STPM Form 6 – Chapter 1: Matter iii.

iii. Acceleration chamber – positive ions are attracted towards the high negative potential plated that
Matter – anything that occupies space and has mass. accelerates the positive ions to a high and constant velocity. (accelerate the positive ions).
Fundamental Particles of Atoms (Historical Point of View) iv. Magnetic Field – accelerated positive ions are deflected into a circular path according to the m/e ratio.
John Dalton (1808) – atomic theory (separate positive ions of different m/e ratio)
Atoms – small indivisible particles. v. Ion detector – positive ions with different m/e ratios will be deflected to the ion detector that can be
Atoms – neither created nor destroyed. recorded on a moving chart. (detect the number and m/e ratio of the positive ions)
Atoms – chemical reactions result from combination / separation of atoms. vi. Recorder – a flow of current which is amplified and recorded as peaks. (plot the mass spectrum of the
J. J. Thomson (1897) sample)
Electrons – negatively-charged particles. Important note:
Atoms – positively-charged sphere. A lighter ion will deflect more than a heavier ion (the same charge)
Ernest Rutherford (1911) Example: 35Cl+ will deflect more than 37Cl+
Atoms – consists of a positively-charged nucleus with a cloud of electrons surrounding nucleus. An ion with a higher charge will deflect more than an ion with a lower charge (the same mass)
Protons – positively-charged particles. Example: 35Cl2+ will deflect more than 35Cl+
Niels Bohr (1913) Isotopic abundance = fractional abundance = percentage abundance
Electrons – surrounding the nucleus (orbit). One mole – the quantity of a substance that contains the same number of particles (atoms, ions or
James Cadwick (1932) molecules) as the number of atoms in exactly 12 grams of carbon-12 isotope.
Neutrons – electrically neutral subatomic particles. Avogadro constant, L or NA – number of particles (atoms, ions or molecules) present in a mole of
Neutrons – mass almost the same with a proton. substance (elements or compounds)
Nucleus of an atom – consists of protons and neutrons. = 6.02 x 1023 (unit is mol-1)
Modern Atomic Model Number of moles = number of atoms or molecules / Avogadro constant (mol-1)
Nucleus of an atom – consists of protons and neutrons. Number of particles in a sample = number of moles x Avogadro constant (mol-1)
Electrons – moving around the nucleus (orbits / electron shells/ quantum shells) Mass (g) = number of moles (n) x M (Ar or Mr)
Atom – smallest particle of an element. Number or moles (n) = mass (g) / molar mass (g mol-1)
Relative atomic mass (Ar) - (an element) average mass of one atom of the element relative to 1/12 times Mass (g) = number of moles x molar mass (g mol-1)
the mass of one atom of carbon-12. Number of moles = volume of gas (dm3) / 22.4 dm3 at s.t.p. (0˚C and 1 atm or 101 kPa)
= (average mass of one atom of the element) / (1/12 x mass of one atom of C-12) Number of moles = volume of gas (dm3) / 24 dm3 at r.t.p. (25˚C and 1 atm or 101 kPa)
Or Volume of gas (dm3) = number of moles x / 22.4 dm3 at s.t.p.
= 12 x [(average mass of one atom of the element) / (mass of one atom of C-12)] Volume of gas (dm3) = number of moles x / 24 dm3 at r.t.p.
Cations – positively-charge ions. Number of moles of solute = MV / 1000
Example: H+, K+, NH4+ and Mg2+ (M = concentration in mol dm-3)
Anions – negatively-charge ions. (V = volume in cm3)
Example: Br-, OH-, O2- and S2O32- Concentration of a solution (g dm-3) = mass of solute (g) / volume of the solution (dm3)
Molecule – a group of two or more atoms. Concentration of a solution (mol dm-3) = number or moles of solute (mol) / volume of the solution (dm3)
Relative molecular mass (Mr) – (an element or compound) average mass of one molecule of the substance MaVa / MbVb = a/b
relative to 1/12 times the mass of one atom of carbon-12. M1V1 = M2V2
= (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)] STPM Form 6 – Chapter 2: Gas
Proton number / Atomic number / Number of protons (Z) Kinetics Theory of Matter
Number of protons in the nucleus of an atom. describe the behaviour of particles in solids, liquid and gas.
Number of electrons (neutral atom). Solid State
Nucleon number / Mass number / Number of nucleon (A) particles are held rigidly in fixed positions by strong attractive forces in an orderly arrangement;
total number of protons and neutrons in the nucleus of an atom. particles cannot move freely;
A=Z+N particles can only vibrate or rotate about their mean position;
N = number of neutrons particles have less energy (compared to liquids and gases);
Isotopes (of the same element) solids cannot be compressed;
atoms having the same proton number but different nucleon number. solids have fixed shapes;
same number of protons, number of electrons, electronic configuration and chemical properties. solids have fixed volume
different nucleon number, relative mass, density and rate of diffusion. Liquid State
Relative isotopic mass – the ratio of the mass of one atom of the isotope relative to 1/12 times the mass of particles are packed closely together in cluster;
one atom of carbon-12 isotope. particles are not in an orderly arrangement;
= (mass of one atom of the isotope) / (1/12 x mass of one atom of C-12) particles can vibrate, rotate and move freely;
= 12 x [(mass of one atom of the isotope) / (mass of one atom of C-12)] particles have more energy (compared to solids) but have less energy (compared to gases);
Mass spectrometry liquids are not easily compressed;
i. Vaporisation chamber – sample is vaporised (produce gaseous atoms or molecules). liquids have no fixed shape (take the shape of the container);
ii. Ionisation chamber – vapour is bombarded with a stream of high-energy electrons to form positive ions. liquids have fixed volume.
X(g) + e –> X+(g) + 2e. (produce positive ions)
Gaseous State volume: m3 (1 cm3 = 1 x 10-6 m3; 1 dm3 = 1 x 10-3 m3)
particles are separated from each other by distance far greater than their own size; temperature: K
particles have no forces between the particles. n = m / Mr
particles are not in an orderly arrangement; where m = mass of gas and Mr = relative molecular mass of gas
particles can vibrate, rotate and move freely within the container; m/V=ρ
particles have more energy (compared to liquids and solids); where ρ = density of a gas
particles are in constant random motion, moving in straight lines; 4. Dalton’s Law
particles collide (elastic) with the walls of the container, they exert a pressure on the container and there is the total pressure of a mixture of gases do not react is the sum of the partial pressures of the constituent
no loss of kinetics energy during the collision; gases on the mixture.
gases are easily compressed; PT = PA + PB + PC + …
gases have no fixed shape (take the shape of the container); where  PT = total pressure of the mixture and
gases have no fixed volume. PA, PB, PC = partial pressure of gases A, B and C.
Kinetics Theory of Gases Mole fraction of A (XA) in a mixture of A and B
describe the behaviour of ideal gas. = (number of moles of A) / (total number of moles of A + B)
the average kinetics energy of gases particles is directly proportional to the absolute temperature of the = nA / (nA + nB)
gas (Kelvin). PA = PT x XA
four assumptions associated with this theory: where PT = total pressure, PA = partial pressure of gas A, XA = mole fraction of gas A
i.) particles are small compared to the distances between particles that their volumes are negligible. 5. Deviation from Ideal Behaviour
ii.) particles move in straight lines. The direction of a particle’s motion is changed only by its collision with Factors:
either another molecule or the walls of the container. All the collisions are to be elastic (no loss of energy). pressure
iii.) particles are in constant random motion. Gas pressure is only caused by collisions of the particles temperature
against the walls of the container. molecular size
iv.) Gas molecules exhibit no intermolecular forces. The particles neither attract nor repel one another. intermolecular forces
Gas Laws Positive deviation (volume of gas molecules):
three common gas laws to know: Avogadro’s Law, Boyle’s Law and Charles’ Law – A, B and C laws of low pressures (molecules are very far apart – volume of the gas molecules by comparison is extremely
gases. small and can be ignored)
1. Avogadro’s Law high pressures (molecules are closer together – volume of the gas molecules cannot be ignored)
Amedeo Avogadro (1811) Negative deviation (intermolecular forces of attraction):
equal volumes of all gases at the same temperature and pressure contain equal numbers of molecules. low temperature (intermolecular forces of attraction between the molecules will reduce the force exerted by
V / n = k (a constant) the impact of the molecules collide the wall of container. Pressure exerted by the gas is reduced).
V1 / n1 = V2 / n2 high temperature (kinetics energy of the molecules is so high that the intermolecular forces between gas
Where n = number of moles of gas molecules can be ignored).
* Molar volume of a gas (volume occupied by 1 mol of any gas) at standard temperature and pressure Negative deviation (polar bonds)
(s.t.p.) is 22.4 dm3 (Condition: 0˚C / 273 K and 101.3 kNm-1 / 1 atm.). Least deviation – hydrogen gas (small molecular size and non-polar. It possesses very weak
2. Boyle’s Law intermolecular forces of attraction).
Robert Boyle (1662) Marked deviation from ideal behaviour – carbon monoxide gas (polar bonds. It possesses stronger
the volume occupied by fixed mass of gas is inversely proportional to its pressure at constant temperature. intermolecular forces)
applies under isothermal conditions in a closed container. Gas Pressure – the force per unit area exerted by a gas through collisions against a defined area of the
pV = k (a constant) container wall.
p1V1 = p2V2 (Gas molecules collide more frequently with the container wall → gas pressure increases)
* Real gases obey Boyle’s law only at low pressures and high temperatures (ideal gas or perfect gas). Collision Frequency – the rate at which molecules in the gas system collide with each other and the wall of
* Real gases do not obey Boyle’s law at high pressures and low temperatures (non-ideal behaviour). the container.
3. Charles’ Law (Collision frequency ↑ when temperature ↑, concentration of gas particle ↑, mean free path ↓)
Jacques Charles (1780) Collision force – the force exerted by a gas particle during collision between it and the container wall.
the volume occupied by fixed mass of gas is directly proportional to its absolute temperature at constant (greater momentum and shorter time of contact increase the force of impact)
pressure. Collision force can be increased by → temperature increase → greater velocity & greater momentum
V / T = k (a constant) Volume – region within the walls of a container.
V1 / T1 = V2 / T2 (actual volume that a gas molecule can occupy is the volume of the container minus the volume of the
* Temperature is the absolute temperature (-273˚C / 0 K) other gas molecules, because no two gas molecules can occupy the same volume at the same time.)
* Absolute temperature scale (Kelvin scale) as the temperature -273˚C was adopted as the ‘zero’. Concentration (gas) – the number of gas particles per unit volume in a container.
Ideal Gas Equation (Homogeneous gas – used to determine the gas concentration)
Combining Avogrado’s law, Boyle’s law and Charles’ law Mean Free Path – the average distance a particle can travel before colliding with another particle.
Ideal gas equation: Temperature (gas) – total kinetic energy of a system.
pV = nRT Average Kinetic Energy – the mean energy of a particle in that system.
where R is a constant and its value of 8.31 J mol-1 K-1 (energy of each particle ↑ , average kinetic energy ↑ →  ↑ temperature)
pressure: Pa or Nm-2 (1 atm = 101 kPa)
STPM Form 6 – Chapter 3: Liquid and Solid States Particles move faster when liquid is heated.
Changes in the States of Matter The vibrations of the particles increase when temperature of the hot liquid increases.
Freezing / Solidification – liquid –> solid The particles in the solid acquired sufficient kinetic energy to overcome the attraction forces between
Melting – solid –> liquid particles.
Evaporation – liquid –> gas / vapour The particles break away from one another.
Condensation – gas / vapour –> liquid Solid has become liquid.
Sublimation – gas / vapour –> solid Velocity of the particle increase when
Sublimation – solid –> gas / vapour Temperature increase
(Sublimation – iodine, ammonium chloride and solid carbon dioxide) Kinetic energy increase
Kinetics Theory of Liquid Crystal lattice – regular arrangement of atoms, molecules or ions in a crystalline solid.
The kinetics energy content of the particles in a liquid is closer to the kinetic energy content of the particles Unit cell – a small repeating unit that contains a group of particles (atoms, ions or molecules) in a crystal.
in a solid than to that of a gas. There are 7 crystal systems (primitive unit cells – all the lattice points are placed at the corners of the cell
Important points: only):
i) Liquid is made up of tiny particles. Unit cell Characteristics Example
ii) Particles in liquid are continually moving in a zigzag. Cubic a = b = c<a = <b = <c = 90˚ Sodium chloride
iii) The motion for particles in liquid are vibration, rotation and translation. Tetragonal a = b not = c<a = <b = <c = 90˚ Tin
iv) Particles in liquid are not in an orderly arrangement. There are loose clusters of particles which are Orthorhombic a not = b not = c<a = <b = <c = 90˚ Rhombic sulphur
packed closely.
v) Particles in liquid have strong forces of attraction between the particles. Monoclinic a not = b not = c<a = <b = 90˚<c not = 90˚ Monoclinic sulphur
vi) Particles in liquid have more kinetic energy than the particles in solid but less kinetic energy than Triclinic a not = b not = c<a not = <b not = <c not = 90˚ Copper(II) sulphate,
particles in gases. potassium dichromate(VI)
Enthalpy of Fusion – The amount of heat required to change one mole of a pure solid into a liquid. Rhombohedral a = b = c<a = <b = <c not = 90˚ Calcite (calcium carbonate)
Enthalpy of Vaporisation – The amount of heat required to change one mole of pure liquid into a gas. Hexagonal a = b not = c<a = <b = 90˚<c = 120˚ Quartz, graphite
The Structure of a Liquid Four types of lattice points:
i) Melting process: Lattice point at the corner of the unit cell (1/8)
Particles move faster when solid is heated. Lattice point on the edge of the unit cell (1/4)
The vibrations of the particles increase when temperature of the hot solid increases. Lattice point on the face of the unit cell (1/2)
The particles in the solid acquired sufficient kinetic energy to overcome the attraction forces between Lattice point in the centre of the unit cell (1)
particles. Coordination number – the number of atoms, molecules or ions (called the nearest neighbours) that
The particles break away from one another. surrounds a given atom, molecule or ion in a crystal lattice.
Solid has become liquid. A) Simple cubic cell
ii) Freezing process: Example: Caesium chloride & Polonium
The motion of particles in liquid slows down when liquid is cooled. Sphere touches six other spheres.
The particles have low kinetic energy. Four sphere in its own layer, one sphere above the layer and one sphere below the layer.
The particles in liquid have strong attraction forces between particles to overcome the motion of the Coordination number = 6
particles. Unit cell contains in total one atom (8 corners x 1/8 = 1)
Particles held in fixed positions in the lattice structure. B) Body-centre cubic lattice
Liquid has become solid. Example: Sodium, Barium, Potassium, Iron, Manganese, Chromium & Vanadium
iii) Vaporisation process (open container that exposed to the atmosphere): Sphere touches eight other spheres.
The particles escape from the surface of the liquid and become gas. Second layer are placed in the hollows between the spheres in the first layer.
The rate of vaporisation increases with a rise in temperature, a decrease in external pressure and an Each sphere atom is in contact with four atoms in the layer above and four atoms in the layer below.
increase in the surface area of the liquid. Coordination number = 8
A rise in temperature Unit cell contains in total of two lattice points per unit cell (8 corners x 1/8 + 1 = 2)
- room temperature: small percentage of particles have high kinetics and sufficient to overcome the C) Close-packed structures
attraction forces between particles and then escape from the surface of the liquid. Example: Sodium chloride
A decrease in external pressure (increase in internal pressure) Unit cell contains in total of four atoms per unit cell (8 corners x 1/8) + (6 faces x 1/2)
- particles that have enough kinetics energy to vaporise. i) Cubic close packing (ABCABCABC) / Face-centered cubic / Simple cubic close packing
- vapour pressure of liquid increases. Thomas Harriot (1585) first pondered the mathematics of the cannonball arrangement or cannonball stack,
- the particles in liquid collided with one another. which has a face-centered cubic lattice.
- particles have enough kinetics energy to vaporise. Sphere touches twelve other spheres.
- a distribution of kinetic energy has formed. First layer of spheres is packed as closely and each sphere atom is in contact with six other atoms.
An increase in the surface area of the liquid Second layer of spheres is placed on top of the first layer, so that each sphere in the second layer rests on
- the particles in liquid are collided with one another. the hollows between the spheres in the first layer.
- liquid exposed to the air will evaporate (on top of the liquid). Each sphere atom is in contact with six atoms in its own layer, three spheres (atoms) in the layer above
- particles with higher kinetics energies than the average kinetic energy will escape as gas particles first. and three spheres (atoms) in the layer below.
iv) Boiling process: Coordination number = 12
ii) Hexagonal close packing (ABABABABA) diamond is a non-conductor of electricity due to all the four valence electrons of the carbon atoms are
Sphere touches twelve other spheres. involved  with covalent bonding, therefore no free/delocalised electrons.
First layer and the second layer of spheres are packed in the same way as cubic close packing. iii) Fullerene / Buckyball / Buckminsterfullerene – used as lubricant, semi-conductor, superconductors and
(Difference = the third layer of spheres is placed on top of the first layer) catalyst
Coordination number = 12 Molecular formulae of fullerene are C20 (smallest member), C32, C60 (most common member), C70, C76, C78,
Allotropy – existence of elements in two or more different forms (allotropes). C84 and C90.
Elements with variable of coordination number or oxidation states tend to exhibit greater numbers of spherical molecules of 20 – 90 carbon atoms (32 sides, 12 pentagons and 20 hexagons).
allotropic forms and typically more noticeable in non-metal (excluding the halogens and the noble gases) simple molecular solid.
and metalloids. each carbon atom is bonded by strong covalent bonds (sp2 hybridisation / trigonal planar) with three other
Example: carbon atoms. It also contains delocalised π electrons which does not exhibit “superaromaticity” that the
i) Different molecular configuration electrons in the hexagonal rings do not delocalise over the whole molecule.
Oxygen – O2 dioxygen (colourless), O3 trioxygen / ozone (blue), O4 tetraoxygen, O8 octaoxygen (red) Fullerene is a superconductor when it mixed with other metals.
ii) Different crystal structures in the solid Allotropes of Sulphur (different molecular arrangement)
Group 14, Group 15, Group 16 of the periodic table i) alpha sulphur / rhombic sulphur (large crystals composed of S8 molecules)
Group 14: Carbon – graphite, amorphous carbon (soot/coal), diamond, fullerenes C60 (buckyball), lemon yellow colour
Ionsdaleite / hexagonal diamond (meteorites containing graphite strike to the Earth) and carbon nanotubes shape of an octahedron.
(buckytubes) is carbon with a cylindrical nanostructure. crystallises with the orthorhombic lattice.
Group 15: Phosphorus – red phosphorus (polymeric solid), white phosphorus (crystalline solid P 4), scarlet more stable at room temperature (formed in temperature below 95.6˚C).
phosphorus, violet phosphorus, black phosphorus (semiconductor) and diphosphorus P2. melting point at 113˚C.
Group 16: Sulphur – rhombic sulphur (large crystals composed of S8 molecules), monoclinic sulphur (fine density is 2.07 g cm3.
needle-like crystals), plastic (amorphous) sulphur (polymeric solid) and other ring molecules S7 and S12. ii) beta sulphur / monoclinic sulphur (fine needle-like crystals of S8 molecules)
Enantiotropy – the allotropes are stable over a temperature range, with a definite transition point at which deeper yellow colour
one changes into the other. shape of long, narrow and thin needle.
Example: crystallises with the monoclinic lattice.
i) Tin has three allotropes / two enantiotropy: stable at temperature above 95.6˚C.
alpha tin is white (metallic) tin stable above 13.2 ˚C. melting point at 119˚C.
beta tin is grey (nonmethallic) tin below 13.2 ˚C. density is 1.94 g cm3.
gamma tin is rhombic tin. Summary: Definition of the states of matter
ii) Iron has four allotropes / four enantiotropy: State Shape of substance Volume of substance
ferrite (alpha iron) stable below 770°C (BCC) and the iron becomes magnetic. Solid Definite Definite
beta iron stable below 912°C (BCC).
Liquid Indefinite Definite
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. Gas Indefinite Indefinite
*BCC – Body-centred cubic Phase – refers to a single homogeneous physical state of a heterogeneous system. There are three
*FCC – Face-centred cubic phases with the same composition solid, liquid and gas.
Allotropes of Carbon Triple point – the point of a condition of temperature and pressure at which the solid, liquid and vapour
i) Graphite – used as lubricant (powder or oily suspension) phases exist simultaneously at equilibrium.
layered lattice structure Critical point – is the highest temperature and highest pressure at which there is a difference between
hexoganal for the crystal system liquid and vapour states. At either a temperature or a pressure over the critical point, only a single fluid
density is 2.25 g cm-3 state exists, and there is a smooth transition from a dense, liquid-like fluid to a tenuous, gas-like fluid/or
each carbon atom is bonded by strong covalent bonds (sp2 hybridisation / trigonal planar) with three other pressure that is required to liquefy a gas at its critical temperature.
carbon atoms to formed hexagonal ring. Supercooling – metastable condition where a liquid can exist below its freezing point.
the layer are held together by weak van der Waals forces. Phase Diagrams
graphite is soft and slippery due to weak van der Waals forces allow the layer to slide over one another. In laboratory, experiments are being carried out on two environmental factors which is temperature and
graphite is a moderate conductor of electricity along its layer (in the direction parallel but not perpendicular pressure (referred to as independent variables).
to the laver) due to a free electron (per carbon atom) which can move throughout the solid lattice. (Each A) The Phase Diagram of Water
carbon atom has one outer shell electron (unhybridised p electron) which is not used to form covalent - ice (solid), water (liquid) and water vapour / steam (gas)
bonds.) Vapour Pressure Curve
ii) Diamond – used as abrasives (high velocity cutting tools) and ornaments (high refractive index) - critical point = critical temperature (374˚C) and critical pressure (200 atmospheres)
crystallises in a face-centred cubic structure. - temperature above 374˚C and critical pressure 200 atmospheres, the vapour and liquid are
single giant molecule. indistinguishable (no longer two separate phases) because the densities of the gas and liquid are equal
density is 3.50 g cm-3 (meniscus separating a liquid from its vapour disappears).
each carbon atom is bonded by strong covalent bonds (sp3 hybridisation / tetrahedral) with four other Melting Temperature Curve
carbon atoms to formed three-dimensional giant structure. - melting temperature point decrease with pressure- supercooling is the cooling of a liquid to below its
diamond has great hardness and high melting point due to the strong covalent bonds in the 3-D structure. 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 Solid – a state having both a definite shape (fixed lattice structure) and a definite volume.
- Water triple point is at temperature 0.01˚C and pressure 0.006 atm (610 N m-2). All the three phases (ice, Unit cell – repeating structure subunits of a solid molecule (fixed lattice structure / crystal structure).
water and water vapour) coexist at equilibrium. Solid
Normal Melting Temperature Point Simple cubic One atom per repeating unit cell
- the temperature at which both the solid and the liquid states of the substance exist in equilibrium at a
Body-centred cubic Two atoms per repeating unit cell
pressure of 1 atm (101 kNm-2)
Normal Freezing Temperature Point Face-centred cubic Four atoms per repeating unit cell
- the temperature at which both the liquid and the solid states of the substance exist in equilibrium at a Liquid – a state having a definite volume but no definite shape.
pressure of 1 atm (101 kNm-2) Liquid
Unsual Behaviour of Water Intermolecular forces Hydrogen bond Polar interaction Dipole moments Van der Waals
i) Why ice can float? Strongest Strong yet Strong yet weaker than Weakest
- the volume of water increase when the change of phase from liquid to solid. weaker than hydrogen bond and
Reasons: Ice (solid) has an open structure (hydrogen bond). hydrogen bond polar interaction
ii) Why the melting temperature curve slopes to the left (melting point decreases with pressure)?
Surface tension – the resistance of a liquid to an increase in its surface area.
- (In most of substances (except water), an increase in pressure will push the molecules even closer /
Viscosity – the resistance of a liquid to flow / the resistance to flow by an object through the liquid.
Increase in pressure favours the physical state which is higher density)
Summary of phase change :
Reasons: Increasing the pressure favours the formation of liquid water due to the latent heat of fusion is
absorbed from the surroundings during melting. Phase Change Term
B) The Phase Diagram of Carbon Dioxide Liquid to gas Vaporisation
- solid carbon dioxide (dry ice), liquid carbon dioxide and gas carbon dioxide Gas to liquid Condensation
Vapour Pressure Curve Solid to liquid Melting
critical point = critical temperature (374˚C) and critical pressure (217 atmospheres) Liquid to solid Freezing
- temperature above 374˚C and critical pressure 217 atmospheres, the vapour and liquid are
Solid to gas Sublimation
indistinguishable because the densities of the gas and liquid are equal. At this point, carbon dioxide gas
can be liquefied. Gas to solid Deposition
Melting Temperature Curve Isothermal – conditions where the temperature of a system does not change.
- melting temperature point increase with pressure Supercritical fluid – Beyond critical point, it is impossible to distinguish between a gas and liquid.
- melting temperature curve slopes to the right Normal boiling point – temperature at which a material boils when the pressure is 1.00 atm.
- density of dry ice (solid carbon dioxide) is higher than the density of liquid carbon dioxide. It is because
the carbon dioxide molecules are held closer together (smaller volume). STPM Form 6 – Chapter 4: The Electronic Structure of Atoms
- Increasing the pressure favours the formation of solid carbon dioxide due to the latent heat of fusion is Spectrum – a display of the components of a beam of radiation.
liberated (given out) to the surroundings. Hydrogen Spectrum
Triple Point Hydrogen molecules break up to form hydrogen atoms when hydrogen gas (at low pressure) in a
- Carbon dioxide triple point is at temperature -57˚C and pressure 5.1 atm. All the three phases (solid, discharge tube that has been passed through by an electrical discharge.
liquid and gas) coexist at equilibrium. Hydrogen molecules do not emit visible light.
Normal Sublime Temperature Point Emission spectrum contains separate sets of lines.
- the temperature at which both the solid and the gas states of the substance exist in equilibrium at a Each line corresponds to a light of a particular frequency / wavelength.
pressure of 1 atm (101 kNm-2) The series of lines is called the Balmer series that consist of four colours lines.
- at atmospheric pressure, solid carbon dioxide (dry ice) sublimes to form carbon dioxide gas at -78˚C. These lines are: 656 nm (red), 486 nm (blue-green), 434 nm (indigo) and 410 nm (violet) – visible to the
Important Points of Water Phase Diagram and Carbon Dioxide Phase Diagram unaided eyes.
Water Carbon dioxide Other sets of lines are: infrared region (Paschen series, Brackett series and Pfund series) and ultraviolet
Phase Diagram ice, water and water vapour / solid carbon dioxide (dry ice), liquid (Lyman series).
steam carbon dioxide and gas carbon dioxide Convergence limit – wavelength / frequency at which the converging spectral lines merge together.
Vapour Pressure Curve Critical Point = 374˚C and 200 Critical Point = 374˚C and 217 Balmer formula: 1/λ = RH (1/22 – 1/n2)
atmospheres atmospheres where λ = wavelength, RH = Rydberg constant, n = 3,4 … ∞
Hydrogen gas also emits light in the ultraviolet and infrared regions of the electromagnetic spectrum.
Triple Point 0.01˚C and 0.006 atm -57˚C and 5.1 atm
Rydberg equation: 1/λ = RH (1/n12 – 1/n22)
Melting Temperature Curve Increasing the pressure Increasing the pressure favours the Important Table of Summary for the Series:
favours the formation of liquid formation of solid carbon dioxide
Series n1 n2 Type of electromagnetic radiation
water
Lyman 1 2, 3, 4 … ∞ Ultraviolet
Difference between the three phases:
Balmer 2 3, 4, 5 … ∞ Visible
Solid Liquid Gas
Paschen 3 4, 5, 6 … ∞ Infrared
Least kinetic energy (vibration More energetic than solid, yet Most kinetic energy (translation,
and rotational forms and do not not as energetic than gas vibrational and rotation forms) Brackett 4 5, 6, 7 … ∞ Infrared
change their positions) (translation, vibrational and Pfund 5 6, 7, 8 … ∞ Infrared
rotational forms) Electronic Energy Levels
The electrons in an atom can exist at certain energy level. Pauli exclusion principle – Each orbital can hold maximum of two electrons with opposite spin
The electron nearest to the nucleus has the lowest energy. Hund’s rule – Orbital with the same energy level (degenerate orbitals), electron will occupy different orbital
The further the electron from the nucleus, the higher the energy. singly/one electron first the parallel spin, before pairing
Excited state: sufficient energy (heating or electricity discharge) is needed to promote an electron from a Electronic Configurations
lower energy level to higher one. The electrons are filled according the orbitals (Aufbau principle).
The electron will not remain at the high energy level because it is unstable. Fills the 1s orbital to: 1s2
Therefore, it will fall back to the level from it started or to the intermediate level. Fills the 2s orbital to: 2s2
It will lose an amount of energy (energy = difference between the two energy levels). Fills the 2p then 3s orbitals to: 2p63s2
Convergence of the spectral lines – difference between successive energy levels becomes smaller with Fills the 3p then 4s orbitals to: 3p64s2
the increasing distance of the energy levels from the nucleus. Fills the 3d, 4p then 5s orbitals to: 3d104p65s2
Quantum radiation – small amount of radiation emitted by an electron when it falls from higher to a lower (Extended knowledge: the process is repeated until all of the electrons have been accounted for. g-, h-
energy level. and j-orbital exist in theory but the periodic table contains no elements that have electrons in either g-, h-
Planck’s equation: Δ E = E1 – E2 = hf = h (c / λ) and j-orbitals.)
where λ = wavelength, h = Planck’s constant = 6.63 X 10-34 Js, The first break from numerical sequencing comes when the 4s level is filled before the 3d level, despite the
c = speed of light = 3.00 X 108 ms-1 fact that the perimeter of the 3d level is closer to the nucleus than the 4s orbital. The reason is that the
Δ E = difference in energy of two energy levels (quantum of radiation) energy of the level is based on an average position of the electron, not the extreme position.
First ionisation energy – minimum energy required to remove one mole of electrons from one mole of the Ionising electrons are not removed from the atom in reverse order! However, the outer shell electrons are
atoms of an element in the gaseous state. always removed first when forming cations.
Example: M –> M+ + e Examples
Ground state – is the energy level nearest to the nucleus and it is the lowest possible energy state. Example 1: Electronic configuration for manganese.
Calculation for the Ionisation Energy of Hydrogen -> Solution 1:
(Convergence limit in Balmer serier) Neutral manganese (Mn) atom must contain 25 electrons.
Step 1: Find frequency difference between the successive lines in the series. Electronic configuration of Mn: 1s22s22p63s23p64s23d5
Step 2: Plot a graph of frequency difference (y-axis) against the lower frequency (x-axis). Example 2: Which column of the periodic table is diamagnetic?
Step 3: Extrapolate the graph to obtain the frequency (x-axis) when frequency difference = 0 (convergence -> Solution 2:
limit) Column 2 (alkaline earth metals) and Column 8 (noble gas). A diamagnetic compound has its entire
Step 4: Calculate the ionisation energy by using ΔE = hf electron spin-paired. There must be an even number of electrons in the element. Valence electronic
Atomic orbital – the region, or volume, of space in an atom within the high probability (95% chance) of configuration for alkaline earth metals is ns2. Valence electronic configuration for noble gas is ns2np6.
finding an electron in an atom. Column 1 (alkali metals) and Column 7 (halogen) are not diamagnetic.
Neil Bohr developed the model of atomic structure assuming that the electrons in an atom are in constant Column 6 (chalcogen) are paramagnetic. Valence electronic configuration for chalcogen is ns 2np4.
motion around the nucleus in circular orbits. Example 3: Electronic configuration for chromium
Heisenberg uncertainty principle states the position and momentum (mass x velocity) of an electron cannot -> Solution 3:
be known with great precision. Charged particles in motion create magnetic fields, therefore it is possible Half-filled d-shell stability in chromium: 1s22s22p63s23p64s13d5 rather than 1s22s22p63s23p64s23d4. (Others
to learn about the pathway and position of the moving electron. half-filled d-shell element are molybdenum and tungsten)
Types of orbital: s, p, d and f orbital Example 4: Electronic configuration for copper.
Core shell – first shell that holds two electrons -> Solution 4:
Valence shell – the outermost shell Fully-filled d-shell stability in copper: 1s22s22p63s23p64s13d10 rather than 1s22s22p63s23p64s23d9.
Effective nuclear charge (Nuclear attraction) accounts for (increases from left to right of the periodic table): Example 5: Which of the following electronic configuration represents an exited state?
i) attraction to the nucleus A. He: 1s2
ii) repulsion from core electrons B. Li: 1s22p1
iii) minimal repulsion by other valence electrons C. N: 1s22s22p3
Ionisation energy is influenced by: D. F: 1s22s22p6
i) nuclear charge (nuclear charge increases, the force of attraction on the electrons becomes stronger and -> Solution 5:
the ionisation energy increases.) B (Li should have 1s22s1 as a ground state and the electronic configuration has the last electron in a 2p-
ii) distance of the electrons from the nucleus (further the outer electrons are from the nucleus, ionisation orbital that is higher energy than the ground state 2s.)
energies will be lower.) An excited state electronic configuration does not follow energetic sequence. An excited state has at least
iii) screening effect (outermost electrons in an atom are shielded from the attraction of the nucleus by the one electron in an energy level higher than the ground state.
repelling effect of the inner effect. The higher the screening effect, lower the ionization energies.) Important: Not to confuse an ion (either cation or anion) with an excited state. A cation is an atom that has
Electronic Structure a deficit of at least one electron and thus carries a positive charge. An anion is an atom that has an excess
Number of electrons in shell = 2(n)2 of at least one electron and thus carries a negative charge.
Example: Lithium atom. Periodic Table can be classified into 4 main groups.
Nucleus = made up of both neutrons and protons 1) The s-block elements:
Core shell = 1st energy level (electron occupancy of 2) Group 1 – general electronic configuration ns1.
Valence shell = 2nd energy level (electron occupancy up to 8 ) Group 2 – ns2.
Arrangement of electrons in an atom 2) The p-block elements
Aufbau principle – Electrons occupy orbitals with the lowest energy level first Group 13 – ns2np1.
Group 14 – ns2 np2. The s-block elements:
Group 15 – ns2 np3. Group 1 – general electronic configuration ns1.
Group 16 – ns2 np4. Group 2 – ns2.
Group 17 – ns2 np5. The p-block elements
Group 18 – ns2 np6. Group 13 – ns2np1.
3) The d-block elements Group 14 – ns2 np2.
Between Group 2 and Group 13 that the d orbitals are partially occupied. Group 15 – ns2 np3.
4) The f-block elements Group 16 – ns2 np4.
Lanthanides (15 elements) – 4f orbitals are partially filled and must have a 6s 2. Group 17 – ns2 np5.
Actinides (15 elements) – 5f orbitals are partially filled and must have a 7s 2. Group 18 – ns2 np6.
The d-block elements
STPM Form 6 – Chapter 5: The Periodic Table Between Group 2 and Group 13 that the d orbitals are partially occupied.
The History of Periodic Table The f-block elements
Döbereiner: Döbereiner’s Triads Lanthanides (15 elements) – 4f orbitals are partially filled and must have a 6s2.
In 1817, Johann Wolfgang Döbereiner a German chemist (1780 – 1849) discovered that trends in certain Actinides (15 elements) – 5f orbitals are partially filled and must have a 7s2. All actinide elements are
properties of selected groups of elements and densities for some of these triads followed a similar pattern. radioactive.
Newlands: Octave Law Atomic Radius – half the distance between the nuclei of the two closest atoms in an element.
In 1865, John Alexander Reina Newlands an English chemist (1837 – 1898) devised a Periodic Table of Atomic Radii – decrease across a period from left to right in the periodic table & increase down a group in
elements arranged in order of their relative atomic masses and name it law of octaves. Law of octaves the periodic table.
states that “any given element will exhibit analogues behaviour to the eighth element following it in the Ionic Radius – measure of the size of an atoms ion in a crystal lattice. Cation is smaller than the
table“. corresponding metal atom and anion is larger than the corresponding nonmetal atom.
Lothar Meyer: Atomic Volume of the Elements Electronegativity – measures the ability of an atom to attract to itself the electron pair forming a covalent
In 1870, Julius Lothar Meyer a German chemist (1836-1907) described 28 elements and arranged the bond. The greater the electronegativity of an atom, the greater the atom attraction for electrons.
atomic volume (relative mass/density) of the elements against their relative atomic masses where similar Ionisation Energy of an Atom – measures of its tendency to lose electrons. The larger the ionisation
chemical and physical properties are repeated at periodic intervals. Meyer presented a series of maxima energy, the more difficult it is to remove an electron.
and minima curve. At the peaks of the curve, Meyer discovered that the most electropositive elements Atomic radii for elements in Periods 2 and 3
appeared at the peak (Li, Na, K, Rb and Cs). Elements Atomic radius (pm)
Mendeleev’s Periodic Table Li 152
In 1869, Dimitri Mendeleev a Russian chemist (1836 – 1907) published the periodic table of all known Be 112
elements and predicted several new elements to complete the table that formed the basis of the modern B 80
Periodic Table. The elements were arranged into Periods (horizontal rows) and Groups (vertical columns).
C 77
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 N 74
(gallium), and eka-boron (scandium). O 74
Moseley: Proton Number F 72
In 1914, Henry Gwyn Jeffrey Moseley an English physicist (1887 – 1915) discovered the relationship Na 156
between an element’s X-ray wavelength and its atomic number (Z), Moseley demonstrated the Mg 136
arrangement by nuclear charge rather than related atomic mass. In Moseley’s experiment the fast moving
Al 125
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 P 110
arrange the elements in the modern Periodic Table in order of increasing proton (atomic number). S 104
The Modern Periodic Table Cl 99
The modern Periodic Table is constructed on the basis of the proton (atomic) numbers of the elements and Atomic radii can be classified into three categories:
their electronic configuration Covalent radius:
A) The short periods Metallic radius
Period 1 – the 1s orbital is being filled. Van der Waals radius
Period 2 – the 2s orbital is filled first, followed by the 2p orbital in the outermost shell (8 elements). Effecting factors of the atomic radius:
Period 3 – the 3s orbital is filled first, followed by the 3p orbital in the outermost shell (8 elements). Screening effect of the inner shell electrons: negatively-charged shells repel one another and are being
B) The long periods pushed further away from the nucleus; screening effect increase; and size of the atoms increase.
Period 4 – the 4s, 3d and 4p orbitals are involved in the outermost shell (18 elements). Nuclear charge (number of protons in the nucleus) that pulls all the electrons closer to the nucleus: The
Period 5 – the 5s, 4d and 5p orbitals are involved in the outermost shell (18 elements). higher the nuclear charge; the stronger the attraction between nucleus and the electron cloud; and the size
Period 6 – the 6s, 4f, 5d and 6p orbitals are involved in the outermost shell (32 elements) and one series of the atom decrease.
known as the lanthanides. Effective nuclear charge = No. of protons – No. of inner electrons
Period 7 – the 7s, 5f, 6d and 7p orbitals are involved in the outermost shell (increasing due to the A) Atomic radius across a period
discovery of new elements) and one series known as the actinides. Example: Period 2 (Li, Be, B, C, N, O, F, Ne) and Period 3 (Na, Mg, Al, Si, P, S, Cl, Ar)
C) The groups in the periodic table 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) Ionic radius (radius of a cation or or an anion) across Period 3
Ion Ionic radius No. of electrons No. of protons
Na+ 0.095 10 11
Mg2+ 0.065 10 12
Al3+ 0.050 10 13
P3- 0.212 18 15
S2- 0.184 18 16
Cl- 0.181 18 17
Isoelectronic – species have the same number of electrons and the same electronic configuration.
When given number of electrons (Na+, Mg2+, Al3+) or (P3-, S2-, 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) Ionic radius down a group
Example: Group 2 (Be2+, Mg2+, Ca2+, Sr2+, Ba2+) & Group 17 (F-, Cl-, Br-, I-)
Going down the Group 2 and Group 17:
Each successive ion has one additional shell filled with electrons.
Screening effect increase
Ionic size increase.