Chem s1 Notes Bbern

STPM Chemistry Form 6 Definition List – Part 1:
ELECTRONIC STRUCTURE OF ATOMS

1. The Hund Rule – orbital with the same energy level (degenerate orbitals), electron will
occupy different orbital singly/one electron first with the parallel spin,
before pairing.(Reject: same spin, spin with same direction) STPM 2008, 2007
2. Pauli Exclusive Principle – Each orbital can hold a maximum of two electrons with opposite
spin. (Reject: different spin) STPM 2007
3. Aufbau principle – Electrons occupy orbitals with the lowest energy level first. (Reject:
occupy lower energy first) STPM 2006, 2007
4. Vapour pressure – the pressure exerted by a vapour that is in equilibrium with its liquid at a
fixed temperature in a closed system. It is due to the collision of the vapour particles on the
walls of the container. STPM 2004
STOICHIOMETRY
1. Molarity (M) [concentration of a fluid solution] – defined as the moles of a solute per
volume of solution.
2. Density [concentration of a fluid solution] – defined as the mass of solution per volume of
solution.
3. Dilution – addition of solvent to a solution resulting in an increase in the volume of the
solution and a decrease in the concentration of the solute in solution.
4. Precipitation reaction (also refer to as double-displacement reaction) – a reaction that
involve two aqueous salts being added together to form ions and a solid salt precipitate.
ACID-BASE EQUILIBRIA
1. Arrhenius acid – acid yields H3O+ when added to water
2. Arrhenius base – base yields OH- when added to water
3. Bronsted-Lowry acid (proton donor) – a substance that donate a proton, H+ to a base.
4. Bronsted-Lowry base (proton acceptor) – a substance that accept a proton, H+ from an acid.
5. Conjugate acid – a species (molecule or ion) formed when a proton is added to a base.
6. Conjugate base – a species (molecule or ion) formed when a proton is removed from an
acid.
7. Lewis acid – an electron-pair acceptor.
8. Lewis base – an electron-pair donor.
9. Electrolyte (also electrolytic conductor) – a chemical compound that will conduct
electricity in the molten state or in aqueous solution.
10. Strong acid – an acid that is almost completely dissociated in aqueous solution. (Stronger
the acid, the weaker its conjugate base)
11. Weak acid – an acid that is only partially dissociated in aqueous solution. (Weaker the acid,
the stronger its conjugate base)
STPM Chemistry Form 6 Definition List – Part 2:
Acid-Base Equilibria
Term Definition Example
Arrhenius acid Yields H3O+ when added to H2O aq: [H3O+] > [OH-]
Arrhenius base Yields OH- when added to H2O aq: [OH-] > [H3O+]
Bronsted-Lowry acid Proton donor HX in protic solvent
Bronsted-Lowry base Proton acceptor KOH in protic solvent
Lewis acid Electron pair acceptor BF3 in aprotic solvent
Lewis base Electron pair donor NH3 in aprotic solvent
Four important concepts (just the berry essence):

1. Acid dissociation – (expressed quantitatively) acid dissociation constant, Ka, is nothing more
than the equilibrium constant for the dissociation reaction of an acid in water.
Relative strength of an acid ↑ (increases), its Ka ↑ (increases) and its pKa ↓(decreases).
(The Ka and pKa of an acid depend on the strength of an acid, but not its concentration.)
2. Base hydrolysis – base hydrolysis constant, Kb, nothing more than the equilibrium
constant for the hydrolysis reaction of a base in water.
Relative strength of a base ↑ (increases), its Kb ↑ (increases) and its pKb ↓ (decreases).
(The Kb and pKb of an acid depend on the strength of an acid, but not its concentration.)
3. Overall Relationship : Acid strength ↑, Ka ↑, pKa ↓, conjugate base strength ↓, Kb ↓, pKb ↑
4. Strength of a reagent (Ka / pKa and Kb / pKb) – the completeness of a reaction in water.
(dissociation = ionisation or electrolytic nature)
The stronger the acid, the more electrolytic it is, because it conducts electricity better due to
the greater number of ions in solution.
The stronger the base, the more readily it undergoes hydrolysis when mixed with water
Acid Name pKa
Cl3CCOOH Trichloroacetic acid 0.64
Cl2HCCOOH Dichloroacetic acid 1.27
H2SO3 Sulfurous acid 1.82
HClO2 Chloroacetic acid 1.90
ClH2CCOOH Chloroacetic acid 2.82
HF Hydrofluoric acid 3.15
HNO2 Nitrous acid 3.41
HCOOH Formic acid 3.74
H3CCOOH Acetic acid 4.74

2,4-(H3C)2C6H3NH3+ 2,4-dimethylanilinium 5.08
4-H2NC6H4NH3+ 4-aminoanilinium 6.18
H3CO3 Carbonic acid 6.36
4-O2NC6H4OH 4-nitrophenol 7.15
HClO Hypochlorous acid 7.46
HBrO Hypobromous acid 8.72
NH4+ Ammonium 9.26
HCN Hydrogen cyanide 9.36
HIO Hypoiodous acid 10.66

STPM Form 6 – Terminology and Concepts: Gases and Gas Law
1. Gas Pressure – the force per unit area exerted by a gas through collisions against a defined
area of the container wall.
(Gas molecules collide more frequently with the container wall → gas pressure increases)
2. Collision Frequency – the rate at which molecules in the gas system collide with each other
and the wall of the container.
(Collision frequency ↑ when temperature ↑, concentration of gas particle ↑, mean free
path ↓)
3. Collision force – the force exerted by a gas particle during collision between it and the
container wall.
(greater momentum and shorter time of contact increase the force of impact)
Collision force can be increased by → temperature increase → greater velocity & greater
momentum
4. Volume – region within the walls of a container.
(actual volume that a gas molecule can occupy is the volume of the container minus the
volume of the other gas molecules, because no two gas molecules can occupy the same
volume at the same time.)
5. Concentration (gas) – the number of gas particles per unit volume in a container.
(Homogeneous gas – used to determine the gas concentration)
6. Mean Free Path – the average distance a particle can travel before colliding with another
particle.
7. Temperature (gas) – total kinetic energy of a system.
8. Average Kinetic Energy – the mean energy of a particle in that system.
(energy of each particle ↑ , average kinetic energy ↑ → ↑ temperature)
Adapted from The Berkeley Review (2004) pg4.
STPM Form 6 – Terminology and Concepts: Phases and Phase Change
Difference between the three phases:
Solid Liquid Gas
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)
change their positions) (translation, vibrational and
rotational forms)
Solid
Solid – a state having both a definite shape (fixed lattice structure) and a definite volume.
Unit cell – repeating structure subunits of a solid molecule (fixed lattice structure / crystal structure).
Solid
Simple cubic One atom per repeating unit cell
Body-centred cubic Two atoms per repeating unit cell
Face-centred cubic Four atoms per repeating unit cell
Liquid
Liquid – a state having a definite volume but no definite shape.
Liquid
Intermolecular forces Hydrogen bond Polar interaction Dipole Van der Waals
moments
Strongest Strong yet weaker Strong yet Weakest

than hydrogen weaker than
bond hydrogen
bond and
polar
interaction
Surface tension – the resistance of a liquid to an increase in its surface area.

Viscosity – the resistance of a liquid to flow / the resistance to flow by an object through the liquid.
Summary of phase change (berry berry important)
Phase Change Term
Liquid to gas Vaporisation
Gas to liquid Condensation
Solid to liquid Melting
Liquid to solid Freezing
Solid to gas Sublimation

Gas to solid Deposition
Isothermal – conditions where the temperature of a system does not change.

Triple point – all three phases (solid, liquid and gas) can coexist simultaneously in the equilibrium
Critical point – highest temperature and pressure at which a liquid may be observed.
Supercritical fluid – Beyond critical point, it is impossible to distinguish between a gas and liquid.
Normal boiling point – temperature at which a material boils when the pressure is 1.00 atm.
Adapted from The Berkeley Review (2001) pg 65
STPM Form 6 – Terminology and Concepts: Matter
Matter – anything that occupies space and has mass.
Fundamental Particles of Atoms (Historical Point of View)
John Dalton (1808) – atomic theory
1. Atoms – small indivisible particles.
2. Atoms – neither created nor destroyed.
3. Atoms – chemical reactions result from combination / separation of atoms.
J. J. Thomson (1897)
1. Electrons – negatively-charged particles.
2. Atoms – positively-charged sphere.
Ernest Rutherford (1911)
1. Atoms – consists of a positively-charged nucleus with a cloud of electrons surrounding
nucleus.
2. Protons – positively-charged particles.
Niels Bohr (1913)
1. Electrons – surrounding the nucleus (orbit).
James Cadwick (1932)
1. Neutrons – electrically neutral subatomic particles.
2. Neutrons – mass almost the same with a proton.
3. Nucleus of an atom – consists of protons and neutrons.
Modern Atomic Model
1. Nucleus of an atom – consists of protons and neutrons.
2. Electrons – moving around the nucleus (orbits / electron shells/ quantum shells)
Atoms
Atom – smallest particle of an element.
Relative atomic mass (Ar) - (an element) average mass of one atom of the element relative to 1/12
times the mass of one atom of carbon-12.
= (average mass of one atom of the element) / (1/12 x mass of one atom of C-12)
Or
= 12 x [(average mass of one atom of the element) / (mass of one atom of C-12)]
Cations – positively-charge ions.
Example: H+, K+, NH4+ and Mg2+
Anions – negatively-charge ions.
Example: Br-, OH-, O2- and S2O32-
Molecule – a group of two or more atoms.
Relative molecular mass (Mr) – (an element or compound) average mass of one molecule of the
substance relative to 1/12 times the mass of one atom of carbon-12.
= (average mass of one molecule of substance) / (1/12 x mass of one atom of C-12)
Or
= 12 x [(average mass of one molecule of substance) / (mass of one atom of C-12)]
Proton number / Atomic number / Number of protons (Z)
 Number of protons in the nucleus of an atom.
 Number of electrons (neutral atom).
Nucleon number / Mass number / Number of nucleon (A)
 total number of protons and neutrons in the nucleus of an atom.
A=Z+N
N = number of neutrons
Isotopes (of the same element)
 atoms having the same proton number but different nucleon number.
 same number of protons, number of electrons, electronic configuration and chemical
properties.
 different nucleon number, relative mass, density and rate of diffusion.
Relative isotopic mass – the ratio of the mass of one atom of the isotope relative to 1/12 times the
mass of one atom of carbon-12 isotope.
= (mass of one atom of the isotope) / (1/12 x mass of one atom of C-12)
Or
= 12 x [(mass of one atom of the isotope) / (mass of one atom of C-12)]
Mass spectrometry
i. Vaporisation chamber – sample is vaporised (produce gaseous atoms or molecules).
ii. Ionisation chamber – vapour is bombarded with a stream of high-energy electrons to form
positive ions. X(g) + e –> X+(g) + 2e. (produce positive ions)
iii. Acceleration chamber – positive ions are attracted towards the high negative potential plated
that accelerates the positive ions to a high and constant velocity. (accelerate the positive ions).
iv. Magnetic Field – accelerated positive ions are deflected into a circular path according to the m/e
ratio. (separate positive ions of different m/e ratio)
v. Ion detector – positive ions with different m/e ratios will be deflected to the ion detector that can
be recorded on a moving chart. (detect the number and m/e ratio of the positive ions)
vi. Recorder – a flow of current which is amplified and recorded as peaks. (plot the mass spectrum of
the sample)
Important note:
 A lighter ion will deflect more than a heavier ion (the same charge)
Example: 35Cl+ will deflect more than 37Cl+
 An ion with a higher charge will deflect more than an ion with a lower charge (the same
mass)
Example: 35Cl2+ will deflect more than 35Cl+
Isotopic abundance = fractional abundance = percentage abundance
One mole – the quantity of a substance that contains the same number of particles (atoms, ions or
molecules) as the number of atoms in exactly 12 grams of carbon-12 isotope.
Avogadro constant, L or NA – number of particles (atoms, ions or molecules) present in a mole of
substance (elements or compounds)
= 6.02 x 1023 (unit is mol-1)
Number of moles = number of atoms or molecules / Avogadro constant (mol-1)
Number of particles in a sample = number of moles x Avogadro constant (mol-1)
Mass (g) = number of moles (n) x M (Ar or Mr)
Number or moles (n) = mass (g) / molar mass (g mol-1)
Mass (g) = number of moles x molar mass (g mol-1)
Number of moles = volume of gas (dm3) / 22.4 dm3 at s.t.p. (0˚C and 1 atm or 101 kPa)
Number of moles = volume of gas (dm3) / 24 dm3 at r.t.p. (25˚C and 1 atm or 101 kPa)
Volume of gas (dm3) = number of moles x / 22.4 dm3 at s.t.p.
Volume of gas (dm3) = number of moles x / 24 dm3 at r.t.p.
Number of moles of solute = MV / 1000
(M = concentration in mol dm-3)
(V = volume in cm3)
Concentration of a solution (g dm-3) = mass of solute (g) / volume of the solution (dm3)
Concentration of a solution (mol dm-3) = number or moles of solute (mol) / volume of the solution
(dm3)
MaVa / MbVb = a/b
M1V1 = M2V2
STPM Chemistry Form 6 – Terminology and Concepts: The Electronic
Structure of Atoms (Part 1)
Spectrum – a display of the components of a beam of radiation.
Hydrogen Spectrum
1. Hydrogen molecules break up to form hydrogen atoms when hydrogen gas (at low pressure)
in a discharge tube that has been passed through by an electrical discharge.
2. Hydrogen molecules do not emit visible light.
3. Emission spectrum contains separate sets of lines.
4. Each line corresponds to a light of a particular frequency / wavelength.
5. The series of lines is called the Balmer series that consist of four colours lines.
6. These lines are: 656 nm (red), 486 nm (blue-green), 434 nm (indigo) and 410 nm (violet) –
visible to the unaided eyes.
7. Other sets of lines are: infrared region (Paschen series, Brackett series and Pfund series) and
ultraviolet (Lyman series).
8. Convergence limit – wavelength / frequency at which the converging spectral lines merge
together.
Balmer formula: 1/λ = RH (1/22 – 1/n2)
where λ = wavelength, RH = Rydberg constant, n = 3,4 … ∞
9. Hydrogen gas also emits light in the ultraviolet and infrared regions of the electromagnetic
spectrum.
Rydberg equation: 1/λ = RH (1/n12 – 1/n22)
Berry Important Table of Summary for the Series:
Series n1 n2 Type of electromagnetic radiation
Lyman 1 2, 3, 4 … ∞ Ultraviolet
Balmer 2 3, 4, 5 … ∞ Visible
Paschen 3 4, 5, 6 … ∞ Infrared
Brackett 4 5, 6, 7 … ∞ Infrared
Pfund 5 6, 7, 8 … ∞ Infrared
Electronic Energy Levels

1. The electrons in an atom can exist at certain energy level.
2. The electron nearest to the nucleus has the lowest energy.
3. The further the electron from the nucleus, the higher the energy.
4. Excited state: sufficient energy (heating or electricity discharge) is needed to promote an
electron from a lower energy level to higher one.
5. The electron will not remain at the high energy level because it is unstable.
6. Therefore, it will fall back to the level from it started or to the intermediate level.
7. It will lose an amount of energy (energy = difference between the two energy levels).
8. Convergence of the spectral lines – difference between successive energy levels becomes
smaller with the increasing distance of the energy levels from the nucleus.
9. Quantum radiation – small amount of radiation emitted by an electron when it falls from
higher to a lower energy level.
Planck’s equation: Δ E = E1 – E2 = hf = h (c / λ)
where λ = wavelength, h = Planck’s constant = 6.63 X 10-34 Js,
c = speed of light = 3.00 X 108 ms-1
Δ E = difference in energy of two energy levels (quantum of radiation)
First ionisation energy – minimum energy required to remove one mole of electrons from one mole
of the atoms of an element in the gaseous state.
Example: M –> M+ + e
Ground state – is the energy level nearest to the nucleus and it is the lowest possible energy state.
Calculation for the Ionisation Energy of Hydrogen
(Convergence limit in Balmer serier)
 Step 1: Find frequency difference between the successive lines in the series.
 Step 2: Plot a graph of frequency difference (y-axis) against the lower frequency (x-axis).
 Step 3: Extrapolate the graph to obtain the frequency (x-axis) when frequency difference = 0
(convergence limit)
 Step 4: Calculate the ionisation energy by using ΔE = hf
STPM Chemistry Form 6 – Terminology and Concepts: The Electronic
Structure of Atoms (Part 2 – Final)
Atomic orbital – the region, or volume, of space in an atom within the high probability (95% chance)
of finding an electron in an atom.
Neil Bohr developed the model of atomic structure assuming that the electrons in an atom are in
constant motion around the nucleus in circular orbits.
Heisenberg uncertainty principle states the position and momentum (mass x velocity) of an electron
cannot be known with great precision. Charged particles in motion create magnetic fields, therefore
it is possible to learn about the pathway and position of the moving electron.
Types of orbital: s, p, d and f orbital
Core shell – first shell that holds two electrons
Valence shell – the outermost shell
Effective nuclear charge (Nuclear attraction) accounts for (increases from left to right of the periodic
table):
 i) attraction to the nucleus
 ii) repulsion from core electrons
 iii) minimal repulsion by other valence electrons
Ionisation energy is influenced by:
 i) nuclear charge (nuclear charge increases, the force of attraction on the electrons becomes
stronger and the ionisation energy increases.)
 ii) distance of the electrons from the nucleus (further the outer electrons are from the
nucleus, ionisation energies will be lower.)
 iii) screening effect (outermost electrons in an atom are shielded from the attraction of the
nucleus by the repelling effect of the inner effect. The higher the screening effect, lower the
ionization energies.)
Electronic Structure
Number of electrons in shell = 2(n)2
 Example: Lithium atom.
Nucleus = made up of both neutrons and protons
Core shell = 1st energy level (electron occupancy of 2)
Valence shell = 2nd energy level (electron occupancy up to 8 )
Arrangement of electrons in an atom
 Aufbau principle – Electrons occupy orbitals with the lowest energy level first
 Pauli exclusion principle – Each orbital can hold maximum of two electrons with opposite
spin
 Hund’s rule – Orbital with the same energy level (degenerate orbitals), electron will occupy
different orbital singly/one electron first the parallel spin, before pairing
Electronic Configurations
The electrons are filled according the orbitals (Aufbau principle).
1. Fills the 1s orbital to: 1s2
2. Fills the 2s orbital to: 2s2
3. Fills the 2p then 3s orbitals to: 2p63s2
4. Fills the 3p then 4s orbitals to: 3p64s2
5. Fills the 3d, 4p then 5s orbitals to: 3d104p65s2
(Extended knowledge: the process is repeated until all of the electrons have been accounted for. g-,
h- and j-orbital exist in theory but the periodic table contains no elements that have electrons in
either g-, h- and j-orbitals.)
The first break from numerical sequencing comes when the 4s level is filled before the 3d level,
despite the fact that the perimeter of the 3d level is closer to the nucleus than the 4s orbital. The
reason is that the energy of the level is based on an average position of the electron, not the
extreme position.
Ionising electrons are not removed from the atom in reverse order! However, the outer shell
electrons are always removed first when forming cations.
Examples
Example 1: Electronic configuration for manganese.
-> Solution 1:
 Neutral manganese (Mn) atom must contain 25 electrons.
 Electronic configuration of Mn: 1s22s22p63s23p64s23d5
Example 2: Which column of the periodic table is diamagnetic?
-> Solution 2:
 Column 2 (alkaline earth metals) and Column 8 (noble gas). A diamagnetic compound has its
entire electron spin-paired. There must be an even number of electrons in the element.
Valence electronic configuration for alkaline earth metals is ns2. Valence electronic
configuration for noble gas is ns2np6.
 Column 1 (alkali metals) and Column 7 (halogen) are not diamagnetic.
 Column 6 (chalcogen) are paramagnetic. Valence electronic configuration for chalcogen is
ns2np4.
Example 3: Electronic configuration for chromium
-> Solution 3:
 Half-filled d-shell stability in chromium: 1s22s22p63s23p64s13d5 rather than
1s22s22p63s23p64s23d4. (Others half-filled d-shell element are molybdenum and tungsten)
Example 4: Electronic configuration for copper.
-> Solution 4:
 Fully-filled d-shell stability in copper: 1s22s22p63s23p64s13d10 rather than
1s22s22p63s23p64s23d9.
Example 5: Which of the following electronic configuration represents an exited state?
A. He: 1s2
B. Li: 1s22p1
C. N: 1s22s22p3
D. F: 1s22s22p6
-> Solution 5:
 B (Li should have 1s22s1 as a ground state and the electronic configuration has the last
electron in a 2p-orbital that is higher energy than the ground state 2s.)
 An excited state electronic configuration does not follow energetic sequence. An excited
state has at least one electron in an energy level higher than the ground state.
Important: Not to confuse an ion (either cation or anion) with an excited state. A cation is an atom
that has a deficit of at least one electron and thus carries a positive charge. An anion is an atom that
has an excess of at least one electron and thus carries a negative charge.
Periodic Table can be classified into 4 main groups.
1) The s-block elements:
 Group 1 – general electronic configuration ns1.
 Group 2 – ns2.
2) The p-block elements
 Group 13 – ns2np1.
 Group 14 – ns2 np2.
3) The d-block elements
 Between Group 2 and Group 13 that the d orbitals are partially occupied.
4) The f-block elements
 Lanthanides (15 elements) – 4f orbitals are partially filled and must have a 6s2.
 Actinides (15 elements) – 5f orbitals are partially filled and must have a 7s2.
STPM Chemistry Form 6 – Terminology and Concepts: Gas
Kinetics Theory of Matter
 describe the behaviour of particles in solids, liquid and gas.
Solid State
 particles are held rigidly in fixed positions by strong attractive forces in an orderly
arrangement;
 particles cannot move freely;
 particles can only vibrate or rotate about their mean position;
 particles have less energy (compared to liquids and gases);
 solids cannot be compressed;
 solids have fixed shapes;
 solids have fixed volume
Liquid State
 particles are packed closely together in cluster;
 particles are not in an orderly arrangement;
 particles can vibrate, rotate and move freely;
 particles have more energy (compared to solids) but have less energy (compared to gases);
 liquids are not easily compressed;
 liquids have no fixed shape (take the shape of the container);
 liquids have fixed volume.
Gaseous State
 particles are separated from each other by distance far greater than their own size;
 particles have no forces between the particles.
 particles are not in an orderly arrangement;
 particles can vibrate, rotate and move freely within the container;
 particles have more energy (compared to liquids and solids);
 particles are in constant random motion, moving in straight lines;
 particles collide (elastic) with the walls of the container, they exert a pressure on the
container and there is no loss of kinetics energy during the collision;
 gases are easily compressed;
 gases have no fixed shape (take the shape of the container);
 gases have no fixed volume.
Kinetics Theory of Gases
 describe the behaviour of ideal gas.
 the average kinetics energy of gases particles is directly proportional to the absolute
temperature of the gas (Kelvin).
 four assumptions associated with this theory:
i.) particles are small compared to the distances between particles that their volumes are negligible.
ii.) particles move in straight lines. The direction of a particle’s motion is changed only by its collision
with either another molecule or the walls of the container. All the collisions are to be elastic (no loss
of energy).
iii.) particles are in constant random motion. Gas pressure is only caused by collisions of the particles
against the walls of the container.
iv.) Gas molecules exhibit no intermolecular forces. The particles neither attract nor repel one
another.
Gas Laws
 three common gas laws to know: Avogadro’s Law, Boyle’s Law and Charles’ Law – A, B and C
laws of gases.
(If you find yourself about to get confused, here is a simple story about how the scientist, Avogadro
might have made his discovery: Avogadro was into counting big numbers, so his law focuses on the
number of molecules. Therefore, Avogadro’s law deals with the relationship between moles of gas
and volume. Big Boy Boyle sat on his lunch and smashed it (decreased the volume of his sandwich),
by increasing the pressure on it. Therefore, Boyle’s law deals with the relationship between pressure
and volume. Good ol’ Chuck overheated his popcorn and it scattered all over (increased its volume).
Therefore, Charles’s law deals with the relationship between temperature and volume.) taken from
General Chemistry Part II Sections VI-X pg 13. (2001) Berkeley Review.
1. Avogadro’s Law
 Amedeo Avogadro (1811)
 equal volumes of all gases at the same temperature and pressure contain equal numbers of
molecules.
V / n = k (a constant)
V1 / n1 = V2 / n2
Where n = number of moles of gas
* Molar volume of a gas (volume occupied by 1 mol of any gas) at standard temperature and
pressure (s.t.p.) is 22.4 dm3 (Condition: 0˚C / 273 K and 101.3 kNm-1 / 1 atm.).
2. Boyle’s Law
 Robert Boyle (1662)
 the volume occupied by fixed mass of gas is inversely proportional to its pressure at constant
temperature.
 applies under isothermal conditions in a closed container.
pV = k (a constant)
p1V1 = p2V2
* Real gases obey Boyle’s law only at low pressures and high temperatures (ideal gas or perfect gas).
* Real gases do not obey Boyle’s law at high pressures and low temperatures (non-ideal behaviour).
3. Charles’ Law
 Jacques Charles (1780)
 the volume occupied by fixed mass of gas is directly proportional to its absolute
temperature at constant pressure.
V / T = k (a constant)
V1 / T1 = V2 / T2
* Temperature is the absolute temperature (-273˚C / 0 K)
* Absolute temperature scale (Kelvin scale) as the temperature -273˚C was adopted as the ‘zero’.
Ideal Gas Equation
Combining Avogrado’s law, Boyle’s law and Charles’ law
 Ideal gas equation:
pV = nRT
where R is a constant and its value of 8.31 J mol-1 K-1
pressure: Pa or Nm-2 (1 atm = 101 kPa)
volume: m3 (1 cm3 = 1 x 10-6 m3; 1 dm3 = 1 x 10-3 m3)
temperature: K
n = m / Mr
where m = mass of gas and Mr = relative molecular mass of gas
m/V=ρ
where ρ = density of a gas
4. Dalton’s Law
 the total pressure of a mixture of gases do not react is the sum of the partial pressures of
the constituent gases on the mixture.
PT = PA + PB + P C + …
where PT = total pressure of the mixture and
PA, PB, PC = partial pressure of gases A, B and C.
Mole fraction of A (XA) in a mixture of A and B
= (number of moles of A) / (total number of moles of A + B)
= nA / (nA + nB)
P A = P T x XA
where PT = total pressure, PA = partial pressure of gas A, XA = mole fraction of gas A
5. Deviation from Ideal Behaviour
Factors:
1. pressure
2. temperature
3. molecular size
4. intermolecular forces
Positive deviation (volume of gas molecules):
1. low pressures (molecules are very far apart – volume of the gas molecules by comparison is
extremely small and can be ignored)
2. high pressures (molecules are closer together – volume of the gas molecules cannot be
ignored)
Negative deviation (intermolecular forces of attraction):
1. low temperature (intermolecular forces of attraction between the molecules will reduce the
force exerted by the impact of the molecules collide the wall of container. Pressure exerted
by the gas is reduced).
2. high temperature (kinetics energy of the molecules is so high that the intermolecular forces
between gas molecules can be ignored).
Negative deviation (polar bonds)
1. Least deviation – hydrogen gas (small molecular size and non-polar. It possesses very weak
intermolecular forces of attraction).
2. Marked deviation from ideal behaviour – carbon monoxide gas (polar bonds. It possesses
stronger intermolecular forces)
STPM Form 6 – Terminology and Concepts: Liquid and Solid States (Part 1)
Changes in the States of Matter
1. Freezing / Solidification – liquid –> solid
2. Melting – solid –> liquid
3. Evaporation – liquid –> gas / vapour
4. Condensation – gas / vapour –> liquid
5. Sublimation – gas / vapour –> solid
6. Sublimation – solid –> gas / vapour
(Sublimation – iodine, ammonium chloride and solid carbon dioxide)
Kinetics Theory of Liquid
The kinetics energy content of the particles in a liquid is closer to the kinetic energy content of the
particles in a solid than to that of a gas.
Important points:
i) Liquid is made up of tiny particles.
ii) Particles in liquid are continually moving in a zigzag.
iii) The motion for particles in liquid are vibration, rotation and translation.
iv) Particles in liquid are not in an orderly arrangement. There are loose clusters of particles which
are packed closely.
v) Particles in liquid have strong forces of attraction between the particles.
vi) Particles in liquid have more kinetic energy than the particles in solid but less kinetic energy than
particles in gases.
Enthalpy of Fusion – The amount of heat required to change one mole of a pure solid into a liquid.
Enthalpy of Vaporisation – The amount of heat required to change one mole of pure liquid into a
gas.
The Structure of a Liquid
i) Melting process:
 Particles move faster when solid is heated.
 The vibrations of the particles increase when temperature of the hot solid increases.
 The particles in the solid acquired sufficient kinetic energy to overcome the attraction
forces between particles.
 The particles break away from one another.
 Solid has become liquid.
ii) Freezing process:
 The motion of particles in liquid slows down when liquid is cooled.
 The particles have low kinetic energy.
 The particles in liquid have strong attraction forces between particles to overcome the
motion of the particles.
 Particles held in fixed positions in the lattice structure.
 Liquid has become solid.
iii) Vaporisation process (open container that exposed to the atmosphere):
 The particles escape from the surface of the liquid and become gas.
 The rate of vaporisation increases with a rise in temperature, a decrease in external pressure
and an increase in the surface area of the liquid.
 A rise in temperature
- room temperature: small percentage of particles have high kinetics and sufficient to overcome the
attraction forces between particles and then escape from the surface of the liquid.
A decrease in external pressure (increase in internal pressure)
- particles that have enough kinetics energy to vaporise.
- vapour pressure of liquid increases.
- the particles in liquid collided with one another.
- particles have enough kinetics energy to vaporise.
- a distribution of kinetic energy has formed.
An increase in the surface area of the liquid
- the particles in liquid are collided with one another.
- liquid exposed to the air will evaporate (on top of the liquid).
- particles with higher kinetics energies than the average kinetic energy will escape as gas particles
first.
iv) Boiling process:
 Particles move faster when liquid is heated.
 The vibrations of the particles increase when temperature of the hot liquid increases.
 The particles in the solid acquired sufficient kinetic energy to overcome the attraction
forces between particles.
 The particles break away from one another.
 Solid has become liquid.
Velocity of the particle increase when
 Temperature increase
 Kinetic energy increase
STPM Chemistry Form 6 – Terminology and Concepts: Liquid and Solid
States (Part 2)
Crystal lattice – regular arrangement of atoms, molecules or ions in a crystalline solid.
Unit cell – a small repeating unit that contains a group of particles (atoms, ions or molecules) in a
crystal.
There are 7 crystal systems (primitive unit cells – all the lattice points are placed at the corners of the
cell only):
Unit cell Characteristics Example
Cubic a = b = c<a = <b = <c = 90˚ Sodium chloride
Tetragonal a = b not = c<a = <b = <c = 90˚ Tin
Orthorhombic a not = b not = c<a = <b = <c = Rhombic sulphur

90˚
Monoclinic a not = b not = c<a = <b = 90˚<c Monoclinic sulphur

not = 90˚
Triclinic a not = b not = c<a not = <b not Copper(II) sulphate, potassium
= <c not = 90˚ dichromate(VI)
Rhombohedral a = b = c<a = <b = <c not = 90˚ Calcite (calcium carbonate)
Hexagonal a = b not = c<a = <b = 90˚<c = Quartz, graphite

120˚
There are 7 multi-primitive lattices (lattice points are located not only at the corners, but also at the
faces or centres of the cells).
There are 14 types of crystal lattices.
Four types of lattice points:
1. Lattice point at the corner of the unit cell (1/8)
2. Lattice point on the edge of the unit cell (1/4)
3. Lattice point on the face of the unit cell (1/2)
4. Lattice point in the centre of the unit cell (1)
Coordination number – the number of atoms, molecules or ions (called the nearest neighbours)
that surrounds a given atom, molecule or ion in a crystal lattice.
A) Simple cubic cell
Example: Caesium chloride & Polonium
 Sphere touches six other spheres.
 Four sphere in its own layer, one sphere above the layer and one sphere below the layer.
 Coordination number = 6
 Unit cell contains in total one atom (8 corners x 1/8 = 1)
B) Body-centre cubic lattice
Example: Sodium, Barium, Potassium, Iron, Manganese, Chromium & Vanadium
 Sphere touches eight other spheres.
 Second layer are placed in the hollows between the spheres in the first layer.
 Each sphere atom is in contact with four atoms in the layer above and four atoms in the
layer below.
 Unit cell contains in total of two lattice points per unit cell (8 corners x 1/8 + 1 = 2)
C) Close-packed structures
Example: Sodium chloride
 Unit cell contains in total of four atoms per unit cell (8 corners x 1/8) + (6 faces x 1/2)
i) Cubic close packing (ABCABCABC) / Face-centered cubic / Simple cubic close packing
Thomas Harriot (1585) first pondered the mathematics of the cannonball arrangement or cannonball
stack, which has a face-centered cubic lattice.
 Sphere touches twelve other spheres.
 First layer of spheres is packed as closely and each sphere atom is in contact with six other
atoms.
 Second layer of spheres is placed on top of the first layer, so that each sphere in the second
layer rests on the hollows between the spheres in the first layer.
 Each sphere atom is in contact with six atoms in its own layer, three spheres (atoms) in the
layer above and three spheres (atoms) in the layer below.
ii) Hexagonal close packing (ABABABABA)
 Sphere touches twelve other spheres.
 First layer and the second layer of spheres are packed in the same way as cubic close
packing.
 (Difference = the third layer of spheres is placed on top of the first layer)
The concept of allotropy was proposed in 1841 by the Swedish scientist Baron Jöns Jakob Berzelius
(1779-1848). The term is derived from the Greek άλλοτροπἱα (allotropia; variation, changeableness).
By 1912, Ostwald proposed that the terms allotrope and allotropy be abandoned and replaced by
polymorph and polymorphism but IUPAC and most chemistry texts still favour the usage of allotrope
and allotropy for elements only.
Allotropy – existence of elements in two or more different forms (allotropes).
Elements with variable of coordination number or oxidation states tend to exhibit greater numbers
of allotropic forms and typically more noticeable in non-metal (excluding the halogens and the noble
gases) and metalloids.
Example:
i) Different molecular configuration
Oxygen – O2 dioxygen (colourless), O3 trioxygen / ozone (blue), O4 tetraoxygen, O8 octaoxygen (red)
ii) Different crystal structures in the solid
Group 14, Group 15, Group 16 of the periodic table
 Group 14: Carbon – graphite, amorphous carbon (soot/coal), diamond, fullerenes
C60(buckyball), Ionsdaleite / hexagonal diamond (meteorites containing graphite strike to the
Earth) and carbon nanotubes (buckytubes) is carbon with a cylindrical nanostructure.
 Group 15: Phosphorus – red phosphorus (polymeric solid), white phosphorus (crystalline
solid P4), scarlet phosphorus, violet phosphorus, black phosphorus (semiconductor) and
diphosphorus P2.
 Group 16: Sulphur – rhombic sulphur (large crystals composed of S8 molecules), monoclinic
sulphur (fine needle-like crystals), plastic (amorphous) sulphur (polymeric solid) and other
ring molecules S7 and S12.
Enantiotropy – the allotropes are stable over a temperature range, with a definite transitionpoint at
which one changes into the other.
Example:
i) Tin has three allotropes / two enantiotropy:
 alpha tin is white (metallic) tin stable above 13.2 ˚C.
 beta tin is grey (nonmethallic) tin below 13.2 ˚C.
 gamma tin is rhombic tin.
ii) Iron has four allotropes / four enantiotropy:
 ferrite (alpha iron) stable below 770°C (BCC) and the iron becomes magnetic.
 beta iron stable below 912°C (BCC).
 gamma irons stable below 1394°C (FCC) crystal structure.
 delta irons stable from cooling down molten iron below 1538°C and has a (BCC) crystal
structure.
 *BCC – Body-centred cubic
 *FCC – Face-centred cubic
Allotropes of Carbon
i) Graphite – used as lubricant (powder or oily suspension)
 layered lattice structure
 hexoganal for the crystal system
 density is 2.25 g cm-3
 each carbon atom is bonded by strong covalent bonds (sp2 hybridisation / trigonal planar)
with three other carbon atoms to formed hexagonal ring.
 the layer are held together by weak van der Waals forces.
 graphite is soft and slippery due to weak van der Waals forces allow the layer to slide over
one another.
 graphite is a moderate conductor of electricity along its layer (in the direction parallel but
not perpendicular to the laver) due to a free electron (per carbon atom) which can move
throughout the solid lattice. (Each carbon atom has one outer shell electron (unhybridised p
electron) which is not used to form covalent bonds.)
ii) Diamond – used as abrasives (high velocity cutting tools) and ornaments (high refractive index)
 crystallises in a face-centred cubic structure.
 single giant molecule.
 density is 3.50 g cm-3
 each carbon atom is bonded by strong covalent bonds (sp3 hybridisation / tetrahedral)
with four other carbon atoms to formed three-dimensional giant structure.
 diamond has great hardness and high melting point due to the strong covalent bonds in the
3-D structure.
 diamond is a non-conductor of electricity due to all the four valence electrons of the carbon
atoms are involved with covalent bonding, therefore no free/delocalised electrons.
iii) Fullerene / Buckyball / Buckminsterfullerene – used as lubricant, semi-conductor,
superconductors and catalyst
 Molecular formulae of fullerene are C20 (smallest member), C32, C60 (most common
member), C70, C76, C78, C84 and C90.
 spherical molecules of 20 – 90 carbon atoms (32 sides, 12 pentagons and 20 hexagons).
 simple molecular solid.
 each carbon atom is bonded by strong covalent bonds (sp2 hybridisation / trigonal planar)
with three other carbon atoms. It also contains delocalised π electrons which does not
exhibit “superaromaticity” that the electrons in the hexagonal rings do not delocalise over
the whole molecule.
 Fullerene is a superconductor when it mixed with other metals.
Allotropes of Sulphur (different molecular arrangement)
i) alpha sulphur / rhombic sulphur (large crystals composed of S8 molecules)
 lemon yellow colour
 shape of an octahedron.
 crystallises with the orthorhombic lattice.
 more stable at room temperature (formed in temperature below 95.6˚C).
 melting point at 113˚C.
 density is 2.07 g cm3.
ii) beta sulphur / monoclinic sulphur (fine needle-like crystals of S8 molecules)
 deeper yellow colour
 shape of long, narrow and thin needle.
 crystallises with the monoclinic lattice.
 stable at temperature above 95.6˚C.
 melting point at 119˚C.
 density is 1.94 g cm3.
STPM Chemistry Form 6 – Terminology and Concepts: Liquid and Solid
States (Part 5)
Summary: Definition of the states of matter
State Shape of substance Volume of substance
Solid Definite Definite
Liquid Indefinite Definite
Gas Indefinite Indefinite
Phase – refers to a single homogeneous physical state of a heterogeneous system. There are three
phases with the same composition solid, liquid and gas.
Triple point – the point of a condition of temperature and pressure at which the solid, liquid and
vapour phases exist simultaneously at equilibrium.
Critical point – is the highest temperature and highest pressure at which there is a difference
between liquid and vapour states. At either a temperature or a pressure over the critical point, only
a single fluid state exists, and there is a smooth transition from a dense, liquid-like fluid to a tenuous,
gas-like fluid/or pressure that is required to liquefy a gas at its critical temperature.
Supercooling – metastable condition where a liquid can exist below its freezing point.
Phase Diagrams
In laboratory, experiments are being carried out on two environmental factors which is temperature
and pressure (referred to as independent variables).
A) The Phase Diagram of Water
- ice (solid), water (liquid) and water vapour / steam (gas)
 Vapour Pressure Curve
- critical point = critical temperature (374˚C) and critical pressure (200 atmospheres)
- temperature above 374˚C and critical pressure 200 atmospheres, the vapour and liquid are
indistinguishable (no longer two separate phases) because the densities of the gas and liquid
are equal (meniscus separating a liquid from its vapour disappears).
 Melting Temperature Curve
- melting temperature point decrease with pressure- supercooling is the cooling of a liquid
to below its freezing point without a change taking place from the liquid to the solid state. A
phenomenon (metastable condition) shows the vapour pressure of water below its freezing
point.
 Triple Point
- Water triple point is at temperature 0.01˚C and pressure 0.006 atm (610 N m -2). All the
three phases (ice, water and water vapour) coexist at equilibrium.
 Normal Melting Temperature Point
- the temperature at which both the solid and the liquid states of the substance exist
in equilibrium at a pressure of 1 atm (101 kNm-2)
 Normal Freezing Temperature Point
- the temperature at which both the liquid and the solid states of the substance exist
Unsual Behaviour of Water
 i) Why ice can float?
- the volume of water increase when the change of phase from liquid to solid.
Reasons: Ice (solid) has an open structure (hydrogen bond).
 ii) Why the melting temperature curve slopes to the left (melting point decreases with
pressure)?
- (In most of substances (except water), an increase in pressure will push the molecules even
closer / Increase in pressure favours the physical state which is higher density)
Reasons: Increasing the pressure favours the formation of liquid water due to the latent
heat of fusion is absorbed from the surroundings during melting.
B) The Phase Diagram of Carbon Dioxide
- solid carbon dioxide (dry ice), liquid carbon dioxide and gas carbon dioxide
 Vapour Pressure Curve
critical point = critical temperature (374˚C) and critical pressure (217 atmospheres)
- temperature above 374˚C and critical pressure 217 atmospheres, the vapour and liquid are
indistinguishable because the densities of the gas and liquid are equal. At this point, carbon
dioxide gas can be liquefied.
 Melting Temperature Curve
- melting temperature point increase with pressure
- melting temperature curve slopes to the right
- density of dry ice (solid carbon dioxide) is higher than the density of liquid carbon dioxide.
It is because the carbon dioxide molecules are held closer together (smaller volume).
- Increasing the pressure favours the formation of solid carbon dioxide due to the latent heat
of fusion is liberated (given out) to the surroundings.
 Triple Point
- Carbon dioxide triple point is at temperature -57˚C and pressure 5.1 atm. All the three
phases (solid, liquid and gas) coexist at equilibrium.
 Normal Sublime Temperature Point
- the temperature at which both the solid and the gas states of the substance exist
- at atmospheric pressure, solid carbon dioxide (dry ice) sublimes to form carbon dioxide gas
at -78˚C.
Berry Important Points of Water Phase Diagram and Carbon Dioxide Phase Diagram
Water Carbon dioxide
Phase Diagram ice, water and water vapour solid carbon dioxide (dry
/ steam ice), liquid carbon dioxide
and gas carbon dioxide
Vapour Pressure Critical Point = 374˚C and Critical Point = 374˚C and
Curve 200 atmospheres 217 atmospheres
Triple Point 0.01˚C and 0.006 atm -57˚C and 5.1 atm
Melting Increasing the pressure Increasing the pressure
Temperature favours the formation of favours the formation of
Curve liquid water solid carbon dioxide
STPM Form 6 – Terminology and Concepts: Reaction Kinetics (Part 1)
Rate of reaction is the change of concentration of a reactant or a product per unit time (seconds /
minutes).
Rate of reaction = rate of increase of the concentration or amount of the product / Rate of
reaction = rate of decrease of the concentration or amount of the reactant.
Average rate is the change in concentration of a substance (reactant or product) over a fixed time
interval.
Instantaneous rate is the rate of the reaction at a specific time (the steeper the slope, the higher the
instantaneous rate).
Tangent is zero, the rate is zero / reaction has stopped.
Rate Equation or Rate Law is the rate of a reaction which is affected by the reactants concentration.
Rate = k [reactant]n , k is rate constant
STPM Chemistry Form 6 Notes – Reaction Kinetics (Part 2)
Nucleophile – Lewis bases / a species that attacks a positively-charged (electron deficient) carbon
atom by donating an electron-pair to form a dative covalent bond.
Electrophile – Lewis acids / a species that attacks a negatively-charged (electron rich) carbon atom
by accepting an electron-pair to form a dative covalent bond.
Important Notes in Organic Chemistry:
 If the concentration of the nucleophile influences the rate of the reaction which means the
rate determining step involves the nucleophile attacking the electrophile to form the
transition state that evolves into product (SN2 reaction mechanism = common in organic
chemistry).
 If the concentration of the nucleophile shows no effect on the rate of reaction, the reaction
is SN1 reaction mechanism.
 Both reaction mechanisms show a rate dependence on the electrophile concentration.
Reaction Order
 There are 3 reaction orders: zero, first and second.
 Zero order reaction proceeds at a constant rate, independent of reaction concentration.
 First order reaction depends only on one reactant (SN1 reaction).
 Second order reaction depends on two reactants (SN2 reaction).
 Zero order First order Second order
Rate law rate = k rate = k[A] rate = k[A]2
Half-life t1/2 = [A]o / 2k t1/2 = ln 2 / k t1/2 = 1 / k[A]o
Unit of rate mol dm-3 s-1 s-1 mol dm3 s-1

constant
Reaction Mechanisms
First order Second order Second order
The slowest step The slowest step The slowest step

involves one molecule involves two involves two molecules
breaking apart (its rate molecules forming a forming a bond (its
determining step). bond (its rate rate determining step).
determining step).
A –> B + C A + B –> C 2A –> B + C
One step One step One step

reactionDissociative reactionAssociative reactionAssociative
mechanism mechanism mechanism
Rate = k[A] Rate = k [A][B] Rate = k [A]2
Not all reactions are concerted. There are reactants that form intermediates (or activated
complexes) before the reactants form products and give a multi-step reaction.
Example 1
Reaction:
NO2(g) + CO(g) –> NO(g) + CO2(g)
Mechanism:
NO2(g) + NO2(g) –> NO(g) + NO3(g) (slow)
NO3(g) + CO(g) –> NO2(g) + CO2(g) (fast)
Which of the following options is the rate law for this reaction, assuming that this reaction
mechanism is correct?
A. k (PNO2) (PCO)
B. k (PNO2)2 (PCO)
C. k (PNO2)2
D. k (PNO2)
Answer: C
Solution: The slowest step in the reaction mechanism is the rate determining step. The rate depends
on the two molecules of NO2 gas and CO has no effect on the rate of this reaction which means the
addition of CO does not increase the rate of reaction.
STPM Chemistry Form 6 Notes – Reaction Kinetics (Part 3)
Collision Theory
 Reaction – reactants particle must collide with one another with sufficient energy to break
chemical bonds in the reactants to form product.
 Activated complex – a very high energetic and highly unstable species is formed.
 Chemical reaction – is the effective collisions of reactant particles.
 Reaction rate – is the measurement of the frequency of effective collisions.
 Activation energy (Ea) – minimum energy required to break the chemical bonds in the
reactant molecules and overcome the repulsion forces of the reactants molecules.
 Energy profile / Reaction profile – the difference in energy between the reactants and
activated complex.
The rate of a reaction is affected by
 temperature (reaction rate increases with increasing temperature)
 physical state of reactants (gas, liquid or solid)
 activation energy (reaction rate increases with increasing temperature)
 catalysts (reaction rate increases with positive catalysts and reaction rate decreases with
negative catalysts)
 solvent (solvents affect the transition state stability)
 collision frequency
 collision orientation
 the concentration of the reactants in the rate determining step
 effect of pressure
Example 1
Which of the following does NOT always affect the rate of reaction?
A. Changing the temperature
B. Adding a catalyst
C. Increasing the volume by adding solvent
D. Adding a reactant
Answer: D
Solution: Changing temperature changes the reaction rate. Adding a catalyst (usually positive
catalyst) lowers the activation energy which results increases the reaction rate. Increasing the
volume reduces the concentration of all reagents (include the reactants in the rate determining
step). Increasing volume of a gas phase reaction results in a decreased in reaction rate. Therefore, if
the reactant being added is not involved in the rate determining step, then it does not influence the
rate.
Rate Constant and Rate Law
Rate constant is determined by the Arrhenius constant (collision orientation and frequency take into
account)
k = A e –Ea/RT
where Ea is the activation energy, R is the molar gas constant, T is the absolute temperature and A is
the frequency factor.
ln k = ln A – (Ea/RT)
lg k = lg A – (Ea/2.303R) (1/T)
A plot of lg k against 1/T will be a linear graph with a slope of – (Ea/2.303R) and an intercept of lg A
First Order Reactions
The rate equation is
rate = k [A]
Example 2
Rate expression for the decomposition of N2O5,
rate = k [N2O5] or –d[N2O5]/dt = k [N2O5]1
Unit of k = mol dm-3 s-1 / mol dm-3 = s-1
ln [N2O5]t = ln [N2O5]0 – kt , where ln = natural logarithm
For the first-order reaction, a plot of ln [N2O5] against t will be linear with a slope of –k and an
intercept of ln [N2O5]0.
or
ln {[N2O5]0 / [N2O5]} = kt
For the first-order reaction, a plot of ln {[N2O5]0 / [N2O5]} against t will be straight line with a slope of
k and an intercept through the origin (0).
Second Order Reactions
rate = k [A]2 or rate = k [A] [B]
Example 3
2NO2(g) –> 2NO(g) + O2(g)
rate = k [NO2]2
Unit of k = mol dm3 s-1/ (mol dm3 s-1)2 = mol dm3 s-1
1/[N2O5]t = kt + 1/[ N2O5]0
For the second-order reaction, a plot of 1/[N2O5] against t will be a slope of k and an intercept of 1/[
N2O5]0
Zero Order Reaction
rate = k [A]0
Example 4
Thermal decomposition of hydrogen iodide on gold:
HI(g) –> ½ H2(g) + ½ I2(g)
rate = k [NO2]2
Unit of k = mol dm-3 s-1
[HI] = [HI]0 – kt
For the zero-order reaction, a plot of [HI] against t will be a straight line with a slope of –k and an
intercept of [HI]0
STPM Chemistry Form 6 Notes – Reaction Kinetics (Part 4 – Final)
Catalysis
 only small amount of catalyst is needed for the reaction
 catalysts lower the activation energy of the reaction
 catalysts speed up the rate of reactions and has no effect on the yield of a reaction
 catalysts are specific for one reaction
Homogeneous catalysis
 catalyst that exists in the same phase as the reactant
 an intermediate species is produced in the reaction
Example 1 (homogeneous catalyst in gas – NO)
Step 1: NO(g) + ½ O2(g) –> NO2(g) where NO2 is an intermediate compound
Step 2: NO2 (g) –> NO(g) + O (g) with sunlight
Step 3: O(g) + O2(g) –> O3(g)
Overall reaction / uncatalysed reaction: 3/2O2(g) –> O3(g)
Example 2 (homogeneous catalyst in aqueous solution – acid catalysis)
CH3COOCH3(aq) + H2O(l) –> CH3COOH(aq) + CH3OH(aq)
Example 3 (homogeneous catalyst in aqueous solution – Fe3+)
Step 1: 2Fe3+(aq) + 2I-(aq) –> 2Fe2+(aq) + I2(aq) where Fe2+ is an intermediate ion
Step 2: 2Fe2+(aq) + S2O82-(aq) –> 2Fe3+(aq) + 2SO42-(aq)
Overall reaction / uncatalysed reaction: S2O82-(aq) + 2I-(aq) –> 2SO42-(aq) + I2(aq)
Example 4 (homogeneous catalyst in aqueous solution – Br2)
Step 1: Br2(aq) + H2O2(aq) –> 2Br-(aq) + 2H+(aq) + O2(g)
Step 2: 2Br-(aq) + H2O2(aq) + 2H+(aq) –> Br2(aq) + 2H2O(l)
Overall equation / uncatalysed reaction: 2H2O2(aq) –> 2H2O(l) + O2(g)
Example 4 (homogeneous catalyst in aqueous solution – NaI)
Step 1: I-(aq) + H2O2(aq) –> IO-(aq) + H2O(l)
Step 2: IO-(aq) + H2O2(aq) –> I-(aq) + O2(g) + H2O(l)
Overall equation / uncatalysed reaction: 2H2O2(aq) –> 2H2O(l) + O2(g)
Heterogeneous catalysis
 catalyst that exists in a different phase from the reactant
 they are transition metals, the oxides of transition metals and the oxides of aluminium and
silicon
 adsorption process which involve formation of bonds between the reactant molecules and
the atoms on the surface (active sites) of the catalyst (solid metal)
 4 steps in heterogeneous catalysis: reactant molecules are adsorbed on the surface, reactant
molecules diffuse along the surface, reactant molecules react to form product molecules and
molecules of product desorb from the surface
Example 1 (heterogeneous catalyst – gold, Au)
Decomposition of N2O
N2O(g) –Au–> N2(g) + 1/2O2(g)
Example 2 (heterogeneous catalyst – nickel, Ni)
Hydrogenation of food oils or semisolid fats
CH3(CH2)7CH=CH(CH2)7COOH + H2 –Ni–> CH3(CH2)7CH2CH2(CH2)7COOH
Example 3 (heterogeneous catalyst – platinum metal mixed with rhodium)
Oxidation of carbon monoxide and unburned hydrocarbon such as benzene
2CO(g) + O2(g) –Pt–> 2CO2(g)
C6H6(l) + 15/2O2(g) –Pt–> 6CO2(g) + 3H2O(l)
2NO(g) –Rd–> N2(g) + O2(g)
Example 4 (heterogeneous catalyst – V2O5)
Contact process
2SO2(g) + O2(g) –V2O5–> 2SO3(g)
Example 5 (heterogeneous catalyst – Iron)
Haber process
N2(g) + 3H2(g) –Fe–> 2NH3(g)
Example 6 (heterogeneous catalyst – Platinum)
Ostwald process
4NH3(g) + 5O2(g) –Pt–> 4NO(g) + 6H2O(g)
Example 7 (heterogeneous catalyst – Nickel, Palladium, Platinum)
Hydrogenation of alkenes (manufacture of margarine)
CH2=CH2(g) + H2(g) –> CH3CH3(g)
Effect of temperature on reaction rates and rate constants
 Temperature increases causes the reaction rates increase
 Reaction rate is doubled for every 10˚C rise in temperature
Kinetics Theory
 Kinetic theory = mv2/2
 Raising the temperature greatly increases the fraction of molecules having very high
velocity and high kinetics energy.
 Most molecules are likely to collide to react
 Increase in the frequency of collision, this causes the fraction of effective collision increases
(kinetic energy equal to or greater than the activation energy, Ea).
Arrhenius equation,
 k = A e –Ea/RT
 In natural logarithm, ln k = ln A – (Ea/RT)
 The graph of ln k versus (1/T) should be linear and the slope of straight line is -(Ea/R)
Clausius-Clapeyron equation (two different temperatures, T2 and T1)
 In natural logarithm, ln k2 – ln k1 = – (Ea/R) [(1/T2) – (1/T1)]
 ln (k2/k1) = (Ea/R) [(1/T2) – (1/T1)]
STPM Form 6 – Terminology and Concepts: Chemical Equilibrium (Part 1)
1) Reversible Reaction
 Chemical reaction is in both directions.
 Forward reaction: from left to right.
 Reverse reaction: from right to left.
 React in a closed container.
 Reversible reaction is never complete (a mixture of reactants and products).
 An intermediate position (equilibrium) is reached.
2. Dynamic Equilibrium
 Reversible reaction is at a position of dynamic equilibrium.
- the rate of the forward reaction = rate of the reverse reaction.
- no change is observed (concentrations of the reactants and the products remain
unchanged.)
- all the external conditions remain unchanged (closed container).
3. The Equilibrium Law and the Equilibrium Constant
 Equilibrium expression / equilibrium equation,
 Kc = [product]x / [reactant]y
 Forward reaction:
 aA + bB <—-> cC + dD
Equilibrium expression / equilibrium equation,
Kc = [C]c[D]d / [A]a[B]b
where
[A] = concentration of A
[B] = concentration of B
[C] = concentration of C
[D] = concentration of D
Kc = equilibrium constant for the reaction (in terms of concentration of the reactant) and the
units depend on the chemical equation.
 Reverse reaction:
cC + dD <—-> aA + bB
Equilibrium expression / equilibrium equation
The equilibrium constant, Kc‘ = [A]a[B]b / [C]c[D]d
 This relationship is equilibrium law / equilibrium expression where:
Equilibrium constant of the reverse reaction is the reciprocal of the equilibrium constant of
the forward reaction, Kc‘ = 1 / Kc
 Equilibrium constant is constant at a particular temperature.
- Exothermic reaction (forward reaction), the value of the equilibrium constant decreases as
temperature increases.
- Endothermic reaction (forward reaction), the value of the equilibrium constant increases as
temperature increases.
 Reaction quotients, Q (predicting the direction of reaction)
Q = Kc, no net reaction will take place (the system is at equilibrium).
Q < Kc, a net forward reaction to the right occurs.
(If the value Kc (equilibrium constant) is very large, the equilibrium position lies very much to
the right and the yield of the products are higher than the reactants.
Q > Kc, a net reverse reaction to the left occurs.
(If the value Kc (equilibrium constant) is very small, the equilibrium position lies more to the
left and the the yield of the products are lower than the reactants.
STPM Form 6 – Terminology and Concepts: Chemical Equilibrium (Part 2)
1. Equilibrium Constant (in terms of partial pressure), Kp
 Kp can only be applied to gas reactions.
 Kc and Kp are not numerically equal.
 The total number of moles (in a gas reaction) is the same.
Example: aA(g) + bB(g) <—-> cC(g) + dD(g)
 The equilibrium constant (in term of partial pressure), Kp
Kp = (PC)c (PD)d / (PA)a (PB)b
 The equilibrium constant (in term of concentration), Kc
Kc = [C]c[D]d / [A]a[B]b
 Kp = Kc
Example: 2HI(g) <–> H2(g) + I2(g)
 The equilibrium constant (in term of partial pressure), Kp
Kp = (PH2) (PI2) / (PHI)2
2. Homogeneous Equilibrium
 All substances are in the same physical states (all gases or all liquids).
Example: N2(g) + 3H2(g) <–> 2NH3(g)
Kp = (PNH3)2 / (PN2) (PH2)3
3. Heterogeneous Equilibrium
 The substances are in different physical states (a mixture of solids, liquids or gases)
Example: CaCO3(s) <–> CaO(s) + CO2(g)
Kp = PCO2
* The concentrations of solids and pure liquids are constants. In the expressions for Kc and Kp, solids
and pure liquids are left out.
STPM Chemistry Form 6 Notes – Chemical Equilibrium (Part 3)
Le Chatelier’s Principle: more (or less) product
 change the concentration of a reactant or product
 change the temperature
 change the pressure on a system that contains gases
A) The effect of concentration on equilibrium
 Add more of a reactant or product to an equilibrium system, the reaction will shift to the
other side to use it up.
 Remove any of a reactant or product in an equilibrium system, the reaction will shift to the
other side to replace it.
Example:
Haber process: N2(g) + 3H2(g) <—-> 2NH3(g) ΔH = – 92.2 kJ
Add nitrogen gas (increase the concentration of nitrogen gas), equilibrium is reestablish and reaction
shifts to the right (forward reaction occurs / shifts from left to right) which forming more ammonia
(product).
B) The effect of temperature:
i) On the position of equilibrium
 Increase the temperature (heating a reaction) causes an equilibrium to shift to the
endothermic (heat adsorbing)
 Decrease the temperature (cooling a reaction) causes an equilibrium to shift to the
exothermic (heat releasing)
Example:
Heat the reaction (increase the temperature of the reaction), equilibrium is reestablish and reaction
shifts to the left (reverse reaction occurs / shifts from right to left) which forming more nitrogen gas
and hydrogen gas (reactants)
ii) On the position of equilibrium constant
 Van’t Hoff equation: ln K = – (ΔH/RT) + C where K is equilibrium constant, ΔH is the heat of
forward reaction, R is gas constant (8.31 J mol-1 K-1 and C is a constant of the particular
reaction.
 Van’t Hoff equation: ln K2/K1 = (ΔH/R)(1/T1 – 1/T2)
 Endothermic reaction, ΔH is positive
 Exothermic reaction, ΔH is negative
C) The effect of pressure on equilibrium that contains gases
 Reactant and/or product must be gases
 Increase the pressure on an equilibrium causes the reaction to shift to the other side
containing the fewest number of gas molecules.
Example:
Increase the pressure (by making the container smaller or by putting in non-reactive gas),
equilibrium is reestablish and reaction shifts to the right (forward reaction occurs / shifts from left to
right) which forming more ammonia (product) – reduce the number of gas molecules in the
container.
Chemical Kinetics
Chemical kinetics is a way to change reaction speeds.
There are 6 factors that affecting the speed of a reaction (same in Reaction Kinetics)
 A) Complexity of the reactants – reactants which are large and complex molecules will need
to take longer time for the molecule to react in a reaction. They may be a lot of collision
occur but only the collision at the reactive site leads to chemical reaction. Sometimes the
reactive site in a molecule is totally block off, as the result no chemical reaction occurs.
 B) Particle size of the reactants – the greater the total surface area, the higher the reaction
rate.
 C) Concentration of the reactants – the more reactant molecules collide, the higher reaction
rate.
 D) Pressure of gaseous reactants – the higher the reactant pressure, the higher the reaction
rate because the increased number of collisions.
 E) Temperature – 10˚C increase in temperature, the reaction rate is doubled.
 F) Catalysts – with catalysts increase the reaction rate by lowering the reaction’s activation
energy
STPM Chemistry Form 6 Notes – Chemical Equilibrium (Part 4 – Final)
Factors affecting the rate of reaction, rate constant, equilibrium constant and composition of
equilibrium mixture
Factor Rate of Rate Equilibrium Composition of

reaction constant (k) constant (Kc, Kp) equilibrium
mixture
Increase in ↑ ↑ Endothermic:↑ Endothermic:

temperature Exothermic: ↓ Yield of the
product↑
Exothermic:
Yield of the
reactant↑
Decrease in ↓ ↓ Endothermic:↓ Exothermic:

temperature Exothermic: ↑ Yield of the
product↑
Endothermic:
Yield of the
reactant↑
Increase in ↑ X X
pressure
Decrease in ↓ X X
pressure
Catalyst ↑ ↑ X X
Note: ↑ increases & ↓ decreases

Perturbations and Shifts
Applied Stress System’s adjustment Direction of shift
Add reactant Remove reactant To the right
Add product Remove product To the left
Decrease volume Decrease gas volume To the side with fewer

molecules
Increase volume Increase gas volume To the side with more

molecules
Decrease React to generate heat To the exothermic direction

temperature
Increase React to absorb heat To the endothermic direction

temperature
STPM Chemistry Form 6 Notes – Ionic Equilibrium (Part 1)
Natural Universal Indicator: Purple cabbage
The Brønsted-Lowry Acid-Base Theory

An acid is a proton (H+) donor
A base is a proton (H+) acceptor
Strong and Weak Acids and Bases

 Strength (strong or weak) – amount of ionisation / dissociation of a particular acid or base.
 Concentration – amount of acid or base
I) Common strong acids
 hydrochloric acid (HCl)
 hydrobromic acid (HBr)
 hydroiodic acid (HI)
 nitric acid (HNO3)
 perchloric acid (HClO4)
 sulphuric acid (H2SO4)
Example: Hydrogen chloride gas dissociate (break) completely in water.
HCl + H2O –> Cl- + H3O+
 H3O+ ion is hydronium ion
 All the HCl ionises completely (≈ 100%) to H3O+ and Cl-
 HCl is a strong acid
 Water acts as a base by accepting the proton from the hydrogen chloride
Calculating ion concentration in solution
Example: Initial concentration of HCl 0.15 mol dm-3 = 0.15 moles of HCl gas bubble into a 1 dm3of
water.
[HCl] = 0.15 because HCl ionises completely in water.
[H3O+] = 0.15 and [Cl-] = 0.15
II) Common strong bases

 sodium hydroxide (NaOH)
 potassium hydroxide (KOH)
 barium hydroxide (Ba(OH)2)
 Caesium hydroxide (CsOH)
 Strontium hydroxide (Sr(OH)2)
 Calcium hydroxide (Ca(OH)2)
 Lithium hydroxide (LiOH)
Example: Sodium hydroxide (a salt) dissociates (break) completely in water.
NaOH –> Na+ + OH-
 All the NaOH dissociates completely (≈ 100%) to Na+ + OH-
 NaOH is a strong base
 Water acts as a acid by donating the proton to sodium hydroxide
Example: Initial concentration of NaOH 0.25 mol dm-3 = 0.25 moles of NaOH into a 1 dm3 of water.
[NaOH] = 0.25 because NaOH ionises completely in water.
[Na+] = 0.25 and [OH-] = 0.25
III) Common weak acids
 ethanoic acid / acetic acid (CH3COOH)
 fluoroacetic acid (C2H3FO2)
 formic acid (HCHO2)
 phosphori(V) acid (H3PO4)
 boric acid (H3BO3)
Example: Ethanoic acid partially ionises in water.
CH3COOH(aq) + H2O(l) <—-> CH3COO- + H3O+
 About 5% of the ethanoic acid ionises and 95% remains in the molecular form
 Ethanoic acid is a weak acid
 Water acts as a base by accepting the proton from the ethanoic acid
Example: Ka expression for the weak acid is
Ka = ([H3O+] [CH3COO-]) / [CH3COOH] = 1.8 x 10-5
[CH3COOH] = molar concentration of CH3COOH at equilibrium not initially.
[H2O] does not appear in Ka expression because it is a constant.
[H3O+] = [CH3COO-] = α
* CH3COOH ionises partially to form hydronium ion and acetate ion, so the amount of ethanoic acid
remaining at equilibrium as the initial amount, 2.0 M, minus the amount that ionises, α.
* α is very small, so that 2.0 – α is approximately equal to 2.0 = equilibrium concentration of the
weak acid with its initial concentration.
[CH3COOH] [CH3COO-] [H3O+]
Initial (M) 2.0 0 0
Equilibrium 2.0 – α 2.0 (α) 2.0 (α)

(M)
Ka = 1.8 x 10-5 = ([α] [α]) / [2.0] = [α]2 / [2.0]

[α]2 = (1.8 x 10-5) [2.0]
[H3O+] = [CH3COO-] = α = 6.0 x 10-3
IV) Common weak bases

 ethylamine (CH3CH2NH2)
 Ammonium hydroxide / ammonia water (NH4OH)
 Ammonia (NH3)
Example: Ammonia partially ionises in water.
NH3(g) + H2O(l) <—-> NH4+ + OH-
 About 5% of the ammonia ionises and 95% remains in the molecular form
 Ammonia is a weak base
 Water acts as a acid by donating the proton from the ammonia
Example: Kb expression for the weak base is
Kb = ([OH-] [NH4+]) / [NH3] = 1.8 x 10-5
[NH3] = molar concentration of NH3 at equilibrium not initially.
[H2O] does not appear in Kb expression because it is a constant.
[NH4+] = [OH-] = β
* NH3 ionises partially to form hydroxide ion and ammonium ion, so the amount of ammonia
remaining at equilibrium as the initial amount, 2.0 M, minus the amount that ionises, β.
* β is very small, so that 2.0 – β is approximately equal to 2.0 = equilibrium concentration of the
weak base with its initial concentration.
[NH3] [NH4+] [OH-]
Initial (M) 2.0 0 0
Equilibrium 2.0 – β 2.0 (β) 2.0 (β)

(M)
Kb = 1.8 x 10-5 = ([β] [β]) / [2.0] = [β]2 / [2.0]

[β]2 = (1.8 x 10-5) [2.0]
[OH-] = [NH4+] = β = 6.0 x 10-3
Ostwald Dilution Law

Ka = (cα)(cα) / c(1-α) = α2c / (1-α)
[H3O+] = √(Ka x c)
Kb = (cβ)(cβ) / c(1-β) = β2c / (1-β)
[OH-] = √(Kb x c)
Arrhenius Theory: Svante Arrhenius (1884), Sweden
 An Arrhenius acid is substances dissociate in water to produce H+ ions
 An Arrhenius base is substances dissociate in water to produce OH- ions
Example:
HCl(aq) –> H+(aq) + Cl-(aq)
CH3COOH(aq) <—-> CH3COO-(aq) + H+(aq)
 HCl and CH3COOH are Arrhenius acids
Example:
NaOH(aq) –> Na+(aq) + OH-(aq)
Ba(OH)2(aq) –> Ba2+(aq) + 2OH-(aq)
 NaOH and Ba(OH)2 are Arrhenius bases
Limitation: Many compound show basic properties but do not contain OH-
Example: NH3, Na2CO3 and C2H5ONa
The Brønsted-Lowry Acid-Base Theory: Johannes Brønsted (1879-1947), Denmark and Thomas
Lowry (1874-1936), England
 A Brønsted-Lowry acid is a proton (H+) donor
 A Brønsted-Lowry base is a proton (H+) acceptor
 In an acid-base reaction, a proton is transferred from an acid to a base
Brønsted-Lowry acid-base reaction:
HB(aq) + A-(aq) <—-> HA(aq) + B-(aq)
 HB and HA act as Brønsted-Lowry acid
 A- and B- act as Brønsted-Lowry base
Conjugate base is the species formed when a proton is removed from an acid
Conjugate acid is the species formed when a proton is added to a base
 B- is the conjugate base of HB
 HA is the conjugate acid of A-
Conjugate acid-base pair differs only in the presence or absence of a proton, H+
Example:
Conjugate acid Conjugate base
NH4+ NH3
HSO4- SO42-
HF F-
Amphiprotic is a species that can either accept or donate a proton.

Example: H2O molecule
Hydronium ion (H3O+) – H2O molecule gain a proton
Hydroxide ion (OH-) – H2O molecule lose a proton
Lewis Theory: G.N. Lewis (1938), America

 A Lewis acid is a species (an atom, ion or molecule) form a dative covalent bond
by acceptingan electron-pair from base
 A Lewis base is a species form a dative covalent bond by donating an unshared electron-
pair with an atom, ion or molecule
Example 1:
B(OH)3(aq) + H2O(l) <—-> B(OH)4-(aq) + H+(aq)
 Lewis acid: Boric acid (H3BO3)
 Lewis base: Water (H2O)
Example 2:
BF3 + NH3 –> BF3•NH3
 Lewis acid: BF3
 Lewis base: NH3
Example 3:
Cu2+(aq) + 4NH3(aq) –> [Cu(NH3)4]2+(aq)
 Lewis acid: Cu2+
 Lewis base: NH3
Example 4:
Ni(s) + 4CO(g) <—-> Ni(CO)4(l)
 Lewis acid: Ni
 Lewis base: CO
Water-based Acid-Base Chemistry
2H2O(l) <—-> H3O+(aq) + OH-(aq)
 water is amphoteric that may act as either an acid or base
 neutral water naturally dissociates into hydronium and hydroxide
 only small fraction of water dissociates into solution
 at 25˚C (in the absence of an acid or base), water dissociates enough to generate a solution
with 10-7M H3O+ and 10-7M OH-
 a neutral aqueous solution, [H3O+ ] = [OH- ]
 pH = pOH = 7.0
Acid Dissociation
HA(aq) + H2O(l) <—-> H3O+(aq) + A-(aq)
 Ka = acid dissociation constant
 Ka = ([H3O+ ] [A- ]) / [HA]
 Each molecule of an acid when added to water, dissociates to form hydronium ion (H3O+)
and its conjugate base upon reaction with one water molecule.
 pKa = -lg Ka
 Ka = 10-pKa
 strength of an acid increases (↑), its Ka (↑) and its pKa (↓)
 it means that stronger acid have higher Ka values and lower pKa values
 Ka and pKa of an acid depend on the strength of the acid, but not its concentration
Base Hydrolysis
A-(aq) + H2O(l) <—-> OH-(aq) + HA(aq)
 Kb = base hydrolysis constant
 Kb = ([OH- ] [HA]) / [A- ]
 Each molecule of a base when added to water, hydrolyses to form hydroxide ion (OH- ) and
its conjugate acid upon reaction with one water molecule.
 pKb = -lg Kb
 Kb = 10-pKb
 strength of a base increases (↑), its Kb (↑) and its pKb decreases (↓)
 it means that stronger base have higher Kb values and lower pKb values
 Kb and pKb of a base depend on the strength of the base, but not its concentration
Overall Relationship
Acid Ka pKa Conjugate Kb pKb
strength base strength
↑ ↑ ↓ ↓ ↓ ↑
Determination of Reagent Strength
pKa(HA) + pKb(A-) = 14
 strength of a reagent is determined strictly from Ka (or pKa) and Kb (or pKb) is a measure of
the completeness of a reaction in water
 dissociation = ionisation = electrolytic nature
 the stronger an acid = the more readily the acid dissociates into water
 the stronger a base = the more readily the base hydrolysis into water
(*Notes: Not to confuse the concentration of a reactant with its strength (a highly concentrated
weak acid may have a lower pH than a strong acid in low concentration.)
Strong acids
HX(aq) + H2O(l) <—-> H3O+(aq) + X-(aq)
 strong acids are acids that dissociate fully when mixed with water
 strong acids ionise completely into hydronium ion and a conjugate base when added to
water
 reactants convert completely into products, so the Ka value of a strong acid is very large
 the equilibrium constant for the acid dissociation reaction has a large numerator and a
minuscule denominator
 Ka = ([H3O+] [X-]) / [HX] >> 1
 pKa < 0
 all the strong acids can be classified as either haloacids or oxyacids
Example:
Acid Name pKa
HCl Hydrochloric acid -7
HBr Hydrobromo acid -7
HI Hydroiodic acid -9
H2SO4 Sulfuric acid -9
HNO3 Nitric acid -2
HClO4 Perchloric acid -10
Weak acids
HX(aq) + H2O(l) <—-> H3O+(aq) + X-(aq)
 weak acids are acids that only dissociate partially when dissolved into water
 weak acids do not fully ionize into hydronium ion and conjugate base when added to water
 Ka = ([H3O+] [X-]) / [HX] where 1 > Ka > 10-14
 0 < pKa < 14
 Weak acids can be classified in a number of different classification as oxyacids of low
oxidation state, one haloacid, carboxylic acids, alkyl ammoniums, and phenol
Example:
Acid Name pKa
H2SO3 Sulfurous acid 1.82
HClO2 Chlorous acid 1.90
HF Hydrofluoric acid 3.15
HNO2 Nitrous acid 3.41
HCO2H Formic acid 3.74
H3CCO2H Acetic acid 4.74
H2CO3 Carbonic acid 6.36
HClO Hypochlorous acid 7.46
HBrO Hypobromous acid 8.72
NH4+ Ammonium 9.26
HCN Hydrogen cyanide 9.32
HIO Hypoiodous acid 10.66
Very weak acids

HX(aq) + H2O(l) <—-> H3O+(aq) + X-(aq)
 very weak acid dissociates less than water (Kw = 1.0 x 10-14)
 Ka = ([H3O+] [X-]) / [HX] where Ka < 10-14
 pKa > 14
Strong bases
MOH(s) + H2O(l) <—-> M+(aq) + OH-(aq)
 strong bases react completely when mixed with water
 strong bases fully hydrolyse water and completely ionize when added water
 Kb = ([M+ ] [OH- ]) / [MOH] >> 1
 pKb < 0
 all the strong bases can be classified as either hydrides, hydroxides, alkoxides, amines or
carbides
Example:
Base Name pKb
LiOH Lithium hydroxide -0.36
Ba(OH)2 Barium hydroxide -2.02
Sr(OH)2 Strontium hydroxide -2.19
Weak bases
A-(aq) + H2O(l) <—-> HA(aq) + OH-(aq)
 weak bases are bases that only react partially when dissolved into water
 weak bases partially hydrolyse water
 weak bases do not fully ionise into when added to water
 Kb = ([HA] [OH- ]) / [A- ] where 10-14 < Kb < 1
 0 < pKb < 14
 weak bases are the conjugate bases of the acids
 common weak bases: carboxylates (RCOO- ), alkyl amines (RNH2), bicarbonate (HCO3- ),
carbonate (CO32- ), phosphate (PO43- ) and phonoxides (C6H5O- )
Example:
Base Name pKb
BeOH Beryllium hydroxide 10.30
C6H5NH2 Aniline 9.4
NH3 Ammonia 4.75
CH3NH2 Methylamine 3.36
Zn(OH)2 Zinc Hydroxide 3.02
Ca(OH)2 Calcium hydroxide 2.37

CsOH Caesium hydroxide 1.76
KOH Potassium hydroxide 0.5
NaOH Sodium hydroxide 0.2
Very weak bases

A-(aq) + H2O(l) <—-> HA(aq) + OH-(aq)
 very weak bases ionise less than water (Kw = 1.0 x 10-14)
 Kb = ([HA] [OH- ]) / [A- ] where Kb < 10-14
 pKb > 14
Relationship between the strength and the pK scale
 strength of the reagent is measured by its ability to react in water
 strong acids are more readily to dissociated in water (do not confuse the concentration of a
reactant with its strength)
 strong acids have very weak conjugate bases
 strong bases have very weak conjugate acids
These are some shortnotes for the previous ionic equilibrium studynotes
Summary – Strong acids / Very weak bases
Compound Ka / pKa Conjugate Kb / pKb
Strong acid - Very weak base -
HCl Ka >> 1 Cl- Kb < 10-14
(pKa = -7) pKa < 0 (pKb = 21) pKb > 14
Summary – Weak acids / Weak bases
Weak acid - Very weak base -
RCOOH 10-14 < Ka < 1 RCOO- 10-14 < Kb < 1
(pKa = 3–5) 0 < pKa < 14 (pKb = 9-11) 0 < pKb < 14
Summary – Very weak acids / Strong bases
Very weak acid - Strong base -
CH4 Ka < 10-14 CH3- Kb >> 1
(pKa = 49) pKa > 14 (pKb = -35) pKb < 0

Ionic product, Kw of water
H2O(l) <—-> H+(aq) + OH-(aq)
 Kc = ([H+] [OH- ]) / [H2O]
 Kw = [H+] [OH- ] where Kw = Kc [H2O]
 In pure water at 25˚C, [H+] = [OH- ] = 10-7 mol dm-3
 Ka (acid) x Kb (conjugate base) = 10-14 at 25˚C
 pKa + pKb = 14.0 = pKw
pH scale
 pH = -lg [H3O+] or pH = -lg [H+]
 pOH = -lg [OH- ]
 pH + pOH = 14.0
 pH = 14.0 + lg [OH- ]
 pH = 14.0 – pOH
pH values of pure water [H3O+] = 1.0 x 10-7 mol dm-3
 pH = -lg [H3O+] or pH = -lg [H+]
 pH = -lg (1.0 x 10-7)
 pH = – (-7.0)
 pH = 7.0
pH values of strong acids of 1.0 mol dm-3 (example: HCl)
 pH = -lg [H3O+] or pH = -lg [H+]
 pH = -lg 1.0 = 0.0
pH values of strong bases of 1.0 mol dm-3
 pOH = -lg [OH- ]
 pOH = -lg 1.0 = 0.0
 pH = 14.0 – pOH
 pH = 14.0 – 0.0 = 14.0
pH values of weak acids of 0.15 mol dm-3 (Ka for the acid at 25˚C is 5.80 x 10-10 mol dm-3) (example:
HCN)
 for weak acid, [H+] = √(Ka x c) or [H3O+] = √(Ka x c)
 for weak acid [H3O+] = √(5.80 x 10-10 x 0.15)
 [H3O+] = 9.33 x 10-6 mol dm-3
 pH = – lg (9.33 x 10-6)
 pH = 5.03
pH values of weak bases of 0.15 mol dm-3 (Kb for the base at 25˚C is 7.30 x 10-10 mol dm-3)
 for weak base, [OH- ] = √(Kb x c)
 for weak base [OH- ] = √(7.30 x 10-10 x 0.15)
 [OH-] = 1.05 x 10-5 mol dm-3
 pOH = – lg (1.05 x 10-5)
 pOH = 4.98
 pH = 14.00 – 4.98
 pH = 9.02
Bonus: One final question to ask yourself as added bonus. Does the pH of water remain the same at
7.0 for all temperatures? For those that answer yes, you are wrong. At high temperature such as
100˚C, the pH value is 6.14. So water is acidic at 100˚C? If you answer yes to that question, you are
wrong again. It is just that the neutral point has shift to 6.14 for that temperature. While this might
not come out in your exams, but it is always good to know to have a better understanding of the
concept.
Conjugate pairs
 consists of an acid and a base that exchange one proton
 acid – deprotonated forms its conjugate base
 base – protonated forms its conjugate acid
Example:
The conjugate base of HCO3- is which of the following?
A H2CO3
B CO32-
C CO2
D HCO2-
Solution: Conjugate base is formed when an acid loses one proton (eliminate option A = conjugate
acid of HCO3-).
Dissociation reaction of bicarbonate into hydronium and carbonate:
HCO3-(aq) + H2O(l) <—-> H3O+(aq) + CO32-(aq)
Answer: B CO32-
Typical conjugate pairs
 Conjugate pair favours the conjugate acid form in the presence of hydronium (H3O+).
 Conjugate pair favours the conjugate base form in the presence of hydroxide (OH- ).
 If pH (solution) > pKa (conjugate acid), the solution is basic relative to the compound, so it is
deprotanated.
 If pH (solution) < pKa (conjugate acid), the solution is acidic relative to the compound, so it is
protonated.
Example of common conjugate pairs:
 carboxylic acids / carboxylates (RCOOH / RCOO- )
 alkyl ammoniums / alkyl amines (RNH3+ / RNH2)
 phenols / phenoxides (C6H5OH / C6H5O- )
Example of specific pairs:
 carbonic acid / bicarbonate (H2CO3 / HCO3- )
 phosphoric acid / dihydrogen phosphate (H3PO4 / H2PO4- )
Physiological compounds and their natural states
 pH refers to the surrounding solution (environment) in which the compound exist
 pKa refers to the conjugate acid that exists in solution
 compound responds to the pH of the solution
Acid Conjugate Base
RCOOH / pKa = 3 – 5 RCOO- / pKb = 9 – 11
RNH3+ / pKa = 9 -10 RNH2 / pKb = 4 – 5
Relationship of pKa and pKb

 an acid when deprotonated forms its conjugate base
 a base when protonated forms its conjugate acid
 Ka x Kb = 10-14
Example:
What is the pKa for ammonia, given that the pKb for ammonia is 4.7?
A 33
B 9.3
C 7.0
D 4.7
Solution:
 the answer is not B 9.3! The compound with a pKa of 9.3 is ammonium (NH4+) – the
conjugate acid of ammonia
 ammonia is a weaker acid than ammonium, so it has a pKa greater than 9.3
 pKa (HA) + pKb (A- ) = 14 is for conjugate pairs, not for the same compound.
Answer: A 33
Titration curves
 quantitative reactions
 acid-base titration – quantitative addition of a titrate acid to a base in solution (or of a titrate
base to an acid in solution
 equivalence point – when the moles of acid (H3O+) are equal to the moles of titrate base
(OH-)
 end point of an acid-base titration – the point at which the indicator changes colour
Two versions of titration
Version 1: titration of a strong reagent by a strong reagent.
Example: strong acid by strong base / strong base by strong acid
Point of curve Species in pH range pH calculation (Extra notes)

solution
Initial Pure strong pH << 7 pH = -lg[HX]initial

acid
Before H3O+ pH < 7 pH = -lg[H3O+]

equivalence
At equivalence H2O & salt pH = 7 pH = 7
Past OH- pH > 7 pOH = -lg[OH-]excess

equivalence
Version 2: titration of a weak reagent by strong reagent.

Example: weak acid by strong base / weak base by strong acid
Point of curve Species in pH range pH calculation (Extra notes)

solution
Initial Pure weak pH < 7 pH = ½ pKa – ½ lg[HA]

acid
Before HA and A- pKa ± 1 pH = pKa + lg ([A- ] / [HA])

equivalence (Buffer)
At equivalence A- (diluted) pH > 7 pOH = ½ pKb – ½ lg[A- ]
Past OH- pH > 7 pOH = -lg[OH- ]excess

equivalence
(there is no titration of a weak reagent with a weak reagent – two weak reagent do not react with
one another)
Important point in curve shapes
Case 1: titration of a strong acid by a strong base / titration of a strong base by a strong acid.
 the shape of the curve – sigmoidal
 equivalence point is at pH = 7.0 (product is neutral salt and water)
 pH is measured on a log scale
 each change of 1.0 in the pH requires ten times less titrate. Example: pH = 1 to pH = 2, the
hydronium concentration goes from 0.10M to 0.01M, a change of 0.09M H3O+
Example of sigmoid
Case 2: titration of a weak acid by a strong base / titration of a weak base by a strong acid
 titration curves exhibit an initial cusp when the reagent being titrated is weak (a lip-o-
weakness)
 pH at half-equivalence point = pKa
 titration of a weak acid by a strong base, the equivalence pH > 7.0 (because the neutralised
product is a weak base / the conjugate base of the weak acid)
 titration of a weak base by a strong acid, the equivalence pH < 7.0 (because the neutralised
product is a weak acid / the conjugate acid of the weak base)
Three types of titration curves
1. concentration effect on titration curve shape
2. strength effect on titration shape
3. polyprotic acid titration curve
Indicators
 an organic compound with extended conjugation
 weak acid (protonated) form and conjugate weak base (deprotonated)
 form two distinct colour
 when the pH of the solution is less than the pKa of the indicator (pH solution < pKa (indicator),
Indicator pH range Colour Colour

change (acid) change
(alkali)
Litmus 4.5-8.3 red blue
Phenolphthalein 8.3-10.0 colourless fuchsia

(pink)
Methyl orange 3.1-4.4 red orange
Methyl red 4.4-6.2 red yellow
Bromothymol blue 6.0-7.6 yellow blue
HIn(aq) + H2O(l) <—-> H3O+(aq) + In-(aq)

HIn = acid (colour A)
In- = conjugate base (colour B)
Case 1:
Environment: < pH values (concentration H3O+ is high)
Le Chatelier’s principle: Equilibrium shifts to the left
Colour: A
Case 2:
Environment: > pH values (concentration H3O+ is low)
Le Chatelier’s principle: Equilibrium shifts to the right
Colour: B
Case 3:
Environment: [HIn] = [In-]
Colour: Intermediate colour
KHIn = ([H3O+] [In]) / [HIn]
KHIn = indicator dissociation constant
Choosing an indicator
I) Strong acid – Strong base Titration
 pH range from 3.5 to 10.5
 Suitable indicator: Phenolphthalein, methyl red, bromothymol blue)
II) Strong acid – Weak base Titration
 Suitable indicator: Methyl orange
III) Weak acid – Strong base Titration
 Suitable indicator: Phenolphthalein
IV) Weak acid – Weak base Titration
 pH range has no sharp
 Suitable indicator: no indicator
V) Weak Polyprotic Acids
 There are few equivalence points
 First equivalence point = pH range at 4.6
 Suitable indicator: Methyl orange, Methyl red
 Second equivalence point = pH range at 9.0
 Suitable indicator: Phenolphthalein
Natural acid-base indicator
Anthocyanin (red in acidic solutions and blue in basic)
 red cabbage leaves
 rose petals
 skin of a lemon
 berries
 hydrangea
[Bonus: it is important to understand that the pH range stated might shift very slightly depending on
the indicator's concentration level in the solution and also the temperature of the solution. So take
special note when you run experiments involving indicators.]
Biology Buffer
Diet Cola is fairly acidic. If you consumed 12 can of diet cola, you might be expected that pH in your
body would become lower than normal neutral condition and you might be dying. But surprisingly,
in our body blood which is a buffer that can resist changes in pH.
Case 1:
HCl + NaCH3COO –> NaCl + CH3COOH
Buffer solution containing:
 Weak acid = acetic acid
 Conjugate base = sodium acetate
When we add hydrochloric acid (strong acid) to this solution, hydrochloric acid will be converted into
a weak acid, CH3COOH.
Therefore, the overall pH of the solution relatively constant / pH value change only very slightly.
Case 2:
NaOH + CH3COOH –> NaCH3COO + H2O
Buffer solution containing:
 Weak acid = acetic acid
 Conjugate base = sodium acetate
When we add sodium hydroxide (strong base) to this solution, sodium hydroxide will be converted
into a weak base, NaCH3COO.
Therefore, the overall pH of the solution relatively constant / pH value change only very slightly.
Henderson-Hasselbalch equation
 pH = – log10 Ka + log10 ([base] / [acid])
 pH = pKa + log10 ([A-] / [HA])
 pH = pKa + log10 ([Moles conjugate base] / [Moles conjugate acid])
This equation is used to :
 determine the pH of a buffered solution.
 it shows that as [conjugate acid] increases, buffer pH decreases.
 it also indicates that if the pH is greater than the pKa, the solution is rich in conjugate base.
Example:
If water is added to a buffer solution with pH = 3.96. What happen to the pH?
A The pH remains the same
B The pH increases slightly
C The pH decreases slightly
D If the pH is greater than 7, then it decreases. If the pH is less than 7, then it increases.
Solution:
 Addition of water to a buffer solution equally dilutes the concentration of the weak acid and
its conjugate base.
 This means that the mole ratio of the weak base to the weak acid does not change upon the
addition of water.
 According to the Henderson-Hasselbalch equation, the pH of the solution does not
change because pKa is constant and the fraction has not changed.
 Therefore, the pH of the buffer does not change when it is diluted.
Answer: A
Buffers
 buffer is a solution where pH remain relatively constant / pH value change only very slightly
after the addition of small amount of either strong acid or strong base
 buffer are made of roughly equal mole mixture of a weak acid and its weak conjugate
base in an aqueous solution.
Example:
Explain why a solution containing a strong base and its salt does not act as a buffer solution?
Solution: Addition of OH- does not shift an equilibrium toward un-ionised base, as it would with a
weak base and its conjugate.
Buffer Recipes
 buffer can be made either by mixing the conjugate pair together or
 buffer can be made by partially titrating either component in a conjugate pair of weak
reagents.
Case 1:
Half-titrate the weak acid with strong base
(Tips: a weak acid must be chosen with a pKa value close to the desired pH)
Case 2:
Half-titrate the weak conjugate base with strong acid
Buffers can be mixed by any of the method below:
 Weak acid + the salt of the conjugate base in roughly equal mole proportions (HCOOH with
HCOONa)
 Weak base + the salt of the conjugate acid in roughly equal mole proportions (NH3 + NH4Cl)
 Weak acid and roughly half of an equivalent of strong base (HOAc with half equivalent KOH)
 Weak base and roughly half of an equivalent of strong acid (H3CNH2 with half equivalent HCl)
Example:
Which of the following combinations of solutes would result in the formation of a buffer solution?
A NaC2H3O2 + HC2H3O2
B NH4Cl + NH3
C HCl + NaCl
D HCl + HC2H3O2
E NaOH + HCl
F NaOH + HC2H3O2 in a 1:1 mole ratio
G NH3 + HCl in a 2:1 mole ratio
H HC2H3O2 + NaOH in a 2:1 mole ratio
Tips:
 CH3COOH same with HC2H3O2.
 Must has roughly equal mole mixture of a weak acid and its weak conjugate base.
Solution: The solution in G contains equimolar quantities of NH4+ and NH3. The NH4+ results from the
reaction.
H+Cl- + NH3 –> NH4+ + Cl
The NH3 was present in excess.
Similar situation occurs in H
Answer: A, B, G and H.
Example:
Which of the following does not form a buffer when added to NaHCO3(s)?
A NaOH(aq)
B HCl(aq)
C H2CO3(aq)
D H2O(l)
Solution:
 Adding ½ of an equivalent of NaOH to a sodium bicarbonate solution converts ½ of the
HCO3- to its conjugate base CO32-. The mixture of the two forms a buffer, so A is correct.
 Adding ½ of an equivalent of HCl to a sodium bicarbonate solution converts ½ of the HCO3-to
its conjugate acid H2CO3. The mixture of the two forms a buffer, so B is correct.
 Adding an equivalent of H2CO3 to a sodium bicarbonate solution results in equal portions of
the HCO3- to its conjugate acid H2CO3. The mixture of the two forms a buffer, so C is correct.
 Adding water does not make a buffer, because water is amphoteric, so it does not convert
sodium bicarbonate to either its conjugate acid or conjugate base. To be a buffer, there
must be both a weak acid and its weak conjugate base present in solution at the same time.
Answer: D
Example:
If 1.0 moles of a weak acid in 1.0 dm3 of water are treated with 0.4 moles of strong base, what is the
pH of the solution? (Ka for the weak acid is 2.0 x 10-4)
A pH < 3.7
B pH = 3.7
C 3.7 < pH < 7
D pH > 7
Solution:
 If the ratio of base to acid were 1:1, the pH would be equal the pKa.
 pKa is –lg 2.0 x 10-4 = 4 – lg 2 = 4 – 0.3 = 3.7
 To be half-titrated, it would require 0.5 moles of strong base. At the half-titration point, the
pH = pKa.
 With only 0.4 moles of base, the halfway point is not yet reached and there is excess weak
acid relative to conjugate base (0.6 moles to 0.4 moles).
 Henderson-Hasselbalch equation, the pH is less than the pKa. Therefore, A is the best choice.
 pH is less than pKa, which is 3.7. Be aware that this question could about the [H+] as well as
the pH of the solution. If a solution is half-titrated, then the Ka = [H+].
 This can be tricky, but the answer is found from the Henderson-Hasselbalch equation. pH =
pKa + lg (0.4/0.6), so pH < pKa.
Answer: A
STPM Chemistry Form 6 Notes – Ionic Equilibrium (Part 14 – Final)
Buffer Solution in Biological System
 Physiological pH is to be 7.4
 Venous and arterial pH vary
 Gastric fluids are highly acidic
Case 1: Physiological buffer = carbonic acid (in blood)
Arterial blood (oxygen rich) = slightly higher pH than venous blood (carbon dioxide rich)
When water added to carbon dioxide, it would undergo the following reaction:
CO2(g) + H2O(l) <—-> H2CO3(aq) <—-> HCO3-(aq) + H+(aq)
 Equilibrium regulates blood pH that affect carbon dioxide levels (= affect the pH) and
buffering of blood.
 The blood can compensate for the reduced uptake of oxygen by increasing heart rate and
producing more red blood cells, but release of carbon dioxide is not easily adjusted.
 This results, blood to be more acidic than normal (respiratory acidosis).
 Vice versa for the respiratory alkalosis results from the excessive loss of carbon dioxide.
Case 2: Physiological buffer = gastric fluids = rich in HCl and highly acidic.
 Loss of gastric fluids results in the loss of acid from the body (metabolic alkalosis).
 This result, vomit or the pumping of the stomach. The acidic solution (in body) must be
replenished to reduce the risk of metabolic alkalosis.
 Vice-versa for the food poisoning and drug overdose patients are given a solution of charcoal
and water to drink to absorb the organic toxin.
STPM Chemistry Form 6 Notes – Heterogeneous Ionic Equilibrium (Part 1)
Heterogeneous Ionic Equilibrium Precipitation

Short Definition:
 Dissolving – the breakdown of intermolecular forces between molecules as a solid becomes
a solute within a solvent. The molecule remains intact when dissolving into solution.
 Dissociation – the breakdown of ionic bonds between atoms within a lattice structure as a
salt turns into a solute within the solvent. The crystal lattice of the salt breaks apart when it
dissociates into solution.
 Solvent – the species in greatest concentration into which the solute dissolves, or salt
dissociates. A solvent must be a fluid.
 Solute – the species not in highest concentration that dissolves into the solvent, or in the
case of a salt, dissociates.
 Solubility – a measurement of the degree of dissolving that a solute undergoes within a
particular solvent.
 Saturated – the state of a solution at the point where no more solid (solute) can dissolve
into solution. When an aqueous salt solution is saturated, the rate of dissociation of the
salt equals the rate of precipitation.
 Supersaturated – the state of a solution where the amount of solid (solute) that
is dissolved into solution is beyond the maximum amount at a given temperature. The
solution is actually a suspension that when disturbed can form a precipitate rapidly.
 Solubility product (Ksp) – the equilibrium constant for a dissociation reaction, determined
from the molar solubility according to standard rules for calculating equilibrium constant.
 Molar solubility – quantitative measurement of the maximum number of moles of solid
(solute) that can dissolve into enough solvent to make one dm3 of solution under standard
conditions.
 Gram solubility – quantitative measurement of the maximum number of grams of solid
(solute) that can dissolve into enough solvent to make one hundred millimeters of solution
under standard condition.
 Common ion effect – this cause in a reduction in the amount of solid (solute) that
can dissolve into solution due to the presence in the solution of an ion that is also present in
the solid. With the common ion effect, the ion causing the reduced solubility is present in
solution at the beginning of the reaction, rather than being added once the solution has
reached solubility equilibrium.
General Solubility Rules (It is a good estimation when no solubility data is provided)
 Most salts containing alkali metal cations (Li+, Na+, K+, Cs+, Rb+) and ammonium (NH4+) are
water-soluble.
 Most nitrate (NO3- ) salts are water-soluble.
 Most salts containing halide anions (SO42- ) are water-soluble (exceptions such as Ba2+, Pb2+,
Hg2+ and Ca2+)
 Most hydroxide anion (OH- ) salts are only slightly water-soluble. KOH and NaOH are
substantially soluble, while Ca(OH)2, Sr(OH)2 and Ba(OH)2 are fairly soluble in water.
 Most carbonate anion (CO32- ) and sulfide anions (S2-) salts are only slightly water-soluble.
Solubility Rules
 Most salts composed of a +1 cation (excluding transition metals) and -1 anions are soluble in
water at room temperature.
 Nitrate (NO3- ) is a large anion that forms weak lattice interactions and forms strong
hydrogen bonds with water, so more nitrate salts are water-soluble.
 Most salts containing sulphate anions (SO42- ) with +1 cations (excluding transition metals)
are water-soluble
 Most salts with -2 or -3 anions are insoluble in water, excluding the sulphate salts.
 Most oxide (O2- ) and hydroxide anion (OH- ) salts are only slightly water-soluble. KOH and
NaOH are exceptions that are substantially soluble.
Solubility Product and Molar Solubility
Short Notes:
 Molar solubility and solubility product are very different terms. If one salt has a lower
Kspvalue than another salt, it does not mean that it is less soluble (has a lower molar
solubility).
 Solubility is determined by the molar solubility of a salt, not the solubility product
 Ksp values are calculated as products over reactants, but because solid are ignored, there is
no denominator.
 Remember to multiply the ions by the coefficient from the balanced equation!
Solubility Reaction Ksp Expression Ksp Calculation
MX(s) <—-> M+(aq) + X-(aq) Ksp = [M+][X-] Ksp = (x)(x) = x2
MX2(s) <—-> M2+(aq) + 2X-(aq) Ksp = [M2+][X-]2 Ksp = (x)(2x)2 = 4x3
MX3(s) <—-> M2+(aq) + 3X-(aq) Ksp = [M2+][X-]3 Ksp = (x)(3x)3 = 27x4
M2X(s) <—-> 2M+(aq) + X2-(aq) Ksp = [M+]2[X2-] Ksp = (2x)2(x) = 4x3
M3X(s) <—-> 3M+(aq) + X3-(aq) Ksp = [M+]3[X3-] Ksp = (3x)3(x) = 27x4
Relative Solubility
 It is difficult to predict relative solubility and the only way to compare is through experiment
or data analysis.
Example: Comparing the solubility of calcium carbonate (CaCO3) and calcium fluoride (CaF2). Which
of the two salts is more soluble? Given the solubility product of CaCO3 is 8.7 x 10-9 mol2dm-6 and the
solubility product for CaF2 is 4.0 x 10-11 mol3 dm-9.
Solution: the question asks for the highest solubility, it refers to the compound that produces the
greatest amount of dissociated salt (the greatest molar solubility) not solubility product. Never
compare numbers with unlike units. Solubility products are used to determine the molar solubility.
 CaCO3 is an MX salt, Ksp = x2
 CaF2 is an MX2 salt, Ksp = 4x3
Therefore, molar solubility for CaCO3 is 9.3 x 10-5 mol dm-3 and CaF2 is 2.2 x 10-4 mol dm-3. CaF2 is
more soluble than CaCO3 even though it has a smaller solubility product. Relative solubility questions
are asked as:
1. Which salt exhibits greater salvation?
2. Which salt precipitate first?
3. Use molar solubility to answer these questions.
Heterogeneous Equilibria
 Homogeneous equilibria – all species are in the same phase
 Heterogeneous equilibria – all the species are not in the same phase. Example:
heterogeneous equilibrium is when an ionic compound partially dissolves (in chemical terms,
dissociates) in water, the undissolved ionic compound is a solid, and the dissolved portion is
aqueous.
Example: Dissociation of CaCO3 in water
CaCO3(s) <—-> Ca2+(aq) + CO32-(aq)
Equilibrium expression
Ksp = [Ca2+][ CO32-] / [CaCO3]
However because CaCO3 is a pure solid, the concentration relative to itself is one. Therefore, we can
ignore it out from the equilibrium expression,
Ksp = [Ca2+][ CO32-]
 The ‘sp’ after the K term in solubility problems = solubility product, giving Ksp the
term solubility product constant.
Solubility Product Constants at 25˚C
AgBr 5.0 x 10-13 CuS 8.5 x 10-36
AgCN 2.2 x 10-16 Fe(OH)2 1.6 x 10-14
Ag2C2O4 6.0 x 10-12 Fe(OH)3 1.1 x 10-36
AgCl 1.0 x 10-10 FeS 3.7 x 10-19
Ag2CrO4 9.0 x 10-12 Hg2Cl2 2.0 x 10-18
AgI 1.5 x 10-16 Hg2I2 1.2 x 10-28
AgOCN 2.3 x 10-7 MgCO3 2.6 x 10-5
AgOH 1.5 x 10-8 MgF2 6.5 x 10-9
Ag2S 1.6 x 10-49 Mg(OH)2 1.2 x 10-11
AgSCN 1.1 x 10-12 Mn(OH)2 4.0 x 10-14
Ag2SO4 1.5 x 10-5 MnS 2.5 x 10-10
Al(OH)3 2.0 x 10-33 Ni(OH)2 2.0 x 10-16
BaCO3 5.0 x 10-9 NiS 2.0 x 10-21
BaCrO4 2.4 x 10-10 PbCO3 3.3 x 10-14
BaF2 1.7 x 10-6 PbCl2 1.7 x 10-4
BaSO4 1.0 x 10-10 PbF2 3.6 x 10-8
CaCO3 1.0 x 10-8 PbI2 1.4 x 10-8

CaF2 3.4 x 10-11 Pb(IO3)2 2.5 x 10-13
CaSO4 2.0 x 10-4 PbSO4 2.0 x 10-8
Cd(OH)2 4.5 x 10-15 RaSO4 4.0 x 10-11
CdS 8.0 x 10-27 SrF2 2.9 x 10-9
CoS 3.0 x 10-26 SrSO4 2.8 x 10-7
CuI 5.0 x 10-12 Zn(OH)2 1.8 x 10-14
Cu(OH)2 1.0 x 10-19 ZnS 1.2 x 10-22
Example:
When a sample of solid AgCl is shaken with water at 25˚C, a solution containing 1.0 x 10-5 mol dm-
3
silver ions is produced. Calculate Ksp.
Solution:
AgCl(s) <—-> Ag+ + Cl-
Ksp = [Ag+][Cl-]
[Ag+] = [Cl-] = 1.0 x 10-5
Ksp = (1.0 x 10-5) (1.0 x 10-5) = 1.0 x 10-10
Solubility Experiments
 Molar solubility of a salt is an empirical value and it can be determined
from experiments involving saturated solutions.
Methods:
 Spectroscopy – the amount of absorbed light at a fixed wavelength depends on the
concentration of ions. This method works only if one of the ions absorbs electromagnetic
radiation.
 Measuring the amount of salt added and then collecting, drying, weighing, and then
subtracting the mass of precipitate from this value. This method works only if the salt is
highly soluble.
 An ion exchange column to exchange the cation in solution for hydronium. The
concentration of hydronium ion determined via pH. This method works only if the salt does
not exhibit acid-base properties and has a cation concentration of at least 10-5 mol dm-3.
Predicting Precipitation
 If Q (ionic product) = Ksp, the solution is just saturated with ions and is at the point of
precipitation.
 If Q < Ksp, the solution is unsaturated and precipitation cannot occur.
 If Q > Ksp, precipitation occur.
STPM Chemistry Form 6 Notes – Heterogeneous Ionic Equilibrium (Part 6 –
Final)
Common Ion Effect
Definition of common ion effect –
 the reduction in solubility of an ionic solid (salt) in solution, because one of the ions in the
salt is already present in solution. / the effect of reducing the solubility of a sparingly soluble
ionic compound when another compound that contains an ion in common with it is added.
 the effect of reducing degree of dissociation of a weak electrolyte when another electrolyte
with a common ion is added to it.
According to common ion effect, if one of the ions is already present in solution, then less salt is
capable of dissociating, so the solubility is reduced.
Case 1:
AgCl(s) + H2O(l) <—->Ag+(aq) + Cl- (aq)
With the addition of either Ag+ or Cl- to solution in this reaction, there is a reduction on the amount
of AgCl that can dissociate into it. This is because the presence of one of the ions constituting (Ag+ or
Cl- ) in the solution.
Example:
At what pH is Ca(OH)2(s) most soluble in water?
A. 11
B. 9
C. 5
D. 3
Solution:
 pH at which Ca(OH)2(s) is most soluble is the pH at which there is the least common ion
(OH- ) present in solution.
 There is the least OH- present at lower pH values, where the solution is acidic.
 Note that basic salts are most soluble in acidic solutions.
Answer: D. 3
Example:
Mercury II cations are most soluble in which of the following solution?
A. 0.10 mol dm-3 NaNO3
B. 0.10 mol dm-3 NaI
C. 0.10 mol dm-3 Na2S
D. 0.10 NaCl
Solution:
 Find the relative solubility of Hg(NO3)2, HgI2, HgS and HgCl2
 Nitrates are infinitely soluble in water.
 Only nitrate (anions) can form hydrogen bonds with water, so it has the greatest salvation
energy of the four anions.
 Nitrate has the largest of anions, therefore it has the weakest electrostatic forces in its
lattice structure.
Answer: A
STPM Chemistry Form 6 Notes – Phase Equilibrium (Part 1)
Fractional Distillation
Definition
Vapour pressure above a liquid – force per unit area above the surface of a liquid exerted by
molecules formed upon evaporation of the liquid.
Vapour pressure of a liquid
 It is the partial pressure exerted by the gas molecules formed by evaporation from
the surface of the liquid, when it is in equilibrium with the gas molecules condensing back
into the liquid.
 It is depends on the temperature (energy of the molecules) of the liquid and ΔHvaporisation(the
energy necessary to overcome intermolecular forces) of the liquid.
 The surface of a liquid is the most favorable points for the molecules to evaporate.
 Molecules can evaporate only from the surface, and tend to evaporate from the corners.
 Corners molecules have the fewest intermolecular forces and because of the minimal forces,
molecules evaporate most readily.
 It can be measured in either an open or closed system
 In a closed system, a partial pressure of vapour exists because the rates of vaporisation
equal the rate of condensation.
 In an open system, the vapour escapes, therefore it does not reach a state
of equilibrium between the rate of vaporisation and the rate of condensation. It is difficult to
measure, so generally in theoretical perspective, the values that have been determined in a
closed system at known temperature are applied in an open system.
 It is independent of the shape and volume of a container.
 The atmospheric pressure does not significantly affect the vapour pressure (Boiling point
depends on the atmospheric pressure).
 Pvapour ↑ as temperature ↑; Pvapour ↓ as ΔHvaporisation ↑
Relationship between vapour pressure and temperature
 Vapour pressure increases as the temperature of the solution increases in a linear form
 Everyday situation: Observe the process of boiling water. This process would take a while for
the bubbles to form in the water as it nears its boiling point. Once the bubbles form, it need
to take a short period of time before the water actually reach the boiling point.
 In conclusion, as the temperature of a liquid increases, the pressure of its vapour increases
but in an exponential graph.
Boiling point
 Definition based on phases: Boiling point is the temperature above which a substance may
not exist as a liquid
 Definition based on vapour pressure: Temperature at which the vapour pressure of a liquid
is equal to the atmospheric pressure
Case 1: In the mountain
The boiling point of a liquid is lower than normal at reduced atmospheric pressure.
Case 2: In a pressure cooker
The boiling point of a liquid is higher than normal at increased atmospheric pressure
 Boiling process involves vaporisation of a compound in its liquid phases and boiling point is
affected by intermolecular forces (hydrogen bonding, molecular mass and polarity) and
atmospheric pressure.
Example:
Which of the following compounds has the highest boiling point?
A H3COH
B H3CNH2
C H3CCH2NH2
D H3CCH2OH
Solution: Highest boiling point = greatest intermolecular forces and greatest molecular mass.
Option A, B, C and D can form hydrogen bond, but alcohols (-OH) are more polar and form stronger
hydrogen bonds than their amine (-NH2) equivalents. This eliminates option B and C.
Option D (ethanol) is heavier than option A (methanol), so the higher boiling point is option D.
Answer: D
Raoult’s Law
 Definition: The partial vapour pressure of a component (A) in a solution at a given
temperature is equal to the vapour pressure of pure liquid (A) at the same temperature,
multiplied by the mole fraction of the component (A) in the solution.
 The vapour pressure depends on the mole fraction and the pure vapour pressure of the
components.
 The understanding of this theory is that the mole fraction of a compound corresponds to the
percentage of the surface of the liquids mixture due to that compound.
 Any component (A) makes up only half of the surface, then only as much as what normally
evaporates from the pure liquid (A), vaporises from the mixture.
 PA = P˚A XA
 Mole fraction of a component in Raoult’s equation is in solution and not in the vapour state.
 Mole fraction of a compound in solution decreases, this results, the vapour pressure of that
component above the solution decreases.
Question:
0.10 moles of AsH3, NH3 and PH3 are placed into a beaker at -100˚C, where all three exist in liquid
phase. What can be said about their relative vapor pressures?
A PAsH3 < PNH3 < PPH3
B PAsH3 < PPH3 < PNH3
C PNH3 < PAsH3 < PPH3
D PPH3 < PNH3 < PAsH3
Solution:
In Raoult’s law, the vapour pressure depends on the mole fraction and the pure vapour pressure of
the component. In the question, the solution contains equal molar quantities of the three
components. Therefore, the highest vapour pressure results from the compound with the lowest
boiling point (highest pure vapour pressure).
 NH3 has the highest boiling point because it can form hydrogen bonds so it has the lowest
vapour pressure.
 AsH3 and PH3 are polar compound so the most significant factor in determining the boiling
point is molecular mass.
 Lighter molecules are easier to vaporize = greater vapour pressur for the compound.
 PH3 is lighter than AsH3
Answer: C
Total Vapour Pressure
 A mixture of two or more liquids is the sum of the individual vapour pressures of each
component liquid.
 Ptotal = PA + PB + PC + …
 At boiling point of the solution, the total vapour pressure of the components equals the
atmospheric pressure.
 Solution obeys Raoult’s law is an ideal solution. However, in real situation, there are other
factors that interferes example intermolecular forces between the liquids. The molecules
interact in both liquid and gas phases, the vapour pressure relationship is not as linear as
Raoult’s law equation.
 Overall increase in attractive forces in solution (components are mixed) –> vapour pressure
decreases = negative deviation.
 Overall decrease in attractive forces in solution (components are mixed) –> vapour pressure
increases = positive deviation.
Distillation Process
Fractional Distillation
 Distillation is used to remove a liquid from a solution.
 Fractional distillation – a series of evaporation and condensation cycles.
 The distilling column / fractionating column has an additional surface area = pack with an
inert material (glass beads) or short pieces of glass tubing or increase the length of the
column.
 Increase the surface area of the distilling column / fractionating column is to purify the
product by increasing the number of evaporation and condensation cycle / process of
vaporization-condensation.
 Distillation flask = richer in the less volatile component
 Distillate / Receiving flask = richer in the more volatile component (lower boiling point
component in the mixture)
 Porcelain chips are used to prevent bumping in the distillation flask.
Example:
Which of the following distillations results in the purest product?
A Benzene (b.p. = 80˚C) from 2,3-dimethylbutane (b.p. = 58˚C)
B Diethyl ether (b.p. = 35˚C) from tetrahydofuran (b.p. = 67˚C)
C Heptane (b.p. = 98˚C) from hexane (b.p. = 69˚C)
D Methanol (b.p. = 56˚C) from ethanol (b.p. = 78˚C)
Solution:
The distillation that generates the purest product is the one with the greatest vapour pressure ratio
of more volatile component to less volatile component. The greatest ratio is found in the pair of
compounds that has the biggest difference in boiling points.
Answer: B
Vacuum Distillation / Distillation under Reduced Pressure
 Reduce the atmospheric pressure results a compound to boil easily.
 Boiling point of components has been reduced.
 It is used when a compound has an extremely high boiling point / has a decomposition
temperature lower than its normal boiling point.
 Disadvantages: danger of implosion and difficult to control bumping because it occurs
vigorously and impurities (low boiling point) may be distillated over.
Ideal solution
 Miscible liquids (A & B)
 The intermolecular forces of attraction between A … A, B … B and A … B (after mixing) are
equal
 No change in volume after mix A & B
 No enthalpy change on mixing
Non-ideal solutions
 Miscible liquids (A & B)
 The intermolecular forces of attraction in liquid mixture A … B are stronger or weaker than
the intermolecular forces of attraction between A … A in pure liquid A and between B … B in
pure liquid B.
 There are changes in volume after mix A and B
 There are enthalpy change on mixing
 Negative deviation and positive deviation from Raoult’s law
Negative deviation from Positive deviation from

Raoult’s law Raoult’s law
Actual vapour pressure Actual vapour pressure

is lower than the predicted by is higher than the predicted by
Raoult’s Law Raoult’s Law
The formation (after mixing A The formation (after mixing A

& B) & B) of weaker intermolecular
of stronger intermolecular forces of attraction
forces of attraction
Decreases in volume after Increases in volume after

mixing mixing
Decreases the tendency of Increases the tendency of

molecules to escape from the molecules to escape from the
liquid mixture liquid mixture
Temperature increases after Temperature decreases after

mixing mixing
Heat is liberated (the heat Heat is absorbed (the heat

energy released to form new energy released to form new
bonds is greater than the heat bonds is less than the heat
energy absorbed to break the energy absorbed to break the
bonds in pure liquids) bonds in pure liquids)
Minimum vapour pressure Maximum vapour pressure

Azeotropic mixtures Azeotropic mixtures
with maximum boiling point with minimum boiling point
Negative azeotrope Positive azeotrope

 Formic acid and water  Chloroform and
methanol
 Hydrochloric acid and
water  Ethanol and water
 Ethanol and benzene
Immiscible Liquid
 Immiscible liquid – liquids do not dissolve in one another
 Two of the immiscible liquids (A & B) are mixed, it form two separate layers
 Lower density liquid – top layer
 Higher density liquid – bottom layer
 The intermolecular forces of attraction between their molecules are different
 Example: benzene and water, mercury and water, chlorobenzene and water, nitrobenzene
and water
 Water is a polar molecule
 Benzene, chlorobenzene and nitrobenzene are non-polar molecule with van der Waals
forces of attraction and mercury atoms are bonded to each other with metallic bond.
Vapour Pressure of Immiscible Liquids
 The total vapour pressure of the mixture is the sum of the vapour pressures of the pure
components
 PT = P˚A + P˚B where PT = Total pressure of the liquid mixture, P˚A = Vapour pressure of pure
liquid A, P˚B = Vapour pressure of pure liquid B
 Method of distillation and purification: Steam distillation and followed by separation process
using separation funnel
 Steam distillation is used to extract fragrant oils from plants (making perfume) and purify
organic compound
 To carry out this process, the liquid must be immiscible with water, have a relatively high
RMM and high vapour pressure (100˚C)
Dalton’s Law of Partial Pressures
 P˚A = XA • PT and P˚B = XB • PT where XA = mole fraction component A in vapour and XB = mole
fraction component B in vapour
 XA = nA / (nA + nB) and XB = nB / (nA + nB) where nA = number of moles A and nB = number of
moles B
 (Dividing P˚A and P˚B) P˚A / P˚B = nA / nB
 Number of moles (n) = mass in gram (m) / molecular mass (M)
 Final equation, mA / mB = P˚A•MA / P˚B•MB
Example:
Water and chlorobenzene are boiled at a pressure of 101 kPa, the temperature is 90˚C and the ratio
of the mass of chlorobenzene to that of water is 2.46. The vapour pressure of water at 90˚C is 72.3
kPa, calculate the relative molecular mass (RMM) of chlorobenzene.
Solution:
 Use formula mA / mB = P˚A•MA / P˚B•MB
 Vapour pressure of chlorobenzene at boiling point, 101 – 72.3 = 28.7 kPa
 2.47 = (28.7 x Mchlorobenzene) / (72.3 x 18)
Answer: Relative molecular mass of chlorobenzene = 112
Boiling Point Elevation
 Boiling point of a solution increases with the addition of impurities (Increase in B.P.,
decreases in vapour pressure)
 Example: Addition of salt in water.
Boiling point elevation is due to two factors:
 Decrease surface area for the liquid to evaporate.
 Water has stronger attraction to the ionic impurities. It requires more energy to break ion-
dipole interaction than the hydrogen bond between water molecules.
Freezing Point Depression
 Freezing point of a compound can be altered by varying the intermolecular forces.
 F.P. decreases as soluble impurities are added.
 Example: Salt is added to the surface of an ice cube and the water molecules on the surface
of the lattice are attracted to the salt. This is an exothermic reaction because addition
energy is released to melt the ice. Therefore, salt can be used to help to melt the ice on
roads and prevent future freezing.
Freezing point depression is due to factor:
 Solute particles exhibit attractive forces in solution.
Colligative Properties: Concentration Effects
 Colligative – properties of a solution that are affected by the concentration of a soluble
impurity. This included boiling point elevation (the same as vapour pressure reduction),
freezing point depression and osmotic pressure (osmotic pressure is not included in STPM
syllabus).
 The greater the number of impurities, the greater the effect.
 Impurities are added to solution –> solvent has greater tendency to remain as a liquid –
increase intermolecular forces in the solution phase.
 Water tends to stay in the liquid phase with the increased energy of impurities (rather
changes to another phase). The boiling point of an aqueous salt solution increases and the
freezing point of an aqueous salt solution decreases.
Conductance
 Pure water does not conduct an electrical current (no ions present).
 The specific conductance of an aqueous salt solution is directly proportional to the
concentration of salt on solution.
 Condosity solution – the molar concentration of an aqueous sodium chloride solution that
has the same specific conductance as the aqueous salt solution.
 Example: the 1.0 mol dm-3 salt (aq) solution has a condosity of 2.0, means 2.0 mol dm-3 NaCl
(aq) solution would have the same conductivity as a 1.0 mol dm-3 salt (aqueous) solution.
Distribution of a Solute (X) between Two Solvent (Solvent A and Solvent B)
Distribution law = partition law – A solute distributes itself between two immiscible liquids so that
the ratio of its concentration in each solvent is constant at constant temperature
Partition coefficient / distribution coefficient, K (a constant)
= (Concentration of X in solvent A / Concentration of X in solvent B)
The partition law follows the condition:
 The temperature is constant
 Two solutions are dilute
 Solute does not react with the solvents
 Solute exists in the same molecular state in the two solvents (does not dissociate or
associate)
Example:
A solution contains 2.0 g of iodine dissolved in 20 cm3 of potassium iodide solution. If this solution is
shaken with 20 cm3 of tetrachloromethane, how much iodine will be extracted by into the
tetrachloromethane?
(partition coefficient of iodine between tetrachloromethane and water = 85)
Solution:
Let the mass of iodine extracted be x
85 = (Concentration of iodine in tetrachloromethane / Concentration of iodine in water)
85 = (x / 12) / [(2 – x) / 20]
x = 1.98 g
Solvent Extraction
 Separating funnels are used for solvent extraction
 Organic compounds can be extracted from aqueous solution by using the solvent
 Example: ether extraction
Ideal Solution: Miscible Liquids
Method: Fractional Distillation
 Boiling point – composition diagram for a mixture (A and B)
 First distillate: Either one of the pure liquid (A) with lower boiling point / more volatile
component
 Residual / Second distillate: pure liquid (B) with higher boiling point
Non-ideal Solution: Miscible Liquids
Method: Fractional Distillation
 Boiling point – composition diagram for a mixture
I) Positive deviation
 Minimum boiling point
 First distillate: Azeotrop
 Residual / Second distillate: Either one of the pure liquid
 Example: ethanol-water system
II) Negative deviation
 Maximum boiling point
 First distillate: Either one of the pure liquid
 Residual / Second distillate: Azeotrope
 Example: trichloromethane-ethanol system
Sketch graph:
Remember three points (SAL):
 S = Shape must be correct
 A = Axes must be with correct unit (if given)
 L = Label the graph (vapor and liquid or reactants and products or azeotrope)
Immiscible Liquids
Method: Steam Distillation (used to purify an organic liquids which has a high boiling point and
decomposes at temperatures near its normal boiling point
Three important points for the steam distillation to be carried out:
 Immiscible with water
 High molecular mass
 High vapour pressure at about 100˚C
STPM Chemistry Form 6 Notes – Phase Equilibrium (Part 10 – Final)
Chromatography
 Definition: Chromatography – technique used to separate the mixture of components by
distributing the mixture between two immiscible phase, the stationary phase and the mobile
phase.
 Types of chromatography: adsorption chromatography & partition chromatography
Adsorption chromatography
 Stationary phase = solid
 Mobile phase = liquid or gas
 Mixture of components are adsorbed on the surface of the stationary phase
 Example: column chromatography, thin layer chromatography (TLC)
Partition chromatography
 Stationary phase = non-volatile liquid film supported on an inert solid
 Mobile phase = liquid or gas
 Mixture of components are partitioned between the liquid film and the mobile phase (Used
partition coefficient / distribution coefficient, K)
 Interpretation: high value K = the component (X) dissolves more readily in the mobile phase
and the component moves rapidly along the stationary phase.
 Interpretation: low value K = the component (X) remain largely adsorbed on the stationary
phase and the components moves slowly along the stationary phase.
 Example: paper chromatography, gas-liquid chromatography (GLC)
Application of chromatography
 Separate mixture components
 Identify components
 Determine the purity of a substance
Example:
 Pigments from plant
 Antibiotics from fungi
 Amino acids

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STPM Chemistry Form 6 Definition List – Part 1:

ELECTRONIC STRUCTURE OF ATOMS

Term Definition Example

Bronsted-Lowry acid Proton donor HX in protic solvent

Bronsted-Lowry base Proton acceptor KOH in protic solvent

Lewis acid Electron pair acceptor BF3 in aprotic solvent

Lewis base Electron pair donor NH3 in aprotic solvent

Four important concepts (just the berry essence):

Acid Name pKa

Cl3CCOOH Trichloroacetic acid 0.64

Cl2HCCOOH Dichloroacetic acid 1.27

H2SO3 Sulfurous acid 1.82

HClO2 Chloroacetic acid 1.90

ClH2CCOOH Chloroacetic acid 2.82

HF Hydrofluoric acid 3.15

HNO2 Nitrous acid 3.41

HCOOH Formic acid 3.74

H3CCOOH Acetic acid 4.74

4-H2NC6H4NH3+ 4-aminoanilinium 6.18

H3CO3 Carbonic acid 6.36

4-O2NC6H4OH 4-nitrophenol 7.15

HClO Hypochlorous acid 7.46

HBrO Hypobromous acid 8.72

NH4+ Ammonium 9.26

HCN Hydrogen cyanide 9.36

HIO Hypoiodous acid 10.66

Solid Liquid Gas

Simple cubic One atom per repeating unit cell

Body-centred cubic Two atoms per repeating unit cell

Face-centred cubic Four atoms per repeating unit cell

Strongest Strong yet weaker Strong yet Weakest

Surface tension – the resistance of a liquid to an increase in its surface area.

Phase Change Term

Liquid to gas Vaporisation

Gas to liquid Condensation

Solid to liquid Melting

Liquid to solid Freezing

Solid to gas Sublimation

Isothermal – conditions where the temperature of a system does not change.

Series n1 n2 Type of electromagnetic radiation

Electronic Energy Levels

Unit cell Characteristics Example

Cubic a = b = c<a = <b = <c = 90˚ Sodium chloride

Tetragonal a = b not = c<a = <b = <c = 90˚ Tin

Orthorhombic a not = b not = c<a = <b = <c = Rhombic sulphur

Monoclinic a not = b not = c<a = <b = 90˚<c Monoclinic sulphur

Rhombohedral a = b = c<a = <b = <c not = 90˚ Calcite (calcium carbonate)

Hexagonal a = b not = c<a = <b = 90˚<c = Quartz, graphite

State Shape of substance Volume of substance

Solid Definite Definite

Liquid Indefinite Definite

Gas Indefinite Indefinite

Water Carbon dioxide

 Zero order First order Second order

Rate law rate = k rate = k[A] rate = k[A]2

Half-life t1/2 = [A]o / 2k t1/2 = ln 2 / k t1/2 = 1 / k[A]o

Unit of rate mol dm-3 s-1 s-1 mol dm3 s-1

First order Second order Second order

The slowest step The slowest step The slowest step

A –> B + C A + B –> C 2A –> B + C

One step One step One step

Rate = k[A] Rate = k [A][B] Rate = k [A]2

Factor Rate of Rate Equilibrium Composition of

Increase in ↑ ↑ Endothermic:↑ Endothermic: