
$\text{M} + \text{H}_2 \rightarrow \text{MH}_2$ (M = Ca, Sr, Ba)
- Reactivity towards Acids: React readily with acids, liberating H$_2$.
$\text{M} + \text{2HCl} \rightarrow \text{MCl}_2 + \text{H}_2$
- Reducing Nature: Strong reducing agents (due to low ionization enthalpies), but weaker than corresponding alkali metals. Reducing power increases down the group (more negative $E^0$).
- Solutions in Liquid Ammonia: Dissolve in liquid ammonia to give blue-black solutions of ammoniated ions and electrons.
Uses
Alkaline earth metals and their compounds have various uses:
- **Beryllium:** In alloys (with Cu for springs), for X-ray tube windows.
- **Magnesium:** In light alloys (for aircraft), in flash powders, as an antacid (milk of magnesia), in toothpaste.
- **Calcium:** In metallurgy, as a getter to remove air from vacuum tubes.
- **Barium:** In metallurgy, as a getter. Barium sulfate is used as a contrast agent in X-rays.
- **Radium:** Radium salts used in radiotherapy for cancer treatment.
General Characteristics Of Compounds Of The Alkaline Earth Metals
Alkaline earth metals predominantly form ionic compounds with a $+2$ oxidation state. These compounds are generally less ionic than corresponding alkali metal compounds. Compounds of Be and Mg show more covalent character.
- **Oxides (MO):** Formed by burning metals in oxygen. BeO is amphoteric; others (MgO, CaO, SrO, BaO) are basic, becoming more basic down the group. They react with water to form sparingly soluble hydroxides.
- **Hydroxides (M(OH)$_2$):** Formed by reacting oxides with water. Solubility, thermal stability, and basic character increase down the group. They are weaker bases than alkali metal hydroxides. Be(OH)$_2$ is amphoteric.
- **Halides (MX$_2$):** Formed by reacting metals with halogens or oxides/carbonates with hydrohalic acids. Be halides are covalent and soluble in organic solvents; others are ionic. Halides show decreasing tendency to form hydrates down the group. Fluorides are less soluble than chlorides due to high lattice energies.
- **Salts of Oxoacids (Carbonates, Sulfates, Nitrates):** * Carbonates (MCO$_3$): Insoluble in water. Thermal stability increases down the group (BeCO$_3$ least stable). Decompose to MO and CO$_2$ on heating. * Sulphates (MSO$_4$): White solids, stable to heat. Solubility decreases down the group (BeSO$_4$, MgSO$_4$ soluble; CaSO$_4$, SrSO$_4$, BaSO$_4$ sparingly soluble). Solubility is determined by the balance of hydration enthalpy (high for small ions) and lattice enthalpy. * Nitrates (M(NO$_3$)$_2$): Soluble in water. Form hydrates (tendency decreases down the group). Decompose on heating to MO, NO$_2$, and O$_2$.
Problem 10.4. Why does the solubility of alkaline earth metal hydroxides in water increase down the group?
Answer:
The dissolution of an ionic compound like an alkaline earth metal hydroxide, M(OH)$_2$, in water involves overcoming the attractive forces holding the ions in the solid lattice (lattice enthalpy) and the energy released when the separated ions are hydrated by water molecules (hydration enthalpy).
M(OH)$_2$(s) $\rightarrow$ M$^{2+}$(aq) + 2OH$^-$ (aq)
Solubility depends on the balance between the lattice enthalpy ($\Delta_{lattice}H$) and the hydration enthalpy ($\Delta_{hyd}H$). Favorable dissolution occurs when the energy released during hydration is sufficient to overcome the energy required to break down the lattice (i.e., $|\Delta_{hyd}H| > |\Delta_{lattice}H|$, net enthalpy change of solution is exothermic or slightly endothermic).
Down the group from Mg to Ba, the size of the cation (M$^{2+}$) increases (Mg$^{2+}$ < Ca$^{2+}$ < Sr$^{2+}$ < Ba$^{2+}$). The anion (OH$^-$) is common to all hydroxides in this group.
- **Lattice enthalpy ($\Delta_{lattice}H$)**: Lattice enthalpy is primarily determined by the charge density of the ions and the distance between them. As the cation size increases down the group, the distance between the cation and anion increases, leading to a **decrease** in lattice enthalpy (weaker attraction).
- **Hydration enthalpy ($\Delta_{hyd}H$)**: Hydration enthalpy depends on the charge density of the ion and its interaction with polar water molecules. As the cation size increases down the group, the charge density decreases (same charge, larger volume), leading to a **decrease** in hydration enthalpy (less energy released upon hydration).
For alkaline earth metal hydroxides, it is observed that the **decrease in lattice enthalpy down the group is more significant than the decrease in hydration enthalpy**. This means that the net energy change for dissolution becomes less endothermic (or more exothermic if it were exothermic) as we go down the group, favouring dissolution.
Therefore, the solubility of alkaline earth metal hydroxides in water **increases down the group**.
Problem 10.5. Why does the solubility of alkaline earth metal carbonates and sulphates in water decrease down the group?
Answer:
Similar to hydroxides, the solubility of carbonates (MCO$_3$) and sulphates (MSO$_4$) depends on the balance between lattice enthalpy and hydration enthalpy. The dissolution equation is MCO$_3$(s) $\rightarrow$ M$^{2+}$(aq) + CO$_3^{2-}$(aq) and MSO$_4$(s) $\rightarrow$ M$^{2+}$(aq) + SO$_4^{2-}$(aq).
Down the group, the cation size (M$^{2+}$) increases. The anions (CO$_3^{2-}$ and SO$_4^{2-}$) are relatively large compared to the cations.
- **Lattice enthalpy ($\Delta_{lattice}H$)**: Lattice enthalpy depends on the cation size and the anion size. Since the anions (CO$_3^{2-}$ and SO$_4^{2-}$) are large, changes in cation size have a relatively smaller impact on the overall interionic distance and thus on the lattice enthalpy compared to smaller anions like OH$^-$. While lattice enthalpy does decrease slightly down the group as cation size increases, the effect might be less pronounced than with smaller anions.
- **Hydration enthalpy ($\Delta_{hyd}H$)**: Hydration enthalpy of the cation (M$^{2+}$) decreases significantly down the group as its size increases and charge density decreases (Mg$^{2+}$ has higher hydration enthalpy than Ca$^{2+}$, etc.). The hydration enthalpy of the anion is constant for a given type of salt (carbonate or sulphate). The hydration energy contributing to dissolution is the sum of cation and anion hydration energies. Since the cation hydration energy decreases significantly down the group, the total hydration energy decreases.
For alkaline earth metal carbonates and sulphates, the **decrease in hydration enthalpy down the group is more significant than the decrease in lattice enthalpy**. This means that the net energy change for dissolution becomes more endothermic (or less exothermic) as we go down the group, making dissolution less favourable.
Therefore, the solubility of alkaline earth metal carbonates and sulphates in water **decreases down the group**.
Anomalous Behaviour Of Beryllium
Beryllium, the first element in Group 2, exhibits anomalous behaviour compared to other alkaline earth metals. This is due to its **exceptionally small atomic and ionic size** and **high ionisation enthalpy**, leading to its compounds having significant **covalent character**. Its properties also show a **diagonal relationship** with aluminium in Group 13.
Points of difference from other alkaline earth metals:
- Small size and high ionisation enthalpy lead to covalent compounds and easy hydrolysis.
- Does not exhibit coordination number greater than 4 (only 4 valence orbitals). Others can use d-orbitals for coordination number 6.
- Oxide (BeO) and hydroxide (Be(OH)$_2$) are **amphoteric**. Others are basic.
Diagonal Relationship Between Beryllium And Aluminium
Be resembles Al due to similar ionic sizes (Be$^{2+}$ 31pm, Al$^{3+}$ 53.5pm) and charge/radius ratios. Similarities:
- Both are not readily attacked by acids due to oxide film formation.
- Their hydroxides are amphoteric and dissolve in excess alkali to form beryllate ([Be(OH)$_4$]$^{2-}$) and aluminate ([Al(OH)$_4$]$^-$ or [Al(H$_2$O)$_2$(OH)$_4$]$^-$) ions.
- Their chlorides (BeCl$_2$, AlCl$_3$) are covalent, soluble in organic solvents, have bridged structures in the vapour phase, and are strong Lewis acids (used as Friedel-Crafts catalysts).
- Both ions form complexes (e.g., BeF$_4^{2-}$, AlF$_6^{3-}$).
Some Important Compounds Of Calcium
Calcium compounds like calcium oxide (quick lime), calcium hydroxide (slaked lime), calcium carbonate (limestone), calcium sulphate (gypsum, plaster of Paris), and cement are industrially important.
- Calcium Oxide (Quick Lime, CaO): Prepared by heating limestone (CaCO$_3$) in a kiln. White amorphous solid, high melting point. Reacts with water (slaking) to form Ca(OH)$_2$. Basic oxide, reacts with acidic oxides (SiO$_2$, P$_4$O$_{10}$). Used in cement, as an alkali, in sugar purification.
- Calcium Hydroxide (Slaked Lime, Ca(OH)$_2$): Prepared by adding water to CaO. White amorphous powder, sparingly soluble in water. Aqueous solution is lime water, suspension is milk of lime. Reacts with CO$_2$ to form CaCO$_3$ (turns lime water milky). Reacts with chlorine to form bleaching powder. Used in mortar, white wash, glass making, tanning, bleaching powder production, sugar purification.
- Calcium Carbonate (CaCO$_3$): Occurs as limestone, chalk, marble. Prepared by reacting Ca(OH)$_2$ with CO$_2$ or CaCl$_2$ with Na$_2$CO$_3$. White powder, almost insoluble in water. Decomposes on heating to CaO and CO$_2$. Reacts with dilute acids to liberate CO$_2$. Used as building material (marble), for quick lime production, as flux in metallurgy, in paper, toothpaste, cosmetics.
- Calcium Sulphate (Plaster of Paris, CaSO$_4$·½H$_2$O): Hemihydrate of calcium sulfate. Obtained by heating gypsum (CaSO$_4$·2H$_2$O) to 393 K. Sets with water to a hard solid (forms gypsum). Used in building, as plasters, for immobilising fractures, in dentistry, for casts.
- Cement (Portland cement): Important building material. Made by strong heating of limestone and clay to form clinker, then mixed with gypsum (2-3%). Main ingredients are dicalcium silicate, tricalcium silicate, tricalcium aluminate. Setting is due to hydration and rearrangement of constituents. Used in concrete, plastering, construction.
Biological Importance Of Magnesium And Calcium
Magnesium and calcium ions are vital in biological systems:
- **Magnesium ions (Mg$^{2+}$):** Cofactor for all enzymes that use ATP in phosphate transfer (energy metabolism). Component of chlorophyll (light absorption in plants).
- **Calcium ions (Ca$^{2+}$):** Major component of bones and teeth ($\approx 99\%$ of body calcium). Essential for neuromuscular function, nerve transmission, cell membrane integrity, and blood coagulation. Blood calcium levels are tightly regulated by hormones.
Calcium is continuously exchanged between bone and plasma, highlighting the dynamic nature of bone tissue.
Exercises
Question 10.1 What are the common physical and chemical features of alkali metals ?
Answer:
Question 10.2 Discuss the general characteristics and gradation in properties of alkaline earth metals.
Answer:
Question 10.3 Why are alkali metals not found in nature ?
Answer:
Question 10.4 Find out the oxidation state of sodium in $Na_2O_2$.
Answer:
Question 10.5 Explain why is sodium less reactive than potassium.
Answer:
Question 10.6 Compare the alkali metals and alkaline earth metals with respect to (i) ionisation enthalpy (ii) basicity of oxides and (iii) solubility of hydroxides.
Answer:
Question 10.7 In what ways lithium shows similarities to magnesium in its chemical behaviour?
Answer:
Question 10.8 Explain why can alkali and alkaline earth metals not be obtained by chemical reduction methods?
Answer:
Question 10.9 Why are potassium and caesium, rather than lithium used in photoelectric cells?
Answer:
Question 10.10 When an alkali metal dissolves in liquid ammonia the solution can acquire different colours. Explain the reasons for this type of colour change.
Answer:
Question 10.11 Beryllium and magnesium do not give colour to flame whereas other alkaline earth metals do so. Why ?
Answer:
Question 10.12 Discuss the various reactions that occur in the Solvay process.
Answer:
Question 10.13 Potassium carbonate cannot be prepared by Solvay process. Why ?
Answer:
Question 10.14 Why is $Li_2CO_3$ decomposed at a lower temperature whereas $Na_2CO_3$ at higher temperature?
Answer:
Question 10.15 Compare the solubility and thermal stability of the following compounds of the alkali metals with those of the alkaline earth metals. (a) Nitrates (b) Carbonates (c) Sulphates.
Answer:
Question 10.16 Starting with sodium chloride how would you proceed to prepare (i) sodium metal (ii) sodium hydroxide (iii) sodium peroxide (iv) sodium carbonate ?
Answer:
Question 10.17 What happens when (i) magnesium is burnt in air (ii) quick lime is heated with silica (iii) chlorine reacts with slaked lime (iv) calcium nitrate is heated ?
Answer:
Question 10.18 Describe two important uses of each of the following : (i) caustic soda (ii) sodium carbonate (iii) quicklime.
Answer:
Question 10.19 Draw the structure of (i) $BeCl_2$ (vapour) (ii) $BeCl_2$ (solid).
Answer:
Question 10.20 The hydroxides and carbonates of sodium and potassium are easily soluble in water while the corresponding salts of magnesium and calcium are sparingly soluble in water. Explain.
Answer:
Question 10.21 Describe the importance of the following : (i) limestone (ii) cement (iii) plaster of paris.
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Question 10.22 Why are lithium salts commonly hydrated and those of the other alkali ions usually anhydrous?
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Question 10.23 Why is LiF almost insoluble in water whereas LiCl soluble not only in water but also in acetone ?
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Question 10.24 Explain the significance of sodium, potassium, magnesium and calcium in biological fluids.
Answer:
Question 10.25 What happens when
(i) sodium metal is dropped in water ?
(ii) sodium metal is heated in free supply of air ?
(iii) sodium peroxide dissolves in water ?
Answer:
Question 10.26 Comment on each of the following observations:
(a) The mobilities of the alkali metal ions in aqueous solution are $Li^+ < Na^+ < K^+ < Rb^+ < Cs^+$
(b) Lithium is the only alkali metal to form a nitride directly.
(c) $E^0$ for $M^{2+}(aq) + 2e^– \rightarrow M(s)$ (where M = Ca, Sr or Ba) is nearly constant.
Answer:
Question 10.27 State as to why
(a) a solution of $Na_2CO_3$ is alkaline ?
(b) alkali metals are prepared by electrolysis of their fused chlorides ?
(c) sodium is found to be more useful than potassium ?
Answer:
Question 10.28 Write balanced equations for reactions between
(a) $Na_2O_2$ and water
(b) $KO_2$ and water
(c) $Na_2O$ and $CO_2$.
Answer:
Question 10.29 How would you explain the following observations?
(i) BeO is almost insoluble but $BeSO_4$ is soluble in water,
(ii) BaO is soluble but $BaSO_4$ is insoluble in water,
(iii) LiI is more soluble than KI in ethanol.
Answer:
Question 10.30 Which of the alkali metal is having least melting point ?
(a) Na
(b) K
(c) Rb
(d) Cs
Answer:
Question 10.31 Which one of the following alkali metals gives hydrated salts ?
(a) Li
(b) Na
(c) K
(d) Cs
Answer:
Question 10.32 Which one of the alkaline earth metal carbonates is thermally the most stable ?
(a) $MgCO_3$
(b) $CaCO_3$
(c) $SrCO_3$
(d) $BaCO_3$
Answer: