S-Block Elements

Li Na K Rb Cs Fr - Radiaoactive
Be Mg Ca Sr Ba Ra - Radioactive

S-Block
S-Block elements are those in which the last e- enters the outermost s-orbital The first element of alkali & alkaline earth metals differs in many respects from the other group elements
S-BLOCK ELEMENTS Group 1 (1s1) Alkali Metals Group 2 (1s2) Alkaline Earth metals

- named so as their hydroxides and oxides - named so as the oxides and are alkaline in nature hydroxides are alkaline in nature & found in the earths crust

ALKALI METALS
Properties Electronic Configuration Atomic & Ionic Radii Ionization enthalpy Trend [Noble Gas] ns1 As expected both increases down the group Size of M+ < size of M ** As expected it decrease down the group ** Values are considerably low in comparison to other elements of the periodic table as the metals are highly electropositive in nature

Hydration enthalpy

Alkali metals Density Flame test General features

is the energy released when an ion gets hydrated in H2O. Generally smaller the ion more is the hydration enthalpy Decreases down the group as the size increases
Increases down the group (except in K, where Na>K) Imparts characteristic colors to the flame Silvery white, soft, light , low MP and BP (indicating weak metallic bonding)

Alkali Metals-Chemical properties

General points:
High reactivity of alkali metals is due to their large size and low ionization enthalpy Due to the increase in size down the group, reactivity also increases

1. Reactivity towards air (mainly O2) & H2O

N2 (air)
Li Na

Li3N
LiO2 (oxide) Na2O2 (peroxide)

H2 + Hydroxides

H2O +

K Rb Cs

+ O2

KO2 RbO2 CsO2 superoxide

H2O
Oxides
A smaller cation can stabilize a smaller anion while a larger cation can stabilize a larger anion - So, the formation of Li2O, Na2O2, KO2 Oxides & peroxides are colorless. superoxides are yellow/orange in color & paramagnetic

Hydroxides
Reaction with H2O becomes increasingly violent down the group Alkali metal hydroxides are the strongest of all the bases & among them basic strength increases from LiOH ----> CsOH (strongest base)

2. Reactivity towards Halogens

M + X2 ------> MX
Order of reactivity of M Li < Na < K < Rb < Cs - X2 F2 > Cl2 > Br2 > I2 Except LiX all MX are ionic in nature Polarisation capacity of cation: Polarisability of anion: Due to the high polarisation capacity of Li+ ion The capacity of the cation to distort the e- cloud of anion. Smaller the cation, more is the polarisation The capacity of the anion to get distorted by the cation. Larger the anion, more is the polarisability

Higher the Polarisation & Polarisability, more would be the Covalent character

M2O/MOH/M2CO3 + HX (aq) ----> MX + H2O

All the MX have negative enthalpy of formation (-Hf) Solubility: halides are water soluble except LiF & CsI which are sparingly soluble. LiF - Due to high lattice energy CsI Smaller hydration enthalpy Li halides being covalent in nature, soluble in organic solvents MP & BP : MF > MCl > MBr > MI

3. With liq.NH3 & H2

Metallic cluster formation >3M
M+
H2 MH Hydrides (Ionic solids)

Bronze colour Diamagnetic

(x + y) NH3 (l)

<3M

[M(NH3)x]+ + [e(NH3)y]on standing MNH2 + H2 amides Deep blue

solution in liq. NH3 which is paramagnetic & conducting

3. With Oxo-Acids ---> Salts

Oxo-acids: are those in which the acidic H+ is on a hydroxyl group with an oxo (C=O, S=O) group attached to the same atom. Eg: O
O C HO OH HO S OH O

H2CO3 carbonic acid

H2SO4 sulphuric acid

M + oxo-acids

Oxo-salts

( carbonates - M2CO3 bicarbonates - MHCO3 sulphates - M2SO4 )

Soluble in H2O Except Li2CO3 (which decomposes on heating to Li2O) and LiHCO3 (which does not exist as a solid at RT) all other carbonates and hydrogen carbonates are thermally stable and their stability increases down the group due to the increase in electropositive character

Reducing property of Alkali Metals

Strong reducing agents Reducing property is measured by Standard electrode potential Value E Smaller the E value, greater will be the reducing character
E
is the overall change of M (s)
Sublimation enthalpy Ionization enthalpy

M(g)

M+ (g) + eH2O

Hydration enthalpy

M+ (aq)

for Li is less compared to other metals due to its high hydration enthalpy, so is the most powerful reducing agent

Anomalous properties of Li
Anomalous properties are due to 1. Small size of Li atom & ion 2. High polarising power 3. Non-availability of d-orbitals

4. Diagonal relationship with Mg

Difference b/w Li & other Alkali Metals

1. 2. Comparatively harder and having high MP & BP Li is comparatively less reactive. But, coming to the reducing property it is the strongest reducing agent It is the alkali metal on reaction with N2 (atm) forms LiN3 LiCl is the only alkali metal chloride which crystallizes in hydrate form i. e. LiCl. 2H2O Li unlike other alkali metals forms no ethynide on reaction with ethyne

3. 4.
5.

Li +
6.

HC CH

X
MNO3

LiC CLi

Lithium nitrate decomposes in a different fashion

Li2O + NO2 + O2 MNO2 + O2 M = Na, K, Cs, Rb M = Li Salts of Li are covalent in nature

7.

Diagonal relationship b/w Li & Mg

Relationship is due to their comparable sizes i. e.
Atomic Radii
Ionic radii Li 76pm Mg 72pm

152pm 160pm

Similarities: 1. 2. 3. 4. 5. 6. 7. 8. Both are harder and lighter than other elements in the group Reaction towards H2O is slow in both the cases Hydroxides of both the compounds decomposes on heating With N2, they form nitrides (LiN3, MgN3) Carbonates of Li & Mg decomposes on heating to give oxides + CO2 Solid hydrogen carbonates are not formed by Li & Mg Solubility properties of their compounds are similar Both LiCl and MgCl2 crystallizes in hydrate form ( LiCl.2H2O , MgCl2. 8H2O )

Industrially important compounds of Na

1. Sodium Carbonate (Na2CO3.10H2O) Washing Soda:

Preparation: by Solvay process Principle: Low solubility of NaHCO3 allows its precipitation from the solution. NaHCO3 thus obtained is heated to get Na2CO3 Process: ** pass CO2 to a concentrated solution of NaCl saturated with ammonia which gives NaHCO3 ** Heat NaHCO3 to get Na2CO3
2 NH3 + H2O + CO2 (NH4)2CO3 H2O + CO2 2 NH4HCO3 NaCl Na2CO3 + CO2 +H2O NaHCO3 (ppt) + NH4Cl Ca(OH)2 2 NH3 + CaCl2 + H2O

NH3-recovered

[Note: Solvay process cant be extended to prepare K2CO3 bcoz KHCO3 is highly soluble]

contd
Properties:
Na2CO3 .10H2O
Washing soda

375K

Na2CO3.H2O + 9H2O

>375K

Na2 CO3 + H2O

Soda ash

It hydrolyses in H2O giving alkaline solution of NaOH

Na2CO3 + 2 H2O 2 NaOH + H2CO3

2 . Sodium Hydrogencarbonate (NaHCO3) Baking Soda:

Preparation: by saturating the solution of Na2CO3 with CO2. NaHCO3 being less soluble precipitates out
Na2CO3 + CO2 +H2O 2 NaHCO3

NaHCO3

Na2CO3 + CO2 +H2O

Evolution of this gas leaves bubbles in baking items making it light

Industrially important compounds of Na

Properties
MP Preparation Procedure

3. NaCl
808 o C (1081 K) By the evaporation of sea water Impurities: CaCl2, MgCl2, CaSO4, Crude salt is dissolved in minimum amount of H2O & filtered to remove insoluble impurities Saturate the solution with HCl gas (common ion effect) Crystals of pure NaCl separates out Impurities being more soluble remain in solution

4. NaOH (Caustic soda)

318 o C (591 K) Electrolysis of brine solution in Castner-Kellner cell Electrolyte: Saturated solution of NaCl Anode (oxidation): Carbon electrode Cathode (reduction): Hg-electrode
Anode Cathode 2 Cl2Na + + 2e2Hg Cl2 + 2e2Na-Hg

Cell

2NaCl +2Hg

2Na -Hg + Cl2 2H2 O

2 NaOH + H 2 + 2Hg

NaOH solution at the surface reacts with atmospheric CO2 giving Na2CO3

Uses of alkali metals & its compounds

Alkali Metals Li -to make alloys In thermonuclear reactions Liq Na is used as a coolant in nuclear reactors Cs in photoelectic cells etc Na2CO3 H2O softening Laundering Used for qualitative & quantitative analysis NaHCO3 Mild antiseptic In fire extinguisher NaCl For domestic purpose For the preparation of Na2O2, NaOH, Na2CO3 etc NaOH in the manufacture of soap, paper etc In the purification of bauxite ore In petroleum refining Preparation of pure fats & oils etc

Biological importance of Na+ & K+

A 70 kg man contains about 90g of Na+ & 170 g of K+ Belonging to the same group both Na & K are chemically similar, but they perform different biological functions
Na+
Abundant in blood plasma & in the interstitial fluid which surrounds the cell Occurrence

K+
Abundant in the cell fluid

Blood Plasma : Na+ = 143mmol/L & K+ = 5mmol/L Within red blood cell: Na+ = 10mmol/L & K+ = 105mmol/L This ionic gradient within & out of the cell is necessary for the functioning of the body. To maintain this a Sodium-Potassium Pump always operates across the cell membrane by consuming the energy. Transmission of nerve signals Regulate the flow of H2O across cell membrane Transport of different sugars & amino acids into cells Transmission of nerve signals To activate a variety of enzymes in the cell fluids Promote the oxidation of glucose into ATP

Function

ALKALINE EARTH METALS

Properties Electronic Configuration Atomic & Ionic Radii Ionization enthalpy Hydration enthalpy Flame test Trend [Noble Gas] ns2 As expected both increases down the group Size of M+ < size of M ** As expected it decrease down the group ** First IE of alkaline earth metals are higher than those of the Gp 1 Metals due to their comparatively smaller size Decreases down the group as the size increases Values are larger in comparison to that of alkali metal ions. As a result compounds of the elements are extensively hydrated Ca, Sr & Ba imparts characteristic colors to the flame As it is difficult to knock of e- from Be & Mg, they do not impart any color Helpful in qualitative analysis Strongly electropositive in character & the behavior increases down the group

General features

Alkaline Earth Metals-Chemical properties

Group 2 elements show the same trends in properties as were observed with Group 1 elements But, Be stands apart from the rest of the group, & differs much more from them than Li does from the rest of Group 1 Reason: Relative increase in size from Be2+ to Mg2+ is 4 times greater than the increase between Li+ & Na+ Elements are highly reactive metals , but are less reactive in comparison to alkali metals Compounds of Group 2 are less ionic compared with Group 1 compounds Compounds of Be & Mg have more covalent property As the electro positivity increases down the group, reactivity also increases

Alkaline Earth Metals-Chemical properties

1. Reactivity towards Air & H2O:
With H2O M + H2O ------> M(OH)2 With Air M + (O2 + N2) ------> MO + M3N2

Be is relatively unreactive in the massive Be does not react with H2O, whereas Mg form, but the powder is much more reactive demands boiling H2O or steam conditions Other members react even with cold H2O
Mg being more electropositive, burns with intense light & evolves a lot of heat which is used in thermite reactions & flash photography Oxides MO + H2O -------> M(OH)2 Except BeO all MO have rock-salt structure Hydroxides Be(OH)2 is amphoteric in nature whereas other hydroxides are basic Solubility & the basic strength increases down the group

BeO is amphoteric, whereas other MO are basic in nature

Solubility:
Solubility of any salt is influenced by lattice enthalpy as well as hydration enthalpy Lattice enthalpy (LE): Energy required to separate the ions from one mole of the solid to infinite distance in the gaseous state Hydration enthalpy (HE): Energy releases due to the hydration of one mole ions of the salt If LE > HE, then salt does not dissolve If LE < HE, then salt dissolves Coming to Group 2, As we move down the group both LE & HE will decrease But the decrease in LE is more compared to HE, so the solubility increases

2.

Reactivity towards Halogens:

M + X2 -------> MX2 (At elevated temperature)
BeO + 2NH3 + 4HF C + Cl2 600-800 K BeCl2 + CO (NH4)2[BeF4] 2BeF 2 + 2NH4F

Halides Tendency to form halide hydrates decreases down the group MgCl2.8H2O, CaCl2.6H2O, SrCl2.6H2O, BaCl2.2H2O All the MX2 are ionic in nature except BeX2 which are covalent & soluble in organic solvents BeCl2

Solid state

Vapour phase
Cl Cl Be Cl Be Cl

High T 1200 K

Cl

Be

Cl

Alkaline Earth Metals-Chemical properties

Towards Hydrogen All the elements form Hydrides upon heating with H2 except BeH2 as it is less stable However impure BeH2 can be prepared by 2 BeCl2 + LiAlH4 ------> 2BeH2 + LiCl + AlCl3 React with acid liberating H2 M + 2 HCl -----> MCl2 + H2 Strong reducing agents indicated by their negative E- values But, reducing power is less compared to alkali metals Reducing property is found to increase down the group Dissolves in liq NH3 giving deep blue black solution of ammoniated ions
[M(NH3)6]2+
ammoniates slow decomp evapor

Towards Acids Reducing property

Solutions in liq. NH3

[M(NH3)x]2+ + 2[e(NH3)y ]on standing M(NH2)2 + H2 amides

M(NH2)2 + 4NH3 + H2

Salts of Oxo-Acids
Carbonates
Decompose on heating to give Oxide & CO2 Thermal stability increases as we move down the group Carbonates are insoluble in H2O & precipitates upon addition of Na2CO3/(NH4)2CO3 (Removal of hardness of H2O) Solubility in H2O decreases as we move down the group --- As the size of the anion is much bigger, the increase in the size of cation down the group will not affect the Lattice enthalpy to a considerable extent. Whereas hydration enthalpy decreases down the group & the solubility decreases Are quite stable to heat upon heating to a very high T may decompose to oxide, SO2 & O2 BeSO4 & MgSO4 are readily soluble in H2O Solubility decreases down the group MCO3 + dil.HNO3 -----> M(NO3)2 + H2O + CO2 2M(NO3)2 decomposes on heating ------> 2MO + 4NO2 +O2 Mg(NO3)2.6H2O crystallizes in the hydrate form whereas Ba(NO3)2 is existing in anhydrous form

Sulphates

Nitrates

Anomalous properties of Be
Be stands apart from the rest of the group, & differs much more from them than Li does from the rest of Group 1 Difference in properties with the group Diagonal relationship b/w Be & Al members Compounds of Be are largely covalent & get easily hydrolyzed Like Al, Be is not readily attacked by acids because of the presence of an oxide film on the surface of the metal

As the valence shell of Be contains only Be(OH)2 dissolves in excess of alkali to give a 4 orbitals (one 2s and three 2p), highest beryllate ion, [Be(OH)4]2 just as Al(OH)3 coordination number exhibited is 4 aluminate ion, [Al(OH)4] The oxide and hydroxide of beryllium, The chlorides of both Be & Al have Cl bridged unlike the hydroxides of other elements structure in vapour phase. Both the chlorides are in the group, are amphoteric in nature soluble in organic solvents and are strong Lewis acids. They are used as Friedel Craft catalysts. Be & Al ions have strong tendency to form complexes, BeF42, AlF6 3.

Industrially important compounds of Ca

CaO Quick lime Prepn
CaCO3 lime stone CaO + CO2

Ca(OH)2 Slaked lime CaO + H2O -----> Ca(OH)2 Lime water : Aqueous solution of Ca(OH)2 Milk of lime : Suspension of slaked lime in water

Addition of limited amount of H2O breaks the quick lime lump & the process is called as Slaking of lime

On exposure to atmosphere, absorbs Moisture On passing CO2 through lime water CO2 & CO2
Ca(OH)2 (aq) CaCO3 + H2O

CaCO3

CO2

CaO

H2O

Ca(OH)2

CO2 excess Ca(HCO3)2

Being a basic oxide it combines with acidic oxides at high temperature

2Ca3(PO4)2 P4O10 CaO SiO2 CaSiO3

Milk of lime + Cl2 ------> Hypochlorite

2Ca(OH)2 2Cl2 Ca(OCl)2 + CaCl2 + 2H2O

Industrially important compounds of Ca

CaCO3 Limestone Prepn: 1. By passing limited amount of CO2 through slaked lime CaSO4.1/2H2O Plaster of Paris Hemihydrate of CaSO4
2(CaSO4. 2H2O) gypsum above 393K CaSO4 anhy 393 K 2(CaSO4). 1/2 H2O + 3H2O

2. CaCl2 + Na2CO3 ------> CaCO3 + 2NaCl

(dead burnt plaster)

Reacts with dilute acids liberating CO2 CaCO3 + 2HCl ------> CaCl2 + CO2 + H2O CaCO3 + H2SO4 -------> CaSO4 + CO= +H2O

On mixing with an adequate quantity of H2O it forms a plastic mass that gets hard in 5-15 min

Cement
Also called as Portland cement (P.Cement) due to its resembles with the natural limestone extracted in Isle of Portland

Average Composition of P.Cement

CaO SiO2 Al2O3

50-60% 20-25% 5-10%

MgO Fe2O3 SO3

2-3% 1-2% 1-2%

Ca2SiO4 Ca3SiO5 Ca3Al2O6

26% 51% 11%

For a good quality cement

1. Silica:Alumina 2. CaO: (SiO2+Al2O3+Fe2O3)

clay & lime cement clinker

in between 2.5 to 4 close to 2

2-3% by weight of gypsum cement

Manufacture of cement

Setting of Cement

When mixed with H2O cement becomes a hard mass due to the hydration & rearrangement of molecules Purpose of addition of gypsum is to slow down the process of setting of cement

Uses of Group 2 elements & its compounds

Group 2 Elements

Cu-Be alloys are used in the manufacture of high strength springs Be metal is used in making windows of X-ray tubes Mg-Al alloys being light is used in air crafts Milk of magnesia {suspension of Mg(OH)2 in H2O} is used as antacid Ca-is used as reducing agent for the extraction of Metals Radium salts are used in Radiotherapy
In the manufacture of cement, dyes and sodium carbonate Cheapest form of alkali In the purification of Sugar Preparation of Mortar A building material Used in white wash due to disinfectant nature In glass making industry, for the preparation of bleaching powder etc Used as a building material in the form of marble As flux in the extraction of metals As an antacid, mild abrasive in tooth paste, a constituent of Chewing gum, filler in cosmetics in the manufacture of high quality paper for making statues Used as plasters

CaO Quick lime Ca(OH)2 Slaked lime

CaCO3Lime stone CaSO4. 1/2H2O Plaster of Paris

Biological importance of Ca2+ & Mg2+

A n adult body contains about 25g of Mg & 1200g of Ca
Ca2+ Functions: neuromuscular functions Interneuronal transmission Cell membrane integrity Blood coagulation Ca concentration in plasma is 100 mg/L Mg2+ All enzymes that utilize ATP in phosphate transfer require Mg as the Cofactor

The main pigment for the absorption of light in plants is chlorophyll which contains Mg