Molecular Orbital Theory

Salient Features of Molecular Orbital (MO) Theory

When two atomic orbitals combine or overlap, they lose their identity and form new orbitals. The new orbitals formed are called molecular orbitals. The electrons in a molecule are present in various molecular orbitals as the electrons of atoms are present in various atomic orbitals. An electron in an atomic orbital is under the influence of only one nucleus while in a molecular orbital, it is under the influence of two or more nuclei depending upon the number of atoms in the molecule. Thus, an atomic orbital is mono-centric while a molecular orbital is polycentric. The number of molecular orbitals formed is equal to the number of combining atomic orbitals. When two atomic orbitals combine, two molecular orbitals are formed. One is called bonding molecular orbital and the other is called antibonding molecular orbital. The bonding MO has greater stability than anti-bonding MO as bonding MO has lower energy than anti-bonding MO. A molecular orbital gives the electron probability distribution around a group of nuclei in a molecule such as an atomic orbital that gives the electron probability distribution around a nucleus in an atom. The molecular orbitals are filled in the same way as atomic orbitals are filled according to the Aufbaus principle (orbitals filled in order of increasing energies) obeying the Paulis exclusion principle (orbital can have maximum two electrons of opposite spin) and the Hunds rule (pairing in degenerate orbitals doesnt take place until each orbital got one electron).

Formation of Molecular orbitals: Linear Combination of Atomic Orbitals (LCAO) Application of LCAO to Homonuclear Diatomic Hydrogen Molecule MO = A B Where, MO = Wave function representing molecular orbital of hydrogen molecule A, B = Wave functions representing atomic orbitals of hydrogen atoms A and B respectively

Two molecular orbitals Bonding molecular orbital, = A + B Anti-bonding molecular orbital, * = A B Energy level diagram depicting formation of bonding and anti-bonding molecular orbitals of hydrogen molecule:

The energy of a bonding MO is always lower than that of an anti-bonding M.O.

Conditions for the Combination of Atomic Orbitals

The combining atomic orbitals must have the same or nearly the same energies. The combining atomic orbitals must have the same symmetry about the molecular axis. The extent of overlapping between the combining atomic orbitals must be maximum.

Types of Molecular Orbitals

(sigma), (pi), (delta), etc. symmetrical unsymmetrical

Energy Level Diagram for Molecular Orbitals

For O2 and F2

Increasing order of energy: 1s < *1s < 2s < *2s < 2pz < (2px = 2py) < (*2px = *2py) < *2pz For Li2, Be2, B2, C2, and N2
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Increasing order of energy: 1s < *1s < 2s < *2s < (2px = 2py) < 2pz < (*2px = *2py) < *2pz

Electronic Configuration and Molecular Orbital

Electronic configuration: Distribution of electrons among various molecular orbitals Information obtained from electronic configuration:

Stability of molecules If Nb = Number of electrons occupying bonding MO Na = Number of electrons occupying anti-bonding MO Then, (i) The molecule is stable if Nb > Na (ii) The molecule is unstable if Nb Na

Bond order: Bond order (b.o) = Nature of bond: Single bond, if b.o. = 1 Double bond, if b.o. = 2 Triple bond, if b.o. = 3 Bond length: Decreases with increase in b.o. Magnetic nature: Diamagnetic, if all the MOs are doubly occupied; and paramagnetic, if one or more MOs are singly occupied

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Hydrogen Bonding

Attractive force between hydrogen atom of one molecule and electronegative atom (F, O, or N) of another molecule Represented by dotted lines (------)

Conditions for Hydrogen bonding: 1. The molecule must contain a highly electronegative atom linked to H-atom. 2. The size of electronegative atom should be small. Cause of Formation of Hydrogen Bonds (only for reading) Hydrogen bond formation takes place when hydrogen is bonded to a strong electronegative atom. This formation is explained in the following flow chart: Displacement of electron pair towards the electronegative atom

 Attainment of fractional positive charge by hydrogen atom and fractional negative charge by the electronegative atom Formation of a polar molecule having electrostatic force of attraction Formation of hydrogen bond Dependence of H-bonding

The magnitude of H-bonding depends upon the physical state of the compound.

Types of Hydrogen Bonds Two types: Intermolecular hydrogen bond Intra-molecular hydrogen bond

Intermolecular hydrogen bond: o Formed between two different molecules of the same or different compounds o Example:

Intra-molecular hydrogen bond: o Formed within the same molecule o Reason when hydrogen atom is present in between two highly electronegative atoms (F, O or N) within the same molecule o Example:

UNIT- 3 (Classification of Elements and Periodicity in Properties)

Significance of Classification (Why do we need to classify Elements?):
It was very difficult to study individually the chemistry of millions of the compounds of a large no of elements. At this stage, scientists felt the need of simple method to systematize the study of their properties. They decided to make periodic table.

Periodic Table:
It may be defined as the table which classifies all the known elements in accordance with their properties in such a way that elements with similar properties are grouped together in the same vertical column and dissimilar elements are supposed from one another.

Historical development of periodic table: 1. Dobereiners Triads

Show a relationship between atomic weights and the chemical properties of elements Certain similar elements exist in groups of three elements called triads. Elements are arranged in order of increasing atomic mass; and the atomic mass of the middle elements is the arithmetic mean of the atomic weights of the other two elements in the triad. Dobereiners Triads lement Atomic weight Element Atomic weight Element Atomic weight Li Na K 7 23 39 Ca Sr Ba 40 88 137 Cl Br I 35.5 80 127

This law of triads is applicable to a limited number of elements.

2. Newlands law of octaves

Elements are arranged in the order of increasing atomic weights and it was noticed that every eighth element had the properties similar to the first element.This relationship was similar to every eighth note that reassembles the first in octaves of music. Newlands Octaves Li Be B C N O F7

Element

At. wt Element At. wt Element At. wt

o

7 Na 23 K 39

9 Mg 24 Ca 40

11 Al 27

12 Si 29

14 P 31

16 S 32

19 Cl 35.5

Law of octaves could not be applied beyond Ca.

3. Lothar-Meyer arrangement:
He (Lothar-Meyer) plotted a graph between atomic volumes and atomic weights of elements and observed that the elements with similar properties occupies similar positions on the curve. Diagram in book.

4. Mendeleevs Periodic Table

a. Mendeleevs Periodic Law The properties of the elements are a periodic function of their atomic weights. b. Elements are arranged in order of increasing atomic weights.

c. Nine vertical columns groups Seven horizontal rows periods or series d. Significance (use): 1. Systematic study of elements: After knowing the properties of one element in a group, the properties of other elements in group can be easily predicted.

2. Prediction of new elements: while arrange known elements, Mendeleev left some blank space for unknown elements. He predicted the properties of those unknown elements on basis of their positions. 3. Correction of doubtful atomic weights: Using periodic table he was able to correct doubtful atomic weights of some elements e.g. Beryllium was assigned an atomic weight of 13.5 on the basis of equivalent weight (4.5) & valence (2). But if it has 13.5 weight it should placed between C & N but there was no vacant space between C & N. So valence 2 was assigned to Be now weight is 4.5*2=9 now it has placed at proper place between Li Lithium (7) & B Boron (11) e. Defects in the Mendeleevs periodic table: i. Position of hydrogen is not justified. ii. Certain elements of higher atomic masses precede those with lower atomic weights. iii. Isotopes are placed in the same position in the table. However, according to Mendeleevs law, they should be placed in different positions.

Modern Periodic Law and the Present Form of Periodic Table o Modern Periodic Law The physical and chemical properties of the elements are periodic functions of their atomic numbers. o Modern periodic table (or log form of the periodic table)

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Horizontal rows periods Vertical columns groups Elements having similar outer electronic configurations in their atoms are arranged in groups or families.

Advantage: 1. Its easy to remember elements in sequence of atomic numbers. 2. Elements of same group are similar due to same outer electronic configuration. 3. It relates the position of element to electronic configuration. Defects:

1. Position of Hydrogen is not settled. 2. Lanthanides & Actinides have not been placed in main body of periodic table.

Prediction of period, Group and Block of a given element:

1. Period is the principal quantum number (n) of valence shell. 2. Block is the type of orbital which receive last electron. 3. Group is the no of electrons in valence shell. a) For s-block elements, group number is equal to no of valence electrons. b) For p- block elements, group number is equal to 10+ no of valence electrons. c) For d- block elements, group number is equal to no of electrons in (n-1) d-subshell + no of electrons in valence shell (nth shell). e.g. Element A Period: 3rd Block: s- block At. No. 12 Group: 2 Electronic configuration 1s2 2s2 2p6 3s2

Electronic Configuration and the Periodic Table

Electronic Configuration in Periods

Period indicates the value of n (principal quantum number) for the outermost or valence shell. Successive period in the periodic table is associated with the filling of the next higher principal energy level (n = 1, n = 2, etc). First period (n = 1) hydrogen (1s1) and helium (1s2) [2 elements] Second period (n = 2) Li (1s2 2s1), Be (1s2 2s2), B (1s2 2s2 2p1) to Ne (2s2 2p6) [8 elements] Third period (n = 3) filling to 3s and 3p orbitals give rise to 8 elements (Na to Ar) Fourth period (n = 4) 18 elements (K to Kr) filling to 4s orbital 3d orbital is filled up before 4p orbitals (3d orbitals energetically favourable) o 3d-transition series Sc (3d1 4s2) to Zn (3d10 4s2) (n = 3) Fifth period (n = 5) 18 elements (Rb to Xe) o 4d-transition series starts at ytterbium and ends at cadmium. Sixth period (n = 6) 32 elements; electrons enter 6s, 4f, 5d, and 6p orbitals successively. Elements from Z = 58 to Z = 71 are called 4f-inner transition series or lanthanoid series (filling up of the 4f orbitals). Seventh period (n = 7) electrons enter at 7s, 5f, 6d, and 7p orbitals successively. Filling up of 5f orbitals after Ac (Z = 89) give 5f-inner transition series or the actinoid series.

Electronic Configuration in Groups

Same number of electrons is present in the outer orbitals (that is, similar valence shell electronic configuration). Electronic configuration of group 1 elements is given in the following table. Atomic number Symbol Electronic configuration

3 11 19 37 55 87

Li Na K Rb Cs Fr

1s2 2s1(or) [He]2s1 1s2 2s2 2p6 3s1(or) [Ne]3s1 1s2 2s2 2p6 3s2 3p6 4s1(or) [Ar]4s1 1s2 2s2 2p6 3s2 3p6 3d10 4s2 4p6 5s1(or) [Kr]5s1 1s2 2s2 2p6 3s2 3p6 3d10 4s2 4p6 4d10 5s2 5p6 6s1(or)[Xe]6s1 [Rn]7s1

Electronic Configurations and Types of Elements

s- Block Elements o Group 1 (alkali metals) ns1 (outermost electronic configuration) o Group 2 (alkaline earth metals) ns2 (outermost electronic configuration) o Alkali metals form +1 ion and alkaline earth metals form +2 ion. o Reactivity increases as we move down the group. o They are never found in pure state in nature. (Reason they are highly reactive) p - Block Elements o Elements belonging to Groups 13 to 18 o Outermost electronic configuration varies from ns2np1 to ns2np6 in each period. o Group 18 (ns2np6) noble gases o Group 17 halogen o Group 16 chalcogens o Non-metallic character increases from left to right across a period. d- Block Elements (Transition Elements) o Elements of group 3 to group 12 o General electronic configuration is (n 1) d110 ns0-2. o Called transition elements o Zn, Cd, and Hg with (n 1) d10 ns2 configuration do not show properties of transition elements. o All are metals. They form coloured ions, exhibit variable oxidation states, paramagnetism, and are used as catalysts. f- Block Elements o Lanthanoids Ce (Z = 58) to Lu (Z = 71) o Actinoids Th (Z = 90) to Lr (Z = 103) o Outer electronic configuration (n 2) f114 (n 1) d01 ns2 o They are called inner-transition elements. o All are metals. o Actinoid elements are radioactive. o Elements after uranium are called Transuranium elements.

Metals, Non-metals, and Metalloids

Metals appear on the left side of the periodic table Non-metals located at the top right hand side of the periodic table Elements change from metallic to non-metallic from left to right.

Elements such as Si, Ge, As, Sb, Te show the characteristic properties of both metals and non-metals. They are called semi-metals or metalloids.

Periodic Trends in Physical Properties

Atomic Radius

Atomic radii decrease with the increase in the atomic number in a period. For example, atomic radii decrease from Li to F in the second period.

Nuclear charge increases progressively by one unit in moving from left to right across the period. As a result, the electron cloud is pulled closer to the nucleus by the increased effective nuclear charge, which causes decrease in atomic size. Atomic radii increase from top to bottom within a group of the periodic table. Variation of atomic radii with atomic number among alkali metals and halogen:

Ionic Radius

Cation is smaller than its parent atom. The size of the anion is larger than its parent atom.

Ionization Enthalpy

Defined as the amount of energy required to remove the most loosely bound electron from the isolated gaseous atom in its ground state

Decreases with the increase in atomic size Increases with the increase in nuclear charge Decreases with the increase in the number of inner electrons Increases with the increase in penetration power of electrons Atom having a more stable configuration has high value of enthalpy. Variation across a period increases with the increase in atomic number across the period. Variation in a group decreases regularly with the increase in atomic number within a group.

Electron Gain Enthalpy

Defined as the enthalpy change taking place when an isolated gaseous atom accepts an electron to form a monovalent gaseous anion

Larger the value of electron gain enthalpy, greater is the tendency of an atom to accept electron. Greater the magnitude of nuclear charge, larger will be the negative value of electron gain enthalpy. Larger the size of the atom, smaller will be the negative value of electron gain enthalpy. More stable the electronic configuration of the atom, more positive will be the value of its electron gain enthalpy. Variation across a period tends to become more negative as we go from left to right across a period Variation down a group becomes less negative on going down the group

Electronegativity

Defined as the tendency of an atom in a molecule to attract the shared pair of electrons towards itself Greater the effective nuclear charge, greater is the electronegativity. Smaller the atomic radius, greater is the electronegativity. In a period increases in moving from left to right In a group decreases on moving down a group

Non Metallic (and Metallic Character) of an Element

Non-metallic elements have strong tendency to gain electrons. Non-metallic character is directly related to electronegativity and metallic character is inversely related to electronegativity. Across a period, electronegativity increases. Hence, non-metallic character increases (and metallic character decreases). Down a group, electronegativity decreases. Hence, non-metallic character decreases (and metallic character increases). The periodic trends of various properties of elements in the periodic table are shown in figure.

Periodic Trends in Chemical Properties

Periodicity of Valence or Oxidation States

Valence of the elements = Number of electrons in the outermost orbitals Or, valence of the element = 8 Number of outermost electrons Group 1 2 13 14 3 3 4 4 15 5 16 6 17 7 18 8

Number of valence electrons 1 2 Valence

1 2

3,5 2,6 1,7 0,8

The given table shows the periodic trends observed in the valence of elements (hydrides and oxides). Group Formula of hydride 1 LiH NaH CaH2 2 13 B2H6 AlH3 14 CH4 SiH4 15 NH3 PH3 16 H2O H2S 17 HF HCl

KH

GeH4 SnH4

AsH3 SbH3 N2O3, N2O5 P4O6, P4O10 As2O3, As2O5

H2Se H2Te

HBr Hl

Formula of oxide

Li2O Na2O K2 O

MgO CaO SrO BaO

B2O3 Al2O3

CO2 SiO2

SO3 SeO3

Cl2O7

Ga2O3 GeO2 In2O3 SnO2 PbO2

Sb2O3,Sb2O5 TeO3 Bi2O3

Many elements exhibit variable valence (particularly transition elements and actinoids).

Anomalous Properties of Second Period Elements

First member of each group (the element in the second period from lithium to fluorine) differs in many respects from the rest of the members of the same group. o For example, the behaviour of Li and Be is more similar with the second element of the following group i.e., Mg and Al respectively. o Such sort of similarity is commonly known as diagonal relationship in periodic properties. Reasons for the different chemical behaviour of the first member of a group of elements in the s-and p-blocks as compared to the other members in the same group are as follows. o Small atomic size of the first element o Large charge/radius ratio o High electronegativity o Absence of d-orbitals in the valence shell o Ability of form p p multiple bonds First member of each group of p-block elements has the tendency to form p p multiple bonds to itself and to the other second period elements. For example, C = C, C C, C = O, C = N o Reason This property of the elements is due to their small size. Higher members of the group have little tendency to form p p bonds.

Periodic Trends and Chemical Reactivity

High chemical reactivity at the two extremes of a period and the lowest in the centre o Maximum chemical reactivity is at the extreme left to a period because of the ease of electron loss (or low ionization enthalpy).

Elements at the extreme left exhibit strong reducing behaviour and elements at the extreme right exhibit strong oxidizing behaviour. Oxides formed by the elements on the left are basic and by the elements on the right are acidic in nature. Oxides of elements in the centre are amphoteric or neutral.
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UNIT- 5 (states of Matter)

Difference between three states of matter (solid, liquid, gas) see in book Intermolecular Forces

Attractive and repulsive forces between interacting particles (atoms and molecules) Do not include ionic and covalent bonds Attractive intermolecular forces are known as van der Waals forces.

Dispersion Forces or London Forces o Forces of attraction between two temporary dipoles o Occur between atoms or non-polar molecules

Atoms or non-polar molecules have no dipole moment as they are electrically symmetrical. However, for some reason, momentarily an atom or non-polar molecule becomes electrically unsymmetrical. As a result, instantaneous dipole is developed on that atom for a very short time. This instantaneous dipole induces dipole on another atom close to it.

E , where E = Interaction energy r = Distance between two interacting particles o Occur only at short distances (~500 pm) o Depend on the polarisability of the particle Dipole-Dipole Forces o Forces between molecules possessing permanent dipole o London force < Dipole-dipole force < Ion-ion force
o

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Increase with decrease in distance For stationary polar molecules, E And for rotating polar molecules, E Where, E = Interaction energy r = Distance between the polar molecules For polar molecules, Total intermolecular forces = Dipole-dipole forces + London forces Dipole-dipole interaction between two HCl molecules:

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Dipole-Induced Dipole forces o Forces between polar molecules and non-polar molecules o Occur because polar molecule induces dipole on non-polar molecule

Depend on dipole moment on the polar molecule polarisability of the nonpolar molecule E , where E = Interaction energy r = Distance between the two molecules Intermolecular forces between polar and non-polar molecules = London forces + Dipole-induced dipole forces

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Hydrogen Bonding

Special case of dipole-dipole interaction Force between hydrogen attached to an electronegative atom of one molecule and an electronegative atom of different molecule Limited to electronegative atoms N, O, and F (sometimes Cl also)

Formation of hydrogen bond:

Repulsive Forces

Increases with decrease in distance Due to this reason , o solids are harder to compress than liquids o liquids are harder to compress than gases

Thermal Energy

Energy of a body resulting from atomic and molecular motion Measure of average kinetic energy of particles of matter Directly proportional to temperature

Intermolecular Forces vs. Thermal Interaction

Intermolecular forces hold molecules together Thermal interactions keep molecules apart Intermolecular forces and thermal energy balance each other to different extent resulting in the three states of matter (solid, liquid, and gas).

The Gaseous State

Physical Properties: o Can be compressed to a large extent o Exerts pressure equally in all directions o Much less denser than solids and liquids o Does not have any shape and volume o Mixes evenly and completely in all proportions Reason for these properties: o Negligible intermolecular forces of interaction

Eleven elements which exist as gases under normal atmospheric condition are as follows:

Boyles Law

Relation between pressure (p) and volume (V) Statement At constant temperature, the pressure of a fixed amount (number of moles, n) of a gas is inversely proportional to its pressure. Mathematically,

, where
o

= Proportionality constant

From the above equation, it is found that at constant temperature, the product of pressure and volume of a fixed amount of a gas is constant.

The value of depends upon o amount of the gas o temperature of the gas o units of p and V Graphical representation of constant temperature

Each line is called isotherm (at constant temperature plot). If at constant temperature, V1 = Volume of a gas at pressure p1 V2 = Volume of the same gas at pressure p2 Then,
o

p1V1 = p2V2 = Constant

Relationship between density (d) and pressure (p): We know that,

Where, m = Mass of a gas V = Volume of the gas

From the above equation, it is known that density is proportional to the pressure of a fixed amount of a gas. Example Rita has two cylinders. One is empty and the other contains compressed nitrogen at 25 atm. She wants to distribute the gas in the two cylinders. To do so, she connects the two cylinders. If the volume of the cylinder containing the gas is 50 L and that of the empty one is 80 L, then what will be the pressure inside the two cylinders? Solution: According to Boyles law,

Given, p1 = 25 atm V1 = 50 L V2 = ( 50 + 80) L = 130 L Now, 25 atm 50 L = p2 130 L

Hence, the pressure inside the cylinders is 9.62 atm.

Charles Law

Relation between temperature (T) and volume (V) Statement At constant pressure, the volume of a fixed amount of a gas is directly proportional to its absolute temperature. Mathematically, , where = Proportionality constant

The value of depends upon o pressure of the gas o amount of the gas o unit of volume Graphical representation

Straight line o Interception on zero volume at 273.15C o Each line is called isobar (constant pressure plot). Derivation
o

For each degree rise in temperature, volume of a gas increases by original volume of the gas at 0C. Suppose, V0 = Volume of a gas at 0C Vt = Volume of the same gas at tC Then,

of the

According to Kelvin temperature scale (also called absolute temperature scale or thermodynamic scale), T = 273.15 + t T0 = 273.15 From equation (i), we obtain

Or, we can write

Example It is desired to increase the volume of 6 L of a gas by 40% without changing the pressure. To what temperature should the gas be heated if its initial temperature is 298 K? Solution: Desired increase in the volume of gas = 40% of 5 L

=2L Therefore, final volume of the gas = (5 + 2 ) L = 7 L Applying Charles law,

Now, V1 = 5 L T1 = 298 K V2 = 7 L

Therefore,

Gay-Lusaacs Law

Relation between pressure and temperature Statement At constant volume, the pressure of a fixed amount of a gas is directly proportional to the temperature. Mathematically, pT = constant = k3 Graphical representation at constant volume

Each line is called isochore (constant volume plot). If at constant volume, p1 = Pressure of a gas at T1 p2 = Pressure of the same gas at T2 Then,
o

Example An iron tank contains helium at a pressure of 3.0 atm at 300 K. The tank can withstand a maximum pressure of 12.0 atm. The building in which the tank has been placed catches fire. Predict whether the tank will blow up first or melt. (Given, melting point of iron is 1808 K) Solution: To calculate the pressure built up in the tank at the melting point of iron, we have to apply Gay-Lussacs law.

According to Gay-Lusaacs Law,

Here, p1 = 3.0 atm T1 = 300 K T2 = 1808 K

Now,

= 18.08 atm It is found that pressure of the gas in the tank is much more than 10 atm at the melting point. Hence, the tank will blow up before reaching the melting point. Avogadro Law

Relation between volume (V) and amount of substance (number of moles n) Statement Under the same conditions of temperature and pressure, equal volumes of all gases contain equal number of molecules. That is, at constant temperature and pressure, the volume of a gas depends upon the amount (number of mole n) of the gas. Mathematically, Vn V = k4n Where, k4 = Proportionality constant Avogadro constant = Number of molecules present in one mole of a gas = 6.022 1023 At STP (273.15 K and 1 bar), molar volume of an ideal gas is 22.71098 L mol1. If m = Mass of a gas M = Molar mass of the gas Then,

Therefore,

(Since V = k4n)

From the above equation, it can be concluded that at a given temperature and pressure, density of a gas is directly proportional to its molar mass.

Ideal Gas Equation

Ideal Gas

The gas which strictly follows Boyles law, Charles law and Avogadro law The intermolecular forces are assumed to be absent between the molecules of an ideal gas. Under a certain specific condition (when the intermolecular forces are negligible), real gases follow the above laws.

Ideal Gas Equation

Equation obtained by the combination of Boyles law, Charles law and Avogadro law Boyles law: V (At constant T and n) Charles law: V T (At constant p and n) Avogadro law: V n (At constant p and T) By combining the above three laws, we have V

pV = nRT .(i) R = Proportionality constant, known as Universal Gas Constant Equation (i) is called ideal gas equation. At STP, for one mole of a gas,R = 8.314 JK1 mol1 Or, R = 8.20578 102 L atm K1 mol1 It is also called the equation of state o Reason: It relates between four variables and describes the state of a gas. Combined gas law: If the temperature, volume and pressure of a fixed amount of a gas vary from T1, V1 and p1 to T2, V2 and p2, then we have

From equations (ii) and (iii), we have

Equation (iv) is called combined gas law. Examples 1. A vessel of 200 mL capacity contains a certain amount of gas at 27C and 0.9 bar pressure. The gas is then transferred into another vessel of capacity 150 mL at 27C. What would be the pressure of the gas in the vessel of capacity 150 mL? Solution: According to combined gas law,

Here, initial pressure of the gas, p1 = 0.9 bar Final pressure of the gas, p2 = ? Initial volume of the gas, V1 = 200 mL Final volume of the gas, V2 = 150 mL Initial temperature of the gas, T1 = (27 + 273) K = 300 K Final temperature of the gas, T2 = (27 + 273) K = 300 K

Now,

= 1.2 bar Hence, the pressure of the gas in the vessel of capacity 150 mL would be 1.2 bar.

Relation between density and molar mass of a gaseous substance: pV = nRT ( Where, m = Mass of the gas, M = Molar mass of the gas)

(Where, Density,

Daltons Law of Partial Pressures

Partial pressure: Pressure exerted by the individual gases in a mixture Statement: At constant temperature, the total pressure exerted by a mixture of two or more non-reacting gases, enclosed in a definite volume, is equal to the sum of the partial pressures of the individual gases. Mathematically, Ptotal = p1 + p2 + p3 + .. (At constant T and V) Where, ptotal = Total pressure exerted by the mixture p1 + p2 + p3, ... = Partial pressures of the individual gases pdry gas = ptotal Aqueous tension Where, pdry gas = Pressure of dry gas ptotal = Total pressure Aqueous tension: Pressure exerted by saturated water vapour Partial pressure in terms of mole fraction: Suppose three gases are enclosed in a vessel of volume, V at temperature, T and exert partial pressures, p1, p2 and p3 respectively. Then, we have

Where, n1, n2, n3 = Number of moles of the gases Now, ptotal = p1 + p2 + p3

By dividing p1 by ptotal, we have

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x1 is called the mole fraction of the first gas General equation pi = xi ptotal pi = Partial pressure of ith gas xi = Mole fraction of ith gas Example

A gaseous mixture of oxygen and nitrogen contains 22.4 g of oxygen and 145.6 g of nitrogen. The pressure of the mixture is 700 Nm2. What are the respective partial pressures of oxygen and nitrogen in the mixture? Solution: Molar mass of O2 = 32 g mol1 Molar mass of N2 = 28 g mol1

Therefore, number of moles of O2 in the mixture

Number of moles of N2 in the mixture = 5.2 mol

Hence, mole fraction of O2,

= 0.119

Mole fraction of N2, = 0.881

= 1 0.119

Given, total pressure, ptotal = 700 Nm2 Therefore, partial pressure of O2, = 0.119 700 Nm2 = 83.3 Nm2 And, partial pressure of N2, = 0.881 700 Nm2 = 616.7 Nm2 ptotal = ptotal

Kinetic Molecular Theory of Gases

This theory attempts to elucidate the behaviour of gases. Postulates: o All gases are made of very large number of extremely small particles (atoms or molecules). The particles are separated by such large spaces that the actual volume of the particles is negligible as compared to the empty spaces between them. This is why gases are compressible to a large extent. o There is no attractive or repulsive force between the particles of a gas; hence, gases occupy all the space available to them. o Particles of a gas are not at rest, but are in constant random motion. o Particles of a gas move in all possible directions in straight lines. During their motion, they collide with one another and also with the walls of the container. The collisions of the particles against the walls of the container result in the pressure of the gas. o The collisions of the particles of a gas are perfectly elastic, i.e., there is no loss or gain of kinetic energy. The total energy of the particles before and after the collisions remains the same. However, there may be an exchange of energy between the colliding particles during such collisions. o At any instant, different particles of a gas possess different speeds, and hence, different kinetic energy. This is because the speed of a particle changes after collision. However, the distribution of speed remains constant at a particular temperature. o The average kinetic energy of the particles of a gas is directly proportional to the absolute temperature.

Behavior of Real Gas

Deviates from ideal gas behaviour According to Boyles law, at constant temperature, pV of a gas is constant, and the pV vs p graph is a straight line parallel to the x-axis at all pressures. But real gases do not behave like this.

Reasons for deviation from the ideal gas behaviour The two postulates of the kinetic theory which do not hold good: o There is no force of attraction and repulsion between the molecules of a gas. o Volume of the molecules of a gas is negligibly small in comparison to the space occupied by the gas. van der Waals equation: o Real gas deviates from ideal gas behaviour as there are forces of attraction and repulsion between the molecules of a gas. At high pressure, while striking the walls of a container, the molecules of a gas are dragged back by other molecules due to the existing force of attraction; therefore, the pressure exerted by the gas is lower than the pressure exerted by an ideal gas.

Where, n = Number of moles of real gas V = Volume of the gas a = van der Waals constant, whose value depends upon the nature of the gas Real gas deviates from ideal gas behaviour as the volume occupied by the gas molecules becomes significant. This is because the movement of the gas particles is restricted to the volume (V nb), instead of V. Here, nb is the approximate total volume of the molecules themselves, excluding the spaces between them. This means, Videal = Vreal nb

Therefore, the ideal gas equation pV = nRT can be rewritten as

This equation is called Van der Waals equation. o Significance of a: It is the measure of the magnitude of attractive forces between the molecules of a gas. Unit: atm L2 mol2 or bar L2 mol2 Larger the value of a, larger will be the intermolecular force of attraction. It is independent of pressure and temperature. o Significance of b: It is the measure of the effective size of gas molecules. Unit: L mol1 Real gases behave like ideal gas under certain specific conditions when the intermolecular forces are negligible. o When pressure approaches zero, real gases behave like ideal gas. o When the volume of a gas is so large that the volume occupied by the molecules is negligible, the gas shows ideal gas behaviour. Compressibility factor (Z): o It is the measure of deviation from ideal behaviour.
o

Or

For ideal gas, Z = 1 o At low pressure, Z 1 At high pressure, Z > 1 At intermediate pressure, Z < 1 Boyle temperature or Boyle point: o The temperature at which a real gas shows ideal gas behaviour over an appreciable range of pressure o Depends upon the nature of the gas o Above Boyle point positive deviation from ideal behaviour o Below Boyle point negative deviation from ideal behaviour At low pressure and high temperature, gases behave ideally.
o

Liquefaction of Gases A gas can be liquefied by increasing its pressure and decreasing its temperature.

Critical temperature (Tc) the temperature at which a gas can be liquefied Critical pressure (pc) the pressure of a gas at critical temperature Critical volume (Vc) the volume of 1 mole of a gas at critical temperature

Isotherm of carbon dioxide is shown in the figure.

Critical temperature, critical pressure and critical volume are called critical constants.

Liquid State

Intermolecular forces are stronger than those in gaseous state

Liquids have definite volume. o Reason: Molecules do not separate due to intermolecular force of attraction. Liquids can flow. o Reason: Molecules can freely move past one another.

Physical Properties of Liquid Shape: No definite shape. Volume: Definite Volume. Density: Higher density than gases. Compressibility: less than gases. Diffusion: Slower than Gas because molecules are quite close, so they undergo large no of collisions
with each other.

Vapour Pressure

Equilibrium vapour pressure or saturated vapour pressure: Vapour pressure in the state of equilibrium between liquid phase and vapour phase Boiling point: o The temperature at which the vapour pressure of a liquid is equal to the external pressure o Normal boiling point Boiling point at 1 atm pressure

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Standard boiling point Boiling point at 1 bar pressure Normal boiling point is less than the standard boiling point. Reason 1 atm pressure is slightly greater than 1 bar pressure. Example Water has a normal boiling point of 100C (373 K) and a standard boiling point of 99.6C (372.6 K). The boiling point of a liquid is lower at high altitudes than at sea level. Reason Atmospheric pressure is lower at high altitudes than at sea level. This means that the boiling point of a liquid can be varied by changing the pressure over the liquid.

Surface Tension

Force acting per unit length perpendicular to the line drawn on the surface of liquid Denoted by Greek letter (gamma) Unit = Nm1 Reason for surface tension A molecule in the bulk of liquid does not experience any net force as it experiences equal intermolecular forces from all the sides. However, there are no intermolecular forces above a molecule on the surface of liquid. Therefore, a molecule on the surface of liquid experiences net attractive force towards the interior of the liquid.

As a result of surface tension, liquid tends to minimize their surface area. Surface energy o Energy required to increase the surface area of the liquid by one unit o Unit = Jm2 Liquid droplets are spherical because sphere has minimum surface area and liquids tend to have minimum surface area due to surface tension. Surface tension causes capillary action. Dependence of surface tension: o The attractive forces between the molecules increase with increase in attractive force. o The temperature decreases with the increase in temperature because with the increase in temperature, kinetic energy of particles increases and hence, effectiveness of intermolecular attraction decreases.

Viscosity

Resistance of flow Stronger the intermolecular forces, higher is the viscosity. Laminar flow

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Type of flow which involves a regular velocity gradation in passing from one layer to the next For a given layer in a flowing liquid, the layer above it accelerates its flow while the layer below it retards its flow.

Velocity gradient (change in velocity with distance) Where, dz = Distance du = Change in velocity We can write, FA Where, F = Force required to maintain the flow of layers A = Area of contact And, Therefore,

Where, = Proportionality constant known as coefficient of viscosity Viscosity coefficient o Force when velocity gradient is unit and the area of contact is unit area o Pleasure of viscosity o SI unit = Ns m2 1 Ns m2 = 1 Pa S = 1 kg m1 s1 CGS unit = poise 1 poise = 1 g cm1 s1 = 101 kg m1 s1 Greater the viscosity, more slowly the liquid flows. Glass is an extremely viscous liquid. With increase in temperature, viscosity of liquids decreases. o Reason With increase in temperature, kinetic energy of molecule increases and therefore, it is harder to overcome the intermolecular forces to slip past one another between the layers.