Ssq Class Xii
Ssq Class Xii
Ssq Class Xii
INDEX
SL.NO CHAPTERS PAGE NO
1 SOLUTIONS 07-20
2 ELECTROCHEMISTRY 21-34
9 AMINES 139-149
10 BIOMOLECULES 150-162
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CHEMISTRY THEORY (043) SYLLABUS FOR SESSION 2024-25
CLASS – XII
Unit I: Solutions (7 marks) 10 Periods
Types of solutions, expression of concentration of solutions of solids in liquids,
solubility of gases in liquids, solid solutions, Raoult's law, colligative properties - relative
lowering of vapour pressure, elevation of boiling point, depression of freezing point,
osmotic pressure, determination of molecular masses using colligative properties,
abnormal molecular mass, Van't Hoff factor.
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Coordination compounds - Introduction, ligands, coordination number, colour, magnetic
properties and shapes, IUPAC nomenclature of mononuclear coordination compounds.
Bonding, Werner's theory, VBT, and CFT; structure and stereoisomerism, the
importance of coordination compounds (in qualitative analysis, extraction of metals and
biological system).
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Carbohydrates - Classification (aldoses and ketoses), monosaccharides (glucose and
fructose), D-L configuration oligosaccharides (sucrose, lactose, maltose), polysaccharides
(starch, cellulose, glycogen); Importance of carbohydrates. Proteins -Elementary idea of -
amino acids, peptide bond, polypeptides, proteins, structure of proteins - primary,
secondary, tertiary structure and quaternary structures (qualitative idea only),
denaturation of proteins; enzymes. Hormones - Elementary idea excluding structure.
Vitamins - Classification and functions. Nucleic Acids: DNA and RNA.
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Chapter 1. SOLUTIONS
QUICK REVISION POINTS:
It is a homogenous mixture of solute and solvent. (Solute + Solvent=Solution)
Types of solutions: -
Sl.No. Solute Solvent Types of Examples
Solutions
1. Solid Solid alloys like brass, bronze, an alloy of
copper and gold
2. Liquid Solid Solid solutions Mercury with Sodium(amalgams)
3. Gas Solid Solution of H2 in Pd, dissolved gases in
minerals
4. Solid Liquid Sugar solution, salt solution
5. Liquid Liquid Liquid Benzene in toluene, alcohol in water.
6. Gas Liquid Solutions CO2 in water, NH3 in water
7. Solid Gas Iodine vapours in air, camphor in N2
8. Liquid Gas Gaseous Water vapours in air, CHCl3 mixed with N2
Solutions gas
9. Gas Gas Air (O2 + N2),any non-reacting gases together
EXPRESSING CONCENTRATION OF SOLUTIONS
Some basic formulae: -
Mass percentage. Mole fraction Molarity (M) =
w/w% For solvent XA=nA/nA+nB no. of moles of
For solute XB=nB/nA+nB solute/volume of solution (L)
XA + XB = 1 Unit=mole/litre [mol/L]
ppm (parts per million)=
Molality (m) =
For liquid solutions no. of moles of solute/mass
v/v % = mass of solute of solvent(kg)
(WB)x106/total mass of Unit=mole/Kilogram
𝑉𝑜𝑙𝑢𝑚𝑒 𝑜𝑓 𝑠𝑜𝑙𝑢𝑡𝑒(𝑉𝐵) solution (WA+WB) [mol/kg]
𝑉𝑜𝑙𝑢𝑚𝑒 𝑜𝑓 𝑠𝑜𝑙𝑢𝑡𝑖𝑜𝑛(𝑉𝐴 + 𝑉𝐴 )
NOTE:, mole fraction, mass percentage, ppm and molality are independent of
temperature, whereas molarity depends on temperature. This is because volume
depends on temperature.
SOLUBILITY (maximum amount of solute present in a specific amount of solvent at a
specified temperature) of gas depends on:
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solubility)
APPLICATIONS: Soft drinks are sealed under high pressure to increase solubility of
CO2.
To avoid BENDS, the tanks used by scuba divers are filled with air diluted with helium
(less soluble than N2)
ANOXIA problem at higher altitudes due to low pressure low concentration of O2 in
Blood cells.
Vapour pressure: -The pressure exerted by the vapours in the equilibrium with liquid at
a given temperature.
For two volatile liquids For one non-volatile and one volatile
liquid
PA = P0AΧA PB = P0BΧB PA = P0AΧA PB =0
Dalton’s partial pressure Dalton’s partial pressure
PTotal= P0AΧA+ PB0ΧB PTotal= P0A(1-XB)+ PB0ΧB PTotal= P0AΧA+0 PTotal= P0AΧA
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Relative lowering Elevation in boiling Depression in Osmosis
in point freezing point
vapour pressure
poA-ps/poA=XB ΔTb =Tb-𝑻𝒐𝒃 ΔTf =Tf-𝑻𝑶
𝒇
π=CRT
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IMPORTANT POINTS:
Antifreeze agent: ethylene glycol used in car radiators at hill stations (Depression in
freezing point)
De-icing agents: common salt (NaCl) or calcium chloride (CaCl2) is scattered on the
roads to melt ice in cold countries (Depression in freezing point)
Biological and Industrial importance of osmosis:
• In animals, circulation of water to all parts of body takes place due to osmosis.
• Plant roots absorb water from soil due to osmosis. Concentration of cell sap inside
the root hair cells is higher than that of water present in the soil. Water enters the
root cells due to endosmosis.
• Water absorbed by plant roots is circulated in the entire plant body and reaches to
the top of a tall tree due to osmosis.
• Osmosis helps in plant growth and germination of seeds.
• Red blood cells burst when placed in water; it is due to endosmosis.
• Various functions of plants are controlled by osmosis, e.g., stretching of leaves and
flowers, opening and closing of flowers.
• Use of salt and sugar in pickles and jams acts as preservatives. It prevents growth
of bacteria and fungi by osmosis.
• Dead bodies swell under water due to endosmosis.
• When dried fruits and vegetables are placed in water, they slowly swell and return
to the original form. It is again due to the endosmosis of water into the fruits and
vegetables.
• Edema: Due to excess intake of salt by a person, the tissues become puffy, it is
called edema. It is due to retention of water in the tissue owing to osmosis.
• The preservation of meat by salting and of fruits by adding sugar protects against
bacterial action. Through the process of osmosis, a bacterium on salted meat or
candid fruit loses water, shrivels and dies.
The osmotic pressure method has got advantages over other colligative properties:
The measurement of osmotic pressure is around the room temperature, gives large
measurable values for molar masses and molarity of the solution is used instead of
molality.
Conditions for normal molar mass (Accurate value)
Solute must be non-volatile, Solution must be dilute and solute should not undergo any
association or dissociation in the solution (non-electrolyte solution).
Abnormal molar mass: ELECTROLYTIC SOLUTIONS: - When the molar mass of a
substance (solute) become higher or lower after its association or dissociation in the
solution it is called abnormal molar mass.
Van’t Hoff factor: i = normal molar mass/abnormal(observed)molar mass
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Colligative property after abnormal
PROPERTY ASSOCIATION DISSOCIATIO
molar masses: -
N
Lowering of vapour pressure: - No. of Less more
molecules
XB = i poA-ps/poA
Colligative Lowers Increases
Elevation in boiling point: - property
Molar mass Greater than lesser
ΔTb=i Kb m
theoretical
Depression in freezing point: - value
i=1 i Less than 1 i More than 1
ΔTf = i Kf m
(extent) 𝑖−1 𝑖−1
Osmotic pressure: - π=iCRT =degree of 1 𝑛−1
dissociation / 𝑛−1 [n = no. of
association [n = no. of dissociated
particles particles.]
associated]
MULTIPLE CHOICE QUESTIONS (1 MARK)
1 KH value for Ar(g), CO2(g), HCHO (g) and CH4(g) are 40.39, 1.67, 1.83 × 10-5 and
0.413 respectively. Arrange these gases in the order of their increasing solubility.
a) HCHO < CH4 < CO2 < Ar b) HCHO < CO2 < CH4 < Ar
c) Ar < CO2 < CH4 < HCHO d) Ar < CH4 < CO2 < HCHO
2 When a non-volatile solid is added to pure water it will:
a) boil above 100oC and freeze above 0oC b) boil below 100oC and freeze
above 0 Co
c) boil above 100oC and freeze below 0oC d) boil below 100oC and freeze
below 0 Co
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(a) Al2(SO4)3 (b) NaCl (c) Al(NO3)3 (d) Na2SO4
10 Pure benzene has vapour pressure three times that of pure toluene. They form
nearly ideal solution. What would be the ratio of their mole fractions in the vapour
phase of a solution having equal mole fractions of benzene and toluene.
a)1 b) 2/3 c) 3 d) 1/3
ANSWERS
1 (a), 2 (a), 3 (d), 4 (c), 5 (b), 6 (d), 7 (b), 8 (c), 9 (a) , 10 (c)
ASSERTION REASON TYPE QUESTIONS (1 MARK)
Note: In the following questions (1-5) a statement of assertion followed by a
statement of reason is given. Choose the correct answer out of the following
choices.
(a) Assertion and reason both are correct statements and reason is the correct
explanation for assertion.
(b) Assertion and reason both are correct statements but the reason is not a
correct explanation for assertion.
(c) Assertion is a correct statement but the reason is the wrong statement.
(d) Assertion is a wrong statement but the reason is a correct statement.
1 Assertion: When methyl alcohol is added to water, the boiling point
of water decreases.
Reason: When a volatile solute is added to a volatile solvent elevation in boiling
point is observed.
2 Assertion: Cooking time in pressure cooker is reduced
Reason: Boiling point inside the pressure cooker is raised
3 Assertion: Vapour pressure of a liquid is constant at a constant temperature
Reason: At equilibrium rate of evaporation becomes equal to the rate of
condensation.
4 Assertion: The components of azeotropic mixture can be separated by distillation
Reason: At a particular composition azeotropic mixture boil at the same
temperature.
5 Assertion: The shrinking of cells is called hemolysis.
Reason: Hemolysis occurs when cell comes in contact with solution of lower
osmotic pressure than that of cell
ANSWERS
1 (c), 2 (a) , 3 (a) , 4 (d) , 5 (d)
Q 3 X and Y liquids on mixing produces cold solution. What type of deviation is shown
by them?
Ans Positive deviation
Q 4 Aquatic species are more comfortable in cold waters rather than in warm waters.
Give reason.
Ans Solubility of gases increases with decrease in temperature as it is an exothermic
process.
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Q 5 If is α the degree of dissociation of Na2SO4, calculate Van't Hoff factor to determine
the molecular mass.
Ans 1+2α
Q 6 Give an example of a substance that can be used as a SPM.
Ans Pig’s bladder or parchment or cellophane.
Q 7. What happens when blood cells are placed in a solution containing more than 0.9%
(mass/volume) sodium chloride?
Ans Water will flow out of the cells and they would shrink
Q 8 People taking lot of salt experience puffiness or swelling of the body. Why ?
Ans People taking lot of salt experience puffiness or swelling of the body due to water
retention in tissue cells and intercellular spaces because of osmosis.
Q 9 What are hypotonic solutions?
Ans A solution which has lower osmotic pressure than the other solution separated by a
semipermeable membrane is called hypotonic solution
Q 10 How can the direction of osmosis be reversed?
Ans The direction of osmosis can be reversed if a pressure larger than the osmotic
pressure is applied to the solution side.
VERY SHORT ANSWER QUESTIONS (2 MARKS)
1 a) Common salt and Calcium chloride are used to clear snow on the roads, both
are of almost same cost but sodium chloride is preferred. Why?
b) How the freezing point changes when mercuric iodide is added to the aqueous
solution of potassium iodide?
Ans a) NaCl is needed in lesser quantity.
b) Freezing point is raised as no. of particles decreases which results in decrease
in colligative property.
2 a) Write the expression for degree of dissociation of a weak electrolyte AxBy in
terms of Van’t Hoff factor.
b) Name a substance that can be used in radiators of vehicles in places where the
temperature is less than zero.
Ans a) = i-1/(x+y-1) b) Ethylene glycol
3 a) How the osmotic pressure of 5 % aqueous solution of glucose (𝜋1) is related to
that of 5 % aqueous solution of urea (𝜋2)?
b) Why do salt water fish die when they are suddenly transferred to a fresh water
aquarium?
Ans a) 𝜋1< 𝜋2
b) Water from aquarium enters in cell causing them to expand and get ruptured.
4 a) Two 500 ml beakers were taken. One filled with 400ml water marked ‘X’ and
another with 400ml of 2M NaCl solution marked ‘Y’. At the same temperature
both were placed in closed containers of same material and same capacity, in
which container the vapour pressure is less.
b) Out of 1M sucrose and 1M urea solution which has more osmotic pressure?
Ans a) Y
b) Both have osmotic pressure.
5 a) Sia’s father is suffering from high blood pressure but he is advised to consume
less quantity of common salt. Why?
b) Two solutions A and B are separated by semi-permeable membrane. If the
liquid flows from A to B then which solution is more concentrated?
Ans a) More salt use will increase ions in the body fluid which increases blood
pressure
b) B
6 a) Why the colligative property of an electrolyte solution is always greater than
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that of a non-electrolyte solution?
b) Mohit wants to put an egg with outer shell removed in a bottle but he is unable
to do so as mouth of bottle is slightly smaller. Suggest one method to help him
putting the peeled egg in the bottle
Ans a) Due to dissociation of electrolyte the number of ions increases
b) Peeled egg shrinks in saturated brine solution.
7 a) Out of 1M and 2M sugar solutions which one has a lower boiling point?
b) While performing practical it is directed that the bottle of liquid ammonia is to
be cooled before opening the seal but Suman forgot to cool it before opening.
What consequence she faced?
a)1M (higher the concentration of solute added higher is the colligative property)
Ans b) It is cooled to lower down the pressure of ammonia else the gas will bump out
of the bottle.
8 a) What is the effect of temperature on the process when shrunk and dried
vegetables are placed in water?
b) The boiling point of 0.2 mol kg–1 solution of X in water is greater than
equimolal solution of Y in water. Which one is undergoing dissociation in
water?
Ans a) Process will be accelerated with increase in temperature as osmosis becomes
faster with increase in temperature.
b) X
9 a) What is the unit of Ebullioscopic constant?
b) Which type of deviation is shown by Carbon tetrachloride and chloroform
mixture?
Ans a) K kg mol-1 or K (molality)-1
b) positive deviation
10 a) What is the significance of Henry’s Law constant KH?
b) How the colligative properties change if the solute undergo dissociation in
solution?
Ans a) Henry’s Law constant (KH) helps in comparing the relative solubilities of
different gases in the same solvent (e.g. water). In general, the lesser the value of
KH, the more the solubility of a gas.
b) increases due to increase in number of particles on dissociation.
SHORT ANSWER TYPE QUESTIONS (3 MARKS)
1 a) If the elevation in boiling point of a solution for which i = 1 in a solvent (K f =x K
kg mol-1 and Kb=y K kg mol-1) is z K,then calculate the depression in freezing point
of the same concentration.
b) Give two examples of materials used for making semi permeable membrane for
carrying out reverse osmosis.
Ans a) z x/y
b) Cellulose acetate, potassium ferrocyanide
2 a) What is the degree of dissociation for 0.1M Ba (NO3)2 if i(Van’t Hoff factor) is
2.74
b) Arrange the following solutions in increasing order of Van’t Hoff factor.
0.1M CaCl2, 0.1M KCl, 0.1M C12H22O11, 0.1 M Al2(SO4)3
Ans a) = ⅈ−1
𝑛−1
= 87%
b) 0.1M C12H22O11 < 0.1M KCl < 0.1M CaCl2 < 0.1 M Al2(SO4)3
3 a) Molal elevation constant for benzene is 2.52 K/m. A solution of some organic
substance in benzene boils at 0.126oC higher than benzene. What is the molality
of the solution?
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b) What are the values of Van’t Hoff factor for NaCl and K2SO4, respectively?
Ans a) ΔTb= Kb m, molality=0.05m
b) 2 and 3
4 a) State Henry’s law.
b) Which cold drink you prefer one chilled or other one at room temperature and
why?
c)At the same temperature hydrogen is more soluble in water than Helium. Which
of them will have higher value of KH and why?
Ans a) Mole fraction of gas in the solution is directly proportional to partial pressure
of gas in the vapour phase
b) Chilled as solubility of CO2 is more at low temp.
c) Helium as greater the KH value lower the solubility
5 a) Account for the reason, marine life like fish prefers to stay at lower level and
stay away from the upper layer of water.
b) Why freezing/melting point of a substance used as a criterion for testing the
purity of a substance?
c) Account for the reason for preservation of fruits against bacterial action by
adding sugar.
Ans a) Temperature is higher in upper layer so solubility of oxygen is less
b) M.P./F.P. changes due to impurities.
c) Bacterium in canned fruit loses water through the process of osmosis, shrivels
and dies.
LONG ANSWER TYPE QUESTIONS (5 MARKS)
1 a) If boiling point of an aqueous solution containing a non-volatile solute is
100.15oC. What is its freezing point? Given latent heat of fusion and vapourisation
of water are 80cal/g and 540 cal/g respectively.
b) Electrolyte A gives 4 ions and B is a non-electrolyte. If 0.1 molar solution of
solute B produces an osmotic pressure ‘p’, then 0.02 molar solution of A will
produce how much osmotic pressure?
Ans 𝑅×𝑀1 ×𝑇𝑓2 𝑅×𝑀1 ×𝑇𝑏2
a) ΔTb=Kb m, ΔTf=Kf m 𝐾𝑓 = 1000×∆ 𝐻 𝐾𝑏 = 1000×∆
𝑓𝑢𝑠 𝐻 𝑣𝑎𝑝
𝑇𝑓2 𝑋 𝑙𝑎𝑡𝑒𝑛𝑡 ℎ𝑒𝑎𝑡 𝑜𝑓 𝑓𝑢𝑠ⅈ𝑜𝑛
Kf/Kb=𝑇 2 𝑋 𝑙𝑎𝑡𝑒𝑛𝑡 ℎ𝑒𝑎𝑡 𝑜𝑓 𝑣𝑎𝑝𝑜𝑢𝑟ⅈ𝑠𝑎𝑡ⅈ𝑜𝑛 = ΔTf/ ΔTb
𝑏
ΔTf= 0.542 Tf=0-0.542=-0.542oC
b) 0.8p
2 a) 0.6 mL of acetic acid 𝐶𝐻3 𝐶𝑂𝑂𝐻, having density 1.06 g/mL, is dissolved in 1 litre
of water. The depression in freezing point observed for this strength of acid was
0.0205°C. Calculate the van’t Hoff factor and the dissociation constant of acid.
𝐾𝑓 = 1.86 K kg /mol.
b) How does Raoult’s law become a special case of Henry’s law?
Ans a) First find out number of moles of acetic acid, mass of acetic acid =volume x
density
mass of acetic acid=0.6 X 1.06= 0.636 g and molar mass of acetic acid = 60 g/
mol
𝑚𝑎𝑠𝑠 𝑜𝑓 𝑎𝑐𝑒𝑡𝑖𝑐 𝑎𝑐𝑖𝑑 0.636
𝑛𝑜. 𝑜𝑓 𝑚𝑜𝑙𝑒𝑠 𝑜𝑓 𝑎𝑐𝑒𝑡𝑖𝑐 𝑎𝑐𝑖𝑑 = = 0.0106
𝑚𝑜𝑙𝑎𝑟 𝑚𝑎𝑠𝑠 𝑜𝑓 𝑎𝑐𝑒𝑡𝑖𝑐 𝑎𝑐𝑖𝑑 60
𝑁𝑜. 𝑜𝑓 𝑚𝑜𝑙𝑒𝑠 0.0106
𝑚𝑜𝑙𝑎𝑙𝑖𝑡𝑦 = 𝑚𝑎𝑠𝑠 𝑜𝑓 𝑠𝑜𝑙𝑣𝑒𝑛𝑡 = 1 = 0.0106 𝑚 (As density of water = 1 g/𝑐𝑚3 ) ∴ 1 𝐿 =
1𝑘𝑔)
0.0205
∆𝑇𝑓 = 𝑖 𝐾𝑓 𝑚 𝑖 = 1.86×0.0106 = 1.04
ⅈ−1 1.04−1
𝛼 = 𝑛−1 = = 0.04 As n=2, 𝐶𝐻3 𝐶𝑂𝑂𝐻 ⇋ 𝐶𝐻3 𝐶𝑂𝑂− + 𝐻 +
2−1
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[𝐶𝐻3 𝐶𝑂𝑂− ][𝐻 + ] 𝑐𝛼 × 𝑐𝛼 𝑐𝛼2 0.0106 ×0.04×0.04
Dissociation constant 𝐾𝑎 = = = = = 1.76 × 10−5
[𝐶𝐻3 𝐶𝑂𝑂𝐻] 𝑐(1−𝛼) 1−𝛼 1−0.04
b) In two laws only the proportionality constant KH differs from PA0. Thus,
Raoult’s law becomes a special case of Henry's law in which KH = PA0
Q1. Boiling point or freezing point of liquid solution would be affected by the dissolved
solids in the liquid phase. A soluble solid in solution has the effect of raising its
boiling point and depressing its freezing point. The addition of non-volatile
substances to a solvent decreases the vapor pressure and the added solute
particles affect the formation of pure solvent crystals. According to many
researches the decrease in freezing point directly correlated to the concentration
of solutes dissolved in the solvent. This phenomenon is expressed as freezing
point depression and it is useful for several applications such as freeze
concentration of liquid food and to find the molar mass of an unknown solute in
the solution. Freeze concentration is a high-quality liquid food concentration
method where water is removed by forming ice crystals. This is done by cooling
the liquid food below the freezing point of the solution. The freezing point
depression is referred as a colligative property and it is proportional to
the molar concentration of the solution (m), along with vapor pressure relative
lowering, boiling point elevation, and osmotic pressure. These are physical
characteristics of solutions that depend only on the identity of the solvent and the
concentration of the solute. The characters are not depending on the solute’s
identity.
(Jayawardena, J. A. E. C., Vanniarachchi, M. P. G., & Wansapala, M. A. J. (2017).
Freezing point depression of different Sucrose solutions and
coconut water.)
A What is the relation between vapour pressure of solid and liquid states at freezing
point?
B Why freezing point of 0.1m solution of acetic acid in benzene is less than freezing
point of 0.01m solution?
C Out of the following 0.10 m aqueous solutions, which one will exhibit the largest
freezing point depression? KCl , C6H12O6 , Al2(SO4)3 , K2SO4
OR
C If Kf for water is 1.86 oC/m, explain why 1m NaCl in water does not have a
freezing point equal to a) -1.86 oC b) -3.72oC
ANS Q1
A Equal
B Depression in FP in 0.1m solution is more than 0.01 solution so FP of first is less.
C C6H12O6
OR
C a) as there are 2 moles of ions per mol of NaCl
b) degree of ionisation is not 100% at freezing point due to stronger interactions
for 1m solution.
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Q2 1. Henna is investigating the melting point of different salt solutions. She makes a
salt solution using 10 mL of water with a known mass of NaCl salt. She puts the
salt solution into a freezer and leaves it to freeze. She takes the frozen salt
solution out of the freezer and measures the temperature when the frozen salt
solution melts. She repeats each experiment.
Assuming the melting point of pure water as 0oC, answer the following questions:
(a) One temperature in the second set of results does not fit in the pattern. Which
temperature is that? Justify your answer. 1
(b) Why did Henna collect two sets of results? 1
(c) In place of NaCl, if Henna had used glucose, what would have been the melting
point of the solution with 0.6 g glucose in it? 2
OR
(c) What is the predicted melting point if 1.2 g of salt is added to 10 mL of water?
Justify your answer.
Ans- a) 3rd reading for 0.5 g there has to be an increase in depression of freezing point
Q2 and therefore decrease in freezing point so also decrease in melting point when
amount of salt is increased but the trend is not followed in this case.
b) Two sets of reading help to avoid error in data collection and give more objective
data.
c.) ΔTf (glucose) = 1 x Kf x 0.6 x 1000 /180x 10 ……….. (1)
ΔTf (NaCl) = 2 x Kf x 0.6 x 1000 / 58.5x10
3.8 = 2 x Kf x 0.6 x 1000 /58.5x 10 ……………. (2)
Divide equation 1 by 2
ΔTf (glucose)/ 3.8 = 58.5/ 2 x 180
ΔTf (glucose) = 0.62
Freezing point or Melting point = - 0.62 oC
OR
depression in freezing point is directly proportional to molality (mass of solute
when
the amount of solvent remains same)
0.3 g depression is 1.9 oC
0.6 g depression is 3.8 oC
1.2 g depression will be 3.8 x2 = 7.6 oC
Q3 Aarav Sharma is very fond of a special drink made by his grandmother using
different fruits available in their hometown. It has an outstanding taste and also
provides great health benefits of natural fruits. He thought of utilizing his
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grandmother recipe to create a new product in the beverage market that provide
health benefits and also contain fizziness of various soft drinks available in the
market. Based on your understanding of solutions chapter, help Aarav Sharma to
accomplish his idea by answering following:
(a) How he can add fizz to the special drink made by his grandmother? 1
(b) What is the law stated in the chapter that can help Aarav to make his drink
fizzy? 1
(c) What precautions he should take while bottling so that his product does not
lose fizz during storage and handling across long distances? 2
OR
(c)The mole fraction of helium in a saturated solution at 20°C is 1.2 x 10-6. Find
the pressure of helium above the solution. Given Henry’s constant at 20°C is
144.97 kbar.
Ans- a) Carbon dioxide is a gas which provides fizz and tangy flavour. He can dissolve
Q3 Carbon dioxide gas in the drink.
b) Henry’s law which states that solubility of a gas in liquid is directly
proportional to partial pressure of the gas.
(c) Bottles should be sealed under high pressure of CO and capping should be
done perfectly to avoid leakage of CO2 as any loss of partial pressure will result
into decrease in solubility.
OR
(c) pHe = KH x XHe
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phase and boil at a constant temperature.
(c) Hexane and heptane form ideal solution. Those compounds of same family
having similar forces of attraction form ideal solution.
Q5 Boiling point or freezing point of liquid solution would be affected by the dissolved
solids in the liquid phase. A soluble solid in solution has the effect of raising its
boiling point and depressing its freezing point. The addition of non-volatile
substances to a solvent decreases the vapor pressure and the added solute
particles affect the formation of pure solvent crystals According to many
researches the decrease in freezing point directly correlated to the concentration
of solutes dissolved in the solvent. This phenomenon is expressed as freezing
point depression and it is useful for several applications such as freeze
concentration of liquid food and to find the molar mass of an unknown solute in
the solution.
Freeze concentration is a high-quality liquid food concentration method where
water is removed by forming ice crystals, this is done by cooling the liquid food
below the freezing point of the solution. The freezing point depression is referred
as a colligative property and it is proportional to the molar concentration of the
solution (m), along with vapour pressure lowering boiling point elevation, and
osmotic pressure. These are physical characteristics of solutions that depend only
on the identity of the solvent and the concentration of the solute. The characters
are not depending on the solute's identity.
(Source: Jayawardena, J. A. E. C., Vanniarachchi, M. P. G., & Wansapala, M. A. J.
(2017). Freezing point depression of different Sucrose solutions and coconut water)
a. Four samples BaCl , NaCl, ZnCl and AICI of 0.5 M are being boiled Which
2 2 3
Ans a. AlCl3
Q5 b. By depression of freezing point (it lowers freezing point of water less than 0
C)
c. ΔTf = i kf m
2=1x 8 x (2.8/Mb )x1000/100 =8x2.8x10/Mb
Mb=8x28/2=8x14=112g/mol
OR
ΔTb = i kb m
0.21= 1x 2.52x2x1000/100xMb
Mb= 2.52x2x10/0.21=240 g/mol
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20 | P a g e
2. ELECTROCHEMISTRY
Quick Revision Points
Electrochemistry: the study of production of electricity from energy released during
spontaneous chemical reactions and the use of electrical energy to bring about non-
spontaneous chemical reactions.
Differences Between
Galvanic cell or Voltaic cell or Electrolytic cell
electrochemical cell
A device in which electric current A device in which a nonspontaneous
(electrical energy) is generated from chemical reaction is carried with the help
spontaneous redox chemical reaction of electric current (electrical energy).
(chemical energy)
eg: Daniel cell, dry cell, lead storage eg : electrolysis of molten NaCl,
battery electrolysis of dilute aq.H2SO4 solution
using Pt electrode
.
Electrochemical cell e.g., Daniel cell
The overall cell reaction is:
Zn(s) + Cu2+ (aq) → Zn2+ (aq) + Cu(s)
The Daniel cell is represented as :
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Note: It is a common practice to express all the electrode potentials as reduction
potentials.
Reduction potential = - Oxidation potential.
𝑜 0.0591 1
𝐸M𝑛+/M = 𝐸M 𝑛+ /M − log 𝑛+ at 298 K
𝑛 [M ]
∘ 0.0591 [Product]
at 298 K, 𝐸cell = 𝐸cell − log
𝑛 [ Reactant]
22 | P a g e
For example, (i) Nernst equation for Daniel cell (Zn – Cu cell) can be written as:
o 0.059 [Zn2+ ]
𝐸(cell) = 𝐸(cell) − log
2 [Cu2+ ]
(ii) Nernst equation for Ni – Ag cell
Ni(s)|Ni2+ (aq) ∥ Ag + (aq)|Ag(s)
The cell reaction is Ni(s) + 2Ag + (aq) → Ni2+ (aq) + 2Ag(s)
The Nernst equation can be written as
o 0.059 [Ni2+ ]
𝐸(cell) = 𝐸(cell) − log
2 [Ag + ]2
Equilibrium Constant from Nernst Equation:
[Zn2+ ]
At equilibrium, Ecell = 0, then [Cu2+ ]
= 𝐾𝑐
∘ 0.0591 𝑛 ∘
In general, 𝐸cell = log 𝐾𝑐 or, log 𝐾𝑐 = 0.0591 𝐸cell
𝑛
Δ𝑟 𝐺 𝑜 = −𝑅𝑇ln 𝐾𝑐 or Δ𝑟 𝐺 𝑜 = −2.303𝑅𝑇log 𝐾𝑐
Maximum work = Δ𝑟 𝐺 𝑜
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Conductance of Electrolytic solutions:
Resistance (R) - Obstruction to the flow of current, R = ρ L/A, Its SI unit is ohm.
Resistivity (ρ) - electrical resistance of a conductor of unit cross-sectional area and unit
length.
ρ = R A /l, Its SI unit is ohm metre.
Cell Constant is defined as the ratio of the distance between the two electrodes to their
area of cross section. Its SI unit is m-1
24 | P a g e
For a strong electrolyte: molar conductivity increases slowly on dilution or decrease in
concentration due to increase in the movement of ions. There is only a small increase in
conductance with dilution. (This is because a strong electrolyte is completely dissociated
in solution, so the number of ions remain constant and on dilution, interionic
attractions decrease as ions move far apart.)
Kohlrausch’s Law: It states that the limiting molar conductivity of an electrolyte can be
represented as the sum of the individual contributions of the anion and cation of the
electrolyte.
In general, if an electrolyte on dissociation gives 𝑣+ cations and 𝑣− anions then its limiting
molar conductivity is given by Λ0𝑚 = 𝑣+ 𝜆0+ + 𝑣− 𝜆0−
Here, 𝜆∘+ and 𝜆∘− are the limiting molar conductivities of cations and anions, respectively.
Products of Electrolysis:
Products Reactions involved
Electrolyte At cathode
At At
At anode
cathode anode
Na+ −
(𝑙) + 𝑒 → Na (𝑙)
Molten Na Cl2 1
NaCl metal gas Cl−
(𝑙) → Cl2(𝑔) + 𝑒
−
2
25 | P a g e
1
H2 O(𝑙) + 𝑒 − → H
Aqueous Cl2 2 2(𝑔) 1
H2 gas −
+ OH(𝑎𝑞) Cl−
(𝑎𝑞) → Cl2(𝑔) + 𝑒
−
NaCl gas 2
+ 1
O2 H(𝑎𝑔) + 𝑒 − → H2(𝑔) +
Dil. H2 SO4 H2 gas 2 2H2 O(𝑙) → O2(𝑔) + 4H(𝑎𝑞) + 4𝑒 −
gas
+ 1
Conc. H(𝑎𝑞) + 𝑒 − → H2(𝑔)
H2 gas S2 O2−
8 2 2SO2− 2−
4(𝑎𝑞) → S2 O8 (𝑎𝑞) + 2𝑒
−
H2 SO4
Overvoltage/Over potential: Oxidation of H2O is relatively slow process and thus needs
extra potential. This extra potential needed to oxidise H2O is called overvoltage/over
potential. Due to overvoltage, the oxidation of chloride ion occurs at anode in preference
to H2O.
Faraday’s first law of electrolysis: The amount of chemical reaction which occurs at
any electrode during electrolysis is proportional to the quantity of electricity passed
through the electrolyte. m=ZQ,
m = Z × I × t, where Z = Electrochemical equivalent =M/nF where n = no of electrons or
valency, F=96487, M= molar mass of the metal
Dry cell (Leclanche cell): The anode consists of a zinc container and the cathode is a
graphite electrode surrounded by powdered MnO2 and C. The space is filled with paste of
NH4Cl and ZnCl2.
At anode: Zn(s) → Zn2+(aq) + 2e–
At cathode: MnO2 (s) + NH4+(aq)+ 2e– → MnO(OH) + NH3
The net reaction: Zn + NH4+(aq) + MnO2 → Zn2+ + MnO(OH) + NH3
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Mercury cell: consists of zinc–mercury amalgam as anode and a paste of HgO and
carbon as the cathode. The electrolyte is a paste of KOH and ZnO. The electrode
reactions are:
Anode: Zn(Hg) + 2OH-→ ZnO(s) + H2O + 2e –
Cathode: HgO(s) + H2O + 2e- → Hg (l) + 2OH–
The cell potential is approximately 1.35 V and remains constant as the ionic
concentration of the solution is not changed during its life
Lead storage battery: Anode - Spongy lead Cathode - Lead packed with Lead dioxide
Electrolyte -Aqueous solution of H2SO4 (38%)
Discharge reaction of cell:
At anode : Pb(s) + SO42–(aq) → PbSO4 (s) +2e–
At cathode: PbO2 filled in lead grid gets reduced to Pb2+ ions which combines with SO42–
ions to form PbSO4 (s). The reaction is PbO2 (s) + 4H+(aq) + SO42–(aq) + 2e– → PbSO4 (s) +
2H2O(l)
Complete cell reaction: Pb(s) + PbO2 (s) + 2H2SO4 (aq) → 2PbSO4 (s) + 2H2O(l)
Recharge reaction of cell (charging): It changes the direction of electrode reaction.
PbSO4 accumulated at cathode gets reduced to Pb.
Overall Reaction: PbSO4 (s) + 2H2O(l) → Pb(s) + PbO2 (s) + 2H2SO4 (aq)
Nickel–cadmium cell which has longer life than the lead storage cell but is costly. Here,
the overall reaction during discharging:
Cd(s) + 2Ni(OH)3 (s)→ CdO(s) + 2Ni(OH)2 (s) + H2O(l)
Fuel cells: Electrical cells that are designated to convert the energy from the combustion
of fuels such as hydrogen, carbon monoxide or methane directly into electrical energy
are called fuel cells. the cell reactions are:
Anode: 2H2 (g) + 4OH– (aq) → 4H2 O (l) + 4e-,
Cathode: O2 (g) + 2H2 O(l) + 4e– → 4OH– (aq)
Net reaction: 2H2 (g) + O2 (g) →2H2O (l)
Advantages: high efficiency, free from pollution (eco-friendly), continuous source of
energy
Corrosion: The process of slow conversion of metals into their undesirable compounds
(usually oxide) by reaction with moisture and other gases present in the atmosphere.
Rusting of iron:
Oxidation: Fe(s) → Fe+2 (aq) + 2e-, Reduction: O2(g) + 4H+(aq) + 4e-→ 2H2O(l)
Atmospheric oxidation: 2Fe (s) + ½ O2 (g) + 2H2O(l) → Fe2O3 + 4H+(aq)
+2
27 | P a g e
(a) Pt(s)| H2 (g, 0.1 bar)| H+ (aq., 1 M) | | Cu2+ (aq., 1M)| Cu(s)
(b) Pt(s)| H2 (g, 1 bar) | H+ (aq., 1 M) | | Cu2+ (aq., 2M)| Cu(s)
(c) Pt(s)| H2 (g, 1 bar) | H+ (aq., 1 M) | | Cu2+ (aq., 1M)| Cu(s)
(d) Pt(s)| H2 (g, 1 bar) | H+ (aq., 0.1 M)| | Cu2+ (aq., 1M)| Cu(s)
Q4. The positive value of the standard electrode potential of Cu2+/Cu indicates that
(a) this redox couple is a stronger reducing agent than the H+ /H2 couple.
(b) this redox couple is a stronger oxidising agent than H+ /H2.
(c) Cu can displace H2 from acid.
(d) Cu can displace H2 from acid
Q5. On increasing temperature,
(a) ionic conductance increases and electronic conductance decreases.
(b) ionic conductance decreases and electronic conductance increases.
(c) both ionic and electronic conductance increase.
(d) both ionic and electronic conductance decrease.
Q6. The electrolyte used in the mercury cell is
(a) paste of NH4Cl and ZnCl2 (b) paste of HgO and carbon
(c) paste of KOH and ZnO (d) paste of PbO and H2SO4
Q7. A device that converts energy of combustion of fuels like hydrogen and methane
directly into electrical energy is known as:
(a) dynamo (b) Ni-Cd cell (c) fuel cell (d)
electrolytic cell
Q8. Which one of the following is always true about the spontaneous cell reaction in a
galvanic cell?
(a) E° cell > 0, ΔG° < 0, Q >KC (b) E° cell < 0, ΔG° < 0, Q <KC
(c) E° cell > 0, ΔG° > 0, Q >KC (d) E° cell > 0, ΔG° < 0, Q <KC
Q9. Charge carried by 1 mole of electrons is
(a) 6.023 × 1023 coulomb (b) 9.65 × 104 coulomb
(c) 1.6 × 10–19 coulomb (d) 6.28 × 1019 coulomb
Q10. To calculate the standard emf of the cell, which of the following options is correct if
E° is reduction potential values?
(a) emf = E°cathode – E°anode (b) emf = E°anode – E°cathode
(c) emf = E°anode + E°cathode (d) None of these
Answers : 1(b), 2(c), 3(c), 4(b), 5(a), 6(c), 7(c), 8(d), 9(b), 10(a)
ASSERTION REASON TYPE QUESTIONS(1MARKS)
Given below are two statements labelled as Assertion (A) and Reason (R)
Select the most appropriate answer from the options given below:
a. Both A and R are true and R is the correct explanation of A
b. Both A and R are true but R is not the correct explanation of A.
c. A is true but R is false.
d. A is false but R is true.
Q1. Assertion (A) : Ecell should have a positive value for the cell to function.
Reason(R) : Ecathode < Eanode
Q2. Assertion (A) : Copper sulphate cannot be stored in zinc vessel.
Reason (R) : Zinc is less reactive than copper.
Q3. Assertion (A) : Current stops flowing when Ecell = 0.
Reason (R) : Equilibrium of the cell reaction is attained.
28 | P a g e
Q4. Assertion (A) : Conductivity of all electrolytes decreases on dilution.
Reason (R) : On dilution number of ions per unit volume decreases.
Q5. Assertion (A) : Conductivity decreases for weak electrolyte and increases for strong
electrolyte with decrease in concentration.
Reason (R) : On dilution, the number of ions per unit volume that carry the
current decreases.
Answers: 1( c), 2( c), 3(a), 4(a), 5(d)
29 | P a g e
Q5. Suggest a way to determine the Λ0𝑚 value of water.
Ans.
Λ𝑜𝑚(H2 O) = 𝜆𝑜(H+) + 𝜆𝑜(OH−)
= 𝜆𝑜(H+) + 𝜆𝑜(OH−) + 𝜆𝑜(Cl−) − 𝜆0(Cl−) + 𝜆0(Na+) − 𝜆0(Na+)
Rearranging we get
Λo𝑚(H2 O) = [𝜆o(H+) + 𝜆o(Cl−) ] + [𝜆o(Na+) + 𝜆o(OH−) ] − [𝜆o(Na+) + 𝜆o(Cl−) ]
Λo𝑚(H2 O) = Λo𝑚(HCl) + Λo𝑚(NaOH) − Λo𝑚(NaCl)
Thus, the molar conductivity of water at infinite dilution can be determined from the
knowledge of Λo𝑚(HCl) , Λo𝑚(NaOH) and Λo𝑚(NaCl) .
Q6. Why on dilution the ⋀m of CH3COOH increases drastically while that of CH3COONa
increases gradually?
Ans. Ans. CH3COOH is a weak electrolyte, the number of ions increase on dilution due
to an increase in degree of dissociation.
Q7. (a) What is the role of ZnCl2 in a dry cell?
(b) Unlike dry cell, the mercury cell has a constant cell potential throughout its
useful life. why?
Ans (a) ZnCl2 combines with the NH3 produced to form the complex salt [Zn(NH3)2 Cl2]
otherwise the pressure developed due to NH3 would crack the seal of the cell
(b) Ions are not involved in the overall cell reaction of mercury cells
Q8. (a) Value of standard electrode potential for the oxidation of Cl– ions is more positive
than that of water, even then in the electrolysis of aqueous sodium chloride, why is Cl–
oxidised at anode instead of water?
(b) How will the pH of brine (aq. NaCl solution) be affected when it is electrolysed?
Ans. (a) On electrolysis of aqueous sodium chloride, oxidation of water at anode requires
over potential hence Cl– is oxidised instead of water.
(b) The pH of the solution will increase as NaOH is formed in the electrolytic cell.
Q9. (a) Which type of a metal can be used in cathodic protection of iron against rusting?
(b) Write the name of the electrolyte used in fuel cell
Ans. (a) More electropositive than iron such as Al, Zn, Mg etc. (b) Conc. Aq. KOH
solution
Q10. Depict the galvanic cell in which the reaction Zn(s) + 2Ag+ (aq) → Zn2+ (aq) + 2Ag(s)
takes place. Further show: (i) Which of the electrode is negatively charged?
(ii) The carriers of the current in the cell.
Ans. Cell can be represented as Zn | Zn2+ (aq) ||Ag+ (aq) |Ag.
(i) zinc electrode is negatively charged (anode)
(ii) Ions are the current carriers within the cell
30 | P a g e
∘ ∘ ∘
𝐸cell = 𝐸cathode − 𝐸anode = 3.36V
Ans. (a)
The net cell reaction is, Zn(𝑠) + Cd2+ 2+
(aq ) → Zn(aq ) + Cd(𝑠) , n=2
∘ 0.0591 [𝑍𝑛2+ ]
𝐸cell = 𝐸cell − log [𝐶𝑑2+] = 0.44 𝑉,
2
ΔG = −nFEcell = −84920J/mol
(b) Cu2+ −
(aq ) + 2𝑒 → Cu(𝑠)
31 | P a g e
electrode, current flows from Cu to Zn. Zn dissolves and copper deposits at their
respective electrodes.
(ii) The reaction stops and no current flows. (iii) Reaction takes place in opposite
directions.
Electrons flow from copper electrode to zinc electrode, current flows from Zn to Cu. cell
functions as an electrolytic cell.
Q5. Explain redox potential. Reduction potentials of some ions are given below. Arrange
them in decreasing order of oxidizing power.
Ion ClO−
4 IO−
4 BrO−
4
Q1. (i) State two advantages of H2—O2 fuel cell over ordinary cell.
(ii) Silver is electrodeposited on a metallic vessel of total surface area 500 cm2 by
passing a current of 0.5 amp for two hours. Calculate the thickness of silver deposited.
[Given: Density of silver = 10.5 g cm–3, Atomic mass of silver = 108 amu, F = 96,500 C
mol–1]
Ans. (i) pollution free, 75% efficiency, continuous source of energy.
(ii) m=ZIt = 4.029g, V=m/d = 0.3837 cm3, thickness of Ag deposited is x, V= A. x =
7.67x10-4cm
Q2. (i) Define limiting molar conductivity and fuel cell.
(ii) Resistance of a conductivity cell filled with 0.1 mol L–1 KCl solution is 100 ohm. If the
resistance of the same cell when filled with 0.02 mol L–1 KCl solution is 520 ohm,
calculate the conductivity and molar conductivity of 0.02 mol L–1 KCl solution. The
conductivity of 0.1 molL–1 KCl solution is 1.29 × 10–2 ohm–1 cm–1.
Ans (i) Limiting Molar conductivity -limiting value of molar conductivity when
concentration approaches to zero. Fuel cell - device which converts energy produced
during the combustion of fuels directly into electrical energy.
(ii) cell constant = conductivity x resistance = 1.29 cm–1, Conductivity, k = Cell
constant/Resistance = 0.00248 ohm–1 cm–1, Λm = k X 1000/M = 124 ohm–1 cm2 mol–1
32 | P a g e
cell. If a redox reaction is allowed to take place in such a way that oxidation half reaction
takes place in one beaker and the reduction half reaction in another beaker, the
electrons given out by the former will be taken by the latter and the current will ow. The
two portions of the cell are called half cells. The values of standard redox potential ( 𝐸 0 )
of two half cell reactions decides in which way the reaction will proceed. A redox reaction
is feasible when the substance having higher reduction potential gets reduced and the
one having lower reduction potential gets oxidised. For example, In Daniel cell, zinc goes
into solution and copper gets deposited.
1.Formulate the galvanic cell for: Zn(𝑠) + 2Ag + (𝑎𝑞) ⟶ Zn2+ (𝑎𝑞) + 2Ag(𝑠)
Ans. The cell is represented as: Zn(𝑠)|Zn2+ (𝑎𝑞) ∥ Ag + (𝑎𝑞)|Ag(𝑠)
2. Is it safe to stir AgNO3 solution with a copper spoon? Why or why not?
0 0
Given: 𝐸Ag + /Ag = 0.80 volt and 𝐸Cu2 +/Cu = 0.34 volt
Ans. No, because copper is more reactive than Ag and can displace Ag from AgNO3
solution.
3. Two half-cell reactions of an electrochemical cell are given below:
MnO− + − 2+ 0
4 (𝑎𝑞) + 8H (𝑎𝑞) + 5𝑒 ⟶ Mn (𝑎𝑞) + 4H2 O(𝑙), 𝐸 = +1.51 V
Sn2+ (𝑎𝑞) ⟶ Sn4+ (𝑎𝑞) + 2𝑒 − , 𝐸 0 = +0.15 V
Construct the redox reaction from the two half-cell reactions and predict if this reaction
favours formation of reactants or products shown in the equation.
Ans.
2MnO− + 2+ 2+ 4+
4 (𝑎𝑞) + 16H (𝑎𝑞) + 5Sn (𝑎𝑞) ⟶ 2Mn (𝑎𝑞) + 5Sn (𝑎𝑞) + 8H2 O(𝑙)
𝑜 ∘ ∘
𝐸Cell = 𝐸Cathode − 𝐸Anode = 1.51 V − 0.15 V = 0.36 V, product forms
OR
(i) State the factors affecting cell potential of: Mg(𝑠)|Mg 2+ (𝑎𝑞) ∥ Ag + (𝑎𝑞)|Ag(𝑠)
0
(ii) Can 𝐸cell or Δ𝑟 𝐺 0 for cell reaction ever be equal to zero?
Ans.(i) concentration of Mg 2+ and Ag + ions in the solution and temperature.
∘
(iii) No, 𝐸cell or Δ𝑟 𝐺 0 for cell reaction can never be zero. ΔG°= -nFE°
33 | P a g e
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3. CHEMICAL KINETICS
QUICK REVISION POINTS
Rate of a Chemical Reaction: It is the change in concentration of a reactant or product
in unit time (or) it is the rate of change of concentration of reacting species.
Consider a reaction,
R→P
−[𝑅] [𝑃]
Rate of a Chemical Reaction = =
− 𝑡 𝑡
Units of rate of a reaction: mol L-1s–1.
NOTE: Rate of reaction always expressed for every one mole.
Consider a general reaction: a A + b B→ c C + d D, then
1 1
Rate of reaction = - [ Rate of disappearance of A] = - [ Rate of disappearance of B]
𝑎 𝑏
1 1
= [ Rate of appearance of C] = [ Rate of appearance of D]
𝑐 𝑑
35 | P a g e
nth order of reaction nth mol(1-n)L(n-1)S-1
Difference between order of reaction and molecularity of reaction:
Order of reaction Molecularity of reaction
1 It is the sum of powers of The number of reacting species (atoms, ions
concentrations of reactants or molecules) taking part in an elementary
expressed in rate law. reaction, which must collide simultaneously
in order to bring about a chemical reaction
2 Order of a reaction is an Molecularity of a reaction is a theoretical
experimental quantity. quantity.
3 It can be zero and even a Molecularity cannot be zero or a non-
fraction integer.
Some enzyme catalysed reactions and reactions which occur on metal surfaces (metal
catalyst) are a few examples of zero order reactions.
(ii) First Order Reactions
Consider first order reaction
R →P
36 | P a g e
Let [R]o be the initial concentration of reactant and [R] be the final concentration at
time‘t’.
For zero order reaction, the rate of the reaction is proportional to the first power of the
concentration of the reactant R.
𝑑[𝑅] 𝑑[𝑅]
Rate =− =kR = −kdt
𝑑𝑡 𝑅
Integrating on both sides, ln [R] = – kt + I, I is the constant of integration.
When t = 0, R becomes [R]0, where [R]0 is the initial concentration of the reactant.
Therefore, ln [R]0 = –k × 0 + Iln [R]0 = I
Substituting the value of I, ln[R] = –kt + ln[R]0
[𝑅] 1 [𝑅]𝑜 2.303 [𝑅]𝑜
Rearranging this equation, ln = kt Or, k = ln k= log
[𝑅 ]𝑜 𝑡 𝑅 𝑡 𝑅
A graph is drawn between log [R] against ‘t’ gives a straight line with slope = –k and
intercept equal to log [R]0
For a first order reaction, half-life period is constant, i.e., it is independent of initial
concentration of the reacting species.
For zero order reaction t½ ∝ [R]0.
For first order reaction t½ is independent of [R]0.
In general, for nth order, t½ = 1/ [R]o(n-1)
Pseudo First Order Reaction: A reaction which appear to
follow higher order but follows the first order kinetics.
Effect of temperature on rate of a reaction
Rate of a reaction always increases with increase of
temperature
37 | P a g e
(i) According to Kinetic theory of Molecular gases, the average kinetic energy of reacting
gaseous molecules is directly proportional to absolute temperature.
K.E T ½ mv2 T
As temperature increases, speed of reacting molecules increases. Thereby, the frequency
of collisions also increases and hence rate of reaction increases.
(ii) Experimental evidence shows that for every 10 degree rise in temperature, the rate of
a reaction will be doubled.
(iii) If ‘E’ is the energy barrier, then the number of molecules that crosses over the energy
barrier is more at higher temperature than at low temperature.
Activated complex (Transition State theory):It is the reaction intermediate possessing
energy that correspond to top of energy barrier.
Activated complex state is highly energy state and hence it is highly unstable state. It is
always reversible state.
Consider a reaction: H2 (g) + I2( g ) → 2HI ( g )
If the total energy of reacting species are equal or higher than threshold energy then the
reaction proceed in forward direction and hence gives the products otherwise it retain as
reactants only.
Effect of Catalyst: A catalyst is a substance which alters the rate of a reaction without
itself undergoing any permanent chemical change.
Catalyst help to increase the rate of chemical reaction. It carries the reaction through
the path of lower activation energy.
38 | P a g e
MULTIPLE CHOICE QUESTIONS:
1. For a given rate, the unit of rate and the rate constant are the same.
(A) zero order reaction (B) first order reaction
(C) second order reaction (D) third order reaction
2. If concentration of reactant ‘A’ is increased 10 times and the rate of reaction
becomes 100 times. What is the order with respect to ‘A’?
(A) 1 (B) 2 (C) 3 (D) 4
3. Which of the following is not a direct factor affecting the rate of a reaction?
(A) Temperature (B) Presence of catalyst
(C) Order of reaction (D) Molecularity
4. In the elementary reaction 2A + B → A2B, if the concentration of A is doubled and
that of B is halved, then the rate of the reaction will
(A) increase 2 times (B) increase 4 times
(C) decrease 2 times (D) remain the same
5. A first order reaction has a half-life length of 10 minutes. In 100 minutes, what
proportion of the response will be completed?
(A) 25% (B) 50% (C) 99.9% (D) 75%
6. What is the order of reaction decomposition of Ammonia on platinum surface is
(A) Zero order reaction (B) First order reaction
(C) Second order reaction (D) Fractional order reaction
7. In the rate equation, when the concentration of reactants is unity then the rate is
equal to:
(A) Specific rate constant (B) Average rate constant
(C) Instantaneous rate constant (D) None of the above
8. The rate constant of zero order reactions has the unit
(A) s-1 (B) mol L-1s-1
(C) L2 mol-2 s-1 (D) L mol-1s-1
9. Radioactive disintegration is an example of
(A) first order reaction (B) zero order reaction
(C) second order reaction (D) third order reaction
10. A catalyst alters, which of the following in a chemical reaction?
(A) Entropy (B) Enthalpy
(C) Internal energy (D) Activation energy
ASSERTION – REASON BASED QUESTIONS
Read the Assertion and Reason statements and choose the appropriate option
from below:
A) Both A and R are true and R is the correct explanation of A
B) Both A and R are true and R is not the correct explanation of A
C) A is true but R is false
D) A is false but R is true
1. Assertion: Increasing the pressure of reactants can increase the rate of a reaction.
Reason: Higher pressure can increase the frequency of collisions between reactant
molecules
2. Assertion: The presence of a catalyst increases the activation energy of a reaction.
Reason: Catalysts provide an alternative reaction pathway with a lower activation
energy.
3. Assertion: Hydrolysis of methyl ethanoate is a pseudo-first-order reaction.
39 | P a g e
Reason: Water is present in large excess and therefore its concentration remained
constant throughout the reaction.
4. Assertion: Average rate and instantaneous rate of a reaction have the same unit.
Reason: Average rate becomes an instantaneous rate when the time interval is too
small.
5. Assertion: All collision of reactant molecules lead to product formation.
Reason: Only those collisions in which molecules have correct orientation and
sufficient kinetics energy lead to compound formation.
VERY SHORT ANSWER QUESTIONS (1 MARK)
1. In some cases, it is found that a large number of colliding molecules have energy more
than threshold value, yet the reaction is slow. Why?
2. For a reaction R→P, half-life (t½ ) is observed to be independent of the initial
concentration of reactants. What is the order of reaction?
3. Why does the rate of a reaction not remain constant throughout the reaction
process?
4. What is elementary reaction?
5. Express the rate of the following in terms of ammonia.
N2(g) + 3H2(g) → 2NH3(g)
6. Mention the factors that affect the rate of a chemical reaction.
7. In a reaction, 2A → Products, the concentration of A decreases from 0.5 mol L–1 to
0.4 mol L–1 in 10 minutes. Calculate the rate during this interval?
8. A graph is drawn between ln[R] and t
for a reaction. What is order of reaction?
40 | P a g e
2. Observe the graph in diagram and answer the following questions.
(i) If slope is equal to -2.0 x10-6 sec-1, what will be the value
of rate constant?
(ii) How does the half-life of zero order reaction relate to its
rate constant?
3. (a) Consider a certain reaction A → Products with k = 2.0 × 10-2 s-1. Calculate the
concentration of a remaining after 100 s if the initial concentration of A is
1.0 mol l-1
(b) The half-life for radioactive decay of C -14 is 5730 years. An archaeological
artefact containing wood had only 80% of the C -14 found in a living tree. Estimate
the age of the sample.
4. If a zero-order reaction starts with the concentration of 10 mol/L, it’s half-life is
2 minutes, what will be the half-life of the same reaction, if it is started with
20 mol/L?
41 | P a g e
CASE BASED QUESTIONS / INTEGRATED BASED QUESTIONS (4 MARKS)
1. Read the passage carefully and answer the questions that follow
Rate of the Reaction
Speed of any event is measured by the change that occurs in any interval of time.
The speed of a reaction (reaction rate) is expressed as the change in concentration
of a reactant or product over a certain amount of time. Sometimes it is more
convenient to express rates as numbers of molecules formed or consumed in unit
time.
42 | P a g e
Answer the following questions:
(a) Calculate the overall order of the reaction which has the following rate
expression:
Rate= k[A]1/2[B]3/2
(b) What is the effect of temperature on rate of the reaction?
(c) What is meant by the rate of reaction?
(d) A first order reaction takes 77.78 minutes for 50% completion. Calculate the
time required for 30% completion of the reaction. (log 10= 1, log 7=0.8450)
OR
A first order reaction has a rate constant 1x10-3 s-1. How long will 5 gm of this
reactant take to reduce to 3 gm? (log 3= 0.4771, log 5=0.6990)
3. Read the passage carefully and answer the questions that follow
Radio Activity
There are nuclear reactions constantly occurring in our bodies, but these are very
few of them compared to the chemical reactions, and they do not affect our bodies
much. All of the physical processes that take place to keep a human body running
are chemical processes. Nuclear reactions can lead to chemical damage, which the
body may notice and try to fix. The nuclear reaction occurring in our bodies is
radioactive decay. This is the change of a less stable nucleus to a more stable
nucleus. Every atom has either a stable nucleus or an unstable nucleus,
depending on how big it is and on the ratio of protons to neutrons. The ratio of
neutrons to protons in a stable nucleus is thus around 1:1 for small nuclei (Z<20).
Nuclei with too many neutrons, too few neutrons, or that are simply too big are
unstable. They eventually transform to a stable form through radioactive decay.
Wherever there are atoms with unstable nuclei (radioactive atoms), there are
nuclear reactions occurring naturally. The interesting thing is that there are small
amounts of radioactive atoms everywhere: in your chair, in the ground, in the food
you eat, and yes, in your body. The most common natural radioactive isotopes in
humans are carbon-14 and potassium-40. Chemically, these isotopes behave
exactly like stable carbon and potassium. For this reason, the body uses carbon-
14 and potassium-40 just like it does normal carbon and potassium; building
them into the different parts of the cells, without knowing that they are
radioactive. In time, carbon-14 atoms decay to stable nitrogen atoms and
potassium-40 atoms decay to stable calcium atoms. Half-life of C-14 is 6000 years
Chemicals in the body that relied on having a carbon14 atom or potassium-40
atom in a certain spot will suddenly have a nitrogen or calcium atom. Such a
change damages the chemical. Normally, such changes are so rare, that the body
can repair the damage or filter away the damaged chemicals.
Answer the following questions:
(a) Why is Carbon -14 radioactive while Carbon -12 not?
(Atomic number of Carbon: 6)
(b) Which are the two most common radioactive decays happening in human
body?
(c) Suppose an organism has 20 g of Carbon -14 at its time of death.
Approximately how much Carbon -14 remains after 10,320 years? (Given antilog
0.517 = 3.289)
OR
(c) Approximately how old is a fossil with 12 g of Carbon -14 if it initially possessed
32 g of Carbon -14? (Given log 2.667 = 0.4260)
43 | P a g e
4. Read the passage carefully and answer the questions that follow
Temperature Dependence of Rate of a Reaction
Temperature influences the rate of a reaction. As the temperature increases, the rate
of a reaction increases. For example, the time taken to melt a metal will be much
higher at a lower temperature but it will decrease as soon as we increase the
temperature. It has been found that the rate constant is nearly doubled for a
chemical reaction with a rise in temperature by 10°. The dependence of the rate of a
chemical reaction on temperature can be explained by Arrhenius equation.
k = A e -Ea/RT
According to the Arrhenius equation, a reaction can only take place when a molecule
of one substance collides with the molecule of another to form an unstable
intermediate. This intermediate exists for a very short time and then breaks up to
form product. The energy required to form this intermediate is known as activation
energy (Ea). The fraction of molecules with kinetic energy equal to or greater than
Ea at a given temperature may lead to the product. As the temperature rises, the
proportion of molecules with energies equal to or greater than activation energy
(≥Ea) increases. As a result, the reaction rate would increase.
Answer the following questions:
(a) How does the half life period of a first order reaction vary with temperature?
OR
For an endothermic reaction, the activation energy of forward reaction will be
equal to or less than or more than activation energy of backward reaction.
(b)The slope of Arrhenius Plot (ln k vs 1/T) of first order reaction is −5×103K.
Calculate the value of Ea of the reaction. [Given R = 8.314JK−1mol−1]
(c) The rate constant of a reaction is 6×10-3 s-1 at 50° and 9×10-3 s-1 at 100° C.
Calculate the energy of activation of the reaction.
5. Read the passage carefully and answer the questions that follow:
The Arrhenius equation, developed by Swedish chemist Svante Arrhenius, is a
fundamental equation in chemical kinetics that relates the rate constant (k) of a
reaction to temperature (T) and the activation energy (Ea). The equation is given
by:
k = A e−Ea/RT
Here, A is the pre-exponential factor or frequency factor, Ea is the activation
energy, R is the ideal gas constant, and T is the absolute temperature.
The Arrhenius equation helps explain the temperature dependence of reaction
rates. As temperature increases, the exponential term e−Ea/RT becomes smaller,
leading to a higher rate constant and consequently, a faster reaction.
Conversely, lower temperatures result in a decrease in the rate constant and a
slower reaction.
In summary, the Arrhenius equation provides valuable insights into the
relationship between temperature and reaction rates, aiding in the understanding
and prediction of chemical reactions under different temperature conditions.
44 | P a g e
c) Calculate the activation energy of a reaction if the slope of its ln k vs 1/T plot is
-3166 K.
OR
c) The activation energy for the reaction 2 HI(g) → H2 + I2 (g) is 209.5 kJ mol–1
at 581K. Calculate the fraction of molecules of reactants having energy equal to
or greater than activation energy?
ANSWERS
MULTIPLE CHOICE QUESTIONS:
1 2 3 4 5 6 7 8 9 10
A B D A C A A B A D
10. Catalyst takes the reaction through the path of lower activation energy.
SHORT ANSWER QUESTIONS TYPE-1 (2 MARKS)
1. Rate of a reaction always increases with increase of temperature
(i) According to Kinetic theory of Molecular gases, the average kinetic energy of
reacting gaseous molecules is directly proportional to absolute temperature.
K.E T ½ mv2 T
45 | P a g e
As temperature increases, speed of reacting molecules increases. Thereby, the
frequency of collisions also increases and hence rate
of reaction increases.
(ii) Experimental evidence shows that for every 10-
degree rise in temperature, the rate of a reaction will
be doubled.
(iii) If ‘E’ is the energy barrier, then the number of
molecules that crosses over the energy barrier is more
at higher temperature than at low temperature.
2. (i) A given temperature, rate is equal to the rate
constant of reaction when concentration of the
reactant in unity. Thus rate constant is also known as
specific reaction rate.
(ii) Additional energy required by the reacting molecules to attain Threshold energy
is called Activation energy.
3.
Order of reaction Molecularity of reaction
1 It is the sum of powers ofThe number of reacting species (atoms, ions
concentrations of reactants
or molecules) taking part in an elementary
expressed in rate law. reaction, which must collide simultaneously
in order to bring about a chemical reaction
2 Order of a reaction is an Molecularity of a reaction is a theoretical
experimental quantity. quantity.
3 It can be zero and even a Molecularity cannot be zero or a non-
fraction integer.
5.
46 | P a g e
3. (a) The integrated rate expression for the first order reaction is as follows:
k=2.303/t log[A]0/ [A] ⟹2.0×10−2=2.303tlog1.0[A]
⟹log1.0[A]=0.868 ⟹[A]=0.135M
(b) Decay constant k=0.693t1/2=0.6935730year=1.209×10−4/years
The rate of counts is proportional to the number of C-14 atoms in the sample.
N0=100, N=80 The age of the sample t=2.303/k log(N0/N)
t=2.303/1.209×10−4 × log(10080)=1846years
4. For zero order reaction-t1/2=[R0]/2k (half-life is directly proportional to initial
concentration)
So t1/2 for 20 mol/L will be 4 minutes.
5. a) The rate constant of a reaction is nearly doubled with rise in temperature by 10
b) Bimolecular reactions become kinetically first order when one of the reactants is
present in excess
c) No, the molecularity can never be zero or a fractional number. As it represents
the total number of reactants taken in a reaction
47 | P a g e
𝛥[𝐻2 𝑂2 ]
(c) Rate = 9.32×10–4 Ms–1 = - 𝛥𝑡
[H2 O2 ]− 0.2546 M
9.32×10–4 Ms–1 = -
(35−0)s
H2O2 = 0.2220 M
OR
1 𝛥[𝑂3 ] 1 𝛥[𝑂2 ]
Rate = - =
2 𝛥𝑡 3 𝛥𝑡
𝛥[𝑂3 ] 2 𝛥[𝑂2 ] 2
=- = = (60.0 ×10-5 M/s) = 4.0 ×10-5 M/s
𝛥𝑡 3 𝛥𝑡 3
2. (a) Rate = k[A]1/2[B]3/2, as it is an elementary reaction,
Order of reaction = 1/2 + 3/2 = 2
(b) Rate of reaction increases with increase in temperature.
(c) Rate of reaction is the rate of change in concentration of a reactant per unit
time.
(d) For first order reaction
R = 0.693/t1/2 = (0. 693)/(77.78min) = 8.90x 10- 3 min
Time required to complete 30% reaction,
t = (2.303)/k x log a / (a - x) = (2.303) / (8.9x 10- 3 min- 1) x log (100 / (100 - 30))
= ((2.303 x103 x 0.155)/(8.9) = 40minutes
OR
For a first order reaction
t = (2.303)/k x log a/(a - x) = 2.303/1x10- 3x log 5/3 = 2.303x 103 x 0.2219 s
= 511 s
3. (a) Ratio of neutrons to protons in C-14 is 1.3: 1 which is not the stable ratio of
1:1 while ratio of neutrons to protons in C-12 is 1:1 which is the stable ratio.
(b) carbon-14 atoms decay to stable nitrogen atoms and potassium-40 atoms
decay to stable calcium
(c) t = 2.303/ k log (Co/Ct)
Co = 20 g Ct = ? t = 10320 years
k = 0.693/6000 (half-life given in passage)
Substituting in equation:
10320 = 2.303 / (0.693/6000) log 20/ Ct 0.517 = log 20 / Ct
Antilog (0.517) = 20/Ct 3.289 = 20/Ct Ct = 6.17 g
OR
t = 2.303/ k log (Co/Ct) Co = 32 g Ct = 12 t=?
k = 0.693/6000 (half-life given in passage)
Substituting in equation:
t = 2.303 / (0.693/6000) log 32/ 12
t = 2.303 x 6000/0.693 log 2.667 = 2.303x6000x0.4260 /0.693 = 8494 years
4. (a) Half-life period increases with temperature.
OR
The activation energy of forward reaction will be more than activation energy of
backward reaction.
(b) k = Ae -Ea/RT ln k = ln A – Ea/RT Slope = -Ea/R = - 5 × 103
Ea = 5 ×103 ×8.314 = 41.57×103 J/mol
(c) k1 = 6 × 10-3 s-1 T1 = 50 + 273 = 323 K
k2 = 9 × 10-3 s-1 T2 = 100 + 273 = 373 K
Substituting these values in the equation:
log (k2 / k1 ) = (Ea / 2.303 R) × ((T2 – T1) / T1 T2)
48 | P a g e
log (9 × 10-3 s-1 / 6 × 10-3 s-1 ) = ((Ea / (2.303 × 8.314)) × ((373 – 323) / (373 × 323))
log (9 / 6) = ((Ea / (2.303 × 8.314)) × (50 / (373 × 323)) Ea = 8.124 kJ mol-1.
5. (a)
(c) Additional energy required by the reacting molecules to attain Threshold energy
is called Activation energy.
(d) 110.115 kJ/mol OR
The fraction of molecules of reactants having energy equal to or greater than
activation energy is 1.471×10−19
49 | P a g e
50 | P a g e
4. THE d- AND f-BLOCK ELEMENTS
QUICK REVISION POINTS:
1. d-block elements
(a) DEFINITION: A transition element is defined as the one which has incompletely
filled d orbitals in its ground state or in any one of its oxidation states. Zinc,
cadmium and mercury of group 12 have full d10 configuration in their ground state
as well as in their common oxidation states and hence, are not regarded as
transition metals. Their Outer electronic configuration is (n -1) d1-10 ns 1-2
(b) MELTING AND BOILING POINTS: High MP & BP which is due to their strong
metallic bond (strong interatomic bonding) due to unpaired electrons in (n-1) d
orbitals. In any row the melting points of these metals rise to a maximum at d5
except for anomalous values of Mn and Tc.
(c) ENTHALPIES OF ATOMIZATION: High enthalpies of atomization because of large
number of unpaired electrons in their atoms they have stronger interatomic
interaction (metal-metal bonding). The metals of the second and third series have
greater enthalpies of atomisation than the corresponding elements of the first series
due to occurrence of much more frequent metal – metal bonding.
(d) VARIATION IN ATOMIC AND IONIC SIZES : In general, ions of the same charge in
a given series show progressive decrease in radius with increasing atomic number
The atomic radii decreases from group 3 to 6 because of increase in effective
nuclear charge gradually, The atomic radii of group 7, 8, 9 &10 elements is almost
same because Screening effect counter balances increased effective nuclear charge,
Group 11 & 12 elements have bigger size due to increase inter-electronic repulsion
as result electron cloud expands and size increases. Members of second (4d) and the
third (5d) series in each group of transition elements have similar radii and shows
similar properties because lanthanoid contraction essentially compensates for the
expected increase in atomic size with increasing atomic number.
(e) DENSITY: The decrease in metallic radius coupled with increase in atomic mass
results in a general increase in the density of these elements. Thus, from titanium
(22) to copper (29) the significant increase in the density may be noted.
(f) VARIATION IN IONISATION ENTHALPIES OF TRANSITION METALS: There is an
increase in ionisation enthalpy along each series of the transition elements from left
to right due to an increase in nuclear charge which accompanies the filling of the
inner d orbitals. Irregular variation of ionisation enthalpies is mainly attributed to
varying degree of stability of different 3d-configurations (e.g., d0, d5, d10 are
exceptionally stable).
(g) OXIDATION STATES: The transition elements show variable oxidation state due to
small energy difference between (n-1) d & ns orbital as a result both (n-1) d & ns
electrons take part in bond formation. The highest oxidation state of an element is
equal to number of unpaired e- present in (n-1) d & ns orbital.
(h) MAGNETIC PROPERTIES: Most of the transition metal ions are paramagnetic due
to the presence of unpaired electrons in d-orbitals. Magnetic moment is given by
51 | P a g e
(i) FORMATION OF COLOURED IONS: Due to the presence of unpaired electrons in d-
orbitals of the transition metal ions & because of d–d transitions occurring in a
transition metal ion by the absorption of visible light.
(j) FORMATION OF COMPLEX COMPOUNDS: Due to smaller sizes of the metal ions,
their high ionic charges and the availability of d orbitals for bond formation.
(k) CATALYTIC PROPERTIES: Due to Variable oxidation states & Large surface area.
(l) FORMATION OF INTERSTITIAL COMPOUNDS: Transition elements form
interstitial compounds because size of C, N, O, and B is similar to size of interstitial
voids of transition metals.
(m) ALLOY FORMATION: As the atomic sizes are very similar, one metal can replace
the other metal from its lattice and form a solid solution which is the alloy.
(n) STANDARD ELECTRODE POTENTIALS: Transition elements have lower negative
value of Standard Electrode Potentials due to high ionization potential, high heat
of sublimation & low enthalpy of hydration. The E0 (M2+/M) values are not regular
which can be explained from the irregular variation of ionization enthalpies and also
the sublimation enthalpies which are relatively much less for manganese and
vanadium.
(o) Oxide of transition metals in lower oxidation states are generally basic while those
in the higher oxidation states are acidic. Acidic character increases with increase in
oxidation state is due to decrease in size of metal ion and increase in effective
nuclear charge. e.g. MnO (basic), Mn3O4 (amphoteric), Mn2O7 (acidic).
2. LANTHANOIDS
(a) The 14 elements after Lanthanum having atomic number 58 to 71 are collectively
known as Lanthanoids. The general electronic configuration of these elements is [Xe]
4f1-14 5d0-1 6s2.
(b) LANTHANOID CONTRACTION (ATOMIC AND IONIC SIZES): The overall decrease in
atomic and ionic radii from lanthanum to lutetium is due to poor shielding of 4f
electrons is known as lanthanoid contraction.
Due to lanthanoid contraction:
(a)basic character of oxides and hydroxides decreases from La(OH)3 to Lu(OH)3
(b) Sizes of 4d and 5d metal pairs like Zr and Hf; Nb and Ta are almost similar.
(c) OXIDATION STATES: Most common oxidation state of these elements is +3,
However, occasionally +2 (Eu+2 and Yb+2) and +4 ions (Ce+4 and Tb+4) in solution or in
solid compounds are also obtained.
(d) COLOUR FORMATION: Many trivalent lanthanoid ions are coloured both in the solid
state and in aqueous solutions. Colour of these ions may be attributed to the
presence of unpaired electrons in f subshell.
(e) MAGNETIC BEHAVIOUR: The lanthanoid ions other than the f 0 type (La3+ and Ce4+)
and the f 14 type (Yb2+ and Lu3+) are all paramagnetic.
(f) USES: A well-known alloy is mischmetall which consists of a lanthanoid metal (~ 95%)
and iron (~5%) and traces of S, C, Ca and Al. A good deal of mischmetall is used in
Mg-based alloy to produce bullets, shell and lighter flint.
3. ACTINOIDS
(a) The 14 elements after Actinium having atomic number 90 to 113 are collectively
known as Actinoids
(b) The actinoids are radioactive elements These facts render their study more
difficult.
52 | P a g e
(c) Electronic Configurations: The general electronic configuration of these elements
is [Rn] 5f1-14 6d0-1 7s2.
(d) Ionic Sizes (Actinoid contraction): The overall decrease in atomic and ionic radii
across the series due to poor shielding of 5f electrons is known as Actinoid
contraction.
(e) The actinoid contraction is, however, greater from element to element in this series
resulting from poor shielding by 5f electrons.
(f) Oxidation States: The actinoids show in general +3 oxidation state. The actinoids
exhibit a larger number of oxidation states, which is in part attributed to the fact
that the 5f, 6d and 7s levels are of comparable energies. The elements, in the first
half of the series frequently exhibit higher oxidation states. For example, the
maximum oxidation state increases from +4 in Th to +5, +6 and +7respectively in
Pa, U and Np but decreases in succeeding elements.
(g) The actinoids are highly reactive metals, especially when finely divided.
(h) The magnetic properties of the actinoids are more complex than those of the
lanthanoids. Although the variation in the magnetic susceptibility of the actinoids
with the number of unpaired 5 f electrons is roughly parallel to the corresponding
results for the lanthanoids
4. POTASSIUM DICHROMATE (K2Cr2O7)
(a) Preparation: - It takes place in three steps-
1. 4FeCr2O4+ 8Na2CO3 +7O2 ⎯ ⎯→ 8Na2CrO4(yellow solution) + 2Fe2O3 +8CO2
2. 2Na2CrO4 + 2H ⎯ +
⎯→ Na2Cr2O7(orange sodium) + 2 Na+ + H2O
3. Na2Cr2O7 + 2 KCl ⎯ ⎯→ K2Cr2O7(Orange crystals) + 2 NaCl
(b) The chromates and dichromates are interconvertible in aqueous solution
depending upon pH of the solution.
2 CrO42– + 2H+→Cr2O72– + H2O
Cr2O72– + 2 OH-→2CrO42– + H2O
(c) Potassium dichromate in acidic solution act as oxidizing agent.
• Cr2O72–+ 6I–+ 14H+→ 2Cr+3+ 3I2 + 7H2O
• Cr2O72–+ 3H2S+ 8H+→2Cr+3+ 3S+ 7H2O
• Cr2O72–+ 3Sn2++ 14H+→2Cr+3+ 3Sn4++ 7H2O
• Cr2O72–+ 6Fe2++ 14H+→2Cr+3+ 6Fe3+ + 7H2O
(d) Structure of chromate and dichromate ion:
(e) Uses: Potassium dichromate is a very important chemical used in leather industry
and as an oxidant for preparation of many azo compounds. Potassium dichromate
is used as a primary standard in volumetric analysis.
5. POTASSIUM PERMANGNATE [KMnO4]
a) Preparation: -- It takes place in two steps:
• 2MnO2 + 4 KOH + O2 ⎯ ⎯→ 2 K2MnO4 (Dark green) + 2H2O
• 3 MnO4 +4H ⎯
2- +
⎯→ 2MnO4-(Purple) + MnO2 +2H2O [Disproportionation]
b) Properties of KMnO4
• Potassium permanganate are isostructural with those of KClO4.
• When heated KMnO4 decomposes at 513 K.
• 2KMnO4 ⎯⎯ ⎯→ K2MnO4 + MnO2 + O2
Heat,
53 | P a g e
• MnO4– + 8H+ + 5e– ⎯ ⎯→ Mn2+ + 4H2O (Acidic)
• 2MnO4– + 16H+ + 5C2O42 ⎯ ⎯→ 2Mn2+ + 8H2O +10CO2
• MnO4– + 8H+ + 5Fe2+ ⎯ ⎯→ Mn2+ + 4H2O + 5Fe3+
• 2MnO4– + 16H+ + 10I– ⎯ ⎯→ 2Mn 2+ + 8H2O +5I2
• 5NO2- +2MnO4–+ 6H+ ⎯ ⎯→ 2Mn 2+ + 3H2O +5NO3-
• 5SO3 +2MnO4 + 6H ⎯
2- – +
⎯→ 2Mn 2+ + 3H2O +5SO42-
Oxidising reactions of KMnO4 in neutral or faintly alkaline solutions.
• 2MnO4–+ H2O + I– ⎯ ⎯→ 2MnO2 + 2OH- + IO3–
• 8 MnO4 +3 S2O3 + H2O ⎯
– 2-
⎯→ 8MnO2 + 2OH- +6 SO42-
• 2 MnO4–+3Mn+2+ 2H2O ⎯ ⎯→ 5MnO2+ 4H+
6. Permanganate titrations in presence of hydrochloric acid are unsatisfactory since
hydrochloric acid is oxidised to chlorine.
7. Uses: Besides its use in analytical chemistry, potassium permanganate is used as
a favourite oxidant in preparative organic chemistry. Its uses for the bleaching of
wool, cotton, silk and other textile fibres and for the decolourisation of oils are
also dependent on its strong oxidising power.
8. Structure of Permanganate & Manganate Ion:
54 | P a g e
8. Transition elements form alloys easily because they have
(a) Same atomic number (b) Same electronic configuration
(c) Nearly same atomic size (d) None of the above.
9. Which of the following ion has magnetic moment value of 5.9?
(a) Mn2+ (b) Fe2+ (c) Ni2+ (d) Cu2+
10. Which of the following lanthanoids show +2 oxidation state besides the
characteristic oxidation state +3 of lanthanoids?
(a) Ce (b) Eu (c) Tb (d) Dy.
ASSERTION REASON TYPE QUESTIONS(1MARKS)
In the Following questions a statement of Assertion(A) is followed by a
statement of Reason(R). Select the most appropriate answer from the options
given below:
a. Both A and R are true and R is the correct explanation of A
b. Both A and R are true but R is not the correct explanation of A.
c. A is true but R is false.
d. A is false but R is true.
11. Assertion(A): Magnetic moment values of actinides are lesser than the
theoretically predicted values.
Reason(R): Actinide elements are strongly paramagnetic.
12. Assertion(A): KMnO4 act as an oxidising agent in acidic, basic or neutral
medium.
Reason(R): KMnO4 oxidises ferrous sulphate to ferric sulphate.
13. Assertion(A): Of the 3d4species Cr2+ is strongly reducing and Mn3+ is strongly
oxidising.
Reason(R): Cr+3 state is stable due to half-filled t2g set, Mn+2 is stable due to
half- filled d orbitals
14. Assertion(A): In the series Sc to Zn the enthalpy of atomisation of Zinc is the
lowest.
Reason(R): Zinc has greater number of unpaired electrons
15. Assertion(A): Magnetic moment of Mn2+ is less than that of Cr2+.
Reason(R): Magnetic moment depends on the number of unpaired electrons.
VERY SHORT ANSWER TYPE QUESTIONS (1 MARK)
16. Which element has highest melting point in 3d series?
17. Out of Cu2Cl2 and CuCl2 which is more stable in aqueous solution.
18. Which element of the first transition series don’t exhibit variable oxidation
states?
19. Name an oxo anion having oxidation number of metal (3d series) equal to its
group number.
20. Name two elements of 3d series which show anomalous electronic configuration.
21. Identify the Transition metal of 3d series that acts as a strong reducing agent in
+2 oxidation state in aqueous solution.
22. Name a member of lanthanoid series which is well-known to show +4 oxidation
state.
23. Among the elements of 3d series which element is soft?
24. Arrange the following in increasing order of acidic character: CrO3,CrO, Cr2O3
25. Complete the following equation :
3MnO42- +4H+
VERY SHORT ANSWER TYPE QUESTIONS (2 MARKS)
26. Name an important alloy which contains some of the lanthanoid metals. Mention
its uses.
27. Among Elements of 3d transition series: Write the element
(a) Which is not regarded as transition element.
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(b) Which shows maximum number of oxidation states.
(c) Which forms stable divalent(M2+) ion
(d) Which shows only +3 state?
28. What is Lanthanoid contraction? Give its cause. What are its Consequences?
29. When pyrolusite ore MnO2 is fused of with KOH in presence of air, a green
coloured compound (A) is obtained which undergoes disproportionation reaction
in acidic medium to give purple coloured compound (B).
(i) Write the formulae of (A) & (B).
(ii) What happens when compound (B) is heated.
30. When chromite ore FeCr2O4 is fused with NaOH or (Na2CO3) in presence of air, a
yellow coloured compound (A) obtained which on acidification with dilute
sulphuric acid gives a compound (B). Compound (B) on reaction with KCl forms
an orange coloured crystalline compound (C).
(a) Write the formulae of (A), (B) & (C).
(b) Write one use of compound (C).
SHORT ANSWER TYPE QUESTIONS (3 MARKS)
31. Explain giving a suitable reason for each of the following
(a) Metal –metal bonding is more frequent for the 4d & 5d series of
transition metals than that for the 3d series.
(b) Cu+ salts are colourless while Cu2+ salts are Coloured
(c) Mn2+ exhibits maximum Para magnetism
32. Account for the following
(a) Although Zr belongs to 4d and Hf belongs to 5d transition series but it is quite
difficult to separate them.
(b) There is in general increase in density of element from titanium to copper.
(c) Most of the transition metals and their compounds act as good catalysts.
33. Explain the following observations.
(a) Mn Shows the highest oxidation state of +7 among 3d series elements.
(b) Mn Shows the highest oxidation state of +7 with oxygen but with fluorine it
shows the highest oxidation state of +4.
(c) MnO is basic while Mn2O7 is acidic in nature.
34. Account for the following
(a) Cu+ ion is not stable in aqueous solutions.
(b) The d1 configuration is very unstable in ions.
(c) Eo value for the Mn2+/Mn much more than expected.
35. Assign reasons for the following.
(a) Scandium is a transition element but Zinc is not.
(b) Silver atom has completely filled d orbital (4d10) in its ground state, yet it is
transition element.
(c) In the series Sc (Z = 21) to Zn (Z = 30), the enthalpy of atomisation of zinc is
the lowest.
LONG ANSWER TYPE QUESTIONS (5 MARKS)
36. Give Reasons for the following
(i) Ce4+ in aqueous solution is a good oxidising agent.
(ii) Actinoids contraction is greater from element to element than lanthanoid
contraction.
(iii) The actinoids exhibit a larger number of oxidation states than the
corresponding lanthanoids.
(iv) La3+ and Lu3+do not show any colour in solutions.
(v) Chemistry of all the lanthanoids are quite similar.
37. Complete & balance the following reactions: -
a) Cr2O72–+ Fe2++ H+→
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b) MnO4– + H+ + C2O42- ⎯⎯→
c) KMnO4 ⎯⎯ Heat,
⎯→
d) MnO4– + H2O+ I- ⎯⎯→
e) Cr2O72– + OH-→
CASE BASED QUESTIONS
The Following questions are case based questions carries 4 (1+1+2) marks.
Read the given passage carefully and answer the questions that follow:
38. The transition metals react with a number of non-metals like oxygen, nitrogen,
Sulphur and halogens to form binary compounds. The first series transition metal
oxides are generally formed from the reaction of metals with oxygen at high
temperatures. These oxides dissolve in acids and bases to form oxo metallic salts.
Potassium dichromate and potassium permanganate are common examples.
Potassium dichromate is prepared from the chromite ore by fusion with alkali in
presence of air and acidifying the extract. Pyrolusite ore (MnO2) is used for the
preparation of potassium permanganate. Both the dichromate and the
permanganate ions are strong oxidising agents.
(a) What happens when Manganate ions (MnO42−) undergoes
disproportionation reaction in acidic medium?
(1)
(b) Explain why the colour of KMnO4 disappears when oxalic acid is added to
its solution in acidic medium. (1)
(c) When an orange solution containing Cr2O72– ion is treated with an alkali,
a yellow solution is formed and when H+ ions are added to a yellow solution,
an orange solution is obtained. Explain why does this happen? (2)
OR
A solution of KMnO4 on reduction yields either colourless solution or a
brown precipitate or a green solution depending on the pH of the solution.
What different stages of the reduction do these represent and how are they
carried out?
39. The d-block, which lies between s and p-blocks contains, elements of groups 3-
12, in which d- orbitals are progressively filled in each of four long periods of
periodic table. These elements are also called transition elements or metals.
The elements constituting the f-block are those in which 4 f and 5 f-orbitals are
progressively filled. They are place in a separate panel at the bottom of the
periodic table. The elements of f-block are also called inner-transition
(a) Transition metal are very good catalyst. Why? (1)
(b) Transition metals form a large number of interstitial compounds. Give
reason. (1)
(c) Why the paramagnetic characteristic in 3d- transition series increases up
to Cr and then decreases?
OR
Out of La(OH)3 and Lu(OH)3, which is more basic and why? (2)
40. In the periodic table, the elements are classified into mainly four blocks, i.e. s, p,
d and f. The d-block elements are called transition elements. The s-block contains
the elements of the group 3-12. They possess properties that are transitional
between the s and p-block elements. Zn, Cd, Hg do not exhibit characteristic
properties of transition elements. All the elements belong to this section are
metals. There are four rows of the transition elements involving filling of 3d, 4d,
5d and 6d orbitals.
(a) Why does the transition element scandium not exhibit variable oxidation
state? (1)
(b) Why chromium is a typical hard metal while mercury is a liquid? (1)
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(c) Fe3+/Fe2+ redox couple has less positive electrode potential than
Mn Mn2+
3+/ couple.Why?
(2) OR
Copper (I) is diamagnetic, whereas copper (II) is paramagnetic.
41. Within the 3d-series, manganese exhibits oxidation states in aqueous solution
from +2 to +7, ranging from Mn2+ (aq) to MnO-4 (aq). Likewise, iron forms both
Fe2+ (aq) and Fe3+(aq) as well as the FeO42- ion. Cr and Mn form oxo anions CrO42-,
MnO4-, owing to their willingness to form multiple bonds. The highest oxidation
states of the 3d-metals may depend upon complex formation (e.g., the
stabilization of Co³+ by ammonia) or upon the pH (thus MnO42-(aq) is prone to
disproportionation in acidic solution). Within the 3d-series, there is considerable
variation in relative stability of oxidation states,
sometimes on moving from one metal to a neighbour; thus, for iron, Fe3+ is more
stable than Fe2+,especially in alkaline conditions, while the reverse is true for
cobalt. The ability of transition metals to exhibit a wide range of oxidation states
is marked with metals such as vanadium, where the standard potentials can be
rather small, making a switch between states relatively easy.
(a) Highest fluoride of Mn is MnF4 whereas the highest oxide is Mn2O7 (1)
(b) Which is more stable Fe2+ or Fe³+? (1)
(c). The higher oxidation states are usually exhibited by the members in the
middle of a series of transition elements? (2)
OR
Electrode potential of copper E0 Cu+2 / Cu is positive, whereas E0 Mn+2 / Mn
is more negative than expected Why ?
42. Potassium permanganate, (KMnO4) is prepared by fusion of pyrolusite, MnO2 with
KOH in the presence of an oxidising agent like KNO3. This produces the dark
green potassium manganate, K2MnO4 which disproportionates in a neutral or
acidic solution to give purple permanganate ion. Potassium permanganate is an
important oxidising agent in acidic, alkaline as well as neutral medium.
(a) What is the state of hybridisation of Mn in MnO4-?
(1)
(b) Write an application of potassium permanganate. (1)
(c) How do the oxides of transition elements in lower oxidation states differ
from those in higher oxidation state in the nature of metal-oxygen bonding
and why? (2)
OR
Draw the structure of permanganate ion. Is it paramagnetic or diamagnetic?
ANSWERS
ANSWERS MULTIPLE CHOICE QUESTIONS:
1. 2. 3. 4. 5. 6. 7. 8. 9. 10.
d b b d b d b c a b
11. 12. 13. 14. 15.
b b a c d
16. Cr
17. CuCl2, due to greater hydration enthalpy of Cu2+
18. Sc
19. MnO - or CrO or VO3-
2-
4 4
20. Cr, Cu
21. Cr
22. Ce
23. Zn
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24. CrO < Cr2O3< CrO3
25. 3MnO42- +4H+ 2MnO4- +MnO2+2H2O
26. Mischmetal which consists of 95% of lanthanoid metals, 5% iron and traces of S,
C, Ca and Al. uses. Mischmetal is used in Mg-based alloy to produce bullets, shell
and lighter flint
27. (a) Zn (b)Mn (c)Mn (d)Sc
28. Lanthanoid contraction: The regular decrease in the atomic and ionic radii of
lanthanoids with increasing atomic number is known as Lanthanoid contraction.
Cause for lanthanoid contraction: Poor shielding of 4f electrons.
Consequences of Lanthanoid contraction:
(i) Difficult to separate the lanthanoids because the change in ionic radii is very
small, their chemical properties are similar. Hence, separation of lanthanoids are
difficult.
(ii) Similarity in size of elements belonging to same group of second and third
transition series due to lanthanoid contraction the size of Zr (160 pm) is same as
that of Hf (159 pm).
29. (i) A= K2MnO4 B= KMnO4
(ii) 2KMnO4 ⎯ ⎯→ 2MnO4 + MnO2 + O2
K
30. (a) A = Na2CrO4 B= Na2Cr2O7 C= K2Cr2O7
(b) Potassium dichromate is used as a primary standard in volumetric analysis
31. (a) 4d and 5d transition elements (2nd and 3rd series) are Larger in size than the
corresponding 3d elements. Hence the valence electrons are less tightly held and
form M-M bond more frequently
(b) Due to the absence of unpaired electrons in d-orbitals, Cu+ salts are colourless
while due to presence of unpaired electrons in d-orbitals, Cu2+ salts are Coloured
(c) Because Mn2+ contain 5 unpaired electrons in their 3d sub shells
32. (a) because of lanthanoid contraction both Zr &Hf have similar radii and similar
properties
(b) The decrease in metallic radius coupled with increase in atomic mass results
in a general increase in the density.
(c) The catalytic activity of transition metal ions is due to following two reasons:
Variable oxidation states & Large surface area.
33. (a) Total 7 electrons are present in 3d and 4s in Mn and hence it can
exhibit maximum oxidation state of +7
(b) Because of ability of oxygen to form multiple bonds using 2p orbitals
of oxygen and 3d orbitals of Mn.
(c) Mn in Mn2O7 is in +7 oxidation state and Mn maximum oxidation state is +7.
Hence it is Acidic. If an element in a compound is in lower oxidation state then it
will show basic character. Mn is in+2 oxidation state in MnO hence basic.
34. (a) It disproportionate to give Cu2+ and Cu. Or Due to greater hydration enthalpy
of Cu2+.
(b) The ions in d1 configuration tend to lose one more electron to get into stable d0
configuration.
(c) due to greater stability of half-filled d-subshell (d5) in Mn+2.
35. (a) Scandium is a transition element because it has incompletely filled d orbitals
but Zinc has completely filled d orbitals i.e 3d10 configuration.
(b) Silver (Z = 47) can exhibit +2 oxidation state wherein it will have incompletely
filled d-orbitals (4d), hence a transition element.
(c) because in the formation of metallic bonds, no electrons from 3d-orbitals are
involved in case of zinc, while in all other metals of the 3d series, electrons from
the d-orbitals are always involved in the formation of metallic bonds.
59 | P a g e
36. (i) because it can readily change to the most stable +3 oxidation state by gaining
one electron.
(ii) due to greater poor shielding by 5f-electrons in actinoids than that by 4f-
electrons in the lanthanoids.
(iii) because of the very small energy gap between 5f, 6d and 7s subshells.
(iv) due to absence of unpaired electron in f orbital.
(v) The change in the size of the lanthanoids due to lanthanoid contraction is very
small.
37. (a) Cr2O72–+ 6Fe2++ 14H+→2Cr+3+ 6Fe3+ + 7H2O
(b) 2MnO4– + 16H+ + 5C2O42 ⎯ ⎯→ 2Mn2+ + 8H2O +10CO2
(c) K2MnO4 ⎯ ⎯→ K2MnO4 + MnO2 + O2
(d) 2 MnO4–+ H2O + I– ⎯ ⎯→ 2MnO2 + 2OH- + IO3–
(e) Cr2O7 + 2 OH →2CrO42– + H2O
2– -
38. (a) MnO42− ions disproportionate in acidic medium to give Permanganate ions and
Manganese (IV) oxide. 3MnO42− + 4 H+ → 2MnO4− + MnO2 + 2H2O
(b) This is a redox titration. The deep purple colour of KMnO4 disappears due to
the formation of MnSO4
(c) When Cr2O72– ion is treated with an alkali:
Cr2O72– (orange) + 2 OH-→2CrO42–(yellow) + H2O
When the yellow solution is treated with an acid, we get back the orange solution:
2 CrO42– (yellow)+ 2H+→Cr2O72–(orange) + H2O
OR
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41. a) As oxygen stabilises highest oxidation state more than Florine by forming
multiple bonds.
(b) Fe3+
(c) It is due to greater number of unpaired electrons in (n-1) d and ns orbitals at
the middle of the series. The lesser number of oxidation states at the extreme
ends stems from either too few electrons to lose or share.
OR
Ans due to less hydration enthalpy of Cu+2. The high energy to form From Cu (s)
to Cu+2 (aq) is not balanced by its hydration enthalpy. due to low sublimation
enthalpy of Mn and stable half-filled d5 configuration of Mn2+.
42. (a) Sp3
(b) It is used as an oxidising agent
(c) In the lower oxidation state the transition metal oxides are basic and they are
acidic if the metal is in higher oxidation state. The oxides are amphoteric when
the metal ion is in intermediate oxidation state.
OR
Tetrahedral, diamagnetic.
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5. COORDINATION COMPOUNDS
Quick Revision Points
Werner’s theory
In coordination compounds, metals show two types of linkages (valences)-primary and
secondary.
Primary valences Secondary valences
are ionisable and satisfied by negative are non-ionisable and satisfied
ions. by neutral molecules or negative
ions
It is equal to the coordination
number
Difference between a double salt and a complex salt
Double salts Complex salts
Dissociate into simple ions completely Do not dissociate into simple
when dissolved in water. ions in water
e.g. Mohr’s salt, FeSO4.(NH4)2SO4.6H2O e.g. K4[Fe(CN)6].Complex ion
[Fe(CN)6]4- does not dissociate
into Fe2+ and CN− ions.
Important Terms
(a)Coordination entity - A coordination entity constitutes a central metal atom or ion
bonded to a fixed number of ions or molecules.
e.g., [CoCl3(NH3 )3] is a coordination entity.
(b)Central atom/ion - In a coordination entity, the atom/ion to which a fixed number of
ions/groups are bound in a definite geometrical arrangement around it, is called the
central atom or ion.
(c) Ligands -Ions or molecules bound to the central atom/ion in the coordination entity
are called ligands.
Unidentate ligand Is bound to a metal ion through a single
donor atom. e.g.,Cl−,H2O or NH3
Didentate ligand Is bound to a metal ion through two donor
atoms. e.g.,H2NCH2CH2NH2 (ethane-
1,2-diamine) C2O42− (oxalate ion)
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(d) Coordination number – It is the number of ligand donor atoms to which the metal is
directly bonded.
[Ni(NH3)4]2+ - the coordination number of Ni is 4
[Fe(C2O4)3 ]3– - the coordination number of Fe is 6
(e) Homoleptic and heteroleptic complexes
Homoleptic complexes Heteroleptic complexes
Metal is bound to only one kind of Metal is bound to more than one kind
donor groups e.g.,[Co(NH3)6]3+ of donor groups. e.g Co(NH3)4Cl2]+
[Ma-a2b2]
[CoCl2(en)2]+
[Ma3b3]
[Co(NH3)3(NO2)3]
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Optical Isomerism: Optical isomers are mirror images that cannot be
superimposed on one another and are called as enantiomers.
Optical isomers of [Co(en)3] +3
Trans isomer of [CoCl2 (en)2] + does not show optical activity as it has a plane of
symmetry.
Structural isomerism
Structural Isomerism: These are isomers which differ in the structural arrangement of
ligands around the central atom.
Ionisation Arises when the counter ion in a complex salt is itself a
Isomerism potential ligand and can displace a ligand
[Co(NH3)5SO4]Br and [Co(NH3)5Br]SO4.
Linkage Seen in a coordination compound containing ambidentate
Isomerism ligand
[Co(NH3)5(NO2)]Cl2 and [Co(NH3)5(ONO)]Cl2
Coordination Arises from the interchange of ligands between cationic
Isomerism and anionic entities
[Co(NH3)6][Cr(CN)6] and [Cr(NH3)6][Co(CN)6]
Solvate Arises due to the presence of solvent molecules as a ligand
Isomerism or as free solvent molecules in the crystal lattice.
[Cr(H2O)6]Cl3 and [Cr(H2O)5Cl]Cl2.H2O
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[Ar]3d84s0
The splitting of degenerate levels due to the presence of ligands in a definite geometry
is termed as crystal field splitting
Ligands arranged in a series in the order of increasing field strength is termed as
Spectrochemical series
Weak field ligands Strong field ligands
∆o < P ∆o > P
Form high spin complexes Form low spin complexes
d4 Configuration
t2g3eg1
t2g4eg0
(b) Crystal field splitting in tetrahedral coordination entities
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Colour of coordination compounds
The crystal field theory attributes the colour of the coordination compounds to d-d
transition of the electron.
In the absence of a ligand, crystal field splitting does not occur and hence the substance
is colourless. For example, the removal of water from [Ti(H2O)6 ]Cl3 on heating renders it
colourless.
Bonding in Metal Carbonyls
In metal carbonyls, the M–C σ bond is formed by the donation of lone pair of electrons on
the carbonyl carbon into a vacant orbital of the metal. The M–C π bond is formed by the
donation of a pair of electrons from a filled d orbital of metal into the vacant antibonding
π* orbital of carbon monoxide. The metal to ligand bonding creates a synergic effect
which strengthens the bond between CO and the metal.
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(C) Coordination isomerism (D) Linkage isomerism
6 The coordination number and oxidation state of Cr in K3[Cr(C2O4)3] are
respectively
(A) 3 and +3 (B) 3 and 0
(C) 6 and +3 (D) 4 and +2
7 The geometry and magnetic behaviour of the complex [Ni(CO)4] are
(A) Square planar and (B) Tetrahedral and diamagnetc
paramagnetic
(C) Square planar and (D) Tetrahedral and
diamagnetic paramagnetic
8 Which of the following complex has minimum magnitude of crystal field
splitting?
(A) [Co(NH3)6]3+ (B) [Cr(H2O)6]3+
(C) [Cr(CN)6]3- (D) [CoCl6]3-
9 The core atom of which of the following biologically significant coordination
molecules is cobalt?
(A) Vitamin B12 (B) Haemoglobin
(C) Chlorophyll (D) Carboxypeptidase-A
10 How many isomers are possible for the complex [Co(NH3)4Cl2]Cl?
(A) 4 (B) 2
(C) 1 (D) 3
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AgCl are precipitated per mole of the compound. Write the structural formula
of the complex.
20 Define denticity of a ligand.
21 Indicate the types of isomerism exhibited by the following complex:
[Co(en)3]Cl3 (en = ethylene diamine)
22 What type of isomerism is shown by the complex [Cr(H2O)6]Cl3?
23 Out of the following two coordination entities which is chiral (optically active)?
(a) cis-[CrCl2(ox)2]3- (b) trans-[ CrCl2(ox)2]3–
24 Find the primary and secondary valences of cobalt in [Co(NH3)6]Cl3.
25 Give two examples of ligands which form coordination compounds useful in
analytical chemistry.
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36 (i) Define the following.
(a) Heteroleptic complexes
(b) Spectrochemical series
(c) Coordination polyhedron
(ii)Give reason.
(a)The pi complexes are known for transition elements only.
(b) CO is a stronger ligand than NH3 for many metals.
37
(i)Using crystal field theory, write electronic configuration of the central metal
atom/ion and determine the magnetic moment value in the following.
(a)[CoF6]3–
(b)[Fe(CN)6]4–
(c)[Fe(H2O)6]2+
(ii) A solution of [Ni(H20)6]2+ is green but a solution of [Ni(CN)4]2-is colourless.
Explain.
Case-Based Questions
Read the passage carefully and answer the questions that follow.
38 Alfred Werner, a Swiss chemist was the first to formulate his idea about the
structure of coordination compounds. He proposed the concept of primary and
secondary valences for a metal ion. The primary valences are normally
ionisable and satisfied by negative ions. The secondary valences are non-
ionisable and it is equal to coordination number and is fixed for a metal. The
groups bound by the secondary linkages to metal have spatial arrangements
corresponding to different coordination numbers. Octahedral, tetrahedral and
square planar geometrical shapes are more common in coordination
compounds of transition metals.
Double salts and coordination complexes are formed by the combination of two
or more stable compounds in stoichiometric ratio. Double salts are dissociated
into simple ions completely when dissolved in water whereas complexes do not
dissociate completely into its ions. Werner was the first to discover optical
activity in certain coordination compounds.
(i)What is the oxidation number of cobalt in coordination entity
[Co(H2O)(CN) (en)2]2+?
(ii) What is the coordination number of chromium in
K[Cr(H2O)2(C2O4)2]?
(iii) Arrange the following complexes in increasing order of conductivity of their
solution. Give reason.
[Co(NH3)3Cl3], [Co(NH3)4Cl2] Cl, [Co(NH3)6] Cl3, [Co(NH3)5Cl] Cl2
OR
(iii)a) How many ions are produced from the complex [Co (NH3)6]Cl3 in
solution?
b) When 1 mol CrCl3.6H2O is treated with excess of AgNO3, 3mol of AgCl
are obtained. Write the formula of the complex.
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39 Valence bond theory considers the bonding between metal ion and ligands as
purely covalent. On the other hand, crystal field theory considers the metal-
ligand bond to be ionic arising from electrostatic interaction between the metal
ion and the ligands. In coordination compounds, the interaction between the
ligand and the metal ion causes the five d-orbitals to split-up. This is called
crystal field splitting and the energy difference between the two sets of energy
levels is called crystal field splitting energy. The crystal field splitting (Δo)
depends upon the nature of the ligand and the charge of the metal ion.The
electronic configuration of the metal ion in the complexes depends on the
relative values of Δo and P (pairing energy)
If Δo < P, then complex will be high spin.
If Δo > P, then complex will be low spin.
(i)Calculate the magnetic moment of the metal ion in the complex
K4[(Fe(CN)6].
(ii)On the basis of crystal field theory, write the electronic configuration of d4 in
terms of t2g and eg in an octahedral field when ΔO > P.
(iii)Explain the violet colour of [Ti (H2O)6]3+ complex on the basis of the crystal
field theory. (Atomic number of Ti = 22)
OR
(iii)State the magnetic property of each of the following complexes.
a) Hexaaminechromium (III) ion (At no of Chromium = 24)
b) Tetraamminezinc(II) ion (At number of Zinc =30)
40 In metal carbonyls, there is synergic bonding interaction between metal and
carbon monoxide. This leads to increase in strength of metal ligand bond and
decrease in bond order of CO in carbonyl complex. Donation of electrons from
a filled d-orbital of metal into the vacant antibonding π* bonding orbital of CO
decreases the bond order three to two and half or slightly more thus increasing
the bond length between C– O.
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41 The coordination compounds are of great importance. These compounds are
widely present in the mineral, plant and animal worlds and are known to play
many important functions in the area of analytical chemistry; metallurgy,
biological system, industry and medicine. Formation of coordination
compound is largely used in analytical chemistry for the qualitative detection
and quantitative estimation of metal ions.
(i)Which ligand’s complex is used for determination of hardness of water?
(ii)Which complex is used in the treatment of cancer?
(iii)a) Haemoglobin present in Blood is a complex of which metal?
b) Name the complex of magnesium metal which is present in green plants.
OR
(iii)Describe how gold is extracted using complex formation.
42 Compounds that have the same chemical formula but different structural
arrangements are called isomers.
Ionization Isomerism-This type of isomerism is due to the exchange of
groups between the complex ion and the ions outside it.
Coordination isomerism - This isomerism occurs in compounds containing
complex anionic and cationic parts and can be thought of as occurring by
interchange of some ligands from the cationic part to the anionic part.
Linkage isomerism -This isomerism occurs with ambidentate ligands that are
capable of coordinating in more than one way.
Hydrate isomerism - This isomerism results from the replacement of a
coordinated group by a solvent molecule (Solvate Isomerism).
(i)What type of isomerism is exhibited by
[Co(ONO)(NH3)5]Cl and [Co(NO2)(NH3)5]Cl ?
(ii)What type of isomerism is exhibited by [CrCl2(H2O)4]Cl.2H2O,
[CrCl(H2O)5]Cl2.H2O,[Cr(H2O)6]Cl3 ?
(iii)What is coordination isomerism? Give one example.
OR
What is an ambidentate ligand? Explain with an example.
Answers
1 2 3 4 5 6 7 8 9 10
B A D C A C B D A B
11 12 13 14 15
D A C A D
16 Diaquadioxalatochromate(III) ion
17 [Co(en)3]3+ is more stable complex than [Co(NH3)6]3+ because of chelate effect.
18 [Co(NH3)4(H2O)Cl]Cl2
19 [Cr(H2O)5Cl]Cl2.H2O
20 The number of donor atoms in a ligand which forms a coordinate bond with
the central metal atom is called denticity of a ligand.
21 Optical isomerism
22 Solvate or Hydrate isomerism
23 cis-[CrCl2(ox)2]-3
24 Primary valency -3 Secondary valency - 6
25 EDTA and Dimethyl glyoxime (DMG)
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26 Optical isomers of [Cr(C2O4)3]3-:
In the presence of CN–, the 3d electrons pair up leaving only one unpaired
electron. The hybridisation involved is d2sp3 forming inner orbital complex
which is weakly paramagnetic.
In the presence of H2O (a weak ligand), 3d electrons do not pair up. The
hybridisation involved is sp3d2 forming an outer orbital complex. As it contains
five unpaired electrons so it is strongly paramagnetic..
29 Chelate effect is the stabilization of coordination compounds due to formation
of metal chelates in which a didentate or a polydentate ligand coordinate with
the central metal ion forming a five or a six-membered ring. Example
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32
(i) The pigment responsible for photosynthesis, chlorophyll, is a coordination
compound of magnesium. Haemoglobin, the red pigment 1 of blood which
acts as oxygen carrier is a coordination compound of iron.
(ii) EDTA is used in the treatment of lead poisoning. Cis -platin effectively
inhibits the growth of tumours
(iii) Used in extraction of metals like silver and gold. Gold, for example,
combines with cyanide in the presence of oxygen and water to form the
coordination entity [Au (CN)2]- in aqueous solution. Gold can be separated in
metallic form from this solution by the addition of zinc
33
36 (i)(a) Complexes in which a metal is bound to more than one kind of donor
groups.
(b)Ligands arranged in a series in the order of increasing field strength is
termed as Spectrochemical series
c) The spatial arrangement of ligand atoms attached to metal ion is termed as
coordination polyhedron.
(ii) (a)Transition metals have vacant d orbitals in their atoms or ions into
which the electron pairs can be donated by ligands containing π electrons,
e.g., C6H6, CH2 = CH2, etc. Thus dπ-pπ bonding is possible.
(b) Because in case of CO back bonding takes place in which the central
metal uses its filled d orbital with empty anti bonding π * molecular orbital of
CO
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37(i)
(a)
(b)
No unpaired electron.Magnetic moment =0
(c )
n=4, so μ=√4×(4+2)
μ=√24 BM
(ii)t2g4 eg0
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(iii)[Ti (H2O)6]3+is an octahedral complex. The oxidation state of Ti is +3 with the
coordination number 6. Its outer electronic configuration is 3d1, which means
that it has one unpaired electron. This unpaired electron is excited from t2g
level to eg level by absorbing yellow light and hence appears violet coloured/(d-
d Transition)
OR
(iii) a) Paramagnetic.
b) Diamagnetic
40 (i)Synergic bonding
(ii)Δ0 value increases in metal carbonyls.
(iii) In metal carbonyl the CO to Metal bond C → M is a sigma (σ) bond. There
is also an overlapping of electrons from filled metal d orbitals into empty
antibonding orbital of CO. This results in the formation of a π bond and is and
called back bonding. The M → C bond strengthens the bond between CO and
the metal and this type of bonding creates a synergic effect.
OR
(iii)[Ni(CO)4]
Oxidation Number of Ni = zero
41 (i)EDTA
(ii)cisplatin
(iii)a)Fe b) Chlorophyll
OR
(iii)Gold combines with cyanide in the presence of oxygen and water to form
complex [Au(CN)2]-in aqueous solution. Gold is separated by the addition of
zinc.
42 (i)Linkage isomerism
(ii)Solvate/ Hydrate Isomerism
(iii)Arises from the interchange of ligands between cationic and anionic entities
[Co (NH3)6] [Cr (CN)6] and [Cr(NH3)6][Co(CN)6]
OR
Ambidentate ligand – It is a ligand that can bind to the central metal atom
through any of the two donor atoms present in it. Ex: NO2−, SCN−
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6. HALOALKANES AND HALOARENES
QUICK REVISION POINTS
The replacement of hydrogen atom(s) in a hydrocarbon, aliphatic or aromatic, by a
halogen atom(s) result in the formation of alkyl halide (haloalkane) and aryl halide
(haloarene), respectively.
Classification: Haloalkanes and haloarenes may be classified as follows-
(c) Benzylic
halides
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Nomenclature:
(b) By electrophilic
substitution
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(d) From alkenes
(i) Addition of hydrogen
halides
3. Halogen Exchange:
Finkelstein
reaction
Swarts reaction
Physical Properties:
a) Alkyl halides are colourless when pure. However, bromides and iodides develop
colour when exposed to light. Many volatile halogen compounds have a sweet
smell
b) Physical State: Lower members of alkyl halides (CH3F, CH3Cl, CH3Br and C2H5Cl)
are colourless gases at room temperature. The higher members up C18 are
colourless liquids whereas other members are colourless solids.
c) Solubility: Despite of polar nature of alkyl halides, they are insoluble in water
due to the inability to form hydrogen bonds. Still, they are soluble in non-polar
solvents.
d) Melting and Boiling Point:
⮚ Due to greater polarity as well as higher molecular mass as compared to the
parent hydrocarbon, the intermolecular forces of attraction (dipole-dipole and van
der Waals) are more robust in the halogen derivatives. That is why the boiling
points of chlorides, bromides, and iodides are considerably higher than those of
the hydrocarbons of comparable molecular mass.
⮚ The boiling points of alkyl halides decrease in the order: RI> RBr> RCl> RF. This is
because the magnitude of van der Waal forces increases with the increase in size
and mass of halogen atom.
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e) Density: The density increases with an increase in the number of carbon atoms,
halogen atoms, and atomic mass of the halogen atoms.
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● We can sum up the order of reactivity of alkyl halides towards SN1 and SN2
reactions as follows:
● For the same reasons, allylic and benzylic halides show high reactivity towards the
SN1 reaction. The carbocation thus formed gets stabilized through resonance.
● For a given alkyl group, the reactivity of the halide, R-X, follows the same order in
both the mechanisms R–I> R–Br>R–Cl>>R–F.
● A SN2 reaction proceeds with complete stereochemical inversion while a SN1
reaction proceeds with racemization.
● The stereoisomers related to each other as non-superimposable mirror images are
called enantiomers. Enantiomers possess identical physical properties namely,
melting point, boiling point, solubility, refractive index, etc. They only differ with
respect to the rotation of plane polarised light. If one of the enantiomers is dextro
rotatory, the other will be laevorotatory.
● A mixture containing two enantiomers in equal proportions will have zero optical
rotation, as the rotation due to one isomer will be cancelled by the rotation due to
the other isomer. Such a mixture is known as a racemic mixture or racemic
modification and the process is known as racemization. A racemic mixture is
represented by prefixing dl or (±) before the name.
● Retention of configuration is the preservation of the integrity of the spatial
arrangement of bonds to an asymmetric centre during a chemical reaction or
transformation.
● Inversion, retention, and racemization: There are three outcomes for a reaction
at an asymmetric carbon atom. Consider the replacement of a group X by Y in the
following reaction;
-If (A) is the only compound
obtained, the process is called
retention of configuration.
-If (B) is the only compound
obtained, the process is called
inversion of configuration.
-If a 50:50 mixture of the above two
is obtained then the process is
called racemization.
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formed as a product. Since the β-hydrogen atom is involved in elimination, it is often
called β-elimination.
If there is the possibility of the formation of more than one alkene due to the availability
of more than one α-hydrogen atom, as per Saytzeff rule, “the preferred product is that
alkene which has the greater number of alkyl groups attached to the doubly bonded
carbon atoms.” Thus, 2-bromopentane gives pent-2-ene as the major product.
Wurtz
reaction
Reactions of Haloarenes:
1. Nucleophilic substitution Aryl halides are extremely less reactive towards
nucleophilic substitution reactions due to the following reasons:
(i) C—Cl bond acquires a partial double bond character due to resonance. As a result,
the bond cleavage in haloarene is more difficult than in haloalkane, and therefore, they
are less reactive toward nucleophilic substitution reaction.
(ii) In haloalkane, the carbon atom attached to halogen is sp3 hybridised while in the
case of haloarene, the carbon atom attached to halogen is sp2-hybridised.
(iii) In the case of haloarenes, the phenyl cation formed as a result of self-ionization will
not be stabilized by resonance and therefore, SN1 mechanism is ruled out.
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(iv) Because of the possible repulsion, it is less likely for the electron-rich nucleophile to
approach electron-rich arenes.
Replacement by hydroxyl group
2. Electrophilic
substitution
reactions
I. Halogenation
II. Nitration
III. Sulphonation
IV. Friedel-Crafts
reaction
3. Reaction Wurtz-Fitting
with metals reaction
Fitting reaction
Polyhalogen Compounds
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chloride)
Triiodomethane It was used as an antiseptic but the antiseptic properties are due
(Iodoform) to the liberation of free iodine and not due to iodoform itself.
p,p’- The DDT is effective against the mosquito that spreads malaria
dichlorobiphenyl and lice that carry typhus.
trichloroethane
(DDT)
(a) (a) < (b) < (c) < (d) (b) (a) < (c) < (d) < (b)
(c) (d) < (c) < (b) < (a) (d) (b) < (d) < (c) < (a)
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(a) Dichloromethane (b) 1,2-dichloroethane (c) Ethylidene chloride (d) Allyl
chloride
9. Which of the following alkyl halides will undergo SN1 reaction most readily?
(a) (CH3)3C—F (b) (CH3)3C—Cl (c) (CH3)3C—Br (d) (CH3)3C—I
10. What should be the correct IUPAC name for Diethyl bromomethane?
(a) 1-Bromo-1,1-diethylmethane (b) 3-Bromopentane
(c) 1-Bromo-1-ethylpropane (d) 1-Bromopentane
11. Assertion: Hydrogen halides (HX) are preferred over thionyl chloride for the
preparation of alkyl halides from alcohols.
Reason: Gaseous side products are formed in the case of thionyl chloride.
12. Assertion: Tertiary alkyl halides are least reactive towards SN1 reaction.
Reason: In SN1 reaction, the rate of reaction depends only on the concentration of alkyl
halide.
13. Assertion: Haloalkanes are sparingly soluble in water.
Reason: Haloalkanes do not form hydrogen bonds with water.
14. Assertion: Propene reacts with HBr to form 2-bromo propene.
Reason: As intermediate formed carbocation is secondary which is more stable than
primary.
15. Assertion: SN2 mechanism leads to the inversion of configuration.
Reason: As in this mechanism optical activity is lost.
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17. Aryl chlorides and bromides can be easily prepared by electrophilic substitution of
arenes with chlorine and bromine respectively in the presence of Lewis acid catalysts.
But why does the preparation of aryl iodides require the presence of an oxidizing agent?
18. Out of o-and p-dibromo benzene which one has a higher melting point and why?
19. Which of the following compounds (a) and (b) will not react with a mixture of NaBr
and H2SO4. Explain why?
20. Which of the products will be the major product in the reaction given below?
Explain.
21. Draw resonance structures of haloarene and find out whether the functional group
present in the molecule is ortho, para directing, or meta directing.
22. Write the structures and names of the compounds formed when compound ‘A’ with
the molecular formula, C7H8 is treated with Cl2 in the presence of FeCl3.
24. Write down the structure and IUPAC name for neo-pentyl bromide.
25. Which of the following haloalkanes reacts with aqueous KOH most easily? Explain
giving reason.
(i) 1-Bromobutane(ii) 2-Bromobutane(iii) 2-Bromo-2-methylpropane(iv) 2-Chlorobutane
27. Why can aryl halides not be prepared by reaction of phenol with HCl in the presence
of ZnCl2?
28. Why is it necessary to avoid even traces of moisture during the use of a Grignard
reagent?
29. Aryl halides are extremely less reactive towards nucleophilic substitution. Predict
and explain the order of reactivity of the following compounds towards nucleophilic
substitution:
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30. Cyanide ion acts as an ambient nucleophile. From which end it acts as a stronger
nucleophile in the aqueous medium? Give a reason for your answer.
Case 2
Chlorofluorocarbons (CFCs) described as ‘miracle chemicals’ have no natural resources.
They were first manufactured in the 1930s and industries soon found variety of
applications for them due to their chemical non-reactivity and heat absorbing properties.
CFCs have been used as refrigerants in air conditioners and refrigerators, in aerosol
spray cans, in manufacturing foams and as cleansing agents in the manufacture of
electronics. These chemicals have been given the tradename ‘Freons’ and the term since
became a household name.
1.What is ‘Freon – 12’? (1)
2. Draw its molecular structure (1)
3. State any two harmful effects of CFCs on the environment. (2)
OR
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3. State any two ways to reduce the harmful effect of CFCs. (2)
Case 3
Alkyl Halides can be readily prepared from Alkenes by addition reactions with Hydrogen
Halides. When the alkene is symmetrical about the double bond, only one product is
obtained. But if the alkene is unsymmetrical the addition of Hydrogen Bromide results
in formation of two products. The addition of HBr to an unsymmetrical alkene in
presence of an organic peroxide also results in the formation of two products. The only
difference is in the quantities of isomeric bromides obtained in each case since the
mechanism is different.
1.What is the major product obtained when Propene reacts with HBr? What rule governs
the formation of this product? (1)
2. What mechanism is adopted in presence of Benzoyl Peroxide. (1)
3. Why does only HBr show these anomalies unlike HI or HCl. (2)
OR
3. Write the mechanism of the addition reaction of Propene with HBr in presence or in
absence of organic peroxides. (2)
Case 4
Alkyl Halides have higher melting and boiling points than Alkanes of comparable
molecular mass. The other trends observed are as follows;
i.For a given Alkyl Halide the melting point and boiling point increases with increase in
molecular mass. So, the order is RCl<RBr<RI.
ii. For a given halogen the boiling point rises with increasing Carbon number.
iii. The boiling point also varies as per the nature of the Carbon i.e primary> secondary>
tertiary.
1.Arrange CH3I, CH3F, CH3Br and CH3Cl in decreasing order of melting points. (1)
2. Which has a lower boiling point – Chloropropane or 2-Chloropropane. Why? (2)
OR
2. Arrange the following in increasing order of boiling points. (2)
(CH3)3CBr, CH3CH(Br)CH2CH3, CH3(CH2)3Br, (CH3)3CCl
3. Among the isomeric Chlorotoluene, which isomer has the highest melting point?
Case 5:
Chloroform is a colourless, volatile liquid with sweetish sickly odour and burning taste.
It is denser than water. It is soluble in organic solvents but insoluble in water. It itself
acts as a good solvent. Chloroform causes temporary unconsciousness when its vapours
are inhaled. For this reason, it was used as an anaesthetic until recently. It is also used
as a preservative for anatomical specimen and as a laboratory reagent.
1.What is the IUPAC name of Chloroform? (1)
2. How is Chloroform commercially prepared? (1)
3. Why should Chloroform be stored in dark bottles which are completely filled? Give
chemical equation in support of your answer. (2)
OR
3. Write a short note on any two-name reactions where Chloroform is used as a reagent.
(2)
ANSWERS
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Multiple choice questions
1 2 3 4 5 6 7 8 9 10
b a a b a b b b d b
11 12 13 14 15
d b a a c
23
24
27 C—O bond in phenols is more stable due to resonance effect and it has double
bond character, hence breaking of this bond is difficult.
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28 Grignard reagents are highly reactive and react with water to give
corresponding hydrocarbons.
Case III
1. 2-Bromopropane; Markovnikov’s Rule
2. Free Radical Electrophilic addition.
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3. The bond dissociation enthalpy of H-Cl is large. In case of HI, the I- oxidises to
I2
OR
Refer Class XI TB for answer
Case IV
1. CH3I > CH3Br > CH3Cl > CH3F
2. 2- Chloropropane, since branching decreases surface area of contact and hence
Vander Waals Forces.
OR
(CH3)3CCl <(CH3)3CBr < CH3CH(Br)CH2CH3 < CH3(CH2)3Br
3. The para-isomer because it is symmetrical and fits better in the crystal lattice.
Case V
1. Trichloromethane
2. By direct halogenation of Methane in presence of sunlight.
3. In presence of air and sunlight, Chloroform produces poisonous gas Phosgene;
CHCl3 + O2 -> COCl2 + HCl
OR
The Reimer-Tiemann reaction is a classic organic reaction that involves the
conversion of phenols to salicylaldehyde (ortho-hydroxybenzaldehyde) in the
presence of chloroform (CHCl3) and a strong base, typically aqueous sodium
hydroxide (NaOH) or potassium hydroxide (KOH).
The Carbylamine Reaction, also known as the Isocyanide Test, involves the
reaction of primary amines with chloroform and alcoholic potassium hydroxide
to form foul-smelling isocyanides (carbylamine), which can be detected by their
characteristic odour.
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7. Alcohols, Phenols and Ethers
Quick Revision Points: -
Alcohols Phenols Ethers
–OH group is attached to —OH group is attached to a —OH group is attached to a sp3—
an sp3 hybridised carbon sp3 hybridised carbon adjacent hybridised carbon atom next to
atom of an alkyl group. to the carbon-carbon double an aromatic ring.
bond, that is to an allylic
carbon
—OH group bonded to a carbon- —OH group bonded to the sp2-hybridised carbon atom
carbon double bond, i.e., to a vinylic of an aromatic ring
carbon
Classification of Ethers
(a) simple or symmetrical ether- if the alkyl Structures of Functional Groups
or aryl groups attached to the oxygen atom
are the same. Diethyl ether, C2H5OC2H5
(b)mixed or unsymmetrical ether- if the two
groups are different. C2H5OCH3 and
C2H5OC6H5
Isomerism in Alcohols: Alcohols exhibit four types of isomerism: (i)Chain isomerism:
𝐶4 𝐻10 𝑂 Butan-1-ol, 2-methylpropan-1-ol (ii)Position isomerism: 𝐶3 𝐻8 𝑂 Propan-1-ol,
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propan-2-ol (iii)Functional isomerism: 𝐶2 𝐻6 𝑂 Ethanol, methoxy methane (iv)Optical
isomerism: Monohydric alcohols containing chiral carbon atoms exhibit optical
isomerism. E.g. Butan-2-ol, Pentan-2-ol
Nomenclature of Alcohols : According to IUPAC system, ‘e’ of the parent alkane is
replaced with the suffix ‘ol’. For naming polyhydric alcohols, the ‘e’ of alkane is retained
and the ending ‘ol’ is added. e.g. CH3CH(OH)CH2CH3 (Butan-2-ol)
Nomenclature of Phenols: - The simplest hydroxy derivative of benzene is phenol. It is
its common name and IUPAC name. For disubstituted compounds the terms ortho (1,2-
disubstituted), meta (1,3 disubstituted) and para (1,4-disubstituted) are often used in
the common names.
Nomenclature of Ethers:- The larger (R) group is chosen as the parent hydrocarbon
and smaller group is written as alkoxy or phenoxy. CH3OCH2CH3 (Methoxyethane)
Preparation of Alcohols
(1) From alkenes
(i)By acid catalysed hydration: Mechanism
Alkenes react with water in the Step 1: Protonation of alkene to form carbocation
presence of acid as catalyst to by electrophilic attack of 𝐻3 𝑂+ 𝑜𝑟 𝐻 + .
form alcohols.
In case of unsymmetrical alkenes,
the addition reaction takes place
in accordance with Markovnikov’s
rule
(ii) By hydroboration–oxidation:
Diborane (BH3)2 reacts with alkenes to give trialkyl boranes as addition product.
This is oxidised to alcohol by hydrogen peroxide in the presence of aqueous sodium
hydroxide
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Methanal→ primary alcohol, Other aldehyde → secondary alcohol, Ketones → tertiary
alcohol
Preparation of Phenols
(1)From haloarenes (3). From benzenesulphonic acid
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Presence of electron withdrawing groups ( −𝑁𝑂2, -CN, -X) increases the acidity of phenol
by stabilizing phenoxide ion while presence of electron releasing groups (-R, -𝑁𝐻2 , -OR)
decreases the acidity of phenol by destabilizing phenoxide ion. Thus, increasing acidic
strength is o-cresol < p-cresol < m-cresol < phenol < o-nitrophenol < 2, 4, 6
Trinitrophenol (picric acid) Higher Ka and lower pKa value correspond to the stronger
acid.
(b) Esterification
Alcohols and phenols react with carboxylic acids, acid chlorides and acid anhydrides to
form esters.
3. Dehydration:
4. Oxidation:
• Oxidation of alcohols involves the formation of a carbon oxygen double bond with
cleavage of an O-H and C-H bonds.
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• also known as catalytic dehydrogenation reactions as it involves loss of dihydrogen
from an alcohol molecule
• Primary alcohol → Aldehyde → Carboxylic acid
• Primary alcohol → Carboxylic acid (strong oxidizing agent, acidified 𝐾𝑀𝑛𝑂4)
• Secondary alcohol → Ketone
• CrO3 (Chromic anhydride)in anhydrous medium is used as the oxidising agent for
the isolation of aldehydes.
2. Kolbe’s reaction
3. Reimer-Tiemann reaction
Preparation of Ethers
1. By dehydration of 2. Williamson synthesis
alcohols
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• an alkyl halide is reacted with sodium alkoxide.
It is not appropriate
for the preparation of
mixed ether like ethyl
methyl ether.
Alkyl aryl ethers are cleaved at the alkyl-oxygen bond due to the more stable aryl-
oxygen bond. The reaction yields phenol and alkyl halide
When primary or secondary alkyl groups are present, it is the lower alkyl group
that forms alkyl iodide (SN2 reaction).
• when one of the alkyl group is a tertiary group, the halide formed is a tertiary
halide (SN1 reaction).
2. Electrophilic substitution
The alkoxy group (-OR) is ortho, para directing and activates the aromatic ring
towards electrophilic substitution
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MULTIPLE CHOICE QUESTIONS (1 MARKS)
1. What is the correct order of reactivity of alcohols in the following reaction?
a) A, B, C, D b) A,D c) B, C d) A
5. Give IUPAC name of the compound
a) 2-Chloro-5-hydroxyhexane c) 5-Chlorohexan-2-ol
b) 2-Hydroxy-5-chlorohexane d) 2-Chlorohexan-5-ol
6. IUPAC name of the following compound
a) 1-methoxy-1-methylethane c) 2-methoxypropane
b) 2-methoxy-2-methylethane d) isopropylmethyl ether
7. Phenol is less acidic than
a) Ethanol b) o-nitrophenol c) o-methylphenol d) o-methoxyphenol
8. Arrange the following compounds in increasing order of boiling point.
Propan-1-ol, butan-1-ol, butan-2-ol, pentan-1-ol
a) Propan-1-ol, butan-2-ol, butan-1-ol, pentan-1-ol c) Pentan-1-ol, butan-2-ol,
butan-1-ol, propan-1-ol
b) Propan-1-ol, butan-1-ol, butan-2-ol, pentan-1-ol d) Pentan-1-ol, butan-1-ol,
butan-2-ol, propan-1-ol
9. Which of the following reagents can be used to oxidise primary alcohols to aldehydes?
(i) 𝐶𝑟𝑂3 in anhydrous medium. (iii) Pyridinium chlorochromate
(ii) 𝐾𝑀𝑛𝑂4 in acidic medium (iv) Heat in the presence of Cu at 573K.
a) (i), (ii) b) (i), (iii), (iv) c) (ii), (iii), (iv) d) (iii), (iv)
10. Which one is secondary alcohol
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(a)(i) b) (ii) c) (iii) d) (iv)
ANSWERS MULTIPLE CHOICE QUESTIONS:
Q.No 1 2 3 4 5 6 7 8 9 10
Answer c) b) c) c) c) c) b) a) b) d)
ASSERTION REASON TYPE QUESTIONS(1MARKS)
The following questions are statement of assertion followed by a statement of reason is
given. Choose the correct answer out of the following choices.
a) Assertion and reason both are correct statements and reason is correct explanation
for assertion.
b) Assertion and reason both are correct statements but reason is not correct
explanation for assertion.
c) Assertion is correct statement but reason is wrong statement.
d) Assertion is wrong statement but reason is correct statement.
1. Assertion: p-nitrophenol is more acidic than phenol.
Reason: Nitro group helps in the stabilisation of the phenoxide ion by dispersal of
negative charge due to resonance.
2. Assertion: Ethanol is a weaker acid than phenol.
Reason: Ethanol reacts with Na and phenol reacts with Na and NaOH
3. Assertion: o-Nitrophenol is more soluble in water than the m-and p-isomers.
Reason: m- and p- Nitrophenols exist as associated molecules because of inter
molecular hydrogen bonding.
4. Assertion: Phenols give o- and p-nitrophenol on nitration with conc. 𝐻𝑁𝑂3 and
Sulphuric acid mixture.
Reason: —OH group in phenol is o–, p– directing.
5. Assertion: Bromination of phenol does not require the presence of Lewis acid.
Reason: -OH group attached to benzene ring has highly activating effect
ANSWERS ASSERTION REASON BASED QUESTIONS:
Q.No 1 2 3 4 5
Answer a) b) d) d) a)
VERY SHORT ANSWER TYPE QUESTIONS (2 MARKS)
1. Out of o-nitrophenol and p-nitrophenol, which is more volatile? Explain
Answer: - o-nitrophenol, due to intramolecular hydrogen bonding, is more volatile in
nature. In para-nitrophenol, there is intermolecular hydrogen bonding.
2. Nitration is an example of aromatic electrophilic substitution and its rate depends
upon the group already present in the benzene ring. Out of benzene and phenol,
which one is more easily nitrated and why?
Answer: -Phenol will be easily nitrated since the —OH group attached to the benzene
ring activates it towards electrophilic substitution due to +R effect.
3. In Kolbe’s reaction, instead of phenol, phenoxide ion is treated with carbon dioxide.
Why?
Answer: -Phenoxide ion is more activating than phenol towards electrophilic
substitution reaction. Hence, it undergoes electrophilic substitution with carbon
dioxide, a weak electrophile.
4. Arrange the following sets of compounds in order of their increasing boiling points:
(a) Pentan-1-ol, butan-1-ol, butan-2-ol, ethanol, propan-1-ol, methanol.
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(b) Pentan-1-ol, n-butane, pentanal, ethoxyethane.
Answer: - (a) Methanol, ethanol, propan-1-ol, butan-2-ol, butan-1-ol, pentan-1-ol.
(b) n-Butane, ethoxyethane, pentanal and pentan-1-ol.
5. The carbon– oxygen bond length (136 pm) in phenol is slightly less than that in
methanol (142 pm). Explain.
Answer: - This is due to
(i) partial double bond character of C-O bond because of resonance in phenol and
(ii) sp2 hybridised state of carbon of phenol to which oxygen is attached.
6. Give reasons: -
a.The bond angle in alcohols is slightly less than the tetrahedral angle (109°-
28’).
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Answer:-b)
4. Give the structures and IUPAC names of the products expected from the following
reactions:
(a) Catalytic reduction of butanal.
(b) Hydration of propene in the presence of dilute sulphuric acid.
(c) Reaction of propanone with methyl magnesium bromide followed by hydrolysis.
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Answer: -
5. Show how are the following alcohols prepared by the reaction of a suitable
Grignard reagent on methanal?
Answer: -(i)
(ii)
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CASE BASED QUESTIONS
Read the passage given below and answer the following questions:
Both alcohols and phenols are acidic in nature, but phenols are more acidic than
alcohols. Acidic strength of alcohols mainly depends upon the inductive effect.
Acidic strength of phenols depends upon a combination of both inductive effect
and resonance effects of the substituent and its position on the benzene ring.
Electron withdrawing groups increases the acidic strength of phenols whereas
electron donating groups decreases the acidic strength of phenols. Phenol is a
weaker acid than carboxylic acid.
1. Arrange the following compounds in increasing order of their acid strength: 1
mark
Propan-1-ol, 2,4,6-trinitrophenol, 3-nitrophenol, 3,5-dinitrophenol, phenol, 4-
methylphenol
Answer: - Propan-1-ol, 4-methylphenol, phenol, 3-nitrophenol, 3,5-dinitrophenol, 2,4,
6-trinitrophenol
2. Alcohols act as Bronsted bases also. Explain 1
mark
Answer: -It is due to the presence of unshared electron pairs on oxygen, which makes
them proton acceptors.
3. Draw the resonating structures of phenol and phenoxide ions 2
mark
Answer:-
OR
Explain why phenoxide ion is more stable than phenol.
Answer: -Resonance structures of phenol have charge separation due to which the
phenol molecule is less stable than phenoxide ion which has charge delocalization.
2. The correct order of boiling points of alcohol of the same molecular mass :
(a) 1° > 2° > 3°
(b) 3° > 2° > 1°
(c) 2° > 1° > 3°
(d) 2° > 3° > 1°
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3. When Phenol is distilled with zinc dust, it gives
(a) Benzene
(b) Toluene
(c) Benzaldehyde
(d) Benzoic acid
Each question consists of two statements, namely, Assertion (A) and Reason (R).For selecting
the correct answer, use the following code:
(a) Both Assertion (A) and Reason (R) are the true and Reason (R) is a correct explanation of
Assertion (A).
(b) Both Assertion (A) and Reason (R) are the true but Reason (R) is not a correct explanation
of Assertion (A).
(c) Assertion (A) is true and Reason (R) is false.
(d) Assertion (A) is false and Reason (R) is true.
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NOMENCLATURE TYPE QUESTIONS
1. Write the IUPAC name of the following compounds.
(a) (b)
(c) (d)
(e)
2. Write the structure of the following compound whose IUPAC name are as follows:
(a) 2-methylpropan- 2-ol molecule.
(b) Hex-l-en-3-ol
(c) Butane-1,3-diol
(d) 1-phenylpropan-2-ol
(e) 2-Methoxypropane
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5. Give one chemical test to distinguish (i) Ethanol and propan-1-ol (ii) Propan-2-ol and
pentan-3-ol
6. Give one chemical test to distinguish
(i) β – naphthol and ethanol
(ii) diethyl ether and n-butane
(iii) Diethyl ether and but-1-ene
NAME REACTION TYPE QUESTIONS
1. Write the following name reaction:
a) Kolbe’s reaction
b) Reimer-Tiemann reaction
c) Williamson synthesis
d) Hydroboration
e) Esterification
MECHANISM TYPE QUESTIONS
1. Write the mechanism of acid catalysed hydration of alkenes.
2. Write the mechanism of acid catalysed dehydration of ethanol to yield ethene at
443K.
3. Write the mechanism of dehydration of Alcohol to form Ether at 413 K.
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WORD PROBLEM TYPE QUESTIONS
1. An organic compound A with molecular formula C8H16O2 was hydrolysed with
sulphuric acid to give a carboxylic acid B and alcohol C. Oxidation of C with chromic
acid produced B. C on dehydration gives but-1-ene. Write reactions involved.
2. When an aromatic organic compound with molecular formula C6H6O is treated with
bromine water, white precipitate of compound Y is obtained. Give the structure and
the name of X and Y and write the chemical reaction involved.
3. An organic compound ‘A’ having molecular formula C3H6 on treatment with aq. H2SO4
give ‘B’ which on treatment with Lucas reagent gives ‘C’. The compound ‘C’ on
treatment with ethanolic KOH gives back ‘A’. Identify A, B, C.
4. An organic compound A (C6H6O) gives a characteristic colour with aq.FeCl3 solution.
(A) On reacting with CO2 and NaOH at 400 K under pressure gives (B) which on
acidification gives a compound (C). The compound (C) reacts with acetyl chloride to
give (D) which is a popular pain killer. Deduce the structure of A, B, C& D.
5. An organic compound (X) when dissolved in ether and treated with magnesium metal
forms a compound Y. The compound, Y, on treatment with acetaldehyde and the
product on acid hydrolysis gives isopropyl alcohol. Identify the compound X. What is
the general name of the compounds of the type Y.
ANSWERS
MULTIPLE CHOICE QUESTIONS (ONE CORRECT ANSWER)
1. (b)o-and p-bromophenols
2. (a) 1° > 2° > 3°
3. (a) Benzene
4. (d) Ditert. butyl ether
5. (a) conc. H2S04 at 413 K
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REASONING TYPE QUESTIONS
1. Intermolecular hydrogen bonding
2. –NO2 is EWG while OCH3 is EDG so H+ release is easy from o-nitrophenol.
3. Where R=alkyl, ROH behaves as Bronsted base and where R=aryl, R’OH behaves as a
Bronsted acid.
4. o-nitrophenol due to intramolecular H-bonding.
5. Phenol, phenoxide ion is resonance stabilized.
6.Alcohols can form H-bonds with water.
7. intermolecular H-bonding.
8. Repulsion between lone pair of electrons of oxygen of alcohols.
9. (CH3)3 is tert. Carbocation which is more stable for SN1 reaction.
10. Tert. Alkyl halide undergo elimination in the presence of strong nucleophile and form
alkene.
CHEMICAL TEST TYPE QUESTIONS
1. Propan-2-ol (2*) alcohol takes 5 minutes to give turbidity with Lucas reagent
(HCl/ZnCl2)
Whereas propan-1-ol(1*) does not give test
CH3CH(OH)CH3 + HCl/ZnCl2-→CH3CH(Cl)CH3 (five minutes)
2. Add 𝑁𝑎𝐻𝐶𝑂3to each. Phenol will not react, whereas acetic acid will give brisk
effervescence due to 𝐶𝑂2.(comparison of acidic nature)
CH3COOH + NaHCO3→CH3COONa + H2O + CO2 (brisk effervescence)
3. Add 𝐼2 and NaOH to each one. Ethanol will give yellow ppt. of iodoform (iodoform
test), whereas methanol will not give yellow ppt.
CH3CH2OH ---- I2/NaOH →CHI3 (YELLOW PPT)
4. (i) Phenol gives violet colouration with neutral FeCl3 where prop-1-ol does not
6 C6H5OH + FeCl3 → [Fe(O C6H5)6]-3 + 3H+ + 3HCl
(ii) Ethanol gives yellow ppt in Iodoform test where di methyl ether does not
CH3CH2OH + I2/NaOH → CHI3 (YELLOW PPT)
(iii)2-methylpropan-2-ol gives turbidity immediately with Lucas reagent while propan-
1-ol does not.
5. (i)Both the alcohols are primary alcohols so can be distinguished by Iodoform test
CH3CH2OH + I2/NaOH →CHI3 (YELLOW PPT) Prop-1-ol does not perform Iodoform test
(ii) Propan-2-ol gives yellow ppt in Iodoform test where Pentan-3-ol does not
CH3CH(OH)CH3 + I2/NaOH→CHI3 (yellow ppt)
6. (i) β – naphthol gives violet colouration with neutral FeCl3 where Ethenol does not
(ii)Di ethyl ether dissolves in con. H2SO4 where n-butane does not
(iii)But-1-ene decolourises potassium permanganate solution where di ethyl ether does
not.
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b. Reimer-Tiemann reaction
c. Williamson synthesis
d. Hydroboration
e. Esterification
2.
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3. Mechanism
(ii)
(iii)
2 (i)
(ii)
(iii)
3 (i)
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(ii)
(iii)
(iv)
e)
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WORD PROBLEM TYPE QUESTIONS
1. A - Butylbutanoate , B - Butanoic acid , C - Butan-1-ol
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OR
Write the equation for reaction of compound A with neutral
FeCl3
2. Read the passage given below and answer the following questions:
Alcohol and phenols are acidic in nature. Electron withdrawing group in phenol
increases its acidic strength whereas electron donating groups decreases it. Alcohols
undergo nucleophilic substitution reactions with hydrogen halide to give alkyl halide.
Oxidation of primary alcohols yields aldehydes with mild oxidising agents and carboxylic
acids with strong oxidising agents while secondary alcohols yield ketones. The presence
of –OH groups in phenols activates the ring towards electrophilic substitution. various
important products are obtained from phenol like salicylaldehyde, salicylic acid, picric
acid.
1.Give the structure of alcohol which is resistant to oxidation?
2.Name any one group that increases the acidic character of phenol.
3.Consider the following equation:
X----(i)NaOH,CO2---------- C6H5OH ---------(i)CHCl3+ NaOH-----→ Y
(ii)H+ (ii) H+
Identify X and Y
OR
p-nitrophenol is a stronger acid than phenol while p-cresol is a weaker acid. why?
3. Read the passage given below and answer the following questions:
Although chlorobenzene is inert towards nucleophilic substitution, however it gives
quantitative yield of phenol when heated with aq. NaOH at high temperature and under
high pressure. As far as electrophilic substitution in phenol is concerned the - OH group
is an activating group, hence, its presence enhances the electrophilic substitution at o-
and p-positions.
1. Name the reaction mechanism involved in conversion of chlorobenzene to phenol?
2. Phenol undergoes electrophilic substitution more readily than benzene. why?
3.Phenol on treatment with excess of conc. HNO3 gives a yellow-coloured explosive
compound. Name the compound and give reaction involved?
OR
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3.X= salicylic acid, Y= salicylic aldehyde
Or
p-nitro phenol is stronger acid than p- cresol because Nitro group is electron
withdrawing group which reduces electron density on benzene ring resulting in increase
in acidic strength.
Case based question 3
1.Unimolecular nucleophilic substitution (SN1)
2.Phenol readily undergoes nucleophilic substitution because hydroxy group in phenol is
activation group, which increases electron density on benzene ring.
3.Picric acid (2,4,6 tri nitro phenol)
Or
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8. Aldehydes, Ketones & Carboxylic Acids
Quick Revision Notes:
General formula: CnH2nO having >C=O group.
Aldehydes: where R = H, e.g., CH3CHO, HCHO,
C6H5CHO, etc.
Ketones: where R = alkyl or aryl group. e.g., CH3COCH3, CH3COC6H5,
C6H5COC6H5, etc.
Structure:
1] In aldehydes, the carbonyl group is bonded to a carbon and hydrogen while in the
ketones; it is bonded to two carbon atoms. The carbonyl compounds in which
carbonyl group is bonded to oxygen are known as carboxylic acids, and their
derivatives (e.g. esters, anhydrides) while in compounds where carbon is attached to
nitrogen and to halogens are called amides and acyl halides respectively.
2] Aldehydes, Ketones are important classes of organic compounds containing carbonyl
groups. They are highly polar molecules. They boil at higher temperatures than the
corresponding hydrocarbons and weakly polar compounds such as ethers. Lower
members are soluble in water because they can form H-bond with water. Higher
members are insoluble in water due to large size of their hydrophobic group.
3] The carbonyl carbon atom is sp2 -hybridised and forms three sigma (σ) bonds. The π
Electron cloud of >C=O is unsymmetrical. On the other hand, due to same
electronegativity of the two carbon atoms, the π-electron of the >C=C< bond is
symmetrical. The structure of the carbonyl group in aldehydes and Ketones is, not
entirely adequately represented by >C=O, nor by the alternative>C+─ O-. The real
structure or resonance hybrid lies somewhere between the following structure:
4] The IUPAC names of open chain aliphatic aldehydes and ketones are derived from the
names of the corresponding alkanes by replacing the ending –e with –al and –one
respectively.
5] General Methods of Preparation:
A} By oxidation of alcohols Aldehydes and ketones are generally prepared by oxidation
of primary and secondary alcohols, respectively.
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Propyne on hydration gives propanone.
.
D} Stephen Reaction: Reduction of nitriles in presence of stannous chloride in presence
of HCl gives imine which on hydrolysis gives corresponding aldehyde.
E} From Hydrocarbons:
(i) By oxidation of methyl benzene:
Etard Reaction: Chromyl chloride (CrO2Cl2) oxidizes methyl group to a chromium
complex, which on hydrolysis gives corresponding benzaldehyde.
Gattermann-Koch reaction:
Benzene or its derivatives on treatment with carbon monoxide and HCl in presence of
anhydrous aluminium chloride or cuprous chloride (CuCl) gives benzaldehyde or
substituted benzaldehydes.
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Acyl chloride on treatment with dialkyl cadmium (prepared by reaction of cadmium
chloride with Grignard reagent gives ketone.
From nitriles:
Nitriles on treatment with Grignard reagent followed by hydrolysis give ketones.
PROPERTIES:
*The boiling points of aldehydes and ketones are higher than hydrocarbons and ethers of
comparable molecular masses. It is due to weak molecular association in aldehydes and
ketones arising out of the dipole-dipole interactions. Also, their boiling points are lower
than those of alcohols of similar molecular masses due to absence of intermolecular
hydrogen bonding.
*The lower members of aldehydes and ketones such as methanal, ethanal and
propanone are miscible with water in all proportions, because they form hydrogen bond
with water
NUCLEOPHILIC ADDITION REACTIONS
*Since aldehydes and ketones both possess the carbonyl functional group, they undergo
similar chemical reactions Aldehydes are generally more reactive than ketones in
nucleophilic addition reactions due to steric and electronic reasons. Sterically, the
presence of two relatively large substituents in ketones hinders the approach of
nucleophile to carbonyl carbon than in aldehydes having only one such substituent.
Electronically, aldehydes are more reactive than ketones because two alkyl groups
reduce the electrophilicity of the carbonyl carbon more effectively than in former.
Order of reactivity of aldehydes and ketones towards nucleophilic addition is :
HCHO > CH3CHO > CH3CH2CHO.
HCHO > RCHO > R CO R.
ArCHO > Ar COR > Ar CO Ar.
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With HCN
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REDUCTION OF ALDEHYDES AND KETONES
Catalytic reduction to obtain alcohols
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Oxidation of aldehydes and ketones:
(i) Aldehydes are oxidized to acids in presence of oxidising agents HNO3, K2Cr2O7, KMnO4
ii)Ketones are oxidized under drastic conditions i.e. with powerful oxidising agents like
HNO3, K2Cr2O7, KMnO4. at higher temperature.: ketones give mixture of carboxylic acids.
2)Fehling’s test: When an aliphatic aldehyde is heated with Fehling’s reagent it forms
reddish brown precipitates of cuprous oxide. Fehling’s reagent: Fehling solution A
(aqueous solution of CuSO4) + Fehling solution B (alkaline solution of sodium potassium
tartarate)
Ketones do not give this test.
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ALDOL CONDENSATION:
Aldehydes and ketones having at least one α-hydrogen condense in the presence of
dilute alkali to form β-hydroxy aldehydes(aldol) or β –hydroxy ketones (ketol).
Cross aldol condensation: Aldol condensation between two different aldehydes and
ketones is called aldol condensation. If both of them contain α -hydrogen atoms, it gives
a mixture of four products.
Cannizzaro Reaction
Aldehydes which do not contain hydrogen when treated with a concentrated solution of
an alkali undergo self oxidation-reduction. As a result, one molecule of aldehyde is
reduced to corresponding alcohol while the other molecule is oxidized to the
corresponding acid.
Haloform reaction: Aldehydes and ketones having at least one methyl group linked to
the carbonyl carbon atom i.e. methyl ketones are oxidised by sodium hypohalite to
sodium salts of corresponding carboxylic acids having one carbon atom less than that of
carbonyl compound. The methyl group is converted to haloform.
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Carboxylic Acids: Carboxylic acids are the compounds containing the carboxyl
functional group (-COOH).
Preparation of carboxylic acid:
(i) From alcohols: Primary alcohols are readily oxidised to carboxylic acids with common
oxidising agents such as potassium permanganate (KMnO4) in neutral, acidic or alkaline
media or by potassium dichromate (K2Cr2O7) and chromium trioxide (CrO3) in acidic
media.
From alkyl benzenes: Aromatic carboxylic acids can be prepared by vigorous oxidation
of alkyl benzenes with chromic acid or acidic or alkaline potassium permanganate.
From Nitriles: Nitriles on hydrolysis in presence of dilute acids or bases forms amide
which on further hydrolysis gives carboxylic acid.
From Grignard reagent: Grignard reagents react with carbon dioxide (dry ice) to form
salts of carboxylic acids which on hydrolysis forms carboxylic acids.
From acyl halides and anhydrides: Acid chlorides when hydrolysed with water give
carboxylic acids. On basic hydrolysis carboxylate ions are formed which on further
acidification forms corresponding carboxylic acids. Anhydrides on hydrolysis forms
corresponding acid(s)From esters: Acidic hydrolysis of esters gives directly carboxylic
acids while basic hydrolysis gives carboxylates, which on acidification give corresponding
carboxylic acids.
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Physical properties of carboxylic acids:
(i)Solubility: As the size of alky group increases solubility of carboxylic acid decreases
because non-polar part of the acid increases.
(ii)Boiling points: Carboxylic acids are higher boiling liquids than aldehydes, ketones and
even alcohols of comparable molecular masses. This is due to extensive association of
carboxylic acid molecules through intermolecular hydrogen bonding.
Acidity of carboxylic acids:
Carboxylic acids are more acidic than phenols. The strength of acid depends on extent of
ionization which in turn depends on stability of anion formed.
(i)Effect of electron donating substituents on the acidity of carboxylic acids: Electron
donating substituent decreases stability of carboxylate ion by intensifying the negative
charge and hence decreases acidity of carboxylic acids.
(ii)Effect of electron withdrawing substituent on the acidity of carboxylic acids: Electron
withdrawing group increases the stability of carboxylate ion by delocalizing negative
charge and hence, increases acidity of carboxylic acid. The effect of the following groups
in increasing acidity order is
Ph < I < Br < Cl < F < CN < NO2 < CF3
Esterification: Carboxylic acids are esterified with alcohols in the presence of a mineral
acid such as concentrated H2SO4 or HCl gas as a catalyst.
(iii) Carboxylic acids react with PCl5, PCl3 and SOCl2 to form acyl chlorides.
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Some Distinguishing tests:
1.
Methanal Ethanal
It does not give yellow ppt of It gives yellow ppt of iodoform with NaOH
iodoform with NaOH and I2 and I2
2 Benzaldehyde Acetophenone
*It gives silver mirror with Tollen’s *It does not gives silver mirror with Tollen's
reagent reagent
*It does not give yellow ppt of *It gives yellow ppt of iodoform with Iodine
iodoform with iodine and NaOH or and NaOH or NaOI
NaOI
3 Methanal Benzaldehyde
It gives brick red ppt with Fehling’s It does not give brick red ppt with Fehling’s
solution A & B solution A & B
4 Propanal Ethanal
It does not give yellow ppt of It gives yellow ppt of iodoform with NaOH
iodoform with NaOH and I2 and I2
5 Phenol Benzoic Acid
Does not give brisk effervescence Gives brisk effervescence with NaHCO3
with NaHCO3
6 Acetic acid Formic acid
It doesn't give silver mirror with It gives silver mirror with Tollen’s reagent
ammonical silver nitrate. (ammonical silver nitrate).
It doesn't give brick red ppt with It gives brick red ppt with Fehling’s solution
Fehling’s solution A & B A&B
7 Phenol Ethanol
Gives violet coloured solution with Does not give violet coloured solution with
neutral FeCl3 solution. neutral FeCl3 solution.
8 Propanol Ethanol
It does not give yellow ppt of It gives yellow ppt of iodoform with NaOH
iodoform with NaOH and I2 and I2
9 Benzophenone Acetophenone
It does not give yellow ppt of It gives yellow ppt of iodoform with NaOH
iodoform with NaOH and I2 and I2
10 Pentan-3-one Pentan-2-one
It does not give yellow ppt of It gives yellow ppt of iodoform with NaOH
iodoform with NaOH and I2 and I2
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MULTIPLE CHOICE QUESTIONS (1 MARKS)
1.) Which aldehyde will give Cannizzaro’s reaction?
(a) CH3CH2CH2CHO (b) CH3CH2CHCHO
(c) (CH3)3CCHO (d) (CH3)2CH2CH2CHO
2.) Carboxylic acids are more acidic than phenol and alcohol because of
(a) Formation of dimers (b) Resonance stabilization of their conjugate base
(c) Highly acidic hydrogen (d) Intermolecular hydrogen bonding
3.) Aldehydes and ketones undergo __________ reactions.
a) electrophilic addition b) electrophilic substitution
c) nucleophilic addition d) nucleophilic substitution
4.) What is the correct order of reactivity of the following towards nucleophilic
addition?
a) Methanal > Ethanal > Acetone b) Acetone > Ethanal > Methanal
c) Methanal > Acetone > Ethanal d) Ethanal > Methanal > Acetone
5.) Identify the reagent for the conversion of but-2-ene to ethanal.
a) O3/H2O-Zn dust b) H2O, H2SO4, HgSO4
c) PCC d) DIBAL-H
6.) Which of the reactions below can result in ketones?
a) Oxidation of primary alcohols
b) Oxidation of secondary alcohols
c) Dehydrogenation of tertiary alcohols
d) Dehydrogenation of primary alcohols
7.) Which of the following orders of relative strengths of acids is correct?
(a) ClCH2COOH > FCH2COOH > BrCH2COOH
(b) ClCH2COOH > BrCH2COOH > FCH2COOH
(c) BrCH2COOH > ClCH2COOH > FCH2COOH
(d) FCH2COOH > ClCH2COOH > BrCH2COOH
8.) The reagent which does not react with both Propanone and
Benzaldehyde:
(a) Grignard reagent (b) Tollen’s reagent
(c) Zn-Hg amalgam (d)Fehling solution
9.) Which of the following compound will not give NaHCO3 test?
(a)Carbolic acid (b)Formic acid (c) Acetic acid (d) Benzoic acid
10.) In Clemmensen Reduction carbonyl compound is treated with __
(a) Zinc amalgam + HCl (b) Sodium amalgam + HCl
(c) Zinc amalgam + nitric acid (d) Sodium amalgam + HNO3
Question 1 2 3 4 5 6 7 8 9 10
Answer c b c a a b b d c a
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ASSERTION REASON TYPE QUESTIONS(1MARKS)
Note : In the following questions a statement of assertion followed by a statement of
reason is given. Choose the correct answer out of the following choices.
a) Assertion and reason both are correct statements and reason is correct
explanation for assertion.
b) Assertion and reason both are correct statements but reason is not correct
explanation for assertion.
c) Assertion is correct statement but reason is wrong statement.
d) Assertion is wrong statement but reason is correct statement.
11.) Assertion: Methanal, ethanal and propanone are miscible with water
in all proportions.
Reason: The lower members of aldehydes and ketones form hydrogen
bond with water.
12.) Assertion: Aldehydes are generally more reactive than ketones in
nucleophilic addition reactions.
Reason: Sterically, the presence of two relatively large substituents in
ketones hinder the approach of nucleophile to carbonyl
carbon than in aldehydes having only one such substituent.
13.) Assertion: Sodium hydrogen sulphite adds to aldehydes and
ketones to form the addition product.
Reason: Reaction of aldehydes with Sodium hydrogen sulphite is
useful for separation and purification of aldehydes.
14.) Assertion: Pka of acetic acid is lower than that of phenol
Reason: Phenoxide ion is more resonance stabilized than acetate ion.
15.) Assertion : α-hydrogen atoms of carbonyl compounds are acidic in nature.
Reason: The strong electron donating effect of the carbonyl group
and resonance destabilisation of the conjugate base makes
the alpha hydrogen acidic.
Question 11 12 13 14 15
Answer a a b d c
VERY SHORT ANSWER TYPE QUESTIONS (1 MARKS)
16) Write the structure of 3-oxopentanal.
Ans:
17) Give a chemical test to distinguish between Benzoic acid and Phenol.
Ans: Benzoic acid forms a brisk effervescence with NaHCO3 solution but
phenol does not respond to this test.
18) Formaldehyde does not undergo aldol condensation reaction. Why?
Ans: Formaldehyde does not contain α-hydrogen atom.
19) Aldehydes and Ketones have lower boiling points than corresponding alcohols.
Why?
Ans: Aldehydes and ketones have weak intermolecular interactions dipole –
dipole interactions whereas alcohols have intermolecular hydrogen bonding.
20) Arrange the following compounds in increasing order of their reactivity
in nucleophilic addition reactions:
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(i)Ethanal, Propanal, Propanone, Butanone.
(ii)Benzaldehyde, p-Tolualdehyde, p-Nitrobenzaldehyde, Acetophenone.
Ans: (i)Butanone<Propanone<Propanal<Ethanal
(ii)Acetophenone < p-Tolualdehyde < Benzaldehyde < p-nitro benzaldehyde
21) Write the structure of the product formed in the following reaction.
Ans:
22) Carboxylic acids do not give characteristic reactions of carbonyl group. Why?
Ans: The carboxylic carbon is less electrophilic due to resonance than
the carbonyl carbon.
23) Write the reagents required in the following reactions.
Ans:
(ii)
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(ii)
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therefore, nucleophilic attack by the CN– ion occurs readily and hence
cyclohexanone cyanohydrin is obtained in good yield.
(ii) Although semicarbazide has two – NH2 groups but one of them (i.e. which is
directly attached to C = O) is involved in resonance as shown above. As a result,
electron density on N of this -NH2 group decreases and hence it does not act as a
nucleophile. In contrast, the other -NH2 group (i.e. attached to NH) is not involved
in resonance and hence lone pair of electrons present on N atom of this -NH2
group is available for nucleophilic attack on the C = O group of aldehydes and
ketones.
(iii) The formation of esters from a carboxylic acid and an alcohol in presence of an
acid catalyst is a reversible reaction. Thus, to shift the equilibrium in the forward
direction, the water or the ester formed should be removed as fast as it is formed.
32. Identify the compounds A, B and C in the following reaction.
Ans:
33. Give simple chemical tests to distinguish between the following pairs of compounds.
(i) Propanal and Propanone (ii) Acetophenone and Benzophenone
(iii)Phenol and Benzoic acid
Ans: (i) Tollen’s test- Propanal on warming with ammoniacal silver nitrate
solution produces bright silver mirror. Propanone does not give this test.
(ii)Iodoform test-Acetophenone gives yellow ppt of iodoform on treating
with I2 and NaOH. Benzophenone does not give this test.
(iii)NaHCO3 test- Benzoic acid gives brisk effervescence when treated
with NaHCO3, Phenol does not give this test.
34. Write structures of compounds A, B and C in the following reactions:
Ans:
A-Ethanal, B- 3-hydroxybutanal, C-But-2-enal
35. Predict the products of the following reactions.
Ans:
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Long Answer Type Questions (5 marks each):
36. Describe the following :
(i) Aldol Condensation (ii)Cannizzaro Reaction
(iii)Clemmensen Reduction (iv)Rosenmund Reduction
(v) Hell Volhard Zelinsky Reaction.
Ans: (i) Aldol Condensation-Aldehydes having α-hydrogen react with a dilute
base to give β-hydroxy aldehydes called aldols.
(ii)Cannizzaro reaction:
Aldehydes which do not contain hydrogen when treated with a concentrated
solution of an alkali undergo self oxidation-reduction. As a result, one molecule of
aldehyde is reduced to corresponding alcohol while the other molecule is oxidized
to the corresponding acid.
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37. An aromatic compound ‘A’ (Molecular formula C8H8O) gives positive 2,4-DNP test. It
gives a yellow precipitate of compound ‘B’ on treatment with iodine and sodium
hydroxide solution. Compound ‘A’ does not give Tollen’s or Fehling’s test. On drastic
oxidation with potassium permanganate, it forms a carboxylic acid ‘C’ (Molecular
formula C7H6O2 ), which is also formed along with the yellow compound in the above
reaction. Identify A, B and C and write all the reactions involved.
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(ii) Ethanal with ammonia
B] A compound gives 2,4 DNP test, further it reduces Tollen’s reagent. what conclusions
can be drawn from this information?
Ans: As the compound gives 2,4-DNP test.it must be an aldehyde or ketone. Further as
it gives Tollen’s test it is an aldehyde.
C]What type of reaction takes place when aldehydes or ketones are treated with
ammonia and its derivatives?
Ans: Nucleophilic addition reaction.
39.) Read the following passage and answer the questions given below the
passage.
The addition reaction of enol or enolate to the carbonyl functional group of aldehyde or
ketone is known as aldol addition. The b-hydroxy aldehyde or b-hydroxyketone so
obtained undergo dehydration in second step to produce a conjugated enone. The first
part of reaction is an addition reaction and the second part is an elimination reaction.
Carbonyl compound having alpha-hydrogen undergoes aldol condensation reaction.
When an aldehyde with no alpha-hydrogen reacts with concentrated aqueous NaOH, half
the aldehyde is converted to carboxylic acid salt and other half is converted to an
alcohol. In other words, half of the reactant is oxidized and another half is reduced. This
reaction is known as Cannizzaro reaction.
A] How will you convert ethanol to But-2-enal?
Ans:
40.) Read the following passage and answer the questions given below the passage.
The carbonyl group of aldehydes and ketones is reduced to -CH2- group on treatment
with zinc amalgam and concentrated hydrochloric acid [Clemmensen reduction] or with
hydrazine followed by heating with sodium or potassium hydroxide in high boiling
solvent such as ethylene glycol (Wolf-Kishner reduction). Aldehydes differ from ketones
in their oxidation reactions. Aldehydes are easily oxidised to carboxylic acids on
treatment with common oxidising agents like nitric acid, potassium permanganate,
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potassium dichromate, etc. Even mild oxidising agents, mainly Tollens’ reagent and
Fehling’s reagent also oxidise aldehydes. Ketones are generally oxidised under vigorous
conditions, i.e., strong oxidising agents and at elevated temperatures. Their oxidation
involves carbon-carbon bond cleavage to afford a mixture of carboxylic acids having
lesser number of carbon atoms than the parent ketone.
A] Write a chemical equation to convert Propanone to propane. Mention the name of the
reaction.
41.) Read the following passage and answer the questions given below the passage.
Aldehydes and ketones are the simplest and most important carbonyl compounds. In
aldehydes, the carbonyl group is bonded to a carbon and hydrogen while in the ketones,
it is bonded to two carbon atoms. The IUPAC names of open chain aliphatic aldehydes
and ketones are derived from the names of the corresponding alkanes by replacing the
ending –e with –al and –one respectively. In case of aldehydes the longest carbon chain is
numbered starting from the carbon of the aldehyde group while in case of ketones the
numbering begins from the end nearer to the carbonyl group. The substituents are
prefixed in alphabetical order along with numerals indicating their positions in the
carbon chain. The same applies to cyclic ketones, where the carbonyl carbon is
numbered one. When the aldehyde group is attached to a ring, the suffix carbaldehyde is
added after the full name of the cycloalkane. The numbering of the ring carbon atoms
starts from the carbon atom attached to the aldehyde group. The name of the simplest
aromatic aldehyde carrying the aldehyde group on a benzene ring is benzene
carbaldehyde. However, the common name benzaldehyde is also accepted by IUPAC.
Other aromatic aldehydes are hence named as substituted benzaldehydes.
A] Write the structures of 4-Fluoroacetophenone & 2-Hydroxybutanal.
Ans:i) ii)
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Ans: 2- methylcyclopentane carbaldehyde
42.) Read the following passage and answer the questions given below the passage.
Effect of substituents on the acidity of carboxylic acids: Substituents may affect the
stability of the conjugate base and thus, also affect the acidity of the carboxylic acids.
Electron withdrawing groups increase the acidity of carboxylic acids by stabilising the
conjugate base through delocalisation of the negative charge by inductive and/or
resonance effects. Conversely, electron donating groups decrease the acidity by
destabilising the conjugate base.
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9. AMINES
Quick Revision Points:
Amines are alkyl / aryl derivatives of ammonia. In amines nitrogen atom is sp3
hybridised and contains one lone pair.
Primary amine (10) Secondary amine (20) Tertiary amine (30)
One- H atom is replaced by Two-H atom is replaced Three-H atom is
R/Ar. by R/Ar. replaced by R/Ar.
IUPAC Name: -
Aliphatic amine:
Alkanamines
Aromatic amine:
Benzenamine/Aniline
CH3-NH2 CH3-NH- CH3 (CH3)3N
Methanamine N-Methylmethanamine N, N-
CH3-CH- CH3 dimethylmethanamine
NH2
Propan-2-amine
CH3-NH- CH2- CH3
N-Methylethanamine
CH3 - CH2-NH- CH2- CH3
N-Ethylethanamine
N, N-
Aniline/benzenamine
Dimethylbenzenamine
Preparation of Amines:
Reduction of Nitro Compounds gives aliphatic
and aromatic primary amines. (Reducing
Agents): -
• Hydrogen and nickel/ palladium or
platinum.
• Iron scrap and hydrochloric acid (Fe + HCl).
• Tin and hydrochloric acid (Sn + HCl).
Ammonolysis of alkyl halides: - NH3 RX RX RX
RX → RNH2 → R 2 NH → R 3 N → R 4 N+ X −
Reagent: Ethanolic solution of ammonia. −HX
Disadvantage: Mixture of amines formed.
Reduction of nitriles Reducing agents: - H2 /Ni or Na(Hg)/C2 H5 OH
R − CN →⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯ R − CH2 NH2
LiAlH4/Catalytic hydrogenation.
Reduction of Amides: CH3 CONH2
LiAll4
→ CH3 CH2 NH2
H2 O
Hoffmann bromamide degradation Reaction: An amide is heated with Bromine in
aq. solution of NaOH/KOH gives primary amine.
R − CONH2 + Br2 + 4NaOH → R − NH2 + Na2 CO3 + 2NaBr + 2H2 O
The amine formed contains one carbon less than that present in the amide.
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Gabriel Phthalimide Synthesis: Only aliphatic
primary amines are prepared by this method.
Aromatic primary amines cannot be prepared
because aryl halides do not undergo
nucleophilic substitution with the anion
formed by phthalimide.
• Aliphatic amines are stronger base than ammonia due to +I effect of alkyl groups.
• Aromatic amines are weaker bases than ammonia due to the electron withdrawing
nature of the aryl group.
Acetylation: (replacement of H-atom of (C2H5)2NH + CH3COCl → CH3CON(C2H5)2 +
–NH2 />N–H group by the acyl group). HCl
Reacting agent: stronger base.
Benzoylation: (replacement of H-atom
of –NH2 />N–H group by the benzoyl CH3NH2 + C6H5COCl →C6H5 CONH-CH3 + HCl
group).
Carbylamine reaction (Isocyanide HEAT
RNH2 + CHCl3 + 3KOH →⎯⎯ RNC + 3KCl + 3H2 O
Test) Secondary and tertiary amines do not show
Primary amines react with chloroform this reaction.
and KOH give isocyanides It is used as a test for primary amines.
(Carbylamine) which has unpleasant
smell (foul smell).
Reaction with nitrous acid (HNO2) NaNO2 +HCl H2 O
RNH2 +HNO2 →⎯⎯⎯⎯⎯⎯⎯ [RN2+ Cl− ] →⎯ ROH + N2 + HCl
Primary aliphatic amines react with
nitrous acid to form aliphatic
diazonium salts (unstable) which 278K
liberate nitrogen gas and alcohols. C 6 H 5 NH 2 + HNO 2 →⎯⎯ C6 H5 N2+ Cl− + NaCl + 2H2 O
Aromatic amines at low temperatures
(273-278 K) forms diazonium salts.
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Reaction with Benzenesulphonyl chloride (Hinsberg's test)(C6H5SO2Cl)
Primary Amine Secondary Amine Tertiary Amine
Primary amines form Secondary amines form Tertiary amines do
N-alkylbenzene sulphonamide N, N- not react with
which is soluble in alkali due dialkylbenzenesulphonamide Hinsberg’s reagent.
to presence of acidic hydrogen which is not soluble in alkali
at N-atom. due to absence of hydrogen
atom at N-atom.
Electrophilic substitution:
–NH2 group is ortho and para directing and a powerful activating group.
In direct Nitration meta product is formed due to formation of anilinium ion which is
meta directing.
Electrophilic substitution:
Aniline is converted into acetanilide by acetylation with acetic anhydride and then the
desired substitution is carried out followed by hydrolysis the lone pair on nitrogen is
less available for donation to benzene ring by resonance. Therefore, activating effect of -
NHCOCH3 group is less than that of amino group.
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Benzene Diazonium Chloride Preparation and Reactions:
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Q: 7 The -NH2 group is o-, p- directing and strongly activates the aromatic ring.
Therefore, aromatic amines undergo electrophilic substitution reactions
readily and it is difficult to stop the reaction at the monosubstitution stage.
However, sometimes monosubstitution product is required. How can the
activating effect of -NH2 group be controlled to get monosubstitution product?
(a) Protecting -NH2 group by chlorination with chlorine
(b) Protecting -NH2 group by nitration with nitric acid
(c) Protecting -NH2 group by alkylation with alkyl chloride
(d) Protecting -NH2 group by acetylation with acetic anhydride
Q: 8 A and B in the folowing reactions are:
Question 1 2 3 4 5
Answer c a b d a
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VERY SHORT ANSWER TYPE QUESTIONS (2 MARKS)
Q: 16 Give the IUPAC name of (i) H2N – CH2 – CH2 – CH = CH2
(ii) CH3—NH—CH2CH3.
Answer: (i) But-3-en-1-amine (ii) N-methylethanamine
Q: 17 Which of the following are tertiary amines
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(ii) C6 H5 N2+ X − + CuCl/HCl → C6 H5 Cl + N2
Q: 24 How will you bring about the following conversions?
(a) Ethanamine into methanamine (b) Aniline into 4-bromoaniline
Answer:
HNO2 CrO3 ,H2 SO4 NH3,∆ Br2, KOH
(i) CH3 CH2 NH2 →⎯⎯ CH3 CH2 OH →⎯⎯⎯⎯⎯⎯⎯ CH3 COOH →⎯⎯ CH3 CONH2 →⎯⎯⎯⎯ CH3 NH2
(ii)
Q: 27 Mr. Krishna, a chemistry teacher gave his class students a sample of an amine
“P” having molecular formula C4H11N to test, identify and write the reaction. The
students observed that it reacts with Hinsberg’s reagent to form an alkali soluble
product. A student Ranu wrote the reaction as follows.
Identify the mistakes committed by Ranu. Write the type of amine in sample “P” and
correct chemical equation.
Answer: The formula of Hinsberg’s reagent and sample of P were written by Ranu are
incorrect. The Sample “P” belongs to primary amine. Therefore, sample “P” is
Butanamine. The correct chemical equation is as follows:
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Q: 28 Account for the following:
(i) Aniline does not undergo Friedel-Crafts reaction.
(ii) Diazonium salts of aromatic amines are more stable than those of aliphatic
amines
(iii) pKb of methylamine is less than that of aniline.
Answer: (i) Aniline being a Lewis base, reacts with Lewis acid AlCl3 to form a salt.
Due to this N atom of aniline acquires positive charge and hence acts as a strong
deactivating group for further reaction.
(ii) 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.
(iii) In aniline due to resonance the lone pair of electrons on the nitrogen atom are
delocalized over the benzene ring. As a result, the electron density on the nitrogen
decreases. On the other hand, in methyl amine +I effect of CH3 increases the electron
density on the nitrogen atom. Therefore, aniline is a weaker base than methyl amine
and hence its pKb value is higher than that of methyl amine
Q: 29 Arrange the following:
(i) CH3NH2, (CH3)2NH, NH3, (CH3)3N [in decreasing order of basic strength in gaseous phase]
(ii) C2H5NH2, C6H5NH2, NH3, C6H5CH2NH2 and (C2H5)2NH [in increasing order of
basic strength]
(iii) C6H5NH2, C6H5N(CH3)2, (C2H5)2NH and CH3NH2 [in increasing order of basic
strength]
Answer: (i) (CH3)3N > (CH3)2NH >CH3NH2 > NH3
(ii) C6H5NH2 < NH3 < C6H5CH2NH2 < C2H5NH2 < (C2H5)2NH
(iii) C6H5NH2 < C6H5N(CH3)2 < CH3NH2 < (C2H5)2NH
Q: 30 Complete the following reactions:
(i) CH3CONH2 + Br2 + NaOH→………. + Na2CO3 + H2O
𝑃𝑑
(ii) ………. + H2 →⎯⎯ CH3-CH2-NH2
(i)LiAlH4 (ii)H2 O
(iii) CH3CONH2 →⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯
Answer:
(i) CH3CONH2 + Br2 + 4NaOH → CH3NH2. + Na2CO3 + 2H2O + 2NaBr
𝑃𝑑
(ii) CH3-CH2-NO2 + H2 →⎯⎯ CH3-CH2-NH2
(i)LiAlH4 (ii)H2 O
(iii) CH3CONH2 →⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯ CH3CH2NH2
LONG ANSWER TYPE QUESTIONS (5 MARKS
Q: 31 in the following reaction chart identify A, B, C, D and E. Write their IUPAC
name and rewrite the following reaction
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Q: 32 (i) An amine “X” with formula C3H9N reacts with benzenesulphonyl chloride to
give a precipitate which is insoluble in alkali. Give the structure and IUPAC name of
amine “X”. Write the chemical reaction
(ii) How will bring out the following conversions: (A) Aniline to Phenol (B) Aniline to
Iodobenzene.
Answer: (i) N methyl ethanamine (C2H5 NH CH3)
273−278K
(ii) (a) C6 H5 − NH2 + HNO2 →⎯⎯⎯⎯⎯⎯ C6 H5 − N2+ Cl− + NaCl + 2H2 O
∆
C6 H5 N2+ Cl− + H2 O → C6 H5 OH + N2 + HCl
273−278K
(b) C6 H5 − NH2 + HNO2 →⎯⎯⎯⎯⎯⎯ C6 H5 − N2+ Cl− + NaCl + 2H2 O
C6 H5 N2+ Cl− + KI → C6 H5 I + N2 + KCl
CASE BASED QUESTIONS
Q 33.Amines are organic bases having the general formula RR’2N, where R is a
hydrocarbon group, ‘R’ may be H or a hydrocarbon group. As with ammonia, the
reaction of amines with water is
RNH2 + H2O →RNH3+ +OH- .
Like all bases, amines form salts when allowed to react with acids.
CH3NH2 + HCl → CH3N+H3Cl
These salts are usually colourless, odourless solids.
Aromatic amines are used mainly in the manufacture of dyes.
Aniline, the simplest aromatic amine itself is a toxic compound; a number of other
aromatic amines such as 2-naphthylamine and benzidine are potent carcinogens.
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(ii)
(iii)
OR
(a)Aniline being basic, reacts with acid to form anilinium ion, which is meta
directing.
(b) The lone pair of electrons on N in aniline are not readily available due to
delocalization with the benzene ring.
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10. BIOMOLECULES
Quick Revision Points
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10- str. of proteins: sequence of amino acids that is said to be the primary structure
of protein
20- str. of proteins: secondary structure of protein refers to the shape in which a
long polypeptide chain can exist.
They are found to exist in two types of structures viz. α -helix
and β -pleated sheet structure.
Tertiary structure further folding of the secondary structure. It gives rise to two
of proteins: major molecular shapes viz. fibrous and globular.
Fibrous proteins Polypeptide chains run parallel, held together by hydrogen and
disulphide bonds, fibre– like structure. Water insoluble. Eg-
are keratin(in hair, wool, silk) and myosin (present in muscles).
Globular proteins chains of polypeptides coil around to give a spherical shape.
water soluble. Eg-Insulin and albumins
Stab. Forces 2°& 3° hydrogen bonds, disulphide linkages, van der Waals and
electrostatic forces of attraction.
Denaturation of When a protein is subjected to physical change like change in
Proteins temperature or chemical change like change in pH, the hydrogen
bonds are disturbed. Due to this, globules unfold and helix get
uncoiled and protein loses its biological activity. This is called
denaturation of protein.
(During denaturation 2° and 3° structures are destroyed but 1º
structure remains intact.)
eg- The coagulation of egg white on boiling, curdling of milk
Enzymes Enzymes are essential biological catalysts which are required to
catalyse biological reactions, e.g., maltase, lactase, invertase,
etc. Almost all the enzymes are globular proteins
Fat soluble vit These are vitamins A, D, E and K. They are stored in liver and
adipose
(fat storing) tissues
Water soluble vit B, C. these vitamins must be supplied regularly in diet because
they are readily excreted in urine
Vitamins –sources- Vit- A (Fish liver oil, carrots)- Night blindness/Vitamin B1 (Yeast,
Deficiency diseases milk,)- Beri beri
Vit-B2 (Milk, egg white)- Cheilosis/Vit- B6 (Yeast, milk,)-
Convulsions /
Vit- B12 (Meat, fish,)- Pernicious anaemia
Vit C(Citrus fruits)- Scurvy, /Vit D(Exposure to sunlight, fish
and egg yolk)- Rickets, osteomalacia
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Phosphodiester link Linkage between two nucleotides in polynucleotides
ANSWERS
1. A 2. D 3. B 4. D 5. C 6. C 7. B 8. D 9. A 10.A
ASSERTION REASON TYPE QUESTIONS(1MARKS)
1. Two statements are given below- one labelled Assertion (A) and the other
labelled Reason (R).
ASSERTION – Vitamin C can’t be stored in our body.
REASON – Vitamin C is water soluble and is excreted from the body through
urine.
(a) A and R both statements are correct and R is the correct explanation of A.
(b) A and R both statements are correct and R is not the correct explanation of A.
(c) A is correct statement but R is not the correct statement.
(d) A is incorrect statement but R is the correct statement.
2. Two statements are given below- one labelled Assertion (A) and the other
labelled Reason (R).
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ASSERTION – Proteins are polymers of alpha amino acids connected by peptide
bonds.
REASON – A tripeptide contains 3 amino acids linked by 3 peptide bonds.
(a) A and R both statements are correct and R is the correct explanation of A.
(b) A and R both statements are correct and R is not the correct explanation of A.
(c) A is correct statement but R is not the correct statement.
(d) A is incorrect statement but R is the correct statement.
3. Two statements are given below- one labelled Assertion (A) and the other
labelled Reason (R).
ASSERTION – Change in pH and heating leads to denaturation of proteins.
REASON – Change in pH and heating cause loss of biological activity of proteins.
(a) A and R both statements are correct and R is the correct explanation of A.
(b) A and R both statements are correct and R is not the correct explanation of A.
(c) A is correct statement but R is not the correct statement.
(d) A is incorrect statement but R is the correct statement.
4. Two statements are given below- one labelled Assertion (A) and the other
labelled Reason (R).
ASSERTION – Adenine and Guanine are the purines present in both nucleic acids.
REASON – Thiamine and Uracil are the pyrimidine present in DNA.
(a) A and R both statements are correct and R is the correct explanation of A.
(b) A and R both statements are correct and R is not the correct explanation of A.
(c) A is correct statement but R is not the correct statement.
(d) A is incorrect statement but R is the correct statement.
5. Two statements are given below- one labelled Assertion (A) and the other
labelled Reason (R).
ASSERTION – Amylopectin is water soluble and contributes 15-20% of starch.
REASON – Amylopectin has C1-C4 & C1-C6 glycosidic linkages.
(a) A and R both statements are correct and R is the correct explanation of A.
(b) A and R both statements are correct and R is not the correct explanation of A.
(c) A is correct statement but R is not the correct statement.
(d) A is incorrect statement but R is the correct statement.
ANSWERS
1.A 2.B 3.A 4.C 5.D
VERY SHORT ANSWER QUESTIONS (1M)
1. What is the basic structural difference between glucose and fructose?
A. Glucose has aldehyde group whereas fructose has keto group.
2. Name the carbohydrate used as storage molecule to store energy in animals?
A. Glycogen
3. Name the vitamin whose deficiency cause pernicious anemia?
A. Vit B12
4. Write down the vitamin which is responsible for the coagulation of blood?
A. Vit K
5. Give one example each for Fibrous protein and Globular protein.
A. Fibrous protein – Keratin, Globular protein – Insulin
6. What type of linkage is responsible for the formation of proteins?
A. Peptide linkage.
7. Name the unit formed by the attachment of a base to 11 positions of sugar.
A. Nucleoside
8. Write the products obtained after hydrolysis of DNA.
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A. Pentose sugar, phosphoric acid and Nitrogen containing heterocyclic compounds
as bases.
9. Name the base that is found in nucleotide of RNA only ?
A. Uracil
10. Name
a) A major sex hormone produced in males b) The main female sex hormone
A. a) Testosterone
b) Estradiol
SHORT ANSWER QUESTIONS TYPE – 1 ( 2M)
1. What is the difference between nucleotide and nucleoside?
A. Nucleoside contains ribose or deoxyribose sugar and heterocyclic base. Nucleotide
contains phosphoric acid residue along with heterocyclic base and pentose sugar.
2. Name a water-soluble vitamin which is a powerful antioxidant? Give one of its
sources.
A. Vit C, citrus fruits like orange, lemon etc.
3. Write 2 differences between RNA and DNA.
A. RNA – a) It has ribose sugar with adenine, uracil, cytosine, guanine as heterocyclic
bases.
b) It is single helix.
DNA – a) It has deoxyribose sugar along with adenine, thiamine, cytosine, guanine as
heterocyclic bases.
b) It is double helix.
4. What are the two types of secondary structure of proteins? How will you
differentiate between them?
A. Alpha – helix and Beta pleated helix structure.
Those polypeptide chains stabilized by intramolecular hydrogen bonds are alpha helix
structure.
Beta pleated structure of proteins are stablilised by intermolecular hydrogen bonding.
5. What are polysaccharides? Give two examples.
A. Those carbohydrates which on hydrolysis give large number of monosaccharides. Eg:-
Starch, Cellulose.
SHORT ANSWER QUESTION TYPE – 2 ( 3M)
1. Differentiate between
a) Amylose and Amylopectin
b) Peptide linkage and Glycosidic linkage
c) Fibrous proteins and Globular proteins.
A. a) Amylose is a branched chain polymer of alpha glucose, water soluble. Amylopectin
is a branched chain polymer of alpha glucose, water insoluble.
b) The bond CONH between two or more amino acids in polypeptides and proteins
is called peptide linkage. The oxide linkage between two or more monosaccharide
units in oligosaccharides and polysaccharides is called glycosidic linkage.
c) Fibrous proteins - Thread like structures, insoluble in water. Eg – Keratin,
Myosin
Globular proteins – Chains of polypeptides coil around spherical shape, soluble in
water. Eg – Insulin, Albumin.
2. Define the following with a suitable example.
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a) Oligosaccharides
b) Denaturation of proteins
c) Vitamins
A. a) Gives two to ten units of monosaccharides on hydrolysis.
Eg – Lactose, Raffinose
b) On heating or change in pH hydrogen bonds are disturbed, globules unfold and
helix get uncoiled and leads to loss of biological activity. Eg – Coagulation of egg white,
milk converted to curd.
c) Group of organic compounds which are required in very small amounts for healthy
growth and functioning of organism. They cannot be made by organism and so have to
be part of our diet. The deficiency of a Vitamin can cause a specific disease. Eg – Fat
soluble vitamins – A, D, E, K
Water soluble vitamins – B ( except B12), C
3. What are essential and non – essential amino acids? Give two examples of each.
A. Amino acids which cannot be synthesized in the body and must be obtained through
diet are known as essential amino acids. Eg – Valine, Leucine
Amino acids which can be synthesized in the body are known as non-essential amino
acids. Eg – Alanine, Glutamic acid.
4. Write chemical reactions to show that open structure of D-glucose contains the
following
a) Straight chain
b) 5 alcohol groups
c) Aldehyde as carbonyl group
A. a) Glucose when reacted with Red P and HI gives n-hexane. It indicates the presence
of straight chain of 6 carbon atoms in glucose.
c) Glucose on oxidation with a mild oxidizing agent like bromine water gives gluconic
acid containing the same 6 carbon atoms as present in glucose.
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5. a) Why Vit C cannot be stored in our body?
b) Write the name of Vitamin whose deficiency causes bone deformities in
children.
c) Deficiency of which Vitamin cause night blindness.
A. a) Vit C is soluble in water and regularly excreted in urine and hence cannot be stored
in body.
b) Vit D
c) Vit A
LONG ANSWER QUESTIONS (5M)
1. Give reasons for the following observations.
a) Amino acids behave like salts rather than simple amines or carboxylic acids.
b) Amino acids show amphoteric behavior.
c) The two strands of DNA are complementary to each other.
d) Pentaacetate of glucose does not react with hydroxyl amine.
e) Starch and cellulose both contain glucose units as monomers yet they are
structurally different.
A. a) Due to the presence of both acidic (carboxyl group ) and basic ( amino group)
groups in the same molecule.
b) They exist as Zwitter ions in R – CH-COO-
NH3+
In Zwitter ionic form amino acids show amphoteric behaviour as they react both with
acids and bases.
c) Since there is specific hydrogen bonding between heterocyclic bases, A can form
hydrogen bond with T, C can form hydrogen bond with G and vice versa.
d) As glucose forms a six membered ring in which – CHO group combines with – OH
group at C5, pentaacetate of glucose does not react with hydroxyl amine due to absence
of free – CHO group.
e) The basic structural difference between starch as cellulose is of linkage between the
glucose units. In starch there is - D – glycosidic linkage. Both the components of
starch, amylose and amylopectin are polymers of - D – glycose. On the other hand,
cellulose is a linear polymer of β – D- glucose in which C1 of one glucose unit is
connected to C4 of the other through β – D- glycosidic linkage.
2. a) Which sugar is called invert sugar? Why is it called so?
b) How can reducing and non-reducing sugars be distinguished?
Mention the structural feature characterizing reducing sugars
A. a) Mixture of glucose and fructose is called invert sugar. It is called invert sugar
because dextro-rotatory sucrose gives mixture of glucose and fructose on
hydrolysis which is laevo-rotatory. Therefore, it is called invert sugar.
b) Those carbohydrates which reduce Tollens’ reagent to give silver mirror or form
brick red precipitate with Fehling’s solution are called reducing sugars whereas
those which do not are non-reducing sugars.
All monosaccharides are re
ducing sugars due to the presence of aldehyde group or -keto group. Those
disaccharides like sucrose are not reducing sugar because aldehydic and ketonic
groups not free. All polysaccharides are non-reducing.
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Case Based Questions
1. Read the paragraph carefully and give the answers of the questions followed.
Glucose, Galactose, and fructose have the same chemical formula but they differ in the
organization of their atoms. The sugars we have looked at so far are linear molecules
(straight chains). That may seem odd because sugars are often drawn as rings. As it
turns out both are correct: many five- and six-carbon sugars can exist either as a linear
chain or in one or more ring-shaped forms. Cyclic sugars show mutarotation. The optical
rotation of the solution depends on the optical rotation of each anomers and their ratio
in the solution. Mutarotation was discovered by French chemist Augustin-Pierre
Dubrunfaut in 1844, when he noticed that the specific rotation of aqueous sugar
solution changes with time. These forms exist in equilibrium with each other, but
equilibrium strongly favours the ring forms (particularly in aqueous, or water-based,
solution). For instance, in solution, glucose’s main configuration is a six-membered ring.
Over 99% of glucose is typically found in this form.
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2. Read the paragraph carefully and give the answers of the questions
followed.
Proteins are the polymers of α -amino acids and they are
connected to each other by peptide bond or peptide
linkage. Chemically, peptide linkage is an amide formed
between–COOH group and –NH2 group. The reaction
between two molecules of similar or different amino acids
proceeds through the combination of the amino group of
one molecule with the carboxyl group of the other. This
results in the elimination of a water molecule and
formation of a peptide bond –CO–NH–. The product of the
reaction is called a dipeptide because it is made up of
two amino acids. For example, when carboxyl group of
glycine combines with the amino group of alanine we get
a dipeptide, glycylalanine. Structure and shape of proteins can be studied at four
different levels, i.e., primary, secondary, tertiary and quaternary, each level being
more complex than the previous one.
The final shape adopted by a newly synthesized protein is typically the most
energetically favourable one. As proteins fold, they test a variety of conformations
before reaching their final form, which is unique and compact. Folded proteins are
stabilized by thousands of noncovalent bonds between amino acids. In addition,
chemical forces between a protein and its immediate environment contribute to
protein shape and stability. For example, the proteins that are dissolved in the cell
cytoplasm have hydrophilic (water-loving) chemical groups on their surfaces,
whereas their hydrophobic (water-averse) elements tend to be tucked inside. In
contrast, the proteins that are inserted into the cell membranes display some
hydrophobic chemical groups on their surface, specifically in those regions where
the protein surface is exposed to membrane lipids. It is important to note,
however, that fully folded proteins are not frozen into shape. Rather, the atoms
within these proteins remain capable of making small movements.
Answer the following questions:
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Answer
(a) The forces which are responsible for tertiary structure of proteins are hydrogen
bonds, disulphide linkage, Vander walls and electrostatic forces of attraction.
(b) On boiling the water-soluble globular proteins unfold and helix get uncoiled.
During this change intermolecular hydrogen bond get disturbed. The water
molecule gets attached to the uncoiled proteins molecule through hydrogen bond.
(c) α-Helix structure: The polypeptide chains are held together (stabilized) by
Intramolecular H-bonding. β-Pleated sheet structure: The two neighbouring
polypeptide chains are held together by intermolecular H-bonding.
OR
(c) Proteins found in a biological system with unique 3D-structure and biological
activity is called native protein. When native protein is subjected to physical
and chemical change, protein loses its biological activity and is called
denatured protein.
3. Read the paragraph carefully and give answers of the questions followed.
Information regarding the sequence of nucleotides in the chain of a nucleic
acid is called its primary structure. Nucleic acids have a secondary structure also.
James Watson and Francis Crick gave a double strand helix structure for DNA.
Two nucleic acid chains are wound about each other and held together by
hydrogen bonds between pairs of bases. The two strands are complementary to
each other because the hydrogen bonds are formed between specific pairs of
bases. Adenine forms hydrogen bonds with thymine whereas cytosine forms
hydrogen bonds with guanine. In secondary structure of RNA single stranded helix
is present which sometimes folds back on itself. RNA molecules are of three types
and they perform different functions. DNA is the chemical basis of heredity and
may be regarded as the reserve of genetic information. DNA is exclusively
responsible for maintaining the identity of different species of organisms over
millions of years. A DNA molecule is capable of self-duplication during cell division
and identical DNA strands are transferred to daughter cells.
Answer the following questions:
(a) Name the segment of DNA which acts as the instrumental manual for the
synthesis of proteins.
(b) Name the chemical change in DNA that leads to the synthesis of proteins
with different amino acids.
(c) (i) Write the sequence of chemicals present in nucleic acids.
(ii) What are the different types of RNA found in the cell?
OR
(c) Write the main functional differences between DNA and RNA.
Of the four bases name those which are common to both DNA and RNA.
Answer
3. (a) Gene
(b) Mutation
(c) (i)Phosphate- sugar-base
(ii) m-RNA, t-RNA, r-RNA
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OR
(c) DNA is the chemical basis of heredity and RNA molecules are responsible for
protein synthesis. Common bases in DNA and RNA Adenine, Guanine and
Cytosine.
4. Read the paragraph carefully and give answers of the questions followed
An average Indian derives 61 to 64% of energy from consumption of food rich in
carbohydrates. A study published in the journal diabetes care has recommended
reducing this to 49 to 56% for remission or prevention of type-2 diabetes one of
the leading causes of death worldwide. Along with reducing carbohydrates intake
the study suggests that one should also increase protein intake. (14-20%) of the
total energy consumption. Fats should contribute not more than 21 to 27% of the
total energy consumption. In simple words 50% of plate should consist of fruits
and green vegetables, 25% carbohydrates of choice, 25% contain food rich in
protein. Physically inactive, obese and older individuals as well as presiding in
urban locations may require greater reduction in carbohydrate intake. The keto
diet, very low-calorie diet is best.
Answer the following questions:
5. Read the paragraph carefully and give answers of the questions followed
Vitamins are vital for life. A, D, E, K are fat soluble vitamins whereas B1, B2, B3,
B5, B6, B7, B9, C are water soluble vitamins. Vitamin A helps in improving eye
sight. Vitamin C prevents scurvy and increases immunity. Vitamin D helps in
strong bones and teeth. Our requirement of vitamin D is 15mcg. We get vitamin D
from sunlight, eggs, dairy products, orange, oats and mushroom etc. Citrus fruits
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contain vitamin C. Carrot contains vitamin A. We should include chick pea flour in
our diet to prevent inflammation. It has phytonutrients and fibres which have
anti-inflammatory properties. It prevents accumulation of fats. It contains Fe, Cu,
Mg, fibre, K which are essential to control our wait. It increases our immune
system. It contains proteins, amino acids, Mg, vitamin B and P. Pomegranates are
good source of vitamin C which our body needs to make collagen. It is rich source
of B-complex, vitamin B5 folates pyridoxine and vitamin K. It contains essential
minerals like Ca, Cu, Mg and Mn. Pomegranates are rich source of insoluble fibres
which help us keep fuller for longer time and regulate bowel function.
Answer the following questions:
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