11chemistry OMEGA PDF
11chemistry OMEGA PDF
11chemistry OMEGA PDF
16. Mass of a substance is the amount of matter present in it while weight is the force exerted
by gravity on an object. The mass of a substance is constant whereas its weight may vary
from one place to another due to change in gravity.
17. Volume has the units of (length) 3. So in SI system, volume has units of m3. A common
unit, litre (L) which is not an SI unit, is used for measurement of volume of liquids. 1 L =
1000 mL , 1000 cm3 = 1 dm3
18. Density of a substance is its amount of mass per unit volume SI units of density kg m–3
This unit is quite large and a chemist often expresses density in g cm–3.
19. There are three common scales to measuretemperature — °C (degree celsius), °F (degree
Fahrenheit) and K (Kelvin). Here, K is the SI unit.
20. The Kelvin scale is related to Celsius scale as follows :K =°C+273.15
21. The °F scale is related to Celsius scale as follows
22. In scientific notation (exponential Notation) any number can be represented in the form
N × 10n where n is an exponent having positive or negative values and N can vary between
1 to 10. Thus, we can write 232.508 as 2.32508 X102 in scientific notation. Note that while
writing it, the decimal had to be moved to the left by two places and same is the exponent
(2) of 10 in the scientific notation. Similarly, 0.00016 can be written as 1.6 X10–4. Here the
decimal has to be moved four places to the right and (– 4) is the exponent in the scientific
notation.
23. Significant figures are meaningful digits which are known with certainty. The uncertainty
is indicated by writing the certain digits and the last uncertain digit. Thus, if we write a
result as 11.2 mL, we say the 11 is certain and 2 is uncertain and the uncertainty would be
1 in the last digit. Unless otherwise stated, an uncertainty of +1 in the last digit is always
understood.
24. There are certain rules for determining the number of significant figures. These are
stated below:
a) All non-zero digits are significant. For example in 285 cm, there are three significant
figures and in 0.25 mL, there are two significant figures.
b) Zeros preceding to first non-zero digit are not significant. Such zero indicates the position
of decimal point. Thus, 0.03 has one significant figure and 0.0052 has two significant
figures.
c) Zeros between two non-zero digits are significant. Thus, 2.005 has four significant figures.
d) Zeros at the end or right of a number are significant provided they are on the right side of
the decimal point. For example, 0.200 g has three significant figures. But, if otherwise, the
terminal zeros are not significant if there is no decimal point. For example, 100 has only
one significant figure, but 100. has three significant figures and 100.0 has four significant
figures. Such numbers are better represented in scientific notation. We can express the
number 100 as 1×102 for one significant figure, 1.0×102 for two significant figures and
1.00×102 for three significant figures.
e) Counting numbers of objects, for example, 2 balls or 20 eggs, have infinite significant
figures as these are exact numbers and can be represented by writing infinite number of
zeros after placing a decimal i.e.,2 = 2.000000 or 20 = 20.000000
f) In numbers written in scientific notation, all digits are significant e.g., 4.01×102 has three
significant figures, and 8.256 × 10–3 has four significant figures.
25. .Law of Conservation of Mass states that matter can neither be created nor destroyed.
26. Law of Definite Proportions states that a given compound always contains exactly the
same proportion of elements by weight.
27. Law of Multiple Proportions states that if two elements can combine to form more than
one compound, the masses of one element that combine with a fixed mass of the other
element, are in the ratio of small whole numbers.
28. Gay Lussac’s Law of Gaseous Volumes: This law was given by Gay Lussac in 1808. He
observed that when gases combine or are produced in a chemical reaction they do so in a
simple ratio by volume provided all gases are at same temperature and pressure.
29. In 1811, Avogadro proposed that equal volumes of gases at the same temperature and
pressure should contain equal number of molecules.
30. In 1808, Dalton published ‗A New System of Chemical Philosophy‘ in which he proposed
the following :
a) Matter consists of indivisible atoms.
b) All the atoms of a given element have identical properties including identical mass.
Atoms of different elements differ in mass.
c) Compounds are formed when atoms of different elements combine in a fixed ratio.
d) Chemical reactions involve reorganization of atoms. These are neither created nor
destroyed in a chemical reaction.
e) Dalton‘s theory could explain the laws of chemical combination.
31. One atomic mass unit is defined as a mass exactly equal to one twelfth the mass of one
carbon - 12 atom.
32. Molecular mass is the sum of atomic masses of the elements present in a molecule. It is
obtained by multiplying the atomic mass of each element by the number of its atoms and
adding them together.
33. The mole is the amount of substance of a system which contains as many elementary
entities as there are atoms in 0.012 kilogram of carbon-12; its symbol is ―mol.‖ When the
mole is used, the elementary entities must be specified and may be atoms, molecules, ions,
electrons, other particles, or specified groups of such particles. This number of entities in 1
mol is so important that it is given a separate name and symbol. It is known as ‗Avogadro
constant‘, denoted by NA in honor of Amedeo Avogadro.
34. An empirical formula represents the simplest whole number ratio of various atoms present
in a compound whereas the molecular formula shows the exact number of different types of
atoms present in a molecule of a compound.
35. Many a time, the reactions are carried out when the reactants are not present in the amounts
as required by a balanced chemical reaction. In such situations, one reactant is in excess
over the other. The reactant which is present in the lesser amount gets consumed after
sometime and after that no further reaction takes place whatever be the amount of the other
reactant present. Hence, the reactant which gets consumed, limits the amount of product
formed and is, therefore, called the limiting reagent.
37. Mole Fraction: It is ratio of number of moles of a particular component to the total number
of moles of all the components.
No. of moles of solute
Mole-fraction of solute =
No. of moles of solute No. of moles of solvent
WB
nB MB
xB
nA nB WA W
B
M A WB
WB
MB W W
xB in case of dilute solution B < < A
WA MB MA
MA
38. Molality (m). It is defined as number of moles of solute (B) per 1000 g or 1 kg of solvent.
No. of moles of solute WB 1000
Molality (M) =
Kg. of solvent MA WB in grams.
39. Molarity (M). It is expressed as the number of moles of solute per litre of solution.
No. of moles of solute WB 1000
Molarity (M) =
Litres of solution M B Volume of solution in ml.
c) The energy of an electron in the orbit does not change with time. However, the electron
will move from a lower stationary state to a higher stationary state when required amount
of energy is absorbed by the electron or energy is emitted when electron moves from
higher stationary state to lower stationary state . The energy change does not take place
in a continuous manner.
d) The frequency of radiation absorbed or emitted when transition occurs between two
stationary states that differ in energy by ΔE, is given by :
15. Bohr‘s theory can also be applied to the ions containing only one electron, similar to that present
in hydrogen atom. For example, He+ Li2+, Be3+ and so on. The energies of the stationary states
associated with these kinds of ions (also known as hydrogen like species) are given by the
expression
16. Limitations of Bohr’s Model: It fails to account for the finer details (doublet, that is two closely
spaced lines) of the hydrogen atom spectrum observed by using sophisticated spectroscopic
techniques. This model is also unable to explain the spectrum of atoms other than hydrogen, for
example, helium atom which possesses only two electrons. Further, Bohr‘s theory was also
unable to explain the splitting of spectral lines in the presence of magnetic field (Zeeman effect)
or an electric field (Stark effect).
17. Dual Behaviour of Matter: The French physicist, de Broglie in 1924 proposed that matter, like
radiation, should also exhibit dual behaviour i.e., both particle and wavelike properties.
18. The de Broglie relation. :de Broglie relation state that the wavelength associated with a moving
object or an electron is inversely proportional to the momentum of the particle.
h h
where p is the momentum of particle = mv.
mv p
19. Heisenberg’s Uncertainty Principle. It is not possible to determine the position and velocity
simultaneously for a sub-atomic particle like electron at any given instant to an arbitary degree of
precision. Consequently, it is not possible to talk of path of the electron in which it moves. If
‗ x‘ is uncertainty in position and ‗ P‘ is uncertainty in momentum then
h
x.P
4
20. Orbital. It is a region or space where there is maximum probability of getting electron.
21. Quantum numbers. They are used to get complete information about electron, i.e., location,
energy, spin, etc. These quantum numbers also help to designate the electron present in an
orbital.
22. Principal quantum number. It specifies the location and energy of an electron. It is measure
of the effective volume of the electron cloud. It is denoted by ‗n‘. Its possible values are 1, 2,
3,4 …..
23. Angular momentum quantum number. It is also called ‗azimuthal quantum number‘. It
determines the shape of the orbital. It is denoted by ‗l‘. The permitted values of ‗l‘ are 0, 1, 2,
etc., upto n–1. For a given value of n, l = 0 to n – 1 ‗. e.g., if value of n is 4, l can have values
h
mvr l (l 1)
0, 1, 2, 3. It determines angular momentum. 2
24. Magnetic quantum number. It is denoted by ‗m‘ and its value depends on value of ‗l‘ since
magnetism is due to angular momentum. It determines the magnetic orientation of an orbital,
i.e., the direction of orbital relative to magnetic field in which it is placed. Its permitted values
are - l to + l including zero, e.g., when l = 1, then m = -1, 0, +1. It has total number of values
equal to 2l + 1.
25. Spin quantum number. It indicates, the direction in which electron revolves. Spin is
magnetic property and is also quantized. It has two permitted values + ½ or – ½. The spin
angular momentum of an electron is constant and cannot be changed.
26. (n+l) rule: The relative order of energies of various sub-shells in a multi-electron atom can be
predicted with the help of (n+l) rule (also called Bohr-Bury rule)According to this rule a sub-
shell with lower values of (n+l) has lower energy.In case two sub-shell has equal value of (n+l),
the sub-shell with lower value of n has lower energy
27. Pauli’s Exclusion Principle. No two electrons in an atom can have all the four quantum
numbers same. It can also be stated as – An orbital can have maximum two electrons and they
must be of opposite spin quantum numbers.
28. Aufbau principle. Electrons are filled in the various orbitals in the increasing order of their
energies, i.e., orbital having lowest energy will be filled first and the orbital having highest
energy will be filled last.Increasing energy ofatomic orbitals for multi-electron atoms
1s < 2s < 2p < 3s <3p < 4s <3d < 4p <5s < 4d <5p < 6s < 4f < 5d < 6p < 7s
29. Hund’s rule of maximum multiplicity. No electron pairing takes place in p, d and f orbitals
until each orbital in the given sub-shell contains one electron, e.g., N (7) has electronic
configuration 1s2 2s2 2 p1x 2 p1y 2 p1z according to Hund‘s rule and not 1s 2 2s 2 2 p x2 2 p1y .
30. The valence electronic configurations of Cr and Cu, therefore, are 3d5 4s1 and 3d104s1
respectively and not 3d4 4s2 and 3d94s2. It has been found that there is extra stability(Stability of
Completely Filled and Half Filled Subshells) associated with these electronic configurations.
31. Three orbitals of 2p subshell (2px, 2py, and 2pz orbitals).
32. Five orbitals of 3d subshell (3dxy, 3dyz, 3dzx 3dx2-y2and 3dx2 orbitals).
3.Classification of elements and periodicity in properties
5. Modern periodic law: Properties of elements are the periodic function of their atomic number.
6. Modern Periodic Table: This table was prepared was Bohr and is based upon the electronic
configuration of elements. The table consists of 18 vertical columns called groups Elements
having similar outer electronic configurations in their atoms are arranged in vertical columns,
referred to as groups . According to the recommendation of International Union of Pure and
Applied Chemistry (IUPAC), the groups are numbered from 1 to 18 and the table consists of 7
horizontal rows called periods. The first period contains 2 elements. The subsequent periods
consists of 8, 8, 18, 18 and 32 elements, respectively. The seventh period is incomplete and like
the sixth period would have a theoretical maximum (on the basis of quantum numbers) of 32
elements. In this form of the Periodic Table, 14 elements of both sixth and seventh periods
(lanthanoids and actinoids, respectively) are placed in separate panels at the bottom
7. .Notation for IUPAC Nomenclature of Elements With Z > 100
8. We can classify the elements into four blocks viz., s-block, p-block, d-block and f-block
depending on the type of atomic orbital that are being filled with electrons.
9. s-Block Elements :The elements of Group 1 (alkali metals) and Group 2 (alkaline earth metals)
which have ns1and ns2 outermost electronic configuration belong to the s-Block Elements.
10. p-Block Elements The p-Block Elements comprise those belonging to Group 13 to 18 and these
together with the s-Block Elements are called the Representative Elements or Main Group
Elements. The outermost electronic configuration varies from ns2np1 to ns2np6 in each period.
11. d-Block Elements These are the elements of Group 3 to 12 in the centre of the Periodic Table.
These are characterised by the filling of inner d orbitals by electrons and are therefore referred to
as d-Block Elements. These elements have the general outer electronic configuration (n-1)d1-
10
ns0-2 .
12. f-Block Elements The two rows of elements at the bottom of the Periodic Table, called the
Lanthanoids, Ce(Z = 58) – Lu(Z = 71) and Actinoids, Th(Z = 90) – Lr (Z = 103) are
characterised by the outer electronic configuration (n-2)f1-14 (n-1)d0–1ns2. The last electron added
to each element is filled in f- orbital. These two series of elements are hence called the Inner-
Transition Elements (f-Block Elements).
13. Variation in Atomic Radius in Period: The atomic size generally decreases across a period It is
because within the period the outer electrons are in the same valence shell and the effective
nuclear charge increases as the atomic number increases resulting in the increased attraction of
electrons to the nucleus.
Li Be B C N O F Ne
14. Variation in Atomic Radius in Group: Within a family or vertical column of the periodic table,
the atomic radius increases regularly with atomic number as). as we descend the groups, the
principal quantum number (n) increases and the valence electrons are farther from the nucleus.
This happens because the inner energy levels are filled with electrons, which serve to shield the
outer electrons from the pull of the nucleus. Consequently the size of the atom increases as
reflected in the atomic radii.
15. The atomic radii of noble gases are not considered here. Being monatomic, their (non-bonded
radii) values are very large. In fact radii of noble gases should be compared not with the covalent
radii but with the van der Waals radii of other elements.
16. A cation is smaller than its parent atom because it has fewer electrons while its nuclear charge
remains the same. The size of an anion will be larger than that of the parent atom because
the addition of one or more electrons would result in increased repulsion among the electrons
and a decrease in effective nuclear charge. For example, the ionic radius of fluoride ion (F– ) is
136 pm whereas the atomic radius of fluorine is only 64 pm. On the other hand, the atomic radius
of sodium is 186 pm compared to the ionic radius of 95 pm for Na+.
17. Isoelectronic species :Atoms and ions which contain the same number of electrons.. For
example, O2–, F–, Na+ and Mg2+ have the same number ofelectrons (10). Their radii would be
different because of their different nuclear charges. The cation with the greater positive charge
will have a smaller radius because of the greater attraction of the electrons to the nucleus. Anion
with the greater negative charge will have the larger radius. In this case, the net repulsion of the
electrons will outweigh the nuclear charge and the ion will expand in size.
18. Ionization Enthalpy: It represents the energy required to remove an electron from an isolated
gaseous atom (X) in its ground state. In other words, the first ionization enthalpy for an element
X is the enthalpy change (ΔiH) for the reaction depicted in equation. X (g) X+(g) + e– . The
ionization enthalpy is expressed in units of kJ mol–1. We can define the second ionization
enthalpy as the energy required to remove the second most loosely bound electron; it is the
energy required to carry out the reaction shown in equation X+(g)X2+(g) + e– . Energy is
always required to remove electrons from an atom and hence ionization enthalpies are always
positive. The second ionization enthalpy will be higher than the first ionization enthalpy because
it is more difficult to remove an electron from a positively charged ion than from a neutral atom.
In the same way the third ionization enthalpy will be higher than the second and so on. The term
―ionization enthalpy‖, if not qualified, is taken as the first ionization enthalpy.
19. Variation in Ionization Enthalpy in Group: As we descend in a group the first ionization
enthalpy generally decreases .Because as we go down a group, the outermost electron being
increasingly farther from the nucleus, there is an increased shielding of the nuclear charge by the
electrons in the inner levels. In this case, increase in shielding outweighs the increasing nuclear
charge and the removal of the outermost electron requires less energy down a group.
20. Variation in Ionization Enthalpy in Period: The first ionization enthalpy generally increases as
we go across a period. When we move from left to right in period, successive electrons are added
to orbitals in the same principal quantum level and the shielding of the nuclear charge by the
inner core of electrons does not increase very much to compensate for the increased attraction of
the electron to the nucleus. Thus, across a period, increasing nuclear charge outweighs the
shielding. Consequently, the outermost electrons are held more and more tightly and the
ionization enthalpy increases across a period
21. Electron Gain Enthalpy: When an electron is added to a neutral gaseous atom (X) to convert it
into a negative ion, the enthalpy change accompanying the process is defined as the Electron
Gain Enthalpy (ΔegH). Electron gain enthalpy provides a measure of the ease with which an atom
adds an electron to form anion as represented by equation. X(g) + e – X–(g) . Depending on the
element, the process of adding an electron to the atom can be either endothermic or exothermic.
For many elements energy is released when an electron is added to the atom and the electron
gain enthalpy is negative. For example, group 17 elements (the halogens) have very high
negative electron gain enthalpies because they can attain stable noble gas electronic
configurations by picking up an electron. On the other hand, noble gases have large positive
electron gain enthalpies because the electron has to enter the next higher principal quantum level
leading to a very unstable electronic configuration.
22. Variation in electron gain enthalpies in Group & period: The variation in electron gain
enthalpies of elements is less systematic than for ionization enthalpies. As a general rule,
electron gain enthalpy becomes more negative with increase in the atomic number across a
period. The effective nuclear charge increases from left to right across a period and consequently
it will be easier to add an electron to a smaller atom since the added electron on an average
would be closer to the positively charged nucleus. We should also expect electron gain enthalpy
to become less negative as we go down a group because the size of the atom increases and the
added electron would be farther from the nucleus. This is generally the case. However, electron
gain enthalpy of O or F is less negative than that of the succeeding element. This is because
when an electron is added to O or F, the added electron goes to the smaller n = 2 quantum level
and suffers significant repulsion from the other electrons present in this level. For the n = 3
quantum level (S or Cl), the added electron occupies a larger region of space and the electron-
electron repulsion is much less.
23. Electronegativity: A qualitative measure of the ability of an atom in a chemical compound to
attract shared electrons to itself is called electro negativity Linus Pauling, an American scientist,
in 1922 assigned arbitrarily a value of 4.0 to fluorine, the element considered to have the greatest
ability to attract electrons. Electronegativity generally increases across a period from left to right
(say from lithium to fluorine) and decrease down a group (say from fluorine to astatine) in the
periodic table.
24. Anomalous Properties of Second Period Elements: The first element of each of the groups 1
(lithium) and 2 (beryllium) and groups 13-17 (boron to fluorine) differs in many respects from
the other members of their respective group. For example, lithium unlike other alkali metals, and
beryllium unlike other alkaline earth metals, form compounds with pronounced covalent
character; the other members of these groups predominantly form ionic compounds. In fact the
behaviour of lithium and beryllium is more similar with the second element of the Group 1, 2
,13, 14, 15, 16 ,17. following group i.e., magnesium and aluminum, respectively. This sort of
similarity is commonly referred to as diagonal relationship in the periodic properties. The
anomalous behaviour is attributed to their small size, large charge/ radius ratio and high
electronegativity of the elements. In addition, the first member of group has only four valence
orbitals (2s and 2p) available for bonding, whereas the second member of the groups have nine
valence orbitals (3s, 3p, 3d). As a consequence of this, the maximum covalency of the first
member of each group is 4 (e.g., boron can only form[BF4]- , whereas the other members of the
groups can expand their valence shell to accommodate more than four pairs of electrons e.g.,
aluminum forms [AlF6]3- ). Furthermore, the first member of p-block elements displays greater
ability to form p∏ – p∏ multiple bonds to itself (e.g., C = C, C C, N = N, N N) and to other
second period elements (e.g., C = O, C = N, C N, N = O) compared to subsequent members of
the same group.
4.Chemical bonding and Molecular Structure
5. Electrovalent bond or Ionic Bond: The chemical bond as result of transfer of electron from one
atom(electropositive) to another atom (electronegative).Ionic bonds will be formed more easily
between elements with comparatively low ionization enthalpies and elements with comparatively
high negative value of electron gain enthalpy. Most ionic compounds have cations derived from
metallic elements and anions from non-metallic elements.
6. Formation of Ionic Bond
7. Bond length is defined as the equilibrium distance between the nuclei of two bonded atoms in a
molecule.
8. Bond Angle:It is defined as the angle between the orbital containing bonding electron pairs
around the central atom in a molecule/complex ion. It gives some idea regarding the distribution
of orbital around the central atom in a molecule/complex ion and hence it helps us in determining
its shape
9. Bond enthalpy: It is defined as the amount of energy required to break one mole of bonds of a
particular type between two atoms in a gaseous state. The unit of bond enthalpy is kJ mol–1
10. Bond Order : The Bond Order is given by the number of bonds between the two atoms in a
molecule. E.g.: Bond Order of O2= 2. With increase in bond order, bond enthalpy increases and
bond length decreases.
11. Resonance: According to the concept of resonance, whenever a single Lewis structure cannot
describe a molecule accurately, a number of structures with similar energy, positions of nuclei,
bonding and the non- bonding pairs of electrons are taken as the canonical structures of the
hybrid which describes the molecule accurately
12. Polarity of bonds: In case of heteronuclear molecules like HCl, the shared pair of electron
between the two atoms gets displaced more towards chlorine since the electronegativity of
chlorine is far greater than that of hydrogen. The resultant covalent bond is called a polar
covalent bond.
13. Dipole moment: As a result of polarization, the molecule possesses the dipole moment which
can be defined as the product of charge and the distance between the centers of positive and
negative charge. It is usually designated by a Greek letter ‗µ‘. Mathematically, it is expressed as
follows:
Dipole moment (µ ) = charge (Q) X distance of separation (r)
17. Molecular orbital. It gives electron probability distribution around a group of nuclei in a
molecule. They are filled in the same way as atomic orbitals. Molecular orbitals are formed by
linear combination of atomic orbitals.
18. Bonding molecular orbital. A molecular orbital that is formed by addition overlap (i.e., when
the lobes of atomic orbitals overlap with the same sign) of two atomic orbitals is known as
bonding molecular orbital. It is represented as
MO A B Its energy is lower than the atomic orbitals from which it is formed. It
favours bonding.
19. Anti-bonding molecular orbital. A molecular orbital that is obtained by the subtraction overlap
(i.e., when the lobes of atomic orbitals overlap with the opposite sign) of two atomic orbitals is
know as anti-bonding molecular orbital. It is represented as
* MO A B Its energy is higher than the atomic orbitals from which it is formed. It
22. Sigma ( ) molecular orbitals. A molecular orbital which is formed from the overlap of two s
atomic orbitlas or head to head overlap of one s and p-atomic orbitals or head to head overlap of
two p-atomic orbitals, is known as sigma molecular orbital.
23. pi ( ) molecular orbitals. A molecular orbital which is formed by lateral overlap of two
parallel p-orbitals is known as pi( ) molecular orbital.
24. Conditions for the Combination of Atomic Orbitals. The linear combination of atomic
orbitals takes place only if the following conditions are satisfied :
(i) The combining atomic orbitals must have same or nearly same energy.
(ii) The combining atomic orbitals must have the same symmetry about the molecular axis. By
convention, z-axis is taken as the molecular axis.
(iii) The combining atomic orbitals must overlap to the maximum extent. Greater the extent of
overlapping, the greater will be electron density between the nuclei of a molecular orbital.
25. Energy level Diagrams for Molecular Orbitals. The increasing order of energies of various
molecular orbitals for O2 and F2 is given below.
* * * * *
1s 1s 2s 2s 2 p z 2 p x 2 p y 2 p x 2 p y 2 p z
However, this sequence of energy levels of molecular orbitals is not correct for
remaining molecules Li2, Be2, B2, C2, N2. For instance, it has been observed
experimentally that for molecules such as B2, C2, N2 etc., the increasing order
of energies of various molecular orbitals is
* * * * *
1s 1s 2s 2s 2 p x 2 p y 2 p z 2 p x 2 p y 2 p z
these molecules.
5.States of Matter
3. Dipole -Induced Dipole Forces: This type of attractive forces operate between
the polar molecules having permanent dipole and the molecules lacking
permanent dipole. Permanent dipole of the polar molecule induces dipole on
the electrically neutral molecule by deforming its electronic cloud.Thus an
induced dipole is developed in the other molecule
.
4. Dispersion Forces or London Forces:Atoms and nonpolar molecules are
electrically symmetrical and have no dipole moment because their electronic
charge cloud is symmetrically distributed. But a dipole may develop
momentarily even in such atoms and molecules. This can be understood as
follows. Suppose we have two atoms ‗A‘ and ‗B‘ in the close vicinity of each
other (Fig. 5.1a NCERT page 133). It may so happen that momentarily
electronic charge distribution in one of the atoms, say ‗A‘, becomes
unsymmetrical i.e., the charge cloud is more on one side than the other (Fig.
5.1 b and c NCERT page 133). This results in the development of
instantaneous dipole on the atom ‗A‘ for a very short time. This instantaneous
or transient dipole distorts the electron density of the other atom ‗B‘, which is
close to it and as a consequence a dipole is induced in the atom ‗B‘. The
temporary dipoles of atom ‗A‘ and ‗B‘ attract each other. Similarly temporary
dipoles are induced in molecules also. This force of attraction was first
proposed by the German physicist Fritz London, and for this reason force of
attraction between two temporary dipoles is known as London force. Another
name for this force is dispersion force.
5. Hydrogen bond: Hydrogen bond is represented by a dotted line (– – –) while a
solid line represents the covalent bond. Thus, hydrogen bond can be defined as
the attractive force which binds hydrogen atom of one molecule with the
electronegative atom (F, O or N) of another molecule this is special case of
dipole-dipole interaction..
6. Boyleís Law (Pressure – Volume Relationship): At constant temperature, the
pressure of a fixed amount (i.e., number of moles n) of gas varies inversely
with its volume. This is known as Boyleís law.
1 1
pά (at constant T & V) i.e. p = K1 pV= K1 p1V1=p2V2
V V
p1 p 2
V1 V 2
7. Charles Law (Temperature – Volume Relationship): It states that pressure
remaining constant, the volume of a fixed mass of a gas is directly proportional
to its absolute temperature.i.e. V ά T (at constant P & V)
V V1 V 2
V =K2T =K2
T T1 T 2
8. Gay Lussacís Law (Pressure-Temperature Relationship): It states that at
constant volume, pressure of a fixed amount of a gas varies directly with the
temperature. Mathematically, . P ά T (at constant V & n)
P
p =K3T =K3
T
19. Significance of Vander wall parameter: Vander wall parameter a is the measure
of intermolecular forces while b is the measure of effective size of gaseous
molecules Unit of a = bar L3 mol-2 Unit of b = L mol-1
20. The deviation from ideal behaviour can be measured in terms of
compressibility factor Z, which is the ratio of product pV and nRT.
pV
Mathematically Z=
nRT
21. The temperature at which a real gas obeys ideal gas law over an appreciable
range of pressure is called Boyle temperature or Boyle point.
22. Critical temperature (TC)of a gas is highest temperature at which liquifaction
of the gas first occurs. Liquifaction of so called permanent gase Volume of one
mole of the gas at critical temperature is called critical volume (VC) and
pressure at this temperature is called critical pressure (pC). The critical
temperature, pressure and volume are called critical constants.
23. Surface tension is defined as the force acting per unit length perpendicular to
the line drawn on the surface of liquid. It is denoted by Greek letter γ . It has
dimensions of kg s–2 and in SI unit it is expressed as N m–1.
24. Viscosity is a measure of resistance to flow which arises due to the internal
friction between layers of fluid as they slip past one another while liquid flows.
Strong intermolecular forces between molecules hold them together and resist
movement of layers past one another. Greater the viscosity, the more slowly
the liquid flows. Viscosity of liquids decreases as the temperature rises because
at high temperature molecules have high kinetic energy and can overcome the
intermolecular forces to slip past one another between the layers.
25. Viscosity coefficient is the force when velocity gradient is unity and the area
of contact is unit area. Thus ‗ η ‘ is measure of viscosity. SI unit of viscosity
coefficient is 1 newton second per square metre (N s m–2) = pascal second (Pa s
= 1kg m–1s–1).
6.Thermodynamics
G TS
r G 2.303RT log K
Some Important Formulas(Thermodynamics)
∆U=q+w
ΔH = ΔU + pΔV
ΔH = ΔU + ΔngRT
Cp -CV=R
ΔrH=∑bondenthapiesreactants- ∑ bondenthapiesproducts
H fusion
∆S fusion =
Tm
G TS
r G = -nFEcell
Addition of Inert gas at const.pressure where the no. of gaseous moles are more
CHAPTER-8
REDOX REACTIONS
oxidation reduction
1. Addition of oxygen 1. Removal of oxygen
2. Removal of hydrogen 2. Addition of hydrogen
3. Addition of an electronegative 3. Removal of an electronegative
element element
4. Removal of an electropositive 4. Addition of an electropositive
element element
5. Loss of electron 5. Gain of electron
Oxidising agent: A reagent which can increase the oxidation number of an element
in a given substance. These reagents are called as oxidants also. Reducing agent:
A reagent which lowers the oxidation number of an element in a given substance.
These reagents are also called as reductants.
Redox reactions: Reactions which involve change in oxidation number of the
interacting species
Balancing of redox reactions:
Oxidation Number Method:
Write the net ionic equation for the reaction of potassium dichromate(VI),
K2Cr2O7 with sodium sulphite,Na2SO3, in an acid solution to give
chromium(III) ion and the sulphate ion.
Step 1: The skeletal ionic equation is:
2–( 2– 3+ 2–
Cr2O7 aq) + SO3 (aq) → Cr (aq)+ SO4 (aq)
Step 2: Assign oxidation numbers forCr and S
+6 –2 +4 –2 +3 +6 –2
2–( 2– 3+ 2–
Cr2O7 aq) + SO3 (aq) → Cr (aq)+ SO4 (aq)
Step 3: Calculate the increase anddecrease of oxidation number, and make them
equal:
+6 –2 +4 –2 +3 +6
2–( 2– 3+ 2–
Cr2O7 aq) + 3SO3 (aq) → 2Cr (aq)+ 3SO4 (aq)
+
Step 4: Balance the charge by adding H as the reaction occurs in theacidic
medium,
2–( 2– + 3+ 2–
Cr2O7 aq) + 3SO3 (aq) 8H → 2Cr (aq)+ 3SO4 (aq)
2H2O(l) O2(g)
The hydrogen prepared by this method is of very high purity. However, this
method is not commonly used because it is very expensive. This method is can be
used only at those places where the electricity is cheap.
2. By the reaction of steam on coke :-
C + H2O(g) CO + H2O
Water gas
Since the mixture of CO and H2 is used for the synthesis of methanol and a
number of hydrocarbons, it is also called synthesis gas or syn gas.
t The process of producing syn gas from coal or coke is called coal gasification.
CO + H2 + H2O CO2 + 2H2
Water gassteam
This reaction is called water gas shift reaction.
Properties of Hydrogen:-
Physical Properties:-
q It is slightly soluble in water (about 2 %)
r It is highly combustible and therefore should be handled carefully.
s It lightest substance. The weight of one litre hydrogen at NTP is only 0.0899 g.
Chemical properties:-Not very reactive due to high bond dissociation energy (435.88 kJ
-1
mol at 298.2 K)
(i)Combustion: - It burns with pale blue flame
2H2 (g) + O2 (g) 2H2O(l)
(ii) Reaction with metals:-Reactive metals like Na, K, Ca, Li and form hydrides.
Ca + H2 CaH2
Metals like Pt, Pd, Ni (elements of d block) form interstitial hydrides by absorbing
large volume of hydrogen. Such hydrogen is called ‘occluded hydrogen and this
property of adsorption of a gas by a metal is called occlusion.
(iii) Reaction with metal oxides:-Hydrogen reduces oxides of less active metals
to corresponding metal.
Fe3O4 + 4H23Fe + 4H2
CuO + H2 Cu + H2O
(iv) Reaction with non-metals:-
3H2 (g) + N2 (g) 2NH3(g) { Haber process}
H = - 92.6 kj/mole
95.7 pm O H H H
O O O
H 104.5° H
H H
Solid state H H
H
Structure of ice:-Ice has a highly ordered 3D
O
hydrogen bonded structure. Each oxygen atom H H H
is surrounded tetrahedrally by four other four
O O
other oxygen atoms at a distance of 276 pm
H H H H H
O O O
H H H H H
O O
H H H
Chemical Properties of water:- O
[i] AMPHOTERIC NATURE:-It has the ability H
Cl HO resin Cl re sin OH
Hard water Anion exchanger
Regeneration of resiners:
H H
95.0 pm 95.8 pm
147.5 pm 147.8 pm
90.2° 90.2°
101.9° 101.9°
H H
The main aim and advantage of hydrogen economy is to transmit energy in four of
hydrogen.
Chapter 10
The s- Block Element
Important points
Groups (1 & 2) belong to the s-block of the Periodic Table.
Group 1 consists of : lithium, sodium, potassium, rubidium, caesium and francium
and collectively known as the alkali metals.
Group 2 include : beryllium, magnesium,calcium, strontium, barium and radium.
Except Beryllium they are known as alkaline
Physical properties-
a) Large atomic radii: The atomic radii of alkali metals are the largest in their
respective periods. These increase as we travel down the group.
b) Large ionic radii: The ionic radii increase as we move down the group due to the
addition of a new energy shell with each succeeding element.
c) Low ionization enthalpy: The ionization enthalpies decrease as we move down
the group.The ionization enthalpies of the alkali metals are the lowest due to
loosely held s- electron.
d) Hydration enthalpy: It decreases with the increase in ionic radii.The hydration
enthalpy of Li ion is the maximum and the hydration enthalpy of Cs ion is the
minimum.
e) Oxidation state: The alkali metals exhibit oxidation state of +1 in their
compounds and are strongly electropositive in character. The electropositive
character increases from Li to Cs.
f) Metallic character: The metallic character increases down the group.
g) Melting point and boiling point:: The m p and b p of alkali metals are very low
and decrease with increase in atomic number.
h) Nature of bonds formed: These metals form ionic bonds. The ionic character
increases as we down the group.
i) Flame colouration: All the alkali metals impart a charactersistic colour to the
flame.
j) Photoelectric effect: Alkali metals (except Li) exhibits photoelectric effect.
Chemical features of alkali metals:
a) Reducing character: As the ionization enthalpies of the alkali metals decrease
down the group their reducing character or reactivity in the gaseous state
increases down the group. i.e., Li < Na < K < Rb < Cs .
b) Reaction with dihydrogen: Alkali metals react with dry hydrogen at about
673 K to form crystalline hydrides which are ionic in nature and have high
melting points.
Heat
+ -
2 M + H2 2M H
c) Oxides and hydroxides: Alkali metals when burnt in air form different
compounds, for example the alkali metals on reaction with limited quantity of
oxygen form normal oxides ( M2O) M= Li, Na, K, Rb, Cs
5) Reaction with halogens: The members of the family combine with halogen to
form corresponding halides which are ionic crystalline solids.
Reactivity of alkali metls with particular halogen increases from Li to Cs.
6) Reaction with water: Alkali metals react with water and other compounds
containing acidic hydrogen atoms such as hydrogen halides, acetylene etc. to
liberate hydrogen gas.
7) Solubility in liquid ammonia: All alkali metals dissolve in liquid ammonia
giving deep blue solutions which are conducting in nature.
8) Reaction with sulphur and phosphorus: Alkali metals react with sulphur and
phosphorus on heating to form sulphides and phosphides respectively.
Diagonal relationship between Li and Al
Li resembles Mg mainly due to similarity in sizes of their atoms and ions. The main
points of similarity are:
4) Both are quite hard.
5) Both LiOH and Mg(OH)2 are weak bases.
6) Carbonates of both on heating decompose to produce oxides and
carbondioxide.
7) Both react with nitrogen to give ionic nitrides.
8) Nitrates of both decompose on heating to give oxides.
9) Both Li and Mg do not form solid bicarbonates.
10) Because of covalent character LiCl and MgCl2 are soluble in ethanol.
11) The hydroxides, bicarbonates and fluorides of both Li and Mg are sparingly
soluble in water.
Biological importance of Na and K
Sodium ions participate in the transmission of nerve signals.
Sodium ions also regulate flow of water across the cell membranes and in
transport of sugars and amino acids into the cells.
Potassium ions are the most abundant cations within cell fluids, where they
activate many enzymes, participate in oxidation of glucose to produce ATP.
Potassium ions in combination with sodium ions are responsible for
transmission of nerve signals.
The functional features of nerve cells depend upon the sodium potassium ion
gradient that is established in the cell.
Group 2 elements: Alkaline earth metals
Atomic radii : The atomic radii of alkaline earth metals are fairly large though
smaller than the corresponding alkali metals and they increase down the group. This
is because on moving down the group, atomic radii increase primarily due to the
addition of an extra shell of electrons in each succeeding element.
Ionic radii: the atoms of these elements form divalent ions which show the same
trend of increase in their size down the group.
Ionization enthalpy: The alkaline earth metals have fairly low Ionizations
enthalpies though greater than those of the corresponding elements of group 1 and
this value decreases down the group.
(d) Hydration enthalpy: the Hydration enthalpies of alkaline earth metal ion
decrease as the size of the metal ion increases down the
2+ 2+ 2+ 2+ 2+
Group Be >Mg >Ca >Sr >Ba
(e) Oxidation State: All the members of the family exhibit +2 oxidation state in their
2+
compounded and the form divalent cations (M )
(f) Electro negativity : The electro negativity values of alkaline earth metals are
quite close to those of alkali metals, though slightly more.
(g) Metallic Character : Alkaline earth metals have stronger metallic bonds as
compared to the alkali metals present in the same period.
(h) Melting and boiling point : The melting and Boiling points of these metals are
higher than those of alkali metals present in the same period.
(i) Colouration to the flame : With the exceptio9n of beryllium and magnesium, the
rest of the elements impart characters in colour to the same flame. For example,
Be Mg Ca Sr Ba Ra
- - Brick Red Crimson Grassy Green Crimson
J) Complex formation: Generally the members do not form complexes. However,
smaller ions ( Be & Mg Ions) form complexes with the electron donor species
(v) Formation of organo-metallic compounds: Both beryllium and magnesium
form a number of organo-metallic compounds containing M-C bond with certain
organic compounds. For example, magnesium reacts with alkyl halide in the
presence of dry ether to give Grignard reagent.
(vi) Reducing character: Alkaline earth metals are weak reducing agent than the
corresponding alkali metals which have lower ionization enthalpies and
comparatively bigger atomic sizes.
(vii) Reaction with oxygen: With the exception of Ba and Ra which form
peroxides ( MO2) rest of the metals form normal oxides (MO) on heating with
excess of oxygen.
(viii) Reaction with halogens: The members of the family combine directly with
halogen at appropriate temperature to form corresponding halides.
(ix) Reaction with water: The members of this group are less reactive towards
water as compared to the corresponding alkali metals because these are less
electropositive in nature.
(x) Reaction with hydrogen: The members except Be combine with hydrogen
directly upon heating to form metal hydrides.
Uses of some important compounds:-
(i) Caustic soda:
It is used: in soap, paper, textile, petroleum
industry ii) Sodium carbonate
It is used:
a) in glass and soap industry
b) in paper making and textile manufacturing
c) in paint and dye stuffs
d) in metal refining
(c) in production of sodium compounds such as borax, caustic soda, sodium
phosphate etc.
iii) Quick lime:
It is used:
(d) in the preparation of cement, glass and calcium carbide.
(e) In the purification of sugar
c. In softening of hard water d. As a flux in the extraction of metal
26. Lime stone: It is used
as building material
in the manufacture of quick lime
in Solvay process to prepare Na2CO3 as it is a source of CO2
in metallurgy for the extraction of iron
in toothpaste and certain cosmetics
27. Cement: It is an important building material. It is used in concrete and reinforced
concrete, in plastering and in the construction of bridges, dams and buildings.
28. Plaster of paris: It is used
in making moulds for pottery and ceramics etc.
in surgical bandages for setting broken bones of the body
for making statues, models, decorative materials and black board chalk.
Biological importance of Ca and Mg
Magnesium ions are concentrated in animal cells and Calcium ions are
concentrated in body fluids, outside the cell.
All enzymes that utilize ATP in phosphate transfer require magnesium ion
as cofactor.
In green plants magnesium is present in chlorophyll.
Calcium and magnesium ions are also essential for the transmission of
impulses along nerve fibres.
Calcium ions are important in blood clotting and are required to trigger the
contraction of muscles.
Calcium ions also regulate the beating of the heart.
CHAPTER 11
Elements in which the last electron enters in the any one of the three p- orbital of
their outermost shells – p-block elements
•
Gen. electronic configuration of outer shell is ns2np1-6
The inner core of e-config.may differ which greatly influences their physical & to
some extent chemical properties.
• The block of elements in the periodic table consisting of the main groups :
• Group 13 (B to Tl)
• Group14 (C to Pb)
• Group15 (N to Bi)
• Group 16 (O to Po)
• Group17 (F to At)
(1) Members at the top and on the right of the p-block are nonmetals (C, N, P, O,
F, S, Cl, Br, I, At).
(2) Those on the left and at the bottom are metals (Al, Ga, In,Tl, Sn, Pb, Sb Bi, Po).
(3) Between the two, from the top left to bottom right, lie an ill-defined group of
metalloid elements (B, Si, Ge, As, Te)
• group members: boron (B), aluminum (Al), gallium (Ga), indium (In)&
thallium (Tl) . All, except boron, are metals.
• Boron compounds are electron deficient, they are lack of an octet of electrons
about the B atom .
• - Boron oxide is acidic (it reacts readily with water to form boric acid)
• In other words, effective nuclear charge increases and thus, size decreases.
Therefore, the elements of this group have smaller size than the corresponding
elements of second group.
• On moving down the group both atomic and ionic radii are expected to
increase due to the addition of new shells. However, the observed atomic
radius of Al (143 pm) is slightly more than that of Ga (l35 pm).
Ionization energies
The first ionization energies of group 13 elements are less than the corresponding
members of the alkaline earths.
The sharp decrease in I.E. from B to Al is due to increase in size. In case of Ga, there
are ten d-electrons in its inner electronic configuration.
The very high value of 3rd I. E. of thallium indicates that +3 O.N. state is not stable,
rather +1 is more stable for thallium .
Oxidation states
The common oxidation states of group 13 elements are +3 and + l .The stability of
the + 1 oxidation state increases in the sequence Al <Ga< In <Tl, Due to Inert pair
effect.
Element B Al Ga In Tl
Oxidation state +3 +3 +3, +1 +3, +1 +3, +1
All elements in their compounds exhibit the oxidation state of + 3 and +1.
Hydrides
• None of the group 13 elements reacts directly with hydrogen. However, a no.
of hydrides of these elements have been prepared by indirect methods. The
boron hydrides are called boranes& classified in two series: (a) BnHn+4
called nidoboranes (b) BnHn+6 called arachnoboranes
• INUDUSTRIAL PREPERATION :-
• Laboratory method:
i) Lower boranes are colourless gases while higher boranes are volatile liquids
or solids.
ii) They undergo spontaneous combustion in air due to strong affinity of boron
for oxygen.
iii) Boranes react with alkali metal hydrides in diethyl ether to form
borohydride complexes.
• Borazine has a cyclic structure similar to benzene and thus is called inorganic
benzene
• The other elements of this group form only a few stable hydrides. The thermal
stability decreases as we move down the group.
• AlH3 is a colourless solid polymerized via Al - H - Al bridging units. These
hydrides are weak Lewis acids and readily form adducts with strong Lewis
base (B:) to give compounds of the type MH3 (M = Al or Ga). They also form
complex-tetrahydrido anions, [MH4]-. The most important tetrahydrido
compound is Li[AlH4]
ether
4LiH + AlCl3 ―――→ LiAlH4 + 3LiCl
• M2O3& M(OH)3
• Boron and silicon exhibit the typical properties of non-metals. These do not
form cations. Both exist in amorphous as well as crystalline forms.
• Boron oxide (B2O3) and silica (SiO2) both are acidic and dissolve in alkali
solutions to form borates and silicates respectively.
• The chlorides of both B and Si get hydrolyzed by water to boric acid and
silicic acid respectively.
The hydrides of Boron and Silicon are quite stable. Numerous volatile
hydrides are also known which catch fire on exposure to air and are easily
hydrolyzed.
Both elements are semiconductors.
2. Al, Ga. In and T1 ions exist as octahedral aqua ions, [M(OH2)6]3+ in aqueous
solution and many salts like halides, sulphates, nitrates and perchlorates exist as
hydrates.
3. Aluminiumsulphate forms double salts - called alum, having the general formula
Group 14 includes carbon (C), silicon (Si), germanium (Ge), tin (Sn) and lead (Pb).
Chemical properties:-
Carbon and silicon mostly show +4 oxidation state. Germanium forms stable
compounds in +4 state and only few compounds in +2 state.
Tin forms compounds in both oxidation states. Lead compounds in +2 state are stable
and in +4 state are strong oxidizing agents.
Since carbon does not have d-orbitals and hence cannot expand its coordination
number beyond 4
SiCl4+4H2O Si(OH)4+4HCl
Silicic acid
Diamond:-In diamond each carbon atom under goes SP3hybridisation. Each carbon is
tetrahedrally linked to four other carbon atoms.
2C+O2(g) → 2CO(g)
Each silicon atom is covalently bonded in a tetrahedral manner to four oxygen atoms.
Position Isomerism : Compounds which have the same structure of carbon chain but
differ in position of double or triple bonds or functional group are called position
isomers and this phenomenon is called Position Isomerism. e g
CH3-CH2-CH=CH2 CH3-CH = CH – CH3
Functional Isomerism :Compounds which have the same molecular formula but
different functional group are called functional isomers and this phenomenon is
called functional Isomerism. e g
CH3 – CH2 – OH CH3 – O – CH3
Metamerism:It is due to the presence of different alkyl groups on either side of
functional group in the molecule. Ex. C4H10O represents C2H5OC2H5 and
CH3OC3H7.
FISSION OF COVALENT BOND
Heterolytic cleavage: In this cleavage the bond breaks in such a way that the shared
pair of electron remains with one of the fragments.
+
H3C – Br CH3 + Br-
Homolytic Cleavage: In this cleavage the shared pair of electron goes with each of
the bonded atom.
R– X R. + X.
Alkyl free radical
Nucleophiles : A reagent that brings an electron pair is called nucleophile ie nucleus
seeking e g -OH , -CN
Electrophiles: A reagent that takes away electron pair is called electrophile I e
electron seeking e g > C= O , R3C – X
Inductive Effect: The displacement of the electron along the chain of the carbon
atoms due to presence of an atom or group at the end of the chain.
ɗ+++ ɗ ++ ɗ+
CH3- C H2 CH2 Cl
Resonance Effect : The polarity produced in the molecule by the interaction of two
pi bonds or between a pi bond and lone pair of electron present on an adjacent atom.
There are two types of resonance effect:
1) Positive resonance effect : In this effect the transfer of electrons is away from
an atom or substituent group attached to the conjugated system.
The atoms or groups which shows +R effect are halogens,-OH , -OR,-
NH2
2) Negative resonance effect : In this effect the transfer of electrons is towards
the atom or substituent group attached to the conjugated system.
The atoms or groups which shows -R effect are –COOH , -CHO , -CN
METHODS OF PURIFICATION OF ORGANIC COMPOUNDS :
Sublimation : This method is used to separate the sublimable compounds from non
sublimable compounds.
Crystallisation: This method is based on the difference in the solubilities of
compound and impurities in a suitable solvent. The impure compound is dissolved in
solvent and heated at higher temp .On cooling, from the hot and conc solution pure
compounds crystallizes out.
Distillation: This method is used to separate volatile liquids from non volatile liquids
and liquids having sufficient difference in their boiling points.
Fractional distillation: If the boiling points of two liquids is not much , they are
separated by this method.
Distillation under reduced pressure : This method is used to purify liquids having
high boiling points and decomposes at or below their boiling points.
Steam distillation : This method is used to separate substances which are steam
volatile and are immiscible with water.
Differential Extraction: When an organic compound is present in an aqueous
medium it is separated by shaking it with organic solvent in which it is more soluble
than in water. The aqueous solution is mixed with organic solvent in a separating
funnel and shaken for sometimes and then allowed to stand for some time .when
organic solvent and water form two separate layers the lower layer is run out by
opening the tap of funnel and organic layer is separated. the process is repeated
several times and pure organic compound is separated.
Chromatography :This technique is used to separate mixtures in to their
components ,purify the compounds and test the purity of compounds.It is classified
as
Adsorption Chromatography : It is based on the fact that different compounds are
adsorbed on an adsorbent to different degrees. Silica jel or alumina is used as
adsorbents.
Partition Chromatography : It is based on the continuous differential portioning of
components of a mixture between stationary and mobile phase.
QUALITATIVE ANALYSIS OF ORGANIC COMPOUNDS
Detection of Carbon and Hydrogen: The Carbon and Hydrogen present in the
Organic compound is detected by heating the compound with Copper II oxide in a
hard glass tube when carbon present in the compound is oxidized to CO2 which can
be tested with lime Water and Hydrogenis converted to water which can be tested
with anhydrous copper sulphate which turns blue.
C + CuO 2Cu + CO2
2 H +CuO Cu + H2O
CO2 +Ca (OH )2 CaCO3 + H2O
5H2O + CuSO4 CuSO4.5H2O
DETECTION OF OTHER ELEMENTS
Sodium Fusion Extract: A small piece of dry Sodium metal is heated with a organic
compound in a fusion tube for 2 -3 minutes and the red hot tube is plunged in to
distilled water contained in a china dish. The content of the china dish is boiled
,cooled and filtered. The filtrate is known as Sodium fusion extract.
Test for Nitrogen : The sodium fusion extract is boiled with iron II sulphate and
then acidified with Concsulphuric acid , the formation of Prussian blue colour
confirms the presence of nitrogen.
6CN- + Fe2+ [Fe(CN)6] 4-
3[Fe(CN)6] 4-+ 4Fe3+ xH O
2 Fe4[Fe(CN)6] 3.xH2O
Test for Sulphur: the sodium fusion extract is acidified with acetic acid and lead
acetate is added to it. A black precipitate of lead sulphide indicates the presence of
sulphur. S2- + Pb2+ PbS
Black
Test for halogens:The sodium fusion extract is acidified with nitric acid and then
treated with silver nitrate. A white precipitate, soluble in ammonium hydroxide
shows the presence of chlorine, a yellowish ppt. sparingly soluble in ammonium
hydroxide shows the presence of bromine, a yellowish ppt. insoluble in ammonium
hydroxide shows the presence of iodine.
X- + Ag+ AgX
QUANTITIVE ANALYSIS(Carbon and Hydrogen)
Let the mass of organic compound be m g. Mass of water and carbon dioxide
produced be m1 and m2 g respectively;
% of carbon = 12 x m2 x 100
44 x m
% of hydrogen = 2 x m1 x 100
18 x m
Nitrogen
DUMAS METHOD: A known mass of organic compound is heated with excess of
CuO in an atmosphere of CO2, when nitrogen of the organic compound is converted
into N2 gas. The volume of N2 thus obtained is converted into STP and the
percentage of nitrogen determined by applying the equation:
Volume of Nitrogen at STP = P1V1 x 273
760 x T1
%N = 28 x vol of N2 at STP x 100
22400 x mass of the substance taken
KJELDAHL’S METHOD: A known mass of organic compound is heated with
conc. H2SO4 in presence of K2SO4 and little CuSO4 or Hg in a long necked flask
called Kjeldahl‘s flask when nitrogen present in the organic compound is
quantitatively converted into (NH4)2SO4. (NH4)2SO4 thus obtained is boiled with
excess of NaOH solution to liberate NH3 gas which is absorbed in a known excess of
a standard acid such as H2SO4 or HCl.
The vol of acid unused is found by titration against a standard alkali solution. From
the vol of the acid used, the percentage of nitrogen is determined by applying the
equation,
%N= 1.4 x Molarity of the acid x Basicity of the acid x Vol of the acid used
Mass of the substance taken
Halogens
Carius method:
A known mass of an organic compound is heated with fuming nitric acid in the
presence of silver nitrate contained in a hard glass test tube known as carius tube in a
furnace. Carbon and hydrogen present in the compound are oxidized to carbon
dioxide and water. The halogen present forms the corresponding silver halide. It is
filtered, dried, and weighed.
Let the mass of the organic compound taken = m g
Mass of AgX formed = m1 g
1 mol of AgX contains 1 mol of of X
Mass of halogen in m1 g of AgX
= at mass of X xm1 g
Molecular mass of AgX
% of halogen
=at mass of X xm1 g x 100 %
Molecular mass of AgX x m
Sulphur
Let the mass of the organic compound taken = m g
Mass of BaSO4 formed = m1 g
% of sulphur = 32 x m1 x 100 %
233 x m
Phosphorous
Let the mass of the organic compound taken = m g
Mass of ammonium phosphomolydate = m1 g
% of phosphorous = 31 x m1 x 100 %
1877 x m
Oxygen
Let the mass of the organic compound taken = m g
Mass of CO2= m1 g
% of oxygen = 32 x m1 x 100 %
44 x m
CHAPTER 13
HYDROCARBON
Hydrocarbons are composed of Carbon and hydrogen.
The important fuels like Petrol, kerosene, coal gas, CNG, LPG etc. are all
hydrocarbons or their mixture.
Sources:
Petroleum and natural gas are the major sources of aliphatic hydrocarbon while coal is an
important source of aromatic hydrocarbons. The oil trapped inside the rocks is known as
petroleum. PETRA – ROCK, OLEUM – OIL. The oil in the petroleum field is covered with
a gaseous mixture known as natural gas. The main constituents of the natural gas are
methane, ethane, propane and butane.
CLASSIFICATION OF HYDROCARBONS:
HYDROCARBON
Alicyclic Aromatic
Alkanes Alkenes Alkyne
RX +Zn+Rx R –R +ZnX2
From Grignard reagent (RMgX)
RMgX+HOH RH+Mg(OH)X
RMgX+R'OH RH+ Mg(OR')X
RMgX+R'NH2 RH+ Mg(NHR')X
Ni /
R C CH H2 R CH2 CH3
Physical Properties:-
(1) Nature:- Non-Polar due to covalent nature of C—C bond and C—H bond. C—
C bond enrgy = 83 kj/mole and C—H bond energy = 99 kj/mole.
C1—C4 = gases, C5—C17 = colourless odourless liquid and > C17 = Solid.
(2) Solubility:- Like dissolve like
Viz, Polar compounds dissolve in polar solvent and Non-Polar compound dissolve in
non polar solvent.
(3) Boiling point:- Low boiling point due to non polar in nature.
The molecules are held together only by weak Van der Waalls‘ forces.
Since we known that the magnitude of Van der Waalls‘ forces is directly
proportional to the molecular size. Therefore, the boiling point increases with
increase the molecular size i.e. with increase in number of carbon atoms.
Note:- T he boiling points of the branched chain a lkanes are less than the straight
chain isomers.
This is due to the fact that branching of the chain makes the molecule more
compact and thereby decreases the surface area and consequently, the magnitudes
of
Van der Waals‘ forces also decrease.
CH3CH2CH2CH2CH3 H3 C — CH — CH2 CH3 CH3
(4)boiling point =
Melting 309 K t he
point:- melting point of Alkanes do
iso-pentane CHnot
3
show
regular variation with boiling point
increase = 301 K size. The
in molecular Alkanes
with even number of
neo-pentane
carbon atoms having higher melting point a s compared to those KA lkanes having
boiling point = 282.5
immediately next lower and immediately next higher odd number of carbon atoms.
Chemical properties
Combustion:- CH4 2 O2 CO2 2H2O
H 217.0 K cal/mole
Oxidation:-
Cu
CH4 O2 2 CH 3OH
573 K
Mo2O3
CH4 O2 HCHO H2O
Methanal
Substitution:-
Halogenation:-
UV
CH4 + Cl2 CH3 Cl + HCl
UV UV
UV
CH3Cl CH2Cl2 CHCl3 CCl4
Note:- Iodination is a reversible reaction. So it is carried out by heating alkane in
the presence of some oxidizing agent like iodic acid (HIO 3) or nitric acid (HNO3) or
mercuric oxide (HgO) which oxidizes HI formed during the reaction.
Noted:- Fluorination of alkane takes place explosively resulting even in the rupture
of C—C bond in higher alkanes.
Features of Halogenations:-
(i) The reactivity of Halogens:- F2 > Cl2 > Br2 > I2.
(ii) The rate of replacement of Hydrogens of alkanes is:
3° > 2° > 1°
C l2
CH 3CH2CH 2CH3 C H 3CH2CH 2CH 2Cl + CH 3CH 2CH2CH3
hv
n - Butane Cl
CH3
CH3 C CH3
1
°
CH3 3° 1°
Cl2
Cl
° CH - CH3
1
CH3 h 36% (3°)
CH3
CH - CH2 Cl
Isobutane
CH3
64% (1°)
Cl Cl Cl CCl
l2 2
CH3 Cl CH3C
Nitration:- l
The reaction takes places by free radicals mechanism at high temp (4500C).
At high temp C—C bond is also broken so that mixture of nitroalkanes is obtained.
450°C
CH3CH2CH3 CH3CH2CH2NO 2 + CH3CHCH3 + CH3CH2NO2+ CH3NO 2
Conc. HNO3
NO 2
25% 40% 10% 25%
The reaction occurs as:
4500C
HO-NO2 Homolytic fission
HOo + oNO2
RH + 0OH Ro + HOH
Ro + oNO2 RNO2
Sulphonation:- replacement of hydrogen atom of alkane by –SO3H group.
CH3
CH3
oleum
CH CH3 CH3 C CH3
CH3
SO 3H
4500C
The reaction occurs as: Homolytic fission
HO-SO3 HOo + oSO3H
RH + 0OH Ro + HOH
Ro + oSO3H RSO3H
Isomerization:-
CH3
AlCl3 / HCl
H3C(CH2) 3CH3 H3CCHCH2CH3
Aromatization:-
Cr2 O3
H3 C(CH2)4 CH3
773 K
Hexane 10-20 atm Benzene
This method is also called dehydrogenation or reforming
Similarly, heptane gives toluene, n-Octane give o-xylene and 2, methyl heptane give
m-xylene.
Thermal decomposition or Pyrolysis or cracking or Fragmentation: - when higher
alkanes are heated at high temp (about 700-800k) in the presence of alumina or silica
catalysts, the alkanes break down to lower alkanes and alkenes.
CH3-CH2-CH3 CH3-CH-CH2 + CH3-CH3 + C2H4 + CH4
Action of steam:- catalyst: nickel, alumina Al2O3
1000 0C
CH4 + H2O(Steam) CO + 3H2
This reaction is used for the industrial preparation of hydrogen from natural gas.
8. Isomerisation:-
CONFORMATIONAL ISOMERISM:
The different molecular arrangements arising as a result of rotation around carbon
carbon single bonds are called conformational isomers or rotational isomers and the
phenomenon is called conformational isomerism.
Numerous possible arrangements of ethane are possible. Two extreme conformations
are known. These are eclipsed conformation and staggered conformation.
SAWHORSE REPRESENTATION
H H
H
H H
H
H H
H H
H
H
STAGGERED ECLIPSED
NEWMAN PROJECTION
H
H H
H
H
H H
H
H H H
H
Preparation:-
1. From Alkynes:- Alkynes on partial reduction with Partially deactivated
palladised charcoal known as Lindlar’s catalyst give alkynes.
–
H H OH H
OH H H H
C C Slow
C
C C + Br- + H 2O
C
H H Br
H
H H H H
H Br
–
Transition state
3. From Dihaloalkanes: - dehalogenation
Zn/HOAC H H
C C + ZnBr2
H H
H H
H C C H
H H
Br Br Na
C C + I2 +2 NaBr
acetone
H H
Mechanism 300° C
H+
CH3 - CH2 - CH2 - OH +
CH3 - CH2 - CH 2 - O H2 -H2O
CH3 CH2 CH2
CH3 CH CH2 H
CH3 CH CH2
1 propen e
H
loss of H2O
OH CH3 C CH CH3
1 2 from 1, 2
H3C C CH2 CH3 position CH3
(major)
CH3 loss of H2O
CH3 C CH2 CH3
3
from 1, 3
position CH2
(Minor)
Chemical Properties:-
Addition Reaction:- Alkene show electrophilic addition reaction.
1. Addition of Hydrogen:-
H2 /Ni
RCH= CH2 RC H2CH3
2. Addition of Halogens:-
CH2 - CH2
CCl4 | |
CH2 = CH2 + Br2 Br Br
Solvent
H2O
CH2 CH2 Br2 Br — CH2 — CH2 — OH HBr
Solvent
Noted:- peroxide effect is applicable only to HBr and not to HF, HCl and HI.
Addition of HF, HCl and HI takes place according to Markovnikov‘s rule even in the
presence of peroxide.
4. Addition of water (Hydration):- Acid catalyzed addition of water
65-70% H2SO4 CH3
CH 3 CH
CH3 CH CH2 + H2O
OH
CH3
H2O/H CH3
C CH2 C CH3
CH3
CH3
OH
Oxidation:-
Combustion:- CO2 + H2O
Hydroboration–oxidation:- Alkanes react with diborane to form trialkyl boranes
which on oxidation with alkaline H2O2 give alcohols.
BH3 H2O2 /OH-
3CH2 = CH2 CH3CH2 3 B 3CH3CH2OH
Triethylborane Ethyl alcohol
Oxymercuration–demercuration:-
Hg(OAC)2 NaBH4
H2C CH2 CH2 CH2 Hg OAC CH3CH2OH + Hg
THF, H2O
OH OH
3 C C H2O ++O4H O
+ 2KMnO Cold 3 C C + 2 MnO2 + 2 KOH
4 2
From KMnO4 OH OH
(pink Colour) (Colourless)
(i) Alk.KMnO4
CH3 CH CH2 CH3 COOH + CO2 + H2O
(ii) H+
O CH3
O3 O O
CH3CH2CH CCH3 CH 3CH 2CH C Zn/H2O
CH 3CH2CH + CH 3CCH 3 + Zn(OH)2
CH3 O O CH3
Ozonide
Noted:- Bromine water test and Baeyer‘s test are used to detect the presence of
double bond while ozonolysis is used to detect the position of double bond.
Alkynes
Unsaturated hydrocarbon which have triple bond.
General molecular formula CnH2n–2
sp hybridization
Shows chain, positional and functional isomerism
Preparation:-
From vicinal dihalides: - dehalogenation
2KOH (alc)
CH3 CH CH2 CH3 C CH + 2KBr + 2H2O
Br Br
Chemical Properties:-
Addition Reaction:- Alkyne show electrophilic addition reaction.
Addition of Hydrogen:- Hydrogenation.
Ni
CH3 C CH + 2H2 CH3 CH2 CH3
Propyne
Noted:- It may be noted that the hydrogenation can be controlled at the alkene stage
only. This is possible by using a Lindlar’s catalysts or sodium in liquid NH3 at 200k
temp..
Noted:- It may be again noted that the catalytic reduction of alkynes in the presence
of Lindlar‘s catalyst gives cis-alkenes while in the presence of sodium in liquid NH3
(Birch reduction) gives trans-alkenes.
H3 C CH3
H2 / Lindlar
CH3 C C CH3 C C
Catalyst H
H
Addition of Halogens:- Br Br
| |
2Br 2
HC CH H C C H
| |
Br Br
Addition of hydrogen halides:-
HC CH 2HBr CH3CH Br2
Polymerisation-
a. Linear polymerisation: of ethyne gives polyacetylene or polyethyne
which is a high molecular weight polyene containing repeating units of
(CH = CH – CH = CH ) and can be represented as —(CH = CH – CH =
CH)n —
b. Cyclic polymerization- results in the formation of aromatic compound.
Acidity of Alkynes- Terminal alkynes are acidic in nature.
Alkanes, alkenes and alkynes follow the following trend in their acidic
behaviour :
AROMATIC HYDROCARBON
Aromatic compounds containing benzene ring are known as benzenoids and those
not containing a benzene ring are known as non-benzenoids.
Structure of Benzene- Kekulé structure
The orbital overlapping picture benzene- All the six carbon atoms in benzene are
sp2 hybridized and these hybrid orbitals form sigma bonds.
The unhybridised p orbital of carbon atoms are close enough to form a π bond by
lateral overlap.
The six π electrons are thus delocalised and can move freely about the six carbon
nuclei. The delocalised π electron cloud is attracted more strongly by the nuclei of
the carbon atoms than the electron cloud localized between two carbon atoms.
Therefore, presence of delocalised π electrons in benzene makes it more stable .
Aromaticity:- The compounds that follow the following features are to be considered
aromatic.
(i) Planarity
(ii) Complete delocalisation of the π electrons in the ring
(iii) Presence of (4n + 2) π electrons in the ring where n is an integer (n = 0, 1,
2, . . .). This is often referred to as Hückel Rule.
Preparation of Benzene:
(i) Cyclic polymerisation of ethyne:
(ii) Decarboxylation of aromatic acids:
(iii) Reduction of phenol: Phenol is reduced to benzene by passing its vapours over
heated zinc dust
Physical properties:
1. Aromatic hydrocarbons are non- polar molecules and are usually colourless
liquids or solids with a characteristic aroma.
2. Aromatic hydrocarbons are immiscible with water but are readily miscible
with organic solvents.
3. They burn with sooty flame.
Chemical properties
Arenes are characterised by electrophilic substitution reactions proceed via the
following three steps:
(a) Generation of the eletrophile
(b) Formation of carbocation intermediate
(c) Removal of proton from the carbocation intermediate
Nitration
Halogenation
+Cl2
Anhyd. AlCl3
Chloro benzene
Sulphonation
Friedel-Crafts alkylation
+C2H5Cl
Ethyl benzene
Anhyd. AlCl3
Friedel-Crafts acylation
+CH3COCl
Anhyd. AlCl3
acetphenone
3. Ortho and para directing groups and deactivating- Halogens because of their
strong – I effect, overall electron density on benzene ring decreases. However,
CHAPTER 14
ENVIRONMENTAL CHEMISTRY
In a greenhouse,visible light passes through the transparent glass and heats up the soil
and the plants.The warm soil and plants emit infrared rays,it partly reflects and partly
absorbs these radiations,this mechanism keeps the energy of the sun trapped in the
greenhouse.
ACID RAIN:When the pH of the rain water drops below5.6, it is called acid rain.Acid
rain is harmful for agriculture, trees and plants as it dissolves and washes away
nutrients needed for their growth. It causes respiratory ailments
in human beings and animals. When acid rain falls and flows as ground water to reach
rivers, lakes etc. it affects plants and animal life in aquatic ecosystem
SMOG:The word smog is derived from smoke and fog.There are two types of
smog:classical and photochemical smog. Classical smog occurs in cool humid climate.
It is a mixture of smoke, fog and sulphur dioxide. It is also called reducing smog.
Whereas photochemical smog occurs in warm and dry sunny climate. It has high
concentration of oxidizing agents and therefore ,it is also called as oxidizing smog
OZONE HOLE:Depletion of ozone layer is known as ozone hole.
EFFECTS OF DEPLETION OF THE OZONE LAYER: With the depletion of ozone
layer, more UV radiation filters into troposphere. UV radiations lead to ageing of skin,
cataract, sunburn, skin cancer, killing of many phytoplanktons, damage to fish
productivity etc
WATER POLLUTION:-contamination of water by foreign substances which make it
harmful for health of animals or plants or aquatic life and make it unfit for domestic,
industrial and agriculture use.
SOURCES/ CAUSES OF WATER POLLUTION-
Sewage and domestic wastes
Industrial effluents
Agriculture effluents
Siltation-mixing of soil or rock into water
Thermal pollutants
Radioactive discharge
EUTROPHICATION:The process in which nutrient enriched water bodies support
a dense plant population, which kills animal life by depriving it of oxygen and
results in subsequent loss of biodiversity is known as Eutrophication
BOD: The amount of oxygen required by bacteria to break down the organic matter
present in a certain volume of a sample of water, is called Biochemical Oxygen Demand
(BOD)
SOIL POLLUTION: Insecticides, pesticides and herbicides cause soil pollution.
GREEN CHEMISTRY: Green chemistry is a way of thinking and is about utilizing
the existing knowledge and principles of chemistry and other
sciences to reduce the adverse impact on environment. Green chemistry is a
production process that would bring out minimum pollution or deterioration to the
environment..Utilization of existing knowledge base for reducing the chemical
hazards along with the development of activities is the foundation of
green chemistry.