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Chemistry Synopsis Handouts

Chemistry Synopsis Handouts

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Published by Osama Hasan
Prepared by Osama Hasan (Chemistry Instructor and Coordinator NSTC-6 Preparation Programme) for students of Aga Khan Higher Secondary School, Karachi.

Could be beneficial for entry test examinations.
Prepared by Osama Hasan (Chemistry Instructor and Coordinator NSTC-6 Preparation Programme) for students of Aga Khan Higher Secondary School, Karachi.

Could be beneficial for entry test examinations.

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Published by: Osama Hasan on Jun 10, 2010
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BASIC CONCEPTS SYNOPSIS HAN ASIC ANDOUT 1

PREPARED BY OSAMA HASAN

Matter: Everything that has mass and occupies space. at Mass: The amount of matte present in a body. matter

Element: A simple substan that couldn’t be ubstance divided further into more substances. (It’s further re subs “The branch of Physical Science Phy classified into metals and non-metals) d non which studies the composition, e co Compound: Two or more elements chemically structure, propertie and changes erties combined together in a fixed proportion. p occurring inside th matter is e the referred as Chemis mistry.” Mixture: A substance that c contains two or more elements or compounds ounds. Homogenous Mixture A mixture that has ure: uniform composition through roughout its mass. Heterogeneous Mixtu ixture: A mixture that has different composition throughout its ion thr mass. Chemical Symbols: A o one- or two-letter designation derived from the name of an n element to represent it conven onveniently. Chemical Formulae: i indicates the composition of a compound through symbols of rough elements present and subscrip to indicate the relative number of atoms of each element. bscripts s ea

INTERNATIONAL SY L SYSTEM OF UNITS (SI):
The modernized metric system using the decimal system as its base is now referred as tric sy SI. It has seven basic quantities. ities. S. o. Property perty Abbreviation Unit Abbrevia breviation Mass m Kilogram Kg 1. Length L Meter M 2. Time t Second S 3. Electric Current urrent I Ampere A 4. Temperature T Kelvin K 5. Amount of Subs f Substance n Mole Mol 6. Luminous Intens Intensity candela cd 7. Derived Quantities: Th quantities obtained by the multiplication or division of SI The n di quantities. Example:

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BASIC CONCEPTS SYNOPSIS HANDOUT 1
PREPARED BY OSAMA HASAN

Mass kg Volume = length x Unit = m x m x m Unit = breadth x height = m3 Volume m Temperature Measurements: Three different scales are widely used for measuring temperature, namely, Celsius (centigrade), Fahrenheit and Kelvin. The conversion formulae for them are as follows: °C °F − 32 = K = °C + 273 5 9 Density =

UNIT CONVERSIONS:
SI units could be derived by combining prefixes with a root unit. Some basic prefixes are as follows: S. o. Prefix Multiple Scientific otation Abbreviation 6 Mega1,000,000 10 M 1. k Kilo1,000 103 2. 2 Hector 100 10 h 3. 1 Deka10 10 da 4. Deci0.1 10-1 d 5. -2 Centi0.01 10 c 6. -3 Milli0.001 10 m 7. -6 µ Micro 0.000,001 10 8. Nano0.000,000,001 10-9 n 9. -12 Pico 0.000,000,000,001 10 p 10.

SIGNIFICANT FIGURES: “The reliable digits which are known with certainty.”
Rules: All non-zero numbers are significant Zeros placed in between non-zero numbers or after a decimal point are significant. Zero that locates the decimal point on number less that (1) is non-significant. Zero that locates the decimal point on number larger than (1) is significant.

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CHEMICAL LANGUAGE SYNOPSIS HANDOUT 2
PREPARED BY OSAMA HASAN

LAWS OF CHEMICAL COMBINATION:
Law of Conservation of Mass (Indestructibility of Matter): “In a chemical reaction, the total mass of reactants is equal to the total mass of products i.e. matter can neither be created nor be destroyed.” It was put forward by Lavoiser in 1785. Law of Definite Proportion: “When elements combine to form compounds, they do so in definite proportions by weight. A compound always has the same proportion by whatever method it is prepared.”It was given by Joseph Proust in 1799. Law of Multiple Proportions: "When two elements combine to form more than one compound, the different weights of one of the elements combining with a fixed weight of the other, bears a simple ratio to each other." The law was proved by Berzilius & Stas. Law of Reciprocal or Equivalent Proportion: "The weights of two elements combining separately with a fixed weight of a third element do so with each other in multiple ratios."

BASIC CONCEPTS:
Mole: “Atomic mass of an element, molecular mass of compounds or formula mass of an ionic substance when expressed in grams.” Mole = Avogadro’s number: “The constant number (6.02 x 1023) atoms, molecules or ions contained by one mole of any substance.” Atom: the basic building block of an element that retains the properties of that element and can enter into a chemical reaction. Molecule: The smallest particle of a substance that retains the physical and chemical properties of that substance. Empirical Formula: The simplest formula of a compound which represents the elements present in a compound and the simplest ratio between them.

DETERMINATION OF EMPIRICAL FORMULA:
S. No Steps

1. 2. 3. 4. 5.

Elements present in the compound Mass of each Element Percentage of Each Element ( Mole Ratio ( Atomic Ratio ( ) )

×

)

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CHEMICAL LANGUAGE SYNOPSIS HANDOUT 2
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Molecular Formula: The formula which represents the elements present and the exact number of atoms of different elements present in a molecule of that compound.

DETERMINATION OF MOLECULAR FORMULA:
Molecular formula = [Empirical Formula] n Where n = Molar Concentrations: The molar concentration (M) is the number of moles of the solute contained in one cubic decimeter (dm3) or litre of solution. Molarity = M = No. of moles of solute 1 litre of solution

Molal Concentrations: A molal concentration (m) is the number of moles of the solute per kilogram of solvent. Molality = m = No. of moles of solute 1 kilogram of solvent

% Aqueous Solutions of Compounds: A 10 % aqueous solution of a solute contains 10 g of solute per 100 g solution i.e. 10 g of solute mixed with 90 g water. Percentage Concentrations: The general formula is: % Concentratiions = No. of grams of solute x 100% No. of grams of solvent

Stoichiometry: the study of relationship between the amount of reactant or product involved in a chemical equation based on balanced chemical equation.

DIRECTIONS FOR STOICHIOMETRY:
Mass-Mass Relationship × × → Mass-Mole Relationship Volume-Volume Relationship Formula Mass × Coef icient Formula Mass × Coef icient → Volume Mass-Volume Relationship Formula Mass Mass → Moles → Moles Required → Volume

No. of Moles → No. of Moles Required

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CHEMICAL LANGUAGE SYNOPSIS HANDOUT 2
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Limiting Reactant: “The reactant which is consumed first of all during the chemical reaction is called Limiting Reactant.”

DIRECTIONS FOR LIMITING REACTANT:
+ → Step 1 Step 2 Step 3 → → → Mass of A → Mole of A Mass of B → Mole of B Mass of C → Mole of C → Mole of D → Mole of D → Mole of D The source that yields the least quantity of moles would be the limiting reactant. +

SOME FACTS TO REMEMBER:
1. 1 mole of a substance element, compound = 6.02 × 10 particles atoms, molecules 1 mole of a gas = 22.4 dm at S. T. P 0°C and 1 atm pressure 1 mole of an ionic compound NaCl = 6.02 × 10 Na ions and 6.02 × 10 = 2 × 6.02 × 10 ions Cl ions

2. 3.

4.

1 mole of covalent compound HCl = 6.02 × 10 molecules of HCl = 6.02 × 10 atoms of H and 6.02 × 10 atoms of Cl = 2 × 6.02 × 10 atoms. 1 atm = 14.7 psi pounds per square inch, lb in =760 mm of Hg=29.921 in. of Hg = 760 torr = 20 tons = 1.01325 bar = 13.6 mm of H20

5.

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CHEMICAL TECHNIQUES SYNOPSIS HANDOUT 3
PREPARED BY OSAMA HASAN

SEPARATION TECHNIQUES:
The separated products could differ in chemical properties or some physical property, such as size, or crystal modification or other separation into different components. “A separation process is used to transform a mixture of substances into two or more distinct products.”

Separation # Technique Explanation Between Solute Solvent 1 Pyrolysis conducted in a distillation apparatus (retort) to S S Destructive allow the volatile products to be collected. O O Distillation L L Alloys can be separated by melting them on their 2 Melting I & I respective temperatures. D D 3 Wind winnowing An agricultural method developed by ancient cultures for S S separating grain from chaff. A chemical solid-liquid separation technique, in which 1 Crystallization mass transfer of a solute from the liquid solution to a pure solid crystalline phase occurs. 2 Mechanical or physical operation which is used for the Filtration separation of solids from liquids by interposing a medium to fluid, through which it can pass. 3 Process for the separation of mixtures, carefully pouring a Decantation L S solution from a container, leaving the precipitate I O (sediments) in the bottom of the container Q & L Used for separating solids dissolved in liquid 4 Distillation U I 5 Water treatment process that clarifies wastewaters (or Dissolved Air I D other waters) by the removal of suspended matter such as Floatation D S oil or solids. S 6 A separation process that is used to remove solid or semiSolid-phase extraction (SPE) solid compounds from a mixture of impurities based on their physical and chemical properties 7 Process by which fine particulates are caused to clump Flocculation together into floc or flakes. The floc or flakes may then float to the top of the liquid, settle to the bottom of the liquid, or can be readily filtered from the liquid 8 Removing particulates from water stream, without the use Cyclonic of filters, through vortex separation. Separation 1 Removing particulates from an air or gas, without the use S Cyclonic of filters, through vortex separation. O G Separation L A & 2 Mechanical or physical operation which is used for the Filtration I S separation of solids from gases by interposing a medium D to fluid, through which it can pass.

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CHEMICAL TECHNIQUES SYNOPSIS HANDOUT 3
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Separating a liquid from a solid sediment Heating of solid materials to produce liquid or gaseous products (which may condense into solids). L S 3 Removing liquid from a solid by vaporizing it Drying Q O 5 The liquids in solids are extracted by applying high Expeller Press U & L pressures. I I 6 n-hexane Method Separation of liquids from solids by dissolving it in D D hexane and later performing distillation of the solution. S S 7 By exposing the solid to Super Critical Fluid which Super Critical Fluid Extraction dissolves the liquid and then separating them by a mere change of pressure or temperature. 1 Centrifugation Involves the use of the centrifugal force for the separation of mixtures. 2 Separating mixtures based on differences in their Distillation volatilities in a boiling liquid mixture. Process in which a fractioning column is used in 3 Fractional distillation apparatus to separate components of a liquid Distillation mixture that have different boiling points. distillation whereby the pressure above the liquid mixture 4 Vacuum to be distilled is reduced to less than its vapor pressure Distillation L L (usually less than atmospheric pressure) causing I I evaporation of the most volatile liquid(s) (those with the Q Q lowest boiling points). U U 5 Method to separate compounds based on their relative Solvent I I & solubilities in two different immiscible liquids. Extraction D D Method S S 6 Electrophoresis Organic molecules, such as protein are placed in a gel. A voltage is applied and the molecules move through the gel because they are charged. The gel restricts the motion so that different proteins will make different amounts of progress in any given time. Process used in process engineering and chemistry to 7 Fractional separate two liquids with different melting points Freezing 8 API oil-water A gravity separation device designed by using Stokes Law to define the rise velocity of oil droplets based on their separator density and size. 1 Demister(Vapour) Removing liquid droplets from gas streams. Liquid & Gas ??? Gas & Solid ??? ??? Gas & Liquid ??? Gas & Gas 1 Elutriation/ air Process for separating lighter particles from heavier ones using a vertically-directed stream of gas. classification GENERAL SEPARATION METHODS: 1 2 Decantation Dry Distillation

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CHEMICAL TECHNIQUES SYNOPSIS HANDOUT 3
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Chromatography: Involves the separation of different dissolved substances as they travel through a material. The dissolved substances are separated based on their interaction with the stationary phase. Steam Distillation: Special type of distillation (a separation process) for temperature sensitive materials like natural aromatic compounds. Evaporation: Process by which molecules in a liquid state (e.g. water) spontaneously become gaseous (e.g. water vapor). Sublimation: Conversion of solid molecules to gaseous state. Precipitation: The formation of a solid in a solution during a chemical reaction Fusion: Conversion of solid molecules to a liquid state. Gravity separation: An industrial method of separating two components from a suspension or any other homogeneous mixture where separating the components with gravity is sufficiently practical. Sieving: Separates wanted/desired elements from unwanted material using a tool such as a mesh, net or other filtration or distillation methods, but it is also used for classification of powders by particle size Stripping is a chemical separation process where one or more components are removed from a liquid stream by a vapor stream. S. o. 1. 2. 3. 4. 5. 6. 7. 8. 9. 10. 11. 12. 13. TERMINOLOGY: Miscible: The liquids that can be dissolved in each other Immiscible: The liquids that do not dissolved and could be separated. Alloy: A Solid Solution Ore: A natural deposit containing a mineral of an element to be extracted Distillate: The material in a distillation apparatus that is collected in the receiver. Technique Centrifugation Cyclonic Separation Elutriation/ air classification API oil-water separator Fractional Freezing Fractional Distillation Electrophoresis Solvent Extraction Method Vacuum Distillation Distillation Dry Distillation Flocculation Expeller Press Respective Property Density difference Rotational Effects/Gravity Size of the particles Density & size of oil-droplets Melting Point Boiling Point Electric Charge Relative Solubility Pressure Volatility Heating on high temperatures Density Pressure

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CHEMICAL TECHNIQUES SYNOPSIS HANDOUT 3
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Distilland: The material in a distillation apparatus that is to be distilled.

SOLUBILITY:
SOME FACTS TO REMEMBER: Soluble All compounds of itrates ( O3-), Acetates (CH3COO-) and Chlorates (???). All chlorides. All sulfates Hydroxides of Ca, Ba, Sr, a, K and H4. Common compounds of a, K and H4. Non-Soluble All normal Carbonates (CO3-), Phosphates (PO33-), Silicates (???) & Sulfides (???) Chlorides of Silver, Mercury and Lead Sulfates of lead, barium, strontium and calcium. All Hydroxides

TRENDS OF SOLUBILITY: State Temperature Effect Usually increases with Solid temperature increase Usually decreases with Gas temperature increase

Pressure Effect Little Effect Solubility varies in dirtect proportion to the pressure applied to it (Henry’s Law1)

FACTOR’S AFFECTING RATE OF SOLUBILITY: The following procedures INCREASE the rate of solubility: Pulverizing Increases surface exposed to solvent Brings more solvent that is unsaturated into contact with solute. Stirring Increases molecular action and gives rise to mixing by convection currents. Heating (This heating affects the solubility as well as the rate of solubility)

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Henry’s Law: “The solubility of a gas (unless the gas is very soluble) is directly proportional to the pressure applied to the gas”

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CHEMICAL TECHNIQUES SYNOPSIS HANDOUT 3
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QUALITATIVE TESTS FOR GASES:
Gas Ammonia H3 Carbon Dioxide CO2 Carbon Monoxide CO Chlorine Cl2 Hydrogen H2 Tests Smell Cautiously Test with Litmus Expose to HCl fumes Pass through lime water (Ca(OH)2) Burn it and pass product through lime water Smell Cautiously Observe color Allow it to mix with some air, then ignite Burn it- trap product Smell Cautiously Exhale over the gas Dissolve in water and test with litmus Add AgNO3 to the solution Smell Cautiously Test with moist lead acetate paper Expose to air Insert glowing splint Add Nitric oxide gas Insert glowing splint Add Nitric oxide gas Smell Cautiously Allow it to bubble into purple potassium permanganate solution Observations Sharp Odour Red litmus turns blue White fumes (NH4Cl) formed White precipitates formed White precipitates formed Irritating Odour Yellowish Green Gas explodes Burns with blue flame- product H2O turns cobalt chloride paper from blue to pink. Choking Odour Vapour fumes form Blue litmus turns red White precipitate formed Rotten Eggs’ Odour Turns brown black (PbS) Colourless gas turns reddish brown Bursts into flame Remains colourless Bursts into flame Turns Reddish Brown Choking Odour Solution becomes colourless.

Hydrogen Chloride HCl Hydrogen Sulfide H2 S itric Oxide O itrous Oxide 2O Oxygen O2 Sulfur Dioxide SO2

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QUALITATIVE TESTS FOR METALS:
Method Procedure Clean a platinum wire by dipping it into dilute HNO3 and heating in the Bunsen flame. Repeat until the flame is colorless. Dip a platinum wire into the substance being tested (either solid or solution), and them hold it in the hot outer part of the Bunsen flame. Observations Na+ Golden Yellow K+ Violet 2+ Ca Orange Red 2+ Sr Bright Red 2+ Ba Yellowish Green Cu2+ Bluish Green Crimson Brown Black Black Black Black Black Black Yellow Light Yellow Orange White Brown Blue Green Light Pink

Flame Test

Hydrogen Sulfide Test

Ash Test

Li+ Pb Cu Ag Hg Bubble Hydrogen Sulfide gas through the solution of a salt Ni of the metal being tested. Check the color of the precipitate Fe formed. Cd As Sb Zn Bi Al3+ Add a few drops of cobalt nitrate to the saturated solution sample of the salt. Dip a piece of filter paper in the solution. Zn2+ Dry it and then burn it gently in the Bunsen flame. Mg2+

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THE PERIODIC TABLE SYNOPSIS HANDOUT 4
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PERIODIC DEVELOPMENT:
1. 2. 3. 4. 5. 1817 1865 1864-69 1870 1911 Germany England Germany Russia England Law of Triads Law of Octaves Meyer’s Hypothesis Mendeleev’s Periodic Law Modern Periodic Law J. W. Dobereiner A. R. Newland Lothar Meyer Dimitri I. Mendeleev Henry Mosely

PERIODIC LAWS:
Law of Triads: “If three elements are arranged in according to their atomic weights, such that the atomic weight of the middle element is mean of the other two, then they will exhibit similar properties.” Law of Octaves: “If elements are arranged according to increasing atomic weights, a given set of properties recurs at every eighth place, by analogy with the musical scales.” Meyer’s Hypothesis: “The physical properties of elements are the periodic function of their atomic weights.” Mendeleev’s Periodic Law: “The properties of the elements as well as the formulae and properties of their compounds depend in a periodic manne on the atomic weight of elements.” Modern Periodic Law: “The physical and chemical properties of elements are periodic function of their atomic numbers.” OR “The physical and chemical properties of the elements are periodic function of their electronic configuration, which vary with increasing atomic numbers in a periodic manner.”

DOBEREINER’S TRIADS:
Expected Mass 7 + 39 = 23 2 35.5 + 127 = 81.25 2 NEWLAND’S LAW OF similar to those of first. Li Be 9 7 a Mg 23 24 K Ca 39 40 Li (7) Cl (35.5) Triads with Atomic Masses Na(23) Br(80) K(39) I(127)

OCTAVES: The properties of every eighth element were
B 11 Al 27 C 12 Si 28 14 P 31 O 16 S 33 F 19 Cl 35

LOTHAR MEYER’S CLASSIFICATION:
Meyer plotted atomic volume (mass + density) against atomic weight and obtained the curves, in which elements with similar physical properties occupied similar position in the curve. i.e.:

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• • • •

Alkali Metals occupied the peak positions Inert gases, halogens and elements giving acidic oxides occur on ascending positions Elements giving basic oxides occur on descending positions. Elements producing amphoteric oxides occupy the curves.

MODERN PERIODIC TABLE:
• • 1 H 3 Li 11 a 19 K 37 Rb 55 Cs 4 Be 12 Mg 20 21 22 23 24 25 26 27 28 Ca Sc Ti V Cr Mn Fe Co i 38 39 40 41 42 43 44 45 46 Sr Y Zr b Mo Tc Ru Rh Pd 56 57 72 73 74 75 76 77 78 Ba La Hf Ta W Re Os Ir Pt 89 104 105 106 Ac Ku Ha 58 59 Ce Pr 90 91 Th Pa
107 108 109 110

So far, 110 elements have been discovered. Out of which 92 are naturally occurring and 18 are artificially made elements. 2 He 5 B 13 Al 29 Cu 47 Ag 79 Au 30 31 Zn Ga 48 49 Cd In 80 81 Hg Tl 6 C 14 Si 32 Ge 50 Sn 82 Pb 7 15 P 8 O 16 S 9 F 17 Cl 10 e 18 Ar

33 34 As Se 51 52 Sb Te 83 84 Bi Po

35 36 Br Kr 53 54 I Xe 85 86 At Rn

87 88 Fr Ra

Lanthanide Series Actinide Series

60 d 92 U

61 62 Pm Sm 93 94 p Pu

63 Eu 95 Am

64 Gd 96 Cm

65 66 67 68 Tb Dy Ho Er 97 98 99 100 Bk Cf Es Fm

69 70 Tm Yb 101 102 Md o

71 Lu 103 Lr

PERIODIC TRENDS:
Atomic Radius: The half of the distance between two nuclei present in a homo-nuclear diatomic molecule. It’s measured in Angstrom A°.

Atomic Radius ∝
Atomic Radius ∝ Electron Shell Ionic Radius: The distance between the nucleus of an

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ion and the point upto which nucleus has influenced electron is called Ionic Radius. Or the radius of a spherical ion. It’s also measured in Angstrom A°. Cations have smaller radii than neutral atom. Anions have larger radii than the neutral atom. Ionic Radius ∝ Electron Cloud

In f-block, atomic radius decreases with the increase in atomic number vertically because in this case, electrons are added to the inner d or f sub-shells.

Ionic Radius ∝
Ionization Potential: The amount of energy required to remove most loosely bonded electron from the outer most shell of an atom in its gaseous state. Its unit is Kilo-joules per mole (KJ/mol) and is also measures in electron volts (eV) Ionization Potential ∝

Ionization Potential ∝
The removal of electron becomes easier towards f-shell > d-shell > p-shell Electron Affinity: The negative of the energy change that occurs when an electron is accepted by an atom in the gaseous state to form an anion. A + e → A + (Energy released) It’s measured in Kilo-joules per mole (KJ/mol).

Electron Af inity ∝ Electron Af inity ∝
Elements with stable electronic configuration have zero electron affinity. The large values of electron affinity show that the elements are very strong oxidizing agents. Chlorine has the highest value of electron affinity. Electronegativity: The force of attraction by which an atom attracts a shared pair of electrons. It’s measured in electron volts (eV) Electronegativity of Fluorine is fixed as 4, which is the highest value.

Electronegativity ∝
Electronegativity ∝ Valence Electrons Electronegativity ∝ Ionization Potential Electronegativity ∝ Electron Af inity

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STATES OF MATTER SYNOPSIS HANDOUT 5 TES HAN
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Matter Gases Liquids Solids Plasma Pla

KINETIC MOLECULAR THEORY
“Kinetic molecular theory explain the physical properties of plains different states o matter.” tes of To be noted that: The molecules of a gas are in s re such rapid motion that they seem to resist the force of grav gravity. The speed and direction of mo motion of any given molecule are at all times unpredictable ble.

In different states of matter, rent st particles of any given substances f differ only in the manner in nly which they are arranged and ey ar are not different in kind. t diffe

FOR GASES:
All gases consist of tiny partic called molecules except inert gases which consist of atoms. particles ich co The molecular size is nearly ne arly negligible as compared to the distances between the molecules. ween t The gas molecules are in conti continuous motion in straight paths but in random directions, om di Molecules collide with one ano ne another and with the walls of container, elastically tically. Gas pressure is the collision of gas molecules with the walls of container. ion In an ideal gas, no attractive or repulsive forces exist in between molecules. tive Average kinetic energy of mol molecules depends upon the absolute temperature. (K.E)avg T ture. (

FOR LIQUIDS:
In a liquid, molecules are fairly randomly arranged. e They consist of clusters in whi they are very close together. which Molecules constitute 70 % of t total volume. the They have a definite volume b do not have any definite shape. ume but

FOR SOLIDS:
In a solid, molecules are closel packed. closely The forces of attraction betwee them are very strong. between They are arranged in a fixed pa ixed pattern, forming a lattice of vibrating masses. They have a definite shape.

GASES:
GAS LAWS:
Boyle’s Law: “The volume of a given mass of a gas is inversely proportional to the pressure me ional t exerted on it provided that tempera emperature is kept constant.” Mathematically, V V k PV k On plotting volume of a gas ag against the total pressure, a parabolic curve is obtained. obt While, on plotting volume of a gas against the reciprocal of total pressure, a straight line is e re, st obtained.

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STATES OF MATTER SYNOPSIS HANDOUT 5
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Charles’s Law: “The volume of a given mass of a gas is directly proportional to its absolute Temperature, provided that pressure is kept constant.” Mathematically, V

T

V

k

T

k

When the volume is plotted against the temperature, a straight line is obtained. At absolute zero the volume of gases is considered to become zero and all the motion ceases to exist. For each Celsius degree rise in temperature, the volume of a gas expands by 1/273 of it’s volume at 0°C Avogadro’s Law: “The volume of a gas is directly proportional to the number of molecules of the gases at constant pressure and temperature.” Mathematically, (at constant temperature and pressure) Graham’s Law of Diffusion: “The rates of diffusion of gases are inversely proportional to the square root of their densities under same conditions of temperature and pressure.” Mathematically, r For Effusion, Dalton’s Law of Partial Pressure: “The total pressure of a mixture of non-reacting gases is the sum of the partial pressures of various gases in the mixture.” Mathematically, P = + + + ⋯+ Gay-Lussac’s Law (Law of Pressures or Law of Combining Volumes): “At constant volume, the pressure of a given mass of a gas is directly proportional to its absolute temperature.” Mathematically, P

r

T

P

kT

k
Units of Universal Gas Constant

Ideal Gas Equation or Equation of State: PV = nRT. This equation is called the equation of state because when the four variables – pressure, volume, temperature and number of moles are specified, we can define the state of gas.

Value of R 0.082058 L.atm.mol-1.K-1 62.364 L.torr. mol-1.K-1 8.3145 J. mol-1.K-1

When P is in atm P is in torr P is in Pa;V is m3

BEHAVIOUR OF GASES:
Real gases deviate from ideal behavior at low temperature and high pressure. Real gases obey the ideal behavior at high temperature and low pressure. GAS DENSITY: Gases are less dense than liquids and solids. Gas Density Pressure Gas Density 1 T Gas Density Molar Masses

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STATES OF MATTER SYNOPSIS HANDOUT 5
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PRESSURE:
Pressure is measured by a device named “Manometer”. ∆P, the difference in barometric pressure Pbar and the pressure of gas Pgas is given by the difference in mercury levels in open and closed arms of the device.∆P = ∆h = hopen - hclosed If Pgas is greater Pbar, Pgas = Pbar + ∆h If Pgas is less Pbar, Pgas = Pbar – ∆h P=g.d.h Where g = 908m/s2;d= density, h= height of column

LIQUIDS:
VISCOSITY (η): The force of internal friction which opposes the displacement of different
layers relative to one another. The S.I unit of viscosity is (N. s m ) Viscosity is an intensive property. Viscosity Molecular Size Viscosity Intermolecular Attraction Viscosity 1 Temperature

Viscosity Molecualr Shape The grading of motor oil is done on the basis of viscosity, e.g. grade 30 oil is less viscous than the grade 40 oil.

SURFACE TENSION (γ): The force per unit length or energy per unit area of the surface
of a liquid. Its units are N/m, J/m2, Dynes/cm, erg/cm2 Surface Tension is an intensive property. Surface Tension Intermolecular forces Surface Tension Hydrogen Bonding Surface Tension 1 Temperature

VAPOUR PRESSURE: The pressure exerted by the vapours when they are in equilibrium
with the liquid phase. It’s constant at constant temperature. Vapour pressure depends upon the nature of liquids. Vapour Pressure Temperature Vapour Pressure 1 Intermolecular Forces The vapour pressure of an aqueous solution is always lowered by addition of more solute. On lowering of vapour pressure, the freezing point is also lowered, while the boiling point is raised.

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SOLIDS:
Solids Crystalline Solids olids Characteristic Geometrica Shape etrical Sharp Melting Point Different phy.prop. in dif. di directions Posses Symmetry etry Amorphous Solids lids Non repeitive 3-D struct tructure Melting Point varies aries Same phy. prop. in all directions l direc Non-symetrical

TYPES OF CRYSTALS:
Crystal Ionic Crystals Structural Pri Principal Particles Fo Forces Cations and Elect Electrostatic Anions Attr Attractions Properties Example

Covalent Crystals

Atoms

Cov Covalent Bond

Cations and Metal Bond Metallic delocalized electrons Atoms or non- Disp Dispersion Molecular Fo Forces Crystal polar molecules ( on-polar) Metallic Crystals

Molecular Crystal (Polar)

Polar Molecules

Disp Dispersion for forces & dipol dipole dipole attra attractions Hyd Hydrogen Bo Bonds

Hydrogen Molecules with Bonded H bonded to N, O or F

Hard, Brittle NaCl, CAF2, High M.P K2S, MgO Nonconductors as solids but good ood conductors as liquids Indefinite growth of crystal. Many are soluble in polar solvents. ents. Very hard Graphite, High Melting Point or Sublime Diamond, Silica, Carborundum, Low Density SiC, AlN, SiO2 High Refractive Index Most are non-conductors of electricity Lustre, Malleable, Ductile Metallic High M.P Crystals Conductors of Electricity and Heat M.P (Extremely low to moderate, Ice, I2, CO2, varying with mol. Wt.) Readily sublime in some cases Soft Soluble in non-polar solvents Low Melting Point HCl, H2S, Non-conduction of heat and CHCl2, electricity (CH3)2O, Soluble in other polar and some (CH3)2CO non-polar solvents M.P (low to moderate) H2O, HF, NH3, Soluble in other hydrogen bonded ded CH3OH, liquids and some polar liquids. CH3COOH

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STATES OF MATTER SYNOPSIS HANDOUT 5
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ISOMORPHISM: The phenomenon in which two substances have the same crystal structure.
E.g. CaCO3 & NaNO3 exist in trigonal crystals|ZnSO4 & NiSO4 exist in Orthorhombic Crystal Properties: They have different physical and chemical properties. They have same empirical formula. Their solutions on mixing form mixed crystals.

POLYMORPHISM: The phenomenon in which the substance can exist in more than one
crystalline form. E.g. CaCO3 occurs in two crystalline forms (i) Calcite (trigonal) (ii) Aragonite (orthorhombic)

UNIT CELL: The basic structural unity which when separated in three dimensions generates
the crystal structure.

CELL DIMENSIONS:
ames Cubic Tetragonal Orthorhombic Trigonal Hexagonal Monoclinic Triclinic Sides ≠ ≠ ≠ ≠ ≠ Angles 90 ° 90 ° 90 ° ≠ 90 ° 90 °; 120° 90 °; ≠ 90° ≠ ≠ ≠ 90 ° Examples NaCl, ZnS SnO2 FeSO4.7H2O CaCO3, NaNO3 Graphite, snow flakes CuSO4.5H2O K2Cr2O7

≠ ≠

CHANGE OF STATE:
Critical Pressure: The minimum pressure to liquefy a gas at its critical temperature. Triple Point: The only temperature and pressure at which three phase a pure substance can exist in equilibrium with one another in a system containing only the pure substance. Boiling Point: the temperature at which the vapour pressure of the liquid equals the outside pressure. Boiling Point Pressure Effect of Concentration on Boiling Point and Freezing Point: Type Concentrations Boiling Freezing Examples Point Point 1 100.51°C -1.86°C Sugar, Urea Molecular on-ionizing 2 101.02°C -3.72°C HCl Molecular Ionizing 2 101.02°C -3.72°C NaCl Ionic dissociated 3 101.53°C -5.58°C CaCl2, Cu(NO3)2 Ionic dissociated This indicates that in a 1 m solution of molecules that do not dissociate, boiling and freezing point differs with a change of (0.51°C) and (-1.86°C) respectively.

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STATES OF MATTER SYNOPSIS HANDOUT 5
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Melting Point: the temperature at which there is equilibrium between solid and liquid phases. Effect of Pressure on Melting Point: Condition Situation Substance Expands on Melting 1 Substance Contracts on Melting

LATENT HEAT VALUES:
Latent Heat of Fusion: The amount of heat required to transform 1 kg of ice into water completely at O°C. Its value is 80 cal/g or 3.34 x 102 J/g. Latent Heat of Vaporization: The amount of heat required to transform 1 kg of water into gas (steam) completely at 100°C. Its value is 540 cal/g or 2.26 x 103 J/g

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ATOMIC STRUCTURE SYNOPSIS HANDOUT 6
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ATOMIC DEVELOPMENT:
1. 2. 3. 4. 5. 6. England America Germany Michael Faraday Robert Millikan William Crookes Goldstein Henry Becquerel James Chadwick Indicated the existence of electrons Measured the charge on an electron Showed the existence of electrons in atoms. Showed the existence of protons in atoms. Through Radioactivity confirmed the presence of electrons and protons Showed the presence of neutrons

England

PROPERTIES OF CATHODE RAYS:
Produce sharp shadows Emerge normally from cathode Penetrate small thicknesses of matter without any perforations Carry a negative charge Easily deflectable by an electrostatic field Easily deflectable by a magnetic field Can exert mechanical pressure

RADIOACTIVITY:
“The spontaneous breakdown of an atom by emission of particles and radiations” Types: α- particles (doubly charged He2+ nuclei) β- particles γ- particles (very short wavelength Positron emission electromagnetic rays) Electron Capture

PROPERTIES OF:
Properties 1. Nature 2. 3. 4. 5. 6. Charge Velocity Penetration Power Ionization Energy Fluorescence α- Rays 4 2He Nucleus Positive 3 x 10 to 3 x 107 m/s Very less Very high Few substance only
6

γ- Rays very short wavelength electromagnetic rays Negative Neutral 7 7 9 x 10 to 27 x 10 m/s 3 x 108 m/s Intermediate Very high.100 times of β Very Small Poor ionizers Many substance Not possible

β- Rays Fast moving electrons

X-RAYS:
“The high energetic radiation emitted by metals and glass on bombardment with cathode rays, that cause fluorescence in a variety of substance is called X-rays or Rontgen Rays ( amed after the discoverer W. Rontgen).” Characteristics: Short Wave Radiations Extremely high penetration power High Ionization Energy Electromagnetic in nature Arise from anode as a result of cathode X rays ∝ rays’ bombardment.

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ATOMIC STRUCTURE SYNOPSIS HANDOUT 6
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SPECTROSCOPY:
“The branch of chemistry which deals with the study of absorption or emission of radiation is called Spectroscopy.” Planck’s Quantum Theory: The emission of radiation is due to the vibrations of charged particles (electrons) in the body. The emission is not continuous but in discrete bundles/packets of energy called “Quanta”. This emitted radiation propagates in the form of waves. The energy associated with each quantum for a particular radiation frequency ν is given by: E = hν Where h = Planck’s constant = 6.625 x 10-35 J.sec = 6.625 x 10-37 erg.sec A body can emit or absorb either one quantum (hν) of energy or some whole number multiple of it. Spectrum: A band of rays of different wavelengths obtained from the decomposition of radiations is called Spectrum. Emission Spectra Absorption Spectra Emission Spectrum: When the radiation (absorbed by the object from an electric arc) is passed through a prism in a spectroscope, it is decomposed into component wavelengths to form an image called an Emission Spectrum. Continuous Spectrum Line Spectrum Continuous Spectrum: When a dispersed light is allowed to fall on a photographic plate, the colors from violet to red (VIBGYOR) are seen without any line of demarcation. Such a spectrum is called Continuous Spectrum. Line Spectrum: If dispersed light falling on the photographic plate is sharp, distinct and well defined by lines of demarcation then such a spectrum is called Line Spectrum. Hydrogen Spectrum: Wavelength Series n1 n2 Spectral Region Lyman Series 1 2, 3, 4, … Ultra violet Region Less than 4000°A Balmer Series 2 3, 4, 5, … Visible Region B/w 4000°A to 7000°A Paschen Series 3 4, 5, 6, … Near Infra Red Region More than 7000°A Brackett Series 4 5, 6, 7, … Far Infra Red Region More than 7000°A Pfund Series 5 6, 7, 8, … Radio Waves Region More than 7000°A

QUANTUM NUMBERS:
“The numbers that describe the distribution of electrons in atoms are called Quantum umbers.” Quantum Numbers are derived from the mathematical solution of Schrodinger’s equation for the Hydrogen atom. It has following four types: Principal Quantum Number Magnetic Quantum Number Azimuthal Quantum Number Spin Quantum Number

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ATOMIC STRUCTURE SYNOPSIS HANDOUT 6
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QUANTUM NO.

FORMULA

VALUES

EXPLAINS ABOUT

MISCELLANEOUS
It was introduced by Bohr. It has all natural no. values. Its values are also designated by alphabets K, L, M. N etc. n=1 1st energy K shell level n=2 2nd energy L shell level n=3 3rd energy M shell level No. of electrons in an orbit could be calculated by the formula 2n2.

Principal

n

All integral values

1, 2, 3, 4, …

Principal Energy State Size of Orbit Maximum Number of Electrons in orbit Period of the element in Periodic Table

Azimuthal/ Orbital/ Angular Momentum/ Subsidiary/ Magnetic

0 1 2 3 s p d f l l = zero > (n1) M = -l +l >0 >

4 g

XXX XXX

Splitting of energy levels Shapes of orbitals Magnitude of angular momentum of orbiting electron. Orientation (axis of electrons) Sub-sub levels inside sub-levels called orbitals

It was introduced by Sommerfeld. It has only whole number values. Maximum values is equals to (2l + 1) e.g. l=3, m can have -3, -2, -1, 0, 1, 2, 3 (total seven values). +½ ↑ Clock-wise Spin up - ½ ↓ Anti-clockwise Spin Down3

m

Max. Values (2l + 1)

Spin

ms or s Spin up & spin down

+½ or -½

Spinning direction of electron Rotation of electrons besides revolution.

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ATOMIC STRUCTURE SYNOPSIS HANDOUT 6
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ELECTRONIC CONFIGURATION:
“The arrangement of electrons in an atom is referred as Electronic Configuration” Electronic configuration of elements is the fundamental property by which they are placed in the periodic table and exhibit periodic properties. Electrons are arranged in different energy levels (K, L, M, N) and sub levels (s, p, d, f) according to their energy state. n 1 2 3 4 K L M N Energy Level (2) (2) (6) (2) (6) (10) (2) (6) (10) (14) s ,p s ,p ,d s ,p ,d ,f s Sub Level 2 8 18 32 Maximum Electron Pauli Exclusion Principle: “No two electrons in the same atom can have all the set of four quantum numbers identical” Or “Only two electrons may occupy the same atomic orbital and these must have opposite spins.” Auf Bau or Building-Up Principle: “For any given atom, the electrons are filled to the orbitals of lowest energy in sequence, two electrons to each orbital”

1s 2s 3s 4s 5s 6s 7s 1s 2p 3p 4p 5p 6p 7p 2s 2p 3s 3p 4s 3d 4p 5s 4d 5p 6s 4f 5d 6p 7s 5f 6d 7p 3d 4d 5d 6d 4f 5f

(n+l) Rule: “In building up the electronic configuration of the elements, the orbitals with the lowest value of (n+l) fills first; when two orbitals have the same value of (n+l), the orbital with the lower value of n fills first.” Hund’s Rule: “When several orbitals of the same type are available, the electrons first fill all the orbitals of same energy singly with parallel spins, before pairing in any one orbital takes place.”

4

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CHEMICA BONDING SYNOPSIS HAN ICAL ANDOUT 7
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CHEMICAL BOND: “The attr e attractive force that holds atoms together in a compound is com known as Chemical Bond.” Chemical Bond Secondary Bonds ds (Van der Waal forces) orces) Hydrogen Bond Coordinate Covalent Bond Dipole-Dipole Attraction London Forces

Primary Bonds onds

Ionic Bond Polar Covalent Bond

Covale Bond ovalent on on-Polar Covalen Bond ovalent

A chemical bond: Holds two identical or differen atoms as a molecule1, which possesses lower energy than the ifferent ower e uncombined atoms. Is formed with the creation of attractive forces which result in the release of energy. on e en Is formed due to the interaction of valence electrons of the combining atoms. raction oms. Makes atoms attain greatest sta test stability when they acquire an inert gas electronic configuration tronic (Octet Rule).

IONIC OR ELECTRO ROVALENT BOND:
“The chemical bond formed as a result of complete transference of valence electrons from one elec atom to the other.”
OR “The electrostatic attraction between positive and negative ions” tatic ons In an ionic bond: If the difference of Electronega ronegativity ∆E is greater than 1.7 between two e elements, then the bond formed is ionic. Only a low electronegative ele ive element (metal) is held along with a high electron lectronegative element (non-metal) and vice versa. The atom that loses electrons b trons becomes positively charged (called Cations) and th atom that gains the electrons becomes negatively c ively charged (called Anions).
1

1

A molecule is defined as the smallest pa llest particle of an element or a compound that retains the characteristics of the chara original substance.

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CHEMICAL BONDING SYNOPSIS HANDOUT 7
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The charged species is called ions, which do not retain the properties of the original atoms. The ions do not form an individual molecule in the liquid or solid phase, but are arranged into a crystal lattice or giant ion-molecule containing many of these ions. The attractive forces in the crystal lattice greatly reduce the energy of the system, making it stable. Formation of an ionic bond occurs in a number of steps, details of these steps are as follows: PATHWAY FOR IONIC BOND FORMATION: Metal (s) ───> Metal (g) + ∆H1 Gas Molecule ───> Gas atom + ∆H2 Metal (g) ───> Metal Ion + ∆H3 Gas Atom ───> Gas Ion+ ∆H4 Metal Ion + Gas Ion ───> Ionic Compound+ ∆H5 CONDITION FOR IONIC BOND FORMATION: (∆H5+ ∆H4) > (∆H3+ ∆H2+ ∆H1) Enthalpy of Sublimation Bond Dissociation Energy First Ionization Potential Electron Affinity Lattice Energy2

For solubility, solvation energy3 must be greater than the lattice energy.

CHARACTERISTICS OF IONIC COMPOUNDS: Each ion is surrounded by a fixed number of oppositely charged ions, so that the strong electrostatic forces between ions act in all directions through the crystal. Ionic compound are soluble in water and similar polar solvents because of the strong electrostatic attractions between the ions and polar molecules of the solvent. Ionic compounds are insoluble in the organic solvents because there’s no attraction between the ions of ionic compound and the molecules of non-polar solvents. In the presence of a polar solvent, such as water, the inter-ionic forces are so weakened that the ions are separated and the free ions are able to move under the influence of electric current i.e. ionic compounds are electrolytes in molten and aqueous state. Ionic compounds have low volatilities and low vapor pressure or they do not vaporize readily at room temperature. Ionic compounds are good electricity conductors in molten state but their conductivity is smaller than that of metallic substances.
“The energy released when one mole of gaseous ions arrange themselves in definite pattern from crystal lattice is referred to as the lattice energy.” 3 “The surrounding of the ions by the solvent molecules for solvation releases the energy which is known as the solvation energy.”
2

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CHEMICAL BONDING SYNOPSIS HANDOUT 7
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COVALENT BONDING:
“The chemical bond in which two atoms, who tend to gain electrons may combine with each other by sharing one or more pairs of electrons.”
In a covalent bond: If the electronegativity difference between two or more atoms is zero or not greater than 0.5, then a Non-Polar Covalent Bond is formed. If the electronegativity difference is between 0.5 and 1.7, there will not be an equal sharing of electrons between the involved atoms. Then a Polar Covalent Bond is formed. The electrons that are shared between the two atoms are the bonding electrons. Bonding electrons spend much of their time between the nuclei, resulting in the attractive forces between negative charges of electrons and positive charges of the two nuclei. In a polar covalent bonded molecule, the shared pair of electrons is attracted more towards more electronegative atom, i.e. a polar bond makes one part of molecules partially negative(δ-) and the other partially positive (δ+). Due to polar bonding, the molecule is observed to enjoy greater stability than expected. In polar molecules, electron cloud shifts towards the more electronegative atom. Characteristics of a Covalent Compound: Exist as separate covalent molecules, electrically neutral and have little attractive forces for each other called Van der Waal Forces. Mostly low volatile liquids or gases or low melting solids. Non-electrolytes Insoluble in water and similar polar solvents but soluble in organic solvents.

COORDINATE OR DATIVE OR CO-IONIC COVALENT BOND:
“The covalent bond in which the bonding electron pair is provided by a single atom”

3
The group VA, VIA or VIIA form such type of bond. Once formed, a co-ordinate covalent bond becomes indistinguishable from a covalent bond.

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CHEMICA BONDING SYNOPSIS HAN ICAL ANDOUT 7
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MULTIPLE BONDS: In multiple covalent bonds the attraction force is bonds, much stronger than the single cova le covalent bonded molecules making molecules much more stab Due to this fact: re stable. Bond energy is higher in multi covalent bonds and multiple Bond lengths in multiple coval bonds are shorter covalent Multiple bonded compounds a much stable than single bonded compounds. unds are unds. Bond stability ∝ Bond energy nergy Bond stability ∝ Electron Den n Density 1 Bond stability ∝ Bond length

METALLIC BOND:
Atoms in metallic crystals are bonded together by electron cloud. ystals

“The strong force of attraction between these differently charged particles forms Metallic ction es fo Bond.”
The valence electrons in a metal ar not held etal are strongly because metals have smal number of e small valence electrons. The forces in m s metallic bonds are electrostatic in origin. They ca be easily hey can released to the common pool due t weak l to binding force. The atomic orbitals holding the rbitals, valence electrons are assumed to m ed merge to produce a delocalized orbital syste l system throughout, on which the electrons are free to ctrons move. Characteristics of a Meta etallic Bond: Ability to act between identica metallic atoms, and at the same time between widely entical ween different metallic atoms. Lack of direction, as shown by the positive retention of properties in the liquid state, and of wn saturation to permit large numb of close neighbors. e number Attractive force varies inversel as some high power of inter atomic distance. versely tance. Ability to permit electron trans from one atom to another atom. n transfer Equilibrium repulsive force, W Which is atomic in nature.

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CHEMICA BONDING SYNOPSIS HAN ICAL ANDOUT 7
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PROTONIC BRIDGE OR HYDROGEN BONDING: GE
“An electrostatic attraction betw between neighboring molecules is setup when the positive pole of p
one molecule attracts the negativ pole of neighboring molecule. This type of attractive force gative a which involves H ves Hydrogen is referred as Hydrogen Bonding.” Hydrogen bonding is the st strongest of the secondary bonds but is still weaker than a l weak normal covalent bond. Hydrogen bonding: Affects the physical properties of the compound. erties Increases the melting and boilin point of the boiling compound. Reduces the vapor pressure. Increases the heat of vaporizatio rization. Water has higher boiling p iling point than hydrogen fluoride. The oxygen atoms have t non-bonded two pairs of electrons and there are two polar hydrogen atoms (Hδ+) present in three dimen dimensional bonding. Conditions: Hydrogen should be bonded to a highly ded electronegative element such a N, O, F etc as Hydrogen bonding ∝ ionic cha ic character Hydrogen bonding ∝ ∆EN

DIPOLE MOMENT (µ µ):
“A dipole (polar molecule) tend to become oriented in an electrical field. The extent of this tends tendency is referred to as the dipole moment.” ency
µ=exd Where, e = magnitude of charge d = distance between the charges. arges. The S.I Unit is coulomb meter (Cm ter (Cm) Dipole moment ∝ ∆EN Dipole moment ∝ geometr of molecule ometry
URE NATUR Diatomic non-polar Diatomic Polar Tri-atomic Line c Linear Tri-atomic Ang c Angular Tetra Atomic Penta Atomic

DIPOLE MOMENT Zero Greater than Zero Zero Greater than Zero Appreciable Zero

EXAMPLE PLES H2, Cl2, Br2 HF, HCl , CO2, CS2 H2O, H2S, CaC2 Ca NH3 CH4, CCl4

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CHEMICAL BONDING SYNOPSIS HANDOUT 7
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BOND ENERGY:
“The energy required to break a bond between two atoms in a diatomic molecules is known as the Bond Energy.”
H–H Hydrogen Molecule O=O Oxygen Molecule ───> 2H Hydrogen Atom 2O Oxygen Atom OR ∆H = 435 KJ/moles

───>

∆H = 435 KJ/moles

“The energy released in forming a bond from the free atoms (not from the atoms in their standard states.)”
H (g) O (g) + + H (g) O (g) ───> ───> H-H O=O ∆H = - 435 KJ/moles ∆H = - -498 KJ/moles

Reminder: Breaking of Bonds is endothermic and making of bonds is exothermic. Bond Energy ∝ Type of Bond Bond Energy ∝ Ionic Character Bond Energy ∝ Stability Bond Energy ∝ 1 Bond Distance Bond Energy Trend: Ionic Bond > Polar Covalent Bond > on-Polar Covalent Bond

BONDING ORBITALS:
“A covalent bond is formed as a result of overlapping of atomic orbitals of combining atoms giving molecular orbitals.”
The overlapping of atomic orbitals is of two types: Sigma(σ) Bonding Pi(π) Bonding

Sigma Bond: “A bond which is formed by the axial overlap of two orbitals belonging to different atoms” It is formed by the axial overlapping of s-s, p-p, s-p orbitals. Pi Bond: “A bond which is formed by side ways (parallel) overlapping of atomic orbitals”

6

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CHEMICAL BONDING SYNOPSIS HANDOUT 7
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Two different theories determine the behavior of electrons in a bonded atom. It is as follows Valence Bond Theory Molecular Orbital Theory The bonding electrons occupy the atomic orbitals4 of the bonded atoms. The bonding electrons occupy molecular orbitals5 which belong to the whole molecule.

Suggests

According to molecular orbital theory, linear combination of atomic orbitals (σ) gives two molecular orbitals: σ-Bonding: A molecular orbital with high electron density in the region between two nuclei having lower energy than either of the parent atomic orbitals from which molecular orbital is derived. σ-Anti Bonding: The molecular orbital having high energy and low electron density between the nuclei, is less stable than either of the parent atomic orbitals from which it is derived.

HYBRIDIZATION:
“The mixing of various atomic orbitals to produce the same number of equivalent orbitals having same shape and energy”
Types of Hybridization: Mixing Orbitals One-s & three-p One-s & two-p One-s & one-p Type of Hybridization sp3 sp2 sp Type of Hybrid Orbitals sp3 orbitals sp2 orbitals sp orbitals Number of Hybrid Orbitals Four Three Two

sp3 (Tetrahedral) Hybridization: Possesses the character of both s- and p- orbitals in the ration of 1:3. sp3 orbitals are directed towards the four corners of a regular tetrahedron in which each angle is 109°.28’. Forms the strongest bonds among hybrid orbitals. Examples: CH4, SiCL4, SnCl4 etc sp2 (Trigonal) Hybridization: Possess one-third character of s-orbitals and two third characters of p-orbitals.

7
4 5

An orbital in which, the electron is influenced by one nucleus (mono-centric) An orbital in which, the electron is influenced by more than one nucleus (poly-centric)

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These orbitals are co-planar and directed towards the corners of an equilateral triangle (trigonal) at angles of 120° to each other. Examples: C2H4, C2H6 etc sp (Diagonal) Hybridization: Possesses the character of both s- and p- orbitals in the ration of 1:1. These orbitals are co-linear at an angle of 180°. Examples: C2H2, BeCl2 etc Hybrid Orbital Model: Hybridization sp sp2 sp3 sp3 sp3 Lone Pairs Zero Zero Zero One Two Bond Angle 180 ° 120° 109°.28’ 107° 104.5°

MOLECULAR GEOMETRY:
The geometrical shape of a molecule depends upon the repulsion factor among the electrons pair of an atom. There are two types of electron pairs surrounding the central atom: Bond Pair: These are the result of sharing of unpaired electrons of central atom with unpaired electrons of surrounding atoms. Lone Pair: These are the paired electrons, which have not taken part in sharing. They are also called “Non Bonding Pairs”. The repulsion factor of these active sets of electrons behaves as follows: Lone Pair – Lone Pair repulsion > Lone pair – Bond Pair repulsion > Bond – Bond Pair repulsion The shape of an atom could be predicted by the number of electrons groups6 in a molecule. A general observation is as follows: 2 Electron Groups: Linear 3 Electron Groups: Trigonal Planar 4 Electron Groups: Tetrahedral 5 Electron Groups: Trigonal Bipyramidal 6 Electron Groups: Octahedral

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An electron group is any collection of valence electrons localized in a region around a central atom that exerts repulsion on other groups of valence electrons
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THERMO MOCHEMISTRY SYNOPSIS HANDOUT 8 HAN
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Thermochemistry: The bran of chemistry which deals with the measurem of heat branch surement evolved or absorbed during a chem chemical reaction. Thermodynamics: The study based on the principles of conservation of energy. e f ener

THERMOCHEMICAL REACTIONS: The chemical reactions which are AL ions w
accompanied by energy changes w the material changes. nges with

Thermochemical Reactions Exothermic Reaction ermic
EXOTHERMIC REACTI CTIONS: The chemical reactions accomp ccompanied by the emission of heat energy with th formation the of product. The chemical reactions which have greater hich energy released as compared to activation ared energy. The chemical reactions in whic chemical n which energy is converted to thermal energy. ermal Reactants ───> Products + H ts Heat H1 > H2 ∆H = H2-H1 = [a negative valu value] Examples: Combustion, Oxida Oxidation, Neutralization etc Exothermic Reac eaction Reactants

Endothermic Reaction ction
ENDOTHERMIC REACTIONS: EAC The chemical reactions accompanied by the s acco absorption of heat during the formation of ing product. The chemical reactions which have greater s whic activation energy than the energy released. en The chemical reactions in which thermal s wh energy is converted to chemical energy. chemi Reactants + Heat ───> Product Pro H1 < H2 ∆H = H2-H1 = [a positive value] va Examples: Reduction, Electrolysis etc Electr Endothermic Reaction Re Products

Enthalpy H ───>

∆H < 0 [negative tive]

Enthalpy H ───>

∆H > 0 [positiv sitive]

Products Extent of Reactio tion───>

Reactants Extent of Reacti action───>

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THERMOCHEMISTRY SYNOPSIS HANDOUT 8
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THERMODYNAMIC PROCESSES: Isothermal Process: “The process in which temperature remains constant.” i.e. dT = 0 Isochoric Process: “The process in which volume remains constant.” i.e. dV = 0 Isobaric Process: “The process in which pressure remains constant.” i.e. dP = 0 Adiabatic Process: “The process in which heat remains constant.” i.e. dH = 0

FIRST LAW OF THERMODYNAMICS: This law was enunciated by
Helmholtz. “Energy can neither be created nor be destroyed, although I may change from one form to another” OR “The total energy of a system and its surrounding must remain constant”. Mathematically, q = (E2-E1) + W → q = ∆E + W → ∆E = q – W→ W = q – ∆E Facts to remember: Heat is supplied to the system: q = [positive] Work is done by the system: W = [positive] Heat is evolved by the system: q = [negative] Work is done on the system: W = [negative] Units of Heat Energy: 1 Calorie = 4.2 J 1 J = 0.239 Calorie

1 BTU = 1055 J

1 J = 107 erg

HESS’S LAW OF CONSTANT HEAT SUMMATION:
“The heat evolved or absorbed in a given reaction must be independent of the particular manner in which the reaction takes place” Let’s consider, for a certain reaction: Pathway 1: A ──────> D + ∆H Pathway 2: A ──────> B + ∆H1 B ──────> C + ∆H2 C ──────> D + ∆H3 According to the law, ∆H = ∆H1 + ∆H2 + ∆H3

MEASUREMENT OF HEAT:
Heat Capacity: “The quantity of heat required to change the temperature of system by 1°C or 1K.” ΔT Q = C ∆T Molar Heat Capacity: “The heat capacity of one mole of a substance.” Specific Heat: “The heat capacity of a one-gram sample.” = = =

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=

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TERMINOLOGY:
System: “Any specified real or imaginary part of the universe that is under consideration.” Types of System: Open System: “The system that interacts readily with the surroundings, exchanging matter and energy.” Closed System: “The system that exchanges energy but not matter with surroundings.” Isolated System: “The system that exchanges neither matter nor energy with the surroundings.” Homogenous System: “The system which is completely uniform throughout i.e. consisting only one phase.” Heterogeneous System: “The system which is not uniform throughout i.e. consisting of two or more phases.” Surroundings: “The environment of the system or rest of the universe which may act on the system is known as Surrounding.” Interactions: “The exchange of energy and/or matter between a system and surroundings.” Heat of Reaction: “The quantity of heat exchanged between a system and its surroundings for a reaction at constant temperature.” State: “A system is said to be in a certain state when all its properties are fixed.” State Function: “The macroscopic properties of a system which has some definite value for each state and independent of path in which the state is reached.” Example: Enthalpy, Temperature, etc Enthalpy: “The sum of internal energy (E) and the pressure-volume product of a system” Enthalpy is an extensive property. Enthalpy is a state function. Enthalpy changes have unique values. Entropy: “The measure of the disorder of the system.” Disorder of system increases: d (entropy) = [positive] Disorder of system decreases: d (entropy) = [negative] Spontaneous changes always occur with an increase of entropy of the universe. Entropy of a system as a whole is an irreversible process. Entropy is expressed in cal/°C or J/K (SI Unit). Gibb’s Free Energy (G): The criterion for spontaneity ∆G = [negative] → Reaction is spontaneous and feasible

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NSTC-6 PREPARATION PROGRAMME | AGA KHAN HIGHER SECONDARY SCHOOL, KARACHI.

THERMOCHEMISTRY SYNOPSIS HANDOUT 8
PREPARED BY OSAMA HASAN

∆G = [positive] → Reaction is impossible ∆G = 0 → Reaction is in equilibrium Internal Energy: “Sum of energies possessed by a system i.e. translational, vibrational, rotational, chemical, bond energy, electronic energy, nuclear energy of constituent atoms and potential energy.” E = Et + Er + Ee + En + EP.E + Ey Macroscopic Properties: “The properties of s system easily measurable for the entire bulk of the molecules.” It is divided into following two groups: Intensive Properties: “The properties of a system those are independent of the amount of material concerned.” Examples: Density, Pressure, Temperature, Refractive index, Viscosity, Surface Tension, Melting Point, Boiling Point etc Extensive Properties: “The properties of a system those are dependent of the amount of material concerned.” Examples: Mass, Volume, Mole, Enthalpy, Entropy, Internal Energy, Gibb’s Free Energy etc Heat of Formation: “The change in enthalpy, when 1 mole of a substance is produced from its elements in the natural state.”

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NSTC-6 PREPARATION PROGRAMME | AGA KHAN HIGHER SECONDARY SCHOOL, KARACHI.

HYDROGEN AND WATER SYNOPSIS HANDOUT 13
PREPARED BY OSAMA HASAN

HYDROGEN GAS:
Hydrogen atom is the simplest of all atoms with 1 proton, 1 electron and zero neutrons. The element has following specifications: I VESTIGATIO S OBSERVATIO S State Gas (colorless, odourless) Electronic configuration 1s1 Atomic Radius 0.37 A°Å Ionic Radius (H ) 1.54 Ionization Potential (1st) 1312 KJ mol-1 Electron Affinity -37 KJ mol-1 Electronegativity 2.1
20.39 K 13.98 K

1. 2. 3. 4. 5. 6. 7.

8. Liquefying Point 9. Solidifying Point

ISOTOPES OF HYDROGEN:
NAMES FORMULA PROTON ELECTRON NEUTRON 1 Protium One One Zero H 1 2 2 Deuterium 1 H or 1 D One One One 3 Tritium* One One Two H 1 *Tritium is a radioactive isotope with the half life of 12.4 years. ATOMIC MASS 1 2 3 %AGE 99.98 % 0.02 % 4x10-15 %

POSITION IN PERIODIC TABLE:
Scientists are still unable to predict the most appropriate position for hydrogen in the Periodic Table. This is mostly because of the fact that hydrogen is the simplest element of all and resembles more than one families of the periodic table. A summarized account of its placement in different groups is as follows: Group I-A(Alkali Metals) Group IV-A(Carbon Family) Group VII-A (Halogens) Similarities Dissimilarities Similarities Dissimilarities Similarities Dissimilarities Outermost Orbit Half Filled Valency Orbit Outermost Electrons Completion Valence Shells Completion Electrons Electronic State Thermodynamic Valence Orbit Valency Valence Orbit Configuration Properties Oxidation Ion Chemical Bond State Diatomic Oxidation State Formation Formation Molecule State Reducing Bond Reducing ature Oxide ature Formation ature Formation

OCCURRENCE:
By mass, hydrogen makes up only 0.9% of Earth’s crust. In number of atoms in Earth’s crust, hydrogen ranks third (15.1%) after Oxygen (53.3%) and Silicon (15.9%). Hydrogen makes up 89% atoms on the sun and 85 to 95% of the atoms in the atmosphere of outer planets (Jupiter, Uranus, Saturn and Neptune). In universe, as a whole, 90% of the atoms are Hydrogen, and the rest are mainly Helium.

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NSTC-6 PREPARATION PROGRAMME | AGA KHAN HIGHER SECONDARY SCHOOL, KARACHI.

HYDROGEN AND WATER SYNOPSIS HANDOUT 13
PREPARED BY OSAMA HASAN

PREPARATION:
By the action of metal on hydrides By electrolysis of water By Steam and Hydrocarbon Process By Action of Steam on Coke By Steam Methanol Process Thermal Decomposition of Hydrocarbons Catalytic Reforming of Alkane Hydrocarbons Thermal Decomposition of Ammonia : : Zn + 2 H+ 2 H2 O
. / ° ° ° °

> Zn2+ + H2 > 2 H2 + O2 > 3 H2 + CO > 3 H2 + CO > CO2 + 3 H2 > C + 2 H2 > C6H6 + 4 H2
°

: CH4(g) + H2O(g) : C + H2O(g) : CH3OH(g) + H2O(g) : CH4 : : C6H14 2 H3

>

2

+ 3 H2

ATOMIC HYDROGEN:
“The product obtained as the result of dissociation of molecular hydrogen.” Preparation: H2 + 104 K. cal >2H ° H2
.

>2H

Properties: It’s more reactive than molecular hydrogen. Some of its reactions are as follows: P + 3 H ──────> PH3 O2 + 2 H ──────> H2O2 S + 2 H ──────> H2S Cl2 + 2H ──────> 2 HCl CuO + 2 H ──────> Cu + H2O AgCl + H ──────> Ag + HCl

BINARY COMPOUNDS OF HYDROGEN:
"The bi-element compounds of hydrogen with metals and non non-metals are termed as hydrides." Ionic Hydride Covalent Hydride Complex Hydride Metallic Hydride Polymeric Hydride Borderline Hydride

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NSTC-6 PREPARATION PROGRAMME | AGA KHAN HIGHER SECONDARY SCHOOL, KARACHI.

HYDROGEN AND WATER SYNOPSIS HANDOUT 13
PREPARED BY OSAMA HASAN

Combination Bonding General Formula Preparation

Ionic/Saline Hydrides s-block metals except Be and Mg Ionic Bond + M H & M2+H-2

Covalent Hydrides p-block elements

Complex Metallic Hydrides Hydrides B and Al with Transition alkali metals elements Covalent Bond Complex Bonding --------A+B3+H4 nonstoichiometric --------Alkali metal hydrides + III-A hydrides Salt like white solids Stable upto 300°C Soluble in water By heating H2 with metal under high pressure Hard Solids with metallic luster Electricity conductors Possess magnetic prop.

Polymeric Hydrides Beryllium & Magnesium ???? M2+H-2 ????

Borderline Hydrides I-B, II-B & IIIA (In, Tl) ???? ???? ????

Properties

Reactions

Examples

Uses

By passing H2 over Direct and metals at high indirect methods. temperature Colorless gases Colorless solids Volatile liquids Non-volatile High M.P Low B.P Insoluble in III-A and IV-A organic solvents are neutral Soluble in water V-A are basic Conduct VI-A and VII-A are acidic. electricity in molten state ???? XH + H2O ──> XOH + H2 XH + HCl ──> XCl + H2 XH+C2H5OH──> C2H5X + H2 B2H6, CH4, NH3, NaH, LiH, KH, RbH, CsH, CaH2, H2O, HF, HCl, SrH2 and BaH2. HI, HBr, H2S Reducing Agents ???? Dehydrating Agents Source of H2

Solid, Volatile, white in color Properties are intermediate between ionic and covalent hydrides.

Properties are intermediate between those of metallic and covalent hydrides.

????

????

????

????

LiAlH4, NaBH4 etc

????

BeH2 and MgH2. ???

????

Reducing Agent Reducing agents Catalyst Source of Atomic Hydrogen

????

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NSTC-6 PREPARATION PROGRAMME | AGA KHAN HIGHER SECONDARY SCHOOL, KARACHI.

HYDROGEN AND WATER SYNOPSIS HANDOUT 13
PREPARED BY OSAMA HASAN

USES OF HYDROGEN: Hydrogen is used:
In the manufacture of NH3, in turn, is used in the manufacture of fertilizers, plastics and explosives. To convert Benzene to Cyclohexane, a cyclic hydrocarbon used as an intermediate in the production of nylon. C6H6 + 3 H2 > C6H12 In the synthesis of methyl alcohol (methanol), an industrial solvent and raw material for making other organic compounds. To extract pure metals from metal oxides, i.e as Reducing Agent. ° WO3 + 3 H2 > W + 3 H2O Liquid Hydrogen is used a rocket fuel. The fuel tank holds 1.5 x 106 L of liquid hydrogen which powers the shuttle for about 8.5 min at the rate of consumption of 3000 L/s. In developing oxyhydrogen welding torch that readily cuts through steel and can be used to melt tungsten (W), which has a melting point of 3400°C.

WATER: HARD WATER AND WATER SOFTENING:
HARD WATER: The ground water that contains significant concentrations of ions from natural sources, principally Ca2+, Mg2+ and sometimes Fe2+ along with associated anions. Temporary Hard Water: The hard water with HCO3- as primary anion. Permanent Hard Water: The hard water with Cl- and SO42-as primary anions. WATER SOFTENING: Temporary Hard Water: Temporary hard water can be softened by boiling. A better way is to treat the water with a base, usually Ca(OH)2 that converts HCO3- to CO32-. Permanent Hard Water: Permanent hard water cannot be softened by boiling. Addition of washing soda (Na2CO3) softens permanent hard water. But soluble salts, such as NaCl and Na2SO4 remain in solution.

HEAVY WATER: The water molecule having the Deuterium isotope ‘D’ attached with
Oxygen atom in place of Hydrogen (Protium) ‘H’ The formula for Heavy Water is D2O and its molecular mass is 20 a.m.u. Uses: Heavy water is used in nuclear reactors as moderators which absorb the neutrons and slow down the process. Heavy water is used in analytical experiments for determining the mechanism of reactions.

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NSTC-6 PREPARATION PROGRAMME | AGA KHAN HIGHER SECONDARY SCHOOL, KARACHI.

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