STPM Form 6 ÷ Chapter 1: MatterMatter ÷ anything that occupies space and has mass. Fundamental Particles of Atoms (Historical Point of View) John Dalton (1808) ÷ atomic theory Atoms ÷ small indivisible particles. Atoms ÷ neither created nor destroyed. Atoms ÷ chemical reactions result from combination / separation of atoms. J. J. Thomson (1897) Electrons ÷ negatively-charged particles. Atoms ÷ positively-charged sphere. Ernest Rutherford (1911) Atoms ÷ consists of a positively-charged nucleus with a cloud of electrons surrounding nucleus. Protons ÷ positively-charged particles. Niels Bohr (1913) Electrons ÷ surrounding the nucleus (orbit). James Cadwick (1932) Neutrons ÷ electrically neutral subatomic particles. Neutrons ÷ mass almost the same with a proton. Nucleus of an atom ÷ consists of protons and neutrons. Modern Atomic Model Nucleus of an atom ÷ consists of protons and neutrons. Electrons ÷ moving around the nucleus (orbits / electron shells/ quantum shells) Atom ÷ smallest particle of an element. Relative atomic mass (Ar) - (an element) average mass of one atom of the element relative to 1/12 times the mass of one atom of carbon-12. = (average mass of one atom of the element) / (1/12 x mass of one atom of C-12) Or = 12 x [(average mass of one atom of the element) / (mass of one atom of C-12)] Cations ÷ positively-charge ions. Example: H + , K + , NH4 + and Mg 2+ Anions ÷ negatively-charge ions. Example: Br - , OH - , O 2- and S2O3 2- Molecule ÷ a group of two or more atoms. Relative molecular mass (Mr) ÷ (an element or compound) average mass of one molecule of the substance relative to 1/12 times the mass of one atom of carbon-12. = (average mass of one molecule of substance) / (1/12 x mass of one atom of C-12) = 12 x [(average mass of one molecule of substance) / (mass of one atom of C-12)] Proton number / Atomic number / Number of protons (Z) Number of protons in the nucleus of an atom. Number of electrons (neutral atom). Nucleon number / Mass number / Number of nucleon (A) total number of protons and neutrons in the nucleus of an atom. A = Z + N N = number of neutrons Ìsotopes (of the same element) atoms having the same proton number but different nucleon number. same number of protons, number of electrons, electronic configuration and chemical properties. different nucleon number, relative mass, density and rate of diffusion. Relative isotopic mass ÷ the ratio of the mass of one atom of the isotope relative to 1/12 times the mass of one atom of carbon-12 isotope. = (mass of one atom of the isotope) / (1/12 x mass of one atom of C-12) = 12 x [(mass of one atom of the isotope) / (mass of one atom of C-12)] Mass spectrometry i. Vaporisation chamber ÷ sample is vaporised (produce gaseous atoms or molecules). ii. Ìonisation chamber ÷ vapour is bombarded with a stream of high-energy electrons to form positive ions. X(g) + e ÷> X + (g) + 2e. (produce positive ions) iii. Acceleration chamber ÷ positive ions are attracted towards the high negative potential plated that accelerates the positive ions to a high and constant velocity. (accelerate the positive ions). iv. Magnetic Field ÷ accelerated positive ions are deflected into a circular path according to the m/e ratio. (separate positive ions of different m/e ratio) v. Ìon detector ÷ positive ions with different m/e ratios will be deflected to the ion detector that can be recorded on a moving chart. (detect the number and m/e ratio of the positive ions) vi. Recorder ÷ a flow of current which is amplified and recorded as peaks. (plot the mass spectrum of the sample) Important note: A lighter ion will deflect more than a heavier ion (the same charge) Example: 35 Cl + will deflect more than 37 Cl + An ion with a higher charge will deflect more than an ion with a lower charge (the same mass) Example: 35 Cl2 + will deflect more than 35 Cl + Ìsotopic abundance = fractional abundance = percentage abundance One mole ÷ the quantity of a substance that contains the same number of particles (atoms, ions or molecules) as the number of atoms in exactly 12 grams of carbon-12 isotope. Avogadro constant, L or NA ÷ number of particles (atoms, ions or molecules) present in a mole of substance (elements or compounds) = 6.02 x 10 23 (unit is mol -1 ) Number of moles = number of atoms or molecules / Avogadro constant (mol -1 ) Number of particles in a sample = number of moles x Avogadro constant (mol -1 ) Mass (g) = number of moles (n) x M (Ar or Mr) Number or moles (n) = mass (g) / molar mass (g mol -1 ) Mass (g) = number of moles x molar mass (g mol -1 ) Number of moles = volume of gas (dm 3 ) / 22.4 dm 3 at s.t.p. (0C and 1 atm or 101 kPa) Number of moles = volume of gas (dm 3 ) / 24 dm 3 at r.t.p. (25C and 1 atm or 101 kPa) Volume of gas (dm 3 ) = number of moles x / 22.4 dm 3 at s.t.p. Volume of gas (dm 3 ) = number of moles x / 24 dm 3 at r.t.p. Number of moles of solute = MV / 1000 (M = concentration in mol dm -3 ) (V = volume in cm 3 ) Concentration of a solution (g dm -3 ) = mass of solute (g) / volume of the solution (dm 3 ) Concentration of a solution (mol dm -3 ) = number or moles of solute (mol) / volume of the solution (dm 3 ) MaVa / MbVb = a/b M1V1 = M2V2 STPM Form 6 ÷ Chapter 2: Gas Kinetics Theory of Matter describe the behaviour of particles in solids, liquid and gas. Solid State particles are held rigidly in fixed positions by strong attractive forces in an orderly arrangement; particles cannot move freely; particles can only vibrate or rotate about their mean position; particles have less energy (compared to liquids and gases); solids cannot be compressed; solids have fixed shapes; solids have fixed volume Liquid State particles are packed closely together in cluster; particles are not in an orderly arrangement; particles can vibrate, rotate and move freely; particles have more energy (compared to solids) but have less energy (compared to gases); liquids are not easily compressed; liquids have no fixed shape (take the shape of the container); liquids have fixed volume. Gaseous State particles are separated from each other by distance far greater than their own size; particles have no forces between the particles. particles are not in an orderly arrangement; particles can vibrate, rotate and move freely within the container; particles have more energy (compared to liquids and solids); particles are in constant random motion, moving in straight lines; particles collide (elastic) with the walls of the container, they exert a pressure on the container and there is no loss of kinetics energy during the collision; gases are easily compressed; gases have no fixed shape (take the shape of the container); gases have no fixed volume. Kinetics Theory of Gases describe the behaviour of ideal gas. the average kinetics energy of gases particles is directly proportional to the absolute temperature of the gas (Kelvin). four assumptions associated with this theory: i.) particles are small compared to the distances between particles that their volumes are negligible. ii.) particles move in straight lines. The direction of a particle's motion is changed only by its collision with either another molecule or the walls of the container. All the collisions are to be elastic (no loss of energy). iii.) particles are in constant random motion. Gas pressure is only caused by collisions of the particles against the walls of the container. iv.) Gas molecules exhibit no intermolecular forces. The particles neither attract nor repel one another. Gas Laws three common gas laws to know: Avogadro's Law, Boyle's Law and Charles' Law ÷ A, B and C laws of gases. 1. Avogadro's Law Amedeo Avogadro (1811) equal volumes of all gases at the same temperature and pressure contain equal numbers of molecules. V / n = k (a constant) V1 / n1 = V2 / n2 Where n = number of moles of gas Molar volume of a gas (volume occupied by 1 mol of any gas) at standard temperature and pressure (s.t.p.) is 22.4 dm 3 (Condition: 0C / 273 K and 101.3 kNm -1 / 1 atm.). 2. Boyle's Law Robert Boyle (1662) the volume occupied by fixed mass of gas is inversely proportional to its pressure at constant temperature. applies under isothermal conditions in a closed container. pV = k (a constant) p1V1 = p2V2 Real gases obey Boyle's law only at low pressures and high temperatures (ideal gas or perfect gas). Real gases do not obey Boyle's law at high pressures and low temperatures (non-ideal behaviour). 3. Charles' Law Jacques Charles (1780) the volume occupied by fixed mass of gas is directly proportional to its absolute temperature at constant pressure. V / T = k (a constant) V1 / T1 = V2 / T2 Temperature is the absolute temperature (-273C / 0 K) Absolute temperature scale (Kelvin scale) as the temperature -273C was adopted as the 'zero'. Ìdeal Gas Equation Combining Avogrado's law, Boyle's law and Charles' law Ìdeal gas equation: pV = nRT where R is a constant and its value of 8.31 J mol -1 K -1 pressure: Pa or Nm -2 (1 atm = 101 kPa) volume: m 3 (1 cm 3 = 1 x 10 -6 m 3 ; 1 dm 3 = 1 x 10 -3 m 3 ) temperature: K n = m / Mr where m = mass of gas and Mr = relative molecular mass of gas m / V = p where p = density of a gas 4. Dalton's Law the total pressure of a mixture of gases do not react is the sum of the partial pressures of the constituent gases on the mixture. PT = PA + PB + PC + . where PT = total pressure of the mixture and PA, PB, PC = partial pressure of gases A, B and C. Mole fraction of A (XA) in a mixture of A and B = (number of moles of A) / (total number of moles of A + B) = nA / (nA + nB) PA = PT x XA where PT = total pressure, PA = partial pressure of gas A, XA = mole fraction of gas A 5. Deviation from Ìdeal Behaviour Factors: pressure temperature molecular size intermolecular forces Positive deviation (volume of gas molecules): low pressures (molecules are very far apart ÷ volume of the gas molecules by comparison is extremely small and can be ignored) high pressures (molecules are closer together ÷ volume of the gas molecules cannot be ignored) Negative deviation (intermolecular forces of attraction): low temperature (intermolecular forces of attraction between the molecules will reduce the force exerted by the impact of the molecules collide the wall of container. Pressure exerted by the gas is reduced). high temperature (kinetics energy of the molecules is so high that the intermolecular forces between gas molecules can be ignored). Negative deviation (polar bonds) Least deviation ÷ hydrogen gas (small molecular size and non-polar. Ìt possesses very weak intermolecular forces of attraction). Marked deviation from ideal behaviour ÷ carbon monoxide gas (polar bonds. Ìt possesses stronger intermolecular forces) Gas Pressure ÷ the force per unit area exerted by a gas through collisions against a defined area of the container wall. (Gas molecules collide more frequently with the container wall ÷ gas pressure increases) Collision Frequency ÷ the rate at which molecules in the gas system collide with each other and the wall of the container. (Collision frequency | when temperature |, concentration of gas particle |, mean free path |) Collision force ÷ the force exerted by a gas particle during collision between it and the container wall. (greater momentum and shorter time of contact increase the force of impact) Collision force can be increased by ÷ temperature increase ÷ greater velocity & greater momentum Volume ÷ region within the walls of a container. (actual volume that a gas molecule can occupy is the volume of the container minus the volume of the other gas molecules, because no two gas molecules can occupy the same volume at the same time.) Concentration (gas) ÷ the number of gas particles per unit volume in a container. (Homogeneous gas ÷ used to determine the gas concentration) Mean Free Path ÷ the average distance a particle can travel before colliding with another particle. Temperature (gas) ÷ total kinetic energy of a system. Average Kinetic Energy ÷ the mean energy of a particle in that system. (energy of each particle | , average kinetic energy | ÷ | temperature) STPM Form 6 ÷ Chapter 3: Liquid and Solid States Changes in the States of Matter Freezing / Solidification ÷ liquid ÷> solid Melting ÷ solid ÷> liquid Evaporation ÷ liquid ÷> gas / vapour Condensation ÷ gas / vapour ÷> liquid Sublimation ÷ gas / vapour ÷> solid Sublimation ÷ solid ÷> gas / vapour ($ublimation ÷ iodine, ammonium chloride and solid carbon dioxide) Kinetics Theory of Liquid The kinetics energy content of the particles in a liquid is closer to the kinetic energy content of the particles in a solid than to that of a gas. Ìmportant points: i) Liquid is made up of tiny particles. ii) Particles in liquid are continually moving in a zigzag. iii) The motion for particles in liquid are vibration, rotation and translation. iv) Particles in liquid are not in an orderly arrangement. There are loose clusters of particles which are packed closely. v) Particles in liquid have strong forces of attraction between the particles. vi) Particles in liquid have more kinetic energy than the particles in solid but less kinetic energy than particles in gases. Enthalpy of Fusion ÷ The amount of heat required to change one mole of a pure solid into a liquid. Enthalpy of Vaporisation ÷ The amount of heat required to change one mole of pure liquid into a gas. The Structure of a Liquid i) Melting process: Particles move faster when solid is heated. The vibrations of the particles increase when temperature of the hot solid increases. The particles in the solid acquired sufficient kinetic energy to overcome the attraction forces between particles. The particles break away from one another. Solid has become liquid. ii) Freezing process: The motion of particles in liquid slows down when liquid is cooled. The particles have low kinetic energy. The particles in liquid have strong attraction forces between particles to overcome the motion of the particles. Particles held in fixed positions in the lattice structure. Liquid has become solid. iii) Vaporisation process (open container that exposed to the atmosphere): The particles escape from the surface of the liquid and become gas. The rate of vaporisation increases with a rise in temperature, a decrease in external pressure and an increase in the surface area of the liquid. A rise in temperature - room temperature: small percentage of particles have high kinetics and sufficient to overcome the attraction forces between particles and then escape from the surface of the liquid. A decrease in external pressure (increase in internal pressure) - particles that have enough kinetics energy to vaporise. - vapour pressure of liquid increases. - the particles in liquid collided with one another. - particles have enough kinetics energy to vaporise. - a distribution of kinetic energy has formed. An increase in the surface area of the liquid - the particles in liquid are collided with one another. - liquid exposed to the air will evaporate (on top of the liquid). - particles with higher kinetics energies than the average kinetic energy will escape as gas particles first. iv) Boiling process: Particles move faster when liquid is heated. The vibrations of the particles increase when temperature of the hot liquid increases. The particles in the solid acquired sufficient kinetic energy to overcome the attraction forces between particles. The particles break away from one another. Solid has become liquid. Velocity of the particle increase when Temperature increase Kinetic energy increase Crystal lattice ÷ regular arrangement of atoms, molecules or ions in a crystalline solid. Unit cell ÷ a small repeating unit that contains a group of particles (atoms, ions or molecules) in a crystal. There are 7 crystal systems (primitive unit cells ÷ all the lattice points are placed at the corners of the cell only): Unit cell Characteristics Example Cubic a = b = c<a = <b = <c = 90 Sodium chloride Tetragonal a = b not = c<a = <b = <c = 90 Tin Orthorhombic a not = b not = c<a = <b = <c = 90 Rhombic sulphur Monoclinic a not = b not = c<a = <b = 90<c not = 90 Monoclinic sulphur Triclinic a not = b not = c<a not = <b not = <c not = 90 Copper(ÌÌ) sulphate, potassium dichromate(VÌ) Rhombohedral a = b = c<a = <b = <c not = 90 Calcite (calcium carbonate) Hexagonal a = b not = c<a = <b = 90<c = 120 Quartz, graphite Four types of lattice points: Lattice point at the corner of the unit cell (1/8) Lattice point on the edge of the unit cell (1/4) Lattice point on the face of the unit cell (1/2) Lattice point in the centre of the unit cell (1) Coordination number ÷ the number of atoms, molecules or ions (called the nearest neighbours) that surrounds a given atom, molecule or ion in a crystal lattice. A) Simple cubic cell Example: Caesium chloride & Polonium Sphere touches six other spheres. Four sphere in its own layer, one sphere above the layer and one sphere below the layer. Coordination number = 6 Unit cell contains in total one atom (8 corners x 1/8 = 1) B) Body-centre cubic lattice Example: Sodium, Barium, Potassium, Ìron, Manganese, Chromium & Vanadium Sphere touches eight other spheres. Second layer are placed in the hollows between the spheres in the first layer. Each sphere atom is in contact with four atoms in the layer above and four atoms in the layer below. Coordination number = 8 Unit cell contains in total of two lattice points per unit cell (8 corners x 1/8 + 1 = 2) C) Close-packed structures Example: Sodium chloride Unit cell contains in total of four atoms per unit cell (8 corners x 1/8) + (6 faces x 1/2) i) Cubic close packing (ABCABCABC) / Face-centered cubic / Simple cubic close packing Thomas Harriot (1585) first pondered the mathematics of the cannonball arrangement or cannonball stack, which has a face-centered cubic lattice. Sphere touches twelve other spheres. First layer of spheres is packed as closely and each sphere atom is in contact with six other atoms. Second layer of spheres is placed on top of the first layer, so that each sphere in the second layer rests on the hollows between the spheres in the first layer. Each sphere atom is in contact with six atoms in its own layer, three spheres (atoms) in the layer above and three spheres (atoms) in the layer below. Coordination number = 12 ii) Hexagonal close packing (ABABABABA) Sphere touches twelve other spheres. First layer and the second layer of spheres are packed in the same way as cubic close packing. (Difference = the third layer of spheres is placed on top of the first layer) Coordination number = 12 Allotropy ÷ existence of elements in two or more different forms (allotropes). Elements with variable of coordination number or oxidation states tend to exhibit greater numbers of allotropic forms and typically more noticeable in non-metal (excluding the halogens and the noble gases) and metalloids. Example: i) Different molecular configuration Oxygen ÷ O2 dioxygen (colourless), O3 trioxygen / ozone (blue), O4 tetraoxygen, O8 octaoxygen (red) ii) Different crystal structures in the solid Group 14, Group 15, Group 16 of the periodic table Group 14: Carbon ÷ graphite, amorphous carbon (soot/coal), diamond, fullerenes C60 (buckyball), Ìonsdaleite / hexagonal diamond (meteorites containing graphite strike to the Earth) and carbon nanotubes (buckytubes) is carbon with a cylindrical nanostructure. Group 15: Phosphorus ÷ red phosphorus (polymeric solid), white phosphorus (crystalline solid P4), scarlet phosphorus, violet phosphorus, black phosphorus (semiconductor) and diphosphorus P2. Group 16: Sulphur ÷ rhombic sulphur (large crystals composed of S8 molecules), monoclinic sulphur (fine needle-like crystals), plastic (amorphous) sulphur (polymeric solid) and other ring molecules S7 and S12. Enantiotropy ÷ the allotropes are stable over a temperature range, with a definite transition point at which one changes into the other. Example: i) Tin has three allotropes / two enantiotropy: alpha tin is white (metallic) tin stable above 13.2 C. beta tin is grey (nonmethallic) tin below 13.2 C. gamma tin is rhombic tin. ii) Ìron has four allotropes / four enantiotropy: ferrite (alpha iron) stable below 770°C (BCC) and the iron becomes magnetic. beta iron stable below 912°C (BCC). gamma irons stable below 1394°C (FCC) crystal structure. delta irons stable from cooling down molten iron below 1538°C and has a (BCC) crystal structure. BCC ÷ Body-centred cubic CC ÷ ace-centred cubic Allotropes of Carbon i) Graphite ÷ used as lubricant (powder or oily suspension) layered lattice structure hexoganal for the crystal system density is 2.25 g cm -3 each carbon atom is bonded by strong covalent bonds (sp 2 hybridisation / trigonal planar) with three other carbon atoms to formed hexagonal ring. the layer are held together by weak van der Waals forces. graphite is soft and slippery due to weak van der Waals forces allow the layer to slide over one another. graphite is a moderate conductor of electricity along its layer (in the direction parallel but not perpendicular to the laver) due to a free electron (per carbon atom) which can move throughout the solid lattice. (Each carbon atom has one outer shell electron (unhybridised p electron) which is not used to form covalent bonds.) ii) Diamond ÷ used as abrasives (high velocity cutting tools) and ornaments (high refractive index) crystallises in a face-centred cubic structure. single giant molecule. density is 3.50 g cm -3 each carbon atom is bonded by strong covalent bonds (sp 3 hybridisation / tetrahedral) with four other carbon atoms to formed three-dimensional giant structure. diamond has great hardness and high melting point due to the strong covalent bonds in the 3-D structure. diamond is a non-conductor of electricity due to all the four valence electrons of the carbon atoms are involved with covalent bonding, therefore no free/delocalised electrons. iii) Fullerene / Buckyball / Buckminsterfullerene ÷ used as lubricant, semi-conductor, superconductors and catalyst Molecular formulae of fullerene are C20 (smallest member), C32, C60 (most common member), C70, C76, C78, C84 and C90. spherical molecules of 20 ÷ 90 carbon atoms (32 sides, 12 pentagons and 20 hexagons). simple molecular solid. each carbon atom is bonded by strong covalent bonds (sp 2 hybridisation / trigonal planar) with three other carbon atoms. Ìt also contains delocalised ¬ electrons which does not exhibit "superaromaticity¨ that the electrons in the hexagonal rings do not delocalise over the whole molecule. Fullerene is a superconductor when it mixed with other metals. Allotropes of Sulphur (different molecular arrangement) i) alpha sulphur / rhombic sulphur (large crystals composed of S8 molecules) lemon yellow colour shape of an octahedron. crystallises with the orthorhombic lattice. more stable at room temperature (formed in temperature below 95.6C). melting point at 113C. density is 2.07 g cm 3 . ii) beta sulphur / monoclinic sulphur (fine needle-like crystals of S8 molecules) deeper yellow colour shape of long, narrow and thin needle. crystallises with the monoclinic lattice. stable at temperature above 95.6C. melting point at 119C. density is 1.94 g cm 3 . Summary: Definition of the states of matter State Shape of substance Volume of substance Solid Definite Definite Liquid Ìndefinite Definite Gas Ìndefinite Ìndefinite Phase ÷ refers to a single homogeneous physical state of a heterogeneous system. There are three phases with the same composition solid, liquid and gas. Triple point ÷ the point of a condition of temperature and pressure at which the solid, liquid and vapour phases exist simultaneously at equilibrium. Critical point ÷ is the highest temperature and highest pressure at which there is a difference between liquid and vapour states. At either a temperature or a pressure over the critical point, only a single fluid state exists, and there is a smooth transition from a dense, liquid-like fluid to a tenuous, gas-like fluid/or pressure that is required to liquefy a gas at its critical temperature. Supercooling ÷ metastable condition where a liquid can exist below its freezing point. Phase Diagrams Ìn laboratory, experiments are being carried out on two environmental factors which is temperature and pressure (referred to as independent variables). A) The Phase Diagram of Water - ice (solid), water (liquid) and water vapour / steam (gas) Vapour Pressure Curve - critical point = critical temperature (374C) and critical pressure (200 atmospheres) - temperature above 374C and critical pressure 200 atmospheres, the vapour and liquid are indistinguishable (no longer two separate phases) because the densities of the gas and liquid are equal (meniscus separating a liquid from its vapour disappears). Melting Temperature Curve - melting temperature point decrease with pressure- supercooling is the cooling of a liquid to below its freezing point without a change taking place from the liquid to the solid state. A phenomenon (metastable condition) shows the vapour pressure of water below its freezing point. Triple Point - Water triple point is at temperature 0.01C and pressure 0.006 atm (610 N m -2 ). All the three phases (ice, water and water vapour) coexist at equilibrium. Normal Melting Temperature Point - the temperature at which both the solid and the liquid states of the substance exist in equilibrium at a pressure of 1 atm (101 kNm -2 ) Normal Freezing Temperature Point - the temperature at which both the liquid and the solid states of the substance exist in equilibrium at a pressure of 1 atm (101 kNm -2 ) Unsual Behaviour of Water i) Why ice can float? - the volume of water increase when the change of phase from liquid to solid. Reasons: Ìce (solid) has an open structure (hydrogen bond). ii) Why the melting temperature curve slopes to the left (melting point decreases with pressure)? - (Ìn most of substances (except water), an increase in pressure will push the molecules even closer / Ìncrease in pressure favours the physical state which is higher density) Reasons: Ìncreasing the pressure favours the formation of liquid water due to the latent heat of fusion is absorbed from the surroundings during melting. B) The Phase Diagram of Carbon Dioxide - solid carbon dioxide (dry ice), liquid carbon dioxide and gas carbon dioxide Vapour Pressure Curve critical point = critical temperature (374C) and critical pressure (217 atmospheres) - temperature above 374C and critical pressure 217 atmospheres, the vapour and liquid are indistinguishable because the densities of the gas and liquid are equal. At this point, carbon dioxide gas can be liquefied. Melting Temperature Curve - melting temperature point increase with pressure - melting temperature curve slopes to the right - density of dry ice (solid carbon dioxide) is higher than the density of liquid carbon dioxide. Ìt is because the carbon dioxide molecules are held closer together (smaller volume). - Ìncreasing the pressure favours the formation of solid carbon dioxide due to the latent heat of fusion is liberated (given out) to the surroundings. Triple Point - Carbon dioxide triple point is at temperature -57C and pressure 5.1 atm. All the three phases (solid, liquid and gas) coexist at equilibrium. Normal Sublime Temperature Point - the temperature at which both the solid and the gas states of the substance exist in equilibrium at a pressure of 1 atm (101 kNm -2 ) - at atmospheric pressure, solid carbon dioxide (dry ice) sublimes to form carbon dioxide gas at -78C. Ìmportant Points of Water Phase Diagram and Carbon Dioxide Phase Diagram Water Carbon dioxide Phase Diagram ice, water and water vapour / steam solid carbon dioxide (dry ice), liquid carbon dioxide and gas carbon dioxide Vapour Pressure Curve Critical Point = 374C and 200 atmospheres Critical Point = 374C and 217 atmospheres Triple Point 0.01C and 0.006 atm -57C and 5.1 atm Melting Temperature Curve Ìncreasing the pressure favours the formation of liquid water Ìncreasing the pressure favours the formation of solid carbon dioxide Difference between the three phases: Solid Liquid Gas Least kinetic energy (vibration and rotational forms and do not change their positions) More energetic than solid, yet not as energetic than gas (translation, vibrational and rotational forms) Most kinetic energy (translation, vibrational and rotation forms) Solid ÷ a state having both a definite shape (fixed lattice structure) and a definite volume. Unit cell ÷ repeating structure subunits of a solid molecule (fixed lattice structure / crystal structure). Solid Simple cubic One atom per repeating unit cell Body-centred cubic Two atoms per repeating unit cell Face-centred cubic Four atoms per repeating unit cell Liquid ÷ a state having a definite volume but no definite shape. Liquid Ìntermolecular forces Hydrogen bond Polar interaction Dipole moments Van der Waals Strongest Strong yet weaker than hydrogen bond Strong yet weaker than hydrogen bond and polar interaction Weakest Surface tension ÷ the resistance of a liquid to an increase in its surface area. Viscosity ÷ the resistance of a liquid to flow / the resistance to flow by an object through the liquid. Summary of phase change : Phase Change Term Liquid to gas Vaporisation Gas to liquid Condensation Solid to liquid Melting Liquid to solid Freezing Solid to gas Sublimation Gas to solid Deposition Ìsothermal ÷ conditions where the temperature of a system does not change. Supercritical fluid ÷ Beyond critical point, it is impossible to distinguish between a gas and liquid. Normal boiling point ÷ temperature at which a material boils when the pressure is 1.00 atm. STPM Form 6 ÷ Chapter 4: The Electronic Structure of Atoms Spectrum ÷ a display of the components of a beam of radiation. Hydrogen Spectrum Hydrogen molecules break up to form hydrogen atoms when hydrogen gas (at low pressure) in a discharge tube that has been passed through by an electrical discharge. Hydrogen molecules do not emit visible light. Emission spectrum contains separate sets of lines. Each line corresponds to a light of a particular frequency / wavelength. The series of lines is called the Balmer series that consist of four colours lines. These lines are: 656 nm (red), 486 nm (blue-green), 434 nm (indigo) and 410 nm (violet) ÷ visible to the unaided eyes. Other sets of lines are: infrared region (Paschen series, Brackett series and Pfund series) and ultraviolet (Lyman series). Convergence limit ÷ wavelength / frequency at which the converging spectral lines merge together. Balmer formula: 1// = RH (1/2 2 ÷ 1/n 2 ) where / = wavelength, RH = Rydberg constant, n = 3,4 . × Hydrogen gas also emits light in the ultraviolet and infrared regions of the electromagnetic spectrum. Rydberg equation: 1// = RH (1/n1 2 ÷ 1/n2 2 ) Ìmportant Table of Summary for the Series: Series n1 n2 Type of electromagnetic radiation Lyman 1 2, 3, 4 . × Ultraviolet Balmer 2 3, 4, 5 . × Visible Paschen 3 4, 5, 6 . × Ìnfrared Brackett 4 5, 6, 7 . × Ìnfrared Pfund 5 6, 7, 8 . × Ìnfrared Electronic Energy Levels The electrons in an atom can exist at certain energy level. The electron nearest to the nucleus has the lowest energy. The further the electron from the nucleus, the higher the energy. Excited state: sufficient energy (heating or electricity discharge) is needed to promote an electron from a lower energy level to higher one. The electron will not remain at the high energy level because it is unstable. Therefore, it will fall back to the level from it started or to the intermediate level. Ìt will lose an amount of energy (energy = difference between the two energy levels). Convergence of the spectral lines ÷ difference between successive energy levels becomes smaller with the increasing distance of the energy levels from the nucleus. Quantum radiation ÷ small amount of radiation emitted by an electron when it falls from higher to a lower energy level. Planck's equation: A E = E1 ÷ E2 = hf = h (c / /) where / = wavelength, h = Planck's constant = 6.63 X 10 -34 Js, c = speed of light = 3.00 X 10 8 ms -1 A E = difference in energy of two energy levels (quantum of radiation) First ionisation energy ÷ minimum energy required to remove one mole of electrons from one mole of the atoms of an element in the gaseous state. Example: M ÷> M + + e Ground state ÷ is the energy level nearest to the nucleus and it is the lowest possible energy state. Calculation for the Ìonisation Energy of Hydrogen (Convergence limit in Balmer serier) Step 1: Find frequency difference between the successive lines in the series. Step 2: Plot a graph of frequency difference (y-axis) against the lower frequency (x-axis). Step 3: Extrapolate the graph to obtain the frequency (x-axis) when frequency difference = 0 (convergence limit) Step 4: Calculate the ionisation energy by using AE = hf Atomic orbital ÷ the region, or volume, of space in an atom within the high probability (95% chance) of finding an electron in an atom. Neil Bohr developed the model of atomic structure assuming that the electrons in an atom are in constant motion around the nucleus in circular orbits. Heisenberg uncertainty principle states the position and momentum (mass x velocity) of an electron cannot be known with great precision. Charged particles in motion create magnetic fields, therefore it is possible to learn about the pathway and position of the moving electron. Types of orbital: s, p, d and f orbital Core shell ÷ first shell that holds two electrons Valence shell ÷ the outermost shell Effective nuclear charge (Nuclear attraction) accounts for (increases from left to right of the periodic table): i) attraction to the nucleus ii) repulsion from core electrons iii) minimal repulsion by other valence electrons Ìonisation energy is influenced by: i) nuclear charge (nuclear charge increases, the force of attraction on the electrons becomes stronger and the ionisation energy increases.) ii) distance of the electrons from the nucleus (further the outer electrons are from the nucleus, ionisation energies will be lower.) iii) screening effect (outermost electrons in an atom are shielded from the attraction of the nucleus by the repelling effect of the inner effect. The higher the screening effect, lower the ionization energies.) Electronic Structure Number of electrons in shell = 2(n) 2 Example: Lithium atom. Nucleus = made up of both neutrons and protons Core shell = 1 st energy level (electron occupancy of 2) Valence shell = 2 nd energy level (electron occupancy up to 8 ) Arrangement of electrons in an atom Aufbau principle ÷ Electrons occupy orbitals with the lowest energy level first Pauli exclusion principle ÷ Each orbital can hold maximum of two electrons with opposite spin Hund's rule ÷ Orbital with the same energy level (degenerate orbitals), electron will occupy different orbital singly/one electron first the parallel spin, before pairing Electronic Configurations The electrons are filled according the orbitals (Aufbau principle). Fills the 1s orbital to: 1s 2 Fills the 2s orbital to: 2s 2 Fills the 2p then 3s orbitals to: 2p 6 3s 2 Fills the 3p then 4s orbitals to: 3p 6 4s 2 Fills the 3d, 4p then 5s orbitals to: 3d 10 4p 6 5s 2 (Extended knowledge: the process is repeated until all of the electrons have been accounted for. g-, h- and j-orbital exist in theory but the periodic table contains no elements that have electrons in either g-, h- and j- orbitals.) The first break from numerical sequencing comes when the 4s level is filled before the 3d level, despite the fact that the perimeter of the 3d level is closer to the nucleus than the 4s orbital. The reason is that the energy of the level is based on an average position of the electron, not the extreme position. Ìonising electrons are not removed from the atom in reverse order! However, the outer shell electrons are always removed first when forming cations. Examples Example 1: Electronic configuration for manganese. -> Solution 1: Neutral manganese (Mn) atom must contain 25 electrons. Electronic configuration of Mn: 1s 2 2s 2 2p 6 3s 2 3p 6 4s 2 3d 5 Example 2: Which column of the periodic table is diamagnetic? -> Solution 2: Column 2 (alkaline earth metals) and Column 8 (noble gas). A diamagnetic compound has its entire electron spin-paired. There must be an even number of electrons in the element. Valence electronic configuration for alkaline earth metals is ns 2 . Valence electronic configuration for noble gas is ns 2 np 6 . Column 1 (alkali metals) and Column 7 (halogen) are not diamagnetic. Column 6 (chalcogen) are paramagnetic. Valence electronic configuration for chalcogen is ns 2 np 4 . Example 3: Electronic configuration for chromium -> Solution 3: Half-filled d-shell stability in chromium: 1s 2 2s 2 2p 6 3s 2 3p 6 4s 1 3d 5 rather than 1s 2 2s 2 2p 6 3s 2 3p 6 4s 2 3d 4 . (Others half-filled d-shell element are molybdenum and tungsten) Example 4: Electronic configuration for copper. -> Solution 4: Fully-filled d-shell stability in copper: 1s 2 2s 2 2p 6 3s 2 3p 6 4s 1 3d 10 rather than 1s 2 2s 2 2p 6 3s 2 3p 6 4s 2 3d 9 . Example 5: Which of the following electronic configuration represents an exited state? A. He: 1s 2 B. Li: 1s 2 2p 1 C. N: 1s 2 2s 2 2p 3 D. F: 1s 2 2s 2 2p 6 -> Solution 5: B (Li should have 1s 2 2s 1 as a ground state and the electronic configuration has the last electron in a 2p- orbital that is higher energy than the ground state 2s.) An excited state electronic configuration does not follow energetic sequence. An excited state has at least one electron in an energy level higher than the ground state. Ìmportant: Not to confuse an ion (either cation or anion) with an excited state. A cation is an atom that has a deficit of at least one electron and thus carries a positive charge. An anion is an atom that has an excess of at least one electron and thus carries a negative charge. Periodic Table can be classified into 4 main groups. 1) The s-block elements: Group 1 ÷ general electronic configuration ns 1 . Group 2 ÷ ns 2 . 2) The p-block elements Group 13 ÷ ns 2 np 1 . Group 14 ÷ ns 2 np 2 . Group 15 ÷ ns 2 np 3 . Group 16 ÷ ns 2 np 4 . Group 17 ÷ ns 2 np 5 . Group 18 ÷ ns 2 np 6 . 3) The d-block elements Between Group 2 and Group 13 that the d orbitals are partially occupied. 4) The f-block elements Lanthanides (15 elements) ÷ 4f orbitals are partially filled and must have a 6s 2 . Actinides (15 elements) ÷ 5f orbitals are partially filled and must have a 7s 2 . STPM Form 6 ÷ Chapter 5: The Periodic Table The History of Periodic Table Döbereiner: Döbereiner's Triads Ìn 1817, Johann Wolfgang Döbereiner a German chemist (1780 ÷ 1849) discovered that trends in certain properties of selected groups of elements and densities for some of these triads followed a similar pattern. Newlands: Octave Law Ìn 1865, John Alexander Reina Newlands an English chemist (1837 ÷ 1898) devised a Periodic Table of elements arranged in order of their relative atomic masses and name it law of octaves. Law of octaves states that "any given element will exhibit analogues behaviour to the eighth element following it in the table". Lothar Meyer: Atomic Volume of the Elements Ìn 1870, Julius Lothar Meyer a German chemist (1836-1907) described 28 elements and arranged the atomic volume (relative mass/density) of the elements against their relative atomic masses where similar chemical and physical properties are repeated at periodic intervals. Meyer presented a series of maxima and minima curve. At the peaks of the curve, Meyer discovered that the most electropositive elements appeared at the peak (Li, Na, K, Rb and Cs). Mendeleev's Periodic Table Ìn 1869, Dimitri Mendeleev a Russian chemist (1836 ÷ 1907) published the periodic table of all known elements and predicted several new elements to complete the table that formed the basis of the modern Periodic Table. The elements were arranged into Periods (horizontal rows) and Groups (vertical columns). The arrangement of the elements in groups of elements is in the order of their atomic weights corresponds to their valences. Mendeleev predicted new elements, namely eka-silicon (germanium), eka-aluminium (gallium), and eka-boron (scandium). Moseley: Proton Number Ìn 1914, Henry Gwyn Jeffrey Moseley an English physicist (1887 ÷ 1915) discovered the relationship between an element's X-ray wavelength and its atomic number (Z), Moseley demonstrated the arrangement by nuclear charge rather than related atomic mass. Ìn Moseley's experiment the fast moving electrons strike a solid anode. From it, an X-ray spectrum is produced. Through this, Moseley's measurement of atomic numbers had an experimentally measurable basis and enable scientists to arrange the elements in the modern Periodic Table in order of increasing proton (atomic number). The Modern Periodic Table The modern Periodic Table is constructed on the basis of the proton (atomic) numbers of the elements and their electronic configuration A) The short periods Period 1 ÷ the 1s orbital is being filled. Period 2 ÷ the 2s orbital is filled first, followed by the 2p orbital in the outermost shell (8 elements). Period 3 ÷ the 3s orbital is filled first, followed by the 3p orbital in the outermost shell (8 elements). B) The long periods Period 4 ÷ the 4s, 3d and 4p orbitals are involved in the outermost shell (18 elements). Period 5 ÷ the 5s, 4d and 5p orbitals are involved in the outermost shell (18 elements). Period 6 ÷ the 6s, 4f, 5d and 6p orbitals are involved in the outermost shell (32 elements) and one series known as the lanthanides. Period 7 ÷ the 7s, 5f, 6d and 7p orbitals are involved in the outermost shell (increasing due to the discovery of new elements) and one series known as the actinides. C) The groups in the periodic table The s-block elements: Group 1 ÷ general electronic configuration ns 1 . Group 2 ÷ ns 2 . The p-block elements Group 13 ÷ ns 2 np 1 . Group 14 ÷ ns 2 np 2 . Group 15 ÷ ns 2 np 3 . Group 16 ÷ ns 2 np 4 . Group 17 ÷ ns 2 np 5 . Group 18 ÷ ns 2 np 6 . The d-block elements Between Group 2 and Group 13 that the d orbitals are partially occupied. The f-block elements Lanthanides (15 elements) ÷ 4f orbitals are partially filled and must have a 6s 2 . Actinides (15 elements) ÷ 5f orbitals are partially filled and must have a 7s 2 . All actinide elements are radioactive. Atomic Radius ÷ half the distance between the nuclei of the two closest atoms in an element. Atomic Radii ÷ decrease across a period from left to right in the periodic table & increase down a group in the periodic table. Ìonic Radius ÷ measure of the size of an atoms ion in a crystal lattice. Cation is smaller than the corresponding metal atom and anion is larger than the corresponding nonmetal atom. Electronegativity ÷ measures the ability of an atom to attract to itself the electron pair forming a covalent bond. The greater the electronegativity of an atom, the greater the atom attraction for electrons. Ìonisation Energy of an Atom ÷ measures of its tendency to lose electrons. The larger the ionisation energy, the more difficult it is to remove an electron. Atomic radii for elements in Periods 2 and 3 Elements Atomic radius (pm) Li 152 Be 112 B 80 C 77 N 74 O 74 F 72 Na 156 Mg 136 Al 125 P 110 S 104 Cl 99 Atomic radii can be classified into three categories: Covalent radius: Metallic radius Van der Waals radius Effecting factors of the atomic radius: Screening effect of the inner shell electrons: negatively-charged shells repel one another and are being pushed further away from the nucleus; screening effect increase; and size of the atoms increase. Nuclear charge (number of protons in the nucleus) that pulls all the electrons closer to the nucleus: The higher the nuclear charge; the stronger the attraction between nucleus and the electron cloud; and the size of the atom decrease. Effective nuclear charge = No. of protons ÷ No. of inner electrons A) Atomic radius across a period Example: Period 2 (Li, Be, B, C, N, O, F, Ne) and Period 3 (Na, Mg, Al, Si, P, S, Cl, Ar) Across the period: Number of protons increase by one. Number of electrons increase by one. Screening effect does not affect much (same quantum shell). Nuclear charge increase (stronger attraction between nucleus and electron cloud). Size of the atoms decrease. B) Atomic radius down a group Example: Group 2 (Be, Mg, Ca, Sr, Ba) Down the group: Screening effect increase. Nuclear charge increase. Effective nuclear charge decrease. Size of the atoms increase (the increase in the screening effect is larger than the increase in the nuclear charge). C) Ìonic radius (radius of a cation or or an anion) across Period 3 Ìon Ìonic radius No. of electrons No. of protons Na + 0.095 10 11 Mg 2+ 0.065 10 12 Al 3+ 0.050 10 13 P 3- 0.212 18 15 S 2- 0.184 18 16 Cl - 0.181 18 17 Ìsoelectronic ÷ species have the same number of electrons and the same electronic configuration. When given number of electrons (Na + , Mg 2+ , Al 3+ ) or (P 3- , S 2- , Cl - ) higher the nuclear charge, higher the force of attraction smaller the atomic size or ionic size. When given nuclear charge, larger the number of electrons in an atom or an ion, greater the repulsion between electrons larger the atomic or ionic size. Conclusion: Cationic size decreases (increasing proton number). Anionic size decreases (increasing proton number). D) Ìonic radius down a group Example: Group 2 (Be 2+ , Mg 2+ , Ca 2+ , Sr 2+ , Ba 2+ ) & Group 17 (F - , Cl - , Br - , Ì - ) Going down the Group 2 and Group 17: Each successive ion has one additional shell filled with electrons. Screening effect increase Ìonic size increase. 9...7. 4/0 :.942 .88.942 ..0:841.5489.94341.0:89.0:8 !749438 5489.974388:774:3/33:.08 9428 5489.0:8 47-98.0:8 47-9 ..74:3/903:.97438 24.438898415749438.79.97.70/3:.70/5.97438 30.70/85070 73089#:907147/ 9428 .97438 8:774:3/3903:..5.942.0:841.0 .8:-.3.438898415749438.08 0:97438 2.3/30:97438 0.4:/4100.79.3/30:97438 4/073942.2489908.0 .0 .805..43889841. 0:97438 00.0 .9428 %42843 0.209.208.3.08 0847 0.70/5.574943 :.3.30:97./.79. 9743808.00. 88 7 .9.6:.942.094.8841430.942419000203970..3002 039 #0.07.0.39:2808 942 82.041.2.02.0895.3002039 .9.79. 94241.8841430.9424190002039 .7-43 ..9208 902.07..02.8841430. . 02.07..2.9424190002039 .8841430.8841430.94241 7 . 02...:041908:-89.0 70.8841430.0 .:0 .3.74:54194472470.9.72.07.4254:3/ .300203947..9428 #0.:.70438 .094.3/ 3438 30.88 7 .9.0240.9438 5489.3/$ 40.70438 .0 .8841430240.94241 ( .2507 .9. 2.250 . 8841430240...8841430.9208902.94241.02.:0418:-89.0 .3.7-43 .07. . 3.2.8841430.94241 .8841430240.:0418:-89.0 .02..07. 8841430. 2.94241 ( !749433:2-07. 3:2-07.942. 942 :2-074100. :2-07415749438 :2-074157494383903:.3.0433:2-07.942 :.0:841..97438 30:97. 883:2-07. . 094.431:7.2.574507908 /11070393:.9041/11:843 #0.0433:2-07 8.3/.9.3/30:974383903:. :2-07413:.205749433:2-07-:9/11070393:.203:2-07415749438 3:2-074100.3:2-07415749438..97438 00.9..20002039 .88 /0389.88 907.0:841.043 949.942419084945070.3908.3.02.8841430.9743.3/7.0433:2-07 70.9441902.02.943.942 3:2-074130:97438 8494508 41908..9428.084945.9. 7-43 849450 2.9208902.8841430.94241.9424190849450 ..8841 430. . 8841430.2.94241 2.8841430.9424190849450 . ..90/5489.0438 .2-07 .007.:.9742097 '.0438.04.70/010.47/394902...241 030700.0.9 .9..4389.7/89030..309.804:8.007.007.3/.:08 438.70.9 .0438 0 0 574/:.54780/ 574/:..0438 ..943.05489.997.75.943.7/0/9...043894.8841430.908905489.8970.. 0/ .7.54:78-42-.5.2-07 5489.2-07 8..0549039.007.943.0438. 2.90905489.39...88850...2508.90/394.974389414725489.90/94.942847240. .90/9.94241 ( .5478..9. 94 805.07.043841/11070392.905489.7. 04389/11070392.07.94 . 43/090.947 5489. 79 /090.9.47/0/43.9903:2-07.3-0 70.24.07.3.9479...90/949043/090.948-0/010.3/2. 38908.8 549902./74.07..07.4.203:2-07415.8:-89.3.3 3439.-:3/.0 30240 906:.924709.250 /010.0 002039847.08 .97:24190 8.943..3.4389.3.9428 43847 240.-:3/.79.0507..9428 43847240.:08 ...0743 908.3.1441. #0.942830.2841.79.70 908.250 /010.8.942847240.924709.39 47 3:2-07415.4254:3/8 :39824 :2-074124083:2-0741.88850.3.850.-:3/.:77039.97.039..439.3/70..20.7-43 849450 .250 25479..3439.88 .9441905489.:08.3 84945.47/07 .407.393490 90743/010.3.08 .9.2510/.0.0438 .8903:2-0741.39941.70/010.09.017.70 .47/0/.3.924709.24041 8:-89.202.924709..:08 57080393.0. .88 .083./74./74.8.39 24 :2-07415.88 3:2-07412408 3 747 7 :2-07472408 3 2.4.4.4389.79.2503:2-07412408.39 24 .4389. 72.24.88 24 .72.88 24 :2-07412408.4:2041.88 3:2-0741240824.8 /2 . 98 9 5 .4:2041.9247 !.8 /2 . /2 .3/. :2-07412408. '4:2041.8 /2 3:2-07412408.97 9 5 ./2 .9247 !.3/. 98 9 5 '4:2041.8 /2 3:2-07412408. /2 . 97 9 5 :2-074124084184:90 './2 . 94341.4:203.43.0397.943324/2 '.2 43. .84:943 /2 2.884184:90 .0397. 94341.84:943 24/2 3:2-074724084184:90 24 .4:20419084:943 /2 43..0397. '...4:20419084:943 /2 . -'-. 9..00880307 .08.010/8.3/.-7.08.425.4809409073.347/07.50 9.90 5.0147.307 6:/8.0908.90.504190.70/94.4:20 .79.08.703493.79.4:7415.808 6:/8..77.01700 5.705.00880307 ..700/7/310/5489438-89743...:8907 5.3349-0.347/07.90 5.3/24.9907 /08.79.08384/8 6:/.8.9047749..334924.439.90.79...70/946:/8.3.79.4:20 6:/$9.79.425.343.-7.42570880/ 6:/8.997.703490.8 309.01700 5.08.79.302039 5.8%04741 .-4:990720..- ' ' $%! 472 .70/9484/8 -:9.03410/8.7-090-0..08.08..808 84/8.5907.79.3548943 5.08.3/.010/.302039 5.79.42570880/ 84/8.8 $4/$9..508 84/8..08.90 749.010/.0/.024700307 .425.77.083.. 79.79.708 .89.08.4:741/0.700.94341..:80/-.-7.90 5.9490.79.3/24.997.088/70.90 749.7-090-0.4:20 309.88:259438.4:20841.08-09003905.8240.4843841905.3/57088:70.. 34488410307 5.089.08.01.7082.-84:90902507.302039 5.08.0309.841 . 40 8.3/4224943 24.3/..3.:.79...9:70.:080-9343907240.79.4:208.90/9989047 5.439.38990.90/17420..80307/:7390.89434.50 9..808 .0 8249438.017009390.4.08.30/43-98.70805.03897.70/946:/8.397.306:.9308 %0/70.3 14:7. .439.3.3/84/8 5..3/4224943 .33897.307 90..8%04741.89.425.79.93477050430.504190.307 5.79.7094-00.79.03410/8.4907-/89..397.34907 ..8030741. 990.9:704190 .84190.4/0 0./74 8.79.3:2-07841240.8.79.8 9700.307 .08-090035.884.08.:08 '.808.0830907.3/.439.808.48439 0907.8085..48438.425. 20/04.70/9490/89.9907.9908..034147.307 ./74 06:.5.770.4.57088:704390.4843 .08 .4.439.857088:70843.804:8$9.:04790.08.3/90708 3448841309.4389.84190.439.. .03410/.808 /08.77.024700307 .7.703.90.439.307 900079.7030-0 5..07.307.79.79.39074380 5.79.808.8 90..0824..7147.8 0.84190.79.4389.08.8.9308 5.8.08.79.703.42243.08.9574547943./74 8.347/07.703493.42570880/ .9079.08 5..0908.439.79.08 %05.3..20902507.808.34907240. 39 '.4389.3 .. 3'. 989.4:2041.3/57088:70 8 9 5 8 /2 43/943 .7..:50/-2441.7/902507.3/.8 4.4:204.8 .3.9:70..3 07033:2-0741240841.8 . 3/ 2 .. 708 .0780574547943.8084-040 8.4389.. .88/70.439.883.39 57088:70 '.9:70 .4:204.9457088:708.9498.307 5' .-84:90902507.9:70.9574547943.92 40 8..43.5508:3/07849072...4389.9.4:204.-0.4:7 ...3/4902507.9.8841..4389.. #4-07940 90.9:708 /0.949857088:70..6:08.708 90..43/94383.:50/-10/2..808/43494-040 8.3/902507..480/.84750710.8841.8 #0.957088:708.39902507.39 5'5' #0.9.9:708 343 /0.:50/-10/2. 4389..39 '.% . %'. -84:90902507.% %02507.9:70 .9:70890. 38.92 !.4389.890 074 /0.. /0.0 .4:202 .9:70 .39..943 5'3#% 070#8.47.:041 24 57088:70!.806:..0 0.9:708. .890902507.3/./4590/.9:70 32. -84:90902507.2 2 /2 2 902507.8 6:.943 42-33...8.3/98./4 8.708 .. 40 8..47 2 . 8 2.8841.8841.9. 7 07022.3/ 770.0240.72.:.8. .98908:241905.43899:039 . 90949.943 8..57088:70419029:70.'Ý 070Ý/038941.8 .79.57088:7084190.3/ 4017.3/ ! ! !5.29:7041.3/ 3:2-0741240841 ..29:7041.57088:7041.94341 3.808439029:70 !%! ! ! 070!%949.808 .57088:7041.808/434970.79. 3:2-0741240841 3. 949. .94341.0/0.0 20.41.8 0.8240.20.07.317005.439.9:70 3907240./0130/.240.0/:73.090147.4:2 04190.70.7147.:08.997.3-03.03902507..7147.7147.3-03470/ 0.9.3-03470/ 57088:708 240.425.070. 3 3 !!% 070!%949.397.:08.307.8240.93.907242039:2.997.:.0 90147.7147.389.08507:39.4/090.:08.:08 -0.85..9.:08.8090147.0.3/90.039.0/0..349075.0 %02507.:08 457088:708 240..90.240.:0870/:.:088849.943 .70.:08.9:.943 0.70.88902 .439.79.9478 57088:70 902507.8 82.85.70.8240.4:204190 4907.9431742/0.943 .9..439....:5908..7147.57088:7041.071.:.000790/-.70//0.:08-.:..8.0309.7-43/8 0.:.3/343 54.439...:.8240. 70..7-43/8 95488088088974307 3907240.0397.4190 .4843-090039.79.0.988902 0307410.943-0900390240.3 700!..9:703.3.85. 907.0841. 307 9020...80/- 902507.00790/-.43..57088:70 !5.8 :80/94/090723090.4/39.0/0.808 4843 706:03.70.907.5.:08.04.9:70 .943 4902507.8 24017..4:209.9 70.79.9 90.307.70.04125..4:2 04190.9908.307 .000790/- 9025.8240.3349-03470/ 0..0397.9.439.94341.5..:08390.8 903:2-0741.9:70 309. .943 /7403..08-09003..4:7 .0309.030741..0 .307 48431706:03.8870/:.0397.9903907240.79..7 9548808808.841.78438097020 82.4:7 ....07.4807940907 .8240.0/ 902507..:08.4/024701706:039990.70.79..307..79..41 90.780 3907240.803074190240.8240.0841.9 4843147.0-01470..888902.:803494.439.0.3/.7-432434/0.943 39072 40.79.439.4:203.-0..307 !7088:7000790/-90.0507:39.780.307 4240304:8.8 240.997.9:70 ..07.3/84790792041.0/89. .94190240.8 949.:5890. 3907240.4907.8!7088:70 90147.4/090..48438.3030741.70.0307 902507.43.34.89/0.5.9431742/0.:.08 .20920 43..9:70 240.34.9:70 .8974:.907242039:2 '4:20 70439390.4:204190.08 !489.:0.7.8 54.3/90.80 70.439.439.943 54.5.30723:890.0.857088:703..7147.:.4:2041.309.4:20.943 .0841...:.79 .9 4843147.79. 3/$4/$9.90841 .908 .$%! 472 .308390$9.59076:/.9907 7003. 943 6:/ 84/ 093 84/ 6:/ ..8..943 6:/ .547.$4/1. .943 .54:7 43/038.8.. 54:7 6:/ $:-2.943 .8... .8.943 84/ .54:7 84/ $:-2.. 943574.41906:/ 7803902507.-7.081789 .54:7 $:-2. .08-090035.8089.79.:89078415./0.7-43.79.889028 5729.3079.943147.943147.50.0307944..38.90 0. %0249431475.30430240415:706:/394.3/8:11.42090.0824.3043024041.03079. . ...79.02470309..0839084/...79.80307089.42090 .41906:/ 905.99.7050.789..0309.997.0808.79.0836:/..439.79.6:/ 39.4206:/ '04..3 5.90/ %0.79.43903941905.8.8:5:7 434.90 ' #42-40/7. !.4/0/9430.08.9:7082.79 7.5:7084/394.547.79.90/ %0.2243:2.1742430.6:70/8:11.79.3..08384/-:9088309.088 !.704480.7.5478.990.08 !.- .70.590 4:7950841.3084/ &39.3/.42090249434190 5.07.0836:/.-.70 5.34907 $4/.54780 .-349.439.089743147.088 !. .9:70 7442902507.0/.0897:.349 45507 8:5.08. .-7.77.79.943 %0.3949.089.501742908:71.79.54780 .8. !..703493.43.79.8-0.997.99.440/ %05.0 .041906:/ /0.34907 5.039309.941.742.07../0:541935..9:7041904984/3.4/0/9430..0307.0 .473074190:39.943.8030794.0034:309.70..8-0.70.905480/9490. ":.9:703.0307944.-..941905..70.0. %070.0836:/.08-70.43.3 3.70.0836:/..390..80339073.083...24.84/9.083.80 309.80 789.08 %05.943 4/30 .943147.93:399. #42-.:08 3..70.9041.7803902507.74:5415.24:39410.0836:/.302 03941.039309.349-349.041906:/..79.34907 6:/05480/9490..08 !.70.33. .0.8003 %02507.943 749.08907309.70.03079.943-09003905.42084/ '.70.0836:/848/43036:/8.70.349-349.8-0.8 %07.79.3905.808 %05.79. !.8 .0839084/.0836:/.8030794.08.08 ..70.08-090035.03.9706:70/94.997.083.8 %0$97:.34907 $4/.79.08 .47/0.7-43/4/0 309.79.08 3.79.9433.0 .1742430..039944..0:39.054398 .997.814720/ 33.70.79.4206:/ 7003574.03073.79.04309.92485070 %05.:2.08-09003 5.79.347/07.0 43 &39..88:2/.90789.79.70.8:5:7 %7.808 39.79.79.82.541'.8003902507.77.0 70:.99.6:70/8:11./897-:94341309.79.9706:70/94.42090.250 :-.79.90 4394541906:/ 5.349 434.088 %024943415..0824.-.5478.79.089743..943841905.789.3/90308. 43574.0415.05439.79.990.08.8 25479....70.541 :843 %0.3/97. %3 794742-..08944.80309073.4730784190.808 %05.99.501742908:71.943 .90.4393:.6:/8.3..0841..-..9:70 6:/.79.08-09003 5.302039 %070..803908:71...083.70..43903941905.70... $4/:2.-349.039.79.38.70.70.349 .57088:70 5.47/0 %097.08.79.9:70 .89070384/80.9:7041.0307 %05.0309.79.507.9.79.0836:/.99.79..054398.57088:70 3.030708.9.07..6:/ 093574.79.07. ..-7.7.90 549.80309073.70.07.3.08 .48079490309.-.54:757088:70416:/3.85..79.79.8907036:/80..808 905.349-349.943147.80307.0836:/.997.08-70.9428 43847240.- .3954398 6:/82.79..8%047416:/ %0309.420.3/84/.01..70.:08474383.9:704190496:/3..0307.57088:70.01.9428 240.088 4503.705..90 ..0/.080/310/5489438390.70.8003902507.0034:309.5478..349-349.08 %05.24:39410..79...480 .789.3/-0.943841905.803908:71.-. 99. .0 .0543943900/04190:39. 0543943901.0 ..04190:39. .99. 090.430.942 240.47/0 !443:2 $507094:.0 ..9 8:774:3/8.708930-4:78 9.08:2.439.07 43085070.:-.789.03..0/9030.0.07.383949. .9428 240.473078.0884907850708 4:78507039843.3/43085070-0490.:047433.250.05439390.942 ..9433:2-07 &39..0 $250.0 447/3.039704190:39.99.-4..99.9433:2-07 903:2-0741.:0847438 .07 447/3. 08094907850708 $0..7:2 !49.439.9914:7.9428390..0 .07 .3/14:7.07.43/.383949.4194.:-.0 .250$4/:2 .0/390448-09003908507083901789.-4.99.85070.0./:2 $507094:.439.054398507:39.3080 742:2 '. 4/ .9428390.03970.9433:2-07 &39.705.3.94283.07-04 447/3.0.99.473078..88:2 743 ..07.3. 0.9428507:39..439.4114:7.383949. 480 5.0 .47/0 &39.9:708 .473078.0/897:.250$4/:2. 08.. 1. :-.3 ...4805. .0 .039070/.:-... 998.902.8.:-...3343-.8.85070.84190.0 $507094:. .07-04 447/3.94283..8.9984907.9428 390.07 ..0/4394541901789..074185070885.$250.:-.0 .07 9700850708 .0/.07 849.9428 390.3/9700850708 ..074185070885.3 %42.3343-.9433:2-07 .1..942839843..039070/.4805.30203947.89.-4.07.85070.0 .43/..0890.439..04907850708 789.9428 $0.43/...077089843 90448-09003908507083901789.8507039080.439.94283...77.480.3/0.9.7749 1789543/070/902.99...90. 908903/940-970.9433:2-07 49745 08903..431:7.7. 0.14728.4/8 .-03343 209.0/4394541901789....0/3908...09097/.:/390.-041.04907850708 789.943 03 /403 .43.447/3.4805.4805.20.705.3 $507094:.3 110703.:-.3/9080.44:7088 97403.3/209.. 0.2470349.4974508 0203989..9433:2-07474/.94389.07 447/3.49745.07.43/.0741850708.9073:2-07841 .8.808 .4038.0.250 1107039240.0410020398394472470/110703914728 .3/95.:.074185070885.3/9034-0..7.0890. 897:..789.403 4.24754:8.9.7-43 7.4430 -:0 9097.7-43 8449.9:70839084/ 74:5 74:5 74:541905074/.590 .-0 74:5.403 70/ 1107039.9. -.243/ 1:070308 -:.. /.4.090. 438/. .709 548547:8 .425480/41$240.7-433.-04.84/ . .7089.3//548547:8! 74:5$:5:7 742-.84/ 90548547:8 .59089709490 .349:-08 -:.9:70 74:5!48547:8 70/548547:8 54207.789.250 %3.3/.409548547:8 -.4974508.34897:.7-439.8:5:7 130 300/0 0.9:707.789.:08 2434..70.8.3949745 90.89700.389435439.8:5:7 .789.3/7.902507.24754:8 8:5:7 54207.243/ 209047908./.4974508.3/490773240.30 9.337.43/:.43.79 .0.548547:8 802.:08$.439.3.308394904907 .947 ..07...../0139097.9.3084/! 8.3/$ 3.89.8 5.9:-08 8. 430.3. 4974508.5..22.0 -09..93 743.9403.938742-.-4. 9389.93870 343209.3949745 .-0. 93-04 .814:7.93890 209. 2 0..03970/.0897:.9:70 04.309.42 082..590 :80/.9:70 /09.-0-04S .3/.9:70 4/ .8.-0-04S .3949745 107790 .74389.789.070/.0 . -09.-0-04 S .14790.22.743 89..743889.897:.39 54/074748:8503843 .3.-01742. 497450841. .943.789.5.8:-7.897:.88902 /03898 . .3/90743-0.7-43 7.039-43/8 85 -7/8.:-.4.:-.9428-43/0/-89743.99.03970/.14:703.743889...443/4324903743-04S.789..7-43. 170000.7-43.943.3/07..0 ...9428-43/0/-89743..:9939448 .3/07.9:70 830.03970/.4.:.:0 /03898 .3.3/85507/:0940.43/:.07..7-43.7.9435.4.08 .0-:9349507503/.24/07.0974:4:99084/.9743.08 7.73 90.039-43/8 85 -7/8.94289414720/0.4398.9474100.5.8349:80/941472..7 9490.43. .7 997004907 .8083.-7.04..039 -43/8 .07 /:094..700/940907-0.8.90.03/0 .34907 7..9743 .99..59088419.97.789..:-.84304:9078000.9743 :3-7/80/500...08.7-43..0 .5908.9743 507..942.20398 7017.8147.942 ..07 390/70..8.3/473.2 0.324.07430.7-43.1.8147.9...39240.9.243/ :80/.9.07948/04.490.897:.. 70 3.9:70 /.9474100.97.0/9.9428.000.3/20935439/:0949089743.03.7-43.974384190..4.2 43/.0/7.9014:7.039-43/3 90701470341700.4..94289414720/9700 /2 03843.9097.2 43/8...7-43.9/:094.870.343 ..43/:.39897:.9:70 /.4.9.7/3088.039-43/8390 897:.. 914:74907 . .80/00./04.97438 :07030. :..-. 0411:07030.43/:.784/ 0.9428-43/0/-89743.71472:.943.8:-7.438 8250240..:.2389071:07030 :80/.:.89 40...7-43.089202-07 2489..9428 8/08 5039..4.3/ .43/:.70 82.42243202-07 .:0841 .3/ 8507.240.:.947 8:507...438.9.039-43/8 85 -7/8.39 802 .7-43.3/ 0..9478. 9428 9.9 9.8 497450841$:5:7 /1107039240.302039 .43/:.:0 :070308.77.990 00.97438.43.8:5:7.9743.804.439.84.38/04.738/4349/04.742 .7 997004907 .:..9.5.079040240..5..80/ 00./4083490-9 8:507.8:507.7-43.974383900.7.3.94703920/94907209. 70.9 /03898 .5041.425480/41$240.8.99.44:7 8.-0.9:70-04 20935439.34.:08 024304.789.97442902507.0/743 .8:5:7.9:70 14720/3902507.789..9.742-.8089904794742-.8:5:7 .2 -09.0 247089. 2 $:22.8 %7505439 90543941.304:8.9..7013943419089.80 70107894.3/.80808982:9.3/.0-09003 6:/.8 01:/.8089908.0790.5439 890089902507.9041.3.3/.90 $..9084/ 6:/.9:7047.709700 5.504143 3.3.9902507.902507.54:7 5.4254894384/ 6:/.8 3/01390 3/01390 !.44:7 8.0 $4/ 01390 01390 6:/ 3/01390 01390 .9:70.3.99..0 '4:20418:-89.8304240304:858.389431742.8244997.3/90708..79.0 89.5439 43.43/94341902507.3/08957088:70.8301:/ 89.789./110703.89.-0.8089902434.3/93300/0 .9:70.090740304:888902 %070.9 /03898 .789.8:5:7 130300/0 0..50418:-89.54:789.2434.774.908412.9907 $9./0380 6:/ 01:/94..3.903:4:8 .841$240.57088:704.900898 .90708.9.9:70.20..0 20935439.906:-7:2 79.3/57088:70.908 90907.:08 /0050704.-4. 80.241.0 84/ ...998.7..70-03.3/ 57088:70 7010770/94.8.907.9:70 $:507.54:7.9478.9:70..28 3.8902507.3089-0498170035439 !.947 050720398.7432 039..7.-47.3/.83/0503/039.443 209.6:/.89.79.7..902507.80.1.907 .-08 %0!..907 6:/ .770/4:9439403.98706:70/946:01.-0.47 57088:709.43/943070. 70....44341.0 .93.9:70 .0 .79.-0 34430794805.5439.7006:.70 3/893:8.57088:70 .3/6:/.905.01742906:/949084/89.80957088:70 8:507.3/.78 093%02507...-0 .54:7/8.43/943 84890.924850708 902507.90 50342 0343 209.79..7.3/6:/.902507.808 -0.8.54:757088:7041.9:705439/0.35.-4.9:70.924850708 90.79.:8090/0389084190.54:7..890. 2038.7..89..8 '.443890..:8805.9:70:7.907-0498170035439 .54:7!7088:70:7.309.6:/174298.2 .550.6:/94-0498 17003543994:9..79.57088:70 .3/.0 2093902507. 92 2 &38:.3/9084/89.8.92 2 9097005.9902507.:7.4807.4:741.30415.907975054398.4:2041.3/906:/89.70.70.0 84/ .314.90841908:-89.9:70!439 90902507.3.-499084/.80357088:705:890240..-49906:/.:080.9 90..92 2 472.0089306:-7:2.0089306:-7:2.9.906:-7:2 472.9073. 093%02507.9:70.808957088:70 32489418:-89. 57088:7041.907.907 .90841908:-89.33.9:70 .9:70 /7403-43/ 902093902507.0 ..3/57088:70 .3/.08 0.3. 7003%02507..808 .0.8017426:/9484/ #0.9.4089.34503897:.3.800390.9:70!439 90902507. 57088:7041.9:70.059.03.907.907 .9.%750!439 .9.54:7 .9:70.70.0845089490019 20935439/0.0.8438. 0 .9902507.8.8.3/6:/.-499084/.80.7-43/4/0.4:20 3.90390.8 .7006:.7-434/0 84/.924850708 90.80957088:70 2093902507.7-43/4/0975054398.3.0 2093902507.807/0389 #0.700/.3/.906:-7:2 472.57088:70 84/.902507.80357088:701.7-43/4/0 /7...5439.9411:8438 -07.7.3/..390/0389416:/..-0-0.9434184/.9:70.839057088:701.0 84/..90390.241.0089306:-7:2.9.$:-20%02507.:7...889.9:70.-847-0/1742908:774:3/38/:732093 %0!.70.70 3/893:8.90.54:7..0 6:/.9:70:7..7-43/4/0 /7..7-43/4/0 !.7.7-43/4/0.808 84/ 6:/.7-43/4/0/:09490.9:70.7-43/4/0 '..79.907.4:78901472.89.70.3/57088:70 .3/.-4.79.:08. 57088:7041. 3.0 8:-2 08941472..0 .57088:70.84383.9.70...9 25479.4089.92 9097005.907.924850708 902507.79.4:789058.2 .39!439841. 9985439 ..79..907/:09490.3/.7-43/4/0.7-43/4/0240.90/ .9:70 .0 .54:7!7088:70:7.2.9411:8438 .4807940907 82.7..:8090/0389084190..034:9 94908:774:3/38 %750!439 .907!.07.9.084508949079 /038941/7.3/6:/.80.839057088:701.4:78901472.9:70!439 90902507..7.:80 90.8 .9248507.80.3-06:010/ 093%02507.7-434/0!...57088:70 .92 2 .3/..8.9:70 .70.907 .3/.3/90.7-43/4/0 98-0.80.9:7054393.2 ..943416:/.7-43/4/0 8079.90841908:-89.54:7. 3-49.943416:/ 1472.3/.7-43/4/0 /7.943.-7.9:70.0307 .3/ .14728.7-43/4/0 .7-43/4/0.84/240.8 0.9:70 .943 .9434184/.90...4:2 0 &39.93897:...70. 84/.3/749.0897:..4:7890 1...309075489438 97.!439 .9:70:7./01390.3/ 749.0307 97.8 .943.-7.8.89.808 $4/ 6:/ .3/749..7-43/4/0 '.3//4349 349.:0 10/.50 10/.8030709.54:7!7088:70:7.0-090039097005.943 470030709.3/ .0897:.3/ ...14728 $4/ .943 ./013908.92 .0 79.89309..2 .-7.9:708:-:39841.924850708 .384/ 09 489309.99.03.38.0 6:/ 890.!439 .94314728 .943.0 7050.3/.4:78901472.9.3.839057088:701..9.924850708 %750!439 .38.943.907 110703.70.99.839057088:70 3.3/ 79.92 093%02507. 93:39.079. %4.73907.0 .041.089 0..70...789.94285077050.0.03970/. 30. 4:7.94285077050.:-.3.:-.897:.03970/./01390.90.0 .70.3 /7403-43/.93:39.93:39.6:/94.3/ /7403-43/ 54.7147..943 $:71.73907.50 6:/ 3907240.803988:71.6:/9414.3.4:2 0-:934/013908.3.079.:.3/07.8 $9743089 $974309 $9743090.943 5402420398 '.3 0..89.0 6:/ .08 /7403-43/ !4.:-. '8.0 4/ .9425077050.9:70 $4/ $250.33...041.0903843 9070889..489 9070889. .97.5439 9825488-094/893:8-09003.943 $4/946:/ 093 6:/9484/ 7003 $4/94..943 ..:.942803/7403.79.:08/4349029./8..:08-70.79.8 .47708543/894..9974:906:/ $:22.90809841308 .-435439 902507.71706:03.8946:/ 43/038..9743.. /8.97:2 .8-09 28843850.80.92 $%! 472 .43/943807090902507.439.-48039057088:708 .97:2 /7403240.89484/ 0548943 849072.30 !..3/6:/ 472.2.30.943 /7403$50.34-0.-0.7.97:2.2417.42543039841.3.88902/408349.9457088:70 3..9:7041.8 $:-2.709:-09.9.9:70.8 '.8.4190.5.943 .5478.907.9:70419428 $50.1:/ 043/.70 /7403240..30 $:507.80. .09414-.9070889.880/974:-.5907%0 0.38805..79./.30 %072 6:/94.8-0035.:5941472/7403.7415.941.300.9.$97:./85. 0380708 7.409 2.0039 %080708413088.438894114:7.9..09980708.70/7043 !.7032 70/ 32 -:0 7003 32 3/4 .44:78308 %080308.0/90.3/ 32 .029 ./0/008 907809841308..8-09490 :3..380708 43.0703.409 ...8.70317.3/:97.207807089.3/!1:3/80708 ..0039. 9..2071472:..97.90.3082070940907 .073850.43.1706:03. # . . 39 3 \ /7403.850.409.3/317.4389.0039 ##/-07.8402989390:97..309.70/70438419000..9742.8.97:2 #/-0706:.3 070.943. # . 3 . 714790$0708 $0708 3 3 %504100.9743.-041$:22.03 \ 317.7.3 \ &97.207 \ '8-0 !.70/ !1:3/ \ 317.3 25479..309.409 .099 \ 317..70/ 7./.943 2.08 . 3070.70/ 0.8.9742.39%. 24:39417.0:8 ":.0-09003909403070.079../.790/479490390720/.01742989.407 03070.0 9480.08-0.300.9.974383.0-0.942.:8098:389.3.97431742903:.24:39410307 0307/110703.08 43.079 903.081742903:.%000.89040890307 %01:79079000.3.300.97.088.3.94302990/-.04190850.97.3089..0 %000.0 !.9/8.3.90/89.83/89.97430391.934700. 806:.420882 .003070.943 1 ..308 /110703.0:8 9007900307 .900..-0 %0701470 91.908:11.97431742.974330./.303070.817420794.3.0-090038:.0:8.09407430 %000. 40703070.0419003070.39:27.0703.70 8300/0/945742490..94900.9743349702...70.943 82.708994903:.99003070.0390307 0.-. 0293.0703.7.39 24943.94394903:.39573.90907.3.974383.9. 907043 47.9:70.5411706:03.997.70.9047-9..0 00.97434.9430307831:03.34/2.9:70 :2-074100.0:8.39 8 .700330110.4389.3/989040895488-0030789..943030708 0.942 :.943 .97434.3002 039390.04302404100.9430307 232:20307706:70/947024.50 . 47080 1789809.97438 '.088.4389.70.8 5 /.997.0:8-90 705030110.20780707 $905 3/1706:03..703.08 6:.9743894554890853 :3/ 87:0 7-9.309.300.3./.0:82. 83.9 41.0:8 705:8431742..942.8990408903070.974383.94/89400.000.2:2419400.:.0703./110703.:.843 .-0 .0 .747-98 0803-07:3.42 088974307.39:2417.708994903:.8500/419 28 /110703.3/242039:2 2../110703.974381742903:.3/548943419024.0 /00307.:594 77.808 90147.9 %007908...54.0.70..88. 070.:5.0./110703.47-9.5089.3.9419033070110.9 4:907248900.94341903:.0450/9024/041.705:843-4907.97438 232.3.08324943.90 89003070.943 789438.47000. .41 3/ '.$97:.300.7..9743..3.70 :.942 047/0..3.8 031706:03.3/ 90438.:.080 03070.030307419403070.:5/110703947-9.902...0:8 438..997.3/147-9.03.90 ..703.90890548943.700330110.97438380 3 .01789 !.3349 -0343970..79.0 41 13/3.94314790438.0039 !.3.70 3:.0.04.5944-9..3901706:03.8 00.3/5749438 89 47080 03070.943 030708-0407 8.7.943 30741/7403 43.10/8 90701470985488-0 940.03.03.030.3.9430307-:83 1 942.943439000.3..942.0:8 1:7907904:90700.0 00.74:3/903:..9908. 8.90 .9743.03./0:541-4930:97438.7..4:398147 3..080 904:907248980 110.942 :1-.041..4:20 4185.9743 %5084147-9.99000.3020394100.997.2003070.:547-9.7.804:889.300.0/- 3:.3.8 .0.030839080708 $905!49.0-09003908:.9 4079043.:843573.701742903:.0 29 $905.97433.0 .70.974383.:573.0419000..:5.250 0 74:3/89...:0.9090438.94303073.7080/0/174290.079.-4:9905.974384.9.73..-9 .70/5.50 0.2509:2.897:.8081742019947941905074/.9.7.88:239. .43.808 /89.9570.9429390574-.942841.97434.9743817424302404190 .97438-0.389904071706:03.8 $905 97.942.97438.0:83.47-9.03:.97438 438. 90.002 0398 74:5 38 35 .9743.000..07 904:9078000.97438.97438390002039 '.431:7...3.3080 $4:943 0:97..742:28 8 5 8 5 8 / 7.4:2341905074/.0853 -014705..45507 $4:943 : 10// 8089.3/4:23 34-0.078047/0740.209..79209.431:7.1 10// 80002039..8 .47/39047-9.-93.90/89.9422:89.3.431:7.%.17423:207..70/ %0702:89-0. '.8 /..0/174290.2.8943000.2.3.250 0.9743.3.2 .97438 0.84389.9431472.97438.705.0548943419000.08939047-:9905074/.2..97438.3/9:8.9743.383400203989.7024-/03:2.990507209074190/0.90.7708.000..9743.431:7.894/ 5 8 903/0/340/090574.79209.9743830907 ..002 0398 74:5 0307.94341 38 8 5 8 5 8 / .9429.742:2 $4:943 .0 /0859090 1.0/17890314723.3438.033:2-074100.403 ..2.07.403838 35 .943147..9743.74:3/89.39074:3/89.38 8 5 8 5 8 / 9078 .309.303070. %070.8900.94338 74:5 38 %05 -4.08887050.4:390/147 .3/9:38903 ..9.480794903:.943/408349144030709.90.431:7.8943000.9743.0.403 .419000.-08/.70 3.431:7.3.0:89. 4:23 .9.309.70 !074/.00.250 0.97433.431:7.9743..390847-9.90/89.2508 .000.8810/3942.439.431:80.9.03..50 890847-9...4254:3/.431:7.941.8838 35 4:23 .8 .374:58 %08 -4.....9000.0810/-0147090/0..8 :1-.9.8945 8 8905903847-9.0-003.03.8 %01789-70..3080 3 .99.-0.8.943147.3/ 47-9.455078 8 5 8 5 8 / 7.90.943147.97431789905.39074:3/89..5 47-9.343 9..08.30.990 030741900.90/:39.806:03.942370.908 30.8838 '.97433.300.:573.9.8 .806:03.9437057080398.943147.90/89.088 41..890.3/9000.97438.250 0.30.9079.30.0 30.9743 34990097020548943 438300.3/ 47-9.431:7. $4:943 4:23 .431:7.9429.70 .250.943..431:7.7.90 08 8 5 8 8 5 8 8 5 $4:943 84:/.3/9:8.80/43.9743.9743.30. .309.38 8 5 8 5 8 / .3-0.7708.73 0..70349/.9438.08 8 .87024.70349702 4.90.431:7..4190144300.9..0079.000..7.3090/89.8945 8 890/ 5903847-9.43000.9438 %000.90 .980703079.4208039080.-0.439.9743.3/4:23 .309.9743.250.300.343 0907.89 43000.9079.300.7010/..9743.8.9743.9743853 5..9438 .89803970 00.39 4994.8.9.948 890847-9.0.94347.03..90 25479.3...94314734-0./01.-93.5489..08-.1 10// 8089.9743.948 8905903847-9. 30/347/074190770.3//038908147842041908097.%..-041 002 0398.4.3.3/.070/9.88.209.%.0.4:20 70.79./81440/.0.942.08 .75. 0.08 89.93/08 0020398 147-9.3/8.079.02.-0 %0894741!074/.072.9 .3/07#03..3/2:89.80/.74:5 38 35 74:5 38 35 74:5 38 35 74:5 38 35 74:5 38 35 %0/ -4.4.3.3341..3 38..705.7 007942.0289 /08.9.3/2:89.0.414.%. 3 430.77.9.30/90 .4:08-0.942.0289 /0.7 007.79.99703/83.39.'4:204190 020398 3 ::849.414.:50/ %01 -4.3/3.9.3.3 57450790841800.90/74:58410020398.705../8 3 4.3/08 0020398 147-9.3-070307..77.990/47-9.705.3/74:59.8 .8.0289 /8.-0 49.-0 -070307-070307 8%7.8.3/8 .0.002 0398 0900374:5.072..8.9.8808..10/.9089.82.4:794900900203914439390 9.79.2.3.!074/.9.030020390-9.99073 0.10/.5907%0!074/.7-0/0020398.002 0398 .8 $%! 472 . 99050.990248900.3/07.550.70.89 /8.9.9743.8..3..974388970.97438 942.8 00757080390/.7488..070/9070.70.97430.810/1789 1440/-90547-9.705..002 0398 .3/8 03/000..30002039894.3/43080708343./:8 110.0.942.810/1789 1440/-90547-9.93.9.8 .90/90 .97:28574/:.3/43080708 343./ /0.9743.9079. 3:2-07841900020398.39.302039-3:. 8.00.8:7041908041.3002039 8 7.-08.90/.0:8 9.-0 %08 -4./:8.390 .94283.0.3/2:89.2.07.94294.431:7.70-03 5:80/1:7907.80/43.0.942.. .3.884190574943 .3/9080 4190..943 30741..#.8924.9419033078000./14700203983!074/8.4.079.9.0419094.43 072...0-09003903:./:8 52 0 ..8:702 03941.4.0.098. 8!074/. $ ! $ 7 ..3/.99498019000.9..77.9079000.94283.5074/174201994793905074/.914720/90-.77.2.943882.7.0/3904:907248980 0020398 !074/ 908 /.4.370.942 9070.7.97438 438.002 0398 74:5 38 35 74:5 38 35 74:5 38 35 74:5 38 35 74:5 38 35 74:5 38 35 %0/ -4.343 002 0398.:7.390.3/.0 99050...3/ 020398 942.97438 %0.3/98.3/0.93/00020398.-0 %024/073!074/.43897:..942.70.99.:2 .#.7079.480794903:.3/547-9..4.0/3904:907248980 3.84190..03:.0 007/8.%.34907.77..3090002039839024/073!074/.0.3/232.#:88.890.931.942..70 7.3/9000.4:/.74:53 905074/.70... #-.9./. -4743 8.4:238 %0.10/.300.0741300020398 ..79.70 3:2-074157494383903:.7488905074/ .3 00.97438. ./:8 20.0:88.94314700./:8 $.703.20.714723.3/547-9.-0 %00020398070.789.002 0398 0900374:5..90/30002 0398 3.3/74:59.88419024/073 !074/.942.30203941900020398374:5841002 0398839047/0741907.997.3-0.03989894 .. ! $ 942.904708 4.%.95074/.88 3 4800 805072039901.7090897430790.3/:2 4800!74943 :2-07 3 037301170 4800.80.0/3904:907248980 0020398 !074/ 908 1 /.7.47708543/3343209.3904:907248980 0020398 %0435074/8 !074/ 908 /.3/74:58 .8810/3949700.942/0.0289 5:-80/905074/.3.997.4.70/.748 .425090909.%.703.9.8..0.:50/ %01 -4.9448000.90790.3002039 942.0:8.039 -43/ %070..942.4.87.7.84/.943-090033:.3.47708543/3209.93/08 0020398 147-9.90/.3/2:89.002 0398 74:5 0307.890.0 ./4.70.574507908.8.9.8.3/547-9./.47708543/8 94907.9743.190/89.-941.7488.97435.03.90/4390-..70/8087050430.3/!074/ ..0 .0:8%0 07903:.9745489./:8 '.942.5074/ .707050.8:7.3/58.250!074/ 0 0 .3/804190..0397.3/08 0020398 147-9.942..7.80.3:2-07 %0 4/073!074/.94385 -09003.1742903:.941..570/.9.-0 43.8-0310/ !074/ 90847-9.703.70790438.83574943 .707..9 20.%.80 110.9428433.7.3:2 0.8.3:2-07 4800/0243897.70..08 03/000.34/0 7429 .9.70 4 415749438 4 41330700.8 .-0 3 297 03/000.3/570/.8.942.3 7.97430.3907.942./:8 09.3/547-9.3/08 !074/ 908 1 /.39.:998947024.. .%.990/47-9.0.94338 74:5 38 %05 -4.3438.3/ 90700.0/3904:907248980 0020398 .9.94784190.90/80.4..8.0.-041..880807082..88..700330110.079.3942 20.9743 942.705.80 :.4.9743830.10/.:7.705.700330110.-09.83/:09490 /8.:23:2 .7..8:70890.943 %084795074/8 !074/ 90847-9./0389 41900020398.3:2-078.0 942.7.3 3858.3.-08.3904:907248980 0020398 !074/ 90847-9.95:8.7 .305072039..-0347/07413.942 0.02.850..80708412.79.0/ %74:98 4800 8 20...93/08 %074:583905074/.7.0039./:8 .2.48089.79.4.-0 3.703.200.9000.3/03.70.#.77..070/9.997.431:7.8:7084198903/03.7.943 0307 902470/11.-0-.38990770.00020398 .30/394!074/8 47439. /:8 7.90790705:843-0900300.70.80 43.997.70..803908./:8/43.043.70.70.97438 .7..700330110.700330110.088.803.9743.70. :2-074157494383.93.8010/900.80-430 $.808 3.80 :.803903:.7./:8 4 4100.2 03:2-074100.7..70/0.343 70.80 942.0.97438 .3903.//943.033:.0.110.70790.7.70.94247.3/00.25074:5 0 .80/0. 74:5 7 43/439074:5.943 82.80 110. 47 ! $ 07903:.7.943-090033:.3.70.80 43.2000.835749433:2-07 343.80-430 :2-074100.70.80/0.703. 439074:5 $.74:5 .70.974383.39:280 :.4743..80 903.7079.70.03:..942.431:7..3.70.700330110.9/408349..08.3/74:5 .7..70 43. $7 .70./:8/43.974383..9428/0.9743.707903:2-074100.92:.9.80 $04190.9743.700330110.93.97438 4 415749438 .033:2-074100.80 8974307.0790.703. 850.80 .8430.3/908. $7 ..70.70.70.0.7.97438 $..25074:5 0 .7.0.94283.0908.041.8:. 8.943.74:5 .0:8.70 .943 03.942.808 3.70 0790147. ! $ 8400.:843 ./:841.804743.7488!074/ 43 43.835749433:2-07 43..98.4:/ $04190.997.9434747..80 03.7...7 .97438.70.0.0.343 .206:.