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Assumed Knowledge
Acid - proton donor
Base - proton acceptor
Acidic oxides (non-metals) react with water to make acids or
bases to form salts (CO2). Basic oxides (metals) react with acids to
form salts but do not react with alkaline solutions (CuO, Fe 2O3).
Amphoteric oxides (Al, Zn, Pb, Sn) react with acids or bases to form
salts. Neutral oxides (CO, N2O) dont react.
acid + metal H2 + salt
acid + carbonate CO2 + H2O + salt
Gases
Distinguishing properties of gases:
very compressible
flow rapidly
take shape of and fill a container (liquids only take
shape)
expand and contract with temperature changes (more
so than liquids, solids is near negligible)
infinitely expandable (unlike liquids, solids)
low density
Gas variables:
Pressure (Pa)
=force/area. Due to particles in motion, colliding with
momentum into each other and walls. 1Pa = 1N/m 2 = 1J/m3
(1N = 1kgm/s2)
1atm
=
760mmHg/Torr
Manometer - measures
difference in pressure
= 101325Pa
= 101.325kPa
= 1.01325bar
= 14.7psi
Barometer - measures
atmospheric pressure
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PV = nRT where
Universal
Gas
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Lyman = UV
Balmer = visible light
Paschen = IR
The value of n for each energy level/shell is the principal
quantum number. The ground state is an atoms lowest state,
however it can undergo transitions to higher excited states by
heating or colliding energetically with other bodies. These are
unstable and result in the lowering of energy levels by emission of
photons.
Complete removal of an electron means the electron has been
moved to n=. The energy required to move a valence electron
upwards is called the ionisation energy.
Solutions to the Schrdinger equation have exact analytical
forms for the hydrogen atom:
=E
where
= Hamiltonian (an operator that corresponds to the
total energy of the system
- encompasses nature of proton
and electron particles and their Coulombic attraction [the
electrostatic attraction or repulsion between protons and
electrons])
E = energy of the state (a constant of proportionality)
(psi) = the wavefunction
An eigenstate (or orbital) is an allowed energy (or shell) under
the contraints of the Schrdinger equation (labelled by quantum
numbers - they are the outcomes or results when solving the
equation). These are wave-like states with 3D shape and amplitude
(this form is a direct consequence of the Schrdinger equation. The
electron density (probability of an electron being at a certain point)
is given by the square of the wavefunction (however the Heisenberg
uncertainty principle limits the ability to know both the position and
energy (thus speed) of a quantum particle like an electron):
=2
As the electron could be at any distance from the nucleus (although
further is less probable, the volume with a 90% chance of an
electron being there is called the boundary surface, and this
surface is thought of as the spatial limit of the atomic orbital. There
are four quantum numbers to label each electron:
principal quantum number (n) - 1, 2, 3, ,
azimuthal (angular momentum) quantum number (l) - 0,
1, 2, , (n-1)
magnetic quantum number (ml) - 0, 1, 2, , l (but
counted from negative to positive: -l, -l+1, , 0, , l-1, l)
spin quantum number (ms) -
A set of orbitals with the same n are called a shell (in hydrogen
all orbitals are in the same shell as there is one electron), and a set
of orbitals with the same n and l are part of the same sub-shell,
labelled by letters (called orbital symbols):
if l=0 s orbital
if l=1 its a p orbital
Remember: Spadoof!
if l=2 its a d orbital
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1s 22s22p4
[He]2p 4
Once you get to the point where 4s is before the 3d due to less
shielding (greater penetration to the nucleus), the 4s is listed before
the 3d.
A different method uses locations on the
periodic table, where the core part of the
configuration is given by the noble gas from the
period above, and the valence part is given by
counting from the left of the table to the element
and filling in shells as you go (staying aware of the
Cr and Cu anomalies).
Anion ground-state electron configuration is simply adds the
number of required electrons to the next available positions,
following the aufbau principle.
Cations are usually done the same way except removing the
last added electrons, with an exception: in neutral atoms, the 4s is
more stable than the 3d and filled up first, but in transition metal
cations, the reverse is true, so all their valence electrons reside in
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the d orbitals and it is these that are removed whilst the d remain
filled.
Fe
[Ar]4s23d6
Fe+ [Ar]3d7
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Elements with low 1st IEs usually lose electrons to form cations,
whilst those with high 1st IEs gain electrons to become anions. IEs
decrease down groups (shielding pushes
electrons out, lower energy required), but
increase across a period from left to right
(greater nuclear charge), however whenever a
subshell has reached a filled or half-filled state,
there will be a small jump.
Electron affinity is the opposite of
ionisation energy, being the energy change
when a gaseous atom gains an electron to
form a gaseous anion (atom (g) + e- (g)
anion- (g)). EAs are negative as the system
loses energy (energy is released, exothermic), and hence larger
negative values are favoured (unlike IE), being located at the top
right of the periodic table. Group II elements have the greatest
electron affinity (being large and positive - represented as zero on
the graph as positive values can only be estimated through
calculations, not measured) as this would result in starting a new,
more unstable orbital.
Bonding Theory and States of Matter
When complete transfer of one or more electrons occurs from
one atom to another, it is an ionic bond (although this never
completely happens, and is very weakly covalent). If main electron
density of the bonding electrons moves to a region between the
atoms, it is a covalent bond, and if it is intermediate (electrons
generally closer to one atom than the other), it is a polar covalent
bond (ionic bonds can be thought of as extreme versions of these. A
special case of covalent bonding is metallic bonding, where the
valence electrons are not localised but instead move freely through
the metal body.
Electronegativity is a means to predict which of these a
compound is, where if there difference in the electronegativity of
two atoms is:
>1.7 ionic
0.4-1.7 polar covalent
<0.4 mostly covalent (or simply covalent)
0 non-polar covalent (or simply covalent)
In polar bonds, bond polarity can be shown with a dipole
arrow (pointing from the positive to the negative (sometimes with a
small vertical line at the positive end to make a + shape). As these
are vectors, they can be combined to give an overall molecular
dipole moment.
The attractive forces between molecules (van der Waals
forces) are weak and take little energy to break in melting/boiling
processes, and hence the more ionic a substance the higher its
melting/boiling point. Some binary polar-covalent compounds dont
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6 (AX6)
Octahedr
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al
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linear
sp2
trigonal
planar
sp3
tetrahed
ral
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equal to the number of atomic orbitals that made them, the bonding
orbitals are lower than the atomic orbitals from which they were
formed whilst antibonding is higher. It follows both Pauli exclusion
principle and Hunds rule, and they form best when composed of
atomic orbitals of like energies. In heteronuclear diatomics, the
more electronegative atom will have lower atomic orbital energies
(as energies are negative and it requires more energy to pull out an
atom). The bigger the difference in energies (or electronegativity),
the greater the chance of orbital mixing (so NO does not have
orbital mixing, whilst CO does) as the different orbitals (e.g. the 1s
of one and the 2pz of another) are likely to cross. Additionally, if both
atoms are below nitrogen (as in CN -) there will also be orbital
mixing. Another means of deducing this is by considering what
something is isoelectronic (having the same electron configuration)
with. So CO would be the same as N2, and hence has orbital mixing.
Intermolecular Forces
The state of a substance (the boiling/melting point) depends
on the strength and nature of the forces between atoms/molecules
of a substance:
Dispersion forces - a molecule with no
permanent dipole that can become
temporarily polar when collisions induce
unsymmetrical
electron
distributions
(distortions of the electron cloud), occurring
in all molecules; polarisability is the ease of
distortion and determines the strength of the force,
increasing with the number of electrons present (as
more electrons means larger molecule which means less
electronegative); molecular shape also determines
strength of the force, with a higher SA:V ratio (so more
SA) being higher forces as they are more polarisable
Dipole-dipole - two molecules with permanent dipole
moments attract each other by the approach of
oppositely charged ends, which can be caused by
asymmetric structure or peripheral atoms of differing
electronegativity, and we label this with + and - or an
arrow
pointing
from
positivenegative with a
perpendicular line through it at the positive end
Hydrogen bonding - the strongest intermolecular force
is the result of a dipole-dipole interaction between a
strongly polarised H (due to high electronegativity of
O/N/F-H) and an O, N or F (note: requires two of these
high electronegativity atoms, one to create the dipole,
the other to bond with; it is almost 10 stronger than
other intermolecular forces, dominating molecular
properties (evident in binary compounds as boiling point
increases drastically despite smaller molecular size); has
the form: donor-Hacceptor (the donor makes the H+,
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Non-Ideal
Gases
The
ideal gas laws
make two assumptions:
there is no attractive force between atoms/molecules
the volume of the atoms/molecules is negligible
In a compressibility isotherm
(graph), we can plot the gas equation
ratio (which should always be 1 in an
ideal gas) against pressure. At 0
pressure, the ratio is 1, however as it
increases it deviates below 1 as
intermolecular forces play a role,
attracting the molecules and reducing
volume, and hence the ratio. However,
as volume of the total gas decreases
the volume of each particle becomes
significant, stopping the volume from
becoming any smaller until the ratio
begins to increase (as pressure is still
increasing but volume isnt decreasing
as much) so it surpasses 1. In noble gases, there are so few
intermolecular forces (as molecules are monatomic and hence
dispersion forces small), so they dont really dip down. If forces
arent as strong (for example, less available valence electrons in N 2
and CH4 compared to halogens), then the dip down is not as strong.
If the volume of the molecules is larger, then the effects of volume
push up the ratio faster as they come into play with a larger effect
sooner.
To correct for this, we use the van der Waals equation:
The pressure correction term (first bracket) takes into account
the intermolecular forces (note: a = strength of intermolecular
forces; larger a means stronger; added as pressure increases). The
volume correction (second bracket) accounts for the molecular
volume (note: b = volume of gas molecules; larger b means larger
molecules, less free volume; subtracted as free volume decreases).
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Liquids are one of the rarest phases, being the narrow phases
where kinetic energy means the substance cannot remain
independent but it higher enough to ensure free movement. They
have a specific volume like solids, but are fluid like gases. They have
three important properties:
Surface Tension - resistance of a liquid to increase its
surface area due to cohesion from the intermolecular
forces between the molecules, with surface molecules
being pulled back into the main body
Capillary Action - adhesive (with cohesion) that leads
water to climb through small-diameter tubes, only
limited by gravity; leads to meniscus
Viscosity - dependent on strength of intermolecular
forces (slows it down) and molecular shape (more
surface area means more places to have forces or to
bump into each other); also dependent upon
temperature, as increasing kinetic
energies allows greater movement by
overcoming intermolecular forces
All substances have a kinetic energy
distribution, so even in a liquid phase some will
continuously vaporise to become gaseous. The
partial pressure of a liquid in a closed container
gradually increases once the system has been
sealed as some gas molecules are released,
however eventually an equilibrium is reached
where the number of molecules that leave the
liquid is the same as the number of gas molecules
that collide with and are recaptured by the liquid. The partial
pressure of the gas above the liquid at equilibrium
is called the vapour pressure of the liquid.
Vapour pressure is approximately proportional to
the a constant from the van der Waals equation.
The temperature at which the vapour
pressure of a substance in an open container
reaches the external pressure is called the boiling
point, and if this occurs at 1atm this is the
normal boiling point.
Phase Changes
Phase
changes
depend
on
intermolecular
and
bonding
(intramolecular) forces. Phase changes
require energy, and hence as heat is
added at particular changes of phase the
energy is not added as temperature but
used as kinetic energy to overcome the
intermolecular forces. Hence temperature
does not increase at these phases.
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If the A:B intermolecular forces are weaker than A:A and B:B,
then the vapour pressure will be higher than expected (as less is
being stored as the solution), resulting in a positive deviation.
Conversely, if they are stronger, more will be stored in solution and
there will be a lower vapour pressure (negative deviation).
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(basicity constant)
Acids are stronger (easier to remove protons) with a higher K a
but lower pKa, and similarly bases are stronger with a higher K b and
lower pKb. For an acid and its conjugate base (or this could be
written vice versa; base with conjugate acid - same thing):
HA + H2O A- + H3O+ Ka
A- + H2O HA + OHKb
+
2H2O H3O + OH Ka Kb = Kw = 10-14
Therefore:
pKa + pKb = pKw =
14
Many acids (particularly organic ones) have more than one
proton that can react with water, and hence are polyprotic. As the
protons may have different bond strengths, they have different
values for pKa. Those attached to more electronegative atoms (like
oxygen) will have a lower pKa and hence dissociate more (as the Ocan then H-bond with H3O+/H2O, filling in this space and limiting the
ability of an H+ to come back and bond, and thus making it a strong
acid). Even when there are identical protons, the pK a for removing
the first is different to the second (as the molecule is now slightly
negative and has a tighter control on its H +). These are written as
pKa (1), pKa (2), and so on. Whilst in the form HA - (losing a proton in
a diprotic acid), they become amphiprotic (becoming either H 2A or
A2-), and you can determine whether they will go acidic or basic by
looking at the pKa (2) and pKb (14 - pKa (1)), converting to Ka and Kb,
and then the larger equilibrium constant will win out (as it produces
more of those products), determining if it is an acid or base.
Zwitterions are molecules that contain both positive and
negative charges (that do not combine), making it overall neutral
(e.g. the amino acid glycine). This means it has both an acidic and a
basic end.
When looking at the pH of salts, consider the anion and cation
differently. If they form part of a strong acid or base, the anion or
cation (respectively), they will be extremely weak conjugates, and
hence not react with water nor alter pH. Weak acids and bases have
moderate-strong conjugates, which can raise or lower the pH.
However if both ions are weak, then we need to consider their Ks
(NOT pK), and the one with the greater equilibrium constant will
produce more product and hence determine if it is acidic or basic
(that is, if Ka > Kb, it is acidic).
Note that when solving equilibriums with acids and bases, we
can only make a small x approximation for [HA] when the initial [HA]
is 400Ka. Also, if the concentration of the acid or base is less than
10-5, then the autoprotolysis of water must be considered, and
rather than using the initial [H3O+] or [OH-] of water as 0 (as we
have been approximating), we must now use 10-7.
Consider CH3COOH (aq) + H2O (l) H3O+ (aq) + CH3COO- (aq).
If we were the add CH3COONa, be Le Chateliers principle, the
equilibrium will shift left to minimise the change, and hence will
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cup calorimeter that is also thermally insulted, and usually used for
liquids in heat of dissolution, heat capacity of solids and aqueous
reactions.
We can have enthalpy of vaporisation
(Hvap>0 as you have to overcome
intermolecular forces) is the energy
required to go from liquid to gas (in J/mol),
enthalpy of combustion (Hc<0 as you are
releasing energy by forming new bonds) is
burning in oxygen, and enthalpy of
atomisation (Hatom>0 as you have to put
in energy to break the bonds) is splitting a
substance into each individual atom (not even into H 2, but 2H).
Atomisation enthalpies can be found by summing all the individual
bond enthalpies. In any chemical reaction (assuming states remain
the same), such as combustion, we can approximate the enthalpy
by finding the atomisation enthalpy and then adding the negative
values of the products bond enthalpies (basically final-initial but
using an alternate pathway). This is Hesss Law: if you add up
chemical equations to form a new overall equation, then the overall
enthalpy is the sum of the individual enthalpies. However in this
case it is only approximate as bond energies depend on the entire
molecule, not just the two atoms involved, and the values on tables
are mere averages (for example we would predict CHClBr 2 wouldnt
decompose in the stratosphere as bond energies appear higher than
the energy of the light there, but in actuality the bond energies are
lower). So instead of using bond enthalpies (which are hard to
measure as isolated atoms in the gas are difficult to measure
experimentally), we use atoms in the state they are most commonly
found in, or their standard state, occurring at 1 bar (105 Pa), 298K
and 1M, and this is denoted by a o (e.g. Ho). Now we use
enthalpy/heat of formation (fHo). For an element in its standard
state (e.g. O2 (g), Fe (s)), fHo = 0. In this, we look at the energy
required to make the products and subtract the energy required to
make the reactants:
rH = fH (products) - fH (reactants)
We can use this to predict the properties of different
substances, for example the thermite reaction (Fe 2O3 + 2Al) is highly
exothermic so we know the safety precautions to use. The thermite
reaction is used to weld railroad tracks (when there is no electricity),
and a variant is used as an igniter for rocket fuel.
A spontaneous reaction means once it has started it will
continue on its own, whilst a non-spontaneous reaction must
constantly have energy applied for it to run, or otherwise it will stop.
H is not the only criterion for spontaneity (despite most exothermic
reactions (H<0) being spontaneous, and the more exothermic the
more vigorous), as endothermic reactions like that between barium
hydroxide and ammonium nitrate can also be spontaneous. The
other criterion is entropy.
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