Hsslive-Xii-Chemistry-Vijayabheri-2024 2021
Hsslive-Xii-Chemistry-Vijayabheri-2024 2021
Hsslive-Xii-Chemistry-Vijayabheri-2024 2021
SOLUTIONS
(Key points:Henry’s law-applications,Raoult’s law-
ideal&non ideal solution,azeotropic mixture,colligative
properties)
P= PA+PB
(ii). ∆H mix = 0
(iii). ∆V mix = 0
(ii). ∆H mix = 0
(iii). ∆V mix = 0
Non ideal solution showing Positive Non ideal solution showing Negative
deviation deviation
Shown by liquid pairs for which A-B Shown by liquid pairs for which A-B
interactions are weaker than A-A and B- interactions are stronger than A-A and
B interactions. B-B interactions.
Colligative properties
Examples;-
1. Relative lowering of Vapour pressure,
2. Elevation of Boiling point,
3. Depression of Freezing point
4. Osmotic Pressure.
Note:
(i).Osmotic pressure is used to measure molecular mass of
proteins, polymers and other macromolecules because of two
reasons :
(a) Osmotic pressure is measured at room temperature.
(b) Molarity is used instead of molality,
(ii) Anti freeze solutions(Glycol) are used in automobile
radiators to prevent the freezing of water(depression of
freezing point).
(iii) NaCl and CaCl2 is used to remove ice from road because
it depress the freezing point of water.
(iv). The osmotic pressure of fluid inside the blood cell and
that of 0.9% (mass/volume) NaCl solution are equal. ie. They
are isotonic (solution having same osmotic pressure).
Therefore, 0.9% (mass/volume) NaCl solution is used in
intravenous injections
Reverse osmosis :
Model question:
Effect of dilution on conductivity and molar conductivity:For both strong and weak
electrolytes, conductivity(κ) decreases with increase in dilution because as dilution increases,
the number of ions per unit volume decreases.For both strong and weak electrolytes,the molar
conductivity(λ) increases with dilution.For strong electrolytes,as dilution increases,the force
of attraction between ions decreases and hence the ionic mobility increases.For weak
electrolytes as dilution increases,degree of dissociation increases.
λm = λ0m + AC1/2
Kohlrausch's law of independent migration of ions: The law states that the limiting molar
conductivity of an electrolyte can be represented as the sum of the individual contributions of
the anion and the cation of the electrolyte. Thus if an electrolyte on dissociation gives n (+)
cations and n (-) anions, its limiting molar conductivity is given as:
λ0m = n(-)λ0(-) + n(+)λ0(+)
Applications of Kohlrausch's law: 1) Determination of λ0m of weak electrolytes: By
knowing the λ0m values of strong electrolytes, we can calculate λ0m of weak electrolytes. For
e.g. we can determine the λ0m of acetic acid (CH3COOH) by knowing the λ0m of
CH3COONa, NaCl and HCI.
λ0m(CH3COOH) = λ0m(CH3COONa) + λ0m(HCl) - λ0m(NaCl)
Faraday's first law: It states that the amount of substance deposited or liberated at the
electrodes (m) is directly proportional to the quantity of electricity (Q) flowing through the
electrolyte m = z Q Where z is a constant called electrochemical equivalent , z = equivalent
weight/96500. But quantity of electricity is the product of current in ampere (I) and time in
second (t). Q = It; Therefore, m= zlt. 1 Faraday is the charge of 1 mole of electron and its value
is 96500 C/mol.
Faraday's second law: It states that when same quantity of electricity is passed through
solutions of different substances, the amount of substance deposited or liberated is directly
proportional to their chemical equivalence . For e.g. when same quantity of electricity is
passed through solutions of two substances A and B,then
𝑀𝑎𝑠𝑠 𝑜𝑓 𝐴 𝑑𝑒𝑝𝑜𝑠𝑖𝑡𝑒𝑑 𝐸𝑞𝑢𝑖𝑣𝑎𝑙𝑒𝑛𝑡 𝑚𝑎𝑠𝑠 𝑜𝑓 𝐴
=
𝑀𝑎𝑠𝑠 𝑜𝑓 𝐵 𝑑𝑒𝑝𝑜𝑠𝑖𝑡𝑒𝑑 𝐸𝑞𝑢𝑖𝑣𝑎𝑙𝑒𝑛𝑡 𝑚𝑎𝑠𝑠 𝑜𝑓 𝐵
Types of Galvanic Cells:. They are of mainly 2 types - primary cells and secondary cells.
1)Primary cells: These are cells which cannot be recharged or reused. Here the reaction
occurs only once and after use over a period of time, they become dead E.g. Dry cell,
mercury button cell etc.
1. Dry Cell. It is a compact form of Leclanche cell. It consists of a zinc container as anode
and a carbon (graphite) rod surrounded by powdered manganese dioxide (MnO₂) and carbon
as cathode. Electrolyte is a moist paste of ammonium chloride (NH,CI) and zinc chloride
(ZnCl₂). Cell potential is 1.5V .Cell potential is not constant because electrolyte is used
during reaction.
Anode : Zn Zn2+ + 2e
Cathode : MnO2 + NH4+ + e MnO(OH) + NH3
2. Mercury cell: Here the anode is zinc - mercury amalgam and cathode is a paste of HgO
and carbon. The electrolyte is a paste of KOH and ZnO.Overall reaction is
Zn(Hg) + HgO ZnO(s) + Hg(l)
The cell has a constant cell potential of 1.35V since the overall reaction does not involve any
ion in solution.
2)Secondary cells: A secondary cell can be recharged and reused again. Here the cell reaction
can be reversed by passing current through it in the opposite direction. Eg. Lead storage
battery ,Ni-Cd cell etc
Lead storage battery is used in automobiles and invertors. It consists of lead as anode and a
grid of lead packed with lead dioxide (PbO₂) as the cathode. The electrolyte is 38% H₂SO4
solution.The cell reactions are:
Anode: Pb(s) + SO42- (aq) PbSO4(s) + 2e-
Cathode: PbO2 (s) + SO42- (aq) + 4H+(aq) + 2e- PbSO4(s) + 2H2O(l)
The overall reaction is Pb(s) + PbO2(s) + 2H2SO4(aq) PbSO4(s) + 2H2O(l)
Fuel cells: These are galvanic cells which convert the energy of combustion of fuels like
hydrogen, methane, methanol, etc. directly into electrical energy. Eg. Hydrogen - Oxygen
fuel cell, which is used in the Apollo space programme. Here hydrogen and oxygen are
bubbled through porous carbon electrodes into concentrated aqueous sodium hydroxide
solution. To increase the rate of electrode reactions, catalysts like finely divided platinum or
palladium metal are filled into the electrodes.The electrode reactions are:
Anode: 2H2(g) + 4OH (aq) 4H2O(l) + 4e-
Cathode:O2(g) + 2H2O(l) + 4e- 4OH-(aq)
Overall reaction is : 2H2(g) + O2(g) 2H2O(l)
Corrosion: The process of formation of oxide or other compounds of a metal on its surface
by the action of air, water-vapour, CO₂ etc. Examples are: The rusting of iron, tarnishing of
silver, formation of green coating on copper and bronze (verdigris) etc.
Electrochemical Theory of rusting: Occurs in presence of water and air. It is a redox reaction.
At a particular spot of the metal, oxidation takes place and that spot behaves as anode. Here
Fe is oxidized to Fe2+. 2Fe(s) 2Fe2+ + 4e-
Electrons released at anodic spot move through the metal and go to another spot on the metal
and reduce oxygen in presence of H+.This spot behaves as cathode.The reaction taking place
at this spot is : O2(g) + 4H+(aq) + 4e- 2H2O(l)
The overall reaction is : 2Fe(s) + O2(g) + 4H+(aq) 2Fe2+ (aq) + 2H2O(l)
The ferrous ions (Fe2+) are further oxidised to ferric ions (Fe3+) and finally to hydrated ferric
oxide (Fe2O3.xH2O),which is called rust.
Methods of prevention of corrosion
1. By barrier protection through coating the metal surface with paint or varnish or
electroplating etc.
2. By coating the metal surface with another electropositive metal like Zn, Mg etc. The
coating of metal with Zn is called galvanisation and the resulting iron is called galvanized
iron.
3. By coating with anti-rust solution (bis phenol).
4. By cathodic protection in which a metal is protected from corrosion by connecting it to
another metal that is more easily oxidised. An electrochemical method is to provide a
sacrificial electrode of another metal (like Mg, Zn, etc.) which corrodes itself but saves the
object.
QUESTION AND ANSWERS
1 a) Represent the galvanic cell based on the cell reaction given below:
Cu(s) + 2 Ag+ (aq) Cu2+(aq) + 2 Ag(s) b) Write the half cell reactions of the above
cell. c) λ0m for NaCl, HCl and NaAc are 126.4, 425.9 and 91.0 S cm2 mol-1 respectively.
Calculate λ0m for HAc.
Ans a) Cu/Cu2+ll Ag+/Ag
b) Anode Cu Cu2+ + 2e cathode Ag+ + e Ag
c) λ0m (CH3COOH) = λ0m(CH3COONa) + λ0m(HCI) - λ0m(NaCI)
= 91+425.9-126=390.5Scm2mol-1
2.Galvanic cells are classified into primary and secondary cells. a) Write any two differences
between primary and secondary cells. b) (i) What is a fuel cell? (1) (ii) Write the overall cell
reaction in H2 – O2 fuel cell?
Ans a) primary cells cannot be recharged or reused. Here the reaction occurs only once and
after use over a period of time, they become dead E.g. Dry cell .A secondary cell can be
recharged and reused again. Here the cell reaction can be reversed by passing current through
it in the opposite direction. Eg. Lead storage battery b) Fuel cells convert the energy of
combustion of fuels like hydrogen, methane, methanol, etc. directly into electrical energy.
c) 2H2 + O2 2H2O
3.We can construct innumerable number of Galvanic cells on the pattern of Daniel cell by
taking combination of different half cells. a) What is a Galvanic cell? b) Name the anode and
cathode used in the Daniel cell? c) Name the cell represented by Pt(s)/H2(g)/H+ (aq). d)
According to the convention, what is the potential of the above cell at all temperatures? e)
Write the use of the above cell?
Ans a) Devices that convert chemical energy of some redox reaction into electrical energy
.E g. Daniel Cell b) anode Zn rod in ZnSO4 solution cathode Cu rod in CuSO4 solution
c)SHE d) Zero e) use to measure standard electrode potential of other half cells
4. With decrease in concentration of an electrolytic solution, conductivity (ƙ) decreases and
molar conductivity (λm) increases. i) Write the equation showing the relationship between
conductivity and molar conductivity. ii) How will you account for the increase in molar
conductivity with decrease in concentration? iii) Limiting molar conductivity (λ0 m) of a
strong electrolyte can be determined by graphical extrapolation method. Suggest a method for
the determination of limiting molar conductivity of a weak electrolyte.
𝜅 1000
Ans i) λm = ii) For strong electrolytes,as dilution increases,the force of attraction
𝑀
between ions decreases and hence the ionic mobility increases.For weak electrolytes as
dilution increases,degree of dissociation increases iii) using Kholrausch’s law
CHAPTER 4:- CHEMICAL KINETICS
Expression of the rate of reaction
For the reaction 𝑨 → 𝑩
∆[𝑨] ∆[𝑩]
Rate of reaction (𝒓) = − =+ … … … … (𝟏)
∆𝒕 ∆𝒕
Here,
∆[𝑨]
− ∆𝒕 = Rate of disappearance of A
∆[𝑩]
+ =Rate of appearance of B
∆𝒕
CHEMISTRY
Equation (5) is the theoretical equation . Theoretical rate equation is correct
for some reactions and is wrong for some other reactions. To all reactions,
experimental rate equation is the valid rate equation.
Experimental rate equation for equation(5) is
𝒓 = 𝒌[𝑷]𝒙 [𝑸]𝒚
The sum of the powers of concentration terms in the experimental rate equation
is known as order of equation.
Order of reaction may have the values may varying from 0 to 3 including
fractional values.
Based on the values of order, reaction is of different types.
1) Zero order reactions: Here order of reaction is zero.
Eg:-
a. Decomposition of NH3 On hot platinum surface.
b. Thermal decomposition of HI on gold surface
2) First order reaction:- Here order of reaction is 1
Eg:- all radioactive decay
3) Reaction having fractional order
Eg:- decomposition of CH3 – CHO
𝐶𝐻3 − 𝐶𝐻𝑂 → 𝐶𝐻4 + 𝐶𝑂
Experimental rate equation r = 𝑘 [𝐶𝐻3 𝐶𝐻𝑂]3/2
Here order of reaction is 3/2
Unit rate constant (k)
Unit of rate constant depends on the order of reaction. If ‘n’ is the order of
reaction the unit of rate constant 𝑳𝒏−𝟏 𝒎𝒐𝒍𝟏−𝒏 𝒔−𝟏
Molecularity of reaction
The number of reacting species (atoms, ions or molecules) taking part in
an elementary reaction that will collide simultaneously is molecularity.
Molecularity of reaction varies from 1 to 3. No fractional values are
permitted for molecularity.
Based on molecularity, reactions are classified as given below.
1. Unimolecular or monomolecular reaction
Here molecularity of reaction is 1
Eg; decomposition of ammonium nitrite
NH4NO2→N2 + 2H2O
2. Bimolecular reaction or dimolecular reaction
Here molecularity of reaction is 2
Eg; H2+I2→2HI
3. Trimolecular or Termolecularreation
Here molecularity of reaction is 3
2NO+O2→2NO2
Order Molecularity
1) The sum of powers of The no. of reacting species taking
concentration terms in the part in an elementary reaction
experimental rate equation that will collide simultaneously
CHEMISTRY
2) It is an experimental quantity It is a theoretical quantity
3) It may have zero value It will never have zero value
4) It may have integral or fractional It will have only integral values
value
Equation (4) is known as integrated rate equation for zero order reaction.
𝑂𝑅
[𝐴] = −𝑘𝑡 + [𝐴]0 ……(1)
𝑇ℎ𝑒 𝑒𝑞𝑢𝑎𝑡𝑖𝑜𝑛 (1)is similar to straight line equation 𝑦 = −𝑚𝑥 + 𝑐 and it can be
graphically represented as follows.
Slope = -k
y – intercept = [𝑨]𝟎
Integrated rate equation for first order reaction
𝟐.𝟑𝟎𝟑 [𝑨]𝟎
𝒍𝒐𝒈 [𝑨]
= 𝒌………….. (6)
𝒕
𝑬𝒒𝒖𝒂𝒕𝒊𝒐𝒏 (𝟔)is known as integrated rate equation for first order reaction.
Graphical representation of integrated equation for first order reaction
Integrated rate equation for first order reaction is
2.303 [𝐴]
𝑘 = 𝑡 𝑙𝑜𝑔 [𝐴]0
𝑂𝑅
𝑘𝑡
𝑙𝑜𝑔 [𝐴] = − 2.303 + 𝑙𝑜𝑔 [𝐴]0 ……..(7)
CHEMISTRY
𝑇ℎ𝑒 𝑒𝑞𝑢𝑎𝑡𝑖𝑜𝑛 (7)is similar to straight line equation 𝑦 = −𝑚𝑥 + 𝑐, which can be
graphically shown as below.
𝒌
𝒔𝒍𝒐𝒑𝒆 = − 𝟐.𝟑𝟎𝟑,𝒚 − 𝒊𝒏𝒕𝒆𝒓𝒄𝒆𝒑𝒕 = 𝒍𝒐𝒈 [𝑨]𝟎
Examples of first order reactions
1) All natural and artificial radioactive decay
2) Decomposition of N2O5.
3) Decomposition of N2O.
Half life of reaction (𝒕𝟏/𝟐)
The time required for a reactant to become half of its initial concentration.
[𝐴]0 −[𝐴]
For zero order reaction, 𝑡 = 𝑘
[𝑨]𝟎
𝒕𝟏/𝟐 = 𝟐𝒌
CHEMISTRY
𝐴 = 𝐴𝑟ℎ𝑒𝑛𝑖𝑢𝑠𝑓𝑎𝑐𝑡𝑜𝑟/𝑐𝑜𝑙𝑙𝑖𝑠𝑠𝑖𝑜𝑛 𝑓𝑟𝑒𝑞𝑢𝑒𝑛𝑐𝑦/pre-exponential factor
𝐸𝑎 = Activation energy
R= Universal gas constant (8.314 𝐽 𝐾 −1 𝑚𝑜𝑙 −1 )
T = Temperature in Kelvin scale
In terms of natural logarithm Arrhenius equation (1) can be expressed as
𝑬
𝒍𝒏 [𝑲] = − 𝑹𝑻𝒂 + 𝒍𝒏 𝑨…………..(2)
𝐸𝑞𝑢𝑎𝑡𝑖𝑜𝑛 (2)can be expressed in terms of common logarithm as given below
−𝐸
𝑙𝑜𝑔 𝑘 = 2.303𝑎𝑅𝑇 + 𝑙𝑜𝑔 𝐴……….(4)
SAMPLE QUESTIONS
1. Give the differences between order and molecularity? (answer: refer the notes)
2. Give Arrhenius equation and explain the terms involved in it? (answer: refer the
notes)
3. What is pseudo order reaction? Give examples (answer: refer the notes)
4. For a reaction 𝑨 + 𝑩 → 𝑪 + 𝑫, the rate equation is. Rate 𝑲 = [𝑨] 𝟑/[𝑩]𝟏/𝟐. Given
that over all order and molecularity of reaction.
Answer: order =( 3/2)+(1/2)=2
5. The rate of reaction quadruples when the temperature changes from 293 K to 313
K, calculate energy of activation?
CHEMISTRY
6. What is half-life period? Suggest the equations to find half-life period of first
order and zero order reaction?(refer the notes)
7. Suggest the integrated rate equation for first order and zero order reaction?
(refer the notes)
CHEMISTRY
D and F BLOCK ELEMENTS
KEY POINTS:-
• Magnetic properties,oxidation state,KMnO4,
K2Cr2O7,Lanthanoid contraction
A transition element is defined as the one which has partially filled d orbitals in its ground
state or in any one of its oxidation states.
Zn,Cd and Hg are not considered as transition elements.[ Zn,Cd and Hg-general
electronic configuration ( n-1) )d 10ns2.The orbitals in these elements are completely filled
(d10) in the ground start as well as in their common oxidation stat es.
• General electronic configuration of d block elements-( n-1) )d 1-10ns1-2
Magnetic Properties :
Paramagnetism -due to the presence of unpaired electrons.
• For the compounds of 1 st row transition elements, it is calculated using only spin
magnetic moment and it is determined by the spin only formula:
√
µ s = n(n+2) where n is the no. of unpaired electrons and µ is the spin only
magnetic moment in the unit of Bohr Magneton (B.M).
• The magnetic moment increases with increase in no. of unpaired electrons.
Reason-Lanthanoid contraction
2. -The yellow solution of sodium chromate is filtered and acidified with sulphuric acid
to orange sodium dichromate.
2 Na2Cr0 4 + 2 H + → Na2Cr207 + 2 Na+ + H20
3.
The solution of sodium dichromate is treated with potassium chloride so that orange
crystals of
potassium dichromate crystallise out.
Na2Cr207 + 2 KCl → K2 Cr2 07 + 2 NaCl
The structures of chromate ion, Cr04 2– and the dichromate ion, Cr07 2– are shown
below.
Oxidising Property
K2 Cr207 is a good oxidising agent in acidic medium. Its oxidising action can
berepresented as follows:
Cr2072– + 14H + + 6e – → 2Cr 3+ + 7H20
Thus, acidified potassium dichromate will oxidise
1) Iodides to iodine
6I – + Cr2072– + 14 H + → 3 I2 + 2 Cr 3+ + 7H2 0
Cr2 07 2– + 14 H + + 6 Fe 2+ → 2 Cr 3+ + 6 Fe 3+ + 7 H20
* In the first step MnO 2 is fused with KOH to form potassium manganate (K2 MnO4 ).
2MnO2+4KOH →2 K2 MnO4+2H2O
1) Iron(II) to iron(III)
Lanthanoid Contraction:
In lanthanoids, the atomic and ionic radii decrease regularly from lanthanum to lutetium.
This regular decrease in the atomic and ionic radii along lanthanoid series is called
lanthanoid contraction.
Reason: In lanthanoids, as theatomic number increases, the nuclear charge increases
one by one and the electrons are added to the anti-penultimate f-Subshell. Due to its
diffused shape, f orbitals have poor shielding effect. So the nucleus can attract the outer
most electrons strongly and as a result the radii decreases.
Consequences:
1) Due to lanthanoid contraction the 2nd and 3rd row transition series elements
have similar radii.
( Zr – 160pm and Hf-159pm).
2) lanthanoids have similar physical properties and they occur together in nature.
So their isolation is difficult.
3) As the size of the lanthanoid ions decreases from La3+ to Lu3+,the covalent
characterof the hydroxides increases and hence the basic strength
decreases. La(OH)3 is most basic while Lu(OH)3 is the least basic.
Uses of Lanthanides
An important alloy is mischmetal which consists of a lanthanoid metal(approx. 95%) and
iron(approx. 5%)and traces of S,C,Ca and Al.A great deal of mischmetal is used in
magnesium based alloy to produce bullets,shell and lighter flint.
Model questions:
Coordination compounds are complex compounds in which transition metal atoms are bound to a number of anions or neutral molecules.
Ligands:
Ions or molecules bound to the central metal atom or ion in the coordination entity
Monodentate ligands
When a ligand is bound to a metal ion through a single donor atom,
–
Didentate – When a ligand can bind through two donor atoms
Ethane 1,2diamin and Oxalate
Eg; EDTA
Ambidentate –
(Can bind through two different atoms)
Coordination number: Number of ligand donor atoms bonded directly to the metal
Structural isomerism –
➢ Linkage isomerism:
Arises due to the presence of ambidentate ligand
➢ Coordination isomerism:
Arises due to the interchange of ligands between cationic and anionic entities of different metal ions
Co NH3 6 Cr CN 6 and Cr NH3 6 Co CN 6
➢ Ionisation isomerism:
Arises due to the interchange of ligands between the inside and the outside of the coordination sphere
Co (NH3) 5SO4 Br and Co (NH3) 5 Br SO4
4 sp3 Tetrahedral
4 dsp2 sp3d Square planar
5 sp3d2 Trigonal bipyramidal
6 d2sp3 Octahedral
6 Octahedral
Chemical Properties
Ambident Nucleophile: Nucleophiles having more than one linking atoms are known
̅ , −NO
as ambident Nucleophile. Eg. −CN ̅2 …
Towards SN2 reaction, various alkyl halides follow the reactivity order CH3 − X > 10 >
20 > 30 .
Stereochemical aspects of nucleophilic substitution reactions
A SN2 reaction proceeds with complete stereochemical inversion while a SN1 reaction proceeds
with racemisation.
Enantiomers
The stereoisomers which are non-super imposable mirror images are called enantiomers.
The process of conversion of enantiomer into a racemic mixture is known as racemisation.
Alkyl halides having two or more β carbon atom on treating alcoholic KOH, more than
one alkene is formed. Among these, the most substituted alkene is the major product
and the latter is the minor product. This rule is known as Zaitsev rule.
Reactions of Haloarenes
1. Nucleophilic substitution
Aryl halides are extremely less reactive towards nucleophilic substitution reactions why?
(i) Resonance effect: In haloarenes, the electron pairs on halogen atom are in conjugation with
π-electrons of the ring.
(ii) Difference in hybridisation of carbon atom in C—X bond In haloalkane, the carbon atom
attached to halogen is sp 3 hybridised while in case of haloarene, the carbon atom attached
to halogen is sp 2 -hybridised.
(iii) Instability of phenyl cation: In case of haloarenes, the phenyl cation formed as a result of
self-ionisation will not be stabilised by resonance and therefore, SN1 mechanism is ruled
out.
(iv) Because of the possible repulsion, it is less likely for the electron rich nucleophile to approach
electron rich arenes.
(ii) Replacement by hydroxyl group
Aryl halides also undergo SN reaction, if aryl halides contain electron with drawing group like –
NO2. As the number of electrons with drawing groups increases, the reactivity of aryl halides
increases towards SN reaction.
why does NO2 group show its effect only at ortho- and para positions and not at meta- position?
The presence of nitro group at ortho- and para-positions withdraws the electron density from the
benzene ring and thus facilitates the attack of the nucleophile on haloarene. The carbanion thus
formed is stabilised through resonance. The negative charge appeared at ortho- and para- positions
with respect to the halogen substituent is stabilised by –NO2 group while in case of meta-
nitrobenzene, none of the resonating structures bear the negative charge on carbon atom bearing the
–NO2 group. Therefore, the presence of nitro group at meta- position does not stabilise the negative
charge and no effect on reactivity is observed by the presence of –NO2 group at meta-position.
b) Nitration:
c) Sulphonation:
POLYHALOGEN COMPOUNDS
Dichloromethane (𝐂𝐇𝟐 𝐂𝐥𝟐 ): It is also known as methylene chloride. It is used as solvent,
as paint remover and used in the manufacture of drugs.
Trichloromethane (𝐂𝐇𝐂𝐥𝟑 ): CHCl3 is used as solvent and is also used in the refrigerant R-
22. CHCl3 is oxidised by air to form COCl2 (Phosgene).
light
2CHCl3 + O2 → 2COCl2 + 2HCl
It is therefore kept in closed dark coloured bottle completely filled, so that air is kept
out.
Triiodomethane (𝐂𝐇𝐈𝟑): It was used as antiseptic. Due to its objectionable smell, it has
been replaced by other formulations containing iodine.
Tetrachloromethane (𝐂𝐂𝐥𝟒 ): It is used as fire extinguisher. When CCl4 is released into
the air, it causes depletion of ozone layer. Depletion of ozone layer leads to skin cancer,
eye disease etc.
Freons: Chloro fluoro carbon compounds of CH4 and C2H6 are freons.
E.g. Freon-12 (CCl2F2). It is manufactured by Swartz reaction.
DDT: It is the first chlorinated insecticide. Paul Muller discovered the effectiveness of
DDT as insecticide. Its structure can be shown below,
Chapter 11 ALCOHOLS, PHENOLS AND ETHERS
Preparation of Alcohols
1. From alkenes:
(a) Alkenes on hydration in presence of catalyst alcohols are formed. Here addition reaction
occurs. If substrate and reagent, both are unsymmetrical Markovnikov’s rule is to be
considered.
NB: - Mechanism of reaction shows that, the reaction is proceeding through the formation of
carbocation intermediate.
(b) Alkenes on hydroboration (treating with B2H6) and addition product on oxidation alcohols are
formed. Here the net effect is the anti markovnikov addition of H2O to alkene.
B2 H6 /H2 O2
CH3 − CH = CH2 → CH3 − CH2 − CH2 − OH
Solubility
Solubility of alcohols and phenols in water is due to their ability to form hydrogen bonds with water
molecules. The solubility decreases with increase in size of alkyl / aryl groups.
Chemical Properties
Alcohols react both as nucleophiles and electrophiles. Alcohols react as nucleophiles when the bond
between O–H is broken. Alcohols act as electrophiles when the bond between C–O is broken.
following order.
(iii) Acidity of phenols
2. Esterification
Alcohols and phenols react with carboxylic acids, acid chlorides and acid anhydrides to form esters.
4. Dehydration
Alcohols undergo dehydration (removal of a molecule of water) to form alkenes on treating with a
protic acid e.g., concentrated H2SO4 or H3PO4 , or catalysts such as anhydrous zinc chloride or
alumina.
5. Oxidation
A primary alcohol is oxidised to an aldehyde which in turn is oxidised to a carboxylic acid.
(b) Bromination
(a) When phenol is treated with bromine water, 2,4,6-tribromophenol is formed
(c) When phenol is treated with bromine in CS2 at 273K we get ortho and para bromophenols.
3. Kolbe’s reaction
When phenol with sodium hydroxide we get Sodium phenoxide which on treatment with CO2 we get
Ortho hydroxybenzoic acid (Salicylic acid).
4. Reimer-Tiemann reaction
On treating phenol with chloroform in the presence of sodium hydroxide, we get ortho hydroxy
benzaldehyde (salicylic aldehyde).
6. Oxidation
Phenols are slowly oxidised In the presence of air and dark condition to give coloured mixtures
containing quinones.
It is highly poisonous in nature. (Ingestion of even small quantities of methanol can cause blindness and
large quantities causes even death.) Methanol is used as a solvent in paints, varnishes and chiefly for
making formaldehyde.
2. Ethanol (C2H5OH)
Ethanol is obtained commercially by fermentation.
Ethers
Preparation Ethers
1. By dehydration of alcohols: Alcohols undergo dehydration in the presence of protic acids (H2SO4,
H3PO4) to give ethers.
2. Williamson synthesis
Alkyl halide is reacted with sodium alkoxide to give ethers.
Physical Properties
1. Boiling Point
Boiling point of alcohols are higher than that of ethers why? Boiling point of alcohols are higher than
that of ethers is due to the presence of hydrogen bonding in alcohols.
Chemical Reactions
1. Cleavage of C–O bond in ethers
When ethers are treated with hydrogen halides, we get alkyl halides and alcohol
2. Electrophilic substitution
(i) Halogenation
Anisole undergoes bromination with bromine in ethanoic acid to give o-bromo anisole and p-bromo
anisole.
(iv) Nitration
Anisole reacts with a mixture of concentrated sulphuric and nitric acids to yield a mixture of ortho and para nitro
anisole.
ALDEHYDES, KETONES AND CARBOXYLIC ACIDS
Aldehydes, Ketones and Carboxylic Acids contain carbonyl group (C=O). so they are known
as carbonyl compound. Carbonyl carbon atom is sp2 hybridised. It forms three sigma (σ)
bonds and one pi (π) bond.C=O double bond is polarised due to higher electronegativity of
oxygen relative to carbon. High polarity of the carbonyl group is explained on the basis of
resonance
1. By oxidation of alcohols: Primary alcohols on oxidation with mild oxidising agents like
CrO3 to give aldehydes while secondary alcohols give ketones.
R-CH2OH (primary alcohol) + [O] R-CHO (aldehyde)
2. Etard reaction: Chromyl chloride oxidises methyl group to a chromium complex, which
on hydrolysis gives corresponding benzaldehyde.
3. By Gatterman – Koch reaction: When benzene is treated with carbon monoxide and
hydrogen
chloride in the presence of anhydrous aluminium chloride , we get benzaldehyde.
4. Preparation of Ketones:
Friedel-Crafts acylation reaction: When benzene or substituted benzene is treated with acid
chloride (R-COCl) in the presence of anhydrous aluminium chloride, we get a ketone.
Chemical reactions
3) Oxidation:
a)Aldehydes are easily oxidised to carboxylic acids on treatment with oxidising agents like
nitric acid. Mild oxidising agents like CrO3 , Tollens’ reagent and Fehlings’ reagent can also
oxidise aldehydes. [O]
CH3 -CHO (aldehyde) CH3 -COOH (carboxylic acid)
Ketones when oxidised using strong oxidising agents and at high temperatures, we get a
mixture of carboxylic acids having lesser number of carbon atoms.
b) Tollens’ test: Tollen’s reagent is freshly prepared ammoniacal Silver nitrate. Tollens’
reagent, give a silver mirror with aldehydes.
c) Fehling’s test: Fehling reagent is a mixture of Fehling solution A and Fehling solution B.
Fehling solution A is aqueous copper sulphate and Fehling solution B is alkaline sodium
potassium tartarate (Rochelle salt). On heating with Fehling’s reagent, aldehyde gives a
reddish brown precipitate of cuprous oxide (Cu2O). Aromatic aldehydes do not give this test.
5) Cannizzaro Reaction:
Aldehydes having no α-hydrogen atom (e.g. HCHO, C6H5 -CHO, CCl3 -CHO etc), when
treated with Conc. Alkali (NaOH or KOH) undergo self oxidation and reduction
(disproportionation) to form one molecule of the alcohol and one molecule of carboxylic acid
salt. This reaction is called Cannizzaro reaction.
CARBOXYLIC ACIDS
Preparation of Carboxylic acids:
1. From aldehydes: Aldehydes on oxidation with mild oxidising agents like CrO 3 or Tollen’s
reagent to give carboxylic acids.
[O]
CH3 -CHO (aldehyde) CH3 -COOH (carboxylic acid)
2. From alkylbenzenes:
Aromatic carboxylic acids can be prepared by vigorous oxidation of alkyl benzenes with
chromic acid. The entire side chain is oxidised to the carboxyl group.
Chemical Reactions:
A) Nitration: Benzoic acids in presence of conc. Nitric acid/Conc. Sulphuric acid gives m-
Nitrobenzoic acid.
SAMPLE QUESTIONS
1) Explain the following reactions:
a) Rosenmund reduction b)Gatterman–Koch c) Clemmensen reduction d) Aldol condensation.
Hint: a) Acid chlorides with H2 , b) benzene treat with CO, c) aldehydes and ketones with
Zn/Hg and HCl, d) aldehydes and ketones having α-hydrogen atom with dilute alkali
2) Explain the acidity of carboxylic acids.
Hint: carboxylic acids are acidic
3) What is Friedel-Crafts acylation reaction?
Hint: benzene with acid chloride/anhydrous aluminium chloride
4) What are the products on the oxidation of primary alcohols and secondary alcohols?
Hint: Primary gives aldehydes, secondary gives ketones.
5) Aromatic aldehydes undergo electrophilic substitution reactions. Write the nitration
reaction of benzaldehyde with chemical equation.
Hint:
Physical Properties
⚫ Lower aliphatic amines are soluble in water because they can form hydrogen bonds with water
molecules.
⚫ the order of boiling points of isomeric amines is as follows Primary > Secondary > Tertiary
amines.
(b) Aromatic amines react with nitrous acid at low temperatures (273-278 K) to form diazonium
salts.
6 Hinsberg's Test (Reaction with aryl sulphonyl chloride)
Aniline reacts with bromine water at room temperature to give a white precipitate of 2,4,6-tribromoaniline.
(b) Nitration
(c) Sulphonation
Aniline reacts with concentrated sulphuric acid to form p-aminobenzene sulphonic acid, commonly known
as sulphanilic acid.
DIAZONIUM SALTS
Method of Preparation of Diazonium Salts Benzene diazonium chloride is prepared by the reaction
of aniline with nitrous acid at 273-278K.
REPLACEMENT REACTION
CHAPTER14 BIOMOLECULES
CARBOHYDRATES
Carbohydrates are defined as polyhydroxy aldehydes or ketones or the compounds, which produce such
units on hydrolysis.
CLASSIFICATION OF CARBOHYDRATES: Based on their behaviour towards hydrolysis, carbohydrates
are classified in to three.
1. MONOSACCHARIDES: These carbohydrates cannot be hydrolysed in to simpler polyhydroxy
aldehydes or ketones. E.g. glucose, fructose etc.
2. OLIGOSACCHARIDES: These carbohydrates will give 2 to 10 monosaccharides on hydrolysis. E.g.
Sucrose, Maltose and Lactose.
REACTIONS OF GLUCOSE
DISACCHARIDES
Here two Monosaccharides are linked through c-o-c linkage (glycosidic linkage).
Sl Sugar Reducing Mono saccharides Glycosidic linkage
No. character
1 Sucrose Non α - D - glucose + - D - fructose C1 of α-glucose and C2 of -fructose
reducing
2 Maltose Reducing α - D - glucose + α - D - glucose C1 of α-glucose and C4 of α-glucose
Sucrose is dextrorotatory, but after hydrolysis gives dextrorotatory glucose and laevorotatory fructose. But
the mixture of glucose and fructose as a whole is laevorotatory. So the process is called inversion of cane
sugar and the product formed is Invert sugar.
POLYSACCHARIDES
Sl Sugar Reducing Mono saccharides Glycosidic linkage between
No. character
1 Starch Non α - D - glucose It has two components – Amylose and
reducing Amylopectine.
1. AMYLOSE: It is linear polymer
of α-D-glucose (C1-C4)
2. AMYLOPECTINE: It is a
branched chain polymer of α-D-
glucose (C1-C4 & C1-C6)
2 Cellulose Non β- D - glucose C1 of one glucose and C4 of another
reducing glucose
3 Glycogen Non α - D - glucose Similar to amylopectin
reducing
IMPORTANCE OF CARBOHYDRATES
1) As storage molecules as starch in plants and glycogen in animals.
2) Cell wall of bacteria and plants are made up of cellulose.
3) Used as raw materials for industries like textiles, paper etc.
4) Carbohydrates in the form of wood is used for making furniture.
PROTEINS
They are polymers of amino acids linked by peptide bonds.
CLASSIFICATION OF AMINO ACIDS:
Amino acids are classified in to two,
A. ESSENTIAL AMINO ACIDS: These are amino acids, which should get through diet. E.g.
Lysine, leucine, isoleucine etc.
B. NON ESSENTIAL AMINO ACIDS: These are amino acids, which one synthesised by a body.
E.g. Alanine, glycine, glutamic acid etc.
Based on the relative number of –COOH and –NH2 groups, amino acids are classified in to three.
1) ACIDIC AMINO ACID: Here the number of –COOH group is more than that of –NH2 group. E.g.
Aspartic acid, glutamic acid.
2) BASIC AMINO ACID: Here the number of –NH2 group is more than that of –COOH group. E.g.
Lysine, Histidine.
3) NEUTRAL AMINO ACID: Here the number of –NH2 and –COOH group is same. E.g. Glycine.
FORMATION OF ZWITTER ION: Since it contains acidic –COOH and basic –NH2, it can form Zwitter
ion.
E.g. NH2 − CH2 − COOH ⇌ NH3+ − CH2 − COO−
PEPTIDE LINKAGE
In proteins, amino acids are linked through –CONH linkage called peptide linkage.
CLASSIFICATION OF PROTEINS
Based on the shape of protein, they are classified in to two,
1) FIBROUS PROTEINS: These are fibre like structure and here α-helixes run parallel and are held
together by Hydrogen bonds. These are water insoluble.
E.g. Keratin, Myosin.
2) GLOBULAR PROTEINS: These are spherical shaped and here the polypeptide chain coils. These
are water soluble.
E.g. Insulin, Albumin.
LEVELS OF PROTEIN STRUCTURE
10 STRUCTURE: It describes the sequence of amino acids.
20 STRUCTURE: It is the shape in which a long poly peptide chain can exist. It is of two types,
a) α-helix: A protein thread is folded in the form of helix. It is maintained by H-bonds. It has only right
hand helices.
b) -pleated sheet: Here polypeptide chains lie side by side in zig-zag manner.
30 STRUCTURE: Long protein chains folded extensively upon itself. It is maintained by H-bond, Van der
Waals force and electrostatic force of attraction. It gives rise to fibrous and globular shape.
40 STRUCTURE: Some proteins are assembly of more than one polypeptide or sub units. There are held
together by hydrophobic interaction.
DENATURATION OF PROTEIN
When a protein in its native form is subjected to change in pH or change in temperature, it loses its
biological activity. It is denaturation of protein.
During denaturation, its 20 and 30 structure are destroyed, but its 10 structure remain intact.
E.g. boiling of egg, curdling of milk etc.
VITAMINS: Organic compounds required in the diet in small amounts to perform specific biological
functions for normal maintenance of optimum growth and health of organism. They are designated by
alphabets A, B, C & D etc.
Vitamins are mainly classified into two,
1. FAT SOLUBLE VITAMINS: These are soluble in fat and oils, but isoluble in H2O. E.g.
Vitamins A, D, E, K…
2. WATER SOLUBLE VITAMINS: These are soluble in water.
E.g. Vitamins B & C.
Water soluble vitamins must be regularly supplied in the diet, because they are readily excreted in
the urine.
Important vitamins and their deficiency disease are given below,
NUCLEIC ACIDS
Nucleic acids are polymers of nucleotides, they are also known as poly nucleotides. It is of two types, DNA
and RNA.
Nucleic acids contain a pentose sugar, phosphoric acid and nitrogen bases. DNA contains pentose sugar, -
D-2-deoxy ribose, nitrogen bases Adenine, Guanine, Cytosine and Thymine. RNA contains pentose sugar -
D-ribose and nitrogen bases Adenine, Guanine, Cytosine and uracil.
In Nucleic acids, pentose sugar combines with Nitrogen bases through their 1 st carbon to form Nucleoside.
These nucleosides on combination with H3PO4 through 5th carbon of nucleoside gives nucleotides. These
Nucleotides on joining through phosphodiester linkage to give Nucleic acids.
RNA molecules are of three types and they perform different functions. They are m-RNA, r-RNA and t-
RNA.
James Watson and Francis crick gave a double strand helix structure for DNA. Two nucleic acid chains are
wound about each other and are held together by hydrogen bonds between pairs of bases. Here Adenine
forms hydrogen bonds with thymine, whereas cytosine forms hydrogen bonds with guanine.
DNA Finger Printing
It is used for,
a) Identification of criminals in forensic labs.
b) To determine the paternity of individual.
c) To identify dead bodies.
BIOLOGICAL FUNCTIONS OF NUCLEIC ACIDS
DNA is responsible for heredity and it is used as reserve for genetic information. Nucleic acids are involved
in protein synthesis.
SAMPLE QUESTIONS
1. Suggest a method for preparation of glucose?(answer: refer the notes)
2. Give two examples of disaccharides? Give the name of linkage of in polysaccharides?(answer:
refer the notes)
3. Give the names of products when glucose is treated with
(a)HI (b) Conc.HNO3
4. Write the importance of carbohydrates?(answer: refer the notes)
5. Name the type of linkage in proteins?(answer: refer the notes)
6. Differentiate between fibrous and globular proteins?(answer: refer the notes)
7. What is denaturation of protein? Give two examples?(answer: refer the notes)
8. Give an example of each of fat soluble and water soluble vitamin?(answer: refer the notes)
9. Name the type of linkage in nucleic acids?(answer: refer the notes)
10. Differentiate between DNA & RNA (answer: refer the notes)