CHEMISTRY

P-BLOCK ELEMENTS
PHOSPHORUS HALIDES

• Phosphorus form two type of halide PX 3 X= (F, Cl, Br, I) and PX5 X =( F, Cl, Br)
• PHOSPHORUS TRICHLORIDE
• PREPARATION
• It is obtained by passing dry chlorine over heated white phosphorus
• It is obtained by the action of thionyl chloride with white phosphorus
• PROPERTIES
• Colorless,oily liquid,hydrolyses in the presence of moisture
• It react with organic compounds containing –OH group such as CH 3COOH,C2H5OH
• It has pyramidal shape ,phosphorus is sp 3hybridised.
• PHOSPHORUS PENTACHLORIDE
• PREPARATION
• Reaction of white phosphorus with excess of dry chlorine
• Action of SO2Cl2 on phosphorus
• PROPERTIES
• Yellowish white powder and in moist air it hydrolyses to POCl3 and finally gets converted to phosphoric acid
• Heated it sublimes,strong heatind decomposes
• It reacts with organic compound containing OH group converting to chloro derivatives.
• Reactiving with metals give corresponding chlorides
• Used in the synthesis of some organic compounds C2H5OH,CH3COCl.
• In gaseous and liquid phases,it has trigonal bipyramidal structure.Th three equatorial P-Cl
bonds are equivalent,two axial bonds are longer than equatorial bonds because axial bond
pairs suffer more repulsion than equatorial bonds.
• QUESTIONS

• Why does PCl3 fume in moisture?

• Are all five bonds in PCl5 molecule equivalent? Justify your answer.

• What happens when PCl5 is heated?

OXOACIDS OF PHOSPHORUS

• The compositions of of the oxoacids are interrelated in terms of loss or gain of H 2O or o- atom.
• In oxoacids phosphorus is tetrahedrally surrounded by other atoms.
• All these acids contain atleast one P=O and one P-OH bond
• The oxoacids in which phosphorus has lower oxidation state(less than +5)contain,in addition to
P=O and P-OH bonds,either P-P or P-H bonds but not both.
• These acids in +3 o.s of phosphorus tend to disproportionate to higher and lower o.s.
• The acids which contain P-H bond have strong reducing properties.
• H3PO3 andH3PO4 are dibasic and tribasic
• QUESTION

• How do you account for the reducing behaviour of H3PO2 on the basis of its structure?

• What is the basicity of H3PO4?

• What happens when H3PO3is heated?

GROUP 16 ELEMENTS

• Oxygen,sulphur,selenium,tellurium,polonium and livermorium

• Chalcogens
• ELECTRONIC CONFIGURATION-ns2np4
• Atomic and ionic radii increase from top to bottom
• Ionisation enthalpy decrease down the group,lower ionization enthalpy compared to group 15
• Oxygen has less negative electron gain enthalpy than sulphur
• From sulphur onwards the value become less negative to polonium
• Electronegativity decreases down the group.
PROPERTIES

• PHYSICAL PROPERTIES ,Large difference between the melting and boiling points of
oxygen and sulphur ?
• Oxidation states:The electronegativity of oxygen is high,so it show -2 o.s,except in OF 2
its stability decreases down the group,Other elements shoe +2,+4,+6.
• S,Se,Te usually show +4,+6
• Anomalous behaviour of oxygen due to small size and high electronegativity.

• Why H2O show hydrogen bonding but not H2S

REACTIVITY
REACTIVITY WITH HYDROGEN
• H2E type(E=O,S,Se,Te)
• Acidic character increases from O to Te
due to decrease in bond enthalpyof H-
E.
• Thermal stability also decreases.
• All hydrides except water show
reducing properties increases from S to
Te.
REACTIVITY WITH OXYGEN
• EO2 andEO3type. E=S,Se,Te,Po
• Reducing property of dioxide decreases
from SO2 to TeO2
• SO2is reducing and TeO2 is an oxidizing
agent
• Both types are acidic in nature
REACTIVITY WITH HALOGENS
• EX6,EX4EX2
• Stability of halide decreases in the
order F->Cl->Br->I-
• Amongst hexahalides,hexafluorides are
the only stable halides,all hexahalides
are gaseous in nature,octahedral
structure
• SF6 is exceptionally stable for steric
reason.
• SF4SP3d hybridization
trigonalbipyramidal shape,equatorial
position occupied by lone pair.
• Monohalides SP3 hybridization
• Dimeric nature S2Cl2 S2F2
• Undergo dispropotionation
QUESTIONS

• Write the order of thermal stability of the hydrides of group 16 elements.

H2S is less acidic than H2Te.Why

DIOXYGEN

• PREPARATION
• Heating oxygen containing salts such as chlorates, nitrates and permagnates.
• By the thermal decomposition of the oxides of metals low in the electrochemical series
• Hydrogen peroxide readily decomposed into water and dioxygen by catalyst.
PROPERTIES

Three stable
Colorless and odourless Soluble in water isotope,paramagnectic,even no
of electrons

Combination with other

React nearly with all metals and
nonmetals(except Au,Pt)
elements is strongly exothermic.
To initiate the reaction some heat
is required because bond
dissociation enthalpy of O-O is
high
QUESTIONS

• Which of the following doesnot react with oxygen directly?

Zn,Ti,Pt,Fe
Complete the following reactions
C2H4 + O2

4Al + 3O2
OXIDES

• A binary compound of oxygen element Is called oxide.

Acidic • An oxide that combine with water to give acid

• Nonmetal oxides are acidic.Some metal with
oxide high o.s are also acidic ex:SO2,CO2,N2O5

• An oxide that combine with water to give base

Basic oxide • Metal oxides are basic CaO,BaO

Amphoteric • Dual behaviour

oxide • React both with acid and base EX:Al2O3

NEUTRAL OXIDES

• Neither acidic nor basic. CO,NO,N2O

OZONE

• Allotrophic form of oxygen.

•  
• Ozone layer protects the earth surface from an excessive concentration of UV radiations
• PREPARATION
• When a slow dry steam of oxygen is passed through a silent discharge ,a conversion of oxygen to oxone occurs.The product is known as
ozonized oxygen.
3O2 O3 ,Endothermic process.
PROPERTIES: Pale blue gas,dark blue liquid,violet black solid
At high concentration (above 100 parts per million) causes nausea and headache
And also dangerously explosive REASON: Ozone is thermodynamically unstable withrespect to oxygen since its decomposition into
oxygen results in the liberation of heat ()
These two effects reinforce each other resulting in large negative Gibbs energychange for its conversion into oxygen
NASCENT OXYGEN

• O3 O2 + O ,Due to the ease with which it liberate atoms of nascent oxygen ,It acts a s powerful oxidizing agent.
• Examples
• PbS + 4O3 PbSO4 + 4O2
QUANTITATIVE METHOD FOR THE ESTIMATION OF OZONE GAS: When ozone reacts with an excess of potassium iodide
solution buffered with a borate buffer,iodine is liberatedwhich can be titrated against a standard solution of sodium thiodulphate.
Nitrogen oxides emitted from the exhaust sydtems of supersonic jet aeroplanes might be slowly depleting the concentration of the
ozone layer in the upper atmosphere
REASON: Nitrogen oxides combine very rapidly with ozone
NO + O3 NO2 + O2
FREONS:Another threat to ozone,which are used in aerosol sprays amd as refrigerants.
USES & QUESTIONS

• Used as germicide,disinfectant,sterilizing water.

• Used as oxidizing agent in the manufacture of potassium permagnate
• QUESTIONS:
• Why does ozone is a powerful oxidizing agent?
• How does ozone estimated quantitatively?
SULPHUR:ALLOTROPHIC FORMS

• Yellow rhombic sulphur( sulphur) and monoclinic ( sulphur)

•  
• Stable at room temp is rhombic sulphur, transforms to monoclinic sulphur when heated above 369 K
• RHOMBIC SULPHUR: Prepared by evaporating roll sulphur with CS2

• Insoluble in water,dissolves in benzene ,alcohol etc,readily dissolve in CS2.

• MONOCLINIC SULPHUR :Prepared by heating rhombic sulphur ina dish and cooling till crust formed,make two holes in crust drain
water,remove crust,needle shaped crystals found.
• It is stable above 369 K and transform into rhombic sulphur below it and viceversa
• At 369 K both are stable .This temp called transition temp.
• Both have S8 molecules.have puckered and has a crown shape

• Different forms of SULPHUR S8(puckered crown shape) S6 (chair form) S2(seen at elevated temp above 1000 K,paramagnetic like
dioxygen)
QUESTIONS

• Which form of sulphur is paramagnectic behaviour?

SULPHUR DIOXIDE

• PREPARATION

S+O2 SO3

SO32- +2H+ H2O +SO2 Treating

sulphite with dilute sulphuric acid

4FeS2 +11O2 2Fe2O3+8SO2 Roasting

of sulphide ore
PROPERTIES

• Colorlrss gas with pungent smell,highly soluble in water

• Passed through water forms sulphurous acid
• SO2+H2O H2SO4
• 2NaOH +SO2 Na2SO3 +H2O, reacts with sodiumhydroxide solution forming sodium sulphite,which inturn react
with sulphurdioxide forming sodium hydrogen sulphite
• Na2SO3 + H2O+SO3 2NaHSO3
• Its behaviour similar to carbondioxide
• SO2+Cl2 SO2Cl2
• 2SO2+O2 V205 2SO3
CONVENIENT TEST FOR SO2GAS

• 2Fe 3+ + SO2 +2H2O 2Fe2+ +SO42- +4H+

• 5SO2+2MnO4-+2H2O 5SO42- +4H+ +2Mn2+

• Sulphurdioxide is angular in shape,

• USES: Refiningg petro and sugar
• Bleaching wool and silk
• Disinfectant,preservative
• Used for the manufacture of sulphuric acid,sodium hydrogen sulphite,calcium hydrogen sulphite etc
QUESTIONS

• What happens when sulphurdioxide is passed through an aqueous solution of Fe(111)salt?

• How is the presence of sulphurdioxide detected?
OXOACIDS OF SULPHUR

• Sulphur forms a number of oxoacids H2SO3,H2S2O3 H2S2O4 H2S2O5, H2SO4 H2S2O7

H2S2O8
SULPHURIC ACID

• MANUFACTURE
• One of the most imp industrial chemical
• Manufactured by contact process involves 3 steps

• Burning of sulphur or sulphide ores in air to generate SO2

• Conversion of SO2 to SO3 by the reaction ton with oxygen in the presence of a catalyst
V 2 O5

• Absorption of SO3 in H2SO4to give oleum.