Physical Chemistry

MOLE CONCEPT

Lecture - 01 FAISAL RAZAQ

Topics to be covered
Revision
QUESTION

Assuming that l, 3, 5-hexatriene has only pure double bonds and pure single bonds,
how many grams of it contain one mole of double bonds?

A 13.3 g

B 26.7 g

C 40 g

D 80 g
QUESTION

An amount of 5 millimoles of LiAlH4 was treated with 20 millimoles of

t-butyl alcohol. A total of 15 millimoles of hydrogen was evolved for the reaction:

LiAlH4 + 3(CH3)3COH → Li[(CH3)3CO]3 AlH + 3H2

The addition of an excess of another alcohol, methanol, to the above reaction

mixture caused the fourth H atom of the LiAlH4 to be replaced according to the
equation:

Li[(CH3)3CO]3AlH + CH3OH → Li[(CH3)3CO]3(CH3O)Al + H2

How many millimoles of H2 was evolved due to the addition of CH3OH?
QUESTION Match the following
Column I Mases of different components Column II Observation
(A) (P) Metal is the limiting reagent

(B) (Q) Halogen is the limiting reagent

(C) (R) Metal and halogen are in stoichiometric amounts

(D) (S) Metal is exhibiting a particular valency in the chloride formation.

(T) Metal is exhibiting variable valency in the chloride formation

QUESTION

A certain metal 'M' forms an insoluble oxalate complex M4O3(C2O4)3. 12H2O. If 3.2 g
of the complex is formed from 1 g of oxalic acid, what is the atomic mass of M?
QUESTION

A magnesium ribbon, when burnt in air, left an ash containing MgO and Mg3N2.
The ash was found to consume 0.6 mole of HCI, when it was taken in solution,
according to the reactions:
MgO + 2HCl → MgCl2 + H2O
Mg3N2 + 8HCl → 3MgCl2 + 2NH4Cl
The solution so obtained was treated with excess of NaOH, when 0.1 mole of NH3
was evolved. The mass (in g) of magnesium burnt is
QUESTION

Consider the following set of reactions :

CH3
O
CH – C – O – H
O
CH – C – O – H + AgNO3 → Silver salt → White residue
O (excess)

CH – C – O – H

CH3 n times
If 0.1 moles of silver salt is taken and wt. of residue obtained is 54 g then what will
be the molecular mass of CH3 – CH – CH – CH – CH3
Br Br Br
QUESTION

In a gravimetric determination of P, an aqueous solution of dihydrogen phosphate ion

H2PO4– is treated with a mixture of ammonium and magnesium ions to precipitate
magnesium ammonium phosphate, Mg(NH4)PO4.6H2O. This is heated and decomposed
to magnesium pyrophosphate, Mg2P2O7, which is weighed. A solution of H2PO4– yielded
1.054 g of Mg2P2O7. What weight of NaH2PO4 was present originally ?
A 1.14 g

B 1.62 g

C 2.34 g

D 1.33 g
Some Important Chemical Reactions
 Combination of Elements with oxygen

(i) Heating mercury at its boiling point in air.

Hg + O2 2HgO (red mercuric oxide)

(ii) Heating magnesium in air. It forms mostly magnesium oxide and some
magnesium nitride
2Mg + O2 2MgO
3Mg + N2 Mg3N2

(iii) Calcium behaves similarly.

2Ca + O2 2CaO
3Ca + N2 Ca3N2

(iv) Silver does not combine with oxygen, as Ag2O is unstable to heat.
(v) Many non-metals burn in O2 forming their respectively oxides.
2H2 + O2 2H2O ; S + O2 SO2
C + O2 CO2 ; P4 + 5O2 P4O10
3000°C
N2 + O2     
  2NO
Cl2, Br2 and I2 do not directly combine with oxygen.
 Action of Heat on Certain oxides

(i) Mercuric oxide and silver oxide are unstable to heat decompose
readily.
∆ ∆
2HgO 2Hg + O2 ; 2Ag2O 4Ag + O2

(ii) Various higher oxides, dioxides, mixed and peroxides are decomposed to
oxygen and a lower oxide.
3Pb3O4 6PbO + O2 ; 2PbO2 2PbO + O2
3MnO2 Mn3O4 + O2 ; 2BaO2 2BO + O2
 Compounds Rich in oxygen Decompose to give oxygen

(i) 2KNO3 2KNO2 + O2 ↑

(ii) 2KMnO4 K2MnO4 + MnO2 + O2 ↑
(purple) (green) (black)
(iii) 4K2Cr2O7 4K2CrO4 + 2Cr2O3 + 3O2 ↑
(orange-red) (yellow) (green)

Potassium chlorate when heated just above its melting point decomposes into potassium
perchlorate and potassium chloride. This reaction is called disproportionation or auto-
oxidation and auto-reduction. On heating further, KClO4 decomposes to KCl and oxygen.

(iv) 4KClO3 3KClO4 + KCl

KClO4 KCl + 2O2
 Action of Heat on Nitrates

Generally heavy metal nitrates decompose to metal oxide, reddish brown nitrogen
dioxide gas and oxygen.
(i) Lead nitrate decomposes to PbO, NO2 & O2.
2Pb(NO3)2 2PbO + 4NO2 ↑ + O2
litharge or lead (II) oxide
(red when hot and yellow when cold)
(ii) Cupric nitrate decomposes to CuO, NO2 & O2.
2Cu(NO3)2 2CuO + 4NO2 ↑ + O2
(green) (black)
(iii) Zinc nitrate decomposes to ZnO, NO2 & O2.
2Zn(NO3)2 2ZnO + 4NO2 ↑ + O2
(zinc oxide, yellow when hot and white when cold)
knowing the colours of some oxides will be useful in qualitative analysis.
(iv) Nitrate of mercury and silver, whose oxides are unstable, decompose into the
metal, NO2 & O2.
Hg(NO3)2 Hg + 2NO2 + O2
2AgNO3 2Ag + 2NO2 + O2
(v) Alkali metal nitrates decompose to give the metal nitrite and O2 (no reddish
brown NO2 gas).
2KNO3 2KNO2 + O2
2NaNO3 2NaNO2 + O2

(vi) Ammonium nitrate on heating leaves no residue and forms nitrous oxide and
steam.
NH4NO3 N2O + 2H2O
 Action of Heat on Ammonium Compounds

Generally an ammonium compound decomposes into ammonia and an acid or acidic

oxide if the acid is unstable to heat.
(i) NH4Cl NH3 + HCl
(ii) (NH4)2SO4 2NH3 + H2SO4
(iii) (NH4)3PO4 3NH3 + H3PO4
(iv) (NH4)2CO3 2NH3 + CO2 + H2O
(V) Ammonium compounds which do not given ammonia on heating are
ammonium nitrate, ammonium dichromate.
NH4NO3 N2O + 2H2O
NH4NO2 N2 + 2H2O
(NH4)2Cr2O7 N2 + 4H2O + Cr2O3
 Action of Heat on Metallic Carbonates

(i) Generally metallic carbonates decompose to give metal oxide and CO2.
900°𝐶𝐶
CaCO3 CaO + CO2 ↑
MgCO3 MgO + CO2 ↑
CuCO3 CuO + CO2 ↑
(pale green) (black)
PbCO3 PbO + CO2 ↑
(yellow)
ZnCO3 ZnO + CO2 ↑
(ii) Carbonates of strongly electropositive metals (alkali metal except lithium) do
not decompose on heating.
(iii) Silver carbonate decomposes to give the metal, CO2 & O2.
2Ag2CO3 2Ag + 2CO2 + O2
(iv) Ammonium carbonate (smelling salt) decomposes to give NH3, H2O & CO2.
All the products are in gaseous phase and there is no residue left.
(NH4)2CO3 2NH3 + H2O + CO2
 Action of Heat on Metallic Bicarbonates

(i) Only NaHCO3 and KHCO3 are solids; others are known in solution. All
bicarbonates decompose to give the metal carbonate, H2O & CO2.
2NaHCO3 Na2CO3 + H2O + CO2 ↑
Ca(HCO3)2 CaCO3 + H2O + CO2 ↑
Mg(HCO3)2 MgCO3 + H2O + CO2 ↑
 Action of Heat on Certain Hydrated Chlorides

Hydrated halides on heating are converted to oxides, H2O and halo acids.
(i) MgCl2.6H2O does not get completely dehydrated because MgCl2 is hdrolysed
by water to give basic MgCl2.
MgCl2.6H2O Mg(OH)Cl + 5H2O + HCl

(ii) Al2Cl6.12H2O Al2O3 + 6HCl + 9H2O

(iii) SnCl2.2H2O undergoes hydrolysis to form basic chloride.

SnCl2.2H2O Sn(OH)Cl + H2O + HCl
(iv) On heating, certain halides of metal ions in higher oxidation state changes to
halides of lower oxidation state.
2FeCl3 2FeCl2 + Cl2 2CuCl2 Cu2Cl2 + Cl2
 Action of Heat on Some Other Compounds

(i) When sodium sulphite is heated, it undergoes disproportionation reaction.

4Na2SO3 2Na2SO4 + Na2S

(ii) Sodium thiosulphate Na2S2O3. 5H2O loses water of hydration and becomes
anhydrous which on further heating gives a mixture of sodium sulphate,
sodium sulphide and Sulphur.
Na2S2O3. 5H2O Na2S2O3 + 5H2O
4Na2S2O3 3Na2SO4 + Na2S + 4S
(iii) When hydrated copper sulphate (blue vitriol) is heated, CuO & CO2 formed.
100°𝐶𝐶
CuSO4 . 5H2O CuSO4 . H2O + 4H2O
230°𝐶𝐶
CuSO4 . H2O CuSO4 + H2O
750°𝐶𝐶
CuSO4 CuO + SO3
2SO3 2SO2 + O2

(iv) Gypsum CaSO4.2H2O, when heated to 120–130° C forms a hemihydrate

called Plaster of Paris.
CaSO4 . 2H2O CaSO4. ½ H2O + 3/2 H2O
If heated above 200° C, it forms anhydrous calcium sulphate which does not
set with water.
(v) Green vitriol, FeSO4.7H2O, when heated forms Fe2O3, SO2, SO3 & H2O
2FeSO4 . 7H2O Fe2O3 + SO2 + SO3 + 14H2O

∆
(vi) MgSO4 . 7H2O MgSO4 + 7H2O
(Epsom salt)
∆
MgSO4 MgO + SO3

∆
(vii) Al2(SO4)3 . 18H2O Al2O3 + 3SO3 + 18H2O
(purple) (white)

∆
(viii) Cr2(SO4)3 . 18H2O Cr2O3 + 3SO3 + 18H2O
(green)
 ∆
(ix) Fe2(SO4)3 Fe2O3 + 3SO3
(yellow) (blackish brown)

∆
(x) 2FeSO4 Fe2O3 + SO3 + SO2
(light green) (blackish brown)

∆
(x) 2FeSO4 Fe2O3 + SO3 + SO2
(light green)
 Some other Useful Reactions

O3 + 2Kl + H2O 2KOH + I2 + O2

BaCO3 + HCl BaCl2 + CO2 + H2O
BaCl2 + H2CrO4 BaCrO4 + 2HCl
2BaCrO4 + 6Kl + 8H2SO4 3I2 + 2BaSO4 + 3H2SO4 + Cr2(SO4)3 + 8H2O
2CuSO4 + 4Kl Cu2I2 + I2 + 2K2SO4
2MnO4– + 5C2O42– + 16H+ 2Mn+2 + 10CO2 + 8H2O
2KMnO4 + 10FeSO4 + 8H2SO4 2MnSO4 + 5Fe2(SO4)3 + K2SO4 + 8H2O
Mn3O4 + 2FeSO4 + 4H2SO4 3MnSO4 + Fe2(SO4)3 + 4H2O
2NH2OH + 4Fe3+ N2O + H2O + 4Fe2+ + 4H+
MnO4– + 5Fe2+ + 8H+ Mn2+ + 5Fe3+ + 4H2O
KMnO4 + 5Kl + 4H2SO4 3K2SO4 + MnSO4 + 5/2 I2 + 4H2O
K2Cr2O7 + 6Kl + 7H2SO4 4K2SO4 + Cr2(SO4)3 + 3I2 + 7H2O