MATTER Chemistry is basically the study of matter and its properties and the changes it undergoes. Under appropriate conditions of pressure and temperature, most substances can exist in any one of the three physical states of matter: Gas, liquid and solid. The physical properties of a gas, liquid or solid can be explained by the kinetic theory. The balance between the kinetic energy of the particles and the strength of the intermolecular attractions determine the physical state of a substance. In a gas, the kinetic energy exceeds all the intermolecular attractive forces, so the particles are far apart. Ina liquid, the intermolecular attractions are stronger as the particles are closer together: In a solid, the intermolecular attractive forces dominate and the particles stay fixed in position. ‘A gas assumes the shape and volume of its container. A liquid has a definite volume but it takes the shape of a container. solid has a definite shape and volume. The state of matter of a substance may be changed by adding or removing heat energy from it. For instance, the addition of heat can melt ice into liquid water and turn water into steam. Concept Map Phase diagram (ideal gas and real gas structure AllotropeCHEM FILE A gas is a substance that is in gaseous state under normal temperature and pressure. ‘A vapour is the gaseous form of a substance that is a liquid or solid under normal conditions. CHEM TODAY Plasmas, fourth state of matter, are ionised gases existing at very high temperatures. The powerful | interionic forces lead to distinctly different properties. (meres LEARNING OUTCOMES Sa CHEM FILE Gas particles possess vibrational, rotational and translational ‘mations (rt CHEM FILE A is a device used to measure pressure. Pressure = h mmHg | a ceenaammemamenened wn Although the chemical behaviour of a gas depends on its composition, all gases have remarkably similar physical behaviours. A gas assumes the shape and volume of its container. The volume of a gas can be altered significantly (expand or contract) by changing the applied external force or temperature. Gases are readily compressible. Gases have relatively low viscosities and can flow freely. Diffusion of gases occurs from a region of higher concentration to a region of lower concentration. Most gases have relatively low densities under normal conditions. Gases are miscible and form a homogeneous mixture when confined in a container. Kinetic Theory of Gases Gases are made up of a large number of tiny particles of negligible volume, spaced far apart. There are no attractive or repulsive forces between the particles. The particles of a gas are in a state of continuous random motion with a distribution of speeds. The rapidly moving particles collide with each other and with the walls of the container. The collisions are perfectly elastic with no loss of kinetic energy. The average kinetic energy of the particles is directly proportional to the absolute temperature. With increase in temperature, the particles move faster as they gain kinetic energy. Gas Pressure Gas pressure arises from the force exerted by collisions of gas molecules with the walls of the container. Gases exert pressure on any surface on which they come in contact because gas molecules are constantly in motion. Pressure is commonly measured in units of kilopascal (kPa), pascal (Pa), atmosphere (atm) and mm Hg.CHEM FILE } Maxwell-Boltzmann Distribution Curve nee mm 1 The Maxwell-Boltzmann distribution curve shows how the 01 kPa speeds (or energies) of a mixture of moving particles vary at jo no hee particular temperatures. Se aaAaEReRORReT umber of rs eke partes te Maxwell-Boltzmann distribution curve of ‘molecular speed at two different temperatures ‘molecular speed 2 The particles of a gas, at a constant temperature, are always in constant random motion. However, the speed of the particles MINKETO: STEM, : 2000/P1/a12 varies over a wide range, from very slow particles (low energy) EL ee to very fast particles (high energy). | 200708 aa 3 Most of the particles move at a speed very close to the average. Only a small fraction of the particles has very low speed or very high speed 4 The peak of each curve represents the most probable speed, that is, the speed of the largest number of particles. S The area under the curve represents the total number of gas ie nue particles. The areas under both curves are as there is no one change in the number of particles at the two temperatures. particles 6 An increase in temperature of the gas from T; to T; results in He an increase in the molecular motion. The ‘i shifts to the right and flattens out. This indicates that at higher | temperature, there are fewer particles with the most probable ree speed but there are a 7 | Graham's law: 5 Rate of euson of a gas « 7 The aver of the molecules of different gases at [[uueea gam eat the same temperature is | Nevertheless, r on average than heavier ones. > Gas Laws The physical behaviour of a sample of a gas can be described by four variables: pressure (P), volume (V), absolute temperature (T) and amount (number of moles, n). The following gas laws express the effect of one variable on another. CHEM FILE Boyle’s Law When you pump up a bicycle |) tire, you push down on a 1 Boyle’s law states that at constant temperature, the volume — | _ handle that squeezes the gas occupied by a fixed amount of gas is inversely proportional to | Inside the pump. A reduction . in volume causes an increase the applied pressure. | in pressure.ved (n, T constant) PV =constant 2. Graphical representation of Boyle’s law pv Pp 3. As long as the amount of gas and the temperature are held constant, for a given sample of gas under two different sets of conditions, PM = PVs where V, and V, are the volumes at pressures P, and Ps respectively. 50 cm’ of a gas at 100 kPa is compressed to a volume of 20.cm? at constant temperature. Determine the final pressure of the gas. Solution PV, = PaVs 100 kPa x 50 cm’ = P; x 20 cm? 100 x 50 20 An inflated balloon with a volume of 0.6 dm at sea level (1.0 atm) is allowed to rise to a height of 6.0 km, where the pressure is 0.4 atm. Assuming that the temperature remains unchanged, what is the final volume of the balloon? Solution 1.0 atm x 0.6 dm’ = 0.4 atm x V; 1.0 x 0.6 04 1.5 dm Charles’ Law 1 Charles’ law stat a fixed amount ¢ temperature. 2. Graphical represe 273 0 3 We can compare for a given sampl where V; and V; respectively. Lei Lid 50 cm’ of a sample. Calculate the final constant A sample of gas at the volume of the gdCharles’ Law 1 Charles’ law states that at constant pressure, the volume of a fixed amount of gas is directly proportional to its absolute temperature. VeT (n, P constant) Vv = = constant T 2 Graphical representation of Charles’ law v v T1K) 3 We can compare two sets of volume-temperature conditions for a given sample of gas at constant pressure which give where V, and V, are the volumes at temperatures T, and T; respectively. [EXAMPLE 4372) Sos Vase ee e Aenea 50 cm’ of a sample of chlorine gas is heated from 25 °C to 200 °C. Calculate the final volume of the gas if the pressure remains constant. Solut eA (273 + 25) ~ (273 + 200) 50x 473 79 cm* A sample of gas at 30 °C was heated. At what temperature would the volume of the gas be doubled, assuming no change in pressure? Solut v Vv. 273 +30) Q3+T) T, =2 x 303 - 273 = 333 K = 60°C LINK TO STPM 2009/P2Q1 Tutorial on Charles law CHEM FILE The linear relation between {225 volume and temperature is used to devise the absolute temperature scale. Theoretically, the volume of all gases is zero at 0K or -273 °C. Dotted line extrapolates to this temperature. However, real gases liquefysolidity long before -273 cCO,(g) + dH,O(g) (a) Balance the above equation to determine the values of b, ¢ and d. (b) What is the volume of O, (in dm’) required for complete combustion of 5.2 dm’ of C,H? (©) What is the volume of CO, produced? Assume all gases are measured at the same temperature and pressure. 4x52 = 18.2 dm (6) 1 mol of C,H, produces 2 mol of CO;. Voo, _2 321 Veo, = 5.2 x 2= 10.4 dm* LEARNING OUTCOMES > Ideal Gas Equation 1 The three gas laws can be combined into one relationship called the or Q PV=nRT TAKE NOTE where P is the pressure of the gas Units of P, Vand Tused in the Vis the volume pa gas law. nis the number of moles of a substance Lond. Ris the gas constant (= 8.31 J K+ mol') Pa_| mK T is the absolute temperature kPa | dm? | K2. The ideal gas equation can be rearranged to determine the density and molar mass of a gas. LINK TO STPM 2000/P 1/02 2002/P2/06 mRT. 2005/P 1/07 PV =nRT =~ 2013/P 1/02 te 2013/P1/019%a) ity, d= = PM 2014/P 1/09 Density, d= 7 =p 2016/P 1/07 2017/P 1/97, 19 lar ma MRT _ ART Molar mass, M, = ""Bp- =F Gas Laws Boye’ Law Chaves’ aw ] [Avogacro'staw | [Dalton taw Va uP [ var [ ven Pr= Pia Pet ao PV= nT 0.01 mol of a sample of gas occupies 250,0 cm’ at 27 °C. If the temperature is raised to 35 °C, calculate (a) the volume occupied if the pressure remains unchanged. (b) the pressure of the gas if the volume is fixed. (©) the volume occupied by the gas at st.p. (273 K, 101 kPa) (a) 7 250.0 Vs O73 +2) ~ G3 +35) V, = 256.7 cm* (b) PV =nRT p= ART _ (0.01 mol(8.31 JK 'mol 273 + 38) K _ 199 cava (250.0 x 10° dm’) obi (c) PV=nRT JK" mol )273 K) 101 kPa ).2246 dm? = 224.6 cm*l hypodermic syringe containing 0.15 g of a volatile liquid was into a graduated gas syringe at a temperature of 90 °C and a of 101 kPa. The expanded vapour was found to occupy a of 62.2 cm’, Determine the relative molecular mass of the liquid. (0.15 g)(8.31 JK! mol)(273 + 90) K (HOT EPay(@22x 10am) 10's law Vex three laws combined as Vo "2 h the introduction of a constant of proportionality, R: a Rp nging, PV = nRT in’s Law Dalton’s law states that the (otal pressure of a gas mixture (with no interaction) is the same as the sum of partial pressures of the gaseous components. Pr=P, Pt: where P, = total pressure of the mixture P,, Py, .-. = partial pressure of gases A, B, Partial pressure of a gas in a mixture is the pressure exerted by the gas if it alone occupies the container at the same temperature. Each component in a mixture contributes a fraction of the total number of moles (n) in the mixture, which is the . X, of that component. np= ny +My ny iy 4 The partial pressure of gas A = mole fraction A x total pressure Py=X,x Pp= tx Py ny CHEM FILE Gas syringe is used to determine molar mass of volatile substances based on the Ideal Gas Law. Lee ‘ero oe aaa = at ‘syringe Ts ah, Neel coro) pee eer TAKE NOTE ‘The sum of the mole fractions of all components in any mixture equals 1. XX enedPartial pressure of a gas does not | 30 change even when other gases A gas mixture consists of 4.4 g of carbon dioxide and 6.4 g of oxygen. Calculate the partial pressures of carbon dioxide and oxygen in the mixture with the total pressure of 150 kPa. 44 Number of moles of COs= 5 scqqH = 0 oO Number of moles of 0; = 707%, = 0.20 Mole fraction of CO, in the mixture = 0-10 _1 - 010+020° 3 0.202 Mole fraction of O, in the mixtur *0.10+020° 3 ml = Peo, = 3 X 150 = 50 kPa Po, = % x 150 = 100 kPa REN in A mixture of gases at a pressure 1.01 x 10° Pa has the volume composition of 30% CO, 50% O, and 20% CO,, (a) Calculate the partial pressure of each gas. (b) If the carbon dioxide is removed by the addition of some pellets of sodium hydroxide, (i) what will be the partial pressures of O,and CO? Gi) what is the total pressure then? (a) Ven Mom v.77, are removed from or added tothe container, as long as the volume ‘and temperature remain constant. =20 = i Peo = Fg X 101 x 10° = 3.03 x 10* Pa = 50 $= i Po,= Fg * LOL x 10° = 5.05 x 10* Pa = 20 _ Poo,= Fog X 101 x 10° = 2.02 x 10* Pa (b) (i) Po, = 5.05 x 10! Pa Poo = 3.03 x 10! Pa (ii) Pp= Po, + Poo = 5.05 x 108 + 3.03 x 10* = 8,08 x 10! PaOe uie 1 A container of volume 45.0 dm’ contains nitrogen gas at 55.0 kPa. Another container of volume 30.0 dm? contains oxygen gas at 85.0 kPa. A valve connects the two containers. If the valve is opened without any temperature change, calculate (a) the partial pressure of each gas, (b) the final pressure in the container, (©) the mole fraction of nitrogen gas and oxygen gas in the mixture. 2. Relative molecular mass of W is 28.0. Calculate the density of gas W in g di at 107 °C and 200.0 kPa. 3 3.0 dm’ of a sample of gas S at 25 °C exerts a pressure of 1.0 atm, How much pressure is required to compress the gas by 20% without any change in temperature? 4 500 cm’ of a gas W at 40 °C and 8.0 x 10* Pa has a mass of 1.8 & Determine the relative molecular mass of the gas W. 5 A balloon can hold 1000 cm! of air before bursting, The balloon contains 950 cm? of air at 20 °C. Determine the temperature at which the balloon will burst. Assume the pressure of the gas in the balloon remains constant. 6 5.0 dm’ of helium gas at 4.0 x 10° Pa and 3.0 dm’ of oxygen gas at 5.0 x 105 Pa is injected into a 2.0 dm’ container. Determine. (a) the partial pressures of helium gas and oxygen gas in the container, (b) the final pressure in the container. 7 Density of solid carbon dioxide is 1.50 g dm’. What is the volume of gas produced by 2.5 dm’ of solid carbon dioxide at s.t.p.? [1 mol of gas occupies 22.4 dm’ at s.t.p.; Relative atomic mass: C, 12; 0, 16] > Real Gas: Deviations from Ideal Behaviour stabs cade tae 1 A gas that obeys the ideal gas law is called an . A real gas that obeys the ideal gas equation is said to exhibit ideal gas behaviour. er eer) ty at very high pressure 2 Two assumptions made by the kinetic theory about ideal gases are: . 1 Seat Ss D of real gases from ideal behaviour occurs becauseLINK TO STPM 2013/P1/Q7 2014/P 1/016 ieee The behaviour of several real gases with increasing external pressure. The horizontal line shows the behaviour of ideal 2s. For 1 mol of ideal gas, PVIRT=1 atall pressures ‘The deviation of nitrogen gas at different temperatures. Deviation is higher at low temperature 4° The deviation of real gases from ideal behaviour is shown by the plot of PV/RT against P (for | mol of gas). 20 ° 300 800 300 Plain) 5 All gases exhibit near ideal behayiour at low pressure and hi mperature, (a) At low pressure, the volume occupied by the gas is large. The volume of gas molecules is comparatively small and can be ignored. As the molecules are far apart, the intermolecular attractive forces can be ignored. (b) At high temperature, the kinetic energy of the molecules is so high that the intermolecular forces is insignificant and can be ignored. 6 Real gases deviate significantly from ideal behaviour at high ressure and low temperature. (a) At high pressure, the volume occupied by the gas is small and the volume of the gas molecules cannot be ignored. At very high pressure, repulsive forces between molecules become significant, and make the gas less compressible. (b) At low temperature, the kinetic energy of the molecules is low. The intermolecular forces become more apparent. 7 PVIRT curve decreases below ideal value at moderately high pressures and then rises above it as pressure increases further. This arises from two overlapping effects of the two characteristics of real gas molecules.(a) Negative deviation PVIRT <1 At moderately high pressure, intermolecular attractions lower the force of collision of molecules with the walls of the container. (b) Positive deviation PVIRT>1 At very high pressure, more gas molecules are packed within the container. The volume of these gas molecules, though small, cannot be ignored. H, and He show positive deviation only at all pressures. Due to the small molecular size and non-polarity of the molecules, the intermolecular attractive force is insignificant. The molecular volume effect predominates at all pressures. Gases with large and polar molecules deviate more from ideal behaviour due to stronger intermolecular forces of attraction. Number of molecules per unt volume is low, volume of gas ‘molecules is comparatively small and can be ignored, ‘As molecules are far apart, intermolecular attractive forces ‘can be ignored. Number of molecules per unt volume is high, volume of gas molecules is significant and cannot be ignored. Intermolecular forces are significant and cannot be ignored. ¥ 4 Low Hon pressure prossire t 4 Ein near Deviate fom ideal behaviour ice behaviour Y ' ton tow temperature temperature t 1 kinetic energy of gas molecules is high, Intermolecular attractive {forces are insigniieant and ‘can be ignored. Kinetic energy of gas molecules is low. Intermolecular attractive forces are significant and cannot be ignored. Checkpoint 4.2 1 (a) What do you understand by the term ideal gas? (b) State two factors that cause a real gas to deviate from ideal behaviour. (c)_ State two conditions where a real gas deviates most from ideal behaviour. CHEM FILE As the temperature is decreased below a critical |__ value, the deviation from ideal gas behaviour becomes severe because the gas liqueties, ee CHEM FILE ‘To correct for the deviations in real gases, the ideal gas law is redesigned as in the van der Waals’ equation: (P+ aVXV— b) = nT L cereal Difference between ideal and real gas behaviour(d) State two conditions where a real gas approaches an (e)_ Name two gases that behave almost ideally. (Name two gases that deviate far from ideal behaviour. 2. Sodium azide, NaN, is used in car air bags. On impact, electronic sensors set off a chemical reaction and this compound rapidly decomposes into its elements, Determine the volume of gas produced by the decomposition of 100 g of NaN, at room temperature and pressure, [1 mol of gas at room temperature and pressure occupies a volume of 24.4 dm’; Relative atomic mass: N, 14; Na, 23] 3. (a) The molar volume of carbon dioxide at 273.0 K and 101.3 kPa is 22.0 dm’, Give one factor why the volume is smaller than the molar volume of an ideal gas. (b) Under what conditions would carbon dioxide behave more ideally? Explain your answers. 4A Proton car has a cylinder volume of 1.00 dm’. The cylinder is full of air at 50 °C and a pressure of 101 kPa. Petrol contains mainly octane, CH. (a) Construct a balanced equation for the complete combustion of octane, (b) Determine the number of moles of air present in the cylinder. (©) Given-the composition by volume of oxygen in air is 21%, determine the number of moles of oxygen present in the cylinder, (@) Determine the number of moles of octane required to react with the oxygen in the cylinder. (€) Given the density of octane is 0.7 g cm, determine the volume of petrol to be injected into the cylinder to react with oxygen. ee eal ga ® 4.2 LiquIDs Neola sy Explain the kinetic concept of the reo Kinetic Concept of the Liquid State 1A liquid has a fixed volume but its shape follows that of the container which holds the liquid. 2. There are much greater forces of attraction between the particles in a liquid compared to gases but not quite as much as in solids. 3 Particles move in an overall rapid and random manner. The particles have vibrational, rotational and some translational motions. 4 The particles are closely packed together. Thus a liquid is not easily compressed.® Changes of State 1 Figure 4.4 summarises the terminologies for the changes of state or phase transition 2 Changes of state are governed by the balance between the kinetic energy which tends to disperse the particles and the intermolecular forces which tend to draw the particles together. 3 As the temperature increases, the average kinetic energy increases and the more energetic particles can overcome the attractive forces more easily. Lower temperatures allow the attractive forces to draw the slower moving particles together. Melting (Solid to Liquid) 1 In solids, the particles are closely packed together in a fixed orderly structure, with vibrational and rotational motions only. When heated, the kinetic energy of the particles increases. 3 At a certain temperature, the energy acquired is sufficient to overcome the intermolecular forces. The particles are liberated from their fixed positions and can now move more freely (translational motion). Melting process occurs. Freezing (Liquid to Solid) 1 Particles move in an overall rapid and random manner in a liquid. 2. As temperature is reduced, the kinetic energy of the particles decreas 3A point is reached when the intermolecular forces are strong enough to hold the particles together in a fixed orderly arrangement. This is known as the freezing process. 4 Melting point or freezing point is the temperature where the solid and the liquid phases exist in equilibrium. Vaporization (Liquid to Gas) 1 Particles in a liquid are in a constant (translational) motion. Due to intermolecular forces, the particles can move throughout the liquid but are not free from interaction with the other particles. Pera elaucwe E sol aud © eau Tie eee LEARNING OUTCOMES See ean: emcee kent eee eet ate Sere en freezing point of liquic CHEM FILE Enthalpy of fusion: Heat energy required to convert 1 mol of solid into liquid at its melting point ‘and at 1 atm, TT CHEM FILE Enthalpy of vaporization; Heat | energy require to convert 1 mol | of liquid into vapour at its boiling point and at 1 atm, nenaCHEM FILE oo the change from | liquid state into gaseous state “> takes place without heating. ; 1 requires heating. | soem CHEM TODAY Water boils at a higher temperature in a pressure | ‘cooker. Thus, food gets | Cooked faster. Water bois at tower temperature at higher | altitudes where the | atmospheric pressure is lower. nitesiiitimeneael LINK TO STPM. 2004/P2/05(a) KEY POINT A liquid with higher vapour pressure has a lower boiling Poi : Vapour Pressure and Bi 1 Some particles at the surface of the liquid may have enough energy to overcome the intermolecular forces and escape into the vapour phase. Vaporization process occurs. The pressure exerted by these escaping particles onto the walls of a closed container is termed the vapour pressure of the liquid. Evaporation in a closed space causes the concentration of molecules in the vapour phase to build up. Some particles, after colliding with the walls of the container or with one another, might strike the surface of the liquid and be held by the attractive forces of the liquid molecules and re-enter the liquid. Condensation takes place. ing Point pour pressure of a liquid is pressure exerted by a vapour in uilibrium with its liquid at a fixed temperature. Vapour pressure is exerted due to the si icles onto Vapour pressure is independent of the amount of liquid present but increases with the increase in temperature. A liquid boils when its vapour press uals the nal ire, At this point, bubbles of vapour are formed within the liquid and escape into the atmosphere as the vapour pressure is high enough to overcome the external pressure. Boiling point is the temperature where liquid and gas exist in equilibrium. Boiling point of a liquid is defined as the temperature at which its vapour pressure equals the external pressure. Boiling point of a liquid depends on the external pressure. The normal boiling point of a liquid is taken at a pressure of 1 atm. ity, Vapour Pressure and Temperature The vapour pressure of a substance depends on the temperature. Raising the temperature of a liquid increases the fraction of molecules moving fast enough to escape the liquid’s surface. A liquid that evaporates readily is said to be volatile. A volatile liquid has weak intermolecular forces. Therefore, the particles have higher tendencies to escape as vapour. At any given temperature, a more volatile liquid has a hivher apour pi and hence a i Figure 4.5 shows the vapour pressure of three liquids as a function of temperature. The normal boiling point of each liquid is also indicated.Platm) tor 10 05 ° 35 78100 TO) More Lower Higher volatile liquid boling point Pour pressure} A graph of vapour pressure versus temperature of water and acetone is shown, vapour pressure (aim) acetone / / temperature (°C) (a) Explain the term vapour pressure. (b) Explain the variation of vapour pressure with the change in temperature using the kinetic theory. (©) Based on the graph, estimate the normal boiling point of acetone, (4) Compare the vapour pressure and volatility of water and acetone. Solution (@) Vapour pressure is the pressure exerted by a vapour in equilibrium with its liquid at a fixed temperature. When the molecules of a vapour collide with the wall of the container, vapour pressure is produced. (b) Vapour pressure increases with the increase in temperature, At higher temperature, molecules gain energy and move faster, The kinetic energy of molecules increases and mote molecules escape into the vapour phase. More molecules collide with the wall of the container. Vapour pressure increases. (©) Normal boiling point is at the vapour pressure of 1 atm, Boiling point of acetone is ~50 °C (4) Vapour pressure of acetone is higher than water at all temperatures. Therefore, acetone is more volatile than water. Water forms strong intermolecular hydrogen bonds. Acetone has only weak intermolecular van der Waals forces. Hence acetone molecules escape into the vapour phase more easily. © CHEM FILE ‘Normal boiling point is the boiling point at 1 atm. «Figure 4.5 «Figure 4.6® 4.3 soLips ® Characteristics of Solids 1A solid has a fixed volume and shape. 2 The particles in a solid are closely packed and strongly held in fixed positions by stroag attractive forces. Therefore, solid cannot flow freely like gas or liquid. 3 Solids are extremely difficult to compress. 4 There are two broad categories of solids based on the orderliness of their particles: crystalline and amorphous. (a) Crystalline solid generally has a well-defined shape because the particles (atoms, molecules or ions) have regular 3-dimensional arrangement. Examples are ice, diamond and sodium chloride. (b) Amorphous solid lacks well-defined faces and shape because the particles are randomly arranged with no order. Examples are glass, rubber and plastics. LEARNING OUTCOMES ® Lattice Structure and Unit Cell Peete §=—| The arrangement of the particles in solids is studied by using ee oe) X-ray diffraction analysis. eee 2. A crystalline solid can be represented by a 3-dimensional array inet gn of points that denotes the particles in the crystal. Such an array rel alec of points is called a crystal lattice, bei 3° The basic repeating unit of a crystalline solid is known as the unit cell, 4 The simplest lattice structure is the cubic unit cell. 5 There are three kinds of cubic unit cells. (a) Simple Cubie ~ eg. KCL (b) Body-Centred Cubic Cell (bee) eg. alkali metals (©) Face ntred Cubic Cell (fee) (also known as cubic close-packed) eg. Cu, I, NaClLattice Structure of an lonic Solid — Sodium Chloride 1 The crystals of ionic compounds are made up of oppositely charged ions that are held in place by strong electrostatic forces, 2 The lattice structure of sodium chloride is shown below: The overall structure consists of two interpenetrat centred cubic arrays. 3 NaCl shows 6 : 6 coordination, Each Na* ion is surrounded by six Cl ions and each CI is in turn surrounded by six Na* ions. fice Structur of a Simple Molecular Solid — lodine In a molecular crystal, the lattice points are occupied by molecules. The attractive forces between them are the van der Waals forces and/or hydrogen bonding. The diagram shows the arrangement of I, molecules in crystalline iodine. Iodine has a face-centred cubic lattice structure. The forces holding the iodine atoms together are the covalent bonds while the attractive forces forming the crystal are ) Waals forces. ‘The coordination number of iodine is 12, der ice Structure of Giant Molecular Solid — Grap| tond and Silicon(IV) Oxide In giant molecular solids, atoms are held together in an extensive 3-dimensional network or lattice entirely by strong covalent bonds. Since covalent bonds are much stronger than intermolecular forces, these solids are much harder and have high melting Points. These solids are also not soluble in any solvent. Examples of giant covalent solids include graphite, diamond and silicon(IV) oxide. ihite fe Graphite consists of layers of interconnected planar hiex.avonal ings of carbon atoms. CHEM FILE The unit cell of an ionic solid has the same cation ; anion ratio as the empirical formula of the ionic compound, CHEM FILE ocsipation umber of a particle | is the number of nearest | neighbours surrounding it. CHEM FILE Giant molecular solids may also be termed as giant covalent solids or macromolecules, RECALL } Electronic configuration of 1s! 2s? 2p?Layered structure ‘of graphite carbon atom covalent bonds 3.0 structure of diamond 2 The carbon atoms are all sp’ hybridised. Each carbon atom is covalently bonded to three other atoms in the same plane. 3° The fourth valence electron from each carbon atom overlaps to form delocalised p bonds that extend over the entire layer. 4° The layers are held together by weak van der Waals forces. Diamond 1 Diamond consists of interconnected 3-dimensional array of strong carbon-carbon covalent bonds. 2 The carbon atoms are sp’ hybridised. Each carbon atom is covalently bonded to four other carbon atoms in a fetraliedral manner. 3 All the four valence electrons are used in bonding, so there are no free electrons. Comparison of the lattice structure of graphite and diamond _ Crystalline covalent solid Crystalline covalent solid Giant covalent structure Giant covalent structure Each C atom sp* hybridised Each C atom sp’ hybridised _ Layered structure of hexagonal rings Tetrahedral geometry _ Strong covalent bonds between C atoms. Strong covalent bonds between ‘Weak van der Waals between layers. atoms Silicon(IV) oxide (Silica), SiO, 1 Silicon(IV) oxide, SiO, can exist in both crystalline and amorphous forms. 2 Crystalline silicon(IV) oxide is hard, brittle, clear and colourless solid known as quartz. It has a 3-dimensional giant covalent lattice, similar to that of diamond. 3 Each silicon atom is covalently bonded to four oxygen atoms in a tetrahedral manner, while each oxygen atom is bonded to two silicon atoms. @5slicon atoms © oxygen atoms, Lattice Structure of Metallic Solid - Copper 1 Metallic crystals generally have body-centred cubic, face- centred cubic or hexagonal close packed lattice structures,2 Copper has a bic structure. Every copper atom is in contact with 12 others. It is said to have a coordination number of ” A unit cell of copper metal orystal For structures consisting of identical atoms, how many atoms are contained in the simple cubic, body-centred cubic and face-centred cubic unit cells? Simple cubic: 8 corners x 1/8 = | atom Body-centred cubic: (8 corners x 1/8) + (1 centre x 1) = 2 atoms Face-centred cubic: (8 corners x 1/8) + (6 faces x 1/2) = 4 atoms Refering to the unit cell of NaCl shown, how many Na’ and CI ions are in each NaCl unit cell? Allotropy 1 Allotropes are different forms of the same element in the same physical state. They occur due to different bonding arrangements 2 Allotropes have different physical and chemical properties Allotropes of Carbon 1 Diamond, graphite and fullerenes are the three allotropes of the element carbon. 2 (a) Diamond fe Sit Hard Due to the interconnected, 3-dimensional array of strong covalent bonds and the geometrical rigidity of the structure, Diamond-tipped tools are used for cutting glass, oil drill and as abrasives. Insulator All the four valence electrons are used in bonding, No free mobile electrons. CHEM FILE To determine the number of particles in a unit cell erry ee Centre 1 Face v2 Edge v4 Comer ve Heol cxe ad ae meray CHEM Topay Examples of allotropes C: diamond, graphite, fullerenes S: rhombic sulfur ($,) & ‘monoctinic sulfur (S,) fed, white, black phosphorus a (grey), B (white, tin gaseous allotropes of oxygen: 02 and 03 RRLINK TO STPM 2013/P1/08 ses, Sop Other forms of fullerene such 2 Cy. are oval shaped Insoluble Very high ‘melting point Sparkling (b) Graphite Electrical conductor Insoluble Very high melting point (c) Fullerene Solvent molecules cannot break up the strong covalent bond network. Strong covalent bond network. Requires large amount of energy to break apart. High refractive index. Used as ornaments and jewelry, plan: Weak van der Waals forces between the layers allow the layers to slide easily over one another. Graphite powder is used as a good high temperature lubricant, The delocalised p electrons are free to move so graphite can conduct electricity. Graphite is commonly used as electrodes. Strong covalent bond network. ] Strong covalent bonds holding the C atoms within the layers. 1 Fullerene, Cio, also known as ‘buckyball’, exists as simple molecules with spherical structure similar to a football. 2 Each molecule consists of 60 carbon atoms covalently bonded in a polyhedron with 20 hexagonal surfaces and 12 pentagonal surfaces. 3 The carbon atoms are sp? hybridised. Each carbon atom is bonded to three other carbon atoms; the fourth electron is delocalised within the molecule. 4 Fullerene has commercial applications as catalyst, lubricant and superconductor. Soft and slippery Covalent bonds holding C atoms in molecules but only weak van der Waals forces between molecules. Electrical insulator No free electrons. Insoluble in water Carbon atoms are bonded very tightly to, ‘one another in the molecules. |Soluble in organic Simple molecular structure. solvents Low melting point Typical of covalent crystals with only weak intermolecular van der Waals interactions. omparison of the properties of the three allotropes of carbon ed esis Hard Soft and slippery Electrical Insulator Electrical insulator Insoluble, No Insoluble in water but solvent soluble in organic solvents Very high melting Low melting point point 4.4 PHASE DIAGRAMS LEARNING OUTCOMES ig Phase Diagrams A phase is a homogenous (components uniformly distributed throughout) part of the system which is physically distinct from ‘the other parts of the system. A phase may be a solid, liquid, gas or even a homogenous Solution or a mixture of gases. A phase diagram summarises the relationship between the solid, Squid and gaseous states of a given substance as a function of © LINK TO STPM ure and temperature. 2000/P2/Q1 re 4.7 shows the general form of a phase diagram of 9 === em exhibiting three phases: Solid, liquid and gas. Pressure g | 98 sos | qua /! [bers i point in this diagram represents a possible combination of rature and pressure for the system. A phase diagram has following features: Each region represents respectively the solid, liquid and gaseous phase of the substance. A particular phase is stable within its region.Pp supercritical uid CHEM FILE ‘Supercritical fluid exists at temperature and pressure above its critical point, where distinct liquid and gas phases do not exist Temuco) en and carbon dioxide, LINK TO STPM 2013/P1/020 2014/P1/07 2015/P1/Q11 2017/P 1/08 (b) The lines separating the regions represent the phi transition curves. Any point along the line specifies t conditions under which the two phases exist in equilibrium. (c) Point O where the three phase-transition c meet. This describes the conditions under which all thi phases coexist in equilibrium. solid —= liquid — gas The phase boundary between liquid and gas does not continue indefinitely. Instead, the liquid-gas line ends at a point called the critical point, C. Critical temperature T. is the temperature above which a gas will not liquefy by increase in pressure. At very high temperatures and pressures, beyond the critical point, the liquid and gaseous phases become indistinguishable. in what is known as a supercritical fluid. (d) Phase Diagram for Carbon Dioxide pressure (atm) 8 -— temperature (°C) “78-57 S110 suit The phase diagram for CO, is typical of most substances. AO line: It shows the sublimation point at different pressures and temperatures, OB line: = It gives the melting (or freezing) point of solid carbon dioxide at different pressures. The positive gradient indicates that the melting point of CO, increases with the increase in pressure. This is expected as a solid is usually denser than a liquid. So an increase in pressure favours the more compact solid phase. OC line: It shows the boiling point of liquid carbon dioxide at different pressures. It also gives the vapour pressure of liquid carbon dioxide at different temperatures. 0 (5 atm, -57 °C) At this point, solid CO, exists in equilibrium together with liquid CO, and CO, vapour.6 Critical point C (73 atm, 31 °C) At this point, the average kinetic energy of the molecules is so high that the vapour cannot be condensed no matter what pressure is applied. Uses of Dry Ice 1. Solid carbon dioxide is known as ‘dry ice’ because it looks and feels like ice but doesn’t wet. Dry ice has the advantage of being relatively cheap and non-toxic. Dry ice is commonly used as refrigerant for food stuff, and, to preserve and ship biological samples. It can maintain very cold temperatures and does not leave messy wet liquid as it sublimes. Fruits frozen with dry ice will thaw firm, not soggy. In the entertainment industry, the “fog” used in special effects is made with dry ice. When dry ice is placed in water, sublimation is accelerated, the cold CO, gas causes nearby water vapour to condense and form a thick white fog. Dry ice is used in cloud seeding to induce rainfall. Sublimation of CO, absorbs heat from the clouds. This lowers the clouds’ temperature, causing water vapour to condense to water. The phase diagram of a substance Z is given. Consider a sample of Zat -20 °C and 1.0 atm. {a) State the phase for this sample of Z. (b) Indicate on the diagram and explain what happens (i) when this sample of Z is cooled at constant pressure, (Gi) when the pressure of the sample is reduced isothermally. (©) Indicate on the diagram the normal freezing point (Ty) and boiling point (Ty) of Z. ution {a) The sample of Z exists as a liquid. (b) (i) The liquid Z freezes to a solid. Initially Z exists as liquid. At point P, solid and liquid Z exist at equilibrium Then Z turns to solid when the temperature is further decreased. i) The liquid Z turns into vapour. Initially Z exists as liquid. At point Q, liquid and gas Z exist at equilibrium Then Z turns to vapour when the pressure is further decreased. (©) Normal freezing point (solid == liquid) and boiling point (liquid = gas) occurs at 1 atm. LEARNING OUTCOME CHEM TODAY Carbon dioxide (CO.) extinguishers contain liquid CO, Under pressure, CO, extinguishers leave behind no harmful residue. CO, is heavy, displaces oxygen ‘and creates a blanket around the burning fuel, smother and ‘extinguish it. Sublimation of CO, also lowers the surrounding temperature, Piatm) =40_ 20 TCO) CHEM TODAY (1 atm, -78 *) ‘The triple point and the entire liquid phase for CO, are situated Well above atmospheric pressure. ‘At 1 atm, solid carbon dioxide does not melt but sublimes when heated to -78 °C. For CO, to exist as a liquid, the | pressure must exceed 5 atm. | Thus, CO, does not have a ‘normal melting point. Instead, it has a normal sublimation point at ~78 °C. TEP(atm) fi 801d | liquid 10 05 Teo) Tw a ® Phase Diagram of Water Pressure (aim) g LINK TO STPM 2004/P1/13 2016/P 1/08 OB: solid = liquid OC: liquid — gas O: triple point (0.01 °C; 0.006 atm) C: critical point (374 °C; 218 atm) DO: supercooling: HO exists in a metastable state (exists as a liquid below its freezing point) Anomalous Behaviour of Water 1 For most solids, melting point increases as pressure increases. hae However, for water, the melting point line (OC) has a negative FR ae gradient. This shows the melting point of water decreases with ea the increase in pressure. ep rp: ie 6 2 Intermolecular hydrogen bonds lead to an open structure in ice. eae ¢ So ice has a lower density than liquid water. pan ancan aes liquid water = solid ice higher density, smaller volume lower density, larger volume 3. Water expands on freezing. An increase in pressure favours the higher density of liquid water. LEARNING OUTCOMES » Effect of a Non-Volatile Solute on the Vapour Pressure of a Solvent base abate Presence of a non-volatile solute will change the physical properties ee) of the solution as compared to the pure liquid (the solvent).Lowering of Vapour Pressure 1 Ifa solute is non-volatile, the vapour pressure of its solution is lower than that of the pure solvent. 2 When a solute dissolves in a solvent, part of the surface of the solution is occupied by the solute particles. Less solvent particles can escape to form vapour. So the vapour pressure of the solution is lowered. Boiling point is the temperature at which the vapour pressure of the liquid equals the external atmospheric pressure. As the vapour pressure of a solution is lowered, a higher temperature is needed to raise the vapour pressure of a solution to equal the external pressure. Hence the boiling point is increased. Freezing point is the temperature at which an equilibrium exists between the liquid and solid phases. The presence of foreign molecules makes the orderly arrangement more difficult to achieve. Temperature has to be lowered further for freezing to occur. Thus, freezing point is depressed. pressure tai freezing feezing boiling baling Point of point of point of point of solution water. water Solution Colligative Properties Colligative properties are properties of a solution that depend ‘on the number of solute particles in a solution and not on the nature of the particles. Colligative properties include lowering of vapour pressure, boiling point elevation, freezing point depression and osmotic pressure. The magnitude of the change depends on the concentration of solute particles. It is also dependent on the nature of the solvent. CHEM FILE The relationship of vapour | pressure and mole fraction is |__ expressed by Raoult’s law. RECALL |The normal boiling point of a liquid or solution is the temperature at which its vapour prea reaches 1 atm, CHEM FILE ‘Sea water contains dissolved | salts which lowers the freezing | point of water. Ice on frozen roads melts when | LINK TO STPM 1998/P 1/051 © 1999/P2/a4() TT CHEM FILE Colligative means “collective”.Summary oanwn 10 n 12 13 14 15 16 7 18 19 20 Kinetic theory of ges: - The volume of the gas molecules is negligible compared to the total volume of the gas. = There is no intermolecular forces of attraction or repulsion. Boyle's law: P= + (n, Tconstant) Charles’ law: V= T(n, Pconstant) Avogadro's law : V« n(T, P constant) Ideal gas law ; PV= nA Dalton’s law states that the total pressure of a gas mixture (with no interaction) is the same as the sum of the partial pressures of the gaseous components. Partial pressure of a gas in a mixture is the pressure exerted by the gas if it alone occupies the container at the same temperature. An ideal gas obeys the ideal gas law which states that a gas has no particle volume and no intermolecular forces between the gas molecules. Real gas deviate from ideal behaviour because — gas molecules have finite volume, ~ intermolecular forces exist. Real gases exhibit near ideal behaviour at low pressure and high temperature. Real gases deviate significantly from ideal behaviour at high pressure and low temperature. Melting point or freezing point is the temperature at which solid and liquid exist in equilibrium. Boiling point is the temperature where liquid and gas exist in equilibrium, and the vapour pressure equals the external pressure. Vapour pressure is the pressure exerted by a vapour in equilibrium with its liquid at a fixed temperature. When the molecules of a vapour collide with the walls of the container, vapour pressure is produced. A more volatile liquid has a higher vapour pressure, a lower boiling point and a lower enthalpy of vaporization. Crystal lattice is the regular arrangement of particles in a crystal structure. Allotropes are different structural forms of an element, Diamond, graphite and fullerene are allotropes of carbon. A phase diagram summarises the relationship between the solid, liquid and gaseous states of a given substance as a function of pressure and temperature. Triple point describes the conditions where all three phases, solid, liquid and gas coexist in equilibrium.Critical point is the temperature above which a gas will not liquefy by an increase in pressure. Beyond the critical temperature, T, the liquid and vapour phases are indistinguishable. For carbon dioxide, melting point increases as pressure increases. For water, melting point decreases as pressure increases. 23 Addition of non-volatile solute to a solvent __ * lowers the vapour pressure of the solvent * causes depression of melting point * causes elevation of boiling point Colligative properties depend on the number of solute particles in a solution and not on the nature of the particles. FOCUS ON STPM 4 OBJECTIVE QUESTIONS 1 A sample of 10 dm’ of polluted air at rtp. is passed through lime water, Ca(OH), so that all the carbon dioxide present is precipitated as calcium carbonate, The mass of calcium carbonate formed is 0.05 g, What is the percentage, by volume, of carbon dioxide in the air sample? [4 H, 1; C, 12; O, 16; Ca, 40; 1 mol of gas at r.t.p. has a volume of 24 dm'] The diagram shows two bulbs containing gas A and gas B respectively. Assume gas A and gas B do not react. If all measurements are made at the same temperature, what is the overall pressure exerted when the valve is opened and the eae aoe system is allowed to attain equilibrium? Oe re A. 167 atm C 3.5 atm i ae . The density of ice is 0.9 gem What Bie aun D 25 atm gp ihe Wollkmsof steamy prodkicéd svtién 4 If the density of a triatomic element is y pers oftibe teliesten tb 2235 C-aba at sip, its relative atomic mass is pressure of 101 kPa? A 3y C 24y A 0.041 dm? C 2.71 dm B 747y B 2.45 dm’ D_ 15.76 dm’ ay| i i j 5 Which of the following exerts the highest pressure? A I mol of ethanol at its normal boiling point B_ 1 mol of O, at a temperature of 0 °C with a volume of 11.2 dm! C 1 mol of CO, at a temperature of 30 °C with a volume of 22.4 dm! D_ 1 mol of water at a temperature of 25 °C with a volume of 2.24 dm* 6 Sulphur dioxide is an example of a non- ideal gas because A. its molecular size is small. B_ it has an unpleasant odour. C it dissolves in water to form an acidie solution. D the intermolecular forces of attraction are strong. 7 Which of the following shows the correct graph of V against 7 for an ideal gas? A vide!) C vm) o Te) Teo) B vim?) D viamy 0 Teo) ol —=- 0) 8 Ina syringe experiment, 0.20 g of a gas is found to occupy 60.0 cm’, measured at standard pressure (1.0 x 10° Pa) and 27 °C. What is the relative molecular mass of the gas? A (0.20 8.31 x 27 1.0 x 10° x 60.0 Bp 0.20 8.31 x 300 0x 10° x 60.0 0.20 x 8.31 x 27 © Tox 105% 60.0 x 10° p _0.20x 8.31 x 300 1.0x 1 x 60.0 x 10% 9 A quantity of 28 g of nitrogen is mixed with 32 g of oxygen at 298 K and 101 kPa. Which statement best describes the mixture of gases formed? A More oxygen than nitrogen molecules are found in the mixture. B_ The average velocities of nitrogen and oxygen molecules are the same. C__ The average kinetic energies of nitrogen and oxygen molecules are the same. D There is no transfer of kinetic energy when nitrogen and oxygen molecules collide. 10 A manometer is a device for measuring 1 gas pressures. A sample of nitrogen gas is placed in a close-end manometer at 25°C until there is an increase of 0.100 ¢ in its mass. The diagram below shows the, height of mercury in the manometer. 600 mm What is the volume of the nitrogen gas in the manometer? [Relative atomic mass: N, 14.0; Molar gas constant = 8.31 J K! mol '; 760 mm Hg = 101 kPa] A 95 cm* C 133 em’ B lllcm* D 266 cm’ 3 If heat is added to a pure liquid substance at its boiling point, the temperature will increase. the temperature will decrease. the temperature will remain constant. the temperature of the vapour will be higher than the temperature of the liquid pam12. A solid melts sharply just above 100 °C. It does not conduct electricity even when molten. It dissolves in hydrocarbon solvents. What is the structure of the solid most likely to be? A A molecular crystal B An ionic crystal C A giant covalent crystal D Anatomic crystal 13 Which of the following does not contain a pair of allotropes? A Hydrogen and tritium B_ Oxygen and ozone C Fullerene and diamond D_ Monoclinic sulphur and rhombic sulphur = The three allotropes of carbon are diamond, graphite and fullerene. Which of the following statements correctly describes all three allotropes? A All three allotropes have carbon atoms, which are covalently bonded to three other carbon atoms. B All three allotropes have good electrical conductivities. All three allotropes will undergo complete combustion to form CO,, D_ All the carbon atoms are tetrahedrally bonded together by strong covalent bonds. 15 When a 52 cm’ flask is filled with a gas at 200 °C, the pressure produced is 1.29 x 10° Pa. If the temperature is then increased to 400 °C, the pressure increases to 3.68 x 10° Pa. Which statement explains these observations? [Gas constant, R, is 8.31 J K! mol".] A The gas obeys Boyle’s law. B_ The gas exists as a dimer at 200 °C. C_ The number of gas molecules increases by 2.85 times at 400 °C. D_ The number of collisions between gas molecules and the wall of the flask doubles at 400 °C. Sa 16 A phase diagram of water is shown below. Pressure(Pa) temperature (k) 273.16 What can be deduced from the phase diagram? A’ An increase in pressure will decrease the freezing point of water. B_ An increase in pressure will decrease the boiling point of water. C Ice sublimes at a pressure higher than 611 Pa. D_ Water exists as liquid at a pressure of 611 Pa and a temperature of 298 K. 17 Which one of the following equations apply to an ideal gas? [P = pressure; V = volume; M = molar mass; p = density; R = gas constant; T= temperature] = PRT, =AT A p=fe c py=At m _ RT P_ RT BPP > aT 18 The graph shows the Boltzmann distribution curve of molecular speeds. Which one of the following statements is correct? ‘number of ‘molecules with ‘a given speed A Raising the temperature always decreases the number of molecules with a given speed. B_ The area under the curve indicates the speed of molecules.C Raising the temperature moves the maximum of the curve to the right. D_ The peak of the curve represents the highest speed of the particles. 19 When a sample of a gas is compressed at constant temperature from 25 atm to 60 atm, its volume changes from 45 em? to 20 cm’. Which of the following statements are possible explanations of this behaviour? A. The gas behaves non-ideally B_ Attractive forces exist between the particles at higher pressure The gas is adsorbed onto the container walls D_ The gas dissociates at higher pressure 20. Which of the following statements correctly describe what happens when salt is added to a mixture of ice and water at 0°C? A. The volume of liquid water increases B_ The freezing point increases C More ice is formed D_ Temperature increases 21 Fullerene is an allotrope of carbon with the structure shown below. The following statements are true of fullerene molecule except A each carbon atom is sp* hybridised. B the bond angles are smaller than that of diamond. C _ its molecule is spherical in shape with 32 surfaces. D the carbon atoms in the molecule have delocalised electrons. 22 0.65 g of a gas G occupies 220 cm’ at a temperature of 50 °C and a pressure of 100 kPa. What is the relative molecular mass of gas G?[R = 8.31 JK“ mot] A 79 C 38.4 B 123 D 79.3 Grane 23 The following statements are true about liquids except ‘A liquids have surface tension. B the viscosity of liquids is higher than that in gases. C._ the rate of diffusion in liquids is lower than that in gases. D_ the particles in liquids vibrate and rotate in an orderly manner. 24 You are required to prepare an aqueous solution that does not freeze until well below 0 °C. The most suitable solute should A. have a low melting point B dissociate into several ions C__ have a high relative molecular mass D_ dissolve easily in water 25. The phase diagram of substance ¥ is shown below. pressure (atm) 735 tp 5ST 31 temperature (°C) Which statement is correct? A At point P, liquid X and gas cannot be distinguished. B_ The melting point of substance X decreases when pressure increases. C At-S7°C and a pressure of | atm, substance X exists in the liquid phase. D_ At temperatures above 31 °C, gas X cannot be liquefied by increasing the pressure.SOT CT STRUCTURED QUESTIONS 1 An analysis of the exhaust gases from a Proton car produced the following data Carbon dioxide Carbon monoxide co 2.0 i | Oxygen oO, 0.80 Unburnt octane GH 0.05 Assume that all gases are ideal and that (a) If 1 mol of gas occupies 22.4 dm? of gas at 200 °C and 1 atm. Calculate the volume, and hence how many 1.0 dm’ of the exhaust gas (c) Calculate the overall volume, and hence how many moles of carbon monoxide and carbon dioxide there are in 1.0 dm? of the exhaust gas, Subsequently determine how many moles of octane produced these oxides on burning. t all measurements are taken at 200 °C. at s.t.p., calculate the volume occupied by I mol ) moles there are, of unburnt octane in oe Assume all carbon monoxide and carbon dioxide are obtained from the combustion of octane. Determine the Percentage of octane that remained unburnt. (4) Suggest why the exhaust gases contained unburnt octane, despite oxygen still being present. 2) Name a gas, not listed above, that is the chief component of the exhaust gases A real gas X behaves almost like an ideal gas. For n mol of gas X at pressure p, the graph of volume V versus temperature T is shown below. Teo) ) What is the most probable identity of gas X? Explain your answer, ) On the graph above, sketch and label a graph of the variation in volume with temperature at a lower pressure p’ while other conditions remain constant. At pressure p and temperature 0 °C, a gas Y shows a negative deviation from an ‘deal gas. Mark the expected volume of gas Y on the above graph. Explain your answer.3. The phase diagram of carbon dioxide is shown below. pressure (atm) | 73-87 temperature (°C) (a) Dry ice is commonly used in concerts to form fog. Explain the formation of the fog. (b) Carbon dioxide in fire extinguishers is in liquid form. Indicate on the above phase diagram the change in the physical state of carbon dioxide when the pressure of a fire extinguisher is reduced. ESSAY QUESTIONS 1 (a) Explain, with reference to intermolecular forces, (i) why real gases are more easily compressible at moderate pressures than at high pressures. (ii) why real gases behave ideally at high temperature, (b) “Molecules of a real gas move at varying speeds”. Draw a suitable graph to explain the phenomenon. (c) A vessel contains 8.0 g oxygen at 30 °C and 50 kPa. (i) Calculate the volume of the vessel. (ii) Determine the final pressure exerted when 1.0 mol of hydrogen gas is added at the same temperature without changing the volume. (iii) If the mixture is then exploded and allowed to cool to 25 °C, determine the pressure of the residual gas in the vessel without changing the volume of the system. 2 (a) What is meant by partial pressure of a gas in a mixture of gases? (b) State Dalton’s law of partial pressure. (©) 100 dm’ of nitrogen gas at a temperature of 25 °C and a pressure of 1.2 x 10° Pa is known to contain traces of carbon dioxide and water. When the gas was bubbled through concentrated sulphuric acid, the loss in mass is 0.20 g. When it is passed through aqueous solution of sodium hydroxide, the loss in mass observed is 9.6 g. (i) State the gas absorbed by concentrated sulphuric acid and sodium hydroxide. Explain. (ii) Calculate the percentage composition by volume and the partial pressure of each component in the gas sample.Using ice and water as an example, explain the major differences in the structures of solid and liquid. Discuss the process that occurs when ice converts into liquid water, Explain the effect of external pressure on a system consisting of ice and water in equilibrium. Explain what do you understand by colligative properties. Explain why sea water evaporates slower than river water at the same temperature and pressure. Discuss if salt water will freeze at a higher or lower temperature than pure water. What do you understand by ideal gas? (Ammonium nitrate is an explosive compound and it decomposes at a high temperature according to the following equation. 2NH,NO\(s) — 4H,O(g) + 2N,(g) + O.(g) Calculate the total volume of gases collected from the decomposition of 100 ¢ of ammonium nitrate at 1.01 x 10° Pa and 25 °C. (ii) Sketch a graph of PV/RT against P for 1.0 mol of ammonia gas at 0 °C. Based on the graph, explain the negative deviation of ammonia gas compared to an ideal gas. Selo 5 Carbon dioxide is a gas at 25 °C and 1.0 atm. Its triple point is at 57 °C and 5.1 atm, and its critical point is at 31 °C and 73.0 atm. (a) Sketch and label the phase diagram for carbon dioxide. (b) Explain why solid carbon dioxide at atmospheric pressure does not melt but sublimes. (©) Explain the phase changes that occur when a sample of carbon dioxide in a closed container under | atm pressure and ~65 °C is pressurised isothermally (constant temperature) to 20 atm, followed by heating at constant pressure to 30 °C.(0) Pr=Px,+ Po, Mole fraction of 0, 242=0.51 70 2 PV =nRT= <1 RT ” im _ PM: Density, d RT 200.0 x 28.0 a= Rane lOy = hem25 atm M: vw Tr 950. 1000 Q73+20)” Q73+1) 75 Number of moles of CO, = 73-5, 1 mol gas occupies 22.4 dm? at sp. 3.75 3.75 Fag Mol gas CO, occupies 375 Checkpoint 4.2 1 (a) An ideal gas obeys the Ideal Gas Law, PV =nRT. Ideal gas has negligible particle volume and no intermolecular forces. (b) Real gas deviates from ideal behaviour because the molecules have finite volume and intermolecular forces acting between them. (©) A teal gas deviates most from ideal behaviour under low temperature and high pressure. (@) A real gas approaches ideal behaviour at high ‘temperature and low pressure. (c) Hydrogen and helium () Carbon dioxide (large molecular size) and ammonia (polar molecules) 2 2NaN\(s) > 3Nx(g) + 2Na(s) 100 33.0+ 3040) x24 91 dm? 100 g NaN, = 1,538 mol 1.538 mol NaN, produces 3 x 1.538 =2.31 mol N, 2.31 mol N,=2.31 x 24.4 = 56.4 dm* 3.(a)CO, consists of large molecules. The intermolecular attractive force is not negligible so the CO, molecules are attracted closer together and thus the volume is smaller. (b) Under high temperature and low pressure. At high temperature, the high kinetic energy of the molecules results in less intermolecular interactions. At low pressure, the molecules are far apart resulting in less intermolecular interactions and the volume of gas molecules is negligible ‘compared to the volume of the system. 4 (a) GH, + 25/2 0, + 8CO, + 9.0 (b) Number of moles of air = PVIRT = (101 kPa) x (1,00 dm'y(8.31 x 323 K) =3.76 x 102 (c) Number of moles of oxygen = (21N00) x 3.76 x 10? = 7.90 x 107 () L mol C,H, reacts with 25/2 mol Os, Number of moles of octane reacting = (2125) x 7.90 x 10 = 6.32 x 10% (©) M, octane CJHy= 114 Mass of octane requires 32x 104 114 20 107 g Density = mass/volume Volume of octane required = 7.20 x 1010.7 .103 om? Focus on STPM 4 Objective Questions 1B 2B 3A 4B 5B 6D 7C 8b 9C Wwe nC RA BA WC ISB WA ITA BC 199A WA 2B 2D BD MB 23D Structured Questions ‘Volume of I mol gas at 200 °C = 38.8 dm’ 0.05 x 1.0 (6) Volume of unburnt CH= "755 = 5.0% 10+ dm" 5.0% 104 ‘ Moles of unburnt CH,,= 5° = 1.29 x 10 (6 Vomeo C0, + CO=12#22,. 9201304 0.130 5 C0, +00 = S257 = 3.35% 10° mol (@) C=335 x10" mol Amount of Cy burt = 3.35109 19x 10+ mol1.2910 ©) [29x 10%+4. 19x10" () As the concentration of O, and octane become low, mixing becomes poor and combustion is slow and thus incomplete (2) Nitrogen 100 2.99% 2 (a) Gas Xs hydrogen or helium gas. The molecular size of H; (or atomic size for He) is small, hence only weak intermolecular van der Waals forces, and can be ignored. Also, molecular volume can be ignored. (b) 300-200-100 0 T¢C) 100 200 (©) Negative deviation means stronger intermolecular attractive force. Therefore the volume occupied by the gas is smaller than an ideal gas. 3 (a) Dry ive or solid CO, sublimes to form CO, gas. This sublimation process absorbs heat, thereby lowering the surrounding temperature, causing moisture in the air to condense into fine water droplets, j (b) pressure 78-7 temperature (°C) Essay Questions 1 (@) (i) At moderate pressures, the molecules are far apart with lots of space in between. Also there exist intermolecular forces of attraction, Thus, gases can be easily compressed at moderate pressures. At high pressures, the molecules are close together with little space in between. Repulsion, ay also exist ‘These make the gas less compressible at high pressures. Gi) At high temperature, the kinetic energy of the molecules is so high that the intermolecular forces is insignificant and can be ignored, (b) number of ‘molecules lsat oeed (©) (@) 8.02 0,=8.0/32. 25 mol. PV ener aOR _ (025N8.31)273430)_ r= # 50x 10 = 0.0126 my = 12.6 dm? () 0, +H,=0.25+ 1,0= 1.25 mol 250 kPa 10.25) x 5K (ii) 2H, +0, > 24,0 0.25 mol O, reacts with (2 x/0.25) mol Hy Residual gas = 1.0 - 0.50 = 0.50 mol Hy Aan P, mT 250 _ 1.25303 P, ~ 0Sx298 P=98 kPa (a) Partial pressure of a gas in a mixture is the pressure ‘exerted by the gas if it alone occupies the container atthe same temperature. (b) Dalton’s law states that the total pressure of a gas mixture is the same as the sum of partial pressures of the constituent gases in the mixture. Pi= Pat Po (©) (i) Concentrated H,SO, absorbs H,0 as it is a dehydrating agent. NaOH absorbs CO;. CO, is acidic, reacts with NaOH. (ii) 0.20 g 1,0 =0.2018.0 = 0.011 mol 9.6 ¢ CO; =9.6/44.0 =0.218 mol 100 dm? N, at 25°C, 1.2 x 10' Pa PV=nRT PV __(1.2x10'Pay(100x 10? m’) “RE” B31TK™ mol )273 +25) K = 4.846 mol 0.218 4346 0.011 4 Tyag* 100= 0.23% 100 — 4,5 - 0,23 = 95.27% %CO, x 100=4.5% Partial pressure of CO, 54x10 Pa0.23 Partial pressure of HO = 55 x 1.2% 10 = 28x 10° Pa 95.27 Partial pressure of Ns = 7p5q"X 1.2 x 10° = 11x10 Pa 3 (@) In solid ice, the H,O molecules are held in a fixed orderly arrangement in a lattice structure, The structure of ice is more open than in water due to the rigid tetrahedral arrangement of the molecules through the formation of hydrogen bonding, In liquid water, the H.O molecules are less orderly arranged and possess translational _ motion, “Molecules in liquid phase have higher kinetic energy. (b) During the melting process (ice to water), molecules absorb energy and vibrate faster. When the energy acquired is sufficient to overcome the intermolecular attractive force, the lattice structure is disrupted. ‘The molecules are freed from their fixed positions and can move freely (©) As external pressure increases, melting point of ice decreases, Due to intermolecular hydrogen bonding, solid ice has an open structure. ‘The density of solid ice is lower than the density of liquid water. When ice melts, its volume contracts, ‘Thus, melting process is preferred at higher pressure. (4) Colligative properties are properties that depend on the number of solute particles in a solution and not on the nature of the particles. These properties include the lowering of vapour pressure, the elevation of boiling point, and the depression of freezing point of a solution, (c) In sea water, there are non-volatile solutes eg. Na’, Mg’, Cl, SO, that form part of the surface area of sea water. These non-volatile solutes do not vaporize casily. Thus they decrease the tendeney for water to vaporize. River water contains less solutes, So river water vaporizes faster than sea water. ( The presence of non-volatile solutes lowers the vapour pressure. These foreign molecules make the orderly arrangement more difficult to achieve, so freezing will occur at a lower temperature. 4 (a) Anideal gas obeys the ideal gas law. ‘An ideal gas has no particle volume and no intermolecular forces. (b) (i) 2 mol NH,NO, forms 3 mol gas (N+ 03) 100 3 100 pmol NH.NO, form: a 30 .875 mol gas (i) 5(a) (6) © PV=nRT Ea (1.875 mol)(8.31 J K mol"')(298 K) TOL x10 Pa = 0.046 m* Pv ar INH, (1.0 mol) wi 19}, sat gs \* P ‘The volume of ideal gas particles is negligible compared to the total volume of the gas and there are no attractive or repulsive forces between the particles. Ammonia is a non-ideal gas because ammonia consists of polar molecules. Attractive forces exist between NH, molecules, causing the molecules to be nearer to each other. So, the measured volume is smaller than expected. The attractive forces also decrease the collisions of the molecules with the walls of the container. Therefore, the measured pressure is lower than < 10, expected, Both of these factors cause FF siving negative deviation, temperature (°C) Liquid CO, does not exist at atmospheric pressure. Ata pressure of 1.0 atm on the CO, phase diagram, only the solid-gas equilibrium curve exists. This shows that if the temperature is increased at atmospheric pressure, solid CO, will never change to liquid but will change directly into gas. At 1 atm and ~65°C, CO, is a gas. Increasing pressure to 20 atm at constant temperature changes, the CO, gas to solid. When heated to 30°C at 20 atm, CO, gas condenses to liquid then vaporizes to gas,