CHEMISTRY STUDY MATERIAL FOR CLASS – XII

SESSION – 2023-24

CHAPTERS INCLUDED –
1. SOLUTIONS – 7 MARKS
2. CHEMICAL KINETICS – 7 MARKS
3. ELECTROCHEMISTRY- 7 MARKS
4. d- & f- BLOCK ELEMENTS – 7 MARKS
5. COORDINATION COMPOUNDS – 7 MARKS
6. AMINES – 6 MARKS
7. BIOMOLECULES – 7 MARKS
8. ORGANIC CHEMISTRY (NAME REACTIONS, REASONING, DISTNCTION, MECHANISM)

SOLUTIONS

TWO MARKS QUESTIONS

1. Define the term molarity and molality. What is the effect of temperature on these concentration terms?
Ans – No of moles of solute in 1 litre of solution is molarity whereas no of moles of solute in 1 kg of solvent is
called molality. Molality does not change with temperature whereas molarity changes because M depends on
volume and volume changes with temperature change.
2. State Henry’s law and explain the effect of it solubility of gases in liquids.
Ans – “Solubility of a gas in a liquid is directly proportional to the partial pressure of the gas present above the
surface of liquid or solution”. More the value of KH, less will be the solubility of the gas.
P=KH x
3. Why an aquatic animals are more comfortable in cold water in comparison to the hot water?
Ans: According to Henry's Law,
p =Kh * χ
Where Kh = Henry's law constant.
Solubility is indirectly proportional to Henry's constant.
As temperature increases, Kh increases, hence, solubility decreases. So, it is difficult for aquatic species to
breathe dissolved oxygen.
4. Helium is added to oxygen used by deep sea divers because:
Ans: Air contains a large amount of nitrogen and the solubility of gases in liquids increases with increase in
pressure according to Henry’s law. When sea divers dive deep into the sea, large amount of nitrogen dissolves in
their blood. When they come back to the surface, solubility of nitrogen decreases, and it separates from the
blood and forms small air bubbles. This leads to a dangerous medical condition called bends. Therefore, air in
oxygen cylinders used for diving is mixed with helium gas. This is done because helium is less soluble in blood
than nitrogen.

5. Give reason for the following: At high altitudes, people suffer from a disease called anoxia. In this disease, they
become weak and cannot think clearly.
Ans: At higher altitudes, the partial pressure of oxygen is less than that at ground level, so that oxygen
concentration becomes less in blood or tissues. Hence, people suffer from anoxia.
6. State Roult’s law if (i) both the components of a solution is volatile and (ii) solution contains a non-volatile
solute.
Ans – (i) Partial vapour pressure of each component in the solution is directly proportional to its mole fraction
present in the solution.
(ii) The vapour pressure of the solution containing non-volatile solute is directly proportional to the mole
fraction of solvent only.
 Raoult’s Law for Solutions Containing Non-Volatile Raoult’s Law for Solution Containing Volatile
Solute Solute

7. Compare ideal and non-ideal solutions.

Ideal Solution Non Ideal Solution

Follows Raoult’s law at all temperature and Does not follow Raoult’s law at all temperature and
concentrations. P = PA + PB pressure. P ≠ PA + PB
Intermolecular forces in resulting solution are Intermolecular forces in resulting solution are different
same as in pure components. from the inter molecular force of pure components. A
A–B=A–A=B–B – B ≠ A – A, B – B
No change in volume while mixing components. Change in volume while mixing components.
Δ V mix = 0 Δ V mix ≠ 0
No heat change take place while mixing the Heat changes take place while mixing the
components. Δ H mix = 0 components. Δ H mix ≠ 0
Eg: n–hexane+ n–heptanes & benzene + toluene Eg: Acetone + Water &Acetone + CHCl3

8. Compare non-ideal solutions showing positive and negative deviations.

Showing Positive elevation from Raoult’s Law Showing Negative Deviation from Raoult’s
Law
PT > PA + PB Resulting intermolecular force PT < PA + PB Resulting intermolecular
isweaker than pure components. force isstronger than pure components.
Δ V mix = +ve Δ V mix =
–ve
Δ H mix = +ve Endothermic mixing process Δ H mix = –ve Exothermic process
Acetone + Water , Alcohol + Water
Carboxylic Acid + Water

9. Azeotropes: (Constant Boiling Mixture) :-Solution in which components are present in a fixed proportion, boils
at a constant temperature irrespective of boiling point of pure components
๏ Minimum Boiling Azeotropes: Boils at a temperature lower than b.ps. of pure components. [95%
Alcohol]
๏ Maximum Boiling Azeotropes: Boils at a temperature higher than b.p.s. of pure components. [68%
HNO3]
10. Define (i) Van't Hoff factor (ii) abnormal molar mass? How will abnormal molar mass be corrected?
Ans – (i) Van't Hoff factor (i) gives the extent of association or dissociation of the solute particles in the
solution. It may be defined as the ratio of observed colligative property to calculated colligative property.
 (ii) Due to association or dissociation of solute particles in the solution the molar mass observed is found
different from actual molar mass of the solute. Now the observed molar mass is called abnormal molar mass. It
will be corrected using vant-Hoff’s factor while using calculation of molar mass of solute using any colligative
property.
11. What will be vant-Hoff factor for the followings?
(a) Acetic acid in water (b) Acetic acid in benzene (c) K4[Fe(CN)6] in water.
Ans – (a) More than 1 (b) less than 1 (if 100% dimerization takes place). (c) 5 if 100% ionisation.
12. To find the molar mass of biomolecules, osmotic pressure method is preferred. Justify.
Ans – because using osmotic pressure method temperature of the solution does not change and therefore correct
molar mass is calculated whereas other methods are based on temperature change and therefore the
biomolecules may decomposed or denaturized.
13. Arrange the following solutions in increasing order of boiling points and freezing points. Give justification also.
0.1 M KCl AND 0.1 M glucose.
Ans – B.P. = 0.1 M glucose < 0.1 M KCl – because KCl is ionized in solution and gives approximately
double number of particles as compared to glucose solution.
F.P. = 0.1 M KCl < 0.1 M glucose – reason is same.
10. What is meant by Colligative Properties? Give types of colligative properties.
Ans – The properties of a solution depends upon no of particles of solute not on the nature, in the solution are
called colligative properties.
(a) Relative lowering of vapour pressure (b) Elevation of boiling point (c) Depression of freezing point (d) Osmotic
pressure. All are directly proportional to the molality of the solution.
1-Relative Lowering 2- Elevation of Boiling 3-Depression of Freezing 4- Osmotic Pressure
Point : Point
ofVapour Pressure ΔTb = Kb m V = nRT
= Osmotic pressure
R =Gas constant
Π =CRT (C= Molarity)

THREE MARKS QUESTIONS

1. Define Osmotic pressure. What do you understand by the term hypertonic and hypotonic solutions? What
happens when blood cells are kept in fresh water?
Ans – Movement of solvent particles through the semipermeable membrane from dilute to concentrate solution
is called osmosis.
The solution which has higher osmotic pressure is called hypertonic whereas the solution which has lower
osmotic pressure is called hypotonic solution. Blood cells swell because of endosmosis.
Under hypertonicity, cell becomes shrink.
Hypotonicity is the presence of a solution that causes cells to swell.
Isotonicity is such a characteristic solution that maintains a balanced cell volume.

2. The molecular masses of polymers are determined by osmotic pressure method and not by measuring other
colligative properties. Give two reasons.
Ans: The osmotic pressure method has the advantage over other colligative properties because
(i) pressure measurement is around the room temperature and the molarity of the solution is used instead of
molality.
(ii) Its magnitude is large as compared to other colligative properties even for very dilute solutions.
 3. Given below is the sketch of a plant for carrying out a process.

(a) Name the process occurring in the above plant.

(b) To which container does the net flow of solvent take place?
(c) Give one practical use of the plant.
Ans - (a) Reverse osmosis
(b) To fresh water container
(c) This can be used as a desalination plant to meet potable water requirements.
4. Calculate the boiling point of a solution prepared by adding 15 g of NaCl to 250 g of water. (Kb for water =
0.512 K Kg mol-1 and molar mass of NaCl = 58.5 g/mol). Assuming that NaCl is 100% ionized in water.
𝑖 𝑥 𝐾𝑏 𝑥 𝑊𝐵 𝑥 1000
Ans - ∆Tb = 𝑀𝐵 𝑥 𝑊𝐴
2 𝑥 0.512 𝑥 15 𝑥 1000
= 58.5 𝑥 250
= 1.052 K
Boiling point of the solution = 373 + 1.052 = 374.052 K
5. The vapour pressure of pure benzene at a certain temperature is 0.850 bar. A non-volatile solute weighing 0.5 g
when added to 39.0 g of benzene (molar mass = 78g/mol). Vapour pressure of the solution, then, is 0.845 bar.
What is the molar mass of the solid substance?
Ans -

6.

Ans –

CHEMICAL KINETICS
TWO MARKS QUESTIONS
1. Define the term average rate and instantaneous rate of reaction.
Ans – Change of concentration of either reactant or product in a measurable time interval is called average
rate and if time interval is taken zero then average rate becomes instantaneous rate. Unit of rate = mol/L/s.
2. Write the rate expression with respect to each reactant and product for the reaction given below.

Ans -
3.

Ans –

4. What are the units of rate constant for the zero, first and second order of reactions?
Ans –
 5.

Ans –

6. Compare molecularity and order of a reaction.

Ans – OR any two considerable points.

7. Write the integrated rate equations for both zero and first order reactions. Also write their formulas to find
half-life.
Ans – For zero order – K = [R]0 – [R]/t & t1/2 = [R]0/2K
For first order – K = 2.303/t . log [R]0/[R] & t1/2 = 0.693/K
8.

9. (a) What is the effect of temperature change by 100C on rate constant?

(b)Define pseudo first order reaction.
Ans – (a) Rate constant becomes doubled.
(b) In a bimolecular reaction, if concentration of one of the reactant is taken in excess, then reaction
becomes first order kinetics. Such reactions are known as pseudo first order reactions.
10. Define activation energy. Explain the effect of catalyst on activation energy of a reaction?
Ans – The minimum amount of energy that is required to cross the energy barrier and form activated complex for
the reactant molecules, is called energy of activation.
A catalyst provides an alternate path of lower activation energy and increase the reaction rate.
THREE MARKS QUESTIONS
1. Explain the key features of Collision theory.
i. Collision between the reactant molecules is must.
ii. Colliding molecules must have proper orientation.
Iii.Collision frequency must be high.
2. A reaction is first order in A and second order in B.
(i) Write the differential rate equation.
(ii) How is the rate affected on increasing the concentration of B three times?
(iii) How is the rate affected when the concentrations of both A and B are doubled?
Ans - . (i) Rate = K[A]1 [B]2
(ii) Rate = K[A]1 [3B]2 = 9K[A]1 [B]2 hence, it becomes 9 times.
(iii)Rate = K[2A]1 2[B]2 = 8K[A]1 [B]2 hence, it becomes 8 times.
3. Draw the graphical representations of zero and first order reactions showing time and conc. Of the reactant.

Ans - (i) zero order (ii) 1st order

4. How is the activation energy of a reaction calculated by graphical method?
Ans -

Find the slope and calculate Ea as slope = -Ea/R

5. A first order reaction is 50% completed in 40 minutes at 300 K and in 20 minutes at 320 K. Calculate the
activation energy of the reaction.
(Given: log 2 = 0.3010, log 4 = 0.6021, R = 8.314 JK-1 mol-1)
Calculate K1 and K2 using two half-lives given and then find Ea.

ELECTROCHEMISTRY
SrNo Terminology
1.
2
3

5 Variation of molar conductivity with concentration

For strong electrolytes λ decreases slightly with increase in concentration
due to increase in number of ions per unit volume. e.g KCl
For weak electrolytes it increases sharply with decrease in concentration
as ionization of weak electrolytes increases on dilution e.g CH3COOH
6 Kohlrausch’s Law : According to this law, molar conductivity of an electrolyte, at infinite dilution can be expressed
as the sum of contributions from its individual ions e.g.  CaCl   (Ca 2 )  2  (Cl )
2
7 Faraday – First law of electrolysis : The amount of
substance deposited during electrolysis is directly
proportional to quantity of electricity passed.
W  zit and W=EIt/96500
8 Nernst equation Equilibrium constant Kc At equilibrium Q = Kc and Ecell = 0
Ecell  E cell 
 0.059 [ product ] 0.059
log Ecell  log Kc
n [react .]
n
9. Electrochemical Cell and Gibbs energy of the
reaction
Products of electrolysis
NaCl (molten) Cathode : Na+(l) + e– → Na(s) Anode : Cl–→ ½Cl2+e–
NaCl (aq) Cathode : H2O (l ) + e– → ½H2(g) + OH– Anode : Cl–→ ½Cl2+e–
AgNO3(aq)-Ag electrodes Cathode : Ag+(aq) + e- Ag(s) Anode: Ag(s)  Ag+(aq) + e-
AgNO3(aq)- Pt electrodes Cathode : Ag+(aq) + e- Ag(s) Anode: 2H2O(l )→ O2(g) + 4H+(aq) + 4e–
CuCl(aq)- Pt electrodes Cathode : Cu+(aq) + e- Cu(s) Anode: 2H2O(l )→ O2(g) + 4H+(aq) + 4e–

Electrochemical Cell Electrolytic Cell

1. It is device to convert chemical energy to electrical energy 1. It is device to convert electrical energy into chemical energy
2. It is based upon redox reaction which is spontaneous. 2. The redox reaction is non-spontaneous and takes place only
when electrical energy is supplied.
SNO Name of cell Electrolyte Chemical Reaction Remark
1 Mercury Cell Paste of Anode:- zinc-mercury amalgam Provide constant voltage and does
KOH & Zn(Hg)  2OH  ZnO(s)  H O  2e 
 
not corroded due to absence of
2
Zn(OH)2 Cathode:- HgO and carbon ion in overall reaction.
 
HgO  H2O  2e  Hg(1)  2OH Voltage 1.35V
Overall reaction:- Zn(Hg) + HgO  ZnO + H2
2 Dry Cell : ZnCl2 and Anode :- Zinc rod Zn(s) → Zn2++2e- Corroded due to the presence of
NH4Cl Cathode:-Carbon rod surrounded by MnO2 ion in overall reaction.
2MnO2 + 2NH4 + 2e Mn2O3 +2NH3 ZnCl2 is used to make a complex
+ -
Overall Reaction:- [Zn(NH3)2Cl2] it saves the bursting
Zn + 2MnO2 + 2NH4+ Zn 2+ + Mn2O3 + 2 NH3 of cell, Voltage 1.5V
3 Lead Storage 38% H2SO4 Anode:- Pb grid Can be Recharged by reversing the
(Secondary PbSO (s)  2e  Pb(s)  SO 2 (aq)
electrodes Reactant become
4 4
Batteries) : Cathode:-Pb grid filled with PbO2 products and products become
PbO2(S) + SO 2-
+ 4H+(aq) +2e- PbSO4(s) + 2H2O(l) reactants
4
Overall Cell Reaction:-
Pb(s)  PbO2 (s)  2H2SO4  2PbSO4 (s)  2H2O(1)

 
4 Fuel Cell : KOH Anode :- 2H2  4OH  4H2O  4e Eco friendly, Efficiency 60-70%
solution
Cathode O (g)  2H O(l)  4e  4OH  (aq)
2 2
Overall Reaction:- 2H2 (g)  O2 (g)  2H2O(l)

5. Corrosion H2CO3 Anode (oxidation) :- Fe(s)  Fe2 (aq)  2e Formula of rustFe2O3. x H2O
Cathode (Reduction) :-
O (g)  4H  (ag)  4e  2H O(l)
2 2

Atmospheric Oxidation:-
2Fe2+(aq) + 2H2O(l)+1/2O2  Fe2O3(s)+4H+(aq)
 By covering the surface with paint or by some chemicals (e.g. bisphenol). / Cover the surface by other
Prevention of
metals (Sn, Zn, etc.) that are inert or react to save the object. An electrochemical method (sacrificial
Corrosion
electrode like Mg, Zn, etc.) which corrodes itself but saves the object.
Observe the graph (a) The curve ‘Y’ is for KCl or CH3COOH? Ans:- It is for CH3COOH.
(b) What is intercept on Λm axis for ‘X’ equal to? Ans:- equal Λm
shown in figure
(c) Give mathematical equation representing straight line.
between Λm(molar
conductivity) Vs C Ans:
(Molar- (d) What is slope equal to? Ans: Slope = –A
concentration) and (e) What happens to molar conductivity on dilution in case of weak
electrolyte and why?
answer the questions
Ans: Λm for weak electrolyte increases sharply on dilution because
based on graph. both number of ions as well as mobility of ions increases.
 COORDINATION COMPOUNDS

Ligand: Provide pair of electron for formation of Coordination Number: Number of coordinate bonds
coordinate bond to central metal atom is called formed by ligands with central metal atom in the complex
ligand. (Lewis Base) is called coordination number of complex.
Types of ligands:- eg. - [Mg(EDTA)]2- [Fe(CN)6]4- [Co(en)3]3+
(a) Monodentate :-One donar atom
(b) Bidentate :- Two donar atom C.N. 6 6 6
(c) Ambidentate:- Two donar atom but at a time 5) Homoleptic and Hetroleptic Complexes:
form only one bond Eg: SCN- and NCS- A complex with same type of ligands surrounding central
F- -Fluorido, Cl- - Chlorido, Br- -Bromido metal atom is called homoleptic complex. E.g.-
I- - Iodido, H- -Hydrido, OH- - [Cu(NH3)4]2+, [Pt(NH3)4]2+
Hydroxido CN- -Cyanido, SCN- - A complex with different types of ligands surrounding
Thiocyanato central metal atom is called hetroleptic complex. E.g.
NCS- - Isothiocyanato, CH3COO- - [Pt(NH3)2 Cl2]
6. Coordination Polyhedron: Spatial arrangement of
Acetato SO42- - Sulphato, CO32- - ligands around central metal atom or ion is called
Carbonato coordination polyhedron.
(COO-)2 or C2O42- - Oxalato (ox), NO3- - Writing Formula of Coordination Complex:
Nitrato NO2- - Nitrito(N), PO43- - 1. Cation is written first followed by anion.
Phosphato 2. In coordination sphere central metal atom is
Neutral ligands- H2O- Aqua , NH3 - written first followed by ligands.
Ammine R NH2 -Alkanamine, CO – 3. If more than one type of ligands are present then
Carbonyl, H2NCH2CH2NH2 - ethane-1,2– alphabet is followed. Na2[Fe(H2O)4 (NO) Br]
diamine Ethylenediaminetetraacetate ion
(EDTA4–)
Ligand which has two different donor atoms and
either of the two ligetes in the complex is called
ambidentate ligand. Examples NO2 – and SCN–
Nomenclature of Coordination Compounds: (5) [Pt (NH3)2 Cl (NO2)]
(1) Na2 [Fe (H2O) Br4 (NO)] Diamminechloridonitritoplatinum(II)
Sodium tetrabromidonitrosylferrate (II) (6) [Ni (CO)4] Tetracarbonyl Nickel (O)
(2) [Fe (H2O)4 Br (NO)] SO4 (7) CO (NH3)5 CO3] Cl
Tetraquabromidonitrosyliron (III)sulphate Pentamminecarbonato cobalt (III)
(3) K4 [Fe (CN)6 ] chloride (8) K3 [Cr (C2O4)3]
Potassium hexacyanoferrate Potassium trioxalate chromate (III)
(II) (4) [Cr (NH3)3 (H2O)3 ] Cl3 (9) Hg [Co (SCN)4]
Triamminetriaquachromium (III) Chloride Mercury tetrathiocyanato cobaltate (III)
Isomerism in Coordination Compounds (b) Stereoisomerism
(a) Structural isomerism (i) Geometrical isomerism-
(i) Linkage isomerism- ambidentate ligand. M– Square planner complexes with formula MA2B2- two
SCN, M–NCS & (–NO2 ), (–ONO) geometrical isomers, MABCD- Three isomers
(ii) Coordination isomerism-Both complex Octahedral complexes- MA4B2, M(aa)2 A2 – Cis
[Co(NH3 )6 ][Cr(CN)6 ] & [Cr(NH3)6 ][Co(CN)6 ] & trans MA3B3- Fac & mer isomers
(iii) Ionisation isomerism- (ii) Optical isomerism- Optical isomers are mirror
[Co(NH3)5(SO4)]Br & [Co(NH3 images that cannot be superimposed on one another.
)5Br]SO4 . These are called as enantiomers.
(iv) Solvate isomerism- exchange of H2O as ligand [PtCl2 (en)2 ] 2+
and counter anion
[Cr(H2O)6]Cl3&[Cr(H2O)5Cl]Cl2.H2O
Bonding in coordination compounds-
(I) Werner’s Coordination Theory-
Primary valence is ionizable and refers charge present on complex ion.
Secondary valence is non-ionizable and refers coordination number of
complex.
The ions/groups bound by the secondary linkages to the metal have characteristic spatial arrangements
corresponding to different coordination numbers.

Q1. Arrange the following complexes in the increasing order of conductivity of their solution:

[Co(NH3)3Cl3], [Co(NH3)4Cl2]CI, [Co(NH3)6]Cl3, [Cr(NH3)5Cl]Cl2

Ans: Ionisable ions or molecules exist outside the coordination sphere. When a complex dissolves, it
releases more ions, making it more conductive.

[Co(NH3)3Cl3] (1 ion) < [Co(NH3)4Cl2]Cl (2 ions) < [Cr(NH3)5Cl]Cl2 (3 ions) < [Co(NH3)6]Cl3 (4
ions)
Here, the number of ions increases and conductivity increases.

Q2. A coordination compound CrCl3, 4H2O precipitates silver chloride when treated with silver nitrate.
The molar conductance of its solution corresponds to a total of two ions. Write the structural formula of the
compound and name it.

Ans: There is chloride ion outside the complex because silver chloride precipitates when treated with silver
nitrate. There is only one chloride ion outside the complex since only two ions are generated. As a result,
the compound’s structural formula and nomenclature are:

Q3. Write IUPAC name of the complex [Cr(NH3)4Cl2]+. Draw structures of geometrical isomers for this
complex.

Tetraaminedichloridocromium(III) ion.

Q4. Using IUPAC norms write the formulae for the following :

(a) Pentaamminenitrito-O-cobalt(III) ion

(b) Potassium tetracyanidonickelate(II)
(c) Dichloridobis(ethylenediamine)Cobalt(III)ion.

Q5. Write the IUPAC name of the following Coordination Compounds:

[Co(NH3)4Cl(NO2)]+
[Co(NH3)4 (H2O)Cl]Cl2
K3[Fe(CN)6]
[CO(NH3)5(C03)]Cl
[CO(NH3)5(N02)](N03)2
Q6. Define and give one example each of linkage and coordination, ionization and hydrate isomerism.

Ans – Linkage isomerism : When more than one atom in an ambidentate ligand is linked with central
metal ion to form two types of complexes, then the formed isomers are called linkage isomers and the
phenomenon is called linkage isomerism.
[Cr(H2O)5(NCS)]2+ Pentaaquathiocyanate chromium (III) ion
[Cr(H2O)5(NCS)]2+ Pentaaquaisothiocyanate chromium (III) ion

Coordination isomerism arises due to exchange of ligands between positive and negative
coordination spheres. [Co(NH3)6] [Cr(CN)6] and [Cr(NH3)6] [CO(CN)6]
Ionization isomerism [Pt (NH3)5 (Br)3] SO4 and [Co (NH3)5 (SO4)] Br

Q7. Define ambidentate ligands and chelating ligands with suitable example.

Ans – An ambidentate ligand has two donor sites but monodentate in nature at a time. NO2-, SCN-
etc

Q8. What is meant by chelate effect?

Ans: Chelate effect : When a bidentate or a polydentate ligand contains donor atoms positioned in such
a way that when they coordinate with the central metal ion, a five or a six membered ring is formed. This
effect is called Chelate effect. As a result, the stability of the complex increases.

Q9. What are homoleptic and heteroleptic complexes?

Ans – In homoleptic complexes all the ligands present are same whereas in heteroleptic complexes
different kind of ligands is present. ,

Q10. Write the state of hybridisation of central metal and structure of the following complexes: [NiCl4]2- &
[Ni(CN)4]2-

Ans - [NiCl4]2- is tetrahedral and sp3 hybrid.

[Ni(CN)4]2- is square planer and dsp2 hybrid.

Q11. Why are low spin tetrahedral complexes not formed?

Ans: In a tetrahedral complex, the d-orbital is split too small as compared to octahedral. For the same metal
and same ligand Δt = 4/9Δo. Hence, the orbital energies are not enough to force pairing. As a result, low
spin configurations are rarely observed in tetrahedral complexes.

Q12. What is meant by crystal field splitting energy? On the basis of crystal field theory, write the
electronic configuration of d4 in terms of tgg and eg in an octahedral field when (i) Δ0 > P (ii) Δ0 < P
Answer:
The difference between energies of two sets of d-orbitals t2g and e is called crystal field splitting energy
(ΔQ).
(i) If Δ0 > P, the configuration will be t2g, eg. Ligands will produce strong field and low spin complex will
be formed.
(ii) If Δ0 < P, the configuration will be t2g, eg and it is in the case of weak field ligands and high spin
complex will be formed.
Q13. Why is geometrical isomerism not possible in tetrahedral complexes having two different types of
unidentate ligands coordinated with the central metal ion ?

1) For geometrical isomerism, the relative position of unidentate ligands attached to central metal atom
shall be unequal.

2)In case of tetrahedral complex, the positons of the unidentate ligands are identical with respect to each
other and hence show optical isomerism and not geometric.

Q14. Out of the following two coordination entities which is chiral (optically active)?
A) cis−[CrCl2(ox)2]3− B) trans−[CrCl2(ox)2]3−

Q15. Give evidence that [Co(NH3)5Cl]SO4 and [Co(NH3)5SO4]Cl are ionization isomers.

F irst will give white ppt with barium chloride whereas the second will give white ppt with silver nitrate, so
these are ionisation isomers.
Q16. [NiCl4]2− is paramagnetic while [Ni(CO)4] is diamagnetic though both are tetrahedral. Why?

Ans – Though both [NiCl4]2− and [Ni(CO)4] are tetrahedral, their magnetic characters are different. This is
due to a difference in the nature of ligands. Cl− is a weak field ligand and it does not cause the pairing of
unpaired 3d electrons. Hence, [NiCl4]2− is paramagnetic.

In Ni(CO)4, Ni is in the zero oxidation state i.e., it has a configuration of 3d8 4s2.

But CO is a strong field ligand. Therefore, it causes the pairing of unpaired 3d electrons. Also, it causes the
4s electrons to shift to the 3d orbital, thereby giving rise to sp3 hybridization. Since no unpaired electrons
are present in this case, [Ni(CO)4] is diamagnetic.
first one has unpaired electrons whereas the second one has no unpaired electron.

Q17. Complexes with Polydentate ligands are more stable than other complexes. Justify by giving
examples.

Ans – Polydentate ligands offer chelating effect which makes the complex more stable.

Q18. Give the electronic configuration of the following complexes on the basis of Crystal Field Splitting
theory:

[CoF6]3-, [Fe(CN)6]4- and [Cu(NH3)6]2+

Ans - [CoF6]3−, Co3+→(3d6)→t2g4eg2

[Fe(CN)6]4−, Fe2+→(3d6)→t2g6eg0
[Cu(NH3)6]2+,Cu2+→(3d9)→t2g6eg3
Q19. CuSO4.5H2O is blue in colour while CuSO4 is colourless. Why?

Ans: Water acts as a ligand in CuSO4.5H2O, causing crystal field splitting. As a result, in CuSO4.5H2O, a
d—d transition is possible and coloured. Crystal field splitting is impossible in anhydrous CuSO4 due to the
lack of water (ligand), hence there is no colour.

Q20. Using crystal field theory, draw an energy level diagram, write electronic configuration of the central
metal atom/ion and determine the magnetic moment value in the following:

(i) [CoF6]3-, [Co(H2O)6]2+, [Co(CN)6]3-

(ii) [FeF6]3-, [Fe(H2O)6]2+, [Fe(CN)6]4-

Q21. Using valence bond theory, explain the following in relation to the complexes given below:
[Mn(CN)6]3-, [Co(NH3)6]3+, [Cr(H2O)6]3+, [FeCl6]4-
(i) Type of hybridisation.
(ii) Inner or outer orbital complex.
(iii) Magnetic behaviour.
(iv) Spin only magnetic moment value.
 Q22. Why are different colours observed in octahedral and tetrahedral complexes for the same metal and
same ligands?
Ans: In the octahedral and tetrahedral fields, the extent of d-orbital splitting differs. In the octahedral and
tetrahedral fields, the crystal field stabilisation energy is strongly related.

THE D- AND F-BLOCK ELEMENTS

1 d-block elements are called transition elements incomplete d-orbitals in neutral or most stable oxidation state.
2 Zn, Hg, Cd, are not included as transition as they have filled d-orbitals in neutral and most stable +2
elements and why? oxidation state.
3 Sc3+ has d0 configuration but it is transition Because of partially filled d1 configuration of Sc
metal
4 First series transition elements shows irregular Due to shielding effect of inner 3d electrons which
trend of atomic radii overcome
ENC.
5 Atomic radii of Zr to Hf are almost same. due to Lanthenoid Contraction.
6 First series transition elements shows irregular It is because of mutual exchange of energy between d and
trend of IE f
orbitals after removal of one electron.
7 Transition metals have high enthalpy of due to presence of unpaired electrons form strong metallic
atomization and melting point. bonding
8 Zn, Cd, Hg are not very hard and have low Due to presence of all paired electrons they have least
M.P. and B.P. enthalpy of atomization, very weak metallic bond & are not
very hard
with low M.P. and B.P.
9 d-block elements shows a large no. of due to presence of unpaired electrons or partially filled d-
oxidation orbitals.
state
10 Which first series transition metal shows highest Mn shows highest number of oxidation state due presence
number of oxidation states and why? of
highest number of unpaired electrons.
11 Which first series transition metal do not show Sc , due to achieving noble gas configuration in +3 O.S
variable oxidation states and why?
12 Cr3+ is more stable as compared to Cr2+ due to stable half filled t2g3 configuration.
13 Cu2+ is more stable in solution than Cu+ due to high hydration enthalpy of Cu2+ ion in solution.
14 Which first series transition metal shows +1 Cu shows +1 oxidation state in gaseous form due to stable
oxidation states and why? full
filled 3d10 configuration.
15 Higher oxidation states of transition because higher oxidation states stabilized by highly
metals electronegative elements such as O and F
found in their oxides and fluorides
16 higher oxidation states are more common in due to formation of dπ-pπ bond between metal and oxygen.
oxides rather than fluorides of transition metals.
17 +2 O.S becomes more stable in first series as number of unpaired electrons decreases.
transition elements moving from left to right
18 Write oxoanions of first series transition metals MnO4-, Cr2O72-, VO3-, CrO42-
in which group number and O.N. of
transition
metal are same-
19 Moving from left to right E0 for M2+/M trends due to irregular variation of IE1 + IE2.
becomes
less negative but it shows irregular trend
20 For copper E0 Cu2+/Cu is +ve (+0.34 V) it is due to low hydration enthalpy of Cu2+ which
cannot
compensate ∆subH0 + IE1 + IE2.
21 0 3+
For Mn , E Mn /Mn is +ve 2+ because by converting into Mn2+ it achieves half
filled
configuration.
22 For Cr , E0 Cr3+/Cr2+ is −ve because Cr3+ is more stable due to half filled t2g
configuration.
23 Most of the compounds of transition metal are It is due to d-d transition
coloured in solid state as well as in their solution
24 (Sc3+, Ti4+) does not exhibit any colour Due to absent of unpaired e- as d-d transition is not possible
25 (Zn2+, Cu+) does not exhibit any colour full filled d-orbitals (d10) as d-d transition is not possible
26 Transition metals or ions are paramagnetic in Due to presence of unpaired electrons (d1-9)
nature
27 Transition metal form large number of High charge by mass ratio, availability of vacant d-orbital
coordination complexes &
Variable oxidation state
28 What are Interstitial compounds? Compounds in which small elements like H, B, C, N trapped
in
the interstitial space of metal lattice.
29 Transition metals form Interstitial compounds. due to availability of interstitial space in metal lattice.
30 Why interstitial compounds are found to be more These compounds have high M.P as compared to pure
useful than pure metal? metals.
These are very hard and are Chemically inert.
31 Transition metals and their compounds are Due to large surface area, variable oxidation state &
widely used as catalyst Availability
of vacant d-orbitals
32 transition metals form alloy. Due to comparable metallic radii
33 Why oxides of Higher oxidation states Higher oxidation states are more polarizing in nature . hence
of are acidic in nature whereas lower O.S. are less polarizing
transition metals are acidic in nature whereas hence are basic in nature.
lower O.S. are basic in nature?
34 Actinoids shows greater number of oxidation Due to comparable energy of 5f, 6d, and 7s orbitals.
states then lanthanoids
35 It is difficult to study chemistry of actinoids. Due to radio active nature and small half life
36 Ce(IV) is a good oxidizing agent in aq. soln because in aq. solution its E0Ce4+/ Ce3+ is +1.74 V
37 Actinoid contraction is greater from element to because of poor shielding by 5f orbitals due to its
element as compared to lanthanoids . superficial
position.
 f-Block Elements Consequences: 1. Resemblance in the properties of
General configuration (n – 2) f 1-14 (n – 1)d 0-1 ns2 second and third transition series from Zr & Hf) atomic
57La [Xe] 5d1 6s2 89Ac [Rn] 6d1 7s2 - size of 2nd and 3rd transition series become same.
2. Similarity in the properties of Lanthanoids:- The
58Ce [Xe] 4f1 5d1 6s2 91Pa [Rn] 5f2 6d1 7s2
decrease in atomic radii from Lanthenoid to
63Eu [Xe] 4f7 5d0 6s2 92U [Rn] 5f3 6d1 7s2
Lanthenoid is very less hence it is very difficult to
64Gd [Xe] 4f7 5d1 6s2 94Pu [Rn] 5f6 6d0 7s2 separate these elements in pure state.
70Yb [Xe] 4f14 5d0 6s2 3. Basic strength of hydroxides of Lanthanoids
Lanthanoid Contraction- Regular decrease in atomic decreases from Lanthenium (La) to Lutesium (Lu).
or ionic radii of Lanthenoid with increase in atomic Misch Metal – It is alloy of Lanthanoids(95%) with
number is called Lanthenoid contraction. iron (5%)and Trace of S, C, Al ,Ca Lanthenoid – 95%
Cause: It is due to imperfect shielding of one 4f Metal + Trace of S, C, Al ,Ca + Iron – 5%
orbital by another 4f orbital due to which ENC Uses- making bullet shells and flinter of lighters.
regularly increases with increase in atomic number.
Lanthanoids Actinoids
Last electron enters in 4f orbital Last electron enters in 5f orbital
Are natural elements and non radioactive in nature Are radioactive in nature and after Np they are
synthetic element
Shows less number of oxidation states [+2,+3,+4] Shows greater number of oxidation states
[+3,+4,+5,+6,+7]
Element to element lanthanoid contraction is less Element to element actinoid contraction is more

Q1.

Ans-
Q2.

Ans-

Q3.

Ans-

Q4.

Ans-
Q5.

Ans-

Q6.

Ans-
Q7.

Ans-

Q8.

Ans-

Q9.

Ans-

Q10.

Ans-
 AMINES
Q1. Arrange the following in increasing order of their basic strength :
(i) C2H5NH2, C6H5NH2, NH3, C6H5CH2NH2, (C2H5)2NH
(ii) C2H5NH2, (C2H5)2NH, (C2H5)3N, C6H5NH2
(iii) CH3NH2, (CH3)2NH, (CH3)3N, C6HsNH2, C6H5CH2NH2

Ans: (C2H5)2NH>C2H5NH2>NH3>C6H5CH2NH2>C6H5NH2
(C2H5)2NH>(C2H5)3N>C2H5NH2>C6H5NH2

Q2. Write IUPAC names of the following compounds and classify them into primary, secondary and
tertiary amines.
(i) (CH3)2 CHNH2 (ii) CH3(CH2)2NH2
(iii) CH3NHCH(CH3)2 (iv) (CH3)3CNH2
(v) C6H5NHCH3 (vi) (CH3CH2)2NCH3
(vii) m−BrC6H4NH2
Solution :
(i) 1-Methylethanamine (10 amine)
(ii) Propan-1-amine (10 amine)
(iii) N−Methyl-2-methylethanamine (20 amine)
(iv) 2-Methylpropan-2-amine (10 amine)
(v) N−Methylbenzamine or N-methylaniline (20 amine)
(vi) N-Ethyl-N-methylethanamine (30 amine)
(vii) 3-Bromobenzenamine or 3-bromoaniline (10 amine)
Q3. Give one chemical test to distinguish between the following pairs of compounds.
(i) Methylamine and dimethylamine
(ii) Secondary and tertiary amines
(iii) Ethylamine and aniline
(iv) Aniline and benzylamine
(v) Aniline and N-methylaniline.
Solution :
(i) Methylamine and dimethylamine can be distinguished by the carbylamine test.
(ii) Secondary and tertiary amines can be distinguished by allowing them to react with Hinsberg’s reagent
(benzenesulphonyl chloride, C6H5SO2Cl).
(iii) Ethylamine and aniline can be distinguished using the azo-dye test.
(iv) Aniline and benzylamine can be distinguished by their reactions with the help of nitrous acid, which is
prepared in situ from a mineral acid and sodium nitrite.
(v) Aniline and N-methylaniline can be distinguished using the Carbylamine test.
Q4. Write short notes on the following:
(i) Carbylamine reaction
(ii) Diazotisation
(iii) ‘Hofmann’s bromamide reaction
(iv) Coupling reaction
(v) Ammonolysis
(vi) Acetylation
(vii) Gabriel phthalimide synthesis

Q5. Give reasons for the following:

(i) pKb of aniline is more than that of methylamine.

(ii) Ethylamine is soluble in water whereas aniline is not.

(iii) Methylamine in water reacts with ferric chloride to precipitate hydrated ferric oxide.
(iv) Although amino group is o, p− directing in aromatic electrophilic substitution reactions, aniline on nitration
gives a substantial amount of m-nitroaniline.

(v) Aniline does not undergo Friedel-Crafts reaction.

(vi) Diazonium salts of aromatic amines are more stable than those of aliphatic amines.

(vii) Gabriel phthalimide synthesis is preferred for synthesising primary amines.

Solution :
(i) Aniline undergoes resonance and as a result, the electrons on the N-atom are delocalized over the benzene
ring. Therefore, the electrons on the N-atom are less available to donate. On the other hand, in case of
methylamine (due to the +I effect of methyl group), the electron density on the N-atom is increased. As a result,
aniline is less basic than methylamine. Thus, pKb of aniline is more than that of methylamine.

(ii) Ethylamine when added to water forms intermolecular H−bonds with water. Hence, it is soluble in water. But
aniline does not undergo H−bonding with water to a very large extent due to the presence of a large hydrophobic
−C6H5 group. Hence, aniline is insoluble in water.

(iii) Due to the +I effect of −CH3 group, methylamine is more basic than water. Therefore, in water, methylamine
produces OH− ions by accepting H+ ions from water. Ferric chloride (FeCl3) dissociates in water to form Fe3+ and
Cl− ions. Then, OH− ion reacts with Fe3+ ion to form a precipitate of hydrated ferric oxide.

(iv) Although amino group is o,p− directing in aromatic electrophilic substitution reactions, aniline on nitration
gives a substantial amount of m-nitroaniline: Nitration is carried out in an acidic medium. In an acidic medium,
aniline is protonated to give anilinium ion (which is meta-directing). For this reason, aniline on nitration gives a
substantial amount of m-nitroaniline.

(v) A Friedel-Crafts reaction is carried out in the presence of AlCl3. But AlCl3 is acidic in nature, while aniline
is a strong base. Thus, aniline reacts with AlCl3 to form a salt. Due to the positive charge on the N-atom,
electrophilic substitution in the benzene ring is deactivated. Hence, aniline does not undergo the Friedel-Crafts
reaction.

(vi) The diazonium ion undergoes resonance as shown below:

This resonance accounts for the stability of the diazonium ion. Hence, diazonium salts of aromatic amines are
more stable than those of aliphatic amines.

(vii) Gabriel phthalimide synthesis is preferred for synthesising primary amines:

Gabriel phthalimide synthesis results in the formation of 1° amine only. 2° or 3° amines are not formed in this
synthesis. Thus, a pure 1° amine can be obtained. Therefore, Gabriel phthalimide synthesis is preferred for
synthesizing primary amines.
Q6. Arrange the following:

(i) In decreasing order of the pKbvalues:

C2H5NH2, C6H5NHCH3, (C2H5)2NH and C6H5NH2

(ii) In increasing order of basic strength:

C6H5NH2, C6H5N(CH3)2, (C2H5)2NH and CH3NH2

(iii) In increasing order of basic strength:

(a) Aniline, p-nitroaniline and p-toluidine

(b) C6H5NH2, C6H5NHCH3, C6H5CH2NH2.

(iv) In decreasing order of basic strength in gas phase:

C2H5NH2, (C2H5)2NH, (C2H5)3N and NH3

(v) In increasing order of boiling point:

C2H5OH, (CH3)2NH, C2H5NH2

(vi) In increasing order of solubility in water:

C6H5NH2, (C2H5)2NH, C2H5NH2.

Solution :
(i) C6H5NH2 > C6H5NHCH3 > C2H5NH2 > (C2H5)2NH

(ii) C6H5NH2 < C6H5N(CH3)2 < CH3NH2 < (C2H5)2NH

(iii) (a) p-Nitroaniline < Aniline < p-Toluidine

(b) C6H5NH2 < C6H5NHCH3 < C6H5CH2NH2.

(iv) (C2H5)3N > (C2H5)2NH > C2H5NH2 > NH3

(v) (CH3)2NH < C2H5NH2 < C2H5OH

(vi) C6H5NH2 < (C2H5)2NH < C2H5NH2

Q7. Accomplish the following conversions:

(i) Nitrobenzene to benzoic acid

(ii) Benzene to m-bromophenol
(iii) Benzoic acid to aniline
(iv) Aniline to 2,4,6-tribromofluorobenzene
(v) Benzyl chloride to 2-phenylethanamine
(vi) Chlorobenzene to p-chloroaniline
(vii) Aniline to p-bromoaniline
(viii) Benzamide to toluene
(ix) Aniline to benzyl alcohol.
Q8. Complete the following reactions:

(i)

(ii)

(iii)

(iv)

(v)

(vi)

(vii)

Solution :
(i)

(ii)

(iii)

(iv)

(v)
(vi)

(vii)

Q9. Why cannot aromatic primary amines be prepared by Gabriel phthalimide synthesis?

Solution : Gabriel phthalimide synthesis is used for the preparation of aliphatic primary amines. It involves
nucleophilic substitution (SN2) of alkyl halides by the anion formed by the phthalimide. But aryl halides do not
undergo nucleophilic substitution with the anion formed by the phthalimide. Hence, aromatic primary amines
cannot be prepared by this process.

Q10. Give plausible explanation for each of the following:

(i) Why are amines less acidic than alcohols of comparable molecular masses?

Since oxygen is more electronegative than nitrogen, So, the alkoxide ion is more stable as compared to an
amide ion. Hence, alcohol is more acidic than amines.

(ii) Why do primary amines have higher boiling point than tertiary amines?

Intermolecular hydrogen bonding is present in primary amines but not in tertiary amines (H-atom absent in
amino group) so primary amines have higher boiling point than tertiary amines.

(iii) Why are aliphatic amines stronger bases than aromatic amines?

In aromatic amines, the −NH2 group is attached to a −C6H5 group, which is an electron withdrawing group.
So, the availability of a lone pair of electrons on N is decreased. Therefore aliphatic amines are more basic than
aromatic amines.

Question17. How will you convert?

(i) Benzene into aniline

(ii) Benzene into N, N-dimethylaniline

(iii) Cl−(CH2)4−Cl into hexan-1, 6-diamine?

Solution :
(i)
(ii)

(iii)

Q11. Convert

(i) 3-Methylaniline into 3-nitrotoluene.

(ii) Aniline into 1,3,5-tribromobenzene.

Solution :
(i)

(ii)

Q12.

Ans-
Q13.

Ans-

Q14.

Ans-

Q15. Why is methylamine more basic than aniline?

Ans - Methylamine is more basic than aniline due to resonance in aniline and lower stability of aniline ions.
Q16. Ethylamine is soluble in water whereas aniline is almost insoluble. Why?
Ans - Due to hydrogen bonding ability of ethylamine.
Q17. Why are diazonium salts of aromatic amines more stable than those of aliphatic amines?
Ans- The diazonium salts of aromatic amines are more stable than those of aliphatic amines due to dispersal
of the positive charge on the benzene ring.
Q18.

Ans-
Q19.

Ans-

Q20.

Ans-
Q21.

Ans-

Q22.

Ans-

Q23.
How will you convert
(ii) Ethyl nitrile to ethyl amide
(iii) Benzene diazonium chloride to benzonitrile
Ans-

Q24.

Ans-
 REASONING TYPE OF QUESTIONS
10. HALOALKANES AND HALOARENES
QUESTION-REASONING ANSWER- REASON
1 Benzyl chloride is highly reactive towards the SN1 Due to the stability of benzyl carbocation due to
reaction. resonance
2 2-bromobutane is optically active but 1- Because 2-Bromobutane has a chiral centre so mirror
bromobutane is optically inactive image are nonsuperimposable
3 Electrophilic substitution reactions in haloarenes Due to – I effect of halogen predominant over +R
occur slowly. effect
4 Which would undergo SN1 reaction faster because 3o carbocation is more stable than
1ocarbocation

5 Why haloarenes are less reactive than haloalkanes In haloarenes C—X bond acquires a partial double
towards nucleophilic substitution reactions bond character due to resonance
6 Which compound in each of the following pairs will (i) iodine is a better leaving group because of its larger
react faster in SN2 reaction? Why? size. (ii) three bulky methyl group hinder the
(i) CH3Br or CH3I (ii) (CH3)3C-Cl or CH3-Cl approaching nucleophile
7 Compound (I) reacts faster in SN1 reaction as it is a 2°
alkyl halide

8 A solution of KOH hydrolyses CH3CH(Cl)CH2CH3 and CH3CH2ClCHCH3 more easily hydrolysed as it forms 20
CH3CH2CH2CH2Cl. Which one of these is more easily carbocation which is more stable than 10 carbocation
hydrolysed and why?
9 State one use each of DDT and iodoform DDT: It is used as insecticide Iodoform: Iodoform is
used as an antiseptic.
10 What is known as a racemic mixture? Give an An equi-molar mixture of d- and l- isomers(50:50 d+l)
example. For example, butan-2-ol. A racemic mixture is optically
inactive due to external compensation
11 Although chlorine is an electron withdrawing Through resonance effect, chlorine tends to stabilize
group, yet it is ortho-, para-directing in the carbocation and the effect is onlyapplicable at
electrophilic aromatic substitution reactions. ortho and para-positions.
Explain why it is so?
12 Grignard’s reagents should be prepared under This is because Grignard reagent forms alkanes by
anhydrous conditions, why? reacting with moisture.

13 the dipole moment of Chlorobenzene is lower than due to resonance ,Chlorobenzene shorter C—Cl
that of Cyclohexyl chloride bond(sp2)than cyclohexyl chloride C—Cl bond(sp3)

14 Chloroform is stored in closed dark brown bottles chloroform is slowly oxidised by air in the presence of
light to form poisonous gas phosgene.COCl2
11. ALCOHOL, PHENOL AND ETHER
1 p-nitro phenol is more acidic than p-methyl phenol Due to –I/–R effect of –NO2 group & +I /+R effect of CH3
2 p-nitrophenol is more acidic than o-nitrophenol OR p-nitro phenol has intermolecular H-bond while o-nitro
O-nitrophenol is steam volatile ,not p-nitrophenol phenol has intramolecular H-bond.
3 Phenol is more acidic than ethanol. phenoxide ion stabilised by resonance)
4 Boiling point of ethanol is higher in comparison to Because of hydrogen bonding in ethanol
methoxymethane.
5 The C – O – H bond angle in alcohols is slightly less Due to lone pair- lone pair repulsion on oxygen
than the tetrahedral angle (109o28’).
6 Although phenoxide ion has more number of carboxylate ion stabilized through equivalent resonance
resonating structures than carboxylate ion, whereas phenoxide ion through non equivalent
carboxylic acid is a stronger acid than phenol. resonance
12. ALDEHYDES KETONES AND CARBOXYLIC ACIDS

1 Increasing order reactivity towards nucleophilic ,

addition OR (reactivity towards HCN) Butanone < Propanone < Propanal < Ethanal
Methyl tert-butyl ketone < Acetone < Acetaldehyde
2 Acidic Character =(1/ pKa)
(CH3)2CHCOOH < CH3CH(Br) CH2COOH < CH3COOH < Cl-CH2-COOH < F-CH2-COOH
CH3CH2CH(Br)COOH 4-Methoxy benzoic acid <Benzoic acid < 4-Nitrobenzoic
acid < 3, 4-Dinitrobenzoic acid.
3 Aldehydes are more reactive than ketones towards due to steric hinderence of 2-alkyl group in ketone
nucleophilic addition and more +I effect of 2-alkyl group in ketone
4 Cyclohexanone forms cyanohydrin in good yield but due to steric hindrance in 2, 4, 6-trimethyl
2, 4, 6-trimethylcyclohexanone does not.
5 Carboxylic acids are higher BP than alcohols due to more intermolecular hydrogen bonding
13. AMINES AND DIAZONIUM SALT
1 increasing order of basic strength , aqueous solutions C6H5-NH2 < CH3-CH2-NH2 < (C2H5)3N < C2H5-NH- C2H5
NH3 < (CH3)3N < CH3—NH2 < (CH3)2NH.
2 increasing order of basic strength , gas phase C6H5-NH2 < CH3-CH2-NH2 < C2H5-NH- C2H5< (C2H5)3N
3 In increasing order of solubility in water
4 p-methylaniline is more basic than p-nitroaniline ―CH3 group +I – effect ,–NO2 group shows –I Effect (
5 Acetylation of – NH2 group is done in aniline before To reduce activating effect of –NH2 group.
preparing its ortho and para compounds.
6 pKb for aniline is more than that for methylamine In aniline due to resonance
7 Aniline does not undergo Friedel-Crafts reaction Aniline Lewis base, reacts lewis acid AlCl3 to form salt.
8 Why do amines behave as nucleophiles? Due to the presence of a lone pair
9 Aniline, p-nitroaniline and p-toluidine p-Toluidine > Aniline > tr-nitroaniline
10 Aromatic primary amines cannot be prepared by aryl halides do not undergo nuleophilic substitution
Gabriel phthalimide synthesis. easily due to presence of partial double character
11 Although amino group is o– and p– directing in In presence of conc HNO3 ,aniline gets protonated to
electrophilic substitution rean, aniline on nitration form the anilinium ion which is meta directing
gives a substantial amount of m-nitroaniline.
 MECHANISM

1. SN1 mechanism
 It is Two step reactions.
 Step I: In the first step slow dissociation of alkyl halide takes place by reversible reaction
forming acarbocation.

 Step II: The carbocation at once combines with the nucleophile to

form finalproduct (racemic mixture)

2. SN2 mechanism
 It is One step reaction

3. Mechanism for the Hydration of alkenes to alcohol

Mechanism- The mechanism of the reaction involves the following three steps:
Step 1: Protonation of alkene to form carbocation by
electrophilic attack of H3O+.

Step 2: Nucleophilic attack of water on carbocation

Step 3: Deprotonation to form an alcohol

4. Mechanism for the acidic Dehydration of alcohols to give alkenes (At 443 K)
Step 1: Formation of protonated alcohol.

Step 2: Formation of carbocation: It is the slowest step

and hence, the rate determining step of the reaction.

Step 3: Formation of ethene by elimination of a proton

5. Mechanism for the acidic Dehydration of alcohols to give ethers (At 413K)

6. Nucleophilic addition reaction in carbonyl compounds.

 BIOMOLECULES

Carbohydrates are classified on the basis of their behavior on hydrolysis :

Monosaccharides: A carbohydrate that cannot be hydrolyzed further to give simpler
unit of examples are glucose, fructose, ribose, etc.
Oligosaccharides: Carbohydrates that yield two to ten monosaccharide units, on hydrolysis. For
example, sucrose , Maltose and Lactose
Polysaccharides: Carbohydrates which yield more than 10 of monosaccharide units on
hydrolysis are called polysaccharides. Some common examples are
starch, cellulose, glycogen, gums, etc.
Reducing sugars: All those carbohydrates which reduce Fehling’s solution and Tollens’ reagent
are referred to as reducing sugars. Examples: All monosaccharides, Maltose and
Lactose.
Non- In disaccharides, if the reducing groups of monosaccharides i.e., aldehydes
reducing or ketone groups are bonded, these are non-reducing sugars e.g. Starch,
sugars: Sucrose
Anomers: α & β - Glucose , which differ in the orientation of − OH group at C1 .
Proteins: proteins are polymer of α- amino acids ,joined by peptide bonds .
They also known as polyamides.
Types of Proteins: (i) Fibrous proteins:- The polypeptide chains run parallel and are held
by H- bond or disulphide linkage , Insoluble in water Eg : Keratin
,Myocin
(ii) Globular proteins:- Polypeptides coil around to give a spherical shape,
Soluble in water Eg : Insulin ,Albumins
Structure and 1) Primary structure : It is a specific sequence of amino acids
shape of 2) Secondary structure: It represent shape ie. α - halix and β- pleated sheet.
Proteins: i) α - halix : polypeptide chain twisted in to a right handed
screw by forming H-bonds b/w NH group and >C=Ogrup.
ii) β- pleated sheet : peptide chains laid side by side and held together by H-
bonds
3) Tertiary structure: It represent further folding of the secondary
structure. It gives rise to two major molecular shapes viz. fibrous and
globular.
4) Quaternary structure of proteins: composed of two or more
polypeptide chains referred to as sub-units. The spatial arrangement of
these subunits with respect to each other.
Denaturati Disturbing the 20 and 30 structures of proteins by heating or changing
on of
pH. eg: coagulation of egg white on boiling .
proteins
Nucleic acids Polymer of nucleotides linked by phosphodiester linkage -3’ 5’ linkage
Nucleotide Each nucleotide contains N-base, Sugar and Phosphate.
Nucleoside Contains N-base & Sugar.
Double Two strand of DNA coiled around each other and held together by H-
helical bonds b/w pairs of bases. Such as − C≡G−, and −A =T−
structure of Purines : Adinine & Guanine And Pyrimidines : Cytosine, Uracil & Thymine
DNA
DNA N-Bases : A,G ,C &T, Double helix, Contains 2-deoxy ribose
sugar, Transfer heredity characters.
RNA N-Bases: A,G C & U, Single helix, Contains Ribose sugar, Helps
in proteins synthesis.
Preparation of
Glucose

Structure of
Glucose

Reactions of
Glucose

Reactions that i. Aldehyde group present but glucose does not react with NaHSO3&
prove cyclic NH3.
structure of ii. Glucose does not give the Schiff’s Test & 2,4-DNP test for aldehyde.
Glucose iii. Glucose penta-acetate does not react hydroxyl amine, which shows
that aldehyde group is absent in glucose.
iv. Glucose exist in two stereo-isomeric forms ( & ).
All observations indicate that free aldehydic group is not present in glucose.
 Cyclic Structure of
Glucose

Structure of Nucleotide

Q.1 List the reactions of glucose which cannot be explained by its open chain structure.
Ans-

Q2. Name two water soluble vitamins, their sources and diseases caused due to their deficiency in diet.
Ans-

Q3. Name two fat soluble vitamins, their sources and the diseases caused due to their deficiency in diet.
Ans.
Q4.

Ans-

Q5. State the differences between a nucleotide and a nucleotide.

Ans-

Q6. What are essential and non-essential amino acids? Give one example of each type.
Ans-

Q7. What are the different type of Mino acids? Explain with example.
Q8. Differentiate between fibrous and globular proteins?

Q9. Describe what you understand by primary and secondary structure of proteins.
Ans-

Q10. Write the structural differences between DNA and RNA. Of the four based, name those which are
common to both DNA and RNA.
Ans-

Q11.

Ans-
Q12. Explain what is meant by the following:
(i) Peptide Linkage
(ii) Pyranose structure of glucose

Ans-

Q13. Name the products of hydrolysis of (i) Sucrose (ii) Lactose.

Ans-

Q14. What is meant by (i) Peptide Linkage (ii) Biocatalysts

Ans-
 Organic Chemistry Explanations
1 Bond enthalpy decreases as : CH3-F > CH3-Cl > CH3-Br > CH3-I

Because C-X bond length increases from F to I due to greater size

2 Phenol can not be converted into chlorobenzene by using HCl

Because C-O bond in phenol has partial double bond character and OH gr is attached to sp 2 carbon,

3 Thionyl chloride is preferred to convert ROH into RCl

Because the side products are gases and the product can be obtained as pure

4 30 alcohol easily can be converted into alkyl halide

Because 30 carbocations are stable

5 Benzene is converted into iodobenzene in presence of oxidizing agent like HNO 3 or HIO3

C6H6 + I2/Fe C6H5I + HI Because HNO3 or HIO3 oxidises HI and prevent backward reaction
6 ROH is converted into RI by using KI in presence of H3PO4 not H2SO4

H2SO4 converts KI into HI and than into I2

7 B.pt. of alkyl halides (RX) is higher than hydrocarbons

Because R-X is polar so there is dipole dipole attraction

8 B.pt : R-I > R-Br > R-Cl > R-F
Because molecular mass decreases so van der Waals force decreases from RI to RF

9 B.pt : CH3-CH2-CH2-CH2-Br > CH3-CH2-CH(Br)-CH3 > (CH3)CBr

Because as the branching increases surface area decreases so van der Waals force of attraction decreases

10 p-dichloro benzene has higher m.pt than ortho and meta isomer
Because p-dichloro benzene has symmetrical structure so it fits well in the crystal lattice

11 Alkyl halide (RX) with KCN gives alkyl cyanide (RCN) where as with AgCN it gives isocyanide(RNC)

KCN is ionic and CN- is ambedent nucleophile but it link through C because C-C bond is more stable than C-N. In the other hand
AgCN is covalent and links through N only
12 SN2 reactivity : CH3-X > CH3CH2-X > CH3-CH(X)-CH3 > (CH3)3C-X ( 10 >20>30)
Due to steric hindrance nucleophile can not approach easily. In S N2 path release of X and linking of Nu- take place
simultaneously

13 SN1 reactivity : CH3-X < CH3CH2-X < CH3-CH(X)-CH3 < (CH3)3C-X ( 10 <20<30)

Because SN1 path involves formation of carbocation intermediate. And stability of carbocation is in the order : CH 3+ < CH3CH2+
< (CH3)2CH+ < (CH3)3C+ ( 10 <20<30)

14 SN reactivity : R-I > R-Br > R-Cl > R-F

Because as the size of halogen increases C-X bond becomes weaker
15 Aryl halides ( C6H5-X) are less reactive than alkyl halides(R-X) towards nucleophilic substitution

Because in aryl halide C-X bond has partial double bond character and X is attached to sp2 C. there is also the repulsion
between Nu- and benzene ring which is electron reach

16 Chloroform is stored in dark coloured bottle as closed and completely filled

Because in air and light it converts into poisonous phosgene gas(COCl2)

17 In many countries DDT has been banned now

Because of its slow metabolism and it gas toxic effect on aquatic animals

18 Cyclohexyl chloride has greater dipole moment than chloro benzene

The lone electron pair of chlorine get delocalized towards benzene ring due to resonance decreasing the polarity of C-Cl bond.

19 Alkyl halides are immiscible in water although they are polar

In water there is intermolecular H-bonding but there is less attraction between R-X and H2O

20 Grignard reagent(RMgX) should be prepared in anhydrous condition

Because RMgX reacts with water and gives corresponding alkane

21 Alkyl halides undergo substitution when treated with aq KOH but in presence of alc KOH elimination takes place

Alcohol + KOH produces RO- which is a strong base so it extract H+ and elimination takes place

22 C-O-H bond angle in alcohol is less than regular tetrahedral angle

Due to lp-lp repulsion

23 In phenol the C-O bond length is less
Due to i) partial double bond character ii) O is attached to sp2 carbon

24 In ether the R-O-R bond angle is greater

Due to repulsion between two bulkier R group

25 To convert acid into alcohol LiAlH4 is not used

Because it is expensive so : RCOOH RCOOR’ then ester is reduced into RCH2OH by using H2/Pd

26 b.pt of alcohol(ROH) is higher than alkane(RH), ether(R-O-R), alkyl halide(R-X) and aryl halide(Ar-X)

Due to inter molecular H-bonding in R-O-H.

27 b.pt : n-butyl alcohol > sec. butyl alcohol > tert. Butyl alcohol

Because as the branching increases surface area decreases so van der Waals force of attraction decreases

28 Alcohols are highly miscible in water

Due to H-bonding with water

29 Acidity of alcohol : R-CH2-OH > R2CH-OH > R3C-OH

Because as the R gr increases +I effect increases so alkoxide ion becomes less stable
30 Alcohol is weaker acid than water

Because R-O- is less stable than HO-

31 Phenol (Ph-OH) is acidic in nature

Because phenoxide ion( Ph-O-) is resonance stabilized.

32 Acidity : nitro phenol > phenol > methyl phenol

Because –NO2 group is electron withdrawing it further increases the stability of phenoxide ion where as-CH3 group is electron
donating it destabilizes phenoxide ion

33 Esterification is carried out in presence of small amount of conc. H2SO4

Because it absorbs the water produced and accelerate the forward reaction.

34
R’COCl + R-OH R’COOR + HCl. Pyridine is used in this reaction

It is to remove HCl produced and to prevent the backward reaction

35 Tert. Alcohols are easier to dehydrate

Because the intermediate tert. carbo cation is stable.

36 -OH group in benzene ring is ortho and para directing for electrophilic substitution

Due to +R effect it increases the electron density at ortho and para positions

37 o-nitro phenol is steam volatile( low b.pt) but p-nitro phenol is not

In o-nitro phenol there is intra molecular H-bonding. But in p-nitro phenol there is inter molecular H-bonding so molecules get
associated and hence it has comparatively higher b.pt

38 Phenol with aq bromine gives 2,4,6-tribromo phenol but in non polar medium mono substitution takes place

In aq. Medium phenoxide ion is the main substrate which is not produced in non-polar medium. the benzene ring is more
activated in phenoxide ion than in phenol itself.
39 CuSO4 and pyridine are mixed with ethanol used for industrial purpose

To prevent its misuse. CuSO4 gives colour pyridine gives smell

40 Ethers ( R-O-R) are polar

Due to angular structure of R-O-R there is net polarity.

41 Ethers are soluble in water

Due to H-bond with water and ether

42 Aldehydes (R-CHO) and ketones (R-CO-R) have higher b.pt than hydrocarbon and ether

Because they are polar so there is dipole-dipole attraction in aldehyde and ketones

43 Lower aldehydes and ketones are miscible with water

Because they form hydrogen bond with water

44 Aldehydes (R-CHO) are more reactive than ketones (R-CO-R) in nucleophilic addition

In ketone the two alkyl groups ( R ) have +I effect so they reduce the electrophilicity co carbonyl carbon. Also there is steric
hindrance in ketone

45 Benzaldehyde ( C6H5CHO ) is less reactive than propanal ( CH3CH2CHO )

Due to resonance the electrophilicity of carbonyl carbon is less in benzaldehyde

46 NaHSO3 is used for separation of aldehydes

It forms a soluble compound with aldehyde which on hydrolysis give back the aldehyde
47 α-H of aldehyde and ketone is acidic in nature
Because the corresponding carbanion is resonance stabilized

48 Carboxylic acids ( R-COOH ) do not give nucleophilic addition reaction like RCHO & RCOR although it has >C=O

due to resonance the carbonyl carbon looses its electrophilicity

49 Carboxylic acids have higher b.pt than aldehyde, ketones and even than alcohols

There is extensive inter molecular H-bonding in carboxylic acid(RCOOH). Even in vapour phase it exists as dimer
50 Carboxylic acids are miscible in water

Due to H-bonding with water

51 R-COOH is acidic in nature

Because the conjugate base R-COO- (carboxylate ion) is stable due to resonance

52 Acidic Strength : Cl-CH2-COOH > CH3-COOH > CH3CH2-COOH

Because Cl has –I effect which stabilizes the conjugate base and ethyl gr has +I effect

53 In amines the C-N-H/C bond angle is less than 109.5o

Due to lp-bp repulsion

54 For reduction of nitro compounds into amines Fe/HCl is preferred instead of Sn/HCl

Because Fe + HCl FeCl2. on hydrolysis FeCl2 gives HCl. So just small quantity of HCl is required to initiate the reaction

55 To convert alkyl halide(R-X) into amines (R-NH2) ammonolysis is not suitable

Because on ammonolysis a mixture of pri, sec, tert and quaternary amine will be produced

56 Aniline on exposure to air and light turns into coloured

Due to atmospheric oxidation

57 Lower amines are soluble in water

Due to H-bonding with water. In case of higher amine alkyl group is larger which is hydrophobic

58 Amines (R-NH2) are less soluble than alcohols (R-OH)

In alcohol the H-bonding with water is stronger because O is more electronegative than N

59 Amines (R-NH2) are lower boiling than alcohols (R-OH)

In alcohol the inter molecular H-bonding is stronger because O is more electronegative than N

60 Order of b.pt : primary amine > sec. amine > tert. amine

The no of N-H bond decreases so extent of H-bonding also decreases

61 In gaseous phase the order os basic strength : 3 0-amine > 20-amine > 10-amine > NH3

Due to +I effect of alkyl groups the electron density on N increases. So 30 is strongest as it has 3 alkyl groups
62 In aqueous state the base strength order

:(C2H5)2NH > (C2H5)3N > C2H5NH2 > NH3 ( 20 > 30 > 10 > NH3)

: (CH3)2NH > CH3NH2 > (CH3)3N > NH3 ( 20 > 10 > 30 > NH3)

In aqueous state +I effect, steric effect and salvation effect interplay. So the order is not regular

63 R-NH2 is stronger base than NH3

Due to +I effect of alkyl group electron density on N increases in R-NH2

64 Aniline ( C6H5-NH2) is weaker base than NH3 and R-NH2

In aniline the lone pair of electron of N is involved in resonance. So it is less available.

65 Base strength : p-methoxy aniline > aniline > p-nitro aniline

Methoxy group (-OCH3) has +R effect where as –NO2 group has –R effect so electron density in the first case increases but in
the second case it decreases.

66 Acylation of aniline is carried out in presence of pyridine

Pyridine removes HCl produced and favours forward reaction

67 -NH2 group in benzene ring is ortho –para directing for electrphilic substitution

Due to +R effect it increases the electron density at ortho and para position

68 Bromination of aniline gives 2,4,6-tribromo aniline

Because –NH2 group activates benzene ring by +R effect. So for mono substitution –NH2 group is acylated.

69 Nitration of aniline gives unusual meta-nitro aniline although –NH2 group is ortho-para directing

In presence of acid –NH2 is converted into –NH3+ which is meta directing

70 Aniline does not undergo Friedel Craft reaction

Aniline is base and reacts with anhydrous AlCl3 so N becomes positive which deactivates benzene ring.