Brilliant STUDY CENTRE LT -2023 (Lecture Note)

s – BLOCK ELEMENTS

In the modern periodic table Group 1& 2 elements having outer EC. ns1 and ns2 are s–block
elements.
n– principal Quantum no. (Bohr)
Group I [Alkali metals ] – outer EC – ns1
They are Li, Na, K, Rb, Cs & Fr is radioactive
227 4 223
Ac He2+ + Fr t 1  22.mm
89 2 87 2
 21.8
 ray/particle
These elements are known as alkali metals, because their compounds are strong bases [supply
OH– ions in aqueous medium]
But the word originated from an Arabic word Alquili/Alquis  Ashes of plants
General characteristics :
1. Alkali metals are silvery white, soft metals, they can be cut with a knife.
They have low M.P & B P due to weak metallic bonding [Drude & Lorentz]. But they are
good conductors.
2. Size & Reactivity : They have biggest size in respective periods & Down the group size
increases, I.E value decreases (due to screening effect of inner electrons) So they are most
reactive elements in P.T.
They have grater tendency to form unipositive ion

M  M   1e
ns1 ns0
 Paramag   diamag 

IE
Li  520 KJ/m
Na = 496
K = 419
Rb = 403
Cs  376
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Brilliant STUDY CENTRE LT -2023 (Lecture Note)

But Li - exception
Li - mainly form covalent compound due to high I.E small size & high polarising power
[Fajans rules]
Eg: LiCl, LiBr, LiI
But Li  F ionic [Due to high EN of F]
Note
LiCl LiBr LiI – soluble in organic solvents pyridine, ether, benzene etc
LiF ionic insoluble in water due to high lattice energy
3. Order of hydration in enthalpy in aq. medium
Li   Na   K   Rb   Cs
So LiCl exist as LiCl. 2H2O
4. Alkali metals have low density
mass of unit cell M Z
d 
Vol. of unit cell N A  a 3
Lowest ‘d’ for Li  0.53 g/cm3
Li < K < Na < Rb < Cs
0.53 0.86 0.99 1.53 1.9 g/cm3

Rb Cs

d Na

Li K

z
5. Alkali metals are normally kept in kerosene, because very reactive, react with air, O2, CO2
moisture & get tarnished in air.
They even catch fire with moisture

2Na + 2H2O 2NaOH + H2 + heat

burn
So they are kept in kerosene. But Li – kept in paraffin wax
6. Alkali metals are powerful reducing agents. They have greater tendency to loss e . This is expressed
in terms of E value.

Eo   3.05V Application of ‘Li’

Li
Li

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Brilliant STUDY CENTRE LT -2023 (Lecture Note)

Chemical Reactions :
1. Reaction with air/O2

M + O2 heat Li2O, Na2O, K2O ....... (s)

monoxides/oxides
Covalent
ionic
excess O 2 Na 2O 2, K 2O 2 (s)
peroxi des

excess O 2
NaO 2 , KO 2 ..........

Superoxides/Dioxides (s)
Li has only one oxide Li2O – small size & small nuclear charge
Others have large size & nuclear charge can form higher oxides.
Most stable oxide – Li2O can’t be hydrolysed (covalent)
But others are hydrolysed.
Na 2 O  H 2 O  2NaOH

Na 2 O 2  2H 2 O  2NaOH  H 2 O2

2NaO2 / 2KO2  2H2O  2NaOH H2O2  O2 

2KOH
Use of KO2 – Used in breathing apparatus by deep sea divers & mine workers
It react with ‘H2O’ in exhaled air lib – O2

CO 2   O2
Oxides & peroxides have no colour
Super oxides have yellow/orange colour due to unpaired e in antibonding M.O – paramag.

Li  Air 

 Li 2 O, Li 3 N
O2 / N 2

Others have no reaction with N2 covalent [N2– prefer to form covalent] high IE.

But Na  N 3 sodium azide ionic 2NaN3   Na  3N2  pure nitrogen
2. Reaction with H2O
vigorous NaOH + H + heat
Na + K+ H2O 2
cold KOH
burn

slow
Li  H 2 O   LiOH
  H 2
hot less stable

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Brilliant STUDY CENTRE LT -2023 (Lecture Note)

2LiOH Li2O + H2O

st able
3. Reaction with acids

2Na  2HCl  2NaCl  H2

2Na  H 2SO 4  Na 2SO 4  H 2

2K  2HCl  2KCl  H 2
4. Reaction with H2

2Na + H2 575 K 2Na+H

ionic hydride
2K + H2 575 K 2K+H

2Li + H2 1075 K 2LiH covalent hydride

g
Order of stability LiH > Na+H– > K+H–
5. Reaction with alcohol & Acetylene :-

2Na  2 C2 H 5OH 
 2 C2 H 5ONa  2  H 
nascent

 Na  C   C  Na   2  H 
2Na  HC  CH 
6. Reaction with Liq. NH3
8a
Tc 
27Rb
Tc for NH 3 132c / 405K

M+ (x+y) NH3 M+( NH3) x+ e ( NH3) y


blue colour,
conductivity & paramag.
Conc. can be increased by adding more alkali metal up to 5M, As conc. increases colour
blue  bronze of diamag. On heating

2Na  2NH 3 

 2NaNH 2  H 2
 sodamide
7. Reaction with halogens

 H 0f  -ve value
2M  X 2   2MX  exo 

M 2 O  2HCl 
HBr/HI
 2MCl  H 2 O

for Fluorides, down the group H 0f  less -ve

 stability decreases 
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Brilliant STUDY CENTRE LT -2023 (Lecture Note)

Stability
LiF > NaF > KF ......

 
For others Cl / Br / I


0
Down the group Hf  more -ve
 stability increases
LiCl < NaCl < KCl ........
LiBr < NaBr < KBr ........
Solubility:-
1. Almost all MX soluble in H2O
(hydration enthalpy > lattice enthalpy)
2. Li+F– ionic insoluble in H2O
(lattice enthalpy > hydration enthalpy) strong lattice
3. LiCl / LiBr / LiI are covalent in soluble in organic solvents  pyridine, ether, alcohol
4. Cs+I insoluble in H2O due to high lattice enthalpy & smaller hydration enthalpy
ionic
order of MP & BP : MF > MCl > MBr > MI
Note
Lithium perchlorate – ionic
LiClO4  soluble in H2O to greater extent
Salts of oxoacids
Acids with H+ present on –OH group, with an oxo group

H 2SO 4
Carbonic acid H2CO3 O O

C S
HO OH OH
O
OH

Alkali metals form salts with oxoacids

NaHCO3 NaHSO4
Na2CO3 Na2SO4
NaHCO3 /Na2CO3 are stable towards heat
Note
As electropositivity of alkali metal increases
Stability of HCO3 & CO32  salts increases
Li2CO3 is less stable decompose on heating
Li 2 CO 3 
  Li 2 O  CO 2
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Brilliant STUDY CENTRE LT -2023 (Lecture Note)

Na 2 CO 3 / K 2CO 3  
  No reacn No CO2
LiHCO3 will not exist solid But NaHCO3/KHCO3 exist as solid
Anomalous nature of ‘Li’
Reasons are 1) Small size of Li atom
2) High I.E 520 KJ/m
3) High polarising powers [Fajans’ rule]
ionic charge

 ionic radius 2
Anomalous properties
1. Li is hardest of alkali metals
2. High MP & BP, but powerful red. agent
3. It can form oxide & nitride Li2O & Li3N covalent
4. Li2O more stable than LiOH
5. Li –halides are covalent except Li+F– ionic
6. LiCl is a deliquescent solid LiCl. 2H2O – soluble in pyridine, alcohol
7. Li2CO3 less stable Li 2 CO3 

 Li 2O  CO 2
others carbonates are stable even at high temp.

8. 4LiNO 3 

 2Li 2 O  4NO 2  O 2 Reddish brown gas
but
2NaNO 3 2NaNO 2 + O 2
2KNO 3  2KNO 2 + O 2
no brown gas
9. All have solid bicarbonate but Li – does not have solid bicarbonate
10. LiF & Li2O – less soluble in H2O
Diagonal relation Li  Mg
Reasons
1. Similar size /radii Li  152 pm Mg = 160 pm
+
Li  76 pm Mg2+ = 72 pm
2. EN values are very close Li =1 Mg = 1.2
3. Same polarising powers
Similarities are
1. Li & Mg – very hard – high MP & BP
2. They form oxide & nitride Li2O, Li3N, MgO, Mg3N2

3. Li2CO3 & MgCO3 – unstable 
  CO 2
4. They have no solid bicarbonate

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Brilliant STUDY CENTRE LT -2023 (Lecture Note)

5. LiCl & M gCl 2  deliquescent solid

LiCl.2H2O & MgCl2.8H2O – Soluble in org.solvents (pyridine, ethanol)
6. Their nitrate on heating give NO2 gas [Reddish brown gas]
7. Their reaction with H2O very slow
8. LiOH & Mg (OH)2 – decompose on heating
Extraction
Alkali metals can’t be extracted by coke reduction, they are powerful reducing agents
& E0 value = –ve sign very high.
So they are extracted by electrolysis of their fused salts  Electrolytic reduction

Li :- exist as
1. Spodumene LiAlSi2O6 ––– ore
2.
3  
Lepidolite  LiAl  K SiAl O F  OH 
Rb
10
4
2

3. Amblygonite (LiNa) Al(PO4 ) F(OH)

LiCl prepared from the ore spodumene
Li – extracted by electrolysis of LiCl & LiF fused mixture
Li  At cathode
Cl2  anode
Uses
1. As a reducing agent
2. For making alloys
3. Li –Al–alloy for making cutting tools
4. Li –used as anode in battery & cells
5. Li – Al – alloys – used in aircraft industry
6. Li Mg – alloy – for making armour plates
Na :- exist as
1. NaCl – common salt – Rocks salt  ore
2. NaNO3 – chile saltpeter
3. NaSO4. 10H2O Glauber salt
4. Na2SO4 – salt cake
5. Na3AlF6 – cryolite
Na  extracted by electrolysis in Downs’ cell/process
NaCl CaCl2 traces
40% 60% of KF

lower MP of NaCl
Na  at cathode Cl2  anode
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Brilliant STUDY CENTRE LT -2023 (Lecture Note)

Use of Na
1. NaHg used as reducing agent
2. Na used for preparation of Na2O2, NaNH2 & NaCN
3. Liquid Na - used as covalent in nuclear reactors
4. Liq. Na/K alloy used in hightemp thermometer
5. Na - Pb alloy used for preparation of TEL (It was used as antiknocking agent in petrol)

4NaPb  4 C 2 H 5 Br   C 2 H 5 4 Pb  4NaBr  3Pb

TEL
6. Na used for detection of N, S & halogens in organic compounds [Lassaigne’s test]
Compounds of alkali metals
1. Na2O2 – sodium peroxide  Oxone
Al trays
Prepn 2Na  O 2   Na 2O 2
S
Air face from H2O & CO2 Pure colourless solid
Some times pale yellow colour due to traces of NaO2
Uses
1. As an Ox. agent
2. As a source of CO2 gas  oxone
3. As a bleaching agent
4. As a lab reagent
5. For prepn H2O2 Na2O2 + H2SO4  Na2SO4+H2O2 (Merck’s process)
2. Nacl–Rock salt/ Common salt
Obtained /manufactured by solar evaporation of sea H2O – NaCl forms
It contain impurities like Na2SO4 CaSO4, MgCl2, CaCl2 - more soluble

deliquescent - solids
So crude NaCl become wet on keeping
Purification :-
1. Prepare salt soln of NaCl in H2O
2. Pass HCl gas - Due to common ion effect NaCl comes out
3. Filter – Dried by heating & add small amount of KIO3  iodised table salt
Uses :-
1. As a taste maker in food stuffs
2. As a food preservative
3. For the prepn of NaOH, Na2CO3, NaHCO3 etc
4. For extraction of soap (salting out process)
5. NaCl + ice  used as freezing mixture
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Brilliant STUDY CENTRE LT -2023 (Lecture Note)

3. Sodium carbonate Na2CO3.10H2O  washing soda

Na2CO3  Soda Ash
By solvay process (Ammonia Soda Process)
Principle
Reagents NH4OH soln, CO2 and Brine (conc NaCl soln)
Process :- CaCl biproduct
2
Solvay process
Note :-
K2CO3 [Pearl Ash] can’t be prepd by
Solvay process –– KHCO3 formed soluble in medium can’t be filtered. So it prepd
by Le–Blanc process
Na2CO3.10H2O  efflorescent salt – soluble in water
Uses:-
1. As a softening agent for hard water
2. Na2CO3+K2CO3–– Fusion mixture
3. For quantitative & quantitative analysis in Analytical chemistry
4. For manufacture of washing soda & washing soap
5. Manufacture glass, paper, borax .....
K2CO3 – for soft soap & hard glass
NaHCO3 – Baking Soda
1. Prepd by solvay process
2. Pass excess CO2 through Na2CO3
Na 2 CO3  H 2O  CO2  2NaHCO3 white solid (Powder)
excess
Uses
1. In prepn of Baking powder & Baking soda
Na–HCO3 + K–H –tartrate
2. Used in medicine – Antacid
3. in fire extinguisher – NaHCO3+ Sand – Dry powder
NaHCO3  Al2  SO 4 3  H 2SO4
dil
Foamite oil fire extinguisher
4. As antiseptic
4. As antiseptic powder – seidlitz powder – for skin infection
NaHCO3+ Na -K- tartrate

Rochelle salt

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Brilliant STUDY CENTRE LT -2023 (Lecture Note)

NaOH – Castic Soda

1. Castner Kellner process
Brine electrolysed H2 & Cl2 + NaOH white deliquescent (translucent)
2. Nelson cell/ Diaphragm cell
3. Nafion membrane cell MP 591 K
Co-polymer – tetrafluoroethylene & perfluoro sulphonyl vinyl ether
When exposed NaOH + CO2  Na2CO3
Uses of NaOH
1. As a lab reagent
2. In the manufacture Dyes & Drugs
3. For purification of Bornite ore of Al (Al2O3)
4. Manufacture of soap, silk, paper
5. Prepn of pure fats & oils
6. For Mercerizing cotton – in textile industry
Biological Importance Na & K
1. Na+ ion blood plasma – for transmission of nerve signals
2. Regulate transport of sugars and amino acids into cells
3. K+ ions in cell fluids activate enzymes
oxdn – glucose to  ATP
Na+ & K+ present in cell membrane /blood plasma – control amount of ATP
KI prepd from sea water
LiI + KF LiF + KI

Seperated by crystallisation
(s)
1. As a lab reagent
2. For prepn of dyes & drugs
3. For prepn of Nessler’s reagent

2KI + HgI2 K2[HgI4] in alkali medn

used for detection of NH3

NH2 Hg O Hg I
Group –2 [Outer EC –ns2]

Be, Mg, Ca, Br, Ba & Ra Ra  t 1  1600 years approx

2

All except Be - are alkaline earth, because Be - rare & its compounds are amphoteric

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Brilliant STUDY CENTRE LT -2023 (Lecture Note)

But compounds of others are basic, less basic than group -1

They exist in earth as CO32  & SO 24
1. Atomic size /radn less than group -1. So high I.E
Down group size increases IE decreases
I.E, Be - 899 KJ/, Mg = 737, Ca = 590, Sr = 549, Ba = 503
IE2 < IE value of alkali metals
2. They form dipositive ion
M M2+ + 2 e
ns2 nso
(diamag) (diamag)
But Be – exception small size, high IE, high polarising power
Be form covalent compounds BeCl2
BeF2 – ionic & soluble in water
due to hydration enthalpy Be2+ high
3. Hydration enthalpy group 2 > group 1
So compounds /salts are hydrated Be2+ > Mg2+ > Ca2+... > Ba2+
MgCl2 .6H2O, CaCl2. 6H2O ...... etc
4. They are weaker red. agents than group -1. due to high IE
5. They have strong metallic bonds. So high MP & BP
6. They have higher densities & harder than group -1

Be  1.85 gm/cm3
Mg 1.74 Sr  2.63
Lowest density Ca  1.55 Ba  5.6
7. Flame colouration
Be & Mg will not give colour to the flame due to high I.E. e are strongly attracted by
nucleus to excite in the flame.
Ca – Brick red, Sr – Crimson, Ba – Pale green / Apple green
Chemical Reactions
1. Reaction with air
2M  O 2 

 2MO H of   ve large values
So thermodynamically unstable
BeO –– Amphoteric oxides
Mg, CaO basic oxides
 All MO  H 2 O  M  OH   heat
2

CaO  H 2 O  Ca  OH  2  heat

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Brilliant STUDY CENTRE LT -2023 (Lecture Note)

Be  OH  2  amphoteric
Order of basic
Mg  OH  2  Ca  OH 2  Sr  OH  2  Ba  OH 2  solubility in H2O increases
hydra enthalpy same, lattice enthalpy decreases
Be / Mg  N 2  Be3 N 2 / Mg 3 N 2
covalent
Use
Mg 3 N 2  6H 2 O  3Mg  OH 2  2NH3 
2moles
2. Reaction with H2O

Mg / Ca  2H 2 O   Mg  OH 2  H 2
hot Ca  OH 2

But Be – no reaction with H2O even at high temp.

3. Reaction with acids

Mg / Ca  2HCl 
 MgCl2  H 2
CaCl2

Mg / Ca  H 2SO 4 
 MgSO 4 / CaSO 4  H 2
Be has no reaction with Acid, But Be -react with base
Be  NaOH 
  Na 2 BeO 2  H 2
Conc
4. Reaction with H2
Strong heat
M  H 2   MH 2
BeH2  covalent all others ionic
CaH2  Hydrolith (used for prepn of H2)
Stru. of BeH2/ prepn
BeCl2 +LiAlH4 
BeH2 + LiCl + AlCl3

exist as (BeH2)n polymeric
with brigdge bond

H H
Be Be Be Solid polymer
H H

5. Reaction with X2
M  X 2  MX 2

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Brilliant STUDY CENTRE LT -2023 (Lecture Note)

 NH 4 2 BeF4 
  BeF2  2NH 4 F

BeO  C  Cl2 

800K
 BeCl2  CO
coke

Cl Cl
Be Be Be Solid
Cl Cl

In vapour
Cl Be Cl at 1200 K
But below 1200 K BeCl2 exist as dimer
Cl
Cl Be Be Cl
Cl
BeCl2 + 2H2O Be(OH)2 + 2HCl 
moisture fumes
CaCl2, MgCl2 - used as drying agent
6. Reaction with liquid NH3
Same as alkali metals
7. Order of stability of CO32 &SO 42 (Oxosalts)

BeCO3 < MgCO3 < CaCO3 < SrCO3 < BaCO3

Stability & MP increases Isomorphous solids

insoluble in water used as refractory
materials for furnaces

BeSO4 < MgSO4 ........ < BaSO4

Soluble solubility in H2O insoluble in
in water decreases water
Nitrates
Mg  NO3 2 exist as Mg  NO3  2 .6H 2 O

Ba  NO3  2 ......... Ba  NO3  2


 hydration enthalpy decreases
All nitrates decompose on heating

2Mg  NO3  2   2MgO  4NO 2   O 2 

  
Brown Gas

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Brilliant STUDY CENTRE LT -2023 (Lecture Note)

Anomalous nature of Be
Reasons :- Small size, high IE, high EN & no ‘d’ orbitals
properties
1. Its oxide & hydroxide – amphoteric
2. It has no reaction with H2O
3. It has no reaction with acid, but react with base
4. BeCO3 – thermally unstable

 2Be  OH 2  CH 4
5. Be 2 C  4H 2 O 

 Mg  OH  2  C 2 H 2
MgC 2 / CaC 2  H 2 O 
Ca  OH 2

6. Be – has maximum co-ordination no - 4 – no d orbitals

Be  Al diagonal relations
1. Similar size, 2. EN values same, 3. Same polarising power
1. Their oxide & hydroxide are amphoteric
2. No reason with H2O
3. They react with base – lib. hydrogen [Be – no reason with acid - due to oxide coating]
4. Be 2 C & Al4 C3  H 2 O  CH 4

5. BeCl2 & AlCl3 exist as dimer in vap.state

6. BeO & Al2 O3  dissolve in excess of NaOH

7. Be3 N 2 & AlN  H 2O  NH 3 

8. They become passive in con.HNO3 – oxide coating
Difference
Be – maximum co-ordination = 4 Al – co-ordination no = 6
2 3
Na 2  BeF4  Na 3  AlF6 
 
sp3 sp3d2

Compounds of Ca & Mg
1. CaO quick lime
1270 K
CaCO3 CaO + CO2

Lime Stone Quick lime
(white amorphous solid)

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Brilliant STUDY CENTRE LT -2023 (Lecture Note)

CaO  H 2 O  Ca  OH 2 / CaO  CO 2  CaCO3

CaO – Basic oxide

CaO  SiO 2  CaSiO3 / 6CaO  P4O10  2 Ca 3  PO 4  2

Use
1. Manufacture of cement
2. Manufacture of Na2CO3, dyes
3. Purification of sugar
2. Ca(OH)2 – slaked lime
CaO + H2O Ca(OH)2
Quik lime white amorphous powder
(Aq.soln  milk of lime)

Ca  OH  2  CO 2  CaCO3  H 2O
soln

Ca  OH  2  A 2 O  CO 2  Ca  HCO3 2
excess Cal.Carbonate soluble

Ca  OH  2  Cl2  CaOCl2  CaCl2  2H 2 O


Bleaching powder
Uses Ca(OH)2
1. Ca(OH)2+ sand – mortar – building material
1:4
2. For white wash
3. Manufacture of glass - tanning of leather
4. manufacture of bleaching powder
5. Purification of sugar
CaCO3 - lime stone
naturally existing

Ca  OH 2  CO 2  CaCO3  H 2O
or

CaCl2  Na 2 CO3  CaCO3  2NaCl

White Powder

1270K
CaCO3   CaO  CO 2
It react with dil. acids. lib – CO2

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Brilliant STUDY CENTRE LT -2023 (Lecture Note)

Uses
1. Used in building industry (marble)
2. As a flux in metallurgy
3. For manufacture of glass /paper
4. Mild abrasive in tooth paste
5. Component in chewing gum & cosmetics
Gypsum & plaster of paris

 373 K
CaSO4.2H2O CaSO4.2H2O  CaSO4. 1 2 H 2 O
1.5 H 2 O
gypsum orthorombic or
(monoclinic) (CaSO4)2H2O
P. O. P
Hardening Add H2O
Setting
above
CaSO 4 .2H 2 O 
393K
 CaSO4
Dead burnt plaster

Uses
Cement Joseph Aspdin (1824)
Raw materials – lime stone, clay & gypsum

Lime stone CaO 50 60%

SiO2 20 25% Ca2SiO4 20%
Al2O2 5 10 % Ca3SiO5 5%
clay  powdered
MgO 2 3% gypsum
Ca3Al2O6 5%
Fe2O3 2 3% added
clinker
cement
Setting of cement
When H2O – added – hydration of molecules present & rearrangement takes place
& sets hard mass
(Presence & % of gypsum control setting time)
Biological importance of Ca & Mg
Mg – acts as co-factor for enzymes for their ATP transfer
Mg – present in chlorophyll – for absorption of light
Ca – present in bones & teeth – for neuro -function
Ca – present in celles
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Brilliant STUDY CENTRE LT -2023 (Lecture Note)

Ca – control - two hormones – calcitonin parathyroid

MgO - Magnesia:

MgCO 3 

 MgO  CO 2

Use:
Used as refractory material
As a flux
Sorel cement MgO.MgCl2.6H2O
Mg(OH)2 – suspension used as milk of magnesia (Antacid)

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