H2 Chemistry

Concept Outline
Fu Siyang
14S7B
Sept 2015

Foundational Chemistry
One mole of a substance
It is the amount of substance that contains the same number of particles as there are atoms in 12 g of
12
C isotope.

Avogadros number
It is the number of atoms in 12 g of 12C isotope.

Avogadros Law
Equal volumes of all gases, under the same temperature and pressure, contain the same number of
particles.

Reduction
A process whereby a substance gains electrons, resulting in a decrease in oxidation number

Oxidation
A process whereby a substance loses electrons, resulting in an increase in oxidation number

Redox reaction
A reaction that involves reduction and oxidation simultaneously

Disproportionation
A redox reaction in which the same substance is both oxidised and reduced

Oxidation number
The number of electrons to be added or subtracted from an atom in a combined state to convert it to
elemental form

Atomic orbital
The region of space with a 90% probability (or more) of finding an electron

Effective nuclear charge

The net nuclear charge experienced by an outer electron

Chemical Bbonding
Metallic bonding
The electrostatic forces of attraction between metal cations and the sea of delocalised electrons in a
metal

Ionic bonding
The electrostatic forces of attraction between oppositely charged ions in an ionic compound

Covalent bonding
The electrostatic forces of attraction between the nuclei of atoms and their shared pair of electrons

The VSEPR theory

1) The electron pairs around a central atom will adopt a geometry that would minimise the
repulsion between them by placing themselves as far away as possible in a 3-dimensional space;
2) Lone pair-lone pair repulsion > lone pair-bond pair repulsion > bond pair-bond pair repulsion

Non-polar molecule
One that has no overall dipole after resolving the dipole moments of every covalent bond in the
structure

Polar molecule
One that has a net dipole moment

Chemical Energetics and Thermodynamics

Activation Energy
The activation energy of a reaction is the minimum energy which the reacting particles must possess in
order to overcome the energy barrier before becoming products

Standard enthalpy change of reaction

The enthalpy change when molar quantities of reactants as specified by the chemical equation react to
form products at 1 atm and 298K.

Standard enthalpy change of formation

The enthalpy change when 1 mol of a substance is formed from its constituent elements in their
standard states at 298K and 1 atm.

Standard enthalpy change of combustion (-ve)

The heat evolved when 1 mol of a substance is completely burnt in excess oxygen at 298K and 1 atm.

Standard enthalpy change of neutralisation (-ve)

The heat evolved when 1 mol of water is formed in the neutralisation reaction between an acid and a
base, at 298K and 1 atm.

Standard enthalpy change of atomisation for an element (+ve)

The energy required when 1 mol of gaseous atoms is formed from the element at 298K and 1 atm.

Standard enthalpy change of atomisation for a compound (+ve)

The energy required to convert 1 mol of the compound into gaseous atoms at 298K and 1 atm.

Standard enthalpy change of hydration (-ve)

The heat evolved when 1 mol of free gaseous ions is dissolved in an infinite volume of water at 298K and
1 atm.

Standard enthalpy change of solution

The enthalpy change when 1 mol of solute is completely dissolved in an infinite volume of solvent at
298K and 1 atm.

Bond dissociation energy (+ve)

The energy required to break 1 mol of a particular covalent bond in a specified molecule in the gaseous
state.

Bond energy (+ve)

The average energy required to break 1 mol of a covalent bond in the gaseous state.

Lattice energy (-ve)

The heat evolved when 1 mol of solid ionic compound is formed from its constituent gaseous ions.

The first ionisation energy (+ve)

The energy required to remove 1 mol of electrons from 1 mol of gaseous atoms to form 1 mol of singly
charged gaseous cations.

The first electron affinity (1st ve; 2nd +ve)

The enthalpy change when 1 mol of electrons is added to 1 mol of gaseous atoms to form 1 mol of singly
charged gaseous anions.

The Hesss Law

The enthalpy change of a reaction is determined only by the initial and final states and is independent of
the reaction pathway taken.

Entropy
It is a measure of the randomness or disorder in a system, reflected in the number of ways that
molecules and energy in a system can be arranged.

Enthalpy Change
The difference in energy level between the products and reactants

Spontaneous process
A spontaneous process is one that, in the absence of any barrier such as activation energy, takes place
naturally in the direction stated.

The Gaseous State

Ideal gas
It is a hypothetical gas of which pressure-volume-temperature behaviour can be completely accounted
for by the ideal gas equation pV=nRT.

Partial pressure
Partial pressure of a gas is the pressure exerted by that individual gas in a mixture of gases on the sides
of a container.

Daltons Law of Partial Pressures

The total pressure of a mixture of gases is the sum of the partial pressures of the constituent gases.

The kinetic theory of gases (important assumptions)

1) The gas particles have negligible volume compared to the volume of their container
2) The intermolecular forces between gas particles are negligible
3) Collisions between gas particles and collisions between gas particles and walls of the container
are perfectly elastic

Chemical equilibria
Le Chateliers Principle
When a system in equilibrium is subjected to a change on conditions which disturbs the equilibrium, the
position of equilibrium will shift in a way so as to reduce that change.

Dynamic equilibrium
When the rate of the forward reaction equals the rate of the reverse reaction, the system is in dynamic
equilibrium.

The equilibrium law

If a reversible reaction is allowed to reach equilibrium, the product of the concentrations of each
product (raised to the appropriate powers) divided by the product of the concentrations of each
reactant (raised to the appropriate powers) has a constant value called the equilibrium constant, K, at a
constant temperature.
=

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Reaction Quotient
At any instant,

The Haber Process

1) 450
2) 250 atm
3) Finely divided Fe catalyst

Ionic Equilibria
Bronsted-Lowry acid-base theory
1) An acid is a proton donor.
2) A base is a proton acceptor.

Lewis acid-base theory

1) An acid is an electron pair acceptor.
2) A base is an electron pair donor.

Conjugate acid-base pair

A conjugate acid-base pair constitutes two species which differ from each other by one proton.

Degree of dissociation
The fraction of molecules which is ionised into ions in water is called the degree of dissociation.

Salt hydrolysis
A reaction in which ions react with water to produce OH- or H3O+ ions.

Buffer solution
A solution that is able to resist pH changes upon addition of small amount of acid or base.
1) Acidic buffer: an aqueous solution of a weak acid and its salt
2) Alkaline buffer: an aqueous solution of a weak base and its salt

Choice of indicators
Working range of an indicator is pH=pKIn 1.
Indicator

Working range

Methyl orange
35
Phenolphthalein 8 10
Thymol Blue
8 10

Before equivalence
point
Red
Colourless
Yellow

At equivalence
point
Orange
Pink
Green-grey

After equivalence
point
Yellow
Red
Blue

Solubility Product
Solubility of a salt
The amount (or mass) of solute (salt) that can be dissolved in 1 dm3 of a given solvent to form a
saturated solution at a given temperature.

Supersaturated solution
A solution that contains more solute than the amount needed to form a saturated solution.

Solubility Product
Ksp of a sparingly soluble salt is the product of the molar concentrations of the constituent ions in a
saturated solution, raised to the appropriate powers at a given temperature.

Ionic product
IP of a sparingly soluble salt is the product of the molar concentrations of the constituent ions in the
solution, raised to the appropriate powers at a given temperature.

Electrochemistry
Standard electrode potential
The standard electrode potential of a half-cell is the potential associated with a given half-reaction when
all components are in their standard states, measured relative to the standard hydrogen electrode.

Standard cell potential

The potential difference between the two half-cells measured at standard conditions.

Electrolysis
A process that involves the lysing or splitting of a substance, often to its component elements, by
supplying electrical energy. The electrical energy from an external source causes a non-spontaneous
redox reaction to occur.

Electrolyte
An electrolyte is a liquid or an aqueous solution, which contains mobile ions and therefore can conduct
electricity.

Reaction Kinetics
Transition State
The arrangement of atomic nuclei and bonding electrons at the maximum potential energy.

Rate of reaction
The change in concentration of a reactant or a product per unit time.

Half life
The time taken for the concentration of a reactant to decrease to half of its initial value.

Clock reaction
A clock reaction is produces a sudden change (usually visual) when a small fixed amount of a product is
formed.

Catalyst
A catalyst is a substance that speeds up a chemical reaction by providing an alternative reaction
pathway with lower activation energy, while remaining chemically unchanged at the end of the reaction.

Autocatalysis
One of the products of the reaction is a catalyst for the reaction itself.

Enzymes
Enzymes are biological catalysts that speed up reactions in living systems while remaining unchanged at
the end of the reaction. They are specific in their action.

Substrate
The reactant that binds to the enzymes active site is the substrate.

Chemical Periodicity
Flame Colour (in oxygen)
Na
Mg
Al

Brilliant yellow flame

Bright white light
NA (oxidised to Al2O3)

Si
White phosphorous P4 (trigonal pyramidal structure)
Red Phosphorous P
S
Cl
Ar

NA (oxidised to SiO2)
Bright white flame
Soft orange flame
Pale blue flame
NA
NA

Chloride salts
NaCl
MgCl2
AlCl3
SiCl4
PCl3
PCl5

White ionic solid

White ionic solid
Pale yellow powder that fumes in moist air; sublimes to form Al2Cl6
Colourless volatile simple covalent liquid
Colourless fuming simple covalent liquid
Off-white solid

Colours of halogens
Element In gaseous
phase
F2
Pale yellow
Cl2
Yellowgreen
Br2
Reddish
brown
I2
Dark purple

In liquid
phase
NA
NA

In solid
phase
NA
NA

Reddish
brown
NA

NA
Shiny
black

In aqueous phase

In non-polar solvent phase

NA
Colourless (dilute)
Pale yellow (conc.)
Yellow (dilute)
Orange (conc.)
Pale yellow (in water)
Brown (in I- (aq))

Very pale yellow

Very pale green
Orange to reddish brown,
depending on concentration
Violet

Organic chemistry
Electrophile
An electron deficient species that accepts an electron pair from an electron rich species in a reaction to
form a new covalent bond

Nucleophile
A species that donates an electron pair to an electron deficient species in a reaction to form a new
covalent bond

Intermediate
A definite species that exists for a finite length of time in a reaction.

Free radical
An atom or group of atoms that has an unpaired electron

Carbocation
A species that contains a carbon atom bearing a positive charge

Carbanion
A species that contains a carbon atom bearing a negative charge

Inductive effect
The withdrawal or donation of electrons through a bond due to electronegativity and the polarity of
bonds in functional groups

Resonance effect
The withdrawal or donation of electrons through a bond due to overlap of a p orbital on the
substituent with a p orbital on the adjacent double bond or aromatic ring

Enantiomer
Non-superimposable mirror images

Geometric isomerism in alkenes

Geometric isomerism arises in alkenes due to restricted rotation about the C=C bond.

Proteins/Amino acids
Zwitterion
Dipolar ions with no overall electrical charge

Isoelectric point
The pH at which the overall net charge on the amino acid is 0 and it exists primarily as the neutral
zwitterion

Electrophoresis
Separation of different amino acids at a certain pH level using an electric field

Transport proteins
Move metabolites around the cell or around the whole organism

Regulatory proteins (hormone)

Coordinate the activities in the body by controlling the level and type of cell functions including
metabolism and reproduction

Defensive proteins (antibody)

Produced by specialised cells of the immune system in response to foreign antigens

Catalytic proteins (enzyme)

Accelerate metabolic processes which produce energy, build up new cell structures and destroy old ones

Primary structure
It is the sequence of amino acid residues in a polypeptide chain through formation of peptide linkages.

Secondary structure
It is the regular coils and folds in localised segments of a polypeptide chain, stabilised by hydrogen
bonds formed between the lone pair electrons on the oxygen atom of a C=O bond in a peptide linkage
and the H atom in a N-H bond in another peptide linkage on the polypeptide backbone.

Tertiary structure
It is the 3-dimensional shape of a polypeptide chain, stabilised by side-chain interactions.

Quaternary structure
It is the overall special arrangement of several polypeptide chains through side chain interactions.

Denaturation
It is the process of destroying the secondary, tertiary and quaternary structures and altering the specific
conformations of a protein, causing it to lose its ability to perform its function.

Transition elements
Transition element
It is a d-block element that forms some compounds containing its ion with an incomplete d-subshell

Complex
A complex is formed by a central metal atom or cation dative-bonded by surrounding anions or
molecules (known as ligands)

Ligand
A ligand is an ion or molecule that has at least one lone pair of electrons that can be donated into the
vacant orbitals in the central metal atom or ion

Coordination number
The coordination number indicates the number of dative bonds around the central atom or ion.

Explanation Questions
D-d electronic transitions
In a free metal atom or ion with partially filled 3d orbitals, the 5 3d orbitals are degenerate. In the
presence of ligands in an octahedral field, the 5 3d orbitals split into two different energy levels with an
energy gap E in between. There are vacancies in the higher energy d orbitals, and the promotion of an
electron from a lower energy level to a higher one requires the absorption of a photon with energy E,
usually in the visible region of the electromagnetic spectrum. Such d-d transition is responsible for the
colour of the complex ion, and the colour observed is the complement colour of the photons absorbed.

Toxicity of CO
Haemoglobin is the Fe-containing protein in red blood cells that transports oxygen in blood. A
haemoglobin molecule in the lungs picks up an O2 molecule and forms reversible dative binding between
the Fe atom and the O2 molecule, enabling haemoglobin to carry oxygen around the body and release it
when needed. However, CO undergoes ligand exchange with oxygen and binds with the Fe atom in
haemoglobin irreversibly to form a very stable complex carboxyhaemoglobin. The affinity of human
haemoglobin for CO is much larger than that for O2, thus a small quantity of CO can inactivate a large
number of haemoglobin molecules for oxygen transport. If the concentration of CO is high and the level
of carboxyhaemoglobin is too high, oxygen transport is shut down and death occurs.

Thermal Stability of Group II compounds

The thermal stability of Group II nitrates, carbonates and hydroxides increases down the group. This is
because the cationic radii increase down the group, while charges remain the same. Charge density of
the cations decreases down the group, thus polarising power of the cations decreases down the group.
They are less able to distort the electron cloud of the anion, weakening the covalent bonds within the
anion to a smaller extent. Covalent bonds within the anion are less likely to be broken down the group,
hence higher temperature (higher energy) is required to break the bonds.

Abnormally low bond energy of F2

From Cl to I, the atomic radii increase and hence the orbital overlap between the atoms becomes less
effective. The bond length increases and the X-X bond becomes weaker.
The F-F bond is so short that the lone pairs of electrons on the F atoms repel each other and weaken the
F-F bond.

Abnormally small (in magnitude) first electron affinity of F atom

From Cl to I, the number of quantum shells increases. Any electron added to the atom is less strongly
attracted to the nucleus. The ability of the halogen atom to accept the electron decreases, thus first
electron affinity becomes less exothermic.
F is an exception due to its extremely small size of the atom. The electron is placed into a region of space
that is crowded with electrons, causing strong repulsion. Hence the electron added is less strongly
attracted to the nucleus.

Electronic configurations of Cr and Cu

The electronic configuration of Cr is [Ar] 3d5 4s1 because equal distribution of electronic density in the 3d
subshell results in the overall reduction of inter-electronic repulsion in the atom.
The electronic configuration of Cu is [Ar] 3d10 4s1 because symmetrical electron distribution in the 3d
subshell is preferred.

Surface lustre of metals

The delocalised electrons do not reside in any orbitals. When light falls on the surface, most photons
simply bounce off as the metal is unable to absorb light. Most of the light is reflected and observed,
accounting for the shininess of the metal.

Deviation of actual gases from ideal gas behaviour

At low temperature, intermolecular forces of attraction becomes significant and collisions become
inelastic. When the particles do not have enough energy to overcome intermolecular forces of
attraction, liquefaction occurs.
At high pressure, intermolecular distances become shorter and intermolecular forces become
significant. The impact of molecules striking on the walls is lowered and the pressure is lower than what
is expected of an ideal gas. The molecules also take up a large portion of the volume of the container,
hence the assumption that volume of the molecules are negligible compared to the volume of the
container is no longer valid.

Mode of action of heterogeneous catalysts

1) Adsorption: the reactant molecules diffuse towards the surface of the solid catalyst and are
adsorbed onto the active sites at the surface. The adsorption process brings reactant molecules
closer together, increasing their surface concentrations and collision frequency. The process also
weakens the bonds in the reactant molecules, thus lowering the activation energy. The reactant
molecules are also correctly oriented for reaction to occur.
2) Desorption: product molecule desorbs and diffuses away from the catalyst surface. The active
sites become free to adsorb new reactant molecules. When the active sites are fully occupied
(i.e. saturated), the order of reaction with respect to the reactant molecules becomes 0.

Relationship between [substrate] and rate of an enzyme-catalysed reaction

At low [substrate], the enzyme concentration is greater than substrate concentration, so as more
substrate is added, the rate of reaction increases. The reaction is first order with respect to the
substrate.
At high [substrate], when all the active sites are filled with substrate molecules (i.e. saturation point),
any further increase in [substrate] does not affect the rate. The reaction is now 0th order with respect to
the substrate.

Mode of action of a buffer (CH3CO2H and CH3CO2- Na+)

The solution contains large reservoirs of unionised CH3CO2H and CH3CO2- ions from CH3CO2- Na+.
When a small amount of H+ is added to this buffer, the H+ ions react with the large reservoir of the
CH3CO2- ions and are removed and pH remains almost constant.
When a small amount of OH- is added to this buffer, the OH- ions react with the large reservoir of the
CH3CO2H molecules and are removed and pH remains almost constant.

The importance of a salt bridge in the electrochemical cell

Without a salt bridge, charge imbalance is given rise in the cell and current will cease. In the salt bridge,
anions in the salt bridge are released into the anode solution to balance the excess cations, and some
cations from the solution will also enter the salt bridge; cations in the salt bridge are released into the
cathode solution to balance the excess anions, and some anions from the solution will also enter the salt
bridge. The salt bridge is necessary to complete the circuit and to maintain electrical neutrality.

Electrolysis of concentrated NaCl solution

For concentrated NaCl solution, the higher concentration of Cl- causes the position of equilibrium
Cl2 + 2 e- <-> 2Clto shift to the left according to Le Chateliers Principle. This results in E(Cl2/Cl-) becoming less positive
than E(O2/H2O). Thus Cl- is preferentially oxidised at the anode instead of H2O.
At the cathode, the difference between E(Na+/Na) -2.71 V and E(H2O/H2) -0.83 V is too large; even
concentrated solution cannot make the value of E(Na+/Na) to be more positive than -0.83 V. Water is
still preferentially reduced.

Electrolytic purification of copper (half equations are omitted)

E(Ni2+/Ni) is the least positive of the four values, and E(Cu2+/Cu) is the 2nd least positive. Ni and Cu are
preferentially oxidised at anode. The anode dissolves. Ag in the impure copper is not oxidised due to
unfavourable electrode potentials, hence it sinks to the bottom once Cu dissolves as the anode sludge
and is collected.
At the cathode, since E(Cu2+/Cu) is the most positive, Cu2+ will be preferentially reduced and Cu metal
will deposit on the cathode. Ni2+ and H2O will not be reduced due to unfavourable electrode potentials.

Geometric isomerism affecting melting/boiling points

The cis isomers tend to have higher boiling points because they tend to be more polar.
The trans isomers tend to have high melting points because they pack better due to their high
symmetry. The dispersion force work more effectively in holding the molecules together, hence more
energy is needed to overcome the forces of attraction.

Effects of CFCs on the ozone layer

In the stratosphere, oxygen atoms are produced when O2 atoms absorb UV light at 250nm wavelength.
Once oxygen atoms form, they can react with oxygen molecules to produce ozone, which by absorption
of UV light, decomposes to reform oxygen atoms and molecules. An equilibrium is set up. CFCs act as a
homogeneous catalyst for the destruction of ozone, and the process uses up the oxygen atoms needed
to make more ozone by the natural ozone formation reaction.